CN109075378B - 非水电解质二次电池 - Google Patents
非水电解质二次电池 Download PDFInfo
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- CN109075378B CN109075378B CN201780009632.6A CN201780009632A CN109075378B CN 109075378 B CN109075378 B CN 109075378B CN 201780009632 A CN201780009632 A CN 201780009632A CN 109075378 B CN109075378 B CN 109075378B
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- positive electrode
- nonaqueous electrolyte
- active material
- electrode plate
- electrode active
- Prior art date
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 54
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 35
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 35
- 239000007774 positive electrode material Substances 0.000 claims abstract description 25
- 238000007789 sealing Methods 0.000 claims abstract description 13
- 229910014508 LixNiyM(1-y)O2 Inorganic materials 0.000 claims abstract description 8
- 239000007773 negative electrode material Substances 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 7
- 230000000903 blocking effect Effects 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims description 18
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 claims description 15
- 150000001555 benzenes Chemical class 0.000 claims description 11
- -1 phenyl lactone Chemical class 0.000 claims description 10
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 claims description 4
- AJKNNUJQFALRIK-UHFFFAOYSA-N 1,2,3-trifluorobenzene Chemical compound FC1=CC=CC(F)=C1F AJKNNUJQFALRIK-UHFFFAOYSA-N 0.000 claims description 2
- QHTJSSMHBLGUHV-UHFFFAOYSA-N 2-methylbutan-2-ylbenzene Chemical compound CCC(C)(C)C1=CC=CC=C1 QHTJSSMHBLGUHV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 2
- XTBFPVLHGVYOQH-UHFFFAOYSA-N methyl phenyl carbonate Chemical compound COC(=O)OC1=CC=CC=C1 XTBFPVLHGVYOQH-UHFFFAOYSA-N 0.000 claims description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 19
- 239000002002 slurry Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 239000002904 solvent Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 150000005676 cyclic carbonates Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000005678 chain carbonates Chemical class 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000009783 overcharge test Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VUAXHMVRKOTJKP-UHFFFAOYSA-M 2,2-dimethylbutanoate Chemical compound CCC(C)(C)C([O-])=O VUAXHMVRKOTJKP-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910016855 F9SO2 Inorganic materials 0.000 description 1
- 229910010820 Li2B10Cl10 Inorganic materials 0.000 description 1
- 229910010903 Li2B12Cl12 Inorganic materials 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910015720 LiNi0.85Co0.12Al0.03O2 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- HHEIMYAXCOIQCJ-UHFFFAOYSA-N ethyl 2,2-dimethylpropanoate Chemical compound CCOC(=O)C(C)(C)C HHEIMYAXCOIQCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000012982 microporous membrane 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M10/052—Li-accumulators
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- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
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- 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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Abstract
本发明的目的在于,利用少量的碳酸锂在过充电时迅速地启动电流阻断机构。本发明的一个方式所述的非水电解质二次电池的特征在于,其包括:包含正极活性物质的正极板、包含负极活性物质的负极板、夹在正极板与负极板之间的间隔件、非水电解质、有底筒状的外装罐、以及具有在规定的电池压力下启动的电流阻断机构的封口体,正极活性物质为通式LixNiyM(1‑y)O2(0<x≤1.2、0.85≤y≤0.99、M为选自Co、Fe、Cu、Mg、Ti、Zr、Ce和W中的至少1种元素)所示的锂镍复合氧化物,相对于正极活性物质的质量为0.01质量%以上且0.2质量%以下的碳酸锂被添加至正极板中。
Description
技术领域
本发明涉及具备设置有电流阻断机构的封口体的非水电解质二次电池。
背景技术
非水电解质二次电池具有高能量密度,因此被广泛用作智能手机、平板型计算机、笔记本电脑和便携型音乐播放器等便携型电子设备的驱动电源。近年来,非水电解质二次电池的用途也扩大至电动工具、电动辅助自行车和电动汽车等,对非水电解质二次电池要求高安全性。
非水电解质二次电池具有密闭结构,因此,非水电解质二次电池因误操作、充电器的故障等而被过充电时,在电池内部产生气体而导致电池内压上升。长期持续过充电时,有导致电池破裂、起火的可能性。因而,在非水电解质二次电池设置了如果电池内压达到规定值则阻断电池内部的电流通路的电流阻断机构。电流阻断机构使用了因电池内压的上升而变形的阀芯,利用阀芯的变形,电池内部的一部分电流通路被断开。
为了迅速地启动电流阻断机构,需要在电池内部迅速地产生气体且该气体不会引发成为热失控原因的化学反应。专利文献1和2公开了向正极板中添加碳酸锂,使其在过充电时产生二氧化碳气体的技术。
此外,作为用于提高过充电时的非水电解质二次电池的安全性的手段,专利文献3~7公开了向非水电解质中添加具有各种取代基的苯衍生物的技术。可以认为:苯衍生物在过充电时也会因正极处的聚合反应或氧化分解反应而促进气体的产生。
现有技术文献
专利文献
专利文献1:日本特开平04-328278号公报
专利文献2:日本特开2008-186792号公报
专利文献3:日本特开平05-036439号公报
专利文献4:日本特开平09-171840号公报
专利文献5:日本特开2001-015155号公报
专利文献6:日本特开2002-260725号公报
专利文献7:日本特开2014-102877号公报
发明内容
发明要解决的问题
如果向非水电解质二次电池的正极板中添加过量的碳酸锂,则会有对高温循环特性、高温保存特性之类的高温环境下的电池特性造成不良影响的情况。因此,向正极板中添加的碳酸锂添加量优选为少量。为了利用少量的碳酸锂来迅速地启动电流阻断机构,需要在过充电时使碳酸锂有效分解的手段。
本发明是鉴于上述情况而进行的,其目的在于,提供能够利用少量的碳酸锂在过充电时迅速地启动电流阻断机构的非水电解质二次电池。
用于解决问题的方案
本发明的第一方式所述的非水电解质二次电池的特征在于,其包括:包含正极活性物质的正极板、包含负极活性物质的负极板、夹在正极板与负极板之间的间隔件、非水电解质、有底筒状的外装罐、以及具有在规定的电池内压下启动的电流阻断机构的封口体,
正极活性物质为通式LixNiyM(1-y)O2(0<x≤1.2、0.85≤y≤0.99、M为选自Al、Co、Fe、Cu、Mg、Ti、Zr、Ce和W中的至少1种元素)所示的锂镍复合氧化物,相对于正极活性物质的质量为0.01质量%以上且0.2质量%以下的碳酸锂被添加至正极板中。
本发明的第二方式所述的非水电解质二次电池的特征在于,其包括:包含正极活性物质的正极板、包含负极活性物质的负极板、夹在正极板与负极板之间的间隔件、非水电解质、有底筒状的外装罐、以及具有在规定的电池内压下启动的电流阻断机构的封口体,
正极活性物质为通式LixNiyM(1-y)O2(0<x≤1.2、0.88≤y≤0.99、M为选自Al、Co、Fe、Cu、Mg、Ti、Zr、Ce和W中的至少1种元素)所示的锂镍复合氧化物,相对于正极活性物质的质量为0.01质量%以上且0.2质量%以下的碳酸锂被添加至正极板中。
发明效果
根据本发明的一个方式,能够利用少量的碳酸锂在过充电时迅速地启动电流阻断机构。因此,根据本发明的一个方式,能够提供兼顾高温环境下的电池特性和过充电时的安全性的非水电解质二次电池。
附图说明
图1是实验例所述的非水电解质二次电池的截面立体图。
具体实施方式
正极活性物质使用通式LixNiyM(1-y)O2所示的锂镍复合氧化物。正极活性物质可以通过例如将成为锂源的氢氧化锂与包含镍、其它金属元素M的复合氧化物一同在氧气气氛下进行烧成来制作。刚刚制作后的锂镍复合氧化物中的x优选为1以上且1.2以下。需要说明的是,由于充电时从锂镍复合氧化物中释放出锂,因此,作为正极活性物质而包含在非水电解质二次电池中的锂镍复合氧化物的x规定为0<x≤1.2。
锂镍复合氧化物中的镍含量越大,则高充电深度(SOC)下的电阻越会增加。换言之,镍含量越大,则过充电时的正极极化变得越大,正极越会迅速地到达碳酸锂的分解电位。上述通式中的y优选为0.85以上、更优选为0.88以上。另一方面,为了提高锂镍复合氧化物的电池特性、安全性,优选将一部分Ni用选自Al、Co、Fe、Cu、Mg、Ti、Zr、Ce和W中的至少1种元素取代。y优选为0.99以下。
正极板可以通过例如将包含正极活性物质的正极合剂浆料涂布至正极集电体上并干燥来制作。正极合剂浆料可以通过将正极活性物质与粘结剂投入至分散介质中并混炼来制作。正极合剂浆料中可以添加有导电剂。
作为负极活性物质,可以使用能够吸储、释放锂离子的碳材料;能够与锂发生合金化的金属材料。作为碳材料,可例示出天然石墨和人造石墨等石墨。作为金属材料,可例示出硅和锡、以及它们的氧化物。碳材料和金属材料可以单独使用,或者混合使用两种以上。
负极板可以通过例如将包含负极活性物质的负极合剂浆料涂布至负极集电体上并干燥来制作。负极合剂浆料可以通过将负极活性物质与粘结剂投入至分散介质中并混炼来制作。负极合剂浆料可以添加有增稠剂。
作为间隔件,可以使用以聚乙烯(PE)、聚丙烯(PP)之类的聚烯烃为主成分的微多孔膜。微多孔膜可以以1层使用,或者层叠2层以上来使用。在2层以上的层叠间隔件中,优选将以熔点低的聚乙烯(PE)为主成分的层作为中间层,并将耐氧化性优异的聚丙烯(PP)作为表面层。进而,可以向间隔件中添加氧化铝(Al2O3)、氧化钛(TiO2)和氧化硅(SiO2)之类的无机粒子。这样的无机粒子可以担载于间隔件中,也可以与粘结剂一起涂布至间隔件表面。
正极板与负极板隔着间隔件卷绕而构成电极体。电极体与非水电解质一起容纳在有底筒状的外装罐中。有底筒状的外装罐的开口部借助垫片进行嵌紧固定,由此使电池内部被密闭。在封口体的内部设置有电池内压达到规定值时阻断电流通路的电流阻断机构。
非水电解质可通过例如向非水溶剂中溶解作为电解质盐的锂盐来制备。
作为非水溶剂,可以使用环状碳酸酯、链状碳酸酯、环状羧酸酯和链状羧酸酯,它们优选混合使用2种以上。作为环状碳酸酯,可例示出碳酸乙烯酯(EC)、碳酸丙烯酯(PC)和碳酸丁烯酯(BC)。此外,也可以使用如氟代碳酸乙烯酯(FEC)那样地用氟取代一部分氢而成的环状碳酸酯。作为链状碳酸酯,可例示出碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)和碳酸甲丙酯(MPC)等。作为环状羧酸酯,可例示出γ-丁内酯(γ-BL)和γ-戊内酯(γ-VL),作为链状羧酸酯,可例示出新戊酸甲酯、新戊酸乙酯、异丁酸甲酯和丙酸甲酯。
作为锂盐,可例示出LiPF6、LiBF4、LiCF3SO3、LiN(CF3SO2)2、LiN(C2F5SO2)2、LiN(CF3SO2)(C4F9SO2)、LiC(CF3SO2)3、LiC(C2F5SO2)3、LiAsF6、LiClO4、Li2B10Cl10和Li2B12Cl12。这些之中,特别优选为LiPF6,非水电解质中的浓度优选为0.5~2.0mol/L。也可以向LiPF6中混合LiBF4等其它锂盐。
以下,使用图1所示的非水电解质二次电池的实验例,详细说明用于实施本发明的方式。需要说明的是,本发明不限定于下述的实验例,可以在不变更其主旨的范围内适当变更并实施。
(实验例1)
(正极板的制作)
以氢氧化锂的摩尔数相对于复合氧化物中的金属元素的总摩尔数之比达到1.025的方式,将氢氧化锂与Ni0.85Co0.12Al0.03O2所示的复合氧化物进行混合。通过将该混合物在750℃的氧气气氛下烧成18小时,从而制作LiNi0.85Co0.12Al0.03O2所示的锂镍复合氧化物。
以如上制作的锂镍复合氧化物达到100质量份、作为导电剂的乙炔黑达到1质量份、作为粘结剂的聚偏二氟乙烯达到0.9质量份、碳酸锂(Li2CO3)达到0.05质量份的方式进行混合。将其混合物投入至作为分散介质的N-甲基-2-吡咯烷酮中,进行混炼而制作正极合剂浆料。将该正极活性物质浆料涂布至由铝箔形成的正极集电体的两面,进行干燥而形成正极合剂层。将该正极合剂层以达到规定厚度的方式进行压缩,将压缩后的极板切割成规定尺寸。最后,在未形成正极合剂层的正极集电体的露出部接合正极接头12,从而制作正极板11。
(负极板的制作)
以作为负极活性物质的石墨达到97质量份、作为粘结剂的苯乙烯丁二烯橡胶达到1.5质量份、作为增稠剂的羧甲基纤维素达到1.5质量份的方式进行混合。将其混合物投入至作为分散介质的水中,进行混炼而制作负极合剂浆料。将该负极合剂浆料涂布至由铜箔形成的负极集电体的两面,进行干燥而形成负极合剂层。将该负极合剂层以达到规定厚度的方式进行压缩,将压缩后的极板切割成规定尺寸。最后,在未形成负极合剂层的负极集电体的露出部接合负极接头14,从而制作负极板13。
(电极体的制作)
通过将正极板11与负极板13隔着由聚乙烯制微多孔膜形成的间隔件15进行卷绕,从而制作电极体16。电极体16的卷绕终止部的间隔件的端部被粘合胶带固定。
(非水电解质的制备)
将碳酸乙烯酯(EC)与碳酸二甲酯(DMC)以3∶7的体积比(1个大气压、25℃)进行混合,从而制作非水溶剂。将作为电解质盐的六氟磷酸锂(LiPF6)以1.0mol/L的浓度溶解至该非水溶剂中,从而制备非水电解质。
(封口体的制作)
将端子盖22、阀芯23、环状的绝缘板24和端子板25层叠而制作封口体21。阀芯23和端子板25由铝板形成,阀芯23可随着电池内压的增加而变形。为了使阀芯23接收电池内压而在端子板25设置有多个通气孔。如果电池内压达到规定值,则阀芯23与端子板25的接合部发生断裂,封口体内部的电流通路被断开。像这样,本实验例中,由阀芯23、绝缘板24和端子板25构成电流阻断机构。
(非水电解质二次电池的制作)
在电极体16的上部和下部分别配置上部绝缘板17和下部绝缘板18,将电极体16插入至外装罐20中。将负极接头14连接于外装罐20的底部,将正极接头12连接于封口体21。将非水电解质注入至外装罐20的内部后,借助垫片19将封口体21嵌紧固定于外装罐20的开口部,从而制作实验例1的非水电解质二次电池10。
(实验例2~5)
除了将碳酸锂的添加量设为表1中记载的值之外,与实验例1同样操作,制作实验例2~5的非水电解质二次电池10。需要说明的是,表1中记载的碳酸锂的添加量用相对于正极活性物质质量的百分率来表示。
(实验例6)
除了非水电解质包含环己基苯之外,与实验例1同样操作,制作实验例6的非水电解质二次电池10。环己基苯的含量相对于非水溶剂的质量设为1质量%。
(实验例7)
除了非水电解质包含叔丁基苯之外,与实验例1同样操作,制作实验例7的非水电解质二次电池10。叔丁基苯的含量相对于非水溶剂的质量设为1质量%。
(实验例8~12)
作为正极活性物质而使用LiNi0.88Co0.09Al0.03O2所示的锂镍复合氧化物,将碳酸锂的添加量设为表1中记载的值,除此之外,与实验例1同样操作,制作实验例8~12的非水电解质二次电池10。
(实验例13~17)
作为正极活性物质而使用LiNi0.91Co0.06Al0.03O2所示的锂镍复合氧化物,将碳酸锂的添加量设为表1中记载的值,除此之外,与实验例1同样操作,制作实验例13~17的非水电解质二次电池10。
(实验例18~22)
作为正极活性物质而使用LiNi0.82Co0.15Al0.03O2所示的锂镍复合氧化物,将碳酸锂的添加量设为表1中记载的值,除此之外,与实验例1同样操作,制作实验例18~22的非水电解质二次电池10。
(实验例23)
除了将碳酸锂的添加量相对于正极活性物质的质量设为0.3质量%之外,与实验例8~12同样操作,制作实验例23的非水电解质二次电池10。
(过充电试验)
将实验例1~22的各电池以0.3It的恒定电流进行充电,测定电流阻断机构启动时的充电深度(SOC)和最高到达温度。表1示出测定结果。
[表1]
使用了将通式LixNiyM(1-y)O2的y设为0.82的锂镍复合氧化物的实验例18~22中,随着碳酸锂添加量的增加,电流阻断机构迅速启动,过充电时的电池的最高到达温度降低。但是,碳酸锂的添加量少的实验例18和19中,电池的最高到达温度超过了100℃。因此,为了提高过充电时的安全性,需要增加碳酸锂的添加量。
另一方面,将通式LixNiyM(1-y)O2的y设为0.85的实验例1~5中,通过向正极板中添加碳酸锂,显示出电池的最高到达温度均小于100℃的高安全性。此外,实验例8~17中,与实验例1~5同样地示出:随着y的增加,电池的最高到达温度降低。换言之,由于锂镍复合氧化物中的镍含量的增加,向正极板中添加的碳酸锂在过充电时有效地分解,二氧化碳气体的产生得以促进。根据上述结果,通过将y设为0.85以上,即使利用少量的碳酸锂也能够提高过充电时的非水电解质二次电池的安全性。但是,通过将y设为0.88以上,过充电时的电池安全性进一步提高,因此,y更优选为0.88以上。
碳酸锂即使为少量,只要其包含在正极板中,就能够提高非水电解质二次电池的过充电时的安全性。碳酸锂的优选添加量相对于正极活性物质的质量为0.01质量%以上,更优选为0.05质量%以上。
非水电解质包含作为苯衍生物的环己基苯的实验例6的电池的最高到达温度,与非水电解质不含环己基苯的实验例1相比大幅降低。此外,非水电解质包含作为苯衍生物的叔丁基苯的实验例7的最高到达温度也为60℃,显示出与实验例6相同的结果。由这些结果可知:优选非水电解质包含苯衍生物。可以认为:本发明的锂镍复合氧化物在过充电时的极化大,因此,在正极上不仅碳酸锂有效地分解,苯衍生物也有效地分解,它们协同性地提高过充电时的安全性。
(高温循环试验)
将实验例8~12和23的各电池以0.3It的恒定电流充电至电池电压达到4.2V为止,接着,以4.2V的低电压充电至电流达到0.02It为止。其后,将各电池以0.5It的恒定电流放电至电池电压达到2.5V为止。将该充放电循环在45℃的环境下重复1000个循环。将第1000个循环的放电容量相对于第1个循环的放电容量的百分率作为容量维持率来计算。将其结果示于表2。
[表2]
将实验例12与实验例23进行对比时,通过向正极板中添加0.3质量%的碳酸锂,循环特性大幅降低。但是,实验例8~11的容量维持率均超过70%,因此,如果向正极板中添加的碳酸锂添加量为0.2质量%以下,则能够抑制碳酸锂对循环特性造成的影响。从高温循环特性的观点出发,向正极板中添加的碳酸锂添加量优选为0.2质量%以下。如果还考虑到表1所示的过充电试验的结果,则为了兼顾过充电时的安全性和高温循环特性,向正极板中添加的碳酸锂添加量优选为0.01质量%以上且0.2质量%以下、更优选为0.05质量%以上且0.2质量%以下。
本实验例中,作为不同种元素而使用了钴(Co)和铝(Al),但除此之外,还可以使用铁(Fe)、铜(Cu)、镁(Mg)、钛(Ti)、锆(Zr)、铈(Ce)和钨(W)。这些不同种元素可以单独使用,或者组合使用多种。
本实验例中,作为苯衍生物而使用了环己基苯和叔丁基苯,但除此之外,还可以使用叔戊基苯、联苯、氟苯、三氟苯、苯、六氟苯、苯基内酯、二苯基醚、碳酸二苯酯和碳酸甲基苯酯。这些苯衍生物可以单独使用,或者组合使用多种。非水电解质中的苯衍生物的含量相对于非水溶剂的质量优选为0.1质量%以上且5质量%以下。
产业上的可利用性
如上所述,根据本发明,能够利用少量的碳酸锂在过充电时迅速地启动电流阻断机构。本发明能够提供兼顾高温环境下的电池特性和过充电时的安全性的非水电解质二次电池,因此在产业上的可利用性大。
附图标记说明
10 非水电解质二次电池
11 正极板
13 负极板
15 间隔件
20 外装罐
21 封口体
Claims (3)
1.一种非水电解质二次电池,其具备:包含正极活性物质的正极板、包含负极活性物质的负极板、夹在所述正极板与所述负极板之间的间隔件、非水电解质、有底筒状的外装罐、以及具有在规定的电池内压下启动的电流阻断机构的封口体,
所述正极活性物质为通式LixNiyM(1-y)O2所示的锂镍复合氧化物,其中,0<x≤1.2、0.85≤y≤0.91、M为选自Al、Co、Fe、Cu、Mg、Ti、Zr、Ce和W中的至少1种元素,
相对于所述正极活性物质的质量为0.15质量%以上且0.2质量%以下的碳酸锂被添加至所述正极板中,
过充电时的电池的最高到达温度为79℃以下。
2.根据权利要求1所述的非水电解质二次电池,其中,
所述正极活性物质为通式LixNiyM(1-y)O2所示的锂镍复合氧化物,其中,0<x≤1.2、0.88≤y≤0.91、M为选自Al、Co、Fe、Cu、Mg、Ti、Zr、Ce和W中的至少1种元素,
过充电时的电池的最高到达温度为56℃以下。
3.根据权利要求1或2所述的非水电解质二次电池,其中,所述非水电解质包含选自环己基苯、叔丁基苯、叔戊基苯、联苯、氟苯、三氟苯、苯、六氟苯、苯基内酯、二苯基醚、碳酸二苯酯和碳酸甲基苯酯中的至少1种苯衍生物。
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