CN115332507B - Carbon-coated sodium iron phosphate composite electrode material and preparation and application thereof - Google Patents
Carbon-coated sodium iron phosphate composite electrode material and preparation and application thereof Download PDFInfo
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- CN115332507B CN115332507B CN202210996876.0A CN202210996876A CN115332507B CN 115332507 B CN115332507 B CN 115332507B CN 202210996876 A CN202210996876 A CN 202210996876A CN 115332507 B CN115332507 B CN 115332507B
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- 239000007772 electrode material Substances 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 62
- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229910052742 iron Inorganic materials 0.000 claims abstract description 29
- 239000011148 porous material Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims abstract description 13
- 235000019799 monosodium phosphate Nutrition 0.000 claims abstract description 13
- 238000000197 pyrolysis Methods 0.000 claims abstract description 13
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims abstract description 13
- 238000012983 electrochemical energy storage Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 7
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 5
- 239000010432 diamond Substances 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 239000013082 iron-based metal-organic framework Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000013110 organic ligand Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [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 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 8
- 229910052708 sodium Inorganic materials 0.000 abstract description 8
- 239000011734 sodium Substances 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 35
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 25
- 238000004146 energy storage Methods 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000013384 organic framework Substances 0.000 description 5
- 229910000358 iron sulfate Inorganic materials 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 241000282412 Homo Species 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010325 electrochemical charging Methods 0.000 description 1
- 238000010326 electrochemical discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 208000016253 exhaustion Diseases 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000447 polyanionic polymer Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The application discloses a carbon-coated sodium iron phosphate composite electrode material, and preparation and application thereof, wherein the composite electrode material is applied to electrochemical energy storage and comprises carbon-coated sodium iron phosphate particles with the particle size of 30-90nm, the carbon-coated sodium iron phosphate is of a three-dimensional diamond structure, and a pore canal is formed in the composite electrode material. The preparation method of the carbon-coated sodium iron phosphate composite electrode material comprises the following steps: step 1: preparing an iron-based metal organic frame; step 2: and mixing the iron-based metal organic frame with sodium dihydrogen phosphate according to a preset proportion, and carrying out pyrolysis reaction in a protective atmosphere to obtain the carbon-coated sodium iron phosphate composite electrode material. The composite electrode material prepared by the application has the advantages of high sodium storage capacity, stable cycle performance, excellent multiplying power performance and the like.
Description
Technical Field
The application belongs to the technical field of electrochemical energy storage electrode materials, and particularly relates to a carbon-coated sodium iron phosphate composite electrode material, and preparation and application thereof.
Background
The energy source provides a material basis for the development of human civilization. With the rapid development of global economy, the demand for energy by humans is increasing. At present, natural gas, petroleum, coal and the like provide main energy sources for human beings. However, the endless exploitation of these fossil energy sources by humans causes great environmental pollution problems. Furthermore, the non-renewable nature of fossil energy itself leads to its progressive exhaustion.
The electrochemical energy storage has the characteristics of high safety, high efficiency, low price, simple operation and the like, and is most suitable for the development of the energy sources at present. The lithium ion battery has the characteristics of high safety, environmental friendliness, high energy density, long cycle time, no memory effect and the like, and has been widely applied to portable electronic products, electric automobiles and large and medium-sized energy storage batteries. However, lithium resources are distributed unevenly worldwide and mainly distributed in south america, and the abundance in the crust is low, so that the price fluctuation of the lithium resources is severe and the lithium resources are likely to become strategic resources; in order to meet the increasing demand, the lithium resources in China are highly dependent on import.
Lithium resource shortage tends to result in limited application of lithium batteries in electric vehicles and large and medium-sized energy storage batteries and devices. Therefore, in order to meet the requirements of a large-scale energy storage system, it is of great importance to find next-generation energy storage devices and electrode materials with high power density and energy density and low cost. Sodium and lithium belong to the same main group element, and show similar 'rocking chair type' electrochemical charging and discharging behaviors in battery operation. The sodium ion battery energy storage system has the advantages of abundant raw materials, low cost, wide distribution, high energy conversion efficiency and the like, and becomes a new generation of battery main angle for replacing lithium ion batteries. The market expects that the sodium battery has wide prospect in application scenes of power grid energy storage, lead-acid battery replacement in low-speed electric vehicle scenes, power supply of large-scale traffic equipment and the like, which have slightly lower energy density requirements and are more sensitive to battery stability and cost. In addition, the positive electrode material of the sodium ion battery does not contain cobalt (or the cobalt content in the multi-element positive electrode material is low), and the nickel content is less, so that the recovery cost for preventing the heavy metal pollution of the waste battery in the later period is reduced to a great extent. Compared with a lithium ion battery, the sodium ion battery has remarkable economic benefit, ensures the energy safety of China, reduces the political significance and social effect of waste battery pollution and the like, and is also worth drawing attention. Therefore, the development of sodium ion batteries for large-scale energy storage has important strategic significance.
However, the radius of sodium ions is larger than that of lithium ions, so that an electrode material applicable to a lithium ion battery is not necessarily well suited for a sodium ion battery, so finding a suitable electrode material for sodium storage and ensuring rapid reversible intercalation/deintercalation of sodium ions in the material is a great challenge. Therefore, searching for a positive electrode material with high specific capacity, stable structure and low price is a key for improving the overall performance of the sodium ion battery.
The currently reported positive electrode materials of the sodium ion battery mainly comprise Prussian blue compounds, metal oxides and polyanion compounds. But sodium ion battery materials are mostly focused on morphology control and modification. And can not provide more channels for rapid transmission of sodium ions with larger radius, and the conductivity and sodium ion diffusion mobility are required to be further improved.
Disclosure of Invention
Aiming at the problems existing in the prior art, the application provides the carbon-coated sodium iron phosphate composite electrode material, and the preparation and application thereof, and the obtained carbon-coated sodium iron phosphate composite electrode material has a large number of pore canals, and has the advantages of high sodium storage capacity, stable cycle performance, excellent multiplying power performance and the like when being used as an anode material for electrochemical energy storage.
In order to achieve the above purpose, the technical scheme of the application is as follows:
the carbon-coated sodium iron phosphate composite electrode material is used for electrochemical energy storage, and comprises carbon-coated sodium iron phosphate particles with the particle size of 30-90nm, wherein the carbon-coated sodium iron phosphate is of a three-dimensional diamond structure, the composite electrode material is provided with pore channels, the average pore diameter of the pore channels is 10-30nm, the porosity of the composite electrode material is 25-40%, and the carbon-coated sodium iron phosphate composite electrode material is prepared by heat treatment of a metal organic framework.
Preferably, the cells include cells having an average pore size of 10-20nm and an average pore size of 20-30 nm.
According to the same inventive concept, the application also provides a preparation method of the carbon-coated sodium iron phosphate composite electrode material, which comprises the following steps:
step 1: preparing an iron-based metal organic frame;
step 2: and mixing the iron-based metal organic frame with sodium dihydrogen phosphate according to a preset proportion, and carrying out pyrolysis reaction in a protective atmosphere to obtain the carbon-coated sodium iron phosphate composite electrode material.
In one embodiment of the present application, the step 1 specifically includes:
step 101: the inorganic ferric salt and the organic ligand are mixed according to the mol ratio of 1:1-5 are respectively dissolved in a solvent to obtain an inorganic ferric salt solution and an organic ligand solution;
step 102: and uniformly mixing the inorganic ferric salt solution and the organic ligand solution in a dropwise adding mode, and standing at 90-180 ℃ for reaction for 4-30 hours to obtain the iron-based metal organic framework.
In one embodiment of the present application, the solvent is a mixed solution of N, N-dimethylformamide and deionized water.
In one embodiment of the present application, the inorganic iron salt is one or more of ferric nitrate, ferric chloride, ferric acetate or ferric sulfate.
In one embodiment of the present application, the organic ligand is fumaric acid, 1, 4-terephthalic acid or 1,3, 5-isophthalic acid.
In one embodiment of the present application, in step 102, after the standing reaction is completed, the reacted mixture needs to be centrifugally separated, and then deionized water and absolute ethyl alcohol are used for cleaning, so as to obtain the iron-based metal-organic frame.
In one embodiment of the present application, in the step 1, the molar ratio of the iron-based metal organic framework to the sodium dihydrogen phosphate is 1: ball milling or grinding and mixing 1-4, heating to 500-900 deg.C at a heating rate of 0.5-10 deg.C/min under the protection of high-purity argon, holding at the temperature for 2-10h for reaction, and cooling.
Based on the same inventive concept, the application also provides application of the carbon-coated sodium iron phosphate composite electrode material, wherein the carbon-coated sodium iron phosphate composite electrode material is obtained by the composite electrode material of the embodiment or the preparation method of the carbon-coated sodium iron phosphate composite electrode material, and the carbon-coated sodium iron phosphate composite electrode material is applied to an anode for electrochemical energy storage.
By adopting the technical scheme, the application has the following advantages and positive effects compared with the prior art:
(1) The iron-based metal organic framework is decomposed into CO and CO during the pyrolysis reaction process due to the organic ligand 2 And H 2 Small molecular gas such as O and the like can form a multi-pore structure in the electrode material, and the multi-pore structure can effectively promote the gap diffusion of sodium ions in the electrode material.
(2) The iron-based metal organic frame is also carbonized in the pyrolysis process, and in the carbonization process, an amorphous carbon layer coating is formed, and meanwhile, an amorphous carbon supporting iron-based metal organic frame is also formed, so that the final composite electrode material is provided with a large number of pore channels, a sodium ion transmission channel is provided, and meanwhile, the conductivity of the electrode material can be greatly improved by the amorphous carbon, and the sodium ion transmission rate is improved. In addition, the protective effect of the carbon layer can also relieve the volume expansion effect of sodium ions in the process of deintercalation in the electrode material, so that the carbon-coated sodium iron phosphate composite electrode material obtained based on the application is used as a positive electrode material of a sodium ion battery, has the advantages of rapid sodium ion transmission, high specific capacity, excellent cycle performance and rate performance and the like, and shows good electrochemical performance.
(3) One of the technical barriers to be overcome for current sodium ion batteries is that the material structure constituting the electrode is not stable, resulting in a short battery cycle life. According to the application, the composite electrode material with the high-porosity porous structure is constructed to be used as the electrode material of the sodium ion energy storage battery, so that the structural stability of the electrode material is realized, the utilization rate of the active material is increased, and the cycling stability of the sodium ion battery is further improved.
(4) The composite electrode material is used as a material of a sodium ion battery, and because the radius of sodium ions is larger, the sodium ions are required to be quickly and reversibly embedded/extracted in the material, the composite electrode material has a large number of pore channels, the pore size of the pore channels is directly related to the embedding/extracting of the sodium ions, the electrochemical activity and the rate performance are higher at 20-30nm with larger pore size, and the cycling stability is better at 10-20nm with smaller pore size. Therefore, the carbon-coated sodium iron phosphate composite electrode material prepared by the application comprises a porous material with graded pore diameters, increases the utilization rate of active materials, and shows excellent rate performance and cycle stability.
(5) The preparation method of the carbon-coated sodium iron phosphate composite electrode material provided by the application has the advantages of simplicity, no pollution, low cost and the like, and is easy to realize industrial large-scale application.
Drawings
FIG. 1 is a scanning electron micrograph of a carbon-coated sodium iron phosphate composite positive electrode material prepared in example 1 of the present application;
FIG. 2 is a graph showing pore size distribution of a carbon-coated sodium iron phosphate composite positive electrode material prepared in example 1 of the present application;
fig. 3 is a graph showing the cycling performance of a sodium ion battery of the carbon-coated sodium iron phosphate composite cathode material prepared in example 1 of the present application.
Detailed Description
The carbon-coated sodium iron phosphate composite electrode material, the preparation and the application thereof are further described in detail below with reference to the accompanying drawings and specific examples. The advantages and features of the present application will become more apparent from the following description.
Ion transport in the electrode material takes two forms: gap diffusion and vacancy diffusion. The rapid transmission of sodium ions can be realized by optimizing and regulating two forms of ion transmission, and the performance of the sodium ion battery can be comprehensively improved. According to the application, the metal organic frame is utilized to regulate and control the gap diffusion and vacancy diffusion of the electrode material, so that the transmission dynamics of sodium ions in the sodium iron phosphate electrode material is improved. The metal organic framework is used as a crystal material formed by metal ions and organic ligands through self-assembly, and has the advantages of high porosity, large specific surface area, adjustable structure and functions and the like, so that the metal organic framework becomes an energy storage material with great development potential.
The features of the application are illustrated in the following specific examples
Example 1
The preparation method of the carbon-coated sodium iron phosphate composite electrode material sequentially comprises the following steps:
step 1: ferric nitrate solution and 1, 4-terephthalic acid are mixed according to a mole ratio of 1:5 respectively dissolving in solvent solutions formed by deionized water and N, N-dimethylformamide;
step 2: uniformly mixing the prepared solutions in a dropwise adding mode, and standing and growing for 10 hours at 180 ℃ to obtain a primary product containing the iron-based metal-organic framework template;
step 3: centrifugally separating a primary product containing the iron-based metal organic framework template, and respectively cleaning the primary product with deionized water and absolute ethyl alcohol for 3 times to obtain a clean iron-based metal organic framework;
step 4: and (3) mixing the clean iron-based metal organic framework obtained in the step (3) with sodium dihydrogen phosphate according to the molar ratio of 1:1, after ball milling treatment, under the protection of high-purity argon, raising the temperature to 500 ℃ at a heating rate of 0.5 ℃/min, and keeping the temperature for 2 hours for reaction;
step 5: after the pyrolysis reaction is finished, the temperature is reduced to room temperature, and the carbon-coated sodium iron phosphate composite electrode material is obtained, and as shown in fig. 1, a scanning electron microscope image of the composite material prepared in the embodiment 1 is of a diamond structure, and the surface of the composite material has a porous characteristic. The pore diameter of the prepared composite material is measured to obtain a pore diameter distribution diagram shown in figure 2, wherein the pore diameter is mainly distributed at 10-30nm, and the porosity is 25-40%.
Example 2
The preparation method of the carbon-coated sodium iron phosphate composite electrode material sequentially comprises the following steps:
step 1: ferric chloride solution and fumaric acid are mixed according to a mole ratio of 1:2 are respectively dissolved in solvent solutions formed by deionized water and N, N-dimethylformamide;
step 2: uniformly mixing the solutions in a dropwise adding mode, and standing and growing for 20 hours at 120 ℃ to obtain a primary product containing the iron-based metal organic framework template;
step 3: centrifugally separating a primary product containing the iron-based metal organic framework template, and respectively cleaning the primary product with deionized water and absolute ethyl alcohol for 3 times to obtain a clean iron-based metal organic framework;
step 4: and (3) mixing the clean iron-based metal organic framework obtained in the step (3) with sodium dihydrogen phosphate according to the molar ratio of 1:2, after ball milling treatment, under the protection of high-purity argon, raising the temperature to 600 ℃ at a heating rate of 1 ℃/min, and keeping the temperature for 3 hours for reaction;
step 5: and after the pyrolysis reaction is finished, the temperature is reduced to room temperature, and the carbon-coated sodium iron phosphate composite electrode material is obtained.
Example 3
The preparation method of the carbon-coated sodium iron phosphate composite electrode material sequentially comprises the following steps:
step 1: iron sulfate and 1,3, 5-m-trimellitic acid are mixed according to a mole ratio of 1:3 in solvent solutions formed by deionized water and N, N-dimethylformamide respectively;
step 2: uniformly mixing the solutions in a dropwise adding mode, and standing and growing for 30 hours at 150 ℃ to obtain a primary product containing the iron-based organic framework template;
step 3: centrifugally separating a primary product containing the iron-based metal organic frame template, and respectively cleaning the primary product with deionized water and absolute ethyl alcohol for 3 times to obtain a clean iron-based organic frame;
step 4: and (3) mixing the clean iron-based metal organic framework obtained in the step (3) with sodium dihydrogen phosphate according to the molar ratio of 1:3, after grinding treatment, under the protection of high-purity argon, raising the temperature to 700 ℃ at a heating rate of 2 ℃/min, and keeping the temperature for 4 hours for reaction;
step 5: and after the pyrolysis reaction is finished, the temperature is reduced to room temperature, and the carbon-coated sodium iron phosphate composite electrode material is obtained.
Example 4
The preparation method of the carbon-coated sodium iron phosphate composite electrode material sequentially comprises the following steps:
step 1: iron sulfate and 1, 4-terephthalic acid are mixed according to a mole ratio of 1:4 in solvent solutions formed by deionized water and N, N-dimethylformamide respectively;
step 2: uniformly mixing the solutions in a dropwise adding mode, and standing and growing for 4 hours at 180 ℃ to obtain a primary product containing the iron-based organic framework template;
step 3: centrifugally separating a primary product containing the iron-based metal organic frame template, and respectively cleaning the primary product with deionized water and absolute ethyl alcohol for 3 times to obtain a clean iron-based organic frame;
step 4: and (3) mixing the clean iron-based metal organic framework obtained in the step (3) with sodium dihydrogen phosphate according to the molar ratio of 1:4, after grinding treatment, under the protection of high-purity argon, raising the temperature to 800 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 5 hours for reaction;
step 5: and after the pyrolysis reaction is finished, the temperature is reduced to room temperature, and the carbon-coated sodium iron phosphate composite electrode material is obtained.
Example 5
The preparation method of the carbon-coated sodium iron phosphate composite electrode material sequentially comprises the following steps:
step 1: iron sulfate and 1,3, 5-m-trimellitic acid are mixed according to a mole ratio of 1:3 in solvent solutions formed by deionized water and N, N-dimethylformamide respectively;
step 2: uniformly mixing the solutions in a dropwise adding mode, and standing and growing for 10 hours at 170 ℃ to obtain a primary product containing the iron-based organic framework template;
step 3: centrifugally separating a primary product containing the iron-based metal organic frame template, and respectively cleaning the primary product with deionized water and absolute ethyl alcohol for 3 times to obtain a clean iron-based organic frame;
step 4: and (3) mixing the clean iron-based metal organic framework obtained in the step (3) with sodium dihydrogen phosphate according to the molar ratio of 1:1, after grinding treatment, under the protection of high-purity argon, the temperature is raised to 900 ℃ at a heating rate of 3 ℃/min, and the reaction is carried out at the temperature for 6 hours;
step 5: and after the pyrolysis reaction is finished, the temperature is reduced to room temperature, and the carbon-coated sodium iron phosphate composite electrode material is obtained.
Example 6
The preparation method of the carbon-coated sodium iron phosphate composite electrode material sequentially comprises the following steps:
step 1: ferric chloride and fumaric acid are mixed according to a mole ratio of 1:2 in deionized water and N, N-dimethylformamide respectively;
step 2: uniformly mixing the solutions in a dropwise adding mode, and standing and growing for 8 hours at 160 ℃ to obtain a primary product containing the iron-based organic framework template;
step 3: centrifugally separating a primary product containing the iron-based metal organic frame template, and respectively cleaning the primary product with deionized water and absolute ethyl alcohol for 3 times to obtain a clean iron-based organic frame;
step 4: and (3) mixing the clean iron-based metal organic framework obtained in the step (3) with sodium dihydrogen phosphate according to the molar ratio of 1:2, after grinding treatment, under the protection of high-purity argon, raising the temperature to 600 ℃ at a heating rate of 4 ℃/min, and keeping the temperature for 7 hours for reaction;
step 5: and after the pyrolysis reaction is finished, the temperature is reduced to room temperature, and the carbon-coated sodium iron phosphate composite electrode material is obtained.
Example 7
The preparation method of the carbon-coated sodium iron phosphate composite electrode material sequentially comprises the following steps:
step 1: iron sulfate and 1, 4-terephthalic acid are mixed according to a mole ratio of 1:3 in solvent solutions formed by deionized water and N, N-dimethylformamide respectively;
step 2: uniformly mixing the solutions in a dropwise adding mode, and standing and growing for 9 hours at 150 ℃ to obtain a primary product containing the iron-based organic frame template;
step 3: centrifugally separating a primary product containing the iron-based metal organic frame template, and respectively cleaning the primary product with deionized water and absolute ethyl alcohol for 3 times to obtain a clean iron-based organic frame;
step 4: and (3) mixing the clean iron-based metal organic framework obtained in the step (3) with sodium dihydrogen phosphate according to the molar ratio of 1:3, after grinding treatment, under the protection of high-purity argon, raising the temperature to 800 ℃ at a heating rate of 6 ℃/min, and keeping the temperature for 8 hours for reaction;
step 5: and after the pyrolysis reaction is finished, the temperature is reduced to room temperature, and the carbon-coated sodium iron phosphate composite electrode material is obtained.
Example 8
The preparation method of the carbon-coated sodium iron phosphate composite electrode material sequentially comprises the following steps:
step 1: iron acetate and 1,3, 5-m-trimellitic acid are mixed according to a mole ratio of 1:2 in deionized water and N, N-dimethylformamide respectively;
step 2: uniformly mixing the solutions in a dropwise adding mode, and standing and growing for 10 hours at 140 ℃ to obtain a primary product containing the iron-based organic framework template;
step 3: centrifugally separating a primary product containing the iron-based metal organic frame template, and respectively cleaning the primary product with deionized water and absolute ethyl alcohol for 3 times to obtain a clean iron-based organic frame;
step 4: and (3) mixing the clean iron-based metal organic framework obtained in the step (3) with sodium dihydrogen phosphate according to the molar ratio of 1:4, after grinding treatment, under the protection of high-purity argon, raising the temperature to 700 ℃ at a heating rate of 10 ℃/min, and keeping the temperature for 10 hours for reaction;
step 5: and after the pyrolysis reaction is finished, the temperature is reduced to room temperature, and the carbon-coated sodium iron phosphate composite electrode material is obtained.
Example 9
Dispersing the carbon-coated sodium iron phosphate composite electrode material prepared in examples 1-8, a binder sodium carboxymethylcellulose and a conductive agent Super-P in deionized water according to a mass ratio of 75:15:10 to prepare slurry, uniformly coating the slurry on aluminum foil with the thickness of 8 mu m, drying in vacuum for 12 hours, and preparing the circular electrode with the diameter of 12mm through a die.
The CR2032 button cell is assembled in a glove box with a metal sodium sheet as a reference electrode and a counter electrode, whatman GF/D as a diaphragm, and water and oxygen content of less than 0.5 ppm. The electrolyte composition is 1M NaClO 4 Dissolving in a mixed solvent of ethylene carbonate, diethyl carbonate and methyl ethyl carbonate in a volume ratio of 1:1:1. The CR2032 button cell was subjected to constant current charge and discharge by a blue cell tester CT2001A, the voltage volt value is 1.5-4.3V, the current density is 100mA/g, the charge and discharge cycle performance of the carbon coated sodium iron phosphate composite electrode material is tested for 200 times, and the electrochemical performance results of the electrode materials prepared in examples 1-8 are shown in Table 1.
TABLE 1
The sodium ion battery was cycled 100 times at a current density of 100mA/g with the CR2032 coin cell assembled in example 1. The obtained result is shown in fig. 3, and the sodium ion battery prepared by the carbon-coated sodium iron phosphate composite electrode material prepared in the embodiment 1 has the cycling performance under the current density of 100mA/g, and the sodium storage capacity after 100 times is 210mAh/g, so that the carbon-coated sodium iron phosphate composite electrode material has better cycling stability.
In summary, the carbon-coated sodium iron phosphate particles in the carbon-coated sodium iron phosphate composite electrode material provided by the application have a three-dimensional diamond structure and a smooth surface. The sodium ion battery is applied to an anode for electrochemical energy storage, and the sodium storage capacity of the sodium ion battery is up to 180-220mAh/g under the current density of 100 mA/g; after 200 times of cyclic charge and discharge, the capacity retention rate is higher than 94%, and the cyclic stability is good. Therefore, the carbon-coated sodium iron phosphate composite electrode material obtained by the application is used as a sodium ion battery anode material, has the advantages of rapid sodium ion transmission, high specific capacity, excellent cycle performance and rate performance and the like, and shows good electrochemical performance.
The embodiments of the present application have been described in detail with reference to the drawings, but the present application is not limited to the above embodiments. Even if various changes are made to the present application, it is within the scope of the appended claims and their equivalents to fall within the scope of the application.
Claims (7)
1. The preparation method of the carbon-coated sodium iron phosphate composite electrode material is characterized by comprising the following steps of:
step 1: preparing an iron-based metal organic frame;
step 2: the molar ratio of the iron-based metal organic framework to the sodium dihydrogen phosphate is 1:1-4, carrying out pyrolysis reaction under a protective atmosphere to obtain the carbon-coated sodium iron phosphate composite electrode material;
the carbon-coated sodium iron phosphate composite electrode material is used for electrochemical energy storage, the composite electrode material comprises carbon-coated sodium iron phosphate particles with the particle size of 30-90nm, the carbon-coated sodium iron phosphate is of a three-dimensional diamond structure, the composite electrode material is internally provided with pore channels, the average pore diameter of the pore channels is 10-30nm, and the porosity of the composite electrode material is 25-40%.
2. The method for preparing a carbon-coated sodium iron phosphate composite electrode material according to claim 1, wherein the step 1 specifically comprises:
step 101: inorganic ferric salt or ferric acetate and organic ligand are mixed according to a mole ratio of 1:1-5 are respectively dissolved in a solvent to obtain an inorganic ferric salt solution and an organic ligand solution;
step 102: and uniformly mixing the inorganic ferric salt solution and the organic ligand solution in a dropwise adding mode, and standing at 90-180 ℃ for reaction for 4-30 hours to obtain the iron-based metal organic frame.
3. The method for preparing a carbon-coated sodium iron phosphate composite electrode material according to claim 2, wherein the solvent is a mixed solution of N, N-dimethylformamide and deionized water.
4. The method for preparing a carbon-coated sodium iron phosphate composite electrode material according to claim 2, wherein the inorganic iron salt is one or more of ferric nitrate, ferric chloride and ferric sulfate.
5. The method for preparing a carbon-coated sodium iron phosphate composite electrode material according to claim 2, wherein the organic ligand is fumaric acid, 1, 4-terephthalic acid or 1,3, 5-trimellitic acid.
6. The method for preparing a carbon-coated sodium iron phosphate composite electrode material according to claim 2, wherein in step 102, after the standing reaction is completed, centrifugal separation is required to be performed on the reacted mixture, and deionized water and absolute ethyl alcohol are used for cleaning for 2-4 times, so as to obtain the iron-based metal organic frame.
7. The method for preparing the carbon-coated sodium iron phosphate composite electrode material according to claim 1, wherein in the step 1, the iron-based metal organic frame is ball milled or ground and mixed with sodium dihydrogen phosphate, the temperature is raised to 500-900 ℃ at a heating rate of 0.5-10 ℃/min under the protection of high-purity argon, the reaction is carried out at the temperature for 2-10h, and the reaction is ended and the reaction is cooled.
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