CN103474687A - Method for preparing a high-performance slab solid oxide fuel single battery - Google Patents
Method for preparing a high-performance slab solid oxide fuel single battery Download PDFInfo
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Abstract
The invention relates to a method for preparing a high-performance slab solid oxide fuel single battery. The preparation method comprises: a support electrode diaphragm and an electrolyte diaphragm are overlapped and are subjected to hot pressing under a vacuum condition so as to form a first complex diaphragm; a non-support electrode diaphragm and a complex diaphragm are overlapped and then are subjected to hot pressing so as to form a second complex diaphragm; one side of an electrolyte of the first complex diaphragm and one side of the non-support electrode of the second complex diaphragm are overlapped in a contact manner so as to form a single battery blank; the single battery blank is sintered so as to manufacture a single battery, wherein the complex diaphragm is burnt out during the sintering process, a anode diaphragm is formed by the support electrode diaphragm and a cathode diaphragm is formed by the non-support electrode diaphragm, or the cathode diaphragm is formed by the support electrode diaphragm and the anode diaphragm is formed by the non-support electrode diaphragm; the complex diaphragm is prepared from substances which can be burnt out at a temperature of 200-1450 DEG C.
Description
Technical field
The present invention relates to a kind of preparation method of high-performance flat-plate solid-oxide individual fuel cell, affiliated field is field of energy source materials.
Background technology
Solid Oxide Fuel Cell (Solid oxide fuel cell, SOFC) be a kind ofly can directly fuel chemical energy be converted into to the device of electric energy, there is energy conversion efficiency high (overall efficiency is up to more than 85%), fuel tolerance is wide, and (available fuel comprises hydrogen, natural gas, synthesis gas, liquid carbon hydrogen fuel), without advantages such as noble metal catalyst and safety non-pollutions, at large-scale power station, the fields such as decentralized power supply and family's cogeneration are with a wide range of applications.
SOFC, according to its working temperature classification, can be divided into high temperature (800-1000 ℃), tri-kinds of middle high temperature (600-800) and low temperature (<600 ℃) SOFC.The SOFC operating temperature of main flow generally, between 700-800 ℃, belongs to middle high temperature category at present.Hot operation has not only improved the SOFC material cost, but also has brought stability problem, has seriously hindered its practical application.The operating temperature of SOFC is reduced, replace expensive pottery as metallic interconnect materials with cheap stainless steel, can effectively reduce the material cost of SOFC pile, low temperature can also reduce the thermal stress between multi-layer ceramics in addition, slow down the rate of ageing of electrode material, improve the long-time stability of pile power output.So the SOFC low temperature is current international research tendency.
An important indicator estimating SOFC monocell performance is exactly impedance.In SOFC, impedance comprises ohmage (Zohm), polarization impedance and interface contact impedance (Zinterface), and wherein polarization impedance is divided into again anode polarization impedance (Zanode) and cathodic polarization impedance (Zcathode).Along with the reduction of SOFC working temperature, ohmage, polarization impedance and interface contact impedance all enlarge markedly, and make battery performance sharply descend.Say to a certain extent, the research of low temperature SOFC be to fall low-impedance research.
The reduction of ohmage can or adopt the novel electrolytes material to meet by the attenuate electrolyte thickness.With regard to current anode-supported or structure for supporting of cathode, electrolyte thickness has been reduced between 5-15 μ m from traditional hundreds of micron, and ohmage has obtained very big reduction.The lanthanum gallate (being LSGM) of novel electrolytes material such as strontium and magnesium doping, and samarium or the cerium oxide (being SDC or GDC) of gadolinium doping, also possessed enough conductivity at low temperatures.The above-mentioned novel electrolytes of 10 micron thick its total ohmage under 550 ℃ is only also 0.1 Ω cm
2.Generally speaking, for the SOFC 550-600 ℃ of work, ohmage has not been the key factor of its performance of restriction.
Visible, the electrode polarization impedance of battery and interface contact impedance are the principal elements that limits its performance.Silk screen printing and solution impregnation are two kinds of main method that prepare at present electrode.Compare with silk screen print method, by the resulting electrode activity component of solution dipping method, become the nano-dispersed state, its performance often will exceed an order of magnitude, is the electrode preparation method of current low temperature SOFC main flow.The dipping anode of take is example, and the preparation method is as follows for Ni/SDC dipping composite anode: the nickel nitrate complex solution is impregnated in the porous electrolyte skeleton by capillary force, through 85 ℃ of dry 30min, after 700-850 ℃ of calcining 2h-10h, forms the dipping composite anode.Because Ni has excellent catalytic performance to H2, so the Ni composite anode often has very low polarization impedance.The polarization impedance of Ni/LSGM dipping anode in the time of 550 ℃ of the reports such as LIU is only 0.01 Ω cm
2, its numerical value can be ignored fully.Impregnated cathode is similar to the dipping anode, and that difference is the active material of cathode use is not Ni, but comprises La
0.5sr
0.5coO
3, La
0.6sr
0.4co
0.8fe
0.2o
3, La
0.6sr
0.4feO
3, Ba
0.5sr
0.5co
0.8fe
0.2o
3and Sm
0.5sr
0.5coO
3deng perovskite structure and GaBaCo
2o
5, SmBaCo
2o
5, PrBaCo
2o
5and La
2niO
4material Deng double-perovskite and laminated perovskite structure.The people such as Xia are at SDC skeleton the inside dipping SSC nano particle, and its polarization impedance under 550 ℃ is 0.1 Ω cm
2, the people such as Zhan are flooded the SSC/SDC mixed solution in the LSGM skeleton, and its polarization impedance is only 0.075 Ω cm at 550 ℃
2, the composite cathode that the people such as Han form at LSGM skeleton the inside dipping SBSCO even is low to moderate 0.035 Ω cm at 550 ℃ of lower polarization impedances
2.
If do not consider the interface contact impedance, only consider ohmage and polarization impedance, take 10 micron thick SDC (GDC) or LSGM is electrolyte, the power density under 550 ℃ can reach 1.5W/cm in theory
2.But in fact, this performance is difficult to realize.Visible, also comprise the interface contact impedance of some in the total impedance of low temperature SOFC.As its name suggests, the interface contact impedance is relevant with the combination degree at interface, so its size has much relations with the preparation technology of battery.Preparation method about the SOFC monocell mainly contains three kinds at present: traditional two-step sintering method, the half-cell pre-burning at first a kind of electrode and electrolyte formed once, then another kind of electrode composition in silk screen printing on the electrolyte after pre-burning can obtain monocell or monocell skeleton after double sintering.With co-sintering, compare, double sintering rear interface contact resistance is often also very large, particularly just more obvious under low temperature condition; The second preparation method is silk screen printing, the i.e. another kind of electrode material of silk screen printing on " electrode/electrolyte " compound green compact, finally co-sintering obtains monocell or monocell skeleton together, domestic Shanghai Communications University and in the world the researcher people such as University of Pennsylvania adopt this method to prepare monocell, the method can reduce the interface contact impedance to a certain extent, but its technique more complicated, rate of finished products is very low simultaneously.The third preparation method is film applicator coating, refer to and stick another kind of electrode casting films on " support electrode/electrolyte " composite body, although this subsides method can be prepared monocell, and rate of finished products is very high, but the reliability of its interface contact can not be guaranteed, difference between different batteries is also very large, and battery performance and its theoretical value also have larger gap.
Summary of the invention
For the problems referred to above, the object of the present invention is to provide a kind of preparation method of high-performance solid oxidate individual fuel cell, to eliminate or to reduce the interface resistance between electrode and electrolyte, prepare the SOFC monocell of excellent performance.
At this, the invention provides a kind of preparation method of high-performance flat-plate solid-oxide individual fuel cell, comprising: by after the stack of support electrode diaphragm and electrolyte membrane under vacuum condition hot pressing form the first compound film sheet; Non-support electrode diaphragm is become to the second compound film sheet with hot pressing after the composite membrane stack; After the non-support electrode of the electrolyte of described the first compound film sheet one side and described the second compound film sheet is simultaneously superposeed in contact, hot pressing becomes the monocell biscuit; And by described monocell biscuit sintering to make monocell, at composite membrane described in described sintering process by after-flame; Wherein, described support electrode diaphragm forms the anode diaphragm and described non-support electrode diaphragm forms the negative electrode diaphragm, or described support electrode diaphragm forms the negative electrode diaphragm and described non-support electrode diaphragm forms the anode diaphragm; Described composite membrane is comprised of material that can after-flame between 200～1450 ℃.
The present invention adopts the replica membrane technology, can realize that " anode, electrolyte and negative electrode " three parts press and co-sintering altogether, thereby effectively eliminate or reduce the interface contact resistance between electrode and electrolyte, and, hot pressing after the stack of non-support electrode diaphragm and composite membrane is become to compound film sheet, can prevent that when hot pressing the electrolyte membrance effect caused in being press-fit into electrode because of electrolyte lost efficacy.In addition, at composite membrane described in sintering process, by after-flame, therefore can not exert an influence to monocell.Prepare electrode with traditional double sintering method, silk screen print method and film applicator coating and compare, the advantage such as the present invention has that technique is simple, rate of finished products is high, reproducible and excellent performance.And, with traditional double sintering method, to compare, once sintered energy consumption reduces by half, and preparation time reduces by half, and cost significantly reduces.Therefore, the present invention is applicable to prepare baby battery or large battery, is particularly useful for preparing the large tracts of land monocell, can do large-scale production.
Preferably, described support electrode diaphragm, electrolyte membrane, non-support electrode diaphragm and/or composite membrane can adopt the tape casting preparation.
Preferably, the platen area of described support electrode diaphragm can be larger than the platen area of described non-support electrode diaphragm.Can between anode and negative electrode, reserve electrolyte space like this, play the effect of isolated anode and negative electrode, to facilitate the encapsulation of later stage battery.
Preferably, the Thickness Ratio of described non-support electrode diaphragm and described composite membrane can be (1～3): 10.
Preferably, described support electrode diaphragm and/or described non-support electrode diaphragm can be any one in the porous electrolyte skeleton consisted of electrolyte, the porous electrode skeleton consisted of electrode active material and the porous composite electrode skeleton that is composited by electrolyte and electrode active material.
Preferably, described electrolyte can be lanthanum gallate, doping bismuth oxide or other bismuth system oxide, the yttrium of strontium magnesium codope stable zirconia, scandium stable zirconia, doped cerium oxide, silicon (lanthanum germanate), calcium hematite structure (Ba2In2O5) or its doping oxide and/or cerium acid barium.
Preferably, described material that can after-flame between 200～1450 ℃ can be graphite, carbon dust, starch or other any organic powder.
Preferably, the thickness of described support electrode diaphragm can be 100 μ m～400 μ m, and porosity can be 30%～80%, is preferably 40%.
Preferably, the thickness of described non-support electrode diaphragm can be 5 μ m～100 μ m, and porosity can be 30%～80%, is preferably 40%.
Preferably, described hot pressing can be hot pressing 5～25 minutes under 50～90 ℃ of pressure at 1000～5000PSI.
Preferably, described sintering can be 1200～1500 ℃ of sintering 2～24 hours.
Preferably, described support electrode diaphragm, non-support electrode diaphragm and/or composite membrane can be the structures by the individual layer base substrate stack separately more than one deck.The number of plies of the individual layer base substrate superposeed by adjusting, can effectively control the thickness of each diaphragm, improves the finished product rate.
The accompanying drawing explanation
Fig. 1 is the preparation flow schematic diagram of the dull and stereotyped SOFC monocell of high-performance of one example according to the present invention;
Fig. 2 is the SEM micro-structure diagram according to the monocell of embodiments of the invention 1;
Fig. 3 is the electrochemical impedance spectrogram according to the monocell of embodiments of the invention 1;
Fig. 4 is the chemical property figure according to the monocell of embodiments of the invention 1;
Fig. 5 is the chemical property comparison diagram according to the monocell of embodiments of the invention 1 and the monocell that obtains by film applicator coating;
Fig. 6 is the chemical property figure according to the monocell of embodiments of the invention 2;
Fig. 7 is the chemical property figure according to the monocell of embodiments of the invention 3.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following execution mode, should be understood that following accompanying drawing and/or execution mode are only for the present invention is described, and unrestricted the present invention.
The present invention adopts the replica membrane technology, and purpose is that the biscuit of realizing " anode/electrolyte/negative electrode " monocell presses and co-sintering altogether.
Fig. 1 illustrates the preparation flow schematic diagram of the dull and stereotyped SOFC monocell of high-performance of one example according to the present invention.With reference to Fig. 1, preparation method of the present invention is described.
At first, difference curtain coating electrolyte membrane, support electrode (male or female) diaphragm, non-support electrode (negative electrode or anode) diaphragm and composite membrane.
Electrolyte membrane can be electrolyte, dispersant, binding agent, plasticiser and solvent ball milling are mixed to rear curtain coating and make.But the casting method that should be understood that electrolyte membrane is not limited to this, so long as can obtain the casting method of dense electrolyte diaphragm, all comprise in the present invention.Wherein said electrolyte includes but not limited to zirconia (SSZ), doped cerium oxide, silicon (lanthanum germanate), calcium hematite structure (Ba2In2O5) or its doping oxide and/or the cerium acid barium that lanthanum gallate (LSGM), doping bismuth oxide or other bismuth system oxide, the yttrium of strontium magnesium codope stable zirconia (YSZ), scandium are stable.
Support electrode diaphragm and/or non-support electrode diaphragm can be only by electrolyte, pore creating material, dispersant, binding agent, plasticiser and solvent ball milling, to mix rear curtain coating and next porous electrolyte skeleton; Can be also to mix rear curtain coating and next porous electrode skeleton by electrode active material (active material of positive electrode or active material of cathode), pore creating material, dispersant, binding agent, plasticiser and solvent ball milling; Can also be to mix rear curtain coating and next porous composite electrode skeleton by electrode active material (active material of positive electrode or active material of cathode), electrolyte, pore creating material, dispersant, binding agent, plasticiser and solvent ball milling.The casting method that should be understood that equally support electrode diaphragm and/or non-support electrode diaphragm is not limited to this, so long as can obtain the casting method of porous support electrode diaphragm and/or the non-support electrode diaphragm of porous, all comprises in the present invention.Wherein said electrolyte includes but not limited to zirconia (SSZ), doped cerium oxide, silicon (lanthanum germanate), calcium hematite structure (Ba2In2O5) or its doping oxide and/or the cerium acid barium that lanthanum gallate (LSGM), doping bismuth oxide or other bismuth system oxide, the yttrium of strontium magnesium codope stable zirconia (YSZ), scandium are stable.Described active material of positive electrode includes but not limited to NiO, and described active material of cathode includes but not limited to La
0.8sr
0.2mnO
3, La
0.5sr
0.5coO
3, La
0.6sr
0.4co
0.8fe
0.2o
3, La
0.6sr
0.4feO
3, Ba
0.5sr
0.5co
0.8fe
0.2o
3and Sm
0.5sr
0.5coO
3, La
0.9sr
0.1perovskite structure and the GaBaCo such as NiO manganate, cobaltatess, ferrite and nickelate
2o
5, SmBaCo
2o
5, PrBaCo
2o
5and La
2niO
4material Deng double-perovskite and laminated perovskite structure.
Again, the thickness of support electrode diaphragm and/or non-support electrode diaphragm can be regulated by curtain coating knife up, slurry viscosity.Wherein the thickness range of support electrode diaphragm is adjustable between 100 μ m～400 μ m, and the thickness range of non-support electrode diaphragm is adjustable between 5 μ m～100 μ m.The porosity of support electrode diaphragm and/or non-support electrode diaphragm can be regulated by pore creating material kind, quantity and monocell sintering shrinkage, for example can 30%～80% adjustable, be preferably 40%.
Composite membrane can be that material that can after-flame between 200～1450 ℃ is mixed to curtain coating and makes with certain additive.By means of this, in following hot pressing, composite membrane can keep, and, in following sintering process, composite membrane can after-flame.Wherein said material that can after-flame between 200～1450 ℃ includes but not limited to graphite, carbon dust or starch etc.Should be understood that equally so long as can access the casting method of composite membrane and all comprise in the present invention.
Then, as described below, respectively by after the stack of support electrode diaphragm and electrolyte membrane under vacuum condition hot pressing form the first compound film sheet, by non-support electrode diaphragm and composite membrane stack afterwards hot pressing become the second compound film sheet.Wherein, can be that the support electrode diaphragm forms the anode diaphragm and non-support electrode diaphragm forms the negative electrode diaphragm, can be also the support electrode diaphragm forms the negative electrode diaphragm and non-support electrode diaphragm forms the anode diaphragm.And, in the present invention, can be that the platen area of support electrode diaphragm is larger than the platen area of non-support electrode diaphragm, thereby reserve electrolyte space between anode and negative electrode, play the effect of isolated anode and negative electrode, to facilitate the encapsulation of later stage battery.Therefore, after making support electrode diaphragm and non-support electrode diaphragm, can first they be cut into to small one and large one structure, then carry out following step.
At first, as shown in " first step " in Fig. 1, requirement according to support electrode to thickness, by multi-disc support electrode diaphragm and electrolyte membrane stack, under vacuum condition, under 50～90 ℃ of pressure at 1000～5000PSI, hot pressing forms the first compound film sheet in 5～25 minutes.Shown in figure, by the stack of 4 support electrode diaphragms, but it illustrates as example, and in the present invention, the sheet of stack is several to be determined the requirement of thickness according to support electrode, can be for example 2～10.By lamination hot pressing, can effectively control the thickness of each layer, improve the finished product rate.
Then, as shown in " second step " in Fig. 1, by Thickness Ratio, be (1～3): after the stack of 10 non-support electrode diaphragm and composite membrane under 50～90 ℃ of pressure at 1000～5000PSI hot pressing within 5～25 minutes, form the second compound film sheet.By means of this, non-support electrode diaphragm is pressed in composite membrane, and their upper surface at grade.Wherein, composite membrane can be according to its thickness requirement, the stack of the composite membrane more than a slice hot pressing to be formed, and similarly, non-support electrode diaphragm can be also according to its thickness requirement, the non-support electrode diaphragm stack hot pressing more than a slice to be formed.By lamination hot pressing, can effectively control the thickness of each layer, improve the finished product rate.
Then, as shown in " the 3rd step " in Fig. 1, by the non-support electrode one side of the electrolyte of the first compound film sheet one side and the second compound film sheet in contact after stack under 50～90 ℃ of pressure at 1000～5000PSI 5～25 minutes formation monocell biscuits of hot pressing.Then by the monocell biscuit 1200～1500 ℃ of sintering 2～24 hours to make monocell.In sintering process, composite membrane is by after-flame, thus the structure of formation anode (large side)/electrolyte/negative electrode (little side) or negative electrode (large side)/electrolyte/anode (little side).
As shown in " contrast step " in Fig. 1, if do not adopt the replica film, " anode/electrolyte/negative electrode " monocell biscuit is directly pressed altogether, electrolyte can be pressed in electrode, directly causes electrolytical barrier film effect to be lost efficacy.
Therefore, compared with prior art, the present invention has following advantage:
(1) prepare electrode with traditional double sintering method, silk screen print method and film applicator coating and compare, the advantage such as preparation method of the present invention has that technique is simple, rate of finished products is high, reproducible and excellent performance;
(2) the present invention has successfully realized that " anode, electrolyte and negative electrode " three parts press and co-sintering altogether, effectively eliminates or has reduced the interface contact resistance between electrode and electrolyte;
(3) the present invention is applicable to prepare baby battery or large battery, is particularly useful for preparing the large tracts of land monocell, can do large-scale production;
(4) with traditional double sintering method, compare, once sintered energy consumption of the present invention reduces by half, and preparation time reduces by half, and cost significantly reduces;
(5) in the present invention, by lamination hot pressing, can effectively control the thickness of each layer, the finished product rate is high.
The foregoing is only preparation flow, but above-mentioned flow process is applicable to prepare different battery structures.That is, the formation difference according to support electrode diaphragm and/or non-support electrode diaphragm, can form different battery structures.Below illustrate four kinds of battery structures, but should understand them only as example, and be not limited to this four kinds of structures.
Battery structure I: " porous electrolyte/dense electrolyte/porous electrolyte " structure
In this structure, electrode formula and electrolyte formula difference are: the electrode formula additionally comprises the pore creating material of some.In dense electrolyte and porous electrolyte, electrolyte can be same material, can be also different materials.The also incomplete monocell prepared by said method, and be the monocell skeleton, by flood respectively anode and cathode activity composition on both sides, finally can obtain complete monocell.
Battery structure II: " anode (negative electrode) supporter/dense electrolyte/porous electrolyte " structure
In this structure, electrode formula and electrolyte formula difference are: the electrode formula additionally comprises the pore creating material of some.In dense electrolyte and porous electrolyte, electrolyte can be same material, can be also different materials.This anode (negative electrode) supporter can be simple anode (negative electrode) supporter, can be also the supporter that is accompanied with active layer.Difference only is that the tape casting diaphragm composition is different.The also incomplete monocell prepared by said method, and be half-cell, form anode or negative electrode by dipping anode or cathode activity composition in porous electrolyte, finally can obtain complete monocell.
Battery structure III: " anode (negative electrode) supporter/dense electrolyte/porous cathode (anode) " structure
Porous cathode in this structure (anode) refers to the cathode material (anode material) that is different from electrolyte.Described cathode material (anode material) can be simple cathode material (anode material), can be also the combination electrode that negative electrode (anode) and electrolyte are composited.This anode (negative electrode) supporter can be simple anode (negative electrode) supporter, can be also the supporter that is accompanied with active layer.Difference only is that the tape casting diaphragm composition is different.The also incomplete monocell prepared by said method, and be half-cell, can form negative electrode or anode by dipping electrolyte in porous cathode (anode), finally can obtain complete monocell.
Battery structure IV: " anode (negative electrode) supporter/dense electrolyte/negative electrode (anode) " structure
Negative electrode in this structure (anode) refers to the cathode material (anode material) that is different from electrolyte.Described negative electrode (anode) material can be simple negative electrode (anode material), can be also the combination electrode that negative electrode (anode) and electrolyte are composited.This anode (negative electrode) supporter can be simple supporter, also can make to be accompanied with the supporter of active layer.This negative electrode (anode) can be single layer structure, can be also the double-decker of subsidiary active layer, or sandwich construction.Difference only is that the tape casting diaphragm composition is different.
Below further exemplify embodiment to describe the present invention in detail.Should understand equally; following examples only are used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention., those skilled in the art can do in suitable scope and select by the explanation of this paper, and not really want to be defined in the hereinafter concrete numerical value of example each parameter that following example is concrete is only also an example in OK range.
Embodiment 1
Battery structure I: " porous electrolyte/dense electrolyte/porous electrolyte " structure
Take appropriate commercialization powder LSGM(lanthanum strontium gallium magnesium), take alcohol and butanone as solvent, add appropriate additive, be made into the slurry that is applicable to curtain coating, curtain coating obtains LSGM electrolyte base substrate; Take appropriate commercialization powder LSGM(lanthanum strontium gallium magnesium), pore creating material, take alcohol and butanone as solvent, add appropriate additive, be made into the slurry that is applicable to curtain coating, curtain coating obtains LSGM porous electrode base substrate; Take the flammable powder carbon dust of appropriate high temperature, take alcohol and butanone as solvent, add appropriate additive, be made into the slurry that is applicable to curtain coating, curtain coating obtains replica film base substrate.To after the stack of 3 layers of porous electrode base substrate and one deck LSGM electrolyte base substrate, hot pressing, obtain " porous electrolyte/dense electrolyte " supporter.To after 2 layers of composite membrane stack, hot pressing, obtain having certain thickness composite membrane.By one deck porous electrolyte biscuit and above-mentionedly obtain the composite membrane that load has electrode after thering is the stack of certain thickness replica film, hot pressing.Obtain complete monocell biscuit after supporter and load being had to the stack of replica film, hot pressing of electrode.The monocell biscuit is put into to high temperature furnace sintering 4 hours between 1400 ℃, obtain the monocell skeleton.Flood respectively Ni (NO on one side at above-mentioned monocell skeleton
3)
3, then heat treatment obtains anode; At above-mentioned monocell skeleton another side, flood by Sm (NO
3)
3, Sr (NO
3)
3, Co (NO
3)
3and Ba (NO
3)
3the SBSCO cathode material that mixed solution forms, then heat treatment obtains negative electrode.
The monocell micro-structure diagram obtained by above-mentioned preparation method as shown in Figure 2.Fig. 3 is its electrochemical impedance spectrogram.Fig. 4 is its chemical property figure.The monocell performance that the monocell performance that Fig. 5 will obtain with the replica membrane technology and film applicator coating obtain contrasts.As can be seen from Figure 2, by above-mentioned replica membrane technology, can successfully obtain " porous LSGM/ fine and close LSGM/ porous LSGM " sandwich structure, electrolyte thickness 8-9 μ m wherein, support electrode 400 μ m left and right, the opposite side thickness of electrode is probably also in 40 μ m left and right.For LSGM, its conductivity in the time of 550 ℃ is generally at 0.01S/cm, and the electrolyte of the 8-9 μ m ohmage of correspondence in theory is 0.08-0.09 Ω cm
2.As can be seen from Figure 3, its ohmage of monocell obtained by above-mentioned replica membrane technology is 0.1 Ω cm in the time of 550 ℃
2, basically suitable with theoretical ohmage value, remaining 0.01-0.02 Ω cm
2even if resistance value be the interface contact impedance fully, its numerical value also can be ignored.As can be seen here, by " anode, electrolyte and negative electrode " three parts are pressed and co-sintering altogether, effectively eliminated the interface contact resistance between electrode and electrolyte.Fig. 4 is its power density diagram, and the performance of this monocell in the time of 550 ℃ reached 1.8W/cm
2.The monocell performance that Fig. 5 will be obtained by replica membrane technology and film applicator coating contrasts, wherein the A representative is the replica embrane method, what B represented is film applicator coating, and as known in the figure, the performance of the monocell obtained by the replica membrane technology is significantly higher than the performance of the monocell obtained by film applicator coating.
Embodiment 2
Battery structure II: " cathode support body/dense electrolyte/anode " structure
Take the lanthanum manganate of appropriate commercialization powder LSM(strontium doping) and NiO, take alcohol and butanone as solvent, add appropriate additive, be made into the slurry that is applicable to curtain coating, curtain coating obtains LSM/NiO cathode support electrode base substrate; Take the complete stable zirconia of appropriate commercialization powder 8YSZ(8% yttrium), take alcohol and butanone as solvent, add appropriate additive, be made into the slurry that is applicable to curtain coating, curtain coating obtains 8YSZ electrolyte base substrate; Take the complete stable zirconia of appropriate commercialization powder 8YSZ(8% yttrium) and NiO, take alcohol and butanone as solvent, add appropriate additive, be made into the slurry that is applicable to curtain coating, curtain coating obtains the anode biscuit; Take the flammable powder carbon dust of appropriate high temperature, take alcohol and butanone as solvent, add appropriate additive, be made into the slurry that is applicable to curtain coating, curtain coating obtains replica film base substrate.To after the stack of 3 layers of strut body electrode base substrate and one deck electrolyte biscuit, hot pressing, obtain " cathode support body/electrolyte " supporter biscuit.To after 2 layers of composite membrane stack, hot pressing, obtain having certain thickness composite membrane.By one deck anode biscuit and above-mentionedly obtain the composite membrane that load has anode after thering is the stack of certain thickness replica film, hot pressing.Obtain complete monocell biscuit after supporter and load being had to the stack of replica film, hot pressing of anode.The monocell biscuit is put into to high temperature furnace sintering 4 hours between 1250 ℃, obtain monocell.Fig. 6 is its chemical property figure, and as known in the figure, the performance of this monocell in the time of 850 ℃ reached 0.63W/cm
2.
Embodiment 3
Battery structure III: " anode support/dense electrolyte/porous electrolyte " structure
Take the complete stable zirconia of appropriate commercialization powder 8YSZ(8% yttrium) and NiO, take alcohol and butanone as solvent, add appropriate additive, be made into the slurry that is applicable to curtain coating, curtain coating obtains YSZ/NiO strut body electrode base substrate; Take the complete stable zirconia of appropriate commercialization powder 8YSZ(8% yttrium), take alcohol and butanone as solvent, add appropriate additive, be made into the slurry that is applicable to curtain coating, curtain coating obtains 8YSZ electrolyte base substrate; Take the complete stable zirconia of appropriate commercialization powder SSZ(10% scandium), pore creating material, take alcohol and butanone as solvent, add appropriate additive, be made into the slurry that is applicable to curtain coating, curtain coating obtains the porous electrolyte base substrate; Take the flammable powder carbon dust of appropriate high temperature, take alcohol and butanone as solvent, add appropriate additive, be made into the slurry that is applicable to curtain coating, curtain coating obtains replica film base substrate.To after the stack of 3 layers of strut body electrode base substrate and one deck electrolyte biscuit, hot pressing, obtain " anode support/electrolyte " supporter biscuit.To after 2 layers of composite membrane stack, hot pressing, obtain having certain thickness composite membrane.By one deck porous electrolyte biscuit and above-mentionedly obtain the composite membrane that load has the porous electrolyte material after thering is the stack of certain thickness replica film, hot pressing.Obtain complete monocell biscuit after supporter and load being had to the stack of replica film, hot pressing of porous electrolysis material.The monocell biscuit is put into to high temperature furnace sintering 4 hours between 1400 ℃, obtain half-cell.Flood Sm in the porous electrolyte skeleton of half-cell
0.5sr
0.5coO
3active material of cathode, obtain complete monocell after heat treatment.Fig. 7 is its chemical property figure, and as known in the figure, the performance of this monocell in the time of 850 ℃ reached 1.1W/cm
2.
Industrial applicability: the present invention can effectively eliminate or reduce the interface contact resistance between electrode and electrolyte; prepare the SOFC monocell of excellent performance; and the inventive method has the advantages such as technique is simple, workable, rate of finished products is high and be produced on a large scale, can be applied to the preparation field of low temperature SOFC.
Claims (12)
1. the preparation method of a high-performance flat-plate solid-oxide individual fuel cell, is characterized in that, comprising:
By after the stack of support electrode diaphragm and electrolyte membrane under vacuum condition hot pressing form the first compound film sheet;
Non-support electrode diaphragm is become to the second compound film sheet with hot pressing after the composite membrane stack;
After the non-support electrode of the electrolyte of described the first compound film sheet one side and described the second compound film sheet is simultaneously superposeed in contact, hot pressing becomes the monocell biscuit; And
By described monocell biscuit sintering to make monocell, at composite membrane described in described sintering process by after-flame;
Wherein, described support electrode diaphragm forms the anode diaphragm and described non-support electrode diaphragm forms the negative electrode diaphragm, or described support electrode diaphragm forms the negative electrode diaphragm and described non-support electrode diaphragm forms the anode diaphragm;
Described composite membrane is comprised of material that can after-flame between 200～1450 ℃.
2. preparation method according to claim 1, is characterized in that, described support electrode diaphragm, electrolyte membrane, non-support electrode diaphragm and/or composite membrane adopt the tape casting preparation.
3. preparation method according to claim 1 and 2, is characterized in that, the platen area of described support electrode diaphragm is larger than the platen area of described non-support electrode diaphragm.
4. according to the described preparation method of any one in claims 1 to 3, it is characterized in that, the Thickness Ratio of described non-support electrode diaphragm and described composite membrane is (1～3): 10.
5. according to the described preparation method of any one in claim 1 to 4, it is characterized in that, described support electrode diaphragm and/or described non-support electrode diaphragm are any one in the porous electrolyte skeleton consisted of electrolyte, the porous electrode skeleton consisted of electrode active material and the porous composite electrode skeleton that is composited by electrolyte and electrode active material.
6. preparation method according to claim 5, it is characterized in that the lanthanum gallate that described electrolyte is strontium magnesium codope, stable stable zirconia, doping bismuth oxide or other bismuth system oxide, doped cerium oxide, silicon (lanthanum germanate), calcium hematite structure (Ba2In2O5) or its doping oxide and/or the cerium acid barium of zirconia, scandium of yttrium.
7. preparation method according to claim 1, is characterized in that, described material that can after-flame between 200～1450 ℃ comprises graphite, carbon dust, starch or other any organic powder.
8. according to the described preparation method of any one in claim 1 to 7, it is characterized in that, the thickness of described support electrode diaphragm is 100 μ m～400 μ m, and porosity is 30%～80%.
9. according to the described preparation method of any one in claim 1 to 8, it is characterized in that, the thickness of described non-support electrode diaphragm is 5 μ m～100 μ m, and porosity is 30%～80%.
10. according to the described preparation method of any one in claim 1 to 9, it is characterized in that, described hot pressing is hot pressing 5～25 minutes under 50～90 ℃ of pressure at 1000～5000PSI.
11. according to the described preparation method of any one in claim 1 to 10, it is characterized in that, described sintering is 1200～1500 ℃ of sintering 2～24 hours.
12. according to the described preparation method of any one in claim 1 to 11, it is characterized in that, described support electrode diaphragm, non-support electrode diaphragm and/or composite membrane are the structures by the individual layer base substrate stack separately more than one deck.
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| CN113969408A (en) * | 2021-10-12 | 2022-01-25 | 清华大学 | Solid oxide fuel electrolytic cell and preparation method thereof |
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