CN105197925A - Preparation method of nitrogen-doped activated carbon and application thereof - Google Patents
Preparation method of nitrogen-doped activated carbon and application thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of nitrogen-doped activated carbon and application thereof, aiming at solving the problems of complex process and high cost of degradation of wastes of nitrogenous bases-contained thermosetting polymers. The method comprises the following steps: preparing a polymer gel substance with an aminal dynamic covalent network structure; preparing a polymer product with the aminal dynamic covalent network structure; then performing high-temperature pyrolysis to obtain the nitrogen-doped activated carbon. The nitrogen-doped activated carbon prepared by the invention is applied to supercapacitors. The preparation method provided by the invention has the advantages that the preparation equipment is simple, environment-friendly and energy-saving, the prepared insoluble and non-melt thermosetting polymers are treated properly to be recycled, and the operation is simple and easy for large-scale production; the obtained activated carbon can be used as an electrode material of the supercapacitors. The invention belongs to the technical field of nano materials.
Description
Technical field
The present invention relates to a kind of preparation method and application thereof of nitrogen-dopped activated carbon.
Background technology
Nitrogenous based thermoset polymkeric substance, such as polymeric amide, polybenzimidazole, polyimide etc., it has good thermomechanical property, and resist chemical performance, electrical property etc. can well for the preparation of foams, sizing agent, automobile, aviation, electronics etc.The performance that but well-known, thermosetting polymer has " insoluble do not melt ".So once the shaping very difficult transformation of preparation, be difficult to process with product later, general degradation technique requires higher, and cost is higher, and its degraded will be for a long time.
Traditional energy sources approach exhaustion day by day, people are stimulated to go to find the alternative energy and effective energy storage device, power density is high, the duration of charging is short, the feature such as long service life, good temp characteristic, save energy and environmental protection because it has for ultracapacitor, good application prospect is had, the extremely concern of people in fields such as hybrid electric vehicle, power truck and backup power sources.
Gac is the advantage such as specific surface, stable chemical performance, preferably conductivity because having super large, one of important materials becoming electrode of super capacitor.
So consider whether obtained nitrogenous based thermoset polymkeric substance can be utilized again, prepare nitrogenous activated carbon material, be applied in electrical condenser.Rationally again utilize, environmental protection and energy saving, technique is simple, and cost is low, has important actual application value.
Summary of the invention
The object of the invention is the waste degradation complex process in order to solve nitrogenous based thermoset polymkeric substance, the higher and problem that can not be used in ultracapacitor of cost, provides a kind of preparation method and application thereof of nitrogen-dopped activated carbon.
The preparation method of a kind of nitrogen-dopped activated carbon of the present invention, carries out as follows:
One, Ursol D, paraformaldehyde and nitrogen methyl-2-pyrrolidone are put into three-necked bottle, nitrogen environment is protected, magnetic agitation, and reaction terminates rear temperature and is down to room temperature, obtains aminal dynamic covalent networks structural polymer spawn;
Two, by the sedimentation of dynamic for aminal covalent networks structural polymer spawn acetone, suction filtration vacuum-drying obtains aminal dynamic covalent networks structural polymer product;
Three, dynamic for aminal covalent networks structural polymer product is placed in tube furnace and carries out high temperature pyrolysis, obtain nitrogen-dopped activated carbon; Wherein the mol ratio of Ursol D and paraformaldehyde is 1:(1 ~ 6), the molecular volume of Ursol D and nitrogen methyl-2-pyrrolidone is than 1mmol:(2ml ~ 5ml).
The application of nitrogen-dopped activated carbon of the present invention refers to and is applied in ultracapacitor by nitrogen-dopped activated carbon, application method is: adopt nickel foam as collector, with nitrogen-dopped activated carbon, acetylene black and PVDF 8:1:1 preparation work electrode in mass ratio, with business gac, acetylene black, PVDF in mass ratio 8:1:1 preparation to electrode, assembling electrochemical capacitor.
Preparation equipment of the present invention is simple, environmental protection and energy saving, is suitably processed by obtained insoluble not molten thermosetting polymer, can again utilize, and simple to operate, is easy to scale operation; The nitrogen-dopped activated carbon obtained can be used as electrode material for super capacitor, and the electrode materials of preparation can keep stablizing reversible electrochemical properties, and along with the increase of sweep velocity, response current increases successively, illustrates to have good high rate performance.
Accompanying drawing explanation
The photo of the ultracapacitor working electrode that Fig. 1 is prepared for the nitrogen-dopped activated carbon that embodiment 1 obtains;
Fig. 2 is the nitrogen-dopped activated carbon that embodiment 1 obtains is the ultracapacitor photo that working electrode is assembled;
Cyclic voltammetry curve under the different scanning speed of the working electrode prepared with nitrogen-dopped activated carbon that Fig. 3 obtains for embodiment 1 in 6M potassium hydroxide electrolyte; Wherein a is 1mV/s, b be 3mV/s, c is 5mV/s;
The constant current charge-discharge curve of working electrode in 6M potassium hydroxide electrolyte prepared with nitrogen-dopped activated carbon that Fig. 4 obtains for the embodiment of the present invention 1; Wherein a is 1A/g, b be 2A/g, c be 3A/g, d be 4A/g, e is 5A/g;
The working electrode prepared with nitrogen-dopped activated carbon that Fig. 5 obtains for the embodiment of the present invention 1 in 6M potassium hydroxide electrolyte according to the ratio capacitance curve of constant current charge-discharge curve calculation gained;
Fig. 6 is the cyclic voltammetry curve under the different scanning speed of the working electrode prepared with nitrogen-dopped activated carbon that obtains of the embodiment of the present invention 2 in 1M sodium sulfate electrolytic solution; Wherein a is 1mV/s, b be 8mV/s, c is 10mV/s;
Fig. 7 is the constant current charge-discharge curve of working electrode in 1M sodium sulfate electrolytic solution prepared with nitrogen-dopped activated carbon that the embodiment of the present invention 3 obtains; Wherein a is 0.5A/g, b be 1A/g, c be 2A/g, d is 3A/g;
Fig. 8 be the working electrode prepared with nitrogen-dopped activated carbon that obtains of the embodiment of the present invention 3 in 1M sodium sulfate electrolytic solution according to the ratio capacitance curve of constant current charge-discharge curve calculation gained.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of a kind of nitrogen-dopped activated carbon of present embodiment, carry out as follows:
One, Ursol D, paraformaldehyde and nitrogen methyl-2-pyrrolidone are put into three-necked bottle, nitrogen environment is protected, magnetic agitation, and reaction terminates rear temperature and is down to room temperature, obtains aminal dynamic covalent networks structural polymer spawn;
Two, by the sedimentation of dynamic for aminal covalent networks structural polymer spawn acetone, suction filtration vacuum-drying obtains aminal dynamic covalent networks structural polymer product;
Three, dynamic for aminal covalent networks structural polymer product (PHDN) is placed in tube furnace and carries out high temperature pyrolysis, obtain nitrogen-dopped activated carbon; Wherein the mol ratio of Ursol D and paraformaldehyde is 1:(1 ~ 6), the molecular volume of Ursol D and nitrogen methyl-2-pyrrolidone is than 1mmol:(2ml ~ 5ml).
The application of the nitrogen-dopped activated carbon of present embodiment refers to and is applied in ultracapacitor by nitrogen-dopped activated carbon, application method is: adopt nickel foam as collector, with nitrogen-dopped activated carbon, acetylene black and PVDF 8:1:1 preparation work electrode in mass ratio, with business gac, acetylene black, PVDF in mass ratio 8:1:1 preparation to electrode, assembling electrochemical capacitor.
The Preparation equipment of present embodiment is simple, environmental protection and energy saving, is suitably processed by obtained insoluble not molten thermosetting polymer, can again utilize, and simple to operate, is easy to scale operation; The gac obtained can be used as electrode material for super capacitor, and the electrode materials of preparation can keep stablizing reversible electrochemical properties, and along with the increase of sweep velocity, response current increases successively, illustrates to have good high rate performance.
Embodiment two: present embodiment and embodiment one unlike: in step one, the mol ratio of Ursol D and paraformaldehyde is 1:5.Other is identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: in step one, Ursol D compares 1mmol:3ml with the molecular volume of nitrogen methyl-2-pyrrolidone.Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: in step one magnetic agitation refer to 50 DEG C condition lower magnetic force stir 24h.Other is identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: the method for the high temperature pyrolysis described in step 3 is: described PHDN is placed in porcelain boat, then puts into tube furnace; Nitrogen or argon gas is passed into except oxygen 3 ~ 8h in tube furnace, and using nitrogen or argon gas as protection gas, again by tube furnace with the ramp to 200 DEG C of 3 ~ 5 DEG C/min, then with the ramp to 450 DEG C of 0.5 ~ 2 DEG C/min, again with the ramp to 600 of 2 ~ 6 DEG C/min DEG C ~ 1100 DEG C, keep 2 ~ 4h; Then be cooled to 400 DEG C with the speed of 3 ~ 5 DEG C/min, then be down to room temperature, namely complete.Other is identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: the method for the high temperature pyrolysis described in step 3 is: described PHDN is placed in porcelain boat, then puts into tube furnace; Nitrogen or argon gas is passed into except oxygen 6h in tube furnace, and using nitrogen or argon gas as protection gas, then by tube furnace with the ramp to 200 DEG C of 5 DEG C/min, then with the ramp to 450 DEG C of 1 DEG C/min, again with the ramp to 700 DEG C of 4 DEG C/min, keep 2h; Then be cooled to 400 DEG C with the speed of 5 DEG C/min, then be down to room temperature, namely complete.Other is identical with one of embodiment one to five.
Embodiment seven: the application of present embodiment nitrogen-dopped activated carbon refers to and is applied in ultracapacitor by nitrogen-dopped activated carbon, application method is: adopt nickel foam as collector, with nitrogen-dopped activated carbon, acetylene black and PVDF 8:1:1 preparation work electrode in mass ratio, with business gac, acetylene black, PVDF in mass ratio 8:1:1 preparation to electrode, assembling electrochemical capacitor.
Embodiment eight: present embodiment and embodiment seven unlike: the concrete grammar of application is: one, porous nickel mesh is cut into 1 × 1cm
2square, with spot welding machine, nickel bar and the nickel foam that cuts out are welded together formation collector subsequently; Two, polyvinylidene difluoride (PVDF) is dissolved in N-Methyl pyrrolidone, is made into the PVDF/NMP solution that massfraction is 4%, as binding agent; Three, by the 8:1:1 mixing in mass ratio of nitrogen-dopped activated carbon, acetylene black, PVDF solid content, be placed in container, magnetic agitation 5 ~ 24h, then uniform blade coating on a current collector, 100 DEG C of vacuum-drying 12h again, then be placed in oil press, then use the pressure of 1 ~ 10MPa by compacting, be ultracapacitor working electrode.Other is identical with embodiment seven.
Embodiment nine: present embodiment and embodiment seven or eight unlike: the reference electrode of described ultracapacitor is mercury/red precipitate, and electrolytic solution is 6M potassium hydroxide.Other is identical with embodiment seven or eight.
Embodiment ten: one of present embodiment and embodiment seven to nine unlike: the reference electrode of described ultracapacitor is silver/silver chloride, and electrolytic solution is 1M sodium sulfate.Other is identical with one of embodiment seven to nine.
Beneficial effect of the present invention is verified by following examples:
The preparation method of embodiment 1, a kind of nitrogen-dopped activated carbon carries out as follows:
One, 10mmol Ursol D, 50mmol paraformaldehyde and 30mL nitrogen methyl-2-pyrrolidone are put into three-necked bottle, nitrogen environment is protected, 50 DEG C of magnetic agitation 24h, reaction terminates rear temperature and is down to room temperature, obtains 1.3000g aminal dynamic covalent networks structural polymer spawn;
Two, by the sedimentation of dynamic for aminal covalent networks structural polymer spawn acetone, suction filtration vacuum-drying obtains aminal dynamic covalent networks structural polymer product;
Three, take 0.8g aminal dynamic covalent networks structural polymer product and put into tube furnace, argon gas or nitrogen is passed into except oxygen 6h in tube furnace, and as protection gas, then by tube furnace with the ramp to 200 DEG C of 4 DEG C/min, the ramp to 450 DEG C of 1 DEG C/min afterwards, then with the ramp to 600 DEG C of 5 DEG C/min, 3h is kept; Be cooled to 400 DEG C with the speed of 5 DEG C/min again, be finally naturally down to room temperature again, obtain nitrogen-dopped activated carbon, weigh 0.384g, productive rate 48.6%.
Be applied in ultracapacitor by the nitrogen-dopped activated carbon of preparation, application method is: first porous nickel mesh is cut into 1 × 1cm
2square, with spot welding machine, nickel bar and the nickel foam that cuts out are welded together formation collector subsequently; Polyvinylidene difluoride (PVDF) (PVDF) is dissolved in N-Methyl pyrrolidone (NMP), is made into the PVDF/NMP solution that massfraction is 4%, as binding agent; By nitrogen-dopped activated carbon, acetylene black, PVDF (solid content) 8:1:1 mixing in mass ratio, be placed in container, magnetic agitation 24h, by the uniform blade coating of paste of becoming reconciled on a current collector, make it be uniformly distributed in the hole of nickel foam, 100 DEG C of vacuum-drying 12h, are finally placed in oil press by electrode slice complete for drying afterwards, with the pressure of 3MPa by electrode slice compacting, be ultracapacitor working electrode.With business gac, acetylene black, PVDF in mass ratio 8:1:1 preparation to electrode, be assembled into ultracapacitor; Reference electrode is mercury/red precipitate; Electrolytic solution is 6M potassium hydroxide.Test specimens product are labeled as PHDN-AC-1.
Ultracapacitor working electrode prepared by the gac obtained the present embodiment carries out the cyclic voltammetric performance test without sweep velocity in 6M potassium hydroxide electrolyte, and result, see Fig. 3, has good cyclic curve under different scanning speed.As known in Fig. 4 constant current charge-discharge figure, curve table reveals good trilateral, and under the current density of 1A/g, ratio capacitance can reach 153.8F/g, and when current density increases, when 5A/g, ratio capacitance still remains on 108F/g, shows good high rate performance.
Ultracapacitor working electrode prepared by the gac obtained the present embodiment carries out the ratio capacitance that constant current charge-discharge performance test obtains and calculates in potassium hydroxide electrolyte, result electric capacity respectively 153.8,128.6,120.6,109.8,108.4F/g, see Fig. 5.
The preparation method of embodiment 2, a kind of nitrogen-dopped activated carbon carries out as follows:
One, 10mmol Ursol D, 50mmol paraformaldehyde and 30mL nitrogen methyl-2-pyrrolidone are put into three-necked bottle, nitrogen environment is protected, 50 DEG C of magnetic agitation 24h, reaction terminates rear temperature and is down to room temperature, obtains 1.3000g aminal dynamic covalent networks structural polymer spawn;
Two, by the sedimentation of dynamic for aminal covalent networks structural polymer spawn acetone, suction filtration vacuum-drying obtains aminal dynamic covalent networks structural polymer product;
Three, take 0.8g aminal dynamic covalent networks structural polymer product and put into tube furnace, argon gas or nitrogen is passed into except oxygen 6h in tube furnace, and as protection gas, then by tube furnace with the ramp to 200 DEG C of 4 DEG C/min, the ramp to 450 DEG C of 1 DEG C/min afterwards, then with the ramp to 600 DEG C of 5 DEG C/min, 3h is kept; Be cooled to 400 DEG C with the speed of 5 DEG C/min again, be finally naturally down to room temperature again, obtain nitrogen-dopped activated carbon, weigh 0.384g, productive rate 48.6%.
Be applied in ultracapacitor by the nitrogen-dopped activated carbon of preparation, application method is: first porous nickel mesh is cut into 1 × 1cm
2square, with spot welding machine, nickel bar and the nickel foam that cuts out are welded together formation collector subsequently; Polyvinylidene difluoride (PVDF) (PVDF) is dissolved in N-Methyl pyrrolidone (NMP), is made into the PVDF/NMP solution that massfraction is 4%, as binding agent; By nitrogen-dopped activated carbon, acetylene black, PVDF (solid content) 8:1:1 mixing in mass ratio, be placed in container, magnetic agitation 18h, by the uniform blade coating of paste of becoming reconciled on a current collector, make it be uniformly distributed in the hole of nickel foam, 100 DEG C of vacuum-drying 12h, are finally placed in oil press by electrode slice complete for drying afterwards, with the pressure of 3MPa by electrode slice compacting, be ultracapacitor working electrode.With business gac, acetylene black, PVDF in mass ratio 8:1:1 preparation to electrode, be assembled into ultracapacitor; Reference electrode is silver/silver chloride; Electrolytic solution is 1M sodium sulfate.Test specimens product are labeled as PHDN-AC-2.
Ultracapacitor working electrode prepared by the gac obtained the present embodiment carries out the cyclic voltammetric performance test without sweep velocity in sodium sulfate electrolytic solution, and result is see Fig. 6.Have good cyclic curve under different scanning speed, in aqueous systems, electrochemical window can reach 1.5V.As known in Fig. 7 constant current charge-discharge figure, curve table reveals good trilateral, and under the current density of 1A/g, ratio capacitance is 88F/g, and when current density increases, when 5A/g, ratio capacitance is about 66F/g, shows good high rate performance.
Ultracapacitor working electrode prepared by the gac obtained the present embodiment carries out the ratio capacitance that constant current charge-discharge performance test obtains and calculates in potassium hydroxide electrolyte, and result ratio capacitance is 153.8F/g, 128.6F/g respectively, 120.6F/g, 109.8F/g, 108.4F/g, see Fig. 8.
The Preparation equipment of embodiment 1 ~ 2 is simple, environmental protection and energy saving, is suitably processed by obtained insoluble not molten thermosetting polymer, can again utilize, and simple to operate, is easy to scale operation; The nitrogen-dopped activated carbon obtained can be used as electrode material for super capacitor, and the electrode materials of preparation can keep stablizing reversible electrochemical properties, and along with the increase of sweep velocity, response current increases successively, illustrates to have good high rate performance.
Claims (10)
1. a preparation method for nitrogen-dopped activated carbon, is characterized in that the method is carried out as follows:
One, Ursol D, paraformaldehyde and nitrogen methyl-2-pyrrolidone are put into three-necked bottle, nitrogen environment is protected, magnetic agitation, and reaction terminates rear temperature and is down to room temperature, obtains aminal dynamic covalent networks structural polymer spawn;
Two, by the sedimentation of dynamic for aminal covalent networks structural polymer spawn acetone, suction filtration vacuum-drying obtains aminal dynamic covalent networks structural polymer product;
Three, dynamic for aminal covalent networks structural polymer product is placed in tube furnace and carries out high temperature pyrolysis, obtain nitrogen-dopped activated carbon; Wherein the mol ratio of Ursol D and paraformaldehyde is 1:(1 ~ 6), the molecular volume of Ursol D and nitrogen methyl-2-pyrrolidone is than 1mmol:(2ml ~ 5ml).
2. the preparation method of a kind of nitrogen-dopped activated carbon according to claim 1, is characterized in that the mol ratio of Ursol D and paraformaldehyde in step one is 1:5.
3. the preparation method of a kind of nitrogen-dopped activated carbon according to claim 1, is characterized in that in step one, Ursol D compares 1mmol:3ml with the molecular volume of nitrogen methyl-2-pyrrolidone.
4. the preparation method of a kind of nitrogen-dopped activated carbon according to claim 1, is characterized in that in step one, magnetic agitation refers to that the condition lower magnetic force at 50 DEG C stirs 24h.
5. the preparation method of a kind of nitrogen-dopped activated carbon according to claim 1, is characterized in that the method for the high temperature pyrolysis described in step 3 is: dynamic for aminal covalent networks structural polymer product is placed in porcelain boat, then puts into tube furnace; Nitrogen or argon gas is passed into except oxygen 3 ~ 8h in tube furnace, and using nitrogen or argon gas as protection gas, again by tube furnace with the ramp to 200 DEG C of 3 ~ 5 DEG C/min, then with the ramp to 450 DEG C of 0.5 ~ 2 DEG C/min, again with the ramp to 600 of 2 ~ 6 DEG C/min DEG C ~ 1100 DEG C, keep 2 ~ 4h; Then be cooled to 400 DEG C with the speed of 3 ~ 5 DEG C/min, then be down to room temperature, namely complete.
6. the preparation method of a kind of nitrogen-dopped activated carbon according to claim 1 or 5, is characterized in that the method for the high temperature pyrolysis described in step 3 is: dynamic for aminal covalent networks structural polymer product is placed in porcelain boat, then puts into tube furnace; Nitrogen or argon gas is passed into except oxygen 6h in tube furnace, and using nitrogen or argon gas as protection gas, then by tube furnace with the ramp to 200 DEG C of 5 DEG C/min, then with the ramp to 450 DEG C of 1 DEG C/min, again with the ramp to 700 DEG C of 4 DEG C/min, keep h; Then be cooled to 400 DEG C with the speed of 5 DEG C/min, then be down to room temperature, namely complete.
7. the application of nitrogen-dopped activated carbon that obtains of preparation method as claimed in claim 1, it is characterized in that this nitrogen-dopped activated carbon is applied in ultracapacitor, application method is: adopt nickel foam as collector, with nitrogen-dopped activated carbon, acetylene black and PVDF 8:1:1 preparation work electrode in mass ratio, with business gac, acetylene black, PVDF in mass ratio 8:1:1 preparation to electrode, assembling electrochemical capacitor.
8. the application of a kind of nitrogen-dopped activated carbon according to claim 7, is characterized in that the concrete grammar applied is: one, porous nickel mesh is cut into 1 × 1cm
2square, with spot welding machine, nickel bar and the nickel foam that cuts out are welded together formation collector subsequently; Two, polyvinylidene difluoride (PVDF) is dissolved in N-Methyl pyrrolidone, is made into the PVDF/NMP solution that massfraction is 4%, as binding agent; Three, by the 8:1:1 mixing in mass ratio of nitrogen-dopped activated carbon, acetylene black, PVDF solid content, be placed in container, magnetic agitation 5 ~ 24h, then uniform blade coating on a current collector, at 100 DEG C of vacuum-drying 12h, then be placed in oil press, then use the pressure of 1 ~ 10MPa by compacting, be ultracapacitor working electrode; With gac, acetylene black, PVDF in mass ratio 8:1:1 preparation to electrode, be assembled into ultracapacitor.
9., according to the application of claim 7 or 8 one kind of nitrogen-dopped activated carbon, it is characterized in that the reference electrode of described ultracapacitor is mercury/red precipitate, electrolytic solution is 6M potassium hydroxide.
10., according to the application of claim 7 or 8 one kind of nitrogen-dopped activated carbon, it is characterized in that the reference electrode of described ultracapacitor is silver/silver chloride, electrolytic solution is 1M sodium sulfate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109534341A (en) * | 2019-01-30 | 2019-03-29 | 中国矿业大学 | A kind of preparation method and applications of N doping pericarp base porous carbon material |
| US10889678B2 (en) | 2019-01-28 | 2021-01-12 | King Fahd University Of Petroleum And Minerals | Amine-based porous polymer for selective carbon dioxide capture |
| CN113800518A (en) * | 2020-06-17 | 2021-12-17 | 厦门稀土材料研究所 | Nitrogen-doped high-specific-surface-area porous carbon material and preparation method and application thereof |
| CN113845107A (en) * | 2021-10-29 | 2021-12-28 | 哈尔滨工业大学 | Method for preparing porous carbon nanosheet by virtue of two-dimensional covalent organic framework pyrolysis |
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| CN101306807A (en) * | 2008-04-30 | 2008-11-19 | 中国科学院上海硅酸盐研究所 | Method for preparing nitrogen-doped porous carbon material |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10889678B2 (en) | 2019-01-28 | 2021-01-12 | King Fahd University Of Petroleum And Minerals | Amine-based porous polymer for selective carbon dioxide capture |
| CN109534341A (en) * | 2019-01-30 | 2019-03-29 | 中国矿业大学 | A kind of preparation method and applications of N doping pericarp base porous carbon material |
| CN109534341B (en) * | 2019-01-30 | 2021-02-26 | 中国矿业大学 | Preparation method and application of nitrogen-doped pericarp-based porous carbon material |
| CN113800518A (en) * | 2020-06-17 | 2021-12-17 | 厦门稀土材料研究所 | Nitrogen-doped high-specific-surface-area porous carbon material and preparation method and application thereof |
| CN113800518B (en) * | 2020-06-17 | 2022-12-09 | 厦门稀土材料研究所 | Nitrogen-doped high-specific-surface-area porous carbon material and preparation method and application thereof |
| CN113845107A (en) * | 2021-10-29 | 2021-12-28 | 哈尔滨工业大学 | Method for preparing porous carbon nanosheet by virtue of two-dimensional covalent organic framework pyrolysis |
| CN113845107B (en) * | 2021-10-29 | 2024-03-15 | 哈尔滨工业大学 | Method for preparing porous carbon nano-sheet by utilizing two-dimensional covalent organic framework pyrolysis |
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