CN102544489A - Method for preparing graphene-coated olivine type lithium ferric phosphate composite material - Google Patents
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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 who coats the olivine-type composite ferric lithium phosphate material based on Graphene.
Background technology
The LiFePO 4 material of olivine-type structure, the advantage of, Nonpoisonous, non-environmental-pollution cheap because of it and good cycling stability just has been considered to the positive electrode of the lithium ion battery of tool potentiality since coming to light.Method preparing phosphate iron lithium is more, mainly contains solid phase method, hydro thermal method, melten gel-gel method and coprecipitation.But, be exactly poor electric conductivity as lithium ion cell electrode with potential problem of LiFePO4, thereby the high rate performance of battery is poor when causing it to use as electrode material, can't fully play its chemical property.It is a kind of main way of improving its electric conductivity that surface carbon coats.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 promptly in the precursor of product, adds carbonaceous material, and it is reacted therewith.In LiFePO4, introduce material with carbon element and proposed by people such as Ravet at first, they add organic substance in the LiFePO4 precursor mixture, obtain the composite ferric lithium phosphate material that carbon coats after the processing.
Graphene has the two-dimensional crystal lattice structure, and the carbon atom in the plane is with sp
2Hybridized orbit is connected to form the hexagonal lattice structure, and promptly carbon atom is connected with three adjacent carbon atoms through very strong σ key, and the C-C key makes Graphene have good structural rigidity.A remaining p electron orbit is perpendicular to the Graphene plane, and with atom formation π key on every side, the delocalizationization of pi-electron in lattice makes Graphene have favorable conductive, and the electron mobility on the room temperature lower plane is 1.5 * 10
4Cm
2/ Vs considerably beyond the conduction velocity of electronics in general conductor, thereby has wide potential application space in the middle of microelectronics, space flight military project, energy storing device, nano electron device, nano composite material.LiFePO4/graphene composite material not only can be alleviated the bulk effect that the LiFePO4 particle in use produces through Graphene, also the media that moves at a high speed as electronics of the electron hole pair of Graphene capable of using.Mainly be to obtain through physical doping at LiFePO4/Graphene mixture at present, the LiFePO4 and the Graphene that are about to prepare directly mix.For example; At application number is 20091055316.7 to be all to be that the simple physics that adopts is mixed and mixed in 201010146161.3 the one Chinese patent application with application number; And number of patent application is the preparation method who discloses a kind of LiFePO4/graphene composite material in 201110083171.1 the one Chinese patent application; But the method that this patent is employed on the ferric lithium phosphate precursor through chemical vapour deposition technique growth Graphene obtains carbon encapsulated material, and method is complicated, and is wayward; And it is long that high temperature feeds the hydric safe poor performance reaction time, is unfavorable for large-scale industrial production.
Summary of the invention
The object of the invention is exactly to provide a kind of novelty simple and direct in order to overcome the defective that above-mentioned prior art exists, the olivine-type composite ferric lithium phosphate material that coats based on Graphene that can produce in batches and preparation method thereof.
The object of the invention can be realized through following technical scheme:
Select the graphene oxide solution materials for use; Molysite, phosphate, reducing agent and surfactant are added in the graphene oxide solution; Obtain the presoma mother liquor after adding lithium salts, obtain elementary product after hydro-thermal or the solvent thermal, after washing, filtration, oven dry; Thermal reduction under the protective atmosphere condition obtains the olivine-type composite ferric lithium phosphate material that Graphene coats.
Preparation method based on Graphene coating olivine-type composite ferric lithium phosphate material may further comprise the steps:
(1) preparation graphene oxide dispersion liquid: under the room temperature, take by weighing graphene oxide and join in deionized water or the organic solvent, ultrasonic 10～60min, magnetic agitation 10～30min is mixed with graphene oxide solution;
(2) by following quality than raw materials weighing: the 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 a molysite quality; The quality of surfactant is 1～10 times of lithium salts quality;
(3) under the situation of room temperature magnetic agitation; Molysite, phosphate, reducing agent and surfactant dissolves in deionized water and be added drop-wise in the graphene oxide dispersion liquid; Be dissolved in lithium salts in the deionized water again and be added drop-wise in the above-mentioned mixed solution; Stir 5～15min, move in the autoclave, 120～180 ℃ were heated 1～24 hour;
(4) in autoclave, take out reactant; At rotating speed is centrifugal under 1000～10000r/min; Intersect washing 3～5 times with ethanol and deionized water then, again through 40～60 ℃ of vacuumize 3～10h, under protective atmosphere at 500 ℃～1000 ℃; Annealed 3～10 hours, and promptly prepared based on Graphene and coat the olivine-type composite ferric lithium phosphate material.
The concentration of the graphene oxide solution that the preparation of graphene oxide and deionized water obtains in the step (1) 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 the step (1) is N, dinethylformamide, 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 the 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 the 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 the sodium borohydride.
Described surfactant is one or more in polyethylene glycol, polyvinyl alcohol or the softex kw.
Protective atmosphere described in the step (4) is that nitrogen, argon gas, hydrogen or wherein any both or three are in the gaseous mixture of any ratio or the mixed atmosphere of inert gas and reducing gas.
Compared with prior art; The invention has the advantages that original position synthesizing olivine type structure lithium iron phosphate/graphene composite material in liquid phase; LiFePO4 is in the growth of Graphene surface in situ in the composite material, not only can realize uniform mixing between the two, and have adhesion preferably; Greatly reduce the contact resistance between LiFePO4 and Graphene, improved the electric conductivity of material itself greatly.
Description of drawings
Fig. 1 is scanning electron microscopy (SEM) collection of illustrative plates of the composite ferric lithium phosphate material of Graphene coating;
Fig. 2 is X-ray diffraction (XRD) collection of illustrative plates of the composite ferric lithium phosphate material of Graphene coating.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is elaborated.
Accurately weighing 0.175g graphene oxide is measured 35ml N, dinethylformamide solution, and being made into concentration is the graphene oxide organic solution of 5mg/ml; Weighing 1.4g FeSO
47H
2The O-H of O, 0.6g 85%
3PO
4Solution, 3.2g polyethylene glycol and 0.12g ascorbic acid are dissolved in the 10mL deionized water together, are added to then in the graphene oxide organic solution, obtain mixed solution 1; With 0.64g LiOHH
2O is dissolved in the 5mL deionized water, and adds in the above-mentioned mixed liquor 1, obtains mixed solution 2; Join mixed solution 2 in the autoclave, reaction 15h under 180 ℃, and through centrifugal, washing, 60 ℃ of vacuumize 4h obtain primary product, and annealing 10h under 700 ℃ of high-purity argon gas are protected obtains composite material with these primary product.
Embodiment 2
Accurately weighing 0.105g graphene oxide is measured the 35ml deionized water, and being made into concentration is the graphite oxide aqueous solution of 3mg/ml; Weighing 0.7g FeSO
47H
2The O-H of O, 0.3g 85%
3PO
4Solution, 1.6g polyethylene glycol and 0.06g ascorbic acid are dissolved in the 10mL deionized water together, are added to then in the graphene oxide organic solution, obtain mixed solution 1; With 0.32g LiOHH
2O is dissolved in the 5mL deionized water, and adds in the above-mentioned mixed liquor 1, obtains mixed solution 2; Join mixed solution 2 in the autoclave, reaction 10h under 180 ℃, and through centrifugal, washing, 40 ℃ of vacuumize 10h obtain primary product, and annealing 3h under 1000 ℃ of high-purity argon gas are protected obtains composite material with these primary product.
Embodiment 3
Accurately weighing 0.035g graphene oxide takes by weighing 35ml N, dinethylformamide solution, and being made into concentration is the graphene oxide organic solution of 1mg/ml; Weighing 0.35g FeSO47H
2The O-H3PO4 solution of O, 0.15g 85%, 0.8g polyethylene glycol and 0.03g ascorbic acid are dissolved in the 10mL deionized water together, are added to then in the graphene oxide organic solution, obtain mixed solution 1; 0.16g LiOHH2O is dissolved in the 5mL deionized water, and adds in the above-mentioned mixed liquor 1, obtain mixed solution 2; Join mixed solution 2 in the autoclave, react 12h down at 180 ℃, and through centrifugal, washing, 40 ℃ of vacuumize 10h obtain primary product, and the 8h that anneals with these primary product and under 500 ℃ of high-purity argon gas protections obtains composite material.
Embodiment 4
Accurately weighing 0.035g graphene oxide takes by weighing the 35ml ethanol solution, and being made into concentration is the graphene oxide organic solution of 1mg/ml; Weighing 0.035g FeSO47H
2The O-H3PO4 solution of O, 0.015g 85%, 0.08g polyethylene glycol and 0.003g ascorbic acid are dissolved in the 10mL deionized water together, are added to then in the graphene oxide organic solution, obtain mixed solution 1; 0.016g LiOHH2O is dissolved in the 5mL deionized water, and adds in the above-mentioned mixed liquor 1, obtain mixed solution 2; Join mixed solution 2 in the autoclave, react 8h down at 180 ℃, and through centrifugal, washing, 40 ℃ of vacuumize 8h obtain primary product, and annealing 5h under 700 ℃ of high-purity argon gas protections of these primary product is obtained composite material.
Embodiment 5
Accurately weighing 0.035g graphene oxide is measured 35ml N, dinethylformamide solution, and being made into concentration is the graphene oxide organic solution of 1mg/ml; Weighing 3.5g FeSO
47H
2The O-H of O, 0.6g 85%
3PO
4Solution, 6.4g polyvinyl alcohol and 0.12g ascorbic acid are dissolved in the 10mL deionized water together, are added to then in the graphene oxide organic solution, obtain mixed solution 1; With 0.64g LiOHH
2O is dissolved in the 5mL deionized water, and adds in the above-mentioned mixed liquor 1, obtains mixed solution 2; Join mixed solution 2 in the autoclave, reaction 15h under 180 ℃, and through centrifugal, washing, 60 ℃ of vacuumize 4h obtain primary product, and annealing 10h under 700 ℃ of high-purity argon gas are protected obtains composite material with these primary product.
Embodiment 6
Accurately weighing 0.035g graphene oxide is measured 35ml N, N-dimethyl formamide solution, and being made into concentration is the graphene oxide organic solution of 1mg/ml; Weighing 1.4g FeSO
47H
2The O-H of O, 0.6g 85%
3PO
4Solution, 0.64g softex kw and 0.175g sodium borohydride are dissolved in the 10mL deionized water together, are added to then in the graphene oxide organic solution, obtain mixed solution 1; With 0.64g LiOHH
2O is dissolved in the 5mL deionized water, and adds in the above-mentioned mixed liquor 1, obtains mixed solution 2; Join mixed solution 2 in the autoclave, reaction 15h under 180 ℃, and through centrifugal, washing, 60 ℃ of vacuumize 4h obtain primary product, and annealing 10h under 700 ℃ of high-purity argon gas are protected obtains composite material with these primary product.
Embodiment 7
Accurately weighing 0.035g graphene oxide is measured 35ml N, dinethylformamide solution, and being made into concentration is the graphene oxide organic solution of 1mg/ml; Weighing 1.4g FeSO
47H
2The O-H of O, 0.6g 85%
3PO
4Solution, 0.64g softex kw and 0.0014g hydrazine are dissolved in the 10mL deionized water together, are added to then in the graphene oxide organic solution, obtain mixed solution 1; With 0.64g LiOHH
2O is dissolved in the 5mL deionized water, and adds in the above-mentioned mixed liquor 1, obtains mixed solution 2; Join mixed solution 2 in the autoclave, reaction 15h under 180 ℃, and through centrifugal, washing, 60 ℃ of vacuumize 4h obtain primary product, and annealing 10h under 700 ℃ of high-purity argon gas are protected obtains composite material with these primary product.
Embodiment 8
Accurately weighing 0.035g graphene oxide is measured 35ml N, dinethylformamide solution, and being made into concentration is the graphene oxide organic solution of 1mg/ml; Weighing 1.4g FeSO
47H
2The O-H of O, 0.6g 85%
3PO
4Solution, 0.64g softex kw and 0.0014g hydrazine are dissolved in the 10mL deionized water together, are added to then in the graphene oxide organic solution, obtain mixed solution 1; With 0.64g LiOHH
2O is dissolved in the 5mL deionized water, and adds in the above-mentioned mixed liquor 1, obtains mixed solution 2; Join mixed solution 2 in the autoclave, reaction 20h under 120 ℃, and through centrifugal, washing, 60 ℃ of vacuumize 4h obtain primary product, and annealing 10h under 700 ℃ of high pure nitrogens are protected obtains composite material with these primary product.
Embodiment 9
Preparation method based on Graphene coating olivine-type composite ferric lithium phosphate material may further comprise the steps:
(1) preparation graphene oxide dispersion liquid: under the room temperature, take by weighing graphene oxide and join in the deionized water, concentration is 1mg/ml, ultrasonic 10min, and magnetic agitation 10min is mixed with graphene oxide solution;
(2) by following quality than raw materials weighing: the 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, and the concentration of lithium salts is 0.01mol/L, and the quality of reducing agent ascorbic acid is 0.1% of a ferrous sulfate quality; The quality of surfactant polyethylene is 1 times of lithium carbonate quality;
(3) under the situation of room temperature magnetic agitation; Be dissolved in ferrous sulfate, ammonium dihydrogen phosphate, reducing agent ascorbic acid and surfactant polyethylene in the deionized water and be added drop-wise in the graphene oxide dispersion liquid; Be dissolved in lithium carbonate in the deionized water again and be added drop-wise in the above-mentioned mixed solution; Stir 5min, move in the autoclave, 120 ℃ were heated 1 hour;
(4) in autoclave, take out reactant; At rotating speed is centrifugal under the 1000r/min; Intersect washing 3 times with ethanol and deionized water then, again through 40 ℃ of vacuumize 3h, under nitrogen protection atmosphere at 500 ℃; Annealed 3 hours, and promptly prepared based on Graphene and coat the olivine-type composite ferric lithium phosphate material.
Preparation method based on Graphene coating olivine-type composite ferric lithium phosphate material may further comprise the steps:
(1) preparation graphene oxide dispersion liquid: under the room temperature, take by weighing graphene oxide and join in the deionized water, concentration is 3mg/ml, ultrasonic 30min, and magnetic agitation 20min is mixed with graphene oxide solution;
(2) by following quality than raw materials weighing: the 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, and the concentration of lithium salts is 0.1mol/L, and the quality of borane reducing agent sodium hydride is 2% of a molysite quality; The quality of surface active agent polyvinyl alcohol is 3 times of lithium salts quality;
(3) under the situation of room temperature magnetic agitation; Be dissolved in ferric trichloride, ammonium phosphate, borane reducing agent sodium hydride and surface active agent polyvinyl alcohol in the deionized water and be added drop-wise in the graphene oxide dispersion liquid; Be dissolved in lithium phosphate in the deionized water again and be added drop-wise in the above-mentioned mixed solution; Stir 10min, move in the autoclave, 150 ℃ were heated 6 hours;
(4) in autoclave, take out reactant; At rotating speed is centrifugal under the 5000r/min; Intersect washing 4 times with ethanol and deionized water then, again through 50 ℃ of vacuumize 5h, under the protective atmosphere of nitrogen and argon gas at 800 ℃; Annealed 5 hours, and promptly prepared based on Graphene and coat the olivine-type composite ferric lithium phosphate material.
Embodiment 11
Preparation method based on Graphene coating olivine-type composite ferric lithium phosphate material may further comprise the steps:
(1) preparation graphene oxide dispersion liquid: under the room temperature, take by weighing graphene oxide and join N, in the dinethylformamide, concentration is 1mg/ml, ultrasonic 40min, and magnetic agitation 15min is mixed with graphene oxide solution;
(2) by following quality than raw materials weighing: the 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, and the concentration of lithium salts is 0.2mol/L, and the quality of borane reducing agent sodium hydride is 2% of a molysite quality; The quality of surface active agent polyvinyl alcohol is 6 times of lithium salts quality;
(3) under the situation of room temperature magnetic agitation; Molysite, phosphate, reducing agent and surfactant dissolves in deionized water and be added drop-wise in the graphene oxide dispersion liquid; Be dissolved in lithium salts in the deionized water again and be added drop-wise in the above-mentioned mixed solution; Stir 10min, move in the autoclave, 150 ℃ were heated 18 hours;
(4) in autoclave, take out reactant; At rotating speed is centrifugal under the 8000r/min; Intersect washing 4 times with ethanol and deionized water then, again through 60 ℃ of vacuumize 10h, under protective atmosphere at 800 ℃; Annealed 8 hours, and promptly prepared based on Graphene and coat the olivine-type composite ferric lithium phosphate material.
Embodiment 12
Preparation method based on Graphene coating olivine-type composite ferric lithium phosphate material may further comprise the steps:
(1) preparation graphene oxide dispersion liquid: under the room temperature, take by weighing graphene oxide and join in the absolute ethyl alcohol, concentration is 5mg/ml, ultrasonic 60min, and magnetic agitation 30min is mixed with graphene oxide solution;
(2) by following quality than raw materials weighing: the 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, and the concentration of lithium salts is 1mol/L, and the quality of reducing agent ascorbic acid is 5% of a molysite quality; The quality of surfactant softex kw is 10 times of lithium salts quality;
(3) under the situation of room temperature magnetic agitation; Ferrous oxalate, ammonium dihydrogen phosphate, reducing agent and surfactant dissolves in deionized water and be added drop-wise in the graphene oxide dispersion liquid; Be dissolved in lithium salts in the deionized water again and be added drop-wise in the above-mentioned mixed solution; Stir 15min, move in the autoclave, 180 ℃ were heated 24 hours;
(4) in autoclave, take out reactant; At rotating speed is centrifugal under the 10000r/min; Intersect washing 5 times with ethanol and deionized water then, again through 60 ℃ of vacuumize 10h, under protective atmosphere at 1000 ℃; Annealed 10 hours, and promptly prepared based on Graphene and coat the olivine-type composite ferric lithium phosphate material.
Claims (9)
1. coat the preparation method of olivine-type composite ferric lithium phosphate material based on Graphene, it is characterized in that this method may further comprise the steps:
(1) preparation graphene oxide dispersion liquid: under the room temperature, take by weighing graphene oxide and join in deionized water or the organic solvent, ultrasonic 10～60min, magnetic agitation 10～30min is mixed with graphene oxide solution;
(2) by following quality than raw materials weighing: the 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 a molysite quality; The quality of surfactant is 1～10 times of lithium salts quality;
(3) under the situation of room temperature magnetic agitation; Molysite, phosphate, reducing agent and surfactant dissolves in deionized water and be added drop-wise in the graphene oxide dispersion liquid; Be dissolved in lithium salts in the deionized water again and be added drop-wise in the above-mentioned mixed solution; Stir 5～15min, move in the autoclave, 120～180 ℃ were heated 1～24 hour;
(4) in autoclave, take out reactant; At rotating speed is centrifugal under 1000～10000r/min; Intersect washing 3～5 times with ethanol and deionized water then, again through 40～60 ℃ of vacuumize 3～10h, under protective atmosphere at 500 ℃～1000 ℃; Annealed 3～10 hours, and promptly prepared based on Graphene and coat the olivine-type composite ferric lithium phosphate material.
2. the preparation method who coats the olivine-type composite ferric lithium phosphate material based on Graphene according to claim 1; It is characterized in that; The concentration of the graphene oxide solution that the preparation of graphene oxide and deionized water obtains in the step (1) 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 coating olivine-type composite ferric lithium phosphate material according to claim 1 is characterized in that the organic solvent described in the step (1) is N, dinethylformamide, 95% ethanol or absolute ethyl alcohol.
4. the preparation method who coats the olivine-type composite ferric lithium phosphate material based on Graphene 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 who coats the olivine-type composite ferric lithium phosphate material based on Graphene 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 the ammonium phosphate, and phosphatic concentration is 0.01～1mol/L.
6. the preparation method who coats the olivine-type composite ferric lithium phosphate material based on Graphene according to claim 1; It is characterized in that; Described lithium salts is selected from one or more in lithium hydroxide, lithium carbonate or the lithium phosphate, and the concentration of lithium salts is 0.01～1mol/L.
7. the preparation method based on Graphene coating 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 the sodium borohydride.
8. the preparation method based on Graphene coating olivine-type composite ferric lithium phosphate material according to claim 1 is characterized in that described surfactant is one or more in polyethylene glycol, polyvinyl alcohol or the softex kw.
9. the preparation method who coats the olivine-type composite ferric lithium phosphate material based on Graphene according to claim 1; It is characterized in that the protective atmosphere described in the step (4) is that nitrogen, argon gas, hydrogen or wherein any both or three are in the gaseous mixture of any ratio or the mixed atmosphere of inert gas and reducing gas.
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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 |
-
2012
- 2012-01-09 CN CN201210005494.3A patent/CN102544489B/en not_active Expired - Fee Related
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 |
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| CN106531998A (en) * | 2016-11-23 | 2017-03-22 | 深圳市山木新能源科技股份有限公司 | Cathode material for lithium ion battery and preparation method thereof |
| CN108199019A (en) * | 2017-12-25 | 2018-06-22 | 深圳市山木新能源科技股份有限公司 | Multi-layer graphene/LiFePO4 intercalation composite material preparation method and application |
| CN108448105A (en) * | 2018-05-16 | 2018-08-24 | 苏州大学 | A kind of preparation method of lithium ion battery anode material lithium iron phosphate/redox graphene |
| CN109167027A (en) * | 2018-08-20 | 2019-01-08 | 合肥国轩电池材料有限公司 | A kind of redox graphene/carbon coating/composite ferric lithium phosphate material preparation method |
| CN111293294A (en) * | 2020-02-22 | 2020-06-16 | 电子科技大学 | Method for synthesizing lithium iron phosphate/graphene composite material by template method in one step |
| CN111293294B (en) * | 2020-02-22 | 2022-04-22 | 电子科技大学 | Method for synthesizing lithium iron phosphate/graphene composite material by template method in one step |
| CN115636401A (en) * | 2022-08-26 | 2023-01-24 | 北京工业大学 | Preparation method of phosphorylated nano-iron |
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