JP2010015986A - 二次電池 - Google Patents
二次電池 Download PDFInfo
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- JP2010015986A JP2010015986A JP2009154992A JP2009154992A JP2010015986A JP 2010015986 A JP2010015986 A JP 2010015986A JP 2009154992 A JP2009154992 A JP 2009154992A JP 2009154992 A JP2009154992 A JP 2009154992A JP 2010015986 A JP2010015986 A JP 2010015986A
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- 239000007773 negative electrode material Substances 0.000 claims abstract description 52
- 239000007774 positive electrode material Substances 0.000 claims abstract description 38
- 230000002427 irreversible effect Effects 0.000 claims abstract description 24
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 13
- 229910000676 Si alloy Inorganic materials 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 7
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 4
- 229910010238 LiAlCl 4 Inorganic materials 0.000 claims description 3
- 229910010090 LiAlO 4 Inorganic materials 0.000 claims description 3
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
- 229910013372 LiC 4 Inorganic materials 0.000 claims description 3
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 3
- 229910013131 LiN Inorganic materials 0.000 claims description 3
- 229910012513 LiSbF 6 Inorganic materials 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 4
- 239000008151 electrolyte solution Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 17
- 229910052744 lithium Inorganic materials 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- -1 nickel metal hydride Chemical class 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910015228 Ni1/3Mn1/3CO1/3 Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 4
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004698 Polyethylene Substances 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
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052987 metal hydride Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 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
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
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- 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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- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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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- H01M4/50—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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Abstract
【解決手段】本発明に係る二次電池は、正極活物質層を含む正極、負極活物質層を含む負極、上記正極および負極間に介するセパレータ、および非水性電解液を含み、上記正極活物質層はリチウムニッケル酸化物を含んでなり、上記負極活物質はシリコン、シリコン酸化物およびシリコン合金から選択される少なくともいずれか一つを含んで形成される。
【選択図】図1
Description
200mlのエタノールに、平均粒度が0.1〜2μmのCoCO3を100g添加してコバルト系前駆体溶液を製造した。沈殿方法によって化学量論比でニッケルヒドロキシド、マンガンヒドロキシド、およびコバルトヒドロキシドを沈殿させて[Ni1/3Mn1/3Co1/3]Oを製造した後、上記エタノール溶液に添加し撹はんして、CoCO3粉末の表面に[Ni1/3Mn1/3Co1/3]Oが均一にコーティングされるようにした。溶媒を除去した後、CoCO3の表面に[Ni1/3Mn1/3Co1/3]Oがコーティングされた粉末をLi2CO3と1:1のモル比で混合し、酸素分雰囲気下、800℃で5時間焼成した後冷却させて、0.1〜2μmの微細粒子が凝集したLiCoO2の表面に[Ni1/3Mn1/3Co1/3]O2層が形成された正極活物質を製造した。
LiPF6が溶解されたエチレンカーボネート、ジエチルカーボネート、ジメチルカーボネート、およびフルオロベンゼン混合溶液(3:5:1:1の体積比)を用いた。
比較例1では、実施例1の負極活物質の量と比較例2の負極活物質の量を同一にしたが、SiO添加剤を投入しなかった。比較例2では、実施例1で測定された負極活物質の充電可能容量と同一に負極活物質を投入し、SiO添加剤を投入しなかった。比較例1および比較例2でその他の条件は実施例1と同一である。
120 正極活物質層
200 負極
220 負極活物質層
300 セパレータ
1000 電極組立体
Claims (9)
- 正極活物質層を含む正極、
負極活物質層を含む負極、
上記正極および負極間に介するセパレータ、および
非水性電解液を含み、
上記正極活物質層はリチウムニッケル酸化物を含んでなり、上記負極活物質はシリコン、シリコン酸化物およびシリコン合金から選択される少なくとも一つを含んで形成されることを特徴とする二次電池。 - 上記負極活物質はSiOを含むことを特徴とする請求項1に記載の二次電池。
- 上記正極活物質層はNi、CoおよびMnを含んで形成されることを特徴とする請求項1に記載の二次電池。
- 上記正極活物質の非可逆容量は上記負極活物質の非可逆容量より大きいことを特徴とする請求項1に記載の二次電池。
- 上記シリコン、シリコン酸化物およびシリコン合金から選択される少なくとも一つは全体負極活物質に対し2〜6重量%で含まれることを特徴とする請求項1に記載の二次電池。
- 上記非水性電解液はリチウム塩と非水性有機溶媒とを含むことを特徴とする請求項1に記載の二次電池。
- 上記リチウム塩は、LiPF6、LiBF4、LiSbF6、LiAsF6、LiClO4、LiCF3SO3、Li(CF3SO2)2N、LiC4F9SO3、LiAlO4、LiAlCl4、LiN(CxF2X+1SO2)(CyF2y+1SO2)(ここで、xおよびyは自然数である。)、LiClおよびLiIからなる群より選択される少なくとも一つであることを特徴とする請求項6に記載の二次電池。
- 上記非水性有機溶媒は、カーボネート、エステル、エーテル、およびケトンからなる群より選択される少なくともいずれか一つであることを特徴とする請求項6に記載の二次電池。
- 上記セパレータは、上記正極と負極間に介して共に巻回されて電極組立体を形成し、
上記電極組立体を収容する缶、および
上記缶の開口領域を閉塞するキャップ組立体をさらに含むことを特徴とする請求項1に記載の二次電池。
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ATE522942T1 (de) | 2011-09-15 |
US20090325061A1 (en) | 2009-12-31 |
CN101621132A (zh) | 2010-01-06 |
CN101621132B (zh) | 2012-08-15 |
KR20100002695A (ko) | 2010-01-07 |
EP2141759B1 (en) | 2011-08-31 |
EP2141759A1 (en) | 2010-01-06 |
US9450240B2 (en) | 2016-09-20 |
KR101126826B1 (ko) | 2012-03-23 |
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