CN115074775A - Integrated composite membrane, preparation method thereof and application thereof in alkaline hydrolysis hydrogen production - Google Patents
Integrated composite membrane, preparation method thereof and application thereof in alkaline hydrolysis hydrogen production Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 144
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 144
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 239000012528 membrane Substances 0.000 title claims abstract description 122
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000005904 alkaline hydrolysis reaction Methods 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 184
- 239000011148 porous material Substances 0.000 claims abstract description 73
- 238000007731 hot pressing Methods 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 60
- 239000006256 anode slurry Substances 0.000 claims description 54
- 239000006257 cathode slurry Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 229920000642 polymer Polymers 0.000 claims description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- 230000003197 catalytic effect Effects 0.000 claims description 25
- 229910045601 alloy Inorganic materials 0.000 claims description 24
- 239000000956 alloy Substances 0.000 claims description 24
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 23
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 20
- 238000006555 catalytic reaction Methods 0.000 claims description 16
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 239000002086 nanomaterial Substances 0.000 claims description 7
- 229910000510 noble metal Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 abstract description 21
- 239000002002 slurry Substances 0.000 abstract description 20
- 239000007789 gas Substances 0.000 abstract description 12
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 229910003294 NiMo Inorganic materials 0.000 description 21
- 239000000843 powder Substances 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 19
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 19
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 19
- 239000001099 ammonium carbonate Substances 0.000 description 19
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 239000012046 mixed solvent Substances 0.000 description 8
- 229910003266 NiCo Inorganic materials 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 4
- 239000010954 inorganic particle Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- 239000003011 anion exchange membrane Substances 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 108091081062 Repeated sequence (DNA) Proteins 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005405 multipole Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 239000012466 permeate Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/02—Diaphragms; Spacing elements characterised by shape or form
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
- C25B11/053—Electrodes comprising one or more electrocatalytic coatings on a substrate characterised by multilayer electrocatalytic coatings
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention relates to the technical field of hydrogen energy, and provides an integrated composite membrane, a preparation method thereof and application thereof in hydrogen production by alkaline hydrolysis. The composite membrane provided by the invention comprises a diaphragm layer, an anode catalyst layer, a hydrogen evolution cathode catalyst layer, an anode conductive net and a cathode conductive net, wherein the two catalyst layers are prepared by attaching slurry to the two sides of the diaphragm layer and then performing a hot pressing method, and can form an integrated structure which is mutually and tightly fused with the diaphragm layer, so that the contact resistance is reduced; the pore diameters of the anode catalyst layer and the hydrogen evolution cathode catalyst layer are both larger than the pore diameter of the diaphragm layer, and the pore diameters of the anode catalyst layer and the hydrogen evolution cathode catalyst layer are gradually increased from inside to outside, which is helpful for guiding gas to diffuse to the outside of the membrane and reducing the phenomena of gas crossing the membrane and gas sink. The composite membrane provided by the invention has the integrated functions and structures of electron conduction, electrocatalysis cathode hydrogen evolution, anodic oxidation and ion conduction, can improve the working performance of high current density, is beneficial to improving the hydrogen production rate of electrolysis equipment, and reduces the cost.
Description
Technical Field
The invention relates to the technical field of hydrogen energy, in particular to an integrated composite membrane, a preparation method thereof and application thereof in hydrogen production by alkaline hydrolysis.
Background
With the increasing scale and decreasing price of renewable power, the hydrogen production by water electrolysis will be rapidly developed into an important way for hydrogen production. Compared with gray hydrogen and blue hydrogen, the renewable electric power electrolysis hydrogen production is a main mode of green hydrogen production and is also an important way for realizing social sustainable development.
The hydrogen production by alkaline water electrolysis is the main mode of hydrogen production by water electrolysis at present, and has the obvious advantages of no need of noble metal catalyst, high scale degree and relatively low cost. However, compared with a proton exchange membrane electrolytic cell, the existing hydrogen production equipment by electrolyzing water by alkaline water has the defects of low current density and relatively high cell pressure.
In order to reduce the voltage of hydrogen production by alkaline water electrolysis, on one hand, a novel high-performance anode catalyst and a hydrogen evolution cathode catalyst need to be developed, and on the other hand, the ohmic drop between an anode and a hydrogen evolution cathode needs to be reduced, so that the interface structure between an electrode and a diaphragm needs to be optimized, the contact between the electrode and the diaphragm needs to be improved, and the equivalent resistance is reduced. Chinese patent CN111304677A discloses a membrane electrode assembly, which is composed of an anion exchange membrane middle layer, cathode catalyst layers on both sides, an anode catalyst layer, a cathode gas-liquid diffusion layer and an anode gas-liquid diffusion layer. In general, an anion membrane has a lower resistance than a porous separator for alkaline water electrolysis, but has a disadvantage of being expensive and having poor stability. In addition, the catalyst is supported on a gas-liquid diffusion layer (carbon paper or stainless steel), and then an anion membrane is sandwiched between a cathode and an anode catalyst layer, and is physically pressed to form a membrane electrode, so that the electrodes and the membrane are not fused with each other sufficiently at interfaces, and the resistances among the cathode, the anode and the membrane are large. Similar structure and method are reported in Chinese patent CN101781769A, and prepared hydrogen evolution cathode catalyst layer and anode catalyst layer are respectively overlapped on two sides of an alkaline polymer electrolyte membrane to prepare membrane electrode, and the defects of weak durability of anion membrane, poor fusion between electrode and membrane and large resistance exist.
Chinese patent CN110023542A reports a multi-pole electrolytic cell for alkaline water electrolysis and a hydrogen production method, wherein an alkaline water electrolytic cell using an inorganic particle porous membrane as a separator, at least one of an anode and a cathode is a porous electrode having an average pore diameter of 10nm to 200nm, and the separator is a porous membrane containing inorganic particles having an average particle diameter of 20nm to 300 nm. The porous membrane prepared by the inorganic particles and the polymer avoids the problems of high cost and insufficient stability when anion exchange resin is used as an ion membrane, but the gas generated by the diaphragm during electrolysis is easy to have transmembrane behavior. Meanwhile, the patent also discloses that the catalyst is coated on the conductive mesh substrate, and then the diaphragm is configured and installed between the cathode and the anode which are coated with the catalyst, so that the problem of large contact resistance still exists.
In summary, the existing alkaline water electrolysis hydrogen production membrane has the defects of large contact resistance and high price of an anion exchange membrane/resin, and although the porous diaphragm mainly constructed by hydrophilic inorganic particles is low in price, the phenomenon of gas transmembrane is easy to occur, so that the hydrogen production rate under low voltage and high current density is not ideal.
Disclosure of Invention
In view of the above, the invention provides an integrated composite membrane, a preparation method thereof and an application thereof in hydrogen production by alkaline hydrolysis. The hydrogen evolution cathode catalyst layer and the anode catalyst layer of the integrated composite membrane provided by the invention are tightly combined, the contact resistance is small, the phenomena of gas transmembrane and gas sink are not easy to occur, and the hydrogen production rate of the electrolysis equipment under low voltage and high current density is favorably improved.
In order to achieve the above object, the present invention provides the following technical solutions:
an integrated composite membrane is of a sandwich structure and comprises a diaphragm layer, an anode catalysis layer and a hydrogen evolution cathode catalysis layer which are arranged at two sides of the diaphragm layer, an anode conductive net arranged at the outer side of the anode catalysis layer and a cathode conductive net arranged at the outer side of the hydrogen evolution cathode catalysis layer;
the membrane layer is formed by hydrophilic inorganic nano materials and polymers;
the average pore diameters of the hydrogen evolution cathode catalyst layer, the anode catalyst layer and the membrane layer are in the following relation: the average pore diameter of the hydrogen evolution cathode catalytic layer is larger than the average pore diameter of the anode catalytic layer is larger than the average pore diameter of the membrane layer; the pore diameters of the anode catalyst layer and the hydrogen evolution cathode catalyst layer are gradually increased from inside to outside;
the meshes of the anode conductive net are larger than the average pore diameter of the anode catalytic layer, and the meshes of the cathode conductive net are larger than the average pore diameter of the hydrogen evolution cathode catalytic layer;
the anode catalyst layer is prepared by attaching anode slurry to one side of the diaphragm and then performing hot pressing; the components of the anode slurry comprise an anode catalyst, a polymer and a pore-forming agent;
the hydrogen evolution cathode catalyst layer is prepared by attaching cathode slurry to the other side of the diaphragm and then performing hot pressing; the components of the cathode slurry comprise a hydrogen evolution cathode catalyst, a polymer and a pore-forming agent.
Preferably, the hydrophilic inorganic nano-material comprises ZrO 2 、WO 2 、TiO 2 And Y 2 O 3 One or more of the above; the thickness of the membrane layer is less than or equal to 500 mu m, and the average pore diameter inside the membrane layer is 10 nm-300 nm.
Preferably, the anode catalyst comprises RuO 2 、IrO 2 And one or more of non-noble metal oxides, hydroxides or phosphides; the thickness of the anode catalyst layer is 10-600 mu m, and the average pore diameter inside the anode catalyst layer is 50-800 nm.
Preferably, the hydrogen evolution cathode catalyst comprises elementary substances of Pt, Ru, Pd and Ir, an alloy thereof and one or more of elementary substances, alloys, phosphide and nitride of Ni, Co, Mo, Cr and Cu; the thickness of the hydrogen evolution cathode catalyst layer is 10-600 mu m, and the internal average pore diameter range is 80-2000 nm.
Preferably, in the anode slurry, the mass ratio of the anode catalyst to the polymer to the pore-forming agent is 100 (10-50) to 5-40; the mass ratio of the hydrogen evolution cathode catalyst, the polymer and the pore-forming agent in the cathode slurry is 100 (10-50) to 8-60; and the pore-forming agent content in the anode slurry is lower than that in the cathode slurry.
Preferably, the pore-forming agent is a thermal decomposition type pore-forming agent or a water-soluble type pore-forming agent.
Preferably, the polymer used in the separator, the anode slurry and the cathode slurry independently includes one or more of polytetrafluoroethylene, polyphenylene sulfide, polysulfone, polyvinylidene fluoride and carboxymethyl cellulose.
Preferably, the anode conductive net and the cathode conductive net are independently carbon fiber nets, nickel nets, stainless steel nets or titanium nets, and the net aperture of the anode conductive net and the mesh aperture of the cathode conductive net are independently 10-500 μm.
The invention also provides a preparation method of the integrated composite membrane, which comprises the following steps:
(1) mixing an anode catalyst, a polymer, a pore-forming agent and a solvent to obtain anode slurry, and attaching the anode slurry to one side of a diaphragm layer; mixing a hydrogen evolution cathode catalyst, a polymer, a pore-forming agent and a solvent to obtain cathode slurry, and attaching the cathode slurry to the other side of the diaphragm layer;
(2) sequentially carrying out hot pressing and water washing on the diaphragm layer attached with the anode slurry and the cathode slurry;
(3) repeating the steps (1) - (2) for a plurality of times, and in the repeating process, according to the repeating sequence, the mass ratio of the pore-forming agent to the anode catalyst in the anode slurry is sequentially increased, and the mass ratio of the pore-forming agent to the hydrogen evolution cathode catalyst in the cathode slurry is sequentially increased; after the repetition is finished, an anode catalyst layer and a hydrogen evolution cathode catalyst layer are obtained on two sides of the membrane;
(4) and hot-pressing an anode conductive net on the surface of the anode catalytic layer, and hot-pressing a cathode conductive net on the surface of the hydrogen evolution cathode catalytic layer to obtain the integrated composite membrane.
The invention also provides application of the integrated composite membrane prepared by the preparation method in the scheme or application of the integrated composite membrane prepared by the preparation method in alkaline hydrolysis hydrogen production.
The invention provides an integrated composite membrane which is of a sandwich structure and comprises a diaphragm layer, an anode catalysis layer and a hydrogen evolution cathode catalysis layer which are arranged on two sides of the diaphragm layer, an anode conductive net arranged on the outer side of the anode catalysis layer and a cathode conductive net arranged on the outer side of the hydrogen evolution cathode catalysis layer. In the integrated composite membrane, the anode catalyst layer and the hydrogen evolution cathode catalyst layer are prepared by attaching anode slurry and cathode slurry on the surface of the membrane and then performing hot pressing, and the slurry containing the catalyst layer raw material directly permeates on the surface of the membrane layer, so that the subsequent close fusion of the catalyst and the membrane layer is facilitated, and the reduction of equivalent resistance of the cathode, the anode and the membrane is realized. In addition, in the integrated composite membrane, the pore diameters of the anode catalyst layer and the hydrogen evolution cathode catalyst layer are larger than that of the diaphragm layer, so that the possibility of gas directly crossing the membrane for transmission is reduced, and the pore diameters of the anode catalyst layer and the hydrogen evolution cathode catalyst layer are gradually increased from inside to outside, so that the gas is guided to diffuse towards the outside of the integrated membrane, the gas sink phenomenon is reduced, the catalyst active area is quickly recovered, and the bubble equivalent resistance is reduced. By the aid of the gradually-increased pore diameter and the integrated structure of the membrane and the catalyst layer, high-current-density working performance can be improved, hydrogen production rate of electrolysis equipment can be improved, and hydrogen production energy consumption and equipment cost can be reduced.
The invention also provides a preparation method of the integrated composite membrane, and the anode catalyst layer and the hydrogen evolution cathode catalyst layer are prepared by a method of preparing layer by layer and sequentially improving the mass ratio of the pore-forming agent to the catalyst in the slurry, so that the pore diameter in the catalyst layer is gradually increased from inside to outside. The method provided by the invention has simple steps and is easy to operate.
The invention also provides the application of the integrated composite membrane in the scheme in the hydrogen production by alkaline hydrolysis, the composite membrane can be applied to the conventional hydrogen production by electrolyzing alkaline water, and can also be applied to the coupled anodic oxidation of the hydrogen production by electrolyzing alkaline water, wherein the former anode generates an oxygen evolution reaction, the latter anode mainly generates an oxidation reaction of organic matters, but the two cathodes generate hydrogen evolution reactions.
Drawings
Fig. 1 is a schematic structural diagram of an integrated composite membrane provided by the present invention, wherein: 1-diaphragm layer, 2-anode catalyst layer, 3-hydrogen evolution cathode catalyst layer, 4-anode conductive net and 5-cathode conductive net.
Detailed Description
The invention provides an integrated composite membrane which is of a sandwich structure and comprises a diaphragm layer, an anode catalysis layer and a hydrogen evolution cathode catalysis layer which are arranged on two sides of the diaphragm layer, an anode conductive net arranged on the outer side of the anode catalysis layer and a cathode conductive net arranged on the outer side of the hydrogen evolution cathode catalysis layer.
The membrane layer is formed by hydrophilic inorganic nano materials and polymers;
the average pore diameters of the hydrogen evolution cathode catalyst layer, the anode catalyst layer and the membrane layer are in the following relation: the average pore diameter of the hydrogen evolution cathode catalytic layer is larger than the average pore diameter of the anode catalytic layer is larger than the average pore diameter of the membrane layer; the pore diameters of the anode catalyst layer and the hydrogen evolution cathode catalyst layer are gradually increased from inside to outside;
the meshes of the anode conductive net are larger than the average pore diameter of the anode catalytic layer, and the meshes of the cathode conductive net are larger than the average pore diameter of the hydrogen evolution cathode catalytic layer;
the anode catalyst layer is prepared by attaching anode slurry to one side of the diaphragm and then performing hot pressing; the components of the anode slurry comprise an anode catalyst, a polymer and a pore-forming agent;
the hydrogen evolution cathode catalyst layer is prepared by attaching cathode slurry to the other side of the diaphragm and then performing hot pressing; the cathode slurry comprises components of a hydrogen evolution cathode catalyst, a polymer and a pore-forming agent.
The integrated composite membrane provided by the invention comprises a diaphragm layer. In the present invention, the membrane layer is formed of a hydrophilic inorganic nanomaterial, preferably including ZrO, and a polymer 2 、WO 2 、 TiO 2 And Y 2 O 3 Preferably, the polymer comprises one or more of polytetrafluoroethylene, polyphenylene sulfide, polysulfone, polyvinylidene fluoride and carboxymethyl cellulose; the thickness of the membrane layer is preferably less than or equal to 500 mu m, and the average pore diameter in the membrane layer is preferably 10-300 nm, and more preferably 150-250 nm; in the invention, a reticular reinforcing rib is preferably arranged in the diaphragm layer for improving the mechanical strength of the diaphragm, and the reticular reinforcing rib is made of a high polymer material. In a specific embodiment of the present invention, a commercially available separator formed of a hydrophilic inorganic nanomaterial and a polymer, such as commercial ZrO, is preferably used 2 -a polyphenylene sulfide membrane.
The integrated composite membrane provided by the invention comprises an anode catalyst layer arranged on one side of a membrane. In the invention, the anode catalyst layer is prepared by attaching anode slurry to one side of the diaphragm and then performing hot pressing; the components of the anode slurry comprise an anode catalyst, a polymer and a pore-forming agent; the anode catalyst preferably comprises RuO 2 、IrO 2 And one or more of oxides, hydroxides or phosphides of non-noble metals, the non-noble metals preferably include Ni, Fe, Co or Mn; in a specific embodiment of the invention, the anode catalyst is preferably a NiFe bimetal hydroxide or a NiCo bimetal hydroxide, the ratio of two metals in the NiFe bimetal hydroxide or the NiCo bimetal hydroxide is not particularly required, and the ratio is determined according to a ratio well known by a person skilled in the art, and in the specific embodiment of the invention, the molar ratio of Ni to Fe in the NiFe bimetal hydroxide is preferably 2-5: 1. In the present invention, the optional range and spacing of the polymers employed in the anode slurryThe selectable range of polymers used in the membrane is consistent and will not be described in detail herein; in the invention, the pore-forming agent used in the anode slurry preferably includes a thermal decomposition type pore-forming agent or a water-soluble type pore-forming agent, and specifically, the pore-forming agent preferably includes one or more of ammonium bicarbonate, sodium bicarbonate, ammonium nitrate and sodium sulfate. In the invention, the mass ratio of the anode catalyst, the polymer and the pore-forming agent in the anode slurry is preferably 100 (10-50): 5-40), and preferably 100 (20-40): 10-30.
In the invention, the average pore diameter of the anode catalyst layer is larger than that of the membrane layer, and the pore diameter in the anode catalyst layer is gradually increased from inside to outside; according to the invention, the aperture of the anode catalyst layer is gradually increased from inside to outside, so that the diffusion of gas to the outside of the integrated membrane is favorably guided. In a specific embodiment of the invention, the anode catalyst layer is prepared layer by layer from anode slurry, and the mass ratio of pore-forming agent to catalyst in the slurry is sequentially increased during layer-by-layer preparation, so that the pore diameter is gradually increased, and the specific preparation method is described in detail later.
In the invention, the thickness of the anode catalyst layer is preferably 10-600 μm, more preferably 100-500 μm, and the average pore diameter inside the anode catalyst layer is preferably 50-800 nm, more preferably 200-600 nm.
The integrated composite membrane provided by the invention comprises a hydrogen evolution cathode catalyst layer arranged on the other side of the diaphragm layer. In the invention, the hydrogen evolution cathode catalyst layer is prepared by attaching cathode slurry to one side of a diaphragm and then performing a hot pressing method; the cathode slurry comprises the components of a hydrogen evolution cathode catalyst, a polymer and a pore-forming agent; the hydrogen evolution cathode catalyst is preferably one or more of simple substances and alloys of Pt, Ru, Pd and Ir, and simple substances, alloys, phosphide and nitrides of Ni, Co, Mo, Cr and Cu, and in a specific embodiment of the invention, the hydrogen evolution cathode catalyst is NiMo alloy powder, the ratio of Ni to Mo in the NiMo alloy powder is not particularly required, the conventional ratio in the field is adopted, and in the specific embodiment of the invention, the molar ratio of Ni to Mo in the NiMo alloy powder is preferably 3-6: 1. In the present invention, the selectable range of the polymer used in the cathode slurry is the same as the selectable range of the polymer used in the separator, and the details are not repeated herein; in the present invention, the selectable range of the pore-forming agent used in the cathode slurry is the same as the selectable range of the pore-forming agent used in the anode slurry, and details thereof are not repeated herein. In the invention, the mass ratio of the hydrogen evolution cathode catalyst, the polymer and the pore-forming agent in the cathode slurry is preferably 100 (10-50) to (8-60), and preferably 100 (20-40) to (10-50); and the pore-forming agent content in the anode slurry is lower than that in the cathode slurry, in the invention, the average pore diameter of the hydrogen evolution cathode catalyst layer is larger than that of the anode catalyst layer, so that more pore-forming agents are used in the cathode slurry, and the pore diameter relation can be ensured.
In the invention, the pore diameter in the hydrogen evolution cathode catalyst layer is gradually increased from inside to outside; the invention sets the aperture of the hydrogen evolution cathode catalyst layer to be gradually increased from inside to outside, which is favorable for guiding gas to diffuse to the outside of the integrated membrane. In a specific embodiment of the invention, the hydrogen evolution cathode catalyst layer is prepared layer by layer from cathode slurry, and the mass ratio of pore-forming agent to catalyst in the slurry is sequentially increased during layer-by-layer preparation, so that the pore diameter is gradually increased, and the specific preparation method is described in detail later.
In the invention, the thickness of the hydrogen evolution cathode catalyst layer is preferably 10-600 μm, more preferably 100-500 μm, and the average pore diameter in the hydrogen evolution cathode catalyst layer is preferably 80-2000 nm, more preferably 300-1500 nm.
The integrated film provided by the invention comprises an anode conductive net arranged outside an anode catalyst layer. In the invention, the mesh of the anode conductive net is larger than the average pore diameter of the anode catalyst layer, specifically more than 5 times, preferably 50-500 times of the average pore diameter of the anode catalyst layer. In the invention, the anode conductive net is preferably a carbon fiber net, a nickel net, a stainless steel net or a titanium net, and the aperture of the anode conductive net is preferably 10-500 μm, and more preferably 100-300 μm.
The integrated membrane provided by the invention comprises a cathode conductive net arranged on the outer layer of the hydrogen evolution cathode catalyst layer. In the invention, the mesh of the cathode conductive net is larger than the average pore diameter of the hydrogen evolution cathode catalyst layer, specifically more than 5 times, preferably 30-200 times of the average pore diameter of the hydrogen evolution cathode catalyst layer; the selectable types of the cathode conductive net are consistent with those of the anode conductive net, and are not described again; the aperture of the mesh of the cathode conductive net is preferably 10-500 μm, and more preferably 100-300 μm.
Fig. 1 is a schematic structural diagram of an integrated composite membrane provided by the present invention, wherein 1 is a membrane layer, 2 is an anode catalytic layer, 3 is a hydrogen evolution cathode catalytic layer, 4 is an anode conductive mesh, 5 is a cathode conductive mesh, the average pore diameter of the membrane layer is d1, the average pore diameter of the anode catalytic layer is d2, the average pore diameter of the hydrogen evolution cathode catalytic layer is d3, the pore diameter of the mesh of the anode conductive mesh is d4, the pore diameter of the mesh of the cathode conductive mesh is d5, and in 1, the relationship between d1 and d5 is as follows: d5 is approximately equal to d4 > d3 > d2 > d1, and the pore diameters in the anode catalytic layer and the hydrogen evolution cathode catalytic layer are gradually increased from inside to outside.
The invention also provides a preparation method of the integrated composite membrane, which comprises the following steps:
(1) mixing an anode catalyst, a polymer, a pore-forming agent and a solvent to obtain anode slurry, and attaching the anode slurry to one side of a diaphragm layer; mixing a hydrogen evolution cathode catalyst, a polymer, a pore-forming agent and a solvent to obtain cathode slurry, and attaching the cathode slurry to the other side of the diaphragm layer;
(2) sequentially carrying out hot pressing and water washing on the diaphragm layer attached with the anode slurry and the cathode slurry;
(3) repeating the steps (1) to (2) for a plurality of times, and in the repeating process, according to the repetition times, the proportion of the pore-forming agent to the anode catalyst in the anode slurry is sequentially increased, and the proportion of the pore-forming agent to the hydrogen evolution cathode catalyst in the cathode slurry is sequentially increased; after the repetition is finished, an anode catalyst layer and a hydrogen evolution cathode catalyst layer are obtained on two sides of the membrane;
(4) and hot-pressing an anode conductive net on the surface of the anode catalytic layer, and hot-pressing a cathode conductive net on the surface of the hydrogen evolution cathode catalytic layer to obtain the integrated composite membrane.
The method comprises the steps of mixing an anode catalyst, a polymer, a pore-forming agent and a solvent to obtain anode slurry, and attaching the anode slurry to one side of a diaphragm layer. In the invention, the solvent is preferably a mixed solvent of water and ethanol, and the volume ratio of water to ethanol in the mixed solvent is preferably 1: 1-3; in the invention, the mass ratio of the solvent to the solid in the slurry is preferably 1-10: 1; the mixing is preferably ultrasonic mixing; before the diaphragm is used, the diaphragm is preferably washed by water, washed by alcohol and dried in sequence; the method for attaching the anode slurry to one side of the separator layer is preferably spraying or coating.
The method comprises the steps of mixing a hydrogen evolution cathode catalyst, a polymer, a pore-forming agent and a solvent to obtain cathode slurry, and attaching the cathode slurry to the other side of a diaphragm layer. In the present invention, the solvent used in the cathode slurry, the mixing manner, and the manner of adhering to the surface of the separator are preferably the same as those of the anode slurry, and will not be described herein again.
After the anode slurry and the cathode slurry are attached to the two sides of the diaphragm, the diaphragm layer attached with the anode slurry and the cathode slurry is sequentially subjected to hot pressing and water washing. In the invention, the hot pressing temperature is preferably 80-240 ℃, more preferably 100-200 ℃, the pressure is preferably 10-50 MPa, more preferably 20-40 MPa, the time is preferably 5-30 min, more preferably 10-20 min; the water for washing is preferably pure water, and the residual pore-forming agent is removed by washing with water in the present invention.
After the hot pressing is finished, the steps of hot pressing and water washing after the anode slurry and the cathode slurry are coated are repeated for a plurality of times, in the repeated process, according to the repeated sequence, the mass ratio of the pore-forming agent to the anode catalyst in the anode slurry is sequentially increased, the mass ratio of the pore-forming agent to the hydrogen evolution cathode catalyst in the cathode slurry is sequentially increased, specifically, the mass ratio of the anode catalyst to the hydrogen evolution cathode catalyst in the slurry is kept unchanged, and the mass ratio of the pore-forming agent to the hydrogen evolution cathode catalyst is increased by adjusting the dosage of the pore-forming agent; after the repetition is finished, an anode catalyst layer and a hydrogen evolution cathode catalyst layer are obtained on two sides of the membrane. In the invention, the repetition frequency is preferably more than 3 times, more preferably 3-5 times, taking the anode slurry used in the case of repeating three times as an example, the proportion of the pore-forming agent to the anode catalyst in the anode slurry in the first time can be 5:100 or 10:100, the proportion of the pore-forming agent to the anode catalyst in the anode slurry in the second time can be 10:100 or 20:100, and the proportion of the pore-forming agent to the anode catalyst in the anode slurry in the third time can be 20:100 or 30: 100; the method has no special requirement on the dosage of the slurry used each time, and the dosage is determined according to the thickness of the target catalytic layer and the repetition times. In the present invention, the ratio ranges of the catalyst and the pore-forming agent in the anode slurry and the cathode slurry are as described above, and the ratio of the pore-forming agent to the catalyst is increased in the above-mentioned ranges in the repetition process.
After the anode catalyst layer and the hydrogen evolution cathode catalyst layer are prepared, the invention carries out hot pressing on the anode conductive net on the surface of the anode catalyst layer and carries out hot pressing on the cathode conductive net on the surface of the hydrogen evolution cathode catalyst layer to obtain the integrated composite membrane. In the invention, the temperature of the hot-pressing anode conductive net and the temperature of the hot-pressing cathode conductive net are preferably 80-240 ℃, more preferably 100-200 ℃, the pressure is preferably 10-50 MPa, more preferably 20-40 MPa, and the time is preferably 5-30 min, more preferably 10-20 min.
The invention also provides application of the integrated composite membrane or the integrated composite membrane prepared by the preparation method in the scheme in alkaline hydrolysis hydrogen production. In the invention, the hydrogen production by alkaline hydrolysis can be conventional hydrogen production by electrolyzing alkaline water, and can also be hydrogen production by electrolyzing alkaline water coupled with anodic oxidation; the method of the present invention is not particularly limited to the method of application, and may be a method well known to those skilled in the art.
The technical solutions in the present invention will be clearly and completely described below with reference to the embodiments of the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
The diaphragm used in this example was commercial ZrO 2 -a polyphenylene sulfide membrane with a thickness of 500 μm and an average pore size of around 50 nm; the anode catalyst layer is an NiFe double-metal hydroxide-polytetrafluoroethylene anode catalyst layer, and the mass ratio of the NiFe double-metal hydroxide to the polytetrafluoroethylene is 100: 15; the hydrogen evolution cathode catalyst layer is an NiMo alloy-polyphenylene sulfide hydrogen evolution catalyst layer, and the mass ratio of the NiMo alloy to the polyphenylene sulfide is 100: 10; an anode 80-mesh nickel mesh conductive net layer with an effective average pore size of about 100 mu m; the hydrogen evolution cathode is a conductive mesh made of 80-mesh stainless steel, and the effective average pore diameter is about 100 mu m.
The preparation method of the integrated composite membrane comprises the following steps: :
(1) commercial ZrO to be commercialized 2 Washing the polyphenylene sulfide membrane with water for 2 times and alcohol for 1 time, and then drying in vacuum at 70 ℃ for later use.
(2) The method comprises the following steps of ultrasonically mixing NiFe double-metal hydroxide powder (the molar ratio of Ni to Fe is about 3:1), polytetrafluoroethylene powder and ammonium bicarbonate in a mixed solvent of water and ethanol according to the mass ratio of 100:15:10 uniformly to form anode slurry, wherein the content of the NiFe double-metal hydroxide powder in the anode slurry is 300 mg/mL. Then spraying on one side of the diaphragm layer;
(3) mixing NiMo alloy powder (the molar ratio of Ni to Mo is about 4:1), polyphenylene sulfide powder and ammonium bicarbonate according to the mass ratio of 100: 10: 15 in a mixed solvent of water and ethanol, carrying out ultrasonic mixing uniformly to form cathode slurry, wherein the content of NiMo alloy powder in the slurry is 300 mg/mL; and then sprayed on one side of the membrane layer.
(4) And after the two steps, carrying out hot pressing treatment on the diaphragm layer coated or sprayed with the anode slurry and the cathode slurry for 15min at the temperature of 120 ℃ under the pressure of 20MPa, washing the diaphragm subjected to hot pressing with pure water, and removing the residue of the pore-forming agent.
(5) Repeating the steps (2) to (4) for 3 times, wherein when preparing the anode catalyst layer slurry, the mass ratio of the ammonium bicarbonate/NiFe double-metal hydroxide catalyst is gradually increased from 10:100 for the first time to 20:100 for the second time to 30:100 for the third time (the mass ratio is realized by adjusting the mass of the ammonium bicarbonate when the mass of the NiFe double-metal hydroxide catalyst in the slurry is unchanged), and when preparing the cathode slurry, the mass ratio of the ammonium bicarbonate/NiMo alloy catalyst is from 15:100 to 30:100 to 45:100 (the mass ratio is realized by adjusting the mass of the ammonium bicarbonate when the mass of the NiMo alloy catalyst in the slurry is unchanged). The aperture of the integrated composite membrane is gradually increased from inside to outside in the catalyst layers on the two sides.
(6) And respectively hot-pressing an 80-mesh stainless steel conductive net and an 80-mesh nickel net on two sides of the hydrogen evolution cathode catalyst layer and the anode catalyst layer, wherein the hot-pressing temperature is 160 ℃, the hot-pressing pressure is 30MPa, and the hot-pressing treatment time is 15 min. Finally, an integrated composite membrane of electron conduction, electrocatalytic cathodic hydrogen evolution, anodic oxidation and ion conduction is formed, wherein the average pore diameter of the membrane layer is about 50nm, the average pore diameter of the anodic catalyst layer is about 200nm, and the average pore diameter of the hydrogen evolution cathodic catalyst layer is about 500 nm.
The integrated composite diaphragm prepared by the embodiment is used in an alkaline water electrolysis hydrogen production electrolytic tank with the effective diameter of 100mm, the electrolyte is 30 percent of potassium hydroxide, the electrolysis temperature is 85 ℃, and the applied current density is 8000A/m 2 The single-chamber cell voltage is only 1.89V, the hydrogen evolution current efficiency is 98.6 percent, and the hydrogen production performance by electrolysis with low voltage and high current density is shown.
Example 2
The diaphragm used in this example was commercial ZrO 2 -a polyphenylene sulfide membrane with a thickness of 220 μm and an average pore size of around 30 nm; the anode catalyst layer is a NiFe bimetal hydroxide-polytetrafluoroethylene anode catalyst layer, and the mass ratio of the NiFe bimetal hydroxide to the polytetrafluoroethylene is 100: 25; the hydrogen evolution cathode catalyst layer is an NiMo alloy-polyphenylene sulfide hydrogen evolution catalyst layer, and the mass ratio of the NiMo alloy to the polyphenylene sulfide is 100: 20; an anode 80-mesh nickel mesh conductive net layer with an effective average pore size of about 100 mu m; the hydrogen evolution cathode is a conductive mesh made of 80-mesh stainless steel, and the effective average pore diameter is about 100 mu m.
The preparation method of the integrated composite membrane comprises the following steps:
(1) will commercial ZrO 2 Washing the polyphenylene sulfide membrane for 1 time and washing the polyphenylene sulfide membrane for 2 times by alcohol, and then drying the polyphenylene sulfide membrane for later use in vacuum at 70 ℃.
(2) The method comprises the following steps of ultrasonically mixing NiFe double-metal hydroxide powder (the molar ratio of Ni to Fe is about 3:1), polytetrafluoroethylene powder and ammonium bicarbonate in a mixed solvent of water and ethanol according to the mass ratio of 100:15:5 uniformly to form anode slurry, wherein the content of the NiFe double-metal hydroxide powder in the anode slurry is 300 mg/mL. And then sprayed on one side of the membrane layer.
(3) Mixing NiMo alloy powder (the molar ratio of Ni to Mo is 4:1), polyphenylene sulfide powder and ammonium bicarbonate according to a mass ratio of 100: 10: 8, ultrasonically and uniformly mixing in a mixed solvent of water and ethanol to form hydrogen evolution cathode slurry, wherein the content of NiMo alloy powder in the slurry is 400 mg/mL. And then sprayed on one side of the membrane layer.
(4) And carrying out hot-pressing treatment on the diaphragm layer coated with the anode slurry and the cathode slurry for 15min at the temperature of 120 ℃ under the pressure of 20MPa, and washing the diaphragm subjected to hot pressing by pure water to remove the residue of the pore-forming agent.
(5) Repeating the steps (2) to (4) for 3 times, wherein when the anode slurry is prepared, the mass ratio of the ammonium bicarbonate/NiFe double-metal hydroxide catalyst is gradually increased from 5:100 to 10:100 to 20:100 (mass of NiFe double metal hydroxide catalyst in the slurry is unchanged, the above mass ratio is achieved by adjusting the mass of ammonium bicarbonate), and the ratio of ammonium bicarbonate/NiMo alloy catalyst is from 8:100 to 20:100 to 40:100 (mass of NiMo alloy catalyst in the slurry is unchanged, the above mass ratio is achieved by adjusting the mass of ammonium bicarbonate) when preparing the cathode slurry. The aperture of the integrated composite membrane is gradually increased from inside to outside in the catalyst layers on the two sides.
(6) And respectively hot-pressing an 80-mesh stainless steel conductive net and an 80-mesh nickel net on two sides of the hydrogen evolution cathode catalyst layer and the anode catalyst layer, wherein the hot-pressing temperature is 160 ℃, the hot-pressing pressure is 30MPa, and the hot-pressing time is 15 min. Finally, an integrated composite membrane of electron conduction, electrocatalytic cathodic hydrogen evolution, anodic oxidation and ion conduction is formed, wherein the average pore diameter of the membrane layer is about 30nm, the average pore diameter of the anodic catalyst layer is about 120nm, and the average pore diameter of the hydrogen evolution cathodic catalyst layer is about 300 nm.
The two-section integrated composite diaphragm prepared by the embodiment is used in an alkaline water electrolysis hydrogen production electrolytic cell with the effective diameter of 100mm, the electrolyte is 30 percent of potassium hydroxide, the electrolysis temperature is 85 ℃, and the applied current density is 10000A/m 2 The voltage of the single-chamber cell is only 1.91V, and the hydrogen evolution current efficiency is 98.4 percent. Exhibit a low voltageHigh current density hydrogen production performance by electrolysis.
Example 3
The barrier layer employed in this example was commercial ZrO 2 -a polyphenylene sulfide membrane with a thickness of 220 μm and an average pore size of around 30 nm; the anode catalyst layer is a NiCo bimetallic hydroxide-polytetrafluoroethylene anode catalyst layer, and the mass ratio of the NiCo bimetallic hydroxide to the polytetrafluoroethylene is 100: 25; the hydrogen evolution cathode catalyst layer is an NiMo alloy-polyphenylene sulfide hydrogen evolution catalyst layer, and the mass ratio of the NiMo alloy to the polyphenylene sulfide is 100: 20; the effective average pore size of the anode 80-mesh nickel mesh conductive net layer is about 100 mu m, and the effective average pore size of the hydrogen evolution cathode 80-mesh stainless steel mesh conductive net layer is about 100 mu m.
The preparation method of the integrated composite membrane comprises the following steps:
(1) to form commercial ZrO 2 Washing the polyphenylene sulfide membrane for 1 time and washing the polyphenylene sulfide membrane for 2 times by alcohol, and then drying the polyphenylene sulfide membrane for later use in vacuum at 70 ℃.
(2) Ultrasonically and uniformly mixing NiCo double-metal hydroxide powder (the molar ratio of Ni to Fe is 3:1), polytetrafluoroethylene powder and ammonium bicarbonate in a mixed solvent of water and ethanol according to the mass ratio of 100:15:5 to form anode slurry, wherein the content of the NiFe double-metal hydroxide powder in the slurry is 500 mg/mL. And then sprayed on one side of the membrane layer.
(3) Mixing NiMo alloy powder (the molar ratio of Ni to Mo is 4:1), polyphenylene sulfide powder and ammonium bicarbonate according to a mass ratio of 100: 10: 8, uniformly mixing in a mixed solvent of water and ethanol by ultrasonic waves to form cathode slurry, wherein the content of NiMo alloy powder in the slurry is 500 mg/mL. And then sprayed on one side of the membrane layer.
(4) And carrying out hot-pressing treatment on the diaphragm layer sprayed with the anode slurry and the cathode slurry for 15min at the temperature of 120 ℃ under the pressure of 20 MPa. And washing the diaphragm subjected to hot pressing with pure water to remove the residual pore-forming agent.
(5) Repeating the steps (2) to (4) for 3 times, wherein when the anode catalyst layer slurry is prepared, the mass ratio of the ammonium bicarbonate/NiCo double metal hydroxide catalyst is gradually increased from 5:100 to 10:100 to 20:100 (the mass of NiCo double metal hydroxide catalyst in the slurry is unchanged, the above mass ratio is achieved by adjusting the mass of ammonium bicarbonate), the ammonium bicarbonate/NiMo alloy catalyst ratio is increased from 8:100 to 20:100, and the third to 40:100 (the mass of NiMo alloy catalyst in the slurry is unchanged, the above mass ratio is achieved by adjusting the mass of ammonium bicarbonate) when formulating the cathode slurry. The aperture of the integrated composite membrane is gradually increased from inside to outside in the catalyst layers on the two sides.
(6) And respectively hot-pressing an 80-mesh stainless steel conductive net and an 80-mesh nickel net on two sides of the hydrogen evolution cathode catalyst layer and the anode catalyst layer, wherein the hot-pressing temperature is 160 ℃, the hot-pressing pressure is 30MPa, and the hot-pressing time is 15 min. Finally, an integrated composite membrane of electron conduction, electrocatalytic cathodic hydrogen evolution, anodic oxidation and ion conduction is formed, wherein the average pore diameter of the membrane layer is about 30nm, the average pore diameter of the anodic catalyst layer is about 120nm, and the average pore diameter of the hydrogen evolution cathodic catalyst layer is about 300 nm.
The integrated composite diaphragm prepared by the embodiment is used for an alkaline water electrolysis hydrogen production electrolytic cell with the effective diameter of 100mm, the electrolyte is 10 percent potassium hydroxide solution added with 0.5M of glycerol, the electrolysis temperature is 50 ℃, and the applied current density is 4000A/M 2 The voltage of the single-chamber cell is only 1.73V, the hydrogen production current efficiency is 98.4%, and the anodic oxidation glycerol current efficiency is 91%, so that the performances of low voltage, high current density, hydrogen production by electrolysis and glycerol oxidation coupling are shown.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. An integrated composite membrane is characterized in that the integrated composite membrane is of a sandwich structure and comprises a diaphragm layer, an anode catalysis layer and a hydrogen evolution cathode catalysis layer which are arranged at two sides of the diaphragm layer, an anode conductive net arranged at the outer side of the anode catalysis layer and a cathode conductive net arranged at the outer side of the hydrogen evolution cathode catalysis layer;
the membrane layer is formed by hydrophilic inorganic nano materials and polymers;
the average pore diameters of the hydrogen evolution cathode catalyst layer, the anode catalyst layer and the membrane layer are in the following relation: the average pore diameter of the hydrogen evolution cathode catalytic layer is larger than the average pore diameter of the anode catalytic layer is larger than the average pore diameter of the diaphragm layer; the pore diameters of the anode catalyst layer and the hydrogen evolution cathode catalyst layer are gradually increased from inside to outside;
the meshes of the anode conductive net are larger than the average pore diameter of the anode catalytic layer, and the meshes of the cathode conductive net are larger than the average pore diameter of the hydrogen evolution cathode catalytic layer;
the anode catalyst layer is prepared by attaching anode slurry to one side of the diaphragm and then performing hot pressing; the components of the anode slurry comprise an anode catalyst, a polymer and a pore-forming agent;
the hydrogen evolution cathode catalyst layer is prepared by attaching cathode slurry to the other side of the diaphragm and then performing hot pressing; the cathode slurry comprises components of a hydrogen evolution cathode catalyst, a polymer and a pore-forming agent.
2. The integrated composite membrane of claim 1, wherein the hydrophilic inorganic nanomaterial comprises ZrO 2 、WO 2 、TiO 2 And Y 2 O 3 One or more of the above; the thickness of the membrane layer is less than or equal to 500 mu m, and the average pore diameter inside the membrane layer is 10 nm-300 nm.
3. The integrated composite membrane of claim 1, wherein the anode catalyst comprises RuO 2 、IrO 2 And one or more of non-noble metal oxides, hydroxides or phosphides; the thickness of the anode catalyst layer is 10-600 mu m, and the average pore diameter inside the anode catalyst layer is 50-800 nm.
4. The integrated composite membrane of claim 1, wherein the hydrogen evolution cathode catalyst comprises one or more of elements of Pt, Ru, Pd and Ir, alloys thereof, and elements, alloys, phosphides and nitrides of Ni, Co, Mo, Cr and Cu; the thickness of the hydrogen evolution cathode catalyst layer is 10-600 mu m, and the internal average pore diameter range is 80-2000 nm.
5. The integrated composite membrane of claim 1, wherein the mass ratio of the anode catalyst, the polymer and the pore-forming agent in the anode slurry is 100 (10-50) to (5-40); the mass ratio of the hydrogen evolution cathode catalyst, the polymer and the pore-forming agent in the cathode slurry is 100 (10-50) to 8-60; and the pore-forming agent content in the anode slurry is lower than that in the cathode slurry.
6. The integrated composite film according to claim 1, wherein the pore-forming agent is a thermally decomposable pore-forming agent or a water-soluble pore-forming agent.
7. The integrated composite membrane of claim 2, wherein the polymers used in the separator, anode slurry and cathode slurry independently comprise one or more of polytetrafluoroethylene, polyphenylene sulfide, polysulfone, polyvinylidene fluoride and carboxymethylcellulose.
8. The integrated composite membrane according to claim 1, wherein the anode conductive mesh and the cathode conductive mesh are independently a carbon fiber mesh, a nickel mesh, a stainless steel mesh or a titanium mesh, and the mesh aperture of the anode conductive mesh and the cathode conductive mesh is independently 10-500 μm.
9. A method for preparing the integrated composite membrane according to any one of claims 1 to 8, characterized by comprising the following steps:
(1) mixing an anode catalyst, a polymer, a pore-forming agent and a solvent to obtain anode slurry, and attaching the anode slurry to one side of a diaphragm layer; mixing a hydrogen evolution cathode catalyst, a polymer, a pore-forming agent and a solvent to obtain cathode slurry, and attaching the cathode slurry to the other side of the diaphragm layer;
(2) sequentially carrying out hot pressing and water washing on the diaphragm layer attached with the anode slurry and the cathode slurry;
(3) repeating the steps (1) - (2) for a plurality of times, and in the repeating process, according to the repeating sequence, the mass ratio of the pore-forming agent to the anode catalyst in the anode slurry is sequentially increased, and the mass ratio of the pore-forming agent to the hydrogen evolution cathode catalyst in the cathode slurry is sequentially increased; after the repetition is finished, an anode catalyst layer and a hydrogen evolution cathode catalyst layer are obtained on two sides of the membrane;
(4) and hot-pressing an anode conductive net on the surface of the anode catalytic layer, and hot-pressing a cathode conductive net on the surface of the hydrogen evolution cathode catalytic layer to obtain the integrated composite membrane.
10. The use of the integrated composite membrane according to any one of claims 1 to 8 or the integrated composite membrane prepared by the preparation method according to claim 9 in alkaline hydrolysis hydrogen production.
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