CN110010913A - A kind of Ti-base Sn-Sb gadolinium oxide anode material and preparation method thereof - Google Patents
A kind of Ti-base Sn-Sb gadolinium oxide anode material and preparation method thereof Download PDFInfo
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- CN110010913A CN110010913A CN201910251808.XA CN201910251808A CN110010913A CN 110010913 A CN110010913 A CN 110010913A CN 201910251808 A CN201910251808 A CN 201910251808A CN 110010913 A CN110010913 A CN 110010913A
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Abstract
The invention discloses Ti-base Sn-Sb gadolinium oxide anode materials of a kind of lead flow battery and preparation method thereof.Titanium base surface preparation；The precursor sol containing pink salt, antimonic salt and gadolinium salt is prepared, using dip-coating method in Titanium base surface forming gel wet film；Desiccant gel wet film obtains gel dry film in Titanium base；Titanium plate matrix gel dry film is subjected to crystallization pretreatment, until the gel dry film is changed into tin antimony gadolinium sull；Molding tin antimony gadolinium sull is subjected to crystallization heat treatment, obtains the Ti-base Sn-Sb gadolinium oxide anode material with conducting function.Lead flow battery Ti-base Sn-Sb gadolinium oxide electrode includes the above-mentioned tin antimony gadolinium oxide coating on Titanium base and its surface.This method can be used for large scale Titanium base surface and form tin antimony gadolinium sull, and the electrode material performance of acquisition is uniform, conductivity is high, electrochemical corrosion resistant is good.Preparation process is easily controllable, process stabilizing, and repeatability is high, is suitable for industrialized production.
Description
Technical field
The invention belongs to new forms of energy new material preparation technical field, it is related to the preparation skill in relation to lead flow battery positive electrode
Art is specifically related to a kind of preparation method of the Ti-base Sn-Sb gadolinium oxide anode material of lead flow battery.
Background technique
Lead flow battery is a kind of novel redox flow battery.Using soluble lead ion as matrix solution, such as
Methane sulfonic acid lead, lead perchlorate, trifluoromethane sulfonic acid lead, lead fluoborate etc., when charging soluble lead ion negative terminal surface also
Original shape aoxidizes to form solid brown lead oxide in positive electrode surface at metallic lead, forms potential difference, due to using single electrolyte, nothing
Need diaphragm, it is only necessary to maintain a certain distance positive and negative anodes.In this way, making the structure of battery more simple, electricity is reduced
Pond cost and operating cost.Wherein electrode material is a critical component, because it provides electrochemical reaction place.It is required that it has
The requirement such as high inoxidizability, corrosion resistance, excellent homogeneous conductivity and excellent mechanical performances.Redox flow galvanic electricity at present
Pond such as all-vanadium flow battery is mainly using addition conductive filler graphite/polymer matrix composite is passed through, with light-weight, easy
It is processed into and the features such as resistivity is adjustable in a big way is widely adopted, but its resistivity compares relative to metal material
Height, electrochemical corrosion resistant is to be improved, and the uniformity of conductivity is not so good as metal material, is particularly directed to lead flow battery,
The uniformity of electrode material conductivity is most important；The conduction of electrode can be improved in the noble metals such as metal material such as platinum, palladium, ruthenium
Property, increase the binding force of coating and matrix, but it is expensive, be not suitable for business application.And cheap Titanium fund
Belong to oxide to be concerned as positive electrode, be aoxidized as metallic titanium surface forms tin antimony oxide coated Ti-base Sn-Sb of preparing
Object electrode has higher electrochemical corrosion resistant, excellent electric conductivity, and the doping of element gadolinium can be further improved the anode material
The physical and chemical performance of material.
According to the literature, the electrode material preparation method that Titanium base surface forms tin antimony gadolinium oxide coating has electro-deposition
Method, thermal decomposition method, hot dipping, metal alkoxide sol-gal process.It is wherein a large amount of in electrodeposition process, thermal decomposition method, hot dipping
Use the reagents such as nitric acid, hydrochloric acid, the tin antimony gadolinium oxidation for it is impossible to meet environmental requirement, being unfavorable for industrialized production, and preparing
Object coating performance uniformity is poor；And in traditional sol-gal process, it is main to be prepared using the hydrolysis of metal alkoxide and polymerization reaction
The colloidal sol of metal oxide or metal hydroxides, then colloidal sol is condensed into clear gel with solvent, catalyst, compounding agent etc.,
The coating uniform that this method obtains, but production cost is higher, and heat treatment process is also immature, finally obtains Ti-base Sn-Sb gadolinium oxygen
The performance of compound electrode is unstable, poor repeatability.
Summary of the invention
The first purpose of the invention is to provide a kind of Titanium base tin antimony gadolinium oxide anode material, have high conductivity with
Corrosion resistant feature.
It is a further object to provide a kind of preparation methods of Titanium base tin antimony gadolinium oxide anode material, have
The characteristics of improving antimony gadolinium oxide anode material conductivity and corrosion resistance.
First technical solution of the present invention is a kind of Titanium base tin antimony gadolinium oxide anode material, including base
Body and coating, matrix are Titanium base, and the coating on Titanium base surface is tin antimony gadolinium oxide coating, and tin antimony gadolinium oxide coating is by two
Tin oxide, antimony pentoxide and three gadolinium oxides composition.
Another technical solution of the present invention is a kind of preparation method of tin antimony gadolinium oxide anode material, tool
Body follows the steps below to implement:
Step 1 pre-processes Titanium base surface；
Step 2 prepares the precursor sol containing pink salt, antimonic salt and gadolinium salt, using the titanium of dip-coating method after the pre-treatment
Matrix surface formed gel wet film；
Step 3,2 gained gel wet film of drying steps, obtain gel dry film；
The gel dry film on the resulting Titanium base surface of step 3 is carried out crystallization pretreatment by step 4, until gel dry film changes
For tin antimony gadolinium sull；
Molding Titanium base tin antimony gadolinium sull is carried out crystallization heat treatment by step 5, obtains having conducting function
Ti-base Sn-Sb gadolinium oxide anode material.
The features of the present invention also characterized in that:
Step 1 specific steps are as follows:
Step 1.1, by after Titanium base sanding and polishing, successively cleaned with acetone and deionized water；
Titanium base after cleaning is put into the NaOH solution that mass percent is 40% by step 1.2,60~100
1~3h is impregnated at DEG C,
Titanium base after step 1.3 is impregnated moves into immersion 1~3 in the oxalic acid solution that the mass percent of boiling is 15%
Hour；
Step 1.4, oxalic acid solution impregnate after Titanium base be cleaned by ultrasonic each 5 in acetone and deionized water respectively~
It is 10 minutes, dry.
Step 2 is specifically implemented according to lower step:
Pink salt is dissolved in the first organic solvent, then adds the first chelating agent by step 2.1, and it is molten that pink salt is formed after stirring
Glue；
Antimonic salt is dissolved in a second organic solvent, then adds the second chelating agent by step 2.2, and it is molten that antimonic salt is formed after stirring
Glue；
Gadolinium salt is dissolved in a second organic solvent, then adds the second chelating agent by step 2.3, and it is molten that gadolinium salt is formed after stirring
Glue；
Pink salt colloidal sol, antimonic salt colloidal sol and gadolinium salt sol are stirred by step 2.4, and being settled to metal ion total concentration is 1
~1.5mol/L obtains the mixed sols containing pink salt, antimonic salt and gadolinium salt；
Step 2.5, using the resulting mixed sols containing pink salt, antimonic salt and gadolinium salt of step 2.4 as precursor sol, pass through leaching
Stain czochralski method prepares gel wet film in titanium-based on piece.
Precursor sol is the mixed sols of pink salt, antimonic salt and gadolinium salt in step 2, wherein Sn4+、Sb3+And Gd3+Mole
Than being 1: 0.1: 0.2；
In pink salt colloidal sol, pink salt is tin acetate, and the first chelating agent is diethylenetriamine, ethanol amine, one in diethanol amine
Kind, the first organic solvent is anhydrous methanol；In antimonic salt colloidal sol, antimonic salt is antimony acetate, and the second chelating agent is acrylic acid, Alpha-Methyl third
One of olefin(e) acid, propionic acid, lactic acid, the second organic solvent are anhydrous methanol；In gadolinium salt sol, gadolinium salt is gadolinium acetate, the second chela
Mixture is one of acrylic acid, α-methacrylic acid, propionic acid, lactic acid, and the second organic solvent is anhydrous methanol.
In pink salt colloidal sol, the molar ratio of pink salt, the first chelating agent and the first organic solvent is 1: 1~3: 20~30；Antimonic salt
In colloidal sol, the molar ratio of antimonic salt, the second chelating agent and the second organic solvent is 1: 2.5~5: 20~40；In gadolinium salt sol, gadolinium
The molar ratio of salt, the second chelating agent and the second organic solvent is 1: 1.5~2.5: 10~20.
The rate of pulling in step 2 is 0.05~0.2cm/s；
The dry temperature of step 3 is 80~100 DEG C, and the time is 10~20mins.
Step 4 is specifically implemented according to the following steps:
Step 4.1 heats the gel dry film on the resulting Titanium base surface of step 3 in dry oxygen ambient, is heated to 100 DEG C
Afterwards, wet oxygen atmosphere is changed, 200~220 DEG C is warming up to the rate of 10 DEG C/min, is warming up to 400 with the speed of 1~5 DEG C/min
~450 DEG C, and keep the temperature 10~15mins；
Dry oxygen ambient is changed after step 4.2, heat preservation, and is cooled to 200 DEG C hereinafter, obtained tin antimony gadolinium oxide is thin
Film.
Step 5 is specifically implemented according to the following steps:
Step 5.1 heats step 4 gained Titanium base tin antimony gadolinium sull in dry nitrogen atmosphere, with 15~25 DEG C/
The speed of min is heated to 510~530 DEG C；Atmosphere is then switched into wet nitrogen/oxygen mixed atmosphere, the partial pressure of oxygen is kept
In 1~2vol%, water vapor pressure is maintained at 7~8kPa, and keeps the temperature 1-2 hours；
Atmosphere is switched to dry nitrogen/oxygen mixed atmosphere by step 5.2, and the partial pressure of oxygen is maintained at 1~2vol%, is protected
20~30mins of temperature；
Step 5.3, cooling, switch to dry oxygen for atmosphere after temperature is cooled to 400~450 DEG C, and in this temperature
3~4h of lower heat preservation；After heat preservation, it is cooled back to room temperature, the Ti-base Sn-Sb gadolinium oxide anode material with conducting function is made
Material.
The beneficial effects of the present invention are:
1, the present invention use a kind of preparation method of tin antimony gadolinium oxide anode material cheap metal acetate salt for
Material synthesis, cost needed for greatly reducing production；
2, the present invention using a kind of tin antimony gadolinium oxide anode material preparation method use heat treatment operation be by
Production decision after optimization, can parameter in more accurate control items actual production, help to obtain quality more preferably titanium-based tin
Antimony gadolinium oxide coating.
Detailed description of the invention
Fig. 1 is a kind of crystallization pretreating process of the preparation method embodiment 1 of tin antimony gadolinium oxide anode material of the present invention
Flow diagram；
Fig. 2 is a kind of crystallization end treatment process of the preparation method embodiment 1 of tin antimony gadolinium oxide anode material of the present invention
Flow diagram；
Fig. 3 is a kind of titanium plate surface prepared by the preparation method embodiment 1 of tin antimony gadolinium oxide anode material of the present invention
The SEM of tin antimony gadolinium sull schemes.
Specific embodiment
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
A kind of Titanium base tin antimony gadolinium oxide anode material, including matrix and coating, matrix are Titanium base, Titanium base surface
Coating be tin antimony gadolinium oxide coating, tin antimony gadolinium oxide coating is made of stannic oxide, antimony pentoxide and three gadolinium oxides.
A kind of preparation method of tin antimony gadolinium oxide anode material, is specifically implemented according to the following steps:
Step 1 pre-processes Titanium base surface；
Step 2 prepares the precursor sol containing pink salt, antimonic salt and gadolinium salt, using the titanium of dip-coating method after the pre-treatment
Matrix surface formed gel wet film；
Step 3,2 gained gel wet film of drying steps, obtain gel dry film；
The gel dry film on the resulting Titanium base surface of step 3 is carried out crystallization pretreatment by step 4, until gel dry film changes
For tin antimony gadolinium sull；
Molding Titanium base tin antimony gadolinium sull is carried out crystallization heat treatment by step 5, obtains having conducting function
Ti-base Sn-Sb gadolinium oxide anode material.
Step 1 specific steps are as follows:
Step 1.1, by after Titanium base sanding and polishing, successively cleaned with acetone and deionized water；
Titanium base after cleaning is put into the NaOH solution that mass percent is 40% by step 1.2,60~100
1~3h is impregnated at DEG C,
Titanium base after step 1.3 is impregnated moves into immersion 1~3 in the oxalic acid solution that the mass percent of boiling is 15%
Hour；
The ultrasonic cleaning 5~10 in acetone and deionized water respectively of Titanium base after step 1.4, oxalic acid solution immersion
Minute, it is dry；
Step 2 is specifically implemented according to lower step:
Pink salt is dissolved in the first organic solvent, then adds the first chelating agent by step 2.1, and it is molten that pink salt is formed after stirring
Glue；
Antimonic salt is dissolved in a second organic solvent, then adds the second chelating agent by step 2.2, and it is molten that antimonic salt is formed after stirring
Glue；
Gadolinium salt is dissolved in a second organic solvent, then adds the second chelating agent by step 2.3, and it is molten that gadolinium salt is formed after stirring
Glue；
Pink salt colloidal sol, antimonic salt colloidal sol and gadolinium salt sol are stirred by step 2.4, and being settled to metal ion total concentration is 1
~1.5mol/L obtains the mixed sols containing pink salt, antimonic salt and gadolinium salt；
Step 2.5, using the resulting mixed sols containing pink salt, antimonic salt and gadolinium salt of step 2.4 as precursor sol, pass through leaching
Stain czochralski method prepares gel wet film in titanium-based on piece；
Precursor sol is the mixed sols of pink salt, antimonic salt and gadolinium salt in step 2, wherein Sn4+、Sb3+And Gd3+Mole
Than being 1: 0.1: 0.2；
In pink salt colloidal sol, pink salt is tin acetate, and the first chelating agent is diethylenetriamine, ethanol amine, one in diethanol amine
Kind, the first organic solvent is anhydrous methanol；In antimonic salt colloidal sol, antimonic salt is antimony acetate, and the second chelating agent is acrylic acid, Alpha-Methyl third
One of olefin(e) acid, propionic acid, lactic acid, the second organic solvent are anhydrous methanol；In gadolinium salt sol, gadolinium salt is gadolinium acetate, the second chela
Mixture is one of acrylic acid, α-methacrylic acid, propionic acid, lactic acid, and the second organic solvent is anhydrous methanol.
In pink salt colloidal sol, the molar ratio of pink salt, the first chelating agent and the first organic solvent is 1: 1~3: 20~30；Antimonic salt
In colloidal sol, the molar ratio of antimonic salt, the second chelating agent and the second organic solvent is 1: 2.5~5: 20~40；In gadolinium salt sol, gadolinium
The molar ratio of salt, the second chelating agent and the second organic solvent is 1: 1.5~2.5: 10~20.
The rate of pulling in step 2 is 0.05~0.2cm/s.
The dry temperature of step 3 is 80~100 DEG C, and the time is 10~20mins.
Step 4 is specifically implemented according to the following steps:
Step 4.1 heats the gel dry film on the resulting Titanium base surface of step 3 in dry oxygen ambient, in dry oxygen ambient
In be heated to 100 DEG C after, change wet oxygen atmosphere, 200~220 DEG C are warming up to the rate of 10 DEG C/min, with 1~5 DEG C/min's
Speed is warming up to 400~450 DEG C, and keeps the temperature 10~15mins；
Dry oxygen ambient is changed after step 4.2, heat preservation, and is cooled to 200 DEG C or less and tin antimony gadolinium sull is made.
Step 5 is specifically implemented according to the following steps:
Step 5.1, step 4 gained Titanium base tin antimony gadolinium sull heat in dry nitrogen atmosphere, with 15~25 DEG C/
The speed of min is heated to 510~530 DEG C；Atmosphere is then switched into wet nitrogen/oxygen mixed atmosphere, the partial pressure of oxygen is kept
In 1~2vol%, water vapor pressure is maintained at 7~8kPa, and keeps the temperature 1-2 hours；
Atmosphere is switched to dry nitrogen/oxygen mixed atmosphere by step 5.2, and the partial pressure of oxygen is maintained at 1~2vol%, is protected
20~30mins of temperature；
Step 5.3, cooling, switch to dry oxygen for atmosphere after temperature is cooled to 400~450 DEG C, and at this temperature
Keep the temperature 3~4h；After heat preservation, it is cooled back to room temperature, the Ti-base Sn-Sb gadolinium oxide anode material with conducting function is made.
Compared with the prior art, the advantages of the present invention are as follows:
The present invention directly prepares tin antimony gadolinium oxide anode material in matrix using sol-gel method and heat treatment process,
Specifically, it uses cheap small molecule metal acetate salt for starting material, is not directed to expensive macromolecular metal carboxylate
Or metal alkoxide, greatly reduce cost；
Using the complexing of diethylenetriamine and acrylic acid by acetate dissolution of raw material foring property in anhydrous methanol
Energy stablizes and the tin antimony gadolinium oxygen solution of good film-forming property, and solution composition is easily adjusted, performance is stable and good film-forming property.Again by exploring, obtain
Optimal heat treatment process is obtained, the heat treatment process taken in the present invention, is the optimal heat treatment process optimized, only sternly
Lattice control the heating rate in heat treatment process, steam partial pressure, and the atmosphere such as partial pressure of oxygen could obtain the titanium-based tin of high conductivity
Antimony gadolinium oxide coating；
It by low temperature drying, 400-450 DEG C of wet oxygen atmosphere thermal decomposition, and is 1- by partial pressure of oxygen using the solution
2vol%, steam partial pressure is the nitrogen of 7-8%kPa, at 510-530 DEG C of high-temperature calcination and last 400-450 DEG C of infiltration oxygen
Reason can get high quality Ti-base Sn-Sb gadolinium oxide coating positive electrode.Meanwhile with currently reported sol-gal process phase
Than not only substantially reducing heat treatment cycle, significantly improving film preparation efficiency, film surface is more fine and close smooth, simultaneously
Solve the problems, such as that film is easy to crack.And Heat Treatment Control equipment is simple, and 1- can be realized using the control of simple flowmeter
The partial pressure of oxygen of 2vol%.Heat-treatment technology method is easy, and easily operated, process cycle is short.Process stabilizing, repeatability are high.It should
Method can be used for preparing large scale Ti-base Sn-Sb oxide electrode material, the tin-antimony oxide film performance of acquisition uniformly, conductance
Rate can reach 100S/cm or more, with the H of 3M2SO4Corrosion rate can be obtained using electrochemistry linear polarization method for electrolyte
1 μ A/cm of <2。
Embodiment 1
Step 1 pre-processes Titanium base surface；
Step 1.1 selects titanium plate as Titanium base, respectively with after the sand paper sanding and polishing of 40,500 and 1200 mesh, successively
It is cleaned with acetone and deionized water；
Titanium base after cleaning is put into the NaOH solution that mass percent is 40% by step 1.2, is soaked at 60 DEG C
1h is steeped,
It is 1 small that Titanium base after step 1.3 immersion moves into immersion in the oxalic acid solution that the mass percent of boiling is 15%
When；
Step 1.4, the Titanium base after oxalic acid solution impregnates are cleaned by ultrasonic each 5 points in acetone and deionized water respectively
Clock, it is dry；
Step 2 prepares the precursor sol containing pink salt, antimonic salt and gadolinium salt, using the titanium of dip-coating method after the pre-treatment
Matrix surface formed gel wet film；
Tin acetate is dissolved in anhydrous methanol by step 2.1, diethylenetriamine is then added, tin acetate: diethylenetriamine
: molar ratio=1 of anhydrous methanol: 1: 20, agitated dissolution forms acetic acid tin oxide sol；
Antimony acetate is dissolved in anhydrous methanol by step 2.2, acrylic acid is then added, antimony acetate: acrylic acid: without water beetle
Molar ratio=1 of alcohol: 2.5: 20, antimony acetate colloidal sol is formed after stirring and dissolving；
Gadolinium acetate is dissolved in anhydrous methanol by step 2.3, acrylic acid is then added, gadolinium acetate: acrylic acid: without water beetle
Molar ratio=1 of alcohol: 1.5: 10, gadolinium acetate colloidal sol is formed after stirring and dissolving；
Acetic acid tin oxide sol and antimony acetate colloidal sol are pressed Sn by step 2.44+∶Sb3+:Gd3+=1:0.1:0.2 mixing, is settled to
Metal ion total concentration is 1mol/L, obtains the mixed sols containing pink salt, antimonic salt and gadolinium salt；
Step 2.5, using the resulting mixed sols containing pink salt, antimonic salt and gadolinium salt of step 2.4 as precursor sol, pass through leaching
Stain czochralski method prepares gel wet film, pull rate 0.05cm/s in titanium-based on piece, and available thickness is about that 1 μm of gel is wet
Film；
Step 3, in air atmosphere and in 80 DEG C of at a temperature of dry 10mins, make moisture, solvent, the organic matter in film
Deng abundant volatilization, gel dry film is obtained；
The gel dry film on the resulting Titanium base surface of step 3 is carried out crystallization pretreatment by step 4, until gel dry film changes
For tin antimony gadolinium sull；
The Titanium base with gel dry film of acquisition is put into and moves on in quartz tube type sintering furnace by step 4.1, as shown in Figure 1,
It is heated to 100 DEG C, after 30min in dry oxygen ambient, changes wet oxygen atmosphere, 200 DEG C is warming up to the rate of 10 DEG C/min, with 1
DEG C/speed of min is warming up to 400 DEG C, and keeps the temperature 10mins；
Dry oxygen ambient is changed after step 4.2, heat preservation, and is cooled to 200 DEG C hereinafter, obtained tin antimony gadolinium oxide is thin
Film.
Molding Titanium base tin antimony gadolinium sull is carried out crystallization heat treatment by step 5, obtains having conducting function
Ti-base Sn-Sb gadolinium oxide anode material；
Step 5.1 will handle molding Titanium base tin antimony gadolinium sull through step 4 and be transferred in quartz ampoule, such as Fig. 2 institute
Show, other atmosphere in quartz ampoule are excluded using the mode of vacuumizing, is heated to 510 in dry nitrogen atmosphere with the speed of 15 DEG C/min
DEG C, after 30min, atmosphere is switched into wet nitrogen/oxygen mixed atmosphere, the partial pressure of oxygen is maintained at 1vol%, and water vapor pressure is protected
It holds in 7.8kPa, and keeps the temperature 1 hour；
Atmosphere is switched to dry nitrogen/oxygen mixed atmosphere by step 5.2, and the partial pressure of oxygen is maintained at 1vol%, heat preservation
20mins；
Step 5.3 closes sintering furnace, and cools down automatically, and after being cooled to 400 DEG C, atmosphere is switched to dry oxygen ambient, and
3 hours are kept the temperature at 400 DEG C.After subsequent furnace cooling to room temperature, closes atmosphere and take out the Ti-base Sn-Sb gadolinium with conducting function
Oxide anode material.
The tin antimony gadolinium oxide coating thickness on gained Titanium base surface is about 240nm, and the conductivity of gained positive electrode can
To reach 4.1 × 102S/cm, in the H of 3M2SO4For the 0.56 μ A/cm of corrosion rate of electrolyte2。
Embodiment 2
Step 1 pre-processes Titanium base surface；
Step 1.1 selects titanium plate as Titanium base, respectively with after the sand paper sanding and polishing of 40,500 and 1200 mesh, successively
It is cleaned with acetone and deionized water；
Titanium base after cleaning is put into the NaOH solution that mass percent is 40% by step 1.2, is soaked at 70 DEG C
1.5h is steeped,
Titanium base after step 1.3 is impregnated moves into immersion 1.5 in the oxalic acid solution that the mass percent of boiling is 15%
Hour；
Step 1.4, the Titanium base after oxalic acid solution impregnates are cleaned by ultrasonic each 7 points in acetone and deionized water respectively
Clock, it is dry；
Step 2 prepares the precursor sol containing pink salt, antimonic salt and gadolinium salt, using the titanium of dip-coating method after the pre-treatment
Matrix surface formed gel wet film；
Tin acetate is dissolved in anhydrous methanol by step 2.1, ethanol amine is then added, tin acetate: ethanol amine: without water beetle
Molar ratio=1 of alcohol: 2: 25, agitated dissolution forms acetic acid tin oxide sol；
Antimony acetate is dissolved in anhydrous methanol by step 2.2, α-methacrylic acid is then added, antimony acetate: Alpha-Methyl third
Olefin(e) acid: molar ratio=1 of anhydrous methanol: 2: 25, antimony acetate colloidal sol is formed after stirring and dissolving；
Gadolinium acetate is dissolved in anhydrous methanol by step 2.3, α-methacrylic acid is then added, gadolinium acetate: Alpha-Methyl third
Olefin(e) acid: molar ratio=1 of anhydrous methanol: 1.5: 15, gadolinium acetate colloidal sol is formed after stirring and dissolving；
Acetic acid tin oxide sol and antimony acetate colloidal sol are pressed Sn by step 2.44+∶Sb3+:Gd3+=1:0.1:0.2 mixing, is settled to
Metal ion total concentration is 1.4mol/L, obtains the mixed sols containing pink salt, antimonic salt and gadolinium salt；
Step 2.5, using the resulting mixed sols containing pink salt, antimonic salt and gadolinium salt of step 2.4 as precursor sol, pass through leaching
Stain czochralski method prepares gel wet film, pull rate 0.15cm/s in titanium-based on piece, and available thickness is about that 1 μm of gel is wet
Film；
Step 3, in air atmosphere and in 85 DEG C of at a temperature of dry 13mins, make moisture, solvent, the organic matter in film
Deng abundant volatilization, gel dry film is obtained；
The gel dry film on the resulting Titanium base surface of step 3 is carried out crystallization pretreatment by step 4, until gel dry film changes
For tin antimony gadolinium sull；
The Titanium base with gel dry film of acquisition is put into and moves on in quartz tube type sintering furnace by step 4.1, in dry oxygen ambient
In be heated to 100 DEG C after, change wet oxygen atmosphere, be warming up to 206 DEG C with the rate of 10 DEG C/min, heated up with the speed of 2 DEG C/min
To 417 DEG C, and keep the temperature 11mins；
Dry oxygen ambient is changed after step 4.2, heat preservation, and is cooled to 200 DEG C hereinafter, obtained tin antimony gadolinium oxide is thin
Film.
Molding Titanium base tin antimony gadolinium sull is carried out crystallization heat treatment by step 5, obtains having conducting function
Ti-base Sn-Sb gadolinium oxide anode material；
Step 5.1 will handle molding Titanium base tin antimony gadolinium sull through step 4 and be transferred in quartz ampoule, such as Fig. 2 institute
Show, other atmosphere in quartz ampoule are excluded using the mode of vacuumizing, is heated to 514 in dry nitrogen atmosphere with the speed of 18 DEG C/min
DEG C, after 30min, atmosphere is switched into wet nitrogen/oxygen mixed atmosphere, the partial pressure of oxygen is maintained at 2vol%, and water vapor pressure is protected
It holds in 7kPa, and keeps the temperature 2 hours；
Atmosphere is switched to dry nitrogen/oxygen mixed atmosphere by step 5.2, and the partial pressure of oxygen is maintained at 2vol%, heat preservation
22mins；
Step 5.3 closes sintering furnace, and cools down automatically, and after being cooled to 400 DEG C, atmosphere is switched to dry oxygen ambient, and
3 hours are kept the temperature at 413 DEG C.After subsequent furnace cooling to room temperature, closes atmosphere and take out the Ti-base Sn-Sb gadolinium with conducting function
Oxide anode material.
The tin antimony gadolinium oxide coating thickness on gained Titanium base surface is about 300nm, and the conductivity of gained positive electrode can
To reach 2.6 × 102S/cm, in the H of 3M2SO4For the 0.35 μ A/cm of corrosion rate of electrolyte2。
Embodiment 3
Step 1 pre-processes Titanium base surface；
Step 1.1 selects titanium plate as Titanium base, respectively with after the sand paper sanding and polishing of 40,500 and 1200 mesh, successively
It is cleaned with acetone and deionized water；
Titanium base after cleaning is put into the NaOH solution that mass percent is 40% by step 1.2, is soaked at 90 DEG C
2.5h is steeped,
It is 2 small that Titanium base after step 1.3 immersion moves into immersion in the oxalic acid solution that the mass percent of boiling is 15%
When；
Step 1.4, the Titanium base after oxalic acid solution impregnates are cleaned by ultrasonic each 8 points in acetone and deionized water respectively
Clock, it is dry；
Step 2 prepares the precursor sol containing pink salt, antimonic salt and gadolinium salt, using the titanium of dip-coating method after the pre-treatment
Matrix surface formed gel wet film；
Tin acetate is dissolved in anhydrous methanol by step 2.1, diethanol amine is then added, tin acetate: diethanol amine: nothing
Molar ratio=1 of water methanol: 2: 25, agitated dissolution forms acetic acid tin oxide sol；
Antimony acetate is dissolved in anhydrous methanol by step 2.2, propionic acid is then added, antimony acetate: propionic acid: anhydrous methanol
Molar ratio=1: 3: 25, antimony acetate colloidal sol is formed after stirring and dissolving；
Gadolinium acetate is dissolved in anhydrous methanol by step 2.3, propionic acid is then added, gadolinium acetate: propionic acid: anhydrous methanol
Molar ratio=1: 2: 15, gadolinium acetate colloidal sol is formed after stirring and dissolving；
Acetic acid tin oxide sol and antimony acetate colloidal sol are pressed Sn by step 2.44+∶Sb3+:Gd3+=1:0.1:0.2 mixing, is settled to
Metal ion total concentration is 1.5mol/L, obtains the mixed sols containing pink salt, antimonic salt and gadolinium salt；
Step 2.5, using the resulting mixed sols containing pink salt, antimonic salt and gadolinium salt of step 2.4 as precursor sol, pass through leaching
Stain czochralski method prepares gel wet film, pull rate 0.15cm/s in titanium-based on piece, and available thickness is about that 1 μm of gel is wet
Film；
Step 3, in air atmosphere and in 90 DEG C of at a temperature of dry 15mins, make moisture, solvent, the organic matter in film
Deng abundant volatilization, gel dry film is obtained；
The gel dry film on the resulting Titanium base surface of step 3 is carried out crystallization pretreatment by step 4, until gel dry film changes
For tin antimony gadolinium sull；
The Titanium base with gel dry film of acquisition is put into and moves on in quartz tube type sintering furnace by step 4.1, as shown in Figure 1,
It is heated to 100 DEG C, after 30min in dry oxygen ambient, changes wet oxygen atmosphere, 210 DEG C is warming up to the rate of 10 DEG C/min, with 3
DEG C/speed of min is warming up to 425 DEG C, and keeps the temperature 12mins；
Dry oxygen ambient is changed after step 4.2, heat preservation, and is cooled to 200 DEG C hereinafter, obtained tin antimony gadolinium oxide is thin
Film.
Molding Titanium base tin antimony gadolinium sull is carried out crystallization heat treatment by step 5, obtains having conducting function
Ti-base Sn-Sb gadolinium oxide anode material；
Step 5.1 will handle molding Titanium base tin antimony gadolinium sull through step 4 and be transferred in quartz ampoule, such as Fig. 2 institute
Show, other atmosphere in quartz ampoule are excluded using the mode of vacuumizing, is heated to 520 in dry nitrogen atmosphere with the speed of 20 DEG C/min
DEG C, after 30min, atmosphere is switched into wet nitrogen/oxygen mixed atmosphere, the partial pressure of oxygen is maintained at 1vol%, and water vapor pressure is protected
It holds in 7.5kPa, and keeps the temperature 1 hour；
Atmosphere is switched to dry nitrogen/oxygen mixed atmosphere by step 5.2, and the partial pressure of oxygen is maintained at 2vol%, heat preservation
25mins；
Step 5.3 closes sintering furnace, and cools down automatically, and after being cooled to 400 DEG C, atmosphere is switched to dry oxygen ambient, and
3.5 hours are kept the temperature at 425 DEG C.After subsequent furnace cooling to room temperature, closes atmosphere and take out the Ti-base Sn-Sb with conducting function
Gadolinium oxide anode material.
The tin antimony gadolinium oxide coating thickness on gained Titanium base surface is about 260nm, and the conductivity of gained positive electrode can
To reach 4.6 × 102S/cm, in the H of 3M2SO4For the 0.21 μ A/cm of corrosion rate of electrolyte2。
Embodiment 4
Step 1 pre-processes Titanium base surface；
Step 1.1 selects titanium plate as Titanium base, respectively with after the sand paper sanding and polishing of 40,500 and 1200 mesh, successively
It is cleaned with acetone and deionized water；
Titanium base after cleaning is put into the NaOH solution that mass percent is 40% by step 1.2, is soaked at 60 DEG C
1h is steeped,
Titanium base after step 1.3 is impregnated moves into immersion 2.5 in the oxalic acid solution that the mass percent of boiling is 15%
Hour；
Step 1.4, the Titanium base after oxalic acid solution impregnates are cleaned by ultrasonic each 9 points in acetone and deionized water respectively
Clock, it is dry；
Step 2 prepares the precursor sol containing pink salt, antimonic salt and gadolinium salt, using the titanium of dip-coating method after the pre-treatment
Matrix surface formed gel wet film；
Tin acetate is dissolved in anhydrous methanol by step 2.1, diethylenetriamine is then added, tin acetate: diethylenetriamine
: molar ratio=1 of anhydrous methanol: 1: 25, agitated dissolution forms acetic acid tin oxide sol；
Antimony acetate is dissolved in anhydrous methanol by step 2.2, lactic acid is then added, antimony acetate: lactic acid: anhydrous methanol
Molar ratio=1: 2.5: 30, antimony acetate colloidal sol is formed after stirring and dissolving；
Gadolinium acetate is dissolved in anhydrous methanol by step 2.3, lactic acid is then added, gadolinium acetate: lactic acid: anhydrous methanol
Molar ratio=1: 1.5: 15, gadolinium acetate colloidal sol is formed after stirring and dissolving；
Acetic acid tin oxide sol and antimony acetate colloidal sol are pressed Sn by step 2.44+∶Sb3+:Gd3+=1:0.1:0.2 mixing, is settled to
Metal ion total concentration is 1.2mol/L, obtains the mixed sols containing pink salt, antimonic salt and gadolinium salt；
Step 2.5, using the resulting mixed sols containing pink salt, antimonic salt and gadolinium salt of step 2.4 as precursor sol, pass through leaching
Stain czochralski method prepares gel wet film, pull rate 0.05cm/s in titanium-based on piece, and available thickness is about that 1 μm of gel is wet
Film；
Step 3, in air atmosphere and in 95 DEG C of at a temperature of dry 17mins, make moisture, solvent, the organic matter in film
Deng abundant volatilization, gel dry film is obtained；
The gel dry film on the resulting Titanium base surface of step 3 is carried out crystallization pretreatment by step 4, until gel dry film changes
For tin antimony gadolinium sull；
The Titanium base with gel dry film of acquisition is put into and moves on in quartz tube type sintering furnace by step 4.1, as shown in Figure 1,
It is heated to 100 DEG C, after 30min in dry oxygen ambient, changes wet oxygen atmosphere, 214 DEG C is warming up to the rate of 10 DEG C/min, with 4
DEG C/speed of min is warming up to 430 DEG C, and keeps the temperature 14mins；
Dry oxygen ambient is changed after step 4.2, heat preservation, and is cooled to 200 DEG C hereinafter, obtained tin antimony gadolinium oxide is thin
Film.
Molding Titanium base tin antimony gadolinium sull is carried out crystallization heat treatment by step 5, obtains having conducting function
Ti-base Sn-Sb gadolinium oxide anode material；
Step 5.1 will handle molding Titanium base tin antimony gadolinium sull through step 4 and be transferred in quartz ampoule, such as Fig. 2 institute
Show, other atmosphere in quartz ampoule are excluded using the mode of vacuumizing, is heated to 525 in dry nitrogen atmosphere with the speed of 22 DEG C/min
DEG C, after 30min, atmosphere is switched into wet nitrogen/oxygen mixed atmosphere, the partial pressure of oxygen is maintained at 2vol%, and water vapor pressure is protected
It holds in 8kPa, and keeps the temperature 2 hours；
Atmosphere is switched to dry nitrogen/oxygen mixed atmosphere by step 5.2, and the partial pressure of oxygen is maintained at 1vol%, heat preservation
26mins；
Step 5.3 closes sintering furnace, and cools down automatically, and after being cooled to 400 DEG C, atmosphere is switched to dry oxygen ambient, and
3.5 hours are kept the temperature at 440 DEG C.After subsequent furnace cooling to room temperature, closes atmosphere and take out the Ti-base Sn-Sb with conducting function
Gadolinium oxide anode material.
The tin antimony gadolinium oxide coating thickness on gained Titanium base surface is about 340nm, and the conductivity of gained positive electrode can
To reach 3.3 × 102S/cm, in the H of 3M2SO4For the 0.27 μ A/cm of corrosion rate of electrolyte2。
Embodiment 5
Step 1 pre-processes Titanium base surface；
Step 1.1 selects titanium plate as Titanium base, respectively with after the sand paper sanding and polishing of 40,500 and 1200 mesh, successively
It is cleaned with acetone and deionized water；
Titanium base after cleaning is put into the NaOH solution that mass percent is 40% by step 1.2, at 100 DEG C
Impregnate 3h；
It is 3 small that Titanium base after step 1.3 immersion moves into immersion in the oxalic acid solution that the mass percent of boiling is 15%
When；
Step 1.4, the Titanium base after oxalic acid solution impregnates are cleaned by ultrasonic each 10 in acetone and deionized water respectively
Minute, it is dry；
Step 2 prepares the precursor sol containing pink salt, antimonic salt and gadolinium salt, using the titanium of dip-coating method after the pre-treatment
Matrix surface formed gel wet film；
Tin acetate is dissolved in anhydrous methanol by step 2.1, ethanol amine is then added, tin acetate: diethanol amine: anhydrous
Molar ratio=1 of methanol: 3: 30, agitated dissolution forms acetic acid tin oxide sol；
Antimony acetate is dissolved in anhydrous methanol by step 2.2, acrylic acid is then added, antimony acetate: acrylic acid: without water beetle
Molar ratio=1 of alcohol: 5: 40, antimony acetate colloidal sol is formed after stirring and dissolving；
Gadolinium acetate is dissolved in anhydrous methanol by step 2.3, acrylic acid is then added, gadolinium acetate: acrylic acid: without water beetle
Molar ratio=1 of alcohol: 2.5: 20, gadolinium acetate colloidal sol is formed after stirring and dissolving；
Acetic acid tin oxide sol and antimony acetate colloidal sol are pressed Sn by step 2.44+∶Sb3+:Gd3+=1:0.1:0.2 mixing, is settled to
Metal ion total concentration is 1.5mol/L, obtains the mixed sols containing pink salt, antimonic salt and gadolinium salt；
Step 2.5, using the resulting mixed sols containing pink salt, antimonic salt and gadolinium salt of step 2.4 as precursor sol, pass through leaching
Stain czochralski method prepares gel wet film, pull rate 0.05cm/s in titanium-based on piece, and available thickness is about that 1 μm of gel is wet
Film；
Step 3, in air atmosphere and in 100 DEG C of at a temperature of dry 20mins, make moisture in film, solvent, organic
Object etc. sufficiently volatilizees, and obtains gel dry film；
The gel dry film on the resulting Titanium base surface of step 3 is carried out crystallization pretreatment by step 4, until gel dry film changes
For tin antimony gadolinium sull；
The Titanium base with gel dry film of acquisition is put into and moves on in quartz tube type sintering furnace by step 4.1, as shown in Figure 1,
It is heated to 100 DEG C, after 30min in dry oxygen ambient, changes wet oxygen atmosphere, 220 DEG C is warming up to the rate of 10 DEG C/min, with 5
DEG C/speed of min is warming up to 450 DEG C, and keeps the temperature 15mins；
Dry oxygen ambient is changed after step 4.2, heat preservation, and is cooled to 200 DEG C hereinafter, obtained tin antimony gadolinium oxide is thin
Film.
Molding Titanium base tin antimony gadolinium sull is carried out crystallization heat treatment by step 5, obtains having conducting function
Ti-base Sn-Sb gadolinium oxide anode material；
Step 5.1 will handle molding Titanium base tin antimony gadolinium sull through step 4 and be transferred in quartz ampoule, such as Fig. 2 institute
Show, other atmosphere in quartz ampoule are excluded using the mode of vacuumizing, is heated to 530 in dry nitrogen atmosphere with the speed of 25 DEG C/min
DEG C, after 30min, atmosphere is switched into wet nitrogen/oxygen mixed atmosphere, the partial pressure of oxygen is maintained at 2vol%, and water vapor pressure is protected
It holds in 8kPa, and keeps the temperature 2 hours；
Atmosphere is switched to dry nitrogen/oxygen mixed atmosphere by step 5.2, and the partial pressure of oxygen is maintained at 2vol%, heat preservation
30mins；
Step 5.3 closes sintering furnace, and cools down automatically, and after being cooled to 400 DEG C, atmosphere is switched to dry oxygen ambient, and
4 hours are kept the temperature at 450 DEG C.After subsequent furnace cooling to room temperature, closes atmosphere and take out the Ti-base Sn-Sb gadolinium with conducting function
Oxide anode material.
The tin antimony gadolinium oxide coating thickness on gained Titanium base surface is about 280nm, and the conductivity of gained positive electrode can
To reach 3.1 × 102S/cm, in the H of 3M2SO4For the 0.52 μ A/cm of corrosion rate of electrolyte2。
| Conductivity (S/cm) | Corrosion rate (μ A/cm2) | |
| Embodiment 1 | 4.1×102 | 0.56 |
| Embodiment 2 | 2.6×102 | 0.35 |
| Embodiment 3 | 4.6×102 | 0.21 |
| Embodiment 4 | 3.3×102 | 0.27 |
| Embodiment 5 | 3.1×102 | 0.52 |
Table 1
As can be seen from Table 1: the conductivity of the positive electrode of embodiment 1-5 and the H in 3M2SO4For the corrosion speed of electrolyte
Rate reaches and is better than U.S. Department of Energy bipolar plates performance standard, i.e. conductivity should be greater than 100S/cm, and corrosion rate should be less than 1 μ A/
cm2。
Show that tin antimony oxide film has flat and smooth surface as seen from Figure 3, and crystallite dimension is small, more
It is even, fine and close.
Claims (9)
1. a kind of Titanium base tin antimony gadolinium oxide anode material, including matrix and coating, which is characterized in that described matrix is titanium-based
The coating of body, the Titanium base surface is tin antimony gadolinium oxide coating, and the tin antimony gadolinium oxide coating is by stannic oxide, five oxygen
Change two antimony and three gadolinium oxides composition.
2. a kind of preparation method of Titanium base tin antimony gadolinium oxide anode material according to claim 1, which is characterized in that tool
Body follows the steps below to implement:
Step 1 pre-processes Titanium base surface；
Step 2 prepares the precursor sol containing pink salt, antimonic salt and gadolinium salt, using the Titanium base of dip-coating method after the pre-treatment
Surface forming gel wet film；
Step 3,2 gained gel wet film of drying steps, obtain gel dry film；
The gel dry film on the resulting Titanium base surface of step 3 is carried out crystallization pretreatment by step 4, until gel dry film is changed into tin
Antimony gadolinium sull；
Molding Titanium base tin antimony gadolinium sull is carried out crystallization heat treatment by step 5, obtains the titanium-based with conducting function
Tin antimony gadolinium oxide anode material.
3. a kind of preparation method of tin antimony gadolinium oxide anode material according to claim 2, which is characterized in that the step
Rapid 1 specific steps are as follows:
Step 1.1, by after Titanium base sanding and polishing, successively cleaned with acetone and deionized water；
Titanium base after cleaning is put into the NaOH solution that mass percent is 40% by step 1.2, at 60~100 DEG C
Impregnate 1~3h；
It is 1~3 small that Titanium base after step 1.3 immersion moves into immersion in the oxalic acid solution that the mass percent of boiling is 15%
When；
Step 1.4, the Titanium base after oxalic acid solution impregnates are cleaned by ultrasonic each 5~10 points in acetone and deionized water respectively
Clock, it is dry.
4. a kind of preparation method of tin antimony gadolinium oxide anode material according to claim 2, which is characterized in that the step
Rapid 2 specifically implement according to lower step:
Pink salt is dissolved in the first organic solvent, then adds the first chelating agent by step 2.1, and pink salt colloidal sol is formed after stirring；
Antimonic salt is dissolved in a second organic solvent, then adds the second chelating agent by step 2.2, and antimonic salt colloidal sol is formed after stirring；
Gadolinium salt is dissolved in a second organic solvent, then adds the second chelating agent by step 2.3, and gadolinium salt sol is formed after stirring；
Pink salt colloidal sol, antimonic salt colloidal sol and gadolinium salt sol are stirred by step 2.4, be settled to metal ion total concentration be 1~
1.5mol/L obtains the mixed sols containing pink salt, antimonic salt and gadolinium salt；
Step 2.5, using the resulting mixed sols containing pink salt, antimonic salt and gadolinium salt of step 2.4 as precursor sol, by dipping mention
Daraf(reciprocal of farad) prepares gel wet film in titanium-based on piece.
5. a kind of preparation method of tin antimony gadolinium oxide anode material according to claim 4, which is characterized in that the step
Precursor sol is the mixed sols of pink salt, antimonic salt and gadolinium salt in rapid 2, wherein Sn4+、Sb3+And Gd3+Molar ratio be 1: 0.1:
0.2；
In the pink salt colloidal sol, the pink salt is tin acetate, and first chelating agent is diethylenetriamine, ethanol amine, diethanol
One of amine, first organic solvent are anhydrous methanol；In the antimonic salt colloidal sol, the antimonic salt is antimony acetate, described the
Two chelating agents are one of acrylic acid, α-methacrylic acid, propionic acid, lactic acid, and second organic solvent is anhydrous methanol；Institute
It states in gadolinium salt sol, the gadolinium salt is gadolinium acetate, and second chelating agent is acrylic acid, in α-methacrylic acid, propionic acid, lactic acid
One kind, second organic solvent be anhydrous methanol.
In the step 2 in pink salt colloidal sol, the molar ratio of the pink salt, the first chelating agent and the first organic solvent is 1: 1~3:
20~30；In the antimonic salt colloidal sol, the molar ratio of the antimonic salt, the second chelating agent and the second organic solvent is 1: 2.5~5: 20
~40；In the gadolinium salt sol, the molar ratio of the gadolinium salt, the second chelating agent and the second organic solvent is 1: 1.5~2.5: 10
~20.
6. a kind of preparation method of tin antimony gadolinium oxide anode material according to claim 2, which is characterized in that the step
The rate of pulling in rapid 2 is 0.05~0.2cm/s.
7. a kind of preparation method of tin antimony gadolinium oxide anode material according to claim 2, which is characterized in that the step
Rapid 3 dry temperature are 80~100 DEG C, and the time is 10~20mins.
8. a kind of preparation method of tin antimony gadolinium oxide anode material according to claim 2, which is characterized in that the step
Rapid 4 are specifically implemented according to the following steps:
Step 4.1 heats the gel dry film on the resulting Titanium base surface of step 3 in dry oxygen ambient, after being heated to 100 DEG C,
Wet oxygen atmosphere is changed, is warming up to 200~220 DEG C with the rate of 10 DEG C/min, 400 are warming up to the speed of 1~5 DEG C/min~
450 DEG C, and keep the temperature 10~15mins；
Dry oxygen ambient is changed after step 4.2, heat preservation, and is cooled to 200 DEG C hereinafter, tin antimony gadolinium sull is made.
9. a kind of preparation method of tin antimony gadolinium oxide anode material according to claim 2, which is characterized in that the step
Rapid 5 are specifically implemented according to the following steps:
Step 5.1 heats step 4 gained Titanium base tin antimony gadolinium sull in dry nitrogen atmosphere, with 15~25 DEG C/min
Speed be heated to 510~530 DEG C；Atmosphere is then switched into wet nitrogen/oxygen mixed atmosphere, the partial pressure of oxygen is maintained at 1
~2vol%, water vapor pressure are maintained at 7~8kPa, and keep the temperature 1-2 hours；
Atmosphere is switched to dry nitrogen/oxygen mixed atmosphere by step 5.2, and the partial pressure of oxygen is maintained at 1~2vol%, heat preservation 20
~30mins；
Step 5.3, cooling, switch to dry oxygen for atmosphere after temperature is cooled to 400~450 DEG C, and protect at this temperature
3~4h of temperature；After heat preservation, it is cooled back to room temperature, the Ti-base Sn-Sb gadolinium oxide anode material with conducting function is made.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105774118A (en) * | 2015-01-09 | 2016-07-20 | Jx日矿日石金属株式会社 | Metal substrate with plating |
| CN108390070A (en) * | 2018-02-10 | 2018-08-10 | 浩发环保科技（深圳）有限公司 | Tin-antimony oxide anode material coating and preparation method thereof, flow battery Ti-base Sn-Sb oxide electrode |
-
2019
- 2019-03-29 CN CN201910251808.XA patent/CN110010913A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105774118A (en) * | 2015-01-09 | 2016-07-20 | Jx日矿日石金属株式会社 | Metal substrate with plating |
| CN108390070A (en) * | 2018-02-10 | 2018-08-10 | 浩发环保科技（深圳）有限公司 | Tin-antimony oxide anode material coating and preparation method thereof, flow battery Ti-base Sn-Sb oxide electrode |
Non-Patent Citations (1)
| Title |
|---|
| CARLOS F.C. MACHADO等: "Time and calcination temperature influence on the electrocatalytic efficiency of Ti/SnO2:Sb(5%),Gd(2%) electrodes towards the electrochemical oxidation of naphthalene", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 * |
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