CN108425132A - A kind of preparation method of ozone electrolytic cell anode catalyst diaphragm plate - Google Patents
A kind of preparation method of ozone electrolytic cell anode catalyst diaphragm plate Download PDFInfo
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- CN108425132A CN108425132A CN201810139367.XA CN201810139367A CN108425132A CN 108425132 A CN108425132 A CN 108425132A CN 201810139367 A CN201810139367 A CN 201810139367A CN 108425132 A CN108425132 A CN 108425132A
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- polytetrafluoroethylene
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/13—Ozone
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
Abstract
The present invention uses frame board of the polytetrafluoroethylene (PTFE) as anode catalyst diaphragm plate, cost is relatively low, and polytetrafluoroethylene (PTFE) itself has corrosion resistant characteristic, it is configured to the form of mesh plate, there is larger contact area, and also assure due physical strength so that the replacement and dismounting of anode diaphragm plate are more simple and convenient.Polytetrafluoroethylene (PTFE) mesh plate is into having crossed laser ablation and plasma polarization process, it is formd on polytetrafluoroethylene (PTFE) mesh plate convenient for accommodating the ability with deposition of carbon nanotubes-brown lead oxide composite material, laser ablation can form pit on polytetrafluoroethylene (PTFE) mesh plate, laser treatment and plasma polarization process can also improve the activation energy of ptfe surface, make carbon nanotube-combination of the brown lead oxide composite material on polytetrafluoroethylene (PTFE) mesh plate more closely by molecule bonding force, and without the interference of extraneous other factors so that catalytic action is more pure.
Description
Technical field
The present invention relates to electrolytic preparation Ozone Water technical field more particularly to a kind of ozone electrolytic cell anode catalyst diaphragm plates
Preparation method.
Background technology
Ozone is light blue gas, is a kind of extremely strong oxidant, by oxidation, inhibits the breeding and life of bacterium
It is long, and lead to the death of bacterium, it is a kind of strong fungicide again.Ozone can be dissolved in water, and the Ozone Water of certain ozone concentration is same
With extremely strong bactericidal effect.Ozone and Ozone Water can be sterilized and sterilized to food, drinking water, be disappeared to drinking water
When malicious, in addition to the bacterium in water can be killed, it is further purified outside the impurity in water, moreover it is possible to increase the oxygen content in water.Ozone and
All kinds of skin diseases that Ozone Water causes bacterium, bacterial inflammation, the diseases such as burn surfaces have certain curative effect.Ozone and
Ozone Water also has many advantages, such as without side-effects, non-toxic, non-secondary pollution.Therefore, it is widely used in drinking water, food
The fields such as processing, health care, chemical industry, environmental protection.
The method for preparing ozone has corona method and electrolysis, electrolysis to be better than corona method again can prepare high-concentrated ozone.
Current electrolytic ozone generator, by electrolysis ozone generator, electrolysis ozone generator power supply, anode water tank, cathode water tank
Composition.
Solid polymer electrolyte water electrolysis technology originates from the research of General Electric Company earliest, is USA space
Plan exploitation low-temperature fuel cell was applied to the apparatus of oxygen supply aspect of spaceship and submarine later.Nowadays, solid polymerization
Object electrolyte technology be widely used hydrogen-oxygen fuel cell, Organic Electrochemical Synthesis,
The fields such as the preparation of sensor, ozone.From in the eighties of last century middle and later periods, solid polymer electrolyte technology is more and more
Use in the ozoniferous research of production.In the structure of solid polymer electrolyte electrolytic ozone generation, solid polymer ion
For this solid electrolyte of exchange membrane instead of traditional liquid electrolyte, electrocatalytic particles are attached directly to solid polymer electrolytic
On plasma membrane both sides, solid polymer electrolyte composite membrane is formed, this structure of composite membrane can increase the contact area of electrode reaction,
The mass transfer velocity for greatly improving reactant is conducive to the separation of reaction product, and reaction is combined together with detaching, electrolysis is simplified
The structure of device.Currently, anode catalyst diaphragm can use the materials such as platinum, glass-like carbon, stannic oxide and brown lead oxide, due to
The product ozone of ozone generator has very strong corrosivity, so the film must be handled with the organic solution containing platinum, antimony, tin
Plate makes its surface and inner passage form the conductive lumarith of one layer of platiniferous, antimony, tin.Such ozone generator anode
Diaphragm plate structure and its manufacture craft have a disadvantage that：Since catalyst brown lead oxide particle is by polytetrafluoroethylene (PTFE) when being film-made piece
It is bonded together, therefore the particle surface of the brown lead oxide just has polytetrafluoroethylene (PTFE), polytetrafluoroethylene (PTFE) is not catalyzed reaction
Function, it reduces effective contact area of brown lead oxide particle, to make reaction efficiency decline, eventually leads to the production of ozone
Raw rate declines.Even if difficult if carefully done upper corrosion protection processing ensure totality channel by described containing platinum, antimony, tin
Conductive anticorrosion layer tightly covers.And diaphragm plate corrosion protection processing quality be influence ozone generator service life and efficiency it is decisive because
Element.
Disadvantage mentioned above is the key limiting link of the efficiency and use cost that improve electrolysis type ozone generator, for smelly
The preparation of oxygen electrolytic cell anode catalyst diaphragm plate, in the industry general technical solution mainly have mull technique, ion-exchange, electrochemistry
Sedimentation etc., but these all do not break away from the processes such as bonding, plating, pressed-powder anode catalyst granules, and existing preparation
Method can't ensure that ozone generator anode construction has high working efficiency and working life.
By the research prior art, the preparation method of ideal ozone electrolytic cell anode catalyst diaphragm plate is not yet found, because
This, needs to develop a kind of new preparation method, and ozone electrolytic cell anode catalyst diaphragm plate is made to have higher working efficiency and work
Make the service life.
Invention content
For the above-mentioned problems in the prior art, the purpose of the present invention is to provide a kind of ozone electrolytic cell anodes to urge
The preparation method of agent diaphragm plate, the present invention are used in combination using carbon nanotube and catalyst brown lead oxide, have high catalytic efficiency,
Advantage with long service life, while the advantages of can preferably play carbon nano tube compound material high conductivity, high intensity, having
Wide application prospect.
In order to achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of ozone electrolytic cell anode catalyst diaphragm plate, includes the following steps：
（1）The dispersion liquid for preparing carbon nanotube, in deionized water by carbon nanotube dispersion, the carbon for being configured to 15-30mg/ml is received
Mitron dispersion liquid；
（2）Dissoluble lead salting liquid is prepared, soluble lead salt is dissolved in deionized water and is configured to saturation lead salt solution；
（3）Prepare alkaline solution, a concentration of 15-20mg/ml of alkaline solution；
（4）Carbon nano tube dispersion liquid, alkaline solution and lead salt solution are added in reaction kettle and carry out hybrid reaction, it is described
The volume ratio of carbon nano tube dispersion liquid, alkaline solution and lead salt solution is 5-15：5-10：75-90；Water-bath keeps temperature 50-
80 DEG C and continue stirring 24-48 hours；The mixed solution after reaction is taken out, 50-100 DEG C of low temperature distillation is carried out in flask, directly
It is removed to solvent, takes out reactant, pickling for several times, washing is repeated, is finally rinsed with deionized water, until material cleaning solution
It is in neutrality, enters back into baking oven drying, obtain carbon nanotube-lead composite material；
（5）Prepare polytetrafluoroethylene (PTFE) mesh plate, the mesh specification on the polytetrafluoroethylene (PTFE) mesh plate is 500-800 mesh；
（6）To step（5）In polytetrafluoroethylene (PTFE) mesh plate obtained carry out double-sided laser etching processing, the laser ablation processing
Used optical maser wavelength is 200-400nm, and the maximum power of laser generator is 10-20W, the repetition rate of laser generator
For 50-150KHz, laser generator pulse width is 30-80ns, feed speed 8-15cm/min, and laser generator energy is close
Degree is 10-20J/cm2, a large amount of pits of two sides appearance of polytetrafluoroethylene (PTFE) mesh plate, the depth of the pit is 70-200 microns,
Pit diameter is 80-160 microns, and the spacing between adjacent pit is 100-300 microns, the porosity of polytetrafluoroethylene (PTFE) mesh plate
For 30%-65%；
（7）To step（6）The polytetrafluoroethylene (PTFE) mesh plate obtained after middle etching is polarised, and obtains polarized polytetrafluoroethyl-ne
Alkene mesh plate；
（8）By step（4）In carbon nanotube-lead composite material for being prepared disperse in deionized water, to stir through ultrasound again
It mixes 24-48 hours, the saturation dispersion liquid of carbon nanotube-lead composite material is prepared；
（9）By step（7）In obtained polytetrafluoroethylene (PTFE) mesh plate be immersed into step（8）In obtained carbon nanotube-lead it is compound
In the saturation dispersion liquid of material, taken out after being kept for 3-10 minutes, natural air drying, is then washed with deionized water repeatedly at room temperature
It washs, and carries out low temperature drying, obtain the polytetrafluoroethylene (PTFE) mesh plate coated with carbon nanotube-lead composite material, as ozone electricity
Solve pond anode catalyst diaphragm.
Preferably, step（4）Hybrid reaction in be also added into reducing agent solution, the reducing agent is oxalic acid, it is described also
A concentration of 5-15mg/ml of former agent solution, the dosage of the reducing agent solution are the 50-90% of the alkaline solution；
Preferably, step（4）In obtained carbon nanotube-lead composite material be carbon nanotube-brown lead oxide composite material.
Preferably, the step（2）In soluble lead salt be the nitrate containing lead element, acetate, carbonate, salt
One or more of hydrochlorate, sulfate and complex salt；The alkaline solution is one kind or mixed of sodium hydroxide, potassium hydroxide
Close object.
Preferably, the step（6）In laser ablation processing be ultraviolet laser etching processing, be single laser pulse or
Multiple laser pulses act on same position progress；Polytetrafluoroethylene (PTFE) mesh plate after laser ablation is first molten in Nafion resins
It is impregnated 15-20 minutes in liquid, takes out natural cooling, it is 7 then to use mass ratio:The mixed solution of 3 isopropyl alcohol and water washs number
It is secondary, until the thickness of polytetrafluoroethylene (PTFE) mesh plate is 0.2-1mm.
Preferably, the step（7）In polarization process be plasma polarization process, at low-temperature plasma polarization
Reason, power 3.5-5kw, sweep speed 400-600mm/min, plasma energy metric density are 1.5-3J/mm2。
Preferably, in the carbon nanotube-brown lead oxide composite material, the content of brown lead oxide is 70-85%, the carbon
The grain size of nanotube-brown lead oxide composite material is 50-150 microns.
Compared with the prior art, the present invention has the advantages that：
（1）, the present invention using carbon nanotube as support construction, brown lead oxide catalyst growth is deposited on to the table of carbon nanotube
Inside face or carbon nanotube, since carbon nanotube has extraordinary orientating type and electric conductivity so that entire anode catalyst
Diaphragm plate has higher electric conductivity and current density, improves the working efficiency of electrolysis；Brown lead oxide is located in carbon nanotube, increases
Effective contact area of the brown lead oxide catalyst and reactive material, can improve catalytic efficiency, and then improve reaction
Efficiency and electrolysis production speed.Carbon nanotube mutual lapping on polytetrafluoroethylene (PTFE) mesh plate forms the close conductive network of matter, carries
The high electric conductivity and current density of entire anode catalyst diaphragm plate, and since the brown lead oxide as catalyst is not wrapped
Cover or cover, Direct precipitation on the carbon nanotubes, in direct exposed or half exposed state, and positioned at electrolysis electrode
Intermediate cation-exchange membrane can be in direct contact, and have relatively high contact area and catalytic efficiency so that electrolytic preparation
The efficiency of ozone significantly improves.
（2）, the present invention use frame board of the polytetrafluoroethylene (PTFE) as anode catalyst diaphragm plate, cost is relatively low, and poly- four
Vinyl fluoride itself has corrosion resistant characteristic, is configured to the form of mesh plate, that is, has larger contact area, but also protect
Due physical strength is demonstrate,proved so that the replacement and dismounting of anode diaphragm plate are more simple and convenient.Polytetrafluoroethylene (PTFE) is to make originally
It is used to prepare catalyst diaphragm for binder, but the diaphragm that this mull technique is prepared can be by the titanium dioxide as catalyst
Lead is embedded therein, can reduce its contact with cation-exchange membrane, and then lead to the reduction of catalytic efficiency.The present invention is using poly-
Tetrafluoroethene is as framework material, not embedded catalyst particle, but these catalyst particle depositions are filled into framework material
Surface, and adherency appropriate is carried out by numerical value material identical with cation-exchange membrane, increases catalyst and cation
The contact area of exchange membrane, improves catalytic efficiency.
（3）, the present invention polytetrafluoroethylene (PTFE) mesh plate into laser ablation and plasma polarization process has been crossed, in polytetrafluoroethyl-ne
It is formd on alkene mesh plate convenient for accommodating and the ability of deposition of carbon nanotubes-brown lead oxide composite material, laser ablation can be
Form pit on polytetrafluoroethylene (PTFE) mesh plate, for accommodating carbon nanotube-brown lead oxide composite material, meanwhile, laser treatment and
Plasma polarization process can also improve the activation energy of ptfe surface, make carbon nanotube-dioxy by molecule bonding force
Change combination of the lead composite material on polytetrafluoroethylene (PTFE) mesh plate more closely, and without the interference of extraneous other factors, makes
It is more pure to obtain catalytic action.The present invention is first in Nafion resin solutions in the polytetrafluoroethylene (PTFE) mesh plate after laser ablation
It impregnates so that polytetrafluoroethylene (PTFE) web plate is reached the standard grade coated with one layer of very thin Nafion resin, this Nafion resin is also electrolysis
The main component of cation-exchange membrane used when preparing Ozone Water, is first arranged one layer of same substance on anode catalyst diaphragm plate
Membrane material, anode catalyst can be promoted to be contacted with the closer of cation-exchange membrane, while making carbon nanotube-brown lead oxide
Composite material attaches more secured on polytetrafluoroethylene (PTFE) mesh plate, further increases catalytic efficiency.
（4）, the present invention using using chemical synthesis directly on the carbon nanotubes beam system for brown lead oxide so that dioxy
Change lead in carbon nanotube combination and deposit it is more secured；The present invention uses twice dispersing redeposition technology, by carbon nanometer
Pipe-brown lead oxide composite material uniform deposition both ensure that the uniformity of deposition and noiseless on polytetrafluoroethylene (PTFE) mesh plate
Property, and make the combination of carbon nanotube-brown lead oxide composite material and polytetrafluoroethylene (PTFE) mesh plate that there is enough intensity, foot
To meet subsequent use demand.
Specific implementation mode
The technical solution further illustrated the present invention below by specific implementation mode.
Embodiment 1
A kind of preparation method of ozone electrolytic cell anode catalyst diaphragm plate, includes the following steps：
（1）The dispersion liquid for preparing carbon nanotube in deionized water by carbon nanotube dispersion is configured to the carbon nanometer of 15mg/ml
Pipe dispersion liquid；
（2）Lead acetate, ceruse mixed solution are prepared, soluble lead salt is dissolved in deionized water and is configured to saturated solution；
（3）Prepare sodium hydroxide solution, a concentration of 15mg/ml of sodium hydroxide solution；
（4）Carbon nano tube dispersion liquid, sodium hydroxide solution and lead salt solution are added in reaction kettle and carry out hybrid reaction,
The volume ratio of the carbon nano tube dispersion liquid, sodium hydroxide solution and lead salt solution is 5：5：75；Add reducing agent oxalic acid
Solution, a concentration of 5mg/ml of the oxalic acid solution, dosage are the 50% of the sodium hydroxide solution, and water-bath keeps temperature 50 C
And continue stirring 24 hours；The mixed solution after reaction is taken out, 50 DEG C of low temperature distillations are carried out in flask, until solvent removes,
Reactant is taken out, pickling for several times, washing is repeated, is finally rinsed with deionized water, until material cleaning solution is in neutrality, then into
Enter baking oven drying, obtains carbon nanotube-brown lead oxide composite material；Brown lead oxide in carbon nanotube-brown lead oxide composite material
Content be 70%, the grain size of carbon nanotube-brown lead oxide composite material is 50 microns；
（5）Prepare polytetrafluoroethylene (PTFE) mesh plate, the mesh specification on the polytetrafluoroethylene (PTFE) mesh plate is 500 mesh；
（6）To step（5）In polytetrafluoroethylene (PTFE) mesh plate obtained carry out double-sided laser etching processing, the laser ablation processing
Used optical maser wavelength is 200nm, and the maximum power of laser generator is 10, and the repetition rate of laser generator is 50KHz,
Laser generator pulse width is 30ns, and feed speed 8cm/min, laser generator energy density is 10J/cm2, use
Single ultraviolet laser corrasion is handled in same position；Polytetrafluoroethylene (PTFE) mesh plate after laser ablation first exists
It is impregnated 15 minutes in Nafion resin solutions, takes out natural cooling, it is 7 then to use mass ratio:The mixing of 3 isopropyl alcohol and water is molten
Liquid washs for several times, until the thickness of polytetrafluoroethylene (PTFE) mesh plate is 0.2mm；The two of polytetrafluoroethylene (PTFE) mesh plate after etched processing
There are a large amount of pits in face, and the depth of the pit is 70 microns, and pit diameter is 80 microns, and the spacing between adjacent pit is
100 microns, the porosity of polytetrafluoroethylene (PTFE) mesh plate is 30%；
（7）To step（6）The polytetrafluoroethylene (PTFE) mesh plate that is obtained after middle etching carries out plasma polarization process, using low temperature etc. from
Muon polarization processing, power 3.5kw, sweep speed 400mm/min, plasma energy metric density are 1.5J/mm2, polarized
Polytetrafluoroethylene (PTFE) mesh plate；
（8）By step（4）In carbon nanotube-brown lead oxide composite material for being prepared disperse again in deionized water, warp
Ultrasonic agitation 24 hours, is prepared the saturation dispersion liquid of carbon nanotube-brown lead oxide composite material；
（9）By step（7）In obtained polytetrafluoroethylene (PTFE) mesh plate be immersed into step（8）In obtained carbon nanotube-titanium dioxide
In the saturation dispersion liquid of lead composite material, taken out after being kept for 3 minutes, at room temperature natural air drying, then repeatedly with deionized water
Washing, and low temperature drying is carried out, obtain the polytetrafluoroethylene (PTFE) mesh plate coated with carbon nanotube-lead composite material, as ozone
Electrolytic cell anode catalyst diaphragm.
Embodiment 2
A kind of preparation method of ozone electrolytic cell anode catalyst diaphragm plate, includes the following steps：
（1）The dispersion liquid for preparing carbon nanotube in deionized water by carbon nanotube dispersion is configured to the carbon nanometer of 30mg/ml
Pipe dispersion liquid；
（2）Lead acetate, ceruse mixed solution are prepared, soluble lead salt is dissolved in deionized water and is configured to saturated solution；
（3）Prepare sodium hydroxide solution, a concentration of 20mg/ml of sodium hydroxide solution；
（4）Carbon nano tube dispersion liquid, sodium hydroxide solution and lead salt solution are added in reaction kettle and carry out hybrid reaction,
The volume ratio of the carbon nano tube dispersion liquid, sodium hydroxide solution and lead salt solution is 15： 10： 90；Add reducing agent
Oxalic acid solution, a concentration of 15mg/ml of the oxalic acid solution, dosage are the 90% of the sodium hydroxide solution, and water-bath keeps temperature
80 DEG C and continue stirring 48 hours；The mixed solution after reaction is taken out, 100 DEG C of low temperature distillations are carried out in flask, until solvent
Reactant is taken out in removal, and pickling for several times, washing is repeated, is finally rinsed with deionized water, until during material cleaning solution is in
Property, baking oven drying is entered back into, carbon nanotube-brown lead oxide composite material is obtained；Two in carbon nanotube-brown lead oxide composite material
The content of lead oxide is 85%, and the grain size of carbon nanotube-brown lead oxide composite material is 150 microns；
（5）Prepare polytetrafluoroethylene (PTFE) mesh plate, the mesh specification on the polytetrafluoroethylene (PTFE) mesh plate is 800 mesh；
（6）To step（5）In polytetrafluoroethylene (PTFE) mesh plate obtained carry out double-sided laser etching processing, the laser ablation processing
Used optical maser wavelength is 400nm, and the maximum power of laser generator is 20W, and the repetition rate of laser generator is
150KHz, laser generator pulse width are 80ns, and feed speed 15cm/min, laser generator energy density is 20J/
cm2, handled in same position using single ultraviolet laser corrasion；Polytetrafluoroethylene (PTFE) mesh after laser ablation
Plate first impregnates 20 minutes in Nafion resin solutions, takes out natural cooling, and it is 7 then to use mass ratio:3 isopropyl alcohol and water
Mixed solution washs for several times, until the thickness of polytetrafluoroethylene (PTFE) mesh plate is 1mm；Polytetrafluoroethylene (PTFE) mesh plate after etched processing
Two sides there are a large amount of pits, the depth of the pit is 200 microns, and pit diameter is 160 microns, between adjacent pit between
Away from being 300 microns, the porosity of polytetrafluoroethylene (PTFE) mesh plate is 65%；
（7）To step（6）The polytetrafluoroethylene (PTFE) mesh plate that is obtained after middle etching carries out plasma polarization process, using low temperature etc. from
Muon polarization processing, power 5kw, sweep speed 600mm/min, plasma energy metric density are 3J/mm2, obtain polarized poly-
Tetrafluoroethene mesh plate；
（8）By step（4）In carbon nanotube-brown lead oxide composite material for being prepared disperse again in deionized water, warp
Ultrasonic agitation 48 hours, is prepared the saturation dispersion liquid of carbon nanotube-brown lead oxide composite material；
（9）By step（7）In obtained polytetrafluoroethylene (PTFE) mesh plate be immersed into step（8）In obtained carbon nanotube-titanium dioxide
In the saturation dispersion liquid of lead composite material, holding is taken out after ten minutes, at room temperature natural air drying, then repeatedly with deionized water
Washing, and low temperature drying is carried out, obtain the polytetrafluoroethylene (PTFE) mesh plate coated with carbon nanotube-lead composite material, as ozone
Electrolytic cell anode catalyst diaphragm.
Embodiment 3
A kind of preparation method of ozone electrolytic cell anode catalyst diaphragm plate, includes the following steps：
（1）The dispersion liquid for preparing carbon nanotube in deionized water by carbon nanotube dispersion is configured to the carbon nanometer of 20mg/ml
Pipe dispersion liquid；
（2）Lead acetate, ceruse mixed solution are prepared, soluble lead salt is dissolved in deionized water and is configured to saturated solution；
（3）Prepare sodium hydroxide solution, a concentration of 18mg/ml of sodium hydroxide solution；
（4）Carbon nano tube dispersion liquid, sodium hydroxide solution and lead salt solution are added in reaction kettle and carry out hybrid reaction,
The volume ratio of the carbon nano tube dispersion liquid, sodium hydroxide solution and lead salt solution is 10：8：85；Add reducing agent oxalic acid
Solution, a concentration of 8mg/ml of the oxalic acid solution, dosage are the 75% of the sodium hydroxide solution, and water-bath keeps temperature 50-80
DEG C and continue stirring 36 hours；The mixed solution after reaction is taken out, 80 DEG C of low temperature distillations are carried out in flask, until solvent is gone
It removes, takes out reactant, pickling for several times, washing is repeated, is finally rinsed with deionized water, until material cleaning solution is in neutrality,
Baking oven drying is entered back into, carbon nanotube-brown lead oxide composite material is obtained；Dioxy in carbon nanotube-brown lead oxide composite material
The content for changing lead is 80%, and the grain size of carbon nanotube-brown lead oxide composite material is 100 microns；
（5）Prepare polytetrafluoroethylene (PTFE) mesh plate, the mesh specification on the polytetrafluoroethylene (PTFE) mesh plate is 750 mesh；
（6）To step（5）In polytetrafluoroethylene (PTFE) mesh plate obtained carry out double-sided laser etching processing, the laser ablation processing
Used optical maser wavelength is 300nm, and the maximum power of laser generator is 15W, and the repetition rate of laser generator is
100KHz, laser generator pulse width are 60ns, and feed speed 10cm/min, laser generator energy density is 15J/
cm2, handled in same position using single ultraviolet laser corrasion；Polytetrafluoroethylene (PTFE) mesh after laser ablation
Plate first impregnates 18 minutes in Nafion resin solutions, takes out natural cooling, and it is 7 then to use mass ratio:3 isopropyl alcohol and water
Mixed solution washs for several times, until the thickness of polytetrafluoroethylene (PTFE) mesh plate is 0.5mm；Polytetrafluoroethylene (PTFE) mesh after etched processing
There are a large amount of pits in the two sides of plate, and the depth of the pit is 100 microns, and pit diameter is 120 microns, between adjacent pit
Spacing is 200 microns, and the porosity of polytetrafluoroethylene (PTFE) mesh plate is 50%；
（7）To step（6）The polytetrafluoroethylene (PTFE) mesh plate that is obtained after middle etching carries out plasma polarization process, using low temperature etc. from
Muon polarization processing, power 4kw, sweep speed 500mm/min, plasma energy metric density are 2J/mm2, obtain polarized poly-
Tetrafluoroethene mesh plate；
（8）By step（4）In carbon nanotube-brown lead oxide composite material for being prepared disperse again in deionized water, warp
Ultrasonic agitation 36 hours, is prepared the saturation dispersion liquid of carbon nanotube-brown lead oxide composite material；
（9）By step（7）In obtained polytetrafluoroethylene (PTFE) mesh plate be immersed into step（8）In obtained carbon nanotube-titanium dioxide
In the saturation dispersion liquid of lead composite material, holding is taken out after five minutes, at room temperature natural air drying, then repeatedly with deionized water
Washing, and low temperature drying is carried out, obtain the polytetrafluoroethylene (PTFE) mesh plate coated with carbon nanotube-lead composite material, as ozone
Electrolytic cell anode catalyst diaphragm.
Embodiment 4
A kind of preparation method of ozone electrolytic cell anode catalyst diaphragm plate, includes the following steps：
（1）The dispersion liquid for preparing carbon nanotube in deionized water by carbon nanotube dispersion is configured to the carbon nanometer of 20mg/ml
Pipe dispersion liquid；
（2）Lead acetate, ceruse mixed solution are prepared, soluble lead salt is dissolved in deionized water and is configured to saturated solution；
（3）Prepare sodium hydroxide solution, a concentration of 16mg/ml of sodium hydroxide solution；
（4）Carbon nano tube dispersion liquid, sodium hydroxide solution and lead salt solution are added in reaction kettle and carry out hybrid reaction,
The volume ratio of the carbon nano tube dispersion liquid, sodium hydroxide solution and lead salt solution is 12：7：80；Add reducing agent oxalic acid
Solution, a concentration of 12mg/ml of the oxalic acid solution, dosage are the 70% of the sodium hydroxide solution, and water-bath keeps temperature 60 C
And continue stirring 40 hours；The mixed solution after reaction is taken out, 70 DEG C of low temperature distillations are carried out in flask, until solvent removes,
Reactant is taken out, pickling for several times, washing is repeated, is finally rinsed with deionized water, until material cleaning solution is in neutrality, then into
Enter baking oven drying, obtains carbon nanotube-brown lead oxide composite material；Brown lead oxide in carbon nanotube-brown lead oxide composite material
Content be 80%, the grain size of carbon nanotube-brown lead oxide composite material is 120 microns；
（5）Prepare polytetrafluoroethylene (PTFE) mesh plate, the mesh specification on the polytetrafluoroethylene (PTFE) mesh plate is 750 mesh；
（6）To step（5）In polytetrafluoroethylene (PTFE) mesh plate obtained carry out double-sided laser etching processing, the laser ablation processing
Used optical maser wavelength is 250nm, and the maximum power of laser generator is 18W, and the repetition rate of laser generator is
135KHz, laser generator pulse width are 75ns, and feed speed 12cm/min, laser generator energy density is 18J/
cm2, handled in same position using single ultraviolet laser corrasion；Polytetrafluoroethylene (PTFE) mesh after laser ablation
Plate first impregnates 17 minutes in Nafion resin solutions, takes out natural cooling, and it is 7 then to use mass ratio:3 isopropyl alcohol and water
Mixed solution washs for several times, until the thickness of polytetrafluoroethylene (PTFE) mesh plate is 0.5mm；Polytetrafluoroethylene (PTFE) mesh after etched processing
There are a large amount of pits in the two sides of plate, and the depth of the pit is 140 microns, and pit diameter is 150 microns, between adjacent pit
Spacing is 250 microns, and the porosity of polytetrafluoroethylene (PTFE) mesh plate is 60%；
（7）To step（6）The polytetrafluoroethylene (PTFE) mesh plate that is obtained after middle etching carries out plasma polarization process, using low temperature etc. from
Muon polarization processing, power 5kw, sweep speed 550mm/min, plasma energy metric density are 3J/mm2, obtain polarized poly-
Tetrafluoroethene mesh plate；
（8）By step（4）In carbon nanotube-brown lead oxide composite material for being prepared disperse again in deionized water, warp
Ultrasonic agitation 40 hours, is prepared the saturation dispersion liquid of carbon nanotube-brown lead oxide composite material；
（9）By step（7）In obtained polytetrafluoroethylene (PTFE) mesh plate be immersed into step（8）In obtained carbon nanotube-titanium dioxide
In the saturation dispersion liquid of lead composite material, taken out after being kept for 9 minutes, at room temperature natural air drying, then repeatedly with deionized water
Washing, and low temperature drying is carried out, obtain the polytetrafluoroethylene (PTFE) mesh plate coated with carbon nanotube-lead composite material, as ozone
Electrolytic cell anode catalyst diaphragm.
Comparative example 1
A kind of preparation method of ozone electrolytic cell anode catalyst diaphragm plate, includes the following steps：
（1）The dispersion liquid for preparing carbon nanotube in deionized water by carbon nanotube dispersion is configured to the carbon nanometer of 20mg/ml
Pipe dispersion liquid；
（2）Lead acetate, ceruse mixed solution are prepared, soluble lead salt is dissolved in deionized water and is configured to saturated solution；
（3）Prepare sodium hydroxide solution, a concentration of 18mg/ml of sodium hydroxide solution；
（4）Carbon nano tube dispersion liquid, sodium hydroxide solution and lead salt solution are added in reaction kettle and carry out hybrid reaction,
The volume ratio of the carbon nano tube dispersion liquid, sodium hydroxide solution and lead salt solution is 10：8：85；Add reducing agent oxalic acid
Solution, a concentration of 8mg/ml of the oxalic acid solution, dosage are the 75% of the sodium hydroxide solution, and water-bath keeps temperature 50-80
DEG C and continue stirring 36 hours；The mixed solution after reaction is taken out, 80 DEG C of low temperature distillations are carried out in flask, until solvent is gone
It removes, takes out reactant, pickling for several times, washing is repeated, is finally rinsed with deionized water, until material cleaning solution is in neutrality,
Baking oven drying is entered back into, carbon nanotube-brown lead oxide composite material is obtained；Dioxy in carbon nanotube-brown lead oxide composite material
The content for changing lead is 80%, and the grain size of carbon nanotube-brown lead oxide composite material is 100 microns；
（5）Prepare polytetrafluoroethylene (PTFE) mesh plate, the mesh specification on the polytetrafluoroethylene (PTFE) mesh plate is 750 mesh；
（6）To step（5）In polytetrafluoroethylene (PTFE) mesh plate obtained carry out double-sided laser etching processing, the laser ablation processing
Used optical maser wavelength is 100nm, and the maximum power of laser generator is 8W, and the repetition rate of laser generator is 40KHz,
Laser generator pulse width is 20ns, and feed speed 5cm/min, laser generator energy density is 5J/cm2, using list
A ultraviolet laser corrasion is handled in same position；Polytetrafluoroethylene (PTFE) mesh plate after laser ablation is first in Nafion
It is impregnated 10 minutes in resin solution, takes out natural cooling, it is 7 then to use mass ratio:The mixed solution of 3 isopropyl alcohol and water washs
For several times, until the thickness of polytetrafluoroethylene (PTFE) mesh plate is 1mm；The two sides of polytetrafluoroethylene (PTFE) mesh plate occurs big after etched processing
Pit is measured, the depth of the pit is 50 microns, and pit diameter is 60 microns, and the spacing between adjacent pit is 80 microns, is gathered
The porosity of tetrafluoroethene mesh plate is 20%；
（7）To step（6）The polytetrafluoroethylene (PTFE) mesh plate that is obtained after middle etching carries out plasma polarization process, using low temperature etc. from
Muon polarization processing, power 2kw, sweep speed 300mm/min, plasma energy metric density are 1J/mm2, obtain polarized poly-
Tetrafluoroethene mesh plate；
（8）By step（4）In carbon nanotube-brown lead oxide composite material for being prepared disperse again in deionized water, warp
Ultrasonic agitation 36 hours, is prepared the saturation dispersion liquid of carbon nanotube-brown lead oxide composite material；
（9）By step（7）In obtained polytetrafluoroethylene (PTFE) mesh plate be immersed into step（8）In obtained carbon nanotube-titanium dioxide
In the saturation dispersion liquid of lead composite material, holding is taken out after five minutes, at room temperature natural air drying, then repeatedly with deionized water
Washing, and low temperature drying is carried out, obtain the polytetrafluoroethylene (PTFE) mesh plate coated with carbon nanotube-lead composite material, as ozone
Electrolytic cell anode catalyst diaphragm.
Comparative example 2
A kind of preparation method of ozone electrolytic cell anode catalyst diaphragm plate, includes the following steps：
（1）The dispersion liquid for preparing carbon nanotube in deionized water by carbon nanotube dispersion is configured to the carbon nanometer of 20mg/ml
Pipe dispersion liquid；
（2）Lead acetate, ceruse mixed solution are prepared, soluble lead salt is dissolved in deionized water and is configured to saturated solution；
（3）Prepare sodium hydroxide solution, a concentration of 16mg/ml of sodium hydroxide solution；
（4）Carbon nano tube dispersion liquid, sodium hydroxide solution and lead salt solution are added in reaction kettle and carry out hybrid reaction, institute
The volume ratio for stating carbon nano tube dispersion liquid, sodium hydroxide solution and lead salt solution is 12：7：80；It is molten to add reducing agent oxalic acid
Liquid, a concentration of 12mg/ml of the oxalic acid solution, dosage are the 70% of the sodium hydroxide solution, and water-bath keeps temperature 60 C simultaneously
Persistently stir 40 hours；The mixed solution after reaction is taken out, 70 DEG C of low temperature distillations are carried out in flask, until solvent removes, is taken
Go out reactant, pickling for several times, washing is repeated, is finally rinsed with deionized water, until material cleaning solution is in neutrality, enters back into
Baking oven is dried, and carbon nanotube-brown lead oxide composite material is obtained；Brown lead oxide in carbon nanotube-brown lead oxide composite material
Content is 80%, and the grain size of carbon nanotube-brown lead oxide composite material is 120 microns；
（5）Prepare polytetrafluoroethylene (PTFE) mesh plate, the mesh specification on the polytetrafluoroethylene (PTFE) mesh plate is 750 mesh；
（6）To step（5）In polytetrafluoroethylene (PTFE) mesh plate obtained carry out double-sided laser etching processing, the laser ablation processing
Used optical maser wavelength is 500nm, and the maximum power of laser generator is 30W, and the repetition rate of laser generator is
200KHz, laser generator pulse width are 90ns, and feed speed 20cm/min, laser generator energy density is 30J/
cm2, handled in same position using multiple ultraviolet laser corrasions；Polytetrafluoroethylene (PTFE) mesh after laser ablation
Plate first impregnates 17 minutes in Nafion resin solutions, takes out natural cooling, and it is 7 then to use mass ratio:3 isopropyl alcohol and water
Mixed solution washs for several times, until the thickness of polytetrafluoroethylene (PTFE) mesh plate is 1mm；Polytetrafluoroethylene (PTFE) mesh plate after etched processing
Two sides there are a large amount of pits, the depth of the pit is 250 microns, and pit diameter is 180 microns, between adjacent pit between
Away from being 300 microns, the porosity of polytetrafluoroethylene (PTFE) mesh plate is 60%；
（7）To step（6）The polytetrafluoroethylene (PTFE) mesh plate that is obtained after middle etching carries out plasma polarization process, using low temperature etc. from
Muon polarization processing, power 8kw, sweep speed 700mm/min, plasma energy metric density are 5J/mm2, obtain polarized poly-
Tetrafluoroethene mesh plate；
（8）By step（4）In carbon nanotube-brown lead oxide composite material for being prepared disperse again in deionized water, warp
Ultrasonic agitation 40 hours, is prepared the saturation dispersion liquid of carbon nanotube-brown lead oxide composite material；
（9）By step（7）In obtained polytetrafluoroethylene (PTFE) mesh plate be immersed into step（8）In obtained carbon nanotube-titanium dioxide
In the saturation dispersion liquid of lead composite material, taken out after being kept for 9 minutes, at room temperature natural air drying, then repeatedly with deionized water
Washing, and low temperature drying is carried out, obtain the polytetrafluoroethylene (PTFE) mesh plate coated with carbon nanotube-lead composite material, as ozone
Electrolytic cell anode catalyst diaphragm.
Anode catalyst diaphragm plate prepared by above example and comparative example is applied to smelly under the conditions of same process
The preparation of Ozone Water is carried out in Oxygen Generator, and blank comparative example is set, and traditional cementi legal system is used in the blank comparative example
Anode catalyst diaphragm plate made of standby carries out the electrolytic preparation of ozone；Timing detects the concentration of its Ozone Water, data such as 1 institute of table
Show.
Table 1：The ozone of each embodiment and comparative example prepares interpretation of result
By the data comparison of table 1 it can be found that by carbon nanotube by brown lead oxide carry out it is compound after can preferably improve
Brown lead oxide catalyst growth is deposited on by the catalytic efficiency of brown lead oxide catalyst using carbon nanotube as support construction
Inside the surface of carbon nanotube or carbon nanotube, since carbon nanotube has extraordinary orientating type and electric conductivity so that whole
A anode catalyst diaphragm plate has higher electric conductivity and current density, improves the working efficiency of electrolysis；Brown lead oxide is located at carbon
On nanotube, effective contact area of the brown lead oxide catalyst and reactive material is increased, catalytic efficiency can be improved, into
And improve reaction efficiency and electrolysis production speed.
The process conditions of laser ablation also have an impact the complete performance of catalytic efficiency, optical maser wavelength in laser ablation,
The maximum power of laser generator, the repetition rate of laser generator, laser generator pulse width, the feed speed of etching,
Laser generator energy density all can be to carbon nanotube-deposition of the brown lead oxide composite material on polytetrafluoroethylene (PTFE) mesh plate
It has a direct impact, the selection of excessively high or too low etch process parameters cannot make carbon nanotube-brown lead oxide composite material
The good combination on polytetrafluoroethylene (PTFE), and then its catalytic efficiency in cell reaction is influenced, therefore, it is necessary to suitable work is arranged
Skill parameter combination, and also there is apparent synergistic effect between these parameter combinations, inconvenient arbitrarily change.Poly- the four of the present invention
Vinyl fluoride mesh plate is formd on polytetrafluoroethylene (PTFE) mesh plate into laser ablation and plasma polarization process has been crossed convenient for accommodating
With the ability of deposition of carbon nanotubes-brown lead oxide composite material, laser ablation can form recessed on polytetrafluoroethylene (PTFE) mesh plate
Hole, for accommodating carbon nanotube-brown lead oxide composite material, meanwhile, laser treatment and plasma polarization process can also improve
The activation energy of ptfe surface makes carbon nanotube-brown lead oxide composite material in polytetrafluoroethylene (PTFE) by molecule bonding force
Combination on mesh plate more closely, and without the interference of extraneous other factors so that catalytic action is more pure.
When by lead dioxide deposition growth on the carbon nanotubes, the reaction condition of deposition growing is also required to accurately set
It sets, inappropriate reaction condition and the cooperation of each content of material cannot reach preferable desired effect.Present invention setting is suitable
Reaction condition, using chemical synthesis directly on the carbon nanotubes beam system for brown lead oxide so that brown lead oxide is received with carbon
Combination and deposition on mitron is more secured；The present invention uses twice dispersing redeposition technology, by carbon nanotube-brown lead oxide
Composite material uniform deposition not only ensure that the uniformity and non interference of deposition, but also make carbon on polytetrafluoroethylene (PTFE) mesh plate
The combination of nanotube-brown lead oxide composite material and polytetrafluoroethylene (PTFE) mesh plate has enough intensity, it is sufficient to meet subsequent
Use demand.Using polytetrafluoroethylene (PTFE) as the frame board of anode catalyst diaphragm plate, cost is relatively low, and polytetrafluoroethylene (PTFE) itself has
There is corrosion resistant characteristic, be configured to the form of mesh plate, that is, there is larger contact area, and also assure due object
Manage intensity so that the replacement and dismounting of anode diaphragm plate are more simple and convenient.
Claims (7)
1. a kind of preparation method of ozone electrolytic cell anode catalyst diaphragm plate, which is characterized in that include the following steps：
（1）The dispersion liquid for preparing carbon nanotube, in deionized water by carbon nanotube dispersion, the carbon for being configured to 15-30mg/ml is received
Mitron dispersion liquid；
（2）Dissoluble lead salting liquid is prepared, soluble lead salt is dissolved in deionized water and is configured to saturation lead salt solution；
（3）Prepare alkaline solution, a concentration of 15-20mg/ml of alkaline solution；
（4）Carbon nano tube dispersion liquid, alkaline solution and lead salt solution are added in reaction kettle and carry out hybrid reaction, it is described
The volume ratio of carbon nano tube dispersion liquid, alkaline solution and lead salt solution is 5-15：5-10：75-90；Water-bath keeps temperature 50-
80 DEG C and continue stirring 24-48 hours；The mixed solution after reaction is taken out, 50-100 DEG C of low temperature distillation is carried out in flask, directly
It is removed to solvent, takes out reactant, pickling for several times, washing is repeated, is finally rinsed with deionized water, until material cleaning solution
It is in neutrality, enters back into baking oven drying, obtain carbon nanotube-lead composite material；
（5）Prepare polytetrafluoroethylene (PTFE) mesh plate, the mesh specification on the polytetrafluoroethylene (PTFE) mesh plate is 500-800 mesh；
（6）To step（5）In polytetrafluoroethylene (PTFE) mesh plate obtained carry out double-sided laser etching processing, the laser ablation processing
Used optical maser wavelength is 200-400nm, and the maximum power of laser generator is 10-20W, the repetition rate of laser generator
For 50-150KHz, laser generator pulse width is 30-80ns, feed speed 8-15cm/min, and laser generator energy is close
Degree is 10-20J/cm2, a large amount of pits of two sides appearance of polytetrafluoroethylene (PTFE) mesh plate, the depth of the pit is 70-200 microns,
Pit diameter is 80-160 microns, and the spacing between adjacent pit is 100-300 microns, the porosity of polytetrafluoroethylene (PTFE) mesh plate
For 30%-65%；
（7）To step（6）The polytetrafluoroethylene (PTFE) mesh plate obtained after middle etching is polarised, and obtains polarized polytetrafluoroethyl-ne
Alkene mesh plate；
（8）By step（4）In carbon nanotube-lead composite material for being prepared disperse in deionized water, to stir through ultrasound again
It mixes 24-48 hours, the saturation dispersion liquid of carbon nanotube-lead composite material is prepared；
（9）By step（7）In obtained polytetrafluoroethylene (PTFE) mesh plate be immersed into step（8）In obtained carbon nanotube-lead it is compound
In the saturation dispersion liquid of material, taken out after being kept for 3-10 minutes, natural air drying, is then washed with deionized water repeatedly at room temperature
It washs, and carries out low temperature drying, obtain the polytetrafluoroethylene (PTFE) mesh plate coated with carbon nanotube-lead composite material, as ozone electricity
Solve pond anode catalyst diaphragm.
2. the preparation method of ozone electrolytic cell anode catalyst diaphragm plate according to claim 1, which is characterized in that step
（4）Hybrid reaction in be also added into reducing agent solution, the reducing agent is oxalic acid, a concentration of 5- of the reducing agent solution
15mg/ml, the dosage of the reducing agent solution are the 50-90% of the alkaline solution.
3. the preparation method of ozone electrolytic cell anode catalyst diaphragm plate according to claim 1 or 2, which is characterized in that step
Suddenly（4）In obtained carbon nanotube-lead composite material be carbon nanotube-brown lead oxide composite material.
4. the preparation method of ozone electrolytic cell anode catalyst diaphragm plate according to claim 2 or 3, which is characterized in that institute
State step（2）In soluble lead salt be the nitrate containing lead element, acetate, carbonate, hydrochloride, sulfate and network
Close one or more of salt；The alkaline solution is sodium hydroxide, one kind of potassium hydroxide or mixture.
5. the preparation method of ozone electrolytic cell anode catalyst diaphragm plate according to claim 4, which is characterized in that the step
Suddenly（6）In laser ablation processing be ultraviolet laser etching processing, acted on together for single laser pulse or multiple laser pulses
One position carries out；Polytetrafluoroethylene (PTFE) mesh plate after laser ablation first impregnates 15-20 minutes in Nafion resin solutions, takes
Go out natural cooling, it is 7 then to use mass ratio:The mixed solution of 3 isopropyl alcohol and water washs for several times, until polytetrafluoroethylene (PTFE) mesh
The thickness of plate is 0.2-1mm.
6. the preparation method of ozone electrolytic cell anode catalyst diaphragm plate according to any one of claims 1-5, feature
It is, the step（7）In polarization process be plasma polarization process, using low-temperature plasma polarization process, power is
3.5-5kw, sweep speed 400-600mm/min, plasma energy metric density are 1.5-3J/mm2。
7. the preparation method of the ozone electrolytic cell anode catalyst diaphragm plate according to any one of claim 1-6, feature
It is, in the carbon nanotube-brown lead oxide composite material, the content of brown lead oxide is 70-85%, the carbon nanotube-dioxy
The grain size for changing lead composite material is 50-150 microns.
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| CN109888302A (en) * | 2019-02-25 | 2019-06-14 | 成都新柯力化工科技有限公司 | A kind of method that scale continuously prepares membrane electrode ordering Catalytic Layer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2150401A1 (en) * | 1971-10-09 | 1973-04-12 | Rheinisch Westfaelisches Elek | Electrodes for electrochemical elements - have skeleton of inert conductor and plastics |
| EP0718903A1 (en) * | 1994-12-07 | 1996-06-26 | Japan Gore-Tex, Inc. | An ion exchange membrane and electrode assembly for an electrochemical cell |
| CN106207131A (en) * | 2016-08-31 | 2016-12-07 | 苏州载物强劲新材料科技有限公司 | Accumulator Graphene/β PbO2the preparation method of nano composite material |
-
2018
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2150401A1 (en) * | 1971-10-09 | 1973-04-12 | Rheinisch Westfaelisches Elek | Electrodes for electrochemical elements - have skeleton of inert conductor and plastics |
| EP0718903A1 (en) * | 1994-12-07 | 1996-06-26 | Japan Gore-Tex, Inc. | An ion exchange membrane and electrode assembly for an electrochemical cell |
| CN106207131A (en) * | 2016-08-31 | 2016-12-07 | 苏州载物强劲新材料科技有限公司 | Accumulator Graphene/β PbO2the preparation method of nano composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109888302A (en) * | 2019-02-25 | 2019-06-14 | 成都新柯力化工科技有限公司 | A kind of method that scale continuously prepares membrane electrode ordering Catalytic Layer |
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