CN106048690B - A kind of titanium-based titanium dioxide nanotube composite anode and preparation method thereof - Google Patents

A kind of titanium-based titanium dioxide nanotube composite anode and preparation method thereof Download PDF

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CN106048690B
CN106048690B CN201610573982.2A CN201610573982A CN106048690B CN 106048690 B CN106048690 B CN 106048690B CN 201610573982 A CN201610573982 A CN 201610573982A CN 106048690 B CN106048690 B CN 106048690B
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titanium
titanium dioxide
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CN106048690A (en
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郭华军
罗树亮
李星海
王志兴
彭文杰
胡启阳
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Central South University
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Abstract

The invention discloses a kind of titanium-based titanium dioxide nanotube composite anodes, including Titanium base layer, Nano tube array of titanium dioxide middle layer and active surface layer；Deposition has manganese metal in the Nano tube array of titanium dioxide middle layer.The preparation method of the present invention：First Titanium base is pre-processed；So that Titanium base surface in situ is grown Nano tube array of titanium dioxide again, then manganese metal is made to be deposited in Nano tube array of titanium dioxide；The salting liquid coating deposition for preparing active surface layer finally has to the Nano tube array of titanium dioxide surface of manganese metal, roasting is to get to titanium-based titanium dioxide nanotube composite anode.In the titanium-based titanium dioxide nanotube composite anode of the present invention, nanometer titanium dioxide layer is to synchronize generated in-situ, connect with Titanium base part very fine and close, does not have crannied appearance, and oxygen that can be in effective suppression solution directly corrodes Titanium base and is passivated.

Description

A kind of titanium-based titanium dioxide nanotube composite anode and preparation method thereof
Technical field
The invention belongs to electrochemical field more particularly to a kind of titanium-based titanium dioxide nanotube composite anode and its preparation sides Method.
Background technology
Metal oxide anode is also known as dimensional stable anode DSA, is invented by H.B.Beer, by Italian De Nora companies head First realize industrialized production (Ti electrode engineering, Beijing：Metallurgical industry publishing house, 2003), wherein metallic matrix plays conductive and bone Frame acts on, and surface active coating then participates in the electrochemical reaction of anode.Currently, DSA has been widely used for electrometallurgy industry, chlorine Alkali industry, plating, wastewater treatment etc..
French scientist Zwilling V were reported equal to 1999 and are prepared two in titanium plate by anodizing for the first time The work of titanium oxide nanotubes, anodizing, which has become, till now prepares important one of the method for titania nanotube. Nano-titanium dioxide is as a kind of inorganic functional material, in storage and application, photoelectric conversion, the photocatalytic degradation air of solar energy And the pollutant etc. in water is widely used, and preliminary application has also been obtained in Ni―Ti anode.
Although the preparation method of titanium-based composite anode is varied, simple for process, the catalytic activity of coating is high, selectivity It is good, but there are one fatal disadvantages：Service life is shorter, is easy passivation and forms the very poor titanium dioxide film of one layer of electric conductivity. Numerous researchers in order to solve this problem, mainly propose following several schemes in recent years：The first is increased using heat coating Add the method for middle layer, generally stannic oxide middle layer, increase matrix and apply the binding force of interlayer so that entire coating causes It is close, and increase the resistance to oxygen in solution, but increase middle layer and only increase coat and matrix to a certain extent Physical bond power, fail fundamentally to stop in solution oxygen from the crack of coating to the erosion of matrix；Second is to use Titanium and other metals are formed into titanium alloy, as applied very extensive titanium manganese alloy, the oxygen on surface inside electrolytic manganese dioxide Change film be titanium manganese composite oxide, corrosion resistance greatly improves, but the complex manufacturing technology of this method, consistency compared with Difference；The third is to introduce rare metal Catalytic Layer, but the catalytic action of rare metal can be only applied to specific area, and its Use cost is excessively high, and introduces titania nanotube middle layer and increase the resistance to corrosion of electrode, this in advance in electricity Although the method that pole surface introduces thin fine and close middle layer can greatly increase the service life of Ni―Ti anode, even titanium dioxide Its electric conductivity of titanium nanotube is still poor, larger so as to cause the pressure drop on entire coating, and energy consumption increases.Therefore, at present These technical solutions all can not fundamentally solve the short technological deficiency of titanium-based composite anode service life.
Invention content
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one The titanium-based titanium dioxide nanotube composite anode and preparation method thereof of kind extra long life.
In order to solve the above technical problems, technical solution proposed by the present invention is：
A kind of titanium-based titanium dioxide nanotube composite anode, including Titanium base layer, Nano tube array of titanium dioxide middle layer And active surface layer；Deposition has manganese metal in the Nano tube array of titanium dioxide middle layer.
Above-mentioned titanium-based titanium dioxide nanotube composite anode, it is preferred that the active surface layer is SnO2、MnO2、 IrO2、PbO2、PdO2And RuO2One or more of metal oxide mixed layer.
Above-mentioned titanium-based titanium dioxide nanotube composite anode, it is preferred that the Titanium base layer is metallic titanium plate, titanium alloy Or titanium thin slice.
The inventive concept total as one, the present invention also provides a kind of preparations of titanium-based titanium dioxide nanotube composite anode Method includes the following steps：
(1) Titanium base is pre-processed；
(2) using pretreated Titanium base as anode, graphite is put into as cathode in anodizing solution, anodic oxidation 5 ~20h makes Titanium base surface in situ grow Nano tube array of titanium dioxide, obtains Titanium base/Nano tube array of titanium dioxide；
(3) after the Titanium base/Nano tube array of titanium dioxide being cleaned up, as cathode, then using graphite as anode, It is electrolysed 5~25min in ammonia electrolytic manganese solution, manganese metal is made to be deposited in Nano tube array of titanium dioxide；
(4) one or several kinds in the salting liquid of tin, manganese, iridium, lead, palladium or ruthenium are coated in step (3) deposition has gold The Nano tube array of titanium dioxide surface for belonging to manganese, is then roasted, obtains the titanium-based titanium dioxide nanotube composite anode.
Above-mentioned preparation method, it is preferred that in the step (2), the voltage of anodic oxidation is 30~50V, anodic oxidation Reaction time is 8~20h.
Above-mentioned preparation method, it is preferred that in the step (3), a concentration of the 10 of bivalent manganese in ammonia electrolytic manganese solution ~20g/L, ammonium sulfate concentrations are 100~120g/L, and the pH of electrolytic manganese solution is 7~8.
Above-mentioned preparation method, it is preferred that the cleaning process in the step (3) refers to being replaced with deionized water and alcohol Washing is for several times.Preferably, alternately the number of washing is 3 times.
Above-mentioned preparation method, it is preferred that coating and roasting process in the step (4) need to repeat 10~15 times.
Above-mentioned preparation method, it is preferred that in the step (1), the preprocessing process of Titanium base specifically includes：First by titanium Matrix carries out sanding and polishing, then is cleaned to the Titanium base after sanding and polishing, is finally putting into HF and HNO3In mixed acid solution into Row etch is handled.
Compared with the prior art, the advantages of the present invention are as follows：
(1) in titanium-based titanium dioxide nanotube composite anode of the invention, nanometer titanium dioxide layer is synchronous in-situ preparation , it is connect with Titanium base part very fine and close, does not have crannied appearance, oxygen that can be effectively in suppression solution directly corrodes Titanium base And it is passivated.
(2) in titanium-based titanium dioxide nanotube composite anode of the invention, manganese metal is grown directly upon nano titania Guan Zhong, the surface cladding process for the prior art that compares are greatly promoted the mixing of titanium manganese；And after baking, part manganese enters In titanium dioxide lattice, and the content of titanous in lattice is increased, to increase the electric conductivity of titanium dioxide layer, reduces sun Extreme pressure drops, and reduces energy consumption.
(3) service life of titanium-based titanium dioxide nanotube composite anode of the invention is long more than common combination electrode.
(4) titanium-based titanium dioxide nanotube composite anode of the invention may be directly applied to electrolytic manganese anode, redeposited After enough manganese, manganese dioxide active layer can be directly formed on surface after heating, production method is simple and efficient, and is extremely caused It is close.As anode in use, objectionable impurities will not be introduced in battery material, and the by-product titanium dioxide of anode can be collected Manganese does further deep processing.
(5) preparation process of titanium-based titanium dioxide nanotube composite anode of the invention is environmentally friendly, does not generate toxic Gaseous contamination environment.
Description of the drawings
Fig. 1 is the structural schematic diagram of the titanium-based titanium dioxide nanotube composite anode of the present invention.
Fig. 2 is the titania nanotube in titanium-based titanium dioxide nanotube composite anode prepared by the embodiment of the present invention 1 Scanning electron microscope (SEM) photograph
Fig. 3 is titanium-based titanium dioxide nanotube composite anode and traditional Ti/MnO prepared by the embodiment of the present invention 22Sun Pole, non-deposited metal manganese titanium-based composite anode reinforcing life test and comparison figure.
Fig. 4 is the titanium of titanium-based titanium dioxide nanotube composite anode and non-deposited metal manganese prepared by the embodiment of the present invention 3 Figure is compared in based composite anode oxidation.
Fig. 5 be 4 neutral solution system of the embodiment of the present invention prepare titanium-based titanium dioxide nanotube composite anode with do not sink The titanium-based composite anode of product manganese metal tank voltage in electrolytic manganese compares figure.
Marginal data：1, Titanium base layer；2, Nano tube array of titanium dioxide middle layer；3, active surface layer.
Specific implementation mode
To facilitate the understanding of the present invention, it is done more entirely below in conjunction with Figure of description and preferred embodiment to inventing herein Face meticulously describes, but protection scope of the present invention is not limited to following specific examples.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art Together.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention's Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city Field is commercially available or can be prepared by existing method.
Embodiment 1：
A kind of titanium-based titanium dioxide nanotube composite anode of the present invention, structural schematic diagram is as shown in Figure 1, include titanium-based Body layer 1, Nano tube array of titanium dioxide middle layer 2 and active surface layer 3；Wherein Titanium base layer 1 is pure titanium sheet, and titanium dioxide is received It is MnO that deposition, which has manganese metal, active surface layer 3, in mitron array middle layer 22。
The preparation method of the titanium-based titanium dioxide nanotube composite anode of the present embodiment, includes the following steps：
(1) pure titanium sheet is chosen as Titanium base, uses the polishing of 360#, 600#, 800#, 1000# sand paper to throw successively pure titanium sheet Light, then it is cleaned by ultrasonic 10min respectively with acetone, ethyl alcohol, deionized water respectively, finally the titanium sheet that surface polishes smooth is put into HF：HNO3=1:Activation 30s is carried out in 2 mixed acid solution, is cleaned, drying；
(2) using step (1) pretreated Titanium base as anode, graphite is put into oxidation solution as cathode (NH4F11.3g/L, glycerine 250mL and water 250mL) in, 8h is aoxidized in the case where temperature is 55 DEG C, voltage is 40V, makes Titanium base Surface in situ grows the compact titanium dioxide nano-tube array that is evenly distributed (note Titanium base/Nano tube array of titanium dioxide), receives A diameter of 90nm of mitron or so, with scanning electron microscopic observation, pattern is as shown in Figure 2；
(3) use deionized water and alcohol alternately after washing 3 times as cathode Titanium base/Nano tube array of titanium dioxide, Again using graphite as anode, the electrolytic deposition in ammonia electrolytic manganese solution (manganese sulfate 17g/L, ammonium sulfate 110g/L, pH7.2) (electrolytic process Anodic current density is 75mA/cm to 10min2, temperature is 40 DEG C), so that manganese metal is deposited on nano titania In pipe array；
(4) 50% manganese nitrate solution is coated in deposition has the Nano tube array of titanium dioxide surface of manganese metal, is placed in 15min is roasted in Muffle furnace at 500 DEG C, then the manganese nitrate solution of coating 50%, roasting, this process repeat 10 again again Secondary, last time roasts 1h to get to titanium-based titanium dioxide nanotube composite anode.
Selection stainless steel is cathode, using titanium-based titanium dioxide nanotube composite anode manufactured in the present embodiment as anode, Pole span is 75mm, using industrial electrolysis manganese electrolyte, with 400A/m at 40 DEG C2Electric current carry out electrolysis 20h, the average electricity of anode Position is 2.2V, average cell voltage 4.1V.Other impurity elements such as lead are not detected in anode by-product, with anode by-product two Manganese oxide is precursor synthetic lithium manganate capacity>112mAh/g, cycle life>500 times.
Embodiment 2：
A kind of titanium-based titanium dioxide nanotube composite anode of the present invention, structural schematic diagram is as shown in Figure 1, include titanium-based Body layer 1, Nano tube array of titanium dioxide middle layer 2 and active surface layer 3；Wherein Titanium base layer 1 is pure titanium sheet, and titanium dioxide is received It is MnO that deposition, which has manganese metal, active surface layer 3, in mitron array middle layer 22。
The preparation method of the titanium-based titanium dioxide nanotube composite anode of the present embodiment, includes the following steps：
(1) pure titanium sheet is chosen as Titanium base, uses the polishing of 360#, 600#, 800#, 1000# sand paper to throw successively pure titanium sheet Light, then it is cleaned by ultrasonic 10min respectively with acetone, ethyl alcohol, deionized water respectively, finally the titanium sheet that surface polishes smooth is put into HF：HNO3=1:Activation 30s is carried out in 2 mixed acid solution, is cleaned, drying；
(2) using step (1) pretreated Titanium base as anode, graphite is put into anodizing solution as cathode (NH4F11.3g/L, glycerine 250mL and water 250mL) in, 10h is aoxidized in the case where temperature is 45 DEG C, voltage is 50V, makes Titanium base Surface in situ grows the compact titanium dioxide nano-tube array that is evenly distributed (note Titanium base/Nano tube array of titanium dioxide)；
(3) use deionized water and alcohol alternately after washing 3 times as cathode Titanium base/Nano tube array of titanium dioxide, Again using graphite as anode, the electrolytic deposition in ammonia electrolytic manganese solution (manganese sulfate 17g/L, ammonium sulfate 110g/L, pH7.2) (electrolytic process Anodic current density is 75mA/cm to 15min2, temperature is 45 DEG C), so that manganese metal is deposited on nano titania In pipe array；
(4) 50% manganese nitrate solution is coated in deposition has the Nano tube array of titanium dioxide surface of manganese metal, is placed in 15min is roasted in Muffle furnace at 500 DEG C, then the manganese nitrate solution of coating 50%, roasting, this process repeat 10 again again Secondary, last time roasts 1h to get to titanium-based titanium dioxide nanotube composite anode.
The titanium-based titanium dioxide nanotube composite anode of the present embodiment is done into reinforcing life test in sulfuric acid solution：As Comparison, selects traditional Ti/MnO2Anode, and it is prepared for unmodified titania nanotube middle layer excessively under the same conditions Three kinds of electrodes have been carried out reinforcing life by titanium-based composite anode (the titania nanotube middle layer for not depositing manganese metal) Test, has obtained result as shown in figure 3：A indicates traditional Ti/MnO2Anode, b are indicated in unmodified titania nanotube The titanium-based composite anode of interbed, c indicate the titanium-based titanium dioxide nanotube composite anode of the present embodiment, can be sent out by comparison Existing, the service life of the titanium-based titanium dioxide nanotube composite anode of the present embodiment is greatly improved.
Embodiment 3：
A kind of titanium-based titanium dioxide nanotube composite anode of the present invention, structural schematic diagram is as shown in Figure 1, include titanium-based Body layer 1, Nano tube array of titanium dioxide middle layer 2 and active surface layer 3；Wherein Titanium base layer 1 is pure titanium sheet, and titanium dioxide is received It is RuO that deposition, which has manganese metal, active surface layer 3, in mitron array middle layer 22。
The preparation method of the titanium-based titanium dioxide nanotube composite anode of the present embodiment, includes the following steps：
(1) pure titanium sheet is chosen as Titanium base, uses the polishing of 360#, 600#, 800#, 1000# sand paper to throw successively pure titanium sheet Light, then it is cleaned by ultrasonic 10min respectively with acetone, ethyl alcohol, deionized water respectively, finally the titanium sheet that surface polishes smooth is put into HF：HNO3=1:Activation 30s is carried out in 2 mixed acid solution, is cleaned, drying；
(2) using step (1) pretreated Titanium base as anode, graphite is put into anodizing solution as cathode (NH4F11.3g/L, glycerine 250mL and water 250mL) in, 12h is aoxidized in the case where temperature is 55 DEG C, voltage is 30V, makes Titanium base Surface in situ grows the compact titanium dioxide nano-tube array that is evenly distributed (note Titanium base/Nano tube array of titanium dioxide)；
(3) use deionized water and alcohol alternately after washing 3 times as cathode Titanium base/Nano tube array of titanium dioxide, Again using graphite as anode, the electrolytic deposition in ammonia electrolytic manganese solution (manganese sulfate 17g/L, ammonium sulfate 110g/L, pH7.2) (electrolytic process Anodic current density is 75mA/cm to 25min2, temperature is 40 DEG C), so that manganese metal is deposited on nano titania In pipe array；
(4) 50% ruthenium acetate solution is coated in deposition has the Nano tube array of titanium dioxide surface of manganese metal, is placed in 15min is roasted in Muffle furnace at 500 DEG C, then the ruthenium acetate solution of coating 50%, roasting, this process repeat 10 again again Secondary, last time roasts 1h to get to titanium-based titanium dioxide nanotube composite anode.
By application of the titanium-based titanium dioxide nanotube composite anode of the present embodiment in industrial wastewater：As a comparison, it makes The composite anode (other structures are identical with the present invention) of non-electro-deposition manganese in standby titania nanotube middle layer, by this two Kind electrode is used to aoxidize the phenol test in industrial wastewater, has obtained as shown in Fig. 4 as a result, a indicates that counter electrode, b indicate Titanium-based titanium dioxide nanotube composite anode manufactured in the present embodiment, by comparison it can be found that the titanium-based dioxy of the present embodiment The activity for changing titanium nanotube composite anode is greatly improved.
Embodiment 4：
A kind of titanium-based titanium dioxide nanotube composite anode of the present invention, structural schematic diagram is as shown in Figure 1, include titanium-based Body layer 1, Nano tube array of titanium dioxide middle layer 2 and active surface layer 3；Wherein Titanium base layer 1 is pure titanium sheet, and titanium dioxide is received It is SnO that deposition, which has manganese metal, active surface layer 3, in mitron array middle layer 22。
The preparation method of the titanium-based titanium dioxide nanotube composite anode of the present embodiment, includes the following steps：
(1) pure titanium sheet is chosen as Titanium base, uses the polishing of 360#, 600#, 800#, 1000# sand paper to throw successively pure titanium sheet Light, then it is cleaned by ultrasonic 10min respectively with acetone, ethyl alcohol, deionized water respectively, finally the titanium sheet that surface polishes smooth is put into HF：HNO3=1:Activation 30s is carried out in 2 mixed acid solution, is cleaned, drying；
(2) using step (1) pretreated Titanium base as anode, graphite is put into anodizing solution as cathode (NH4F11.3g/L, glycerine 250mL and water 250mL) in, 20h is aoxidized in the case where temperature is 55 DEG C, voltage is 30V, makes Titanium base Surface in situ grows the compact titanium dioxide nano-tube array that is evenly distributed (note Titanium base/Nano tube array of titanium dioxide)；
(3) use deionized water and alcohol alternately after washing 3 times as cathode Titanium base/Nano tube array of titanium dioxide, Again using graphite as anode, the electrolytic deposition 5min in ammonia electrolytic manganese solution (manganese sulfate 17g/L, ammonium sulfate 110g/L, pH7.2) (electrolytic process Anodic current density is 75mA/cm2, temperature is 45 DEG C), so that manganese metal is deposited on titania nanotube battle array In row；
(4) stannic chloride pentahydrate is dissolved in citric acid and ethylene glycol polymer precursor solution, respectively will with hairbrush Acquired solution, which is coated in deposition, the Nano tube array of titanium dioxide surface of manganese metal, 20min is first dried in 130 DEG C, then 550 20min is roasted at DEG C, this process is repeated 10 times, and roasts 1h at 550 DEG C for the last time to get to titanium-based titanium dioxide nanotube Composite anode.
Application of the titanium-based titanium dioxide nanotube composite anode of the present embodiment in electrolytic manganese：As a comparison, it is prepared for The composite anode (other structures identical with the present invention) of non-electro-deposition manganese in titania nanotube middle layer, to two electrodes into Row reinforcing life is tested, as shown in figure 5, a indicates titanium-based titanium dioxide nanotube composite anode manufactured in the present embodiment；B is indicated Comparison electrode.From fig. 5, it can be seen that the service life of the titanium-based titanium dioxide nanotube composite anode of the present invention will lengthen significantly, and And current potential is relatively low, this is because deposition has the titania nanotube layer electric conductivity of manganese metal to enhance, the pressure drop on coating It reduces, slows down the erosion of oxygen in solution.

Claims (8)

1. a kind of preparation method of titanium-based titanium dioxide nanotube composite anode, which is characterized in that the titanium-based titanium dioxide is received Mitron composite anode includes Titanium base layer, Nano tube array of titanium dioxide middle layer and active surface layer；The titanium dioxide is received Deposition has manganese metal in mitron array middle layer；The preparation method of the titanium-based titanium dioxide nanotube composite anode includes following Step：
(1) Titanium base is pre-processed；
(2) using pretreated Titanium base as anode, graphite is put into as cathode in anodizing solution, and anodic oxidation 5~ 20h makes Titanium base surface in situ grow Nano tube array of titanium dioxide, obtains Titanium base/Nano tube array of titanium dioxide；
(3) after cleaning up the Titanium base/Nano tube array of titanium dioxide, as cathode, then using graphite as anode, in ammonia Property electrolytic manganese solution in be electrolysed 5~25min, so that manganese metal is deposited in Nano tube array of titanium dioxide；
(4) one or several kinds in the salting liquid of tin, manganese, iridium, lead, palladium or ruthenium are coated in step (3) deposition has manganese metal Nano tube array of titanium dioxide surface, then roasted, obtain the titanium-based titanium dioxide nanotube composite anode.
2. preparation method as described in claim 1, which is characterized in that in the step (2), the voltage of anodic oxidation is 30~ 50V, anodic oxidation reactions time are 8~20h.
3. preparation method as described in claim 1, which is characterized in that in the step (3), divalent in ammonia electrolytic manganese solution A concentration of 10~20g/L of manganese, ammonium sulfate concentrations are 100~120g/L, and the pH of electrolytic manganese solution is 7~8.
4. preparation method as described in claim 1, which is characterized in that the cleaning process in the step (3) refer to spend from Sub- water and alcohol alternately wash for several times.
5. preparation method as described in claim 1, which is characterized in that coating and roasting process in the step (4) need weight It is 10~15 times multiple.
6. preparation method as described in claim 1, which is characterized in that in the step (1), the preprocessing process of Titanium base has Body includes：Titanium base is first subjected to sanding and polishing, then the Titanium base after sanding and polishing is cleaned, is finally putting into HF and HNO3 Etch processing is carried out in mixed acid solution.
7. preparation method as described in claim 1, which is characterized in that the active surface layer is SnO2、MnO2、IrO2、PbO2、 PdO2And RuO2One or more of metal oxide mixed layer.
8. preparation method as described in claim 1, which is characterized in that the Titanium base layer is layer of titanium metal or titanium alloy layer.
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