CN112018365B - Aluminum-doped lithium vanadium fluorophosphate/phosphated graphene oxide composite material, preparation method thereof and application thereof in lithium ion battery - Google Patents
Aluminum-doped lithium vanadium fluorophosphate/phosphated graphene oxide composite material, preparation method thereof and application thereof in lithium ion battery Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 50
- QRVIVVYHHBRVQU-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O Chemical compound [Li+].[V+5].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O QRVIVVYHHBRVQU-UHFFFAOYSA-H 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 claims abstract description 7
- 238000004108 freeze drying Methods 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000012002 vanadium phosphate Substances 0.000 claims description 2
- 159000000001 potassium salts Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 238000005245 sintering Methods 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 13
- 239000012071 phase Substances 0.000 description 7
- 239000010405 anode material Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive 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 discloses an aluminum-doped lithium vanadium fluorophosphate/phosphated graphene oxide composite material, a preparation method thereof and application thereof in a lithium ion battery. The preparation method adopts a step-by-step process, and comprises the following steps: (1) Preparing a precursor of the lithium vanadium phosphate/graphene composite material by a microwave solvothermal method; (2) Preparing an aluminum-doped lithium vanadium fluorophosphate/phosphated graphene oxide composite material by a molten salt method; (3) And after washing the sample, freeze-drying to obtain the pure-phase aluminum-doped lithium vanadium fluorophosphate/phosphated graphene oxide composite material. The composite material can be obtained through one-time sintering, the used process is simple, the purity of the sample is high, the graphene is uniformly coated, the ionic conductivity and the electronic conductivity of the composite material are obviously improved, and the assembled lithium ion battery has excellent electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to an aluminum-doped vanadium lithium fluorophosphate/phosphated graphene oxide composite material, a preparation method thereof and application thereof in a lithium ion battery.
Background
The lithium ion battery is widely applied to various electronic equipment and electric automobiles as an energy system due to the characteristics of no pollution, high specific energy, long cycle life and the like, and is currently becoming a hot spot and a focus of competitive research in various countries. The positive electrode material is an important component of the lithium ion battery, and lithium required for positive and negative electrode deintercalation and SEI film formation is provided in the charge and discharge process of the lithium ion battery, so that the development of the positive electrode material with high performance is a key for the development of the lithium ion battery.
The lithium vanadium fluorophosphate has the advantages of high voltage, high specific capacity, good thermal stability, excellent cycle performance, high safety performance and the like, and compared with the lithium iron phosphate, the lithium vanadium fluorophosphate has a two-dimensional channel which is favorable for lithium ion transmission, but the application of the pure-phase lithium vanadium fluorophosphate in a lithium ion battery is restricted due to low electronic conductivity and low lithium ion diffusion coefficient of the pure-phase lithium vanadium fluorophosphate.
At present, no related report exists on the preparation of aluminum-doped lithium vanadium fluorophosphate/phosphated graphene oxide composite material by a molten salt method, the aluminum-doped lithium vanadium fluorophosphate/phosphated graphene oxide composite material is prepared by a step method, and the nano porous composite material prepared by the process has the advantages of high ion and electron conductivity, and is beneficial to improving the rate capability and low-temperature performance of the lithium vanadium fluorophosphate material.
Disclosure of Invention
The invention provides a method for preparing an aluminum-doped lithium vanadium fluorophosphate/phosphorized graphene oxide composite material by a molten salt method for the first time, and obtaining a pure-phase composite anode material by adopting a freeze-drying method. The invention effectively solves the problem of poor conductivity of the lithium vanadium fluorophosphate material and improves the reversible specific capacity of the material.
In order to realize the technical scheme, the technical scheme of the invention is as follows:
the preparation method of the aluminum-doped lithium vanadium fluorophosphate/phosphated graphene oxide composite material comprises the following steps:
1) Adding the suspension containing graphene into DMF, and heating in a water bath to 70-90 ℃ to prepare a graphene solution;
2) Adding a lithium source, a vanadium source, a phosphorus source and an aluminum source into a graphene solution according to a certain stoichiometric ratio, uniformly stirring, transferring the mixed solution into a polytetrafluoroethylene lining, and carrying out microwave heating at 200-350 ℃ for reaction for 30-60 min;
3) After the reaction is finished, centrifugally washing the solution, collecting precipitate, and drying in a drying oven to obtain a vanadium-lithium phosphate composite material precursor;
4) Uniformly mixing and grinding a precursor of the lithium vanadium phosphate composite material, lithium fluoride, a phosphorus source and molten salt in proportion, and calcining for 1-3 hours at 300-400 ℃ and then for 4-6 hours at 700-850 ℃ in an inert gas atmosphere;
5) And centrifugally washing the collected product by using deionized water, and freeze-drying to obtain the pure aluminum-doped lithium vanadium fluorophosphate/phosphated graphene oxide composite material.
Further, the suspension containing graphene accounts for 50-70% of the volume of the graphene solution.
Further, the lithium source is one of lithium carbonate, lithium nitrate, lithium hydroxide and lithium oxalate, the phosphorus source is one of phosphorus pentoxide, diammonium phosphate and phosphoric acid, the vanadium source is one of vanadium pentoxide, vanadium phosphate and ammonium metavanadate, and the aluminum source is one of aluminum nitrate nonahydrate, lithium metaaluminate and aluminum sulfate.
Further, in the step 4), the molten salt is lithium, sodium and potassium salt with a melting point of 500-900 ℃, and the inert gas is one of nitrogen, argon or helium.
Further, in the step 5), the porous property of the material can be maintained by adopting a freeze drying method, which is beneficial to the ion transmission.
The aluminum-doped lithium vanadium fluorophosphate/phosphated graphene oxide composite material can be used as a positive electrode material of a lithium ion battery.
The invention has the beneficial effects that:
(1) The reactants of the invention realize atomic scale mixing in the liquid phase, the reaction is converted from solid-solid reaction to solid-liquid reaction, and compared with the conventional solid phase method, the method has the advantages of simple process, uniform chemical components of the synthesized powder material, good crystal morphology and high phase purity. The phosphorized graphene oxide disclosed by the invention is characterized in that phosphorus atoms replace part of carbon atoms in graphene at high temperature, and are bonded with other surrounding carbon atoms, so that the energy band structure of the graphene is changed, and p-type doping is formed. Al replaces part V to form an aluminum doped lithium vanadium fluorophosphate solid solution material, so that the conductivity of the material is improved.
(2) The aluminum-doped lithium vanadium fluorophosphate/phosphorized graphene oxide composite material prepared by the invention is a nano material of phosphorus-doped graphene-coated aluminum-doped lithium vanadium fluorophosphate. The phosphorus doped graphene has ion and electron conductivity higher than that of a common graphene oxide material, and the molten salt method can accelerate the ion diffusion rate, so that the uniform doping of phosphorus elements in the graphene material is facilitated; the aluminum element bulk phase doping is beneficial to improving the conductivity, and simultaneously, the defect concentration of the material is increased through doping, and the diffusion channel of lithium ions is expanded, so that the ion and electron conductivity of the lithium vanadium fluorophosphate is improved. Therefore, the rate capability, the cycle performance, the low-temperature performance and the like of the lithium vanadium fluorophosphate material can be improved.
Drawings
FIG. 1 is a scanning electron microscope image of an aluminum-doped lithium vanadium fluorophosphate/phosphated graphene oxide composite;
fig. 2 is a graph comparing the rate performance of aluminum doped lithium vanadium fluorophosphate/phosphated graphene oxide composite in a lithium ion battery.
Detailed Description
Example 1:
the preparation of the lithium vanadium fluorophosphate composite anode material and the application thereof in the lithium ion battery comprise the following steps:
1) Adding a graphene-containing suspension into DMF, sequentially adding a lithium source, a vanadium source, a phosphorus source and an aluminum source into the graphene suspension of 60 ml according to a stoichiometric ratio of 1:1:1:0.2, stirring for 15 min by a magnetic stirrer, transferring the mixed solution into a polytetrafluoroethylene lining, and heating by microwaves at 350 ℃ for 30 min;
2) After the reaction is finished, centrifugally washing the solution, collecting precipitate, and drying in a drying oven;
3) Mixing and grinding a lithium vanadium phosphate/graphene precursor, a fluorine source, a phosphorus source and molten salt uniformly according to a mass ratio of 1:1:1:10, and calcining at 350 ℃ for 2 h and then at 750 ℃ for 5 h in an inert gas atmosphere;
4) And centrifugally washing the collected product, and then freeze-drying to obtain the pure-phase aluminum-doped lithium vanadium fluorophosphate/phosphated graphene oxide composite material.
Fig. 1 is a scanning electron microscope image of a phosphorus-doped graphene-coated aluminum-doped lithium vanadium fluorophosphate composite anode material, and it can be seen from the image that the material is a composite material of lithium vanadium fluorophosphate and carbon, and is a nano material.
Fig. 2 is a comparison graph of the rate performance of the phosphorus-doped graphene-coated aluminum-doped lithium vanadium fluorophosphate composite cathode material in a lithium ion battery, and it can be seen from the graph that the modified lithium vanadium fluorophosphate composite cathode material has excellent rate performance.
Example 2:
the preparation of the lithium vanadium fluorophosphate composite anode material and the application thereof in the lithium ion battery comprise the following steps:
1) Adding a graphene-containing suspension into DMF, sequentially adding a lithium source, a vanadium source, a phosphorus source and an aluminum source into the graphene suspension of 70 ml according to a stoichiometric ratio of 1:1:1:0.5, stirring for 25 min by a magnetic stirrer, transferring the mixed solution into a polytetrafluoroethylene lining, and heating by microwaves at 250 ℃ for 45 min;
2) After the reaction is finished, centrifugally washing the solution, collecting precipitate, and drying in a drying oven;
3) Mixing and grinding a lithium vanadium phosphate/graphene precursor, a fluorine source, a phosphorus source and molten salt uniformly according to a mass ratio of 1:1:2:20, and calcining at 400 ℃ for 2 h and then at 800 ℃ for 3 h in an inert gas atmosphere;
4) And centrifugally washing the collected product, and then freeze-drying to obtain the pure-phase aluminum-doped lithium vanadium fluorophosphate/phosphated graphene oxide composite material.
Fig. 1 is a scanning electron microscope image of a phosphorus-doped graphene-coated aluminum-doped lithium vanadium fluorophosphate composite anode material, and it can be seen from the image that the material is a composite material of lithium vanadium fluorophosphate and carbon, and is a nano material.
Fig. 2 is a comparison graph of the rate performance of the phosphorus-doped graphene-coated aluminum-doped lithium vanadium fluorophosphate composite cathode material in a lithium ion battery, and it can be seen from the graph that the modified lithium vanadium fluorophosphate composite cathode material has excellent rate performance.
The above description is only of embodiments of the present invention and not intended to limit the scope of the invention, and it will be apparent to those skilled in the art from this description that modifications and variations can be made thereto, all of which shall fall within the scope of the appended claims.
Claims (1)
1. The aluminum-doped lithium vanadium fluorophosphate/graphene phosphide composite material is characterized in that: the preparation method of the composite material comprises the following steps:
adding the suspension containing graphene into DMF, and heating in a water bath to 70-90 ℃ to prepare a graphene solution;
adding a lithium source, a vanadium source, a phosphorus source and an aluminum source into a graphene solution according to a stoichiometric ratio of 1:1:1:0.2, uniformly stirring, transferring the mixed solution into a polytetrafluoroethylene lining, and carrying out microwave heating at 200-350 ℃ for reaction for 30-60 min;
3) After the reaction is finished, centrifugally washing the solution, collecting precipitate, and drying in a drying oven to obtain a vanadium-lithium phosphate composite material precursor;
4) Uniformly mixing and grinding a precursor of the lithium vanadium phosphate composite material, lithium fluoride, a phosphorus source and molten salt according to a mass ratio of 1:1:1:10, calcining for 1-3 hours at 300-400 ℃ and then calcining for 4-6 hours at 700-850 ℃ in an inert gas atmosphere;
5) Centrifugally washing the collected product by deionized water, and freeze-drying to obtain a pure aluminum-doped lithium vanadium fluorophosphate/graphene phosphide composite material; the aluminum-doped lithium vanadium fluorophosphate/graphene phosphide composite material is specifically a composite nano material of phosphorus-doped graphene coated aluminum-doped lithium vanadium fluorophosphate;
in the step 4), the molten salt is lithium, sodium and potassium salts with melting points of 500-900 ℃, and the inert gas is argon or helium; the suspension containing graphene accounts for 50-70% of the volume of the graphene solution; the lithium source is one of lithium carbonate, lithium nitrate, lithium hydroxide and lithium oxalate; the phosphorus source is one of phosphorus pentoxide, diammonium hydrogen phosphate and phosphoric acid; the vanadium source is one of vanadium pentoxide, vanadium phosphate and ammonium metavanadate; the aluminum source is one of aluminum nitrate nonahydrate, lithium metaaluminate and aluminum sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010934268.8A CN112018365B (en) | 2020-09-08 | 2020-09-08 | Aluminum-doped lithium vanadium fluorophosphate/phosphated graphene oxide composite material, preparation method thereof and application thereof in lithium ion battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010934268.8A CN112018365B (en) | 2020-09-08 | 2020-09-08 | Aluminum-doped lithium vanadium fluorophosphate/phosphated graphene oxide composite material, preparation method thereof and application thereof in lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112018365A CN112018365A (en) | 2020-12-01 |
| CN112018365B true CN112018365B (en) | 2024-03-08 |
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