CN107706380B - Method for preparing lithium vanadium phosphate/graphene composite cathode material on metal base - Google Patents
Method for preparing lithium vanadium phosphate/graphene composite cathode material on metal base Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 48
- 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 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 35
- 239000002184 metal Substances 0.000 title claims abstract description 35
- 239000010406 cathode material Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims description 20
- 150000003682 vanadium compounds Chemical class 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 230000001681 protective effect Effects 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 61
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical group O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 30
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 15
- 239000001509 sodium citrate Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 235000021317 phosphate Nutrition 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000007900 aqueous suspension Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 150000002642 lithium compounds Chemical class 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 21
- 238000002360 preparation method Methods 0.000 abstract description 9
- 239000010405 anode material Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 8
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 8
- 235000019837 monoammonium phosphate Nutrition 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- -1 phosphorus ions Chemical class 0.000 description 3
- 229910001456 vanadium ion Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229940071260 lithium gluconate Drugs 0.000 description 1
- ZOTSUVWAEYHZRI-JJKGCWMISA-M lithium;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Li+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O ZOTSUVWAEYHZRI-JJKGCWMISA-M 0.000 description 1
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical Kinetics & Catalysis (AREA)
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- 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 particularly relates to a preparation method of a lithium vanadium phosphate/graphene composite cathode material. Then horizontally placing the metal matrix with the vanadium compound attached to the surface in the mixed solution for soaking for several days, taking out the soaked metal matrix for drying, then carrying out high-temperature calcination for a period of time under a protective atmosphere, and then taking out and cooling; repeating the steps for a plurality of times to obtain the lithium vanadium phosphate/graphene composite anode material. The lithium vanadium phosphate/graphene composite cathode material disclosed by the invention has the advantages of high specific capacity, good cycle performance, good rate performance and the like, and integrates the advantages of low cost, environmental friendliness and the like.
Description
Technical Field
The invention belongs to the technical field of battery positive electrode composite materials, and particularly relates to a method for preparing a lithium vanadium phosphate/graphene composite positive electrode material on a metal base.
Background
Since Goodenough and the like put forward a polyanionic lithium battery anode material lithium iron phosphate for the first time, researchers have developed a great deal of research on polyanionic phosphates, wherein the most successful is to realize the industrial production of the polyanionic lithium iron phosphate anode material, but people have not reported many research on lithium vanadium phosphate, and the industrial production is still not realized at present. However, lithium vanadium phosphate is a material with better performance than lithium iron phosphate, and has the following advantages: a. the lithium iron phosphate has excellent thermal stability, and is only slightly lower than lithium iron phosphate in the currently researched anode material; b. the lithium ion battery has high discharge voltage and a plurality of discharge voltage platforms, the average discharge voltage is 4.1V, which is higher than the 3.4V discharge voltage of lithium iron phosphate, and 3.5V, 3.6V, 4.1V and 4.6V 4 discharge platforms are arranged; c. excellent cycling stability and high discharge capacity, and the theoretical capacity is 197 mAh/g and is higher than that of 170 mAh/g of lithium iron phosphate. It can be seen that the research space for lithium vanadium phosphate is large.
Graphene has high electronic conductivity, wherein the movement rate of electrons reaches 1/300 of the speed of light, and is an excellent electron conductor, and graphene has lithium storage characteristics. Therefore, the lithium vanadium phosphate is compounded with the graphene sheet to prepare the lithium vanadium phosphate/graphene composite electrode material, so that lithium vanadium phosphate particles are attached to or wrapped on the graphene sheet, the conductivity of the material can be effectively improved, the growth of the particles can be effectively inhibited, the conductive capacity of the lithium vanadium phosphate material can be greatly improved, and the specific capacity and the rate capability of the material can be effectively improved. Chinese patent publication No. CN102386410A discloses a lithium vanadium phosphate/graphene composite material and a preparation method thereof, which is composed of lithium vanadium phosphate and graphene or graphene and other amorphous carbon, but the method has a complex process, and the obtained composite material has unstable performance and low specific charge capacity when used as a lithium ion battery anode material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing a lithium vanadium phosphate/graphene composite cathode material on a metal base, which is simple, environment-friendly, stable in structure, good in cycle performance and low in production cost.
The invention also aims to provide a lithium vanadium phosphate/graphene composite cathode material.
The purpose of the invention is realized by the following technical scheme:
the method for preparing the lithium vanadium phosphate/graphene composite cathode material on the metal base comprises the following steps:
s1, mixing soluble lithium compounds, iron compounds and phosphates according to the atomic ratio of lithium to iron to phosphorus of 3:2:3, putting the mixture into deionized water, adding a proper amount of sodium citrate and graphene oxide, and fully stirring at a certain temperature to form a mixed solution;
s2, horizontally placing the metal matrix with the vanadium compound attached to the surface in the mixed solution obtained in the step S1 for soaking for several days, taking out the soaked metal matrix for drying, then carrying out high-temperature calcination for a period of time in a protective atmosphere, and then taking out and cooling;
s3, repeating the steps S1 and S2 for not less than 2 times by taking the calcined and cooled substrate as an object;
and S4, sequentially carrying out low-temperature carbonization treatment and high-temperature synthesis treatment on the matrix obtained in the step S3 in a protective atmosphere to obtain the lithium vanadium phosphate/graphene composite cathode material.
The invention creatively puts the metal matrix with the vanadium compound attached on the surface into the mixed solution containing lithium ions, vanadium ions, phosphorus ions, sodium citrate and graphene oxide to be soaked for a plurality of days, simultaneously carrying out three groups of reactions, namely reacting graphene oxide with lithium ions, vanadium ions and phosphorus ions, reacting sodium citrate with lithium ions, vanadium ions and phosphorus ions, carrying out reduction reaction on graphene oxide and sodium citrate, and finally forming a primary composite material by the three groups of reactions, after the substrate is immersed in the mixed solution, the vanadium compound attached to the surface of the metal substrate can be used as a seed crystal to grow and enlarge the periphery of the composite material seed until the composite material with excellent performance is formed, and the formed lithium vanadium phosphate/graphene composite material has excellent performance.
Preferably, in the step S1, the mass fraction of the added sodium citrate is 5-25%, the mass fraction of the added graphene oxide is 5-10%, and the temperature is 70-90%oStirring for 0.5-2 h under C.
Preferably, the number of days for immersing the metal matrix with the vanadium compound attached to the surface in the mixed solution in the step S2 is 3-5 days;
preferably, the high-temperature calcination in step S2 is performed in a tube furnace, the temperature is 800 to 1000 ℃, the calcination time is 0.5 to 1 hour, and the protective atmosphere is nitrogen.
Preferably, the preparation method of the metal matrix with the vanadium compound attached to the surface comprises the following steps: mixing a proper amount of vanadium compound and pure water to form solution or suspension, uniformly spraying the solution or suspension on the surface of a matrix in a spraying mode, then drying the metal matrix sprayed with the vanadium compound solution in vacuum, putting the metal matrix into a tubular furnace, and calcining the metal matrix in a protective atmosphere at a certain temperature for a certain time.
Further preferably, the vanadium compound on the substrate is V2O5、NH4VO3、V2O3One or more of (a), the vanadium compoundThe concentration of the product prepared into an aqueous solution or suspension is 0.1-0.15 mmol/ml;
further preferably, the vacuum drying specifically comprises the step of drying the substrate for 1-5 hours in a vacuum drying oven at the temperature of 110-120 ℃;
further preferably, the calcining temperature in the tube furnace is 300-600 ℃, the time is 1-2 hours, and the protective gas is nitrogen.
The invention also discloses a lithium vanadium phosphate/graphene composite cathode material prepared by the preparation method of the composite cathode material.
Compared with the prior art, the invention has the advantages that:
(1) the lithium vanadium phosphate/graphene composite anode material synthesized by the method has the characteristic of multiple pore channels, and the structure can enable electrolyte to enter easily, increase the contact area between the electrolyte and the composite material, greatly shorten the transmission path of lithium ions, improve the transmission efficiency of the lithium ions and further obtain good electrochemical performance.
(2) When the metal matrix with the vanadium compound on the surface is prepared, the vanadium compound is creatively prepared into the aqueous solution, the aqueous solution of the vanadium compound is uniformly sprayed on the surface of the matrix through a spraying method, the vanadium compound on the surface of the matrix is the seed crystal, when the matrix is immersed in the mixed solution, the existence of the seed crystal is beneficial to the formation of the lithium vanadium phosphate crystal, and the formed particles are uniformly distributed on the matrix, so that the performance of the formed composite material is more excellent.
(3) The lithium vanadium phosphate/graphene composite cathode material disclosed by the invention has the advantages of high specific capacity, good cycle performance, good rate performance and the like, and integrates the advantages of low cost, environmental friendliness and the like. Meanwhile, the preparation method of the lithium vanadium phosphate/graphene composite cathode material has the advantages of simple process, easiness in operation and lower cost, and provides an effective way for obtaining the lithium vanadium phosphate/graphene composite cathode material with excellent performance.
Detailed Description
The invention is further illustrated by the following specific examples. The following examples are illustrative only and are not to be construed as unduly limiting the invention which may be embodied in many different forms as defined and covered by the summary of the invention. Reagents, compounds and apparatus employed in the present invention are conventional in the art unless otherwise indicated.
The graphene oxide used in the embodiment of the invention is prepared by adopting improved hummers.
Example 1
Having a surface V2O5Preparation of the matrix of (1): will V2O5Dissolving in pure water to prepare 0.1 mmol/ml V2O5The aqueous solution is uniformly sprayed on a stainless steel substrate by a simple spraying device, then the stainless steel substrate is placed in a vacuum drying oven to be dried for 1 hour at 120 ℃, then the stainless steel substrate is placed in a tube furnace to be calcined for 5 hours at 400 ℃ in nitrogen atmosphere, and the surface V is obtained2O5The stainless steel substrate of (1).
S1, dissolving lithium acetate, vanadium pentoxide and ammonium dihydrogen phosphate in a molar ratio of 3:1:3 in deionized water, adding 15% of sodium citrate, and stirring on a magnetic stirrer at 70 ℃ to completely dissolve the sodium citrate and the vanadium pentoxide and the ammonium dihydrogen phosphate to form a transparent mixed solution;
s2, horizontally placing the substrate with the vanadium pentoxide on the surface into the transparent mixed solution obtained in the step S1 for soaking for 5 days, taking out the soaked substrate, placing the substrate into a vacuum drying oven for drying, then placing the substrate into a tubular furnace for calcining at 750 ℃ for 3 hours under the nitrogen protection atmosphere, and then taking out the substrate for cooling;
and S3, repeating the steps S1 and S22 times to obtain the lithium vanadium phosphate/graphene composite cathode material by taking the calcined and cooled substrate obtained in the step S2 as an object.
When the obtained lithium vanadium phosphate/graphene composite cathode material is charged and discharged at a multiplying power of 5C, the first discharge specific capacity at room temperature can reach 131 mAh/g; after 50 cycles, the capacity retention rate was 93.1%.
Example 2
Having a surface V2O3Preparation of the matrix of (1): will V2O3Dissolving in pure water to prepare 0.05 mmol/ml V2O3By simple sprayingUniformly spraying on a stainless steel substrate, placing the stainless steel substrate in a vacuum drying oven, baking at 120 ℃ for 1 hour, placing the stainless steel substrate in a tube furnace, calcining at 400 ℃ for 2 hours in a nitrogen atmosphere to obtain a product with V on the surface2O3The stainless steel substrate of (1).
S1, dissolving lithium acetate, vanadium pentoxide and ammonium dihydrogen phosphate in a molar ratio of 3:1:3 in deionized water, adding 16% of sodium citrate, and stirring at 80 ℃ on a magnetic stirrer to completely dissolve the sodium citrate and the vanadium pentoxide and the ammonium dihydrogen phosphate to form a transparent mixed solution;
s2, horizontally placing the substrate with the vanadium trioxide on the surface into the transparent mixed solution obtained in the step S1 for soaking for 15 days, taking out the soaked substrate, placing the substrate into a vacuum drying oven for drying, then placing the substrate into a tubular furnace for 850 ℃ calcination for 3 hours under the nitrogen protection atmosphere, and then taking out and cooling;
and S3, repeating the steps S1 and S24 times to obtain the lithium vanadium phosphate/graphene composite cathode material with a flower-shaped structure by taking the calcined and cooled substrate obtained in the step S2 as an object.
When the obtained lithium vanadium phosphate/graphene composite positive electrode material is charged and discharged at a multiplying power of 5C, the first discharge specific capacity at room temperature can reach 149 mAh/g; after 50 cycles, the capacity retention rate was 94.1%.
Example 3
Having a surface V2O5Preparation of the matrix of (1): will V2O5Dissolving in pure water to prepare 0.01 mmol/ml V2O5The aqueous solution is uniformly sprayed on a stainless steel substrate by a simple spraying device, then the stainless steel substrate is placed in a vacuum drying oven to be dried for 3 hours at the temperature of 80 ℃, and then the stainless steel substrate is placed in a tube furnace to be calcined for 1 hour at the temperature of 400 ℃ in the nitrogen atmosphere to obtain the aqueous solution with V on the surface2O5The stainless steel substrate of (1).
S1, dissolving lithium gluconate, vanadium pentoxide and ammonium dihydrogen phosphate in a molar ratio of 3:1:3 in deionized water, adding 20% of sodium citrate, and stirring at 80 ℃ on a magnetic stirrer to completely dissolve the sodium citrate and the vanadium pentoxide and the ammonium dihydrogen phosphate to form a transparent mixed solution;
s2, horizontally placing the substrate with the vanadium pentoxide on the surface into the transparent mixed solution obtained in the step S1 for soaking for 5 days, taking out the soaked substrate, placing the substrate into a vacuum drying oven for drying, then placing the substrate into a tubular furnace for calcining at 950 ℃ for 4 hours under the nitrogen protection atmosphere, and then taking out the substrate for cooling;
and S3, repeating the steps S1 and S22 times to obtain the lithium vanadium phosphate/graphene composite cathode material by taking the calcined and cooled substrate obtained in the step S2 as an object.
When the obtained lithium vanadium phosphate/graphene composite cathode material is charged and discharged at a multiplying power of 5C, the first discharge specific capacity at room temperature can reach 131 mAh/g; after 50 cycles, the capacity retention rate was 91.9%.
Example 4
Having NH on the surface4VO3Preparation of the matrix of (1): reacting NH4VO3Dissolving in pure water to prepare 0.1 mmol/ml NH4VO3The aqueous solution of (A) was uniformly sprayed onto the copper plate substrate by a simple spraying device, the copper plate substrate was then dried in a vacuum drying oven at 120 ℃ for 1 hour, and then the copper plate substrate was calcined in a tube furnace at 600 ℃ for 1 hour in a nitrogen atmosphere to obtain an aqueous solution having V-shaped surfaces2O5The copper plate base body.
S1, dissolving lithium formate, vanadium pentoxide and ammonium dihydrogen phosphate in a molar ratio of 3:1:3 in deionized water, adding 13% of sodium citrate, and stirring at 90 ℃ on a magnetic stirrer to completely dissolve the sodium citrate and the vanadium pentoxide and the ammonium dihydrogen phosphate to form a transparent mixed solution;
s2, horizontally placing the substrate with the ammonium metavanadate on the surface into the transparent mixed solution obtained in the step S1 for soaking for 5 days, taking out the soaked substrate, placing the substrate into a vacuum drying box for drying, then placing the substrate into a tubular furnace for 700-DEG calcination for 3 hours under the nitrogen protection atmosphere, and then taking out and cooling;
and S3, repeating the steps S1 and S27 times to obtain the lithium vanadium phosphate/graphene composite cathode material by taking the calcined and cooled substrate obtained in the step S2 as an object.
When the obtained lithium vanadium phosphate/graphene composite cathode material is charged and discharged at a multiplying power of 5C, the first discharge specific capacity at room temperature can reach 129 mAh/g; after 50 cycles, the capacity retention rate was 92.6%.
The inventor states that the invention is illustrated by the above embodiments, but the invention is not limited to the above detailed process equipment and process flow, i.e. the invention is not meant to be dependent on the above detailed process equipment and process flow. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (7)
1. A method for preparing a lithium vanadium phosphate/graphene composite cathode material on a metal base is characterized by comprising the following steps:
s1, mixing soluble lithium compounds, vanadium compounds and phosphates according to the atomic ratio of lithium to iron to phosphorus of 3:2:3, placing the mixture into deionized water, adding a proper amount of sodium citrate and graphene oxide, and fully stirring at a certain temperature to form a mixed solution;
s2, mixing a proper amount of vanadium compound and pure water to form a solution or a suspension, uniformly spraying the solution or the suspension on the surface of a substrate in a spraying mode, then drying the metal substrate sprayed with the vanadium compound solution in vacuum, placing the dried metal substrate in a tube furnace, calcining the metal substrate at a certain temperature in a protective atmosphere for a certain time to obtain a metal substrate with a vanadium compound attached to the surface, horizontally laying the metal substrate with the vanadium compound attached to the surface, soaking the metal substrate in the mixed solution obtained in the step S1 for several days, taking out the soaked metal substrate, drying the metal substrate, then calcining the metal substrate at a high temperature in the protective atmosphere for a period of time, and taking out the metal substrate for cooling;
and S3, repeating the steps S1 and S2 for not less than 2 times by taking the calcined and cooled substrate as an object, and obtaining the lithium vanadium phosphate/graphene composite cathode material on the surface of the substrate.
2. The method for preparing the lithium vanadium phosphate/graphene composite cathode material on the metal substrate according to claim 1, wherein in the step S1, the mass fraction of the added sodium citrate is 5-25%, the mass fraction of the added graphene oxide is 5-10%, and the mixture is stirred at the temperature of 70-90 ℃ for 0.5-2 h.
3. The method for preparing a lithium vanadium phosphate/graphene composite positive electrode material on a metal substrate according to claim 1, wherein the number of days for which the metal substrate with the vanadium compound attached to the surface is immersed in the mixed solution in step S2 is 3 to 5 days.
4. The method for preparing the lithium vanadium phosphate/graphene composite cathode material on the metal base according to claim 1, wherein the high-temperature calcination in the step S2 is performed in a tube furnace, the temperature is 800-1000 ℃, the calcination time is 0.5-1 h, and the protective atmosphere is nitrogen.
5. The method for preparing the lithium vanadium phosphate/graphene composite cathode material on the metal base according to claim 1, wherein the vanadium compound on the substrate is V2O5、NH4VO3、V2O3The concentration of the vanadium compound prepared into an aqueous solution or suspension is 0.1-0.15 mmol/ml.
6. The method for preparing the lithium vanadium phosphate/graphene composite cathode material on the metal substrate according to claim 1, wherein the vacuum drying is carried out by placing the substrate in a vacuum drying oven at a temperature of 110-120 ℃ for drying for 1-5 hours.
7. The method for preparing the lithium vanadium phosphate/graphene composite cathode material on the metal base according to claim 1, wherein the calcining temperature in the tubular furnace is 300-600 ℃ and the time is 1-2 hours, and the protective gas is nitrogen.
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