CN102891319A - Preparation method of graphite composite material of lithium ion battery - Google Patents
Preparation method of graphite composite material of lithium ion battery Download PDFInfo
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- CN102891319A CN102891319A CN2012103575393A CN201210357539A CN102891319A CN 102891319 A CN102891319 A CN 102891319A CN 2012103575393 A CN2012103575393 A CN 2012103575393A CN 201210357539 A CN201210357539 A CN 201210357539A CN 102891319 A CN102891319 A CN 102891319A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a preparation method of a graphene composite material of a lithium ion battery, wherein the preparation method comprises the following steps of: preparing graphene oxide; on the basis of taking tin chloride, sodium hydroxide as well as the graphene as raw materials, sequentially adding tin chloride, sodium hydroxide, graphene oxide and deionized water, and mixing and blending, thereby obtaining a mixed solution of graphene oxide and a tin dioxide precursor; transferring the mixed solution into a hydrothermal reaction kettle for reaction, and cleaning a product to be neutral; then soaking the product by use of an HNO3 solution, then filtering out an acid liquid, and then cleaning the product to be neutral by use of deionized water and absolute ethyl alcohol respectively; and collecting precipitation, and sintering after drying, thereby obtaining a graphene-tin dioxide composite material. According to the graphene composite material provided by the invention, two types of graphene and tin dioxide materials with excellent performances are combined perfectly by adopting a specific preparation technology, so that the specific capacity of the material for a lithium battery is increased, the conductivity is improved, the cycling stability is good, and the service life is long.
Description
Technical field
The present invention relates to a kind of graphene composite material preparation method, relate in particular to a kind of preparation method of graphene composite material of lithium ion battery.
Background technology
Lithium ion battery is because its energy density is high, and good cycle has been widely used since its commercialization, has replaced gradually traditional chemical power sources such as lead-acid battery.Particularly along with day by day the highlighting of energy and environment problem, New Energy Industry has obtained increasing attention.
Commercial lithium ion battery negative material is take graphite as main at present, and the graphite cost is low, and wide material sources are suitable for commercialization, but its capacity is lower, and theoretical capacity only is 372 mAh/g, and the application in the field that needs high-energy output is restricted.Metal oxide such as TiO2, SnO
2Deng have very high specific capacity as lithium ion battery negative material.SnO wherein
2Specific capacity is up to 782 mAh/g, but SnO
2Change in volume is up to 200～300% in charge and discharge process as electrode material, and the efflorescence that this can cause electrode causes opening circuit of active material and collector.
Graphene is a kind of cellular two-dimentional carbonaceous new material of periodicity that is formed with hexagonal array by the carbon atom of sp2 hydridization, and the structure that it is special is so that it has a lot of special performances.The report of lithium ion battery negative material has appearred being applied to about Graphene and graphene composite material in recent years, so that its excellent electric conductivity is in the also to some extent development of application of electrochemical field.When but the graphene composite material of appearance is as lithium cell cathode material at present, also have many problems, be not with such as the tool specific area, conductivity is not good enough, and electrochemical lithium storage content does not reach high value, and cycle performance is general.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of graphene composite material of lithium ion battery uses the lithium ion battery of the graphene composite material of the method preparation to have the characteristics such as specific area is high, capacity large, good cycle, long service life.
To achieve these goals, the preparation method of the graphene composite material of a kind of lithium ion battery provided by the invention comprises the steps:
Step 1, the preparation graphene oxide
The preparation of graphene oxide is that the concentrated sulfuric acid solution of graphite, 98wt% was mixed 1: 10 in molar ratio, stirs 30min in ice-water bath, then adds KMnO
4Continue to stir 1 hour, be warming up to subsequently 40 ℃ of stirring reaction 30min; Be 5% H with distilled water with adding a small amount of mass fraction after the reactant liquor dilution
2O
2The aqueous solution filters while hot, successively with mass fraction be 5% the HCl aqueous solution and distilled water washing to neutrality, obtain graphene oxide after 60 ℃ of dryings;
Step 2, mix and blend
Take stannic chloride and NaOH and above-mentioned graphene oxide as raw material, water is solvent, quality (g) in stannic chloride: the quality of NaOH (g): the quality of graphene oxide (g): the ratio of the volume of deionized water (ml) is 1: the ratio of 1-1.5: 0.1-0.3: 20-30, in container, add successively stannic chloride, NaOH, graphene oxide and deionized water, mix and blend 20-40 minute, obtain the mixed solution of graphene oxide and tin ash predecessor;
Step 3, hydro-thermal reaction
The mixed solution that step 2 is got moves in the hydrothermal reaction kettle that liner is polytetrafluoroethylene, carries out hydro-thermal reaction 10-24h, and reaction temperature is 140-180 ℃, and the product of gained is repeatedly extremely neutral with washed with de-ionized water, is 0.1mol/L HNO with concentration again
3Solution soaked 30 minutes, and immersion process is followed mechanical agitation, and then elimination acid solution is cleaned to neutral with deionized water and absolute ethyl alcohol respectively again;
Step 4, drying and sintering
With the last precipitation of collecting of step 3, drying is placed on dried powder body material in the crucible, and 450 ℃ of sintering 0.5h-1h of temperature can obtain Graphene-tin ash composite material under inert gas shielding.
Inert gas described in the step 4 is preferably and is selected from nitrogen, argon gas.
Drying means is preferably described in the step 4: be positioned in the drier, at 70-100 ℃ of lower dry 10-20h
The present invention also provides a kind of graphene composite material of lithium ion battery of above-mentioned any means preparation.
The graphene composite material of the present invention's preparation, owing to having adopted distinctive preparation technology that Graphene and the tin dioxide material of two kinds of function admirables are perfectly gathered together, so that the specific capacity of this material when being used for lithium battery increases, conductivity gets a promotion, good cycling stability, long service life.
Embodiment
Embodiment one
The preparation graphene oxide
The concentrated sulfuric acid solution of graphite, 98wt% was mixed 1: 10 in molar ratio, in ice-water bath, stir 30min, then add an amount of KMnO
4Continue to stir 1 hour, be warming up to subsequently 40 ℃ of stirring reaction 30min; Be 5% H with distilled water with adding a small amount of mass fraction after the reactant liquor dilution
2O
2The aqueous solution filters while hot, successively with mass fraction be 5% the HCl aqueous solution and distilled water washing to neutrality, obtain graphene oxide after 60 ℃ of dryings.
Mix and blend
Take stannic chloride and NaOH and above-mentioned graphene oxide as raw material, water is solvent, quality (g) in stannic chloride: the quality of NaOH (g): the quality of graphene oxide (g): the ratio of the volume of deionized water (ml) is 1: 1: 0.1: 20 ratio, in container, add successively stannic chloride, NaOH, graphene oxide and deionized water, mix and blend 20 minutes obtains the mixed solution of graphene oxide and tin ash predecessor.
Hydro-thermal reaction
The mixed solution that makes is moved in the hydrothermal reaction kettle that liner is polytetrafluoroethylene, carry out hydro-thermal reaction 10h, reaction temperature is 140 ℃, and the product of gained is repeatedly extremely neutral with washed with de-ionized water, is 0.1mol/L HNO with concentration again
3Solution soaked 30 minutes, and immersion process is followed mechanical agitation, and then elimination acid solution is cleaned to neutral with deionized water and absolute ethyl alcohol respectively again.
Drying and sintering
Precipitation with collecting at last is positioned in the drier, at 70 ℃ of lower dry 10h, dried powder body material is placed in the crucible, and 450 ℃ of sintering 0.5h of temperature under nitrogen or argon atmospher protection can obtain Graphene-tin ash composite material.
Embodiment two
The preparation graphene oxide
With embodiment one.
Mix and blend
Take stannic chloride and NaOH and above-mentioned graphene oxide as raw material, water is solvent, quality (g) in stannic chloride: the quality of NaOH (g): the quality of graphene oxide (g): the ratio of the volume of deionized water (ml) is 1: 1.5: 0.3: 30 ratio, in container, add successively stannic chloride, NaOH, graphene oxide and deionized water, mix and blend 40 minutes obtains the mixed solution of graphene oxide and tin ash predecessor.
Hydro-thermal reaction
The mixed solution that makes is moved in the hydrothermal reaction kettle that liner is polytetrafluoroethylene,, carry out hydro-thermal reaction 24h, reaction temperature is 180 ℃, the product of gained is repeatedly extremely neutral with washed with de-ionized water, is 0.1mol/L HNO with concentration again
3Solution soaked 30 minutes, and immersion process is followed mechanical agitation, and then elimination acid solution is cleaned to neutral with deionized water and absolute ethyl alcohol respectively again.
Drying and sintering
Precipitation with collecting at last is positioned in the drier, at 100 ℃ of lower dry 20h, dried powder body material is placed in the crucible, and 450 ℃ of sintering 1h of temperature under nitrogen or argon atmospher protection can obtain Graphene-tin ash composite material.
Comparative example
Adopt tin ash to replace embodiment one and two Graphene-tin ash composite material.
Adopt respectively embodiment one, two and the tin ash of comparative example make the negative plate of same size, again take the lithium sheet as to electrode, electrolyte is the EC(ethyl carbonate ester of 1.5mol/L LiPF6)+the DMC(dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, be assembled into button cell, and under the condition of constant current 0.2C, carry out the cycle performance test.This embodiment one with two material compare with the material of comparative example, first discharge specific capacity has promoted more than 50%, cycle life has improved more than 60%.
Above-described embodiment is several exemplary embodiments of the present invention, is not to limit the present invention, therefore all equivalences of being done with the described structure of claim of the present invention, feature and principle change or modify, all should be included within the protection range of the present invention.
Claims (4)
1. the preparation method of the graphene composite material of a lithium ion battery is characterized in that, comprises the steps:
Step 1, the preparation graphene oxide
The preparation of graphene oxide is that the concentrated sulfuric acid solution of graphite, 98wt% was mixed 1: 10 in molar ratio, stirs 30min in ice-water bath, then adds KMnO
4Continue to stir 1 hour, be warming up to subsequently 40 ℃ of stirring reaction 30min; Be 5% H with distilled water with adding a small amount of mass fraction after the reactant liquor dilution
2O
2The aqueous solution filters while hot, successively with mass fraction be 5% the HCl aqueous solution and distilled water washing to neutrality, obtain graphene oxide after 60 ℃ of dryings;
Step 2, mix and blend
Take stannic chloride and NaOH and above-mentioned graphene oxide as raw material, water is solvent, quality (g) in stannic chloride: the quality of NaOH (g): the quality of graphene oxide (g): the ratio of the volume of deionized water (ml) is 1: the ratio of 1-1.5: 0.1-0.3: 20-30, in container, add successively stannic chloride, NaOH, graphene oxide and deionized water, mix and blend 20-40 minute, obtain the mixed solution of graphene oxide and tin ash predecessor;
Step 3, hydro-thermal reaction
The mixed solution that step 2 is got moves in the hydrothermal reaction kettle that liner is polytetrafluoroethylene, carries out hydro-thermal reaction 10-24h, and reaction temperature is 140-180 ℃, and the product of gained is repeatedly extremely neutral with washed with de-ionized water, is 0.1mol/L HNO with concentration again
3Solution soaked 30 minutes, and immersion process is followed mechanical agitation, and then elimination acid solution is cleaned to neutral with deionized water and absolute ethyl alcohol respectively again;
Step 4, drying and sintering
With the last precipitation of collecting of step 3, drying is placed on dried powder body material in the crucible, and 450 ℃ of sintering 0.5h-1h of temperature can obtain Graphene-tin ash composite material under inert gas shielding.
2. method according to claim 1, its feature exists, and inert gas described in the step 4 is selected from nitrogen, argon gas.
3. method according to claim 1, its feature exists, and drying means described in the step 4 is:
Be positioned in the drier, at 70-100 ℃ of lower dry 10-20h.
4. graphene composite material of the lithium ion battery of method preparation as claimed in claim 1.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103326007A (en) * | 2013-06-25 | 2013-09-25 | 上海交通大学 | Preparation method and application of three-dimensional graphene-based stannic oxide composite material |
| CN103904313A (en) * | 2014-04-15 | 2014-07-02 | 山东省科学院能源研究所 | Preparation method and application of tin oxide-aza graphene aerosol composite material |
| CN103904312A (en) * | 2014-04-15 | 2014-07-02 | 山东省科学院能源研究所 | Preparation method of tin oxide-graphene composite carbon film |
| CN104671232A (en) * | 2013-11-29 | 2015-06-03 | 上海悦达墨特瑞新材料科技有限公司 | Preparation method of graphene and application of prepared graphene |
| CN105140488A (en) * | 2015-09-21 | 2015-12-09 | 江苏津谊新能源科技有限公司 | Anode material for lithium batteries |
| CN105470484A (en) * | 2015-12-04 | 2016-04-06 | 厦门大学 | Preparation method of graphene/stannic oxide composite nanofiber membrane and application |
| CN106299313A (en) * | 2016-10-15 | 2017-01-04 | 成都育芽科技有限公司 | A kind of li-ion electrode composite nano materials and preparation method thereof |
| CN106340633A (en) * | 2016-11-24 | 2017-01-18 | 杭州启澄科技有限公司 | Composite nano material for high performance lithium ion battery and preparation method thereof |
| CN108091844A (en) * | 2017-12-11 | 2018-05-29 | 合肥国轩电池材料有限公司 | A kind of composite cathode material of lithium ion battery stannic oxide/graphene and preparation method thereof |
| TWI632112B (en) * | 2013-12-11 | 2018-08-11 | 安炬科技股份有限公司 | Method for preparing nano graphene sheets |
| CN117038915A (en) * | 2023-08-29 | 2023-11-10 | 文登市金叶实业有限公司 | Preparation method and application of three-dimensional porous tin dioxide graphene composite microsphere |
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| CN102324502A (en) * | 2011-09-14 | 2012-01-18 | 重庆大学 | Preparation method of flower-like tin dioxide and graphene composite material |
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| CN102324502A (en) * | 2011-09-14 | 2012-01-18 | 重庆大学 | Preparation method of flower-like tin dioxide and graphene composite material |
| CN102437321A (en) * | 2011-12-20 | 2012-05-02 | 中国科学院新疆理化技术研究所 | Graphene-TiO2(B) nanotube composite material and preparation method thereof |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103326007B (en) * | 2013-06-25 | 2015-12-09 | 上海交通大学 | The preparation method of three-dimensional graphite thiazolinyl tin dioxide composite material and application thereof |
| CN103326007A (en) * | 2013-06-25 | 2013-09-25 | 上海交通大学 | Preparation method and application of three-dimensional graphene-based stannic oxide composite material |
| CN104671232A (en) * | 2013-11-29 | 2015-06-03 | 上海悦达墨特瑞新材料科技有限公司 | Preparation method of graphene and application of prepared graphene |
| TWI632112B (en) * | 2013-12-11 | 2018-08-11 | 安炬科技股份有限公司 | Method for preparing nano graphene sheets |
| CN103904312B (en) * | 2014-04-15 | 2016-06-29 | 山东省科学院能源研究所 | A kind of preparation method of stannum oxide-Graphene compound carbon film |
| CN103904313A (en) * | 2014-04-15 | 2014-07-02 | 山东省科学院能源研究所 | Preparation method and application of tin oxide-aza graphene aerosol composite material |
| CN103904313B (en) * | 2014-04-15 | 2016-01-20 | 山东省科学院能源研究所 | The preparation method of a kind of tin oxide-nitrogen-doped graphene aerosol composite material and application thereof |
| CN103904312A (en) * | 2014-04-15 | 2014-07-02 | 山东省科学院能源研究所 | Preparation method of tin oxide-graphene composite carbon film |
| CN105140488A (en) * | 2015-09-21 | 2015-12-09 | 江苏津谊新能源科技有限公司 | Anode material for lithium batteries |
| CN105470484A (en) * | 2015-12-04 | 2016-04-06 | 厦门大学 | Preparation method of graphene/stannic oxide composite nanofiber membrane and application |
| CN106299313A (en) * | 2016-10-15 | 2017-01-04 | 成都育芽科技有限公司 | A kind of li-ion electrode composite nano materials and preparation method thereof |
| CN110233256A (en) * | 2016-11-24 | 2019-09-13 | 杭州启澄科技有限公司 | A kind of composite nano materials and preparation method thereof |
| CN106340633B (en) * | 2016-11-24 | 2019-09-06 | 杭州启澄科技有限公司 | A kind of high performance lithium ion battery composite nano materials and preparation method thereof |
| CN106340633A (en) * | 2016-11-24 | 2017-01-18 | 杭州启澄科技有限公司 | Composite nano material for high performance lithium ion battery and preparation method thereof |
| CN110311092A (en) * | 2016-11-24 | 2019-10-08 | 杭州启澄科技有限公司 | A kind of SnO2/ carbon/V2O5Application of/the graphene composite nano material as cell negative electrode material |
| CN110311092B (en) * | 2016-11-24 | 2020-11-27 | 杭州启澄科技有限公司 | SnO (stannic oxide)2carbon/V2O5Application of/graphene composite nano material as battery negative electrode material |
| CN110233256B (en) * | 2016-11-24 | 2020-12-01 | 杭州启澄科技有限公司 | Composite nano material and preparation method thereof |
| CN108091844A (en) * | 2017-12-11 | 2018-05-29 | 合肥国轩电池材料有限公司 | A kind of composite cathode material of lithium ion battery stannic oxide/graphene and preparation method thereof |
| CN117038915A (en) * | 2023-08-29 | 2023-11-10 | 文登市金叶实业有限公司 | Preparation method and application of three-dimensional porous tin dioxide graphene composite microsphere |
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Application publication date: 20130123 |