WO2011125410A1 - 非水電解質二次電池 - Google Patents
非水電解質二次電池 Download PDFInfo
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- WO2011125410A1 WO2011125410A1 PCT/JP2011/055657 JP2011055657W WO2011125410A1 WO 2011125410 A1 WO2011125410 A1 WO 2011125410A1 JP 2011055657 W JP2011055657 W JP 2011055657W WO 2011125410 A1 WO2011125410 A1 WO 2011125410A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a non-aqueous electrolyte secondary battery including a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, and a non-aqueous electrolyte solution in which a solute is dissolved in a non-aqueous solvent.
- a lithium-containing transition metal composite oxide having a layered structure containing a large amount of nickel as a transition metal is used as a substance, the lithium-containing transition metal composite oxide is prevented from being deteriorated by exposure to the atmosphere, and the atmosphere It is characterized in that the output characteristics after exposure, in particular, the output characteristics at low temperatures are improved.
- nickel-hydrogen storage batteries are widely used as power sources for such electric vehicles.
- nonaqueous electrolyte secondary batteries as power sources with higher capacity and higher output is being studied. .
- a lithium-containing transition metal composite oxide mainly composed of cobalt such as lithium cobalt oxide (LiCoO 2 ) is mainly used as the positive electrode active material of the positive electrode. It has been.
- cobalt used in the above positive electrode active material is a scarce resource, and there are problems such as high cost and difficulty in stable supply.
- it is used as a power source for hybrid electric vehicles and the like.
- a large amount of cobalt is required, and the cost as a power source becomes very high.
- lithium nickelate (LiNiO 2 ) having a layered structure is expected as a material capable of obtaining a large discharge capacity, but is inferior in thermal stability at a high temperature, increases in overvoltage, and is exposed to the atmosphere. As a result, the discharge capacity and output are reduced, which makes it difficult to handle in an atmospheric environment.
- a lithium-containing transition metal composite oxide having a layered structure in which the main component of the transition metal is composed of two elements of nickel and manganese as a positive electrode active material that is low in cost and excellent in thermal stability. Is attracting attention.
- the lithium-containing transition metal composite oxide having a layered structure in which the main component of the transition metal is composed of two elements of nickel and manganese is remarkably inferior to lithium cobaltate in high rate charge / discharge characteristics, and the atmosphere. There is a problem that handling in the environment is difficult.
- Patent Document 1 proposes a single-phase cathode material in which a part of the nickel and manganese is substituted with cobalt in a lithium-containing transition metal composite oxide having a layered structure containing at least nickel and manganese.
- Patent Document 2 a surface treatment layer with a coupling agent is provided on the surface of the positive electrode mixture layer.
- Patent Document 2 when a surface treatment layer with a coupling agent is provided on the surface of the positive electrode mixture layer, the surface treatment layer inhibits lithium ions from entering and exiting the positive electrode, resulting in a large output characteristic. There is a problem of lowering.
- the electroconductive coating layer using a carbon material etc. is formed in the surface of the primary particle of a positive electrode active material, the volume change of the positive electrode active material layer by charging / discharging is suppressed, and positive electrode active material particle It has been proposed to suppress the isolation from the conductive network in the positive electrode active material layer, and to increase the capacity and life of the nonaqueous electrolyte secondary battery.
- Patent Document 3 even when a conductive coating layer using a carbon material or the like is formed on the surface of the primary particles of the positive electrode active material, the entry and exit of lithium ions into the positive electrode active material is inhibited. However, there is a problem that the output characteristics are greatly deteriorated.
- the present invention solves the above problems in a non-aqueous electrolyte secondary battery comprising a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, and a non-aqueous electrolyte solution in which a solute is dissolved in a non-aqueous solvent.
- the problem is to be solved.
- the lithium-containing transition metal composite oxide when a lithium-containing transition metal composite oxide having a layered structure containing a large amount of nickel as a transition metal is used as the positive electrode active material, the lithium-containing transition metal composite oxide is exposed to the atmosphere. It is an object of the present invention to prevent the deterioration of the output characteristics after exposure to the atmosphere, and in particular, to prevent the output characteristics at low temperatures from deteriorating.
- the present invention includes a positive electrode in which a positive electrode mixture layer including a mixture of a positive electrode active material and a conductive carbon material is formed on the surface, and a negative electrode active material.
- a non-aqueous electrolyte secondary battery including a negative electrode and a non-aqueous electrolyte solution in which a solute is dissolved in a non-aqueous solvent
- a general formula Li a Ni x M (1-x) O 2 In the formula, M is one or more elements and satisfies the conditions of 0 ⁇ a ⁇ 1.2 and 0.4 ⁇ x ⁇ 1.0.
- the ratio of carbon atoms to all atoms on the surface of the positive electrode was 80% or more.
- the ratio of carbon atoms to all atoms on the surface of the positive electrode is a value measured from the surface of the positive electrode using an energy dispersive X-ray fluorescence spectrometer (EDX).
- EDX energy dispersive X-ray fluorescence spectrometer
- the lithium-containing transition metal composite oxide used for the positive electrode active material is one having a nickel Ni molar ratio x of 0.4 or more in order to increase the charge / discharge capacity of the positive electrode active material. is there.
- the lithium-containing transition metal composite oxide having a large Ni ratio is used as the positive electrode active material, the positive electrode active material tends to absorb moisture and deteriorate when exposed to the atmosphere as described above.
- the above M is not particularly limited as long as it can constitute a lithium-containing transition metal composite oxide having a layered structure.
- Al, Mn, Cu, Mg, Ba, Ti, Zr, and Nb can be used.
- the ratio of carbon atoms to all atoms is 80% or more.
- the coupling agent provided on the surface of the positive electrode mixture layer as in the prior art.
- the surface treatment layer prevents the lithium ions from entering and exiting the positive electrode, and the conductive coating layer formed on the surface of the primary particles of the positive electrode active material inhibits the lithium ions from entering and leaving the positive electrode active material.
- the lithium ions enter and exit the positive electrode appropriately.
- the carbon material the smaller the particle size, the lighter the carbon material becomes and the more easily appears on the surface of the positive electrode mixture layer, and the ratio of carbon atoms to all atoms on the surface of the positive electrode increases.
- the ratio of carbon atoms to all atoms on the surface of the positive electrode can be easily set to 80% or more.
- the proportion of carbon atoms increases from the surface of the positive electrode to a certain depth. It is preferable. For this reason, it is preferable that the ratio of the carbon atom with respect to all the atoms in the area
- disconnected the positive electrode in the thickness direction of the positive mix layer is an energy dispersive X-ray fluorescence spectrometer (EDX). It is the value measured using.
- the above positive electrode active material and other positive electrode active materials can be mixed and used.
- the other positive electrode active material to be mixed is not particularly limited as long as it is a compound that can reversibly insert and desorb lithium.
- lithium can be inserted and desorbed while maintaining a stable crystal structure. It is preferable to use a layered structure, a spinel structure, or an olivine structure.
- the negative electrode active material used for the negative electrode is not particularly limited as long as it can reversibly occlude and release lithium.
- a carbon material or an alloy with lithium is formed.
- a metal or alloy material, a metal oxide, or the like can be used.
- a carbon material for the negative electrode active material For example, natural graphite, artificial graphite, mesophase pitch-based carbon fiber (MCF), mesocarbon microbeads (MCMB), coke, hard carbon Fullerenes, carbon nanotubes, and the like can be used.
- a carbon material obtained by coating a graphite material with low crystalline carbon is preferable to use.
- nonaqueous solvent used in the nonaqueous electrolyte a known nonaqueous solvent that has been conventionally used in nonaqueous electrolyte secondary batteries can be used,
- cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate
- chain carbonates such as dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate can be used.
- a mixed solvent of a cyclic carbonate and a chain carbonate as a non-aqueous solvent having a low viscosity, a low melting point and a high lithium ion conductivity, and the volume ratio of the cyclic carbonate and the chain carbonate in the mixed solvent is A range of 2: 8 to 5: 5 is preferred.
- an ionic liquid can also be used as the non-aqueous solvent for the non-aqueous electrolyte.
- the cation species and the anion species are not particularly limited, but low viscosity, electrochemical stability, hydrophobicity
- a combination using a pyridinium cation, an imidazolium cation, or a quaternary ammonium cation as the cation and a fluorine-containing imide anion as the anion is particularly preferable.
- a solute used for the non-aqueous electrolyte a known lithium salt that is conventionally used in a non-aqueous electrolyte secondary battery can be used.
- a lithium salt a lithium salt containing one or more elements among P, B, F, O, S, N, and Cl can be used.
- LiPF 6 LiBF 4 , LiCF 3 SO 3 , LiN (FSO 2 ) 2 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ), Lithium salts such as LiC (C 2 F 5 SO 2 ) 3 , LiAsF 6 , LiClO 4 and mixtures thereof can be used.
- LiPF 6 is preferably used in order to enhance the high rate charge / discharge characteristics and durability of the nonaqueous electrolyte secondary battery.
- the separator interposed between the positive electrode and the negative electrode prevents a short circuit due to contact between the positive electrode and the negative electrode and impregnates the non-aqueous electrolyte
- the material is not particularly limited as long as the material can obtain ion conductivity.
- a polypropylene or polyethylene separator, a polypropylene-polyethylene multilayer separator, or the like can be used.
- the general formula Li a Ni x M (1-x) O 2 (wherein M is one or more elements and 0 ⁇ a ⁇ 1 .2., A condition in which 0.4 ⁇ x ⁇ 1.0 is satisfied.)
- the ratio of carbon atoms to all atoms on the surface of the positive electrode is 80% or more, so that the positive electrode active material comprising the above lithium-containing transition metal composite oxide is exposed to the atmosphere. As a result, it is possible to prevent the lithium ions from entering and exiting from the positive electrode.
- the output characteristics after exposure to the atmosphere are prevented from being deteriorated, and excellent output characteristics can be obtained even at low temperatures.
- nonaqueous electrolyte secondary battery according to the present invention will be specifically described with reference to examples, and in the nonaqueous electrolyte secondary battery according to this example, the output characteristics at low temperature decreased after exposure to the atmosphere. It will be clarified by giving a comparative example that this is suppressed.
- the nonaqueous electrolyte secondary battery of the present invention is not limited to the following examples, and can be implemented with appropriate modifications within a range not changing the gist thereof.
- Example 1 in preparing the positive electrode active material composed of the lithium-containing transition metal composite oxide represented by the above general formula, nickel sulfate, cobalt sulfate, and manganese sulfate were used. An aqueous solution containing ions and manganese ions was prepared, and the molar ratio of nickel, cobalt, and manganese in the aqueous solution was adjusted to 5: 2: 3.
- the temperature of the aqueous solution was set to 50 ° C., and an aqueous sodium hydroxide solution was added dropwise to the aqueous solution to adjust the pH of the aqueous solution to 9 to 12 to obtain a precipitate containing nickel, cobalt, and manganese.
- the precipitate is filtered and washed with water, and then the precipitate is heat-treated at 300 ° C. in an air stream containing oxygen to obtain a composite oxide of nickel, cobalt, and manganese (Ni 0.5 Co 0.2 was obtained Mn 0.3) 3 O 4.
- lithium carbonate is added to the composite oxide of nickel, cobalt, and manganese so that the molar ratio with respect to the total sum of nickel, cobalt, and manganese is 1.15. Firing was performed at 980 ° C. for 15 hours.
- the fired product was pulverized and sieved to obtain a positive electrode active material composed of Li 1.15 Ni 0.5 Co 0.2 Mn 0.3 O 2 .
- the average particle diameter of this positive electrode active material was about 6 ⁇ m.
- the above positive electrode active material Li 1.15 Ni 0.5 Co 0.2 Mn 0.3 O 2 , furnace black as a conductive agent having an average particle size of 230 nm, and polyvinylidene fluoride as a binder are dissolved.
- the prepared N-methyl-2-pyrrolidone solution was adjusted so that the mass ratio of the positive electrode active material, the conductive agent and the binder was 92: 5: 3, and mixed to obtain a slurry of the positive electrode mixture was made.
- this slurry was applied onto a positive electrode current collector made of aluminum foil at a coating speed of 1.0 m / min, and this was dried under drying conditions of a drying temperature of 90 ° C. and an air volume of 5 m / sec. After rolling with a rolling roller, an aluminum current collecting tab was attached to produce a positive electrode.
- the ratio of carbon atoms to the total atoms on the surface of the positive electrode (atomic concentration) is It was 83%.
- the atomic concentration of carbon atoms calculated from the mass ratio of the positive electrode active material, the conductive agent, and the binder is about 42%, and the atomic concentration of carbon atoms on the surface of the positive electrode is high. I understand.
- the positive electrode was cut in the thickness direction of the positive electrode mixture layer, and the cross section was measured by the energy dispersive X-ray fluorescence analyzer.
- the atomic concentration of carbon atoms relative to all atoms in the region is 54%
- the atomic concentration of carbon atoms relative to all atoms in the region from the surface of the positive electrode to 30% to 60% in the thickness direction of the positive electrode mixture layer is 48%.
- the atomic number concentration of carbon atoms decreased as the depth increased from the surface of the positive electrode in the thickness direction of the positive electrode mixture layer.
- the positive electrode produced as described above is used as the working electrode 11, while metallic lithium is used for the counter electrode 12 and the reference electrode 13 serving as the negative electrode, and ethylene is used as the non-aqueous electrolyte 14.
- LiPF 6 was dissolved to a concentration of 1 mol / l in a mixed solvent in which carbonate, methyl ethyl carbonate, and dimethyl carbonate were mixed at a volume ratio of 3: 3: 4, and 1% by mass of vinylene carbonate was further dissolved. Using this, a three-electrode test cell of Example 1 was produced.
- the positive electrode produced as described above was kept in a constant temperature and humidity chamber at a temperature of 30 ° C. and a humidity of 60% for 5 days to be exposed to the atmosphere, and the positive electrode after exposure to the atmosphere was used as the working electrode 11 as described above.
- a three-electrode test cell after exposure to the atmosphere was obtained.
- Comparative Example 1 a positive electrode mixture slurry was prepared by using vapor grown carbon fiber (VGCF) instead of the above furnace black as the conductive agent in the production of the positive electrode in Example 1, and this slurry was used as the positive electrode.
- the coating speed applied on the current collector was changed to 0.5 m / min, and the drying conditions for drying this were changed to a drying temperature of 120 ° C. and an air volume of 10 m / sec.
- a positive electrode was produced in the same manner as in 1. Then, using the positive electrode produced in this way as the working electrode 11, a three-electrode test cell of Comparative Example 1 was produced in the same manner as in Example 1 above.
- the ratio of carbon atoms to the total atoms on the surface of the positive electrode (atomic concentration) was 74%.
- the surface from the positive electrode to the thickness direction of the positive electrode mixture layer is 30%.
- the atomic concentration of carbon atoms with respect to all atoms in the region is 32%, and the atomic concentration of carbon atoms with respect to all atoms in the region from the surface of the positive electrode to 30% to 60% in the thickness direction of the positive electrode mixture layer is 60%.
- the atomic number concentration of carbon atoms increased from the surface of the positive electrode in the thickness direction of the positive electrode mixture layer.
- Example 1 the positive electrode produced as described above was kept in a constant temperature and humidity chamber at a temperature of 30 ° C. and a humidity of 60% for 5 days to be exposed to the atmosphere. Using the positive electrode thus exposed to the atmosphere as the working electrode 11, a three-electrode test cell after exposure to the atmosphere was produced.
- Comparative Example 2 In Comparative Example 2, in the production of the positive electrode in Example 1, the same slurry as in Example 1 was applied onto the positive electrode current collector made of aluminum foil at a coating speed of 2.0 m / min, and this was dried at a drying temperature. A positive electrode was produced in the same manner as in Example 1 except that drying was performed under the drying conditions of 120 ° C. and an air volume of 8 m / sec. Then, using the positive electrode produced in this way as the working electrode 11, a three-electrode test cell of Comparative Example 1 was produced in the same manner as in Example 1 above.
- Example 2 the positive electrode produced as described above was kept in a constant temperature and humidity chamber at a temperature of 30 ° C. and a humidity of 60% for 5 days to be exposed to the atmosphere. Using the positive electrode thus exposed to the atmosphere as the working electrode 11, a three-electrode test cell after exposure to the atmosphere was produced.
- each of the above three-electrode test cells is charged to 50% of the rated capacity, that is, when the depth of charge (SOC) reaches 50%
- each of the three-electrode test cells is placed in a low temperature environment of ⁇ 30 ° C., respectively.
- the cell voltage after 10 seconds in each case was plotted against the current value, the current value (Ip value) at the cut voltage was determined, and the output of each three-electrode test cell in a low temperature environment of ⁇ 30 ° C. was calculated.
- a mixture of a positive electrode active material composed of a lithium-containing transition metal composite oxide having a layered structure containing a large amount of Ni represented by the above general formula and a conductive carbon material In the case of using a positive electrode in which a positive electrode material mixture layer containing a positive electrode material layer is used, the three-electrode test cell of Example 1 in which the number concentration of carbon atoms with respect to all atoms on the positive electrode surface is 80% or more is the surface of the positive electrode.
- the furnace black used as the conductive carbon material in Example 1 and Comparative Example 2 has an average particle size of 230 nm, and the average particle size compared to the vapor growth carbon fiber (VGCF) used in Comparative Example 1. Is small, and it is easy to increase the atomic concentration of carbon atoms with respect to all atoms on the surface of the positive electrode.
- VGCF vapor growth carbon fiber
- Example 1 in which the number concentration of carbon atoms with respect to all atoms on the surface of the positive electrode is higher than that in Comparative Example 2 is exposed to the atmosphere.
- the output drop under the low temperature environment was greatly reduced.
- increasing the number concentration of carbon atoms with respect to all atoms on the surface of the positive electrode can improve the output characteristics in a low-temperature environment after exposure to the atmosphere. I understand.
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Abstract
Description
実施例1においては、前記の一般式に示すリチウム含有遷移金属複合酸化物からなる正極活物質を作製するにあたり、硫酸ニッケル、硫酸コバルト、硫酸マンガンを用いて、反応槽内に、ニッケルイオン、コバルトイオン、マンガンイオンを含有する水溶液を準備し、この水溶液中のニッケルとコバルトとマンガンとが5:2:3のモル比になるように調整した。
比較例1においては、実施例1における正極の作製において、導電剤として、上記のファーネスブラックに代えて気相成長炭素繊維(VGCF)を用いて正極合剤のスラリーを作製し、このスラリーを正極集電体の上に塗布する塗布速度を0.5m/分に変更し、さらにこれを乾燥させる乾燥条件を、乾燥温度120℃、風量10m/秒に変更させ、それ以外は、上記の実施例1の場合と同様にして正極を作製した。そして、このように作製した正極を作用極11に用い、上記の実施例1と同様にして、比較例1の三電極式試験セルを作製した。
比較例2においては、実施例1における正極の作製において、実施例1と同じスラリーをアルミニウム箔からなる正極集電体の上に、2.0m/分の塗布速度で塗布し、これを乾燥温度120℃、風量8m/秒の乾燥条件で乾燥させるようにし、それ以外は、上記の実施例1の場合と同様にして正極を作製した。そして、このように作製した正極を作用極11に用い、上記の実施例1と同様にして、比較例1の三電極式試験セルを作製した。
12 対極(負極)
13 参照極
14 非水電解液
Claims (4)
- 正極活物質と導電性の炭素材料とが混合されたものを含む正極合剤層が表面に形成された正極と、負極活物質を含む負極と、非水系溶媒に溶質を溶解させた非水電解液とを備えた非水電解質二次電池において、上記の正極活物質に、一般式LiaNixM(1-x)O2(式中、Mは1種類以上の元素であり、0<a≦1.2、0.4≦x≦1.0の条件を満たす。)で表される層状構造を有するリチウム含有遷移金属複合酸化物が用いられると共に、上記の正極の表面における全原子に対する炭素原子の割合が80%以上であることを特徴とする非水電解質二次電池。
- 請求項1に記載の非水電解質二次電池において、上記の正極の表面から正極合剤層の厚み方向30%までの領域における全原子に対する炭素原子の割合が50%以上である非水電解質二次電池。
- 請求項1に記載の非水電解質二次電池において、上記の導電性の炭素材料の平均粒径が230nm以下である非水電解質二次電池。
- 請求項2に記載の非水電解質二次電池において、上記の導電性の炭素材料の平均粒径が230nm以下である非水電解質二次電池。
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Application Number | Priority Date | Filing Date | Title |
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CN201180016878.9A CN102834954B (zh) | 2010-04-01 | 2011-03-10 | 非水电解质二次电池 |
US13/637,682 US20130017448A1 (en) | 2010-04-01 | 2011-03-10 | Nonaqueous electrolyte secondary battery |
JP2012509363A JP5666561B2 (ja) | 2010-04-01 | 2011-03-10 | 非水電解質二次電池 |
KR1020127025597A KR20130042471A (ko) | 2010-04-01 | 2011-03-10 | 비수 전해질 이차 전지 |
EP11765312A EP2555283A1 (en) | 2010-04-01 | 2011-03-10 | Nonaqueous electrolyte secondary battery |
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JPWO2011016553A1 (ja) * | 2009-08-07 | 2013-01-17 | 三洋電機株式会社 | 非水電解質二次電池 |
KR101675970B1 (ko) * | 2014-05-08 | 2016-11-14 | 주식회사 엘지화학 | 베어 셀의 성능을 평가하기 위한 비이커 셀 및 그것을 포함하고 있는 3전극 시스템 |
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JP3571671B2 (ja) | 2000-09-14 | 2004-09-29 | イリオン テクノロジー コーポレイション | リチオ化酸化物材料およびその製造方法 |
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JP2009064714A (ja) * | 2007-09-07 | 2009-03-26 | Toyota Motor Corp | 電極体およびそれを用いたリチウム二次電池 |
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2011
- 2011-03-10 EP EP11765312A patent/EP2555283A1/en not_active Withdrawn
- 2011-03-10 WO PCT/JP2011/055657 patent/WO2011125410A1/ja active Application Filing
- 2011-03-10 JP JP2012509363A patent/JP5666561B2/ja active Active
- 2011-03-10 US US13/637,682 patent/US20130017448A1/en not_active Abandoned
- 2011-03-10 CN CN201180016878.9A patent/CN102834954B/zh active Active
- 2011-03-10 KR KR1020127025597A patent/KR20130042471A/ko not_active Application Discontinuation
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JPH11224664A (ja) * | 1998-02-06 | 1999-08-17 | Nikki Chemcal Co Ltd | 高耐湿性、高安全性リチウムイオン二次電池 |
JP3571671B2 (ja) | 2000-09-14 | 2004-09-29 | イリオン テクノロジー コーポレイション | リチオ化酸化物材料およびその製造方法 |
JP2005251684A (ja) * | 2004-03-08 | 2005-09-15 | Toshiba Corp | 非水電解質二次電池 |
JP2008235090A (ja) | 2007-03-22 | 2008-10-02 | Matsushita Electric Ind Co Ltd | リチウムイオン二次電池用正極およびそれを用いたリチウムイオン二次電池 |
JP2008270175A (ja) | 2007-03-29 | 2008-11-06 | Matsushita Electric Ind Co Ltd | 非水電解質二次電池用正極および非水電解質二次電池 |
JP2009135045A (ja) * | 2007-11-30 | 2009-06-18 | Sanyo Electric Co Ltd | 非水電解質二次電池 |
Also Published As
Publication number | Publication date |
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EP2555283A1 (en) | 2013-02-06 |
CN102834954B (zh) | 2015-03-18 |
JPWO2011125410A1 (ja) | 2013-07-08 |
US20130017448A1 (en) | 2013-01-17 |
KR20130042471A (ko) | 2013-04-26 |
CN102834954A (zh) | 2012-12-19 |
JP5666561B2 (ja) | 2015-02-12 |
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