CN113912063B - Ti (titanium) 3 C 2 T x Base electrode material, preparation method and application thereof - Google Patents
Ti (titanium) 3 C 2 T x Base electrode material, preparation method and application thereof Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000010936 titanium Substances 0.000 title 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title 1
- 229910052719 titanium Inorganic materials 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229920000767 polyaniline Polymers 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 38
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000006229 carbon black Substances 0.000 claims abstract description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 238000005119 centrifugation Methods 0.000 claims abstract 2
- 239000006185 dispersion Substances 0.000 claims description 66
- 239000000243 solution Substances 0.000 claims description 45
- 239000002131 composite material Substances 0.000 claims description 20
- 238000012360 testing method Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 238000002242 deionisation method Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 238000005530 etching Methods 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- -1 pour in the beaker Substances 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 25
- 239000002048 multi walled nanotube Substances 0.000 abstract description 6
- 230000037427 ion transport Effects 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000010612 desalination reaction Methods 0.000 abstract description 3
- 239000013535 sea water Substances 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract 2
- 238000000034 method Methods 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 238000011160 research Methods 0.000 description 5
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
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Abstract
本发明公开了一种Ti3C2T x 基电极材料及其制备方法和应用，该制备包括以下步骤：（1）将Ti3C2T x 超声离心后稀释；（2）将Ti3C2T x 和多壁碳纳米管(MWNT)置于烧杯中，稀释后超声搅拌，加入浓盐酸震荡均匀；（3）倒入四氯化碳与苯胺的混合溶液；（4）在混合溶液中加入过硫酸铵，充分反应后，离心、水洗、冷冻干燥，得到Ti3C2T x /MWNT/PANI粉体；（5）Ti3C2T x /MWNT/PANI粉体分散在乙醇中，并加入炭黑和PTFE，涂覆于衬底上，烘干后即得到Ti3C2T x /MWNT/PANI基电极材料。本发明制备得到的电极材料比表面积大，吸附容量高达258 mg·g‑1，Ti3C2T x 提供离子运输通道并缩短离子运输路径，实现了高容量、快速率，制备方法简单，为Ti3C2T x 在海水淡化领域的应用提供了前景。
The invention discloses a Ti 3 C 2 T x -based electrode material and its preparation method and application. The preparation includes the following steps: (1) Dilute the Ti 3 C 2 T x after ultrasonic centrifugation; (2) Dilute the Ti 3 C 2 T x 2 T x and multi-walled carbon nanotubes (MWNT) were placed in a beaker, diluted and stirred ultrasonically, and concentrated hydrochloric acid was added to shake evenly; (3) Pour the mixed solution of carbon tetrachloride and aniline; (4) In the mixed solution Add ammonium persulfate, after fully reacting, centrifuge, wash with water, and freeze-dry to obtain Ti 3 C 2 T x /MWNT/PANI powder; (5) Ti 3 C 2 T x /MWNT/PANI powder is dispersed in ethanol, And adding carbon black and PTFE, coating on the substrate, drying to obtain Ti 3 C 2 T x /MWNT/PANI base electrode material. The electrode material prepared by the present invention has a large specific surface area and an adsorption capacity of up to 258 mg·g ‑1 . Ti 3 C 2 T x provides ion transport channels and shortens the ion transport paths, thereby achieving high capacity and fast rate. The preparation method is simple and is The application of Ti 3 C 2 T x in the field of seawater desalination provides prospects.
Description
技术领域technical field
本发明属于新材料技术领域，具体涉及一种Ti3C2Tx基电极材料及其制备方法和应用。The invention belongs to the technical field of new materials, and in particular relates to a Ti3C2Tx - based electrode material and its preparation method and application.
背景技术Background technique
地球上淡水资源不足，且分布不均，人口面临极度缺水危机。充分利用海水资源是目前解决供水不足的有效方式之一，探求一种绿色环保的处理方式成为热点话题。反渗透、电渗析等技术占据市场主流，但均需要很高的电力消耗和运营成本，或是大规模的基础设施且易结垢。而电容去离子(CDI)作为一种低耗高效、低成本、无二次污染的新型技术，被认为是最有前景的为人类提供可利用淡水的方法。然而，传统的CDI系统存在去离子能力低、循环稳定性差、电吸附容量低等问题，严重阻碍其实际应用。Fresh water resources on the earth are insufficient and unevenly distributed, and the population is facing an extreme water shortage crisis. Making full use of seawater resources is one of the effective ways to solve the shortage of water supply, and seeking a green and environmentally friendly treatment method has become a hot topic. Reverse osmosis, electrodialysis and other technologies occupy the mainstream of the market, but they all require high power consumption and operating costs, or large-scale infrastructure and are prone to fouling. Capacitive deionization (CDI), as a new technology with low consumption, high efficiency, low cost, and no secondary pollution, is considered to be the most promising method to provide humans with usable fresh water. However, the traditional CDI system has problems such as low deionization ability, poor cycle stability, and low electrosorption capacity, which seriously hinder its practical application.
针对电极材料的研究能够有效改善CDI器件的性能，各种碳材料及复合碳电极材料被相继应用于电容脱盐这一领域。Drewes等人利用碳气凝胶作为电极材料处理NaCl溶液，在电压为1.3V时，吸附容量达到7.0mg/g(Xu Pei et al.,Water Research,2008,42(10-11),2605-2617)。邱介山等人所制备的活性炭纤维电极，在1.6V时电吸附容量达到4.46mg/g(Wang Gang et al.,Electrochimica Acta,2012,69,65-70)。此类碳材料具有可利用的高比表面积和多维孔洞、良好的导电性、高比电容、优异的电化学稳定性等，可以有效提升电容去离子的吸附容量及吸脱附效率。Research on electrode materials can effectively improve the performance of CDI devices. Various carbon materials and composite carbon electrode materials have been successively applied in the field of capacitive desalination. Drewes et al. used carbon airgel as an electrode material to treat NaCl solution. When the voltage was 1.3V, the adsorption capacity reached 7.0mg/g (Xu Pei et al., Water Research, 2008, 42(10-11), 2605- 2617). The activated carbon fiber electrode prepared by Qiu Jieshan et al. has an electric adsorption capacity of 4.46mg/g at 1.6V (Wang Gang et al., Electrochimica Acta, 2012, 69, 65-70). This kind of carbon material has available high specific surface area and multi-dimensional pores, good electrical conductivity, high specific capacitance, excellent electrochemical stability, etc., which can effectively improve the adsorption capacity and adsorption and desorption efficiency of capacitive deionization.
MXene是Gogotsi和Barsoum在2011年发现了一类新型过渡金属碳化物和氮化物的二维材料，通过二维层状结构之间的离子嵌入来存储电荷，表现为理想的赝电容。其中，Ti3C2Tx是目前最常见的MXene材料之一，因其类石墨烯的层状结构，巨大的比表面积和丰富的活性位点，提供离子运输通道并缩短离子运输路径。加之其具有亲水性、离子传导性、优良的电导率等优点，是一种很具前景的电容去离子电极材料。Pattarachai Srimuk与Mohammad Torkamanzadeh等人先后利用Ti3C2Tx的赝电容特性，制备出吸附容量达到12-13mg/g的电极材料(Srimuk Pattarachai et al.,J.Mater.Chem.A,2016,4(47),18265-18271&Torkamanzadeh Mohammad et al.,ACS Appl.Mater.Interfaces,2020,12(23),26013–26025)。但Ti3C2Tx片层易堆叠，离子在层间的运输路径长，限制了其微观结构的调控方向，使其吸附容量及吸脱附速率较差。MXene is a new type of two-dimensional material of transition metal carbides and nitrides discovered by Gogotsi and Barsoum in 2011. It stores charges through ion intercalation between two-dimensional layered structures, and behaves as an ideal pseudocapacitance. Among them, Ti 3 C 2 T x is one of the most common MXene materials at present, because of its graphene-like layered structure, huge specific surface area and abundant active sites, it provides ion transport channels and shortens the ion transport path. In addition, it has the advantages of hydrophilicity, ion conductivity, and excellent electrical conductivity. It is a promising electrode material for capacitive deionization. Pattarachai Srimuk and Mohammad Torkamanzadeh have successively used the pseudocapacitive properties of Ti 3 C 2 T x to prepare electrode materials with an adsorption capacity of 12-13 mg/g (Srimuk Pattarachai et al., J.Mater.Chem.A, 2016, 4(47), 18265-18271 & Torkamanzadeh Mohammad et al., ACS Appl. Mater. Interfaces, 2020, 12(23), 26013–26025). However, Ti 3 C 2 T x sheets are easy to stack, and the transport path of ions between layers is long, which limits the direction of regulation of its microstructure, making its adsorption capacity and adsorption-desorption rate poor.
发明内容Contents of the invention
针对现有技术Ti3C2Tx材料在电容去离子实际应用存在的限制的不足，本发明的目的在于提供一种吸附容量大、吸附速率高的Ti3C2Tx基电极材料。本发明制备得到的电极材料，具有较大的比表面积，Ti3C2Tx片层间吸附离子，与MWNT形成网络结构，为溶液浸入和离子扩散提供了通道，有效提升吸附速率，增大吸附容量，PANI的引入使其具有较高的比电容为Ti3C2Tx在海水淡化领域的应用提供了更好的前景。Aiming at the limitations of existing Ti 3 C 2 T x materials in the practical application of capacitive deionization, the purpose of the present invention is to provide a Ti 3 C 2 T x -based electrode material with large adsorption capacity and high adsorption rate. The electrode material prepared by the present invention has a relatively large specific surface area, and ions are adsorbed between Ti 3 C 2 T x sheets, forming a network structure with MWNT, providing channels for solution immersion and ion diffusion, effectively improving the adsorption rate, increasing the Adsorption capacity, the introduction of PANI makes it have a higher specific capacitance, which provides a better prospect for the application of Ti 3 C 2 T x in the field of seawater desalination.
为了实现上述目的，本发明采取如下技术方案：In order to achieve the above object, the present invention takes the following technical solutions:
一种Ti3C2Tx基电极材料的制备方法，包括以下步骤：A method for preparing a Ti3C2Tx - based electrode material, comprising the following steps:
(1)将制备的Ti3C2Tx分散液超声，离心，去除沉淀，取上清液稀释得到Ti3C2Tx分散溶液；(1) Ultrasonicate the prepared Ti 3 C 2 T x dispersion, centrifuge to remove the precipitate, take the supernatant and dilute to obtain a Ti 3 C 2 T x dispersion;
(2)向步骤(1)所得Ti3C2Tx分散溶液中加入MWNT，加水稀释、超声、搅拌，得到Ti3C2Tx/MWNT复合物分散液，并加入浓盐酸；(2) Add MWNT to the Ti 3 C 2 T x dispersion solution obtained in step (1), add water to dilute, sonicate, and stir to obtain a Ti 3 C 2 T x /MWNT composite dispersion, and add concentrated hydrochloric acid;
(3)取四氯化碳与苯胺单体，倒入烧杯中，混合均匀；(3) get carbon tetrachloride and aniline monomer, pour in the beaker, mix;
(4)将步骤(2)与步骤(3)所得到的溶液混合，之后加入过硫酸铵水溶液，充分反应，得到Ti3C2Tx/MWNT/PANI复合物分散液；(4) Mix the solution obtained in step (2) with step (3), then add an aqueous ammonium persulfate solution, and react fully to obtain a Ti 3 C 2 T x /MWNT/PANI composite dispersion;
(5)将步骤(4)所得Ti3C2Tx/MWNT/PANI复合物分散液，离心、水洗、冷冻干燥，得到Ti3C2Tx/MWNT/PANI粉体；(5) Centrifuge, wash and freeze-dry the Ti 3 C 2 T x /MWNT/PANI composite dispersion obtained in step (4) to obtain Ti 3 C 2 T x /MWNT/PANI powder;
(6)将步骤(5)得到的粉体分散在乙醇中，并加入炭黑和PTFE，超声，涂覆于衬底上，烘干后即得到Ti3C2Tx/MWNT/PANI基电极材料。(6) Disperse the powder obtained in step (5) in ethanol, add carbon black and PTFE, ultrasonically apply it on the substrate, and obtain Ti 3 C 2 T x /MWNT/PANI-based electrode after drying Material.
优选的，步骤(1)中所述Ti3C2Tx分散液的制备方法为：取15mL的12MHCl注入50mL的试管中，加入1g的LiF溶解，得到刻蚀液；然后，将1g的Ti3AlC2加入到上述制备好的溶液中，摇匀，将试管置于60℃水浴锅中反应72h，反应结束后，用去离子水离心洗涤、离心，得到Ti3C2Tx粉末，再将Ti3C2Tx粉末分散到水中即得所述Ti3C2Tx分散液。Preferably, the preparation method of the Ti 3 C 2 T x dispersion described in step (1) is as follows: inject 15 mL of 12M HCl into a 50 mL test tube, add 1 g of LiF to dissolve to obtain an etching solution; then, add 1 g of Ti 3 Add AlC 2 to the above-prepared solution, shake well, place the test tube in a 60°C water bath for 72 hours, after the reaction, wash and centrifuge with deionized water to obtain Ti 3 C 2 T x powder, and then The Ti 3 C 2 T x dispersion is obtained by dispersing the Ti 3 C 2 T x powder into water.
优选的，步骤(1)中所述Ti3C2Tx分散液在300-400W细胞破碎中超声3h-4h，离心为3000-3500r/min下离心25-35min，Ti3C2Tx分散液的浓度为5mg·ml-1。Preferably, the Ti 3 C 2 T x dispersion in step (1) is sonicated in 300-400W cell disruption for 3h-4h, centrifuged at 3000-3500r/min for 25-35min, and Ti 3 C 2 T x is dispersed The concentration of the solution is 5mg·ml -1 .
优选的，步骤(2)中Ti3C2Tx与MWNT粉体的质量比为1:9-9:1，加水稀释后的体积20ml，超声是于400-500W下超声10-20min，搅拌是在400-600r/min下搅拌4-5h，浓盐酸的加入量为1ml。Preferably, the mass ratio of Ti 3 C 2 T x to MWNT powder in step (2) is 1:9-9:1, the volume after dilution with water is 20ml, ultrasonication is at 400-500W for 10-20min, stirring It is stirred at 400-600r/min for 4-5h, and the amount of concentrated hydrochloric acid added is 1ml.
优选的，步骤(3)中将90-100ml四氯化碳和1ml苯胺单体混合均匀。Preferably, in step (3), 90-100ml of carbon tetrachloride and 1ml of aniline monomer are mixed evenly.
优选的，步骤(4)中所述的过硫酸铵水溶液为称取0.276g过硫酸铵加入1.5-2ml去离子水配制而成；所述反应是在20-30℃下反应10-12h。Preferably, the ammonium persulfate aqueous solution described in step (4) is prepared by weighing 0.276g of ammonium persulfate and adding 1.5-2ml of deionized water; the reaction is carried out at 20-30°C for 10-12h.
优选的，步骤(5)所述复合物分散液于7000-8000r/min离心15-20min，洗涤3-4次，冷冻干燥36-48h。Preferably, the complex dispersion in step (5) is centrifuged at 7000-8000 r/min for 15-20 min, washed 3-4 times, and freeze-dried for 36-48 h.
优选的，步骤(6)中所述衬底为石墨纸，称取50mg Ti3C2Tx/MWNT/PANI粉体分散在1-2ml乙醇后加入6-6.5mg炭黑和4-4.1μl PTFE，300-400W超声10-15min，在真空干燥箱中60℃干燥24h。Preferably, the substrate described in step (6) is graphite paper, weigh 50mg Ti 3 C 2 T x /MWNT/PANI powder and disperse it in 1-2ml ethanol, add 6-6.5mg carbon black and 4-4.1μl PTFE, 300-400W ultrasonic 10-15min, dry in a vacuum oven at 60°C for 24h.
本发明还要求保护由所述的制备方法所制备的Ti3C2Tx基电极材料以及所述的Ti3C2Tx基电极材料在电容去离子中的应用。The present invention also claims to protect the Ti 3 C 2 T x -based electrode material prepared by the preparation method and the application of the Ti 3 C 2 T x -based electrode material in capacitive deionization.
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明通过刻蚀Ti3AlC2、超声方法所制得的Ti3C2Tx具有类石墨烯的层状结构，有利于扩大离子的可存储空间以提升离子的吸附容量。在制备过程中，通过机械混合的方式，将片层状的Ti3C2Tx与MWNT复合，利用多壁碳纳米管的一维结构，以增加其比表面积，并且插入纳米片片层内的MWNT，能够起到连接各片层的作用，与Ti3C2Tx构成网络结构，从而促进电子的运输，提高吸附速率。之后以原位聚合的方式，使具有较大比电容的PANI牢固的与Ti3C2Tx/MWNT结合，有效增加材料的吸附容量，最终获得电容去离子性能优异的复合电极材料。另外，MWNT、Ti3C2Tx、PANI构成网络结构，提高了层间电子传输速率及离子的吸脱附速率。The Ti 3 C 2 T x prepared by etching Ti 3 AlC 2 and ultrasonic methods in the present invention has a graphene-like layered structure, which is beneficial to expanding the storage space of ions and improving the adsorption capacity of ions. During the preparation process, the layered Ti 3 C 2 T x is combined with MWNT by mechanical mixing, and the one-dimensional structure of multi-walled carbon nanotubes is used to increase its specific surface area and insert into the nanosheets. The MWNT can play the role of connecting each sheet, and form a network structure with Ti 3 C 2 T x , thereby promoting the transport of electrons and increasing the adsorption rate. Afterwards, in-situ polymerization is used to firmly combine PANI with large specific capacitance with Ti 3 C 2 T x /MWNT, effectively increase the adsorption capacity of the material, and finally obtain a composite electrode material with excellent capacitive deionization performance. In addition, MWNT, Ti 3 C 2 T x , and PANI form a network structure, which improves the interlayer electron transport rate and ion adsorption and desorption rate.
附图说明Description of drawings
图1是实施例3所制备的Ti3C2Tx/MWNT/PANI的XPS图；(a)全谱图(b)N 1s(c)Ti 2p(d)C 1s；Figure 1 is the XPS diagram of Ti 3 C 2 T x /MWNT/PANI prepared in Example 3; (a) full spectrum (b)
图2是实施例3所制备的Ti3C2Tx/MWNT/PANI的SEM图；Fig. 2 is the SEM figure of Ti3C2Tx / MWNT /PANI prepared in embodiment 3 ;
图3是本发明CDI性能测试过程示意图。Fig. 3 is a schematic diagram of the CDI performance testing process of the present invention.
具体实施方式Detailed ways
以下通过具体较佳实施例对本发明作进一步详细说明，但本发明并不仅限于以下的实施例。The present invention will be further described in detail through specific preferred embodiments below, but the present invention is not limited to the following embodiments.
需要说明的是，无特殊说明外，本发明中涉及到的化学试剂均通过商业渠道购买。It should be noted that, unless otherwise specified, the chemical reagents involved in the present invention were purchased through commercial channels.
本实施例中Ti3AlC2颗粒小于40微米，购于Beijing Lianli New TechnologyCo.Ltd.China。The Ti 3 AlC 2 particles in this example are smaller than 40 microns and purchased from Beijing Lianli New Technology Co. Ltd. China.
实施例1Example 1
一种Ti3C2Tx基电极材料的制备方法，其特征在于，包括以下步骤：A method for preparing a Ti3C2Tx - based electrode material, characterized in that it comprises the following steps:
(1)Ti3C2Tx分散液的制备：取15mL的12M HCl注入50mL的试管中，加入1g的LiF溶解，得到刻蚀液；然后，将1g的Ti3AlC2加入到上述制备好的溶液中，摇匀，将试管置于60℃水浴锅中反应72h，反应结束后，用去离子水离心洗涤三次、5000rpm离心5min，得到Ti3C2Tx粉末，再将Ti3C2Tx粉末分散到水中即得所述Ti3C2Tx分散液。(1) Preparation of Ti 3 C 2 T x dispersion: Take 15mL of 12M HCl and inject it into a 50mL test tube, add 1g of LiF to dissolve to obtain an etching solution; then, add 1g of Ti 3 AlC 2 to the above prepared solution, shake well, and place the test tube in a 60°C water bath for 72 hours of reaction. After the reaction, centrifuge three times with deionized water and centrifuge at 5000rpm for 5 minutes to obtain Ti 3 C 2 T x powder, and then Ti 3 C 2 The T x powder is dispersed in water to obtain the Ti 3 C 2 T x dispersion.
(2)将步骤(1)制备的Ti3C2Tx分散液在300W细胞破碎仪中超声3h，3500r/min离心30min，去除沉淀，取上清液稀释至5mg mL-1得到Ti3C2Tx分散溶液；(2) Sonicate the Ti 3 C 2 T x dispersion prepared in step (1) in a 300W cell disruptor for 3h, centrifuge at 3500r/min for 30min, remove the precipitate, take the supernatant and dilute to 5mg mL -1 to obtain Ti 3 C 2 T x dispersion solution;
(3)向0.8ml步骤(2)所得Ti3C2Tx分散溶液中加入36mgMWNT，加水稀释至20ml、400W超声15min，在500r/min下搅拌4h后，得到Ti3C2Tx/MWNT复合物分散液，并加入1ml浓盐酸；(3) Add 36mgMWNT to 0.8ml of the Ti 3 C 2 T x dispersion solution obtained in step (2), dilute with water to 20ml, 400W ultrasonic for 15min, and stir at 500r/min for 4h to obtain Ti 3 C 2 T x /MWNT Complex dispersion, and add 1ml concentrated hydrochloric acid;
(4)取100ml四氯化碳与1ml苯胺单体，倒入烧杯中，混合均匀；(4) Take 100ml of carbon tetrachloride and 1ml of aniline monomer, pour them into a beaker, and mix well;
(5)称取0.276mg过硫酸铵，加入1.5ml去离子水，震荡均匀；(5) Weigh 0.276mg of ammonium persulfate, add 1.5ml of deionized water, and shake evenly;
(6)将步骤(3)与步骤(4)所得到的溶液混合，之后加入步骤(5)过硫酸铵水溶液，25℃下反应10h，得到Ti3C2Tx/MWNT/PANI复合物分散液；(6) Mix the solution obtained in step (3) with step (4), then add the aqueous solution of ammonium persulfate in step (5), and react at 25°C for 10 hours to obtain a Ti 3 C 2 T x /MWNT/PANI composite dispersion liquid;
(7)将步骤(6)所得Ti3C2Tx/MWNT/PANI复合物分散液，8000r/min离心15min、水洗3次、冷冻干燥48h，得到Ti3C2Tx/MWNT/PANI粉体；(7) Centrifuge the Ti 3 C 2 T x /MWNT/PANI composite dispersion obtained in step (6) at 8000r/min for 15 minutes, wash with water 3 times, and freeze-dry for 48 hours to obtain Ti 3 C 2 T x /MWNT/PANI powder body;
(8)将50mg步骤(7)得到的粉体分散在1.5ml乙醇中，并加入6.25mg炭黑和4.1μlPTFE，400W超声10min，之后涂覆于石墨纸衬底上，在真空干燥箱中60℃干燥24h，烘干后即得到Ti3C2Tx/MWNT/PANI基电极材料。(8) Disperse 50 mg of the powder obtained in step (7) in 1.5 ml of ethanol, add 6.25 mg of carbon black and 4.1 μl of PTFE, ultrasonicate at 400 W for 10 min, and then apply it on a graphite paper substrate and place it in a vacuum oven for 60 ℃ drying for 24 hours, and the Ti 3 C 2 T x /MWNT/PANI-based electrode material can be obtained after drying.
实施例2Example 2
一种Ti3C2Tx基电极材料的制备方法，其特征在于，包括以下步骤：A method for preparing a Ti3C2Tx - based electrode material, characterized in that it comprises the following steps:
(1)Ti3C2Tx分散液的制备：取15mL的12M HCl注入50mL的试管中，加入1g的LiF溶解，得到刻蚀液；然后，将1g的Ti3AlC2加入到上述制备好的溶液中，摇匀，将试管置于60℃水浴锅中反应72h，反应结束后，用去离子水离心洗涤三次、5000rpm离心5min，得到Ti3C2Tx粉末，再将Ti3C2Tx粉末分散到水中即得所述Ti3C2Tx分散液。(1) Preparation of Ti 3 C 2 T x dispersion: Take 15mL of 12M HCl and inject it into a 50mL test tube, add 1g of LiF to dissolve to obtain an etching solution; then, add 1g of Ti 3 AlC 2 to the above prepared solution, shake well, and place the test tube in a 60°C water bath for 72 hours of reaction. After the reaction, centrifuge three times with deionized water and centrifuge at 5000rpm for 5 minutes to obtain Ti 3 C 2 T x powder, and then Ti 3 C 2 The T x powder is dispersed in water to obtain the Ti 3 C 2 T x dispersion.
(2)将步骤(1)制备的Ti3C2Tx分散液在300W细胞破碎仪中超声3h，3500r/min离心30min，去除沉淀，取上清液稀释至5mg mL-1得到Ti3C2Tx分散溶液；(2) Sonicate the Ti 3 C 2 T x dispersion prepared in step (1) in a 300W cell disruptor for 3h, centrifuge at 3500r/min for 30min, remove the precipitate, take the supernatant and dilute to 5mg mL -1 to obtain Ti 3 C 2 T x dispersion solution;
(3)向2.4ml步骤(2)所得Ti3C2Tx分散溶液中加入28mgMWNT，加水稀释至20ml、400W超声15min，在500r/min下搅拌4h后，得到Ti3C2Tx/MWNT复合物分散液，并加入1ml浓盐酸；(3) Add 28 mg MWNT to 2.4 ml of the Ti 3 C 2 T x dispersion solution obtained in step (2), dilute with water to 20 ml, 400W ultrasonic for 15 min, and stir at 500 r/min for 4 h to obtain Ti 3 C 2 T x /MWNT Complex dispersion, and add 1ml concentrated hydrochloric acid;
(4)取100ml四氯化碳与1ml苯胺单体，倒入烧杯中，混合均匀；(4) Take 100ml of carbon tetrachloride and 1ml of aniline monomer, pour them into a beaker, and mix well;
(5)称取0.276mg过硫酸铵，加入1.5ml去离子水，震荡均匀；(5) Weigh 0.276mg of ammonium persulfate, add 1.5ml of deionized water, and shake evenly;
(6)将步骤(3)与步骤(4)所得到的溶液混合，之后加入步骤(5)过硫酸铵水溶液，25℃下反应10h，得到Ti3C2Tx/MWNT/PANI复合物分散液；(6) Mix the solution obtained in step (3) with step (4), then add the aqueous solution of ammonium persulfate in step (5), and react at 25°C for 10 hours to obtain a Ti 3 C 2 T x /MWNT/PANI composite dispersion liquid;
(7)将步骤(6)所得Ti3C2Tx/MWNT/PANI复合物分散液，8000r/min离心15min、水洗3次、冷冻干燥48h，得到Ti3C2Tx/MWNT/PANI粉体；(7) Centrifuge the Ti 3 C 2 T x /MWNT/PANI composite dispersion obtained in step (6) at 8000r/min for 15 minutes, wash with water 3 times, and freeze-dry for 48 hours to obtain Ti 3 C 2 T x /MWNT/PANI powder body;
(8)将50mg步骤(7)得到的粉体分散在1.5ml乙醇中，并加入6.25mg炭黑和4.1μlPTFE，400W超声10min，之后涂覆于石墨纸衬底上，在真空干燥箱中60℃干燥24h，烘干后即得到Ti3C2Tx/MWNT/PANI基电极材料。(8) Disperse 50 mg of the powder obtained in step (7) in 1.5 ml of ethanol, add 6.25 mg of carbon black and 4.1 μl of PTFE, ultrasonicate at 400 W for 10 min, and then apply it on a graphite paper substrate and place it in a vacuum oven for 60 ℃ drying for 24 hours, and the Ti 3 C 2 T x /MWNT/PANI-based electrode material can be obtained after drying.
将本实施例所制备的样品用于电容去离子性能研究。The samples prepared in this embodiment were used for the research on capacitive deionization performance.
根据表1所示，对于不同浓度的NaCl溶液，在2000mg·L-1时，材料的吸附容量达到最大值210mg·g-1，而吸附速率则是在1000mg·L-1时达到最高值。According to Table 1, for different concentrations of NaCl solutions, the adsorption capacity of the material reaches the maximum value of 210 mg·g -1 at 2000 mg·L -1 , and the adsorption rate reaches the highest value at 1000 mg·L -1 .
实施例3Example 3
一种Ti3C2Tx基电极材料的制备方法，其特征在于，包括以下步骤：A method for preparing a Ti3C2Tx - based electrode material, characterized in that it comprises the following steps:
(1)Ti3C2Tx分散液的制备：取15mL的12M HCl注入50mL的试管中，加入1g的LiF溶解，得到刻蚀液；然后，将1g的Ti3AlC2加入到上述制备好的溶液中，摇匀，将试管置于60℃水浴锅中反应72h，反应结束后，用去离子水离心洗涤三次、5000rpm离心5min，得到Ti3C2Tx粉末，再将Ti3C2Tx粉末分散到水中即得所述Ti3C2Tx分散液。(1) Preparation of Ti 3 C 2 T x dispersion: Take 15mL of 12M HCl and inject it into a 50mL test tube, add 1g of LiF to dissolve to obtain an etching solution; then, add 1g of Ti 3 AlC 2 to the above prepared solution, shake well, and place the test tube in a 60°C water bath for 72 hours of reaction. After the reaction, centrifuge three times with deionized water and centrifuge at 5000rpm for 5 minutes to obtain Ti 3 C 2 T x powder, and then Ti 3 C 2 The T x powder is dispersed in water to obtain the Ti 3 C 2 T x dispersion.
(2)将步骤(1)制备的Ti3C2Tx分散液在300W细胞破碎仪中超声3h，3500r/min离心30min，去除沉淀，取上清液稀释至5mg mL-1得到Ti3C2Tx分散溶液；(2) Sonicate the Ti 3 C 2 T x dispersion prepared in step (1) in a 300W cell disruptor for 3h, centrifuge at 3500r/min for 30min, remove the precipitate, take the supernatant and dilute to 5mg mL -1 to obtain Ti 3 C 2 T x dispersion solution;
(3)向4ml步骤(2)所得Ti3C2Tx分散溶液中加入20mgMWNT，加水稀释至20ml、400W超声15min，在500r/min下搅拌4h后，得到Ti3C2Tx/MWNT复合物分散液，并加入1ml浓盐酸；(3) Add 20 mg MWNT to 4 ml of the Ti 3 C 2 T x dispersion solution obtained in step (2), dilute with water to 20 ml, 400W ultrasonic for 15 min, and stir at 500 r/min for 4 h to obtain a Ti 3 C 2 T x /MWNT composite material dispersion, and add 1ml of concentrated hydrochloric acid;
(4)取100ml四氯化碳与1ml苯胺单体，倒入烧杯中，混合均匀；(4) Take 100ml of carbon tetrachloride and 1ml of aniline monomer, pour them into a beaker, and mix well;
(5)称取0.276mg过硫酸铵，加入1.5ml去离子水，震荡均匀；(5) Weigh 0.276mg of ammonium persulfate, add 1.5ml of deionized water, and shake evenly;
(6)将步骤(3)与步骤(4)所得到的溶液混合，之后加入步骤(5)过硫酸铵水溶液，25℃下反应10h，得到Ti3C2Tx/MWNT/PANI复合物分散液；(6) Mix the solution obtained in step (3) with step (4), then add the aqueous solution of ammonium persulfate in step (5), and react at 25°C for 10 hours to obtain a Ti 3 C 2 T x /MWNT/PANI composite dispersion liquid;
(7)将步骤(6)所得Ti3C2Tx/MWNT/PANI复合物分散液，8000r/min离心15min、水洗3次、冷冻干燥48h，得到Ti3C2Tx/MWNT/PANI粉体；(7) Centrifuge the Ti 3 C 2 T x /MWNT/PANI composite dispersion obtained in step (6) at 8000r/min for 15 minutes, wash with water 3 times, and freeze-dry for 48 hours to obtain Ti 3 C 2 T x /MWNT/PANI powder body;
(8)将50mg步骤(7)得到的粉体分散在1.5ml乙醇中，并加入6.25mg炭黑和4.1μlPTFE，400W超声10min，之后涂覆于石墨纸衬底上，在真空干燥箱中60℃干燥24h，烘干后即得到Ti3C2Tx/MWNT/PANI基电极材料。(8) Disperse 50 mg of the powder obtained in step (7) in 1.5 ml of ethanol, add 6.25 mg of carbon black and 4.1 μl of PTFE, ultrasonicate at 400 W for 10 min, and then apply it on a graphite paper substrate and place it in a vacuum oven for 60 ℃ drying for 24 hours, and the Ti 3 C 2 T x /MWNT/PANI-based electrode material can be obtained after drying.
将取出的样品通过扫描电镜、X射线光电子能谱等进行分析观察，并将样品用于电容去离子性能研究。The samples taken out were analyzed and observed by scanning electron microscopy, X-ray photoelectron spectroscopy, etc., and the samples were used for capacitive deionization performance research.
根据图1和图2，Ti3C2Tx、MWNT与PANI三者成功的复合在一起，MWNT在Ti3C2T的表面与层间，构成层间网络，起到促进电子运输的作用。根据表1，对于不同浓度的NaCl溶液，在2000mg·L-1时，材料的吸附容量和吸附速率达到最大值分别为258mg·g-1和8.6mg·g-1·min-1，与实施例2所测数据相比，由于实例3中所含MWNT比例更高，在层间构建了更多的电子传输桥梁，比表面积更大，所以，实施例3所制备的电极材料的吸附容量更大，吸附速率高出两倍。According to Figure 1 and Figure 2, Ti 3 C 2 T x , MWNT and PANI are successfully compounded together. MWNT forms an interlayer network on the surface and interlayer of Ti 3 C 2 T, which plays a role in promoting electron transport. . According to Table 1, for different concentrations of NaCl solutions, at 2000 mg·L -1 , the adsorption capacity and adsorption rate of the material reach the maximum value of 258 mg·g -1 and 8.6 mg·g -1 ·min -1 , respectively. Compared with the measured data of Example 2, because the proportion of MWNT contained in Example 3 is higher, more electron transport bridges are built between the layers, and the specific surface area is larger, so the adsorption capacity of the prepared electrode material in Example 3 is higher. Larger, the adsorption rate is twice as high.
实施例4Example 4
一种Ti3C2Tx基电极材料的制备方法，其特征在于，包括以下步骤：A method for preparing a Ti3C2Tx - based electrode material, characterized in that it comprises the following steps:
(1)Ti3C2Tx分散液的制备：取15mL的12M HCl注入50mL的试管中，加入1g的LiF溶解，得到刻蚀液；然后，将1g的Ti3AlC2加入到上述制备好的溶液中，摇匀，将试管置于60℃水浴锅中反应72h，反应结束后，用去离子水离心洗涤三次、5000rpm离心5min，得到Ti3C2Tx粉末，再将Ti3C2Tx粉末分散到水中即得所述Ti3C2Tx分散液。(1) Preparation of Ti 3 C 2 T x dispersion: Take 15mL of 12M HCl and inject it into a 50mL test tube, add 1g of LiF to dissolve to obtain an etching solution; then, add 1g of Ti 3 AlC 2 to the above prepared solution, shake well, and place the test tube in a 60°C water bath for 72 hours of reaction. After the reaction, centrifuge three times with deionized water and centrifuge at 5000rpm for 5 minutes to obtain Ti 3 C 2 T x powder, and then Ti 3 C 2 The T x powder is dispersed in water to obtain the Ti 3 C 2 T x dispersion.
(2)将步骤(1)制备的Ti3C2Tx分散液在300W细胞破碎仪中超声3h，3500r/min离心30min，去除沉淀，取上清液稀释至5mg mL-1得到Ti3C2Tx分散溶液；(2) Sonicate the Ti 3 C 2 T x dispersion prepared in step (1) in a 300W cell disruptor for 3h, centrifuge at 3500r/min for 30min, remove the precipitate, take the supernatant and dilute to 5mg mL -1 to obtain Ti 3 C 2 T x dispersion solution;
(3)向5.6ml步骤(2)所得Ti3C2Tx分散溶液中加入12mgMWNT，加水稀释至20ml、400W超声15min，在500r/min下搅拌4h后，得到Ti3C2Tx/MWNT复合物分散液，并加入1ml浓盐酸；(3) Add 12 mg MWNT to 5.6 ml of the Ti 3 C 2 T x dispersion solution obtained in step (2), dilute with water to 20 ml, 400W ultrasonic for 15 min, and stir at 500 r/min for 4 h to obtain Ti 3 C 2 T x /MWNT Complex dispersion, and add 1ml concentrated hydrochloric acid;
(4)取100ml四氯化碳与1ml苯胺单体，倒入烧杯中，混合均匀；(4) Take 100ml of carbon tetrachloride and 1ml of aniline monomer, pour them into a beaker, and mix well;
(5)称取0.276mg过硫酸铵，加入1.5ml去离子水，震荡均匀；(5) Weigh 0.276mg of ammonium persulfate, add 1.5ml of deionized water, and shake evenly;
(6)将步骤(3)与步骤(4)所得到的溶液混合，之后加入步骤(5)过硫酸铵水溶液，25℃下反应10h，得到Ti3C2Tx/MWNT/PANI复合物分散液；(6) Mix the solution obtained in step (3) with step (4), then add the aqueous solution of ammonium persulfate in step (5), and react at 25°C for 10 hours to obtain a Ti 3 C 2 T x /MWNT/PANI composite dispersion liquid;
(7)将步骤(6)所得Ti3C2Tx/MWNT/PANI复合物分散液，8000r/min离心15min、水洗3次、冷冻干燥48h，得到Ti3C2Tx/MWNT/PANI粉体；(7) Centrifuge the Ti 3 C 2 T x /MWNT/PANI composite dispersion obtained in step (6) at 8000r/min for 15 minutes, wash with water 3 times, and freeze-dry for 48 hours to obtain Ti 3 C 2 T x /MWNT/PANI powder body;
(8)将50mg步骤(7)得到的粉体分散在1.5ml乙醇中，并加入6.25mg炭黑和4.1μlPTFE，400W超声10min，之后涂覆于石墨纸衬底上，在真空干燥箱中60℃干燥24h，烘干后即得到Ti3C2Tx/MWNT/PANI基电极材料。(8) Disperse 50 mg of the powder obtained in step (7) in 1.5 ml of ethanol, add 6.25 mg of carbon black and 4.1 μl of PTFE, ultrasonicate at 400 W for 10 min, and then apply it on a graphite paper substrate and place it in a vacuum oven for 60 ℃ drying for 24 hours, and the Ti 3 C 2 T x /MWNT/PANI-based electrode material can be obtained after drying.
实施例5Example 5
一种Ti3C2Tx基电极材料的制备方法，其特征在于，包括以下步骤：A method for preparing a Ti3C2Tx - based electrode material, characterized in that it comprises the following steps:
(1)Ti3C2Tx分散液的制备：取15mL的12M HCl注入50mL的试管中，加入1g的LiF溶解，得到刻蚀液；然后，将1g的Ti3AlC2加入到上述制备好的溶液中，摇匀，将试管置于60℃水浴锅中反应72h，反应结束后，用去离子水离心洗涤三次、5000rpm离心5min，得到Ti3C2Tx粉末，再将Ti3C2Tx粉末分散到水中即得所述Ti3C2Tx分散液。(1) Preparation of Ti 3 C 2 T x dispersion: Take 15mL of 12M HCl and inject it into a 50mL test tube, add 1g of LiF to dissolve to obtain an etching solution; then, add 1g of Ti 3 AlC 2 to the above prepared solution, shake well, and place the test tube in a 60°C water bath for 72 hours of reaction. After the reaction, centrifuge three times with deionized water and centrifuge at 5000rpm for 5 minutes to obtain Ti 3 C 2 T x powder, and then Ti 3 C 2 The T x powder is dispersed in water to obtain the Ti 3 C 2 T x dispersion.
(2)将步骤(1)制备的Ti3C2Tx分散液在300W细胞破碎仪中超声3h，3500r/min离心30min，去除沉淀，取上清液稀释至5mg mL-1得到Ti3C2Tx分散溶液；(2) Sonicate the Ti 3 C 2 T x dispersion prepared in step (1) in a 300W cell disruptor for 3h, centrifuge at 3500r/min for 30min, remove the precipitate, take the supernatant and dilute to 5mg mL -1 to obtain Ti 3 C 2 T x dispersion solution;
(3)向7.2ml步骤(2)所得Ti3C2Tx分散溶液中加入4mgMWNT，加水稀释至20ml、400W超声15min，在500r/min下搅拌4h后，得到Ti3C2Tx/MWNT复合物分散液，并加入1ml浓盐酸；(3) Add 4 mg MWNT to 7.2 ml of Ti 3 C 2 T x dispersion solution obtained in step (2), dilute with water to 20 ml, 400W ultrasonic for 15 min, and stir at 500 r/min for 4 h to obtain Ti 3 C 2 T x /MWNT Complex dispersion, and add 1ml concentrated hydrochloric acid;
(4)取100ml四氯化碳与1ml苯胺单体，倒入烧杯中，混合均匀；(4) Take 100ml of carbon tetrachloride and 1ml of aniline monomer, pour them into a beaker, and mix well;
(5)称取0.276mg过硫酸铵，加入1.5ml去离子水，震荡均匀；(5) Weigh 0.276mg of ammonium persulfate, add 1.5ml of deionized water, and shake evenly;
(6)将步骤(3)与步骤(4)所得到的溶液混合，之后加入步骤(5)过硫酸铵水溶液，25℃下反应10h，得到Ti3C2Tx/MWNT/PANI复合物分散液；(6) Mix the solution obtained in step (3) with step (4), then add the aqueous solution of ammonium persulfate in step (5), and react at 25°C for 10 hours to obtain a Ti 3 C 2 T x /MWNT/PANI composite dispersion liquid;
(7)将步骤(6)所得Ti3C2Tx/MWNT/PANI复合物分散液，8000r/min离心15min、水洗3次、冷冻干燥48h，得到Ti3C2Tx/MWNT/PANI粉体；(7) Centrifuge the Ti 3 C 2 T x /MWNT/PANI composite dispersion obtained in step (6) at 8000r/min for 15 minutes, wash with water 3 times, and freeze-dry for 48 hours to obtain Ti 3 C 2 T x /MWNT/PANI powder body;
(8)将50mg步骤(7)得到的粉体分散在1.5ml乙醇中，并加入6.25mg炭黑和4.1μlPTFE，400W超声10min，之后涂覆于石墨纸衬底上，在真空干燥箱中60℃干燥24h，烘干后即得到Ti3C2Tx/MWNT/PANI基电极材料。(8) Disperse 50 mg of the powder obtained in step (7) in 1.5 ml of ethanol, add 6.25 mg of carbon black and 4.1 μl of PTFE, ultrasonicate at 400 W for 10 min, and then apply it on a graphite paper substrate and place it in a vacuum oven for 60 ℃ drying for 24 hours, and the Ti 3 C 2 T x /MWNT/PANI-based electrode material can be obtained after drying.
对比例1Comparative example 1
一种Ti3C2Tx基电极材料的制备方法，其特征在于，包括以下步骤：A method for preparing a Ti3C2Tx - based electrode material, characterized in that it comprises the following steps:
(1)Ti3C2Tx分散液的制备：取15mL的12M HCl注入50mL的试管中，加入1g的LiF溶解，得到刻蚀液；然后，将1g的Ti3AlC2加入到上述制备好的溶液中，摇匀，将试管置于60℃水浴锅中反应72h，反应结束后，用去离子水离心洗涤三次、5000rpm离心5min，得到Ti3C2Tx粉末，再将Ti3C2Tx粉末分散到水中即得所述Ti3C2Tx分散液。(1) Preparation of Ti 3 C 2 T x dispersion: Take 15mL of 12M HCl and inject it into a 50mL test tube, add 1g of LiF to dissolve to obtain an etching solution; then, add 1g of Ti 3 AlC 2 to the above prepared solution, shake well, and place the test tube in a 60°C water bath for 72 hours of reaction. After the reaction, centrifuge three times with deionized water and centrifuge at 5000rpm for 5 minutes to obtain Ti 3 C 2 T x powder, and then Ti 3 C 2 The T x powder is dispersed in water to obtain the Ti 3 C 2 T x dispersion.
(2)将步骤(1)制备的Ti3C2Tx分散液在300W细胞破碎仪中超声3h，3500r/min离心30min，去除沉淀，取上清液得到Ti3C2Tx分散溶液；(2) Sonicate the Ti 3 C 2 T x dispersion prepared in step (1) in a 300W cell disruptor for 3 hours, centrifuge at 3500 r/min for 30 min, remove the precipitate, and take the supernatant to obtain a Ti 3 C 2 T x dispersion;
(3)将步骤(2)所得Ti3C2Tx分散液，冷冻干燥48h，得到Ti3C2Tx粉体；(3) Freeze-dry the Ti 3 C 2 T x dispersion obtained in step (2) for 48 hours to obtain Ti 3 C 2 T x powder;
(4)将50mg步骤(3)得到的粉体分散在1.5ml乙醇中，并加入6.25mg炭黑和4.1μlPTFE，400W超声10min，之后涂覆于石墨纸衬底上，在真空干燥箱中60℃干燥24h，烘干后即得到Ti3C2Tx基电极材料。(4) Disperse 50 mg of the powder obtained in step (3) in 1.5 ml of ethanol, add 6.25 mg of carbon black and 4.1 μl of PTFE, ultrasonicate at 400 W for 10 min, and then coat it on a graphite paper substrate and place it in a vacuum oven for 60 °C for 24 hours, and the Ti 3 C 2 T x -based electrode material can be obtained after drying.
将本实施例2-3以及对比例1所制备的样品用于电容去离子性能研究。CDI性能测试方法：The samples prepared in Examples 2-3 and Comparative Example 1 were used for capacitive deionization performance research. CDI performance test method:
(1)涂覆前称量石墨纸的质量，涂氟烘干后得到电极材料的质量；(1) weigh the quality of the graphite paper before coating, and obtain the quality of the electrode material after fluorine-coating and drying;
(2)配置100-3000mg·ml-1的NaCl溶液200ml；(2) Configure 200ml of NaCl solution of 100-3000mg·ml -1 ;
(3)采用实施例2-3以及对比例1所制备的样品作为负极，以活性炭电极为正极，按照图3所示连接各设备；(3) adopt the sample prepared by embodiment 2-3 and comparative example 1 as the negative pole, take the activated carbon electrode as the positive pole, connect each equipment as shown in Figure 3;
(4)使用电化学工作站提供电压1.2V；(4) Use an electrochemical workstation to provide a voltage of 1.2V;
(5)打开蠕动泵，出水后开始运行电导率仪，在运行电化学工作站；(5) Turn on the peristaltic pump, start running the conductivity meter after the water comes out, and run the electrochemical workstation;
(6)通过电导率仪来获得溶液浓度，并计算材料的吸附容量和吸附速率，计算公式如下：(6) Obtain the solution concentration through a conductivity meter, and calculate the adsorption capacity and adsorption rate of the material. The calculation formula is as follows:
表1实施例2-3以及对比例1所制备电极材料的电容去离子性能测试数据表Table 1 embodiment 2-3 and the capacitive deionization performance test data table of the prepared electrode material of comparative example 1
根据表1所示，纯Ti3C2Tx基电极材料的吸附容量仅有18mg·g-1，吸附速率仅为1mg·g-1·min-1，有待提升。According to Table 1, the adsorption capacity of pure Ti 3 C 2 T x based electrode material is only 18 mg·g -1 , and the adsorption rate is only 1 mg·g -1 ·min -1 , which needs to be improved.
最后需要说明的是：以上实施例不以任何形式限制本发明。对本领域技术人员来说，在本发明基础上，可以对其作一些修改和改进。因此，凡在不偏离本发明精神的基础上所做的任何修改或改进，均属于本发明要求保护的范围之内。Finally, it should be noted that the above embodiments do not limit the present invention in any form. For those skilled in the art, some modifications and improvements can be made on the basis of the present invention. Therefore, any modification or improvement made on the basis of not departing from the spirit of the present invention falls within the protection scope of the present invention.
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