CN105304875A - Preparation method of lithium ion battery composite cathode material - Google Patents

Preparation method of lithium ion battery composite cathode material Download PDF

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Publication number
CN105304875A
CN105304875A CN201510640646.0A CN201510640646A CN105304875A CN 105304875 A CN105304875 A CN 105304875A CN 201510640646 A CN201510640646 A CN 201510640646A CN 105304875 A CN105304875 A CN 105304875A
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lithium
acid
phosphate
preparation
vanadium
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伍凌
钟胜奎
张晓萍
刘洁群
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Suzhou University
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Suzhou 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
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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 invention discloses a preparation method of a lithium ion battery composite cathode material. The composite material is of a multi-core type core-shell structure; inner cores are formed by lithium manganese phosphate particles coated by lithium vanadium phosphate; an outer shell layer is formed by amorphous carbon. Firstly, lithium vanadium phosphate precursor sol is prepared, then lithium manganese phosphate powder is added and is uniformly dispersed, and spray pyrolysis is carried out in inert atmosphere to obtain the lithium manganese phosphate inner cores coated by the lithium vanadium phosphate; then an organic carbon matrix precursor is dissolved in deionized water, the inner core materials are added, spray drying is carried out after the inner core materials are uniformly dispersed, and calcinations is carried out in non-oxidizing atmosphere to obtain the composite cathode material. The composite material prepared by the preparation method has excellent electrochemical performance; the lithium vanadium phosphate improves ionic conductivity and electronic conductivity of the material; the amorphous carbon improves electronic conductivity of the material. Meanwhile, the multi-core type core-shell structure similar to a nano-micro structure enables the material to have high tap density and excellent machinability.

Description

A kind of preparation method of lithium ion battery composite cathode material
Technical field
The invention belongs to the preparation method field of lithium ion battery electrode material, relate to the preparation method of a kind of lithium manganese phosphate-phosphoric acid vanadium lithium composite positive pole.
Background technology
LiMnPO 4because of its have that theoretical specific capacity is high, operating voltage is high, inexpensive, safety, the multiple advantage such as environmental protection, be it is believed that it is the very promising anode material for lithium-ion batteries of one.But extremely low electronic conductivity and ionic conductivity cause LiMnPO 4electro-chemical activity very poor.Therefore, current to LiMnPO 4study on the modification emphasis concentrate on and improve its electronic conductivity and ionic conductivity two aspects, the main method improving electronic conductivity has: 1) Surface coating electronic conductor, as carbon, metal, conducting polymer etc.; 2) gas ions is phase-doped modified.The main method improving ionic conductance speed has: 1) Surface coating fast-ionic conductor; 2) micronized particles and synthesize the particle etc. of special nanostructure.
At LiMnPO 4middle dispersion or coated with conductive carbon, can strengthen the conductivity between particle and particle on the one hand, reduces polarization of electrode; It can also hinder particle growth, micronized particles on the other hand, can also play the effect of reducing agent simultaneously, prevent Mn 2+oxidation.
Improving ionic conductivity at the coated fast-ionic conductor of phosphate cathode material particle surface is improve the effective ways of its chemical property.Such as, the Ceder etc. (Nature, 2009,458:190-193) of masschusetts, u.s.a science and engineering has prepared the Surface coating fast-ionic conductor (Li of hyaloid material 3pO 4) nanometer LiFePO 4, the specific discharge capacity of this material under 2C and 50C multiplying power is up to 166mAhg -1and 136mAhg -1, even still can discharge 60mAhg under 400C multiplying power -1.Result of study shows, LiFePO 4the amorphous fast lithium ion conductor layer that surface is formed compensate for the deficiency of its surface anisotropy, improves the lithium ion transport speed from plane of crystal to (010) face, thus high rate performance is greatly improved.In view of LiMnPO 4and LiFePO 4there is identical crystal structure, Li +at LiMnPO 4body mutually in be also by one dimension channels spread, its transmission mechanism is consistent.Therefore, by increasing LiMnPO 4the Li of grain surface +transmission channel greatly can improve LiMnPO 4chemical property.
Monoclinic Li 3v 2(PO 4) 3a kind of polyanionic lithium ion battery anode material with NASCION structure, relative to LiMnPO 4, its most obvious characteristic has isotropic three-dimensional lithium ion tunnel, is a kind fast-ionic conductor, if it is coated on LiMnPO 4grain surface, can increase the lithium ion transport passage of grain surface to (010) face, thus improve its ionic conductivity; Relative to Li 3pO 4deng fast-ionic conductor, Li 3v 2(PO 4) 3advantage be that itself there is electro-chemical activity (theoretical specific capacity 197mAhg -1), if it is as coating layer, the capacity of material can not be reduced.In addition, Li 3v 2(PO 4) 3electronic conductivity (~ 10 -7scm -1) far above LiMnPO 4(10 -14~ 10 -10scm -1), the therefore coated electronic conductivity that can also improve material.
In recent years, nanometer is also an important development direction of lithium ion battery electrode material.Lithium ion battery electrode material can produce many at the inaccessiable excellent properties of micro-meter scale after nanometer, such as high power capacity, excellent high rate during charging-discharging etc., and the high-energy-density of these performances and battery, high power density are closely related.A kind of effective means so applying nano technological development high-energy and high-power electrode material be can yet be regarded as.But bring outstanding irreversible surface reaction that its cycle performance and security performance are challenged after material nano, and design have the effective way that the nano and micron composite structure of " dynamic stabilization " feature and Surface coating are expected to become practical application.Because lithium ion is at LiMnPO 4in diffusion rate very slow, and LiMnPO 4the reduction of grain diameter is conducive to shortening the path that lithium ion spreads in the material, improves the diffusivity of lithium ion, finally reaches and improve LiMnPO 4the object of positive electrode electrical property.
At this, we propose to adopt aerosol spray cracking-spraying dry combination method to prepare a kind of lithium ion battery phosphate composite positive pole of multinuclear type nucleocapsid structure, and this composite material is by multiple lithium fast-ionic conductor Li 3v 2(PO 4) 3coated LiMnPO 4many core-shell particles that particle kernel and amorphous carbon monoshell layer are formed, and shell and kernel, kernel and interior internuclear gap are connected by conductive carbon mesh.This material not only has excellent chemical property, and has very high tap density, is applicable to high-energy density type lithium-ion-power cell.
Summary of the invention
An object of the present invention is to provide a kind of lithium ion battery composite cathode material, improve the chemical property of cathode material lithium manganese phosphate, tap density and energy density, improve the processing characteristics of nanoscale lithium manganese phosphate, make it be more suitable for high-energy density type lithium ion battery.
A kind of lithium ion battery composite cathode material, the multinuclear type nucleocapsid structure positive electrode be made up of the coated multiple kernel of outer shell, described kernel is the monokaryon particle of the coated lithium manganese phosphate of phosphoric acid vanadium lithium, described outer shell is amorphous carbon, and described amorphous carbon is calcined by a kind of organic carbon source in oxalic acid, glucose, sucrose, citric acid, tartaric acid, adipic acid, polyethylene glycol, polyvinyl alcohol, fructose and ascorbic acid and is transformed.
Described kernel particle size scope 10 ~ 1000nm; The particle size scope of described composite positive pole is 0.5 ~ 20 μm.
Described lithium manganese phosphate is 0.1 ~ 50 times of phosphoric acid vanadium lithium quality; The quality of outer shell institute carbon containing is 0.1 ~ 10% of interior nuclear mass.
Second object of the present invention is to provide a kind of preparation method of above-mentioned lithium ion battery composite cathode material, specifically comprises the steps:
A. cracking is sprayed for kernel: take lithium source, vanadium source, phosphoric acid root by the stoichiometric proportion of phosphoric acid vanadium lithium, add the complexing agent of carbon containing, and mix in deionized water, stir and form colloidal sol, then lithium manganese phosphate powder is added wherein, form suspension-turbid liquid after being uniformly dispersed, cracking of being sprayed in inert atmosphere at 500 ~ 850 DEG C by suspension-turbid liquid, namely obtains the kernel of the mononuclear structure of the coated lithium manganese phosphate of phosphoric acid vanadium lithium after cooling;
B. spraying dry prepares the composite positive pole of multinuclear type nucleocapsid structure: be dissolved in by organic carbon source in deionized water, add obtained kernel wherein, after being uniformly dispersed at 110 ~ 300 DEG C spraying dry, then by gained precursor powder 500 ~ 850 DEG C of calcining 0.5 ~ 24h in non-oxidizing atmosphere, cool with stove and obtain composite positive pole.
The addition of described lithium manganese phosphate is 0.1 ~ 50 times of phosphoric acid vanadium lithium quality;
Described lithium source is the one in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithium lactate, lithium oxalate, lithia and lithium dihydrogen phosphate; Described vanadium source is ammonium metavanadate, vanadic oxide, oxalic acid cross one in vanadyl and vanadium metal; Described phosphoric acid root is the one in phosphoric acid, lithium dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and triammonium phosphate; The complexing agent of described carbon containing is the one in citric acid, oxalic acid, adipic acid, polyethylene glycol, salicylic acid, tartaric acid, EDTA, diethylene triamine pentaacetic acid, hydroxyl EDTA and gluconic acid; Described organic carbon source is the one in oxalic acid, glucose, sucrose, citric acid, tartaric acid, adipic acid, polyethylene glycol, polyvinyl alcohol, fructose and ascorbic acid.
In described step b, the addition of carbon source is that 0.1 ~ 10% of interior nuclear mass calculates by the quality of its carbon containing.
The beneficial effect that the present invention produces is:
The present invention proposes to adopt aerosol spray cracking-spraying dry combination method to prepare a kind of lithium ion battery composite cathode material of multinuclear type nucleocapsid structure, and kernel is the monokaryon particle (LiMnPO of the coated lithium manganese phosphate of phosphoric acid vanadium lithium 4/ Li 3v 2(PO 4) 3).Outer shell material is amorphous carbon, shell and kernel and kernel and interior internuclear gap connect by conductive carbon mesh (organic carbon source added during spraying dry is calcined and formed).Wherein fast-ionic conductor phosphoric acid vanadium lithium coating layer can improve ionic conductivity and the electronics conductance of lithium manganese phosphate; Carbon shell not only can improve the ionic conductivity of electrode material effectively, and wrap up that nano-micro structure that several nanoscale nuclear particle forms can make nano level inner nuclear material uniform particle by monoshell layer be scattered in carbonaceous conductive network, avoid the reunion of nano level inner nuclear material particle, make it in charge and discharge process, maintain dynamic stabilization, and add drawing abillity.By the methods combining of these two kinds of modified phosphate manganese lithiums, the chemical property of material, especially high rate charge-discharge performance and cycle life will be significantly improved.In addition, due to the spherical morphology of phosphoric acid vanadium lithium coating layer and material, make its tap density up to 1.6 ~ 2.0gcm -3, drastically increase the energy density of material.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of nanoscale lithium manganese phosphate in embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of composite positive pole in embodiment 1.
Fig. 3 is the first charge-discharge curve of nanoscale lithium manganese phosphate under 0.1C multiplying power in embodiment 1.
Fig. 4 is the first charge-discharge curve of composite positive pole under 0.1C multiplying power in embodiment 1.
Fig. 5 is the cycle performance of nanoscale lithium manganese phosphate under different multiplying in embodiment 1.
Fig. 6 is the cycle performance of composite positive pole under different multiplying in embodiment 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1:
A. aerosol spray cracking is for kernel: with lithium hydroxide, vanadic oxide, ammonium dihydrogen phosphate, citric acid (adding by the mol ratio 1:1 of citric acid and vanadium) for raw material, add appropriate amount of deionized water, in 70 DEG C of waters bath with thermostatic control, stirring 5h to forming colloidal sol, then pressing LiMnPO 4with Li 3v 2(PO 4) 3mass ratio 2:1 add nanoscale LiMnPO 4powder, ultrasonic disperse is even, and by the 650 DEG C of spraying cracking in inert atmosphere of gained mixture, namely cooling obtains the core LiMnPO of the coated lithium manganese phosphate of phosphoric acid vanadium lithium 4/ Li 3v 2(PO 4) 3.
B. the composite positive pole of multinuclear type nucleocapsid structure is prepared in spraying dry-calcining: be dissolved in deionized water by a certain amount of sucrose (quality of its carbon containing is 5% of inner nuclear material quality), add obtained inner nuclear material wherein, normal temperature magnetic force dispersed with stirring evenly after at 120 DEG C spraying dry, gained precursor powder calcines 8h at 650 DEG C in argon gas atmosphere, cool with stove and obtain composite positive pole, its tap density reaches 1.92g/cm 3.
Embodiment 2:
A. aerosol spray cracking is for kernel: with lithium acetate, ammonium metavanadate, phosphoric acid, oxalic acid (adding by the mol ratio 1.2:1 of oxalic acid and vanadium) for raw material, add appropriate amount of deionized water, in 60 DEG C of waters bath with thermostatic control, stirring 8h to forming colloidal sol, then pressing LiMnPO 4with Li 3v 2(PO 4) 3mass ratio 0.1:1 add nanoscale LiMnPO 4powder, magnetic agitation is uniformly dispersed, and by the 850 DEG C of spraying cracking in inert atmosphere of gained mixture, namely cooling obtains the core LiMnPO of the coated lithium manganese phosphate of phosphoric acid vanadium lithium 4/ Li 3v 2(PO 4) 3.
B. the composite positive pole of multinuclear type nucleocapsid structure is prepared in spraying dry-calcining: be dissolved in deionized water by a certain amount of glucose (quality of its carbon containing is 10% of inner nuclear material quality), add obtained inner nuclear material wherein, normal temperature magnetic force dispersed with stirring evenly after at 300 DEG C spraying dry, gained precursor powder calcines 2h at 700 DEG C in nitrogen atmosphere, cool with stove and obtain composite positive pole, its tap density reaches 1.60g/cm 3.
Embodiment 3:
A. aerosol spray cracking is for kernel: with lithium nitrate, ammonium metavanadate, diammonium hydrogen phosphate, polyethylene glycol (adding by the mol ratio 1.05:1 of polyethylene glycol and vanadium) for raw material, add appropriate amount of deionized water, in 80 DEG C of waters bath with thermostatic control, stirring 5h to forming colloidal sol, then pressing LiMnPO 4with Li 3v 2(PO 4) 3mass ratio 50:1 add nanoscale LiMnPO 4powder, ultrasonic disperse is even, and by the 500 DEG C of spraying cracking in inert atmosphere of gained mixture, namely cooling obtains the core LiMnPO of the coated lithium manganese phosphate of phosphoric acid vanadium lithium 4/ Li 3v 2(PO 4) 3.
B. the composite positive pole of multinuclear type nucleocapsid structure is prepared in spraying dry-calcining: be dissolved in deionized water by a certain amount of polyvinyl alcohol (quality of its carbon containing is 0.1% of inner nuclear material quality), add obtained inner nuclear material wherein, normal temperature magnetic force dispersed with stirring evenly after at 110 DEG C spraying dry, gained precursor powder calcines 0.5h at 850 DEG C in hydrogen atmosphere, cool with stove and obtain composite positive pole, its tap density reaches 2.0g/cm 3.
Embodiment 4:
A. aerosol spray cracking is for kernel: cross vanadyl, triammonium phosphate, EDTA (adding by the mol ratio 0.95:1 of EDTA and vanadium) for raw material with lithium lactate, oxalic acid, add appropriate amount of deionized water, in 75 DEG C of waters bath with thermostatic control, stirring 4h to forming colloidal sol, then pressing LiMnPO 4with Li 3v 2(PO 4) 3mass ratio 10:1 add nanoscale LiMnPO 4powder, ultrasonic disperse is even, and by the 750 DEG C of spraying cracking in inert atmosphere of gained mixture, namely cooling obtains the core LiMnPO of the coated lithium manganese phosphate of phosphoric acid vanadium lithium 4/ Li 3v 2(PO 4) 3.
B. the composite positive pole of multinuclear type nucleocapsid structure is prepared in spraying dry-calcining: be dissolved in deionized water by a certain amount of ascorbic acid (quality of its carbon containing is 2% of inner nuclear material quality), add obtained inner nuclear material wherein, normal temperature magnetic force dispersed with stirring evenly after at 200 DEG C spraying dry, gained precursor powder calcines 24h at 600 DEG C in argon gas atmosphere, cool with stove and obtain composite positive pole, its tap density reaches 1.84g/cm 3.
Although the present invention is described in each preferred embodiment, but the present invention of those skilled in the art's easy understand is not limited to foregoing description, it can be undertaken changing or improving by multiple alternate manner, and does not depart from the spirit and scope illustrated in the claims in the present invention.

Claims (4)

1. a preparation method for lithium ion battery composite cathode material, is characterized in that, specifically comprises the steps:
A. cracking is sprayed for kernel: take lithium source, vanadium source, phosphoric acid root by the stoichiometric proportion of phosphoric acid vanadium lithium, add the complexing agent of carbon containing, and mix in deionized water, stir and form colloidal sol, then lithium manganese phosphate powder is added wherein, form suspension-turbid liquid after being uniformly dispersed, cracking of being sprayed in inert atmosphere at 500 ~ 850 DEG C by suspension-turbid liquid, namely obtains the kernel of the mononuclear structure of the coated lithium manganese phosphate of phosphoric acid vanadium lithium after cooling;
B. spraying dry prepares the composite positive pole of multinuclear type nucleocapsid structure: be dissolved in by organic carbon source in deionized water, add obtained kernel wherein, after being uniformly dispersed at 110 ~ 300 DEG C spraying dry, then by gained precursor powder 500 ~ 850 DEG C of calcining 0.5 ~ 24h in non-oxidizing atmosphere, cool with stove and obtain composite positive pole.
2. preparation method according to claim 1, is characterized in that, the addition of described lithium manganese phosphate is 0.1 ~ 50 times of phosphoric acid vanadium lithium quality.
3. preparation method according to claim 1, is characterized in that, described lithium source is the one in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithium lactate, lithium oxalate, lithia and lithium dihydrogen phosphate; Described vanadium source is ammonium metavanadate, vanadic oxide, oxalic acid cross one in vanadyl and vanadium metal; Described phosphoric acid root is the one in phosphoric acid, lithium dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and triammonium phosphate; The complexing agent of described carbon containing is the one in citric acid, oxalic acid, adipic acid, polyethylene glycol, salicylic acid, tartaric acid, EDTA, diethylene triamine pentaacetic acid, hydroxyl EDTA and gluconic acid; Described organic carbon source is the one in oxalic acid, glucose, sucrose, citric acid, tartaric acid, adipic acid, polyethylene glycol, polyvinyl alcohol, fructose and ascorbic acid.
4. preparation method according to claim 1, is characterized in that, in step b, the addition of carbon source is that 0.1 ~ 10% of interior nuclear mass calculates by the quality of its carbon containing.
CN201510640646.0A 2015-09-30 2015-09-30 Preparation method of lithium ion battery composite cathode material Pending CN105304875A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105895910A (en) * 2016-05-17 2016-08-24 浙江美达瑞新材料科技有限公司 Multi-core structured positive electrode material of lithium ion battery and fabrication method of positive electrode material
CN106602038A (en) * 2017-01-21 2017-04-26 三峡大学 Particle-rod mixed morphology lithium vanadium phosphate/carbon composite cathode material prepared by sol-assisted solvothermal method and preparation method thereof
CN107204428A (en) * 2017-06-16 2017-09-26 中南大学 A kind of method of phosphoric acid vanadium lithium coated lithium ion battery ternary material

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CN102903896A (en) * 2012-10-22 2013-01-30 深圳清华大学研究院 Silicon carbon composite negative electrode material for lithium ion battery as well as preparation method and applications of material
CN103000888A (en) * 2012-11-28 2013-03-27 上海交通大学 Composite anode material LiMnPO4-Li3V2(PO4)3/C for lithium ion battery and preparation method of material
CN103435105A (en) * 2013-08-07 2013-12-11 浙江凯恩电池有限公司 Iron oxide/carbon composite lithium ion battery anode material as well as preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102244263A (en) * 2011-06-15 2011-11-16 中南大学 Lithium ion battery phosphatic composite cathode material and preparation method thereof
CN102903896A (en) * 2012-10-22 2013-01-30 深圳清华大学研究院 Silicon carbon composite negative electrode material for lithium ion battery as well as preparation method and applications of material
CN103000888A (en) * 2012-11-28 2013-03-27 上海交通大学 Composite anode material LiMnPO4-Li3V2(PO4)3/C for lithium ion battery and preparation method of material
CN103435105A (en) * 2013-08-07 2013-12-11 浙江凯恩电池有限公司 Iron oxide/carbon composite lithium ion battery anode material as well as preparation method and application thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105895910A (en) * 2016-05-17 2016-08-24 浙江美达瑞新材料科技有限公司 Multi-core structured positive electrode material of lithium ion battery and fabrication method of positive electrode material
CN105895910B (en) * 2016-05-17 2018-12-14 浙江美达瑞新材料科技有限公司 Anode material for lithium-ion batteries of coenocytism and preparation method thereof
CN106602038A (en) * 2017-01-21 2017-04-26 三峡大学 Particle-rod mixed morphology lithium vanadium phosphate/carbon composite cathode material prepared by sol-assisted solvothermal method and preparation method thereof
CN106602038B (en) * 2017-01-21 2018-04-20 三峡大学 A kind of hot method of colloidal sol secondary solvent prepares grain rod mixing pattern phosphoric acid vanadium lithium/carbon composite anode material and preparation method thereof
CN107204428A (en) * 2017-06-16 2017-09-26 中南大学 A kind of method of phosphoric acid vanadium lithium coated lithium ion battery ternary material

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Application publication date: 20160203