CN103833032A - Graphene-based composite cathode material - Google Patents
Graphene-based composite cathode material Download PDFInfo
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- CN103833032A CN103833032A CN201410087435.4A CN201410087435A CN103833032A CN 103833032 A CN103833032 A CN 103833032A CN 201410087435 A CN201410087435 A CN 201410087435A CN 103833032 A CN103833032 A CN 103833032A
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
- Y02E60/13—Energy storage using capacitors
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Abstract
The invention relates to a graphene-based composite cathode material. The graphene-based composite cathode material is characterized in that the graphene is of a porous structure; cathode material particles are evenly distributed between the surface and the sheet; the graphene accounts for 10-50wt% of the composite cathode material. The charge and discharge performances of a cathode active substance can be improved by the graphene with a porous structure; and more diffusion channels also can be provided for transmission of ions. The composite material is simple in preparation technology, and easy to achieve scale expansion, and the graphene-based composite cathode material can be used as an electrode material of a lithium ion battery, a sodium-ion battery, a super capacitor and the like.
Description
Technical field
The present invention relates to grapheme material, the particularly composite negative pole material based on Graphene, belongs to new energy materials technical field.
Background technology
The breakthrough of power battery technology is energy-conservation and the key of new-energy automobile mass-producing application, and power cell energy density at present used is lower, and bulking value is large, and work-ing life is short, and cost is higher, and operating temperature range is narrow, and the duration of charging is long.In order to improve these disadvantageous effects, people carry out the research and development of power cell from aspects such as positive electrode material, negative material, barrier film and electrolytic solution.
Graphene is a kind of novel Two-dimensional Carbon nano material, has broad prospects in energy storage field.Existing a lot of research is devoted to improve by negative electrode active material and Graphene composition matrix material the performance of battery device.The Chinese patent of application publication number CN 103050661 A discloses Graphene composite lithium ion battery cathode material and preparation method thereof, the Chinese patent of application publication number CN 102969508 A discloses carbon in lithium ion battery coating graphite alkene composite material and preparation method thereof and application, the Chinese patent of application publication number CN 103050666 A discloses a kind of preparation method of graphene coated silicon-carbon composite cathode material, the Chinese patent of application publication number CN 103050672 A discloses a kind of preparation method of used as negative electrode of Li-ion battery silicon-graphene composite material, the Chinese patent of application publication number CN 103035888 A discloses silicon, the preparation method of graphene composite material, the Chinese patent of application publication number CN 103035889 A discloses graphene/nanometer silicon compound electric pole piece and preparation method thereof, the Chinese patent of application publication number CN 103022453 A discloses lithium ion battery negative material Si@SiOx/ graphene complex and preparation method thereof, the Chinese patent of application publication number CN 101877405 A discloses the preparation method of lithium titanate-graphene combination electrode material, the Chinese patent of application publication number CN 103022459 A discloses a kind of preparation method of Graphene/lithium titanate composite negative pole material, the Chinese patent of application publication number CN 102874799 A discloses a kind of method that gas phase reduction process is prepared Graphene and composite titania material, the Chinese patent of application publication number CN 101937985 A discloses a kind of graphene/titanium dioxide lithium ion battery cathode material, the Chinese patent of application publication number CN 102891319 A discloses a kind of Graphene-tindioxide composite material and preparation method thereof of lithium ion battery.
But, because making it, the two-dimensional nano laminated structure of Graphene very easily reunites together, and the performance advantage of Graphene can not be brought into play greatly.Recently, people begin one's study and have the preparing high-specific surface area graphene material of pore structure, for example, the Chinese patent of application publication number CN 102115069 A discloses has Graphene of vesicular structure and preparation method thereof, the Chinese patent of application publication number CN 102107868 A discloses a kind of preparation method of porous graphene material, the Chinese patent of application publication number CN 102757036 A discloses the preparation method of porous graphene, the Chinese patent of application publication number CN 102992313 A discloses high-ratio surface Graphene of a kind of mesopore prosperity and preparation method thereof, the Chinese patent of application publication number CN 102849734 A discloses a kind of preparation method of porous graphene, the Chinese patent of application publication number CN 102826542 A discloses a kind of high-ratio surface Activated Graphite alkene with mesopore, Its Preparation Method And Use, the Chinese patent of application publication number CN 103011152 A discloses a kind of grapheme material with vesicular structure and preparation method thereof, the Chinese patent of application publication number CN 102874800 A discloses a kind of activation Graphene of mesopore, its preparation method.
Except research has the preparation method of grapheme material of vesicular structure, existing people starts high-specific surface area, porous graphene material to be applied to energy storage field as active substance.For example, the Chinese patent of application publication number CN 103011143 A discloses Graphene and preparation method thereof, ultracapacitor, the Chinese patent of application publication number CN 102923698 A discloses the preparation method of the three-dimensional porous Graphene of a kind of ultracapacitor, the Chinese patent of application publication number CN 102891014 A discloses Graphene electrodes active substance and method for making and electrode materials and electrode slice and application, the Chinese patent of application publication number CN 102992308 A discloses a kind of Graphene with high specific capacitance and preparation method thereof, the Chinese patent of application publication number CN 101982408 A discloses graphene three-dimensional structure body material and its preparation method and application.
Comprehensively above analysis can be found out, in order to expand the application of Graphene in energy storage field, people begin one's study and have the vesicular structure Graphene of high-specific surface area.But the Graphene that mostly concentrates at present vesicular structure as single-activity material for energy storage field.
Summary of the invention
The object of the invention is to provide a kind of Graphene composite negative pole material, Graphene used has vesicular structure, the pore structure on Graphene surface has improved specific surface area greatly, not only can improve negative electrode active material charge-discharge performance, and can provide more diffusion admittance for the transmission of ion.
Technical solution of the present invention is achieved in that the composite negative pole material based on Graphene, and Graphene is vesicular structure, is uniformly distributed negative material particle between surface and lamella, and the mass percent that Graphene accounts for composite negative pole material is 10～50%.
Described negative material is graphite, MCMB, activated carbon fiber, hard charcoal, Si, Co
3o
4, Fe
3o
4, TiO
2, SnO
2, Li
4ti
5o
12, Na
xnbS
2one in (0.1≤x≤0.9).
Described Graphene specific surface area is 800～2300 m
2/ g.
The preparation method of described composite negative pole material is physical mixed, a kind of during chemical original position is compound or their combination.
Described physical mixed method be stir, a kind of in ultrasonic, ball milling or their combination, in mixing process, can be dry mixed, add solvent wet mixing or be dry mixed-wet mixing combination.Described solvent is deionized water or ethanol.
The step of described physical mixed is as follows: takes Graphene according to mass ratio and puts in mixing vessel, add solvent that Graphene is infiltrated completely, according to mass ratio, negative material is added in mixing vessel and is uniformly dispersed, and dry, obtain composite negative pole material.
Described chemical in-situ compounding process is that Graphene mixes with the raw material of synthetic negative material, forms composite negative pole material in building-up process.
Described negative material can be used as the negative material of lithium ion battery, ultracapacitor, sodium-ion battery.
Positively effect of the present invention is to adopt the Graphene with vesicular structure can improve charge-discharge performance, can also provide more diffusion admittance for the transmission of ion.This composite material preparation process is simple, is easy to mass-producing.Graphene composite negative pole material can be used as the electrode materials of lithium ion battery, sodium-ion battery and ultracapacitor etc.
Accompanying drawing explanation
Fig. 1 is the charge-discharge test curve of the composite negative pole material of the embodiment of the present invention 1.
Fig. 2 is the cyclic voltammetry curve of the composite negative pole material of the embodiment of the present invention 1.
Embodiment
The present invention will be further described for structure drawings and Examples below: described embodiment is the specific descriptions to claim of the present invention just, and claim includes but not limited to described embodiment content.
Embodiment 1
Taking specific surface area according to mass percent 20% is 2200m
2/ g, the Graphene that aperture is 3～8nm and Li
4ti
5o
12.Graphene is put in the ball grinder of ball mill, added a small amount of ethanol ball milling 2min, make Graphene complete wetting, add Li
4ti
5o
12continue ball milling 1h, take out the material having mixed, 60 ℃ are dried and remove ethanol, obtain Li
4ti
5o
12/ graphene combination electrode material, makes pole piece with polyvinylidene difluoride (PVDF) according to mass ratio 95:5, can be used as the negative pole of ultracapacitor.As shown in Figure 1, 2.
Embodiment 2
Taking specific surface area according to mass percent 20% is 2200m
2/ g, the Graphene that aperture is 3～8nm.Graphene is put in the ball grinder of ball mill, added a small amount of water for ball milling 3min, make Graphene complete wetting, add sucrose ball milling to dissolve, add again deionized water and stirring 2min, add Si sphere of powder mill 30min, take out the material having mixed, electrostatic spinning, dry, then, at 700 ℃ of calcining 2h of atmosphere of inert gases, obtain composite negative pole material, make pole piece with polyvinylidene difluoride (PVDF) according to mass ratio 90:10, can be used as lithium ion battery negative.
Embodiment 3
Taking specific surface area according to mass percent 10% is 2200m
2/ g, the Graphene that aperture is 3～8nm, forms dispersion liquid with tin chloride, sodium hydroxide in deionized water and stirring.The dispersion liquid obtaining is put into 140 ℃ of reaction 12h in hydrothermal reaction kettle, generates product washing, dry, then at 500 ℃ of calcining 30min of atmosphere of inert gases, obtain composite negative pole material, make pole piece with polyvinylidene difluoride (PVDF) according to mass ratio 90:10, can be used as lithium ion battery negative.
Embodiment 4
Taking specific surface area according to mass percent 30% is 1200m
2/ g, the Graphene that aperture is 3～8nm makes dispersion liquid with hard charcoal at deionized water and stirring 4h.By ultrasonic dispersion liquid 2h, dry, obtain composite negative pole material, make pole piece with polyvinylidene difluoride (PVDF) according to mass ratio 90:10, can be used as the negative pole of sodium-ion battery.
Claims (8)
1. the composite negative pole material based on Graphene, is characterized in that: Graphene is vesicular structure, is uniformly distributed negative material particle between surface and lamella, and the mass percent that Graphene accounts for composite negative pole material is 10～50%.
2. the composite negative pole material based on Graphene according to claim 1, is characterized in that described negative material is graphite, MCMB, activated carbon fiber, hard charcoal, Si, Co
3o
4, Fe
3o
4, TiO
2, SnO
2, Li
4ti
5o
12, Na
xnbS
2one in (0.1≤x≤0.9).
3. the composite negative pole material based on Graphene according to claim 1, is characterized in that described Graphene specific surface area is 800～2300 m
2/ g.
4. the composite negative pole material based on Graphene according to claim 1, is characterized in that the preparation method of described composite negative pole material is physical mixed, a kind of during chemical original position is compound or their combination.
5. according to claim 4 based on Graphene composite negative pole material, it is characterized in that described physical mixed method be stir, a kind of in ultrasonic, ball milling or their combination, in mixing process, can be dry mixed, add solvent wet mixing or be dry mixed-wet mixing combination.
6. according to the composite negative pole material based on Graphene described in claim 4,5, the step that it is characterized in that described physical mixed is as follows: take Graphene according to mass ratio and put in mixing vessel, add solvent that Graphene is infiltrated completely, according to mass ratio, negative material is added in mixing vessel and is uniformly dispersed, dry, obtain composite negative pole material.
7. the composite negative pole material based on Graphene according to claim 4, is characterized in that described chemical in-situ compounding process is that Graphene mixes with the raw material of synthetic negative material, forms composite negative pole material in building-up process.
8. the composite negative pole material based on Graphene according to claim 1, is characterized in that described negative material can be used as the negative material of lithium ion battery, ultracapacitor, sodium-ion battery.
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Cited By (17)
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| CN104733694A (en) * | 2014-12-25 | 2015-06-24 | 曲婕 | Preparation method of cheap and effective graphite cathode for sodium-ion battery |
| CN105448540A (en) * | 2015-11-18 | 2016-03-30 | 福建翔丰华新能源材料有限公司 | Super-capacitor high-conductive active carbon electrode manufacturing method |
| CN105529440A (en) * | 2014-09-29 | 2016-04-27 | 凤凰新能源(惠州)有限公司 | High-rate high-capacity lithium ion negative electrode material |
| CN105762359A (en) * | 2016-03-04 | 2016-07-13 | 深圳市翔丰华科技有限公司 | Preparation method of sodium ion battery high capacity graphite negative electrode material |
| CN106115673A (en) * | 2016-06-24 | 2016-11-16 | 安徽桑瑞斯环保新材料有限公司 | A kind of preparation of two dimension class grapheme material |
| CN106486646A (en) * | 2015-08-28 | 2017-03-08 | 张明东 | Lithium ion battery negative material and preparation method thereof and lithium ion battery |
| CN106784747A (en) * | 2017-03-10 | 2017-05-31 | 天津大学 | A kind of graphene-based lithium ion battery negative material |
| CN106856241A (en) * | 2016-12-29 | 2017-06-16 | 南京邮电大学 | A kind of multiphase composite nanostructure negative material and preparation method thereof |
| CN107248454A (en) * | 2017-06-06 | 2017-10-13 | 唐春霞 | A kind of graphene crystalline material and preparation method and application |
| CN107887581A (en) * | 2017-10-30 | 2018-04-06 | 北京万源工业有限公司 | Porous graphene coated graphite, preparation and the application on lithium ion battery |
| CN109103029A (en) * | 2018-08-27 | 2018-12-28 | 四川理工学院 | A kind of spiral nanometer carbon fiber/TiO2Composite material and its application |
| CN109585821A (en) * | 2018-11-23 | 2019-04-05 | 四川大学 | Graphite composite material, preparation method, application and negative electrode of lithium ion battery |
| CN109638270A (en) * | 2018-12-29 | 2019-04-16 | 内蒙古杉杉科技有限公司 | A kind of silicon-graphene-porous carbon composite electrode material and its preparation method and application |
| CN109742343A (en) * | 2018-12-20 | 2019-05-10 | 中南民族大学 | High-valued electrode active material of nylon engineering plastic and preparation method thereof |
| CN110034294A (en) * | 2019-05-17 | 2019-07-19 | 浙江卡波恩新材料有限公司 | A kind of preparation method of the carbon coating graphene as lithium cell cathode material |
| CN110246702A (en) * | 2018-03-09 | 2019-09-17 | 广州墨羲科技有限公司 | A kind of porous metals/three-dimensional graphene composite material |
| CN111777063A (en) * | 2020-07-09 | 2020-10-16 | 西安交通大学 | Preparation method of nano material |
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105529440A (en) * | 2014-09-29 | 2016-04-27 | 凤凰新能源(惠州)有限公司 | High-rate high-capacity lithium ion negative electrode material |
| CN104733694A (en) * | 2014-12-25 | 2015-06-24 | 曲婕 | Preparation method of cheap and effective graphite cathode for sodium-ion battery |
| CN104733694B (en) * | 2014-12-25 | 2017-04-26 | 曲婕 | Preparation method of graphite cathode for sodium-ion battery |
| CN106486646A (en) * | 2015-08-28 | 2017-03-08 | 张明东 | Lithium ion battery negative material and preparation method thereof and lithium ion battery |
| CN105448540A (en) * | 2015-11-18 | 2016-03-30 | 福建翔丰华新能源材料有限公司 | Super-capacitor high-conductive active carbon electrode manufacturing method |
| CN105762359A (en) * | 2016-03-04 | 2016-07-13 | 深圳市翔丰华科技有限公司 | Preparation method of sodium ion battery high capacity graphite negative electrode material |
| CN106115673A (en) * | 2016-06-24 | 2016-11-16 | 安徽桑瑞斯环保新材料有限公司 | A kind of preparation of two dimension class grapheme material |
| CN106856241B (en) * | 2016-12-29 | 2020-08-11 | 南京邮电大学 | Multiphase composite nano-structure cathode material and preparation method thereof |
| CN106856241A (en) * | 2016-12-29 | 2017-06-16 | 南京邮电大学 | A kind of multiphase composite nanostructure negative material and preparation method thereof |
| CN106784747B (en) * | 2017-03-10 | 2019-07-05 | 天津大学 | A kind of graphene-based lithium ion battery negative material |
| CN106784747A (en) * | 2017-03-10 | 2017-05-31 | 天津大学 | A kind of graphene-based lithium ion battery negative material |
| CN107248454A (en) * | 2017-06-06 | 2017-10-13 | 唐春霞 | A kind of graphene crystalline material and preparation method and application |
| CN107887581A (en) * | 2017-10-30 | 2018-04-06 | 北京万源工业有限公司 | Porous graphene coated graphite, preparation and the application on lithium ion battery |
| CN110246702A (en) * | 2018-03-09 | 2019-09-17 | 广州墨羲科技有限公司 | A kind of porous metals/three-dimensional graphene composite material |
| CN109103029A (en) * | 2018-08-27 | 2018-12-28 | 四川理工学院 | A kind of spiral nanometer carbon fiber/TiO2Composite material and its application |
| CN109585821A (en) * | 2018-11-23 | 2019-04-05 | 四川大学 | Graphite composite material, preparation method, application and negative electrode of lithium ion battery |
| CN109742343A (en) * | 2018-12-20 | 2019-05-10 | 中南民族大学 | High-valued electrode active material of nylon engineering plastic and preparation method thereof |
| CN109638270A (en) * | 2018-12-29 | 2019-04-16 | 内蒙古杉杉科技有限公司 | A kind of silicon-graphene-porous carbon composite electrode material and its preparation method and application |
| CN110034294A (en) * | 2019-05-17 | 2019-07-19 | 浙江卡波恩新材料有限公司 | A kind of preparation method of the carbon coating graphene as lithium cell cathode material |
| CN111777063A (en) * | 2020-07-09 | 2020-10-16 | 西安交通大学 | Preparation method of nano material |
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