CN102544489B - Method for preparing graphene-coated olivine type lithium ferric phosphate composite material - Google Patents
Method for preparing graphene-coated olivine type lithium ferric phosphate composite material Download PDFInfo
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Abstract
The invention relates to a method for preparing a graphene-coated olivine type lithium ferric phosphate composite material. The method comprises the following steps of: under the circumstances of magnetic stirring at room temperature, dissolving a ferric salt, a phosphate, a reductant and a surfactant into deionized water to form a mixture, and dropwise adding the mixture into a graphene oxide dispersion solution to form a mixed solution; dissolving a lithium salt into deionized water to form a mixture, and dropwise adding the mixture into the mixed solution; and stirring, reacting, centrifuging, washing, carrying out vacuum drying and annealing to obtain a product. Compared with the prior art, according to the invention, the olivine type lithium ferric phosphate/graphene composite material is compounded in situ in a liquid phase, the lithium ferric phosphate in the composite material grows on the surface of the graphene in situ, the even mixing between the lithium ferric phosphate and the graphene can be realized, and the lithium ferric phosphate and the graphene have a better bonding force, so that the contact resistance between the lithium ferric phosphate and the graphene is greatly lowered, and the conductive properties of the composite material are greatly improved.
Description
Technical field
The present invention relates to a kind of preparation method of composite material, especially relate to a kind of preparation method based on graphene coated olivine-type composite ferric lithium phosphate material.
Background technology
The LiFePO 4 material of olivine-type structure, because it is cheap, the advantage of Nonpoisonous, non-environmental-pollution and good cycling stability has just been considered to the positive electrode of the lithium ion battery of tool potentiality since being found.The preparation method of LiFePO4 is more, mainly contains solid phase method, hydro thermal method, melten gel-gel method and coprecipitation.But, as lithium ion cell electrode, by potential problem of LiFePO4, be exactly poor electric conductivity, thereby while causing it to use as electrode material, the high rate performance of battery is poor, cannot fully play its chemical property.Material with carbon-coated surface is a kind of main way of improving its electric conductivity.At present, the method for coated with carbon mainly contains two kinds, and a kind of is carbonaceous material and raw material mixed calcining in certain proportion, another kind ofly in the precursor of product, adds carbonaceous material, and it is reacted therewith.In LiFePO4, introduce material with carbon element and by people such as Ravet, proposed at first, they add organic substance in LiFePO4 precursor mixture, obtain the coated composite ferric lithium phosphate material of carbon after processing.
Graphene has Colloidal particles, and the carbon atom in plane is with sp
2hybridized orbit is connected to form hexagonal lattice structure, and carbon atom is connected with three adjacent carbon atoms by very strong σ key, and C-C key makes Graphene have good structural rigidity.A remaining p electron orbit, perpendicular to Graphene plane, forms π key with atom around, and the delocalization of pi-electron in lattice, makes Graphene have good conduction, and the electron mobility on room temperature lower plane is 1.5 * 10
4cm
2/ Vs, the conduction velocity considerably beyond electronics in general conductor, thereby in the middle of microelectronics, space flight military project, energy storing device, nano electron device, nano composite material, have wide potential application space.LiFePO4/graphene composite material not only can be alleviated the bulk effect that lithium iron phosphate particles in use produces by Graphene, the medium that also can utilize the electron hole pair of Graphene to move at a high speed as electronics.At LiFePO4/Graphene mixture, be mainly to obtain by physical doping at present, the LiFePO4 and the Graphene that are about to prepare directly mix.For example, application number be 20091055316.7 and the application number Chinese patent application that is 201010146161.3 in be all that the simple physical doping adopting mixes, and a kind of preparation method of LiFePO4/graphene composite material is disclosed in the Chinese patent application that number of patent application is 201110083171.1, but this patent adopts the method by chemical vapour deposition technique growing graphene on ferric lithium phosphate precursor to obtain carbon encapsulated material, method is complicated, wayward, and it is long that high temperature passes into the hydric safe poor performance reaction time, be unfavorable for large-scale industrial production.
Summary of the invention
Object of the present invention is exactly to provide a kind of novelty simple and direct in order to overcome the defect of above-mentioned prior art existence, olivine-type composite ferric lithium phosphate material based on graphene coated can be mass and preparation method thereof.
Object of the present invention can be achieved through the following technical solutions:
Select graphene oxide solution materials; molysite, phosphate, reducing agent and surfactant are added in graphene oxide solution; after adding lithium salts, obtain presoma mother liquor; after hydro-thermal or solvent heat, obtain Primary product; after washing, filtration, drying; thermal reduction under protective atmosphere condition, the olivine-type composite ferric lithium phosphate material of acquisition graphene coated.
Preparation method based on graphene coated olivine-type composite ferric lithium phosphate material, comprises the following steps:
(1) prepare graphene oxide dispersion liquid: under room temperature, take graphene oxide and join in deionized water or organic solvent, ultrasonic 10～60min, magnetic agitation 10～30min, is mixed with graphene oxide solution;
(2) by following quality than raw materials weighing: molysite quality is 1～100 times of graphene oxide quality, and lithium salts, molysite and phosphatic mol ratio are (1～3): (1～3): 1, the quality of reducing agent is 0.1%～5% of molysite quality; The quality of surfactant is 1～10 times of lithium salts quality;
(3) in the situation that of room temperature magnetic agitation, molysite, phosphate, reducing agent and surfactant dissolves in deionized water and be added drop-wise in graphene oxide dispersion liquid, again lithium salts be dissolved in deionized water and be added drop-wise in above-mentioned mixed solution, stir 5～15min, in immigration autoclave, 120～180 ℃ are heated 1～24 hour;
(4) in autoclave, take out reactant; at rotating speed, be centrifugal under 1000～10000r/min; then use ethanol and deionized water cross washing 3～5 times; again through 40～60 ℃ of vacuumize 3～10h; under protective atmosphere at 500 ℃～1000 ℃; anneal 3～10 hours, prepare based on graphene coated olivine-type composite ferric lithium phosphate material.
The concentration of the graphene oxide solution that in step (1), graphene oxide and deionized water preparation obtain is 1～3mg/ml, and the concentration of the graphene oxide solution that graphene oxide and organic solvent preparation obtain is 1～5mg/ml.
Organic solvent described in step (1) is DMF, 95% ethanol or absolute ethyl alcohol.
Described molysite is the mixture of one or more any ratios in ferrous sulfate, ferric sulfate, ferric trichloride, frerrous chloride, ferric nitrate, ferrous nitrate, ferric acetate, ferrous acetate, ferric oxalate, ferrous oxalate, ironic citrate or ferrous sulfate two ammoniums, and the concentration of molysite is 0.01～1mol/L.
Described phosphate is selected from one or more in ammonium dihydrogen phosphate, diammonium hydrogen phosphate or ammonium phosphate, and phosphatic concentration is 0.01～1mol/L.
Described lithium salts is selected from one or more in lithium hydroxide, lithium carbonate or lithium phosphate, and the concentration of lithium salts is 0.01～1mol/L.
Described reducing agent is selected from one or more in ascorbic acid, hydrazine or sodium borohydride.
Described surfactant is one or more in polyethylene glycol, polyvinyl alcohol or softex kw.
Protective atmosphere described in step (4) be nitrogen, argon gas, hydrogen or wherein any both or three in the mixed atmosphere of the gaseous mixture of any ratio or inert gas and reducing gas.
Compared with prior art, the invention has the advantages that at liquid phase situ synthesizing olivine type structure lithium iron phosphate/graphene composite material, in composite material, LiFePO4 is to grow at Graphene surface in situ, not only can realize uniform mixing between the two, and there is good adhesion, greatly reduce the contact resistance between LiFePO4 and Graphene, greatly improved the electric conductivity of material itself.
Accompanying drawing explanation
Fig. 1 is scanning electron microscopy (SEM) collection of illustrative plates of the composite ferric lithium phosphate material of graphene coated;
Fig. 2 is X-ray diffraction (XRD) collection of illustrative plates of the composite ferric lithium phosphate material of graphene coated.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
Accurately weigh 0.175g graphene oxide, measure 35ml DMF solution, being made into concentration is the graphene oxide organic solution of 5mg/ml; Weigh 1.4g FeSO
47H
2the O-H of O, 0.6g 85%
3pO
4solution, 3.2g polyethylene glycol and 0.12g ascorbic acid, be dissolved in 10mL deionized water together, is then added in graphene oxide organic solution, obtains mixed solution 1; By 0.64g LiOHH
2o is dissolved in 5mL deionized water, and adds in above-mentioned mixed liquor 1, obtains mixed solution 2; Mixed solution 2 is joined in autoclave, at 180 ℃, react 15h, and through centrifugal, washing, 60 ℃ of vacuumize 4h obtain primary product, and 10h that these primary product are annealed under 700 ℃ of high-purity argon gas protections obtains composite material.
Embodiment 2
Accurately weigh 0.105g graphene oxide, measure 35ml deionized water, being made into concentration is the graphite oxide aqueous solution of 3mg/ml; Weigh 0.7g FeSO
47H
2the O-H of O, 0.3g 85%
3pO
4solution, 1.6g polyethylene glycol are dissolved in 10mL deionized water together with 0.06g ascorbic acid, are then added in graphene oxide organic solution, obtain mixed solution 1; By 0.32g LiOHH
2o is dissolved in 5mL deionized water, and adds in above-mentioned mixed liquor 1, obtains mixed solution 2; Mixed solution 2 is joined in autoclave, at 180 ℃, react 10h, and through centrifugal, washing, 40 ℃ of vacuumize 10h obtain primary product, and 3h that these primary product are annealed under 1000 ℃ of high-purity argon gas protections obtains composite material.
Embodiment 3
Accurately weigh 0.035g graphene oxide, take 35ml DMF solution, being made into concentration is the graphene oxide organic solution of 1mg/ml; Weigh 0.35g FeSO47H
2the O-H3PO4 solution of O, 0.15g 85%, 0.8g polyethylene glycol and 0.03g ascorbic acid, be dissolved in 10mL deionized water together, is then added in graphene oxide organic solution, obtains mixed solution 1; 0.16g LiOHH2O is dissolved in 5mL deionized water, and adds in above-mentioned mixed liquor 1, obtain mixed solution 2; Mixed solution 2 is joined in autoclave, at 180 ℃, react 12h, and through centrifugal, washing, 40 ℃ of vacuumize 10h obtain primary product, and the 8h that anneals by these primary product and under 500 ℃ of high-purity argon gas protections obtains composite material.
Embodiment 4
Accurately weigh 0.035g graphene oxide, take 35ml ethanol solution, being made into concentration is the graphene oxide organic solution of 1mg/ml; Weigh 0.035g FeSO47H
2the O-H3PO4 solution of O, 0.015g 85%, 0.08g polyethylene glycol and 0.003g ascorbic acid, be dissolved in 10mL deionized water together, is then added in graphene oxide organic solution, obtains mixed solution 1; 0.016g LiOHH2O is dissolved in 5mL deionized water, and adds in above-mentioned mixed liquor 1, obtain mixed solution 2; Mixed solution 2 is joined in autoclave, at 180 ℃, react 8h, and through centrifugal, washing, 40 ℃ of vacuumize 8h obtain primary product, and the lower annealing 5h of 700 ℃ of high-purity argon gas protections of these primary product is obtained to composite material.
Embodiment 5
Accurately weigh 0.035g graphene oxide, measure 35ml DMF solution, being made into concentration is the graphene oxide organic solution of 1mg/ml; Weigh 3.5g FeSO
47H
2the O-H of O, 0.6g 85%
3pO
4solution, 6.4g polyvinyl alcohol and 0.12g ascorbic acid, be dissolved in 10mL deionized water together, is then added in graphene oxide organic solution, obtains mixed solution 1; By 0.64g LiOHH
2o is dissolved in 5mL deionized water, and adds in above-mentioned mixed liquor 1, obtains mixed solution 2; Mixed solution 2 is joined in autoclave, at 180 ℃, react 15h, and through centrifugal, washing, 60 ℃ of vacuumize 4h obtain primary product, and 10h that these primary product are annealed under 700 ℃ of high-purity argon gas protections obtains composite material.
Embodiment 6
Accurately weigh 0.035g graphene oxide, measure 35ml N, N-dimethyl formamide solution, being made into concentration is the graphene oxide organic solution of 1mg/ml; Weigh 1.4g FeSO
47H
2the O-H of O, 0.6g 85%
3pO
4solution, 0.64g softex kw and 0.175g sodium borohydride, be dissolved in 10mL deionized water together, is then added in graphene oxide organic solution, obtains mixed solution 1; By 0.64g LiOHH
2o is dissolved in 5mL deionized water, and adds in above-mentioned mixed liquor 1, obtains mixed solution 2; Mixed solution 2 is joined in autoclave, at 180 ℃, react 15h, and through centrifugal, washing, 60 ℃ of vacuumize 4h obtain primary product, and 10h that these primary product are annealed under 700 ℃ of high-purity argon gas protections obtains composite material.
Embodiment 7
Accurately weigh 0.035g graphene oxide, measure 35ml DMF solution, being made into concentration is the graphene oxide organic solution of 1mg/ml; Weigh 1.4g FeSO
47H
2the O-H of O, 0.6g 85%
3pO
4solution, 0.64g softex kw and 0.0014g hydrazine, be dissolved in 10mL deionized water together, is then added in graphene oxide organic solution, obtains mixed solution 1; By 0.64g LiOHH
2o is dissolved in 5mL deionized water, and adds in above-mentioned mixed liquor 1, obtains mixed solution 2; Mixed solution 2 is joined in autoclave, at 180 ℃, react 15h, and through centrifugal, washing, 60 ℃ of vacuumize 4h obtain primary product, and 10h that these primary product are annealed under 700 ℃ of high-purity argon gas protections obtains composite material.
Embodiment 8
Accurately weigh 0.035g graphene oxide, measure 35ml DMF solution, being made into concentration is the graphene oxide organic solution of 1mg/ml; Weigh 1.4g FeSO
47H
2the O-H of O, 0.6g 85%
3pO
4solution, 0.64g softex kw and 0.0014g hydrazine, be dissolved in 10mL deionized water together, is then added in graphene oxide organic solution, obtains mixed solution 1; By 0.64g LiOHH
2o is dissolved in 5mL deionized water, and adds in above-mentioned mixed liquor 1, obtains mixed solution 2; Mixed solution 2 is joined in autoclave, at 120 ℃, react 20h, and through centrifugal, washing, 60 ℃ of vacuumize 4h obtain primary product, and 10h that these primary product are annealed under 700 ℃ of high pure nitrogen protections obtains composite material.
Embodiment 9
Preparation method based on graphene coated olivine-type composite ferric lithium phosphate material, comprises the following steps:
(1) prepare graphene oxide dispersion liquid: under room temperature, take graphene oxide and join in deionized water, concentration is 1mg/ml, ultrasonic 10min, magnetic agitation 10min, is mixed with graphene oxide solution;
(2) by following quality than raw materials weighing: ferrous sulfate quality is 1 times of graphene oxide quality, the mol ratio of lithium carbonate, ferrous sulfate and ammonium dihydrogen phosphate is 1: 1: 1, the concentration of molysite is 0.01mol/L, phosphatic concentration is 0.01mol/L, the concentration of lithium salts is 0.01mol/L, and the quality of reducing agent ascorbic acid is 0.1% of ferrous sulfate quality; The quality of surfactant polyethylene is 1 times of lithium carbonate quality;
(3) in the situation that of room temperature magnetic agitation, ferrous sulfate, ammonium dihydrogen phosphate, reducing agent ascorbic acid and surfactant polyethylene are dissolved in deionized water and are added drop-wise in graphene oxide dispersion liquid, again lithium carbonate be dissolved in deionized water and be added drop-wise in above-mentioned mixed solution, stir 5min, in immigration autoclave, 120 ℃ are heated 1 hour;
(4) in autoclave, take out reactant; at rotating speed, be centrifugal under 1000r/min; then use ethanol and deionized water cross washing 3 times; again through 40 ℃ of vacuumize 3h; under nitrogen protection atmosphere at 500 ℃; anneal 3 hours, prepare based on graphene coated olivine-type composite ferric lithium phosphate material.
Embodiment 10
Preparation method based on graphene coated olivine-type composite ferric lithium phosphate material, comprises the following steps:
(1) prepare graphene oxide dispersion liquid: under room temperature, take graphene oxide and join in deionized water, concentration is 3mg/ml, ultrasonic 30min, magnetic agitation 20min, is mixed with graphene oxide solution;
(2) by following quality than raw materials weighing: ferric trichloride quality is 10 times of graphene oxide quality, the mol ratio of lithium phosphate, ferric trichloride and ammonium phosphate is 2: 3: 1, the concentration of molysite is 0.05mol/L, phosphatic concentration is 0.08mol/L, the concentration of lithium salts is 0.1mol/L, and the quality of borane reducing agent sodium hydride is 2% of molysite quality; The quality of surface active agent polyvinyl alcohol is 3 times of lithium salts quality;
(3) in the situation that of room temperature magnetic agitation, ferric trichloride, ammonium phosphate, borane reducing agent sodium hydride and surface active agent polyvinyl alcohol are dissolved in deionized water and are added drop-wise in graphene oxide dispersion liquid, again lithium phosphate be dissolved in deionized water and be added drop-wise in above-mentioned mixed solution, stir 10min, in immigration autoclave, 150 ℃ are heated 6 hours;
(4) in autoclave, take out reactant; at rotating speed, be centrifugal under 5000r/min; then use ethanol and deionized water cross washing 4 times; again through 50 ℃ of vacuumize 5h; under the protective atmosphere of nitrogen and argon gas at 800 ℃; anneal 5 hours, prepare based on graphene coated olivine-type composite ferric lithium phosphate material.
Embodiment 11
Preparation method based on graphene coated olivine-type composite ferric lithium phosphate material, comprises the following steps:
(1) prepare graphene oxide dispersion liquid: under room temperature, take graphene oxide and join in DMF, concentration is 1mg/ml, ultrasonic 40min, magnetic agitation 15min, is mixed with graphene oxide solution;
(2) by following quality than raw materials weighing: ferric nitrate quality is 10 times of graphene oxide quality, the mol ratio of lithium hydroxide, ferric nitrate and ammonium phosphate is 1: 3: 1, the concentration of molysite is 0.1mol/L, phosphatic concentration is 0.5mol/L, the concentration of lithium salts is 0.2mol/L, and the quality of borane reducing agent sodium hydride is 2% of molysite quality; The quality of surface active agent polyvinyl alcohol is 6 times of lithium salts quality;
(3) in the situation that of room temperature magnetic agitation, molysite, phosphate, reducing agent and surfactant dissolves in deionized water and be added drop-wise in graphene oxide dispersion liquid, again lithium salts be dissolved in deionized water and be added drop-wise in above-mentioned mixed solution, stir 10min, in immigration autoclave, 150 ℃ are heated 18 hours;
(4) in autoclave, take out reactant; at rotating speed, be centrifugal under 8000r/min; then use ethanol and deionized water cross washing 4 times; again through 60 ℃ of vacuumize 10h; under protective atmosphere at 800 ℃; anneal 8 hours, prepare based on graphene coated olivine-type composite ferric lithium phosphate material.
Embodiment 12
Preparation method based on graphene coated olivine-type composite ferric lithium phosphate material, comprises the following steps:
(1) prepare graphene oxide dispersion liquid: under room temperature, take graphene oxide and join in absolute ethyl alcohol, concentration is 5mg/ml, ultrasonic 60min, magnetic agitation 30min, is mixed with graphene oxide solution;
(2) by following quality than raw materials weighing: ferrous oxalate quality is 100 times of graphene oxide quality, the mol ratio of lithium hydroxide, ferrous oxalate and ammonium dihydrogen phosphate is 3: 2: 1, the concentration of molysite is 1mol/L, phosphatic concentration is 1mol/L, the concentration of lithium salts is 1mol/L, and the quality of reducing agent ascorbic acid is 5% of molysite quality; The quality of surfactant softex kw is 10 times of lithium salts quality;
(3) in the situation that of room temperature magnetic agitation, ferrous oxalate, ammonium dihydrogen phosphate, reducing agent and surfactant dissolves in deionized water and be added drop-wise in graphene oxide dispersion liquid, again lithium salts be dissolved in deionized water and be added drop-wise in above-mentioned mixed solution, stir 15min, in immigration autoclave, 180 ℃ are heated 24 hours;
(4) in autoclave, take out reactant; at rotating speed, be centrifugal under 10000r/min; then use ethanol and deionized water cross washing 5 times; again through 60 ℃ of vacuumize 10h; under protective atmosphere at 1000 ℃; anneal 10 hours, prepare based on graphene coated olivine-type composite ferric lithium phosphate material.
Claims (8)
1. the preparation method based on graphene coated olivine-type composite ferric lithium phosphate material, is characterized in that, the method comprises the following steps:
(1) prepare graphene oxide dispersion liquid: under room temperature, take graphene oxide and join in deionized water or organic solvent, ultrasonic 10～60min, magnetic agitation 10～30min, is mixed with graphene oxide solution;
(2) by following quality than raw materials weighing: molysite quality is 1～100 times of graphene oxide quality, and lithium salts, molysite and phosphatic mol ratio are (1～3) ︰ (1～3) ︰ 1, and the quality of reducing agent is 0.1%～5% of molysite quality; The quality of surfactant is 1～10 times of lithium salts quality;
(3) in the situation that of room temperature magnetic agitation, molysite, phosphate, reducing agent and surfactant dissolves in deionized water and be added drop-wise in graphene oxide dispersion liquid, again lithium salts be dissolved in deionized water and be added drop-wise in graphene oxide dispersion liquid, stir 5～15min, in immigration autoclave, 120～180 ℃ are heated 1～24 hour;
(4) in autoclave, take out reactant, at rotating speed, be centrifugal under 1000～10000r/min, then use ethanol and deionized water cross washing 3～5 times, again through 40～60 ℃ of vacuumize 3～10h, under protective atmosphere at 500 ℃～1000 ℃, anneal 3～10 hours, prepare based on graphene coated olivine-type composite ferric lithium phosphate material;
Described surfactant is one or more in polyethylene glycol, polyvinyl alcohol or softex kw.
2. the preparation method based on graphene coated olivine-type composite ferric lithium phosphate material according to claim 1, it is characterized in that, the concentration of the graphene oxide solution that in step (1), graphene oxide and deionized water preparation obtain is 1～3mg/ml, and the concentration of the graphene oxide solution that graphene oxide and organic solvent preparation obtain is 1～5mg/ml.
3. the preparation method based on graphene coated olivine-type composite ferric lithium phosphate material according to claim 1, is characterized in that, the organic solvent described in step (1) is DMF, 95% ethanol or absolute ethyl alcohol.
4. the preparation method based on graphene coated olivine-type composite ferric lithium phosphate material according to claim 1, it is characterized in that, described molysite is the mixture of one or more any ratios in ferrous sulfate, ferric sulfate, ferric trichloride, frerrous chloride, ferric nitrate, ferrous nitrate, ferric acetate, ferrous acetate, ferric oxalate, ferrous oxalate, ironic citrate or ferrous sulfate two ammoniums, and the concentration of molysite is 0.01～1mol/L.
5. the preparation method based on graphene coated olivine-type composite ferric lithium phosphate material according to claim 1, it is characterized in that, described phosphate is selected from one or more in ammonium dihydrogen phosphate, diammonium hydrogen phosphate or ammonium phosphate, and phosphatic concentration is 0.01～1mol/L.
6. the preparation method based on graphene coated olivine-type composite ferric lithium phosphate material according to claim 1, is characterized in that, described lithium salts is selected from one or more in lithium carbonate or lithium phosphate, and the concentration of lithium salts is 0.01～1mol/L.
7. the preparation method based on graphene coated olivine-type composite ferric lithium phosphate material according to claim 1, is characterized in that, described reducing agent is selected from one or more in ascorbic acid, hydrazine or sodium borohydride.
8. the preparation method based on graphene coated olivine-type composite ferric lithium phosphate material according to claim 1; it is characterized in that, the protective atmosphere described in step (4) be nitrogen, argon gas, hydrogen or wherein any both or three in the mixed atmosphere of the gaseous mixture of any ratio or inert gas and reducing gas.
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| CN102044666A (en) * | 2010-11-19 | 2011-05-04 | 杭州电子科技大学 | Method for preparing lithium iron phosphate composite material for lithium cells |
| CN102104143A (en) * | 2010-11-29 | 2011-06-22 | 唐品利 | Hydrothermal synthesis method of composite material for high-performance power battery |
| CN102299326A (en) * | 2011-08-04 | 2011-12-28 | 浙江工业大学 | Graphene modified lithium iron phosphate/carbon composite material and its application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102044666A (en) * | 2010-11-19 | 2011-05-04 | 杭州电子科技大学 | Method for preparing lithium iron phosphate composite material for lithium cells |
| CN102104143A (en) * | 2010-11-29 | 2011-06-22 | 唐品利 | Hydrothermal synthesis method of composite material for high-performance power battery |
| CN102299326A (en) * | 2011-08-04 | 2011-12-28 | 浙江工业大学 | Graphene modified lithium iron phosphate/carbon composite material and its application |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108039474A (en) * | 2017-12-13 | 2018-05-15 | 南京红太阳新能源有限公司 | A kind of preparation method of grapheme lithium iron phosphate vanadium oxide cell positive material |
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