High-performance high-temperature proton exchange membrane fuel cell membrane electrode, preparation process and device

Abstract

The present invention discloses a high-performance high-temperature proton exchange membrane fuel cell membrane electrode, the membrane electrode comprising a proton exchange membrane, a catalyst layer and a gas diffusion layer; the present invention also discloses a high-performance high-temperature proton exchange membrane fuel cell membrane electrode preparation device, comprising a base, an L-shaped plate fixedly connected to the base, two electric push rods installed on the upper end of the L-shaped plate, the output ends of the two electric push rods are fixedly connected to a moving plate, and an upper hot pressing assembly is movably installed on the moving plate. Compared with the prior art, the present invention performs solvent annealing treatment on the coating after the slurry coating is dried, and adopts this method to improve the uniformity of the coating, reduce the internal resistance of the coating, and improve the battery performance.

Description

Technical Field

[0001] The present invention relates to the field of membrane electrode technology, and in particular to a high-performance, high-temperature proton exchange membrane fuel cell membrane electrode, a preparation process and a device. Background Art

[0002] As the core component of fuel cells, the preparation process of membrane electrode directly affects the performance, cost and life of the entire battery stack.

[0003] Generally, we coat the catalyst slurry on the substrate, then dry it to obtain the ideal catalyst layer, and then assemble it according to the coating process to obtain the membrane electrode. However, at present, the resistance of the membrane electrode used in high-temperature proton exchange membrane fuel cells is relatively large, which seriously affects the battery performance.

[0004] Therefore, there is an urgent need for a membrane electrode preparation process that can avoid or reduce the above-mentioned problems. Summary of the invention

[0005] The purpose of the present invention is to solve the above technical problems and to propose a high-performance, high-temperature proton exchange membrane fuel cell membrane electrode, a preparation process and a device.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] A high-performance, high-temperature proton exchange membrane fuel cell membrane electrode comprises a proton exchange membrane, a catalyst layer and a gas diffusion layer.

[0008] Preferably, the preparation process of the high-performance high-temperature proton exchange membrane fuel cell membrane electrode comprises the following steps:

[0009] S1, the catalytic layer is prepared by coating a uniform mixture of a catalyst, ultrapure water, a solvent and a resin on a substrate, and the substrate is one of a proton exchange membrane and a gas diffusion layer;

[0010] S2, drying the catalyst layer and the substrate;

[0011] S3, performing solvent annealing treatment on the catalyst layer and the substrate;

[0012] S4, hot pressing the gas diffusion layer, the catalyst layer, the proton exchange membrane, the catalyst layer, and the gas diffusion layer in the above-mentioned order to obtain a membrane electrode.

[0013] Preferably, the preparation process of the high-performance high-temperature proton exchange membrane fuel cell membrane electrode comprises the following steps:

[0014] S1, the catalytic layer is prepared by coating a uniform mixture of a catalyst, ultrapure water, a solvent and a resin on a substrate, and the substrate is a transfer film;

[0015] S2, drying the catalytic layer and the transfer membrane;

[0016] S3, performing solvent annealing treatment on the catalyst layer and the transfer film;

[0017] S4, transferring the catalyst layer on the transfer membrane to the proton exchange membrane by hot pressing;

[0018] S5, hot pressing the gas diffusion layer, the catalyst layer, the proton exchange membrane, the catalyst layer, and the gas diffusion layer in the above-mentioned order to obtain a membrane electrode.

[0019] Preferably, the coating method is one of slit coating, spray coating, electrodeposition and scraping coating.

[0020] The present invention also discloses a preparation device for a membrane electrode of a high-performance and high-temperature proton exchange membrane fuel cell, comprising a base, an L-shaped plate fixedly connected to the base, two electric push rods installed on the upper end of the L-shaped plate, a movable plate fixedly connected to the output ends of the two electric push rods, an upper hot pressing assembly movably installed on the movable plate, a processing table fixedly connected to the base, a through groove penetrating the bottom of the processing table at the front and back, a movable groove provided at the upper end of the processing table, a movable frame slidably connected in the movable groove, the movable frame is installed on the processing table through two limit mechanisms, and a resettable lower hot pressing assembly is slidably connected in the movable frame

[0021] Preferably, the upper hot pressing assembly includes a first mounting plate, a first heating plate is fixed to the bottom of the first mounting plate, a first heat conducting plate is fixed to the bottom of the first heating plate, four first guide rods are fixed to the upper end of the first mounting plate, the four first guide rods all pass through the movable plate and are slidably connected thereto, a first spring is fixed to the bottom of the movable plate, the lower end of the first spring is fixedly connected to the upper end of the first mounting plate, and the first spring sleeve is arranged on the outside of the first guide rod.

[0022] Preferably, the lower hot pressing assembly includes a slide plate slidably connected in the through groove, a second guide rod is fixed to the upper end of the slide plate, the second guide rod passes through the processing table and is slidably arranged with it, the second guide rod extends into the movable groove and a second mounting plate is fixed to the upper end of the second guide rod, a second heating plate is fixed to the upper end of the second mounting plate, a second heat conducting plate is fixed to the upper end of the second heating plate, a second spring is fixed to the bottom of the second mounting plate, the lower end of the second spring is fixedly connected to the inner bottom of the movable groove, and the second spring sleeve is arranged on the outside of the second guide rod.

[0023] Preferably, the limiting mechanism includes a U-shaped block fixed on the processing table, a slider is slidably connected in the U-shaped block, a limiting rod is passed through the slider and fixedly connected to it, the limiting rod passes through the processing table and the U-shaped block and is slidably connected thereto, a limiting groove is provided on the outer wall of the movable frame, the limiting rod is movably connected in the limiting groove, a third spring is provided between the slider and the U-shaped block, the third spring is sleeved on the outside of the limiting rod, a pulling block is fixed on the limiting rod, and a short rod that abuts against the side wall of the U-shaped block is fixed on the pulling block.

[0024] Preferably, it also includes a cooling mechanism, which includes two air bags fixed on the upper end of the slide, the upper ends of the air bags are fixedly connected to the inner top of the through groove, two through holes are penetrated on the processing table, and a hose connected to the air bags is slidably connected in the through holes, a mounting seat is fixed on the processing table, a fixed tube is installed on the mounting seat, an air jet hole is penetrated on the fixed tube, and the fixed tube is connected to the hose through a connecting tube.

[0025] The beneficial effects of the present invention are:

[0026] Compared with the prior art, the present invention performs solvent annealing treatment on the coating after the slurry coating is dried. This method is used to improve the uniformity of the coating, reduce the internal resistance of the coating, and improve the battery performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is a schematic structural diagram of a device for preparing a membrane electrode for a high-performance, high-temperature proton exchange membrane fuel cell proposed in the present invention;

[0028] Figure 2 A schematic diagram of a processing station in a device for preparing a membrane electrode for a high-performance, high-temperature proton exchange membrane fuel cell proposed in the present invention;

[0029] Figure 3 This is a schematic diagram of the structure at A in the device for preparing the membrane electrode of a high-performance high-temperature proton exchange membrane fuel cell proposed by the present invention;

[0030] Figure 4 This is a side view of the pulling block in the device for preparing the membrane electrode of a high-performance and high-temperature proton exchange membrane fuel cell proposed by the present invention.

[0031] In the figure: 1 base, 2 L-shaped plate, 3 electric push rod, 4 moving plate, 5 first heating plate, 6 first mounting plate, 7 first heat conducting plate, 8 first guide rod, 9 first spring, 10 processing table, 11 slide plate, 12 through groove, 13 movable groove, 14 second mounting plate, 15 second heating plate, 16 second heat conducting plate, 17 second guide rod, 18 second spring, 19 support block, 20 hose, 21 connecting pipe, 22 mounting seat, 23 fixed pipe, 24 jet hole, 25 through hole, 26 airbag, 27 movable frame, 28 limit groove, 29 limit rod, 30 U-shaped block, 31 slider, 32 third spring, 33 pull block, 34 short rod. DETAILED DESCRIPTION

[0032] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments.

[0033] Example 1

[0034] A high-performance, high-temperature proton exchange membrane fuel cell membrane electrode comprises a proton exchange membrane, a catalyst layer and a gas diffusion layer.

[0035] The preparation process of a high-performance high-temperature proton exchange membrane fuel cell membrane electrode comprises the following steps:

[0036] S1, the catalytic layer is prepared by coating a uniform mixture of a catalyst, ultrapure water, a solvent and a resin on a substrate, and the substrate is one of a proton exchange membrane and a gas diffusion layer;

[0037] S2, drying the catalyst layer and the substrate;

[0038] S3, performing solvent annealing treatment on the catalyst layer and the substrate;

[0039] S4, hot pressing the gas diffusion layer, the catalyst layer, the proton exchange membrane, the catalyst layer, and the gas diffusion layer in the above-mentioned order to obtain a membrane electrode.

[0040] The coating method is one of slit coating, spray coating, electrodeposition and scraping coating.

[0041] In the present invention, the substrate can be a transfer membrane. After solvent annealing in step S3, the catalyst layer on the transfer membrane is transferred to the proton exchange membrane by hot pressing. That is to say, the proton exchange membrane and the gas diffusion layer can be used as substrates. Only when the transfer membrane is the substrate, the catalyst layer on the transfer membrane needs to be transferred to the proton exchange membrane by hot pressing, and then the membrane electrode is obtained by hot pressing treatment in step S4.

[0042] Among them, the explanation of annealing treatment is: the annealing process is to heat the azeotrope of organic solvent and water to a certain temperature, and anneal the above-mentioned material containing the catalyst layer. Among them, the organic solvent includes alcohol, ether, ketone, cyclic hydrocarbon, etc. Preferably, the azeotrope includes a binary azeotrope formed by alcohols such as ethanol, isopropanol, n-propanol, xylene, n-butanol, isobutanol, n-pentanol, isopentanol and water. The annealing assembly includes an anode catalyst layer, a cathode catalyst layer and a cathode and cathode catalyst layers. The annealing treatment range can be the entire range and a local range (such as around or in the center), and the annealing treatment methods include soaking, spraying and fumigation.

[0043] Wherein, the corresponding membrane electrode is prepared according to the selected membrane electrode preparation process (gas diffusion electrode process, catalyst layer coated proton membrane process and ordered membrane electrode process, etc.). If the substrate in S1 is a gas diffusion layer, the two gas diffusion layers prepared by the above process are respectively placed on both sides of the high-temperature proton exchange membrane, and are combined together with a seal by hot pressing, bonding or pasting, so as to obtain a membrane electrode for a high-temperature proton exchange membrane fuel cell; if the substrate in S1 is a proton exchange membrane, the proton exchange membrane with a catalyst layer prepared by the above process is placed between the two gas diffusion layers, and is combined together with a seal by hot pressing, bonding or pasting, so as to obtain a membrane electrode for a high-temperature proton exchange membrane fuel cell; if the substrate in S1 is a transfer membrane, the catalyst layer on the transfer membrane is transferred to both sides of the proton exchange membrane, and then placed between the two gas diffusion layers, and are combined together with a seal by hot pressing, bonding or pasting, so as to obtain a membrane electrode for a high-temperature proton exchange membrane fuel cell;

[0044] Use solvent annealing method to improve coating distribution uniformity, reduce internal resistance and improve battery performance;

[0045] 1) Using a mixture of a highly dispersible organic solvent and water as the annealing solvent is beneficial to improving the uniformity of the coating.

[0046] 2) Multiple annealing methods such as immersion, fumigation or spraying can be selectively used to achieve the best match between each membrane electrode preparation process and annealing step.

[0047] 3) According to the membrane electrode preparation process and application requirements, solvent annealing treatment can be selectively carried out over the entire range or locally to maximize the utilization of raw materials while achieving uniform distribution of the coating.

[0048] Example 2

[0049] (1) A uniform mixture of catalyst, ultrapure water, solvent and resin is coated onto the gas diffusion layer by slit coating and then dried at 40-80°C.

[0050] (2) Using an azeotrope of isopropyl alcohol and water, heated to boiling point, the coated sample was fumigated for 5 minutes.

[0051] Two gas diffusion electrodes obtained in step 1 are placed on both sides of the high-temperature proton exchange membrane respectively, and combined together with the seal by hot pressing, bonding or pasting to obtain a membrane electrode for high-temperature proton exchange membrane fuel cell, which is recorded as membrane electrode 1.

[0052] The two gas diffusion electrodes obtained through steps (1) and (2) are placed on both sides of the high-temperature proton exchange membrane respectively, and combined together with the seal by hot pressing, bonding or pasting, so as to obtain a membrane electrode for high-temperature proton exchange membrane fuel cell, which is recorded as membrane electrode 2.

[0053] Table: Conductivity of membrane electrode 1 and membrane electrode 2;

[0054] Membrane electrode 1 Membrane Electrode 2 <![CDATA[Conductivity (S·cm -1 )]]> <![CDATA[4X10 -6 ]]> <![CDATA[2X10 -5 ]]>

[0055] The present invention also discloses a high-performance, high-temperature proton exchange membrane fuel cell membrane electrode, which includes a proton exchange membrane, a catalyst layer and a gas diffusion layer. The proton exchange membrane, the catalyst layer and two gas diffusion layers are connected together by hot pressing.

[0056] Reference Figure 1-4 The present invention also discloses a preparation device for a membrane electrode of a high-performance and high-temperature proton exchange membrane fuel cell, comprising a base 1, an L-shaped plate 2 is fixedly connected to the base 1, two electric push rods 3 are installed on the upper end of the L-shaped plate 2, a moving plate 4 is fixedly connected to the output ends of the two electric push rods 3, an upper hot pressing assembly is movably installed on the moving plate 4, the upper hot pressing assembly comprises a first mounting plate 6, a first heating plate 5 is fixed to the bottom of the first mounting plate 6, a first heat conducting plate 7 is fixed to the bottom of the first heating plate 5, four first guide rods 8 are fixed to the upper end of the first mounting plate 6, the four first guide rods 8 all penetrate the moving plate 4 and are slidably connected thereto, a first spring 9 is fixed to the bottom of the moving plate 4, the lower end of the first spring 9 is fixedly connected to the upper end of the first mounting plate 6, and the first spring 9 is sleeved on the outside of the first guide rod 8;

[0057] The base 1 is fixedly connected to a processing table 10, a through slot 12 is penetrated through the bottom of the processing table 10, a movable slot 13 is provided at the upper end of the processing table 10, a movable frame 27 is slidably connected in the movable slot 13, and the movable frame 27 is installed on the processing table 10 through two limiting mechanisms, and the limiting mechanism includes a U-shaped block 30 fixed to the processing table 10, a slider 31 is slidably connected in the U-shaped block 30, and a limiting rod 29 fixedly connected to the slider 31 is penetrated through the slider 31, and the limiting rod 29 penetrates The processing table 10 and the U-shaped block 30 are slidably connected therewith, a limit groove 28 is provided on the outer wall of the movable frame 27, a limit rod 29 is movably connected in the limit groove 28, a third spring 32 is provided between the slider 31 and the U-shaped block 30, the third spring 32 is sleeved on the outside of the limit rod 29, a pull block 33 is fixed on the limit rod 29, and a short rod 34 is fixed on the pull block 33 to abut against the side wall of the U-shaped block 30; wherein, a support block 19 for supporting the lower hot pressing assembly is fixed in the movable groove 13;

[0058] A lower hot pressing assembly that can be reset is slidably connected in the movable frame 27, and the lower hot pressing assembly includes a slide plate 11 slidably connected in the through groove 12, a second guide rod 17 is fixed to the upper end of the slide plate 11, the second guide rod 17 penetrates the processing table 10 and is slidably arranged therewith, the second guide rod 17 extends into the movable groove 13 and a second mounting plate 14 is fixed to the upper end of the second guide rod 17, a second heating plate 15 is fixed to the upper end of the second mounting plate 14, a second heat conducting plate 16 is fixed to the upper end of the second heating plate 15, a second spring 18 is fixed to the bottom of the second mounting plate 14, the lower end of the second spring 18 is fixedly connected to the inner bottom of the movable groove 13, and the second spring 18 is sleeved on the outside of the second guide rod 17;

[0059] It also includes a cooling mechanism, which includes two air bags 26 fixed on the upper end of the slide plate 11, the upper ends of the air bags 26 are fixedly connected to the inner top of the through groove 12, two through holes 25 are penetrated on the processing table 10, and a hose 20 connected to the air bags 26 is slidably connected in the through holes 25, a mounting seat 22 is fixed on the processing table 10, a fixed pipe 23 is installed on the mounting seat 22, an injection hole 24 is penetrated on the fixed pipe 23, and the fixed pipe 23 is connected to the hose 20 through a connecting pipe 21.

[0060] Specifically, the gas diffusion electrodes are placed on both sides of the high-temperature proton exchange membrane and on the second heat-conducting plate 16, and the second heat-conducting plate 16 can be heated by the second heating plate 15, and then the electric push rod 3 is started to drive the movable plate 4 and the upper hot pressing assembly to move downward, and the first heating plate 5 can work to heat the first heat-conducting plate 7. As the movable plate and the upper hot pressing assembly move downward, the first heat-conducting plate 7 abuts against the substrate and drives the second mounting plate 14, the second heating plate 15, the second heat-conducting plate 16, and the second guide rod 17 to move downward. At this time, the second spring 18 is compressed (the elastic force of the second spring 18 is less than the elastic force of the first spring 9), and finally the second mounting plate 14 abuts against the support block 19 and cannot move downward, and the movable plate 4 continues to move downward. At this time, the first spring 9 is compressed, so that the gas diffusion electrode and the high-temperature proton exchange membrane can be hot-pressed together;

[0061] The second guide rod 17 moves downward to drive the slide plate 11 downward, and the airbag 26 is stretched;

[0062] After the hot pressing is completed, the electric push rod 3 drives the moving plate 4 and the upper hot pressing assembly to reset. Under the action of the second spring 18, the second mounting plate 14, the second heating plate 15, the second heat conducting plate 16 and the second guide rod 17 can be reset to lift the membrane electrode upwards for the staff to take;

[0063] At the same time, the airbag 26 is compressed to transport air to the fixed pipe 23 through the hose 20 and the connecting pipe 21, and then blown out through the air jet hole 24 to the membrane electrode, so as to cool the membrane electrode and prevent the staff from being scalded;

[0064] If the movable frame 27 needs to be replaced, the staff pulls the pull block 33 by hand and rotates it so that the short rod 34 abuts against the U-shaped block 30. At this time, the limit rod 29 is disengaged from the limit groove 28. In this way, a single staff member can take out the movable frame 27 for replacement or cleaning, which is convenient and quick.

[0065] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. Preparation device for high-performance and high-temperature proton exchange membrane fuel cell membrane electrode, It is characterized in that The membrane electrode comprises a proton exchange membrane, a catalyst layer and a gas diffusion layer; The invention comprises a base (1), an L-shaped plate (2) being fixedly connected to the base (1), two electric push rods (3) being mounted on the upper end of the L-shaped plate (2), the output ends of the two electric push rods (3) being fixedly connected to a movable plate (4), an upper hot pressing assembly being movably mounted on the movable plate (4), a processing table (10) being fixedly connected to the base (1), a through groove (12) being provided through the bottom of the processing table (10) from front to back, a movable groove (13) being provided at the upper end of the processing table (10), a movable frame (27) being slidably connected in the movable groove (13), the movable frame (27) being mounted on the processing table (10) via two limit mechanisms, and a lower hot pressing assembly which can be reset being slidably connected in the movable frame (27); The upper hot pressing assembly comprises a first mounting plate (6), a first heating plate (5) is fixed to the bottom of the first mounting plate (6), a first heat conducting plate (7) is fixed to the bottom of the first heating plate (5), four first guide rods (8) are fixed to the upper end of the first mounting plate (6), the four first guide rods (8) all pass through the movable plate (4) and are slidably connected thereto, a first spring (9) is fixed to the bottom of the movable plate (4), the lower end of the first spring (9) is fixedly connected to the upper end of the first mounting plate (6), and the first spring (9) is sleeved on the outside of the first guide rod (8); The lower hot pressing assembly comprises a slide plate (11) slidably connected in the through groove (12), a second guide rod (17) being fixed to the upper end of the slide plate (11), the second guide rod (17) passing through the processing table (10) and being slidably arranged therewith, the second guide rod (17) extending into the movable groove (13) and a second mounting plate (14) being fixed to the upper end of the second guide rod (17), a second heating plate (15) being fixed to the upper end of the second mounting plate (14), a second heat conducting plate (16) being fixed to the upper end of the second heating plate (15), a second spring (18) being fixed to the bottom of the second mounting plate (14), the lower end of the second spring (18) being fixedly connected to the inner bottom of the movable groove (13), and the second spring (18) being sleeved on the outside of the second guide rod (17); The limiting mechanism comprises a U-shaped block (30) fixed on the processing table (10), a slider (31) is slidably connected inside the U-shaped block (30), a limiting rod (29) fixedly connected to the slider (31) is penetrated by the slider (31), the limiting rod (29) penetrates the processing table (10) and the U-shaped block (30) and is slidably connected thereto, a limiting groove (28) is provided on the outer wall of the movable frame (27), the limiting rod (29) is movably connected in the limiting groove (28), a third spring (32) is provided between the slider (31) and the U-shaped block (30), the third spring (32) is sleeved on the outside of the limiting rod (29), a pulling block (33) is fixed on the limiting rod (29), and a short rod (34) abutting against the side wall of the U-shaped block (30) is fixed on the pulling block (33); The invention also comprises a cooling mechanism, the cooling mechanism comprising two air bags (26) fixed to the upper end of the slide plate (11), the upper end of the air bags (26) being fixedly connected to the inner top of the through groove (12), the processing table (10) being provided with two through holes (25), a hose (20) connected to the air bags (26) being slidably connected in the through holes (25), a mounting seat (22) being fixed on the processing table (10), a fixing pipe (23) being installed on the mounting seat (22), a jet hole (24) being provided on the fixing pipe (23), and the fixing pipe (23) being connected to the hose (20) via a connecting pipe (21).

2. The preparation process of the high-performance high-temperature proton exchange membrane fuel cell membrane electrode preparation device according to claim 1, It is characterized in that The following steps are involved: S1, the catalytic layer is prepared by coating a uniform mixture of a catalyst, ultrapure water, a solvent and a resin on a substrate, and the substrate is one of a proton exchange membrane and a gas diffusion layer; S2, drying the catalyst layer and the substrate; S3, performing solvent annealing treatment on the catalyst layer and the substrate; S4, hot pressing the gas diffusion layer, the catalyst layer, the proton exchange membrane, the catalyst layer, and the gas diffusion layer in the above-mentioned order to obtain a membrane electrode.

3. The preparation process of the high-performance high-temperature proton exchange membrane fuel cell membrane electrode preparation device according to claim 1, The following steps are involved: S1, the catalytic layer is prepared by coating a uniform mixture of a catalyst, ultrapure water, a solvent and a resin on a substrate, and the substrate is a transfer film; S2, drying the catalytic layer and the transfer membrane; S3, performing solvent annealing treatment on the catalyst layer and the transfer film; S4, transferring the catalyst layer on the transfer membrane to the proton exchange membrane by hot pressing; S5, hot pressing the gas diffusion layer, the catalyst layer, the proton exchange membrane, the catalyst layer, and the gas diffusion layer in the above-mentioned order to obtain a membrane electrode.

4. The preparation process of the high-performance high-temperature proton exchange membrane fuel cell membrane electrode preparation device according to claim 2 or 3, It is characterized in that The coating method is one of slit coating, spray coating, electrodeposition and scraping coating.

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