CN109148165B - 一种共价有机框架/石墨烯复合材料的制备及应用 - Google Patents
一种共价有机框架/石墨烯复合材料的制备及应用 Download PDFInfo
- Publication number
- CN109148165B CN109148165B CN201810860222.9A CN201810860222A CN109148165B CN 109148165 B CN109148165 B CN 109148165B CN 201810860222 A CN201810860222 A CN 201810860222A CN 109148165 B CN109148165 B CN 109148165B
- Authority
- CN
- China
- Prior art keywords
- organic framework
- covalent organic
- graphene
- composite material
- graphene composite
- Prior art date
- Legal status (The legal status 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 status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 56
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 9
- CPNAVTYCORRLMH-UHFFFAOYSA-N 6-phenylphenanthridine-3,8-diamine Chemical compound C=1C(N)=CC=C(C2=CC=C(N)C=C22)C=1N=C2C1=CC=CC=C1 CPNAVTYCORRLMH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000002378 acidificating effect Effects 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical group C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007772 electrode material Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 2
- -1 5-mesitylene-al aldehyde Chemical class 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 239000002262 Schiff base Substances 0.000 abstract description 6
- 150000004753 Schiff bases Chemical class 0.000 abstract description 6
- CLWRFNUKIFTVHQ-UHFFFAOYSA-N [N].C1=CC=NC=C1 Chemical group [N].C1=CC=NC=C1 CLWRFNUKIFTVHQ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- KNYSZSHKNRNJGQ-UHFFFAOYSA-N 1,3,5-trimethylcyclohexane-1,3,5-tricarbaldehyde Chemical compound O=CC1(C)CC(C)(C=O)CC(C)(C=O)C1 KNYSZSHKNRNJGQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 150000003934 aromatic aldehydes Chemical class 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
本发明公开了一种共价有机框架/石墨烯复合材料的制备方法及其电学性能。在室温下,以在体相中均匀分散的还原氧化石墨烯为模板,基于席夫碱聚合反应原位生长共价有机框架结构。共价有机框架由1,3,5‑均苯三甲醛和3,8‑二氨基‑6‑苯基菲啶作为前体分子,利用6M的醋酸提供酸性条件。通过席夫碱聚合反应将吡啶氮原子均匀分布于共价有机框架中,提供均匀的活性位点。以石墨烯作为模板来合成共价有机框架材料,得到的结构具有一致的孔道形状。石墨烯是一种导电性好的材料,将共价有机框架和石墨烯复合起来,能够进一步提高其电化学性能。本发明首次采用室温条件下原位合成共价有机框架/石墨烯复合材料,制备方法条件温和,适合实际生产的需要。
Description
一、所属领域
一种共价有机框架/石墨烯复合材料的制备及应用,属于纳米复合材料的制备及在超级电容器中的应用领域。
二、背景技术
过去的几十年,工业化和都市化引发了传统能源利用量的增长,有可能导致地球的能源耗尽以及全球变暖。于是科学家们逐渐转去开发新的绿色清洁能源,如太阳能和风能,以及努力提高储能装置的性能。超级电容器是一种重要的能量存储器件,有高的功率密度,比传统电容器更高的能量密度,宽的温度范围和长的循环寿命。过去的几年研究较多的高效率能量存储材料包括金属氧化物,多孔有机聚合物,石墨烯,共轭多孔聚合物以及多种碳材料等等。在这些多孔纳米材料中,共价有机框架(COF)是一类周期性的多孔有机材料,具有密度低,力学稳定性好,比表面积高等特点。在COF中,有机结构单元周期性的连接成二维或三维的多孔晶体结构,孔的组成和形貌可以通过单体的大小和形貌来调节。这些多孔结构可以通过可逆反应来实现,如芳香胺和芳香醛的席夫碱聚合反应等。由于其高的比表面积,纳米尺寸的孔径结构,高的热稳定性和力学稳定性以及共轭的结构使得COF成为能量存储器件材料的有力竞争者。如果连接特定的功能基团或者功能材料到框架结构中可使它们有更广泛的应用。
借助于共价有机框架多孔结构的特点,可以将具有赝电容活性的吡啶氮原子引入到共价有机框架的孔道中,使得吡啶氮原子在孔道中均匀的分散,能够更充分的与电解液接触。此外,石墨烯是一种导电性很好的材料,将具有赝电容活性的共价有机框架和石墨烯复合起来,能够更进一步提高其电化学性能,我们采用原位合成的方法制备了了共价有机框架/石墨烯复合材料,又进一步探索了复合材料作为电极材料应用于超级电容器。
三、发明内容
本发明的目的是提供一种共价有机框架/石墨烯复合材料的简单低成本的制备方法,并进一步研究其应用于超级电容器。
本发明采用三次对称性的芳香醛和含有吡啶氮原子的二胺作为单体分子,通过可逆的席夫碱反应,以在体相中均匀分散的石墨烯为模板,在石墨烯上原位生长共价有机框架材料。
本发明的技术方案:
采用的芳香醛的结构式为:
采用的含有吡啶氮原子的芳香二胺的结构式为:
两者发生席夫碱聚合反应的化学反应式如下:
一种共价有机框架/石墨烯复合材料的制备方法是:称取1,3,5-均苯三甲醛0.08g,3,8-二氨基-6-苯基菲啶0.21g,加20mL1,4-二氧六环溶解,得到淡黄色溶液,称取0.015g石墨烯置于上述溶液中,室温搅拌30分钟分散均匀,然后缓慢滴加4mL 6M的醋酸,滴加完毕后室温搅拌24小时,得到的固体离心,用1,4-二氧六环洗涤三次,二甲基亚砜洗涤三次,去离子水洗涤三次,无水乙醇洗涤三次。80度真空干燥。通过改变石墨烯的质量,分别得到了石墨烯含量为1%和石墨烯含量为5%的共价有机框架/石墨烯复合材料。
采用这种方法所得到的石墨烯含量为5%的共价有机框架/石墨烯复合材料,其作为超级电容器电极材料,电化学性能相比于共价有机框架材料粉末有了显著的提升。共价有机框架/石墨烯复合材料作为超级电容器电极材料,在0.5A/g的电流密度下,放电比容量最高可以达到240.9F/g,相比于共价有机框架粉体材料在0.5A/g电流密度下的97.9F/g有了大幅提升。此外,共价有机框架/石墨烯复合材料,在1A/g的电流密度下,放电比容量可以达到192.7F/g,在2A/g的电流密度下,放电比容量可以达到158.1F/g。
四、附图说明
图1是本发明所制备的共价有机框架/石墨烯复合材料的X射线光电子能谱的N1s光谱分解图。测定的结合能通过扣除石墨烯的C1s的结合能(285.0eV)经过了校正。结合能在398.5eV和399.1eV处有两个峰位,位于398.5eV处的峰对应着吡啶氮,位于399.1eV处对应着1,3,5-均苯三甲醛与3,8-二氨基-6-苯基菲啶发生席夫碱反应形成的-C=N-。
图2是本发明所制备的共价有机框架/石墨烯复合材料的扫描电子显微镜图像,可以看出共价有机框架完全覆盖了石墨烯表面。
图3是本发明所制备的共价有机框架/石墨烯复合材料的透射电子显微镜图像,可以看出共价有机框架的孔道结构,孔径约为2nm。
图4是本发明所制备的共价有机框架和共价有机框架/石墨烯复合材料在5mV/s扫速下的循环伏安对比图。黑色表示的是共价有机框架粉末作为超级电容器电极材料的循环伏安曲线,红色表示的是共价有机框架/石墨烯复合材料作为超级电容器电极材料的循环伏安曲线。
图5是本发明所制备的共价有机框架/石墨烯复合材料在0.5A/g、1A/g、2A/g电流密度下的充放电曲线对比图。
五、具体实施方式
实施例1:
称取1,3,5-均苯三甲醛0.08g,3,8-二氨基-6-苯基菲啶0.21g,加30mL 1,4-二氧六环溶解,得到淡黄色溶液,称取0.015g石墨烯置于上述溶液中,室温搅拌30分钟分散均匀,然后缓慢滴加4mL 6M的醋酸,滴加完毕后室温搅拌24小时。
得到的固体离心,用1,4-二氧六环洗涤三次,二甲基亚砜洗涤三次,去离子水洗涤三次,无水乙醇洗涤三次。80度真空干燥。得到了石墨烯含量为5%的共价有机框架/石墨烯复合材料。
按照质量比8:1:1分别称取共价有机框架/石墨烯复合材料、乙炔黑、聚偏氟乙烯,放入玛瑙研钵混合,逐滴滴加分散剂N-甲基吡咯烷酮,研磨成糊状物,然后将糊状物均匀涂覆于烘干的1×1cm的泡沫镍表面,80度真空干燥12小时。干燥好的电极片用大小为2.5×2.5cm的泡沫镍包裹,用压片机压成薄片,作为工作电极,计算工作电极上共价有机框架/石墨烯复合材料的质量。
用汞/氧化汞电极作为参比电极,铂片电极作为辅助电极,采用2M KOH水溶液做电解液,测试共价有机框架/石墨烯复合材料的电化学性能。
Claims (8)
1.共价有机框架/石墨烯复合材料的制备方法,其特征在于,包括如下步骤:称取1,3,5-均苯三甲醛和3,8-二氨基-6-苯基菲啶,加溶剂溶解,得到淡黄色溶液,称取石墨烯置于上述溶液中,室温搅拌30分钟分散均匀,然后缓慢滴加6 M的醋酸,滴加完毕后室温搅拌24小时,得到的固体离心,洗涤,干燥,得到了共价有机框架/石墨烯复合材料,共价有机框架在石墨烯表面均匀生长,为海胆状结构。
2.根据权利要求1所述的共价有机框架/石墨烯复合材料的制备方法,其特征在于,所述1,3,5-均苯三甲醛和3,8-二氨基-6-苯基菲啶的摩尔比为2:3。
3.根据权利要求1所述的共价有机框架/石墨烯复合材料的制备方法,其特征在于,所采用的溶剂是1,4-二氧六环,利用6 M的醋酸作为酸性条件,两者的体积比为5:1。
4.根据权利要求1所述的共价有机框架/石墨烯复合材料的制备方法,其特征在于,反应时间为24小时,反应温度为室温。
5.根据权利要求1所述的共价有机框架/石墨烯复合材料的制备方法,其特征在于,洗涤过程包括1,4-二氧六环洗涤3次,二甲基亚砜洗涤3次,去离子水洗涤3次,无水乙醇洗涤3次。
6.根据权利要求1所述的共价有机框架/石墨烯复合材料的制备方法,其特征在于:所述共价有机框架结构为孔径为2.1纳米的孔道结构。
7.一种根据权利要求1-6任一项所述的共价有机框架/石墨烯复合材料的制备方法得到的共价有机框架/石墨烯复合材料。
8.一种根据权利要求7所述的共价有机框架/石墨烯复合材料作为超级电容器的活性电极材料的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810860222.9A CN109148165B (zh) | 2018-08-01 | 2018-08-01 | 一种共价有机框架/石墨烯复合材料的制备及应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810860222.9A CN109148165B (zh) | 2018-08-01 | 2018-08-01 | 一种共价有机框架/石墨烯复合材料的制备及应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109148165A CN109148165A (zh) | 2019-01-04 |
CN109148165B true CN109148165B (zh) | 2020-10-13 |
Family
ID=64798927
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810860222.9A Active CN109148165B (zh) | 2018-08-01 | 2018-08-01 | 一种共价有机框架/石墨烯复合材料的制备及应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109148165B (zh) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109755534B (zh) * | 2019-01-21 | 2022-02-08 | 中国科学院宁波材料技术与工程研究所 | 一种基于有机共价框架材料的电极材料及其制备和应用 |
CN110183676B (zh) * | 2019-05-31 | 2021-07-13 | 上海交通大学 | 一种全共轭碳碳双键连接的富氮共价有机框架材料的制备方法 |
CN110231380A (zh) * | 2019-06-13 | 2019-09-13 | 复旦大学 | 一种抗污染场效应晶体管传感器及其制备方法 |
CN110556537B (zh) * | 2019-08-28 | 2021-04-20 | 华中科技大学 | 一种改善阴离子嵌入型电极材料电化学性能的方法 |
CN111682208A (zh) * | 2020-05-21 | 2020-09-18 | 上海大学 | 复合有机框架纳米电极材料及其制备方法 |
CN111604035B (zh) * | 2020-06-04 | 2023-06-16 | 中国农业科学院蔬菜花卉研究所 | 三维石墨烯/COFs复合材料、及其制备方法和应用 |
CN112038647B (zh) * | 2020-08-31 | 2021-07-27 | 江南大学 | 一种基于COFs衍生纳米碳管催化ORR反应的方法 |
CN112126236B (zh) * | 2020-10-13 | 2022-03-25 | 济南大学 | 卟啉共价有机骨架/石墨烯气凝胶复合材料及其电化学传感器和应用 |
CN114835930B (zh) * | 2021-02-01 | 2023-03-24 | 中国科学院化学研究所 | 一种二维希夫碱共价有机框架聚合物薄膜及其制备方法 |
CN114854214B (zh) * | 2021-02-03 | 2023-03-31 | 中国科学院化学研究所 | 一种原位生长石墨烯二维共价有机框架复合材料及其制备方法 |
CN114551818B (zh) * | 2021-07-08 | 2023-10-03 | 万向一二三股份公司 | 一种纳米硅复合颗粒、负极片和固体锂电池 |
CN115304730A (zh) * | 2022-07-11 | 2022-11-08 | 上海大学 | 一种柔性共价有机框架基复合纤维及其制备方法和应用 |
CN116496460B (zh) * | 2023-06-20 | 2023-10-20 | 吉林省卓材新研科技有限公司 | 一种共价有机框架材料及其配体和应用 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9499555B2 (en) * | 2012-10-12 | 2016-11-22 | Council Of Scientific And Industrial Research | Porous crystalline frameworks, process for the preparation therof and their mechanical delamination to covalent organic nanosheets (CONS) |
CN103755588B (zh) * | 2014-01-09 | 2015-09-23 | 兰州大学 | 一种共价有机框架材料的合成方法及应用 |
CN104319107B (zh) * | 2014-10-28 | 2017-11-10 | 郑州轻工业学院 | 一种共价有机骨架/石墨烯复合材料及制法和用途 |
CN104538596B (zh) * | 2014-12-22 | 2017-03-15 | 哈尔滨工业大学 | 一种碳材料/共价有机二维网格复合电极材料及其制备方法与应用 |
CN107151006B (zh) * | 2017-06-02 | 2021-05-04 | 江西师范大学 | 在三维多孔洋麻杆碳上生长类石墨烯片层结构的方法 |
-
2018
- 2018-08-01 CN CN201810860222.9A patent/CN109148165B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
CN109148165A (zh) | 2019-01-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109148165B (zh) | 一种共价有机框架/石墨烯复合材料的制备及应用 | |
Cui et al. | All-carbon lithium capacitor based on salt crystal-templated, N-doped porous carbon electrodes with superior energy storage | |
Liao et al. | Hierarchical nickel nanowire@ NiCo 2 S 4 nanowhisker composite arrays with a test-tube-brush-like structure for high-performance supercapacitors | |
Sun et al. | Facile and green synthesis of 3D honeycomb-like N/S-codoped hierarchically porous carbon materials from bio-protic salt for flexible, temperature-resistant supercapacitors | |
CN103112846B (zh) | 一种石墨烯-碳纳米管-纳米二氧化锡三维复合材料的制备方法及其产品 | |
KR101213475B1 (ko) | 중형 다공성 탄소 복합체, 그 제조방법 및 이를 이용한연료전지 | |
CN109637831B (zh) | 一种超级电容器用氮磷共掺杂多孔碳片的制备方法 | |
WO2018103386A1 (zh) | 一种片状氮磷共掺杂多孔碳材料及其制备方法与用途 | |
CN110467182B (zh) | 一种基于反应模板的多级孔碳基材料及其制备方法和应用 | |
CN108565129B (zh) | 一种碳纳米管/硼氮共掺杂多孔碳复合材料的制备方法 | |
CN113178338B (zh) | 一种咔唑基多孔碳/聚苯胺复合电极材料及其制备方法 | |
CN107804833B (zh) | 一种三维网状氮磷硫共掺杂多孔碳材料及制备方法与用途 | |
CN110265226B (zh) | 一种硫化镍/碳化三聚氰胺泡沫复合电极材料及其制备方法 | |
CN108922790A (zh) | 一种钠离子嵌入的二氧化锰/氮掺杂多孔碳复合材料的制备方法和应用 | |
CN109879264A (zh) | 一种三维多孔碳基超级电容器电极材料的制备方法 | |
CN112701268B (zh) | 柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极及其制备方法 | |
CN112357900B (zh) | 一种高密度氮氧氯共掺杂碳颗粒材料、以及制备方法与应用 | |
CN106024424A (zh) | 一种氢氧化镍/石墨烯卷-碳纳米管复合碳气凝胶及其制备和应用 | |
Liang et al. | A simple approach towards one-dimensional mesoporous carbon with superior electrochemical capacitive activity | |
Liu et al. | Co 3 O 4@ Highly ordered macroporous carbon derived from a mollusc shell for supercapacitors | |
CN114783782B (zh) | 一种3d打印的三维石墨烯-金属有机框架电极、其制备方法及应用 | |
CN109390163B (zh) | 二维Cu-MOF衍生的多孔碳纳米片的制备方法 | |
CN108039283A (zh) | 一种基于原位聚合的富氮掺杂多级孔碳材料及其制备方法与应用 | |
CN114031737A (zh) | 大尺寸三聚氰胺基共价有机框架材料及制备方法和应用 | |
KR101095863B1 (ko) | 고출력 슈퍼 커패시터의 전극 및 그의 제조방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |