CN107732257A - Gradient electrode and solid-oxide battery - Google Patents
Gradient electrode and solid-oxide battery Download PDFInfo
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- CN107732257A CN107732257A CN201711075823.0A CN201711075823A CN107732257A CN 107732257 A CN107732257 A CN 107732257A CN 201711075823 A CN201711075823 A CN 201711075823A CN 107732257 A CN107732257 A CN 107732257A
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8636—Inert electrodes with catalytic activity, e.g. for fuel cells with a gradient in another property than porosity
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
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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
- 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
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8636—Inert electrodes with catalytic activity, e.g. for fuel cells with a gradient in another property than porosity
- H01M4/8642—Gradient in composition
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/1231—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte with both reactants being gaseous or vaporised
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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- 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
Abstract
The invention discloses a kind of gradient electrode and solid-oxide battery, and the gradient electrode is used for solid-oxide fuel cell or solid oxide electrolysis pond, and the reactivity of the gradient electrode is increased along airflow direction with gradient profile.The gradient electrode of the present invention and the solid-oxide fuel cell comprising the gradient electrode or solid oxide electrolysis pond can avoid or effectively reduce in the process of running the electrode polarization performance profile difference along airflow direction, so as to ensure battery operation efficiency and slow down cell decay.
Description
Technical field
The present invention relates to new energy field of batteries, in particular to a kind of gradient electrode and solid-oxide battery.
Background technology
Solid-oxide fuel cell (Solid Oxide Fuel Cells, SOFC) is considered as clean and effective thermoelectricity connection
Most one of ideal source of production, distributed power generation, energy internet etc., the past, America and Japan Ou Deng developed countries threw for over ten years
Enter huge fund research and development.
SOFC typically operates in more than 600 DEG C of high temperature, based on solid oxide electrolysis matter conduction oxonium ion and separates sun
Pole and the reacting gas of negative electrode, electrode reaction use relatively inexpensive transition metal or dilute independent of noble metal catalyst
Native oxide.Another outstanding advantages of SOFC are that suitability of fuel is wide, and hydrogen, carbon monoxide, ammonia, methane etc. can all be used as fuel
Use, and power density is high, and generating efficiency is up to 60%, and cogeneration of heat and power efficiency is up to more than 90%, also with noiseless, nothing
The advantages that pollution, modularization assembling.
On the other hand, above-mentioned battery can carry out contrary operation, i.e., as solid oxide electrolysis pond (Solid Oxide
Electrolysis Cells, SOEC) there is the fuel gas or synthesis gas of higher-value using electrical energy production.For example use SOEC
Electrolysis water prepares pure hydrogen (H2O→H2+1/2O2), or electrolysis carbon dioxide production carbon monoxide (CO2→CO+1/2O2), or
Person's water has the CO-H of extensive chemical industry purposes with the common electrolytic preparation of carbon dioxide2Synthesis gas (H2O+CO2→H2+CO+O2).SOEC can
To dock the new energy such as the wind energy of redundancy and fluctuation, solar energy, for the extensive energy conversion currently needed badly.SOEC's is excellent
Point closes except without using noble metal catalyst, battery cost is low, conversion gas making efficiency is high, can effectively utilize industrial high temperature steam
Key is far below other kinds of electrolysis pool technology also in terms of power consumption, so as to prominent economic advantages.
Above-mentioned SOFC and SOEC are collectively referred to as solid-oxide battery (Solid Oxide Cells, SOC), when it is used as combustion
When expecting cell power generation operation, fuel electrode is anode, and oxygen electrode is negative electrode；When carrying out electrolysis gas as electrolytic cell, just
In turn, fuel electrode is negative electrode, and oxygen electrode is anode.Title during to avoid different operations is obscured, fuel electricity used below
Pole and oxygen electrode refer to two lateral electrodes.
Solid-oxide battery is generally divided into tubular type and flat two kinds of structure types.Tubular solid-state oxide cell seals
Simply, thermal circulation performance is preferable, but afflux has certain difficulty, and equal conditions power density is more much lower than flat.Flat board
Type solid-oxide battery possesses inexpensive mass manufacture advantage because power density is very high, nearly ten years as phase
To the structure type of main flow.
To ensure larger generated output or electrolysis gas yield, the work of every solid-oxide fuel cell/electrolytic cell
Property electrode area (or effective area) is typically at tens to hundreds of square centimeters.The performance of solid-oxide battery depends on electricity
All many reference amounts inside pond, including the structural factor such as thickness of electrode, the porosity, pore-size distribution, and gas, composition, temperature, electric current
The status considerations such as load.Skewness of these parameters in cell plane, can cause the performance difference in cell plane, not only
Overall operational efficiency is influenceed, and is unfavorable for the longtime running life-span of battery.
Existing solid-oxide battery still has improved space in performance.
The content of the invention
In view of the above problems, the solid oxide the invention provides a kind of new gradient electrode and comprising the gradient electrode
Thing fuel cell and solid oxide electrolysis pond.
An embodiment of the invention provides a kind of gradient electrode, and the gradient electrode is used for solid-oxide battery,
And the reactivity of the gradient electrode is increased along airflow direction with gradient profile.
In above-mentioned gradient electrode, the gradient electrode is divided into multiple reactivity regions, and adjacent is described anti-
It is 0-5mm to answer the gap width scope between active region.
In above-mentioned gradient electrode, the gradient profile is smooth type gradient or step gradient.
In above-mentioned gradient electrode, when the gradient profile is step gradient, uniformly included in same stepped area
The catalyst of same particle size, and the particle diameter of at least one of described catalyst catalyst along the airflow direction in different institutes
Staged in stepped area is stated to fall progressively.
It is same comprising the gas transport hole formed by pore creating material in the gradient electrode in above-mentioned gradient electrode
Uniformly include the hole in stepped area, and the density of the hole along the airflow direction in the different stepped regions
Increased in domain with gradient profile.
Alternatively, the gradient electrode is used as fuel electrode or oxygen electrode.
In above-mentioned gradient electrode, the density of the reaction site of the gradient electrode is increased along airflow direction with gradient profile
Add.
In above-mentioned gradient electrode, the reaction site be catalyst and ion conductor support and reacting gas three
Boundary.The quantity of reaction site is embodied by the loading and particle diameter of catalyst.Usually, electrochemical catalysis performance with it is anti-
It is monotone increasing relation to answer bit number of points, and reaction site quantity and catalyst granules particle diameter are dull reduction relation.
In above-mentioned gradient electrode, the catalyst includes multiple catalysts, the loading edge of at least one catalyst
The airflow direction is increased with gradient profile, and remaining catalyst is uniformly distributed along the airflow direction or increased with gradient profile
Add.
The hole formed by pore creating material, and the density edge of the hole are included in above-mentioned electrode, in the electrode
The airflow direction is increased with gradient profile.
Another embodiment of the invention provides a kind of solid-oxide fuel cell, the Solid oxide fuel electricity
It is above-mentioned gradient electrode that pond, which includes at least one of oxygen electrode and fuel electrode, the oxygen electrode and fuel electrode,.
The further embodiment of the present invention provides a kind of solid oxide electrolysis pond, the solid oxide electrolysis Chi Bao
It is above-mentioned gradient electrode to include at least one of oxygen electrode and fuel electrode, the oxygen electrode and fuel electrode.
The reactivity of gradient electrode of the present invention is increased along airflow direction with gradient profile, this novel gradient electrode with
And the solid-oxide battery comprising the gradient electrode can avoid or effectively reduce in the process of running the electrode along airflow direction
Polarization performance distributional difference, so as to ensure battery operation efficiency and slow down cell decay.
Brief description of the drawings
In order to illustrate more clearly of technical scheme, letter will be made to the required accompanying drawing used in embodiment below
Singly introduce, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, therefore be not construed as to the present invention
The restriction of protection domain.In various figures, it is similarly comprised part and uses similar numbering.
Fig. 1 is the schematic cross-section of the solid-oxide fuel cell of prior art.
Fig. 2 is the schematic cross-section of the solid-oxide battery of one embodiment of the present invention.
Fig. 3 is the schematic cross-section of the variation of the solid-oxide battery shown in Fig. 2.
Fig. 4 is the schematic cross-section of the solid-oxide battery of another embodiment of the invention.
Fig. 5 is the schematic cross-section of the variation of the solid-oxide battery shown in Fig. 4.
Fig. 6 is the floor map of an example of the smooth type gradient electrode of the solid-oxide battery of the present invention.
Fig. 7 is the floor map of an example of the step gradient electrode of the solid-oxide battery of the present invention.
Fig. 8 is that the local current densities of an example of the electrode of non-gradient distribution are carried out to simulate calculating and measurement acquisition
Along the gradient distribution map of airflow direction.
Embodiment
Below in conjunction with accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Ground describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Generally exist
The component of the embodiment of the present invention described and illustrated in accompanying drawing can be configured to arrange and design with a variety of herein.Cause
This, the detailed description of the embodiments of the invention to providing in the accompanying drawings is not intended to limit claimed invention below
Scope, but it is merely representative of the selected embodiment of the present invention.Based on embodiments of the invention, those skilled in the art are not doing
The every other embodiment obtained on the premise of going out creative work, belongs to the scope of protection of the invention.
Fig. 1 shows the schematic cross-section of the solid-oxide fuel cell of prior art.Solid-oxide shown in Fig. 1
Fuel cell includes dielectric substrate 1, oxygen electrode layer 2, fuel electrode layer 3, oxygen electrode current collector layer 4 and fuel electrode supporting layer 5.So
And the battery failure shown in existing Fig. 1 is very fast, it is impossible to meet actual use demand well.
Therefore, present inventor is for influenceing battery performance structural factor (such as thickness of electrode, the porosity, aperture point
Cloth etc.) and numerous factor such as status consideration (such as gas, composition, temperature, current capacity etc.) carried out substantial amounts of research.
Final research is found, because the fuel electrode or oxygen electrode of the solid-oxide fuel cell are in electrode plane direction
On structure and composition, identical everywhere in whole cell active area, i.e., fuel electrode side is in whole active area plane
The structure in direction (airflow direction shown in Fig. 1) is consistent everywhere with composition, and oxygen electrode side is in whole active area in-plane
Structure and composition it is also identical everywhere, therefore, existing solid-oxide fuel cell in the process of running, enters with electrode reaction
OK, fuel gas and oxygen progressively consume along airflow direction, and great changes will take place for gas componant or partial pressure meeting.
Because the local polarization resistance of electrode is for the sensitiveness of gas componant, along the electrode polarization of flow field diverse location,
Current density and ohm heating will produce very big difference.Especially under the larger operating condition of total load electric current, this is not
Highly significant is caused larger local attenuation speed difference by uniformity, finally accelerates the failure of battery.
Further say, because effecting reaction thing is gradually diluted along airflow direction by product, reactant partial pressure gradually reduces.
Because battery two-side current collecting body can be approximately equipotentiality body, i.e. the potential of collector is identical everywhere in respective plane.And from air-flow
On swim over to downstream part electromotive force and gradually reduce, this will cause electrode polarization to be become larger along airflow direction, local current densities
Gradually reduce, ohm heating is uneven in battery face and produces transverse current in larger face.Local current densities difference in face, point
Cloth is uneven, and the current density for causing some regions is much higher than into average value, will aggravate battery local attenuation, and then can cause one
Serial Regime during recession promotes, and causes battery to accelerate failure.
Therefore, one embodiment of the invention provides one kind forms gradient components in battery face, along flow field direction
And/or the novel gradient electrode of gradient-structure.Fuel electrode and oxygen electrode may each be the gradient electrode with the structure.This hair
Bright gradient electrode structure or composition make avtive spot density gradually increase along airflow direction, to ensure along under flow field gradual change atmosphere
Electrode polarization performance it is throughout basically identical or difference is smaller, it is above-mentioned so as to solve the problems, such as.
Another embodiment of the present invention provides the solid-oxide fuel cell for including above-mentioned gradient electrode.Due to above-mentioned
The composition and/or micro-structural of gradient electrode are distributed along airflow direction gradient, can avoid or effectively reduce in the process of running along gas
The electrode polarization performance profile difference in direction is flowed, so as to ensure battery operation efficiency and slow down cell decay.
A further embodiment of the invention provides the solid oxide electrolysis pond for including above-mentioned gradient electrode.Due to above-mentioned ladder
The composition and/or micro-structural for spending electrode are distributed along airflow direction gradient, can avoid or effectively reduce in the process of running along air-flow
The electrode polarization performance profile difference in direction, so as to ensure electrolytic cell operational efficiency and slow down electrolytic cell decay.
Solid-oxide battery described below can be used as solid-oxide fuel cell or solid oxide electrolysis pond.Figure
2 be the schematic cross-section of the solid-oxide battery of one embodiment of the present invention.Solid-oxide battery includes dielectric substrate
210th, oxygen electrode layer 220, fuel electrode layer 230, oxygen electrode current collector layer 240 and fuel electrode supporting layer 250.Oxygen electrode layer 220
It is located at the side of dielectric substrate 210 with oxygen electrode current collector layer 240；Fuel electrode layer 230 and fuel electrode supporting layer 250 are positioned at electricity
Solve the opposite side of matter layer 210.Dielectric substrate 210 can be oxygen ion conductor electrolyte, or proton conductor electrolyte.
Fuel electrode supporting layer 250 has the function that mechanical support and transmission electric charge, that is to say, that fuel electrode supports
Layer 250 also functions to the effect of fuel electrode afflux.During using electrode supporting, both sides thickness of electrode can be 10-50 microns, such as
15th, 20,25,30,35,40 or 45 microns, porosity can be 20%-50%, for example, can be 25%, 30%, 35%, 40% or
45%；Oxygen electrode current collector layer thickness can be 10-100 microns, such as can be micro- with 15,20,30,40,50,60,70,80 or 90
Rice, porosity can be 30%-80%, for example, 35%, 40%, 50%, 60%, 70 or 75%.Fuel electrode supports thickness
Degree 0.15-1mm, such as 0.2,0.4,0.6,0.8 or 1.0mm, fuel electrode support layer porosity 30%-70%, such as 35%,
45%th, 55% or 65%.The thickness of dielectric substrate can be 2-20 microns, for example, 5,8,10,12,15 or 18 microns.Electrolysis
The consistency of matter layer is higher than 90%.
As an alternate embodiment, Fig. 3 shows that the section of the variation of the solid-oxide battery shown in Fig. 2 shows
It is intended to.Fig. 3 solid-oxide battery includes dielectric substrate 310, oxygen electrode layer 320, fuel electrode layer 330, oxygen electrode afflux
Layer 340 and fuel electrode supporting layer 350.Unlike the solid-oxide battery shown in Fig. 2, in oxygen electrode layer 320 and electricity
Electrolyte barrier (or electrolyte buffer layer) 310 ' is also included between solution matter layer 310.The effect of electrolyte barrier will be under
Illustrate in text.
Fig. 4 is the schematic cross-section of the solid-oxide battery of another embodiment of the invention.Solid-oxide battery
Including electrolyte-supported layer 410, oxygen electrode layer 420, fuel electrode layer 430, oxygen electrode current collector layer 440 and fuel electrode current collector layer
450.Oxygen electrode layer 420 and oxygen electrode current collector layer 440 are located at the side of electrolyte-supported layer 410；Fuel electrode layer 430 and fuel
Electrode current collecting layer 450 is located at the opposite side of electrolyte-supported layer 410.Dielectric substrate 410 can be oxygen ion conductor electrolyte, or
Person's proton conductor electrolyte.
Different from the embodiment of Fig. 2 and 3, fuel electrode current collector layer 450 is not re-used as supporting layer, but mainly by being electrolysed
Matter supporting layer 410 plays a part of mechanical support.During using electrolyte-supported, both sides thickness of electrode can be preferably 10-50 micro-
Rice, such as 15,20,25,30,35,40 or 45 microns, porosity preferably be 20%-50%, for example, can for 25%, 30%,
35%th, 40% or 45%；Electrode current collecting thickness degree can be preferably 10-100 microns, for example, can with 15,20,30,40,50,60,
70th, 80 or 90 microns, porosity can be preferably 30%-80%, for example, 35%, 40%, 50%, 60%, 70 or 75%.Electricity
The thickness of solution matter layer can be preferably 100-400 microns, for example, 120,150,200,250,300 or 350 microns.Dielectric substrate
Consistency be higher than 90%.
As an alternate embodiment, Fig. 5 shows that the section of the variation of the solid-oxide battery shown in Fig. 4 shows
It is intended to.Fig. 5 solid-oxide fuel cell includes electrolyte-supported layer 510, oxygen electrode layer 520, fuel electrode layer 530, oxygen
Electrode current collecting layer 540 and fuel electrode current collector layer 550.Unlike Fig. 4 solid-oxide battery, in oxygen electrode layer 520
Electrolyte barrier 510 ' is also included between electrolyte-supported layer 510.
Gradient distribution is presented in fuel electrode layer and oxygen electrode layer in Fig. 2 to Fig. 5 in electrode plane, and along each reflexive
Answer reactivity gradient increase on the airflow direction of gas.That is, downstream is from upstream to along electrode reaction gas transport direction, instead
Should activity for gradually increase, so as to effective compensation or offset originally due to constantly being diluted by product along airflow direction reactant,
The problem of electrode polarization impedance becomes larger, local current densities gradually reduce caused by reactant partial pressure gradually reduces.
It should be noted that although in Fig. 2 into Fig. 5, the airflow direction of two electrode layers is consistent, however, two electrodes
Airflow direction can also be different, but electrode graded direction needs to be consistent i.e. with the airflow direction of homonymy
Can.In addition, representing each layer position relationship shown in figure, the thickness proportion between each layer is not represented accurately deliberately.
The gradient profile of fuel electrode layer and oxygen electrode layer in electrode plane in Fig. 2 to Fig. 5 is smooth type gradient.
That is, the reactivity of electrode is smoothly incremented by along airflow direction.Fig. 6 shows the smooth type of the solid-oxide battery of the present invention
The floor map of one example of gradient electrode.
In smooth type gradient electrode, all catalyst particle sizes can be essentially identical, and along the air-flow side
Increase to density (loading, content in other words) gradient of catalyst granules, i.e. the catalyst granules close to air flow inlet region
Density it is minimum, the density close to the catalyst granules in air stream outlet region is maximum.
Alternatively, catalyst can include multiple catalysts, at least one catalyst along airflow direction with
Gradient profile increase, remaining catalyst are uniformly distributed along airflow direction or increased with gradient profile.A kind of for example, catalyst granules
Density (loading, content) identical along airflow direction, the density of remaining catalyst granules increases along airflow direction gradient.
In addition, at least one gradient shape in electrode plane in fuel electrode layer and oxygen electrode layer in Fig. 2 to Fig. 5
Formula can also be step gradient.
Step gradient electrode is that electrode activity is identical in each zoning, in the direction of the air flow, any catchment
Increased activity of the domain than contiguous upstream zone.Regional can continuously be connected and form complete electrode plane (not shown),
Can also be into some discrete regions (as shown in Figure 7) by clearance gap.Therefore, the electrode layer of step gradient can include
By some intervals or the separate areas of gap division, its interval or gap width are chosen as 0-5mm, for example, 0.5mm, 1mm, 2mm,
3mm, 4mm or 5mm.When interval or gap width are 0, as one continuous continual electrode plane.
In step gradient electrode, the particle diameter of catalyst can be identical in all stepped areas, in difference
Stepped area in catalyst granules density (loading, content) it is different, and along airflow direction arrangement not on the same stage
The density gradient increase of catalyst granules in rank region, i.e., the density of the catalyst granules of the stepped area of close air flow inlet is most
Small, the density close to the catalyst granules of the stepped area of air stream outlet is maximum.
Alternatively, the catalyst of same particle size can be included in same stepped area, and different
Catalyst described in the stepped area diminishes along the airflow direction particle diameter.Urged for example, combination electrode component includes activity
Catalyst particles, the submicron order (such as 0.5~1 μm) in middle reaches is transitioned into by the micron particles (such as 1~5 μm) of upstream position
And the nano-scale particle (such as 0.05~0.5 μm) in downstream.It is preferred that catalyst in combination electrode component carrying body (i.e. from
Sub- conductor supports) also use and the above-mentioned particle size range of catalyst granules identical.In addition, become more meticulous electrode structure is micro-nano
Likewise it is preferred that pore creating material is added in electrode slurry ensures sufficient hole (with the mass ratio of electrode component between 0~15%)
Gap rate is as gas diffusion paths.
Different pore creating material quantity is adjusted in the diverse location of gradient electrode, it is fast to may further ensure that reaction participates in gas
Unimpededly diffusion is fed to electrode reaction site to speed.Such as apply pore creating material in electrode quantity (i.e. with the quality of electrode component
Than) increase to exit at air flow inlet, preferably increase by 0~15%.It is preferred that become more meticulous with electrode microstructure nanometer with reference to same
Step uses, and while active site quantity i.e. enhancing electrochemical catalysis activity is increased, reduces the biography of reactant and product
Defeated resistance reduces concentration polarization loss.
Alternatively, catalyst can include multiple catalysts, and at least one catalyst is along the air-flow side
Increase to gradient profile, remaining catalyst is uniformly distributed along the airflow direction or increased with gradient profile.
Although figure 7 illustrates step gradient electrode to be divided into multiple reactivity regions, smooth type ladder
Degree electrode can also be divided into multiple reactivity regions, and its interval or gap width are chosen as 0-5mm, such as 0.5mm, 1mm,
2mm, 3mm, 4 or 5mm.When interval or gap width are 0, as one continuous continual electrode plane, the reaction of electrode is lived
Property along airflow direction it is smooth, be continuously incremented by.
The preparation of above-mentioned gradient electrode, can by electrode surface diverse location adjust the different particle diameter of electrode catalyst or
Different mass fraction, increase the approach such as another single-phase or compound phase nano electro-catalytic particle to realize.
Gradient electrode is realized by particle diameter distribution, i.e., is tapered into along the particle diameter of flow field direction catalyst, makes its catalysis
Three phase boundary quantity become larger in other words for surface area, the phase boundary length of catalytic reaction three.
Catalyst quality mark control, changes of contents can be supported to realize gradient by active catalyst, that is, changed
Ratio of the active catalyst in combination electrode (being combined by the carrying body that is, ion conductor of active catalyst+catalyst)
To realize.
Increasing that another single-phase or compound phase nano electro-catalytic particle refers to can be in original electrode surface or internal structure
In, on the basis of original catalyst is uniformly distributed in electrode surface, apply along the another of flow field direction quantity gradient distribution distribution
The compound of kind catalyst or several catalyst.It is of course also possible to make multiple catalysts gradient increase in the direction of the air flow, or
Person makes the particle diameter gradient reduction in the direction of the air flow of multiple catalysts.
For example, each constituent of combination electrode can be prepared into slurry respectively, above-mentioned each component slurry is then controlled to press
Quantitative proportion consecutive variations or stepped change are mixed and are applied on load matrix, obtain gradient components electrode.Application side
Formula may include the methods of silk-screen printing, roller coat, spraying, printing, sputtering, dipping, injection, can directly apply catalyst pellets subgroup
Point, or pre-applied catalyst precursor, then post-treated generation catalyst particle.
For example, electrode active ingredient can be passed through ceramic ink jet printing or silk-screen printing a series of (such as prefabricated differences
The slurry of catalyst component, content), and aforementioned gradient electrode layer is directly prepared the methods of physical deposition on electrolyte.
Can be according to the gradient design requirement of electrode activity, the methods of using dipping, injection or deposition, in electrode skeleton prefabricated in advance
Network diverse location adds the catalyst nanoparticles of varying number.
Electrolyte can be individual layer, or the bilayer or MULTILAYER COMPOSITE electrolyte of heterogeneity.Composite electrolyte be for
Avoid the electrode in battery high-temperature sintering or During Process of Long-term Operation that interfacial reaction occurs with electrolyte, avoid generating high resistance,
The secondary thing phase of low activity, and optimize electrode interface performance.
For example, the bilayer that dielectric substrate 310 (or electrolyte-supported layer 510) and electrolyte barrier 310 ' or 510 ' form
Composite electrolyte, wherein dielectric substrate 310 (or electrolyte-supported layer 510) provide preferable ionic conductance, mechanical strength and
Compactness, isolate the reacting gas of two electrodes；Electrolyte barrier 310 ' or 510 ' play stop dielectric substrate 310 (or electricity
Solving matter supporting layer 510) interfacial reaction, optimization interface ion between oxygen electrode layer 320 or 520 are transmitted and reduction electrochemistry is anti-
Answer the effect of polarization impedance.
The composition of dielectric substrate 310 (or electrolyte-supported layer 510) can be one or more co-dopeds such as Y, Sc, Ce
Zirconium oxide base electrolyte (such as YSZ, ScSZ, ScYSZ, ScCeSZ etc.).Electrolyte barrier 310 ' or 510 ' can be Gd,
The ceria-based electrolyte (such as GDC, SDC, LDC, YDC etc.) of one or more co-dopeds such as Sm, La, Y.
Oxygen electrode layer 320 or 520 can be containing La1-xSrxCoyFe1-yO3-δ(LSCF)、La1-xSrxCoO3-δ(LSC)、Sm1- xSrxCoO3-δ(LSC) active electrode of catalyst such as, δ is represented because Lacking oxygen amount caused by doping, x and y are less than 1 in formula.
Electrolyte barrier 310 ' or 510 ' can stop dielectric substrate 310 (or electrolyte-supported layer 510) and oxygen electrode layer
320 or 520, which occur interfacial reaction, forms SrZrO3Or La2Zr2O7High resistance oxide.
Alternatively, another compound scheme of electrolyte is that electrolyte barrier is arranged on dielectric substrate
Between 310 (or 510) and fuel electrode layer 330 (or fuel electrode supporting layer 530), play stop they between interfacial reaction,
Optimize interface ion transmission and reduce the effect of electrochemical reaction polarization impedance, and dielectric substrate 310 (or 510) is directly electric with oxygen
Pole layer 320 (or 520) is adjacent.Now, the composition of electrolyte barrier can be that the one or more in Gd, Sm, La and Y etc. are total to
With the ceria-based electrolyte (such as GDC, SDC, LDC, YDC etc.) of doping, dielectric substrate 310 (or 510) can be lanthanum-strontium gallium
Magnesium LSGM electrolyte, fuel electrode layer 330 (or fuel electrode supporting layer 530) be the catalyst containing Ni active electrode, electrolyte
Barrier layer can avoid Ni and dielectric substrate 310 (or 510) La in fuel electrode layer 330 (or fuel electrode supporting layer 530)1- xSrxGa1-yMgyO3-δ(LSGM, x and y are less than 1) reaction generation LaSrGa3O7、LaSrGaO4Or LaNiO3High resistance phase.
The advantages of gradient electrode and solid-oxide battery of the present invention, is：Electrode polarization performance is along flow field gradual change gas
Difference everywhere under atmosphere is smaller, and electrode local current densities are more uniform in battery face internal ratio, not with airflow direction reactant concentration
Reduce and strongly reduce, effectively avoid transverse current in face, ohm heating is uniform in battery face, reduces electrochemistry decay and heat should
Power failure risk, be advantageous to the prolonged cell life-span.
The gradient electrode of the present invention can be applied to the solid oxygen based on oxygen ion conductor electrolyte or proton conductor electrolyte
Compound battery, and the SOFC/SOEC (anode-supported, electrolyte-supported, cathode support) of different supporting types is can be applied to, it is different
The SOFC/SOEC (different anodes, negative electrode, electrolyte ingredient) of composition, and the SOFC/SOEC of different structure profile are (tubular type, micro-
Tubular type, flat, flat tubular SOFC/SOEC).It is preferably applied to fuel electrode support type flat plate cell, electrolyte-supporting type
Flat plate cell.
For example, fuel electrode can be one or more metal co-doped zirconium oxide (ratios such as Ni catalyst and Y, Sc, Ce
Such as YSZ, ScSZ, ScYSZ or ScCeSZ) composition the porous compound of metal-ceramic or Ni catalyst and Gd, Sm, La, Y
The porous compound of metal-ceramic of one or more metal co-doped cerium oxide (such as GDC, SDC, LDC or YDC) compositions.
Oxygen electrode can be La1-xSrxMnO3-δ(LSM)、La1-xSrxCoyFe1-yO3-δ(LSCF)、La1-xSrxCoO3-δ
(LSC)、Sm1-xSrxCoO3-δ(SSC) the one or more and metal-doped zirconium oxide of catalyst or the metal-doped cerium oxide group such as
Into porous ceramics compound, wherein x and y are less than 1.
Electrolyte can be metal-doped zirconium oxide (such as YSZ, ScSZ, ScYSZ or ScCeSZ), and it connects with oxygen electrode
Tactile one side can previously prepared layer of metal doped cerium oxide dielectric substrate (such as GDC, SDC, LDC or YDC) with avoid with
Interfacial reaction containing cobalt or iron content Oxygen Electrode Material (such as LSCF, LSC, SSC).
Zirconium oxide, oxygen of the oxygen ion conductor electrolyte of above-mentioned solid-oxide battery except cubic fluorite structure can be used
Change cerium base oxide, can also be perovskite oxide electrolytic condenser such as La1-xSrxGa1-yMgyO3-δ(1) LSGM, x and y are less than,
One layer of electrolyte barrier, preferably ceria-based electrolyte can be pre-set in the side that it is contacted with electrode containing Ni such as
GDC, LDC, to avoid LSGM and Ni interfacial reaction.
Gradient electrode of the present invention can be also used for the solid-oxide battery based on high-temperature proton-conductor electrolyte, such as electricity
Solve the BaCe that matter uses proton conducting1-x-yZrxYyO3-δ(BCZY, x+y are less than 1) perovskite oxide or its is metal-doped compound
Oxide.
Gradient electrode of the present invention offset or slow down originally along flow field gas componant change caused by electrode polarization, electric current
The difference of density, and the condition phase such as the initial performance of this difference and solid-oxide battery, gas conversions, total current load
Close, so electrode concrete activity gradient of the present invention can be configured according to intended operating conditions.
For example, the electrode-supported solid-oxide battery for non-functionally graded design as follows：300 μ m thick Ni-YSZ branch
Support | 15 μ m thick Ni-YSZ fuel electrodes | 10 μ m thick YSZ electrolyte | 20 μ m thick LSM-YSZ oxygen electrodes, running temperature 870
DEG C, average current density 1.5A/cm2, water electrolytic gas conversion ratio 45%, current collector layer is approximately that equipotentiality plane i.e. voltage is equal everywhere
V=1.4 lie prostrate, by simulation calculate with experiment measurement can obtain local current densities i along airflow direction gradient distribution as shown in figure 8, and
Polarization resistance distribution can be obtained simply from R=V/i.According to this distribution situation and reactivity and reaction site density
Proportional relationship, feed back and design and prepare in gradient electrode, should make reactivity gradient just with diagram i reversely, to offset original
Carry out the i gradients as caused by atmosphere difference to be distributed.Specifically, it is distributed, makes from air-flow for the gradient of the current density i shown in Fig. 8
Entrance reacts effective site density to the fuel electrode in exit and is incremented by amplitude 14.3%, can obtain electric current in the less face of difference
Distribution.
Embodiment 1
The electrode-supported solid-oxide battery of non-functionally graded design：300 μ m thick Ni-YSZ are supported | 15 μ m thicks
Ni-YSZ fuel electrodes | 10 μ m thick YSZ electrolyte | 20 μ m thick LSM-YSZ oxygen electrodes, 870 DEG C of running temperature, average current
Density 1.5A/cm2, water electrolytic gas 45%CO2+ 45%H2O+10%H2Gaseous mixture, conversion ratio 45%, current collector layer are approximately
Equipotentiality plane is voltage equal V=1.4 volts everywhere.
By adjusting the particle diameter of Ni catalyst and ion conductor 8YSZ in Ni-YSZ fuel electrodes, and use step
Gradient makes electrode progressively become more meticulous by swimming over to downstream on air-flow, i.e., along airflow direction battery be divided into 4 rectangular areas and mutually
Gap is not present in linking, and it is respectively 25%, 50% and 75% that its adjacent boundary accounts for flow field total length with entrance distance, and each region is adopted
With the median particle size of Ni catalyst be followed successively by~2.0 μm ,~1.5 μm ,~0.8 μm and~0.4 μm, each region uses identical
8YSZ and median particle size are~0.4 μm.
CURRENT DISTRIBUTION difference situation can be by being positioned between 5 detection contacts of fuel electrode upstream and downstream collection liquid surface
The electrical potential difference measured simply reflects, equidistantly (flow field total length is accounted for from air flow inlet along airflow direction potential detection contact
0%th, 25%, 50%, 75% and 100%) arrange successively, by the direction of transverse current in the height differentiation face of surveyed potential, by
Surveyed electrical potential difference calculates the size of transverse current with known collector resistivity.By being positioned over battery afflux liquid surface close to gas
Inflow entrance, centre, the otherness of the 3 thermocouple monitoring battery the temperature in the face exported.Solid-oxide battery Ni-YSZ fuel
Electrode is prepared through gradient distribution, is greatly improved under above-mentioned equal operating condition along the performance uniformity of airflow direction, electric current
Difference is cut within 5%, and maximum temperature difference is reduced within 2 DEG C.Thus it is guaranteed that battery operational efficiency everywhere and subtracting
Slow cell decay.
Embodiment 2
Difference from Example 1 is that solid-oxide battery basic structure supports for 300 μ m thick Ni-YSZ | 15 μ
M thickness Ni-SSZ fuel electrodes | 10 μ m thick SSZ electrolyte | 5 μ m thick GDC barrier layers | 20 μ m thick LSCF-GDC oxygen electricity
The porosity of pole, wherein LSCF-GDC is 35%~50%.By increasing catalyst newly in LSCF-GDC oxygen electrodes and regulating and controlling it
Content obtains smooth type gradient so that the electrochemical catalysis performance enhancement from air flow inlet to exit.Specifically, using liquid
Microinjection method is in electrode surface and internal application La0.6Sr0.4CoO3-δAnd CeO2Corresponding metal ion nitrate precursors are molten
Liquid, content of material is controlled by injection speed, make to increase to~15% (neighbouring outlet) from 0 relative to the amplification of porch, slowly
Dry and decompose and be heated to 650-850 DEG C of processing, obtain high-activity nano La0.6Sr0.4CoO3-δAnd CeO2(weight is than 3:2) urge
Agent, it is derived from the solid-oxide battery with gradient electrode.Analyzed through in site measurement, there is consolidating for above-mentioned gradient electrode
State oxide cell is in the process of running along the homogeneous current distribution of airflow direction, and total amplitude of variation is within 5%, maximum temperature
Difference is reduced within 2 DEG C, so as to ensure battery operation efficiency, slow down cell decay.
The embodiment that unitary electrode is gradient electrode is presented above, in the case that two electrodes are gradient electrode,
Runnability otherness can be further reduced, improves battery operation efficiency and slows down cell decay.
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any
Those familiar with the art the invention discloses technical scope in, change or replacement can be readily occurred in, should all be contained
Cover within protection scope of the present invention.
Claims (10)
1. a kind of gradient electrode, it is characterised in that the gradient electrode is used for solid-oxide fuel cell or solid-oxide
Electrolytic cell, and the reactivity of the gradient electrode is increased along airflow direction with gradient profile.
2. gradient electrode according to claim 1, it is characterised in that the gradient electrode is divided into multiple reactivities
Region, the gap width scope between the adjacent reactivity region is 0-5mm.
3. gradient electrode according to claim 1, it is characterised in that the gradient profile is smooth type gradient or step
Gradient.
4. gradient electrode according to claim 3, it is characterised in that same when the gradient profile is step gradient
The catalyst of same particle size is uniformly included in stepped area, and the particle diameter of at least one of described catalyst catalyst is described in
Airflow direction staged in the different stepped areas falls progressively.
5. gradient electrode according to claim 1, it is characterized in that, the gradient electrode is used as fuel electrode or oxygen electrode.
6. gradient electrode according to claim 1, it is characterised in that the density of the reaction site of the gradient electrode is along gas
Stream direction is increased with gradient profile.
7. gradient electrode according to claim 6, it is characterised in that the reaction site is that catalyst is carried on a shoulder pole with ion conductor
The three phase boundary of load and reacting gas.
8. gradient electrode according to claim 7, it is characterised in that the catalyst includes multiple catalysts, at least one
The loading of kind catalyst is increased along the airflow direction with gradient profile, and remaining catalyst is uniformly distributed along the airflow direction
Or also increased with gradient profile.
9. a kind of solid-oxide fuel cell, it is characterised in that the solid-oxide fuel cell includes oxygen electrode and combustion
It is the gradient electrode any one of claim 1-8 to expect at least one of electrode, the oxygen electrode and fuel electrode.
10. a kind of solid oxide electrolysis pond, it is characterised in that the solid oxide electrolysis pond includes oxygen electrode and fuel electricity
At least one of pole, the oxygen electrode and fuel electrode is the gradient electrode any one of claim 1-8.
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| CN108598493A (en) * | 2018-06-04 | 2018-09-28 | 西安交通大学 | A kind of solid oxide fuel cell gradient porosity anode and fuel cell |
| CN112615033A (en) * | 2021-01-19 | 2021-04-06 | 泰州市海创新能源研究院有限公司 | Direct methanol fuel cell catalyst layer gradient membrane electrode and preparation method thereof |
| CN114171744A (en) * | 2022-02-11 | 2022-03-11 | 北京新研创能科技有限公司 | Polar plate of fuel cell, preparation method of polar plate, fuel cell stack, fuel cell system and cold start method of fuel cell system |
| CN114934291A (en) * | 2022-04-29 | 2022-08-23 | 同济大学 | Alkaline water electrolytic tank partition electrode based on non-uniform electrodeposition and preparation method |
| CN115074769A (en) * | 2022-05-06 | 2022-09-20 | 同济大学 | Large-area electrode support body structure of alkaline water electrolytic cell |
| JP7188625B1 (en) | 2022-02-02 | 2022-12-13 | トヨタ自動車株式会社 | water electrolysis cell |
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| CN112615033A (en) * | 2021-01-19 | 2021-04-06 | 泰州市海创新能源研究院有限公司 | Direct methanol fuel cell catalyst layer gradient membrane electrode and preparation method thereof |
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| CN114934291A (en) * | 2022-04-29 | 2022-08-23 | 同济大学 | Alkaline water electrolytic tank partition electrode based on non-uniform electrodeposition and preparation method |
| CN114934291B (en) * | 2022-04-29 | 2023-08-04 | 同济大学 | Alkaline water electrolysis bath partition electrode based on non-uniform electrodeposition and preparation method |
| CN115074769A (en) * | 2022-05-06 | 2022-09-20 | 同济大学 | Large-area electrode support body structure of alkaline water electrolytic cell |
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