CN116799190A - Lithium iron phosphate coated lithium-rich manganese-based positive electrode material and preparation method and application thereof - Google Patents
Lithium iron phosphate coated lithium-rich manganese-based positive electrode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN116799190A CN116799190A CN202310926618.XA CN202310926618A CN116799190A CN 116799190 A CN116799190 A CN 116799190A CN 202310926618 A CN202310926618 A CN 202310926618A CN 116799190 A CN116799190 A CN 116799190A
- Authority
- CN
- China
- Prior art keywords
- lithium
- rich manganese
- iron phosphate
- positive electrode
- lithium iron
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 129
- 239000011572 manganese Substances 0.000 title claims abstract description 124
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 119
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 118
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 104
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 60
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 30
- 238000005245 sintering Methods 0.000 claims abstract description 23
- 239000011258 core-shell material Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229940116007 ferrous phosphate Drugs 0.000 claims description 7
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 7
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000010405 anode material Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 239000005955 Ferric phosphate Substances 0.000 claims description 2
- 229910015118 LiMO Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 229940032958 ferric phosphate Drugs 0.000 claims description 2
- 229960001781 ferrous sulfate Drugs 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims 1
- 235000019837 monoammonium phosphate Nutrition 0.000 claims 1
- 239000006012 monoammonium phosphate Substances 0.000 claims 1
- 235000011007 phosphoric acid Nutrition 0.000 claims 1
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 16
- 239000007788 liquid Substances 0.000 description 13
- 239000010406 cathode material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- -1 sulfur anion Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a lithium iron phosphate coated lithium-rich manganese-based positive electrode material, a preparation method and application thereof, wherein the lithium iron phosphate coated lithium-rich manganese-based positive electrode material is of a core-shell structure, the core-shell structure takes the lithium iron phosphate as an inner core, and the lithium iron phosphate as an outer shell, so that the lithium iron phosphate is uniformly and densely coated on the surface of the lithium-rich manganese-based material in a drying and sintering combined mode, and the lithium iron phosphate can have synergistic effect, so that the long-cycle characteristic of the lithium iron phosphate is fully exerted, the characteristic of high capacity of the lithium iron phosphate-rich manganese-based material is not lost, the obtained lithium iron phosphate coated lithium-rich manganese-based positive electrode material has higher capacity and stability, and the cycle performance and the multiplying power performance of a lithium ion battery prepared by the lithium iron phosphate are greatly improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium iron phosphate coated lithium-rich manganese-based positive electrode material, and a preparation method and application thereof.
Background
At present, the positive electrode material is a key factor for limiting the high specific capacity of the lithium ion battery, and the lithium-rich manganese-based material has a discharge specific capacity which is much higher than that of conventional positive electrode materials such as a lithium cobalt oxide material, a nickel cobalt manganese ternary material and the like, and the cost is low, so that the positive electrode material can meet the market demand, and is widely studied as a very ideal positive electrode material of the lithium ion battery.
Although lithium-rich manganese-based materials have many advantages such as high specific capacity, low cost, environmental friendliness, etc., they also have some fatal drawbacks such as poor cycle performance, poor rate performance, poor conductivity, and serious voltage drop problems, etc., mainly due to structural transformation and interfacial side reactions of the lithium-rich manganese-based materials; based on this, how to improve the rate performance and the cycle stability of the lithium-rich manganese-based positive electrode material has become an important point of research in recent years.
CN106229502a discloses a preparation method of a sulfur anion doped lithium-rich cathode material, which comprises the following steps: weighing a certain amount of nickel sulfate and manganese sulfate according to a molar ratio, dissolving the nickel sulfate and the manganese sulfate in deionized water, slowly adding a NaOH solution into the solution, and precipitating to obtain a mixed metal salt precipitate with a certain proportion; uniformly mixing a small amount of lithium sulfide powder, lithium salt powder and the mixed metal salt precipitate; then placing the powder into a muffle furnace, heating to 200-500 ℃ for presintering, and then heating to 600-1000 ℃ for calcining to obtain sintered powder; adding an activating agent into the sintered powder, activating, drying, placing in a muffle furnace, and sintering at 200-500 ℃ for 3-8 hours to obtain a sulfur anion doped lithium-rich anode material; however, the method has the advantages that the doping temperature is too high, so that the energy cost is increased, meanwhile, sulfur in the finally obtained positive electrode material is doped in bulk, the surface side reaction is less restrained, and partial capacity loss is caused by substitution of bulk doping relative to oxygen.
CN114649522a discloses a Mo-doped Fe 2 O 3 Cladding lithium-rich manganese-based positive electrode material and preparation method thereof, and Mo-doped Fe obtained by cladding lithium-rich manganese-based positive electrode material 2 O 3 The coated lithium-rich manganese-based positive electrode material combines molybdenum doping and ferric oxide modification, and after double-effect modification, the cycle stability, the multiplying power performance, the initial discharge specific capacity and other electrochemical performances of the lithium-rich manganese-based positive electrode material are improved; however, the method cannot form a uniform and compact coating layer, and has no obvious effect on the structural stability of the lithium-rich manganese-based material.
CN103904311a discloses a cathode material for lithium secondary batteries with high capacity, high charge-discharge efficiency and excellent rate capability, the inner layer of the surface-coated composite lithium-rich manganese-based cathode material provided by the method is a lithium-rich manganese-based material, the surface-coated composite layer is a lithium iron phosphate material, the lithium iron phosphate of the surface-coated layer is a new phase generated in the coating and compositing process, and the lithium source is from the lithium-rich manganese-based cathode material; according to the invention, lithium iron phosphate is coated on the surface of the lithium-rich manganese base to form a coating layer by mainly utilizing lithium of the lithium-rich manganese base through a water bath drying and annealing treatment mode, although the lithium iron phosphate is successfully coated on the surface of the lithium-rich manganese base; however, the "surplus" lithium in the lithium-rich manganese-based material is consumed, so that the lithium-rich manganese-based material is not rich any more, and the characteristic of high capacity is lost.
Therefore, in order to solve the above technical problems, development of a lithium iron phosphate coated lithium-rich manganese-based positive electrode material having both high capacity and high stability is urgently needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the lithium iron phosphate coated lithium-rich manganese-based positive electrode material, and the preparation method and the application thereof, wherein the lithium iron phosphate coated lithium-rich manganese-based positive electrode material takes a lithium-rich manganese-based material as an inner core, takes a lithium iron phosphate positive electrode material as an outer shell, has high capacity and high stability, and can enable a lithium ion battery prepared by adopting the lithium iron phosphate coated lithium-rich manganese-based positive electrode material to have excellent cycle performance and rate performance.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a lithium iron phosphate coated lithium-rich manganese-based positive electrode material, wherein the lithium iron phosphate coated lithium-rich manganese-based positive electrode material is of a core-shell structure;
the shell layer of the core-shell structure comprises lithium iron phosphate, and the core of the core-shell structure comprises a lithium-rich manganese-based material.
According to the lithium iron phosphate coated lithium-rich manganese-based positive electrode material, the core-shell structure takes the lithium iron phosphate as an inner core, the lithium iron phosphate as an outer shell, the lithium iron phosphate is uniformly and densely coated on the surface of the lithium iron phosphate-rich manganese-based material by a method of drying and high-temperature sintering, so that direct contact between the lithium iron phosphate-rich manganese-based material and electrolyte can be effectively isolated, side reactions between the lithium iron phosphate-rich manganese-based material and the electrolyte can be effectively slowed down or inhibited, meanwhile, active lithium generated by phase change of the core lithium iron phosphate-rich manganese-based material can be directly embedded into the lithium iron phosphate of the outer shell, loss of active lithium of the whole positive electrode material is effectively reduced, the lithium in the lithium iron phosphate-rich manganese-based material can not consume the lithium to cause loss of high capacity of the lithium iron phosphate-rich manganese-based material, the long-cycle characteristic of the lithium iron phosphate-rich manganese-based material in the outer shell can be fully exerted, and the lithium iron phosphate-rich manganese-based material can be supplemented into the coated lithium iron phosphate by the active lithium with continuous phase change release, so that the obtained lithium iron phosphate coated lithium iron phosphate positive electrode material has high capacity and high stability and good cycle performance of the battery can be prepared by adopting the lithium ion battery.
Preferably, the particle size of the lithium-rich manganese-based material is 5 to 10 μm, for example 5.5 μm, 6m, 6.5 μm, 7 μm, 7.5 μm, 8 μm, 8.5 μm, 9 μm or 9.5 μm, etc.
As a preferable technical scheme of the invention, the particle size of the lithium-rich manganese-based material is limited to be 5-10 mu m, if the particle size of the lithium-rich manganese-based material is too small, the specific surface area of the lithium-rich manganese-based material is too large, so that side reaction with electrolyte is increased, the capacity of the finally obtained lithium ion battery is low, and if the particle size of the lithium-rich manganese-based material is too large, li is caused + Is transmitted by (a)The conductive performance of the cable is affected by the overlong transmission path.
Preferably, the chemical formula of the lithium-rich manganese-based positive electrode material is xLi 2 MnO 3 ·(1-x)LiMO 2 Wherein 0 is<x<1 (e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9, etc.), M is any one or a combination of at least two of Ni, co, or Mn.
Preferably, the thickness of the shell layer is 5 to 30nm, for example 7nm, 9nm, 11nm, 13nm, 15nm, 17nm, 19nm, 21nm, 23nm, 25nm, 27nm or 29nm, etc.
Preferably, the particle size of the lithium iron phosphate is 1 to 20nm, for example 2nm, 4nm, 6nm, 8nm, 10nm, 12nm, 14nm, 16nm or 18nm, etc.
In a second aspect, the present invention provides a method for preparing the lithium iron phosphate coated lithium-rich manganese-based positive electrode material according to the first aspect, the method comprising the following steps:
(1) Mixing a phosphorus source, an iron source, a lithium source and a lithium-rich manganese-based material in a solvent to obtain a precursor suspension;
(2) And (3) drying and sintering the precursor suspension obtained in the step (1) to obtain the lithium iron phosphate coated lithium-rich manganese-based anode material.
Firstly, the method adopts an external lithium source to provide lithium for lithium iron phosphate of a shell layer, does not consume the lithium of the lithium-rich manganese-based material, and further can fully ensure the characteristic of 'lithium enrichment' of the lithium-rich manganese-based material; and secondly, the lithium iron phosphate coated lithium-rich manganese-based anode material is prepared by adopting a mode of combining drying and sintering, and has the advantages of environmental protection, no introduction of any impurity, low production cost and realization of large-scale production.
Preferably, the mixing in step (1) specifically includes: firstly mixing a phosphorus source and an iron source in a solvent, adding a lithium source for mixing, and then adding a lithium-rich manganese-based material for mixing to obtain the precursor suspension.
Preferably, the phosphorus source of step (1) comprises any one or a combination of at least two of phosphoric acid, diammonium hydrogen phosphate or monoammonium dihydrogen phosphate.
Preferably, the iron source of step (1) comprises any one or a combination of at least two of ferrous phosphate, ferrous sulfate, ferrous chloride, ferrous nitrate, ferric nitrate or ferric phosphate.
Preferably, the lithium source of step (1) comprises any one or a combination of at least two of lithium hydroxide, lithium carbonate, lithium acetate or lithium nitrate.
Preferably, the solvent of step (1) comprises water.
Preferably, the molar ratio of the phosphorus source, the iron source and the lithium source in step (1) is 1:1 (1.2-3.5), such as 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8, 1:3, 1:3.2 or 1:3.4, etc.
Preferably, the iron source is present in a molar amount of 1 to 5mol, e.g. 1.5mol, 2mol, 2.5mol, 3mol, 3.5mol, 4mol or 4.5mol, etc., based on 1L of the precursor suspension of step (1).
Preferably, the mass percentage of the lithium-rich manganese-based material in the precursor suspension of step (1) is 10-30%, such as 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26% or 28%, etc.
In the present invention, the thickness of the shell layer can be reasonably controlled by controlling the solid content of the lithium-rich manganese-based material in the precursor suspension so as to be within the preferred range defined by the present invention.
Preferably, the drying of step (2) is spray drying.
Preferably, the specific method of spray drying comprises: atomizing the precursor liquid obtained in the step (1) into small liquid drops, spraying the small liquid drops into a heating chamber, and drying the small liquid drops by contacting with hot air.
Preferably, the temperature of the heating chamber is 100 to 150 ℃, for example 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, or the like.
Preferably, the sintering of step (2) is performed in a sintering furnace.
Preferably, the sintering temperature in step (2) is 450-850 ℃, e.g., 470 ℃, 490 ℃, 510 ℃, 530 ℃, 550 ℃, 580 ℃, 610 ℃, 630 ℃, 650 ℃, 680 ℃, 710 ℃, 740 ℃, 780 ℃, 810 ℃, 830 ℃, or the like.
Preferably, the sintering time in step (2) is 6 to 12 hours, for example 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours or 11.5 hours, etc.
In the present invention, the particle size of lithium iron phosphate of the shell layer can be reasonably controlled by controlling the sintering time period so as to be within the preferred range defined by the present invention.
In a third aspect, the present invention provides a lithium ion battery comprising a lithium iron phosphate coated lithium-rich manganese-based cathode material according to the first aspect.
Preferably, the negative electrode material of the lithium ion battery comprises a silicon carbon material.
In a fourth aspect, the invention provides an application of the lithium ion battery in a new energy automobile.
Compared with the prior art, the invention has the following beneficial effects:
(1) The lithium iron phosphate coated lithium-rich manganese-based positive electrode material provided by the invention is of a core-shell structure, the lithium iron phosphate is taken as an inner core, and the lithium iron phosphate is taken as an outer shell, and the lithium iron phosphate are combined by a drying and sintering method, so that the lithium iron phosphate is uniformly and densely coated on the surface of the lithium-rich manganese-based material to form a uniform and compact coating outer shell, the long-cycle characteristic of the lithium iron phosphate can be fully exerted, the high-capacity characteristic of the lithium iron phosphate-rich manganese-based material can not be lost, the obtained lithium iron phosphate coated lithium-rich manganese-based positive electrode material has higher capacity and stability, and the cycle performance and the multiplying power performance of a lithium ion battery prepared by the lithium iron phosphate coated lithium-rich manganese-based positive electrode material can be greatly improved.
(2) The preparation method of the lithium iron phosphate coated lithium-rich manganese-based positive electrode material provided by the invention is simple and efficient to operate, does not introduce any impurity, has low production cost, and can realize large-scale production.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
A lithium iron phosphate coated lithium-rich manganese-based positive electrode material is of a core-shell structure;
wherein the core is a lithium-rich manganese-based material with the particle diameter of 7 mu m, and the chemical formula is 0.5Li 2 MnO 3 ·0.5LiNi 0.6 Co 0.1 Mn 0.3 O 2 The method comprises the steps of carrying out a first treatment on the surface of the The thickness of the shell layer is 20nm, and the material is lithium iron phosphate with the particle size of about 3 nm;
the preparation method of the lithium iron phosphate coated lithium-rich manganese-based positive electrode material provided by the embodiment comprises the following steps:
(1) Firstly, mixing ferrous phosphate, phosphoric acid and lithium hydroxide according to a molar ratio of 1:1:2.5 to enable the molar concentration of the ferrous phosphate to be 3mol/L, and then adding a lithium-rich manganese-based material into the mixed solution to obtain a precursor suspension with the solid content of 20% of the lithium-rich manganese-based material;
(2) Atomizing the precursor suspension liquid obtained in the step (1) into small liquid drops, spraying the small liquid drops into a heating chamber with the temperature of 100 ℃, and removing the solvent through contact with hot air of the heating chamber to obtain a lithium iron phosphate coated lithium-rich manganese-based precursor;
(3) And (3) sintering the lithium iron phosphate coated lithium-rich manganese-based precursor obtained in the step (2) for 8 hours in a sintering furnace at 600 ℃ under the protection of nitrogen, so as to obtain the lithium iron phosphate coated lithium-rich manganese-based positive electrode material.
Example 2
A lithium iron phosphate coated lithium-rich manganese-based positive electrode material is of a core-shell structure;
wherein the core is a lithium-rich manganese-based material with the particle diameter of 8 mu m, and the chemical formula is 0.6Li 2 MnO 3 ·0.4LiNi 0.6 Co 0.1 Mn 0.3 O 2 The method comprises the steps of carrying out a first treatment on the surface of the The thickness of the shell layer is 10nm, and the material is lithium iron phosphate with the particle size of about 2 nm;
the preparation method of the lithium iron phosphate coated lithium-rich manganese-based positive electrode material provided by the embodiment comprises the following steps:
(1) Firstly, mixing ferrous sulfate, phosphoric acid and lithium carbonate according to a molar ratio of 1:1:2.5 to enable the molar concentration of the ferrous phosphate to be 3mol/L, and then adding a lithium-rich manganese-based material into the mixed solution to obtain a precursor suspension with the solid content of 30% of the lithium-rich manganese-based material;
(2) Atomizing the precursor suspension liquid obtained in the step (1) into small liquid drops, spraying the small liquid drops into a heating chamber with the temperature of 110 ℃, and removing the solvent by contacting with hot air of the heating chamber to obtain a lithium iron phosphate coated lithium-rich manganese-based precursor;
(3) And (3) sintering the lithium iron phosphate coated lithium-rich manganese-based precursor obtained in the step (2) for 8 hours in a sintering furnace at 600 ℃ under the protection of nitrogen, so as to obtain the lithium iron phosphate coated lithium-rich manganese-based positive electrode material.
Example 3
A lithium iron phosphate coated lithium-rich manganese-based positive electrode material is of a core-shell structure;
wherein the core is a lithium-rich manganese-based material with the particle diameter of 10 mu m, and the chemical formula is 0.5Li 2 MnO 3 ·0.5LiNi 0.8 Co 0.1 Mn 0.1 O 2 The method comprises the steps of carrying out a first treatment on the surface of the The thickness of the shell layer is 30nm, and the material is lithium iron phosphate with the particle size of about 10 nm;
the preparation method of the lithium iron phosphate coated lithium-rich manganese-based positive electrode material provided by the embodiment comprises the following steps:
(1) Firstly, mixing ferrous chloride, phosphoric acid and lithium nitrate according to a molar ratio of 1:1:2.5 to enable the molar concentration of the ferrous phosphate to be 3mol/L, and then adding a lithium-rich manganese-based material into the mixed solution to obtain a precursor suspension with the solid content of 20% of the lithium-rich manganese-based material;
(2) Atomizing the precursor suspension liquid obtained in the step (1) into small liquid drops, spraying the small liquid drops into a heating chamber with the temperature of 100 ℃, and removing the solvent by contacting with hot air of the heating chamber to obtain a lithium iron phosphate coated lithium-rich manganese-based precursor;
(3) And (3) sintering the lithium iron phosphate coated lithium-rich manganese-based precursor obtained in the step (2) for 8 hours in a sintering furnace at 800 ℃ under the protection of nitrogen, so as to obtain the lithium iron phosphate coated lithium-rich manganese-based positive electrode material.
Examples 4 to 7
The lithium iron phosphate coated lithium-rich manganese-based cathode material was different from example 1 only in that the particle diameters of the core lithium-rich manganese-based material were 5 μm, 10 μm, 4 μm and 11 μm, respectively, and other materials, structures and preparation methods were the same as those of example 1.
Examples 8 to 11
The lithium iron phosphate coated lithium-rich manganese-based positive electrode material was different from example 1 only in that the particle size of the lithium iron phosphate of the shell layer was about 1nm, 20nm, 0.5nm and 25nm, respectively, by changing the sintering time of step (3) in the preparation method, and other substances, structures and steps were the same as in example 1.
Examples 12 to 15
The lithium iron phosphate coated lithium-rich manganese-based positive electrode material was different from example 1 only in that the thickness of the shell layer was 5nm, 30nm, 3nm and 35nm, respectively, by changing the molar concentration of ferrous phosphate in the precursor suspension in step (1) of the preparation method, and other substances, structures and steps were the same as in example 1.
Comparative example 1
A lithium iron phosphate positive electrode material has a particle size of 20nm.
Comparative example 2
A lithium-rich manganese-based positive electrode material with a particle diameter of 7 μm and a chemical formula of 0.5Li 2 MnO 3 ·0.5LiNi 0.6 Co 0.1 Mn 0.3 O 2 。
Application example 1
A lithium ion battery comprising a positive electrode, a negative electrode, a separator and an electrolyte;
wherein the materials of the positive electrode comprise 90%, 5%, 2.5% and 2.5% of lithium iron phosphate coated lithium-rich manganese-based positive electrode materials (example 1), PVDF, multi-wall carbon tubes and SP;
the materials of the negative electrode comprise graphite, silicon oxide, SBR, CMC and SP with the percentage content of 76.4%, 19.1%, 1.4%, 1.1% and 2% respectively;
the diaphragm is a ceramic diaphragm;
the electrolyte comprises EC, PC, EMC, VC and PS with the volume ratio of 35:5:60:1:1, and then LiPF is added 6 So that LiPF 6 The concentration of (2) is 1mol/L;
the preparation process of the lithium ion battery provided by the application example comprises the following steps:
(1) Mixing a material of the positive electrode with NMP to obtain positive electrode slurry with the solid content of 55%, and performing coating, rolling and die cutting to obtain a positive electrode plate;
mixing the material of the negative electrode with water to obtain negative electrode slurry with the solid content of 48%, and performing coating, rolling and die cutting to obtain a negative electrode plate;
(2) And (3) assembling the positive electrode plate, the negative electrode plate and the diaphragm obtained in the step (1), injecting electrolyte, and carrying out capacity division and formation to obtain the lithium ion battery.
Application examples 2 to 15
A lithium ion battery was different from application example 1 only in that the lithium iron phosphate coated lithium-rich manganese-based cathode materials obtained in examples 2 to 15 were used instead of the lithium iron phosphate coated lithium-rich manganese-based cathode material obtained in example 1, and other substances, amounts and preparation methods were the same as those of application example 1.
Comparative application example 1
A lithium ion battery differs from application example 1 only in that the lithium iron phosphate cathode material obtained in comparative example 1 is used to replace the lithium iron phosphate coated lithium-rich manganese-based cathode material obtained in example 1, and other substances, amounts and preparation methods are the same as application example 1.
Comparative application example 2
A lithium ion battery differs from application example 1 only in that the lithium-rich manganese-based cathode material obtained in comparative example 2 is used in place of the lithium iron phosphate coated lithium-rich manganese-based cathode material obtained in example 1, and other substances, amounts and preparation methods are the same as those of application example 1.
Performance test:
(1) Cycle performance: 1C circulation is carried out at 25 ℃, and the number of circulation turns with the recording capacity lower than 80% SOH is recorded;
(2) 3C rate performance: and after the lithium ion battery is fully charged according to a constant current and a constant voltage of 1C, discharging according to 3C, and testing the capacity retention rate.
The lithium ion batteries provided in application examples 1 to 15 and comparative application examples 1 to 2 were tested according to the above test methods, and the test results are shown in table 1:
TABLE 1
| Cycle performance/times | 3C rate Performance/% | |
| Application example 1 | 1700 | 85 |
| Application example 2 | 1650 | 82 |
| Application example 3 | 1600 | 83 |
| Application example 4 | 1600 | 86 |
| Application example 5 | 1650 | 83 |
| Application example 6 | 1500 | 80 |
| Application example 7 | 1450 | 81 |
| Application example 8 | 1700 | 82 |
| Application example 9 | 1650 | 81 |
| Application example 10 | 1300 | 79 |
| Application example 11 | 1250 | 78 |
| Application example 12 | 1550 | 82 |
| Application example 13 | 1600 | 83 |
| Application example 14 | 1350 | 78 |
| Application example 15 | 1300 | 76 |
| Comparative application example 1 | 1300 | 80 |
| Comparative application example 2 | 670 | 55 |
From the data in table 1, it can be seen that:
the cycle performance tests of the lithium ion batteries obtained in application examples 1 to 15 show that the cycle number of the lithium ion batteries with the capacity lower than 80% SOH is 1250-1700, and the 3C rate performance test shows that the capacity retention rate is 78-85%.
As can be seen from the comparison of the data of application example 1 and comparative application examples 1 to 2, the lithium ion battery provided in comparative application example 1 is not very poor in cycle performance and rate performance, but is difficult to use alone because the gram capacity of lithium iron phosphate is low, namely, only 143 mAh/g; the lithium ion battery provided in comparative application example 2 has poor cycle performance and rate capability, which indicates that the lithium-rich manganese-based positive electrode material has poor effect when used alone; the lithium iron phosphate is taken as a shell layer, the lithium iron phosphate coated lithium-rich manganese-based positive electrode material obtained by taking the lithium iron phosphate-rich manganese-based material as a core can realize synergistic effect, so that the cycle performance and the rate capability of the lithium ion battery prepared by the lithium iron phosphate coated lithium-rich manganese-based positive electrode material are greatly improved, and the gram capacity of the obtained lithium iron phosphate coated lithium-rich manganese-based positive electrode material is not lower than 300mAh/g.
Comparing the data of application example 1 and application examples 4 to 7, it can be further found that the particle size of the core lithium-rich manganese-based material is also a very critical parameter, and the too large or too small particle size can deteriorate the cycle performance and the rate performance of the finally prepared lithium ion battery.
Finally, it can be seen from the data of application example 1, application examples 8 to 11 and application examples 12 to 15 that the particle size of the shell layer lithium iron phosphate and the thickness of the shell layer are not within the preferred range defined in the present invention, and also the cycle performance and the rate performance of the lithium ion battery are reduced.
The applicant states that the present invention is described by the above examples as a lithium iron phosphate coated lithium-rich manganese-based positive electrode material, and a preparation method and application thereof, but the present invention is not limited to the above examples, i.e., it does not mean that the present invention must be implemented depending on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The lithium iron phosphate coated lithium-rich manganese-based positive electrode material is characterized in that the lithium iron phosphate coated lithium-rich manganese-based positive electrode material is of a core-shell structure;
the shell layer of the core-shell structure comprises lithium iron phosphate, and the core of the core-shell structure comprises a lithium-rich manganese-based material.
2. The lithium iron phosphate coated lithium-rich manganese-based positive electrode material according to claim 1, wherein the particle size of the lithium-rich manganese-based material is 5-10 μm;
preferably, the lithium-rich manganese-based material has the chemical formula xLi 2 MnO 3 ·(1-x)LiMO 2 Wherein 0 is<x<1, M is any one or a combination of at least two of Ni, co or Mn.
3. The lithium iron phosphate coated lithium-rich manganese-based positive electrode material according to claim 1 or 2, wherein the thickness of the shell layer is 5-30 nm;
preferably, the particle size of the lithium iron phosphate is 1-20 nm.
4. A method for preparing the lithium iron phosphate coated lithium-rich manganese-based positive electrode material according to any one of claims 1 to 3, comprising the following steps:
(1) Mixing a phosphorus source, an iron source, a lithium source and a lithium-rich manganese-based material in a solvent to obtain a precursor suspension;
(2) And (3) drying and sintering the precursor suspension obtained in the step (1) to obtain the lithium iron phosphate coated lithium-rich manganese-based anode material.
5. The method of claim 4, wherein the phosphorus source of step (1) comprises any one or a combination of at least two of phosphoric acid, diammonium phosphate, or monoammonium phosphate;
preferably, the iron source of step (1) comprises any one or a combination of at least two of ferrous phosphate, ferrous sulfate, ferrous chloride, ferrous nitrate, ferric nitrate or ferric phosphate;
preferably, the lithium source of step (1) comprises any one or a combination of at least two of lithium hydroxide, lithium carbonate, lithium acetate or lithium nitrate;
preferably, the solvent of step (1) comprises water.
6. The method according to claim 4 or 5, wherein the molar ratio of the phosphorus source, the iron source and the lithium source in the step (1) is 1:1 (1.2 to 3.5);
preferably, the iron source is present in a molar amount of 1 to 5mol based on 1L of the precursor suspension of step (1);
preferably, the mass percentage of the lithium-rich manganese-based material in the precursor suspension in the step (1) is 10-30%.
7. The method of claim 5 or 6, wherein the drying in step (2) is spray drying;
preferably, the specific method of spray drying comprises: atomizing the precursor suspension obtained in the step (1) into small droplets, spraying the droplets into a heating chamber, and contacting the droplets with hot air for drying;
preferably, the temperature of the heating chamber is 100-150 ℃;
preferably, the sintering of step (2) is performed in a sintering furnace;
preferably, the sintering temperature in the step (2) is 450-850 ℃;
preferably, the sintering time in the step (2) is 6-12 h.
8. A lithium ion battery comprising the lithium iron phosphate coated lithium-rich manganese-based positive electrode material according to any one of claims 1 to 3.
9. The lithium ion battery of claim 8, wherein the negative electrode material of the lithium ion battery comprises a silicon carbon material.
10. Use of a lithium ion battery according to claim 8 or 9 in a new energy vehicle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310926618.XA CN116799190A (en) | 2023-07-26 | 2023-07-26 | Lithium iron phosphate coated lithium-rich manganese-based positive electrode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310926618.XA CN116799190A (en) | 2023-07-26 | 2023-07-26 | Lithium iron phosphate coated lithium-rich manganese-based positive electrode material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116799190A true CN116799190A (en) | 2023-09-22 |
Family
ID=88049800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310926618.XA Pending CN116799190A (en) | 2023-07-26 | 2023-07-26 | Lithium iron phosphate coated lithium-rich manganese-based positive electrode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116799190A (en) |
-
2023
- 2023-07-26 CN CN202310926618.XA patent/CN116799190A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109390563B (en) | Modified lithium iron phosphate positive electrode material, preparation method thereof, positive plate and lithium secondary battery | |
| CN113066969A (en) | Preparation method of conductive polymer coated lithium manganese iron phosphate cathode material | |
| CN107482182B (en) | Carbon-coated ion-doped manganese phosphate lithium electrode material and preparation method thereof | |
| CN114709391B (en) | Positive electrode lithium supplementing material, preparation method thereof and lithium ion battery | |
| CN109449429B (en) | Lithium iron phosphate/silicon carbide composite material and preparation method thereof | |
| CN102637877A (en) | Lithium ion battery anode material and manufacturing method thereof | |
| CN114597376B (en) | Method for preparing carbon-coated lithium iron phosphate material from ferrous phosphate | |
| CN112701281B (en) | Composite olivine structure positive electrode material and preparation method and application thereof | |
| EP4276947A1 (en) | Preparation method for lithium iron phosphate coated with ferroboron alloy | |
| CN115504526B (en) | Oxide sodium ion battery positive electrode material, and preparation method and application thereof | |
| CN116986572A (en) | Modified lithium iron manganese phosphate positive electrode material, preparation method thereof and lithium ion battery | |
| CN117219777B (en) | Lithium supplementing agent, preparation method thereof, positive electrode plate and secondary battery | |
| CN111668448B (en) | Lithium iron phosphate modified composite material and preparation method thereof | |
| CN115849327B (en) | Lithium iron manganese phosphate positive electrode material and preparation method thereof | |
| CN115676915B (en) | Layered oxide positive electrode material and preparation method and application thereof | |
| CN114455563B (en) | Modified lithium iron phosphate material and preparation method and application thereof | |
| CN108023079B (en) | Mixed transition metal borate anode material and preparation method thereof | |
| CN116344763A (en) | Metal/carbon coated lithium oxide composite positive electrode material, preparation method thereof, positive electrode plate containing positive electrode material and battery | |
| CN101200422B (en) | Method for preparing lithium iron phosphate ferrous oxalate | |
| CN113526552B (en) | Composite positive electrode active material of lithium ion battery and preparation method thereof | |
| KR20090108964A (en) | Manufacturing method of active electrode materials nano carbon coated with humic acid for lithium batteries | |
| CN116799190A (en) | Lithium iron phosphate coated lithium-rich manganese-based positive electrode material and preparation method and application thereof | |
| CN113764633A (en) | Surface modified lithium ion battery positive electrode material and preparation method thereof | |
| CN110767887A (en) | Vanadium-manganese borate material, carbon-coated vanadium-manganese borate material, and preparation methods and applications thereof | |
| CN114436234B (en) | Use of FePO 4 Lithium iron phosphate material prepared from/C composite material and preparation method 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 |