JP7225279B2 - 被覆黒鉛系負極活物質 - Google Patents
被覆黒鉛系負極活物質 Download PDFInfo
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- JP7225279B2 JP7225279B2 JP2021014356A JP2021014356A JP7225279B2 JP 7225279 B2 JP7225279 B2 JP 7225279B2 JP 2021014356 A JP2021014356 A JP 2021014356A JP 2021014356 A JP2021014356 A JP 2021014356A JP 7225279 B2 JP7225279 B2 JP 7225279B2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 124
- 229910002804 graphite Inorganic materials 0.000 title claims description 105
- 239000010439 graphite Substances 0.000 title claims description 105
- 239000007773 negative electrode material Substances 0.000 title claims description 83
- 239000010410 layer Substances 0.000 claims description 111
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 45
- 229910052796 boron Inorganic materials 0.000 claims description 45
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 31
- 238000005229 chemical vapour deposition Methods 0.000 claims description 29
- 239000011247 coating layer Substances 0.000 claims description 22
- 239000007833 carbon precursor Substances 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 32
- 229910001416 lithium ion Inorganic materials 0.000 description 31
- 239000007774 positive electrode material Substances 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000011255 nonaqueous electrolyte Substances 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- -1 lithium nickel cobalt aluminum Chemical compound 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 2
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- JIUHVFMKOJAZDA-UHFFFAOYSA-N 1,1,2-trifluoroethyl hydrogen carbonate Chemical compound OC(=O)OC(F)(F)CF JIUHVFMKOJAZDA-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000289517 Colletotrichum lini Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- 229910015561 LiNi0.8Co0.15Al0.5O2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001941 electron spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
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- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002203 sulfidic glass Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
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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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0428—Chemical vapour deposition
-
- 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
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M2004/027—Negative electrodes
-
- 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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- Engineering & Computer Science (AREA)
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- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
- Chemical Vapour Deposition (AREA)
Description
(比較例1)
平均粒子径(D50)が約8μmの球状黒鉛(伊藤黒鉛工業社製:SG-BH8)を用意した。管状炉を備える回転式CVD装置において、炭素前駆体にメタン(CH4)を用いて、温度950℃、Ar導入量50sccm、CH4導入量150sccmの条件で60分間、当該黒鉛20gに対して化学蒸着を行った。これにより、比較例1の被覆黒鉛系負極活物質を得た。
比較例1と同じ方法により、黒鉛20gに対して化学蒸着を行って被覆層を形成した。得られた被覆黒鉛系負極活物質に対し、その後、Ar雰囲気下で1500℃で6時間焼成を行った。これにより、比較例2の被覆黒鉛系負極活物質を得た。
平均粒子径(D50)が約8μmの球状黒鉛(伊藤黒鉛工業社製:SG-BH8)を用意した。管状炉を備える回転式CVD装置において、炭素前駆体にメタン(CH4)を用い、かつホウ素前駆体に四塩化ホウ素を用いて、温度950℃で5分間、当該黒鉛20gに対して化学蒸着(第1化学蒸着)を行った。その後、炭素前駆体としてメタン(CH4)のみを用い、温度950℃で40分間、得られた黒鉛に対して化学蒸着(第2化学蒸着)を行った。これにより、実施例1の被覆黒鉛系負極活物質を得た。
第1化学蒸着の時間を10分間に変更し、第2化学蒸着の時間を35分間に変更した以外は実施例1と同じ方法により、実施例2の被覆黒鉛系負極活物質を得た。
第1化学蒸着の時間を15分間に変更し、第2の化学蒸着時間を30分間に変更した以外は実施例1と同じ方法により、実施例3の被覆黒鉛系負極活物質を得た。
平均粒子径(D50)が約8μmの球状黒鉛(伊藤黒鉛工業社製:SG-BH8)を用意した。管状炉を備える回転式CVD装置において、炭素前駆体にメタン(CH4)を用い、ホウ素前駆体に四塩化ホウ素を用いて、温度950℃で45分間、当該黒鉛20gに対して化学蒸着を行った。これにより、比較例3の被覆黒鉛系負極活物質を得た。
各実施例および各比較例の被覆黒鉛系負極活物質に対して、被覆層の組成を、XPS装置を用いて分析した。具体的には、これらの被覆黒鉛系負極活物質に対して、XPS装置(ULVAC-PHI社製「PHI 5000 VersaProbe2」)を用いて、X線源:AlKα線(単色光)、照射範囲:φ100μm、電流・電圧:25kW 15kVの条件で測定を行った。そして、Arモノマーイオンを用いて、電圧:3kV、電流:10nA、面積:3mm×3mm、レート:3.05nm/分の条件で深さ方向分析を行った。このとき、被覆層の最下部において組成分析を行った。具体的には、被覆がホウ素を含有する場合、コア部となる黒鉛と被覆層との界面に対して、ホウ素が未検出となる直前の深さでの検出値を採用した。組成分析結果を表1に示す。
正極活物質粉末としてのLiNi1/3Co1/3Mn1/3O2(LNCM)と、導電材としてのアセチレンブラック(AB)と、バインダとしてのポリフッ化ビニリデン(PVdF)とを、LNCM:AB:PVdF=92:5:3の質量比でN-メチルピロリドン(NMP)と混合し、正極活物質層形成用スラリーを調製した。このスラリーを、厚み15μmのアルミニウム箔の表面に塗布して乾燥した後、ロールプレスすることにより、正極シートを作製した。
活性化した各評価用リチウムイオン二次電池を、SOC60%に調製した後、-10℃の環境下に置いた。この各評価用リチウムイオン二次電池に対し、15Cの電流値で2秒間の充電を行った。このときの電圧変化量ΔVを取得し、電流値とΔVを用いて電池抵抗を算出した。比較例1の被覆黒鉛系負極活物質を用いた評価用リチウムイオン二次電池の抵抗を100とした場合の、他の比較例および実施例の被覆黒鉛系負極活物質を用いた評価用リチウムイオン二次電池の抵抗の比を求めた。結果を表1に示す。
12 黒鉛
14 中間層
16 非晶質炭素層
20 捲回電極体
30 電池ケース
36 安全弁
42 正極端子
42a 正極集電板
44 負極端子
44a 負極集電板
50 正極シート(正極)
52 正極集電体
52a 正極活物質層非形成部分
54 正極活物質層
60 負極シート(負極)
62 負極集電体
62a 負極活物質層非形成部分
64 負極活物質層
70 セパレータシート(セパレータ)
100 リチウムイオン二次電池
Claims (4)
- 黒鉛と、
前記黒鉛を被覆する非晶質炭素層と、
前記黒鉛と、前記非晶質炭素層との間に位置する中間層と、
を備える、被覆黒鉛系負極活物質であって、
前記中間層は、ホウ素がドープされた炭素層であり、
前記非晶質炭素層は、ホウ素を実質的に含んでいない、
被覆黒鉛系負極活物質。 - 前記中間層におけるホウ素のドープ量が、0.1原子%以上5.5原子%以下である、請求項1に記載の被覆黒鉛系負極活物質。
- 炭素前駆体およびホウ素前駆体を含むガスを用いて化学蒸着法によって、黒鉛に、炭素およびホウ素を含有する第1被覆層を形成する工程と、
ホウ素前駆体を含まず炭素前駆体を含むガスを用いて化学蒸着法によって、前記第1被覆層上に、炭素を含有する第2被覆層を形成する工程と、
を包含する、被覆黒鉛系負極活物質の製造方法。 - 正極と、負極と、電解質と、を備える二次電池であって、前記負極が、請求項1または2に記載の被覆黒鉛系負極活物質を含む、二次電池。
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JP2007122975A (ja) | 2005-10-26 | 2007-05-17 | Sanyo Electric Co Ltd | 非水電解質二次電池 |
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JP2018163833A (ja) * | 2017-03-27 | 2018-10-18 | 三洋電機株式会社 | 非水電解質二次電池及びその製造方法 |
US20180337424A1 (en) * | 2017-05-16 | 2018-11-22 | Panasonic Intellectual Property Management Co., Ltd. | Negative-electrode active material for non-aqueous secondary battery and non-aqueous secondary battery |
JP2018195434A (ja) * | 2017-05-16 | 2018-12-06 | パナソニックIpマネジメント株式会社 | 非水二次電池 |
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JP2008288153A (ja) | 2007-05-21 | 2008-11-27 | Sumitomo Metal Ind Ltd | 炭素材料粉末およびその製造方法 |
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