CN108615899B - Porous carbon material, preparation method thereof and application thereof in zinc-air battery - Google Patents
Porous carbon material, preparation method thereof and application thereof in zinc-air battery Download PDFInfo
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- H01M4/90—Selection of catalytic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses a heteroatom-doped porous carbon material, a preparation method thereof and application thereof in a zinc-air battery. The method comprises the following steps of self-assembling a biomass material in an alkaline solution to form a three-dimensional network structure self-assembly body, freeze-drying the three-dimensional network structure self-assembly body, placing the three-dimensional network structure self-assembly body in a protective atmosphere, and carbonizing the three-dimensional network structure self-assembly body to obtain the heteroatom-doped porous carbon material. The heteroatom doped porous carbon material has high catalytic activity and good stability, can replace the existing Pt/C, and can be used as an oxygen reduction catalyst to be applied to a zinc-air battery to obtain the zinc-air battery with stable discharge voltage and large capacity. And the heteroatom doped porous carbon material has simple preparation process and low cost, and is expected to be applied to industrial production.
Description
Technical Field
The invention relates to a porous carbon material and a preparation method and application thereof, in particular to a method for preparing a heteroatom-doped porous carbon material by forming a three-dimensional network structure self-assembly body through self-assembly of a biomass material in an alkaline solution and then performing freeze drying and high-temperature carbonization, and also relates to application of the heteroatom-doped porous carbon material as an oxygen reduction catalyst in a zinc-air battery anode material, belonging to the field of electrocatalytic energy storage materials.
Background
With the increasing global energy demand, the utilization of traditional fossil fuels (such as coal, oil and natural gas) in large quantities not only causes the change which is difficult to reverse in the environmental climate, but also causes the serious energy crisis due to the overuse of the primary energy. In the face of the increasingly exhausted energy, on one hand, energy is saved, new energy is developed, and meanwhile, the use efficiency of the energy is improved, but the use efficiency of the primary energy is only about 40 percent at present. The fuel cell is used as a novel energy conversion device, and the utilization rate of energy can be improved to about 70%. The oxygen reduction catalyst is a key component of fuel cells and metal air (the anode material of the cell), which determines the performance of fuel cells and metal zinc air cells. In recent years, a positive electrode material for a fuel cell has been a hot point of research as an energy source material. Platinum-based materials are currently commercially used in fuel cells, but their use is limited by their high cost and scarcity of resources. At present, various non-noble metals, including transition metals such as Fe, Co and the like, and compound material base catalysts of compounds of the transition metals and carbon are widely regarded, wherein the catalytic efficiency of some materials can be comparable to the performance of the Pt base catalyst, and particularly, the catalyst is superior to the Pt base catalyst in the aspects of stability, methanol resistance, CO resistance and the like. However, the problems such as poor stability under acidic conditions have not been solved effectively.
Non-metal doped carbon materials have been widely used in recent years as ORR catalysts, applied to positive electrode materials for fuel cells, having high stability and good electrical conductivity [ Gong K, Du F, Xia Z, et al, Nitrogen-doped carbon n anode catalysts with high electrochemical activity for oxygen production [ J ] Science,2009,323(5915): 760-. At present, people synthesize various non-metallic Carbon materials applied to Oxygen Reduction Catalysts, mainly comprising nitrogen, phosphorus, sulfur, boron and other atom doping and double-element doping thereof, and multi-element doping Carbon materials [ Zhang J, Qu L, Shi G, et al.N, P-doped Carbon Networks as effective metals-free Bifunctional Catalysts for Oxygen Reduction and Hydrogen Evolution Reactions [ J ]. Angew Chem Int Ed Engl,2016,55(6):2230 ]. The traditional preparation method at present is to obtain the heteroatom-doped carbon material by carbonizing a carbon source precursor and a precursor containing heteroatoms at high temperature. The commonly used nitrogen source materials at present are doped by urea, melamine, ammonia gas and the like at high temperature, and the doping form needs an additional nitrogen source. The existing preparation method of the porous material mainly adopts a template method and post-treatment thereof, and has complex process and high cost.
Disclosure of Invention
Aiming at the defects of low catalytic activity, limited material source, high preparation cost and the like of the anode material of the existing fuel cell and metal-air cell, the invention aims to provide the heteroatom-doped porous carbon material which has equivalent electrochemical activity with Pt/C and better stability, methanol poisoning resistance and the like than Pt/C.
The second purpose of the invention is to provide a method for preparing the heteroatom-doped porous carbon material with low raw material cost and simple process; compared with the existing preparation method, the method does not need to adopt a template agent or a pore-forming agent, has simple post-treatment and simplifies the process steps for preparing the porous carbon material.
The third purpose of the invention is to provide an application of the heteroatom-doped porous carbon material in a metal-air battery, wherein the porous carbon material is used as a zinc-air battery positive electrode material and shows higher catalytic activity, and the prepared zinc-air battery has the advantages of stable discharge voltage, large capacity and the like.
In order to achieve the technical purpose, the invention provides a preparation method of a heteroatom-doped porous carbon material, which comprises the steps of forming a three-dimensional network structure self-assembly body by self-assembly of a biomass material in an alkaline solution, freeze-drying the three-dimensional network structure self-assembly body, placing the three-dimensional network structure self-assembly body in a protective atmosphere, and carbonizing the three-dimensional network structure self-assembly body to obtain the heteroatom-doped porous carbon material.
According to the preferable scheme, the biomass material is dissolved in water, alkaline substances are added, and the mixture is stirred for 5-300 min at the temperature of 0-60 ℃ to obtain the three-dimensional network structure self-assembly. The reaction temperature is preferably room temperature. The reaction time is more preferably 30 min.
More preferably, the biomass material comprises at least one of protein, saccharide and natural lipid compound. Preferably protein Bovine Serum Albumin (BSA).
More preferably, the alkaline substance includes at least one of an alkali metal hydroxide and ammonia water. The alkali metal hydroxide is preferably sodium hydroxide and/or potassium hydroxide.
In a more preferable scheme, the concentration range of the biomass material in the alkaline solution is 1.0 mg/mL-100 mg/mL; the concentration of alkaline substances in the alkaline solution is 0.01-1.0M. The most preferred biomass material is BSA at a concentration of 75mg/mL in alkaline solution, relative to the concentration of sodium hydroxide used, of 0.4M.
The proportion of the biomass material to the sodium hydroxide in the technical scheme of the invention is directly related to the performance of the material, the specific surface area of the material is influenced by too little amount of the sodium hydroxide, so that the active sites of the material are exposed less, the electrochemical activity is reduced, a large amount of carbon material is corroded due to too much amount of the sodium hydroxide, the yield of the obtained carbon material is reduced to a great extent, and even the carbon material cannot be obtained due to complete corrosion.
In a preferred scheme, the carbonization temperature is 500-1200 ℃. According to the technical scheme, the carbonization temperature has a large influence on the porous material, the alkali substance sodium hydroxide etches the material at different temperatures, the higher the temperature is, the larger the reaction degree is, and in the carbonization process of the carbon material, the higher the temperature is, the better the crystallinity of the material is, and the better the performance of the material is. The preferred high-temperature carbonization temperature is 700-900 ℃.
In the technical scheme of the invention, the protective atmosphere is nitrogen or inert atmosphere or the mixed atmosphere of the nitrogen and the inert atmosphere, such as argon.
The invention provides a heteroatom doped porous carbon material, which is prepared by the preparation method.
In a preferable scheme, the pore size distribution range of the heteroatom-doped porous carbon material is 0.4-110 nm.
Preferably, the heteroatom-doped porous carbon material is a heteroatom in-situ doped porous carbon material.
In a preferred scheme, the porous carbon material is subjected to an electrocatalytic test of oxygen reduction, and the oxygen reduction electrocatalytic performance is equivalent to that of the existing platinum catalyst.
The invention also provides application of the porous carbon material, and the porous carbon material is used as an ORR catalyst to be applied to a zinc-air battery.
The heteroatom doped porous carbon material has the initial potential of (0.93V v/s RHE) under the alkaline condition and the half-wave potential of (0.83-0.84 v/s RHE) in the oxygen reduction process as an oxygen reduction catalyst, and has equivalent catalytic activity compared with Pt/C.
According to the technical scheme, the biomass materials such as protein, saccharides and the like adopted in the technical scheme can change the molecular structure of the biomass under the action of alkali, such as hydrolysis reaction and the like, so that the biomass can be partially degraded to generate small molecules containing amino groups, carboxyl groups, hydroxyl groups and other groups, in a solution system, due to good hydrophilicity of the groups, a hydrolysate can be dispersed in the solution system, and meanwhile, the groups can generate crosslinking through the action of hydrogen bonds or ionic bonds to carry out self-assembly, so that the whole solution system forms gel with a three-dimensional network structure, the gel adopts a freeze drying technology to maintain the three-dimensional network structure in a liquid phase, and thus a self-assembly with the three-dimensional porous structure is obtained, and the porous carbon material is obtained through high-temperature carbonization. The biomass material contains abundant heteroatoms such as P, S, N, and the heteroatoms are doped in the porous carbon material in situ during high-temperature carbonization.
In the technical scheme of the invention, the alkaline solution plays an important role in the whole preparation process of the porous carbon material, on one hand, the alkaline solution is used as an activator of the reaction of the biomass material and can promote the biomass material to form an assembly body with a three-dimensional structure in a solution system, on the other hand, the alkali has the function of activating the carbon material, the alkali is remained in the self-assembly body with the three-dimensional network structure after freeze drying, the alkali plays a role of a pore-forming agent in the high-temperature carbonization process and corrodes and forms pores on the carbon material, so that the carbon material obtains a large number of microporous structures, the specific surface area of the porous carbon material is greatly improved, a large number of active sites are exposed, and the.
According to the technical scheme, the porous carbon material obtained by self-assembling and carbonizing the natural product in the alkaline solution has a better effect in electrochemical oxygen reduction catalysis than the material obtained by directly carbonizing the natural product.
The preferred method for preparing the porous carbon material by utilizing the biomass material self-assembly body comprises the steps of selecting artificially purified BSA as a biomass material, dissolving the biomass material in water, adding alkali such as sodium hydroxide, continuously stirring to enable the biomass material to be self-assembled to obtain a gelatinous assembly body, then adopting an anhydrous assembly body of a freeze drying method, and finally carrying out high-temperature carbonization on the assembly body in a tube furnace under an inert atmosphere to obtain the heteroatom-doped porous carbon material.
The more preferable method for preparing the porous carbon material comprises the following specific steps:
step (1): preparation of biomass self-assembly
Dissolving a biomass material BSA in water, adding sodium hydroxide, continuously stirring at room temperature for 30min to obtain a biomass self-assembly body, and removing water by adopting a freeze drying method to obtain a dried biomass self-assembly body.
Step (2): obtaining the heteroatom-doped porous carbon material
And (3) placing the dried biomass self-assembly obtained in the step (1) in a tubular furnace, and carrying out high-temperature carbonization treatment in an inert atmosphere to obtain the heteroatom-doped porous carbon material.
The oxygen reduction electrocatalysis test method for the heteroatom doped porous carbon material comprises the following steps:
1. washing the obtained carbon material with secondary water for several times, vacuum drying, grinding a small amount of carbon material into superfine powder, and dispersing in ethanol solution;
2. dropping the dispersed liquid obtained in the step 1 on a glassy carbon electrode, adding Nafion for fixation, and testing the oxygen reduction potential under alkaline conditions and acidic conditions by using a rotary disc and an electrochemical workstation respectively;
3. and (2) dripping the dispersion obtained in the step (1) on carbon paper, then assembling a zinc-air battery by using the carbon paper as a positive electrode material, using a zinc sheet as a negative electrode material and using a sodium hydroxide solution as an electrolyte, and testing the battery performance of the zinc-air battery in a blue test system (LAND CT 2001A).
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) according to the invention, a biomass material is firstly utilized to react and self-assemble under an alkaline condition to obtain a self-assembly body with a three-dimensional network structure, and then the self-assembly body is subjected to freeze drying and high-temperature carbonization to obtain the heteroatom-doped porous carbon material. The biomass material is self-assembled to obtain the self-assembled body with the three-dimensional network structure, so that the defect that a template agent or a pore-forming agent is required for preparing the porous carbon material in the prior art is overcome, and the pore-forming step is simplified. Meanwhile, the biomass material contains a large amount of heteroatoms, and a heteroatom source does not need to be additionally added.
2) According to the invention, the biomass material is adopted as the starting material in the process of preparing the heteroatom-doped porous carbon material, and the material has the advantages of wide source, reproducibility, environmental friendliness, low cost and contribution to large-scale production.
3) The heteroatom doped porous carbon material shows electrochemical activity equivalent to that of Pt/C, and the performances of stability, methanol poisoning resistance and the like are superior to those of Pt/C.
4) The heteroatom-doped porous carbon material is used as an ORR catalyst and applied to a zinc-air battery, high catalytic activity is shown, and the prepared zinc-air battery has the advantages of stable discharge voltage, large capacity and the like.
5) The heteroatom doped porous carbon material disclosed by the invention is simple in preparation method and mild in condition, and meets the requirements of industrial production.
Drawings
FIG. 1 is an SEM image of self-assembly of biomass material under alkaline condition in example 1, wherein the three-dimensional network structure after gel formation is observed to have fine particles in enlarged part, and the substance is sodium hydroxide solid particles distributed in the biomass material;
fig. 2 is an optical image, an SEM image and a TEM image of the heteroatom-doped porous carbon material obtained after high-temperature carbonization in example 1, and it can be seen from the images that the material has a bulky porous structure on a macroscopic scale and also has a porous structure on a microscopic level;
fig. 3 shows the nitrogen isothermal elution curves and the pore size distribution diagrams of the three carbon materials in examples 1, 2 and 3, in which the specific surface area is increased and the pore structure distribution is wider with the same amount of alkali along with the increase of temperature;
FIG. 4 shows the nitrogen isothermal adsorption and desorption curves and the pore size distribution plots of the three carbon materials of examples 1 and 4; by regulating and controlling the amount of different alkalis, the specific surface area is increased and the distribution range of the pore structure is enlarged along with the increase of the amount of the alkalis;
FIG. 5 a) oxygen reduction alkaline conditions test LVS plots for 4 different carbon materials and commercial Pt/C materials in example 1, showing that the carbon materials have increasing catalytic activity for oxygen reduction with increasing alkali concentration and temperature, where the catalytic activity of BSA-8-900 is comparable to commercial Pt/C, b) LSV and K-L plots for BSA-8-900 in example 1;
FIG. 6 shows the LVS test of oxygen reduction reaction acid conditions of 4 different carbon materials and commercial Pt/C materials in example a) shows that the carbon material has an increasing catalytic activity for oxygen reduction with increasing alkali concentration and temperature, wherein BSA-8-900 has the best catalytic activity but some difference from Pt/C; b) LSV and K-L profiles for BSA-8-900 in example 1;
fig. 7 is a graph of data of the test of different carbon materials and commercial Pt/C materials as the positive electrode material of the zinc-air battery in example 4, a) is a model graph of the zinc-air battery; b) the figure is a polarization curve test of the material as the positive electrode material of the zinc-air battery, and the result shows that the performance of BSA-8-900 is good, the energy density is the highest, and is slightly higher than commercial Pt/C; c) the picture shows that the self-made button zinc-air battery lights up the LED lamp, and the curve is the change of long-time constant current discharge voltage; d) the graph is a voltage variation graph of discharge with different current densities.
Detailed Description
The following examples are intended to further illustrate the present invention, but not to limit the protection of the claims of the present invention.
Example 1
Step (1): preparation of biomass self-assembly
Dissolving 1.5g of biomass precursor BSA in 20mL of water, adding 8mmol of sodium hydroxide, continuously stirring at room temperature for 30min to obtain the biomass self-assembly. And removing water by adopting a freeze drying method to obtain a dried biomass self-assembly.
Step (2): obtaining the heteroatom-doped porous carbon material
Placing the dried biomass self-assembly obtained in the step (1) in a tubular furnace, and carbonizing at 900 ℃ in an inert atmosphere to obtain a heteroatom-doped porous carbon material, marked as BSA-8-900, with a specific surface area of 1274.1305m2 g-1The pore diameter is distributed in micropores, mesopores and macropores and is distributed in a multi-level pore mode.
And (3): testing of oxygen reduction reaction of carbon material and zinc-air battery assembly and testing:
1. the obtained carbon material is washed with secondary water for several times, dried in vacuum, and then a small amount of carbon material is taken, ground into ultrafine powder and dispersed in ethanol solution.
2. And (3) dropping the dispersed liquid obtained in the step (1) on a glassy carbon electrode, adding Nafion for fixation, and testing the oxygen reduction potential under alkaline conditions and acidic conditions by using a rotary disc and an electrochemical workstation respectively.
3. And (2) dripping the dispersion obtained in the step (1) on carbon paper, then assembling a zinc-air battery by using the carbon paper as a positive electrode material, using a zinc sheet as a negative electrode material and using a sodium hydroxide solution as an electrolyte, and testing the battery performance of the zinc-air battery in a blue test system (LAND CT 2001A).
Example 2
Step (1): dissolving 1.5g of biomass precursor BSA in 20mL of water, adding 8mmol of sodium hydroxide, continuously stirring at room temperature for 30min to obtain the biomass self-assembly. And removing water by adopting a freeze drying method to obtain a dried biomass self-assembly.
Step (2): obtaining the heteroatom-doped porous carbon material
Placing the dried biomass self-assembly obtained in the step (1) in a tube furnace, and carbonizing at 700 ℃ in an inert atmosphere to obtain a heteroatom-doped porous carbon material, marked as BSA-8-700, with the surface area of 548.7413m2g-1The pore size distribution is mainly concentrated in the microporous region, and the macroporous region has a small distribution.
And (3): testing of oxygen reduction reaction of carbon material and zinc-air battery assembly and testing:
1. the obtained carbon material is washed with secondary water for several times, dried in vacuum, and then a small amount of carbon material is taken, ground into ultrafine powder and dispersed in ethanol solution.
2. And (3) dropping the dispersed liquid obtained in the step (1) on a glassy carbon electrode, adding Nafion for fixation, and testing the oxygen reduction potential under alkaline conditions and acidic conditions by using a rotary disc and an electrochemical workstation respectively.
3. And (2) dripping the dispersion obtained in the step (1) on carbon paper, then assembling a zinc-air battery by using the carbon paper as a positive electrode material, using a zinc sheet as a negative electrode material and using a sodium hydroxide solution as an electrolyte, and testing the battery performance of the zinc-air battery in a blue test system (LAND CT 2001A).
Example 3
Step (1): dissolving 1.5g of biomass precursor BSA in 20mL of water, adding 8mmol of sodium hydroxide, continuously stirring at room temperature for 30min to obtain the biomass self-assembly. And removing water by adopting a freeze drying method to obtain a dried biomass self-assembly.
Step (2): obtaining the heteroatom-doped porous carbon material
Placing the dried biomass self-assembly obtained in the step (1) in a tube furnace, and carbonizing at 500 ℃ in an inert atmosphere to obtain a heteroatom-doped porous carbon material, marked as BSA-8-500, with a specific surface area of 17.3566m2g-1The pore size distribution is mainly distributed in a small amount in a large pore area.
And (3) testing the oxygen reduction reaction of the carbon material and assembling and testing the zinc-air battery:
1. the obtained carbon material is washed with secondary water for several times, dried in vacuum, and then a small amount of carbon material is taken, ground into ultrafine powder and dispersed in ethanol solution.
2. And (3) dropping the dispersed liquid obtained in the step (1) on a glassy carbon electrode, adding Nafion for fixation, and testing the oxygen reduction potential under alkaline conditions and acidic conditions by using a rotary disc and an electrochemical workstation respectively.
3. And (2) dripping the dispersion obtained in the step (1) on carbon paper, then assembling a zinc-air battery by using the carbon paper as a positive electrode material, using a zinc sheet as a negative electrode material and using a sodium hydroxide solution as an electrolyte, and testing the battery performance of the zinc-air battery in a blue test system (LAND CT 2001A).
Example 4
Step (1): dissolving 1.5g of biomass precursor BSA in 20mL of water, adding 2mmol of sodium hydroxide, stirring continuously at room temperature for 30min to obtain the biomass self-assembly. And removing water by adopting a freeze drying method to obtain a dried biomass self-assembly.
Step (2): obtaining the heteroatom-doped porous carbon material
Putting the dried biomass self-assembly obtained in the step (1) into a tube furnace, and carbonizing at 900 ℃ in an inert atmosphere to obtain a heteroatom-doped porous carbon material, marked as BSA-2-900, with a specific surface of 619.9392m2g-1The pore size distribution is mainly microporous and mesoporous regions.
And (3) testing the oxygen reduction reaction of the carbon material and assembling and testing the zinc-air battery:
1. the obtained carbon material is washed with secondary water for several times, dried in vacuum, and then a small amount of carbon material is taken, ground into ultrafine powder and dispersed in ethanol solution.
2. And (3) dropping the dispersed liquid obtained in the step (1) on a glassy carbon electrode, adding Nafion for fixation, and testing the oxygen reduction potential under alkaline conditions and acidic conditions by using a rotary disc and an electrochemical workstation respectively.
3. And (2) dripping the dispersion obtained in the step (1) on carbon paper, then assembling a zinc-air battery by using the carbon paper as a positive electrode material, using a zinc sheet as a negative electrode material and using a sodium hydroxide solution as an electrolyte, and testing the battery performance of the zinc-air battery in a blue test system (LAND CT 2001A).
Claims (6)
1. A preparation method of a heteroatom-doped porous carbon material is characterized by comprising the following steps: forming a three-dimensional network structure self-assembly body by self-assembly of protein in an alkaline solution, freeze-drying the three-dimensional network structure self-assembly body, and then placing the three-dimensional network structure self-assembly body in a protective atmosphere for carbonization to obtain a heteroatom-doped porous carbon material;
dissolving a biomass material in water, adding an alkaline substance, and stirring and reacting at 0-60 ℃ for 5-300 min to obtain a three-dimensional network structure self-assembly;
the concentration range of the protein in the alkaline solution is 1.0 mg/mL-100 mg/mL; the concentration of alkaline substances in the alkaline solution is 0.01-1.0M.
2. The method according to claim 1, wherein the heteroatom-doped porous carbon material comprises: the alkaline substance comprises alkali metal hydroxide and/or ammonia water.
3. The method according to any one of claims 1 to 2, wherein the method comprises the steps of: the carbonization temperature is 500-1200 ℃.
4. A heteroatom-doped porous carbon material characterized by: the method of any one of claims 1 to 3.
5. The heteroatom-doped porous carbon material of claim 4, wherein: the pore size distribution range of the porous carbon material is 0.4-110 nm.
6. The application of the heteroatom-doped porous carbon material is characterized in that: the catalyst is used as an ORR catalyst for zinc-air batteries.
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| CN110482526B (en) * | 2019-09-17 | 2022-02-08 | 哈尔滨工业大学 | Preparation method of biomass porous carbon electromagnetic wave-absorbing material with egg white as precursor |
| CN111151283B (en) * | 2020-01-15 | 2021-04-20 | 中南大学 | Nitrogen-cobalt co-doped porous carbon loaded sulfur-zinc-cobalt catalytic material and preparation method and application thereof |
| CN112777583B (en) * | 2021-01-26 | 2022-07-01 | 哈尔滨工业大学 | Preparation method of green heteroatom modified integrated biochar cathode |
| CN113410470A (en) * | 2021-05-21 | 2021-09-17 | 河南师范大学 | Preparation method of 3D cross-linked hierarchical pore heteroatom-doped carbon cathode catalyst |
| CN113430565B (en) * | 2021-06-16 | 2022-10-11 | 江西师范大学 | Method for preparing carbon-based transition metal nano composite catalyst from tremella |
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| CN102951636A (en) * | 2012-11-19 | 2013-03-06 | 大连理工大学 | Nitrogen-doped chitosan-based activated carbon and preparation method thereof |
| CN104843668A (en) * | 2015-04-23 | 2015-08-19 | 北京理工大学 | Method for preparing nitrogen doped porous carbon material by using biologic proteins |
| CN105752969A (en) * | 2016-02-29 | 2016-07-13 | 武汉理工大学 | Method for preparing polyatomic self-doped graphene by using natural porous and laminated vegetables |
| CN107331525A (en) * | 2017-07-10 | 2017-11-07 | 北京化工大学 | A kind of porous charcoal nanometer sheet electrode material of polyatom codope and its preparation method and application |
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