CN109768334A - Preparation method of bipolar solid-state lithium secondary battery - Google Patents
Preparation method of bipolar solid-state lithium secondary battery Download PDFInfo
- Publication number
- CN109768334A CN109768334A CN201811590375.2A CN201811590375A CN109768334A CN 109768334 A CN109768334 A CN 109768334A CN 201811590375 A CN201811590375 A CN 201811590375A CN 109768334 A CN109768334 A CN 109768334A
- Authority
- CN
- China
- Prior art keywords
- lithium
- solid
- bipolarity
- preparation
- lithium secondary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 52
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000007787 solid Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims description 22
- -1 polypropylene carbonate Polymers 0.000 claims description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 9
- 239000005030 aluminium foil Substances 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 9
- 159000000002 lithium salts Chemical class 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000006258 conductive agent Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000011888 foil Substances 0.000 claims description 7
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000000231 atomic layer deposition Methods 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 239000011256 inorganic filler Substances 0.000 claims description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229920001610 polycaprolactone Polymers 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 5
- 210000002469 basement membrane Anatomy 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 5
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 claims description 4
- 229910006194 Li1+xAlxGe2-x(PO4)3 Inorganic materials 0.000 claims description 4
- 229910006196 Li1+xAlxGe2−x(PO4)3 Inorganic materials 0.000 claims description 4
- 229910009218 Li1.3Ti1.7Al0.3(PO4)3 Inorganic materials 0.000 claims description 4
- 229910011244 Li3xLa2/3-xTiO3 Inorganic materials 0.000 claims description 4
- 229910011245 Li3xLa2/3−xTiO3 Inorganic materials 0.000 claims description 4
- 229910010685 Li5La3M2O12 Inorganic materials 0.000 claims description 4
- 229910010092 LiAlO2 Inorganic materials 0.000 claims description 4
- 229910015694 LiNi0.85Co0.1Al0.05O2 Inorganic materials 0.000 claims description 4
- 229910012305 LiPON Inorganic materials 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 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
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 229910015965 LiNi0.8Mn0.1Co0.1O2 Inorganic materials 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 238000007731 hot pressing Methods 0.000 claims description 3
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 238000005240 physical vapour deposition Methods 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 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
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002449 FKM Polymers 0.000 claims description 2
- 229910000733 Li alloy Inorganic materials 0.000 claims description 2
- 229910009297 Li2S-P2S5 Inorganic materials 0.000 claims description 2
- 229910009228 Li2S—P2S5 Inorganic materials 0.000 claims description 2
- 229910011671 Li4-xGe1-xPxS4 Inorganic materials 0.000 claims description 2
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 claims description 2
- 229910011572 Li4−xGe1−xPxS4 Inorganic materials 0.000 claims description 2
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 2
- 229910010941 LiFSI Inorganic materials 0.000 claims description 2
- 229910001305 LiMPO4 Inorganic materials 0.000 claims description 2
- 229910012406 LiNi0.5 Inorganic materials 0.000 claims description 2
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims description 2
- 229910011322 LiNi0.6Mn0.2Co0.2O2 Inorganic materials 0.000 claims description 2
- 229910014422 LiNi1/3Mn1/3Co1/3O2 Inorganic materials 0.000 claims description 2
- 229910003005 LiNiO2 Inorganic materials 0.000 claims description 2
- 229910013179 LiNixCo1-xO2 Inorganic materials 0.000 claims description 2
- 229910013171 LiNixCo1−xO2 Inorganic materials 0.000 claims description 2
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000000443 aerosol Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 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
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-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
- 238000005566 electron beam evaporation Methods 0.000 claims description 2
- 238000004110 electrostatic spray deposition (ESD) technique Methods 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 238000001659 ion-beam spectroscopy Methods 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920000867 polyelectrolyte Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 150000003233 pyrroles Chemical class 0.000 claims description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 230000003319 supportive effect Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011366 tin-based material Substances 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- IDGCBXSROJHVOG-UHFFFAOYSA-N [Li].[SH2]=N.[F] Chemical compound [Li].[SH2]=N.[F] IDGCBXSROJHVOG-UHFFFAOYSA-N 0.000 claims 1
- 239000007767 bonding agent Substances 0.000 claims 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- 229960002645 boric acid Drugs 0.000 claims 1
- 235000010338 boric acid Nutrition 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229920006184 cellulose methylcellulose Polymers 0.000 claims 1
- 239000000945 filler Substances 0.000 claims 1
- 235000006408 oxalic acid Nutrition 0.000 claims 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims 1
- 239000007784 solid electrolyte Substances 0.000 abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- 238000005234 chemical deposition Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000011244 liquid electrolyte Substances 0.000 abstract 1
- 238000005289 physical deposition Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000011261 inert gas Substances 0.000 description 6
- 230000005611 electricity Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- XJGIGXYFHBOWDQ-UHFFFAOYSA-N B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+].[F] Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+].[F] XJGIGXYFHBOWDQ-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- OQPHEVHDBFEJRQ-UHFFFAOYSA-N [Li].P(O)(O)(O)=O Chemical compound [Li].P(O)(O)(O)=O OQPHEVHDBFEJRQ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000005404 monopole Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a bipolar solid-state lithium secondary battery, belonging to the technical field of chemical power supplies, wherein a used bipolar current collector is a bipolar aluminum copper-plated current collector obtained by a physical or chemical deposition method, and the thickness and the weight of the bipolar current collector are controllable; the solid electrolyte is high ionic conductivity solid electrolyte, and can work at room temperature or low temperature. The solid electrolyte system is used in the bipolar structure battery, so that the problem of internal short circuit caused by liquid electrolyte is effectively avoided, and the bipolar solid lithium secondary battery prepared by the method provided by the invention has the outstanding advantages of controllable voltage, high safety and easiness in large-scale production.
Description
Technical field
The invention belongs to technical field of chemical power, more particularly to a kind of preparation side of bipolarity solid lithium secondary cell
Method.
Background technique
Bipolar structure electrode is by the positive active material of intermediate conducting base and one side and the negative electrode active of another side
Material composition, internal series-connection may be implemented in battery based on this, to regulate and control voltage on demand.Although bipolar electrode is general
Read it is long-standing, but its never by large-scale application in lithium ion battery, mainly limited by electrolyte system.
Since monomeric unit is series relationship inside bipolar battery, the electrolyte of strong mobility and contains more liquid, protects liquid
Property bad conventional gel electrolyte be easy to form electronic conduction access in inside battery, cause internal short-circuit.
The fast-developing large-scale application to bipolar structure battery of solid electrolyte brings hope.Bipolarity solid-state electricity
The advantage in pond includes: that 1. solid electrolyte is instead of traditional electrolyte and diaphragm, and short-circuit problem is eliminated between battery unit；
2. voltage can be regulated and controled on demand, volt not equal from more than ten volts to 1000 (electric current can be equivalent under Same Efficieney demand and drops to original
The 1/10-1/1000 come, and be evenly distributed；Or in the case that electric current is constant, power density is increased dramatically)；3. electronics
Inner heat and the active material extent of reaction and degree of aging is greatly reduced in the shortening of conductive path and the increase of conductive area
Inhomogeneities；4. more efficiently stacking can be obtained between monomer, simplifies process flow, reduces quality, battery is each
The active material surface electric current of component and being uniformly distributed for voltage are advantageously reduced because energy damages caused by connecting between single battery
It loses, promotes the energy density of battery significantly, reduce costs.
Currently, bipolar structure being particularly true in hull cell in solid state battery, heavy by physics or chemistry
Long-pending mode obtains thin layer bipolarity hull cell, but since capacity is effective, limits this kind of battery answering in more areas
With.The present invention passes through the preparation of solid-state electrolyte layer, bipolar electrode, and acquisition voltage is successfully constructed using stacked method can
It adjusts, large capacity bipolarity solid lithium secondary cell.
Summary of the invention
The technical problem to be solved by the invention is to provide a kind of preparation methods of bipolarity solid lithium secondary cell, lead to
The regulation and optimization for crossing solid electrolyte component ratio prepare the solid-state electrolyte layer with more high ionic conductivity, lead to
The preferred acquisition for crossing the composition to bipolar electrode, structure and bipolar current collector has the bipolar electrode of machinability,
Prepare that voltage is adjustable, large capacity bipolarity solid lithium secondary cell using wet coating and stacked method.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is that: a kind of bipolarity solid lithium secondary cell
Preparation method, comprising the following steps:
1) lithium salts, polymer, inorganic filler are mixed in proportion, is dissolved in organic solvent and forms precursor solution, poured
Form film or with the basement membrane that plays a supportive role is compound prepares solid polyelectrolyte；Polymer and lithium salts mass ratio are 1:10-4:
1, inorganic filler adding proportion is the 1%-400% of polymer quality；
2) bipolar current collector is selected, the bipolarity metal tape that aluminium foil and copper foil are combined into is prepared, with a thickness of 13-50
μm；
3) modified positive electrode material or unmodified positive active material, conductive agent, binder are dissolved separately in organic
In solvent, coating obtains unipolarity anode pole piece；
4) negative electrode active material, conductive agent, binder are dissolved separately in organic solvent, coating obtains unipolarity cathode
Pole piece, or metallic lithium foil is compressed on copper current collector, with a thickness of 1-50 μm；
5) side of the uncoated electrode of unipolarity anode pole piece obtained in step 3) is coated with according to method in step 4)
Cathode or compacting lithium foil, obtain bipolar electrode, with a thickness of 80-1000 μm；
6) multi-layer double-pole electrode, solid-state electrolyte layer and monopolar electrode are superimposed in order, assembling bipolarity is solid
State lithium secondary battery, wherein bipolar electrode side of the positive electrode and another bipolar electrode negative side or terminal cathode/unipolarity are negative
Extremely adjacent, centre is inserted with solid-state electrolyte layer, constitutes a monomer；Battery core outermost is terminal anode and terminal cathode/monopole
Property cathode, adjacent thereto is respectively the negative side and side of the positive electrode of bipolar electrode, and centre is inserted with solid-state electrolyte layer, bipolarity
Amount of monomer is no less than 2 inside lithium secondary solid state batteries battery core；
7) flexible package bipolarity lithium secondary solid state batteries are prepared using packaging by hot pressing technique.
The highly polar carbonates polymer of polymeric oxidizer described in step 1), including polyethylene glycol oxide PEO, poly- carbonic acid third
Enester PPC, poly- ethylene carbonate PEC, polytrimethylene carbonate PTMC, the modified macromer list obtained with PEO ring-opening polymerisation
Copolymer p TMC-PCL, the cyanogen that body M-PEOEC, poly-epsilon-caprolactone PCL and monomer and TMC monomer obtain after ring opening copolymer
One of base rubber NBR or multiple combinations.
Lithium salts described in step 1) includes lithium hexafluoro phosphate LiPF6, LiBF4 LiBF4, lithium perchlorate LiClO4, two
Fluorine Lithium bis (oxalate) borate LiODFB, di-oxalate lithium borate LiBOB, two (trimethyl fluoride sulfonyl) imine lithium LiTFSI, double fluorine sulphonyl are sub-
One of amine lithium LiFSI or multiple combinations.
Inorganic filler described in step 1) includes aluminum oxide Al2O3, titanium dioxide TiO2, silica SiO2, phosphoric acid
Lithium Li3PO4, zirconium dioxide ZrO2, silicon nitride Si3N4, magnesia MgO, lithium aluminate LiAlO2, montmorillonite, kaolin, metal it is organic
Frame MOF, Li3xLa2/3-xTiO3、Li5La3M2O12(M=Nb, Ta), Li1.3Ti1.7Al0.3(PO4)3、Li1+xAlxGe2-x(PO4)3、
LiPON、Li4-xGe1-xPxS4、Li7P2S8I、Li2S-P2S5、Li3OX (X=F, Cl, Br, I), LLTO, LLZTO, Li3One in N
Kind or multiple combinations.
Organic solvent described in step 1) is tetrahydrofuran, propene carbonate, dimethyl carbonate, methyl ethyl carbonate, carbonic acid
Diethylester, ethyl acetate, acetonitrile, isopropyl ether, acetone, butanone, isopropanol, butanol, hexane, hexamethylene, N-N dimethylacetamide
One of amine, n-methyl-2-pyrrolidone, benzene, toluene, dimethyl sulfoxide, carbon tetrachloride, tri-chlorination alkene, pyrroles are a variety of
Combination.
Basement membrane described in step 1) includes cellulose, glass fibre, polyimides, polyacrylonitrile, poly-methyl methacrylate
One of ester, polyvinyl alcohol, Pioloform, polyvinyl acetal, polyethylene, polypropylene or multiple combinations.
Unmodified positive electrode described in step 3) includes stratiform LiCoO2、LiNiO2And LiNixCo1-xO2, NCA material
LiNi0.85Co0.1Al0.05O2, ternary LiNi1/3Mn1/3Co1/3O2、LiNi0.8Mn0.1Co0.1O2、LiNi0.6Mn0.2Co0.2O2With
LiNi0.5Mn0.2Co0.3O2, spinelle LiMn2O4, 5V spinelle LiNi0.5Mn1.5O4, phosphate LiMPO4(M=Fe, Mn) and
Lithium-rich manganese-based anode material Li [Lix(MnM)1-x]O2(M=Ni, Co, Fe)；Positive electrode method of modifying is conductive layer in step 3)
Modification, decorative material includes carbon material, aluminum oxide Al2O3, titanium dioxide TiO2, lithium phosphate Li3PO4, zirconium dioxide ZrO2、
Lithium aluminate LiAlO2、Li3xLa2/3-xTiO3、Li5La3M2O12(M=Nb, Ta), Li1.3Ti1.7Al0.3(PO4)3、Li1+xAlxGe2-x
(PO4)3、LiPON、LLTO、LLZTO、Li3One of N or multiple combinations.
Negative electrode material described in step 4) includes lithium metal, lithium alloy LixM (M=In, B, Al, Ga, Sn, Si, Ge, Pb,
As, Bi, Sb, Cu, Ag, Zn), carbon-based material, silica-base material, tin-based material and lithium titanate Li4Ti5O12One of or it is a variety of
Combination, carbon-based material are graphite, amorphous carbon, carbonaceous mesophase spherules, silicon carbon material, and silica-base material is silicon carbon material, nano-silicon.
Conductive agent described in step 3) and step 4) include acetylene black, Super P, Super S, 350G, carbon fiber VGCF,
One or more combinations in carbon nanotube CNTs, Ketjen black, graphite agent and graphene, graphite agent are KS-6, KS-
15,SFG-6,SFG-15；Binder is Kynoar PVdF, polytetrafluoroethylene PTFE, polyethylene glycol oxide PEO, poly- carbonic acid third
Enester PPC, poly- ethylene carbonate PEC, polytrimethylene carbonate PTMC, PVAC polyvinylalcohol, sodium carboxymethylcellulose CMC, gather
One of olefines, cyano rubber NBR, modified SBR, Viton, polyurethane or multiple combinations, polyolefins are poly- second
Alkene, polypropylene and its copolymer, polyolefins are polyethylene, polypropylene and its copolymer.
Bipolar current collector described in step 2) is to be deposited on Cu on Al collector to prepare, and preparation method includes magnetic
Control sputtering, pulse laser deposition, chemical vapor deposition, metal oxide chemical vapor deposition, atomic layer deposition, ion beam sputtering
Plating method, electron beam evaporation method atomization pyrolytic deposition, sol-gel deposition, Electrostatic Spray Deposition, aerosol deposition, chemical plating or object
Reason vapor deposition, the bipolar current collector prepared is with a thickness of 13-50 μm.
The beneficial effects of the present invention are: using solid state electrolysis plastidome in bipolar structure battery, liquid is effectively evaded
State electrolyte bring internal short-circuit problem, provides possibility for the large-scale application of bipolar battery；It effectively controls bipolar
Property collector thickness, and can using lithium metal as cathode, further improve the energy density of battery；Simultaneously as
New Solid electrolyte is used, so that battery can be in room temperature application.The bipolarity solid-state lithium two that the method for the present invention prepares
Primary cell has controllable voltage, high security, the outstanding advantage for being easy to be mass produced.
Detailed description of the invention
Fig. 1 be bipolarity solid lithium secondary cell structure chart of the present invention (wherein 1 is bipolar current collector, and 2 be anode layer, 3
It is solid-state electrolyte layer for negative electrode layer, 4).
Specific embodiment
In order to further understand the content, features and effects of the present invention, the following examples are hereby given, and cooperate attached drawing
Detailed description are as follows:
Embodiment 1
A kind of preparation method of bipolarity solid lithium secondary cell, by bipolar electrode, solid-state electrolyte layer, unipolarity electricity
Pole assembling is laminated in order, solid state battery is made.Specific preparation process:
(1) preparation of bipolar current collector
Cu is deposited using the method for atomic layer deposition ALD in aluminium foil surface, forms bipolar current collector.
Specific preparation process is as follows:
A) vacuum reaction for the aluminium foil for being cut into 10cm × 10cm in advance being placed in atomic layer deposition apparatus is intracavitary, to anti-
Chamber is answered to do vacuumize process；
B) with the hexafluoroacetylacetone complex of copper (Cu (hfac)2) and methanol as preceding aggressiveness, in inert gas Ar
In atmosphere, atomic layer deposition cycles are carried out, depositing temperature is set as 220 DEG C, and pressure is maintained at 10Pa, deposition thickness in reaction chamber
It is 1 μm；
C) after to be deposited, it is filled with inert gas to vacuum reaction is intracavitary, cooled to room temperature is taken out.
(2) preparation of unipolarity anode
By 80g LiNi0.85Co0.1Al0.05O2Anode is mixed with 10g conductive agent SP, is added 10g polypropylene carbonate (PPC)
It with the mixture and 400mlNMP of lithium salts (LiTFSI), stirs 3h and obtains anode sizing agent, coated on aluminium foil, dried at 70 DEG C
Dry, 24 hours dry at 1 hour, 70 DEG C of vacuum dry, single side anode carrying capacity is 15mg/cm2。
(3) preparation of unipolarity cathode
Metallic lithium foil is compressed on the Cu collection liquid surface with a thickness of 6 μm, pressure 6MPa.
(4) preparation of bipolar electrode
According to method in (2), bipolar current collector Al foil side is coated with anode sizing agent in (1), after dry, by lithium metal
It is compressed on the Cu foil side of bipolar current collector, pressure 6MPa, lithium layer is with a thickness of 12 μm.
(5) preparation of solid-state electrolyte layer
4g polypropylene carbonate (PPC) is mixed with 1g lithium salts (LiTFSI), 50mlDMAc solvent is added, is stirred at 70 DEG C
It is uniformly mixed it, 0.8g inorganic filler LLZTO is added, stirring 6 hours to being uniformly dispersed；Cellulose basement membrane is shifted to an earlier date
Well cutting pours electrolyte precursor solution, dries at 70 DEG C, 48 hours dry, obtains high ionic conductivity solid state electrolysis
Matter layer.
(6) preparation of bipolarity solid state battery
A) bipolar electrode side of the positive electrode in (4) and solid electrolyte in (5) is stacked together, it is another in electrolyte layer later
Side is superimposed the negative side of another bipolar electrode；
B) bipolar electrode negative side in a) and solid electrolyte in (5) is stacked together, it is another in electrolyte layer later
The side of the positive electrode of side superposition third piece piece bipolar electrode；
C) it is alternately repeated a) and b)；
D) the multi-layer stacks both ends in c) are superimposed solid-state electrolyte layer in (5) respectively, then folded in electrolyte layer another side
The opposite terminal electrode of additive polarity；
E) packaging by hot pressing obtains bipolarity solid lithium secondary cell.Test cycle performance of battery, voltage range 6V-
8.6V, current density 50mA/g, test temperature are 25 DEG C.
Embodiment 2
A kind of preparation method of bipolarity solid lithium secondary cell, by bipolar electrode, solid-state electrolyte layer, unipolarity electricity
Pole assembling is laminated in order, solid state battery is made.Specific preparation process:
1) preparation of bipolar current collector
Cu is deposited using the method for magnetron sputtering in aluminium foil surface, forms bipolar current collector.
Specific preparation process is as follows:
A) vacuum reaction for the aluminium foil for being cut into 10cm × 10cm in advance being placed in magnetron sputtering apparatus is intracavitary, to reaction
Chamber does vacuumize process；
B) sputtering reaction is carried out in inert gas Ar atmosphere using copper target, reaction temperature is set as room temperature, reaction chamber
Interior pressure is maintained at 0.2Pa, and deposition thickness is 1 μm；
C) after to be sputtered, it is filled with inert gas to vacuum reaction is intracavitary, takes out sample.
The step of step (2)~(6) reference implementation example 1 (2)~(6).
Embodiment 3
A kind of preparation method of bipolarity solid lithium secondary cell, by bipolar electrode, solid-state electrolyte layer, unipolarity electricity
Pole assembling is laminated in order, solid state battery is made.Specific preparation process:
1) preparation of bipolar current collector
Cu is deposited using the method for physical vapor deposition in aluminium foil surface, forms bipolar current collector.
Specific preparation process is as follows:
A) vacuum reaction for the aluminium foil for being cut into 10cm × 10cm in advance being placed in evaporated device is intracavitary, does to reaction chamber
Vacuumize process；
B) using metallic copper as reaction source, in inert gas Ar atmosphere, physical vapor deposition, reaction temperature 1100 are carried out
DEG C, pressure is maintained at 0.001Pa in reaction chamber, and deposition thickness is 2 μm；
C) after to be deposited, it is filled with inert gas to vacuum reaction is intracavitary, cooled to room temperature is taken out.
The step of step (2)~(6) reference implementation example 1 (2)~(6).
Embodiment 4
Step and condition are referring to embodiment 1, the difference is that positive electrode active materials are by LiNi0.85Co0.1Al0.05O2Replacement
For LiNi0.8Mn0.1Co0.1O2。
Embodiment 5
Step and condition are referring to embodiment 1, the difference is that the preparation of (3) unipolarity cathode and (4) bipolar electrode
Preparation, be changed to:
(3) preparation of unipolarity cathode
85g silicon carbon material is mixed with 5g conductive agent SP, 10g polypropylene carbonate (PPC) and lithium salts (LiTFSI) is added
Mixture and 400mlNMP, stirring 3h obtains negative electrode slurry, coated on copper foil, dries at 70 DEG C, 1 hour dry, very
24 hours dry at 70 DEG C empty, single side cathode carrying capacity is 7mg/cm2。
(4) preparation of bipolar electrode
It is coated with anode sizing agent in bipolar current collector Al foil side according to the method in embodiment 1 in (2), after dry,
The Cu foil side of bipolar current collector is coated with negative electrode material, carrying capacity 7mg/cm according to method in (3)2。
Table 1 is bipolarity solid lithium secondary cell cycle performance in 1-5 of the embodiment of the present invention.
| Discharge capacity (milliampere hour) | Voltage range (V) | |
| Embodiment 1 | 3.64 | 6-8.2 |
| Embodiment 2 | 3.35 | 5.9-8.2 |
| Embodiment 3 | 3.75 | 6.1-8.3 |
| Embodiment 4 | 4.50 | 6.2-8.7 |
| Embodiment 5 | 4.89 | 5.0-8.4 |
Embodiment described above is merely to illustrate technical idea and feature of the invention, in the art its object is to make
Technical staff it will be appreciated that the contents of the present invention and implement accordingly, patent model of the invention only cannot be limited with the present embodiment
It encloses, i.e., same changes or modifications made by all disclosed spirit are still fallen in the scope of the patents of the invention.
Claims (10)
1. a kind of preparation method of bipolarity solid lithium secondary cell, which comprises the following steps:
1) lithium salts, polymer, inorganic filler are mixed in proportion, is dissolved in organic solvent and forms precursor solution, poured into
Film or with the basement membrane that plays a supportive role is compound prepares solid polyelectrolyte；Polymer and lithium salts mass ratio are 1:10-4:1, nothing
Machine filler adding proportion is the 1%-400% of polymer quality；
2) bipolar current collector is selected, the bipolarity metal tape that aluminium foil and copper foil are combined into is prepared, with a thickness of 13-50 μm；
3) modified positive electrode material or unmodified positive active material, conductive agent, binder are dissolved separately in organic solvent
In, coating obtains unipolarity anode pole piece；
4) negative electrode active material, conductive agent, binder are dissolved separately in organic solvent, coating obtains unipolarity cathode pole
Piece, or metallic lithium foil is compressed on copper current collector, with a thickness of 1-50 μm；
5) side of the uncoated electrode of unipolarity anode pole piece obtained in step 3) is coated with cathode according to method in step 4)
Or compacting lithium foil, bipolar electrode is obtained, with a thickness of 80-1000 μm；
6) multi-layer double-pole electrode, solid-state electrolyte layer and monopolar electrode are superimposed in order, assemble bipolarity solid-state lithium
Secondary cell, wherein bipolar electrode side of the positive electrode and another bipolar electrode negative side or terminal cathode/unipolarity cathode phase
Neighbour, centre are inserted with solid-state electrolyte layer, constitute a monomer；Battery core outermost is that terminal anode and terminal cathode/unipolarity are negative
Pole, adjacent thereto is respectively the negative side and side of the positive electrode of bipolar electrode, and centre is inserted with solid-state electrolyte layer, bipolarity lithium two
Amount of monomer is no less than 2 inside secondary solid state battery battery core；
7) flexible package bipolarity lithium secondary solid state batteries are prepared using packaging by hot pressing technique.
2. the preparation method of bipolarity solid lithium secondary cell according to claim 1, which is characterized in that described in step 1)
The highly polar carbonates polymer of polymeric oxidizer, including polyethylene glycol oxide PEO, polypropylene carbonate PPC, poly- ethylene carbonate
PEC, polytrimethylene carbonate PTMC, modified macromer monomer M-PEOEC, the poly-epsilon-caprolactone obtained with PEO ring-opening polymerisation
One of copolymer p TMC-PCL, cyano rubber NBR that PCL and monomer and TMC monomer obtain after ring opening copolymer or
Multiple combinations.
3. the preparation method of bipolarity solid lithium secondary cell according to claim 1, which is characterized in that described in step 1)
Lithium salts includes lithium hexafluoro phosphate LiPF6, LiBF4 LiBF4, lithium perchlorate LiClO4, it is difluorine oxalic acid boracic acid lithium LiODFB, double
One of Lithium bis (oxalate) borate LiBOB, two (trimethyl fluoride sulfonyl) imine lithium LiTFSI, double fluorine sulfimide lithium LiFSI or more
Kind combination.
4. the preparation method of bipolarity solid lithium secondary cell according to claim 1, which is characterized in that described in step 1)
Inorganic filler includes aluminum oxide Al2O3, titanium dioxide TiO2, silica SiO2, lithium phosphate Li3PO4, zirconium dioxide
ZrO2, silicon nitride Si3N4, magnesia MgO, lithium aluminate LiAlO2, montmorillonite, kaolin, metal organic frame MOF, Li3xLa2/3- xTiO3、Li5La3M2O12(M=Nb, Ta), Li1.3Ti1.7Al0.3(PO4)3、Li1+xAlxGe2-x(PO4)3、LiPON、Li4-xGe1- xPxS4、Li7P2S8I、Li2S-P2S5、Li3OX (X=F, Cl, Br, I), LLTO, LLZTO, Li3One of N or multiple combinations.
5. the preparation method of bipolarity solid lithium secondary cell according to claim 1, which is characterized in that described in step 1)
Organic solvent be tetrahydrofuran, propene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethyl acetate, acetonitrile,
Isopropyl ether, acetone, butanone, isopropanol, butanol, hexane, hexamethylene, N-N dimethyl acetamide, n-methyl-2-pyrrolidone,
One of benzene, toluene, dimethyl sulfoxide, carbon tetrachloride, tri-chlorination alkene, pyrroles or multiple combinations.
6. the preparation method of bipolarity solid lithium secondary cell according to claim 1, which is characterized in that described in step 1)
Basement membrane includes cellulose, glass fibre, polyimides, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, polyvinyl alcohol
One of acetal, polyethylene, polypropylene or multiple combinations.
7. the preparation method of bipolarity solid lithium secondary cell according to claim 1, which is characterized in that described in step 3)
Unmodified positive electrode includes stratiform LiCoO2、LiNiO2And LiNixCo1-xO2, NCA material LiNi0.85Co0.1Al0.05O2, three
First LiNi1/3Mn1/3Co1/3O2、LiNi0.8Mn0.1Co0.1O2、LiNi0.6Mn0.2Co0.2O2And LiNi0.5Mn0.2Co0.3O2, spinelle
LiMn2O4, 5V spinelle LiNi0.5Mn1.5O4, phosphate LiMPO4(M=Fe, Mn) and lithium-rich manganese-based anode material Li [Lix
(MnM)1-x]O2(M=Ni, Co, Fe)；Positive electrode method of modifying is conductive layer modification in step 3), and decorative material includes carbon materials
Material, aluminum oxide Al2O3, titanium dioxide TiO2, lithium phosphate Li3PO4, zirconium dioxide ZrO2, lithium aluminate LiAlO2、Li3xLa2/3- xTiO3、Li5La3M2O12(M=Nb, Ta), Li1.3Ti1.7Al0.3(PO4)3、Li1+xAlxGe2-x(PO4)3、LiPON、LLTO、
LLZTO、Li3One of N or multiple combinations.
8. the preparation method of bipolarity solid lithium secondary cell according to claim 1, which is characterized in that described in step 4)
Negative electrode material includes lithium metal, lithium alloy LixM (M=In, B, Al, Ga, Sn, Si, Ge, Pb, As, Bi, Sb, Cu, Ag, Zn), carbon
Sill, silica-base material, tin-based material and lithium titanate Li4Ti5O12One of or multiple combinations, carbon-based material be graphite,
Amorphous carbon, carbonaceous mesophase spherules, silicon carbon material, silica-base material are silicon carbon material, nano-silicon.
9. the preparation method of bipolarity solid lithium secondary cell according to claim 1, which is characterized in that step 3) and step
4) conductive agent described in include acetylene black, Super P, Super S, 350G, carbon fiber VGCF, carbon nanotube CNTs, Ketjen black,
One or more combinations in graphite agent and graphene, graphite agent are KS-6, KS-15, SFG-6, SFG-15；Bonding
Agent is Kynoar PVdF, polytetrafluoroethylene PTFE, polyethylene glycol oxide PEO, polypropylene carbonate PPC, poly- ethylene carbonate
PEC, polytrimethylene carbonate PTMC, PVAC polyvinylalcohol, sodium carboxymethylcellulose CMC, polyolefins, cyano rubber NBR,
One of modified SBR, Viton, polyurethane or multiple combinations, polyolefins are polyethylene, polypropylene and its copolymer,
Polyolefins is polyethylene, polypropylene and its copolymer.
10. the preparation method of bipolarity solid lithium secondary cell according to claim 1, which is characterized in that institute in step 2)
Stating bipolar current collector is to be deposited on Cu on Al collector to prepare, and preparation method includes that magnetron sputtering, pulse laser are heavy
Product, chemical vapor deposition, metal oxide chemical vapor deposition, atomic layer deposition, ion beam sputtering plating method, electron beam evaporation method
It is atomized pyrolytic deposition, sol-gel deposition, Electrostatic Spray Deposition, aerosol deposition, chemical plating or physical vapor deposition, is prepared
Bipolar current collector is with a thickness of 13-50 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811590375.2A CN109768334A (en) | 2018-12-25 | 2018-12-25 | Preparation method of bipolar solid-state lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811590375.2A CN109768334A (en) | 2018-12-25 | 2018-12-25 | Preparation method of bipolar solid-state lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109768334A true CN109768334A (en) | 2019-05-17 |
Family
ID=66451646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811590375.2A Pending CN109768334A (en) | 2018-12-25 | 2018-12-25 | Preparation method of bipolar solid-state lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109768334A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110556568A (en) * | 2019-09-27 | 2019-12-10 | 安徽坤宇塑金新能源技术有限公司 | high-voltage monomer solid-state lithium ion battery and preparation method thereof |
| CN110994014A (en) * | 2019-12-05 | 2020-04-10 | 南方科技大学 | All-solid-state polymer electrolyte, preparation method and lithium ion battery |
| CN111900467A (en) * | 2020-07-08 | 2020-11-06 | 西北工业大学 | Metal organic framework material modified PEO-based fire-safe solid polymer electrolyte and preparation method thereof |
| CN112186130A (en) * | 2020-08-25 | 2021-01-05 | 合肥国轩高科动力能源有限公司 | Bipolar composite electrode plate and preparation method thereof |
| CN112289969A (en) * | 2020-10-19 | 2021-01-29 | 中国电子科技集团公司第十八研究所 | Bipolar current collector and preparation method of bipolar solid-state lithium secondary battery |
| CN112310348A (en) * | 2019-08-02 | 2021-02-02 | 上海汽车集团股份有限公司 | All-solid-state lithium ion battery composite positive electrode and preparation method thereof |
| CN112490433A (en) * | 2020-11-05 | 2021-03-12 | 中国电子科技集团公司第十八研究所 | Solid-state battery and method for improving rate capability and safety of solid-state battery |
| CN112542610A (en) * | 2020-11-16 | 2021-03-23 | 欣旺达电动汽车电池有限公司 | All-solid-state battery and preparation method thereof |
| CN112582666A (en) * | 2019-09-27 | 2021-03-30 | 荣盛盟固利新能源科技有限公司 | Bipolar lithium ion battery and preparation method thereof |
| CN113151790A (en) * | 2021-02-05 | 2021-07-23 | 电子科技大学 | Ion/electron common conductor film, preparation method thereof, solid-state battery and electric vehicle |
| CN113258127A (en) * | 2021-05-31 | 2021-08-13 | 浙江大学 | Current collector-negative electrode integrated bipolar lithium secondary battery and method thereof |
| CN113555532A (en) * | 2021-07-12 | 2021-10-26 | 成都巴莫科技有限责任公司 | Preparation method of integrated high-performance electrode for solid-state battery |
| CN113871626A (en) * | 2021-09-06 | 2021-12-31 | 苏州领湃新能源科技有限公司 | Bipolar current collector of secondary battery and manufacturing process thereof |
| CN117913351A (en) * | 2024-03-19 | 2024-04-19 | 蜂巢能源科技股份有限公司 | All-solid-state battery and preparation method thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002075455A (en) * | 2000-08-24 | 2002-03-15 | Matsushita Electric Ind Co Ltd | Lithium secondary cell |
| CN1397654A (en) * | 2002-05-27 | 2003-02-19 | 长沙力元新材料股份有限公司 | Process and apparatus for preparing porous metal by combined physical gas-phase deposition techinque |
| JP2004071405A (en) * | 2002-08-07 | 2004-03-04 | Nissan Motor Co Ltd | Bipolar battery |
| CN101312245A (en) * | 2007-05-24 | 2008-11-26 | 日产自动车株式会社 | Current collector for nonaqueous solvent secondary battery, and electrode and battery, which use the current collector |
| US20110177370A1 (en) * | 2008-10-03 | 2011-07-21 | Toyota Jidosha Kabushiki Kaisha | Electrode body, all solid state battery element, and all solid state battery |
| CN102201605A (en) * | 2010-03-22 | 2011-09-28 | 中国电子科技集团公司第十八研究所 | Electrochemical energy storage and conversion device having bipolar structure |
| US20120189912A1 (en) * | 2010-01-29 | 2012-07-26 | Nissan Motor Co., Ltd. | Collector for bipolar lithium ion secondary battery |
| CN102668225A (en) * | 2009-11-18 | 2012-09-12 | 株式会社Lg化学 | Bipolar electrode pair/separation membrane assembly, bipolar battery including same, and production method thereof |
| CN103219521A (en) * | 2012-01-20 | 2013-07-24 | 北京好风光储能技术有限公司 | Bipolarity current collector and preparation method |
| JP2016173915A (en) * | 2015-03-17 | 2016-09-29 | 古河機械金属株式会社 | Bipolar type lithium ion battery and manufacturing method thereof |
| CN107123814A (en) * | 2017-06-06 | 2017-09-01 | 李涛 | The copper aluminum composite material and production method of a kind of lithium battery collector negative pole |
| CN107681190A (en) * | 2016-08-01 | 2018-02-09 | 北京好风光储能技术有限公司 | The bipolar structure body and battery core of a kind of high-voltage battery |
| US20180138513A1 (en) * | 2016-11-11 | 2018-05-17 | GM Global Technology Operations LLC | Metal deposition methods for forming bimetallic structures, batteries incorporating bipolar current collectors made therefrom, and applications thereof |
| CN108110257A (en) * | 2017-12-29 | 2018-06-01 | 暨南大学 | A kind of bipolar current collector and the bipolarity solid lithium secondary cell by its assembling |
-
2018
- 2018-12-25 CN CN201811590375.2A patent/CN109768334A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002075455A (en) * | 2000-08-24 | 2002-03-15 | Matsushita Electric Ind Co Ltd | Lithium secondary cell |
| CN1397654A (en) * | 2002-05-27 | 2003-02-19 | 长沙力元新材料股份有限公司 | Process and apparatus for preparing porous metal by combined physical gas-phase deposition techinque |
| JP2004071405A (en) * | 2002-08-07 | 2004-03-04 | Nissan Motor Co Ltd | Bipolar battery |
| CN101312245A (en) * | 2007-05-24 | 2008-11-26 | 日产自动车株式会社 | Current collector for nonaqueous solvent secondary battery, and electrode and battery, which use the current collector |
| US20110177370A1 (en) * | 2008-10-03 | 2011-07-21 | Toyota Jidosha Kabushiki Kaisha | Electrode body, all solid state battery element, and all solid state battery |
| CN102668225A (en) * | 2009-11-18 | 2012-09-12 | 株式会社Lg化学 | Bipolar electrode pair/separation membrane assembly, bipolar battery including same, and production method thereof |
| US20120189912A1 (en) * | 2010-01-29 | 2012-07-26 | Nissan Motor Co., Ltd. | Collector for bipolar lithium ion secondary battery |
| CN102201605A (en) * | 2010-03-22 | 2011-09-28 | 中国电子科技集团公司第十八研究所 | Electrochemical energy storage and conversion device having bipolar structure |
| CN103219521A (en) * | 2012-01-20 | 2013-07-24 | 北京好风光储能技术有限公司 | Bipolarity current collector and preparation method |
| JP2016173915A (en) * | 2015-03-17 | 2016-09-29 | 古河機械金属株式会社 | Bipolar type lithium ion battery and manufacturing method thereof |
| CN107681190A (en) * | 2016-08-01 | 2018-02-09 | 北京好风光储能技术有限公司 | The bipolar structure body and battery core of a kind of high-voltage battery |
| US20180138513A1 (en) * | 2016-11-11 | 2018-05-17 | GM Global Technology Operations LLC | Metal deposition methods for forming bimetallic structures, batteries incorporating bipolar current collectors made therefrom, and applications thereof |
| CN107123814A (en) * | 2017-06-06 | 2017-09-01 | 李涛 | The copper aluminum composite material and production method of a kind of lithium battery collector negative pole |
| CN108110257A (en) * | 2017-12-29 | 2018-06-01 | 暨南大学 | A kind of bipolar current collector and the bipolarity solid lithium secondary cell by its assembling |
Non-Patent Citations (1)
| Title |
|---|
| HYUN-SEOP SHIN ET AL.: "Multilayered,Bipoar,All-Solid-State Battery Enabled by a Perovskite-Based Biphasic Solid Electrolyte", 《CHEMISTRY-SUSTAINABILITY-ENERGY-MATERIALS》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112310348A (en) * | 2019-08-02 | 2021-02-02 | 上海汽车集团股份有限公司 | All-solid-state lithium ion battery composite positive electrode and preparation method thereof |
| CN112582666A (en) * | 2019-09-27 | 2021-03-30 | 荣盛盟固利新能源科技有限公司 | Bipolar lithium ion battery and preparation method thereof |
| CN110556568A (en) * | 2019-09-27 | 2019-12-10 | 安徽坤宇塑金新能源技术有限公司 | high-voltage monomer solid-state lithium ion battery and preparation method thereof |
| CN110994014A (en) * | 2019-12-05 | 2020-04-10 | 南方科技大学 | All-solid-state polymer electrolyte, preparation method and lithium ion battery |
| CN111900467A (en) * | 2020-07-08 | 2020-11-06 | 西北工业大学 | Metal organic framework material modified PEO-based fire-safe solid polymer electrolyte and preparation method thereof |
| CN112186130A (en) * | 2020-08-25 | 2021-01-05 | 合肥国轩高科动力能源有限公司 | Bipolar composite electrode plate and preparation method thereof |
| CN112289969A (en) * | 2020-10-19 | 2021-01-29 | 中国电子科技集团公司第十八研究所 | Bipolar current collector and preparation method of bipolar solid-state lithium secondary battery |
| CN112490433A (en) * | 2020-11-05 | 2021-03-12 | 中国电子科技集团公司第十八研究所 | Solid-state battery and method for improving rate capability and safety of solid-state battery |
| CN112542610A (en) * | 2020-11-16 | 2021-03-23 | 欣旺达电动汽车电池有限公司 | All-solid-state battery and preparation method thereof |
| CN113151790A (en) * | 2021-02-05 | 2021-07-23 | 电子科技大学 | Ion/electron common conductor film, preparation method thereof, solid-state battery and electric vehicle |
| CN113258127A (en) * | 2021-05-31 | 2021-08-13 | 浙江大学 | Current collector-negative electrode integrated bipolar lithium secondary battery and method thereof |
| CN113258127B (en) * | 2021-05-31 | 2023-09-15 | 浙江大学 | Current collector-negative electrode integrated bipolar lithium secondary battery and method thereof |
| CN113555532A (en) * | 2021-07-12 | 2021-10-26 | 成都巴莫科技有限责任公司 | Preparation method of integrated high-performance electrode for solid-state battery |
| CN113871626A (en) * | 2021-09-06 | 2021-12-31 | 苏州领湃新能源科技有限公司 | Bipolar current collector of secondary battery and manufacturing process thereof |
| CN113871626B (en) * | 2021-09-06 | 2023-03-14 | 湖南领湃达志科技股份有限公司 | Bipolar current collector of secondary battery and manufacturing process thereof |
| CN117913351A (en) * | 2024-03-19 | 2024-04-19 | 蜂巢能源科技股份有限公司 | All-solid-state battery and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109768334A (en) | Preparation method of bipolar solid-state lithium secondary battery | |
| JP7389857B2 (en) | Lithium anode device stack manufacturing | |
| KR102378583B1 (en) | Separator Having Coating Layer of Lithium-Containing Composite, and Lithium Secondary Battery Comprising the Separator and Preparation Method Thereof | |
| US6649033B2 (en) | Method for producing electrode for lithium secondary battery | |
| WO2019146296A1 (en) | Positive electrode material and battery using same | |
| CN111758176A (en) | Method for predoping negative electrode active material, method for producing negative electrode, and method for producing power storage device | |
| WO2018191843A1 (en) | Pre-lithiated silicon-based anode, and manufacturing method thereof | |
| JP4575487B2 (en) | Lithium ion secondary battery and manufacturing method thereof | |
| KR20020095448A (en) | Lithium secondary battery with an improved negative electrode structure and method of forming the same | |
| KR20190017651A (en) | Pre-lithiation method of lithium secondary battery anode using lithium metal-ceramic thin layer | |
| US10615449B2 (en) | Electrode material for secondary battery and secondary battery | |
| CN111095626B (en) | Negative active material for lithium secondary battery and method for preparing same | |
| CN112736277A (en) | Solid electrolyte-lithium negative electrode complex, method for producing same, and all-solid-state lithium secondary battery | |
| KR20220116144A (en) | Multifunctional Processed Particles for Secondary Batteries and Method for Manufacturing Same | |
| CN116670849A (en) | Method for preparing electrolyte-filled high quality load electrode for high energy density battery | |
| CN112714971A (en) | Negative electrode active material for lithium secondary battery, and negative electrode and lithium secondary battery comprising same | |
| KR20190035483A (en) | Positive Electrode Active Material for High Voltage Comprising Lithium Manganese-Based Oxide and Preparation Method Thereof | |
| WO2009147833A1 (en) | Nonaqueous electrolytic secondary battery and the manufacturing method thereof | |
| KR20160008270A (en) | Coin type lithium rechargeable battery | |
| KR20080086121A (en) | Negative active material for a lithium secondary battery, method of preparing thereof, and lithium secondary battery comprising the same | |
| KR102199431B1 (en) | Composite negative active material, electrochemical device including the same, and method of preparing the composite negative active material | |
| JP2021106074A (en) | Negative electrode active material | |
| JP2013054999A (en) | Method for producing electrode thin film, electrode thin film produced by the method, and battery including the electrode thin film | |
| US20240088360A1 (en) | Coated active material, electrode material, and battery | |
| KR20190143256A (en) | Si Anode and Lithium Secondary Battery Comprising The Same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| 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 |
Application publication date: 20190517 |
|
| RJ01 | Rejection of invention patent application after publication |