CN107369827A - A kind of preparation method of phosphoric acid vanadium lithium/carbon composite anode material of flower-like structure - Google Patents

A kind of preparation method of phosphoric acid vanadium lithium/carbon composite anode material of flower-like structure Download PDF

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CN107369827A
CN107369827A CN201710677236.2A CN201710677236A CN107369827A CN 107369827 A CN107369827 A CN 107369827A CN 201710677236 A CN201710677236 A CN 201710677236A CN 107369827 A CN107369827 A CN 107369827A
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lithium
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flower
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CN107369827B (en
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陈晗
李永海
向楷雄
周伟
朱裔荣
陈宪宏
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Hunan University of Technology
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    • 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
    • H—ELECTRICITY
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Abstract

Present invention relates particularly to a kind of preparation method of phosphoric acid vanadium lithium/carbon composite anode material of flower-like structure, by the lithium compound of solubility, vfanadium compound, phosphate and citric acid are added in deionized water according to proper proportion prepares solution, then proper amount of sodium citrate is added, it is sufficiently stirred to form clear solution, the matrix that surface there are vanadium compounds is placed in the clear solution, drying is taken out after impregnating a couple of days, then cooling is taken out after matrix is calcined into a period of time in protective atmosphere at 500 ~ 1000 DEG C, then the matrix after calcining is repeated the above steps for several times, wherein dipping need to prepare identical clear solution again every time, the matrix finally obtained is subjected to low-temperature carbonization processing under protective atmosphere successively and high―temperature nuclei can obtain the composite positive pole of flower-shaped phosphoric acid vanadium lithium carbon.The vanadium phosphate cathode 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, green some advantages of grade.

Description

A kind of preparation method of phosphoric acid vanadium lithium/carbon composite anode material of flower-like structure
Technical field
The invention belongs to the technical field of battery anode composite material, more particularly to a kind of phosphoric acid of flower-like structure The preparation method of vanadium lithium/carbon composite anode material.
Background technology
Lithium ion battery as a kind of novel green battery, with its operating voltage it is high, it is in light weight, bigger than energy, put certainly The advantages that electric rate is small, have extended cycle life, memory-less effect, non-environmental-pollution, in the traditional secondary cell of substitution progressively, As the miniaturization such as video camera, mobile phone, notebook computer and Portable Measurement Instrument electronic installation and environment-friendly type The ideal source of electric automobile.Lithium-ion-power cell industry development is promoted, a huge pollution-free industry cluster can be driven fast Speed emerges, and has great strategic significance and pulling production to national economy.Lithium-ion-power cell belongs to energy-conservation and new energy simultaneously Source domain, meet the demand for development of national policy.For a long time, the U.S. supports multiple National Laboratories and enterprise to undertake car together With the development of lithium ion battery.European Union has then formulated the development plan of high-energy-density battery, and the stage is born in not stopping pregnancy Property achievement.Japan is the country of lithium-ion-power cell technological precedence, succeeds in developing lithium ion battery from nineteen ninety Japan and throws Since putting market, because its unique performance at home and abroad forms one Study on Li-ion batteries upsurge.Lithium ion battery is to work as Develop a kind of very wide high-energy secondary battery of very fast, application prospect in modern chargeable battery.In lithium ion battery, just The usage amount of pole material is very big, and which increase the production cost of lithium ion battery.At present, as anode material for lithium-ion batteries Material is mainly lithium-containing transition metal oxide, includes the LiMO of layer structure（M=Co、Ni、Mn）With spinel-type LiMn2O4.However, these materials are due to price（LiCoO2）, security（LiNiO2）, high-temperature electrochemical properties（LiMn2O4）Deng Reason makes them in the application aspect of high-capacity battery by many restrictions.Therefore, find new cheap, function admirable Positive electrode turns into the emphasis of Study on Li-ion batteries.
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.
The synthetic method of vanadium phosphate lithium/carbon composite material has a variety of at present, and its conventional method has：High temperature solid-state method, it is molten Sol-gel, microwave method, hydro-thermal method.But high temperature solid-state method is cumbersome, cost is high, and obtained material granule it is larger, It is uneven, and it is also easy to produce impurity；Although microwave method energy consumption is low, heat time and temperature are difficult to control, and influence properties of product； The bad control of hydro-thermal method concentration, properties of product are impacted；Phosphoric acid vanadium lithium particle prepared by existing sol-gal process is larger, influences The charging capacity and cycle performance of product.Meanwhile from the point of view of research, granule-morphology has huge shadow to lithium vanadium phosphate material performance Ring, there is the lithium vanadium phosphate material that particle is uniform, porous larger specific surface area can improve its chemical property.
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, Li of good cycle, low production cost3V2（PO3）4The preparation method of/C composite positive poles.
The present invention also provides a kind of phosphoric acid vanadium lithium/carbon composite anode material with flower-like structure.
The purpose of the present invention is achieved by the following technical programs：
The preparation method of phosphoric acid vanadium lithium/carbon composite anode material of specially a kind of flower-like structure, comprises the following steps：
S1, by solubility lithium compound, vfanadium compound, phosphate according to proper proportion mix be placed in deionized water, simultaneously Appropriate citric acid is added, stirring at a certain temperature to formation clear mixed liquor；
S2, the matrix that surface attachment is had vfanadium compound, which lay flat on one's back to be placed in transparent mixed liquor obtained by step S1, impregnates a couple of days, takes The 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 is for several times；
S4, matrix obtained by step S3 is subjected to low-temperature carbonization processing and high―temperature nuclei successively under protective atmosphere handled, obtain flower Phosphoric acid vanadium lithium/carbon composite anode material of shape structure.
The matrix that surface attachment is had to vfanadium compound of the invention is placed in containing lithium ion, vanadium ion, phosphonium ion With impregnate a couple of days in the mixed solution of citric acid, the vfanadium compound of matrix surface attachment can be used as crystal seed, allow phosphoric acid vanadium lithium/carbon to exist Seed surrounding growth, become big, until the excellent composite of forming properties, the Li formed3V2（PO3）4/ C composite performance It is superior, while the preparation method technique of the present invention is simple, easily operation, cost are relatively low.
Preferably, lithium compound soluble described in step S1, vfanadium compound, phosphate according to lithium, vanadium, phosphorus atom Than for 3:2:3 mixing, the mass fraction after citric acid adds is 2 ~ 20%, and 0.5-2 hours are stirred under temperature 30-70oC.
Preferably, step S2 described matrixes are metal_based material or carbon-based material, such as：Stainless steel, titanium plate, copper coin, carbon The rush after Oroxylum indicum, carbonization after change.
Preferably, the number of days that the matrix that there is vanadic anhydride on surface described in step S2 impregnates in transparent mixed liquor is 5 ~ 15 My god；The high-temperature calcination is carried out in tube furnace, and temperature is 500 ~ 1000 DEG C, and calcination time is 2 ~ 6 hours, and protective atmosphere is nitrogen One kind in gas, argon gas, helium, carbon dioxide.
Preferably, number of repetition is 2 ~ 7 times in step S3.
Preferably, in step s 4, the low-temperature carbonization processing design parameter is：At 200-400 DEG C low-temperature carbonization 2 ~ 8h, the low-temperature carbonization 5h preferably at 350 DEG C；The high―temperature nuclei handles design parameter：The high―temperature nuclei at 600-850 DEG C 3 ~ 15h, the high―temperature nuclei 10h preferably at 750 DEG C.
Preferably, the preparation method that the surface attachment has the matrix of vfanadium compound is：By appropriate vfanadium compound and pure water Solution or suspension are mixed to form, using the form of spraying by above-mentioned solution or suspension even application in matrix surface, so Afterwards being coated with the matrix vacuum drying of vanadium solution, then it is placed in tube furnace, is forged in an inert atmosphere under certain temperature Burn certain time.
It is further preferred that the vfanadium compound is V on matrix2O5、NH4VO3、V2O3One or more, the vanadium It is 0.01 ~ 0.1mmol/ml that the aqueous solution or the concentration of suspension, which is made, in compound；The vacuum drying concrete operations are by matrix It is placed in the vacuum drying chamber that temperature is 80 DEG C ~ 120 DEG C and dries 1 ~ 5 hour；Calcining heat is 300 ~ 600 DEG C in tube furnace, when Between be 1 ~ 8 hour, the inert gas is nitrogen, argon gas, helium, one kind in carbon dioxide.
Phosphoric acid vanadium lithium/carbon composite anode material has been prepared according to the preparation method of above-mentioned composite positive pole in the present invention Material.
Preferably, the phosphoric acid vanadium lithium/carbon composite anode material is flower-shaped spherical structure, the flower-shaped spherical structure it is straight Footpath is 30 ~ 50 μm, and petal spacing is 5 ~ 15 μm.
Compared with prior art, the advantage of the invention is that：
（1）The Li for the flower-like structure that the present invention synthesizes3V2（PO3）4/ C composite positive poles have multi-pore channel feature, this structure Electrolyte can be allowed easily to come in, increase electrolyte and Li3V2（PO3）4The contact area of/C composite, is greatly shortened The transmission path of lithium ion, the efficiency of transmission of lithium ion is improved, so as to obtaining good chemical property.This Li3V2 （PO3）4/ C composite is under 5C multiplying powers during discharge and recharge, and first charge-discharge specific capacity reaches as high as 163mAh/g at room temperature, passes through After 50 circulations, capability retention reaches as high as 95.3%.
（2）When having the matrix of vfanadium compound on preparation surface, vfanadium compound is prepared the aqueous solution by the invention, is led to Spray-on process is crossed by the aqueous solution even application of vfanadium compound in specific surface, the vfanadium compound as crystalline substance of these matrix surfaces Kind, 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 to be formed It is evengranular be distributed on matrix, so as to formed Li3V2（PO3）4The performance of/C composite is more superior.
（3）Phosphoric acid vanadium lithium/carbon anode composite material of the present invention is not only high with specific capacity, and good cycle is forthright again Advantage can be waited well, it is low also to have gathered cost, the green a little advantages of grade.Meanwhile phosphoric acid vanadium lithium of the present invention/carbon anode composite material Preparation method technique it is simple, easily operation, cost are relatively low, to obtain the Li of above-mentioned function admirable3V2（PO3）4/ C anode composites Material provides effective way.
Brief description of the drawings
Fig. 1 is the Li for having in embodiment 1 flower-like structure3V2（PO3）4The XRD diffraction patterns of/C composite positive poles.
Fig. 2 is the Li for having in embodiment 4 flower-like structure3V2（PO3）4/ C composite positive poles amplify 3000 times of SEM Figure.
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.
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% citric acid is added, then is placed on magnetic stirring apparatus in 60 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；
S4, matrix obtained by step S3 is placed in the tube furnace of logical protective gas carries out low-temperature carbonization 5h in 350 DEG C, then heat up High―temperature nuclei 10h are carried out to 750 DEG C, finally obtain phosphoric acid vanadium lithium/carbon composite anode material of flower-like structure.
The Li of gained3V2（PO3）4/ C composite positive poles are under 5C multiplying powers during discharge and recharge, first discharge specific capacity at room temperature Up to 120mAh/g；After 50 circulations, capability retention 94%.
Embodiment 2
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 on titanium plate matrix, then titanium plate matrix is placed in vacuum drying chamber and dries 1 at 100 DEG C Hour, then stainless steel base is placed in tube furnace, in nitrogen atmosphere, 300 DEG C calcine 6 hours, obtaining surface has NH4VO3Titanium Plate matrix.
S1, by mol ratio be 3:2 lithium dihydrogen phosphate, ammonium metavanadate are dissolved in deionized water, then add 15% lemon Acid, it is placed on magnetic stirring apparatus in 70 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 drying after stain, then it is put into tube furnace and 800 degree of calcining 2h, rear taking-up cooling is carried out under protective atmosphere；
Matrix after calcining cooling obtained by S3, step S2 is object, repeats step S1, S2 2 times；
S4, matrix obtained by step S3 is placed in the tube furnace of logical protective gas carries out low-temperature carbonization 5h in 350 DEG C, then heat up High―temperature nuclei 10h are carried out to 750 DEG C, finally obtain phosphoric acid vanadium lithium/carbon composite anode material of flower-like structure.
The Li of gained3V2（PO3）4/ C composite positive poles are under 5C multiplying powers during discharge and recharge, first discharge specific capacity at room temperature Up to 131mAh/g；After 50 circulations, capability retention is 92.8 %.
Embodiment 3
There is V on surface2O5Matrix preparation：By V2O5It is dissolved in pure water and prepares 0.05 mmol/ml V2O5The aqueous solution, with simple Then sprayer unit is placed in stainless steel base in vacuum drying chamber that 4 are dried at 80 DEG C is small to uniformly spraying on Oroxylum indicum matrix When, then Oroxylum indicum matrix is placed in tube furnace, in argon gas atmosphere, 500 DEG C calcine 2 hours, obtaining surface has V2O5Oroxylum indicum Matrix.
S1, by mol ratio be 3:1:3 lithium acetate, vanadic anhydride and ammonium dihydrogen phosphate is dissolved in deionized water, then 15% citric acid is added, is placed on magnetic stirring apparatus in 60 DEG C of stirrings, is completely dissolved it, form 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 1000 degree of the progress under argon atmosphere and forges 6h is burnt, it is rear to take out cooling；
Matrix after calcining cooling obtained by S3, step S2 is object, repeat step S1, S2 4 times；
S4, matrix obtained by step S3 is placed in the tube furnace of logical protective gas carries out low-temperature carbonization 5h in 400 DEG C, then heat up High―temperature nuclei 10h are carried out to 800 DEG C, finally obtain phosphoric acid vanadium lithium/carbon composite anode material of flower-like structure.
The Li of gained3V2（PO3）4/ C composite positive poles are under 5C multiplying powers during discharge and recharge, first discharge specific capacity at room temperature Up to 153mAh/g；After 50 circulations, capability retention is 94.2 %.
Embodiment 4
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 rush matrix in vacuum drying chamber that 5 are dried at 80 DEG C is small to uniformly spraying on rush matrix When, then rush matrix is placed in tube furnace, in nitrogen atmosphere, 300 DEG C calcine 8 hours, obtaining surface has V2O5Rush Matrix.
S1, by mol ratio be 3:1:3 lithium acetate, vanadic anhydride and ammonium dihydrogen phosphate is dissolved in deionized water, then 18% citric acid is added, is placed on magnetic stirring apparatus in 60 DEG C of stirrings, is completely dissolved it, form 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 10 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 900 degree 2h is calcined, it is rear to take out cooling；
Matrix after calcining cooling obtained by S3, step S2 is object, repeat step S1, S24 times；
S4, matrix obtained by step S3 is placed in the tube furnace of logical protective gas carries out low-temperature carbonization 8h in 200 DEG C, then heat up High―temperature nuclei 15h are carried out to 800 DEG C, finally obtain phosphoric acid vanadium lithium/carbon composite anode material of flower-like structure.
The Li of gained3V2（PO3）4/ C composite positive poles are under 5C multiplying powers during discharge and recharge, first discharge specific capacity at room temperature Up to 163mAh/g；After 50 circulations, capability retention is 95.3 %.
Embodiment 5
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% citric acid is added, is placed on magnetic stirring apparatus in 60 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 argon 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, repeat step S1, S24 times；
S4, matrix obtained by step S3 is placed in the tube furnace of logical protective gas carries out low-temperature carbonization 5h in 300 DEG C, then heat up High―temperature nuclei 10h are carried out to 600 DEG C, finally obtain phosphoric acid vanadium lithium/carbon composite anode material of flower-like structure.
The Li of gained3V2（PO3）4/ C composite positive poles are under 5C multiplying powers during discharge and recharge, first discharge specific capacity at room temperature Up to 132mAh/g；After 50 circulations, capability retention is 93.1 %.
Embodiment 6
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% citric acid is added, is placed on magnetic stirring apparatus in 60 DEG C of stirrings, is completely dissolved it, form 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 950 degree of the progress under argon 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；
S4, matrix obtained by step S3 is placed in the tube furnace of logical protective gas carries out low-temperature carbonization 2h in 350 DEG C, then heat up High―temperature nuclei 3h are carried out to 750 DEG C, finally obtain phosphoric acid vanadium lithium/carbon composite anode material of flower-like structure.
The Li of gained3V2（PO3）4/ C composite positive poles are under 5C multiplying powers during discharge and recharge, first discharge specific capacity at room temperature Up to 126mAh/g；After 50 circulations, capability retention is 91.4 %.
Embodiment 7
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% citric acid is added, is placed on magnetic stirring apparatus in 60 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 helium protective atmosphere 3h, it is rear to take out cooling；
Matrix after calcining cooling obtained by S3, step S2 is object, repeat step S1, S27 times；
S4, matrix obtained by step S3 is placed in the tube furnace of logical protective gas carries out low-temperature carbonization 3h in 300 DEG C, then heat up High―temperature nuclei 8h are carried out to 700 DEG C, finally obtain phosphoric acid vanadium lithium/carbon composite anode material of flower-like structure.
The Li of gained3V2（PO3）4/ C composite positive poles are under 5C multiplying powers during discharge and recharge, first discharge specific capacity at room temperature Up to 136mAh/g；After 50 circulations, capability retention is 92.4 %.
Embodiment 8
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 rush matrix in vacuum drying chamber that 1 is dried at 120 DEG C is small to uniformly spraying on rush matrix When, then rush matrix is placed in tube furnace, in nitrogen atmosphere, 400 DEG C calcine 1 hour, obtaining surface has V2O5Rush Matrix.
S1, by mol ratio be 3:1:3 lithium acetate, vanadic anhydride and ammonium dihydrogen phosphate is dissolved in deionized water, then 16% citric acid is added, is placed on magnetic stirring apparatus in 60 DEG C of stirrings, is completely dissolved it, form 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 10 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, repeat step S1, S25 times；
S4, matrix obtained by step S3 is placed in the tube furnace of logical protective gas carries out low-temperature carbonization 5h in 250 DEG C, then heat up High―temperature nuclei 5h are carried out to 650 DEG C, finally obtain phosphoric acid vanadium lithium/carbon composite anode material of flower-like structure.
The Li of gained3V2（PO3）4/ C composite positive poles are under 5C multiplying powers during discharge and recharge, first discharge specific capacity at room temperature Up to 150mAh/g；After 50 circulations, capability retention is 93.3 %.
Embodiment 9
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 Oroxylum indicum matrix in vacuum drying chamber that 2 are dried at 80 DEG C is small to uniformly spraying on Oroxylum indicum matrix When, then Oroxylum indicum matrix is placed in tube furnace, in nitrogen atmosphere, 600 DEG C calcine 1 hour, obtaining surface has V2O5Oroxylum indicum Matrix.
S1, by mol ratio be 3:1:3 lithium acetate, vanadic anhydride and ammonium dihydrogen phosphate is dissolved in deionized water, then 19% citric acid is added, is placed on magnetic stirring apparatus in 60 DEG C of stirrings, is completely dissolved it, form 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 650 degree of the progress under argon atmosphere and forges 5h is burnt, it is rear to take out cooling；
Matrix after calcining cooling obtained by S3, step S2 is object, repeat step S1, S27 times；
S4, matrix obtained by step S3 is placed in the tube furnace of logical protective gas carries out low-temperature carbonization 5h in 350 DEG C, then heat up High―temperature nuclei 10h are carried out to 750 DEG C, finally obtain phosphoric acid vanadium lithium/carbon composite anode material of flower-like structure.
The Li of gained3V2（PO3）4/ C composite positive poles are under 5C multiplying powers during discharge and recharge, first discharge specific capacity at room temperature Up to 160mAh/g；After 50 circulations, capability retention is 93.1 %.
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 (10)

1. the preparation method of phosphoric acid vanadium lithium/carbon composite anode material of a kind of flower-like structure, it is characterised in that including following step Suddenly：
S1. the lithium compound, vfanadium compound, phosphate of solubility are mixed according to proper proportion and are placed in deionized water, simultaneously Appropriate citric acid is added, stirring at a certain temperature to formation clear mixed liquor；
S2. the matrix that surface attachment has vfanadium compound is laid flat on one's back to be placed in transparent mixed liquor obtained by step S1 and impregnates a couple of days, taken The 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. the matrix after being cooled down using calcining is object, and repeat step S1, S2 is for several times；
S4. matrix obtained by step S3 is carried out into low-temperature carbonization processing and high―temperature nuclei successively under protective atmosphere to handle, obtains flower Phosphoric acid vanadium lithium/carbon composite anode material of shape structure.
2. the preparation method of composite positive pole according to claim 1, it is characterised in that soluble described in step S1 Lithium compound, vfanadium compound, phosphate are 3 according to the atomic ratio of lithium, vanadium, phosphorus:2:3 mixing, the quality after citric acid adds are divided Number is 2 ~ 20%, in temperature 30-70oStirred 0.5 ~ 2 hour under C.
3. the preparation method of composite positive pole according to claim 1, it is characterised in that step S2 described matrixes are metal Sill or carbon-based material.
4. the preparation method of composite positive pole according to claim 1, it is characterised in that there are five oxygen on surface described in step S2 It is 5 ~ 15 days to change the number of days that the matrixes of two vanadium impregnates in transparent mixed liquor；The high-temperature calcination is carried out in tube furnace, temperature For 500 ~ 1000 DEG C, calcination time is 2 ~ 6 hours, and protective atmosphere is one kind in nitrogen, argon gas, helium, carbon dioxide.
5. the preparation method of composite positive pole according to claim 1, it is characterised in that in step S3 number of repetition be 2 ~ 7 times.
6. the preparation method of composite positive pole according to claim 1, it is characterised in that in step s 4, the low temperature Carbonization treatment design parameter is：2 ~ 8h of low-temperature carbonization at 200 ~ 400 DEG C, the low-temperature carbonization 5h preferably at 350 DEG C；The height Temperature synthesis handles design parameter：3 ~ 15h of high―temperature nuclei at 600 ~ 850 DEG C, the high―temperature nuclei 10h preferably at 750 DEG C.
7. according to the preparation method of any one of claim 1 ~ 6 composite positive pole, it is characterised in that the surface attachment The preparation method for having the matrix of vfanadium compound is：Appropriate vfanadium compound and pure water are mixed to form solution or suspension, using spray The form of mist by above-mentioned solution or suspension even application in matrix surface, then the matrix for being coated with vanadium solution Vacuum drying, then be placed in tube furnace, certain time is calcined under certain temperature in an inert atmosphere.
8. the preparation method of composite positive pole according to claim 7, it is characterised in that the vfanadium compound is on matrix V2O5、NH4VO3、V2O3One or more, the vfanadium compound be made the concentration of the aqueous solution or suspension for 0.01 ~ 0.1mmol/ml；The vacuum drying concrete operations are that matrix is placed in the vacuum drying chamber that temperature is 80 DEG C ~ 120 DEG C to dry 1 ~ 5 hour；Calcining heat is 300 ~ 600 DEG C in tube furnace, and the time is 1 ~ 8 hour, and the inert gas is nitrogen, argon gas, helium One kind in gas, carbon dioxide.
A kind of 9. vanadium phosphate that preparation method according to any one of claim 1 ~ 6,8 composite positive pole is prepared Lithium/carbon composite anode material.
10. phosphoric acid vanadium lithium/carbon composite anode material according to claim 9, it is characterised in that the phosphoric acid vanadium lithium/carbon is multiple Conjunction positive electrode is flower-shaped spherical structure, and a diameter of 30 ~ 50 μm of the flower-shaped spherical structure, petal spacing is 5 ~ 15 μm.
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CN108054025A (en) * 2017-12-22 2018-05-18 湖南工业大学 Use the preparation method of the lithium-ion capacitor of LiFePO4/expansion micro crystal graphite/carbon composite
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