CN114695852B - Organic matter coated multi-element positive electrode material, preparation method and application thereof, and lithium ion battery - Google Patents
Organic matter coated multi-element positive electrode material, preparation method and application thereof, and lithium ion battery Download PDFInfo
- Publication number
- CN114695852B CN114695852B CN202111652415.3A CN202111652415A CN114695852B CN 114695852 B CN114695852 B CN 114695852B CN 202111652415 A CN202111652415 A CN 202111652415A CN 114695852 B CN114695852 B CN 114695852B
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- electrode material
- source
- element positive
- equal
- 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 217
- 239000005416 organic matter Substances 0.000 title claims abstract description 63
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011159 matrix material Substances 0.000 claims abstract description 71
- 239000011247 coating layer Substances 0.000 claims abstract description 64
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 78
- 239000000243 solution Substances 0.000 claims description 66
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 47
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 36
- 239000010405 anode material Substances 0.000 claims description 32
- 239000012266 salt solution Substances 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 29
- 239000008139 complexing agent Substances 0.000 claims description 28
- 239000011572 manganese Substances 0.000 claims description 28
- 238000005245 sintering Methods 0.000 claims description 27
- -1 alkyl oxalate Chemical compound 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 23
- 238000012216 screening Methods 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 21
- 239000011268 mixed slurry Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- 229910019142 PO4 Inorganic materials 0.000 claims description 18
- 239000010452 phosphate Substances 0.000 claims description 18
- 239000002019 doping agent Substances 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 14
- 230000001590 oxidative effect Effects 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229920000128 polypyrrole Polymers 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 150000007942 carboxylates Chemical class 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 9
- 239000012716 precipitator Substances 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 8
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 8
- 229940044175 cobalt sulfate Drugs 0.000 claims description 8
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 229940099596 manganese sulfate Drugs 0.000 claims description 8
- 239000011702 manganese sulphate Substances 0.000 claims description 8
- 235000007079 manganese sulphate Nutrition 0.000 claims description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 8
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 8
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000000975 co-precipitation Methods 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 7
- 150000002696 manganese Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 150000002815 nickel Chemical class 0.000 claims description 7
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 6
- KUJRRRAEVBRSIW-UHFFFAOYSA-N niobium(5+) pentanitrate Chemical compound [Nb+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUJRRRAEVBRSIW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 235000001014 amino acid Nutrition 0.000 claims description 5
- 150000001413 amino acids Chemical group 0.000 claims description 5
- 125000005228 aryl sulfonate group Chemical group 0.000 claims description 5
- 150000002891 organic anions Chemical class 0.000 claims description 5
- JRMAQQQTXDJDNC-UHFFFAOYSA-M 2-ethoxy-2-oxoacetate Chemical compound CCOC(=O)C([O-])=O JRMAQQQTXDJDNC-UHFFFAOYSA-M 0.000 claims description 4
- AFPHTEQTJZKQAQ-UHFFFAOYSA-N 3-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1 AFPHTEQTJZKQAQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 4
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 claims description 4
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims description 4
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims description 4
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 claims description 4
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 125000005600 alkyl phosphonate group Chemical group 0.000 claims description 4
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 4
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- FTMKAMVLFVRZQX-UHFFFAOYSA-N octadecylphosphonic acid Chemical compound CCCCCCCCCCCCCCCCCCP(O)(O)=O FTMKAMVLFVRZQX-UHFFFAOYSA-N 0.000 claims description 4
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims description 4
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 claims description 4
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 3
- 235000004279 alanine Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 2
- QPKFVRWIISEVCW-UHFFFAOYSA-N 1-butane boronic acid Chemical compound CCCCB(O)O QPKFVRWIISEVCW-UHFFFAOYSA-N 0.000 claims description 2
- GWIAAIUASRVOIA-UHFFFAOYSA-M 2-aminonaphthalene-1-sulfonate Chemical compound C1=CC=CC2=C(S([O-])(=O)=O)C(N)=CC=C21 GWIAAIUASRVOIA-UHFFFAOYSA-M 0.000 claims description 2
- GWIAAIUASRVOIA-UHFFFAOYSA-N 2-aminonaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(N)=CC=C21 GWIAAIUASRVOIA-UHFFFAOYSA-N 0.000 claims description 2
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 claims description 2
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 claims description 2
- WQPMYSHJKXVTME-UHFFFAOYSA-N 3-hydroxypropane-1-sulfonic acid Chemical compound OCCCS(O)(=O)=O WQPMYSHJKXVTME-UHFFFAOYSA-N 0.000 claims description 2
- NYYSPVRERVXMLJ-UHFFFAOYSA-N 4,4-difluorocyclohexan-1-one Chemical compound FC1(F)CCC(=O)CC1 NYYSPVRERVXMLJ-UHFFFAOYSA-N 0.000 claims description 2
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 claims description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- JEHKKBHWRAXMCH-UHFFFAOYSA-M benzenesulfinate Chemical compound [O-]S(=O)C1=CC=CC=C1 JEHKKBHWRAXMCH-UHFFFAOYSA-M 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- SCNCIXKLOBXDQB-UHFFFAOYSA-K cobalt(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Co+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SCNCIXKLOBXDQB-UHFFFAOYSA-K 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- QLZHNIAADXEJJP-UHFFFAOYSA-L dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [O-]P([O-])(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-L 0.000 claims description 2
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims description 2
- 229940043264 dodecyl sulfate Drugs 0.000 claims description 2
- 229940044658 gallium nitrate Drugs 0.000 claims description 2
- 229930195712 glutamate Natural products 0.000 claims description 2
- 235000013922 glutamic acid Nutrition 0.000 claims description 2
- 239000004220 glutamic acid Substances 0.000 claims description 2
- SSILHZFTFWOUJR-UHFFFAOYSA-N hexadecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCCCS(O)(=O)=O SSILHZFTFWOUJR-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- 235000005772 leucine Nutrition 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- MSUZXYWQEDRGFN-UHFFFAOYSA-M lithium;4-methylbenzenesulfinate Chemical compound [Li+].CC1=CC=C(S([O-])=O)C=C1 MSUZXYWQEDRGFN-UHFFFAOYSA-M 0.000 claims description 2
- YFVGRULMIQXYNE-UHFFFAOYSA-M lithium;dodecyl sulfate Chemical compound [Li+].CCCCCCCCCCCCOS([O-])(=O)=O YFVGRULMIQXYNE-UHFFFAOYSA-M 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 239000011564 manganese citrate Substances 0.000 claims description 2
- 235000014872 manganese citrate Nutrition 0.000 claims description 2
- 229940097206 manganese citrate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 2
- XNEFVTBPCXGIRX-UHFFFAOYSA-M methanesulfinate Chemical compound CS([O-])=O XNEFVTBPCXGIRX-UHFFFAOYSA-M 0.000 claims description 2
- UZZYXUGECOQHPU-UHFFFAOYSA-M n-octyl sulfate Chemical compound CCCCCCCCOS([O-])(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-M 0.000 claims description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229940067739 octyl sulfate Drugs 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 235000008729 phenylalanine Nutrition 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 229940067741 sodium octyl sulfate Drugs 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- CSKVLUWCGPWCQR-UHFFFAOYSA-M sodium;3-hydroxypropane-1-sulfonate Chemical compound [Na+].OCCCS([O-])(=O)=O CSKVLUWCGPWCQR-UHFFFAOYSA-M 0.000 claims description 2
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 2
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 claims description 2
- CHLCPTJLUJHDBO-UHFFFAOYSA-M sodium;benzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=CC=C1 CHLCPTJLUJHDBO-UHFFFAOYSA-M 0.000 claims description 2
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 claims description 2
- LYPGDCWPTHTUDO-UHFFFAOYSA-M sodium;methanesulfinate Chemical compound [Na+].CS([O-])=O LYPGDCWPTHTUDO-UHFFFAOYSA-M 0.000 claims description 2
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 claims description 2
- WFRKJMRGXGWHBM-UHFFFAOYSA-M sodium;octyl sulfate Chemical compound [Na+].CCCCCCCCOS([O-])(=O)=O WFRKJMRGXGWHBM-UHFFFAOYSA-M 0.000 claims description 2
- UZZYXUGECOQHPU-UHFFFAOYSA-N sulfuric acid monooctyl ester Natural products CCCCCCCCOS(O)(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-N 0.000 claims description 2
- FYNXQOUDSWHQQD-UHFFFAOYSA-N tantalum(5+) pentanitrate Chemical compound [Ta+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYNXQOUDSWHQQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 claims description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 235000002374 tyrosine Nutrition 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 20
- 239000003792 electrolyte Substances 0.000 description 18
- 239000000306 component Substances 0.000 description 16
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 238000007600 charging Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000007599 discharging Methods 0.000 description 9
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 8
- 238000007086 side reaction Methods 0.000 description 8
- 229940053662 nickel sulfate Drugs 0.000 description 7
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- AZJLMWQBMKNUKB-UHFFFAOYSA-N [Zr].[La] Chemical compound [Zr].[La] AZJLMWQBMKNUKB-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- RINWGRJHXCCLOV-UHFFFAOYSA-N BPO Chemical compound BPO RINWGRJHXCCLOV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- GNKHOVDJZALMGA-UHFFFAOYSA-N [Y].[Zr] Chemical compound [Y].[Zr] GNKHOVDJZALMGA-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- PUUPYXQOFNNGRK-UHFFFAOYSA-N cerium niobium Chemical compound [Nb].[Ce] PUUPYXQOFNNGRK-UHFFFAOYSA-N 0.000 description 2
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 2
- 238000010280 constant potential charging Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- MPDDTAJMJCESGV-CTUHWIOQSA-M (3r,5r)-7-[2-(4-fluorophenyl)-5-[methyl-[(1r)-1-phenylethyl]carbamoyl]-4-propan-2-ylpyrazol-3-yl]-3,5-dihydroxyheptanoate Chemical compound C1([C@@H](C)N(C)C(=O)C2=NN(C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)=C2C(C)C)C=2C=CC(F)=CC=2)=CC=CC=C1 MPDDTAJMJCESGV-CTUHWIOQSA-M 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- AFPHTEQTJZKQAQ-UHFFFAOYSA-M 3-nitrobenzoate Chemical compound [O-]C(=O)C1=CC=CC([N+]([O-])=O)=C1 AFPHTEQTJZKQAQ-UHFFFAOYSA-M 0.000 description 1
- FXJVNINSOKCNJP-UHFFFAOYSA-M 4-methylbenzenesulfinate Chemical compound CC1=CC=C(S([O-])=O)C=C1 FXJVNINSOKCNJP-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-UHFFFAOYSA-M alaninate Chemical compound CC(N)C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene 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
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the field of lithium ion batteries, and discloses an organic matter coated multi-element positive electrode material, a preparation method and application thereof, and a lithium ion battery. The multi-element positive electrode material comprises a multi-element positive electrode material matrix and an organic coating layer formed on the inner part and the outer part of the matrix; the composition of the matrix of the multi-element positive electrode material is shown as a formula I: li (Li) a (Ni x Co y Mn 1‑x‑ y M δ ) 1‑z M’ z O 2 A formula I; m and M' are each independently selected from at least one element of Al, ba, zr, ti, nb, ta, ga, Y, W, ca, sr, sc, cr, mo, hf, si, sm, V, la, ce, mg and B; the organic coating layer has a composition represented by formula II: p (PyR') formula II; the organic matter coated multi-element positive electrode material has the advantages of excellent structural stability, low interface impedance and the like, and can remarkably improve the battery capacity and prolong the cycle life when being used for batteries.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to an organic matter coated multi-element positive electrode material, a preparation method and application thereof, and a lithium ion battery.
Background
The lithium ion battery is widely used in the fields of portable electric appliances, electric automobiles, energy storage power stations and the like due to the comprehensive advantages of high working voltage, light weight, small volume, long cycle life, no memory effect and the like. Among core components of the positive electrode, the negative electrode, the separator, the electrolyte, and the like of the battery, the positive electrode has become a key factor in determining the performance and price of the battery. The positive electrode material mainly comprises layered lithium cobalt oxide (LiCoO) 2 LCO), lithium nickelate (LiNiO) 2 LNO), spinel type lithium manganate (LiMn 2 O 4 LMO), olivine lithium iron phosphate (LiFePO) 4 LFP), layered nickel cobalt lithium aluminate (LiNi 1-x-y Co x Al y O 2 NCA), lithium nickel cobalt manganate (LiNi 1-x-y Co x Mn y O 2 NCM) and nickel-rich cathode material (LiNi 1-x-y Co x Mn y O 2 And LiNi 1-x-y Co x Al y O 2 ) Etc. The NCM material combines the advantages of LCO, LNO, LMO, has higher discharge capacity, excellent multiplying power performance, longer cycle life and better thermal stability, and becomes the positive electrode material with the largest market occupation ratio.
Due to Ni 2+ /Ni 3+ 、Ni 3+ /Ni 4+ Potential lower than Co 3+ /Co 4+ When the charged cutoff voltage is equal to 4.2V, the high nickel NCM material can release more Li + More electric quantity is charged. Thus, increasing the nickel content can effectively increase the specific capacity of the material. However, the high nickel NCM undergoes severe phase transition of the crystal structure during repeated charge/discharge and accompanies volume change, resulting in local collapse and cracking in the crystal, thereby increasing difficulty in lithium ion deintercalation, resulting in an increase in polarization resistance and a decrease in cycle life.
The technical means for improving the high nickel NCM mainly comprise bulk phase doping, surface coating, doping and the like. The type and amount of coating also has a significant impact on the properties of the ternary material. CN108963239a adopts vapor deposition method to prepare titanium dioxide coated lithium nickel cobalt manganese oxide positive electrode material, but titanium dioxide is used as semiconductor, and the independent coating can affect the specific capacity of the material. CN109244439a provides a ternary positive electrode material of a multi-stage layer coated lithium ion battery, and the reaction between the positive electrode material and the electrolyte is slowed down by multi-stage coating, so that the operation process is complex. The coating mode can not realize simultaneous coating of the inner part and the surface of the multi-element positive electrode material.
Disclosure of Invention
The invention aims to solve the problems of unstable high nickel NCM structure, multiple side reactions with electrolyte and the like in the prior art, and provides an organic matter coated multi-element positive electrode material, a preparation method and application thereof, and a lithium ion battery.
In order to achieve the above object, a first aspect of the present invention provides an organic matter coated multi-component positive electrode material, characterized in that the multi-component positive electrode material comprises a multi-component positive electrode material substrate and an organic coating layer formed inside and outside the substrate;
the composition of the multielement anode material matrix is shown as a formula I:
Li a (Ni x Co y Mn 1-x-y M δ ) 1-z M’ z O 2 a formula I;
m and M' are each independently selected from at least one element of Al, ba, zr, ti, nb, ta, ga, Y, W, ca, sr, sc, cr, mo, hf, si, sm, V, la, ce, mg and B; a is more than or equal to 0.90 and less than or equal to 1.30,0, x is more than or equal to 1,0.001 and less than or equal to y is more than or equal to 1, delta is more than 0 and less than or equal to 0.1, and z is more than 0 and less than or equal to 0.1;
The organic coating layer has a composition represented by formula II: p (PyR') formula II;
wherein P (PyR ') is an organic anion doped polypyrrole and R' is at least one selected from the group consisting of C1-C20 alkylsulfate, C1-C20 alkylsulfonate, C6-C20 arylsulfonate, C1-C20 alkylsulfinate, C6-C20 arylsulfinate, C1-C20 alkylphosphonate, C6-C20 arylphosphonate, primary phosphate, secondary phosphate, amino acid, carboxylate, mono-C1-C20 alkyl oxalate, C1-C20 alkylborate, and C6-C20 arylborate.
The second aspect of the invention provides a preparation method of an organic matter coated multi-element material, which is characterized by comprising the following steps:
(1) Preparing a mixed salt solution by using nickel salt, cobalt salt and manganese salt according to the molar ratio of Ni to Co to Mn=x to y (1-x-y); preparing an M source salt solution, a precipitator solution and a complexing agent solution respectively from an M source, a precipitator and a complexing agent;
(2) Adding the mixed salt solution, the M source salt solution, the precipitator solution and the complexing agent solution into a reaction kettle, and performing coprecipitation reaction to obtain solid-liquid mixed slurry, wherein the solid-liquid mixed slurry is filtered, washed, dried and screened to obtain a multi-element anode material precursor;
(3) Mixing, sintering, crushing and screening the multi-element material precursor, the lithium source and the M' source to obtain a multi-element positive electrode material matrix;
(4) Mixing a dispersing agent with a solvent to obtain a dispersing agent solution, and adding the multi-element material matrix, pyrrole, a doping agent R' and an oxidant into the dispersing agent solution in sequence under the stirring condition to perform chemical oxidative polymerization reaction to obtain mixed slurry;
(5) And filtering, washing, drying and screening the mixed slurry to obtain the organic matter coated multi-element anode material.
The third aspect of the invention provides an organic matter coated multi-element positive electrode material prepared by the preparation method.
The fourth aspect of the invention provides an application of the organic matter coated multi-element positive electrode material in a lithium ion battery.
In a fifth aspect of the present invention, there is provided a lithium ion battery comprising the above organic-coated multi-element positive electrode material as a positive electrode material.
Through the technical scheme, the organic matter coated multi-element positive electrode material provided by the invention and the preparation method and application thereof have the following beneficial effects:
(1) According to the organic matter coated multi-element positive electrode material provided by the invention, the lattice doping of the positive electrode material in a molecular/ion scale is realized by introducing the M source, the doping of the positive electrode material in a nanometer scale is realized by introducing the nanometer-scale M' source, and the structural stability of the multi-element positive electrode material can be obviously improved by the cooperative doping of different scales, so that the cycling stability of the multi-element positive electrode material in the charging and discharging processes is improved.
(2) The elastic coating layers exist in the matrix and on the surface of the multi-element positive electrode material coated by the organic matters, so that the volume expansion caused by the lithium ion intercalation/deintercalation of the positive electrode material can be adapted, the side reaction between the electrolyte and the multi-element positive electrode material can be slowed down, and the generation of cracks in particles in the charge and discharge process can be inhibited.
(3) The organic matter coated multi-element positive electrode material provided by the invention adopts the organic anion doped polypyrrole with low crystallinity and high conductivity, so that a coating layer is easily formed inside the multi-element positive electrode material, and meanwhile, the transmission of lithium ions and electrons is not influenced.
(4) The organic coating layer in the organic matter coated multi-element positive electrode material provided by the invention can effectively isolate the contact between the matrix and carbon dioxide and moisture, reduce the sensitivity of the positive electrode material to carbon dioxide and moisture, and improve the processability and storage property of the positive electrode material.
(5) According to the preparation method of the organic matter coated multi-element positive electrode material, disclosed by the invention, the monomer which penetrates into the multi-element positive electrode material and is adhered to the surface of the multi-element positive electrode material can be polymerized by a chemical oxidation polymerization method, so that the coating layer with controllable thickness is formed in and on the multi-element positive electrode material.
(6) When the organic matter coated multi-element positive electrode material provided by the invention is used for a liquid battery, the side reaction of the positive electrode material and liquid electrolyte can be effectively reduced, and gas production is inhibited; when the solid-state battery is used for a solid-state battery, the rigid solid-solid connection can be thixotropic to be elastic solid-solid connection, so that the positive electrode material and the solid electrolyte are tightly contacted, and the interface impedance is reduced.
Drawings
FIG. 1 is a scanning electron microscope image of the multi-component positive electrode material of example 1;
FIG. 2 is a scanning electron microscope image of the multi-component positive electrode material of comparative example 1;
FIG. 3 is an X-ray diffraction pattern of the multi-component positive electrode material of example 1;
fig. 4 is a charge-discharge graph at 0.1C for liquid lithium ion batteries made from the multi-element positive electrode materials of example 1 and comparative example 1;
fig. 5 is a graph of the cycle performance at 1C of liquid lithium ion batteries made from the multi-element positive electrode materials of example 1 and comparative example 1;
fig. 6 is a charge-discharge graph at 0.1C for solid state lithium batteries made from the multi-element positive electrode materials of example 1 and comparative example 1.
Fig. 7 is a graph of the cycle performance at 0.2C of solid state lithium batteries made from the multi-element positive electrode materials of example 1 and comparative example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides an organic matter coated multi-element positive electrode material, which is characterized by comprising a multi-element positive electrode material matrix and an organic coating layer formed in the matrix and on the surface of the matrix;
the composition of the multielement anode material matrix is shown as a formula I:
Li a (Ni x Co y Mn 1-x-y M δ ) 1-z M’ z O 2 a formula I;
m and M' are each independently selected from at least one element of Al, ba, zr, ti, nb, ta, ga, Y, W, ca, sr, sc, cr, mo, hf, si, sm, V, la, ce, mg and B; a is more than or equal to 0.90 and less than or equal to 1.30,0, x is more than or equal to 1,0.001 and less than or equal to y is more than or equal to 1, delta is more than 0 and less than or equal to 0.1, and z is more than 0 and less than or equal to 0.1;
the composition of the organic coating layer is shown as a formula II:
p (PyR') formula II;
wherein P (PyR ') is an organic anion doped polypyrrole and R' is at least one selected from the group consisting of C1-C20 alkylsulfate, C1-C20 alkylsulfonate, C6-C20 arylsulfonate, C1-C20 alkylsulfinate, C6-C20 arylsulfinate, C1-C20 alkylphosphonate, C6-C20 arylphosphonate, primary phosphate, secondary phosphate, amino, carboxylate, mono-C1-C20 alkyl oxalate, C1-C20 alkylborate, and C6-C20 arylborate.
In the invention, the organic matter coated multi-element positive electrode material comprises a multi-element positive electrode material matrix doped with molecules/ions and nanometer multi-scale and an organic coating layer formed inside and on the surface of the matrix. The structural stability of the material can be effectively improved through doping in different scales, and the elastic coating layers are formed in and on the surfaces of the multi-element positive electrode material, so that the volume expansion caused by the fact that lithium ions are removed from the positive electrode material can be adapted, the multi-element positive electrode material is restrained from generating cracks, the side reaction between the multi-element positive electrode material and electrolyte is slowed down, the interface impedance is reduced, and the cycle life of the multi-element positive electrode material is prolonged.
Further, in the multi-element positive electrode material coated by the organic matter, the organic coating layer formed in the multi-element positive electrode material matrix and on the surface of the multi-element positive electrode material matrix can effectively isolate the matrix from being contacted with carbon dioxide and moisture, so that the sensitivity of the positive electrode material to the carbon dioxide and the moisture is reduced, and the processability and the storage property of the positive electrode material are improved.
Furthermore, the organic anion doped polypyrrole in the organic coating layer has high conductivity, and is beneficial to the transmission of lithium ions and electrons.
Further, in formula I, M and M' are each independently selected from at least one element of Zr, ti, nb, ta, ga, Y, W, cr, mo, hf, si, sm, V, la and Ce; a is more than or equal to 0.96 and less than or equal to 1.08,0.01, x is more than or equal to 0.98,0.001, y is more than or equal to 1,0.001, delta is more than or equal to 0.05,0.001, and z is more than or equal to 0.05.
Further, in formula II, R' is selected from at least one of C3-C18 alkylsulfate, C3-C18 alkylsulfonate, C6-C18 arylsulfonate, C3-C18 alkylsulfinate, C6-C18 arylsulfinate, C3-C18 alkylphosphonate, C6-C18 aryl phosphonate, primary phosphate, secondary phosphate, amino, carboxylate, mono-C6-C18 alkyl oxalate, C3-C18 alkylborate, and C6-C18 arylborate.
Still further, in formula II, R' is at least one of octyl sulfate, dodecyl sulfate, p-toluenesulfonate, naphthalenesulfonate, 2-naphthylamine-1-sulfonate, 3-hydroxy-1-propanesulfonate, p-styrenesulfonate, hexadecylsulfonate, p-toluenesulfinate, phenylsulfinate, formamidinesulfinate, methane sulfinate, octadecylphosphonate, phenylphosphonate, poly (vinylphosphonic acid), glycinate, phenylalanine, alaninate, glutamate, leucine, tyrosine, carboxylate, monoethyloxalate, butylborate, and 3-nitrobenzoate.
According to the invention, the molar ratio Py to R' of the organic coating layer is formed is 1: (0.001-1).
For example, the molar ratio of Py to R' includes, but is not limited to, 1: (0.05-0.5), 1: (0.01-0.9), 1: (0.03-0.7), 1: (0.07-0.5) or 1: (0.1-0.5), etc.
In the invention, the molar ratio of Py to R' in the organic coating layer is measured by an infrared spectrum method.
In the invention, the polypyrrole doped with the large anionic group R' can reduce the crystallinity of the polypyrrole, so that the polypyrrole can easily enter into a multi-element material to form a coating layer. When the molar ratio of Py to R' satisfies the above range, the coating layer has higher conductivity and stability, thereby further improving the conductivity and stability of the multi-element positive electrode material including the coating layer. Further, the molar ratio of Py to R' forming the organic coating layer is 1: (0.05-0.5).
According to the present invention, the ratio of Py forming the organic coating layer to the multi-element positive electrode material base is such that the ratio of n (Py) [ n (Ni) +n (Co) +n (Mn) ] is (0.001-0.1): 1.
for example, the ratio of Py forming the organic coating layer to the multi-element positive electrode material base is such that the ratio of n (Py) [ n (Ni) +n (Co) +n (Mn) ] is (0.001-0.09): 1. (0.005-0.05): 1, (0.008-0.04): 1, (0.01-0.04): 1, (0.02-0.03): 1, (0.008-0.1): 1, (0.01-0.1): 1, (0.03-0.1): 1, (0.05-0.1): 1, (0.06-0.09): 1 or 0.08:1, etc.
In the invention, when the ratio of the organic coating layer to the multi-element positive electrode material matrix satisfies the above range, the coating layer is easy to form an elastic coating layer in and on the multi-element positive electrode material, thereby improving the stability of the multi-element positive electrode material and inhibiting the generation of cracks in the circulating process. Too many coating layers can obstruct the transmission rate of lithium ions and electrons in the multi-element positive electrode material matrix, and the rate capability of the battery is reduced; too few coating layers can not effectively inhibit side reactions between the multi-element positive electrode material matrix and the electrolyte, and further can not improve the cycle life of the battery.
Further, the ratio of Py forming the organic coating layer to the multi-element positive electrode material base is such that the ratio of n (Py) [ n (Ni) +n (Co) +n (Mn) ] is (0.005-0.05): 1.
According to the present invention, the thickness of the organic coating layer is 200nm or less, preferably 2 to 50nm.
In the invention, the thickness of the organic coating layer is measured by a transmission electron microscope.
In the preparation process of the organic matter coated multi-element positive electrode material, the conditions of the proportion among the multi-element positive electrode material matrix, pyrrole and doping agent, the temperature in the chemical oxidation polymerization reaction process and the like are required to be comprehensively controlled.
The ratio of pyrrole and dopant forming the organic coating layer is 1: (0.01-1);
the ratio of Py forming the organic coating layer to the multi-element positive electrode material base is such that the ratio of n (Py) [ n (Ni) +n (Co) +n (Mn) ] is (0.001-0.1): 1, a step of;
in the present invention, the chemical oxidative polymerization is performed at 0 to 10 ℃.
The second aspect of the invention provides a preparation method of an organic matter coated multi-element positive electrode material, which is characterized by comprising the following steps:
(1) Preparing a mixed salt solution by using nickel salt, cobalt salt and manganese salt according to the molar ratio of Ni to Co to Mn=x to y (1-x-y); preparing an M source salt solution, a precipitator solution and a complexing agent solution respectively from an M source, a precipitator and a complexing agent;
(2) Adding the mixed salt solution, the M source salt solution, the precipitator solution and the complexing agent solution into a reaction kettle, and performing coprecipitation reaction to obtain solid-liquid mixed slurry, wherein the solid-liquid mixed slurry is filtered, washed, dried and screened to obtain a multi-element anode material precursor;
(3) Mixing, sintering, crushing and screening the multi-element positive electrode material precursor, the lithium source and the M' source to obtain a multi-element positive electrode material matrix;
(4) Mixing a dispersing agent with a solvent to obtain a dispersing agent solution, and adding the multi-element anode material matrix, pyrrole, a doping agent R' and an oxidant into the dispersing agent solution in sequence under the stirring condition to perform chemical oxidation polymerization reaction to obtain mixed slurry;
(5) And filtering, washing, drying and screening the mixed slurry to obtain the organic matter coated multi-element anode material.
According to the invention, the uniform coating layer with controllable thickness can be formed in situ in the interior and the surface of the multi-element positive electrode material matrix by a chemical oxidation polymerization method.
According to the invention, the concentration of the mixed salt solution is 1-3mol/L, the concentration of the precipitant solution is 1-15mol/L, the concentration of the complexing agent solution is 1-15mol/L, and the concentration of the M source salt solution is 0.01-1mol/L.
In the present invention, the precipitant solution may be a precipitant solution conventional in the art, for example, the precipitant solution is a sodium hydroxide solution.
In the present invention, the complexing agent solution may be a complexing agent solution conventional in the art, for example, the complexing agent solution is an aqueous ammonia solution.
In the invention, the amounts of the precipitant solution and the complexing agent solution are not particularly limited, and can be controlled according to the morphology and the granularity of the prepared multi-element positive electrode material precursor.
Further, the concentration of the mixed salt solution is 1.5-2.5mol/L, the concentration of the precipitant solution is 5-10mol/L, the concentration of the complexing agent solution is 5-10mol/L, and the concentration of the M source salt solution is 0.05-0.5mol/L.
According to the present invention, the nickel salt, the cobalt salt, and the manganese salt are each independently selected from at least one of sulfate, nitrate, chloride, oxalate, acetate, and citrate.
According to the present invention, the nickel salt is selected from at least one of nickel sulfate, nickel nitrate, nickel chloride, nickel oxalate, nickel acetate and nickel citrate; the cobalt salt is at least one selected from cobalt sulfate, cobalt nitrate, cobalt chloride, cobalt oxalate, cobalt acetate and cobalt citrate; the manganese salt is at least one selected from manganese sulfate, manganese nitrate, manganese chloride, manganese oxalate, manganese acetate and manganese citrate.
According to the invention, the M source and the M' source are selected from compounds of at least one element of Al, ba, zr, ti, nb, ta, ga, Y, W, ca, sr, sc, cr, mo, hf, si, sm, V, la, ce, mg and B.
In the present invention, the M source and the M' source may be the same or different.
Further, the compound of the M source is a water-soluble salt of the M source, preferably at least one selected from the group consisting of sodium metaaluminate, barium nitrate, zirconium chloride, titanium sulfate, niobium nitrate, tantalum nitrate, gallium nitrate, yttrium nitrate, ammonium tungstate, calcium chloride, lanthanum nitrate, cerium nitrate, magnesium nitrate, and sodium borate.
Further, the M 'source compound is selected from at least one of an oxide of an M' source, a hydroxide of an M 'source, and a carbonate of an M' source.
According to the invention, D of the M' source compound 50 Less than 200nm, and the specific surface area is more than 20m 2 /g。
In the invention, D is selected 50 Less than 200nm and a specific surface area of more than 20m 2 The M ' source compound per gram is capable of uniformly mixing the M ' source with the multi-element positive electrode material precursor, preferably the M ' source compound D 50 Less than 10-150nm, and a specific surface area of 50-500m 2 /g。
According to the present invention, in step (2), the conditions of the coprecipitation reaction include: the pH value is 10-13, the reaction temperature is 40-70 ℃, and the reaction time is 5-20h.
Further, the conditions of the coprecipitation reaction include: the pH value is 11-12, the reaction temperature is 50-60 ℃, and the reaction time is 8-16h.
In the present invention, in the step (2), the specific operations of filtering, washing, drying and sieving are not particularly limited, as long as solid-liquid separation can be achieved and a solid material can be obtained. For example, the filtration can be realized by suction filtration, filter pressing, centrifugation and the like; drying can be realized by adopting hot air, infrared, microwave and other modes.
In the invention, the particle diameter D of the precursor of the multi-element positive electrode material 50 Is 1-30 μm, preferably 3-20 μm.
According to the present invention, the lithium source is added in an amount of 0.90.ltoreq.n (Li) ]/[ n (Ni) +n (Co) +n (Mn) +n (M). Ltoreq.1.30 by mole.
In the invention, when the dosage of the lithium source satisfies the above range, the prepared multi-element positive electrode material has higher specific capacity.
Further, the lithium source is added in an amount of 0.96.ltoreq.n (Li) ]/[ n (Ni) +n (Co) +n (Mn) +n (M) ].ltoreq.1.08 in terms of a molar ratio.
According to the present invention, the lithium source is selected from at least one of lithium carbonate, lithium hydroxide, and lithium nitrate.
According to the invention, the M source is added in a molar ratio of 0 < [ n (M) ]/[ n (Ni) +n (Co) +n (Mn) ]. Ltoreq.0.1.
In the invention, when the dosage of the M source meets the range, the M element can better enter into the crystal lattice of the precursor of the multi-element positive electrode material, so that the doping of the crystal lattice of the precursor of the positive electrode material on the molecular/ion scale is realized, and meanwhile, the lattice distortion is not seriously caused to prevent lithium ion transmission.
Further, the M source is used in an amount of 0.001.ltoreq.n (M)/[ n (Ni) +n (Co) +n (Mn) ].ltoreq.0.05.
According to the invention, the M 'source is added in a molar ratio of 0 < [ n (M') ]/[ n (Ni) +n (Co) +n (Mn) ]. Ltoreq.0.1.
In the invention, when the dosage of the M 'source and the precursor of the multi-element positive electrode material meets the range, the M' element enters the precursor crystal lattice of the multi-element positive electrode material in the form of nano groups, so that the doping is realized in the nano scale, and meanwhile, the deformation of the unit cell is not seriously caused to prevent the transmission of lithium ions.
Further, the M 'source is added in an amount of 0.001.ltoreq.n (M')/[ n (Ni) +n (Co) +n (Mn) ].ltoreq.0.05 in terms of a molar ratio.
According to the present invention, in step (3), the sintering conditions include: the sintering temperature is 650-1000 ℃, preferably 800-950 ℃; the sintering time is 4-20 hours, preferably 6-15 hours.
According to the invention, in the step (4), the dispersant is used in an amount of 0.001 to 1wt% based on the total weight of the multi-element positive electrode material matrix.
In the invention, when the dosage of the dispersing agent and the multi-element positive electrode material matrix meets the range, the combination between the multi-element positive electrode material and the coating layer can be more compact.
Further, the dispersant is used in an amount of 0.05 to 0.5wt% based on the total weight of the multi-element positive electrode material matrix.
According to the invention, the pyrrole is used in an amount of 0.1 to 10wt% based on the total weight of the matrix of the multi-component positive electrode material.
In the invention, when the dosage of the pyrrole and the multielement positive electrode material matrix meets the range, the organic coating layer can form a compact coating layer with proper thickness on the surface of the multielement positive electrode material, thereby ensuring the effective transmission of ionic electrons and simultaneously slowing down the corrosion of electrolyte to a certain extent.
Further, the amount of pyrrole is 0.5 to 6wt% based on the total weight of the multi-element positive electrode material matrix.
According to the invention, the molar ratio of pyrrole, dopant and oxidant is 1: (0.001-1): (0.01-1).
In the present invention, the molar contents of pyrrole, dopant and oxidant are calculated based on the respective relative molecular weights.
In the invention, when the molar ratio of the pyrrole, the doping agent and the oxidizing agent satisfies the above range, the coating layer easily forms an elastic coating layer inside and on the surface of the multi-element positive electrode material, thereby improving the stability of the multi-element positive electrode material and inhibiting the generation of cracks in the circulating process.
Further, the molar ratio of the pyrrole, the dopant and the oxidant is 1: (0.05-0.5): (0.05-0.5).
According to the present invention, the dopant R' is selected from at least one of C1-C20 alkyl sulfate, C1-C20 alkyl sulfonate, C6-C20 aryl sulfonate, C1-C20 alkyl sulfinate, C6-C20 aryl sulfinate, C1-C20 alkyl phosphonate, C6-C20 aryl phosphonate, primary phosphate, secondary phosphate, amino acid, carboxylate, oxalic acid mono-C1-C20 alkyl ester, C1-C20 alkyl boric acid, and C6-C20 aryl boric acid.
Further, the dopant R' is selected from at least one of C3-C18 alkyl sulfate, C3-C18 alkyl sulfonate, C6-C18 aryl sulfonate, C3-C18 alkyl sulfinate, C6-C18 aryl sulfinate, C3-C18 alkyl phosphonate, C6-C18 aryl phosphonate, primary phosphate, secondary phosphate, amino acid, carboxylate, mono-C6-C18 alkyl oxalate, C3-C18 alkyl boric acid, and C6-C18 aryl boric acid.
Still further, the dopant R' is selected from at least one of sodium octyl sulfate, sodium dodecyl sulfate, lithium dodecyl sulfate, sodium p-toluenesulfonate, sodium naphthalene sulfonate, sodium 2-naphthylamine-1-sulfonic acid, sodium 3-hydroxy-1-propane sulfonate, sodium p-styrenesulfonate, naphthalene sulfonic acid, sodium hexadecyl sulfonate, lithium p-toluene sulfinate, sodium benzene sulfinate, formamidine sulfinic acid, sodium methane sulfinate, octadecylphosphonic acid, phenylphosphonic acid, poly (vinyl phosphonic acid), glycine, phenylalanine, alanine, glutamic acid, leucine, tyrosine, carboxylate, monoethyl oxalate, butyl boric acid, and 3-nitrobenzoic acid.
According to the invention, the oxidizing agent is selected from (NH) 4 ) 2 SO 8 、K 2 Cr 2 O 7 、KClO 4 、KIO 3 、NaClO 3 、H 2 O 2 、MnO 2 、FeCl 3 And at least one of benzoyl peroxide;
according to the present invention, the dispersant is at least one selected from polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyacrylate and polyacrylamide.
In the present invention, the solvent may be a solvent conventional in the art, and specifically, the solvent is at least one selected from acetonitrile, N dimethylformamide, N dimethylacetamide, N-methyl-2-pyrrolidone, acetone, butanone, ethanol, propanol, isopropanol, butanol, toluene, xylene, methylethyl ketone, dimethyl sulfoxide, tetrahydrofuran, dioxane, ethyl acetate, methyl formate, chloroform, dimethyl carbonate, diethyl carbonate, and deionized water. The amount of the solvent is not particularly limited as long as the dispersing agent, the matrix of the multi-component positive electrode material, the pyrrole, the dopant and the oxidizing agent can be sufficiently dispersed.
According to the present invention, in the step (4), the conditions of the chemical oxidative polymerization include: the reaction temperature is 0-10 ℃ and the reaction time is 5-20h.
In the present invention, the chemical oxidative polymerization is performed under the above-described conditions, and a uniform coating layer can be formed inside and on the surface of the multi-component positive electrode material.
Further, the conditions of the chemical oxidative polymerization reaction include: the reaction temperature is 3-7 ℃ and the reaction time is 8-16h.
The chemical polymerization reaction is too fast due to the too high reaction temperature, a loose coating layer is generated, and the side reaction between the multi-element positive electrode material matrix and the electrolyte cannot be effectively inhibited; meanwhile, too high reaction temperature can reduce lithium in the multi-element positive electrode material matrix and damage the structural stability of the multi-element positive electrode material matrix. When the temperature is too low, the chemical polymerization reaction is insufficient or impossible to proceed, resulting in low waste efficiency.
In the present invention, in the step (5), the specific operations of filtering, washing, drying and sieving are not particularly limited, as long as solid-liquid separation can be achieved and a solid material can be obtained. For example, the filtration can be realized by suction filtration, filter pressing, centrifugation and the like; drying can be realized by adopting hot air, infrared, microwave and other modes.
The third aspect of the invention provides an organic matter coated multi-element positive electrode material prepared by the preparation method.
The fourth aspect of the invention provides an application of the organic matter coated multi-element positive electrode material in a lithium ion battery.
In a fifth aspect of the present invention, there is provided a lithium ion battery comprising the above organic-coated multi-element positive electrode material as a positive electrode material.
The present invention will be described in detail by examples. In the following examples of the present invention,
the granularity of the precursor of the multi-element positive electrode material is measured by a Mastersizer 2000 laser granularity meter;
the thickness of the coating layer in the anode material is measured by using a Hitachi HF5000 transmission electron microscope and an X-ray energy spectrometer;
charge-discharge capacity and cycle performance of liquid lithium ion batteries:
the test temperature was kept at 25 ℃. Charging to 4.3V by using a charging current of 0.1C on a charging and discharging tester, converting constant voltage charging to a charging current less than or equal to 0.01C, discharging to 3V by using a discharging current of 0.1C to form 2 periods, and repeating charging and discharging by using a current of 1C. The charge-discharge capacity and the cycle performance of the positive electrode material in the liquid lithium ion battery are examined.
Charge-discharge capacity and cycle performance of solid-state lithium ion batteries:
the test temperature was maintained at 60 ℃. Charging to 4.2V by using a charging current of 0.1C on a charging and discharging tester, converting constant voltage charging to a charging current less than or equal to 0.01C, discharging to 3V by using a discharging current of 0.1C to form 2 periods, and repeating charging and discharging by using a current of 0.2C. The charge-discharge capacity and the cycle performance of the cathode material in the solid lithium ion battery are examined.
Example 1
Preparing a 2mol/L mixed salt solution according to the mol ratio of nickel sulfate, cobalt sulfate and manganese sulfate of 8:1:1. Preparing 0.1mol/L zirconium nitrate solution, 2mol/L NaOH solution and 6mol/L NH 3 ·H 2 O complexing agent solution.
Step two, mixing a salt solution, a zirconium nitrate solution (M source), a NaOH solution and NH 3 ·H 2 The O complexing agent solution was continuously added to the stirred reactor in a co-current manner to effect the reaction. Controlling the pH value in the reaction system to be 11.2-11.8, controlling the temperature of the whole system to be 60 ℃ and waiting for slurry D 50 The reaction was stopped until reaching 10. Mu.m. Washing, filtering and drying the product to obtain zirconium doped multiple elementsA positive electrode material precursor, wherein zirconium nitrate is added in an amount such that the molar ratio is Zr/(ni+co+mn) =0.001.
Step three, uniformly mixing the zirconium-doped multi-element positive electrode material precursor, lanthanum hydroxide and lithium hydroxide in the step two, wherein lanthanum hydroxide D 50 =30nm, specific surface area of 100m 2 Lanthanum hydroxide (M' source) was mixed in a molar ratio La/(ni+co+mn) =0.001, and lithium hydroxide was mixed in a molar ratio Li/(ni+co+mn+zr+la) =1.05. And then sintering the mixture for 10 hours at 850 ℃, and crushing and screening to obtain the zirconium-lanthanum doped multi-element anode material matrix.
Step four, adding PVA and deionized water into a dissolution tank, and stirring until uniform; then adding the zirconium-lanthanum doped multi-element positive electrode material matrix obtained in the step three; finally, pyrrole, naphthalene sulfonic acid and ammonium persulfate are added for chemical oxidation polymerization reaction, and a coating layer is generated inside and on the surface of the multi-element anode material; wherein, based on the total weight of the multi-element positive electrode material matrix, the PVA is used in an amount of 0.1wt%, the pyrrole is used in an amount of 2wt%, the reaction temperature is 5 ℃, the reaction time is 13h, and the molar ratio of the pyrrole to the naphthalene sulfonic acid to the ammonium persulfate is 1:0.3:0.5.
And step five, filtering, washing, drying and screening the mixed slurry in the step four to obtain the organic matter coated multi-element anode material A1. The composition of the organic-coated multi-element positive electrode material A1 is shown in table 1.
Example 2
Step one and step two are the same as in example 1.
Step three, uniformly mixing the zirconium-doped multi-element positive electrode material precursor, zirconium oxide and lithium hydroxide in the step two, wherein the zirconium oxide D 50 =30nm, specific surface area of 100m 2 Zirconium oxide (M' source) was mixed in a molar ratio Zr/(ni+co+mn) =0.001, and lithium hydroxide was mixed in a molar ratio Li/(ni+co+mn+zr) =1.05. And then sintering the mixture for 10 hours at 850 ℃, and crushing and screening to obtain the zirconium doped multi-element anode material matrix.
Step four and step five are the same as in example 1. And (3) preparing the organic matter coated multi-element positive electrode material A2. The composition of the organic-coated multi-element positive electrode material A2 is shown in table 1.
Example 3
Preparing a 2mol/L mixed salt solution according to the molar ratio of nickel sulfate, cobalt sulfate and manganese sulfate of 7:1:2. Preparing 0.1mol/L zirconium nitrate solution, 2mol/L NaOH solution and 6mol/L NH 3 ·H 2 O complexing agent solution.
Step two, mixing a salt solution, a zirconium nitrate solution (M source), a NaOH solution and NH 3 ·H 2 The O complexing agent solution was continuously added to the stirred reactor in a co-current manner to effect the reaction. Controlling the pH value in the reaction system to be 11.2-11.8, controlling the temperature of the whole system to be 60 ℃ and waiting for slurry D 50 The reaction was stopped until 14. Mu.m. And washing, filtering and drying the product to obtain a zirconium-doped multi-element positive electrode material precursor, wherein zirconium nitrate is added according to the molar ratio of Zr/(Ni+Co+Mn) =0.001.
Step three, uniformly mixing the zirconium-doped multi-element positive electrode material precursor, yttrium oxide and lithium hydroxide in the step two, wherein the yttrium oxide D 50 =30nm, specific surface area 200m 2 Yttrium oxide (M' source) was mixed in a molar ratio Y/(ni+co+mn) =0.002, and lithium hydroxide was mixed in a molar ratio Li/(ni+co+mn+zr+y) =1.04. And then sintering the mixture at 820 ℃ for 10 hours, and crushing and screening to obtain the zirconium-yttrium doped multi-element anode material matrix.
Step four, adding sodium polyacrylate and deionized water into a dissolution tank, and stirring until uniform; then adding the zirconium-yttrium doped multi-element positive electrode material matrix obtained in the step three; finally adding pyrrole, sodium dodecyl sulfate and KClO 4 Performing chemical oxidation polymerization reaction to generate a coating layer in and on the surface of the multi-element positive electrode material; wherein, based on the total weight of the multi-element positive electrode material matrix, the dosage of sodium polyacrylate is 0.08wt%, the dosage of pyrrole is 2wt%, the reaction temperature is 7 ℃, the reaction time is 10h, and the pyrrole, sodium dodecyl sulfate and KClO 4 The molar ratio is 1:0.08:0.2.
And step five, filtering, washing, drying and screening the mixed slurry in the step four to obtain the organic matter coated multi-element anode material A3. The composition of the organic-coated multi-element positive electrode material A3 is shown in table 1.
Example 4
Preparing a 2mol/L mixed salt solution according to the mol ratio of nickel sulfate, cobalt sulfate and manganese sulfate of 6:1:3. Preparing 0.1mol/L zirconium nitrate solution, 2mol/L NaOH solution and 6mol/L NH 3 ·H 2 O complexing agent solution.
Step two, mixing a salt solution, a niobium nitrate solution (M source), a NaOH solution and NH 3 ·H 2 The O complexing agent solution was continuously added to the stirred reactor in a co-current manner to effect the reaction. Controlling the pH value in the reaction system to be 11-11.5, controlling the temperature of the whole system to be 65 ℃ and waiting for slurry D 50 The reaction was stopped until 5. Mu.m. And washing, filtering and drying the product to obtain a niobium doped multi-element positive electrode material precursor, wherein niobium nitrate is added according to the molar ratio of Nb/(Ni+Co+Mn) =0.001.
Step three, uniformly mixing the niobium-doped multi-element positive electrode material precursor, cerium hydroxide and lithium hydroxide in the step two, wherein the cerium hydroxide D 50 =30nm, specific surface area of 100m 2 The molar ratio Ce/(ni+co+mn) =0.003, and the molar ratio Li/(ni+co+mn+nb+ce) =1.02. And then sintering the mixture for 10 hours at 850 ℃, and crushing and screening to obtain the niobium-cerium doped multi-element anode material matrix.
Step four, PVP and deionized water are added into a dissolution tank and stirred until uniform; then adding the zirconium gradient doped multi-element positive electrode material matrix obtained in the step three; finally add pyrrole, phenylphosphonic acid and H 2 O 2 Performing chemical oxidation polymerization reaction to generate a coating layer in and on the surface of the multi-element positive electrode material; wherein, based on the total weight of the multi-element positive electrode material matrix, the PVA is used in an amount of 0.15wt%, the pyrrole is used in an amount of 2wt%, the reaction temperature is 5 ℃, the reaction time is 13H, and the pyrrole, the phenylphosphonic acid and the H are mixed 2 O 2 The molar ratio is 1:0.1:0.5.
And step five, filtering, washing, drying and screening the mixed slurry in the step four to obtain the organic matter coated multi-element anode material A4. The composition of the organic-coated multi-element positive electrode material A4 is shown in table 1.
Example 5
Preparing a 2mol/L mixed salt solution according to the molar ratio of nickel sulfate, cobalt sulfate and manganese sulfate of 5:2:3. Preparing 0.1mol/L zirconium nitrate solution, 2mol/L NaOH solution and 6mol/L NH 3 ·H 2 O complexing agent solution.
Step two, mixing a salt solution, a niobium nitrate solution (M source), a NaOH solution and NH 3 ·H 2 The O complexing agent solution was continuously added to the stirred reactor in a co-current manner to effect the reaction. Controlling the pH value in the reaction system to be 11.2-11.8, controlling the temperature of the whole system to be 60 ℃ and waiting for slurry D 50 The reaction was stopped until 5. Mu.m. And washing, filtering and drying the product to obtain a niobium doped multi-element positive electrode material precursor, wherein niobium nitrate is added according to the molar ratio of Nb/(Ni+Co+Mn) =0.001.
Step three, uniformly mixing the niobium-doped multi-element positive electrode material precursor, yttrium oxide and lithium hydroxide in the step two, wherein the yttrium oxide D 50 =30nm, specific surface area of 100m 2 Yttrium oxide (M' source) was mixed in a molar ratio Y/(ni+co+mn) =0.01, and lithium hydroxide was mixed in a molar ratio Li/(ni+co+mn+nb+y) =1.03. And then sintering the mixture for 10 hours at 850 ℃, and crushing and screening to obtain the niobium-cerium doped multi-element anode material matrix.
Step four, adding sodium polyacrylate and deionized water into a dissolution tank, and stirring until uniform; then adding the yttrium-doped multi-element positive electrode material matrix obtained in the step three; finally, pyrrole, 3-nitrobenzoic acid and BPO are added to carry out chemical oxidative polymerization reaction, and a coating layer is generated inside and on the surface of the multi-element anode material; wherein, based on the total weight of the multi-element positive electrode material matrix, the dosage of sodium polyacrylate is 0.08wt%, the dosage of pyrrole is 2wt%, the reaction temperature is 5 ℃, the reaction time is 13h, and the molar ratio of pyrrole, 3-nitrobenzoic acid and BPO is 1:0.08:0.06.
And step five, filtering, washing, drying and screening the mixed slurry in the step four to obtain the organic matter coated multi-element anode material A5. The composition of the organic-coated multi-element positive electrode material A5 is shown in table 1.
Example 6
Step one, step two and step three are the same as in example 1.
Step four, adding PVA and deionized water into a dissolution tank, and stirring until uniform; then adding the zirconium-lanthanum doped multi-element positive electrode material matrix obtained in the step three; finally, pyrrole, naphthalene sulfonic acid and ammonium persulfate are added for chemical oxidation polymerization reaction, and a coating layer is generated inside and on the surface of the multi-element anode material; wherein, based on the total weight of the multi-element positive electrode material matrix, the PVA is used in an amount of 0.1wt%, the pyrrole is used in an amount of 2wt%, the reaction temperature is 5 ℃, the reaction time is 13h, and the molar ratio of the pyrrole to the naphthalene sulfonic acid to the ammonium persulfate is 1:2:0.5.
And step five, filtering, washing, drying and screening the mixed slurry in the step four to obtain the organic matter coated multi-element anode material A6. The composition of the organic-coated multi-element positive electrode material A6 is shown in table 1.
Example 7
Step one and step two are the same as in example 1.
Step three, uniformly mixing the zirconium-doped multi-element positive electrode material precursor, lanthanum hydroxide and lithium hydroxide in the step two, wherein lanthanum hydroxide D 50 =5μm, specific surface area 10m 2 Lanthanum hydroxide (M' source) was mixed in a molar ratio La/(ni+co+mn) =0.001, and lithium hydroxide was mixed in a molar ratio Li/(ni+co+mn+zr+la) =1.05. And then sintering the mixture for 10 hours at 850 ℃, and crushing and screening to obtain the zirconium-lanthanum doped multi-element anode material matrix.
Step four and step five are the same as in example 1. And (3) preparing the organic matter coated multi-element positive electrode material A7. The composition of the organic-coated multi-element positive electrode material A7 is shown in table 1.
Example 8
Step one, step two and step three are the same as in example 1.
Step four, adding PVA and deionized water into a dissolution tank, and stirring until uniform; then adding the zirconium-lanthanum doped multi-element positive electrode material matrix obtained in the step three; finally, pyrrole, naphthalene sulfonic acid and ammonium persulfate are added for chemical oxidation polymerization reaction, and a coating layer is generated inside and on the surface of the multi-element anode material; wherein, based on the total weight of the multi-element positive electrode material matrix, the PVA is used in an amount of 0.1wt%, the pyrrole is used in an amount of 2wt%, the reaction temperature is 25 ℃, the reaction time is 13h, and the molar ratio of the pyrrole to the naphthalene sulfonic acid to the ammonium persulfate is 1:0.3:0.5.
And step five, filtering, washing, drying and screening the mixed slurry in the step four to obtain the organic matter coated multi-element anode material A8. The composition of the organic-coated multi-element positive electrode material A8 is shown in table 1.
Comparative example 1
Preparing a 2mol/L mixed salt solution according to the mol ratio of nickel sulfate, cobalt sulfate and manganese sulfate of 8:1:1. Preparing 2mol/L NaOH solution and 6mol/L NH 3 ·H 2 O complexing agent solution.
Step two, mixing the salt solution, the NaOH solution and the NH 3 ·H 2 The O complexing agent solution was continuously added to the stirred reactor in a co-current manner to effect the reaction. Controlling the pH value in the reaction system to be 11.2-11.8, controlling the temperature of the whole system to be 60 ℃ and waiting for slurry D 50 The reaction was stopped until reaching 10. Mu.m. And (3) washing, filtering and drying the product to obtain the multi-element positive electrode material precursor.
And thirdly, uniformly mixing the precursor of the multi-element positive electrode material in the second step with lithium hydroxide, wherein the lithium hydroxide is mixed according to the mole ratio of Li/(Ni+Co+Mn) =1.05. And then sintering the mixture for 10 hours at 850 ℃, and crushing and screening to obtain the multi-element positive electrode material D1. The composition of the multi-component positive electrode material D1 is shown in table 1.
Comparative example 2
Step one, step two and step three are the same as in example 1.
Step four, adding PVA and deionized water into a dissolution tank, and stirring until uniform; then adding the zirconium-doped multi-element positive electrode material matrix obtained in the step three; finally, pyrrole and ammonium persulfate are added for chemical oxidation polymerization reaction to generate a coating layer; wherein, based on the total weight of the multi-element positive electrode material matrix, the dosage of PVA is 0.1wt%, the dosage of pyrrole is 2wt%, the reaction temperature is 5 ℃, the reaction time is 13h, and the molar ratio of pyrrole to ammonium persulfate is 1:0.5.
And step five, filtering, washing, drying and screening the mixed slurry in the step four to obtain the organic matter coated multi-element anode material D2. The composition of the multi-component positive electrode material D2 is shown in table 1.
Comparative example 3
Step one, step two and step three are the same as in example 1.
Step four, adding PVA and deionized water into a dissolution tank, and stirring until uniform; then adding the zirconium-doped multi-element positive electrode material matrix obtained in the step three; finally, pyrrole, lithium nitrate and ammonium persulfate are added for chemical oxidation polymerization reaction, and a coating layer is generated inside and outside the multi-element positive electrode material; wherein, based on the total weight of the multi-element positive electrode material matrix, the PVA is used in an amount of 0.1wt%, the pyrrole is used in an amount of 2wt%, the reaction temperature is 5 ℃, the reaction time is 13h, and the molar ratio of the pyrrole to the lithium nitrate to the ammonium persulfate is 1:0.3:0.5.
And step five, filtering, washing, drying and screening the mixed slurry in the step four to obtain the organic matter coated multi-element anode material D3. The composition of the organic-coated multi-component positive electrode material D3 is shown in table 1.
Comparative example 4
Preparing a 2mol/L mixed salt solution according to the mol ratio of nickel sulfate, cobalt sulfate and manganese sulfate of 8:1:1. Preparing 2mol/L NaOH solution and 6mol/L NH 3 ·H 2 O complexing agent solution.
Step two, mixing the salt solution, the NaOH solution and the NH 3 ·H 2 The O complexing agent solution was continuously added to the stirred reactor in a co-current manner to effect the reaction. Controlling the pH value in the reaction system to be 11.2-11.8, controlling the temperature of the whole system to be 60 ℃ and waiting for slurry D 50 The reaction was stopped until reaching 10. Mu.m. And (3) washing, filtering and drying the product to obtain the multi-element positive electrode material precursor.
Step three, uniformly mixing the multi-element positive electrode material precursor, lanthanum hydroxide and lithium hydroxide in the step two, wherein lanthanum hydroxide D 50 =30nm, specific surface area of 100m 2 Per gram, lanthanum hydroxide (M' source) in molar ratio La/(ni+co+mn) =0.001, lithium hydroxide in molar ratioThe molar ratio was Li/(ni+co+mn+la) =1.05. And then sintering the mixture for 10 hours at 850 ℃, and crushing and screening to obtain the lanthanum-doped multi-element anode material matrix.
Step four and step five are the same as in example 1. And (3) preparing the organic matter coated multi-element positive electrode material D4. The composition of the organic-coated multi-element positive electrode material D4 is shown in table 1.
Comparative example 5
Step one and step two are the same as in example 1.
And thirdly, uniformly mixing the zirconium-doped multi-element positive electrode material precursor in the second step with lithium hydroxide, wherein the lithium hydroxide is mixed according to the molar ratio of Li/(Ni+Co+Mn+Zr) =1.05. And then sintering the mixture for 10 hours at 850 ℃, and crushing and screening to obtain the zirconium doped multi-element anode material matrix.
Step four and step five are the same as in example 1. And (5) preparing the organic matter coated multi-element positive electrode material D5. The composition of the organic-coated multi-element positive electrode material D5 is shown in table 1.
TABLE 1
Note that: in Table 1, "coating layer: matrix" means a ratio of n (Py) forming the organic coating layer to the multi-element positive electrode material matrix [ n (Ni) +n (Co) +n (Mn) ].
Fig. 1 is an SEM photograph of the organic-coated multi-component positive electrode material A1 prepared in example 1, and fig. 2 is an SEM photograph of the multi-component positive electrode material D1 prepared in comparative example 1. As can be seen from fig. 1 and 2, the organic matter coated multi-element positive electrode material A1 in fig. 1 has a uniform coating layer on the surface, while the multi-element positive electrode material D1 in fig. 2 has a smooth surface without any adhering matter.
FIG. 3 is an XRD pattern of the organic-coated multi-element positive electrode material A1 obtained in example 1, and it can be seen from FIG. 3 that the organic-coated multi-element positive electrode materialA1 is alpha-NaFeO 2 The layered structure illustrates that the surface coating does not alter the crystal structure of the matrix itself of the multi-component positive electrode material.
Test example 1
The positive electrode materials prepared in the examples and the comparative examples are used for assembling a liquid lithium ion battery, and specifically comprise the following steps: the positive electrode material, acetylene black and polyvinylidene fluoride are mixed according to the mass ratio of 95:2.5:2.5 dispersing in a proper amount of NMP, coating on aluminum foil, drying, cutting into positive pole pieces with the diameter of 12mm, and vacuum-sealing and preserving the positive pole pieces after vacuum drying at 120 ℃ for 12 hours. The anode uses a lithium metal sheet with the diameter of 16mm and the thickness of 1 mm; the membrane is a Celgard porous membrane with the thickness of 25 μm; electrolyte is LiPF 6 As solute, with equal volume of ethylene carbonate, dimethyl carbonate and diethyl carbonate as solvent, liPF 6 The concentration of (C) was 1mol/L.
And assembling the positive electrode plate, the diaphragm, the negative electrode plate and the electrolyte into the 2025 type button cell in an argon-filled glove box with water content and oxygen content of less than 5 ppm. The electrochemical performance of the liquid lithium ion battery was tested, and the test results are shown in table 3.
TABLE 3 Table 3
The charge-discharge curve graph of the liquid lithium ion battery obtained by respectively assembling the organic matter coated multi-element positive electrode material A1 and the multi-element positive electrode material D1 of the comparative example 1 is shown in fig. 4, and as can be seen from fig. 4, the discharge specific capacities of the liquid lithium ion battery are 213.3mAh/g and 206.4mAh/g respectively.
The cycle performance diagram of the liquid lithium ion battery assembled by the organic matter coated multi-element positive electrode material A1 and the multi-element positive electrode material D1 at 1C is shown in fig. 5, and as can be seen from fig. 5, compared with the liquid lithium ion battery assembled by the multi-element positive electrode material D1, the cycle performance of the liquid lithium ion battery assembled by the organic matter coated multi-element positive electrode material A1 is more excellent, and the coating layer can effectively avoid side reaction between the positive electrode and the electrolyte, thereby improving the battery Performance. Due to the high crystallinity of Py, the transmission rate of lithium ions and electrons is low, so that the capacity of the multi-element positive electrode material D2 coated by Py is low; inorganic anion NO 3 - The crystallinity of Py cannot be reduced as effectively as the large group anion R' in the present invention, increasing the conductivity, and also results in low capacity of the multi-component positive electrode material D3.
The capacity of the organic matter coated multi-element positive electrode material A1 in the liquid lithium ion battery system is higher than that of the organic matter coated multi-element positive electrode material A6, the capacity retention rate of the organic matter coated multi-element positive electrode material A1 is higher than that of the organic matter coated multi-element positive electrode material A6, and the organic matter coated multi-element positive electrode material A1 shows that an active coating layer with higher ion/electron conductivity and stable electrolyte can be obtained through reasonable organic coating, and the capacity and the structural stability of the multi-element positive electrode material are improved. The capacity of the organic matter coated multi-element positive electrode material A1 is higher than that of the organic matter coated multi-element positive electrode materials A7 and A8, and the capacity retention rate of the organic matter coated multi-element positive electrode material A1 is also higher than that of the organic matter coated multi-element positive electrode materials A7 and A8, which shows that the multi-element positive electrode materials with stable structures can be obtained through doping at different scale levels.
Test example 2
The positive electrode materials prepared in the examples and the comparative examples are used for assembling solid-state lithium ion batteries, and the specific steps are as follows:
PEO and LiTFSI are banburying according to the mass ratio of 3:1, then hot pressing is carried out to form a film with the thickness of 30 mu m, and then an electrolyte film cut into the diameter of 19mm is placed into a 60 ℃ for vacuum drying for 10 hours, and then vacuum sealing storage is carried out.
The method comprises the following steps of (1) mixing a positive electrode material, acetylene black, PVDF and LiTFSI according to a mass ratio of 90:2:2:6 dispersing in a proper amount of NMP, coating on aluminum foil, drying, cutting into positive pole pieces with the diameter of 12mm, and vacuum-sealing and preserving the positive pole pieces after vacuum drying at 120 ℃ for 12 hours.
And taking metal lithium as a negative electrode, and assembling the positive electrode plate and the PEO electrolyte membrane into the 2025 button cell in an argon-filled glove box with water content and oxygen content of less than 5 ppm. The electrochemical properties of the solid-state lithium ion batteries were tested and the results are shown in table 4.
TABLE 4 Table 4
The charge-discharge curve diagram of the solid lithium ion battery assembled by the organic matter coated multi-element positive electrode material A1 and the multi-element positive electrode material D1 at 0.1C is shown in FIG. 6, and the discharge specific capacities of the solid lithium ion battery are respectively 216.1mAh/g and 205.8mAh/g as shown in FIG. 6, which shows that the discharge specific capacities of the organic matter coated multi-element positive electrode material are superior to those of the matrix, and the polypyrrole coating layer can provide corresponding capacities; the charge-discharge electrode of the organic matter coated multi-element positive electrode material is smaller than that of the matrix, which means that the polypyrrole coating layer can reduce the impedance between the positive electrode and the electrolyte.
The cycle performance diagram of the solid lithium ion battery assembled by the organic matter coated multi-element positive electrode material A1 and the multi-element positive electrode material D1 at 0.2C is shown in figure 7, and as can be seen from figure 7, the capacity retention rates of the solid lithium ion battery after 80 weeks of cycle are 76.5% and 68%, respectively. The organic matter coated multi-element positive electrode material has obviously better cycle performance than the matrix, which indicates that the coating layer can effectively avoid side reaction between the positive electrode and the electrolyte, thereby prolonging the cycle life of the battery. The impedance of the solid-state battery is far greater than that of the liquid-state battery, so that the organic coating layer with low crystallinity, high elasticity and high conductivity can improve the contact between the anode and the solid-state electrolyte and reduce the interface impedance of the anode and the solid-state electrolyte. Therefore, the capacity of the solid-state battery is lower and the cycle is worse by simply adopting the multi-element positive electrode materials D2 and D3 which are coated by Py and cannot reduce the crystallinity.
The capacity of the organic matter coated multi-element positive electrode material in the table 4 is higher than that of the organic matter coated multi-element positive electrode material in the solid lithium ion battery system, which shows that the organic matter coated multi-element positive electrode material provided by the invention is more suitable for the solid lithium ion battery.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (16)
1. The organic matter coated multi-element positive electrode material is characterized by comprising a multi-element positive electrode material matrix and an organic coating layer formed in the matrix and on the surface of the matrix;
the composition of the multielement anode material matrix is shown as a formula I:
Li a (Ni x Co y Mn 1-x-y M δ ) 1-z M’ z O 2 a formula I;
wherein M and M' are each independently selected from at least one element of Al, ba, zr, ti, nb, ta, ga, Y, W, ca, sr, sc, cr, mo, hf, si, sm, V, la, ce, mg and B; a is more than or equal to 0.90 and less than or equal to 1.30,0, x is more than or equal to 1,0.001 and less than or equal to y is more than or equal to 1, delta is more than 0 and less than or equal to 0.1, and z is more than 0 and less than or equal to 0.1;
the composition of the organic coating layer is shown as a formula II:
p (PyR') formula II;
wherein P (PyR ') is an organic anion doped polypyrrole and R' is at least one selected from the group consisting of C1-C20 alkylsulfate, C1-C20 alkylsulfonate, C6-C20 arylsulfonate, C1-C20 alkylsulfinate, C6-C20 arylsulfinate, C1-C20 alkylphosphonate, C6-C20 arylphosphonate, primary phosphate, secondary phosphate, amino, carboxylate, mono-C1-C20 alkyl oxalate, C1-C20 alkylborate, and C6-C20 arylborate.
2. The organic-coated multi-element positive electrode material according to claim 1, wherein in formula I, M and M' are each independently selected from at least one element of Zr, ti, nb, ta, ga, Y, W, cr, mo, hf, si, sm, V, la and Ce; a is more than or equal to 0.96 and less than or equal to 1.08,0.01, x is more than or equal to 0.98,0.001, y is more than or equal to 1,0.001, delta is more than or equal to 0.05,0.001, and z is more than or equal to 0.05;
And/or, in formula II, R' is selected from at least one of C3-C18 alkylsulfate, C3-C18 alkylsulfonate, C6-C18 arylsulfonate, C3-C18 alkylsulfinate, C6-C18 arylsulfinate, C3-C18 alkylphosphonate, C6-C18 arylsulfonate, primary phosphate, secondary phosphate, amino, carboxylate, mono-C6-C18 alkyl oxalate, C3-C18 alkylborate, and C6-C18 arylborate.
3. The organic-coated multi-component positive electrode material of claim 2, wherein in formula II, R' is at least one of octyl sulfate, dodecyl sulfate, p-toluenesulfonate, naphthalenesulfonate, 2-naphthylamine-1-sulfonate, 3-hydroxy-1-propanesulfonate, p-styrenesulfonate, hexadecylsulfonate, p-toluenesulfonate, phenylsulfinate, formamidinesulfinate, methane sulfinate, octadecylphosphonate, phenylphosphonate, poly (vinylphosphonic acid), glycinate, phenylalanine, alanine, glutamate, leucine, tyrosine, carboxylate, monoethyl oxalate, butylborate, and 3-nitrobenzeneborate.
4. The organic-coated multi-element positive electrode material according to any one of claims 1 to 3, wherein a molar ratio of Py to R' forming the organic coating layer is 1: (0.001-1);
and/or, the ratio of Py forming the organic coating layer to the multi-element positive electrode material base is such that the ratio of n (Py) [ n (Ni) +n (Co) +n (Mn) ] is (0.001-0.1): 1, a step of;
and/or the thickness of the organic coating layer is less than or equal to 200nm.
5. The organic-coated multi-element positive electrode material according to claim 4, wherein the thickness of the organic coating layer is 2 to 50nm.
6. A method for preparing the organic matter-coated multi-element positive electrode material according to any one of claims 1 to 5, comprising the steps of:
(1) Preparing a mixed salt solution by using nickel salt, cobalt salt and manganese salt according to the molar ratio of Ni to Co to Mn=x to y (1-x-y); preparing an M source salt solution, a precipitator solution and a complexing agent solution respectively from an M source, a precipitator and a complexing agent;
(2) Adding the mixed salt solution, the M source salt solution, the precipitator solution and the complexing agent solution into a reaction kettle, and performing coprecipitation reaction to obtain solid-liquid mixed slurry, wherein the solid-liquid mixed slurry is filtered, washed, dried and screened to obtain a multi-element anode material precursor;
(3) Mixing, sintering, crushing and screening the multi-element positive electrode material precursor, the lithium source and the M' source to obtain a multi-element positive electrode material matrix;
(4) Mixing a dispersing agent with a solvent to obtain a dispersing agent solution, and adding the multi-element anode material matrix, pyrrole, a doping agent R' and an oxidant into the dispersing agent solution in sequence under the stirring condition to perform chemical oxidation polymerization reaction to obtain mixed slurry;
(5) And filtering, washing, drying and screening the mixed slurry to obtain the organic matter coated multi-element anode material.
7. The preparation method according to claim 6, wherein the concentration of the mixed salt solution is 1-3mol/L, the concentration of the precipitant solution is 1-15mol/L, the concentration of the complexing agent solution is 1-15mol/L, and the concentration of the M source salt solution is 0.01-1mol/L;
and/or, the nickel salt, the cobalt salt, the manganese salt are each independently selected from at least one of sulfate, nitrate, chloride, oxalate, acetate, and citrate;
and/or, the M source and the M' source are each independently selected from compounds of at least one element of Al, ba, zr, ti, nb, ta, ga, Y, W, ca, sr, sc, cr, mo, hf, si, sm, V, la, ce, mg and B;
And/or, the particle size of the compound of the M' source is less than 200nm;
and/or, a compound of said M' sourceHas a specific surface area of more than 20m 2 /g；
And/or the lithium source is selected from at least one of lithium carbonate, lithium hydroxide and lithium nitrate;
and/or the dopant R' is selected from at least one of C1-C20 alkyl sulfate, C1-C20 alkyl sulfonate, C6-C20 aryl sulfonate, C1-C20 alkyl sulfinate, C6-C20 aryl sulfinate, C1-C20 alkyl phosphonate, C6-C20 aryl phosphonate, primary phosphate, secondary phosphate, amino acid, carboxylate, oxalic acid mono-C1-C20 alkyl ester, C1-C20 alkyl boric acid, and C6-C20 aryl boric acid;
and/or the oxidizing agent is selected from (NH 4 ) 2 SO 8 、K 2 Cr 2 O 7 、KClO 4 、KIO 3 、NaClO 3 、H 2 O 2 、MnO 2 、FeCl 3 And at least one of benzoyl peroxide;
and/or the dispersing agent is at least one selected from polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, polyacrylate and polyacrylamide.
8. The production method according to claim 7, wherein the nickel salt is at least one selected from the group consisting of nickel sulfate, nickel nitrate, nickel chloride, nickel oxalate, nickel acetate and nickel citrate; the cobalt salt is at least one selected from cobalt sulfate, cobalt nitrate, cobalt chloride, cobalt oxalate, cobalt acetate and cobalt citrate; the manganese salt is selected from at least one of manganese sulfate, manganese nitrate, manganese chloride, manganese oxalate, manganese acetate and manganese citrate;
And/or the compound of the M source is at least one of sodium metaaluminate, barium nitrate, zirconium chloride, titanium sulfate, niobium nitrate, tantalum nitrate, gallium nitrate, yttrium nitrate, ammonium tungstate, calcium chloride, lanthanum nitrate, cerium nitrate, magnesium nitrate and sodium borate;
and/or the dopant R' is selected from at least one of C3-C18 alkyl sulfate, C3-C18 alkyl sulfonate, C6-C18 aryl sulfonate, C3-C18 alkyl sulfinate, C6-C18 aryl sulfinate, C3-C18 alkyl phosphonate, C6-C18 aryl phosphonate, primary phosphate, secondary phosphate, amino acid, carboxylate, oxalic acid mono-C6-C18 alkyl ester, C3-C18 alkyl boric acid, and C6-C18 aryl boric acid.
9. The production method according to claim 8, wherein the M 'source compound is selected from at least one of an oxide of an M' source, a hydroxide of an M 'source, and a carbonate of an M' source;
and/or the dopant R' is selected from at least one of sodium octyl sulfate, sodium dodecyl sulfate, lithium dodecyl sulfate, sodium p-toluenesulfonate, sodium naphthalene sulfonate, sodium 2-naphthylamine-1-sulfonic acid, sodium 3-hydroxy-1-propane sulfonate, sodium p-styrenesulfonate, naphthalene sulfonic acid, sodium hexadecyl sulfonate, lithium p-toluene sulfinate, sodium benzene sulfinate, formamidine sulfinic acid, sodium methane sulfinate, octadecylphosphonic acid, phenylphosphonic acid, poly (vinyl phosphonic acid), glycine, phenylalanine, alanine, glutamic acid, leucine, tyrosine, carboxylate, monoethyl oxalate, butyl boric acid, and 3-nitrobenzoic acid.
10. The production method according to any one of claims 6 to 9, wherein the lithium source is added in an amount of 0.90.ltoreq.n (Li) ]/[ n (Ni) +n (Co) +n (Mn) +n (M) ].ltoreq.1.30;
and/or, the M source is added according to the molar ratio of 0 < [ n (M) ]/[ n (Ni) +n (Co) +n (Mn) ]lessthan or equal to 0.1;
and/or, the M 'source is added according to the molar ratio of 0 < [ n (M') ]/[ n (Ni) +n (Co) +n (Mn) ]lessthan or equal to 0.1;
and/or, based on the total weight of the multi-element positive electrode material matrix, the dosage of the dispersing agent is 0.001-1wt%, and the dosage of the pyrrole is 0.1-10wt%;
and/or the molar ratio of the pyrrole, the dopant R' and the oxidizing agent is 1: (0.001-1): (0.01-1).
11. The production method according to any one of claims 6 to 9, wherein the conditions of the coprecipitation reaction include: the pH value is 10-13, the reaction temperature is 40-70 ℃, and the reaction time is 5-20h;
and/or, the sintering conditions include: the sintering temperature is 650-1000 ℃ and the sintering time is 4-20h;
and/or, the conditions of the chemical oxidative polymerization reaction include: the reaction temperature is 0-10 ℃ and the reaction time is 5-20h.
12. The method of manufacturing according to claim 11, wherein the sintering conditions include: the sintering temperature is 800-950 ℃; the sintering time is 6-15h.
13. The preparation method according to claim 10, wherein the conditions of the coprecipitation reaction include: the pH value is 10-13, the reaction temperature is 40-70 ℃, and the reaction time is 5-20h;
and/or, the sintering conditions include: the sintering temperature is 650-1000 ℃ and the sintering time is 4-20h;
and/or, the conditions of the chemical oxidative polymerization reaction include: the reaction temperature is 0-10 ℃ and the reaction time is 5-20h.
14. The method of manufacturing according to claim 13, wherein the sintering conditions include: the sintering temperature is 800-950 ℃; the sintering time is 6-15h.
15. Use of the organic matter-coated multi-element positive electrode material according to any one of claims 1 to 5 in lithium ion batteries.
16. A lithium ion battery, characterized in that the lithium ion battery uses the organic matter coated multi-element positive electrode material as a positive electrode material according to any one of claims 1-5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111652415.3A CN114695852B (en) | 2021-12-30 | 2021-12-30 | Organic matter coated multi-element positive electrode material, preparation method and application thereof, and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111652415.3A CN114695852B (en) | 2021-12-30 | 2021-12-30 | Organic matter coated multi-element positive electrode material, preparation method and application thereof, and lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114695852A CN114695852A (en) | 2022-07-01 |
| CN114695852B true CN114695852B (en) | 2023-09-22 |
Family
ID=82137190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111652415.3A Active CN114695852B (en) | 2021-12-30 | 2021-12-30 | Organic matter coated multi-element positive electrode material, preparation method and application thereof, and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114695852B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007250466A (en) * | 2006-03-17 | 2007-09-27 | Japan Carlit Co Ltd:The | Conductive polymer coating material and metal coating method |
| CN105390699A (en) * | 2015-11-04 | 2016-03-09 | 宁德新能源科技有限公司 | Conductive material and lithium ion battery comprising same |
| CN109713239A (en) * | 2017-10-26 | 2019-05-03 | 荆门市格林美新材料有限公司 | Ion doping, nickel cobalt lithium aluminate cathode material of cladding and preparation method thereof |
| CN109768232A (en) * | 2018-12-11 | 2019-05-17 | 广东邦普循环科技有限公司 | A kind of complex phase doping nickel-cobalt-manganternary ternary anode material and its preparation method and application |
-
2021
- 2021-12-30 CN CN202111652415.3A patent/CN114695852B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007250466A (en) * | 2006-03-17 | 2007-09-27 | Japan Carlit Co Ltd:The | Conductive polymer coating material and metal coating method |
| CN105390699A (en) * | 2015-11-04 | 2016-03-09 | 宁德新能源科技有限公司 | Conductive material and lithium ion battery comprising same |
| CN109713239A (en) * | 2017-10-26 | 2019-05-03 | 荆门市格林美新材料有限公司 | Ion doping, nickel cobalt lithium aluminate cathode material of cladding and preparation method thereof |
| CN109768232A (en) * | 2018-12-11 | 2019-05-17 | 广东邦普循环科技有限公司 | A kind of complex phase doping nickel-cobalt-manganternary ternary anode material and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114695852A (en) | 2022-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106505195B (en) | High-nickel cathode material, preparation method thereof and lithium ion battery | |
| KR100943193B1 (en) | Cathode active material and lithium battery using the same | |
| KR101473322B1 (en) | Cathode active material and cathode and lithium battery containing the material | |
| KR101595322B1 (en) | Manufacturing method of positive active material for lithium rechargeable batteries and positive active material made by the same | |
| CN108886142B (en) | Method for manufacturing anode active material for lithium secondary battery and anode active material for lithium secondary battery manufactured thereby | |
| KR101378580B1 (en) | Cathod active material, lithium rechargeble battery including the same, and method of activiting the same | |
| KR101550741B1 (en) | Manufacturing method of positive active material for lithium rechargeable batteries and positive active material made by the same | |
| CN107369815B (en) | Lithium ion secondary battery composite positive electrode material and preparation method thereof | |
| JP2000077071A (en) | Nonaqueous electrolyte secondary battery | |
| JP2012146662A (en) | Cathode active material, cathode and lithium battery employing the same, and method of preparing the same | |
| KR20160091172A (en) | Manufacturing method of positive active material containing reduced residual lithium and positive active material manufactured by the same | |
| KR20180059736A (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| KR20140119621A (en) | Precusor for lithium rich active material and lithium rich active material made by the same | |
| US20210328217A1 (en) | Lithium battery and anode material thereof | |
| CN109755530B (en) | Surface coating method for titanium barium bimetallic oxide of high-pressure lithium cobalt oxide positive electrode material | |
| CN113363477B (en) | Preparation method of multilayer coated ternary cathode material | |
| CN113745487A (en) | Positive electrode material and preparation method and application thereof | |
| CN117154046A (en) | Sodium-rich tunnel transition metal oxide positive electrode material and preparation method and application thereof | |
| JP6624631B2 (en) | Lithium transition metal composite oxide and method for producing the same | |
| KR102027460B1 (en) | Manufacuring method of cathode active material for lithium rechargeable battery, and cathode active material made by the same | |
| CN114695852B (en) | Organic matter coated multi-element positive electrode material, preparation method and application thereof, and lithium ion battery | |
| KR101762282B1 (en) | High capacity cathode material improved thermal stability for lithium ion battery and a method of manufacturing the same | |
| CN109037607B (en) | Preparation method of coated lithium manganate composite material | |
| KR101556299B1 (en) | Cathode for lithium secondary battery comprising amorphous lithium transition metal oxide coating layer and manufacturing method thereof | |
| US20170324085A1 (en) | Precursor for Producing Lithium-rich Cathode Active Material, and Lithium-rich Cathode Active Material Produced Thereby |
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 |