CN104759272A - Membrane electrode of membrane electrode low-voltage electrolysis type ozone generator and manufacturing method for positive and negative electrodes of membrane electrode low-voltage electrolysis type ozone generator - Google Patents
Membrane electrode of membrane electrode low-voltage electrolysis type ozone generator and manufacturing method for positive and negative electrodes of membrane electrode low-voltage electrolysis type ozone generator Download PDFInfo
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Abstract
The invention relates to membrane electrodes of electrolysis type ozone generators and provides a membrane electrode of a membrane electrode low-voltage electrolysis type ozone generator and a manufacturing method for the positive and negative electrodes of the membrane electrode low-voltage electrolysis type ozone generator. According to the invention, boron-doped diamond with high electrocatalytic activity, high corrosion resistance and no secondary pollution is used as a positive electrode catalyst; then the boron-doped diamond is directly deposited on a porous titanium plate by using a vapor deposition method; and the porous titanium with the deposited boron-doped diamond and a polymer proton exchange membrane are subjected to hot pressing so as to form a positive electrode structure in which the porous titanium, the positive electrode catalyst and the polymer proton exchange membrane are integrated into one. Compared with the prior art, the positive electrode structure prepared in the invention is simple to prepare and convenient to assembly and can be produced in batch; moreover, a boron-doped diamond film deposited on the surface of the porous titanium plate has a porous structure, so water permeation and air permeation performances are effectively improved, the phenomena like decrease of the performance of the catalyst and rise of groove pressure and temperature caused by unsmooth water permeation and air permeation are avoided, the service life of the membrane electrode is improved, and long-term stable operation of the membrane electrode electrolysis type ozone generator is guaranteed.
Description
Technical field
The present invention relates to electrolysis type ozone generator technical field, be specifically related to the membrane electrode of electrolysis ozone generator.
Background technology
Ozone is a kind of extremely strong oxidant; there is strong sterilizing effect and the ability of oxidative degradation organic pollution; and reacted product is the oxygen useful to human body; have no side effect, the advantage such as nontoxicity, non-secondary pollution, become more and more extensive in the application in the field such as advanced oxidation process, drinking water deep purification, environmental protection, food processing, medical treatment and nursing, preserving fruit and vegetable utilizing of waste water.
The method that ozone is produced in current existing market is mainly divided into corona discharge method, UV radiation and solid polymer membrane (PEM film) electrode low tension solution.Wherein, PEM membrane electrode low tension solution is that a kind of novel electrochemical method prepares ozone, compare with corona discharge method and UV radiation, the advantages such as the method has that the carcinogens such as high, the nonnitrogenous oxide of preparation concentration of ozone gas, preparation cost are low, membrane electrode long service life, equipment installation and maintenance are simple, become a kind of Ozone generation method of the most market competitiveness.
PEM membrane electrode is the core component of low-voltage electrolysis formula ozone generator.Current typical PEM membrane electrode assembly comprises POROUS TITANIUM PLATE, anode catalyst, cathod catalyst and solid polymer proton exchange membrane etc.Wherein, anode catalyst and anode construction (being made up of POROUS TITANIUM PLATE, anode catalyst and proton exchange polymer membrane) play a key effect to generator performance.
Electrochemistry formated ozone technology requires that anode catalyst material has good electro catalytic activity and corrosion resistance to ozone precipitation.Graphite, vitreous carbon, Pt metal once used anode material in the research of early stage electrochemistry formated ozone technology, but due to Pt metal electrode price too expensive; Easily be corroded and the shortcomings such as consumption in graphite and vitreous carbon use procedure, the low-voltage electrolysis formula ozone generator product on existing market adopts that electro catalytic activity is high usually, corrosion resistance is good, price brown lead oxide material is inexpensively as the anode catalyst of membrane electrode.
Anode construction is also the key factor affecting electrochemistry formated ozone efficiency.In current electrochemistry formated Ozonizer system, be that anode material is formed catalyst and membrane electrode assembly through being hot-pressed onto in solid polymer proton exchange membrane after batch mixing film-making, then form anode construction with POROUS TITANIUM PLATE (POROUS TITANIUM PLATE plays the effect of water conservancy diversion, conduction and support catalyst) by mechanical compaction.Being separated with tradition is compared with electrode, and this membrane electrode integrated technology has that equipment is simple, volume is little, current efficiency is high, low power consumption and other advantages.
Although PEM anode catalyst that membrane electrode adopts and the anode construction of above-mentioned low-voltage electrolysis formula ozone generator have many advantages in electrochemistry formated ozone performance, but also there is the shortcoming that can not be ignored: on the one hand, brown lead oxide is as anode catalyst, no matter from the raw-material preparation link of brown lead oxide, brown lead oxide diaphragm process or in electrochemistry formated ozone process, toxic Pb ions in fact all cannot be avoided to cause secondary pollution to environment; On the other hand, at present adopt the relative very complicated of anode construction preparation process, be not easy to ensure product quality, and in running, catalyst easily blocks POROUS TITANIUM PLATE, cause water, gas to circulate smooth, superpressure raises, and reduces membrane electrode service life.The shortcoming of these two aspects all will hinder business promotion and the practical application of PEM membrane electrode low-voltage electrolysis ozone generator product.
Summary of the invention
The object of the present invention is to provide a kind of anode catalyst of membrane electrode low-voltage electrolysis formula ozone generator.
The present invention also aims to the anode construction that a kind of membrane electrode low-voltage electrolysis formula ozone generator is provided.
The present invention also aims to the anode fabrication method that a kind of membrane electrode low-voltage electrolysis formula ozone generator is provided.
The present invention also aims to the membrane electrode that a kind of membrane electrode low-voltage electrolysis formula ozone generator is provided.
The present invention can realize for achieving the above object by the following technical solutions:
An anode catalyst for membrane electrode low-voltage electrolysis formula ozone generator, is characterized in that, adopts boron-doped diamond material as the anode catalyst of low-voltage electrolysis ozone generator membrane electrode.Boron-doped diamond not only has very strong mechanical strength, chemical inertness, heat endurance and corrosion resistance, there is wider electrochemical window simultaneously, yield of ozone can be improved further, and no matter be also mounted in ozone generator from the preparation of its raw material and run, boron carbon does not have toxicity to environment, can not produce secondary pollution to environment.Therefore, boron-doped diamond belongs to environmental type anode catalyst.
A kind of anode construction of membrane electrode low-voltage electrolysis formula ozone generator, comprise a proton exchange polymer membrane, it is characterized in that, described proton exchange polymer membrane compresses the POROUS TITANIUM PLATE having to deposit anode catalyst, form the anode construction of described membrane electrode low-voltage electrolysis formula ozone generator.
Described anode catalyst, is characterized in that, adopt boron-doped diamond material to be deposited directly in POROUS TITANIUM PLATE, the boron-doped diamond Catalytic Layer that described boron-doped diamond deposition of material is formed has loose structure.
Described POROUS TITANIUM PLATE is provided with a plurality of hole, and preferably, the porosity of POROUS TITANIUM PLATE is preferably 30-45%, and aperture is preferably 15-48 μm.Preferably average grain diameter is 25 μm further, is of a size of 30mm × 30mm square sheet POROUS TITANIUM PLATE.Described boron-doped diamond deposition of material is in the hole of the lower surface of described POROUS TITANIUM PLATE and the bottom of described POROUS TITANIUM PLATE.
A kind of anode fabrication method of membrane electrode low-voltage electrolysis formula ozone generator, it is characterized in that, by chemical vapour deposition technique, anode catalyst is deposited directly in POROUS TITANIUM PLATE, form the membrane electrode anode construction integrating POROUS TITANIUM PLATE, anode catalyst and proton exchange polymer membrane again with proton exchange polymer membrane hot pressing, described anode catalyst adopts boron-doped diamond material.This structure is completely free of and existing is prepared abrasive dust involved by ozone generator membrane electrode anode construction, bonds, rolls the complex techniques process such as sheet and hot pressing, and manufacture craft is simple, easy to assembly, is conducive to batch production.And, due to the loose structure of titanium plate, deposit its on the surface Boron-doped diamond also present loose structure, the anode catalyst film of this loose structure can effectively improve permeable, permeability, avoid because water-permeable and air permeable does not freely cause the decline of catalyst performance, groove pressure and the phenomenon such as temperature rising, improve membrane electrode service life, ensure that membrane electrode electrolysis ozone generator can steady in a long-termly run.
A kind of anode fabrication method of membrane electrode low-voltage electrolysis formula ozone generator is as follows:
Step one, pre-treatment is carried out to POROUS TITANIUM PLATE: first soak with potassium hydroxide, tertiary sodium phosphate and edta solution and carry out oil removing degreasing, acid etch is carried out to remove POROUS TITANIUM PLATE surface and the oxide-film of its apparent gap with aqueous sulfuric acid after deionized water rinsing, thus build alligatoring, active matrix surface.
Before step one, first POROUS TITANIUM PLATE can also be cut into the size that the anode construction that meets existing low-voltage electrolysis formula ozone generator membrane electrode requires.The POROUS TITANIUM PLATE porosity ranges chosen requires that aperture is 15-48 μm for 30-45%.
Step 2, grinds the POROUS TITANIUM PLATE processed through step one with bortz powder, then Ultrasonic Cleaning in acetone soln and deionized water solution successively, then dries up with nitrogen that to put into Dewar bottle stand-by.This step is for subsequent chemistry vapor diamond deposition provides favourable forming core point, has the diamond nucleation density and the effect of raising deposition film quality that increase POROUS TITANIUM PLATE surface.Bortz powder particle diameter is preferably less than 5 μm.
Step 3, utilizes heated filament auxiliary chemical vapor deposition method at the uniform anode catalyst of POROUS TITANIUM PLATE surface deposition one deck through step 2 process, and described anode catalyst adopts boron-doped diamond material.Reactant gas source is methane, hydrogen and borine.Wherein, methane is carbon source, and borine is boron source, and hydrogen is as the carrier of methane and borine source of the gas.In enforcement vapor deposition processes, being controlled the incorporation of boron in diamond thin by the atomic ratio (B/C) changing boron and carbon in source of the gas, regulating and controlling Catalytic Layer film thickness by controlling sedimentation time.
Step 4, the side adopting hot press POROUS TITANIUM PLATE to be coated with boron-doped diamond material compresses with proton exchange polymer membrane hot pressing and combines, and obtains anode construction.
In step 4, by proton exchange polymer membrane with the POROUS TITANIUM PLATE mechanical hot pressing being coated with Boron-doped diamond before, also need to use sand paper to carry out roughening treatment to its surface, to improve Boron-doped diamond with rete in conjunction with effect.
A membrane electrode for membrane electrode low-voltage electrolysis formula ozone generator, is made up of an anode construction and a cathode construction;
Described anode construction comprises a proton exchange polymer membrane, described proton exchange polymer membrane compresses the POROUS TITANIUM PLATE having to deposit anode catalyst, forms a kind of anode construction of membrane electrode low-voltage electrolysis formula ozone generator.Described anode catalyst adopts boron-doped diamond material, and described cathode construction comprises a carbon and carries platinum cathode catalyst diaphragm.
Accompanying drawing explanation
Fig. 1 is a kind of structural representation of membrane electrode of the present invention;
Fig. 2 be adopt the electrolysis type ozone generator of the electrolysis type ozone generator of anode construction of the present invention and prior art in running yield of ozone (mg/h) with prolongation (24 hours running times of the every day time cycle of operation, by hour in units of, h) variation diagram.
Detailed description of the invention
The technological means realized to make the present invention, creation characteristic, reaching object and effect is easy to understand, setting forth the present invention further below in conjunction with concrete diagram.
With reference to Fig. 1, the present invention adopts that electro catalytic activity is high, corrosion resistance is high, the boron-doped diamond of non-secondary pollution is as anode catalyst, further, utilize vapour deposition process to be deposited directly in POROUS TITANIUM PLATE by boron-doped diamond, and be hot pressed into proton exchange polymer membrane the anode construction integrating POROUS TITANIUM PLATE, anode catalyst and proton exchange polymer membrane.Compared with prior art, this anode construction not only preparation technology is simple, easy to assembly, be conducive to batch production, and the Boron-doped diamond being deposited on POROUS TITANIUM PLATE surface has loose structure, effectively improve permeable, permeability, avoid freely not causing the phenomenons such as the decline of catalyst performance, groove pressure and temperature rising due to water-permeable and air permeable, improve membrane electrode service life, ensure that membrane electrode electrolysis ozone generator can steady in a long-termly run.
Specific embodiment is as follows:
To choose average grain diameter be the POROUS TITANIUM PLATE of 25 μm is research matrix, and it cuts into and is of a size of 30mm × 30mm square sheets.
Above-mentioned POROUS TITANIUM PLATE base material is put into the aqueous solution be made up of potassium hydroxide, tertiary sodium phosphate and ethylenediamine tetra-acetic acid, soak at 50-60 DEG C and remove surperficial grease in 5 minutes, and utilize 20% aqueous sulfuric acid to carry out within acid etch 5-8 minute, obtaining the fresh matrix surface that surface has certain roughness to POROUS TITANIUM PLATE at 50-60 DEG C.
Carry out milled processed to above-mentioned POROUS TITANIUM PLATE sill surface, employing particle diameter is that the diamond paste of 2.5 μm grinds 2-5 minute on polished machine, and speed of grinding plate is 300r/h.Successively at acetone soln and remove ultrasonic cleaning 5-10 minute in dried up solution after grinding, and dry up with nitrogen that to put into Dewar bottle stand-by.
Utilize heated filament auxiliary chemical vapor deposition method at above-mentioned POROUS TITANIUM PLATE substrate surface deposition Boron-doped diamond.In chemical vapor deposition processes, be strict with methane and hydrogen volume than for 1:99 and borine and hydrogen volume are than being 2:98, and atomic ratio (B/C) volume ratio controlling boron and carbon is in the present embodiment 2.5%.Reaction temperature is 800 DEG C, chamber pressure 5kPa, and sedimentation time is 6 hours.To obtain Boron-doped diamond average thickness be 6 μm.By above-mentioned steps, prepare a kind of porous type Boron-doped diamond that to be deposited directly in POROUS TITANIUM PLATE as the anode catalyst of low-voltage electrolysis formula ozone generator.
Adopt hot press that above-mentioned POROUS TITANIUM PLATE is coated with Boron-doped diamond side and proton exchange polymer membrane hot pressing, hot pressing temperature is 80-100 DEG C, and hot pressing time is 5-10 minute.For ensureing that Boron-doped diamond and proton exchange polymer membrane bond in good condition, before hot pressing, adopt 1500 or No. 2000 sand paper to carry out roughening treatment to proton exchange polymer membrane surface, and utilize nozzle to a small amount of Nafion solution of Boron-doped diamond surface coating on POROUS TITANIUM PLATE surface.By above-mentioned steps, preparing a kind of take Boron-doped diamond as the anode construction of the novel membrane electrode of anode catalyst.
By above-mentioned novel boron-doped diamond membrane electrode anode construction, carry platinum cathode catalyst diaphragm with carbon, be assembled into complete membrane electrode, as shown in Figure 1.A membrane electrode for membrane electrode low-voltage electrolysis formula ozone generator, is made up of an anode construction and a cathode construction; Anode construction comprises a proton exchange polymer membrane 1, and proton exchange polymer membrane 1 compresses the POROUS TITANIUM PLATE 3 having to deposit anode catalyst 2, anode catalyst 2 adopts boron-doped diamond material; Anode catalyst layer has loose structure, and cathode construction comprises a carbon and carries platinum cathode catalyst diaphragm 4.POROUS TITANIUM PLATE 3 is provided with a plurality of hole, and boron-doped diamond deposition of material is in the hole of the lower surface of POROUS TITANIUM PLATE and the bottom of POROUS TITANIUM PLATE; The porosity of POROUS TITANIUM PLATE is 30-45%, and aperture is 15-48 μm.
This membrane electrode is installed in ozone generator, put on constant-current supply trial run, and test this membrane electrode ozone generator gas generation property having Novel boron doped diamond anode construction, and compare with the existing membrane electrode ozone generator performance forming anode construction by brown lead oxide under same service condition.Gas generation property comparative result is as follows:
As can be seen from Figure 2, ozone generator gas generation property of the present invention is obviously better than the gas generation property of the ozone generator of prior art.Within 3 first quarter moon trial run cycles by a definite date, the yield of ozone of the ozone generator of prior art presents attenuation trend, along with the cycle of operation extends, 300-400mg/h is decayed to from initial stage higher 600-700mg/h, and the not significant decay of performance within the whole trial run cycle of the yield of ozone of ozone generator of the present invention, and remain essentially within the scope of 700-800mg/h.This result not only illustrates that membrane electrode anode catalyst of the present invention can improve ozone output further, but also illustrate that the porous type membrane electrode anode construction that has that constructs of the present invention has good structural stability, ozone generator also can be kept relative stability aerogenesis yield efficiency in long-play situation.
More than show and describe general principle of the present invention and principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and description just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (14)
1. an anode catalyst for membrane electrode low-voltage electrolysis formula ozone generator, is characterized in that, adopts boron-doped diamond material as the anode catalyst of low-voltage electrolysis ozone generator membrane electrode.
2. the anode construction of a membrane electrode low-voltage electrolysis formula ozone generator, comprise a proton exchange polymer membrane, it is characterized in that, described proton exchange polymer membrane compresses the POROUS TITANIUM PLATE having to deposit anode catalyst, form the anode construction of described membrane electrode low-voltage electrolysis formula ozone generator.
3. anode catalyst according to claim 2, is characterized in that, adopt boron-doped diamond material to be deposited directly in POROUS TITANIUM PLATE, the boron-doped diamond Catalytic Layer that described boron-doped diamond deposition of material is formed has loose structure.
4. the anode construction of a kind of membrane electrode low-voltage electrolysis formula ozone generator according to claim 2, it is characterized in that, described POROUS TITANIUM PLATE is provided with a plurality of hole, and described boron-doped diamond deposition of material is in the hole of the lower surface of described POROUS TITANIUM PLATE and the bottom of described POROUS TITANIUM PLATE.
5. the anode construction of a kind of membrane electrode low-voltage electrolysis formula ozone generator according to claim 3, it is characterized in that, the porosity of described POROUS TITANIUM PLATE is 30-45%, and aperture is 15-48 μm.
6. the anode fabrication method of a membrane electrode low-voltage electrolysis formula ozone generator, it is characterized in that, by chemical vapour deposition technique, anode catalyst is deposited directly in POROUS TITANIUM PLATE, then forms with proton exchange polymer membrane hot pressing the membrane electrode anode construction integrating POROUS TITANIUM PLATE, anode catalyst and proton exchange polymer membrane.
7. the anode fabrication method of a kind of membrane electrode low-voltage electrolysis formula ozone generator according to claim 6, is characterized in that, described anode catalyst adopts boron-doped diamond material.
8. the anode fabrication method of a kind of membrane electrode low-voltage electrolysis formula ozone generator according to claim 7, is characterized in that,
Step one, pre-treatment is carried out to POROUS TITANIUM PLATE: first soak with potassium hydroxide, tertiary sodium phosphate and edta solution and carry out oil removing degreasing, acid etch is carried out to remove POROUS TITANIUM PLATE surface and the oxide-film of its apparent gap with aqueous sulfuric acid after deionized water rinsing, thus build alligatoring, active matrix surface;
Step 2, grinds the POROUS TITANIUM PLATE processed through step one with bortz powder, then Ultrasonic Cleaning in acetone soln and deionized water solution successively, then dries up with nitrogen that to put into Dewar bottle stand-by;
Step 3, utilize heated filament auxiliary chemical vapor deposition method at the uniform anode catalyst of POROUS TITANIUM PLATE surface deposition one deck through step 2 process, described anode catalyst adopts boron-doped diamond material, reactant gas source is methane, hydrogen and borine, wherein, methane is carbon source, and borine is boron source, and hydrogen is as the carrier of methane and borine source of the gas;
Step 4, the side adopting hot press POROUS TITANIUM PLATE to be coated with boron-doped diamond material compresses with proton exchange polymer membrane hot pressing and combines, and obtains anode construction.
9. the anode fabrication method of a kind of membrane electrode low-voltage electrolysis formula ozone generator according to claim 8, it is characterized in that, in step 4, by proton exchange polymer membrane with the POROUS TITANIUM PLATE mechanical hot pressing being coated with Boron-doped diamond before, also need to use sand paper to carry out roughening treatment to its surface, to improve Boron-doped diamond with rete in conjunction with effect.
10. a membrane electrode for membrane electrode low-voltage electrolysis formula ozone generator, is made up of an anode construction and a cathode construction;
Described anode construction comprises a proton exchange polymer membrane, it is characterized in that, described proton exchange polymer membrane compresses the POROUS TITANIUM PLATE having to deposit anode catalyst, forms described anode construction.
The membrane electrode of 11. a kind of membrane electrode low-voltage electrolysis formula ozone generators according to claim 10, it is characterized in that, described POROUS TITANIUM PLATE is provided with a plurality of hole, and described anode catalyst is deposited in the hole of the lower surface of described POROUS TITANIUM PLATE and the bottom of described POROUS TITANIUM PLATE; The porosity of described POROUS TITANIUM PLATE is 30-45%, and aperture is 15-48 μm.
The membrane electrode of 12. a kind of membrane electrode low-voltage electrolysis formula ozone generators according to claim 10, it is characterized in that, described anode construction obtains by the following method:
By chemical vapour deposition technique, anode catalyst is deposited directly in POROUS TITANIUM PLATE, form the membrane electrode anode construction integrating POROUS TITANIUM PLATE, anode catalyst and proton exchange polymer membrane again with proton exchange polymer membrane hot pressing, described anode catalyst adopts boron-doped diamond material.
The membrane electrode of 13. a kind of membrane electrode low-voltage electrolysis formula ozone generators according to claim 10,11 or 12, is characterized in that, described anode catalyst adopts boron-doped diamond material.
The membrane electrode of 14. a kind of membrane electrode low-voltage electrolysis formula ozone generators according to claim 10,11 or 12, it is characterized in that, described cathode construction comprises a carbon and carries platinum cathode catalyst diaphragm.
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CN108396307A (en) * | 2018-01-18 | 2018-08-14 | 昆明理工大学 | A kind of preparation method of the diamond thin with strong film base adhesion strength |
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