WO2021027100A1 - 一种氮掺杂多孔炭材料及其制备方法与应用 - Google Patents

一种氮掺杂多孔炭材料及其制备方法与应用 Download PDF

Info

Publication number
WO2021027100A1
WO2021027100A1 PCT/CN2019/115808 CN2019115808W WO2021027100A1 WO 2021027100 A1 WO2021027100 A1 WO 2021027100A1 CN 2019115808 W CN2019115808 W CN 2019115808W WO 2021027100 A1 WO2021027100 A1 WO 2021027100A1
Authority
WO
WIPO (PCT)
Prior art keywords
nitrogen
porous carbon
doped porous
carbon material
carbon
Prior art date
Application number
PCT/CN2019/115808
Other languages
English (en)
French (fr)
Inventor
韩奎华
齐建荟
牛胜利
张晓峰
张继刚
李金晓
滕召才
王梅梅
李明
纪童童
曹阳
Original Assignee
山东大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 山东大学 filed Critical 山东大学
Priority to US17/049,802 priority Critical patent/US20230115681A1/en
Publication of WO2021027100A1 publication Critical patent/WO2021027100A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/342—Preparation characterised by non-gaseous activating agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/342—Preparation characterised by non-gaseous activating agents
    • C01B32/348—Metallic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/90—Other properties not specified above
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention belongs to the technical field of porous carbon material preparation, and specifically relates to a nitrogen-doped porous carbon material and a preparation method and application thereof.
  • Supercapacitors are the third generation of new energy storage devices following mechanical energy storage and chemical energy storage. Its power density is 10-100 times that of batteries, and it can realize high current charge and discharge, and has high charge and discharge efficiency and cycle life. Long and other characteristics. Widely demanded in the fields of electronic products, power systems, automobiles, rail transit, and aerospace, it has become a hot spot in the research of many green energy conversion and secondary energy storage devices.
  • Porous carbon is currently the preferred material for commercial supercapacitors due to its large specific surface area, developed pore structure and good electrical conductivity. Increasing the specific surface area of carbon materials can increase its specific capacitance to a certain extent, but its electrical storage performance and specific surface area are not simply linear. The purer the carbon material has fewer functional groups on the surface, resulting in its high specific surface area cannot be fully utilized. Simply increasing the specific surface area of the carbon material to increase its specific capacitance has great limitations. Heteroatom doping modification of carbon materials is an effective way to improve the performance of porous carbon materials. Nitrogen atoms and carbon atoms have similar atomic radii.
  • the structure of carbon itself is not easily destroyed, and it can change the six-membered ring structure of carbon into a five-membered ring structure, which leads to the surface structure and affinity of the material.
  • the changes in water and conductivity have greatly expanded the application fields of carbon materials.
  • Chinese Patent (Publication No. CN 108922794 A) discloses a preparation method of nitrogen-doped biomass-based activated carbon electrode material.
  • the doping process is set before the thermochemical treatment process, and the consumption of nitrogen source material is large; the thermochemical treatment temperature is high , The time is long, which greatly increases the cost of the preparation process.
  • Chinese Patent (Publication No. CN 108622877 A) discloses a nitrogen-doped porous carbon material with hierarchical pore structure and its preparation method and application. It uses cellulosic biomass as raw materials and organic matter urea and glycine as nitrogen sources. The steps include nitrogen source pretreatment, carbon source nitrogen source mixing, low-temperature carbonization, high-temperature activation, etc. The process is complicated and the consumption of nitrogen source materials is large.
  • the carbon material prepared by this process has a specific surface area of 2600m 2 g -1 , and at a current density of 3A g -1 , the specific capacitance can reach 210F g -1 , which is not up to the current standard of high-performance capacitive carbon.
  • Chinese Patent (Publication No. CN 108483442 A) discloses a method for preparing nitrogen-doped carbon electrode materials with high mesoporosity from bamboo shoot shells.
  • the steps include hydrothermal pretreatment, low-temperature carbonization simultaneous nitrogen doping, and activation treatment.
  • the steps are complicated.
  • the consumption of nitrogen source materials is large. In which a current density of 0.5A g -1 when the electric capacitance of 209F g -1, reach today's high performance carbon capacitance standard.
  • Chinese Patent (Publication No. CN 109319778 A) discloses a preparation method and application of a nitrogen-doped pine nut shell-based porous carbon material.
  • the nitrogen source material adopts chain nitrogen sources such as semicarbazide, urea, and guanidine carbonate.
  • the amount is large and the doping effect is not obvious.
  • the pretreatment process uses a low-temperature carbonization process, which cannot completely remove the volatiles in the raw materials, and a large number of H and O atoms are still retained in the carbonized product, resulting in low doping process efficiency.
  • the current density is 0.5A g -1 , its specific capacitance reaches 278-380F g -1 , and there is still room for further improvement.
  • the current related research and patents process biomass raw materials, although the specific surface area can be 300-2800m 2 g -1 , the specific capacitance can reach 100-380F g -1 , but there are still complex preparation processes and unreasonable process flow. , Carbon precursor raw materials are united, the consumption of nitrogen source materials is large, the nitrogen doping efficiency is low, and the doping structure is not stable enough. Its specific capacitance still does not reach the standard of high-performance capacitor carbon, and the doping method is not simple enough and environmentally friendly.
  • the purpose of the present invention is to provide a nitrogen-doped porous carbon material and its preparation method and application.
  • the technical solution of the present invention is:
  • the first object of the present invention is to provide a nitrogen-doped porous carbon material with a specific surface area of 1600-3500 m 2 g -1 , and the ratio of mesopores with a pore diameter of 2-50 nm to all pores is 20-40%, The average pore diameter is 2-20nm, and the mass percentage of nitrogen atoms in the porous carbon material is 13.6wt%-19.3wt%, which is much higher than the current level of related patents. Higher nitrogen content can effectively improve the surface structure, conductivity, and moisture of the material. Moisture, improve the electrochemical performance and adsorption performance of the material.
  • the porous carbon material When used as a supercapacitor materials, it has a greater capacitance than the capacitance and better retention, having a ratio of about 847F g -1 capacitor at a current density of 0.1A g -1, 5000 charge and discharge cycles After that, the capacitance retention rate was around 99.7%.
  • the porous carbon material has good CO 2 adsorption performance due to its excellent pore structure distribution.
  • the second object of the present invention is to provide a method for preparing nitrogen-doped porous carbon material, which includes the following steps:
  • the biomass powder is carbonized at a high temperature in a protective gas or ammonia atmosphere at a temperature of 600-800°C to obtain a carbonized product;
  • the impregnated product is heated and hybridized under an inert atmosphere to obtain biological nitrogen-doped porous carbon.
  • a high-temperature carbonization step is used in the preparation process, so that more volatiles and H and O atoms are removed during the carbonization process, and more active sites are provided.
  • the carbonized product is more easily combined with N atoms in further reactions, the efficiency of nitrogen doping is improved, and the amount of nitrogen source material used is reduced.
  • high-temperature carbonization makes the carbonized product have a higher porosity and a larger pore size, which is conducive to a larger area of contact between the carbon material and the activator and the doping material, and is conducive to the further progress of the reaction.
  • Ammonia can provide amino groups and assist the nitrogen doping process. When the volatilization is analyzed, it can be combined with the active site vacant on the carbon ring in time.
  • the product After the impregnation, the product is heated and hybridized under an inert atmosphere, so that nitrogen atoms replace carbon atoms on the carbon ring and form a part of a five-membered ring structure.
  • cyclic nitrogen source has higher stability than the chain nitrogen source.
  • cyclic nitrogen sources such as melamine, polyaniline, and pyridine are used to dope porous carbon with nitrogen, the preparation process parameters Optimized to make the porous carbon material have better stability, even after thousands of charging and discharging, there is still no obvious loss of specific capacitance.
  • Ultrasonic treatment of the impregnation system can effectively promote the mixing of chemical activators and nitrogen source materials, avoiding too complicated material pretreatment methods (such as immersion and mixing at high temperature, immersion and mixing in dilute solution and then evaporation, and nitrogen source material pretreatment Re-dipping, mixing, etc.), which greatly shortens the processing time and improves the processing efficiency.
  • the carbonaceous precursor includes, but is not limited to, garlic braid, sargassum, wood chips, husk, and straw.
  • the carbonaceous precursor is pulverized and passed through an 80-mesh sieve.
  • An excessively large particle size will cause insufficient reaction of the material in the next steps, and an excessively small particle size will increase the cost of material preparation.
  • the carbonization time is 1.5-2.5h.
  • the saturated solution of the chemical activator is a saturated solution of KOH.
  • the nitrogen source material of the present invention is difficult to dissolve in water, and a too low concentration will affect the efficiency of the dipping process, and the saturated KOH solution can ensure the full infiltration of KOH.
  • the mass ratio of the carbonized product, the saturated solution of the chemical activator and the nitrogen source material is 1-3:1-5:0.1-2.
  • the amount of nitrogen source material used in the present invention is small, but better nitrogen doping can be achieved.
  • the temperature of ultrasonic immersion is room temperature.
  • the frequency of the ultrasonic treatment is 10-50kHz
  • the power is 80-150W
  • the time of the ultrasonic treatment is 4-8min.
  • the temperature of the heat treatment is 750-800°C, and the time of the heat treatment is 2-2.5h.
  • the preparation method further includes the steps of washing and drying the obtained biological nitrogen-doped porous carbon.
  • the porous carbon is washed to remove impurities in the porous carbon.
  • the obtained biological nitrogen-doped porous carbon is acid washed with 10-20 wt% hydrochloric acid, and then washed with deionized water to neutrality.
  • the third object of the present invention is to provide nitrogen-doped porous carbon prepared by the above preparation method.
  • the fourth objective of the present invention is to provide the application of the aforementioned nitrogen-doped porous carbon in the preparation of supercapacitor materials.
  • the fifth object of the present invention is to provide an activated carbon electrode, the composition of which includes the aforementioned nitrogen-doped porous carbon.
  • the components of the activated carbon electrode further include a conductive agent and a binder
  • the conductive agent is conductive carbon black, acetylene black, graphite additives or carbon nanotube additives
  • the binder is PTFE (polytetrafluoroethylene), PVDF (polyvinylidene fluoride), polyvinyl alcohol, sodium light methyl cellulose, polyolefins, rubber or polyurethane.
  • the sixth object of the present invention is to provide a method for preparing the above activated carbon electrode, which includes the following steps:
  • the slurry is heated and pressed into a shape.
  • the current collector is copper foil, aluminum foil, nickel mesh or stainless steel foil.
  • the seventh object of the present invention is to provide the application of the above-mentioned nitrogen-doped porous carbon as a CO 2 adsorbent.
  • the high-temperature carbonization step is used in the preparation process of the present invention, so that more volatile components and H and O atoms are removed during the carbonization process, and more active sites are provided.
  • the carbonized products are easier to combine with N atoms in further reactions, which improves the efficiency of nitrogen doping and reduces the amount of nitrogen source materials used.
  • high-temperature carbonization makes the carbonized product have a higher porosity and a larger pore size, which is conducive to a larger area of contact between the carbon material and the activator and the doping material, and is conducive to the further progress of the reaction.
  • the molecular structure of the nitrogen source used in the present invention is cyclic, which has higher stability than chain nitrogen sources.
  • the porous carbon material prepared according to the process of the present invention is mainly composed of pyrrole nitrogen and graphitic nitrogen. Stable, so the material still has no obvious loss of capacitance after thousands of charging and discharging.
  • the present invention uses optimized process steps, avoids overly complicated material pretreatment methods, introduces ultrasound to mix the activator and the nitrogen source material, greatly shortens the processing time and improves the processing efficiency.
  • the invention has simple process, wide source of raw materials, low cost, easy control of the reaction process, easy large-scale production, and has broad application prospects in the fields of supercapacitor electrode materials and CO 2 adsorption materials, which are embodied in the following aspects: (1) Application The nitrogen-doped porous carbon material prepared by the technical process of the invention has a three-dimensional hierarchical pore structure with a specific surface area of 1600-3500 m 2 g -1 ; (2) a larger specific capacitance and better capacitance retention: when it is used as a super The capacitor electrode material has a specific capacitance of 847F g -1 at a current density of 0.1A g -1 .
  • the CO 2 adsorption test shows that The adsorption capacity at 25°C and 0°C is as high as 3.59 and 6.11mmol/g, respectively, showing excellent pore structure distribution and CO 2 adsorption performance.
  • Figure 1 is a graph of nitrogen adsorption-desorption curve obtained in Example 1 of the present invention.
  • Figure 2 is a pore size distribution diagram obtained in Example 1 of the present invention.
  • Fig. 3 is a cycle performance graph obtained in Example 1 of the present invention.
  • Fig. 4 is a cyclic voltammetry curve obtained by testing the electrode material prepared in Example 2 of the present invention at a sweep rate of 200 mV s -1 .
  • Figure 5 is a constant current charge and discharge curve obtained by testing the electrode material prepared in Example 2 of the present invention at a current density of 5A g -1 .
  • Fig. 6 is a graph showing the rate performance obtained by the electrode material prepared in Example 2 of the present invention.
  • FIG. 7 is an SEM image of the nitrogen-doped porous carbon material prepared in Example 3 of the present invention.
  • This embodiment relates to a method for preparing nitrogen-doped porous carbon, including the following steps:
  • Step one Wash the raw garlic braids, place them in a blast drying oven at 120°C for 48 hours, crush them and pass through an 80-mesh sieve.
  • Step 2 Place the product obtained in Step 1 in a tube furnace and carbonize at 600°C for 2 hours. Use nitrogen as a protective gas.
  • Step 3 Wash and dry the product obtained in Step 2.
  • Step 4 The products obtained in the three steps are ultrasonically treated with a saturated KOH solution and melamine at a mass ratio of 1:4:0.2 for 6 minutes, the ultrasonic frequency is 40kHz, and the power is 120W.
  • Step 5 Put the product obtained in Step 4 in a muffle furnace and treat it at 800°C for 2 hours. Nitrogen is used as a protective gas.
  • Step 6 The product obtained in Step 5 is first pickled with hydrochloric acid, then washed with deionized water to neutrality, and dried to obtain nitrogen-doped biomass-based porous carbon material.
  • the nitrogen atom mass ratio of the product is as high as 19.3wt%.
  • the specific surface area calculated by the BET method is 2642m 2 /g, the pore volume is 1.41cm 3 /g, and the average pore diameter is 2.14nm. It is a kind of high specific surface area.
  • the electrode material for supercapacitors prepared by mixing this carbon material, conductive agent and binder at a mass ratio of 8:1:1, using 6mol/L KOH as the electrolyte for constant current charge and discharge test, the current density is 0.1
  • the specific capacitance value at A/g reaches 847F/g, as shown in Figure 6, it can still reach 649F/g when the current density is 10A/g.
  • This embodiment relates to a method for preparing nitrogen-doped porous carbon, including the following steps:
  • Step 1 Wash the Sargasso raw material, place it in a blast drying oven at 120°C for 48 hours, crush and pass through an 80-mesh sieve.
  • Step 2 Place the product obtained in Step 1 in a tube furnace, raise it to 800°C, and keep it at this temperature for 1.5 hours.
  • Argon is used as a protective gas.
  • Step 3 Wash and dry the product obtained in Step 2.
  • Step 4 Mix the products obtained in the three steps with the saturated KOH solution and polyaniline at a mass ratio of 1:5:0.3, ultrasonic treatment for 10 minutes, ultrasonic frequency of 50kHz, and power of 100W.
  • Step 5 Put the product obtained in Step 4 in a muffle furnace and treat it at 750°C for 2.5 hours. Nitrogen is used as a protective gas.
  • Step 6 The product obtained in Step 5 is first pickled with 15wt% hydrochloric acid, then washed with deionized water to neutrality, and dried to obtain nitrogen-doped biomass-based porous carbon material.
  • the product has a nitrogen atom mass ratio of 15.4wt%.
  • the specific surface area calculated by the BET method is 2543m 2 /g, the pore volume is 1.52cm 3 /g, and the average pore size is 2.39nm, which is a kind of high specific surface area.
  • the electrode material for supercapacitors prepared by mixing this carbon material, conductive agent and binder at a mass ratio of 8:1:1, using 6mol/L KOH as the electrolyte for constant current charge and discharge test, the current density is 0.1
  • the specific capacitance value at A/g reaches 594F/g, and it can still reach 463F/g at a current density of 10A/g.
  • This embodiment relates to a method for preparing nitrogen-doped porous carbon, including the following steps:
  • Step 1 Wash the raw wood chips, place them in a blast drying oven at 105°C for 72 hours, crush them and pass through a 120-mesh sieve.
  • Step 2 Place the product obtained in Step 1 in a tube furnace and keep it at 600°C for 2 hours. Helium is used as a protective gas.
  • Step 3 Wash and dry the product obtained in Step 2.
  • Step 4 Mix the product obtained in step 3 with a KOH saturated solution with a mass ratio of 3:1 (charcoal: activator) and a 1:7 (charcoal: nitrogen source) pyridine, ultrasonic treatment for 4 minutes, ultrasonic frequency of 30kHz, power 140W.
  • Step 5 Place the product obtained in Step 4 in a muffle furnace and keep it at 750°C for 2.5 hours. Ammonia is used as a protective gas.
  • Step 6 Wash and dry the product obtained in Step 5 to obtain nitrogen-doped biomass-based porous carbon material.
  • the product has a nitrogen atom mass ratio of 13.6wt%.
  • the specific surface area calculated by the BET method is 2098m 2 /g, the pore volume is 1.40cm 3 /g, and the average pore size is 2.14nm, which is a kind of high specific surface area.
  • the electrode material for supercapacitors prepared by mixing this carbon material, conductive agent and binder at a mass ratio of 8:1:1, using 6mol/L KOH as the electrolyte for constant current charge and discharge test, the current density is 0.1
  • the specific capacitance value at A/g reaches 330F/g, and it can still reach 260F/g at a current density of 10A/g.
  • Fig. 7 is an SEM picture of the nitrogen-doped porous carbon material prepared in Example 3. It can be seen from the picture that the material has a rich pore structure.
  • This embodiment relates to a method for preparing biomass-based nitrogen-doped porous carbon, including the following steps:
  • Step one Wash the raw garlic braids, place them in a blast drying oven at 120°C for 48 hours, crush them and pass through an 80-mesh sieve.
  • Step 2 Place the product obtained in Step 1 in a tube furnace and carbonize at 600°C for 2 hours. Use nitrogen as a protective gas.
  • Step 3 Wash and dry the product obtained in Step 2.
  • Step 4 Mix the products obtained in the three steps with KOH and melamine in a mass ratio of 1:3:0.2, ultrasonic treatment for 8 minutes, ultrasonic frequency of 10kHz, and power of 80W.
  • Step 5 Put the product obtained in Step 4 in a muffle furnace and treat it at 800°C for 2 hours. Nitrogen is used as a protective gas.
  • Step 6 The product obtained in Step 5 is first pickled with hydrochloric acid, then washed with deionized water to neutrality, and dried to obtain nitrogen-doped biomass-based porous carbon material.
  • This embodiment relates to a method for preparing biomass-based nitrogen-doped porous carbon, including the following steps:
  • Step 1 Wash the raw wood chips, place them in a blast drying oven at 105°C for 72 hours, crush them and pass through a 120-mesh sieve.
  • Step 2 Place the product obtained in Step 1 in a tube furnace and keep it at 600°C for 2 hours. Helium is used as a protective gas.
  • Step 3 Wash and dry the product obtained in Step 2.
  • Step 4 Mix the product obtained in Step 3 with a KOH saturated solution with a mass ratio of 3:1 (charcoal: activator) and a 1:7 (charcoal: nitrogen source) pyridine, ultrasonic treatment for 5 minutes, ultrasonic frequency of 50kHz, and power 150W.
  • a KOH saturated solution with a mass ratio of 3:1 (charcoal: activator) and a 1:7 (charcoal: nitrogen source) pyridine, ultrasonic treatment for 5 minutes, ultrasonic frequency of 50kHz, and power 150W.
  • Step 5 Put the product obtained in Step 4 in a muffle furnace and keep it at 750°C for 2.5 hours. Ammonia is used as a protective gas.
  • Step 6 Wash and dry the product obtained in Step 5 to obtain nitrogen-doped biomass-based porous carbon material.
  • Table 1 is the relevant information on the carbon source, nitrogen source, doping method and doping efficiency in the patents of nitrogen-doped carbon materials compiled by the inventor in recent years. Through statistics, it is found that the current nitrogen doping process still has the problem of complicated process and unsatisfactory doping efficiency.

Abstract

一种氮掺杂多孔炭材料及其制备方法与应用，氮掺杂多孔炭材料，其比表面积为1600-3500m 2g -1，孔径为2-50nm的介孔所占全部孔的比例为20-40％，平均孔径为2-20nm，多孔炭材料中氮原子质量百分数为13.6wt％-19.3wt％。该多孔炭材料用作超级电容器材料时，具有更大的比电容和更好的电容保持率，在0.1A g -1的电流密度下具有847F g -1左右的比电容，循环5000次充放电后，电容保持率在99.7％左右。同时，该多孔炭材料由于优异的孔结构分布，具有良好的CO 2吸附性能。

Description

一种氮掺杂多孔炭材料及其制备方法与应用 技术领域
本发明属于多孔炭材料制备技术领域，具体涉及一种氮掺杂多孔炭材料及其制备方法与应用。
背景技术
公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。
超级电容器是继机械储能、化学储能后的第三代新型储能器件，其功率密度是电池的10-100倍，且可以实现大电流的充放电，以及具有充放电效率高、循环寿命长等特点。在电子产品、电力系统、汽车、轨道交通及航空航天等领域需求广泛，成为诸多绿色能量转换及二次储能器件研究的热点。
多孔炭因具有较大的比表面积、发达的孔结构以及良好的导电特性等优势，是目前商用超级电容器的首选材料。增加炭材料的比表面积可以在一定程度上增加其比电容，但其储电性能与比表面积并非简单的成线性关系。越纯净的炭材料表面官能团越少，导致其高比表面积不能得到充分利用，单纯通过提高炭材料的比表面积来提高其比电容具有很大的局限性。通过对碳材料进行杂原子掺杂改性是提升多孔炭材料性能的有效方法。氮原子和碳原子具有相近的原子半径，在掺杂过程中碳自身的结构不易发生破坏，且其可以将碳的六元环状结构变成五元环状结构，从而导致材料表面结构、亲水性、导电性的改变，大大拓宽了炭材料的应用领域。
中国专利(公开号CN 108922794 A)公开了一种氮掺杂生物质基活性炭电极材料的制备方法，其掺杂过程设置在热化学处理工艺前，氮源材料消耗量大；热化学处理温度高，时间长，极大的增加了制备工艺的成本。应用该工艺制备的碳材料比表面积达825.3m 2g -1，在0.5A g -1的电流密度下，比电容为259F g -1，仍达不到目前高性能电容炭的标准。
中国专利(公开号CN 108622877 A)公开了一种具有多级孔构造的氮掺杂多孔炭材料及其制备方法和应用，利用纤维素类生物质为原料，有机物尿素、甘氨酸作为氮源，其步骤包括氮源预处理、碳源氮源混合、低温碳化、高温活化等步骤，工艺复杂，氮源材料消耗量大。应用该工艺制备的碳材料比表面积达2600m 2g -1，在3A g -1的电流密度下，比电容可达210F g -1，达不到目前高性能电容炭的标准。
中国专利(公开号CN 108483442 A)公开了一种竹笋壳制备高介孔率氮掺杂炭电极材料的方法，其步骤包括水热预处理、低温碳化同步氮掺杂、活化处理，步骤复杂，氮源材 料消耗量大。其在电流密度为0.5A g -1时电容量为209F g -1，达不到目前高性能电容炭的标准。
中国专利(公开号CN 109319778 A)公开了一种氮掺杂松子壳基多孔炭材料的制备方法及应用，其氮源材料采用氨基脲、尿素、碳酸胍等链状氮源，掺杂材料消耗量大，掺杂效果不明显。预处理过程采用低温碳化工艺，不能完全去除原材料中的挥发分，炭化产物中仍然保留着大量的H、O原子，导致掺杂过程效率较低。在电流密度为0.5A g -1时，其比电容达278-380F g -1，仍有进一步提升的空间。
目前的相关研究和专利通过对生物质原料进行处理，虽然已经可以得到比表面积300-2800m 2g -1，比电容可达100-380F g -1，但是仍存在制备工艺复杂、工艺流程不够合理，炭质前驱体原料单一化、氮源材料消耗量大、氮掺杂效率低、掺杂结构不够稳定等问题。其比电容仍然达不到高性能电容炭的标准，且掺杂方法不够简单、环保。
发明内容
针对上述现有技术中存在的技术问题，本发明的目的是提供一种氮掺杂多孔炭材料及其制备方法与应用。
为了解决以上技术问题，本发明的技术方案为：
本发明的第一个目的是提供一种氮掺杂多孔炭材料，其比表面积为1600-3500m 2g -1，孔径为2-50nm的介孔所占全部孔的比例为20-40％，平均孔径为2-20nm，多孔炭材料中氮原子质量百分数为13.6wt％-19.3wt％，远高于目前相关专利的水平，较高的氮含量可有效改善材料的表面结构、导电性、润湿性，提高材料的电化学性能和吸附性能。
该多孔炭材料用作超级电容器材料时，具有更大的比电容和更好的电容保持率，在0.1A g -1的电流密度下具有847F g -1左右的比电容，循环5000次充放电后，电容保持率在99.7％左右。
同时，该多孔炭材料由于优异的孔结构分布，具有良好的CO 2吸附性能。
本发明的第二个目的是提供一种氮掺杂多孔炭材料的制备方法，包括如下步骤：
将炭质前驱体洗净、烘干、粉碎，得生物质粉末；
将生物质粉末在保护性气体或氨气氛围内高温碳化，碳化的温度为600-800℃，得碳化产物；
将碳化产物、化学活化剂饱和溶液和氮源材料超声混合浸渍，所述氮源材料为三聚氰胺、聚苯胺和吡啶；
将浸渍后产物在惰性气氛下加热杂化处理，即得生物氮掺杂多孔炭。
本发明在制备过程中使用了高温炭化的步骤，使炭化过程中去除了更多的挥发分和H、 O原子，提供了更多的活性位点。使碳化产物在进一步的反应中更容易与N原子结合，提高了氮掺杂的效率，降低了氮源材料的使用量。同时，高温炭化使炭化产物具有更高的孔隙率和较大的孔径，有利于炭材料与活化剂和掺杂材料更大面积的接触，利于反应的进一步进行。
氨气可以提供氨基，辅助氮掺杂过程。当挥发分析出时，可及时与碳环上空出的活性位结合。
浸渍后产物在惰性气氛下加热杂化处理，使氮原子取代碳环上的碳原子，并形成部分的五元环状结构。
发明人经过试验发现，环状氮源与链状氮源相比具有更高的稳定性，当应用三聚氰胺、聚苯胺和吡啶等环状氮源对多孔炭进行掺氮时，通过对制备工艺参数进行优化，使得多孔炭材料具有更好的稳定性，即使经过上千次充放电后，比电容仍然没有明显损失。
对浸渍体系进行超声处理，可以有效促进化学活化剂和氮源材料的混合，避免了过于复杂的材料前处理方式(如高温下浸渍混合、稀溶液下浸渍混合再蒸干、氮源材料预处理再浸渍混合等)，极大地缩短了处理时间，提高了处理效率。
在高温炭化、超声浸渍和惰性气氛加热杂化的综合作用下，大大提高了多孔炭中的生物氮掺杂量。
在一些实施例中，所述炭质前驱体包括但不限于蒜辫、马尾藻、木屑、果壳、秸秆。
在一些实施例中，所述炭质前驱体经粉碎后过80目筛，过大的粒度会使材料在接下来的步骤中反应不够充分，过小的粒度会提升材料的制备成本。
在一些实施例中，所述碳化的时间为1.5-2.5h。
在一些实施例中，所述化学活化剂饱和溶液为KOH饱和溶液。本发明的氮源材料难溶于水，过低的浓度会影响浸渍过程的效率，KOH饱和溶液能保证KOH的充分浸润。
进一步的，碳化产物、化学活化剂饱和溶液和氮源材料的质量比为1-3:1-5:0.1-2。本发明中氮源材料的使用量较少，但可以实现较好的氮掺杂。
进一步的，超声浸渍的温度为室温条件。
进一步的，超声处理的频率为10-50kHz，功率为80-150W，超声处理的时间为4-8min。
在一些实施例中，所述加热处理的温度为750-800℃，加热处理的时间为2-2.5h。
在一些实施例中，所述制备方法还包括将所得生物氮掺杂多孔炭进行洗涤和烘干的步骤。对多孔炭进行洗涤，以除去多孔炭中的杂质。
进一步的，采用10-20wt％的盐酸对所得的生物氮掺杂多孔炭进行酸洗，再用去离子水洗至中性。
本发明的第三个目的是提供上述制备方法制备得到的氮掺杂多孔炭。
本发明的第四个目的是提供上述氮掺杂多孔炭在制备超级电容器材料中的应用。
本发明的第五个目的是提供一种活性炭电极，其组分中包括上述氮掺杂多孔炭。
进一步的，所述活性炭电极的组分还包括导电剂和粘结剂，导电剂为导电炭黑、乙炔黑、石墨类添加剂或碳纳米管添加剂，粘结剂为PTFE(聚四氟乙烯)、PVDF(聚偏氟乙烯)、聚乙烯醇、轻甲基纤维素钠、聚烯烃类、橡胶类或聚氨醋。
本发明的第六个目的是提供上述活性炭电极的制备方法，包括如下步骤：
向氮掺杂多孔炭、粘结剂和导电剂的混合物中加入溶剂，调制成浆料；
将浆料均匀涂到集流体上，经干燥制得；
或将浆料加热压制成型，制得。
在一些实施例中，所述集流体为铜箔、铝箔、镍网或不锈钢箔。
本发明的第七个目的是提供上述氮掺杂多孔炭在作为CO 2吸附剂中的应用。
本发明的有益效果为：
本发明的制备工艺中使用高温炭化的步骤，使炭化过程中去除了更多的挥发分和H、O原子，提供了更多的活性位点。碳化产物在进一步的反应中更容易与N原子结合，提高了氮掺杂的效率，降低了氮源材料的使用量。同时，高温炭化使炭化产物具有更高的孔隙率和较大的孔径，有利于炭材料与活化剂和掺杂材料更大面积的接触，利于反应的进一步进行。
本发明采用的氮源分子结构为环状，与链状氮源相比具有更高的稳定性，根据本发明工艺制备的多孔炭材料的掺氮类型以吡咯氮和石墨型氮为主，结构稳定，因此材料在上千次充放电后比电容仍然没有明显损失。
本发明使用优化的工艺步骤，避免了过于复杂的材料前处理方式，引入超声的方式进行活化剂和氮源材料的混合，极大了缩短了处理时间，提高了处理效率。
本发明工艺简单，原料来源广泛，成本低廉，反应过程便于控制，易于规模化生产，在超级电容器电极材料及CO 2吸附材料领域有着广泛的应用前景，具体体现在以下方面：(1)应用本发明技术流程制备的氮掺杂多孔炭材料具有三维分级孔隙结构，比表面积为1600-3500m 2g -1；(2)具有更大的比电容及更好的电容保持率：当其用作超级电容器电极材料时，在0.1A g -1的电流密度下具有847F g -1的比电容，循环5000次充放电后，电容保持率在99.7％；(3)用以CO 2吸附测试表明，在25℃和0℃时的吸附量分别高达3.59和6.11mmol/g，表现出优异的孔结构分布和CO 2吸附性能。
附图说明
构成本申请的一部分的说明书附图用来提供对本申请的进一步理解，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。
图1为本发明实施例1所得到的氮气吸附-脱吸附曲线图。
图2为本发明实施例1所得到的孔径分布图。
图3为本发明实施例1所得到的循环性能图。
图4为本发明实施例2制备的电极材料在200mV s -1的扫速下测试得到的循环伏安曲线。
图5为本发明实施例2制备的电极材料在5A g -1的电流密度下测试所得到的恒电流充放电曲线。
图6为本发明实施例2制备的电极材料所得到的倍率性能图。
图7为本发明实施例3所制得的氮掺杂多孔炭材料的SEM图片。
具体实施方式
应该指出，以下详细说明都是例示性的，旨在对本申请提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本申请所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本申请的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。
实施例1
本实施例涉及一种氮掺杂多孔炭的制备方法，包括如下步骤：
步骤一，将蒜辫原料洗净，置于鼓风干燥箱中120℃干燥48h，粉碎后过80目筛。
步骤二：将步骤一种所得产物置于管式炉内，600℃碳化2h。使用氮气作为保护气。
步骤三：将步骤二中所得产物进行洗涤干燥。
步骤四：将步骤三种所得产物以1:4:0.2的质量比与KOH饱和溶液和三聚氰胺超声处理6min，超声频率为40kHz，功率为120W。
步骤五：将步骤四所得产物置于马弗炉内，以800℃处理2h。氮气作为保护气。
步骤六：将步骤五所得产物先用盐酸酸洗，再用去离子水洗到中性，干燥后即得氮掺杂生物质基多孔炭材料。
实施效果：该产物氮原子质量比高达19.3wt％，通过BET法计算得到比表面积为2642m 2/g，孔容为1.41cm 3/g，平均孔径为2.14nm，是一种具有较高比表面积的碳材料。将 此碳材料与导电剂、粘结剂以8:1:1的质量比混合制备的超级电容器用电极材料，以6mol/L的KOH作为电解液进行恒电流充放电测试，在电流密度为0.1A/g时的比电容值达到847F/g，如图6所示，在电流密度为10A/g时仍能达到649F/g。
由图1可知，材料的等温吸附-脱吸附曲线出现明显的滞后环，说明材料具有典型的三维分级孔隙结构。由图2可知，掺杂后材料仍具有大量的层次结构。由图3可知，在5000次循环后，材料仍能保持较高的电容量。
实施例2
本实施例涉及一种氮掺杂多孔炭的制备方法，包括如下步骤：
步骤一，将马尾藻原料洗净，置于鼓风干燥箱中120℃干燥48h，粉碎后过80目筛。
步骤二：将步骤一中所得产物置于管式炉内，升到800℃，并在此温度下保持1.5h。氩气作为保护气。
步骤三：将步骤二中所得产物进行洗涤干燥。
步骤四：将步骤三种所得产物与KOH饱和溶液和聚苯胺按质量比1:5:0.3混合，超声处理10min，超声频率为50kHz，功率为100W。
步骤五：将步骤四所得产物置于马弗炉内，以750℃处理2.5h。氮气作为保护气。
步骤六：将步骤五所得产物先用15wt％的盐酸酸洗，再用去离子水洗到中性，干燥后即得氮掺杂生物质基多孔炭材料。
实施效果：该产物氮原子质量比达15.4wt％，通过BET法计算得到比表面积为2543m 2/g，孔容为1.52cm 3/g，平均孔径为2.39nm，是一种具有较高比表面积的碳材料。将此碳材料与导电剂、粘结剂以8:1:1的质量比混合制备的超级电容器用电极材料，以6mol/L的KOH作为电解液进行恒电流充放电测试，在电流密度为0.1A/g时的比电容值达到594F/g，在电流密度为10A/g时仍能达到463F/g。
由图4及图5的形状可知，材料的循环伏安曲线呈近似矩形，其恒电流充放电曲线呈较好的等腰三角形特征，说明材料主要以双电层电容为主，氮掺杂引入了较多的结构氮而不是含氮官能团。由图6可知，在较大的电流密度下，材料的电容值仍能保持稳定，具有较好的倍率性能。
实施例3
本实施例涉及一种氮掺杂多孔炭的制备方法，包括如下步骤：
步骤一，将杂木木屑原料洗净，置于鼓风干燥箱中105℃干燥72h，粉碎后过120目筛。
步骤二：将步骤一种所得产物置于管式炉内，在600℃下保持2h。氦气作为保护气。
步骤三：将步骤二中所得产物进行洗涤干燥。
步骤四：将步骤三中所得产物与质量比3:1(炭：活化剂)的KOH饱和溶液和1:7(炭：氮源)的吡啶混合，超声处理4min，超声频率为30kHz，功率为140W。
步骤五：将步骤四所得产物置于马弗炉内，在750℃下保持2.5h。氨气作为保护气。
步骤六：将步骤五所得产物洗涤干燥，即得氮掺杂生物质基多孔炭材料。
实施效果：该产物氮原子质量比达13.6wt％，通过BET法计算得到比表面积为2098m 2/g，孔容为1.40cm 3/g，平均孔径为2.14nm，是一种具有较高比表面积的碳材料。将此碳材料与导电剂、粘结剂以8:1:1的质量比混合制备的超级电容器用电极材料，以6mol/L的KOH作为电解液进行恒电流充放电测试，在电流密度为0.1A/g时的比电容值达到330F/g，在电流密度为10A/g时仍能达到260F/g。
图7为实施例3所制得的氮掺杂多孔炭材料的SEM图片，由图可见，材料具有丰富的孔隙结构。
实施例4
本实施例涉及一种基于生物质的氮掺杂多孔炭的制备方法，包括如下步骤：
步骤一，将蒜辫原料洗净，置于鼓风干燥箱中120℃干燥48h，粉碎后过80目筛。
步骤二：将步骤一种所得产物置于管式炉内，600℃碳化2h。使用氮气作为保护气。
步骤三：将步骤二中所得产物进行洗涤干燥。
步骤四：将步骤三种所得产物以1:3:0.2的质量比与KOH和三聚氰胺混合，超声处理8min，超声频率为10kHz，功率为80W。
步骤五：将步骤四所得产物置于马弗炉内，以800℃处理2h。氮气作为保护气。
步骤六：将步骤五所得产物先用盐酸酸洗，再用去离子水洗到中性，干燥后即得氮掺杂生物质基多孔炭材料。
实施效果：该产物在常压条件下，CO 2的吸附测试表明，在25℃和0℃时的吸附量分别高达3.59和6.11mmol/g，该吸附量在多孔炭材料中属于较高水平。
实施例5
本实施例涉及一种基于生物质的氮掺杂多孔炭的制备方法，包括如下步骤：
步骤一，将杂木木屑原料洗净，置于鼓风干燥箱中105℃干燥72h，粉碎后过120目筛。
步骤二：将步骤一种所得产物置于管式炉内，在600℃下保持2h。氦气作为保护气。
步骤三：将步骤二中所得产物进行洗涤干燥。
步骤四：将步骤三中所得产物与质量比3:1(炭：活化剂)的KOH饱和溶液和1:7(炭： 氮源)的吡啶混合，超声处理5min，超声频率为50kHz，功率为150W。
步骤五：将步骤四所得产物置于马弗炉内，在750℃，下保持2.5h。氨气作为保护气。
步骤六：将步骤五所得产物洗涤干燥，即得氮掺杂生物质基多孔炭材料。
实施效果：该产物在常压条件下，CO 2的吸附测试表明，在25℃和0℃时的吸附量分别高达3.86和6.17mmol/g，该吸附量在多孔炭材料中属于较高水平。
表1氮掺杂专利中碳源、氮源、方法及掺氮效果统计
Figure PCTCN2019115808-appb-000001
表1中是发明人整理的近年来关于氮掺杂碳材料专利中碳源、氮源、掺杂方法及掺杂效率的相关信息。经过统计发现，目前的氮掺杂工艺仍然存在流程复杂，掺杂效率不够理想的问题。
以上所述仅为本申请的优选实施例而已，并不用于限制本申请，对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。

Claims (10)

  1. 一种氮掺杂多孔炭材料，其特征在于：其比表面积为1600-3500m 2g -1，孔径为2-50nm的介孔所占全部孔的比例为20-40％，平均孔径为2-20nm，多孔炭材料中氮原子质量百分数为13.6wt％-19.3wt％。
  2. 一种氮掺杂多孔炭材料的制备方法，其特征在于：包括如下步骤：
    将炭质前驱体洗净、烘干、粉碎，得生物质粉末；
    将生物质粉末在保护性气体或氨气氛围内高温碳化，碳化的温度为600-800℃，得碳化产物；
    将碳化产物、化学活化剂饱和溶液和氮源材料超声混合浸渍，所述氮源材料为三聚氰胺、聚苯胺或吡啶；
    将浸渍后产物在惰性气氛下加热处理，即得生物氮掺杂多孔炭。
  3. 根据权利要求2所述的氮掺杂多孔炭材料的制备方法，其特征在于：所述炭质前驱体包括但不限于蒜辫、马尾藻、木屑、果壳和秸秆；
    优选的，所述炭质前驱体经粉碎后过80目筛；
    优选的，所述碳化的时间为1.5-2.5h；
    优选的，所述化学活化剂饱和溶液为KOH饱和溶液；
    优选的，碳化产物、化学活化剂饱和溶液和氮源材料的质量比为1-3:1-5:0.1-2。
  4. 根据权利要求2所述的氮掺杂多孔炭材料的制备方法，其特征在于：超声处理的频率为10-50kHz，功率为80-150W，超声处理的时间为4-8min。
  5. 根据权利要求2所述的氮掺杂多孔炭材料的制备方法，其特征在于：所述加热处理的温度为750-800℃，加热处理的时间为2-2.5h；
    优选的，所述制备方法还包括将所得生物氮掺杂多孔炭进行洗涤和烘干的步骤；
    优选的，采用10-20wt％的盐酸对所得的生物氮掺杂多孔炭进行酸洗，再用去离子水洗至中性。
  6. 权利要求2-5任一所述制备方法制备得到的氮掺杂多孔炭。
  7. 权利要求6所述氮掺杂多孔炭在制备超级电容器材料中的应用。
  8. 一种活性炭电极，其特征在于：其组分中包括上述氮掺杂多孔炭；
    进一步的，所述活性炭电极的组分还包括导电剂和粘结剂，导电剂为导电炭黑、乙炔黑、石墨类添加剂或碳纳米管添加剂，粘结剂为PTFE、PVDF、聚乙烯醇、轻甲基纤维素钠、聚烯烃类、橡胶类或聚氨醋。
  9. 权利要求8所述活性炭电极的制备方法，其特征在于：包括如下步骤：
    向氮掺杂多孔炭、粘结剂和导电剂的混合物中加入溶剂，调制成浆料；
    将浆料均匀涂到集流体上，经干燥制得；
    或将浆料加热压制成型，制得；
    优选的，所述集流体为铜箔、铝箔、镍网或不锈钢箔。
  10. 权利要求6所述氮掺杂多孔炭在作为CO 2吸附剂中的应用。
PCT/CN2019/115808 2019-08-12 2019-11-05 一种氮掺杂多孔炭材料及其制备方法与应用 WO2021027100A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US17/049,802 US20230115681A1 (en) 2019-08-12 2019-11-05 Nitrogen-doped porous carbon material and preparation method and application thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910739372.9A CN111453726A (zh) 2019-08-12 2019-08-12 一种氮掺杂多孔炭材料及其制备方法与应用
CN201910739372.9 2019-08-12

Publications (1)

Publication Number Publication Date
WO2021027100A1 true WO2021027100A1 (zh) 2021-02-18

Family

ID=71673497

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/115808 WO2021027100A1 (zh) 2019-08-12 2019-11-05 一种氮掺杂多孔炭材料及其制备方法与应用

Country Status (3)

Country Link
US (1) US20230115681A1 (zh)
CN (1) CN111453726A (zh)
WO (1) WO2021027100A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115231568A (zh) * 2022-05-27 2022-10-25 塔里木大学 类石墨烯碳纳米片大孔交联棉秆生物质碳电极材料及其制备方法
CN115400780A (zh) * 2022-08-30 2022-11-29 天津大学浙江研究院 Koh活化氮掺杂碳材料负载型催化剂及制备方法

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112023880B (zh) * 2020-08-17 2021-12-03 盐城工学院 一种氮掺杂活性炭纤维毡的制备方法及其应用
CN112473624A (zh) * 2020-12-15 2021-03-12 安徽省灵磁新材料科技股份有限公司 一种磁性碳纳米复合材料制备工艺
CN113753892B (zh) * 2021-10-10 2023-02-03 山东省科学院菏泽分院 一种生物质基活性炭材料
US20230191651A1 (en) * 2021-12-16 2023-06-22 Northrop Grumman Systems Corporation Methods of forming a structure, and related tools for additively manufacturing the structure
CN115007155B (zh) * 2022-07-07 2024-03-26 中国科学院青岛生物能源与过程研究所 一种负载型含镍催化剂，其制备方法以及采用其催化炔烃加氢制备烯烃的方法
CN116062941B (zh) * 2023-03-02 2023-09-08 北京神舟茂华环保科技有限公司 一种光伏行业高含氟含氯废水的协同除氟脱氯的方法
CN116443875A (zh) * 2023-04-11 2023-07-18 淮阴工学院 一种氮掺杂多孔炭材料的制备方法及应用
CN117683336B (zh) * 2024-02-01 2024-04-23 国际竹藤中心 一种竹炭生物降解导电复合材料及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008280203A (ja) * 2007-05-10 2008-11-20 National Institute For Materials Science 窒素ドープメソポーラスカーボン（ｎ−ｋｉｔ−６）およびその製造方法
CN106910893A (zh) * 2017-03-21 2017-06-30 桂林电子科技大学 一种富氮掺杂多孔结构碳材料及其制备方法和应用
CN107055531A (zh) * 2017-05-25 2017-08-18 上海应用技术大学 一种生物质基氮掺杂多孔碳材料的制备方法
CN107128893A (zh) * 2017-03-08 2017-09-05 北京化工大学常州先进材料研究院 一种利用生物质高效制备多孔氮掺杂碳纳米片的方法及其应用
EP3249669A1 (en) * 2016-05-25 2017-11-29 Universiteit van Amsterdam Supercapacitor and nitrogen-doped porous carbon material
CN108059145A (zh) * 2017-12-14 2018-05-22 同济大学 一种多级孔氮掺杂多孔碳的制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102557026A (zh) * 2011-11-09 2012-07-11 南京邮电大学 以柳絮、杨絮或梧桐絮为原料制备多孔碳微米管的方法
CN103406096B (zh) * 2013-07-17 2015-06-03 国家纳米科学中心 一种氮掺杂多孔炭材料、制备方法及其用途
CN106517197A (zh) * 2016-11-14 2017-03-22 天津工业大学 超级电容器用氮掺杂多孔碳材料的制备方法
CN109987603A (zh) * 2019-03-18 2019-07-09 毛舜义 一种氮掺杂多孔碳生物质基电极材料的制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008280203A (ja) * 2007-05-10 2008-11-20 National Institute For Materials Science 窒素ドープメソポーラスカーボン（ｎ−ｋｉｔ−６）およびその製造方法
EP3249669A1 (en) * 2016-05-25 2017-11-29 Universiteit van Amsterdam Supercapacitor and nitrogen-doped porous carbon material
CN107128893A (zh) * 2017-03-08 2017-09-05 北京化工大学常州先进材料研究院 一种利用生物质高效制备多孔氮掺杂碳纳米片的方法及其应用
CN106910893A (zh) * 2017-03-21 2017-06-30 桂林电子科技大学 一种富氮掺杂多孔结构碳材料及其制备方法和应用
CN107055531A (zh) * 2017-05-25 2017-08-18 上海应用技术大学 一种生物质基氮掺杂多孔碳材料的制备方法
CN108059145A (zh) * 2017-12-14 2018-05-22 同济大学 一种多级孔氮掺杂多孔碳的制备方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115231568A (zh) * 2022-05-27 2022-10-25 塔里木大学 类石墨烯碳纳米片大孔交联棉秆生物质碳电极材料及其制备方法
CN115231568B (zh) * 2022-05-27 2024-04-02 塔里木大学 类石墨烯碳纳米片大孔交联棉秆生物质碳电极材料及其制备方法
CN115400780A (zh) * 2022-08-30 2022-11-29 天津大学浙江研究院 Koh活化氮掺杂碳材料负载型催化剂及制备方法
CN115400780B (zh) * 2022-08-30 2024-03-05 天津大学浙江研究院 Koh活化氮掺杂碳材料负载型催化剂及制备方法

Also Published As

Publication number Publication date
CN111453726A (zh) 2020-07-28
US20230115681A1 (en) 2023-04-13

Similar Documents

Publication Publication Date Title
WO2021027100A1 (zh) 一种氮掺杂多孔炭材料及其制备方法与应用
JP7236391B2 (ja) 活性炭の製造方法
CN108483442B (zh) 一种高介孔率氮掺杂炭电极材料的制备方法
CN108529587B (zh) 一种磷掺杂生物质分级孔炭材料的制备方法及其应用
WO2018188422A1 (zh) 一种用于超级电容器的蒜皮基活性炭电极材料及制备方法
CN106365163B (zh) 一种剑麻纤维活性炭的制备方法及该剑麻纤维活性炭在锂离子电容器中的应用
CN111017927A (zh) 一种基于秸秆水热炭化的氮掺杂多孔炭制备及应用方法
CN108439402B (zh) 一种超级电容器用姜秸秆基活性炭及其制备方法
Zhang et al. Recent progress of transition metal-based biomass-derived carbon composites for supercapacitor
CN107958797A (zh) 一种强碱氨气共活化生物质基活性炭电极材料的制备方法
WO2023104141A1 (zh) N/o共掺杂的硫化钼@多孔碳复合电极材料及其制备方法、负极材料及其制备方法和应用
CN109467082B (zh) 一种石墨化多孔玉米芯衍生炭电极材料的制备方法
CN109110756A (zh) 一种均质玉米芯衍生炭电极材料及其制备方法
CN105236406A (zh) 一种超级电容器用球形活性炭的制备方法
CN113307254A (zh) 采用低温双盐化合物制备三维多孔石墨烯片的方法及应用
Yin et al. Synthesis of honeycomb-like hierarchical porous carbon via molten salt pyrolysis in a novel sequencing integration system for high-performance supercapacitors
Bassey et al. Molten salt synthesis of capacitive porous carbon from Allium cepa (onion) for supercapacitor application
Xu et al. Self-template bagasse-based porous carbons for high performance supercapacitors
CN109637843A (zh) 一种以芹菜为电极原料制备超级电容器的方法
Guo et al. Fabrication of nitrogen-doped hierarchical porous carbons from Sargassum as advanced electrode materials for supercapacitors
CN112133572A (zh) 用作超级电容器的三维多孔生物质碳材料及其制备方法
CN109003828B (zh) 小麦秸秆衍生的多孔生物质炭电极材料及其制备方法
Liang et al. Post-modified biomass derived carbon materials for energy storage supercapacitors: a review
JP2017204628A (ja) 電気二重層キャパシタ電極用活性炭の製造方法及び当該方法で製造された電気二重層キャパシタ電極用活性炭
CN107680826A (zh) 一种用于超级电容器的分层多孔活性炭电极材料的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19941139

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19941139

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 19941139

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 25.01.2023)