JP5729588B2 - 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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- JP5729588B2 JP5729588B2 JP2010210073A JP2010210073A JP5729588B2 JP 5729588 B2 JP5729588 B2 JP 5729588B2 JP 2010210073 A JP2010210073 A JP 2010210073A JP 2010210073 A JP2010210073 A JP 2010210073A JP 5729588 B2 JP5729588 B2 JP 5729588B2
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 54
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 54
- 239000000203 mixture Substances 0.000 claims description 78
- 239000011148 porous material Substances 0.000 claims description 50
- 229910052744 lithium Inorganic materials 0.000 claims description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 29
- 239000007773 negative electrode material Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 16
- 238000009826 distribution Methods 0.000 claims description 14
- 239000003575 carbonaceous material Substances 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 7
- 239000003125 aqueous solvent Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000004438 BET method Methods 0.000 claims description 5
- 150000002642 lithium compounds Chemical class 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims 1
- 239000010410 layer Substances 0.000 description 50
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 238000007600 charging Methods 0.000 description 16
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- 229910052751 metal Inorganic materials 0.000 description 15
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- 238000010281 constant-current constant-voltage charging Methods 0.000 description 5
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-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
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013372 LiC 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 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
- 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
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- 229910052804 chromium Inorganic materials 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910021469 graphitizable carbon Inorganic materials 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000011254 layer-forming composition Substances 0.000 description 1
- 229910021439 lithium cobalt complex oxide Inorganic materials 0.000 description 1
- 229910021445 lithium manganese complex oxide Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
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- 229920002647 polyamide Polymers 0.000 description 1
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- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
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- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
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Classifications
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- 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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- Battery Mounting, Suspending (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
比表面積の異なる8種類の黒鉛粉末C1〜C8を用意し、これらの黒鉛粉末を負極活物質に用いた負極を作製した。すなわち、各黒鉛粉末とSBRとCMCとを、これら材料の質量比が98:1:1であり且つNVが45質量%となるようにイオン交換水と混合して、負極合剤層形成用の組成物を調製した。この組成物を、厚さ10μmの長尺状銅箔(負極集電体)の両面に塗布して乾燥させることにより、負極合剤層を形成した。上記組成物の目付け、すなわち塗布量(固形分基準)は、両面合わせて9.4mg/cm2となるように調整した。乾燥温度120℃の条件下で乾燥後、負極集電体とその両面の負極合剤層とを合わせた全体の厚みが60μmとなるようにプレスした。このようにして、各黒鉛粉末C1〜C8に対応する合計8種類のシート状負極(すなわち、負極シートN1〜N8)を作製した。なお、上記黒鉛粉末C1〜C8の平均粒径は、いずれも6.5μm〜22μmの範囲にある。
負極シートN1〜N8について、直径が0.1μm〜0.4μmの細孔の単位質量当たりの容積A[cc/g]を測定した。測定には、Quantachtome社製の「Pore master GT60」(圧力範囲0.7psi〜33000psi)を使用した。得られた値を表3に示す。なお、表3では細孔容量A[cc/g]と表記している。
負極シートN1〜N8について、比表面積B[m2/g]を測定した。測定には、MOUNTECH社製の「Macsorb」を使用した。120℃の温度条件下で1時間乾燥させ(プレ乾燥)、120℃の温度条件下で5分間の予備脱気を行った後、測定を行った。得られた値を表3に示す。
例A1〜A8の電池に対し、下記表1に示す条件にて初期充放電(コンディショニング)を行った。すなわち、25℃の温度条件下において、以下の充電、休止、および放電を行った。具体的には、まず、端子間電圧が4.1Vになるまで1/4Cの定電流にて充電し、続いて合計充電時間が6時間になるまで定電圧で充電した(CCCV充電)。その後、10分間休止した後、1/3Cの定電流にて端子間電圧が3.0Vになるまで放電した(CC放電)。次に、10分間休止した後、端子間電圧が4.1Vになるまで1Cの定電流にて充電し、続いて合計充電時間が2時間になるまで定電圧で充電した(CCCV充電)。その後、10分間休止した後、1Cの定電流にて端子間電圧が3.0Vになるまで放電した(CC放電)。次に、10分間休止した後、端子間電圧が4.1Vになるまで1Cの定電流にて充電し、続いて合計充電時間が2.5時間になるまで定電圧で充電した(CCCV充電)。その後、10分間休止した後、1/3Cの定電流にて端子間電圧が3.0Vになるまで放電し(CC放電)、10分間休止した後、さらに合計放電時間が4時間になるまで定電圧で放電した(CV放電)後、10分間休止した。
例A1〜A8の電池について、所定の高温条件下で保存した後に容量がどの程度維持されているかを調べる試験を行った。
負極シートN1〜N8を用いたラミネート型電池セルを作製し、リチウムの析出しにくさを評価する試験を行った。すなわち、それぞれ負極シートN1〜N8を含む電極体を両端子部の一部が露出するようにラミネートフィルム(7cm×7cm(片面))で覆って、電解液を注入し、ラミネートフィルムを封止して8種類のラミネート型電池セルB1〜B8を作製した。正極、セパレータ、および電解液は、例A1〜A8の電池と同様である。
10 リチウムイオン二次電池
11 容器
14 正極端子
16 負極端子
30 捲回電極体
32 正極シート
34 負極シート
35 セパレータシート
Claims (7)
- 正極と、負極集電体と該負極集電体上に形成された負極合剤層とを有する負極と、前記正極と前記負極との間に介在するセパレータと、前記正極と前記負極と前記セパレータとに含浸されリチウムイオンを含む非水電解液と、を備えたリチウムイオン二次電池であって、
前記負極合剤層は、カーボン材料からなる負極活物質を有し、
前記負極合剤層における直径0.1μm〜0.4μmの細孔の単位質量当たりの容積をA[cc/g]とし、BET法により測定した前記負極の表面積を前記負極合剤層の単位質量当たりの表面積に換算した比表面積をB[m2/g]としたときに、A/B=0.0079〜0.0091[cc/m2]である、リチウムイオン二次電池。 - 前記負極合剤層は、0.1μm〜0.4μmの範囲内の所定の直径にて第1のピークを有し、0.4μmよりも大きな直径で第2のピークを有する細孔分布を備えている、請求項1に記載のリチウムイオン二次電池。
- 前記負極活物質は、少なくとも一部にグラファイト構造を有するカーボン材料を含んでいる、請求項1または2に記載のリチウムイオン二次電池。
- 前記負極活物質は、平均粒径が5μm〜50μmのカーボン粒子からなっている、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。
- 前記非水電解液は、非プロトン性の非水溶媒と、該溶媒に溶解してリチウムイオンを供給し得るリチウム化合物とを含んでいる、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。
- 前記負極集電体は、銅または銅を主成分とする合金からなっている、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。
- 車両駆動電源として用いられる、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。
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