CN106920963A - 非水电解质二次电池 - Google Patents
非水电解质二次电池 Download PDFInfo
- Publication number
- CN106920963A CN106920963A CN201610927843.5A CN201610927843A CN106920963A CN 106920963 A CN106920963 A CN 106920963A CN 201610927843 A CN201610927843 A CN 201610927843A CN 106920963 A CN106920963 A CN 106920963A
- Authority
- CN
- China
- Prior art keywords
- electrolytic battery
- nonaqueous electrolytic
- nonaqueous electrolyte
- rechargeable nonaqueous
- lithium
- 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.)
- Pending
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 55
- -1 fluorosulfonyl Chemical group 0.000 claims abstract description 54
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 27
- 239000007774 positive electrode material Substances 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 150000002466 imines Chemical class 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000007769 metal material Substances 0.000 claims description 4
- 150000004702 methyl esters Chemical class 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 230000009467 reduction Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000007747 plating Methods 0.000 description 10
- 239000002002 slurry Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 229920002521 macromolecule Polymers 0.000 description 6
- 238000009784 over-discharge test Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910015608 LiNi0.82Co0.15Al0.03O2 Inorganic materials 0.000 description 3
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000012491 analyte Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910012416 LiNi0.50Co0.20Mn0.30O2 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 229940084030 carboxymethylcellulose calcium Drugs 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- OIAQMFOKAXHPNH-UHFFFAOYSA-N 1,2-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1 OIAQMFOKAXHPNH-UHFFFAOYSA-N 0.000 description 1
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- PKHMHHNNLFQNBU-UHFFFAOYSA-N B(Cl)(Cl)Cl.[Li] Chemical compound B(Cl)(Cl)Cl.[Li] PKHMHHNNLFQNBU-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910020596 CmF2m+1SO2 Inorganic materials 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910011131 Li2B4O7 Inorganic materials 0.000 description 1
- 229910003253 LiB10Cl10 Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910012161 LiPF6-x Inorganic materials 0.000 description 1
- 229910012171 LiPF6−x Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910014508 LixNiyM(1-y)O2 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 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
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical compound [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 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
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- HSFDLPWPRRSVSM-UHFFFAOYSA-M lithium;2,2,2-trifluoroacetate Chemical compound [Li+].[O-]C(=O)C(F)(F)F HSFDLPWPRRSVSM-UHFFFAOYSA-M 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 210000004508 polar body Anatomy 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N trifluoroacetic acid Substances OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- PRZWBGYJMNFKBT-UHFFFAOYSA-N yttrium Chemical compound [Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y][Y] PRZWBGYJMNFKBT-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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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Abstract
本公开的一个技术方案涉及非水电解质二次电池,该非水电解质二次电池具备正极、负极和非水电解质,所述正极包含以锂复合氧化物为主成分的正极活性物质,所述锂复合氧化物中,镍相对于除了锂以外的金属元素的总摩尔数的比例为50摩尔%以上。非水电解质含有双(氟磺酰基)亚胺锂、以及在α位具有氢的氟代链状羧酸酯。
Description
技术领域
本公开涉及非水电解质二次电池。
背景技术
在专利文献1中公开了一种作为非水电解质的溶剂成分含有氟代碳酸亚乙酯(FEC)和氟代链状羧酸酯的非水电解质二次电池。还公开了以下内容:该非水电解质二次电池在高温条件下的电池容量的降低少,具有良好的高温保存特性和循环特性。
在先技术文献
专利文献
专利文献1:日本专利第5235437号公报
发明内容
如上所述,通过作为非水电解质使用FEC和氟代链状羧酸酯,高温保存特性提高,但在将该非水电解质与包含镍(Ni)含有比率高的正极活性物质的正极组合的情况下,存在电池的初始充放电效率降低这样的课题。
本公开的一个技术方案涉及的非水电解质二次电池,具备正极、负极和非水电解质,所述正极包含以锂复合氧化物为主成分的正极活性物质,所述锂复合氧化物中,镍相对于除了锂以外的金属元素的总摩尔数的比例为50摩尔%以上,非水电解质含有双(氟磺酰基)亚胺锂(lithium bis(fluorosulfonyl)amide)、以及由下述通式表示的氟代链状羧酸酯(在α位具有氢的氟代链状羧酸酯)。
(式中,R1、R2是H、F、CH3-xFx(x为1、2或3)中的任一种,R1和R2可以相同也可以不同。R3是碳原子数为1~3的烷基,可以含有F)
根据本公开的一个技术方案涉及的非水电解质二次电池,循环特性良好,并能得到高的初始充放电效率。
附图说明
图1是表示作为实施方式的一例的非水电解质二次电池的外观的立体图。
图2是图1中的I-I截面图。
图3是表示作为实施方式的一例的非水电解质二次电池的底部外表面的图。
图4是表示作为实施方式的一例的非水电解质二次电池的底部内表面的图。
附图标记说明
1正极;2负极;3隔板;4电极体;5外装罐;5a底部;5b薄壁部;5c沟槽部;6封口体;7密封垫;8盖;9上阀体;9a薄壁部;10下阀体;10a薄壁部;11排气孔;12过滤器;12a开口部;13、14绝缘板;15正极引线;16负极引线。
具体实施方式
已知在非水电解质二次电池中,在初次充电时非水电解质成分的一部分被分解而在负极表面形成由其分解物构成的被膜。负极表面意指有助于反应的非水电解质与负极活性物质的界面,也就是负极活性物质的表面。该被膜也被称为SEI(固体电解质界面:SolidElectrolyte Interface)形成被膜,给电池特性带来良好的影响。
但是,如果通过非水电解质的分解而在负极表面过度地形成被膜,则在初次充电时嵌入到负极中的锂(Li)无法在放电时脱离,从而初始充放电效率降低。初始充放电效率可以由下式表示。
初始充放电效率(%)=(初次放电容量/初次充电容量)×100
在使用Ni含有比率高且较多地含有碱性成分的正极活性物质的情况下,当非水电解质含有由下述通式表示的在α位具有氢的氟代链状羧酸酯时,初始充放电效率降低。推测这是因为,如下述的反应式(I)所表示的那样,氟代链状羧酸酯与正极活性物质中所含的碱性成分、例如碳酸锂发生分解反应,所产生的H2O、R1R2C=CHOOR3向负极侧扩散,在负极表面过度地形成上述被膜。特别是推测到由于Ni含有比率高的正极活性物质
中碱性成分较多,因此初始充放电效率的降低较显著。
(式中,R1、R2是H、F、CH3-xFx(x为1、2或3)中的任一种,R1和R2可以相同也可以不同。R3是碳原子数为1~3的烷基,可以含有F)
本发明人为解决上述课题而进行了认真研究,结果得到了下述见解:通过将在α位具有氢的氟代链状羧酸酯和由下述通式表示的双(氟磺酰基)亚胺锂并用,能够维持良好的循环特性并且改善初始充放电效率。再者,如果非水电解质含有在α位具有氢的氟代链状羧酸酯,则如上所述电池的高温保存特性也提高。
然而,在使用由以铁(Fe)为主成分的金属材料构成的电池外装罐的情况下,通常为了防止罐腐蚀而实施镀Ni,但本发明人得到以下见解:如果在非水电解质中含有硫化合物,则在高温过放电时会发生罐腐蚀。推测该罐腐蚀的原因是来自硫化合物的分解生成物与Ni反应而使Fe露出。可以认为,当在高温下进行过放电试验时,由于外装罐处于相对于Li基准为3V左右的电位,因此在镀Ni层剥离了的部位Fe会溶出而发生罐腐蚀。
根据本公开涉及的非水电解质二次电池,能够防止上述罐腐蚀。这是由于非水电解质中所含有的氟代链状羧酸酯在α位具有氢,因此如下述的反应式(II)所示那样被分解,从而会在外装罐的内表面形成被膜。推测由于该被膜作为外装罐的保护层发挥作用,因而能抑制上述罐腐蚀。也就是说,该保护层(保护被膜)抑制来自硫化合物的分解物与外装罐的表面的Ni的反应,从而抑制Fe的露出。由此可以认为即使是在高温下进行过放电试验的情况Fe也不会溶出,能够抑制罐腐蚀。
以下,一边参照附图一边对作为实施方式的一例的非水电解质二次电池进行详细说明。在实施方式的说明中参照的附图是示意性地记载的图,具体的尺寸比率等应参照以下的说明来判断。
图1是表示作为实施方式的一例的非水电解质二次电池的外观的立体图,图2是图1中的I-I截面图。如图1和图2所例示,作为实施方式的一例的非水电解质二次电池具备电极体4、非水电解质(未图示)、以及收纳电极体4和非水电解质的外装罐5。电极体4例如具有正极1和负极2介由隔板3而被卷绕的结构。外装罐5具有例如有底圆筒形状。在外装罐5的上部沿着周向形成有向内侧凹陷的沟槽部5c。在形成有沟槽部5c的部分,外装罐5的内表面突出,封口体6被该突出部支撑,从而将外装罐5的开口部密封。优选在外装罐5与封口体6之间设置密封垫(gasket)7。
封口体6包含盖8、上阀体9、下阀体10和过滤器(filter)12。盖8具有排气孔11,作为正极外部端子发挥作用。在过滤器12上形成有开口部12a。上阀体9和下阀体10作为安全阀发挥作用,即,在由于因内部短路等导致的发热而产生气体从而内压上升时断裂,将气体向电池外排出。上阀体9和下阀体10分别具有在电池内压达到规定值时发生断裂的薄壁部9a、10a。
在电极体4的上下分别配置有绝缘板13、14。正极1上安装的正极引线15通过绝缘板13的贯通孔而向封口体6侧延伸,负极2上安装的负极引线16通过绝缘板14的外侧而向外装罐5的底部5a侧延伸。正极引线15通过焊接等与封口体6的底板即过滤器12连接。负极引线16通过焊接等与外装罐5的底部5a连接。即,负极2与外装罐5电连接。
外装罐5例如由以Fe为主成分的金属材料构成。为了防止罐腐蚀,优选在外装罐5的内表面形成有镀Ni层(未图示)。镀Ni层的厚度例如为2μm以下,优选为1μm以下。在本实施方式的非水电解质二次电池中,即使镀Ni层的厚度为1μm以下,也能够充分抑制罐腐蚀。
图3是表示外装罐5的底部5a的外表面的图。优选如图3所例示的那样在外装罐5的底部5a形成有当电池内压达到规定值时发生断裂的环状的薄壁部5b。薄壁部5b例如是在底部5a的外表面形成的凹部。薄壁部5b在电池内压上升时发生断裂,防止外装罐5的侧壁部断裂。使薄壁部5b断裂的内压(启动压力)例如被设定得比使形成于上阀体9的薄壁部9a发生断裂的内压高。
图4是表示外装罐5的底部5a的内表面的图。如图4所例示,在外装罐5的底部5a形成有薄壁部5b的情况下,优选在底部5a的内表面的由薄壁部5b包围的区域内焊接负极引线16。一般地,底部5a的内表面的与薄壁部5b相对应的部分隆起。再者,图4所示的黑圆表示底部5a的内表面与负极引线16的焊接部位。由此,容易防止薄壁部5b的断裂被负极引线16妨碍。
在外装罐5的底部5a的内表面的、与薄壁部5b对应的部分,镀Ni层的厚度容易变薄。在镀Ni层的厚度薄的部分,通过来自硫化合物的分解生成物与Ni反应,Fe容易溶出,容易发生罐腐蚀,但根据本实施方式的非水电解质二次电池,那样的部分的罐腐蚀也能够充分抑制。
以下,对作为实施方式的一例的非水电解质二次电池的各构成要素进行详述。
〔正极〕
正极1由例如金属箔等的正极集电体、和形成于正极集电体上的正极活性物质层构成。作为正极集电体,可使用在正极1的电位范围稳定的金属的箔、或将在正极1的电位范围稳定的金属配置为表层的薄膜等。作为在正极1的电位范围稳定的金属,优选使用铝(Al)。正极活性物质层例如是将正极合剂浆液涂布在正极集电体上之后,进行干燥、轧制而形成的层,所述正极合剂浆液除了包含正极活性物质以外还包含导电剂、粘结剂和适当的溶剂等的。
正极活性物质以锂复合氧化物(以下有时称为“复合氧化物A”)为主成分,所述锂复合氧化物中,Ni相对于除了Li以外的金属元素的总摩尔数的比例为50摩尔%以上。主成分意指构成正极活性物质的材料之中含量最多的成分。正极活性物质例如也可以包含复合氧化物A以外的锂复合氧化物。但是,复合氧化物A相对于正极活性物质的总量优选含有50重量%以上,更优选为80重量%以上,也可以为100重量%。在正极活性物质的粒子表面,可以存在无机化合物的微粒,例如氧化铝(Al2O3)等氧化物、含有镧系元素的化合物等。
复合氧化物A优选为由通式LixNiyM(1-y)O2{0.9≤x≤1.2,0.5<y≤0.95,M为至少一种金属元素}表示的氧化物。再者,该通式表示完全放电状态的组成。Ni的含有比率,从低成本化的观点出发,相对于除了Li以外的金属元素的总摩尔数优选为50摩尔%以上,更优选为80摩尔%以上。特别是Ni的含有比率为80摩尔%以上的正极活性物质,除了低成本化以外还可期待高容量化,但另一方面由于较多地含有碱性成分,因此会如反应式(1)所示那样引起氟代链状羧酸酯的分解。因此,存在初始充放电效率降低、得不到高容量化的效果这样的问题。与此相对,在本公开的非水电解质二次电池中,双(氟磺酰基)亚胺锂与碱性成分选择性地反应,抑制反应式(1)的反应,由此能够不降低初始效率而使用Ni的含有比率为80摩尔%以上的正极活性物质。复合氧化物A具有层状岩盐型的晶体结构。
复合氧化物A中所含有的金属元素M,是选自例如硼(B)、镁(Mg)、铝(Al)、钙(Ca)、钪(Sc)、钛(Ti)、钒(V)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、铜(Cu)、锌(Zn)、镓(Ga)、锗(Ge)、钇(Y)、锆(Zr)、锡(Sn)、锑(Sb)、铅(Pb)、铋(Bi)之中的至少一种。其中,金属元素M优选为选自Co、Mn、Al之中的至少一种。作为优选的复合氧化物A,可例示出锂镍钴铝复合氧化物(NCA)、锂镍钴锰复合氧化物(NCM)。
导电剂具有提高正极活性物质层的电子传导性的功能。作为导电剂可使用具有导电性的碳材料、金属粉末、有机材料等。具体而言,作为碳材料可举出乙炔黑、科琴黑和石墨等,作为金属粉末可举出铝等,作为有机材料可举出亚苯基衍生物等。这些导电剂可以单独仅使用一种,也可以组合两种以上来使用。
粘结剂具有维持正极活性物质与导电剂之间的良好的接触状态、并且提高正极活性物质等相对于正极集电体表面的粘结性的功能。作为粘结剂,可使用氟系高分子、橡胶系高分子等。具体而言,作为氟系高分子可举出聚四氟乙烯(PTFE)、聚偏二氟乙烯(PVdF)、或它们的改性体等,作为橡胶系高分子可举出乙烯-丙烯-异戊二烯共聚物、乙烯-丙烯-丁二烯共聚物等。粘结剂也可以与羧甲基纤维素(CMC)、聚环氧乙烷(PEO)等增粘剂并用。
〔负极〕
负极2由例如金属箔等的负极集电体和形成于负极集电体上的负极活性物质层构成。作为负极集电体可使用在负极2的电位范围不与锂形成合金的金属的箔、或将在负极2的电位范围不与锂形成合金的金属配置为表层的薄膜等。作为在负极2的电位范围不与锂形成合金的金属,优选使用低成本、易加工且电子传导性良好的铜(Cu)。负极活性物质层例如是将负极合剂浆液涂布在负极集电体上之后,进行干燥、轧制而形成的层,所述负极合剂浆液除了包含负极活性物质以外还包含粘结剂和适当的溶剂等。
负极活性物质只要是能够吸藏和释放锂离子的材料就不特别限定。作为负极活性物质,可以使用例如碳材料、金属、合金、金属氧化物、金属氮化物、以及预先吸藏了锂离子的碳、硅等。作为碳材料,可举出天然石墨、人造石墨、沥青系碳纤维等。作为金属或合金的具体例,可举出Li、硅(Si)、Sn、Ga、Ge、铟(In)、锂合金、硅合金、锡合金等。负极活性物质可以单独仅使用一种,也可以组合两种以上来使用。
作为粘结剂,可以与正极1的情形同样地使用氟系高分子、橡胶系高分子等,但优选使用作为橡胶系高分子的苯乙烯-丁二烯共聚物(SBR)或其改性体等。粘结剂也可以与CMC等增粘剂并用。
〔隔板〕
作为隔板3,可使用配置于正极1与负极2之间的具有离子透过性和绝缘性的多孔性薄膜。作为多孔性薄膜,可举出微多孔薄膜、织布、无纺布等。隔板所使用的材料例如为聚烯烃,更具体而言,优选聚乙烯、聚丙烯。
〔非水电解质〕
非水电解质包含非水溶剂和溶解于非水溶剂的电解质盐。非水电解质中作为非水溶剂至少含有由下述通式表示的在α位具有氢的氟代链状羧酸酯。另外,非水电解质含有双(氟磺酰基)亚胺锂(LiFSA)。LiFSA作为电解质盐发挥作用。在非水电解质中,通过并用该氟代链状羧酸酯和LiFSA,能够得到循环特性良好且初始充放电效率高的非水电解质二次电池。
(式中,R1、R2是H、F、CH3-xFx(x为1、2或3)中的任一种,R1和R2可以相同也可以不同。R3是碳原子数为1~3的烷基,可以含有F)
上述氟代链状羧酸酯,从低粘度且可得到高的导电率出发,优选为3,3,3-三氟丙酸甲酯(FMP)。氟代链状羧酸酯的含量,相对于非水电解质中的非水溶剂的总量,优选为50体积%以上,特别优选为70体积%以上。通过使氟代链状羧酸酯的含量为50体积%以上,能够具有作为非水溶剂的功能、并且在负极表面容易形成良好的保护被膜。
再者,已知在负极表面,氟代链状羧酸酯在Li基准1.2V左右被还原分解(参照日本特开2009-289414号公报)。因此,为了防止过度地引起该还原分解,优选向非水溶剂中添加用于在负极表面形成能够抑制该分解的被膜的被膜形成化合物。
非水电解质优选含有氟代碳酸亚乙酯(FEC)作为非水溶剂。通过向非水电解质添加FEC,容易在负极表面形成抑制上述氟代链状羧酸酯的还原分解的被膜,循环特性进一步提高。FEC的含量,相对于非水溶剂的总量优选为2~40体积%,特别优选为5~30体积%。如果FEC的量过多,则有时非水电解质的粘度上升从而负载特性降低。
非水电解质,除了上述氟代链状羧酸酯和FEC以外,也可以含有其它的非水溶剂。作为其它的非水溶剂,可以使用例如碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯(MP)等酯类,1,3-二氧杂戊环等醚类、乙腈等腈类、二甲基甲酰胺等酰胺类、以及它们中的两种以上的混合溶剂。另外,作为其它的非水溶剂也可以使用氟系溶剂。
LiFSA抑制正极中的碱性成分与上述氟代链状羧酸酯的反应,使初始充放电效率提高。LiSO3F的含量,相对于非水电解质的总量优选为0.02~2.0M(摩尔/升),更优选为0.1~1.5M,特别优选为0.5~1.2M。如果LiFSA的含量过少,则有时无法充分得到抑制上述氟代链状羧酸酯的分解反应的效果。另一方面,如果LiFSA的含量过多,则有时非水电解质的粘度上升从而负载特性降低。
对于不含上述氟代链状羧酸酯的通常的电解液而言,如果添加0.5M以上的LiFSA,则随着充放电循环,正极的集电体所使用的Al溶解,存在长期可靠性降低这样的问题。另一方面,在使用了上述氟代链状羧酸酯的情况下,通过氟化而使羧基氧的电子密度降低,因此与Al离子的相互作用降低,能够抑制Al的溶解。因此,通过将本公开的氟代链状羧酸酯作为非水溶剂使用,能够使用0.5M以上的LiFSA。
如上所述,如果非水电解质中含有LiFSA等硫化合物,则在高温过放电时,实施了镀Ni的铁制外装罐容易发生腐蚀,但在非水电解质中含有上述氟代链状羧酸酯的情况下,该罐腐蚀得到抑制。可以认为这是因为,由于会在外装罐的内表面形成由上述氟代链状羧酸酯的分解生成物构成的被膜,因此抑制了来自LiFSA的分解物与Ni的反应的缘故。
非水电解质也可以含有除了LiFSA以外的锂盐。作为可与LiFSA并用的锂盐,可例示出LiBF4、LiClO4、LiPF6、LiAsF6、LiSbF6、LiAlCl4、LiSCN、LiCF3SO3、LiCF3CO2、Li(P(C2O4)F4)、LiPF6-x(CnF2n+1)x(1<x<6,n为1或2)、LiB10Cl10、LiCl、LiBr、LiI、氯化硼锂、低级脂肪族羧酸锂、Li2B4O7、Li(B(C2O4)F2)等硼酸盐类、LiN(SO2CF3)2、LiN(ClF2l+1SO2)(CmF2m+1SO2){l、m为1以上的整数}等酰胺盐类等。这些物质之中,从离子传导性、电化学稳定性等观点出发,优选使用LiPF6。
锂盐的浓度,按与LiFSA的合计量计,优选是相对于1升非水溶剂为0.8~1.8摩尔(0.8~1.8M)。在将LiFSA与其它的锂盐并用的情况下,LiFSA的含量相对于锂盐的总摩尔数例如为10~90摩尔%,优选为40~80摩尔%。
非水电解质也可以含有碳酸亚乙烯酯(VC)、亚硫酸亚乙酯(ES:ethylenesulfite)、双(草酸)硼酸锂(LiBOB)、环己基苯(CHB)、邻三联苯(OTP)等添加剂。其中,优选使用VC。VC在负极表面容易分解,在上述氟代链状羧酸酯进行分解反应时会协调性地反应,通过添加VC能够与氟代链状羧酸酯一同形成致密的复合被膜。添加剂的含量只要是能够充分形成被膜的量即可,优选相对于非水电解质的总量为3质量%以下。添加剂可以单独仅使用一种,也可以组合两种以上来使用。
实施例
以下通过实施例来进一步说明本公开,但本公开并不被这些实施例限定。
<实施例1>
[正极的制作]
作为正极活性物质,使用了由LiNi0.82Co0.15Al0.03O2(NCA)表示的含锂的过渡金属氧化物。将该活性物质、乙炔黑和聚偏二氟乙烯以质量比成为100:1:0.9的方式混合后,添加适量的N-甲基-2-吡咯烷酮(NMP),来调制出正极合剂浆液。接着,将该正极合剂浆液涂布在由铝箔构成的正极集电体的两面。将涂膜干燥后,使用轧制辊进行轧制,由此制作出在正极集电体的两面形成有正极活性物质层的正极。正极的填充密度为3.7g/cm3。
[负极的制作]
将人造石墨、羧甲基纤维素的钠盐(CMC-Na)和苯乙烯丁二烯共聚物(SBR)以100:1:1的质量比在水溶液中混合,调制出负极合剂浆液。接着,将该负极合剂浆液均匀涂布在由铜箔构成的负极集电体的两面。使涂膜干燥后,使用轧制辊进行轧制,由此制作出在负极集电体的两面形成有负极合剂层的负极。负极的填充密度为1.7g/cm3。
[非水电解质的调制]
在将氟代碳酸亚乙酯(FEC)和3,3,3-三氟丙酸甲酯(FMP)以15:85的体积比混合而成的混合溶剂中,以1.2M的浓度溶解双(氟磺酰基)亚胺锂(LiFSA),调制出非水电解质。
[外装罐的制作]
对在表面施加了镀Ni层的铁制板材进行拉深加工,制作了有底圆筒状的外装罐。在外装罐的上部沿侧壁部的周向形成了宽1.0mm、深1.5mm的截面大致为U字状的沟槽部。外装罐的侧壁部的厚度为0.25mm,外装罐的底部的厚度为0.3mm。另外,底部的直径设为18mm。进行SEM观察的结果,在外装罐的底部内表面形成的镀Ni层的厚度为2μm以下。
[电池的制作]
将上述正极和上述负极介由作为聚乙烯制的微多孔膜的隔板而进行卷绕,由此制作了卷绕型的电极体。在上述外装罐内收纳该电极体,填充上述非水电解质之后,将外装罐的开口部隔着密封垫由封口体密封,由此制作了设计容量为3250mAh的18650圆筒型的非水电解质二次电池。再者,正极经由正极引线与封口体的过滤器焊接,负极经由负极引线与外装罐的底部焊接。
对上述电池进行了初始充放电效率、高温循环特性和高温过放电试验(罐腐蚀)的评价,将评价结果示于表1。
[初始充放电效率的评价]
在25℃的环境温度下,以650mA[0.2It]进行恒流充电直到电池电压成为4.2V为止,进而以4.2V的电压进行恒压充电直到电流值成为65mA为止。休止10分钟后,以650mA[0.2It]进行放电直到电池电压变为2.5V为止,然后休止20分钟。初始充放电效率可采用以下的式子求出。
初始充放电效率=(初次放电容量/初次充电容量)×100
[高温循环特性的评价]
在45℃的环境温度下,在与求算初始充放电效率的试验相同的充放电条件下反复进行600次充放电,利用下述式子算出了600次循环后的容量维持率。
容量维持率=(第600次循环的放电容量/第1次循环的放电容量)×100
[高温过放电试验]
将陶瓷电阻器与电池的正负极连接,在外部短路的状态下将电池放置于60℃的恒温槽中,观察了20天后的电池(外装罐)的状态。
<实施例2>
将LiFSA和LiPF6分别以0.5M、0.7M的浓度溶解于非水溶剂中来调制了非水电解质,除此以外与实施例1同样地制作电池,进行了上述各评价。
<实施例3>
将LiFSA和LiPF6分别以0.2M、1.0M的浓度溶解于非水溶剂中来调制了非水电解质,除此以外与实施例1同样地制作电池,进行了上述各评价。
<实施例4>
作为正极活性物质,使用由LiNi0.50Co0.20Mn0.30O2(NCM)表示的含锂的过渡金属氧化物来代替LiNi0.82Co0.15Al0.03O2(NCA),除此以外与实施例1同样地制作电池,按电池设计容量2300mAh进行换算从而将充放电时的电流变更为460mAh,关于上述各评价进行了测定。
<比较例1>
在非水电解质的调制中,使用LiPF6来代替LiFSA,除此以外与实施例1同样地制作电池,进行了上述各评价。
<比较例2>
在非水电解质的调制中,使用碳酸甲乙酯(EMC)来代替FMP,除此以外与实施例3同样地制作电池,进行了上述各评价。
<比较例3>
在非水电解质的调制中,使用EMC来代替FMP,除此以外与比较例1同样地制作电池,进行了上述各评价。
<比较例4>
在非水电解质的调制中,使用碳酸亚乙酯(EC)来代替FEC,除此以外与比较例2同样地制作电池,进行了上述各评价。
<比较例5>
在非水电解质的调制中,使用EC来代替FEC,除此以外与比较例3同样地制作电池,进行了上述各评价。
<比较例6>
作为正极活性物质,使用由LiNi0.50Co0.20Mn0.30O2(NCM)表示的含锂的过渡金属氧化物来代替LiNi0.82Co0.15Al0.03O2(NCA),除此以外与比较例1同样地制作电池,进行了上述各评价。
如表1所示,实施例的电池,都得到了良好的高温循环特性(高的容量维持率)和高的初始充放电效率。另外,实施例的电池,在高温过放电试验中都没有确认到外装罐的腐蚀。与此相对,比较例的电池,其容量维持率或初始充放电效率低,未得到兼具这两种性能的电池。另外,关于在非水电解质中添加有LiFSA、且不含FMP的比较例2、比较例4的电池,在高温过放电试验中确认到了外装罐的腐蚀。也就是说,只有在非水电解质中含有在α位具有氢的氟代链状羧酸酯和LiFSA的情况下,不会发生外装罐的腐蚀,且能得到良好的循环特性和高的初始充放电效率。
本公开的非水电解质二次电池,不限于上述的实施方式,例如具备以下的项目所记载的构成。
[项目1]
一种非水电解质二次电池,具备正极、负极和非水电解质,所述正极包含以锂复合氧化物为主成分的正极活性物质,所述锂复合氧化物中,镍相对于除了锂以外的金属元素的总摩尔数的比例为50摩尔%以上,所述非水电解质含有双(氟磺酰基)亚胺锂、以及由下述通式表示的氟代链状羧酸酯。
(式中,R1、R2是H、F、CH3-xFx(x为1、2或3)中的任一种,R1和R2可以相同也可以不同。R3是碳原子数为1~3的烷基,可以含有F)
[项目2]
根据项目1所述的非水电解质二次电池,所述非水电解质含有氟代碳酸亚乙酯。
[项目3]
根据项目1或2所述的非水电解质二次电池,所述氟代链状羧酸酯是3,3,3-三氟丙酸甲酯。
[项目4]
根据项目1~3的任一项所述的非水电解质二次电池,所述氟代链状羧酸酯的含量相对于所述非水电解质中的非水溶剂的总量为70体积%以上。
[项目5]
根据项目1~4的任一项所述的非水电解质二次电池,双(氟磺酰基)亚胺锂的含量相对于所述非水电解质的总量为0.02~2.0M。
[项目6]
根据项目1~5的任一项所述的非水电解质二次电池,所述锂复合氧化物中,镍相对于除了锂以外的金属元素的总摩尔数的比例为80摩尔%以上。
[项目7]
根据项目1~6的任一项所述的非水电解质二次电池,具备外装罐,所述外装罐由以铁为主成分的金属材料构成,收纳所述正极、所述负极和所述非水电解质。
[项目8]
根据项目7所述的非水电解质二次电池,在所述外装罐的内表面形成有镀镍层,所述镀镍层的厚度为1μm以下。
Claims (8)
1.一种非水电解质二次电池,具备正极、负极和非水电解质,
所述正极包含以锂复合氧化物为主成分的正极活性物质,
所述锂复合氧化物中,镍相对于除了锂以外的金属元素的总摩尔数的比例为50摩尔%以上,
所述非水电解质含有双(氟磺酰基)亚胺锂、以及由下述通式表示的氟代链状羧酸酯,
式中,R1、R2是H、F、CH3-xFx中的任一种,R1和R2可以相同也可以不同,x为1、2或3,R3是碳原子数为1~3的烷基,可以含有F。
2.根据权利要求1所述的非水电解质二次电池,所述非水电解质含有氟代碳酸亚乙酯。
3.根据权利要求1所述的非水电解质二次电池,所述氟代链状羧酸酯是3,3,3-三氟丙酸甲酯。
4.根据权利要求1所述的非水电解质二次电池,所述氟代链状羧酸酯的含量相对于所述非水电解质中的非水溶剂的总量为70体积%以上。
5.根据权利要求1所述的非水电解质二次电池,双(氟磺酰基)亚胺锂的含量相对于所述非水电解质的总量为0.02~2.0M。
6.根据权利要求1所述的非水电解质二次电池,所述锂复合氧化物中,镍相对于除了锂以外的金属元素的总摩尔数的比例为80摩尔%以上。
7.根据权利要求1所述的非水电解质二次电池,具备外装罐,所述外装罐由以铁为主成分的金属材料构成,收纳所述正极、所述负极和所述非水电解质。
8.根据权利要求7所述的非水电解质二次电池,在所述外装罐的内表面形成有镀镍层,所述镀镍层的厚度为1μm以下。
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