CN103854881A - Preparation method for graphene/carbon nano-tube combined electrode - Google Patents
Preparation method for graphene/carbon nano-tube combined electrode Download PDFInfo
- Publication number
- CN103854881A CN103854881A CN201210504799.9A CN201210504799A CN103854881A CN 103854881 A CN103854881 A CN 103854881A CN 201210504799 A CN201210504799 A CN 201210504799A CN 103854881 A CN103854881 A CN 103854881A
- Authority
- CN
- China
- Prior art keywords
- tube
- carbon nano
- graphene
- preparation
- dispersion liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the field of electrode preparation, and discloses a preparation method for a graphene/carbon nano-tube combined electrode. The method comprises the following steps: the carbon nano-tube is immersed in strong acid, and backflow treatment is performed so that an acyl chloride carbon nano-tube is obtained; then the backflow treatment is performed on the acyl chloride carbon nano-tube in the mixed solution of ethene diamine and toluene so that an amidation carbon nano-tube is obtained; and the amidation carbon nano-tube and graphene oxide are respectively prepared into dispersion liquid, and finally a current collector is immersed into dispersion liquid of the amidation carbon nano-tube and dispersion liquid of the graphene oxide in an alternating way so that the combined electrode is obtained after drying. According to the preparation method for the graphene/carbon nano-tube combined electrode, a layer-upon-layer self-assembly mode is adopted so that a problem of reuniting between graphene sheet layers in the preparation process can be avoided and double electric layer capacity of the material can be enhanced. Meanwhile, electron conduction can be performed between the graphene layers by the carbon nano-tube so that the electrode material is ensured to be high in power density.
Description
Technical field
The present invention relates to the preparation of electrode, relate in particular to a kind of preparation method of graphene/carbon nanometer tube combination electrode.
Background technology
The strong K sea nurse of the peace moral of Univ Manchester UK (Andre K.Geim) etc. was prepared grapheme material in 2004, pay attention to widely because its unique structure and photoelectric property have been subject to people.Mono-layer graphite is due to its large specific area, good conduction, heat conductivility and low thermal coefficient of expansion and be considered to desirable material.As: 1, high strength, Young mole, (1,100GPa), fracture strength: (125GPa); 2, high heat conductance, (5,000W/mK); 3, high conductivity, carrier transport rate, (200,000cm2/V*s); 4, high specific area, (calculated value: 2,630m2/g).Especially its high conductivity matter, the structural property of large specific surface character and the nanoscale of its monolayer two dimension can be used as electrode material in ultracapacitor and lithium ion battery.Up to the present, known to the method for preparing Graphene have multiple, as (1) micromechanics stripping method.This method can only produce the very limited graphene film of quantity, can be used as basic research; (2) ultra high vacuum Graphene epitaxial growth method.The structural limitations of the expensive and sequin of this method its application; (3) chemical vapour deposition technique (CVD).The method can meet the requirement that high-quality graphene is prepared in scale, but cost is higher, complex process.(4) solvent stripping method.The method shortcoming is that productive rate is very low, limits its business application; (5) oxidation-reduction method.
Ruoff group utilizes the Graphene of chemical modification as electrode material, has tested the performance of the ultracapacitor based on Graphene.The capacity of the capacitive property of this grapheme material in water system and organic electrolyte can reach respectively 135F/g and 99F/g.The people such as Rao have compared the capacitive property of the Graphene of preparing by two kinds of methods.In sulfuric acid electrolyte, the Graphene obtaining by graphite oxide dilatometry and Nano diamond conversion method has higher capacity, can reach 117F/g; In organic electrolyte, when voltage is 3.5V, its capacity and energy density can reach 71F/g and 31.9Wh/kg.
Above method is all to adopt the graphene powder of preparation to make electrode slice through techniques such as batch mixing, coating, roll-in, sections, in the preparation of Graphene with always there is the problem of the reunion of grapheme material in making the process of pole piece, and then make the energy density that affects battery after battery, the actual energy density of grapheme material is far smaller than its theoretical value.
Summary of the invention
Based on the problems referred to above, problem to be solved by this invention is to provide a kind of preparation method of graphene/carbon nanometer tube combination electrode
Technical scheme of the present invention is as follows:
A preparation method for graphene/carbon nanometer tube combination electrode, comprises the steps:
Carbon nano-tube is refluxed in strong acid at 50-80 ℃ 0.5-2h, then filters, and by the screening obtaining through washing, filter, dry, obtain carboxylic carbon nano-tube; Wherein, the solid-to-liquid ratio of carbon nano-tube and strong acid is 0.1-2g:100ml;
Described carboxylic carbon nano-tube is being added to chloride reagent, and the 5-15h that refluxes at 50-80 ℃, obtains chloride carbon nano-tube; Wherein, the solid-to-liquid ratio of carboxylic carbon nano-tube and chloride reagent is 0.1-2g:100ml;
Described chloride carbon nano-tube and amidation reagent are added in organic solvent, and react 24-48h at 50-80 ℃, subsequent filtration, and by the screening obtaining through ethanol and washing, dry after, obtain amidatioon carbon nano-tube; Wherein, chloride carbon nano-tube: amidation reagent: the solid-to-liquid ratio of organic solvent is 0.1-1g:100:200ml;
Described chloride carbon nano-tube is added to the water to ultrasonic dispersion, forms the amidatioon carbon nano tube dispersion liquid of 0.2-0.8mg/ml; Meanwhile, graphite oxide is added to the water to ultrasonic dispersion, forms the graphene oxide dispersion liquid of 0.2-0.8mg/ml;
Collector is soaked to 30 ~ 60min at amidatioon carbon nano tube dispersion liquid, and then soak 1 ~ 5min in described graphene oxide dispersion liquid; Then in amidatioon carbon nano tube dispersion liquid and dispersion liquid, alternately soak 30 ~ 500 times again, and soak time is 1 ~ 5min in every kind of dispersion liquid, after being dried, obtain graphene oxide/carbon nano-tube combination electrode;
By described graphene oxide/carbon nano-tube combination electrode under inert gas shielding, in 500 ~ 1000 ℃ of pyroreaction 1 ~ 5h, cooling after, obtain described graphene/carbon nanotube electrode sheet.
The preparation method of described graphene/carbon nanometer tube combination electrode, wherein, described strong acid is the mixed acid that 68% red fuming nitric acid (RFNA) and 98% concentrated sulfuric acid are mixed to get according to the volume ratio of 3:1.
The preparation method of described graphene/carbon nanometer tube combination electrode, wherein, described chloride reagent is the sub-phenol of dichloro, phosphorus oxychloride or thionyl chloride.
The preparation method of described graphene/carbon nanometer tube combination electrode, wherein, described amidation reagent is ethylenediamine, triethylamine or urea.
The preparation method of described graphene/carbon nanometer tube combination electrode, wherein, described organic solvent is dry toluene, oxolane or carrene.
The preparation method of described graphene/carbon nanometer tube combination electrode, wherein, described collector is aluminium foil, nickel screen, titanium foil or steel foil.
The preparation method of described graphene/carbon nanometer tube combination electrode, wherein, dry in described chloride carbon nano-tube preparation process is 50 ℃ of dry 24h in vacuum drying chamber.
The preparation method of described graphene/carbon nanometer tube combination electrode, wherein, described inert gas is one or more in nitrogen, argon gas, helium and neon.
The invention provides the preparation method of graphene/carbon nanometer tube combination electrode, adopt the mode of self assembly layer by layer, grapheme material is prepared into electrode slice, the electrode slice of preparation can be used as the positive plate of lithium ion battery or battery capacitor, in the process of making electrode slice, avoid the agglomeration traits between graphene sheet layer, improve the electric double layer capacity of material, carbon nano-tube can be carried out electrical conductivity between layers at Graphene simultaneously, guarantees that electrode material has height power density; Also the method does not also add common electrode and prepares required binding agent and conductive agent simultaneously.
Accompanying drawing explanation
Fig. 1 is preparation technology's flow chart of graphene/carbon nanometer tube combination electrode of the present invention.
Embodiment
The invention provides a kind of preparation method of graphene/carbon nanometer tube combination electrode, as shown in Figure 1, its technological process is as follows:
(1), by carbon nano-tube 50-80 ℃ of backflow 0.5-2h in strong acid (mixed acid that 68% red fuming nitric acid (RFNA): 98% concentrated sulfuric acid=3:1 obtains), then by the product washing obtaining, filter, the dry carboxylic carbon nano-tube that obtains; Wherein, the solid-to-liquid ratio of carbon nano-tube and mixed acid is 0.1-2g:100ml;
(2), by the carboxylic carbon nano-tube obtaining in chloride reagent, 50-80 ℃ of backflow 5-15h, obtains chloride carbon nano-tube; Wherein, the solid-to-liquid ratio of carboxylic carbon nano-tube and chloride reagent is 0.1-2g:100ml;
Preferably, chloride reagent is the sub-phenol of dichloro, phosphorus oxychloride or thionyl chloride;
(3) above-mentioned chloride carbon nano-tube and amidation reagent are added in organic solvent, 50-80 ℃ reaction 24-48h, subsequent filtration, and by the screening obtaining through ethanol and washing, after 50 ℃ of vacuumize 24h, obtain amidatioon carbon nano-tube; Wherein, chloride carbon nano-tube: amidation reagent: the solid-to-liquid ratio of organic solvent is 0.1-1g:100:200ml;
Preferably, amidation reagent is ethylenediamine, triethylamine or urea;
Preferably, organic solvent is dry toluene, oxolane or carrene;
(4), described amidatioon carbon nano-tube is added to the water to ultrasonic dispersion, the amidatioon carbon nano tube dispersion liquid of formation 0.2-0.8mg/ml; Meanwhile, graphite oxide is added to the water to ultrasonic dispersion, forms the graphene oxide dispersion liquid of 0.2-0.8mg/ml;
(5), first collector is soaked to 30 ~ 60min in amidatioon carbon nano tube dispersion liquid, and then soak 1 ~ 5min in described graphene oxide dispersion liquid; Then successively in amidatioon carbon nano tube dispersion liquid and graphene oxide dispersion liquid, alternately soak 30 ~ 500 times successively again, and soak time is 1 ~ 5min in every kind of dispersion liquid, after being dried, obtains graphene oxide/carbon nano-tube combination electrode;
(6), by described graphene oxide/carbon nano-tube combination electrode under inert gas shielding, in 500 ~ 1000 ℃ of pyroreaction 1 ~ 5h, carry out roll-in after cooling, obtain described graphene/carbon nanotube electrode sheet.
In above-mentioned steps (5), collector can be selected aluminium foil, nickel screen, titanium foil, steel foil etc.
In above-mentioned steps (6), inert gas can be one or more mixing in nitrogen, argon gas, helium and neon.
The invention provides the preparation method of graphene/carbon nanometer tube combination electrode, adopt the mode of self assembly layer by layer, grapheme material is prepared into electrode slice, the electrode slice of preparation can be used as the positive plate of lithium ion battery or battery capacitor, in the process of making electrode slice, avoid the agglomeration traits between graphene sheet layer, improve the electric double layer capacity of material, carbon nano-tube can be carried out electrical conductivity between layers at Graphene simultaneously, guarantees that electrode material has height power density; Also the method does not also add common electrode and prepares required binding agent and conductive agent simultaneously.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
(1) by carbon nano-tube 50 ℃ of backflow 2h in mixed acid (68% red fuming nitric acid (RFNA): 98% concentrated sulfuric acid=3:1), then by the product washing obtaining, filtration, the dry carboxylic carbon nano-tube that obtains; The solid-to-liquid ratio of carbon nano-tube and mixed acid is 0.1g:100ml;
(2) by the carboxylic carbon nano-tube obtaining at the sub-phenol (SOCl of dichloro
2) in 50 ℃ of backflow 15h, obtain chloride carbon nano-tube; The solid-to-liquid ratio of carboxylic carbon nano-tube and SOCl2 is 0.1g:100ml;
(3) by above-mentioned chloride carbon nano-tube and ethylenediamine in dry toluene 50 ℃ react 24h, ethanol and washing, obtain amidatioon carbon nano-tube after 50 ℃ of vacuumize 24h; Chloride carbon nano-tube: ethylenediamine: the addition of dry toluene is 0.1g:100ml:200ml;
(4) by the ultrasonic chloride carbon nano-tube amidatioon carbon nano tube dispersion liquid that forms 0.2mg/ml that is dispersed in water;
(5) by the ultrasonic graphite oxide graphene oxide dispersion liquid that forms 0.2mg/ml that is dispersed in water;
(6) first aluminium foil is soaked to 30min in chloride carbon nano tube dispersion liquid, then disperse 1min at graphene oxide dispersion liquid; In chloride carbon nano tube dispersion liquid and the dispersion of graphene oxide dispersion liquid, alternately soak successively subsequently, in every kind of dispersion liquid, soak time is 1min, after being dried, obtains electrode;
(7) electrode slice obtaining is put into the Muffle furnace of nitrogen gas protection, 500 ℃ of pyroreaction 5h, carry out roll-in after cooling, obtain graphene/carbon nanotube electrode sheet.
(1) by carbon nano-tube 80 ℃ of backflow 0.5h in mixed acid (68% red fuming nitric acid (RFNA): 98% concentrated sulfuric acid=3:1), then by the product washing obtaining, filtration, the dry carboxylic carbon nano-tube that obtains; The addition of carbon nano-tube and mixed acid is 2g:100ml;
(2) by the carboxylic carbon nano-tube obtaining 80 ℃ of backflow 5h in phosphorus oxychloride, obtain chloride carbon nano-tube; The solid-to-liquid ratio of carboxylic carbon nano-tube and phosphorus oxychloride is 2g:100ml;
(3) by above-mentioned chloride carbon nano-tube and triethylamine in oxolane 80 ℃ react 48h, ethanol and washing, obtain amidatioon carbon nano-tube after 50 ℃ of vacuumize 24h; Chloride carbon nano-tube: triethylamine: the solid-to-liquid ratio of oxolane is 1g:100ml:200ml;
(4) by the ultrasonic chloride carbon nano-tube amidatioon carbon nano tube dispersion liquid that forms 0.8mg/ml that is dispersed in water;
(5) by the ultrasonic graphite oxide graphene oxide dispersion liquid that forms 0.8mg/ml that is dispersed in water;
(6) first nickel screen is soaked to 60min in chloride carbon nano tube dispersion liquid, then soak 5min at graphene oxide dispersion liquid; Successively in amidatioon carbon nano tube dispersion liquid and graphene oxide dispersion liquid, alternately soak 50 times successively more subsequently, in every kind of dispersion liquid, soak time is 5min, after being dried, obtains electrode;
(7) electrode slice obtaining is put into the Muffle furnace of argon gas protection, 1000 ℃ of pyroreaction 1h, carry out roll-in after cooling, obtain graphene/carbon nanotube electrode sheet.
(1) by carbon nano-tube 60 ℃ of backflow 1h in mixed acid (68% red fuming nitric acid (RFNA): 98% concentrated sulfuric acid=3:1), then by the product washing obtaining, filtration, the dry carboxylic carbon nano-tube that obtains; The solid-to-liquid ratio of carbon nano-tube and mixed acid is 0.8g:100ml;
(2) by the carboxylic carbon nano-tube obtaining 60 ℃ of backflow 8h in thionyl chloride, obtain chloride carbon nano-tube; The solid-to-liquid ratio of carboxylic carbon nano-tube and thionyl chloride is 0.8g:100ml;
(3) by above-mentioned chloride carbon nano-tube and urea in carrene 60 ℃ react 30h, ethanol and washing, obtain amidatioon carbon nano-tube after 50 ℃ of vacuumize 24h; Chloride carbon nano-tube: urea: the solid-to-liquid ratio of carrene is 0.4g:100ml:200ml;
(4) by the ultrasonic amidatioon carbon nano-tube amidatioon carbon nano tube dispersion liquid that forms 0.4mg/ml that is dispersed in water;
(5) by the ultrasonic graphite oxide graphene oxide dispersion liquid that forms 0.4mg/ml that is dispersed in water;
(6) first titanium foil is soaked to 40min in amidatioon carbon nano tube dispersion liquid, then soak 2min at graphene oxide dispersion liquid; Successively in amidatioon carbon nano tube dispersion liquid and graphene oxide dispersion liquid, alternately soak 500 times successively more subsequently, in every kind of dispersion liquid, soak time is 2min, after being dried, obtains electrode;
(7) electrode slice obtaining is put into the Muffle furnace of helium atmosphere protection, 800 ℃ of pyroreaction 2h, carry out roll-in after cooling, obtain graphene/carbon nanotube electrode sheet.
(1) by carbon nano-tube 70 ℃ of backflow 1.5h in mixed acid (68% red fuming nitric acid (RFNA): 98% concentrated sulfuric acid=3:1), then by the product washing obtaining, filtration, the dry carboxylic carbon nano-tube that obtains; The solid-to-liquid ratio of carbon nano-tube and mixed acid is 1.5g:100ml;
(2) by the carboxylic carbon nano-tube obtaining at SOCl
270 ℃ of backflow 12h in (the sub-phenol of dichloro), obtain chloride carbon nano-tube; Carboxylic carbon nano-tube and SOCl
2solid-to-liquid ratio be 1.5g:100ml;
(3) by above-mentioned chloride carbon nano-tube and ethylenediamine in dry toluene 70 ℃ react 36h, ethanol and washing, obtain amidatioon carbon nano-tube after 50 ℃ of vacuumize 24h; The solid-to-liquid ratio of chloride carbon nano-tube and ethylenediamine, dry toluene is 0.7g:100ml:200ml;
(4) by the amidatioon carbon nano-tube ultrasonic amidatioon carbon nano tube dispersion liquid that forms 0.6mg/ml that is dispersed in water respectively;
(5) by the ultrasonic graphite oxide graphene oxide dispersion liquid that forms 0.6mg/ml that is dispersed in water;
(6) first steel foil is soaked to 50min in amidatioon carbon nano tube dispersion liquid, then soak 3min at graphene oxide dispersion liquid; Successively in amidatioon carbon nano tube dispersion liquid and graphene oxide dispersion liquid, alternately soak 200 times successively more subsequently, in every kind of dispersion liquid, soak time is 3min, after being dried, obtains electrode;
(7) electrode slice obtaining is put into the Muffle furnace of neon Buchholz protection, 700 ℃ of pyroreaction 3h, carry out roll-in after cooling, obtain graphene/carbon nanotube electrode sheet.
(1) by carbon nano-tube 70 ℃ of backflow 1.5h in mixed acid (68% red fuming nitric acid (RFNA): 98% concentrated sulfuric acid=3:1), then by the product washing obtaining, filtration, the dry carboxylic carbon nano-tube that obtains; The solid-to-liquid ratio of carbon nano-tube and mixed acid is 1.5g:100ml;
(2) by the carboxylic carbon nano-tube obtaining at SOCl
270 ℃ of backflow 12h in (the sub-phenol of dichloro), obtain chloride carbon nano-tube; Carboxylic carbon nano-tube and SOCl
2solid-to-liquid ratio be 1.5g:100ml;
(3) by above-mentioned chloride carbon nano-tube and ethylenediamine in dry toluene 70 ℃ react 36h, ethanol and washing, obtain amidatioon carbon nano-tube after 50 ℃ of vacuumize 24h; The solid-to-liquid ratio of chloride carbon nano-tube and ethylenediamine, dry toluene is 0.7g:100ml:200ml;
(4) by the ultrasonic amidatioon carbon nano-tube amidatioon carbon nano tube dispersion liquid that forms 0.6mg/ml that is dispersed in water;
(5) by the ultrasonic graphite oxide graphene oxide dispersion liquid that forms 0.6mg/ml that is dispersed in water;
(6) first aluminium foil is soaked to 45min in amidatioon carbon nano tube dispersion liquid, then soak 4min at graphene oxide dispersion liquid; Successively in amidatioon carbon nano tube dispersion liquid and graphene oxide dispersion liquid, alternately soak 400 times successively more subsequently, in every kind of dispersion liquid, soak time is 4min, after being dried, obtains electrode;
(7) electrode slice obtaining is put into the Muffle furnace of argon gas protection, 600 ℃ of pyroreaction 4h, carry out roll-in after cooling, obtain graphene/carbon nanotube electrode sheet.
Comparative example 1
The preparation method of conventional electrodes sheet: be 1000m by specific area
2/ g Graphene mixes with the ratio of mass ratio 90:5:5 with conductive agent acetylene black, binding agent PVDF, obtains active slurry, and active slurry is coated on aluminium foil, and after dry 24h, compressing tablet obtains electrode slice.
The button cell that above embodiment and the prepared electrode slice of comparative example and lithium sheet and barrier film are assembled into carries out constant current charge-discharge test, and electrolyte adopts ionic liquid BMIMBF
4.The capacity that obtains embodiment is as follows:
Table 1 obtains energy content of battery density measurement result for each embodiment and comparative example.
Table 1
| ? | |
|
|
|
|
Comparative example 1 |
| Energy density wh/kg | 112 | 99 | 103 | 107 | 110 | 60 |
As shown in Table 1, adopt the electrode material energy density for preparing of the present invention can reach 110wh/kg left and right, higher than the electrode slice that in comparative example 1 prepared by conventional method, also higher than the highest energy density 85.6wh/kg of bibliographical information at present.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (8)
1. a preparation method for graphene/carbon nanometer tube combination electrode, is characterized in that, comprises the steps:
Carbon nano-tube is refluxed in strong acid at 50-80 ℃ 0.5-2h, then filters, and by the screening obtaining through washing, filter, dry, obtain carboxylic carbon nano-tube; Wherein, the solid-to-liquid ratio of carbon nano-tube and strong acid is 0.1-2g:100ml;
Described carboxylic carbon nano-tube is being added to chloride reagent, and the 5-15h that refluxes at 50-80 ℃, obtains chloride carbon nano-tube; Wherein, carboxylic carbon nano-tube and chloride reagent solid-to-liquid ratio are 0.1-2g:100ml;
Described chloride carbon nano-tube and amidation reagent are added in organic solvent, and react 24-48h at 50-80 ℃, subsequent filtration, and by the screening obtaining through ethanol and washing, dry after, obtain amidatioon carbon nano-tube; Wherein, chloride carbon nano-tube: amidation reagent: the solid-to-liquid ratio of organic solvent is 0.1-1g:100:200ml;
Described amidatioon carbon nano-tube is added to the water to ultrasonic dispersion, forms the amidatioon carbon nano tube dispersion liquid of 0.2-0.8mg/ml; Meanwhile, graphite oxide is added to the water to ultrasonic dispersion, forms the graphene oxide dispersion liquid of 0.2-0.8mg/ml;
Collector is soaked to 30 ~ 60min at amidatioon carbon nano tube dispersion liquid, and then soak 1 ~ 5min in described graphene oxide dispersion liquid; Then successively in amidatioon carbon nano tube dispersion liquid and graphene oxide dispersion liquid, alternately soak 30 ~ 500 times successively again, and soak time is 1 ~ 5min in every kind of dispersion liquid, after being dried, obtains graphene oxide/carbon nano-tube combination electrode;
By described graphene oxide/carbon nano-tube combination electrode under inert gas shielding, in 500 ~ 1000 ℃ of pyroreaction 1 ~ 5h, cooling after, obtain described graphene/carbon nanotube electrode sheet.
2. the preparation method of graphene/carbon nanometer tube combination electrode according to claim 1, is characterized in that, described strong acid is the mixed acid that 68% red fuming nitric acid (RFNA) and 98% concentrated sulfuric acid are mixed to get according to the volume ratio of 3:1.
3. the preparation method of graphene/carbon nanometer tube combination electrode according to claim 1, is characterized in that, described chloride reagent is the sub-phenol of dichloro, phosphorus oxychloride or thionyl chloride.
4. the preparation method of graphene/carbon nanometer tube combination electrode according to claim 1, is characterized in that, described amidation reagent is ethylenediamine, triethylamine or urea.
5. the preparation method of graphene/carbon nanometer tube combination electrode according to claim 1, is characterized in that, described organic solvent is dry toluene, oxolane or carrene.
6. the preparation method of graphene/carbon nanometer tube combination electrode according to claim 1, is characterized in that, described collector is aluminium foil, nickel screen, titanium foil or steel foil.
7. the preparation method of graphene/carbon nanometer tube combination electrode according to claim 1, is characterized in that, dry in described amidatioon carbon nano-tube preparation process is 50 ℃ of dry 24h in vacuum drying chamber.
8. the preparation method of graphene/carbon nanometer tube combination electrode according to claim 1, is characterized in that, described inert gas is one or more in nitrogen, argon gas, helium and neon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210504799.9A CN103854881B (en) | 2012-11-30 | 2012-11-30 | A kind of preparation method of graphene/carbon nano-tube combination electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210504799.9A CN103854881B (en) | 2012-11-30 | 2012-11-30 | A kind of preparation method of graphene/carbon nano-tube combination electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103854881A true CN103854881A (en) | 2014-06-11 |
| CN103854881B CN103854881B (en) | 2016-12-21 |
Family
ID=50862411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210504799.9A Active CN103854881B (en) | 2012-11-30 | 2012-11-30 | A kind of preparation method of graphene/carbon nano-tube combination electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103854881B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105244190A (en) * | 2015-10-21 | 2016-01-13 | 山东科技大学 | Preparation method of graphene/carbon nano tube co-reinforced conducting polymer hydrogel |
| CN106129374A (en) * | 2016-08-26 | 2016-11-16 | 深圳博磊达新能源科技有限公司 | A kind of transition metal oxide/binary carbon net anode composite material and aluminium ion battery |
| CN106442668A (en) * | 2016-09-28 | 2017-02-22 | 北京农学院 | Method for preparing carbon nano-tube modified electrode |
| CN106784700A (en) * | 2016-12-27 | 2017-05-31 | 电子科技大学 | A kind of multilayer silicon/Graphene composite lithium ion battery negative material and preparation method thereof |
| CN106848313A (en) * | 2017-01-19 | 2017-06-13 | 深圳市金百纳纳米科技有限公司 | A kind of composite of one-dimensional graphene material |
| CN106935312A (en) * | 2017-03-29 | 2017-07-07 | 浙江师范大学 | A kind of aqueous mixed type electrocondution slurry and preparation method thereof |
| CN107146889A (en) * | 2017-04-24 | 2017-09-08 | 西北工业大学 | A kind of graphene/CNTs crossbreds do lithium metal battery collector and preparation method thereof |
| CN108152353A (en) * | 2017-12-31 | 2018-06-12 | 西北师范大学 | The preparation of graphene-based carboxymethylcellulose sodium rice crystal composite material and the application as chiral Recognition material |
| CN113174117A (en) * | 2021-04-26 | 2021-07-27 | 中科院长春应化所黄埔先进材料研究院 | Dual-functional-layer polymer composite material and preparation method thereof |
| CN113488654A (en) * | 2021-07-27 | 2021-10-08 | 深圳齐锂纳米科技有限公司 | Graphene composite layered conductive agent supported by carbon nano tube |
| CN114156445A (en) * | 2021-10-28 | 2022-03-08 | 西安交通大学 | Electrode material with bionic shell layered structure and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417176A (en) * | 2011-09-06 | 2012-04-18 | 天津大学 | Preparation method of graphene-carbon nanotube compound film based on three-dimensional network appearance |
| CN102522217A (en) * | 2011-12-12 | 2012-06-27 | 北京航空航天大学 | Supercapacitor and preparation method thereof |
| US20120164539A1 (en) * | 2010-12-23 | 2012-06-28 | Aruna Zhamu | Surface -controlled lithium ion-exchanging energy storage device |
-
2012
- 2012-11-30 CN CN201210504799.9A patent/CN103854881B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120164539A1 (en) * | 2010-12-23 | 2012-06-28 | Aruna Zhamu | Surface -controlled lithium ion-exchanging energy storage device |
| CN102417176A (en) * | 2011-09-06 | 2012-04-18 | 天津大学 | Preparation method of graphene-carbon nanotube compound film based on three-dimensional network appearance |
| CN102522217A (en) * | 2011-12-12 | 2012-06-27 | 北京航空航天大学 | Supercapacitor and preparation method thereof |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105244190A (en) * | 2015-10-21 | 2016-01-13 | 山东科技大学 | Preparation method of graphene/carbon nano tube co-reinforced conducting polymer hydrogel |
| CN106129374A (en) * | 2016-08-26 | 2016-11-16 | 深圳博磊达新能源科技有限公司 | A kind of transition metal oxide/binary carbon net anode composite material and aluminium ion battery |
| CN106129374B (en) * | 2016-08-26 | 2019-08-27 | 深圳博磊达新能源科技有限公司 | A kind of transition metal oxide/binary carbon net anode composite material and aluminium ion battery |
| CN106442668A (en) * | 2016-09-28 | 2017-02-22 | 北京农学院 | Method for preparing carbon nano-tube modified electrode |
| CN106442668B (en) * | 2016-09-28 | 2019-06-14 | 北京农学院 | A kind of preparation method of carbon nano tube modified electrode |
| CN106784700A (en) * | 2016-12-27 | 2017-05-31 | 电子科技大学 | A kind of multilayer silicon/Graphene composite lithium ion battery negative material and preparation method thereof |
| CN106848313A (en) * | 2017-01-19 | 2017-06-13 | 深圳市金百纳纳米科技有限公司 | A kind of composite of one-dimensional graphene material |
| CN106935312B (en) * | 2017-03-29 | 2018-09-28 | 浙江师范大学 | A kind of aqueous mixed type electrocondution slurry and preparation method thereof |
| CN106935312A (en) * | 2017-03-29 | 2017-07-07 | 浙江师范大学 | A kind of aqueous mixed type electrocondution slurry and preparation method thereof |
| CN107146889A (en) * | 2017-04-24 | 2017-09-08 | 西北工业大学 | A kind of graphene/CNTs crossbreds do lithium metal battery collector and preparation method thereof |
| CN107146889B (en) * | 2017-04-24 | 2019-06-28 | 西北工业大学 | A kind of graphene/CNTs hybrid does lithium metal battery collector and preparation method thereof |
| CN108152353A (en) * | 2017-12-31 | 2018-06-12 | 西北师范大学 | The preparation of graphene-based carboxymethylcellulose sodium rice crystal composite material and the application as chiral Recognition material |
| CN113174117A (en) * | 2021-04-26 | 2021-07-27 | 中科院长春应化所黄埔先进材料研究院 | Dual-functional-layer polymer composite material and preparation method thereof |
| CN113488654A (en) * | 2021-07-27 | 2021-10-08 | 深圳齐锂纳米科技有限公司 | Graphene composite layered conductive agent supported by carbon nano tube |
| CN113488654B (en) * | 2021-07-27 | 2022-04-19 | 深圳齐锂纳米科技有限公司 | Graphene composite layered conductive agent supported by carbon nano tube |
| CN114156445A (en) * | 2021-10-28 | 2022-03-08 | 西安交通大学 | Electrode material with bionic shell layered structure and preparation method and application thereof |
| CN114156445B (en) * | 2021-10-28 | 2023-12-19 | 西安交通大学 | Electrode material with bionic shell lamellar structure and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103854881B (en) | 2016-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103854881A (en) | Preparation method for graphene/carbon nano-tube combined electrode | |
| Luo et al. | Graphene quantum dots encapsulated tremella-like NiCo2O4 for advanced asymmetric supercapacitors | |
| Guo et al. | Synthesis of carbon self-repairing porous g-C3N4 nanosheets/NiCo2S4 nanoparticles hybrid composite as high-performance electrode materials for supercapacitors | |
| CN102941042B (en) | A kind of Graphene/metal oxide hybrid aeroge, preparation method and application thereof | |
| CN102760866B (en) | Preparation method of nitrogen-doped graphene | |
| CN102544459B (en) | Method for preparing graphene-coated carbon microsphere material by coating graphene oxide on carbon microsphere | |
| CN102923698B (en) | Preparation method for three-dimensional porous graphene for supercapacitor | |
| CN101527202B (en) | Oxidized grapheme/polyaniline super capacitor composite electrode material and preparation method | |
| Yin et al. | The synthesis of Co3O4/C composite with aloe juice as the carbon aerogel substrate for asymmetric supercapacitors | |
| CN105098160A (en) | Hollow porous graphene-doped carbon/silicon nanofiber lithium battery anode material and preparation method thereof | |
| CN102568855B (en) | Carbon material-loading manganese dioxide nanowire array composite and method for producing same | |
| Li et al. | Facile synthesis of CoS porous nanoflake for high performance supercapacitor electrode materials | |
| Liu et al. | Three-dimensional carbon foam surrounded by carbon nanotubes and Co-Co3O4 nanoparticles for stable lithium-ion batteries | |
| CN102765715B (en) | Graphene-loaded lamellar cupric oxide composite material and hydro-thermal synthesis method thereof | |
| Dong et al. | The synthesis of graphene/PVDF composite binder and its application in high performance MnO2 supercapacitors | |
| CN102956864B (en) | A kind of preparation method of nitrating Graphene electrodes | |
| CN102569736B (en) | Carbon-coated graphene oxide composite material as well as preparation method and application thereof | |
| CN103578796A (en) | Preparation method of super-capacitor electrode without adhesives | |
| CN103715430A (en) | Three-dimensional graphene reticular structure loaded carbon-coated tin nanometer material as well as preparation method and application thereof | |
| CN103165862A (en) | High-performance negative material of lithium ion cell and preparation method of material | |
| CN104269514A (en) | A preparing method of a transition metal compound-graphene composite material with a three-dimensional porous structure | |
| CN102760870A (en) | Graphene/polythiophene derivative composite material as well as preparation method and application thereof | |
| CN103839683A (en) | Graphene electrode plate and preparation method thereof | |
| CN110416539B (en) | Preparation method of polypyrrole-coated three-dimensional graphene cobaltosic oxide lithium battery cathode material | |
| US20180034055A1 (en) | Composite including porous graphene and carbon nanotube material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |