CN109524687A - A kind of slurry and preparation method of gradient microporous configuration anode support - Google Patents

A kind of slurry and preparation method of gradient microporous configuration anode support Download PDF

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CN109524687A
CN109524687A CN201811175673.5A CN201811175673A CN109524687A CN 109524687 A CN109524687 A CN 109524687A CN 201811175673 A CN201811175673 A CN 201811175673A CN 109524687 A CN109524687 A CN 109524687A
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anode
slurry
layer
parts
presoma
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CN109524687B (en
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陈长城
李隆
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Xian University of Architecture and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/8807—Gas diffusion layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8817—Treatment of supports before application of the catalytic active composition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Fuel Cell (AREA)
  • Inert Electrodes (AREA)

Abstract

The present invention provides the slurries and preparation method of a kind of gradient microporous configuration anode support, based on parts by weight, be prepared from the following raw materials: anode powder body material is 100 parts, Solvents N-methyl -2-Pyrrolidone is 100~160 parts, binder polyether sulfone is 1~3 part, polyethylene of dispersing agent pyrrolidones is 20~40 parts, and pore creating material starch or graphite are 2~10 parts.Gradient microporous configuration anode support made from the slurry is three-decker, from the inside to the outside successively includes the uniform internal layer of anodic porous, anode finger-like porous layer and anodic porous external uniform layer.Anode slurry of the invention can obtain the anode support of three-decker by infusion process, and make the available quantitative control of the porosity of the anode support of three-decker.The anode-supported physical efficiency of three-decker ensures the effective fast transport of fuel, reduces the concentration polarization of gas transport resistance.

Description

A kind of slurry and preparation method of gradient microporous configuration anode support
Technical field
The invention belongs to green energy resource/electrochemical fields, are related to micro-pipe solid oxide fuel battery system, and in particular to A kind of slurry and preparation method of gradient microporous configuration anode support.
Background technique
Solid oxide fuel cell (Solid Oxide Fuel Cell, abbreviation SOFC) have high-energy conversion efficiency, The advantages that structure of whole solid state, pollution-free and pluralities of fuel gas extensive adaptability, be one kind need not move through Thermal Cycling will Chemical energy is directly translated into efficient, the environmentally friendly energy conversion system of electric energy.
Solid oxide fuel cell is usually made of anode, electrolyte and cathode, and electrode (including anode and cathode) rises Gas catalysis decompose, the effect of electric current transmission, thin dense electrolyte layer plays conductive oxonium ion and proton, and isolation combustion The effect of material and oxidizing gas.Solid oxide fuel cell can indicate are as follows: anode (fuel electrodes) | electrolyte | cathode (air Pole).
The support electrode of solid oxide fuel cell can be anode, cathode or electrolyte, and support electrode needs one Fixed mechanical strength, it is therefore desirable to certain thickness.Electrolyte needs avoid reacting with electrode, it is necessary to compact structure, There are biggish ohmic internal resistances in battery system, so electrolyte usually requires thickness as thin as possible.Therefore, soild oxide The support electrode of fuel cell is usually anode or cathode.
For ideal solid oxide fuel cell, support electrode that there is unsymmetric structure, such as gradient pore configuration.Gradient Pore structure is from the electrode surface far from electrolyte side to the entire section top electrode porosity of close bath surface and hole Diameter size gradually decreases.In this way, lower in the electrode porosity near effecting reaction active region, there may be more Active position, and as support body portion electrode porosity reduce gas transport resistance enough, can be effectively reduced due to Concentration polarization phenomenon caused by gas transport.Currently, gradient pore configuration preparation method main screen print process, the tape casting, freezing The tape casting and dry-pressing formed method etc. can prepare the electrode structure of multilayer different aperture.
The configuration of solid oxide fuel cell can be mainly divided into flat, tubular type, bushing type and corrugated etc., at present Structure type is mainly flat and tubular type.Tubular solid oxide fuel cell (Tubular Solid Oxide Fuel Cell, abbreviation T-SOFC) have battery work area larger, it does not need to seal between monocell, it can be using the gold of low cost The advantages that belonging to as current collection material.Due to tubular solid oxide fuel cell, the length of caliber and current channel is determined The internal resistance of battery, longer current channel result in the reduction of the power of battery and efficiency, therefore, reduce the size of battery unit (" miniaturization ") is a kind of mode of effective enhancing fuel battery performance, that is, reduces the diameter of cell support pipe.According to tubular type Solid oxide fuel cell supports the size of pipe diameter, and tubular solid oxide fuel cell is divided into the big tubular type of the first generation- Solid oxide fuel cell (caliber >=20mm), the small tubular solid oxide fuel cell of the second generation-(5mm < caliber < 20mm and the third generation-micro-pipe solid oxide fuel cell (caliber≤5mm).Big tubular cells are by porous electrode, electrolyte It is formed with connector, strut body electrode is mostly extrusion forming, and EVD is respectively adopted in electrolyte and connector and plasma spraying method exists It is deposited on electrode.Small tubular cells mainly use the extrusion molding and the preparation of slurry coating processes of low cost.
Micro-pipe solid oxide fuel cell (Micro Tubular Solid Oxide Fuel Cell, abbreviation MT- SOFC) due to low running temperature, excellent heat resistanceheat resistant cycle performance, quick start ability and higher volumetric power density Etc. advantages, become a kind of future thrust of solid oxide fuel cell.Micro-pipe solid oxide fuel cell automobile, The fields such as communication, aerospace vehicle, ships, sentry post, beacon, hospital, school, illumination and advertisement tool has been widely used, market It has a extensive future.
With the reduction of cell diameter and the increase of number of batteries, electrode active area increases significantly in unit volume. However, the pressure difference for being used for transmission fuel gas also sharp increases after battery size is less than 0.1mm.Therefore, in order to obtain Higher volumetric power density, micro-pipe solid oxide fuel cell diameter is generally between 0.5mm~5.0mm.
Currently, silk screen print method, the tape casting, freezing the tape casting and dry-pressing formed method etc. are only capable of being applied to preparation method letter Single slab construction solid oxide fuel cell, and preparation process is more complicated, the period is long, can't prepare tubular type (packet Include micro-pipe) solid oxide fuel cell.
The method of tubular type (including micro-pipe) solid oxide fuel cell mainly includes plastic mass extrusion forming, Leng Dengjing The methods of molded, injection forming, gel injection-moulding and dip coating.These methods, which are all only capable of preparation, has uniform distribution of pores The support electrode of tubular type (including micro-pipe) solid oxide fuel cell can not achieve the system such as gradient pore structured support electrode It is standby, therefore, the performance of micro-pipe solid oxide fuel cell is limited, output power density is not able to satisfy the need of market application still It asks, seriously restricts the functionization of micro-pipe solid oxide fuel cell.
For this purpose, a kind of method for having researcher to use inversion of phases-sintering, positive development is micro- for preparation asymmetric apertures gap structure New process (the Tan little Yao of pipe solid oxide fuel cell；Zhao Zihang；Liu Xu；Chen Zongpeng；Wang Chen；Zhang Min micro-tubular solid oxygen Compound fuel cell asymmetric compound anode and preparation method thereof Chinese patent 201210401826.X, 2012), by non-right Claim gel environment spinning technique, obtains the micro-pipe solid oxygen of the double-deck unsymmetric structure of porous electrolyte layer supporting anodes thin layer Compound fuel cell.However, there are 3 major defects for battery system described in above-mentioned patent: (A) supporter is electrolyte: for The mechanical strength of the entire battery system of guarantee, electrolyte need sufficiently large thickness, necessarily cause to exist very in battery system Big ohmic internal resistance, so that the output power density of battery system reduces；(B) electrolyte is porous structure: the electricity of porous structure Solution matter layer is necessarily difficult to realize the effect of isolation fuel and oxidizing gas, so that the open-circuit voltage of battery system reduces；(C) anode Porosity quantitative control is not implemented: qualitative porosity necessarily causes fuel in the accumulation (fuel reacted not in time) of anode Or lack and (run out of gas), so that the output power density of battery system is unstable.
Summary of the invention
In view of the above shortcomings of the prior art with defect, the purpose of the present invention is to provide a kind of gradient microporous configuration anodes The slurry and preparation method of supporter solve the low technical problem of the output power density of battery system in the prior art.
In order to solve the above-mentioned technical problem, the application, which adopts the following technical scheme that, is achieved:
A kind of slurry of gradient microporous configuration anode support is prepared from the following raw materials based on parts by weight: anode powder Material is 100 parts, and Solvents N-methyl -2-Pyrrolidone is 100~160 parts, and binder polyether sulfone is 1~3 part, the poly- second of dispersing agent Alkene pyrrolidone is 20~40 parts, and pore creating material starch or graphite are 2~10 parts.
The present invention also has following technical characteristic:
Gradient microporous configuration anode support made from the slurry is three-decker, from the inside to the outside successively includes anode Porous uniform internal layer, anode finger-like porous layer and anodic porous external uniform layer.
The porosity of the uniform internal layer of the anodic porous is 24%~34%；The hole of the anode finger-like porous layer Rate is 37%~63%；The porosity of anodic porous external uniform layer is 18%~36%.
The uniform internal layer of the anodic porous with a thickness of 18~33 μm, the anode finger-like porous layer with a thickness of 115~235 μm, the anodic porous external uniform layer with a thickness of 12~42 μm.
The present invention gives a kind of preparation method of gradient microporous configuration anode support, and this method is using as described above The slurry of gradient microporous configuration anode support.
This method specifically includes following steps；
Anode slurry is placed in vacuum degasser, under the action of vacuum pump, the air in anode slurry is through vacuum pump Exhaust pipe excludes container, and vacuum degree of vessel reaches 5 × 10-2Bar~1 × 10-1Bar is kept for 30~60 minutes, sufficiently removes sun Air in the slurry of pole；
Anode slurry after vacuum degassing is placed in the rustless steel container for cleaning drying, by anode mold closed at one end In anode slurry after immersing vacuum degassing, stablize 6~12 seconds, then vertically propose anode mold, anode presoma is made；
Coagulant is placed in anode presoma phase conversion reaction device, anode presoma is immediately placed on 10 in coagulant~ 15 minutes, so that phase conversion reaction sufficiently occurs for the anode slurry and coagulant on anode presoma, repeat the process 4~10 It is secondary, then anode presoma is vertically proposed from coagulant；
Anode presoma after abundant phase conversion reaction is 12~24 hours dry in dry air, form dry sun Pole presoma.By dry anode presoma with 2~5 DEG C of min-1Rate is warming up to 1000~1200 DEG C, keeps the temperature 2~6 hours Sintering obtains anode support.
Compared with prior art, the present invention beneficial has the technical effect that
(I) anode slurry of the invention can obtain the anode support of three-decker by infusion process, and make three The available quantitative control of porosity of the anode support of layer structure.The anode-supported physical efficiency of three-decker ensures that fuel is effective Fast transport reduces the concentration polarization of gas transport resistance.
(II) the available quantitative control of the porosity of anode support of the invention further ensures that fuel is effectively quick It transports, reduces the concentration polarization of gas transport resistance, the interfacial polarization resistance (Rp) of battery system can be reduced, improve battery system The output power density of system.
Detailed description of the invention
Fig. 1 is the schematic diagram of the section structure of fuel cell system of the present invention.
Fig. 2 is the external structure schematic diagram of fuel cell system of the present invention.
The meaning of each label in figure are as follows: 1- air intake duct, 2- anode support, 3- electrolyte layer, 4- cathode, 5- anode increase Strong layer, the uniform internal layer of 6- anodic porous, 7- anode finger-like porous layer, 8- anodic porous external uniform layer.
Explanation is further explained in detail to particular content of the invention below in conjunction with drawings and examples.
Specific embodiment
In the present invention, anode support and anode enhancement layer are the supporter of battery system, fuel gas H2By supporter Inside enters anode internal layer, is transported into finger-like porous structure by the fine-porous of internal layer, reaches anode enhancement layer；Anode enhancing Layer is the electrochemical reaction region of battery system, and the Lattice Oxygen ion capture of anode enhancement layer transports the proton of arrival, releases Electronics e-, the interface of diffusion arrival anode enhancement layer and electrolyte layer loses the H of proton+It is transported with by cathode by electrolyte layer The O of arrival2-In conjunction with oxidation reaction occurs, reaction product H is generated2O。
Electrolyte layer is the separation layer of battery system, for two sides atmosphere H to be isolated2And O2Direct contact, and with rotate jump The mode of moving carries out conduction ion O2-Transport.
Cathode is the conduction ion O of battery system2-Generation layer, oxygen molecule are dissociated and are charged, and are anode by electrolyte layer Enhancement layer provides the conduction ion O of reaction2-。
Fuel cell system working principle of the invention is as follows:
Oxygen molecule O2It adsorbs, is dissociated in cathode, oxygen molecule O in the outer surface of cathode2It is reduced into oxonium ion O2-；Oxygen from Sub- O2-The interface for reaching cathode and electrolyte layer is spread or transported under the driving of draught head, is transported under the driving of difference in chemical potential By electrolyte layer, the interface of electrolyte layer and anode enhancement layer is reached；Meanwhile fuel H is isolated in electrolyte layer2And oxygen molecule O2Directly chemically react；Oxonium ion O2-It spreads or transports under the driving of difference in chemical potential and reach anode enhancement layer, anode increases The proton H at the interface of strong layer and anode-It spreads or transports under the driving of difference in chemical potential and reach anode enhancement layer, oxonium ion O2-With Proton H-Chemical bonding reaction occurs in anode enhancement layer and generates hydrone H2O (gaseous state).Fuel hydrogen molecule H2In draught head The inner surface for reaching anode, hydrogen molecule H are spread or transported under driving2Arrival anode is transported by the uniform internal layer of anodic porous Finger-like porous layer.In diffusion or transport process, hydrogen molecule H2It is adsorbed and is dissociated into proton H-, and discharge electronics e-.Proton H- It spreads or transports under the driving of difference in chemical potential and reach anodic porous external uniform layer, electronics e-The outer of cathode is reached by external circuit Surface.Meanwhile hydrone H2O (gaseous state) transports discharge battery system by anode.
The three layers of anode support and anode enhancement layer of battery system of the invention act synergistically, and can ensure that fuel is effective Fast transport, reduces the concentration polarization of gas transport resistance, and can effectively improve the active site of effecting reaction active region, will be positive The fuel fast reaction of pole supporter conveying realizes fuel " zero inventory ", collaboration improves the output power density of battery system.
Anode enhancement layer of the invention can effectively improve the active site of effecting reaction active region, and anode support is conveyed Fuel fast reaction, realize fuel " zero inventory ".
The electrolyte layer of battery system of the invention is very fine and close, and without the crack of any perforation, aperture or other are visible Defect, the theoretical value that the open-circuit voltage of battery system is calculated close to Nernst equation.Electrolyte layer very thin thickness can reduce Ohmic internal resistance (the R of battery systemΩ), so that the output power density of battery system gets a promotion.
Specific embodiments of the present invention are given below, it should be noted that the invention is not limited to implement in detail below Example, all equivalent transformations made on the basis of the technical solutions of the present application each fall within protection scope of the present invention.
Embodiment 1:
The present embodiment provides a kind of fuel cell system of high-output power density, from the inside to the outside includes: air intake duct 1, sun Pole supporter 2, electrolyte layer 3 and cathode 4 further include anode enhancement layer 5, and the anode enhancement layer 5 is located at anode support 2 Between electrolyte layer 3；
The anode support 2 is three-decker, is successively referred to from the inside to the outside including the uniform internal layer 6 of anodic porous, anode Shape porous layer 7 and anodic porous external uniform layer 8；
Air intake duct 1, anode support 2, anode enhancement layer 5, electrolyte layer 3 and the cathode 4 sequentially coaxially contacts cloth If.
The preparation method of the fuel cell system of the high-output power density of the present embodiment, wherein the anode-supported Body is made of anode slurry, and the anode enhancement layer is made of anode enhancement layer suspension；The electrolyte layer is by being electrolysed Matter layer suspension is made；The cathode is made of cathode slurry.
Specifically includes the following steps:
Step 1: the preparation of anode support:
Anode slurry is placed in vacuum degasser, under the action of vacuum pump, the air in anode slurry is through vacuum pump Exhaust pipe excludes container, and vacuum degree of vessel reaches 5 × 10-2Bar~1 × 10-1Bar is kept for 30~60 minutes, sufficiently removes sun Air in the slurry of pole；
Anode slurry after vacuum degassing is placed in the rustless steel container for cleaning drying, by anode mold closed at one end In anode slurry after immersing vacuum degassing, stablize 10 seconds, then vertically propose anode mold, anode presoma is made；
Coagulant is placed in anode presoma phase conversion reaction device, anode presoma is immediately placed in coagulant 10 points Clock repeats the process 6 times, then will so that phase conversion reaction sufficiently occurs for the anode slurry and coagulant on anode presoma Anode presoma is slowly vertical from coagulant to be proposed；
Anode presoma after abundant phase conversion reaction is 12~24 hours dry in dry air, form dry sun Pole presoma.By dry anode presoma with 2~5 DEG C of min-1Rate is warming up to 1000~1200 DEG C, keeps the temperature 2~6 hours Sintering obtains anode support.
Step 2: the preparation of anode enhancement layer:
By anode enhancement layer suspension be added ball mill in, with the rate of 30 cycle per minute clocks to anode enhancement layer suspension into Row ball milling continuous ball milling 24~48 hours, so that anode powder body material is fully dispersed in Polymer Solution, is formed uniformly, surely Fixed anode enhancement layer suspension；
Uniform and stable anode enhancement layer suspension is placed in anode enhancement layer dip forming preparing device, lifting is passed through Anode is immersed in anode enhancement layer suspension, stablizes 5 seconds, then vertically propose anode by the adjusting of controller, repeats the mistake Journey 4 times, anode is made | anode enhancement layer presoma；
By anode obtained | anode enhancement layer presoma is 24 hours dry in dry air, is made and is attached with anode increasing The anode of the drying of strong layer | anode enhancement layer presoma.
Step 3: the preparation of electrolyte layer:
Electrolyte suspension is added in ball mill, ball milling is carried out to electrolyte suspension with the rate of 60 cycle per minute clocks, even Continuous ball milling 24~48 hours, form uniform and stable electrolyte suspension；
Uniform and stable electrolyte suspension is placed in electrolyte layer dip forming preparing device, lifting controller is passed through Adjusting, by anode | anode enhancement layer presoma immerse electrolyte suspension in, stablize 5 seconds, then by anode | anode enhancing Layer | electrolyte precursor slowly, vertically proposes, repeats the process 4 times；
By the anode after dip forming | anode enhancement layer | electrolyte precursor is 24 hours dry in dry air, is formed Dry anode | anode enhancement layer | electrolyte precursor.By anode | anode enhancement layer | electrolyte precursor is with 10~15 DEG C min-1Rate is warming up to 1400 DEG C, keeps the temperature 2~4 hours and is sintered, and electrolyte layer is made.
Step 4: the preparation of cathode:
Cathode slurry is prepared using brush coating process in anode with hairbrush | anode enhancement layer | electrolyte outer surface；
By anode | anode enhancement layer | electrolyte | cathode presoma is with 3~5 DEG C of min-1Rate is warming up to 1100~1150 DEG C, it keeps the temperature 2~4 hours and is sintered, cathode is made, obtain the fuel cell system of high-output power density.
Wherein:
The anode slurry is prepared from the following raw materials based on parts by weight: anode powder body material is 100 parts, solvent N- N-methyl-2-2-pyrrolidone N is 130 parts, and binder polyether sulfone A300 is 1 part, and polyethylene of dispersing agent pyrrolidones is 33 parts, pore-creating Agent starch or graphite are 6 parts.
The anode enhancement layer suspension is prepared from the following raw materials based on parts by weight: anode powder body material is 100 Part, Solvents N-methyl -2-Pyrrolidone is 100 parts, and surfactant triethanolamine is 5 parts, polyethylene of dispersing agent pyrrolidones It is 20 parts.
The electrolyte layer suspension is prepared from the following raw materials based on parts by weight: electrolyte layer powder body material is 100 parts, solvent 2- butanone is 160 parts, and surfactant triethanolamine is 5 parts, and binder polyvinyl butyral is 12 parts, is increased Moulding agent dibutyl phthalate is 4 parts, and lubricant polyethylene glycol is 3 parts.
The cathode slurry is prepared from the following raw materials based on parts by weight: anode powder body material is 100 parts, solvent third Ketone is 60 parts, and dispersing agent azodicarbonamide is 100 parts.
Anode powder body material is that nickel oxide and barium stablize yttrium ytterbium doped cerium oxide zirconium oxide, yttria-stabilized zirconia, samarium The mixture of doped cerium oxide or gadolinium doped-ceria ceramic electrolyte, the weight ratio of the two are 55:45, diameter of particle 0.5 ~5 μm.
Coagulant is dehydrated alcohol.
Binder is polyether sulfone, and number-average molecular weight is 30,000.
Dispersing agent is polyvinylpyrrolidone, and number-average molecular weight is 200,000, density: 1.144g/cm3。
Binder polyvinyl butyral, number-average molecular weight are 30,000~50,000.Density 1.08g/cm3。
Lubricant polyethylene glycol, number-average molecular weight 6000.
Starch is selected from one of tapioca and potato starch, and the density of graphite is 2.25g/cm3。
In fuel cell system manufactured in the present embodiment, the porous uniform internal layer 6 of anode support with a thickness of 20 μm, hole Rate is 30%；Anode finger-like porous layer 7 with a thickness of 160 μm, porosity 50%；Anodic porous external uniform layer 8 with a thickness of 20 μm, porosity 30%；Anode enhancement layer 5 with a thickness of 60 μm, porosity 30%；Electrolyte 3 with a thickness of 12 μm, hole Gap rate is 2%；Cathode 4 with a thickness of 30 μm, porosity 30%.
Fuel cell system manufactured in the present embodiment, with humidification (H2O gas concentration about 3v%) pure hydrogen (purity 99.99%) As fuel, air is as oxidant, and in 750 DEG C and 600 DEG C, peak power density is respectively 1.05Wcm2With 0.70W·cm2, open-circuit voltage is respectively 0.98V and 1.02V, Ohmic resistance (RΩ) it is respectively 0.10 Ω cm2With 0.30 Ω cm2, Interfacial polarization resistance (Rp) it is respectively 0.03 Ω cm2With 0.21 Ω cm2。
Embodiment 2: anode-supported body thickness increases
The present embodiment provides a kind of fuel cell system of high-output power density, and the system structure and embodiment 1 are basic It is identical.
The preparation method of the fuel cell system of the high-output power density of the present embodiment is substantially the same manner as Example 1, area It is not only that step 1 difference.
Step 1: the preparation of anode support:
Anode slurry is placed in vacuum degasser, under the action of vacuum pump, the air in anode slurry is through vacuum pump Exhaust pipe excludes container, and vacuum degree of vessel reaches 5 × 10-2Bar~1 × 10-1Bar is kept for 30~60 minutes, sufficiently removes sun Air in the slurry of pole；
Anode slurry after vacuum degassing is placed in the rustless steel container for cleaning drying, by anode mold closed at one end In anode slurry after immersing vacuum degassing, stablize 15 seconds, then vertically propose anode mold, anode presoma is made；
Coagulant is placed in anode presoma phase conversion reaction device, anode presoma is immediately placed in coagulant 12 points Clock repeats the process 10 times, then will so that phase conversion reaction sufficiently occurs for the anode slurry and coagulant on anode presoma Anode presoma is slowly vertical from coagulant to be proposed；
Anode presoma after abundant phase conversion reaction is 12~24 hours dry in dry air, form dry sun Pole presoma.By dry anode presoma with 2~5 DEG C of min-1Rate is warming up to 1000~1200 DEG C, keeps the temperature 2~6 hours Sintering obtains anode support.
Step 2: the preparation of anode enhancement layer: identical as the step of embodiment 1 two.
Step 3: the preparation of electrolyte layer: identical as the step of embodiment 1 three.
Step 4: the preparation of cathode: identical as the step of embodiment 1 four.
Wherein:
The anode slurry is identical as the anode slurry of embodiment 1.
The anode enhancement layer suspension is identical as the anode enhancement layer suspension of embodiment 1.
The electrolyte layer suspension is identical as the electrolyte layer suspension of embodiment 1.
The cathode slurry is identical as the cathode slurry of embodiment 1.
The raw material used in the present embodiment and raw material used in Example 1 are all the same.
In fuel cell system manufactured in the present embodiment, the porous uniform internal layer 6 of anode support with a thickness of 33 μm, hole Rate is 28%；Anode finger-like porous layer 7 with a thickness of 235 μm, porosity 48%；Anodic porous external uniform layer 8 with a thickness of 42 μm, porosity 30%；Anode enhancement layer 5 with a thickness of 60 μm, porosity 30%；Electrolyte 3 with a thickness of 12 μm, hole Gap rate is 2%；Cathode 4 with a thickness of 30 μm, porosity 30%.
Fuel cell system manufactured in the present embodiment, with humidification (H2O gas concentration about 3v%) pure hydrogen (purity 99.99%) As fuel, air is as oxidant, and in 750 DEG C and 600 DEG C, peak power density is respectively 1.00Wcm2With 0.64W·cm2, open-circuit voltage is respectively 0.98V and 1.02V, Ohmic resistance (RΩ) it is respectively 0.10 Ω cm2With 0.30 Ω cm2, Interfacial polarization resistance (Rp) it is respectively 0.10 Ω cm2With 0.40 Ω cm2。
Embodiment 3: anode-supported body thickness is reduced
The present embodiment provides a kind of fuel cell system of high-output power density, and the system structure and embodiment 1 are basic It is identical.
The preparation method of the fuel cell system of the high-output power density of the present embodiment is substantially the same manner as Example 1, area It is not only that step 1 difference.
Step 1: the preparation of anode support:
Anode slurry is placed in vacuum degasser, under the action of vacuum pump, the air in anode slurry is through vacuum pump Exhaust pipe excludes container, and vacuum degree of vessel reaches 5 × 10-2Bar~1 × 10-1Bar is kept for 30~60 minutes, sufficiently removes sun Air in the slurry of pole；
Anode slurry after vacuum degassing is placed in the rustless steel container for cleaning drying, by anode mold closed at one end In anode slurry after immersing vacuum degassing, stablize 10 seconds, then vertically propose anode mold, anode presoma is made；
Coagulant is placed in anode presoma phase conversion reaction device, anode presoma is immediately placed in coagulant 10 points Clock repeats the process 4 times, then will so that phase conversion reaction sufficiently occurs for the anode slurry and coagulant on anode presoma Anode presoma is slowly vertical from coagulant to be proposed；
Anode presoma after abundant phase conversion reaction is 12~24 hours dry in dry air, form dry sun Pole presoma.By dry anode presoma with 2~5 DEG C of min-1Rate is warming up to 1000~1200 DEG C, keeps the temperature 2~6 hours Sintering obtains anode support.
Step 2: the preparation of anode enhancement layer: identical as the step of embodiment 1 two.
Step 3: the preparation of electrolyte layer: identical as the step of embodiment 1 three.
Step 4: the preparation of cathode: identical as the step of embodiment 1 four.
Wherein:
The anode slurry is identical as the anode slurry of embodiment 1.
The anode enhancement layer suspension is identical as the anode enhancement layer suspension of embodiment 1.
The electrolyte layer suspension is identical as the electrolyte layer suspension of embodiment 1.
The cathode slurry is identical as the cathode slurry of embodiment 1.
The raw material used in the present embodiment and raw material used in Example 1 are all the same.
In fuel cell system manufactured in the present embodiment, the porous uniform internal layer 6 of anode support with a thickness of 18 μm, hole Rate is 33%；Anode finger-like porous layer 7 with a thickness of 115 μm, porosity 50%；Anodic porous external uniform layer 8 with a thickness of 12 μm, porosity 30%；Anode enhancement layer 5 with a thickness of 60 μm, porosity 30%；Electrolyte 3 with a thickness of 12 μm, hole Gap rate is 2%；Cathode 4 with a thickness of 30 μm, porosity 30%.
Fuel cell system manufactured in the present embodiment, with humidification (H2O gas concentration about 3v%) pure hydrogen (purity 99.99%) As fuel, air is as oxidant, and in 750 DEG C and 600 DEG C, peak power density is respectively 1.01Wcm2With 0.65W·cm2, open-circuit voltage is respectively 0.98V and 1.02V, Ohmic resistance (RΩ) it is respectively 0.10 Ω cm2With 0.30 Ω cm2, Interfacial polarization resistance (Rp) it is respectively 0.03 Ω cm2With 0.20 Ω cm2。
Embodiment 4:
The present embodiment provides a kind of fuel cell system of high-output power density, and the system structure and embodiment 1 are basic It is identical.
The preparation method of the fuel cell system of the high-output power density of the present embodiment is substantially the same manner as Example 1:
Step 1: the preparation of anode support: identical as the step of embodiment 1 one.
Step 2: the preparation of anode enhancement layer: identical as the step of embodiment 1 two.
Step 3: the preparation of electrolyte layer: identical as the step of embodiment 1 three.
Step 4: the preparation of cathode: identical as the step of embodiment 1 four.
Wherein:
The anode enhancement layer suspension is identical as the anode enhancement layer suspension of embodiment 1.
The electrolyte layer suspension is identical as the electrolyte layer suspension of embodiment 1.
The cathode slurry is identical as the cathode slurry of embodiment 1.
The raw material used in the present embodiment and raw material used in Example 1 are all the same.
The present embodiment and the difference of embodiment 1 are only in that the anode slurry of the anode slurry and embodiment 1 is not Together.Anode slurry in the present embodiment is prepared from the following raw materials based on parts by weight: anode powder body material is 100 parts, solvent N-methyl-2-pyrrolidone is 160 parts, and binder polyether sulfone A300 is 3 parts, and polyethylene of dispersing agent pyrrolidones is 40 parts, is made Hole agent starch or graphite are 10 parts.
In fuel cell system manufactured in the present embodiment, the porous uniform internal layer 6 of anode support with a thickness of 15 μm, hole Rate is 34%；Anode finger-like porous layer 7 with a thickness of 125 μm, porosity 63%；Anodic porous external uniform layer 8 with a thickness of 14 μm, porosity 36%；Anode enhancement layer 5 with a thickness of 58 μm, porosity 32%；Electrolyte 3 with a thickness of 12 μm, hole Gap rate is 2%；Cathode 4 with a thickness of 30 μm, porosity 30%.
Fuel cell system manufactured in the present embodiment, with humidification (H2O gas concentration about 3v%) pure hydrogen (purity 99.99%) As fuel, air is as oxidant, and in 750 DEG C and 600 DEG C, peak power density is respectively 0.92Wcm2With 0.58W·cm2, open-circuit voltage is respectively 0.96V and 1.00V, Ohmic resistance (RΩ) it is respectively 0.10 Ω cm2With 0.30 Ω cm2, Interfacial polarization resistance (Rp) it is respectively 0.06 Ω cm2With 0.27 Ω cm2。
Embodiment 5:
The present embodiment provides a kind of fuel cell system of high-output power density, and the system structure and embodiment 1 are basic It is identical.
The preparation method of the fuel cell system of the high-output power density of the present embodiment is substantially the same manner as Example 1:
Step 1: the preparation of anode support: identical as the step of embodiment 1 one.
Step 2: the preparation of anode enhancement layer: identical as the step of embodiment 1 two.
Step 3: the preparation of electrolyte layer: identical as the step of embodiment 1 three.
Step 4: the preparation of cathode: identical as the step of embodiment 1 four.
Wherein:
The anode enhancement layer suspension is identical as the anode enhancement layer suspension of embodiment 1.
The electrolyte layer suspension is identical as the electrolyte layer suspension of embodiment 1.
The cathode slurry is identical as the cathode slurry of embodiment 1.
The raw material used in the present embodiment and raw material used in Example 1 are all the same.
The present embodiment and the difference of embodiment 1 are only in that the anode slurry of the anode slurry and embodiment 1 is not Together.Anode slurry in the present embodiment is prepared from the following raw materials based on parts by weight: anode powder body material is 100 parts, solvent N-methyl-2-pyrrolidone is 100 parts, and binder polyether sulfone A300 is 1 part, and polyethylene of dispersing agent pyrrolidones is 20 parts, is made Hole agent starch or graphite are 2 parts.
In fuel cell system manufactured in the present embodiment, the porous uniform internal layer 6 of anode support with a thickness of 26 μm, hole Rate is 24%；Anode finger-like porous layer 7 with a thickness of 180 μm, porosity 37%；Anodic porous external uniform layer 8 with a thickness of 26 μm, porosity 18%；Anode enhancement layer 5 with a thickness of 63 μm, porosity 28%；Electrolyte 3 with a thickness of 12 μm, hole Gap rate is 2%；Cathode 4 with a thickness of 30 μm, porosity 30%.
Fuel cell system manufactured in the present embodiment, with humidification (H2O gas concentration about 3v%) pure hydrogen (purity 99.99%) As fuel, air is as oxidant, and in 750 DEG C and 600 DEG C, peak power density is respectively 0.95Wcm2With 0.60W·cm2, open-circuit voltage is respectively 0.98V and 1.01V, Ohmic resistance (RΩ) it is respectively 0.10 Ω cm2With 0.30 Ω cm2, Interfacial polarization resistance (Rp) it is respectively 0.12 Ω cm2With 0.38 Ω cm2。
Embodiment 6: anode support porosity increases
The present embodiment provides a kind of fuel cell system of high-output power density, and the system structure and embodiment 1 are basic It is identical.
The preparation method of the fuel cell system of the high-output power density of the present embodiment is substantially the same manner as Example 1, area It is not step 1 difference.
Step 1: the preparation of anode support:
Anode slurry is placed in vacuum degasser, under the action of vacuum pump, the air in anode slurry is through vacuum pump Exhaust pipe excludes container, and vacuum degree of vessel reaches 5 × 10-2Bar~1 × 10-1Bar is kept for 30~60 minutes, sufficiently removes sun Air in the slurry of pole；
Anode slurry after vacuum degassing is placed in the rustless steel container for cleaning drying, by anode mold closed at one end In anode slurry after immersing vacuum degassing, stablize 12 seconds, then vertically propose anode mold, anode presoma is made；
Coagulant is placed in anode presoma phase conversion reaction device, anode presoma is immediately placed in coagulant 15 points Clock repeats the process 9 times, then will so that phase conversion reaction sufficiently occurs for the anode slurry and coagulant on anode presoma Anode presoma is slowly vertical from coagulant to be proposed；
Anode presoma after abundant phase conversion reaction is 12~24 hours dry in dry air, form dry sun Pole presoma.By dry anode presoma with 2~5 DEG C of min-1Rate is warming up to 1000~1200 DEG C, keeps the temperature 2~6 hours Sintering obtains anode support.
Step 2: the preparation of anode enhancement layer: identical as the step of embodiment 1 two.
Step 3: the preparation of electrolyte layer: identical as the step of embodiment 1 three.
Step 4: the preparation of cathode: identical as the step of embodiment 1 four.
Wherein:
The anode enhancement layer suspension is identical as the anode enhancement layer suspension of embodiment 1.
The electrolyte layer suspension is identical as the electrolyte layer suspension of embodiment 1.
The cathode slurry is identical as the cathode slurry of embodiment 1.
The raw material used in the present embodiment and raw material used in Example 1 are all the same.
The present embodiment and the difference of embodiment 1 also reside in, and the anode slurry is different from the anode slurry of embodiment 1. The anode slurry is identical as the anode slurry of embodiment 4.
In fuel cell system manufactured in the present embodiment, the porous uniform internal layer 6 of anode support with a thickness of 18 μm, hole Rate is 34%；Anode finger-like porous layer 7 with a thickness of 155 μm, porosity 63%；Anodic porous external uniform layer 8 with a thickness of 15 μm, porosity 36%；Anode enhancement layer 5 with a thickness of 58 μm, porosity 32%；Electrolyte 3 with a thickness of 12 μm, hole Gap rate is 2%；Cathode 4 with a thickness of 30 μm, porosity 30%.
Fuel cell system manufactured in the present embodiment, with humidification (H2O gas concentration about 3v%) pure hydrogen (purity 99.99%) As fuel, air is as oxidant, and in 750 DEG C and 600 DEG C, peak power density is respectively 0.94Wcm2With 0.59W·cm2, open-circuit voltage is respectively 0.96V and 1.00V, Ohmic resistance (RΩ) it is respectively 0.10 Ω cm2With 0.30 Ω cm2, Interfacial polarization resistance (Rp) it is respectively 0.08 Ω cm2With 0.29 Ω cm2。
Embodiment 7: anode support porosity is reduced
The present embodiment provides a kind of fuel cell system of high-output power density, and the system structure and embodiment 1 are basic It is identical.
The preparation method of the fuel cell system of the high-output power density of the present embodiment is substantially the same manner as Example 1, area It is not step 1 difference.
Step 1: the preparation of anode support:
Anode slurry is placed in vacuum degasser, under the action of vacuum pump, the air in anode slurry is through vacuum pump Exhaust pipe excludes container, and vacuum degree of vessel reaches 5 × 10-2Bar~1 × 10-1Bar is kept for 30~60 minutes, sufficiently removes sun Air in the slurry of pole；
Anode slurry after vacuum degassing is placed in the rustless steel container for cleaning drying, by anode mold closed at one end In anode slurry after immersing vacuum degassing, stablize 6 seconds, then vertically propose anode mold, anode presoma is made；
Coagulant is placed in anode presoma phase conversion reaction device, anode presoma is immediately placed in coagulant 15 points Clock repeats the process 5 times, then will so that phase conversion reaction sufficiently occurs for the anode slurry and coagulant on anode presoma Anode presoma is slowly vertical from coagulant to be proposed；
Anode presoma after abundant phase conversion reaction is 12~24 hours dry in dry air, form dry sun Pole presoma.By dry anode presoma with 2~5 DEG C of min-1Rate is warming up to 1000~1200 DEG C, keeps the temperature 2~6 hours Sintering obtains anode support.
Step 2: the preparation of anode enhancement layer: identical as the step of embodiment 1 two.
Step 3: the preparation of electrolyte layer: identical as the step of embodiment 1 three.
Step 4: the preparation of cathode: identical as the step of embodiment 1 four.
Wherein:
The anode enhancement layer suspension is identical as the anode enhancement layer suspension of embodiment 1.
The electrolyte layer suspension is identical as the electrolyte layer suspension of embodiment 1.
The cathode slurry is identical as the cathode slurry of embodiment 1.
The raw material used in the present embodiment and raw material used in Example 1 are all the same.
The present embodiment and the difference of embodiment 1 also reside in, and the anode slurry is different from the anode slurry of embodiment 1. The anode slurry is identical as the anode slurry of embodiment 5.
In fuel cell system manufactured in the present embodiment, the porous uniform internal layer 6 of anode support with a thickness of 22 μm, hole Rate is 24%；Anode finger-like porous layer 7 with a thickness of 168 μm, porosity 37%；Anodic porous external uniform layer 8 with a thickness of 24 μm, porosity 18%；Anode enhancement layer 5 with a thickness of 63 μm, porosity 28%；Electrolyte 3 with a thickness of 12 μm, hole Gap rate is 2%；Cathode 4 with a thickness of 30 μm, porosity 30%.
Fuel cell system manufactured in the present embodiment, with humidification (H2O gas concentration about 3v%) pure hydrogen (purity 99.99%) As fuel, air is as oxidant, and in 750 DEG C and 600 DEG C, peak power density is respectively 0.95Wcm2With 0.60W·cm2, open-circuit voltage is respectively 0.98V and 1.01V, Ohmic resistance (RΩ) it is respectively 0.10 Ω cm2With 0.30 Ω cm2, Interfacial polarization resistance (Rp) it is respectively 0.11 Ω cm2With 0.36 Ω cm2。
It was found from from above-described embodiment 1 to embodiment 7: fuel electricity can be greatly reduced in the anode-supported body thickness of (A) appropriateness The interfacial polarization resistance (Rp) of cell system.(B) appropriate anode-supported body thickness larger can improve the defeated of fuel cell system Power density out.(C) the interfacial polarization resistance (Rp) of fuel cell system can be greatly reduced in appropriate anode layer porosity. (D) appropriate anode layer porosity, can greatly improve the output power density of fuel cell system.(E) in identical anode Under slurry conditions, the thickness of anode support bigger (including the uniform internal layer of anodic porous, anode finger-like porous layer and anodic porous External uniform layer), the interfacial polarization resistance (Rp) of fuel cell system is bigger.(F) in essentially identical anode support (including sun Extremely porous uniform internal layer, anode finger-like porous layer and anodic porous external uniform layer) under thickness condition, the porosity of anode support Too big or too small, the interfacial polarization resistance (Rp) of fuel cell system can all become larger.
Embodiment 8:
The present embodiment provides a kind of slurry of gradient microporous configuration anode support, based on parts by weight, by following raw material Be made: anode powder body material is 100 parts, and Solvents N-methyl -2-Pyrrolidone is 130 parts, and binder polyether sulfone A300 is 1 part, Polyethylene of dispersing agent pyrrolidones is 33 parts, and pore creating material starch or graphite are 6 parts.
The raw material used in the present embodiment and raw material used in Example 1 are all the same.
Embodiment 9:
The present embodiment provides a kind of gradient microporous configuration anode support, and the anode support 2 is three-decker, by It is interior to outside successively include the uniform internal layer 6 of anodic porous, anode finger-like porous layer 7 and anodic porous external uniform layer 8.
The gradient microporous configuration anode support of the present embodiment, is made of the slurry in embodiment 8.
Embodiment 10:
The present embodiment provides a kind of preparation method of gradient microporous configuration anode support, and this method is using in embodiment 8 Slurry；This method specifically includes the following steps:
Anode slurry is placed in vacuum degasser, under the action of vacuum pump, the air in anode slurry is through vacuum pump Exhaust pipe excludes container, and vacuum degree of vessel reaches 5 × 10-2Bar~1 × 10-1Bar is kept for 30~60 minutes, sufficiently removes sun Air in the slurry of pole.
Anode slurry after vacuum degassing is placed in the rustless steel container for cleaning drying, by anode mold closed at one end In anode slurry after immersing vacuum degassing, stablize 10 seconds, then vertically propose anode mold, anode presoma is made.
Coagulant is placed in anode presoma phase conversion reaction device, anode presoma is immediately placed in coagulant 10 points Clock repeats the process 6 times, then will so that phase conversion reaction sufficiently occurs for the anode slurry and coagulant on anode presoma Anode presoma is slowly vertical from coagulant to be proposed.
Anode presoma after abundant phase conversion reaction is 12~24 hours dry in dry air, form dry sun Pole presoma.By dry anode presoma with 2~5 DEG C of min-1Rate is warming up to 1000~1200 DEG C, keeps the temperature 2~6 hours Sintering obtains anode support.
Comparative example 1: without anode enhancement layer
This comparative example provides a kind of fuel cell system, and the system structure is different from embodiment 1, and difference is only that this comparison Without anode enhancement layer in the fuel cell system of example.
The preparation method of the fuel cell system of the high-output power density of the present embodiment is substantially the same manner as Example 1, area It is not only that the preparation process of no anode enhancement layer.
Step 1: the preparation of anode support: identical as the step of embodiment 1 one.
Step 2: the preparation of electrolyte layer: identical as the step of embodiment 1 three.
Step 3: the preparation of cathode: identical as the step of embodiment 1 four.
Wherein:
Anode slurry is identical as the anode slurry of embodiment 1.
Electrolyte layer suspension is identical as the electrolyte layer suspension of embodiment 1.
Cathode slurry is identical as the cathode slurry of embodiment 1.
The raw material used in this comparative example and raw material used in Example 1 are all the same.
In fuel cell system manufactured in the present embodiment, the porous uniform internal layer 6 of anode support with a thickness of 20 μm, hole Rate is 30%；Anode finger-like porous layer 7 with a thickness of 160 μm, porosity 50%；Anodic porous external uniform layer 8 with a thickness of 20 μm, porosity 30%；Electrolyte 3 with a thickness of 12 μm, porosity 2%；Cathode 4 with a thickness of 30 μm, porosity is 30%.
The fuel cell system of this comparative example preparation, with humidification (H2O gas concentration about 3v%) pure hydrogen (purity 99.99%) As fuel, air is as oxidant, and in 750 DEG C and 600 DEG C, peak power density is respectively 0.90Wcm2With 0.56W·cm2, open-circuit voltage is respectively 0.96V and 1.00V, Ohmic resistance (RΩ) it is respectively 0.10 Ω cm2With 0.30 Ω cm2, Interfacial polarization resistance (Rp) it is respectively 0.03 Ω cm2With 0.20 Ω cm2。
Comparative example 2: anode support is double-layer structure
This comparative example provides a kind of fuel cell system, and the system structure is different from embodiment 1, and difference is only that this comparison The fuel cell system Anodic supporter of example is double-layer structure, i.e., only the uniform internal layer of anodic porous and anode finger-like are porous Layer.
The preparation method of the fuel cell system of the high-output power density of the present embodiment is substantially the same manner as Example 1, area It is not only that the anode slurry in step 1 is different.
Step 1: the preparation of anode support: essentially identical with the step of embodiment 1 one.
Step 2: the preparation of anode enhancement layer: identical as the step of embodiment 1 two.
Step 3: the preparation of electrolyte layer: identical as the step of embodiment 1 three.
Step 4: the preparation of cathode: identical as the step of embodiment 1 four.
Wherein:
Anode enhancement layer suspension is identical as the anode enhancement layer suspension of embodiment 1.
Electrolyte layer suspension is identical as the electrolyte layer suspension of embodiment 1.
Cathode slurry is identical as the cathode slurry of embodiment 1.
The raw material used in this comparative example and raw material used in Example 1 are all the same.
Anode slurry in this comparative example is prepared from the following raw materials based on parts by weight: anode powder body material is 100 parts, Solvents N-methyl -2-Pyrrolidone is 110 parts, and binder polyether sulfone is 2 parts, and polyethylene of dispersing agent pyrrolidones is 25 parts, is made Hole agent starch or graphite are 2 parts.
In the fuel cell system of this comparative example preparation, the porous uniform internal layer 6 of anode support with a thickness of 22 μm, hole Rate is 26%；Anode finger-like porous layer 7 with a thickness of 172 μm, porosity 33%；Anode enhancement layer 5 with a thickness of 60 μm, hole Gap rate is 30%；Electrolyte 3 with a thickness of 12 μm, porosity 2%；Cathode 4 with a thickness of 30 μm, porosity 30%.
The fuel cell system of this comparative example preparation, with humidification (H2O gas concentration about 3v%) pure hydrogen (purity 99.99%) As fuel, air is as oxidant, and in 750 DEG C and 600 DEG C, peak power density is respectively 0.96Wcm2With 0.61W·cm2, open-circuit voltage is respectively 0.98V and 1.00V, Ohmic resistance (RΩ) it is respectively 0.10 Ω cm2With 0.30 Ω cm2, Interfacial polarization resistance (Rp) it is respectively 0.11 Ω cm2With 0.36 Ω cm2。
Comparative example 3: anode support is for double-layer structure and without anode enhancement layer
This comparative example provides a kind of fuel cell system, and the system structure is different from embodiment 1, and difference is only that this comparison The fuel cell system Anodic supporter of example is double-layer structure, i.e., only the uniform internal layer of anodic porous and anode finger-like are porous Layer, and without anode enhancement layer.
The preparation method of the fuel cell system of the high-output power density of the present embodiment is substantially the same manner as Example 1, area It is not that the anode slurry in step 1 is different, and the preparation process without anode enhancement layer.
Step 1: the preparation of anode support: essentially identical with the step of embodiment 1 one.
Step 2: the preparation of electrolyte layer: identical as the step of embodiment 1 three.
Step 3: the preparation of cathode: identical as the step of embodiment 1 four.
Wherein:
Electrolyte layer suspension is identical as the electrolyte layer suspension of embodiment 1.
Cathode slurry is identical as the cathode slurry of embodiment 1.
The raw material used in this comparative example and raw material used in Example 1 are all the same.
Anode slurry in this comparative example is identical as comparative example 2.
In the fuel cell system of this comparative example preparation, the porous uniform internal layer 6 of anode support with a thickness of 22 μm, hole Rate is 26%；Anode finger-like porous layer 7 with a thickness of 172 μm, porosity 33%；Electrolyte 3 with a thickness of 12 μm, porosity It is 2%；Cathode 4 with a thickness of 30 μm, porosity 30%.
The fuel cell system of this comparative example preparation, with humidification (H2O gas concentration about 3v%) pure hydrogen (purity 99.99%) As fuel, air is as oxidant, and in 750 DEG C and 600 DEG C, peak power density is respectively 0.82Wcm2With 0.51W·cm2, open-circuit voltage is respectively 0.97V and 1.00V, Ohmic resistance (RΩ) it is respectively 0.10 Ω cm2With 0.30 Ω cm2, Interfacial polarization resistance (Rp) it is respectively 0.12 Ω cm2With 0.37 Ω cm2。
It was found from above-described embodiment 1 and comparative example 1 to 3: (A) (including anodic porous is uniform in identical anode support Internal layer, anode finger-like porous layer and anodic porous external uniform layer) under the conditions of thickness and porosity, anode enhancement layer can be mentioned substantially The output power density of high fuel cell system.(B) in identical anode support (including the uniform internal layer of anodic porous, anode Finger-like porous layer and anodic porous external uniform layer) under the conditions of thickness and porosity, anode enhancement layer does not increase fuel cell system Interfacial polarization resistance (the R of systemp).(C) identical anode support (including the uniform internal layer of anodic porous and anode finger-like it is porous Layer) under the conditions of thickness and porosity, anode enhancement layer can greatly improve the output power density of fuel cell system.(D) exist Under the conditions of identical anode support (including the uniform internal layer of anodic porous and anode finger-like porous layer) thickness and porosity, anode Enhancement layer does not increase the interfacial polarization resistance (R of fuel cell systemp).(E) in identical electrolyte and cathode thickness and hole Under the conditions of gap rate, three-decker anode support can the larger output power density for improving fuel cell system.(F) identical Electrolyte and cathode thickness and porosity under the conditions of, three-decker anode support can ensure the effective fast transport of fuel, The concentration polarization for reducing gas transport resistance, is greatly reduced the interfacial polarization resistance (R of fuel cell systemp)。

Claims (6)

1. a kind of slurry of gradient microporous configuration anode support, which is characterized in that based on parts by weight, by following raw material system At: anode powder body material is 100 parts, and Solvents N-methyl -2-Pyrrolidone is 100~160 parts, and binder polyether sulfone is 1~3 Part, polyethylene of dispersing agent pyrrolidones is 20~40 parts, and pore creating material starch or graphite are 2~10 parts.
2. the slurry of gradient microporous configuration anode support as described in claim 1, which is characterized in that the slurry is made Gradient microporous configuration anode support be three-decker, from the inside to the outside successively include that the uniform internal layer of anodic porous (6), anode refer to Shape porous layer (7) and anodic porous external uniform layer (8).
3. the slurry of gradient microporous configuration anode support as claimed in claim 2, which is characterized in that the anodic porous The porosity of uniform internal layer is 24%~34%；The porosity of the anode finger-like porous layer is 37%~63%；Anode is more The porosity of hole external uniform layer is 18%~36%.
4. the slurry of gradient microporous configuration anode support as claimed in claim 2, which is characterized in that the anodic porous Uniform internal layer with a thickness of 18~33 μm, the anode finger-like porous layer with a thickness of 115~235 μm, the anode is more Hole external uniform layer with a thickness of 12~42 μm.
5. a kind of preparation method of gradient microporous configuration anode support, which is characterized in that this method use as claim 1 to The slurry of gradient microporous configuration anode support described in 4 any claims.
6. preparation method as claimed in claim 5, which is characterized in that this method specifically includes following steps；
Anode slurry is placed in vacuum degasser, under the action of vacuum pump, the air in anode slurry is through vacuum pump discharges Pipe excludes container, and vacuum degree of vessel reaches 5 × 10-2Bar~1 × 10-1Bar keeps 30~60 minutes, sufficiently removing anode slurry Air in material；
Anode slurry after vacuum degassing is placed in the rustless steel container for cleaning drying, anode mold closed at one end is immersed In anode slurry after vacuum degassing, stablize 6~12 seconds, then vertically propose anode mold, anode presoma is made；
Coagulant is placed in anode presoma phase conversion reaction device, anode presoma is immediately placed in coagulant 10~15 points Clock, so that phase conversion reaction sufficiently occurs for the anode slurry and coagulant on anode presoma, repeatedly the process 4~10 times, so Anode presoma is vertically proposed from coagulant afterwards；
Anode presoma after abundant phase conversion reaction is 12~24 hours dry in dry air, before forming dry anode Drive body.By dry anode presoma with 2~5 DEG C of min-1Rate is warming up to 1000~1200 DEG C, keeps the temperature 2~6 hours and is sintered, Obtain anode support.
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