CN104798244B - 锂二次电池 - Google Patents
锂二次电池 Download PDFInfo
- Publication number
- CN104798244B CN104798244B CN201480003028.9A CN201480003028A CN104798244B CN 104798244 B CN104798244 B CN 104798244B CN 201480003028 A CN201480003028 A CN 201480003028A CN 104798244 B CN104798244 B CN 104798244B
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- CN
- China
- Prior art keywords
- secondary battery
- lithium secondary
- ionomer
- carbonate
- chemical formula
- 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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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 70
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229920000554 ionomer Polymers 0.000 claims abstract description 86
- 230000004888 barrier function Effects 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 25
- -1 Cyclic carbonate compound Chemical class 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- 150000001450 anions Chemical class 0.000 claims description 9
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 7
- 239000008199 coating composition Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 4
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 150000003951 lactams Chemical class 0.000 claims description 4
- 150000002596 lactones Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 150000003462 sulfoxides Chemical class 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical class CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910017048 AsF6 Inorganic materials 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical class COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims 2
- 150000000094 1,4-dioxanes Chemical class 0.000 claims 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims 1
- 229940093499 ethyl acetate Drugs 0.000 claims 1
- 229940017219 methyl propionate Drugs 0.000 claims 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims 1
- 229940090181 propyl acetate Drugs 0.000 claims 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 description 24
- 210000004027 cell Anatomy 0.000 description 22
- 239000007772 electrode material Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 230000010287 polarization Effects 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000004020 conductor Substances 0.000 description 7
- 239000004411 aluminium Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000011267 electrode slurry Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 229910013872 LiPF Inorganic materials 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910018039 Cu2V2O7 Inorganic materials 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910004170 Li(NiaCObMnc)O2 Inorganic materials 0.000 description 1
- 229910003349 Li2CuO2 Inorganic materials 0.000 description 1
- 229910010228 Li2Mn3MO8 Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910011279 LiCoPO4 Inorganic materials 0.000 description 1
- 229910010521 LiFe3O4 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910010785 LiFexMn1-xPO4 Inorganic materials 0.000 description 1
- 229910010782 LiFexMn1−xPO4 Inorganic materials 0.000 description 1
- 229910014172 LiMn2-xMxO2 Inorganic materials 0.000 description 1
- 229910014437 LiMn2−XMXO2 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910014713 LiMnO3 Inorganic materials 0.000 description 1
- 229910014114 LiNi1-xMxO2 Inorganic materials 0.000 description 1
- 229910014907 LiNi1−xMxO2 Inorganic materials 0.000 description 1
- 229910012970 LiV3O8 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910016622 LixFe2O3 Inorganic materials 0.000 description 1
- 229910015103 LixWO2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 1
- 229910000411 antimony tetroxide Inorganic materials 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000417 bismuth pentoxide Inorganic materials 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(II,IV) oxide Inorganic materials O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000006163 transport media Substances 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M10/052—Li-accumulators
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Abstract
本发明涉及一种包括负、正、插在负极和正之间的隔膜以及无水电解液的锂二次电池,其中,提供的锂二次电池在选自负极、正极、隔膜以及无水电解液的至少一个组件中包含一种离聚物。
Description
技术领域
本发明涉及一种通过在正极(cathode)、负极(anode)和隔膜的至少一个组件中包含一种离聚物来实现高温稳定性和高功率的锂二次电池,所述离聚物具有氟代烷基磺酸酯取代基。
背景技术
随着储能技术的应用领域扩大至手机、摄像机、笔记本电脑以及电动车辆,在研究和开发电池方面的努力越来越具体化,并且电化学装置在这方面得到最多的关注。
具体而言,根据电子器件的趋势,不断努力开发尺寸小、重量轻并且充放电容量高的锂二次电池。
锂二次电池由正极和负极、插在正极和负极之间的隔膜以及作为锂离子传输介质的电解液所构成,所述正极和负极含可以嵌入和脱嵌锂离子的电极活性材料。
与此同时,随着上述锂二次电池应用领域的逐渐扩大,在构成锂二次电池的至少一个组件中包含有机聚合物(例如“离聚物”化合物)的电池被认为可以在恶劣环境(如高温或低温环境)中保持良好性能,其中所述有机聚合物含有离子侧基(参见专利文献1)。
换言之,在将一种离聚物型化合物引入构成锂二次电池的至少一个组件中的情况下,在构成组件的表面形成离子传导膜或者形成凝胶型电解质等,从而可以实现使用液体电解液时通常难于获得的电池性能。
现有技术文献
专利文献1:韩国公开专利公报第10-2000-0052944号
专利文献2:韩国注册专利公报第10-0541312号
发明内容
技术问题
本发明是由正极、负极、隔膜和电解液构成的锂二次电池,本发明是在如下前提下完成的:通过在制造上述构成组件中的至少一个组件的过程中引入具有氟代烷基磺酸酯取代基的离聚物,认为能够确保锂二次电池在高温或高电压环境中的电池性能。
具体而言,本发明的目的在于提供一种锂二次电池,其是由正极、负极、插在正极和负极之间的隔膜以及无水电解液构成的锂二次电池,所述锂二次电池在选自正极、负极、隔膜和无水电解液的至少一个组件中包含具有氟代烷基磺酸酯取代基的离聚物。
技术方案
为克服上述缺陷,本发明提供一种包括正极、负极、插在正极和负极之间的隔膜以及无水电解液的锂二次电池,其中由下述化学式1表示的离聚物包含在选自正极、负极、隔膜和无水电解液的至少一个组件中。
[化学式1]
在上式中,A和B独立地为H、F、CH3、CF3或CF2H,–CF-O-(CF2)2-SO3 -Li+:-CF2-的摩尔比为10至100:0至90,且k是至少为1的整数。
此外,由上述化学式1表示的离聚物的重均分子量为240至200,000。
本发明中,所述正极中,正极可以正极的组合物或正极的涂布组分的形式包含由上述化学式1表示的离聚物。
本发明中,所述负极中,负极可以负极的组合物或负极的涂布组分的形式包含由上述化学式1表示的离聚物。
此外,所述隔膜中,隔膜可以隔膜的组合物或隔膜的涂布组分的形式包含由上式1表示的离聚物。
此外,所述无水电解液中,无水电解液可以添加剂的形式包含由上式1表示的离聚物。
有益效果
本发明的二次电池通过在构成所述二次电池的至少一个组件中包含具有氟代烷基磺酸酯取代基的离聚物可以确保高的离子电导率、改善的机械性能等,并且还可以实现二次电池的稳定性,所述稳定性是借由通过解决二次电池的浓差极化以获得高功率效果和借由通过防止过渡金属在更高的温度或高电压环境中的解吸以改善寿命效果而实现的。
附图说明
本发明的优选实施方案将参照所附附图进行说明。附图旨在进一步理解上述发明的内容和本发明的技术构思,并且本发明不应理解为限于附图中所公开的内容。
图1是示出本发明实验性实施例1的高电压下循环寿命测量结果的图;
图2是示出本发明实验性实施例2的放电容量随着充电速率(C-rate)的提高的而变化的图;
图3和4是示出本发明实验性实施例3的放电容量与放电曲线的图;
图5是示出本发明实验性实施例4的循环寿命测量结果的图。
图6是示出本发明实验性实施例5的充电情况随着充电速率提高而变化的图。
具体实施方式
下文中,对本发明进行更加详细的描述以帮助理解本发明。应理解,在本说明书和权利要求中使用的术语或词语不应理解为一般含义或字典中定义的含义,而应在术语的概念由发明人进行了合适的定义以更好的理解本发明的原则的基础上,理解为所述术语或词语具有与它们在本发明上下文中的含义相一致的含义。
在现有的锂二次电池中,二次电池在高温或高压下运行的过程中,通过渗入二次电池中的水与无水电解质中包含的电解质盐的阴离子的反应可引发电解质盐分解的副反应,包括产生气体如HF气体,诱发电池腐蚀。所述副反应可随温度的上升而加剧。此外,所产生的HF气体可能加速正极材料过渡金属的解吸,从而成为阻碍二次电池循环寿命和稳定性的一个因素。为了改善该缺陷,最近已经提出一种减少电解液中电解质盐的含量的方法。在这种情况下,高电压安全性得到改善,但是由于存在浓差极化现象等,电池电阻提高,从而产生了另外的二次电池的功率降低和循环寿命减少的缺陷。
最近,提出一种向构成锂二次电池的构成组件中引入离聚物型化合物的方法,以改善上述缺点。根据上述方法,可以实现使用液体电解液难以实现的锂二次电池在高温或高电压环境下的性能。
但是,在具有长侧链的离聚物化合物中,例如含有允许Li取代的SO3 -的长侧链中,即使引入具有相同结构的聚合物,Li取代的重量比例也会降低。因此,与离子传输相关的、用于形成微通道效应的自组装性能可能变差,并且可能得到低离子电导率。此外,在形成主链的重复单元结构包含氧或者形成主链的重复单元结构长的情况下,Li离子的迁移可能成为问题。
因此,本发明提供一种这样一种锂二次电池:即使降低无水电解液中电解质盐的含量,也能够获得高离子电导率、或通过解决所述二次电池的浓差极化而实现的高功率,并且通过阻止高温或高电压环境中过渡金属的解吸而确保循环寿命性能和安全性。
具体而言,本发明提供一种包括正极、负极、插在正极和负极之间的隔膜以及无水电解液的锂二次电池,其中,一种由下述化学式1表示的离聚物包含于选自正极、负极、隔膜和无水电解液的至少一个组件中。
[式1]
在上式中,A和B独立地为H、F、CH3、CF3或CF2H,–CF-O-(CF2)2-SO3 -Li+:-CF2-的摩尔比为10至100:0至90,且k是至少为1的整数。
此外,由上述化学式1表示的离聚物的重均分子量为240至200,000,特别地为240至10,000。
具体而言,由上述化学式1表示的离聚物包括由碳组成的主链和含有氟代烷基磺酸酯取代基的侧链,所述碳组成的主链中氢原子完全地或部分地被氟原子取代。
此外,由上述化学式1表示的离聚物是一种单离子导体,其代替电解液中所含有的电解质发挥不含阴离子的锂源的作用。换言之,在引入由上述化学式1表示的离聚物的情况下,阴离子作为电池中的固定相,且可以仅提供电池中的锂源,从而能够减少包含于无水电解液中的电解质盐的含量,并且能够通过解决浓差极化来获得高功率效果,能够提高锂离子在电解液中的自由度。此外,电解质盐的阴离子引起的副反可受到限制,从而能够实现高温和高电压下的二次电池的循环寿命性能和稳定性。在由上述化学式1表示的离聚物包含于电解液中的情况下,上述化学式1中的–CF-O-(CF2)2-SO3 -Li+:-CF2-的摩尔比可以为10至100:0至90,并且可以特别地为10至90:10至90。
此外,使用由上述化学式1表示的离聚物将阴离子作为固定相而引入电极的情况下,在负极,通过放电后期可能会产生的浓差极化而使减小电阻,在正极,可能避免因正极完全充电期间Li盐的阴离子浓差极化而产生的放电初始阶段的电阻增大的现象。在由上述化学式1表示的离聚物包含于电极的情况下,上述化学式1中的–CF-O-(CF2)2-SO3 -Li+:-CF2-的摩尔比优选为10至90:10至90。
具体而言,如本发明,在含有允许Li取代的SO3 -的离聚物的侧链长度短并且具有小于或等于5个碳原子的情况下,由于离子电导率高,且形成主链的重复单元的结构是含氟结构,因此能够提高电化学稳定性。
在这种情况下,包含于构成二次电池的组件中的由上式1表示的离聚物的含量没有特别的限定,可以根据构成锂二次电池的组件的种类例如电极活性材料、电极和隔膜进行合适的控制,条件是,将所述离聚物的含量控制这样的范围内:通过解决所述二次电池的浓差极化问题而实现的高功率效果,以及实现所述二次电池在高温和高电压下的循环寿命和稳定性效果。换言之,不管所述离聚物的含量、用途、引入位置等,只要构成所述二次电池的组件中包含所述离聚物就可以获得上述效果。
具体而言,包含由上述化学式1表示的离聚物的构成二次电池的组件可以具有以下实施方案,但是本发明不限于此。
(A)包含由化学式1表示的离聚物的电极
首先,本发明提供了一种包含由上述化学式1表示的离聚物的电极。具体而言,本发明的电极可以包含作为电极活性材料的涂层组分、电极组合物或电极表面涂布成分的由上述化学式1表示的离聚物。在这种情况下,所述电极可以是负极或正极,并且对其应用范围没有特别的限定。
此外,电极中的离聚物的含量没有特别的限定,条件是,其在可以实现所述二次电池在高温和高电压下的循环寿命和稳定性的含量范围内。具体而言,所述离聚物的含量可以为约0.01至约20重量%,基于于电极混合物的总量计。
(A-1)电极活性材料的涂层组分
具体而言,本发明提供了一种包含电极活性材料和涂层的电极,所述涂层包含由上式1表示的离聚物并且所述涂层形成在电极活性材料表面。
所述电极可以是正极或者负极。在所述电极是正极的情况下,电极活性材料可以是用于现有锂二次电池正极中的常规正极活性材料,而没有特别的限定。在这种情况下,可以使用的正极活性材料的代表实例可包括为锂镍锰复合氧化物(LNMO)和其他材料,除此之外还可结合使用:例如,层状结构化合物,例如钴锂氧化物(LiCoO2)、镍锂氧化物(LiNiO2)等);经过渡金属取代的锂过渡金属复合氧化物,例如Li(NiaCobMnc)O2(0<a<1、0<b<1、0<c<1,并且a+b+c=1);锰锂氧化物,例如LiMnO3、LiMn2O4、LiMnO2等;铜锂氧化物(Li2CuO2);钒的氧化物,例如LiV3O8、V2O5、Cu2V2O7等;LiFe3O4;锂磷酸盐,例如LiFePO4、LiCoPO4、LiFexMn1-xPO4等;由式LiNi1-xMxO2表示的Ni位型镍锂氧化物(其中M=Co、Mn、Al、Cu、Fe、Mg、B或Ga,并且x=0.01至0.3);由式LiMn2-xMxO2等表示的锰锂复合氧化物(其中M=Co、Ni、Fe、Cr、Zn或Ta,并且x=0.01至0.1),或Li2Mn3MO8(其中M=Fe、Co、Ni、Cu或Zn);但并不限定与此。
此外,在所述电极为负极的情况下,电极活性材料可以用于现有锂二次电池负极中的常规负极活性材料和其他材料,,而没有特别的限定。可使用的负极活性材料的代表实例为钛锂氧化物(LTO)和其他材料,除此之外还可结合使用:例如,碳,如硬碳、石墨、石墨基碳等;金属复合氧化物,如LixFe2O3(0≤x≤1)、LixWO2(0≤x≤1)、SnxMe1-xMe'yOz(Me:Mn、Fe、Pb、Ge;Me':Al、B、P、Si、元素周期表第Ⅰ、第Ⅱ和第Ⅲ族的元素,卤素;0<x≤1;1≤y≤3;1≤z≤8);锂金属;锂合金;硅合金;锡合金;金属氧化物,如SnO、SnO2、PbO、PbO2、Pb2O3、Pb3O4、Sb2O3、Sb2O4、Sb2O5、GeO、GeO2、Bi2O3、Bi2O4和Bi2O5;导电聚合物,如聚乙炔;Li-Co-Ni-基材料;氧化钛等。
此外,在本发明中,电极活性材料的涂布方法可以是在该领域中的常规涂布方法,例如,溶剂蒸发法、共沉淀法、沉淀法、溶胶-凝胶法、吸附后过滤法(filtration afteradsorption method)、溅射法、CVD法等。上述电极活性材料的涂布方法并无特别的限定。一个优选的实施方案可以包括:(a)通过将由上式1表示的离聚物分散在粘合剂溶液中而制备涂布溶液的步骤,所述涂布溶液包含由上式1表示的离聚物;(b)通过将电极活性材料的颗粒加入到涂布溶液中并搅拌后进行涂布的步骤;以及(c)热处理涂布有由上式1表示的离聚物的电极活性材料的步骤。
(A-2)电极组合物
此外,本发明提供了一种包括电极集电器(electrode collector)和涂布在电极集电器上的电极组合物的电极,其中所述电极组合物包含电极活性材料和由上式1表示的离聚物。
在这种情况下,所述电极组合物没有特别的限定,但是,除电极活性材料和由上式1表示的离聚物外,可以任选地包含粘合剂、导电材料和溶剂。
此外,本发明中,制造电极的方法没有特别的限定,可以包括:(a)制备粘合剂溶液的步骤;(b)通过在粘合剂溶液中分散并混合电极活性材料、由上式1表示的离聚物以及任选的导电材料而制备电极浆料的步骤;(c)将所制备的电极浆料施用或涂布于电极集电器上的步骤;以及(d)通过热处理而干燥的步骤。
在所述电极集电器中,正极集电器可以无限定地为铝、镍或这由它们的结合物形成的薄片等,并且负极集电器可以无限定地为铜、金、镍、铝、铜合金,或者由它们的结合物形成的薄片等。
此外,所述粘合剂溶液可以通过向溶剂中或分散介质(例如,N-甲基吡咯烷酮(NMP))加入粘合剂(例如,聚偏氟乙烯(PVDF))而制备。
在这种情况下,溶剂或分散介质可以是在该领域中使用的所有常用溶剂,且可包括例如,有机溶剂,例如N-甲基-2-吡咯烷酮、丙酮、二甲基乙酰胺、二甲基甲醛等;无机溶剂,例如水;或其混合物。考虑到电极浆料的涂布厚度和产品产量,溶剂的使用量为能够充分溶解并分散活性材料、导电材料、电极粘合剂和粘合添性添加剂的量。将电极浆料涂布在集电器上之后,通过干燥去除溶剂。
此外,作为粘合剂,可以适量使用常规粘合材料,并且其非限定性实例可以包括PVDF、丁苯橡胶、特氟龙及其混合物。
此外,作为用于制备电极浆料的导电材料,只要是该领域中常规使用的导电材料,则其种类和含量没有特别的限定。其非限定性实例可以包括乙炔黑、炭黑或石墨。
此外,电极浆料的施用或涂布步骤以及电极的干燥步骤也可以是任何本领域中已知的常用方法。电极的干燥步骤可以是例如热空气干燥。
(A-3)电极的涂布组分
此外,本发明提供了一种电极,其包括事先在电极表面上通过使用由上式1表示的离聚物形成的涂层。
在事先形成的电极表面上涂布由上式1表示的离聚物的方法也可以是在本领域中已知的常用方法。在一个实施方案中,使所述离聚物分散在粘合剂溶液或溶剂中,从而制备含有离聚物的分散体,并且将所述分散体涂布在事先形成的电极的表面上并干燥。
在根据以上各种方法形成的本发明的电极的整个或部分表面上,形成有包含由上式1表示的离聚物的涂层。
(B)包含由式1表示的离聚物的隔膜
此外,本发明提供了一种包含由上式1表示的离聚物的隔膜。在这种情况下,所述隔膜可以是仅仅使用由上式1表示的离聚物所形成的薄膜型独立式隔膜,或者是在多孔基材上包含涂层的复合多孔隔膜,所述涂层包含由上式1表示的离聚物。
只要在能够实现所述二次电池在高温和高电压环境中的循环寿命或稳定性,则隔膜中离聚物的含量没有特别的限定。具体而言,所述含量可以为0.01至20重量份,基于100重量份的隔膜的全部组分计。
(B-1)使用离聚物形成的独立式隔膜
具体而言,本发明提供了一种仅仅由上式1表示的离聚物形成的独立式隔膜。
所述独立式隔膜可以使用由上式1表示的离聚物与一种粘合剂聚合物的混合物形成。例如,由上式1表示的离聚物可以通过粘合剂聚合物而彼此结合或连接以形成独立式隔膜。在这种情况下,可以在独立式隔膜中形成一种具有均匀尺寸的孔隙结构。
在独立式隔膜中形成的孔隙的尺寸和孔隙率没有特别的限定,具体而言,孔隙率可以为5至95%,以及孔隙尺寸(直径)可以为0.01至50μm。
(B-2)包含含有离聚物的涂层的多孔隔膜
此外,本发明的另一个实施方案提供了一种复合(多孔)隔膜,其包括在用于常规二次电池的隔膜(多孔隔膜)上的含有由上式1表示的离聚物的涂层。
例如,在多孔基材上形成有包含含有由上式1表示的离聚物的涂层的隔膜,可以通过将聚烯烃基多孔隔膜基材浸渍在含有由上式1表示的离聚物的涂布溶液中而制造,或通过借由常规涂布方法而涂布所述涂布溶液后去除溶剂而制造。在这种情况下,含有离聚物的涂层可以根据情况作为与无机材料混合的涂层而获得。
在这种情况下,可以引入由上式1表示的离聚物的多孔隔膜可以是任何能够阻挡两个电极内部短路并且浸渍于电解液的多孔材料,而无特别的限制。隔膜的孔隙直径通常可以为0.01至10μm,并且其厚度通常可以为5至300μm的范围。
所述隔膜可以使用例如,烯烃基聚合物,如耐化学腐蚀的且疏水的聚丙烯;复合多孔隔膜,器通过在多孔隔膜基材中加入无机材料而获得;薄片或非织造物,器使用玻璃纤维或聚乙烯等形成。当使用固体电解质(例如聚合物)作为电解质时,所述固体电解质也可以用作隔膜。
(C)包含由式1表示的离聚物的电解液
此外,本发明提供了包含由式1表示的离聚物的电解液。具体而言,提供了一种包含电解质盐和无水有机溶剂并且还包含由上式1表示的离聚物作为添加剂的无水电解液。
具体而言,在所述无水电解液中,因为引入构成锂二次电池组件中的离聚物可以替代包含于电解液中的电解质盐而发挥锂盐的作用,因此,除了作为必要成分而被包括的电解质盐以外,仅仅包含无水有机溶剂。
所述无水有机溶剂是可以用作常规无水电解液溶剂的任何有机溶剂,而无限定。无水有机溶剂的代表实例可以包括至少一种选自以下的有机溶剂:环状碳酸酯化合物、线性碳酸酯化合物、内酯、醚化合物、酯化合物、亚砜、内酰胺和酮。
所述环状碳酸酯化合物例如为:碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸亚丁酯(BC)和氟代碳酸亚乙酯(FEC)等,所述线性碳酸酯化合物例如为:碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸二丙酯(DPC)、碳酸甲乙酯(EMC)和碳酸甲丙酯(MPC)等。所述内酯例如为γ丁内酯(GBL),且所述醚化合物例如为二丁醚、四氢呋喃、2-甲基四氢呋喃、1,4-二噁烷二氧六环、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷等。所述酯化合物例如为甲酸甲酯、甲酸乙酯、甲酸丙酯、丙酸乙酯、丙酸丁酯、新特戊酸甲酯等。此外,所述亚砜例如为二甲亚砜等,且所述内酰胺例如为N-甲基-2-吡咯烷酮(NMP)等,且所述酮例如为聚甲基乙烯基酮。此外,也可以使用有机溶剂的卤素衍生物。这些有机溶剂可以单独使用或作为混合物使用。
此外,在本发明的无水电解液中含有电解质盐的情况下,所述电解质盐可以是用于常规电化学装置的电解质盐,并且可以是以下物质的结合:(i)选自Li+、Na+和K+的至少一种阳离子以及(ii)选自PF6 -、BF4 -、Cl-、Br-、I-、ClO4 -、AsF6 -、CH3CO2 -、CF3SO3 -、N(CF3SO2)2 -和C(CF2SO2)3 -的至少一种阴离子,而无限定。这些电解质盐可以单独使用或作为混合物使用。电解质盐的含量没有特别的限定,并且基于无水电解液的总量计可以少于或者等于50重量%,并且特别地可以为0至30重量%。所述电解质盐具体例如为锂盐或者锂酰亚胺盐。
此外,电解液中由上式1表示的离聚物的含量没有特别的限定,只要能够减少电解质盐的含量,并且通过解决浓差极化实现高功率效果,提高电解液中锂粒子的自由度,抑制电解质盐的阴离子引起的副反应,从而能够实现高温和高电压下的二次电池的循环寿命和稳定性的含量,则没有特别的限制,具体而言,所述含量可以为0.01至20重量份,基于100重量份的电解液的总量计。
此外,所述锂二次电池可以混合使用各种的电解液组合物(例如聚合物电解液)来替代无水电解液,并且电解液组合物的种类没有特别的限定。
与此同时,本发明的锂离子二次电池可以通过本领域已知的常规方法制备,作为一个实施方案,通过将隔膜插在正极和负极之间并组装,之后注入无水电解液,从而制备锂离子二次电池。在这种情况下,可以将由上式1表示的离聚物引入电极和隔膜的至少一个中。
实施例
在上述本发明的详细描述中,已经描述了具体的实施方案。但是,本发明可以在本发明的范围内以不同的形式体现。本发明的技术构思不应理解为限制在文中所描述的实施方案中,而应由权利要求及其等同内容确定。
实施例
1.包含离聚物的负极
(实施例1)
将96重量%的作为负极活性材料的LTO、4重量%的作为粘合剂的PVdF、2重量%的上述化学式1的离聚物(重均分子量约308)以及1重量%的作为导电材料的炭黑加入N-甲基吡咯烷酮(NMP)溶剂中,以制备负极混合物浆料。将所述负极混合物浆料涂布在作为负极集电器的厚度为10μm的铝薄膜上,并干燥以制备负极。
然后,将92重量%的作为正极活性材料的LNMO尖晶石化合物、4重量%的作为导电材料的炭黑以及4重量%的作为粘结材料的PVdF加入NMP溶剂中,以制备正极浆料。将所述正极浆料涂布在作为正极集电器的厚度为20μm的铝(Al)薄膜上,并干燥以制备正极。
将聚烯烃基隔膜***以上述方式制备的负极与正极之间,从而制造电极组件,之后将0.5M的LiPF6无水电解液(EC/PC/DEC=30/20/50重量%)加入其中,从而经由引入LTO负极而制造5V级的高电压全电池(Full cell)。
(比较实施例1)
除了在制备负极过程中包含6重量%的PVdF作为粘合剂来代替由上述化学式1表示的离聚物、以及在制造电解液过程中加入0.5M的LiPF6无水电解液之外,以与上述实施例1相同的步骤制备5V级的高电压电池。
(实验性实施例1)改善循环寿命的实验
进行以下实验以评估包含本发明离聚物的锂二次电池的充电率(C-rate)性能。即,将实施例1的锂二次电池和比较实施例1的锂二次电池在45℃下以1C/1C的充放电倍率循环充放电,并且将其充放电容量示于图1。
由该实验结果可以确定,相比于比较实施例1的锂二次电池的循环寿命性能,本发明实施例1的锂二次电池的循环寿命性能有所改善。
(实验性实施例2)通过减小浓差极化而改善电池电阻的实验
通过将实施例1和比较实施例1的各个锂二次电池在45℃下的充电倍率固定为0.5C并且将放电倍率由0.5C改变至5C而观察容量变化,并且评估速率性能。结果示于图2。
由该实验可见,如本发明实施例1的锂二次电池,在引入离聚物并减少无水电解液中电解质盐含量的情况下,能够确认如下情况:与比较实施例1的锂二次电池相比,由浓差极化导致的电阻减小,从而在充电率增大时放电容量也很低。
2.包含离聚物的正极
(实施例2)
将92重量%的作为正极活性材料的LNMO尖晶石基化合物、4重量%的作为导电材料的炭黑、2重量%的作为粘合材料的PVdF、2重量%的上述化学式1的离聚物(重均分子量约308)加入NMP溶剂中,以制备正极浆料。将所述正极浆料涂布在作为正极集电器的厚度为20μm的铝薄膜上,并干燥以制备正极。Li金属用作负极。
将聚烯烃基隔膜***以上述方式制备的负极和正极之间,以制造电极组件,之后将0.5M的LiPF6无水电解液(EC/PC/DEC=30/20/50重量%)加入其中,从而经由引入LNMO正极活性材料而制备5V级的高电压半电池(half cell)。
(比较实施例2)
除了在制备电解液过程中包含4重量%的PVdF作为粘合剂来代替由上述化学式1表示的离聚物、以及在制造电解液过程中加入0.5M的LiPF6无水电解液之外,以与上述实施例2相同的步骤制备5V级的高电压电池。
(实验性实施例3)经由放电曲线抑制极化
进行以下实验以观察包含离聚物的本发明锂二次电池的极化现象的抑制性能。即,将上述实施例2的锂二次电池和上述比较实施例2的锂二次电池在23℃下以1C充电,且其放电容量和放电曲线示于图3和4。
由该实验结果可以确定,相比于比较实施例2的锂二次电池,本发明实施例2的锂二次电池的极化现象得到控制,从而电阻降低,在相同倍率下,其容量增大。
(实验性实施例4)寿命性能的评估
观察实施例2和比较实施例2各锂二次电池在45℃下的1C/1C充放电性能。且结果示于图5。
由该实验结果可见,如本发明实施例2的锂二次电池,在引入离聚物并减少无水电解液中电解质盐含量的情况下,能够确认如下情况:与比较实施例2的锂二次电池相比,寿命保持率相等,但其容量增大。
3.包含离聚物的负极
(实施例3)
将96重量%的作为负极活性材料的石墨、5重量%的作为粘合剂的PVdF、5重量%的上式1的离聚物(重均分子量约308)以及1重量%的作为导电材料的炭黑加入NMP溶剂中,以制备负极混合物浆料。将所述负极浆料涂布在作为负极集电体的厚度为10μm的铝薄膜上,并干燥以制备负极。
Li金属用作正极。
将聚烯烃基隔膜***由此制备的负极和正极之间,以制备电极组件,并且将0.5M的LiPF6的无水电解液(EC/PC/DEC=30/20/50重量%)加入其中,从而经由引入石墨负极活性材料而制造5V级的高电压半电池(Half cell)。
(比较实施例3)
除了在制备负极的过程中包含10重量%PVdF的作为粘合剂来代替由上式1表示的离聚物、以及在制造电解液过程中加入0.5M的LiPF6的无水电解液之外,以与上述实施例3中相同的步骤制造5V级的高电压电池。
(实验性实施例5)通过抑制极化确保电阻减小
进行以下实验以观察包含离聚物的本发明锂二次电池的电阻减小效果。即,将上述实施例3的锂二次电池和上述比较实施例3的锂二次电池在23℃下以1C进行充电,并且将其充电曲线示于图6。
由该实验结果可以确定,相比于比较实施例3的锂二次电池的电阻,实施例3的锂二次电池的电阻有所减少。
Claims (8)
1.一种锂二次电池,其为包括正极、负极、插在所述正极和所述负极之间的隔膜以及无水电解液的锂二次电池,其特征在于,
由下述化学式1表示的离聚物包含在所述正极或所述负极中,
由所述化学式1表示的离聚物的重均分子量为240至10,000,并且由所述化学式1表示的离聚物的含量为0.01至20重量%,基于正极混合物或负极混合物的总量计:
[化学式1]
其中A和B独立地为H、F、CH3、CF3或CF2H,
–CF-O-(CF2)2-SO3 -Li+:-CF2-的摩尔比为10至90:10至90,
k是至少为1的整数。
2.根据权利要求1所述的锂二次电池,其特征在于,
由所述化学式1表示的离聚物发挥锂离子源的作用。
3.根据权利要求1所述的锂二次电池,其特征在于,
所述正极中,以如下方式包含由所述化学式1表示的离聚物:作为正极活性材料涂布组分、正极组合物或正极涂布组分。
4.根据权利要求1所述的锂二次电池,其特征在于,
所述负极中,以如下方式包含由所述化学式1表示的离聚物:作为负极活性材料涂布组分、负极组合物或负极涂布组分。
5.根据权利要求1所述的锂二次电池,其特征在于,
所述无水电解液包含电解质盐和无水有机溶剂。
6.根据权利要求5所述的锂二次电池,其特征在于,
所述电解质盐包括以下物质的结合:(i)选自Li+、Na+和K+的至少一种阳离子以及(ii)选自PF6 -、BF4 -、Cl-、Br-、I-、ClO4 -、AsF6 -、CH3CO2 -、CF3SO3 -、N(CF3SO2)2 -和C(CF2SO2)3 -的至少一种阴离子。
7.根据权利要求5所述的锂二次电池,其特征在于,
所述无水有机溶剂包括至少一种选自以下的有机溶剂:环状碳酸酯化合物、线性碳酸酯化合物、内酯、醚化合物、酯化合物、亚砜、内酰胺和酮。
8.根据权利要求7所述的锂二次电池,其特征在于,
所述环状碳酸酯化合物包括至少一种选自以下的物质:碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸亚丁酯(BC)和氟代碳酸亚乙酯(FEC),
所述线性碳酸酯化合物包括至少一种选自以下的物质:碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸二丙酯(DPC)、碳酸甲乙酯(EMC)和碳酸甲丙酯(MPC),
所述内酯包括γ丁内酯,
所述醚化合物包括至少一种选自以下的物质:二丁醚、四氢呋喃、2-甲基四氢呋喃、1,4-二噁烷、1,2-二甲氧基乙烷和1,2-二乙氧基乙烷,
所述酯化合物包括至少一种选自以下的物质:甲酸甲酯、甲酸乙酯、甲酸丙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丁酯和特戊酸甲酯,
所述亚砜包括二甲亚砜,
所述内酰胺包括N-甲基-2-吡咯烷酮,且
所述酮包括聚甲基乙烯基酮。
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