CN103204499B - Method for preparing spongy graphene - Google Patents
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Abstract
The invention relates to a method for preparing spongy graphene. The method comprises the steps: with graphite oxide as a raw material, preparing spongy oxidized graphene by lyophilization, wherein the prepared spongy oxidized graphene is used as a precursor; putting the prepared precursor into a crucible; then putting the crucible into a micro-wave vacuum sintering furnace, and irradiating by microwaves after vacuumizing, so as to obtain the spongy graphene. The prepared spongy graphene has a loose and porous unique structure, so that the spongy graphene has wide application prospect in the fields such as a super capacitor, a hydrogen storage material, a sensor and an adsorbing material. According to the method, microwave energy is instantaneously converted into internal energy of a sample based on a high-energy microwave irradiation mode; and by drastic thermal motion of molecules, oxygen-containing groups on the oxidized graphene are reduced into gas which rapidly volatiles and escape. Thus, the graphene can be obtained in a reducing manner and the loose and porous spongy aggregation structure can be remained.
Description
Technical field
The invention belongs to graphene preparation technology category, belong to the graphene preparation method of spongy specific morphology.
Background technology
Graphene, refers to the two-dimensional atomic crystal material be made up of less than 10 layers carbon atom close-packed arrays.Due to the structure of its uniqueness and electricity, the performance such as calorifics and mechanics of excellence, Graphene is with a wide range of applications in nano electron device, matrix material, solar cell, ultracapacitor, hydrogen storage material etc.Compared to film like, pulverous Graphene, spongy graphene has larger specific surface area and surface property, more loose pore structure and surface tissue, has larger using value in fields such as ultracapacitor, absorption, support of the catalyst.But obtain in spongy graphene at Fast back-projection algorithm, also there is no very effective method at present.And utilize microwave technology to prepare the work of spongy graphene, be not yet seen in report especially.
For microwave technology, at radar science and technology, ADS directed energy weapon, microwave oven, plasma generator, Radio Network System (as cell phone network, bluetooth, satellite television and WLAN technology etc.), sensing system has extensive and important application.In order to prevent microwave to the interference of radio communication, broadcast, radar, the frequency range that clear stipulaties can be applicable to microwave heating and microwave drying in the world only has four sections, and be namely respectively: L section, frequency is 890 ~ 940MHz, and centre wavelength is 0.330m; S section, frequency is 2.40 ~ 2.50GHz, and centre wavelength is 0.122m; C section, frequency is 5.725 ~ 5.875GMHz, and centre wavelength is 0.052m; K section, frequency is 22.0 ~ 22.25GHz, and centre wavelength is 0.008m.In order to prevent civilian microwave power, interference is caused to radio communication, broadcast, TV and radar etc., provision wavelengths is specifically designed to radar at the wave band of 1-25cm in the world, rest part is used for telecommunication transmission, L section and S section is only used in household microwave oven, and the frequency that can be used for the application such as industry, scientific research and medical science is mainly 915MHz, 2.45GHz, 28GHz.Therefore, the frequency range of material is prepared at the microwave that reality is available very limited.But utilize the rapid heating characteristic of microwave and carry out functional materials preparation synthesis, still achieve very large development, wherein also include paper and patent that microwave technology prepares Graphene.
Analyze the research paper published can find, existing microwave method prepares the efficiency of Graphene, effect is generally not ideal enough.Analyze the above results can find, these process are by lower powered microwave substantially, and with the regulation frequency range of 2.45GHz, irradiation oxidation graphite and obtain Graphene, cannot realize original position rapidly and thoroughly and peel off/reduce due to lower energy density.Therefore, the product that these investigation and application obtain is nearly all the more graphene nanometer sheet of lamella stacking or graphene microchip (i.e. Graphene nano-sheets, or Graphene sheets), and the Graphene of really (Graphene).Wherein, the Xue Lu equality of the Wang Can of East China University of Science etc., Nanjing Aero-Space University, household microwave oven (power≤900W) is utilized to carry out stripping and reduction-oxidation graphite, although assisting respectively at organic solvent, or obtain Graphene in solid state process stripping, or graphene microchip, but in product, there is the residual of oxygen groups, the functional performance such as electricity, calorifics of the Graphene that is unfavorable for fully volatilizing.
About the patent utilizing microwave technology to prepare Graphene, the representational application number mainly containing University Of Tianjin's application is 201010281619.6, patent name is: the method for microwave radiation preparation and purifying graphene under vacuum, in this invention, " graphite oxide is placed in reactor, and under forming 0.01Pa ~ 10KPa pressure, employings frequency is 300MHz ~ 300GHz; power is that the microwave of 50W ~ 2000W carries out radiation 2s ~ 600s to graphite oxide, graphite oxide be heated cleavage acquisition Graphene ".But as previously mentioned, for preventing the interference to communication, remote sensing, military use etc., the microwave frequency band that can be applied to heating and process material is according to the rules very limited.In addition, microwave exposure under a high vacuum very easily causes phenomenons such as " sparkings ", thus causes the dissipation of micro-wave energy, and causes damage to microwave sources such as magnetrons.Therefore, in this patent, in all wave band microwave of 300MHz ~ 300GHz, carry out the microwave exposure that vacuum lower limit is 0.1Pa, not only unrealistic, also there is certain danger.In addition, the verity of this patent that let us not go into the question now and feasibility, as carried out the microwave radiation of lower limit 50W according to this patent, based on the restriction that the required quantization of energy of reaction absorbs, its energy density cannot go beyond potential barrier needed for chemical reaction from principle, and the microwave that consequently can not realize Graphene peels off reduction.And if improve microwave power, as used the microwave power upper limit only up to 2000W, known according to the many sections of researchs reported above, what obtain will be the more graphene microchip (Graphenesheets) of the number of plies, the also Graphene (Graphene) of really meaning.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of simple and efficient efficient method preparing spongy graphene.
For solving the problem, the technical solution used in the present invention is: a kind of method preparing spongy graphene, comprises the steps: to adopt lyophilization, take graphite oxide as raw material, prepares spongiform graphene oxide as presoma; Obtained presoma is put into crucible, then crucible is put into microwave vacuum sintering oven, vacuumize rear microwave and carry out irradiation, obtain spongy graphene.
The porosity of described presoma is not less than 20%.
Described when vacuumizing, microwave vacuum sintering oven internal gas pressure scope is 15 ~ 50KPa.
The power range of described microwave is 4 ~ 10kW.
The time range of described irradiation is: 10 ~ 200 seconds.
Described crucible is made up of the material not absorbing microwave.Described crucible is made up of aluminum oxide or silica material.
The invention has the beneficial effects as follows: (1) process is simple and quick, easy to operate.Graphene oxide is excellent microwave absorbing medium, when suffering microwave exposure, can be heat energy by microwave energy rapidly.Whole microwave radiation process is very fast, only needs the extremely short time, can complete microwave cleavage and the reduction of graphene oxide.
(2) non-environmental-pollution in preparation process, technique environmental protection.
(3) controllability is strong: by power and the time of adjustment vacuum tightness, microwave exposure, can control the porosity of product spongy graphene.
(4) product property is homogeneous.Microwave radiation belongs to the heating of body phase penetration, irrelevant with the accumulation form, modes of emplacement etc. of sample, the performance of product will be caused to occur difference because the position residing for presoma is different.
Embodiment
Below by specific embodiment, a kind of method preparing spongy graphene of the present invention is described in further detail.
Prepare a method for spongy graphene, comprise the steps: to adopt lyophilization, take graphite oxide as raw material, prepare spongiform graphene oxide as presoma, the porosity of presoma is not less than 20%; Obtained presoma is put into crucible, and described crucible is made up of the material not absorbing microwave.Described crucible is made up of aluminum oxide or silica material, then crucible is put into microwave vacuum sintering oven, in order to improve microwave treatment effect, as much as possible crucible should be placed in the central position of the multimode cavity of microwave vacuum sintering oven, being evacuated to microwave vacuum sintering oven internal gas pressure scope is 15 ~ 50KPa, vacuumize rear unlatching microwave, the power range of microwave is 4 ~ 10kW, microwave irradiation time scope is: 10 ~ 200 seconds, after microwave treatment terminates, open vacuum valve, after multimode cavity air pressure balance, the Graphene of Sponge Porosity porous can be obtained in crucible.
Embodiment 1:
First prepare spongy graphene oxide as presoma using lyophilization.Utilize Hummers method to prepare on the basis of graphite oxide, getting 1.5g graphite oxide and be dissolved in 150ml deionized water, 40 DEG C of water-baths magnetic agitation 20 minutes, obtain the finely dispersed graphite oxide aqueous solution.Use freeze drier, first freezing chamber temperature is down to-50 DEG C, put into the graphite oxide aqueous solution again, quick-frozen about 1 hour, open vacuum pump after solidifying completely, make vacuum tightness maintain below 100Pa, freezing chamber temperature is about-10 ~ 0 DEG C, keep this state about 24 hours, allow water distil completely and namely obtain spongy graphene oxide presoma.Utilize N2 adsorption continuous flow method, determine that the porosity of spongy graphene oxide presoma is 40%.
Spongy for 1g graphene oxide is put into aluminum oxide (Al
2o
3) in crucible, crucible is placed on the central position of microwave vacuum sintering oven resonator cavity.Be evacuated to 25KPa after closing fire door, microwave power and irradiation time are set as 4.5kW and 60 second respectively, then carry out microwave exposure to sample.After process terminates, in crucible, obtain the spongy product of black.Utilize N2 adsorption continuous flow method, measuring product porosity is 48%, and using X-ray diffraction (XRD) to demonstrate product is Graphene, utilizes high-resolution-ration transmission electric-lens, can confirm that carbocyclic ring lamella accumulation horizon number is distributed between 2 ~ 5 layers substantially.
Utilize STA449F3 type thermogravimetric/differential thermal Thermal Synthetic Analysis instrument, the thermal properties analysis carried out within the scope of room temperature ~ 1000 DEG C with 10 DEG C/min heat-up rate finds, except the slight fluctuations that 50 DEG C of initial air-flows cause, sample quality free of losses, in view of the temperature of the oxydants such as dehydration general more than 100 DEG C, therefore can determine, after High-Power Microwave process, in product, anaerobic remains.
Embodiment 2:
Spongy graphene oxide precursor power process is with embodiment 1, and by the concentration of the adjustment graphite oxide aqueous solution, obtain spongy presoma, its porosity is 30%.
Vacuum microwave irradiation process is with embodiment 1, and adjustment microwave power and irradiation time are respectively 0.5kW and 200 second, and the vacuum degree control of resonator cavity, at below 50KPa, then carries out microwave exposure to sample.After process terminates, in crucible, obtain the spongy product of black.Utilize N2 adsorption continuous flow method, measuring product porosity is 33%, and use X-ray diffraction (XRD) and high-resolution-ration transmission electric-lens to prove that product is Graphene, carbocyclic ring lamella piles up the number of plies mainly between 3 ~ 8 layers.
Embodiment 3:
Spongy graphene oxide precursor power process is with embodiment 1, and by the concentration of the adjustment graphite oxide aqueous solution, obtain spongy presoma, its porosity is 60%.
Vacuum microwave irradiation process is with embodiment 1, and adjustment microwave power and irradiation time are respectively 8kW and 30 second, and the vacuum degree control of resonator cavity, at below 30KPa, then carries out microwave exposure to sample.After process terminates, in crucible, obtain the spongy product of black.Utilize N2 adsorption continuous flow method, measuring product porosity is 65%, using X-ray diffraction (XRD) and high-resolution-ration transmission electric-lens to prove that product is Graphene, substantially between 4 ~ 7 layers, and there is more individual layer or bilayer graphene structure in carbocyclic ring lamella accumulation horizon number.
Embodiment 4:
Spongy graphene oxide precursor power process is with embodiment 1, and by the concentration of the adjustment graphite oxide aqueous solution, obtain spongy presoma, its porosity is 45%.
Vacuum microwave irradiation process is with embodiment 1, and adjustment microwave power and irradiation time are set as 10kW and 15 second respectively, and the vacuum degree control of resonator cavity, at 15KPa, then carries out microwave exposure to sample.After process terminates, in crucible, obtain the spongy product of black.Utilize N2 adsorption continuous flow method, measuring product porosity is 49%, and use X-ray diffraction (XRD) and high-resolution-ration transmission electric-lens to prove that product is Graphene, carbocyclic ring lamella is piled up the number of plies and is mainly distributed between 2 ~ 4 layers.
Embodiment 5:
Spongy graphene oxide precursor power method is with embodiment 1, and by the concentration of the adjustment graphite oxide aqueous solution, obtain spongy presoma, its porosity is 50%.
Vacuum microwave irradiation process, with embodiment 1, keeps microwave power 4.5kW constant, and adjustment irradiation time is 100 seconds, and the vacuum degree control of resonator cavity, at below 40KPa, then carries out microwave exposure to sample.After process terminates, in crucible, obtain the spongy product of black.Utilize N2 adsorption continuous flow method, measuring product porosity is 60%, and use X-ray diffraction (XRD) and high-resolution-ration transmission electric-lens to prove that product is Graphene, carbocyclic ring lamella piles up the number of plies mainly between 4 ~ 6 layers.
Embodiment 6:
Spongy graphene oxide precursor power method is with embodiment 1, and by the concentration of the adjustment graphite oxide aqueous solution, obtain spongy presoma, its porosity is 70%.
Vacuum microwave irradiation process is with embodiment 1, and adjustment microwave power and irradiation time are respectively 5kW and 40 second, and in microwave resonator, vacuum tightness is 20KPa, then carries out microwave exposure to sample.After process terminates, in crucible, obtain the spongy product of black.Utilize N2 adsorption continuous flow method, measuring product porosity is 79%, and use X-ray diffraction (XRD) and high-resolution-ration transmission electric-lens to prove that product is Graphene, carbocyclic ring lamella piles up the number of plies mainly between 3 ~ 8 layers.
Embodiment 7:
Spongy graphene oxide precursor power method is with embodiment 1, and by the concentration of the adjustment graphite oxide aqueous solution, obtain spongy presoma, its porosity is 40%.
Vacuum microwave irradiation process is with embodiment 1, and adjustment microwave power and irradiation time are respectively 3kW and 180 second, and in microwave resonator, vacuum tightness is below 50KPa, then carries out microwave exposure to sample.After process terminates, in crucible, obtain the spongy product of black.Utilize N2 adsorption continuous flow method, measuring product porosity is 47%, and use X-ray diffraction (XRD) and high-resolution-ration transmission electric-lens to prove that product is Graphene, carbocyclic ring lamella piles up the number of plies mainly between 4 ~ 6 layers.
Embodiment 8:
Spongy graphene oxide precursor power method is with embodiment 1, and by the concentration of the adjustment graphite oxide aqueous solution, obtain spongy presoma, its porosity is 25%.
Vacuum microwave irradiation process is with embodiment 1, and adjustment microwave power and irradiation time are respectively 4kW and 50 second, and the vacuum degree control of resonator cavity, at below 30KPa, then carries out microwave exposure to sample.After process terminates, in crucible, obtain the spongy product of black.Utilize N2 adsorption continuous flow method, measuring product porosity is 30%, and use X-ray diffraction (XRD) and high-resolution-ration transmission electric-lens to prove that product is Graphene, carbocyclic ring lamella piles up the number of plies mainly between 5 ~ 7 layers.
Embodiment 9:
Spongy graphene oxide precursor power method is with embodiment 1, and by the concentration of the adjustment graphite oxide aqueous solution, obtain spongy presoma, its porosity is 20%.
Vacuum microwave irradiation process is with embodiment 1, and adjustment microwave power and irradiation time are respectively 10kW and 30 second, and the vacuum degree control of resonator cavity, at below 40KPa, then carries out microwave exposure to sample.After process terminates, in crucible, obtain the spongy product of black.Utilize N2 adsorption continuous flow method, measuring product porosity is 22%, and use X-ray diffraction (XRD) and high-resolution-ration transmission electric-lens to prove that product is Graphene, carbocyclic ring lamella piles up the number of plies mainly between 2 ~ 7 layers.
Embodiment 10:
Spongy graphene oxide precursor power method is with embodiment 1, and by the concentration of the adjustment graphite oxide aqueous solution, obtain spongy presoma, its porosity is 80%.
Vacuum microwave irradiation process is with embodiment 1, and adjustment microwave power and irradiation time are respectively 6kW and 90 second, and the vacuum degree control of resonator cavity, at below 30KPa, then carries out microwave exposure to sample.After process terminates, in crucible, obtain the spongy product of black.Utilize N2 adsorption continuous flow method, measuring product porosity is 86%, and use X-ray diffraction (XRD) and high-resolution-ration transmission electric-lens to prove that product is Graphene, carbocyclic ring lamella piles up the number of plies mainly between 4 ~ 8 layers.
Comparative example 1: with the contrast using liquid-phase reduction method to prepare Graphene.
Liquid-phase reduction method is graphene oxide method of reducing the most common.Spongy graphene oxide precursor power method and operation are with embodiment 1, and product porosity is 40%.Get 1g graphene oxide, add 200ml deionized water, after wiring solution-forming, namely the spongy of graphene oxide destroyed.
Heating in water bath at 80 DEG C, adds 10g sodium borohydride or hydrazine hydrate as reductive agent, reacts after 2 hours, goes washing and suction filtration with deionized water, at 40 DEG C dry 24 hours, obtains powdery graphite alkene.
Similar to solution phase chemical reduction, solvothermal method is also carry out reduction reaction in the solution, due to all that graphene oxide is water-soluble before reacting, also all will carry out drying treatment again after having reacted, therefore can only obtain pulverous Graphene product, cannot spongy graphene be prepared., there is certain harm to environment in a large amount of uses of the toxic chemical such as hydrazine hydrate, sodium borohydride simultaneously.
Comparative example 2: the effect comparison of the spongy graphene oxide of hot reducing method process
Spongy graphene oxide precursor power method and operation are with embodiment 1, and product porosity is 40%.
Retort furnace is heated to 1000 DEG C and constant temperature, then takes the spongy graphene oxide of 1g, put into aluminum oxide (Al
2o
3) crucible, put into rapidly the retort furnace of 1000 DEG C of constant temperature after building crucible cover.Take out sample observation after 1 minute, find the expanded one-tenth graphite worm of graphite oxide.Utilize scanning electron microscopic observation, graphite synusia is curled, and still remains crosslinked between synusia, and the thickness of synusia reduces, but thickness only reaches micron order, cannot obtain Graphene.In addition, the thermal reduction under normal pressure atmospheric environment, also results in sample and there occurs serious oxidation, loss of material is larger.
Comparative example 3: the effect comparison of vacuum low energy microwave spoke process graphite oxide
The preparation of the Graphene carried out according to patent " under vacuum microwave radiation preparation and the method for purifying graphene, CN 201010281619.6) " contrasts.
Because the microwave generator of other frequency ranges cannot be obtained, magnetron that frequency is 915MHz and 2.45GHz can only be utilized as microwave source, respectively at the microwave power of 50W ~ 2000W, under 0.01Pa ~ 10KPa vacuum pressure condition, carry out the process of graphite oxide.When attempting to carry out irradiation with the microwave power of 50W, in any case conversion vacuum pressure and irradiation time, all do not realize the stripping/reduction of graphite oxide.When carrying out irradiation with the microwave power of 2kW, there is cleavage in graphite oxide, and be stripped of oxy radical about 40 seconds time.But it is visible to utilize high-resolution-ration transmission electric-lens to detect, products distribution is uneven, is mingled with more to be stacked in 10 multilayers, even more multi-layered carbocyclic ring packed structures, and the effect peeled off/reduce, efficiency are not ideal.
The Comparative result of comparative example 4:900W microwave exposure liquid phase method process graphite oxide
East China University of Science utilizes " microwave exposure liquid phase method " (Wang Can, Wang Yanli, Zhan Liang, Deng .. Journal of Inorganic Materials, 2012,27:769-774.) ", for the 120mg graphite oxide be dispersed in the high boiling N-Methyl pyrrolidone of 40ml (NMP) organic solvent; utilize the Glanz microwave oven irradiation 3 minutes of 900W, obtain greatly about the Graphene of 2-5 layer.Although the use of organic solvent, make the lamella stacking of Graphene thinner, compared with vapor phase process, because treatment temp is difficult to rise to thousands of degree, removing of oxygen is not thorough, and residual oxygen is greatly about 13.2 ~ 13.6wt%.And there is the harm of chronic intoxicating in N-Methyl pyrrolidone (NMP) organic solvent, central nervous system dysfunction can be caused, cause the pathology etc. of respiratory organs, kidney, vascular system, working space maximum permissible concentration must not more than 100mg/m3, and therefore environmental issue is very important link.
Comparative example 5:800W Microwave Solid peels off the effect comparison of graphene oxide
Nanjing Aero-Space University utilizes " Microwave Solid stripping method " (Xue Luping, Zheng Mingbo, Shen Chenfei, Deng .. Chinese Journal of Inorganic Chemistry, 2010,26:1375-1381), the microwave treatment 30 ~ 240 seconds that power is 800W has been carried out to graphite oxide, what obtain is there is the residual graphene microchip (Graphene sheets) of oxygen, the functional performance such as electricity, calorifics of the Graphene that is unfavorable for fully volatilizing.
Comparative example 6:300W Microwave Solid peels off the effect comparison of graphene oxide
(the SHANMUGHARAJ A M such as Janowska, CHOI W S, LEE C W.Electrochemical performances of graphene nanosheets prepared through microwaveradiation.Journal of Power Sources, 2011,196:10249-10253.) expanded graphite is dispersed in supersound process 30min after ammonia soln, heats 1h ~ the 2h of recycling 300W, what obtain is the graphene microchip of tens layers substantially.
The summary of comparative example:
Hot reducing method principle and microwave radiation method similar, quick high-temp thermal treatment is carried out to graphene oxide, makes the oxygen-containing functional group of graphene oxide resolve into CO
2, gases such as water vapour and overflowing.Use the spongy graphene oxide of hot reducing method process, should can obtain spongiform Graphene equally principle.But fail to prepare Graphene in comparative example, its reason is that temperature rise rate is lower.When temperature rise rate is at least 2000 DEG C/min, react the temperature of carrying out more than 1000 DEG C time, just can obtain spongiform graphene oxide.These treatment condition just needing higher temperature and great temperature rise rate etc. harsh, therefore the method requires very high to the experiment equipment such as heating installation, vacuum pump, and cost is also high.In addition, in order to prevent graphene oxide to be direct oxidation into CO
2, need the reaction environment of ultravacuum (< 10-5Torr, about 1.3 × 10-3Pa) or a large amount of protection gas.And this is for the requirement improving heat conduction efficiency, run counter to again.And the vacuum microwave radiotreatment based on high-energy-density that the present invention uses, simple and fast, science is feasible, can realize the re-set target in operation and effect.
The above embodiments are the principle of illustrative the invention and effect thereof only, and the embodiment that part is used, but not for limiting the present invention; It should be pointed out that for the person of ordinary skill of the art, without departing from the concept of the premise of the invention, can also make some distortion and improvement, these all belong to protection scope of the present invention.
Claims (6)
1. prepare the method for spongy graphene for one kind, it is characterized in that: comprise the steps: to adopt lyophilization, take graphite oxide as raw material, use freeze drier, first freezing chamber temperature is down to-50 ° of C, put into the graphite oxide aqueous solution again, quick-frozen 1 hour, vacuum pump is opened after solidifying completely, vacuum tightness is made to maintain below 100Pa, freezing chamber temperature is-10 ~ 0 ° of C, keep this state 24 hours, allow water distil completely and namely obtain spongy graphene oxide presoma, prepare spongiform graphene oxide as presoma, the porosity of described presoma is not less than 20%, obtained presoma is put into crucible, then crucible is put into microwave vacuum sintering oven, vacuumize rear microwave and carry out irradiation, obtain spongy graphene.
2. a kind of method preparing spongy graphene according to claim 1, is characterized in that: described in when vacuumizing, microwave vacuum sintering oven internal gas pressure scope is 15 ~ 50KPa.
3. a kind of method preparing spongy graphene according to claim 1, is characterized in that: the power range of described microwave is 4 ~ 10kW.
4. a kind of method preparing spongy graphene according to claim 1, is characterized in that: the time range of described irradiation is: 10 ~ 200 seconds.
5. a kind of method preparing spongy graphene according to claim 1, is characterized in that: described crucible is made up of the material not absorbing microwave.
6. a kind of method preparing spongy graphene according to claim 5, is characterized in that: described crucible is made up of aluminum oxide or silica material.
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| CN103440995A (en) * | 2013-08-08 | 2013-12-11 | 中国科学院宁波材料技术与工程研究所 | Electrode material for super capacitor and preparing method thereof |
| CN104163423A (en) * | 2014-08-13 | 2014-11-26 | 东华大学 | Method for preparing spongy graphene by freeze drying |
| CN104671238B (en) * | 2015-02-06 | 2017-01-11 | 中国科学院山西煤炭化学研究所 | Method for quickly preparing high-performance graphene |
| CN105692598B (en) * | 2016-01-22 | 2017-11-17 | 浙江大学 | A kind of preparation method of lamella porous oxidation graphene and products thereof |
| WO2018044762A1 (en) * | 2016-08-31 | 2018-03-08 | Rutgers, The State University Of New Jersey | High-quality graphene and method of producing same via microwave reduction of graphene oxide |
| CN106629681A (en) * | 2016-12-27 | 2017-05-10 | 东南大学 | Preparation method of graphene foam |
| CN106985238A (en) * | 2017-03-27 | 2017-07-28 | 南通海鹰木业股份有限公司 | A kind of preparation method of the timber of composite graphite alkene layer |
| CN107328826A (en) * | 2017-08-08 | 2017-11-07 | 肇庆高新区长光智能技术开发有限公司 | A kind of portable ethanol detection means |
| CN107502765B (en) * | 2017-10-12 | 2018-10-09 | 钢铁研究总院 | A kind of high-throughput micro manufacturing method of multi-component material |
| CN108246268A (en) * | 2018-01-08 | 2018-07-06 | 兰州理工大学 | A kind of graphene oxide adsorbing material of Aminosilylation and preparation method thereof |
| CN108358191B (en) * | 2018-05-10 | 2022-04-29 | 郑州新世纪材料基因组工程研究院有限公司 | Low-defect graphene and preparation method thereof |
| CN114031071B (en) * | 2021-09-28 | 2023-07-18 | 云南华谱量子材料有限公司 | Method and equipment for preparing graphene by microwave excitation catalysis self-propagating |
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