CN209607852U - A kind of film electrode structure, fuel cell and battery pile - Google Patents
A kind of film electrode structure, fuel cell and battery pile Download PDFInfo
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- CN209607852U CN209607852U CN201920484752.8U CN201920484752U CN209607852U CN 209607852 U CN209607852 U CN 209607852U CN 201920484752 U CN201920484752 U CN 201920484752U CN 209607852 U CN209607852 U CN 209607852U
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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
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Abstract
A kind of film electrode structure, fuel cell and battery pile, belong to field of batteries.Film electrode structure is applied to battery, especially fuel cell.Film electrode structure has multilayered structure and first electrode layer, the second electrode lay and electrolyte layer including successively lamination contact arrangement, and electrolyte layer is between first electrode layer and the second electrode lay.One of first electrode layer and the second electrode lay and the two have network-like structure.Wherein, network-like structure includes separating materials layer and optional electrode material layer, and optional electrode material layer is between electrolyte layer and electrode material layer.The thermal expansion coefficient of separating materials layer is less than or equal to the thermal expansion coefficient of electrolyte layer.Degree of being mutually matched is high between electrode and electrolyte in film electrode structure, is not easy to remove, be detached from each other because the difference of thermal expansion is too big each other.
Description
Technical field
The utility model relates to field of batteries, in particular to a kind of film electrode structure, fuel cell and battery pile.
Background technique
With the fast development of mobile Internet and Internet of Things, various portable mobile apparatus (such as palm PC, mobile phone,
The various e-machines such as various wearable devices such as wrist-watch) it is more more and more universal.In use, equipment some in this way can usually be related to
To continuation of the journey problem, i.e. electricity shortage.And with the prosperity of semiconductor technology, various equipment are constantly to miniaturization.To have
Power supply of the fuel cell of special performance for these equipment has quite ideal prospect.
Fuel cell is exactly the device for the chemical energy of chemical reaction being converted into electric energy.It is made with fuel and oxidant
For the raw material that generates electricity.There are many type of fuel cell, classification method also there are many.
As an important types of fuel cells, solid oxide fuel cell (Solid Oxide Fuel Cell, SOFC)
Has the advantages that itself uniqueness.And also there is more excellent service performance and value accordingly.For example, solid oxide fuel is electric
Pond has relatively high operating temperature (such as 800~1000 DEG C).Solid oxide fuel cell as a kind of all solid state device,
Two-phase (gas-solid) reaction is related merely to during its fuel reaction, thus, without carrying out complicated electrolyte management, Ke Yi
Simplify structure to a certain extent.
There is membrane structure design in current some SOFC.This structure based on SOFC, manufacturing process need special
It does not investigate, in conjunction with conditions such as its operating temperatures, using there is also certain problems.These all limit template SOFC's
Further development.
Normally, the main problem of SOFC first is that: during actual make and use, template SOFC is often showed
The situations such as crackle easy to form, cracking, removing out.
The information disclosed in the background technology section is intended only to deepen the reason to the general background technology of the utility model
Solution, and it is known to those skilled in the art existing to be not construed as recognizing or imply that the information is constituted in any form
Technology.
Utility model content
For improve, even solve the problems, such as it is in the prior art at least one, the utility model proposes a kind of membrane electrode knots
Structure, fuel cell and battery pile.
The utility model is realized in this way:
In a first aspect, the example of the utility model provides a kind of film electrode structure.
Film electrode structure in example can be applied to battery, especially fuel cell, especially solid oxide fuel
Battery.
Film electrode structure has multilayered structure.
Film electrode structure includes first electrode layer, the second electrode lay and the electrolyte layer of successively lamination contact arrangement, and
And electrolyte layer is between first electrode layer and the second electrode lay.
One of first electrode layer and the second electrode lay and the two have network-like structure.
Wherein, network-like structure includes separating materials layer and optional electrode material layer, and optional electrode material layer
Between electrolyte layer and electrode material layer.
The thermal expansion coefficient of separating materials layer is less than or equal between the thermal expansion coefficient of electrolyte layer.
Network-like structure is divided electrode, it is made to be subdivided into multiple relatively smaller areas by complete continuous structure
Domain continuously or discontinuously structure, to play the effect of release stress.By being split to the electrode in film electrode structure,
The thermal expansion of electrode is set to be inhibited and be weakened to a certain extent, so as to preferably avoid the heat between electrode and electrolyte swollen
Swollen mismatch.Since the thermal expansion mismatch between electrode and electrolyte is reduced, film electrode structure stress as caused by mismatch also by
Greatly reduce, excessively adds up caused the problems such as cracking, removing by stress so as to avoid between electrode and electrolyte.
With reference to first aspect, in some optional examples of the first possible embodiment of the utility model, segmentation
Material layer is Continuum Structure or discrete bodies structure.
The possible embodiment of with reference to first aspect the first, in second possible embodiment of first aspect
In some optional examples, the shape of Continuum Structure includes the first regular figure or the first irregular figure.
Optionally, the first regular figure includes array shape, honeycombed, and the shape in the hole of array shape includes triangle, four sides
Shape or polygon.
With reference to first aspect the first possible embodiment, in the third possible embodiment of first aspect
In some optional examples, separating materials layer is discrete bodies structure, and the shape of discrete bodies structure includes Second Rule figure or second
Irregular figure.
Optionally, Second Rule figure is forked.
Various structures appropriate are arranged by selection in separating materials layer according to different requirements, can reach electrode point
Being segmented into multiple smaller regions is advisable.Different separating materials layer structures can be as required according to the difficulty or ease progress for realizing technique
Selection.Since separating materials layer has the implementation of plurality of optional, the flexibility of film electrode structure production can be improved.
With reference to first aspect or the first or second or the third possible embodiment of first aspect, practical at this
In some optional examples of 4th kind of possible embodiment of novel first aspect, separating materials layer has by first electrode
Layer to the direction of the second electrode lay thickness, and with a thickness of 1~50 micron.
Optionally, with a thickness of 6~45 microns.
Optionally, with a thickness of 16~30 microns.
Optionally, with a thickness of 20~26 microns.
The size of film electrode structure is usually one of an important factor for limiting its application scenarios and field.Therefore, based on suitable
Work as demand, comprehensive consideration its production, technique, raw material and in terms of the case where, it will be beneficial for adjusting thickness appropriate
's.As a kind of pair of advantageous selection of portable battery, it will be appropriate for controlling the thickness of separating materials layer.Normally, divide
Material layer is made the too thick easy combination influenced between electrode and electrolyte.Of course, separating materials layer is made too
Bao Ze may cause the obvious rising of the difficulty of manufacture craft, and may thus cause under its segmentation effect to electrode
Drop.
4th kind of possible embodiment with reference to first aspect, the 5th kind in the first aspect of the utility model are possible
In some optional examples of embodiment, first electrode layer and the second electrode lay all have network-like structure, and first electrode
The material of separating materials layer in the material and the second electrode lay of separating materials layer in layer is identical or different.
It is apparent that being carried out to improve the performance and stability of film electrode structure to first electrode layer and the second electrode lay
Segmentation can effectively make the thermal expansion mismatch problems of the two be improved in a manner of relative ideal, even solve.
In different batteries, the separating materials layer in first electrode and second electrode, which can according to need, to be selected by each
Kind suitable material production.In view of the possibility of replacement or alternative materials is difficult in manufacture craft, perhaps can using identical material
Bring technologic convenience.It certainly, can also be in the condition for being suitably modified technique according to the demand of different function and performance
Under, select different materials.
With reference to first aspect, optional show in some of the 6th kind of possible embodiment of the first aspect of the utility model
In example, first electrode layer is anode, and anode is metal electrode or cermet electrodes.
As a kind of application in a fuel cell, anode be can choose as micropore gas diffusion electrode.Correspondingly, anode
The selection of material can be metal simple-substance electrode or ceramal or cermet (such as metal oxide) electrode.
Such electrode can satisfy the needs of stability, fuel mass transfer etc., be conducive to electrode reaction it is normal into
Row.
With reference to first aspect, optional show in some of the 7th kind of possible embodiment of the first aspect of the utility model
In example, the second electrode lay is cathode, and cathode is metal oxide electrode.
As a kind of application in a fuel cell, similarly with anode, cathode be can choose as micro-porous electrode.It is such
Electrode can satisfy compound etc. the needs of electronics conduction, ion, be conducive to being normally carried out for electrode reaction.
Correspondingly, the selection of cathode material can be such as above-mentioned material, or such as ceramic material (ceramal), either
The perovskite or strontium doping lanthanum manganite of such as semiconductor structure.
In second aspect, the example of the utility model provides a kind of fuel cell.
Fuel cell includes above-mentioned film electrode structure.
The above film electrode structure can be produced and use in the form of a film, fire so as to be used for soild oxide such as
Expect battery.Its structure is more compact, reduces numerous severe electrolyte management requirement, or even in some schemes adjusted, also
It is able to bear the problem of overload, low load or short circuit.It further, can also be in energy conservation based on this solid oxide fuel cell
Etc. obtain original performance.In addition, it can also be modulated to use under conditions of relatively-high temperature, thus, using neck
Domain is wider.
In the third aspect, the example of the utility model provides a kind of battery pile.
Battery pile includes at least two fuel cells as the aforementioned, and is passed through between two adjacent fuel cells
Bipolar plates connection.
The application in the form of battery pile by fuel cell, higher voltage and power output can be obtained, to meet
The power demand of actual various equipment.
The utility model has the advantages that
In film electrode structure provided by the embodiment of the utility model, electrode (first electrode layer and/or the second electrode lay) quilt
It is separated by separating materials layer, electrode is made to be provided with subtleer structure.The thermal expansion of electrode is due to separating materials
Layer and suitably inhibited, thus make thermal expansion generate stress conduction and local accumulation also limited, therefore, electrode and electricity
Removing, cracking between solution matter are also able to preferably be prevented, so as to be based on changing film electrode structure in improvement to a certain degree
Battery (such as fuel cell) service life and performance.
Detailed description of the invention
It, below will be to use required in embodiment in order to illustrate more clearly of the technical solution of the utility model embodiment
Attached drawing be briefly described, it should be understood that the following drawings illustrates only some embodiments of the utility model, therefore should not be by
Regard the restriction to range as, for those of ordinary skill in the art, without creative efforts, may be used also
To obtain other relevant attached drawings according to these attached drawings.
Fig. 1 is the structural schematic diagram at the first visual angle of the first film electrode structure in the utility model example；
Fig. 2 shows the structural schematic diagrams at the second visual angle of film electrode structure shown in FIG. 1；
Fig. 3 is shown as the structural schematic diagram at the second visual angle of second of film electrode structure in the utility model example；
Fig. 4 is shown as the structural schematic diagram at the second visual angle of the third film electrode structure in the utility model example；
Fig. 5 is shown as the structural schematic diagram at the second visual angle of the 4th kind of film electrode structure in the utility model example；
Fig. 6 is shown as the structural schematic diagram at the first visual angle of the 5th kind of film electrode structure in the utility model example.
Icon: 100- film electrode structure；102- anode；103- electrolyte layer；104- cathode；The region 1041a-；105a- points
Cut material layer；The region 1041b-；105b- separating materials layer；The region 1041c-；105c- separating materials layer；The region 1041d-；
105d- separating materials layer；105- separating materials layer；200- fuel cell；204- cathode；205- separating materials layer.
Specific embodiment
During realizing the utility model, inventor has found under study for action, although solid oxide fuel cell has
Its unique advantage, but there is also certain urgent problems to be solved.
For example, the problems such as battery is easy to appear cracking, structure sheaf peels off.Such problems either in its manufacturing process,
Still there is performance in use.For such a problem, the prior art has carefully been investigated, in correlative study and technology
Generally, it is considered that this is because peel off layer by layer between combination it is insecure caused by.Inventor has found to draw in further studying
A main cause for playing the problem is mismatch problems between different structure layer.For example, due between different structure layer by
(principal element), the degree difference by cold events are thermally expanded, when opposite deformation (expansion) occurs, the two cannot match well
It closes.It can lead to the accumulative of stress between the big substance of thermal expansion coefficient and the small substance of thermal expansion coefficient by differences in expansion, in turn
Cause the situation of faying face being separated from each other.
For example, cathode problem: the perovskites cathode such as LSC, LSCF, SSC exists in some solid oxide fuel cell
Catalytic activity and conductivity with higher under middle low temperature, but thermal expansion coefficient is significantly higher than electrolyte.Alternatively, its anode is asked
Topic: as Ni content increases, the thermal expansion coefficient of Ni metal anode increases.In order to keep good thermal expansion matching, often adopt
With lower Ni content, the decline of anode conducting performance.
For this, inventor thinks to improve or alleviate above ask by the thermal expansion coefficient adjustment to different structure layer
Topic.
Although person can be adjusted by the selection to material, it is contemplated that the own characteristic of battery, as electrode is anti-
It answers, working environment etc., only changing material may result in some degradations of battery itself.In other words, only with adjustment
The material of electrode and/or electrolyte realizes the problem of matching of thermal expansion perhaps can cause other, and leads to such trial
It is possible and undesirable or not be better choice.
In view of this, inventor attempts to improve the film electrode structure of battery in the utility model example.
In example, by being split to electrode, the electrode formation multiple regions more tiny relative to full size, and
Separating materials layer is constructed at the boundary of the adjacent area of multiple regions, and using the separating materials layer as two neighboring region
Boundary.
Due to the presence of the separating materials layer as boundary, the structural intergrity of electrode as a whole is broken,
Deformation (volume expansion) as a whole will disperse in each region and become smaller deformation.The thermal expansion shape of such electrode
Varying stress is released, and is not easy to separate with electrolyte.Simultaneously as the thermal expansion coefficient of separating materials layer is by choosing appropriate
It selects, is also less likely to occur biggish volume change, thus be also easier to be adapted to electrolyte and electrode.
Below with reference to attached drawing, film electrode structure, fuel cell and the battery pile in the utility model example are carried out
More detailed explanation.
In order to which the technical solution of the utility model embodiment is more clearly understood, the utility model embodiment is with solid
It is illustrated for film electrode structure in oxide body fuel cell.
Fuel cell generally includes anode, cathode, electrolyte and some other support system or device, for example, carrying out
The shell of encapsulation, fuel supply device, collector, etc..
It should be understood that since fuel cell is the equipment that the chemical energy of fuel is converted into electric energy, and in order to
It realizes and concentrates or power to large number of equipment, fuel cell is usually used in a manner of battery pile.I.e. by multiple fuel cell units
Conjunction is carried out using to provide more appropriate voltage and power.
And for the fuel cell system of such battery pile, the fuel cell in practical application can also correspond to outfit fuel
(such as hydrogen, hydrogen-rich reformed gas, hydrazine/diamine) feeding mechanism.Or it can also be equipped with some gases, liquids recovery as needed
System etc..
Film electrode structure in the utility model example has multilayered structure.That is the film electrode structure knot that is certain quantity
Structure layer is arranged in a manner of being laminated, and can be combined together by way of sintering between each layer.
In example, film electrode structure includes first electrode layer, the second electrode lay and the electrolysis of successively lamination contact arrangement
Matter layer, and electrolyte layer is between first electrode layer and the second electrode lay.Such film electrode structure can be applied to
In tubular type or board-like SOFC.
In order to inhibit and weaken the stripping problem between electrode and electrolyte, in example, first electrode layer and second electrode
One of layer and the two have network-like structure.I.e. first electrode layer has network with network-like structure or the second electrode lay
Shape structure or first electrode layer and the second electrode lay all have network-like structure.Corresponding to SOFC, anode has network-like structure
Or there is cathode network-like structure or anode and cathode to all have network-like structure.
Just it has been observed that electrode district is divided into multiple regions by network-like structure.In as an example, network-like structure includes
Separating materials layer and optional electrode material layer.Wherein, optional electrode material layer be located at electrolyte layer and electrode material layer it
Between.
In other words, network-like structure can be is made of separating materials layer completely.In such an example, separating materials layer
Capable of extending outwardly from electrolyte layer, (extending direction can be electrolyte layer to the second electrode lay and/or electrolyte layer to
One electrode layer), and run through corresponding electrode.As separating materials layer from electrolyte to first electrode layer extend, and through first electricity
Pole layer.In optional scheme, the extension of separating materials layer be carried out in a manner of perpendicular to electrolyte, alternatively, can be with
Surface with electrolyte layers is at non-perpendicular fashion (such as acute angle, including 30 °, 45 °, 55 °, 60 ° or obtuse angle, including 120 °, 130 °).
Alternatively, network-like structure can also be by separating materials layer and electrode material layer (first electrode layer or the second electrode lay)
It collectively forms, and separating materials layer is between electrolyte layer and electrode material layer.For example, having in first electrode layer network-like
In the example of structure, the surface of electrolyte layer forms separating materials layer and first electrode layer, and first electrode layer is to cover net
Network shape structure (i.e. the separating materials layer of network-like structure).That is, network-like structure can also be by separating materials layer and electrode
Material layer collectively forms, and separating materials layer, in the scheme between electrolyte layer and electrode material layer, separating materials layer is simultaneously
Non- penetrating electrode.
Simultaneously in order to avoid the selection of the separating materials layer for the composition network-like structure being introduced into as segmentation electrode is lost
When and the problem of cause mismatch again, the thermal expansion coefficient of separating materials layer is selected.For example, the thermal expansion coefficient of separating materials layer
Less than or equal to the thermal expansion coefficient of electrolyte layer.Thermal expansion coefficient in view of electrode in general SOFC is to be greater than electrolysis significantly
The thermal expansion coefficient of plasma membrane, therefore, the thermal expansion coefficient of separating materials layer can choose smaller in example, i.e., than electrode material
Thermal expansion coefficient is much smaller.
Material selection for film electrode structure, those skilled in the art can according to need the various materials appropriate of selection
Expect, it is not particularly limited in utility model.Some example effects, can for the different structure layer in film electrode structure
To make enumerating for following example shape.
For constituting one of the component of network-like structure, the material selection of separating materials layer is as follows: for example, separating materials layer
Material include doping cerium oxide, undoped cerium oxide, the zirconium oxide of doping, undoped zirconium oxide, aluminium oxide, magnalium
The combination of any one or more in spinelle, silicate.Wherein, a variety of combinations can be the combination of the two (as aoxidized
Aluminium and magnesium aluminate spinel；Magnesium aluminate spinel and silicate；Cerium oxide and the zirconium oxide of doping of doping etc.) or three
Combination is (such as the zirconium oxide and aluminium oxide of the cerium oxide, doping that adulterate；Zirconium oxide, aluminium oxide and the magnalium point crystalline substance of doping
Stone), the combining forms such as four combination.In addition, rare earth element can be used and be doped in the metal oxide of doping,
And rare earth element include it is one or more, rare earth element is, for example, lanthanum (La), cerium (Ce), yttrium (Y).
Moreover, it is noted that the segmentation in the material and the second electrode lay of the separating materials layer in first electrode layer
The material of material layer can be identical or be also possible to difference.
The material selection of first electrode layer and the second electrode lay for composition electrode is as follows: according to the concrete function of electrode
Difference, the two can have different selections.For example, first electrode layer is anode.So, anode can then be selected as metal electrode
Or cermet electrodes.Further, the material of anode can be nickel or nickel alloy or nickeliferous ceramics.For example, the second electrode lay
For cathode.So, cathode can then be selected as metal oxide electrode.Optionally, the material of metal oxide electrode is ternary
Alloyed oxide or quaternary alloy oxide.Optionally, the metallic element in ternary alloy three-partalloy oxide includes the first element combinations
Or second element combination, wherein the first element combinations include samarium, strontium, cobalt, therefore ternary alloy three-partalloy oxide can be SmxSryCoz
(SSC).It can be with Sm in some specific examples0.5Sr0.5Co3O3.Second element combination includes lanthanum, strontium, cobalt, therefore.Ternary alloy three-partalloy
Oxide can be LaxSryCoOz(LSC).In some specific examples, ternary alloy three-partalloy oxide can be La0.5Sr0.5CoO3。
Or cathode can be selected as perovskite electrode, such as LaSrCoO4、LaNiO3.Metallic element packet in quaternary alloy oxide
Include lanthanum, strontium, cobalt, iron, such as LaxSryCoFeOz(LSCF).In some specific examples, quaternary alloy oxide can be La1- xSrxCo0.2Fe0.8O3(wherein 0.1 < x < 0.6).
As follows for the material selection for constituting the electrolyte layer of electrolyte: the material of electrolyte layer can be undoped gold
Belong to the metal oxide of oxide or doping.Optionally, metal oxide includes zirconium oxide and cerium oxide.Optionally, doping
Doped chemical in metal oxide is rare earth element, and rare earth element includes one or more.
Particularly, more narration in detail will be carried out to the network-like structure for being formed in electrode in example below.
It has been observed that network-like structure is designed for dividing electrode, in example, network-like structure is by separating materials
Layer is constituted.Alternatively, network-like structure is made of separating materials layer and electrode material layer.When network-like structure is formed in first electrode
When layer, network-like structure is made of separating materials layer or separating materials layer and first electrode material layer collectively form.When network-like
When structure is formed in the second electrode lay, network-like structure is made of separating materials layer or separating materials layer and second electrode material layer
It collectively forms.
It will (be only below that cathode is divided i.e. in film electrode structure with the second electrode lay for being provided with network-like structure；
Certainly in other examples, also can choose is only anode be divided or anode and cathode be divided) for said
It is bright.
In addition, usually can choose in the example of such cathode segmentation using anode as support.In other words, anode
It plays and reinforces fuel cell, support electrolyte layer and cathode etc. are used.That is cathode segmentation, anode-supported.Similarly, fuel cell
With anode segmentation, cathode support type；Alternatively, fuel cell has anode segmentation, cathode segmentation, electrolyte-supported type.
For cathode segmentation, anode-supported SOFC, divide cathode network-like structure can make under illustrate.
Film electrode structure 100 has structure as shown in Figure 1.According to orientation shown in FIG. 1, film electrode structure includes being located at
The anode 102 of bottom is located in the middle electrolyte layer 103 and superposed cathode 104.Also, also have in cathode 104
In separating materials layer 105 arranged in a vertical direction, separating materials layer 105 has run through cathode 104.
Although anode, cathode and electrolyte layer have opposite thickness size, for example, anode 102 in Fig. 1
Thickness be greater than the thickness of cathode 104, the thickness of cathode 104 is greater than the thickness of electrolyte layer 103.But the utility model is negative
The thickness of pole, anode and electrolyte layer particularly limiting, can be needed according to specific manufacture craft and function and
Selection is adjusted.However, it should be understood that the thickness of electrolyte layers is relative to cathode in most film electrode structure
Thickness and the thickness of anode be all smaller.
The thickness of separating materials layer 105 can also carry out adjustment appropriate.For example, the thickness of separating materials layer 105 is equal to
The thickness of cathode 104；Alternatively, the thickness of separating materials layer 105 be less than cathode 104 thickness (this can in subsequent narration quilt
It refers to, and can also be illustrated from Fig. 6).
Separating materials layer is intended for the example of network-like structure and divides electrode, therefore, the shape of separating materials layer
Shape can have the scheme of plurality of optional, and is limited with that can play substantially segmentation electrode.Generally, separating materials layer is to connect
Continuous body structure or discrete bodies structure.In the example for the thickness that the thickness of separating materials layer is equal to cathode, when separating materials layer is
When Continuum Structure, cathode is discrete；Of course, when separating materials layer is discrete bodies structure, cathode is Continuum Structure
's.
In the example for the thickness that the thickness of separating materials layer is less than cathode, separating materials layer is Continuum Structure or discrete
When structure, cathode is all that continuously, cathode is divided material layer (discrete) in the part of neighbouring electrolyte layer.And due to dividing material
The thickness of the bed of material is less than the thickness of cathode, and therefore, cathode also has the part of covering separating materials layer, and the covering part is
Continuously.In other words, in such an example, so-called cathode is the covering for continuously referring to aforementioned a part for belonging to cathode
Part.
It optionally, include that the first regular figure or first are non-as the shape of the Continuum Structure of exemplary separating materials layer
Regular figure.Wherein, the first regular figure includes array shape, honeycombed.The hole of array shape may be, for example, triangle, quadrangle or
Polygon；
Optionally, separating materials layer is discrete bodies structure, and the shape of discrete bodies structure includes Second Rule figure or second
Irregular figure, it is highly preferred that Second Rule figure is forked.Second Rule figure, such as can be and the first regular figure
Identical shape, naturally it is also possible to be and the different figure of the first regular figure institute.
The cathode that arrangement above has separating materials layer is more clearly understood that and implemented for the ease of those skilled in the art, is asked
Refering to Fig. 2-Fig. 5.
By taking Fig. 2 as an example, wherein greyish black color part is in cathode because of the region 1041a (electrode material that is divided to form
Layer), white portion is separating materials layer 105a.On the whole, tessellate is presented in cathode 104.Wherein, cathode has compartment of terrain in length and breadth
12 × 12 region 1041a of arrangement.Each region is the electrode material layer that electrode material (LSC as the aforementioned) is formed, and electric
Pole material layer is discrete bodies.Separating materials layer 105a have be spaced in length and breadth and alternately arrange 11 × 11 latitude and longitude/bands/
Item, and separating materials layer is non-individual body.
By taking Fig. 3 as an example, wherein greyish black color part is in cathode because of the region 1041b that is divided to form, substantially three
The combination shape structure of regular hexagon, and be discrete bodies.White portion is separating materials layer 105b, the group of substantially multiple line segments
It closes, and is non-individual body.
By taking Fig. 4 as an example, wherein greyish black color part is substantially to be positive four in cathode because of the region 1041c that is divided to form
Side shape structure, and be discrete bodies.White portion be separating materials layer 105c, the combination of substantially multiple line segments, and for connect
Continuous body.
By taking Fig. 5 as an example, wherein greyish black color part is substantially to be positive four in cathode because of the region 1041d that is divided to form
Side shape structure, and be non-individual body.White portion is separating materials layer 105d, " ten " word that substantially two line segments are composed
Shape structure, it is multiple to be somebody's turn to do " ten " character form structure compartment of terrain arrangement and be discrete bodies.
It should be pointed out that the above structure as described in Fig. 2 to Fig. 5 can be only the part of cathode, in complete device
Or in device, the structure of cathode usually can be the simple repetition of Fig. 2 structure in any figure into Fig. 5.For example, for Fig. 1
Shown in scheme, complete cathode construction can be being arranged in juxtaposition for two cathode constructions as shown in figure 1.
In addition, figure 2 above, into structure shown in fig. 5, the network-like structure for dividing cathode is by separating materials layer
Constitute, and in such example, separating materials layer be through cathode (i.e. separating materials layer extends from electrolyte layer to cathode
To the whole of cathode thickness).Further, separating materials layer processing has except structural form enumerated above, can be with
With other construction (such as pentagon, triangles, etc. appropriate.), it is limited so that cathode can be split.
In other some examples, other cathode constructions are also possible to have structure similar with above-mentioned cathode.And
The main distinction is, the network-like structure for dividing cathode is made of separating materials layer and electrode material layer, therefore in this way
Example in, separating materials layer does not run through cathode, and (in other words, electrode material layer is covered on separating materials layer, that is, divides
Material layer extends to the part of cathode thickness from electrolyte layer to cathode；In other words, separating materials layer is from electrolyte layer to cathode
The top surface of cathode is extended close to, is formed between one fixed width between the top surface of separating materials and the top surface of the cathode
Gap).Film electrode structure (fuel cell 200) can be illustrated in attached drawing as shown in FIG. 6 in this way.
Just it has been observed that being also resided in for dividing one of different factor of network-like structure of cathode other than its shape:
The length difference D1 of separating materials (in the difference of the extended distance of the thickness direction of film electrode structure).In order to more clearly to this
It is illustrated, referring to Fig. 6.
Film electrode structure (fuel cell 200) definition has thickness direction (shown in this filled arrows of Fig. 6), separating materials layer
205 have direction (the i.e. anode 102 to cathode 204 by first electrode layer (anode 102) to the second electrode lay (cathode 204)
Direction) thickness D1, the distance between separating materials layer 205 to the top surface of cathode 204 be D2.The sum of D1 and D2 are cathode
In the length of thickness direction.The value of D1 and D2 can freely be carried out selection cooperation, and the utility model does not do it specifically
It limits.In example, D1 is with a thickness of 1~50 micron.Or thickness D1 is 6~45 microns；Alternatively, thickness D1 is 16~30 microns；
Alternatively, thickness D1 is 20~26 microns.Also, D1 is greater than D2.
In addition, being to be run through with separating materials layer and do not described through cathode respectively in examples above.But it answers
Work as understanding, in other other examples, separating materials layer also can have other distribution modes, for example, partial point
It cuts material layer and has run through cathode, and the separating materials layer of another part has run through cathode.
The above-mentioned film electrode structure (the first film electrode structure) to anode-supported, cathode segmentation is described.And it is right
The main distinction in the film electrode structure (the second film electrode structure) that cathode support, anode are divided, with the first film electrode structure
One of be: divided is the difference of which electrode (or can be two electrodes while being divided), and the side divided
Formula may refer to 2~Fig. 5 of earlier figures.Further, for the film electrode structure of electrolyte-supported, cathode segmentation, anode segmentation
(third film electrode structure), is with one of the first film electrode structure and the main distinction of the second film electrode structure, anode and
Cathode is divided.Also, the partitioning scheme of cathode and anode can be selected as identical partitioning scheme or
To be different partitioning scheme.
In addition, in order to make those skilled in the art be more easily performed the utility model, below in the utility model example
Anode-supported, the film electrode structure preparation method of cathode segmentation are illustrated.
Make anode.The anode can use the cermet anode of Ni or Ni alloy.
Electrolyte is made on a face of anode.Electrolyte can use rear-earth-doped cerium oxide or rear earth doping oxygen
Change zirconium.
Oxide network is made away from the surface of anode in electrolyte.Production method can be using silk-screen printing, ceramics spray
Ink printing etc..
The structure made above is sintered, the temperature of sintering is 1000~1500 DEG C.
Then, it is provided with the surface coated cathode material of oxide network in electrolyte, is then burnt at 900~1200 DEG C
Knot.
Film electrode structure in the prior art, including anode, electrolyte and cathode.And preparation method and the above method
The main distinction be: the oxide network more than not making.
It is found by examining, in existing technology, in subsequent assembling process after being sintered to cathode or after sintering,
Film electrode structure is easy to happen cracking or removing, and yield rate only has 40-60% or so.And use the side in the utility model example
Anode-supported prepared by method, cathode segmentation film electrode structure in production and application process, the cracking situation of cathode by compared with
Inhibit well, yield rate is promoted to 95% or more.
In order to make those skilled in the art be more easily performed the utility model, to the production side of the film electrode structure in example
Method is illustrated.
Since solid oxide fuel cell has plate, cast, corrugated plate type, flat-tube type or other shapes etc.
Various types of constructions, and film electrode structure proposed in the utility model example can be adapted for the electricity of the above various constructions
Pond type.
One, by anode-supported, cathode divide flat plate cell for, structure be anode/electrolyte/oxide network/
Cathode, the production method is as follows:
1, anode is prepared
Using the cermet anode (tabular) of the methods of curtain coating, extrusion forming preparation alloy containing Ni or Ni, such as Ni-
YSZ, Ni-GDC anode etc., the percent by volume of Ni is between 20-80%.
2, anode/electrolyte is prepared
Electrolytic thin-membrane is prepared in anode surface using the methods of curtain coating, spin coating, silk-screen printing, material is rear-earth-doped
Cerium oxide or rear-earth-doped oxidation zirconium, 1-50 microns of thickness.
3, anode/electrolyte/oxide network is prepared
Oxide network is prepared in electrolyte membrane surface using the methods of silk-screen printing, ceramic ink jet printing.Material: dilute
Cerium oxide or rear-earth-doped oxidation zirconium, aluminium oxide, Mg-Al spinelle, silicate of soil doping etc., height: 1-50 microns.
4, sintered plate is prepared
Plate by anode/electrolyte/oxide network co-sintering, sintering temperature: 1200-1500 DEG C of sintering temperature.
5, flat plate cell processed
Cathode is formed on the oxide network surface of the above sintered plate.Cathode can choose LSC cathode, LSCF cathode or
SSC cathode.The method for preparing cathode includes 900-1200 DEG C of sintering after coating.
It can have the various size selected such as 5cm × 5cm thus to obtain flat plate cell, 10cm × 10cm, 20cm ×
20cm, 20cm × 30cm, 30cm × 50cm equidimension.
Two, by anode-supported, cathode divide tubular cells for, structure be anode/electrolyte/oxide network/
Cathode, the production method is as follows:
1, anode is prepared
Using the cermet anode (cast shape) of the methods of extrusion forming preparation alloy containing Ni or Ni, such as Ni-YSZ, Ni-
GDC anode etc., the percent by volume of Ni is between 20-80%.
2, anode/electrolyte is prepared
Using the methods of silk-screen printing, dip-coating, electrophoresis, magnetron sputtering, plasma-deposited tubulose anode appearance
For wheat flour for electrolytic thin-membrane, material is rear-earth-doped cerium oxide or rear-earth-doped oxidation zirconium, 1-50 microns of thickness.
3, anode/electrolyte/oxide network is prepared
Oxide network is prepared in electrolyte membrane surface using the methods of silk-screen printing, ceramic ink jet printing.Material: dilute
Cerium oxide or rear-earth-doped oxidation zirconium, aluminium oxide, Mg-Al spinelle, silicate of soil doping etc., height: 1-50 microns.
4, sintered plate is prepared
Tubulose by anode/electrolyte/oxide network co-sintering, sintering temperature: 1200-1500 DEG C of sintering temperature.
5, tubular cells processed
Cathode is formed on the oxide network surface of the above sintered plate.Cathode can choose LSC cathode, LSCF cathode or
SSC cathode.The method for preparing cathode includes 900-1200 DEG C of sintering after coating.
It should be understood that the various implementations of the film electrode structure in the utility model example can desirably make
Battery for various structural types (plate, cast, corrugated plate type, flat-tube type).Also, each structure in film electrode structure
The partitioning scheme of material and its manufacture craft and electrode with functional layer can also be by on-demand selection collocation.
The above descriptions are merely preferred embodiments of the present invention, is not intended to limit the utility model, for this
For the technical staff in field, various modifications and changes may be made to the present invention.It is all in the spirit and principles of the utility model
Within, any modification, equivalent replacement, improvement and so on should be included within the scope of protection of this utility model.
Claims (12)
1. a kind of film electrode structure, be applied to battery, which is characterized in that the film electrode structure with multi-layer structure include according to
First electrode layer, the second electrode lay and the electrolyte layer of secondary lamination contact arrangement, the electrolyte layer are located at first electricity
Between pole layer and the second electrode lay；
One of the first electrode layer and the second electrode lay and the two have network-like structure；
The network-like structure includes separating materials layer and optional electrode material layer, and the optional electrode material layer is located at institute
It states between electrolyte layer and the electrode material layer；
The thermal expansion coefficient of the separating materials layer is less than or equal to the thermal expansion coefficient of the electrolyte layer.
2. film electrode structure according to claim 1, which is characterized in that the separating materials layer be Continuum Structure or from
Granular media structure.
3. film electrode structure according to claim 2, which is characterized in that the shape of the Continuum Structure includes the first rule
Then figure or the first irregular figure, first regular figure include array shape, honeycombed, the shape in the hole of the array shape
Including polygon.
4. film electrode structure according to claim 3, which is characterized in that the shape in the hole of the array shape is triangle.
5. film electrode structure according to claim 3, which is characterized in that the shape in the hole of the array shape is quadrangle.
6. film electrode structure according to claim 2, which is characterized in that the separating materials layer is discrete bodies structure, institute
The shape for stating discrete bodies structure includes Second Rule figure or the second irregular figure, and the shape of the Second Rule figure includes
It is forked.
7. film electrode structure as claimed in any of claims 1 to 6, which is characterized in that the separating materials layer tool
There is the thickness by first electrode layer to the direction of the second electrode lay, and described with a thickness of 1~50 micron.
8. film electrode structure according to claim 7, which is characterized in that described with a thickness of 6~45 microns；Or, the thickness
Degree is 16~30 microns；Or, described with a thickness of 20~26 microns.
9. film electrode structure according to claim 7, which is characterized in that the first electrode layer and the second electrode lay
Network-like structure is all had, and the segmentation in the material and the second electrode lay of the separating materials layer in the first electrode layer
The material of material layer is identical or different.
10. film electrode structure according to claim 1, which is characterized in that the first electrode layer is anode, and the sun
Extremely metal electrode or cermet electrodes；
Or the second electrode lay is cathode, and the material of the cathode includes oxide electrode.
11. a kind of fuel cell, which is characterized in that including the film electrode structure as described in any one of claims 1 to 10.
12. a kind of battery pile, which is characterized in that including at least two fuel cells as claimed in claim 11, adjacent two
It is connected between a fuel cell by bipolar plates.
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