WO2015096592A1 - 单壁碳纳米管均匀分散的方法 - Google Patents

单壁碳纳米管均匀分散的方法 Download PDF

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WO2015096592A1
WO2015096592A1 PCT/CN2014/092467 CN2014092467W WO2015096592A1 WO 2015096592 A1 WO2015096592 A1 WO 2015096592A1 CN 2014092467 W CN2014092467 W CN 2014092467W WO 2015096592 A1 WO2015096592 A1 WO 2015096592A1
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acid
carbon nanotubes
walled carbon
dispersion
carbon nanotube
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French (fr)
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郝海燕
曹西亮
戴雷
蔡丽菲
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北京阿格蕾雅科技发展有限公司
广东阿格蕾雅光电材料有限公司
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Priority to KR1020167012296A priority Critical patent/KR101812552B1/ko
Priority to US15/106,733 priority patent/US9745477B2/en
Priority to JP2016559486A priority patent/JP6152492B2/ja
Publication of WO2015096592A1 publication Critical patent/WO2015096592A1/zh

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    • C—CHEMISTRY; METALLURGY
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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    • Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
    • Y10S977/742—Carbon nanotubes, CNTs
    • Y10S977/75—Single-walled
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10S977/00—Nanotechnology
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    • Y10S977/00—Nanotechnology
    • Y10S977/902—Specified use of nanostructure
    • Y10S977/932—Specified use of nanostructure for electronic or optoelectronic application

Definitions

  • the invention relates to a method for treating carbon nanotubes, in particular to a method for uniformly dispersing single-walled carbon nanotubes.
  • Carbon nanotubes are carbon materials with typical lamellar hollow structure characteristics.
  • the tube body constituting carbon nanotubes is composed of hexagonal graphite carbon ring structural units and has a special structure (radial size is nanometer order One-dimensional quantum material with an axial dimension of the order of microns.
  • Its pipe wall constitutes a coaxial pipe mainly composed of several layers to several tens of layers. The layer is maintained at a fixed distance between the layers of about 0.34 nm and a diameter of typically 2-20 nm.
  • the P electrons of the carbon atoms on the carbon nanotubes form a wide range of delocalized ⁇ bonds, and thus the conjugation effect is remarkable. Since the structure of the carbon nanotubes is the same as that of the graphite, it has good electrical properties.
  • Single-walled carbon nanotube materials have been identified as transparent electrodes that can replace ITO, especially by scientific research and industry because of their high electron mobility.
  • the main dispersion methods of carbon nanotubes in a solvent are: non-covalent functionalization, covalent functionalization, and solvent stripping.
  • the commonality of these methods requires the use of large mechanical forces, such as high-frequency ultrasound, ball milling, etc. to promote the dispersion of carbon nanotubes, and then high-speed centrifugation to remove large bundles. Large mechanical forces inevitably damage carbon nanotubes, and large tube bundles are separated by high-speed centrifugation to lose carbon nanotubes.
  • the non-covalent functionalization method introduces additives such as surfactants or polymers that are difficult to completely remove, and reduces the electrical and thermodynamic properties of the carbon nanotube network itself; the covalent functionalization method destroys carbon.
  • the sp2 structure of the nanotube functionalization site; the solvent used in the solvent stripping method is generally toxic, has a high boiling point, and has low dispersion efficiency. Therefore, under the premise of maintaining structural integrity and no additives, the effective dispersion of carbon nanotubes in common solvents is still an important issue in the research and application of single-walled carbon nanotubes.
  • the solvent for dispersion is usually a solvent such as water or a low-boiling alcohol (for example, an alcohol such as methanol or 2-propanol), and such a solvent has poor wettability to single-walled carbon nanotubes and poor dispersibility.
  • an organic solvent such as tetrahydrofuran or dimethylformamide has a slightly better solvent dispersibility than water and an alcohol.
  • tetrahydrofuran is highly toxic.
  • the boiling point of dimethylformamide is too high. Therefore, the concentration of the carbon nanotube dispersion prepared by dispersing the single-walled carbon nanotubes by a single solvent is small.
  • a surfactant such as sodium dodecylbenzenesulfonate, octylphenol polyethylene glycol ester, polyvinylpyrrolidone or the like is added to water or an alcohol solvent to assist in dispersing single-walled carbon nanotubes, but a large surfactant amount is used.
  • Some surfactant concentrations up to More than 10%, but the concentration of dispersible single-walled carbon nanotubes is still very low.
  • the single-walled carbon nanotube film formed in the dispersion has poor conductivity and heat transfer performance due to the influence of a large amount of surfactant.
  • the present invention provides a method for uniformly dispersing single-walled carbon nanotubes, and does not require an external surface-active auxiliary agent to realize uniformity of single-walled carbon nanotubes under the premise of structural integrity of single-walled carbon nanotubes. dispersion.
  • the carbon nanotube composite transparent electrode film material was developed on the surface of the PET film by using the single-walled carbon nanotube ethanol dispersion as the raw material.
  • the method for uniformly dispersing single-walled carbon nanotubes includes the following steps:
  • the ultraviolet light machine has an irradiation power of 250 W-500 W and is irradiated for 30-60 minutes.
  • the oxidation reaction is carried out in the presence of a strong oxidizing acid or a mixture of a strong acid and an oxidizing agent.
  • the strong oxidizing acid is one or more of concentrated nitric acid, concentrated sulfuric acid or trifluoroacetic acid, and the strong acid and oxidizing agent mixture is concentrated nitric acid or concentrated sulfuric acid to which peroxide is added.
  • the peroxide is hydrogen peroxide or ammonium peroxide.
  • the strong oxidizing acid is concentrated nitric acid, concentrated sulfuric acid, or the mixture of the strong acid and the oxidizing agent is concentrated nitric acid or concentrated sulfuric acid added with peroxide, and the reaction condition is at 80-120 ° C, and the reaction is 0.5-5 hours.
  • the reaction condition is ultrasonic dispersion at room temperature for 30-120 minutes, followed by centrifugation, and repeated normal temperature oxidation for 2-5 times.
  • the step (1) or/and the step (2) are repeated 1-2 times.
  • the dispersion in the step (1) is dispersed by ultrasonic dispersion or a cell pulverizer.
  • the low boiling point alcohol is methanol, ethanol.
  • the invention combines the ultraviolet light machine oxidation process method and the chemical oxidation wet chemical process method to realize the cleaning of the single-walled carbon nanotube powder, and reduces or eliminates the impurities adsorbed on the surface of the single-walled carbon nanotube, so that the single-wall carbon nanometer
  • the surface of the tube is grafted with a functionalized group to achieve dispersion of the single-walled carbon nanotubes in a polar solvent.
  • the principle of the invention is mainly based on carbonaceous by-products and metal catalysts such as amorphous carbon, carbon nanoparticles and carbon fragments which generally contain high chemical activity and low crystallinity between single-walled carbon nanotube surfaces or single-walled carbon nanotubes.
  • carbonaceous by-products and metal catalysts such as amorphous carbon, carbon nanoparticles and carbon fragments which generally contain high chemical activity and low crystallinity between single-walled carbon nanotube surfaces or single-walled carbon nanotubes.
  • the process technology involved in the present invention is to firstly use a UV light machine to attach a small molecular substance to the surface of a single-walled carbon nanotube, easily decompose the organic substance or the like to oxidize or decompose or change its morphology on the surface of the single-walled carbon nanotube, and then pass the control.
  • the condition that the acidic substance functionalizes the carbon nanotubes causes the carbonaceous by-products attached to the surface of the carbon nanotubes to be carboxylated, and the functionalized groups are grafted on the surface of the intact carbon nanotubes.
  • the solubility of single-walled carbon nanotubes also maintains the structural integrity and electrical properties of the single-walled carbon nanotubes themselves.
  • Step 1 Dispersing the single-walled carbon nanotube powder in a low-boiling alcohol or aqueous solution, dispersing by ultrasonic dispersion or a cell pulverizer, and filtering the dispersion, and then the filtrate is placed in an ultraviolet machine for a certain period of time.
  • the power of the UV machine is controlled between 250-500W, and the illumination time is controlled at 10-60min.
  • Step 2 The carbon nanotubes irradiated by the ultraviolet machine are washed with a strong acid to control the reaction conditions, and then washed.
  • Step 3 The single-walled carbon nanotubes cleaned by strong acid are separated by repeated centrifugation, and ultrasonic cleaning is repeated to obtain a uniform single-walled carbon nanotube dispersion.
  • the process steps in this process require multiple iterations and adjustments. Especially in process step 2, the effect of using different strong acids on amorphous carbon is also different.
  • the solubility of the obtained single-walled carbon nanotubes and the cleanliness of the carbon nanotubes are also greatly different.
  • the strong acid used in the present invention is an easily decomposable acid such as trifluoroacetic acid (TFA), nitric acid, concentrated sulfuric acid or hydrogen peroxide which does not leave an inorganic salt on the surface of the carbon nanotube.
  • Corresponding solvents are low boiling alcohols such as methanol, ethanol; water; N,N-dimethylformamide (DMF) and the like.
  • the treatment temperature of DMF and TFA mixed acid is normal temperature, the treatment time is 40-120 min, the treatment temperature of the remaining acid or mixed acid is controlled by 80-120 degrees Celsius, and the treatment time is controlled within 30-300 min.
  • the invention develops a carbon nano-composite transparent electrode material as a basis for application, and develops uniformity of single-walled carbon nanotubes in water or alcohol solvent without the need of external dispersing aid under the premise of structural integrity of single-walled carbon nanotubes. dispersion.
  • the carbon nanotube concentration is characterized by the absorbance value of the carbon nanotube dispersion. Generally, the absorbance of carbon nanotubes with poor dispersion is about 16000-17000.
  • the absorbance value of the carbon nanotube dispersion liquid designed by the invention can be reduced by 10 times to about 1500.
  • the carbon nanotube composite transparent electrode film material was developed on the surface of the PET film by using the single-walled carbon nanotube ethanol dispersion as the raw material.
  • the obtained single-walled carbon nanotube dispersion with good dispersibility is added as a conductive material to the conductive polymer system, and a high-performance carbon nanocomposite flexible transparent electrode material can be prepared without adding a surfactant, and the transmittance is obtained. High, square resistance is small.
  • the obtained single-walled carbon nanotube dispersion with good dispersibility can be used as a nano-catalyst or other functionalized nano-material carrier to realize its application in special environments.
  • A is untreated single-walled carbon nanotubes, B-treated single-walled carbon nanotubes, C-treated single-walled carbon nanotubes, and D-treated single-walled carbon nanotubes E, single-walled carbon nanotubes treated in Example 4, and single-walled carbon nanotubes treated in F Example 5.
  • a single-walled carbon nanotube suspension was formed after ultrasonic dispersion of 0.05 g of single-walled carbon nanotubes in 20 ml of ethanol for 20 min.
  • the single-walled carbon nanotube suspension was placed in a UV light washer for 40 min.
  • the obtained single-walled carbon nanotube powder was ultrasonically washed with 20 ml of DMF and TFA mixture (9:1/Vol) for 30-60 min, centrifuged at 7000 rpm, and then ultrasonically washed for 5 times, and finally dispersed by ultrasonication with ethanol. After 20 min, it was centrifuged again and twice, and finally an ethanol dispersion of SWCNT was obtained.
  • the dispersion of single-walled carbon nanotubes is shown in Figure 1.
  • the absorbance value was determined to be 1655.
  • a single-walled carbon nanotube suspension was formed after ultrasonic dispersion of 0.05 g of single-walled carbon nanotubes in 20 ml of ethanol for 20 min.
  • the single-walled carbon nanotube suspension was placed in a UV light washer for 40 min to obtain a single-walled carbon nanotube powder; 20 ml of deionized water was placed in a single-mouth flask, and 10 ml of concentrated HNO 3 (68 wt. %), a 5 wt% aqueous solution of ammonium persulfate (APS) was added, and after mixing, the purified single-walled carbon nanotube powder was added, and the magnetic particles were stirred, and refluxed at 120 ° C for 5 hours.
  • APS ammonium persulfate
  • the deionized water was repeatedly centrifuged (7000 rpm, 10 min) three times, and the obtained single-walled carbon nanotubes were finally ultrasonically dispersed with ethanol for 20 min, and then centrifuged twice, and finally, an ethanol dispersion of SWCNT was obtained.
  • the dispersion of single-walled carbon nanotubes is shown in Figure 1.
  • the absorbance was measured to be 1745.
  • single-walled carbon nanotubes were dispersed in 20 ml of ethanol, and dispersed for 20 min after ultrasonication to form a single-walled carbon nanotube suspension.
  • the single-walled carbon nanotube suspension was placed in a UV light washer for 40 min, and the obtained single-walled carbon nanotube powder was ultrasonically washed with 20 ml of DMF and TFA mixture (9:1/Vol) for 30 min, centrifuged and separated. Repeat the ultrasonic cleaning for a total of 5 times. It was then ultrasonically washed with ethanol for 20 min, then centrifuged again and twice.
  • the SWCNT ethanol dispersion was poured into a Petri dish and placed in a UV light washer for 40 min to obtain single-walled carbon nanotube powder; 20 ml of deionized water was placed in a single-necked flask, and 10 ml of concentrated HNO3 was added ( 68 wt%), 1.5 g of ammonium persulfate (APS) was added, and after mixing, the purified single-walled carbon nanotube powder was added, magnetically stirred, and refluxed at 85 ° C for 5 h.
  • APS ammonium persulfate
  • the obtained single-walled carbon nanotubes were finally ultrasonically dispersed with ethanol for 20 min, and then centrifuged twice, and finally, the SWCNT ethanol dispersion was obtained by repeated centrifugation (7000 rpm, 10 min) with deionized water.
  • the dispersion of single-walled carbon nanotubes is shown in Figure 1.
  • the absorbance value was determined to be 1544.
  • single-walled carbon nanotubes were dispersed in 20 ml of ethanol, and dispersed for 20 min after ultrasonication to form a single-walled carbon nanotube suspension.
  • the single-walled carbon nanotube suspension was placed in a UV light washer for 40 minutes to obtain a single-walled carbon nanotube powder; 20 ml of concentrated sulfuric acid was placed in a single-mouth flask, and the purified single-walled carbon nanotube powder was added.
  • the mixed concentrated sulfuric acid solution of the single-walled carbon nanotubes was diluted with 10:1 water, and then centrifuged and repeated four times. Finally, a single-walled carbon nanotube powder is obtained.
  • the powder was placed in a one-necked flask, 20 ml of deionized water was added, 10 ml of concentrated HNO 3 (68 wt%) was added, 1.5 g of ammonium persulfate (APS) was added, and the mixture was magnetically stirred and refluxed at 85 ° C for 5 hours.
  • the obtained single-walled carbon nanotubes were finally ultrasonically dispersed with ethanol for 20 min, and then centrifuged twice, and finally, the SWCNT ethanol dispersion was obtained by repeated centrifugation (7000 rpm, 10 min) with deionized water.
  • the dispersion of single-walled carbon nanotubes is shown in Figure 1.
  • the absorbance value was determined to be 1487.
  • single-walled carbon nanotubes were dispersed in 20 ml of ethanol, and dispersed for 20 min after ultrasonication to form a single-walled carbon nanotube suspension.
  • the single-walled carbon nanotube suspension was placed in a UV light washer for 40 minutes to obtain a single-walled carbon nanotube powder; 20 ml of concentrated sulfuric acid was placed in a single-mouth flask, and the purified single-walled carbon nanotube powder was added.
  • the mixed concentrated sulfuric acid solution of the single-walled carbon nanotubes was diluted with 10:1 water, and then centrifuged and repeated four times. Finally, a single-walled carbon nanotube powder is obtained.
  • the powder was placed in a one-necked flask, 20 ml of deionized water was added, 10 ml of concentrated HNO3 (68 wt%) was added, 10 ml of H 2 O 2 was added , and the mixture was stirred magnetically, and refluxed at 85 ° C for 5 h.
  • the obtained single-walled carbon nanotubes were finally ultrasonically dispersed with ethanol for 20 min, and then centrifuged twice, and finally, the SWCNT ethanol dispersion was obtained by repeated centrifugation (7000 rpm, 10 min) with deionized water.
  • the dispersion of single-walled carbon nanotubes is shown in Figure 1.
  • the absorbance value was determined to be 1766.
  • the carbon nanotube dispersion liquid of Example 1 was added with 10 ml of PEDOT:PSS (poly 3,4-ethylenedioxythiophene: sodium polystyrene sulfonate aqueous solution, commercially available, containing 1.8% PEDOT), and ultrasonically dispersed to obtain Carbon nanotube ink solution.
  • the ink solution was prepared on the surface of the PET film by a spin coating process to prepare a transparent conductive electrode film.
  • the control filming process was 3000 rpm for 40 s.
  • the transmittance of the prepared transparent electrode film at a light wavelength of 550 nm was 80% or more.
  • the square resistance is 100-150 ⁇ / ⁇ .
  • the single-walled carbon nanotube dispersion prepared by the invention has good dispersibility and is added into the conductive polymer system as a conductive material, and the high-performance carbon nano-composite flexible transparent electrode material is prepared without the addition of a surfactant. Sexuality, small resistance.
  • the single-walled carbon nanotube dispersion prepared by the invention with good dispersibility can be used as a nano-catalyst or other functionalized nano-material carrier to realize its application in special environments.

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Abstract

提供一种单壁碳纳米管均勾分散的方法，包括：（1）将单壁碳纳米管粉体分散在低沸点醇类或水或DMF中，放入紫外光机中紫外光照射氧化；（2）将紫外光机清洗后的碳纳米管用强酸进行氧化反应，再离心清洗；（3）强酸清洗过的单壁碳纳米管通过2-3次乙醇或水超声分散、离心清洗后，溶于低沸点醇或水或DMF溶液中得到单壁碳纳米管分散液。通过本方法可使得完整的碳纳米管表面嫁接了功能化的基团，实现了单壁碳纳米管的可溶性，还能制备高性能碳纳米复合柔性透明电极材料，透过率高，方阻小。

Description

单壁碳纳米管均匀分散的方法 技术领域
本发明涉及碳纳米管的一种处理方法，特别是涉及单壁碳纳米管均匀分散的方法。
背景技术
碳纳米管是一种具有典型的层状中空结构特征的碳材料，构成碳纳米管的管身由六边形石墨碳环结构单元组成，是一种具有特殊结构(径向尺寸为纳米量级，轴向尺寸为微米量级)的一维量子材料。它的管壁构成主要为数层到数十层的同轴圆管。层与层之间保持固定的距离，约为0.34nm，直径一般为2～20nm。碳纳米管上碳原子的P电子形成大范围的离域π键，因此共轭效应显著。由于碳纳米管的结构与石墨的片层结构相同，具有很好的电学性能。单壁碳纳米管材料因为其高电子迁移率，低电阻率尤其被科研和产业界认定为可代替ITO的透明电极。然而，由于单壁碳纳米管之间很强的范德华作用力(～500eV/μm)和大的长径比(>1000)，通常容易形成大的管束，难以分散，极大地制约了其优异性能的发挥和实际应用。
目前，碳纳米管在溶剂中的主要分散方法为：非共价功能化、共价功能化和溶剂剥离。这些方法的共性是都需要借助较大的机械力，如以高频超声、球磨等促进碳纳米管的分散，然后采用高速离心分离去除大的管束。大的机械力不可避免地会损伤碳纳米管，高速离心分离出大的管束而损失碳纳米管。此外，非共价功能化法会引入难以完全去除的表面活性剂或聚合物等辅助碳纳米管分散的添加剂，降低了碳纳米管网络本身的电学，热力学性能；共价功能化法会破坏碳纳米管功能化位点的sp2结构；溶剂剥离法所用溶剂通常毒性大、沸点高且分散效率低。因此，在保持结构完整和无添加剂的前提下，将碳纳米管在普通溶剂中进行有效分散仍是单壁碳纳米管研究与应用面临的重要问题。
在碳纳米管中，单壁碳纳米管的导电性最高。但是，单壁碳纳米管在溶剂中最难以分散。分散溶剂通常采用水、低沸点醇类(例如甲醇、2-丙醇等醇)等溶剂，此类溶剂对单壁碳纳米管的润湿性差，分散性差。此外有机溶剂，如四氢呋喃、二甲基甲酰胺等有机溶剂相比水和醇类的溶剂分散性略好一些。但是，四氢呋喃的毒性高。而且二甲基甲酰胺的沸点过高。因此通过单一的溶剂来分散单壁碳纳米管的方法制备的碳纳米管分散液的浓度很小。
此外，在水或醇类溶剂加入表面活性剂十二烷基苯磺酸钠，辛基苯酚聚乙二醇酯，聚乙烯基吡咯烷酮等来辅助分散单壁碳纳米管，但使用表面活性剂量大，有的表面活性剂浓度达 到10％以上，但可分散的单壁碳纳米管的浓度还是很低。在分散液中由于大量表面活性剂的影响，形成单壁碳纳米管膜导电性和传热性能较差。
发明内容
针对上述领域中的缺陷，本发明提供一种单壁碳纳米管均匀分散的方法，无需外加表面活性助剂，在单壁碳纳米管的结构完整性的前提下，实现单壁碳纳米管均匀分散。并以此单壁碳纳米管乙醇分散液为原材料在PET薄膜表面开发碳纳米管复合透明电极薄膜材料。
单壁碳纳米管均匀分散的方法，包括如下步骤：
(1)将单壁碳纳米管粉体分散在低沸点醇类或水或DMF中，放入紫外光机中紫外光照射氧化；
(2)将紫外光机清洗后的碳纳米管用强酸进行氧化反应，再离心清洗，
(3)强酸清洗过的单壁碳纳米管通过2-3次乙醇或水超声分散、离心清洗后，溶于低沸点醇或水或DMF溶液中得到单壁碳纳米管分散液。
所述紫外光机的照射功率为250W-500W，照射一定30-60分钟。
所述氧化反应在强氧化性酸或强酸与氧化剂混合物存在下进行。
所述强氧化性酸为浓硝酸、浓硫酸或三氟乙酸中的一种或多种，所述强酸与氧化剂混合物为加入有过氧化物的浓硝酸或浓硫酸。
所述过氧化物为双氧水或过氧化铵。
所述强氧化性酸为浓硝酸、浓硫酸，或者所述强酸与氧化剂混合物为加入有过氧化物的浓硝酸或浓硫酸时，其反应条件为于80-120℃下，反应0.5-5小时；或者强氧化性酸为三氟乙酸时，其反应条件为于常温超声分散30-120分钟，再离心清洗，重复常温氧化2-5次。
所述步骤(1)或/和步骤(2)重复1-2次。
所述步骤(1)中的分散为通过超声波分散或细胞粉碎机分散。
所述低沸点醇为甲醇，乙醇。
本发明结合紫外光机氧化的工艺方法和化学氧化的湿化学工艺方法实现了对单壁碳纳米管粉体进行清洗，减少或消除吸附在单壁碳纳米管表面的杂质，使得单壁碳纳米管表面嫁接了功能化的基团，从而达到了单壁碳纳米管在极性溶剂中的分散。
该发明的原理主要是基于单壁碳纳米管表面或单壁碳纳米管之间通常含有高化学活性和低结晶性的无定形碳、碳纳米颗粒以及碳片段等碳质副产物和金属催化剂，通过控制紫外光照射功率和时间以及控制湿化学氧化条件可实现单壁碳纳米管表面选择性功能化，达到单壁碳纳米管在溶剂中的均匀分散而碳纳米管的结构和性能基本不受影响。
本发明所涉及的工艺技术是首先利用紫外光机将单壁碳纳米管表面附着的小分子物质，易分解有机物质等氧化分解或改变其在单壁碳纳米管表面的形态，然后通过控制强酸性物质使碳纳米管功能化的条件，使活性较大的依附在碳纳米管表面的碳质副产物等被羧基化，进而使得完整的碳纳米管表面嫁接了功能化的基团，实现了单壁碳纳米管的可溶性，同时也保持了单壁碳纳管本身的结构完整性和本身的电学特性。
具体工艺方法如下
步骤一：将单壁碳纳米管粉体分散在低沸点醇类或水溶液中，通过超声波分散或细胞粉碎机分散，分散液经过滤后，所得滤液放入紫外光机中照射一定时间。紫外光机的功率控制在250-500W之间，照射时间控制在10-60min
步骤二：将紫外光机照射清洗后的碳纳米管用强酸控制反应条件，进行清洗。
步骤三：强酸清洗过的单壁碳纳米管通过多次离心分离，重复超声波清洗后，得到均匀的单壁碳纳米管分散液。
此工艺方法中的工艺步骤需要多次重复和调整。尤其是工艺步骤二中，采用不同的强酸对非晶态碳的作用也各不相同。所得单壁碳纳米管的可溶性和碳纳米管的洁净度也有很大的差异。本发明中采用的强酸有三氟乙酸(TFA)，硝酸，浓硫酸，双氧水等在碳纳米管表面不会残留无机盐的易分解的酸。相应的溶剂有低沸点醇类如甲醇，乙醇；水；N,N-二甲基甲酰胺(DMF)等。
不同的酸处理工艺不同其中，DMF和TFA混合酸的处理温度是常温，处理时间是40-120min，其余的酸或混酸其处理温度控制80-120摄氏度，处理时间控制在30-300min内。
本发明以开发碳纳米复合透明电极材料为应用基础，开发了无需外加分散辅助剂，在单壁碳纳米管的结构完整性的前提下，实现单壁碳纳米管在水或醇类溶剂中均匀分散。通过碳纳米管分散液的吸光度值来表征碳纳米管浓度。一般来说分散不好的碳纳米管的吸光度值大约是16000-17000之间。而本发明所设计到的碳纳米管分散液的吸光度值可降低10倍，达到1500左右。并以此单壁碳纳米管乙醇分散液为原材料在PET薄膜表面开发碳纳米管复合透明电极薄膜材料。
得到的具有良好分散性的单壁碳纳米管分散液，作为导电质加入导电高分子体系中，在无需加入表面活性剂的情况下，能制备高性能碳纳米复合柔性透明电极材料，透过率高，方阻小。
得到的具有良好分散性的单壁碳纳米管分散液可作为纳米催化剂或其它功能化纳米质的载体，实现其在特殊环境中的应用。
附图说明
图1单壁碳纳米管的SEM照片
其中A为未处理前单壁碳纳米管，B实施例1处理后的单壁碳纳米管，C实施例2处理后的单壁碳纳米管，D实施例3处理后的单壁碳纳米管，E实施例4处理后的单壁碳纳米管，F实施例5处理后的单壁碳纳米管。
具体实施方式
下面结合实施例对本发明做进一步的详细说明
实施例1：
0.05g的单壁碳纳米管在20ml乙醇中超声分散20min后形成单壁碳纳米管悬浊液。将此单壁碳纳米管悬浊液放入UV光清洗机中处理40min。所得单壁碳纳米管粉体用DMF和TFA混合液(9：1/Vol)20ml超声清洗30-60min，在7000rpm转速下离心分离，再重复超声清洗，共反复5次，最后用乙醇超声分散20min,再离心，反复两次，最后得SWCNT的乙醇分散液。单壁碳纳米管分散情况见图1。测定其吸光度值1655。
实施例2
0.05g的单壁碳纳米管在20ml乙醇中超声分散20min后形成单壁碳纳米管悬浊液。将此单壁碳纳米管悬浊液放入UV光清洗机中处理40min，得到单壁碳纳米管粉体；取20ml的去离子水放入单口烧瓶中，再加入10ml的浓HNO3(68wt％)，加入5wt％过硫酸铵(APS)水溶液，混合均匀后加入提纯过的单壁碳纳米管粉体，磁子搅拌，120℃下回流反应5h。去离子水反复离心冲洗(7000rpm，10min)3次，将所得的单壁碳纳米管最后用乙醇超声分散20min,再离心，反复两次，最后得SWCNT的乙醇分散液。单壁碳纳米管分散情况见图1。测定其吸光度值为1745。
实施例3
0.05g的单壁碳纳米管分散在20ml乙醇中，超声分散20min后形成单壁碳纳米管悬浊液。将此单壁碳纳米管悬浊液放入UV光清洗机中处理40min,所得单壁碳纳米管粉体用DMF和TFA混合液(9：1/Vol)20ml超声清洗30min，离心分离后再重复超声清洗，共反复5次。然后用乙醇超声清洗20min,再离心，反复两次。最后将SWCNT的乙醇分散液倒入培养皿中，放入UV光清洗机中处理40min得到单壁碳纳米管粉体；取20ml的去离子水放入单口烧瓶中，再加入10ml的浓HNO3(68wt％)，加入1.5g过硫酸铵(APS)，混合均匀后加入提纯过的单壁碳纳米管粉体，磁力搅拌，85℃下回流反应5h。
用去离子水反复离心冲洗(7000rpm，10min)3次，将所得的单壁碳纳米管最后用乙醇超声分散20min,再离心，反复两次，最后得SWCNT的乙醇分散液。单壁碳纳米管分散情况见图1。测定其吸光度值1544。
实施例4
0.05g的单壁碳纳米管分散在20ml乙醇中，超声分散20min后形成单壁碳纳米管悬浊液。将此单壁碳纳米管悬浊液放入UV光清洗机中处理40min,得到单壁碳纳米管粉体；取20ml的浓硫酸放入单口烧瓶中，加入提纯过的单壁碳纳米管粉体，磁力搅拌，室温溶胀12h。将单壁碳纳米管的混合浓硫酸溶液用10：1的水稀释后，进行离心分离，反复4次。最后得单壁碳纳米管粉体。将此粉体放入单口烧瓶中，加入20ml的去离子水，再加入10ml的浓HNO3(68wt％)，加入1.5g过硫酸铵(APS)，磁力搅拌，85℃下回流反应5h。
用去离子水反复离心冲洗(7000rpm，10min)3次，将所得的单壁碳纳米管最后用乙醇超声分散20min,再离心，反复两次，最后得SWCNT的乙醇分散液。单壁碳纳米管分散情况见图1。测定其吸光度值1487。
实施例5
0.05g的单壁碳纳米管分散在20ml乙醇中，超声分散20min后形成单壁碳纳米管悬浊液。将此单壁碳纳米管悬浊液放入UV光清洗机中处理40min,得到单壁碳纳米管粉体；取20ml的浓硫酸放入单口烧瓶中，加入提纯过的单壁碳纳米管粉体，磁力搅拌，室温溶胀12h。将单壁碳纳米管的混合浓硫酸溶液用10：1的水稀释后，进行离心分离，反复4次。最后得单壁碳纳米管粉体。将此粉体放入单口烧瓶中，加入20ml的去离子水，再加入10ml的浓HNO3(68wt％)，加10ml H2O2，磁力搅拌，85℃下回流反应5h。
用去离子水反复离心冲洗(7000rpm，10min)3次，将所得的单壁碳纳米管最后用乙醇超声分散20min,再离心，反复两次，最后得SWCNT的乙醇分散液。单壁碳纳米管分散情况见图1。测定其吸光度值1766。
实施例6：
将实施例1中的碳纳米管分散液中加入10mlPEDOT：PSS(聚3,4-乙撑二氧噻吩:聚苯乙烯磺酸钠水溶液，市售，含1.8％PEDOT)，超声分散后，得碳纳米管墨水溶液。将此墨水溶液在PET薄膜表面通过旋涂工艺制备透明导电电极薄膜。控制匀膜工艺为3000rpm 40s。
制备的透明电极薄膜在光波长550nm的透过率是80％以上。方阻是100-150Ω/□。
本发明制备的有良好分散性的单壁碳纳米管分散液作为导电质加入导电高分子体系中，不需要加入表面活性剂的情况下，制备高性能碳纳米复合柔性透明电极材料，其透过性度，方阻小。
本发明制备的具有良好分散性的单壁碳纳米管分散液可作为纳米催化剂或其它功能化纳米质的载体，实现其在特殊环境中的应用。

Claims (9)

  1. 单壁碳纳米管均匀分散的方法，包括如下步骤：
    (1)将单壁碳纳米管粉体分散在低沸点醇类或水或DMF中，放入紫外光机中紫外光照射氧化；
    (2)将紫外光机清洗后的碳纳米管用强酸进行氧化反应，再离心清洗，
    (3)强酸清洗过的单壁碳纳米管通过2-3次乙醇或水超声分散、离心清洗后，溶于低沸点醇或水或DMF溶液中得到单壁碳纳米管分散液。
  2. 根据权利要求1所述的方法，所述紫外光机的照射功率为250W-500W，照射一定30-60分钟。
  3. 根据权利要求1所述的方法，所述氧化反应在强氧化性酸或强酸与氧化剂混合物存在下进行。
  4. 根据权利要求3所述的方法，所述强氧化性酸为浓硝酸、浓硫酸或三氟乙酸中的一种或多种，所述强酸与氧化剂混合物为加入有过氧化物的浓硝酸或浓硫酸。
  5. 根据权利要求4所述的方法，所述过氧化物为双氧水或过氧化铵。
  6. 根据权利要求5所述的方法，所述强氧化性酸为浓硝酸、浓硫酸，或者所述强酸与氧化剂混合物为加入有过氧化物的浓硝酸或浓硫酸时，其反应条件为于80-120℃下，反应0.5-5小时；或者强氧化性酸为三氟乙酸时，其反应条件为于常温超声分散30-120分钟，再离心清洗，重复常温氧化2-5次。
  7. 根据权利要求1所述的方法，所述步骤(1)或/和步骤(2)重复1-2次。
  8. 根据权利要求1所述的方法，所述步骤(1)中的分散为通过超声波分散或细胞粉碎机分散。
  9. 根据权利要求1所述的方法，所述低沸点醇为甲醇，乙醇。
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TW201527209A (zh) 2015-07-16
JP6152492B2 (ja) 2017-06-21
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