POSITIVE ELECTRODE PLATE, SECONDARY BATTERY AND POWER CONSUMING DEVICE
20230420677 ยท 2023-12-28
Assignee
Inventors
Cpc classification
H01M4/5825
ELECTRICITY
H01M4/505
ELECTRICITY
H01M4/583
ELECTRICITY
H01M2220/20
ELECTRICITY
International classification
H01M4/505
ELECTRICITY
H01M4/58
ELECTRICITY
H01M4/583
ELECTRICITY
H01M4/36
ELECTRICITY
H01M4/62
ELECTRICITY
Abstract
The present application provides a positive electrode plate, a secondary battery and a power consuming device. The positive electrode plate may comprise a positive electrode current collector, a positive electrode film layer provided on at least one surface of the positive electrode current collector, and a conductive undercoat layer between the positive electrode current collector and the positive electrode film layer, wherein the positive electrode film layer may include a positive electrode film layer comprising a positive electrode active material with a core-shell structure, the positive electrode active material may comprise an inner core and a shell coating the inner core, and the conductive primer layer may comprise a first polymer, a first water-based binder and a first conductive agent.
Claims
1. A positive electrode plate, comprising a positive electrode current collector, a positive electrode film layer provided on at least one surface of the positive electrode current collector, and a conductive undercoat layer between the positive electrode current collector and the positive electrode film layer, wherein the positive electrode film layer comprises a positive electrode active material with a core-shell structure; the positive electrode active material comprises an inner core and a shell coating the inner core; the inner core includes Li.sub.1+xMn.sub.1yA.sub.yP.sub.1zR.sub.zO.sub.4, where x=0.100 to 0.100, y=0.001 to 0.005, z=0.001 to 0.100, A is selected from one or more of Zn, Al, Na, K, Mg, Mo, W, Ti, V, Zr, Fe, Ni, Co, Ga, Sn, Sb, Nb and Ge, and R is selected from one or more of B, Si, N and S; the shell includes a first coating layer coating the inner core and a second coating layer coating the first coating layer, wherein the first coating layer includes pyrophosphate of MP.sub.2O.sub.7 and phosphate of XPO.sub.4, wherein M and X are each independently selected from one or more of Li, Fe, Ni, Mg, Co, Cu, Zn, Ti, Ag, Zr, Nb or Al; and the second coating layer includes carbon; and the conductive undercoat layer includes a first polymer, a first water-based binder, and a first conductive agent, wherein the first polymer comprises a first monomer unit represented by formula 1; a second monomer unit selected from at least one of a group consisting of a monomer unit represented by formula 2 and a monomer unit represented by formula 3; a third monomer unit selected from at least one of a group consisting of a monomer unit represented by formula 4 and a monomer unit represented by formula 5; and a fourth monomer unit represented by formula 6, in which R.sup.1, R.sup.2, and R.sup.3 each independently represent H, a carboxyl, an ester group, and groups of substituted or unsubstituted C1-C10 alkyl, C1-C10 alkoxy, C2-C10 alkenyl, and C6-C10 aryl, and R.sup.4 represents H, and groups of substituted or unsubstituted C1-C10 alkyl, C1-C10 alkoxy, C2-C10 alkenyl, and C6-C10 aryl; ##STR00014##
2. The positive electrode plate according to claim 1, wherein based on the total mass of the first polymer, the mass percentage content of the first monomer unit is M1, and M1 is 10%-55%; and/or the mass percentage content of the second monomer unit is M2, and M2 is 40%-80%; and/or the mass percentage content of the third monomer unit is M3, and M3 is 0%-10%; and/or the mass percentage content of the fourth monomer unit is M4, and M4 is 0%-10%.
3. The positive electrode plate according to claim 2, wherein M3/(M2+M3) is 0%-5%.
4. The positive electrode plate according to claim 1, wherein the first polymer includes one or more selected from hydrogenated nitrile rubbers, and hydrogenated carboxylated nitrile rubbers; and/or the first polymer has a weight-average molecular weight of 50,000 -1,500,000.
5. The positive electrode plate according to claim 1, wherein the first water-based binder includes one or more selected from a water-based polyacrylic resin and a derivative thereof, a water-based amino-modified polypropylene resin and a derivative thereof, and a polyvinyl alcohol and a derivative thereof; and/or the first water-based binder has a weight-average molecular weight of 200,000 -1,500,000.
6. The positive electrode plate according to claim 1, wherein the first conductive agent includes one or more selected from superconductive carbon, conductive graphite, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
7. The positive electrode plate according to claim 1, wherein based on the total mass of the conductive undercoat layer, the mass percentage content of the first polymer is X1, and X1 is 5%-20%; and/or the mass percentage content of the first water-based binder is X2, and X2 is 30%-80%; and/or the mass percentage content of the first conductive agent is X3, and X3 is 10%-50%.
8. The positive electrode plate according to claim 1, wherein the conductive undercoat layer has a thickness of 1 m -20 m.
9. The positive electrode plate according to claim 1, wherein the positive electrode film layer further includes one or more selected from an infiltration agent and a dispersant.
10. The positive electrode plate according to claim 9, wherein the infiltration agent has a surface tension of 20 mN/m -40 mN/m, and optionally, the infiltration agent includes at least one of the functional groups of: CN, NH.sub.2, NH, N, OH, COO, and C(O)OC(O).
11. The positive electrode plate according to claim 9, wherein the infiltration agent includes one or more selected from a small molecule organic solvent and a low molecular weight polymer, and optionally, the small molecule organic solvent includes one or more selected from an alcohol amine compound, an alcohol compound, and a nitrile compound, and optionally, the alcohol amine compound has a number of carbon atom of 1-16; and optionally, the low molecular weight polymer includes one or more selected from a maleic anhydride-styrene copolymer, polyvinylpyrrolidone, and polysiloxane, and optionally, the low molecular weight polymer has a weight-average molecular weight of no more than 6000.
12. The positive electrode plate according to claim 9, wherein the dispersant includes a second polymer, and the second polymer comprises: a fifth monomer unit represented by formula 7; a sixth monomer unit selected from at least one of a group consisting of a monomer unit represented by formula 8 and a monomer unit represented by formula 9; and a seventh monomer unit selected from at least one of a group consisting of a monomer unit represented by formula 10 and a monomer unit represented by formula 11; ##STR00015##
13. The positive electrode plate according to claim 12, wherein based on the total mass of the second polymer, the mass percentage content of the fifth monomer unit is M5, and M5 is 10%-55%; and/or the mass percentage content of the sixth monomer unit is M6, and M6 is 40%-80%; and/or the mass percentage content of the seventh monomer unit is M7, and M7 is 0%-10%.
14. The positive electrode plate according to claim 13, wherein M7/(M6+M7) is 0%-5%.
15. The positive electrode plate according to claim 12, wherein the second polymer is a hydrogenated nitrile rubber; and/or the second polymer has a weight-average molecular weight of 50,000 -500,000.
16. The positive electrode plate according to claim 9, wherein based on the total mass of the positive electrode film layer, the mass percentage content of the dispersant is Y1, and Y1 is 0.05%-1%; and/or the mass percentage content of the infiltration agent is Y2, and Y2 is 0.05%-2%.
17. The positive electrode plate according to claim 16, wherein Y1/Y2 is 0.05-20.
18. The positive electrode plate according to claim 9, wherein in the positive electrode plate, the mass ratio of the first polymer to the second polymer is 1.5-5.
19. The positive electrode plate according to claim 1, wherein the first coating layer has an interplanar spacing of the phosphate of 0.345-0.358 nm, and an angle of the crystal direction (111) of 24.25-26.45; and the first coating layer has an interplanar spacing of the pyrophosphate of 0.293-0.326 nm, and an angle of the crystal direction (111) of 26.41-32.57.
20. The positive electrode plate according to claim 1, wherein in the inner core, the ratio of y to 1-y is 1:10 to 10:1; and/or in the inner core, the ratio of z to 1-z is 1:9 to 1:999.
21. The positive electrode plate according to claim 1, wherein the coating amount of the first coating layer is greater than 0 wt % and less than or equal to 7 wt %, based on the weight of the inner core.
22. The positive electrode plate according to claim 1, wherein the weight ratio of the pyrophosphate to phosphate in the first coating layer is 1:3 to 3:1.
23. The positive electrode plate according to claim 1, wherein the pyrophosphate and the phosphate each independently have a crystallinity of 10% to 100%.
24. The positive electrode plate according to claim 1, wherein the coating amount of the second coating layer is greater than 0 wt % and less than or equal to 6 wt %, based on the weight of the inner core.
25. The positive electrode plate according to claim 1, wherein A is selected from at least two of Fe, Ti, V, Ni, Co and Mg.
26. The positive electrode plate according to claim 1, wherein the Li/Mn antisite defect concentration of the positive electrode active material is 4% or less.
27. The positive electrode plate according to claim 1, wherein the lattice change 10 rate of the positive electrode active material is 6% or less.
28. The positive electrode plate according to claim 1, wherein the surface oxygen valence state of the positive electrode active material is no more than 1.88.
29. The positive electrode plate according to claim 1, wherein the compacted density of the positive electrode active material under 3 ton is 2.0 g/cm.sup.3 or more.
30. A secondary battery, comprising a positive electrode plate according to claim 1.
31. A power consuming device, comprising a secondary battery according to claim
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0120]
[0121]
[0122]
[0123]
[0124]
[0125]
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[0127]
[0128]
[0129]
LIST OF REFERENCE SIGNS
[0130] 1 battery pack; 2 upper box body; 3 lower box body; 4 battery module; 5 secondary battery; 51 housing; 52 electrode assembly; 53 top cover assembly; 11 positive electrode current collector; 112 surface; 12 conductive undercoat layer; 13 positive electrode film layer; 510 steel plate; 520 double-sided tape; 530 electrode plate;
DETAILED DESCRIPTION OF EMBODIMENTS
[0131] Hereinafter, embodiments of a positive electrode active material and a preparation method therefor, a positive electrode plate, a negative electrode plate, a secondary battery, a battery module, a battery pack, and a device of the present application are described in detail and specifically disclosed with reference to the accompanying drawings as appropriate. However, unnecessary detailed illustrations may be omitted in some instances. For example, there are situations where detailed description of well known items and repeated description of actually identical structures are omitted. This is to prevent the following description from being unnecessarily verbose, and facilitates understanding by those skilled in the art. Moreover, the accompanying drawings and the descriptions below are provided for enabling those skilled in the art to fully understand the present application, rather than limiting the subject matter disclosed in claims.
[0132] Ranges disclosed in the present application are defined in the form of lower and upper limits, and a given range is defined by selection of a lower limit and an upper limit, the selected lower and upper limits defining the boundaries of the particular range.
[0133] Ranges defined in this manner may be inclusive or exclusive, and may be arbitrarily combined, that is, any lower limit may be combined with any upper limit to form a range. For example, if the ranges of 60-120 and 80-110 are listed for a particular parameter, it should be understood that the ranges of 60-110 and 80-120 are also contemplated. Additionally, if minimum range values 1 and 2 are listed, and maximum range values 3, 4, and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In the present application, unless stated otherwise, the numerical range a-b denotes an abbreviated representation of any combination of real numbers between a and b, where both a and b are real numbers. For example, the numerical range 0-5 means that all real numbers between 0-5 have been listed herein, and 0-5 is just an abbreviated representation of combinations of these numerical values. In addition, when a parameter is expressed as an integer of 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, and the like.
[0134] All the implementations and optional implementations of the present application can be combined with one another to form new technical solutions, unless otherwise stated.
[0135] All technical features and optional technical features of the present application can be combined with one another to form a new technical solution, unless otherwise stated.
[0136] Unless otherwise stated, all the steps of the present application can be carried out sequentially or randomly, preferably sequentially. For example, the method including steps (a) and (b) indicates that the method may include steps (a) and (b) performed sequentially, and may also include steps (b) and (a) performed sequentially. For example, reference to the method may further include step (c) indicates that step (c) may be added to the method in any order, e.g., the method may include steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc.
[0137] The terms comprise and include mentioned in the present application are open-ended or closed-ended, unless otherwise stated. For example, comprise and include may mean that other components not listed may further be comprised or included, or only the listed components may be comprised or included.
[0138] In the present application, the term or is inclusive unless otherwise specified. For example, the phrase A or B means A, B, or both A and B. More specifically, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present); A is false (or not present) and B is true (or present); or both A and B are true (or present).
Secondary Battery
[0139] A secondary battery, also known as a rechargeable battery or an accumulator, refers to a battery of which active materials can be activated by means of charging for reuse of the battery after the battery is discharged.
[0140] Generally, the secondary battery comprises a positive electrode plate, a negative electrode plate, a separator and an electrolyte. During a charge/discharge process of the battery, active ions (e.g., lithium ions) are intercalated and de-intercalated back and forth between the positive electrode plate and the negative electrode plate. The separator is provided between the positive electrode plate and the negative electrode plate, and mainly prevents positive and negative electrodes from short-circuiting and enables the active ions to pass through. The electrolyte is provided between the positive electrode plate and the negative electrode plate and mainly functions for active ion conduction.
[Positive Electrode Plate]
[0141] In a first aspect, the present application provides a positive electrode plate, comprising a positive electrode current collector, a positive electrode film layer provided on at least one surface of the positive electrode current collector, and a conductive undercoat layer between the positive electrode current collector and the positive electrode film layer, wherein [0142] the positive electrode film layer comprises a positive electrode active material with a core-shell structure; the positive electrode active material comprises an inner core and a shell coating the inner core; [0143] the inner core includes Li.sub.1+xMn.sub.1yA.sub.yP.sub.1zR.sub.zO.sub.4, where x=0.100 to 0.100, y=0.001 to 0.500, z=0.001 to 0.100; A is selected from one or more of Zn, Al, Na, K, Mg, Mo, W, Ti, V, Zr, Fe, Ni, Co, Ga, Sn, Sb, Nb and Ge, optionally one or more of Fe, Ti, V, Ni, Co and Mg; and R is selected from one or more of B, Si, N and S; [0144] the shell includes a first coating layer coating the inner core and a second coating layer coating the first coating layer, wherein [0145] the first coating layer includes pyrophosphate of MP.sub.2O.sub.7 and phosphate of XPO.sub.4, wherein M and X are each independently selected from one or more of Li, Fe, Ni, Mg, Co, Cu, Zn, Ti, Ag, Zr, Nb or Al; and [0146] the second coating layer includes carbon; and [0147] the conductive undercoat layer includes a first polymer, a first water-based binder, and a first conductive agent, [0148] the first polymer comprises [0149] a first monomer unit represented by formula 1; [0150] a second monomer unit selected from at least one of a group consisting of a monomer unit represented by formula 2 and a monomer unit represented by formula 3; [0151] a third monomer unit selected from at least one of a group consisting of a monomer unit represented by formula 4 and a monomer unit represented by formula 5; and [0152] a fourth monomer unit represented by formula 6, in which R.sup.1, R.sup.2, and R.sup.3 each independently represent H, a carboxyl, an ester group, and groups of substituted or unsubstituted C1-C10 alkyl, C1-C10 alkoxy, C2-C10 alkenyl, and C6-C10 aryl, and R.sup.4 C10 alkenyl, and C6-C10 aryl;
##STR00003##
[0153] In the positive electrode plate based on the above solution, the positive electrode film layer and the positive electrode current collector have enhanced bonding strength. Without being limited by theory, during the process of coating the surface of the conductive undercoat layer with the positive electrode active material slurry (containing a solvent of N-methylpyrrolidone, referred to as NMP for short), the first polymer in the conductive undercoat layer will be dissolved again after coming into contact with the solvent of NMP, so as to interdiffuse with the positive electrode active material slurry, and after curing, the active material layer can be integrated with the undercoat layer, thereby effectively increasing the bonding strength between the positive electrode film layer and the positive electrode current collector.
[0154] In some embodiments, the first polymer is a random copolymer.
[0155] Nitrile rubber (NBR) is a random copolymer formed by polymerization (such as emulsion polymerization) of acrylonitrile and butadiene monomers, and has a general structure of:
##STR00004##
[0156] In the nitrile rubber, butadiene (B) and acrylonitrile (A) segments are generally linked in a manner of BAB, BBA or ABB, ABA and BBB tridas, but with the increase of acrylonitrile content, there are also AABAA linked in pentad, and even as a bulk acrylonitrile polymer. In the nitrile rubber, the sequence distribution of butadiene is mainly in a trans-1,4 structure, and the microstructure thereof depends on the polymerization conditions.
[0157] A hydrogenated nitrile rubber (HNBR) refers to the product obtained by hydrogenating the carbon-carbon double bonds on the molecular chain of a nitrile rubber to partial or full saturation. The chemical formula of a fully saturated hydrogenated nitrile rubber is as follows:
##STR00005##
[0158] There are three main methods for the preparation of a hydrogenated nitrile rubber (HNBR): an ethylene-acrylonitrile copolymerization method, an NBR solution hydrogenation method and an NBR emulsion hydrogenation method.
[0159] A hydrogenated carboxybutyl rubber (HXNBR) is a polymer formed by copolymerization of nitrile (such as acrylonitrile), a conjugated diene (such as butadiene) and an ester of a unsaturated carboxylic acid, followed by selective hydrogenation of CC.
[0160] The so-called hydrogenated carboxybutyl rubber involves the further introduction of carboxyl groups on the basis of a hydrogenated nitrile rubber.
[0161] The ester of an unsaturated carboxylic acids includes, for example, an ester of an ,-unsaturated monocarboxylic acid. The esters of ,-unsaturated monocarboxylic acids which can be used are the alkyl esters and alkoxyalkyl esters thereof; optionally, alkyl esters of ,-unsaturated monocarboxylic acids, such as C1-C18 alkyl esters, optionally alkyl esters of acrylic acid or methacrylic acid, such as C1-C18 alkyl esters, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, n-dodecyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate; also optionally alkoxyalkyl esters of ,-unsaturated monocarboxylic acids, optionally alkoxyalkyl esters of acrylic or methacrylic acid, for example C2-C12-alkoxyalkyl of acrylic or methacrylic acid, very optionally methoxymethyl acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate and methoxyethyl (meth)acrylate. Mixtures of alkyl esters such as those described above with alkoxyalkyl esters such as those described above may also be used. Hydroxyalkyl acrylate and hydroxyalkyl methacrylate in which the number of carbon atoms in the hydroxyalkyl group is 1-12 can also be used, for example 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 3-hydroxypropyl acrylate. Likewise, epoxy-containing esters such as glycidyl methacrylate may be used. Cyanoalkyl acrylates and cyanoalkyl methacrylates with 2-12 C atoms in the cyanoalkyl can also be used, for example -cyanoethyl acrylate, -cyanoethyl acrylate and cyanobutyl methacrylate. Acrylates or methacrylates containing fluorine-substituted benzyl groups can also be used, for example, fluorobenzyl acrylate and fluorobenzyl methacrylate. Acrylates and methacrylates containing fluoroalkyl groups can also be used, for example trifluoroethyl acrylate and tetrafluoropropyl methacrylate. Amino group-containing ,-unsaturated carboxylic acid esters such as dimethylaminomethyl acrylate and diethylaminoethyl acrylate can also be used.
[0162] In some embodiments, based on the total mass of the first polymer, [0163] the mass percentage content of the first monomer unit is M1, and M1 is 10%-55%, optionally 25%-55%; and/or [0164] the mass percentage content of the second monomer unit is M2, and M2 is 40%-80%, optionally 50%-70%; and/or [0165] the mass percentage content of the third monomer unit is M3, and M3 is 0%-10%, optionally 0.001%-2%; and/or [0166] the mass percentage content of the fourth monomer unit is M4, and M4 is 0%-10%, optionally 0.1%-1%.
[0167] The conductive undercoat layer based on this solution can be moderately dissolved during the coating process, thereby forming an enhanced bond with the positive electrode film layer.
[0168] In some embodiments, based on the total mass of the first polymer, [0169] the mass percentage content of the first monomer unit is M1, and M1 is 10%-55%, optionally 10%-15%, 15%-20%, 20%-25%, 25%-30%, 30%-35%, 35%-40%, 40% -45%, 45%-50% or 50%-55%; and/or [0170] the mass percentage content of the second monomer unit is M2, and M2 is 40%-80%, optionally 40%-45%, 45%-50%, 50%-55%, 55%-60%, 60%-65%, 65%-70%, 70% -75% or 75%-80%; and/or [0171] the mass percentage content of the third monomer unit is M3, M3 is 0%-10%, optionally 0.001%, -1%, 1%-2%, 2%-3%, 3%-4%, 4%-5%, 5%-6%, 6%-7%, 7%-8%, 8% -9% or 9%-10%; and/or [0172] the mass percentage content of the fourth monomer unit is M4, and M4 is 0%-10%, optionally 0.01%-1%, 1%-2%, 2%-3%, 3%-4%, 4%-5%, 5%-6%, 6%-7%, 7% -8%, 8%-9% or 9%-10% . The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved. The conductive undercoat layer based on this solution can be moderately dissolved during the coating process, thereby forming an enhanced bond with the positive electrode film layer.
[0173] In some embodiments, M3/(M2+M3) is 0%-5%, optionally 0.001%-1%. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0174] In some embodiments, M3/(M2+M3) is 0.01%-1%, 1%-2%, 2%-3%, 3%-4% or 4%-5%.
[0175] In some embodiments, the first polymer includes one or more selected from hydrogenated nitrile rubbers, and hydrogenated carboxylated nitrile rubbers; and/or, the weight-average molecular weight of the first polymer is 50,000-1,500,000, optionally 200,000-400,000. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0176] In some embodiments, the first polymer has a weight-average molecular weight of 100,000-300,000, 300,000-500,000, 500,000-700,000, 700,000-900,000, 900,000-1,100,000, 1,100,000-1,300,000 or 1,300,000-1,500,000.
[0177] In some embodiments, the first water-based binder includes one or more selected from a water-based polyacrylic resin and a derivative thereof, a water-based amino-modified polypropylene resin and a derivative thereof, and a polyvinyl alcohol and a derivative thereof, optionally a water-based acrylic acid-acrylate copolymers; and/or the first water-based binder has a weight-average molecular weight of 200,000-1,500,000, optionally 300,000-400,000. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0178] In some embodiments, the first water-based binder has a weight-average molecular weight of 100,000-300,000, 300,000-500,000, 500,000-700,000, 700,000-900,000, 900,000-1,100,000, or 1,100,000-1,300,000.
[0179] In some embodiments, the first conductive agent includes one or more selected from superconductive carbon, conductive graphite, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers, optionally one or more selected from carbon nanotubes, graphene, and carbon nanofibers. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0180] In some embodiments, based on the total mass of the conductive undercoat layer, [0181] the mass percentage content of the first polymer is X1, and X1 is 5%-20%, optionally 5%-10%; and/or [0182] the mass percentage content of the first water-based binder is X2, and X2 is 30%-80%, optionally 40%-50%; and/or [0183] the mass percentage content of the first conductive agent is X3, and X3 is 10%-50%, optionally 40%-50%. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0184] In some embodiments, the conductive undercoat layer has a thickness of 1 m-20 m, optionally 3 m -10 m. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0185] In some embodiments, the positive electrode film layer further includes one or more selected from an infiltration agent and a dispersant, optionally, the positive electrode film layer further includes both an infiltration agent and a dispersant. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0186] In some embodiments, the infiltration agent has a surface tension of 20 mN/m-40 mN/m, optionally, the infiltration agent includes at least one of the functional groups of: CN, NH.sub.2, NH, N, OH, COO, and C(O)OC(O). The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0187] In some embodiments, the surface tension can be measured using the Wilhelmy Plate Method. For the specific test steps, reference can be made to general standards in the field, such as GBT/22237-2008 Surface Active Agents-Determination of Surface Tension, such as ASTM D1331-14. Standard Test Methods for Surface and Interfacial Tension of Solutions of Paints, Solvents, and Solutions of Surface-Active Agents and Related Materials.
[0188] In some embodiments, the infiltration agent includes one or more selected from a small molecule organic solvent and a low molecular weight polymer.
[0189] Optionally, the small molecule organic solvent includes one or more selected from an alcohol amine compound, an alcohol compound, and a nitrile compound, and optionally, the alcohol amine compound has a number of carbon atom of 1-16, optionally 2-6.
[0190] Optionally, the low molecular weight polymer includes one or more selected from a maleic anhydride-styrene copolymer, polyvinylpyrrolidone, and polysiloxane, and optionally, the low molecular weight polymer has a weight-average molecular weight of no more than 6000, optionally 3000-6000. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0191] In some embodiments, the dispersant includes a second polymer, and the second polymer comprises: [0192] a fifth monomer unit represented by formula 7; [0193] a sixth monomer unit selected from at least one of a group consisting of a monomer unit represented by formula 8 and a monomer unit represented by formula 9; and [0194] a seventh monomer unit selected from at least one of a group consisting of a monomer unit represented by formula 10 and a monomer unit represented by formula 11;
##STR00006##
[0195] The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0196] In some embodiments, based on the total mass of the second polymer, [0197] the mass percentage content of the fifth monomer unit is M5, and M5 is 10%-55%, optionally 25%-55%; and/or [0198] the mass percentage content of the sixth monomer unit is M6, and M6 is 40%-80%, optionally 50%-70%; and/or [0199] the mass percentage content of the seventh monomer unit is M7, and M7 is 0%-10%, optionally 0.001%-2%.
[0200] In some embodiments, based on the total mass of the second polymer, [0201] the mass percentage content of the fifth monomer unit is M5, and M5 is 10%-55%, optionally 10%-15%, 15%-20%, 20%-25%, 25%-30% , 30%-35%, 35%-40%, 40%-45%, 45%-50% or 50%-55%; and/or [0202] the mass percentage content of the sixth monomer unit is M6, and M6 is 40%-80%, optionally 40%-45%, 45%-50%, 50%-55%, 55%-60% , 60%-65%, 65%-70%, 70%-75% or 75%-80%; and/or [0203] the mass percentage content of the seventh monomer unit is M7, and M7 is 0%-10%, optionally 0.01%-1%, 1%-2%, 2%-3%, 3%-4%, 4%-5%, 5%-6%, 6%-7%, 7% -8%, 8%-9% or 9%-10%.
[0204] In some embodiments, M7/(M6+M7) is 0%-5%, optionally 0.001%-1%. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0205] In some embodiments, the second polymer is a hydrogenated nitrile rubber; and/or [0206] the second polymer has a weight-average molecular weight of 50,000-500,000, optionally 150,000-350,000. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0207] In some embodiments, based on the total mass of the positive electrode film layer, the mass percentage content of the dispersant is Y1, and Y1 is 0.05%-1%, optionally 0.1%-0.5%, and/or the mass percentage content of the infiltration agent is Y2, and Y2 is 0.05%-2%, optionally 0.2%-0.8%. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0208] In some embodiments, Y1/Y2 is 0.05-20, optionally 0.1-1, further 0.3-0.8. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0209] In some embodiments, in the positive electrode plate, the mass ratio of the first polymer to the second polymer is 1.5-5, optionally 2-3. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0210] In some embodiments, the first coating layer has an interplanar spacing of the phosphate of 0.345-0.358 nm, and an angle of the crystal direction (111) of 24.25-26.45; and the first coating layer has an interplanar spacing of the pyrophosphate of 0.293-0.326 nm, and an angle of the crystal direction (111) of 26.41-32.57. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0211] In some embodiments, in the inner core, the ratio of y to 1-y is 1:10 to 10:1, optionally 1:4 to 1:1; and/or, in the inner core, the ratio of z to 1-z is 1:9 to 1:999, optionally 1:499 to 1:249. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0212] In some embodiments, the coating amount of the first coating layer is greater than 0 wt % and less than or equal to 7 wt %, optionally 4-5.6 wt %, based on the weight of the inner core. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0213] In some embodiments, the weight ratio of the pyrophosphate to phosphate in the first coating layer is 1:3 to 3:1, optionally 1:3 to 1:1. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0214] In some embodiments, the pyrophosphate and the phosphate each independently have a crystallinity of 10% to 100%, optionally 50% to 100%. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0215] In some embodiments, the coating amount of the second coating layer is greater than 0 wt % and less than or equal to 6 wt %, optionally 3-5 wt %, based on the weight of the inner core. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0216] In some embodiments, A is selected from at least two of Fe, Ti, V, Ni, Co and Mg. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0217] In some embodiments, the Li/Mn antisite defect concentration of the positive electrode active material is 4% or less, optionally 2% or less. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0218] In any embodiment, a lattice change rate of the positive electrode active material is no more than 6%, optionally no more than 4%. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0219] In some embodiments, the surface oxygen valence state of the positive electrode active material is no more than 1.88, optionally 1.98 to 1.88. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0220] In some embodiments, the compacted density of the positive electrode active material under 3 tons is no less than 2.0 g/cm.sup.3, optionally no less than 2.2 g/cm.sup.3. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
[0221] In some embodiments, the present application provides a secondary battery, comprising the positive electrode plate according to any one of the above aspects.
[0222] In some embodiments, the present application provides a power consuming device comprising the above secondary battery.
[0223] In some embodiments, the positive electrode plate generally includes a positive electrode current collector and a positive film layer provided on at least one surface of the positive electrode current collector, the positive film layer including a positive electrode active material.
[0224]
[0225] As an example, the positive electrode current collector has two surfaces opposite in its own thickness direction, and the positive electrode film layer is provided on either or both of opposite surfaces of the positive electrode current collector.
[0226] In some embodiments, the positive current collector can be a metal foil or a composite current collector. For example, as a metal foil, an aluminum foil can be used. The composite current collector may comprise a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. The composite current collector can be formed by forming a metal material (aluminum, an aluminum alloy, nickel, a nickel alloy, titanium, a titanium alloy, silver and a silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
[0227] In some embodiments, the positive electrode film layer may optionally comprise a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluorine-containing acrylate resin.
[0228] In some embodiments, the positive electrode film layer also optionally comprises a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketj en black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
[0229] In some embodiments, the positive electrode plate can be prepared as follows: dispersing the above-mentioned components for preparing the positive electrode plate, such as a positive electrode active material, a conductive agent, a binder and any other components, in a solvent (e.g., N-methyl pyrrolidone) to form a positive electrode slurry; and coating the positive electrode current collector with the positive electrode slurry, followed by the procedures such as drying and cold pressing, so as to obtain the positive electrode plate.
Negative Electrode Plate
[0230] The negative electrode plate comprises a negative electrode current collector and a negative electrode film layer provided on at least one surface of the negative electrode current collector, the negative electrode film layer comprising a negative electrode active material.
[0231] As an example, the negative electrode current collector has two surfaces opposite in its own thickness direction, and the negative electrode film layer is provided on either or both of the two opposite surfaces of the negative electrode current collector.
[0232] In some embodiments, the negative current collector may be a metal foil or a composite current collector. For example, as a metal foil, a copper foil can be used. The composite current collector may comprise a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. The composite current collector can be formed by forming a metal material (copper, a copper alloy, nickel, a nickel alloy, titanium, a titanium alloy, silver and a silver alloy, etc.) on a polymer material substrate (e.g., polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
[0233] In some embodiments, the negative electrode active material can be a negative electrode active material known in the art for batteries. As an example, the negative electrode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, a silicon-based material, a tin-based material and lithium titanate, etc. The silicon-based material may be selected from at least one of elemental silicon, silicon oxides, silicon carbon composites, silicon nitrogen composites and silicon alloys. The tin-based material may be selected from at least one of elemental tin, tin oxides, and tin alloys. However, the present application is not limited to these materials, and other conventional materials that can be used as negative electrode active materials for batteries can also be used. These negative electrode active materials may be used alone or in combination of two or more.
[0234] In some embodiments, the negative electrode film layer may optionally comprise a binder. As an example, the binder may be selected from at least one of a styrene butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
[0235] In some embodiments, the negative electrode film layer may optionally comprise a conductive agent. As an example, the conductive agent may be selected from at least one of superconductive carbon, acetylene black, carbon black, ketj enblack, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
[0236] In some embodiments, the negative electrode film layer may optionally comprise other auxiliary agents, such as thickener (e.g. sodium carboxymethyl cellulose (CMC-Na)) and the like.
[0237] In some embodiments, the negative electrode plate can be prepared as follows: dispersing the above-mentioned components for preparing the negative electrode plate, such as negative electrode active material, conductive agent, binder and any other components, in a solvent (e.g. deionized water) to form a negative electrode slurry; and coating a negative electrode current collector with the negative electrode slurry, followed by procedures such as drying and cold pressing, so as to obtain the negative electrode plate.
[Electrolyte]
[0238] The electrolyte functions to conduct ions between the positive electrode plate and the negative electrode plate. The type of the electrolyte is not specifically limited in the present application, and can be selected according to actual requirements. For example, the electrolyte may be in a liquid state, a gel state or an all-solid state.
[0239] In some embodiments, the electrolyte is liquid and includes an electrolyte salt and a solvent.
[0240] In some embodiments, the electrolyte salt may be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bisfluorosulfonimide, lithium bistrifluoromethanesulfonimide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalate borate, lithium dioxalate borate, lithium difluorodioxalate phosphate and lithium tetrafluorooxalate phosphate.
[0241] In some embodiments, the solvent may be selected from at least one of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1,4-butyrolactone, sulfolane, dimethyl sulfone, ethyl methyl sulfone, and diethyl sulfone.
[0242] In some embodiments, the electrolyte solution further optionally comprises an additive. As an example, the additive may include a negative electrode film-forming additive and a positive electrode film-forming additive, and may further include an additive that can improve some performance of the battery, such as an additive that improves overcharge performance of the battery, or an additive that improves high-temperature performance or low-temperature performance of the battery.
Separator
[0243] In some embodiments, the secondary battery further comprises a separator. The type of the separator is not particularly limited in the present application, and any well known porous-structure separator with good chemical stability and mechanical stability may be selected.
[0244] In some embodiments, the material of the separator may be selected from at least one of glass fibers, non-woven fabrics, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be either a single-layer film or a multi-layer composite film, and is not limited particularly. When the separator is a multi-layer composite film, the materials in the respective layers may be same or different, which is not limited particularly.
[0245] In some embodiments, an electrode assembly may be formed by a positive electrode plate, a negative electrode plate and a separator by a winding process or a stacking process.
[0246] In some embodiments, the secondary battery may comprise an outer package. The outer package can be used to encapsulate the above-mentioned electrode assembly and electrolyte.
[0247] In some embodiments, the outer package of the secondary battery can be a hard shell, for example, a hard plastic shell, an aluminum shell, a steel shell, etc. The outer package of the secondary battery may also be a soft bag, such as a pouch-type soft bag. The material of the soft bag may be plastics, and the examples of plastics may include polypropylene, polybutylene terephthalate, polybutylene succinate, etc.
[0248] The shape of the secondary battery is not particularly limited in the present application, and may be cylindrical, square or of any other shape. For example,
[0249] In some embodiments, with reference to
[0250] In some embodiments, the secondary battery can be assembled into a battery module, and the number of the secondary batteries contained in the battery module may be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery module.
[0251]
[0252] Optionally, the battery module 4 may also comprise a housing with an accommodating space, and a plurality of secondary batteries 5 are accommodated in the accommodating space.
[0253] In some embodiments, the above battery module may also be assembled into a battery pack, the number of the battery modules contained in the battery pack may be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery pack.
[0254]
[0255] In addition, the present application further provides a power consuming device. The power consuming device comprises at least one of the secondary battery, battery module, or battery pack provided by the present application. The secondary battery, battery module or battery pack can be used as a power source of the power consuming device or as an energy storage unit of the power consuming device. The power consuming device may include a mobile device (e.g., a mobile phone, a laptop computer, etc.), an electric vehicle (e.g., a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck, etc.), an electric train, ship, and satellite, an energy storage system, etc., but is not limited thereto.
[0256] As for the power consuming device, the secondary battery, battery module or battery pack can be selected according to the usage requirements thereof.
[0257]
Specific Examples of New Positive Electrode Active Material
[0258] Hereinafter, the examples of the present application will be explained. The examples described below are exemplary and are merely for explaining the present application, and should not be construed as limiting the present application. The examples in which techniques or conditions are not specified are based on the techniques or conditions described in documents in the art or according to the product introduction. The reagents or instruments used therein for which manufacturers are not specified are all conventional products that are commercially available. The content of each component in the examples of the present disclosure is based on the dry mass without crystal water, unless otherwise stated.
[0259] The sources of the raw materials involved in the examples of the present application are as follows:
TABLE-US-00001 Name Chemical formula Manufacturer Specification Manganese MnCO.sub.3 Shandong Xiya Chemical Industry 1 Kg carbonate Co., Ltd. Lithium carbonate Li.sub.2CO.sub.3 Shandong Xiya Chemical Industry 1 Kg Co., Ltd. Magnesium MgCO.sub.3 Shandong Xiya Chemical Industry 1 Kg carbonate Co., Ltd. Zinc carbonate ZnCO.sub.3 Wuhan Xinru Chemical Co., Ltd. 25 Kg Ferrous carbonate FeCO.sub.3 Xi'an Lanzhiguang Fine Materials 1 Kg Co., Ltd. Nickel sulfate NiCO.sub.3 Shandong Xiya Chemical Industry 1 Kg Co., Ltd. Titanium sulfate Ti(SO.sub.4)2 Shandong Xiya Chemical Industry 1 Kg Co., Ltd. Cobalt sulfate CoSO.sub.4 Xiamen Zhixin Chemical Co., Ltd. 500 g Vanadium VCl.sub.2 Shanghai Jinjinle Industrial Co., 1 Kg dichloride Ltd. Oxalic acid C.sub.2H.sub.2O.sub.42H.sub.2O Shanghai Jinjinle Industrial Co., 1 Kg dihydrate Ltd. Ammonium NH.sub.4H.sub.2PO.sub.4 Shanghai Chengshao 500 g dihydrogen Biotechnology Co., Ltd. phosphate Sucrose C.sub.12H.sub.22O.sub.11 Shanghai Yuanye Biotechnology 100 g Co., Ltd. Sulfuric acid H.sub.2SO.sub.4 Shenzhen Hisian Biotechnology Mass fraction Co., Ltd. 60% Nitric acid HNO.sub.3 Anhui Lingtian Fine Chemical Mass fraction Co., Ltd. 60% Siliceous acid H.sub.2SiO.sub.3 Shanghai Yuanye Biotechnology 100 g Co., Ltd. Boric acid H.sub.3BO.sub.3 Changzhou Qidi Chemical Co., 1 Kg Ltd.
EXAMPLE 1-1
Preparation of Lithium Manganese Phosphate Double-Coated Positive Electrode Active Material
(1) Preparation of Co-Doped Lithium Manganese Phosphate Inner Core
[0260] Preparation of Fe, Co and V co-doped manganese oxalate: 689.5 g of manganese carbonate (in MnCO.sub.3, the same below), 455.2 g of ferrous carbonate (in FeCO.sub.3, the same below), 4.6 g of cobalt sulfate (in CoSO.sub.4, the same below) and 4.9 g of vanadium dichloride (in VCl.sub.2, the same below) are mixed thoroughly for 6 hours in a mixer. The mixture is transferred into a reaction kettle, and 5 L of deionized water and 1260.6 g of oxalic acid dihydrate (in C.sub.2H.sub.2O.sub.4.Math.2H.sub.2O, the same below) are added. The reaction kettle is heated to stirring is performed for 6 hours at a rotation speed of 600 rpm until the reaction is completed (no bubbles are generated), so as to obtain an Fe, Co, V and S co-doped manganese oxalate suspension. Then, the suspension is filtered, and the resulting filter cake is dried at 120 C. and then ground, so as to obtain Fe, Co, and V co-doped manganese oxalate dihydrate particles with a median particle size D.sub.V50 of 100 nm.
[0261] Preparation of Fe, Co, V and S co-doped lithium manganese phosphate: Manganese oxalate dihydrate particles (1793.4 g) obtained in the previous step, 369.0 g of lithium carbonate (in Li.sub.2CO.sub.3, the same below), 1.6 g of 60% dilute sulfuric acid (in 60% H.sub.2SO.sub.4, the same below) and 1148.9 g of ammonium dihydrogen phosphate (in NH.sub.4H.sub.2PO.sub.4, the same below) are added to 20 L of deionized water, and the mixture is stirred for 10 hours for mixing uniformly, so as to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, where the drying temperature is set at 250 C. and the drying time is 4 h, so as to obtain a powder. The above powder is sintered at 700 C. for 4 hours in a protective atmosphere of nitrogen (90% by volume)+hydrogen (10% by volume), so as to obtain 1572.1 g of Fe, Co, V and S co-doped lithium manganese phosphate.
(2) Preparation of Lithium Iron Pyrophosphate and Lithium Iron Phosphate
[0262] Preparation of lithium iron pyrophosphate powder: 4.77 g of lithium carbonate, 7.47 g of ferrous carbonate, 14.84 g of ammonium dihydrogen phosphate and 1.3 g of oxalic acid dihydrate are dissolved in 50 ml of deionized water. The pH of the mixture is 5, and stirring is performed for 2 hours such that the reaction mixture is fully reacted. Then, the reacted solution is heated to 80 C. and kept at this temperature for 4 hours to obtain a suspension of Li.sub.2FeP.sub.2O.sub.7, which is filtered, washed with deionized water, and dried at 120 C. for 4 hours to obtain a powder. The powder is sintered at 650 C. under a nitrogen atmosphere for 8 h, cooled naturally to room temperature and then ground to obtain a Li.sub.2FeP.sub.2O.sub.7 powder.
[0263] Preparation of lithium iron phosphate suspension: 11.1 g of lithium carbonate, 34.8 g of ferrous carbonate, 34.5 g of ammonium dihydrogen phosphate, 1.3 g of oxalic acid dihydrate and 74.6 g of sucrose (in C.sub.12H.sub.22O.sub.11, the same below) are dissolved in 150 ml of deionized water to obtain a mixture, and then stirring is performed for 6 hours such that the mixture is fully reacted. Then, the reacted solution is heated to 120 C. and kept at this temperature for 6 hours to obtain a suspension of LiFePO.sub.4.
(3) Coating
[0264] 1572.1 g of the above Fe, Co, V and S co-doped lithium manganese phosphate and 15.72 g of the above lithium iron pyrophosphate (Li.sub.2FeP.sub.2O.sub.7) powder are added into the suspension of lithium iron phosphate (LiFePO.sub.4) prepared in the previous step, stirred and mixed uniformly, then transferred to a vacuum oven and dried at 150 C. for 6 h. The resulting product is then dispersed by sanding. After dispersion, the obtained product is sintered at 700 C. under a nitrogen atmosphere for 6 hours to obtain the target product of double-coated lithium manganese phosphate.
Preparation of Positive Electrode Plate
[0265] The double-coated lithium manganese phosphate positive electrode active material prepared above, a conductive agent acetylene black and a binder polyvinylidene fluoride (PVDF) are added to N-methylpyrrolidone (NMP) in a weight ratio of 92:2.5:5.5, followed by stirring and uniformly mixing to obtain a positive electrode slurry. The positive electrode slurry is uniformly coated onto an aluminum foil in 0.280 g/1540.25 mm.sup.2, followed by drying, cold pressing, and slitting to obtain the positive electrode plate.
Preparation of Negative Electrode Plate
[0266] Negative electrode active materials artificial graphite and hard carbon, a conductive agent acetylene black, a binder styrene butadiene rubber (SBR) and a thickening agent sodium carboxymethylcellulose (CMC-Na) are dissolved in deionized water in a weight ratio of 90:5:2:2:1, followed by stirring and uniformly mixing to prepare a negative electrode slurry. The negative electrode slurry is uniformly coated onto a negative electrode current collector copper foil in 0.117 g/1540.25 mm.sup.2, followed by drying, cold pressing, and slitting to obtain the negative electrode plate.
Preparation of Electrolyte Solution
[0267] In an argon atmosphere glove box (H.sub.2O<0.1 ppm, and O.sub.2<0.1 ppm), the organic solvents ethylene carbonate (EC)/ethyl methyl carbonate (EMC) are mixed uniformly in a volume ratio of 3/7, and 12.5 wt % (on the basis of the weight of the organic solvent) of LiPF.sub.6 is dissolved in the above organic solvent and stirred uniformly to obtain the electrolyte solution.
Separator
[0268] A commercially available PP-PE copolymer microporous film having a thickness of 20 m and an average pore size of 80 nm (Model 20, from Zhuogao Electronic Technology Co. Ltd.) is used.
Preparation of Full Batter
[0269] The above obtained positive electrode plate, separator and negative electrode plate are stacked in sequence, such that the separator is located between the positive electrode plate and the negative electrode plate to function for isolation, and are then wound to obtain a bare cell. The bare cell is placed in an outer package, injected with the above electrolyte solution and packaged to obtain a full battery.
Preparation of Button Battery
[0270] The double-coated lithium manganese phosphate positive electrode active material prepared above, PVDF and acetylene black are added into NMP in the weight ratio of 90:5:5, and stirred in a drying room to make a slurry. An aluminum foil is coated with the above slurry, followed by drying and cold pressing, so as to obtain a positive electrode plate. The coating amount is 0.02 g/cm.sup.2, and the compacted density is 2.0 g/cm.sup.3.
[0271] A lithium plate is used as a negative electrode, a solution of 1 mol/L LiPF.sub.6 in ethylene carbonate (EC)+diethyl carbonate (DEC)+dimethyl carbonate (DMC) in a volume ratio of 1:1:1 is used as an electrolyte solution, and the lithium plate and the electrolyte solution are assembled, together with the positive electrode plate prepared above, into a button battery in a button battery box.
EXAMPLES 1-2 to 1-6
[0272] In the preparation process of the co-doped lithium manganese phosphate inner core, except that vanadium dichloride and cobalt sulfate are not used, and 463.4 g of ferrous carbonate, 1.6 g of 60% dilute sulfuric acid, 1148.9 g of ammonium dihydrogen phosphate and 369.0 g of lithium carbonate are used, the preparation conditions of the lithium manganese phosphate inner core in examples 1-2 to 1-6 are the same as in example 1-1.
[0273] In addition, in the preparation process of lithium iron pyrophosphate and lithium iron phosphate and in the process of coating the first coating layer and the second coating layer, except that the raw materials used are adjusted correspondingly according to the ratio of the coating amount shown in Table 1 to the coating amount corresponding to example 1-1, such that the amount of Li.sub.2FeP.sub.2O.sub.7/LiFePO.sub.4 in examples 1-2 to 1-6 is 12.6 g/37.7 g, 15.7 g/47.1 g, 18.8 g/56.5 g, 22.0/66.0 g and 25.1 g/75.4 g, respectively, and the amount of sucrose in the Examples 1-2 to 1-6 is 37.3 g, other conditions are the same as in example 1-1.
EXAMPLES 1-7 to 1-10
[0274] Except that the amounts of sucrose are 74.6 g, 149.1 g, 186.4 g and 223.7 g, respectively, such that the corresponding coating amounts of the carbon layer as the second coating layer are 31.4 g, 62.9 g, 78.6 g and 94.3 g, respectively, the conditions of examples 1-7 to 1-10 are the same as in example 1-3.
EXAMPLES 1-11 to 1-14
[0275] In the preparation process of lithium iron pyrophosphate and lithium iron phosphate, except that the amounts of the raw materials are adjusted correspondingly according to the coating amount shown in Table 1, such that the amount of Li.sub.2FeP.sub.2O.sub.7/LiFePO.sub.4 is 23.6 g/39.3 g, 31.4 g/31.4 g, 39.3 g/23.6 g and 47.2 g/15.7 g, respectively, the conditions of examples 1-11 to 1-14 are the same as in example 1-7.
EXAMPLE 1-15
[0276] In the preparation process of co-doped lithium manganese phosphate inner core, except that iron ferrous carbonate is replaced by 492.80 g of ZnCO.sub.3, the conditions of example 1-15 are the same as in example 1-14.
EXAMPLES 1-16 to 1-18
[0277] Except that in the preparation process of co-doped lithium manganese phosphate inner core of example 1-16, ferrous carbonate is replaced by 466.4 g of NiCO.sub.3, 5.0 g of zinc carbonate and 7.2 g of titanium sulfate; except that in the preparation process of co-doped lithium manganese phosphate inner core of example 1-17, 455.2 g of ferrous carbonate and 8.5 g of vanadium dichloride are used; and except that in the preparation process of co-doped lithium manganese phosphate inner core of example 1-18, 455.2 g of ferrous carbonate, 4.9 g of vanadium dichloride and 2.5 g of magnesium carbonate are used, the conditions of examples 1-17 to 1-19 are the same as in example 1-7.
EXAMPLES 1-19 to 1-20
[0278] Except that in the preparation process of co-doped lithium manganese phosphate inner core of example 1-19, 369.4 g of lithium carbonate is used, and dilute sulfuric acid is replaced by 1.05 g of 60% dilute nitric acid; and except that in the preparation process of co-doped lithium manganese phosphate inner core of example 1-20, 369.7 g of lithium carbonate is used, and dilute sulfuric acid is replaced by 0.78 g of siliceous acid, the conditions of examples 1-19 to 1-20 are the same as in example 1-18.
EXAMPLES 1-21 to 1-22
[0279] Except that in the preparation process of co-doped lithium manganese phosphate inner core of example 1-21, 632.0 g of manganese carbonate, 463.30 g of ferrous carbonate, 30.5 g of vanadium dichloride, 21.0 g of magnesium carbonate and 0.78 g of siliceous acid are used; and except that in the preparation process of co-doped lithium manganese phosphate inner core of example 1-22, 746.9 g of manganese carbonate, 289.6 g of ferrous carbonate, 60.9 g of vanadium dichloride, 42.1 g of magnesium carbonate and 0.78 g of siliceous acid are used, the conditions of examples 1-21 to 1-22 are the same as in example 1-20.
EXAMPLES 1-23 to 1-24
[0280] Except that in the preparation process of co-doped lithium manganese phosphate inner core of example 1-23, 804.6 g of manganese carbonate, 231.7 g of ferrous carbonate, 1156.2 g of ammonium dihydrogen phosphate, 1.2 g of boric acid (with a mass fraction of 99.5%) and 370.8 g of lithium carbonate are used; and except that in the preparation process of co-doped lithium manganese phosphate inner core of example 1-24, 862.1 g of manganese carbonate, 173.8 g of ferrous carbonate, 1155.1 g of ammonium dihydrogen phosphate, 1.86 g of boric acid (with a mass fraction of 99.5%) and 371.6 g of lithium carbonate are used, the conditions of examples 1-23 to 1-24 are the same as in example 1-22.
EXAMPLE 1-25
[0281] Except that in the preparation process of co-doped lithium manganese phosphate inner core of example 1-25, except that 370.1 g of manganese carbonate, 1.56 g of siliceous acid and 1147.7 g of ammonium dihydrogen phosphate are used, the conditions of example 1-25 are the same as in example 1-20.
EXAMPLE 1-26
[0282] Except that in the preparation process of co-doped lithium manganese phosphate inner core of example 1-26, 368.3 g of lithium carbonate, 4.9 g of 60% dilute sulfuric acid, 919.6 g of manganese carbonate, 224.8 g of ferrous carbonate, 3.7 g of vanadium dichloride, 2.5 g of magnesium carbonate and 1146.8 g of ammonium dihydrogen phosphate are used, the conditions of example 1-26 are the same as in example 1-20.
EXAMPLE 1-27
[0283] Except that in the preparation process of co-doped lithium manganese phosphate inner core of example 1-27, 367.9 g of lithium carbonate, 6.5 g of 60% dilute sulfuric acid and 1145.4 g of ammonium dihydrogen phosphate are used, the conditions of example 1-27 are the same as in example 1-20.
EXAMPLES 1-28 to 1-33
[0284] Except that in the preparation process of co-doped lithium manganese phosphate inner core of examples 1-28 to 1-33, 1034.5 g of manganese carbonate, 108.9 g of ferrous carbonate, 3.7 g of vanadium dichloride and 2.5 g of magnesium carbonate are used; the amounts of lithium carbonate are respectively: 367.6 g, 367.2 g, 366.8 g, 366.4 g, 366.0 g and 332.4 g; the amounts of ammonium dihydrogen phosphate are respectively: 1144.5 g, 1143.4 g, 1142.2 g, 1141.1 g, 1139.9 g and 1138.8 g; and the amounts of 60% dilute sulfuric acid are respectively: 8.2 g, 9.8 g, 11.4 g, 13.1 g, 14.7 g and 16.3 g, the conditions of examples 1-28 to 1-33 are the same as in example 1-20.
EXAMPLES 2-1 to 2-4
EXAMPLE 2-1
[0285] Except that in the preparation process of lithium iron pyrophosphate (Li.sub.2FeP.sub.2O.sub.7), in the powder sintering step, the sintering temperature is 550 C. and the sintering time is 1 h to control the crystallinity of Li.sub.2FeP.sub.2O.sub.7 to be 30%; and except that in the preparation process of lithium iron phosphate (LiFePO.sub.4), in the coating sintering step, the sintering temperature is 650 C. and the sintering time is 2 h to control the crystallinity of LiFePO.sub.4 to be 30%, other conditions are the same as in example 1-1.
EXAMPLE 2-2
[0286] Except that in the preparation process of lithium iron pyrophosphate (Li.sub.2FeP.sub.2O.sub.7), in the powder sintering step, the sintering temperature is 550 C. and the sintering time is 2 h to control the crystallinity of Li.sub.2FeP.sub.2O.sub.7 to be 50%; and except that in the preparation process of lithium iron phosphate (LiFePO.sub.4), in the coating sintering step, the sintering temperature is 650 C. and the sintering time is 3 h to control the crystallinity of LiFePO.sub.4 to be 50%, other conditions are the same as in example 1-1.
EXAMPLE 2-3
[0287] Except that in the preparation process of lithium iron pyrophosphate (Li.sub.2FeP.sub.2O.sub.7), in the powder sintering step, the sintering temperature is 600 C. and the sintering time is 3 h to control the crystallinity of Li.sub.2FeP.sub.2O.sub.7 to be 70%; and except that in the preparation process of lithium iron phosphate (LiFePO.sub.4), in the coating sintering step, the sintering temperature is 650 C. and the sintering time is 4 h to control the crystallinity of LiFePO.sub.4 to be 70%, other conditions are the same as in example 1-1.
EXAMPLE 2-4
[0288] Except that in the preparation process of lithium iron pyrophosphate (Li.sub.2FeP.sub.2O.sub.7), in the powder sintering step, the sintering temperature is 650 C. and the sintering time is 4 h to control the crystallinity of Li.sub.2FeP.sub.2O.sub.7 to be 100%; and except that in the preparation process of lithium iron phosphate (LiFePO.sub.4), in the coating sintering step, the sintering temperature is 700 C. and the sintering time is 6 h to control the crystallinity of LiFePO.sub.4 to be 100%, other conditions are the same as in example 1-1.
EXAMPLES 3-1 to 3-12
[0289] Except that in the preparation process of Fe, Co, and V co-doped manganese oxalate particles, the heating temperature/stirring time in the reaction kettle in example 3-1 is 60 C./120 min; the heating temperature/stirring time in the reaction kettle in example 3-2 is respectively 70 C./120 min; the heating temperature/stirring time in the reaction kettle in example 3-3 is respectively 80 C./120 min; the heating temperature/stirring time in the reaction kettle in example 3-4 is respectively 90 C./120 min; the heating temperature/stirring time in the reaction kettle in example 3-5 is respectively 100 C./120 min; the heating temperature/stirring time in the reaction kettle in example 3-6 is respectively 110 C./120 min; the heating temperature/stirring time in the reaction kettle in example 3-7 is respectively 120 C./120 min; the heating temperature/stirring time in the reaction kettle in example 3-8 is respectively 130 C./120 min; the heating temperature/stirring time in the reaction kettle in example 3-9 is respectively 100 C./60 min; the heating temperature/stirring time in the reaction kettle in example 3-10 is respectively 100 C./90 min; the heating temperature/stirring time in the reaction kettle in example 3-11 is respectively 100 C./150 min; and the heating temperature/stirring time in the reaction kettle in example 3-12 is respectively 100 C./180 min, other conditions of examples 3-1 to 3-12 are the same as in example 1-1.
EXAMPLES 4-1 to 4-7
[0290] Examples 4-1 to 4-4: Except that in the preparation process of lithium iron pyrophosphate (Li.sub.2FeP.sub.2O.sub.7), in the drying step, the drying temperature/drying time is 100 C./4 h, 150 C./6 h, 200 C./6 h and 200 C./6 h, respectively; and except that in the preparation process of lithium iron pyrophosphate (Li.sub.2FeP.sub.2O.sub.7), in the sintering step, the sintering temperature and sintering time are 700 C./6 h, 700 C./6 h, 700 C./6 h and 600 C./6 h, respectively, other conditions are the same as in example 1-7.
[0291] Examples 4-5 to 4-7: Except that in the coating process, the drying temperature/drying time in the drying step is 150 C./6 h, 150 C./6 h and 150 C./6 h, respectively; and except that in the coating process, the sintering temperature and sintering time in the sintering step are 600 C./4 h, 600 C./6 h and 800 C./8 h, respectively, other conditions are the same as in example 1-12.
Comparative Example 1
[0292] Preparation of manganese oxalate: 1149.3 g of manganese carbonate is added into a reaction kettle, and 5 L of deionized water and 1260.6 g of oxalic acid dihydrate (in C2H2O4.2H2O, the same below) are added. The reaction kettle is heated to 80 C., stirring is performed for 6 hours at a rotation speed of 600 rpm until the reaction is completed (no bubbles are generated), so as to obtain a manganese oxalate suspension. Then, the suspension is filtered, and the resulting filter cake is dried at 120 C. and then ground to obtain manganese oxalate dihydrate particles with a median particle size D.sub.V50 of 100 nm.
[0293] Preparation of carbon-coated lithium manganese phosphate: 1789.6 g of manganese oxalate dihydrate particles obtained above, 369.4 g of lithium carbonate (in Li.sub.2CO.sub.3, the same below), 1150.1 g of ammonium dihydrogen phosphate (in NH4H2PO4, the same below) and 31 g of sucrose (in C.sub.12H.sub.22O.sub.11, the same below) are added to 20 L of deionized water, and the mixture is stirred for 10 hours to be uniformly mixed, so as to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, where the drying temperature is set at 250 C. and the drying time is 4 h, so as to obtain a powder. The above powder is sintered at 700 C. for 4 hours in a protective atmosphere of nitrogen (90% by volume)+hydrogen (10% by volume), so as to obtain carbon doped lithium manganese phosphate.
Comparative Example 2
[0294] Except that 689.5 g of manganese carbonate is used and 463.3 g of ferrous carbonate is additionally added, other conditions of comparative example 2 are the same as in comparative example 1
Comparative Exampl3
[0295] Except that 1148.9 g of ammonium dihydrogen phosphate and 369.0 g of lithium carbonate are used, and 1.6 g of 60% dilute sulfuric acid is additionally added, other conditions of comparative example 3 are the same as in comparative example 1.
Comparative Example 4
[0296] Except that 689.5 g of manganese carbonate, 1148.9 g of ammonium dihydrogen phosphate and 369.0 g of lithium carbonate are used, and 463.3 g of ferrous carbonate and 1.6 g of 60% dilute sulfuric acid are additionally added, other conditions of comparative example 4 are the same as in comparative example 1.
Comparative Example 5
[0297] Except for the following additional steps: preparation of lithium iron pyrophosphate powder: 9.52 g of lithium carbonate, 29.9 g of ferrous carbonate, 29.6 g of ammonium dihydrogen phosphate and 32.5 g of oxalic acid dihydrate are dissolved in 50 ml of deionized water; the pH of the mixture is 5, and stirring is performed for 2 hours such that the reaction mixture is fully reacted; then, the reacted solution is heated to 80 C. and kept at this temperature for 4 hours to obtain a suspension of Li.sub.2FeP.sub.2O.sub.7, which is filtered, washed with deionized water, and dried at 120 C. for 4 hours to obtain a powder; the powder is sintered at 500 C. under a nitrogen atmosphere for 4 h, and then ground after cooling to room temperature naturally to control the crystallinity of Li.sub.2FeP.sub.2O.sub.7 to be 5%; and when preparing a carbon-coated material, the amount of Li.sub.2FeP.sub.2O.sub.7 is 62.8 g, other conditions of comparative example 5 are the same as comparative example 4.
Comparative Example 6
[0298] Except for the following additional steps: preparation of lithium iron phosphate suspension: 14.7 g of lithium carbonate, 46.1 g of ferrous carbonate, 45.8 g of ammonium dihydrogen phosphate and 50.2 g of oxalic acid dihydrate are dissolved in 500 ml of deionized water, and then stirred for 6 hours such that the mixture is fully reacted; then, the reacted solution is heated to 120 C. and kept at this temperature for 6 hours to obtain a LiFePO.sub.4 suspension; in the preparation process of lithium iron phosphate (LiFePO.sub.4), the sintering temperature is 600 C. and the sintering time is 4 hours in the coating sintering step to control the crystallinity of LiFePO.sub.4 to be 8%; and when preparing a carbon-coated material, the amount of LiFePO.sub.4 is 62.8 g, other conditions of comparative example 6 are the same as comparative example 4.
Comparative Example 7
[0299] Preparation of lithium iron pyrophosphate powder: 2.38 g of lithium carbonate, 7.5 g of ferrous carbonate, 7.4 g of ammonium dihydrogen phosphate and 8.1 g of oxalic acid dihydrate are dissolved in 50 ml of deionized water. The pH of the mixture is 5, and stirring is performed for 2 hours such that the reaction mixture is fully reacted. Then, the reacted solution is heated to 80 C. and kept at this temperature for 4 hours to obtain a suspension of Li.sub.2FeP.sub.2O.sub.7, which is filtered, washed with deionized water, and dried at 120 C. for 4 hours to obtain a powder. The powder is sintered at 500 C. under a nitrogen atmosphere for 4 h, cooled naturally to room temperature and then ground to control the crystallinity of Li.sub.2FeP.sub.2O.sub.7 to be 5%.
[0300] Preparation of lithium iron phosphate suspension: Except that 11.1 g of lithium carbonate, 34.7 g of ferrous carbonate, 34.4 g of ammonium dihydrogen phosphate, 37.7 g of oxalic acid dihydrate and 37.3 g of sucrose (in C.sub.12H.sub.22O.sub.11, the same below) are dissolved in 1500 ml of deionized water, and then stirred for 6 hours such that the mixture is fully reacted; then, the reacted solution is heated to 120 C. and kept at this temperature for 6 hours to obtain a suspension of LiFePO.sub.4.
[0301] 15.7 g of the obtained lithium iron pyrophosphate powder is added to the above lithium iron phosphate (LiFePO.sub.4) and sucrose suspension; and in the preparation process, the sintering temperature is 600 C. and the sintering time is 4 h in the coating sintering step to control the crystallinity of LiFePO.sub.4 to be 8%, other conditions of comparative example 7 are the same as in comparative example 4, and amorphous lithium iron pyrophosphate, amorphous lithium iron phosphate, and the carbon-coated positive electrode active material are obtained.
Comparative Examples 8-11
[0302] Except that in the preparation process of lithium iron pyrophosphate (Li.sub.2FeP.sub.2O.sub.7), in comparative examples 8-10, the drying temperature/drying time in the drying step is 80 C./3 h, 80 C./3 h and 80 C./3 h, respectively; in the preparation process of lithium iron pyrophosphate (Li.sub.2FeP.sub.2O.sub.7), in comparative examples 8-10, the sintering temperature/sintering time in the sintering step is 400 C./3 h, 400 C./3 h and 350 C./2 h, respectively; in comparative example 11, in the preparation process of lithium iron phosphate (LiFePO.sub.4), the drying temperature/drying time in the drying step is 80 C./3 h; and in comparative examples 8-11, the amount of Li.sub.2FeP.sub.2O.sub.7/LiFePO.sub.4 is 47.2 g/15.7 g, 15.7 g/47.2 g, 62.8 g/0 g, and 0 g/62.8 g, respectively, other conditions are the same as in example 1-7.
[0303] The [Preparation of positive electrode plate], [Preparation of negative electrode plate], [Preparation of electrolyte solution], [Preparation of separator] and [Preparation of battery] of the above examples and comparative examples are all the same as in example 1-1.
Measurement for Associated Parameters
1. Measurement for Initial Gram Capacity of Button Battery:
[0304] At 2.5 to 4.3 V, a button battery prepared as above is charged at 0.1C to 4.3 V, then charged at a constant voltage of 4.3 V until the current is less than or equal to 0.05 mA, allowed to stand for 5 min, and then discharged at 0.1C to 2.0 V; and the discharge capacity at this moment is the initial gram capacity, marked as DO.
2. Average Discharge Voltage (V) Test of Button Battery:
[0305] The button battery prepared above is allowed to stand for 5 min at a constant temperature of 25 C., discharged at 0.1C to 2.5 V, allowed to stand for 5 min, charged at 0.1C to 4.3 V, and then charged at a constant voltage of 4.3 V until the current is less than or equal to 0.05 mA, and allowed to stand for 5 min; then the button battery is discharged at 0.1C to 2.5 V, and the discharge capacity at this moment is the initial gram capacity, which is recorded as DO; the discharge energy is the initial energy, which is recorded as EO; and the average discharge voltage V of the button battery is EO/DO.
3. Test of Expansion of Full Battery at 60 C.:
[0306] At 60 C., a full battery at 100% SOC (State of Charge) as prepared above is stored. Before and after and during the storage, the open-circuit voltage (OCV) and AC internal impedance (IMP) of a cell are measured for monitoring the SOC, and the volume of the cell is measured. Herein, the full battery is taken out after every 48 h of storage, and allowed to stand for 1 h, then the OCV and the IMP are measured, and the cell volume is measured by using the displacement method after the full battery is cooled to room temperature. The displacement method means that the gravity Fi of the cell is measured separately using a balance of which the on-board data is subjected to automatic unit conversion, then the cell is completely placed in deionized water (with a density known as 1 g/cm.sup.3), the gravity F.sub.2 of the cell at this moment is measured, the buoyancy F.sub.buoyancy on the cell is F.sub.1F.sub.2, and then the cell volume is calculated as V=(F.sub.1F.sub.2)/(g) according to the Archimedes principle F.sub.buoyancy=gV.sub.displacement.
[0307] From the test results of OCV and IMP, the batteries of all examples always maintain a SOC of no less than 99% in the experimental process till the end of the storage.
[0308] After 30 days of storage, the cell volume is measured, and a percentage increase in cell volume after the storage relative to the cell volume before the storage is calculated.
[0309] In addition, residual capacity of the cell is measured. At 2.5 to 4.3 V, the full battery is charged at 1C to 4.3 V, and then charged at a constant voltage of 4.3 V until the current is less than or equal to 0.05 mA. The full battery is allowed to stand for 5 min, and the charge capacity at this moment is recorded as the residual capacity of the cell.
4. Test of Cycling Performance of Full Battery at 45 C.:
[0310] In a constant-temperature environment at 45 C., at 2.5 to 4.3 V, a full battery as prepared above is charged at 1C to 4.3 V, and then charged at a constant voltage of 4.3 V until the current is less than or equal to 0.05 mA. The full battery is allowed to stand for 5 min, and then discharged at 1C to 2.5 V, and the discharge capacity at this moment is recorded as D0. The above-mentioned charge/discharge cycle is repeated until the discharge capacity is reduced to 80% of DO. The number of cycles experienced by the battery at this moment is recorded.
5. Test of Lattice Change Rate:
[0311] In a constant-temperature environment at 25 C., a positive electrode active material sample as prepared above is placed in XRD (model: Bruker D8 Discover) and tested at 1 /min, and the test data are organized and analyzed; and with reference to the standard PDF card, lattice constants a0, b0, c0 and v0 at this moment are calculated (a0, b0 and c0 represent the lengths of a unit cell on all sides, and v0 represents the volume of the unit cell, which may be obtained directly from XRD refinement results).
[0312] By using the method for preparing a button battery above, the positive electrode active material sample is made into a button battery, and the button battery is charged at a small rate of 0.05C until the current is reduced to 0.01C. Then a positive electrode plate in the button battery is taken out and soaked in dimethyl carbonate (DMC) for 8 h. Then the positive electrode plate is dried, powder is scraped off, and particles with a particle size of less than 500 nm are screened out. Sampling is performed, and a cell volume vl is calculated in the same way as that for testing the fresh sample as described above. (v0v1)/v0100% is shown in the table as a lattice change rate (cell volume change rate) of the sample before and after complete lithium intercalation and de-intercalation.
6. Li/Mn Antisite Defect Concentration Test:
[0313] The XRD results determined in the Method for measuring lattice change rate are compared with the PDF (Powder Diffraction File) card of a standard crystal, so as to obtain a Li/Mn antisite defect concentration. Specifically, the XRD results determined in the
[0314] Method for measuring lattice change rate are imported into a general structure analysis system (GSAS) software, and refinement results are obtained automatically, including the occupancies of different atoms; and a Li/Mn antisite defect concentration is obtained by reading the refinement results.
7. Transition Metal Dissolution Test:
[0315] A full battery after cycling to 80% attenuated capacity at 45 C. is discharged to a cut-off voltage of 2.0 V at a rate of 0.1C. Then the battery is disassembled, a negative electrode plate is taken out, a round piece of 30 unit areas (1540.25 mm.sup.2) is randomly taken from the negative electrode plate, and inductively coupled plasma (ICP) emission spectroscopy is performed with Agilent ICP-OES730. The amounts of Fe (if the Mn position of the positive electrode active material is doped with Fe) and Mn therein are calculated according to the ICP results, and then the dissolution of Mn (and Fe doping the Mn position) after cycling is calculated. The testing standard is in accordance with EPA-6010D-2014.
8. Surface Oxygen Valence State Test:
[0316] 5 g of a positive electrode active material prepared above is made into a button battery according to the method for preparing the above button battery. The button battery is charged at a small rate of 0.05C until the current is reduced to 0.01C. Then a positive electrode plate in the button battery is taken out and soaked in dimethyl carbonate (DMC) for 8 h. Then the positive electrode plate is dried, powder is scraped off, and particles with a particle size of less than 500 nm are screened out. The obtained particles are measured with electron energy loss spectroscopy (EELS, instrument model used: Talos F200S), so as to obtain an energy loss near-edge structure (ELNES) which reflects the density of states and energy level distribution of an element. According to the density of states and energy level distribution, the number of occupied electrons is calculated by integrating the data of valence-band density of states, and then a valence state of surface oxygen after the charging is extrapolated.
9. Measurement for Compacted Density:
[0317] 5 g of positive electrode active material powder prepared above is put into a compaction dedicated mold (U.S. CARVER mold, model: 13 mm), and then the mold is placed on a compacted density instrument. A pressure of 3T is exerted, the thickness (after pressure relief, the area of the container for measurement is 1540.25 mm.sup.2) of the powder under pressure is read from the instrument, and a compacted density is calculated through =m/v.
10. Test of the Crystallinity of Pyrophosphate and Phosphate by X-ray Diffraction
[0318] 5 g of the positive electrode active material powder prepared above is taken and measured for total scattering intensity by X-rays, which is the sum of the scattering intensity of the entire space material, and is only related to the intensity of the primary ray, the chemical structure, and the total number of electrons participating in the diffraction, that is, the mass, but has nothing to do with the order of the sample; then the crystalline scattering and non-crystalline scattering are separated from the diffraction pattern, and the degree of crystallinity is the ratio of the scattering of the crystalline part to the total intensity of the scattering.
11. Interplanar Spacing and Angle
[0319] 1 g of each positive electrode active material powder prepared above is placed in a 50 mL test tube, and 10 mL of alcohol with a mass fraction of 75% is injected into the test tube, then fully stirred and dispersed for 30 min, and then a clean disposable plastic straw is used to take an appropriate amount of the solution, which is dripped on a 300-mesh copper mesh, at this moment, part of the powder will remain on the copper mesh. The copper mesh and the sample are transferred to TEM (Tabs F200s G2) sample chamber for testing, the original picture of the TEM test is obtained and the original picture format (xx.dm3) is saved.
[0320] The original picture obtained from the above TEM test is opened in DigitalMicrograph software, and Fourier transform (automatically completed by the software after the clicking operation) is performed to obtain a diffraction pattern, and the distance from the diffraction spot to the center position in the diffraction pattern is measured to obtain the interplanar spacing, and the angle is calculated according to the Bragg equation.
TABLE-US-00002 TABLE 1 Performance test results of examples 1-1 to 1-33 and comparative examples 1-7 Expan- Number Gram Average sion of of cycles Dis- capacity dis- cell corre- Li/Mn solution of charge when sponding antisite of Fe button voltage stored to 80% Lattice defect and Mn Surface battery of at capacity First Second change concen- after oxygen at button 60 C. retention Example coating coating rate tration/ cycling valence 0.1 C. battery for 30 rate at No. Inner core layer layer (%) % (ppm) state (mAh/g) (V) d (%) 45 C. Example Li.sub.0.999Mn.sub.0.60Fe.sub.0.393 1% 2% of 2.4 0.4 8 1.98 158.2 3.78 1.9 1328 1-1 V.sub.0.004Co.sub.0.003P.sub.0.999 Li.sub.2FeP.sub.2O.sub.7/ carbon S.sub.0.001O.sub.4 3% LiFePO.sub.4 Example Li.sub.0.999Mn.sub.0.60Fe.sub.0.40 0.8% 1% of 6.6 1.2 63 1.97 148.9 3.75 6.4 804 1-2 P.sub.0.999S.sub.0.001O.sub.4 Li.sub.2FeP.sub.2O.sub.7/ carbon 2.4% LiFePO.sub.4 Example Li.sub.0.999Mn.sub.0.60Fe.sub.0.40 1% 1% of 6.5 1.1 48 1.97 148.5 3.74 5.3 918 1-3 P.sub.0.999S.sub.0.001O.sub.4 Li.sub.2FeP.sub.2O.sub.7/ carbon 3% LiFePO.sub.4 Example Li.sub.0.999Mn.sub.0.60Fe.sub.0.40 1.2% 1% of 6.5 0.8 32 1.97 147.3 3.73 4.8 968 1-4 P.sub.0.999S.sub.0.001O.sub.4 Li.sub.2FeP.sub.2O.sub.7/ carbon 3.6% LiFePO.sub.4 Example Li.sub.0.999Mn.sub.0.60Fe.sub.0.40 1.4% 1% of 6.5 0.7 20 1.98 146.8 3.73 3.6 1064 1-5 P.sub.0.999S.sub.0.001O.sub.4 Li.sub.2FeP.sub.2O.sub.7/ carbon 4.2% LiFePO.sub.4 Example Li.sub.0.999Mn.sub.0.60Fe.sub.0.40 1.6% 1% of 6.6 0.6 15 1.98 145.9 3.72 2.8 1189 1-6 P.sub.0.999S.sub.0.001O.sub.4 Li.sub.2FeP.sub.2O.sub.7/ carbon 4.8% LiFePO.sub.4 Example Li.sub.0.999Mn.sub.0.60Fe.sub.0.40 1% 2% of 6.5 1.0 42 1.97 147.5 3.73 4.8 968 1-7 P.sub.0.999S.sub.0.001O.sub.4 Li.sub.2FeP.sub.2O.sub.7/ carbon 3% LiFePO.sub.4 Example Li.sub.0.999Mn.sub.0.60Fe.sub.0.40 1% 4% of 6.5 1.0 38 1.97 146.4 3.73 4.3 1012 1-8 P.sub.0.999S.sub.0.001O.sub.4 Li.sub.2FeP.sub.2O.sub.7/ carbon 3% LiFePO.sub.4 Example Li.sub.0.999Mn.sub.0.60Fe.sub.0.40 1% 5% of 6.4 1.1 29 1.98 144.3 3.73 3.7 1108 1-9 P.sub.0.999S.sub.0.001O.sub.4 Li.sub.2FeP.sub.2O.sub.7/ carbon 3% LiFePO.sub.4 Example Li.sub.0.999Mn.sub.0.60Fe.sub.0.40 1% 6% of 6.4 1.1 18 1.98 142.1 3.73 2.8 1219 1-10 P.sub.0.999S.sub.0.001O.sub.4 Li.sub.2FeP.sub.2O.sub.7/ carbon 3% LiFePO.sub.4 Example Li.sub.0.999Mn.sub.0.60Fe.sub.0.40 1.5% 2% of 6.5 1.1 34 1.97 147.8 3.74 5.2 927 1-11 P.sub.0.999S.sub.0.001O.sub.4 Li.sub.2FeP.sub.2O.sub.7/ carbon 2.5% LiFePO.sub.4 Example Li.sub.0.999Mn.sub.0.60Fe.sub.0.40 2% 2% of 6.6 1.0 22 1.96 147.6 3.74 6.1 897 1-12 P.sub.0.999S.sub.0.001O.sub.4 Li.sub.2FeP.sub.2O.sub.7/ carbon 2% LiFePO.sub.4 Example Li.sub.0.999Mn.sub.0.60Fe.sub.0.40 2.5% 2% of 6.7 1.2 18 1.96 147.2 3.74 6.9 816 1-13 P.sub.0.999S.sub.0.001O.sub.4 Li.sub.2FeP.sub.2O.sub.7/ carbon 1.5% LiFePO.sub.4 Example Li.sub.0.999Mn.sub.0.60Fe.sub.0.40 3% 2% of 6.7 1.1 9 1.97 |147.0 3.75 7.5 764 1-14 P.sub.0.999S.sub.0.001O.sub.4 Li.sub.2FeP.sub.2O.sub.7/ carbon 1% LiFePO.sub.4 Example Li.sub.0.999Mn.sub.0.60Zn.sub.0.40 3% 2% of 7.5 2.5 18 1.97 |138.7 3.86 8.4 857 1-15 P.sub.0.999S.sub.0.001O.sub.4 Li.sub.2FeP.sub.2O.sub.7/ carbon 1% LiFePO.sub.4 Example Li.sub.0.993Mn.sub.0.6Ni.sub.0.393 1% 2% of 5.4 0.8 14 1.97 |139.4 3.86 4.5 974 1-16 Zn.sub.0.004Ti.sub.0.003P.sub.0.999 Li.sub.2FeP.sub.2O.sub.7/ carbon S.sub.0.001O.sub.4 3% LiFePO.sub.4 Example Li.sub.0.999Mn.sub.0.60Fe.sub.0.393 1% 2% of 4.2 0.6 13 1.97 153.2 3.78 3.2 1241 1-17 V.sub.0.007P.sub.0.999S.sub.0.001 Li.sub.2FeP.sub.2O.sub.7/ carbon O.sub.4 3% LiFePO.sub.4 Example Li.sub.0.999Mn.sub.0.60Fe.sub.0.393 1% 2% of 2.6 0.5 10 1.97 155.6 3.80 2.7 1245 1-18 V.sub.0.004Mg.sub.0.003P.sub.0.999 Li.sub.2FeP.sub.2O.sub.7/ carbon S.sub.0.001O.sub.4 3% LiFePO.sub.4 Example LiMn.sub.0.60Fe.sub.0.393V.sub.0.004 1% 2% of 2.3 0.5 9 1.98 157.6 3.80 2.1 1349 1-19 Mg.sub.0.003P.sub.0.999N.sub.0.001 Li.sub.2FeP.sub.2O.sub.7/ carbon O.sub.4 3% LiFePO.sub.4 Example Li.sub.1.001Mn.sub.0.60Fe.sub.0.393 1% 2% of 2.4 0.7 11 1.98 157.4 3.80 2.4 1368 1-20 V.sub.0.004Mg.sub.0.003P.sub.0.999 Li.sub.2FeP.sub.2O.sub.7/ carbon Si.sub.0.001O.sub.4 3% LiFePO.sub.4 Example Li.sub.1.001Mn.sub.0.55Fe.sub.0.40 1% 2% of 2.2 0.5 8 1.98 158.4 3.72 2.0 1459 1-21 V.sub.0.025Mg.sub.0.025P.sub.0.999 Li.sub.2FeP.sub.2O.sub.7/ carbon Si.sub.0.001O.sub.4 3% LiFePO.sub.4 Example Li.sub.1.001Mn.sub.0.65Fe.sub.0.25 1% 2% of 2.5 0.8 12 1.98 156.9 3.83 2.8 1283 1-22 V.sub.0.05Mg.sub.0.05P.sub.0.999 Li.sub.2FeP.sub.2O.sub.7/ carbon Si.sub.0.001O.sub.4 3% LiFePO.sub.4 Example Li.sub.1.004Mn.sub.0.7Fe.sub.0.2 1% 2% of 2.6 0.8 11 1.98 157.1 3.83 2.5 1268 1-23 V.sub.0.05Mg.sub.0.05P.sub.0.998 Li.sub.2FeP.sub.2O.sub.7/ carbon B.sub.0.002O.sub.4 3% LiFePO.sub.4 Example Li.sub.1.006Mn.sub.0.75Fe.sub.0.15 1% 2% of 2.6 0.8 10 1.98 157.4 3.83 2.6 1329 1-24 V.sub.0.05Mg.sub.0.05P.sub.0.997 Li.sub.2FeP.sub.2O.sub.7/ carbon B.sub.0.003O.sub.4 3% LiFePO.sub.4 Example Li.sub.1.002Mn.sub.0.60Fe.sub.0.393 1% 2% of 2.3 0.7 10 1.98 157.3 3.78 2.4 1369 1-25 V.sub.0.004Mg.sub.0.003P.sub.0.998 Li.sub.2FeP.sub.2O.sub.7/ carbon Si.sub.0.002O.sub.4 3% LiFePO.sub.4 Example Li.sub.0.997Mn.sub.0.80Fe.sub.0.194 1% 2% of 2.8 0.9 12 1.98 156.1 3.85 2.9 1128 1-26 V.sub.0.003Mg.sub.0.003P.sub.0.997 Li.sub.2FeP.sub.2O.sub.7/ carbon S.sub.0.003O.sub.4 3% LiFePO.sub.4 Example Li.sub.0.996Mn.sub.0.60Fe.sub.0.393 1% 2% of 2.2 0.6 11 1.98 157.5 3.78 2.4 1394 1-27 V.sub.0.004Mg.sub.0.003P.sub.0.996 Li.sub.2FeP.sub.2O.sub.7/ carbon S.sub.0.004O.sub.4 3% LiFePO.sub.4 Example Li.sub.0.995Mn.sub.0.9Fe.sub.0.094 1% 2% of 3.2 1.1 13 1.96 156.8 3.89 3.2 1089 1-28 V.sub.0.003Mg.sub.0.003P.sub.0.995 Li.sub.2FeP.sub.2O.sub.7/ carbon S.sub.0.005O.sub.4 3% LiFePO.sub.4 Example Li.sub.0.994Mn.sub.0.90Fe.sub.0.094 1% 2% of 3.0 1.2 14 1.95 156.1 3.89 3.2 1038 1-29 V.sub.0.003Mg.sub.0.003P.sub.0.994 Li.sub.2FeP.sub.2O.sub.7/ carbon S.sub.0.006O.sub.4 3% LiFePO.sub.4 Example Li.sub.0.993Mn.sub.0.90Fe.sub.0.094 1% 2% of 2.8 1.4 16 1.95 155.8 3.89 3.1 948 1-30 V.sub.0.003Mg.sub.0.003P.sub.0.993 Li.sub.2FeP.sub.2O.sub.7/ carbon S.sub.0.007O.sub.4 3% LiFePO.sub.4 Example Li.sub.0.992Mn.sub.0.90Fe.sub.0.094 1% 2% of 2.6 1.4 17 1.94 155.4 3.89 3.0 917 1-31 V.sub.0.003Mg.sub.0.003P.sub.0.992 Li.sub.2FeP.sub.2O.sub.7/ carbon S.sub.0.008O.sub.4 3% LiFePO.sub.4 Example Li.sub.0.991Mn.sub.0.90Fe.sub.0.094 1% 2% of 2.4 1.2 18 1.94 154.8 3.89 2.8 897 1-32 V.sub.0.003Mg.sub.0.003P.sub.0.991 Li.sub.2FeP.sub.2O.sub.7/ carbon S.sub.0.009O.sub.4 3% LiFePO.sub.4 Example Li.sub.0.9Mn.sub.0.90Fe.sub.0.094 1% 2% of 2.1 0.9 20 1.94 154.5 3.89 2.7 879 1-33 V.sub.0.003Mg.sub.0.003P.sub.0.9 Li.sub.2FeP.sub.2O.sub.7/ carbon S.sub.0.1O.sub.4 3% LiFePO.sub.4 Com- LiMnPO.sub.4 1% of 11.4 3.2 2060 1.55 125.6 4.02 48.6 185 parative carbon example 1 Com- LiMn.sub.0.60Fe.sub.0.40PO.sub.4 1% of 8.7 2.8 1597 1.76 134.8 3.76 42.5 358 parative carbon example 2 Com- Li.sub.0.999MnP.sub.0.999S.sub.0.001 1% of 9.8 2.5 1895 1.66 128.6 4.05 45.5 267 parative O.sub.4 carbon example 3 Com- Li.sub.0.999Mn.sub.0.60Fe.sub.0.40 1% of 6.7 1.8 1279 1.83 140.5 3.78 38.5 417 parative P.sub.0.999S.sub.0.001O.sub.4 carbon example 4 Com- Li.sub.0.999Mn.sub.0.60Fe.sub.0.40 4% of 1% of 6.5 1.8 208 1.90 140.3 3.73 12.5 519 parative P.sub.0.999S.sub.0.001O.sub.4 amorphous carbon example Li.sub.2FeP.sub.2O.sub.7 5 Com- Li.sub.0.999Mn.sub.0.60Fe.sub.0.40 4% of 1% of 6.6 1.8 318 1.91 140.2 3.74 11.5 528 parative P.sub.0.999S.sub.0.001O.sub.4 amorphous carbon example LiFePO.sub.4 6 Com- Li.sub.0.999Mn.sub.0.60Fe.sub.0.40 1% of 1% of 6.6 1.8 174 1.90 140.1 3.75 8.6 682 parative P.sub.0.999S.sub.0.001O.sub.4 amorphous carbon example Li.sub.2FeP.sub.2O.sub.7 + 7 3% of amorphous LiFePO.sub.4 *Note: 1) The crystallinity of Li.sub.2FeP.sub.2O.sub.7 and LiFePO.sub.4 in examples 1-1 to 1-33 are all 100%; and 2) in comparative examples 5-7, the crystallinity of Li.sub.2FeP.sub.2O.sub.7 is 5%, and the crystallinity of LiFePO.sub.4 is 8%.
[0321] From the combination of examples 1-1 to 1-33 and comparative examples 1-4, it can be seen that the existence of the first coating layer is conducive to reduce the Li/Mn antisite defect concentration of the obtained material and the dissolution of Fe and Mn after cycling, increase the gram capacity of button battery of the battery, and improve the safety performance and cycling performance of the battery. When other elements are doped on the Mn site and phosphorus site respectively, the lattice change rate, antisite defect concentration and Fe and Mn dissolution of the obtained material can be significantly reduced, the gram capacity of the battery can be increased, and the safety performance and cycling performance of the battery can be improved.
[0322] From the combination of examples 1-1 to 1-6, it can be seen that with the increase of the amount of the first coating layer from 3.2% to 6.4%, the Li/Mn anti site defect concentration of the obtained material gradually decreases, and the Fe and Mn dissolution gradually decreases after cycling, and the safety performance and cycling performance at 45 C. of the corresponding battery are also improved, but the gram capacity of the button battery decreases slightly. Optionally, when the total amount of the first coating layer is 4-5.6 wt %, the overall performance of the corresponding battery is the best.
[0323] From the combination of example 1-3 and examples 1-7 to 1-10, it can be seen that with the increase of the amount of the second coating layer from 1% to 6%, the Li/Mn anti site defect concentration of the obtained material gradually decreases, and the Fe and Mn dissolution gradually decreases after cycling, and the safety performance and cycling performance at 45 C. of the corresponding battery are also improved, but the gram capacity of the button battery decreases slightly. Optionally, when the total amount of the second coating layer is 3-5 wt %, the overall performance of the corresponding battery is the best.
[0324] From the combination of examples 1-11 to 1-15 and comparative examples 5-6, it can be seen that when Li.sub.2FeP.sub.2O.sub.7 and LiFePO.sub.4 exist simultaneously in the first coating layer, and especially the weight ratio of Li.sub.2FeP.sub.2O.sub.7 to LiFePO.sub.4 is 1:3 to 3:1, and especially 1:3 to 1:1, the improvement of battery performance is more obvious.
TABLE-US-00003 TABLE 2 Performance test results of examples 2-1 to 2-4 Crystal- linity of Dissolu- Capacity Average Expansion Capacity pyroph Li/Mn tion of Fe of discharge of cell retention osphate Lattice antisite and Mn Surface button voltage of when rate First and change defect after oxygen battery button stored at during Example coating phosph rate concentra- cycling valence at 0.1 C. battery 60 C. for cycling No. layer atel (%) tion/% (ppm) state (mAh/g) (V) 30 d (%) at 45 C. Example 1% 30% 6.3 1.9 147 1.88 145.2 3.72 5.6 698 2-1 Li.sub.2FeP.sub.2O.sub.7/ 3% LiFePO.sub.4 Example 1% 50% 4.7 1.2 97 1.89 149.2 3.74 4.7 869 2-2 Li.sub.2FeP.sub.2O.sub.7/ 3% LiFePO.sub.4 Example 1% 70% 3.5 0.8 29 1.91 151.3 3.75 3.8 1027 2-3 Li.sub.2FeP.sub.2O.sub.7/ 3% LiFePO.sub.4 Example 1% 100% 2.4 0.4 8 1.98 158.2 3.79 1.9 1328 2-4 Li.sub.2FeP.sub.2O.sub.7/ 3% LiFePO.sub.4 .sup.1refers to the crystallinity of Li.sub.2FeP.sub.2O.sub.7 and LiFePO.sub.4 are 30%, 50%, 70%, and 100%, respectively.
[0325] It can be seen from Table 2 that as the crystallinity of pyrophosphate and phosphate in the first coating layer gradually increases, the lattice change rate of the corresponding material, the Li/Mn antisite defect concentration, and the dissolution of Fe and Mn gradually decrease, the button battery capacity of the battery is gradually increased, and the safety performance and cycling performance are also gradually improved.
TABLE-US-00004 TABLE 3 Performance test results of Examples 3-1 to 3-12 Number Expan- of sion of cycles Dissolu- Average cell for Li/Mn tion of Capacity discharge when capacity Doping antisite Fe and of voltage stored retention element Tempera- Lattice defect Mn Surface button of at rate Exam- type and ture in Stirring change concen- after oxygen battery button 60 C. of ple doping reaction time/ rate tration/ cycling valence at 0.1 C. battery for 30 80% at No. amount kettle( C.) min (%) % (ppm) state (mAh/g) (V) d (%) 45 C. Exam- Li.sub.0.999Mn.sub.0.60 60 120 5.6 2.4 49 1.98 155.2 3.67 5.6 1102 ple 3- Fe.sub.0.393V.sub.0.004 1 Co.sub.0.003P.sub.0.999 S.sub.0.001O.sub.4 Exam- Li.sub.0.999Mn.sub.0.60 70 120 4.8 1.9 37 1.98 155.7 3.69 4.7 1203 ple 3- Fe.sub.0.393V.sub.0.004 2 Co.sub.0.003P.sub.0.999 S.sub.0.001O.sub.4 Exam- Li.sub.0.999Mn.sub.0.60 80 120 3.7 1.3 28 1.98 156.4 3.72 3.8 1275 ple 3- Fe.sub.0.393V.sub.0.004 3 Co.sub.0.003P.sub.0.999 S.sub.0.001O.sub.4 Exam- Li.sub.0.999Mn.sub.0.60 90 120 2.9 1.1 17 1.98 157.8 3.75 3.1 1305 ple 3- Fe.sub.0.393V.sub.0.004 4 Co.sub.0.003P.sub.0.999 S.sub.0.001O.sub.4 Exam- Li.sub.0.999Mn.sub.0.60 100 120 2.5 0.5 9 1.98 158.5 3.78 2.4 1327 ple 3- Fe.sub.0.393V.sub.0.004 5 Co.sub.0.003P.sub.0.999 S.sub.0.001O.sub.4 Exam- Li.sub.0.999Mn.sub.0.60 110 120 2.8 1.2 19 1.98 156.7 3.73 3.6 1257 ple 3- Fe.sub.0.393V.sub.0.004 6 Co.sub.0.003P.sub.0.999 S.sub.0.001O.sub.4 Exam- Li.sub.0.999Mn.sub.0.60 120 120 3.7 2.1 38 1.98 154.8 3.69 4.8 1179 ple 3- Fe.sub.0.393V.sub.0.004 7 Co.sub.0.003P.sub.0.999 S.sub.0.001O.sub.4 Exam- Li.sub.0.999Mn.sub.0.60 130 120 4.5 3.4 46 1.98 153.7 3.64 6.3 986 ple 3- Fe.sub.0.393V.sub.0.004 8 Co.sub.0.003P.sub.0.999 S.sub.0.001O.sub.4 Exam- Li.sub.0.999Mn.sub.0.60 100 60 4.9 3.1 38 1.98 155.4 3.76 4.9 1021 ple 3- Fe.sub.0.393V.sub.0.004 9 Co.sub.0.003P.sub.0.999 S.sub.0.001O.sub.4 Exam- Li.sub.0.999Mn.sub.0.60 100 90 4.1 2.5 27 1.98 156.3 3.77 4.2 1097 ple 3- Fe.sub.0.393V.sub.0.004 10 Co.sub.0.003P.sub.0.999 S.sub.0.001O.sub.4 Exam- Li.sub.0.999Mn.sub.0.60 100 150 3.5 1.1 15 1.98 157.8 3.79 3.1 1184 ple 3- Fe.sub.0.393V.sub.0.004 11 Co.sub.0.003P.sub.0.999 S.sub.0.001O.sub.4 Exam- Li.sub.0.999Mn.sub.0.60 100 180 2.5 0.5 11 1.98 158.1 3.79 2.4 1297 ple 3- Fe.sub.0.393V.sub.0.004 12 Co.sub.0.003P.sub.0.999 S.sub.0.001O.sub.4 Note 1. The temperature and stirring time in the reaction kettle are the parameters during the preparation of element A doped manganese oxalate (i.e, step (1)).
[0326] It can be seen from Table 3 that by adjusting the reaction temperature and reaction time in the reaction kettle during the preparation of manganese oxalate particles, various performances of the positive electrode material of the present application can be further improved. For example, when the reaction temperature gradually increases from 60 C. to 130 C., the lattice change rate and Li/Mn antisite defect concentration first decreases and then increases, and the corresponding metal dissolution and safety performance after cycling also show similar rules, while the button battery capacity and cycling performance first increase and then decrease with the increase of temperature. Keeping the reaction temperature constant and adjusting the reaction time can also show a similar rule.
TABLE-US-00005 TABLE 4a Performance test results of examples 4-1 to 4-7 and comparative examples 8-11 Drying Drying Sintering Sintering Example Li.sub.2FeP.sub.2O.sub.7:LiFePO.sub.4 temperature time temperature time No. (weight ratio) ( C.) (h) ( C.) (h) Example 4-1 1:3 100 4 700 6 Example 4-2 1:3 150 6 700 6 Example 4-3 1:3 200 6 700 6 Example 4-4 1:3 200 6 600 6 Example 4-5 1:1 150 6 600 4 Example 4-6 1:1 150 6 600 6 Example 4-7 1:1 150 6 800 8 Comparative 1:3 80 3 400 3 example 8 Comparative 1:1 80 3 400 3 example 9 Comparative Only Li.sub.2FeP.sub.2O.sub.7 80 3 350 2 example 10 Comparative Only LiFePO.sub.4 80 3 example 11
TABLE-US-00006 TABLE 4b Performance test results of examples 4-1 to 4-7 and comparative examples 8-11 Lattice Lattice spacing Angle Expan- spacing of of the Average sion of Number of Angle of phos- phos- dis- cell of cycles pyrophos- the phate phate Capacity charge when for phate in pyrophos- in the of the Li/Mn of voltage stored capacity the first phate of first first Lattice antisite Surface button of at retention coating the first coating coating change defect oxygen battery button 60 C. rate of Example layer coating layer layer rate concentra- valence at 0.1 C. battery for 30 80% at No. (nm) layer () (nm) () (%) tion/% state (mAh/g) (V) d (%) 45 C. Example 0.303 29.496 0.348 25.562 2.9 0.6 1.97 155.4 3.71 3.4 1183 4-1 Example 0.303 29.496 0.348 25.562 2.6 0.6 1.98 157.8 3.78 2.4 1347 4-2 Example 0.303 29.496 0.348 25.562 2.7 0.6 1.98 156.5 3.73 3.1 1277 4-3 Example 0.303 29.496 0.348 25.562 2.9 1.1 1.95 153.8 3.69 3.9 984 4-4 Example 0.303 29.496 0.348 25.562 2.8 1.2 1.94 155.5 3.71 3.5 895 4-5 Example 0.303 29.496 0.348 25.562 2.6 0.8 1.95 156.3 3.72 3.1 963 4-6 Example 0.303 29.496 0.348 25.562 2.5 0.4 1.97 156.9 3.74 2.7 1043 4-7 Com- 3.9 1.8 1.91 148.0 3.67 9.4 779 parative example 8 Com- 3.6 1.6 1.93 149.4 3.70 6.8 683 parative example 9 Com- 3.7 1.7 1.86 147.5 3.68 11.5 385 parative example 10 Com- 3.4 1.4 1.93 150.3 3.72 4.7 526 parative example 11
[0327] It can be seen from Tables 4a and 4b that when preparing lithium iron pyrophosphate by the method of the present application, by adjusting the drying temperature/time and sintering temperature/time during the preparation process, the performance of the obtained material can be improved, thereby improving the battery performance. From comparative examples 8-11, it can be seen that when the drying temperature in the preparation process of lithium iron pyrophosphate is lower than 100 C. or the temperature in the sintering step is lower than 400 C., Li.sub.2FeP.sub.2O.sub.7, which is expected to be prepared in the present application, will not be obtained, thereby failing to improve the material properties as well as the performance of the battery comprising the resulting material.
Specific Examples of New Conductive Undercoat Layer
[0328] Hereinafter, the examples of the present application will be explained. The examples described below are exemplary and are merely for explaining the present application, and should not be construed as limiting the present application. The examples in which techniques or conditions are not specified are based on the techniques or conditions described in documents in the art or according to the product introduction. The reagents or instruments used therein for which manufacturers are not specified are all conventional products that are commercially available.
[0329] For the distinguishment from the new positive electrode material in the above specific examples, the specific examples of the new conductive undercoat layer are marked with a suffix [] after the number.
Example 1-1 (with a Positive Electrode Active Material of Example 1-1)
1. Providing First Polymer
[0330] In the following examples, the first polymer is a hydrogenated carboxylated nitrile rubber, which comprises a first monomer unit, a second monomer unit, a third monomer unit and a fourth monomer unit. The weight percentages of the first monomer unit, the second monomer unit, the third monomer unit and the fourth monomer unit in the polymer, and the weight-average molecular weight of the first polymer are shown in Table 1P.
[0331] The first monomer unit is a monomer unit represented by formula 1;
##STR00007##
[0332] the second monomer unit is selected from at least one of a group consisting of a monomer unit represented by formula 2 and a monomer unit represented by formula 3;
##STR00008##
[0333] the third monomer unit is selected from at least one of a group consisting of a monomer unit represented by formula 4 and a monomer unit represented by formula 5;
##STR00009##
[0334] the fourth monomer unit is a monomer unit represented by formula 6:
##STR00010##
[0335] In this example, R.sup.1, R.sup.2 and R.sup.3 are all H, and R.sup.4 is n-butyl.
TABLE-US-00007 TABLE 1P First monomer Second monomer Third monomer Fourth monomer Weight-average unit unit unit unit molecular weight weight weight weight weight/ percentage M1 percentage M2 percentage M3 percentage M4 10,000 34% 64% 1% 1% 25
2. Preparation of Aluminum Foil with Conductive Undercoat Layer
[0336] The first polymer, the first water-based binder (a polyacrylic acid-acrylate copolymer, a weight-average molecular weight of 340,000) and the first conductive agent (SP) are dissolved/dispersed at a weight ratio of 15:40:45 into an NMP solvent and formulated as a conductive undercoat layer slurry.
[0337] The conductive undercoat layer slurry is coated on both sides of the aluminum foil, and after drying, a conductive undercoat layer with a thickness of 5 m is formed on each side. An aluminum foil with a conductive undercoat layer is obtained.
3) Preparation of Positive Electrode Plate
[0338] The double-coated lithium manganese phosphate positive electrode active material prepared in the above example 1-1, a conductive agent acetylene black and a binder polyvinylidene fluoride (PVDF) are mixed uniformly in an N-methylpyrrolidone solvent system at a weight ratio of 92:2.5:5.5, to obtain the positive electrode slurry, the positive electrode slurry is coated on both sides of the aluminum foil with a conductive undercoat layer, followed by drying and cold pressing, to form a positive electrode film layer, and obtain a positive electrode plate. The positive electrode film layer has a single-side surface density of 0.025 g/cm 2 and a compacted density of 2.4 g/cm.sup.3.
4) Preparation of Negative Electrode Plate
[0339] Negative electrode active materials artificial graphite and hard carbon, a conductive agent acetylene black, a binder styrene butadiene rubber (SBR) and a thickening agent sodium carboxymethylcellulose (CMC) are uniformly mixed in deionized water in a weight ratio of 90:5:2:2:1, and the mixture is applied to a copper foil, followed by drying and cold pressing, so as to form a negative electrode film layer, to obtain a negative electrode plate. The negative electrode film layer has a single-side surface density of 0.013 g/cm.sup.2 and a compacted density of 1.7 g/cm.sup.3.
5) Packaging of Full Battery
[0340] With a polyethylene (PE) porous polymer film as a separator, the positive electrode plate, the separator and the negative electrode plate are stacked in sequence, such that the separator is located between the positive electrode and the negative electrode to play a role of isolation, and then winding is performed to obtain a bare cell. The bare cell is placed in an outer package, injected with the electrolyte solution and packaged to obtain a full battery.
[0341] The weight of the positive electrode active material in a single full battery is 565.66 g. The weight of the negative electrode active material is 309.38 g.
Examples 1-2 to 1-33 (with Positive Electrode Active Materials of Examples 1-2 to 1-33)
[0342] Examples 1-2 to 1-33 are different from example 1-1 by step 3). Other step parameters are the same as those in example 1-1.
[0343] The positive electrode active materials used in step 3) in examples 1-2 to 1-33 are the positive electrode active materials in the above examples 1-2 to 1-33 respectively.
Examples 2-1 to 2-3 (with Positive Electrode Active Materials of Examples 2-1 to 2-3)
[0344] Examples 2-1 to 2-3 are different from example 1-1 by step 3). Other step parameters are the same as those in example 1-1.
[0345] The positive electrode active materials used in step 3) in examples 2-1 to 2-3 are the positive electrode active materials in the above examples 2-1 to 2-3 respectively.
Comparative Examples 1 to 8 (Without Conductive Undercoat Layer)
[0346] Comparative examples 1 to 8 are different from example 1-1 by steps 2) and 3). Other step parameters are the same as those in example 1-1.
[0347] In comparative examples 1 to 8, in steps 2) and 3), no aluminum foil with a conductive undercoat layer is prepared, and the positive electrode slurry is directly coated onto the aluminum foil, followed by drying, and cold pressing to form the positive electrode film layer, to obtain the positive electrode plate.
[0348] The positive electrode active materials used in step 3) of comparative examples 1 to 7 are the positive electrode active materials of the above comparative examples 1-1 to 1-7, respectively.
[0349] The positive electrode active material used in step 3) of comparative example 8 is the positive electrode active materials of the above example 1-1.
Comparative Example 9 (Without First Polymer)
[0350] Comparative example 9 is different from example 1-1 by step 2). Other step parameters are the same as those in example 1-1.
[0351] In step 2) of comparative example 9, the first water-based binder (a polyacrylic acid-acrylate copolymer) and the first conductive agent (SP), at a weight ratio of 40:45, are dissolved/dispersed in deionized water, and formulated as a conductive undercoat layer slurry. The conductive undercoat layer slurry is coated onto an aluminum foil, and dried to form a conductive undercoat layer with a thickness of 5 An aluminum foil with a conductive undercoat layer is obtained.
Comparative Example 10 (Replacing the First Polymer With Polymer I)
[0352] Comparative Example 10 is different from example 1-1 by step 2). Other step parameters are the same as those in example 1-1.
[0353] In step 2) of comparative example 10, the polymer I, the first water-based binder (a polyacrylic acid-acrylate copolymer) and the first conductive agent (SP), at a weight ratio of 15:40:45, are dissolved/dispersed in deionized water, and formulated as a conductive undercoat layer slurry. The conductive undercoat layer slurry is coated onto an aluminum foil, and dried to form a conductive undercoat layer with a thickness of 5 An aluminum foil with a conductive undercoat layer is obtained.
[0354] The difference between the polymer I and the first polymer is that the compositions of the polymer are different, and the composition and weight-average molecular weight of the polymer I are shown in Table 2P below.
TABLE-US-00008 TABLE 2P First monomer Second monomer Third monomer Fourth monomer Weight-average unit unit unit unit molecular weight weight weight weight weight/ percentage M1 percentage M2 percentage M3 percentage M4 10,000 30% 59% 10% 1% 25
Comparative Example 11 (replacing the first water-based binder with I binder)
[0355] Comparative Example 11 is different from example 1-1 by step 2). Other step parameters are the same as those in example 1-1.
[0356] In step 2) of comparative example 11, the first polymer, the I binder (polyacrylic acid, a weight-average molecular weight of 350,000) and the first conductive agent (SP), at a weight ratio of 15:40:45, are dissolved/dispersed in deionized water, and formulated as a conductive undercoat layer slurry. The conductive undercoat layer slurry is coated onto an aluminum foil, and dried to form a conductive undercoat layer with a thickness of 5 An aluminum foil with a conductive undercoat layer is obtained.
Analysis and test
1. Testing for Adhesive Force of Positive Electrode Plate
[0357] (a)-(d) of
2. Direct-Current Resistance Test
[0358] At 25 C., the battery is charged to 4.3 V at a 1.0 C constant current and constant voltage (1.0 C refers to the nominal capacity); the battery power is adjusted to 50% SOC at 1.0 C rate, left to stand for 5 min, then discharge at a 4 C constant current (I.sub.m) for 30 s (with the voltage data collected every 1s), and the initial voltage U.sub.0 and the voltage U.sub.30 after 30 s of discharge are recorded. The direct current resistance (DCR) value is calculated by the following formula.
direct-current resistance value=(U.sub.0U.sub.30)/I.sub.m
[0359] Taking the direct-current resistance value of the battery of example 1-1 as 100%, the changes of other examples and comparative examples relative to example 1-1 are expressed in percentage form.
3. Number of Cycles of Battery for Capacity Retention Rate of 80% at 45 C. (Hereinafter Referred to as Cycle Number for 80% Capacity)
[0360] In a constant-temperature environment at 45 C., at 2.5 to 4.3 V, a full battery is charged at 1C to 4.3 V, and then charged at a constant voltage of 4.3 V until the current is less than or equal to 0.05 mA. The full battery is allowed to stand for 5 min, and then discharged at 1C to 2.5 V, and the discharge capacity at this moment is recorded as DO. The above-mentioned charge/discharge cycle is repeated until the discharge capacity is reduced to 80% of DO. The number of cycles experienced by the battery at this moment is recorded.
[0361] According to the above-mentioned testing and analysis methods, the adhesive force, the direct-current resistance value of the battery and the number of cycles for capacity retention rate of 80% at 45 C. from the positive electrode plates prepared in the above examples 1-1 to 1-33, examples 2-1 to 2-3 and comparative examples 1 to 11 are tested, and the results are shown in Table 3P below.
TABLE-US-00009 TABLE 3P Adhesive force of direct-current Number of positive electrode resistance cycles for plate/N example 1-1-based 80% capacity Example 1-1 13 100% 1650 Example 1-2 15.2 110% 800 Example 1-3 15.0 110% 910 Example 1-4 14.3 110% 982 Example 1-5 14.7 107% 1103 Example 1-6 14.1 106% 1200 Example 1-7 8.2 111% 1000 Example 1-8 6.8 109% 1107 Example 1-9 5.0 110% 1201 Example 1-10 4.0 101% 1302 Example 1-11 7.7 108% 1007 Example 1-12 8.2 108% 963 Example 1-13 7.3 112% 907 Example 1-14 8 116% 800 Example 1-15 8 117% 842 Example 1-16 7.3 110% 1047 Example 1-17 7 104% 1300 Example 1-18 7 104% 1308 Example 1-19 7 100% 1484 Example 1-20 8 100% 1462 Example 1-21 9 95% 1577 Example 1-22 8.1 99% 1352 Example 1-23 7.8 98% 1369 Example 1-24 8 95% 1466 Example 1-25 8 94% 1495 Example 1-26 7.5 104% 1244 Example 1-27 7.9 105% 1500 Example 1-28 9 110% 1022 Example 1-29 7.3 110 1155 Example 1-30 7 111% 1083 Example 1-31 8.5 111% 1044 Example 1-32 7.9 120% 1002 Example 1-33 7.7 120% 957 Example 2-1 10.1 155% 598 Example 2-2 10.5 157% 769 Example 2-3 10.5 132% 1127 Comparative 4 231% 105 example 1 Comparative 4.1 208% 367 example 2 Comparative 4.3 200% 300 example 3 Comparative 4 200% 500 example 4 Comparative 3.7 180% 625 example 5 Comparative 3.9 176% 590 example 6 Comparative 4.6 155% 740 example 7 Comparative 5.5 118% 1406 example 8 Comparative 7.3 116% 1584 example 9 Comparative 14.2 280% 630 example 10 Comparative 10.4 103% 1500 example 11
[0362] It can be seen from Table 3P that the positive electrode plates of examples 1-1 to 1-33 and examples 2-1 to 2-3 show improved adhesive forces, and the batteries of examples 1-1 to 1-33, examples 2-1 to 2-3 show reduced direct-current resistance and increased cycle capacity retention rate.
[0363] Comparative example 8 (without a conductive undercoat layer), comparative example 9 (without a first polymer), comparative example 10 (replacing the first polymer with an polymer I), comparative example 11 (replacing the first water-based binder with an I binder) fail to achieve the effect of the above-mentioned improvement.
Examples 3-1 to 3-7 (with Changes in Composition of the First Polymer)
[0364] Examples 3-1 to 3-7 are different from example 1-1 by step 2). Other step parameters are the same as those in example 1-1.
[0365] In step 2), the compositions of the first polymer used in examples 3-1 to 3-7 are different from those in example 1-1, and specifically the weight percentages of the second monomer unit and the third monomer unit are different from those in example 1-1. The compositions of the first polymers of examples 3-1 to 3-7 are shown in Table 4P below.
TABLE-US-00010 TABLE 4P First monomer Second Third monomer Fourth monomer unit monomer unit unit unit weight weight weight weight M3/ percentage M1 percentage M2 percentage M3 percentage M4 (M2 + M3) Example 1-1 0.64 0.01 0.01 0.015 0.34 Example 3-1 0.65 0 0.01 0 0.34 Example 3-2 0.649675 0.000325 0.01 0.0005 0.34 Example 3-3 0.64935 0.00065 0.01 0.001 0.34 Example 3-4 0.6487 0.0013 0.01 0.002 0.34 Example 3-5 0.64805 0.00195 0.01 0.003 0.34 Example 3-6 0.64675 0.00325 0.01 0.005 0.34 Example 3-7 0.598 0.052 0.01 0.08 0.34
[0366] Examples 3-8 to 3-12 (with changes in conductive undercoat layer thickness)
[0367] Examples 3-8 to 3-12 are different from example 1-1 by step 2). Other step parameters are the same as those in example 1-1.
[0368] In step 2), the thickness of the conductive undercoat layer in examples 3-8 to 3-12 is different from that in example 1-1, see Table 5P for details.
TABLE-US-00011 TABLE 5P Example Example Example Example Example Example 1-1 3-8 3-9 3-10 3-11 3-12 Conductive 5 m 1 m 3 m 7 m 10 m 20 m undercoat layer thickness
Examples 3-13 to 3-18 (with Changes in Composition of the Conductive Undercoat Layer)
[0369] Examples 3-13 to 3-18 are different from example 1-1 by step 2). Other step parameters are the same as those in example 1-1.
[0370] In step 2), the compositions of the conductive undercoat layer (the ratio of the first polymer, the first water-based binder to the first conductive agent) of examples 3-13 to 3-18 are different from those in example 1-1, see Table 6P for details.
TABLE-US-00012 TABLE 6P First water- First conductive First polymer based binder agent weight part weight part weight part Example 1-1 15 40 45 Example 3-13 5 45 50 Example 3-14 10 40 50 Example 3-15 20 30 50 Example 3-16 10 80 10 Example 3-17 10 65 25 Example 3-18 10 50 40
[0371] According to the above-mentioned testing and analysis methods, the adhesive force, the direct-current resistance value of the battery and the number of cycles for capacity retention rate of 80% at 45 C. of the positive electrode plates prepared in the above example 1-1 and examples 3-1 to 3-18 are tested, and the results are shown in Table 7P below.
TABLE-US-00013 TABLE 7P Number of cycles Adhesive force of direct- for 80% electrode plate current resistance capacity Example 1-1 13 100% 1650 Example 3-1 12.7 100% 1700 Example 3-2 13 97% 1688 Example 3-3 12.5 100% 1703 Example 3-4 13.1 99% 1600 Example 3-5 13.8 98% 1660 Example 3-6 13.9 99% 1655 Example 3-7 12 258% 731 Example 3-8 8.5 110% 1540 Example 3-9 7.3 101% 1720 Example 3-10 9.9 100% 1779 Example 3-11 21.1 120% 1600 Example 3-12 32.5 150% 1678 Example 3-13 8.1 100% 1630 Example 3-14 10.5 105% 1680 Example 3-15 11.6 103% 1701 Example 3-16 10.7 145% 1600 Example 3-17 14.5 130% 1635 Example 3-18 15 110% 1630
[0372] It can be seen from Table 7P that the positive electrode plates of examples 1-1, and 3-1 to 3-18 show improved adhesive forces, and the batteries of examples 1-1 and 3-1 to 3-18 show reduced direct-current resistance and increased cycle capacity retention rate. When the value of M3/(M2+M3) is 0-5%, the direct current resistance of the battery shows a significant decrease.
Examples 4-1 to 4-9
[0373] Examples 4-1 to 4-9 are different from example 1-1 by step 3). Other step parameters are the same as those in example 1-1.
[0374] In step 3) in examples 4-1 to 4-9, the double-coated lithium manganese phosphate positive electrode active material prepared in the above example 1-1, a conductive agent acetylene black, a binder polyvinylidene fluoride (PVDF), a dispersant and an infiltration agent are mixed uniformly in an N-methylpyrrolidone solvent system at a weight ratio of (92-Y.sub.1-Y.sub.2):2.5:5.5:Y.sub.1:Y.sub.2, to obtain the positive electrode slurry, the positive electrode slurry is coated on both sides of the aluminum foil with a conductive undercoat layer, followed by drying and cold pressing, to form a positive electrode film layer, and a positive electrode plate is obtained. The positive electrode film layer has a single-side surface density of 0.025 g/cm.sup.2 and a compacted density of 2.4 g/cm.sup.3.
[0375] The infiltration agent in examples 4-1 to 4-9 is a maleic anhydride-styrene copolymer (molecular weight: 5000). The dispersant in examples 4-1 to 4-9 is the second polymer.
[0376] The second polymer is a hydrogenated nitrile rubber comprising a fifth monomer unit, a sixth monomer unit and a seventh monomer unit. The weight percentages of the five monomer unit, the sixth monomer unit and the seventh monomer unit in the polymer, and the weight-average molecular weight of the second polymer are shown in Table 8P.
[0377] The fifth monomer unit is a monomer unit represented by formula 1;
##STR00011##
[0378] the sixth monomer unit is selected from at least one of a group consisting of a monomer unit represented by formula 8 and a monomer unit represented by formula 9;
##STR00012##
[0379] 20 the seventh monomer unit is selected from at least one of a group consisting of a monomer unit represented by formula 10 and a monomer unit represented by formula 11;
##STR00013##
TABLE-US-00014 TABLE 8P Fifth monomer Sixth monomer Seventh monomer Weight-average unit weight unit weight unit weight molecular percentage M5 percentage M6 percentage M7 weight/10,000 45% 54.9% 0.1% 22
[0380] In the positive electrode plates of examples 4-1 to 4-9, the mass ratio of the first polymer (from the conductive undercoat layer) to the second polymer (from the positive electrode film layer) is 2:1.
[0381] In step 3) in examples 4-1 to 4-9, the proportions of the dispersant (second polymer) Y.sub.1 and the proportions of the infiltration agent (a maleic anhydride-styrene copolymer) Y.sub.2 and the ratio thereof Y.sub.1/Y.sub.2 are shown in Table 9P below.
TABLE-US-00015 TABLE 9P Y.sub.1 Y.sub.2 Y.sub.1/Y.sub.2 Example 4-1 0.2 0.3 0.67 Example 4-2 0.1 0.5 0.20 Example 4-3 0.5 0.5 1.00 Example 4-4 1 0.5 2.00 Example 4-5 0.25 0.05 5.00 Example 4-6 0.25 0.2 1.25 Example 4-7 0.25 0.3 0.83 Example 4-8 0.25 0.8 0.31 Example 4-9 0.25 2 0.13
[0382] According to the above-mentioned testing and analysis methods, the adhesive force, the direct-current resistance value of the battery and the number of cycles for capacity retention rate of 80% at 45 C. of the positive electrode plates prepared in the above example 1-1 and examples 4-1 to 4-9 are tested, and the results are shown in Table 10P below.
TABLE-US-00016 TABLE 10P Adhesive force of Direct-current Number electrode plate resistance of cycles Example 1-1 13 100% 1650 Example 4-1 64 93% 1762 Example 4-2 60 95% 1770 Example 4-3 178 104% 1310 Example 4-4 193 160% 1308 Example 4-5 105 100% 1700 Example 4-6 105 99% 1830 Example 4-7 110 98% 1781 Example 4-8 108 106% 1690 Example 4-9 109 116% 1410
[0383] As shown in Table 10P, on the basis of the above new conductive undercoat layer, combined with a new positive electrode film layer containing a dispersant and an infiltration agent, the adhesive force of the electrode plate can be further improved, and/or the direct-current resistance of the battery can be reduced, and/or the cycling performance of the battery is improved.
[0384] In view of the above experiment data, the present application provides a new positive electrode plate, a secondary battery and a power consuming device. The positive electrode plate comprises a new positive electrode active material and a new conductive premier layer.
[0385] The new positive electrode active materials have achieved better effects in one or even all aspects of cycling performance, high-temperature storage performance and safety performance.
[0386] The new conductive undercoat layer achieves better effects in one or even all aspects of providing the adhesive force of the electrode plate, reducing the direct-current resistance of the battery, and improving the cycling performance of the battery.
[0387] It should be noted that the present application is not limited to the above embodiments. The above embodiments are exemplary only, and any embodiment that has substantially same constitutions as the technical ideas and has the same effects within the scope of the technical solution of the present application falls within the technical scope of the present application. In addition, without departing from the gist of the present application, various modifications that can be conceived by those skilled in the art to the embodiments, and other modes constructed by combining some of the constituent elements of the embodiments also fall within the scope of the present application.