CN117987860A - PEM (PEM) electrolytic cell diffusion layer based on drawn fibers and preparation method thereof - Google Patents
PEM (PEM) electrolytic cell diffusion layer based on drawn fibers and preparation method thereof Download PDFInfo
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- 238000009792 diffusion process Methods 0.000 title claims abstract description 70
- 229920006240 drawn fiber Polymers 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 132
- 239000000835 fiber Substances 0.000 claims abstract description 131
- 239000010936 titanium Substances 0.000 claims abstract description 90
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 90
- 238000005245 sintering Methods 0.000 claims abstract description 51
- 238000005520 cutting process Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims description 43
- 238000007747 plating Methods 0.000 claims description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 238000005554 pickling Methods 0.000 claims description 29
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 27
- 229910017604 nitric acid Inorganic materials 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 25
- 229910052802 copper Inorganic materials 0.000 claims description 25
- 239000002131 composite material Substances 0.000 claims description 24
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 20
- 238000000137 annealing Methods 0.000 claims description 19
- 238000013329 compounding Methods 0.000 claims description 17
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 9
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 8
- 239000011148 porous material Substances 0.000 abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001257 hydrogen Substances 0.000 abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 11
- 238000005868 electrolysis reaction Methods 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 10
- 238000002791 soaking Methods 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 229910052574 oxide ceramic Inorganic materials 0.000 description 7
- 239000011224 oxide ceramic Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 238000005192 partition Methods 0.000 description 6
- 230000003213 activating effect Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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Abstract
The invention provides a PEM (proton exchange membrane) electrolytic tank diffusion layer based on drawn fibers and a preparation method thereof, belonging to the technical field of hydrogen production by water electrolysis. The preparation method comprises the following steps: and (3) carrying out non-woven paving on the drawn titanium fibers, sintering, and then flattening and cutting to obtain the titanium porous fiber diffusion layer product. The invention adopts drawn titanium fiber to replace common cut titanium fiber, greatly improves the uniformity of the fiber sintering diffusion layer and improves the product quality. More importantly, the drawn fiber can produce titanium fiber with finer wire diameter, so that the pore distribution of the diffusion layer is more uniform and finer, and the diffusion layer structure improves the catalytic efficiency of the PEM electrolytic cell catalyst, so that the electrolytic efficiency is improved.
Description
Technical Field
The invention belongs to the technical field of hydrogen production by water electrolysis, and particularly relates to a PEM (PEM) electrolytic tank diffusion layer based on drawn fibers and a preparation method thereof.
Background
Hydrogen is a clean and efficient green energy source, and as hydrogen fuel cells, hydrogen energy storage, hydrogen metallurgy and other hydrogen energy industry applications are mature, the demand for green hydrogen is continuously increasing. The proton exchange membrane electrolyzed water (PEMWE) hydrogen production technology is regarded as the most promising green hydrogen production technology due to the advantages of high adaptability to renewable energy sources such as wind, photoelectricity and the like, high efficiency, no pollution and the like in the hydrogen production process. The diffusion layer is a critical component of PEM electrolyzed water tanks that has the function of conducting electricity, transporting water/gas, mechanically supporting a proton exchange membrane. Because PEM anodes have high corrosion potentials and a strongly acidic environment, which place higher demands on the corrosion resistance and chemical stability of the anode diffusion layer material, titanium with high corrosion resistance is currently the main preparation material for anode diffusion layers.
There are two main types of titanium diffusion layer materials used in the market: titanium powder sintered porous material and titanium fiber sintered porous material. Compared with the titanium powder sintered porous material, the titanium fiber sintered porous material can realize thinner thickness and higher porosity, and simultaneously maintain high bending strength and flexibility of the diffusion layer. This makes it easier to achieve higher current densities and higher electrolysis efficiencies for the titanium fiber sintered porous material, while also maintaining better overall mechanical properties in the high pressure PEM electrolyzer.
However, the conventional titanium fiber sintered porous diffusion layer mainly adopts cut titanium fiber, and has the following problems:
1. The uniformity of the wire diameter of the cutting fiber is poor, so that the pore diameter of the porous diffusion layer of the cutting fiber is unevenly distributed, and partial pores with far-exceeding average pore diameter can exist. Therefore, the proton membrane can be sunk into the pores to form large bubbles under the air pressure in the use process, and the proton membrane can be broken to cause safety accidents when serious;
2. The cutting fiber is irregularly shaped. Some fibers have sharp corners where stress concentrations and charge concentrations can form, thereby reducing the useful life of the film.
3. The cutting fiber has a relatively large wire diameter. The wire diameter of the titanium fiber prepared by the current cutting method is more than 20 mu m, so that the average pore of the cut fiber diffusion layer is larger.
Therefore, there is a need to develop a more uniform and efficient fiber sintered porous diffusion layer.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a PEM electrolytic cell diffusion layer based on drawn fibers and a preparation method thereof, wherein the prepared diffusion layer has high uniformity, smoother microscopic surface and smaller pore diameter under high porosity.
The invention is realized by the following technical scheme:
In a first aspect of the invention, a method for preparing a PEM electrolytic cell diffusion layer based on drawn fibers is provided, wherein drawn titanium fibers are subjected to non-woven laying, sintering, leveling and cutting to obtain a titanium porous fiber diffusion layer product.
Further, the method comprises the steps of,
The gram weight of the nonwoven is controlled to be 400-1000 g/m 2 in the process of laying.
Further, the method comprises the steps of,
The sintering temperature is 900-1300 ℃ and the time is 4-8 h in the sintering process, and the vacuum degree is within 2X 10 -2 Pa.
Further, the method comprises the steps of,
The preparation method of the drawn titanium fiber comprises the following steps:
Step 1: pretreating pure titanium wires to obtain copper-plated titanium wires;
Step 2: bundling and compounding the copper-plated titanium wires;
step 3: carrying out bundling stretching and annealing on the bundled and compounded composite until the fiber size is stretched to the required size;
step 4: and (3) sequentially carrying out acid washing, ultrasonic cleaning and drying on the fiber composite body subjected to cluster drawing to obtain drawn titanium fibers.
Further, the method comprises the steps of,
In the step 1, the pure titanium wire is pretreated to obtain copper-plated titanium wire, and the specific operation comprises the following steps:
and sequentially carrying out ultrasonic cleaning, acid washing and surface copper plating on the pure titanium wire to obtain the copper-plated titanium wire.
Further, the method comprises the steps of,
The pickling is to soak the pure titanium wire after ultrasonic cleaning in the first pickling solution for 20-60 s, remove the oxide layer on the surface and activate;
the first pickling solution is a mixture of nitric acid and hydrofluoric acid, wherein the volume concentration of the nitric acid in the mixture is 15-30%, and the volume concentration of the hydrofluoric acid is 2-10%.
Further, the method comprises the steps of,
The surface copper plating is to soak the pickled pure titanium wire in a plating solution until the thickness of the plating layer is 0.2-1 mu m, wherein the plating solution is anhydrous copper sulfate with the concentration of 140 g/L.
Further, the method comprises the steps of,
And 3, carrying out cluster stretching and annealing on the composite body after cluster compounding until the composite body is stretched to the required fiber size, wherein the specific operation comprises the following steps:
And (3) stretching the composite body after bundling and compounding for 3-7 times, and then annealing, wherein the single-pass stretching rate is 30% -60%, the annealing temperature is 500-800 ℃ and the annealing time is 5-40 min, and repeating the process until the fiber diameter is 12-28 mu m.
Further, the method comprises the steps of,
In the step 4, the fiber complex is put into a second pickling solution to be soaked for 2 to 8 hours, and the copper coating on the surface of the fiber is washed off;
the second pickling solution is a mixture of nitric acid and hydrochloric acid, wherein the concentration of the nitric acid is 10-50 ml/L, and the concentration of the hydrochloric acid is 40-100 ml/L.
In a second aspect of the present invention, there is provided a drawn fiber based PEM electrolyser diffusion layer prepared by the drawn fiber based PEM electrolyser diffusion layer preparation method described above.
Compared with the prior art, the invention has the beneficial effects that:
The invention adopts drawn titanium fiber to replace common cut titanium fiber, greatly improves the uniformity of the fiber sintering diffusion layer and improves the product quality. More importantly, the drawn fiber can produce titanium fiber with finer wire diameter, so that the pore distribution of the diffusion layer is more uniform and finer, and the diffusion layer structure improves the catalytic efficiency of the PEM electrolytic cell catalyst, so that the electrolytic efficiency is improved.
Drawings
In order to more clearly illustrate the innovations and advantages of embodiments or prior art solutions of the present application, a brief description is provided below using the accompanying drawings.
FIG. 1 is a scanning electron micrograph of drawn titanium fibers prepared in example 1;
FIG. 2 is a scanning electron micrograph of drawn titanium fibers prepared in example 2;
FIG. 3 is a scanning electron micrograph of drawn titanium fibers prepared in example 3;
FIG. 4 is a scanning electron micrograph of cut titanium fibers used in comparative example 1;
FIG. 5 is a scanning electron micrograph of the diffusion layer product prepared in example 1;
FIG. 6 is a scanning electron micrograph of the diffusion layer product prepared in example 2;
FIG. 7 is a scanning electron micrograph of the diffusion layer product prepared in example 3;
FIG. 8 is a scanning electron micrograph of the diffusion layer product prepared in comparative example 1;
FIG. 9 is a cross-sectional metallographic photograph of a diffusion layer product prepared in example 1;
FIG. 10 is a cross-sectional metallographic photograph of a diffusion layer product prepared in comparative example 1;
FIG. 11 is an electrovoltammetric characteristic curve of the diffusion layer product obtained in example 1 and comparative example 1.
Detailed Description
The invention is described in further detail below with reference to the attached drawing figures:
The invention provides a method for preparing a diffusion layer of a PEM (PEM) electrolytic cell based on drawn fibers, which mainly comprises the following steps:
Step 1: pretreating pure titanium wires to obtain copper-plated titanium wires;
The specific operation comprises the following steps:
sequentially carrying out ultrasonic cleaning, acid washing and surface copper plating on the pure titanium wire to obtain copper-plated titanium wire;
The pickling is to soak the pure titanium wire after ultrasonic cleaning in a first pickling solution for 20-60 s, remove an oxide layer on the surface and activate, wherein the first pickling solution is a mixture of nitric acid and hydrofluoric acid, the volume concentration of the nitric acid in the mixture is 15-30%, and the volume concentration of the hydrofluoric acid is 2-10%;
The surface copper plating is to soak the pickled pure titanium wire in a plating solution until the thickness of the plating layer is 0.2-1 mu m, wherein the plating solution is anhydrous copper sulfate with the concentration of 140 g/L. The purpose of the surface copper plating is here to prevent sticking between the fibers due to mechanical action during drawing.
Step 2: bundling and compounding the copper-plated titanium wires;
In order to improve the efficiency, 100-1000 cores of copper-plated titanium wires are selected to be clustered and compounded.
Step 3: carrying out bundling stretching and annealing on the bundled and compounded composite until the fiber size is stretched to the required size;
The specific operation comprises the following steps:
And (3) stretching the composite body after bundling and compounding for 3-7 times, and then annealing, wherein the single-pass stretching rate is 30% -60%, the annealing temperature is 500-800 ℃ and the annealing time is 5-40 min, and repeating the process until the fiber diameter is 12-28 mu m.
In the invention, the titanium fiber is drawn to the wire diameter of 12-28 mu m, which is favorable for reducing the average pore diameter of the diffusion layer and obtaining a smoother diffusion layer surface.
Step 4: sequentially carrying out acid washing, ultrasonic cleaning and drying on the fiber composite body subjected to cluster drawing to obtain drawn titanium fibers;
The acid washing is to soak the fiber composite in the second acid washing liquid for 2-8 hr to wash off copper coating on the fiber surface, and the second acid washing liquid is mixture of nitric acid and hydrochloric acid with nitric acid concentration of 10-50 ml/L and hydrochloric acid concentration of 40-100 ml/L.
Step 5: carrying out non-woven paving after ultrasonic cleaning and drying on the drawn titanium fiber obtained in the step 4, wherein the paving gram weight is controlled to be 400-1000 g/m 2;
the weight of the spreading gram is controlled to be 400-1000 g/m 2 in the non-woven spreading process, so that the porosity of the finally prepared diffusion layer is 50% -80%, the diffusion layer has more excellent substance transmission efficiency, water can flow to the anode film conveniently for reaction, and generated oxygen can be transmitted timely.
Step 6: sintering the fiber felt after the nonwoven laid net in the step 5;
The specific operation comprises the following steps:
Because the fiber mat after being laid into a net is bigger, the fiber mat is cut into a certain size and then stacked one by one to be placed in a vacuum sintering furnace for sintering, wherein a partition board is needed to be separated between two adjacent layers, so that different layers are prevented from being sintered together, and the sintering effect is influenced;
The separator may be a molybdenum plate surface-sprayed with high-temperature oxide ceramic powder, wherein the oxide ceramic powder is alumina (Al 2O 3), zirconia (ZrO), or the like.
The sintering temperature is 900-1300 ℃ and the time is 4-8 h in the sintering process, and the vacuum degree is within 2X 10 -2 Pa. The reasonable sintering process ensures that the titanium diffusion layer has good surface quality, low resistance and good mechanical property.
And 7, flattening and cutting the sintered titanium fiber felt to obtain a titanium porous fiber diffusion layer, namely the PEM electrolytic cell diffusion layer.
The specific operation comprises the following steps:
and (3) flattening the titanium fiber felt sintered in the step (6) on a high-precision numerical control flattening machine, and cutting the flattened titanium fiber into titanium porous fiber diffusion layer products with different shapes to obtain the PEM electrolytic cell diffusion layer.
The invention adopts drawn titanium fiber to replace common cut titanium fiber, greatly improves the uniformity of the fiber sintering diffusion layer and improves the product quality. More importantly, the drawn fiber can produce titanium fiber with a smaller wire diameter, and the diffusion layer structure improves the catalytic efficiency of the PEM electrolytic cell catalyst, so that the electrolytic efficiency is improved.
Example 1
Step 1: firstly, ultrasonically cleaning 0.5mm TA1 titanium wire, then soaking the titanium wire in a first pickling solution consisting of 15% nitric acid and 2% hydrofluoric acid for 20s, removing an oxide layer on the surface of the titanium wire, activating the titanium wire, and then soaking the pickled pure titanium wire in a plating solution until the thickness of the plating layer is 1 mu m, wherein the plating solution is anhydrous copper sulfate with the concentration of 140 g/L. The purpose of the surface copper plating is here to prevent sticking between the fibers due to mechanical action during drawing.
Step 2: and (3) cleaning and drying the copper-plated titanium wires obtained in the step (1), and then carrying out cluster compounding on the 100-core copper-plated titanium wires, and packaging the cluster into a copper pipe.
Step 3: the composite body after cluster compounding is stretched for 3 times and then annealed, wherein the single-pass stretching rate is 60 percent, the annealing temperature is 800 ℃ and the time is 5 minutes, and the process is repeated until the fiber diameter is 28 mu m.
Step 4: and (3) immersing the fiber composite body in a second pickling solution for 8 hours, washing off the copper plating layer on the surface of the fiber, wherein the second pickling solution is a mixture of nitric acid and hydrochloric acid, the concentration of the nitric acid is 50ml/L, the concentration of the hydrochloric acid is 100ml/L, and then carrying out ultrasonic cleaning and drying to obtain the drawn titanium fiber.
Step 5: and (3) carrying out non-woven paving on the drawn titanium fiber obtained in the step (4) on a felt paving machine, wherein the paving gram weight is controlled at 400g/m 2.
Step 6: cutting the fiber mats formed by the non-woven paving in the step 5 into a certain size, stacking one by one, and placing the fiber mats in a vacuum sintering furnace for sintering, wherein a partition board is needed between two adjacent layers to separate, so that different layers are prevented from being burned together, and the sintering effect is prevented from being influenced; the separator may be a molybdenum plate with a surface coated with a high temperature oxide ceramic powder of alumina (Al 2O 3), zirconia (ZrO), or the like;
The sintering temperature is 900 ℃, the time is 8 hours, and the vacuum degree is within 2X 10 -2 Pa in the sintering process.
Step 7: and flattening the fiber felt after vacuum sintering to 0.4mm, detecting the thickness uniformity of the fiber felt, and ensuring the thickness deviation to be within +/-5%.
Step 8: the titanium diffusion layer was cut to specification size and shape using a full automatic cutting machine.
Example 2
Step 1: firstly, ultrasonically cleaning 0.5mm TA1 titanium wire, then soaking the titanium wire in a first pickling solution consisting of 30% nitric acid and 10% hydrofluoric acid for 30s, removing an oxide layer on the surface of the titanium wire, activating the titanium wire, and then soaking the pickled pure titanium wire in a plating solution until the thickness of the plating layer is 0.2 mu m, wherein the plating solution is anhydrous copper sulfate with the concentration of 140 g/L. The purpose of the surface copper plating is here to prevent sticking between the fibers due to mechanical action during drawing.
Step 2: and (3) cleaning and drying the copper-plated titanium wires obtained in the step (1), and then bundling and compounding the 500-core copper-plated titanium wires into a copper pipe.
Step 3: the composite body after cluster compounding is stretched for 7 times and then annealed, wherein the single-pass stretching rate is 30 percent, the annealing temperature is 500 ℃ and the time is 40 minutes, and the process is repeated until the fiber diameter is 16 mu m.
Step 4: and (3) immersing the fiber composite body in a second pickling solution for 2 hours, washing off the copper plating layer on the surface of the fiber, wherein the second pickling solution is a mixture of nitric acid and hydrochloric acid, the concentration of the nitric acid is 10ml/L, the concentration of the hydrochloric acid is 40ml/L, and then carrying out ultrasonic cleaning and drying to obtain the drawn titanium fiber.
Step 5: and (3) carrying out non-woven paving on the drawn titanium fiber obtained in the step (4) on a felt paving machine, wherein the paving gram weight is controlled at 1000g/m 2.
Step 6: cutting the fiber mats formed by the non-woven paving in the step 5 into a certain size, stacking one by one, and placing the fiber mats in a vacuum sintering furnace for sintering, wherein a partition board is needed between two adjacent layers to separate, so that different layers are prevented from being burned together, and the sintering effect is prevented from being influenced; the separator may be a molybdenum plate with a surface coated with a high temperature oxide ceramic powder of alumina (Al 2O 3), zirconia (ZrO), or the like;
The sintering temperature is 1300 ℃, the time is 4 hours, and the vacuum degree is within 2X 10 -2 Pa in the sintering process.
Step 7: and flattening the fiber felt after vacuum sintering to 0.4mm, detecting the thickness uniformity of the fiber felt, and ensuring the thickness deviation to be within +/-5%.
Step 8: the titanium diffusion layer was cut to specification size and shape using a full automatic cutting machine.
Example 3
Step 1: firstly, ultrasonically cleaning 0.5mm TA1 titanium wire, then soaking the titanium wire in a first pickling solution consisting of nitric acid with the volume concentration of 20% and hydrofluoric acid with the volume concentration of 5% for 30 seconds, removing an oxide layer on the surface of the titanium wire, activating the titanium wire, and then soaking the pickled pure titanium wire in a plating solution until the thickness of the plating layer is 0.5 mu m, wherein the plating solution is anhydrous copper sulfate with the concentration of 140 g/L. The purpose of the surface copper plating is here to prevent sticking between the fibers due to mechanical action during drawing.
Step 2: and (3) cleaning and drying the copper-plated titanium wires obtained in the step (1), and then bundling and compounding 1000 cores of copper-plated titanium wires and filling the copper-plated titanium wires into a copper pipe.
Step 3: the composite body after bundling and compounding is stretched for 4 times and then annealed, wherein the single-pass stretching rate is 20 percent, the annealing temperature is 700 ℃ and the time is 30 minutes, and the process is repeated until the fiber diameter is 12 mu m.
Step 4: and (3) immersing the fiber composite body in a second pickling solution for 4 hours, washing off the copper plating layer on the surface of the fiber, wherein the second pickling solution is a mixture of nitric acid and hydrochloric acid, the concentration of the nitric acid is 25ml/L, the concentration of the hydrochloric acid is 60ml/L, and then carrying out ultrasonic cleaning and drying to obtain the drawn titanium fiber.
Step 5: and (3) carrying out non-woven paving on the drawn titanium fiber obtained in the step (4) on a felt paving machine, wherein the paving gram weight is controlled at 600g/m 2.
Step 6: cutting the fiber mats formed by the non-woven paving in the step 5 into a certain size, stacking one by one, and placing the fiber mats in a vacuum sintering furnace for sintering, wherein a partition board is needed between two adjacent layers to separate, so that different layers are prevented from being burned together, and the sintering effect is prevented from being influenced; the separator may be a molybdenum plate with a surface coated with a high temperature oxide ceramic powder of alumina (Al 2O 3), zirconia (ZrO), or the like;
The sintering temperature is 1000 ℃ and the time is 4 hours in the sintering process, and the vacuum degree is within 2 multiplied by 10 -2 Pa.
Step 7: and flattening the fiber felt after vacuum sintering to 0.4mm, detecting the thickness uniformity of the fiber felt, and ensuring the thickness deviation to be within +/-5%.
Step 8: the titanium diffusion layer was cut to specification size and shape using a full automatic cutting machine.
Example 4
Step 1: firstly, ultrasonically cleaning 0.5mm TA1 titanium wire, then, soaking the titanium wire in a first pickling solution consisting of 25% nitric acid and 6% hydrofluoric acid for 60 seconds, removing an oxide layer on the surface of the titanium wire, and activating the titanium wire, and then, soaking the pickled pure titanium wire in a plating solution until the thickness of the plating layer is 0.7 mu m, wherein the plating solution is anhydrous copper sulfate with the concentration of 140 g/L. The purpose of the surface copper plating is here to prevent sticking between the fibers due to mechanical action during drawing.
Step 2: and (3) cleaning and drying the copper-plated titanium wires obtained in the step (1), and then bundling and compounding 1000 cores of copper-plated titanium wires and filling the copper-plated titanium wires into a copper pipe.
Step 3: the composite body after bundling and compounding is stretched for 5 times and then annealed, wherein the single-pass stretching rate is 40%, the annealing temperature is 600 ℃, the time is 20min, and the process is repeated until the fiber diameter is 20 mu m.
Step 4: and (3) immersing the fiber composite body in a second pickling solution for 6 hours, washing off the copper plating layer on the surface of the fiber, wherein the second pickling solution is a mixture of nitric acid and hydrochloric acid, the concentration of the nitric acid is 20ml/L, the concentration of the hydrochloric acid is 80ml/L, and then carrying out ultrasonic cleaning and drying to obtain the drawn titanium fiber.
Step 5: and (3) carrying out non-woven paving on the drawn titanium fiber obtained in the step (4) on a felt paving machine, wherein the paving gram weight is controlled at 800g/m 2.
Step 6: cutting the fiber mats formed by the non-woven paving in the step 5 into a certain size, stacking one by one, and placing the fiber mats in a vacuum sintering furnace for sintering, wherein a partition board is needed between two adjacent layers to separate, so that different layers are prevented from being burned together, and the sintering effect is prevented from being influenced; the separator may be a molybdenum plate with a surface coated with a high temperature oxide ceramic powder of alumina (Al 2O 3), zirconia (ZrO), or the like;
The sintering temperature is 1200 ℃, the time is 5 hours, and the vacuum degree is within 2X 10 -2 Pa in the sintering process.
Step 7: and flattening the fiber felt after vacuum sintering to 0.4mm, detecting the thickness uniformity of the fiber felt, and ensuring the thickness deviation to be within +/-5%.
Step 8: the titanium diffusion layer was cut to specification size and shape using a full automatic cutting machine.
Example 5
Step 1: firstly, ultrasonically cleaning 0.5mm TA1 titanium wire, then soaking the titanium wire in a first pickling solution consisting of nitric acid with the volume concentration of 20% and hydrofluoric acid with the volume concentration of 8% for 50s, removing an oxide layer on the surface of the titanium wire, activating the titanium wire, and then soaking the pickled pure titanium wire in a plating solution until the thickness of the plating layer is 0.9 mu m, wherein the plating solution is anhydrous copper sulfate with the concentration of 140 g/L. The purpose of the surface copper plating is here to prevent sticking between the fibers due to mechanical action during drawing.
Step 2: and (3) cleaning and drying the copper-plated titanium wires obtained in the step (1), and then bundling and compounding 1000 cores of copper-plated titanium wires and filling the copper-plated titanium wires into a copper pipe.
Step 3: the composite body after bundling and compounding is stretched for 4 times and then annealed, wherein the single-pass stretching rate is 50%, the annealing temperature is 800 ℃, the time is 10min, and the process is repeated until the fiber diameter is 25 mu m.
Step 4: and (3) immersing the fiber composite body in a second pickling solution for 7 hours, washing off the copper plating layer on the surface of the fiber, wherein the second pickling solution is a mixture of nitric acid and hydrochloric acid, the concentration of the nitric acid is 35ml/L, the concentration of the hydrochloric acid is 90ml/L, and then carrying out ultrasonic cleaning and drying to obtain the drawn titanium fiber.
Step 5: and (3) carrying out non-woven paving on the drawn titanium fiber obtained in the step (4) on a felt paving machine, wherein the paving gram weight is controlled at 500g/m 2.
Step 6: cutting the fiber mats formed by the non-woven paving in the step 5 into a certain size, stacking one by one, and placing the fiber mats in a vacuum sintering furnace for sintering, wherein a partition board is needed between two adjacent layers to separate, so that different layers are prevented from being burned together, and the sintering effect is prevented from being influenced; the separator may be a molybdenum plate with a surface coated with a high temperature oxide ceramic powder of alumina (Al 2O 3), zirconia (ZrO), or the like;
the sintering temperature is 1100 ℃, the time is 6 hours, and the vacuum degree is within 2X 10 -2 Pa in the sintering process.
Step 7: and flattening the fiber felt after vacuum sintering to 0.4mm, detecting the thickness uniformity of the fiber felt, and ensuring the thickness deviation to be within +/-5%.
Step 8: the titanium diffusion layer was cut to specification size and shape using a full automatic cutting machine.
Comparative example 1
Step 1, dispersing cut titanium fibers with the average fiber diameter of 28 mu m obtained by a vibration cutting method
Step 2: and (5) carrying out non-woven paving on the dispersed cut titanium fibers by using a felt paving machine. The gram weight of the paving is controlled at 400g/m 2.
Step 3: separating the multi-layer fiber web felt blank obtained in the step 5 by using a separation layer, performing high-temperature diffusion sintering in a vacuum sintering furnace, controlling the vacuum degree within 2X 10 -2 Pa, and controlling the sintering temperature at 900 ℃ for 8 hours.
Step 4: and flattening the fiber felt after vacuum sintering to 0.4mm, detecting the thickness uniformity of the fiber felt, and ensuring the thickness deviation to be within +/-5%.
Step 5: the titanium diffusion layer was cut to specification size and shape using a full automatic cutting machine.
The titanium fibers used in examples 1 to 3 and comparative example 1 were observed in a scanning electron microscope as shown in fig. 1 to 4. The comparative results show that the drawn titanium fibers obtained in examples 1-3 are more concentrated and uniform in wire diameter distribution and have an average wire diameter smaller than the cut titanium fibers used in the comparative examples.
The titanium diffusion layer products obtained in examples 1 to 3 and comparative example 1 were observed in a scanning electron microscope as shown in fig. 5 to 8. The comparison results show that the diffusion layer products obtained in examples 1-3 have more uniform pore size distribution and finer pore sizes.
The diffusion layer products obtained in example 1 and comparative example 1 were subjected to cross-sectional metallographic examination along the cross section, and the microstructure morphology of the contact surface of the fiber on the diffusion layer and the PME film was observed. As shown in fig. 9 and 10, the drawn titanium fiber has a relatively smooth cross section, while the cut titanium fiber has sharp corners in cross section, as shown by the comparison.
The diffusion layer products obtained in example 1 and comparative example 1 were tested for their electrolytic efficiency in PEM electrolysers. The lower the electrolysis voltage, the higher the electrolysis efficiency under the same current density conditions, the electrolytic current and the electrolysis voltage are obtained, as shown in fig. 11. The comparison result shows that the diffusion layer prepared by drawing the titanium fiber has higher electrolytic efficiency.
The foregoing technical solution is only one embodiment of the present invention, and various modifications and variations can be easily made by those skilled in the art based on the principles disclosed in the present invention, and are not limited to the technical solutions described in the foregoing specific examples of the present invention, therefore, the foregoing description is only preferred and not in any limiting sense.
Claims (10)
1. A method for preparing a PEM electrolytic cell diffusion layer based on drawn fibers is characterized in that drawn titanium fibers are subjected to non-woven laying and then sintering, and then flattening and cutting are carried out to obtain a titanium porous fiber diffusion layer product.
2. The method of preparing a drawn fiber based PEM electrolyser diffusion layer of claim 1 wherein the lay-up grammage is controlled between 400 and 1000g/m 2 during the nonwoven lay-up process.
3. The method for preparing a diffusion layer of a drawn fiber-based PEM electrolyzer of claim 1 wherein the sintering temperature during sintering is 900-1300 ℃ for 4-8 hours and the vacuum is within 2 x10 -2 Pa.
4. The method of preparing a drawn fiber-based PEM electrolyser diffusion layer of claim 1 wherein said method of preparing drawn titanium fibers is as follows:
Step 1: pretreating pure titanium wires to obtain copper-plated titanium wires;
Step 2: bundling and compounding the copper-plated titanium wires;
step 3: carrying out bundling stretching and annealing on the bundled and compounded composite until the fiber size is stretched to the required size;
step 4: and (3) sequentially carrying out acid washing, ultrasonic cleaning and drying on the fiber composite body subjected to cluster drawing to obtain drawn titanium fibers.
5. The method for preparing a diffusion layer of a drawn fiber-based PEM electrolytic cell according to claim 4, wherein the step 1 of pretreating pure titanium wire to obtain copper-plated titanium wire comprises the following specific operations:
and sequentially carrying out ultrasonic cleaning, acid washing and surface copper plating on the pure titanium wire to obtain the copper-plated titanium wire.
6. The method for preparing a diffusion layer of a drawn fiber-based PEM electrolytic cell according to claim 5, wherein the pickling is to soak pure titanium wires after ultrasonic cleaning in a first pickling solution for 20-60 s, remove an oxide layer on the surface and activate the titanium wires;
the first pickling solution is a mixture of nitric acid and hydrofluoric acid, wherein the volume concentration of the nitric acid in the mixture is 15-30%, and the volume concentration of the hydrofluoric acid is 2-10%.
7. The method for preparing a diffusion layer of a drawn fiber-based PEM electrolytic cell according to claim 5, wherein the surface copper plating is carried out by immersing the pickled pure titanium wire in a plating solution until the thickness of the plating layer is 0.2-1 μm, wherein the plating solution is 140g/L anhydrous copper sulfate.
8. The method of preparing a drawn fiber-based PEM electrolyser diffusion layer of claim 4 wherein step 3 comprises bundle stretching and annealing the bundle compounded composite until it is stretched to the desired fiber size, the specific operations comprising:
And (3) stretching the composite body after bundling and compounding for 3-7 times, and then annealing, wherein the single-pass stretching rate is 30% -60%, the annealing temperature is 500-800 ℃ and the annealing time is 5-40 min, and repeating the process until the fiber diameter is 12-28 mu m.
9. The method for preparing a diffusion layer of a drawn-fiber-based PEM electrolytic cell according to claim 4, wherein the pickling in the step 4 is to soak the fiber composite in a second pickling solution for 2-8 hours to wash out copper plating on the surface of the fiber;
the second pickling solution is a mixture of nitric acid and hydrochloric acid, wherein the concentration of the nitric acid is 10-50 ml/L, and the concentration of the hydrochloric acid is 40-100 ml/L.
10. A drawn fiber-based PEM electrolyser diffusion layer prepared by the method of preparing a drawn fiber-based PEM electrolyser diffusion layer as claimed in any of claims 1-9.
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