CN113782708A - Positive electrode and electrochemical device containing same - Google Patents
Positive electrode and electrochemical device containing same Download PDFInfo
- Publication number
- CN113782708A CN113782708A CN202111056355.9A CN202111056355A CN113782708A CN 113782708 A CN113782708 A CN 113782708A CN 202111056355 A CN202111056355 A CN 202111056355A CN 113782708 A CN113782708 A CN 113782708A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- lithium
- positive
- electrolyte
- layer
- 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.)
- Granted
Links
- 239000002131 composite material Substances 0.000 claims abstract description 100
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 58
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 47
- 239000007774 positive electrode material Substances 0.000 claims abstract description 42
- 239000002322 conducting polymer Substances 0.000 claims abstract description 28
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 28
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical group [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 23
- 239000011149 active material Substances 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims description 54
- -1 polyethylene Polymers 0.000 claims description 20
- 239000006256 anode slurry Substances 0.000 claims description 19
- 239000002033 PVDF binder Substances 0.000 claims description 18
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 13
- 239000011267 electrode slurry Substances 0.000 claims description 12
- 229920001610 polycaprolactone Polymers 0.000 claims description 10
- 239000004632 polycaprolactone Substances 0.000 claims description 10
- 239000010416 ion conductor Substances 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000004014 plasticizer Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 4
- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical group FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000006183 anode active material Substances 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 3
- 239000004626 polylactic acid Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 3
- 239000011118 polyvinyl acetate Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002227 LISICON Substances 0.000 claims description 2
- 239000002228 NASICON Substances 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-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
- PGRMNXHYAZYNPG-UHFFFAOYSA-N fluoro hydrogen carbonate Chemical compound OC(=O)OF PGRMNXHYAZYNPG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002223 garnet Substances 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- ZQCQTPBVJCWETB-UHFFFAOYSA-N 4-fluoro-1,3-dioxol-2-one Chemical compound FC1=COC(=O)O1 ZQCQTPBVJCWETB-UHFFFAOYSA-N 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 63
- 238000010041 electrostatic spinning Methods 0.000 abstract description 20
- 239000007784 solid electrolyte Substances 0.000 abstract description 11
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 238000007599 discharging Methods 0.000 abstract description 2
- 238000004880 explosion Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 82
- 238000009987 spinning Methods 0.000 description 82
- 239000005518 polymer electrolyte Substances 0.000 description 51
- 238000002156 mixing Methods 0.000 description 44
- 238000000034 method Methods 0.000 description 25
- 239000002002 slurry Substances 0.000 description 22
- 238000001035 drying Methods 0.000 description 20
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 19
- 239000011230 binding agent Substances 0.000 description 19
- 239000002243 precursor Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- 238000000576 coating method Methods 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 15
- 239000006258 conductive agent Substances 0.000 description 15
- 239000011888 foil Substances 0.000 description 14
- 238000001523 electrospinning Methods 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000005096 rolling process Methods 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 229910013716 LiNi Inorganic materials 0.000 description 8
- 238000000280 densification Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000006230 acetylene black Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000005486 organic electrolyte Substances 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910018632 Al0.05O2 Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910009515 Li1.5Al0.5Ti1.5(PO4)3 Inorganic materials 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910006194 Li1+xAlxGe2-x(PO4)3 Inorganic materials 0.000 description 1
- 229910006196 Li1+xAlxGe2−x(PO4)3 Inorganic materials 0.000 description 1
- 229910006210 Li1+xAlxTi2-x(PO4)3 Inorganic materials 0.000 description 1
- 229910006212 Li1+xAlxTi2−x(PO4)3 Inorganic materials 0.000 description 1
- 229910009297 Li2S-P2S5 Inorganic materials 0.000 description 1
- 229910009311 Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910009228 Li2S—P2S5 Inorganic materials 0.000 description 1
- 229910009225 Li2S—P2S5—GeS2 Inorganic materials 0.000 description 1
- 229910009433 Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910011244 Li3xLa2/3-xTiO3 Inorganic materials 0.000 description 1
- 229910011245 Li3xLa2/3−xTiO3 Inorganic materials 0.000 description 1
- 229910011671 Li4-xGe1-xPxS4 Inorganic materials 0.000 description 1
- 229910011572 Li4−xGe1−xPxS4 Inorganic materials 0.000 description 1
- 229910011201 Li7P3S11 Inorganic materials 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910012097 LiSbF Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 1
- 229910006180 NixCoyAl1-x-yO2 Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- YCOASTWZYJGKEK-UHFFFAOYSA-N [Co].[Ni].[W] Chemical compound [Co].[Ni].[W] YCOASTWZYJGKEK-UHFFFAOYSA-N 0.000 description 1
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 description 1
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- NKLLZZNEDKQOOB-UHFFFAOYSA-N [O-2].[Mg+2].[Ti+4].[Ni+2].[Li+] Chemical compound [O-2].[Mg+2].[Ti+4].[Ni+2].[Li+] NKLLZZNEDKQOOB-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 238000001467 acupuncture Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- OKVJWADVFPXWQD-UHFFFAOYSA-N difluoroborinic acid Chemical compound OB(F)F OKVJWADVFPXWQD-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical group [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- XKLXIRVJABJBLQ-UHFFFAOYSA-N lithium;2-(trifluoromethyl)-1h-imidazole-4,5-dicarbonitrile Chemical compound [Li].FC(F)(F)C1=NC(C#N)=C(C#N)N1 XKLXIRVJABJBLQ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000002203 sulfidic glass Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a positive electrode and an electrochemical device containing the same, wherein a composite positive plate comprises a current collector, a first positive layer positioned on the surface of the current collector and a second positive layer positioned on the surface of the first positive layer; the first positive electrode layer includes a positive electrode active material and a lithium conducting polymer in a continuous phase form; the second positive electrode layer includes a positive electrode active material and a lithium conducting polymer in a continuous phase form; the positive active material in the first positive layer is selected from lithium iron phosphate; the positive electrode active material in the second positive electrode layer is selected from other active materials than lithium iron phosphate. The lithium conducting polymer in the laminated structure composite positive plate prepared by electrostatic spinning is more uniformly distributed, and the transmission efficiency of lithium ions and electrons is effectively improved, so that the resistance of the interface of a positive electrode and a solid electrolyte is obviously reduced, the lithium conducting capacity of the positive electrode is further improved, the safety performance of the battery can be further improved by the LFP solid composite positive electrode primer, and fire and explosion do not occur even though deep charging and discharging.
Description
Technical Field
The invention belongs to the technical field of electrochemical devices, and particularly relates to a positive electrode and an electrochemical device containing the same.
Background
Lithium ion batteries have been rapidly developed in the fields of notebooks, mobile phones, digital products, etc. because of their excellent characteristics of small size, light weight, high specific energy, no pollution, small self-discharge, long life, etc. Nowadays, the application of high-energy-density and high-power lithium ion batteries to the field of new energy vehicles is becoming a core technology, but higher requirements are provided for the structure and performance of the lithium ion batteries, and new challenges are faced to the key materials of the lithium ion batteries. At present, the industrialization of lithium ion batteries taking graphite as a negative electrode is difficult to meet the increasing demand of high specific energy. The solid electrolyte has higher mechanical strength, excellent compactness, certain capability of resisting the growth of lithium dendrites, and no characteristics of easy volatilization, flammability, explosiveness and the like of liquid organic electrolyte, so that the safety of the lithium ion battery in the use process can be greatly improved if the solid electrolyte is adopted to replace the liquid organic electrolyte to develop the all-solid lithium ion battery. However, the core components in solid-state lithium ion batteries are solid-solid contact between the solid electrolyte and the electrode, and thus the interface problem between the solid electrolyte and the electrode is mainly focused on: (1) the interface between the electrolyte and the positive electrode has poor contact wettability, so that the interface resistance is easily increased, and the interface transmission of lithium ions is influenced; (2) in the continuous circulation process of the lithium ion battery, the mutual diffusion of elements at the interface can cause the transmission capability of lithium ions at the interface to be reduced, so that the performance of the lithium ion battery is further deteriorated, and the water is recycled; (3) the solid electrolyte is different from the liquid organic electrolyte, and cannot infiltrate the pole piece to finish the migration of lithium ions, so that the lithium ion conducting capability of the traditional solid electrolyte composite anode is poor, and the lithium conducting capability of the bottom layer on one side close to the current collector is poorer for the anode with larger surface density, so that the lithium ions are more difficult to be inserted and removed. At present, the stability and adhesion between interfaces are mainly increased by adding a small amount of polymer electrolyte to the positive electrode, however, due to the influence of the active material, conductive agent and binder contained in the positive electrode, the polymer actually added to the positive electrode for conducting lithium is not uniformly distributed, and even agglomeration problem occurs, thereby affecting the conduction of lithium ions. And when the lithium ion battery is further assembled, the collapse of the structure in the positive pole piece can further accelerate the occurrence of interface side reaction along with the circulation of the battery, so that a lithium guide channel in the electrode is damaged, and further the capacity exertion of the battery is limited, the internal resistance of the battery is increased, and the cycle performance is deteriorated.
Therefore, it is desirable to provide a solid-state positive electrode sheet with high safety, which can improve the transmission of lithium ions in the solid-state positive electrode sheet.
Disclosure of Invention
In order to improve the technical problems, the invention provides the LFP composite positive electrode containing the polymer existing in the continuous phase form, the side close to the current collector is the LFP composite positive electrode with the three-dimensional continuous phase structure, the side close to the electrolyte is the LCO/NCM composite positive electrode layer with the three-dimensional continuous phase structure, the resistance of the interface of the positive electrode and the electrolyte can be obviously reduced, the lithium conduction capability of the positive electrode piece is improved, and importantly, the LFP priming coating further improves the safety of the composite positive electrode on the battery.
The composite positive plate is characterized in that positive slurry and a lithium-conducting polymer are uniformly coated on a current-collecting foil by an electrostatic spinning method, and compared with the traditional mode of directly adding the lithium-conducting polymer into the positive electrode for mixed coating, the layered-structure solid composite positive electrode prepared by electrostatic spinning is more uniform in performance, the transport efficiency of ions and electrons is effectively improved, the process is simple, the operation is convenient, the safety is high, and the method is suitable for industrial application.
Still another object of the present invention is to provide an electrochemical device (such as a solid-state lithium ion battery) using the composite positive electrode, which has low internal resistance, good cycle performance and high safety.
In order to achieve the purpose, the invention adopts the technical scheme that:
a composite positive plate comprises a current collector, a first positive plate layer and a second positive plate layer, wherein the first positive plate layer is positioned on the surface of the current collector; the first positive electrode layer includes a positive electrode active material and a lithium conducting polymer in a continuous phase form; the second positive electrode layer includes a positive electrode active material and a lithium conducting polymer in a continuous phase form; the positive active material in the first positive layer is selected from lithium iron phosphate; the positive electrode active material in the second positive electrode layer is selected from other active materials than lithium iron phosphate.
According to the invention, the first positive electrode layer and the second positive electrode layer contain three-dimensional polymer conductive channels, namely three-dimensional lithium conducting and conductive networks which are continuously penetrated.
In the present invention, the "lithium iron phosphate" may be at least one of lithium iron phosphate (LFP) and a dopant, a modifier, and a coating of lithium iron phosphate.
According to the invention, the positive plate comprises a current collector, a first positive layer and a second positive layer, wherein the first positive layer and the second positive layer are coated on the surface of the current collector, and the first positive layer close to the current collector comprises 50-90% of positive slurry containing lithium iron phosphate positive active materials and 10-50% of lithium conducting polymer in a continuous phase form; the second anode layer positioned above the first anode layer comprises 50-90% of anode slurry of other anode active materials except ferric lithium phosphate and 10-50% of lithium conducting polymer in a continuous phase form.
According to the present invention, the thickness of the first positive electrode layer may be 1 to 200 μm; exemplary are 1 μm, 10 μm, 50 μm, 100 μm, 200 μm.
According to the present invention, the thickness of the second positive electrode layer may be 1 to 300 μm; exemplary are 1 μm, 10 μm, 50 μm, 100 μm, 200 μm, 300 μm.
According to the invention, the thickness of the whole composite positive plate can be 2-500 μm; exemplary are 2 μm, 10 μm, 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm.
According to the invention, the composite positive plate is formed by coating the raw materials including the positive slurry and the lithium-conducting polymer on the surface of the current-collecting foil through an electrostatic spinning method.
Preferably, the positive electrode slurry includes a positive electrode active material, a conductive agent, and a binder;
preferably, the mass ratio of the positive electrode active material to the conductive agent to the binder is 80-98%: 0.5-10%: 0.5-10%; exemplary are 80:10:10, 90:5:6, 94:4:2, 95:0.5:4.5, 96:3:1, 98:1.5: 0.5.
Illustratively, the positive electrode active material in the first positive electrode layer is selected from at least one of lithium iron phosphate (LFP) and doping, modification, and cladding of lithium iron phosphate.
For example, the positive electrode active material contains one, two or more of lithium element, iron element, phosphorus element, cobalt element, manganese element, nickel element, and aluminum element; preferably, the positive active material is an active material coated with one or two or more elements selected from aluminum, magnesium, titanium, zirconium, nickel, manganese, yttrium, lanthanum, strontium and the like.
Illustratively, the positive active material in the second positive electrode layer is selected from one or more of lithium cobaltate, nickel cobalt manganese ternary battery material, lithium manganate, nickel cobalt aluminum ternary battery material and lithium-rich manganese-based material.
For exampleThe positive electrode active material in the second positive electrode layer is selected from lithium cobaltate (LiCoO)2) Lithium nickel cobalt manganese oxide (LizNi)xCoyMn1-x-yO2Wherein: z is more than or equal to 0.95 and less than or equal to 1.05, x>0，y>0，x+y<1) Lithium manganate (LiMnO)2) Lithium nickel cobalt aluminate (Li)zNixCoyAl1-x-yO2Wherein: z is more than or equal to 0.95 and less than or equal to 1.05, x>0，y>0，0.8≤x+y<1) Lithium nickel cobalt manganese aluminate (Li)zNixCoyMnwAl1-x-y-wO2Wherein: z is more than or equal to 0.95 and less than or equal to 1.05, x>0，y>0，w>0，0.8≤x+y+w<1) Nickel cobalt aluminum tungsten material, lithium-rich manganese-based solid solution positive electrode material, lithium nickel cobalt oxide (LiNi)xCoyO2Wherein: x is the number of>0，y>0, x + y ═ 1), lithium nickel titanium magnesium oxide (LiNi)xTiyMgzO2Wherein: x is the number of>0，y>0，z>0, x + y + z ═ 1), lithium nickelate (Li)2NiO2) Spinel lithium manganate (LiMn)2O4) And nickel-cobalt-tungsten material, and the like.
According to the present invention, the conductive agent is selected from at least one of conductive carbon black (SP), ketjen black, acetylene black, Carbon Nanotubes (CNT), graphene, and flake graphite.
According to the invention, the binder is selected from at least one of polytetrafluoroethylene, polyvinylidene fluoride (PVDF) and polyvinylidene fluoride-hexafluoropropylene.
According to the invention, the lithium conducting polymer comprises a polymer, an electrolyte salt, a plasticizer and optionally an added or not added fast ion conductor.
According to the invention, the mass ratio of the polymer, the electrolyte salt, the plasticizer and the fast ion conductor is 50-80%: 10-40%, 1-10%: 0-10%, exemplary 50:40:10:0, 55:20:17:8, 60:30:5:5, 65:24:9:2, 68:18:7:7, 70:19:5:6, 80:10:1: 9.
According to the invention, the polymer is a polymer suitable for electrospinning, for example at least one selected from the group consisting of polymethylmethacrylate, polystyrene, polyvinyl chloride, polyethylene, polypropylene, polycarbonate, polyvinyl acetate, polyethylene oxide, polyacetimide, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene, polyvinyl alcohol, polyacrylonitrile, polylactic acid and Polycaprolactone (PCL).
According to the present invention, the electrolyte salt includes at least one of a lithium salt, a sodium salt, a magnesium salt, and an aluminum salt, preferably lithium. Illustratively, the lithium salt is lithium perchlorate (LiClO)4) Lithium hexafluorophosphate (LiPF)6) Lithium hexafluoroarsenate (LiAsF)6) Lithium tetrafluoroborate (LiBF)4) Lithium bis (oxalato) borate (LiBOB), lithium bis (oxalato) difluoroborate (LiDFOB), lithium bis (difluorosulfonimide) (LiFSI), lithium bis (trifluoromethylsulfonimide) (LiTFSI), lithium (trifluoromethylsulfonate) (LiCF)3SO3) Bis (malonic) boronic acid (LiBMB), lithium oxalatoborate malonate (LiMOB), lithium hexafluoroantimonate (LiSbF)6) Lithium difluorophosphate (LiPF)2O2) Lithium 4, 5-dicyano-2-trifluoromethylimidazole (LiDTI), lithium bis (trifluoromethylsulfonyl) imide (LiN (SO)2CF3)2)、LiN(SO2C2F5)2、LiC(SO2CF3)3And LiN (SO)2F)2One, two or more.
According to the invention, the plasticizer is selected from at least one of methoxy polyethylene glycol acrylate, polyethylene glycol methyl ether methacrylate, succinonitrile, ethylene carbonate, propylene carbonate, vinylene carbonate, ethylene sulfite, propylene sulfite, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, fluoro carbonate, tetraethylene glycol dimethyl ether, 1,3 dioxolane, fluorobenzene, fluoro ethylene carbonate, ionic liquid and the like.
According to the invention, the fast ion conductor may be a combination of one or more of a perovskite type electrolyte, an anti-perovskite type electrolyte, a Garnet type electrolyte, a NASICON type electrolyte, a LISICON type electrolyte, a sulphide electrolyte.
Illustratively, the perovskite-type electrolyte is Li3xLa2/3-xTiO3Wherein: x is more than 0.04 and less than 0.17.
Illustratively, the calcium counteractionThe titanium ore type electrolyte is Li3-n(OHn) Cl (n is more than or equal to 0.83 and less than or equal to 2) and Li3-n(OHn)Br(1≤n≤2)。
Illustratively, the garnet-type electrolyte is a lithium lanthanum zirconium oxide electrolyte and Al, Ga, Fe, Ge, Ca, Ba, Sr, Y, Nb, Ta, W, Sb element doped derivatives thereof; preferably Li7-nLa3Zr2-nTanO12、Li7-nLa3Zr2-nNbnO12Or Li6.4- xLa3Zr2-xTaxAl0.2O12(ii) a Wherein: n is more than or equal to 0 and less than or equal to 0.6; x is 0.2 to 0.5.
Illustratively, the NASICON-type electrolyte is Li1+xTi2-xMx(PO4)3(M ═ Al, Cr, Ga, Fe, Sc, In, Lu, Y, La), preferably Li1+xAlxTi2-x(PO4)3(LATP) (x is more than or equal to 0.2 and less than or equal to 0.5) or Li1+xAlxGe2-x(PO4)3(LAGP)(0.4≤x≤0.5)。
Illustratively, the LISICON-type electrolyte is Li4-xGe1-xPxS4(x ═ 0.4 or x ═ 0.6).
Illustratively, the sulfide solid electrolyte is selected from Li2S-SiS2、Li2S-P2S5、Li2S-P2S5-GeS2、Li7P3S11And Li6PS5And X (X ═ Cl, Br, I) is at least one.
The invention also provides an electrochemical device which comprises the composite positive plate.
According to the present invention, the electrochemical device is, for example, a lithium ion battery; specifically, the lithium ion battery is a solid-state lithium ion battery.
According to the invention, the solid-state lithium ion battery can be a button battery, a die battery, a pouch battery or an aluminum-case battery.
According to the invention, the lithium ion battery further comprises an electrolyte.
According to the invention, in the lithium ion battery, the composite positive plate and the electrolyte are in an integral structure.
The invention has the beneficial effects that:
(1) in the composite positive plate, the positive slurry and the lithium-conducting polymer are uniformly coated on the current-collecting foil by an electrostatic spinning method. Compared with the traditional mode of directly adding the lithium conducting polymer into the positive electrode for mixed coating, the lithium conducting polymer in the composite positive electrode plate with the layered structure prepared by electrostatic spinning is more uniformly distributed, and the lithium conducting polymer can exist in a continuous phase form, so that a continuous through three-dimensional polymer lithium conducting channel can be formed, and the transmission efficiency of lithium ions and electrons is effectively improved; the layered composite solid positive plate can be matched with all positive materials on the market, and the LFP solid composite positive primer can further improve the safety performance of the battery, so that fire and explosion do not occur even if the battery is charged and discharged deeply.
(2) The composite solid-state positive electrode provided by the invention is provided with the continuously-through three-dimensional lithium-conducting network, and the ion transmission channel is smooth, so that the problems of difficult lithium conduction in the positive electrode and uneven ion transmission of a solid-state battery are solved, the resistance of the positive electrode and a solid-state electrolyte interface can be obviously reduced, and the lithium conduction capability of a positive electrode plate is further improved.
(3) The composite solid-state positive plate can greatly reduce the concentration polarization in the electrode when discharging with high load capacity and high multiplying power so as to effectively improve the transport efficiency of ions in the solid-state plate and further improve the specific capacity and specific energy of an electrochemical device (such as a lithium ion battery). The composite positive plate is simple in preparation process, convenient to operate, remarkable in effect and suitable for industrial application.
Drawings
Fig. 1 is a schematic structural diagram of the composite positive plate of the present invention.
FIG. 2 is a schematic diagram of the structure of a lithium ion battery prepared in example 2 of the present invention
Fig. 3 is a schematic view of a positive electrode layer (first positive electrode layer or second positive electrode layer) produced by an electrospinning method according to the present invention.
FIG. 4 is an SEM micrograph of a cross section of a composite positive electrode made in example 3.
Fig. 5 is a first charge-discharge curve diagram of the lithium ion battery assembled by the composite positive electrode sheet in example 4.
Detailed Description
As described above, the present invention provides a composite positive plate with a special structure, and based on the positive plate, the present invention also provides a method for preparing the composite positive plate, wherein the method comprises the steps of using positive electrode slurry and a lithium-conducting polymer as raw materials, and coating the raw materials on the surface of a current-collecting foil by an electrostatic spinning method to prepare the composite positive plate.
According to the present invention, the positive electrode slurry and the lithium conducting polymer have the selection and the amount ratio as described above.
According to the invention, the preparation method of the composite positive plate comprises the following steps:
s1: uniformly mixing an electrostatic spinning polymer, electrolyte salt, a plasticizer and an optionally added fast ion conductor in a solvent, and ultrasonically dispersing to prepare a polymer electrolyte spinning solution 1;
s2: mixing and stirring a lithium iron phosphate LFP positive electrode active material, a conductive agent and a binder in a solvent to prepare a positive electrode precursor solution 2;
s3: mixing and stirring a non-lithium iron phosphate positive active material, a conductive agent and a binder in a solvent to prepare a positive precursor liquid 3;
s4: mixing the polymer electrolyte spinning solution 1 and the anode precursor solution 2 to prepare an anode spinning solution A; mixing the polymer electrolyte spinning solution 1 and the positive electrode precursor solution 3 to prepare a positive electrode spinning solution B;
s5: spinning the positive electrode spinning solution A onto a current-collecting foil by an electrostatic spinning method to form an LFP first positive electrode layer bottom coating; then carrying out electrostatic spinning on the positive spinning solution B on the basis of the first LFP positive layer base coat to obtain a second positive layer;
s6: drying and rolling to obtain the layered composite positive plate.
According to the present invention, in step S1, the organic solvent is at least one of Acetonitrile (ACN), N-methylpyrrolidone (NMP), Dimethylformamide (DMF), Dimethylacetamide (DMAC), Dimethylsulfoxide (DMSO), ethanol, acetone, dichloromethane, chloroform, xylene, and Tetrahydrofuran (THF).
According to the present invention, in step S1, the solid content of the polymer electrolyte spinning solution 1 is 5 to 40%, and exemplary is 5%, 10%, 20%, 30%, 40%.
According to the present invention, the solvent described in steps S2, S3 is N-methylpyrrolidone (NMP).
According to the invention, the solid content of the positive electrode slurry in the steps S2 and S3 is 20-80%, and is exemplified by 20%, 30%, 40%, 50%, 60%, 70% and 80%.
According to the present invention, in step S4, the first positive electrode layer spinning solution a on the side of the near current collector includes 50% to 90% of positive electrode slurry containing a lithium iron phosphate-containing positive electrode active material and 10% to 50% of a lithium conducting polymer;
the second anode layer spinning solution positioned above the first anode layer comprises 50-90% of anode slurry of other anode active materials except ferric lithium phosphate and 10-50% of lithium conducting polymer.
According to the present invention, in step S5, the distance between the injection needle and the receiving plate of the electrospinning method may be 5-40cm, preferably 10-30 cm; exemplary are 5cm, 10cm, 14cm, 20cm, 30cm, 40 cm.
According to the invention, in step S5, the moving speed of the current-collecting foil during the electrospinning process is 0.1-4m/min, preferably 0.5-2 m/min; illustrative are 0.1m/min, 0.5m/min, 0.8m/min, 1m/min, 1.2m/min, 2m/min, 3m/min, 4 m/min.
According to the invention, in step S5, in the electrostatic spinning process, the high-voltage power supply is 5-40kV, preferably 10-25 kV; exemplary are 5KV, 10KV, 15KV, 20KV, 25KV, 30KV, 40 KV.
According to the present invention, in step S6, the drying temperature may be 60-120 ℃; exemplary are 60 deg.C, 80 deg.C, 100 deg.C, 120 deg.C.
According to the present invention, the method for preparing the composite positive electrode sheet may further optionally include step S7: and (3) performing electrolyte coating on the surface of the composite positive plate prepared in the step S6 and/or performing electrostatic spinning on the polymer electrolyte spinning solution 1 on the surface of the composite positive plate prepared in the step S6 to prepare a composite positive electrode-electrolyte integrated structure.
As described above, the present invention also provides an electrochemical device including the composite positive electrode sheet described above.
According to the invention, the electrochemical device is, for example, a lithium ion battery, in particular an all solid-state lithium ion battery.
According to the invention, the lithium ion battery further comprises a negative electrode. Preferably, the negative electrode active material in the negative electrode is, for example, at least one selected from the group consisting of carbon materials, metal bismuth, metal lithium, metal copper, metal indium, nitrides, lithium-based alloys, magnesium-based alloys, indium-based alloys, boron-based materials, silicon-based materials, tin-based materials, antimony-based alloys, gallium-based alloys, germanium-based alloys, aluminum-based alloys, lead-based alloys, zinc-based alloys, oxides of titanium, oxides of iron, oxides of chromium, oxides of molybdenum, and phosphides, etc.
According to the present invention, the lithium ion battery further optionally comprises an electrolyte, the electrolyte being located between the composite positive electrode sheet and the negative electrode.
Preferably, the electrolyte may be a solid electrolyte. Further, the solid electrolyte may be one of an inorganic solid electrolyte and an organic polymer electrolyte, and is preferably an organic polymer electrolyte.
Illustratively, the inorganic solid electrolyte may be either an oxide electrolyte or a sulfide electrolyte.
Illustratively, the organic polymer electrolyte is selected from the group consisting of polymethylmethacrylate, polystyrene, polyvinyl chloride, polyethylene, polypropylene, polycarbonate, polyvinyl acetate, polyethylene oxide, polyacetimide, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene, polyvinyl alcohol, polyacrylonitrile, polylactic acid, Polycaprolactone (PCL), polycarbonate, polyether, polyethylene glycol, polyphenylene oxide, polyethylene diamine, polyethylene glycol thiol, and the like, and copolymerized derivatives thereof.
According to the invention, the electrolyte and the composite positive plate are in an integral structure.
According to the invention, the lithium-conducting polymer spinning solution is subjected to electrostatic spinning on the surface of the composite positive plate to prepare the electrolyte and the composite positive plate with an integrated structure.
The invention also provides a preparation method of the lithium ion battery, which comprises the steps of sequentially assembling the composite positive plate, the optional electrolyte and the negative electrode together, and carrying out vacuum packaging to obtain the lithium ion battery.
Specifically, the composite electrode plate and the electrolyte exist in an integrated structure form, and the composite electrode plate is prepared by a method comprising the following steps:
preparing the composite electrode slice by adopting the method for preparing the composite electrode slice;
carrying out electrolyte coating on the surface of the composite positive plate and/or carrying out electrostatic spinning on the lithium-conducting polymer spinning solution on the surface of the composite positive plate to prepare a composite positive electrode-electrolyte integrated structure;
then the lithium ion battery is assembled with the cathode and is packaged in vacuum to obtain the lithium ion battery.
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
The test methods for each example and comparative example are as follows:
1. AC impedance test at room temperature
The method for testing the alternating current impedance of the lithium ion battery comprises the following steps:
the test was carried out using the Shanghai Chenghua CHI600E electrochemical workstation, with the parameters set: the amplitude is 10mV, and the frequency range is 0.1 Hz-3 MHz.
2. Cycle life testing of lithium ion batteries
The test instrument is Wuhan blue battery test equipment;
and (3) testing conditions are as follows: the specific capacity exertion, the cycle number and the first turn coulombic efficiency are measured under the conditions of 25 ℃ and 0.2C/0.2C.
3. Lithium ion battery safety performance test-acupuncture test
The high-temperature resistant steel needle with the diameter phi of (5 +/-0.5) mm penetrates through the battery cell from the direction vertical to the polar plate of the battery cell at the speed of (25 +/-5) mm/s, the puncture position is preferably close to the geometric center of the punctured surface (the steel needle stays in the battery cell), and the battery cell is marked as passing when the battery cell does not catch fire and explode. The test quantity of the electric cores is 10, and the needling passing rate of the electric cores is respectively tested.
Example 1
The composite positive electrode structure provided by the invention is shown in figure 1, and the composite positive electrode comprises a solid composite positive electrode layer I and a current collector layer II. The solid-state composite positive electrode layer comprises a first positive electrode layer on the side close to the current collector and a second positive electrode layer above the first positive electrode layer.
The process for preparing composite solid state positive electrodes and solid state batteries by electrospinning is as follows:
s1: polyvinylidene fluoride, lithium bistrifluoromethylsulfonyl imide (LiTFSI), polyethylene glycol methyl ether methacrylate and Li6.6La3Zr1.6Ta0.4O12Uniformly mixing the fast ion conductor in DMAC according to the mass ratio of 68:21:7:4, and ultrasonically dispersing to prepare a polymer electrolyte spinning solution 1 with the solid content of 11%;
s2: preparing a slurry with the solid content of 72% from a positive electrode active material lithium iron phosphate, a conductive agent acetylene black and a binder PVDF in NMP according to the mass ratio of 94:3:3, and uniformly mixing and stirring to obtain a positive electrode precursor solution 2;
s3: preparing a slurry with solid content of 72% from a positive electrode active material lithium cobaltate, a conductive agent acetylene black and a binder PVDF in NMP according to a mass ratio of 94:3:3, and uniformly mixing and stirring to obtain a positive electrode precursor liquid 3;
s4: mixing the polymer electrolyte spinning solution 1 and the positive electrode LFP precursor solution 2 according to the proportion of 25:75 of solid content to prepare a first positive electrode layer spinning solution A; mixing the polymer electrolyte spinning solution 1 and the positive electrode precursor solution 3 according to the proportion of solid content of 30:70 to prepare a second positive electrode layer spinning solution B;
s5: mounting an Al foil current collector on a receiving plate, adjusting the distance between an injector and the receiving plate to be 15cm, adjusting the moving speed of the current collector to be 0.8m/min, setting a high-voltage power supply to be 16kV, setting the internal spinning temperature of electrostatic spinning equipment to be 45 ℃, adding a first positive pole layer spinning solution A into the injector, and controlling the thickness of a first positive pole layer after spinning and drying to be 30 mu m; then, an injector containing a second anode layer spinning solution B is used, the same step is carried out, and the thickness of the dried second anode layer is controlled to be 50 micrometers;
s6: after drying for 12h at 80 ℃, performing rolling densification on the composite positive electrode to obtain the composite positive electrode sheet;
s7: preparation of solid-state batteries: the polymer electrolyte spinning solution 1 was further coated on the surface of the positive electrode sheet rolled in step S6 (to ensure good connection of the interface), and the electrolyte membrane thickness was 40 μm;
s8: and (5) assembling the composite positive plate and the PVDF integrated structure prepared in the step (S7) with a metal lithium negative electrode to form the all-solid-state battery.
Comparative example 1
The process for preparing composite solid state positive electrodes and solid state batteries by electrospinning is as follows:
s1: polyvinylidene fluoride, lithium bistrifluoromethylsulfonyl imide (LiTFSI), polyethylene glycol methyl ether methacrylate and Li6.6La3Zr1.6Ta0.4O12Uniformly mixing the fast ion conductor in DMAC according to the mass ratio of 68:21:7:4, and ultrasonically dispersing to prepare a polymer electrolyte spinning solution 1 with the solid content of 11%;
s2: preparing a slurry with solid content of 72% from a positive electrode active material lithium cobaltate, a conductive agent acetylene black and a binder PVDF in NMP according to a mass ratio of 94:3:3, and uniformly mixing and stirring to obtain a positive electrode precursor liquid 3;
s3: mixing the polymer electrolyte spinning solution 1 and the positive electrode precursor solution 3 according to the proportion of solid content of 30:70 to prepare a positive electrode layer spinning solution B;
s4: mounting an Al foil current collector on a receiving plate, adjusting the distance between an injector and the receiving plate to be 15cm, adjusting the moving speed of the current collector to be 0.8m/min, setting the internal spinning temperature of electrostatic spinning equipment to be 45 ℃, adding a spinning solution B of a positive electrode layer into the injector, and controlling the thickness of the positive electrode layer after spinning and drying to be 80 mu m;
s5: after drying for 12h at 80 ℃, performing rolling densification on the composite positive electrode to obtain the composite positive electrode sheet;
s6: preparation of solid-state batteries: the polymer electrolyte spinning solution 1 was further coated on the surface of the positive electrode sheet rolled in step S5 (to ensure good connection of the interface), and the electrolyte membrane thickness was 40 μm;
s7: and (5) assembling the composite positive plate and the PVDF integrated structure prepared in the step (S6) with a metal lithium negative electrode to form the all-solid-state battery.
Example 2
The solid-state battery structure provided by the invention is shown in fig. 2 and comprises a solid-state composite positive electrode layer, a current collector layer, a solid-state electrolyte layer and a negative electrode layer, wherein the solid-state composite positive electrode layer comprises a first positive electrode layer on the side close to the current collector, a second positive electrode layer above the first positive electrode layer, and a solid-state electrolyte layer positioned between the solid-state composite positive electrode layer and the negative electrode layer.
The process for preparing composite solid state positive electrodes and solid state batteries by electrospinning is as follows:
s1: polyacrylonitrile, lithium trifluoromethanesulfonate (LiCF)3SO3) Diethyl carbonate and succinonitrile are uniformly mixed in DMSO according to the mass ratio of 68:18:7:7 and ultrasonically dispersed to prepare a polymer electrolyte spinning solution 1 with the solid content of 9%;
s2: preparing a positive electrode active material lithium iron phosphate, a conductive agent SP and a binder polyvinylidene fluoride-hexafluoropropylene into NMP according to a mass ratio of 96:3:1 to obtain slurry with a solid content of 62%, and uniformly mixing and stirring to obtain positive electrode slurry 2;
s3: LiNi serving as a positive electrode active material0.5Co0.1Mn0.3Al0.1O2Preparing slurry with the solid content of 70% by using SP, carbon nano tubes and a binder polyvinylidene fluoride-hexafluoropropylene in NMP according to the mass ratio of 92:2:3:3, and uniformly mixing and stirring to obtain anode slurry 3;
s4: mixing the polymer electrolyte spinning solution 1 and the LFP positive electrode slurry 2 according to the proportion of the solid content of 28:72 to prepare a first positive electrode layer spinning solution A; mixing the polymer electrolyte spinning solution 1 and the anode slurry 3 according to the solid content of 28:72 to prepare a second anode layer spinning solution B;
s5: mounting an Al foil current collector on a receiving plate, adjusting the distance between an injector and the receiving plate to be 14cm, adjusting the moving speed of the current collector to be 1.2m/min, setting the high-voltage power supply to be 15kV, setting the internal spinning temperature of electrostatic spinning equipment to be room temperature, adding a first positive electrode layer spinning solution A into the injector, and controlling the thickness of a first positive electrode layer after spinning and drying to be 40 mu m; then, an injector containing a second anode layer spinning solution B is used, the same step is carried out, and the thickness of the dried second anode layer is controlled to be 60 mu m;
s6: after drying for 24 hours at 80 ℃, performing rolling densification on the composite positive electrode to obtain the composite positive electrode sheet;
s7: the preparation of the polymer electrolyte adopts the traditional process: coating the polymer electrolyte spinning solution 1 on a release film substrate to form a film, wherein the thickness of the finally prepared polymer electrolyte film is 30 micrometers;
s8: and (4) assembling the composite positive plate prepared in the step S6, the polymer electrolyte prepared in the step S7 and the silicon oxide negative electrode into an all-solid-state battery.
Comparative example 2
The process for preparing composite solid state positive electrodes and solid state batteries by electrospinning is as follows:
s1: polyacrylonitrile, lithium trifluoromethanesulfonate (LiCF)3SO3) Diethyl carbonate and succinonitrile are uniformly mixed in DMSO according to the mass ratio of 68:18:7:7And ultrasonically dispersing to prepare a polymer electrolyte spinning solution 1 with the solid content of 9 percent;
s2: preparing a positive electrode active material lithium iron phosphate, a conductive agent SP and a binder polyvinylidene fluoride-hexafluoropropylene into NMP according to a mass ratio of 96:3:1 to obtain slurry with a solid content of 62%, and uniformly mixing and stirring to obtain positive electrode slurry 2;
s3: LiNi serving as a positive electrode active material0.5Co0.1Mn0.3Al0.1O2Preparing slurry with the solid content of 70% by using SP, carbon nano tubes and a binder polyvinylidene fluoride-hexafluoropropylene in NMP according to the mass ratio of 92:2:3:3, and uniformly mixing and stirring to obtain anode slurry 3;
s4: mixing the polymer electrolyte spinning solution 1 and the LFP positive electrode slurry 2 according to the proportion of the solid content of 28:72 to prepare a first positive electrode layer spinning solution A; mixing the polymer electrolyte spinning solution 1 and the anode slurry 3 according to the solid content of 28:72 to prepare a second anode layer spinning solution B;
s5: mounting an Al foil current collector on a receiving plate, adjusting the distance between an injector and the receiving plate to be 14cm, adjusting the moving speed of the current collector to be 1.2m/min, setting the high-voltage power supply to be 15kV, setting the internal spinning temperature of electrostatic spinning equipment to be room temperature, adding a first positive pole layer spinning solution A into the injector, and controlling the thickness of a first positive pole layer after spinning and drying to be 50 micrometers; preparing a second positive electrode layer by adopting a traditional coating method to coat slurry, adopting a second positive electrode spinning solution B, drying and controlling the thickness of the dried second positive electrode layer to be 100 mu m;
s6: after drying for 24 hours at 80 ℃, performing rolling densification on the composite positive electrode to obtain the composite positive electrode sheet;
s7: the preparation of the polymer electrolyte adopts the traditional process: coating the polymer electrolyte spinning solution 1 on a release film substrate to form a film, wherein the thickness of the finally prepared electrolyte film is 30 micrometers;
s8: and (4) assembling the composite positive plate prepared in the step S6, the polymer electrolyte prepared in the step S7 and the silicon monoxide negative electrode into an all-solid-state battery.
Example 3
The process for preparing composite solid state positive electrodes and solid state batteries by electrospinning is as follows:
s1: uniformly mixing polyvinylpyrrolidone, polymethyl methacrylate, lithium oxalyldifluoroborate and fluoroethylene carbonate in DMF according to the mass ratio of 55:20:17:8, and ultrasonically dispersing to prepare a polymer electrolyte spinning solution 1 with the solid content of 13%;
s2: preparing a slurry with a solid content of 60% from a positive active material lithium iron phosphate, acetylene black, Ketjen black and a binder PVDF in NMP according to a mass ratio of 94:2:2:2, and uniformly mixing and stirring to obtain a positive slurry 2;
s3: LiNi serving as a positive electrode active material0.8Co0.15Al0.05O2Preparing slurry with the solid content of 60% in NMP according to the mass ratio of 94:2:2:2, and uniformly mixing and stirring to obtain anode slurry 3;
s4: mixing the polymer electrolyte spinning solution 1 and the anode slurry 2 according to the solid content of 16:84 to prepare a first anode layer spinning solution A; mixing the polymer electrolyte spinning solution 1 and the anode slurry 2 according to the proportion of the solid content of 21:79 to prepare a second anode layer spinning solution B;
s5: mounting an Al foil current collector on a receiving plate, adjusting the distance between an injector and the receiving plate to be 18cm, adjusting the moving speed of the current collector to be 0.6m/min, setting a high-voltage power supply to be 18kV, adding a first positive electrode layer spinning solution A into the injector, and controlling the thickness of a first positive electrode layer after spinning and drying to be 15 mu m; then, an injector containing a second anode layer spinning solution B is used, the same step is carried out, and the thickness of the dried second anode layer is controlled to be 45 micrometers;
s6: after drying for 24 hours at 80 ℃, performing rolling densification on the composite positive electrode to obtain the composite positive electrode sheet;
s7: the preparation of the polymer electrolyte adopts the traditional process: coating the polymer electrolyte spinning solution 1 on a release film substrate to form a film, wherein the thickness of the finally prepared polymer electrolyte film is 50 microns;
s8: and (4) assembling the composite positive plate obtained in the step S6, the polymer electrolyte obtained in the step S7 and the metallic lithium negative electrode into an all-solid-state battery.
Fig. 3 is a schematic view of a positive electrode layer according to the present invention produced by an electrospinning method (both the first positive electrode layer and the second positive electrode layer can be understood according to this schematic view), in which: the black material is a positive electrode active material, and the wire is a lithium conducting polymer.
Fig. 4 is an SEM micrograph of a cross section of the composite positive electrode obtained in step S6 of this example. As can be seen from the figure: the cross sections (particles, pores and compacted) of the first positive electrode Layer (LFP) and the second positive electrode layer have obvious boundary lines, but the lithium conducting polymer and the positive active material in the first positive electrode layer and the second positive electrode layer are combined to exist in a continuous phase form, so that a continuous through three-dimensional polymer lithium conducting and conducting channel is formed, the resistance of the interface of the positive electrode and the electrolyte can be reduced, and the lithium conducting capacity and the safety performance of the positive electrode piece are improved.
Comparative example 3
The process for preparing composite solid state positive electrodes and solid state batteries by electrospinning is as follows:
s1: uniformly mixing polyvinylpyrrolidone, polymethyl methacrylate, lithium oxalyldifluoroborate and fluoroethylene carbonate in DMF according to the mass ratio of 55:20:17:8, and ultrasonically dispersing to prepare a polymer electrolyte precursor solution 1 with the solid content of 13%;
s2: preparing a slurry with a solid content of 60% from a positive active material lithium iron phosphate, acetylene black, Ketjen black and a binder PVDF in NMP according to a mass ratio of 94:2:2:2, and uniformly mixing and stirring to obtain a positive slurry 2;
s3: LiNi serving as a positive electrode active material0.8Co0.15Al0.05O2Preparing slurry with the solid content of 60% in NMP according to the mass ratio of 94:2:2:2, and uniformly mixing and stirring to obtain anode slurry 3;
s4: mixing the polymer electrolyte precursor solution 1 and the anode slurry 2 according to the solid content of 16:84 to prepare a first anode layer precursor solution A; mixing the polymer electrolyte spinning solution 1 and the anode slurry 2 according to the proportion of the solid content of 21:79 to prepare a second anode layer precursor solution B;
s5: coating a first positive electrode layer precursor solution A on an Al foil current collector and drying to obtain a first positive electrode layer with the thickness of 15 microns; then coating a second positive electrode layer precursor liquid B on the basis of the first positive electrode layer, drying and controlling the thickness of the dried second positive electrode layer to be 45 mu m;
s6: after drying for 24 hours at 80 ℃, performing rolling densification on the composite positive electrode to obtain the composite positive electrode sheet;
s7: the preparation of the polymer electrolyte adopts the traditional process: coating the polymer electrolyte precursor solution 1 on a release film substrate to form a film, wherein the thickness of the finally prepared polymer electrolyte film is 50 micrometers;
s8: and (4) assembling the composite positive plate obtained in the step S6, the polymer electrolyte obtained in the step S7 and the metallic lithium negative electrode into an all-solid-state battery.
Example 4
The process for preparing composite solid state positive electrodes and solid state batteries by electrospinning is as follows:
s1: mixing polyoxyethylene, polycaprolactone, lithium bis (difluorosulfonimide) (LiFSI), propylene carbonate, ethyl methyl carbonate and Li1.5Al0.5Ti1.5(PO4)3Uniformly mixing the materials in ACN according to the mass ratio of 10:55:18:6:9:2, and ultrasonically dispersing to prepare a polymer electrolyte spinning solution 1 with the solid content of 15%;
s2: preparing a positive electrode active material lithium iron phosphate, a conductive agent SP and a binder PVDF into slurry with a solid content of 60% in NMP according to a mass ratio of 96:3:1, and uniformly mixing and stirring to obtain a positive electrode slurry 2;
s3: LiNi serving as a positive electrode active material0.8Co0.1Mn0.1O2Preparing slurry with the solid content of 60% by mass of a conductive agent SP and a binder PVDF in NMP according to the mass ratio of 96:3:1, and uniformly mixing and stirring to obtain anode slurry 3;
s4: mixing the polymer electrolyte spinning solution 1 and the anode slurry 2 according to the solid content of 24:76 to prepare a first anode layer spinning solution A; mixing the polymer electrolyte spinning solution 1 and the anode slurry 2 according to the solid content of 24:76 to prepare a second anode layer spinning solution B;
s5: mounting an Al foil current collector on a receiving plate, adjusting the distance between an injector and the receiving plate to be 12cm, adjusting the moving speed of the current collector to be 0.9m/min, setting a high-voltage power supply to be 16kV, setting the internal spinning temperature of electrostatic spinning equipment to be 30 ℃, adding a first positive electrode layer spinning solution A into the injector, and controlling the thickness of a first positive electrode layer after spinning and drying to be 10 mu m; then, an injector containing a second anode layer spinning solution B is used, the same step is carried out, and the thickness of the dried second anode layer is controlled to be 90 micrometers;
s6: after drying for 15h at 60 ℃, performing rolling densification on the composite positive electrode to obtain the composite positive electrode sheet;
s7: preparation of solid-state batteries: the polymer electrolyte spinning solution 1 was further coated on the surface of the positive electrode sheet rolled in step S6 (to ensure good connection of the interface), and the electrolyte membrane thickness was 60 μm;
s8: and (5) assembling the composite positive plate and the polyoxyethylene-polycaprolactone-based polymer film integrated structure prepared in the step (S7) with a graphite negative electrode to form the all-solid-state battery.
Fig. 4 is a first charge-discharge curve diagram of a lithium ion battery assembled by using the composite positive electrode sheet in this embodiment. As can be seen from the figure: a charge-discharge interval: 3-4.2V; charge-discharge multiplying power: at 0.2C/0.2C, the lithium ion battery prepared in this example exhibited a typical LiNi0.8Co0.1Mn0.1O2 capacity-voltage curve, with a gram capacity exertion of 206 mAh/g. This indicates that: the composite positive plate has excellent capacity exertion and good lithium-conducting performance.
Comparative example 4
The process for preparing composite solid state positive electrodes and solid state batteries by electrospinning is as follows:
s1: mixing polyoxyethylene, polycaprolactone, lithium bis (difluorosulfonimide) (LiFSI), propylene carbonate, ethyl methyl carbonate and Li1.5Al0.5Ti1.5(PO4)3Evenly mixing the components in ACN according to the mass ratio of 10:55:18:6:9:2 and preparing the mixture into solid content by ultrasonic dispersionA polymer electrolyte spinning solution 1 in an amount of 15%;
s2: preparing a positive electrode active material lithium iron phosphate, a conductive agent SP and a binder PVDF into slurry with a solid content of 60% in NMP according to a mass ratio of 96:3:1, and uniformly mixing and stirring to obtain a positive electrode slurry 2;
s3: LiNi serving as a positive electrode active material0.8Co0.1Mn0.1O2Preparing slurry with the solid content of 60% by mass of a conductive agent SP and a binder PVDF in NMP according to the mass ratio of 96:3:1, and uniformly mixing and stirring to obtain anode slurry 3;
s4: mixing the polymer electrolyte spinning solution 1 and the anode slurry 2 according to the solid content of 24:76 to prepare a first anode layer spinning solution A; mixing the polymer electrolyte spinning solution 1 and the anode slurry 2 according to the solid content of 24:76 to prepare a second anode layer spinning solution B; then, fully and uniformly mixing the first positive electrode layer spinning solution A and the second positive electrode layer spinning solution B according to the mass ratio of 10: 90;
s5: mounting an Al foil current collector on a receiving plate, adjusting the distance between an injector and the receiving plate to be 12cm, adjusting the moving speed of the current collector to be 0.9m/min, setting the internal spinning temperature of electrostatic spinning equipment to be 30 ℃, adding the mixed positive electrode layer spinning solution in the previous step into the injector, and controlling the thickness of the first positive electrode layer after spinning and drying to be 100 mu m;
s6: drying for 15h at 60 ℃, and then performing rolling densification on the composite positive electrode to obtain the composite positive electrode sheet;
s7: preparation of solid-state batteries: the polymer electrolyte spinning solution 1 is further coated on the surface of the composite positive electrode sheet rolled in step S6 (to ensure good connection of the interface), and the electrolyte membrane thickness is 60 μm;
s8: and (5) assembling the composite positive plate and the polyoxyethylene-polycaprolactone-based polymer film integrated structure prepared in the step (S7) with a graphite negative electrode to form the all-solid-state battery.
Table 1 shows the gram capacity play ratio, internal resistance, cycle life, first-turn coulombic efficiency, and needle penetration test pass rate of the lithium ion batteries provided in examples 1 to 4 and comparative examples of the present invention at room temperature.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The composite positive plate is characterized by comprising a current collector, a first positive layer positioned on the surface of the current collector and a second positive layer positioned on the surface of the first positive layer; the first positive electrode layer includes a positive electrode active material and a lithium conducting polymer in a continuous phase form; the second positive electrode layer includes a positive electrode active material and a lithium conducting polymer in a continuous phase form; the positive active material in the first positive layer is selected from lithium iron phosphate; the positive electrode active material in the second positive electrode layer is selected from other active materials than lithium iron phosphate.
2. The composite positive electrode sheet according to claim 1, wherein the positive electrode sheet comprises a current collector and a first positive electrode layer and a second positive electrode layer coated on the surface of the current collector, the first positive electrode layer on the side close to the current collector comprising 50% to 90% of a positive electrode slurry containing a lithium iron phosphate positive electrode active material and 10% to 50% of a lithium conducting polymer in a continuous phase; the second anode layer positioned above the first anode layer comprises 50-90% of anode slurry of other anode active materials except ferric lithium phosphate and 10-50% of lithium conducting polymer in a continuous phase form.
3. The composite positive electrode sheet according to claim 1 or 2, wherein the lithium conducting polymer comprises a polymer, an electrolyte salt, a plasticizer and optionally an added or not added fast ion conductor.
4. The composite positive electrode sheet according to any one of claims 1 to 3, wherein the mass ratio of the polymer, the electrolyte salt, the plasticizer and the fast ion conductor is 50 to 80%: 10-40%, 1-10%: 0 to 10 percent.
5. The composite positive electrode sheet according to claim 4, wherein the polymer is at least one selected from the group consisting of polymethylmethacrylate, polystyrene, polyvinyl chloride, polyethylene, polypropylene, polycarbonate, polyvinyl acetate, polyethylene oxide, polyacetimide, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene, polyvinyl alcohol, polyacrylonitrile, polylactic acid, and Polycaprolactone (PCL).
6. The composite positive electrode sheet according to claim 4, wherein the electrolyte salt includes at least one of a lithium salt, a sodium salt, a magnesium salt, and an aluminum salt.
7. The composite positive electrode sheet according to claim 4, wherein the plasticizer is at least one selected from the group consisting of methoxypolyethylene glycol acrylate, polyethylene glycol methyl ether methacrylate, succinonitrile, ethylene carbonate, propylene carbonate, vinylene carbonate, ethylene sulfite, propylene sulfite, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, fluoro carbonate, tetraethylene glycol dimethyl ether, 1,3 dioxolane, fluorobenzene, fluoro ethylene carbonate, ionic liquids, and the like;
and/or the fast ion conductor is one or more of perovskite type electrolyte, anti-perovskite type electrolyte, Garnet type electrolyte, NASICON type electrolyte, LISICON type electrolyte and sulfide electrolyte.
8. An electrochemical device comprising the composite positive electrode sheet according to any one of claims 1 to 7.
9. The electrochemical device of claim 8, wherein the electrochemical device is a lithium ion battery;
and/or the lithium ion battery further comprises an electrolyte.
10. The electrochemical device according to claim 9, wherein the composite positive electrode sheet and the electrolyte are integrated in the lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111056355.9A CN113782708B (en) | 2021-09-09 | 2021-09-09 | Positive electrode and electrochemical device comprising same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111056355.9A CN113782708B (en) | 2021-09-09 | 2021-09-09 | Positive electrode and electrochemical device comprising same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113782708A true CN113782708A (en) | 2021-12-10 |
| CN113782708B CN113782708B (en) | 2023-06-16 |
Family
ID=78842051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111056355.9A Active CN113782708B (en) | 2021-09-09 | 2021-09-09 | Positive electrode and electrochemical device comprising same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113782708B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114122326A (en) * | 2022-01-26 | 2022-03-01 | 清陶(昆山)能源发展股份有限公司 | Lithium supplementing method of lithium ion battery |
| CN114447307A (en) * | 2022-02-10 | 2022-05-06 | 湖北亿纬动力有限公司 | Composite positive electrode material, preparation method thereof and electrochemical energy storage device |
| CN115763965A (en) * | 2022-12-20 | 2023-03-07 | 上海屹锂新能源科技有限公司 | Semisolid electrolyte membrane and preparation method and application thereof |
| CN116265400A (en) * | 2021-12-17 | 2023-06-20 | 中国科学院过程工程研究所 | Preparation method of lithium battery positive electrode material, lithium battery positive electrode material and lithium battery |
| CN116364894A (en) * | 2023-04-10 | 2023-06-30 | 宁夏宝丰昱能科技有限公司 | Thick electrode and preparation method and application thereof |
| CN118588938A (en) * | 2024-08-02 | 2024-09-03 | 远景动力技术(鄂尔多斯市)有限公司 | All-solid-state battery positive plate, preparation method thereof and all-solid-state battery |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003297427A (en) * | 2002-03-29 | 2003-10-17 | Mitsubishi Materials Corp | Lithium ion polymer secondary battery and method of manufacturing the same |
| US20040029014A1 (en) * | 2002-08-07 | 2004-02-12 | Samsung Sdi Co., Ltd. | Positive electrode for lithium-sulfur battery, method of producing same, and lithium-sulfur battery |
| CN109671985A (en) * | 2018-12-15 | 2019-04-23 | 华南理工大学 | A kind of application of integral structure in solid lithium ion battery |
| CN111342001A (en) * | 2020-03-06 | 2020-06-26 | 上海汽车集团股份有限公司 | Composite sulfur positive electrode for solid-state lithium-sulfur battery, and preparation method and application thereof |
| CN111900456A (en) * | 2020-07-27 | 2020-11-06 | 珠海冠宇电池股份有限公司 | Composite positive pole piece, preparation method thereof and all-solid-state lithium ion battery |
| CN112599850A (en) * | 2020-12-11 | 2021-04-02 | 珠海冠宇电池股份有限公司 | Solid electrolyte composite layer and lithium ion battery |
| CN112768702A (en) * | 2021-01-25 | 2021-05-07 | 珠海冠宇动力电池有限公司 | Positive plate and high-safety lithium ion battery thereof |
| US20210143440A1 (en) * | 2019-05-31 | 2021-05-13 | Contemporary Amperex Technology Co., Limited | Lithium-ion secondary battery |
-
2021
- 2021-09-09 CN CN202111056355.9A patent/CN113782708B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003297427A (en) * | 2002-03-29 | 2003-10-17 | Mitsubishi Materials Corp | Lithium ion polymer secondary battery and method of manufacturing the same |
| US20040029014A1 (en) * | 2002-08-07 | 2004-02-12 | Samsung Sdi Co., Ltd. | Positive electrode for lithium-sulfur battery, method of producing same, and lithium-sulfur battery |
| CN109671985A (en) * | 2018-12-15 | 2019-04-23 | 华南理工大学 | A kind of application of integral structure in solid lithium ion battery |
| US20210143440A1 (en) * | 2019-05-31 | 2021-05-13 | Contemporary Amperex Technology Co., Limited | Lithium-ion secondary battery |
| CN111342001A (en) * | 2020-03-06 | 2020-06-26 | 上海汽车集团股份有限公司 | Composite sulfur positive electrode for solid-state lithium-sulfur battery, and preparation method and application thereof |
| CN111900456A (en) * | 2020-07-27 | 2020-11-06 | 珠海冠宇电池股份有限公司 | Composite positive pole piece, preparation method thereof and all-solid-state lithium ion battery |
| CN112599850A (en) * | 2020-12-11 | 2021-04-02 | 珠海冠宇电池股份有限公司 | Solid electrolyte composite layer and lithium ion battery |
| CN112768702A (en) * | 2021-01-25 | 2021-05-07 | 珠海冠宇动力电池有限公司 | Positive plate and high-safety lithium ion battery thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116265400A (en) * | 2021-12-17 | 2023-06-20 | 中国科学院过程工程研究所 | Preparation method of lithium battery positive electrode material, lithium battery positive electrode material and lithium battery |
| CN114122326A (en) * | 2022-01-26 | 2022-03-01 | 清陶(昆山)能源发展股份有限公司 | Lithium supplementing method of lithium ion battery |
| CN114447307A (en) * | 2022-02-10 | 2022-05-06 | 湖北亿纬动力有限公司 | Composite positive electrode material, preparation method thereof and electrochemical energy storage device |
| CN114447307B (en) * | 2022-02-10 | 2024-03-15 | 湖北亿纬动力有限公司 | Composite positive electrode material, preparation method thereof and electrochemical energy storage device |
| CN115763965A (en) * | 2022-12-20 | 2023-03-07 | 上海屹锂新能源科技有限公司 | Semisolid electrolyte membrane and preparation method and application thereof |
| CN115763965B (en) * | 2022-12-20 | 2024-02-13 | 上海屹锂新能源科技有限公司 | Semi-solid electrolyte membrane and preparation method and application thereof |
| CN116364894A (en) * | 2023-04-10 | 2023-06-30 | 宁夏宝丰昱能科技有限公司 | Thick electrode and preparation method and application thereof |
| CN116364894B (en) * | 2023-04-10 | 2024-02-02 | 宁夏宝丰昱能科技有限公司 | Thick electrode and preparation method and application thereof |
| CN118588938A (en) * | 2024-08-02 | 2024-09-03 | 远景动力技术(鄂尔多斯市)有限公司 | All-solid-state battery positive plate, preparation method thereof and all-solid-state battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113782708B (en) | 2023-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107834104B (en) | Composite solid electrolyte, preparation method thereof and application thereof in all-solid-state lithium battery | |
| CN113782708B (en) | Positive electrode and electrochemical device comprising same | |
| CN110785886B (en) | Lithium secondary battery | |
| CN110165284B (en) | Lithium ion secondary battery | |
| CN109980164A (en) | Isolation film and electrochemical appliance | |
| KR102255538B1 (en) | Polymer electrolyte for secondary battery and secondary battery comprising the same | |
| CN113764615B (en) | Positive electrode and electrochemical device comprising same | |
| CN112599850A (en) | Solid electrolyte composite layer and lithium ion battery | |
| CN111900456B (en) | Composite positive pole piece, preparation method thereof and all-solid-state lithium ion battery | |
| CN111834662B (en) | Interface functional layer, preparation method thereof and lithium ion battery | |
| CN113451580B (en) | Interfacial layer and lithium ion battery comprising same | |
| KR102204939B1 (en) | Positive electrode active material for lithium secondary battery and producing method thereof, positive electrode and lithum secondary battery comprising the same | |
| CN115172654B (en) | Lithium supplementing negative electrode plate and secondary battery | |
| CN105810940A (en) | Positive electrode active substance and preparation method thereof, positive electrode material containing positive electrode active substance and battery | |
| CN116247277A (en) | High-energy-density lithium battery and application thereof | |
| CN112635818A (en) | Composite solid electrolyte, preparation method thereof and all-solid-state lithium ion battery | |
| CN111834620A (en) | Lithium metal battery positive electrode, lithium metal battery and preparation method thereof | |
| JP2009026514A (en) | Nonaqueous electrolyte secondary battery | |
| CN113782826B (en) | Solid electrolyte and solid battery containing same | |
| KR20190143292A (en) | Positive electrode active material for lithium secondary battery and lithium secondary battery | |
| CN116995235A (en) | Negative electrode adhesive, negative electrode plate, lithium ion battery and preparation method of negative electrode adhesive | |
| KR20210011342A (en) | Lithium secondary battery | |
| CN112701347B (en) | Electrochemical device and electronic equipment | |
| CN111816916B (en) | Composite solid electrolyte membrane, preparation method thereof and lithium ion battery | |
| CN113632258A (en) | Lithium secondary 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 |