Irreversible Additive Contained in Cathode Material for Secondary Battery, Cathode Material Including the Same, and Secondary Battery Including Cathode Material

Abstract

An irreversible additive contained in a cathode material for a secondary battery according to one embodiment of the present disclosure, the irreversible additive being an oxide represented by the following chemical formula 1, wherein the oxide has a trigonal crystal structure,

Li.sub.2+aNi.sub.1−bTi.sub.bO.sub.2+c   (1) in the above formula, −0.2≤a≤0.2, 0<b≤0.2, and 0≤c≤0.2.

Claims

1. An irreversible additive contained in a cathode material for a secondary battery, comprising, an oxide represented by the following chemical formula 1, wherein the oxide has a trigonal crystal structure,
Li.sub.2+aNi.sub.1−bTi.sub.bO.sub.2+c   (1) in the above formula, −0.2≤a≤0.2, 0<b≤0.2, and 0≤c≤0.2.

2. The irreversible additive according to claim 1, wherein: the oxide belongs to a space group of P3-m1.

3. The irreversible additive according to claim 1, wherein: the oxide has a crystal lattice of a=3.0964 Å, c=5.0760 Å, and γ=120.00°.

4. The irreversible additive according to claim 1, wherein: the oxide is Li.sub.2Ni.sub.0.97Ti.sub.0.03O.sub.2.

5. The irreversible additive according to claim 1, wherein: the oxide has an oxygen formation energy of 4.25 eV or more and 5.0 eV or less.

6. A cathode material comprising the irreversible additive of claim 1 and a cathode active material.

7. The cathode material according to claim 6, wherein: a content of the irreversible additive is 0.1% by weight to 10% by weight based on the total weight of the cathode material.

8. A secondary battery comprising a cathode in which the cathode material of claim 6 is coated onto a cathode current collector, wherein the irreversible additive is converted into a monoclinic system within an operating voltage range of 4.0V or more.

9. The secondary battery according to claim 8, wherein: the irreversible additive belongs to a space group of C2/m when having a monoclinic crystal structure.

10. The secondary battery according to claim 8, wherein: the cathode active material comprises an oxide represented by the following chemical formula 2.
Li(Ni.sub.aCo.sub.bMn.sub.c)O.sub.2   (2) in the above formula, 0<a<1, 0<b<1, 0<c<1, and a+b+c=1.

11. The secondary battery according to claim 8, wherein: the secondary battery has a structure in which an electrode assembly is built in a battery case together with an electrolyte, with the electrode assembly comprising: the cathode; an anode in which an anode material including an anode active material is coated onto an anode current collector; and a separator that is interposed between the cathode and the anode.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0028] FIG. 1 is a graph showing the XRD measurement results of Comparative Example 1 according to Experimental Example 1;

[0029] FIG. 2 is a graph showing the XRD measurement results of Comparative Example 2 according to Experimental Example 1; and

[0030] FIG. 3 is a graph showing the XRD measurement results of Example 1 according to Experimental Example 1.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0031] Hereinafter, embodiments of the present disclosure will be described in detail so that those skilled in the art can easily implement them. However, the present disclosure may be modified in various different ways, and as such the present disclosure is not limited to the embodiments set forth herein

[0032] An irreversible additive contained in a cathode material for a secondary battery, a cathode material including the same, and a secondary battery including the cathode material according to embodiments of the present disclosure will be described below.

[0033] Conventionally, as the irreversible additive, an oxide of LNO(Li.sub.2NiO.sub.2) was prepared by mixing a lithium raw material and a nickel raw material and then heat-treating the mixture. When general raw materials were mixed and heat-treated in this manner, the oxide was produced into a material having an orthorhombic crystal structure, which is the most stable form. Therefore, conventionally, an oxide having an orthorhombic crystal structure has been added as the irreversible additive.

[0034] In contrast, according to the embodiments of the present disclosure, when the oxide used as the irreversible additive is added as a material having a trigonal crystal structure from the beginning, the trigonal and monoclinic crystal structures can be reversibly maintained according to the voltage of the secondary battery within the operating voltage range of the secondary battery.

[0035] According to one embodiment of the present disclosure, the irreversible additive contained in a cathode material for a secondary battery is an oxide represented by the following chemical formula 1, wherein the oxide has a trigonal crystal structure,

Li.sub.2+aNi.sub.1−bTi.sub.bO.sub.2+c   (1) [0036] in the above formula, −0.2≤a≤0.2, 0<b≤0.2, and 0≤c≤0.2.

[0037] Unlike a conventional irreversible additive, according to the present embodiment, the oxide represented by the chemical formula 1 may be added as an irreversible additive. The irreversible additive has a trigonal crystal structure while being an excessive lithiated oxide in which a molar ratio of Li is about twice that of the transition metal, as represented by the chemical formula 1.

[0038] The irreversible additive represented by the chemical formula 1 according to the present embodiment has a trigonal crystal structure while having an excessive amount of lithium, unlike the case where the conventional oxide becomes LiNiO.sub.2 by de-intercalation of Li ions and has a trigonal crystal structure. Therefore, if the irreversible additive according to the present embodiment has only a lithium-excess trigonal crystal structure, it does not have an orthorhombic crystal structure, which is a stable crystal structure, and thus, subsequently, the crystal structure changes according to the voltage, so that the structural stability may be deteriorated.

[0039] In this regard, according to the present embodiment, as shown in the chemical formula 1, a part of Ni is substituted by Ti in the irreversible additive unlike the conventional oxide, thereby capable of enhancing the structural stability, further reducing by-products and increasing the stability.

[0040] At this time, the Ti may be substituted by a part of Ni in an amount of more than 0 to 20% or less on a molar basis. More preferably, the Ti may be substituted by a part of Ni in an amount of more than 0 to 10% or less on a molar basis. In one example, the oxide may be Li.sub.2Ni.sub.0.97Ti.sub.0.03O.sub.2.

[0041] The irreversible additive represented by the chemical formula 1 as described above may, specifically, belong to a space group of P3-m1, and more specifically, the crystal lattice of the oxide may be a=3.0964 Å, c=5.0760 Å, and γ=120.00°.

[0042] The oxide represented by the chemical formula 1 according to the present embodiment may be an oxygen formation energy of 4.25 eV or more and 5.0 eV or less. More specifically, the oxygen formation energy of the oxide may be 4.4 eV or more and 4.9 eV or less. In one example, the oxygen formation energy of the oxide may be 4.5 eV or more and 4.8 eV or less.

[0043] Accordingly, the oxide represented by the chemical formula 1 according to the present embodiment can have a relatively high oxygen formation energy compared to the conventional oxide not substituted with Ti, thereby having a high structural stability of the crystal structure and reducing by-products caused by side reactions.

[0044] On the other hand, when the oxygen formation energy of the oxide is less than 4.25 eV, the oxide can have a relatively low oxygen formation energy and thus, the structural stability of the crystal structure is relatively low, so that structural changes can easily occur, and by-products caused by side reactions may also be increased. In addition, when the oxygen formation energy of the oxide is more than 5.0 eV, there is a problem that the production of oxides is not easy.

[0045] The material as described above prepared by a process in which Ti-substituted LiNi.sub.1−bTi.sub.bO.sub.2 (where 0<b≤0.2) is mixed with Li.sup.+benzophenone.sup.− and reacted under THF to obtain a trigonal Li.sub.2Ni.sub.1−bTi.sub.bO .sub.2 (where 0<b≤0.2) having weak crystallinity, which is then heat-treated under an inert atmosphere to obtain a trigonal Li.sub.2Ni.sub.1−bTi.sub.bO.sub.2 (where 0<b≤0.2) having high crystallinity.

[0046] The reaction under THF is specifically performed by a process in which the mixture is stirred, filtered, washed with dry THF, and then dried under vacuum.

[0047] The heat treatment is performed at 200 to 400° C. for 10 to 24 hours under an inert atmosphere. More preferably, the heat treatment may be performed at 200 to 300° C. for 12 to 16 hours under an inert atmosphere. In one example, the heat treatment is performed at 225° C. for 14 hours under an inert atmosphere.

[0048] The inert atmosphere may be a helium or argon atmosphere, and the heat treatment is performed while flowing the gases.

[0049] Further, the preparation must be performed within the range of temperature and time during the heat treatment, and thereby only the crystallinity can be improved without giving changes in the crystal structure of the trigonal Li.sub.2Ni.sub.1−bTi.sub.bO.sub.2 (where 0<b≤0.2) formed by reacting under THF. When the temperature is too low or the time is short, the crystallinity is not sufficiently improved, and when the temperature is too high or the time is long, it can give changes in the crystal structure itself, which is thus not preferable.

[0050] The Li.sub.2Ni.sub.1−bTi.sub.bO.sub.2 (where 0<b≤0.2) can be prepared by a method of substituting Ti in a conventionally known method for producing LiNiO.sub.2.

[0051] For example, it is prepared by mixing a lithium raw material and a nickel raw material together with a titanium raw material in a molar ratio satisfying the composition ratio and then heat-treating the mixture.

[0052] The heat treatment is performed at 650 to 800° C. for 10 to 24 hours under an air atmosphere. In the case of wet method, a drying process may be further included. More preferably, the heat treatment may be performed under a nitrogen (N.sub.2) atmosphere. More preferably, the heat treatment may be performed at 650 to 750° C. for 16 to 20 hours. In one example, the heat treatment may be performed at 680° C. for 18 hours. The preparation must be performed within the range of the temperature and time of the heat treatment, so that the reaction between the lithium raw material and the nickel raw material and further the titanium raw material can sufficiently occur, and unreacted materials can be minimized

[0053] As the lithium raw material, lithium-containing oxides, sulfates, nitrates, acetates, carbonates, oxalates, citrates, halides, hydroxides or oxyhydroxides, and the like can be used, and specific examples thereof include Li.sub.2CO.sub.3, LiNO.sub.3, LiNO.sub.2, LiOH, LiOH.H.sub.2O, LiH, LiF, LiCl, LiBr, LiI, CH.sub.3COOLi, Li.sub.2O, Li.sub.2SO.sub.4, CH.sub.3COOLi, Li.sub.3C.sub.6H.sub.5O.sub.7 or the like. Any one alone or a mixture of two or more of them may be used.

[0054] As the nickel raw material, nickel-containing oxides, sulfates, nitrates, acetates, carbonates, oxalates, citrates, halides, hydroxides or oxyhydroxides, and the like can be used, and specific examples thereof include NiO, Ni(NO.sub.3).sub.2, LiNO.sub.2, NiSO.sub.4, Ni(OH).sub.2, and the like. Any one alone or a mixture of two or more of them may be used.

[0055] The titanium raw material may be a titanium-containing oxide. In one example, the titanium raw material may be TiO.sub.2.

[0056] The irreversible additive of the crystal structure as described above can provide sufficient Li at the initial charge due to an excessive amount of lithium to solve the irreversibility problem and also omit one stage of change in crystal structure within the operating voltage range, thereby being able to not only minimize incidental problems such as generation of impurities or gas resulting from de-intercalation of an excessive amount of Li ions, but also improve the structural stability to minimize side reactions.

[0057] Meanwhile, according to another embodiment of the present disclosure, there is provided a cathode material including the irreversible additive and a cathode active material. At this time, the content of the irreversible additive may be 0.1% to 10% by weight, specifically 1% to 5% by weight, and more specifically 1% to 3% by weight based on the total weight of the cathode material.

[0058] When the content of the irreversible additive is less than 0.1% by weight outside the above range, the anode efficiency compensation effect due to the addition of an irreversible additive cannot be obtained, and when the content exceeds 10% by weight, problems such as volume expansion of the electrode caused by the generation of impurities or gas, and deterioration of life may occur.

[0059] Further, according to one embodiment of the present disclosure, there is provided a secondary battery including a cathode in which a cathode material is coated onto a cathode current collector, wherein the cathode material includes an irreversible additive including an oxide represented by the following chemical formula 1, and a cathode active material, and the irreversible additive has a trigonal system and is converted into a monoclinic system within a range in which the operating voltage range of the secondary battery is 4.0V or more.

Li.sub.2+aNi.sub.1−bTi.sub.bO.sub.2+c   (1) [0060] in the above formula, −0.2≤a≤0.2, 0<b≤0.2, and 0≤c≤0.2.

[0061] As described above, the crystal structure of the irreversible additive of lithium nickel titanium oxide changes in the operating voltage range of the secondary battery, which is similar even at the time of using the irreversible additive according to the present disclosure.

[0062] Therefore, according to the present disclosure, even if the oxide represented by the chemical formula 1 having a trigonal crystal structure is added as an irreversible additive, the crystal structure of the oxide can change to a monoclinic crystal system within the operating voltage range of the secondary battery in accordance with the intercalation and de-intercalation of Li ions.

[0063] In other words, the irreversible additive according to the present disclosure is added in the form of a trigonal crystal structure to the cathode material, and can be reversibly converted into a monoclinic crystal system within the operating voltage range of the secondary battery. At this time, the oxide having a monoclinic crystal structure may, specifically, belong to a space group of C2/m.

[0064] On the other hand, the cathode active material contained in the cathode material may be, for example, LiCoO.sub.2, LiNiO.sub.2, LiMnO.sub.2, LiMn.sub.2O.sub.2, Li(Ni.sub.aCo.sub.bMn.sub.c)O.sub.2 (0<a<1, 0<b<1, 0<c<1, a+b+c=1), LiNi.sub.1−dCo.sub.dO.sub.2, LiCo.sub.1−d, Mn.sub.dO.sub.2, LiNi.sub.1−dMn.sub.dO.sub.2(0≤d <1), Li(Ni.sub.aCo.sub.bMn.sub.c)O.sub.4 (0<a<2, 0<b<2, 0<c<2, a+b+c=2), LiMn.sub.2−eNi.sub.eO.sub.4, LiMn.sub.2−eCo.sub.eO.sub.4 (0<e<2), LiCoPO.sub.4, LiFePO.sub.4, or the like, and any one alone or a mixture of two or more of them may be used.

[0065] Of these, specifically, the cathode active material may include an oxide represented by the following chemical formula 2.

Li(Ni.sub.aCo.sub.bMn.sub.c)O.sub.2  (2) [0066] in the above formula, 0<a<1, 0<b<1, 0<c<1, and a+b+c=1.

[0067] The oxide of the chemical formula 2 is easily changed in the crystal structure from hexagonal to monoclinic while Li ions being de-intercalated and intercalated in the operating voltage range of the secondary battery. Therefore, since the oxide can have a structure similar to that of the irreversible additive of the present disclosure within the operating range, it is more effective in the use of the irreversible additive according to the present disclosure.

[0068] More specifically, the oxide represented by the chemical formula 2 may be contained in an amount of 80% by weight or more based on the total weight of the cathode active material.

[0069] The cathode material may further include a conductive material, a binder, a filler and the like, in addition to the cathode active material and the irreversible additive.

[0070] The conductive material is used to impart conductivity to the electrode, and the conductive material can be used without particular limitation as long as it has electronic conductivity without causing chemical changes to the battery to be configured.

[0071] The binder plays a role of improving adhesion between the cathode active material particles and adhesive strength between the cathode active material and the current collector. Specific examples thereof include polyvinylidene fluoride (PVDF), vinylidene fluoride- hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene- diene polymer (EPDM), sulfonated-EPDM, styrene butadiene rubber (SBR), fluororubber, or various copolymers thereof, and any one alone or a mixture of two or more of them may be used.

[0072] The cathode current collector is not particularly limited as long as it has conductivity while not causing chemical changes to the battery, and for example, stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel having a surface treated with carbon, nickel, titanium, silver, etc. may be used.

[0073] The secondary battery may have a structure in which an electrode assembly is built in a battery case together with an electrolyte, with the electrode assembly including: the cathode; an anode in which an anode material including an anode active material is coated onto an anode current collector; and a separator that is interposed between the cathode and the anode. Specifically, the secondary battery may be a lithium secondary battery.

[0074] The anode may also be produced in a form in which an anode material including an anode active material is coated onto an anode current collector, and the anode material may further include a conductive material and a binder as described above, together with an anode active material.

[0075] The anode current collector is not particularly limited as long as it has high conductivity without causing chemical changes to the battery. For example, copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel having a surface treated with carbon, nickel, titanium, silver, etc., aluminum-cadmium alloy, and the like may be used.

[0076] The separator separates the anode and the cathode, and provides a passage for lithium ions to move. Any separator may be used without particular limitation as long as it is generally used as a separator in a lithium secondary battery. Particularly, a separator having excellent moisture-retention ability for an electrolyte while having low resistance to the migration of electrolyte ions is preferable.

[0077] The lithium secondary battery according to the present disclosure as described above may be used as a power source of devices in portable devices such as mobile phones, notebook computers, digital cameras, and electric vehicles such as hybrid electric vehicles (HEVs).

[0078] Hereinafter, the details of experiments in Examples of the present disclosure described above and Comparative Examples to be compared therewith will be described.

Comparative Example 1

[0079] 22.9 g of Li.sub.2O and 30 g of NiO (molar ratio 1:1) were mixed, and then heat-treated at 685 degrees Celsius for 18 hours under an N.sub.2 atmosphere, and then the resulting reaction product was cooled to obtain irreversible additive particles Li.sub.2NiO.sub.2.

Comparative Example 2

[0080] LiNiO.sub.2 and more than 1.5M Li.sup.+Thenzophenone.sup.− were reacted in the presence of THF (tetrahydrofuran) under an inert atmosphere.

[0081] Specifically, the mixture of the above materials was stirred for one day, and the mixed powders were filtered. The obtained mixed powder was washed with dry THF and dried under vacuum to obtain a pre-powder in which a small amount of trigonal Li.sub.2NiO.sub.2 and LiNiO.sub.2 were mixed.

[0082] Subsequently, the pre-powder was heat-treated at 225° C. for 14 hours under dry helium flow to obtain a Li.sub.2NiO.sub.2 powder having a trigonal crystal structure with improved crystallinity.

Example 1

[0083] 22.9 g of Li.sub.2O, 30 g of NiO and 2.39 g of TiO.sub.2 (molar ratio 1:1:0.03) were mixed, and then heat-treated at 685 degrees Celsius for 18 hours under an N.sub.2 atmosphere, and then the resulting reaction product was cooled to obtain irreversible additive particles LiN.sub.0.97Ti.sub.0.03O.sub.2.

[0084] LiNi.sub.0.97Ti.sub.0.03O.sub.2 and more than 1.5M Li.sup.+Thenzophenone.sup.− were reacted in the presence of THF (tetrahydrofuran) under an inert atmosphere.

[0085] Specifically, the mixture of the above materials was stirred for one day, and the mixed powders were filtered. The obtained mixed powder was washed with dry THF and dried under vacuum to obtain a pre-powder in which a small amount of trigonal Li.sub.2Ni.sub.0.97Ti.sub.0.30O.sub.2 and LiNi.sub.0.97Ti.sub.0.03O.sub.2 were mixed.

[0086] Subsequently, the pre-powder was heat-treated at 225° C. for 14 hours under dry helium flow to obtain a Li.sub.2Ni.sub.0.97Ti.sub.0.03O.sub.2 powder having a trigonal crystal structure with improved crystallinity.

Experimental Example 1—XRD Analysis

[0087] 2 g of the irreversible additive particles prepared in Comparative Examples 1 and 2 and Example 1 were collected as samples, respectively, and subjected to XRD analysis. The results are shown in FIGS. 1 to 3, respectively.

[0088] XRD analysis was measured with a Bruker XRD D4 instrument, and experiment was performed from 10 to 80 degrees in 0.02 steps using a Cu source target.

[0089] Referring to FIGS. 1 to 3, it can be seen that the irreversible additives having mutually different structures according to Comparative Examples 1, 2 and Example 1 are formed. Specifically, it can be seen that Comparative Example 1 is formed in an orthorhombic type crystal structure, and Comparative Example 2 and Example 1 are formed in a trigonal crystal structure.

Production of Cathode and Lithium Secondary Battery

[0090] Using the irreversible additives prepared in Comparative Example 2 and Example 1, a cathode and a lithium secondary battery were produced by the following method.

[0091] Specifically, the irreversible additive prepared in Comparative Example 2 and Example 1, LiNi.sub.0.4Mn.sub.0.3Co.sub.0.3O.sub.2 as a cathode active material, a carbon black conductive material and a PVdF binder were mixed in a weight ratio of 4.6:87.9:3.5:4 in an N-methylpyrrolidone solvent to prepare a cathode slurry. The slurry was coated onto an aluminum current collector, and dried and rolled to produce a cathode.

[0092] In addition, MCMB (mesocarbon microbead), which is an artificial graphite mixed with 10 wt. % of SiO as an anode active material, a carbon black conductive material and PVdF binder were mixed in a weight ratio of 90:5:5 in an N-methylpyrrolidone solvent to prepare a composition for forming an anode, which was coated onto a copper current collector to produce an anode.

[0093] A porous polyethylene separator was interposed between the cathode and the anode produced as described above to produce an electrode assembly. The electrode assembly was placed inside a case, and then an electrolyte was injected into the case to produce a lithium secondary battery. At this time, the electrolyte was prepared by dissolving 1.15M lithium hexafluorophosphate (LiPF.sub.6) in an organic solvent consisting of ethylene carbonate/dimethyl carbonate/ethylmethyl carbonate (EC/DMC/EMC mixing volume ratio=3/4/3).

Experimental Example 2

[0094] 2 g of the irreversible additive particles prepared in Comparative Example 1, Comparative Example 2 and Example 1 were collected as samples, respectively, and their oxygen formation energies were measured. The results are shown in Table 1 below.

[0095] Specifically, the calculation of oxygen formation energy was performed based on the calculated value for DFT (density functional theory), PBE functional PAW_PBE pseudopotential, cut-off energy=520 eV, calculation model: supercell with Li.sub.48Ni.sub.24O.sub.48 atoms-substituting one Ni with Ti (ratio˜4.17at %), oxygen vacancy (VO) production concentration= 1/48 (˜2.1 at. %) O.sub.2 gas (O-rich environment).

TABLE-US-00001 TABLE 1 Oxygen (V.sub.0) formation energy (eV) Comparative Example 1 3.77 Comparative Example 2 4.21 Example 1 4.69

[0096] Referring to Table 1, it is confirmed that the energy of the trigonal irreversible additives of Comparative Examples 2 and Example 1 is higher than that of the orthorhombic irreversible additive of Comparative Example 1. It is expected that, during charging and discharging, the orthorhombic irreversible additive undergoes structural changes in the intercalation of Li ions via the trigonal system and then to the monoclinic system, whereas the trigonal irreversible additive is reduced in a structural change stage from the viewpoint that it progresses to the monoclinic system, and the trigonal system does not cause a side reaction as compared with the tetragonal system.

[0097] In addition, considering that the energy of the trigonal irreversible additive of Example 1 is higher than that of the trigonal additive of Comparative Example 2, it is presumed that the structural change in the intercalation of Li ions during charging and discharging will form more robust structure than the trigonal system without substitution. Therefore, it is expected that no side reactions will occur compared to the trigonal irreversible additives not substituted with Ti.

[0098] Although the present disclosure has been shown and described above with reference to the preferred embodiments, the scope of the present disclosure is not limited thereto, and numerous other modifications and embodiments can be devised by those skilled in the art, without departing from the spirit and scope of the principles of the present disclosure described in the appended claims. Further, these modified embodiments should not be understood individually from the technical spirit or perspective of the present disclosure.