CN106972192A - For the method and electrolytic cell device, lithium-ion energy storage device of the prefabricated lithium of lithium-ion energy storage device negative pole - Google Patents
For the method and electrolytic cell device, lithium-ion energy storage device of the prefabricated lithium of lithium-ion energy storage device negative pole Download PDFInfo
- Publication number
- CN106972192A CN106972192A CN201710155541.5A CN201710155541A CN106972192A CN 106972192 A CN106972192 A CN 106972192A CN 201710155541 A CN201710155541 A CN 201710155541A CN 106972192 A CN106972192 A CN 106972192A
- Authority
- CN
- China
- Prior art keywords
- lithium
- prefabricated
- cathode
- electrode
- ion
- 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
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 145
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 70
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000004146 energy storage Methods 0.000 title claims abstract description 29
- 239000000919 ceramic Substances 0.000 claims abstract description 38
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 36
- 239000007864 aqueous solution Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 18
- 239000010406 cathode material Substances 0.000 claims abstract description 10
- 241001131796 Botaurus stellaris Species 0.000 claims abstract description 5
- 239000002699 waste material Substances 0.000 claims abstract description 5
- 239000011521 glass Substances 0.000 claims description 34
- 239000010935 stainless steel Substances 0.000 claims description 30
- 229910001220 stainless steel Inorganic materials 0.000 claims description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 16
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000002033 PVDF binder Substances 0.000 claims description 10
- 230000005611 electricity Effects 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 9
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000002241 glass-ceramic Substances 0.000 claims description 7
- -1 oxygen metal Oxide Chemical class 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- 239000011135 tin Substances 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 238000010606 normalization Methods 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 3
- 239000002228 NASICON Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000006056 electrooxidation reaction Methods 0.000 claims description 3
- 230000037427 ion transport Effects 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000007614 solvation Methods 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 2
- 125000006091 1,3-dioxolane group Chemical class 0.000 claims description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-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
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- WEVMDWQCQITELQ-UHFFFAOYSA-N [O-]B(O)O.[Li+].F.F.F.F Chemical compound [O-]B(O)O.[Li+].F.F.F.F WEVMDWQCQITELQ-UHFFFAOYSA-N 0.000 claims description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 238000009417 prefabrication Methods 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims 1
- 229910000831 Steel Inorganic materials 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229920002239 polyacrylonitrile Polymers 0.000 claims 1
- 239000010959 steel Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 41
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 12
- 239000011245 gel electrolyte Substances 0.000 description 9
- 229910001290 LiPF6 Inorganic materials 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000005486 organic electrolyte Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 239000011149 active material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910008550 Li2O—Al2O3—SiO2—P2O5—TiO2—GeO2 Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000032258 transport Effects 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a kind of method and electrolytic cell device, lithium-ion energy storage device for the prefabricated lithium of lithium-ion energy storage device negative pole, designed using lithium ion half-cell type, it is covered on gel polymer electrolyte between lithium cell cathode material and ceramic base solid electrolyte film, good ionic conduction is provided, gel polymer electrolyte can load full battery together with cathode of lithium battery after prefabricated lithium, manufacture poly-lithium battery.Secondly, the electrolytic cell anode is using lithium ion aqueous solution as electrolyte and lithium source, and lithium source materials are extensive, can be that lithium bittern or waste lithium cell lithium reclaim the aqueous solution, it is environment-friendly, it is nontoxic, chemical property is stable, it is not necessary to strict storage and transporting equipment, reduces the cost of prefabricated lithium.
Description
Technical field
The invention belongs to electrochemical field, it is related to and a kind of does not use lithium metal for the prefabricated lithium of lithium-ion energy storage device negative pole
The lithium-ion energy storage device that negative pole after method and electrolytic cell device, and prefabricated lithium is constituted.
Background technology
Lithium-ion energy storage device includes lithium ion battery and lithium-ion capacitor, high with higher energy density, puts certainly
Electricity is small, has extended cycle life, the advantages of memory-less effect, is widely used in portable electric appts, energy storage communication, space flight, electricity
In the field such as motor-car and honourable energy storage.Along with lithium-ion capacitor and Large Copacity sulfenyl, air (oxygen) base and metal oxidation
The development of thing base lithium ion battery, the prefabricated lithium of negative electrode of lithium ion battery has become lithium-ion energy storage research and field of industrial production
Very important direction of scientific rersearch and sport technique segment.Traditional prefabricated lithium method uses metallic lithium foil or lithium powder for the prefabricated lithium of negative pole.
There is inborn shortcoming in this method：First, the production of lithium metal generally uses high temperature fused salt electrolysis method, it is necessary in protective atmosphere
It is lower to carry out, the transport of lithium metal and the strict safeguard procedures of preservation needs and equipment requirement, so lithium metal is not saved in itself
Environmental protection.Secondly, lithium metal is the excellence conductor of electronics, easily occurs short circuit with negative pole during prefabricated lithium, there is safety
Hidden danger.Again, lithium metal chemism is strong, and can be reacted life with the electrolyte and electrolysis additive of spontaneous same prefabricated lithium
Into passivating film, the controllability of prefabricated lithium is have impact on, the recycling of lithium metal equally exists difficulty.
The content of the invention
It is the prefabricated lithium of lithium-ion energy storage device negative pole green the invention provides one kind for Shortcomings in the prior art
Method and electrolytic cell device, the process of prefabricated lithium uses wider lithium source not against lithium metal, by lithium ion from water-soluble
It is directly prefabricated in liquid to arrive lithium-ion energy storage device negative pole, prefabricated lithium technique will be made more environmentally friendly, cheap and safe.
Be the prefabricated lithium of negative pole the process employs a kind of new electrolytic cell device, during need not use lithium metal.
Negative pole after prefabricated lithium is matched with positive pole, lithium-ion energy storage device is assembled into, preferable chemical property is shown.
To achieve these goals, technical scheme is as follows.
A kind of electrolytic cell device for the prefabricated lithium of lithium-ion energy storage device negative pole, mainly includes cathode half-cell and anode half
Two parts of battery, it is characterised in that：The cathode half-cell includes cathode chamber, the lithium ion battery anode material being placed in cathode chamber
Material, gel polymer electrolyte, ceramic base solid electrolyte film, and it is wrapped in the negative electrode glass sock outside cathode chamber；Institute
Stating cathode chamber one end has a through hole, the ceramic base solid electrolyte film be located at the through hole of cathode chamber and with the negative electrode
Epoxy resin is set to be sealed between room, the gel polymer electrolyte is located at negative material, ceramic base solid electrolyte
Between film, the gel polymer electrolyte is combined by polymer, three kinds of components of electrolytic salt and small molecular organic solvent
Gel-type system；The ceramic base solid electrolyte film is oxide system NASICON type glass ceramics solid electricity
Xie Zhi；
Glass anode chamber of the anodic half-cell including being equipped with lithium ion aqueous solution, the silver being placed in the anode chamber/
Silver chloride reference electrode, titanium collector, inert electrode or sacrificial electrode, the protection gas；The glass anode chamber is tubulose, institute
The one end for stating glass anode chamber is connected with the through hole of the cathode chamber end, and the bottom of the anode chamber is logical provided with protective gas
Tracheae.
Preferably, the lithium ion aqueous solution is the water-soluble of the aqueous solution, the aqueous solution of lithium sulfate, lithium chloride of lithium nitrate
Liquid, the aqueous solution of lithium perchlorate, the lithium of the bittern of lithium or waste lithium cell reclaim the aqueous solution.
Preferably, the titanium collector is corrosion resistant Ti alloy.Electrochemical corrosion can not be produced in salt solution.
Preferably, the inert electrode include carbon paper, analysis oxygen metal oxide, the analysis oxygen metal oxide be titanium, zirconium,
Ruthenium, iridium, tin, the oxide of tantalum or wherein two or more hopcalite；The sacrificial electrode can be in saline solution
Middle generation electrochemical corrosion, is zinc, iron, tin, lead or copper.
Preferably, the protective gas is nitrogen, argon gas or carbon dioxide.
Preferably, the second seal with elastometic washer is set between the glass anode chamber and the cathode chamber.
Preferably, the cathode chamber is made up of stainless steel bolt and STAINLESS STEEL NUTS, one end tool of the STAINLESS STEEL NUTS
There is annular end face, the stainless steel bolt screws in the other end of the STAINLESS STEEL NUTS, and the bottom of the bolt is covered on negative pole
Material.
Preferably, the junction of stainless steel bolt and negative electrode glass sock is sealed using the first rubber ring.
Preferably, the negative material is graphite, silicon, germanium, tin, metal oxide, silicon-base alloy, acieral or tinbase
Alloy；The metal oxide is the oxide of germanium, tin, titanium, vanadium, manganese, iron, cobalt, nickel, molybdenum or tungsten.
Preferably, the polymer in the gel polymer electrolyte is polyoxyethylene, polymethyl methacrylate, poly- third
Alkene nitrile or polyvinylidene fluoride, the electrolytic salt are lithium hexafluoro phosphate, tetrafluoride lithium borate, lithium perchlorate, trifluoromethanesulfonic acid
Lithium, double trifluoromethanesulfonimide lithiums or biethyl diacid lithium borate, the small molecular organic solvent are dimethyl carbonate, carbonic acid two
Ethyl ester, ethylene carbonate, propene carbonate, 1,3- dioxolanes or 1,2- dimethoxy-ethanes.
For the method for the prefabricated lithium of lithium-ion energy storage device negative pole, it is characterised in that fill lithium ion aqueous solution in anode chamber,
Cathode chamber is connected with anode chamber, using the ceramic base solid electrolyte film being placed in inside cathode chamber as lithium ion transport
Window, selective prevention hydrone, proton, the ion of hydrated and solvation pass through；Be covered on lithium cell cathode material and
Gel polymer electrolyte between ceramic base solid electrolyte film provides good conduction for lithium ion；By negative electrode stainless steel
Bolt is connected with the working electrode interface of electrochemical workstation, the titanium of inert electrode or sacrificial electrode will be loaded with anode chamber
Collector is connected with electrochemical workstation to electrode interface, by ginseng of the silver/silver chloride reference electrode with electrochemical workstation
It is connected than electrode interface, uses the prefabricated lithium of negative pole that the electrochemical method of constant cathode electric current is lithium ion.
Further, use the cathode-current density after the area normalization of ceramic base solid electrolyte film for 1~
40A/m2, the time required to the shortest time of prefabricated lithium is negative material Surface Creation SEI films, maximum duration is to reach negative material
The time required to the biggest quality specific capacity of initial prefabrication lithium.
A kind of lithium-ion energy storage device of negative pole composition after prefabricated lithium of method by prefabricated lithium of the present invention, it is special
Levy and be, the negative pole after the prefabricated lithium of method of prefabricated lithium of the present invention is matched with positive pole, lithium-ion energy storage is assembled into
Device, the positive electrode used be activated carbon, transition group metallic oxide, sulfenyl, air, oxygen, LiMn2O4, cobalt acid lithium,
LiFePO4 or tertiary cathode material.
Compared with prior art, first, the cathode of electrolytic tank uses lithium to the electrolytic cell device of prefabricated lithium of the present invention
Ion half-cell type is designed, and lithium cell cathode material and ceramic base solid electrolyte film are covered on gel polymer electrolyte
Between there is provided good ionic conduction, gel polymer electrolyte can load full electricity together with cathode of lithium battery after prefabricated lithium
Pond, manufactures poly-lithium battery.Secondly, the electrolytic cell anode is used as electrolyte and lithium source, the lithium source using lithium ion aqueous solution
Materials are extensive, can be lithium bittern or the waste lithium cell lithium recovery aqueous solution, environment-friendly, nontoxic, chemical property is stable, is not required to
Strict storage and transporting equipment are wanted, the cost of prefabricated lithium is reduced.Using inert electrode, generation oxygen or chlorine can be collected
Utilize, the hydrogen ion generated in electrolyte can add alkali to neutralize, electrolyte recycling.Using sacrificial electrode, the metal of generation
Salting liquid can carry out recycling by the method for chemical precipitation.Again, the negative electrode of the electrolytic cell and anode are using ceramics
Base solid electrolyte is used to completely cut off air and water enters negative electrode, and the ceramic base solid electrolyte manufacturing process is ripe, without expensive
Metal, is encapsulated into after electrolytic cell, may be reused, and reduce further the cost of prefabricated lithium.The ceramic base solid electrolyte
It is the insulator of electronics, effectively prevent short-circuit generation during prefabricated lithium, eliminate potential safety hazard.The ceramic base solid-state
Chemical property of the electrolyte in organic electrolyte is stable, will not make prefabricated lithium process with electrolyte and additive spontaneous reaction
Controllability enhancing.Finally, the electrochemical process of prefabricated lithium is easy to control the electricity of prefabricated lithium using three electrodes and the method for constant current
Pressure, electric current and time, it is easy to control the stoichiometry of prefabricated lithium.
The electrolytic cell device of prefabricated lithium of the present invention is (i.e. ceramic by lithium ion conducting window after engineering amplification
Base solid electrolyte) cathode of electrolytic tank end is encapsulated in, prevent moisture from oozing out, lithium ion aqueous solution passes in and out the moon at a flow way
Pole, installing aqueous solution recycling system, there is provided enough lithium sources.And the device of prefabricated lithium is integrated into manufacture energy storage device
It is further cost-effective in streamline.
The method of prefabricated lithium of the present invention, does not use lithium metal, lithium source is more extensively, cheaply in the process of prefabricated lithium
With it is environment-friendly；The process control of prefabricated lithium is strong；High safety, is prevented effectively from the generation of prefabricated lithium short-circuit conditions.It is described pre-
The electrolytic cell device and method of lithium processed can be widely used for the prefabricated lithium of integrated circuit micro cell, the prefabricated lithium of lithium-ion capacitor, or
Negative electrode of lithium ion battery chemical conversion and lithiumation etc., are carried to manufacture safer, environment-friendly and Large Copacity lithium-ion energy storage equipment
Technical strategies are supplied.
Negative pole after the prefabricated lithium of method of prefabricated lithium of the present invention is matched with positive pole, lithium-ion energy storage is assembled into
Device, shows higher specific discharge capacity and preferable cycle performance.It is assembled into the positive pole that lithium-ion energy storage device is used
Material is the oxide of activated carbon, transition group metallic oxide, such as vanadium, manganese, iron or cobalt, sulfenyl, air or oxygen, LiMn2O4,
Cobalt acid lithium, LiFePO4 or tertiary cathode material etc..
Brief description of the drawings
Fig. 1 is the schematic diagram of the electrolytic cell device of the present invention for being the prefabricated lithium of lithium-ion energy storage device negative pole.
Continuity schematic device after electrolytic cell engineering described in Fig. 2.
Fig. 3 is to the curve of the prefabricated lithium of silicon substrate cathode of lithium battery constant current in example 1 using Novel electrolytic tank.
Fig. 4 is the first charging and discharging curve for the full battery of manganese oxide/silicon lithium ion tested in example 1, and the negative pole is use
Silicon substrate cathode of lithium battery after the prefabricated lithium of new method.Show higher specific discharge capacity.
Fig. 5 is the first charging and discharging curve for the full battery of sulphur/silicon lithium ion tested in example 2, and the negative pole is using new side
Silicon substrate cathode of lithium battery after the prefabricated lithium of method.
Fig. 6 is to the curve of the prefabricated lithium of silicon substrate cathode of lithium battery constant current in example 1 using Novel electrolytic tank.
Fig. 7 is the first charging and discharging curve for the LiMn2O4/full battery of manganese oxide lithium ion tested in example 3, and the negative pole is
Using the manganese oxide base cathode of lithium battery after the prefabricated lithium of new method.
Fig. 8 is the cycle performance for the LiMn2O4/full battery of manganese oxide lithium ion tested in example 3.
Fig. 9 is the first charging and discharging curve for the LiMn2O4/full battery of manganese oxide lithium ion tested in example 4, and the negative pole is
Using the manganese oxide base cathode of lithium battery after the prefabricated lithium of new method.
Figure 10 is the cycle performance for the LiMn2O4/full battery of manganese oxide lithium ion tested in example 4.
In figure：1st, negative material, 2, gel polymer electrolyte, 3, ceramic base solid electrolyte film, 4, stainless steel spiral shell
Cap cathode chamber, 5, epoxy resin, 6, negative electrode glass sock, 7, stainless steel bolt, 8, rubber ring, 9, rubber ring, 10, fill lithium ion
The glass anode chamber of the aqueous solution, 11, silver/silver chloride reference electrode, 12, titanium collector, 13, inert electrode or sacrificial electrode, 14,
Protective gas breather pipe.
Embodiment
Below in conjunction with the accompanying drawings and specific embodiment the present invention is further illustrated, but protection scope of the present invention is simultaneously
Not limited to this.
As shown in figure 1, the electrolytic cell device of the present invention for the prefabricated lithium of lithium-ion energy storage device negative pole, mainly includes
Two parts of cathode half-cell and anodic half-cell.The cathode half-cell includes cathode chamber 4, the lithium electricity being placed in cathode chamber 4
Pond negative material 1, gel polymer electrolyte 2, ceramic base solid electrolyte film 3, and it is wrapped in the moon outside cathode chamber 4
Pole glass sock 6.The outside negative electrode glass sock 6 of cathode chamber, which is wrapped up, to be caused on the outside of cathode chamber waterproof and is electrically insulated.The cathode chamber 4
One end has through hole, and the ceramic base solid electrolyte film 3 is located at the through hole of cathode chamber 4 and between the cathode chamber 4
Epoxy resin 5 is set to be sealed, to prevent air and water from entering in cathode chamber 4,.The ceramic base solid electrolyte film
3 be oxide system NASICON type glass ceramics solid electrolytes, and its component includes lithium, aluminium, titanium, silicon, phosphorus, germanium and oxygen.Ceramics
Base solid electrolyte film is as the window of lithium ion transport, and hydrone, proton, the ion of hydrated and solvation can not lead to
Cross.The gel polymer electrolyte 2 is located between negative material 1, ceramic base solid electrolyte film 3, the gel polymerisation
Thing electrolyte is the gel-type system being composited by polymer, three kinds of components of electrolytic salt and small molecular organic solvent.Specifically
, the cathode chamber 4 is made up of stainless steel bolt and STAINLESS STEEL NUTS, and one end of the STAINLESS STEEL NUTS has annular end face,
The stainless steel bolt screws in the other end of the STAINLESS STEEL NUTS, and the bottom of the bolt is covered on negative material 1.Stainless steel
The junction of bolt and negative electrode glass sock is sealed using the first rubber ring 8, to prevent air and water from entering cathode chamber 4.
The anodic half-cell includes the glass anode chamber 10 equipped with lithium ion aqueous solution, is placed in the anode chamber 10
Silver/silver chloride reference electrode 11, titanium collector 12, inert electrode or sacrificial electrode 13, the protection gas 14；The glass anode
Room 10 is tubulose, and one end of the glass anode chamber 10 is connected with the through hole of the end of cathode chamber 4, the glass anode
The second rubber ring 9 is set to seal between room 10 and the cathode chamber 4, the spilling for preventing lithium ion aqueous solution.The glass
Lithium ion aqueous solution in anode chamber 10 is the aqueous solution, the aqueous solution of lithium sulfate, the aqueous solution of lithium chloride, the perchloric acid of lithium nitrate
The lithium of the aqueous solution of lithium, the bittern of lithium or waste lithium cell reclaims the aqueous solution.The bottom of the anode chamber 10 is provided with protective gas
Breather pipe 14, is passed through nitrogen, argon gas or carbon dioxide, for stirring lithium ion aqueous solution so that in electricity to the anode chamber 10
The concentration of the lithium ion of solution in chemical process is more uniform.
Embodiment 1
For for the prefabricated lithium of silicon substrate lithium cell cathode material, first by electrolytic cell device of the present invention according to Fig. 1 groups
Dress.First, the negative electrode of electrolytic cell is assembled in the glove box full of argon gas, the gel electrolyte used is 3 for infiltration volume ratio:
7 1M LiPF6PVDF/PMMA/PVDF in EC/DE C organic electrolytes, is placed in STAINLESS STEEL NUTS, and be covered on
Ceramic base solid electrolyte film, the ceramic base solid electrolyte film used is Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2
Glass ceramic film.Silicon-based anode is covered on gel electrolyte, screwed after stainless steel bolt.Then by the same glass of cathode of electrolytic tank
Glass anode assembling is to together, using the second seal with elastometic washer.Ag/AgCl reference electrodes and the titanium rod for being wound with copper cash are placed in glass
Glass anode, 0.5MLi is poured into glass anode2SO4The aqueous solution, and argon gas is passed through, device assembling is finished.It is with wire that negative electrode is stainless
Steel bolt is connected with the working electrode interface of electrochemical workstation, and titanium rod is connected with to electrode interface, Ag/AgCl is joined
It is connected than electrode with reference electrode interface.Using constant cathode electric current to the prefabricated lithium of silicon-based anode, using ceramic base solid-state electricity
Solve after the thin area normalization of matter, cathode-current density is 2A/m2, the time of prefabricated lithium is 4.2 hours, and the silicon-based anode is new
The curve of the prefabricated lithium of constant current is shown in Fig. 3 in type electrolytic cell.After prefabricated lithium terminates, negative electrode is opened in glove box, after prefabricated lithium
Silicon-based anode and gel polymer electrolyte are taken out together, and battery, both positive and negative polarity active material are helped with oxidation manganese-based anode assembling
Mass ratio be 6:1, volume ratio is used for 3:7 1M LiPF6EC/DEC is used as organic electrolyte.The full battery is in C/10 (1
C=150mA/g, by both positive and negative polarity active material gross mass calculate) under initial discharge specific discharge capacity be 249mAh/g, see figure
It is the 50% of initial capacity after 4,0.5C circulations 100 times.
Embodiment 2
For for the prefabricated lithium of silicon substrate lithium cell cathode material, the present apparatus is assembled according to Fig. 1 first.First, full of argon
The negative electrode of electrolytic cell is assembled in the glove box of gas, the gel electrolyte used is 3 in volume ratio for infiltration:7 1M LiPF6EC/
PVDF/PMMA/PVDF in DEC organic electrolytes, is placed in STAINLESS STEEL NUTS, and is covered on ceramic base solid state electrolysis
Matter film, the ceramic base solid electrolyte film used is Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2Glass ceramic film.By silicon
Base negative pole is covered on gel electrolyte, is screwed after stainless steel bolt.Then by cathode of electrolytic tank with glass anode assembling to one
Rise, using the second seal with elastometic washer.Ag/AgCl reference electrodes and the titanium rod for being wound with copper cash are placed in glass anode, to glass
Anode pours into 0.5MLi2SO4The aqueous solution, and argon gas is passed through, device assembling is finished.With wire by negative electrode stainless steel bolt with electrification
The working electrode interface for learning work station is connected, and titanium rod is connected with to electrode interface, by the same reference of Ag/AgCl reference electrodes
Electrode interface is connected.Using constant cathode electric current to the prefabricated lithium of silicon-based anode, using the thin area of ceramic base solid electrolyte
Cathode-current density after normalization is 2A/m2, the time of prefabricated lithium is 5.2 hours.After prefabricated lithium terminates, beaten in glove box
Negative electrode is opened, the silicon-based anode after prefabricated lithium is taken out, battery, the mass ratio of both positive and negative polarity active material are helped with sulfur-based positive electrode assembling
For 2:1, using volume ratio 3:7 organic electrolyte 1M LiPF6EC/DEC.The full battery (presses both positive and negative polarity active matter in 33mA/g
The gross mass of matter is calculated) under initial discharge specific discharge capacity be 693mAh/g, see Fig. 5.
Embodiment 3
For for the prefabricated lithium of manganese oxide base lithium cell cathode material, the present apparatus is assembled according to Fig. 1 first.First, filling
The negative electrode of electrolytic cell is assembled in the glove box of full argon gas, the gel electrolyte used is infiltration in volume ratio 3:7 1M LiPF6
PVDF/PMMA/PVDF in EC/DEC organic electrolytes, is placed in STAINLESS STEEL NUTS, and is covered on ceramics
Base solid electrolyte film, the ceramic base solid electrolyte film used is Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2Glass
Ceramic membrane.Manganese oxide base negative pole is covered on gel electrolyte, screwed after stainless steel bolt.Then by the same glass of cathode of electrolytic tank
Glass anode assembling is to together, using seal with elastometic washer.Ag/AgCl reference electrodes and the titanium rod for being wound with copper cash are placed in glass sun
Pole, 0.5MLi is poured into glass anode2SO4The aqueous solution, and argon gas is passed through, device assembling is finished.With wire by negative electrode stainless steel spiral shell
Bolt is connected with the working electrode interface of electrochemical workstation, and titanium rod is connected with to electrode interface, by Ag/AgCl references electricity
Extremely it is connected with reference electrode interface.Using constant cathode electric current to the prefabricated lithium of silicon-based anode, cathode-current density is 4A/m2
(after the thin area normalization of ceramic base solid electrolyte), the time of prefabricated lithium is 42min.The manganese oxide base negative pole is new
The curve of the prefabricated lithium of constant current is shown in Fig. 6 in type electrolytic cell.After prefabricated lithium terminates, negative electrode is opened in glove box, after prefabricated lithium
Manganese oxide base negative pole takes out, and helps battery with the assembling of LiMn2O4 base positive pole, the mass ratio of both positive and negative polarity active material is 5:1, use
Volume ratio 3:7 obtain 1M LiPF6EC/DEC organic electrolytes.The full battery (presses total matter of both positive and negative polarity active material in 33mA/g
Amount calculate) under initial discharge specific discharge capacity be 57mAh/g, see Fig. 7.It is the 47% of initial capacity after circulating 100 times, sees figure
8。
Embodiment 4
For the prefabricated lithium of metal aluminum foil negative pole, using the continuity device after engineering, as shown in Figure 2.First, this is continuous
Property device run under protective atmosphere, the gel electrolyte used be infiltration in volume ratio 3:7 1M LiPF6EC/DEC is organic
The ceramic base solid electrolyte film used in PVDF/PMMA/PVDF in electrolyte, lithium ion window is Li2O-Al2O3-
SiO2-P2O5-TiO2-GeO2Oxygen electrode is analysed using titanium oxide inertia by glass ceramic film, anode chamber, and lithium source is 0.5 M Li2SO4
The aqueous solution.By roll-to-roll mode, gel electrolyte is covered on metal aluminum foil negative pole, lithium ion beneath window is entered.
Lithium ion window, which is pushed, to be pasted with gel electrolyte, turn-on current between oxygen anodes and aluminium foil is analysed in inertia, and cathode current is close
Spend for 40A/m2(after the thin area normalization of ceramic base solid electrolyte), the time of prefabricated lithium is 4min.Prefabricated lithium knot
Lifted on Shu Hou, lithium ion window, the aluminium foil section after prefabricated lithium removes lithium ion window region with roller, pastes and is assembled into carbon-based positive pole
Full battery, using volume ratio 3:7 obtain 1M LiPF6EC/DEC organic electrolytes.The full battery is in 100mA/g (by both positive and negative polarity activity
The gross mass of material is calculated) under initial discharge specific discharge capacity be 150mAh/g, see Fig. 9.It is initial hold after circulating 2000 times
The 97% of amount is shown in Figure 10.
For the present invention preferred embodiment, but the present invention is not limited to above-mentioned embodiment to the embodiment, not
In the case of the substantive content of the present invention, any conspicuously improved, replacement that those skilled in the art can make
Or modification belongs to protection scope of the present invention.
Claims (10)
1. a kind of electrolytic cell device for the prefabricated lithium of lithium-ion energy storage device negative pole, mainly includes cathode half-cell and the electricity of anode half
Two, pond part, it is characterised in that：The cathode half-cell includes cathode chamber (4), the cathode of lithium battery being placed in cathode chamber (4)
Material (1), gel polymer electrolyte (2), ceramic base solid electrolyte film (3), and it is wrapped in cathode chamber (4) outside
Negative electrode glass sock (6)；Described cathode chamber (4) one end has through hole, and the ceramic base solid electrolyte film (3) is located at cathode chamber
(4) through hole and epoxy resin (5) is set to be sealed between the cathode chamber (4), the gel polymer electrolyte
(2) it is located between negative material (1), ceramic base solid electrolyte film (3), the gel polymer electrolyte is by polymerizeing
The gel-type system that thing, three kinds of components of electrolytic salt and small molecular organic solvent are composited；The ceramic base solid electrolyte
Film (3) is oxide system NASICON type glass ceramics solid electrolytes；
The anodic half-cell includes the glass anode chamber (10) equipped with lithium ion aqueous solution, is placed in the anode chamber (10)
Silver/silver chloride reference electrode (11), titanium collector (12), inert electrode or sacrificial electrode (13), the protection gas (14)；It is described
Glass anode chamber (10) is tubulose, and one end of the glass anode chamber (10) is connected with the through hole of the cathode chamber (4) end,
The bottom of the anode chamber (10) is provided with protective gas breather pipe (14).
2. electrolytic cell device according to claim 1, it is characterised in that：The lithium ion aqueous solution is water-soluble for lithium nitrate
Liquid, the aqueous solution of lithium sulfate, the aqueous solution of lithium chloride, the aqueous solution of lithium perchlorate, the lithium of the bittern of lithium or waste lithium cell are returned
Receive the aqueous solution.
3. electrolytic cell device according to claim 1, it is characterised in that：The inert electrode includes carbon paper, analysis oxygen metal
Oxide, the analysis oxygen metal oxide is titanium, zirconium, ruthenium, iridium, tin, the oxide of tantalum or wherein two or more oxide
Mixture；Electrochemical corrosion can occur in saline solution for the sacrificial electrode, be zinc, iron, tin, lead or copper.
4. electrolytic cell device according to claim 1, it is characterised in that：The glass anode chamber (10) and the cathode chamber
(4) the second rubber ring (9) is set to seal between, the junction of stainless steel bolt and negative electrode glass sock uses the first rubber ring (8)
Sealed.
5. electrolytic cell device according to claim 1, it is characterised in that：The cathode chamber (4) is by stainless steel bolt and not
The steel nut that becomes rusty is constituted, and one end of the STAINLESS STEEL NUTS has annular end face, and the stainless steel bolt screws in the stainless steel spiral shell
The other end of cap, the bottom of the bolt is covered on negative material (1).
6. electrolytic cell device according to claim 1, it is characterised in that：The negative material is graphite, silicon, germanium, tin, gold
Belong to oxide, silicon-base alloy, acieral or kamash alloy；The metal oxide be germanium, tin, titanium, vanadium, manganese, iron, cobalt, nickel,
The oxide of molybdenum or tungsten.
7. electrolytic cell device according to claim 1, it is characterised in that：Polymer in the gel polymer electrolyte
For polyoxyethylene, polymethyl methacrylate, polyacrylonitrile or polyvinylidene fluoride, the electrolytic salt be lithium hexafluoro phosphate,
Tetrafluoride lithium borate, lithium perchlorate, trifluoromethanesulfonic acid lithium, double trifluoromethanesulfonimide lithiums or biethyl diacid lithium borate, it is described
Small molecular organic solvent be dimethyl carbonate, diethyl carbonate, ethylene carbonate, propene carbonate, 1,3- dioxolanes or
1,2- dimethoxy-ethanes.
8. electrolytic cell device according to claim 1 is the method for the prefabricated lithium of lithium-ion energy storage device negative pole, its feature exists
In, lithium ion aqueous solution is filled in anode chamber, cathode chamber is connected with anode chamber, it is solid using the ceramic base being placed in inside cathode chamber
State electrolytic thin-membrane is used as the window of lithium ion transport, the selective ion for preventing hydrone, proton, hydrated and solvation
Pass through；The gel polymer electrolyte being covered between lithium cell cathode material and ceramic base solid electrolyte film is lithium ion
Good conduction is provided；Negative electrode stainless steel bolt (7) is connected with the working electrode interface of electrochemical workstation, by anode chamber
In be loaded with inert electrode or the titanium collector (12) of sacrificial electrode (13) is connected with electrochemical workstation to electrode interface,
Silver/silver chloride reference electrode is connected with the reference electrode interface of electrochemical workstation, the electrification of constant cathode electric current is used
Method is the prefabricated lithium of negative pole of lithium ion.
9. the method for prefabricated lithium according to claim 8, it is characterised in that using ceramic base solid electrolyte film (3)
Area normalization after cathode-current density be 1~40A/m2, the shortest time of prefabricated lithium is negative material Surface Creation SEI
The time required to film, the time required to maximum duration is the biggest quality specific capacity for reaching negative material initial prefabrication lithium.
10. the lithium-ion energy storage device of the negative pole composition after the prefabricated lithium of method of prefabricated lithium according to claim 9, it is special
Levy and be, the negative pole after the prefabricated lithium is matched with positive pole, lithium-ion energy storage device is assembled into, the positive electrode used
It is activated carbon, transition group metallic oxide, sulfenyl, air, oxygen, LiMn2O4, cobalt acid lithium, LiFePO4 or tertiary cathode material
Material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710155541.5A CN106972192A (en) | 2017-03-16 | 2017-03-16 | For the method and electrolytic cell device, lithium-ion energy storage device of the prefabricated lithium of lithium-ion energy storage device negative pole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710155541.5A CN106972192A (en) | 2017-03-16 | 2017-03-16 | For the method and electrolytic cell device, lithium-ion energy storage device of the prefabricated lithium of lithium-ion energy storage device negative pole |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106972192A true CN106972192A (en) | 2017-07-21 |
Family
ID=59328546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710155541.5A Pending CN106972192A (en) | 2017-03-16 | 2017-03-16 | For the method and electrolytic cell device, lithium-ion energy storage device of the prefabricated lithium of lithium-ion energy storage device negative pole |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106972192A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109755474A (en) * | 2018-12-29 | 2019-05-14 | 三明学院 | A kind of the benefit lithium method and benefit lithium device of lithium ion battery negative material |
| CN110106369A (en) * | 2019-05-06 | 2019-08-09 | 清华大学 | Elemental lithium extracting method and device based on lithium ion solid electrolyte |
| CN111342121A (en) * | 2020-02-10 | 2020-06-26 | 江苏大学 | Pre-lithiated polyphenylene sulfide with high solid lithium solubility, and preparation method and application thereof |
| WO2021119310A1 (en) * | 2019-12-10 | 2021-06-17 | Alpha-En Corporation | Pre-lithiated electrode |
| CN114551818A (en) * | 2021-07-08 | 2022-05-27 | 万向一二三股份公司 | Nano silicon composite particle, negative plate and solid lithium battery |
| CN115029734A (en) * | 2022-05-19 | 2022-09-09 | 上海交通大学 | Integrated device for extracting lithium from salt lake and measuring lithium based on garnet type solid electrolyte |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000054175A (en) * | 1998-07-31 | 2000-02-22 | Mitsubishi Heavy Ind Ltd | Solid polymer membrane-type water electrolyzer |
| CN101018893A (en) * | 2004-09-14 | 2007-08-15 | 巴斯福股份公司 | Electrolysis cell for producing alkali metal |
| CN103556181A (en) * | 2013-10-28 | 2014-02-05 | 奉新赣锋锂业有限公司 | Metallic lithium electrolytic cell |
| CN104201320A (en) * | 2014-09-16 | 2014-12-10 | 赵前永 | Method for pre-lithiating electrode material of lithium ion battery |
-
2017
- 2017-03-16 CN CN201710155541.5A patent/CN106972192A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000054175A (en) * | 1998-07-31 | 2000-02-22 | Mitsubishi Heavy Ind Ltd | Solid polymer membrane-type water electrolyzer |
| CN101018893A (en) * | 2004-09-14 | 2007-08-15 | 巴斯福股份公司 | Electrolysis cell for producing alkali metal |
| CN103556181A (en) * | 2013-10-28 | 2014-02-05 | 奉新赣锋锂业有限公司 | Metallic lithium electrolytic cell |
| CN104201320A (en) * | 2014-09-16 | 2014-12-10 | 赵前永 | Method for pre-lithiating electrode material of lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| HAITAO ZHOU ET AL: "Li-Metal-Free Prelithiation of Si-Based Negative Electrodes for Full Li-Ion Batteries", 《CHEMSUSCHEM》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109755474A (en) * | 2018-12-29 | 2019-05-14 | 三明学院 | A kind of the benefit lithium method and benefit lithium device of lithium ion battery negative material |
| CN110106369A (en) * | 2019-05-06 | 2019-08-09 | 清华大学 | Elemental lithium extracting method and device based on lithium ion solid electrolyte |
| CN110106369B (en) * | 2019-05-06 | 2020-10-16 | 清华大学 | Lithium ion solid electrolyte-based lithium element extraction method and device |
| WO2021119310A1 (en) * | 2019-12-10 | 2021-06-17 | Alpha-En Corporation | Pre-lithiated electrode |
| CN111342121A (en) * | 2020-02-10 | 2020-06-26 | 江苏大学 | Pre-lithiated polyphenylene sulfide with high solid lithium solubility, and preparation method and application thereof |
| CN111342121B (en) * | 2020-02-10 | 2022-03-11 | 江苏镇江固利纳新能源科技合伙企业(有限合伙) | Pre-lithiated polyphenylene sulfide with high solid lithium solubility, and preparation method and application thereof |
| CN114551818A (en) * | 2021-07-08 | 2022-05-27 | 万向一二三股份公司 | Nano silicon composite particle, negative plate and solid lithium battery |
| CN114551818B (en) * | 2021-07-08 | 2023-10-03 | 万向一二三股份公司 | Nano silicon composite particles, negative plate and solid lithium battery |
| CN115029734A (en) * | 2022-05-19 | 2022-09-09 | 上海交通大学 | Integrated device for extracting lithium from salt lake and measuring lithium based on garnet type solid electrolyte |
| CN115029734B (en) * | 2022-05-19 | 2024-04-16 | 上海交通大学 | Integrated device for extracting lithium from salt lake and measuring lithium based on garnet type solid electrolyte |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106972192A (en) | For the method and electrolytic cell device, lithium-ion energy storage device of the prefabricated lithium of lithium-ion energy storage device negative pole | |
| US20220263336A1 (en) | Rechargeable aluminum ion battery | |
| CN208637537U (en) | A kind of solid state battery of low interfacial resistance | |
| CN105098291B (en) | Liquid metal gas cell and preparation method thereof | |
| CN104201320A (en) | Method for pre-lithiating electrode material of lithium ion battery | |
| CN103199224B (en) | The preparation method of a kind of lithium sulfur battery anode material and using method thereof | |
| JP2017059342A (en) | All-solid battery manufacturing method | |
| CN104037468B (en) | A kind of method reclaiming manganese and copper resource from waste and old lithium ion battery | |
| CN104795567B (en) | Aquo-lithium ion/sodium-ion battery based on iodide ion solution anode and organic matter cathode | |
| CN108039454A (en) | A kind of preparation method of lithium anode, lithium anode and lithium battery | |
| CN107017450A (en) | Aluminium-air cell | |
| CN107069133B (en) | A kind of method of lithium in recycling lithium cell cathode material | |
| CN102157753A (en) | Fast-charging high-power winding column type lithium ion battery | |
| CN102130359A (en) | Lithium sulfur battery and preparation method thereof | |
| CN105206856A (en) | Novel lithium ion flow cell | |
| CN108711636A (en) | A kind of combination electrolyte double ion rocking chair type secondary cell and preparation method thereof | |
| CN106532145A (en) | Liquid metal battery | |
| CN102356498A (en) | Non-aqueous electrolyte secondary battery, and method for charging same | |
| CN105006600A (en) | Magnesium alloy storage battery | |
| CN110957467B (en) | Bromine ion battery | |
| Vayenas et al. | Investigation of alternative materials as bifunctional catalysts for electrochemical applications | |
| CN105671363B (en) | A kind of antimony-containing alloy material and its application | |
| CN104610569B (en) | A kind of preparation method of sodium-sulphur battery and its barrier film | |
| JP2010086924A (en) | Magnesium air secondary battery | |
| JP4433021B2 (en) | Non-aqueous electrolyte battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170721 |