CN103107023A - Preparation method of graphene/zinc-aluminium oxide composite material and application of composite material in super capacitor - Google Patents
Preparation method of graphene/zinc-aluminium oxide composite material and application of composite material in super capacitor Download PDFInfo
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Abstract
The invention belongs to the field of chemical and provides a preparation method of a graphene/zinc-aluminium oxide composite material and application of the composite material in a super capacitor. The preparation method comprises the steps of: dissolving a graphite oxide precursor, a zinc salt precursor and an aluminium salt precursor in an organic solvent, adding a small amount of deionized water, and ultrasonically dispersing the mixture to be uniform; transferring a mixed solution to a microwave reactor and then slowly dropwise adding an alkali source compound; and washing a product with alcohol for multiple times, then drying the product in vacuum, putting the product in a tubular furnace, introducing Ar/H2 mixed gas, and carrying out high-temperature thermal pyrolysis, thereby obtaining the finished product, namely the graphene/zinc-aluminium oxide composite material. No toxic chemical agent is used in the reduction of graphene, so that harm to human bodies and environment pollution, caused by a great quantity of harmful chemical agents such as hydrazine hydrate serving as a strong reducing agent used in a chemical reduction method, are eliminated fundamentally.
Description
Technical field
The invention belongs to technical field of electrochemistry, particularly a kind of Graphene/Zinc-aluminium composite manufacture method and the application in ultracapacitor thereof.
Background technology
Ultracapacitor is called again electrochemical capacitor or capacitor with super capacity, it is a kind of a kind of Novel energy storage apparatus between traditional capacitor and rechargeable battery, main dependence electric double layer and redox pseudo-capacitance store electrical energy, thereby be different from traditional chemical power source.Ultracapacitor is short because of its charging interval, discharge and recharge that the life-span is long, power density is high and the characteristics such as serviceability temperature wide ranges, be widely used in field (Niu Yulian, Jin Xin, the Zheng Jia such as national defence, railway, electric automobile, electronics, communication, Aero-Space, Li Zaijun, Gu Zhiguo, Yan Tao, Fang Yinjun, Chinese Journal of Inorganic Chemistry, 2012,28 (9), 1878-1884).Super capacitor can be divided into two kinds according to energy storage mechanism difference: a kind of electric capacity by being formed by physical absorption by ion and electronics between electrode material and electrolyte interface, i.e. electric double layer capacitance; Another kind of produce the electric capacity higher than electric double layer capacitance, i.e. Faraday pseudo-capacitance because reversible redox reaction occurs electrode material.In the situation that identical volume or weight, the pseudo capacitance specific capacitance often more than 10～100 times of electric double layer capacitance specific capacitance (Hao Jiang, Jan Ma and Chunzhong Li, Chem.Commun., 2012,48,4465-4467).Therefore, the performance of electrode material directly determines the energy storage quality of capacitor.
At present, the material that is applied to ultracapacitor mainly contains carbon-based material (active carbon, carbon nano-tube, charcoal-aero gel, Graphene), transition metal oxide or hydroxide and conducting polymer (polyaniline).Wherein, the carbon-based material specific area is large, the electric double layer spacing is little and cycle life is high, but discharge capacity is lower.Transition metal oxide or hydroxide good conductivity, specific capacitance are large, but cyclical stability is not good.Conducting polymer is cheap, but thermal stability, chemical stability and recyclability are relatively poor, has limited to a certain extent its application.Therefore, the different attribute material is carried out compound, develop a kind of high capacitance, stability, circulative super capacitor material of having concurrently and be very important.
In recent years, metal oxide receives very big concern as the research of electrode material for super capacitor.The fake capacitance of its generation is obviously greater than store the electric double layer capacitance of the Carbon Materials of electric charge with electric double layer.RuO
2, due to its electrical conductance and have three different oxidation state in 1.2V preferably, obtained broad research.But because it is expensive, and environment is had very large pollution, therefore seeking low-cost, nontoxic and high performance metal oxide materials has become the emphasis of present research as the electrode material of ultracapacitor.The zinc oxide source is abundant, cheap, in widespread attention (Xinjuan Liu, Likun Pan, Tian Lv, Zhuo Sun, Journal of Colloid and Interface Science, 394,441-444).It is very fast that but zinc oxide discharges and recharges the rate of decay, and resistivity is larger, limits it and further develop.
Graphene is the crystal of the hexagon honeycomb lattice structure of the tightly packed formation of monolayer carbon atom, and the two-dimensional structure of its uniqueness makes it have excellent electricity, calorifics, mechanics and chemical property, therefore obtains broad research.(Tao Lihua, Cai Yan, Li Zaijun, Ren Guoxiao, Liu Junkang, Journal of Inorganic Materials, 2011,26 (9): 912-916).Recently, Yan-Zhen Liu Wang etc. introduce Graphene and form Graphene/zinc oxide composite in zinc oxide and be used for ultracapacitor, its specific capacitance and cyclical stability obtain obviously to improve (Yan-Zhen Liu, Yong-Feng Li, Yong-Gang Yang, Yue-Fang Wen, Mao-Zhang Wang, Scripta Materialia, 68,301-304).Existing Graphene/Zinc-aluminium composite manufacture method is: first graphene oxide is reduced to Graphene take hydrazine hydrate etc. as strong reductant, mix take urea as the alkali source hydro thermal method with zinc and aluminium source presoma again and prepare Graphene/Zinc-aluminium, form Graphene/Zinc-aluminium composite material by thermal cracking at last.There are three aspect deficiencies in this chemical method.(1) not only use a large amount of poisonous chemical reagent hydrazine hydrates to cause human health damage and environmental pollution in the reduction process of graphene oxide, and the specific area decrease that serious reunion makes material occured in graphene nanometer sheet, affects the Compound Degree of Graphene and zinc-aluminium double-metal hydroxide.(2) the synthetic zinc-aluminium double-metal hydroxide particle diameter of hydro thermal method is larger, and a large amount of waste water of simultaneous are emitted, and are totally unfavorable to suitability for industrialized production.(3) prepared composite material bad dispersibility, thus cause specific capacitance low.Therefore set up green, efficient, controlled ultracapacitor imperative with Graphene/Zinc-aluminium composite manufacture method.
Microwave is electromagnetic a kind of, can produce the variation of Electric and magnetic fields in the space, causes that in material, polar molecule changes polarised direction, makes the molecular motion aggravation, obtains heat energy.Compare with traditional hydro thermal method, microwave method has its distinctive high reaction efficiency as synthetic a kind of new method of receiving grain, and method of operation is simple and be easy to reappear.Find through research widely and experiment repeatedly, first adopt microwave method to prepare graphite oxide/zinc-aluminium double-metal hydroxide composite material, method by high temperature pyrolysis again, double-metal hydroxide is decomposed the generation metal oxide in reduction-oxidation graphite, obtain the abundant Graphene that reduces/Zinc-aluminium composite material.
Summary of the invention
The technical problem to be solved in the present invention is exactly, the shortcomings such as Graphene reunite seriously, bimetallic oxide particle diameter large, composite material bad dispersibility, reaction time length serious for the environmental pollution of existing Graphene/Zinc-aluminium composite material existence, and a kind of new Graphene/Zinc-aluminium composite manufacture method is provided.The method has improved conductibility, the dispersiveness and stable of Graphene/Zinc-aluminium composite material significantly, and also environmental protection can not cause environmental pollution.
According to the technical scheme that the inventor provides, a kind of Graphene/Zinc-aluminium composite manufacture method and the application in ultracapacitor, step is:
1) graphite oxide, zinc salt and aluminium salt precursor body are dissolved in organic solvent, add a small amount of deionized water, ultrasonic being uniformly dispersed.
2) with 1) prepared mixed solution joins in microwave reactor, sets reaction temperature, microwave power and reaction time, opens microwave device, and the system of being stirred to begins to reflux.
3) organic solvent and alkali source compound are mixed, slowly drop to 2 from condenser pipes) in the backflow system of reacting, stir a period of time, cooling rear centrifugal, collecting precipitation, alcohol wash, vacuumize.
4) with 3) product that makes puts into tube furnace, passes into Ar/H
2Mist, high temperature pyrolysis makes Graphene/Zinc-aluminium composite material.
5) with 4) Graphene/Zinc-aluminium of making, acetylene black and polytetrafluoroethylene mix, and stirs, and then be coated with and the foam zinc surface, and be assembled into ultracapacitor.
Step 1) volume of described deionized water is 0.5～2mL.
Step 1) the concentration 0.0001～0.01g/mL of described graphene oxide.
Step 1) described organic solvent is to be selected from any in methyl alcohol, absolute ethyl alcohol, the tert-butyl alcohol, acetone, perhaps their mixture.
Step 1) described zinc and aluminium salt precursor body are to be selected from any in the sulfate that contains positive divalent zinc ion or positive trivalent aluminium ion or nitrate.
Step 1) mass ratio of described graphite oxide and zinc and aluminium salt precursor body total amount is 1: 1～10.The mass ratio of described zinc and aluminium salt precursor body and organic solvent is 1: 100～300.
Step 2) described microwave reaction temperature and time is respectively 50～80 ℃ and 0.5～1.0h.
Step 3) described alkali source compound is that be selected under hydrothermal condition can fast decoupled and discharge any in the ammoniacal liquor, urea, ammonium chloride of ammonia, perhaps their mixture.
Step 3) mass ratio of described alkali source compound and zinc and aluminium salt precursor body total amount is 1: 1～5.
Step 4) described Ar/H
2Mist volume ratio Ar: H
2Be 15～20: 1, the thermal cracking temperature is 500～800 ℃, and the thermal cracking time is 100～150min.
Step 5) described Graphene/Zinc-aluminium composite material and acetylene black and polytetrafluoroethylene are by 1: 0.1～0.3: 0.05～0.15.
Step 5) barrier film used of described assembling ultracapacitor is to be selected from any in the barrier film series that poly-the third vinyl material makes.The electrolyte that described assembling ultracapacitor is used is the potassium hydroxide solution of 3～6mol/L.
The microwave preparation of a kind of Graphene of the present invention/Zinc-aluminium composite material and application one preferred embodiment in ultracapacitor comprise the following steps:
1) take the 0.1g graphite oxide, 0.446gZn (NO
3)
26H
2O and 0.281gAl (NO
3)
39H
2O is dissolved in 150mL absolute ethyl alcohol water, adds the 1mL deionized water, ultrasonic being uniformly dispersed.
2) mixed solution is joined in microwave reactor, set 50～70 ℃ of reaction temperature lower limits, 80 ℃ of the upper limits are regulated microwave power 200W～500W, and reaction time 1.0h opens microwave device, and the system of being stirred to begins to reflux.
3) (V: V=9.5: 0.5) mixed solution, about adjusting microwave power 300～500W, control 0.5h drips and finishes, successive reaction 1h slowly dropwise to add the pre-configured absolute ethyl alcohol-ammoniacal liquor of 10mL from condenser pipe.Experiment finishes, and closes the microwave reaction device, and room temperature is cooling, vacuum filtration, and ethanol washing 5 times, 70 ℃ of dry 12h of vacuum obtain graphite oxide/zinc-aluminium double-metal hydroxide composite material.
4) graphite oxide/zinc-aluminium double-metal hydroxide composite material is placed in tube furnace, passes into Ar and H
2Volume ratio is the mist of 95: 5, is warming up to 600 ℃, and then insulation 120min is cooled to room temperature and makes Graphene/Zinc-aluminium composite material.
5) electrode preparation.Weighing 30mg Graphene/Zinc-aluminium and 5.6mg acetylene black are ground after mixing, add a little polyfluortetraethylene of binding element (15%), with the ultrasonic dispersion of a small amount of absolute ethyl alcohol 20min, after dispersion, it is coated in the foam zinc surface, obtain required electrode slice after 60 ℃ of lower vacuumize 12h.
In this preferred embodiment, first ultrasonic dispersion graphite oxide is in absolute ethyl alcohol, and zinc salt presoma, aluminium salt precursor body and alkali source compound microwave method prepare graphite oxide/zinc-aluminium double-metal hydroxide, then high temperature pyrolysis, pass into Ar/H
2Generate Graphene/Zinc-aluminium composite material.Studies show that, resulting Graphene/Zinc-aluminium is as the electrode material of ultracapacitor, and specific capacitance is greater than 700Fg
-1, after circulation charge-discharge 1000 times, its capacity can also keep 96% left and right.
The raw material that the present invention is used or reagent except specifying, equal commercially available getting.
Each preferred version of the present invention can be used in combination mutually.
Compared with prior art, the present invention has following significant advantage:
(1) under microwave action, the reaction of zinc salt and aluminium salt precursor body and alkali source compound generates double-metal hydroxide, is attached to the graphene oxide surface.At Ar/H
2In reducing atmosphere, the graphene oxide high temperature pyrolysis, oxy radical is stripped from, and prepares to reduce to get Graphene more thoroughly.The party's legal system need not to use poisonous chemical reducing agent, can make Graphene, environmental protection.In addition, double-metal hydroxide is attached to the graphene oxide surface, makes nanoscale twins separated from one another, has alleviated the reunion of Graphene.
(2) adopting absolute ethyl alcohol is solvent, the nanoscale zinc-aluminium double-metal hydroxide that forerunner's physical efficiency height of formation on the graphene oxide lamella is orderly.
(3) double-metal hydroxide that synthesizes by hydro thermal method is long reaction time, and the double-metal hydroxide particle diameter is large, bad dispersibility, and a large amount of waste water of simultaneous are emitted, thereby have limited its industrialized production and application.The double-metal hydroxide particle diameter that synthesizes by microwave method is very little, and specific area increases, and is convenient to fully contacting of electrode material and electrolyte, thereby causes the obviously increase of electric double layer capacitance amount part of super capacitor.Also significantly reduced the material preparation cycle in addition, and power consumption is few, cost is low, and step is simple, environmental protection.
(4) utilize the ultracapacitor that prepared Graphene/the Zinc-aluminium composite material assembles, charge/discharge capacity is greater than 700Fg
-1, after circulation charge-discharge 1000 times, its capacity can also keep more than 96%.This material obviously is better than traditional RuO in price and aspect of performance
2Deng metal oxide containing precious metals, be fit to the various high power capacities of suitability for industrialized production.
Embodiment
The below further illustrates the present invention with embodiment, but the present invention is not limited.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer." room temperature " described in the present invention, " normal pressure " refer to temperature and the air pressure between regular job, are generally 25 ℃, an atmospheric pressure.
In following embodiment, the electro-chemical test of electric capacity work electrode used is the foam zinc metal sheet that scribbles composite material (10mm * 10mm * 1mm), be that (10mm * 10mm * 1mm), reference electrode is the saturated calomel electrode electrode to platinum plate electrode to electrode.Electro-chemical test adopts time-measuring electric potential, and operating voltage is 0.0～0.5V, and the constant current charge-discharge current density is 1.0A/g.
Embodiment 1
Take the 0.1g graphite oxide, 0.446gZn (NO
3)
26H
2O and 0.281gAl (NO
3)
39H
2O is dissolved in 150mL absolute ethyl alcohol water, adds the 1mL deionized water, and ultrasonic being uniformly dispersed joins mixed solution in microwave reactor.Open microwave device, set 50 ℃ of reaction temperature lower limits, 80 ℃ of the upper limits are regulated microwave power 250W, and the system of being stirred to begins to reflux.(V: V=9.5: 0.5) mixed solution, about adjusting microwave power 300W, control 0.5h drips and finishes, successive reaction 1h slowly dropwise to add the pre-configured deionized water-ammoniacal liquor of 10mL.Close microwave oven, room temperature is cooling, vacuum filtration, and ethanol washing 5 times, 70 ℃ of dry 12h of vacuum obtain graphite oxide/zinc-aluminium double-metal hydroxide composite material.Graphite oxide/zinc-aluminium double-metal hydroxide composite material is placed in tube furnace, passes into Ar and H
2Volume ratio is the mist of 95: 5, is warming up to 600 ℃, and then insulation 120min is cooled to room temperature and makes Graphene/Zinc-aluminium composite material.Weighing 30mg Graphene/Zinc-aluminium and 5.6mg acetylene black are ground after mixing, add a little polytetrafluoroethylene (15%), with the ultrasonic dispersion of a small amount of absolute ethyl alcohol 20min, after dispersion, it is coated in the foam zinc surface, obtain required electrode slice after 60 ℃ of lower vacuumize 12h.As work electrode, platinum plate electrode is to electrode with resulting Graphene/Zinc-aluminium electrode, and saturated calomel electrode is reference electrode, and the 6.0mol/L potassium hydroxide solution is electrolyte assembling super capacitor.Electrochemical property test shows, its specific capacitance is 703.8F/g, and after discharging and recharging 1000 times, capacitance keeps 96.2%.
Embodiment 2
Take the 0.1g graphite oxide, 0.446gZn (NO
3)
26H
2O and 0.281gAl (NO
3)
39H
2O is dissolved in 150mL absolute ethyl alcohol water, adds the 1mL deionized water, and ultrasonic being uniformly dispersed joins mixed solution in microwave reactor.Open microwave device, set 60 ℃ of reaction temperature lower limits, 80 ℃ of the upper limits are regulated microwave power 250W, and the system of being stirred to begins to reflux.(V: V=9.5: 0.5) mixed solution, about adjusting microwave power 300W, control 0.5h drips and finishes, successive reaction 1h slowly dropwise to add the pre-configured deionized water-ammoniacal liquor of 10mL.Close microwave oven, room temperature is cooling, vacuum filtration, and ethanol washing 5 times, 70 ℃ of dry 12h of vacuum obtain graphite oxide/zinc-aluminium double-metal hydroxide composite material.Graphite oxide/zinc-aluminium double-metal hydroxide composite material is placed in tube furnace, passes into Ar and H
2Volume ratio is the mist of 95: 5, is warming up to 600 ℃, and then insulation 120min is cooled to room temperature and makes Graphene/Zinc-aluminium composite material.Weighing 30mg Graphene/Zinc-aluminium and 5.6mg acetylene black are ground after mixing, add a little polytetrafluoroethylene (15%), with the ultrasonic dispersion of a small amount of absolute ethyl alcohol 20min, after dispersion, it is coated in the foam zinc surface, obtain required electrode slice after 60 ℃ of lower vacuumize 12h.As work electrode, platinum plate electrode is to electrode with resulting Graphene/Zinc-aluminium electrode, and saturated calomel electrode is reference electrode, and the 6.0mol/L potassium hydroxide solution is electrolyte assembling super capacitor.Electrochemical property test shows, its specific capacitance is 689.4.3F/g, and after discharging and recharging 1000 times, capacitance keeps 95.8%.
Embodiment 3
Take the 0.1g graphite oxide, 0.446gZn (NO
3)
26H
2O and 0.281gAl (NO
3)
39H
2O is dissolved in 150mL absolute ethyl alcohol water, adds the 1mL deionized water, and ultrasonic being uniformly dispersed joins mixed solution in microwave reactor.Open microwave device, set 65 ℃ of reaction temperature lower limits, 80 ℃ of the upper limits are regulated microwave power 300W, and the system of being stirred to begins to reflux.(V: V=9.5: 0.5) mixed solution, about adjusting microwave power 350W, control 0.5h drips and finishes, successive reaction 1h slowly dropwise to add the pre-configured deionized water-ammoniacal liquor of 10mL.Close microwave oven, room temperature is cooling, vacuum filtration, and ethanol washing 5 times, 70 ℃ of dry 12h of vacuum obtain graphite oxide/zinc-aluminium double-metal hydroxide composite material.Graphite oxide/zinc-aluminium double-metal hydroxide composite material is placed in tube furnace, passes into Ar and H
2Volume ratio is the mist of 95: 5, is warming up to 600 ℃, and then insulation 120min is cooled to room temperature and makes Graphene/Zinc-aluminium composite material.Weighing 30mg Graphene/Zinc-aluminium and 5.6mg acetylene black are ground after mixing, add a little polytetrafluoroethylene (15%), with the ultrasonic dispersion of a small amount of absolute ethyl alcohol 20min, after dispersion, it is coated in the foam zinc surface, obtain required electrode slice after 60 ℃ of lower vacuumize 12h.As work electrode, platinum plate electrode is to electrode with resulting Graphene/Zinc-aluminium electrode, and saturated calomel electrode is reference electrode, and the 6.0mol/L potassium hydroxide solution is electrolyte assembling super capacitor.Electrochemical property test shows, its specific capacitance is 708.3F/g, and after discharging and recharging 1000 times, capacitance keeps 96.4%.
Embodiment 4
Take the 0.1g graphite oxide, 0.446gZn (NO
3)
26H
2O and 0.281gAl (NO
3)
39H
2O is dissolved in 150mL absolute ethyl alcohol water, adds the 1mL deionized water, and ultrasonic being uniformly dispersed joins mixed solution in microwave reactor.Open microwave device, set 70 ℃ of reaction temperature lower limits, 80 ℃ of the upper limits are regulated microwave power 350W, and the system of being stirred to begins to reflux.(V: V=9.5: 0.5) mixed solution, about adjusting microwave power 400W, control 0.5h drips and finishes, successive reaction 1h slowly dropwise to add the pre-configured deionized water-ammoniacal liquor of 10mL.Close microwave oven, room temperature is cooling, vacuum filtration, and ethanol washing 5 times, 70 ℃ of dry 12h of vacuum obtain graphite oxide/zinc-aluminium double-metal hydroxide composite material.Graphite oxide/zinc-aluminium double-metal hydroxide composite material is placed in tube furnace, passes into Ar and H
2Volume ratio is the mist of 95: 5, is warming up to 600 ℃, and then insulation 120min is cooled to room temperature and makes Graphene/Zinc-aluminium composite material.Weighing 30mg Graphene/Zinc-aluminium and 5.6mg acetylene black are ground after mixing, add a little polytetrafluoroethylene (15%), with the ultrasonic dispersion of a small amount of absolute ethyl alcohol 20min, after dispersion, it is coated in the foam zinc surface, obtain required electrode slice after 60 ℃ of lower vacuumize 12h.As work electrode, platinum plate electrode is to electrode with resulting Graphene/Zinc-aluminium electrode, and saturated calomel electrode is reference electrode, and the 6.0mol/L potassium hydroxide solution is electrolyte assembling super capacitor.Electrochemical property test shows, its specific capacitance is 658.3F/g, and after discharging and recharging 1000 times, capacitance keeps 95.2%.
Embodiment 5
Take the 0.1g graphite oxide, 0.446gZn (NO
3)
26H
2O and 0.281gAl (NO
3)
39H
2O is dissolved in 150mL absolute ethyl alcohol water, adds the 1mL deionized water, and ultrasonic being uniformly dispersed joins mixed solution in microwave reactor.Open microwave device, set 50 ℃ of reaction temperature lower limits, 80 ℃ of the upper limits are regulated microwave power 400W, and the system of being stirred to begins to reflux.(V: V=9.5: 0.5) mixed solution, about adjusting microwave power 500W, control 0.5h drips and finishes, successive reaction 1h slowly dropwise to add the pre-configured deionized water-ammoniacal liquor of 10mL.Close microwave oven, room temperature is cooling, vacuum filtration, and ethanol washing 5 times, 70 ℃ of dry 12h of vacuum obtain graphite oxide/zinc-aluminium double-metal hydroxide composite material.Graphite oxide/zinc-aluminium double-metal hydroxide composite material is placed in tube furnace, passes into Ar and H
2Volume ratio is the mist of 95: 5, is warming up to 600 ℃, and then insulation 120min is cooled to room temperature and makes Graphene/Zinc-aluminium composite material.Weighing 30mg Graphene/Zinc-aluminium and 5.6mg acetylene black are ground after mixing, add a little polytetrafluoroethylene (15%), with the ultrasonic dispersion of a small amount of absolute ethyl alcohol 20min, after dispersion, it is coated in the foam zinc surface, obtain required electrode slice after 60 ℃ of lower vacuumize 12h.As work electrode, platinum plate electrode is to electrode with resulting Graphene/Zinc-aluminium electrode, and saturated calomel electrode is reference electrode, and the 6.0mol/L potassium hydroxide solution is electrolyte assembling super capacitor.Electrochemical property test shows, its specific capacitance is 718.3F/g, and after discharging and recharging 1000 times, capacitance keeps 96.8%.
Claims (12)
1. the microwave preparation of Graphene/Zinc-aluminium composite material and the application in ultracapacitor, comprise
1) graphite oxide, zinc salt and aluminium salt precursor body are dissolved in organic solvent, add a small amount of deionized water, ultrasonic being uniformly dispersed.
2) with 1) prepared mixed solution joins in microwave reactor, sets reaction temperature, microwave power and reaction time, opens microwave device, and the system of being stirred to begins to reflux.
3) organic solvent and alkali source compound are mixed, slowly drop to 2 from condenser pipes) in the backflow system of reacting, stir a period of time, cooling rear centrifugal, collecting precipitation, alcohol wash, vacuumize.
4) with 3) product that makes puts into tube furnace, passes into Ar/H
2Mist, high temperature pyrolysis makes Graphene/Zinc-aluminium composite material.
5) with 4) Graphene/Zinc-aluminium of making, acetylene black and polytetrafluoroethylene mix, and stirs, and then be coated with and the foam zinc surface, and be assembled into ultracapacitor.
2. the method for claim 1, is characterized in that, the volume of described deionized water is 0.5～2mL.
3. the method for claim 1, is characterized in that, the concentration 0.0001～0.01g/mL of described graphene oxide.
4. the method for claim 1, is characterized in that, described organic solvent is to be selected from any in methyl alcohol, absolute ethyl alcohol, the tert-butyl alcohol, acetone, perhaps their mixture.
5. the method for claim 1, is characterized in that, described zinc and aluminium salt precursor body are to be selected from any in the sulfate that contains positive divalent zinc ion or positive trivalent aluminium ion or nitrate.
6. the method for claim 1, is characterized in that, the mass ratio of described graphite oxide and zinc and aluminium salt precursor body total amount is 1: 1～10.The mass ratio of described zinc and aluminium salt precursor body and organic solvent is 1: 100～300.
7. described microwave reaction temperature and time is respectively 50～80 ℃ and 0.5～1.0h.
8. the method for claim 1, is characterized in that, described alkali source compound is that be selected under hydrothermal condition can fast decoupled and discharge any in the ammoniacal liquor, urea, ammonium chloride of ammonia, perhaps their mixture.
9. the method for claim 1, is characterized in that, the mass ratio of described alkali source compound and zinc and aluminium salt precursor body total amount is 1: 1～5.
10. the method for claim 1, is characterized in that, described Ar/H
2Mist volume ratio Ar: H
2Be 15～20: 1, the thermal cracking temperature is 500～800 ℃, and the thermal cracking time is 100～150min.
11. the method for claim 1 is characterized in that, described Graphene/Zinc-aluminium composite material and acetylene black and polytetrafluoroethylene are by 1: 0.1～0.3: 0.05～0.15.
12. the method for claim 1 is characterized in that, the barrier film that described assembling ultracapacitor is used is to be selected from any in the barrier film series that poly-the third vinyl material makes.The electrolyte that described assembling ultracapacitor is used is the potassium hydroxide solution of 3～6mol/L.
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| CN109503888A (en) * | 2018-11-28 | 2019-03-22 | 沈阳理工大学 | A kind of preparation method of boehmite/graphene composite material |
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| CN105761948A (en) * | 2016-03-16 | 2016-07-13 | 辽宁博艾格电子科技有限公司 | Graphene supercapacitor |
| CN105761948B (en) * | 2016-03-16 | 2018-10-26 | 辽宁博艾格电子科技有限公司 | Graphene ultracapacitor |
| CN108314030A (en) * | 2018-03-29 | 2018-07-24 | 北京联合大学 | Mercury ion pollution waters restoration material |
| CN108314030B (en) * | 2018-03-29 | 2020-11-17 | 北京联合大学 | Mercury ion polluted water body repairing material |
| CN109503888A (en) * | 2018-11-28 | 2019-03-22 | 沈阳理工大学 | A kind of preparation method of boehmite/graphene composite material |
| CN109503888B (en) * | 2018-11-28 | 2020-09-08 | 沈阳理工大学 | Preparation method of boehmite/graphene composite material |
| CN114464760A (en) * | 2022-02-10 | 2022-05-10 | 合肥福纳科技有限公司 | Electron transport layer material and preparation method thereof, semiconductor device and preparation method thereof |
| CN114464760B (en) * | 2022-02-10 | 2024-03-26 | 合肥福纳科技有限公司 | Electron transport layer material, semiconductor device and preparation method of electron transport layer material and semiconductor device |
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