WO2018188419A1 - Preparation method for use with graphene-based porous carbon network - Google Patents

Preparation method for use with graphene-based porous carbon network Download PDF

Info

Publication number
WO2018188419A1
WO2018188419A1 PCT/CN2018/077170 CN2018077170W WO2018188419A1 WO 2018188419 A1 WO2018188419 A1 WO 2018188419A1 CN 2018077170 W CN2018077170 W CN 2018077170W WO 2018188419 A1 WO2018188419 A1 WO 2018188419A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene oxide
graphene
porous carbon
carbon network
mold
Prior art date
Application number
PCT/CN2018/077170
Other languages
French (fr)
Chinese (zh)
Inventor
高超
陈琛
韩燚
Original Assignee
杭州高烯科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 杭州高烯科技有限公司 filed Critical 杭州高烯科技有限公司
Publication of WO2018188419A1 publication Critical patent/WO2018188419A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/536—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite based on expanded graphite or complexed graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
    • C04B38/063—Preparing or treating the raw materials individually or as batches
    • C04B38/0635—Compounding ingredients
    • C04B38/0645—Burnable, meltable, sublimable materials
    • C04B38/0675—Vegetable refuse; Cellulosic materials, e.g. wood chips, cork, peat, paper
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Definitions

  • the invention belongs to the field of graphene materials and relates to a preparation method of a graphene-based porous carbon network.
  • Activated carbon is a material with high carbon content and relatively developed voids, such as coal, nutshell, wood, bone, petroleum residue, etc., which is first carbonized and then subjected to high temperature activation treatment at 800 to 1500 degrees to form a developed micro.
  • the pores and mesopores make their specific surface area and adsorption capacity meet certain requirements.
  • Activated carbon is divided into hundreds of kinds of decolorizing activated carbon, water-purifying activated carbon, air-purifying activated carbon, heavy metal recycling activated carbon, etc. It is widely used and is the most effective adsorbing material that can be achieved at the current scientific level.
  • graphene As a new type of two-dimensional carbon material, graphene has attracted more and more attention from the world. Due to its superior mechanical properties, electrical properties, thermal properties and unique electromagnetic properties, graphene has shown broad application prospects in many fields and has gradually moved to practical applications. In particular, the ultra-high specific surface area of graphene (2600 m 2 /g) has great application potential in the field of adsorbent materials. However, at present, graphene materials are faced with problems such as low strength and difficulty in maintaining pore structure. Therefore, combining graphene with other materials can achieve an effect of one plus one greater than one.
  • Patent 201310590113.7 "Preparation method of graphene modified activated carbon” adopts simple mixing to match graphene with traditional wood or straw activated carbon, and obtains graphene-modified activated carbon after activation, which has high specific surface area and can be used in capacitor field. . However, it is more promising to simply mix and match the high specific surface area of graphene itself and explore new composite methods.
  • the object of the present invention is to provide a method for preparing a porous carbon network based on graphene in view of the deficiencies of the prior art.
  • a method for preparing a graphene-based porous carbon network comprising the following steps:
  • the atomization drying temperature described in the step (1) is 100 to 200 °C.
  • potassium hydroxide is further added to the graphene oxide dispersion described in the step (1), and the mass ratio of potassium hydroxide to graphene oxide is 0.1 to 1:1.
  • the biomass carbon source described in the step (2) is one or more of straw, coconut shell, sucrose residue, wood chips, walnut shell, apricot shell, and hay, and the activator is potassium hydroxide or sodium hydroxide.
  • the activator is potassium hydroxide or sodium hydroxide.
  • the carbonization temperature in the step (3) is 300 to 500 ° C
  • the carbonization time is 1 to 6 hours
  • the activation temperature is 500 to 1000 ° C
  • the activation time is 1 to 4 hours.
  • the invention has the beneficial effects that the present invention firstly prepares the graphene oxide microspheres by the atomization drying method, and then mixes with the biomass carbon source and the activator uniformly, and performs high temperature treatment together to obtain a porous carbon network.
  • the surface of the graphene oxide has a rich oxygen-containing functional group, and the group is rapidly removed under the heated condition to generate a gas, so that the graphene layer stack structure is opened to obtain a microporous structure.
  • the graphene oxide microspheres obtained by atomization drying rapidly expand like popcorn during heat treatment to produce a rich pore structure, and at the same time, the gas released by the biomass carbon source during carbonization can further expand the graphene sphere.
  • the activated carbon between the expanded graphene sphere and the sphere is squeezed such that a uniform layer of activated carbon is formed between the sphere and the sphere to form a carbon network.
  • the activator (potassium hydroxide) reacts with both activated carbon and graphene to create new pores.
  • the porous material obtained by the invention has high specific surface area, high porosity and low density, and has good stability, and can be used in the fields of air purification, water treatment, catalytic carrier, electrochemical material and the like.
  • a method of preparing a graphene-based porous carbon network includes the following steps:
  • the atomization drying temperature is 100 to 200 ° C; and the potassium oxide oxide dispersion is further added with potassium hydroxide.
  • the mass ratio of potassium hydroxide to graphene oxide is 0.1 to 1:1;
  • the graphene oxide microspheres obtained in the step (1) are mixed with the biomass carbon source and the activator, and the mass ratio is 100:10 ⁇ 200: 100 ⁇ 300, grinding to 300 ⁇ 400 mesh, transferred to the mold, the filling rate is 90 ⁇ 100%;
  • the biomass carbon source is straw, coconut shell, sucrose residue, wood chips, walnut shell, apricot shell, One or more kinds of dry grass, the activator is one of potassium hydroxide and sodium hydroxide;
  • the carbonization temperature The temperature is from 300 to 500 ° C, the carbonization time is from 1 to 6 hours, the activation temperature is from 500 to 1000
  • microspheres described in the present invention are common technical terms in the art and are not intended to define the diameter.
  • the diameter of the microspheres is not the object of the present invention.
  • the diameter of the microspheres prepared by the method of the present invention varies from 100 nm to 50 um.
  • the graphene oxide microspheres obtained in the step (1) are mixed with a coconut shell and potassium hydroxide at a mass ratio of 100:10:100, ground to 300-400 mesh, and transferred to a mold at a filling ratio of 90. %;
  • a graphene-based porous carbon network is obtained, which is a black fluffy block.
  • the density was 0.17 g/cm 3
  • the specific surface area was 1840 m 2 /g
  • the pore volume was 1.75 cm 3 /g.
  • the graphene oxide microspheres obtained in the step (1) are mixed with a coconut shell and potassium hydroxide at a mass ratio of 100:10:100, ground to 300-400 mesh, and transferred to a mold at a filling ratio of 90. %;
  • a graphene-based porous carbon network is obtained, which is a black fluffy block.
  • the density was 0.14 g/cm 3
  • the specific surface area was 2030 m 2 /g
  • the pore volume was 2.28 cm 3 /g.
  • the graphene oxide microspheres obtained in the step (1) are mixed with a coconut shell and potassium hydroxide at a mass ratio of 100:120:200, ground to 300-400 mesh, and transferred to a mold at a filling ratio of 90. %;
  • the mixture was carbonized at 300 ° C for 6 h, activated at 800 ° C for 2 h, and washed to obtain a porous carbon network.
  • a graphene-based porous carbon network is obtained, which is a black fluffy block.
  • the density was 0.37 g/cm 3
  • the specific surface area was 1510 m 2 /g
  • the pore volume was 1.24 cm 3 /g.
  • the graphene oxide microspheres obtained in the step (1) are mixed with a coconut shell and potassium hydroxide at a mass ratio of 100:200:300, ground to 300-400 mesh, and transferred to a mold at a filling ratio of 90. %;
  • a graphene-based porous carbon network is obtained, which is a black fluffy block.
  • the density was 0.46 g/cm 3
  • the specific surface area was 1270 m 2 /g
  • the pore volume was 0.94 cm 3 /g.
  • the graphene oxide microspheres obtained in the step (1) are mixed with straw and potassium hydroxide at a mass ratio of 100:60:150, ground to 300-400 mesh, transferred to a mold, and the filling ratio is 100%. ;
  • a graphene-based porous carbon network is obtained, which is a black fluffy block.
  • the density was 0.22 g/cm 3
  • the specific surface area was 1360 m 2 /g
  • the pore volume was 0.97 cm 3 /g.
  • the graphene oxide microspheres obtained in the step (1) are mixed with wood chips and potassium hydroxide at a mass ratio of 100:60:150, ground to 300-400 mesh, and transferred to a mold at a filling rate of 95%. ;
  • a graphene-based porous carbon network is obtained, which is a black fluffy block.
  • the density was 0.19 g/cm 3
  • the specific surface area was 1480 m 2 /g
  • the pore volume was 1.02 cm 3 /g.
  • the graphene oxide microspheres obtained in the step (1) are mixed with a coconut shell and potassium hydroxide at a mass ratio of 100:60:110, ground to 300-400 mesh, and transferred to a mold at a filling ratio of 95. %;
  • the mixture was carbonized at 300 ° C for 2 h, activated at 1000 ° C for 2 h, and washed to obtain a porous carbon network.
  • a graphene-based porous carbon network is obtained, which is a black fluffy block.
  • the density was 0.16 g/cm 3
  • the specific surface area was 1870 m 2 /g
  • the pore volume was 2.17 cm 3 /g.

Abstract

A preparation method for use with a graphene-based porous carbon network. The method comprises: firstly, preparing and obtaining graphene oxide microspheres by means of a spray drying method by using a single-layer graphene oxide dispersion liquid; then uniformly mixing the graphene oxide microspheres with a biomass carbon source and an activator; processing at a high temperature within a limited space, and then obtaining a porous carbon network. The graphene-based porous carbon network has abundant pore structures, has a large specific surface area and pore volume, and is low density; the present invention may be used in the fields of air purification, water treatment, wave-absorbtion materials, electrochemical materials and the like.

Description

一种基于石墨烯的多孔碳网络的制备方法Preparation method of graphene-based porous carbon network 技术领域Technical field
本发明属于石墨烯材料领域，涉及一种基于石墨烯的多孔碳网络的制备方法。The invention belongs to the field of graphene materials and relates to a preparation method of a graphene-based porous carbon network.
背景技术Background technique
随着工业社会的不断发展，空气污染成为影响人类生活的重要威胁之一，例如装修后室内涂层和家具会散发的甲醛，具有高致癌性，以及近年来受到广泛关注的PM2.5，对人们的呼吸道和肺功能造成难以恢复的影响。因此，研究高效吸附材料是一大热点。活性炭是以含炭量较高和空隙比较发达的物质，如煤、果壳、木材、骨、石油残渣等为原料，先经过炭化，再经过800到1500度的高温活化处理，形成发达的微孔和中孔，使其比表面积及吸附能力达到一定的要求。普通活性炭的生产一般分为两个过程，第一：炭化，第二：活化。活性炭分为脱色活性炭、水净化活性炭、空气净化活性炭、重金属回收活性炭等几百个种类，用途及其广泛，是目前科学水平所能达到的最有效的吸附材料。With the continuous development of industrial society, air pollution has become one of the important threats to human life. For example, formaldehyde, which is emitted from indoor coatings and furniture after decoration, has high carcinogenicity and PM2.5, which has received extensive attention in recent years. People's respiratory and lung functions cause irreversible effects. Therefore, research on high-efficiency adsorption materials is a hot spot. Activated carbon is a material with high carbon content and relatively developed voids, such as coal, nutshell, wood, bone, petroleum residue, etc., which is first carbonized and then subjected to high temperature activation treatment at 800 to 1500 degrees to form a developed micro. The pores and mesopores make their specific surface area and adsorption capacity meet certain requirements. The production of ordinary activated carbon is generally divided into two processes, first: carbonization, and second: activation. Activated carbon is divided into hundreds of kinds of decolorizing activated carbon, water-purifying activated carbon, air-purifying activated carbon, heavy metal recycling activated carbon, etc. It is widely used and is the most effective adsorbing material that can be achieved at the current scientific level.
作为一种新型的二维碳材料，石墨烯越来越受到世人的关注。由于其出众的力学性能，电学性能，热学性能和独特的电磁学性能，石墨烯在许多领域显示出广阔的应用前景，并已逐步走向实际应用。特别是石墨烯超高的比表面积(2600m 2/g)在吸附材料领域具有很大的应用潜力。但是目前石墨烯材料面临强度不高，孔结构难保持等问题，因此将石墨烯与其他材料相结合可实现一加一大于一的效应。专利201310590113.7《一种石墨烯改性活性炭的制备方法》中采用简单混合将石墨烯和传统木质或者秸秆活性炭相匹配，经活化后得到石墨烯改性的活性炭，具有高比表面积，可用于电容器领域。但是简单地混合难以利用石墨烯本身高比表面积的性能，探索新的复合方法更加具有前景。 As a new type of two-dimensional carbon material, graphene has attracted more and more attention from the world. Due to its superior mechanical properties, electrical properties, thermal properties and unique electromagnetic properties, graphene has shown broad application prospects in many fields and has gradually moved to practical applications. In particular, the ultra-high specific surface area of graphene (2600 m 2 /g) has great application potential in the field of adsorbent materials. However, at present, graphene materials are faced with problems such as low strength and difficulty in maintaining pore structure. Therefore, combining graphene with other materials can achieve an effect of one plus one greater than one. Patent 201310590113.7 "Preparation method of graphene modified activated carbon" adopts simple mixing to match graphene with traditional wood or straw activated carbon, and obtains graphene-modified activated carbon after activation, which has high specific surface area and can be used in capacitor field. . However, it is more promising to simply mix and match the high specific surface area of graphene itself and explore new composite methods.
发明内容Summary of the invention
本发明的目的是针对现有的技术不足，提供一种基于石墨烯的多孔碳网络的制备方法。The object of the present invention is to provide a method for preparing a porous carbon network based on graphene in view of the deficiencies of the prior art.
本发明的目的是通过以下技术方案实现的：一种基于石墨烯的多孔碳网络的制备方法，包括以下步骤：The object of the present invention is achieved by the following technical solutions: a method for preparing a graphene-based porous carbon network, comprising the following steps:
(1)通过雾化干燥法将单层氧化石墨烯分散液干燥，得到氧化石墨烯微球；(1) drying a single layer of graphene oxide dispersion by an atomization drying method to obtain graphene oxide microspheres;
(2)将步骤(1)得到的氧化石墨烯微球，与生物质碳源、活化剂混合，质量比为100:10～200:100～300，研磨至300～400目，转移到模具中，填充率为90～100％；(2) mixing the graphene oxide microspheres obtained in the step (1) with a biomass carbon source and an activator at a mass ratio of 100:10 to 200:100 to 300, grinding to 300 to 400 mesh, and transferring to a mold. , the filling rate is 90 to 100%;
(3)将模具密封后，对其中的混合物进行炭化、活化、洗涤得到多孔碳网络。(3) After the mold is sealed, the mixture is carbonized, activated, and washed to obtain a porous carbon network.
进一步地，步骤(1)中所述的雾化干燥温度为100～200℃。Further, the atomization drying temperature described in the step (1) is 100 to 200 °C.
进一步地，步骤(1)中所述的氧化石墨烯分散液中还加入氢氧化钾，氢氧化钾和氧化石墨烯的质量比为0.1～1:1。Further, potassium hydroxide is further added to the graphene oxide dispersion described in the step (1), and the mass ratio of potassium hydroxide to graphene oxide is 0.1 to 1:1.
进一步地，步骤(2)中所述的生物质碳源为秸秆、椰子壳、蔗糖渣、木屑、核桃壳、杏壳、枯草的一种或多种，活化剂为氢氧化钾、氢氧化钠的一种。Further, the biomass carbon source described in the step (2) is one or more of straw, coconut shell, sucrose residue, wood chips, walnut shell, apricot shell, and hay, and the activator is potassium hydroxide or sodium hydroxide. One kind.
进一步地，步骤(3)中所述的炭化温度为300～500℃，炭化时间为1～6h，活化温度为500～1000℃，活化时间为1～4h。Further, the carbonization temperature in the step (3) is 300 to 500 ° C, the carbonization time is 1 to 6 hours, the activation temperature is 500 to 1000 ° C, and the activation time is 1 to 4 hours.
本发明的有益效果在于：本发明首先通过雾化干燥法制备得到氧化石墨烯微球，再与生物质碳源、活化剂混合均匀，一起进行高温处理得到多孔碳网络。氧化石墨烯表面具有丰富的含氧官能团，在受热条件下基团快速脱除，产生气体，使石墨烯层层堆叠结构撑开得到微孔结构。通过雾化干燥得到的氧化石墨烯微球在热处理时会像爆米花一样急剧膨胀，产生丰富的孔结构，同时，生物质碳源在碳化时放出的气体能进一步膨胀石墨烯球。膨胀的石墨烯球与球之间的活性碳受到挤压，使得球与球之间形成均匀的活性炭层，形成碳网络。活化剂(氢氧化钾)同时与活性炭和石墨烯反应，产生新的孔洞。本发明所得多孔材料具有高比表面积、高孔隙率和低密度，稳定性好，可用于空气净化、水处理、催化载体、电化学材料等领域。The invention has the beneficial effects that the present invention firstly prepares the graphene oxide microspheres by the atomization drying method, and then mixes with the biomass carbon source and the activator uniformly, and performs high temperature treatment together to obtain a porous carbon network. The surface of the graphene oxide has a rich oxygen-containing functional group, and the group is rapidly removed under the heated condition to generate a gas, so that the graphene layer stack structure is opened to obtain a microporous structure. The graphene oxide microspheres obtained by atomization drying rapidly expand like popcorn during heat treatment to produce a rich pore structure, and at the same time, the gas released by the biomass carbon source during carbonization can further expand the graphene sphere. The activated carbon between the expanded graphene sphere and the sphere is squeezed such that a uniform layer of activated carbon is formed between the sphere and the sphere to form a carbon network. The activator (potassium hydroxide) reacts with both activated carbon and graphene to create new pores. The porous material obtained by the invention has high specific surface area, high porosity and low density, and has good stability, and can be used in the fields of air purification, water treatment, catalytic carrier, electrochemical material and the like.
具体实施方式detailed description
制备基于石墨烯的多孔碳网络的方法包括如下步骤：A method of preparing a graphene-based porous carbon network includes the following steps:
(1)通过雾化干燥法将单层氧化石墨烯分散液干燥，得到氧化石墨烯微球；雾化干燥温度为100～200℃；所述的氧化石墨烯分散液中还加入氢氧化钾，氢氧化钾和氧化石墨烯的质量比为0.1～1:1；(2)将步骤(1)得到的氧化石墨烯微球，与生物质碳源、活化剂混合，质量比为100:10～200:100～300，研磨至300～400目，转移到模具中，填充率为90～100％；所述的生物质碳源为秸秆、椰子壳、蔗糖渣、木屑、核桃壳、杏壳、枯草的一种或多种，活化剂为氢氧化钾、氢氧化钠的一种； (3)将模具密封后，对其中的混合物进行炭化、活化、洗涤得到多孔碳网络；所述的炭化温度为300～500℃，炭化时间为1～6h，活化温度为500～1000℃，活化时间为1～4h。(1) drying the single-layer graphene oxide dispersion by an atomization drying method to obtain graphene oxide microspheres; the atomization drying temperature is 100 to 200 ° C; and the potassium oxide oxide dispersion is further added with potassium hydroxide. The mass ratio of potassium hydroxide to graphene oxide is 0.1 to 1:1; (2) the graphene oxide microspheres obtained in the step (1) are mixed with the biomass carbon source and the activator, and the mass ratio is 100:10~ 200: 100 ~ 300, grinding to 300 ~ 400 mesh, transferred to the mold, the filling rate is 90 ~ 100%; the biomass carbon source is straw, coconut shell, sucrose residue, wood chips, walnut shell, apricot shell, One or more kinds of dry grass, the activator is one of potassium hydroxide and sodium hydroxide; (3) after sealing the mold, carbonizing, activating and washing the mixture to obtain a porous carbon network; the carbonization temperature The temperature is from 300 to 500 ° C, the carbonization time is from 1 to 6 hours, the activation temperature is from 500 to 1000 ° C, and the activation time is from 1 to 4 hours.
下面通过实施例对本发明进行具体描述，本实施例只用于对本发明做进一步的说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据上述发明的内容做出一些非本质的改变和调整均属本发明的保护范围。The present invention will be specifically described by the following examples, which are only used to further illustrate the present invention, and are not to be construed as limiting the scope of the present invention. Those skilled in the art will make some non-essential changes according to the contents of the above invention. And adjustments are within the scope of protection of the present invention.
本发明中所述的微球为本领域的常用技术术语，并不是对直径的限定，微球直径不是本发明研究的目的。此外，本发明所述方法制备得到的微球直径在100nm～50um不等。The microspheres described in the present invention are common technical terms in the art and are not intended to define the diameter. The diameter of the microspheres is not the object of the present invention. In addition, the diameter of the microspheres prepared by the method of the present invention varies from 100 nm to 50 um.
实施例1：Example 1:
(1)通过雾化干燥法将单层氧化石墨烯和氢氧化钾的混合分散液干燥，其中，氢氧化钾和氧化石墨烯的质量比为0.1:1，得到氧化石墨烯微球，雾化温度为130℃；(1) drying a mixed dispersion of a single layer of graphene oxide and potassium hydroxide by an atomization drying method, wherein a mass ratio of potassium hydroxide to graphene oxide is 0.1:1, obtaining graphene oxide microspheres, and atomizing The temperature is 130 ° C;
(2)将步骤(1)得到的氧化石墨烯微球，与椰子壳、氢氧化钾混合，质量比为100:10:100，研磨至300～400目，转移到模具中，填充率为90％；(2) The graphene oxide microspheres obtained in the step (1) are mixed with a coconut shell and potassium hydroxide at a mass ratio of 100:10:100, ground to 300-400 mesh, and transferred to a mold at a filling ratio of 90. %;
(3)将模具密封后，对其中的混合物进行500℃炭化2h，800℃活化2h，洗涤得到多孔碳网络。(3) After the mold was sealed, the mixture was carbonized at 500 ° C for 2 h, activated at 800 ° C for 2 h, and washed to obtain a porous carbon network.
经以上步骤，得到基于石墨烯的多孔碳网络，为黑色蓬松块体。密度为0.17g/cm 3，比表面积为1840m 2/g，孔体积为1.75cm 3/g。 Through the above steps, a graphene-based porous carbon network is obtained, which is a black fluffy block. The density was 0.17 g/cm 3 , the specific surface area was 1840 m 2 /g, and the pore volume was 1.75 cm 3 /g.
实施例2：Example 2:
(1)通过雾化干燥法将单层氧化石墨烯和氢氧化钾的混合分散液干燥，其中，氢氧化钾和氧化石墨烯的质量比为1:1，得到氧化石墨烯微球，雾化温度为130℃；(1) drying a mixed dispersion of a single layer of graphene oxide and potassium hydroxide by an atomization drying method, wherein a mass ratio of potassium hydroxide to graphene oxide is 1:1, obtaining graphene oxide microspheres, and atomizing The temperature is 130 ° C;
(2)将步骤(1)得到的氧化石墨烯微球，与椰子壳、氢氧化钾混合，质量比为100:10:100，研磨至300～400目，转移到模具中，填充率为90％；(2) The graphene oxide microspheres obtained in the step (1) are mixed with a coconut shell and potassium hydroxide at a mass ratio of 100:10:100, ground to 300-400 mesh, and transferred to a mold at a filling ratio of 90. %;
(3)将模具密封后，对其中的混合物进行500℃炭化2h，800℃活化2h，洗涤得到多孔碳网络。(3) After the mold was sealed, the mixture was carbonized at 500 ° C for 2 h, activated at 800 ° C for 2 h, and washed to obtain a porous carbon network.
经以上步骤，得到基于石墨烯的多孔碳网络，为黑色蓬松块体。密度为0.14g/cm 3，比表面积为2030m 2/g，孔体积为2.28cm 3/g。 Through the above steps, a graphene-based porous carbon network is obtained, which is a black fluffy block. The density was 0.14 g/cm 3 , the specific surface area was 2030 m 2 /g, and the pore volume was 2.28 cm 3 /g.
实施例3：Example 3:
(1)通过雾化干燥法将单层氧化石墨烯分散液干燥，得到氧化石墨烯微球， 雾化温度为130℃；(1) drying a single layer of graphene oxide dispersion by atomization drying method to obtain graphene oxide microspheres, the atomization temperature is 130 ° C;
(2)将步骤(1)得到的氧化石墨烯微球，与椰子壳、氢氧化钾混合，质量比为100:120:200，研磨至300～400目，转移到模具中，填充率为90％；(2) The graphene oxide microspheres obtained in the step (1) are mixed with a coconut shell and potassium hydroxide at a mass ratio of 100:120:200, ground to 300-400 mesh, and transferred to a mold at a filling ratio of 90. %;
(3)将模具密封后，对其中的混合物进行300℃炭化6h，800℃活化2h，洗涤得到多孔碳网络。(3) After sealing the mold, the mixture was carbonized at 300 ° C for 6 h, activated at 800 ° C for 2 h, and washed to obtain a porous carbon network.
经以上步骤，得到基于石墨烯的多孔碳网络，为黑色蓬松块体。密度为0.37g/cm 3，比表面积为1510m 2/g，孔体积为1.24cm 3/g。 Through the above steps, a graphene-based porous carbon network is obtained, which is a black fluffy block. The density was 0.37 g/cm 3 , the specific surface area was 1510 m 2 /g, and the pore volume was 1.24 cm 3 /g.
实施例4：Example 4:
(1)通过雾化干燥法将单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，雾化温度为130℃；(1) drying a single layer of graphene oxide dispersion by atomization drying method to obtain graphene oxide microspheres, the atomization temperature is 130 ° C;
(2)将步骤(1)得到的氧化石墨烯微球，与椰子壳、氢氧化钾混合，质量比为100:200:300，研磨至300～400目，转移到模具中，填充率为90％；(2) The graphene oxide microspheres obtained in the step (1) are mixed with a coconut shell and potassium hydroxide at a mass ratio of 100:200:300, ground to 300-400 mesh, and transferred to a mold at a filling ratio of 90. %;
(3)将模具密封后，对其中的混合物进行500℃炭化1h，500℃活化4h，洗涤得到多孔碳网络。(3) After sealing the mold, the mixture was carbonized at 500 ° C for 1 h, activated at 500 ° C for 4 h, and washed to obtain a porous carbon network.
经以上步骤，得到基于石墨烯的多孔碳网络，为黑色蓬松块体。密度为0.46g/cm 3，比表面积为1270m 2/g，孔体积为0.94cm 3/g。 Through the above steps, a graphene-based porous carbon network is obtained, which is a black fluffy block. The density was 0.46 g/cm 3 , the specific surface area was 1270 m 2 /g, and the pore volume was 0.94 cm 3 /g.
实施例5：Example 5:
(1)通过雾化干燥法将单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，雾化温度为200℃；(1) drying a single layer of graphene oxide dispersion by atomization drying method to obtain graphene oxide microspheres, the atomization temperature is 200 ° C;
(2)将步骤(1)得到的氧化石墨烯微球，与秸秆、氢氧化钾混合，质量比为100:60:150，研磨至300～400目，转移到模具中，填充率为100％；(2) The graphene oxide microspheres obtained in the step (1) are mixed with straw and potassium hydroxide at a mass ratio of 100:60:150, ground to 300-400 mesh, transferred to a mold, and the filling ratio is 100%. ;
(3)将模具密封后，对其中的混合物进行500℃炭化2h，1000℃活化1h，洗涤得到多孔碳网络。(3) After the mold was sealed, the mixture was carbonized at 500 ° C for 2 h, activated at 1000 ° C for 1 h, and washed to obtain a porous carbon network.
经以上步骤，得到基于石墨烯的多孔碳网络，为黑色蓬松块体。密度为0.22g/cm 3，比表面积为1360m 2/g，孔体积为0.97cm 3/g。 Through the above steps, a graphene-based porous carbon network is obtained, which is a black fluffy block. The density was 0.22 g/cm 3 , the specific surface area was 1360 m 2 /g, and the pore volume was 0.97 cm 3 /g.
实施例6：Example 6
(1)通过雾化干燥法将单层氧化石墨烯分散液干燥，得到氧化石墨烯微球，雾化温度为100℃；(1) drying a single layer of graphene oxide dispersion by atomization drying method to obtain graphene oxide microspheres, the atomization temperature is 100 ° C;
(2)将步骤(1)得到的氧化石墨烯微球，与木屑、氢氧化钾混合，质量比为100:60:150，研磨至300～400目，转移到模具中，填充率为95％；(2) The graphene oxide microspheres obtained in the step (1) are mixed with wood chips and potassium hydroxide at a mass ratio of 100:60:150, ground to 300-400 mesh, and transferred to a mold at a filling rate of 95%. ;
(3)将模具密封后，对其中的混合物进行300℃炭化2h，1000℃活化2h， 洗涤得到多孔碳网络。(3) After the mold was sealed, the mixture was carbonized at 300 ° C for 2 h, activated at 1000 ° C for 2 h, and washed to obtain a porous carbon network.
经以上步骤，得到基于石墨烯的多孔碳网络，为黑色蓬松块体。密度为0.19g/cm 3，比表面积为1480m 2/g，孔体积为1.02cm 3/g。 Through the above steps, a graphene-based porous carbon network is obtained, which is a black fluffy block. The density was 0.19 g/cm 3 , the specific surface area was 1480 m 2 /g, and the pore volume was 1.02 cm 3 /g.
实施例7：Example 7
(1)通过雾化干燥法将单层氧化石墨烯分散液干燥，将单层氧化石墨烯和氢氧化钾的混合分散液干燥，其中，氢氧化钾和氧化石墨烯的质量比为1:1，得到氧化石墨烯微球，雾化温度为100℃；(1) drying a single-layer graphene oxide dispersion by an atomization drying method, and drying a mixed dispersion of a single layer of graphene oxide and potassium hydroxide, wherein the mass ratio of potassium hydroxide to graphene oxide is 1:1. , obtaining graphene oxide microspheres, the atomization temperature is 100 ° C;
(2)将步骤(1)得到的氧化石墨烯微球，与椰子壳、氢氧化钾混合，质量比为100:60:110，研磨至300～400目，转移到模具中，填充率为95％；(2) The graphene oxide microspheres obtained in the step (1) are mixed with a coconut shell and potassium hydroxide at a mass ratio of 100:60:110, ground to 300-400 mesh, and transferred to a mold at a filling ratio of 95. %;
(3)将模具密封后，对其中的混合物进行300℃炭化2h，1000℃活化2h，洗涤得到多孔碳网络。(3) After sealing the mold, the mixture was carbonized at 300 ° C for 2 h, activated at 1000 ° C for 2 h, and washed to obtain a porous carbon network.
经以上步骤，得到基于石墨烯的多孔碳网络，为黑色蓬松块体。密度为0.16g/cm 3，比表面积为1870m 2/g，孔体积为2.17cm 3/g。 Through the above steps, a graphene-based porous carbon network is obtained, which is a black fluffy block. The density was 0.16 g/cm 3 , the specific surface area was 1870 m 2 /g, and the pore volume was 2.17 cm 3 /g.

Claims (5)

  1. 一种基于石墨烯的多孔碳网络的制备方法，其特征在于，包括以下步骤：A method for preparing a graphene-based porous carbon network, comprising the steps of:
    (1)通过雾化干燥法将单层氧化石墨烯分散液干燥，得到氧化石墨烯微球；(1) drying a single layer of graphene oxide dispersion by an atomization drying method to obtain graphene oxide microspheres;
    (2)将步骤(1)得到的氧化石墨烯微球，与生物质碳源、活化剂混合，质量比为100:10～200:100～300，研磨至300～400目，转移到模具中，填充率为90～100％；(2) mixing the graphene oxide microspheres obtained in the step (1) with a biomass carbon source and an activator at a mass ratio of 100:10 to 200:100 to 300, grinding to 300 to 400 mesh, and transferring to a mold. , the filling rate is 90 to 100%;
    (3)将模具密封后，对其中的混合物进行炭化、活化、洗涤得到多孔碳网络。(3) After the mold is sealed, the mixture is carbonized, activated, and washed to obtain a porous carbon network.
  2. 根据权利要求1所述的方法，其特征在于，步骤(1)中所述的雾化干燥温度为100～200℃。The method according to claim 1, wherein the atomization drying temperature in the step (1) is from 100 to 200 °C.
  3. 根据权利要求1所述的方法，其特征在于，步骤(1)中所述的氧化石墨烯分散液中还加入氢氧化钾，氢氧化钾和氧化石墨烯的质量比为0.1～1:1。The method according to claim 1, wherein potassium oxide is further added to the graphene oxide dispersion in the step (1), and the mass ratio of potassium hydroxide to graphene oxide is from 0.1 to 1:1.
  4. 根据权利要求1所述的方法，其特征在于，步骤(2)中所述的生物质碳源为秸秆、椰子壳、蔗糖渣、木屑、核桃壳、杏壳、枯草的一种或多种，活化剂为氢氧化钾、氢氧化钠的一种。The method according to claim 1, wherein the biomass carbon source in the step (2) is one or more of straw, coconut shell, sucrose residue, wood chips, walnut shell, apricot shell, and hay. The activator is one of potassium hydroxide and sodium hydroxide.
  5. 根据权利要求1所述的方法，其特征在于，步骤(3)中所述的炭化温度为300～500℃，炭化时间为1～6h，活化温度为500～1000℃，活化时间为1～4h。The method according to claim 1, wherein the carbonization temperature in the step (3) is 300 to 500 ° C, the carbonization time is 1 to 6 hours, the activation temperature is 500 to 1000 ° C, and the activation time is 1 to 4 hours. .
PCT/CN2018/077170 2017-04-14 2018-02-26 Preparation method for use with graphene-based porous carbon network WO2018188419A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710244352.5 2017-04-14
CN201710244352.5A CN106986647B (en) 2017-04-14 2017-04-14 A kind of preparation method of the porous carbon network based on graphene

Publications (1)

Publication Number Publication Date
WO2018188419A1 true WO2018188419A1 (en) 2018-10-18

Family

ID=59415017

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/077170 WO2018188419A1 (en) 2017-04-14 2018-02-26 Preparation method for use with graphene-based porous carbon network

Country Status (2)

Country Link
CN (1) CN106986647B (en)
WO (1) WO2018188419A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109950520A (en) * 2019-03-15 2019-06-28 深圳市本征方程石墨烯技术股份有限公司 A kind of nitrogenous graphene coated biomass carbon negative electrode material and preparation method thereof
CN113023723A (en) * 2021-02-04 2021-06-25 南京航空航天大学 Electromagnetic wave-absorbing material prepared from shaddock peel and preparation method thereof
US11814292B2 (en) 2021-07-23 2023-11-14 Nanotech Energy, Inc. Methods of graphene production and compositions thereof

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106986647B (en) * 2017-04-14 2019-09-06 杭州高烯科技有限公司 A kind of preparation method of the porous carbon network based on graphene
CN108031436A (en) * 2017-12-22 2018-05-15 湖南工业大学 A kind of alumina composite absorbent charcoal material and its preparation method and application
CN108383106A (en) * 2018-01-16 2018-08-10 湖南国盛石墨科技有限公司 A kind of preparation method of graphene/activated carbon microballon
CN108557799B (en) * 2018-06-04 2020-10-09 高彪峰 High-purity high-conductivity graphene-like hierarchical porous carbon and preparation method thereof
CN108795020A (en) * 2018-06-30 2018-11-13 杭州高烯科技有限公司 A kind of graphene-polyurathamc composite material and preparation method
CN108865061A (en) * 2018-07-14 2018-11-23 合肥艾飞新材料有限公司 A kind of hollow plumbago alkene microballoon and preparation method thereof
CN108975791B (en) * 2018-09-03 2020-11-06 洛阳炼化奥油化工股份有限公司 Regenerative aerated concrete with excellent freezing resistance and preparation method thereof
CN109455715B (en) * 2018-11-14 2022-07-05 中山火炬职业技术学院 Preparation method of graphene modified hydrophobic activated carbon
CN114408922B (en) * 2021-12-30 2023-08-25 海南大学 Method for preparing activated carbon by using encapsulation to assist chemical activation

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140183415A1 (en) * 2012-12-31 2014-07-03 Cheil Industries Inc. Graphene-Based Composite and Method of Preparing the Same
CN106241778A (en) * 2016-07-15 2016-12-21 浙江大学 A kind of high-specific surface area many folds hollow graphite alkene microsphere and preparation method thereof
CN106486295A (en) * 2016-10-29 2017-03-08 大英聚能科技发展有限公司 The preparation method of the Graphene of high specific capacitance/high surface carbon composite
CN106532026A (en) * 2016-12-19 2017-03-22 中国科学院山西煤炭化学研究所 Sulfur-activated carbon/graphene composite material and application thereof
CN106986647A (en) * 2017-04-14 2017-07-28 杭州高烯科技有限公司 A kind of preparation method of the porous carbon network based on graphene

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103253658B (en) * 2013-05-13 2016-06-29 常州第六元素材料科技股份有限公司 A kind of high volumetric capacitance Graphene and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140183415A1 (en) * 2012-12-31 2014-07-03 Cheil Industries Inc. Graphene-Based Composite and Method of Preparing the Same
CN106241778A (en) * 2016-07-15 2016-12-21 浙江大学 A kind of high-specific surface area many folds hollow graphite alkene microsphere and preparation method thereof
CN106486295A (en) * 2016-10-29 2017-03-08 大英聚能科技发展有限公司 The preparation method of the Graphene of high specific capacitance/high surface carbon composite
CN106532026A (en) * 2016-12-19 2017-03-22 中国科学院山西煤炭化学研究所 Sulfur-activated carbon/graphene composite material and application thereof
CN106986647A (en) * 2017-04-14 2017-07-28 杭州高烯科技有限公司 A kind of preparation method of the porous carbon network based on graphene

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109950520A (en) * 2019-03-15 2019-06-28 深圳市本征方程石墨烯技术股份有限公司 A kind of nitrogenous graphene coated biomass carbon negative electrode material and preparation method thereof
CN109950520B (en) * 2019-03-15 2022-05-31 深圳市本征方程石墨烯技术股份有限公司 Nitrogen-containing graphene-coated biomass carbon negative electrode material and preparation method thereof
CN113023723A (en) * 2021-02-04 2021-06-25 南京航空航天大学 Electromagnetic wave-absorbing material prepared from shaddock peel and preparation method thereof
CN113023723B (en) * 2021-02-04 2023-12-01 南京航空航天大学 Electromagnetic wave-absorbing material prepared from shaddock peel and preparation method thereof
US11814292B2 (en) 2021-07-23 2023-11-14 Nanotech Energy, Inc. Methods of graphene production and compositions thereof

Also Published As

Publication number Publication date
CN106986647B (en) 2019-09-06
CN106986647A (en) 2017-07-28

Similar Documents

Publication Publication Date Title
WO2018188419A1 (en) Preparation method for use with graphene-based porous carbon network
US8603935B2 (en) Method for manufacturing photocatalyst multifunctional dust-free active carbon color ball
CN109516458A (en) A kind of biomass-based graded porous carbon and preparation method thereof
CN104289179B (en) Method for preparing attapulgite/carbon composite adsorbent by one-step carbonization-activation
WO2021027100A1 (en) Nitrogen-doped porous carbon material, preparation method therefor and use thereof
CN108217733B (en) Preparation method of carbon-manganese dioxide composite material
CN109081342A (en) A kind of biomass porous active carbon of nipa palm leaf and its preparation method and application
CN101961644B (en) Chloride-carbonaceous skeleton composite adsorbent and preparation method thereof
CN102838105B (en) Preparation method of grading porous carbon material
CN111099587B (en) Preparation method of bamboo leaf-based carbon material with high specific surface area
CN109437202A (en) A kind of two dimension magnesium-yttrium-transition metal carbon (nitrogen) compound aeroge and its preparation method and application
CN108773844A (en) A kind of method that micro-calcium addition catalytic activation prepares coal base porous carbon materials
CN103979533A (en) Preparation method for nitrogen-sulfur double-doped active carbon for supercapacitors
CN103641111A (en) Preparation method of graded porous graphene material for super-capacitor
CN103787327A (en) One-step preparation method of hollow spherical porous graphite for supercapacitor
CN107081127A (en) A kind of preparation method of graphene/activated carbon composite porous microspheres
CN106629723A (en) Biomass-based N, S and P-containing co-doped porous carbon and application thereof
CN105709689B (en) Carbon-based functional material and preparation method thereof
CN107456948A (en) A kind of preparation method of purification of air graphene composite activated carbon
CN106334502A (en) Preparation method of reduced-oxidized graphene/aspergillus niger cellulose aerogel
CN108630453A (en) One-step method prepares the method and application thereof of class graphene carbon nanometer sheet material
CN108046254A (en) A kind of corncob derives active carbon electrode material and preparation method thereof
CN110156013B (en) Active carbon surface pore-forming method
CN107903575A (en) A kind of preparation method of electrode for capacitors graphene phenolic-resin based composite fibre film
CN109192524B (en) Preparation method of activated carbon-graphene composite porous material

Legal Events

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

Ref document number: 18784329

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18784329

Country of ref document: EP

Kind code of ref document: A1