JP2016058236A - リチウムイオン二次電池 - Google Patents
リチウムイオン二次電池 Download PDFInfo
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- JP2016058236A JP2016058236A JP2014183742A JP2014183742A JP2016058236A JP 2016058236 A JP2016058236 A JP 2016058236A JP 2014183742 A JP2014183742 A JP 2014183742A JP 2014183742 A JP2014183742 A JP 2014183742A JP 2016058236 A JP2016058236 A JP 2016058236A
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- negative electrode
- positive electrode
- mixture layer
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- lithium ion
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 74
- 239000011888 foil Substances 0.000 claims abstract description 32
- 229910000676 Si alloy Inorganic materials 0.000 claims abstract description 15
- 239000002210 silicon-based material Substances 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- 239000007773 negative electrode material Substances 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 7
- 239000010935 stainless steel Substances 0.000 claims abstract description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 239000004332 silver Substances 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000007599 discharging Methods 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 5
- 239000011135 tin Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 238000003466 welding Methods 0.000 description 10
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 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 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 239000005001 laminate film Substances 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000011883 electrode binding agent Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- OIXUJRCCNNHWFI-UHFFFAOYSA-N 1,2-dioxane Chemical compound C1CCOOC1 OIXUJRCCNNHWFI-UHFFFAOYSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CAQYAZNFWDDMIT-UHFFFAOYSA-N 1-ethoxy-2-methoxyethane Chemical compound CCOCCOC CAQYAZNFWDDMIT-UHFFFAOYSA-N 0.000 description 1
- HTWIZMNMTWYQRN-UHFFFAOYSA-N 2-methyl-1,3-dioxolane Chemical compound CC1OCCO1 HTWIZMNMTWYQRN-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- LJPCNSSTRWGCMZ-UHFFFAOYSA-N 3-methyloxolane Chemical compound CC1CCOC1 LJPCNSSTRWGCMZ-UHFFFAOYSA-N 0.000 description 1
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013131 LiN Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000491 Polyphenylsulfone Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
(ラミネートセルの仕様)
表1は、実施例及び比較例の1Ah級ラミネートセルの仕様を示したものである。表2は、30Ah級ラミネートセルの仕様を示したものである。いずれも同じ仕様で電極の積層枚数とセル寸法とを変えることで2種類のセルを作製した。表1に示す実施例1〜30及び比較例1〜10は、表2に示す実施例31〜60及び比較例11〜20に対応している。
まず、前述の負極活物質及びバインダ以外に、アセチレンブラックを導電材として用い、その質量比率は順に92:5:3で作製し、粘度が5000〜8000mPaとなるように、また固形分比が70%以上90%以下となるように、溶媒(N−メチル−2−ピロリドン(NMP))を混合しながら、負極スラリーを作製した。なお、本明細書における粘度は、0.5rpmで600秒目の値である。また、スラリーの作製は、プラネタリミキサを用いた。
図1は、ラミネートセル内部の積層型電極群の分解図を示したものである。
作製したラミネートセルを用いて、電圧4.3V、電流1/3CAの定電流充電をした後、2時間定電圧充電した。放電は、電圧2.0V、電流1/3CAで定電流放電をした。これを10サイクル行い、10サイクル目の容量と1サイクル目の容量との商から、容量維持率を算出した。そして、短絡調査をするために、電圧3.7V、電流1/3CAの定電流充電をした後、2時間定電圧充電をし、1週間放置した。放置後に3.4V以下となっていたものを「短絡」と定義し、10セル中の短絡本数を短絡発生率として算出した。
Claims (8)
- 長方形状の正極と、
長方形状の負極と、
セパレータと、を含むリチウムイオン二次電池であって、
前記正極、前記負極及び前記セパレータは、積層型電極群を構成し、
前記正極は、正極集電箔と、正極活物質を含む正極合剤層と、を含み、
前記負極は、負極集電箔と、負極活物質を含む負極合剤層と、を含み、
前記負極活物質は、シリコン系材料と、炭素質材料と、を含有し、
前記シリコン系材料と前記炭素質材料との質量比は、20:80〜80:20であり、
前記シリコン系材料は、Si合金又はSiOx(0.5≦x≦1.5)であり、
前記正極及び前記負極は、前記積層型電極群の共通する一辺から突出した集電端子を有し、
前記負極集電箔は、ステンレス鋼、又は純度99.9%以上の銅にジルコニウム、銀及びスズのうち少なくとも1種類以上の元素を混合した銅合金若しくは純度99.99%以上の銅で形成され、
前記一辺から前記集電端子が突出した方向における前記正極合剤層及び前記負極合剤層の長さは、前記正極合剤層の長さが前記負極合剤層の長さ以上であることを特徴とするリチウムイオン二次電池。 - 前記負極集電箔は、ステンレス鋼、又は純度99.9%以上の銅にジルコニウム、銀及びスズのうち少なくとも1種類以上の元素を混合した銅合金で形成され、
前記一辺から前記集電端子が突出した方向における前記正極合剤層、前記負極合剤層及び前記セパレータの長さは、前記負極合剤層の長さを100とした場合に、前記正極合剤層が100以上102以下であり、前記セパレータが102以上104以下である、請求項1記載のリチウムイオン二次電池。 - 前記負極集電箔は、純度99.99%以上の銅で形成され、
前記一辺から前記集電端子が突出した方向における前記正極合剤層、前記負極合剤層及び前記セパレータの長さは、前記負極合剤層の長さを100とした場合に、前記正極合剤層が100以上104以下であり、前記セパレータが104以上106以下である、請求項1記載のリチウムイオン二次電池。 - 前記負極の対極Li基準で0V〜1.5Vの範囲の放電容量が600Ah/kg以上1100Ah/kg以下である、請求項1〜3のいずれか一項に記載のリチウムイオン二次電池。
- 前記Si合金は、Siと、Al、Ni、Cu、Fe、Ti及びMnからなる群から選択される1種類以上の異種金属元素と、を含み、前記Siと前記異種金属元素との原子比率は、50:50〜90:10である、請求項1〜4のいずれか一項に記載のリチウムイオン二次電池。
- 前記シリコン系材料は、前記Si合金であり、
前記炭素質材料は、黒鉛であり、
前記シリコン系材料と前記炭素質材料との質量比は、40:60〜70:30である、請求項1〜5のいずれか一項に記載のリチウムイオン二次電池。 - 前記セパレータは、袋状である、請求項1〜6のいずれか一項に記載のリチウムイオン二次電池。
- 前記セパレータは、前記負極を包む構成である、請求項7記載のリチウムイオン二次電池。
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