CN117758307A - Porous layer treatment method for anion-cation exchange membrane electrolyzed water and application - Google Patents
Porous layer treatment method for anion-cation exchange membrane electrolyzed water and application Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000012528 membrane Substances 0.000 title claims abstract description 18
- 238000005341 cation exchange Methods 0.000 title claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 110
- 238000004140 cleaning Methods 0.000 claims abstract description 36
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 35
- 238000002791 soaking Methods 0.000 claims abstract description 27
- 239000000956 alloy Substances 0.000 claims abstract description 19
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 124
- 229910052759 nickel Inorganic materials 0.000 claims description 62
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000007747 plating Methods 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 238000004381 surface treatment Methods 0.000 claims description 14
- 238000004544 sputter deposition Methods 0.000 claims description 12
- 238000005868 electrolysis reaction Methods 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000003014 ion exchange membrane Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 137
- 229910052751 metal Inorganic materials 0.000 description 23
- 239000002184 metal Substances 0.000 description 23
- 238000005303 weighing Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000428 dust Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- Electroplating Methods And Accessories (AREA)
Abstract
The invention relates to the technical field of ion exchange membrane electrolyzed water, and discloses a porous layer treatment method for anion-cation exchange membrane electrolyzed water and application thereof, wherein the method specifically comprises the following steps: 1) Pretreating the porous layer substrate; 2) Soaking the pretreated porous layer substrate in ammonia water, and cleaning to obtain a cleaned porous layer substrate; 3) Placing the cleaned porous layer substrate in concentrated sulfuric acid to carry out surface hydrogenation treatment under the constant potential condition; and (3) carrying out alloy coating on the surface of the porous layer substrate subjected to surface hydrogenation treatment to obtain the porous layer. According to the invention, the porous layer is subjected to pretreatment, soaking, surface hydrogenation treatment and alloy coating, and the steps are matched with each other, so that the alloy coating can well cover the porous layer substrate, and the electrochemical performance and the durability of the porous layer are effectively improved.
Description
Technical Field
The invention relates to the technical field of ion exchange membrane electrolyzed water, in particular to a porous layer treatment method for anion-cation exchange membrane electrolyzed water and application thereof.
Background
The hydrogen can be used as an energy storage medium to convert and store large-scale renewable energy, can be used as an important chemical raw material to be widely applied to the industrial field, and can be used as fuel to provide energy sources for power devices such as fuel cell engines and the like. The proton exchange membrane electrolyzed water and the anion exchange membrane electrolyzed water can produce hydrogen under safe, clean and high-pressure conditions, and simultaneously has higher electrolysis efficiency than the prior alkaline water electrolysis technology because of using a thinner diaphragm.
The porous diffusion layer (hereinafter referred to as porous layer) is an important part in the water electrolysis reaction device of the anion-cation exchange membrane, and the position of the porous diffusion layer is between the membrane electrode and the flow field, so that the porous diffusion layer plays an important role in water vapor transmission, conductive channels and supporting the membrane electrode. In the working process, the porous layer is in an environment with high potential and high oxygen concentration or high hydrogen concentration, and is extremely easy to generate problems of corrosion, hydrogen embrittlement and the like, so that the porous layer is generally required to be subjected to surface treatment to improve the durability.
The porous layers currently used in commercial water electrolysis devices are based on thin webs, thin powder hot pressed sheets or thin fiber mats made of nickel/titanium materials. The porous layer usually needs to be subjected to surface acid treatment before assembly so as to remove an oxide layer on the surface of the porous layer; and then, carrying out noble metal electroplating on the surface of the substrate to form an oxidation-resistant corrosion-resistant protective layer. However, the main disadvantage of this method is that the precious metal layer on the surface cannot completely cover the surface of the base material (as shown in fig. 1), so that corrosion occurs when exposed metal exists.
Disclosure of Invention
The invention aims to overcome the defect that the electrochemical performance and durability of a porous layer are limited due to the fact that the existing surface treatment method for the porous layer in the water by anion-cation exchange membrane electrolysis cannot cover a porous layer substrate material well, and further provides the porous layer treatment method for the water by anion-cation exchange membrane electrolysis.
The invention adopts the following technical scheme:
the invention provides a porous layer treatment method for anion-cation exchange membrane electrolyzed water, which comprises the following steps:
1) Pretreating the porous layer substrate;
2) Soaking the pretreated porous layer substrate in ammonia water, and cleaning to obtain a cleaned porous layer substrate;
3) Placing the cleaned porous layer substrate in concentrated sulfuric acid to carry out surface hydrogenation treatment under the constant potential condition;
4) And (3) carrying out alloy coating on the surface of the porous layer substrate subjected to surface hydrogenation treatment to obtain the porous layer.
The mass concentration of the ammonia water in the step 2) is 5-10%.
And/or, the soaking time is 20-30 minutes.
Further, the cleaning step in the step 2) includes cleaning the soaked porous layer substrate by sequentially adopting hydrogen peroxide and deionized water.
Further, the mass concentration of the hydrogen peroxide is 5-10%, the cleaning time of the hydrogen peroxide is 5-10 minutes, and the cleaning time of the deionized water is 5-10 minutes.
Further, in the step 3), the step of surface hydrotreating includes placing the cleaned porous layer substrate in concentrated sulfuric acid with a concentration of 98wt%, and then connecting the cleaned porous layer substrate and the platinum electrode to the positive electrode and the negative electrode of the potentiostat, respectively, and performing surface hydrotreating on the porous layer substrate in a potentiostatic mode.
Further, the porous layer substrate is selected from a porous layer nickel substrate or a porous layer titanium substrate.
Further, the porous layer nickel substrate is subjected to surface hydrogenation treatment, the potential range is-0.25V to 0V, and the treatment time is 15-20 minutes.
Further, the porous layer titanium substrate is subjected to surface hydrogenation treatment, the potential range is-1.63V to 0V, and the treatment time is 15-20 minutes.
Further, in the step 4), the alloy plating coating step includes plating a metal Nb layer on the surface of the porous layer substrate after the surface hydrogenation treatment, and then plating a metal Ir layer on the surface of the metal Nb layer.
Further, the plating step is performed by a magnetron sputtering method, preferably, a direct current magnetron sputtering method.
Further, the plating pressure is 3-5Pa, and the sputtering time is 2-5 minutes.
Further, the method further comprises the steps of cleaning and drying the porous layer substrate after the surface hydrogenation treatment before the alloy plating coating is carried out on the surface of the porous layer substrate after the surface hydrogenation treatment.
Further, when the porous layer substrate is a porous layer titanium substrate, the pretreatment of step 1) includes a step of immersing the porous layer substrate in an acid solution and then washing with water.
Preferably, the acid solution is hydrochloric acid solution, the concentration of the hydrochloric acid solution is 0.1M, the soaking time is 10-20 minutes, and the water cleaning time is 5-10 minutes.
Wherein "M" means "1mol/L".
Further, when the porous layer substrate is a porous layer nickel substrate, the pretreatment of step 1) includes a step of ultrasonic immersing the porous layer substrate in an organic solvent and then washing with water.
Preferably, the organic solvent is acetone, the soaking time is 10-20 minutes, and the water cleaning time is 5-10 minutes.
The invention also provides an electrolytic water reaction device comprising a porous layer obtained by the surface treatment method.
The invention also provides an application of the porous layer in water electrolysis.
The invention has the beneficial effects that:
the invention provides a porous layer treatment method for anion-cation exchange membrane electrolyzed water, which comprises the steps of firstly, preprocessing a porous layer substrate; soaking the pretreated porous layer substrate in ammonia water, cleaning, soaking the porous layer substrate in the ammonia water, wherein ammonia molecules in the ammonia water can form coordination bonds with metal atoms, so that an ammonia-metal ion complex is formed, on one hand, the surface roughness and the surface area of the porous layer are improved, and further more sites are provided for subsequent noble metal coating; on the other hand, the hydrophilicity of the surface of the porous layer is improved, so that the transportation and diffusion of reactant water to a reaction area are facilitated; meanwhile, the structural strength reduction caused by excessive acid treatment can be effectively avoided; then placing the cleaned porous layer substrate in concentrated sulfuric acid to carry out surface hydrogenation treatment under the condition of constant potential, and carrying out surface hydrogenation treatment in the sulfuric acid to enable the substrate metal to form a metal hydride film on the surface of the substrate metal, wherein the film has higher activity and is convenient for the modification of the alloy plating layer on the surface of the subsequent metal; and finally, carrying out alloy coating on the surface of the porous layer substrate subjected to surface hydrogenation treatment to obtain the porous layer. According to the invention, the porous layer is subjected to pretreatment, soaking, surface hydrogenation treatment and alloy coating, and the steps are matched with each other, so that the alloy coating can well cover the porous layer substrate, and the electrochemical performance and the durability of the porous layer are effectively improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a typical construction diagram of a conventional porous layer (plated layer).
Fig. 2 is a flowchart of a surface treatment method of the porous layer of example 1 of the present invention.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Porous layer nickel base material (porosity 56%, thickness 1000 μm, pore diameter 50 μm, area 3×3 cm), porous layer titanium base material (porosity 56%, thickness 1000 μm, pore diameter 50 μm, area 3×3 cm)
The invention is described in further detail below in connection with specific examples which are not to be construed as limiting the scope of the invention as claimed.
Example 1
The embodiment provides a porous layer treatment method for anion-cation exchange membrane electrolyzed water, which comprises the following steps:
(1) Pretreatment: ultrasonic soaking the porous layer nickel substrate in 500mL of acetone for 15 minutes to remove dust and greasy dirt on the nickel surface, and then placing the treated porous layer nickel substrate in deionized water for vibration cleaning for 8 minutes to obtain a pretreated porous layer nickel substrate;
(2) Soaking: soaking the pretreated porous layer nickel substrate in 500mL of 10% ammonia water for 30 min, and then vibrating and cleaning in 500mL of 10% hydrogen peroxide for 8 min to remove residual ammonia water on the surface; then vibrating and cleaning in deionized water for 10 minutes to obtain a cleaned porous layer nickel substrate;
(3) Surface hydrotreating: placing the cleaned porous layer nickel substrate in 500mL of concentrated sulfuric acid with the concentration of 98wt%, connecting the cleaned porous layer nickel substrate and a platinum electrode to the positive electrode and the negative electrode of a potentiostat, and carrying out surface hydrogenation treatment on the porous layer nickel substrate in a potentiostat mode, wherein the potential is set to be-0.25V, and the surface hydrogenation treatment time is 20 minutes; vibrating and cleaning the hydrotreated porous layer nickel substrate in deionized water for 8 minutes, drying and weighing;
(4) Alloy coating: plating a metal Nb layer on the surface of the nickel substrate with the surface subjected to the hydrogenation treatment by direct current magnetron sputtering, adjusting the pressure to 3Pa, and weighing the sputtering time to 5 minutes; and then performing direct-current magnetron sputtering on a metal Ir layer on the surface of the metal Nb layer, regulating the pressure to 3Pa, sputtering for 2 minutes, weighing and packaging to obtain the porous layer.
Experimental example 2
The embodiment provides a porous layer treatment method for anion-cation exchange membrane electrolyzed water, which comprises the following steps:
(1) Pretreatment: ultrasonic soaking the porous layer nickel substrate in 500mL of acetone for 20 minutes to remove dust and greasy dirt on the nickel surface, and then placing the treated porous layer nickel substrate in deionized water for vibration cleaning for 10 minutes to obtain a pretreated porous layer nickel substrate;
(2) Soaking: soaking the pretreated porous layer nickel substrate in 500mL of ammonia water with the mass concentration of 8% for 20 minutes, and then vibrating and cleaning in 500mL of hydrogen peroxide with the mass concentration of 10% for 10 minutes to remove the residual ammonia water on the surface; then vibrating and cleaning in deionized water for 10 minutes to obtain a cleaned porous layer nickel substrate;
(3) Surface hydrotreating: placing the cleaned porous layer nickel substrate in 500mL of concentrated sulfuric acid with the concentration of 98wt%, connecting the cleaned porous layer nickel substrate and a platinum electrode to the positive electrode and the negative electrode of a potentiostat, and carrying out surface hydrogenation treatment on the porous layer nickel substrate in a potentiostat mode, wherein the potential is set to be-0.25V, and the surface hydrogenation treatment time is 20 minutes; vibrating and cleaning the hydrotreated porous layer nickel substrate in deionized water for 8 minutes, drying and weighing;
(4) Alloy coating: plating a metal Nb layer on the surface of the nickel substrate with the surface subjected to the hydrogenation treatment by direct current magnetron sputtering, adjusting the pressure to 3Pa, and weighing the sputtering time to 5 minutes; and then performing direct-current magnetron sputtering on a metal Ir layer on the surface of the metal Nb layer, regulating the pressure to 3Pa, sputtering for 2 minutes, weighing and packaging to obtain the porous layer.
Comparative example 1
The embodiment provides a porous layer treatment method for anion-cation exchange membrane electrolyzed water, which comprises the following steps:
(1) Pretreatment: ultrasonic soaking the porous layer nickel substrate in 500mL of acetone for 15 minutes to remove dust and greasy dirt on the nickel surface, and then placing the treated porous layer nickel substrate in deionized water for vibration cleaning for 8 minutes to obtain a pretreated porous layer nickel substrate;
(2) Surface hydrotreating: placing the cleaned porous layer nickel substrate in 500mL of concentrated sulfuric acid with the concentration of 98wt%, connecting the cleaned porous layer nickel substrate and a platinum electrode to the positive electrode and the negative electrode of a potentiostat, and carrying out surface hydrogenation treatment on the porous layer nickel substrate in a potentiostat mode, wherein the potential is set to be-0.25V, and the surface hydrogenation treatment time is 20 minutes; vibrating and cleaning the hydrotreated porous layer nickel substrate in deionized water for 8 minutes, drying and weighing;
(3) Alloy coating: plating a metal Nb layer on the surface of the nickel substrate with the surface subjected to the hydrogenation treatment by direct current magnetron sputtering, adjusting the pressure to 3Pa, and weighing the sputtering time to 5 minutes; and then performing direct-current magnetron sputtering on a metal Ir layer on the surface of the metal Nb layer, regulating the pressure to 3Pa, sputtering for 2 minutes, weighing and packaging to obtain the porous layer.
Comparative example 2
The embodiment provides a porous layer treatment method for anion-cation exchange membrane electrolyzed water, which comprises the following steps:
(1) Pretreatment: ultrasonic soaking the porous layer nickel substrate in 500mL of acetone for 15 minutes to remove dust and greasy dirt on the nickel surface, and then placing the treated porous layer nickel substrate in deionized water for vibration cleaning for 8 minutes to obtain a pretreated porous layer nickel substrate;
(2) Soaking: soaking the pretreated porous layer nickel substrate in 500mL of deionized water for 30 minutes, and then vibrating and cleaning in 500mL of hydrogen peroxide with the mass concentration of 5% for 8 minutes to remove ammonia water remained on the surface; then vibrating and cleaning in deionized water for 10 minutes to obtain a cleaned porous layer nickel substrate;
(3) Surface hydrotreating: placing the cleaned porous layer nickel substrate in 500mL of concentrated sulfuric acid with the concentration of 98wt%, connecting the cleaned porous layer nickel substrate and a platinum electrode to the positive electrode and the negative electrode of a potentiostat, and carrying out surface hydrogenation treatment on the porous layer nickel substrate in a potentiostat mode, wherein the potential is set to be-0.25V, and the surface hydrogenation treatment time is 20 minutes; vibrating and cleaning the hydrotreated porous layer nickel substrate in deionized water for 8 minutes, drying and weighing;
(4) Alloy coating: plating a metal Nb layer on the surface of the nickel substrate with the surface subjected to the hydrogenation treatment by direct current magnetron sputtering, adjusting the pressure to 3Pa, and weighing the sputtering time to 5 minutes; and then performing direct-current magnetron sputtering on a metal Ir layer on the surface of the metal Nb layer, regulating the pressure to 3Pa, sputtering for 2 minutes, weighing and packaging to obtain the porous layer.
Comparative example 3
The embodiment provides a porous layer treatment method for anion-cation exchange membrane electrolyzed water, which comprises the following steps:
(1) Pretreatment: ultrasonic soaking the porous layer nickel substrate in 500mL of acetone for 15 minutes to remove dust and greasy dirt on the nickel surface, and then placing the treated porous layer nickel substrate in deionized water for vibration cleaning for 8 minutes to obtain a pretreated porous layer nickel substrate;
(2) Soaking: soaking the pretreated porous layer nickel substrate in 500mL of ammonia water with the mass concentration of 10% for 30 minutes, and then vibrating and cleaning in 500mL of hydrogen peroxide with the mass concentration of 5% for 8 minutes to remove the ammonia water remained on the surface; then vibrating and cleaning in deionized water for 10 minutes to obtain a cleaned porous layer nickel substrate;
(3) Surface hydrotreating: placing the cleaned porous layer nickel substrate in 500mL of dilute sulfuric acid with the concentration of 20wt%, connecting the cleaned porous layer nickel substrate and a platinum electrode to the positive electrode and the negative electrode of a potentiostat, and carrying out surface hydrogenation treatment on the porous layer nickel substrate in a potentiostat mode, wherein the potential is set to be-0.25V, and the surface hydrogenation treatment time is 20 minutes; vibrating and cleaning the hydrotreated porous layer nickel substrate in deionized water for 8 minutes, drying and weighing;
(4) Alloy coating: plating a metal Nb layer on the surface of the nickel substrate with the surface subjected to the hydrogenation treatment by direct current magnetron sputtering, adjusting the pressure to 3Pa, and weighing the sputtering time to 5 minutes; and then performing direct-current magnetron sputtering on a metal Ir layer on the surface of the metal Nb layer, regulating the pressure to 3Pa, sputtering for 2 minutes, weighing and packaging to obtain the porous layer.
The porous layers prepared in examples 1 and 2 and comparative examples 1 to 3 were subjected to electrochemical performance and durability tests, wherein the electrochemical performance test method was to load the prepared samples into an electrolysis apparatus and test the corresponding voltages at the current densities given in the table; the durability test method was to monitor the decay of the electrolytic voltage with a constant current density and an electrolysis apparatus temperature of 70℃and a pressure of 0.1MPa, and to use the voltage decay rate as a criterion for evaluating the durability, the test results are shown in Table 1.
TABLE 1
As can be seen from the data in table 1, the electrochemical performance and durability of the porous layer can be significantly enhanced by pre-treating the nickel/titanium porous layer, immersing, surface hydrotreating and coating the alloy plating layer. Electrochemical performance is expressed as electrolysis voltage under the same current density, and compared with a comparative example, the electrochemical performance is better when the voltage is small; the durability is expressed as a voltage increase range or a voltage decay rate before and after the test period, and the voltage decay rate is smaller and the durability is better in the examples compared with the comparative examples.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. A surface treatment method for a porous layer in anion-cation exchange membrane electrolyzed water, which is characterized by comprising the following steps:
1) Pretreating the porous layer substrate;
2) Soaking the pretreated porous layer substrate in ammonia water, and cleaning to obtain a cleaned porous layer substrate;
3) Placing the cleaned porous layer substrate in concentrated sulfuric acid to carry out surface hydrogenation treatment under the constant potential condition;
4) And (3) carrying out alloy coating on the surface of the porous layer substrate subjected to surface hydrogenation treatment to obtain the porous layer.
2. The surface treatment method according to claim 1, wherein the mass concentration of the aqueous ammonia in step 2) is 5 to 10%;
and/or, the soaking time is 20-30 minutes.
3. The surface treatment method according to claim 1, wherein the cleaning step in step 2) includes cleaning the soaked porous layer substrate with hydrogen peroxide and deionized water in order.
4. A surface treatment method according to claim 3, wherein the mass concentration of the hydrogen peroxide is 5-10%, the cleaning time with hydrogen peroxide is 5-10 minutes, and the cleaning time with deionized water is 5-10 minutes.
5. The surface treatment method according to claim 1, wherein in the step 3), the step of surface hydrogenation treatment comprises placing the washed porous layer substrate in concentrated sulfuric acid having a concentration of 98wt%, and then connecting the washed porous layer substrate and the platinum electrode to a positive electrode and a negative electrode of a potentiostat, respectively, and subjecting the porous layer substrate to surface hydrogenation treatment in a potentiostat mode;
preferably, the porous layer substrate is selected from a porous layer nickel substrate or a porous layer titanium substrate;
preferably, the porous layer nickel substrate is subjected to surface hydrogenation treatment, wherein the potential range is-0.25V to 0V, and the treatment time is 15-20 minutes;
preferably, the porous layer titanium substrate is subjected to surface hydrogenation treatment with a potential ranging from-1.63V to 0V for 15-20 minutes.
6. The surface treatment method according to claim 1, wherein in the step 4), the alloy plating layer coating step includes plating a metallic Nb layer on the surface of the surface-hydrotreated porous layer substrate, and then plating a metallic Ir layer on the surface of the metallic Nb layer;
the plating step is performed by a magnetron sputtering method, preferably by a direct current magnetron sputtering method;
the plating pressure is 3-5Pa, and the sputtering time is 2-5 minutes.
7. The surface treatment method according to claim 6, further comprising the step of cleaning and drying the surface-hydrotreated porous layer substrate before the alloy plating layer is applied to the surface of the surface-hydrotreated porous layer substrate.
8. The surface treatment method according to claim 1, wherein when the porous layer substrate is a porous layer titanium substrate, the pretreatment of step 1) includes a step of immersing the porous layer substrate in an acid solution and then washing with water;
preferably, the acid solution is hydrochloric acid solution, the concentration of the hydrochloric acid solution is 0.1M, the soaking time is 10-20 minutes, and the water cleaning time is 5-10 minutes;
preferably, when the porous layer substrate is a porous layer nickel substrate, the pretreatment of step 1) includes a step of firstly ultrasonic-soaking the porous layer substrate in an organic solvent and then washing with water;
preferably, the organic solvent is acetone, the soaking time is 10-20 minutes, and the water cleaning time is 5-10 minutes.
9. An electrolyzed water reaction apparatus comprising a porous layer obtained by the surface treatment method according to any one of claims 1 to 8.
10. Use of the porous layer obtained by the surface treatment method according to any one of claims 1 to 8 in electrolysis of water.
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