CN109638298A - A kind of structure-integrated method for preparing membrane electrode of 3D - Google Patents
A kind of structure-integrated method for preparing membrane electrode of 3D Download PDFInfo
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
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- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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Abstract
The invention belongs to hydrogen fuel cell and SPE water electrolysis technical field, in particular to it is a kind of can be with the technology of preparing of the matched high-performance membrane electrode of a variety of current collectings with 3D structure.Specially utilize the method for CCM of the slot die extruded type coating technique preparation without membrane structure.The process passes through extrusion coated three layers of (cathode catalysis layer, the film and anode catalyst layer) structure for successively constructing membrane electrode of slit, by being continuously cast, stacking gradually, coating forms three-dimensional space membrane electrode (3D-MEA), this is a kind of manufacturing method of expansible, based on curtain coating coating technology three-dimensional membrane electrode (3D-MEA).Process optimization membrane electrode three phase boundary structure, reduces the interface resistance at different interfaces；It avoids using expensive diaphragm, and membrane electrode performance is made to have the promotion of the order of magnitude；In addition, preparation process is simple, it is low in cost, while preparation time is shortened, it is conducive to large scale preparation.
Description
Technical field
The invention belongs to hydrogen fuel cell and SPE water electrolysis technical field, in particular to a kind of 3D knot without additional diaphragm
Structure integrated film electrode preparation method.
Background technique
Membrane electrode (Membrane Electrode Assemblies, MEA) is Proton Exchange Membrane Fuel Cells and SPE electricity
Multiphase mass transfer is carried out in solution slot and electrochemical reaction place, performance decide the work of SPE electrolytic cell or fuel cell
Performance, service life and cost.Membrane electrode is mainly prepared by catalyst, proton exchange membrane and its solution, gas diffusion layers,
Preparation process is always the core technology of electrochemical field.Study high-performance, long-life and low-cost membrane electrode technology of preparing pair
It is had a very important significance in quickening SPE electrolytic cell and commercializing fuel cells process.Efficient Pt base catalyst is being developed, is being adjusted
The exposure crystal face (111) of whole Pt nanocrystal prepares more metallic nano crystals of the alloy of Pt, nucleocapsid, branch or inhomogeneous structure
Body is conducive to improve film electricity with metal cluster, molecule, ion, organic or inorganic compound Modified Platinum nano grain surface etc.
Pole electrochemical reaction activity, the active platinum base of high quality is porous/and hollow structure nanoparticle catalyst is concerned.It is urged in improvement
In terms of the durability of agent, focuses primarily upon and research and develop high-graphitized carbon material (such as carbon fiber, carbon pipe, graphite are dilute) conduct
Pt based catalyst carrier.But only improve the cost of SPE electrolytic cell or fuel cell and durable from the raw material such as catalyst angle
Property problem is also far from enough, because the membrane electrode by catalyst preparation must also take into account electrochemical reaction three phase boundary and electricity
The mass transfer microchannel of son, proton, gas and water etc. is multifactor, could obtain best power generation performance, therefore, membrane electrode material and system
The integrated and innovation of standby technique prepares high-performance membrane electrode significant.
General Electric Company the 1960s is using platinum black as catalyst, and membrane electrode Pt carrying capacity was more than at that time
4mg/cm2；In the early 1990s, Los Alamos National Laboratories, the U.S. (LANL) replace platinum using pallium-on-carbon (Pt/C)
After black ink (Ink) manufacturing process, so that the Pt carrying capacity of membrane electrode exponentially reduces, which generally adopts so far
With；After 2000, low temperature, all solid state membrane electrode technology are graduallyd mature, so that using the electrochemical appliance entering surface of membrane electrode
To the stage of Demonstration Application.Develop along with membrane electrode decades, membrane electrode technology experienced several generations innovation, can be generally divided into
Pressure sintering, CCM (Catalyst Coating Membrane) method and ordering membrane electrode three types, as shown in table 1.First
Generation is that the catalyst pulp for mixing catalyst, PTFE emulsion or Nafion solution with alcohols solvent is prepared into gas diffusion layers
Form electrode on the Multifunctional layered of (GDL, Gas Diffusion Layer), then by proton exchange membrane be clipped in two layers of electrode it
Between carry out hot pressing at membrane electrode, i.e. pressure sintering, this method Catalytic Layer is thicker, and pt utilization is low；The second generation is to lead to Catalytic Layer
Cross transfer printing or direct spraying method be prepared on proton exchange membrane two sides, formed CCM three in one membreane electrode, this method Catalytic Layer compared with
Thin (generally at 10 μm or less), CCM preparation process has been widely adopted, and is the commercialization preparation method of current mainstream.Due to
The exchange current density (10 of H/Pt-3A.cm-2) it is O/Pt (10-9A.cm-2) about 1000 times, and electrochemical reaction process is different, because
This membrane electrode Anodic and cathode often use asymmetric design, if cathode Pt carrying capacity is usually the several times of anode carrying capacity, simultaneously
Nafion content, pore-size, additional functional layer are different in anode and cathode, to reach promotion oxygen reduction reaction, prevent water
It floods and dries up, reduce concentration polarization, increase endurance quality, improve the effect of generated output density and reduce Pt dosage.
Table 1, membrane electrode classification
Table 1 MEA Classification
With the development of nanometer filamentary material, people attempt to be introduced into membrane electrode catalytic layer, mainly include nanotube
Material, catalyst nano line and high proton conductive nano fiber.The introducing of nanometer filamentary material, has expedited the emergence of ordering membrane electrode
Concept.Ordering membrane electrode can take into account ultrathin electrodes and structure control, possess huge unit volume reactivity area and
The new kink characteristics that pore structure is mutually communicated, outstanding advantages include: the transmission of (1) high-efficiency three-phase；(2) high Pt utilization rate；(3) resistance to
Long property is improved.In recent years, ordering membrane electrode is also in phase of basic research.
Develop from the fabricating technology of membrane electrode, SPE electrolytic cell or fuel cell tradition membrane electrode assembly can lead to
A variety of distinct methods are crossed to prepare.Catalyst dispersion is applied directly on film or dispersion is coated in first on applique substrate, then
Catalyst layer is transferred on film, and resulting membrane electrode is also referred to as catalyst coat film (CCM).Another common method
It is to be applied directly to dispersion on porous gas diffusion layer (GDL), then carries out hot pressing with film, ultimately form MEA.However,
Either CCM method or pressure sintering, these methods are all come using commercial membrane material compound.In contrast, Ding et al. is studied
One kind spraying catalyst on GDL and forms gas-diffusion electrode, and it is molten that ionomer is then cast in gas-diffusion electrode
Liquid forms film, finally catalyst is dispersed in the Directly depositing membrane electrode technology of preparing of second electrode is formed on film can be to avoid
The commodity in use film and technology of preparing for freely adjusting proton conductor thickness degree is of great significance.Electrochemical research shows the party
Method ratio sprays catalyst ink on product film can get better performance.Klingele et al. describes a kind of direct film deposition
(DMD) technology wherein the direct ink jet printing of ionomer solution or is sprayed on the GDL of catalyst cladding, replaces common
Product film, then assembling film coated anode and membrane coat cathode form MEA.This technology can not only reduce interface resistance, also
It can change film thickness, this is of great significance for research membrane electrode interface resistance.Membrane electrode, SPE are prepared using DMD technology
The performance of electrolytic cell or fuel cell can significantly improve
Summary of the invention
The present invention proposes a kind of method that 3D integration prepares CCM membrane electrode without diaphragm.Constituting membrane electrode in this method
Three layers (cathode, film and anode) pass sequentially through continuous curtain coating, stacked together, are formed three-dimensional space membrane electrode (3D-MEA).The
One coating is coated on transfer substrate, so that entire membrane electrode is then stripped from transfer substrate.Then every layer of ingredient is adjusted
With proportion, it is attached to later layer in previous sublayer and forms a film and do not dissolve.This is that one kind is expansible, is based on curtain coating coating skill
Three-dimensional membrane electrode (3D-MEA) technology of preparing of art, as shown in Figure 1.Each layer is applied directly in preceding layer, it can be effective
Each layer of formation, performance, composition and thickness are controlled, and reduces interface resistance, additional gas diffusion layers support is not needed and applies
Layer, and allow the unrestricted choice gas diffusion layers in different electrochemical appliances operates.This method is not only SPE water electrolysis,
And high activity 3D-MEA preparation method is provided for the electrochemical energies conversion equipment such as fuel cell, innovate membrane electrode knot
Structure optimizes membrane electrode technology of preparing.
The specific technical solution of the present invention is as follows.
A kind of structure-integrated method for preparing membrane electrode of 3D, comprising the following steps:
(1) prepared by anode catalyst layer: configuration anode catalyst layer slurry first, and catalyst, deionized water, Nafion is molten
The mixing such as liquid, dispersion solvent and molding additive are fully dispersed；Then, (slot die is cast by slot die
Coating mode) is cast in easily peelable substrate, and drying and moulding, forms anode catalyst layer；
(2) supporting frame adds: placing first layer frame, frame inside dimension and electrochemical appliance at above-mentioned Catalytic Layer edge
Active region it is consistent, be mainly made of polymer material；
(3) prepared by Direct precipitation electrolyte membrane layer: using slot die casting method by high scores such as proton conductor Nafion
Sub- solution is coated on the above-mentioned anode catalyst layer with frame and drying and moulding, forms electrolyte membrane layer, electrolyte membrane layer covering
Entire Catalytic Layer and frame.
(4) another pole (to electrode) Catalytic Layer preparation: progress Catalytic Layer slurry preparation first, by catalyst, deionized water,
Nafion solution, dispersion solvent and molding additive are sufficiently mixed dispersion, then are cast by slot die in above-mentioned electrolyte
In film layer, in the frame of effective coverage, drying and moulding is formed to electrode catalyst layer control coating range；
(5) supporting frame adds: placing second layer frame, frame inside dimension and electrochemical appliance at above-mentioned Catalytic Layer edge
Active region it is consistent, be mainly made of polymer material；Second layer frame and first layer frame are symmetrical, form multiple-layer stand
The membrane electrode of body structure；
(6) above-mentioned multilayered structure membrane electrode is hot-forming under certain temperature and pressure.
(7) membrane electrode after basal layer and hot pressing is removed, forms the 3D membrane electrode of the absolute construction with frame.
It is the easily peelable polymer films such as PTFE film, fluorine element film, fep film, silicon oil membrane that the membrane electrode, which prepares basal layer,；
The cathode and anode catalyst is the electrochemical nano catalyst for meeting application system, as Pt, Ir, Pt/C, Pt are closed
Gold, metal nitrogen C catalyst, MOF, RuO2、IrO2Etc. high activities, polymolecularity electrochemical catalyst.Catalyst quality in slurry
Content is 3~45%.
Proton conductor Nafion concentration is 3~30% in the coating sizing-agent, in slurry Nafion mass content be 20~
80%.
Deionized water quality percentage composition is 0.1~60% in the slurry.
Solvent is volatile to be easy to catalyst dispersion and solvent in the coating sizing-agent, and easily well mixes with other solvents
One of organic matter, such as methanol, ethyl alcohol, isopropanol, propyl alcohol, ether easy volatile solvent or a variety of mixed liquors.
The molding additive is high-viscosity alcohol type organic, such as enanthol, alcohol, butanol, 2- methyl -2- butanol, 2- first
The mixture etc. of one or more of base -1- propyl alcohol.
The supporting frame material is the thermoplastic materials such as PET film, polyester, polyimides, and seal ring thickness is at 5~300 μm.
Coating layer polymer film thickness is not less than 10 μm among the membrane electrode.
The membrane electrode packaging by hot pressing temperature be 100~150 DEG C, pressure be 0.5~50MPa, hot pressing time be 30s~
20min。
Beneficial effects of the present invention:
(1) catalyst and proton conductor are sequentially overlapped by the present invention by way of slot coated is coated on basement membrane, makes
Standby 3D structural stratification deposits stereo film electrode, does not need using additional membrane material, and each interface comes into full contact with, and reduces contact electricity
Resistance, significantly improves membrane electrode performance than traditional membrane electrode, and implementation process is easy to operate, quick, low in cost.
(2) present invention can accurately prepare the film layer for needing thickness, size, it is flexible and efficient, and membrane electrode can with it is various
Current-collecting member well contacts.Catalytic Layer and film form integral structure, substantially reduce interface impedance, and are conducive to ensure membrane electrode knot
Structure stability, prolongs the service life；Also there is good application prospect in electro-catalysis and other catalytic fields.
(3) additional diaphragm material is not needed, combines direct film deposition (DMD) using slot die extruded type coating technique
The integrated solid CCM that method building is made of anode, film layer and cathode.By the way that successively continuously curtain coating and stacking form three layer three
Dimension space, that is, 3D-MEA.First layer is coated on transfer substrate first, so that entire membrane electrode is then shelled from transfer substrate
From.Then successively coating is superimposed other coatings.Need to adjust the ingredient and proportion of every layer of control, to keep the base of coating insoluble
Solution.Each layer is applied directly on other layers, enables us to finally control each layer of formation, performance and composition, and is dropped
Low interfacial resistance.
Detailed description of the invention
Fig. 1 is three-dimensional membrane electrode (3D-MEA) artwork of the method for the present invention preparation.
Fig. 2 is three-dimensional membrane electrode (3D-MEA) electron microscope of the method for the present invention preparation.
Fig. 3 be the method for the present invention preparation 3D membrane electrode compared with conventional film electrode polarization curve figure.
Fig. 4 is 3D membrane electrode and tradition the membrane electrode figure compared with polarization curve in a fuel cell of the method for the present invention preparation.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples.
Embodiment 1:
The preparation of SPE electrolytic cell membrane electrode: cathode catalysis layer slurry is with 46wt% deionized water, 25wt%Nafion solution
(concentration 5%), 9wt% methanol, 9wt%2- methyl-2- butanol, 7wt%Pt/C, 4wt%2- methyl-1-propyl alcohol are prepared, and are used
Above-mentioned slurry is cast on ptfe substrate (PTFE) by desk-top coating machine, and drying and moulding, cathode catalysis layer with a thickness of
20 microns.First layer PET frame, the active region of frame size and 5cm*5cm square are placed at above-mentioned cathode catalysis layer edge
It is consistent, with a thickness of 20 microns.Using Nafion solution (30% concentration) by slot die be applied directly to above-mentioned cathode and
On frame, electrolyte membrane layer is formed, film thickness is 50 microns.Then, by anode slurry (by 22wt% iridium dioxide, 25wt%
Nafion and 53wt%1- enanthol is constituted) preparation is cast in above-mentioned film surface.Anode catalyst layer is formed after drying, it is anode-catalyzed
Thickness is 200 microns, places second layer PET frame at above-mentioned anode catalyst layer edge, symmetrical with first layer frame, frame is thick
Degree is 200 microns, forms the membrane electrode of layer stereo structure；By above-mentioned multilayered structure membrane electrode under 130 DEG C, 0.5MPa pressure
It is hot-forming, and separated with PTFE substrate, form the independent 3D structure SPE water electrolysis hydrogen production membrane electrode for having frame.Film electricity
It is as shown in Figure 2 that pole Electronic Speculum tests cross-section diagram.
Embodiment 2:
3D membrane electrode described in embodiment 1 is made into cathode and anode using two Toray paper (TGP-H-120), and is assembled
It is tested in the electrolytic cell that anode and cathode side has single snake-like flow field.To avoid long-term corrosion, plated in anode flow field
Platinum, cathode flow field are gold-plated.Using silica gel pad hermetic electrolyte pond.Anode-side and cathode side are injected separately into deionized water (R=1M
Ω .cm), flow velocity 35mLmin-1.To avoid the temperature gradient in electrolytic cell, electrolytic cell temperature is adjusted to 80 DEG C, anode
80 DEG C are preheating to the water of cathode two sides.Simultaneously under the conditions of identical material and catalyst loading, using Nafion HP conventional film
Electrode is compared with 3D membrane electrode of the present invention carries out performance.Fig. 3 gives 3D-MEA and conventional film polarization of electrode curve comparison.It is logical
Cross comparing voltage value, it can be seen that 3D membrane electrode of the present invention can obtain higher current density under identical decomposition voltage, such as
Under the decomposition voltage of 1.8V, 3D membrane electrode current density of the present invention reaches 6Acm-2, it is higher than traditional membrane electrode 5Acm-2。
In 7Acm-2Under current density, 3D membrane electrode electrolysis pond efficiency reaches 80%.It is tested simultaneously by accelerated ageing, 3D of the present invention
The durability of membrane electrode has reached 10,000 hours, and the conventional film electrode durability of Nafion HP film is only 2000 hours.
Embodiment 3:
Membrane electrode of fuel batter with proton exchange film preparation: anode catalyst layer slurry is with 3wt% deionized water, 29wt%
Nafion solution (concentration 10%), 50wt% isopropanol, 8wt%2- methyl -2- butanol, 10wt%Pt/C are prepared, and use is desk-top
Above-mentioned slurry is cast on ptfe substrate (PTFE) by coating machine, and drying and moulding, anode catalyst layer are micro- with a thickness of 5
Rice.First layer polyimides frame, the active region of frame size and 10cm*10cm square are placed at above-mentioned cathode catalysis layer edge
Domain is consistent, with a thickness of 5 microns.Using Nafion solution (5% concentration) by slot die be applied directly to above-mentioned cathode and
On frame, electrolyte membrane layer is formed, film thickness is 15 microns.Then, by cathode slurry (by 20wt%Pt/C, 29wt%Nafion
Constituted with 51wt% isopropanol) preparation is cast in above-mentioned film surface.Anode catalyst layer is formed after drying, cathode catalysis thickness is
15 microns, second layer polyimides frame, seal ring thickness symmetrical with first layer frame are placed at above-mentioned cathode catalysis layer edge
It is 15 microns, forms the membrane electrode of layer stereo structure；By above-mentioned multilayered structure membrane electrode in 150 DEG C of temperature and 50MPa pressure
Under it is hot-forming, and separated with PTFE substrate, form the fuel cell membrane electrode of the independent 3D with frame.
Above-mentioned 3D membrane electrode is made into cathode and anode using two Toray paper (TGP-H-60), and be assembled in anode and
Cathode side have single snake-like flow field fuel cell in test.To avoid long-term corrosion, anode flow field platinum plating, cathode flow field plating
Gold.Using silica gel pad sealed cell.Anode-side and cathode side each lead into high-purity hydrogen and air, and metering ratio is respectively as follows: 1.5
With 2.3.Battery operational temperatures are 70 DEG C, and reaction gas humidifies RH 50%, and reaction pressure is normal pressure.Simultaneously in identical material and
Under the conditions of catalyst loading, using traditional membrane electrode of 15 micron membranes of GORE compared with 3D membrane electrode of the present invention carries out performance.Figure
3 give 3D-MEA and conventional film polarization of electrode curve.From maximum power generation, 3D membrane electrode peak power is more than
1W/cm2, the peak power of traditional membrane electrode is only 0.8W/cm2Left and right, performance boost nearly 30%, this shows 3D film electricity of the present invention
Pole preparation method can greatly reduce membrane electrode contact resistance, optimize multiphase mass transfer, to reach high performance target.Lead to simultaneously
Accelerated ageing test is crossed, the durability of 3D membrane electrode of the present invention has reached 20,000 hours, and the conventional film electrode durability of GORE film
Only 1000 hours
Technical solution of the present invention is described in detail in above-described embodiment.It is apparent that the present invention is not limited being retouched
The embodiment stated.Based on the embodiments of the present invention, those skilled in the art can also make a variety of variations accordingly, but appoint
What is equal with the present invention or similar variation shall fall within the protection scope of the present invention.
Claims (11)
1. a kind of structure-integrated method for preparing membrane electrode of 3D, it is characterised in that: the following steps are included:
1) prepared by anode catalyst layer: by catalyst, deionized water, Nafion solution, solvent and molding additive configuration catalysis
Layer slurry is then coated on separation basal layer simultaneously drying and moulding, forms anode catalyst layer；
2) supporting frame adds: first layer frame is placed at the Catalytic Layer edge obtained by step 1), and frame inside dimension and electrochemistry fill
The active region set is consistent；
3) directly film deposition electrolyte film layer preparation: Nafion Polymer Solution is coated on step 2) gains and is dried to
Type, forms electrolyte membrane layer, and electrolyte membrane layer covers entire Catalytic Layer and frame；
4) prepared by cathode catalysis layer: by catalyst, deionized water, Nafion solution, solvent and molding additive configuration catalysis
Layer slurry, is then coated in the electrolyte membrane layer obtained by step 3), and controls in frame, and drying and moulding, shape paired electrode is urged
Change layer；
5) supporting frame adds: second layer frame is placed at the Catalytic Layer edge obtained by step 4), and frame inside dimension and electrochemistry fill
The active region set is consistent；The second layer frame and first layer frame are symmetrical, form the membrane electrode of layer stereo structure；
6) membrane electrode is hot-forming: layer stereo structure membrane electrode obtained by step 5) is hot pressed under certain temperature and pressure
Type is formed with the 3D membrane electrode of supporting frame；
7) it removes basal layer: basal layer is removed, form the layer stereo structure membrane electrode of support frame support.
2. preparation method according to claim 1, it is characterised in that: pass through slit in step 1), step 3) and step 4)
Die head curtain coating mode is coated.
3. preparation method according to claim 1, it is characterised in that: basal layer described in step 1) is PTFE film, fluorine
Plain film, fep film or silicon oil membrane.
4. preparation method according to claim 1, it is characterised in that: step 1) and 4) described in catalyst include Pt,
Ir, Pt/C, Pt alloy, metal nitrogen C catalyst, MOF, RuO2、IrO2Electrochemical catalyst；Catalyst quality contains in the slurry
Amount is 3~45%.
5. preparation method according to claim 1, it is characterised in that: step 1) and 4) described in Nafion solution concentration
It is 20~80% for 3~30%, Nafion mass content.
6. preparation method according to claim 1, it is characterised in that: step 1) and 4) described in deionized water quality content
It is 0.1~60%.
7. preparation method according to claim 1, it is characterised in that: step 1) and 4) described in solvent be methanol, ethyl alcohol,
The mixture of one or more of isopropanol, propyl alcohol, ether.
8. preparation method according to claim 1, it is characterised in that: step 1) and 4) described in molding additive be heptan
The mixture of one or more of alcohol, hexanol, butanol, 2- methyl-2- butanol, 2- methyl-1-propyl alcohol.
9. preparation method according to claim 1, it is characterised in that: step 2) and 5) described in the material of supporting frame be
PET film, polyester or polyimides, the seal ring thickness are 5~300 μm.
10. preparation method according to claim 1, it is characterised in that: coated described in step 1), step 3) and step 4)
Thicknesses of layers be not less than 10 μm.
11. preparation method according to claim 1, it is characterised in that: hot-forming temperature described in step 6) is 100
~150 DEG C, pressure is 0.5~50MPa, and hot pressing time is 30s~20min.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN114400335A (en) * | 2022-01-05 | 2022-04-26 | 海南大学 | Preparation method and device of novel two-dimensional patterned electrode |
| CN114597460A (en) * | 2022-01-17 | 2022-06-07 | 北京化工大学 | Preparation of integrated membrane electrode for reducing interface impedance |
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