JP7068496B2 - リチウムイオン二次電池およびその製造方法 - Google Patents
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 56
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 55
- 239000002245 particle Substances 0.000 claims description 191
- 239000007774 positive electrode material Substances 0.000 claims description 165
- 239000010410 layer Substances 0.000 claims description 151
- 239000002002 slurry Substances 0.000 claims description 112
- 239000002344 surface layer Substances 0.000 claims description 81
- 239000011888 foil Substances 0.000 claims description 75
- 239000000203 mixture Substances 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000003825 pressing Methods 0.000 claims description 14
- 238000005520 cutting process Methods 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims 1
- 238000004804 winding Methods 0.000 description 42
- 239000000463 material Substances 0.000 description 15
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000008151 electrolyte solution Substances 0.000 description 8
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000005336 cracking Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000009830 intercalation Methods 0.000 description 6
- 230000002687 intercalation Effects 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 4
- 238000009831 deintercalation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
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- 238000005304 joining Methods 0.000 description 3
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
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- 239000004020 conductor Substances 0.000 description 2
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- 239000013078 crystal Substances 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- OFHQVNFSKOBBGG-UHFFFAOYSA-N 1,2-difluoropropane Chemical compound CC(F)CF OFHQVNFSKOBBGG-UHFFFAOYSA-N 0.000 description 1
- KXJGSNRAQWDDJT-UHFFFAOYSA-N 1-acetyl-5-bromo-2h-indol-3-one Chemical compound BrC1=CC=C2N(C(=O)C)CC(=O)C2=C1 KXJGSNRAQWDDJT-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910004403 Li(Ni0.6Co0.2Mn0.2)O2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
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- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 229910008484 TiSi Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
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- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
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- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
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- 230000008719 thickening Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
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- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
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- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
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- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H01M4/043—Processes of manufacture in general involving compressing or compaction
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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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Description
31a 正極集電箔
31b 正極合剤層
31d 深層部
31s 表層部
32 負極電極
33 セパレータ
33 セパレータ
L 積層体
M リチウムイオン二次電池の製造方法
Pd 正極活物質粒子(第1の正極活物質粒子)
Ps 正極活物質粒子(第2の正極活物質粒子)
S1 塗布工程
S2 乾燥工程
S3 プレス工程
S4 裁断工程
S5 電極群製造工程
SL1 第1のスラリー
SL2 第2のスラリー
Claims (5)
- 正極電極と負極電極とをセパレータを介して対向させたリチウムイオン二次電池の製造方法であって、
正極集電箔の表面に第1の正極活物質粒子を含む第1のスラリーを塗布するとともに、該第1のスラリーの表面に前記第1の正極活物質粒子よりも平均粒子径が大きくかつタップ密度が高い第2の正極活物質粒子を含む第2のスラリーを塗布する塗布工程と、
前記正極集電箔の表面に塗布された前記第1のスラリーと該第1のスラリーの表面に塗布された前記第2のスラリーを乾燥させて、前記正極集電箔の表面に前記第1の正極活物質粒子を含む深層部を形成するとともに、該深層部の表面に前記第2の正極活物質粒子を含む表層部を形成する乾燥工程と、
前記乾燥工程を経て前記正極集電箔の表面に前記深層部が設けられ該深層部の表面に前記表層部が設けられた積層体を加圧して、前記表層部における正極活物質粒子間の空間率が前記深層部における正極活物質粒子間の空間率よりも低い前記積層体を得るプレス工程と、
前記プレス工程を経た前記積層体を裁断して、前記表層部と前記深層部を含む正極合剤層を有する正極電極を得る裁断工程と、
前記正極電極と前記負極電極とを、前記セパレータを介して対向させ、前記正極合剤層の前記表層部を、前記セパレータを介して前記負極電極に対向させる電極群製造工程と、
を含むことを特徴とするリチウムイオン二次電池の製造方法。 - 前記表層部に含まれる正極活物質粒子のコバルト含有率は、前記深層部に含まれる正極活物質粒子のコバルト含有率よりも高いことを特徴とする請求項1に記載のリチウムイオン二次電池の製造方法。
- 前記表層部に含まれる正極活物質粒子の平均粒子径は、5[μm]以上かつ12[μm]以下であり、
前記深層部に含まれる正極活物質粒子の平均粒子径は、3[μm]以上かつ8[μm]以下であることを特徴とする請求項1に記載のリチウムイオン二次電池の製造方法。 - 前記表層部に含まれる正極活物質粒子のタップ密度は、2.0[g/cm3]以上かつ2.8[g/cm3]以下であり、
前記深層部に含まれる正極活物質粒子のタップ密度は、1.5[g/cm3]以上かつ2.2[g/cm3]以下であることを特徴とする請求項1に記載のリチウムイオン二次電池の製造方法。 - 前記表層部における前記空間率は、25[%]以上かつ14[%]以下であり、
前記深層部における前記空間率は、28[%]以上かつ15[%]以下であることを特徴とする請求項1に記載のリチウムイオン二次電池の製造方法。
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