CN115072801A - Positive electrode material precursor, positive electrode material, preparation method and application thereof - Google Patents
Positive electrode material precursor, positive electrode material, preparation method and application thereof Download PDFInfo
- Publication number
- CN115072801A CN115072801A CN202210714671.9A CN202210714671A CN115072801A CN 115072801 A CN115072801 A CN 115072801A CN 202210714671 A CN202210714671 A CN 202210714671A CN 115072801 A CN115072801 A CN 115072801A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- precursor
- electrode material
- temperature
- transition metal
- 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.)
- Pending
Links
- 239000002243 precursor Substances 0.000 title claims abstract description 72
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 47
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 45
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000012266 salt solution Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 26
- 150000003624 transition metals Chemical class 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 238000000975 co-precipitation Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 18
- 239000010405 anode material Substances 0.000 claims abstract description 15
- 239000010406 cathode material Substances 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims abstract description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 239000010936 titanium Substances 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000011135 tin Substances 0.000 claims abstract 2
- 239000011734 sodium Substances 0.000 claims description 48
- 239000011572 manganese Substances 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 21
- 229910001415 sodium ion Inorganic materials 0.000 claims description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 20
- 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 19
- 229910052708 sodium Inorganic materials 0.000 claims description 19
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 18
- 238000001694 spray drying Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 15
- 238000009818 secondary granulation Methods 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008139 complexing agent Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 11
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 239000000945 filler Substances 0.000 description 7
- 238000010168 coupling process Methods 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 5
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 4
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 4
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 4
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 2
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000010981 drying operation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229940039748 oxalate Drugs 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 transition metal salt ions Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a positive electrode material precursor, a positive electrode material, and a preparation method and application thereof. The preparation method of the precursor of the cathode material comprises the following steps: mixing a salt solution of transition metal and a precipitant solution under a supergravity condition, and carrying out coprecipitation reaction to obtain a precipitate; wherein the transition metal is selected from one or more of nickel, iron, manganese, copper, aluminum, cerium, cobalt, zinc, tin and titanium; the rotation speed under the condition of supergravity is 500-3000 rpm. The preparation method has the advantages of low energy consumption, short time consumption and continuous and controllable reaction, and can realize large-scale, quick and high-quality production of the precursor. The precursor prepared by the method has good appearance, particle size and consistency, and the anode material prepared from the precursor has excellent electrochemical performance.
Description
Technical Field
The invention relates to a positive electrode material precursor, a positive electrode material, and a preparation method and application thereof.
Background
Batteries are increasingly used in daily life and work of people and in industrial production, such as electronic products in daily use, low-speed electric vehicles and electric automobiles for transportation, battery devices for energy storage, and the like. The production of the electrode material of the battery usually needs to firstly manufacture a precursor, which has the functions of realizing the uniform mixing of metal ions on the microscale and simultaneously forming nano or micron-sized particles with the sizes and the appearances meeting the requirements, thereby facilitating the subsequent firing of the material and the manufacture of the electrode and exerting the intrinsic electrochemical capacity of the material. The ternary lithium battery positive electrode material widely used in the electric automobile is manufactured by the production process. The sodium ion battery has the characteristics of high safety, abundant raw materials, low cost and the like, and becomes a research and development hotspot of battery technology in recent years.
The positive electrode material of the sodium ion battery is one of the key materials of the sodium ion battery, wherein the transition metal oxide with the layered structure has higher specific capacity and a plurality of similarities with the positive electrode material of the lithium battery which is mature in the market at present in the aspects of synthesis and battery manufacturing, and is one of the materials which have potential to be commercially produced. The more optimized manufacturing process of the layered structure transition metal oxide cathode material of the sodium-ion battery also starts from the production of a coprecipitated precursor.
The method for producing the coprecipitation precursor material matured in industry at present isIn a stirred reactor. The solution of the metal ion salt to be precipitated is fed to the stirred reactor by means of a metering pump, while the precipitating agent (e.g. NaOH, Na) is added 2 CO 3 Sodium oxalate Na 2 C 2 O 4 Etc.). In order to ensure uniform concentration in the reactor, proper stirrer design and high stirring speed are required. In addition, the feeding is slow as much as possible and the concentration of the feed liquid is low as much as possible, so that the phenomenon that local reactant is too high in concentration to form particles with different sizes and low compactness is avoided. Therefore, the method for producing the precursor by stirring kettle coprecipitation has low efficiency, the coprecipitation equipment reaching a certain yield is very large, and the consistency of the produced product is difficult to control, so that the production difficulty and the production cost are higher.
Disclosure of Invention
The invention aims to overcome the defects of low efficiency and difficult control of consistency in the production of a battery anode material precursor by a coprecipitation method in the prior art, and provides an anode material precursor, an anode material, and preparation methods and applications thereof. The preparation method of the precursor of the cathode material has high efficiency, and the prepared precursor of the cathode material has good consistency.
The invention solves the technical problems through the following technical scheme:
a preparation method of a precursor of a positive electrode material comprises the following steps:
mixing a salt solution of transition metal with a precipitator under a supergravity condition, and carrying out coprecipitation reaction to obtain a precipitate; wherein,
the transition metal is selected from one or more of nickel, iron, manganese, copper, aluminum, cobalt, zinc, cerium, tin and titanium;
the rotating speed under the supergravity condition is 500-3000 rpm.
In the invention, the precursor of the positive electrode material is preferably a precursor of a positive electrode material for a sodium-ion battery.
In the invention, the precursor of the cathode material is preferably a nickel-iron-manganese ternary precursor.
In the present invention, preferably, the transition metal is preferably nickel, iron and manganese. Wherein, the molar ratio of nickel, iron and manganese is preferably (0-8): (1-8): (1-5), for example, 1:1: 1.
In the present invention, preferably, the kind of the salt in the salt solution of the transition metal may be a salt conventional in the art, such as a sulfate.
In the present invention, preferably, the salt solution of the transition metal includes a mixed solution of nickel sulfate, manganous sulfate, and ferrous sulfate.
In the present invention, preferably, the concentration of the salt solution of the transition metal is 0.5 to 4mol/L, and more preferably 2mol/L, wherein the concentration refers to the total concentration of all transition metal ions in the salt solution.
In the present invention, the precipitant in the precipitant solution may be a precipitant conventional in the art, such as sodium hydroxide.
In the present invention, the anion in the precipitant solution may be selected from OH - ，CO 3 2- 、HCO 3 - Or oxalate radical C 2 O 4 2- For example: the precipitant solution is sodium hydroxide solution.
In the present invention, the concentration of the precipitant solution is preferably 0.5 to 8mol/L, more preferably 2 mol/L.
In the present invention, a complexing agent may be added to the precipitant solution as is conventional in the art.
The complexing agent can be a complexing agent conventional in the art, such as ammonia water, and the concentration of the ammonia water is preferably 0.3-1mol/L, such as 0.56 mol/L.
In the present invention, the rotation speed under the supergravity condition is preferably 1800-3000rpm, such as 2200rpm, 2500rpm or 2700 rpm.
In the present invention, supergravity means the acceleration of a substance in a specific gravity (9.8 m/s) of the earth 2 ) Much larger forces are experienced in much larger environments than the gravitational force of the earth, and hypergravity is typically achieved by high speed rotation. Different reactants are fed into the reaction cavity rotating at high speed according to the proportion, and the interior of the reaction cavity is filled with fillers with different structures. The fluid entering the cavity is generated by high-speed rotationIs rapidly dispersed and mixed under the action of centrifugal force, thereby realizing rapid micro-scale mixing reaction between fluids.
In the invention, the salt solution and the precipitant (alkali) solution can be rapidly mixed in a micro scale by virtue of supergravity, so that the concentration is consistent during the coprecipitation reaction, and the formed precipitate particles are more uniform in size.
In the present invention, the overweight condition can be achieved by a hypergravity mixer. The filler of the hypergravity mixer can be columnar or reticular. The hypergravity mixer may be selected from conventional commercially available hypergravity mixers available, such as those manufactured by Kyoto technologies, Inc. of Beijing Kaimei, with the hypergravity mixer equipment model KMN-BCUT-2021-06.
Wherein, in the super-gravity mixer, the salt solution of the transition metal and the precipitant solution are pumped into the super-gravity mixer at a certain flow rate to carry out rapid reaction.
Preferably, the salt solution of the transition metal and the precipitant solution are pumped into the hypergravity mixer at a flow ratio (L/min: L/min) of (0.8-1.2) to (0.8-1.2). The ratio of the flow rates is preferably 1:1 (L/min: L/min).
In the present invention, preferably, the rate at which the salt solution of the transition metal is pumped into the hypergravity mixer is 0.5 to 4L/min, such as 1L/min or 2L/min.
In the present invention, preferably, the flow rate at which the precipitant solution is pumped into the hypergravity mixer is 0.5 to 4L/min, such as 1L/min or 2L/min.
In the present invention, the temperature of the coprecipitation reaction is preferably 40 to 60 ℃, and more preferably 50 ℃.
In the present invention, the time of the coprecipitation reaction is preferably 0.01 to 0.1 s. The reaction time is the retention time of the material in the hypergravity mixer, can be determined according to the diameter and the thickness of the reactor packing and the rotating speed of the reactor, and can be calculated according to a basic physical equation.
In the present invention, after the coprecipitation reaction and before the precipitate is obtained, solid-liquid separation, washing, and drying may be performed according to a conventional method in the art, so as to obtain the precipitate.
The solid-liquid separation operation can be a solid-liquid separation operation conventional in the art, such as suction filtration, centrifugation or pressure filtration.
Wherein the drying operation may be a drying operation conventional in the art. Preferably the drying temperature is 100-. The drying time is 10-18 h. The drying may be performed under an air atmosphere.
In the present invention, preferably, the method further comprises the following steps: and carrying out secondary granulation on the precipitate. By combining secondary granulation and hypergravity, the anode material precursor with uniform particle appearance and size and good performance can be quickly synthesized in a multi-field reaction process in a coupling manner, and the microstructure and the crystal structure of the precursor synthesized by a single hypergravity field are improved.
Wherein, the second granulation comprises spray drying, hydrothermal method or aging method, preferably spray drying or hydrothermal method, more preferably hydrothermal method.
When the spray drying is employed for the secondary granulation, the spray drying preferably includes the steps of: dissolving the precipitate in solvent, and spraying at inlet temperature of 150-200 deg.C and outlet temperature of 80-150 deg.C.
Wherein the inlet temperature is preferably 200 ℃ and the outlet temperature is preferably 120 ℃.
Among them, the solvent may be a solvent conventional in the art, and preferably is water or an ethanol-water solution.
The equipment used for spray drying may be equipment conventionally used in spray drying processes in the art, such as a spray dryer.
Through coupling spray drying, secondary granulation can be carried out to form spherical secondary particles with large particle size, and the tap density of the anode material and the stability of the material in the charging and discharging processes are increased.
When the hydrothermal method is used for secondary granulation, the method generally comprises the following steps: keeping the precipitate at a constant temperature for a certain time.
Wherein the heating temperature used in the hydrothermal method is preferably 120-180 ℃, more preferably 180 ℃.
Wherein the heating time in the hydrothermal method is preferably 8-20h, such as 10, 12 or 14h, and more preferably 12 h. In the present invention, it was found that the hydrothermal time varies and has an influence on the product properties (e.g., cycle stability).
In the present invention, the equipment used in the hydrothermal method can be equipment conventionally used in hydrothermal method treatment in the art, such as a hydrothermal kettle.
Spherical particles with uniform appearance are obtained by dissolution-recrystallization through a coupled hydrothermal method, and a single crystal anode material can be synthesized, so that the cycling stability of the anode material is greatly improved. Meanwhile, the small-particle single crystal material synthesized by the supergravity-hydrothermal method is also beneficial to reducing the sintering temperature, time and the like during the subsequent preparation of the anode material.
The invention also provides the precursor of the cathode material prepared by the preparation method.
The invention also provides a preparation method of the cathode material, which comprises the following steps: and sintering the mixture of the precursor of the cathode material and the sodium source.
In the invention, preferably, the positive electrode material is a nickel-iron-manganese ternary sodium ion positive electrode material Na [ Ni ] 1/3 Fe 1/ 3 Mn 1/3 ]O 2 。
In the present invention, the sodium source may be a sodium source conventional in the art, such as sodium carbonate.
In the present invention, the molar ratio of the positive electrode material precursor to the sodium source may be in a conventional stoichiometric ratio, preferably 2: 1.
In the present invention, the sintering may be performed by a sintering method that is conventional in the art.
In the present invention, the sintering may be performed in an air atmosphere.
In the present invention, preferably, the sintering includes the steps of: the first stage of the process: keeping the temperature constant at 500-600 ℃ for 4-8h, and carrying out a second stage of procedure: keeping the temperature for 15-24h at 870-1000 ℃.
The temperature in the first stage procedure and the second stage procedure can be raised in a programmed temperature raising manner, and the temperature raising rate is preferably 2-8 ℃/min, more preferably 5 ℃/min.
Preferably, the first stage procedure includes the following steps: keeping the temperature at 550 ℃ for 5 h.
Preferably, the second procedure includes the following steps: keeping the temperature at 900 ℃ for 18 h.
More preferably, the sintering comprises the following steps: 5 ℃/min is increased to 550 ℃ and is kept constant for 5h, and then 5 ℃/min is increased to 900 ℃ and is kept constant for 18 h.
The invention also provides the cathode material prepared by the preparation method of the cathode material.
The invention also provides the application of the precursor of the positive electrode material or the positive electrode material in the battery.
The battery is preferably a sodium ion battery.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) the preparation method of the precursor of the cathode material, provided by the invention, is based on a supergravity technology, realizes the rapid and uniform mixing of transition metal salt ions and a precipitator or a complexing agent on a microscale through rapid micro-mixing reaction, enhances the production efficiency, produces precursor particles with uniform components, and greatly shortens the mixing time and the reaction time compared with the existing coprecipitation method (the mixing and aging time of the existing coprecipitation process is about 20 hours, and the time for synthesizing the precursor is less than 1 hour). In addition, the preparation method has the advantages of low energy consumption, short time consumption, continuous and controllable reaction, high equipment utilization rate and simple process, can meet the requirement of large-scale production, and realizes large-scale, rapid and high-quality production of the precursor.
(2) The invention further provides a method for continuously preparing the transition metal precipitate as a material precursor based on a multi-field coupling process of a supergravity technology and other technologies (spray drying and a hydrothermal method), further realizes accurate regulation and control of particle size and morphology, improves the consistency of the particle size of the product, improves the electrochemical performance (especially the cycle performance) of the precursor and the anode material, and avoids long-time heating and aging treatment processes.
(3) The precursor prepared by the method has good appearance, particle size and consistency, and the anode material prepared from the precursor has excellent electrochemical performance, and particularly the cycle stability is obviously improved.
Drawings
FIG. 1 is a schematic flow diagram of a supergravity rapid microscale mixing reaction coupled with other techniques;
FIG. 2 shows the synthesis of Na [ Ni ] in example 1 1/3 Fe 1/3 Mn 1/3 ]O 2 SEM pictures of the compounds;
FIG. 3 shows the synthesis of Na [ Ni ] in example 1 1/3 Fe 1/3 Mn 1/3 ]O 2 A charge-discharge curve chart of the compound button cell;
FIG. 4 shows the synthesis of Na [ Ni ] in example 1 1/3 Fe 1/3 Mn 1/3 ]O 2 A change diagram of the cyclic charge-discharge capacity of the compound button cell;
FIG. 5 shows the synthesis of Na [ Ni ] in example 1 1/3 Fe 1/3 Mn 1/3 ]O 2 An XRD pattern of the compound;
FIG. 6 shows the synthesis of Na [ Ni ] in example 2 1/3 Fe 1/3 Mn 1/3 ]O 2 A charge-discharge curve chart of the compound button cell;
FIG. 7 shows the synthesis of Na [ Ni ] in example 2 1/3 Fe 1/3 Mn 1/3 ]O 2 A change diagram of the cyclic charge-discharge capacity of the compound button cell;
FIG. 8 shows the synthesis of Na [ Ni ] in example 3 1/3 Fe 1/3 Mn 1/3 ]O 2 SEM pictures of the compounds;
FIG. 9 shows the synthesis of Na [ Ni ] in example 3 1/3 Fe 1/3 Mn 1/3 ]O 2 A charge-discharge curve chart of the compound button cell;
FIG. 10 is a schematic view ofEXAMPLE 3 Synthesis of Na [ Ni ] 1/3 Fe 1/3 Mn 1/3 ]O 2 A change diagram of the cyclic charge-discharge capacity of the compound button cell;
FIG. 11 shows the synthesis of Na [ Ni ] in example 3 1/3 Fe 1/3 Mn 1/3 ]O 2 An XRD pattern of the compound;
FIG. 12 shows the synthesis of Na [ Ni ] in example 4 1/3 Fe 1/3 Mn 1/3 ]O 2 SEM spectra of the compounds;
FIG. 13 shows the synthesis of Na [ Ni ] in example 4 1/3 Fe 1/3 Mn 1/3 ]O 2 A charge-discharge curve chart of the compound button cell;
FIG. 14 shows the synthesis of Na [ Ni ] in example 4 1/3 Fe 1/3 Mn 1/3 ]O 2 A change diagram of the cyclic charge-discharge capacity of the compound button cell;
FIG. 15 shows the synthesis of Na [ Ni ] in example 4 1/3 Fe 1/3 Mn 1/3 ]O 2 XRD pattern of compound.
FIG. 16 shows the synthesis of Na [ Ni ] in example 5 1/3 Fe 1/3 Mn 1/3 ]O 2 A charge-discharge curve chart of the compound button cell;
FIG. 17 shows the synthesis of Na [ Ni ] in example 5 1/3 Fe 1/3 Mn 1/3 ]O 2 And (3) a change chart of the cyclic charge-discharge capacity of the compound button cell.
The reference numerals in fig. 1 are as follows: 1. a raw material kettle filled with a transition metal salt solution; 2. a raw material kettle filled with a precipitant solution; 3. a flow meter; 4. a hypergravity reactor; 5. a spray dryer; 6. a hydrothermal kettle.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
A flow chart of an experimental device for synthesizing a precursor by rapidly mixing a ternary precursor of nickel, iron and manganese (molar ratio 1:1:1) is shown in fig. 1. The raw materials in the raw material kettle 1 filled with the transition metal salt solution and the raw material kettle 2 filled with the precipitant solution enter a hypergravity reactor 4 through a flow meter 3 to carry out mixing reaction, and then secondary granulation can be carried out through a spray dryer 5 or a hydrothermal kettle 6.
In the following examples, a hypergravity mixer with a volume of 0.8L was used.
Example 1
A preparation method of a precursor of a positive electrode material specifically comprises the following steps:
1) weighing 175.2g of nickel sulfate hexahydrate, 112.7g of manganous sulfate hydrate and 185.3g of ferrous sulfate heptahydrate according to the molar ratio of Ni to Fe to Mn being 1 to 1, adding 791.3g of deionized water into a salt solution tank, and stirring until the solution is dissolved, wherein the concentration of the salt solution is 2 mol/L; wherein the concentration of the salt solution refers to the total concentration of all transition metal ions in the salt solution;
2) preparing 2mol/L NaOH solution into an alkali liquor tank, adding ammonia water in a certain proportion into the alkali liquor tank as a complexing agent, wherein the concentration of the ammonia water in the alkali liquor is 0.56 mol/L;
3) starting the super-gravity mixer, and adjusting the rotating speed to 2500 rpm;
4) adjusting the flow rates of the saline solution and alkali solution metering pumps to 1L/min, and simultaneously starting the two metering pumps; the salt solution and the alkali solution are subjected to coprecipitation reaction in a hypergravity mixer, and the pH value of the solution after the salt solution and the alkali solution are mixed is controlled to be 9-11; the reaction temperature is controlled at 50 ℃, the reaction time is represented by the rotating speed of the super-gravity filler, and is generally 0.01-0.1s (the discharge rate is consistent with the feeding rate, the reaction time is the retention time of the material in the reactor, and is related to the volume of the reactor and the rotating speed of the super-gravity filler);
5) and collecting the discharged material of the hypergravity reactor, and carrying out vacuum filtration and washing. And (3) placing the filter cake in a blast oven to be dried for 10h at 120 ℃ for removing water. The dried solid powder is the nickel-iron-manganese ternary precursor.
Preparing a positive electrode material:
the precursor prepared above was uniformly mixed with a desired sodium source (Na) 2 CO 3 ) The molar ratio of the sodium source to the precursor is 1: 2, preparing the nickel-iron-manganese ternary sodium ion positive electrode material Na [ Ni ] through a sintering process (sintering in air atmosphere, raising the temperature of 5 ℃/min to 550 ℃, keeping the temperature for 5 hours, then raising the temperature of 5 ℃/min to 900 ℃, keeping the temperature for 18 hours) 1/3 Fe 1/3 Mn 1/3 ]O 2 。
Example 2
A method for producing a precursor of a positive electrode material, this comparative example being the same as example 1 except for the following conditions:
the rotating speed of the hypergravity mixer in the step (3) is 1800 rpm.
Preparing a positive electrode material:
the preparation steps are the same as those of the example 1, and the nickel-iron-manganese ternary sodium ion positive electrode material Na [ Ni ] is prepared 1/3 Fe 1/3 Mn 1/3 ]O 2 。
Example 3
A preparation method of a precursor of a positive electrode material is used for preparing a transition metal precipitate as the precursor through a rapid microscale mixing reaction coupled spray drying process, and specifically comprises the following steps:
1) weighing 175.2g of nickel sulfate hexahydrate, 112.7g of manganous sulfate hydrate and 185.3g of ferrous sulfate heptahydrate according to the molar ratio of Ni to Fe to Mn being 1 to 1, adding 791.3g of deionized water into a salt solution tank, and stirring until the mixture is dissolved; the concentration of the salt solution is 2 mol/L;
2) preparing 2mol/L NaOH solution into an alkali liquor tank, adding ammonia water in a certain proportion into the alkali liquor tank as a complexing agent, wherein the concentration of the ammonia water in the alkali liquor is 0.56 mol/L;
3) starting the super-gravity mixer, and adjusting the rotating speed to 2500 rpm;
4) adjusting the flow rates of the saline solution and alkali solution metering pumps to 1L/min, and simultaneously starting the two metering pumps; the salt solution and the alkali solution are subjected to coprecipitation reaction in a hypergravity mixer, and the pH value of the solution after the salt solution and the alkali solution are mixed is controlled to be 9-11; the reaction temperature is controlled at 50 ℃, the rotating speed of the super-gravity filler is embodied, and is generally 0.01-0.1 s;
5) and collecting the discharged material of the hypergravity reactor, and carrying out vacuum filtration and washing. Dissolving the obtained solid in deionized water, and performing secondary granulation by spray drying (inlet temperature is 200 ℃, outlet temperature is 120 ℃, and equipment is a spray dryer) to obtain powder, namely the nickel-iron-manganese ternary precursor after spray drying treatment.
Preparing a positive electrode material:
uniformly mixing the precursor prepared in the step (5) with a required sodium source ((Na) 2 CO 3 ) The molar ratio of the sodium source to the precursor is 1: 2, preparing the nickel-iron-manganese ternary sodium ion positive electrode material Na [ Ni ] through a sintering process (sintering in air atmosphere, raising the temperature of 5 ℃/min to 550 ℃, keeping the temperature for 5 hours, then raising the temperature of 5 ℃/min to 900 ℃, keeping the temperature for 18 hours) 1/3 Fe 1/3 Mn 1/3 ]O 2 。
Example 4
A preparation method of a precursor of a positive electrode material is used for preparing a transition metal precipitate as the precursor by coupling a rapid microscale mixing reaction with a hydrothermal process, and specifically comprises the following steps:
1) weighing 175.2g of nickel sulfate hexahydrate, 112.7g of manganous sulfate hydrate and 185.3g of ferrous sulfate heptahydrate according to the molar ratio of Ni to Fe to Mn being 1 to 1, adding 791.3g of deionized water into a salt solution tank, and stirring until the solution is dissolved, wherein the concentration of the salt solution is 2 mol/L;
2) preparing 2mol/L NaOH solution, adding ammonia water in a certain proportion into an alkali liquor tank to serve as a complexing agent, wherein the concentration of the ammonia water in the alkali liquor is 0.56 mol/L;
3) starting the super-gravity mixer, and adjusting the rotating speed to 2500 rpm;
4) adjusting the flow rates of the metering pumps of the saline solution and the alkali solution to be 1L/min, and simultaneously starting the two metering pumps; the salt solution and the alkali solution are subjected to coprecipitation reaction in a hypergravity mixer, and the pH value of the solution after the salt solution and the alkali solution are mixed is controlled to be 9-11; the reaction temperature is controlled at 50 ℃, and the reaction time is represented by the rotating speed of the super-gravity filler, and is generally 0.01-0.1 s;
5) collecting the discharge of the supergravity reactor, directly placing the discharge in a hydrothermal kettle, keeping the temperature at 180 ℃ for 12h, carrying out vacuum filtration and washing on the hydrothermal material, and placing the filter cake in a blast oven for drying at 120 ℃ for 10h for removing water. The obtained powder is the nickel-iron-manganese ternary precursor after hydrothermal treatment.
Preparing a positive electrode material:
uniformly mixing the precursor prepared in the step (5) with a required sodium source (Na) 2 CO 3 ) The molar ratio of the sodium source to the precursor is 1: 2, by sinteringThe process (sintering in air atmosphere, 5 ℃/min rising to 550 ℃ and keeping the temperature for 5h, then 5 ℃/min rising to 900 ℃ and keeping the temperature for 18h) is carried out to prepare the nickel-iron-manganese ternary sodium ion anode material Na [ Ni ] 1/3 Fe 1/3 Mn 1/3 ]O 2 。
Example 5
A preparation method of a precursor of a positive electrode material is used for preparing a transition metal precipitate as the precursor by coupling a rapid microscale mixing reaction with a hydrothermal process, and specifically comprises the following steps:
1) weighing 175.2g of nickel sulfate hexahydrate, 112.7g of manganous sulfate hydrate and 185.3g of ferrous sulfate heptahydrate according to the molar ratio of Ni to Fe to Mn being 1 to 1, adding 791.3g of deionized water into a salt solution tank, and stirring until the solution is dissolved, wherein the concentration of the salt solution is 2 mol/L;
2) preparing 2mol/L NaOH solution in an alkali liquor tank;
3) starting the super-gravity mixer, and adjusting the rotating speed to 2500 rpm;
4) adjusting the flow rates of the metering pumps of the saline solution and the alkali solution to be 2L/min, and simultaneously starting the two metering pumps; the salt solution and the alkali solution are subjected to coprecipitation reaction in a hypergravity mixer, and the pH value of the solution after the salt solution and the alkali solution are mixed is controlled to be 9-11; the reaction temperature is controlled at 50 ℃, and the reaction time is represented by the rotating speed of the super-gravity filler, and is generally 0.01-0.1 s;
5) collecting the discharge of the hypergravity reactor, directly placing the discharge in a hydrothermal kettle, keeping the temperature at 180 ℃ for 14h, carrying out vacuum filtration and washing on the hydrothermal material, and placing the filter cake in a blast oven for drying at 120 ℃ for 10h for removing water. The obtained powder is the nickel-iron-manganese ternary precursor after hydrothermal treatment.
Preparing a positive electrode material:
uniformly mixing the precursor prepared in the step (5) with a required sodium source (Na) 2 CO 3 ) The molar ratio of the sodium source to the precursor is 2:1, and the nickel-iron-manganese ternary sodium ion anode material Na [ Ni ] is prepared through a sintering process (sintering in air atmosphere, raising the temperature of 5 ℃/min to 550 ℃, keeping the temperature for 5h, then raising the temperature of 5 ℃/min to 900 ℃, keeping the temperature for 18h) 1/3 Fe 1/3 Mn 1/3 ]O 2 。
Effects of the embodiment
1. Material characterization
SEM and XRD characterization were performed on the nickel-iron-manganese ternary sodium ion positive electrode materials prepared in examples 1, 3, and 4, fig. 2, 8, and 12 are SEM images of the nickel-iron-manganese ternary sodium ion positive electrode materials obtained in examples 1, 3, and 4, respectively, and fig. 5, 11, and 15 are XRD images of the nickel-iron-manganese ternary sodium ion positive electrode materials obtained in examples 1, 3, and 4, respectively.
According to XRD patterns, the ternary sodium-ion battery cathode material with good crystal form is synthesized by the synthesis process.
2. Electrochemical performance test
Manufacturing a button cell for electrochemical performance test: the nickel-iron-manganese ternary sodium ion positive electrode material prepared in the examples 1-5, the conductive agent and the binder are uniformly mixed according to the mass ratio of 8:1:1, coated on an aluminum foil, and dried in a vacuum oven for 12 hours to prepare the pole piece. Taking out the pole piece, and cutting the pole piece into a circular sheet with the diameter of 12 mm. And (3) manufacturing the button cell in a glove box, taking a positive electrode shell, placing a pole piece on the positive electrode shell, dripping a certain amount of electrolyte, and then placing a diaphragm for standby. And cutting, rolling and punching the metal sodium to obtain the round sodium tablet. And (3) placing the nickel screen on the sodium sheet, then placing the sodium sheet into the positive electrode shell, adding the electrolyte, then covering the negative electrode shell, and finally punching and sealing to obtain the button cell. (note: the button cell is a half cell, the half cell is generally used for laboratory tests, the performance is generally lower than that of a full cell, and the normal phenomenon is observed.)
And (3) electrochemical performance testing: the button cell (half cell) prepared above was tested at 0.2C, 25 ℃, 2-4V, respectively, to obtain the charge and discharge curves, as shown in fig. 3, 6, 9, 13, 16. The cyclic charge-discharge capacity variation diagram is obtained by testing at 1C, 25 ℃ and 2-4V, and is shown in figures 4, 7, 10, 14 and 17.
The electrochemical performance test shows that the electrochemical performance results are shown in the following table 1:
table 1 examples 1-5 results of electrochemical performance testing of nickel-iron-manganese ternary sodium ion positive electrode materials
According to electrochemical performance test results, the anode material prepared by the direct super-gravity method has high initial capacity, but has general cycle performance; after secondary granulation in the coupling spray drying process, the initial capacity is reduced a little, but the cycle performance is greatly improved; after the hydrothermal process is coupled, the precursor is subjected to a 'dissolving-recrystallization' process, so that the morphology of the material is greatly improved, and although the initial capacity is slightly reduced, the cycle stability is greatly improved.
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and that the scope of the invention is defined by the appended claims. Various changes and modifications to these embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications are within the scope of the invention.
Claims (10)
1. A preparation method of a precursor of a positive electrode material is characterized by comprising the following steps:
mixing a salt solution of transition metal and a precipitant solution under a supergravity condition, and carrying out coprecipitation reaction to obtain a precipitate; wherein,
the transition metal is selected from one or more of nickel, iron, manganese, copper, aluminum, cerium, cobalt, zinc, tin and titanium;
the rotating speed under the supergravity condition is 500-3000 rpm.
2. The method for preparing a precursor of a positive electrode material according to claim 1, wherein the precursor of a positive electrode material is a precursor of a positive electrode material for a sodium-ion battery;
and/or the precursor of the anode material is a nickel-iron-manganese ternary precursor;
and/or the transition metal is nickel, iron and manganese; wherein, the molar ratio of nickel, iron and manganese is preferably (0-8): (1-8): (1-5), e.g., 1:1: 1;
and/or the salt in the transition metal salt solution is sulfate;
and/or the salt solution of the transition metal comprises a mixed solution of nickel sulfate, manganous sulfate and ferrous sulfate;
and/or the concentration of the salt solution of the transition metal is 0.5-4mol/L, preferably 2mol/L, wherein the concentration refers to the total concentration of all transition metal ions in the salt solution;
and/or the anion in the precipitant solution is selected from OH - 、CO 3 2- 、HCO 3 - Or oxalate radical C 2 O 4 2- For example, the precipitant solution is a sodium hydroxide solution;
and/or the concentration of the precipitant solution is 0.5-8mol/L, preferably 2 mol/L;
and/or, the precipitant solution further comprises a complexing agent, wherein the complexing agent can be ammonia water, and the concentration of the ammonia water is preferably 0.3-1mol/L, such as 0.56 mol/L.
3. The method for preparing a precursor of a positive electrode material according to claim 1, wherein the rotational speed of the supergravity mixer is 1800-3000rpm, such as 2200rpm, 2500rpm or 2700 rpm;
and/or, the overweight condition is achieved by a hypergravity mixer; wherein,
preferably, said salt solution of a transition metal and said precipitant solution are pumped into said hypergravity mixer at a ratio of (0.8-1.2) to (0.8-1.2) flow rate; the ratio of the flow rates is preferably 1: 1;
preferably, the rate at which the salt solution of the transition metal is pumped into the hypergravity mixer is from 0.5 to 4L/min, such as 1L/min or 2L/min;
preferably, the flow rate at which the precipitant solution is pumped into the hypergravity mixer is 0.5-4L/min, such as 1L/min or 2L/min;
and/or the temperature of the coprecipitation reaction is 40-60 ℃, preferably 50 ℃;
and/or the time of the coprecipitation reaction is 0.01-0.1 s;
and/or after the coprecipitation reaction and before the precipitate is obtained, carrying out solid-liquid separation, washing and drying to obtain the precipitate; wherein,
the solid-liquid separation operation can be suction filtration, centrifugation or filter pressing;
the drying temperature can be 100-180 ℃, preferably 120 ℃; the drying time can be 10-18 h; the drying may be performed under an air atmosphere.
4. The method for producing a precursor of a positive electrode material according to any one of claims 1 to 3, further comprising the steps of: and carrying out secondary granulation on the precipitate.
5. The method for preparing a precursor of a positive electrode material according to claim 4, wherein the second granulation comprises spray drying, hydrothermal method or aging method, preferably spray drying or hydrothermal method, more preferably hydrothermal method; wherein,
when the spray drying is adopted for secondary granulation, the spray drying comprises the following steps: dissolving the precipitate in a solvent, and spraying out the precipitate at the inlet temperature of 150-200 ℃ and the outlet temperature of 80-150 ℃;
the inlet temperature is preferably 200 ℃ and the outlet temperature is preferably 120 ℃;
the solvent is preferably water or an ethanol-water solution;
when the hydrothermal method is adopted for secondary granulation, the heating temperature adopted by the hydrothermal method is 120-180 ℃, and preferably 180 ℃;
wherein the heating time in the hydrothermal method is preferably 8-20h, such as 10, 12 or 14 h.
6. A precursor for a positive electrode material produced by the method for producing a precursor for a positive electrode material according to any one of claims 1 to 5.
7. The preparation method of the cathode material is characterized by comprising the following steps of: sintering the mixture of the precursor of the positive electrode material according to claim 6 and a sodium source.
8. The method for preparing the positive electrode material according to claim 7, wherein the positive electrode material is a nickel-iron-manganese ternary sodium ion positive electrode material Na [ Ni ] 1/3 Fe 1/3 Mn 1/3 ]O 2 ；
And/or the sodium source is sodium carbonate;
and/or the molar ratio of the positive electrode material precursor to the sodium source is 2: 1;
and/or, the sintering is carried out in an air atmosphere;
and/or, the sintering comprises the following steps: the first stage of the process: keeping the temperature constant at 500-600 ℃ for 4-8h, and carrying out a second stage of procedure: keeping the temperature for 15-24h at 870-1000 ℃;
wherein, preferably, the temperature in the first stage procedure and the second stage procedure is raised in a programmed temperature raising manner, and the rate of raising the temperature is preferably 2-8 ℃/min, more preferably 5 ℃/min;
preferably, the first stage procedure includes the following steps: keeping the temperature at 550 ℃ for 5 hours;
wherein the second procedure comprises the steps of: keeping the temperature at 900 ℃ for 18 h;
more preferably, the sintering comprises the following steps: 5 ℃/min is increased to 550 ℃ and is kept constant for 5h, and then 5 ℃/min is increased to 900 ℃ and is kept constant for 18 h.
9. A positive electrode material produced by the method for producing a positive electrode material according to claim 7 or 8.
10. Use of the positive electrode material precursor according to claim 6 or the positive electrode material according to claim 9 in a battery;
wherein the battery is preferably a sodium ion battery.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210714671.9A CN115072801A (en) | 2022-06-22 | 2022-06-22 | Positive electrode material precursor, positive electrode material, preparation method and application thereof |
| PCT/CN2023/101190 WO2023246724A1 (en) | 2022-06-22 | 2023-06-20 | Anode material precursor, anode material, method for preparing same, and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210714671.9A CN115072801A (en) | 2022-06-22 | 2022-06-22 | Positive electrode material precursor, positive electrode material, preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115072801A true CN115072801A (en) | 2022-09-20 |
Family
ID=83253844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210714671.9A Pending CN115072801A (en) | 2022-06-22 | 2022-06-22 | Positive electrode material precursor, positive electrode material, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115072801A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115432718A (en) * | 2022-11-08 | 2022-12-06 | 浙江钠创新能源有限公司 | Hypergravity synthesis method and application of prussian blue material |
| CN115872461A (en) * | 2022-12-07 | 2023-03-31 | 电子科技大学长三角研究院(湖州) | Method for preparing nickel-iron-manganese carbonate spherical precursor of sodium ion battery positive electrode material |
| CN116374986A (en) * | 2023-04-14 | 2023-07-04 | 河南佰利新能源材料有限公司 | Lithium iron phosphate positive electrode material, and preparation method and application thereof |
| WO2023246724A1 (en) * | 2022-06-22 | 2023-12-28 | 浙江钠创新能源有限公司 | Anode material precursor, anode material, method for preparing same, and use thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104953172A (en) * | 2015-07-24 | 2015-09-30 | 上海中聚佳华电池科技有限公司 | Sodium-ion battery cathode materials, preparation method of sodium-ion battery cathode materials, and sodium-ion batteries |
| CN105322155A (en) * | 2014-06-06 | 2016-02-10 | 安泰科技股份有限公司 | Lithium-rich manganese-based layered composite oxide cathode material, preparation method and application thereof |
| CN106564967A (en) * | 2016-10-31 | 2017-04-19 | 安泰科技股份有限公司 | Lithium-rich manganese-based cathode material precursor, cathode material and preparation method thereof |
| CN107946591A (en) * | 2017-11-21 | 2018-04-20 | 山东理工大学 | A kind of nickelic presoma of sodium-ion battery and its preparation method with positive electrode |
| CN109817970A (en) * | 2019-01-31 | 2019-05-28 | 上海紫剑化工科技有限公司 | A kind of monocrystalline sodium ion battery electrode material and preparation method thereof |
| US20190386293A1 (en) * | 2016-12-20 | 2019-12-19 | Byd Company Limited | Ternary material and preparation method thereof, battery slurry, positive electrode and lithium battery |
-
2022
- 2022-06-22 CN CN202210714671.9A patent/CN115072801A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105322155A (en) * | 2014-06-06 | 2016-02-10 | 安泰科技股份有限公司 | Lithium-rich manganese-based layered composite oxide cathode material, preparation method and application thereof |
| CN104953172A (en) * | 2015-07-24 | 2015-09-30 | 上海中聚佳华电池科技有限公司 | Sodium-ion battery cathode materials, preparation method of sodium-ion battery cathode materials, and sodium-ion batteries |
| CN106564967A (en) * | 2016-10-31 | 2017-04-19 | 安泰科技股份有限公司 | Lithium-rich manganese-based cathode material precursor, cathode material and preparation method thereof |
| US20190386293A1 (en) * | 2016-12-20 | 2019-12-19 | Byd Company Limited | Ternary material and preparation method thereof, battery slurry, positive electrode and lithium battery |
| CN107946591A (en) * | 2017-11-21 | 2018-04-20 | 山东理工大学 | A kind of nickelic presoma of sodium-ion battery and its preparation method with positive electrode |
| CN109817970A (en) * | 2019-01-31 | 2019-05-28 | 上海紫剑化工科技有限公司 | A kind of monocrystalline sodium ion battery electrode material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023246724A1 (en) * | 2022-06-22 | 2023-12-28 | 浙江钠创新能源有限公司 | Anode material precursor, anode material, method for preparing same, and use thereof |
| CN115432718A (en) * | 2022-11-08 | 2022-12-06 | 浙江钠创新能源有限公司 | Hypergravity synthesis method and application of prussian blue material |
| CN115872461A (en) * | 2022-12-07 | 2023-03-31 | 电子科技大学长三角研究院(湖州) | Method for preparing nickel-iron-manganese carbonate spherical precursor of sodium ion battery positive electrode material |
| CN116374986A (en) * | 2023-04-14 | 2023-07-04 | 河南佰利新能源材料有限公司 | Lithium iron phosphate positive electrode material, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115072801A (en) | Positive electrode material precursor, positive electrode material, preparation method and application thereof | |
| CN103825016B (en) | A kind of rich nickelic positive electrode of lithium and preparation method thereof | |
| CN103296263B (en) | Preparation method of lithium-ion battery positive electrode material spherical nickel-cobalt-lithium aluminate | |
| CN112531158B (en) | High-nickel ternary single crystal material and preparation method thereof | |
| CN107482172B (en) | High-rate layered lithium-rich manganese-based cathode material and preparation method thereof | |
| CN104409716A (en) | Nickel lithium ion battery positive material with concentration gradient, and preparation method thereof | |
| CN105304893A (en) | Preparation method of lithium ion battery anode active material lithium nickel manganese oxide | |
| CN105161679A (en) | Lithium-rich cathode material and preparation method and application thereof | |
| CN107293744A (en) | High-voltage monocrystal-like ternary cathode material and preparation method thereof | |
| CN109678219B (en) | Preparation method of nano layered lithium nickel cobalt manganese oxide | |
| WO2015039490A1 (en) | Lithium-rich anode material and preparation method thereof | |
| CN109817901B (en) | Preparation method of nickel-cobalt-aluminum doped spherical precursor | |
| WO2012020769A1 (en) | Method for producing nickel-containing complex compound | |
| CN108767216A (en) | Anode material for lithium-ion batteries and its synthetic method with the full concentration gradient of variable slope | |
| CN109626447A (en) | Nickelic anode material for lithium-ion batteries of a kind of concentration gradient magnesium doping and preparation method thereof | |
| CN105552363B (en) | A kind of nickel cobalt aluminum oxide presoma, nickel cobalt aluminum oxide and preparation method thereof | |
| WO2024040903A1 (en) | Method for preparing ferromanganese phosphate by coprecipitation and use thereof | |
| CN108987740B (en) | Nickel-cobalt lithium aluminate anode material, preparation method thereof and battery applying nickel-cobalt lithium aluminate anode material | |
| CN106910887A (en) | A kind of lithium-rich manganese-based anode material, its preparation method and the lithium ion battery comprising the positive electrode | |
| CN103647070B (en) | A kind of rare earth samarium is modified the preparation method of tertiary cathode material | |
| CN103570083A (en) | Preparation method of nickel-cobalt-aluminum spherical precursor of positive material of lithium ion battery | |
| CN114162881A (en) | Preparation method of anion in-situ doped high-nickel ternary cathode material | |
| CN114426313A (en) | High-energy-density ternary cathode material and preparation method and application thereof | |
| CN114835173A (en) | Positive electrode material precursor, preparation method thereof and positive electrode material | |
| WO2023246724A1 (en) | Anode material precursor, anode material, method for preparing same, and use thereof |
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 |