CN116230888B - Method for preparing carbon-coated sodium iron sulfate material, carbon-coated sodium iron sulfate material and battery - Google Patents
Method for preparing carbon-coated sodium iron sulfate material, carbon-coated sodium iron sulfate material and battery Download PDFInfo
- Publication number
- CN116230888B CN116230888B CN202310134154.9A CN202310134154A CN116230888B CN 116230888 B CN116230888 B CN 116230888B CN 202310134154 A CN202310134154 A CN 202310134154A CN 116230888 B CN116230888 B CN 116230888B
- Authority
- CN
- China
- Prior art keywords
- carbon
- ball milling
- carbon source
- iron sulfate
- sodium iron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 187
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 176
- 239000000463 material Substances 0.000 title claims abstract description 81
- YPPMLCHGJUMYPZ-UHFFFAOYSA-L sodium;iron(2+);sulfate Chemical compound [Na+].[Fe+2].[O-]S([O-])(=O)=O YPPMLCHGJUMYPZ-UHFFFAOYSA-L 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 57
- 238000000498 ball milling Methods 0.000 claims abstract description 72
- 239000002904 solvent Substances 0.000 claims abstract description 27
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 22
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 21
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 21
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 18
- 239000012159 carrier gas Substances 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000011324 bead Substances 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 238000009766 low-temperature sintering Methods 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 21
- 238000000576 coating method Methods 0.000 abstract description 21
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 239000011734 sodium Substances 0.000 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 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 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 description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000002245 particle Substances 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of batteries, in particular to a method for preparing a carbon-coated sodium iron sulfate material, the carbon-coated sodium iron sulfate material and a battery. The method for preparing the carbon-coated sodium iron sulfate material comprises the following steps: s1, performing first ball milling on a mixed solution containing a first solvent, ferrous sulfate heptahydrate, sodium sulfate and an inorganic carbon source in inert gas filled with the mixed solution to obtain viscous precursor slurry, and drying the precursor slurry in vacuum atmosphere or inert atmosphere to obtain dry precursor powder; s2, repeatedly grinding the dried precursor powder, and then sintering at a low temperature in an atmosphere containing an organic carbon source. The method for preparing the carbon-coated sodium iron sulfate material can realize in-situ carbon coating, so that the prepared carbon-coated sodium iron sulfate material is uniform in coating and good in conductivity; the carbon-coated sodium iron sulfate material has a purer phase, is uniformly coated with carbon and has good conductivity; the battery has good multiplying power performance and stable cycle performance.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a method for preparing a carbon-coated sodium iron sulfate material, the carbon-coated sodium iron sulfate material prepared by the method and a battery comprising the carbon-coated sodium iron sulfate material.
Background
With the rapid development of new energy industry, lithium batteries play a significant role in the fields of 3C, power and energy storage. However, the faster the lithium battery industry develops, the more lithium resources are required to be consumed, the reserve of lithium ores in the world is inherently low, and the development technology is immature, the capacity release is slower, and the lithium salts are continuously increased. Sodium ion batteries are receiving attention from more and more researchers and investors because of the abundance and wide sources of raw materials and the low cost of raw materials.
The positive electrode material of the sodium ion battery mainly has three directions: layered oxides, polyanionic compounds and prussian blue analogues. However, the main current positive electrode material has a plurality of technical bottlenecks and mass production difficulties in the current industrialized application. The layered oxide material has the main problems of higher residual alkali content, easy gas generation in the circulation process and poor circulation stability; the crystal water in the crystal structure of the Prussian blue or white positive electrode material is difficult to remove in the preparation process, so that the crystallinity of the material is low, the electrochemical performance is not ideal, and meanwhile, cyanide has toxicity, so that the industrialization is difficult to realize. In contrast, polyanions are stable in crystal structure and three-dimensional sodium ions (Na + ) The diffusion channel has the characteristics of high voltage, high multiplying power, excellent low-temperature working performance, excellent cycle performance and the like, and particularly has the advantages of low raw material cost, low synthesis temperature, low energy consumption and the like compared with other polyanion materials.
The common synthetic method of the sodium ferric sulfate material generally needs to remove crystal water in ferrous sulfate firstly, and Fe is contained in the material in the preparation process 2+ Is easy to oxidize and is difficult to synthesize a purer phase; and because the synthesis temperature is low, in-situ carbon coating cannot be performed, the coating uniformity is poor, the conductivity is poor, and the large-scale application of the carbon-coated carbon is limited.
Therefore, the invention is very important to invent a method for preparing the carbon-coated sodium iron sulfate material with uniform coating and good conductivity.
Disclosure of Invention
The present invention has been made to overcome the above-mentioned problems occurring in the prior art, and an object of the present invention is to provide a method for preparing a carbon-coated sodium iron sulfate material, a carbon-coated sodium iron sulfate material prepared by the method, and a battery including the carbon-coated sodium iron sulfate material. The method for preparing the carbon-coated sodium iron sulfate material can realize in-situ carbon coating, so that the prepared carbon-coated sodium iron sulfate material is uniform in coating and good in conductivity; the carbon-coated sodium iron sulfate material prepared by the method has a purer phase, uniform carbon coating and good conductivity; the battery comprising the carbon-coated sodium iron sulfate material has good rate capability and stable cycle performance.
The first aspect of the invention provides a method for preparing a carbon-coated sodium iron sulfate material, comprising the steps of:
s1, performing first ball milling on a mixed solution containing a first solvent, ferrous sulfate heptahydrate, sodium sulfate and an inorganic carbon source in inert gas filled with the mixed solution to obtain viscous precursor slurry, and drying the precursor slurry in vacuum atmosphere or inert atmosphere to obtain dry precursor powder;
s2, repeatedly grinding the dry precursor powder, and then sintering at a low temperature in an atmosphere containing an organic carbon source.
In one example, the molar ratio of the ferrous sulfate heptahydrate to the sodium sulfate in step S1 is (0.5-2.5): 1.
In one example, the inorganic carbon source is present in the carbon coated sodium iron sulfate material in an amount of 0.1wt% to 10wt%.
In one example, the inorganic carbon source is selected from one or more of carbon nanotubes, carbon fibers, graphene, reduced graphene oxide, and amorphous carbon.
In one example, the first solvent is selected from one or more of distilled water, ethanol, methanol, acetone, ethylene glycol, and azamethylpyrrolidone.
In one example, the first ball milling conditions in step S1 are: revolution speed is 100-1000r/min, rotation speed is 200-2000r/min, and ball milling time is 1-24h; the ball milling medium of the first ball milling is selected from one or more of zirconia beads, agate beads and steel balls, the diameter of the ball milling medium is 0.1mm-20mm, and the diameter of the ball milling medium at least comprises 3 different specifications.
In one example, the ratio of the weight of the ball milling medium to the sum of the weight of the ferrous sulfate heptahydrate, the sodium sulfate, and the inorganic carbon source is (1-100): 1.
In an example, in the step S1, the drying conditions include: the drying temperature is 40-250 ℃ and the drying time is 1-48h.
In an example, the method further comprises: and (3) carrying out pretreatment on the inorganic carbon source, wherein the pretreatment comprises the step of carrying out second ball milling pre-dispersion on the inorganic carbon source, a second solvent and a dispersing agent.
In one example, the dispersant is selected from one or more of polyvinylpyrrolidone, cetyltrimethylammonium bromide, sodium dodecylbenzene sulfonate, and sodium lauryl sulfate.
In one example, the second solvent is selected from one or more of distilled water, ethanol, methanol, acetone, ethylene glycol, and azamethylpyrrolidone.
In one example, the ratio of the amount of the dispersant to the amount of the inorganic carbon source is (0.01-0.5): 1.
In one example, the ratio of the amount of the inorganic carbon source to the amount of the second solvent is (0.01-0.1): 1.
In one example, the conditions of the second ball milling are: revolution speed is 100-1000r/min, rotation speed is 200-2000r/min, and ball milling time is 0.1-12h; the ball milling medium of the second ball milling is selected from one or more of zirconia beads, agate beads and steel balls, the diameter of the ball milling medium is 0.1mm-10mm, and the diameter of the ball milling medium at least comprises 2 different specifications.
In one example, the ratio of the weight of the ball milling medium to the sum of the weight of the inorganic carbon source and the dispersant is (1-300): 1.
In an example, the organic carbon source in step S2 is blown and volatilized into the sintering equipment by a carrier gas, wherein the carrier gas is an inert gas, and the flow rate of the carrier gas is 10ml/min-3000ml/min.
In an example, in step S2, the low temperature sintering temperature is 300 ℃ to 450 ℃, and the low temperature sintering time is 6 to 48 hours.
In one example, the organic carbon source has a boiling point below 120 ℃ at atmospheric pressure.
In one example, the organic carbon source is selected from one or more of ethanol, acetone, methanol, diethyl ether, isopropanol, and acetonitrile.
In an example, the method further comprises: and (2) carrying out preheating treatment on the organic carbon source in the step (S2), wherein the preheating temperature is 30-100 ℃.
In a second aspect, the invention provides a carbon-coated sodium iron sulfate material prepared by the method of the first aspect.
The third aspect of the invention provides a battery, which comprises a positive plate, wherein the positive plate comprises the carbon-coated sodium iron sulfate material prepared by the method of the first aspect and/or the carbon-coated sodium iron sulfate material of the second aspect.
Through the technical scheme, compared with the prior art, the invention has at least the following advantages:
(1) The method for preparing the carbon-coated sodium iron sulfate material can realize in-situ carbon coating, so that the prepared carbon-coated sodium iron sulfate material is uniform in coating and good in conductivity;
(2) The method for preparing the carbon-coated sodium ferric sulfate material can remove the crystal water existing in the ferrous sulfate heptahydrate and ensure sufficient reducing atmosphere;
(3) The method for preparing the carbon-coated sodium ferric sulfate material does not need to dry in advance to remove the bound water in the ferrous sulfate heptahydrate, shortens the production period and reduces the production cost;
(4) According to the method for preparing the carbon-coated sodium iron sulfate material, disclosed by the invention, the carbon is coated in a mode of combining an inorganic carbon source and an organic carbon source, so that the utilization rate of the inorganic carbon source with high price is reduced, and the raw material cost is reduced;
(5) The method for preparing the carbon-coated sodium iron sulfate material has low production cost and is suitable for industrial production;
(6) The carbon-coated sodium iron sulfate material has a purer phase;
(7) The carbon-coated sodium iron sulfate material is uniformly coated with carbon;
(8) The carbon-coated sodium iron sulfate material has good conductivity;
(9) The battery gram capacity of the invention plays a role highly;
(10) The battery has good multiplying power performance;
(11) The battery of the invention has stable cycle performance.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Fig. 1 shows a diffraction pattern of a prepared carbon-coated sodium iron sulfate material according to an embodiment of the present invention.
Fig. 2 is an SEM schematic diagram of a carbon-coated sodium iron sulfate material according to an embodiment of the present invention.
Fig. 3 is a schematic charge-discharge curve of a battery including a prepared carbon-coated sodium iron sulfate material according to an embodiment of the present invention.
Fig. 4 is a schematic diagram showing the capacity retention rate of a battery including the prepared carbon-coated sodium iron sulfate material according to an embodiment of the present invention.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The first aspect of the invention provides a method for preparing a carbon-coated sodium iron sulfate material, comprising the steps of:
s1, performing first ball milling on a mixed solution containing a first solvent, ferrous sulfate heptahydrate, sodium sulfate and an inorganic carbon source in inert gas filled with the mixed solution to obtain viscous precursor slurry, and drying the precursor slurry in vacuum atmosphere or inert atmosphere to obtain dry precursor powder;
s2, repeatedly grinding the dry precursor powder, and then sintering at a low temperature in an atmosphere containing an organic carbon source.
According to the method disclosed by the invention, a Chemical Vapor Deposition (CVD) in-situ carbon coating and inorganic carbon coating mode is adopted, the crystallization water is removed through the reaction of an organic carbon source and the crystallization water existing in the raw materials, different defects are formed by the reaction of the organic carbon source and the crystallization water, and the carbon layer with the defects has better conductivity, so that the prepared carbon-coated sodium iron sulfate material has a purer phase, is more uniform in carbon coating and has better conductivity.
In the invention, the carbon coating is carried out by adopting a Chemical Vapor Deposition (CVD) method and combining an inorganic carbon source and an organic carbon source, so that the prepared carbon-coated sodium iron sulfate material can realize more uniform coating and better conductivity than the prior art. In order to further enhance the effect, one or more of the technical features may be further preferred.
The mixed solution contains a first solvent, ferrous sulfate heptahydrate, sodium sulfate, and an inorganic carbon source. The method of preparing the mixed solution is not limited, and thus the mixed solution containing the first solvent, ferrous sulfate heptahydrate, sodium sulfate and inorganic carbon source is the mixed solution according to the present invention. For example, the mixed solution may be prepared by: dispersing ferrous sulfate heptahydrate in a first solvent, and adding sodium sulfate and an inorganic carbon source to obtain a mixed solution.
According to a specific embodiment, the molar ratio of the ferrous sulfate heptahydrate to the sodium sulfate in step S1 is (0.5-2.5): 1 (e.g., 0.5:1, 0.7:1, 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.2:1, 2.5:1).
In one example, the molar ratio of the ferrous sulfate heptahydrate to the sodium sulfate in step S1 is (1-2): 1.
According to a specific embodiment, the weight content of the inorganic carbon source in the carbon coated sodium iron sulfate material is 0.1wt% to 10wt% (e.g., 0.1wt%, 0.5wt%, 1wt%, 3wt%, 5wt%, 8wt%, 10 wt%). The carbon-coated sodium iron sulfate material is prepared by the method of the first aspect of the invention.
In one example, the inorganic carbon source is present in the carbon coated sodium iron sulfate material in an amount of 3wt% to 8wt%.
In one example, the inorganic carbon source is selected from one or more of carbon nanotubes, carbon fibers, graphene, reduced graphene oxide, and amorphous carbon.
In one example, the first solvent is selected from one or more of distilled water, ethanol, methanol, acetone, ethylene glycol, and azamethylpyrrolidone.
According to a specific embodiment, the revolution speed of the first ball mill in step S1 is 100-1000r/min (e.g., 100r/min, 200r/min, 300r/min, 400r/min, 500r/min, 600r/min, 700r/min, 800r/min, 900r/min, 1000 r/min), preferably 200-800r/min.
In one example, the rotation speed of the first ball mill in step S1 is 200-2000r/min (e.g., 200r/min, 500r/min, 800r/min, 1000r/min, 1200r/min, 1500r/min, 1800r/min, 2000 r/min), preferably 300-1000r/min.
In one example, the ball milling time of the first ball milling in step S1 is 1-24h (e.g., 1h, 5h, 10h, 15h, 20h, 24 h).
The first ball milling in step S1 may be performed in a ball milling apparatus. The ball milling apparatus may be a conventional ball milling apparatus, such as a ball mill, a sand mill.
In one example, the ball milling media of the first ball mill is selected from one or more of zirconia beads, agate beads, and steel balls.
In one example, the ball milling media has a diameter of 0.1mm-20mm (e.g., 0.1mm, 0.5mm, 1mm, 5mm, 10mm, 15mm, 20 mm).
In one example, the diameter of the ball milling media comprises at least 3 different gauges. The different specifications represent different diameters of the ball milling media. Illustratively, the diameter of the ball milling media comprises 3 different specifications of 1+ -0.3 mm, 2+ -0.3 mm, 3+ -0.3 mm, respectively; the diameters of the ball milling media comprise 5 different specifications, namely 0.5+/-0.3 mm, 1+/-0.3 mm, 3+/-0.3 mm, 10+/-0.5 mm and 20+/-1 mm. The ball milling media with at least 3 different diameter specifications are selected, so that the raw materials can be fully mixed, and the particle size of the raw materials is controlled, so that the prepared carbon-coated sodium iron sulfate material has purer phase, smaller primary particles and better multiplying power performance.
According to a specific embodiment, the ratio of the weight of the ball milling medium to the sum of the weight of the ferrous sulfate heptahydrate, the sodium sulfate, and the inorganic carbon source is (1-100): 1 (e.g., 1:1, 5:1, 10:13, 0:1, 50:1, 70:1, 100:1).
In an example, in the step S1, the drying conditions include: the drying temperature is 40-250deg.C (e.g., 40deg.C, 80deg.C, 100deg.C, 150deg.C, 200deg.C, 230deg.C, 250deg.C), and the drying time is 1-48h (e.g., 1h, 5h, 10h, 20h, 30h, 40h, 48 h).
According to a specific embodiment, the method further comprises: and (3) pretreating the inorganic carbon source. Wherein the pretreatment of the inorganic carbon source is performed before the mixed solution is prepared in step S1.
In one example, the pre-treatment includes a second ball milling pre-dispersion of the inorganic carbon source with a second solvent, a dispersant. By pretreating the inorganic carbon source, the inorganic carbon source is not easy to agglomerate, so that the carbon coating is further uniform, the utilization rate of the inorganic carbon source is improved, and the cost of raw materials is reduced.
In one example, the dispersant is selected from one or more of polyvinylpyrrolidone (PVP), cetyltrimethylammonium bromide, sodium dodecylbenzene sulfonate, and sodium lauryl sulfate.
In one example, the second solvent is selected from one or more of distilled water, ethanol, methanol, acetone, ethylene glycol, and azamethylpyrrolidone.
According to a specific embodiment, the ratio of the amount of dispersant to the amount of inorganic carbon source is (0.01-0.5) 1 (e.g., 0.01:1, 0.02:1, 0.05:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1). By limiting the weight ratio of the dispersant to the inorganic carbon source within a certain range, the inorganic carbon source can be dispersed more sufficiently, so that the inorganic carbon source is not easily agglomerated.
In one example, the ratio of the amount of the dispersant to the amount of the inorganic carbon source is (0.02-0.2): 1.
In one example, the ratio of the amount of the inorganic carbon source to the amount of the second solvent is (0.01-0.1): 1 (e.g., 0.01:1, 0.02:1, 0.05:1, 0.08:1, 0.1:1).
According to a specific embodiment, the revolution speed of the second ball mill is 100-1000r/min (e.g., 100r/min, 200r/min, 300r/min, 400r/min, 500r/min, 600r/min, 700r/min, 800r/min, 900r/min, 1000 r/min), preferably 200-800r/min.
In one example, the second ball mill rotates at a speed of 200-2000r/min (e.g., 200r/min, 500r/min, 800r/min, 1000r/min, 1200r/min, 1500r/min, 1800r/min, 2000 r/min), preferably 300-1000r/min.
In one example, the second ball milling time is 0.1-12h (e.g., 0.1h, 0.5h, 1h, 5h, 10h, 12 h).
The second ball milling may be performed in a ball milling apparatus. The ball milling apparatus may be a conventional ball milling apparatus, such as a ball mill, a sand mill.
In one example, the ball milling media of the second ball mill is selected from one or more of zirconia beads, agate beads, and steel balls.
In one example, the ball milling media has a diameter of 0.1mm to 10mm, e.g., 0.1mm, 0.5mm, 1mm, 5mm, 10 mm).
In one example, the ball milling media includes at least 2 different gauges in diameter. The different specifications represent different diameters of the ball milling media. Illustratively, the diameter of the ball milling media comprises 2 different gauges of 0.6+ -0.3 mm, 0.8+ -0.3 mm, respectively; the diameters of the ball milling media comprise 4 different specifications, namely 0.5+/-0.3 mm, 1+/-0.3 mm, 3+/-0.3 mm and 6+/-0.3 mm. At least 2 ball milling media with different diameter specifications are selected, so that inorganic carbon source particles can be separated, the inorganic carbon source is better dispersed, and the occurrence of agglomeration is reduced.
According to a specific embodiment, the ratio of the weight of the ball milling medium to the sum of the weight of the inorganic carbon source and the dispersant is (1-300): 1 (e.g., 1:1, 5:1, 10:1, 30:1, 50:1, 70:1, 100:1, 200:1, 300:1).
According to a specific embodiment, the organic carbon source is blown by a carrier gas into the sintering device in step S2. The carrier gas is used for bringing a low-boiling-point organic carbon source, and the organic carbon source is decomposed and carbonized at a low temperature to form a carbon layer with good conductivity and uniform cladding, so that the problem that the conductivity is poor due to the fact that in-situ carbon cladding cannot be carried out due to the fact that the crystallization temperature of sodium iron sulfate is too low is solved. The organic carbon source is carbonized at low temperature and reacts with the residual crystal water in the dry precursor powder to generate carbon monoxide and hydrogen, so that on one hand, a sufficient reducing atmosphere is provided for the sodium iron sulfate material in the sintering process, and the Fe in the process of preparing the sodium iron sulfate is overcome 2+ A problem of being easily oxidized; on the other hand, the residual crystal water in the dry precursor powder participates in the reaction, and the crystal water in the final product can be prevented, so that the gram capacity of the carbon-coated sodium iron sulfate material is further improved, and the carbon-coated sodium iron sulfate material has higher capacity.
In one example, the sintering apparatus is an atmosphere furnace.
In one example, the carrier gas is an inert gas.
In one example, the inert gas is selected from one or more of argon and nitrogen.
According to a specific embodiment, the carrier gas has a flow rate of 10ml/min to 3000ml/min (e.g., 10ml/min, 50ml/min, 100ml/min, 500ml/min, 1000ml/min, 1500ml/min, 2000ml/min, 2500ml/min, 3000 ml/min).
In one example, the carrier gas flow is 100ml/min to 1000ml/min.
According to a specific embodiment, in step S2, the low temperature sintering is performed at a temperature of 300 ℃ -450 ℃ (e.g., 300 ℃, 330 ℃, 350 ℃, 370 ℃, 400 ℃) and the low temperature sintering is performed for a time of 6-48 hours (e.g., 6 hours, 8 hours, 10 hours, 15 hours, 20 hours, 24 hours, 30 hours, 35 hours, 40 hours, 48 hours).
In an example, in step S2, the low temperature sintering temperature is 330 ℃ to 400 ℃ and the low temperature sintering time is 8 to 24 hours.
In one example, the organic carbon source has a boiling point below 120 ℃ at atmospheric pressure.
In one example, the organic carbon source is selected from one or more of ethanol, acetone, methanol, diethyl ether, isopropanol, and acetonitrile.
In an example, the method further comprises: and (2) carrying out preheating treatment on the organic carbon source in the step (S2). Wherein the preheating treatment of the organic carbon source is performed before the carrier gas is introduced.
In one example, the temperature of the preheating is from 30 ℃ to 100 ℃ (e.g., 30 ℃, 50 ℃, 80 ℃,100 ℃).
The first and second are not shown in order in the present invention. For example, the first and second solvents are used in a first and second manner merely to distinguish between the solvents and are not representative of the order in which the first and second solvents appear in the process; the first and second ball mills are merely for distinguishing between the ball mills and do not represent the order in which the first and second ball mills occur in the method.
In a second aspect, the invention provides a carbon-coated sodium iron sulfate material prepared by the method of the first aspect.
For example, fig. 1 is a diffraction chart (XRD) of a carbon-coated sodium iron sulfate material prepared according to an embodiment of the present invention, and as shown in fig. 1, it can be seen that the intensity of diffraction peaks is high, and the impurity peaks are few, which indicates that the prepared carbon-coated sodium iron sulfate material has good crystallinity and has a purer phase.
For example, fig. 2 is an SEM schematic diagram of a carbon-coated sodium iron sulfate material prepared according to an embodiment of the present invention, as shown in fig. 2, it can be seen that the tubular carbon nanotubes are dispersed uniformly in the sodium iron sulfate material, and no obvious agglomeration exists, which indicates that the carbon coating is more uniform.
The carbon-coated sodium iron sulfate material is prepared by the method provided by the invention, and has the advantages of purer phase, more uniform carbon coating and better conductivity.
The third aspect of the invention provides a battery, which comprises a positive plate, wherein the positive plate comprises the carbon-coated sodium iron sulfate material prepared by the method of the first aspect and/or the carbon-coated sodium iron sulfate material of the second aspect.
The materials of the battery except the carbon-coated sodium ferric sulfate material in the positive plate can be all carried out according to the mode in the field, and the effects of higher capacity, better multiplying power performance and more stable cycle performance can be realized.
The battery provided by the invention has the advantages that the capacity, the multiplying power performance and the circulation stability performance of the battery are improved due to the inclusion of the carbon-coated sodium iron sulfate material prepared by the method.
The present invention will be described in detail by examples. The described embodiments of the invention are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The following examples are presented to illustrate the method of preparing carbon coated sodium iron sulfate materials and the resulting carbon coated sodium iron sulfate materials of the present invention.
Example 1
(1) Preparing components:
50.38g (equivalent to 0.18 mol) of ferrous sulfate heptahydrate;
12.87g (corresponding to 0.09 mol) of sodium sulfate;
inorganic carbon source: 2.13g of carbon nano tube;
organic carbon source: 30ml of methanol;
a first solvent: ethanol 50ml;
a second solvent: ethanol 100ml;
dispersing agent: PVP0.22g;
ball milling medium of first ball milling: 3 zirconia beads with diameters of 1mm, 2mm and 3mm respectively;
ball milling medium for second ball milling: 2 zirconia beads with diameters of 0.6mm and 0.8mm respectively.
(2) Preparation of carbon-coated sodium iron sulfate material
Pretreatment of an inorganic carbon source: dispersing an inorganic carbon source and a dispersing agent in a second solvent to form slurry, carrying out ultrasonic treatment on the slurry for 5min, transferring the slurry after ultrasonic treatment into a ball mill, wherein the revolution speed of the ball mill is 300r/min, the rotation speed of the ball mill is 600r/min, the ratio of the weight of a ball milling medium to the sum of the weight of the inorganic carbon source and the dispersing agent is 10:1, and the ball milling time is 4h;
s1: dispersing ferrous sulfate heptahydrate in a first solvent, adding sodium sulfate and pretreated inorganic carbon source slurry to obtain a mixed solution, transferring the mixed solution into a ball mill filled with inert gas for ball milling, wherein the revolution speed of the ball mill is 200r/min, the rotation speed of the ball mill is 400r/min, the ratio of the weight of a ball milling medium to the sum of the weight of the ferrous sulfate heptahydrate, the weight of the sodium sulfate and the weight of the inorganic carbon source is 15:1, the ball milling time is 10 hours, obtaining viscous precursor slurry, drying the precursor slurry in a vacuum oven after the separation of the ball materials, and the drying temperature is 80 ℃ and the drying time is 24 hours, thereby obtaining dry precursor powder;
s2: repeatedly grinding the dry precursor powder, then sintering in a tube furnace, wherein a gas blowing device is arranged at the air inlet end of the tube furnace, an organic carbon source is added into the device, the organic carbon source is preheated by a heating plate, the heating temperature is 60 ℃, the flow rate of carrier gas is 200ml/min, the stability of low-temperature sintering is 350 ℃, and the low-temperature sintering time is 24 hours, so that the carbon-coated sodium iron sulfate material is obtained. In the carbon-coated sodium iron sulfate material, the weight content of the inorganic carbon source is 5wt%.
Example 2 group
This set of examples is intended to illustrate the effect of varying the molar ratio of ferrous sulfate heptahydrate to sodium sulfate.
Example 2a
This example was conducted with reference to example 1 except that the molar ratio of ferrous sulfate heptahydrate to sodium sulfate was adjusted to 1.5:1.
Example 2b
This example was conducted with reference to example 1 except that the molar ratio of ferrous sulfate heptahydrate to sodium sulfate was adjusted to 1.33:1.
Example 2c
This example was conducted with reference to example 1 except that the molar ratio of ferrous sulfate heptahydrate to sodium sulfate was adjusted to 2.2:1.
Example 3 group
The present set of embodiments is used to illustrate the effect that occurs when the flow rate of the carrier gas is changed in step S2.
Example 3a
This example was conducted with reference to example 1, except that the flow rate of the carrier gas in step S2 was adjusted to 1000ml/min.
Example 3b
This example was conducted with reference to example 1, except that the flow rate of the carrier gas in step S2 was adjusted to 3000ml/min.
Example 3c
This example was conducted with reference to example 1, except that the flow rate of the carrier gas in step S2 was adjusted to 50ml/min.
Example 4
This example was conducted with reference to example 1, except that the organic carbon source in step S2 was adjusted to acetonitrile.
Example 5
This example was conducted with reference to example 1, except that the ball milling media in step S1 was adjusted to have only one diameter specification of zirconia beads, each having a diameter of 2mm.
Comparative example 1
This example was conducted with reference to example 1, except that the operation of the organic carbon source in step S2 was not conducted.
Preparation example
The carbon-coated sodium iron sulfate materials obtained in examples and comparative examples were each prepared as follows.
(1) Preparation of positive plate
The carbon-coated sodium iron sulfate material, the conductive agent SP and the binder PVDF are prepared from the following materials in percentage by weight: SP: preparing positive electrode slurry by PVDF=8:1:1, uniformly coating the positive electrode slurry on one side of the surface of the aluminum foil, and drying to obtain the positive electrode plate.
(2) Preparation of negative plate
The negative plate is commercial sodium plate, the other surface of the sodium plate is made of aluminum foil, and the diameter of the sodium plate is 16mm.
(3) Electrolyte solution
The electrolyte is 1M NaClO 4 The solvent is PC, and no other additive is added.
(4) Preparation of a Battery
The battery assembly sequence is negative electrode shell, sodium sheet, diaphragm, electrolyte, positive electrode sheet, gasket, elastic sheet and positive electrode shell.
Test case
The batteries obtained in examples and comparative examples were each subjected to the following test:
(1) Rate capability test
The test voltage is 2-4.5V, the constant-current and constant-voltage process step is adopted for charging, the constant-current process step is adopted for discharging, the theoretical capacity is 120mAh/g, and after the 0.1C is activated for 2 circles, the charging and discharging are sequentially carried out on 1C,2C,5C and 10C.
(2) Cycle performance test
The test voltage is 2-4.5V, the constant-current and constant-voltage process step is adopted for charging, the constant-current process step is adopted for discharging, the theoretical capacity is 120mAh/g, and after 2 circles of 0.1C activation, 1C circulation charging and discharging are carried out.
(3) Discharge capacity test
The test voltage is 2-4.5V, and the constant-current constant-voltage process step is adopted for charging and the constant-current process step is adopted for discharging.
TABLE 1
As can be seen from table 1, the comparative example and the example show that the battery prepared from the carbon-coated sodium iron sulfate material of the example has higher gram capacity performance, better rate capability and more stable cycle performance, and the carbon coating is performed by combining an inorganic carbon source and an organic carbon source, so that the carbon-coated sodium iron sulfate material has more uniform carbon coating and better conductivity, and the gram capacity performance, the rate capability and the cycle stability of the battery are improved.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A method for preparing a carbon-coated sodium iron sulfate material, comprising the steps of:
s1, performing first ball milling on a mixed solution containing a first solvent, ferrous sulfate heptahydrate, sodium sulfate and an inorganic carbon source in inert gas to obtain viscous precursor slurry, and drying the precursor slurry in vacuum atmosphere or inert atmosphere to obtain dry precursor powder;
s2, repeatedly grinding the dry precursor powder, and then sintering at a low temperature in an atmosphere containing an organic carbon source;
in the step S2, the organic carbon source is blown and volatilized into the sintering equipment by a carrier gas, wherein the carrier gas is an inert gas;
in the step S2, the temperature of the low-temperature sintering is 300-450 ℃, and the time of the low-temperature sintering is 6-48h;
the organic carbon source is selected from one or more of ethanol, acetone, methanol, diethyl ether, isopropanol and acetonitrile.
2. The process according to claim 1, wherein the molar ratio of the ferrous sulfate heptahydrate to the sodium sulfate in step S1 is (0.5-2.5): 1;
and/or, in the carbon-coated sodium iron sulfate material, the weight content of the inorganic carbon source is 0.1wt% to 10wt%;
and/or the inorganic carbon source is selected from one or more of carbon nanotubes, carbon fibers, graphene, reduced graphene oxide and amorphous carbon;
and/or the first solvent is selected from one or more of distilled water, ethanol, methanol, acetone, ethylene glycol and azamethylpyrrolidone.
3. The method according to claim 1, wherein the conditions of the first ball milling in step S1 are: revolution speed is 100-1000r/min, rotation speed is 200-2000r/min, and ball milling time is 1-24h; the ball milling medium of the first ball milling is selected from one or more of zirconia beads, agate beads and steel balls, the diameter of the ball milling medium is 0.1mm-20mm, and the diameter of the ball milling medium at least comprises 3 different specifications;
and/or the ratio of the weight of the ball milling medium to the sum of the weight of the ferrous sulfate heptahydrate, the weight of the sodium sulfate and the weight of the inorganic carbon source is (1-100): 1.
4. The method according to claim 1, wherein in the step S1, the drying conditions include: the drying temperature is 40-250 ℃ and the drying time is 1-48h.
5. The method of claim 1, wherein the method further comprises: pretreating the inorganic carbon source, wherein the pretreatment comprises the steps of performing second ball milling and pre-dispersing on the inorganic carbon source, a second solvent and a dispersing agent;
and/or the dispersing agent is selected from one or more of polyvinylpyrrolidone, cetyltrimethylammonium bromide, sodium dodecyl benzene sulfonate and sodium laurylsulfate;
and/or the second solvent is selected from one or more of distilled water, ethanol, methanol, acetone, ethylene glycol and azomethyl pyrrolidone;
and/or the ratio of the amount of the dispersant to the amount of the inorganic carbon source is (0.01-0.5): 1;
and/or the ratio of the amount of the inorganic carbon source to the amount of the second solvent is (0.01-0.1): 1.
6. The method of claim 5, wherein the conditions of the second ball milling are: revolution speed is 100-1000r/min, rotation speed is 200-2000r/min, and ball milling time is 0.1-12h; the ball milling medium of the second ball milling is selected from one or more of zirconia beads, agate beads and steel balls, the diameter of the ball milling medium is 0.1mm-10mm, and the diameter of the ball milling medium at least comprises 2 different specifications;
and/or the ratio of the weight of the ball milling medium to the sum of the weight of the inorganic carbon source and the weight of the dispersant is (1-300): 1.
7. The method of claim 1, wherein the carrier gas has a flow rate of 10ml/min to 3000ml/min.
8. The method of claim 1, wherein the organic carbon source has a boiling point of less than 120 ℃ at atmospheric pressure;
and/or, the method further comprises: and (2) carrying out preheating treatment on the organic carbon source in the step (S2), wherein the preheating temperature is 30-100 ℃.
9. A carbon-coated sodium iron sulfate material prepared according to the method of any one of claims 1-8.
10. A battery, characterized in that the battery comprises a positive plate, and the positive plate comprises the carbon-coated sodium iron sulfate material prepared by the method for preparing the carbon-coated sodium iron sulfate material according to any one of claims 1-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310134154.9A CN116230888B (en) | 2023-02-17 | 2023-02-17 | Method for preparing carbon-coated sodium iron sulfate material, carbon-coated sodium iron sulfate material and battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310134154.9A CN116230888B (en) | 2023-02-17 | 2023-02-17 | Method for preparing carbon-coated sodium iron sulfate material, carbon-coated sodium iron sulfate material and battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116230888A CN116230888A (en) | 2023-06-06 |
| CN116230888B true CN116230888B (en) | 2024-03-08 |
Family
ID=86580068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310134154.9A Active CN116230888B (en) | 2023-02-17 | 2023-02-17 | Method for preparing carbon-coated sodium iron sulfate material, carbon-coated sodium iron sulfate material and battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116230888B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333650A (en) * | 2007-06-27 | 2008-12-31 | 中国科学院金属研究所 | Method for uniformly and controllably coating conducting carbon layer at surface of LiFePO4 granule surface |
| CN101577328A (en) * | 2009-05-21 | 2009-11-11 | 北京化工大学 | Preparation method of LiFePO4/C composite cathode material |
| CN102760880A (en) * | 2012-08-07 | 2012-10-31 | 杨志宽 | High power iron phosphate ion battery material and preparation method thereof |
| CN103985867A (en) * | 2014-05-19 | 2014-08-13 | 电子科技大学 | Method for preparing carbon-coated lithium iron silicate composite material |
| CN109313988A (en) * | 2016-01-26 | 2019-02-05 | 加利福尼亚大学董事会 | Graphene frame for supercapacitor |
| CN115663155A (en) * | 2022-11-15 | 2023-01-31 | 浙江吉利控股集团有限公司 | Composite cathode material and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170237064A1 (en) * | 2016-02-12 | 2017-08-17 | Sumitomo Osaka Cement Co., Ltd | Electrode material for lithium-ion secondary battery, method for manufacturing same, electrode for lithium-ion secondary battery, and lithium-ion secondary battery |
-
2023
- 2023-02-17 CN CN202310134154.9A patent/CN116230888B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333650A (en) * | 2007-06-27 | 2008-12-31 | 中国科学院金属研究所 | Method for uniformly and controllably coating conducting carbon layer at surface of LiFePO4 granule surface |
| CN101577328A (en) * | 2009-05-21 | 2009-11-11 | 北京化工大学 | Preparation method of LiFePO4/C composite cathode material |
| CN102760880A (en) * | 2012-08-07 | 2012-10-31 | 杨志宽 | High power iron phosphate ion battery material and preparation method thereof |
| CN103985867A (en) * | 2014-05-19 | 2014-08-13 | 电子科技大学 | Method for preparing carbon-coated lithium iron silicate composite material |
| CN109313988A (en) * | 2016-01-26 | 2019-02-05 | 加利福尼亚大学董事会 | Graphene frame for supercapacitor |
| CN115663155A (en) * | 2022-11-15 | 2023-01-31 | 浙江吉利控股集团有限公司 | Composite cathode material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Saule Kokhmetova 等.Effect of the MoS2 surface layer on the kinetics of intercalation processes in the NaFe(SO4)2/C composite.《Materials Today Communications》.2021,第28卷文献号：102723. * |
| 颜晨星.硫酸铁钠类材料的制备与电化学性能研究.《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》.2018,(第03期),第C042-2592页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116230888A (en) | 2023-06-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111063870B (en) | Nano material and preparation method thereof, electrode and secondary battery | |
| CN110993949B (en) | Cathode material with multiple coating structures, preparation method and application thereof | |
| CN111082006B (en) | Silicon monoxide composite negative electrode material, preparation method thereof and lithium ion battery | |
| WO2016184355A1 (en) | Method for preparing graphene using coal as raw material | |
| CN113104828B (en) | Preparation method of porous carbon modified sodium iron pyrophosphate phosphate/sodium carbonate ion battery positive electrode material | |
| CN111710845A (en) | Silica composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN113023734A (en) | Porous nitrogen-doped silicon-based negative electrode material and preparation method thereof, negative electrode plate and lithium ion battery | |
| CN112661163B (en) | Silica-based composite anode material, preparation method thereof and lithium ion battery | |
| CN114373909A (en) | Negative electrode material and preparation method and application thereof | |
| CN110395728B (en) | Preparation method of porous carbon sphere negative electrode material for lithium battery | |
| CN109638231B (en) | Silicon monoxide composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN113321198A (en) | Binary metal phosphate anode material and preparation method and application thereof | |
| CN116230888B (en) | Method for preparing carbon-coated sodium iron sulfate material, carbon-coated sodium iron sulfate material and battery | |
| CN113241429A (en) | Preparation method of negative electrode active material | |
| CN117383540A (en) | Preparation method of high-magnification modified biomass hard carbon material | |
| CN110504450B (en) | Preparation method of heteroatom-doped hierarchical pore carbon material and application of heteroatom-doped hierarchical pore carbon material in lithium battery negative electrode slurry | |
| CN109192929B (en) | Lithium ion battery negative plate and preparation method thereof | |
| CN116021007A (en) | Sodium ion battery negative electrode pre-sodium agent and preparation method and application thereof | |
| CN115588734A (en) | Composite lithium supplement agent and preparation method thereof | |
| CN110350191B (en) | Preparation method of sodium/lithium ion battery phosphate anode material | |
| CN114335475A (en) | Metal fluoride/porous carbon composite positive electrode material and positive plate and battery comprising same | |
| CN113735121A (en) | Coral-like strip-shaped porous carbon, and preparation method and application thereof | |
| CN113363433A (en) | Preparation method of silicon-based composite lithium battery negative electrode material | |
| CN112382740A (en) | Graphene-like carbon coated silicon/carbon/graphene composite material, preparation method thereof and negative electrode material | |
| CN115832254B (en) | Silicon-carbon composite anode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |