技术领域technical field
本发明属于电化学领域，尤其涉及一种钛基二氧化钛纳米管复合阳极及其制备方法。The invention belongs to the field of electrochemistry, and in particular relates to a titanium-based titanium dioxide nanotube composite anode and a preparation method thereof.
背景技术Background technique
金属氧化物阳极又称为形稳阳极DSA，由H.B.Beer发明，由意大利De Nora公司首先实现工业化生产(钛电极工学，北京：冶金工业出版社，2003)，其中金属基体起导电和骨架作用，表面活性涂层则参加阳极的电化学反应。目前，DSA已经广泛应用于电冶金工业、氯碱工业、电镀、废水处理等。The metal oxide anode, also known as the shape-stable anode DSA, was invented by H.B.Beer and was first industrialized by the Italian company De Nora (Titanium Electrode Engineering, Beijing: Metallurgical Industry Press, 2003), in which the metal matrix acts as a conductor and a skeleton. The surface active coating participates in the electrochemical reaction of the anode. At present, DSA has been widely used in electrometallurgy industry, chlor-alkali industry, electroplating, wastewater treatment, etc.
法国科学家Zwilling V等于1999年首次报道了通过阳极氧化法在钛板上制备二氧化钛纳米管的工作，到现在阳极氧化法已经成为制备二氧化钛纳米管重要的方法之一。纳米二氧化钛作为一种无机功能材料，在太阳能的存储与应用、光电转化、光催化降解大气以及水中的污染物等方面得到了广泛的应用，并且在钛阳极中也得到了初步的应用。French scientist Zwilling V et al. first reported the preparation of titanium dioxide nanotubes on titanium plates by anodic oxidation in 1999. Up to now, anodic oxidation has become one of the important methods for preparing titanium dioxide nanotubes. As an inorganic functional material, nano-titanium dioxide has been widely used in the storage and application of solar energy, photoelectric conversion, photocatalytic degradation of pollutants in the atmosphere and water, and has also been initially used in titanium anodes.
虽然钛基复合阳极的制备方法多种多样，工艺简单，涂层的催化活性高，选择性好，但是有一个致命的缺点：使用寿命较短，容易钝化形成一层导电性很差的二氧化钛膜。近年来众多研究者为了解决这一问题，主要提出了以下几种方案：第一种是采用热涂覆增加中间层的方法，一般为二氧化锡中间层，增加基体与涂层间的结合力，使得整个涂层致密，而增加对溶液中氧的抵抗力，但是增加中间层只是在一定程度上增加了涂覆层与基体的物理结合力，未能从根本上阻挡溶液中氧从涂层的裂缝中对基体的侵蚀；第二种是采用将钛与其它金属形成钛合金，如电解二氧化锰里面应用十分广泛的钛锰合金，其表面的氧化膜为钛锰复合氧化物，其耐腐蚀性大大提高，但是这种方法的制作工艺复杂，一致性较差；第三种是引入稀有金属催化层，但是稀有金属的催化作用只能应用于特定领域，并且其使用成本过高，而且引入二氧化钛纳米管中间层来增加电极的抗腐蚀能力，这种预先在电极表面引入薄的致密中间层的方法虽然能大大增加钛阳极的使用寿命，但是即使是二氧化钛纳米管其导电性仍然较差，从而导致在整个涂层上面的压降较大，能耗增加。因此，目前的这些技术方案都无法从根本上解决钛基复合阳极使用寿命短的技术缺陷。Although the preparation methods of titanium-based composite anodes are various, the process is simple, the coating has high catalytic activity and good selectivity, but there is a fatal disadvantage: short service life and easy passivation to form a layer of titanium dioxide with poor conductivity. membrane. In recent years, in order to solve this problem, many researchers have mainly proposed the following schemes: The first is to use thermal coating to increase the intermediate layer, usually a tin dioxide intermediate layer, to increase the bonding force between the substrate and the coating , making the entire coating denser, and increasing the resistance to oxygen in the solution, but adding the middle layer only increases the physical bonding force between the coating layer and the substrate to a certain extent, and fails to fundamentally block the oxygen in the solution from the coating. The corrosion of the substrate in cracks; the second is to use titanium and other metals to form titanium alloys, such as titanium-manganese alloys that are widely used in electrolytic manganese dioxide, and the oxide film on the surface is titanium-manganese composite oxides. Corrosion is greatly improved, but the manufacturing process of this method is complicated and the consistency is poor; the third is to introduce a rare metal catalytic layer, but the catalytic effect of rare metals can only be applied to specific fields, and its use cost is too high, and The introduction of a titanium dioxide nanotube intermediate layer to increase the corrosion resistance of the electrode, although this method of introducing a thin and dense intermediate layer on the electrode surface in advance can greatly increase the service life of the titanium anode, but even the titanium dioxide nanotubes still have poor conductivity , resulting in a larger pressure drop across the coating and increased energy consumption. Therefore, none of these current technical solutions can fundamentally solve the technical defect of short service life of titanium-based composite anodes.
发明内容Contents of the invention
本发明所要解决的技术问题是，克服以上背景技术中提到的不足和缺陷，提供一种超长寿命的钛基二氧化钛纳米管复合阳极及其制备方法。The technical problem to be solved by the present invention is to overcome the deficiencies and defects mentioned in the background technology above, and provide a titanium-based titanium dioxide nanotube composite anode with an ultra-long life and a preparation method thereof.
为解决上述技术问题，本发明提出的技术方案为：In order to solve the problems of the technologies described above, the technical solution proposed by the present invention is:
一种钛基二氧化钛纳米管复合阳极，包括钛基体层、二氧化钛纳米管阵列中间层和活性表面层；所述二氧化钛纳米管阵列中间层中沉积有金属锰。A titanium-based titanium dioxide nanotube composite anode comprises a titanium matrix layer, a titanium dioxide nanotube array middle layer and an active surface layer; metal manganese is deposited in the titanium dioxide nanotube array middle layer.
上述的钛基二氧化钛纳米管复合阳极，优选的，所述活性表面层为SnO2、MnO2、IrO2、PbO2、PdO2和RuO2中的一种或几种金属氧化物混合层。In the aforementioned titanium-based titanium dioxide nanotube composite anode, preferably, the active surface layer is a mixed layer of one or more metal oxides among SnO2 , MnO2 , IrO2 , PbO2 , PdO2 and RuO2 .
上述的钛基二氧化钛纳米管复合阳极，优选的，所述钛基体层为金属钛板、钛合金或钛薄片。In the aforementioned titanium-based titanium dioxide nanotube composite anode, preferably, the titanium matrix layer is a metal titanium plate, titanium alloy or titanium sheet.
作为一个总的发明构思，本发明还提供一种钛基二氧化钛纳米管复合阳极的制备方法，包括以下步骤：As a general inventive concept, the present invention also provides a method for preparing a titanium-based titanium dioxide nanotube composite anode, comprising the following steps:
(1)对钛基体进行预处理；(1) pretreating the titanium substrate;
(2)将预处理后的钛基体作为阳极，石墨作为阴极，放入阳极氧化液中，阳极氧化5～20h，使钛基体表面原位生长出二氧化钛纳米管阵列，得到钛基体/二氧化钛纳米管阵列；(2) Put the pretreated titanium substrate as the anode and the graphite as the cathode, put it into the anodic oxidation solution, anodize for 5-20 hours, and grow the titanium dioxide nanotube array on the surface of the titanium substrate in situ, and obtain the titanium substrate/titanium dioxide nanotube array;
(3)将所述钛基体/二氧化钛纳米管阵列清洗干净后，作为阴极，再以石墨为阳极，在氨性电解锰溶液中电解5～25min，使金属锰沉积在二氧化钛纳米管阵列中；(3) After cleaning the titanium matrix/titanium dioxide nanotube array, use it as a cathode, then use graphite as an anode, and electrolyze it in an ammoniacal electrolytic manganese solution for 5 to 25 minutes, so that metal manganese is deposited in the titanium dioxide nanotube array;
(4)将锡、锰、铱、铅、钯或钌的盐溶液中的一种或者几种涂覆在步骤(3)沉积有金属锰的二氧化钛纳米管阵列表面，然后进行焙烧，得到所述钛基二氧化钛纳米管复合阳极。(4) One or more of the salt solutions of tin, manganese, iridium, lead, palladium or ruthenium are coated on the surface of the titanium dioxide nanotube array deposited with metal manganese in step (3), and then roasted to obtain the described Titanium-based titanium dioxide nanotube composite anode.
上述的制备方法，优选的，所述步骤(2)中，阳极氧化的电压为30～50V，阳极氧化反应时间为8～20h。In the above preparation method, preferably, in the step (2), the anodic oxidation voltage is 30-50V, and the anodic oxidation reaction time is 8-20h.
上述的制备方法，优选的，所述步骤(3)中，氨性电解锰溶液中二价锰的浓度为10～20g/L，硫酸铵浓度为100～120g/L，电解锰溶液的pH为7～8。The above-mentioned preparation method, preferably, in the step (3), the concentration of divalent manganese in the ammoniacal electrolytic manganese solution is 10-20g/L, the concentration of ammonium sulfate is 100-120g/L, and the pH of the electrolytic manganese solution is 7-8.
上述的制备方法，优选的，所述步骤(3)中的清洗过程是指用去离子水和酒精交替洗涤数次。优选的，交替洗涤的次数为3次。In the above preparation method, preferably, the cleaning process in the step (3) refers to alternately washing several times with deionized water and alcohol. Preferably, the number of times of alternate washing is 3 times.
上述的制备方法，优选的，所述步骤(4)中的涂覆和焙烧过程需重复10～15次。In the above preparation method, preferably, the coating and firing process in the step (4) needs to be repeated 10-15 times.
上述的制备方法，优选的，所述步骤(1)中，钛基体的预处理过程具体包括：先将钛基体进行打磨抛光，再对打磨抛光后的钛基体进行清洗，最后放入HF和HNO3混酸溶液中进行浸蚀处理。In the above preparation method, preferably, in the step (1), the pretreatment process of the titanium substrate specifically includes: first grinding and polishing the titanium substrate, then cleaning the polished titanium substrate, and finally putting HF and HNO3 Etching treatment in mixed acid solution.
与现有技术相比，本发明的优点在于：Compared with the prior art, the present invention has the advantages of:
(1)本发明的钛基二氧化钛纳米管复合阳极中，纳米二氧化钛层是同步原位生成的，与钛基体件连接十分致密，没有裂缝的出现，可以有效抑制溶液中的氧直接侵蚀钛基体而钝化。(1) In the titanium-based titanium dioxide nanotube composite anode of the present invention, the nano-titanium dioxide layer is generated synchronously in situ, and is very densely connected with the titanium matrix, without the appearance of cracks, which can effectively inhibit the oxygen in the solution from directly corroding the titanium matrix. passivation.
(2)本发明的钛基二氧化钛纳米管复合阳极中，金属锰直接生长在二氧化钛纳米管中，相比较现有技术的表面涂覆法，极大地促进了钛锰混合；并且在焙烧后，部分锰进入二氧化钛晶格中，并且增加了晶格中三价钛的含量，从而增大二氧化钛层的导电性，降低阳极压降，减少能耗。(2) In the titanium-based titania nanotube composite anode of the present invention, metal manganese is directly grown in the titania nanotube, which greatly promotes the mixing of titanium and manganese compared with the surface coating method of the prior art; and after roasting, part Manganese enters the titanium dioxide lattice, and increases the content of trivalent titanium in the lattice, thereby increasing the conductivity of the titanium dioxide layer, reducing the anode voltage drop, and reducing energy consumption.
(3)本发明的钛基二氧化钛纳米管复合阳极的使用寿命远比普通的复合电极长。(3) The service life of the titanium-based titanium dioxide nanotube composite anode of the present invention is much longer than that of ordinary composite electrodes.
(4)本发明的钛基二氧化钛纳米管复合阳极可以直接应用于电解锰阳极，再沉积足够多的锰后，加热后会在表面直接形成二氧化锰活性层，制作方法简单高效，并且十分致密。作为阳极使用时，不会在电池材料中引入有害杂质，并且可以收集阳极的副产物二氧化锰，做进一步深加工。(4) The titanium-based titanium dioxide nanotube composite anode of the present invention can be directly applied to the electrolytic manganese anode. After depositing enough manganese, an active layer of manganese dioxide will be formed directly on the surface after heating. The manufacturing method is simple, efficient and very dense. . When used as an anode, no harmful impurities will be introduced into the battery material, and manganese dioxide, a by-product of the anode, can be collected for further processing.
(5)本发明的钛基二氧化钛纳米管复合阳极的制备过程对环境友好，不产生有毒气体污染环境。(5) The preparation process of the titanium-based titanium dioxide nanotube composite anode of the present invention is environmentally friendly and does not produce toxic gas to pollute the environment.
附图说明Description of drawings
图1为本发明的钛基二氧化钛纳米管复合阳极的结构示意图。FIG. 1 is a schematic structural view of the titanium-based titanium dioxide nanotube composite anode of the present invention.
图2为本发明实施例1制备的钛基二氧化钛纳米管复合阳极中的二氧化钛纳米管扫描电镜图.Figure 2 is a scanning electron micrograph of titanium dioxide nanotubes in the titanium-based titanium dioxide nanotube composite anode prepared in Example 1 of the present invention.
图3为本发明实施例2制备的钛基二氧化钛纳米管复合阳极与传统的Ti/MnO2阳极、未沉积金属锰的钛基复合阳极的强化寿命测试比较图。Fig. 3 is a comparison chart of the enhanced life test of the titanium-based titanium dioxide nanotube composite anode prepared in Example 2 of the present invention and the traditional Ti/MnO2 anode and the titanium-based composite anode without metal manganese deposition.
图4为本发明实施例3制备的钛基二氧化钛纳米管复合阳极与未沉积金属锰的钛基复合阳极氧化比较图。Fig. 4 is an oxidation comparison diagram of the titanium-based titanium dioxide nanotube composite anode prepared in Example 3 of the present invention and the titanium-based composite anode without metal manganese deposition.
图5为本发明实施例4中性溶液体系制备的钛基二氧化钛纳米管复合阳极与未沉积金属锰的钛基复合阳极在电解锰中槽电压比较图。Fig. 5 is a comparison diagram of the cell voltage of the titanium-based titanium dioxide nanotube composite anode prepared by the neutral solution system in Example 4 of the present invention and the titanium-based composite anode without metal manganese deposition in electrolytic manganese.
图例说明：1、钛基体层；2、二氧化钛纳米管阵列中间层；3、活性表面层。Legend: 1. Titanium matrix layer; 2. Intermediate layer of titanium dioxide nanotube array; 3. Active surface layer.
具体实施方式Detailed ways
为了便于理解本发明，下文将结合说明书附图和较佳的实施例对本文发明做更全面、细致地描述，但本发明的保护范围并不限于以下具体实施例。In order to facilitate the understanding of the present invention, the invention will be described more comprehensively and in detail below in conjunction with the accompanying drawings and preferred embodiments, but the protection scope of the present invention is not limited to the following specific embodiments.
除非另有定义，下文中所使用的所有专业术语与本领域技术人员通常理解含义相同。本文中所使用的专业术语只是为了描述具体实施例的目的，并不是旨在限制本发明的保护范围。Unless otherwise defined, all technical terms used hereinafter have the same meanings as commonly understood by those skilled in the art. The terminology used herein is only for the purpose of describing specific embodiments, and is not intended to limit the protection scope of the present invention.
除非另有特别说明，本发明中用到的各种原材料、试剂、仪器和设备等均可通过市场购买得到或者可通过现有方法制备得到。Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.
实施例1：Example 1:
一种本发明的钛基二氧化钛纳米管复合阳极，其结构示意图如图1所示，包括钛基体层1、二氧化钛纳米管阵列中间层2和活性表面层3；其中钛基体层1为纯钛片，二氧化钛纳米管阵列中间层2中沉积有金属锰，活性表面层3为MnO2。A titanium-based titanium dioxide nanotube composite anode of the present invention, its structural schematic diagram is shown in Figure 1, comprises titanium matrix layer 1, titanium dioxide nanotube array intermediate layer 2 and active surface layer 3; Wherein titanium matrix layer 1 is pure titanium sheet , metal manganese is deposited in the middle layer 2 of the titanium dioxide nanotube array, and the active surface layer 3 is MnO2 .
本实施例的钛基二氧化钛纳米管复合阳极的制备方法，包括以下步骤：The preparation method of the titanium-based titanium dioxide nanotube composite anode of this embodiment comprises the following steps:
(1)选取纯钛片作为钛基体，将纯钛片依次用360#、600#、800#、1000#砂纸打磨抛光，再分别用丙酮、乙醇、去离子水分别超声清洗10min，最后将表面打磨光滑的钛片放入HF：HNO3＝1:2的混酸溶液中进行活化30s，清洗，烘干；(1) Select pure titanium sheet as the titanium substrate, grind and polish the pure titanium sheet with 360#, 600#, 800#, 1000# sandpaper in sequence, then ultrasonically clean the sheet with acetone, ethanol, and deionized water for 10 minutes, and finally clean the surface Put the polished and smooth titanium sheet into the mixed acid solution of HF:HNO3 =1:2 for activation for 30s, clean and dry;
(2)将步骤(1)预处理后的钛基体作为阳极，石墨作为阴极，放入氧化液(NH4F11.3g/L、丙三醇250mL和水250mL)中，在温度为55℃、电压为40V下氧化8h，使钛基体表面原位生长出分布均匀致密二氧化钛纳米管阵列(记钛基体/二氧化钛纳米管阵列)，纳米管的直径为90nm左右，用扫描电镜观察，其形貌如图2所示；(2) The titanium substrate pretreated in step (1) was used as the anode, graphite was used as the cathode, and put into the oxidation solution (NH4 F11.3g/L, glycerin 250mL and water 250mL), at a temperature of 55°C, The voltage is 40V and oxidized for 8h, so that the surface of the titanium substrate grows in situ uniformly distributed and dense titanium dioxide nanotube array (referred to as titanium substrate/titanium dioxide nanotube array). As shown in Figure 2;
(3)将钛基体/二氧化钛纳米管阵列用去离子水和酒精交替洗涤3次后作为阴极，再以石墨为阳极，在氨性电解锰溶液(硫酸锰17g/L、硫酸铵110g/L、pH7.2)中电解沉积10min(电解过程中阳极电流密度为75mA/cm2，温度为40℃)，使金属锰沉积在二氧化钛纳米管阵列中；(3) The titanium matrix/titanium dioxide nanotube array was alternately washed with deionized water and alcohol for 3 times as a cathode, and then graphite was used as an anode. Electrolytic deposition in pH 7.2) for 10 minutes (the anode current density during electrolysis is 75mA/cm2 , the temperature is 40°C), so that metal manganese is deposited in the titanium dioxide nanotube array;
(4)将50％的硝酸锰溶液涂覆在沉积有金属锰的二氧化钛纳米管阵列表面，置于马弗炉中在500℃下焙烧15min，然后再重新涂覆50％的硝酸锰溶液、焙烧，此过程重复10次，最后一次焙烧1h，即得到钛基二氧化钛纳米管复合阳极。(4) Coating 50% manganese nitrate solution on the surface of the titanium dioxide nanotube array deposited with metal manganese, placing it in a muffle furnace and roasting at 500°C for 15min, then re-coating 50% manganese nitrate solution, roasting , this process was repeated 10 times, and the final firing was performed for 1 h to obtain a titanium-based titanium dioxide nanotube composite anode.
选取不锈钢为阴极，将本实施例制备的钛基二氧化钛纳米管复合阳极作为阳极，极距为75mm，采用工业电解锰电解液，在40℃下以400A/m2的电流进行电解20h，阳极平均电位为2.2V，平均槽电压为4.1V。阳极副产物中未检测到铅等其它杂质元素，以阳极副产物二氧化锰为前躯体合成锰酸锂容量>112mAh/g，循环寿命>500次。Stainless steel was selected as the cathode, and the titanium-based titanium dioxide nanotube composite anode prepared in this example was used as the anode. The pole distance was 75mm. The industrial electrolytic manganese electrolyte was used to conduct electrolysis at 40°C with a current of 400A/m2 for 20h, and the anode averaged The potential was 2.2V and the average cell voltage was 4.1V. No other impurity elements such as lead were detected in the anode by-product, and the lithium manganese oxide was synthesized with the anode by-product manganese dioxide as the precursor. The capacity was >112mAh/g, and the cycle life was >500 times.
实施例2：Example 2:
一种本发明的钛基二氧化钛纳米管复合阳极，其结构示意图如图1所示，包括钛基体层1、二氧化钛纳米管阵列中间层2和活性表面层3；其中钛基体层1为纯钛片，二氧化钛纳米管阵列中间层2中沉积有金属锰，活性表面层3为MnO2。A titanium-based titanium dioxide nanotube composite anode of the present invention, its structural schematic diagram is shown in Figure 1, comprises titanium matrix layer 1, titanium dioxide nanotube array intermediate layer 2 and active surface layer 3; Wherein titanium matrix layer 1 is pure titanium sheet , metal manganese is deposited in the middle layer 2 of the titanium dioxide nanotube array, and the active surface layer 3 is MnO2 .
本实施例的钛基二氧化钛纳米管复合阳极的制备方法，包括以下步骤：The preparation method of the titanium-based titanium dioxide nanotube composite anode of this embodiment comprises the following steps:
(1)选取纯钛片作为钛基体，将纯钛片依次用360#、600#、800#、1000#砂纸打磨抛光，再分别用丙酮、乙醇、去离子水分别超声清洗10min，最后将表面打磨光滑的钛片放入HF：HNO3＝1:2的混酸溶液中进行活化30s，清洗，烘干；(1) Select pure titanium sheet as the titanium substrate, grind and polish the pure titanium sheet with 360#, 600#, 800#, 1000# sandpaper in sequence, then ultrasonically clean the sheet with acetone, ethanol, and deionized water for 10 minutes, and finally clean the surface Put the polished and smooth titanium sheet into the mixed acid solution of HF:HNO3 =1:2 for activation for 30s, clean and dry;
(2)将步骤(1)预处理后的钛基体作为阳极，石墨作为阴极，放入阳极氧化液(NH4F11.3g/L、丙三醇250mL和水250mL)中，在温度为45℃、电压为50V下氧化10h，使钛基体表面原位生长出分布均匀致密二氧化钛纳米管阵列(记钛基体/二氧化钛纳米管阵列)；(2) The titanium substrate pretreated in step (1) is used as the anode, graphite is used as the cathode, and put into an anodic oxidation solution (NH4 F11.3g/L, glycerin 250mL and water 250mL), at a temperature of 45°C , Oxidation at a voltage of 50V for 10 hours, so that the surface of the titanium substrate grows in situ with a uniformly distributed and dense titanium dioxide nanotube array (referred to as titanium substrate/titanium dioxide nanotube array);
(3)将钛基体/二氧化钛纳米管阵列用去离子水和酒精交替洗涤3次后作为阴极，再以石墨为阳极，在氨性电解锰溶液(硫酸锰17g/L、硫酸铵110g/L、pH7.2)中电解沉积15min(电解过程中阳极电流密度为75mA/cm2，温度为45℃)，使金属锰沉积在二氧化钛纳米管阵列中；(3) The titanium matrix/titanium dioxide nanotube array was alternately washed with deionized water and alcohol for 3 times as a cathode, and then graphite was used as an anode. Electrolytic deposition in pH 7.2) for 15 minutes (the anode current density during electrolysis is 75mA/cm2 , and the temperature is 45°C), so that metal manganese is deposited in the titanium dioxide nanotube array;
(4)将50％的硝酸锰溶液涂覆在沉积有金属锰的二氧化钛纳米管阵列表面，置于马弗炉中在500℃下焙烧15min，然后再重新涂覆50％的硝酸锰溶液、焙烧，此过程重复10次，最后一次焙烧1h，即得到钛基二氧化钛纳米管复合阳极。(4) Coating 50% manganese nitrate solution on the surface of the titanium dioxide nanotube array deposited with metal manganese, placing it in a muffle furnace and roasting at 500°C for 15min, then re-coating 50% manganese nitrate solution, roasting , this process was repeated 10 times, and the final firing was performed for 1 h to obtain a titanium-based titanium dioxide nanotube composite anode.
将本实施例的钛基二氧化钛纳米管复合阳极在硫酸溶液中做强化寿命测试：作为对比，选择传统的Ti/MnO2阳极，并在相同条件下制备了未修饰过二氧化钛纳米管中间层的钛基复合阳极(即未沉积有金属锰的二氧化钛纳米管中间层)，对三种电极进行了强化寿命测试，得到了如图3的所示结果：a表示传统的Ti/MnO2阳极，b表示未修饰二氧化钛纳米管中间层的钛基复合阳极，c表示本实施例的钛基二氧化钛纳米管复合阳极，通过对比可以发现，本实施例的钛基二氧化钛纳米管复合阳极的寿命得到了大大提高。The titanium-based titanium dioxide nanotube composite anode of this embodiment is tested in a sulfuric acid solution for enhanced life: as a comparison, a traditional Ti/MnO anode is selected, and an unmodified titanium dioxide nanotube intermediate layer is prepared under the same conditions. Based composite anode (i.e. the middle layer of titanium dioxide nanotubes without metal manganese deposition), the three kinds of electrodes were tested for enhanced life, and the results shown in Figure 3 were obtained: a represents the traditional Ti/MnO2 anode, b represents The titanium-based composite anode of the unmodified titanium dioxide nanotube intermediate layer, c represents the titanium-based titanium dioxide nanotube composite anode of this embodiment. Through comparison, it can be found that the life of the titanium-based titanium dioxide nanotube composite anode of this embodiment has been greatly improved.
实施例3：Example 3:
一种本发明的钛基二氧化钛纳米管复合阳极，其结构示意图如图1所示，包括钛基体层1、二氧化钛纳米管阵列中间层2和活性表面层3；其中钛基体层1为纯钛片，二氧化钛纳米管阵列中间层2中沉积有金属锰，活性表面层3为RuO2。A titanium-based titanium dioxide nanotube composite anode of the present invention, its structural schematic diagram is shown in Figure 1, comprises titanium matrix layer 1, titanium dioxide nanotube array intermediate layer 2 and active surface layer 3; Wherein titanium matrix layer 1 is pure titanium sheet , metal manganese is deposited in the middle layer 2 of the titanium dioxide nanotube array, and the active surface layer 3 is RuO2 .
本实施例的钛基二氧化钛纳米管复合阳极的制备方法，包括以下步骤：The preparation method of the titanium-based titanium dioxide nanotube composite anode of this embodiment comprises the following steps:
(1)选取纯钛片作为钛基体，将纯钛片依次用360#、600#、800#、1000#砂纸打磨抛光，再分别用丙酮、乙醇、去离子水分别超声清洗10min，最后将表面打磨光滑的钛片放入HF：HNO3＝1:2的混酸溶液中进行活化30s，清洗，烘干；(1) Select pure titanium sheet as the titanium substrate, grind and polish the pure titanium sheet with 360#, 600#, 800#, 1000# sandpaper in sequence, then ultrasonically clean the sheet with acetone, ethanol, and deionized water for 10 minutes, and finally clean the surface Put the polished and smooth titanium sheet into the mixed acid solution of HF:HNO3 =1:2 for activation for 30s, clean and dry;
(2)将步骤(1)预处理后的钛基体作为阳极，石墨作为阴极，放入阳极氧化液(NH4F11.3g/L、丙三醇250mL和水250mL)中，在温度为55℃、电压为30V下氧化12h，使钛基体表面原位生长出分布均匀致密二氧化钛纳米管阵列(记钛基体/二氧化钛纳米管阵列)；(2) The titanium substrate pretreated in step (1) was used as the anode, graphite was used as the cathode, and put into an anodic oxidation solution (NH4 F11.3g/L, glycerol 250mL and water 250mL), at a temperature of 55°C 1. Oxidation at a voltage of 30V for 12 hours, so that the surface of the titanium substrate grows in situ with a uniformly distributed and dense titanium dioxide nanotube array (referred to as titanium substrate/titanium dioxide nanotube array);
(3)将钛基体/二氧化钛纳米管阵列用去离子水和酒精交替洗涤3次后作为阴极，再以石墨为阳极，在氨性电解锰溶液(硫酸锰17g/L、硫酸铵110g/L、pH7.2)中电解沉积25min(电解过程中阳极电流密度为75mA/cm2，温度为40℃)，使金属锰沉积在二氧化钛纳米管阵列中；(3) The titanium matrix/titanium dioxide nanotube array was alternately washed with deionized water and alcohol for 3 times as a cathode, and then graphite was used as an anode. Electrolytic deposition in pH 7.2) for 25 minutes (the anode current density during the electrolysis process is 75mA/cm2 , the temperature is 40°C), so that metal manganese is deposited in the titanium dioxide nanotube array;
(4)将50％的醋酸钌溶液涂覆在沉积有金属锰的二氧化钛纳米管阵列表面，置于马弗炉中在500℃下焙烧15min，然后再重新涂覆50％的醋酸钌溶液、焙烧，此过程重复10次，最后一次焙烧1h，即得到钛基二氧化钛纳米管复合阳极。(4) Coating 50% ruthenium acetate solution on the surface of the titanium dioxide nanotube array deposited with metal manganese, placing it in a muffle furnace and roasting at 500° C. for 15 min, then re-coating 50% ruthenium acetate solution, roasting , this process was repeated 10 times, and the final firing was performed for 1 h to obtain a titanium-based titanium dioxide nanotube composite anode.
将本实施例的钛基二氧化钛纳米管复合阳极在工业废水中的应用：作为对比，制备了二氧化钛纳米管中间层中未电沉积锰的复合阳极(其它结构均和本发明相同)，将这两种电极用于氧化工业废水中的苯酚测试，得到了如图4的所示结果，a表示对比阳极，b表示本实施例制备的钛基二氧化钛纳米管复合阳极，通过对比可以发现，本实施例的钛基二氧化钛纳米管复合阳极的活性得到了大大提高。The application of the titanium-based titanium dioxide nanotube composite anode of the present embodiment in industrial wastewater: as a comparison, a composite anode (other structures are the same as the present invention) that has not electrodeposited manganese in the titanium dioxide nanotube intermediate layer has been prepared, and the two This kind of electrode is used for the phenol test in oxidizing industrial waste water, has obtained the result as shown in Figure 4, and a represents the comparison anode, and b represents the titanium-based titanium dioxide nanotube composite anode prepared in this embodiment. It can be found by comparison that the present embodiment The activity of the titanium-based titania nanotube composite anode has been greatly improved.
实施例4：Example 4:
一种本发明的钛基二氧化钛纳米管复合阳极，其结构示意图如图1所示，包括钛基体层1、二氧化钛纳米管阵列中间层2和活性表面层3；其中钛基体层1为纯钛片，二氧化钛纳米管阵列中间层2中沉积有金属锰，活性表面层3为SnO2。A titanium-based titanium dioxide nanotube composite anode of the present invention, its structural schematic diagram is shown in Figure 1, comprises titanium matrix layer 1, titanium dioxide nanotube array intermediate layer 2 and active surface layer 3; Wherein titanium matrix layer 1 is pure titanium sheet , metal manganese is deposited in the middle layer 2 of the titanium dioxide nanotube array, and the active surface layer 3 is SnO2 .
本实施例的钛基二氧化钛纳米管复合阳极的制备方法，包括以下步骤：The preparation method of the titanium-based titanium dioxide nanotube composite anode of this embodiment comprises the following steps:
(1)选取纯钛片作为钛基体，将纯钛片依次用360#、600#、800#、1000#砂纸打磨抛光，再分别用丙酮、乙醇、去离子水分别超声清洗10min，最后将表面打磨光滑的钛片放入HF：HNO3＝1:2的混酸溶液中进行活化30s，清洗，烘干；(1) Select pure titanium sheet as the titanium substrate, grind and polish the pure titanium sheet with 360#, 600#, 800#, 1000# sandpaper in sequence, then ultrasonically clean the sheet with acetone, ethanol, and deionized water for 10 minutes, and finally clean the surface Put the polished and smooth titanium sheet into the mixed acid solution of HF:HNO3 =1:2 for activation for 30s, clean and dry;
(2)将步骤(1)预处理后的钛基体作为阳极，石墨作为阴极，放入阳极氧化液(NH4F11.3g/L、丙三醇250mL和水250mL)中，在温度为55℃、电压为30V下氧化20h，使钛基体表面原位生长出分布均匀致密二氧化钛纳米管阵列(记钛基体/二氧化钛纳米管阵列)；(2) The titanium substrate pretreated in step (1) was used as the anode, graphite was used as the cathode, and put into an anodic oxidation solution (NH4 F11.3g/L, glycerol 250mL and water 250mL), at a temperature of 55°C , Oxidation at a voltage of 30V for 20 hours, so that the surface of the titanium substrate grows in situ a uniformly distributed and dense titanium dioxide nanotube array (referred to as titanium substrate/titanium dioxide nanotube array);
(3)将钛基体/二氧化钛纳米管阵列用去离子水和酒精交替洗涤3次后作为阴极，再以石墨为阳极，在氨性电解锰溶液(硫酸锰17g/L、硫酸铵110g/L、pH7.2)中电解沉积5min(电解过程中阳极电流密度为75mA/cm2，温度为45℃)，使金属锰沉积在二氧化钛纳米管阵列中；(3) The titanium matrix/titanium dioxide nanotube array was alternately washed with deionized water and alcohol for 3 times as a cathode, and then graphite was used as an anode. Electrolytic deposition in pH 7.2) for 5 minutes (the anode current density during electrolysis is 75mA/cm2 , and the temperature is 45°C), so that metal manganese is deposited in the titanium dioxide nanotube array;
(4)将五水四氯化锡溶解于柠檬酸和乙二醇聚合物前驱体溶液中，用毛刷分别将所得溶液涂覆在沉积有金属锰的二氧化钛纳米管阵列表面，先在130℃中烘20min，再在550℃下焙烧20min，此过程重复10次，最后一次在550℃下焙烧1h，即得到钛基二氧化钛纳米管复合阳极。(4) Dissolve tin tetrachloride pentahydrate in citric acid and ethylene glycol polymer precursor solutions, and coat the resulting solution on the surface of titanium dioxide nanotube arrays deposited with metal manganese with a brush, first at 130 ° C Medium baking for 20 minutes, followed by calcination at 550°C for 20 minutes, this process was repeated 10 times, and the final calcination was at 550°C for 1 hour to obtain a titanium-based titanium dioxide nanotube composite anode.
本实施例的钛基二氧化钛纳米管复合阳极在电解锰中的应用：作为对比，制备了二氧化钛纳米管中间层中未电沉积锰的复合阳极(其它结构均和本发明相同)，对两电极进行强化寿命测试，如图5所示，a表示本实施例制备的钛基二氧化钛纳米管复合阳极；b表示对比电极。从图5可以看出，本发明的钛基二氧化钛纳米管复合阳极的寿命要大大加长，而且电位也较低，这是因为沉积有金属锰的二氧化钛纳米管层导电性增强，在涂层上的压降降低，减缓了溶液中氧的侵蚀。Application of the titanium-based titanium dioxide nanotube composite anode of the present embodiment in electrolytic manganese: as a comparison, a composite anode (other structures are all the same as the present invention) without electrodeposited manganese in the titanium dioxide nanotube intermediate layer was prepared, and the two electrodes were carried out Intensified life test, as shown in Figure 5, a represents the titanium-based titanium dioxide nanotube composite anode prepared in this example; b represents the comparative electrode. As can be seen from Fig. 5, the life-span of the titanium-based titanium dioxide nanotube composite anode of the present invention will be lengthened greatly, and electric potential is also lower, and this is because the conductivity of the titanium dioxide nanotube layer deposited with metal manganese is enhanced, and on the coating The reduced pressure drop slows down the attack of oxygen in the solution.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610573982.2ACN106048690B (en) | 2016-07-20 | 2016-07-20 | A kind of titanium-based titanium dioxide nanotube composite anode and preparation method thereof |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610573982.2ACN106048690B (en) | 2016-07-20 | 2016-07-20 | A kind of titanium-based titanium dioxide nanotube composite anode and preparation method thereof |
| Publication Number | Publication Date |
|---|---|
| CN106048690A CN106048690A (en) | 2016-10-26 |
| CN106048690Btrue CN106048690B (en) | 2018-07-20 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610573982.2AActiveCN106048690B (en) | 2016-07-20 | 2016-07-20 | A kind of titanium-based titanium dioxide nanotube composite anode and preparation method thereof |
| Country | Link |
|---|---|
| CN (1) | CN106048690B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4063539A1 (en)* | 2021-03-24 | 2022-09-28 | TVS Motor Company Limited | A method for preparing a titanium nanotube electrode |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106835192B (en)* | 2017-02-02 | 2018-12-21 | 桂林理工大学 | A kind of preparation method of electrolytic manganese dioxide titanium substrate anode surface composite coating |
| CN107916446B (en)* | 2017-11-16 | 2019-07-30 | 重庆大学 | The clean manufacturing of chloroacetaldehyde oxime and its RuO used2@TNTs anode |
| CN109628957A (en)* | 2018-12-27 | 2019-04-16 | 西安泰金工业电化学技术有限公司 | A kind of preparation method of Zinc electrolysis titanium-based nano composite anode |
| CN111962131B (en)* | 2020-07-14 | 2021-06-22 | 广东省科学院稀有金属研究所 | Composite oxide catalytic coating for oxygen evolution electrode and preparation method thereof |
| CN114134542B (en)* | 2021-12-08 | 2024-05-10 | 昆明理工大学 | Porous titanium-based carbon nanotube reinforced amorphous metal oxide coated electrode and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102268689A (en)* | 2011-06-24 | 2011-12-07 | 太原理工大学 | Titanium-based oxide acid resistant anode and preparation method thereof |
| CN102766882A (en)* | 2012-08-10 | 2012-11-07 | 华南理工大学 | Manufacture method for chlorine-evolution dimensionally stable anode (DSA) electro-catalytic electrode with three dimensional structure |
| CN104593818A (en)* | 2014-12-24 | 2015-05-06 | 中南大学 | Titanium-based composite anode as well as preparation method and application thereof |
| CN105274561A (en)* | 2015-11-25 | 2016-01-27 | 哈尔滨工业大学 | Method for preparing nano-structure DSA electro-catalysis electrode with interlayer |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140119314A (en)* | 2013-03-28 | 2014-10-10 | 인텔렉추얼디스커버리 주식회사 | Electrode for photoelectrochemical cell, method of manufacturing the same and photoelectrochemical cell including the same |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102268689A (en)* | 2011-06-24 | 2011-12-07 | 太原理工大学 | Titanium-based oxide acid resistant anode and preparation method thereof |
| CN102766882A (en)* | 2012-08-10 | 2012-11-07 | 华南理工大学 | Manufacture method for chlorine-evolution dimensionally stable anode (DSA) electro-catalytic electrode with three dimensional structure |
| CN104593818A (en)* | 2014-12-24 | 2015-05-06 | 中南大学 | Titanium-based composite anode as well as preparation method and application thereof |
| CN105274561A (en)* | 2015-11-25 | 2016-01-27 | 哈尔滨工业大学 | Method for preparing nano-structure DSA electro-catalysis electrode with interlayer |
| Title |
|---|
| 电化学沉积锰修饰TiO2纳米管阵列的正交试验研究;熊中平 等;《钢铁钒钛》;20160225;第37卷(第1期);第51页试验部分* |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4063539A1 (en)* | 2021-03-24 | 2022-09-28 | TVS Motor Company Limited | A method for preparing a titanium nanotube electrode |
| Publication number | Publication date |
|---|---|
| CN106048690A (en) | 2016-10-26 |
| Publication | Publication Date | Title |
|---|---|---|
| CN106048690B (en) | A kind of titanium-based titanium dioxide nanotube composite anode and preparation method thereof | |
| CN101857288B (en) | Preparation method of titanium-based titanium dioxide nanotube stannic oxide electrode | |
| CN111170415B (en) | A titanium oxide/ruthenium oxide composite electrode and its preparation method and application | |
| CN102766882B (en) | A kind of preparation method analysing chlorine DSA electro catalytic electrode of three-dimensional structure | |
| CN101880891B (en) | High-stability DSA anode for preparing chlorine by electrolysis and preparation method thereof | |
| CN108677221B (en) | A kind of titanium-based β-MnO2 composite coating anode and preparation method thereof | |
| CN106086989B (en) | A kind of titania modified by Argentine nanotube composite anode and preparation method thereof | |
| CN106283125A (en) | Metal electro-deposition coated titanium electrode and preparation method thereof | |
| CN103014755A (en) | Fabrication method of long-life titanium base electrode | |
| CN110803743B (en) | A kind of preparation method of defect state titanium oxide-alumina-graphene ceramic electrode | |
| CN103700813B (en) | A kind of Ti base β-PbO 2the preparation method of dimensional stable anode | |
| CN113816468B (en) | A kind of DSA electrode and its preparation method and application | |
| CN103253743A (en) | Preparation method and application of Fe-doped PTFE-PbO2/TiO2-NTs/Ti electrode | |
| CN102899683A (en) | A kind of preparation method of Ti-based nano CeO2/PbO2 modified electrode | |
| CN102320683B (en) | Titanium-based tin-antimony-platinum oxide electrode material and preparation method thereof | |
| CN1772955A (en) | A kind of mixed metal oxide electrode and preparation method thereof | |
| CN115354384A (en) | Coating titanium anode for electrodeposited copper and preparation method thereof | |
| CN102864465B (en) | A kind of preparation method of high reactivity Ti/Pr2O3-PbO2 modified electrode | |
| CN112195482B (en) | Composite titanium anode plate and preparation method thereof | |
| CN102560561A (en) | DSA (Dimensionally Stable Anode) electrode and manufacturing method thereof | |
| CN106809918A (en) | A kind of carbon nano tube modified lead dioxide electrode and preparation method thereof | |
| CN109504987B (en) | Titanium-based composite anode for electrolytic manganese and preparation method and application thereof | |
| CN106835192A (en) | A kind of electrolytic manganese dioxide preparation method of titanium substrate anode surface composite coating | |
| CN112376047B (en) | Titanium-based iridium dioxide composite graphene and Mn-Mo oxide electrode and preparation method thereof | |
| CN108411349A (en) | A kind of porous RuO of graphene doping2The preparation method of anode |
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |