CN113903897B - High specific energy lithium primary battery positive electrode composite material and preparation method thereof - Google Patents
High specific energy lithium primary battery positive electrode composite material and preparation method thereof Download PDFInfo
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- CN113903897B CN113903897B CN202111149980.8A CN202111149980A CN113903897B CN 113903897 B CN113903897 B CN 113903897B CN 202111149980 A CN202111149980 A CN 202111149980A CN 113903897 B CN113903897 B CN 113903897B
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- Prior art keywords
- primary battery
- positive electrode
- lithium primary
- composite material
- fluoride
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012798 spherical particle Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- 150000004703 alkoxides Chemical class 0.000 claims description 13
- -1 bismuth alkoxides Chemical class 0.000 claims description 13
- 238000005118 spray pyrolysis Methods 0.000 claims description 13
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011669 selenium Substances 0.000 claims description 10
- 239000012159 carrier gas Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 7
- 229910052711 selenium Inorganic materials 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- 229910052714 tellurium Inorganic materials 0.000 claims description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052790 beryllium Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052773 Promethium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 claims description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052712 strontium Inorganic materials 0.000 claims 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000007774 positive electrode material Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 239000013543 active substance Substances 0.000 abstract description 5
- 230000007246 mechanism Effects 0.000 abstract description 5
- 230000020169 heat generation Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000006276 transfer reaction Methods 0.000 abstract description 2
- 238000005507 spraying Methods 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 229910000831 Steel Inorganic materials 0.000 description 16
- 239000010959 steel Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 10
- 208000028659 discharge Diseases 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000011267 electrode slurry Substances 0.000 description 5
- 239000003273 ketjen black Substances 0.000 description 5
- 239000005077 polysulfide Substances 0.000 description 5
- 229920001021 polysulfide Polymers 0.000 description 5
- 150000008117 polysulfides Polymers 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- YBDACTXVEXNYOU-UHFFFAOYSA-N C(F)(F)(F)F.[Li] Chemical compound C(F)(F)(F)F.[Li] YBDACTXVEXNYOU-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- MIMCEMSZHORAOF-UHFFFAOYSA-N butan-1-olate;cobalt(2+) Chemical compound [Co+2].CCCC[O-].CCCC[O-] MIMCEMSZHORAOF-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004334 fluoridation Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 description 1
- 229910016509 CuF 2 Inorganic materials 0.000 description 1
- 229910018091 Li 2 S Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- SOZVEOGRIFZGRO-UHFFFAOYSA-N [Li].ClS(Cl)=O Chemical compound [Li].ClS(Cl)=O SOZVEOGRIFZGRO-UHFFFAOYSA-N 0.000 description 1
- GJCNZQUZWSHFHP-UHFFFAOYSA-N [Li].O=S=O Chemical compound [Li].O=S=O GJCNZQUZWSHFHP-UHFFFAOYSA-N 0.000 description 1
- FBDMJGHBCPNRGF-UHFFFAOYSA-M [OH-].[Li+].[O-2].[Mn+2] Chemical compound [OH-].[Li+].[O-2].[Mn+2] FBDMJGHBCPNRGF-UHFFFAOYSA-M 0.000 description 1
- VVJRYKIRUIWNGU-UHFFFAOYSA-N [Sr].[Sr] Chemical compound [Sr].[Sr] VVJRYKIRUIWNGU-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- WZJQNLGQTOCWDS-UHFFFAOYSA-K cobalt(iii) fluoride Chemical compound F[Co](F)F WZJQNLGQTOCWDS-UHFFFAOYSA-K 0.000 description 1
- VNGORJHUDAPOQZ-UHFFFAOYSA-N copper;propan-2-olate Chemical compound [Cu+2].CC(C)[O-].CC(C)[O-] VNGORJHUDAPOQZ-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- MYXUYXMJVQWRPU-UHFFFAOYSA-N triethoxybismuthane Chemical compound [Bi+3].CC[O-].CC[O-].CC[O-] MYXUYXMJVQWRPU-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
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- 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
- H01M4/366—Composites as layered products
-
- 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
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/582—Halogenides
-
- 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)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application relates to a positive electrode composite material for a lithium primary battery and a preparation method thereof. Aiming at the problems that the energy density and the high-rate performance of the lithium primary battery can not be combined and the heat generation is serious when the lithium primary battery is used under the working condition of high-rate, the application designs and develops a multi-layer composite structure of non-lithium-containing positive electrode materials, the multi-electron transfer reaction of active substances in the structure realizes the high specific energy of the lithium primary battery, and meanwhile, the electrode active substances are utilized to coordinate and continue the discharge strategy, so as to simulate the weakness of self discharge of the composite positive electrode, improve the discharge rate performance and realize the discharge of a synergistic mechanism. The lithium primary battery anode composite material is prepared by spraying and heat treatment of fluoride and oxygen element material simple substance or compound, wherein the fluoride is formed by porous hollow spherical particles formed by fluorocarbon coated fluoric metal. The composite positive electrode material prepared by the application remarkably improves the discharge specific energy and specific power of the lithium primary battery, and the discharge specific energy of the prepared lithium primary battery at a rate of 20 hours is more than 800Wh/kg.
Description
Technical Field
The application belongs to the field of lithium batteries, and particularly relates to a positive electrode composite material for a lithium primary battery and a preparation method thereof.
Background
The reaction mechanism of the traditional lithium ion secondary battery is the deintercalation and intercalation reaction of lithium ions, and the metal oxidation valence state of the positive electrode active material is not fully utilized, so that the gram capacity is low, and the energy density of the battery system is low. The adoption of multiple-variable elements to construct a multi-electron reaction system to obtain higher energy density is a feasible way for improving the energy density of the lithium battery. The lithium primary battery takes metal lithium as a negative electrode and non-lithium-containing materials as a positive electrode, and the reaction mechanism of most materials is different from the phase inversion reaction mechanism of intercalation reaction of the lithium ion battery, and a multi-electron transfer process exists during the reaction, so that the battery type has higher energy density. It plays an important and irreplaceable role in both military and civilian fields.
The lithium primary battery mainly comprises a lithium-manganese dioxide battery, a lithium-thionyl chloride battery, a lithium-sulfur dioxide battery and a lithium-carbon fluoride battery. Wherein the theoretical mass specific energy of the lithium-carbon fluoride batteryThe energy density of the actual mass can reach 800-900Wh/kg and the energy density has better shelving performance, so the energy density is greatly concerned by the market and is practically applied. However, the fluorocarbon material has the problems of difficult synthesis, high cost and low electronic conductivity (10) -12 -10 -14 S/cm), the problems of serious voltage hysteresis at the initial stage of discharge, poor high-rate discharge performance, serious heat release and the like exist, and the application of the high-rate discharge power is restricted in wider fields. Other types of lithium primary batteries have the phenomenon that the specific energy and specific power of discharge are opposite, so that the lithium primary batteries with the performance are hardly available on the market, and the application field of the lithium primary batteries is severely limited.
Chinese patent CN110112394a discloses a method for preparing a fluorocarbon/metal fluoride composite positive electrode material, specifically, carbonizing at least one of copper-based, iron-based, cobalt-based, nickel-based and manganese-based metal organic frame materials at high temperature in an inert gas atmosphere, and then cooling to room temperature to obtain a composite precursor; and (3) placing the precursor of the composite material into a reaction kettle for drying, then introducing mixed gas consisting of fluorine gas and nitrogen gas, then carrying out fluoridation under the heating condition, and carrying out vacuum drying to obtain the carbon fluoride/metal fluoride composite material serving as a final product. The method has the defects that the high-temperature carbonization and fluorination are carried out, the structure of the prepared composite material cannot be well mastered, the appearance cannot be well controlled, and the like. Chinese patent CN109167040a discloses a method for using a fluorocarbon additive in lithium sulfur battery and application thereof, wherein the fluorocarbon, active material sulfur, conductive carbon and binder PVDF are mechanically ground to compound and manufacture the lithium sulfur battery, and the cycle life and rate capability of the lithium sulfur battery are improved by using fluorine-doped carbon generated by discharging the fluorocarbon. The method prepares the composite electrode by simple physical mixing, and has limited improvement on the performance of the battery. Chinese patent CN104716296a discloses a sulfur-containing composite positive electrode, in which an electrochemically active fluorocarbon additive is added during the processing of the sulfur positive electrode to prepare a composite sulfur positive electrode, so as to increase the first discharge specific energy of the lithium sulfur battery, and the result shows that the effect of physically mixing the fluorocarbon and elemental sulfur on improving the performance of the battery is limited.
The metal fluoride is used as the positive electrode material,not only can the intercalation/deintercalation reaction of lithium ions be carried out to store capacity, but also all oxidation states of metal elements and lithium ions can be utilized to carry out chemical conversion reaction, and the reaction is accompanied by the transfer of a plurality of electrons, so that the lithium ion battery has the advantages of higher theoretical specific capacity and high battery voltage. However, the metal fluoride has strong ionic bond characteristics, and the material has large energy band gap and poor conductivity, so that the electrochemical performance of the metal fluoride cannot be fully exerted. Oxygen elements such as sulfur, selenium, tellurium are also typical chemical conversion reactions when involved in electrochemical reactions, with the transfer of two electrons, illustrated by the common lithium sulfur cell, as follows: s is S 8 +Li→Li 2 S x (x is more than or equal to 1 and less than or equal to 8), the theoretical specific capacity of elemental sulfur is 1675mAh/g, the theoretical specific capacity of metallic lithium is 3860mAh/g, the theoretical energy density of the lithium-sulfur battery is as high as 2600Wh/kg, the lithium-sulfur battery has the remarkable advantage of high specific energy, and the application prospect is wide. The main problems restricting the practical application of the lithium-sulfur battery are concentrated on poor shelving performance, poor cycling stability and to be improved in safety performance. Research shows that in the discharging process of the lithium sulfur battery, elemental sulfur is reduced to form lithium polysulfide which is soluble in electrolyte, and diffuses to the surface of a negative electrode to react with lithium to form low-valence lithium polysulfide, and in the charging process, the low-valence lithium polysulfide diffuses to the surface of a positive electrode to form high-valence lithium polysulfide again, so-called 'shuttle effect'. As the cycling of the lithium sulfur battery proceeds, the soluble lithium polysulfide is eventually reduced to Li which is extremely poorly conductive and insoluble in the electrolyte 2 S is gradually deposited on the surface of the positive electrode, so that the conductivity and electrochemical reaction activity of the sulfur positive electrode are poor, and the circulation stability of the sulfur positive electrode is further deteriorated.
The active materials with different types and the same reaction mechanism are fused and constructed in a microcosmic level by a proper preparation method, so that the composite material with excellent comprehensive performance is one direction for constructing a novel battery system. The application starts from the thought, a novel positive electrode composite material is prepared and successfully used for a lithium primary battery, and extremely high specific energy and specific power advantages are obtained.
Disclosure of Invention
Aiming at the problems that the energy density and the high-rate performance of a lithium primary battery can not be combined and the heat generation is serious when the lithium primary battery is used under the working condition of high-rate, the non-lithium-containing positive electrode material is compounded, and the active substances in the composite material are subjected to energy conversion through multiple electron transfer reactions, so that the characteristic of high energy density of the battery is realized.
A high specific energy lithium primary battery positive electrode composite material is characterized in that:
the lithium primary battery anode composite material is formed by compounding a fluoride coated oxygen element simple substance or a compound, wherein the fluoride is formed by metal fluoride with surface coated with fluorocarbon, and the structure of the fluoride is porous hollow spherical particles; in the lithium primary battery positive electrode composite material, the mass ratio of fluorinated metal is 10% -20%, the mass ratio of fluorinated carbon is 10% -20%, and the mass ratio of oxygen group element simple substance or compound is 60% -80%. The preparation method of the lithium primary battery anode composite material comprises the following steps:
(1) Dissolving metal alkoxide in an alcohol solvent to prepare a uniform metal alkoxide solution;
(2) Using a fluorine-containing gas source as a carrier gas, and carrying out pyrolysis treatment on the metal alkoxide solution prepared in the step (1) by using a spray pyrolysis method to prepare fluoride of porous hollow spherical particles;
(3) And (3) compositing the fluoride obtained in the step (2) with an oxygen element material simple substance or compound by a low-temperature roasting method to obtain the high specific energy lithium primary battery anode composite material.
In the step (1), the concentration of the metal alkoxide solution is 0.1moL/L to 10moL/L.
In step (1), the metal alkoxide is rare earth metal lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium,Holmium saltErbium, thulium, ytterbium, lutetium, yttrium, transition metals iron, copper, cobalt, nickel, zinc, manganese, chromium, vanadium, titanium, alkaline earth metalsBeryllium (beryllium)Magnesium, calcium,Strontium (strontium)、Barium (Ba)And one of other main group metal tin, lead, bismuth alkoxides.
In the step (2), the spray pyrolysis temperature is 300-1300 ℃.
The carrier gas is F 2 /N 2 Mixed gas, HF, NF 3 One of them.
Said F 2 /N 2 F in the mixed gas 2 The volume content is 1-20%.
The flow rate of the spray pyrolysis carrier gas is 1ml/s-500ml/s; the flow rate of the metal alkoxide solution is 1ml/s to 60ml/s.
The oxygen group element material is one or two or more of elemental sulfur, selenium, tellurium and sulfur doped selenium or tellurium binary solid solution.
The low-temperature roasting method is that inert gas N is adopted 2 Or under Ar protection, sealing and roasting the fluoride and the simple substance or compound of the oxygen group element at 150-450 ℃.
The sealing roasting time is 2-20 h.
In the process of preparing fluoride by spray pyrolysis of metal alkoxide, the air tightness and corrosion resistance of equipment are strictly ensured, and the discharged tail gas is strictly purified and absorbed and can be discharged.
The composite material for the positive electrode of the high specific energy lithium primary battery and the preparation method thereof have remarkable advantages, and are specifically expressed in the following aspects:
(1) The positive electrode material is a composite material, the reaction of active substances and metallic lithium is a phase transfer chemical reaction, multiple electrons are transferred in the process, a material system belongs to a high-energy density system, and a lithium primary battery prepared from the material has extremely high specific energy;
(2) The three active substances are not simply physically mixed, but reasonably designed in material structure through a chemical reaction process of spray pyrolysis, porous metal fluoride spherical particles coated with a fluorocarbon layer are prepared, and the active components of oxygen group elements are dispersed in hollow spaces inside the particles through sealing roasting;
(3) The porous metal fluoride spherical particles coated with the fluorocarbon are prepared by a spray pyrolysis one-step method, complex processes such as preparing synthetic sol of high-specific surface metal fluoride by a sol-gel method, drying, removing solvent, fluoridation and the like are omitted, and fluoride materials with uniform morphology and complex structure are prepared, so that the porous metal fluoride spherical particles have great industrialization potential;
(4) The three active material discharge voltage platforms have gradient difference, the metal fluoride, the carbon fluoride and the oxygen group element active material are sequentially discharged, and the metal and carbon particles of the earlier-stage discharge products play a positive role in the rate performance of the subsequent oxygen group element active material discharge.
Drawings
FIG. 1 is an electron micrograph of the positive composite material.
Fig. 2 is a discharge curve of the positive electrode composite material.
Fig. 3 is a photograph of a soft pack lithium primary cell.
Detailed Description
The present application is further specifically illustrated by examples, and is not intended to limit the scope of the application. The materials or medicines involved in the specific examples are commercial products, and are commercially available unless specified otherwise.
Example 1
1. Dissolving bismuth ethoxide in isopropanol solvent to prepare 0.5mol/L bismuth alkoxide solution;
2. HF is used as carrier gas, and the bismuth alkoxide solution is atomized and sprayed into a spray pyrolysis furnace at 800 ℃. Wherein, the flow rate of HF is controlled to be about 50ml/s, the flow rate of bismuth alkoxide solution is controlled to be about 20ml/s, and the prepared porous fluoride spherical particles with uniform morphology are reserved;
3. mixing the porous fluoride prepared in the step 2 with elemental sulfur according to the mass ratio of 1:4, placing the mixture into a closed steel container, then placing the steel container into a sintering furnace in an argon atmosphere, treating the steel container for 6 hours at 150 ℃, naturally cooling the steel container, and taking out the product to obtain the BiF 3 @CF x Spherical positive electrode composite material @ S.
Example 2
1. BiF is to 3 @CF x @ S positive electrode composite materialMixing the materials, ketjen black and a binder PVDF in a ratio of 8:1:1, and preparing slurry in an NMP solvent; 2. the positive electrode slurry is coated on aluminum foil by a scraper, dried in a blast oven at 80 ℃ for standby,
3. cutting the dried positive electrode intoA button cell is assembled with the lithium sheet to evaluate the material performance;
4. and discharging the button half cell at a rate of 0.05C, wherein the gram capacity of the positive electrode composite material reaches 1208mAh/g.
Example 3
1. Dissolving copper isopropoxide in isopropanol solvent to prepare copper alkoxide solution with the concentration of 0.5 mol/L;
2. HF is used as carrier gas, and the copper alkoxide solution is atomized and sprayed into a spray pyrolysis furnace at 800 ℃. Wherein, the HF flow rate is controlled to be about 50ml/s, the copper alcohol solution is controlled to be about 20ml/s, and the prepared porous fluoride spherical particles with uniform morphology are reserved;
3. mixing the porous fluoride prepared in the step 2 with elemental sulfur according to the mass ratio of 1:4, placing the mixture into a closed steel container, then placing the steel container into a sintering furnace in an argon atmosphere, treating the steel container at 150 ℃ for 6 hours, naturally cooling the steel container, and taking out the product to obtain CuF 2 @CF x Spherical positive electrode composite material @ S.
Example 4
1. CuF is processed 2 @CF x Mixing an @ S positive electrode composite material, ketjen black and a binder PVDF in a ratio of 8:1:1, and preparing slurry in an NMP solvent; 2. the positive electrode slurry is coated on aluminum foil by a scraper, dried in a blast oven at 80 ℃ for standby,
3. cutting the dried positive electrode intoA button cell is assembled with the lithium sheet to evaluate the material performance;
4. and discharging the button half cell at a rate of 0.05C, wherein the gram capacity of the positive electrode composite material reaches 1320mAh/g.
Example 5
1. Dissolving cobalt n-butoxide in an n-butanol solvent to prepare a cobalt alkoxide solution with the concentration of 1 moL/L;
2. using HF as carrier gas, atomizing the cobalt alkoxide solution at 1000 ℃ and introducing the solution into a spray pyrolysis furnace, controlling the flow rate of the HF to be about 100ml/s, controlling the flow rate of the cobalt alkoxide solution to be about 20ml/s, and reserving the prepared porous fluoride spherical particles with uniform morphology;
3. mixing the product obtained in the step 2 with elemental sulfur according to a mass ratio of 1:4, placing the mixture into a closed steel container, then placing the steel container into a sintering furnace in an argon atmosphere, treating the steel container at 150 ℃ for 6 hours, naturally cooling the steel container, and taking out the product to obtain CoF 3 @CF x Spherical positive electrode composite material @ S.
Example 6
1. CoF is to 3 @CF x Mixing an @ S positive electrode composite material, ketjen black and a binder PVDF in a ratio of 8:1:1, and preparing slurry in an NMP solvent;
2. the positive electrode slurry is coated on aluminum foil by a scraper, dried in a blast oven at 80 ℃ for standby,
3. cutting the dried positive electrode intoA button cell is assembled with the lithium sheet to evaluate the material performance;
4. the button half cell is discharged at the multiplying power of 0.05C, and the gram capacity of the positive electrode composite material reaches 1346mAh/g.
Example 7
1. Dissolving cobalt n-butoxide in an n-butanol solvent to prepare a cobalt alkoxide solution with the concentration of 1 moL/L;
2. using HF as carrier gas, atomizing the cobalt alkoxide solution at 1000 ℃ and introducing the solution into a spray pyrolysis furnace, controlling the flow rate of the HF to be about 100ml/s, controlling the flow rate of the cobalt alkoxide solution to be about 20ml/s, and reserving the prepared porous fluoride spherical particles with uniform morphology;
3. fully mixing sulfur and selenium in an atomic ratio of 95% to 5% to obtain a mixture of the sulfur and the selenium;
4. mixing the product obtained in the step 2 and the mixture obtained in the step 3 according to the mass ratio of 1:4, placing the mixture into a closed steel container, then placing the steel container into a sintering furnace in an argon atmosphere, treating the steel container at 300 ℃ for 6 hours, naturally cooling the steel container, and taking out the product to obtain the CoF 3 @CF x Spherical positive electrode composite material @ S-Se. The electron microscope photograph of the material is shown in figure 1.
Example 8
1. CoF is to 3 @CF x Mixing an @ S-Se positive electrode composite material, ketjen black and a binder PVDF in a ratio of 8:1:1, and preparing slurry in an NMP solvent;
2. the positive electrode slurry is coated on aluminum foil by a scraper, dried in a blast oven at 80 ℃ for standby,
3. cutting the dried positive electrode intoA button cell is assembled with the lithium sheet to evaluate the material performance;
4. and discharging the button half cell at a rate of 0.05C, wherein the gram capacity of the positive electrode composite material reaches 1296mAh/g.
Example 9
The soft package lithium primary battery is prepared, and the electrical property is tested, and the steps are as follows:
1. the CoF3@CFx@S-Se positive electrode composite material prepared in the example 5 is mixed with ketjen black and a binder PVDF in a ratio of 8:1:1, and then positive electrode slurry is prepared in a slurry mixer;
2. coating by a small-sized coating machine to prepare a double-sided coated positive electrode plate with high loading capacity;
3. cutting the positive plate and the lithium negative plate, and preparing an 8Ah high-capacity soft-package lithium primary battery by using a winding method;
4. the soft package lithium primary battery is discharged at the rate of 0.05C, and the mass specific energy of the battery reaches 806Wh/kg. The discharge curve of the positive electrode composite material is shown in fig. 2, and the soft-package lithium primary battery is shown in fig. 3.
Claims (4)
1. A preparation method of a high specific energy lithium primary battery positive electrode composite material is characterized by comprising the following steps:
the lithium primary battery anode composite material is formed by compounding fluoride coated oxygen element materials, wherein the fluoride is formed by metal fluoride with surface coated with fluorocarbon, and the structure of the fluoride is porous hollow spherical particles; in the lithium primary battery positive electrode composite material, the mass ratio of fluorinated metal is 10% -20%, the mass ratio of fluorinated carbon is 10% -20%, and the mass ratio of oxygen group element material is 60% -80%; the oxygen group element material is one or two or more of elemental sulfur, selenium, tellurium and sulfur doped selenium or tellurium binary solid solution; the method comprises the following specific steps:
(1) Dissolving metal alkoxide in an alcohol solvent to prepare a uniform metal alkoxide solution;
(2) Performing pyrolysis treatment on the metal alkoxide solution prepared in the step (1) by using HF as a carrier gas and using a spray pyrolysis method to prepare fluoride of porous hollow spherical particles; the spray pyrolysis temperature is 800-1000 ℃;
(3) Compounding the fluoride obtained in the step (2) with an oxygen element material by a low-temperature roasting method to obtain a high specific energy lithium primary battery anode composite material; the low-temperature roasting method is that inert gas N is adopted 2 Or under Ar protection, sealing and roasting the fluoride and the oxygen group element material at 150-300 ℃ for 6h.
2. The method for preparing the high specific energy lithium primary battery positive electrode composite material according to claim 1, which is characterized in that: in the step (1), the concentration of the metal alkoxide solution is 0.1moL/L to 10moL/L.
3. The method for preparing the high specific energy lithium primary battery positive electrode composite material according to claim 1, which is characterized in that: in the step (1), the metal alkoxide is one of rare earth metal lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, transition metal iron, copper, cobalt, nickel, zinc, manganese, chromium, vanadium, titanium, alkaline earth metal beryllium, magnesium, calcium, strontium, barium, and other main group metal tin, lead, bismuth alkoxides.
4. The method for preparing the high specific energy lithium primary battery positive electrode composite material according to claim 1, which is characterized in that: the flow rate of the spray pyrolysis carrier gas is 1ml/s-500ml/s; the flow rate of the metal alkoxide solution is 1ml/s to 60ml/s.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106946296A (en) * | 2017-03-03 | 2017-07-14 | 中南大学 | A kind of micron order monocrystalline lithium nickelate and its preparation method and application |
| KR20170120735A (en) * | 2016-04-21 | 2017-11-01 | 주식회사 비츠로셀 | Method for menufacturing a cathode of lithium primary battery |
| CN108565430A (en) * | 2018-04-20 | 2018-09-21 | 河北工业大学 | Preparation method of high-energy-density primary battery positive electrode material |
| CN109659561A (en) * | 2018-12-29 | 2019-04-19 | 中南大学 | Fluorophosphoric acid vanadium lithium/carbon composite anode material and preparation method thereof |
| CN110112394A (en) * | 2019-05-14 | 2019-08-09 | 中国民航大学 | A kind of preparation method of fluorocarbons/metal fluoride composite positive pole |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170120735A (en) * | 2016-04-21 | 2017-11-01 | 주식회사 비츠로셀 | Method for menufacturing a cathode of lithium primary battery |
| CN106946296A (en) * | 2017-03-03 | 2017-07-14 | 中南大学 | A kind of micron order monocrystalline lithium nickelate and its preparation method and application |
| CN108565430A (en) * | 2018-04-20 | 2018-09-21 | 河北工业大学 | Preparation method of high-energy-density primary battery positive electrode material |
| CN109659561A (en) * | 2018-12-29 | 2019-04-19 | 中南大学 | Fluorophosphoric acid vanadium lithium/carbon composite anode material and preparation method thereof |
| CN110112394A (en) * | 2019-05-14 | 2019-08-09 | 中国民航大学 | A kind of preparation method of fluorocarbons/metal fluoride composite positive pole |
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