CN108511786B - All-solid-state lithium battery and preparation method thereof - Google Patents
All-solid-state lithium battery and preparation method thereof Download PDFInfo
- Publication number
- CN108511786B CN108511786B CN201710111544.9A CN201710111544A CN108511786B CN 108511786 B CN108511786 B CN 108511786B CN 201710111544 A CN201710111544 A CN 201710111544A CN 108511786 B CN108511786 B CN 108511786B
- Authority
- CN
- China
- Prior art keywords
- lithium
- solid
- state
- solid electrolyte
- positive
- 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.)
- Active
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title description 13
- 239000010410 layer Substances 0.000 claims abstract description 65
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 30
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 28
- 239000011737 fluorine Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000010406 cathode material Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 239000011247 coating layer Substances 0.000 claims abstract description 8
- 239000013543 active substance Substances 0.000 claims abstract description 6
- 239000011230 binding agent Substances 0.000 claims description 44
- 239000007774 positive electrode material Substances 0.000 claims description 41
- 239000007773 negative electrode material Substances 0.000 claims description 29
- -1 polytetrafluoroethylene Polymers 0.000 claims description 27
- 239000010405 anode material Substances 0.000 claims description 20
- 229910003002 lithium salt Inorganic materials 0.000 claims description 19
- 159000000002 lithium salts Chemical class 0.000 claims description 19
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 18
- 239000006258 conductive agent Substances 0.000 claims description 16
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 16
- 239000002241 glass-ceramic Substances 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 239000002033 PVDF binder Substances 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910052732 germanium Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- 239000011135 tin Substances 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000005062 Polybutadiene Substances 0.000 claims description 7
- 239000002174 Styrene-butadiene Substances 0.000 claims description 7
- 229920002857 polybutadiene Polymers 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 239000001856 Ethyl cellulose Substances 0.000 claims description 6
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- 235000010980 cellulose Nutrition 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229920006026 co-polymeric resin Polymers 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229920001249 ethyl cellulose Polymers 0.000 claims description 6
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 229920001973 fluoroelastomer Polymers 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000004816 latex Substances 0.000 claims description 6
- 229920000126 latex Polymers 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 229920001225 polyester resin Polymers 0.000 claims description 6
- 239000004645 polyester resin Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 229920000128 polypyrrole Polymers 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 229920000123 polythiophene Polymers 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 6
- 239000011115 styrene butadiene Substances 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000002019 doping agent Substances 0.000 claims description 5
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 5
- 229940071264 lithium citrate Drugs 0.000 claims description 5
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229910001216 Li2S Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 239000010416 ion conductor Substances 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 4
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910005871 GeS4 Inorganic materials 0.000 claims description 3
- 229910000733 Li alloy Inorganic materials 0.000 claims description 3
- 229910003349 Li2CuO2 Inorganic materials 0.000 claims description 3
- 229910001367 Li3V2(PO4)3 Inorganic materials 0.000 claims description 3
- 229910010699 Li5FeO4 Inorganic materials 0.000 claims description 3
- 229910011297 LiCox Inorganic materials 0.000 claims description 3
- 229910011386 LiCoxNi1-xO2 Inorganic materials 0.000 claims description 3
- 229910011384 LiCoxNi1−xO2 Inorganic materials 0.000 claims description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 3
- 229910003005 LiNiO2 Inorganic materials 0.000 claims description 3
- 229910001319 LiVPO4F Inorganic materials 0.000 claims description 3
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 3
- 229910019695 Nb2O6 Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910020269 SiP2 Inorganic materials 0.000 claims description 3
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 3
- 229910010252 TiO3 Inorganic materials 0.000 claims description 3
- 229910003092 TiS2 Inorganic materials 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 239000001989 lithium alloy Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052960 marcasite Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 229910052683 pyrite Inorganic materials 0.000 claims description 3
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 7
- 238000009792 diffusion process Methods 0.000 abstract description 6
- 239000006182 cathode active material Substances 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910009866 Ti5O12 Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002228 NASICON Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000010406 interfacial reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000000992 sputter etching Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 1
- 229910012463 LiTaO3 Inorganic materials 0.000 description 1
- 101100495393 Rattus norvegicus Ceacam3 gene Proteins 0.000 description 1
- 229910010342 TiF4 Inorganic materials 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910021561 transition metal fluoride Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The all-solid-state lithium battery comprises a positive plate, a negative plate and a solid electrolyte layer, wherein the positive plate comprises a positive active substance, and the positive active substance comprises positive material particles and a fluorine-containing lithium titanate layer coated on the surfaces of the positive material particles. According to the method for preparing the cathode active material with the cathode material surface coated with the fluorine-containing lithium titanate layer by mixing and sintering the cathode material, the surface of the cathode material can be uniformly modified to obtain the cathode material with controllable surface fluorine content and fluorine-containing lithium titanate layer thickness, when the cathode material is used for an all-solid-state lithium battery, the coating layer structure can be stabilized, interface reaction or element diffusion between the cathode material and a solid electrolyte is avoided, and interface impedance is reduced.
Description
Technical Field
The disclosure relates to the field of solid-state lithium batteries, in particular to an all-solid-state lithium battery and a preparation method thereof.
Background
In the all-solid-state lithium battery, because of the serious interface effect between the anode material and the solid electrolyte and the diffusion problem of elements appearing at the interface, the interface impedance between the anode and the solid electrolyte is greatly increased, thereby greatly influencing the performance of the battery, the prior art usually adopts a method of surface coating the anode material to solve the technical problem, wherein the coating is usually oxide, lithium-containing transition metal oxide or fluoride, and the like, the anode material is usually selected from L iNbO3、LiTaO3、Li4Ti5O12、Al2O3、BaF2Or CaF2Etc., in which the pairs L iNbO3The cathode material coated on the surface is most widely used.
Typically, binary or ternary oxide materials (e.g., L iNbO) are used3) The surface of the anode material is coated, but oxygen atoms and sulfur atoms in the existing sulfur-based electrolyte can diffuse mutually, and the structure of the coating layer is not stable enough, so that the reduction of the interface impedance between the anode material and the electrolyte is not obvious, or the impedance can be gradually increased in the charging and discharging process, the charging and discharging process is blocked, and the service life can be reduced.
Disclosure of Invention
The purpose of the disclosure is to provide an all-solid-state lithium battery and a preparation method thereof, which can solve the problems of large interfacial resistance between a positive electrode and a solid electrolyte and mutual diffusion of elements in a circulation process in the prior art.
In order to achieve the above object, the present disclosure provides an all-solid-state lithium battery including a positive electrode sheet, a negative electrode sheet, and a solid electrolyte layer, wherein the positive electrode sheet includes a positive electrode active material, and the positive electrode active material includes positive electrode material particles and a fluorine-containing lithium titanate layer coated on the surfaces of the positive electrode material particles.
The present disclosure also provides a method of manufacturing an all-solid-state lithium battery including a positive electrode sheet, a negative electrode sheet, and a solid electrolyte layer, the method including the steps of:
(1) adding titanium Tetrafluoride (TiF) to the solvent4) And lithium salt, adding the anode material after stirring until the lithium salt is dissolved, fully stirring, and evaporating the solvent to obtain a reaction precursor; sintering the reaction precursor to obtain a positive active material with a fluorine-containing lithium titanate layer coated on the surface of a positive material;
(2) and sequentially pressing a solid electrolyte layer containing a solid electrolyte and a negative plate on the positive plate containing the positive active material to obtain the all-solid-state lithium battery.
The disclosure also provides an all-solid-state lithium battery prepared by the method.
The inventors of the present disclosure have made numerous experiments and have unexpectedly found that a fluorine-containing lithium titanate layer having a uniform thickness can be formed on the surface of a positive electrode material particle by high-temperature sintering after mixing titanium tetrafluoride, a lithium salt and a positive electrode material in a solution. The anode material coated by the fluorine-containing lithium titanate can avoid interface side reaction between the anode material and the solid electrolyte, prevent elements between interfaces from diffusing, and greatly reduce the interface impedance between the anode material and the solid electrolyte. While the present disclosure proposes the use of titanium Tetrafluoride (TiF)4) The method for preparing the positive active material with the surface of the positive material coated with the fluorine-containing lithium titanate layer by mixing the lithium salt and the positive material in the solution and then sintering at high temperature can uniformly coat the surface of the positive material to obtain the positive material with the controllable coating thickness, and when the positive material is used for the all-solid-state lithium battery, the positive material can be usedThe method has the advantages of avoiding interface reaction or element diffusion between the anode material and the solid electrolyte, reducing interface impedance, improving the cycling stability of the anode material, prolonging the service life of the all-solid-state lithium battery and improving the electrochemical performance of the all-solid-state lithium battery.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The utility model provides an all solid-state lithium battery, including positive plate, negative pole piece and solid electrolyte layer, the positive plate includes anodal active material, anodal active material includes anodal material granule and cladding in the lithium titanate layer that contains fluorine on anodal material granule surface.
The all-solid-state lithium battery adopts the anode material of which the surface is coated with the fluorine-containing lithium titanate layer, the coating layer has uniform thickness, can avoid the interfacial reaction between the anode material and the solid electrolyte, prevent the diffusion of elements between interfaces, greatly reduce the interfacial impedance between the anode material and the solid electrolyte, improve the cycling stability of the anode material, prolong the service life of the all-solid-state battery and improve the electrochemical performance of the all-solid-state battery.
According to the present disclosure, the fluorine-containing lithium titanate layer is a fluorine-doped lithium titanate coating layer formed on the surface of the positive electrode material particles after being treated with titanium tetrafluoride and lithium salt; the F/O atomic ratio of the lithium fluorotitanate layer refers to a value obtained by dividing the percentage content of fluorine element in all atoms in the surface layer of the tested positive electrode material by the percentage content of oxygen element in all elements, and the F/O atomic ratio can represent the fluorine content of the lithium fluorotitanate layer, and can be determined by methods well known to those skilled in the art, for example, the F/O atomic ratio described in the present disclosure is determined by an X-ray photoelectron spectroscopy method. The coating effect is uniform, preferably, the F/O atomic ratio of the fluorine-containing lithium titanate layer can be 0.01-100, and the fluorine content in the coating layer does not change along with the thickness of the coating layer.
According to the present disclosure, the molar ratio of fluorine atoms to titanium atoms in the fluorine-containing lithium titanate coating layer may vary widely, preferably 0.01 to 2.4: 1.
according to the present disclosure, the particle size of the positive electrode active material may vary widely, preferably 0.05 to 1000 μm, and more preferably 1 to 100 μm; the thickness of the lithium fluorotitanate-containing layer is controllable and can be varied within a wide range, and in order to further uniformly coat the positive electrode material and avoid interfacial reaction, the thickness of the lithium fluorotitanate-containing layer is preferably 10nm to 2000nm, and more preferably 50 nm to 1000 nm.
According to the present disclosure, the lithium salt may specifically be L i2O、Li2S、LiOH、LiF、LiCl、LiBr、LiI、Li2CO3、Li2SO4、Li3PO4、LiNO3And at least one of lithium acetate, lithium methoxide, lithium ethoxide, lithium citrate, and lithium amide.
According to the present disclosure, the solid electrolyte layer is one or more of a sodium fast ion conductor structure type (NASICON type) solid electrolyte, a perovskite type solid electrolyte, and a sulfur type solid electrolyte.
The NASICON type solid electrolyte is L iM2(PO4)3And a dopant thereof, wherein M is at least one of Ti, Zr, Ge, Sn or Pb, and L iM2(PO4)3The doping element adopted by the dopant of (1) is at least one selected from Mg, Ca, Sr, Ba, Sc, Al, Ga, In, Nb, Ta and V.
The active solid-state electrolyte of the calcium and titanium is AxByTiO3、AxByTa2O6、AxByNb2O6Or AhMkDnTiwO3Wherein x +3Y =2, h +2k +5n +4w =6, 0 < x < 2, 0 < Y < 2/3, h, k, n, w are all more than 0, A is L i, at least one of Na elements, B is L a, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd elements, M is SrCa, Ba, Ir and Pt, D is at least one of Nb and Ta.
The sulfur-based solid electrolyte may be a sulfur-containing solid electrolyte well known to those skilled in the art, preferably L i of crystalline titaniumxMyPzSwL i in glassy state2S-P2S5L i in the form of glass-ceramic2S-P2S5Wherein M can be at least one of Si, Ge and Sn, x +4y +5z =2w, x is 2. ltoreq. x.ltoreq.11, y is 0. ltoreq. y.ltoreq.1.5, z is 0. ltoreq. z.ltoreq.3, and w is 3. ltoreq. w.ltoreq.13;
l i of the crystalline titaniumxMyPzSwCan be selected from L i in crystalline state3PS4L i in crystalline form4SnS4L i in crystalline form4GeS4L i in crystalline form10SnP2S12L i in crystalline form10GeP2S12And L i in the crystalline state10SiP2S12L i in the glassy state2S-P2S5Selected from the group consisting of 70L i in glassy state2S-30P2S5Glassy 75L i2S-25P2S5And 80L i in glassy state2S-20P2S5L i in the glass-ceramic state2S-P2S570L i selected from the glass-ceramic state2S-30P2S575L i in the glass-ceramic state2S-25P2S5And 80L i in the form of a glass-ceramic2S-20P2S5At least one of (1).
According to the present disclosure, the cathode material is not particularly limited, and may be a cathode material of a kind conventional in the art, preferably selected from L ico2、LiNiO2、LiMn2O4、LiFePO4、Li3V2(PO4)3、Li3V3(PO4)3、LiVPO4F、Li2CuO2、Li5FeO4、TiS2、V2S3、FeS、FeS2、TiO2、Cr3O8、V2O5、MnO2、LiCoxNi1-xO2、LiCoxNi1-x-yAlyO2、LiFepMnqX1-p-qO4、Li1＋sL1－p－qMpNqO2And L iYSrAt least one of;
wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, p is more than or equal to 0 and less than or equal to 1, q is more than or equal to 0 and less than or equal to 1, p + q is more than or equal to 0 and less than or equal to 1, s is more than or equal to 0.1 and less than or equal to 0.2;
x is at least one of Al, Mg, Ga, Cr, Co, Ni, Cu, Zn or Mo, L and M, N are at least one of L I, Co, Mn, Ni, Fe, Al, Mg, Ga, Ti, Cr, Cu, Zn, Mo, F, I, S and B respectively and Y is at least one of Ti, Fe, Ni, Cu and Mo.
In order to further improve the stability of the positive electrode sheet, the positive electrode sheet may further include a positive electrode conductive agent and a first binder, and the content of the positive electrode conductive agent and the first binder may vary widely, and preferably, the content of the positive electrode conductive agent may be 0.1 to 20 parts by weight and the content of the first binder may be 0.01 to 10 parts by weight with respect to 100 parts by weight of the positive electrode active material.
The positive electrode conductive agent and the first binder are well known to those skilled in the art, may be of conventional kinds, and the present invention does not particularly require, and the positive electrode conductive agent is preferably at least one of acetylene black, carbon nanotubes, carbon fibers, and carbon black; the first binder is preferably at least one of polyvinylidene fluoride, polytetrafluoroethylene, and styrene-butadiene rubber.
According to the present disclosure, in order to improve stability and electrical properties of the solid electrolyte layer, the solid electrolyte layer may further include a second binder, which may be used in an amount conventional in the art, and preferably, may be contained in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the solid electrolyte.
The second binder may be a binder of a kind conventional in the art, and is preferably at least one selected from the group consisting of polythiophene, polypyrrole, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-propylene-diene copolymer resin, styrene butadiene rubber, polybutadiene, fluororubber, polyethylene oxide, polyvinylpyrrolidone, polyester resin, acrylic resin, phenol resin, epoxy resin, polyvinyl alcohol, carboxypropyl cellulose, ethyl cellulose, polyethylene oxide, sodium carboxymethylcellulose, and styrene butadiene latex.
According to the present disclosure, the negative electrode sheet includes a negative electrode current collector and a negative electrode material layer located on a surface of the negative electrode current collector, the negative electrode material layer is lithium or a lithium alloy, or the negative electrode material layer includes a negative electrode active material and a third binder;
in another embodiment of the present disclosure, the negative electrode material layer may be a layer including a negative electrode active material, a third binder, wherein the relative content of the negative electrode active material and the third binder may vary widely, and preferably, the content of the third binder may be 0.01 to 10 parts by weight with respect to 100 parts by weight of the negative electrode active material.
According to the present disclosure, the negative electrode active material may be a conventional type used in lithium ion batteries, which is well known to those skilled in the art, and is preferably at least one selected from a carbon material, a tin alloy, a silicon alloy, silicon, tin and germanium, and as a common general knowledge of those skilled in the art, when the negative electrode active material is a silicon type material, the negative electrode material layer further contains a negative electrode conductive agent, the function and specific type of which are well known to those skilled in the art, and thus, the description thereof is omitted.
The third binder may be any of various negative binders known to those skilled in the art, and is preferably at least one of polythiophene, polypyrrole, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-propylene-diene copolymer resin, styrene butadiene rubber, polybutadiene, fluororubber, polyethylene oxide, polyvinylpyrrolidone, polyester resin, acrylic resin, phenol resin, epoxy resin, polyvinyl alcohol, carboxypropyl cellulose, ethyl cellulose, sodium carboxymethylcellulose, and styrene butadiene latex.
The present disclosure also provides a method of manufacturing an all-solid-state lithium battery including a positive electrode sheet, a negative electrode sheet, and a solid electrolyte layer, the method including the steps of:
(1) adding titanium tetrafluoride and lithium salt into solvent, stirring to dissolve, adding anode material, stirring, evaporating solvent to obtain reaction precursor, sintering the reaction precursor to obtain anode material with fluorine-containing lithium titanate layer coated on the surface (F-L i)4Ti5O12Layer) of a positive electrode active material;
(2) and sequentially pressing a solid electrolyte layer containing a solid electrolyte and a negative plate on the positive plate containing the positive active material to obtain the all-solid-state lithium battery.
The preparation method disclosed by the invention can be used for uniformly modifying the surface of the anode material to obtain the anode active substance with the surface coated with the fluorine-containing lithium titanate layer with controllable thickness, and when the anode active substance is used for the all-solid-state lithium battery, the anode material and the solid-state electrolyte can be prevented from generating interface reaction or element diffusion, so that the interface impedance is reduced.
In addition to the preparation method disclosed herein, the positive electrode active material having a surface coated with a fluorine-containing lithium titanate layer may be prepared by a chemical vapor deposition method, a chemical vapor transport method, or a vacuum laser sputtering method, but the above method is very expensive. When the preparation method disclosed by the disclosure is adopted, the fluorine-containing lithium titanate layer with uniform coating and controllable thickness can be obtained, and meanwhile, the used raw materials are simple and have a remarkable cost advantage.
According to the present disclosure, the lithium salt may be L i2O、Li2S、LiOH、LiF、LiCl、LiBr、LiI、Li2CO3、Li2SO4、Li3PO4、LiNO3And at least one of lithium acetate, lithium methoxide, lithium ethoxide, lithium citrate, and lithium amide.
According to the present disclosure, the solvent is at least one of water, methanol, ethanol, lithium citrate, and lithium amide.
According to the present disclosure, in order to further improve the interfacial performance between the positive electrode material and the solid electrolyte, the electrolyte layer is at least one of a NASICON-type solid electrolyte, a perovskite-type solid electrolyte, and a sulfur-based solid electrolyte.
Wherein the NASICON type solid electrolyte is L iM2(PO4)3And at least one of the dopants thereof, wherein M is Ti, Zr, Ge, Sn or Pb, and the dopant adopts at least one doping element selected from Mg, Ca, Sr, Ba, Sc, Al, Ga, In, Nb, Ta and V.
The chemical formula of the titanium-calcium open type solid electrolyte is AxByTiO3、AxByTa2O6、AxByNb2O6Or AhMkDnTiwO3Wherein x +3Y =2, h +2k +5n +4w =6, 0 < x < 2, 0 < Y < 2/3, h, k, n, w are all more than 0, A is at least one of L i and Na elements, B is at least one of L a, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd elements, M is at least one of Sr, Ca, Ba, Ir, Pt elements, and D is at least one of Nb and Ta elements.
The sulfur-based solid electrolyte may be a sulfur-containing solid electrolyte well known to those skilled in the art, preferably L i in a crystalline statexMyPzSwL i in glassy state2S-P2S5L i in the form of glass-ceramic2S-P2S5Wherein M is at least one of Si, Ge and Sn, x +4y +5z =2w, x is 2. ltoreq. x.ltoreq.11, y is 0. ltoreq. y.ltoreq.1.5, z is 0. ltoreq. z.ltoreq.3, w is 3. ltoreq. w.ltoreq.13, wherein L i is in the crystalline statexMyPzSwL i selected from crystalline state3PS4L i in crystalline form4SnS4L i in crystalline form4GeS4L i in crystalline form10SnP2S12L i in crystalline form10GeP2S12L i in crystalline form10SiP2S12L i in the glassy state2S-P2S5Selected from the group consisting of 70L i in glassy state2S-30P2S5Glassy 75L i2S-25P2S5Glassy state 80L i2S-20P2S5L i in the glass-ceramic state2S-P2S570L i selected from the glass-ceramic state2S-30P2S575L i in the glass-ceramic state2S-25P2S580L i in the form of a glass-ceramic2S-20P2S5At least one of (1).
The positive electrode material is not particularly limited, and may be a positive electrode material of a type conventional in the art, and preferably, the positive electrode material is selected from L iCoO2、LiNiO2、LiMn2O4、LiFePO4、Li3V2(PO4)3、Li3V3(PO4)3、LiVPO4F、Li2CuO2、Li5FeO4、TiS2、V2S3、FeS、FeS2、TiO2、Cr3O8、V2O5、MnO2、LiCoxNi1-xO2、LiCoxNi1-x- yAlyO2、LiFepMnqX1-p-qO4、Li1＋sL1－p－qMpNqO2And L iYSrWherein X is more than or equal to 0 and less than or equal to 1, Y is more than or equal to 0 and less than or equal to 1, p is more than or equal to 0 and less than or equal to 1, q is more than or equal to 0 and less than or equal to 1, S is more than or equal to 0.1 and less than or equal to 0.2, r is more than or equal to 1 and less than or equal to 2.5, X is at least one of Al, Mg, Ga, Cr, Co, Ni, Cu, Zn or Mo, L and M, N are at least one of L I, Co, Mn, Ni, Fe, Al, Mg, Ga, Ti, Cr, Cu, Zn, Mo, F, I, S and B, and Y is at least one of Ti, Fe, Ni, Cu and Mo.
According to the present disclosure, in step (1), the reaction conditions of the cathode material and the titanium tetrafluoride may be varied within a wide range as long as it is satisfied that the titanium tetrafluoride and the lithium salt on the surface of the cathode material may be reacted. Preferred reaction conditions include: the solvent evaporation temperature is 20-100 ℃, and the sintering temperature is 400-1000 ℃; more preferably, it comprises: the evaporation temperature is 70-90 ℃, and the sintering temperature is 650-850 ℃.
In experiments, the inventors of the present disclosure found that when the conditions of the contact reaction of the cathode material with the lithium salt and titanium tetrafluoride are controlled to be within the above range, the cathode material after being treated with the fluorine-containing lithium titanate has a more excellent interface effect with the solid electrolyte.
The relative amounts of the cathode material and the lithium salt and titanium tetrafluoride can be varied in a wide range, and in order to further improve the reaction efficiency, the molar ratio of the cathode material, titanium tetrafluoride and lithium salt (calculated by lithium element) can be preferably 1: (0.01-100): (0.01-100).
According to the present disclosure, the method for preparing the positive electrode sheet may further include: uniformly mixing the positive active material, the positive conductive agent and the first binder in a solvent, coating the mixture on the surface of a positive current collector, and drying and tabletting the mixture to obtain the positive plate containing the positive active material layer;
the relative amounts of the positive electrode active material, the positive electrode conductive agent and the first binder may vary widely, and preferably, the positive electrode conductive agent may be used in an amount of 0.1 to 20 parts by weight and the first binder may be used in an amount of 0.01 to 10 parts by weight, based on 100 parts by weight of the positive electrode active material; within the preferable dosage range, the positive plate prepared by the method has more stable structure and better electrical property.
Wherein, the positive electrode conductive agent and the first binder may be of a kind conventional in the art, and preferably, the positive electrode conductive agent may be at least one of acetylene black, carbon nanotubes, carbon fibers, and carbon black; the first binder may be at least one of polyvinylidene fluoride, polytetrafluoroethylene, and styrene butadiene rubber.
According to the present disclosure, the method of preparing the solid electrolyte layer may further include: uniformly mixing the solid electrolyte and a second binder in a solvent, coating the mixture on the surface of the positive plate, and drying and tabletting the mixture to obtain the positive plate containing the solid electrolyte layer;
the relative amounts of the above solid electrolyte and second binder may vary widely, and preferably, the second binder may be used in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the solid electrolyte; within the above preferred range of the amount, the solid electrolyte layer prepared by the above method is superior in charge and discharge performance.
Wherein the second binder may be of a kind conventional in the art, and preferably, the second binder may be at least one selected from the group consisting of polythiophene, polypyrrole, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-propylene-diene copolymer resin, styrene butadiene rubber, polybutadiene, fluororubber, polyethylene oxide, polyvinylpyrrolidone, polyester resin, acrylic resin, phenol resin, epoxy resin, polyvinyl alcohol, carboxypropyl cellulose, ethyl cellulose, polyethylene oxide, sodium carboxymethyl cellulose, and styrene butadiene latex.
According to the present disclosure, the lithium-ion battery comprises a negative electrode current collector and a negative electrode material layer located on the surface of the negative electrode current collector, wherein the negative electrode material layer is lithium or a lithium alloy, or comprises a negative electrode active material and a third binder;
when the negative electrode material layer includes a negative electrode active material and a third binder, the method for preparing the negative electrode sheet may further include: and uniformly mixing the negative electrode active material and the third binder in a solvent, coating the mixture on the surface of a negative electrode current collector, and drying and tabletting to obtain the negative electrode sheet.
The relative amounts of the negative electrode active material and the third binder may vary widely, and preferably, the third binder is used in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the negative electrode active material.
Wherein the negative electrode active material and the third binder may be of a kind conventional in the art, and preferably, the negative electrode active material may be at least one selected from the group consisting of a carbon material, a tin alloy, a silicon alloy, silicon, tin, and germanium; the third binder may be at least one of polythiophene, polypyrrole, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-propylene-diene copolymer resin, styrene butadiene rubber, polybutadiene, fluororubber, polyethylene oxide, polyvinylpyrrolidone, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxypropyl cellulose, ethyl cellulose, sodium carboxymethyl cellulose, and styrene butadiene latex. As a common knowledge of those skilled in the art, when the negative active material is a silicon-based material, the negative material layer further contains a negative conductive agent, and the function, specific type and content thereof are well known to those skilled in the art and will not be described herein again.
The disclosure also provides an all-solid-state lithium battery prepared by the method.
The present disclosure is further described below by way of examples, but the present disclosure is not limited thereto in any way.
Example 1
(1) Containing F-L i4Ti5O12Preparation of positive electrode active material of layer
100 g (g) of the positive electrode active material L iCoO212g of TiF4Uniformly mixing with 2g of anhydrous L iOH, adding into 500 m L of ethanol, stirring for 2 h, evaporating to dryness at 70 ℃, fully grinding the obtained precursor, and sintering at 700 ℃ to obtain a final product F-L i4Ti5O12L iCoO coated with material2And (3) a positive electrode material.
(2) Preparation of Positive electrode sheet C
930g of a catalyst containing a catalyst carrier F-L i4Ti5O12L iCoO coated with material2The positive electrode material (93%), 30g of binder PVDF (3%), 20 g of acetylene black (2%) and 20 g of conductive agent carbon fiber (2%) were added to 1500 g of solvent NMP (N-methylpyrrolidone), and then stirred in a vacuum stirrer to form stable and uniform positive electrode slurry. The positive electrode slurry was uniformly coated intermittently on both sides of an aluminum foil (aluminum foil size: width 160 mm, thickness 16 μm), and then dried at 393K, and pressed into sheets by a roll press to obtain C.
(3) Preparation of Positive electrode sheet CE containing solid electrolyte layer
In a glove box, 600 g of 70L i in a glass state2S-30P2S5And 1200 g of a toluene solution containing 30g of a butadiene rubber binder, followed by heating and stirring to a stable and uniform solution, the solution was continuously coated on the positive electrode sheet C obtained in step 2, and then dried at 333K, and cut into a 485 mm (length) × 46 mm (width) positive electrode sheet CE containing a solid electrolyte layer.
(4) Preparation of negative electrode A
940 g of negative active material artificial graphite (94%), 30g of binder CMC (3%) and 30g of binder SBR (3%) were added to 1200 g of deionized water, and then stirred in a vacuum stirrer to form stable and uniform negative slurry, which was uniformly coated intermittently on both sides of a copper foil (copper foil size: 160 mm in width, 16 μm in thickness), dried at 393K, and cut into negative electrode sheets A of 480 mm (length) × 45 mm (width) after being pressed into sheets by a roll press.
(5) Preparation of all-solid-state lithium battery CEA
And (3) in a glove box, cutting the CE obtained in the step (3) and the A obtained in the step (4), aligning, placing in a hot press, performing 423K hot pressing for 1 h, vacuumizing and sealing by using an aluminum plastic film, and taking out a sample. The above-described pressed sample was pressed in an isostatic press at 200 MPa for 300 seconds to obtain the all-solid-state lithium battery CEA1 of the present example.
Example 2
The electrolyte and lithium ion battery of this example were prepared using the method of example 1, except that: in the step (1), TiF is added4The amount of the anhydrous L iOH was changed to 6 g and 1 g, and the other steps and operations were the same, to obtain the all-solid lithium battery CEA2 of this example.
Example 3
The electrolyte and lithium ion battery of this example were prepared by the method of example 1, except that L iFePO was used as the positive electrode material in step (1)4Replacement L iCoO2. The whole solid of the present example was obtainedThe lithium battery CEA 3.
Example 4
The electrolyte and lithium ion battery of this example were prepared using the method of example 1, except that: in the step (1), the obtained precursor is sintered at a high temperature of 900 ℃, and other steps and operations are the same. The all-solid-state lithium battery CEA4 of this example was obtained.
Comparative example 1
The electrolyte and lithium ion battery of this example were prepared using the method of example 1, except that: in the step (1), 285ml of tetrabutyl titanate is used for replacing 12gTiF4。
Comparative example 2
An electrolyte and a lithium ion battery of this example were manufactured by the method of example 1, except that L iCoO was used in step (1)2The material was directly subjected to the preparation of positive electrode C, CE, negative electrode A and CEA, but not to L iCoO2Carrying out F-L i4Ti5O12The coating operation of (1).
Test example 1
SEM test and XPS test were performed on the positive electrode active material containing the fluorinated modification layer obtained in examples 1 to 4 and the positive electrode active material obtained in comparative examples 1 to 2, respectively, and the atomic ratio of F/O on the surface of the positive electrode active material, the particle diameter, and the thickness data of the fluorinated modification layer are shown in table 1;
subjecting the positive electrode active material to Ar+After ion etching, the surface F/O atomic ratio was measured, where Ar+The step size of the ion etching is 2 min, and the energy of the used ion beam is 2 keV.
TABLE 1
Test example 2
The all-solid-state lithium batteries CEA1-CEA5 obtained in examples 1-3 and comparative examples 1-2 were subjected to a cycle life test of a battery cell, as follows:
the method comprises the steps of taking 20 batteries prepared in each example AND each comparative example, carrying out charge-discharge cycle test on the batteries at 0.1C on an L AND CT 2001C secondary battery performance detection device under the condition of 298 +/-1K, standing for 10min, charging at constant voltage until 4.2V/0.05C is cut off, standing for 10min, discharging at constant current until 3.0V is obtained, namely 1 cycle, repeating the step, when the battery capacity is lower than 80% of the first discharge capacity in the cycle process, ending the cycle, namely the cycle life of the batteries, AND averaging each group.
TABLE 2
From tables 1-2, the data for examples 1-4 compared to comparative examples 1-2 show that: the all-solid-state lithium battery provided by the disclosure has excellent cycle performance, and the cathode material is subjected to surface treatment to form the cathode active material containing the uniformly covered fluorine-containing lithium titanate layer.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. In order to avoid unnecessary repetition, various possible combinations will not be separately described in this disclosure.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (18)
1. The all-solid-state lithium battery comprises a positive plate, a negative plate and a solid electrolyte layer, and is characterized in that the positive plate comprises a positive active substance, and the positive active substance comprises positive material particles and a fluorine-containing lithium titanate layer coated on the surfaces of the positive material particles.
2. The all-solid-state lithium battery according to claim 1, wherein the fluorine-containing lithium titanate layer is a coating layer of fluorine-doped lithium titanate formed on the surface of the positive electrode material particles after being treated with titanium tetrafluoride and a lithium salt.
3. The all-solid-state lithium battery according to claim 1, wherein a molar ratio of fluorine atoms in the fluorine-containing lithium titanate to titanium atoms in the lithium titanate is 0.01 to 2.4: 1.
4. the all-solid lithium battery according to claim 1, wherein the particle diameter of the positive electrode active material is 0.05 to 1000 μm; the thickness of the fluorine-containing lithium titanate layer is 10-2000 nm.
5. The all solid-state lithium battery according to claim 2, wherein the lithium salt is L i2O、Li2S、LiOH、LiF、LiCl、LiBr、LiI、Li2CO3、Li2SO4、Li3PO4、LiNO3And at least one of lithium acetate, lithium methoxide, lithium ethoxide, lithium citrate, and lithium amide.
6. The all solid-state lithium battery according to claim 1, wherein the F/O atomic ratio of the lithium fluorotitanate-containing layer is 0.01 to 100.
7. The all solid-state lithium battery according to claim 1, wherein the solid electrolyte layer is at least one of a sodium fast ion conductor structure type solid electrolyte, a perovskite type solid electrolyte, and a sulfur type solid electrolyte.
8. The all solid-state lithium battery according to claim 7, wherein the sodium fast ion conductor structure type solid electrolyte is L iM2(PO4)3And their blendsAt least one of impurities, wherein M is at least one of Ti, Zr, Ge, Sn or Pb, L iM2(PO4)3The doping element adopted by the dopant of (1) is at least one of Mg, Ca, Sr, Ba, Sc, Al, Ga, In, Nb, Ta and V;
the perovskite type solid electrolyte is AxByTiO3、AxByTa2O6、AxByNb2O6Or AhMkDnTiwO3Wherein x +3Y =2, h +2k +5n +4w =6, 0 < x < 2, 0 < Y < 2/3, h, k, n, w are all more than 0, a is at least one of L i and Na elements, B is at least one of L a, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd elements, M is at least one of Sr, Ca, Ba, Ir, Pt elements, D is at least one of Nb, Ta elements;
the sulfur-based solid electrolyte is L i in a crystalline statexMyPzSwL i in glassy state2S-P2S5L i in the form of glass-ceramic2S-P2S5Wherein M is at least one of Si, Ge and Sn, x +4y +5z =2w, x is 2. ltoreq. x.ltoreq.11, y is 0. ltoreq. y.ltoreq.1.5, z is 0. ltoreq. z.ltoreq.3, and w is 3. ltoreq. w.ltoreq.13;
l i of the crystalline statexMyPzSwL i selected from crystalline state3PS4L i in crystalline form4SnS4L i in crystalline form4GeS4L i in crystalline form10SnP2S12L i in crystalline form10GeP2S12And L i in the crystalline state10SiP2S12L i in the glassy state2S-P2S5Selected from the group consisting of 70L i in glassy state2S-30P2S5Glassy 75L i2S-25P2S5And 80L i in glassy state2S-20P2S5L i in the glass-ceramic state2S-P2S570L i selected from the glass-ceramic state2S-30P2S575L i in the glass-ceramic state2S-25P2S5And 80L i in the form of a glass-ceramic2S-20P2S5At least one of (1).
9. The all solid-state lithium battery according to claim 1, wherein the positive electrode material is selected from L iCoO2、LiNiO2、LiMn2O4、LiFePO4、Li3V2(PO4)3、Li3V3(PO4)3、LiVPO4F、Li2CuO2、Li5FeO4、TiS2、V2S3、FeS、FeS2、TiO2、Cr3O8、V2O5、MnO2、LiCoxNi1-xO2、LiCoxNi1-x-yAlyO2、LiFepMnqX1-p-qO4、Li1＋ sL1－p－qMpNqO2And L iYSrAt least one of;
wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, p is more than or equal to 0 and less than or equal to 1, q is more than or equal to 0 and less than or equal to 1, p + q is more than or equal to 0 and less than or equal to 1, s is more than or equal to 0.1 and less than or equal to 0.2;
x is at least one of Al, Mg, Ga, Cr, Co, Ni, Cu, Zn or Mo, L and M, N are at least one of L I, Co, Mn, Ni, Fe, Al, Mg, Ga, Ti, Cr, Cu, Zn, Mo, F, I, S and B respectively and Y is at least one of Ti, Fe, Ni, Cu and Mo.
10. The all-solid lithium battery according to claim 1, wherein the positive electrode sheet further comprises a positive electrode conductive agent and a first binder, the positive electrode conductive agent is contained in an amount of 0.1 to 20 parts by weight and the first binder is contained in an amount of 0.01 to 10 parts by weight, relative to 100 parts by weight of the positive electrode active material;
the positive conductive agent is at least one of acetylene black, carbon nano tubes, carbon fibers and carbon black; the first binder is at least one of polyvinylidene fluoride, polytetrafluoroethylene and styrene butadiene rubber.
11. The all-solid lithium battery according to claim 1, wherein the solid electrolyte layer further comprises a second binder, the content of the second binder being 0.01 to 10 parts by weight with respect to 100 parts by weight of the solid electrolyte;
the second binder is at least one selected from polythiophene, polypyrrole, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-propylene-diene copolymer resin, styrene butadiene rubber, polybutadiene, fluororubber, polyethylene oxide, polyvinylpyrrolidone, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxypropyl cellulose, ethyl cellulose, polyethylene oxide, sodium carboxymethyl cellulose and styrene-butadiene latex.
12. The all-solid-state lithium battery according to claim 1, wherein the negative electrode sheet comprises a negative electrode current collector and a negative electrode material layer on the surface of the negative electrode current collector, the negative electrode material layer is lithium or a lithium alloy, or the negative electrode material layer comprises a negative electrode active material and a third binder.
13. The all solid-state lithium battery according to claim 12, wherein a content of the third binder is 0.01 to 10 parts by weight with respect to 100 parts by weight of the negative electrode active material;
the negative electrode active material is at least one selected from carbon materials, tin alloys, silicon, tin and germanium; the third binder is at least one selected from polythiophene, polypyrrole, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-propylene-diene copolymer resin, styrene butadiene rubber, polybutadiene, fluororubber, polyethylene oxide, polyvinylpyrrolidone, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxypropyl cellulose, ethyl cellulose, sodium carboxymethyl cellulose and styrene butadiene latex.
14. A method of producing an all-solid-state lithium battery including a positive electrode sheet, a negative electrode sheet, and a solid electrolyte layer, characterized by comprising the steps of:
(1) adding titanium tetrafluoride and lithium salt into a solvent, stirring until the titanium tetrafluoride and the lithium salt are dissolved, adding a positive electrode material, fully stirring, and evaporating the solvent to obtain a reaction precursor; sintering the reaction precursor to obtain a positive active material with a fluorine-containing lithium titanate layer coated on the surface of a positive material;
(2) and sequentially pressing a solid electrolyte layer containing a solid electrolyte and a negative plate on the positive plate containing the positive active material to obtain the all-solid-state lithium battery.
15. The method of claim 14, wherein the lithium salt is L i2O、Li2S、LiOH、LiF、LiCl、LiBr、LiI、Li2CO3、Li2SO4、Li3PO4、LiNO3And at least one of lithium acetate, lithium methoxide, lithium ethoxide, lithium citrate, and lithium amide.
16. The method according to claim 14, wherein in the step (1), the reaction conditions of the reaction of the cathode material with the titanium tetrafluoride and the lithium salt include: the evaporation temperature is 20-100 ℃, the sintering temperature is 400-1000 ℃, and the molar ratio of the anode material, the titanium tetrafluoride and the lithium salt in terms of lithium element is 1: (0.01-100): (0.01-100).
17. The method of claim 14, wherein the solid electrolyte layer is at least one of a sodium fast ion conductor structure type solid electrolyte, a perovskite type solid electrolyte, and a sulfur based solid electrolyte.
18. An all solid-state lithium battery prepared by the method of any one of claims 14 to 17.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710111544.9A CN108511786B (en) | 2017-02-28 | 2017-02-28 | All-solid-state lithium battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710111544.9A CN108511786B (en) | 2017-02-28 | 2017-02-28 | All-solid-state lithium battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108511786A CN108511786A (en) | 2018-09-07 |
| CN108511786B true CN108511786B (en) | 2020-07-10 |
Family
ID=63373162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710111544.9A Active CN108511786B (en) | 2017-02-28 | 2017-02-28 | All-solid-state lithium battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108511786B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110911634B (en) * | 2018-09-14 | 2022-03-15 | 比亚迪股份有限公司 | Positive electrode material and preparation method thereof, lithium battery positive plate and solid-state lithium battery |
| CN109346697B (en) * | 2018-10-12 | 2020-11-20 | 桑顿新能源科技有限公司 | Positive electrode active material, preparation method thereof and all-solid-state lithium battery |
| CN111129423B (en) * | 2018-10-30 | 2021-08-06 | 深圳市比亚迪锂电池有限公司 | Lithium ion battery cathode material and preparation method thereof, lithium ion battery cathode and lithium ion battery |
| CN111370751B (en) * | 2018-12-25 | 2021-12-07 | 深圳市比亚迪锂电池有限公司 | Solid-state battery, preparation method thereof and electric automobile |
| CN109768215B (en) * | 2018-12-27 | 2022-02-18 | 杭州阳名新能源设备科技有限公司 | Method for processing low-impedance interface of anode of solid-state lithium battery and anode structure |
| CN110600794B (en) * | 2019-09-03 | 2021-12-10 | 南方科技大学 | Solid-state lithium battery and preparation method thereof |
| CN110518283B (en) * | 2019-09-12 | 2024-11-15 | 深圳先进技术研究院 | All-solid-state secondary battery and its preparation process, electric vehicle |
| EP4123754A4 (en) * | 2020-03-18 | 2023-09-13 | Panasonic Intellectual Property Management Co., Ltd. | Positive electrode material, and battery |
| CN111403703A (en) * | 2020-03-18 | 2020-07-10 | 武汉理工大学 | Method for double coating of ternary positive electrode material by fluoride and sulfide |
| JPWO2022004397A1 (en) * | 2020-06-29 | 2022-01-06 | ||
| CN111682200B (en) * | 2020-07-14 | 2021-10-22 | 万华化学集团股份有限公司 | Positive electrode material for lithium ion battery and preparation method thereof |
| CN112768626B (en) * | 2021-01-25 | 2022-07-15 | 欣旺达电动汽车电池有限公司 | Positive pole piece, preparation method thereof and solid-state battery |
| CN114614012B (en) * | 2022-03-14 | 2024-06-18 | 宁波容百新能源科技股份有限公司 | Ternary composite material for all-solid-state battery, preparation method and application 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5586837B2 (en) * | 2007-10-11 | 2014-09-10 | 国立大学法人福井大学 | Positive electrode material for non-aqueous electrolyte secondary battery |
| JP5144845B2 (en) * | 2008-01-31 | 2013-02-13 | 株式会社オハラ | Solid battery |
| CN103107324B (en) * | 2013-03-04 | 2016-03-02 | 江苏大学 | A kind of preparation method of fluorine-containing lithium ionic cell cathode material lithium titanate |
| CN103825020A (en) * | 2013-12-17 | 2014-05-28 | 中国科学院宁波材料技术与工程研究所 | Cobalt-based cathode material for all-solid-state lithium secondary battery and preparation method for cobalt-based cathode material |
-
2017
- 2017-02-28 CN CN201710111544.9A patent/CN108511786B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108511786A (en) | 2018-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108511786B (en) | All-solid-state lithium battery and preparation method thereof | |
| CN111276690B (en) | Low-porosity positive pole piece, preparation method thereof and application of positive pole piece in solid-state lithium metal battery | |
| CN111384377B (en) | Positive electrode material and preparation method and application thereof | |
| CN108172891B (en) | All-solid-state lithium battery and preparation method thereof | |
| CN110931849B (en) | Gradient composite solid electrolyte, preparation method thereof and solid lithium battery | |
| CN111557057B (en) | Positive electrode material and battery using the same | |
| EP3414787A1 (en) | Pre-lithiated electrode materials and cells employing the same | |
| CN107408686A (en) | Cathode active material for lithium ion secondary battery, method for producing same, and lithium ion secondary battery comprising same | |
| CN104659343A (en) | Negative active material and negative electrode and lithium battery containing the material, and method of manufacturing the same | |
| KR20200007325A (en) | Lithium Secondary Battery Comprising Liquid Inorganic Electrolyte | |
| CN110828783A (en) | Lithium battery positive electrode material and preparation method and application thereof | |
| JP2011100745A (en) | Nonaqueous electrolyte secondary battery | |
| CN106663815B (en) | Method for producing conductive material, conductive material produced thereby, and lithium secondary battery including the same | |
| JP2009245917A (en) | Positive electrode active material for nonaqueous electrolyte secondary battery, method for manufacturing same, and positive electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery | |
| CN111864256B (en) | Sulfide solid electrolyte and all-solid-state lithium secondary battery | |
| CN102097623B (en) | Anode for lithium battery active material and manufacture method, positive pole and lithium battery | |
| WO2022194219A1 (en) | Composite solid electrolyte material for battery negative electrode, negative electrode plate and all-solid-state lithium battery | |
| CN112420977A (en) | Lithium battery and preparation method thereof | |
| CN102867948B (en) | Compound, its method for making, negative active core-shell material, negative pole and lithium secondary battery | |
| CN110911736B (en) | Solid electrolyte, preparation method thereof and solid lithium battery | |
| CN110911634B (en) | Positive electrode material and preparation method thereof, lithium battery positive plate and solid-state lithium battery | |
| JP7523591B2 (en) | All-solid-state battery containing silicon (Si) as the negative electrode active material | |
| CN113614948B (en) | Positive electrode material and battery | |
| CN112242519B (en) | Positive electrode material, preparation method thereof and solid-state lithium battery | |
| CN112448021B (en) | Composite solid electrolyte and solid lithium battery |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |