EP1880435A1 - Matiere active de cathode recouverte de compose de fluor pour batteries secondaires au lithium et leur procede de preparation - Google Patents
Matiere active de cathode recouverte de compose de fluor pour batteries secondaires au lithium et leur procede de preparationInfo
- Publication number
- EP1880435A1 EP1880435A1 EP06716437A EP06716437A EP1880435A1 EP 1880435 A1 EP1880435 A1 EP 1880435A1 EP 06716437 A EP06716437 A EP 06716437A EP 06716437 A EP06716437 A EP 06716437A EP 1880435 A1 EP1880435 A1 EP 1880435A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- active material
- cathode active
- fluorine compound
- coated
- fluorine
- 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.)
- Withdrawn
Links
- 239000006182 cathode active material Substances 0.000 title claims abstract description 146
- 150000002222 fluorine compounds Chemical class 0.000 title claims abstract description 63
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 62
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims description 35
- 229910052731 fluorine Inorganic materials 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000011737 fluorine Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- 229910052749 magnesium Inorganic materials 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 229910052804 chromium Inorganic materials 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- 229910052725 zinc Inorganic materials 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 229910017709 Ni Co Inorganic materials 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 229910052718 tin Inorganic materials 0.000 claims description 9
- -1 Hg^ Chemical compound 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- KWVVTSALYXIJSS-UHFFFAOYSA-L silver(ii) fluoride Chemical compound [F-].[F-].[Ag+2] KWVVTSALYXIJSS-UHFFFAOYSA-L 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910052596 spinel Inorganic materials 0.000 claims description 5
- 239000011029 spinel Substances 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052765 Lutetium Inorganic materials 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 150000004703 alkoxides Chemical group 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 claims description 3
- 229910016468 DyF3 Inorganic materials 0.000 claims description 3
- 229910016653 EuF3 Inorganic materials 0.000 claims description 3
- 229910005270 GaF3 Inorganic materials 0.000 claims description 3
- 229910005693 GdF3 Inorganic materials 0.000 claims description 3
- 229910004650 HoF3 Inorganic materials 0.000 claims description 3
- 229910021620 Indium(III) fluoride Inorganic materials 0.000 claims description 3
- 229910002319 LaF3 Inorganic materials 0.000 claims description 3
- 229910013482 LuF3 Inorganic materials 0.000 claims description 3
- 229910021570 Manganese(II) fluoride Inorganic materials 0.000 claims description 3
- 229910021571 Manganese(III) fluoride Inorganic materials 0.000 claims description 3
- 229910017557 NdF3 Inorganic materials 0.000 claims description 3
- 229910019322 PrF3 Inorganic materials 0.000 claims description 3
- 229910018096 ScF3 Inorganic materials 0.000 claims description 3
- 229910021608 Silver(I) fluoride Inorganic materials 0.000 claims description 3
- 229910021175 SmF3 Inorganic materials 0.000 claims description 3
- 229910004299 TbF3 Inorganic materials 0.000 claims description 3
- 229910010346 TiF Inorganic materials 0.000 claims description 3
- 229910010348 TiF3 Inorganic materials 0.000 claims description 3
- 229910008903 TmF3 Inorganic materials 0.000 claims description 3
- GUNJVIDCYZYFGV-UHFFFAOYSA-K antimony trifluoride Chemical compound F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 claims description 3
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 3
- LVEULQCPJDDSLD-UHFFFAOYSA-L cadmium fluoride Chemical compound F[Cd]F LVEULQCPJDDSLD-UHFFFAOYSA-L 0.000 claims description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 3
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 claims description 3
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 claims description 3
- FMSYTQMJOCCCQS-UHFFFAOYSA-L difluoromercury Chemical compound F[Hg]F FMSYTQMJOCCCQS-UHFFFAOYSA-L 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 claims description 3
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims description 3
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 3
- SRVINXWCFNHIQZ-UHFFFAOYSA-K manganese(iii) fluoride Chemical compound [F-].[F-].[F-].[Mn+3] SRVINXWCFNHIQZ-UHFFFAOYSA-K 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- HHQFLEDKAVLHOM-UHFFFAOYSA-N oxovanadium;trihydrofluoride Chemical compound F.F.F.[V]=O HHQFLEDKAVLHOM-UHFFFAOYSA-N 0.000 claims description 3
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Inorganic materials [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 claims description 3
- OEKDNFRQVZLFBZ-UHFFFAOYSA-K scandium fluoride Chemical compound F[Sc](F)F OEKDNFRQVZLFBZ-UHFFFAOYSA-K 0.000 claims description 3
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Inorganic materials [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 3
- FDIFPFNHNADKFC-UHFFFAOYSA-K trifluoroholmium Chemical compound F[Ho](F)F FDIFPFNHNADKFC-UHFFFAOYSA-K 0.000 claims description 3
- JNLSTWIBJFIVHZ-UHFFFAOYSA-K trifluoroindigane Chemical compound F[In](F)F JNLSTWIBJFIVHZ-UHFFFAOYSA-K 0.000 claims description 3
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 claims description 3
- LKNRQYTYDPPUOX-UHFFFAOYSA-K trifluoroterbium Chemical compound F[Tb](F)F LKNRQYTYDPPUOX-UHFFFAOYSA-K 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000010450 olivine Substances 0.000 claims description 2
- 229910052609 olivine Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 101100274801 Caenorhabditis elegans dyf-3 gene Proteins 0.000 claims 1
- 229910020186 CeF4 Inorganic materials 0.000 claims 1
- 229910006160 GeF4 Inorganic materials 0.000 claims 1
- 229910004504 HfF4 Inorganic materials 0.000 claims 1
- 229910017698 Ni 1-x-y Co Inorganic materials 0.000 claims 1
- 229910004014 SiF4 Inorganic materials 0.000 claims 1
- 229910008449 SnF 2 Inorganic materials 0.000 claims 1
- 229910009527 YF3 Inorganic materials 0.000 claims 1
- 229910009520 YbF3 Inorganic materials 0.000 claims 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims 1
- PPMWWXLUCOODDK-UHFFFAOYSA-N tetrafluorogermane Chemical compound F[Ge](F)(F)F PPMWWXLUCOODDK-UHFFFAOYSA-N 0.000 claims 1
- 229910012820 LiCoO Inorganic materials 0.000 description 33
- 239000011572 manganese Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 27
- 239000011248 coating agent Substances 0.000 description 21
- 238000000576 coating method Methods 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 238000002441 X-ray diffraction Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000000975 co-precipitation Methods 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910015672 LiMn O Inorganic materials 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 238000000840 electrochemical analysis Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000011149 active material Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 229910017855 NH 4 F Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 229910001512 metal fluoride Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 2
- 229910020187 CeF3 Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910021564 Chromium(III) fluoride Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910013292 LiNiO Inorganic materials 0.000 description 2
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910021587 Nickel(II) fluoride Inorganic materials 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- FPHIOHCCQGUGKU-UHFFFAOYSA-L difluorolead Chemical compound F[Pb]F FPHIOHCCQGUGKU-UHFFFAOYSA-L 0.000 description 2
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 2
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 description 2
- 229960005235 piperonyl butoxide Drugs 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 2
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 2
- 229910001637 strontium fluoride Inorganic materials 0.000 description 2
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 2
- IGELFKKMDLGCJO-UHFFFAOYSA-N xenon difluoride Chemical compound F[Xe]F IGELFKKMDLGCJO-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910015679 LiMn 2 O4 Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
- C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/50—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO2]n-, e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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Definitions
- the present invention relates to a method for treating the surface of a cathode active material for lithium secondary batteries with superior cycle characteristics and excellent high-rate characteristics. More particularly, the present invention relates to an improvement in the charge-discharge characteristics, cycle characteristics, high-voltage characteristics and thermal stability of lithium secondary batteries by coating a cathode active material for the lithium secondary batteries with a fluorine compound.
- Lithium secondary batteries are classified into lithium metal batteries using lithium as an anode and lithium ion batteries using an interlayer compound, e.g., carbon, capable of intercalation/deintercalation of lithium ions. Further, lithium secondary batteries are classified into liquid type batteries using a liquid electrolyte, gel type polymer batteries using a mixture of liquid and polymer electrolytes, and solid type polymer batteries using a pure polymer electrolyte according to the kind of electrolytes used.
- LiCoO LiCoO
- carbon LiMn O
- LiCoO 2 LiCo x Ni 1-x O 2
- LiMn 2 O 4 LiCoO 2 is a promising material in terms of its stable charge-discharge char- acteristics, high electronic conductivity, superior thermal stability and constant discharge voltage characteristics, but has disadvantages of insufficient cobalt deposits, high price and toxicity.
- LiNiO has problems that it is difficult to synthesize and is thermally unstable, which make LiNiO unsuitable for commercialization.
- Commercial applications of LiMn 2 O 4 are currently limited to some low-priced products.
- LiMn 2 O 4 is has a spinel structure and deliverers a lower theoretical capacity (-148 mAh/g) than other active materials.
- LiMn 2 O 4 has poor cycle characteristics due to the Mn dissolution into electrolyte. Particularly, since LiMn O has poor high-temperature characteristics at 55°C or higher when compared to LiCoO , it has not yet been put to practical use in batteries.
- Li[Ni Mn ]O is extremely low, which causes difficulty in the commercialization of the material (J. of Power Sources, ' 112 ( V 2002) ' 41-48) '.
- LiCoO 2 and LiMn 2 O 4 show poor high-power characteristics over LiCoO 2 and LiMn 2 O 4 , which makes them unsuitable as materials for hybrid power sources for use in electric automobiles.
- Japanese Patent Laid-open No. 2003-59491 suggests a method for treating the surface of a cathode active material with conductive carbon black.
- significant improvement has not hitherto been reported.
- Lithium secondary batteries have problems in that the cycle life is drastically shortened due to repeated charge-discharge cycles, especially at high temperatures. The reason for this is that electrolytes are decomposed, active materials are degraded, and the internal resistance of batteries is increased due to the presence of moisture within batteries and other factors. A number of efforts to solve these problems have been made.
- Korean Patent No. 10-277796 discloses a cathode active material surface-coated with a metal oxide, such as an oxide of Mg, Al, Co, K, Na or Ca, by annealing.
- a metal oxide such as an oxide of Mg, Al, Co, K, Na or Ca
- a technique for improving the energy density and high-rate characteristics of lithium secondary batteries by adding TiO to an active material, e.g., LiCoO is suggested (Electrochemical and Solid-State Letters, 4 (6) A65-A67 2001).
- a technique for prolonging the cycle life of lithium secondary batteries by treating the surface of natural graphite with aluminum is known (Electrochemical and Solid-State Letters, 4 (8) A109-A112 2001).
- Korean Patent Laid-open No. 2003-0032363 describes a technique for coating the surface of a cathode active material with a hydroxide, oxyhydroxide, oxycarbonate or hydroxy carbonate of Mg, Al, Co, K, Na, Ca, Si, Ti, Sn, V, Ge, Ga, B, As, or Zr.
- the present invention has been made in view of the above problems, and it is an object of the present invention to provide a cathode active material coated with a fluorine compound powder that is capable of preventing deterioration in the performance of batteries, such as cycle characteristics, particularly at high voltage and high rate by coating of nano-sized fluorine compound.
- a cathode active material for lithium secondary batteries wherein the surface of the cathode active material is coated with a fluorine compound.
- the fluorine compound is at least one compound selected from the group consisting of CsF, KF, LiF, NaF, RbF, TiF, AgF, AgF 2 , BaF 2 , CaF 2 , CuF 2 , CdF 2 , FeF 2 , HgF 2 , Hg ⁇ , MnF 2 , MgF 2 , NiF 2 , PbF 2 , SnF 2 , SrF 2 , XeF 2 , ZnF 2 , AlF 3 , BF 3 , BiF 3 , CeF 3 , CrF 3 , DyF 3 , EuF 3 , GaF 3 , GdF 3 , FeF 3 , HoF 3 , InF 3 , LaF 3 , LuF 3 , MnF 3 , NdF 3 , VOF 3 , PrF 3 , SbF 3 , ScF 3 , SmF 3 , TbF
- the cathode active material coated with the fluorine compound is Li[Co M ]O F or Li [Co M ]O S (0 ⁇ a ⁇ 0.1, 0 ⁇ x ⁇ l-x x 2-a a 1-x x 2-a a
- the cathode active material coated with the fluorine compound is Li [Ni M ]O F or Li [Ni M ]O S (0.01 ⁇ a ⁇ 0.2, 0 l+a l-x x 2-b b 1+a l-x x 2-b b ⁇ b ⁇ 0.1, 0.01 ⁇ x ⁇ 0.5, and M is at least one metal selected from the group consisting of Mg, Al, Co, Mn, Zn, Fe, Cr, Ga, Mo and W) having a hexagonal layered rock-salt structure.
- the cathode active material coated with the fluorine compound is Li [Ni Co Mn ]O F or Li [Ni Co Mn ]O S (0.01 l+a 1-x-y x y 2-b b 1+a 1-x-y x y 2-b b
- the cathode active material coated with the fluorine compound is Li[Li (Ni Co Mn ) ]O F or Li[Li (Ni Co Mn ) ]O S a x l-2x x 1-a 2-b b a x l-2x x 1-a 2 b
- the cathode active material coated with the fluorine compound is Li[Li a (Ni x Co l-2x Mn x-y/2 M y) 1-a ]O 2-b F b or Li[Li a (Ni x Co l-2x Mn x-y/2
- M is at least one metal selected from the group consisting of Mg, Ca, Cu and Zn, 0.01 ⁇ a ⁇ 0.2, 0.05 ⁇ x ⁇ 0.5, 0.01 ⁇ y ⁇ 0.1, and 0 ⁇ b ⁇ 0.1) having a hexagonal layered rock-salt structure.
- the cathode active material coated with the fluorine compound is Li[Li a (Ni 1/3 Co (l/3-2x) Mn (1/3+x) M x) 1-a ]O 2-b F b or Li[Li a (Ni 1/3 Co (l/3-2x)
- M is at least one metal selected from the g toroup f consisting to of Mg to,'
- the cathode active material coated with the fluorine compound is Li[Li a (Ni x Co l-2x-y Mn x M y) 1-a ]O 2-b F b or Li[Li a (Nix Co l-2x-y Mn x M y )
- M is at least one metal selected from the group consisting of B, Al, Fe and Cr, 0.01 ⁇ a ⁇ 0.2, 0.05 ⁇ x ⁇ 0.5, 0.01 ⁇ y ⁇ 0.1, and 0 ⁇ b ⁇ 0.1) having a hexagonal layered rock-salt structure.
- the cathode active material coated with the fluorine compound is Li[Li a (Ni x Co l-2x-y Mn x-z/2 M yN z) 1-a ]O 2-b F b or Li[Li a (Ni x Co l-2x-y Mn x-z/2 M yN z) 1-a ]O 2-b S b (M is at least one metal selected from the g toroup r consisting to of B,> Al,>
- N is Mg or Ca, 0.01 ⁇ a ⁇ 0.2, 0 ⁇ x ⁇ 0.5, 0.01 ⁇ y ⁇ 0.1, and 0 ⁇ b ⁇ 0.1) having a hexagonal layered rock-salt structure.
- the cathode active material coated with the fluorine comp *ound is LiM x Fe l-x PO 4 (M is at least one metal selected from the group consisting of Co, Ni and Mn, and 0 ⁇ x ⁇ 1) having an olivine structure.
- the cathode active material coated with the fluorine compound is spinel Li l+a [Mn 2-x M x ]O 4-b F b or Li l+a [Mn 2-x M x ]O 4-b S b (0.01 ⁇ a
- the cathode active material coated with the fluorine compound is spinel Li [Ni Mn M IO F or Li [Ni Mn M IO S l+a 0.5 1.5-x x 4-b b 1+a 0.5 1.5-x x 4-b b
- M is at least one metal selected from the group consisting of Co, Ni, Cr, Mg, Al, Zn, Mo and W) having a cubic structure.
- a preferred method for preparing a cathode active material coated with a fluorine compound for lithium secondary batteries comprising mixing a fluorine (F) compound with an elemental precursor in an aqueous solution to obtain a fluorine compound powder with a high degree of dispersion therein, adding a solution of a cathode active material for lithium secondary batteries to the aqueous solution, and reacting the mixed solution at 50-100°C for 3-48 hours to coat the cathode active material with the fluorine compound.
- F fluorine
- a method for preparing a cathode active material coated with a fluorine compound for lithium secondary batteries comprising mixing a cathode active material for lithium secondary batteries with 0.1-10% by weight of an elemental precursor, relative to the weight of the cathode active material, in an aqueous solution, adding a solution of a fluorine (F) compound to the aqueous solution, and reacting the mixed solution at 50-100°C for 3-48 hours to coat the cathode active material with the fluorine compound.
- F fluorine
- the methods of the present invention further comprise drying the coated cathode active material at 110°C for 6-24 hours, followed by annealing in an oxidizing or reducing atmosphere or under vacuum at 150-900°C for 1-20 hours.
- the elemental precursor is an alkoxide, sulfate, nitrate, acetate, chloride or phosphate of at least one element selected from the group consisting of Cs, K, Li, Na, Rb, Ti, Ag (I), Ag (II), Ba, Ca, Cu, Cd, Fe, Hg (H), Hg (I), Mn (H), Mg, Ni, Pb, Sn, Sr, Xe, Zn, Al, B, Bi (HT), Ce (III), Cr, Dy, Eu, Ga, Gd, Fe, Ho, In, La, Lu, Mn (III), Nd, VO, Pr, Sb (UI), Sc, Sm, Tb, Ti (JlI), Tm, Y, Yb, TL Ce (IV), Ge, Hf, Si, Sn, Ti (IV), V, Zr, Nb, Sb (V), Ta, Bi (V), Mo, Re, S, and W.
- FIG. 1 is a flow chart illustrating the procedure of a method for coating a cathode active material in Example 1 of the present invention
- Fig. 2 shows X-ray diffraction (XRD) patterns of a cathode active material prepared in Example 1 and a cathode active material used in Comparative Example 1 of the present invention
- Fig. 3 is a field emission scanning electron microscopy (FESEM) image of a cathode active material prepared in Example 1 of the present invention
- Fig. 4 is a field emission scanning electron microscopy (FESEM) image of a cathode active material used in Comparative Example 1 of the present invention
- FIG. 5 and 6 are images showing the results of a cathode active material prepared in Example 1 of the present invention by energy dispersive spectroscopy (EDS);
- Fig. 7 is a graph showing discharge capacity versus number of cycles of half-cells using a cathode active material prepared in Example 1 and a cathode active material used in Comparative Example 1 of the present invention in the voltage range of
- Fig. 8 is a graph showing discharge capacity versus number of cycles of half-cells using a cathode active material prepared in Example 1 and a cathode active material used in Comparative Example 1 of the present invention in the voltage range of
- Fig. 9 is a graph showing discharge capacity versus number of cycles of half-cells using a cathode active material prepared in Example 1 and a cathode active material used in Comparative Example 1 of the present invention in the voltage range of
- Fig. 10 is a graph showing discharge capacity versus number of cycles of half-cells using a cathode active material prepared in Example 1 and a cathode active material used in Comparative Example 1 of the present invention according to C-rates in the voltage range of 3.0-4.5 V at room temperature (30°C); [40] Fig.
- FIG. 11 is a graph showing discharge capacity versus number of cycles of half-cells using a cathode active material prepared in Example 1 and a cathode active material used in Comparative Example 1 of the present invention according to C-rates in the voltage range of 3.0-4.5 V at a high temperature (55°C);
- Fig. 12 is a graph showing the Co dissolution rate of a cathode active material prepared in Example 1 and a cathode active material used in Comparative Example 1 of the present invention as a function of time;
- Fig. 13 shows XRD patterns of cathode active materials prepared in Examples 1 to
- FIG. 14 is a graph showing discharge capacity versus number of cycles of half-cells using cathode active materials prepared in Examples 1 to 3 and a cathode active material used in Comparative Example 1 of the present invention in the voltage range of 3.0-4.5V at 30°C and a constant current density of 0.2 mA/cm 2 ;
- Fig. 15 shows XRD patterns of cathode active materials prepared in Examples 4 to
- Fig. 16 is a graph showing discharge capacity versus number of cycles of half-cells using cathode active materials prepared in Examples 4 to 6 and a cathode active material used in Comparative Example 2 of the present invention in the voltage range of 3.4-4.3V at 55°C and a constant current density of 1.1 mA/cm (1C); and
- Fig. 17 is a graph showing discharge capacity versus number of cycles of half-cells using a cathode active material prepared in Example 7 and a cathode active material used in Comparative Example 1 of the present invention in the voltage range of 3.0-4.5 V at 30°C and a constant current density of 0.8 mA/cm .
- the present invention provides a cathode active material coated with a fluorine compound powder that is capable of preventing deterioration in the performance of lithium secondary batteries, such as cycle characteristics, particularly at high temperature and high rate.
- the fluorine compound coated on the surface of the cathode active material may be at least one compound selected from the group consisting of CsF, KF, LiF, NaF, RbF, TiF, AgF, AgF 2 , BaF 2 , CaF 2 , CuF 2 , CdF 2 , FeF 2 , HgF 2 , Hg ⁇ , MnF 2 , MgF 2 , NiF 2 , PbF 2 , SnF 2 , SrF 2 , XeF 2 , ZnF 2 , AlF 3 , BF 3 , BiF 3 , CeF 3 , CrF 3 , DyF 3 , EuF 3 , GaF 3 , GdF 3 , FeF 3 , HoF 3 , InF 3 , LaF 3 , LuF 3 , MnF 3 , NdF 3 , VOF 3 , PrF 3 , SbF 3 , ScF 3 , SmF 3 , S
- the coating with the fluorine compound reduces the influence of acids formed in the vicinity of the cathode active material and inhibits the reactivity between the cathode active material and an electrolyte so that a drastic reduction in the capacity of batteries can be prevented, thereby improving the charge-discharge characteristics, cycle characteristics, high- voltage and high-rate characteristics, and thermal stability of the final cathode active material for batteries.
- the surface of the cathode active material to be coated with the fluorine compound is amorphous, crystalline, or a mixed state thereof.
- the present invention also provides a preferred method for preparing a cathode active material coated with a fluorine compound for lithium secondary batteries, the method comprising the steps of mixing a fluorine (F) compound with an elemental precursor in an aqueous solution to obtain a fluorine compound powder with a high degree of dispersion therein, adding a solution of a cathode active material for lithium secondary batteries to the aqueous solution, and reacting the mixed solution at 50-100°C for 3-48 hours to coat the cathode active material with the fluorine compound.
- F fluorine
- the reason for the high co-precipitation reaction temperature is that the co- precipitation of the elemental precursor enables the formation of a precipitate with a high degree of dispersion in a complex state.
- the fluorine compound powder with a high degree of dispersion is obtained after a certain time of the mixing of the fluorine (F) compound with the elemental precursor. Since the coating is carried out after the formation of the fluorine compound powder with a high degree of dispersion, the necessity of controlling the precipitation rate is avoided when the fluorine (F) compound is added. In addition, since the fluorine compound is previously obtained by mixing the fluorine (F) compound and the elemental precursor, the amount of a solvent used, e.g., an alcohol, which is a more expensive reagent than distilled water, can be reduced, thus reducing the coating cost.
- a solvent used e.g., an alcohol, which is a more expensive reagent than distilled water
- the cathode active material coated with the fluorine compound is prepared in accordance with the following procedure.
- the amount of the fluorine (F)-containing solution used is preferably in the range of
- the coating element there can be used an alkoxide, such as methoxide, ethoxide, isopropoxide or butoxide, sulfate, nitrate, acetate, chloride, or oxide.
- the amount of the coating element used is desirably in the range of 0.1 to 10% by weight, relative to the weight of the cathode active material. If the coating element is used in an amount of less than 0.1% by weight, coating effects are not exhibited. Meanwhile, if the coating element is used in an amount exceeding 10% by weight, the excessive weight of the coating element causes a reduction in the capacity and energy density of batteries.
- the mixed solution containing the cathode active material for lithium secondary batteries and the fluorine compound is reacted at 50-150°C for 3-48 hours.
- the present invention also provides a method for preparing a cathode active material coated with a fluorine compound for lithium secondary batteries, comprising mixing a cathode active material for lithium secondary batteries with 0.1-10% by weight of an elemental precursor, relative to the weight of the cathode active material, in an aqueous solution, adding a solution of a fluorine (F) compound to the aqueous solution, and reacting the mixed solution at 50-100°C for 3-48 hours to coat the cathode active material with the fluorine compound.
- a fluorine (F) compound a fluorine (F) compound
- the fluorine compound powder obtained from the mixture of the fluorine (F) compound and the elemental precursor may not have a high degree of dispersion in view of the characteristics of the elemental precursor and has a strong tendency to aggregate so that it has a large size. As a result, an improvement in characteristics may not be expected. Accordingly, it is desirable to control the precipitation rate so that the fluorine compound is slowly formed, and at the same time, it is coated on the surface of the cathode active material.
- the cathode active material coated with the fluorine compound is prepared in accordance with the following procedure.
- at least one elemental precursor selected from Cs, K, Li, Na, Rb, Ti, Ag (I), Ag (II), Ba, Ca, Cu, Cd, Fe, Hg (II), Hg (I), Mn (II), Mg, Ni, Pb, Sn, Sr, Xe, Zn, Al, B, Bi (HI), Ce (III), Cr, Dy, Eu, Ga, Gd, Fe, Ho, In, La, Lu, Mn (JlI), Nd, VO, Pr, Sb (III), Sc, Sm, Tb, Ti (HI), Tm, Y, Yb, TI, Ce (IV), Ge, Hf, Si, Sn, Ti (IV), V, Zr, Nb, Sb (V), Ta, Bi (V), Mo, Re, S and W is dissolved in an alcohol, such as a monohydric (e.g., a monohydric (
- the amount of the fluorine (F)-containing solution used is preferably in the range of
- the metal salt there can be used an alkoxide, such as methoxide, ethoxide, isopropoxide or butoxide, sulfate, nitrate, acetate, chloride, or oxide.
- the amount of the coating element used is desirably in the range of 0.1 to 10% by weight, relative to the weight of the cathode active material. If the coating element is used in an amount of less than 0.1% by weight, coating effects are not exhibited. Meanwhile, if the coating element is used in an amount exceeding 10% by weight, the excessive weight of the coating element causes a reduction in the capacity and energy density of batteries.
- the mixed solution containing the cathode active material for lithium secondary batteries and the fluorine compound is reacted at 50-150°C for 3-48 hours.
- the methods of the present invention may further comprise drying the coated cathode active material at 110°C for 6-24 hours, followed by annealing in an oxidizing or reducing atmosphere or under vacuum at 150-900°C for 1-20 hours.
- the annealing serves to remove remaining impurities to obtain the fluorine compound in a desired form and to enhance the binding force of the fluorine compound powder coated on the surface of the cathode active material.
- the reason for the high co- precipitation reaction temperature is that the co-precipitation of AlF enables the formation of a precipitate with a high degree of dispersion in a complex state.
- the LiCoO coated with the fluorine compound was washed with distilled water, dried in a hot-air thermostat at 110°C for 12 hours, and annealed in an inert atmosphere at 400°C, giving the final AlF -coatedLiCoO .
- a 2032 coin cell was fabricated by using the cathode, a lithium foil as a counter electrode, a porous polyethylene film (thickness: 25 D, Celgard 2300, Celgard LLC) as a separator, and a IM LiPF 6 solution in a mixed solvent of ethylene carbonate and dimethyl carbonate (1:1 (Wv)) as a liquid electrolyte in accordance with procedures well known in the art.
- charge-discharge tests were conducted at room temperature (30°C) and a current density of 0.8 mA/cm (Fig. 7), at a high temperature (55°C) and a current density of 0.8 mA/cm (Fig.
- the reason for the high co- precipitation reaction temperature is that the co-precipitation of ZnF enables the formation of a precipitate with a high degree of dispersion in a complex state.
- the LiCoO coated with the fluorine compound was washed with distilled water, dried in a hot-air thermostat at 110°C for 12 hours, and annealed in an inert atmosphere at 400°C, giving the final ZnF -coatedLiCoO .
- a cathode was produced using the ZnF -coated LiCoO , and a coin cell comprising the cathode was fabricated in accordance with the procedure of Example 1.
- a charge-discharge test was conducted at 30°C and a current density of 0.2 mA/cm in the voltage range of 3.0-4.5 V using an electrochemical analysis system (Toscat3000U, Toyo, Japan). Changes in discharge capacity with increasing number of cycles are shown in Fig. 13. The graph shows that there is a slight decrease in the discharge capacity of the coin cell with increasing number of cycles, indicating superior cycle characteristics.
- the reason for the high co-precipitation reaction temperature is that the co-precipitation of LiF enables the formation of a precipitate with a high degree of dispersion in a complex state.
- the LiCoO coated with the fluorine compound was washed with distilled water, dried in a hot-air thermostat at 110°C for 12 hours, and annealed in an inert atmosphere at 400°C, giving the final LiF-coatedLiCoO .
- a cathode was produced using the LiF-coated LiCoO , and a coin cell comprising the cathode was fabricated.
- a charge- discharge test was conducted using an electrochemical analysis system (Toscat3000U, Toyo, Japan) at 30°C and a current density of 0.2 mA/cm in the voltage range of 3.0-4.5 V. Changes in discharge capacity with increasing number of cycles are shown in Fig. 14. The graph shows that there is a slight decrease in the discharge capacity of the coin cell with increasing number of cycles, indicating superior cycle characteristics.
- AlF 3 -coated LiMn 2 O 4 was p r rep rared, ⁇ > the characteristics of the AlF 3 -coated LiMn 2 O 4 were evaluated, and a cell comprising the AlF -coated LiMn O was fabricated in accordance with the procedure of Example 1.
- a charge-discharge test was conducted using an electrochemical analysis system (Toscat3000U, Toyo, Japan) at 55°C and a current density of 1.1 mA/cm (1C) in the voltage range of 3.4-4.3 V. Changes in discharge capacity with increasing number of cycles are shown in Fig. 16. The graph shows that there is a slight decrease in the discharge capacity of the coin cell with increasing number of cycles, indicating superior cycle characteristics.
- ZnF 2 -coated LiMn 2 O was p V rep *ared,> the characteristics of the ZnF 2 -coated LiMn 2 O were evaluated, and a cell comprising the ZnF -coated LiMn O was fabricated in accordance with the procedure of Example 1.
- a charge-discharge test was conducted using an electrochemical analysis system (Toscat3000U, Toyo, Japan) at 55°C and a current density of 1.1 mA/cm (1C) in the voltage range of 3.4-4.3 V. Changes in discharge capacity with increasing number of cycles are shown in Fig. 16. The graph shows that there is a slight decrease in the discharge capacity of the coin cell with increasing number of cycles, indicating superior cycle characteristics.
- LiF-coated LiMn O was prepared, the characteristics of the LiF-coated LiMn O were evaluated, and a cell comprising the LiF-coated LiMn O was fabricated in accordance with the procedure of Example 1.
- a charge-discharge test was conducted using an electrochemical analysis system (Toscat3000U, Toyo, Japan) at 55°C and a current density of 1.1 mA/cm 2 (1C) in the voltage range of 3.4-4.3 V. Changes in discharge capacity with increasing number of cycles are shown in Fig. 16. The graph shows that there is a slight decrease in the discharge capacity of the coin cell with increasing number of cycles, indicating superior cycle characteristics.
- Fig. 2 shows XRD patterns of the cathode active material prepared in Example 1 and the cathode active material used in Comparative Example 1.
- Fig. 4 is a FESEM image of the cathode active material used in Comparative Example 1.
- Fig. 7 is a graph showing discharge capacity versus number of cycles of the half-cells using the cathode active material prepared in Example 1 and the cathode active material used in Comparative Example 1 in the voltage range of 3.0-4.5 V at room temperature (30°C) and a constant current density of
- Fig. 8 is a graph showing discharge capacity versus number of cycles of the half-cells using the cathode active material prepared in Example 1 and the cathode active material used in Comparative Example 1 in the voltage range of 3.0-4.5 V at a high temperature (55°C) and a constant current density of 0.8 mA/cm .
- Fig. 9 is a graph showing discharge capacity versus number of cycles of the half-cells using the cathode active material prepared in Example 1 and the cathode active material used in Compara tive Example 1 in the voltage range of 3.0-4.5 V at room temperature (30°C) and a constant current density of 0.2 mA/cm 2 .
- Fig. 8 is a graph showing discharge capacity versus number of cycles of the half-cells using the cathode active material prepared in Example 1 and the cathode active material used in Comparative Example 1 in the voltage range of 3.0-4.5 V at a high temperature (55°C) and a constant current density of 0.8 mA/cm
- Fig. 10 is a graph showing discharge capacity versus number of cycles of the half-cells using the cathode active material prepared in Example 1 and the cathode active material used in Comparative Example 1 according to C-rates in the voltage range of 3.0-4.5V at room temperature (30°C).
- Fig. 11 is a graph showing discharge capacity versus number of cycles of the half-cells using the cathode active material prepared in Example 1 and the cathode active material used in Comparative Example 1 according to C-rates in the voltage range of 3.0-4.5 V at a high temperature (55°C).
- Fig. 12 is a graph showing the Co dissolution rate of the cathode active material prepared in Example 1 and the cathode active material used in Comparative Example 1 as a function of time.
- Fig. 12 is a graph showing the Co dissolution rate of the cathode active material prepared in Example 1 and the cathode active material used in Comparative Example 1 as a function of time.
- FIG. 13 shows XRD patterns of the cathode active materials prepared in Examples 1 to 3 and the cathode active material used in Comparative Example 1.
- FIG. 14 is a graph showing discharge capacity versus number of cycles of the half-cells using the cathode active materials prepared in Examples 1 to 3 and the cathode active material used in Comparative Example 1 in the voltage range of 3.0-4.5 V at 30°C and a constant current density of 0.2 mA/cm .
- [124] [ 125] Comparative Example 2
- Fig. 15 shows XRD patterns of the cathode active materials prepared in Examples 4 to 6 and the cathode active material used in Comparative Example 2.
- Fig. 16 is a graph showing discharge capacity versus number of cycles of the half-cells using the cathode active materials prepared in Examples 4 to 6 and the cathode active material used in Comparative Example 2 in the voltage range of 3.4-4.3 V at 55°C and a constant current density of Ll mA/cm 2 (lC).
- the coating of a cathode active material for lithium secondary batteries with a fluorine compound reduces the influence of acids formed in the vicinity of the cathode active material and inhibits the reactivity between the cathode active material and an electrolyte so that a drastic reduction in the capacity of batteries can be prevented, thereby improving the charge-discharge characteristics, cycle characteristics, high- voltage and high-rate characteristics, and thermal stability of the final cathode active material for batteries.
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Abstract
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KR20050031309 | 2005-04-15 | ||
KR1020060023501A KR100822013B1 (ko) | 2005-04-15 | 2006-03-14 | 불소화합물코팅 리튬이차전지 양극 활물질 및 그 제조방법 |
PCT/KR2006/000987 WO2006109930A1 (fr) | 2005-04-15 | 2006-03-17 | Matiere active de cathode recouverte de compose de fluor pour batteries secondaires au lithium et leur procede de preparation |
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Families Citing this family (59)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5276795B2 (ja) * | 2007-03-30 | 2013-08-28 | パナソニック株式会社 | 非水電解質二次電池用正極活物質およびそれを用いた非水電解質二次電池 |
JP4518125B2 (ja) * | 2007-09-27 | 2010-08-04 | トヨタ自動車株式会社 | 正極活物質およびリチウム二次電池 |
JP5271275B2 (ja) * | 2007-12-14 | 2013-08-21 | パナソニック株式会社 | 非水電解質二次電池の製造方法 |
US8187752B2 (en) | 2008-04-16 | 2012-05-29 | Envia Systems, Inc. | High energy lithium ion secondary batteries |
WO2009131700A2 (fr) | 2008-04-25 | 2009-10-29 | Envia Systems, Inc. | Batteries lithium-ion à haute énergie avec compositions d'électrode négative particulaires |
US8916294B2 (en) | 2008-09-30 | 2014-12-23 | Envia Systems, Inc. | Fluorine doped lithium rich metal oxide positive electrode battery materials with high specific capacity and corresponding batteries |
US8389160B2 (en) * | 2008-10-07 | 2013-03-05 | Envia Systems, Inc. | Positive electrode materials for lithium ion batteries having a high specific discharge capacity and processes for the synthesis of these materials |
US9012073B2 (en) | 2008-11-11 | 2015-04-21 | Envia Systems, Inc. | Composite compositions, negative electrodes with composite compositions and corresponding batteries |
US8465873B2 (en) | 2008-12-11 | 2013-06-18 | Envia Systems, Inc. | Positive electrode materials for high discharge capacity lithium ion batteries |
US10056644B2 (en) | 2009-07-24 | 2018-08-21 | Zenlabs Energy, Inc. | Lithium ion batteries with long cycling performance |
US8475959B2 (en) | 2009-08-27 | 2013-07-02 | Envia Systems, Inc. | Lithium doped cathode material |
US8535832B2 (en) | 2009-08-27 | 2013-09-17 | Envia Systems, Inc. | Metal oxide coated positive electrode materials for lithium-based batteries |
US9190694B2 (en) | 2009-11-03 | 2015-11-17 | Envia Systems, Inc. | High capacity anode materials for lithium ion batteries |
US9843041B2 (en) * | 2009-11-11 | 2017-12-12 | Zenlabs Energy, Inc. | Coated positive electrode materials for lithium ion batteries |
US8993177B2 (en) | 2009-12-04 | 2015-03-31 | Envia Systems, Inc. | Lithium ion battery with high voltage electrolytes and additives |
JP5149927B2 (ja) | 2010-03-05 | 2013-02-20 | 株式会社日立製作所 | リチウム二次電池用正極材料、リチウム二次電池及びそれを用いた二次電池モジュール |
US8765306B2 (en) | 2010-03-26 | 2014-07-01 | Envia Systems, Inc. | High voltage battery formation protocols and control of charging and discharging for desirable long term cycling performance |
US8741484B2 (en) | 2010-04-02 | 2014-06-03 | Envia Systems, Inc. | Doped positive electrode active materials and lithium ion secondary battery constructed therefrom |
US9083062B2 (en) | 2010-08-02 | 2015-07-14 | Envia Systems, Inc. | Battery packs for vehicles and high capacity pouch secondary batteries for incorporation into compact battery packs |
US8928286B2 (en) | 2010-09-03 | 2015-01-06 | Envia Systems, Inc. | Very long cycling of lithium ion batteries with lithium rich cathode materials |
EP2619838A1 (fr) * | 2010-09-21 | 2013-07-31 | Basf Se | Procédé de fabrication de matériaux d'électrodes |
US8663849B2 (en) | 2010-09-22 | 2014-03-04 | Envia Systems, Inc. | Metal halide coatings on lithium ion battery positive electrode materials and corresponding batteries |
US9166222B2 (en) | 2010-11-02 | 2015-10-20 | Envia Systems, Inc. | Lithium ion batteries with supplemental lithium |
US9601228B2 (en) | 2011-05-16 | 2017-03-21 | Envia Systems, Inc. | Silicon oxide based high capacity anode materials for lithium ion batteries |
US9159990B2 (en) | 2011-08-19 | 2015-10-13 | Envia Systems, Inc. | High capacity lithium ion battery formation protocol and corresponding batteries |
JP5544342B2 (ja) * | 2011-09-21 | 2014-07-09 | 株式会社日立製作所 | リチウムイオン二次電池 |
KR20130033154A (ko) * | 2011-09-26 | 2013-04-03 | 전자부품연구원 | 리튬 이차전지용 양극 활물질, 그의 제조방법 및 그를 포함하는 리튬이차전지 |
WO2013090263A1 (fr) | 2011-12-12 | 2013-06-20 | Envia Systems, Inc. | Oxydes de lithium-métal avec phases multiples et cyclage électrochimique à haute énergie stable |
US9139441B2 (en) | 2012-01-19 | 2015-09-22 | Envia Systems, Inc. | Porous silicon based anode material formed using metal reduction |
US9070489B2 (en) | 2012-02-07 | 2015-06-30 | Envia Systems, Inc. | Mixed phase lithium metal oxide compositions with desirable battery performance |
KR20140125856A (ko) * | 2012-02-15 | 2014-10-29 | 바스프 에스이 | 입자, 이의 제조 방법 및 이의 용도 |
JP5601338B2 (ja) * | 2012-03-27 | 2014-10-08 | Tdk株式会社 | 正極活物質、及びそれを用いたリチウムイオン二次電池 |
US10553871B2 (en) | 2012-05-04 | 2020-02-04 | Zenlabs Energy, Inc. | Battery cell engineering and design to reach high energy |
US9780358B2 (en) | 2012-05-04 | 2017-10-03 | Zenlabs Energy, Inc. | Battery designs with high capacity anode materials and cathode materials |
US9552901B2 (en) | 2012-08-17 | 2017-01-24 | Envia Systems, Inc. | Lithium ion batteries with high energy density, excellent cycling capability and low internal impedance |
US10115962B2 (en) | 2012-12-20 | 2018-10-30 | Envia Systems, Inc. | High capacity cathode material with stabilizing nanocoatings |
WO2014119973A1 (fr) * | 2013-01-31 | 2014-08-07 | 한양대학교 산학협력단 | Matière d'anode active pour une batterie secondaire au lithium, son procédé de fabrication et batterie secondaire au lithium l'utilisant |
AU2013377013B2 (en) | 2013-02-01 | 2016-06-30 | Emd Acquisition Llc | Improved lithium manganese oxide compositions |
US10020491B2 (en) | 2013-04-16 | 2018-07-10 | Zenlabs Energy, Inc. | Silicon-based active materials for lithium ion batteries and synthesis with solution processing |
US10886526B2 (en) | 2013-06-13 | 2021-01-05 | Zenlabs Energy, Inc. | Silicon-silicon oxide-carbon composites for lithium battery electrodes and methods for forming the composites |
KR102214826B1 (ko) * | 2013-07-31 | 2021-02-10 | 삼성전자주식회사 | 복합 양극 활물질, 이를 포함하는 리튬 전지, 및 이의 제조방법 |
US11476494B2 (en) | 2013-08-16 | 2022-10-18 | Zenlabs Energy, Inc. | Lithium ion batteries with high capacity anode active material and good cycling for consumer electronics |
CN106029577A (zh) * | 2014-02-27 | 2016-10-12 | 巴斯夫欧洲公司 | 制备氟化锂化混合过渡金属氧化物的方法 |
US10193135B2 (en) | 2015-01-15 | 2019-01-29 | Zenlabs Energy, Inc. | Positive electrode active materials with composite coatings for high energy density secondary batteries and corresponding processes |
CN105552311B (zh) * | 2016-01-11 | 2017-03-08 | 山东玉皇新能源科技有限公司 | 一种抑制正极材料放电中值电压衰减的改性方法 |
CN105789555A (zh) * | 2016-04-26 | 2016-07-20 | 中国科学院长春应用化学研究所 | 一种硅复合材料及其制备方法、电池负极和锂离子电池 |
WO2017222967A2 (fr) | 2016-06-21 | 2017-12-28 | Sion Power Corporation | Revêtements pour composants de cellules électrochimiques |
KR102331069B1 (ko) | 2016-11-30 | 2021-11-25 | 삼성에스디아이 주식회사 | 복합양극활물질, 이를 포함하는 양극 및 리튬전지 |
US20200176770A1 (en) | 2017-06-26 | 2020-06-04 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing positive electrode active material, and secondary battery |
JP6852653B2 (ja) * | 2017-11-07 | 2021-03-31 | トヨタ自動車株式会社 | 正極活物質およびフッ化物イオン電池 |
US11094925B2 (en) | 2017-12-22 | 2021-08-17 | Zenlabs Energy, Inc. | Electrodes with silicon oxide active materials for lithium ion cells achieving high capacity, high energy density and long cycle life performance |
JP7000239B2 (ja) | 2018-04-16 | 2022-01-19 | トヨタ自動車株式会社 | 正極活物質粒子、正極、リチウムイオン二次電池、および正極活物質粒子の製造方法 |
CN108329485A (zh) * | 2018-04-16 | 2018-07-27 | 天津师范大学 | 双发射镧系铕金属有机骨架材料及其制备方法与应用 |
WO2020068134A1 (fr) * | 2018-09-30 | 2020-04-02 | Seeo, Inc. | Particules de matériau de cathode à haute énergie ayant des surfaces d'oxyfluorure pour traitement aqueux |
US20220029159A1 (en) * | 2018-12-13 | 2022-01-27 | Semiconductor Energy Laboratory Co., Ltd. | Positive electrode active material, method for manufacturing the same, and secondary battery |
KR102386904B1 (ko) | 2020-04-29 | 2022-04-15 | 주식회사 에스엠랩 | 리튬 이차전지용 양극활물질, 그의 제조방법 및 이를 포함하는 리튬이차전지 |
CN112670510B (zh) * | 2020-12-23 | 2023-05-26 | 中南大学 | 一种NaCrO2@MFx/C复合材料及其制备和在钠离子电池中的应用 |
WO2023081532A1 (fr) | 2021-11-08 | 2023-05-11 | Advanced Cell Engineering, Inc. | Empilement d'électrodes à fentes et cellules électrochimiques et batteries contenant un empilement d'électrodes à fentes |
CN114373902A (zh) * | 2021-11-25 | 2022-04-19 | 西安交通大学 | 制备表面包覆氟化物的三元ncm的方法、ncm及电极 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08264183A (ja) * | 1995-03-27 | 1996-10-11 | Sanyo Electric Co Ltd | リチウム二次電池 |
EP1267431A1 (fr) * | 2001-06-14 | 2002-12-18 | Samsung SDI Co., Ltd. | Materiau actif pour pile et sa méthode de préparation |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100441520B1 (ko) * | 2002-05-28 | 2004-07-23 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 양극 활물질 및 그 제조방법 |
-
2006
- 2006-03-17 EP EP06716437A patent/EP1880435A4/fr not_active Withdrawn
- 2006-03-17 WO PCT/KR2006/000987 patent/WO2006109930A1/fr active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08264183A (ja) * | 1995-03-27 | 1996-10-11 | Sanyo Electric Co Ltd | リチウム二次電池 |
EP1267431A1 (fr) * | 2001-06-14 | 2002-12-18 | Samsung SDI Co., Ltd. | Materiau actif pour pile et sa méthode de préparation |
Non-Patent Citations (3)
Title |
---|
D. AURBACH , B. MARKOVSKY, A. RODKIN, E. LEVI, Y.S. COHEN, H.-J. KIM, M. SCHMIDT: "On the capacity fading of LiCoO2 intercalation electrodes: the effect of cycling, storage, temperature, and surface film forming additives" ELECTROCHIMICA ACTA, vol. 47, 2002, pages 4291-4306, XP002529709 * |
See also references of WO2006109930A1 * |
Y.-K. SUN, K.-J. HONG, JAI PRAKASH, K.AMINE: "Electrochemical performance of nano-sized ZnO-coated LiNi0:5Mn1:5O4 spinel as 5 V materials at elevated temperatures" ELECTROCHEMISTRY COMMUNICATIONS, vol. 4, no. 4, 2002, pages 344-348, XP002529710 * |
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