CN112079352A - Preparation method and application of biomass-based porous nitrogen-doped carbon material - Google Patents
Preparation method and application of biomass-based porous nitrogen-doped carbon material Download PDFInfo
- Publication number
- CN112079352A CN112079352A CN201910509749.1A CN201910509749A CN112079352A CN 112079352 A CN112079352 A CN 112079352A CN 201910509749 A CN201910509749 A CN 201910509749A CN 112079352 A CN112079352 A CN 112079352A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- carbon material
- biomass
- doped carbon
- based porous
- 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.)
- Granted
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
- C01B32/348—Metallic compounds
-
- 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
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- 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)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
本发明公开了一种生物质基多孔氮掺杂碳材料的制备方法，将生物质原材料与氮源化学物质、活化剂按照一定的质量配比，通过水热反应和高温活化制备得到生物质氮掺杂多孔碳材料，制备工艺简单，操作性强，可得到高能量密度、高倍率性能以及长循环寿命的多孔氮掺杂碳材料。生物质原材料为金盘八角种子，预处理工艺简单，有效降低了成本提高了产率，且绿色可持续。还公开了一种生物质基多孔氮掺杂碳材料应用于超级电容器中电极的制备，有效提高超级电容器电极材料的比电容和循环寿命。
The invention discloses a preparation method of a biomass-based porous nitrogen-doped carbon material. Biomass nitrogen is prepared by hydrothermal reaction and high-temperature activation by combining biomass raw materials, nitrogen source chemical substances and activators according to a certain mass ratio. The doped porous carbon material has a simple preparation process and strong operability, and can obtain a porous nitrogen-doped carbon material with high energy density, high rate performance and long cycle life. The raw material of biomass is golden plate star anise seeds, the pretreatment process is simple, the cost is effectively reduced, the yield is improved, and it is green and sustainable. Also disclosed is a biomass-based porous nitrogen-doped carbon material applied to the preparation of electrodes in a supercapacitor, which effectively improves the specific capacitance and cycle life of the supercapacitor electrode material.
Description
技术领域technical field
本发明属于碳材料技术领域，具体涉及一种生物质基多孔氮掺杂碳材料的制备方法及应用。The invention belongs to the technical field of carbon materials, and in particular relates to a preparation method and application of a biomass-based porous nitrogen-doped carbon material.
背景技术Background technique
多孔碳材料具有高比表面积、可调控的孔隙率和孔径、良好的导电性以及可表面改性等特点。以生物质为原材料制备的多孔碳材料，相比起传统碳材料，具有资源丰富，成本更低以及可表面改性等优势。Porous carbon materials have the characteristics of high specific surface area, tunable porosity and pore size, good electrical conductivity, and surface modification. Compared with traditional carbon materials, porous carbon materials prepared from biomass have the advantages of abundant resources, lower cost and surface modification.
目前有很多研究者选用不同的生物质原材料（如纤维素、木质素、果壳、动物毛发等），不同的用于掺杂的氮源材料，采用不同的工艺技术制备多孔氮掺杂碳材料。不同的生物质材料和氮源材料，以及不同的工艺技术的采用都会影响到产品的产率和应用性能。如Ben-Xue Z 等通过低分子量酚醛树脂对真丝纤维进行水热组装后，再进行炭化和活化，进而得到N和O-掺杂的多孔碳材料。在该制备方法中，低分子量酚醛树脂衍生碳薄层石墨化结构的引入，提供了更丰富的结构、低电阻、分级孔隙度，使得BET表面积高达1927 m2·g1。所得到的碳复合材料在0.5 A·g1下比电容高达330 F·g1 (1000 mF·cm 2)，速率能力好，在6m KOH电解液中循环稳定性好(10000次循环后电容保持率为91%),（文献Journal ofNanomaterials，2018, 2018:1-12）.Chen MF等以豆浆为原料采用硬模板活化和KOH活化相结合的方法，制备了N掺杂多孔碳纳米片材料。碳酸钙纳米球的硬模板、KOH活化和钾种的熔融模板分别形成大孔、微孔和纳米片状形貌。前驱体中含有丰富的氮、氧元素，使产物中杂原子比例较高，不产生电容，但能促进电子转移和电导率。所得到的碳具有良好的电荷存储能力，比电容为240.7 F/g，初始比电容保持良好(92.2% ~ 20A/g)，（文献Journal ofenergy storage,2018,105-112）。Li等选择聚丙烯腈和乙酰丙酮镍分别作为CNF和Ni源的前驱体。双氰胺不仅提高了PCNF的比表面积和孔隙体积，而且提高了PCNF的n掺杂水平。受益于氧化镍纳米粒子之间的协同效应，所制备的NiO / PCNF电极表现出高的比电容850 Fg 1的电流密度1 g 1 6 m KOH水溶液，良好的能力，以及优秀的长期循环稳定性。（文献Small，2018,1704203）At present, many researchers choose different biomass raw materials (such as cellulose, lignin, nut shell, animal hair, etc.), different nitrogen source materials for doping, and use different process technologies to prepare porous nitrogen-doped carbon materials . Different biomass materials and nitrogen source materials, as well as the adoption of different process technologies will affect the yield and application performance of the product. For example, Ben-Xue Z et al. used low molecular weight phenolic resin to hydrothermally assemble silk fibers, followed by carbonization and activation to obtain N and O-doped porous carbon materials. In this preparation method, the introduction of the graphitized structure of the low molecular weight phenolic resin-derived carbon thin layer provides a richer structure, low electrical resistance, and hierarchical porosity, resulting in a BET surface area as high as 1927 m2·g1. The obtained carbon composite has a specific capacitance of up to 330 F·g1 (1000 mF·cm 2 ) at 0.5 A·g1, good rate capability, and good cycling stability in 6 m KOH electrolyte (capacitance retention after 10,000 cycles). 91%), (Journal of Nanomaterials, 2018, 2018: 1-12). Chen MF et al. prepared N-doped porous carbon nanosheets by combining hard template activation and KOH activation with soymilk as raw material. The hard template of calcium carbonate nanospheres, KOH activation, and molten template of potassium species form macroporous, microporous, and nanosheet-like morphologies, respectively. The precursor is rich in nitrogen and oxygen elements, so that the proportion of heteroatoms in the product is high, which does not produce capacitance, but can promote electron transfer and conductivity. The obtained carbon has a good charge storage capacity with a specific capacitance of 240.7 F/g, and the initial specific capacitance is well maintained (92.2% ~ 20A/g), (Journal of energy storage, 2018, 105-112). Li et al. chose polyacrylonitrile and nickel acetylacetonate as precursors for CNF and Ni sources, respectively. Dicyandiamide not only increased the specific surface area and pore volume of PCNF, but also increased the n-doping level of PCNF. Benefiting from the synergistic effect between NiO nanoparticles, the as-prepared NiO/PCNF electrodes exhibit a high specific capacitance of 850 Fg 1, a current density of 1 g 1 6 m KOH aqueous solution, good capacity, and excellent long-term cycling stability . (Literature Small, 2018, 1704203)
然而，目前具有较好电化学性能的生物质原材料选用大多较为昂贵，氮源材料的选用如乙二胺等具有较大的毒性、所采用的工艺技术，如模板法以及喷雾干燥法等技术成本较高以及制备工艺较复杂。因而制备生物质基多孔碳材料的方法仍然具有局限性，不能广泛投入生产。寻找成本低廉且绿色可持续的生物质原材料、采用简单的工艺技术以制得高产率，具有良好的电化学应用性能的生物质基多孔碳材料已迫在眉睫。However, at present, biomass raw materials with good electrochemical performance are mostly expensive, and the selection of nitrogen source materials such as ethylenediamine has greater toxicity, and the technology used, such as template method and spray drying method, costs higher and the preparation process is more complicated. Therefore, methods for preparing biomass-based porous carbon materials still have limitations and cannot be widely put into production. It is urgent to find low-cost, green and sustainable biomass raw materials, adopt simple process technology to obtain high-yield biomass-based porous carbon materials with good electrochemical application performance.
超级电容器作为目前一大电化学能源储存技术之一，因具有高功率密度、长循环寿命以及可快速充放电等优势而广泛应用于重型车辆、轻轨和混合电动汽车等。现已商用于超级电容器的电极材料，主要来源于传统的化石原料。而目前能源逐渐枯竭，充分利广阔的生物质资源以积极开发出具有低成本、绿色环保以高价值的生物质碳材料成为未来在超级电容器应用上的大趋势。As one of the current electrochemical energy storage technologies, supercapacitors are widely used in heavy-duty vehicles, light rails, and hybrid electric vehicles due to their high power density, long cycle life, and fast charge-discharge capability. The electrode materials used in supercapacitors are mainly derived from traditional fossil raw materials. At present, energy is gradually depleted, and it will become a general trend in the application of supercapacitors in the future to fully utilize the vast biomass resources to actively develop biomass carbon materials with low cost, green environmental protection and high value.
发明内容SUMMARY OF THE INVENTION
本发明提供了一种生物质基多孔氮掺杂碳材料的制备方法，解决了制备成本高、工艺复杂、产率低的问题；进一步提供了生物质基多孔氮掺杂碳材料在超级电容器中的应用，解决了超级电容器成本高、不环保、超级电容器能量密度不高的问题。The invention provides a preparation method of a biomass-based porous nitrogen-doped carbon material, which solves the problems of high preparation cost, complicated process and low yield; and further provides a biomass-based porous nitrogen-doped carbon material in a super capacitor. The application of supercapacitors solves the problems of high cost, unenvironmental protection and low energy density of supercapacitors.
为了解决上述技术问题，本发明所采用的技术方案是：一种生物质基多孔氮掺杂碳材料的制备方法，其特征在于，包括以下步骤：In order to solve the above-mentioned technical problems, the technical solution adopted in the present invention is: a preparation method of a biomass-based porous nitrogen-doped carbon material, which is characterized in that comprising the following steps:
S1、生物质原材料的预处理：将新鲜的金盘八角种子洗净后在乙醇和水的混合溶液中浸泡，浸泡一段时间后将金盘八角种子取出再浸没在盐酸溶液中，直至种子褪色，再用去离子水将种子洗净，直至用去离子水浸泡种子1~2h后水溶液呈中性，再干燥种子，得到预处理好的生物质原材料；S1. Pretreatment of biomass raw materials: Wash the fresh anise seeds in ethanol and water and soak them in a mixed solution of ethanol and water. After soaking for a period of time, take out the anise seeds and immerse them in a hydrochloric acid solution until the seeds fade. Then wash the seeds with deionized water until the aqueous solution becomes neutral after soaking the seeds with deionized water for 1-2 hours, and then dry the seeds to obtain pretreated biomass raw materials;
S2、配制混合液：将步骤S1中预处理好的生物质原材料和氮源材料进行混合，得到混合液；所述混合液中生物质原材料和氮源材料的质量配比范围为1:1~1:5；S2, preparing a mixed solution: mixing the pretreated biomass raw materials and nitrogen source materials in step S1 to obtain a mixed solution; the mass ratio of the biomass raw materials and nitrogen source materials in the mixed solution is in the range of 1:1~ 1:5;
S3、制备氮掺杂碳材料：将步骤S2中的混合液加入高压反应釜中300℃反应12h，之后再干燥，得到氮掺杂碳材料；S3. Preparation of nitrogen-doped carbon material: adding the mixture in step S2 into an autoclave at 300° C. for 12 hours, and then drying to obtain a nitrogen-doped carbon material;
S4、制得多孔氮掺杂碳材料：将步骤S3中得到的氮掺杂碳材料与活化剂按照1:4的质量比混合，放入管式炉中高温活化，得到黑色多孔固体，将黑色多孔固体清洗后再不断用去离子水冲洗直至上清液呈中性，再进行真空干燥，制得多孔氮掺杂碳材料。S4. Preparation of porous nitrogen-doped carbon material: Mix the nitrogen-doped carbon material obtained in step S3 with an activator in a mass ratio of 1:4, and put it into a tube furnace for high-temperature activation to obtain a black porous solid. The porous solid is washed and then rinsed with deionized water continuously until the supernatant is neutral, and then vacuum dried to obtain the porous nitrogen-doped carbon material.
进一步地，所述步骤S1中，乙醇和水的质量配比为1:2；浸泡时间为1~2h。Further, in the step S1, the mass ratio of ethanol and water is 1:2; the soaking time is 1~2h.
进一步地，所述步骤S2中，氮源材料包括三聚氰胺、脲素；生物质原材料和三聚氰胺的质量配比范围为1:4~1:5，生物质原材料和脲素的质量配比范围为1:1~1:4。起到了毒性小的作用。Further, in the step S2, the nitrogen source material includes melamine and urea; the mass ratio range of biomass raw material and melamine is 1:4~1:5, and the mass ratio range of biomass raw material and urea is 1 :1~1:4. played a less toxic role.
进一步地，所述步骤S3中，干燥的时间为10~13h。Further, in the step S3, the drying time is 10-13 hours.
进一步地，所述步骤S4中，活化剂包括氯化锌、氢氧化钾。Further, in the step S4, the activator includes zinc chloride and potassium hydroxide.
进一步地，所述步骤S4中，高温活化包括在管式炉里通入氮气，以500℃~700℃的温度活化并保温一段时间。Further, in the step S4, the high-temperature activation includes introducing nitrogen into the tube furnace, activating at a temperature of 500°C to 700°C, and maintaining the temperature for a period of time.
进一步地，所述保温时间为1h。Further, the holding time is 1h.
进一步地，所述步骤S4中，清洗为超声清洗。Further, in the step S4, the cleaning is ultrasonic cleaning.
进一步地，所述步骤S4中，管式炉里的温度在0~400℃时升温速率为5℃/min，大于400℃时升温速率为2℃/min。400℃以下5℃/min的升温速率更有利于种子中的其他有机物或半纤维素等的充分分解，同时可有效阻止掺杂的氮在材料表面的脱落以致于氮掺杂失效。Further, in the step S4, when the temperature in the tube furnace is 0 to 400°C, the heating rate is 5°C/min, and when the temperature is greater than 400°C, the heating rate is 2°C/min. The heating rate of 5°C/min below 400°C is more conducive to the full decomposition of other organic substances or hemicelluloses in the seeds, and at the same time, it can effectively prevent the doped nitrogen from falling off the surface of the material, resulting in the failure of nitrogen doping.
一种生物质基多孔氮掺杂碳材料的应用，其特征在于，将权利要求1~8任一所述的方法制备的生物质基多孔氮掺杂碳材料应用于超级电容器中电极的制备。An application of a biomass-based porous nitrogen-doped carbon material, characterized in that the biomass-based porous nitrogen-doped carbon material prepared by the method according to any one of claims 1 to 8 is applied to the preparation of electrodes in a supercapacitor.
本发明所达到的有益效果：Beneficial effects achieved by the present invention:
（1）金盘八角种子作为生物质原材料，来源广泛、成本低廉，而且无需对其剥皮去囊，可直接现摘现用，预处理工艺简单，有效降低了成本提高了产率，且绿色可持续。(1) As a biomass raw material, star anise seeds have a wide range of sources and low cost, and they can be directly picked and used without peeling and decapsulating them. The pretreatment process is simple, effectively reducing the cost and improving the yield. continued.
（2）金盘八角种子与氮源化学物质、活化剂按照一定的质量配比，通过水热反应和高温活化制备得到生物质氮掺杂多孔碳材料，制备工艺简单，操作性强，可得到高能量密度、高倍率性能以及长循环寿命的多孔氮掺杂碳材料。(2) Biomass nitrogen-doped porous carbon materials are prepared by hydrothermal reaction and high-temperature activation of golden plate star anise seeds, nitrogen source chemicals and activators according to a certain mass ratio. The preparation process is simple, the operability is strong, and it can be obtained Porous nitrogen-doped carbon materials with high energy density, high rate capability, and long cycle life.
（3）相比于纯活性炭材料，多孔氮掺杂碳材料具有更高的能量密度，循环稳定性长浸、润性好的优点。通过引入富含电子的N基团在多孔碳材料结构中，使质子吸引至电极材料表面，以提高其浸润性，使电解液中的离子更多地扩散在电极材料内部，形成赝电容现象，从而达到更高的比电容和电流密度。应用在超级电容器中，有效提高超级电容器电极材料的比电容和循环寿命。(3) Compared with pure activated carbon materials, porous nitrogen-doped carbon materials have the advantages of higher energy density, long cycle stability and good wettability. By introducing electron-rich N groups into the porous carbon material structure, the protons are attracted to the surface of the electrode material to improve its wettability, so that the ions in the electrolyte diffuse more inside the electrode material, forming a pseudocapacitance phenomenon. Thereby achieving higher specific capacitance and current density. Applied in supercapacitors, it can effectively improve the specific capacitance and cycle life of supercapacitor electrode materials.
附图说明Description of drawings
图1为不同扫描速率下，脲素与原材料1:3得到的循环伏安图。Figure 1 shows the cyclic voltammograms of urea and raw materials at 1:3 at different scan rates.
图2为不同电流密度下，脲素与原材料1:3得到的充放电图。Figure 2 shows the charge-discharge diagrams obtained with urea and raw materials at 1:3 at different current densities.
具体实施方式Detailed ways
下面结合附图1和2，对本发明作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案，而不能以此来限制本发明的保护范围。The present invention will be further described below in conjunction with accompanying drawings 1 and 2 . The following examples are only used to illustrate the technical solutions of the present invention more clearly, and cannot be used to limit the protection scope of the present invention.
实施例1：Example 1:
S1、生物质原材料的预处理：将新鲜的金盘八角种子洗净后在质量配比为1:2的乙醇和水的混合溶液中浸泡，浸泡1.5h后将金盘八角种子取出再浸没在盐酸溶液中，直至溶液呈深色且种子表层褪色，再用去离子水将种子洗净，直至用去离子水浸泡种子2h后水溶液测试呈中性，再干燥种子，得到预处理好的生物质原材料。S1. Pretreatment of biomass raw materials: After washing the fresh Anise seeds, soak them in a mixed solution of ethanol and water with a mass ratio of 1:2. After soaking for 1.5 hours, take out the Anise seeds and then immerse them in In the hydrochloric acid solution, until the solution turns dark and the surface of the seeds fades, then wash the seeds with deionized water until the seeds are soaked in deionized water for 2 hours and the aqueous solution test is neutral, and then dry the seeds to obtain pretreated biomass raw materials.
S2、配制混合液：将步骤S1中预处理好的生物质原材料和三聚氰胺进行混合，得到混合液；所述混合液中生物质原材料和三聚氰胺的质量配比为1:5。S2, preparing a mixed solution: mixing the pretreated biomass raw material and melamine in step S1 to obtain a mixed solution; the mass ratio of the biomass raw material and melamine in the mixed solution is 1:5.
S3、制备氮掺杂碳材料：将步骤S2中的混合液加入高压反应釜中300℃反应12h，之后再干燥12h，得到氮掺杂碳材料。S3. Preparation of nitrogen-doped carbon material: adding the mixture in step S2 into an autoclave at 300° C. for 12 hours, and then drying for 12 hours to obtain a nitrogen-doped carbon material.
S4、制得多孔氮掺杂碳材料：将步骤S3中得到的氮掺杂碳材料与氢氧化钾按照1:4的质量比混合，放入管式炉中高温活化，在管式炉里通入氮气、以650℃的温度活化并保温1h，得到黑色多孔固体，将黑色多孔固体超声清洗后再不断用去离子水冲洗直至上清液呈中性，再进行真空干燥，制得多孔氮掺杂碳材料。过程中管式炉里的温度在0~400℃时升温速率为5℃/min，大于400℃时升温速率为2℃/min。S4. Preparation of porous nitrogen-doped carbon material: Mix the nitrogen-doped carbon material obtained in step S3 with potassium hydroxide in a mass ratio of 1:4, put it into a tube furnace for high temperature activation, and pass through the tube furnace. Enter nitrogen, activate at 650°C, and keep for 1 h to obtain black porous solids. The black porous solids are ultrasonically cleaned and then rinsed with deionized water until the supernatant is neutral, and then vacuum dried to obtain porous nitrogen-doped solids. Miscellaneous carbon materials. During the process, the temperature in the tube furnace is 5°C/min when the temperature is between 0 and 400°C, and 2°C/min when the temperature is greater than 400°C.
实施例2：Example 2:
S1、生物质原材料的预处理：将新鲜的金盘八角种子洗净后在质量配比为1:2的乙醇和水的混合溶液中浸泡，浸泡1h后将金盘八角种子取出再浸没在盐酸溶液中，直至溶液呈深色且种子表层褪色，再用去离子水将种子洗净，直至用去离子水浸泡种子1.5h后水溶液测试呈中性，再干燥种子，得到预处理好的生物质原材料。S1. Pretreatment of biomass raw materials: After washing the fresh Anise seeds, soak them in a mixed solution of ethanol and water with a mass ratio of 1:2. After soaking for 1 hour, take out the Anise seeds and then immerse them in hydrochloric acid. In the solution, until the solution turns dark and the surface of the seeds fades, then wash the seeds with deionized water until the seeds are soaked in deionized water for 1.5 hours and the aqueous solution test is neutral, and then dry the seeds to obtain pretreated biomass raw materials.
S2、配制混合液：将步骤S1中预处理好的生物质原材料和三聚氰胺进行混合，得到混合液；所述混合液中生物质原材料和三聚氰胺的质量配比为1:4。S2, preparing a mixed solution: mixing the pretreated biomass raw material and melamine in step S1 to obtain a mixed solution; the mass ratio of the biomass raw material and melamine in the mixed solution is 1:4.
S3、制备氮掺杂碳材料：将步骤S2中的混合液加入高压反应釜中300℃反应12h，之后再干燥11h，得到氮掺杂碳材料。S3. Preparation of nitrogen-doped carbon material: adding the mixture in step S2 into an autoclave at 300° C. for 12 hours, and then drying for 11 hours to obtain a nitrogen-doped carbon material.
S4、制得多孔氮掺杂碳材料：将步骤S3中得到的氮掺杂碳材料与氢氧化钾按照1:4的质量比混合，放入管式炉中高温活化，在管式炉里通入氮气、以500℃的温度活化并保温1h，得到黑色多孔固体，将黑色多孔固体超声清洗后再不断用去离子水冲洗直至上清液呈中性，再进行真空干燥，制得多孔氮掺杂碳材料。过程中管式炉里的温度在0~400℃时升温速率为5℃/min，大于400℃时升温速率为2℃/min。S4. Preparation of porous nitrogen-doped carbon material: Mix the nitrogen-doped carbon material obtained in step S3 with potassium hydroxide in a mass ratio of 1:4, put it into a tube furnace for high temperature activation, and pass through the tube furnace. Nitrogen was introduced, activated at 500 °C and kept for 1 h to obtain a black porous solid. The black porous solid was ultrasonically cleaned and then rinsed with deionized water until the supernatant became neutral, and then vacuum-dried to obtain a porous nitrogen-doped solid. Miscellaneous carbon materials. During the process, the temperature in the tube furnace is 5°C/min when the temperature is between 0 and 400°C, and 2°C/min when the temperature is greater than 400°C.
实施例3：Example 3:
S1、生物质原材料的预处理：将新鲜的金盘八角种子洗净后在质量配比为1:2的乙醇和水的混合溶液中浸泡，浸泡2h后将金盘八角种子取出再浸没在盐酸溶液中，直至溶液呈深色且种子表层褪色，再用去离子水将种子洗净，直至用去离子水浸泡种子2h后水溶液测试呈中性，再干燥种子，得到预处理好的生物质原材料。S1. Pretreatment of biomass raw materials: Wash the fresh Anise seeds of Golden Disc and soak them in a mixed solution of ethanol and water with a mass ratio of 1:2. After soaking for 2 hours, take out the Anise Seeds and then immerse them in hydrochloric acid. In the solution, until the solution becomes dark and the surface of the seeds fades, then wash the seeds with deionized water until the seeds are soaked in deionized water for 2 hours and the aqueous solution test is neutral, and then dry the seeds to obtain pretreated biomass raw materials .
S2、配制混合液：将步骤S1中预处理好的生物质原材料和三聚氰胺进行混合，得到混合液；所述混合液中生物质原材料和脲素的质量配比为1:1。S2, preparing a mixed solution: mixing the pretreated biomass raw material and melamine in step S1 to obtain a mixed solution; the mass ratio of the biomass raw material and urea in the mixed solution is 1:1.
S3、制备氮掺杂碳材料：将步骤S2中的混合液加入高压反应釜中300℃反应12h，之后再干燥10h，得到氮掺杂碳材料。S3. Preparation of nitrogen-doped carbon material: adding the mixture in step S2 into an autoclave at 300° C. for 12 hours, and then drying for 10 hours to obtain nitrogen-doped carbon material.
S4、制得多孔氮掺杂碳材料：将步骤S3中得到的氮掺杂碳材料与氢氧化钾按照1:4的质量比混合，放入管式炉中高温活化，在管式炉里通入氮气、以700℃的温度活化并保温1h，得到黑色多孔固体，将黑色多孔固体超声清洗后再不断用去离子水冲洗直至上清液呈中性，再进行真空干燥，制得多孔氮掺杂碳材料。过程中管式炉里的温度在0~400℃时升温速率为5℃/min，大于400℃时升温速率为2℃/min。S4. Preparation of porous nitrogen-doped carbon material: Mix the nitrogen-doped carbon material obtained in step S3 with potassium hydroxide in a mass ratio of 1:4, put it into a tube furnace for high temperature activation, and pass through the tube furnace. Nitrogen gas was introduced, activated at 700°C, and kept for 1 h to obtain a black porous solid. The black porous solid was ultrasonically cleaned and then rinsed with deionized water until the supernatant became neutral, and then vacuum-dried to obtain a porous nitrogen-doped solid. Miscellaneous carbon materials. During the process, the temperature in the tube furnace is 5°C/min when the temperature is between 0 and 400°C, and 2°C/min when the temperature is greater than 400°C.
实施例4：Example 4:
S1、生物质原材料的预处理：将新鲜的金盘八角种子洗净后在质量配比为1:2的乙醇和水的混合溶液中浸泡，浸泡1.5h后将金盘八角种子取出再浸没在盐酸溶液中，直至溶液呈深色且种子表层褪色，再用去离子水将种子洗净，直至用去离子水浸泡种子2h后水溶液测试呈中性，再干燥种子，得到预处理好的生物质原材料。S1. Pretreatment of biomass raw materials: After washing the fresh Anise seeds, soak them in a mixed solution of ethanol and water with a mass ratio of 1:2. After soaking for 1.5 hours, take out the Anise seeds and then immerse them in In the hydrochloric acid solution, until the solution turns dark and the surface of the seeds fades, then wash the seeds with deionized water until the seeds are soaked in deionized water for 2 hours and the aqueous solution test is neutral, and then dry the seeds to obtain pretreated biomass raw materials.
S2、配制混合液：将步骤S1中预处理好的生物质原材料和三聚氰胺进行混合，得到混合液；所述混合液中生物质原材料和脲素的质量配比为1:3。S2, preparing a mixed solution: mixing the pretreated biomass raw material and melamine in step S1 to obtain a mixed solution; the mass ratio of the biomass raw material and urea in the mixed solution is 1:3.
S3、制备氮掺杂碳材料：将步骤S2中的混合液加入高压反应釜中300℃反应12h，之后再干燥13h，得到氮掺杂碳材料。S3. Preparation of nitrogen-doped carbon material: adding the mixed solution in step S2 into an autoclave at 300° C. for 12 hours, and then drying for 13 hours to obtain nitrogen-doped carbon material.
S4、制得多孔氮掺杂碳材料：将步骤S3中得到的氮掺杂碳材料与氢氧化钾按照1:4的质量比混合，放入管式炉中高温活化，在管式炉里通入氮气、以600℃的温度活化并保温1h，得到黑色多孔固体，将黑色多孔固体超声清洗后再不断用去离子水冲洗直至上清液呈中性，再进行真空干燥，制得多孔氮掺杂碳材料。过程中管式炉里的温度在0~400℃时升温速率为5℃/min，大于400℃时升温速率为2℃/min。S4. Preparation of porous nitrogen-doped carbon material: Mix the nitrogen-doped carbon material obtained in step S3 with potassium hydroxide in a mass ratio of 1:4, put it into a tube furnace for high temperature activation, and pass through the tube furnace. Nitrogen gas was introduced, activated at 600°C, and kept for 1 h to obtain a black porous solid. The black porous solid was ultrasonically cleaned and then rinsed with deionized water until the supernatant became neutral, and then vacuum-dried to obtain a porous nitrogen-doped solid. Miscellaneous carbon materials. During the process, the temperature in the tube furnace is 5°C/min when the temperature is between 0 and 400°C, and 2°C/min when the temperature is greater than 400°C.
实施例5：Example 5:
将实施例1~4所得到的多孔氮掺杂碳材料与导电剂、PVDF按照7:2:1的质量配比，以N-甲基吡咯烷酮为分散液形成浆液，将浆液均匀涂抹在泡沫镍上，涂抹面积为1*1cm2。选择6MKOH的电解液，以三电极方式（参比电极为***，对比电极为铂片）测量电化学性能。比表面积可达到1500~2500m2/g，比电容可达到200~300F/g，能量密度可达到20~30Wh/kg。The porous nitrogen-doped carbon materials obtained in Examples 1 to 4, the conductive agent, and PVDF are in a mass ratio of 7:2:1, and N-methylpyrrolidone is used as a dispersion to form a slurry, and the slurry is evenly smeared on the nickel foam. , the application area is 1*1cm 2 . The electrolyte of 6MKOH was selected, and the electrochemical performance was measured by a three-electrode method (the reference electrode was mercury oxide, and the reference electrode was platinum sheet). The specific surface area can reach 1500~2500m 2 /g, the specific capacitance can reach 200~300F/g, and the energy density can reach 20~30Wh/kg.
本发明是基于已经有实验证明的300℃预碳化再与氢氧化钾高温600℃活化得到最佳的多孔碳材料的基础上而设定的技术方案。其中得到的碳材料具有丰富的介孔和大孔，类似薄片蜂窝状。相比起纯活性炭材料，该多孔碳材料具有更高的能量密度，循环稳定性长，但是浸润性较差。通过计算，300℃碳化，600℃活化的多孔碳材料的比电容达到121.636F/g，能量密度达到20.44Wh/kg。The present invention is a technical scheme based on the pre-carbonization at 300°C and activation at a high temperature of 600°C with potassium hydroxide which has been proved by experiments to obtain the best porous carbon material. The obtained carbon materials have abundant mesopores and macropores, similar to flake honeycombs. Compared with pure activated carbon materials, the porous carbon materials have higher energy density, longer cycle stability, but poor wettability. By calculation, the specific capacitance of the porous carbon material carbonized at 300 °C and activated at 600 °C reaches 121.636 F/g, and the energy density reaches 20.44 Wh/kg.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变形，这些改进和变形也应视为本发明的保护范围。The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the technical principle of the present invention, several improvements and modifications can also be made. These improvements and modifications It should also be regarded as the protection scope of the present invention.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910509749.1A CN112079352B (en) | 2019-06-13 | 2019-06-13 | Preparation method and application of biomass-based porous nitrogen-doped carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910509749.1A CN112079352B (en) | 2019-06-13 | 2019-06-13 | Preparation method and application of biomass-based porous nitrogen-doped carbon material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112079352A true CN112079352A (en) | 2020-12-15 |
| CN112079352B CN112079352B (en) | 2021-12-14 |
Family
ID=73733486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910509749.1A Expired - Fee Related CN112079352B (en) | 2019-06-13 | 2019-06-13 | Preparation method and application of biomass-based porous nitrogen-doped carbon material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112079352B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112736252A (en) * | 2020-12-30 | 2021-04-30 | 广州流行色服饰有限公司 | Mesoporous nickel oxide loaded nitrogen-doped porous carbon negative electrode material and preparation method thereof |
| CN114408917A (en) * | 2022-01-17 | 2022-04-29 | 华南理工大学 | Lignin-based high specific surface area nitrogen-doped porous carbon material and its preparation method and application |
| CN115403041A (en) * | 2022-09-15 | 2022-11-29 | 中国地质大学（北京） | Hemicellulose-based hollow porous carbon, preparation method thereof and application thereof in zinc ion energy storage device |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103466598A (en) * | 2013-09-13 | 2013-12-25 | 中盈长江国际新能源投资有限公司 | Method for preparing nitrogen-containing ordered mesoporous carbon (OMC) materials based on biomass bases |
| CN104250003A (en) * | 2014-09-11 | 2014-12-31 | 安徽大学 | Method for preparing nitrogen-doped porous carbon nanoflakes |
| CN105692611A (en) * | 2016-03-21 | 2016-06-22 | 中国科学院理化技术研究所 | Preparation method of biomass activated carbon rich in nitrogen and oxygen |
| CN106601490A (en) * | 2016-06-21 | 2017-04-26 | 中国科学院青岛生物能源与过程研究所 | A preparation method of biomass-based nitrogen-containing porous carbon and the porous carbon prepared by the method and its application |
| JP2018111617A (en) * | 2017-01-10 | 2018-07-19 | セイコーインスツル株式会社 | Method for producing porous carbon material, method for producing porous activated carbon material, and method for producing electrode material |
| CN108878909A (en) * | 2018-07-13 | 2018-11-23 | 中南大学 | A kind of three-dimensional porous composite material and preparation method and application based on biomass |
| CN109133030A (en) * | 2018-09-25 | 2019-01-04 | 桂林电子科技大学 | A kind of preparation method and applications of nitrogen-doped porous carbon material |
-
2019
- 2019-06-13 CN CN201910509749.1A patent/CN112079352B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103466598A (en) * | 2013-09-13 | 2013-12-25 | 中盈长江国际新能源投资有限公司 | Method for preparing nitrogen-containing ordered mesoporous carbon (OMC) materials based on biomass bases |
| CN104250003A (en) * | 2014-09-11 | 2014-12-31 | 安徽大学 | Method for preparing nitrogen-doped porous carbon nanoflakes |
| CN105692611A (en) * | 2016-03-21 | 2016-06-22 | 中国科学院理化技术研究所 | Preparation method of biomass activated carbon rich in nitrogen and oxygen |
| CN106601490A (en) * | 2016-06-21 | 2017-04-26 | 中国科学院青岛生物能源与过程研究所 | A preparation method of biomass-based nitrogen-containing porous carbon and the porous carbon prepared by the method and its application |
| JP2018111617A (en) * | 2017-01-10 | 2018-07-19 | セイコーインスツル株式会社 | Method for producing porous carbon material, method for producing porous activated carbon material, and method for producing electrode material |
| CN108878909A (en) * | 2018-07-13 | 2018-11-23 | 中南大学 | A kind of three-dimensional porous composite material and preparation method and application based on biomass |
| CN109133030A (en) * | 2018-09-25 | 2019-01-04 | 桂林电子科技大学 | A kind of preparation method and applications of nitrogen-doped porous carbon material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112736252A (en) * | 2020-12-30 | 2021-04-30 | 广州流行色服饰有限公司 | Mesoporous nickel oxide loaded nitrogen-doped porous carbon negative electrode material and preparation method thereof |
| CN114408917A (en) * | 2022-01-17 | 2022-04-29 | 华南理工大学 | Lignin-based high specific surface area nitrogen-doped porous carbon material and its preparation method and application |
| CN115403041A (en) * | 2022-09-15 | 2022-11-29 | 中国地质大学（北京） | Hemicellulose-based hollow porous carbon, preparation method thereof and application thereof in zinc ion energy storage device |
| CN115403041B (en) * | 2022-09-15 | 2023-11-21 | 中国地质大学（北京） | Hemicellulose-based hollow porous carbon, preparation method thereof and application thereof in zinc ion energy storage device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112079352B (en) | 2021-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109037704B (en) | Nitrogen-doped 3D porous carbon material and preparation method and application thereof | |
| Qian et al. | Recent development in the synthesis of agricultural and forestry biomass-derived porous carbons for supercapacitor applications: a review | |
| US20230115681A1 (en) | Nitrogen-doped porous carbon material and preparation method and application thereof | |
| CN108529587B (en) | Preparation method and application of phosphorus-doped biomass graded porous carbon material | |
| CN111320172B (en) | A kind of directional synthesis method and application of biomass activated carbon-based electrode material containing micropore-mesoporous channels | |
| CN110330016A (en) | An a kind of step cooperative development method of anthracite-base porous carbon graphite microcrystal and hole | |
| CN109133030A (en) | A kind of preparation method and applications of nitrogen-doped porous carbon material | |
| CN107244664B (en) | Preparation method and application of graphene-like structure carbon electrode material | |
| CN106365163A (en) | Preparation method of sisal fiber activated carbon, and application of the sisal fiber activated carbon in lithium ion capacitor | |
| AU2020101283A4 (en) | Method for Manufacturing Straw-Based Activated Carbon Electrode Material for Super Capacitor with Energy Storage Efficiency Enhanced Through Acid Mine Drainage | |
| CN110697714A (en) | A radish-derived nitrogen-doped hierarchical porous carbon and its preparation method and application | |
| CN108892138A (en) | One kind is based on biomass derived nitrogen/oxygen codope hierarchical porous structure carbon material and preparation method thereof | |
| CN112079352A (en) | Preparation method and application of biomass-based porous nitrogen-doped carbon material | |
| CN112794324A (en) | A kind of high mesoporosity lignin hierarchical porous carbon material and its preparation method and application | |
| Liang et al. | Post-modified biomass derived carbon materials for energy storage supercapacitors: a review | |
| CN111547723A (en) | A kind of hemp-based hierarchical porous carbon material and its preparation method and application | |
| CN109467082B (en) | Preparation method of graphitized porous corncob derived carbon electrode material | |
| CN111847451A (en) | Biomass porous carbon nanofoam, preparation method and application thereof | |
| CN117525396A (en) | Preparation method of biomass-derived hard carbon anode material and energy storage battery | |
| CN105788881B (en) | A kind of preparation method of nitrogen doped corrugated carbon nanotube | |
| CN115285991A (en) | Method for generating hierarchical porous carbon based on self-assembly of biomass derivative and application thereof | |
| CN110240143A (en) | A nitrogen-doped carbon aerogel material for supercapacitor, preparation method and application | |
| CN112670097B (en) | Preparation method of loofah-based carbon electrode material with three-dimensional network structure | |
| CN114506838A (en) | Three-dimensional conductive network reinforced nickel-doped carbon aerogel material, and preparation method and application thereof | |
| CN111313020B (en) | A kind of preparation method of sulfur-doped nitrogen-rich carbon material, electrode and its application in sodium/potassium ion battery |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20211214 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |