WO2012133016A1 - 非水電解液二次電池 - Google Patents
非水電解液二次電池 Download PDFInfo
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- WO2012133016A1 WO2012133016A1 PCT/JP2012/057108 JP2012057108W WO2012133016A1 WO 2012133016 A1 WO2012133016 A1 WO 2012133016A1 JP 2012057108 W JP2012057108 W JP 2012057108W WO 2012133016 A1 WO2012133016 A1 WO 2012133016A1
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- positive electrode
- electrolyte secondary
- electrode plate
- secondary battery
- aqueous electrolyte
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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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
- H01M10/058—Construction or manufacture
-
- 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
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a non-aqueous electrolyte secondary battery, and particularly to a non-aqueous electrolyte secondary battery excellent in high-temperature storage characteristics and cycle characteristics.
- non-aqueous electrolyte secondary batteries typified by high-capacity lithium ion secondary batteries are widely used.
- lithium-cobalt composite oxides and heterogeneous metal element-added lithium-cobalt composite oxides are often used because various battery characteristics are superior to others.
- cobalt is expensive and has a small abundance as a resource. Therefore, in order to continue using these lithium cobalt composite oxides and lithium cobalt composite oxides added with different metal elements as the positive electrode active material of the non-aqueous electrolyte secondary battery, further enhancement of the performance of the non-aqueous electrolyte secondary battery Is desired.
- Patent Document 1 and Patent Document 2 listed below disclose nonaqueous electrolyte secondary batteries in which an inorganic particle layer is provided as a coating on the surface of a positive electrode active material layer.
- JP 2007-134279 A Japanese Patent Laid-Open No. 2007-28017 International Publication WO2006 / 038532
- Patent Document 3 polyethylene and polypropylene are used as a separator for a lithium ion battery having both the impregnation property of a non-aqueous electrolyte, mechanical strength, permeability, and an effect of improving high-temperature storage characteristics when used in a battery.
- a polyolefin microporous film composed of a laminate film of two or more layers, and at least one surface layer of the separator includes inorganic particles, but the inorganic particle layer is provided on the surface of the positive electrode active material layer.
- the inventor has conducted various studies on the cause of the increase in battery thickness during high-temperature storage when an inorganic particle layer is disposed on the surface of the positive electrode active material layer, and as a result, the layer is disposed on the surface of the positive electrode active material layer. It was found that the inorganic particle layer easily holds the electrolytic solution, and therefore, the oxidative decomposition reaction of the electrolytic solution on the surface side of the positive electrode active material layer is more likely to occur.
- the present inventors have found that by disposing inorganic particles also on the negative electrode side, excessive electrolyte solution retention on the positive electrode side can be suppressed, and specific oxidative decomposition of the electrolyte solution on the positive electrode side can be suppressed, The present invention has been completed.
- an object of the present invention is to obtain a non-aqueous electrolyte secondary battery in which both improvement of storage characteristics in a high temperature environment and suppression of battery expansion are compatible.
- the non-aqueous electrolyte secondary battery of the present invention includes a positive electrode plate including a positive electrode active material capable of reversibly occluding and releasing lithium, and a negative electrode capable of reversibly occluding and releasing lithium.
- a nonaqueous electrolyte secondary battery comprising a negative electrode plate containing an active material, a separator separating the positive electrode plate and the negative electrode plate, and a nonaqueous electrolyte solution containing a nonaqueous solvent and an electrolyte salt
- An inorganic particle layer containing inorganic particles and a binder is formed on the surface of the positive electrode plate, and the separator is a polyolefin microporous film composed of a laminate film of two or more layers, and at least a surface layer on the negative electrode side Is characterized by containing inorganic particles.
- an inorganic particle layer is formed on the surface of the positive electrode active material layer, and a multilayer film having two or more layers and containing inorganic particles in the surface layer.
- the use of the microporous membrane as a separator not only improves the storage characteristics in a high-temperature environment, but also significantly suppresses the generation of gas that can be generated by the formation of an inorganic particle layer on the surface of the positive electrode active material layer.
- the polyolefin microporous membrane used for the separator preferably contains polyethylene because of its excellent permeability and shutdown characteristics as the separator.
- content of the inorganic particle contained in a separator surface layer is 3 mass% or more and 60 mass% or less. If the content of the inorganic particles contained in the surface layer is small, the effect of adding inorganic particles is difficult to appear. If the content is too large, the rigidity of the separator is increased, and the separator is easily entangled with the equipment during winding. Is more preferable to be 5 mass% or more and 40 mass% or less.
- the thickness of the inorganic particle layer formed on the surface of the positive electrode plate is 0.1 ⁇ m or more, the effect of forming the inorganic particle layer is excellent, but if the thickness of the inorganic particle layer exceeds 4 ⁇ m, the battery internal resistance increases. As a result, the load characteristics are lowered, and the energy density of the battery is lowered due to a decrease in the amount of each active material of the positive electrode plate and the negative electrode plate. Therefore, in the nonaqueous electrolyte secondary battery of the present invention, the thickness of the inorganic particle layer is preferably 0.1 ⁇ m or more and 4 ⁇ m or less.
- the inorganic particles contained in at least the negative electrode surface layer of the separator and the inorganic particle layer formed on the surface of the positive electrode plate are at least one of oxides or nitrides of silicon, aluminum, and titanium. Silicon dioxide, aluminum oxide and titanium oxide are more preferable.
- the positive electrode active material that can be used in the non-aqueous electrolyte secondary battery of the present invention is not particularly limited as long as it is a material capable of reversibly occluding and releasing lithium, and has been commonly used from the above-described conventional ones.
- the positive electrode active material can be used.
- the negative electrode active material that can be used in the non-aqueous electrolyte secondary battery of the present invention is not particularly limited as long as it is a material capable of reversibly occluding and releasing lithium, and graphite, non-graphitizable carbon, and easy Carbon materials such as graphitizable carbon, titanium oxides such as LiTiO 2 and TiO 2 , metalloid elements such as silicon and tin, or Sn—Co alloys can be used.
- nonaqueous solvent examples include cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC), and fluorinated cyclic esters.
- cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC)
- fluorinated cyclic esters examples include fluorinated cyclic esters.
- Carbonic acid esters such as ⁇ -butyrolactone ( ⁇ -BL), ⁇ -valerolactone ( ⁇ -VL), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), methyl propyl carbonate (MPC), chain carbonates such as dibutyl carbonate (DBC), fluorinated chain carbonates, chain carboxylates such as methyl pivalate, ethyl pivalate, methyl isobutyrate, methyl propionate, N, N'-dimethylformamide Amide compounds such as N- methyl-oxazolidinone, sulfur compounds such as sulfolane, etc.
- ⁇ -BL ⁇ -butyrolactone
- ⁇ -VL dimethyl carbonate
- EMC ethyl methyl carbonate
- DEC diethyl carbonate
- MPC methyl propyl carbonate
- chain carbonates such as dibutyl carbonate (DBC)
- ambient temperature molten salt such as tetrafluoroboric acid 1-ethyl-3-methylimidazolium
- molten salt such as tetrafluoroboric acid 1-ethyl-3-methylimidazolium
- vinylene carbonate (VC), vinyl ethyl carbonate (VEC), succinic anhydride ( Add SUCAH), maleic anhydride (MAAH), glycolic anhydride, ethylene sulfite (ES), divinyl sulfone (VS), vinyl acetate (VA), vinyl pivalate (VP), catechol carbonate, biphenyl (BP), etc. May be. Two or more of these compounds can be appropriately mixed and used.
- a lithium salt generally used as an electrolyte salt in the non-aqueous electrolyte secondary battery can be used.
- Such lithium salts include LiPF 6 (lithium hexafluorophosphate), LiBF 4 , LiCF 3 SO 3 , 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), LiC (CF 3 SO 2) 3, LiC (C 2 F 5 SO 2) 3, LiAsF 6, LiClO 4, Li 2 B 10 Cl 10, Li 2 B 12 Cl 12 and mixtures thereof are exemplified.
- LiPF 6 is particularly preferable.
- the amount of electrolyte salt dissolved in the non-aqueous solvent is preferably 0.5 to 2.0 mol / L.
- the non-aqueous electrolyte secondary battery of the present invention may be not only liquid but also gelled.
- the specific manufacturing method of the nonaqueous electrolyte secondary battery concerning each Example and each comparative example is demonstrated.
- positive electrode active material a mixture of different element-added lithium cobalt oxide and layered nickel manganese lithium cobalt oxide was used.
- the different element-added lithium cobalt oxide was prepared as follows.
- lithium carbonate (Li 2 CO 3 ) was used for the lithium source, and 0.2 mol% of Zr and 0.5 mol% of Mg were added to the cobalt source as different elements during the synthesis of cobalt carbonate.
- Zr and Mg-added tricobalt tetroxide (Co 3 O 4 ) obtained by coprecipitation from an aqueous solution and then obtained by a thermal decomposition reaction were used. A predetermined amount of these were weighed and mixed, and then calcined at 850 ° C. for 24 hours in an air atmosphere to obtain Zr and Mg-added lithium cobalt oxide. This was pulverized with a mortar to an average particle size of 14 ⁇ m to obtain a positive electrode active material A.
- the layered nickel manganese lithium cobaltate was prepared as follows.
- Li 2 CO 3 was used as a lithium source, and a coprecipitated hydroxide represented by Ni 0.33 Mn 0.33 Co 0.34 (OH) 2 was used as a transition metal source.
- a predetermined amount of these were weighed and mixed, and then fired at 1000 ° C. for 20 hours in an air atmosphere to obtain a layer nickel manganese cobaltate represented by LiNi 0.33 Mn 0.33 Co 0.34 O 2 . .
- This was pulverized to an average particle size of 5 ⁇ m with a mortar to obtain a positive electrode active material B.
- the positive electrode active material A and the positive electrode active material B obtained as described above are mixed in a mass ratio of 7: 3, and used for the non-aqueous electrolyte secondary batteries of the examples and the comparative examples.
- a positive electrode active material was obtained.
- inorganic particle layer For the nonaqueous electrolyte secondary batteries of Examples 1 to 4 and Comparative Example 1, an inorganic particle layer was further formed on the surface of the positive electrode plate obtained as described above. Acetone is used as a solvent, rutile type titanium oxide (TiO 2 : KR380 manufactured by Titanium Industry Co., Ltd.) having a particle size of 0.38 ⁇ m as inorganic particles is 10% by mass with respect to acetone, and acrylonitrile structure (unit) as a binder. 10% by mass of a copolymer (rubber-like polymer) containing bismuth was mixed with a special mechanized film, and a titanium oxide dispersion slurry was prepared.
- rutile type titanium oxide TiO 2 : KR380 manufactured by Titanium Industry Co., Ltd.
- acrylonitrile structure unit
- inorganic particle layers of titanium oxide were laminated on both surfaces of the positive electrode plate by a die coating method, and the solvent was dried and removed to form inorganic particle layers on both surfaces of the positive electrode plate.
- the thickness of the inorganic particle layer in Examples 1 to 3 and Comparative Example 1 was 4 ⁇ m, and the thickness of the inorganic particle layer in Example 4 was 0.1 ⁇ m. This thickness is the thickness of the inorganic particle layer provided on one side of the positive electrode plate.
- a slurry was prepared by dispersing 96 parts by mass of graphite powder as a negative electrode active material, 2 parts by mass of carboxymethyl cellulose as a thickener, and 2 parts by mass of styrene butadiene rubber (SBR) as a binder.
- This slurry was applied to both sides of a copper negative electrode collector having a thickness of 8 ⁇ m by the doctor blade method and then dried to form an active material layer on both sides of the negative electrode collector.
- the negative electrode plate which the length of the short side 37.5mm used in common with the nonaqueous electrolyte secondary battery of each Example and each comparative example was produced by compressing using a compression roller.
- the potential of graphite is 0.1 V based on lithium.
- the active material filling amount of the positive electrode plate and the negative electrode plate is such that the charge capacity ratio between the positive electrode plate and the negative electrode plate (negative electrode charge capacity / positive electrode charge capacity) is 1. It adjusted so that it might be set to 1.
- each layer is kneaded and heated and melted so that the layer containing inorganic particles becomes a separator disposed on the surface layer on both sides Using a coextrusion method, a sheet having three layers was formed. Then, after stretching, extracting and removing the plasticizer, drying and stretching, a microporous film made of polyethylene consisting of 3 layers each having two surface layers of 2 ⁇ m and an intermediate layer of 10 ⁇ m was prepared. A separator used in the non-aqueous electrolyte secondary battery of Comparative Example 2 was used.
- the separator used for the non-aqueous electrolyte secondary battery of Comparative Examples 1 and 3 is made by using polyethylene as a raw material, kneading with liquid paraffin which is a plasticizer, extruding while heating and melting, and forming into a sheet shape. did.
- This separator does not contain inorganic particles and has a single layer structure of polyethylene.
- Capacity recovery rate (%) (Capacity after storage) / (Initial capacity) x 100
- Table 1 summarizes the results of the capacity recovery rate and battery thickness after high-temperature charge storage obtained as described above.
- the battery of Comparative Example 3 that does not have an inorganic particle layer on the surface of the positive electrode active material layer has a poor capacity recovery rate, and the deterioration of the battery under a high temperature environment is quick.
- the battery of Comparative Example 1 provided with the inorganic particle layer on the surface of the positive electrode active material layer has an improved capacity recovery rate after storage at high temperature compared to the battery of Comparative Example 3, and the positive electrode active material It has been shown that the storage characteristics in a high temperature environment are improved by forming an inorganic particle layer on the surface of the layer. However, while the battery of Comparative Example 1 shows improved storage characteristics in a high temperature environment, the battery thickness has greatly increased.
- a microporous membrane having a three-layer structure that can be stably produced in the film forming process is used as a separator.
- the present invention is a microporous membrane composed of a laminated film of two or more layers. The same effect can be obtained if the surface layer on the negative electrode side contains inorganic particles.
- the content of the inorganic particles contained in the surface layer of the separator is preferably 3% by mass or more and 60% by mass or less. However, if the content of the inorganic particles contained in the surface layer is small, the effect of adding the inorganic particles hardly appears. If the amount is too large, the rigidity of the separator is increased, and the productivity is reduced due to the separator being easily entangled with the equipment during winding. Therefore, the amount is more preferably 5% by mass or more and 40% by mass or less.
- silicon dioxide is used as the inorganic particles to be included in the separator surface layer.
- any material that is insulative and does not easily react with the non-aqueous electrolyte can be used.
- oxides or nitrides of silicon, aluminum and titanium can also be used. Of these, silicon dioxide and aluminum oxide are preferable.
- the thickness of the inorganic particle layer formed on the surface of the positive electrode plate is 0.1 ⁇ m or more, the effect of forming the inorganic particle layer is excellent, but if the thickness of the inorganic particle layer exceeds 4 ⁇ m, the resistance inside the battery As a result, the load characteristics deteriorate, and the energy density of the battery decreases due to the decrease in the amount of each active material of the positive electrode plate and the negative electrode plate. Therefore, in the nonaqueous electrolyte secondary battery of the present invention, the thickness of the inorganic particle layer is preferably 0.1 ⁇ m or more and 4 ⁇ m or less.
- a rectangular nonaqueous electrolyte secondary battery using a flat wound electrode body is shown as an example, but the present invention depends on the shape of the electrode body of the nonaqueous electrolyte secondary battery. Not what you want. Therefore, the present invention provides a nonaqueous electrolyte secondary battery having a circular or elliptical shape using a wound electrode body, or a laminated nonaqueous electrolyte solution in which a positive electrode plate and a negative electrode plate are stacked with a separator interposed therebetween. It can also be applied to secondary batteries.
Abstract
Description
[正極活物質の作製]
正極活物質には、異種元素添加コバルト酸リチウムと層状ニッケルマンガンコバルト酸リチウムの混合物を用いた。異種元素添加コバルト酸リチウムは次のようにして作製した。出発原料としては、リチウム源には炭酸リチウム(Li2CO3)を用い、コバルト源には炭酸コバルト合成時に異種元素としてZrをCoに対して0.2mol%及びMgを0.5mol%添加した水溶液から共沈させ、その後、熱分解反応によって得られたZr及びMg添加四酸化三コバルト(Co3O4)を用いた。これらを所定量秤量して混合した後、空気雰囲気下において850℃で24時間焼成し、Zr及びMg添加コバルト酸リチウムを得た。これを乳鉢で平均粒径14μmまで粉砕し、正極活物質Aとした。
以上のようにして得られた正極活物質を94質量部、導電剤としての炭素粉末を3質量部、結着剤としてのポリフッ化ビニリデン(PVdF)粉末を3質量部となるよう混合し、これをN-メチルピロリドン(NMP)溶液と混合してスラリーを調製した。このスラリーを厚さ15μmのアルミニウム製の正極集電体の両面にドクターブレード法により塗布、乾燥して、正極集電体の両面に活物質層を形成した。その後、圧縮ローラーを用いて圧縮し、各実施例及び各比較例の非水電解液二次電池に用いる短辺の長さが36.5mmの正極極板を作製した。
実施例1~4及び比較例1の非水電解液二次電池については、以上のようにして得られた正極極板の表面に更に以下のようにして無機粒子層を形成した。溶剤としてアセトンを用い、無機粒子としての粒径0.38μmのルチル型酸化チタン(TiO2:チタン工業株式会社製KR380)をアセトンに対して10質量%、結着剤としてのアクリロニトリル構造(単位)を含む共重合体(ゴム性状高分子)を酸化チタンに対して10質量%混合し、特殊機化製Filmicsを用いて混合分散処理を行い、酸化チタン分散スラリーを調製した。このスラリーを用いて、ダイコート方式で前記正極極板の両面に酸化チタンの無機粒子層を積層させ、溶剤を乾燥・除去することで、正極極板の両表面に無機粒子層を形成した。
なお、実施例1~3及び比較例1の無機粒子層の厚みは4μm、実施例4の無機粒子層の厚みは0.1μmとした。
また、この厚みは、正極極板の片面に設けられた無機粒子層の厚みである。
負極活物質としての黒鉛粉末96質量部、増粘剤としてのカルボキシメチルセルロース2質量部、結着剤としてのスチレンブタジエンゴム(SBR)2質量部を水に分散させスラリーを調製した。このスラリーを厚さ8μmの銅製の負極集電体の両面にドクターブレード法により塗布後、乾燥して負極集電体の両面に活物質層を形成した。その後、圧縮ローラーを用いて圧縮することで、各実施例及び各比較例の非水電解液二次電池で共通して用いる短辺の長さが37.5mmの負極極板を作製した。
エチレンカーボネート(EC):ジエチルカーボネート(DEC):メチルエチルカーボネート(MEC)が、20:30:50(体積比)となるように混合した混合溶媒にLiPF6を1.0mol/L溶解させることで、各実施例及び各比較例の非水電解液二次電池で用いる非水電解液を調製した。
[実施例1~4及び比較例2]
実施例1~4及び比較例2の非水電解液二次電池に用いるセパレータとしては3層からなるポリエチレン製微多孔膜を用いた。表面に相当する2つの層は、ポリエチレンと無機粒子としての二酸化ケイ素(SiO2)を、各種質量比(実施例1=86:14、実施例2=95:5、実施例3=60:40、実施例4=86:14、比較例2=86:14)で混合し、ミキサーで撹拌したものを原料とし、上記2つの表面層に挟まれる中間層はポリエチレンを原料とした。表面層及び中間層の原料について、それぞれ可塑剤である流動パラフィンと混練した後、無機粒子を含む層が両側の表面層に配置されたセパレータとなるように各々の層を混練・加熱溶融しながら共押出法を用いて、3層を有するシート状に成形した。その後延伸し、可塑剤を抽出除去した後、乾燥及び延伸することで、2つの表面層がそれぞれ2μm、中間層が10μmである3層からなるポリエチレン製微多孔膜を作製し、各実施例及び比較例2の非水電解液二次電池で用いるセパレータとした。
また、比較例1及び3の非水電解液二次電池に用いるセパレータは、ポリエチレンを原料とし、可塑剤である流動パラフィンと混錬した後、加熱溶融しながら押し出し、シート状に成形して作製した。このセパレータは、無機粒子を含有せず、ポリエチレンの単層構造からなるものである。
上記の各実施例及び各比較例に対応する正極極板と負極極板との間に、各実施例及び各比較例に対応するセパレータを介在させて巻回することによって巻回電極体となし、これを金属製角形外装缶に収納した後、上記の電解液を注液することで、各実施例及び各比較例にかかる角形非水電解液二次電池(厚み5.5mm×幅34mm×高さ43mm)を作製した。得られた非水電解液二次電池の設計容量は800mAhである。
各実施例及び各比較例の電池に対して、25℃の環境下で、1It=800mAの定電流で電池電圧が4.4V(正極電位はリチウム基準で4.5V)となるまで充電し、電池電圧が4.4Vに達した以降は、4.4Vの定電圧で、充電電流が1/40It=20mAとなるまで充電し、満充電状態の電池を得た。その後、1It=800mAの定電流で電池電圧が3.0Vとなるまで放電し、このときの放電容量を測定して初期容量とした。
容量復帰率(%) = (保存後容量)/(初期容量)×100
Claims (3)
- リチウムを可逆的に吸蔵・放出可能な正極活物質を含む正極極板と、リチウムを可逆的に吸蔵・放出可能な負極活物質を含む負極極板と、前記正極極板及び前記負極極板を隔離するセパレータと、非水溶媒及び電解質塩を含む非水電解液と、を備えた非水電解液二次電池において、
前記正極極板の表面には無機粒子とバインダーとを含有する無機粒子層が形成され、
前記セパレータは、二層以上の積層フィルムからなるポリオレフィン微多孔膜であり、かつ、少なくとも負極側の表面層には無機粒子を含有していることを特徴とする非水電解液二次電池。 - 前記表面層中の無機粒子の含有量は5質量%以上40質量%以下であることを特徴とする請求項1に記載の非水電解液二次電池。
- 前記無機粒子層の厚みは0.1μm以上4μm以下であることを特徴とする請求項1又は2に記載の非水電解液二次電池。
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US14/006,119 US20140011068A1 (en) | 2011-03-29 | 2012-03-21 | Non-aqueous electrolyte secondary battery |
CN2012800156678A CN103477493A (zh) | 2011-03-29 | 2012-03-21 | 非水电解液二次电池 |
JP2013507415A JP6092096B2 (ja) | 2011-03-29 | 2012-03-21 | 非水電解液二次電池 |
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JP2015056208A (ja) * | 2013-09-10 | 2015-03-23 | 株式会社豊田自動織機 | 活物質層上に形成された保護層を具備する電極 |
WO2015053177A1 (ja) * | 2013-10-11 | 2015-04-16 | 株式会社村田製作所 | 非水電解質電池およびその製造方法 |
US20150188107A1 (en) * | 2012-09-27 | 2015-07-02 | Sanyo Electric Co., Ltd. | Non-aqueous electrolyte secondary battery |
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CN115663286B (zh) * | 2022-12-08 | 2023-09-08 | 深圳新宙邦科技股份有限公司 | 一种锂离子电池 |
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