CN102714314B - 正极活性材料和包含所述正极活性材料的锂二次电池 - Google Patents
正极活性材料和包含所述正极活性材料的锂二次电池 Download PDFInfo
- Publication number
- CN102714314B CN102714314B CN201180006232.2A CN201180006232A CN102714314B CN 102714314 B CN102714314 B CN 102714314B CN 201180006232 A CN201180006232 A CN 201180006232A CN 102714314 B CN102714314 B CN 102714314B
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- electrode active
- active materials
- secondary battery
- lithium secondary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 27
- 229910052744 lithium Inorganic materials 0.000 title claims description 27
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000006182 cathode active material Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 25
- 229910052723 transition metal Inorganic materials 0.000 claims description 19
- 150000003624 transition metals Chemical class 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011149 active material Substances 0.000 description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 23
- -1 nickel metal hydride Chemical class 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 239000004020 conductor Substances 0.000 description 10
- 239000011255 nonaqueous electrolyte Substances 0.000 description 10
- 239000011572 manganese Substances 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000000975 co-precipitation Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000007784 solid electrolyte Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 3
- 229910014689 LiMnO Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 229910020121 Li0.02(Ni0.78Mn0.12Co0.10)0.98 Inorganic materials 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910016768 Ni0.5Mn0.4Co0.1 Inorganic materials 0.000 description 2
- 241001597008 Nomeidae Species 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 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
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 150000004862 dioxolanes Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- HLXZNVUGXRDIFK-UHFFFAOYSA-N nickel titanium Chemical compound [Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni] HLXZNVUGXRDIFK-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- 125000006091 1,3-dioxolane group Chemical class 0.000 description 1
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229910000925 Cd alloy Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 1
- 229910020120 Li0.02(Ni0.53Mn0.27Co0.20)0.98 Inorganic materials 0.000 description 1
- 229910020434 Li0.1(Ni0.5Mn0.4Co0.1)0.9 Inorganic materials 0.000 description 1
- 229910012722 Li3N-LiI-LiOH Inorganic materials 0.000 description 1
- 229910012716 Li3N-LiI—LiOH Inorganic materials 0.000 description 1
- 229910012734 Li3N—LiI—LiOH Inorganic materials 0.000 description 1
- 229910013043 Li3PO4-Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910013035 Li3PO4-Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910012810 Li3PO4—Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910012797 Li3PO4—Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910012047 Li4SiO4-LiI-LiOH Inorganic materials 0.000 description 1
- 229910012075 Li4SiO4-LiI—LiOH Inorganic materials 0.000 description 1
- 229910012057 Li4SiO4—LiI—LiOH Inorganic materials 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910015044 LiB Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 229910012573 LiSiO Inorganic materials 0.000 description 1
- 229910012346 LiSiO4-LiI-LiOH Inorganic materials 0.000 description 1
- 229910012345 LiSiO4-LiI—LiOH Inorganic materials 0.000 description 1
- 229910012348 LiSiO4—LiI—LiOH Inorganic materials 0.000 description 1
- 229920000914 Metallic fiber Polymers 0.000 description 1
- ZHGDJTMNXSOQDT-UHFFFAOYSA-N NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O Chemical compound NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O ZHGDJTMNXSOQDT-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- BEKPOUATRPPTLV-UHFFFAOYSA-N [Li].BCl Chemical compound [Li].BCl BEKPOUATRPPTLV-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- PHMPXRLILNXEIS-UHFFFAOYSA-N carbonic acid 1-fluoroprop-1-ene Chemical compound C(O)(O)=O.FC=CC PHMPXRLILNXEIS-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical class NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002409 silicon-based active material Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L50/00—Electric propulsion with power supplied within the vehicle
- B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
-
- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Power Engineering (AREA)
- Transportation (AREA)
- Mechanical Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Organic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
本发明公开了一种二次电池用正极活性材料,其包含选自下式1的至少一种化合物:(1-s-t)[Li(LiaMn(1-a-x-y)NixCoy)O2]*s[Li2CO3]*t[LiOH](1),其中0<a<0.2,0<x<0.9,0<y<0.5,a+x+y<1,0<s<0.03,且0<t<0.03;且a、x和y表示摩尔比,且s和t表示重量比。尽管在高电流下重复充放电,但是所述正极活性材料在室温和高温下具有长寿命,且提供优异的稳定性。
Description
技术领域
本发明涉及二次电池用正极活性材料。更具体地,本发明涉及一种二次电池用正极活性材料,所述二次电池在室温和高温下具有长寿命并具有优异的稳定性,因为其包含具有特定组成的化合物。
背景技术
移动装置的技术开发和增加的需求,导致对作为能源的二次电池的需求急剧增加。在这些二次电池中,具有高能量密度和电压、长寿命和低自放电的锂二次电池可商购获得并被广泛使用。
另外,对环境问题的增加的关注导致了大量与作为使用化石燃料的车辆如汽油车辆和柴油车辆的替代品的电动车辆(EV)和混合电动车辆(HEV)有关的研究,所述使用化石燃料的车辆是空气污染的主要因素。这些电动车辆通常使用镍金属氢化物(Ni-MH)二次电池作为电动车辆(EV)、混合电动车辆(HEV)等的电源。然而,正在进行与具有高能量密度和放电电压的锂二次电池的使用相关的大量研究且其中的一些已经可商购获得。
特别地,用于电动车辆的锂二次电池应具有高能量密度,在短时间内展示大功率并在短时间内重复基于高电流的充放电的苛刻条件下可使用10年以上,由此与常规的小型锂二次电池相比,需要显著优异的稳定性和长寿命。
作为用于小型电池的锂离子二次电池的正极活性材料,可使用具有层状结构的含锂的钴氧化物如LiCoO2。另外,已经考虑了使用含锂的锰氧化物如具有层状晶体结构的LiMnO2和具有尖晶石晶体结构的LiMnO2以及含锂的镍氧化物(LiNiO2)。
在这些正极活性材料中,LiCoO2由于其寿命性能和高充放电效率而最常用,但其具有如下劣势:结构稳定性低且由于用作原料的钴的来源限制而造成成本高,由此在价格竞争性方面存在限制。
锂锰氧化物如LiMnO2和LiMn2O4具有热稳定性优异且成本低的优势,但具有容量小且高温性能差的劣势。
另外,LiNiO2正极活性材料展示优异充电容量的更好性能,但由于Li与过渡金属之间的阳离子混合问题而导致非常难以合成,由此具有与倍率特性相关的严重问题。
发明内容
技术问题
因此,为了解决尚未解决的上述和其他技术问题而完成了本发明。
作为为了解决上述问题而进行的各种广泛和细致的研究和实验的结果,本发明的发明人开发了包含式1的化合物的二次电池用正极活性材料,并发现,当使用所述正极活性材料制造二次电池时,所述活性材料有助于提高电池稳定性并能够提高诸如寿命特性的性能。基于这种发现而完成了本发明。
技术方案
根据本发明的一方面,提供一种二次电池用正极活性材料,其包含选自下式1的至少一种化合物:
(1-s-t)[Li(LiaMn(1-a-x-y)NixCoy)O2]*s[Li2CO3]*t[LiOH](1)
其中0<a<0.2,0<x<0.9,0<y<0.5,a+x+y<1;0<s<0.03,且0<t<0.03;以及
a、x和y表示摩尔比,且s和t表示重量比。
根据上述能够看出,本发明使用具有层状结构、特定元素和化合物组成的锂镍锰钴复合氧化物作为正极活性材料。
式1中的a为如上所限定的大于0且小于0.2,并优选为0.01~0.19。式1中的x为如上所限定的大于0且小于0.9,并优选为0.2~0.8。
碳酸锂和氢氧化锂会将可能存在于电池中的强酸HF吸引至所述式的化合物处并由此抑制HF的副反应,从而有助于提高电池的稳定性并提高诸如寿命性能的性能。
如上所限定的,碳酸锂和氢氧化锂以相对于活性材料的总重量为低于0.03重量比的量存在。当碳酸锂和氢氧化锂的含量过高时,它们会不利地造成电池容量的劣化。碳酸锂对氢氧化锂之比也是重要的,作为本发明人进行重复研究的结果,通过控制合成程序、合成之后的控制等能够获得所述比例。这种原理由式1的活性材料表示,但不简单限制为所述化合物。
通常,在式1的化合物中,过渡金属如Mn、Ni和Co中的至少一种可以被可布置在六配位结构中的其他元素置换。置换量为过渡金属总量的约10%以下。
在式1的化合物中,可利用其他阴离子在预定量范围内对氧(O)内容物进行置换。如本领域中所熟知的,置换阴离子优选为选自卤素、硫族化物元素和氮中的至少一种。
阴离子置换可提高与过渡金属的结合力并防止正极活性材料的结构转变,由此提高电池的寿命。另一方面,当阴离子的置换量过高(相对于阴离子的总量超过0.2摩尔比)时,式1的化合物不能保持其稳定结构,从而不利地造成寿命劣化。因此,相对于阴离子的总量,阴离子的置换量优选为0.01~0.2摩尔比,更优选0.01~0.1摩尔比。
包含选自式1的至少一种的本发明正极活性材料可单独使用或以与选自其他锂过渡金属氧化物和锂过渡金属磷氧化物中的至少一种化合物组合的方式使用。
可以基于其组成式来制备包含本发明正极活性材料的式1的化合物。例如,可以通过在含氧的气氛下对锂前体与混合过渡金属前体的混合物进行焙烧来制备所述化合物。可将碳酸锂、氢氧化锂等用作锂前体并可以将过渡金属氧化物、过渡金属氢氧化物等用作混合过渡金属前体。所述混合过渡金属前体可以为各过渡金属前体的混合物或所有过渡金属的前体。可以通过共沉淀等来制备后一种混合前体。
在优选实施方案中,通过本申请人提交的韩国专利公开2009-0105868中所公开的方法来制备具有组成M(OH1-d)2(其中0<d<0.5)的混合前体,将所述过渡金属前体与锂化合物混合,随后进行焙烧。作为参考将韩国专利公开2009-0105868中所公开的内容并入本文中。
可以通过将导电材料和粘合剂添加到本发明的正极活性材料中来制备正极混合物。
例如,通过将所述正极混合物与诸如水或NMP的溶剂进行混合以制备浆体,然后将所述浆体涂布到正极集电器上,随后对其进行干燥和压制,可制造正极。
通过将含有根据本发明的正极活性材料、导电材料和粘合剂的混合物涂布到正极集电器上,随后进行干燥可制造正极。含有正极活性材料、导电材料和粘合剂的混合物(正极混合物)可任选地含有选自粘度控制剂和填料中的至少一种物质。
通常将正极集电器制成具有3~500μm的厚度。所述正极集电器没有特别限制,只要其具有合适的导电性而不会在电池中造成不利的化学变化即可。正极集电器的实例包括不锈钢;铝;镍;钛;烧结碳;以及利用碳、镍、钛或银进行了表面处理的铝或不锈钢。如果需要,还可以对这些集电器进行加工以在其表面上形成细小的不规则,从而提高对正极活性材料的粘合力。另外,可以以包括膜、片、箔、网、多孔结构、泡沫和无纺布的各种形式使用所述集电器。
基于包含正极活性材料的混合物的总重量,通常以0.01~30重量的量添加所述导电材料。可以使用任意导电材料而无特别限制,只要其具有合适的导电性而不会在电池中造成不利的化学变化即可。导电材料的实例包括包括如下的导电材料:石墨;炭黑如炭黑、乙炔黑、科琴黑、槽法炭黑、炉黑、灯黑和热裂法炭黑;碳衍生物如碳纳米管或富勒烯;导电纤维如碳纤维和金属纤维;金属粉末如氟化碳粉末、铝粉末和镍粉末;导电须如氧化锌和钛酸钾;导电金属氧化物如二氧化钛;和聚亚苯基衍生物。
粘合剂为增强电极活性材料对导电材料和集电器的粘合的成分。基于包含正极活性材料的混合物的总重量,通常以1~50重量的量添加所述粘合剂。粘合剂的实例包含聚偏二氟乙烯、聚乙烯醇、羧甲基纤维素(CMC)、淀粉、羟丙基纤维素、再生纤维素、聚乙烯基吡咯烷酮、四氟乙烯、聚乙烯、聚丙烯、乙烯-丙烯-二烯三元共聚物(EPDM)、磺化的EPDM、苯乙烯丁二烯橡胶、氟橡胶和各种共聚物。
粘度控制剂对电极混合物的粘度进行控制以促进电极混合物的混合以及其到集电器上的涂布,且基于电极混合物的总重量,可以以30重量%的量添加所述粘度控制剂。所述粘度控制剂的实例包括但不限于羧甲基纤维素、聚丙烯酸和聚偏二氟乙烯。如果需要,所述溶剂也可充当粘度控制剂。
填料为任选用于抑制电极膨胀的成分。可使用任意填料而无特别限制,只要其不会在制造的电池中造成不利的化学变化且为纤维材料即可。填料的实例包括烯烃聚合物如聚乙烯和聚丙烯;以及纤维材料如玻璃纤维和碳纤维。
可以将由此制造的正极与负极、隔膜和含锂盐的非水电解质组合使用以制造锂二次电池。
例如,通过将含有负极活性材料的负极混合物涂布到负极集电器上,然后进行干燥来制备负极。如果需要,所述负极混合物可包含上述成分即导电材料、粘合剂和填料。
通常将负极集电器制造成具有3~500μm的厚度。负极集电器没有特别限制,只要其具有合适的电导率而不会在制造的电池中造成不利的化学变化即可。负极集电器的实例包括铜;不锈钢;铝;镍;钛;烧结碳;和利用碳、镍、钛或银进行了表面处理的铜或不锈钢;以及铝-镉合金。与正极集电器类似,如果需要,还可以对这些集电器进行加工以在其表面上形成细小的不规则,从而提高对负极活性材料的粘合强度。另外,可以以包括膜、片、箔、网、多孔结构、泡沫和无纺布的各种形式使用所述集电器。
所述负极活性材料的实例包括碳和石墨材料如天然石墨、人造石墨、膨胀石墨、碳纤维、硬碳、炭黑、碳纳米管、二萘嵌苯、活性炭;可与锂形成合金的金属如Al、Si、Sn、Ag、Bi、Mg、Zn、In、Ge、Pb、Pd、Pt和Ti以及含有这些元素的化合物;碳和石墨材料与金属及其化合物的复合材料;和含锂的氮化物。其中,更优选碳基活性材料、硅基活性材料、锡基活性材料或硅-碳基活性材料。所述材料可单独或以其两种以上组合的方式使用。
隔膜插入在所述正极与所述负极之间。作为隔膜,可使用具有高离子渗透率和机械强度的绝缘薄膜。所述隔膜典型地具有0.01~10μm的孔径和5~300μm的厚度。作为隔膜,使用由烯烃聚合物如聚丙烯和/或玻璃纤维或聚乙烯制成的片或无纺布,其具有耐化学性和疏水性。当使用诸如聚合物的固体电解质作为电解质时,所述固体电解质还可以充当隔膜和电解质两者。
所述含锂盐的非水电解质由非水电解质和锂盐构成。作为所述非水电解质,可利用非水电解质、固体电解质和无机固体电解质。
能够用于本发明中的非水电解质的实例包括非质子性有机溶剂如N-甲基-2-吡咯烷酮、碳酸亚丙酯、碳酸亚乙酯、碳酸亚丁酯、碳酸二甲酯、碳酸二乙酯、γ-丁内酯、1,2-二甲氧基乙烷、四羟基Franc、2-甲基四氢呋喃、二甲亚砜、1,3-二氧戊环、甲酰胺、二甲基甲酰胺、二氧戊环、乙腈、硝基甲烷、甲酸甲酯、乙酸甲酯、磷酸三酯、三甲氧基甲烷、二氧戊环衍生物、环丁砜、甲基环丁砜、1,3-二甲基-2-咪唑烷酮、碳酸亚丙酯衍生物、四氢呋喃衍生物、乙醚、丙酸甲酯和丙酸乙酯。
用于本发明中的有机固体电解质的实例包括聚乙烯衍生物、聚环氧乙烷衍生物、聚环氧丙烷衍生物、磷酸酯聚合物、polyagitationlysine、聚酯硫化物、聚乙烯醇、聚偏二氟乙烯和含有离子离解基团的聚合物。
所述无机固体电解质的实例包括锂的氮化物、卤化物和硫酸盐如Li3N、LiI、Li5NI2、Li3N-LiI-LiOH、LiSiO4、LiSiO4-LiI-LiOH、Li2SiS3、Li4SiO4、Li4SiO4-LiI-LiOH和Li3PO4-Li2S-SiS2。
所述锂盐是易溶于上述非水电解质中的材料且其实例包括LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、(CF3SO2)2NLi、氯硼烷锂、低级脂族羧酸锂、四苯基硼酸锂和酰亚胺。
另外,为了提高充放电特性和阻燃性,例如可以向非水电解质中添加吡啶、亚磷酸三乙酯、三乙醇胺、环醚、乙二胺、正甘醇二甲醚、六磷酸三酰胺(hexaphosphorictriamide)、硝基苯衍生物、硫、醌亚胺染料、N-取代的唑烷酮、N,N-取代的咪唑烷、乙二醇二烷基醚、铵盐、吡咯、2-甲氧基乙醇、三氯化铝等。如果需要,为了赋予不燃性,所述非水电解质可还包含含卤素的溶剂如四氯化碳和三氟乙烯。此外,为了提高高温储存特性,所述非水电解质可还包含二氧化碳气体等且可还包含氟代碳酸亚乙酯(FEC)、丙烯磺酸内酯(PRS)、氟代碳酸亚丙酯(FPC)等。
包含根据本发明的正极活性材料的锂二次电池可用作电池模块的单元电池,所述电池模块是需要高温稳定性、长循环性能和优异倍率性能的中型和大型装置的电源。
优选地,所述中型和大型装置可以为电动车辆(EV)、混合电动车辆(HEV)或插电式混合电动车辆(PHEV)。
具体实施方式
现在,参考如下实施例对本发明进行更详细的说明。提供这些实例仅用于说明本发明且不应将其解释为限制本发明的范围和主旨。
实施例1
根据韩国专利公开2009-0105868中所公开的方法通过共沉淀合成了Ni0.53Mn0.27Co0.2(OH0.53)2以作为过渡金属前体,然后将其与Li2CO3混合,在940℃下的炉子中对所得混合物进行焙烧并然后通过在500L/分钟下并入空气而进行冷却,从而合成0.9978Li(Li0.02(Ni0.53Mn0.27Co0.20)0.98)O2*0.0012LiOH*0.0010Li2CO3以作为活性材料。
通过将10g制备的活性材料添加至200mL水中并测量利用0.1NHCl进行滴定所用的碱的量,确定了制备的活性材料中LiOH和LiCO3的量。
比较例1
以与实施例1中相同的方式制备了0.9971Li(Li0.02(Ni0.53Mn0.27Co0.20)0.98)O2*0.0029Li2CO3以作为活性材料,不同之处在于,通过本领域中已知的普通共沉淀法制备其中Ni、Mn和Co的摩尔比(Ni:Mn:Co)为53:27:20的过渡金属前体,并且通过在振动烘箱中在150℃下通过时以100L/分钟并入CO2以作为冷却气氛并持续一小时而使碳酸盐的量最大化。
实施例2
以与实施例1中相同的方式制备了0.9972Li(Li0.02(Ni0.53Mn0.27Co0.20)0.98)O2*0.0018LiOH*0.0010Li2CO3以作为活性材料,不同之处在于在300L/分钟下通过空气的同时通过冷却来提高OH的量。
实施例3
以与实施例1中相同的方式制备了0.9972Li(Li0.02(Ni0.53Mn0.27Co0.20)0.98)O2*0.0008LiOH*0.0020Li2CO3以作为活性材料,不同之处在于在振动烘箱中在150℃下通过时在100L/分钟下并入CO2以作为冷却气氛并持续15分钟。
比较例2
以与实施例1中相同的方式制备了Li(Li0.02(Ni0.53Mn0.27Co0.20)0.98)O2,不同之处在于利用蒸馏水对活性材料进行洗涤以除去在实施例1中制备的活性材料的碱并在烘箱中于130℃下干燥24小时。
实施例4
根据韩国专利公开2009-0105868中所公开的方法通过共沉淀合成了Ni0.78Mn0.12Co0.10(OH0.53)2以作为过渡金属前体,然后将其与Li2CO3混合,在890℃下的炉子中对所得混合物进行焙烧并然后在200L/分钟下通过氧(O2)而进行冷却,从而合成0.9952Li(Li0.02(Ni0.78Mn0.12Co0.10)0.98)O2*0.0026LiOH*0.0022Li2CO3以作为活性材料。
通过将10g制备的活性材料添加至200mL水中并通过利用0.1NHCl进行滴定测量碱的量,确定了制备的材料中LiOH和LiCO3的量。
比较例3
以与实施例4中相同的方式制备了0.9948Li(Li0.02(Ni0.78Mn0.12Co0.10)0.98)O2*0.0052Li2CO3以作为活性材料,不同之处在于,通过本领域中已知的普通共沉淀法制备其中Ni、Mn和Co的摩尔比(Ni:Mn:Co)为78:12:10的过渡金属前体,并且通过在振动烘箱中在150℃下通过时以100L/分钟并入CO2以作为冷却气氛并持续一小时而使碳酸盐的量最大化。
比较例4
通过以与比较例2中相同的方式对实施例4中制备的活性材料进行处理,制备了Li(Li0.02(Ni0.78Mn0.12Co0.10)0.98)O2以作为活性材料。
实施例5
根据韩国专利公开2009-0105868中所公开的方法通过共沉淀合成了Ni0.5Mn0.4Co0.1(OH0.53)2以作为过渡金属前体,然后将其与Li2CO3混合,在950℃下的炉子中对所得混合物进行焙烧并然后通过在500L/分钟下通过空气而进行冷却,从而合成0.9967Li(Li0.1(Ni0.5Mn0.4Co0.1)0.9)O2*0.0021LiOH*0.0012Li2CO3以作为活性材料。
通过将10g制备的活性材料添加至200mL水中并通过利用0.1NHCl进行滴定测量碱的量,确定了制备的材料中LiOH和LiCO3的量。
比较例5
以与实施例4中相同的方式制备了0.9966Li(Li0.1(Ni0.5Mn0.4Co0.1))O2*0.0034Li2CO3以作为活性材料,不同之处在于,通过本领域中的普通共沉淀法制备了其中Ni、Mn和Co的摩尔比(Ni:Mn:Co)为5:4:1的过渡金属前体并在振动烘箱中在150℃下通过时以100L/分钟并入CO2以作为冷却气氛并持续一小时而使碳酸盐的量最大化。
比较例6
通过以与比较例2中相同的方式对实施例5中制备的活性材料进行处理,制备了Li(Li0.1(Ni0.5Mn0.4Co0.1))O2以作为活性材料。
试验例1
使用在实施例1~5和比较例1~6中合成的各活性材料,以活性材料:导电材料:粘合剂为95:2.5:2.5的方式制备了浆体,然后将其涂布在Al箔上。对得到的电极进行压制,使得孔隙率为23%,并以圆形对得到的电极进行冲切以制造硬币型电池。此时,将Li金属用作负极并将1MLiPF6在碳酸酯混合溶剂(EC:DMC:DEC=1:2:1,体积比)中的溶液用作电解质。
在下表1中所述的条件下对由此制造的电池进行了试验。
表1:电化学试验结果
从上表1能够看出,LiOH和Li2CO3在活性材料中发挥了极其重要的作用。从比较例2、4和6能够看出,当在活性材料中不存在LiOH和Li2CO3时,倍率特性和循环特性急剧下降。作为实际的电池循环,当将活性材料使用300或500个循环时,这种特性之差是上面显示的差的10~15倍,特别地,当应用于电动车辆用电池时,所述差会进一步增大。另外,从比较例2、4和6的结果能够看出,尽管仅存在Li2CO3,但性能仍然劣化。
尽管出于示例性目的而公开了本发明的优选实施方案,但是本领域的技术人员应理解,在不背离附属权利要求书中所公开的本发明范围和主旨的条件下,各种改变、添加和替代是可能的。
工业实用性
根据上述可清楚,根据本发明的包含锂镍锰钴复合氧化物的正极活性材料,在短时间和高温范围内在高电流充电条件下能够确保稳定性并提高寿命性能。
Claims (11)
1.一种二次电池用正极活性材料,其由选自下式1的至少一种化合物组成:
(1-s-t)[Li(LiaMn(1-a-x-y)NixCoy)O2]*s[Li2CO3]*t[LiOH](1)
其中0<a<0.2,0<x<0.9,0<y<0.5,a+x+y<1,0.01<s<0.03,0.01<t<0.03;以及
a、x和y表示摩尔比,且s和t表示重量比,
其中所述正极活性材料由具有下式2的过渡金属前体得到:
M(OH1-d)2(2)
其中0<d<0.5,M包括Mn、Ni和Co。
2.如权利要求1所述的正极活性材料,其中a满足条件0.01<a≤0.19。
3.如权利要求1所述的正极活性材料,其中x不小于0.02且小于0.8。
4.如权利要求1所述的正极活性材料,其中y大于0且不大于0.3。
5.一种二次电池用正极混合物,包含权利要求1~4中任一项的正极活性材料。
6.一种锂二次电池用正极,其中权利要求5的正极混合物被涂布到集电器上。
7.一种锂二次电池,包含权利要求6的正极。
8.如权利要求7所述的锂二次电池,其中所述锂二次电池用作单元模块的单元电池,所述单元模块是中型和大型装置的电源。
9.如权利要求8所述的锂二次电池,其中所述中型或大型装置是电动车辆。
10.如权利要求9所述的锂二次电池,其中所述电动车辆是混合电动车辆。
11.如权利要求9所述的锂二次电池,其中所述电动车辆是插电式混合电动车辆。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20100041015 | 2010-04-30 | ||
KR10-2010-0041015 | 2010-04-30 | ||
PCT/KR2011/003066 WO2011136550A2 (ko) | 2010-04-30 | 2011-04-27 | 양극 활물질 및 이를 이용한 리튬 이차전지 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102714314A CN102714314A (zh) | 2012-10-03 |
CN102714314B true CN102714314B (zh) | 2016-01-20 |
Family
ID=44862038
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201180006232.2A Active CN102714314B (zh) | 2010-04-30 | 2011-04-27 | 正极活性材料和包含所述正极活性材料的锂二次电池 |
Country Status (5)
Country | Link |
---|---|
US (2) | US9786911B2 (zh) |
EP (1) | EP2511972B1 (zh) |
KR (1) | KR101240174B1 (zh) |
CN (1) | CN102714314B (zh) |
WO (1) | WO2011136550A2 (zh) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101240174B1 (ko) | 2010-04-30 | 2013-03-07 | 주식회사 엘지화학 | 양극 활물질 및 이를 이용한 리튬 이차전지 |
KR101326088B1 (ko) | 2010-09-17 | 2013-11-07 | 주식회사 엘지화학 | 양극 활물질 및 이를 이용한 리튬 이차전지 |
WO2014010849A1 (ko) | 2012-07-09 | 2014-01-16 | 주식회사 엘지화학 | 리튬 복합 전이금속 산화물 제조용 전구체 |
JP2015528789A (ja) * | 2012-07-20 | 2015-10-01 | スリーエム イノベイティブ プロパティズ カンパニー | リチウムイオンバッテリー用高電圧カソード組成物 |
US9450278B2 (en) * | 2012-12-20 | 2016-09-20 | International Business Machines Corporation | Cathode material for lithium—oxygen battery |
US20160197341A1 (en) * | 2013-08-22 | 2016-07-07 | 3M Innovative Properties Company | Cathode compositions for lithium-ion batteries |
JP6201277B2 (ja) * | 2013-09-13 | 2017-09-27 | 住友金属鉱山株式会社 | 非水系電解質二次電池用正極活物質とその製造方法 |
Family Cites Families (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11233113A (ja) * | 1998-02-19 | 1999-08-27 | Sony Corp | 二次電池用Li−Co系複合酸化物の製造方法 |
JP3611188B2 (ja) | 2000-03-03 | 2005-01-19 | 日産自動車株式会社 | 非水電解質二次電池用正極活物質および非水電解質二次電池 |
US6660432B2 (en) * | 2000-09-14 | 2003-12-09 | Ilion Technology Corporation | Lithiated oxide materials and methods of manufacture |
JP4678457B2 (ja) | 2000-10-24 | 2011-04-27 | 株式会社豊田中央研究所 | リチウム二次電池正極活物質用リチウム遷移金属複合酸化物およびそれを用いたリチウム二次電池 |
US7358009B2 (en) | 2002-02-15 | 2008-04-15 | Uchicago Argonne, Llc | Layered electrodes for lithium cells and batteries |
JP2004281253A (ja) * | 2003-03-17 | 2004-10-07 | Hitachi Metals Ltd | 非水系リチウム二次電池用正極活物質とその製造方法及びその正極活物質を用いた非水系リチウム二次電池 |
US20050069771A1 (en) * | 2003-09-30 | 2005-03-31 | Manev Vesselin G. | Positive electrode material for lithium-ion battery |
US7211237B2 (en) * | 2003-11-26 | 2007-05-01 | 3M Innovative Properties Company | Solid state synthesis of lithium ion battery cathode material |
JP2005327644A (ja) * | 2004-05-17 | 2005-11-24 | Shin Kobe Electric Mach Co Ltd | リチウム二次電池用正極材の製造方法、正極材及びリチウム二次電池 |
KR100598491B1 (ko) * | 2004-10-21 | 2006-07-10 | 한양대학교 산학협력단 | 이중층 구조를 가지는 리튬이차전지용 양극 활물질, 그제조 방법 및 그를 사용한 리튬이차전지 |
JP4213659B2 (ja) * | 2004-12-20 | 2009-01-21 | 株式会社東芝 | 非水電解質電池および正極活物質 |
EP1831943B1 (en) | 2004-12-31 | 2014-12-10 | IUCF-HYU (Industry-University Cooperation Foundation Hanyang University) | Method for preparing double-layer cathode active materials for lithium secondary batteries |
US7648693B2 (en) | 2005-04-13 | 2010-01-19 | Lg Chem, Ltd. | Ni-based lithium transition metal oxide |
US20070292761A1 (en) | 2005-04-13 | 2007-12-20 | Lg Chem, Ltd. | Material for lithium secondary battery of high performance |
KR100790834B1 (ko) | 2006-05-10 | 2008-01-03 | 주식회사 엘지화학 | 고성능 리튬 이차전지용 재료 |
KR100794142B1 (ko) | 2006-05-10 | 2008-01-16 | 주식회사 엘지화학 | 고성능 리튬 이차전지용 재료 |
KR100925854B1 (ko) * | 2006-06-13 | 2009-11-06 | 주식회사 엘지화학 | 리튬 전이 금속 산화물의 제조방법 |
KR100834053B1 (ko) * | 2006-09-29 | 2008-06-02 | 한양대학교 산학협력단 | 양극, 이를 포함하는 리튬 이차 전지, 및 이를 포함하는 하이브리드 커패시터 |
JP2008147068A (ja) | 2006-12-12 | 2008-06-26 | Ise Chemicals Corp | 非水電解液二次電池用リチウム複合酸化物 |
JP4979432B2 (ja) * | 2007-03-28 | 2012-07-18 | 三洋電機株式会社 | 円筒型リチウム二次電池 |
US20080280205A1 (en) * | 2007-05-07 | 2008-11-13 | 3M Innovative Properties Company | Lithium mixed metal oxide cathode compositions and lithium-ion electrochemical cells incorporating same |
JP5077131B2 (ja) * | 2007-08-02 | 2012-11-21 | ソニー株式会社 | 正極活物質、並びにそれを用いた正極、および非水電解質二次電池 |
KR100959589B1 (ko) * | 2008-04-03 | 2010-05-27 | 주식회사 엘지화학 | 리튬 복합 전이금속 산화물 제조용 신규 전구체 |
HUE060257T2 (hu) * | 2008-04-03 | 2023-02-28 | Lg Energy Solution Ltd | Új prekurzor lítium kompozit átmenetifém-oxid elõállítására |
KR100998684B1 (ko) | 2008-06-09 | 2010-12-07 | 주식회사 엘지화학 | 안전성이 향상된 이차전지 |
KR101059757B1 (ko) | 2008-09-10 | 2011-08-26 | 주식회사 엘지화학 | 리튬 이차전지용 양극 활물질 |
KR101082468B1 (ko) * | 2009-02-13 | 2011-11-11 | 주식회사 엘지화학 | 에너지 밀도가 향상된 리튬이차전지 |
BR112012012515B1 (pt) * | 2009-11-25 | 2019-07-16 | Lg Chem, Ltd. | Cátodo com base em dois tipos de compostos e bateria secundária de lítio compreendendo o mesmo |
BR112012012518B1 (pt) | 2009-11-25 | 2019-07-16 | Lg Chem, Ltd. | Catodo baseado em dois tipos de compostos e bateria secundária de lítio compreendendo o mesmo |
WO2011122865A2 (ko) | 2010-04-01 | 2011-10-06 | 주식회사 엘지화학 | 양극 활물질 및 이를 이용한 리튬 이차전지 |
KR101240174B1 (ko) | 2010-04-30 | 2013-03-07 | 주식회사 엘지화학 | 양극 활물질 및 이를 이용한 리튬 이차전지 |
-
2011
- 2011-04-27 KR KR1020110039363A patent/KR101240174B1/ko active IP Right Grant
- 2011-04-27 EP EP11775255.0A patent/EP2511972B1/en active Active
- 2011-04-27 WO PCT/KR2011/003066 patent/WO2011136550A2/ko active Application Filing
- 2011-04-27 CN CN201180006232.2A patent/CN102714314B/zh active Active
-
2012
- 2012-06-21 US US13/529,430 patent/US9786911B2/en active Active
-
2017
- 2017-08-30 US US15/691,036 patent/US10559821B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
KR20110121554A (ko) | 2011-11-07 |
US10559821B2 (en) | 2020-02-11 |
EP2511972A2 (en) | 2012-10-17 |
US9786911B2 (en) | 2017-10-10 |
EP2511972B1 (en) | 2017-05-31 |
US20170365849A1 (en) | 2017-12-21 |
WO2011136550A3 (ko) | 2012-03-01 |
WO2011136550A2 (ko) | 2011-11-03 |
EP2511972A4 (en) | 2013-07-10 |
KR101240174B1 (ko) | 2013-03-07 |
CN102714314A (zh) | 2012-10-03 |
US20130122363A1 (en) | 2013-05-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101451196B1 (ko) | 양극 활물질 및 그것을 포함한 리튬 이차전지 | |
CN101821879B (zh) | 锂二次电池的阴极活性材料 | |
CN102668179B (zh) | 基于两种组分的正极以及包含其的锂二次电池 | |
EP2869369B1 (en) | Cathode active material for secondary battery and secondary battery comprising same | |
US10741841B2 (en) | Electrode active material having improved energy density and lithium secondary battery including the same | |
CN102668186B (zh) | 正极活性材料和包含其的锂二次电池 | |
EP2811562B1 (en) | Method of manufacturing electrode for lithium secondary cell | |
KR20150037085A (ko) | 리튬 이차전지용 양극 활물질 및 이를 포함하는 리튬 이차전지 | |
CN103109401B (zh) | 正极活性材料和包含所述正极活性材料的锂二次电池 | |
US10559821B2 (en) | Cathode active material and lithium secondary battery comprising the same | |
CN104969400A (zh) | 新型二次电池 | |
CN104025346A (zh) | 正极活性材料和含其的控制杂质或溶胀的锂二次电池及提高产率的制备正极活性材料的方法 | |
KR101501440B1 (ko) | 이차전지용 신규 양극 | |
CN102804458B (zh) | 锂二次电池用正极活性材料 | |
US10008720B2 (en) | Method of preparing positive electrode active material for lithium secondary batteries | |
US8852806B2 (en) | Positive active material for secondary battery of improved rate capability | |
US10424781B2 (en) | Cathode active material and lithium secondary battery comprising the same | |
CN102859764B (zh) | 二次电池用正极 | |
US10573880B2 (en) | Cathode active material for secondary battery with enhanced lifespan characteristics and method of preparing the same | |
CN102906909B (zh) | 二次电池用正电极活性材料 | |
CN102870257B (zh) | 二次电池用正极活性材料 | |
CN103098267B (zh) | 二次电池用正极活性材料 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right | ||
TR01 | Transfer of patent right |
Effective date of registration: 20211213 Address after: Seoul, South Kerean Patentee after: LG Energy Solution Address before: Seoul, South Kerean Patentee before: LG CHEM, Ltd. |