CN106602005B - V2(PO4) O/C material preparation method, the cathode and method of lithium ion battery is made - Google Patents

V2(PO4) O/C material preparation method, the cathode and method of lithium ion battery is made Download PDF

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CN106602005B
CN106602005B CN201610312236.8A CN201610312236A CN106602005B CN 106602005 B CN106602005 B CN 106602005B CN 201610312236 A CN201610312236 A CN 201610312236A CN 106602005 B CN106602005 B CN 106602005B
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cathode
lithium ion
ion battery
lithium
solution
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CN106602005A (en
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南喜会
曹国忠
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Beijing Institute of Nanoenergy and Nanosystems
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/36—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to V2(PO4) O/C material preparation method, the cathode and method of lithium ion battery is made.Preparation method includes step: by vanadic anhydride and dissolving oxalic acid in deionized water, forming blue-tinted transparent solution under the conditions of oil bath, ammonium dihydrogen phosphate and glucose are added into solution；Ethylene glycol is added into solution again and obtains mixed liquor；Mixed liquor is subjected to hydro-thermal reaction, obtains solid sediment；Wherein, the molar ratio of vanadic anhydride, oxalic acid, ammonium dihydrogen phosphate are as follows: 1:3:1.The present invention also provides by V made from the above method2(PO4) cathode and method of lithium ion battery is made in O/C material: by V2(PO4) O/C material and acetylene black, Lithium polyacrylate aqueous solution be coated on copper foil after being mixed with certain weight ratio and electrode film is made, the cathode as lithium ion battery.Technical solution of the present invention makes V2(PO4) O/C material be used as ion cathode material lithium when, compared with the negative electrode materials such as existing lithium titanate, nitride, show excellent reversible capacity, high rate performance and cyclical stability.

Description

V2(PO4) O/C material preparation method, the cathode and method of lithium ion battery is made
Technical field
The invention mainly relates to a kind of preparation method and applications of chemical composite materials, and in particular to a kind of V2(PO4)O/ The preparation method of C-material, the cathode and method that lithium ion battery is made.
Background technique
As lithium ion battery is constantly applied to the fields such as portable electronic device, electric car and energy-accumulating power station, people Requirement to the energy of lithium ion battery, power density and security performance it is higher and higher.Although negative electrode material is not at present The development bottleneck of lithium ion battery also needs constantly to develop to meet the needs of social continuous advancement.
In general, lithium ion battery negative material is divided into Intercalation material, conversion hysteria material and conjunction according to charge-discharge mechanism Three kinds of aurification material.
Graphite is typical Intercalation material, and since it is cheap, electric conductivity is high, and thermal stability and chemical stability wait well spies Point is widely used in the negative electrode material of lithium ion battery.But it also has itself many limitations, as specific capacity is low (372mAh g-1), the problems such as being also easy to produce dendrite under high magnification, and the insertion of electrolyte solvent molecule makes its hair in use process Raw irreversible removing, so that the reversible capacity of material be greatly lowered.The battery of specific capacity, that is, Unit Weight or volume or The electricity that active material can release.
Another Intercalation material Li4Ti5O12, stability and invertibity with higher, but its high discharge platform is led The energy density for sending a telegraph pond is lower.
Conversion hysteria material mainly includes metal sulfide and transition metal oxide, such as Co3O4、CuO、 Fe2O3Deng.This A kind of material usually has very high reversible capacity and energy density, but its first charge-discharge coulombic efficiency is low, voltage delay Greatly, poor circulation.
The alloy type negative materials such as Si, Ge, Sn have high specific capacity, moderate to lithium current potential and good safety Energy.But the biggish volume of material is caused to become because the lithium ion of intercalation/deintercalation is excessive during alloying/removal alloying Change, it is broken so as to cause active material particle, or even be detached from electrode slice and fall into electrolyte, cause biggish irreversible capacity Problem.
Vanadium base negative electrode material is widely studied in the past few decades, mainly includes Li3VO4、VPO4、 Li3V2(PO4)3 And VOPO4.The Li of embedded type3VO4Have many advantages, such as stable crystal structure, quick lithium ion diffusion rate, but it is theoretical Low (the 394mAh g of specific capacity-1), poor (~5.8 × 10-6S cm of electron conduction-1)。VPO4Crystal structure is more stable, theoretical ratio Capacity height (550mAh g-1), but its cycle performance and high rate performance are unsatisfactory.Discharge performance under multiplying power, that is, different electric currents. Li3V2(PO4)3It is a kind of lithium ion battery electrode material that not only can be used as anode but also can be used as cathode.Although it has non- Often stable crystal structure, but its specific capacity and electron conduction be not advantageous.Nevertheless, the valence state due to vanadium is abundant Changeable, vanadium base electrode material still has very big potentiality and researching value.
V2(PO4) O/C composite material have stable crystal structure.V2(PO4) O/C is by [VO6] octahedra and [PO4] four sides Body composition.[VO6] octahedron between be face contact, [PO4] it is then point contact between tetrahedron.[VO6] octahedral two vertex It is four two-by-two common to symmetrical octahedron, remaining four oxygen atom is then [a PO4] tetrahedron and two Symmetrical [VO6] octahedron common to.And [PO4] tetrahedral oxygen atom is then in relatively simple environment, they are For common to a tetrahedron and two symmetrical octahedrons.With Li3V2(PO4)3In [VO6] octahedra different, V2 (PO4) octahedra there is no being come by tetrahedron isolation in O/C, [VO6] plane-plane contact between octahedron, and along a axis and b Axis forms a line.The octahedron of face contact ensures lesser V-V spacing, this is more conducive to electronics in high-valence state and lower valency Vanadium ion between transmit, substantially increase the intrinsic conductivity of material.High electronic conductivity and good lithium ion expand Dissipate coefficient.These characteristics impart the excellent chemical property of this material jointly.
However rarely have at present about V2(PO4) O/C composite material open preparation method, more this kind of material is not used as The precedent of the negative electrode material of lithium ion.
Therefore, it is necessary to invent a kind of V2(PO4) O/C material preparation method so that V2(PO4) O/C material preparation Method is simple and easy；Simultaneously it is also proposed that a kind of V2(PO4) O/C material be used as lithium-ion negative pole effective method and should Cathode, when so that the material obtained being used as ion cathode material lithium, with the negative electrode materials phase such as existing lithium titanate, nitride Than showing excellent reversible capacity, high rate performance and cyclical stability.
Summary of the invention
In view of the above-mentioned problems, the present invention is intended to provide a kind of V2(PO4) O/C material preparation method, lithium ion battery is made Cathode and method, to provide a kind of new technology of ion cathode material lithium, so that V2(PO4) O/C material preparation method more Reversible capacity, high rate performance and cyclical stability simple and easy, that keep lithium ion battery more excellent.
The present invention provides a kind of V2(PO4) O/C material preparation method, the method contains step: by vanadic anhydride With dissolving oxalic acid in deionized water, blue-tinted transparent solution is formed under the conditions of oil bath, then be successively added into the clear solution Ammonium dihydrogen phosphate and glucose obtain homogeneous solution；Ethylene glycol is added into the homogeneous solution again with the liquid that is uniformly mixed； The mixed liquor is subjected to hydro-thermal reaction, to obtain solid sediment；Wherein, the vanadic anhydride, oxalic acid, ammonium dihydrogen phosphate Molar ratio are as follows: 1:3:1；The quality of the glucose is 0.6-2 times of vanadic anhydride quality, and the ethylene glycol accounts for institute The volume fraction for stating mixed liquor is 3%-6%.
In the above method, the oil bath temperature is 60 DEG C -100 DEG C, and the molar concentration of the vanadic anhydride is 0.05- 0.08mol L-1。
In the above method, the temperature of the hydro-thermal reaction is 150-200 DEG C, reaction time 10-20h.
Further, the method also includes steps: calcining, obtains by being put into atmosphere furnace after solid sediment drying To V2(PO4) O/C material.
In the above method, the atmosphere in the atmosphere furnace is argon gas.
Further, the number calcined in the atmosphere furnace is that twice, first time calcination temperature is 300 DEG C -400 DEG C, Calcination time is 3-5h；Second of calcination temperature is 700 DEG C -800 DEG C, calcination time 7-9h.
In the above method, drying temperature when dry is 80-120 DEG C, and drying time is 10-15 hours.
The present invention, which provides, a kind of utilizes V made from the above method2(PO4) O/C material be made lithium ion battery cathode side Method, i.e., by the V2(PO4) after O/C material and acetylene black, Lithium polyacrylate aqueous solution mix with the weight ratio of 70:20:10 Coated in electrode film is made on copper foil, the cathode as lithium ion battery.
V made from the above method is utilized the present invention also provides a kind of2(PO4) lithium ion battery made of O/C material it is negative Pole, the electrode film of the electrode is with the V of constant weight ratio2(PO4) O/C material, acetylene black, Lithium polyacrylate aqueous solution it is mixed Conjunction object is coated on copper foil and is made, wherein active material V2(PO4) O/C material be 70%-90%, acetylene black 5%-20%, Binder Lithium polyacrylate is 5% -10%.
Technical solution of the present invention, provide a kind of production cost is low, method is simple and easy to control, be easily industrialized batch Production preparation V2(PO4) O/C material method, and no coupling product.The present invention is by V made from the technical program2(PO4) O/C material Material, for the first time be applied to ion secondary battery cathode material lithium, when serving as ion cathode material lithium, with existing lithium titanate, The negative electrode materials such as nitride are compared, and excellent reversible capacity, high rate performance and cyclical stability are shown.
Detailed description of the invention
Fig. 1 is V in first embodiment2(PO4) O/C phase structure diffracting spectrum；
Fig. 2 is in first embodiment with V2(PO4) O/C material as lithium ion battery negative material when measure difference electricity Multiplying power property under current density；
Fig. 3 is in first embodiment with V2(PO4) O/C material as lithium ion battery negative material when the lithium ion that measures Charging and discharging curve of the battery under different current densities；
Fig. 4 is in first embodiment with V2(PO4) O/C material as lithium ion battery negative material when the lithium ion that measures The secondary cell cycle characteristics at 1,2,5A/g respectively.
Specific embodiment
Below in conjunction with drawings and examples, a specific embodiment of the invention is described in more details, so as to energy The advantages of enough more fully understanding the solution of the present invention and various aspects.However, specific embodiments described below and implementation Example is for illustrative purposes only, rather than limiting the invention.
The present invention provides a kind of V2(PO4) O/C material preparation method, comprising the following steps:
(1) vanadic anhydride and oxalic acid are proportionally dissolved in deionized water, are stirred 1 hour under the conditions of oil bath, shape Au bleu clear solution.Then, ammonium dihydrogen phosphate and glucose are sequentially added and is stirred uniform to solution.Oil bath temperature is 60 DEG C -100 DEG C, the molar concentration of vanadic anhydride is 0.05-0.08mol L-1.Vanadic anhydride, oxalic acid and biphosphate The feed ratio of ammonium are as follows: V2O5: H2C2O4·2H2O:NH4H2PO4=1:3:1.Wherein, glucose and ethylene glycol can appropriate dispensing, one As glucose amount be that quality is vanadic anhydride quality 0.6-2 times, the ethylene glycol accounts for the volume fraction of above-mentioned mixed liquor For 3%-6%.
(2) mixed liquor is put into 100mL water heating kettle, carries out hydro-thermal reaction, reaction temperature is 150-200 DEG C, reaction Time is 10-20h.
(3) end of reaction obtains solid sediment, and solid sediment is dry, and after grinding, through 80-120 DEG C, 10-15 Hour oven drying, then put it into argon gas atmosphere stove and calcine, ventilation flow rate is 100sccm (standard milliliters/minute), is first existed It is sintered 3-5h under conditions of 300 DEG C -400 DEG C, 7-9h is then sintered under conditions of 700 DEG C -800 DEG C, is obtained after furnace cooling V2(PO4) O/C material.The V obtained according to this method2(PO4) O/C material phase structure diffracting spectrum it is as shown in Figure 1.
The V of method preparation as described above2(PO4) O/C material, it is made into the cathode of lithium ion battery, is by V2 (PO4) the certain weight ratio of materials (the active material 70%- such as O/C and acetylene black, Lithium polyacrylate (Li-PAA) aqueous solution 90%, acetylene black 5%-20%, binder accounts for 5% -10%) it can be on conductive metal as painted electrode on copper foil after mixing Film, the cathode as lithium ion secondary battery.
The overall process of assembly battery carries out (water oxygen value is respectively less than 0.1ppm) in glove box, and battery case is the 2032 of buying Button cell shell.The preparation process of electrode slice includes the production of electrode film, the electrode slice for drying, cutting into certain specification；Electricity Detailed process is as follows for the assembly in pond: it is sequentially placed into the electrode slice cut in the anode coat of battery, diaphragm, and lithium piece, and Electrolyte is injected in battery, and gasket, elastic slice and last positive shell are then covered above lithium piece.Finally with hydraulic sealing The sealing of machine completion button cell.Battery standing 10-12h can be subjected to charge-discharge test.
Use V2(PO4) materials such as O/C are assembled into the performance that lithium ion secondary battery is tested after half-cell, with 0.1A/g, When 1A/g and 2A/g current density charge and discharge, specific discharge capacity respectively up to 673mAh/g, 541mAh/g and 382mAh/g.200 charge and discharge are carried out with the current density of 1A/g and 5A/g, capacity retention ratio is respectively up to 90% He 79.8%.
Compared with prior art, the marked improvement having is as follows for embodiments of the present invention:
The present invention provides a kind of production cost is low, method is simple and easy to control, and process is easy, it is easy to accomplish industrial mass is raw The preparation V of production2(PO4) O/C material method, preparation process is simple to operation, no coupling product；
The resulting V of the present invention2(PO4) O/C material, it is applied to ion secondary battery cathode material lithium for the first time, specific capacity is high, Good cycling stability.
Illustrate technical solution of the present invention combined with specific embodiments below.
Institute's taking technique condition value is illustrative in following embodiments, be can use in numberical range book as indicated above It is shown.
First embodiment
By the V of 0.752g2O5The H of (vanadic anhydride) and 1.512g2C2O4(oxalic acid) is dissolved in the deionized water of 70mL, And it is stirred 60 minutes under the conditions of 70 DEG C of oil bath.Then sequentially add the NH of 0.46g4H2PO4(ammonium dihydrogen phosphate) and 0.6g Glucose, every time be added drug after stir 5 minutes, guarantee drug sufficiently dissolve and be uniformly mixed.Then to reaction system The middle ethylene glycol (EG) that 3mL is added, and 10min is futher stirred, solution is finally transferred to 100mL polytetrafluoroethylene (PTFE) material Hydro-thermal liner, and be sealed in stainless steel water heating kettle, the hydro-thermal reaction 10 hours under conditions of 150 DEG C.After hydro-thermal reaction Product is 10 hours dry under conditions of 80 DEG C, is then pre-sintered 4 hours under conditions of 350 DEG C, is finally sintered at 750 DEG C Final product V is obtained after 8 hours2(PO4)O/C。
2032 button cell of battery case model of electro-chemical test is used in this research, all batteries to be in water oxygen Value is respectively less than in the glove box of 0.1ppm (parts per million) and assembles.Glove box is that high purity inert gas is filled in cabinet, and follows Ring filters out the laboratory equipment of active material therein.Negative electrode material slurry by 70% active material V2(PO4) O/C material, 20% acetylene black conductor and 10% binder (Li-PAA) are uniformly mixed through ultrasound.Slurry is uniformly coated on copper On foil, be placed in air dry oven 80 DEG C at a temperature of dry 4 hours, then toasted 12 hours under conditions of 120 DEG C.Battery Lithium piece is taken to be used as to electrode in manufacturing process, Celgard polypropylene screen is the diaphragm of battery.Electrolyte is dissolved in by 1M LiPF6 It is formulated in the ethylene carbonate (EC) and dimethyl carbonate (DMC) mixed solution that mass ratio is 1:1.By manufactured electrode Be assembled into shell it is packaged after, the amount of the active material for the electrode slice being finally made is 0.8-1.0mg cm-2.
It is illustrated in figure 2 in the present embodiment with V obtained2(PO4) O/C material as lithium ion battery negative material when survey Multiplying power property (discharge performance under i.e. different electric currents) under the different current densities obtained；Be illustrated in figure 3 in the present embodiment with V2(PO4) O/C material as lithium ion battery negative material when the charge and discharge under different current densities of the lithium ion battery that measures Curve；It is illustrated in figure 4 in the present embodiment with V2(PO4) O/C material as lithium ion battery negative material when the lithium ion that measures The secondary cell cycle characteristics at 1,2,5A/g respectively.
It can be seen that the method for the embodiment of the present invention is simple and easy to control, no coupling product；V of the present invention2(PO4) O/C material answers For ion secondary battery cathode material lithium, specific capacity is high, good cycling stability.
Second embodiment
By the H of the V2O5 of 0.752g and 1.512g2C2O4(oxalic acid) is dissolved in the deionized water of 70mL, and in 100 DEG C of oil It is stirred 60 minutes under the conditions of bath.Then sequentially add the NH of 0.46g4H2PO4The glucose of (ammonium dihydrogen phosphate) and 1g adds every time It is stirred 5 minutes after entering drug, guarantees that drug is sufficiently dissolved and is uniformly mixed.Then the second two of 2mL is added into reaction system Alcohol (EG), and 10min is futher stirred, solution is finally transferred to the hydro-thermal liner of 100mL polytetrafluoroethylene (PTFE) material, and seal In stainless steel water heating kettle, the hydro-thermal reaction 20 hours under conditions of 200 DEG C.Product after hydro-thermal reaction is under conditions of 80 DEG C It is 15 hours dry, it is then pre-sintered under conditions of 350 DEG C 4 hours, final produce is obtained after being finally sintered 8 hours at 750 DEG C Object V2(PO4)O/C。
3rd embodiment
By the V of 0.752g2O5With the H of 1.512g2C2O4It is dissolved in the deionized water of 70mL, and under the conditions of 70 DEG C of oil bath Stirring 60 minutes.Then sequentially add 0.46g NH4H2PO4With the glucose of 0.8g, stirred 5 minutes after drug is added every time, Guarantee that drug is sufficiently dissolved and is uniformly mixed.Then the ethylene glycol (EG) of 4mL is added into reaction system, and futher stirs Solution, is finally transferred to the hydro-thermal liner of 100mL polytetrafluoroethylene (PTFE) material by 10min, and is sealed in stainless steel water heating kettle, Hydro-thermal reaction 12 hours under conditions of 180 DEG C.Product after hydro-thermal reaction is 12 hours dry under conditions of 120 DEG C, then exists It is pre-sintered under conditions of 350 DEG C 4 hours, final product V is obtained after being finally sintered 8 hours at 800 DEG C2(PO4)O/C。
It can be seen that above mentioned embodiment provide a kind of production costs is low, method is simple and easy to control, it is raw to be easily industrialized batch The preparation V of production2(PO4) O/C material method, and no coupling product.
Finally, it should be noted that obviously, the above embodiment is merely an example for clearly illustrating the present invention, and simultaneously The non-restriction to embodiment.For those of ordinary skill in the art, it can also do on the basis of the above description Other various forms of variations or variation out.There is no necessity and possibility to exhaust all the enbodiments.And thus drawn The obvious changes or variations that Shen goes out are still in the protection scope of this invention.

Claims (10)

1. a kind of V2(PO4) O/C material preparation method, the method includes steps:
By vanadic anhydride and dissolving oxalic acid in deionized water, blue-tinted transparent solution is formed under the conditions of oil bath, then successively to institute It states addition ammonium dihydrogen phosphate and glucose in clear solution and obtains homogeneous solution；Again into the homogeneous solution be added ethylene glycol with Be uniformly mixed liquid；
The mixed liquor is subjected to hydro-thermal reaction, to obtain solid sediment；
It is calcined being put into atmosphere furnace after solid sediment drying, obtains V2(PO4) O/C material；
Wherein, the molar ratio of the vanadic anhydride, oxalic acid, ammonium dihydrogen phosphate are as follows: 1:3:1；
The quality of the glucose is 0.6-2 times of vanadic anhydride quality, and the ethylene glycol accounts for the volume point of the mixed liquor Number is 3%-6%.
2. described five aoxidize the method according to claim 1, wherein the oil bath temperature is 60 DEG C -100 DEG C The molar concentration of two vanadium is 0.05-0.08mol L-1。
3. the method according to claim 1, wherein the temperature of the hydro-thermal reaction is 150-200 DEG C, when reaction Between be 10-20h.
4. the method according to claim 1, wherein the atmosphere in the atmosphere furnace is argon gas.
5. the method according to claim 1, wherein the number calcined in the atmosphere furnace is twice first Secondary calcination temperature is 300 DEG C -400 DEG C, calcination time 3-5h；Second of calcination temperature is 700 DEG C -800 DEG C, and calcination time is 7-9h。
6. the method according to claim 1, wherein drying temperature when dry is 80-120 DEG C, drying time It is 10-15 hours.
7. a kind of utilize V made from any one of claim 1 to 6 the method2(PO4) the negative of lithium ion battery is made in O/C material The method of pole, which is characterized in that by the V2(PO4) O/C material and acetylene black, Lithium polyacrylate aqueous solution be with certain weight It is coated in after ratio mixing on copper foil and electrode film is made, the cathode as lithium ion battery.
8. the method according to the description of claim 7 is characterized in that the V2(PO4) O/C material be 70%-90%, acetylene black For 5%-20%, binder Lithium polyacrylate aqueous solution is 5% -10%.
9. a kind of utilize V made from any one of claim 1 to 6 the method2(PO4) lithium ion battery made of O/C material Cathode, which is characterized in that the cathode by constant weight ratio V2(PO4) O/C material, acetylene black, Lithium polyacrylate aqueous solution Mixture be coated in copper foil on be made.
10. the cathode of lithium ion battery according to claim 9, which is characterized in that the V2(PO4) O/C material is 70%-90%, acetylene black 5%-20%, binder Lithium polyacrylate aqueous solution are 5% -10%.
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JP2003068304A (en) * 2001-08-30 2003-03-07 Yusaku Takita Electrode active material for secondary nonaqueous electrolyte battery, electrode containing the same and battery
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JP2003068304A (en) * 2001-08-30 2003-03-07 Yusaku Takita Electrode active material for secondary nonaqueous electrolyte battery, electrode containing the same and battery
CN102306789A (en) * 2011-08-10 2012-01-04 东莞市迈科科技有限公司 Li4Ti5O12/Li3V2(PO4)3 composite material and preparation method thereof

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