CN107074588B - 过渡金属氧化物的前体、锂和过渡金属氧化物的复合物、包含所述复合物的正极和二次电池 - Google Patents
过渡金属氧化物的前体、锂和过渡金属氧化物的复合物、包含所述复合物的正极和二次电池 Download PDFInfo
- Publication number
- CN107074588B CN107074588B CN201580059467.6A CN201580059467A CN107074588B CN 107074588 B CN107074588 B CN 107074588B CN 201580059467 A CN201580059467 A CN 201580059467A CN 107074588 B CN107074588 B CN 107074588B
- Authority
- CN
- China
- Prior art keywords
- lithium
- transition metal
- compound
- metal oxide
- precursor
- 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
- 229910000314 transition metal oxide Inorganic materials 0.000 title claims abstract description 52
- 239000002243 precursor Substances 0.000 title claims abstract description 37
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 65
- 150000001875 compounds Chemical class 0.000 title claims description 44
- 229910021450 lithium metal oxide Inorganic materials 0.000 title claims description 15
- 239000000126 substance Substances 0.000 claims abstract description 26
- 229910005565 NiaMnb Inorganic materials 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 48
- 150000001450 anions Chemical class 0.000 claims description 28
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 14
- 150000002642 lithium compounds Chemical class 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 239000012702 metal oxide precursor Substances 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 33
- 239000007774 positive electrode material Substances 0.000 description 33
- -1 zirconium cation Chemical class 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 21
- 229910052723 transition metal Inorganic materials 0.000 description 21
- 239000011572 manganese Substances 0.000 description 16
- 150000003624 transition metals Chemical class 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229910052759 nickel Inorganic materials 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 229910052751 metal Chemical group 0.000 description 11
- 239000002184 metal Chemical group 0.000 description 11
- 229910019142 PO4 Inorganic materials 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- 229910052748 manganese Inorganic materials 0.000 description 9
- 229910052726 zirconium Inorganic materials 0.000 description 9
- 239000002033 PVDF binder Substances 0.000 description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000005611 electricity Effects 0.000 description 8
- 239000010955 niobium Substances 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000004020 conductor Substances 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000004411 aluminium Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000011255 nonaqueous electrolyte Substances 0.000 description 6
- 229910006504 ZrSO4 Inorganic materials 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000007784 solid electrolyte Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910013292 LiNiO Inorganic materials 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003839 salts Chemical class 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 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
- 229910012820 LiCoO Inorganic materials 0.000 description 3
- 229910003005 LiNiO2 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
- 229910020350 Na2WO4 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000006229 carbon black Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 229910001317 nickel manganese cobalt oxide (NMC) Inorganic materials 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003623 transition metal compounds Chemical class 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 241001597008 Nomeidae Species 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 235000019593 adhesiveness Nutrition 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000004862 dioxolanes Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 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
- 239000000945 filler Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000001976 improved effect Effects 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 150000002641 lithium Chemical class 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
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002927 oxygen compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 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
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-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
- WDGCBNTXZHJTHJ-UHFFFAOYSA-N 2h-1,3-oxazol-2-id-4-one Chemical compound O=C1CO[C-]=N1 WDGCBNTXZHJTHJ-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910001558 CF3SO3Li Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910000925 Cd alloy Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 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
- 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
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-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
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910007969 Li-Co-Ni Inorganic materials 0.000 description 1
- 229910007177 Li1+zNi0.4Mn0.4Co0.2O2 Inorganic materials 0.000 description 1
- 229910007180 Li1+zNi1/3Co1/3Mn1/3O2 Inorganic materials 0.000 description 1
- 229910007558 Li2SiS3 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
- 229910010739 Li5Ni2 Inorganic materials 0.000 description 1
- 229910003253 LiB10Cl10 Inorganic materials 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910014383 LiNi1-yMyO2 Inorganic materials 0.000 description 1
- 229910014952 LiNi1−yMyO2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001290 LiPF6 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
- 101150058243 Lipf gene Proteins 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910016622 LixFe2O3 Inorganic materials 0.000 description 1
- 229910015103 LixWO2 Inorganic materials 0.000 description 1
- 229910006555 Li—Co—Ni Inorganic materials 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229920000914 Metallic fiber Polymers 0.000 description 1
- 229910002651 NO3 Inorganic materials 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
- 241000080590 Niso Species 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910004367 OH1-x Inorganic materials 0.000 description 1
- 229910004345 OH1−x 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
- 229910006145 SO3Li Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- BEKPOUATRPPTLV-UHFFFAOYSA-N [Li].BCl Chemical compound [Li].BCl BEKPOUATRPPTLV-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-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
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 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
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000006232 furnace black 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
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- HSFDLPWPRRSVSM-UHFFFAOYSA-M lithium;2,2,2-trifluoroacetate Chemical compound [Li+].[O-]C(=O)C(F)(F)F HSFDLPWPRRSVSM-UHFFFAOYSA-M 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- DMFXUAWAYAOUIP-UHFFFAOYSA-N n-nitrobenzenesulfonamide Chemical class [O-][N+](=O)NS(=O)(=O)C1=CC=CC=C1 DMFXUAWAYAOUIP-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000008569 process Effects 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 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
- 238000004381 surface treatment Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
- C01G33/006—Compounds containing, besides niobium, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/006—Compounds containing, besides tungsten, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- 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
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明提供一种由如下化学式1表示的过渡金属氧化物的前体。[化学式1] NiaMnbCo1‑(a+b+c+d)ZrcMd[OH(1‑x)2‑y]A(y/n)
Description
技术领域
本发明涉及过渡金属氧化物的前体、锂和过渡金属氧化物的复合物、以及包含所述复合物的正极和二次电池,且更具体地,涉及具有低电阻和高输出的过渡金属氧化物的前体、锂和过渡金属氧化物的复合物、以及包含所述复合物的正极和二次电池。
本申请要求2014年10月31日在韩国提交的韩国专利申请10-2014-0149818号的优先权,其公开内容通过参考并入本文中。
背景技术
近来,对能量存储技术的兴趣日益增长。随着能量储存技术的应用领域已经扩展到移动电话、摄像机、膝上型计算机以及甚至电动汽车,已经对电化学装置的研究和开发做了很多努力。在这方面,电化学装置受到最多的关注,且其中,重点关注能够再充电的二次电池的开发,且最近在开发这种电池时,正在进行新电极和电池设计的研究和开发以提高容量密度和比能量。
对于锂二次电池的正极活性材料,主要使用含锂的钴氧化物(LiCoO2),且此外,可以设想使用: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LiMn2O4;以及含锂的镍氧化物(LiNiO2)。
在上述正极活性材料中,如今LiCoO2由于具有包括良好循环特性的良好性能而被广泛使用,但其缺点是安全性低且由于作为原料的钴的资源有限而价格高。由于锂锰氧化物如LiMnO2和LiMn2O4使用资源丰富且环境友好的锰作为原料,所以作为能够代替LiCoO2的正极活性材料而受到大量关注。然而,锂锰氧化物的缺点是容量低且循环特性差。
此外,诸如LiNiO2的锂/镍类氧化物比钴类氧化物更便宜并且当充电至4.25V时显示出高的放电容量,并且掺杂的LiNiO2的可逆容量接近约200mAh/g,高于LiCoO2的容量(约153mAh/g)。因此,虽然平均放电电压和体积密度稍低,但是包含LiNiO2正极活性材料的商业电池具有改善的能量密度,并因此近来正在大力开展关于镍类正极活性材料的研究以开发高容量电池。
因此,许多较早的技术集中在改善LiNiO2类正极活性材料的性能和生产LiNiO2的方法,并已经提出了通过过渡金属如Co和Mn对部分镍取代的锂过渡金属氧化物。然而,仍然存在未解决的问题,LiNiO2类正极活性材料的生产成本高、因电池产生气体而造成膨胀、化学稳定性低且pH高。
为了解决这些问题,一些现有技术试图通过将诸如LiF、Li2SO4、Li3PO4的材料应用到锂/镍-锰-钴氧化物的表面来改善电池性能,但在这种情况下,所述材料仅被定位在锂/镍-锰-钴氧化物的表面上,引起问题;在发挥期望水平的效果方面存在限制,并且需要额外的工艺以将材料施加到锂/镍-锰-钴氧化物的表面。
然而,尽管进行了各种尝试,但尚没有开发出具有令人满意的性能的锂和过渡金属氧化物的复合物。
发明内容
技术问题
本发明旨在解决所述问题,并且旨在提供包含特定阳离子和阴离子的前体、和具有低电阻和高输出的包含由所述前体制造的锂和过渡金属氧化物的复合物的二次电池。
本发明的这些和其它目的和优势将从如下详细描述中变得显而易见。此外,将容易理解,本发明的目的和优势可以通过所附权利要求及其组合中阐述的手段或方法来实现。
技术方案
为了实现所述目的,根据本发明的一个方面,提供了由如下化学式1表示的过渡金属氧化物的前体:
[化学式1] NiaMnbCo1-(a+b+c+d)ZrcMd[OH(1-x)2-y]A(y/n)
其中,M是W和Nb中的至少一者,A是除了OH之外的一种或多种阴离子,0.3≤a≤0.9,0.05≤b≤0.5,0<c<0.05,0<d<0.05,a+b+c+d≤1,0<x<0.5,0≤y≤0.05,n是A的氧化数。
当M为W或Nb时,c:d摩尔比可以为2:1~3:2。
A可以是选自如下中的至少一种:PO4、CO3、BO3和F。
A可以包含PO4和F。
所述过渡金属氧化物的前体可具有1.0~2.5g/cc的振实密度。
根据本发明的另一个方面,提供了一种锂和过渡金属氧化物的复合物,所述复合物包含通过对过渡金属氧化物的前体和锂化合物进行煅烧而得到的生成物。
所述锂化合物可以是选自如下物质中的至少一种物质:氢氧化锂、碳酸锂和锂氧化物。
相对于1摩尔的过渡金属氧化物的前体,所述锂化合物为0.95~1.2mol。
所述煅烧可以在600~1000℃下实施。
此外,为了达到所述目的,根据本发明的又一个方面,提供了一种包含锂和过渡金属氧化物的复合物的正极。
另外,根据本发明的又一个方面,提供了包含所述正极的二次电池。
有益效果
本发明通过将包含锆的阳离子添加到基于多成分的正极活性材料用前体中来确保结构稳定性,所述基于多成分的正极活性材料包含镍-锰-钴的过渡金属。
此外,通过包含具有最佳摩尔比的基于多成分的复合过渡金属阳离子,对电阻的降低和输出的改进具有效果。
此外,还有另外使用羟基离子和特定阴离子的优势:能够制备具有高密度的正极活性材料,并最终能够提供具有高容量和优异寿命特性的二次电池。
附图说明
附图显示了本发明的优选实施方案,并且与上述描述一起用于进一步理解本发明的技术主旨。然而,不能将本发明解释为限于附图。
图1是显示本发明的实施例和比较例中制造的锂二次电池之间的容量的比较的图。
图2是显示本发明的实施例和比较例中制造的锂二次电池之间的电阻的比较的图。
具体实施方式
下文中,对本发明进行详细说明。应当理解,在说明书和所附权利要求中使用的术语不应被解释为限于一般和词典的含义,而是在发明人被允许适当定义术语以进行最佳解释的原则的基础上基于与本发明的技术方面相对应的含义和概念来解释。因此,说明书中所述的实施方案和附图中所示的描述仅仅是用于说明的目的的优选实例,而不旨在显示本发明的所有技术方面,并且应当理解,在提交本发明时可以对其完成多种可选等价体和变体。
本发明提供了由如下化学式1表示的过渡金属氧化物的前体:
[化学式1] NiaMnbCo1-(a+b+c+d)ZrcMd[OH(1-x)2-y]A(y/n)
其中,M被选自如下中的至少一种取代:W(钨)、Nb(铌)、Al(铝)、Cu(铜)、Fe(铁)、Mg(镁)、B(硼)、Cr(铬)和其他过渡金属,优选被W(钨)和Nb(铌)中的一种取代。
A是除OH以外的一种或多种阴离子,0.3≤a≤0.9,0.05≤b≤0.5,0<c<0.05,0<d<0.05,a+b+c+d≤1,0<x<0.5,0≤y≤0.05,n是A的氧化数。
过渡金属氧化物的前体包含大量的镍,且可以特别期望用于制备高容量锂二次电池用正极活性材料。即,基于总量(摩尔标准),镍含量(a)如上所述为0.3~0.9,且优选为0.33~0.8,即镍比锰和钴以相对更大的量存在。当镍含量小于0.3时,难以预期高容量。当镍含量大于0.9时,稳定性大大下降。
此外,锰含量(b)如上所述为0.05~0.5,且优选0.1~0.5。
锆和金属取代可以有助于由于在晶体中的取代而导致结晶度改善、以及由于形成具有良好离子传输性质的局部相而导致输出特性的改善。
锆含量(c)和金属M的摩尔量(d)之和可以在大于或等于0.1的范围内,并且优选地可以在大于或等于0.03且小于或等于0.08的范围内被取代。当锆含量(c)和金属M的摩尔量(d)之和大于0.1时,在合成期间在固溶度极限之外,均匀取代失败并形成沉淀相的可能性很高。此外,在煅烧期间由于过量的取代物而发生煅烧抑制现象,且可能会降低正极活性材料的性能。相反,当锆含量(c)和金属M的摩尔量(d)之和小于0.03时,取代的效果可能几乎丧失。
锆含量(c)和金属M的摩尔量(d)的比例可以为2:1,且更优选3:2。当金属M的摩尔量(d)的比例保持超过50%时,强烈的煅烧抑制现象提供诸如如下的效果:正极活性材料的初级粒子生长被抑制、结晶度降低和煅烧后的Li副产物较少。
钴含量(1-(a+b+c+d))依赖于镍、锰、锆和金属M的含量(a+b+c+d),且当钴含量过高时,由于钴的含量高,原料总体成本增加且可逆容量略有下降,且当钴含量过低时,可能难以同时实现电池的足够的倍率特性和高粉末密度。因此,镍、锰、锆和金属M的含量(a+b+c+d)优选为0.05~0.4。
用包含特定阴离子如F-、PO4 3-、CO3 2-的锂化合物来掺杂或表面处理锂二次电池的电极活性材料或将其与锂化合物混合的一些常规技术是已知的。例如,一些现有技术提出使用已知的锂/镍类氧化物和磷酸锂的具有特定结构的混合物作为电极活性材料的二次电池,并且一些现有技术公开了通过使用涂布有磷酸锂的锂/锰类氧化物作为电极活性材料来阻止锰离子从电解液的溶出。
然而,这些现有技术在制备电极活性材料之后需要用锂化合物进行表面处理的额外工艺,并且这种表面处理可能导致锂二次电池的生产成本增加。此外,由于特定的阴离子仅存在于电极活性材料的表面上,所以在发挥预定水平的效果方面存在限制。
因此,根据本发明的实施方案的过渡金属氧化物的前体可以单独地包含(OH1-x),或者优选可以与以特定量取代的一种或多种阴离子一起包含。当使用包含以特定量取代的一种或多种阴离子的这种过渡金属氧化物的前体来制备锂和过渡金属氧化物的复合物时,阴离子可以均匀地包含在复合物的表面和内部。该特征使得二次电池具有优异的输出特性和寿命特性并且显示高充/放电效率。
即,均匀包含在复合物的表面和内部的特定阴离子有助于改善晶粒之间的离子传导性并且诱导更少的晶粒或晶体生长,减少在活化步骤中产生氧时的结构变化并增加表面积,从而提高包括倍率特性在内的整体电池性能。
在化学式1中,阴离子A离子不限于特定的种类,条件是有助于提高晶粒间的离子传导性。
在优选实例中,A可以是选自如下中的至少一种:PO4、CO3、BO3和F,且其中特别地,PO4和F对于锂和过渡金属氧化物的复合物的稳定性的提高是理想的,因为结构非常稳定且锂的扩散系数高。
当阴离子A的含量太高时,包含其的锂和过渡金属氧化物的复合物的结晶化受到阻碍,使得难以提高活性材料的性能,并且当阴离子A的含量太低时,难以展示预定的效果,并因此,A在复合过渡金属氧化物中基于总量(摩尔基准)的含量优选为0.01~0.05mol,特别优选大于或等于0.02mol且小于或等于0.03mol。
作为参考,阴离子A的含量当然基于如前定义的阴离子的氧化数而确定在上述范围内。
因为其包含阴离子A,所以过渡金属氧化物的前体具有高的振实密度,并且作为优选实例,其振实密度可以为1.0~2.5g/cc。
此外,由于过渡金属氧化物的前体优选通过在制备步骤中添加包含阴离子A的化合物来制备,所以在制备锂和过渡金属氧化物的复合物之后,不需要另外的工艺以引起与包含阴离子A的化合物的反应,实现了简单且容易的工艺和高经济效率。此外,与另外制备的物质相比,由此制备的锂复合过渡金属化合物具有作为正极活性材料的杰出性能。
下文中,将对本发明的制备过渡金属氧化物的前体的方法进行说明。
过渡金属氧化物的前体可以通过使用包含以特定量溶解的含过渡金属的盐和包含阴离子A的化合物的碱性材料的共沉淀法来制备。
共沉淀法是使用沉淀反应在水溶液中同时沉淀两种以上过渡金属元素的制备方法。在特定实例中,可以通过考虑过渡金属的含量将含过渡金属的盐以期望的摩尔比进行混合以制备水溶液,并通过在添加诸如氢氧化钠的强碱且在一些情况中添加诸如氨源的添加剂来保持碱性pH的同时实施共沉淀来制备包含两种以上过渡金属的复合过渡金属化合物。在这种情况下,通过适当地控制温度、pH、反应时间、浆料浓度和离子浓度,可以调节期望的平均粒径、粒径分布和粒子密度。pH范围为9~13,且优选10~12,并且在一些情况下可以进行多步反应。
优选地,含过渡金属的盐具有易于在煅烧期间分解和挥发的阴离子,例如硫酸盐或硝酸盐,且特别优选硫酸盐。例如,可以使用硫酸镍、硫酸钴、硫酸锰、硝酸镍、硝酸钴和硝酸锰,但不限于此。
所述碱性材料包括氢氧化钠、氢氧化钾和氢氧化锂,且优选氢氧化钠,但不限于此。
此外,包含阴离子A的化合物可以用化学式Zx'Ay'表示,且在该式中,Z是选自Na、NH4和H中的至少一者,A是选自PO4、CO3、BO3和F中的至少一者,且Z的氧化数×x'+A的氧化数×y'=0在0<x'<4和0<y'<4的范围内满足。在优选实例中,Zx'Ay'可以是选自如下中的至少一种:Na3PO4、(NH4)3PO4、(NH4)2HPO4和(NH4)2H2PO4。
化合物Zx'Ay'可以溶解在水中,并且优选可以以0.01~0.05mol的范围溶解在如上所定义的碱性材料中并引入反应罐中,引起与用于制备前体的过渡金属盐的反应,且优选地可以将溶解状态的化合物Zx'Ay'放入氢氧化钠溶液中。在一些情况下,化合物Zx'Ay'可以与含过渡金属的盐一起引入。
在优选实例中,可以进一步添加能够在共沉淀过程期间与过渡金属形成络合物的添加剂和/或碱金属碳酸盐。添加剂可以是例如铵离子源、乙二胺类化合物和柠檬酸类化合物。铵离子源可以是例如氨水、硫酸铵水溶液和硝酸铵水溶液。碱金属碳酸盐可以选自如下物质:碳酸铵、碳酸钠、碳酸钾和碳酸锂。在一些情况下,可以使用其混合物。
添加剂和碱金属碳酸盐的量可以考虑含过渡金属的盐的量和pH来适当确定。
根据反应条件,可以制备仅包含根据化学式1的复合过渡金属化合物的过渡金属氧化物的前体,或者可以制备同时包含其它复合过渡金属化合物的过渡金属氧化物的前体。关于其详细描述,可以参考如下实施方案。
本发明还提供了锂和由过渡金属氧化物的前体制备的过渡金属氧化物的复合物。具体地,将过渡金属氧化物的前体和含锂材料进行煅烧以制备作为锂二次电池用正极活性材料的锂和过渡金属氧化物的复合物,并且含锂材料可以是如下中的至少一种:氢氧化锂、碳酸锂和锂氧化物。
相对于1mol过渡金属氧化物的前体,锂化合物可以为0.95~1.2mol,且优选1.0~1.1的摩尔比,并且在所述数值范围内对容量和寿命特性的改善有效果。
此外,煅烧反应在600~1000℃、优选700~950℃的温度下进行,且当煅烧温度低于600℃时,过渡金属氧化物的前体未完全煅烧,且当煅烧温度高于1000℃时,暴露于高温的前体和锂化合物的性能发生变化。
当阴离子A的含量太高时,锂和包含所述阴离子A的过渡金属氧化物的复合物的结晶化受到阻碍,使得难以提高活性材料的性能,并且当阴离子A的含量太低时,难以发挥预定的效果,因此,复合过渡金属氧化物中A基于总量(摩尔基准)的含量优选为0.01~0.05mol%,尤其优选大于或等于0.02mol%且小于或等于0.03mol%。
作为参考,阴离子A的含量当然基于如前定义的阴离子的氧化数而确定在上述范围内。
锂和过渡金属氧化物的复合物可以优选用作锂二次电池用电极活性材料,并且可以单独使用和与其它已知的锂二次电池用电极活性材料组合使用。
此外,锂和过渡金属氧化物的复合物包含两种以上的过渡金属,但不限于例如,层状化合物如被一种或多种过渡金属取代的锂钴氧化物(LiCoO2)、锂/镍氧化物(LiNiO2);被一种或多种过渡金属取代的锂锰氧化物;由化学式LiNi1-yMyO2(此处,M=Co、Mn、Al、Cu、Fe、Mg、B、Cr、Zn或Ga并且包含至少一种所述元素,0.01≤y≤0.7)表示的锂/镍类氧化物;由Li1+zNibMncCo1-(b+c+d)MdO(2-e)Ne(此处,-0.5≤z≤0.5,0.3≤b≤0.9,0.1≤c≤0.9,0≤d≤0.1,0≤e≤0.05,b+c+d<1,M=Al、Mg、Cr、Ti、Si或Y,N=F、P或Cl))表示的锂/镍钴锰复合氧化物如Li1+zNi1/3Co1/3Mn1/3O2、Li1+zNi0.4Mn0.4Co0.2O2。
锂和过渡金属氧化物的复合物可以尤其优选为锂和包含Co、Ni和Mn的过渡金属氧化物的复合物。
用于制备锂和过渡金属氧化物的复合物的过渡金属氧化物的前体和含锂材料的反应条件在本领域内是已知的,并且本文中省略其详细描述。
本发明还提供一种正极和包含所述正极的锂二次电池,所述正极包含锂和过渡金属氧化物的复合物作为正极活性材料。
正极例如通过将本发明的正极活性材料、导电材料和粘合剂的混合物施加到正极集电器上并对其进行干燥来制造,并且可以根据需要将填料进一步添加到所述混合物。
正极集电器的厚度通常制造成3~500μm。正极集电器不限于任何特定的类型,条件是其在不对相应的电池造成化学变化的同时具有高导电性,且例如可以包括:不锈钢、铝、镍、钛、烧结碳、或经碳、镍、钛和银表面处理过的铝或不锈钢。集电器可以具有其纳米尺度的纹理表面以增加正极活性材料的粘附性,并且可以呈多种类型,包括膜、片、箔、网、多孔材料、泡沫和无纺布。
基于包含正极活性材料的混合物的总重量,导电材料通常以1~20重量%的量存在。导电材料不限于任何特定类型,条件是其在不会对相应的电池造成化学变化的同时具有导电性能,并且包括例如:石墨如天然石墨或人造石墨;炭黑类材料如炭黑、乙炔黑、科琴黑、槽法炭黑、炉黑、灯黑和热裂法炭黑;导电纤维如碳纤维或金属纤维;金属粉末如氟碳化合物、铝、镍的粉末;导电晶须如氧化锌和钛酸钾;导电金属氧化物如氧化钛;和导电材料如聚亚苯基衍生物。
粘合剂是有助于对活性材料和导电材料的结合以及对集电器的结合的物质,且通常基于包含正极活性材料的混合物的总重量以1~20重量%的量添加。粘合剂的实例包括聚偏二氟乙烯、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、丁苯橡胶、氟橡胶、和各种共聚物。
填充剂是抑制正极膨胀并任选使用的物质,并且不限于任何特定类型,条件是其是纤维材料而不对相应电池造成化学变化,并且包括例如:烯烃类聚合物如聚乙烯和聚丙烯;纤维材料如玻璃纤维和碳纤维。
锂二次电池通常包含正极、负极、隔膜和含锂盐的非水电解质,且下面将对根据本发明的锂二次电池的其它成分进行说明。
通过将负极材料涂布在负极集电器上并对其进行干燥来制造负极,且根据需要可以进一步包含上述成分。
负极材料包括例如:碳如难石墨化碳和石墨类碳;金属复合氧化物如LixFe2O3(0≤x≤1)、LixWO2(0≤x≤1)、SnxMe1-xMe'yOz(Me:Mn、Fe、Pb、Ge;Me':Al,B,P,Si,周期表中1、2和3族的元素,卤素;0<x≤1;1≤y≤3;1≤z≤8);锂金属;锂合金;硅类合金;锡类合金;金属氧化物如SnO、SnO2、PbO;导电聚合物如聚乙炔;和Li-Co-Ni类材料。
负极集电器的厚度通常为3~500μm。负极集电器不限于特定类型,条件是其具有导电性而不会对相应的电池造成化学变化,且例如可以包括:铜、不锈钢、铝、镍、钛、烧结碳、经碳、镍、钛和银表面处理过的铜或不锈钢、和铝-镉合金。此外,与正极集电器类似,负极集电器可以具有其纳米尺度的纹理表面以增加负极活性材料的粘附性,并且可以呈多种类型,包括膜、片、箔、网、多孔材料、泡沫和无纺布。
隔膜设置在正极与负极之间,并且使用具有高离子透过性和机械强度的绝缘薄膜。隔膜的孔径通常为0.01~10μm,且厚度通常为5~300μm。隔膜包括例如:烯烃类聚合物如具有耐化学性和疏水性的聚丙烯;以及由玻璃纤维或聚乙烯制成的片或无纺布。当使用聚合物的固体电解质作为电解质时,固体电解质可以充当隔膜。
含锂的非水电解质包含非水电解质和锂盐。非水电解质包括非水电解液、固体电解质和无机固体电解质。
非水电解液包括例如非质子有机溶剂如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、四氢呋喃、2-甲基四氢呋喃、二甲基亚砜、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、醚、丙酸甲酯和丙酸乙酯。
有机固体电解质包括例如: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、聚海藻酸盐-赖氨酸、聚酯硫化物、聚乙烯醇、聚偏二氟乙烯和具有离子离解基团的聚合物。
无机固体电解质包括例如Li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。
锂盐是易溶于非水电解质的材料,且包括例如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锂。
此外,为了提高充/放电特性和阻燃性,可以将例如如下物质添加到非水电解质: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、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-甲氧基乙醇和三氯化铝。在一些情况下,为了提供不燃性,可以进一步包含含卤素的溶剂如四氯化碳和三氟乙烯,并且为了改善高温保持性,可以进一步包含二氧化碳气体,并可以还包含FEC(氟代碳酸亚乙酯)、PRS(丙烯磺酸内酯)和FPC(氟代碳酸亚丙酯)。
下文中,将描述实施方案以详细描述本发明。然而,根据本发明的实施方案可以以许多不同的形式进行修改,并且本发明的范围不应被解释为限于下面描述的实施方案。将本发明的实施方案提供给本领域普通技术人员以完整并全面地描述本发明。
制备正极活性材料
[制备例1]
以Ni:Mn:Co:Zr的摩尔比为60:20:19.5:0.5的方式使用原料NiSO4、MnSO4、CoSO4和ZrSO4制备了1.5M的金属溶液。此外,以OH和PO4的比例为1.98:0.02的方式使用NaOH和Na3PO4制备了3M的阴离子源。由此,使用45℃的恒温连续共沉淀反应器合成了正极活性材料的前体。将合成的前体与LiOH源以1:1.07的比例混合,并在大气环境中在850℃下煅烧10小时以制备正极活性材料。
[制备例2]
除了以Ni:Mn:Co:Zr:Nb的摩尔比为60:20:19:0.6:0.4的方式使用ZrSO4和Nb2(SO4)3之外,以与制备例1相同的方式制备了正极活性材料。
[制备例3]
除了以Ni:Mn:Co:Zr:W的摩尔比为60:20:19:0.6:0.4的方式使用ZrSO4和Na2WO4之外,以与制备例1相同的方式制备了正极活性材料。
[制备例4]
除了以Ni:Mn:Co的摩尔比为60:20:20的方式使用NiSO4、MnSO4和CoSO4之外,以与制备例1相同的方式制备了正极活性材料。
[制备例5]
除了以Ni:Mn:Co:Zr:W的摩尔比为60:20:19.8:0.1:0.1的方式使用ZrSO4和Na2WO4之外,以与制备例1相同的方式制备了正极活性材料。
[制备例6]
除了以Ni:Mn:Co:Zr:W的摩尔比为60:20:18:0.8:1.2的方式使用ZrSO4和Na2WO4之外,以与制备例1相同的方式制备了正极活性材料。
制造二次电池
[实施例1]
制造负极
将96重量份作为负极活性材料的人造石墨、3重量份作为粘合剂聚合物的聚偏二氟乙烯(PVdF)和1重量份作为导电材料的炭黑添加到N-甲基-2-吡咯烷酮(NMP)溶剂以制备混合的负极浆料。将混合的负极浆料涂布在用于负极集电器的10μm厚的铜(Cu)薄膜的两个表面上,随后进行干燥和辊压,以制造负极。
制造正极
将92重量份制备例1的正极活性材料、4重量份作为导电材料的炭黑和4重量份作为粘合剂聚合物的聚偏二氟乙烯(PVDF)加入到N-甲基-2吡咯烷酮(NMP)溶剂以制备混合的正极浆料。将混合的正极浆料涂布在用于正极集电器的20μm厚的铝(Al)薄膜的两个表面上,随后进行干燥和辊压,以制造正极。
制造隔膜
将聚偏二氟乙烯(PVdF)溶解在丙酮中以制备粘合剂聚合物溶液。将氧化铝(Al2O3)以聚偏二氟乙烯/氧化铝(Al2O3)的重量比=7.15/92.5的量添加到制备的粘合剂聚合物溶液中,并且使用球磨法将氧化铝(Al2O3)研磨并分散3小时以上以制备浆料。所制备的浆料中氧化铝(Al2O3)的粒度可以根据球磨机中使用的珠的粒度(粒度分布)和球磨时间来控制,但是通过研磨制备浆料以达到实施例1中约400mm的粒度。将如上制备的浆料涂布在12μm厚的聚乙烯多孔聚合物膜(孔隙率为45%)的一个表面上并进行干燥。
制造电池
将如上制造的负极和正极按照正极/隔膜/负极/隔膜/正极的顺序使用设置在其间的第一隔膜来进行堆叠,并且在高温下施加压力以制造单元双电池。将如上制造的21个单元双电池布置在如上制造的第二隔膜的一个表面上并进行折叠以制备电极组件,并且将含有溶解在碳酸亚乙酯和碳酸甲乙酯(EC/EMC=1:2,体积比)中的1M的六氟磷酸锂(LiPF6)的电解液注入到组装的电池中以制造锂二次电池。
[实施例2]
除了使用制备例2的正极活性材料之外,以与实施例1相同的方式制造了锂二次电池。
[实施例3]
除了使用制备例3的正极活性材料之外,以与实施例1相同的方式制造了锂二次电池。
[比较例1]
除了使用制备例4的正极活性材料之外,以与实施例1相同的方式制造了锂二次电池。
[比较例2]
除了使用制备例5的正极活性材料之外,以与实施例1相同的方式制造了锂二次电池。
[比较例3]
除了使用制备例6的正极活性材料之外,以与实施例1相同的方式制造了锂二次电池。
表1
表1显示了实施例1~3和比较例1~3的充放电效率的比较。
图1是显示实施例1~3和比较例1~3的容量的比较的图,且图2是显示实施例1~3和比较例1~3的电阻的比较的图。
从表1和图1和2能够看出,根据本发明,在包含镍-锰-钴过渡金属的基于多成分的正极活性材料用前体中包含最佳摩尔比率的锆,从而提供优异的充/放电效率、高容量和由电阻下降而改善的输出。
尽管在上面已经针对有限数量的实施方案和附图对本发明进行了描述,但是本发明不限于此,并且显而易见的是,在本发明的技术主旨和与所附权利要求等同的范围内,本发明所属技术领域的普通技术人员能够完成多种变体和变化。
Claims (10)
1.一种由如下化学式1表示的过渡金属氧化物的前体:
[化学式1]NiaMnbCo1-(a+b+c+d)ZrcMd[OH(1-x)2-y]A(y/n)
其中,M是W和Nb中的至少一者,A是除了OH之外的一种或多种阴离子,0.3≤a≤0.9,0.05≤b≤0.5,0<c<0.05,0<d<0.05,a+b+c+d<1,0<x<0.5,0<y≤0.05,n是A的氧化数,
所述A是选自如下中的至少一种:PO4、CO3、BO3和F。
2.根据权利要求1所述的过渡金属氧化物的前体,其中当所述M为W或Nb时,c:d摩尔比为2:1~3:2。
3.根据权利要求1所述的过渡金属氧化物的前体,其中所述A包含PO4和F。
4.根据权利要求1所述的过渡金属氧化物的前体,其中所述过渡金属氧化物的前体具有1.0g/cc~2.5g/cc的振实密度。
5.一种锂和过渡金属氧化物的复合物,所述复合物包含通过对权利要求1~4中任一项的过渡金属氧化物的前体和锂化合物进行煅烧而得到的生成物。
6.根据权利要求5所述的锂和过渡金属氧化物的复合物,其中所述锂化合物是如下中的至少一种:氢氧化锂、碳酸锂和锂氧化物。
7.根据权利要求5所述的锂和过渡金属氧化物的复合物,其中相对于1mol所述过渡金属氧化物的前体,所述锂化合物为0.95~1.2mol。
8.根据权利要求5所述的锂和过渡金属氧化物的复合物,其中所述煅烧在600℃~1000℃下进行。
9.一种正极,所述正极包含权利要求5的锂和过渡金属氧化物的复合物。
10.一种二次电池,所述二次电池包含权利要求9的正极。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2014-0149818 | 2014-10-31 | ||
KR20140149818 | 2014-10-31 | ||
PCT/KR2015/011662 WO2016068682A1 (ko) | 2014-10-31 | 2015-11-02 | 전이금속 산화물 전구체, 리튬 복합 전이금속 산화물, 이를 포함하는 양극 및 이차전지 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107074588A CN107074588A (zh) | 2017-08-18 |
CN107074588B true CN107074588B (zh) | 2019-05-14 |
Family
ID=55857884
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201580059467.6A Active CN107074588B (zh) | 2014-10-31 | 2015-11-02 | 过渡金属氧化物的前体、锂和过渡金属氧化物的复合物、包含所述复合物的正极和二次电池 |
Country Status (4)
Country | Link |
---|---|
US (1) | US10811676B2 (zh) |
KR (1) | KR101848979B1 (zh) |
CN (1) | CN107074588B (zh) |
WO (1) | WO2016068682A1 (zh) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018160023A1 (ko) * | 2017-02-28 | 2018-09-07 | 주식회사 엘지화학 | 리튬 이차전지용 양극 활물질, 그 제조방법 및 이를 포함하는 리튬 이차전지 |
KR102176633B1 (ko) | 2017-02-28 | 2020-11-09 | 주식회사 엘지화학 | 리튬 이차전지용 양극 활물질, 그 제조방법 및 이를 포함하는 리튬 이차전지 |
CN108807928B (zh) | 2018-06-25 | 2021-04-20 | 宁德新能源科技有限公司 | 一种金属氧化物及锂离子电池的合成 |
CN110697801B (zh) | 2019-10-29 | 2020-12-04 | 山东泽石新材料科技有限公司 | 一种过渡金属锂氧化合物的制备方法及装置 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103094576A (zh) * | 2011-10-31 | 2013-05-08 | 北京有色金属研究总院 | 一种镍基正极材料及其制备方法和电池 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100616475B1 (ko) | 2005-05-07 | 2006-08-29 | 한국과학기술연구원 | 리튬이차전지 양극활물질 전구체, 이를 이용한 양극활물질및 리튬이차전지 및 그 제조방법 |
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 |
KR101217453B1 (ko) * | 2009-12-24 | 2013-01-02 | 제이에이치화학공업(주) | 리튬이차전지 양극활물질용 전구체인 니켈계 복합금속수산화물 및 그 제조방법 |
WO2011161754A1 (ja) | 2010-06-21 | 2011-12-29 | トヨタ自動車株式会社 | リチウムイオン二次電池 |
WO2011161755A1 (ja) * | 2010-06-21 | 2011-12-29 | トヨタ自動車株式会社 | リチウム二次電池 |
PT2619140T (pt) * | 2010-09-22 | 2016-08-17 | Freeport Cobalt Oy | Hidróxido oxidado metálico misto e método para produção |
WO2012164752A1 (ja) | 2011-05-30 | 2012-12-06 | 住友金属鉱山株式会社 | 非水系二次電池用正極活物質とその製造方法、ならびに該正極活物質を用いた非水系電解質二次電池 |
JP5692617B2 (ja) * | 2011-05-31 | 2015-04-01 | トヨタ自動車株式会社 | リチウム二次電池 |
KR101446491B1 (ko) | 2012-03-16 | 2014-10-06 | 주식회사 엘지화학 | 리튬 복합 전이금속 산화물 제조용 전구체 및 그 제조방법 |
JP5626602B2 (ja) * | 2012-06-29 | 2014-11-19 | トヨタ自動車株式会社 | 非水電解質二次電池 |
JP6072235B2 (ja) | 2012-07-09 | 2017-02-01 | エルジー・ケム・リミテッド | リチウム複合遷移金属酸化物製造用前駆体、及びその製造方法 |
KR20140115201A (ko) * | 2013-03-20 | 2014-09-30 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 양극 활물질 및 이를 포함하는 리튬 이차 전지 |
-
2015
- 2015-11-02 WO PCT/KR2015/011662 patent/WO2016068682A1/ko active Application Filing
- 2015-11-02 CN CN201580059467.6A patent/CN107074588B/zh active Active
- 2015-11-02 KR KR1020150153453A patent/KR101848979B1/ko active IP Right Grant
- 2015-11-02 US US15/516,715 patent/US10811676B2/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103094576A (zh) * | 2011-10-31 | 2013-05-08 | 北京有色金属研究总院 | 一种镍基正极材料及其制备方法和电池 |
Also Published As
Publication number | Publication date |
---|---|
KR20160052427A (ko) | 2016-05-12 |
KR101848979B1 (ko) | 2018-05-24 |
CN107074588A (zh) | 2017-08-18 |
WO2016068682A1 (ko) | 2016-05-06 |
US20170294645A1 (en) | 2017-10-12 |
US10811676B2 (en) | 2020-10-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6471025B2 (ja) | リチウム含有複合酸化物およびその製造方法 | |
JP6345218B2 (ja) | リチウム複合遷移金属酸化物製造用前駆体及びその製造方法 | |
US10763507B2 (en) | Precursor for the production of positive electrode active material comprising metal oxides having multilayered structure and positive electrode active material for lithium secondary battery produced using the same | |
CN104303345B (zh) | 用于制备锂复合过渡金属氧化物的前体及其制备方法 | |
CN101855755B (zh) | 非水电解液二次电池用Li-Ni类复合氧化物颗粒粉末及其制造方法,和非水电解质二次电池 | |
JP6732010B2 (ja) | 多層構造の金属酸化物を含む正極活物質製造用前駆体およびこれを用いて製造されたリチウム二次電池用正極活物質 | |
CN102931391B (zh) | 用于制备锂过渡金属氧化物的前体 | |
KR100959589B1 (ko) | 리튬 복합 전이금속 산화물 제조용 신규 전구체 | |
CN107074587B (zh) | 过渡金属氧化物的前体、其制备方法、锂复合过渡金属氧化物、包含其的正极和二次电池 | |
CN104364944B (zh) | 正极活性材料和包含其的锂二次电池 | |
CN110383541A (zh) | 包含形成有含贫锂过渡金属氧化物的涂层的富锂锂锰基氧化物的正极活性材料和包含其的锂二次电池 | |
CN107799733B (zh) | 二次电池用正极活性材料、其制备方法及包含其的正极和锂二次电池 | |
CN102983320A (zh) | 锂二次电池 | |
CN111771302B (zh) | 锂二次电池正极活性材料及其制备方法、锂二次电池 | |
CN109314230A (zh) | 包含具有芯-壳结构的锂钴氧化物的锂二次电池用正极活性材料、其制造方法以及包含该正极活性材料的正极和二次电池 | |
CN107074588B (zh) | 过渡金属氧化物的前体、锂和过渡金属氧化物的复合物、包含所述复合物的正极和二次电池 | |
JP5556844B2 (ja) | 非水電解質二次電池用正極活物質、非水電解質二次電池用正極活物質の製造方法、非水電解質二次電池用正極及び非水電解質二次電池 | |
KR102077180B1 (ko) | 리튬 이차전지용 양극 활물질 전구체 및 그 제조방법, 리튬 이차전지용 양극 활물질 및 그 제조방법, 리튬 이차전지 | |
CN105264695B (zh) | 制备锂二次电池用正极活性材料的方法 | |
CN109478646A (zh) | 用于制备金属掺杂的二次电池正极活性材料的钴前体 | |
CN102867948A (zh) | 复合物、其制法、负极活性材料、负极、及锂二次电池 | |
KR101352836B1 (ko) | 리튬 과잉의 리튬 망간계 산화물의 제조 방법 및 이를 이용한 리튬 이차전지 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right | ||
TR01 | Transfer of patent right |
Effective date of registration: 20211209 Address after: Seoul, South Kerean Patentee after: LG Energy Solution Address before: Seoul, South Kerean Patentee before: LG CHEM, Ltd. |