CN117317199B - Antimony-based negative electrode material and preparation method thereof - Google Patents
Antimony-based negative electrode material and preparation method thereof Download PDFInfo
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- CN117317199B CN117317199B CN202311549580.5A CN202311549580A CN117317199B CN 117317199 B CN117317199 B CN 117317199B CN 202311549580 A CN202311549580 A CN 202311549580A CN 117317199 B CN117317199 B CN 117317199B
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 39
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 38
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 34
- KIQKNTIOWITBBA-UHFFFAOYSA-K antimony(3+);phosphate Chemical compound [Sb+3].[O-]P([O-])([O-])=O KIQKNTIOWITBBA-UHFFFAOYSA-K 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 235000019832 sodium triphosphate Nutrition 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims abstract description 8
- 150000001462 antimony Chemical class 0.000 claims abstract description 7
- 238000004729 solvothermal method Methods 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 4
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- JRLDUDBQNVFTCA-UHFFFAOYSA-N antimony(3+);trinitrate Chemical compound [Sb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JRLDUDBQNVFTCA-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052744 lithium Inorganic materials 0.000 abstract description 15
- 239000010405 anode material Substances 0.000 abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229940093429 polyethylene glycol 6000 Drugs 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the field of battery anode materials, in particular to an antimony-based anode material and a preparation method thereof, wherein the antimony phosphate is hexagonal prism, and the preparation method of the antimony phosphate is as follows: respectively dissolving water-soluble antimony salt and tripolyphosphate in a polyalcohol solvent to obtain a solution A and a solution B, uniformly mixing the solution A and the solution B, adding dilute hydrochloric acid into the obtained mixed solution to enable the pH value to be 4-5, transferring the mixed solution into a reaction kettle for solvothermal reaction, washing and drying reaction products, and obtaining the lithium battery assembled by the antimony-based negative electrode material.
Description
Technical Field
The invention relates to the field of battery anode materials, in particular to an antimony-based anode material and a preparation method thereof.
Background
In recent years, large-scale electric facilities such as electric automobiles, unmanned aerial vehicles and smart grids are rapidly developed, and the development prospect of lithium ion batteries is influenced by unprecedented electric energy consumption, so that high-capacity lithium ion batteries are just needed in the electric facilities industry, and in the lithium ion batteries, good negative electrode materials have the characteristics of high energy density, long service life and the like.
At present, antimony phosphate has been studied as a negative electrode material in the field of batteries, but the antimony phosphate material itself is poor in conductivity, and meanwhile, volume expansion easily occurs during charge and discharge cycles, so that the application of the antimony phosphate material is limited.
Disclosure of Invention
The invention aims to: aiming at the technical problems, the invention provides an antimony-based negative electrode material and a preparation method thereof.
The technical scheme adopted is as follows:
an antimony-based negative electrode material: comprises antimony phosphate which is in a hexagonal prism shape.
Further, the preparation method of the antimony phosphate comprises the following steps:
respectively dissolving water-soluble antimony salt and tripolyphosphate in a polyalcohol solvent to obtain a solution A and a solution B, uniformly mixing the solution A and the solution B, adding dilute hydrochloric acid into the obtained mixed solution to enable the pH value to be 4-5, transferring the mixed solution into a reaction kettle for solvothermal reaction, washing a reaction product, and drying.
Further, the water-soluble antimony salt is any one or a combination of more of antimony chloride, antimony nitrate and soluble organic antimony salt.
Further, the tripolyphosphate is sodium tripolyphosphate and/or potassium tripolyphosphate.
Further, the solvothermal reaction temperature is 130-150 ℃.
Further, the solvothermal reaction time is 24-36h.
Further, nitrogen-doped carbon is also included.
Further, the nitrogen-doped carbon is coated on the outer surface of the antimony phosphate.
The invention also provides a preparation method of the antimony-based negative electrode material, which comprises the following steps:
generating a precursor on the outer surface of the antimony phosphate through polymerization reaction, and then heating to 350-800 ℃ under the protection of inert gas for carbonization for 1-5 h.
Further, the precursor is polypyrrole.
The invention has the beneficial effects that:
the invention provides an antimony-based negative electrode material, which controls the morphology of generated antimony phosphate to obtain hexagonal prism-shaped antimony phosphate through the hydrolysis of tripolyphosphate and the control of reaction conditions, shortens the transmission distance of lithium ions/electrons through a special microstructure, improves the reaction kinetics, provides abundant electrochemical active sites through a larger specific surface area, improves the lithium storage capacity, coats a nitrogen-doped carbon layer on the outer surface of the antimony phosphate, can further improve the conductivity of the antimony-based negative electrode material, can effectively prevent the expansion and fragmentation of the antimony phosphate, and can provide a necessary transmission path for electrolyte.
Drawings
Fig. 1 is an SEM image of the antimony-based negative electrode material prepared in example 1, in which a hexagonal prism-like structure is clearly observed, and in which agglomerated particles may be generated due to agglomeration of nitrogen-doped carbon generated during carbonization due to non-uniform coating of polypyrrole.
Detailed Description
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. The technology not mentioned in the present invention refers to the prior art, and unless otherwise indicated, the following examples and comparative examples are parallel tests, employing the same processing steps and parameters.
Example 1:
the embodiment provides an antimony-based negative electrode material, in particular to hexagonal prism-shaped antimony phosphate with nitrogen-doped carbon coated on the surface;
the preparation method comprises the following steps:
dissolving 6.84g of antimony chloride and 3.68g of sodium tripolyphosphate in 50ml of ethylene glycol respectively to obtain a solution A and a solution B, mixing the solution A and the solution B, stirring for 30min to uniformly mix, dropwise adding 0.1M dilute hydrochloric acid into the obtained mixed solution until the pH value of the system is 4, transferring into a reaction kettle to be sealed and heated to 150 ℃ for reaction for 32h, filtering out precipitate after reaction, washing with ethanol and drying to obtain antimony phosphate, uniformly mixing 0.2g of sodium dodecyl sulfate, 0.35g of polyethylene glycol 6000, 0.1g of polyvinylpyrrolidone, 0.15g of ethanol, 0.07g of butanol, 2.5g of pyrrole monomer and 90ml of chloroform, adding 5g of antimony phosphate, ultrasonically oscillating for 30min, adding 5g of benzoyl peroxide, dropwise adding 40% of peracetic acid to react for 5h at room temperature, filtering out precipitate, washing with chloroform and drying, transferring into a muffle furnace to be carbonized for 3h at 550 ℃ under the protection of argon.
The antimony-based negative electrode material prepared by the method is mixed with acetylene black and PVDF according to the weight ratio of 8:1:1 weighing materials, mixing, dripping proper amount of N-methyl pyrrolidone (NMP) to prepare slurry with certain viscosity, uniformly coating the slurry on aluminum foil, drying, cutting into 12mm wafer to serve as a prototype current collector, putting the prototype current collector into a 2032 type button battery shell to serve as a negative electrode, taking metal lithium as a counter electrode, taking Celgard type polyethylene film as a diaphragm, and taking 1 mm wafer as a prototype current collector under the protection of argon in a glove boxLiPF of mol/L 6 The lithium battery assembled by the antimony-based negative electrode material prepared in the embodiment has good electrochemical performance and good cycling stability, and the lithium battery assembled by the antimony-based negative electrode material prepared in the embodiment has good electrochemical performance.
Example 2:
the embodiment provides an antimony-based negative electrode material, in particular to hexagonal prism-shaped antimony phosphate with nitrogen-doped carbon coated on the surface;
the preparation method comprises the following steps:
dissolving 6.84g of antimony chloride and 3.68g of sodium tripolyphosphate in 50ml of ethylene glycol respectively to obtain a solution A and a solution B, mixing the solution A and the solution B, stirring for 30min to uniformly mix, dropwise adding 0.1M dilute hydrochloric acid into the obtained mixed solution until the pH value of the system is 4, transferring into a reaction kettle to be sealed and heated to 150 ℃ for reaction for 36h, filtering out precipitate after reaction, washing with ethanol and drying to obtain antimony phosphate, uniformly mixing 0.2g of sodium dodecyl sulfate, 0.35g of polyethylene glycol 6000, 0.1g of polyvinylpyrrolidone, 0.15g of ethanol, 0.07g of butanol, 2.5g of pyrrole monomer and 90ml of chloroform, adding 5g of antimony phosphate, ultrasonically oscillating for 30min, adding 5g of benzoyl peroxide, dropwise adding 40% of peracetic acid to react for 5h at room temperature, filtering out precipitate, washing with chloroform and drying, transferring into a muffle furnace to be carbonized for 5h at 800 ℃ under the protection of argon.
The antimony-based negative electrode material prepared by the method is mixed with acetylene black and PVDF according to the weight ratio of 8:1:1 weighing materials, mixing, dripping proper amount of N-methyl pyrrolidone (NMP) to prepare slurry with certain viscosity, uniformly coating the slurry on aluminum foil, drying, cutting into 12mm wafer to be used as prototype current collector, putting the prototype current collector into 2032 type button cell shell to be used as a negative electrode under the protection of argon in a glove box, and taking metal lithium as a negative electrodeAs a counter electrode, celgard type polyethylene film was used as a separator with 1mol/L LiPF 6 The lithium battery assembled by the antimony-based negative electrode material prepared in the embodiment has good electrochemical performance and good cycling stability, and the lithium battery assembled by the antimony-based negative electrode material prepared in the embodiment has good electrochemical performance.
Example 3:
the embodiment provides an antimony-based negative electrode material, in particular to hexagonal prism-shaped antimony phosphate with nitrogen-doped carbon coated on the surface;
the preparation method comprises the following steps:
dissolving 6.84g of antimony chloride and 3.68g of sodium tripolyphosphate in 50ml of ethylene glycol respectively to obtain a solution A and a solution B, mixing the solution A and the solution B, stirring for 30min to uniformly mix, dropwise adding 0.1M dilute hydrochloric acid into the obtained mixed solution until the pH value of the system is 4, transferring into a reaction kettle to be sealed and heated to 130 ℃ for reaction for 24h, filtering out precipitate after reaction, washing with ethanol and drying to obtain antimony phosphate, uniformly mixing 0.2g of sodium dodecyl sulfate, 0.35g of polyethylene glycol 6000, 0.1g of polyvinylpyrrolidone, 0.15g of ethanol, 0.07g of butanol, 2.5g of pyrrole monomer and 90ml of chloroform, adding 5g of antimony phosphate, ultrasonically oscillating for 30min, adding 5g of benzoyl peroxide, dropwise adding 40% of peracetic acid to enable the pH value of the system to be 2, filtering out precipitate after reaction for 5h at room temperature, washing with chloroform and drying, transferring into a muffle furnace to be carbonized for 3h under the protection of argon.
The antimony-based negative electrode material prepared by the method is mixed with acetylene black and PVDF according to the weight ratio of 8:1:1 weighing materials, mixing, dripping proper amount of N-methyl pyrrolidone (NMP) to prepare slurry with certain viscosity, uniformly coating the slurry on aluminum foil, drying, cutting into 12mm wafer to serve as prototype current collector, and protecting the prototype current collector with argon in a glove boxPutting the lithium ion battery into a 2032 button battery shell to serve as a negative electrode, taking metal lithium as a counter electrode, taking a Celgard type polyethylene film as a diaphragm, and taking 1mol/L LiPF 6 The lithium battery assembled by the antimony-based negative electrode material prepared in the embodiment has good electrochemical performance and good cycling stability, and the lithium battery assembled by the antimony-based negative electrode material prepared in the embodiment has good electrochemical performance.
Example 4:
the embodiment provides an antimony-based negative electrode material, in particular to hexagonal prism-shaped antimony phosphate with nitrogen-doped carbon coated on the surface;
the preparation method comprises the following steps:
dissolving 6.84g of antimony chloride and 3.68g of sodium tripolyphosphate in 50ml of ethylene glycol respectively to obtain a solution A and a solution B, mixing the solution A and the solution B, stirring for 30min to uniformly mix, dropwise adding 0.1M dilute hydrochloric acid into the obtained mixed solution until the pH value of the system is 4, transferring into a reaction kettle to be sealed and heated to 150 ℃ for reaction for 24h, filtering out precipitate after reaction, washing with ethanol and drying to obtain antimony phosphate, uniformly mixing 0.2g of sodium dodecyl sulfate, 0.35g of polyethylene glycol 6000, 0.1g of polyvinylpyrrolidone, 0.15g of ethanol, 0.07g of butanol, 2.5g of pyrrole monomer and 90ml of chloroform, adding 5g of antimony phosphate, ultrasonically oscillating for 30min, adding 5g of benzoyl peroxide, dropwise adding 40% of peracetic acid to react for 5h at room temperature, filtering out precipitate, washing with chloroform and drying, transferring into a muffle furnace to be carbonized for 5h at 650 ℃ under the protection of argon.
The antimony-based negative electrode material prepared by the method is mixed with acetylene black and PVDF according to the weight ratio of 8:1:1 weighing materials, mixing, dripping proper amount of N-methyl pyrrolidone (NMP) to prepare slurry with certain viscosity, uniformly coating the slurry on aluminum foil, drying, and cutting into 12mm wafer as prototypeUnder the protection of argon in a glove box, placing a prototype current collector into a 2032 button battery shell to serve as a negative electrode, taking metallic lithium as a counter electrode, taking a Celgard type polyethylene film as a diaphragm, and taking 1mol/L LiPF 6 The lithium battery assembled by the antimony-based negative electrode material prepared in the embodiment has good electrochemical performance and good cycling stability, and is proved to be good in cycling stability.
Comparative example 1:
substantially the same as in example 1, except that antimony phosphate was directly used as a negative electrode material without being subjected to nitrogen-doped carbon coating;
the preparation method comprises the following steps:
6.84g of antimony chloride and 3.68g of sodium tripolyphosphate are respectively dissolved in 50ml of ethylene glycol to obtain a solution A and a solution B, the solution A and the solution B are mixed and stirred for 30min to be uniformly mixed, 0.1M dilute hydrochloric acid is dropwise added into the obtained mixed solution until the pH value of the system is 4, the mixed solution is transferred into a reaction kettle to be sealed and heated to 150 ℃ for reaction for 32h, and after the reaction is finished, the precipitate is filtered out, washed by ethanol and dried to obtain the antimony phosphate.
The antimony-based negative electrode material prepared by the method is mixed with acetylene black and PVDF according to the weight ratio of 8:1:1 weighing materials, mixing uniformly, dripping a proper amount of N-methyl pyrrolidone (NMP) to prepare slurry with certain viscosity, uniformly coating the slurry on an aluminum foil, drying, cutting into a wafer with the thickness of 12mm to serve as a prototype current collector, putting the prototype current collector into a 2032 type button battery shell to serve as a negative electrode, taking metal lithium as a counter electrode, taking a Celgard type polyethylene film as a diaphragm, and taking 1mol/L LiPF under the protection of argon in a glove box 6 A 2032 type coin cell was assembled with a mixture of Ethyl Carbonate (EC) and dimethyl carbonate (DMC) as electrolyte (EC: dmc=1:1 (v/v), and the chemical performance test passed by blueThe test of the electric test system is carried out, the activation is carried out for three circles under the small multiplying power of 0.1C, then the test is carried out under the condition of 1C, the activation is carried out under the multiplying power of 0.1C, the specific capacity 773.2mAh/g of the first discharge is carried out, the specific capacity of the 1C is 324.8mAh/g after the cycle is carried out for 5000 circles, the capacity retention rate is 42%, and compared with the embodiment 1, the nitrogen-doped carbon coating plays a positive role in improving the electrochemical performance and the cycle stability of the lithium battery assembled by the antimony-based negative electrode material.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. An antimony-based negative electrode material, comprising antimony phosphate, wherein the antimony phosphate has a hexagonal prism shape.
2. The antimony-based negative electrode material according to claim 1, wherein the method for preparing antimony phosphate comprises the steps of:
respectively dissolving water-soluble antimony salt and tripolyphosphate in a polyalcohol solvent to obtain a solution A and a solution B, uniformly mixing the solution A and the solution B, adding dilute hydrochloric acid into the obtained mixed solution to enable the pH value to be 4-5, transferring the mixed solution into a reaction kettle for solvothermal reaction, washing a reaction product, and drying.
3. The antimony-based negative electrode material according to claim 2, wherein the water-soluble antimony salt is any one or a combination of more of antimony chloride, antimony nitrate, or soluble organic antimony salts.
4. The antimony-based negative electrode material according to claim 2, wherein the tripolyphosphate is sodium tripolyphosphate and/or potassium tripolyphosphate.
5. The antimony-based negative electrode material according to claim 2, wherein the solvothermal reaction temperature is 130-150 ℃.
6. The antimony-based negative electrode material according to claim 2, wherein the solvothermal reaction time is 24-36h.
7. The antimony-based negative electrode material according to claim 1, further comprising nitrogen-doped carbon.
8. The antimony-based negative electrode material according to claim 7, wherein the nitrogen-doped carbon is coated on an outer surface of the antimony phosphate.
9. The method for preparing an antimony-based negative electrode material according to claim 8, wherein the precursor is formed on the outer surface of the antimony phosphate by polymerization, and is carbonized by heating to 350-800 ℃ under the protection of inert gas for 1-5 hours.
10. The method for producing an antimony-based negative electrode material according to claim 9, wherein the precursor is polypyrrole.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB792997A (en) * | 1955-09-23 | 1958-04-09 | Ass Lead Mfg Ltd | Improvements in the manufacture of antimony phosphate |
| JP2002200495A (en) * | 2000-12-28 | 2002-07-16 | National Institute Of Advanced Industrial & Technology | Method of removing antimony and removing agent for the same |
| CN106185858A (en) * | 2016-07-26 | 2016-12-07 | 南京信息工程大学 | The simple method for preparing of a kind of uniform phosphoric acid antimony micron bar and photocatalysis performance thereof |
| CN106219508A (en) * | 2016-07-26 | 2016-12-14 | 南京信息工程大学 | A kind of simple method for preparing of mixed style structure phosphoric acid antimony |
| CN113479860A (en) * | 2021-07-01 | 2021-10-08 | 中国石油大学(华东) | SbPO4Preparation method of/nitrogen-doped carbon composite material |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB792997A (en) * | 1955-09-23 | 1958-04-09 | Ass Lead Mfg Ltd | Improvements in the manufacture of antimony phosphate |
| JP2002200495A (en) * | 2000-12-28 | 2002-07-16 | National Institute Of Advanced Industrial & Technology | Method of removing antimony and removing agent for the same |
| CN106185858A (en) * | 2016-07-26 | 2016-12-07 | 南京信息工程大学 | The simple method for preparing of a kind of uniform phosphoric acid antimony micron bar and photocatalysis performance thereof |
| CN106219508A (en) * | 2016-07-26 | 2016-12-14 | 南京信息工程大学 | A kind of simple method for preparing of mixed style structure phosphoric acid antimony |
| CN113479860A (en) * | 2021-07-01 | 2021-10-08 | 中国石油大学(华东) | SbPO4Preparation method of/nitrogen-doped carbon composite material |
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