CN115332507A - 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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- CN115332507A CN115332507A CN202210996876.0A CN202210996876A CN115332507A CN 115332507 A CN115332507 A CN 115332507A CN 202210996876 A CN202210996876 A CN 202210996876A CN 115332507 A CN115332507 A CN 115332507A
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- 239000007772 electrode material Substances 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 65
- 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 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000013082 iron-based metal-organic framework Substances 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000011148 porous material Substances 0.000 claims abstract description 25
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims abstract description 13
- 235000019799 monosodium phosphate Nutrition 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 7
- 239000002245 particle Substances 0.000 claims abstract description 6
- 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 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 22
- 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
- 238000000197 pyrolysis Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000013110 organic ligand Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000203 mixture Substances 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
- 238000000227 grinding Methods 0.000 claims description 8
- 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 6
- 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
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 238000000498 ball milling Methods 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
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 11
- 239000011734 sodium Substances 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 9
- 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 7
- 238000003860 storage Methods 0.000 abstract description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 36
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 229910052742 iron Inorganic materials 0.000 description 12
- 239000013384 organic framework Substances 0.000 description 12
- 238000004146 energy storage Methods 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000005955 Ferric phosphate Substances 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 229940032958 ferric phosphate Drugs 0.000 description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 4
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 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
- 238000003763 carbonization 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
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- 239000006245 Carbon black Super-P Substances 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
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 1
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005518 electrochemistry Effects 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
- 239000011888 foil Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material 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
- 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
- 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
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention 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 the composite electrode material is provided with a pore channel. 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 framework; step 2: mixing the iron-based metal organic framework and sodium dihydrogen phosphate according to a preset proportion, and carrying out pyrolytic reaction under a protective atmosphere to obtain the carbon-coated sodium iron phosphate composite electrode material. The composite electrode material prepared by the invention has the advantages of high sodium storage capacity, stable cycle performance, excellent rate performance and the like.
Description
Technical Field
The invention 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
Energy provides a material basis for the development of human civilization. With the rapid development of global economy, the human needs for energy are 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 human beings poses a great environmental pollution problem. Furthermore, the non-renewable nature of fossil energy itself leads to its gradual depletion.
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 current energy. 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 is widely applied to portable electronic products, electric vehicles and large and medium-sized energy storage batteries. However, the lithium resource is extremely unevenly distributed in the world, mainly distributed in south america, and has low abundance in the crusta, so the price fluctuation of the lithium resource is severe, and the lithium resource is bound to become a strategic resource; and to meet the increasing demand, lithium resources in China highly depend on imports.
The shortage of lithium resources has led to the restriction of the use of lithium batteries in electric vehicles as well as large and medium-sized energy storage batteries and devices. Therefore, in order to meet the requirements of large-scale energy storage systems, it is of great significance to find the next generation of 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 both show similar 'rocking chair' electrochemical charge-discharge behaviors in battery operation. The energy storage system of the sodium ion battery is a new generation battery leading corner for replacing the lithium ion battery by using various advantages of rich raw materials, low cost, wide distribution, high energy conversion efficiency and the like. The market expects that sodium batteries will have broad prospects in the application scenarios of power grid energy storage, lead-acid battery replacement in low-speed electric vehicle scenarios, power supply of large-scale transportation equipment, and the like, with slightly lower requirements for energy density, and more sensitivity 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 lower) and contains less nickel, so that the recovery cost for preventing 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 benefits, ensures energy safety of China, reduces political significance and social effect such as pollution of waste batteries and the like, and is also worthy of attention. Therefore, the development of sodium ion batteries for large-scale energy storage is of great strategic importance.
However, the radius of sodium ion is larger than that of lithium ion, so that the electrode material suitable for lithium ion battery is not necessarily well suitable for sodium ion battery, and therefore, it is a great challenge to find a suitable electrode material for storing sodium and ensuring that sodium ions can be rapidly and reversibly inserted/extracted in the material. Therefore, the search for a positive electrode material with high specific capacity, stable structure and low price is the key to improve the overall performance of the sodium ion battery.
The anode materials of the sodium-ion battery reported at present mainly comprise Prussian blue compounds, metal oxides and polyanion compounds. However, sodium ion battery materials are mostly focused on morphology control and modification. More channels cannot be provided for the rapid transmission of sodium ions with larger radius, and the conductivity and the sodium ion diffusion mobility need to be further improved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a carbon-coated sodium iron phosphate composite electrode material and preparation and application thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the utility model provides a carbon cladding ferric phosphate sodium composite electrode material for electrochemistry energy storage, composite electrode material includes that the particle diameter is 30-90 nm's carbon cladding ferric phosphate sodium granule, carbon cladding ferric phosphate sodium is three-dimensional diamond structure, the pore has among the composite electrode material, the average pore diameter in pore is 10-30nm, composite electrode material's porosity is 25-40%, carbon cladding ferric phosphate sodium composite electrode material passes through the preparation of heat treatment metal organic frame.
Preferably, the channels include channels having an average pore diameter of 10 to 20nm and an average pore diameter of 20 to 30 nm.
According to the same inventive concept, the invention also provides a preparation method of the carbon-coated sodium iron phosphate composite electrode material, which comprises the following steps of:
step 1: preparing an iron-based metal organic framework;
step 2: mixing an iron-based metal organic framework and sodium dihydrogen phosphate according to a preset proportion, and carrying out a pyrolysis reaction under a protective atmosphere to obtain the carbon-coated sodium iron phosphate composite electrode material.
In one embodiment of the present invention, the step 1 specifically includes:
step 101: mixing inorganic iron salt and organic ligand according to a molar ratio of 1:1-5 are respectively dissolved in a solvent to obtain an inorganic iron salt solution and an organic ligand solution;
step 102: and (3) uniformly mixing the inorganic iron salt solution and the organic ligand solution in a dropwise manner, and standing and reacting for 4-30 hours at 90-180 ℃ to obtain the iron-based metal organic framework.
In one embodiment of the present invention, the solvent is a mixed solution of N, N-dimethylformamide and deionized water.
In one embodiment of the present invention, the inorganic ferric salt is one or more selected from ferric nitrate, ferric chloride, ferric acetate and ferric sulfate.
In one embodiment of the present invention, the organic ligand is fumaric acid, 1, 4-terephthalic acid or 1,3, 5-isophthalic acid.
In one embodiment of the present invention, in step 102, after the standing reaction is completed, the mixture after the reaction needs to be subjected to centrifugal separation, and then is washed with deionized water and absolute ethyl alcohol to obtain the iron-based metal organic framework.
In one embodiment of the present invention, in the step 1, the molar ratio of the iron-based metal organic framework to the sodium dihydrogen phosphate is 1:1-4 ball milling or grinding and mixing, heating to 500-900 ℃ at the heating rate of 0.5-10 ℃/min under the protection of high-purity argon, keeping the temperature for 2-10h for reaction, and cooling after the reaction.
Based on the same inventive concept, the invention also provides an 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.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages and positive effects:
(1) The iron-based metal organic framework is decomposed into CO and CO due to the organic ligand in the pyrolysis reaction process 2 And H 2 And O and other small molecule gases can form a porous channel structure in the electrode material, and the porous channel structure can effectively promote the gap diffusion of sodium ions in the electrode material.
(2) The iron-based metal organic framework is also a carbonization process in the pyrolysis process, and in the carbonization process, an amorphous carbon layer coating is formed, and an amorphous carbon supported iron-based metal organic framework is formed, so that the final composite electrode material has a large number of pores, a sodium ion transmission channel is provided, and meanwhile, amorphous carbon can greatly improve the conductivity of the electrode material and improve the sodium ion transmission rate. In addition, the volume expansion effect of sodium ions in the process of de-intercalation of the sodium ions in the electrode material can be relieved by the protection effect of the carbon layer, so that the carbon-coated iron phosphate sodium composite electrode material obtained based on the method 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 when being used as the positive electrode material of the sodium ion battery.
(3) One of the technical barriers to be overcome with current sodium ion batteries is that the material structure of the electrodes is not stable, resulting in a short cycle life of the battery. According to the invention, the composite electrode material with a high-porosity porous structure is constructed and 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 cycle 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 the radius of sodium ions is large, so that the sodium ions can be rapidly and reversibly embedded/de-embedded 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/de-embedding of the sodium ions, 20-30nm with a large pore size has higher electrochemical activity and rate capability, and 10-20nm with a small pore size shows more excellent cycling stability. Therefore, the carbon-coated sodium iron phosphate composite electrode material prepared by the invention contains a porous material with graded pore diameter, increases the utilization rate of an active material, and shows excellent rate capability and cycle stability.
(5) The carbon-coated sodium iron phosphate composite electrode material provided by the invention has the advantages of simple preparation method, 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 invention;
FIG. 2 is a pore size distribution diagram of a carbon-coated sodium iron phosphate composite cathode material prepared in example 1 of the present invention;
fig. 3 is a sodium ion battery cycle performance diagram of the carbon-coated sodium iron phosphate composite positive electrode material prepared in example 1 of the present invention.
Detailed Description
The carbon-coated sodium iron phosphate composite electrode material and the preparation and application thereof provided by the invention are further described in detail with reference to the accompanying drawings and specific examples. The advantages and features of the present invention will become more apparent from the following description.
There are two forms of ion transport in the electrode material: interstitial diffusion and vacancy diffusion. The rapid transmission of sodium ions can be realized only by optimizing and regulating two forms of ion transmission, and the performance of the sodium ion battery can be comprehensively improved. The invention utilizes the metal organic framework to regulate and control the gap diffusion and vacancy diffusion of the electrode material, and improves the transmission dynamics of sodium ions in the iron phosphate sodium electrode material. The metal organic framework is used as a crystal material formed by self-assembly of metal ions and organic ligands, and has the advantages of high porosity, large specific surface area, adjustable structure and function and the like, so that the metal organic framework becomes an energy storage material with great development potential.
The features of the invention are illustrated by the following specific examples
Example 1
The preparation method of the carbon-coated sodium iron phosphate composite electrode material sequentially comprises the following steps of:
step 1: mixing ferric nitrate solution and 1, 4-terephthalic acid according to a molar ratio of 1:5, respectively dissolving the mixture in a solvent solution formed by deionized water and N, N-dimethylformamide;
step 2: uniformly mixing the prepared solution in a dropwise manner, and then statically growing for 10 hours at 180 ℃ to obtain a primary product containing the iron-based metal organic framework template;
and step 3: centrifugally separating a primary product containing the iron-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean iron-based metal organic framework;
and 4, step 4: mixing the clean iron-based metal organic framework obtained in the step 3 with sodium dihydrogen phosphate in a molar ratio of 1:1, after ball milling treatment, under the protection of high-purity argon, raising the temperature to 500 ℃ at a temperature rise rate of 0.5 ℃/min, and keeping the temperature for 2 hours for reaction;
and 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, as shown in fig. 1, a scanning electron microscope image of the composite material prepared in example 1 is a diamond structure, and the surface of the composite material has a porous characteristic. The pore size distribution diagram shown in fig. 2 is obtained by measuring the pore size of the prepared composite material, the pore size 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 of:
step 1: mixing ferric chloride solution and fumaric acid according to a molar ratio of 1:2 are respectively dissolved in solvent solution formed by deionized water and N, N-dimethylformamide;
and 2, step: uniformly mixing the solution in a dropwise manner, and then standing and growing for 20 hours at 120 ℃ to obtain a primary product containing the iron-based metal organic framework template;
and 3, step 3: centrifugally separating a primary product containing the iron-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean iron-based metal organic framework;
and 4, step 4: mixing the clean iron-based metal organic framework obtained in the step 3 with sodium dihydrogen phosphate in a molar ratio of 1:2, after ball milling treatment, under the protection of high-purity argon, heating to 600 ℃ at a heating rate of 1 ℃/min, and keeping the temperature for 3 hours for reaction;
and 5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the carbon-coated sodium iron phosphate composite electrode material.
Example 3
The preparation method of the carbon-coated sodium iron phosphate composite electrode material sequentially comprises the following steps of:
step 1: mixing ferric sulfate and 1,3, 5-m-benzene tricarboxylic acid according to a molar ratio of 1:3 respectively putting the mixture into solvent solutions formed by deionized water and N, N-dimethylformamide;
and 2, step: uniformly mixing the solution in a dropwise manner, and then standing and growing for 30 hours at 150 ℃ to obtain an initial product containing the iron-based organic framework template;
and step 3: centrifugally separating a primary product containing the iron-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean iron-based organic framework;
and 4, step 4: and (3) mixing the clean iron-based metal organic framework obtained in the step (3) with sodium dihydrogen phosphate in a molar ratio of 1:3, after grinding, under the protection of high-purity argon, raising the temperature to 700 ℃ at a temperature rise rate of 2 ℃/min, and keeping the temperature for 4 hours for reaction;
and 5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the carbon-coated sodium iron phosphate composite electrode material.
Example 4
The preparation method of the carbon-coated sodium iron phosphate composite electrode material sequentially comprises the following steps of:
step 1: mixing ferric sulfate and 1, 4-terephthalic acid according to a molar ratio of 1:4 respectively putting the mixture into solvent solutions formed by deionized water and N, N-dimethylformamide;
step 2: uniformly mixing the solution in a dropwise manner, and then standing and growing for 4 hours at 180 ℃ to obtain a primary product containing the iron-based organic framework template;
and step 3: centrifugally separating a primary product containing the iron-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean iron-based organic framework;
and 4, step 4: and (3) mixing the clean iron-based metal organic framework obtained in the step (3) with sodium dihydrogen phosphate in a molar ratio of 1:4, after grinding, under the protection of high-purity argon, raising the temperature to 800 ℃ at a temperature rise rate of 5 ℃/min, and keeping the temperature for 5 hours for reaction;
and 5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the carbon-coated sodium iron phosphate composite electrode material.
Example 5
The preparation method of the carbon-coated sodium iron phosphate composite electrode material sequentially comprises the following steps of:
step 1: mixing ferric sulfate and 1,3, 5-m-benzene tricarboxylic acid according to a molar ratio of 1:3 respectively putting the mixture into solvent solutions formed by deionized water and N, N-dimethylformamide;
step 2: uniformly mixing the solution in a dropwise manner, and then standing and growing for 10 hours at 170 ℃ to obtain a primary product containing the iron-based organic framework template;
and step 3: centrifugally separating a primary product containing the iron-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean iron-based organic framework;
and 4, step 4: mixing the clean iron-based metal organic framework obtained in the step 3 with sodium dihydrogen phosphate in a molar ratio of 1:1, grinding, heating to 900 ℃ at a heating rate of 3 ℃/min under the protection of high-purity argon, and keeping the temperature for 6 hours for reaction;
and 5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the carbon-coated sodium iron phosphate composite electrode material.
Example 6
The preparation method of the carbon-coated sodium iron phosphate composite electrode material sequentially comprises the following steps of:
step 1: mixing ferric chloride and fumaric acid according to a molar ratio of 1:2 respectively putting the mixture into solvent solutions formed by deionized water and N, N-dimethylformamide;
step 2: uniformly mixing the solution in a dropwise manner, and then standing and growing for 8 hours at 160 ℃ to obtain a primary product containing the iron-based organic framework template;
and step 3: centrifugally separating a primary product containing the iron-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean iron-based organic framework;
and 4, step 4: and (3) mixing the clean iron-based metal organic framework obtained in the step (3) with sodium dihydrogen phosphate in a molar ratio of 1:2, after grinding treatment, under the protection of high-purity argon, raising the temperature to 600 ℃ at a temperature rise rate of 4 ℃/min, and keeping the temperature for 7 hours for reaction;
and 5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the carbon-coated sodium iron phosphate composite electrode material.
Example 7
The preparation method of the carbon-coated sodium iron phosphate composite electrode material sequentially comprises the following steps of:
step 1: mixing ferric sulfate and 1, 4-terephthalic acid according to a molar ratio of 1:3 respectively putting the mixture into solvent solutions formed by deionized water and N, N-dimethylformamide;
and 2, step: uniformly mixing the solution in a dropwise manner, and then standing and growing for 9 hours at 150 ℃ to obtain an initial product containing the iron-based organic framework template;
and 3, step 3: centrifugally separating a primary product containing the iron-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean iron-based organic framework;
and 4, step 4: and (3) mixing the clean iron-based metal organic framework obtained in the step (3) with sodium dihydrogen phosphate in a molar ratio of 1:3, after grinding, under the protection of high-purity argon, raising the temperature to 800 ℃ at a temperature rise rate of 6 ℃/min, and keeping the temperature for 8 hours for reaction;
and 5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the carbon-coated sodium iron phosphate composite electrode material.
Example 8
The preparation method of the carbon-coated sodium iron phosphate composite electrode material sequentially comprises the following steps of:
step 1: mixing iron acetate and 1,3, 5-m-benzene tricarboxylic acid according to a molar ratio of 1:2 respectively putting the mixture into solvent solutions formed by deionized water and N, N-dimethylformamide;
step 2: uniformly mixing the solution in a dropwise manner, and then standing and growing for 10 hours at 140 ℃ to obtain an initial product containing the iron-based organic framework template;
and step 3: centrifugally separating a primary product containing the iron-based metal organic framework template, and respectively cleaning the primary product for 3 times by using deionized water and absolute ethyl alcohol to obtain a clean iron-based organic framework;
and 4, step 4: and (3) mixing the clean iron-based metal organic framework obtained in the step (3) with sodium dihydrogen phosphate in a molar ratio of 1:4, after grinding treatment, under the protection of high-purity argon, raising the temperature to 700 ℃ at a temperature rise rate of 10 ℃/min, and keeping the temperature for 10 hours for reaction;
and 5: and after the pyrolysis reaction is finished, cooling the temperature to room temperature to obtain the carbon-coated sodium iron phosphate composite electrode material.
Example 9
The carbon-coated sodium iron phosphate composite electrode material prepared in examples 1 to 8, the binder carboxymethyl cellulose sodium and the conductive agent Super-P were dispersed in deionized water at a mass ratio of 75: 15: 10 to prepare a slurry, which was uniformly applied on an aluminum foil 8 μm thick, and after vacuum drying for 12 hours, a circular electrode having a diameter of 12mm was prepared by a mold.
A CR2032 button cell is assembled in a glove box with water and oxygen contents less than 0.5ppm by taking a metal sodium sheet as a reference electrode and a counter electrode and Whatman GF/D as a diaphragm. The electrolyte is composed of a mixed solvent of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate, wherein 1M NaClO4 is dissolved in the mixed solvent of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate in a volume ratio of 1. The CR2032 button cell is charged and discharged with constant current through a blue battery tester CT2001A, the voltage volt value is 1.5-4.3V, the current density is 100mA/g, the cycle performance of the carbon-coated sodium iron phosphate composite electrode material after charging and discharging for 200 times is tested, and the electrochemical performance results of the electrode materials prepared in the embodiments 1-8 are shown in the table 1.
TABLE 1
The sodium ion battery was cycled 100 times at a current density of 100mA/g using the CR2032 button cell assembled in example 1. The obtained result is shown in fig. 3, the sodium ion battery prepared in example 1 has the cycle performance of the carbon-coated sodium iron phosphate composite electrode material under the current density of 100mA/g, the sodium storage capacity after 100 times is 210mAh/g, and the cycle stability is better.
To sum up, the carbon-coated sodium iron phosphate particles in the carbon-coated sodium iron phosphate composite electrode material provided by the application are of a three-dimensional diamond structure, and the surface is smooth. The sodium ion battery is applied to an anode of 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 the cyclic charge and discharge for 200 times, the capacity retention rate is higher than 94%, and the cyclic stability is better. Therefore, the carbon-coated sodium iron phosphate composite electrode material obtained by the invention 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 when being used as a sodium ion battery anode material.
The embodiments of the present invention have been described in detail with reference to the drawings, but the present invention is not limited to the embodiments. Even if various changes are made to the present invention, it is still within the scope of the present invention if they fall within the scope of the claims of the present invention and their equivalents.
Claims (10)
1. The carbon-coated sodium iron phosphate composite electrode material is used for electrochemical energy storage and is characterized by comprising 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 pores, the average pore diameter of the pores is 10-30nm, and the porosity of the composite electrode material is 25-40%.
2. The carbon-coated sodium iron phosphate composite electrode material according to claim 1, wherein the pores comprise pores having an average pore diameter of 10-20nm and an average pore diameter of 20-30 nm.
3. A method for preparing the carbon-coated sodium iron phosphate composite electrode material according to claim 1 or 2, comprising the steps of:
step 1: preparing an iron-based metal organic framework;
step 2: mixing the iron-based metal organic framework and sodium dihydrogen phosphate according to a preset proportion, and carrying out pyrolysis reaction under a protective atmosphere to obtain the carbon-coated sodium iron phosphate composite electrode material.
4. The method for preparing the carbon-coated sodium iron phosphate composite electrode material according to claim 3, wherein the step 1 specifically comprises:
step 101: mixing inorganic ferric salt and organic ligand according to a molar ratio of 1:1-5 are respectively dissolved in a solvent to obtain an inorganic iron salt solution and an organic ligand solution;
step 102: and (3) uniformly mixing the inorganic iron salt solution and the organic ligand solution in a dropwise manner, and standing and reacting for 4-30 hours at 90-180 ℃ to obtain the iron-based metal organic framework.
5. The method for preparing the carbon-coated sodium iron phosphate composite electrode material according to claim 4, wherein the solvent is a mixed solution of N, N-dimethylformamide and deionized water.
6. The preparation method of the carbon-coated sodium iron phosphate composite electrode material according to claim 4, wherein the inorganic ferric salt is one or more of ferric nitrate, ferric chloride, ferric acetate or ferric sulfate.
7. The method for preparing the carbon-coated sodium iron phosphate composite electrode material according to claim 4, wherein the organic ligand is fumaric acid, 1, 4-terephthalic acid or 1,3, 5-isophthalic acid.
8. The method for preparing the carbon-coated sodium iron phosphate composite electrode material according to claim 4, wherein in the step 102, after the standing reaction is completed, the mixture after the reaction needs to be centrifugally separated, and then deionized water and absolute ethyl alcohol are adopted to clean for 2-4 times, so as to obtain the iron-based metal organic framework.
9. The method for preparing the carbon-coated sodium iron phosphate composite electrode material according to claim 3, wherein in the step 1, the molar ratio of the iron-based metal organic framework to the sodium dihydrogen phosphate is 1:1-4 ball milling or grinding and mixing, heating to 500-900 ℃ at the heating rate of 0.5-10 ℃/min under the protection of high-purity argon, keeping the temperature for 2-10h for reaction, and cooling after the reaction.
10. An application of a carbon-coated sodium iron phosphate composite electrode material, which is characterized in that the carbon-coated sodium iron phosphate composite electrode material is obtained by the preparation method of the carbon-coated sodium iron phosphate composite electrode material according to claim 1 or 2 or any one of claims 3 to 9, and the carbon-coated sodium iron phosphate composite electrode material is applied to a positive electrode for electrochemical energy storage.
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