WO2020019507A1 - Preparation method for n/s-double doped graphene – graphene nanoribbon aerogel - Google Patents

Preparation method for n/s-double doped graphene – graphene nanoribbon aerogel Download PDF

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WO2020019507A1
WO2020019507A1 PCT/CN2018/108554 CN2018108554W WO2020019507A1 WO 2020019507 A1 WO2020019507 A1 WO 2020019507A1 CN 2018108554 W CN2018108554 W CN 2018108554W WO 2020019507 A1 WO2020019507 A1 WO 2020019507A1
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graphene
double
aerogel
doped
graphene oxide
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郑玉婴
周珺
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福州大学
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    • 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
    • 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
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • 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
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • 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
    • 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
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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
    • 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 electrode material preparation, and particularly relates to a method for preparing N and S double-doped graphene-graphene nanobelt aerogel.
  • graphene is excellent for its extraordinary electronic and mechanical properties For other carbon materials.
  • graphene has made considerable progress in supercapacitors, its performance is still unsatisfactory. This is because the strong van der Waals forces between the graphene layers and the ⁇ - ⁇ stacking interaction make them easily aggregate to form a graphite-like structure, which results in the loss of effective specific surface area and reduces its specific capacitance. Therefore, in order to make full use of the electrochemical performance of graphene, it is necessary to effectively suppress its self-stacking problem.
  • graphene aerogel represents a new type of integrated carbonaceous material. Its developed pores, ultra-low density, and excellent conductive properties have given graphene aerogels a broad application prospect in the fields of energy, environmental protection and catalysis. It is a research hotspot in recent years.
  • the purpose of the present invention is to provide a method for preparing N and S double-doped graphene-graphene nanobelt aerogels in view of the shortcomings of the prior art.
  • the present invention adopts the following technical solutions:
  • a method for preparing N and S double-doped graphene-graphene nanobelt aerogels includes the following steps:
  • step (3) The graphene oxide nanoribbons obtained in step (1) and the graphene oxide obtained in step (2) are mixed, and deionized water is added, and the concentration is 2 after being homogenized by ultrasound. mg / mL mixed solution;
  • step (3) Add pyrrole and thiophene to the mixture obtained in step (3), and perform a hydrothermal reaction at a reaction temperature of 165-180 ° C and a reaction time of 3-5 hours to obtain a hydrogel;
  • step (4) The hydrogel obtained in step (4) is put into a 2 M KNO 3 solution, and a secondary hydrothermal reaction is performed.
  • the reaction temperature is 120 to 130 ° C. and the reaction time is 2 to 3 h. After cooling to room temperature , And then filtered, washed and freeze-dried;
  • step (5) The product obtained after freeze-drying in step (5) is thermally cracked in an argon atmosphere at 1050 ⁇ 1100 ° C for 2 h to prepare the N and S double-doped graphene-graphene nanobelt aerogel.
  • the mass ratio of the graphene oxide nanobelt and the graphene oxide in the step (3) is 1: 1.
  • the mass ratio of pyrrole and thiophene in step (4) is 1: 1, and the amount of pyrrole added is 1 wt% of graphene oxide.
  • the prepared N and S double-doped graphene-graphene nanobelt aerogel is used in electrode materials, and the specific steps are: N and S double-doped graphene-graphene nanobelt aerogel, acetylene black 2.
  • nickel foam as the current collector and apply the paste material. Cover the foamed nickel and vacuum-dry at 120 ° C for 24 hours, and finally obtain the required electrode.
  • the present invention inserts a graphene nanobelt between graphene layers, which helps to improve the conductivity of the graphene layer, and the carbon nanotubes can also be used as spacers to prevent the aggregation of the graphene layer; in addition, the low-dimensional
  • the self-assembly of carbon materials into a three-dimensional porous nanostructure network can greatly increase its specific surface area, provide a large electrode / electrolyte contact area for charge transfer reactions, shorten the ion transport length, and thereby improve electrochemical performance;
  • N and S in the graphene aerogel of the present invention in which the double doping of N and S can further enhance the reactivity and conductivity of the carbon material, compared with a single N or S doped material, by introducing More active sites, which improves its electrochemical performance.
  • a method for preparing N and S double-doped graphene-graphene nanobelt aerogels includes the following steps:
  • step (3) Take 50 mg of graphene oxide nanoribbons obtained in step (1) and 50 mg of graphene oxide prepared in step (2), add 50 mL of deionized water, and obtain a mixed solution with a concentration of 2 mg / mL after homogenizing by ultrasound. ;
  • step (4) The hydrogel obtained in step (4) is put into a 2M KNO 3 solution, and a secondary hydrothermal reaction is performed.
  • the reaction temperature is 120 ° C. and the reaction time is 3 hours. After cooling to room temperature, it is filtered and washed. And freeze-dried;
  • step (5) The product obtained after freeze-drying in step (5) is thermally cracked at 1050 ° C for 2 h in an argon atmosphere to obtain the N and S double-doped graphene-graphene nanobelt aerogel.
  • a method for preparing N and S double-doped graphene-graphene nanobelt aerogels includes the following steps:
  • step (3) Take 50 mg of graphene oxide nanoribbons obtained in step (1) and 50 mg of graphene oxide prepared in step (2), add 50 mL of deionized water, and obtain a mixed solution with a concentration of 2 mg / mL after homogenizing by ultrasound. ;
  • step (4) The hydrogel obtained in step (4) is put into a 2M KNO 3 solution, and a secondary hydrothermal reaction is performed.
  • the reaction temperature is 130 ° C. and the reaction time is 2 hours. After cooling to room temperature, it is filtered and washed. And freeze-dried;
  • step (5) The product obtained after the freeze drying in step (5) is thermally cracked at 1100 ° C for 2 h in an argon atmosphere to obtain the N and S double-doped graphene-graphene nanobelt aerogel.
  • a method for preparing N and S double-doped graphene-graphene nanobelt aerogels includes the following steps:
  • step (3) Take 50 mg of graphene oxide nanoribbons obtained in step (1) and 50 mg of graphene oxide prepared in step (2), add 50 mL of deionized water, and obtain a mixed solution with a concentration of 2 mg / mL after homogenizing by ultrasound. ;
  • step (4) The hydrogel obtained in step (4) is put into a 2M KNO 3 solution, and a secondary hydrothermal reaction is performed.
  • the reaction temperature is 125 ° C and the reaction time is 2.5h. After cooling to room temperature, it is filtered, Washing and freeze drying;
  • step (5) The product obtained after freeze-drying in step (5) is thermally cracked at 1080 ° C. for 2 h in an argon atmosphere to prepare the N and S double-doped graphene-graphene nanobelt aerogel.
  • a method for preparing an N-doped graphene-graphene nanobelt aerogel specifically includes the following steps:
  • step (3) Take 50 mg of graphene oxide nanoribbons obtained in step (1) and 50 mg of graphene oxide prepared in step (2), add 50 mL of deionized water, and obtain a mixed solution with a concentration of 2 mg / mL after homogenizing by ultrasound. ;
  • step (4) The hydrogel obtained in step (4) is put into a 2M KNO 3 solution, and a secondary hydrothermal reaction is performed.
  • the reaction temperature is 125 ° C and the reaction time is 2.5h. After cooling to room temperature, it is filtered, Washing and freeze drying;
  • step (5) The product obtained after freeze drying in step (5) is thermally cracked at 1080 ° C. for 2 h in an argon atmosphere to obtain the N-doped graphene-graphene nanobelt aerogel.
  • a method for preparing an S-doped graphene-graphene nanobelt aerogel specifically includes the following steps:
  • step (3) Take 50 mg of graphene oxide nanoribbons obtained in step (1) and 50 mg of graphene oxide prepared in step (2), add 50 mL of deionized water, and obtain a mixed solution with a concentration of 2 mg / mL after homogeneous ;
  • step (4) Put the hydrogel obtained in step (4) into a 2M KNO 3 solution, and conduct a secondary hydrothermal reaction at a reaction temperature of 125 ° C and a reaction time of 2.5h. After cooling to room temperature, filter, Washing and freeze drying;
  • step (5) The product obtained after freeze drying in step (5) is thermally cracked at 1080 ° C. for 2 h in an argon atmosphere to obtain the S-doped graphene-graphene nanobelt aerogel.
  • the N and S double-doped graphene-graphene nanobelt aerogel, the N-doped graphene-graphene nanobelt aerogel, and the S-doped graphene-graphene nanobelt aerogel are used.
  • the specific steps are: N and S doped graphene / carbon nanotube aerogel (or N-doped graphene-graphene nanobelt aerogel, S-doped graphene-graphene nano With aerogel), acetylene black, and polytetrafluoroethylene emulsion were added to the same weighing bottle according to a mass ratio of 90: 5: 5, stirred and mixed uniformly, and the sample was blown to a paste with a hair dryer.
  • the current collector was coated with a paste-like material on nickel foam and vacuum-dried at 120 ° C. for 24 hours to finally obtain a desired electrode.
  • the obtained electrodes were tested for density, specific surface area, and electrochemical performance. The results are shown in Table 1.

Abstract

The present invention relates to the technical field of electrode material preparation. Disclosed is a preparation method for an N/S-double doped graphene – graphene nanoribbon aerogel. The method comprises: first, mixing a graphene oxide nanoribbon with graphene oxide, adding deionized water, and performing uniform ultrasound to obtain the mixing solution; adding pyrrole and thiophene to the mixing solution, and performing one hydrothermal reaction to obtain a hydrogel; placing the obtained hydrogel into the KNO 3 solution, performing a second hydrothermal reaction, cooling to the room temperature, filtering, washing, and performing freeze drying; and performing thermal pyrolysis on the product obtained by freeze drying in an argon atmosphere to prepare the N/S-double doped graphene – graphene nanoribbon aerogel. According to the present invention, the graphene aerogel is doped with N/S. The N/S-double doping can further improve the reactivity and the conductivity of a carbon material. Compared with a single N- or S-doped material, more active sites are introduced to the N/S-double doped graphene aerogel to improve the electrochemical performance thereof, and the N/S-double doped graphene aerogel is expected to apply in the electrode material of a supercapacitor.

Description

N和S双掺杂石墨烯-石墨烯纳米带气凝胶的制备方法Preparation method of N and S double-doped graphene-graphene nanobelt aerogel 技术领域Technical field
本发明属于电极材料制备技术领域，具体涉及一种N和S双掺杂石墨烯-石墨烯纳米带气凝胶的制备方法。The invention belongs to the technical field of electrode material preparation, and particularly relates to a method for preparing N and S double-doped graphene-graphene nanobelt aerogel.
背景技术Background technique
在所有碳材料中，如碳纳米管、纳米纤维、多孔碳、空心纳米球、碳胶囊、石墨烯纳米片、石墨烯纳米带及其复合材料，石墨烯由于其非凡的电子和机械性能而优于其他碳材料。虽然石墨烯在超级电容器中已经取得了相当大的进展，但性能仍然差强人意。这是因为石墨烯层之间的强范德华力和π-π叠层相互作用使得它们容易聚集形成石墨状结构，从而导致有效比表面积的损失，降低其比电容。因此，为了充分利用石墨烯的电化学性能，必须有效抑制其自堆叠问题。Among all carbon materials, such as carbon nanotubes, nanofibers, porous carbon, hollow nanospheres, carbon capsules, graphene nanosheets, graphene nanoribbons and their composite materials, graphene is excellent for its extraordinary electronic and mechanical properties For other carbon materials. Although graphene has made considerable progress in supercapacitors, its performance is still unsatisfactory. This is because the strong van der Waals forces between the graphene layers and the π-π stacking interaction make them easily aggregate to form a graphite-like structure, which results in the loss of effective specific surface area and reduces its specific capacitance. Therefore, in order to make full use of the electrochemical performance of graphene, it is necessary to effectively suppress its self-stacking problem.
技术问题technical problem
虽然石墨烯在超级电容器中已经取得了相当大的进展，但性能仍然差强人意。这是因为石墨烯层之间的强范德华力和π-π叠层相互作用使得它们容易聚集形成石墨状结构，从而导致有效比表面积的损失，降低其比电容。石墨烯气凝胶代表着一类新型的整体性碳质材料，其发达的孔隙、超低的密度以及优异的导电特性赋予了石墨烯气凝胶在能源、环保以及催化等领域广阔的应用前景，是近年来的研究热点。Although graphene has made considerable progress in supercapacitors, its performance is still unsatisfactory. This is because the strong van der Waals forces between the graphene layers and the π-π stacking interaction make them easily aggregate to form a graphite-like structure, which results in the loss of effective specific surface area and reduces its specific capacitance. Graphene aerogel represents a new type of integrated carbonaceous material. Its developed pores, ultra-low density, and excellent conductive properties have given graphene aerogels a broad application prospect in the fields of energy, environmental protection and catalysis. It is a research hotspot in recent years.
技术解决方案Technical solutions
本发明的目的在于针对现有技术不足，提供一种N和S双掺杂石墨烯-石墨烯纳米带气凝胶的制备方法。The purpose of the present invention is to provide a method for preparing N and S double-doped graphene-graphene nanobelt aerogels in view of the shortcomings of the prior art.
为实现上述目的，本发明采用如下技术方案：To achieve the above objective, the present invention adopts the following technical solutions:
一种N和S双掺杂石墨烯-石墨烯纳米带气凝胶的制备方法，具体包括以下步骤：A method for preparing N and S double-doped graphene-graphene nanobelt aerogels includes the following steps:
（1）氧化石墨烯纳米带的制备；(1) Preparation of graphene oxide nanoribbons;
（2）氧化石墨烯的制备；(2) Preparation of graphene oxide;
（3）将步骤（1）制得的氧化石墨烯纳米带和步骤（2）制得的氧化石墨烯混合后，加入去离子水，超声均匀后得到浓度为2 mg/mL的混合液；(3) The graphene oxide nanoribbons obtained in step (1) and the graphene oxide obtained in step (2) are mixed, and deionized water is added, and the concentration is 2 after being homogenized by ultrasound. mg / mL mixed solution;
（4）往步骤（3）得到的混合液中加入吡咯和噻吩，进行一次水热反应，反应温度为165~180 ℃，反应时间为3~5 h，得到水凝胶；(4) Add pyrrole and thiophene to the mixture obtained in step (3), and perform a hydrothermal reaction at a reaction temperature of 165-180 ° C and a reaction time of 3-5 hours to obtain a hydrogel;
（5）将步骤（4）得到的水凝胶放入2 M的KNO 3溶液中，进行二次水热反应，反应温度为120~130 ℃，反应时间为2~3 h，冷却至室温后，再经过滤、洗涤和冷冻干燥； (5) The hydrogel obtained in step (4) is put into a 2 M KNO 3 solution, and a secondary hydrothermal reaction is performed. The reaction temperature is 120 to 130 ° C. and the reaction time is 2 to 3 h. After cooling to room temperature , And then filtered, washed and freeze-dried;
（6）将步骤（5）冷冻干燥后所得产物在氩气气氛中于1050~1100 ℃下热裂解2 h，制得所述N和S双掺杂石墨烯-石墨烯纳米带气凝胶。(6) The product obtained after freeze-drying in step (5) is thermally cracked in an argon atmosphere at 1050 ~ 1100 ° C for 2 h to prepare the N and S double-doped graphene-graphene nanobelt aerogel.
步骤（3）中所述的氧化石墨烯纳米带和氧化石墨烯的质量比为1:1。The mass ratio of the graphene oxide nanobelt and the graphene oxide in the step (3) is 1: 1.
步骤（4）中所述的吡咯和噻吩的质量比为1:1，其中吡咯的加入量为氧化石墨烯的1wt%。The mass ratio of pyrrole and thiophene in step (4) is 1: 1, and the amount of pyrrole added is 1 wt% of graphene oxide.
将制得的N和S双掺杂石墨烯-石墨烯纳米带气凝胶用于电极材料中，具体步骤为：将N和S双掺杂石墨烯-石墨烯纳米带气凝胶、乙炔黑、聚四氟乙烯乳液按照质量比为90:5:5的比例加入同一称量瓶中，搅拌混合均匀并用电吹风将样品吹至糊状，以泡沫镍为集流体，将糊状材料涂覆到泡沫镍上，在120℃下真空干燥24h，最终制得所需电极。The prepared N and S double-doped graphene-graphene nanobelt aerogel is used in electrode materials, and the specific steps are: N and S double-doped graphene-graphene nanobelt aerogel, acetylene black 2. Add the polytetrafluoroethylene emulsion into the same weighing bottle according to the mass ratio of 90: 5: 5, stir and mix well, and blow the sample to a paste with an electric hair dryer. Use nickel foam as the current collector and apply the paste material. Cover the foamed nickel and vacuum-dry at 120 ° C for 24 hours, and finally obtain the required electrode.
有益效果Beneficial effect
（1）本发明在石墨烯层片之间***石墨烯纳米带，有助于提高石墨烯层的导电性，并且碳纳米管也可作为间隔物以防止石墨烯层的聚集；此外，低维碳材料自组装成三维多孔纳米结构网络，可以大大提高其比表面积，为电荷转移反应提供大的电极/电解质接触面积，缩短离子输运长度，从而提高电化学性能；(1) The present invention inserts a graphene nanobelt between graphene layers, which helps to improve the conductivity of the graphene layer, and the carbon nanotubes can also be used as spacers to prevent the aggregation of the graphene layer; in addition, the low-dimensional The self-assembly of carbon materials into a three-dimensional porous nanostructure network can greatly increase its specific surface area, provide a large electrode / electrolyte contact area for charge transfer reactions, shorten the ion transport length, and thereby improve electrochemical performance;
（2）本发明在石墨烯气凝胶中N和S，其中N和S的双掺杂可以进一步增强碳材料的反应性和导电性，相比于单一的N或S掺杂材料，通过引入更多的活性位点，从而提高其电化学性能。(2) N and S in the graphene aerogel of the present invention, in which the double doping of N and S can further enhance the reactivity and conductivity of the carbon material, compared with a single N or S doped material, by introducing More active sites, which improves its electrochemical performance.
本发明的实施方式Embodiments of the invention
以下结合具体实施例对本发明做进一步说明，但本发明不仅仅限于这些实施例。The present invention is further described below with reference to specific embodiments, but the present invention is not limited to these embodiments.
氧化石墨烯纳米带的制备：Preparation of graphene oxide nanoribbons:
（A）在36 mL的浓H 2SO 4中加入0.15 g多壁碳纳米管（MWCNTs），磁力搅拌2 h后加入4 mL H 3PO 4，继续搅拌15 min；加入1.2 g KMnO 4后，移至65 ℃油浴中加热搅拌2 h。待反应结束冷却至室温后，加入100 mL冰水（含5 mL的30%的H 2O 2），静置14 h； (A) Add 0.15 g of multi-walled carbon nanotubes (MWCNTs) to 36 mL of concentrated H 2 SO 4 , magnetically stir for 2 h, add 4 mL of H 3 PO 4 , and continue stirring for 15 min; after adding 1.2 g of KMnO 4 , Move to 65 ℃ oil bath and stir for 2 h. After the reaction was cooled to room temperature, 100 mL of ice water (containing 5 mL of 30% H 2 O 2 ) was added and left for 14 h;
（B）静置完成后倒去上层清液，将剩余溶液用220 µm的微孔滤膜进行抽滤，用6 mL 20%的HCl洗涤两次；将抽滤所得固体重新分散在60 mL的超纯水中搅拌2 h后超声，得到分散均匀的溶液，将其加入到40 mL 30%的HCl，静置14 h；(B) After standing, pour off the supernatant and use the remaining solution with 220 The μm microporous membrane was suction-filtered and washed twice with 6 mL of 20% HCl; the solid obtained by suction filtration was re-dispersed in 60 mL of ultrapure water, stirred for 2 h, and then sonicated to obtain a uniformly dispersed solution. Add to 40 mL of 30% HCl and let stand for 14 h;
（C）以相同的滤膜抽滤并将所得产物重新分散在40 mL无水甲醇中搅拌2 h，加60 mL无水***静置1 h，然后用滤膜过滤并用10 mL***洗涤，最终将所得固体分散在适当的超纯水中超声至均匀，最终得到氧化石墨烯纳米带悬浮液，将其冷冻干燥可得呈黑褐色的氧化石墨烯纳米带粉末（GONRs）。(C) Suction filtration with the same filter membrane and redisperse the obtained product in 40 mL of anhydrous methanol and stir for 2 h, add 60 mL of anhydrous ether to stand for 1 h, then filter through the filter and wash with 10 mL of ether. The obtained solid was dispersed in appropriate ultrapure water and sonicated until homogeneous, and finally a graphene oxide nanoribbon suspension was obtained, which was freeze-dried to obtain black brown graphene oxide nanoribbon powder (GONRs).
氧化石墨烯的制备：将石墨与浓硫酸/浓磷酸体系（v/v=9:1）均匀混合后，缓慢加入高锰酸钾，均匀搅拌0.5h后，在50℃水浴中搅拌12h，缓慢加入去离子水，并保持温度低于100℃，逐滴加入5wt%的双氧水，当混合液变成金黄色时，加入盐酸洗涤，反应5分钟后，用去离子水洗涤至中性，并用BaCl 2检测有无SO 4 2-残留，随后冷冻干燥24h制得氧化石墨粉末；将制得的氧化石墨粉末加入到去离子水中，超声1h，然后于2000r/min的转速下离心10min，去除下层沉淀物，取上层液，将上层液于0℃下冷冻12h后，置于冷冻干燥机中进行冷冻干燥36h，即制得所述氧化石墨烯。 Preparation of graphene oxide: After uniformly mixing graphite with a concentrated sulfuric acid / concentrated phosphoric acid system (v / v = 9: 1), slowly add potassium permanganate, stir evenly for 0.5h, and then stir in a 50 ° C water bath for 12h. Add deionized water and keep the temperature below 100 ° C. Add 5 wt% hydrogen peroxide dropwise. When the mixture turns golden brown, add hydrochloric acid and wash. After 5 minutes of reaction, wash with deionized water until neutral, and use BaCl. 2 Detect the presence of SO 4 2- , and then freeze-dry for 24 hours to obtain graphite oxide powder; add the obtained graphite oxide powder to deionized water, sonicate for 1 hour, and then centrifuge at 2000 r / min for 10 minutes to remove the lower sediment After taking the upper layer liquid, the upper layer liquid was frozen at 0 ° C. for 12 hours, and then placed in a freeze dryer for freeze drying for 36 hours to obtain the graphene oxide.
实施例1Example 1
一种N和S双掺杂石墨烯-石墨烯纳米带气凝胶的制备方法，具体包括以下步骤：A method for preparing N and S double-doped graphene-graphene nanobelt aerogels includes the following steps:
（1）氧化石墨烯纳米带的制备；(1) Preparation of graphene oxide nanoribbons;
（2）氧化石墨烯的制备；(2) Preparation of graphene oxide;
（3）取50mg步骤（1）制得的氧化石墨烯纳米带和50mg步骤（2）制得的氧化石墨烯混合后，加入50mL去离子水，超声均匀后得到浓度为2mg/mL的混合液；(3) Take 50 mg of graphene oxide nanoribbons obtained in step (1) and 50 mg of graphene oxide prepared in step (2), add 50 mL of deionized water, and obtain a mixed solution with a concentration of 2 mg / mL after homogenizing by ultrasound. ;
（4）往步骤（3）得到的混合液中加入0.5mg的吡咯和0.5mg的噻吩，进行一次水热反应，反应温度为165℃，反应时间为5h，得到水凝胶；(4) Add 0.5 mg of pyrrole and 0.5 mg of thiophene to the mixed solution obtained in step (3), and perform a hydrothermal reaction at a reaction temperature of 165 ° C and a reaction time of 5 hours to obtain a hydrogel;
（5）将步骤（4）得到的水凝胶放入2M的KNO 3溶液中，进行二次水热反应，反应温度为120℃，反应时间为3h，冷却至室温后，再经过滤、洗涤和冷冻干燥； (5) The hydrogel obtained in step (4) is put into a 2M KNO 3 solution, and a secondary hydrothermal reaction is performed. The reaction temperature is 120 ° C. and the reaction time is 3 hours. After cooling to room temperature, it is filtered and washed. And freeze-dried;
（6）将步骤（5）冷冻干燥后所得产物在氩气气氛中于1050℃下热裂解2h，制得所述N和S双掺杂石墨烯-石墨烯纳米带气凝胶。(6) The product obtained after freeze-drying in step (5) is thermally cracked at 1050 ° C for 2 h in an argon atmosphere to obtain the N and S double-doped graphene-graphene nanobelt aerogel.
实施例2Example 2
一种N和S双掺杂石墨烯-石墨烯纳米带气凝胶的制备方法，具体包括以下步骤：A method for preparing N and S double-doped graphene-graphene nanobelt aerogels includes the following steps:
（1）氧化石墨烯纳米带的制备；(1) Preparation of graphene oxide nanoribbons;
（2）氧化石墨烯的制备；(2) Preparation of graphene oxide;
（3）取50mg步骤（1）制得的氧化石墨烯纳米带和50mg步骤（2）制得的氧化石墨烯混合后，加入50mL去离子水，超声均匀后得到浓度为2mg/mL的混合液；(3) Take 50 mg of graphene oxide nanoribbons obtained in step (1) and 50 mg of graphene oxide prepared in step (2), add 50 mL of deionized water, and obtain a mixed solution with a concentration of 2 mg / mL after homogenizing by ultrasound. ;
（4）往步骤（3）得到的混合液中加入0.5mg的吡咯和0.5mg的噻吩，进行一次水热反应，反应温度为180℃，反应时间为3h，得到水凝胶；(4) Add 0.5 mg of pyrrole and 0.5 mg of thiophene to the mixture obtained in step (3), and perform a hydrothermal reaction at a reaction temperature of 180 ° C and a reaction time of 3 hours to obtain a hydrogel;
（5）将步骤（4）得到的水凝胶放入2M的KNO 3溶液中，进行二次水热反应，反应温度为130℃，反应时间为2h，冷却至室温后，再经过滤、洗涤和冷冻干燥； (5) The hydrogel obtained in step (4) is put into a 2M KNO 3 solution, and a secondary hydrothermal reaction is performed. The reaction temperature is 130 ° C. and the reaction time is 2 hours. After cooling to room temperature, it is filtered and washed. And freeze-dried;
（6）将步骤（5）冷冻干燥后所得产物在氩气气氛中于1100℃下热裂解2h，制得所述N和S双掺杂石墨烯-石墨烯纳米带气凝胶。(6) The product obtained after the freeze drying in step (5) is thermally cracked at 1100 ° C for 2 h in an argon atmosphere to obtain the N and S double-doped graphene-graphene nanobelt aerogel.
实施例3Example 3
一种N和S双掺杂石墨烯-石墨烯纳米带气凝胶的制备方法，具体包括以下步骤：A method for preparing N and S double-doped graphene-graphene nanobelt aerogels includes the following steps:
（1）氧化石墨烯纳米带的制备；(1) Preparation of graphene oxide nanoribbons;
（2）氧化石墨烯的制备；(2) Preparation of graphene oxide;
（3）取50mg步骤（1）制得的氧化石墨烯纳米带和50mg步骤（2）制得的氧化石墨烯混合后，加入50mL去离子水，超声均匀后得到浓度为2mg/mL的混合液；(3) Take 50 mg of graphene oxide nanoribbons obtained in step (1) and 50 mg of graphene oxide prepared in step (2), add 50 mL of deionized water, and obtain a mixed solution with a concentration of 2 mg / mL after homogenizing by ultrasound. ;
（4）往步骤（3）得到的混合液中加入0.5mg的吡咯和0.5mg的噻吩，进行一次水热反应，反应温度为170℃，反应时间为4h，得到水凝胶；(4) Add 0.5 mg of pyrrole and 0.5 mg of thiophene to the mixed solution obtained in step (3), and perform a hydrothermal reaction at a reaction temperature of 170 ° C. and a reaction time of 4 h to obtain a hydrogel;
（5）将步骤（4）得到的水凝胶放入2M的KNO 3溶液中，进行二次水热反应，反应温度为125℃，反应时间为2.5h，冷却至室温后，再经过滤、洗涤和冷冻干燥； (5) The hydrogel obtained in step (4) is put into a 2M KNO 3 solution, and a secondary hydrothermal reaction is performed. The reaction temperature is 125 ° C and the reaction time is 2.5h. After cooling to room temperature, it is filtered, Washing and freeze drying;
（6）将步骤（5）冷冻干燥后所得产物在氩气气氛中于1080℃下热裂解2h，制得所述N和S双掺杂石墨烯-石墨烯纳米带气凝胶。(6) The product obtained after freeze-drying in step (5) is thermally cracked at 1080 ° C. for 2 h in an argon atmosphere to prepare the N and S double-doped graphene-graphene nanobelt aerogel.
对比例1Comparative Example 1
一种N掺杂石墨烯-石墨烯纳米带气凝胶的制备方法，具体包括以下步骤：A method for preparing an N-doped graphene-graphene nanobelt aerogel specifically includes the following steps:
（1）氧化石墨烯纳米带的制备；(1) Preparation of graphene oxide nanoribbons;
（2）氧化石墨烯的制备；(2) Preparation of graphene oxide;
（3）取50mg步骤（1）制得的氧化石墨烯纳米带和50mg步骤（2）制得的氧化石墨烯混合后，加入50mL去离子水，超声均匀后得到浓度为2mg/mL的混合液；(3) Take 50 mg of graphene oxide nanoribbons obtained in step (1) and 50 mg of graphene oxide prepared in step (2), add 50 mL of deionized water, and obtain a mixed solution with a concentration of 2 mg / mL after homogenizing by ultrasound. ;
（4）往步骤（3）得到的混合液中加入0.5mg的吡咯和0.5mg的噻吩，进行一次水热反应，反应温度为170℃，反应时间为4h，得到水凝胶；(4) Add 0.5 mg of pyrrole and 0.5 mg of thiophene to the mixed solution obtained in step (3), and perform a hydrothermal reaction at a reaction temperature of 170 ° C. and a reaction time of 4 h to obtain a hydrogel;
（5）将步骤（4）得到的水凝胶放入2M的KNO 3溶液中，进行二次水热反应，反应温度为125℃，反应时间为2.5h，冷却至室温后，再经过滤、洗涤和冷冻干燥； (5) The hydrogel obtained in step (4) is put into a 2M KNO 3 solution, and a secondary hydrothermal reaction is performed. The reaction temperature is 125 ° C and the reaction time is 2.5h. After cooling to room temperature, it is filtered, Washing and freeze drying;
（6）将步骤（5）冷冻干燥后所得产物在氩气气氛中于1080℃下热裂解2h，制得所述N掺杂石墨烯-石墨烯纳米带气凝胶。(6) The product obtained after freeze drying in step (5) is thermally cracked at 1080 ° C. for 2 h in an argon atmosphere to obtain the N-doped graphene-graphene nanobelt aerogel.
对比例2Comparative Example 2
一种S掺杂石墨烯-石墨烯纳米带气凝胶的制备方法，具体包括以下步骤：A method for preparing an S-doped graphene-graphene nanobelt aerogel specifically includes the following steps:
（1）氧化石墨烯纳米带的制备；(1) Preparation of graphene oxide nanoribbons;
（2）氧化石墨烯的制备；(2) Preparation of graphene oxide;
（3）取50mg步骤（1）制得的氧化石墨烯纳米带和50mg步骤（2）制得的氧化石墨烯混合后，加入50mL去离子水，超声均匀后得到浓度为2mg/mL的混合液；(3) Take 50 mg of graphene oxide nanoribbons obtained in step (1) and 50 mg of graphene oxide prepared in step (2), add 50 mL of deionized water, and obtain a mixed solution with a concentration of 2 mg / mL after homogeneous ;
（4）往步骤（3）得到的混合液中加入0.5mg的吡咯和0.5mg的噻吩，进行一次水热反应，反应温度为170℃，反应时间为4h，得到水凝胶；(4) Add 0.5 mg of pyrrole and 0.5 mg of thiophene to the mixture obtained in step (3), and perform a hydrothermal reaction at a reaction temperature of 170 ° C and a reaction time of 4 hours to obtain a hydrogel;
（5）将步骤（4）得到的水凝胶放入2M的KNO 3溶液中，进行二次水热反应，反应温度为125℃，反应时间为2.5h，冷却至室温后，再经过滤、洗涤和冷冻干燥； (5) Put the hydrogel obtained in step (4) into a 2M KNO 3 solution, and conduct a secondary hydrothermal reaction at a reaction temperature of 125 ° C and a reaction time of 2.5h. After cooling to room temperature, filter, Washing and freeze drying;
（6）将步骤（5）冷冻干燥后所得产物在氩气气氛中于1080℃下热裂解2h，制得所述S掺杂石墨烯-石墨烯纳米带气凝胶。(6) The product obtained after freeze drying in step (5) is thermally cracked at 1080 ° C. for 2 h in an argon atmosphere to obtain the S-doped graphene-graphene nanobelt aerogel.
将上述制得的N和S双掺杂石墨烯-石墨烯纳米带气凝胶、N掺杂石墨烯-石墨烯纳米带气凝胶和S掺杂石墨烯-石墨烯纳米带气凝胶用于电极材料中，具体步骤为：将N和S双掺杂石墨烯/碳纳米管气凝胶（或N掺杂石墨烯-石墨烯纳米带气凝胶、S掺杂石墨烯-石墨烯纳米带气凝胶）、乙炔黑、聚四氟乙烯乳液按照质量比为90:5:5的比例加入同一称量瓶中，搅拌混合均匀并用电吹风将样品吹至糊状，以泡沫镍为集流体，将糊状材料涂覆到泡沫镍上，在120℃下真空干燥24h，最终制得所需电极。The N and S double-doped graphene-graphene nanobelt aerogel, the N-doped graphene-graphene nanobelt aerogel, and the S-doped graphene-graphene nanobelt aerogel are used. In the electrode material, the specific steps are: N and S doped graphene / carbon nanotube aerogel (or N-doped graphene-graphene nanobelt aerogel, S-doped graphene-graphene nano With aerogel), acetylene black, and polytetrafluoroethylene emulsion were added to the same weighing bottle according to a mass ratio of 90: 5: 5, stirred and mixed uniformly, and the sample was blown to a paste with a hair dryer. The current collector was coated with a paste-like material on nickel foam and vacuum-dried at 120 ° C. for 24 hours to finally obtain a desired electrode.
将制得的电极进行密度、比表面积以及电化学性能测试，结果如表1所示。The obtained electrodes were tested for density, specific surface area, and electrochemical performance. The results are shown in Table 1.
表1 气凝胶电极的各项性能Table 1 Performance of aerogel electrodes
Figure dest_path_image001
Figure dest_path_image001
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。The above descriptions are merely preferred embodiments of the present invention, and any equivalent changes and modifications made in accordance with the scope of patent application of the present invention shall fall within the scope of the present invention.

Claims (4)

  1. 一种N和S双掺杂石墨烯-石墨烯纳米带气凝胶的制备方法，其特征在于：具体包括以下步骤：A method for preparing N and S double-doped graphene-graphene nanobelt aerogels, which is characterized in that it specifically includes the following steps:
    （1）氧化石墨烯纳米带的制备；(1) Preparation of graphene oxide nanoribbons;
    （2）氧化石墨烯的制备；(2) Preparation of graphene oxide;
    （3）将步骤（1）制得的氧化石墨烯纳米带和步骤（2）制得的氧化石墨烯混合后，加入去离子水，超声均匀后得到浓度为2 mg/mL的混合液；(3) after mixing the graphene oxide nanoribbons obtained in step (1) and the graphene oxide obtained in step (2), adding deionized water, and sonicating to obtain a mixed solution with a concentration of 2 mg / mL;
    （4）往步骤（3）得到的混合液中加入吡咯和噻吩，进行一次水热反应，反应温度为165~180 ℃，反应时间为3~5 h，得到水凝胶；(4) Add pyrrole and thiophene to the mixture obtained in step (3), and perform a hydrothermal reaction at a reaction temperature of 165-180 ° C and a reaction time of 3-5 hours to obtain a hydrogel;
    （5）将步骤（4）得到的水凝胶放入2 M的KNO 3溶液中，进行二次水热反应，反应温度为120~130 ℃，反应时间为2~3 h，冷却至室温后，再经过滤、洗涤和冷冻干燥； (5) The hydrogel obtained in step (4) is put into a 2 M KNO 3 solution, and a secondary hydrothermal reaction is performed. The reaction temperature is 120 to 130 ° C. and the reaction time is 2 to 3 h. After cooling to room temperature , And then filtered, washed and freeze-dried;
    （6）将步骤（5）冷冻干燥后所得产物在氩气气氛中于1050~1100 ℃下热裂解2 h，制得所述N和S双掺杂石墨烯-石墨烯纳米带气凝胶。(6) The product obtained after freeze-drying in step (5) is thermally cracked in an argon atmosphere at 1050 ~ 1100 ° C for 2 h to prepare the N and S double-doped graphene-graphene nanobelt aerogel.
  2. 根据权利要求1所述的N和S双掺杂石墨烯-石墨烯纳米带气凝胶的制备方法，其特征在于：步骤（3）中所述的氧化石墨烯纳米带和氧化石墨烯的质量比为1:1。The method for preparing an N and S double-doped graphene-graphene nanobelt aerogel according to claim 1, characterized in that: the mass of the graphene oxide nanobelt and the graphene oxide in step (3) The ratio is 1: 1.
  3. 根据权利要求1所述的N和S双掺杂石墨烯-石墨烯纳米带气凝胶的制备方法，其特征在于：步骤（4）中所述的吡咯和噻吩的质量比为1:1，其中吡咯的加入量为氧化石墨烯的1wt%。The method for preparing an N and S double-doped graphene-graphene nanobelt aerogel according to claim 1, characterized in that the mass ratio of the pyrrole and thiophene in step (4) is 1: 1, The added amount of pyrrole is 1% by weight of graphene oxide.
  4. 一种如权利要求1所述的制备方法制得的N和S双掺杂石墨烯-石墨烯纳米带气凝胶在电极材料中的应用，其特征在于：将N和S双掺杂石墨烯-石墨烯纳米带气凝胶、乙炔黑、聚四氟乙烯乳液按照质量比为90:5:5的比例加入同一称量瓶中，搅拌混合均匀并用电吹风将样品吹至糊状，以泡沫镍为集流体，将糊状材料涂覆到泡沫镍上，在120℃下真空干燥24h，最终制得所需电极。The application of N and S double-doped graphene-graphene nanobelt aerogels prepared by the preparation method according to claim 1 in electrode materials, characterized in that: N and S double-doped graphene -Graphene nanoribbon aerogel, acetylene black, and polytetrafluoroethylene emulsion are added to the same weighing bottle according to a mass ratio of 90: 5: 5, stirred and mixed uniformly, and the sample is blown to a paste with an electric blower to Nickel foam is a current collector. The paste-like material is coated on the nickel foam and dried under vacuum at 120 ° C for 24 hours, and finally the required electrode is obtained.
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