CN109678494A - A kind of Asia Titanium oxide electrode piece and its preparation method and application - Google Patents
A kind of Asia Titanium oxide electrode piece and its preparation method and application Download PDFInfo
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- CN109678494A CN109678494A CN201910134215.5A CN201910134215A CN109678494A CN 109678494 A CN109678494 A CN 109678494A CN 201910134215 A CN201910134215 A CN 201910134215A CN 109678494 A CN109678494 A CN 109678494A
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Abstract
The present invention provides a kind of sub- Titanium oxide electrode pieces and its preparation method and application.The preparation method comprises the following steps: (1) sub- titanium oxide fine powder is vacuumized and apply pressure carry out it is preforming, obtain preformed product；(2) discharge plasma sintering is carried out to step (1) preformed product, obtains the sub- Titanium oxide electrode piece.Preparation method provided by the invention passes through high Ti4O7The sub- titanium oxide of content and the mutual cooperation of discharge plasma sintering, effectively increase the electric conductivity and corrosion resistance of sub- Titanium oxide electrode piece, it is conducive to extend the service life of electrode, the compactness of prepared sub- Titanium oxide electrode piece is improved, improves its toughness and post-production.In preparation method provided by the invention, binder is uniformly mixed with sub- titanium oxide fine powder, can reduce electrode slice flaw by pre-molding, promotes the performance of sub- Titanium oxide electrode piece.
Description
Technical field
The invention belongs to ceramic electrode technical field, be related to sub- titanium oxide more particularly to a kind of sub- Titanium oxide electrode piece and
Preparation method and use.
Background technique
Sub- titanium oxide (TinO2n-1) possess unique physics, chemistry and chemical property, including excellent electric conductivity, extremely strong
Chemical stability, corrosion resistance and wide electrochemically stable potential window.Based on sub- titanium oxide in physics, chemistry and electrochemistry
The characteristics of aspect of performance, sub- titanium oxide are increasingly used for preparing the electrode of diversified forms, and being applied to battery and wastewater treatment etc.
Field.
To realize the application of sub- titanium oxide in the electrodes, a variety of utilization ways and preparation method have been formd at present.First,
It is that sub- titanium oxide is formed to high electric conductivity, corrosion proof combination electrode material, such as CN102496704A and CN105932261A.
Second, being using sub- titanium oxide is as substrate surface clad or sub- titanium oxide is made middle layer lives set on basis material and surface
Between property layer.CN102817020A makes public for the first time a kind of titanium-based Asia oxidation titanium plate and preparation method thereof, is heat-treated using colloidal sol
Technology, high-temp in-situ synthesizes sub- thin film of titanium oxide on titanium-base.Then, similar sub- titanium-oxide-coated electrode is disclosed in succession
The patented technology of plate, the preparation method of the copper-based sub- Titanium oxide electrode plate of one kind as disclosed in CN105297073A；
CN105967281A discloses a kind of titanium-based Asia Titanium oxide electrode preparation method.By titanium-based noble metal oxide coating (DSA)
It inspires, is attempted to addition intermediate layer to protect Titanium base not to be corroded and aoxidize, and then reach and improve ti-based coating electricity
The performance of pole, if CN104218245A discloses a kind of titanium/Asia titanium oxide/lead composite substrate preparation method, this method is first
Then roughening treatment titanium-based plate surface forms one layer of sub- titanium oxide through dipping, drying and sintering, then in one layer of gold of its electroplating surface
Belong to lead, obtains a kind of composite substrate for bipolar lead-acid accumulator.CN105058916A discloses a kind of with sub- oxidation
The electrode material of titanium inter coat is coated using cladding process on its surface using titanium, aluminium and its alloy as the core arrangement of electrode
Sub- titanium oxide layer, then plate metal oxide coating on its surface using galvanoplastic or use thermal decomposition method preparation high activity dilute expensive
Metal oxide layer.Third, being sub- titanium oxide powder directly to be formed sheet or bulk is used to make electrode, such as
CN105948733A discloses sub- titanium oxide soluble electrode and preparation method thereof and the application that is prepared in high purity titanium in molten-salt electrolysis,
Raw material is prepared into sub- titanium oxide block, or sub- titanium oxide and stud or the combined sub- titanium oxide composite block of graphite rod
Body, then finished and sub- titanium oxide soluble electrode can be obtained, gained titanium soluble electrode contains extremely low C, N content, thus
It is to obtain not when anode and/or catholyte prepare Titanium by the high pure metal of anode pollution using this sub- titanium oxide soluble electrode
Titanium.
Just from the point of view of the technology of preparing of existing sub- Titanium oxide electrode plate, Asia titanium oxide powder or fabricated in situ Asia titanium oxide used
It is by serial titanium oxide (such as TiO, T3O5, Ti4O7, Ti5O9, Ti6O11, Ti7O14, Ti8O15Or Ti9O17) composition, by a variety of titaniums
The sub- Titanium oxide electrode of oxide composition is difficult to keep high conductivity and corrosion resistance.It is well known that different titanium oxides have
Different electric conductivity, corrosion resistance and electrochemical windows, wherein with Ti4O7Electric conductivity be it is best, but with sub- titanium oxide powder
For raw material, it is difficult to obtain that compactness is good and the sheet or block materials of holding high conductivity by having technology of preparing, in reality
There are poor toughness in, the problems such as post-production is poor.
Summary of the invention
For the above-mentioned problems in the prior art, the purpose of the present invention is to provide a kind of sub- Titanium oxide electrode piece and
Preparation method and use.Asia Titanium oxide electrode piece electric conductivity and corrosion resistance provided by the invention are good, and electrode slice flaw is few, toughness
It is good with post-production.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of preparation method of sub- Titanium oxide electrode piece, the described method comprises the following steps:
(1) sub- titanium oxide fine powder is vacuumized and apply pressure carry out it is preforming, obtain preformed product；
(2) discharge plasma sintering is carried out to step (1) preformed product, obtains the sub- Titanium oxide electrode piece.
It is preforming by being carried out to sub- titanium oxide, it is possible to reduce electrode slice flaw mentions in preparation method provided by the invention
Rise the overall quality of electrode slice.And use discharge plasma sintering, then it can be matched with this raw material of sub- titanium oxide fine powder, it can
Electric conductivity, corrosion resistance and the oxygen deposition potential for enhancing electrode slice improve the compactness of prepared electrode slice, improve its toughness and
Post-production realizes that electrode shape is stablized.Here, if not directly using sub- titanium oxide fine powder, but TiO is used2、
H2TiO3Or TiOSO4It, can be because of technique in reduction process Deng the mixture as titanium source and reducing agent (such as carbon system reducing agent)
Condition is difficult to control, and causes to restore or restore deficiency, so that product is the mixture object phase of titanium oxide, it is difficult to be made
The Ti of high-purity high conductivity4O7, meanwhile, the easily carbon impurity of remained unreacted in product also brings unfavorable effect to product.
It is used as currently preferred technical solution below, but not as the limitation to technical solution provided by the invention, leads to
Following preferred technical solution is crossed, can preferably reach and realize technical purpose and beneficial effect of the invention.
As the present invention preferably technical solution, such as 40 μm of partial size≤40 μm of step (1) the sub- titanium oxide fine powder,
39 μm, 38 μm, 37 μm, 36 μm or 35 μm etc..Here, if the partial size of sub- titanium oxide fine powder is excessive, it will lead to granular boundary and connect
Contacting surface product is small, influences product compactness.
Preferably, the Ti in step (1) the sub- titanium oxide fine powder4O7Mass fraction >=90wt%, such as 90wt%,
91wt%, 92wt%, 93wt%, 94wt%, 95wt%, 96wt%, 97wt%, 98wt% or 99wt% etc..In the present invention, protect
Demonstrate,prove the Ti in sub- titanium oxide fine powder4O7Mass fraction >=90wt% of the sub- titanium oxide of this Magn é li phase, can preferably with put
Electric plasma agglomeration matches, preferably promotion electric conductivity and corrosion resistance, is conducive to extend the service life of electrode slice, mentions simultaneously
The compactness of electrode slice prepared by height improves its toughness and post-production.
As currently preferred technical solution, the preparation method of step (1) the sub- titanium oxide fine powder includes: by sub- oxygen
Change titanium to be crushed under vacuum or protective atmosphere, sieve later, obtains the sub- titanium oxide fine powder.
Preferably, Ti in the sub- titanium oxide4O7Mass fraction >=90wt%, for example, 90wt%, 91wt%, 92wt%,
93wt%, 94wt%, 95wt%, 96wt%, 97wt%, 98wt% or 99wt% etc..
Preferably, vacuum degree is reduced to < 10Pa, such as 9Pa, 8Pa, 7Pa, 6Pa, 5Pa, 4Pa, 3Pa by described vacuumize
Or 2Pa etc..
Preferably, the protective atmosphere includes nitrogen atmosphere and/or argon atmosphere.The nitrogen atmosphere and/or argon gas
It can be nitrogen atmosphere that atmosphere, which refers to, or argon atmosphere can also be the combination of nitrogen atmosphere and argon atmosphere.Here
Nitrogen and argon gas be both preferably high-purity gas.
Preferably, the broken method is ball milling.
Preferably, it is described sub- titanium oxide is carried out under vacuum or protective atmosphere broken method include: by Asia aoxidize
Titanium is placed in ball grinder, and sealing vacuumizes or be filled with protective atmosphere, ball milling.
In the present invention, ball grinder is sealed, and the ball grinder of sealing is vacuumized or is filled with protective atmosphere,
Be in order to avoid sub- titanium dioxide powder in high speed mechanical milling process because of high temperature and contact oxygen due to is oxidized to other Magn é li phases
Sub- titanium oxide (such as Ti6O11, Ti7O14, Ti8O15Or Ti9O17) and TiO2, and the sub- titanium oxide of these Magn é li phases and TiO2It can be significant
Reduce the electric conductivity of pressure titania meterial.
As currently preferred technical solution, vacuum degree is reduced to < 10Pa by described vacuumize of step (1), such as
9Pa, 8Pa, 7Pa, 6Pa, 5Pa, 4Pa, 3Pa or 2Pa etc..
Preferably, step (1) is described applies stressed pressure size as 10-100MPa, such as such as 10MPa, 20MPa,
40MP or 60MPa, 80MPa or 100MPa etc., it is not limited to cited numerical value, other are unlisted in the numberical range
Numerical value is equally applicable.
Preferably, step (1) further include: sub- titanium oxide fine powder is vacuumized and apply pressure carry out it is preforming before,
The sub- titanium oxide fine powder is first fitted into graphite jig and graphite jig is placed in discharge plasma sintering furnace.
As currently preferred technical solution, step (1) further includes vacuumizing to sub- titanium oxide fine powder and applying pressure
Before power progress is preforming, first the sub- titanium oxide fine powder is mixed with binder.
In the present invention, the operation hardly possible that can reduce subsequent mold compacting is uniformly mixed with sub- titanium oxide fine powder using binder
Degree, and then electrode slice flaw can be reduced by pre-molding.
Preferably, the binder is polyethylene (PE), polypropylene (PP), polyvinyl butyral (PVB), poly- methyl-prop
In e pioic acid methyl ester (PMMA) or polyimides (PI) any one or at least two combination.It is typical but be non-limiting group
Conjunction has: polyethylene and polyacrylic combination, the combination of polypropylene and polyvinyl butyral, polyvinyl butyral and poly- methyl
The combination etc. of the combination of methyl acrylate, polymethyl methacrylate and polyimides.
It preferably, is in terms of 100% by the quality of the sub- titanium oxide fine powder, the mass fraction of the binder is 0-
20wt% and do not include 0, such as 2wt%, 5wt%, 10wt%, 15wt% or 20wt% etc., it is not limited to cited
Numerical value, other interior unlisted numerical value of the numberical range are equally applicable, preferably 5-20wt%.In the present invention, if binder
Additional amount it is excessive, leave a large amount of stomatas in carbon after will lead to binder pyrolytic residual or pole plate, influence product use
Performance.
As currently preferred technical solution, the sintering temperature of step (2) described discharge plasma sintering is 900-
1600 DEG C, such as 900 DEG C, 1000 DEG C, 1100 DEG C, 1200 DEG C, 1300 DEG C, 1400 DEG C, 1500 DEG C or 1600 DEG C etc., but simultaneously not only
It is limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, the pressure of step (2) described discharge plasma sintering be 10-100MPa, such as 10MPa, 2 0MPa,
40MP or 60MPa, 80MPa or 100MPa etc., it is not limited to cited numerical value, other are unlisted in the numberical range
Numerical value is equally applicable.In the present invention, if the pressure of discharge plasma sintering is excessive, will lead to can be prematurely formed envelope between powder
Closed pore hole, gas are difficult to be discharged, and can not eliminate after sintering there are still certain hole；If the pressure mistake of discharge plasma sintering
It is small, it can only make powder particle that relative movement and lesser deformation occur, pole plate consistency is relatively low after will lead to sintering, influences pole plate
Service performance.
Preferably, the time of step (2) described discharge plasma sintering be 5-30min, such as 5min, 10min, 15min,
20min, 25min or 30min etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same
Sample is applicable in.
Preferably, step (2) discharge plasma sintering is constant temperature and pressure sintering.
As currently preferred technical solution, step (2) discharge plasma sintering is in vacuum condition or is filled with guarantor
It is carried out under conditions of shield property gas.
Preferably, the vacuum degree of the vacuum and step (1) to vacuumize vacuum degree identical.
Preferably, the protective gas includes nitrogen and/or argon gas.It can be nitrogen that the nitrogen and/or argon gas, which refer to,
Gas, or argon gas can also be the combination of nitrogen and argon gas.Here nitrogen and argon gas is both preferably high-purity gas.
Preferably, step (2) described discharge plasma sintering carries out in discharge plasma sintering furnace.
Preferably, step (2) further include: after discharge plasma sintering, naturally cool to 15-35 DEG C, i.e. nature
It is cooled to room temperature.
As the further preferred technical solution of preparation method of the present invention, the described method comprises the following steps:
(1) ball grinder is sealed after sub- titanium oxide being placed in ball grinder, then to the ball grinder of sealing vacuumized by
Vacuum degree is reduced to < 10Pa or is filled with protective atmosphere, carries out ball milling, sieves later, obtain the sub- titanium oxide of partial size≤40 μm
Fine powder；
Wherein, Ti in the sub- titanium oxide4O7Mass fraction >=90wt%
(2) step (1) the sub- titanium oxide fine powder is mixed with binder, obtained mixture is packed into graphite jig simultaneously
Graphite jig is placed in discharge plasma sintering furnace, vacuumizes and vacuum degree is reduced to < 10Pa, application pressure size is 10-
The pressure progress of 100MPa is preforming, obtains preformed product；
It wherein, is in terms of 100% by the quality of the sub- titanium oxide fine powder, the mass fraction of the binder is 0-20wt%
And do not include 0；
(3) described preforming to step (2) under conditions of keeping the vacuum degree of step (2) or being filled with protective gas
Product carries out 5-30min constant temperature and pressure discharge plasma sintering in discharge plasma sintering furnace, naturally cools to 15- after sintering
35 DEG C, obtain the sub- Titanium oxide electrode piece；
Wherein, the sintering temperature of the discharge plasma sintering is 900-1600 DEG C, the pressure of the discharge plasma sintering
It is by force 10-100MPa.
Second aspect, the present invention provide a kind of sub- titanium oxide being prepared that preparation method obtains as described in relation to the first aspect
Electrode slice.
Preferably, Ti in the sub- Titanium oxide electrode piece4O7Mass fraction >=90wt%, such as 90wt%, 91wt%,
92wt%, 93wt%, 94wt%, 95wt%, 96wt%, 97wt%, 98wt% or 99wt% etc..Sub- oxidation provided by the invention
The sub- Titanium oxide electrode of Ti electrode piece is mainly by Ti4O7It constitutes, there is high conductivity and high compactness.
Preferably, the conductivity of the sub- Titanium oxide electrode piece is 3000-5000sm-1, such as 3000sm-1、
3500s·m-1、4000s·m-1、4500s·m-1Or 5000sm-1Deng it is not limited to cited numerical value, the numerical value model
Other unlisted numerical value are equally applicable in enclosing.
The third aspect, the present invention provide a kind of purposes of Titanium oxide electrode piece sub- as described in second aspect, the sub- oxidation
Ti electrode piece is used for the electrode or battery grid of electrocatalytic oxidation.The battery grid include high-energy battery anode light plate grid with
And bipolar battery grid.
Compared with prior art, the invention has the following advantages:
Preparation method provided by the invention passes through high Ti4O7The phase interworking of the sub- titanium oxide of content and discharge plasma sintering
It closes, effectively increases the electric conductivity and corrosion resistance of sub- Titanium oxide electrode piece, be conducive to extend the service life of electrode, improve made
The compactness of standby sub- Titanium oxide electrode piece, improves its toughness and post-production.In preparation method provided by the invention, bonding
Agent is uniformly mixed with sub- titanium oxide fine powder, can reduce electrode slice flaw by pre-molding, promotes sub- Titanium oxide electrode piece
Performance.The conductivity of the sub- Titanium oxide electrode piece of method preparation provided by the invention is up to 5000sm-1, oxygen overpotential (V/
SHE) up to 1.74, porosity can be down to 0.85%.
Detailed description of the invention
Fig. 1 is the macro morphology figure of sub- Titanium oxide electrode piece prepared by the embodiment of the present invention 1.
Fig. 2 is the macro morphology figure of sub- Titanium oxide electrode piece prepared by the embodiment of the present invention 2.
Fig. 3 is the scanning electron microscope diagram of sub- Titanium oxide electrode piece prepared by the embodiment of the present invention 3.
Fig. 4 is the scanning electron microscope diagram of sub- Titanium oxide electrode piece prepared by the embodiment of the present invention 4.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only simple example of the invention, does not represent or limit the scope of the present invention, this
Invention protection scope is subject to claims.
The following are typical but non-limiting embodiments of the invention:
Embodiment 1
The present embodiment is prepared as follows sub- Titanium oxide electrode piece:
(1) ball milling: by Ti4O7The sub- titanium dioxide powder that content is 90% carries out ball milling under an argon atmosphere, sieves after ball milling
Obtain the sub- titanium oxide fine powder that grain diameter is not more than 40 microns；
(2) preforming: by above-mentioned sub- titanium oxide fine powder (Ti4O7Content is 90%) to be uniformly mixed to be packed into stone with binder PI
Black mold, the additional amount of the binder PI are the 2wt% of sub- titania weight, and graphite jig is then placed in plasma discharging
In sintering furnace, vacuum degree is evacuated to as 9.5Pa and applying 10MPa pressure keeps mixed-powder preforming；
(3) it is sintered: being warming up to 900 DEG C of sintering temperature under the conditions of keeping argon gas, carry out constant temperature and pressure plasma discharging burning
Heating power supply is closed after the knot 30min time, sub- Titanium oxide electrode piece is taken out after being cooled to room temperature；
Wherein, the pressure of the discharge plasma sintering is 10MPa.
Fig. 1 is the macro morphology figure of sub- Titanium oxide electrode piece provided in this embodiment, can observe the present embodiment by the figure
The macro morphology of product.
Ti in Asia Titanium oxide electrode piece manufactured in the present embodiment4O7Mass fraction is 90wt%, Asia oxygen manufactured in the present embodiment
The conductivity for changing Ti electrode piece is 3200sm-1, in the sulfuric acid solution of 1M/L, oxygen overpotential (V/SHE) is 1.65, hole
Rate is 3.50%, and corrosion resistance is good, and toughness and post-production are good, and electrode slice flaw is few.
Embodiment 2
The present embodiment is prepared as follows sub- Titanium oxide electrode piece:
(1) ball milling: by Ti4O7The sub- titanium dioxide powder that content is 99% carries out ball milling under vacuum conditions, sieves after ball milling
Obtain the sub- titanium oxide fine powder that grain diameter is not more than 38 microns；
(2) preforming: by above-mentioned sub- titanium oxide fine powder (Ti4O7Content is 99%) to be uniformly mixed loading with binder PE+PP
Graphite jig, the additional amount of the binder PE+PP are that the proportion of 20wt%, PE and the PP of sub- titania weight are 1:1, then
Graphite jig is placed in discharge plasma sintering furnace, vacuum degree is evacuated to and is 8Pa and applies 60MPa pressure and make mixed-powder
It is preforming；
(3) it is sintered: being warming up to 1600 DEG C of sintering temperature under the conditions of keeping argon gas, carry out constant temperature and pressure plasma discharging burning
Heating power supply is closed after the knot 15min time, sub- Titanium oxide electrode piece is taken out after being cooled to room temperature；
Wherein, the pressure of the discharge plasma sintering is 60MPa.
Fig. 2 is the macro morphology figure of sub- Titanium oxide electrode piece provided in this embodiment, can observe the present embodiment by the figure
The macro morphology of product.
Ti in Asia Titanium oxide electrode piece manufactured in the present embodiment4O7Mass fraction is 96wt%, Asia oxygen manufactured in the present embodiment
The conductivity for changing Ti electrode piece is 5000sm-1, in the sulfuric acid solution of 1M/L, oxygen overpotential (V/SHE) is 1.74, hole
Rate is 0.85%, and corrosion resistance is good, and toughness and post-production are good, and electrode slice flaw is few.
Embodiment 3
The present embodiment is prepared as follows sub- Titanium oxide electrode piece:
(1) ball milling: by Ti4O7The sub- titanium dioxide powder that content is 93% carries out ball milling under an argon atmosphere, sieves after ball milling
Obtain the sub- titanium oxide fine powder that grain diameter is not more than 30 microns；
(2) preforming: by above-mentioned sub- titanium oxide fine powder (Ti4O7Content is 93%) to be uniformly mixed to be packed into stone with binder PVB
Black mold, the additional amount of the binder PVB are the 5wt% of sub- titania weight, then by graphite jig be placed in electric discharge etc. from
In sub- sintering furnace, vacuum degree is evacuated to as 9Pa and applying 100MPa pressure keeps mixed-powder preforming；
(3) it is sintered: being warming up to 1200 DEG C of sintering temperature under the conditions of keeping argon gas, carry out constant temperature and pressure plasma discharging burning
Heating power supply is closed after the knot 5min time, sub- Titanium oxide electrode piece is taken out after being cooled to room temperature；
Wherein, the pressure of the discharge plasma sintering is 100MPa.
Fig. 3 is the scanning electron microscope diagram of sub- Titanium oxide electrode piece provided in this embodiment, can be seen that this by the figure
The product structure of embodiment is comparatively dense, and hole is less.
.Ti in Asia Titanium oxide electrode piece manufactured in the present embodiment4O7Mass fraction is 92wt%, Asia manufactured in the present embodiment
The conductivity of Titanium oxide electrode piece is 4000sm-1, in the sulfuric acid solution of 1M/L, oxygen overpotential (V/SHE) is 1.68, hole
Gap rate is 2.25%, and corrosion resistance is good, and toughness and post-production are good, and electrode slice flaw is few.
Embodiment 4
The present embodiment is prepared as follows sub- Titanium oxide electrode piece:
(1) ball milling: by Ti4O7The sub- titanium dioxide powder that content is 96% carries out ball milling in a nitrogen atmosphere, sieves after ball milling
Obtain the sub- titanium oxide fine powder that grain diameter is not more than 40 microns；
(2) preforming: by above-mentioned sub- titanium oxide fine powder (Ti4O7Content is 96%) to be uniformly mixed to be packed into stone with binder PVB
Black mold, the additional amount of the binder PMMA are the 2wt% of sub- titania weight, then by graphite jig be placed in electric discharge etc. from
In sub- sintering furnace, vacuum degree is evacuated to lower than 10Pa and applying 40MPa pressure keeps mixed-powder preforming；
(3) it is warming up to 900 DEG C of sintering temperature in the case where keeping vacuum condition, carries out constant temperature and pressure discharge plasma sintering
20min closes heating power supply after the time, and sub- Titanium oxide electrode piece is taken out after being cooled to room temperature；
Wherein, the pressure of the discharge plasma sintering is 50MPa.
Fig. 4 is the scanning electron microscope diagram of sub- Titanium oxide electrode piece provided in this embodiment, can be seen that this by the figure
The product structure of embodiment is comparatively dense, and hole is less.
Ti in Asia Titanium oxide electrode piece manufactured in the present embodiment4O7Mass fraction is 95wt%, Asia oxygen manufactured in the present embodiment
The conductivity for changing Ti electrode piece is 4500sm-1, in the sulfuric acid solution of 1M/L, oxygen overpotential (V/SHE) is 1.71, hole
Rate is 1.30%, and corrosion resistance is good, and toughness and post-production are good, and electrode slice flaw is few.
Embodiment 5
The present embodiment is prepared as follows sub- Titanium oxide electrode piece:
(1) ball milling: by Ti4O7The sub- titanium dioxide powder that content is 90% carries out ball milling under an argon atmosphere, sieves after ball milling
Obtain the sub- titanium oxide fine powder that grain diameter is not more than 40 microns；
(2) preforming: by above-mentioned sub- titanium oxide fine powder (Ti4O7Content is 90%) to be packed into graphite jig, then by graphite mo(u)ld
Tool is placed in discharge plasma sintering furnace, is evacuated to vacuum degree lower than 10Pa and is applied 100MPa pressure and make sub- titanium dioxide powder
It is preforming；
(3) it is sintered: being warming up to 1500 DEG C of sintering temperature under the conditions of keeping argon gas, carry out constant temperature and pressure plasma discharging burning
Heating power supply is closed after the knot 20min time, sub- Titanium oxide electrode piece is taken out after being cooled to room temperature；
Wherein, the pressure of the discharge plasma sintering is 100MPa.
Ti in Asia Titanium oxide electrode piece manufactured in the present embodiment4O7Mass fraction is 90wt%, Asia oxygen manufactured in the present embodiment
The conductivity for changing Ti electrode piece is 3350sm-1, in the sulfuric acid solution of 1M/L, oxygen overpotential (V/SHE) is 1.66, hole
Rate is 1.85%, and corrosion resistance is good, and toughness and post-production are good, and electrode slice flaw is few.
Comparative example 1
This comparative example is other than the pressure of discharge plasma sintering in step (3) is 5MPa, other operations and embodiment 1
It is identical.
Ti in the sub- Titanium oxide electrode piece of this comparative example preparation4O7Mass fraction is 90wt%, the sub- oxygen of this comparative example preparation
The conductivity for changing Ti electrode piece is 2800sm-1, in the sulfuric acid solution of 1M/L, oxygen overpotential (V/SHE) is 1.55, hole
Rate is 5.35%, and toughness and post-production are to be improved.
Comparative example 2
This comparative example is other than the pressure of discharge plasma sintering in step (3) is 200MPa, other operations and implementation
Example 1 is identical.
Ti in the sub- Titanium oxide electrode piece of this comparative example preparation4O7Mass fraction is 90wt%, the sub- oxygen of this comparative example preparation
The conductivity for changing Ti electrode piece is that oxygen deposition potential is 3000sm-1, in the sulfuric acid solution of 1M/L, oxygen overpotential (V/
It SHE) is 1.58, porosity 5.00%, toughness and post-production are to be improved.
Comparative example 3
This comparative example is in addition to not sub- titanium dioxide powder, the nano-TiO of molar ratio 4:1.2 used in step (1)2
Except powder and nano carbon black powder, other operations are same as Example 1.
Ti in the sub- Titanium oxide electrode piece of this comparative example preparation4O7Mass fraction is 0wt%, the sub- oxygen of this comparative example preparation
The conductivity for changing Ti electrode piece is 400sm-1, in the sulfuric acid solution of 1M/L, oxygen overpotential (V/SHE) is 1.13, hole
Rate is 3.10%, and toughness and post-production are to be improved.
Based on the above embodiments with comparative example it is found that the sub- Titanium oxide electrode piece electricity that preparation method provided by the invention obtains
Chemical property is good, and corrosion resistance is good, and compactness is high, and porosity is small, and toughness and post-production are good.Comparative example does not use this
The scheme of invention, therefore effect of the invention can not be obtained.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of preparation method of Asia Titanium oxide electrode piece, which is characterized in that the described method comprises the following steps:
(1) sub- titanium oxide fine powder is vacuumized and apply pressure carry out it is preforming, obtain preformed product；
(2) discharge plasma sintering is carried out to step (1) preformed product, obtains the sub- Titanium oxide electrode piece.
2. preparation method according to claim 1, which is characterized in that the partial size of step (1) the sub- titanium oxide fine powder≤
40μm；
Preferably, the Ti in step (1) the sub- titanium oxide fine powder4O7Mass fraction >=90wt%.
3. preparation method according to claim 1 or 2, which is characterized in that the preparation of step (1) the sub- titanium oxide fine powder
Method includes: to be crushed sub- titanium oxide under vacuum or protective atmosphere, is sieved later, and it is thin to obtain the sub- titanium oxide
Powder；
Preferably, Ti in the sub- titanium oxide4O7Mass fraction >=90wt%；
Preferably, vacuum degree is reduced to < 10Pa by described vacuumize；
Preferably, the protective atmosphere includes nitrogen atmosphere and/or argon atmosphere；
Preferably, the broken method is ball milling；
It is preferably, described that sub- titanium oxide is carried out broken method under vacuum or protective atmosphere includes: to set sub- titanium oxide
In ball grinder, sealing, vacuumize or be filled with protective atmosphere, ball milling.
4. preparation method according to claim 1-3, which is characterized in that step (1) is described to be vacuumized vacuum
Degree is reduced to < 10Pa；
Preferably, step (1) is described applies stressed pressure size as 10-100MPa；
Preferably, step (1) further include: sub- titanium oxide fine powder is vacuumized and apply pressure carry out it is preforming before, first will
The Asia titanium oxide fine powder is fitted into graphite jig and graphite jig is placed in discharge plasma sintering furnace.
5. preparation method according to claim 1-4, which is characterized in that step (1) further includes aoxidizing to Asia
Titanium fine powder vacuumize and apply pressure carry out it is preforming before, first the sub- titanium oxide fine powder is mixed with binder；
Preferably, the binder is that polyethylene, polypropylene, polyvinyl butyral, polymethyl methacrylate or polyamides are sub-
In amine any one or at least two combination；
Preferably, be in terms of 100% by the quality of the sub- titanium oxide fine powder, the mass fraction of the binder be 0-20wt% and
Not comprising 0, preferably 5-20wt%.
6. preparation method according to claim 1-5, which is characterized in that step (2) plasma discharging is burnt
The sintering temperature of knot is 900-1600 DEG C；
Preferably, the pressure of step (2) described discharge plasma sintering is 10-100MPa；
Preferably, the time of step (2) described discharge plasma sintering is 5-30min；
Preferably, step (2) discharge plasma sintering is constant temperature and pressure sintering.
7. preparation method according to claim 1-6, which is characterized in that step (2) plasma discharging is burnt
Knot is carried out in vacuum condition or be filled with protective gas under conditions of；
Preferably, the vacuum degree of the vacuum and step (1) to vacuumize vacuum degree identical；
Preferably, the protective gas includes nitrogen and/or argon gas；
Preferably, step (2) described discharge plasma sintering carries out in discharge plasma sintering furnace；
Preferably, step (2) further include: after discharge plasma sintering, naturally cool to 15-35 DEG C.
8. preparation method according to claim 1-7, which is characterized in that the described method comprises the following steps:
(1) ball grinder is sealed after sub- titanium oxide being placed in ball grinder, then the ball grinder of sealing is vacuumized vacuum
Degree is reduced to < 10Pa or is filled with protective atmosphere, carries out ball milling, sieves later, the sub- titanium oxide for obtaining partial size≤40 μm is thin
Powder；
Wherein, Ti in the sub- titanium oxide4O7Mass fraction >=90wt%；
(2) step (1) the sub- titanium oxide fine powder is mixed with binder, by obtained mixture loading graphite jig and by stone
Black mold is placed in discharge plasma sintering furnace, vacuumizes vacuum degree being reduced to < 10Pa, and application pressure size is 10-
The pressure progress of 100MPa is preforming, obtains preformed product；
It wherein, is that the mass fraction of the binder is 0-20wt% and not in terms of 100% by the quality of the sub- titanium oxide fine powder
Include 0；
(3) under conditions of keeping the vacuum degree of step (2) or being filled with protective gas, to step (2) preformed product
5-30min constant temperature and pressure discharge plasma sintering is carried out in discharge plasma sintering furnace, naturally cools to 15-35 after sintering
DEG C, obtain the sub- Titanium oxide electrode piece；
Wherein, the sintering temperature of the discharge plasma sintering is 900-1600 DEG C, and the pressure of the discharge plasma sintering is
10-100MPa。
9. a kind of sub- Titanium oxide electrode piece that the preparation method as described in claim any one of 1-8 is prepared；
Preferably, Ti in the sub- Titanium oxide electrode piece4O7Mass fraction >=90wt%；
Preferably, the conductivity of the sub- Titanium oxide electrode piece is 3000-5000sm-1。
10. a kind of purposes of sub- Titanium oxide electrode piece as claimed in claim 9, which is characterized in that the Asia Titanium oxide electrode piece
Electrode or battery grid for electrocatalytic oxidation.
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| CN115818796B (en) * | 2023-01-10 | 2024-05-24 | 东莞理工学院 | Zr metal atom doped Ti4O7Preparation and application methods of composite electrode |
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