CN116525827A - Composite electrode material and preparation method and application thereof - Google Patents
Composite electrode material and preparation method and application thereof Download PDFInfo
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- CN116525827A CN116525827A CN202310480663.7A CN202310480663A CN116525827A CN 116525827 A CN116525827 A CN 116525827A CN 202310480663 A CN202310480663 A CN 202310480663A CN 116525827 A CN116525827 A CN 116525827A
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- electrode material
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- sulfonic acid
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- 239000007772 electrode material Substances 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 238000001354 calcination Methods 0.000 claims abstract description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 28
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000011247 coating layer Substances 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 59
- 229910001416 lithium ion Inorganic materials 0.000 claims description 59
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 claims description 44
- 238000000498 ball milling Methods 0.000 claims description 25
- 229960003080 taurine Drugs 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000011268 mixed slurry Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 description 32
- 239000007774 positive electrode material Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 238000005524 ceramic coating Methods 0.000 description 16
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 16
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 15
- 239000010405 anode material Substances 0.000 description 12
- 229910021383 artificial graphite Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 230000006872 improvement Effects 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000007773 negative electrode material Substances 0.000 description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229910021382 natural graphite Inorganic materials 0.000 description 6
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 description 2
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- DOCYQLFVSIEPAG-UHFFFAOYSA-N [Mn].[Fe].[Li] Chemical compound [Mn].[Fe].[Li] DOCYQLFVSIEPAG-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000010351 charge transfer process Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001351 cycling effect Effects 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
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/58—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
- H01M4/36—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a composite electrode material, a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing an electrode main material with an organic sulfonic acid substance, and calcining to obtain the composite electrode material; wherein the elements in the organic sulfonic acid substance comprise carbon element, nitrogen element and sulfur element. According to the invention, the nitrogen-sulfur doped carbon coating layer is introduced, so that not only are the multiplying power performance and the cycle performance of the electrode material improved, but also the high-multiplying power charge-discharge capacity of the electrode material is improved. The preparation method has simple process, low cost and good development potential.
Description
Technical Field
The invention belongs to the field of lithium ion battery materials, and particularly relates to a composite electrode material, a preparation method and application thereof.
Background
In practical application, the rate capability and cycle performance of the lithium battery can influence the charging speed and service life of the battery. The main reasons for the influence of the electrode materials on the rate performance and the cycle performance of the battery are as follows: (1) The migration capability of lithium ions on the anode, the cathode, the electrolyte and the interface thereof is limited, and the high-rate charge and discharge requires the accelerated transmission of lithium ions, which can lead to the increase of the internal resistance of the battery cell and the reduction of the performance; (2) The negative electrode has insufficient capacity, and after hundreds of cycles, the negative electrode structure is seriously damaged and cannot completely receive lithium ions provided by the positive electrode to generate a lithium precipitation phenomenon, so that the capacity is reduced prematurely, and the service life is reduced.
At present, citric acid and glucose are added into the anode and cathode electrode materials to form a coated carbon layer or nitrogen or sulfur is doped into the anode and cathode electrode materials to improve the rate capability and the cycle performance of the battery, and a certain effect is achieved.
For example, CN106299359a discloses a carbon-coated lithium vanadium phosphate positive electrode material and a preparation method thereof, the method comprising the steps of: mixing a lithium source, a vanadium source, a phosphorus source and a carbon source, adding absolute ethyl alcohol, placing the mixture into a ball milling tank for ball milling, drying, placing the mixture into a three-temperature-zone rotary furnace for sintering, and cooling to room temperature to obtain a carbon-coated lithium vanadium phosphate anode material; wherein the carbon source is a mixed carbon source of sucrose and citric acid.
CN105336924A discloses a preparation method of a carbon-coated sodium vanadium phosphate anode material, which comprises the steps of taking glucose as a reducing agent and a carbon source, taking water as a dispersing agent, and taking NH 4 VO 3 、NaH 2 PO 4 ·2H 2 O and glucose are ball-milled in water, and after spray drying and calcination, the carbon-coated vanadium sodium phosphate anode material is obtained.
CN115050945a discloses a preparation method of biomass nitrogen-doped carbon-coated lithium-rich lithium iron phosphate positive electrode material, which comprises the following steps: adding deionized water dropwise into lithium hydroxide, and stirring to dissolve the lithium hydroxide; and (3) placing silk in a lithium hydroxide solution, heating, stirring and dissolving, adding the carbon-coated lithium iron phosphate anode material, and drying and sintering the mixed slurry to obtain the biomass nitrogen-doped carbon-coated lithium iron phosphate anode material.
However, the problems of the prior art, such as high cost and limited improvement of the rate performance and cycle performance of the counter electrode material, have been difficult to solve.
In view of the above, it is an urgent technical problem to be solved at present to provide a preparation method of an electrode material with low cost, so that the prepared electrode material can obtain excellent rate performance and cycle performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a composite electrode material, and a preparation method and application thereof. The invention mixes the organic sulfonic acid substance containing carbon element, nitrogen element and sulfur element with the electrode main material, and calcines to obtain the carbon-coated electrode material with nitrogen-sulfur doping. By introducing the nitrogen-sulfur doped carbon coating, the rate capability and the cycle performance of the electrode material are improved, and the high-rate charge-discharge capacity of the electrode material is also improved. The preparation method has simple process, low cost and good development potential.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a composite electrode material, the method comprising the steps of:
mixing an electrode main material with an organic sulfonic acid substance, and calcining to obtain the composite electrode material;
wherein the elements in the organic sulfonic acid substance comprise carbon element, nitrogen element and sulfur element.
According to the invention, the organic sulfonic acid substances containing carbon, nitrogen and sulfur are introduced into the electrode material, so that the nitrogen-sulfur doped carbon coating layer is formed on the surface of the electrode material particles, the active sites on the electrode surface are increased, the conductivity of the material is improved, the structure is more stable, the rate capability and the cycle performance of the electrode material are improved, and the high-rate charge-discharge capacity of the electrode material is improved. The preparation method has simple process, low cost and good development potential.
The invention adopts organic sulfonic acid substances, can effectively reduce the temperature rise caused by ohmic polarization increase under high-rate charge and discharge of the battery, and the doping of sulfur and nitrogen atoms can enlarge the interlayer spacing of the electrode material and slow down the irreversible collapse of the interlayer structure of the electrode material.
It should be noted that the electrode host material is not limited in the present invention, and the electrode host material may be an anode material, for example, lithium iron phosphate, lithium cobalt oxide, lithium manganate, or the like, or may be a cathode material, for example, artificial graphite, natural graphite, or the like.
Preferably, the organic sulfonic acid substance comprises taurine and/or sulfamic acid.
In the invention, taurine is sulfur-containing amino acid with a simple structure in an animal body, sulfamic acid is inorganic solid acid formed by substituting hydroxyl groups of sulfuric acid with amino groups, nitrogen elements in the amino groups can accelerate the charge transfer process of electrode reaction on the surface of an electrode when the taurine is applied to an electrode material, and sulfur elements in sulfonic acid groups can stabilize the interlayer structure of the electrode.
Preferably, the mass ratio of the electrode main material to the organic sulfonic acid substances is (120-150): (1-18), wherein the selection range of the electrode main material "120-150" can be 120, 125, 130, 135, 140, 145 or 150, and the like, and the selection range of the organic sulfonic acid substances "1-18" can be 1, 3, 5, 7, 9, 12, 14, 16 or 18, and the like.
In the invention, if the mass ratio of the electrode main material to the organic sulfonic acid substances is too small, namely the consumption of the organic sulfonic acid substances is too large, the lithium ion intercalation or deintercalation channel is lengthened, and the lithium ion migration difficulty is increased; if the mass ratio of the electrode main material to the organic sulfonic acid substances is too large, namely the consumption of the organic sulfonic acid substances is too small, the electrode main material structure cannot be completely covered, and the improvement effect is not obvious.
Preferably, the method of mixing comprises ball milling.
Preferably, the ball-milling mixing comprises dry ball milling or wet ball milling, preferably wet ball milling.
The invention adopts wet ball milling, and can fully mix electrode main materials and organic sulfonic acid substances.
Preferably, the specific steps of wet ball milling include:
dispersing the electrode main material and the organic sulfonic acid substance in a solvent to obtain mixed slurry, and ball-milling the mixed slurry.
Preferably, the solvent comprises any one or a combination of at least two of methanol, ethanol or N-methylpyrrolidone.
Preferably, the ball milling is carried out at a rate of 200-300rpm, for example, 200rpm, 225rpm, 250rpm, 275rpm, 300rpm, etc.
Preferably, the temperature of the mixing is 40-80 ℃, for example, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or the like can be used.
Preferably, the mixing time is 5-7h, for example, 5h, 5.5h, 6h, 6.5h, 7h, etc.
Preferably, the calcination is performed under a protective atmosphere.
Preferably, the gas in the protective atmosphere comprises any one or a combination of at least two of nitrogen, argon or helium.
As a preferable technical scheme, the calcination method is fractional calcination.
Preferably, the step calcination includes a first order calcination and a second order calcination.
Preferably, the temperature of the first-order calcination is 200 to 300 ℃, and may be 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, or the like, for example.
In the invention, if the temperature of the first-order calcination is too low, the coating is agglomerated and cannot form a layered structure; if the first-order calcination temperature is too high, the coating layer is cracked, and the structure is destroyed.
Preferably, the time of the first-stage calcination is 2-4h, and may be, for example, 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h, 3.8h, or 4h, etc.
Preferably, the second order calcination temperature is 450-600deg.C, and may be, for example, 450deg.C, 470 deg.C, 490 deg.C, 500 deg.C, 520 deg.C, 540 deg.C, 560 deg.C, 580 deg.C, 600 deg.C, etc.
In the invention, if the temperature of the second-order calcination is too low, the carbonization of the coating layer is uneven, and the improvement effect is reduced; if the second-order calcining temperature is too high, the pore diameter of the coating layer is contracted, and the ion charge transfer is hindered.
Preferably, the second-order calcination time is 2-5h, and may be, for example, 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h, 4.2h, 4.4h, 4.6h, 4.8h, or 5h, etc.
Preferably, the protective atmosphere of the first-order calcination is the same as that of the second-order calcination.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) Ball-milling and mixing the electrode main material with the mass ratio of (120-150) (1-18) and organic sulfonic acid substances in a solvent at 200-300rpm for 5-7h, wherein the mixing temperature is 40-80 ℃ to obtain a mixture;
(2) And (3) calcining the mixture in the step (1) for 2-4 hours in a first-order under the protective atmosphere at 200-300 ℃ and then calcining for 2-5 hours in a second-order under the protective atmosphere at 450-600 ℃ to obtain the composite electrode material.
In a second aspect, the invention provides a composite electrode material prepared by the preparation method in the first aspect, wherein the composite electrode material comprises an electrode material inner core and a sulfur-nitrogen doped carbon coating layer positioned on the surface of the inner core.
In the present invention, the electrode material may be a positive electrode material, for example, lithium iron phosphate or lithium manganate, or a negative electrode material, for example, a graphite negative electrode material, or the like.
In a third aspect, the present invention provides an electrode sheet comprising a composite electrode material as described in the second aspect.
In a fourth aspect, the present invention provides a lithium ion battery comprising an electrode sheet according to the third aspect.
The numerical ranges recited herein include not only the above-listed point values, but also any point values between the above-listed numerical ranges that are not listed, and are limited in space and for the sake of brevity, the present invention is not intended to be exhaustive of the specific point values that the stated ranges include.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the organic sulfonic acid substances containing carbon, nitrogen and sulfur are introduced into the electrode material, so that the nitrogen-sulfur doped carbon coating layer is formed on the surface of the electrode material particles, the active sites on the electrode surface are increased, the conductivity of the material is improved, the structure is more stable, the rate capability and the cycle performance of the electrode material are improved, and the high-rate charge-discharge capacity of the electrode material is improved;
(2) The preparation method provided by the invention has the advantages of simple process, low cost and good development potential.
Drawings
Fig. 1 is a schematic view of a preparation process of a composite electrode material according to example 1 of the present invention.
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
The embodiment provides a preparation method of a composite positive electrode material, as shown in fig. 1. The preparation method comprises the following steps:
(1) Mixing electrode main materials with the mass ratio of 135:10 with organic sulfonic acid substances in a solvent to obtain mixed slurry, and ball-milling and mixing for 7 hours at 200rpm, wherein the mixing temperature is 60 ℃ to obtain a mixture;
wherein the electrode main material is lithium iron phosphate, and the organic sulfonic acid substance is taurine; the solvent is methanol;
(2) And (3) calcining the mixture in the step (1) for 4 hours in the first order under the protective atmosphere (namely nitrogen) at 300 ℃, and then calcining for 3 hours in the second order under the protective atmosphere (namely nitrogen) at 550 ℃ to obtain the composite electrode material, namely the lithium iron phosphate anode material with the sulfur-nitrogen doped carbon coating layer.
Example 2
The embodiment provides a preparation method of a composite positive electrode material, which comprises the following steps:
(1) Mixing lithium manganate and sulfamic acid in a mass ratio of 120:18 in ethanol to obtain mixed slurry, and ball-milling and mixing for 6 hours at 250rpm, wherein the mixing temperature is 40 ℃, so as to obtain a mixture;
(2) And (3) calcining the mixture in the step (1) for 2 hours in a first step in an argon atmosphere at 300 ℃, and then calcining for 5 hours in a second step in an argon atmosphere at 450 ℃ to obtain the lithium manganate anode material with the sulfur-nitrogen doped carbon coating layer.
Example 3
The embodiment provides a preparation method of a composite anode material, which comprises the following steps:
(1) Mixing artificial graphite and taurine in a mass ratio of 142:5 in N-methyl pyrrolidone to obtain mixed slurry, and ball-milling and mixing at 275rpm for 5.5 hours at a temperature of 50 ℃ to obtain a mixture;
(2) And (3) calcining the mixture in the step (1) for 3 hours in a helium atmosphere at 250 ℃ for the first time, and then calcining the mixture in a helium atmosphere at 500 ℃ for the second time for 4 hours to obtain the graphite anode material with the sulfur-nitrogen doped carbon coating layer.
Example 4
The embodiment provides a preparation method of a composite anode material, which comprises the following steps:
(1) Mixing natural graphite with the mass ratio of 150:1 with sulfamic acid in ethanol to obtain mixed slurry, and ball-milling and mixing for 5 hours at 300rpm, wherein the mixing temperature is 80 ℃ to obtain a mixture;
(2) And (3) calcining the mixture in the step (1) for 4 hours in a first step in a nitrogen atmosphere at 200 ℃, and then calcining for 2 hours in a second step in a nitrogen atmosphere at 600 ℃ to obtain the graphite anode material with the sulfur-nitrogen doped carbon coating layer.
Example 5
The difference between this example and example 1 is that the mass ratio of lithium iron phosphate to taurine in step (1) is 110:18.
The remaining preparation methods and parameters remain the same as in example 1.
Example 6
The difference between this example and example 1 is that the mass ratio of lithium iron phosphate to taurine in step (1) is 160:1.
The remaining preparation methods and parameters remain the same as in example 1.
Example 7
This example differs from example 1 in that the temperature of the first-stage calcination in step (2) is 150 ℃.
The remaining preparation methods and parameters remain the same as in example 1.
Example 8
This example differs from example 1 in that the temperature of the first-stage calcination in step (2) is 350 ℃.
The remaining preparation methods and parameters remain the same as in example 1.
Example 9
This example differs from example 1 in that the second calcination in step (2) is carried out at a temperature of 400 ℃.
The remaining preparation methods and parameters remain the same as in example 1.
Example 10
This example differs from example 1 in that the second order calcination in step (2) is at a temperature of 650 ℃.
The remaining preparation methods and parameters remain the same as in example 1.
Comparative example 1
This comparative example differs from example 1 in that the taurine described in step (1) is replaced by benzenesulfonic acid.
The remaining preparation methods and parameters remain the same as in example 1.
Comparative example 2
This comparative example differs from example 1 in that the taurine described in step (1) is replaced by benzenesulfonamide.
The remaining preparation methods and parameters remain the same as in example 1.
Comparative example 3
This comparative example provides the same lithium iron phosphate cathode material as in example 1, except that no taurine was used for coating.
Application example 1
The application example provides a lithium ion battery, wherein the lithium ion battery adopts the positive electrode plate prepared from the composite positive electrode material provided in the embodiment 1, adopts conventional artificial graphite as a negative electrode plate, adopts a ceramic coating diaphragm as the diaphragm, adopts lithium hexafluorophosphate electrolyte as the electrolyte, and is assembled to obtain the lithium ion battery.
Application example 2
The application example provides a lithium ion battery, wherein the lithium ion battery adopts the positive electrode plate prepared from the composite positive electrode material provided in the embodiment 2, adopts conventional artificial graphite as a negative electrode plate, adopts a ceramic coating diaphragm as a diaphragm, adopts lithium hexafluorophosphate electrolyte as electrolyte, and is assembled to obtain the lithium ion battery.
Application example 3
The application example provides a lithium ion battery, wherein the lithium ion battery adopts the positive electrode plate prepared from the composite positive electrode material provided in the embodiment 5, adopts conventional artificial graphite as a negative electrode plate, adopts a ceramic coating diaphragm as the diaphragm, adopts lithium hexafluorophosphate electrolyte as the electrolyte, and is assembled to obtain the lithium ion battery.
Application example 4
The application example provides a lithium ion battery, wherein the lithium ion battery adopts the positive electrode plate prepared from the composite positive electrode material provided in the embodiment 6, adopts conventional artificial graphite as a negative electrode plate, adopts a ceramic coating diaphragm as the diaphragm, adopts lithium hexafluorophosphate electrolyte as the electrolyte, and is assembled to obtain the lithium ion battery.
Application example 5
The application example provides a lithium ion battery, wherein the lithium ion battery adopts the positive electrode plate prepared from the composite positive electrode material provided in the embodiment 7, adopts conventional artificial graphite as a negative electrode plate, adopts a ceramic coating diaphragm as the diaphragm, adopts lithium hexafluorophosphate electrolyte as the electrolyte, and is assembled to obtain the lithium ion battery.
Application example 6
The application example provides a lithium ion battery, wherein the lithium ion battery adopts the positive electrode plate prepared from the composite positive electrode material provided in the embodiment 8, adopts conventional artificial graphite as a negative electrode plate, adopts a ceramic coating diaphragm as a diaphragm, adopts lithium hexafluorophosphate electrolyte as electrolyte, and is assembled to obtain the lithium ion battery.
Application example 7
The application example provides a lithium ion battery, wherein the lithium ion battery adopts the positive electrode plate prepared from the composite positive electrode material provided in the embodiment 9, adopts conventional natural graphite as a negative electrode plate, adopts a ceramic coating diaphragm as a diaphragm, adopts lithium hexafluorophosphate electrolyte as electrolyte, and is assembled to obtain the lithium ion battery.
Application example 8
The application example provides a lithium ion battery, wherein the lithium ion battery adopts the positive electrode plate prepared from the composite positive electrode material provided in the embodiment 10, adopts conventional natural graphite as a negative electrode plate, adopts a ceramic coating diaphragm as a diaphragm, adopts lithium hexafluorophosphate electrolyte as electrolyte, and is assembled to obtain the lithium ion battery.
Application example 9
The application example provides a lithium ion battery, wherein the lithium ion battery adopts the negative electrode plate prepared from the composite negative electrode material provided in the embodiment 3, adopts conventional lithium manganate as a positive electrode plate, adopts a ceramic coating diaphragm as a diaphragm, adopts lithium hexafluorophosphate as electrolyte, and is assembled to obtain the lithium ion battery.
Application example 10
The application example provides a lithium ion battery, wherein the lithium ion battery adopts the negative electrode plate prepared from the composite negative electrode material provided in the embodiment 4, adopts conventional lithium iron phosphate as a positive electrode plate, adopts a ceramic coating diaphragm, adopts lithium hexafluorophosphate electrolyte as electrolyte, and is assembled to obtain the lithium ion battery.
Application example 11
The application example provides a lithium ion battery, wherein the lithium ion battery adopts the positive electrode plate prepared by the composite positive electrode material provided in the embodiment 1, adopts the negative electrode plate prepared by the composite negative electrode material provided in the embodiment 3, and the diaphragm is a ceramic coating diaphragm, and the electrolyte is lithium hexafluorophosphate electrolyte, so that the lithium ion battery is obtained through assembly.
Application example 12
The application example provides a lithium ion battery, wherein the lithium ion battery adopts the positive electrode plate prepared by the composite positive electrode material provided in the embodiment 2, adopts the negative electrode plate prepared by the composite negative electrode material provided in the embodiment 4, and the diaphragm is a ceramic coating diaphragm, and the electrolyte is lithium hexafluorophosphate electrolyte, so that the lithium ion battery is obtained through assembly.
Application example 13
The application example provides a lithium ion battery, wherein the lithium ion battery adopts the positive electrode plate prepared by the composite positive electrode material provided in the embodiment 1, adopts the negative electrode plate prepared by the composite negative electrode material provided in the embodiment 4, and the diaphragm is a ceramic coating diaphragm, and the electrolyte is lithium hexafluorophosphate electrolyte, so that the lithium ion battery is obtained through assembly.
Comparative example 1 was used
The application comparative example provides a lithium ion battery, wherein the lithium ion battery adopts the positive electrode plate prepared from the composite positive electrode material provided in comparative example 1, adopts conventional artificial graphite as a negative electrode plate, adopts a ceramic coating diaphragm as the diaphragm, adopts lithium hexafluorophosphate electrolyte as the electrolyte, and is assembled to obtain the lithium ion battery.
Comparative example 2 was used
The application comparative example provides a lithium ion battery, wherein the lithium ion battery adopts the positive electrode plate prepared by the composite positive electrode material provided in comparative example 2, adopts conventional artificial graphite as a negative electrode plate, adopts a ceramic coating diaphragm as the diaphragm, adopts lithium hexafluorophosphate electrolyte as the electrolyte, and is assembled to obtain the lithium ion battery.
Comparative example 3 was used
The application comparative example provides a lithium ion battery, wherein the lithium ion battery adopts the positive electrode plate prepared by the positive electrode material provided in comparative example 3, adopts conventional natural graphite as a negative electrode plate, adopts a ceramic coating diaphragm as a diaphragm, adopts lithium hexafluorophosphate electrolyte as electrolyte, and is assembled to obtain the lithium ion battery.
Performance testing
Electrochemical performance tests were performed on the lithium ion batteries provided in application examples 1 to 13 and application comparative examples 1 to 3.
Test conditions: measuring the multiplying power under 1C, measuring the cycling stability under 4000 circles, and measuring the charging and discharging capacity under 3C.
The test results are shown in Table 1.
TABLE 1
Analysis:
from the data results of application examples 1-2, the effect of taurine on improving the rate performance and the cycle performance of the battery by being applied to the lithium iron phosphate material coating is superior to that of sulfamic acid by being applied to the lithium iron manganese material coating; from the data results of application examples 9-10, the effect of taurine on improving the rate performance and the cycle performance of the battery by applying the taurine to the artificial graphite material coating is superior to that of the taurine by applying the taurine to the natural graphite material coating; from the data of application examples 11 to 13, it was found that the positive electrode and negative electrode materials were coated with taurine at the same time to provide the best improvement effect.
As can be seen from comparison of the data results of application examples 1 and application examples 3-4, the excessive amount of taurine lengthens the lithium ion intercalation or deintercalation channel, and the lithium ion migration difficulty is increased, so that the improvement effect of the rate performance and the cycle performance of the battery is not obvious; if the taurine is excessively used, the electrode main material structure cannot be completely covered, and the improvement effect of the rate performance and the cycle performance of the battery is not obvious.
As is clear from comparison of the data results of application examples 1 and application examples 5 to 6, the temperature of the first-order calcination is too low, the coating is agglomerated, a layered structure cannot be formed, and the rate performance and the cycle performance of the battery are reduced; when the first-order calcination temperature is too high, the coating layer is cracked, the structure is destroyed, and the rate performance and the cycle performance of the battery are reduced.
As can be seen from the comparison of the data results of application example 1 and application examples 7-8, the second-order calcination temperature is too low, so that the carbonization of the coating is uneven, and the improvement effect is reduced; and if the second-order calcining temperature is too high, the aperture of the coating layer is contracted to block the ion charge transmission, so that the rate performance and the cycle performance of the battery are reduced.
As can be seen from comparison of the data of application example 1 and comparative example 1, the application of taurine to the coated lithium iron phosphate material has better improvement effect on the rate performance and cycle performance of the battery than that of benzenesulfonic acid.
As can be seen from comparison of the data results of application example 1 and application comparative example 2, the application of taurine to the coated lithium iron phosphate material has better improvement effect on the rate performance and cycle performance of the battery than that of benzenesulfonamide
As can be seen from comparison of the data results of application example 1 and application comparative example 3, the application of taurine to the coated lithium iron phosphate material has obvious improvement on the rate performance and the cycle performance of the battery.
The applicant states that the process of the invention is illustrated by the above examples, but the invention is not limited to, i.e. does not mean that the invention must be carried out in dependence on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A method for preparing a composite electrode material, which is characterized by comprising the following steps:
mixing an electrode main material with an organic sulfonic acid substance, and calcining to obtain the composite electrode material;
wherein the elements in the organic sulfonic acid substance comprise carbon element, nitrogen element and sulfur element.
2. The method according to claim 1, wherein the organic sulfonic acid substance comprises taurine and/or sulfamic acid;
preferably, the mass ratio of the electrode main material to the organic sulfonic acid substance is (120-150): 1-18.
3. The method of preparation according to claim 1 or 2, wherein the method of mixing comprises ball milling mixing;
preferably, the ball-milling mixing comprises dry ball milling or wet ball milling, preferably wet ball milling;
preferably, the specific steps of wet ball milling include:
dispersing the electrode main material and organic sulfonic acid substances in a solvent to obtain mixed slurry, and ball-milling the mixed slurry;
preferably, the solvent comprises any one or a combination of at least two of methanol, ethanol or N-methylpyrrolidone;
preferably, the ball milling is carried out at a rate of 200-300rpm.
4. A method of preparation according to any one of claims 1 to 3 wherein the temperature of mixing is 40 to 80 ℃;
preferably, the mixing is for a period of time ranging from 5 to 7 hours.
5. The method according to any one of claims 1 to 4, wherein the calcination is performed under a protective atmosphere;
preferably, the gas in the protective atmosphere comprises any one or a combination of at least two of nitrogen, argon or helium.
6. The method of any one of claims 1-5, wherein the method of calcining is fractional calcination;
preferably, the step calcination includes first-order calcination and second-order calcination;
preferably, the temperature of the first order calcination is 200-300 ℃;
preferably, the first-order calcination is carried out for a time of 2 to 4 hours;
preferably, the temperature of the second order calcination is 450-600 ℃;
preferably, the second order calcination is for a period of 2 to 5 hours.
7. The preparation method according to any one of claims 1 to 6, characterized in that the preparation method comprises the steps of:
(1) Ball-milling and mixing the electrode main material with the mass ratio of (120-150) (1-18) and organic sulfonic acid substances in a solvent at 200-300rpm for 5-7h, wherein the mixing temperature is 40-80 ℃ to obtain a mixture;
(2) And (3) calcining the mixture in the step (1) for 2-4 hours in a first-order under the protective atmosphere at 200-300 ℃ and then calcining for 2-5 hours in a second-order under the protective atmosphere at 450-600 ℃ to obtain the composite electrode material.
8. A composite electrode material prepared by the preparation method of any one of claims 1 to 7, wherein the composite electrode material comprises an electrode material core and a sulfur-nitrogen doped carbon coating layer positioned on the surface of the core.
9. An electrode sheet comprising the composite electrode material of claim 8.
10. A lithium ion battery comprising the electrode sheet of claim 9.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017190363A1 (en) * | 2016-05-06 | 2017-11-09 | 深圳先进技术研究院 | Negative electrode active material, preparation method therefor, negative electrode and secondary battery comprising negative electrode active material |
| CN108493424A (en) * | 2018-04-11 | 2018-09-04 | 中科锂电新能源有限公司 | A kind of nitrogen phosphate and sulfur codope complex carbon material, preparation method and lithium ion battery |
| CN112599730A (en) * | 2020-11-30 | 2021-04-02 | 重庆特瑞新能源材料有限公司 | Preparation method of carbon-coated lithium iron phosphate cathode material |
| CN114188511A (en) * | 2020-09-14 | 2022-03-15 | 湖南中科星城石墨有限公司 | Nitrogen-doped carbon-coated graphite composite material and preparation method and application thereof |
| CN115050945A (en) * | 2022-07-15 | 2022-09-13 | 湖北工业大学 | Preparation method of biomass nitrogen-doped carbon-coated lithium-rich lithium iron phosphate positive electrode material |
| CN115072693A (en) * | 2022-06-29 | 2022-09-20 | 蜂巢能源科技股份有限公司 | Lithium iron phosphate cathode material, preparation method thereof and lithium ion battery |
| CN115966667A (en) * | 2022-12-15 | 2023-04-14 | 天津巴莫科技有限责任公司 | Lithium-rich manganese-based positive electrode material and preparation method and application thereof |
-
2023
- 2023-04-28 CN CN202310480663.7A patent/CN116525827A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017190363A1 (en) * | 2016-05-06 | 2017-11-09 | 深圳先进技术研究院 | Negative electrode active material, preparation method therefor, negative electrode and secondary battery comprising negative electrode active material |
| CN108493424A (en) * | 2018-04-11 | 2018-09-04 | 中科锂电新能源有限公司 | A kind of nitrogen phosphate and sulfur codope complex carbon material, preparation method and lithium ion battery |
| CN114188511A (en) * | 2020-09-14 | 2022-03-15 | 湖南中科星城石墨有限公司 | Nitrogen-doped carbon-coated graphite composite material and preparation method and application thereof |
| CN112599730A (en) * | 2020-11-30 | 2021-04-02 | 重庆特瑞新能源材料有限公司 | Preparation method of carbon-coated lithium iron phosphate cathode material |
| CN115072693A (en) * | 2022-06-29 | 2022-09-20 | 蜂巢能源科技股份有限公司 | Lithium iron phosphate cathode material, preparation method thereof and lithium ion battery |
| CN115050945A (en) * | 2022-07-15 | 2022-09-13 | 湖北工业大学 | Preparation method of biomass nitrogen-doped carbon-coated lithium-rich lithium iron phosphate positive electrode material |
| CN115966667A (en) * | 2022-12-15 | 2023-04-14 | 天津巴莫科技有限责任公司 | Lithium-rich manganese-based positive electrode material and preparation method and application thereof |
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