CN113178558A - Composite manganese-based positive electrode material and preparation method thereof - Google Patents
Composite manganese-based positive electrode material and preparation method thereof Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 104
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 54
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 229910006554 Li1+xMn2-x-yMyO4 Inorganic materials 0.000 claims abstract description 3
- 229910006601 Li1+xMn2−x−yMyO4 Inorganic materials 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 76
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 61
- 238000002156 mixing Methods 0.000 claims description 42
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 41
- 229910019142 PO4 Inorganic materials 0.000 claims description 38
- 238000002844 melting Methods 0.000 claims description 36
- 230000008018 melting Effects 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 33
- 235000021317 phosphate Nutrition 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 28
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 27
- 229910021529 ammonia Inorganic materials 0.000 claims description 26
- 230000001590 oxidative effect Effects 0.000 claims description 26
- 238000003786 synthesis reaction Methods 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910052782 aluminium Inorganic materials 0.000 claims description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 23
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 21
- 229910052759 nickel Inorganic materials 0.000 claims description 21
- 230000002194 synthesizing effect Effects 0.000 claims description 21
- 239000010452 phosphate Substances 0.000 claims description 20
- 229910002651 NO3 Inorganic materials 0.000 claims description 19
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 19
- 229910017052 cobalt Inorganic materials 0.000 claims description 19
- 239000010941 cobalt Substances 0.000 claims description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 17
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 17
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 13
- 229910010227 LiAlF4 Inorganic materials 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 13
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 11
- 229910012140 Li3AlF6 Inorganic materials 0.000 claims description 11
- 229910016130 LiNi1-x Inorganic materials 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 125000005341 metaphosphate group Chemical group 0.000 claims description 11
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 9
- 239000010406 cathode material Substances 0.000 claims description 9
- 150000002222 fluorine compounds Chemical class 0.000 claims description 9
- 150000004677 hydrates Chemical class 0.000 claims description 9
- 150000003891 oxalate salts Chemical class 0.000 claims description 9
- 229910021582 Cobalt(II) fluoride Inorganic materials 0.000 claims description 8
- 150000004767 nitrides Chemical class 0.000 claims description 8
- 229910003005 LiNiO2 Inorganic materials 0.000 claims description 7
- 229910021570 Manganese(II) fluoride Inorganic materials 0.000 claims description 7
- 229910002706 AlOOH Inorganic materials 0.000 claims description 6
- 229910010092 LiAlO2 Inorganic materials 0.000 claims description 6
- 229910021587 Nickel(II) fluoride Inorganic materials 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910014330 LiNi1-x-yCoxAlyO2 Inorganic materials 0.000 claims description 5
- 229910014360 LiNi1−x−yCoxAlyO2 Inorganic materials 0.000 claims description 5
- 229910004014 SiF4 Inorganic materials 0.000 claims description 5
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims description 5
- 229910014336 LiNi1-x-yCoxMnyO2 Inorganic materials 0.000 claims description 4
- 229910014446 LiNi1−x-yCoxMnyO2 Inorganic materials 0.000 claims description 4
- 229910014825 LiNi1−x−yCoxMnyO2 Inorganic materials 0.000 claims description 4
- 150000004679 hydroxides Chemical class 0.000 claims description 4
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 claims description 4
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 4
- 239000012448 Lithium borohydride Substances 0.000 claims description 3
- 229910013100 LiNix Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 4
- 238000004146 energy storage Methods 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 abstract 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 37
- 238000011068 loading method Methods 0.000 description 24
- 238000005303 weighing Methods 0.000 description 19
- 238000000227 grinding Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 15
- 239000004576 sand Substances 0.000 description 8
- 238000001694 spray drying Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 229910001679 gibbsite Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 4
- -1 oxides Chemical class 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 3
- 229910018632 Al0.05O2 Inorganic materials 0.000 description 2
- 229910012527 LiNi0.4Co0.6O2 Inorganic materials 0.000 description 2
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 2
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 2
- 229910015694 LiNi0.85Co0.1Al0.05O2 Inorganic materials 0.000 description 2
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013649 LiNixMn2-xO4 Inorganic materials 0.000 description 1
- 229910013663 LiNixMn2—xO4 Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- ZJRWDIJRKKXMNW-UHFFFAOYSA-N carbonic acid;cobalt Chemical compound [Co].OC(O)=O ZJRWDIJRKKXMNW-UHFFFAOYSA-N 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/582—Halogenides
-
- 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
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- 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
Abstract
The invention is applicable to the technical field of battery anode materials, and provides a composite manganese-based anode material and a preparation method thereof. The composite manganese-based positive electrode material has a general formula: (1-q) Li1+ xMn2-x-yMyO4 & qLi1+ zMn2-z-a-b-cNiaCobAlcO4-d/2 Fd; wherein: m is a doping element. According to the invention, through doping modification and formation of mixed crystals on the surface, the LiMn2O4 structure is improved and stabilized, the stability, safety, charge-discharge efficiency, rate discharge performance, normal-temperature cycle life, storage and cycle performance at high temperature of the composite manganese-based anode material are improved, and the service life is long; the preparation method is simple, easy for large-scale production and low in material cost; the battery can be widely applied to the fields of digital codes, electric automobiles, electric bicycles, high-end clean energy storage batteries and the like.
Description
Technical Field
The invention belongs to the technical field of battery anode materials, and particularly relates to a composite manganese-based anode material and a preparation method thereof.
Background
Lithium ion batteries are favored for their advantages of high voltage, high energy density, long cycle life, and the like. With the development of new industries such as new generation information technology, high-end equipment, new materials, biology, new energy automobiles, new energy, energy conservation, environmental protection, digital originality and the like, lithium ion batteries are widely applied in the fields of electric vehicles (electric automobiles, electric ships, low-speed electric vehicles, electric bicycles and the like), energy storage (wind energy, solar energy, power grid peak and valley regulation, virtual power plants, 5G communication base stations and the like), communication (mobile phones, notebook computers and the like), substituted lead acid batteries (audio-visual equipment, industrial instruments, medical instruments, starting power supplies, electric tools and the like) and the like.
The anode material is the core and key material of the lithium ion battery. The composite manganese-based cathode material is concerned because the performance of the composite manganese-based cathode material is far superior to that of a cathode material with a single component, but the rate discharge performance, the first charge-discharge efficiency, the normal-temperature cycle life and the storage and cycle performance at high temperature of the composite manganese-based cathode material need to be further improved.
Disclosure of Invention
The embodiment of the invention aims to provide a composite manganese-based positive electrode material and a preparation method thereof, and aims to solve the problems in the prior art pointed out in the background art.
The embodiment of the invention is realized by the following steps that the composite manganese-based positive electrode material has a general composition formula: (1-q) Li1+xMn2-x-yMyO4·qLi1+zMn2-z-a-b-cNiaCobAlcO4-d/2Fd；
Wherein: m is a doping element, x is more than or equal to 0 and less than or equal to 0.1, y is more than or equal to 0.001 and less than or equal to 0.1, z is more than or equal to 0 and less than or equal to 0.25, a is more than or equal to 0.001 and less than or equal to 0.1, b is more than or equal to 0.001 and less than or equal to 0.1, c is more than or equal to 0.001 and less than or equal to 0.1, d is more than 0 and less than or equal to 0.25, and q is more than or equal to 0.001 and less than or equal to 0.2.
Another object of an embodiment of the present invention is to provide a method for preparing a composite manganese-based positive electrode material, including the following steps:
mixing a part of lithium source, a nickel source, a cobalt source, an aluminum source, a part of manganese source and a fluorine source to obtain a mixed material;
the mixed material is subjected to decomposition, oxidation, melting, crystallization synthesis, cooling and crushing to obtain Li1+zMn2-z-a-b- cNiaCobAlcO4-d/2Fd；
Mixing Li1+zMn2-z-a-b-cNiaCobAlcO4-d/2FdMixing and crushing the dispersing agent and water;
adding the balance of lithium source, the balance of manganese source and M source, and mixing;
and decomposing, oxidizing, melting, crystallizing, synthesizing, cooling and crushing the obtained product to obtain the composite manganese-based positive electrode material.
As another preferred scheme of the embodiment of the present invention, the mixed material is synthesized through decomposition, oxidation, melting and crystallization, specifically: placing the mixed material in an oxygen-enriched atmosphere, and decomposing, oxidizing and melting the mixed material at the temperature of 300-650 ℃ for 3-6 hours; heating to 660-850 ℃, and crystallizing and synthesizing for 3-20 hours;
the obtained product is subjected to the processes of decomposition, oxidation, melting and crystallization synthesis, and specifically comprises the following steps: placing the obtained product in an oxygen-enriched atmosphere, and decomposing, oxidizing and melting the obtained product for 3-6 hours at the temperature of 300-650 ℃; heating to 660-850 ℃, crystallizing and synthesizing for 5-20 hours, cooling to 400-650 ℃, and carrying out repairability roasting on the crystals for 3-8 hours.
As another preferable scheme of the embodiment of the invention, the lithium source is Li2CO3、LiOH、LiOH·H2O、Li3PO4、LiF、Li3N and lithium borohydride.
In another preferred embodiment of the present invention, the Manganese source is at least one of a hydroxide, an oxide, a nitride, a boride, a carbonate, a nitrate, an oxalate, an acetate, an ammonia complex, a carbonyl complex and EMD (Electrolytic Manganese Dioxide).
In another preferred embodiment of the present invention, the M source is at least one of a hydroxide, an oxide, a carbonate, a phosphate, an acetate, an oxalate, a nitrate, an ammonia complex, a carbonyl complex, and a hydrate of Ti, Mg, Ca, Ta, V, Sr, Cs, In, Zn, Nb, Y, Mo, Rb, Zr, Si, Cr, B, Sb, Bi, Ga, Sn, W, Ge, and La elements, or a composite compound containing these elements.
As another preferable mode of the embodiment of the present invention, the nickel source is at least one of a hydroxide, a carbonate, an oxide, a boride, a fluoride, a phosphate, an acetate, an oxalate, an ammonia complex, a carbonyl complex, and a hydrate containing a Ni element;
or the nickel source is at least one of the following substances: LiNiO2；LiNi1-xCOxO2，0≤x＜1.0；LiNi1-x-yCOxAlyO2，x+y＜1.0；LiNi1-x-yCOxMnyO2，x+y＜1.0；LiNixMn2-xO4，0＜x≤1.0。
As another preferable scheme of the embodiment of the invention, the cobalt source contains COAt least one of hydroxides, carbonates, oxides, borides, fluorides, phosphates, acetates, oxalates, ammonia complexes, carbonyl complexes, and hydrates of the elements;
or the cobalt source is at least one of the following substances: LiCOO2；LiNi1-xCOxO2，0＜x≤1.0；LiCO1-x- yNixAlyO2，x+y＜1.0；LiCO1-x-yNixMnyO2，x+y＜1.0。
As another preferable mode of the embodiment of the present invention, the aluminum source is at least one of hydroxide, oxide, boride, fluoride, phosphate, metaphosphate, nitrate, acetate, oxalate, ammonia complex, carbonyl complex, and hydrate containing Al;
or the aluminum source is at least one of the following substances: LiAlO2；LiCO1-x-yNixAlyO2，x+y≤1.0；LiAlF4；Al(H2PO4)3；Li3AlF6；AlOOH·nH2O。
As another preferable scheme of the embodiment of the invention, the fluorine source is LiF or AlF3、MnF2、CoF2、NiF2、LiAlF4、Li3AlF6、SiF4At least one of (1).
The invention improves and stabilizes LiMn through doping modification and mixed crystal formation on the surface2O4The structure improves the stability, safety, charge-discharge efficiency, rate discharge performance, normal-temperature cycle life, storage and cycle performance at high temperature of the composite manganese-based anode material, and has long service life; the preparation method is simple, easy for large-scale production and low in material cost; the battery can be widely applied to the fields of digital codes, electric automobiles, electric bicycles, high-end clean energy storage batteries and the like.
Drawings
FIG. 1 shows the particle morphology of a composite manganese-based positive electrode material according to an embodiment of the present invention;
fig. 2 is a particle size distribution diagram of the composite manganese-based positive electrode material according to the embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Specific implementations of the present invention are described in detail below with reference to specific embodiments.
Example 1
The embodiment provides a composite manganese-based positive electrode material, and the preparation method comprises the following steps:
(1) adding the required Li2CO3、NiCO3、Co3O4、Al(OH)3、MnCO3LiF according to Li: ni: co: al: mn: the F molar ratio is 1.09: 0.05: 0.03: 0.1: 1.63: 0.1, weighing, preparing, then loading into high-efficiency mixing equipment, and uniformly mixing the materials;
(2) loading the prepared material into a sagger, feeding into a synthesis furnace in oxygen-rich atmosphere, decomposing, oxidizing and melting at 650 deg.C for 3 hr, crystallizing and synthesizing at 750 deg.C for 15 hr, cooling to room temperature, and crushing to obtain Li1.19Mn1.63Ni0.05Co0.03Al0.1O3.95F0.1The raw materials and a dispersing agent are weighed according to a ratio of 95:5 and then are added into a dispersion tank, pure water with the mass of 2 times is added for full and uniform stirring, then the raw materials are sent into a sand mill for fine grinding and superfine grinding to reach 200nm, the ground materials are sent into a spray drying tower for drying, and the product is called Q1 for short.
(3) Adding the required Li2CO3、MnO2MgO, Q1, according to Li: mn: mg: q1 molar ratio 0.981: 1.701: 0.018: 0.1, weighing, preparing, and then putting into high-efficiency mixing equipment for uniform mixing;
(4) loading the prepared material into a sagger, putting the sagger into an oxygen-enriched atmosphere synthesis furnace, decomposing, oxidizing and melting for 3 hours at the temperature of 600 ℃, then increasing the temperature to 750 ℃, crystallizing and synthesizing for 16 hours, then reducing the temperature to 480 ℃, carrying out repairability roasting on the crystal for 4 hours, then reducing the temperature to room temperature, and crushing to obtain the composite manganese-based positive electrode material 0.9Li1.09Mn1.89Mg0.02O4·0.1Li1.19Mn1.63Ni0.05Co0.03Al0.1O3.95F0.1。
Example 2
The embodiment provides a composite manganese-based positive electrode material, and the preparation method comprises the following steps:
(1) reacting the desired LiOH. H2O、Ni(OH)2、CoCO3、Al(OH)3、Mn2O3LiF according to Li: ni: co: al: mn: the F molar ratio is 1.04: 0.06: 0.04: 0.1: 1.64: 0.12, weighing, preparing, then loading into high-efficiency mixing equipment, and uniformly mixing the materials;
(2) loading the prepared materials into a sagger, feeding into a synthesis furnace in oxygen-rich atmosphere, decomposing, oxidizing and melting at 620 deg.C for 5 hr, crystallizing at 760 deg.C for 16 hr, and coolingCooling to room temperature and crushing to obtain Li1.16Mn1.64Ni0.06Co0.04Al0.1O3.94F0.12The raw materials and a dispersing agent are weighed according to a proportion of 94:6 and are added into a dispersion tank, pure water with the mass of 2.2 times of that of the raw materials is added and is fully and uniformly stirred, then the raw materials are sent into a sand mill for fine grinding and superfine grinding to reach 100 plus 200nm, the ground materials are sent into a spray drying tower for drying, and the product is called Q1 for short.
(3) Adding the required Li2CO3、MnO2、ZrO2And Q1, according to Li: mn: zr: the molar ratio of Q1 is 0.9592: 1.6588: 0.022: 0.12, weighing, preparing, and then putting into high-efficiency mixing equipment for uniform mixing;
(4) loading the prepared material into a sagger, putting the sagger into a synthesis furnace in an oxygen-rich atmosphere, decomposing, oxidizing and melting for 4 hours at the temperature of 610 ℃, then increasing the temperature to 740 ℃, crystallizing and synthesizing for 17 hours, then reducing the temperature to 580 ℃, carrying out restorative roasting on the crystal for 4 hours, then reducing the temperature to room temperature, and crushing to obtain the composite manganese-based positive electrode material 0.88Li1.09Mn1.885Zr0.025O4·0.12Li1.16Mn1.64Ni0.06Co0.04Al0.1O3.94F0.12。
Example 3
The embodiment provides a composite manganese-based positive electrode material, and the preparation method comprises the following steps:
(1) reacting the desired LiOH. H2O、NiO、Al2O3、Mn2O3、CoF2According to the weight ratio of Li: ni: co: al: mn: the F molar ratio is 1.15: 0.02: 0.11: 1.67: 0.1, weighing, preparing, then loading into high-efficiency mixing equipment, and uniformly mixing the materials;
(2) loading the prepared materials into a sagger, feeding into an oxygen-enriched atmosphere synthesis furnace, decomposing, oxidizing and melting at 640 deg.C for 3 hr, heating to 780 deg.C, crystallizing and synthesizing for 15 hr, cooling to room temperature, and crushing to obtain Li1.15Mn1.67Ni0.02Co0.05Al0.11O3.95F0.1Mixing it with disperser in 93:7Weighing the materials, adding the materials into a dispersion tank, adding pure water with the mass of 2.1 times of that of the materials, fully and uniformly stirring, sending the materials into a sand mill for fine grinding and superfine grinding to reach 100-200nm, and sending the ground materials into a spray drying tower for drying, wherein the product is Q1 for short.
(3) Adding the required Li2CO3、MnO2、Cr2O3And Q1, according to Li: mn: mg: the molar ratio of Q1 is 0.8925: 1.632: 0.051: 0.15, weighing, preparing, and then putting into high-efficiency mixing equipment for uniform mixing;
(4) loading the prepared material into a sagger, putting the sagger into a synthesis furnace in an oxygen-rich atmosphere, decomposing, oxidizing and melting for 4 hours at the temperature of 610 ℃, then increasing the temperature to 740 ℃, crystallizing and synthesizing for 17 hours, then reducing the temperature to 580 ℃, carrying out restorative roasting on the crystal for 4 hours, then reducing the temperature to room temperature, and crushing to obtain the composite manganese-based positive electrode material 0.85Li1.05Mn1.92Cr0.03O4·0.15Li1.15Mn1.67Ni0.02Co0.05Al0.11O3.95F0.1。
Example 4
The embodiment provides a composite manganese-based positive electrode material, and the preparation method comprises the following steps:
(1) reacting the desired LiOH. H2O、LiNi0.35CO0.6Al0.05O2、MnO2、AlF3According to the weight ratio of Li: (LiNi)0.35CO0.6Al0.05O2: mn: the F molar ratio is 1.158: 0.04: 1.692: 0.21, weighing, preparing, then loading into high-efficiency mixing equipment, and uniformly mixing the materials;
(2) loading the prepared material into a sagger, feeding into an oxygen-enriched atmosphere synthesis furnace, decomposing, oxidizing and melting at 600 deg.C for 6 hr, heating to 770 deg.C, crystallizing and synthesizing for 18 hr, cooling to room temperature, and crushing to obtain Li1.198Mn1.692Ni0.014Co0.024Al0.072O3.895F0.21Adding the mixture and a dispersing agent into a dispersing tank together according to the weight ratio of 93:7, and adding pure water with the mass of 2.1 times of that of the mixture to fully stirUniformly mixing, then sending into a sand mill for fine grinding and superfine grinding to reach 100-200nm, sending the ground material into a spray drying tower for drying, and then obtaining the product Q1 for short.
(3) Adding the required Li2CO3、MnO2、MOO3And Q1, according to Li: mn: mo: q1 molar ratio 0.9116: 1.6512: 0.0172: 0.14, weighing, preparing, and then putting into high-efficiency mixing equipment for uniform mixing;
(4) loading the prepared material into a sagger, putting the sagger into a synthesis furnace in an oxygen-rich atmosphere, decomposing, oxidizing and melting for 4 hours at the temperature of 610 ℃, then increasing the temperature to 740 ℃, crystallizing and synthesizing for 17 hours, then reducing the temperature to 580 ℃, carrying out restorative roasting on the crystal for 4 hours, then reducing the temperature to room temperature, and crushing to obtain the composite manganese-based positive electrode material 0.86Li1.06Mn1.92MO0.02O4·0.14Li1.198Mn1.692Ni0.014Co0.024Al0.072O3.895F0.21。
Example 5
The embodiment provides a composite manganese-based positive electrode material, and the preparation method comprises the following steps:
(1) reacting the desired LiOH. H2O、LiNi0.4CO0.6O2、AlOOH·2H 2O、MnO2、MnF2According to the weight ratio of Li: LiNi0.4CO0.6O2: al: mn: the F molar ratio is 1.16: 0.04: 0.12: 1.57: 0.14, weighing, preparing, then loading into high-efficiency mixing equipment, and uniformly mixing the materials;
(2) loading the prepared material into a sagger, feeding into a synthesis furnace in oxygen-rich atmosphere, decomposing, oxidizing and melting at 580 deg.C for 3 hr, heating to 770 deg.C, crystallizing for 18 hr, cooling to room temperature, and crushing to obtain Li1.2Mn1.64Ni0.016Co0.024Al0.12O3.93F0.14Adding the mixture and a dispersant into a dispersion tank together according to the weight ratio of 92:8, adding pure water with the mass of 2.1 times of that of the mixture, fully and uniformly stirring, sending the mixture into a sand mill for fine grinding and superfine grinding to reach 100 plus 200nm, and grinding the mixture to obtain a productThe material is sent to a spray drying tower for drying, and the product is called Q1.
(3) Adding the required Li2CO3、MnO2、Bi2O3、Y2O3And Q1, according to Li: mn: bi: y: the molar ratio of Q1 is 0.9523: 1.6821: 0.0178: 0.0178: 0.11, weighing, preparing, and then putting into high-efficiency mixing equipment for uniform mixing;
(4) loading the prepared material into a sagger, putting the sagger into an oxygen-enriched atmosphere synthesis furnace, decomposing, oxidizing and melting for 3 hours at the temperature of 600 ℃, then increasing the temperature to 775 ℃, crystallizing and synthesizing for 20 hours, then reducing the temperature to 630 ℃, carrying out repairability roasting on the crystal for 5 hours, then reducing the temperature to room temperature, and crushing to obtain the composite manganese-based positive electrode material 0.89Li1.07Mn1.89Bi0.02Y0.02O4·0.11Li1.2Mn1.692Ni0.014Co0.024Al0.07O3.895F0.21。
Example 6
The embodiment provides a composite manganese-based positive electrode material, and the preparation method comprises the following steps:
(1) reacting the desired LiOH. H2O、LiNi0.5CO0.2Mn0.3O2、Al(OH)3、MnO2LiF according to Li: LiNi0.5CO0.2Mn0.3O2: al: mn: the F molar ratio is 1.1: 0.05: 0.12: 1.56: 0.12, weighing, preparing, then loading into high-efficiency mixing equipment, and uniformly mixing the materials;
(2) loading the prepared material into a sagger, feeding into a synthesis furnace in oxygen-rich atmosphere, decomposing, oxidizing and melting at 580 deg.C for 3 hr, heating to 770 deg.C, crystallizing for 18 hr, cooling to room temperature, and crushing to obtain Li1.27Mn1.575Ni0.02 5Co0.01Al0.12O3.94F0.12Adding the mixture and a dispersing agent into a dispersion tank together according to the weighing ratio of 92:8, adding pure water with the mass of 2.1 times of that of the mixture, fully and uniformly stirring, sending the mixture into a sand mill for fine grinding and superfine grinding to reach the thickness of 100 plus 200nm, and sending the ground material to a grinding machineDrying in a spray drying tower, wherein the product is called Q1 for short.
(3) Adding the required Li2CO3、MnO2、Bi2O3、Sb2O3ZnO and Q1, according to Li: mn: mg: the molar ratio of Q1 is 0.8904: 1.5792: 0.0168: 0.0168: 0.0168: 0.16, weighing, preparing, and then putting into high-efficiency mixing equipment for uniform mixing;
(4) loading the prepared material into a sagger, putting the sagger into an oxygen-enriched atmosphere synthesis furnace, decomposing, oxidizing and melting for 3 hours at the temperature of 600 ℃, then increasing the temperature to 775 ℃, crystallizing and synthesizing for 20 hours, then reducing the temperature to 630 ℃, carrying out repairability roasting on the crystal for 5 hours, then reducing the temperature to room temperature, and crushing to obtain the composite manganese-based positive electrode material 0.84Li1.06Mn1.88Bi0.02Sb0.02Zn0.02O4·0.16Li1.22Mn1.625Ni0.025Co0.01Al0.12O3.94F0.12。
Example 7
The embodiment provides a composite manganese-based positive electrode material, and the preparation method comprises the following steps:
(1) reacting the desired LiOH. H2O、LiNi0.5Mn1.5O4、LiCOO2、Al(OH)3、MnO2LiF according to Li: LiNi0.5Mn1.5O4: co: al: mn: the F molar ratio is 1.05: 0.05: 0.04: 0.11: 1.55: 0.1, weighing, preparing, then loading into high-efficiency mixing equipment, and uniformly mixing the materials;
(2) loading the prepared material into sagger, feeding into oxygen-rich atmosphere synthesis furnace, decomposing at 595 deg.C, oxidizing, melting for 3.5 hr, heating to 772 deg.C, crystallizing for 18.5 hr, cooling to room temperature, and crushing to obtain Li1.2Mn1.625Ni0.025Co0.04Al0.11O3.95F0.1Adding the mixture and a dispersing agent into a dispersing tank together according to the weighing ratio of 92:8, adding pure water with the mass of 2.1 times of that of the mixture, fully and uniformly stirring, and then sending the mixture into a sand mill for fine grinding and superfine grinding to reach 100The particle size is minus 200nm, and the ground material is sent into a spray drying tower for drying, wherein the product is Q1 for short;
(3) adding the required Li2CO3、MnO2、V2O5、SnO2、La2O3And Q1, according to Li: mn: mg: the molar ratio of Q1 is 0.8798: 1.5604: 0.0166: 0.0166: 0.0166: 0.16, weighing, preparing, and then putting into high-efficiency mixing equipment for uniform mixing;
(4) loading the prepared material into a sagger, putting the sagger into an oxygen-enriched atmosphere synthesis furnace, decomposing, oxidizing and melting for 3 hours at the temperature of 600 ℃, then increasing the temperature to 775 ℃, crystallizing and synthesizing for 20 hours, then reducing the temperature to 630 ℃, carrying out repairability roasting on the crystal for 5 hours, then reducing the temperature to room temperature, and crushing to obtain the composite manganese-based positive electrode material 0.83Li1.06Mn1.88V0.02Sn0.02La0.02O4·0.17Li1.2Mn1.625Ni0.025Co0.04Al0.11O3.95F0.1。
Example 8
The embodiment provides a composite manganese-based positive electrode material, and the preparation method comprises the following steps:
(1) reacting the desired LiOH. H2O、LiNi1/3CO1/3Mn1/3O2、LiNi0.85CO0.1Al0.05O2、Al(OH)3、MnO2、CoF2According to the weight ratio of Li: LiNi1/3CO1/3Mn1/3O2：LiNi0.85CO0.1Al0.05O2: al: mn: the F molar ratio is 1.1: 0.03: 0.05: 0.1: 1.64: 0.2, weighing, preparing, then loading into high-efficiency mixing equipment, and uniformly mixing the materials;
(2) loading the prepared material into sagger, feeding into oxygen-rich atmosphere synthesis furnace, decomposing at 595 deg.C, oxidizing, melting for 3.5 hr, heating to 772 deg.C, crystallizing for 18.5 hr, cooling to room temperature, and crushing to obtain Li1.18Mn1.65Ni0.0525Co0.015Al0.1025O3.9F0.2To make itAdding the dispersant and the dispersant into a dispersion tank together according to the weighing of 92:8, adding pure water with the mass of 2.1 times of that of the dispersant, fully and uniformly stirring, then sending into a sand mill for fine grinding and superfine grinding to reach 200nm, sending the ground material into a spray drying tower for drying, and at this time, the product is called Q1 for short;
(3) adding the required Li2CO3、MnO2、WO3、TiO2、SrCO3And Q1, according to Li: mn: w: ti: sr: q1 molar ratio 0.848: 1.504: 0.024: 0.008: 0.008: 0.20, weighing, preparing, and then putting into high-efficiency mixing equipment for uniform mixing;
(4) loading the prepared material into a sagger, putting the sagger into an oxygen-enriched atmosphere synthesis furnace, decomposing, oxidizing and melting for 3 hours at the temperature of 600 ℃, then increasing the temperature to 775 ℃, crystallizing and synthesizing for 20 hours, then reducing the temperature to 630 ℃, carrying out repairability roasting on the crystal for 5 hours, then reducing the temperature to room temperature, and crushing to obtain the composite manganese-based positive electrode material 0.80Li1.06Mn1.88W0.03Ti0.01Sr0.01O4·0.20Li1.18Mn1.65Ni0.0525Co0.015Al0.1025O3.9F0.2。
Example 9
The difference from example 1 is:
in the step (2), the synthesis process of decomposition, oxidation, melting and crystallization specifically comprises the following steps: putting the prepared materials into a sagger, feeding the sagger into a synthesis furnace in an oxygen-rich atmosphere, and decomposing, oxidizing and melting the sagger at the temperature of 300 ℃ for 6 hours; heating to 660 ℃, crystallizing and synthesizing for 20 hours;
in the step (4), the synthesis process of decomposition, oxidation, melting and crystallization specifically comprises the following steps: putting the prepared materials into a sagger, putting the sagger into a synthetic furnace in an oxygen-rich atmosphere, and decomposing, oxidizing and melting the sagger at the temperature of 300 ℃ for 6 hours; raising the temperature to 660 ℃, crystallizing and synthesizing for 20 hours, reducing the temperature to 400 ℃, and carrying out repairability roasting on the crystals for 8 hours.
Example 10
The difference from example 1 is:
in the step (2), the synthesis process of decomposition, oxidation, melting and crystallization specifically comprises the following steps: putting the prepared materials into a sagger, feeding the sagger into a synthesis furnace in an oxygen-rich atmosphere, and decomposing, oxidizing and melting the sagger for 3 hours at the temperature of 650 ℃; heating to 850 ℃, crystallizing and synthesizing for 3 hours;
in the step (4), the synthesis process of decomposition, oxidation, melting and crystallization specifically comprises the following steps: putting the prepared materials into a sagger, putting the sagger into a synthetic furnace in an oxygen-rich atmosphere, and decomposing, oxidizing and melting the sagger for 3 hours at the temperature of 650 ℃; raising the temperature to 850 ℃, crystallizing and synthesizing for 5 hours, reducing the temperature to 650 ℃, and carrying out repairability roasting on the crystals for 3 hours.
Example 11
The difference from example 1 is:
the lithium source being Li2CO3And LiOH.
The manganese source is hydroxide and oxide containing Mn element.
The M source is one of hydroxides, oxides, carbonates, phosphates, acetates, oxalates, nitrates, ammonia coordination compounds, carbonyl coordination compounds and hydrates of Ti, Mg, Ca, Ta, V, Sr, Cs, In, Zn, Nb, Y, Mo, Rb, Zr, Si, Cr, B, Sb, Bi, Ga, Sn, W, Ge and La elements.
The nickel source is hydroxide and carbonate containing Ni element;
the cobalt source being COHydroxides and carbonates of elements.
The aluminum source is hydroxide, oxide, boride, fluoride, phosphate, metaphosphate, nitrate, acetate, oxalate, ammonia coordination compound, carbonyl coordination compound and hydrate containing Al element.
The fluorine source is LiF and AlF3。
Example 12
The difference from example 1 is:
the lithium source being Li2CO3LiOH and LiOH H2O。
The manganese source is hydroxide, oxide and nitride containing Mn element.
The M source is a mixture of a plurality of hydroxides, oxides, carbonates, phosphates, acetates, oxalates, nitrates, ammonia complexes, carbonyl complexes and hydrates of Ti, Mg, Ca, Ta, V, Sr, Cs, In, Zn, Nb, Y, Mo, Rb, Zr, Si, Cr, B, Sb, Bi, Ga, Sn, W, Ge and La elements.
The nickel source is hydroxide, carbonate and oxide containing Ni element;
the cobalt source being COHydroxides, carbonates and oxides of the elements.
The aluminum source is hydroxide, oxide, boride, fluoride, phosphate, metaphosphate, nitrate, acetate, oxalate, ammonia coordination compound and carbonyl coordination compound containing Al element.
The fluorine source is LiF or CoF2And NiF2。
Example 13
The difference from example 1 is:
the lithium source being Li2CO3、LiOH、LiOH·H2O and Li3PO4。
The manganese source is hydroxide, oxide, nitride and boride containing Mn element.
The M source is a composite compound containing multiple elements of Ti, Mg, Ca, Ta, V, Sr, Cs, In, Zn, Nb, Y, Mo, Rb, Zr, Si, Cr, B, Sb, Bi, Ga, Sn, W, Ge and La;
the nickel source is hydroxide, carbonate, oxide and boride containing Ni element;
the cobalt source being COFluorides, phosphates, acetates and oxalates of elements.
The aluminum source is hydroxide, fluoride, phosphate, metaphosphate, nitrate, acetate, oxalate, ammonia coordination compound, carbonyl coordination compound and hydrate containing Al element.
The fluorine source is LiF or LiAlF4、Li3AlF6And SiF4。
Example 14
The difference from example 1 is:
the lithium source being Li2CO3、LiOH、LiOH·H2O、Li3PO4And LiF.
The manganese source is hydroxide, oxide, nitride, boride and carbonate containing Mn element.
The M source is a mixture of a plurality of composite compounds of a plurality of elements of Ti, Mg, Ca, Ta, V, Sr, Cs, In, Zn, Nb, Y, Mo, Rb, Zr, Si, Cr, B, Sb, Bi, Ga, Sn, W, Ge and La.
The nickel source is hydroxide, carbonate, oxide, boride and fluoride containing Ni element;
the cobalt source being COOxides, borides, fluorides, phosphates and ammonia complexes of the elements.
The aluminum source is hydroxide, boride, fluoride, metaphosphate, nitrate, acetate, oxalate, ammonia coordination compound and carbonyl coordination compound containing Al element.
The fluorine source is LiF or MnF2、CoF2、LiAlF4And Li3AlF6。
Example 15
The difference from example 1 is:
the lithium source being Li2CO3、LiOH、LiOH·H2O、Li3PO4LiF and Li3N。
The Manganese source is nitrate, oxalate, acetate, ammonia complex, carbonyl complex and EMD (Electrolytic Manganese Dioxide) containing Mn element.
The nickel source is hydroxide, carbonate, oxide, boride, fluoride and phosphate containing Ni element;
the cobalt source being COHydroxides, carbonates, phosphates, ammonia complexes, carbonyl complexes and hydrates of the elements.
The aluminum source is hydroxide, boride, fluoride, phosphate, metaphosphate, acetate, oxalate and ammonia coordination compound containing Al element.
The fluorine source is LiF or AlF3、MnF2、CoF2、NiF2And LiAlF4。
Example 16
The difference from example 1 is:
the lithium source being Li2CO3、LiOH、LiOH·H2O、Li3PO4、LiF、Li3N and lithium borohydride.
The Manganese source is carbonate, nitrate, oxalate, acetate, ammonia complex, carbonyl complex and EMD (Electrolytic Manganese Dioxide) containing Mn element.
The nickel source is hydroxide, carbonate, oxide, boride, fluoride, phosphate and acetate containing Ni element;
the cobalt source being COHydroxides, oxides, borides, fluorides, phosphates, acetates and ammonia coordination compounds of the elements.
The aluminum source is hydroxide, phosphate, metaphosphate, nitrate, acetate, oxalate and ammonia coordination compound containing Al element.
The fluorine source is LiF or AlF3、MnF2、NiF2、LiAlF4、Li3AlF6And SiF4。
Example 17
The difference from example 1 is:
the Manganese source is boride, carbonate, nitrate, oxalate, acetate, ammonia complex, carbonyl complex and EMD (Electrolytic Manganese Dioxide) containing Mn element.
The nickel source is hydroxide, carbonate, oxide, boride, fluoride, phosphate, acetate and oxalate containing Ni element;
the cobalt source being COHydroxides, fluorides, phosphates, acetates, oxalates, ammonia complexes, carbonyl complexes and hydrates of the elements.
The aluminum source is hydroxide, phosphate, metaphosphate, nitrate, acetate and oxalate containing Al element.
The fluorine source is LiF or AlF3、MnF2、CoF2、NiF2、LiAlF4、Li3AlF6And SiF4。
Example 18
The difference from example 1 is:
the Manganese source is a nitride, boride, carbonate, nitrate, oxalate, acetate, ammonia complex, carbonyl complex, and EMD (Electrolytic Manganese Dioxide) containing an Mn element.
The nickel source is hydroxide, carbonate, oxide, boride, fluoride, phosphate, acetate, oxalate and ammonia coordination compound containing Ni element;
the cobalt source being COHydroxides, carbonates, borides, fluorides, phosphates, oxalates, ammonia complexes, carbonyl complexes, and hydrates of the elements.
The aluminum source is fluoride, phosphate, oxalate, ammonia coordination compound and carbonyl coordination compound containing Al element.
Example 19
The difference from example 1 is:
the Manganese source is a hydroxide, nitride, boride, carbonate, nitrate, oxalate, acetate, ammonia complex, carbonyl complex, and EMD (Electrolytic Manganese Dioxide) containing an Mn element.
The nickel source is hydroxide, carbonate, oxide, boride, fluoride, phosphate, acetate, oxalate, ammonia coordination compound and carbonyl coordination compound containing Ni element;
the cobalt source being COHydroxides, carbonates, oxides, borides, fluorides, phosphates, acetates, oxalates, ammonia complexes and hydrates of the elements.
The aluminum source is phosphate, metaphosphate, nitrate and acetate containing Al element.
Example 20
The difference from example 1 is:
the Manganese source is a hydroxide, oxide, nitride, boride, carbonate, nitrate, oxalate, acetate, ammonia complex, carbonyl complex, and EMD (Electrolytic Manganese Dioxide) containing an Mn element.
The nickel source is hydroxide, carbonate, oxide, boride, fluoride, phosphate, acetate, oxalate, ammonia coordination compound, carbonyl coordination compound and hydrate containing Ni element;
the cobalt source is LiCOO2And LiNi1-xCOxO2(0＜x≤1.0)。
The aluminum source is hydroxide, oxide and boride containing Al element.
Example 21
The difference from example 1 is:
the nickel source is LiNiO2。
The cobalt source being COHydroxides, carbonates, oxides, borides, fluorides, phosphates, acetates, oxalates, ammonia complexes, carbonyl complexes, and hydrates of the elements.
The aluminum source is hydroxide, boride, fluoride, metaphosphate, acetate and oxalate containing Al element.
Example 22
The difference from example 1 is:
the nickel source is LiNiO2And LiNi1-xCOxO2(0≤x＜1.0)。
The cobalt source is LiCOO2、LiNi1-xCOxO2(x is more than 0 and less than or equal to 1.0) and LiCO1-x-yNixAlyO2(x+y＜1.0)。
The aluminum source is oxide and boride containing Al element.
Example 23
The difference from example 1 is:
the nickel source is LiNiO2、LiNi1-xCOxO2(x is more than or equal to 0 and less than 1.0) and LiNi1-x-yCOxAlyO2(x+y＜1.0)。
The cobalt source is LiCOO2、LiNi1-xCOxO2(0＜x≤1.0)、LiCO1-x-yNixAlyO2(x + y < 1.0) and LiCO1-x- yNixMnyO2(x+y＜1.0)。
The aluminum source is LiAlO2And LiCO1-x-yNixAlyO2(x+y≤1.0)。
Example 24
The difference from example 1 is:
the nickel source is LiNiO2、LiNi1-xCOxO2(0≤x＜1.0)、LiNi1-x-yCOxAlyO2(x + y < 1.0) and LiNi1-x- yCOxMnyO2(x+y＜1.0)。
The aluminum source is LiAlO2、LiAlF4And Al (H)2PO4)3。
Example 25
The difference from example 1 is:
the nickel source is LiNiO2、LiNi1-xCOxO2(0≤x＜1.0)、LiNi1-x-yCOxAlyO2(x+y＜1.0)、LiNi1-x- yCOxMnyO2(x + y < 1.0) and LiNixMn2-xO4(0＜x≤1.0)。
The aluminum source is LiAlF4、Al(H2PO4)3、Li3AlF6And AlOOH. nH2O。
Example 26
The difference from example 1 is:
the aluminum source is LiAlO2、LiAlF4、Al(H2PO4)3、Li3AlF6And AlOOH. nH2O。
Example 27
The difference from example 1 is:
the aluminum source is LiAlO2、LiCO1-x-yNixAlyO2(x+y≤1.0)、LiAlF4、Al(H2PO4)3、Li3AlF6And AlOOH. nH2O。
Examples of the experiments
The properties of the composite manganese-based cathode material prepared by the invention are shown in table 1.
Table 1 properties of composite manganese-based positive electrode material prepared according to the present invention
Note: limiting the charging and discharging voltage: 4.2-3.0V.
As can be seen from table 1, compared with the manganese-based cathode material prepared by the prior art process, the composite manganese-based cathode material prepared by the invention has the advantages of good stability, high safety, good rate discharge performance, high first charge-discharge efficiency, long normal temperature cycle life, and good storage and cycle performance at high temperature.
The performance test results of the composite manganese-based cathode materials prepared in examples 1 to 8 are shown in table 2.
Table 2 results of performance tests of composite manganese-based positive electrode materials prepared in examples 1 to 8
Note: limiting the charging and discharging voltage: 4.2-3.0V.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The composite manganese-based cathode material is characterized by comprising the following componentsThe general formula is: (1-q) Li1+xMn2-x-yMyO4·qLi1+zMn2-z-a-b-cNiaCobAlcO4-d/2Fd；
Wherein: m is a doping element, x is more than or equal to 0 and less than or equal to 0.1, y is more than or equal to 0.001 and less than or equal to 0.1, z is more than or equal to 0 and less than or equal to 0.25, a is more than or equal to 0.001 and less than or equal to 0.1, b is more than or equal to 0.001 and less than or equal to 0.1, c is more than or equal to 0.001 and less than or equal to 0.1, d is more than 0 and less than or equal to 0.25, and q is more than or equal to 0.001 and less than or equal to 0.2.
2. The method for preparing the composite manganese-based positive electrode material according to claim 1, comprising the steps of:
mixing a part of lithium source, a nickel source, a cobalt source, an aluminum source, a part of manganese source and a fluorine source to obtain a mixed material;
the mixed material is subjected to decomposition, oxidation, melting, crystallization synthesis, cooling and crushing to obtain Li1+zMn2-z-a-b- cNiaCobAlcO4-d/2Fd；
Mixing Li1+zMn2-z-a-b-cNiaCobAlcO4-d/2FdMixing and crushing the dispersing agent and water;
adding the balance of lithium source, the balance of manganese source and M source, and mixing;
and decomposing, oxidizing, melting, crystallizing, synthesizing, cooling and crushing the obtained product to obtain the composite manganese-based positive electrode material.
3. The preparation method of the composite manganese-based positive electrode material according to claim 2, wherein the mixed material is synthesized by decomposition, oxidation, melting and crystallization, and specifically comprises the following steps: placing the mixed material in an oxygen-enriched atmosphere, and decomposing, oxidizing and melting the mixed material at the temperature of 300-650 ℃ for 3-6 hours; heating to 660-850 ℃, and crystallizing and synthesizing for 3-20 hours;
the obtained product is subjected to the processes of decomposition, oxidation, melting and crystallization synthesis, and specifically comprises the following steps: placing the obtained product in an oxygen-enriched atmosphere, and decomposing, oxidizing and melting the obtained product for 3-6 hours at the temperature of 300-650 ℃; heating to 660-850 ℃, crystallizing and synthesizing for 5-20 hours, cooling to 400-650 ℃, and carrying out repairability roasting on the crystals for 3-8 hours.
4. The method of claim 2, wherein the lithium source is Li2CO3、LiOH、LiOH·H2O、Li3PO4、LiF、Li3N and lithium borohydride.
5. The method for preparing a composite manganese-based positive electrode material according to claim 2, wherein the manganese source is at least one of a hydroxide, an oxide, a nitride, a boride, a carbonate, a nitrate, an oxalate, an acetate, an ammonia complex, a carbonyl complex, and EMD containing an Mn element.
6. The method according to claim 2, wherein the M source is at least one of a hydroxide, an oxide, a carbonate, a phosphate, an acetate, an oxalate, a nitrate, an ammonia complex, a carbonyl complex, and a hydrate of Ti, Mg, Ca, Ta, V, Sr, Cs, In, Zn, Nb, Y, Mo, Rb, Zr, Si, Cr, B, Sb, Bi, Ga, Sn, W, Ge, and La, or a composite compound containing the above elements.
7. The method for producing a composite manganese-based positive electrode material according to claim 2, characterized in that the nickel source is at least one of a hydroxide, a carbonate, an oxide, a boride, a fluoride, a phosphate, an acetate, an oxalate, an ammonia complex, a carbonyl complex, and a hydrate containing Ni element;
or the nickel source is at least one of the following substances: LiNiO2；LiNi1-xCOxO2，0≤x＜1.0；LiNi1-x- yCOxAlyO2，x+y＜1.0；LiNi1-x-yCOxMnyO2，x+y＜1.0；LiNixMn2-xO4，0＜x≤1.0。
8. The method of claim 2, wherein the cobalt source is C-containingOAt least one of hydroxides, carbonates, oxides, borides, fluorides, phosphates, acetates, oxalates, ammonia complexes, carbonyl complexes, and hydrates of the elements;
or the cobalt source is at least one of the following substances: LiCOO2；LiNi1-xCOxO2，0＜x≤1.0；LiCO1-x- yNixAlyO2，x+y＜1.0；LiCO1-x-yNixMnyO2，x+y＜1.0。
9. The method for preparing a composite manganese-based positive electrode material according to claim 2, wherein the aluminum source is at least one of a hydroxide, an oxide, a boride, a fluoride, a phosphate, a metaphosphate, a nitrate, an acetate, an oxalate, an ammonia complex, a carbonyl complex, and a hydrate of an Al-containing element;
or the aluminum source is at least one of the following substances: LiAlO2；LiCO1-x-yNixAlyO2，x+y≤1.0；LiAlF4；Al(H2PO4)3；Li3AlF6；AlOOH·nH2O。
10. The method of claim 2, wherein the fluorine source is LiF or AlF3、MnF2、CoF2、NiF2、LiAlF4、Li3AlF6、SiF4At least one of (1).
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003157844A (en) * | 2001-11-20 | 2003-05-30 | Sagaken Chiiki Sangyo Shien Center | Positive electrode active material for nonaqueous secondary battery, its manufacturing method, and nonaqueous secondary battery |
| CN102208611A (en) * | 2011-04-22 | 2011-10-05 | 王明月 | Induced crystallization synthesis method for anode powder material of lithium ion secondary battery |
| CN103700834A (en) * | 2012-09-27 | 2014-04-02 | 清华大学 | Preparation method for lithium ion battery anode composite material |
| CN105552335A (en) * | 2016-01-11 | 2016-05-04 | 山东玉皇新能源科技有限公司 | Iron and vanadium synergistically doped lithium-rich manganese-based positive electrode material and preparation method thereof |
| CN109560284A (en) * | 2018-11-06 | 2019-04-02 | 山西北斗星新材料有限公司 | A kind of high performance doping type lithium manganate positive electrode and preparation method thereof |
| WO2020111545A1 (en) * | 2018-11-30 | 2020-06-04 | 주식회사 엘지화학 | Positive electrode active material, and positive electrode and lithium secondary battery comprising positive electrode active material |
| CN112047394A (en) * | 2020-09-10 | 2020-12-08 | 江西智锂科技有限公司 | Method for preparing composite manganese-based lithium battery cathode material by two-step crystallization method |
-
2021
- 2021-04-27 CN CN202110461219.1A patent/CN113178558A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003157844A (en) * | 2001-11-20 | 2003-05-30 | Sagaken Chiiki Sangyo Shien Center | Positive electrode active material for nonaqueous secondary battery, its manufacturing method, and nonaqueous secondary battery |
| CN102208611A (en) * | 2011-04-22 | 2011-10-05 | 王明月 | Induced crystallization synthesis method for anode powder material of lithium ion secondary battery |
| CN103700834A (en) * | 2012-09-27 | 2014-04-02 | 清华大学 | Preparation method for lithium ion battery anode composite material |
| CN105552335A (en) * | 2016-01-11 | 2016-05-04 | 山东玉皇新能源科技有限公司 | Iron and vanadium synergistically doped lithium-rich manganese-based positive electrode material and preparation method thereof |
| CN109560284A (en) * | 2018-11-06 | 2019-04-02 | 山西北斗星新材料有限公司 | A kind of high performance doping type lithium manganate positive electrode and preparation method thereof |
| WO2020111545A1 (en) * | 2018-11-30 | 2020-06-04 | 주식회사 엘지화학 | Positive electrode active material, and positive electrode and lithium secondary battery comprising positive electrode active material |
| CN112047394A (en) * | 2020-09-10 | 2020-12-08 | 江西智锂科技有限公司 | Method for preparing composite manganese-based lithium battery cathode material by two-step crystallization method |
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