WO2012116593A1 - Chemical processing method for graphene material having high specific surface area by using strong alkali - Google Patents

Chemical processing method for graphene material having high specific surface area by using strong alkali Download PDF

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WO2012116593A1
WO2012116593A1 PCT/CN2012/071068 CN2012071068W WO2012116593A1 WO 2012116593 A1 WO2012116593 A1 WO 2012116593A1 CN 2012071068 W CN2012071068 W CN 2012071068W WO 2012116593 A1 WO2012116593 A1 WO 2012116593A1
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graphite oxide
surface area
specific surface
filtration
graphene
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PCT/CN2012/071068
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瞿研
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无锡第六元素高科技发展有限公司
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/182Graphene
    • C01B32/184Preparation
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/20Graphite
    • C01B32/21After-treatment
    • C01B32/23Oxidation
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00Structure or properties of graphene
    • C01B2204/20Graphene characterized by its properties
    • C01B2204/32Size or surface area

Definitions

  • the invention relates to a method for producing a graphene material by a chemical treatment method, and belongs to the technical field of preparation of graphene materials.
  • Graphene the English name Graphene, has the same carbon atom arrangement as the monoatomic layer of graphite. It is a single-layer two-dimensional crystal composed of carbon atoms arranged in a sp2 mixed orbital domain as a honeycomb crystal lattice. It can be imagined as carbon. A network of atomic sizes formed by atoms and their covalent bonds.
  • the name of graphene comes from the English graphite ( graphite) + -ene (end of the olefin).
  • the structure of graphene is very stable, and the connection between the carbon atoms inside is very flexible.
  • the surface of the carbon atom is bent and deformed, so that the carbon atoms do not have to be rearranged to adapt to the external force, thereby keeping the structure stable.
  • This stable lattice structure gives graphene excellent thermal conductivity.
  • electrons in the graphene move in orbit, they do not scatter due to lattice defects or introduction of foreign atoms. Since the interaction between the atoms is very strong, even at the normal temperature, even if the surrounding carbon atoms collide, the internal electrons of the graphene are very little disturbed.
  • Graphene is considered to be a planar polycyclic aromatic hydrocarbon atom crystal. As a single-layer carbon atom planar material, graphene can be obtained by peeling off a graphite material. Since the graphite crystal film was discovered by scientists at the University of Manchester in 2004, graphene has become the focus of attention in the scientific and industrial circles. Graphene has a thickness of only 0.335 nm, which is not only the thinnest of the known materials, but also very strong and hard; as a simple substance, it transmits electrons at room temperature faster than all known conductors and semiconductors (: graphene The migration speed of medium electrons reaches 1/300 of the speed of light).
  • Mechanical methods include micromechanical separation or tear tape (paste HOPG), orientation epitaxy, and methods of heating SiC; chemical methods are chemical reduction and chemical cleavage, metal substrate chemical vapor deposition, and chemical dispersion.
  • micromechanical separation method which directly cuts the graphene sheets from the larger crystals.
  • a typical micromechanical separation method is to rub with another material that puffs or introduces defective pyrolytic graphite.
  • the surface of the bulk graphite produces flake-like crystals, and the flake-like crystals contain a single layer of graphene.
  • the disadvantage of the micromechanical separation method is that the method is to use a sheet obtained by rubbing the graphite surface to screen a single layer of graphene sheet, the size of which is difficult to control, and it is impossible to reliably produce a graphite sheet sample for the length of the supply.
  • the orientation epitaxy method uses the growth matrix atomic structure to "specify" graphene.
  • the carbon atoms are infiltrated into the crucible at 1150 ° C, and then cooled. After cooling to 850 ° C, a large amount of carbon atoms absorbed before will float to the crucible.
  • a single layer of carbon atoms "islands" in the shape of the lens fill the entire surface of the substrate, and eventually they can grow into a complete layer of graphene. After the first layer covers 80%, the second layer begins to grow.
  • the underlying graphene has a strong interaction with the ruthenium, while the second layer is almost completely separated from the ruthenium, leaving only the weakly coupled, and the resulting single-layer graphene sheets perform satisfactorily.
  • the graphene sheets produced by this method tend to be uneven in thickness, and the adhesion between the graphene and the matrix affects the characteristics of the carbon layer, and the substrate used in the orientation epitaxy method is a rare metal crucible, which limits its application.
  • Si is removed by heating single crystal 6H-SiC, and a graphene sheet layer is decomposed on a single crystal (0001) plane.
  • the specific process is: passing the sample obtained by etching with oxygen or hydrogen under high vacuum Sub-bombardment heats up to remove oxides. After the Auchen electron spectroscopy is used to confirm that the surface oxide is completely removed, the sample is heated to raise the temperature to 1250 ⁇ 1450 ° C and then the temperature is 1 mm ⁇ 20 mm, thereby forming a very thin graphite layer.
  • Berger et al. have been able to controllably prepare single or multi-layer graphene.
  • this method has a drawback in that its thickness is determined by the heating temperature, and it is difficult to prepare a graphene having a large area and a single thickness.
  • a typical chemical dispersion method includes the following steps: Graphite oxide is formed by hydrolysis of graphite under the action of a strong acid such as H 2 S0 4 , HNO 3 , HC 10 4 or a strong oxidizing agent or electrochemical peroxidation. Graphite oxide is also a layered covalent compound with a interlayer distance of about 0.8 nm (graphite is 0.335 nm), which varies depending on the preparation method. It is considered that the graphite oxide contains a group such as -C-OH, -C-0-C, or even -COOH.
  • the graphite oxide can be peeled off in water or other polar solvent under the action of an external force such as ultrasonic waves to form a single layer of graphene oxide 0 to obtain graphene oxide, and then to reduce the graphite oxide produced by reduction.
  • the olefin is de-graphitized and regains its electrical conductivity when it retains its geometry.
  • the reduction method includes a chemical reduction method, for example, using a strong reducing agent such as hydrazine hydrate, high-temperature heat treatment, microwave irradiation treatment, electrochemical reduction, or the like, to obtain a conductive graphene material having a high specific surface area.
  • a strong reducing agent such as hydrazine hydrate, high-temperature heat treatment, microwave irradiation treatment, electrochemical reduction, or the like.
  • the graphene powder obtained by several methods currently has a specific surface area of less than 1000 m 2 /g, generally less than 700 m 2 /g, which is much lower than the theoretical specific surface area of graphene. This technical bottleneck constrains the further application of graphene materials.
  • the technical problem to be solved by the present invention is to overcome the defect that the specific surface area of the graphene material obtained by the prior chemical dispersion method is small, and to provide a preparation method, and the obtained graphene has a large specific surface area while maintaining high conductance of the material.
  • a method for obtaining a high specific surface area graphene material by treatment with a strong alkali comprising the following preparation steps:
  • step (3) Performing solid-liquid separation on the condensed graphite oxide suspension in step (2), drying the obtained solid;
  • step (3) The solid particles or powder obtained after drying in step (3) are sintered at a temperature of ⁇ ;
  • step (4) The solid after sintering in step (4) is washed, filtered and dried.
  • Step (1) The graphite oxide suspension is obtained by dissolving ultrasonically by taking graphite oxide in a solvent.
  • the solvent is preferably water, especially deionized water; the ultrasonic dispersion is prior art, and the ultrasonic dispersion device and the ultrasonic dispersion process are both prior art, and those skilled in the art can obtain it from the market or prepare it by themselves.
  • the ultrasonic dispersion time is 2 to 3 hours.
  • the concentration of the graphite oxide suspension in the step (1) is 0.01 to: 10 mg/ml, preferably 0.1 to 9.5 mg/ml, further preferably 0.5 to 9 mg/ml, for example, 1 mg/ml, 1.5 mg/ml, 2 mg/ml, 2.5 mg/ml, 3 mg/ml, 3.5 mg/ml, 4 mg/ml, 4.5 mg/ml, 5 mg/ml, 5.5 mg/ml > 6 mg/ml, 6.5 mg/ml, 7 mg/mK 7.5 mg/mK 8 mg/ml, 8.5 mg/ml.
  • the strong base is a strong base well known in the art, and a typical strong base is potassium hydroxide, sodium hydroxide, calcium hydroxide or a mixture of at least two thereof; further preferably potassium hydroxide or sodium hydroxide Or a mixture thereof.
  • Step (2) The mixing ratio of the medium-strong alkali aqueous solution and the graphite oxide suspension is such that cloud agglomeration occurs in the stirring.
  • the mixing ratio of the strong alkali aqueous solution and the graphite oxide suspension is such that the mass ratio of the strong base to the oxidized graphite is 1 to 50:1.
  • the solid-liquid separation described in the step (3) is a process well known in the art, and the solid-liquid separation does not change the physicochemical properties of the obtained solid.
  • Typical solid-liquid separation processes include filtration, centrifugation, precipitation, gravity settling, centrifugal sedimentation, etc.
  • the present invention preferably employs a filtration, centrifugal separation process, and further preferably a filtration process.
  • the filtration process is a unit operation known in the art, including unit operations such as suction filtration, pressure filtration, vacuum filtration, centrifugal filtration, vacuum filtration, membrane filtration, ultrafiltration, and the like.
  • Sintering is carried out at a high temperature as described in the step (4), and the high temperature is 500 to 1500 ° C, preferably 700 to 1200 ° C, and more preferably 800 to 1100 ° C.
  • the high temperature is 500 to 1500 ° C, preferably 700 to 1200 ° C, and more preferably 800 to 1100 ° C.
  • Those skilled in the art can freely select specific sintering temperatures according to specific process requirements and field conditions in the range of 500 to 150 (TC range) given by the present invention, for example, 750 ° C, 850 ° C, 900 ° C, 950. °C, 1000 °C, 1050 °C, 1150 ° C, etc.
  • the sintering may be performed by constant temperature sintering or temperature swing sintering, and may be gradient temperature sintering or temperature programming.
  • the sintering is preferably carried out under the protection of an inert gas, preferably nitrogen or argon.
  • the washing process is a prior art which aims to remove the washable impurities present in the solid, particularly the alkaline substance remaining in the previous process.
  • the present invention preferably employs a water washing process which can be carried out a plurality of times, for example 2 to 6 times, preferably 3 to 5 times.
  • the pH of the washing liquid after washing the solid matter is generally controlled to about ⁇ .
  • the method of the present invention for obtaining a high specific surface area graphene material by chemical treatment with a strong alkali comprises the following preparation steps:
  • step (2) adding the strong alkali aqueous solution of step (1) to the graphite oxide suspension of step (1), stirring until cloud condensation occurs; wherein, the mass ratio of strong alkali to graphite oxide in the mixture is 1 to 50:1;
  • step (4) The solid after sintering in step (4) is washed with water, filtered, and dried to obtain a high specific surface area graphene material.
  • the high specific surface area graphene material is obtained by a specific preparation method of the present invention.
  • the present invention is capable of increasing the specific surface area of graphene, specifically, from the current maximum of 700 m 2 /g to several times to 1500 to 3000 m 2 /g, while maintaining high conductivity of the material.
  • the invention utilizes the reaction of the strong base and the carbon at a high temperature to carry out further chemical treatment on the graphene powder obtained by the heat treatment or the microwave irradiation, thereby rapidly and massively etching the micropores of the nanometer order on the surface of the graphene. Greatly increase its specific surface area.
  • the high temperature treatment can further reduce the graphene, thereby ensuring high conductivity of the obtained material.
  • Figure 1 is a process flow diagram of the process of the present invention. detailed description
  • a method of modifying a graphene material using potassium hydroxide comprising the following preparation steps:
  • step (3) Pour the agglomerate obtained in step (3) into a vacuum filter device, and open the vacuum valve for filtration until no water drops are dropped;
  • step (4) Put the material obtained in step (4) into a vacuum oven, draw the vacuum to the limit, set the temperature to 60 ° C, and dry for 24 hours;
  • step (7) The solid obtained in the step (7) is again placed in a glass container, 200 ml of deionized water is added, magnetically stirred at 800 rpm for 1 hour, and then poured into a vacuum suction container to filter off water; (9) repeating step (8) until the pH of the suspension after stirring is 7;
  • step (10) The solid obtained in the step (9) is placed in a vacuum oven and dried at 70 ° C for 2 hours;
  • a method of modifying a graphene material using potassium hydroxide comprising the following preparation steps:
  • step (3) Pour the agglomerate obtained in step (3) into a vacuum filter device, and open the vacuum valve for filtration until no water drops are dropped;
  • step (4) Put the material obtained in step (4) into a vacuum oven, draw the vacuum to the limit, set the temperature to 60 ° C, and dry for 24 hours;
  • step (7) The solid obtained in the step (7) is again placed in a glass container, 50 ml of deionized water is added, magnetically stirred at 800 rpm for 1 hour, and then poured into a vacuum suction container to filter off water;
  • step (9) Repeat step (8) until the pH of the suspension after stirring is 7;
  • step (10) The solid obtained in the step (9) is placed in a vacuum oven and dried at 70 ° C for 2 hours;
  • a method of modifying a graphene material with sodium hydroxide comprising the following preparation steps:
  • step (3) Pour the agglomerate obtained in step (3) into a vacuum filter device, and open the vacuum valve for filtration until no water drops are dropped;
  • step (4) Put the material obtained in step (4) into a vacuum oven, draw the vacuum to the limit, set the temperature to 60 ° C, and dry for 24 hours;
  • step (7) The solid obtained in the step (7) is again placed in a glass container, 200 ml of deionized water is added, magnetically stirred at 800 rpm for 1 hour, and then poured into a vacuum suction container to filter off water;
  • step (9) Repeat step (8) until the pH of the suspension after stirring is 7;
  • step (10) The solid obtained in the step (9) is placed in a vacuum oven and dried at 70 ° C for 2 hours;
  • a method of modifying a graphene material with sodium hydroxide comprising the following preparation steps:
  • step (3) Pour the agglomerate obtained in step (3) into a vacuum filter device, and open the vacuum valve for filtration until no water drops are dropped;
  • step (4) Put the material obtained in step (4) into a vacuum oven, draw the vacuum to the limit, and set the temperature to Dry at 60 ° C for 24 hours;
  • step (7) The solid obtained in the step (7) is again placed in a glass container, 50 ml of deionized water is added, magnetically stirred at 800 rpm for 1 hour, and then poured into a vacuum suction container to filter off water;
  • step (9) Repeat step (8) until the pH of the suspension after stirring is 7;
  • step (10) The solid obtained in the step (9) is placed in a vacuum oven and dried at 70 ° C for 2 hours;
  • the graphene powder modified by potassium hydroxide treatment can be obtained, and the specific surface area is 1590 m 2 /g.
  • the graphene materials prepared in Examples 1 to 4 of the present invention have a specific surface area of 1,500 to 3,000 m 2 /g, which is much higher than the prior art. Moreover, the graphene materials prepared in the first to fourth embodiments of the present invention maintain high conductivity of the graphene material while ensuring a high specific surface area.

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Abstract

Provided is a chemical processing method for graphene material having a high specific surface area by using strong alkali, comprising the following steps: (1) a graphite oxide suspension is prepared; a strong alkali water solution having a concentration of 0.2 to 20 mol/L is prepared; (2) the strong alkali water solution in step (1) is added to the graphite oxide suspension in step (1), and then stirred till cloud-like condensation occurs; (3) solid-liquid separation is performed on the flocculated graphite oxide suspension in step (2), and the obtained solid is dried; (4) the dried solid granules or powder in step (3) is sintered at a high temperature; (5) the sintered solid in step (4) is washed, filtered, and dried. Also provided are graphene having a high specific surface area prepared using said method, and applications thereof, the graphene having a specific surface area of 1500 to 3000 m2/g.

Description

说 明 书 一种利用强碱化学处理得到高比表面积石墨烯材料的方法 技术领域  Method for obtaining high specific surface area graphene material by chemical treatment with strong alkali
本发明涉及一种化学处理法生产石墨烯材料的方法, 属于石墨烯材料制备 技术领域。  The invention relates to a method for producing a graphene material by a chemical treatment method, and belongs to the technical field of preparation of graphene materials.
背景技术 Background technique
石墨烯, 英文名 Graphene, 其碳原子排列与石墨的单原子层相同, 是碳原 子以 sp2混成轨域呈蜂巢晶格 (honeycomb crystal lattice) 排列构成的单层二维 晶体, 可想像为由碳原子和其共价键所形成的原子尺寸网。 石墨烯的命名来自 英文的 graphite (石墨) + -ene (烯类结尾)。  Graphene, the English name Graphene, has the same carbon atom arrangement as the monoatomic layer of graphite. It is a single-layer two-dimensional crystal composed of carbon atoms arranged in a sp2 mixed orbital domain as a honeycomb crystal lattice. It can be imagined as carbon. A network of atomic sizes formed by atoms and their covalent bonds. The name of graphene comes from the English graphite ( graphite) + -ene (end of the olefin).
石墨烯的结构非常稳定, 其内部的碳原子之间的连接很柔韧, 当施加外力 于石墨烯时, 碳原子面会弯曲变形, 使得碳原子不必重新排列来适应外力, 从 而保持结构稳定。 这种稳定的晶格结构使石墨烯具有优秀的导热性。 另外, 石 墨烯中的电子在轨道中移动时, 不会因晶格缺陷或引入外来原子而发生散射。 由于原子间作用力十分强, 在常温下, 即使周围碳原子发生挤撞, 石墨烯内部 电子受到的干扰也非常小。  The structure of graphene is very stable, and the connection between the carbon atoms inside is very flexible. When an external force is applied to the graphene, the surface of the carbon atom is bent and deformed, so that the carbon atoms do not have to be rearranged to adapt to the external force, thereby keeping the structure stable. This stable lattice structure gives graphene excellent thermal conductivity. In addition, when electrons in the graphene move in orbit, they do not scatter due to lattice defects or introduction of foreign atoms. Since the interaction between the atoms is very strong, even at the normal temperature, even if the surrounding carbon atoms collide, the internal electrons of the graphene are very little disturbed.
石墨烯被认为是平面多环芳香烃原子晶体。 作为单层碳原子平面材料, 石 墨烯可以通过剥离石墨材料而得到。 这种石墨晶体薄膜自 2004年被曼彻斯特大 学的科学家发现之后, 石墨烯就成为科学界和工业界关注的焦点。 石墨烯的厚 度只有 0.335纳米,不仅是已知材料中最薄的一种,还非常牢固坚硬;作为单质, 它在室温下传递电子的速度比已知所有的导体和半导体都快 (:石墨烯中电子的迁 移速度达到了光速的 1/300)。 由于石墨烯的特殊原子结构, 其中载流子(电子和 空穴) 的行为必须用相对论量子力学 (relativistic quantum mechanics)才能描绘。 同时, 作为单层碳原子结构, 石墨烯的理论比表面积高达 2630 m2/g。 如此高的 比表面积使得以基于石墨烯的材料成为极有前途的能量储存活性材料, 使得石 墨烯材料有可能在储氢、 新型锂离子电池、 超级电容器或者燃料电池得到应用。 Graphene is considered to be a planar polycyclic aromatic hydrocarbon atom crystal. As a single-layer carbon atom planar material, graphene can be obtained by peeling off a graphite material. Since the graphite crystal film was discovered by scientists at the University of Manchester in 2004, graphene has become the focus of attention in the scientific and industrial circles. Graphene has a thickness of only 0.335 nm, which is not only the thinnest of the known materials, but also very strong and hard; as a simple substance, it transmits electrons at room temperature faster than all known conductors and semiconductors (: graphene The migration speed of medium electrons reaches 1/300 of the speed of light). Due to the special atomic structure of graphene, the behavior of carriers (electrons and holes) must be characterized by relativistic quantum mechanics. At the same time, as a single-layer carbon atom structure, the theoretical specific surface area of graphene is as high as 2630 m 2 /g. Such a high specific surface area makes the graphene-based material a promising energy storage active material, making it possible to use graphene materials in hydrogen storage, new lithium ion batteries, supercapacitors or fuel cells.
目前石墨烯的合成方法主要有两种: 机械方法和化学方法。 机械方法包括 微机械分离法或撕胶带发 (粘贴 HOPG)、 取向附生法和加热 SiC的方法; 化学 方法是化学还原法与化学解理法、 金属衬底化学气相沉积法和化学分散法等。  At present, there are two main methods for the synthesis of graphene: mechanical methods and chemical methods. Mechanical methods include micromechanical separation or tear tape (paste HOPG), orientation epitaxy, and methods of heating SiC; chemical methods are chemical reduction and chemical cleavage, metal substrate chemical vapor deposition, and chemical dispersion.
最普通的是微机械分离法, 直接将石墨烯薄片从较大的晶体上剪裁下来。  The most common is the micromechanical separation method, which directly cuts the graphene sheets from the larger crystals.
2004年 Novoselovt等用这种方法制备出了单层石墨烯, 并可以在外界环境下稳 定存在。 典型微机械分离法是用另外一种材料膨化或者引入缺陷的热解石墨进 行摩擦, 体相石墨的表面会产生絮片状的晶体, 在这些絮片状的晶体中含有单 层的石墨烯。 但微机械分离法缺点是, 此法是利用摩擦石墨表面获得的薄片来 筛选出单层的石墨烯薄片, 其尺寸不易控制, 无法可靠地制造长度足供应用的 石墨薄片样本。 In 2004, Novoselovt et al. prepared a single layer of graphene in this way and it was stable in the external environment. A typical micromechanical separation method is to rub with another material that puffs or introduces defective pyrolytic graphite. The surface of the bulk graphite produces flake-like crystals, and the flake-like crystals contain a single layer of graphene. However, the disadvantage of the micromechanical separation method is that the method is to use a sheet obtained by rubbing the graphite surface to screen a single layer of graphene sheet, the size of which is difficult to control, and it is impossible to reliably produce a graphite sheet sample for the length of the supply.
取向附生法是利用生长基质原子结构 "种" 出石墨烯, 首先让碳原子在 1150°C下渗入钌, 然后冷却, 冷却到 850°C后, 之前吸收的大量碳原子就会浮到 钌表面, 镜片形状的单层的碳原子 "孤岛"布满了整个基质表面, 最终它们可 长成完整的一层石墨烯。 第一层覆盖 80%后, 第二层开始生长。 底层的石墨烯 会与钌产生强烈的交互作用, 而第二层后就几乎与钌完全分离, 只剩下弱电耦 合, 得到的单层石墨烯薄片表现令人满意。 但采用这种方法生产的石墨烯薄片 往往厚度不均匀, 且石墨烯和基质之间的黏合会影响碳层的特性, 另外所述取 向附生法使用的基质是稀有金属钌, 这限制了其应用。  The orientation epitaxy method uses the growth matrix atomic structure to "specify" graphene. First, the carbon atoms are infiltrated into the crucible at 1150 ° C, and then cooled. After cooling to 850 ° C, a large amount of carbon atoms absorbed before will float to the crucible. On the surface, a single layer of carbon atoms "islands" in the shape of the lens fill the entire surface of the substrate, and eventually they can grow into a complete layer of graphene. After the first layer covers 80%, the second layer begins to grow. The underlying graphene has a strong interaction with the ruthenium, while the second layer is almost completely separated from the ruthenium, leaving only the weakly coupled, and the resulting single-layer graphene sheets perform satisfactorily. However, the graphene sheets produced by this method tend to be uneven in thickness, and the adhesion between the graphene and the matrix affects the characteristics of the carbon layer, and the substrate used in the orientation epitaxy method is a rare metal crucible, which limits its application.
加热 SiC法是通过加热单晶 6H-SiC脱除 Si, 在单晶 (0001)面上分解出石墨 烯片层。 具体过程是: 将经氧气或氢气刻蚀处理得到的样品在高真空下通过电 子轰击加热, 除去氧化物。 用俄歇电子能谱确定表面的氧化物完全被移除后, 将样品加热使之温度升高至 1250~1450°C后恒温 lmm~20mm, 从而形成极薄的 石墨层。 经过几年的探索, Berger 等人已经能可控地制备出单层或是多层石墨 烯。 但该方法的缺陷是, 其厚度由加热温度决定, 制备大面积且具有单一厚度 的石墨烯比较困难。 In the heating SiC method, Si is removed by heating single crystal 6H-SiC, and a graphene sheet layer is decomposed on a single crystal (0001) plane. The specific process is: passing the sample obtained by etching with oxygen or hydrogen under high vacuum Sub-bombardment heats up to remove oxides. After the Auchen electron spectroscopy is used to confirm that the surface oxide is completely removed, the sample is heated to raise the temperature to 1250~1450 ° C and then the temperature is 1 mm ~ 20 mm, thereby forming a very thin graphite layer. After several years of exploration, Berger et al. have been able to controllably prepare single or multi-layer graphene. However, this method has a drawback in that its thickness is determined by the heating temperature, and it is difficult to prepare a graphene having a large area and a single thickness.
在石墨烯的现有制备方法中, 以化学分散法最为适应于大规模生产石墨烯 材料, 尤其是粉末状石墨烯材料。 具体地, 典型的化学分散法包括如下步骤: 氧化石墨是石墨在 H2S04、 HN03、 HC104等强酸和强氧化剂的作用下, 或 电化学过氧化作用下, 经水解后形成的。 氧化石墨同样是一层状共价化合物, 层间距离大约为 0.8nm (石墨为 0.335nm), 依制备方法而异。 一般认为, 氧化 石墨中含有 -C-OH、 -C-0-C, 甚至 -COOH等基团。 和石墨不同, 由于极性基团 的存在, 氧化石墨片层之间存在静电排斥作用。 因此, 氧化石墨在外力, 如超 声波的作用下在水中或其它极性溶剂中可以发生剥离, 形成单层氧化石墨烯 (graphene oxide )0 制得氧化石墨烯后, 再通过还原使所制氧化石墨烯脱氧重新 石墨化, 保持其几何形貌时可恢复部分其导电性。 In the existing preparation method of graphene, the chemical dispersion method is most suitable for mass production of graphene materials, especially powdered graphene materials. Specifically, a typical chemical dispersion method includes the following steps: Graphite oxide is formed by hydrolysis of graphite under the action of a strong acid such as H 2 S0 4 , HNO 3 , HC 10 4 or a strong oxidizing agent or electrochemical peroxidation. Graphite oxide is also a layered covalent compound with a interlayer distance of about 0.8 nm (graphite is 0.335 nm), which varies depending on the preparation method. It is considered that the graphite oxide contains a group such as -C-OH, -C-0-C, or even -COOH. Unlike graphite, electrostatic repulsion exists between the layers of graphite oxide due to the presence of polar groups. Therefore, the graphite oxide can be peeled off in water or other polar solvent under the action of an external force such as ultrasonic waves to form a single layer of graphene oxide 0 to obtain graphene oxide, and then to reduce the graphite oxide produced by reduction. The olefin is de-graphitized and regains its electrical conductivity when it retains its geometry.
具体地, 还原方法包括化学还原法, 比如利用水合肼等强还原剂、 高温加 热处理、 微波辐照处理、 电化学还原等, 可得到导电的具有较高比表面积的石 墨烯材料。 但是, 目前几种方法得到的石墨烯粉末的比表面积均在 1000 m2/g以 下,一般小于 700 m2/g, 远低于石墨烯的理论比表面积。此技术瓶颈约束了石墨 烯材料的进一歩应用。 Specifically, the reduction method includes a chemical reduction method, for example, using a strong reducing agent such as hydrazine hydrate, high-temperature heat treatment, microwave irradiation treatment, electrochemical reduction, or the like, to obtain a conductive graphene material having a high specific surface area. However, the graphene powder obtained by several methods currently has a specific surface area of less than 1000 m 2 /g, generally less than 700 m 2 /g, which is much lower than the theoretical specific surface area of graphene. This technical bottleneck constrains the further application of graphene materials.
因此, 如何制备得到比表面积大, 同时保持材料的高电导的石墨烯, 是本 领域所面临的技术难题。  Therefore, how to prepare graphene having a large specific surface area while maintaining a high conductance of a material is a technical problem faced in the art.
发明内容 本发明要解决的技术问题是克服现有化学分散法所得石墨烯材料的比表面 积小的缺陷, 提供了一种制备方法, 所得石墨烯比表面积大, 同时保持材料的 高电导。 Summary of the invention The technical problem to be solved by the present invention is to overcome the defect that the specific surface area of the graphene material obtained by the prior chemical dispersion method is small, and to provide a preparation method, and the obtained graphene has a large specific surface area while maintaining high conductance of the material.
为了解决上述技术问题, 本发明的目的之一在于提供一种制备得到高比表 面积石墨烯材料的方法。  In order to solve the above technical problems, it is an object of the present invention to provide a method of preparing a graphene material having a high specific surface area.
一种利用强碱处理得到高比表面积石墨烯材料的方法, 包括以下制备步骤: A method for obtaining a high specific surface area graphene material by treatment with a strong alkali, comprising the following preparation steps:
(1) . 配制氧化石墨悬浮液; 配制浓度为 0.2〜20 mol/L的强碱水溶液;(1). Preparing a graphite oxide suspension; preparing a strong alkali aqueous solution having a concentration of 0.2 to 20 mol/L;
(2) . 将步骤(1 )所述的强碱水溶液加入步骤(1 ) 的氧化石墨悬浮液中, 搅 拌至出现云状凝聚; (2) The aqueous solution of the strong alkali described in the step (1) is added to the graphite oxide suspension of the step (1), and stirred until cloud aggregation occurs;
(3) . 对步骤 (2 ) 凝聚后的氧化石墨悬浮液进行固液分离, 将得到的固体干 燥;  (3). Performing solid-liquid separation on the condensed graphite oxide suspension in step (2), drying the obtained solid;
(4) . 将步骤 (3 ) 干燥后所得固体颗粒或者粉末在髙温下进行烧结;  (4). The solid particles or powder obtained after drying in step (3) are sintered at a temperature of 髙;
(5) . 将步骤 (4 ) 烧结后的固体进行洗涤, 过滤和干燥。  (5). The solid after sintering in step (4) is washed, filtered and dried.
步骤 (1 ) 所述的氧化石墨悬浮液通过取氧化石墨置于溶剂中, 超声分散得 到。 所述溶剂优选水, 特别是去离子水; 所述超声分散是现有技术, 其超声分 散设备以及超声分散工艺均是现有技术, 所属技术领域的技术人员均可从市场 获得或自己制备得到。 优选地, 所述超声分散时间为 2〜3小时。  Step (1) The graphite oxide suspension is obtained by dissolving ultrasonically by taking graphite oxide in a solvent. The solvent is preferably water, especially deionized water; the ultrasonic dispersion is prior art, and the ultrasonic dispersion device and the ultrasonic dispersion process are both prior art, and those skilled in the art can obtain it from the market or prepare it by themselves. . Preferably, the ultrasonic dispersion time is 2 to 3 hours.
步骤(1 )所述的氧化石墨悬浮液浓度为 0.01〜: 10 mg/ml,优选 0.1~9.5 mg/ml, 进一歩优选 0.5-9 mg/ml,例如 1 mg/ml、 1.5 mg/ml、 2 mg/ml、 2.5 mg/ml、 3 mg/ml、 3.5 mg/ml、 4 mg/ml、 4.5 mg/ml、 5 mg/ml、 5.5 mg/ml > 6 mg/ml、 6.5 mg/ml、 7 mg/mK 7.5 mg/mK 8 mg/ml、 8.5 mg/ml。  The concentration of the graphite oxide suspension in the step (1) is 0.01 to: 10 mg/ml, preferably 0.1 to 9.5 mg/ml, further preferably 0.5 to 9 mg/ml, for example, 1 mg/ml, 1.5 mg/ml, 2 mg/ml, 2.5 mg/ml, 3 mg/ml, 3.5 mg/ml, 4 mg/ml, 4.5 mg/ml, 5 mg/ml, 5.5 mg/ml > 6 mg/ml, 6.5 mg/ml, 7 mg/mK 7.5 mg/mK 8 mg/ml, 8.5 mg/ml.
优选地, 所述强碱为所属技术领域所公知的强碱, 典型的强碱为氢氧化钾、 氢氧化钠、 氢氧化钙或其至少二者的混合物; 进一步优选氢氧化钾、 氢氧化钠 或其混合物。 Preferably, the strong base is a strong base well known in the art, and a typical strong base is potassium hydroxide, sodium hydroxide, calcium hydroxide or a mixture of at least two thereof; further preferably potassium hydroxide or sodium hydroxide Or a mixture thereof.
步骤 (2) 中强碱水溶液与氧化石墨悬浮液的混合比例, 使得搅拌出现云状 凝聚为准。 优选地, 强碱水溶液与氧化石墨悬浮液的混合比例, 使得强碱与氧 化石墨的质量比达到 1~50: 1为准。  Step (2) The mixing ratio of the medium-strong alkali aqueous solution and the graphite oxide suspension is such that cloud agglomeration occurs in the stirring. Preferably, the mixing ratio of the strong alkali aqueous solution and the graphite oxide suspension is such that the mass ratio of the strong base to the oxidized graphite is 1 to 50:1.
步骤 (3 ) 中所述的固液分离, 为本技术领域所公知的工艺, 所述固液分离 以不改变所获得的固体的物理化学性质为准。 典型的固液分离工艺包括过滤、 离心分离、 沉淀、 重力沉降、 离心沉降等, 本发明优选采用过滤、 离心分离工 艺, 进一步优选过滤工艺。  The solid-liquid separation described in the step (3) is a process well known in the art, and the solid-liquid separation does not change the physicochemical properties of the obtained solid. Typical solid-liquid separation processes include filtration, centrifugation, precipitation, gravity settling, centrifugal sedimentation, etc. The present invention preferably employs a filtration, centrifugal separation process, and further preferably a filtration process.
所述过滤工艺是所属技术领域已知的单元操作, 包括抽滤、 压滤、 真空过 滤、 离心过滤、 真空抽滤、 膜过滤、 超滤等单元操作。  The filtration process is a unit operation known in the art, including unit operations such as suction filtration, pressure filtration, vacuum filtration, centrifugal filtration, vacuum filtration, membrane filtration, ultrafiltration, and the like.
步骤 (4 ) 中所述的高温下进行烧结, 所述高温为 500~1500°C, 优选 700〜 1200 °C, 进一步优选 800〜1100 °C。 所属技术领域的技术人员在本发明给出的 500~150(TC范围内, 可以根据具体的工艺要求及现场条件, 自由选择具体烧结 温度, 例如 750°C、 850°C、 900°C、 950°C、 1000 °C、 1050°C、 1150°C等。 所述 烧结可以采用恒温烧结或变温烧结, 可以是梯度变温烧结, 也可以是程序升温。  Sintering is carried out at a high temperature as described in the step (4), and the high temperature is 500 to 1500 ° C, preferably 700 to 1200 ° C, and more preferably 800 to 1100 ° C. Those skilled in the art can freely select specific sintering temperatures according to specific process requirements and field conditions in the range of 500 to 150 (TC range) given by the present invention, for example, 750 ° C, 850 ° C, 900 ° C, 950. °C, 1000 °C, 1050 °C, 1150 ° C, etc. The sintering may be performed by constant temperature sintering or temperature swing sintering, and may be gradient temperature sintering or temperature programming.
所述烧结优选在惰性气体保护下进行, 所述惰性气体优选氮气、 氩气。 步骤 (5 ) 所述洗涤工艺为现有技术, 其以除去固体中存在的可洗涤杂质为 目的, 特别是之前工艺歩骤残存的碱性物质。 本发明优选采用水洗工艺, 所述 洗涤工艺可以进行多次, 例如 2~6次, 优选 3~5次。 本发明的洗涤工艺, 一般 将洗涤固体物质后的洗涤液 pH值控制在 Ί左右为准。  The sintering is preferably carried out under the protection of an inert gas, preferably nitrogen or argon. Step (5) The washing process is a prior art which aims to remove the washable impurities present in the solid, particularly the alkaline substance remaining in the previous process. The present invention preferably employs a water washing process which can be carried out a plurality of times, for example 2 to 6 times, preferably 3 to 5 times. In the washing process of the present invention, the pH of the washing liquid after washing the solid matter is generally controlled to about Ί.
优选的, 本发明的一种利用强碱化学处理得到高比表面积石墨烯材料的方 法, 包括以下制备步骤:  Preferably, the method of the present invention for obtaining a high specific surface area graphene material by chemical treatment with a strong alkali comprises the following preparation steps:
(1) 取氧化石墨置于水中, 超声处理 2〜3小时, 氧化石墨浓度为 0.01〜10 mg/ml; 配制浓度为 0.2〜20 mol/L强碱水溶液; (1) Take graphite oxide in water, sonicate for 2 to 3 hours, and the concentration of graphite oxide is 0.01~10 Mg/ml; a concentration of 0.2~20 mol/L strong alkali aqueous solution;
(2) 将步骤 (1 ) 的强碱水溶液加入到步骤 (1 ) 的氧化石墨悬浮液, 搅拌至 出现云状凝聚; 其中, 混合物中强碱与氧化石墨的质量比为 1~50:1;  (2) adding the strong alkali aqueous solution of step (1) to the graphite oxide suspension of step (1), stirring until cloud condensation occurs; wherein, the mass ratio of strong alkali to graphite oxide in the mixture is 1 to 50:1;
(3) 过滤歩骤 (2 ) 凝聚后的氧化石墨悬浮液, 将滤饼干燥;  (3) Filtration step (2) The condensed graphite oxide suspension is dried, and the filter cake is dried;
(4) 将步骤 (3 ) 干燥后所得固体颗粒或者粉末在 700〜120(TC下进行烧结; (4) The solid particles or powder obtained after drying in step (3) are sintered at 700 to 120 (TC);
(5) 将步骤 (4 ) 烧结后的固体进行水洗、 过滤和干燥, 得到高比表面积石 墨烯材料。 (5) The solid after sintering in step (4) is washed with water, filtered, and dried to obtain a high specific surface area graphene material.
本发明的目的之一还在于提供一种高比表面积石墨烯材料, 所述石墨烯材 料比表面积为 1500〜3000 m2/g, 并且同时保持材料的高电导。 所述高比表面积 石墨烯材料通过本发明的特定制备方法得到。 It is also an object of the present invention to provide a high specific surface area graphene material having a specific surface area of from 1500 to 3000 m 2 /g while maintaining high electrical conductance of the material. The high specific surface area graphene material is obtained by a specific preparation method of the present invention.
本发明的目的之一还在于提供一种高比表面积石墨烯材料的用途, 其用于 储氢、 锂离子电池、 超级电容器或者燃料电池, 以及纳电子器件、 高频电路、 光子传感器、 基因电子测序和减少噪音。  It is also an object of the present invention to provide a high specific surface area graphene material for use in hydrogen storage, lithium ion batteries, supercapacitors or fuel cells, as well as nanoelectronic devices, high frequency circuits, photon sensors, gene electronics Sequencing and noise reduction.
本发明能够提高石墨烯比表面积, 具体地, 从目前的最高 700 m2/g提高数 倍至 1500〜3000 m2/g, 并且同时保持材料的高电导。 本发明利用强碱和碳在高 温下的反应, 对热处理或者微波辐照得到的石墨烯粉末进行进一歩化学处理, 从而快速的、 大批量的在石墨烯表面腐蚀出纳米量级的微孔, 极大地提高其比 表面积。 于此同时, 高温处理可进一步还原石墨烯, 从而保证所得到材料的高 导电性。 The present invention is capable of increasing the specific surface area of graphene, specifically, from the current maximum of 700 m 2 /g to several times to 1500 to 3000 m 2 /g, while maintaining high conductivity of the material. The invention utilizes the reaction of the strong base and the carbon at a high temperature to carry out further chemical treatment on the graphene powder obtained by the heat treatment or the microwave irradiation, thereby rapidly and massively etching the micropores of the nanometer order on the surface of the graphene. Greatly increase its specific surface area. At the same time, the high temperature treatment can further reduce the graphene, thereby ensuring high conductivity of the obtained material.
附图说明 DRAWINGS
附图用来提供对本发明的进一步理解, 并且构成说明书的一部分, 与本发 明的实施例一起用于解释本发明, 并不构成对本发明的限制。  The drawings are intended to provide a further understanding of the invention, and are intended to be a part of the description of the invention.
图 1是本发明方法的工艺流程图。 具体实施方式 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a process flow diagram of the process of the present invention. detailed description
以下结合附图对本发明的优选实施例进行说明, 应当理解, 此处所描述的 优选实施例仅用于说明和解释本发明, 并不用于限定本发明。  The preferred embodiments of the present invention are described in the following with reference to the accompanying drawings, which are intended to illustrate and illustrate the invention.
实施例 1  Example 1
利用氢氧化钾改性石墨烯材料的方法, 包括以下制备步骤:  A method of modifying a graphene material using potassium hydroxide, comprising the following preparation steps:
( 1 ) 称取 11.2g纯氢氧化钾颗粒置于氧化铝烧杯, 加入 20ml的去离子水, 得到 20mol/L的氢氧化钾水溶液;  (1) Weigh 11.2 g of pure potassium hydroxide particles in an alumina beaker, and add 20 ml of deionized water to obtain a 20 mol/L potassium hydroxide aqueous solution;
(2)称取 0.224g氧化石墨颗粒置于玻璃烧杯, 加入 2.24L的去离子水, 用 针状超声设备超声 3小时, 得到 0.1g/L的氧化石墨悬浮液;  (2) Weigh 0.224 g of graphite oxide particles in a glass beaker, add 2.24 L of deionized water, and sonicate with a needle-shaped ultrasonic device for 3 hours to obtain a 0.1 g/L graphite oxide suspension;
(3 ) 将步骤 (1 ) 得到的氢氧化钾溶液倒入步骤 (2) 得到的氧化石墨悬浮 液, 置于磁搅拌平板上以 1000转 /分钟的速度进行搅拌 30分钟;  (3) pouring the potassium hydroxide solution obtained in the step (1) into the graphite oxide suspension obtained in the step (2), and stirring on the magnetic stirring plate at a speed of 1000 rpm for 30 minutes;
(4) 将步骤 (3 ) 得到的凝聚物倒入真空过滤装置, 开启真空阀门进行抽 滤, 直至无水滴滴下;  (4) Pour the agglomerate obtained in step (3) into a vacuum filter device, and open the vacuum valve for filtration until no water drops are dropped;
( 5 ) 将步骤 (4 ) 得到的物质放入真空烘箱, 将真空抽到极限, 温度设至 60°C, 干燥 24小时;  (5) Put the material obtained in step (4) into a vacuum oven, draw the vacuum to the limit, set the temperature to 60 ° C, and dry for 24 hours;
(6)将歩骤(5 )得到固体颗粒置入管式电炉, 以每分钟 5°C的速度将温度 升至 800°C, 然后保持 1小时, 同时通入 150cm3/min的氩气气流进行保护, 压 强设为 1个大气压; (6) The solid particles obtained in the step (5) were placed in a tubular electric furnace, and the temperature was raised to 800 ° C at a rate of 5 ° C per minute, and then maintained for 1 hour while introducing an argon gas flow of 150 cm 3 /min. Protected, the pressure is set to 1 atmosphere;
(7) 待电炉冷却至室温后, 取出固体颗粒, 置入玻璃容器, 加入 200ml的 去离子水, 在 800转 /分钟的速度下磁搅拌 1小时, 然后倒入真空抽滤溶液滤掉 水;  (7) After the electric furnace is cooled to room temperature, the solid particles are taken out, placed in a glass container, 200 ml of deionized water is added, magnetically stirred at a speed of 800 rpm for 1 hour, and then poured into a vacuum filtration solution to filter off water;
( 8) 将步骤 (7 ) 得到的固体重新置入玻璃容器, 加入 200ml的去离子水, 在 800转 /分钟的速度下磁搅拌 1小时, 然后再次倒入真空抽滤容器滤掉水; (9) 重复步骤 (8) 直至得到搅拌后的悬浮液 pH值为 7; (8) The solid obtained in the step (7) is again placed in a glass container, 200 ml of deionized water is added, magnetically stirred at 800 rpm for 1 hour, and then poured into a vacuum suction container to filter off water; (9) repeating step (8) until the pH of the suspension after stirring is 7;
(10)将歩骤 (9) 得到的固体置入真空烘箱在 70°C下干燥 2小时;  (10) The solid obtained in the step (9) is placed in a vacuum oven and dried at 70 ° C for 2 hours;
(11)将步骤 (10) 得到的固体在管式炉中 800°C下真空中处理 2小时; (11) The solid obtained in the step (10) is treated in a tube furnace at 800 ° C for 2 hours in a vacuum;
(12) 待炉子冷却到室温, 即可得到氢氧化钾处理改性后的石墨烯粉末, 比表面积为 2073 m2/g。 实施例 2 (12) After the furnace is cooled to room temperature, the graphene powder modified by potassium hydroxide treatment can be obtained, and the specific surface area is 2073 m 2 /g. Example 2
利用氢氧化钾改性石墨烯材料的方法, 包括以下制备步骤:  A method of modifying a graphene material using potassium hydroxide, comprising the following preparation steps:
(1)称取 0.112g纯氢氧化钾颗粒置于氧化铝烧杯, 加入 20ml的去离子水, 得到 0.2mol/L的氢氧化钾水溶液;  (1) Weigh 0.112 g of pure potassium hydroxide particles in an alumina beaker, and add 20 ml of deionized water to obtain a 0.2 mol/L potassium hydroxide aqueous solution;
(2)称取 O.lg氧化石墨颗粒置于玻璃烧杯, 加入 0.01 L的去离子水,用针 状超声设备超声 1小时, 得到 10g/L的氧化石墨悬浮液; (2) Weigh O.lg graphite particles in a glass beaker, add 0.01 L of deionized water, and sonicate with a needle-shaped ultrasonic device for 1 hour to obtain a 10 g / L graphite oxide suspension;
(3)将步骤 1得到的氢氧化钾溶液倒入歩骤(2)得到的氧化石墨悬浮液, 置于磁搅拌平板上以 200转 /分钟的速度进行搅拌 30分钟;  (3) pouring the potassium hydroxide solution obtained in the step 1 into the graphite oxide suspension obtained in the step (2), and stirring on a magnetic stirring plate at a speed of 200 rpm for 30 minutes;
(4) 将步骤 (3) 得到的凝聚物倒入真空过滤装置, 开启真空阀门进行抽 滤, 直至无水滴滴下;  (4) Pour the agglomerate obtained in step (3) into a vacuum filter device, and open the vacuum valve for filtration until no water drops are dropped;
(5) 将步骤 (4) 得到的物质放入真空烘箱, 将真空抽到极限, 温度设至 60°C, 干燥 24小时;  (5) Put the material obtained in step (4) into a vacuum oven, draw the vacuum to the limit, set the temperature to 60 ° C, and dry for 24 hours;
(6)将歩骤(5)得到固体颗粒置入管式电炉, 以每分钟 5°C的速度将温度 升至 800°C, 然后保持 1小时, 同时通入 150cm3/min的氩气气流进行保护, 压 强设为 1个大气压; (6) The solid particles obtained in the step (5) were placed in a tubular electric furnace, and the temperature was raised to 800 ° C at a rate of 5 ° C per minute, and then maintained for 1 hour while introducing an argon gas flow of 150 cm 3 /min. Protected, the pressure is set to 1 atmosphere;
(7) 待电炉冷却至室温后, 取出固体颗粒, 置入玻璃容器, 加入 50ml的 去离子水, 在 800转 /分钟的速度下磁搅拌 1小时, 然后倒入真空抽滤溶液滤掉 水; (7) After the furnace is cooled to room temperature, the solid particles are taken out, placed in a glass container, added with 50 ml of deionized water, magnetically stirred at 800 rpm for 1 hour, and then poured into a vacuum pumping solution to filter off. Water
(8) 将步骤 (7) 得到的固体重新置入玻璃容器, 加入 50ml的去离子水, 在 800转 /分钟的速度下磁搅拌 1小时, 然后再次倒入真空抽滤容器滤掉水; (8) The solid obtained in the step (7) is again placed in a glass container, 50 ml of deionized water is added, magnetically stirred at 800 rpm for 1 hour, and then poured into a vacuum suction container to filter off water;
(9) 重复步骤 (8) 直至得到搅拌后的悬浮液 pH值为 7; (9) Repeat step (8) until the pH of the suspension after stirring is 7;
(10)将步骤 (9) 得到的固体置入真空烘箱在 70°C下干燥 2小时; (10) The solid obtained in the step (9) is placed in a vacuum oven and dried at 70 ° C for 2 hours;
(11)将步骤 (10) 得到的固体在管式炉中 800°C下真空中处理 2小时;(11) The solid obtained in the step (10) is treated in a tube furnace at 800 ° C for 2 hours in a vacuum;
(12) 待炉子冷却到室温, 即可得到氢氧化钾处理改性后的石墨烯粉末, 比表面积为 1825 m2/g。 实施例 3 (12) After the furnace is cooled to room temperature, the graphene powder modified by potassium hydroxide treatment can be obtained, and the specific surface area is 1825 m 2 /g. Example 3
利用氢氧化钠改性石墨烯材料的方法, 包括以下制备步骤:  A method of modifying a graphene material with sodium hydroxide, comprising the following preparation steps:
(1) 称取 5.6g纯氢氧化钠颗粒置于氧化铝烧杯, 加入 20ml的去离子水, 得到 10mol/L的氢氧化钾水溶液;  (1) Weigh 5.6 g of pure sodium hydroxide pellets in an alumina beaker, and add 20 ml of deionized water to obtain a 10 mol/L potassium hydroxide aqueous solution;
(2) 称取 lg氧化石墨颗粒置于玻璃烧杯, 加入 0.2L的去离子水, 用针状 超声设备超声 3小时, 得到 5g/L的氧化石墨悬浮液;  (2) Weighing lg graphite particles in a glass beaker, adding 0.2L of deionized water, and sonicating with a needle-shaped ultrasonic device for 3 hours to obtain a 5 g/L graphite oxide suspension;
(3)将步骤(1) 得到的氢氧化钠溶液倒入步骤 (2) 得到的氧化石墨悬浮 液, 置于磁搅拌平板上以 1000转 /分钟的速度进行搅拌 30分钟;  (3) pouring the sodium hydroxide solution obtained in the step (1) into the graphite oxide suspension obtained in the step (2), and stirring on the magnetic stirring plate at a speed of 1000 rpm for 30 minutes;
(4) 将步骤 (3) 得到的凝聚物倒入真空过滤装置, 开启真空阀门进行抽 滤, 直至无水滴滴下;  (4) Pour the agglomerate obtained in step (3) into a vacuum filter device, and open the vacuum valve for filtration until no water drops are dropped;
(5) 将步骤 (4) 得到的物质放入真空烘箱, 将真空抽到极限, 温度设至 60°C, 干燥 24小时;  (5) Put the material obtained in step (4) into a vacuum oven, draw the vacuum to the limit, set the temperature to 60 ° C, and dry for 24 hours;
(6)将歩骤(5)得到固体颗粒置入管式电炉, 以每分钟 5°C的速度将温度 升至 800°C, 然后保持 1小时, 同时通入 150cm3/min的氩气气流进行保护, 压 强设为 1个大气压; (6) The solid particles obtained in the step (5) were placed in a tubular electric furnace, and the temperature was raised to 800 ° C at a rate of 5 ° C per minute, and then maintained for 1 hour while passing an argon gas flow of 150 cm 3 /min. Protection, pressure Strongly set to 1 atmosphere;
(7)待电炉冷却至室温后, 取出固体颗粒, 置入玻璃容器, 加入 200ml的 去离子水, 在 800转 /分钟的速度下磁搅拌 1小时, 然后用倒入真空抽滤溶液滤 掉水;  (7) After the electric furnace is cooled to room temperature, the solid particles are taken out, placed in a glass container, 200 ml of deionized water is added, magnetically stirred at 800 rpm for 1 hour, and then the water is filtered off by pouring the vacuum filtration solution. ;
(8)将步骤(7)得到的固体重新置入玻璃容器, 加入 200ml的去离子水, 在 800转 /分钟的速度下磁搅拌 1小时, 然后再次倒入真空抽滤容器滤掉水; (8) The solid obtained in the step (7) is again placed in a glass container, 200 ml of deionized water is added, magnetically stirred at 800 rpm for 1 hour, and then poured into a vacuum suction container to filter off water;
(9) 重复步骤 (8) 直至得到搅拌后的悬浮液 pH值为 7; (9) Repeat step (8) until the pH of the suspension after stirring is 7;
(10)将歩骤 (9) 得到的固体置入真空烘箱在 70°C下干燥 2小时; (10) The solid obtained in the step (9) is placed in a vacuum oven and dried at 70 ° C for 2 hours;
(11)将步骤 (10) 得到的固体在管式炉中 800°C下真空中处理 2小时;(11) The solid obtained in the step (10) is treated in a tube furnace at 800 ° C for 2 hours in a vacuum;
(12) 待炉子冷却到室温, 即可得到氢氧化钾处理改性后的石墨烯粉末, 比表面积为 2542 m2/g0 实施例 4 (12) furnace to be cooled to room temperature, to obtain graphene potassium hydroxide powder after modification, specific surface area of 2542 m 2 / g 0 EXAMPLE 4
利用氢氧化钠改性石墨烯材料的方法, 包括以下制备步骤:  A method of modifying a graphene material with sodium hydroxide, comprising the following preparation steps:
(1)称取 0.112g纯氢氧化钠颗粒置于氧化铝烧杯, 加入 20ml的去离子水, 得到 0.2mol/L的氢氧化钾水溶液;  (1) Weigh 0.112 g of pure sodium hydroxide pellets in an alumina beaker, and add 20 ml of deionized water to obtain a 0.2 mol/L potassium hydroxide aqueous solution;
(2) 称取 O.lg氧化石墨颗粒置于玻璃烧杯, 加入 1L的去离子水, 用针状 超声设备超声 1小时, 得到 O.lg/L的氧化石墨悬浮液;  (2) Weighing O.lg graphite oxide particles in a glass beaker, adding 1 L of deionized water, and ultrasonicating with a needle-shaped ultrasonic device for 1 hour to obtain an O.lg/L graphite oxide suspension;
(3)将步骤(1) 得到的氢氧化钠溶液倒入步骤 (2) 得到的氧化石墨悬浮 液, 置于磁搅拌平板上以 200转 /分钟的速度进行搅拌 30分钟;  (3) pouring the sodium hydroxide solution obtained in the step (1) into the graphite oxide suspension obtained in the step (2), and stirring on a magnetic stirring plate at a speed of 200 rpm for 30 minutes;
(4) 将步骤 (3) 得到的凝聚物倒入真空过滤装置, 开启真空阀门进行抽 滤, 直至无水滴滴下;  (4) Pour the agglomerate obtained in step (3) into a vacuum filter device, and open the vacuum valve for filtration until no water drops are dropped;
(5) 将步骤 (4) 得到的物质放入真空烘箱, 将真空抽到极限, 温度设至 60°C, 干燥 24小时; (5) Put the material obtained in step (4) into a vacuum oven, draw the vacuum to the limit, and set the temperature to Dry at 60 ° C for 24 hours;
(6)将歩骤(5 )得到固体颗粒置入管式电炉, 以每分钟 5°C的速度将温度 升至 800°C, 然后保持 1小时, 同时通入 150cm3/min的氩气气流进行保护, 压 强设为 1个大气压;  (6) The solid particles obtained in the step (5) were placed in a tubular electric furnace, and the temperature was raised to 800 ° C at a rate of 5 ° C per minute, and then maintained for 1 hour while passing an argon gas flow of 150 cm 3 /min. Protection, the pressure is set to 1 atmosphere;
(7) 待电炉冷却至室温后, 取出固体颗粒, 置入玻璃容器, 加入 50ml 的 去离子水, 在 800转 /分钟的速度下磁搅拌 1小时, 然后用倒入真空抽滤溶液滤 掉水;  (7) After the furnace is cooled to room temperature, the solid particles are taken out, placed in a glass container, 50 ml of deionized water is added, magnetically stirred at 800 rpm for 1 hour, and then the water is filtered off by pouring the vacuum filtration solution. ;
( 8) 将步骤 (7 ) 得到的固体重新置入玻璃容器, 加入 50ml的去离子水, 在 800转 /分钟的速度下磁搅拌 1小时, 然后再次倒入真空抽滤容器滤掉水; (8) The solid obtained in the step (7) is again placed in a glass container, 50 ml of deionized water is added, magnetically stirred at 800 rpm for 1 hour, and then poured into a vacuum suction container to filter off water;
(9) 重复步骤 (8) 直至得到搅拌后的悬浮液 pH值为 7; (9) Repeat step (8) until the pH of the suspension after stirring is 7;
( 10) 将歩骤 (9 ) 得到的固体置入真空烘箱在 70°C下干燥 2小时;  (10) The solid obtained in the step (9) is placed in a vacuum oven and dried at 70 ° C for 2 hours;
( 11 ) 将步骤 (10) 得到的固体在管式炉中 800°C下真空中处理 2小时; (11) The solid obtained in the step (10) is treated in a tube furnace at 800 ° C for 2 hours in a vacuum;
( 12 ) 待炉子冷却到室温, 即可得到氢氧化钾处理改性后的石墨烯粉末, 比表面积为 1590 m2/g。 (12) After the furnace is cooled to room temperature, the graphene powder modified by potassium hydroxide treatment can be obtained, and the specific surface area is 1590 m 2 /g.
本发明实施例 1〜4制备得到的石墨烯材料, 比表面积为 1500〜3000 m2/g, 其远远高于现有技术。 并且, 本发明实施例 1~4制备得到的石墨烯材料在保证 高比表面积的同时, 保持了石墨烯材料的高电导。 The graphene materials prepared in Examples 1 to 4 of the present invention have a specific surface area of 1,500 to 3,000 m 2 /g, which is much higher than the prior art. Moreover, the graphene materials prepared in the first to fourth embodiments of the present invention maintain high conductivity of the graphene material while ensuring a high specific surface area.
最后应说明的是: 以上所述仅为本发明的优选实施例而已, 并不用于限制 本发明, 尽管参照前述实施例对本发明进行了详细的说明, 对于本领域的技术 人员来说, 其依然可以对前述各实施例所记载的技术方案进行修改, 或者对其 中部分技术特征进行等同替换。 凡在本发明的精祌和原则之内, 所作的任何修 改、 等同替换、 改进等, 均应包含在本发明的保护范围之内。  It should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art The technical solutions described in the foregoing embodiments may be modified, or some of the technical features may be equivalently replaced. Any modifications, equivalent substitutions, improvements, etc., which are within the scope of the invention, are intended to be included within the scope of the invention.

Claims

权 利 要 求 书 Claim
1、 一种利用强碱化学处理得到高比表面积石墨烯材料的方法, 包括以下制 备步骤:  1. A method for obtaining a high specific surface area graphene material by chemical treatment with a strong alkali, comprising the following steps of preparation:
(1) 配制氧化石墨悬浮液; 配制浓度为 0.2〜20 mol/L的强碱水溶液; (1) preparing a graphite oxide suspension; preparing a strong alkali aqueous solution having a concentration of 0.2 to 20 mol/L;
(2) 将步骤(1 )所述的强碱水溶液加入歩骤(1 ) 的氧化石墨悬浮液中, 搅 拌至出现云状凝聚; (2) adding the strong alkali aqueous solution described in the step (1) to the graphite oxide suspension of the step (1), and stirring until a cloud-like aggregation occurs;
(3) 对步骤 (2 ) 凝聚后的氧化石墨悬浮液进行固液分离, 将得到的固体干 燥;  (3) Step (2) solid-liquid separation of the condensed graphite oxide suspension, and drying the obtained solid;
(4) 将步骤 (3 ) 干燥后所得固体颗粒或者粉末在高温下进行烧结;  (4) The solid particles or powder obtained after drying in the step (3) are sintered at a high temperature;
(5) 将步骤 (4 ) 烧结后的固体进行洗涤, 过滤和干燥。  (5) The solid after sintering in step (4) is washed, filtered and dried.
2、 根据权利要求 1所述的方法, 其特征在于, 步骤 (1 ) 所述的氧化石墨 悬浮液浓度为 0.01〜10 mg/ml, 优选 0.1~9.5 mg/ml, 进一步优选 0.5~9 mg/ml; 步骤(1 )所述的氧化石墨悬浮液通过取氧化石墨置于溶剂中, 超声分散得 到; 优选地, 所述超声分散时间为 2〜3小时;  The method according to claim 1, wherein the concentration of the graphite oxide suspension in the step (1) is 0.01 to 10 mg/ml, preferably 0.1 to 9.5 mg/ml, further preferably 0.5 to 9 mg/ The oxidized graphite suspension of the step (1) is obtained by dissolving ultrasonically by taking graphite oxide in a solvent; preferably, the ultrasonic dispersion time is 2 to 3 hours;
所述溶剂优选水, 特别是去离子水。  The solvent is preferably water, especially deionized water.
3、 根据权利要求 1或 2所述的方法, 其特征在于, 所述强碱为氢氧化钾、 氢氧化钠、 氢氧化钙或其至少二者的混合物; 进一步优选氢氧化钾、 氢氧化钠 或其混合物。  3. The method according to claim 1 or 2, wherein the strong base is potassium hydroxide, sodium hydroxide, calcium hydroxide or a mixture of at least two thereof; further preferably potassium hydroxide or sodium hydroxide Or a mixture thereof.
4、 根据权利要求 1-3 之一所述的方法, 其特征在于, 步骤 (2 ) 中强碱水 溶液与氧化石墨悬浮液的混合比例, 使得搅拌出现云状凝聚为准;  The method according to any one of claims 1 to 3, characterized in that the mixing ratio of the strong alkaline water solution and the graphite oxide suspension in the step (2) is such that cloud agglomeration occurs in the stirring;
优选地, 强碱水溶液与氧化石墨悬浮液的混合比例, 使得强碱与氧化石墨 的质量比达到 1 50:1为准。  Preferably, the mixing ratio of the aqueous solution of the strong alkali to the suspension of the graphite oxide is such that the mass ratio of the strong base to the graphite oxide is 1 50:1.
5、 根据权利要求 1-4之一所述的方法, 其特征在于, 步骤 (3 ) 中所述的 固液分离, 包括过滤、 离心分离、 沉淀、 重力沉降、 离心沉降; 优选过滤、 离 心分离; The method according to any one of claims 1 to 4, characterized in that the solid-liquid separation in the step (3) comprises filtration, centrifugation, sedimentation, gravity sedimentation, centrifugal sedimentation; preferably filtration, separation Heart separation
所述过滤包括抽滤、 压滤、 真空过滤、 离心过滤、 真空抽滤、 膜过滤、 超 滤。  The filtration includes suction filtration, pressure filtration, vacuum filtration, centrifugal filtration, vacuum filtration, membrane filtration, and ultrafiltration.
6、 根据权利要求 1-5 之一所述的方法, 其特征在于, 步骤 (4) 中所述的 高温下进行烧结, 所述高温为 500~1500°C, 优选 700〜1200°C, 进一步优选 800-1100 °C ;  The method according to any one of claims 1 to 5, characterized in that the sintering is performed at a high temperature as described in the step (4), the high temperature is 500 to 1500 ° C, preferably 700 to 1200 ° C, further Preferably 800-1100 ° C;
所述烧结可以采用恒温烧结或变温烧结, 可以是梯度变温烧结, 也可以是 程序升温;  The sintering may be performed by constant temperature sintering or variable temperature sintering, may be gradient temperature sintering, or may be programmed;
所述烧结优选在惰性气体保护下进行, 所述惰性气体优选氮气、 氩气。 The sintering is preferably carried out under the protection of an inert gas, preferably nitrogen or argon.
7、 根据权利要求 1-6之一所述的方法, 其特征在于, 步骤 (5 ) 所述洗涤 优选采用水洗; The method according to any one of claims 1 to 6, wherein the step (5) is preferably washing with water;
所述洗涤进行多次, 例如 2〜6次, 优选 3〜5次。  The washing is carried out a plurality of times, for example, 2 to 6 times, preferably 3 to 5 times.
8、 根据权利要求 1所述的方法, 其特征在于, 包括以下制备步骤:  8. The method according to claim 1, comprising the following steps of preparing:
(1) 取氧化石墨置于水中,超声处理 2〜3小时,得到浓度为 0.01〜10 mg/ml 的氧化石墨悬浮液; 配制浓度为 0.2〜20 mol/L强碱水溶液;  (1) taking graphite oxide in water, sonicating for 2 to 3 hours to obtain a graphite oxide suspension having a concentration of 0.01 to 10 mg/ml; preparing a strong alkali aqueous solution having a concentration of 0.2 to 20 mol/L;
(2) 将步骤(1 ) 的强碱水溶液加入到歩骤(1 ) 的氧化石墨悬浮液, 搅拌至 出现云状凝聚; 其中, 混合物中强碱与氧化石墨的质量比为 1~50:1;  (2) adding the strong alkali aqueous solution of step (1) to the graphite oxide suspension of the step (1), stirring until cloud aggregation occurs; wherein the mass ratio of the strong base to the graphite oxide in the mixture is 1 to 50:1 ;
(3) 过滤歩骤 (2) 凝聚后的氧化石墨悬浮液, 将滤饼干燥;  (3) Filtration step (2) The condensed graphite oxide suspension is dried, and the filter cake is dried;
(4) 将步骤(3 )干燥后所得固体颗粒或者粉末在 700〜1200°C下进行烧结; (4) The solid particles or powder obtained after drying in the step (3) are sintered at 700 to 1200 ° C;
(5) 将步骤 (4) 烧结后的固体进行水洗、 过滤和干燥, 得到高比表面积石 墨烯材料。 (5) The solid after the step (4) is washed with water, filtered, and dried to obtain a high specific surface area graphene material.
9、 一种高比表面积石墨烯材料, 其特征在于, 所述石墨烯材料比表面积为 1500〜3000 m2/g, 所述高比表面积石墨烯材料由权利要求 1-8之一所述方法制 备得到。 9. A high specific surface area graphene material, characterized in that the graphene material has a specific surface area of 1500 to 3000 m 2 /g, and the high specific surface area graphene material is produced by the method according to any one of claims 1-8. System Ready.
10、 一种如权利要求 9所述高比表面积石墨烯材料的用途, 其用于储氢、 锂离子电池、 超级电容器或者燃料电池, 以及纳电子器件、 高频电路、 光子传 感器、 基因电子测序和减少噪音。  10. Use of a high specific surface area graphene material according to claim 9 for hydrogen storage, lithium ion batteries, supercapacitors or fuel cells, and nanoelectronic devices, high frequency circuits, photon sensors, gene electronic sequencing And reduce noise.
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