Slurry including carbon black, electrode paste, method for producing electrode, and method for producing secondary battery

Abstract

A slurry including at least a carbon black and a dispersion medium, wherein a concentration of the carbon black in the slurry is 5% by mass or more and 25% by mass or less, and wherein in a volume-based frequency distribution of particle size of the carbon black measured by a laser diffraction/scattering method, provided that a volume concentration of carbon black with a particle size of 0.6 μm or more is x (%), a volume concentration of carbon black with a particle size of 0.3 μm or more and less than 0.6 μm is y (%), and a volume concentration of carbon black having a particle size of less than 0.3 μm is 100−(x+y) (%), the slurry satisfies 10≤x≤70, 30≤y≤90, and 0≤100−(x+y)≤30.

Claims

1. A slurry comprising at least a carbon black and a dispersion medium, wherein a concentration of the carbon black in the slurry is 5% by mass or more and 25% by mass or less, and wherein in a volume-based frequency distribution of particle size of the carbon black measured by a laser diffraction/scattering method, provided that a volume concentration of carbon black with a particle size of 0.6 μm or more is x (%), a volume concentration of carbon black with a particle size of 0.3 μm or more and less than 0.6 μm is y (%), and a volume concentration of carbon black having a particle size of less than 0.3 μm is 100−(x+y) (%), the slurry satisfies 10≤x≤70, 30≤y≤90, and 0≤100−(x+y)≤30.

2. The slurry according to claim 1, wherein a cumulative 50% particle size (D50) in the volume-based cumulative distribution of particle size of the carbon black measured by the laser diffraction/scattering method is 0.40 to 0.85 μm.

3. The slurry according to claim 1, wherein a cumulative 90% particle size (D90) in the volume-based cumulative distribution of particle size of the carbon black measured by the laser diffraction/scattering method is 1.0 to 30.0 μm.

4. The slurry according to claim 1, comprising N-methyl-2-pyrrolidone as a dispersion medium.

5. The slurry according to claim 1, comprising a dispersant.

6. The slurry according to claim 5, wherein a content of the dispersant in the slurry is 5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the carbon black.

7. The slurry according to claim 5, comprising a nonionic dispersant as the dispersant.

8. The slurry according to claim 5, comprising polyvinyl alcohol as the dispersant.

9. The slurry according to claim 8, wherein a degree of saponification of the polyvinyl alcohol is 86 to 97 mol %.

10. The slurry according to claim 1, satisfying 30≤x≤60,30≤y≤60, and 10≤100−(x+y)≤30.

11. An electrode paste, comprising the slurry according to claim 1, an electrode active material, and a binder.

12. A method for producing an electrode, comprising applying the electrode paste according to claim 11 to a current collector.

13. A method for producing a secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, the method comprising producing one or both of the positive electrode and the negative electrode by carrying out the method for producing an electrode according to claim 12.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a diagram showing an example of a basic configuration of a lithium-ion secondary battery.

DETAILED DESCRIPTION OF THE INVENTION

(2) (1. Slurry Including Carbon Black)

(3) According to one embodiment of the present invention, a slurry including at least a carbon black and a dispersion medium is provided. Carbon black maintains the conductivity of the entire electrode and also serves as a cushioning material for expansion and contraction of the active materials. Examples of carbon black include thermal black, furnace black, lamp black, channel black, and acetylene black. Among these, acetylene black is preferable because of its high purity.

(4) The carbon black concentration in the slurry is preferably 5% by mass or more and 25% by mass or less. If the lower limit of the carbon black concentration in the slurry is less than 5% by mass, the concentration is too low and the proportion of transportation cost and dispersion medium cost get high, resulting in a relatively high price. The lower limit of the carbon black concentration in the slurry is more preferably 6% by mass or more, and even more preferably 7% by mass or more. On the other hand, if the upper limit of the carbon black concentration in the slurry exceeds 25% by mass, the viscosity gets too high and dispersion becomes difficult, and it becomes difficult to obtain the desired conductivity-imparting effect. The upper limit of the carbon black concentration in the slurry is more preferably 23% by mass or less, even more preferably 20% by mass or less, even more preferably 14% by mass or less, and even more preferably 11% by mass or less.

(5) In a volume-based frequency distribution of particle size of the carbon black measured by a laser diffraction/scattering method, provided that a volume concentration of carbon black with a particle size of 0.6 μm or more is x (%), a volume concentration of carbon black with a particle size of 0.3 μm or more and less than 0.6 μm is y (%), and a volume concentration of carbon black having a particle size of less than 0.3 μm is 100−(x+y) (%), it is preferable that the carbon black in the slurry satisfy 10≤x≤70, 30≤y≤90, and 0≤100−(x+y)≤30. By using carbon black having such a particle size distribution as a conductive material, the internal resistance of the battery can be significantly reduced. It is more preferable that 10≤x≤60, 30≤y≤80, and 5≤100−(x+y)≤30 be satisfied, and even more preferable that 30≤x≤60, 30≤y≤60, and 10≤100−(x+y)≤30 be satisfied.

(6) As the carbon black in the slurry, it is preferable that a cumulative 50% particle size (D50) in the volume-based cumulative distribution of particle size of the carbon black measured by the laser diffraction/scattering method be 0.40 to 0.85 μm. By controlling the D50 in combination with the volume-based frequency distribution of particle size of the carbon black described above, the internal resistance of the battery can be further reduced. The D50 is more preferably 0.45 to 0.80 μm, and even more preferably 0.45 to 0.75 μm.

(7) As the carbon black in the slurry, it is preferable that a cumulative 90% particle size (D90) in the volume-based cumulative distribution of particle size of the carbon black measured by the laser diffraction/scattering method be 1.0 to 30.0 μm. By controlling the D90 in combination with the volume-based frequency distribution of particle size of the carbon black described above, the internal resistance of the battery can be further reduced. The D90 is more preferably 1.0 to 27.5 μm, and even more preferably 1.0 to 25.0 μm.

(8) In the present specification, the volume-based distribution of particle size of the carbon black measured by the laser diffraction/scattering method can be measured by the following method using a particle size distribution measuring device (example: “Microtrac MT3300EXII”, “Ultra-Small Volume Recirculator (USVR)” produced by MicrotracBEL).

(9) Measurement conditions: Measuring range=0.02 to 2000 μm; particle permeability=absorption; particle shape=non-spherical; solvent=N-methylpyrrolidone; recirculating output=5

(10) Sample charging amount: Add and adjust the slurry so that it is within the optimum concentration range displayed at the time of sample charge.

(11) In addition, the particle size distribution of carbon black measured here is not the particle size distribution of the primary particle size of carbon black, but the particle size distribution of the structure formed by the aggregation of the primary particles of carbon black.

(12) Examples of the dispersion medium include, but not limited to, aliphatic hydrocarbon solvents such as pentane, normal hexane, octane, cyclopentane and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene and cymene; aldehyde solvents such as furfural; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone; ester solvents such as butyl acetate, ethyl acetate, methyl acetate, butyl propionate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and ethylene glycol diacetate; ether solvents such as tetrahydrofuran, dioxane and ethylene glycol dimethyl ether; alcohol solvents such as methanol, ethanol, normal propyl alcohol, isopropyl alcohol, butyl alcohol, octyl alcohol, cyclohexanol, allyl alcohol, benzyl alcohol, cresol and furfuryl alcohol; polyol solvents such as glycerol, ethylene glycol and diethylene glycol; alcohol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether and diethylene glycol monobutyl ether; aprotic polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide and dimethylformamide; and water. As the solvent, one type may be used alone, or two or more types may be used in combination. Among these, N-methyl-2-pyrrolidone is preferable in terms of solubility when polyvinylidene fluoride is used as the binder.

(13) The slurry preferably contains a dispersant in order to enhance the dispersion stability of the carbon black. As the dispersant, those that do not affect the battery characteristics and do not decompose when a voltage is applied in the battery are preferable. As the dispersant, for example, a non-ionic dispersant having no ionic functional group can be used. However, the non-ionic dispersant may contain a small amount of ionic functional groups. Specific examples of the dispersant include polyvinylidene fluoride, polytetrafluoroethylene, polyhexafluoropropylene, polyethylene, polypropylene, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyacrylic acid, polyvinyl butyral, polyacrylamide, polyurethane, polydimethylsiloxane, epoxy resin, acrylic resin, polyester resin, melamine resin, phenol resin, various rubbers, lignin, pectin, gelatin, xanthan gum, welan gum, succinoglycan, polyvinyl alcohol, polyvinyl acetal, cellulose resin, polyalkylene oxide, polyvinyl ether, polyvinylpyrrolidone, chitins, chitosans, starches and polyamines, and the like. As the dispersant, one type may be used alone, or two or more types may be used in combination.

(14) As the dispersant, polyvinyl alcohol, which also has an effect as a binder, is preferable. The polyvinyl alcohol may be either a fully saponified type or a partially saponified type, but a polyvinyl alcohol having a degree of saponification of 86 to 97 mol % is more preferable, and polyvinyl alcohol having a degree of saponification of 86 to 90 mol % is even more preferable because there are extremely few side reactions when a high voltage is applied to the positive electrode. The degree of saponification is measured in accordance with JIS K6726: 1994. That is, it can be obtained by quantifying the residual acetic acid group (mol %) in the sample with sodium hydroxide and subtracting it from 100.

(15) The content of the dispersant in the slurry is preferably 5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the carbon black. When the lower limit of the content of the dispersant in the slurry is less than 5 parts by mass with respect to 100 parts by mass of the carbon black, the dispersibility is poor when dispersed, and when mixed with active materials, dispersion tends to be poor due to reaggregation. The lower limit of the content of the dispersant in the slurry is more preferably 6 parts by mass or more, and even more preferably 7 parts by mass or more with respect to 100 parts by mass of the carbon black. Further, if the upper limit of the content of the dispersant in the slurry exceeds 20 parts by mass with respect to 100 parts by mass of the carbon black, there is a concern that the battery characteristics may be deteriorated, and cutting of the carbon black structure may be further promoted during the dispersion process. The upper limit of the content of the dispersant in the slurry is more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less with respect to 100 parts by mass of the carbon black.

(16) (2. Production of Slurry Including Carbon Black)

(17) An example of method for producing the above-mentioned slurry including carbon black will be described. First, a raw material gas such as hydrocarbon is supplied from a nozzle installed at the top of a reactor, carbon black powder is produced by a thermal decomposition reaction and/or a partial combustion reaction, and collected by a bag filter directly connected to the lower portion of the reactor. The raw material gas used is not particularly limited, and gaseous hydrocarbons such as acetylene, methane, ethane, propane, ethylene, propylene and butadiene, and gasified oily hydrocarbons such as toluene, benzene, xylene, gasoline, kerosene, light oil and heavy oil can be used. As the raw material gas, one type may be used alone, or two or more types may be used in combination. As the raw material gas, it is preferable to use acetylene gas which has a small amount of impurities such as sulfur.

(18) The appropriate average particle size of the primary particles of the carbon black powder is 15 to 30 nm. If the average particle size is smaller than 15 nm, the dispersion processing, which will be described later, cannot be performed, and if it is larger than 30 nm, it is difficult to obtain an appropriate structure size, and the target conductivity-imparting ability cannot be obtained. The average particle size of the primary particles herein means the average particle size measured based on a photograph taken with a transmission electron microscope or the like. Further, the particle size is a circle-equivalent diameter calculated from the area of the primary particles. Specific examples of the carbon black powder include those available in the market, and mention can be made to acetylene black Li-435 and FX-35 produced by Denka Co., Ltd. and processed products thereof.

(19) Next, a predetermined amount of carbon black powder and a dispersant are charged into a dispersion medium, and a dispersion processing is carried out to manufacture a slurry including carbon black. As long as the particle size distribution of the carbon black can be controlled, a dispersion processor used for ordinary dispersion processing or the like can be used. For example, mention can be made to mixers such as dispersers, homomixers, Henschel mixers and planetary mixers; dispersion processing equipment using mediums such as bead mills; and medium-free dispersion processing equipment such as ultrasonic homogenizers and wet atomizers. The dispersion processor is not limited to these. Further, one type of the dispersion processor may be used, but a plurality of types of processors may be used in combination as appropriate.

(20) Regardless of which dispersion processor is used, it is important to set the dispersion processing conditions such that the volume concentration (%) of carbon black with a particle size of 0.6 μm or more, the volume concentration (%) of carbon black with a particle size of 0.3 μm or more and less than 0.6 μm, and the volume concentration (%) of carbon black with a particle size of less than 0.3 μm are within the predetermined range. In the dispersion processing, the larger the energy and the longer the time are, the larger the volume concentration (%) of carbon black having a particle size of less than 0.3 μm becomes, due to progress of the elimination of secondary aggregation of the carbon black powder and the cutting of the structure.

(21) Further, in the dispersion processing, the smaller the energy and the shorter the time are, the larger the volume concentration (%) of carbon black having a particle size of 0.6 μm or more becomes because the elimination of secondary aggregation of the carbon black powder and the cutting of the structure do not progress,

(22) (3. Production of Electrode Paste)

(23) An electrode paste can be produced by adding an electrode active material and a binder to the slurry including the carbon black according to the present invention. For example, 95 to 99 parts by mass of the electrode active material can be added, and 97 to 99 parts by mass can be preferably added to 1 part by mass of the carbon black in the slurry. The binder can be added in an amount of 1 to 2 parts by mass, preferably 0.5 to 1 part by mass to 1 part by mass of the carbon black in the slurry. Electrode active material includes positive electrode active materials and negative electrode active materials. The slurry according to the present invention can be used for producing either a positive electrode paste or a negative electrode paste.

(24) The positive electrode active materials that can be used include, but not limited to, a lithium composite oxide mainly composed of Li.sub.xMO.sub.2 (where M is one or more types of transition metals and 0.05≤x≤1.0), and lithium-free metal sulfides and metal oxides such as TiS.sub.2, FeS, MoS.sub.2, NbSe.sub.2, and V.sub.2O.sub.5. Among them, lithium-containing transition metal oxides containing cobalt and/or manganese such as LiCoO.sub.2, LiNi.sub.1/3Mn.sub.1/3CO.sub.1/3O.sub.2, and LiMn.sub.2O.sub.4 are preferable in that they can increase the electromotive force of the battery. Other positive electrode active materials that can be used include LiNi.sub.xCo.sub.yAl.sub.zO.sub.2 in which a part of cobalt is replaced with nickel or aluminum, LiNi.sub.xMn.sub.yCo.sub.zO.sub.2 (x>y, z) in which a part of cobalt and manganese is replaced with nickel to increase the nickel content, and LiNi.sub.xMn.sub.2O.sub.4 in which a part of manganese is replaced with nickel, or the like. Furthermore, conductive polymers such as polyaniline, polyacetylene, polypyrrole, and polythiophene can also be used. As the positive electrode active material, one type may be used alone, or two or more types may be used in combination.

(25) The negative electrode active materials that can be used include, but not limited to various carbonaceous materials such as natural graphite, artificial graphite, graphite, activated carbon, coke, needle coke, fluid coke, mesophase microbeads, carbon fibers, and pyrolytic carbon. Further, as the negative electrode active material, mention can be made to metallic lithium or its alloys (LiSn alloys, LiSi alloys, LiBi alloys, LiPb alloys, and the like), lithium composite oxides (lithium titanate, lithium vanadate, lithium silicate, lithium-containing iron oxides, and the like), conductive polymers (polyacetylene, poly-p-phenylene, and the like). As the negative electrode active material, one type may be used alone, or two or more types may be used in combination.

(26) Examples of the binder include, but not limited to, those that are normally used, such as polyethylene, nitrile rubber, polybutadiene, butyl rubber, polystyrene, styrene-butadiene rubber, polysulfide rubber, nitrocellulose, cetylmethylcellulose, polyvinyl alcohol, ethylene tetrafluoride resin, polyvinylidene fluoride, polychloroprene fluoride, and the like. As the binder, one type may be used alone, or two or more types may be used in combination.

(27) The electrode active material preferably has an average particle size in the range of 0.05 to 100 μm, and more preferably in the range of 0.1 to 50 μm. In the present specification, the average particle size of the electrode active material is an average value of the particle size of the electrode active material as measured with an electron microscope. Further, the particle size is a circle-equivalent diameter calculated from the area of a primary particle.

(28) (4. Manufacture of Electrodes)

(29) The electrode can be produced as a laminate in which an electrode mixture layer is laminated on a current collector by applying an electrode paste to a current collector such as a metal foil and then evaporating the solvent for drying. As the electrode, either a positive electrode or a negative electrode can be produced. Examples of the material of the current collector used for the electrode include, but not limited to, metals such as gold, silver, copper, platinum, aluminum, iron, nickel, chromium, manganese, lead, tungsten, and titanium, and alloys containing any one of these as a main component (stainless steel, and the like). Among these, it is preferable to use aluminum for the positive electrode and copper for the negative electrode. The current collector is generally provided in the form of a foil, but the current collector is not limited to that, and a perforated foil-shaped or mesh-shaped current collector can also be used.

(30) Examples of the method of applying the electrode paste to a current collector include, but not limited to, die coating method, dip coating method, roll coating method, doctor coating method, knife coating method, spray coating method, gravure coating method, screen printing method, electrostatic coating method, and the like. As the drying method, left-to-dry, a blowing dryer, a warm gas-blowing dryer, an infrared heater, a far infrared heater and the like can be used, but the drying method is not particularly limited thereto.

(31) Further, after the coating, a flatting process such as a flat-plate press or a calendar roll may be performed. The target electrode can be obtained by pressurizing the current collector and the electrode mixture layer with a roll press or the like to bring them into close contact with each other.

(32) (5. Manufacture of Battery)

(33) According to one embodiment of the present invention, a secondary battery can be produced using one or both of the positive electrode and the negative electrode obtained in the above procedure. Examples of the secondary battery include, but not limited to, lithium-ion secondary batteries, as well as sodium-ion secondary batteries, magnesium secondary batteries, alkaline secondary batteries, lead storage batteries, sodium sulfur secondary batteries, lithium air secondary batteries, and the like. Conventionally known electrolytes, separators, and the like can be appropriately used in each secondary battery.

(34) For example, in the case of a lithium-ion secondary battery, an electrolyte containing lithium can be used by dissolving it in a non-aqueous solvent. As specific examples, mention can be made to LiBF.sub.4, LiClO.sub.4, LiPF.sub.6, LiAsF.sub.6, LiSbF.sub.6, LiCF.sub.3SO.sub.3, Li(CF.sub.3SO.sub.2).sub.2N, LiC.sub.4F.sub.9SO.sub.3, Li(CF.sub.3SO.sub.2).sub.3C, Lil, LiBr, LiCl, LiAlCl, LiHF.sub.2, LiSCN, or LiBPh.sub.4, or the like. As the electrolyte, one type may be used alone, or two or more types may be used in combination.

(35) Examples of the non-aqueous solvent include, but not limited to, carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethylmethyl carbonate and diethyl carbonate; lactones such as γ-butyrolactone, γ-valerolactone and γ-octanoic lactone; glymes such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,2-methoxyethane, 1,2-ethoxyethane and 1,2-dibutoxyethane; esters such as methylformate, methylacetate and methylpropionate; sulfoxides such as dimethyl sulfoxide and sulfolane; and nitriles such as acetonitrile, and the like. As the solvent, one type may be used alone, or two or more types may be used in combination.

(36) Further, as the electrolyte, an organic solid electrolyte and/or an inorganic solid electrolyte can also be used. Examples of the organic solid electrolyte include, but not limited to, polyelectrolyte such as polyethylene oxide (PEO) and organic electrolyte salts such as lithium bis (trifluoromethanesulfonyl) imide (LiTFSI). Examples of the inorganic solid electrolyte include, but not limited to, sulfide type inorganic solid electrolytes (example: LPS type, LGPS type) and oxide type inorganic solid electrolytes (example: LLZ type).

(37) As the separator sandwiched between the positive electrode and the negative electrode as needed, any material having sufficient strength, such as an electrically insulating porous film, a net, and a non-woven fabric, can be used. In particular, it is preferable to use a separator having low resistance to ion transfer of the electrolytic solution and excellent in solution retention. The material is not particularly limited, but mention can be made to inorganic fibers such as glass fibers or organic fibers, synthetic resins such as polyethylene, polypropylene, polyester, polytetrafluoroethylene, polyflon, and the like, and layered composites thereof, and the like. From the viewpoint of adhesiveness and safety, polyethylene, polypropylene or a layered composite film thereof is desirable. Examples include, but not limited to, polyethylene non-woven fabrics, polypropylene non-woven fabrics, polyamide non-woven fabrics, and those obtained by subjecting them to a hydrophilic treatment.

(38) The structure of the secondary battery can be various shapes depending on the purpose of use, such as a paper type, a cylindrical type, a button type, and a laminated type.

(39) The application of the lithium-ion secondary battery according to the present invention is not particularly limited. For example, it can be used as a power source for small consumer devices such as smart mobile phones, tablet personal computers, household electric appliances, and electric tools. Further, it can also be used as a power source for power of electric vehicles and hybrid vehicles, industrial equipment such as an elevator having a system for recovering at least a part of kinetic energy, and various large power sources such as a power source for various commercial and household power storage systems.

EXAMPLES

(40) Examples of the present invention are shown below together with Comparative Examples, but the Examples are provided for a better understanding of the present invention and its advantages, and are not intended to limit the invention.

Example 1

(41) (1. Preparation of Slurry)

(42) To 89.0 parts by mass of N-methyl-2-pyrrolidone, 1.0 part by mass of polyvinyl alcohol (Poval B05 produced by Denka Co., Ltd., degree of saponification: 87%) and 10.0 parts by mass of carbon black powder (acetylene black Li-435 produced by Denka Co., Ltd.) were added and stirred with a planetary mixer (HIVIS DISPER MIX Model 3D-5 produced by PRIMIX Corporation) for 120 minutes to prepare a slurry including carbon black. The obtained slurry was put into a bead mill (Mugenflow MGF2-ZA produced by Ashizawa Finetech Co., Ltd.) equipped with zirconia beads (diameter 0.5 mm) and subjected to a dispersion processing. After the dispersion processing, the zirconia beads were removed by filtration to prepare a slurry.

(43) The volume-based frequency distribution and cumulative distribution of particle size of the carbon black in the slurry thus obtained were measured according to the method described above using a laser diffraction/scattering type particle size distribution measuring device (Microtrac MT3300EXII produced by MicrotracBEL Corp.). In this Example, provided that the volume concentration of carbon black with a particle size of 0.6 μm or more is x (%), the volume concentration of carbon black with a particle size of 0.3 μm or more and less than 0.6 μm is y (%), and the volume concentration of carbon black having a particle size of less than 0.3 μm is 100−(x+y) (%), the result was x=40.5%, y=44.1%, and 100−(x+y)=15.4%.

(44) (2. Preparation of Positive Electrode Paste)

(45) With respect to 1.0 part by mass of the carbon black in the slurry obtained above, 2.0 parts in solute mass of polyvinylidene fluoride in N-methyl-2-pyrrolidone solution as a binder, and 97 parts by mass of lithium nickel cobalt manganese composite oxide LiNi.sub.0.5Mn.sub.0.3Co.sub.0.2O.sub.2 (produced by Jiangxi Jiangte Lithium Battery Materials Co., Ltd, “S532”) as a positive electrode active material were added and mixed. Further, in order to improve the coatability, N-Methyl-2-pyrrolidone was added as a dispersion medium and mixed to prepare a positive electrode paste such that in the viscosity curve measured with a rheometer (MCR300 produced by Anton Pearl Co., Ltd.), the viscosity at a shear rate of 1 sec.sup.−1 was 10000 mPa.Math.sec or less.

(46) (3. Preparation of Positive Electrode)

(47) The positive electrode paste was applied onto an aluminum foil having a thickness of 20 μm using a baker-type applicator, followed by drying pressing and cutting to prepare a positive electrode.

(48) (4. Preparation of Negative Electrode)

(49) A negative electrode paste (96.0% by mass of graphite (“AGP-2A” produced by Shenzhen BTR Co., Ltd.), 1.0% by mass of carbon black (“Li-400” produced by Denka Co., Ltd.), 1.0% by mass of sodium carboxymethyl cellulose, and 2.0% by mass of styrene-butadiene copolymer) was applied onto a copper foil having a thickness of 10 μm using a baker-type applicator, followed by drying, pressing and cutting to prepare a negative electrode.

(50) (5. Preparation of Secondary Battery)

(51) As shown in FIG. 1, an aluminum tab 5 was connected to the above-described positive electrode 1, a nickel tab 6 was connected to the above-described negative electrode 2, and the above-described positive electrode 1, a polyolefin microporous film (separator) 3, and the above-described negative electrode 2 were overlapped together and laminated. Then, the exterior (aluminum laminated film) 4 was packed and pre-sealed, and then electrolytic solution was injected, and battery formatting and vacuum sealing were performed to prepare a laminate type secondary battery.

(52) (6. Measurement of Internal Resistance)

(53) Using the prepared secondary battery, the voltage when a current of 0.2, 0.4, 0.6, 0.8, and 1.0 mA was applied at 25° C. for 10 seconds was measured. At this time, the SOC (State Of Charge) was set to 50%. The battery internal resistance R was calculated from R=V/I, and the average value of R was obtained. The internal resistance of the battery in Example 1 was 1.45Ω.

(54) (7. Output Properties (Capacity Retention Rate at 3 C Discharge))

(55) The prepared secondary battery was charged at a constant current and constant voltage of 4.2 V with the limitation of 0.2 C at 25° C., and then discharged to 2.75 V at a constant current with 0.2 C. Next, the discharge current was changed to 0.2 C and 3 C, and the discharge capacity for each discharge current was measured. Then, the capacity retention rate at the time of 3 C discharge with respect to the time of 0.2 C discharge was calculated. The capacity retention rate at the time of 3 C discharge of this Example 1 was 82.4%.

Example 2

(56) A slurry, an electrode paste, a positive electrode, and a secondary battery were prepared in the same manner as in Example 1 except that the dispersion processing time and peripheral speed of the bead mill in Example 1 were changed, and each evaluation was carried out. The results are shown in Table 1.

Example 3

(57) A slurry, an electrode paste, a positive electrode, and a secondary battery were prepared in the same manner as in Example 1 except that based on Example 1, a slurry including carbon black in which the N-methyl-2-pyrrolidone was changed to 85.5 parts by mass and the carbon black powder was changed to 13.5 parts by mass was used, and each evaluation was carried out. The results are shown in Table 1.

Example 4

(58) A slurry, an electrode paste, a positive electrode, and a secondary battery were prepared in the same manner as in Example 1 except that based on Example 1, a slurry including carbon black in which the N-methyl-2-pyrrolidone was changed to 83.5 parts by mass, the polyvinyl alcohol was changed to 1.5 parts by mass and the carbon black powder was changed to 15.0 parts by mass was used, and each evaluation was carried out. The results are shown in Table 1.

Example 5

(59) A slurry, an electrode paste, a positive electrode, and a secondary battery were prepared in the same manner as in Example 1 except that based on Example 1, a slurry including carbon black in which the N-methyl-2-pyrrolidone was changed to 80.2 parts by mass, the polyvinyl alcohol was changed to 1.8 parts by mass and the carbon black powder was changed to 18.0 parts by mass was used, and each evaluation was carried out. The results are shown in Table 1.

Example 6

(60) A slurry, an electrode paste, a positive electrode, and a secondary battery were prepared in the same manner as in Example 1 except that based on Example 1, a slurry including carbon black in which the N-methyl-2-pyrrolidone was changed to 78.0 parts by mass, the polyvinyl alcohol was changed to 2.0 parts by mass and the carbon black powder was changed to 20.0 parts by mass was used, and each evaluation was carried out. The results are shown in Table 1.

Example 7

(61) A slurry, an electrode paste, a positive electrode, and a secondary battery were prepared in the same manner as in Example 2 except that the dispersion processing time and peripheral speed of the bead mill were changed, and each evaluation was carried out. The results are shown in Table 1.

Example 8

(62) A slurry, an electrode paste, a positive electrode, and a secondary battery were prepared in the same manner as in Example 1 except that based on Example 1, a slurry including carbon black in which the N-methyl-2-pyrrolidone was changed to 72.5 parts by mass, the polyvinyl alcohol was changed to 2.5 parts by mass and the carbon black powder was changed to 25.0 parts by mass was used, and each evaluation was carried out. The results are shown in Table 1.

Example 9

(63) A slurry, an electrode paste, a positive electrode, and a secondary battery were prepared in the same manner as in Example 1 except that a slurry including carbon black was prepared by loading 95.0 parts by mass of N-methyl-2-pyrrolidone and 5.0 parts by mass of carbon black powder (Acetylene Black Li-435 produced by Denka Co., Ltd.) into a 50 ml vial, and stirring for 60 minutes with an ultrasonic cleaner (ASU-6 produced by AS ONE Corporation). Each evaluation was then carried out. The results are shown in Table 1.

Comparative Example 1

(64) A slurry, an electrode paste, a positive electrode, and a secondary battery were prepared in the same manner as in Example 3 except that the dispersion processing time and peripheral speed of the bead mill were changed, and each evaluation was carried out. The results are shown in Table 1.

Comparative Example 2

(65) A slurry, an electrode paste, a positive electrode, and a secondary battery were prepared in the same manner as in Example 4 except that the dispersion processing time and peripheral speed of the bead mill were changed, and each evaluation was carried out. The results are shown in Table 1.

Comparative Example 3

(66) A slurry, an electrode paste, a positive electrode, and a secondary battery were prepared in the same manner as in Comparative Example 1 except that the dispersion processing time and peripheral speed of the bead mill were changed, and each evaluation was carried out. The results are shown in Table 1.

Comparative Example 4

(67) A slurry, an electrode paste, a positive electrode, and a secondary battery were prepared in the same manner as in Example 1 except that based on Example 1, a slurry including carbon black in which the N-methyl-2-pyrrolidone was changed to 94.5 parts by mass, the polyvinyl alcohol was changed to 0.5 parts by mass and the carbon black powder was changed to 5.0 parts by mass was used, and further the dispersion processing time and peripheral speed of the bead mill were changed. Each evaluation was then carried out. The results are shown in Table 1.

Comparative Example 5

(68) A slurry, an electrode paste, a positive electrode, and a secondary battery were prepared in the same manner as in Example 8 except that the dispersion processing time and peripheral speed of the bead mill were changed, and each evaluation was carried out. The results are shown in Table 1.

Comparative Example 6

(69) A slurry, an electrode paste, a positive electrode, and a secondary battery were prepared in the same manner as in Example 1 except that based on Example 1, a slurry including carbon black in which the N-methyl-2-pyrrolidone was changed to 69.2 parts by mass, the polyvinyl alcohol was changed to 2.8 parts by mass and the carbon black powder was changed to 28.0 parts by mass was used, and each evaluation was carried out. The results are shown in Table 1.

Comparative Example 7

(70) A slurry, an electrode paste, a positive electrode, and a secondary battery were prepared in the same manner as in Comparative Example 1 except that based on Comparative Example 1, a slurry comprising carbon black in which the N-methyl-2-pyrrolidone was changed to 95.6 parts by mass, the polyvinyl alcohol was changed to 0.4 parts by mass and the carbon black powder was changed to 4.0 parts by mass was used, and each evaluation was carried out. The results are shown in Table 1.

(71) TABLE-US-00001 TABLE 1 Carbon black Volume concentration Battery concentration of carbon black (%) internal Output (% by mass) in 0.6 μm 0.3 μm or more and Less than D50 D90 resistance properties Test number the slurry or more less than 0.6 μm 0.3 μm μm μm Ω % Example 1 10 40.5 44.1 15.4 0.51 2.27 1.45 82.4 Example 2 10 31.5 48.0 20.5 0.44 1.44 1.51 81.9 Example 3 13.5 45.1 39.8 15.1 0.57 2.78 1.58 79.1 Example 4 15 43.1 40.1 16.8 0.53 2.43 1.78 78.1 Example 5 18 38.3 42.6 19.1 0.51 1.93 1.71 77.5 Example 6 20 13.4 81.0 5.6 0.62 1.55 1.73 76.9 Example 7 10 10.9 60.0 29.1 0.41 1.33 1.75 76.0 Example 8 25 52.3 33.7 14.0 0.75 11.7 1.80 75.5 Example 9 5 61.2 31.6 7.2 0.78 15.8 1.80 75.2 Comparative Example 1 13.5 9.5 61.4 29.1 0.35 1.23 1.98 72.1 Comparative Example 2 15 55.8 28.2 16.0 0.76 10.2 2.01 70.9 Comparative Example 3 13.5 27.3 38.3 34.4 0.42 1.35 2.19 69.1 Comparative Example 4 5 13.5 28.7 57.8 0.40 1.21 2.81 56.1 Comparative Example 5 25 70.5 22.0 7.5 0.90 21.3 3.05 54.2 Comparative Example 6 28 72.0 26.5 1.5 0.92 23.1 3.11 52.0 Comparative Example 7 4 12.0 29.8 58.2 0.39 1.18 3.31 48.9

DESCRIPTION OF REFERENCE NUMERALS

(72) 1 Non-aqueous secondary battery positive electrode 2 Non-aqueous secondary battery negative electrode 3 Insulation layer (microporous polyolefin film) 4 Exterior 5 Aluminum tab 6 Nickel tab