CN103879992B - The method of preparing a graphene nanoribbons - Google Patents

The method of preparing a graphene nanoribbons Download PDF

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CN103879992B
CN103879992B CN201210558228.3A CN201210558228A CN103879992B CN 103879992 B CN103879992 B CN 103879992B CN 201210558228 A CN201210558228 A CN 201210558228A CN 103879992 B CN103879992 B CN 103879992B
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carbon nano
carbon
graphene nanoribbons
metal substrate
wall
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CN103879992A (en
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周明杰
袁新生
王要兵
刘大喜
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海洋王照明科技股份有限公司
深圳市海洋王照明技术有限公司
深圳市海洋王照明工程有限公司
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Abstract

一种石墨烯纳米带的制备方法,利用紫外光作为光催化剂,碳源经过光催化化学气相沉积反应在经过刻蚀的金属衬底上生成碳纳米壁,将该碳纳米壁刮下得到碳纳米壁粉末,以该碳纳米壁粉末作为原料,采用三电极体系反应制备插层碳纳米壁,按固液比为1g:10~100ml将插层碳纳米壁分散于离子液体中得到分散液,将分散液在功率为40~100w/cm的快中波辐射器里加热剥离,然后进行过滤,洗涤滤渣并干燥得到石墨烯纳米带。 A method of preparing a graphene nanoribbon, as a photocatalyst with ultraviolet light, carbon through chemical vapor deposition of photocatalytic reaction wall carbon nano metal substrate after etching, the carbon nano-wall carbon nano scraped off to give powder walls, to the wall carbon nano powder as a starting material, the reaction layer three-electrode system using carbon nano wall plug prepared according to the solid-liquid ratio of 1g: 10 ~ 100ml the intercalated carbon nanowall dispersed in the ionic liquid to obtain a dispersion liquid, dispersion power of 40 ~ 100w / cm fast medium wave radiator's heat release and then filtered, washed and dried to give residue graphene nanoribbons. 将该碳纳米壁粉末作为石墨烯纳米带的原料,在快中波辐射器里加热剥离得到尺寸均一性较高的石墨烯纳米带,并且这种方法在制备过程中不会在最终得到的石墨烯纳米带引入含氧基团,制备得到质量较好的石墨烯纳米带。 The wall carbon nano powder as a raw material of graphene nanoribbons, fast medium wave radiator heating resulting in the release of high dimensional uniformity graphene nanoribbons, and this method does not graphite finally obtained in the manufacturing process alkenyl nanoribbon introducing oxygen-containing group, to give a better quality prepared graphene nanoribbons.

Description

石墨稀纳米带的制备方法 Preparation graphene nanoribbons

技术领域 FIELD

[0001] 本发明设及纳米碳材料的合成领域,特别是设及一种石墨締纳米带的制备方法。 [0001] The present invention synthesis of nano-carbon material is provided and, in particular, graphite is provided and the associated preparation method nanoribbons.

背景技术阳002] 石墨締纳米带是在二维石墨締平面的基础上,经过一定的剪切而形成的带状结构。 BACKGROUND male 002] Graphite is associated with belt-like nano-dimensional graphite structure on the basis of the associated plane, after a certain shear formed. 石墨締纳米带不仅拥有石墨締的性能,还具备一些特殊的性能,例如其长径比较大,可高达上千倍,在集成电路方面可代替铜导线,进一步提高集成度,亦可对其结构进行改性制备成开关器件。 Graphite Graphite association nanoribbons only has associated properties, but also has some special properties, such as its large aspect ratio, up to a thousand times, the integrated circuits can be used instead of copper wire, to further improve the degree of integration, the structure may prepared modified switching device.

[0003]目前,石墨締纳米带的制备方法通常采用切割碳纳米管法,运种方法首先将碳纳米管浸泡在硫酸中,加入强氧化剂后进行加热,在高溫作用下利用强氧化剂使碳纳米管开环而得到石墨締纳米带。 [0003] Currently, the method of preparing the graphite nanoribbons usually associated cutting method of carbon nanotubes, carbon nanotubes operation method first soaked in sulfuric acid, heating after addition of a strong oxidizing agent, at a high temperature by using a strong oxidizing agent nanocarbon graphite obtained by ring-opening tube associated nanoribbons. 运种方制备得到的石墨締纳米带的通常会引入含氧官能团而石墨締纳米带的导电性能,并且尺寸的均一性难W控制,使得最终得到的石墨締纳米带质量的较差,难W满足实际需求。 Preparation transported species associated side graphite obtained nanoribbons typically introduce an oxygen-containing functional group and the conductive properties of graphite associated nanoribbons, and homogeneity is difficult to control the size of W, with such poor quality of the resulting nano-graphite associative difficult W meet the actual demand.

发明内容 SUMMARY

[0004] 基于此,有必要提供一种石墨締纳米带的制备方法,W制备质量较好的石墨締纳米带。 [0004] Based on this, it is necessary to provide a method for producing a graphite nano associated with, preferably graphite prepared mass W associated nanoribbons. 阳〇化]一种石墨締纳米带的制备方法,包括如下步骤: A method of preparing a male square] associated nano graphite tape, comprising the steps of:

[0006] 使用稀酸溶液对金属衬底进行刻蚀; [0006] The use of dilute acid solution to etch the metal;

[0007] 在无氧和保护气体的氛围下,将所述金属衬底加热至600°C~900°C; [0007] Under oxygen-free protective gas atmosphere and, the metal substrate is heated to 600 ° C ~ 900 ° C;

[0008] 在紫外光的照射下,向所述金属衬底表面通入甲烧、乙烧、丙烷、乙烘及乙醇中的一种,经过光催化化学气相沉积反应30分钟~300分钟,在所述金属衬底表面生成碳纳米壁; [0008] In the UV irradiation, for methane into the metal to the substrate surface, burning B, propane, ethylene, and one ethanol bake, light passing through the catalytic chemical vapor deposition for 30 minutes to 300 minutes, in the metal substrate surface to generate the carbon-nanowall;

[0009] 反应完成后,在所述保护气体的氛围下将附有碳纳米壁的金属衬底冷却至室溫, 然后将所述碳纳米壁从所述金属衬底的表面刮下,得到碳纳米壁粉末; [0009] After completion of the reaction, the atmosphere of the protective gas with the carbon nano-wall metal substrate was cooled to room temperature, and then the carbon nano-wall is scraped off the surface of the metal substrate to obtain a carbon nanowall powder;

[0010] 将所述碳纳米壁粉末放置于集流体上并压制成碳纳米壁片层得到工作电极; W11] 将对电极、参比电极及所述工作电极共同浸泡于电解液中,在5mA/cm2~lOOmA/cm2 的电流密度、室溫下反应1小时~20小时后,将反应后的电解液进行过滤、洗涂滤渣并干燥得到插层碳纳米壁;及 [0010] The powder was placed in a carbon nano-wall carbon nano-wall and pressed into sheets to obtain a working electrode on a current collector; W11 of] the counter electrode, the reference electrode and the working electrode is immersed in a common electrolyte, at 5mA after the current density / cm2 ~ lOOmA / cm2, and 1 hour to 20 hours at room temperature, the electrolytic solution after the reaction was filtered, the filter cake washed and dried to give coated intercalated carbon nano wall; and

[0012] 按固液比为Ig: 10~100mL将所述插层碳纳米壁分散于离子液体中得到分散液,将所述分散液在功率为40~lOOw/cm的快中波福射器里加热剥离后进行过滤,洗涂滤渣并干燥得到石墨締纳米带。 [0012] Press ratio of solid Ig: 10 ~ 100mL said intercalated carbon nanowall dispersion to give a dispersion in the ionic liquid, the dispersion liquid at a power of 40 ~ lOOw / cm emitters fast in Bofu after heat release was filtered, washed and dried to obtain a graphite coating residue associated nanoribbons.

[0013] 在其中一个实施例中,所述使用稀酸溶液对金属衬底进行刻蚀的步骤具体为:将所述金属衬底放入浓度为0.Olmol/L~Imol/L的稀酸溶液中刻蚀0. 5分钟~10分钟。 L of the metal substrate is placed in a dilute acid concentration 0.Olmol / L ~ Imol /: [0013] In one embodiment, the step of dilute acid solution to etch the metal is specifically etching solution 0.5 minutes to 10 minutes.

[0014] 在其中一个实施例中,所述使用稀酸溶液对金属衬底进行刻蚀步骤具体为:将所述金属衬底放入浓度为0.Imol/L~0. 5mol/L的稀酸溶液中刻蚀1分钟~3分钟。 [0014] In one embodiment, the dilute acid solution to etch the metal in step is specifically: the concentration of the metal substrate is placed 0.Imol L ~ 0 5mol L lean / /. acid etching solution of 1 minute to 3 minutes.

[0015] 在其中一个实施例中,所述紫外光的波长为200~400nm。 [0015] In one embodiment, the ultraviolet light having a wavelength of 200 ~ 400nm.

[0016] 在其中一个实施例中,所述甲烧、乙烧、丙烷、乙烘及乙醇中的一种的流量为IOsccm~lOOOsccm。 [0016] In one embodiment, the burn A, B burning a flow of propane, ethanol and acetate drying of IOsccm ~ lOOOsccm.

[0017] 在其中一个实施例中,所述甲烧、乙烧、丙烷、乙烘及乙醇中的一种与所述保护气体的体积比为2~10:1。 [0017] In one embodiment, the A burn, burn B A propane, ethanol and acetate drying of the protective gas to the volume ratio of from 2 to 10: 1.

[001引在其中一个实施例中,所述电解液选自甲酸、乙酸、丙酸、硝酸、硝基甲烧中的至少一种。 [001 incorporated in one embodiment, the electrolyte selected from formic acid, acetic acid, propionic acid, nitric acid, nitromethane burning at least one.

[0019] 在其中一个实施例中,所述洗涂滤渣并干燥得到插层碳纳米壁的步骤具体为:用去离子水洗涂所述滤渣,并于60°c~80°C真空干燥12小时~24小时。 Step [0019] In one embodiment, the filter cake washed and dried to obtain a coated carbon nanowall layer interposed specifically comprises: coating the filter cake washed with deionized water, and dried in vacuo to ~ 80 ° C to 60 ° c 12 hours to 24 hours.

[0020] 在其中一个实施例中,所述离子液体选自1-乙基-3-甲基咪挫四氣棚酸、1-乙基-3-甲基咪挫S氣甲横酷亚胺、1-乙基-3-甲基咪挫S氣甲横酸、1-乙基-3-甲基咪挫S氣乙酸、1-乙基-3-甲基咪挫S氣甲横酷碳、1-乙基-3-甲基咪挫五氣乙酷亚胺、1-乙基-3-甲基咪挫二氯化氮、1-乙基-3, 5-二甲基咪挫=氣甲横酷亚胺、1,3-二乙基-4-甲基咪挫=氣甲横酷亚胺及1,3-二乙基-5-甲基咪挫=氣甲横酷亚胺中的一种。 [0020] In one embodiment, the ionic liquid is selected from 1-ethyl-3-methyl-imidazol setback four gas shed acid, 1-ethyl-3-methylimidazolium cross setback S A cool air imine , 1-ethyl-3-methyl imidazole A setback S gas cross acid, 1-ethyl-3-methyl-imidazol setback S gas acetate, ethyl-3-methylimidazolium setback S A cross cool gas carbon , ethyl-3-methylimidazolium acetate cool gas fell five imide, 1-ethyl-3- methylimidazolium chloride dinitrogen setback, 1-ethyl-3,5-dimethyl-imidazol setback = A cool air cross-imine, 1,3-diethyl-4-methyl imidazole setback A = gas cross cool imine and 1,3-diethyl-5-methyl-imidazol setback A = gas cross cool imine in kind.

[0021] 在其中一个实施例中,所述洗涂滤渣并干燥得到石墨締纳米带的步骤具体为将所述滤渣用1-甲基-2-化咯烧酬或N,N-二甲基甲酯胺洗涂3~6次,再依次用乙醇、丙酬及去离子水洗涂,然后于60°C~100°C下真空干燥至恒重得到石墨締纳米带。 [0021] In one embodiment, the filter cake washed and dried to give a step-coated graphite nanoribbons associated specifically with the residue of 1-methyl-paid slightly burned or N, N- dimethyl methyl amine washcoated 3 to 6 times, and then washed with ethanol, propanol pay deionized water coating, and then dried in vacuo at 60 ° C ~ 100 ° C to a constant weight to give graphite associated nanoribbons.

[0022] 上述石墨締纳米带的制备方法首先利用光催化化学气相沉积制备结构完整、尺寸均一性较高的碳纳米壁粉末,将该碳纳米壁粉末作为石墨締纳米带的原料,进行快中波福射器里加热剥离,受热集中,效率高,得到尺寸均一性较高的石墨締纳米带,并且运种方法在制备过过程中不会在最终得到的石墨締纳米带引入含氧基团,制备得到质量较好的石墨締纳米带。 [0022] Preparation of the graphite is first associated nanoribbons catalytic chemical vapor deposition using light structures complete preparation, uniform size of the powder high carbon nanowall, a carbon nanowall the graphite powder as a raw material associated nanoribbons, the fast- Bofu transmitter release in heating, heating concentration, high efficiency, uniform size to obtain a high graphite associative nanoribbons, and operation methods associated not nano graphite tape finally obtained in the process of introduction of oxygen-containing groups through the preparation of , good quality graphite prepared associated nanoribbons.

附图说明 BRIEF DESCRIPTION

[0023] 图1为一实施方式的石墨締纳米带的制备方法流程图; Preparation Method [0023] FIG. 1 is an embodiment of a flowchart of graphite associated nanoribbons;

[0024] 图2为实施例1制备的碳纳米壁的沈M图; 阳02引图3为实施例1制备的石墨締纳米带的SEM图。 [0024] FIG. 2 is a carbon sink M nanowall prepared according to Example 1; FIG. 3 is a positive lead 02 Example 1 SEM graphite associated nanoribbons prepared.

具体实施方式 Detailed ways

[00%] 为使本发明的上述目的、特征和优点能够更加明显易懂,下面结合附图对本发明的具体实施方式做详细的说明。 [00%] to make the above-described objects, features and advantages of the invention more comprehensible, a detailed description of the drawings embodiments of the present invention will be binding. 在下面的描述中阐述了很多具体细节W便于充分理解本发明。 Numerous specific details are set forth in the following description in which W facilitating full understanding of the present invention. 但是本发明能够W很多不同于在此描述的其它方式来实施,本领域技术人员可W在不违背本发明内涵的情况下做类似改进,因此本发明不受下面公开的具体实施的限制。 However, the present invention can be W many other ways than described herein to embodiments, those skilled in the art can make similar modifications W without departing from the intension of the present invention, the present invention is not limited so particular embodiments disclosed below.

[0027] 请参阅图1,一实施方式的石墨締纳米带的制备方法,包括如下步骤: [0027] Referring to FIG. 1, a method for preparing nano-graphite associated with the embodiment of the embodiment, comprising the steps of:

[0028] 步骤Sl10 :使用稀酸溶液对金属衬底进行刻蚀。 [0028] Step Sl10: using dilute acid solution to etch the metal.

[0029] 金属衬底优选为铁锥、儀锥及钻锥中的一种。 [0029] The metal substrate is preferably Tiezhui, and cone apparatus of one cone drill.

[0030] 使用稀酸溶液对金属衬底进行刻蚀的步骤具体为:将金属衬底放入浓度为0. 01mol/l~lmol/L的稀酸溶液中刻蚀0. 5分钟~10分钟。 [0030] Step dilute acid solution to etch the metal is specifically: the metal substrate into a concentration of 0. 01mol / l ~ lmol / L dilute solution of etched 0.5 minutes to 10 minutes .

[0031] 稀酸溶液为稀盐酸溶液、稀硫酸溶液或稀硝酸溶液。 [0031] The dilute acid solution is a dilute hydrochloric acid solution, a dilute sulfuric acid solution or nitric acid solution. 阳0巧优选地,稀酸溶液的浓度为0.Imol/L~0. 5mol/L,刻蚀的时间为1分钟~3分钟。 0 clever male Preferably, the concentration of the dilute acid solution was 0.Imol / L ~ 0. 5mol / L, the etching time is 1 minute to 3 minutes.

[0033] 对金属衬底进行刻蚀,使金属衬底表面产生缺陷,能够有效地改善金属衬底的表面结构,W为碳纳米壁提供一个有利的生长基底,使得碳纳米壁能够在金属衬底的表面生长。 [0033] The etching of the metal substrate, the metal substrate surface defects, can effectively improve the surface structure of a metal substrate, W provides a favorable growth substrate is a carbon nanowall, a carbon nanowall can be such that the metal back the surface of the growth substrate.

[0034] 将铁锥、儀锥及钻锥中的一种金属衬底放入浓度为0.Imol/L~0. 5mol/L的稀酸溶液中刻蚀1分钟~3分钟,能够达到良好的刻蚀效果,有利于提高碳纳米壁的生长效率。 [0034] The metal substrate Tiezhui, instrument and cone drill cone placed concentration 0.Imol / L ~ 0. 5mol / L solution of diluted acid etching for 1 minute to 3 minutes, to achieve good etching effect, help to improve the efficiency of the growth of carbon nano wall.

[0035] 步骤S120 :在无氧和保护气体的氛围下,将金属衬底加热至600°C~90(TC。 [0035] Step S120: In the absence of oxygen and a protective gas atmosphere, the metal substrate is heated to 600 ° C ~ 90 (TC.

[0036] 首先将经过刻蚀的金属衬底依次用去离子水、乙醇和丙酬清洗干净并干燥,备用。 [0036] First, the metal substrate after etching with deionized water, ethanol and propan-pay clean and dry standby.

[0037] 将清洗干燥后的经过刻蚀的金属衬底放入反应室中。 [0037] After cleaning the metal substrate is etched dried into the reaction chamber. 排除反应室中的空气并通入保护气体,使反应室完全处于无氧状态,避免氧气的参与而影响碳纳米壁的生长,为碳纳米壁的生长提供一个稳定的环境。 Exclusion of air in the reaction chamber and protective gas into the reaction chamber completely free of oxygen, to avoid the involvement of oxygen and affect the growth of carbon nano walls, providing a stable environment for the growth of carbon nano wall.

[0038] 将金属衬底加热至600°C~900°C,并保溫至反应结束。 [0038] The metal substrate was heated to 600 ° C ~ 900 ° C, and incubated until the end of the reaction.

[0039] 保护气体优选为氮气、氮气、氣气中的至少一种。 [0039] at least one protective gas preferably nitrogen, nitrogen gas is air.

[0040] 步骤S130 :在紫外光的照射下,向金属衬底表面通入甲烧、乙烧、丙烷、乙烘及乙醇中的一种,经过光催化化学气相沉积反应30分钟~300分钟,在金属衬底表面生成碳纳米壁。 [0040] Step S130: In the UV irradiation, the burning of the substrate into the surface of the metal A, burning B, propane, ethylene, and one ethanol bake, light passing through the catalytic chemical vapor deposition for 30 minutes to 300 minutes, generating a carbon nano wall surface of the metal substrate.

[0041] 紫外光源设备与金属衬底正对。 [0041] ultraviolet light source device and the metal substrate of-sight. 开启紫外光源设备,使紫外光照射在金属衬底的表面。 Turn on the ultraviolet light source device, ultraviolet light is irradiated on the surface of the metal substrate.

[0042] 紫外光作为光催化剂。 [0042] ultraviolet light as a photocatalyst. 紫外光的波长优选为200~400nm。 The wavelength of ultraviolet light is preferably 200 ~ 400nm.

[0043] 在紫外光的照射下,向反应室中通入碳源,使金属衬底处于碳源的氛围中。 [0043] In the UV irradiation, the carbon source into the reaction chamber, the metal substrate is in an atmosphere of carbon. 碳源选自甲烧、乙烧、丙烷、乙烘及乙醇中的一种。 A carbon source is selected firing, burning B, propane, ethylene, and one ethanol drying.

[0044] 碳源的流量为IOsccm~lOOOsccm。 [0044] The flow rate of the carbon source IOsccm ~ lOOOsccm. W45] 优选地,碳源与保护气体的体积比为2~10:1。 W45] Preferably, the volume ratio of the carbon source and the shielding gas is 2 to 10: 1.

[0046] 在紫外光照射下及在保护气体氛围中,甲烧、乙烧、丙烷、乙烘及乙醇中的一种经过光催化化学气相沉积反应30分钟-300分钟,在金属衬底上生成碳纳米壁。 [0046] In the UV irradiation and in a protective gas atmosphere, for methane, burning B, propane, ethanol, acetate, drying, and one photocatalytic reaction through chemical vapor deposition -300 minutes to 30 minutes to produce a metal substrate carbon nano wall.

[0047] 步骤S140 :反应完成后,在保护气体的氛围下将附有碳纳米壁的金属衬底冷却至室溫,然后将碳纳米壁从金属衬底的表面刮下,得到碳纳米壁粉末。 [0047] Step S140: After completion of the reaction, in an atmosphere of protective gas with the carbon nano-wall metal substrate was cooled to room temperature and then scraped from the surface of the carbon nano-wall of the metal substrate to obtain a carbon powder nanowall . W48] 反应30分钟~300分钟后,停止通入碳源,关闭加热设备及关闭紫外光源设备,待反应室和附有碳纳米壁的金属衬底冷却至室溫后停止通入保护气体,将金属衬底表面的碳纳米壁刮下,得到碳纳米壁粉末。 W48] for 30 minutes to 300 minutes, the carbon source was stopped, heating equipment and close off the ultraviolet light source device, and to be attached to the reaction chamber wall carbon nano metal substrate is cooled to room temperature after stopping the flow of protective gas, the carbon nano-wall surface of the metal substrate scraped wall carbon nano powders obtained.

[0049] 待反应室和附有碳纳米壁的金属衬底冷却至室溫后再停止通入保护气体,防止生成的碳纳米壁在高溫下氧化,进一步保证得到碳纳米壁粉末的质量。 [0049] of the reaction chamber wall and with carbon nano metal substrate was cooled to room temperature before stopping the flow of protective gas to prevent the formation of carbon nano wall at high temperature oxidation, to further ensure the quality of the carbon nanowall to give powder.

[0050] 步骤S150 :将碳纳米壁粉末放置于集流体上并压制成碳纳米壁片层得到工作电极。 [0050] Step S150: The powder was placed in a carbon nanowall on a current collector and pressed into a carbon nanowall working electrode sheet obtained.

[0051] 将碳纳米壁粉末和粘结剂放置于集流体上,然后用模具压制,使集流体上形成碳纳米壁片层,得到=电极体系的工作电极。 [0051] The wall carbon nano powder and a binder on a current collector is placed, then pressed with a mold, a carbon nano-wall formed sheet, to obtain a working electrode = electrode system on the current collector. 集流体优选采用不诱钢集流体。 The current collector is preferable not trap steel current collector.

[0052] 碳纳米壁片层的尺寸为75*40*7mm3。 Size [0052] The carbon nano-wall sheet is 75 * 40 * 7mm3. W53] 步骤S160 :将对电极、参比电极及工作电极共同浸泡于电解液中,在5mA/cm2~lOOmA/cm2的电流密度、室溫下反应1小时~20小时后,将反应后的电解液进行过滤、洗涂滤渣并干燥得到插层碳纳米壁。 W53] Step S160: After the counter electrode, the reference electrode and the working electrode is immersed in a common electrolyte, the current density at 5mA / cm2 ~ lOOmA / cm2, the reaction for 1 hour to 20 hours at room temperature, the reaction after the electrolysis solution was filtered, the filter cake washed and dried to give coated intercalated carbon nano wall.

[0054] 采用铅板作为对电极,化/Hg2S〇4作为参比电极。 [0054] using a lead plate as the counter electrode, of / Hg2S〇4 as the reference electrode. 阳05引电解液选自甲酸、乙酸、丙酸、硝酸、硝基甲烧中的至少一种。 05 male primer electrolyte selected from formic acid, at least one of acetic acid, propionic acid, nitric acid, burning of nitromethane. 电解液同时也起到插层剂的作用,在电场作用下,电解液在工作电极表面形成电势差,在电势差的驱动下不断克服碳纳米壁层间的作用力,插到碳纳米壁层间,得到插层碳纳米壁。 Electrolyte also acts as the intercalant, in the electric field, the electrolyte potential difference is formed at the working electrode surface, overcoming the biasing force between the carbon nanowall potential difference in the drive, into the carbon nano parietal, to obtain a carbon nanowall intercalation.

[0056] 反应1小时~20小时后,将反应后的电解液进行过滤,然后将得到的滤渣用去离子水洗涂,再将洗涂后的滤渣于60°C~80°C下真空干燥12小时~24小时,得到干燥、纯净的插层碳纳米壁。 After drying [0056] 1 hour to 20 hours, the electrolytic solution after the reaction was filtered and the resulting filter cake washed with deionized water coating, and then wash the residue after vacuum coating at 60 ° C ~ 80 ° C 12 to 24 hours to give a dried, pure intercalated carbon nano wall.

[0057] 步骤S170 :按固液比为Ig:10~100mL将插层碳纳米壁分散于离子液体中得到分散液,将分散液在功率为40~lOOw/cm的快中波福射器里加热剥离后进行过滤,洗涂滤渣并干燥得到石墨締纳米带。 [0057] Step S170: according to solid-liquid ratio of Ig: 10 ~ 100mL intercalated carbon nanowall the dispersion to give a dispersion in the ionic liquid, the dispersion liquid at a power of 40 ~ lOOw / cm fast in the reflector Bofu after heating peeling was filtered, washed and dried to obtain a graphite coating residue associated nanoribbons.

[0058] 插层碳纳米壁分散于离子液体中便于快速加热剥离,剥离后得到的石墨締纳米带也分散于离子液体中。 [0058] The intercalated carbon nanowall dispersed in the ionic liquid is heated to facilitate rapid release, after peeling obtained with graphite nano-associated or dispersed in the ionic liquid. 用离子液体作为分散液能够防止石墨締纳米带团聚,从而提高石墨締纳米带的产率。 Using an ionic liquid as a dispersion of graphite can be prevented from associating with nano aggregates, thereby increasing the yield of graphite associated nanoribbons.

[0059] 为了达到较好的分散效果,W提高剥离效率及石墨締纳米带的产率,插层碳纳米壁与离子液体的固液比优选为Ig:10~100ml。 [0059] In order to achieve better dispersion, W stripping efficiency and improve the yield associated nanoribbons graphite, carbon nano wall intercalated ionic liquid and solid-liquid ratio is preferably from Ig: 10 ~ 100ml. W60] 离子液体选自1-乙基-3-甲基咪挫四氣棚酸巧tMeImBF4)、1-乙基-3-甲基咪挫S氣甲横酷亚胺巧tMeImN(CF3S〇2)2)、1-乙基-3-甲基咪挫S氣甲横酸巧tMelmCFsSOj)、 1-乙基-3-甲基咪挫S氣乙酸巧tMeImCF3C〇2)、l-乙基-3-甲基咪挫S氣甲横酷碳巧tMeImC(CF3S〇2)3)、1-乙基-3-甲基咪挫五氣乙酷亚胺巧tMeImN(C2FsS〇2)2)、1-乙基-3-甲基咪挫二氯化氮巧tMeImN(CN)2)、1-乙基-3, 5-二甲基咪挫S氣甲横酷亚胺(I-Et -3, 5-Me2ImN(CF3S〇2)2)、1,3-二乙基-4-甲基咪挫^氣甲横酷亚胺(1,3-Et2-4-MeImN(CF3 S〇2)2)及1,3-二乙基-5-甲基咪挫立氣甲横酷亚胺(1,3-Et2-5-MeImN(CF3S〇2)2)中的一种。 W60] ionic liquid is selected from 1-ethyl-3-methyl-imidazol setback four shed acid gas clever tMeImBF4), 1- ethyl-3-methylimidazolium cross setback S A cool air imine Qiao tMeImN (CF3S〇2) 2), 1-ethyl-methylimidazole cross-carboxylic acid setback S gas clever tMelmCFsSOj), 1- ethyl-3-methylimidazolium acetate clever tMeImCF3C〇2 gas setback S), L-ethyl-3- A setback S methylimidazole cross cool gas carbon Qiao tMeImC (CF3S〇2) 3), 1-ethyl-3-methylimidazolium acetate cool gas fell five imine Qiao tMeImN (C2FsS〇2) 2), 1-ethyl N-3-methylimidazole setback dichloride Qiao tMeImN (CN) 2), 1- ethyl-3,5-dimethyl-imidazol setback S A cross cool air imine (I-Et -3, 5- Me2ImN (CF3S〇2) 2), 1,3-diethyl-4-methyl-imidazol ^ setback cool air A cross-imine (1,3-Et2-4-MeImN (CF3 S〇2) 2) and 1 , 3-ethyl-5-methylimidazole a setback vertical cross cool air imine (1,3-Et2-5-MeImN (CF3S〇2) 2) one of.

[0061] 上述离子液体在常溫下为液态,W使插层石墨分散于离子液体中,W在常溫下进行快中波福射器加热剥离,加热快,能耗低,制备成本低。 [0061] The ionic liquid is liquid at room temperature, W intercalated graphite so dispersed in the ionic liquid, W is the fast-release Bofu emitted heated at ordinary temperature, heating speed, low energy consumption and low production cost.

[0062] 分散液在功率为40~lOOw/cm的快中波福射器里加热剥离1分钟~30分钟后进行初次过滤,再将滤渣用1-甲基-2-化咯烧酬(NI巧或N,N-二甲基甲酯胺值M巧洗涂3~6次, W充分除去滤渣中的离子液体。然后,依次用乙醇、丙酬及去离子水洗涂,再于60°C~100°C 下真空干燥至恒重得到石墨締纳米带。 [0062] The dispersion power of 40 ~ lOOw / cm Bofu exit the fast release for initial heating Lane filter 1 minute to 30 minutes, and then with 1-methyl-2 residues of burning pay slightly (NI Coincidentally or N, N- dimethyl ester amine value M How to wash coating 3 to 6 times, W sufficiently remove ionic liquid residue is then washed with ethanol, propanol and deionized water coating pay, then at 60 ° C in vacuo at ~ 100 ° C and dried to a constant weight to give graphite associated nanoribbons.

[0063] 在功率为40~lOOw/cm的快中波福射器里加热剥离,能实现快速加热,W保证一定的剥离效率,使剥离时间较短,生产效率较高;另一方面,避免微波的功率过高,对石墨締纳米带的结构产生破坏作用。 [0063] In a power of 40 ~ lOOw / cm fast in the reflector heating Bofu release, rapid heating can be achieved, W guarantee the efficiency of the release, the peeling shorter, higher production efficiency; on the other hand, to avoid the microwave power is too high, damaging effects on the structure of the graphite associated nanoribbons.

[0064] 在快中波福射器里加热剥离过程中不引入杂质,过滤的得到的滤液,即离子液体可W回收而重复使用,有利于降低制备成本。 [0064] In the fast heating Bofu Lane exit the stripping process does not introduce impurity, the filtrate was filtered, i.e., the ionic liquid can be recovered and reused W, help to reduce manufacturing costs. 阳0化]上述石墨締纳米带的制备方法,首先利用紫外光作为光催化剂,碳源经过光催化化学气相沉积反应在经过刻蚀的金属衬底上生成碳纳米壁,将该碳纳米壁刮下得到碳纳米壁粉末,W该碳纳米壁粉末作为原料,采用=电极体系反应制备插层碳纳米壁,对该插层碳纳米壁进行快中波福射器里加热剥离得到石墨締纳米壁。 Of male 0] The method of preparing the graphite associated nanoribbons, first with ultraviolet light as a photocatalyst, the photocatalytic carbon through chemical vapor deposition reaction wall carbon nano metal substrate after etching, scraping the wall carbon nano to give the wall carbon nano powder, W powder as the raw material carbon nano wall, the electrode system employed = intercalation prepared by reacting a carbon nanowall, fast graphitization in association nanowalls Bofu exit Lane heating the obtained release layer interposed wall carbon nano .

[0066] 利用紫外光作为光催化剂,碳源经过光催化化学气相沉积反应在经过刻蚀的金属衬底上生成碳纳米壁的方法避免了传统的在等离子体氛围中制备方法中等离子体对碳纳米壁的破坏,能够生成结构较为完整、尺寸均一性较高的碳纳米壁。 Method [0066] As a photocatalyst with ultraviolet light, carbon through chemical vapor deposition of photocatalytic reaction on the carbon nano wall etched through the metal substrate to avoid the traditional production method of a plasma in a plasma atmosphere of carbon nanowall damage, it is possible to generate more complete structure, high dimensional uniformity of the carbon nanowall.

[0067] 该方法采用自行制备的碳纳米壁粉末作为原料制备的石墨締纳米带,碳纳米壁粉末的制备W甲烧、乙烧、丙烷、乙烘及乙醇中一种作为碳源,运几种碳源较为廉价,相对于采用市售的碳纳米管作为石墨締纳米带的原料,其成本相对较低,并且光催化能有效降低反应溫度,减少能耗,降低了生产成本。 [0067] The method uses wall carbon nano graphite powder prepared self-association nanoribbons prepared starting materials, wall carbon nano powders prepared W A burn, burn acetate, propane, ethanol and drying of one acetate as a carbon source, several transport relatively inexpensive carbon sources, with respect to a commercially available carbon nanotubes as a raw material graphite associated nanoribbons, which is relatively low cost, and can effectively reduce the photocatalytic reaction temperature, reduce energy consumption, reduce production costs.

[0068] 该石墨締纳米带的制备方法工艺简单,条件易控,快中波福射器里加热剥离效率高,提高了生产效率。 [0068] The preparation method of the graphite nano associated with a simple, easy to control conditions, in the high speed peeling Bofu exit Lane heating efficiency, improve production efficiency.

[0069] 该石墨締纳米带的制备方法所用的设备都是普通的化工设备,对设备的要求较低,工艺简单,条件易控,适合大规模生产。 [0069] Preparation of the graphite nanoribbons associated equipment used are ordinary chemical equipment, low equipment requirements, the process is simple, easy to control conditions, suitable for mass production.

[0070]W下为具体实施例。 The [0070] W to the specific embodiments. 阳0川实施例1 Example 1 River male 0

[0072] 1.将儀锥放入浓度为Imol/L的稀盐酸溶液中刻蚀0. 5分钟,刻蚀好后用去离子水、乙醇、丙酬进行清洗并干燥; [0072] 1. The instrument into a cone concentration Imol / L diluted hydrochloric acid solution to etch 0.5 minutes, good etch deionized water, ethanol, propanol pay washed and dried;

[0073] 2.排除反应室中的空气并通入氮气,将清洗干燥后的儀锥放入通有氮气的反应室中,并将儀锥加热至90(TC并保溫,然后开启紫外光光源设备,令紫外光照射在儀锥表面,紫外光的波长为250nm,接着通入甲烧200sccm,甲烧与氮气的体积比为2:1,保持100分钟; [0073] 2. the exclusion of air in the reaction chamber and purged with nitrogen, the cleaning instrument after drying cone placed through the reaction chamber with nitrogen, and heated to taper instrument 90 (TC and incubated, and then turn on the ultraviolet light source apparatus, so that the ultraviolet light irradiation apparatus conical surface, the ultraviolet light having a wavelength of 250 nm, and then passed through 200 sccm for methane, nitrogen by volume for methane and the ratio of 2: 1, for 100 min;

[0074] 3.反应完成后,停止通入甲烧,停止对儀锥加热及关闭紫外光光源设备,待反应室冷却至室溫后停止通入氮气,儀锥表面生成碳纳米壁,将其从儀锥表面刮下,便得到碳纳米壁粉末; After completion of the [0074] 3. The reaction was stopped and the burning A, stop the heating device on and off cone UV light source device, after stopping of the reaction chamber was cooled to room temperature, nitrogen gas, carbon nano meter cone generated surface wall, which conical surface scraped from the instrument, it will have a carbon nanowall powder;

[007引4.插层碳纳米壁的制备:采用不诱钢片作为集流体,将上述制备得到的碳纳米壁粉末放入集流体上,在集流体上压制成规格为75*40*7mm3 (约2g)的碳纳米壁片层作为工作电极,W铅板作为对电极,Hg/Hg2S04作为参比电极,甲酸作为电解液,将立电极放入电解池并完全浸泡在电解液中,在5mA/cm2的电流密度、室溫下进行反应20小时,然后将反应后的电解液进行过滤,将得到的滤渣用去离子水清洗后置于真空干燥箱中于60°C干燥24小时后可得到纯净、干燥的插层碳纳米壁; [Preparation of carbon-nanowall 007 primer 4. Intercalation: do not use steel as a current collector trap, the above prepared powder was placed in a carbon nanowall on a current collector, into a size press on the current collector is 75 * 40 * 7mm3 (about 2g) carbon nanowall sheet as the working electrode, W lead plate as the counter electrode, Hg / Hg2S04 as the reference electrode, formic acid as the electrolytic solution, the electrolytic cell into discrete electrodes and immersed in the electrolyte completely, in a current density of 5mA / cm2, the reaction was carried out at room temperature for 20 hours and then the electrolytic solution after the reaction was filtered, the residue obtained after washing with deionized water was placed in the vacuum oven dried at 60 ° C 24 hours to give pure, dried intercalated carbon nanowall;

[0076] 5.取插层碳纳米壁,按质量体积比为Ig:IOml加入到装有化MeImBFA离子液体的容器中,将该容器放置功率为80w/cm的快中波福射器里加热剥离10分钟,然后初次过滤, 得到的滤渣用NMP过滤洗涂6次,再依次用乙醇、丙酬、去离子水洗涂,过滤,将收集到的滤渣在真空干燥箱于60°C下干燥至恒重得到石墨締纳米带。 [0076] 5. Remove the intercalated carbon nanowall, mass volume ratio of Ig: IOml of MeImBFA added to the ionic liquid containing container, the container is placed power 80w / cm fast in the reflector heating Bofu peeling 10 minutes and then filtered for the first time, the resulting filter cake washed with NMP coating 6 times, then washed with ethanol, propanol paid, coating deionized water, filtered, and the collected filter cake in a vacuum oven dried at 60 ° C to to give a constant weight of graphite associated nanoribbons. 阳077] 图2和图3分别为实施例1的碳纳米壁和石墨締纳米带的SEM图。 Male 077] Figures 2 and 3 are SEM images of carbon nano-wall associated and graphite nanoribbons Example 1.

[0078] 从图2和图3可W看出,碳纳米壁垂直于衬底密集生长,厚度均匀,约为30~60nm, 由碳纳米壁为原料所制备的石墨締纳米带宽度分布集中,约为20~40nm,长度约为2~20um, 长径比约为50~1000。 [0078] W can be seen from FIGS. 2 and 3, carbon nano walls perpendicular to the substrate growth of dense, uniform thickness, 30 ~ 60nm approximately, by the association of nano-graphite carbon nano wall width distribution prepared as a raw material concentration, about 20 ~ 40nm, a length of about 2 ~ 20um, an aspect ratio of about 50 to 1000.

[0079] 该石墨締纳米带的不引入含氧官能团,宽度分布较为均匀,且剥离过程中能够最大限度地保持石墨締纳米带结构的完整性,制备得到的石墨締纳米带的质量较好。 [0079] The graphite nano associated with the introduction of oxygen-containing functional group is not, a more uniform distribution width, and to maximize the stripping process to maintain the integrity of the structure of graphite associated nanoribbons, good quality graphite prepared associated nanoribbons obtained.

[0080] 实施例2 [0080] Example 2

[0081] 1.采用铁锥作为衬底,将铁锥放入浓度为0.5mol/L的稀硫酸溶液中刻蚀4分钟, 刻蚀好后用去离子水、乙醇、丙酬进行清洗并干燥; [0081] 1. Tiezhui employed as the substrate, the concentration of Tiezhui into 0.5mol / L dilute sulfuric acid etching solution for 4 minutes with deionized water, ethanol, propanol paid good etching after washing and drying ;

[0082] 2.排除反应室中的空气并通入氣气,将清洗干燥后的铁锥放入通有氣气的反应室中,并将铁锥加热至60(TC并保溫,然后开启紫外光光源设备,令紫外光照射在铁锥表面,紫外光的波长为200nm,接着通入乙烧lOOsccm,乙烧与氣气的体积比为5:1,保持200分钟; [0082] 2. The reaction chamber to exclude the air and gas into gas, washing through Tiezhui dried into the reaction chamber with a gas in a gas, and was heated to Tiezhui 60 (TC and incubated, and then turn on the ultraviolet light source apparatus, so that the ultraviolet light irradiation surface Tiezhui, ultraviolet light having a wavelength of 200 nm, and then passed acetate burning lOOsccm, b and gas fired gas volume ratio 5: 1, for 200 min;

[0083] 3.反应完成后,停止通入乙烧,停止对铁锥加热及关闭紫外光光源设备,待反应室冷却至室溫后停止通入氣气,铁锥表面生成碳纳米壁,将其从铁锥表面刮下,便得到碳纳米壁粉末; After completion of the [0083] 3. The reaction was stopped and the burning acetate, and heating is stopped Tiezhui off ultraviolet light source apparatus, a reaction chamber to be cooled to room temperature gas into the gas was stopped, the carbon nano-wall formed on the surface Tiezhui the Tiezhui scraped from the surface thereof to thus give carbon nanowall powder;

[0084] 4.插层碳纳米壁的制备:采用不诱钢片作为集流体,将上述制备得到的碳纳米壁粉末放入集流体上,在集流体上压制成规格为75*40*7mm3 (约2g)的碳纳米壁片层作为工作电极,W铅板作为对电极,Hg/Hg2S〇4作为参比电极,乙酸作为电解液,将立电极放入电解池并完全浸泡在电解液中,在20mA/cm2的电流密度、室溫下进行反应1小时,然后将反应后的电解液进行过滤,将得到的滤渣用去离子水清洗后置于真空干燥箱中于70°C干燥20小时后可得到纯净、干燥的插层碳纳米壁; Preparation of [0084] 4. The carbon nano wall interposed layer: steel trap as does the current collector, the above prepared powder was placed in a carbon nanowall on a current collector, into a size press on the current collector is 75 * 40 * 7mm3 (about 2g) carbon nanowall sheet as the working electrode, W lead plate as the counter electrode, Hg / Hg2S〇4 as the reference electrode, acetic acid as the electrolyte, the Li electrode into the cell and completely immersed in the electrolyte carried out at a current density of 20mA / cm2, and reacted for 1 hour at room temperature, and then the electrolytic solution after the reaction was filtered, the cake washed with deionized water was placed in a vacuum oven dried at 70 ° C 20 hours after the obtained clean, dry intercalated carbon nanowall;

[00化]5.取插层碳纳米壁,按质量体积比为Ig:100mL加入到装有化MeImN(CFsSOz)Z离子液体的容器中,将该容器放置在功率为40w/cm的快中波福射器里加热剥离30分钟,然后初次过滤,得到的滤渣用DMF过滤洗涂3次,再依次用乙醇、丙酬、去离子水洗涂,过滤,将收集到的滤渣在真空干燥箱于80°C下干燥至恒重得到石墨締纳米带。 . [Of 00] 5 taken intercalated carbon nanowall, mass volume ratio of Ig: 100mL was added to a flask of MeImN (CFsSOz) Z ionic liquid container, the container is placed at a power of 40w / cm in fast Bofu transmitter release was heated for 30 minutes and then filtered for the first time, the resulting filter cake washed with DMF coating 3 times, then washed with ethanol, propanol paid, coating deionized water, filtered, and the collected filter cake in a vacuum oven at 80 ° C for drying to a constant weight to give graphite associated nanoribbons.

[0086] 实施例3 [0086] Example 3

[0087] 1.采用钻锥作为衬底,将钻锥放入浓度为0.Olmol/L的稀硝酸溶液中刻蚀10分钟,刻蚀好后用去离子水、乙醇、丙酬进行清洗并干燥; [0087] As the substrate 1 using a cone drilling, the drill into the cone concentration 0.Olmol / L dilute nitric acid etch solution for 10 minutes, deionized water, ethanol, propanol paid after a good etching and cleaning dry;

[0088] 2.排除反应室中的空气并通入氮气,将清洗干燥后的钻锥放入通有氮气的反应室中,并将钻锥加热至700°C保溫,然后开启紫外光光源设备,令紫外光照射在钻锥表面,紫外光的波长为350nm,接着通入乙烘lOsccm,乙烘与氮气的体积比为8:1,保持300分钟; [0088] 2. the exclusion of air in the reaction chamber and purged with nitrogen, after washing cone drill Add dry nitrogen through the reaction chamber, and was heated to cone drill 700 ° C incubation, and then turn on the ultraviolet light source apparatus , so that the drill conical surface UV irradiation, ultraviolet light having a wavelength of 350nm, followed by drying into b lOsccm, the volume ratio of nitrogen and baked acetate is 8: 1, for 300 min;

[0089] 3.反应完成后,停止通入乙烘,停止对钻锥加热及关闭紫外光光源设备,待反应室冷却至室溫后停止通入氮气,钻锥表面生成碳纳米壁,将其从钻锥表面刮下,便得到碳纳米壁粉末; After completion of the [0089] 3. The reaction was stopped and the acetate drying, heating is stopped and the drill taper off UV light source device is stopped until the reaction chamber was cooled to room temperature nitrogen gas, drilling generates carbon nanowall conical surface, which scraped from the drill conical surface, it will have a carbon nanowall powder;

[0090] 4.插层碳纳米壁的制备:采用不诱钢片作为集流体,将上述制备得到的碳纳米壁粉末放入集流体上,在集流体上压制成规格为75*40*7mm3 (约2g)的碳纳米壁片层作为工作电极,W铅板作为对电极,Hg/Hg2S〇4作为参比电极,丙酸作为电解液,将立电极放入电解池并完全浸泡在电解液中,在50mA/cm2的电流密度、室溫下进行反应2小时,然后将反应后的电解液进行过滤,将得到的滤渣用去离子水清洗后置于真空干燥箱中于80°C干燥12小时后可得到纯净、干燥的插层碳纳米壁; Preparation of [0090] 4. The carbon nano wall interposed layer: steel trap as does the current collector, the above prepared powder was placed in a carbon nanowall on a current collector, into a size press on the current collector is 75 * 40 * 7mm3 (about 2g) carbon nanowall sheet as the working electrode, W lead plate as the counter electrode, Hg / Hg2S〇4 as the reference electrode, propionic acid as the electrolyte, the Li electrode into the cell and completely immersed in the electrolyte , the reaction was carried out for 2 hours at a current density of 50mA / cm2, and at room temperature, and then the electrolytic solution after the reaction was filtered, the residue washed with deionized water was placed in a 80 ° C was dried in a vacuum oven at 12 after hours to obtain clean, dry intercalated carbon nanowall;

[0091] 5.取插层碳纳米壁,按质量体积比为Ig: 50ml加入到装有化MeImCFsSOs离子液体的容器中,将该容器放置在功率为lOOw/cm的快中波福射器里加热剥离1分钟,然后初次过滤,得到的滤渣用NMP过滤洗涂5次,再依次用乙醇、丙酬、去离子水洗涂,过滤,将收集到的滤渣在真空干燥箱于l〇〇°C下干燥至恒重得到石墨締纳米带。 [0091] 5. Remove the intercalated carbon nanowall, mass volume ratio of Ig: 50ml was added to a flask of MeImCFsSOs ionic liquid container, the container is placed in the power lOOw / cm fast in the reflector Bofu release was heated for 1 minute and then filtered for the first time, the resulting filter cake washed with NMP 5 passes, and then washed with ethanol, propanol paid, coating deionized water, filtered, and the collected filter cake in a vacuum oven at l〇〇 ° C dried to constant weight to give graphite associated nanoribbons. 阳OW] 实施例4 Male OW] Example 4

[0093] 1.采用儀锥作为衬底,将儀锥放入浓度为0. 2mol/L的稀盐酸溶液中刻蚀2分钟, 刻蚀好后用去离子水、乙醇、丙酬进行清洗并干燥; [0093] 1. The use of a cone instrument as the substrate, the cone into the instrument concentration 0. 2mol / L diluted hydrochloric acid solution to etch for 2 minutes, deionized water, ethanol, propanol paid after a good etching and cleaning dry;

[0094] 2.排除反应室中的空气并通入氮气,将清洗干燥后的儀锥放入通有氮气的反应室中,并将儀锥加热至750°C并保溫,然后开启紫外光光源设备,令紫外光照射在儀锥表面,紫外光的波长为400nm,接着通入丙烷lOOOsccm,丙烷与氮气的体积比为10:1,保持30分钟; [0094] 2. the exclusion of air in the reaction chamber and purged with nitrogen, the cleaning instrument after drying cone placed through the reaction chamber with nitrogen, and the apparatus was heated to 750 ° C cone and incubated, and then turn on the ultraviolet light source apparatus, so that the ultraviolet light irradiation apparatus conical surface, the ultraviolet light having a wavelength of 400 nm, and then passed through propane lOOOsccm, propane and nitrogen volume ratio was 10: 1, for 30 minutes;

[0095] 3.反应完成后,停止通入丙烷,停止对儀锥加热及关闭紫外光光源设备,待反应室冷却至室溫后停止通入氮气,儀锥表面生成碳纳米壁,将其从儀锥表面刮下,便得到碳纳米壁粉末; After completion of the [0095] 3. Reaction, stopping the flow of propane, heating is stopped and closed cone instrument UV light source device, after stopping of the reaction chamber was cooled to room temperature, nitrogen gas, carbon nano meter cone generated surface wall, from which instrument conical surface scraped, they will have a carbon nanowall powder;

[0096] 4.插层碳纳米壁的制备:采用不诱钢片作为集流体,将上述制备得到的碳纳米壁粉末放入集流体上,在集流体上压制成规格为75*40*7mm3 (约2g)的碳纳米壁片层作为工作电极,W铅板作为对电极,化/略5〇4作为参比电极,质量分数为68%的硝酸作为电解液, 将=电极放入电解池并完全浸泡在电解液中,在lOOmA/cm2的电流密度、室溫下进行反应5 小时,然后将反应后的电解液进行过滤,将得到的滤渣用去离子水清洗后置于真空干燥箱中于75°C干燥15小时后可得到纯净、干燥的插层碳纳米壁; Preparation of [0096] 4. The carbon nano wall interposed layer: steel trap as does the current collector, the above prepared powder was placed in a carbon nanowall on a current collector, into a size press on the current collector is 75 * 40 * 7mm3 (about 2g) carbon nanowall sheet as the working electrode, W lead plate as the counter electrode, of / 5〇4 slightly as the reference electrode, the mass fraction of 68% nitric acid as an electrolyte, the electrode into the electrolytic cells = and completely immersed in the electrolytic solution, for reaction for 5 hours at a current density lOOmA / cm2, and at room temperature, and then the electrolytic solution after the reaction was filtered, the cake washed with deionized water was placed in a vacuum oven after drying at 75 ° C 15 hours to obtain clean, dry intercalated carbon nanowall;

[0097] 5.取插层碳纳米壁,按质量体积比为Ig: 20ml加入到装有化MeImCFsCOs离子液体的容器中,将该容器放置在功率为50w/cm的快中波福射器里加热剥离5分钟,然后初次过滤,得到的滤渣用DMF过滤洗涂3次,再依次用乙醇、丙酬、去离子水洗涂,过滤,将收集到的滤渣在真空干燥箱于90°C下干燥至恒重得到石墨締纳米带。 [0097] 5. Remove the intercalated carbon nanowall, mass volume ratio of Ig: 20ml was added to a flask of MeImCFsCOs ionic liquid container, the container is placed in the power of 50w / cm fast in the reflector Bofu release was heated for 5 minutes and then filtered for the first time, the resulting filter cake washed with DMF coating 3 times, then washed with ethanol, propanol paid, coating deionized water, filtered, and the collected filter cake was dried in a vacuum oven at 90 ° C under to a constant weight to give graphite associated nanoribbons. 阳〇9引实施例5 Example 5 male lead 〇9

[0099] 1.采用铁锥作为衬底,将铁锥放入浓度为0.Imol/L的稀硫酸溶液中刻蚀5分钟, 刻蚀好后用去离子水、乙醇、丙酬进行清洗并干燥; 阳100] 2.排除反应室中的空气并通入氣气,将清洗干燥后的铁锥放入通有氣气的反应室中,并将铁锥加热至80(TC并保溫,然后开启紫外光光源设备,令紫外光照射在铁锥表面,紫外光的波长为300nm,接着通入乙醇SOOsccm,乙醇与氣气的体积比为6:1,保持50分钟; 阳101] 3.反应完成后,停止通入乙醇,停止对铁锥加热及关闭紫外光光源设备,待反应室冷却至室溫后停止通入氣气,铁锥表面生成碳纳米壁,将其从铁锥表面刮下,便得到碳纳米壁粉末; 阳102] 4.插层碳纳米壁的制备:采用不诱钢片作为集流体,将上述制备得到的碳纳米壁粉末放入集流体上,在集流体上压制成规格为75*40*7mm3(约2g)的碳纳米壁片层作为工作电极,W铅板 [0099] 1. Tiezhui employed as the substrate, the concentration of Tiezhui into 0.Imol / L dilute sulfuric acid etching solution for 5 minutes, deionized water, ethanol, propanol paid after a good etching and cleaning drying; male 100] 2. exclude air and the reaction chamber through the gas into the air, after washing Tiezhui Add dry air through the reaction chamber with a gas, and the Tiezhui was heated to 80 (TC and incubated, and then UV light source device is turned on, so that the ultraviolet light irradiation surface Tiezhui, ultraviolet light having a wavelength of 300 nm, and then passed through ethanol SOOsccm, ethanol gas and gas volume ratio of 6: 1, for 50 min; male 101] 3. reaction after completion, the ethanol was stopped, and heating is stopped Tiezhui off ultraviolet light source apparatus, a reaction chamber to be cooled to room temperature gas into the gas was stopped, the generated surface Tiezhui carbon nanowall, which is scraped from the surface Tiezhui , they will have a carbon nanowall powder; male preparing a carbon nanowall 102] 4. intercalation: not using steel as a current collector trap, the above prepared powder was placed in a carbon nanowall on the current collector, pressing on the current collector specifications into 75 * 40 * 7mm3 (about 2g) carbon nanowall sheet as the working electrode, W grid 为对电极,Hg/Hg2S〇4作为参比电极,甲酸作为电解液,将立电极放入电解池并完全浸泡在电解液中,在80mA/cm2的电流密度、室溫下进行反应10小时,然后将反应后的电解液进行过滤,将得到的滤渣用去离子水清洗后置于真空干燥箱中于65°C干燥18小时后可得到纯净、干燥的插层碳纳米壁; As the counter electrode, Hg / Hg2S〇4 as the reference electrode, formic acid as the electrolyte, the Li electrode into the cell and completely immersed in the electrolytic solution, at a current density of 80mA / cm2, and 10 hours at room temperature, then the electrolytic solution after the reaction was filtered and the resulting filter cake in a vacuum oven and dried to obtain 18 hours 65 ° C for pure, dry intercalated layers of carbon nanowall after rinsing with deionized water;

[0103] 5.取插层碳纳米壁,按质量体积比为Ig:80ml加入到装有化MeImC(CFsSOz)S离子液体的容器中,将该容器放置在功率为90w/cm的快中波福射器里加热剥离3分钟,然后初次过滤,得到的滤渣用NMP过滤洗涂4次,再依次用乙醇、丙酬、去离子水洗涂,过滤,将收集到的滤渣在真空干燥箱于70°C下干燥至恒重得到石墨締纳米带。 [0103] 5. Remove the intercalated carbon nanowall, mass volume ratio of Ig: 80ml was added to a flask of MeImC (CFsSOz) ionic liquid S container, the container is placed in the fast medium-wave power of 90w / cm of Four transmitter release was heated for 3 minutes, and then the initial filtration, the resulting filter cake washed with NMP 4 times a coating, and then washed with ethanol, propanol paid, coating deionized water, filtered, and the collected filter cake in a vacuum oven at 70 under ° C to constant weight to give graphite associated nanoribbons. 阳104] 实施例6 阳1化]1.采用钻锥作为衬底,将钻锥放入浓度为0. 4mol/L的稀硝酸溶液中刻蚀8分钟, 刻蚀好后用去离子水、乙醇、丙酬进行清洗并干燥; 阳106] 2.排除反应室中的空气并通入氮气,将清洗干燥后的钻锥放入通有氮气的反应室中,并将钻锥加热至850°C并保溫,然后开启紫外光光源设备,令紫外光照射在钻锥表面,紫外光的波长为230nm,接着通入甲烧SOOsccm,甲烧与氮气的体积比为4:1,保持90分钟; 阳107] 3.反应完成后,停止通入甲烧,停止对钻锥加热及关闭紫外光光源设备,待反应室冷却至室溫后停止通入氮气,钻锥表面生成碳纳米壁,将其从钻锥表面刮下,便得到碳纳米壁粉末; Male 104] Example 6 of the male 1] 1. Using as a substrate cone drilling, the drill into the cone at a concentration of 0. 4mol / L dilute nitric acid etch solution for 8 minutes after a good etch deionized water, ethanol, propanol pay washing and drying; male 106] 2. exclude air and the reaction chamber is purged with nitrogen, after washing cone drill Add dry nitrogen through the reaction chamber, and was heated to 850 ° cone drill C and incubated, and then turn on the ultraviolet light source apparatus, so that ultraviolet irradiation of the surface of the cone drilling, ultraviolet light having a wavelength of 230nm, and then passed for methane SOOsccm, volume ratio for methane and nitrogen is 4: 1, for 90 min; male 107] 3. after completion of the reaction, stopping the flow a burning, heating is stopped and the drill taper off ultraviolet light source apparatus, to be introduced into the reaction chamber with nitrogen to stop after cooling to room temperature, the drill conical surface generated carbon nanowall, which is scraped from the drill conical surface, it will have a carbon nanowall powder;

[0108] 4.插层碳纳米壁的制备:采用不诱钢片作为集流体,将上述制备得到的碳纳米壁粉末放入集流体上,在集流体上压制成规格为75*40*7mm3 (约2g)的碳纳米壁片层作为工作电极,W铅板作为对电极,Hg/Hg2S〇4作为参比电极,硝基甲烧作为电解液,将立电极放入电解池并完全浸泡在电解液中,在40mA/cm2的电流密度、室溫下进行反应15小时,然后将反应后的电解液进行过滤,将得到的滤渣用去离子水清洗后置于真空干燥箱中于60°C干燥20小时后可得到纯净、干燥的插层碳纳米壁; Preparation of [0108] 4. The carbon nano wall interposed layer: steel trap as does the current collector, the above prepared powder was placed in a carbon nanowall on a current collector, into a size press on the current collector is 75 * 40 * 7mm3 (about 2g) carbon nanowall sheet as the working electrode, W lead plate as the counter electrode, Hg / Hg2S〇4 as a reference electrode, an electrolytic solution as nitromethane burning, discrete electrodes into the electrolytic cell and completely immersed in electrolytic solution, at a current density of 40mA / cm2, and reacted for 15 hours at room temperature, and then the electrolytic solution after the reaction was filtered, the residue washed with deionized water was placed in a vacuum oven at 60 ° C after drying 20 hours to obtain clean, dry intercalated carbon nanowall;

[0109] 5.取插层碳纳米壁,按质量体积比为Ig:60ml加入到装有化MeImN(CzFsSOz)2离子液体的容器中,将该容器放置在功率为75w/cm的快中波福射器里加热剥离8分钟,然后初次过滤,得到的滤渣用DMF过滤洗涂5次,再依次用乙醇、丙酬、去离子水洗涂,过滤,将收集到的滤渣在真空干燥箱于60°C下干燥至恒重得到石墨締纳米带。 [0109] 5. Remove the intercalated carbon nanowall, mass volume ratio of Ig: 60ml was added to a flask of MeImN (CzFsSOz) ionic liquid container 2, the container is placed in the fast medium-wave power of 75w / cm of Four transmitter release was heated in 8 minutes and then filtered for the first time, the resulting filter cake washed with DMF coating 5 times, then washed with ethanol, propanol paid, coating deionized water, filtered, and the collected filter cake in a vacuum oven at 60 under ° C to constant weight to give graphite associated nanoribbons.

[0110] 实施例7 阳111] 1.采用儀锥作为衬底,将儀锥放入浓度为0. 25mol/L的稀盐酸溶液中刻蚀3分钟, 刻蚀好后用去离子水、乙醇、丙酬进行清洗并干燥; [0110] Example 7 male 111] 1. The use of a cone instrument as the substrate, the cone into the instrument concentration 0. 25mol / L diluted hydrochloric acid solution to etch for 3 minutes with deionized water after a good etching ethanol , washed and dried pay propoxy;

[0112] 2.排除反应室中的空气并通入氮气,将清洗干燥后的儀锥放入通有氮气的反应室中,并将儀锥加热至900°C并保溫,然后开启紫外光光源设备,令紫外光照射在儀锥表面,紫外光的波长为380nm,接着通入乙烧300sccm,乙烧与氮气的体积比为3:1,保持120分钟; [0112] 2. the exclusion of air in the reaction chamber and purged with nitrogen, the cleaning instrument after drying cone placed through the reaction chamber with nitrogen, and the apparatus was heated to 900 ° C cone and incubated, and then turn on the ultraviolet light source apparatus, so that the ultraviolet light irradiation apparatus conical surface, the ultraviolet light has a wavelength of 380 nm, and then passed through 300 sccm acetate burn, burn acetate nitrogen volume ratio of 3: 1, 120 minutes;

[0113] 3.反应完成后,停止通入乙烧,停止对儀锥加热及关闭紫外光光源设备,待反应室冷却至室溫后停止通入氮气,儀锥表面生成碳纳米壁,将其从儀锥表面刮下,便得到碳纳米壁粉末; After completion of the [0113] 3. The reaction was stopped and the burning B, heating is stopped and closed cone instrument UV light source device, after stopping of the reaction chamber was cooled to room temperature, nitrogen gas, carbon nano meter cone generated surface wall, which conical surface scraped from the instrument, it will have a carbon nanowall powder;

[0114] 4.插层碳纳米壁的制备:采用不诱钢片作为集流体,将上述制备得到的碳纳米壁粉末放入集流体上,在集流体上压制成规格为75*40*7mm3 (约2g)的碳纳米壁片层作为工作电极,W铅板作为对电极,Hg/Hg2S〇4作为参比电极,乙酸和硝基甲烧按体积比1:1混合的混合液作为电解液,将=电极放入电解池并完全浸泡在电解液中,在lOmA/cm2的电流密度、 室溫下进行反应6小时,然后将反应后的电解液进行过滤,将得到的滤渣用去离子水清洗后置于真空干燥箱中于80°C干燥12小时后可得到纯净、干燥的插层碳纳米壁; 阳115] 5.取插层碳纳米壁,按质量体积比为Ig:40ml加入到装有化MeImN(CN)2离子液体的容器中,将该容器放置在功率为60w/cm的快中波福射器里加热剥离20分钟,然后初次过滤,得到的滤渣用NMP过滤洗涂3次,再依次用乙醇、丙酬、去离子水洗涂,过滤,将收集到的 Preparation of [0114] 4. The carbon nano wall interposed layer: steel trap as does the current collector, the above prepared powder was placed in a carbon nanowall on a current collector, into a size press on the current collector is 75 * 40 * 7mm3 (about 2g) carbon nanowall sheet as the working electrode, W lead plate as the counter electrode, Hg / Hg2S〇4 as the reference electrode, nitromethane and acetic acid burning volume ratio of 1: 1 mixture as an electrolyte , = the electrode into the cell and completely immersed in the electrolyte, reaction was carried out for 6 hours at a current density of lOmA / cm2, and at room temperature, and then the electrolytic solution after the reaction was filtered, the filter cake with deionized water and the resulting after washing in a vacuum oven at 80 ° C after dried for 12 hours to obtain clean, dry intercalated carbon nanowall; male 115] 5. Remove intercalated carbon nanowall, mass volume ratio of Ig: 40ml was added to the with of MeImN (CN) 2 ionic liquid container, the container is placed at a power of 60w / cm Bofu the fast release heat emitted Lane 20 minutes, then the initial filtration, the resulting filter cake washed with NMP coating 3 times, then washed with ethanol, propanol paid, coating deionized water, filtered, and the collected 滤渣在真空干燥箱于l〇〇°C下干燥至恒重得到石墨締纳米带。 Cake in a vacuum oven at l〇〇 ° C to constant weight to give graphite associated nanoribbons.

[0116] 实施例8 [0116] Example 8

[0117] 1.采用铁锥作为衬底,将铁锥放入浓度为Imol/L的稀盐酸溶液中刻蚀4分钟,刻蚀好后用去离子水、乙醇、丙酬进行清洗并干燥; [0117] 1. Tiezhui employed as the substrate, the concentration of Tiezhui into Imol / L dilute hydrochloric acid etching solution for 4 minutes with deionized water, ethanol and the good etching, washing and drying propan pay;

[0118] 2.排除反应室中的空气并通入氣气,将清洗干燥后的铁锥放入通有氣气的反应室中,并将铁锥加热至65(TC并保溫,然后开启紫外光光源设备,令紫外光照射在铁锥表面,紫外光的波长为200nm,接着通入乙烘200sccm,乙烘与氣气的体积比为2:1,保持180分钟; [0118] 2. The reaction chamber to exclude the air and gas into gas, washing through Tiezhui dried into the reaction chamber with a gas in a gas, and was heated to Tiezhui 65 (TC and incubated, and then turn on the ultraviolet light source apparatus, so that the ultraviolet light irradiation surface Tiezhui, ultraviolet light having a wavelength of 200 nm, followed by drying 200 sccm into acetate, acetic drying gas and gas volume ratio of 2: 1, for 180 min;

[0119] 3.反应完成后,停止通入乙烘,停止对铁锥加热及关闭紫外光光源设备,待反应室冷却至室溫后停止通入氣气,铁锥表面生成碳纳米壁,将其从铁锥表面刮下,便得到碳纳米壁粉末; After completion of the [0119] 3. The reaction was stopped and the acetate drying, heating is stopped and the closing Tiezhui UV light source apparatus, a reaction chamber to be cooled to room temperature gas into the gas was stopped, the carbon nano-wall formed on the surface Tiezhui the Tiezhui scraped from the surface thereof to thus give carbon nanowall powder;

[0120] 4.插层碳纳米壁的制备:采用不诱钢片作为集流体,将上述制备得到的碳纳米壁粉末放入集流体上,在集流体上压制成规格为75*40*7mm3 (约2g)的碳纳米壁片层作为工作电极,W铅板作为对电极,Hg/Hg2S〇4作为参比电极,甲酸和质量分数为68%的硝酸按体积比4:1混合的混合液作为电解液,将=电极放入电解池并完全浸泡在电解液中,在30mA/cm2 的电流密度、室溫下进行反应8小时,然后将反应后的电解液进行过滤,将得到的滤渣用去离子水清洗后置于真空干燥箱中于70°C干燥15小时后可得到纯净、干燥的插层碳纳米壁; 阳121] 5.取插层碳纳米壁,按质量体积比为lg:30ml加入到装有l-Et-3,S-MezImN(CFsSOz)2离子液体的容器中,将该容器放置在功率为7〇w/cm的快中波福射器里加热剥离25分钟,然后初次过滤,得到的滤渣用DMF过滤洗涂6次,再依次用乙醇、 丙酬、去离子水洗 Preparation of [0120] 4. The carbon nano wall interposed layer: steel trap as does the current collector, the above prepared powder was placed in a carbon nanowall on a current collector, into a size press on the current collector is 75 * 40 * 7mm3 (about 2g) carbon nanowall sheet as the working electrode, W lead plate as the counter electrode, Hg / Hg2S〇4 as reference 68% by volume nitric electrode 4, and the mass fraction of formic acid: mixing a mixture of 1 as the electrolyte, the electrode into the cell and = completely immersed in the electrolyte, carried out at a current density of 30mA / cm2, and reacted for 8 hours at room temperature, and then the electrolytic solution after the reaction was filtered, the residue obtained by after washing with deionized water and dried in a vacuum oven after 15 hours at 70 ° C to obtain clean, dry intercalated carbon nanowall; male 121] 5. Remove intercalated carbon nanowall, mass volume ratio of lg: was added to 30ml with l-Et-3, S-MezImN (CFsSOz) ionic liquid container 2, the container is placed in the power 7〇w / cm Bofu the fast release heat emitted Lane 25 minutes, then initial filtration, the resulting filter cake washed with DMF six times the coating, and then washed with ethanol, propanol paid, deionized water ,过滤,将收集到的滤渣在真空干燥箱于80°C下干燥至恒重得到石墨締纳米带。 , Filtered, and the collected residue dried to constant weight to give graphite nanoribbons associate in a vacuum oven at 80 ° C. 阳122] 实施例9 Male 122] Example 9

[0123] 1.采用钻锥作为衬底,将钻锥放入浓度为0.3mol/L的稀硫酸溶液中刻蚀2分钟, 刻蚀好后用去离子水、乙醇、丙酬进行清洗并干燥; [0123] As the substrate 1 using a cone drilling, the drill into the cone at a concentration of 0.3mol / L dilute sulfuric acid was etched for 2 minutes, deionized water, ethanol, propanol paid good etching after washing and drying ;

[0124] 2.排除反应室中的空气并通入氣气,将清洗干燥后的钻锥放入通有氮气的反应室中,并将钻锥加热至700°C并保溫,然后开启紫外光光源设备,令紫外光照射在钻锥表面,紫外光的波长为330nm,接着通入丙烷50sccm,丙烷与氮气的体积比为5:1,保持240分钟; [0124] 2. exclude air and the reaction chamber through the gas into the air, the cleaning cone drill through the reaction chamber into the drying nitrogen gas, and was heated to cone drill 700 ° C and incubated, and then turn on the ultraviolet light light source apparatus, so that ultraviolet irradiation of the surface of the cone drilling, the ultraviolet light has a wavelength of 330 nm, and then passed through 50 sccm of propane, propane and nitrogen volume ratio of 5: 1, for 240 min;

[01巧]3.反应完成后,停止通入丙烷,停止对钻锥加热及关闭紫外光光源设备,待反应室冷却至室溫后停止通入氮气,钻锥表面生成碳纳米壁,将其从钻锥表面刮下,便得到碳纳米壁粉末。 [01 Qiao] 3. After completion of the reaction, stopping the flow of propane, heating is stopped and the closing cone drill UV light source device, after stopping of the reaction chamber was cooled to room temperature, nitrogen gas, carbon nano drill cone generated surface wall, which scraped from the drill conical surface, it will have a carbon nanowall powder.

[0126] 4.插层碳纳米壁的制备:采用不诱钢片作为集流体,将上述制备得到的碳纳米壁粉末放入集流体上,在集流体上压制成规格为75*40*7mm3(约2g)的碳纳米壁片层作为工作电极,W铅板作为对电极,Hg/Hg2S〇4作为参比电极,丙酸和质量分数为68%的硝酸按体积比1:2混合的混合液作为电解液,将=电极放入电解池并完全浸泡在电解液中,在5mA/cm2的电流密度、室溫下进行反应15小时,然后将反应后的电解液进行过滤,将得到的滤渣用去离子水清洗后置于真空干燥箱中于80°C干燥20小时后可得到纯净、干燥的插层碳纳米壁; Preparation of [0126] 4. The carbon nano wall interposed layer: steel trap as does the current collector, the above prepared powder was placed in a carbon nanowall on a current collector, into a size press on the current collector is 75 * 40 * 7mm3 (about 2g) carbon nanowall sheet as the working electrode, W lead plate as the counter electrode, Hg / Hg2S〇4 as reference 68% by volume of nitric acid 1 electrode, and a mass fraction of acid: 2 mixed in the mixing solution as the electrolyte, the electrode into the cell and = completely immersed in the electrolytic solution, at a current density of 5mA / cm2, and reacted for 15 hours at room temperature, and then the electrolytic solution after the reaction was filtered, and the resulting residue after washing with deionized water was placed in a vacuum oven at 80 ° C after drying 20 hours to obtain clean, dry intercalated carbon nanowall;

[0127] 5.取插层碳纳米壁,按质量体积比为Ig:100mL加入到装有1,3-Et2-4-MeImN(CF3S〇2)2离子液体的容器中,将该容器放置在功率为65w/cm的快中波福射器里加热剥离15分钟,然后初次过滤,得到的滤渣用NMP过滤洗涂3次,再依次用乙醇、 丙酬、去离子水洗涂,过滤,将收集到的滤渣在真空干燥箱于90°C下干燥至恒重得到石墨締纳米带。 [0127] 5. Remove the intercalated carbon nanowall, mass volume ratio of Ig: 100mL, were added 1,3-Et2-4-MeImN (CF3S〇2) ionic liquid container 2, the container was placed power of 65w / cm Bofu the fast release heat emitted Lane 15 minutes and then filtered for the first time, the resulting filter cake washed with NMP coating 3 times, then washed with ethanol, propanol paid, coating deionized water, filtered, and the collected the residue was dried to constant weight to obtain a graphite nanoribbons associate in a vacuum oven at 90 ° C. 阳12引实施例10 Example 10 male 12 primer

[0129] 1.采用儀锥作为衬底,将儀锥放入浓度为0.5mol/L的稀硝酸溶液中刻蚀5分钟, 刻蚀好后用去离子水、乙醇、丙酬进行清洗并干燥; [0129] 1. The use of a cone instrument as the substrate, the cone into the instrument concentration 0.5mol / L dilute nitric acid etch solution for 5 minutes, deionized water, ethanol, propanol paid good etching after washing and drying ;

[0130] 2.排除反应室中的空气并通入氮气,将清洗干燥后的儀锥放入通有氮气的反应室中,并将儀锥加热至800°C并保溫,然后开启紫外光光源设备,令紫外光照射在儀锥表面,紫外光的波长为400nm,接着通入乙醇20sccm,乙醇与氮气的体积比为8:1,保持300分钟; 阳131] 3.反应完成后,停止通入乙醇,停止对儀锥加热及关闭紫外光光源设备,待反应室冷却至室溫后停止通入氮气,儀锥表面生成碳纳米壁,将其从儀锥表面刮下,便得到碳纳米壁粉末; 阳13引4.插层碳纳米壁的制备:采用不诱钢片作为集流体,将上述制备得到的碳纳米壁粉末放入集流体上,在集流体上压制成规格为75*40*7mm3(约2g)的碳纳米壁片层作为工作电极,W铅板作为对电极,Hg/Hg2S〇4作为参比电极,乙酸作为电解液,将立电极放入电解池并完全浸泡在电解液中,在lOOmA/cm2的电流密度、室溫下 [0130] 2. the exclusion of air in the reaction chamber and purged with nitrogen, the cleaning instrument after drying cone placed through the reaction chamber with nitrogen, and the apparatus was heated to 800 ° C cone and incubated, and then turn on the ultraviolet light source apparatus, so that the ultraviolet light irradiation apparatus conical surface, the ultraviolet light having a wavelength of 400 nm, of 20 sccm and then into ethanol, the volume ratio of ethanol to nitrogen was 8: 1, for 300 min; after completion of the male 131] 3. the reaction was stopped the ethanol, heating is stopped and the closing device cone UV light source device, after stopping of the reaction chamber was cooled to room temperature, nitrogen gas, carbon nano meter conical surface generated wall which was scraped from the surface of the cone device, it will have a carbon nanowall powder; male 13 carbon nano wall 4. preparation of intercalation primers: not using steel as a current collector trap, the above prepared powder was placed in a carbon nanowall on a current collector, into a size press on the current collector 75 * 40 * 7mm3 (about 2g) carbon nanowall sheet as the working electrode, W lead plate as the counter electrode, Hg / Hg2S〇4 as the reference electrode, acetic acid as the electrolyte, the Li electrode into the cell and completely immersed in the electrolytic solution at a current density lOOmA / cm2, and at room temperature 行反应2小时,然后将反应后的电解液进行过滤,将得到的滤渣用去离子水清洗后置于真空干燥箱中于60°C干燥18小时后可得到纯净、干燥的插层碳纳米壁; Line 2 hours, and then the electrolytic solution after the reaction was filtered, the cake washed with deionized water was placed in a vacuum oven 18 hours at 60 ° C and dried to obtain clean, dry intercalated carbon nanowall ;

[013引5.取插层碳纳米壁,按质量体积比为Ig:IOml加入到装有1,3-Et2-5-MeImN(CF3S02)2离子液体的容器中,将该容器放置在功率为40w/cm的快中波福射器里加热剥离10分钟,然后初次过滤,得到的滤渣用DMF过滤洗涂4次,再依次用乙醇、 丙酬、去离子水洗涂,过滤,将收集到的滤渣在真空干燥箱于70°C下干燥至恒重得到石墨締纳米带。 [013 5. Remove the primer layer interposed carbon nanowall, mass volume ratio of Ig: IOml charged to a 1,3-Et2-5-MeImN (CF3S02) 2 ionic liquid container, the container is placed in a power 40w / cm fast in Bofu ejector's release was heated for 10 minutes and then filtered for the first time, the resulting filter cake washed with DMF four times coating and then washed with ethanol, propanol paid, coating deionized water, filtered, and the collected obtained residue was dried to a constant weight of graphite in a vacuum oven nanoribbons associate at 70 ° C under. 阳134] 实施例11 Male 134] Example 11

[0135] 1.采用钻锥作为衬底,将钻锥放入浓度为0.05mol/L的稀盐酸溶液中刻蚀1分钟, 刻蚀好后用去离子水、乙醇、丙酬进行清洗并干燥; 阳136] 2.排除反应室中的空气并通入氣气,将清洗干燥后的钻锥放入通有氣气的反应室中,并将钻锥加热至90(TC并保溫,然后开启紫外光光源设备,令紫外光照射在钻锥表面,紫外光的波长为250nm,接着通入甲烧lOOsccm,甲烧与氣气的体积比为10:1,保持30分钟; 阳137] 3.反应完成后,停止通入甲烧,停止对钻锥加热及关闭紫外光光源设备,待反应室冷却至室溫后停止通入氣气,钻锥表面生成碳纳米壁,将其从钻锥表面刮下,便得到碳纳米壁粉末; 阳13引4.插层碳纳米壁的制备:采用不诱钢片作为集流体,将上述制备得到的碳纳米壁粉末放入集流体上,在集流体上压制成规格为75*40*7mm3(约2g)的碳纳米壁片层作为工作电极,W铅 [0135] As the substrate 1 using a cone drilling, the drill into the cone at a concentration of 0.05mol / L diluted hydrochloric acid solution in the etching for 1 minute with deionized water, ethanol, propanol paid good etching after washing and drying ; Yang 136] 2. exclude air and the reaction chamber through the gas into the air, the cleaning cone drill into the drying gas through the reaction chamber with a gas, and the cone drill was heated to 90 (TC and incubated, and then open the UV light source apparatus, so that the ultraviolet light irradiation drilling conical surface, the ultraviolet light having a wavelength of 250 nm, and then passed for methane lOOsccm, for methane gas and gas volume ratio of 10: 1, 30 minutes; the male 137] 3. after completion of the reaction, stopping the flow a burning, heating is stopped and the drill taper off ultraviolet light source apparatus, a reaction chamber to be cooled to room temperature gas into the gas was stopped, the drill production of carbon nanowall conical surface, which conical surface from the drill scraped, they will have a carbon nanowall powder; male 13 carbon nano wall 4. preparation of intercalation primers: not using steel as a current collector trap, the above prepared powder was placed in a carbon nanowall on a current collector, a current collector pressed to the specifications for the 75 * 40 * 7mm3 (about 2g) carbon nanowall sheet as the working electrode, W lead 板作为对电极,Hg/Hg2S〇4作为参比电极,硝基甲烧作为电解液,将立电极放入电解池并完全浸泡在电解液中,在50mA/cm2的电流密度、室溫下进行反应1小时,然后将反应后的电解液进行过滤,将得到的滤渣用去离子水清洗后置于真空干燥箱中于80°C干燥20 小时后可得到纯净、干燥的插层碳纳米壁; Plate as the counter electrode, Hg / Hg2S〇4 as a reference electrode, an electrolytic solution as nitromethane burning, discrete electrodes into the electrolytic cell and completely immersed in the electrolyte, carried out at a current density 50mA / cm2, and at room temperature for 1 hour, and then the electrolytic solution after the reaction was filtered and the resulting filter cake in a vacuum oven at 80 ° C after drying 20 hours to obtain clean, dry intercalated carbon nanowall after rinsing with deionized water;

[0139] 5.取插层碳纳米壁,按质量体积比为Ig:50ml加入到装有化MeImBFA离子液体的容器中,将该容器放置在功率为lOOw/cm的快中波福射器里加热剥离2分钟,然后初次过滤,得到的滤渣用NMP过滤洗涂5次,再依次用乙醇、丙酬、去离子水洗涂,过滤,将收集到的滤渣在真空干燥箱于l〇〇°C下干燥至恒重得到石墨締纳米带。 [0139] 5. Remove the intercalated carbon nanowall, mass volume ratio of Ig: 50ml was added to a flask of MeImBFA ionic liquid container, the container is placed in the power lOOw / cm fast in the reflector Bofu release was heated for 2 minutes, then the initial filtration, the resulting filter cake washed with NMP 5 passes, and then washed with ethanol, propanol paid, coating deionized water, filtered, and the collected filter cake in a vacuum oven at l〇〇 ° C dried to constant weight to give graphite associated nanoribbons.

[0140] 实施例1~11的工艺参数见表1。 Process parameters of Examples 1 to 11 [0140] Embodiment shown in Table 1. 阳141] 表1实施例1~11的工艺参数阳142] Male 141] Table 1 Example of process parameters 1 to 11 male 142]

Figure CN103879992BD00131

Figure CN103879992BD00141

[0144]W上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制。 [0144] The embodiments of the W expressed only several embodiments of the present invention, and detailed description thereof is more specific, but can not therefore be understood as limiting the scope of the present invention. 应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可W做出若干变形和改进,运些都属于本发明的保护范围。 It should be noted that those of ordinary skill in the art, without departing from the inventive concept premise, W may make various modifications and improvements fall within the protection scope of some operation of the present invention. 因此,本发明专利的保护范围应W所附权利要求为准。 Therefore, the protection scope of the present invention shall W appended claims.

Claims (9)

1. 一种石墨稀纳米带的制备方法,其特征在于,包括如下步骤: 使用稀酸溶液对金属衬底进行刻蚀,所述金属衬底为铁箱、镍箱及钴箱中的一种; 在无氧和保护气体的氛围下,将所述金属衬底加热至600°C~900°C ; 在紫外光的照射下,向所述金属衬底表面通入甲烷、乙烷、丙烷、乙炔及乙醇中的一种, 经过光催化化学气相沉积反应30分钟~300分钟,在所述金属衬底表面生成碳纳米壁; 反应完成后,在所述保护气体的氛围下将附有碳纳米壁的金属衬底冷却至室温,然后将所述碳纳米壁从所述金属衬底的表面刮下,得到碳纳米壁粉末; 将所述碳纳米壁粉末放置于集流体上并压制成碳纳米壁片层得到工作电极; 将对电极、参比电极及所述工作电极共同浸泡于电解液中,在5mA/cm2~100mA/cm 2的电流密度、室温下反应1小时~20小时后,将反应后的电解液进行过滤、 1. A method for preparing graphene nanoribbon, characterized by comprising the steps of: using dilute acid solution to etch the metal, the metal substrate is a metal box, box of nickel and cobalt in a tank ; and under oxygen-free protective gas atmosphere, the metal substrate is heated to 600 ° C ~ 900 ° C; under UV irradiation, the surface of the metal substrate into methane, ethane, propane, acetylene, and one ethanol, light passing through the catalytic chemical vapor deposition for 30 minutes to 300 minutes, to generate carbon nano wall surface of the metal substrate; after completion of the reaction, the atmosphere of the protective gas with the carbon nano stave metal substrate to room temperature and then the carbon nano-wall is scraped off the surface of the metal substrate to obtain a carbon nanowall powder; the wall carbon nano powder was placed on a current collector and pressed into a carbon nano wall sheet to give a working electrode; the counter electrode, the reference electrode and the working electrode is immersed in a common electrolyte, the reaction at a current density 5mA / cm2 ~ 100mA / cm 2, the temperature for 1 hour to 20 hours, the electrolytic solution after the reaction was filtered, 涤滤渣并干燥得到插层碳纳米壁,所述电解液选自甲酸、乙酸、丙酸、硝酸、硝基甲烷中的至少一种;及按固液比为Ig: 10~100mL将所述插层碳纳米壁分散于离子液体中得到分散液,将所述分散液在功率为40~100w/cm的快中波辐射器里加热剥离后进行过滤,洗涤滤渣并干燥得到石墨稀纳米带。 Wash the filter cake and dried to give a carbon nanowall layer is interposed, the electrolyte is selected from formic acid, acetic acid, propionic acid, nitric acid, at least one of nitromethane; and by the solid-liquid ratio of Ig: 10 ~ 100mL said plug carbon nanowall layer dispersed in the ionic liquid to obtain a dispersion, the dispersion liquid 40 ~ 100w / cm in the fast medium-wave radiators heated by filtration peeling power, residue was washed and dried to obtain graphene nanoribbons.
2. 根据权利要求1所述的石墨烯纳米带的制备方法,其特征在于,所述使用稀酸溶液对金属衬底进行刻蚀的步骤具体为:将所述金属衬底放入浓度为〇. 〇lmol/L~lmol/L的稀酸溶液中刻蚀〇. 5分钟~10分钟。 2. The method of claim 1 prepared graphene nanoribbons claim, wherein the step of using said dilute acid solution to etch the metal is specifically: the concentration of the metal substrate into the square . 〇lmol / L ~ lmol / L of a dilute acid solution etching billion 5 to 10 minutes.
3. 根据权利要求2所述的石墨烯纳米带的制备方法,其特征在于,所述使用稀酸溶液对金属衬底进行刻蚀步骤具体为:将所述金属衬底放入浓度为〇. lmol/L~0. 5mol/L的稀酸溶液中刻蚀1分钟~3分钟。 3. The method of claim 2 prepared graphene nanoribbons claim, wherein said dilute acid solution to etch the metal in step is specifically: the concentration of the metal substrate into the square. lmol / L ~ 0. 5mol / L dilute solution of etched 1 minute to 3 minutes.
4. 根据权利要求1所述的石墨稀纳米带的制备方法,其特征在于,所述紫外光的波长为200 ~400nm。 4. The method of claim 1 prepared graphene nanoribbons claim, wherein said ultraviolet light has a wavelength of 200 ~ 400nm.
5. 根据权利要求1所述的石墨烯纳米带的制备方法,其特征在于,所述甲烷、乙烧、丙烧、乙炔及乙醇中的一种的流量为IOsccm~lOOOsccm。 The method of preparing a graphene nanoribbons according to claim 1, wherein said methane, burning B, propyl burning a flow of acetylene and ethanol is IOsccm ~ lOOOsccm.
6. 根据权利要求1所述的石墨烯纳米带的制备方法,其特征在于,所述甲烷、乙烧、丙烷、乙炔及乙醇中的一种与所述保护气体的体积比为2~10:1。 6. The method of claim 1 prepared graphene nanoribbons claim, wherein said methane, burning B, propane, acetylene, and one kind of ethanol and the volume ratio of the protective gas is 2 to 10: 1.
7. 根据权利要求1所述的石墨稀纳米带的制备方法,其特征在于,所述洗涤滤渣并干燥得到插层碳纳米壁的步骤具体为:用去离子水洗涤所述滤渣,并于60°C~80°C真空干燥12小时~24小时。 The method for preparing graphene nanoribbons according to claim 1, characterized in that, the residue was washed and dried to give a carbon nanowall step intercalation is specifically: the residue was washed with deionized water, and 60 ° C ~ 80 ° C was dried under vacuum for 12 hours to 24 hours.
8. 根据权利要求1所述的石墨稀纳米带的制备方法,其特征在于,所述离子液体选自1-乙基-3-甲基咪唑四氟硼酸、1-乙基-3-甲基咪唑三氟甲磺酰亚胺、1-乙基-3-甲基咪唑三氟甲磺酸、1-乙基-3-甲基咪唑三氟乙酸、1-乙基-3-甲基咪唑三氟甲磺酰碳、1-乙基-3-甲基咪唑五氟乙酰亚胺、1-乙基-3-甲基咪唑二氰化氮、1-乙基-3, 5-二甲基咪唑三氟甲磺酰亚胺、1,3-二乙基-4-甲基咪唑三氟甲磺酰亚胺及1,3-二乙基-5-甲基咪唑三氟甲磺酰亚胺中的一种。 8. A method for preparing graphene nanoribbons according to claim 1, wherein the ionic liquid is selected from 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methyl trifluoromethanesulfonimide imidazole, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium trifluoro-acetic acid, 1-ethyl-3-methylimidazolium three carbon trifluoromethanesulfonyl, 1-ethyl-3-methylimidazolium imide pentafluoroethyl, 1-ethyl-3-methylimidazolium two nitrogen cyanide, 1-ethyl-3,5-dimethyl-imidazole trifluoromethanesulfonimide, 1,3-diethyl-4-methyl imidazole and trifluoromethanesulfonimide 1,3-diethyl-5-methylimidazole in trifluoromethanesulfonimide a.
9. 根据权利要求1所述的石墨稀纳米带的制备方法,其特征在于,所述洗涤滤渣并干燥得到石墨烯纳米带的步骤具体为:将所述滤渣用1-甲基-2-吡咯烷酮或N,N-二甲基甲酰胺洗涤3~6次,再依次用乙醇、丙酮及去离子水洗涤,然后于60°C~100°C下真空干燥至恒重得到石墨稀纳米带。 9. A method for preparing graphene nanoribbons according to claim 1, wherein the step of washing the filter residue and dried graphene nanoribbons obtained specifically as follows: the residue using 1-methyl-2-pyrrolidone or N, N- dimethylformamide was washed 3-6 times, then washed with ethanol, acetone and deionized water, and then at 60 ° C ~ 100 ° C and dried in vacuo to constant weight to give graphene nanoribbons.
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JPH04193953A (en) * 1990-11-27 1992-07-14 Shimadzu Corp Method and device for forming hard carbon film
CN1277145A (en) * 1999-06-11 2000-12-20 李铁真 Method for synthetizing vertical arrangement high-purity carbon nanometre tube in large-scale on large size substrate using hot CVD method
WO2012035551A1 (en) * 2010-09-14 2012-03-22 Council Of Scientific & Industrial Research Electrochemical process for synthesis of graphene
CN102807213A (en) * 2012-08-30 2012-12-05 中国科学院苏州纳米技术与纳米仿生研究所 Method for electrochemically preparing graphene

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04193953A (en) * 1990-11-27 1992-07-14 Shimadzu Corp Method and device for forming hard carbon film
CN1277145A (en) * 1999-06-11 2000-12-20 李铁真 Method for synthetizing vertical arrangement high-purity carbon nanometre tube in large-scale on large size substrate using hot CVD method
WO2012035551A1 (en) * 2010-09-14 2012-03-22 Council Of Scientific & Industrial Research Electrochemical process for synthesis of graphene
CN102807213A (en) * 2012-08-30 2012-12-05 中国科学院苏州纳米技术与纳米仿生研究所 Method for electrochemically preparing graphene

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