CN105118968B - A kind of nido V2O3Coat the lithium ion anode material of phosphoric acid vanadium lithium - Google Patents

A kind of nido V2O3Coat the lithium ion anode material of phosphoric acid vanadium lithium Download PDF

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CN105118968B
CN105118968B CN201510636851.XA CN201510636851A CN105118968B CN 105118968 B CN105118968 B CN 105118968B CN 201510636851 A CN201510636851 A CN 201510636851A CN 105118968 B CN105118968 B CN 105118968B
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lithium
nido
anode material
coat
vanadium
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CN105118968A (en
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张宝
王小玮
明磊
刘益
田业成
张佳峰
童汇
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Central South University
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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
    • 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
    • H01M4/136—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
    • H01M4/1397—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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

A kind of nido V2O3The lithium ion anode material of phosphoric acid vanadium lithium is coated, preparation method includes the following steps：（1）Li source compound, vanadium source compound, P source compound, reducing agent are added in deionized water, ultrasonic agitation 0.5~2h of reaction is carried out, obtains mixed solution；Wherein, elemental lithium, v element, P elements, reducing agent molar ratio be 1.5:1.05~1.2:1.5:1.1~1.5；（2）Solution is spray-dried, solid powder is obtained；（3）By step（2）Obtained solid powder is in protective atmosphere, at 400 ~ 500 DEG C, after roasting 4 ~ 6h, cools to room temperature with the furnace to get nido V2O3Coat Li3V2(PO4)3Lithium ion anode material.Operating process of the present invention is simple, and covered effect is good, and gained composite material has excellent high rate performance.

Description

A kind of nido V2O3Coat the lithium ion anode material of phosphoric acid vanadium lithium
Technical field
The present invention relates to the positive electrodes and its manufacturing method of phosphoric acid vanadium lithium, being used as lithium-ion electric more particularly to one kind The lithium vanadium phosphate material and its manufacturing method of pond positive electrode, belong to field of lithium ion battery.
Background technology
Primary energy crisis just causes more and more problems in the world with environmental pollution.In this context, green The free of contamination novel high-energy electrochmical power source of color has become the hot spot that countries in the world are competitively developed.Lithium ion battery is a kind of novel Electrochmical power source uses two compounds that are reversibly embedded and deviating from lithium ion to be constituted as positive and negative anodes respectively.When battery fills When electric, lithium ion deintercalation from anode comes out, embedded in cathode；Lithium ion deintercalation from cathode comes out when electric discharge, in anode Middle insertion.For lithium ion battery since with high-energy density, high voltage is pollution-free, cycle life is high, and memory-less effect etc. is excellent Point has been widely used at present in laptop, mobile phone and other portable electronics.
Phosphoric acid vanadium lithium is the compound of monocline, is deemed likely to be polyanionic more better than LiFePO4 performance Positive electrode, and its cycle and high rate performance decaying are very fast, fail extensive use.
Cladding is always to improve the effective means of positive electrode performance, and effective cladding can be carried with the structure of stabilizing material The properties of high material.Vanadium trioxide is a kind of with satisfactory electrical conductivity（）Metal oxide, but at present It not be used to also coat lithium vanadium phosphate material.
CN104269530A discloses a kind of method of hydrothermal synthesis LiFePO4-phosphoric acid vanadium lithium composite material, including with Lower step：The vanadium source solution of the source of iron solution of 0.5~2mol/L and 0.5~2mol/L are added in autoclave, are added Appropriate urea makes pH 1~7, and stirring obtains suspended slurry；Li source compound, P source compound and compounded carbons are added, make Iron, vanadium, lithium, phosphorus and carbon molar ratio are 1:1:2.5:2.5:2.5~7.5, react 10~30h, obtained precipitation is washed, Filtering, then be freeze-dried, controlled at-30~-50 DEG C, control drying time is 10~20h, obtains LiFePO4-phosphorus Sour vanadium lithium composite feed powder end.Although its synthetic method is simple, calcination temperature is low, and the XRD of its synthetic sample is more mixed and disorderly, Crystal form is not sufficiently stable, and cycle performance is bad（1C is recycled 40 times, capacity retention ratio 91.45%）.
CN104347852A discloses a kind of preparation method of lithium manganese phosphate-phosphoric acid vanadium lithium composite material, be by 0.1~ The ammonium metavanadate solution of 0.4mol/L is added with the speed of 0.5~2.0L/h to filling 0.05~0.20mol/L acetic acid manganese solutions Reaction kettle in, control final manganese, v element molar ratio be Mn:V=1:2,50~90 DEG C of controlling reaction temperature and mixing speed 200~1200rpm after the completion of charging, adjusts pH value of solution to 4~7, stands, dry after being filtered, washed, and obtains MnV2O6· 2H2O；By MnV2O6·2H2O, Li source compound, P source compound and compounded carbons are with manganese, vanadium, phosphorus, lithium, carbon molar ratio It being mixed for 1: 2: 4: 4: 0.1~10 proportioning, ball milling is dry, sintering.Though gained lithium manganese phosphate has firm phosphoric acid vanadium lithium The effect of structure, but process is complex..
CN103985863A disclose a kind of cerium oxide and carbon coat altogether phosphoric acid vanadium lithium anode material for lithium-ion batteries and Preparation method uses vanadic anhydride, citric acid, ammonium dihydrogen phosphate, lithium carbonate for raw material, molar ratio 2: 4: 6: 3, system Standby carbon coating phosphoric acid vanadium lithium；Using cerium nitrate hexahydrate as cerium source, it is 0.5~10% that CeO2 contents, which account for phosphoric acid vanadium lithium mass percent,. But it coats process complexity, and sintering temperature is high.
Invention content
The technical problem to be solved by the present invention is to it is excellent to overcome the deficiencies of the prior art and provide a kind of high rate performance, closes Simpler at process, cladding process is simple, the lower nido V of reaction required temperature2O3Coat the lithium ion anode material of phosphoric acid vanadium lithium Material.
The technical solution adopted by the present invention to solve the technical problems is as follows：A kind of nido V2O3Coat the lithium of phosphoric acid vanadium lithium Ion positive electrode, preparation method include the following steps：
（1）Li source compound, vanadium source compound, P source compound, reducing agent are added in deionized water, ultrasound is carried out and stirs 0.5~2h of reaction is mixed, mixed solution is obtained；Wherein, elemental lithium, v element, P elements, reducing agent molar ratio be 1.5: 1.05 ~ 1.2∶1.5∶1.1~1.5；
Step（1）In, a concentration of 0.05~0.4mol/L of vanadium ion in the mixed solution, concentration is too low to reduce production Amount, excessive concentration are then unfavorable for the generation of nido structure；
（2）By step（1）The spraying drying of gained mixed solution, obtains solid powder；
（3）By step（2）Obtained solid powder is in protective atmosphere, at 400 ~ 500 DEG C, after roasting 4 ~ 6h, with furnace cooling But to room temperature to get nido V2O3Coat Li3V2(PO4)3Lithium ion anode material.
Further, step（1）In, supersonic frequency is 20 ~ 40KHz.
Further, step（1）In, stir speed (S.S.) is 100 ~ 4000rpm/min.
Further, step（1）In, the Li source compound is lithium oxalate, lithium dihydrogen phosphate, lithium hydroxide, lithium acetate, carbon At least one of sour lithium, lithium phosphate, lithium chloride, lithium nitrate.
Further, step（1）In, the vanadium source compound is vanadic anhydride, ammonium metavanadate, vanadium dioxide, three oxidations At least one of two vanadium.
Further, step（1）In, phosphorus source compound be monoammonium phosphate, ammonium dihydrogen phosphate, ammonium phosphate, lithium phosphate, At least one of lithium dihydrogen phosphate, tertiary sodium phosphate, triethyl phosphate, tributyl phosphate, phosphate.
Further, step（1）In, the reducing agent is at least one of oxalic acid, formic acid.
Further, step（2）In, the spray drying intake air temperature is 200 ~ 260 DEG C, is spray-dried wriggling revolution speed For 500 ~ 1800rpm/min, spray drying rotation speed of fan is 40 ~ 150HZ.Solution moment can be volatilized and helped by spray drying Form nido clad structure.
Further, step（3）In, the protective atmosphere be argon gas, nitrogen, hydrogen, carbon dioxide or carbon monoxide, or Hydrogen/argon-mixed；The volumetric concentration of the hydrogen/argon-mixed middle hydrogen is 1~80%.Under the conditions of such so that material is relatively low Under calcination temperature, rock-steady structure can be also formed, shows outstanding chemical property.
Protective atmosphere used in the present invention is high-purity gas, purity >=99.99%.
The technical principle of the method for the present invention is：The present invention generates soluble chemical combination using acidic reduction agent and vanadium-containing compound Object is being added phosphorus source with after lithium source, is being evaporated solution using spray drying technology, because each element is evenly distributed in solution, in shape Extra v element can form barium oxide and wrap material when at vanadium phosphate cathode material, form cladding.Subsequent low Nido V is formed in warm roasting process2O3Coat Li3V2(PO4)3Lithium ion anode material.The clad of the present invention aoxidizes for vanadium Object, it is more close with main body positive electrode, nido clad structure can be grown on material of main part, compared to common cladding, It is more conducive to the deintercalation of lithium ion and electronics, improves the cycle performance of material.
Advantage of the invention is that carrying out cladding in situ to positive electrode using same materials, not only coat more It is even, and reaction required temperature is low, can effectively stablize the structure of phosphoric acid vanadium lithium, improves cycle performance.
Description of the drawings
Fig. 1 is the nido V obtained by the embodiment of the present invention 12O3Coat Li3V2(PO4)3Lithium ion anode material XRD Figure；
Fig. 2 is the nido V obtained by the embodiment of the present invention 12O3Coat Li3V2(PO4)3Lithium ion anode material SEM Figure；
Fig. 3 is the nido V obtained by the embodiment of the present invention 12O3Coat Li3V2(PO4)3Lithium ion anode material at 3C times Cyclic curve figure under rate.
Fig. 4 is cyclic curve figure of the lithium ion anode material under 3C multiplying powers obtained by comparative example of the present invention.
Specific implementation mode
With reference to embodiment and attached drawing, the invention will be further described.
The purity of high-purity argon gas, high-purity hydrogen and high pure nitrogen used in the embodiment of the present invention is 99.99%；It is used Other chemical reagent obtained unless otherwise specified by routine business approach.
Embodiment 1
The present embodiment includes the following steps：
（1）Weigh ammonium metavanadate 12.87g（0.11mol）, lithium dihydrogen phosphate 15.59g（0.15mol, while as phosphorus source And lithium source）, two oxalic acid hydrate 14.50g（0.12mol）, it is mixed and is added in 0.37L deionized waters, vanadium ion in solution A concentration of 0.3mol/L；At supersonic frequency 30kHz, mixing speed 250r/min, it is stirred to react 1h, obtains mixed solution；
（2）By step（1）Gained mixed solution is spray-dried, and spray drying intake air temperature is 230 DEG C, and spraying is dry Dry wriggling revolution speed is 1000rpm/min, and spray drying rotation speed of fan is 100HZ, obtains solid powder；
（3）By step（2）Obtained solid powder is under high-purity argon gas protection, at 450 DEG C, after roasting 5h, and furnace cooling To room temperature to get nido V2O3Coat Li3V2(PO4)3Lithium ion anode material.Wherein V2O3Opposite Li3V2(PO4)3Quality hundred Divide than being 3.68%.
Fig. 1 is the nido V obtained by the present embodiment2O3Coat Li3V2(PO4)3Lithium ion anode material XRD diagram；Figure 2 be the nido V obtained by the present embodiment2O3Coat Li3V2(PO4)3Lithium ion anode material SEM figure；Fig. 3 is the present embodiment Obtained nido V2O3Coat Li3V2(PO4)3Cyclic curve figure of the lithium ion anode material under 3C multiplying powers.
Nido V as shown in Figure 12O3Coat Li3V2(PO4)3Lithium ion anode material XRD diagram it is found that low-temperature bake Material has preferable crystal form, diffraction maximum and V2O3And Li3V2(PO4)3Standard card it is corresponding, it was demonstrated that there are two-phases for it.
Nido V as shown in Figure 22O3Coat Li3V2(PO4)3Lithium ion anode material SEM scheme it is found that V2O3In nido packet Cover spherical Li3V2(PO4)3。
The assembling of battery：Weigh the nido V obtained by 0.40g2O3Coat Li3V2(PO4)30.05g acetylene is added in positive electrode It is black to make conductive agent and 0.05g NMP（N-Methyl pyrrolidone）Make binder, be coated on aluminium foil positive plate is made after mixing, It is diaphragm, 1mol/L LiPF with Celgard 2300 using metal lithium sheet as cathode in vacuum glove box6/EC∶DMC（Volume Than 1: 1）For electrolyte, it can be assembled into the button cell of CR2025.
By battery in 3.0 ~ 4.3V voltage ranges, its charge/discharge capacity and big circulation performance are measured, 3C is for the first time Electric discharge gram volume is 127.5 mAh/g, and capacity retention ratio is 97.95% after being recycled 50 times under 3C multiplying powers（As shown in Figure 3）.
Embodiment 2
The present embodiment includes the following steps：
（1）Weigh ammonium metavanadate 6.43g（0.055mol）, vanadic anhydride 4.55g（0.0275mol）, lithium hydroxide 3.59g（0.15mol）, ammonium dihydrogen phosphate 17.25g（0.15mol）, formic acid 1.38g（0.03mol）, two oxalic acid hydrate 10.08g （0.08mol）；It is mixed and is added in 0.525L deionized waters；At supersonic frequency 20kHz, mixing speed 100r/min, stir Reaction 1.5h is mixed, mixed solution is obtained；
（2）By step（1）Gained mixed solution is spray-dried, and spray drying intake air temperature is 200 DEG C, and spraying is dry Dry wriggling revolution speed is 500rpm/min, and spray drying rotation speed of fan is 40HZ, obtains solid powder；
（3）By step（2）Obtained solid powder is in High Purity Hydrogen/argon-mixed（Hydrogen volume a concentration of 5%）Under protection, in At 500 DEG C, after roasting 6h, room temperature is cooled to the furnace to get nido V2O3Coat Li3V2(PO4)3Lithium ion anode material, Middle V2O3Opposite Li3V2(PO4)3Mass ratio is 1.84%.
The assembling of battery：Weigh the nido V obtained by 0.40g2O3Coat Li3V2(PO4)30.05g acetylene is added in positive electrode It is black to make conductive agent and 0.05g NMP（N-Methyl pyrrolidone）Make binder, be coated on aluminium foil positive plate is made after mixing, It is diaphragm, 1mol/L LiPF with Celgard 2300 using metal lithium sheet as cathode in vacuum glove box6/EC∶DMC（Volume Than 1: 1）For electrolyte, it can be assembled into the button cell of CR2025.
By battery in 3.0 ~ 4.3V voltage ranges, its charge/discharge capacity and big circulation performance are measured, 3C is for the first time Electric discharge gram volume is 120.5 mAh/g, and capacity retention ratio is 95.20% after being recycled 50 times under 3C multiplying powers.
Embodiment 3
The present embodiment includes the following steps：
（1）Weigh vanadic anhydride 10.91g（0.06mol）, lithium carbonate 5.54g（0.075mol）, ammonium dihydrogen phosphate 17.25g（0.15mol）, two oxalic acid hydrate 18.99g（0.15mol）, it is mixed and is added in 0.3L deionized waters；In supersonic frequency Under rate 40kHz, mixing speed 400r/min, it is stirred to react 2h, obtains mixed solution；
（2）By step（1）Acquired solution is spray-dried, and spray drying intake air temperature is 260 DEG C, and spray drying is compacted Dynamic revolution speed is 1800rpm/min, and spray drying rotation speed of fan is 150HZ, obtains solid powder；
（3）By step（2）Obtained solid powder is under high-purity argon gas protection, at 500 DEG C, after roasting 6h, and furnace cooling To room temperature to get nido V2O3Coat Li3V2(PO4)3Lithium ion anode material.Wherein V2O3Opposite Li3V2(PO4)3Mass ratio It is 7.35%.
The assembling of battery：Weigh the nido V obtained by 0.40g2O3Coat Li3V2(PO4)30.05g acetylene is added in positive electrode It is black to make conductive agent and 0.05g NMP（N-Methyl pyrrolidone）Make binder, be coated on aluminium foil positive plate is made after mixing, It is diaphragm, 1mol/L LiPF with Celgard 2300 using metal lithium sheet as cathode in vacuum glove box6/EC∶DMC（Volume Than 1: 1）For electrolyte, it can be assembled into the button cell of CR2025.
By battery in 3.0 ~ 4.3V voltage ranges, its charge/discharge capacity and big circulation performance are measured, 3C is for the first time Electric discharge gram volume is 115.5 mAh/g, and capacity retention ratio is 97.20% after being recycled 50 times under 3C multiplying powers.
Comparative example
（1）Weigh ammonium metavanadate 11.70g（0.1mol）, lithium dihydrogen phosphate 15.59g（0.15mol simultaneously as phosphorus source and Lithium source）, two oxalic acid hydrate 14.50g（0.12mol）, it is mixed and is added in 0.33L deionized waters, vanadium ion is dense in solution Degree is 0.3mol/L；At supersonic frequency 30kHz, mixing speed 250r/min, it is stirred to react 1h, obtains mixed solution；
（2）By step（1）Gained mixed solution is spray-dried, and spray drying intake air temperature is 230 DEG C, and spraying is dry Dry wriggling revolution speed is 1000rpm/min, and spray drying rotation speed of fan is 100HZ, obtains solid powder；
（3）By step（2）Obtained solid powder is under high-purity argon gas protection, at 450 DEG C, after roasting 5h, and furnace cooling To room temperature to get Li3V2(PO4)3Lithium ion anode material.
The assembling of battery：Weigh the Li obtained by 0.40g3V2(PO4)3Positive electrode is added 0.05g acetylene blacks and makees conductive agent With 0.05g NMP（N-Methyl pyrrolidone）Make binder, is coated on aluminium foil positive plate is made after mixing, in vacuum glove It is diaphragm, 1mol/L LiPF with Celgard 2300 using metal lithium sheet as cathode in case6/EC∶DMC（Volume ratio 1: 1）For electricity Liquid is solved, the button cell of CR2025 is can be assembled into.
By battery in 3.0 ~ 4.3V voltage ranges, its charge/discharge capacity and big circulation performance are measured, 3C is for the first time Electric discharge gram volume is 120.5 mAh/g, and capacity retention ratio is 73.65% after being recycled 50 times under 3C multiplying powers（As shown in Figure 4）.
As it can be seen that the molar ratio of v element is 1.5: 1 in elemental lithium and vanadium source in lithium source in this comparative example, gained positive electrode Good cladding cannot be formed.Its cycle performance is bad.

Claims (8)

1. a kind of nido V2O3Coat the lithium ion anode material of phosphoric acid vanadium lithium, which is characterized in that preparation method, including it is following Step：
（1）Li source compound, vanadium source compound, P source compound, reducing agent are added in deionized water, be stirred by ultrasonic anti- 0.5~2h is answered, mixed solution is obtained；Wherein, elemental lithium, v element, P elements, reducing agent molar ratio be 1.5: 1.05 ~ 1.2: 1.5∶1.1~1.5；
A concentration of 0.05~0.4mol/L of vanadium ion in the mixed solution；
（2）By step（1）The spraying drying of gained mixed solution, obtains solid powder；
The spray drying intake air temperature is 200 ~ 260 DEG C, and spray drying wriggling revolution speed is 500 ~ 1800rpm/min, spray Mist drying air fan rotating speed is 40 ~ 150HZ；
（3）By step（2）Obtained solid powder is in protective atmosphere, at 400 ~ 500 DEG C, after roasting 4 ~ 6h, cools to the furnace Room temperature is to get nido V2O3Coat Li3V2(PO4)3Lithium ion anode material；
Step（3）In, the protective atmosphere is argon gas, nitrogen, hydrogen, carbon dioxide or carbon monoxide or hydrogen/argon-mixed.
2. nido V according to claim 12O3Coat the lithium ion anode material of phosphoric acid vanadium lithium, which is characterized in that it is made Preparation Method step（1）In, supersonic frequency is 20 ~ 40KHz.
3. nido V according to claim 1 or 22O3Coat the lithium ion anode material of phosphoric acid vanadium lithium, which is characterized in that its Preparation method step（1）In, stir speed (S.S.) is 100 ~ 4000rpm/min.
4. nido V according to claim 1 or 22O3Coat the lithium ion anode material of phosphoric acid vanadium lithium, which is characterized in that its Preparation method step（1）In, the Li source compound is lithium oxalate, lithium dihydrogen phosphate, lithium hydroxide, lithium acetate, lithium carbonate, phosphorus At least one of sour lithium, lithium chloride, lithium nitrate.
5. nido V according to claim 1 or 22O3Coat the lithium ion anode material of phosphoric acid vanadium lithium, which is characterized in that its Preparation method step（1）In, the vanadium source compound is in vanadic anhydride, ammonium metavanadate, vanadium dioxide, vanadium trioxide It is at least one.
6. nido V according to claim 1 or 22O3Coat the lithium ion anode material of phosphoric acid vanadium lithium, which is characterized in that its Preparation method step（1）In, phosphorus source compound is monoammonium phosphate, ammonium dihydrogen phosphate, ammonium phosphate, lithium phosphate, di(2-ethylhexyl)phosphate At least one of hydrogen lithium, tertiary sodium phosphate, triethyl phosphate, tributyl phosphate, phosphate.
7. nido V according to claim 1 or 22O3Coat the lithium ion anode material of phosphoric acid vanadium lithium, which is characterized in that its Preparation method step（1）In, the reducing agent is at least one of oxalic acid, formic acid.
8. nido V according to claim 1 or 22O3Coat the lithium ion anode material of phosphoric acid vanadium lithium, which is characterized in that its Preparation method step（3）In, the volumetric concentration of the hydrogen/argon-mixed middle hydrogen is 1~80%.
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