CN107706380A - A kind of method that phosphoric acid vanadium lithium/grapheme composite positive electrode material is prepared in Metal Substrate - Google Patents
A kind of method that phosphoric acid vanadium lithium/grapheme composite positive electrode material is prepared in Metal Substrate Download PDFInfo
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- CN107706380A CN107706380A CN201710886025.XA CN201710886025A CN107706380A CN 107706380 A CN107706380 A CN 107706380A CN 201710886025 A CN201710886025 A CN 201710886025A CN 107706380 A CN107706380 A CN 107706380A
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- Prior art keywords
- phosphoric acid
- positive electrode
- electrode material
- acid vanadium
- composite positive
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- 239000002131 composite material Substances 0.000 title claims abstract description 44
- ZVKRVGZVXQYLPZ-UHFFFAOYSA-N [Li].[V].P(O)(O)(O)=O Chemical compound [Li].[V].P(O)(O)(O)=O ZVKRVGZVXQYLPZ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims description 25
- 229910052751 metal Inorganic materials 0.000 title claims description 15
- 239000002184 metal Substances 0.000 title claims description 15
- 239000000758 substrate Substances 0.000 title claims description 14
- 239000011159 matrix material Substances 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 238000007598 dipping method Methods 0.000 claims abstract description 6
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 3
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 3
- 239000010452 phosphate Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 11
- 239000001509 sodium citrate Substances 0.000 claims description 11
- 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 11
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 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
- 239000007789 gas Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 6
- FNLJLQUTIUDEHI-UHFFFAOYSA-N phosphoric acid vanadium Chemical compound [V].OP(O)(O)=O FNLJLQUTIUDEHI-UHFFFAOYSA-N 0.000 abstract description 3
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 abstract 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 19
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 4
- 230000004087 circulation Effects 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
- 238000003760 magnetic stirring Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- DMEJJWCBIYKVSB-UHFFFAOYSA-N lithium vanadium Chemical compound [Li].[V] DMEJJWCBIYKVSB-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- -1 oxygen Graphite alkene Chemical class 0.000 description 3
- 229910001456 vanadium ion Inorganic materials 0.000 description 3
- 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 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical group [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910003481 amorphous carbon Chemical group 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [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
- 230000008859 change Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229940071260 lithium gluconate Drugs 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
- 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
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 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
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 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
- H01M4/364—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
-
- 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
Abstract
Present invention relates particularly to a kind of preparation method of phosphoric acid vanadium lithium/grapheme composite positive electrode material, lithium compound, vfanadium compound and the phosphate of solubility are added in deionized water according to proper proportion and prepare solution, then adds proper amount of sodium citrate sodium and graphene oxide.Then the metallic matrix that surface attachment has vfanadium compound is laid flat on one's back to be placed in mixed liquor and impregnates a couple of days, taken out the metallic matrix drying after dipping, then carry out high-temperature calcination for a period of time under protective atmosphere, it is rear to take out cooling；Repeat the above steps for several times, obtain phosphoric acid vanadium lithium/grapheme composite positive electrode material.Phosphoric acid vanadium lithium/grapheme composite positive electrode material of the present invention not only has that specific capacity is high, good cycle, the advantage such as good rate capability, and it is low also to have gathered cost, it is green the advantages that.
Description
Technical field
The invention belongs to the technical field of battery anode composite material, more particularly to a kind of prepare in Metal Substrate
The method of phosphoric acid vanadium lithium/grapheme composite positive electrode material.
Background technology
Since Goodenough etc. proposes polyanion lithium electricity LiFePO 4 of anode material first, researcher is to poly- the moon
Iron phosphate expands numerous studies, wherein being exactly the most successfully the industrial metaplasia for realizing lithium iron phosphate positive material
Production, and research report of the people to phosphoric acid vanadium lithium is not a lot, and industrialized production is still not implemented at present.But phosphoric acid vanadium lithium is performance
A kind of material more excellent than LiFePO4, has advantages below：A, it has excellent heat endurance, what is studied at present
LiFePO 4 is only slightly lower than in positive electrode；B, there are high discharge voltage and multiple discharge voltage plateaus, average discharge volt
For 4.1 V, higher than 3.4 V discharge voltages of LiFePO 4, and there are 3.5 V, 3.6 V, 4.1 V and 4.6 V 4
Discharge platform；C, excellent cyclical stability and high discharge capacity, theoretical capacity is 197 mAh/g, higher than LiFePO 4
170 mAh/g theoretical capacity.As can be seen that the research space of phosphoric acid vanadium lithium is very big.
Graphene has very high electronic conductivity, and the movement rate of wherein electronics reaches the 1/300 of the light velocity, is a kind of pole
Good electronic conductor, and graphene has storage lithium characteristic in itself.Therefore, it is phosphoric acid vanadium lithium and graphene film is mutually compound, prepare phosphorus
Sour vanadium lithium/graphene combination electrode material, phosphoric acid vanadium lithium particle is adhered to or is wrapped on graphene film, not only can effectively carry
The conductance of high material, can also effectively suppress the growth of particle, as a result can greatly improve the conductive energy of lithium vanadium phosphate material
Power, and effectively improve the specific capacity and high rate performance of material.China Patent Publication No. is that CN102386410A discloses a kind of phosphorus
Sour vanadium lithium/graphene composite material and preparation method thereof, by phosphoric acid vanadium lithium and graphene or graphene and other amorphous carbon groups
Into but this method complex process, obtained composite property is unstable, charge ratio during as anode material for lithium-ion batteries
Capacity is not high.
The content of the invention
The technical problem to be solved in the present invention is overcome the deficiencies in the prior art, there is provided one kind is simple and environmentally-friendly, structure is steady
The fixed, method that phosphoric acid vanadium lithium/grapheme composite positive electrode material is prepared in Metal Substrate of good cycle, low production cost.
Another technical problem solved of the present invention is to provide a kind of phosphoric acid vanadium lithium/grapheme composite positive electrode material.
The purpose of the present invention is achieved by the following technical programs：
A kind of method that phosphoric acid vanadium lithium/grapheme composite positive electrode material is prepared in Metal Substrate is provided, comprised the following steps：
S1, by solubility lithium compound, iron compound, phosphate according to lithium, iron, phosphorus atomic ratio be 3:2:3 mixing are placed in
In deionized water, while proper amount of sodium citrate and graphene oxide are added, be sufficiently stirred to form mixed liquor at a certain temperature；
S2, the metallic matrix that surface attachment is had vfanadium compound, which lay flat on one's back to be placed in mixed liquor obtained by step S1, impregnates a couple of days, takes
The metallic matrix drying gone out after dipping, then carries out high-temperature calcination for a period of time under protective atmosphere, rear to take out cooling；
S3, using calcining cool down after matrix as object, repeat step S1, S2 be no less than 2 times；
S4, matrix obtained by step S3 is subjected to low-temperature carbonization processing and high―temperature nuclei successively under protective atmosphere handled, obtain phosphorus
Sour vanadium lithium/grapheme composite positive electrode material.
The metallic matrix that surface attachment is had to vfanadium compound of the invention is placed in containing lithium ion, vanadium ion, phosphorus
Impregnate a couple of days in the mixed solution of ion, sodium citrate and graphene oxide, in mixed solution, while carry out three groups of reactions, oxygen
Graphite alkene and lithium ion, vanadium ion, phosphonium ion react, and sodium citrate and lithium ion, vanadium ion, phosphonium ion occur instead
Should, with sodium citrate reduction reaction occurs for graphene oxide, and final three groups of reactions can form preliminary composite, when matrix immerses
After mixed liquor, the vfanadium compound of metal base surface attachment can be used as crystal seed, make composite seed surrounding growth, change big, directly
The composite excellent to forming properties, the lithium vanadium phosphate/graphene composite material superior performance formed, while the present invention's
Preparation method technique is simple, easily operation, cost are relatively low.
Preferably, the mass fraction after sodium citrate described in step S1 adds is 5 ~ 25%, and the graphene oxide adds
Mass fraction afterwards is 5 ~ 10%, in temperature 70 ~ 90o0.5 ~ 2h is stirred under C.
Preferably, the number of days that the metallic matrix that surface attachment described in step S2 has vfanadium compound impregnates in mixed liquor be 3 ~
5 days；
Preferably, high-temperature calcination is carried out in tube furnace described in step S2, temperature be 800 ~ 1000 DEG C, calcination time be 0.5 ~
1h, protective atmosphere are nitrogen.
Preferably, the preparation method that the surface attachment has the metallic matrix of vfanadium compound is：By appropriate vfanadium compound with
Pure water is mixed to form solution or suspension, using the form of spraying by above-mentioned solution or suspension even application in matrix table
Face, then being coated with the metallic matrix vacuum drying of vanadium solution, then it is placed in tube furnace, is being protected under certain temperature
Certain time is calcined in atmosphere.
It is further preferred that the vfanadium compound is V on matrix2O5、NH4VO3、V2O3One or more, the vanadium
It is 0.1 ~ 0.15mmol/ml that the aqueous solution or the concentration of suspension, which is made, in compound；
It is further preferred that the vacuum drying concrete operations are that matrix is placed in into the vacuum drying that temperature is 110 DEG C ~ 120 DEG C
Dried 1 ~ 5 hour in case；
It is further preferred that calcining heat is 300 ~ 600 DEG C in tube furnace, the time is 1 ~ 2 hour, and the protective gas is nitrogen
Gas.
Phosphoric acid vanadium lithium/graphene anode composite material that the present invention is also prepared by the preparation method of composite positive pole
Material.
Compared with prior art, the advantage of the invention is that：
（1）Phosphoric acid vanadium lithium/grapheme composite positive electrode material that the present invention synthesizes has a multi-pore channel feature, and this structure can allow electricity
Solution liquid is easily come in, and is increased the contact area of electrolyte and composite, is substantially reduced the transmission path of lithium ion,
The efficiency of transmission of lithium ion is improved, so as to obtain good chemical property.
（2）When having the metallic matrix of vfanadium compound on preparation surface, the preparing vfanadium compound of the invention is water-soluble
Liquid, it is in matrix surface, the vfanadium compound of these matrix surfaces by the aqueous solution even application of vfanadium compound by spray-on process
For crystal seed, when matrix is immersed in mixed solution, the presence of these crystal seeds is not only beneficial to the formation of phosphoric acid vanadium lithium crystal, also makes
The evengranular of formation is distributed on matrix, so as to which the performance of the composite formed is more superior.
（3）Phosphoric acid vanadium lithium/grapheme composite positive electrode material of the present invention is not only high with specific capacity, good cycle, times
The advantages such as rate performance is good, it is low also to have gathered cost, the green a little advantages of grade.Meanwhile phosphoric acid vanadium lithium of the present invention/graphene positive pole
The preparation method technique of composite is simple, easily operation, cost are relatively low, to obtain phosphoric acid vanadium lithium/stone of above-mentioned function admirable
Black alkene composite positive pole provides effective way.
Embodiment
The present invention is further illustrated with reference to specific embodiment.Following examples are only illustrative examples, not structure
Into inappropriate limitation of the present invention, the multitude of different ways that the present invention can be limited and covered by the content of the invention is implemented.It is unless special
Do not mentionlet alone bright, the present invention reagent, compound and the equipment that use is the art conventional reagent, compound and equipment.
Graphene oxide used is prepared using improved hummers in the embodiment of the present invention.
Embodiment 1
There is V on surface2O5Matrix preparation：By V2O5It is dissolved in pure water and prepares 0.1 mmol/ml V2O5The aqueous solution, with simple
Then sprayer unit is placed in stainless steel base in vacuum drying chamber that 1 is dried at 120 DEG C is small to uniformly spraying on stainless steel base
When, then stainless steel base is placed in tube furnace, in nitrogen atmosphere, 400 DEG C calcine 5 hours, obtaining surface has V2O5Stainless steel
Matrix.
S1, by mol ratio be 3:1:3 lithium acetate, vanadic anhydride and ammonium dihydrogen phosphate is dissolved in deionized water, then
15% sodium citrate is added, then is placed on magnetic stirring apparatus in 70 DEG C of stirrings, it is completely dissolved, forms transparent mixed solution；
S2, the matrix that there is vanadic anhydride on surface, which lay flat on one's back to be placed in transparent mixed solution obtained by step S1, to be impregnated 5 days, is taken out
Matrix after dipping, which is placed in vacuum drying chamber, dries, and is then put into tube furnace 750 degree of the progress under nitrogen protection atmosphere and forges
3h is burnt, it is rear to take out cooling；
Matrix after calcining cooling obtained by S3, step S2 is object, repeats step S1, S2 2 times, obtains phosphoric acid vanadium lithium/graphene
Composite positive pole.
Phosphoric acid vanadium lithium/grapheme composite positive electrode material of gained is under 5C multiplying powers during discharge and recharge, and discharge ratio first at room temperature
Capacity is up to 131mAh/g；After 50 circulations, capability retention 93.1%.
Embodiment 2
There is V on surface2O3Matrix preparation：By V2O3It is dissolved in pure water and prepares 0.05 mmol/ml V2O3The aqueous solution, with simple
Then sprayer unit is placed in stainless steel base in vacuum drying chamber that 1 is dried at 120 DEG C is small to uniformly spraying on stainless steel base
When, then stainless steel base is placed in tube furnace, in nitrogen atmosphere, 400 DEG C calcine 2 hours, obtaining surface has V2O3Stainless steel
Matrix.
S1, by mol ratio be 3:1:3 lithium acetate, vanadic anhydride and ammonium dihydrogen phosphate is dissolved in deionized water, then
16% sodium citrate is added, is placed on magnetic stirring apparatus in 80 DEG C of stirrings, is completely dissolved it, form transparent mixed solution；
S2, the matrix that there is vanadium trioxide on surface, which lay flat on one's back to be placed in transparent mixed solution obtained by step S1, to be impregnated 15 days, is taken
The matrix gone out after dipping, which is placed in vacuum drying chamber, dries, and is then put into tube furnace under nitrogen protection atmosphere and carries out 850 degree
3h is calcined, it is rear to take out cooling；
Matrix after calcining cooling obtained by S3, step S2 is object, repeats step S1, S2 4 times, finally obtains flower-like structure
Phosphoric acid vanadium lithium/grapheme composite positive electrode material.
Phosphoric acid vanadium lithium/grapheme composite positive electrode material of gained is under 5C multiplying powers during discharge and recharge, and discharge ratio first at room temperature
Capacity is up to 149mAh/g；After 50 circulations, capability retention is 94.1 %.
Embodiment 3
There is V on surface2O5Matrix preparation：By V2O5It is dissolved in pure water and prepares 0.01 mmol/ml V2O5The aqueous solution, with simple
Then sprayer unit is placed in stainless steel base in vacuum drying chamber that 3 are dried at 80 DEG C is small to uniformly spraying on stainless steel base
When, then stainless steel base is placed in tube furnace, in nitrogen atmosphere, 400 DEG C calcine 1 hour, obtaining surface has V2O5Stainless steel
Matrix.
S1, by mol ratio be 3:1:3 lithium gluconate, vanadic anhydride and ammonium dihydrogen phosphate is dissolved in deionized water,
Then 20% sodium citrate is added, is placed on magnetic stirring apparatus in 80 DEG C of stirrings, is completely dissolved it, it is molten to form transparent mixing
Liquid；
S2, the matrix that there is vanadic anhydride on surface, which lay flat on one's back to be placed in transparent mixed solution obtained by step S1, to be impregnated 5 days, is taken out
Matrix after dipping, which is placed in vacuum drying chamber, dries, and is then put into tube furnace 950 degree of the progress under nitrogen protection atmosphere and forges
4h is burnt, it is rear to take out cooling；
Matrix after calcining cooling obtained by S3, step S2 is object, repeats step S1, S2 2 times, obtains phosphoric acid vanadium lithium/graphene
Composite positive pole.
Phosphoric acid vanadium lithium/grapheme composite positive electrode material of gained is under 5C multiplying powers during discharge and recharge, and discharge ratio first at room temperature
Capacity is up to 131mAh/g；After 50 circulations, capability retention is 91.9 %.
Embodiment 4
There is NH on surface4VO3Matrix preparation：By NH4VO3It is dissolved in pure water and prepares 0.1 mmol/ml NH4VO3The aqueous solution,
With simple sprayer unit to uniformly spraying in copper plate base body, then copper plate base body is placed in vacuum drying chamber and dries 1 at 120 DEG C
Hour, then copper plate base body is placed in tube furnace, in nitrogen atmosphere, 600 DEG C calcine 1 hour, obtaining surface has V2O5Copper coin base
Body.
S1, by mol ratio be 3:1:3 lithium formate, vanadic anhydride and ammonium dihydrogen phosphate is dissolved in deionized water, then
13% sodium citrate is added, is placed on magnetic stirring apparatus in 90 DEG C of stirrings, is completely dissolved it, form transparent mixed solution；
S2, the matrix that there is ammonium metavanadate on surface, which lay flat on one's back to be placed in transparent mixed solution obtained by step S1, to be impregnated 5 days, takes out leaching
Matrix after stain, which is placed in vacuum drying chamber, dries, and is then put into tube furnace and 700 degree of calcinings are carried out under nitrogen protection atmosphere
3h, it is rear to take out cooling；
Matrix after calcining cooling obtained by S3, step S2 is object, repeats step S1, S2 7 times, obtains phosphoric acid vanadium lithium/graphene
Composite positive pole.
Phosphoric acid vanadium lithium/grapheme composite positive electrode material of gained is under 5C multiplying powers during discharge and recharge, and discharge ratio first at room temperature
Capacity is up to 129mAh/g；After 50 circulations, capability retention is 92.6 %.
Inventor states that the present invention illustrates the detailed process equipment of the present invention and technological process by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, selection of concrete mode etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (9)
- A kind of 1. method that phosphoric acid vanadium lithium/grapheme composite positive electrode material is prepared in Metal Substrate, it is characterised in that including following Step：S1, by solubility lithium compound, vfanadium compound, phosphate according to lithium, iron, phosphorus atomic ratio be 3:2:3 mixing are placed in In deionized water, while proper amount of sodium citrate and graphene oxide are added, be sufficiently stirred to form mixed liquor at a certain temperature；S2, the metallic matrix that surface attachment is had vfanadium compound, which lay flat on one's back to be placed in mixed liquor obtained by step S1, impregnates a couple of days, takes The metallic matrix drying gone out after dipping, then carries out high-temperature calcination for a period of time under protective atmosphere, rear to take out cooling；S3, using calcining cool down after matrix as object, repeat step S1, S2 be no less than 2 times, matrix surface obtain phosphoric acid vanadium lithium/ Grapheme composite positive electrode material.
- 2. the method for phosphoric acid vanadium lithium/grapheme composite positive electrode material is prepared in Metal Substrate according to claim 1, its feature It is, the mass fraction after sodium citrate described in step S1 adds is 5 ~ 25%, and the quality after the graphene oxide adds is divided Number is 5 ~ 10%, in temperature 70 ~ 90o0.5 ~ 2h is stirred under C.
- 3. the method for phosphoric acid vanadium lithium/grapheme composite positive electrode material is prepared in Metal Substrate according to claim 1, its feature It is, the number of days that the metallic matrix that surface attachment described in step S2 has vfanadium compound impregnates in mixed liquor is 3 ~ 5 days.
- 4. the method for phosphoric acid vanadium lithium/grapheme composite positive electrode material is prepared in Metal Substrate according to claim 1, its feature It is, high-temperature calcination described in step S2 is carried out in tube furnace, and temperature is 800 ~ 1000 DEG C, and calcination time is 0.5 ~ 1h, protection Atmosphere is nitrogen.
- 5. the side of phosphoric acid vanadium lithium/grapheme composite positive electrode material is prepared in Metal Substrate according to any one of claim 1 ~ 4 Method, it is characterised in that the preparation method that the surface attachment has the metallic matrix of vfanadium compound is：By appropriate vfanadium compound with it is pure Water is mixed to form solution or suspension, using the form of spraying by above-mentioned solution or suspension even application in matrix surface, Then being coated with the metallic matrix vacuum drying of vanadium solution, then it is placed in tube furnace, in protection gas under certain temperature Certain time is calcined in atmosphere.
- 6. the method for phosphoric acid vanadium lithium/grapheme composite positive electrode material is prepared in Metal Substrate according to claim 5, its feature It is, the vfanadium compound is V on matrix2O5、NH4VO3、V2O3One or more, the vfanadium compound be made the aqueous solution or The concentration of person's suspension is 0.1 ~ 0.15mmol/ml.
- 7. the method for phosphoric acid vanadium lithium/grapheme composite positive electrode material is prepared in Metal Substrate according to claim 5, its feature It is, the vacuum drying concrete operations are that matrix is placed in into temperature is that drying 1 ~ 5 is small in 110 DEG C ~ 120 DEG C of vacuum drying chamber When.
- 8. the method for phosphoric acid vanadium lithium/grapheme composite positive electrode material is prepared in Metal Substrate according to claim 5, its feature It is, calcining heat is 300 ~ 600 DEG C in tube furnace, and the time is 1 ~ 2 hour, and the protective gas is nitrogen.
- 9. one kind prepares phosphoric acid vanadium lithium/graphene anode composite according to claim 1 ~ 4,6 ~ 8 any one in Metal Substrate Phosphoric acid vanadium lithium/grapheme composite positive electrode material that the method for material is prepared.
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