CN106048690A - Titanium-based titanium dioxide nanotube composite anode and preparation method thereof - Google Patents

Titanium-based titanium dioxide nanotube composite anode and preparation method thereof Download PDF

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CN106048690A
CN106048690A CN201610573982.2A CN201610573982A CN106048690A CN 106048690 A CN106048690 A CN 106048690A CN 201610573982 A CN201610573982 A CN 201610573982A CN 106048690 A CN106048690 A CN 106048690A
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titanium
titanium dioxide
composite anode
dioxide nanotube
nanotube composite
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CN106048690B (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 titanium-based titanium dioxide nanotube composite anode. The titanium-based titanium dioxide nanotube composite anode comprises a titanium substrate layer, a titanium dioxide nanotube array intermediate layer and an active surface layer. Metal manganese is deposited in the titanium dioxide nanotube array intermediate layer. A preparation method of the titanium-based titanium dioxide nanotube composite anode includes the steps that a titanium substrate is preprocessed; a titanium dioxide nanotube array is made to grow on the surface of the titanium substrate in situ, and then the metal manganese is made to deposit in the titanium dioxide nanotube array; and finally, a saline solution for preparing the active surface layer is sprayed on the surface of the titanium dioxide nanotube array where the metal manganese is deposited, calcination is conducted, and then the titanium-based titanium dioxide nanotube composite anode is obtained. In the titanium-based titanium dioxide nanotube composite anode, the nanometer titanium dioxide layer is synchronously generated in situ and is quite tightly connected with a titanium substrate piece, no cracks appear, and passivation caused by the fact that oxygen in the solution directly erodes the titanium substrate can be effectively restrained.

Description

A kind of titanium-based titanium dioxide nanotube composite anode and preparation method thereof
Technical field
The invention belongs to electrochemical field, particularly relate to a kind of titanium-based titanium dioxide nanotube composite anode and preparation side thereof Method.
Background technology
Metal oxide anode is also called dimensional stable anode DSA, H.B.Beer invent, first by De Nora company of Italy First realizing industrialized production (Ti electrode engineering, Beijing: metallurgical industry publishing house, 2003), wherein metallic matrix plays conduction and bone Frame effect, surface active coating then participates in the electrochemical reaction of anode.At present, DSA has been widely used for electrometallurgy industry, chlorine Alkali industry, plating, waste water process etc..
French scientist Zwilling V prepares two by anodizing equal to reported first in 1999 on titanium plate The work of titanium oxide nanotubes, anodizing has become as and prepares one of important method of titania nanotube till now. Nano titanium oxide is as a kind of inorganic functional material, at storage and application, photoelectric conversion, the photocatalytic degradation air of solar energy And the aspect such as pollutant in water is widely used, and in Ni-Ti anode, have also been obtained preliminary application.
Although the preparation method of titanio composite anode is varied, technique is simple, and the catalysis activity of coating is high, selectivity Good, but there is a fatal shortcoming: and service life is shorter, and easily passivation forms the titanium dioxide film that one layer of electric conductivity is very poor. The most numerous researcheres, in order to solve this problem, mainly propose following several scheme: the first is to use heat coating to increase The method adding intermediate layer, generally tin ash intermediate layer, increase matrix and the adhesion being coated with interlayer so that whole coating causes Close, and increase the resistance of oxygen in solution, but be to increase intermediate layer and simply add coat and matrix to a certain extent Physical bond power, fail fundamentally to stop the erosion to matrix from the crack of coating of oxygen in solution；The second is to use Titanium is formed titanium alloy with other metal, as applied quite varied titanium manganese alloy, the oxygen on its surface inside electrolytic manganese dioxide Changing film is titanium manganese composite oxide, and its corrosion resistance is greatly improved, but the complex manufacturing technology of this method, and concordance is relatively Difference；The third is introduced into rare metal Catalytic Layer, but the catalytic action of rare metal can be only applied to specific area, and its Use cost is too high, and introduces titania nanotube intermediate layer to increase the resistance to corrosion of electrode, this in advance at electricity Although surface, pole introduces the method in thin fine and close intermediate layer and can be greatly increased the service life of Ni-Ti anode, but even titanium dioxide Its electric conductivity of titanium nanotube is the most poor, thus causes the pressure drop on whole coating relatively big, and energy consumption increases.Therefore, at present These technical schemes all cannot fundamentally solve short technological deficiency in titanio composite anode service life.
Summary of the invention
The technical problem to be solved is, overcomes the deficiency and defect mentioned in background above technology, it is provided that one Plant titanium-based titanium dioxide nanotube composite anode of extra long life and preparation method thereof.
For solving above-mentioned technical problem, the technical scheme that the present invention proposes is:
A kind of titanium-based titanium dioxide nanotube composite anode, including Titanium base layer, Nano tube array of titanium dioxide intermediate layer And active surface layer；In described Nano tube array of titanium dioxide intermediate layer, deposition has manganese metal.
Above-mentioned titanium-based titanium dioxide nanotube composite anode, it is preferred that described active surface layer is SnO2、MnO2、 IrO2、PbO2、PdO2And RuO2In one or more metal-oxide mixed layers.
Above-mentioned titanium-based titanium dioxide nanotube composite anode, it is preferred that described Titanium base layer is metallic titanium plate, titanium alloy Or titanium thin slice.
As a total inventive concept, the present invention also provides for the preparation of a kind of titanium-based titanium dioxide nanotube composite anode Method, comprises the following steps:
(1) Titanium base is carried out pretreatment；
(2) using pretreated Titanium base as anode, graphite, as negative electrode, is put in anodizing solution, anodic oxidation 5 ～20h, make Titanium base surface in situ grow Nano tube array of titanium dioxide, obtain Titanium base/Nano tube array of titanium dioxide；
(3) after described Titanium base/Nano tube array of titanium dioxide being cleaned up, as negative electrode, then with graphite as anode, In ammonia electrolytic manganese solution, it is electrolysed 5～25min, makes manganese metal be deposited in Nano tube array of titanium dioxide；
(4) one or several in the saline solution of stannum, manganese, iridium, lead, palladium or ruthenium are coated in step (3) deposition and have gold Belong to the Nano tube array of titanium dioxide surface of manganese, then carry out roasting, obtain described titanium-based titanium dioxide nanotube composite anode.
Above-mentioned preparation method, it is preferred that in described step (2), anodised voltage is 30～50V, anodic oxidation Response time is 8～20h.
Above-mentioned preparation method, it is preferred that in described step (3), in ammonia electrolytic manganese solution, the concentration of bivalent manganese is 10 ～20g/L, ammonium sulfate concentrations is 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 described step (3) refers to replace with deionized water and ethanol Washing is for several times.Preferably, the number of times of alternately washing is 3 times.
Above-mentioned preparation method, it is preferred that coating and roasting process in described step (4) need to repeat 10～15 times.
Above-mentioned preparation method, it is preferred that in described step (1), the preprocessing process of Titanium base specifically includes: first by titanium Matrix carries out sanding and polishing, then is carried out the Titanium base after sanding and polishing, is finally putting into HF and HNO3Mixed acid solution enters Row etch processes.
Compared with prior art, it is an advantage of the current invention that:
(1), in the titanium-based titanium dioxide nanotube composite anode of the present invention, nanometer titanium dioxide layer is to synchronize in-situ preparation , it is connected the finest and close with Titanium base part, does not has crannied appearance, effectively can directly corrode Titanium base by the oxygen in suppression solution And be passivated.
(2), in the titanium-based titanium dioxide nanotube composite anode of the present invention, manganese metal is grown directly upon nano titania Guan Zhong, the surface-coated method of the prior art that compares, it is greatly promoted the mixing of titanium manganese；And after baking, part manganese enters In titanium dioxide lattice, and add the content of titanous in lattice, thus increase the electric conductivity of titanium dioxide layer, reduce sun Extreme pressure drops, and reduces energy consumption.
(3) service life of the titanium-based titanium dioxide nanotube composite anode of the present invention is long more than common combination electrode.
(4) the titanium-based titanium dioxide nanotube composite anode of the present invention may be directly applied to electrolytic manganese anode, redeposited After abundant manganese, can directly form manganese dioxide active layer after heating on surface, manufacture method is simply efficient, and extremely causes Close.When using as anode, 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 the titanium-based titanium dioxide nanotube composite anode of the present invention is environmentally friendly, does not produce poisonous Gaseous contamination environment.
Accompanying drawing explanation
Fig. 1 is the structural representation of the titanium-based titanium dioxide nanotube composite anode of the present invention.
Fig. 2 is the titania nanotube in the titanium-based titanium dioxide nanotube composite anode of the embodiment of the present invention 1 preparation Scanning electron microscope (SEM) photograph.
Fig. 3 is the titanium-based titanium dioxide nanotube composite anode of the embodiment of the present invention 2 preparation and traditional Ti/MnO2Sun Pole, do not deposit the reinforcing life test and comparison figure of the titanio composite anode of manganese metal.
Fig. 4 is the titanium-based titanium dioxide nanotube composite anode of the embodiment of the present invention 3 preparation and the titanium not depositing manganese metal Based composite anode oxidation comparison diagram.
Fig. 5 is the titanium-based titanium dioxide nanotube composite anode prepared of the embodiment of the present invention 4 neutral solution system and do not sink Titanio composite anode tank voltage comparison diagram in electrolytic manganese of long-pending manganese metal.
Marginal data: 1, Titanium base layer；2, Nano tube array of titanium dioxide intermediate layer；3, active surface layer.
Detailed description of the invention
For the ease of understanding the present invention, below in conjunction with Figure of description and preferred embodiment, invention herein is done more complete Face, describe meticulously, but protection scope of the present invention is not limited to specific examples below.
Unless otherwise defined, all technical term used hereinafter is generally understood that implication phase with those skilled in the art With.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to limit the present invention's Protection domain.
Unless otherwise specified, the various raw materials used in the present invention, reagent, instrument and equipment etc. all can pass through city Field is commercially available or can be prepared by existing method.
Embodiment 1:
The titanium-based titanium dioxide nanotube composite anode of a kind of present invention, its structural representation is as it is shown in figure 1, include titanio Body layer 1, Nano tube array of titanium dioxide intermediate layer 2 and active surface layer 3；Wherein Titanium base layer 1 is pure titanium sheet, and titanium dioxide is received In mitron array intermediate layer 2, deposition has manganese metal, active surface layer 3 is MnO2。
The preparation method of the titanium-based titanium dioxide nanotube composite anode of the present embodiment, comprises the following steps:
(1) choose pure titanium sheet as Titanium base, pure titanium sheet is thrown with 360#, 600#, 800#, 1000# sand papering successively Light, more respectively with acetone, ethanol, deionized water ultrasonic cleaning 10min respectively, finally the titanium sheet that surface polishes smooth is put into HF:HNO3The mixed acid solution of=1:2 is carried out activate 30s, clean, dry；
(2) using step (1) pretreated Titanium base as anode, graphite, as negative electrode, puts into oxidation solution (NH4F11.3g/L, glycerol 250mL and water 250mL) in, temperature be 55 DEG C, voltage be oxidation 8h under 40V, make 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 about 90nm of mitron, with scanning electron microscopic observation, its pattern is as shown in Figure 2；
(3) as negative electrode after Titanium base/Nano tube array of titanium dioxide deionized water and ethanol alternately being washed 3 times, Again with graphite as anode, electrolytic deposition in ammonia electrolytic manganese solution (manganese sulfate 17g/L, ammonium sulfate 110g/L, pH7.2) (electrolytic process Anodic electric current density is 75mA/cm to 10min2, temperature is 40 DEG C), make manganese metal be deposited on nano titania In pipe array；
(4) manganese nitrate solution of 50% is coated in deposition and has the Nano tube array of titanium dioxide surface of manganese metal, be placed in Roasting 15min, the most again manganese nitrate solution of coating 50%, roasting at 500 DEG C in Muffle furnace, this process repeats 10 Secondary, last roasting 1h, i.e. obtain titanium-based titanium dioxide nanotube composite anode.
Choosing rustless steel is negative electrode, titanium-based titanium dioxide nanotube composite anode prepared by the present embodiment as anode, Pole span is 75mm, uses industrial electrolysis manganese electrolyte, with 400A/m at 40 DEG C2Electric current carry out be electrolysed 20h, anode is the most electric Position is 2.2V, and average cell voltage is 4.1V.Anode by-product is not detected by other impurity elements such as lead, with anode by-product two Manganese oxide is precursor synthetic lithium manganate capacity > 112mAh/g, cycle life > 500 times.
Embodiment 2:
The titanium-based titanium dioxide nanotube composite anode of a kind of present invention, its structural representation is as it is shown in figure 1, include titanio Body layer 1, Nano tube array of titanium dioxide intermediate layer 2 and active surface layer 3；Wherein Titanium base layer 1 is pure titanium sheet, and titanium dioxide is received In mitron array intermediate layer 2, deposition has manganese metal, active surface layer 3 is MnO2。
The preparation method of the titanium-based titanium dioxide nanotube composite anode of the present embodiment, comprises the following steps:
(1) choose pure titanium sheet as Titanium base, pure titanium sheet is thrown with 360#, 600#, 800#, 1000# sand papering successively Light, more respectively with acetone, ethanol, deionized water ultrasonic cleaning 10min respectively, finally the titanium sheet that surface polishes smooth is put into HF:HNO3The mixed acid solution of=1:2 is carried out activate 30s, clean, dry；
(2) using step (1) pretreated Titanium base as anode, graphite, as negative electrode, puts into anodizing solution (NH4F11.3g/L, glycerol 250mL and water 250mL) in, temperature be 45 DEG C, voltage be oxidation 10h under 50V, make 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) as negative electrode after Titanium base/Nano tube array of titanium dioxide deionized water and ethanol alternately being washed 3 times, Again with graphite as anode, electrolytic deposition in ammonia electrolytic manganese solution (manganese sulfate 17g/L, ammonium sulfate 110g/L, pH7.2) (electrolytic process Anodic electric current density is 75mA/cm to 15min2, temperature is 45 DEG C), make manganese metal be deposited on nano titania In pipe array；
(4) manganese nitrate solution of 50% is coated in deposition and has the Nano tube array of titanium dioxide surface of manganese metal, be placed in Roasting 15min, the most again manganese nitrate solution of coating 50%, roasting at 500 DEG C in Muffle furnace, this process repeats 10 Secondary, last roasting 1h, i.e. obtain titanium-based titanium dioxide nanotube composite anode.
The titanium-based titanium dioxide nanotube composite anode of the present embodiment is done strengthening life test in sulfuric acid solution: as Contrast, selects traditional Ti/MnO2Anode, and be prepared for unmodified under the same conditions and cross titania nanotube intermediate layer Titanio composite anode (does not i.e. deposit the titania nanotube intermediate layer of manganese metal), and three kinds of electrodes have been carried out reinforcing life Test, has obtained the Ti/MnO that result as shown in figure 3: a represents traditional2Anode, b represents in unmodified titania nanotube The titanio composite anode of interbed, c represents the titanium-based titanium dioxide nanotube composite anode of the present embodiment, can be sent out by contrast Existing, the life-span of the titanium-based titanium dioxide nanotube composite anode of the present embodiment is greatly improved.
Embodiment 3:
The titanium-based titanium dioxide nanotube composite anode of a kind of present invention, its structural representation is as it is shown in figure 1, include titanio Body layer 1, Nano tube array of titanium dioxide intermediate layer 2 and active surface layer 3；Wherein Titanium base layer 1 is pure titanium sheet, and titanium dioxide is received In mitron array intermediate layer 2, deposition has manganese metal, active surface layer 3 is RuO2。
The preparation method of the titanium-based titanium dioxide nanotube composite anode of the present embodiment, comprises the following steps:
(1) choose pure titanium sheet as Titanium base, pure titanium sheet is thrown with 360#, 600#, 800#, 1000# sand papering successively Light, more respectively with acetone, ethanol, deionized water ultrasonic cleaning 10min respectively, finally the titanium sheet that surface polishes smooth is put into HF:HNO3The mixed acid solution of=1:2 is carried out activate 30s, clean, dry；
(2) using step (1) pretreated Titanium base as anode, graphite, as negative electrode, puts into anodizing solution (NH4F11.3g/L, glycerol 250mL and water 250mL) in, temperature be 55 DEG C, voltage be oxidation 12h under 30V, make 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) as negative electrode after Titanium base/Nano tube array of titanium dioxide deionized water and ethanol alternately being washed 3 times, Again with graphite as anode, electrolytic deposition in ammonia electrolytic manganese solution (manganese sulfate 17g/L, ammonium sulfate 110g/L, pH7.2) (electrolytic process Anodic electric current density is 75mA/cm to 25min2, temperature is 40 DEG C), make manganese metal be deposited on nano titania In pipe array；
(4) ruthenium acetate solution of 50% is coated in deposition and has the Nano tube array of titanium dioxide surface of manganese metal, be placed in Roasting 15min, the most again ruthenium acetate solution of coating 50%, roasting at 500 DEG C in Muffle furnace, this process repeats 10 Secondary, last roasting 1h, i.e. obtain titanium-based titanium dioxide nanotube composite anode.
By the application in industrial wastewater of the titanium-based titanium dioxide nanotube composite anode of the present embodiment: as a comparison, system The composite anode (other structure is all identical with the present invention) of non-electro-deposition manganese in standby titania nanotube intermediate layer, by this two Planting electrode to test for the phenol aoxidizing in industrial wastewater, obtained the shown result such as Fig. 4, a represents that counter electrode, b represent Titanium-based titanium dioxide nanotube composite anode prepared by the present embodiment, by contrast it is found that the titanio dioxy of the present embodiment The activity changing titanium nanotube composite anode is greatly improved.
Embodiment 4:
The titanium-based titanium dioxide nanotube composite anode of a kind of present invention, its structural representation is as it is shown in figure 1, include titanio Body layer 1, Nano tube array of titanium dioxide intermediate layer 2 and active surface layer 3；Wherein Titanium base layer 1 is pure titanium sheet, and titanium dioxide is received In mitron array intermediate layer 2, deposition has manganese metal, active surface layer 3 is SnO2。
The preparation method of the titanium-based titanium dioxide nanotube composite anode of the present embodiment, comprises the following steps:
(1) choose pure titanium sheet as Titanium base, pure titanium sheet is thrown with 360#, 600#, 800#, 1000# sand papering successively Light, more respectively with acetone, ethanol, deionized water ultrasonic cleaning 10min respectively, finally the titanium sheet that surface polishes smooth is put into HF:HNO3The mixed acid solution of=1:2 is carried out activate 30s, clean, dry；
(2) using step (1) pretreated Titanium base as anode, graphite, as negative electrode, puts into anodizing solution (NH4F11.3g/L, glycerol 250mL and water 250mL) in, temperature be 55 DEG C, voltage be oxidation 20h under 30V, make 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) as negative electrode after Titanium base/Nano tube array of titanium dioxide deionized water and ethanol alternately being washed 3 times, Again with graphite as anode, electrolytic deposition 5min in ammonia electrolytic manganese solution (manganese sulfate 17g/L, ammonium sulfate 110g/L, pH7.2) (electrolytic process Anodic electric current density is 75mA/cm2, temperature is 45 DEG C), make manganese metal be 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 Gained solution is coated in deposition the Nano tube array of titanium dioxide surface of manganese metal, first dries 20min in 130 DEG C, then 550 Roasting 20min at DEG C, this process is repeated 10 times, and roasting 1h at 550 DEG C, i.e. obtains titanium-based titanium dioxide nanotube for the last time Composite anode.
The titanium-based titanium dioxide nanotube composite anode of the present embodiment application in electrolytic manganese: as a comparison, be prepared for In titania nanotube intermediate layer, two electrodes are entered by the composite anode (other structure is all identical with the present invention) of non-electro-deposition manganese Row reinforcing life is tested, as it is shown in figure 5, a represents titanium-based titanium dioxide nanotube composite anode prepared by the present embodiment；B represents Comparison electrode.From fig. 5, it can be seen that the life-span of the titanium-based titanium dioxide nanotube composite anode of the present invention to lengthen significantly, and And current potential is relatively low, this is because deposition has the titania nanotube layer electric conductivity of manganese metal to strengthen, the pressure drop in coating Reduce, slow down the erosion of oxygen in solution.

Claims (9)

1. a titanium-based titanium dioxide nanotube composite anode, it is characterised in that the compound sun of described titanium-based titanium dioxide nanotube Pole includes Titanium base layer, Nano tube array of titanium dioxide intermediate layer and active surface layer；In described Nano tube array of titanium dioxide In interbed, deposition has manganese metal.
2. titanium-based titanium dioxide nanotube composite anode as claimed in claim 1, it is characterised in that described active surface layer is SnO2、MnO2、IrO2、PbO2、PdO2And RuO2In one or more metal-oxide mixed layers.
3. titanium-based titanium dioxide nanotube composite anode as claimed in claim 1, it is characterised in that described Titanium base layer is gold Belong to titanium plate, titanium alloy or titanium thin slice.
4. the preparation method of a titanium-based titanium dioxide nanotube composite anode, it is characterised in that comprise the following steps:
(1) Titanium base is carried out pretreatment；
(2) using pretreated Titanium base as anode, graphite, as negative electrode, is put 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 described Titanium base/Nano tube array of titanium dioxide being cleaned up, as negative electrode, then with graphite as anode, at ammonia Property electrolytic manganese solution in be electrolysed 5～25min, make manganese metal be deposited in Nano tube array of titanium dioxide；
(4) one or several in the saline solution of stannum, manganese, iridium, lead, palladium or ruthenium are coated in step (3) deposition and have manganese metal Nano tube array of titanium dioxide surface, then carry out roasting, obtain described titanium-based titanium dioxide nanotube composite anode.
5. preparation method as claimed in claim 4, it is characterised in that in described step (2), anodised voltage be 30～ 50V, the anodic oxidation reactions time is 8～20h.
6. preparation method as claimed in claim 4, it is characterised in that in described step (3), bivalence in ammonia electrolytic manganese solution The concentration of manganese is 10～20g/L, and ammonium sulfate concentrations is 100～120g/L, and the pH of electrolytic manganese solution is 7～8.
7. preparation method as claimed in claim 4, it is characterised in that the cleaning process in described step (3) refer to spend from The alternately washing of sub-water and ethanol is for several times.
8. preparation method as claimed in claim 4, it is characterised in that coating and roasting process in described step (4) need weight Multiple 10～15 times.
9. preparation method as claimed in claim 4, it is characterised in that in described step (1), the preprocessing process tool of Titanium base Body includes: Titanium base first carries out sanding and polishing, then is carried out the Titanium base after sanding and polishing, be finally putting into HF and HNO3 Mixed acid solution carries out etch process.
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