JP5609706B2 - 非水電解液二次電池 - Google Patents
非水電解液二次電池 Download PDFInfo
- Publication number
- JP5609706B2 JP5609706B2 JP2011034855A JP2011034855A JP5609706B2 JP 5609706 B2 JP5609706 B2 JP 5609706B2 JP 2011034855 A JP2011034855 A JP 2011034855A JP 2011034855 A JP2011034855 A JP 2011034855A JP 5609706 B2 JP5609706 B2 JP 5609706B2
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- JP
- Japan
- Prior art keywords
- lithium
- secondary battery
- positive electrode
- lithium salt
- electrolyte secondary
- 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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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 33
- 229910003002 lithium salt Inorganic materials 0.000 claims description 77
- 159000000002 lithium salts Chemical class 0.000 claims description 77
- 239000008151 electrolyte solution Substances 0.000 claims description 55
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 28
- 229910001416 lithium ion Inorganic materials 0.000 claims description 28
- 230000003647 oxidation Effects 0.000 claims description 26
- 238000007254 oxidation reaction Methods 0.000 claims description 26
- 229910052744 lithium Inorganic materials 0.000 claims description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 22
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 8
- 150000001639 boron compounds Chemical class 0.000 claims description 8
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- -1 cyclic carbonate compound Chemical class 0.000 description 35
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- 238000007599 discharging Methods 0.000 description 6
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- 239000010439 graphite Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
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- 229910010941 LiFSI Inorganic materials 0.000 description 2
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
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- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- GKQWYZBANWAFMQ-UHFFFAOYSA-M lithium;2-hydroxypropanoate Chemical compound [Li+].CC(O)C([O-])=O GKQWYZBANWAFMQ-UHFFFAOYSA-M 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
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- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
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- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- WAHQBNXSPALNEA-UHFFFAOYSA-L lithium succinate Chemical compound [Li+].[Li+].[O-]C(=O)CCC([O-])=O WAHQBNXSPALNEA-UHFFFAOYSA-L 0.000 description 1
- 229960004254 lithium succinate Drugs 0.000 description 1
- ZPPPLBXXTCVBNC-ZVGUSBNCSA-M lithium;(2r,3r)-2,3,4-trihydroxy-4-oxobutanoate Chemical compound [Li+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O ZPPPLBXXTCVBNC-ZVGUSBNCSA-M 0.000 description 1
- JTEOOCAGEXVCBQ-BJILWQEISA-M lithium;(e)-4-oxopent-2-en-2-olate Chemical compound [Li+].C\C([O-])=C/C(C)=O JTEOOCAGEXVCBQ-BJILWQEISA-M 0.000 description 1
- PSBOOKLOXQFNPZ-UHFFFAOYSA-M lithium;2-hydroxybenzoate Chemical compound [Li+].OC1=CC=CC=C1C([O-])=O PSBOOKLOXQFNPZ-UHFFFAOYSA-M 0.000 description 1
- CILZBARDXHWUSX-UHFFFAOYSA-M lithium;2-hydroxybutanoate Chemical compound [Li+].CCC(O)C([O-])=O CILZBARDXHWUSX-UHFFFAOYSA-M 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- IIDVGIFOWJJSIJ-UHFFFAOYSA-M lithium;2-methylpropanoate Chemical compound [Li+].CC(C)C([O-])=O IIDVGIFOWJJSIJ-UHFFFAOYSA-M 0.000 description 1
- OFJHGWPRBMPXCX-UHFFFAOYSA-M lithium;2-oxopropanoate Chemical compound [Li+].CC(=O)C([O-])=O OFJHGWPRBMPXCX-UHFFFAOYSA-M 0.000 description 1
- UTLRZTUJSMCBHB-UHFFFAOYSA-M lithium;3-oxobutanoate Chemical compound [Li+].CC(=O)CC([O-])=O UTLRZTUJSMCBHB-UHFFFAOYSA-M 0.000 description 1
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 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
- WIAVVDGWLCNNGT-UHFFFAOYSA-M lithium;butanoate Chemical compound [Li+].CCCC([O-])=O WIAVVDGWLCNNGT-UHFFFAOYSA-M 0.000 description 1
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 description 1
- RQZHWDLISAJCLK-UHFFFAOYSA-M lithium;heptanoate Chemical compound [Li+].CCCCCCC([O-])=O RQZHWDLISAJCLK-UHFFFAOYSA-M 0.000 description 1
- BZMIKKVSCNHEFL-UHFFFAOYSA-M lithium;hexadecanoate Chemical compound [Li+].CCCCCCCCCCCCCCCC([O-])=O BZMIKKVSCNHEFL-UHFFFAOYSA-M 0.000 description 1
- PNDUWCHQCLZPAH-UHFFFAOYSA-M lithium;hexanoate Chemical compound [Li+].CCCCCC([O-])=O PNDUWCHQCLZPAH-UHFFFAOYSA-M 0.000 description 1
- BTAUEIDLAAYHSL-UHFFFAOYSA-M lithium;octanoate Chemical compound [Li+].CCCCCCCC([O-])=O BTAUEIDLAAYHSL-UHFFFAOYSA-M 0.000 description 1
- KDDRURKXNGXKGE-UHFFFAOYSA-M lithium;pentanoate Chemical compound [Li+].CCCCC([O-])=O KDDRURKXNGXKGE-UHFFFAOYSA-M 0.000 description 1
- AXMOZGKEVIBBCF-UHFFFAOYSA-M lithium;propanoate Chemical compound [Li+].CCC([O-])=O AXMOZGKEVIBBCF-UHFFFAOYSA-M 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- ODKLEQPZOCJQMT-UHFFFAOYSA-N n,n-diethylpyridin-4-amine Chemical compound CCN(CC)C1=CC=NC=C1 ODKLEQPZOCJQMT-UHFFFAOYSA-N 0.000 description 1
- WLFOHIVICZSIKG-UHFFFAOYSA-N n,n-dimethyl-1h-imidazol-2-amine Chemical compound CN(C)C1=NC=CN1 WLFOHIVICZSIKG-UHFFFAOYSA-N 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 235000011835 quiches Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- MBDNRNMVTZADMQ-UHFFFAOYSA-N sulfolene Chemical compound O=S1(=O)CC=CC1 MBDNRNMVTZADMQ-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
Images
Classifications
-
- 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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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明の第1実施形態に関して、図1〜図4を用いて説明する。図1は、本実施形態の非水電解液二次電池10の一例を断面図である。図2は、本実施形態の非水電解液二次電池10Aの他の例を示す断面斜視図である。図3は、非水電解液二次電池10Aの電極部分を示す説明模式図を示す。非水電解液二次電池10は、形状は特に限定するものでなく、図1に示すようにコイン型、および図2に示す円筒型のように様々な形態によって実現することができる。先ず、図1に基づいて非水電解液二次電池10を説明し、図1の構成と同様の構成について、図2に同じ符号を付し説明を省略することがある。
LiFePO4/AB/PVDF=80/10/10 であり、
また負極16は、実施例および比較例ともに、
グラファイト/CMC/SBR=98/1/1 であり、
また電解液17のリチウム塩を除く主成分は、実施例および比較例ともに、
EC/DMC/EMC=30/30/40 である。
LiPF6:1.0mol/L
LiB(CH3)4:0.3mol/L であり、
充電条件は、
CV電位:4.2V
CV時間:2時間 である。
充電容量=劣化電池容量+期待回復容量(酸化分解) となる。
11…ガスケット
12…正極ケース
13…負極ケース
14…セパレータ
15…正極
15a…正極集合体
16…負極
16a…負極集合体
17…電解液
20…正極端子
21…負極端子
22…絶縁板
23…電池缶
24…負極リード
25…正極リード
26…安全弁
Claims (6)
- リチウムイオンを吸蔵および放出する正極と、
前記リチウムイオンを吸蔵および放出する負極と、
非水溶媒に少なくとも1種のリチウム塩を溶解している電解液と、を含む非水電解液二次電池であって、
前記電解液に溶解している前記リチウム塩のうち少なくとも1種は、前記正極の充電電位よりも高電圧な領域であって、前記電解液の主成分の酸化電位よりも低電圧な領域で酸化する性質を有し、
前記電解液中の前記リチウムイオンが減少した場合、前記酸化する電圧領域で充電されることを特徴とする非水電解液二次電池。 - 前記性質を有する前記リチウム塩の酸化電圧は、リチウム基準に対して3.6V以上4.3V以下であることを特徴とする請求項1に記載の非水電解液二次電池。
- 前記正極は、LiFePO4であることを特徴とする請求項1または2に記載の非水電解液二次電池。
- 前記電解液は、エチレンカーボネート、プロピレンカーボネート、エチルメチルカーボネート、ジメチルカーボネート、およびジエチルカーボネートの少なくともいずれか1つ含むことを特徴とする請求項1〜3のいずれか1つに記載の非水電解液二次電池。
- 前記性質を有するリチウム塩は、ホウ素化合物であることを特徴とする請求項1〜4のいずれか1つに記載の非水電解液二次電池。
- 前記リチウム塩は、LiB(C2H5)4であることを特徴とする請求項5に記載の非水電解液二次電池。
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