CN116354325A - Positive electrode material, preparation method thereof and lithium ion battery - Google Patents
Positive electrode material, preparation method thereof and lithium ion battery Download PDFInfo
- Publication number
- CN116354325A CN116354325A CN202211678841.9A CN202211678841A CN116354325A CN 116354325 A CN116354325 A CN 116354325A CN 202211678841 A CN202211678841 A CN 202211678841A CN 116354325 A CN116354325 A CN 116354325A
- Authority
- CN
- China
- Prior art keywords
- source
- positive electrode
- electrode material
- lithium
- sulfate
- 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
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 56
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 54
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910015645 LiMn Inorganic materials 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 229910052738 indium Inorganic materials 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000008247 solid mixture Substances 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052787 antimony Inorganic materials 0.000 claims description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 6
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical group [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910000379 antimony sulfate Inorganic materials 0.000 claims description 4
- MVMLTMBYNXHXFI-UHFFFAOYSA-H antimony(3+);trisulfate Chemical group [Sb+3].[Sb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MVMLTMBYNXHXFI-UHFFFAOYSA-H 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 4
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical group [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical group [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229910021550 Vanadium Chloride Inorganic materials 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 3
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 3
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 3
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical group [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 3
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 claims description 3
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940077478 manganese phosphate Drugs 0.000 claims description 3
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 3
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical group [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 claims description 3
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 abstract description 9
- 230000014759 maintenance of location Effects 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000002041 carbon nanotube Substances 0.000 abstract description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The embodiment of the application discloses a positive electrode material, a preparation method thereof and a lithium ion battery, wherein the positive electrode material is doped with three-dimensional graphene in a lithium manganese iron phosphate positive electrode material by ion doping to form LiMn 0.6 Fe 0.4‑x‑y Me x Ne y PO 4 The three-dimensional graphene composite material has a three-dimensional conductive network structure, has strong electron transmission capability, improves the cycle capacity retention rate, the primary charging efficiency, and the like of the lithium ion battery,The charging rate performance is used as a positive electrode material or a high-nickel coating material of the lithium ion battery, the conductive carbon can be used for coating less or no, and the carbon nano tube and the conductive carbon can be omitted in the manufacturing of the positive electrode plate, so that the process is simplified, and the production cost is reduced.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a positive electrode material, a preparation method thereof and a lithium ion battery.
Background
The single lithium iron manganese phosphate material has poor conductivity, so that the electrochemical performance of the material is difficult to fully develop, and the lower electronic conductivity and ion diffusion rate lead to LiMn x Fe 1-x PO 4 The high-current charge and discharge performance is poor, and the conductivity of the material is still poor although the conductivity of the material is improved to a certain extent after the carbon coating.
Disclosure of Invention
The embodiment of the application provides a positive electrode material, a preparation method thereof and a lithium ion battery, which can solve the problem of poor conductivity of the existing manganese iron lithium phosphate positive electrode material.
A first aspect of the present application provides a positive electrode material comprising LiMn 0.6 Fe 0.4-x- y Me x Ne y PO 4 The three-dimensional graphene composite material is characterized in that x is more than or equal to 0 and less than or equal to 0.1, y is more than or equal to 0 and less than or equal to 0.1, and Me and Ne are respectively selected from one of In, sb, bi, sr, V.
Optionally, the LiMn 0.6 Fe 0.4-x-y Me x Ne y PO 4 And the mass ratio of the three-dimensional graphene is (10-30): 1.
a second aspect of the present application provides a method for preparing a positive electrode material, including the steps of:
mixing a lithium source, a manganese source, an iron source, a Me source, a Ne source and a phosphorus source to obtain a solid mixture, adding water, stirring and mixing to form a mixed solution, and drying the mixed solution at 180-400 ℃ to obtain a precursor;
regulating the pH value of the multilayer graphene oxide solution to 8-12, performing hydrothermal reaction to obtain a reaction solution, cooling the reaction solution to room temperature, and then soaking, freezing and drying to obtain the three-dimensional graphene;
heating and sintering the precursor and the three-dimensional graphene to obtain LiMn 0.6 Fe 0.4-x-y Me x Ne y PO 4 Three-dimensional graphene composite.
Optionally, the weight ratio of water to solid mixture in the mixed solution is (5-20): 1.
optionally, the molar ratio of the lithium source, the manganese source, the iron source, the Me source, the Ne source and the phosphorus source is (1.0-1.1): (0.1-0.8): (0.2-0.9): (0-0.02): (0-0.02): 1.
optionally, the lithium source is one or any two of lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate, lithium sulfate and lithium chloride; the manganese source is ferric manganese oxalate, ferric manganese phosphate, manganese sulfate or manganese chloride; the iron source is ferric sulfate or ferric chloride; the Me source and the Ne source are respectively one of an indium source, an antimony source, a bismuth source, a strontium source and a vanadium source, wherein the indium source is indium sulfate or indium chloride, the antimony source is antimony sulfate or antimony chloride, the bismuth source is bismuth sulfate or bismuth chloride, the strontium source is strontium sulfate or strontium chloride, and the vanadium source is vanadium sulfate or vanadium chloride; the phosphorus source is one or any two of lithium dihydrogen phosphate, ammonium dihydrogen phosphate and ferromanganese phosphate.
Optionally, the concentration of the multilayer graphene oxide solution is 1 g/L-30 g/L.
Optionally, the reaction temperature of the hydrothermal reaction is 150-300 ℃ and the reaction time is 8-20 h.
Optionally, the temperature of heating and sintering is 600-900 ℃ and the sintering time is 6-20 h.
A third aspect of the present application provides a lithium ion battery comprising the positive electrode material as described above or comprising the positive electrode material prepared by the method of preparing the positive electrode material as described above.
The positive electrode material has the beneficial effects that the positive electrode material, the preparation method thereof and the lithium ion battery with the positive electrode material are provided, and the positive electrode material is doped with three-dimensional graphene in the lithium manganese iron phosphate positive electrode material through ion doping to form LiMn 0.6 Fe 0.4-x-y Me x Ne y PO 4 The three-dimensional graphene composite material has a three-dimensional conductive network structure, has high electron transmission capacity, improves the cycle capacity retention rate, the first charging efficiency and the charging multiplying power performance of the lithium ion battery, can be used as a positive electrode material or a high-nickel coating material of the lithium ion battery, can be coated with little or no conductive carbon, and can also cancel carbon nanotubes and conductive carbon on the manufacturing of a positive electrode plate, thereby simplifying the process and reducing the production cost.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly introduced below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a scanning electron microscope image of the positive electrode material provided in example 1 of the present application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application. Furthermore, it should be understood that the detailed description is presented herein for purposes of illustration and explanation only and is not intended to limit the present application.
In the detailed description and claims, a list of items connected by the term "at least one of" may mean any combination of the listed items. For example, if items a and B are listed, the phrase "at least one of a and B" means only a; only B; or A and B. In another example, if items A, B and C are listed, then the phrase "at least one of A, B and C" means only a; or only B; only C; a and B (excluding C); a and C (excluding B); b and C (excluding A); or A, B and C. Item a may comprise a single element or multiple elements. Item B may comprise a single element or multiple elements. Item C may comprise a single element or multiple elements. At least one of the terms "has the same meaning as at least one of the terms".
In the present specification, a numerical range shown by using "to" means a range including numerical values described before and after "to" as a minimum value and a maximum value, respectively.
The embodiment of the application provides a positive electrode material, a preparation method thereof and a lithium ion battery with the positive electrode material, wherein the positive electrode material is prepared from the following components in percentage by weightThe positive electrode material is doped with three-dimensional graphene in the lithium manganese iron phosphate positive electrode material by ion doping to form LiMn 0.6 Fe 0.4-x-y Me x Ne y PO 4 The three-dimensional graphene composite material has a three-dimensional conductive network structure, has high electron transmission capacity, improves the cycle capacity retention rate, the first charging efficiency and the charging multiplying power performance of the lithium ion battery, can be used as a positive electrode material or a high-nickel coating material of the lithium ion battery, can be coated with little or no conductive carbon, and can also cancel carbon nanotubes and conductive carbon on the manufacturing of a positive electrode plate, thereby simplifying the process and reducing the production cost. As a typical application, the positive electrode material may be applied to manufacture of lithium ion batteries, which may be applied in electric vehicles to provide electric energy to electric devices or energy storage devices.
In some embodiments of the present application, a positive electrode material is provided, the positive electrode material including LiMn 0.6 Fe 0.4-x- y Me x Ne y PO 4 The three-dimensional graphene composite material is characterized in that x is more than or equal to 0 and less than or equal to 0.1, y is more than or equal to 0 and less than or equal to 0.1, and Me and Ne are respectively selected from one of In, sb, bi, sr, V.
By introducing lithium manganese iron phosphate matrix material LiMn 0.6 Fe 0.4-x-y Me x Ne y PO 4 Intermediate doping of three-dimensional graphene to form LiMn 0.6 Fe 0.4-x-y Me x Ne y PO 4 Three-dimensional graphene composite material, lithium iron manganese phosphate matrix material LiMn 0.6 Fe 0.4-x- y Me x Ne y PO 4 Has an orthogonal olivine crystal structure, has good thermal stability and chemical stability, has a working voltage of 4.1V, is positioned in a stable electrochemical window of an organic electrolyte system, and has energy density compared with LiFePO 4 The improvement is 15% -20%, the composite material is formed by adding the three-dimensional graphene and the lithium iron manganese phosphate matrix material, so that the positive electrode material has a three-dimensional conductive network structure, the electron transmission capacity is high, and the cycle capacity retention rate, the primary charging efficiency and the charging rate performance of the lithium ion battery are improved.
In some embodimentsIn LiMn 0.6 Fe 0.4-x-y Me x Ne y PO 4 And the mass ratio of the three-dimensional graphene is (10-30): 1, in particular, liMn 0.6 Fe 0.4-x-y Me x Ne y PO 4 And the mass ratio of the three-dimensional graphene is in a range of 10:1, 15:1, 20:1, 25:1, 30:1 or any two ratios thereof. Preferably, liMn 0.6 Fe 0.4-x-y Me x Ne y PO 4 And the mass ratio of the three-dimensional graphene is (15-20): 1. when LiMn 0.6 Fe 0.4-x-y Me x Ne y PO 4 When the mass ratio of the three-dimensional graphene is in the range, the positive electrode material has excellent electron transmission capacity, and meanwhile, the transmission of lithium ions in the lithium iron manganese phosphate matrix material is not affected. If the mass ratio of the three-dimensional graphene in the positive electrode material is too high, the transmission of lithium ions in the positive electrode material can be influenced, and the cycle capacity retention rate of the lithium ion battery can be influenced. If the mass ratio of the three-dimensional graphene in the positive electrode material is too low, the conductivity of the positive electrode material is affected, and the first charge efficiency and the charging rate performance of the lithium ion battery are affected.
In some embodiments, there is also provided a method of preparing a positive electrode material, comprising the steps of:
s1) mixing a lithium source, a manganese source, an iron source, a Me source, a Ne source and a phosphorus source to obtain a solid mixture, then adding water, stirring and mixing to form a mixed solution, and drying the mixed solution at 180-400 ℃ to obtain a precursor;
s2) regulating the pH value of the multilayer graphene oxide solution to 8-12, performing hydrothermal reaction to obtain a reaction solution, cooling the reaction solution to room temperature, and then soaking and freeze-drying to obtain the three-dimensional graphene;
s3) heating and sintering the precursor and the three-dimensional graphene to obtain LiMn 0.6 Fe 0.4-x-y Me x Ne y PO 4 Three-dimensional graphene composite.
In some embodiments, the weight ratio of water to solid mixture in the mixed solution in step S1) is (5-20): 1.
in some embodiments, the molar ratio of the lithium source, the manganese source, the iron source, the Me source, the Ne source, and the phosphorus source is (1.0-1.1): (0.1-0.8): (0.2-0.9): (0-0.02): (0-0.02): 1.
in some embodiments, the Me source and the Ne source are each one of an indium source, an antimony source, a bismuth source, a strontium source, and a vanadium source.
In some embodiments, the Me source is an indium source and the Ne source is an antimony source, and then the molar ratio of the lithium source, the manganese source, the iron source, the indium source, the antimony source, and the phosphorus source is (1.0-1.1): (0.1-0.8): (0.2-0.9): (0-0.02): (0-0.02): 1.
in some embodiments, the lithium source is one or any two of lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate, lithium sulfate, or lithium chloride.
In some embodiments, the manganese source is ferric manganese oxalate, ferric manganese phosphate, manganese sulfate, or manganese chloride.
In some embodiments, the iron source is ferric sulfate or ferric chloride.
In some embodiments, the indium source is indium sulfate or indium chloride.
In some embodiments, the antimony source is antimony sulfate or antimony chloride.
In some embodiments, the bismuth source is bismuth sulfate or bismuth chloride.
In some embodiments, the strontium source is strontium sulfate or strontium chloride.
In some embodiments, the vanadium source is vanadium sulfate or vanadium chloride.
In some embodiments, the phosphorus source is one or any two of lithium dihydrogen phosphate, ammonium dihydrogen phosphate, and iron manganese phosphate.
In some embodiments, the concentration of the multi-layered graphene oxide solution in step S2) is 1g/L to 30g/L, specifically, the concentration of the multi-layered graphene oxide solution may be 1g/L, 5g/L, 10g/L, 15g/L, 20g/L, 25g/L, 30g/L, or a range of any two numbers therein. When the concentration of the multilayered graphene oxide solution is in the above range, the subsequently produced LiMn may be adjusted 0.6 Fe 0.4-x-y Me x Ne y PO 4 The mass content of the three-dimensional graphene in the three-dimensional graphene composite material avoids the excessively high or excessively low content of the three-dimensional graphene。
In some embodiments, the reaction temperature of the hydrothermal reaction of step S2) is 150 ℃ to 300 ℃ and the reaction time is 8 hours to 20 hours.
In some embodiments, the temperature of the heating sintering in step S3) is 600 ℃ to 900 ℃ and the sintering time is 6h to 20h.
The following description is made with reference to specific examples for the preparation method of the positive electrode material provided in the present application:
example 1
S1) mixing lithium hydroxide, manganese sulfate, ferric sulfate, indium sulfate, antimony sulfate and lithium dihydrogen phosphate according to the proportion of 1.02:0.6:0.36:0.02:0.02:1, adding the mixture into a refiner together in a molar ratio, fully and uniformly mixing to obtain a solid mixture, and then adding deionized water and the solid mixture into the mixture to be stirred and mixed to form a solution, wherein the weight ratio of water to the solid mixture is 10:1, spray drying the solution at 200 ℃ to obtain a precursor.
S2) placing the multilayer graphene into a beaker, adding water, stirring for 1h by using a magnetic rotor, stirring at the rotating speed of 200r/min, adding ammonia water to adjust the pH value to be=12, transferring into a reaction kettle with a lining of polytetrafluoroethylene, performing hydrothermal reaction at 180 ℃ for 10h, washing after the hydrothermal reaction, and then performing freeze drying at-50 ℃ for 36h to obtain the three-dimensional graphene.
S3) adding the precursor and the three-dimensional graphene into a mixer for fully and uniformly mixing to obtain mixed powder, loading the mixed powder into a crucible, and placing the crucible into an industrial microwave oven for heating and sintering reaction, wherein the reaction atmosphere is inert gas argon, and the argon flow is 1m 3 And/h, heating to 800 ℃, sintering for 10h, and cooling after sintering to obtain the anode material LiMn 0.6 Fe 0.38 In 0.1 Sb 0.1 PO 4 Three-dimensional graphene. LiMn 0.6 Fe 0.38 In 0.1 Sb 0.1 PO 4 The mass ratio of the three-dimensional graphene to the anode material is 15:1, and a scanning electron microscope image of the anode material is shown in figure 1.
Example 2
A cathode material was prepared according to the preparation method provided in example 1, except for the following differences:
LiMn 0.6 Fe 0.38 In 0.1 Sb 0.1 PO 4 and the mass ratio of the three-dimensional graphene is 10:1.
Example 3
A cathode material was prepared according to the preparation method provided in example 1, except for the following differences:
LiMn 0.6 Fe 0.38 In 0.1 Sb 0.1 PO 4 and the mass ratio of the three-dimensional graphene is 30:1.
Example 4
A cathode material was prepared according to the preparation method provided in example 1, except for the following differences:
LiMn 0.6 Fe 0.38 In 0.1 Sb 0.1 PO 4 and the mass ratio of the three-dimensional graphene is 20:1.
Example 5
A cathode material was prepared according to the preparation method provided in example 1, except for the following differences:
LiMn 0.6 Fe 0.38 In 0.1 Sb 0.1 PO 4 and the mass ratio of the three-dimensional graphene is 25:1.
Example 6
A cathode material was prepared according to the preparation method provided in example 1, except for the following differences:
the temperature of heating and sintering in the step S3) is 900 ℃, and the sintering time is 20h.
Example 7
A cathode material was prepared according to the preparation method provided in example 1, except for the following differences:
the temperature of heating and sintering in the step S3) is 600 ℃, and the sintering time is 6 hours.
Comparative example 1
LiMn 0.6 Fe 0.38 In 0.1 Sb 0.1 PO 4 And the mass ratio of the three-dimensional graphene is 5:1.
Comparative example 2:
LiMn 0.6 Fe 0.38 In 0.1 Sb 0.1 PO 4 and the mass ratio of the three-dimensional graphene is 40:1.
Electrochemical testing:
the positive electrode materials obtained in examples 1 to 7 and comparative examples 1 to 2 were mixed with a binder PVDF in a mass ratio of 95:5, mixing uniformly, adding 1-methyl-2 pyrrolidone NMP, ball milling for 1 hour by using zirconia beads to prepare slurry, uniformly coating the slurry on an aluminum sheet, and carrying out vacuum drying and rolling to prepare the positive electrode sheet. And assembling the single-piece soft package battery by taking graphite as a negative electrode. The blue electric test system is adopted for electric performance test (the charge-discharge voltage is 2.75-4.45V, and the temperature condition is 45 ℃). The results of the electrochemical performance test are shown in table 1.
TABLE 1
As can be seen from Table 1, liMn in the positive electrode materials prepared in examples 1 to 7 0.6 Fe 0.38 In 0.1 Sb 0.1 PO 4 And the mass ratio of the three-dimensional graphene is (10-30): 1, the single-chip soft-package batteries prepared in examples 1-7 have better charge-discharge capacity, higher primary charging efficiency and better cycle capacity retention rate.
Comparative example 1 was viewed reversely, and LiMn in the positive electrode material prepared therefrom 0.6 Fe 0.38 In 0.1 Sb 0.1 PO 4 And the mass ratio of the three-dimensional graphene is up to 5:1, and the cycle capacity retention rate of the single-chip soft-package battery is obviously reduced although the single-chip soft-package battery has better charge and discharge capacity and first charge efficiency. LiMn in the positive electrode material prepared in comparative example 2 0.6 Fe 0.38 In 0.1 Sb 0.1 PO 4 And the mass ratio of the three-dimensional graphene is only 40:1, so that the charge-discharge capacity, the first charge efficiency, the cyclic capacity retention rate and the actual state of the prepared single-chip soft-package battery are causedThere was a significant drop in each of examples 1-7.
The above describes in detail a positive electrode material, a preparation method thereof and a lithium ion battery provided in the embodiments of the present application, and specific examples are applied herein to illustrate principles and embodiments of the present application, where the above description of the examples is only for helping to understand the method and core ideas of the present application; meanwhile, those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present application, and the present description should not be construed as limiting the present application in view of the above.
Claims (10)
1. A positive electrode material, characterized in that the positive electrode material comprises LiMn 0.6 Fe 0.4-x-y Me x Ne y PO 4 The three-dimensional graphene composite material is characterized in that x is more than or equal to 0 and less than or equal to 0.1, y is more than or equal to 0 and less than or equal to 0.1, and Me and Ne are respectively selected from one of In, sb, bi, sr, V.
2. The positive electrode material of claim 1, wherein the LiMn 0.6 Fe 0.4-x-y Me x Ne y PO 4 And the mass ratio of the three-dimensional graphene is (10-30): 1.
3. a method for producing the positive electrode material according to claim 1 or 2, comprising the steps of:
mixing a lithium source, a manganese source, an iron source, a Me source, a Ne source and a phosphorus source to obtain a solid mixture, adding water, stirring and mixing to form a mixed solution, and drying the mixed solution at 180-400 ℃ to obtain a precursor;
regulating the pH value of the multilayer graphene oxide solution to 8-12, performing hydrothermal reaction to obtain a reaction solution, cooling the reaction solution to room temperature, and then soaking, freezing and drying to obtain the three-dimensional graphene;
heating and sintering the precursor and the three-dimensional graphene to obtain LiMn 0.6 Fe 0.4-x-y Me x Ne y PO 4 Three-dimensional graphene composite.
4. The method for producing a positive electrode material according to claim 3, wherein the weight ratio of water to the solid mixture in the mixed solution is (5 to 20): 1.
5. the method for producing a positive electrode material according to claim 3, wherein the molar ratio of the lithium source, the manganese source, the iron source, the Me source, the Ne source and the phosphorus source is (1.0 to 1.1): (0.1-0.8): (0.2-0.9): (0-0.02): (0-0.02): 1.
6. the method for producing a positive electrode material according to claim 5, wherein the lithium source is one or any two of lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate, lithium sulfate and lithium chloride;
the manganese source is ferric manganese oxalate, ferric manganese phosphate, manganese sulfate or manganese chloride;
the iron source is ferric sulfate or ferric chloride;
the Me source and the Ne source are respectively one of an indium source, an antimony source, a bismuth source, a strontium source and a vanadium source, wherein the indium source is indium sulfate or indium chloride, the antimony source is antimony sulfate or antimony chloride, the bismuth source is bismuth sulfate or bismuth chloride, the strontium source is strontium sulfate or strontium chloride, and the vanadium source is vanadium sulfate or vanadium chloride;
the phosphorus source is one or any two of lithium dihydrogen phosphate, ammonium dihydrogen phosphate and ferromanganese phosphate.
7. The method for producing a positive electrode material according to claim 3, wherein the concentration of the multilayered graphene oxide solution is 1g/L to 30g/L.
8. The method for preparing a positive electrode material according to claim 3, wherein the reaction temperature of the hydrothermal reaction is 150 to 300 ℃ and the reaction time is 8 to 20 hours.
9. The method for preparing a positive electrode material according to claim 3, wherein the temperature of the heating and sintering is 600 ℃ to 900 ℃ and the sintering time is 6h to 20h.
10. A lithium ion battery comprising the positive electrode material according to claim 1 or 2 or comprising the positive electrode material prepared by the method for preparing a positive electrode material according to any one of claims 3 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211678841.9A CN116354325A (en) | 2022-12-26 | 2022-12-26 | Positive electrode material, preparation method thereof and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211678841.9A CN116354325A (en) | 2022-12-26 | 2022-12-26 | Positive electrode material, preparation method thereof and lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116354325A true CN116354325A (en) | 2023-06-30 |
Family
ID=86904845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211678841.9A Pending CN116354325A (en) | 2022-12-26 | 2022-12-26 | Positive electrode material, preparation method thereof and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116354325A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105390682A (en) * | 2015-12-08 | 2016-03-09 | 广东石油化工学院 | Preparation method for lithium iron phosphate microsphere/three-dimensional graphene composite electrode material and application of composite electrode material |
| CN106129387A (en) * | 2016-09-23 | 2016-11-16 | 河北工业大学 | A kind of preparation method of iron manganese phosphate for lithium/three-dimensional carbon skeleton/carbon composite |
| CN109244391A (en) * | 2018-08-22 | 2019-01-18 | 江苏元景锂粉工业有限公司 | A kind of nitrogen mixes carbon coating iron manganese phosphate lithium material and preparation method thereof |
| CN111933915A (en) * | 2020-09-14 | 2020-11-13 | 天津斯科兰德科技有限公司 | Lithium iron manganese phosphate positive electrode material and preparation method and application thereof |
| CN113066969A (en) * | 2021-03-26 | 2021-07-02 | 深圳市鹏冠新材料科技有限公司 | Preparation method of conductive polymer coated lithium manganese iron phosphate cathode material |
| CN113912045A (en) * | 2021-09-27 | 2022-01-11 | 格林美（无锡）能源材料有限公司 | NaTi2V(PO4)4Three-dimensional graphene composite material and preparation method and application thereof |
-
2022
- 2022-12-26 CN CN202211678841.9A patent/CN116354325A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105390682A (en) * | 2015-12-08 | 2016-03-09 | 广东石油化工学院 | Preparation method for lithium iron phosphate microsphere/three-dimensional graphene composite electrode material and application of composite electrode material |
| CN106129387A (en) * | 2016-09-23 | 2016-11-16 | 河北工业大学 | A kind of preparation method of iron manganese phosphate for lithium/three-dimensional carbon skeleton/carbon composite |
| CN109244391A (en) * | 2018-08-22 | 2019-01-18 | 江苏元景锂粉工业有限公司 | A kind of nitrogen mixes carbon coating iron manganese phosphate lithium material and preparation method thereof |
| CN111933915A (en) * | 2020-09-14 | 2020-11-13 | 天津斯科兰德科技有限公司 | Lithium iron manganese phosphate positive electrode material and preparation method and application thereof |
| CN113066969A (en) * | 2021-03-26 | 2021-07-02 | 深圳市鹏冠新材料科技有限公司 | Preparation method of conductive polymer coated lithium manganese iron phosphate cathode material |
| CN113912045A (en) * | 2021-09-27 | 2022-01-11 | 格林美（无锡）能源材料有限公司 | NaTi2V(PO4)4Three-dimensional graphene composite material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 杨永强: "《石墨烯材料及其应用研究进展概述》", 31 July 2021, 吉林大学出版社, pages: 112 - 113 * |
| 贺志龙等: ""磷酸锰铁锂复合三元体系及对复合方式的研究"", 《电源技术》, vol. 43, no. 11, 20 November 2019 (2019-11-20), pages 1745 - 1748 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112670516B (en) | Three-dimensional composite current collector and preparation method thereof | |
| CN110400929B (en) | Phosphate-coated metal-doped ternary positive electrode active material and preparation and application thereof | |
| CN107403913A (en) | A kind of nickel cobalt lithium aluminate cathode material of surface modification and preparation method thereof | |
| CN112864385A (en) | Ternary cathode material, preparation method thereof and lithium ion battery | |
| CN103956485A (en) | Lithium iron phosphate electrode material having three-dimensional hierarchical structure, and preparation method thereof | |
| CN111009659A (en) | Preparation method and application of biomass carbon/poly-sodium manganese fluorophosphate composite material | |
| CN110970618A (en) | Preparation method of low-cost lithium iron phosphate composite material | |
| CN112054174A (en) | Potassium ion battery negative electrode material and preparation method and application thereof | |
| CN109904450B (en) | Preparation method of carbon-coated sodium vanadium phosphate composite positive electrode material | |
| CN112038638A (en) | Lithium ion positive electrode material lithium supplement modification method | |
| CN104332628B (en) | The preparation method and its lithium ion battery of anode material for lithium-ion batteries | |
| CN109817968B (en) | Surface-coated lithium nickel manganese oxide particles and method for producing same | |
| JP2017069177A (en) | Electrode material for lithium ion secondary battery, electrode for lithium ion secondary battery and lithium ion secondary battery | |
| CN114388745B (en) | High-performance lithium ion battery self-supporting polymer thick pole piece and preparation method thereof | |
| CN113517438B (en) | Internal confinement heterojunction yolk-shell electrode material and preparation method and application thereof | |
| CN115275168A (en) | High-rate lithium ion battery negative electrode material and preparation method thereof | |
| CN115520911A (en) | Lithium-nickel composite oxide positive electrode material and preparation method thereof | |
| CN114497507A (en) | Quick-filling graphite composite material and preparation method thereof | |
| CN114566647A (en) | Calcium phosphate coated high-nickel ternary cathode material and preparation method and application thereof | |
| CN116354325A (en) | Positive electrode material, preparation method thereof and lithium ion battery | |
| CN114204035A (en) | Cellulose-supported solid electrolyte membrane and preparation method and application thereof | |
| CN110783544A (en) | Carbon nanotube coated H 3PO 4Modified lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN114583137B (en) | Method for modifying carbon surface by sulfur doped phosphorus and application thereof | |
| CN116544418B (en) | Lithium cobalt oxide positive electrode material, preparation method thereof and battery | |
| CN108682798B (en) | Preparation method of cubic carbon-coated vanadium-based positive electrode material |
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 |