JP7442061B2 - 二次電池 - Google Patents
二次電池 Download PDFInfo
- Publication number
- JP7442061B2 JP7442061B2 JP2020553819A JP2020553819A JP7442061B2 JP 7442061 B2 JP7442061 B2 JP 7442061B2 JP 2020553819 A JP2020553819 A JP 2020553819A JP 2020553819 A JP2020553819 A JP 2020553819A JP 7442061 B2 JP7442061 B2 JP 7442061B2
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- secondary battery
- resin
- oxygen
- active material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920005989 resin Polymers 0.000 claims description 83
- 239000011347 resin Substances 0.000 claims description 83
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 61
- 229910052760 oxygen Inorganic materials 0.000 claims description 61
- 239000001301 oxygen Substances 0.000 claims description 61
- 239000000203 mixture Substances 0.000 claims description 47
- 239000000654 additive Substances 0.000 claims description 26
- 230000000996 additive effect Effects 0.000 claims description 25
- 239000007774 positive electrode material Substances 0.000 claims description 23
- 229940123973 Oxygen scavenger Drugs 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 14
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- 239000007773 negative electrode material Substances 0.000 claims description 11
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 238000009830 intercalation Methods 0.000 claims description 8
- 239000006096 absorbing agent Substances 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 235000002639 sodium chloride Nutrition 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 3
- 229910010586 LiFeO 2 Inorganic materials 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
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- 239000000956 alloy Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 229910014458 Ca-Si Inorganic materials 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
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- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 12
- 230000002427 irreversible effect Effects 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
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- 238000000034 method Methods 0.000 description 10
- 230000002000 scavenging effect Effects 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000003125 aqueous solvent Substances 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 5
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- 239000002904 solvent Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
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- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
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- 239000010949 copper Substances 0.000 description 2
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- 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
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
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- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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Images
Classifications
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- 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
-
- 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
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Description
樹脂溶液と、樹脂溶液中に分散している脱酸素剤とを含む脱酸素剤の分散液(以下、脱酸素剤を含む樹脂溶液とも称する。)を調製する。得られた分散液を正極またはセパレータに塗布し、乾燥により樹脂溶液中の溶媒を除去する。このようにして、正極またはセパレータの表面に脱酸素樹脂層を形成する。溶媒を除去することで、多孔質な脱酸素樹脂層を形成し得るため、正極と非水電解質との間でのリチウムイオンの移動は円滑に行われる。樹脂溶液に溶解する樹脂は、酸素吸収速度の制御等の役割とともに、正極またはセパレータの表面に脱酸素剤を付着させる結着剤の役割を兼ねることができる。塗布方法としては、例えば、グラビアコート法、スプレーコート法、ダイコート法、ロールコート法、ディップコート法、スクリーン印刷法等が用いられる。
正極の表面に脱酸素樹脂を担持させる場合、樹脂溶液の溶媒(脱酸素樹脂の分散媒)は、正極スラリーに含まれる分散媒と同じでもよく、異なっていてもよい。
正極21は、正極集電体21aと、正極集電体21aの両面に形成された正極合剤層21bとを有する。負極22は、負極集電体22aと、負極集電体22aの両面に形成された負極合剤層22bとを有する。セパレータ23が、正極21と負極22との間に配されている。脱酸素シート24が、正極21とセパレータ23との間に配置されている。
(正極)
正極は、例えば、正極集電体と、正極集電体の表面に形成された正極合剤層と、を具備する。正極合剤層は、正極合剤を分散媒に分散させた正極スラリーを、正極集電体の表面に塗布し、乾燥させることにより形成できる。乾燥後の塗膜を、必要により圧延してもよい。正極合剤層は、正極集電体の一方の表面に形成してもよく、両方の表面に形成してもよい。正極合剤は、必須成分として正極活物質および正極添加剤を含み、任意成分として、結着剤、導電剤、および増粘剤等を含むことができる。
負極は、例えば、負極集電体と、負極集電体の表面に形成された負極合剤層と、を具備する。負極合剤層は、負極合剤を分散媒に分散させた負極スラリーを、負極集電体の表面に塗布し、乾燥させることにより形成できる。乾燥後の塗膜を、必要により圧延してもよい。負極合剤層は、負極集電体の一方の表面に形成してもよく、両方の表面に形成してもよい。負極合剤は、必須成分として負極活物質を含み、任意成分として、結着剤、導電剤、および増粘剤等を含むことができる。結着剤、増粘剤、および分散媒としては、正極で例示したものを用いることができる。また、導電剤としては、黒鉛を除き、正極で例示したものを用いることができる。
セパレータとしては、樹脂製の微多孔フィルム、不織布、織布等が用いられる。樹脂には、ポリオレフィン、ポリアミド、ポリアミドイミド等が用いられる。ポリオレフィンとしては、例えば、ポリエチレン、ポリプロピレンが挙げられる。
非水電解質は、非水溶媒と、非水溶媒に溶解するリチウム塩とを含む。
非水溶媒としては、プロピレンカーボネート(PC)、エチレンカーボネート(EC)、フルオロエチレンカーボネート(FEC)、ビニレンカーボネート(VC)等の環状炭酸エステル;ジエチルカーボネート(DEC)、エチルメチルカーボネート(EMC)、ジメチルカーボネート(DMC)等の鎖状炭酸エステル;γ-ブチロラクトン、γ-バレロラクトン等の環状カルボン酸エステル等が挙げられる。非水溶媒は、一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
Claims (15)
- 電気化学的にリチウムイオンを吸蔵および放出可能な正極活物質を含む正極と、
電気化学的にリチウムイオンを吸蔵および放出可能な負極活物質を含む負極と、
前記正極と前記負極との間に配置されるセパレータと、
非水電解質と、を備える二次電池であって、
前記正極は、前記正極活物質と正極添加剤とを含む正極合剤を備え、
前記正極添加剤は、一般式:LiaFexMyOzで表される化合物を含み、0≦a≦5、0≦x≦5、0≦y≦1および0≦z≦4を満たし、かつ、a、x、yおよびzのうち少なくとも2つは0超であり、Mは、Mn、Zn、Al、Ga、Ge、Ti、Si、Sn、Ce、Y、Zr、SおよびNaよりなる群から選択される少なくとも1種を含み、
前記二次電池の内部に脱酸素剤が配置され、
前記脱酸素剤は、セリウム酸化物、ゼオライトおよびCa-Si合金よりなる群から選択される少なくとも1種を含む、二次電池。 - 前記正極合剤中の前記正極添加剤の含有量は、前記正極合剤の総量に対して0.1質量%以上5質量%以下である、請求項1に記載の二次電池。
- 前記正極添加剤は、Li5FeO4、Li4Fe4、LiFeO2、Li2OおよびFeO2よりなる群から選択される少なくとも1種を含む、請求項1または2に記載の二次電池。
- 前記正極活物質は、層状岩塩型の結晶構造を有するリチウム含有遷移金属酸化物を含む、請求項1~3のいずれか1項に記載の二次電池。
- 前記負極活物質は、ケイ素含有材料を含む、請求項1~4のいずれか1項に記載の二次電池。
- 前記セリウム酸化物は、一般式:CeO2-xで表され、0<x<2を満たす、請求項1~5のいずれか1項に記載の二次電池。
- 前記正極合剤中の前記正極添加剤に含まれるFeに対する、前記電池中の前記セリウム酸化物に含まれるCeの原子比:Ce/Feが、0.1以上80以下である、請求項1~6のいずれか1項に記載の二次電池。
- 前記二次電池の内部に、酸素を透過可能な樹脂と、前記樹脂中に分散している前記脱酸素剤と、を含む脱酸素樹脂が配置されている、請求項1~7のいずれか1項に記載の二次電池。
- 前記脱酸素樹脂は、前記正極合剤中に分散している、請求項8に記載の二次電池。
- 前記正極合剤中の前記脱酸素樹脂の含有量は、前記正極活物質の総量に対して1質量%以上10質量%以下である、請求項9に記載の二次電池。
- 前記脱酸素樹脂は、前記正極の表面または前記セパレータの表面に担持されている、請求項8に記載の二次電池。
- 前記二次電池の内部に、前記脱酸素樹脂がシート状に加工された脱酸素シートが配置されている、請求項8に記載の二次電池。
- 前記脱酸素シートは、定格容量1mAhあたり0.15mg以上4.7mg以下で配置されている、請求項12に記載の二次電池。
- 前記脱酸素シートは、前記正極と前記セパレータとの間に配置されている、請求項12または13に記載の二次電池。
- 電気化学的にリチウムイオンを吸蔵および放出可能な正極活物質を含む正極と、
電気化学的にリチウムイオンを吸蔵および放出可能な負極活物質を含む負極と、
前記正極と前記負極との間に配置されるセパレータと、
非水電解質と、を備える二次電池であって、
前記正極は、前記正極活物質と正極添加剤とを含む正極合剤を備え、
前記正極添加剤は、、一般式:Li a Fe x M y O z で表される化合物を含み、0≦a≦5、0≦x≦5、0≦y≦1および0≦z≦4を満たし、かつ、a、x、yおよびzのうち少なくとも2つは0超であり、Mは、Mn、Zn、Al、Ga、Ge、Ti、Si、Sn、Ce、Y、Zr、SおよびNaよりなる群から選択される少なくとも1種を含み、
前記正極と前記負極とが、前記セパレータを介して捲回された電極群を備え、
前記電極群の中心部に形成された空間に、脱酸素樹脂がシート状に加工された脱酸素シートが捲回された状態で配置され、
前記脱酸素樹脂は、酸素を透過可能な樹脂と、前記樹脂中に分散している脱酸素剤と、を含む、二次電池。
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JP2005174655A (ja) | 2003-12-09 | 2005-06-30 | Toyota Motor Corp | リチウム電池 |
JP2006114256A (ja) | 2004-10-12 | 2006-04-27 | Toyota Motor Corp | 二次電池用正極及びその利用 |
JP2009135084A (ja) | 2007-11-02 | 2009-06-18 | Panasonic Corp | リチウムイオン二次電池 |
WO2015011884A1 (ja) | 2013-07-25 | 2015-01-29 | 株式会社豊田自動織機 | 非水系二次電池用正極及び非水系二次電池 |
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US20220006069A1 (en) | 2022-01-06 |
CN112913051B (zh) | 2024-06-04 |
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