CN108336386B - Flat tube structure solid oxide electrochemical device and preparation method thereof - Google Patents

Flat tube structure solid oxide electrochemical device and preparation method thereof Download PDF

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CN108336386B
CN108336386B CN201711462243.7A CN201711462243A CN108336386B CN 108336386 B CN108336386 B CN 108336386B CN 201711462243 A CN201711462243 A CN 201711462243A CN 108336386 B CN108336386 B CN 108336386B
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electrode
slurry
oxygen
electrochemical device
heater
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胡强
吴剑
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Zhejiang Zhen Tai Energy Technology Co Ltd
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    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
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Abstract

The invention relates to the field of electrochemistry and discloses a solid oxide electrochemical device with a flat tube structure and a preparation method thereof, wherein the electrochemical device comprises an outer electrode, an outer electrode connecting wire, an electrolyte, an inner electrode connecting wire and an isolation structure; the outer electrode and the outer electrode connecting wire are connected and arranged on the outer side surface of the electrolyte, and the inner electrode connecting wire are connected and arranged on the inner side surface of the electrolyte; the isolation structure is formed by enclosing electrolyte, two gas channel walls and a partition plate; an air passage with two open ends is arranged in the isolation structure. The flat tube type electrochemical device has good sealing performance and high reliability; the yield is high, and the mass production is easy; meanwhile, the stack is flexible, the hot replacement operation of the failed battery under the high-temperature condition is supported, the service life of the SOC electric stack can be obviously prolonged, the operation flexibility is enhanced, and the operation cost is reduced.

Description

Flat tube structure solid oxide electrochemical device and preparation method thereof
Technical Field
The invention relates to the fields of solid oxide fuel cells, solid oxide fuel electrolysis cells, new energy sources, new materials and electrochemistry, in particular to a solid oxide electrochemical device with a flat tube structure and a preparation method thereof.
Background
SOC (solid oxide cells) is a solid oxide electrochemical device consisting of at least one layer of electrolyte, typically doped stabilized zirconia, such as 8 mol% Y2O, and at least two electrodes3Stabilized zirconia (8 YSZ) or Sc2O3Doped stabilized zirconia, such as ScSZ, or calcia, CaO Stabilized Zirconia (CSZ). The electrolyte can also be other fluorite-structured oxides, such as gadolinium oxide or samarium oxide doped stabilized cerium oxide (GDC, SDC), and perovskite-structured oxides, such as lasrgmgo, and the like. The material composition of the electrode may be an oxide of perovskite structure, such as LaSrMnO3(LSM), or a composite, such as a composite of LSM and YSZ, or a precious metal, such as Pt, or a precious metal-containing composite, such as a composite of Pt and YSZ.
The oxygen-rich atmosphere is typically air and the corresponding electrode is referred to as an air electrode, and typically oxygen-poor atmospheres are hydrogen/water mixtures, hydrogen/carbon monoxide/water mixtures, carbon monoxide/carbon dioxide mixtures, nitrogen oxides (NOx)/nitrogen mixtures, and the corresponding electrode is referred to as a fuel electrode. The oxygen-deficient and oxygen-rich electrodes are separated by an electrolyte. Charge conduction of the SOC electrolyte is generally carried by oxygen ions, i.e. oxygen ion conductance, and if there is significant electron conductance at the same time, there is a short circuit current inside the SOC, the larger the short circuit current, the lower the SOC efficiency.
The solid oxide element SOC works in a temperature range of 500-1000 ℃, and two working modes can be provided: a power generation mode (Solid Oxide Fuel Cell mode, SOFC mode) and an electrolysis mode (Solid Oxide electrolysis Cell, SOEC mode). When the SOC works in a power generation mode, oxygen molecules in the oxygen-enriched electrode are subjected to reduction reaction to be changed into oxygen ions, the oxygen ions migrate from one side of the oxygen-enriched electrode to one side of the oxygen-deficient electrode through the electrolyte, the oxygen ions are oxidized into the oxygen molecules in the oxygen-deficient electrode and then escape from the oxygen-deficient electrode, the macroscopic expression of the whole process is that the oxygen molecules migrate from one side of the oxygen-enriched gas to one side of the oxygen-deficient gas through the electrolyte, and the oxygen concentration difference between the oxygen-enriched gas and the oxygen-deficient gas is reduced.
In the power generation mode, the SOC converts the chemical energy of the oxygen-deficient gas into electric energy and outputs the electric energy to the outside. Taking the hydrogen and oxygen electrodes as an example, the SOFC mode can be represented as:
anode (oxygen deficient electrode): h2+ O2-→ H2O + 2e-
Cathode (oxygen-rich electrode): 1/2O2+2e-→ 2O2-
And (3) total reaction: h2+1/2 O2→ H2O
When the SOC works in an electrolysis mode, under the action of an external electric field, oxygen molecules are subjected to reduction reaction in the oxygen-poor electrode to be changed into oxygen ions, the oxygen ions migrate to the oxygen-rich electrode through electrolyte, and the oxygen ions are subjected to oxidation reaction in the oxygen-rich electrode to be changed into oxygen molecules and escape from the oxygen-rich electrode. The macroscopic expression of the whole process is that oxygen molecules are transferred from the oxygen-poor gas side to the oxygen-rich gas side through the electrolyte under the action of an external electric field, and the oxygen concentration difference between the oxygen-rich gas and the oxygen-poor gas is increased. In the electrolysis mode, the SOC absorbs externally input electrical energy and converts it into chemical energy of the oxygen-depleted gas. For example, with hydrogen and oxygen electrodes, the SOEC mode can be expressed as:
anode (oxygen-enriched electrode): 2O2-→ 1/2 O2+2e-
Cathode (oxygen deficient electrode): h2O + 2e-→ H2+ O2-
And (3) total reaction: h2O → H2+1/2 O2
When the SOC is operated between the two modes, a conversion between electrical energy and chemical energy may be achieved, which may be accompanied by the release or absorption of heat. Whether the SOC is operating in a battery or electrolysis mode, it may accept external thermal energy input or release thermal energy to the outside itself. Therefore, the mutual conversion among the electric energy, the thermal energy and the chemical energy can be realized by utilizing the SOC technology. When the SOC works in an electrolysis mode, the electric energy is converted into chemical energy to be stored, and when the SOC works in a battery mode, the chemical energy of oxygen-poor gas is directly converted into the electric energy, so that the limitation of Carnot circulation is avoided, and efficient chemical energy utilization is realized.
Typical oxygen-depleted gases such as H2And H2Mixture of O, the overall reaction of SOC in battery mode is: h2+O2→H2O; in cell mode, the overall reaction of SOC is: h2O→H2+O2. A typical oxygen-depleted gas may also be, for example, CO2，H2O，CO，H2The resulting mixture, in cell mode, has a total reaction of SOC: h2+O2→H2O, CO+O2→CO2In the electrolysis mode, the overall reaction of SOC is H2O→H2+O2，CO2→CO+O2Containing CO, H2The electrolysis products can be continuously converted into liquid fuels such as hydrocarbon, gasoline and diesel oil and the like by a mature Fischer-Tropsch synthesis process. When the gas component containing oxygen is Nitrogen Oxide (NO)x) Sulfur Oxides (SO)x) And removing the pollutants by using the electrolytic technology of the SOC at the time of typical environmental pollutants, wherein the chemical process can be expressed as:
NOx→N2+O2(x =1 or 2) or SOx → S + O2(x =1 or 2);
the oxygen-depleted gas may contain a variety of fuel-like components such as carbon monoxide, methane, methanol, hydrogen, etc., and the oxygen-enriched gas may contain oxygen, nitrogen, argon, helium, most commonly air.
The existing SOC mainly comprises a split type and a tubular type. The stack structure of the chip SOC is realized by sequentially connecting an SOC element, a sealing ring (sealing), a connecting plate (interconnect) and the like, and the whole stack is arranged in a high-temperature environment. The sealing ring is generally made of glass or metal (such as gold, silver, etc.), and the material of the connecting plate is usually a high-temperature-resistant alloy. Alloy connection plates also typically require a conductive oxidation-resistant coating to be sprayed on the surface to enhance oxidation resistance under high temperature conditions and reduce stack resistance loss. In most cases, one or more layers of soft metal or ceramic pads are arranged between the electrodes on the two sides of the SOC element and the alloy connecting plate to realize good electrical contact between the SOC element and the connecting plate, and Ag mesh is used on the two sides of the cell in a considerable part of chip SOC technology to ensure good electrical contact. In a chip SOC stack, air flows (oxygen-poor and oxygen-rich) flow in an isolated space formed by a connecting plate, SOC components and a sealing ring, and leakage outside the stack is avoided. The elements of the chip SOC galvanic pile, including SOC element, sealing ring and connecting plate, need to be made separately, and finally combined into a pile. The chip SOC stack has the advantages of straight and regular electrode shape, short current path, relatively large power density and easy stack assembly. The chip SOC stack is difficult to be put into practical use because:
1) the seal ring is not highly reliable. The sealing ring must ensure gas tightness, resist thermal cycling, have certain mechanical strength and flexibility, and have a thermal expansion coefficient close to that of the alloy connecting plate and the SOC battery piece (i.e., thermal expansion matching, i.e., the sealing ring is required to be consistent with the dimensional change of the sealing member under the condition of temperature change), and the performance requirements are difficult to achieve simultaneously by the glass or metal sealing ring. Such as glass seal rings, are often fragile and are very susceptible to failure during stack-up and thermal cycling operations of the SOC.
2) Because each group of stack components needs to be manufactured independently, the technical requirements are high (such as high requirements on flatness, strength, toughness, oxidation resistance and thermal expansion matching of each component), the stack cost of the chip SOC group is usually high, and the practical application of the chip SOC group is also limited.
3) The flexibility of the stack is low. The connection mode of each single battery of the chip SOC stack is in series connection, the sealing ring is a disposable element, once one chip SOC stack is subjected to heat treatment (namely, after the sealing ring and the sealing piece are fused at high temperature (for example, 750 ℃), each element of the stack assembly, including each single battery and the connecting plate, cannot be replaced, and therefore any element in the whole stack fails to work, the whole stack fails, the risk of actually using one chip SOC stack is greatly increased, and the use cost is remarkably increased.
The tubular SOC element is cylindrical, and the cathode and anode are respectively arranged on the inner surface and the outer surface of the tube. Compared with a sheet type structure, the tubular SOC has the advantage that the cold end can be sealed, namely the tubular SOC single battery can be long-span and high-temperature area is up to the cold end. The SOC component is sealed at the cold end (for example, the temperature at the sealing position is 200 degrees or higher than the temperature near the electrode), the technical difficulty is low, and the sealing reliability is greatly improved. The tubular SOC has the following disadvantages:
1) since the tubular SOC is cylindrical, flatness is difficult to achieve in actual preparation, and the adhesion of an electrode connecting material and a cylindrical electrode is difficult to ensure tightness particularly under a high-temperature condition, so that the contact resistance of a single battery is large.
2) During battery preparation, the geometric dimension change of each part of the tubular battery is difficult to be consistent (the shrinkage of a blank is generally consistent) under a curved surface configuration, so that the tubular SOC single battery has poor geometric dimension consistency, the residual stress in the battery is large, and the yield and the stability of the battery performance are influenced.
3) When the unit cell stack is stacked, the inner electrode needs to be connected to the inner (when in parallel connection) or outer electrode (when in series connection) of other unit cells by an intermediate passage. The intermediate passages need to pass through the electrolyte, sometimes referred to as tie plates. In a typical tubular cell, the connecting passages are distributed along the entire (or most of the) axial direction of the inner electrode, covering a portion of the inner electrode. The tubular cell with the intermediate channel design has a complex structure, the electrolyte and the intermediate channel are difficult to seal, and the cell is easy to lose gas to cause cell failure.
4) The structure of the battery stack formed by mutually connecting the inner electrode and the outer electrode of each single battery is complex, the current resistance of the whole tubular SOC battery stack is large, and the current density/power density is generally low.
5) Like a chip SOC stack, in a tubular SOC stack, if a single cell fails, the failure of the single cell may cause the performance reduction of the non-repairability of the entire stack of cells, and even may cause the entire stack failure because the good contact between the new cell and other cells cannot be ensured, and the replacement of a failed cell under a high temperature condition cannot be realized.
Disclosure of Invention
In order to solve the technical problems, the invention provides a solid oxide electrochemical device with a flat tube structure and a preparation method thereof. The flat tube type electrochemical device has good sealing performance and high reliability; the yield is high, and the mass production is easy; meanwhile, the stack is flexible, the hot replacement operation of the failed battery under the high-temperature condition is supported, the service life of the SOC electric stack can be obviously prolonged, the operation flexibility is enhanced, and the operation cost is reduced.
The specific technical scheme of the invention is as follows: a solid oxide electrochemical device with a flat tube structure comprises an outer electrode, an outer electrode connecting wire, an electrolyte, an inner electrode connecting wire, an isolation structure, a heater and a substrate; wherein the outer and inner electrodes are in a planar form; and the outer electrode and the inner electrode are respectively an oxygen-enriched electrode and an oxygen-deficient electrode or respectively an oxygen-deficient electrode and an oxygen-enriched electrode.
The outer electrode and the outer electrode connecting wire are connected and arranged on the outer side face of the electrolyte, and the inner electrode connecting wire are connected and arranged on the inner side face of the electrolyte.
The isolating structure is formed by surrounding an electrolyte, two gas channel walls and a partition plate, and the electrolyte, the two gas channel walls and the partition plate are made of the same material or materials with similar compositions; an air passage with two open ends is arranged in the isolation structure, and gas enters from one open end of the air passage, flows through the inner electrode and exits from the other open end; the air passage is in a straight path shape or a bent shape.
The heater is integrated on the inner side surface of the substrate, and the inner side surface of the substrate is connected with the outer side surface of the isolation structure in an opposite mode.
Preferably, the cross section of the electrochemical device is rectangular, and the cross section of the air channel is rectangular.
Preferably, the electrolyte, the separator, and other main housing components of the electrochemical device are all formed by heat treatment sintering.
Preferably, the heater is an electrically conductive heating track deposited on the substrate.
The heater is formed by depositing a specially designed conductive heating track on a substrate that is integrated with the other structure of the cell via lamination or pressing processes. The heating circuit can also reach the pins through the hole structure, and connection with other external equipment is realized.
Preferably, a first insulating layer is deposited on the inner side of the substrate, a conductive heating line as a heater is deposited on the first insulating layer, and a second insulating layer is deposited on the outer side of the isolation structure. The conductive heating line may also be deposited not directly on the substrate, but first of all on the substrate by depositing a layer of insulating material, such as Al2O3And then depositing on the insulating layer to prepare the heater. The heater interlayer in the insulating material is possible to avoid interference on other pins of the flat tube SOC battery when the current of the heater changes, such as when the heating current is switched off.
Preferably, the material of the first and second insulating layers is alumina.
Preferably, the substrate is integrated with the isolation structure by a lamination or pressing process.
Preferably, the electrochemical device further includes an inner electrode pin. An outer electrode pin and a heater pin; the outer electrode pin is arranged on the outer side surface of the electrolyte and is connected with the outer electrode connecting wire; the inner electrode pin is arranged on the outer side surface of the electrolyte and is far away from the edge of one end of the outer electrode pin, and the inner electrode connecting wire penetrates through a through hole arranged on the electrolyte and is connected with the inner electrode pin;
the heater is connected with the heater pin arranged on the outer side surface of the substrate through a through hole arranged on the substrate;
preferably, the gap at least one of the through holes is filled with a sealing material.
Preferably, the outer electrode pin and the inner electrode pin are respectively connected with a lead.
Preferably, the outer electrode connecting wire, the outer electrode pin and the inner electrode pin are in the same plane.
Preferably, during operation, the tail ends of the inner and outer electrode connecting lines or the inner and outer electrode pins on the electrochemical device are at the cold ends, and the temperature of the cold ends is lower than the highest temperature in the middle area of the electrochemical device by more than 50 ℃.
Preferably, the cold end temperature is more than 200 ℃ lower than the highest temperature in the middle region of the electrochemical device during operation.
Preferably, the inner and outer electrode leads and/or the inner and outer electrode connecting wires are covered by the sealing material.
Preferably, the sealing material is a high temperature resistant sealing material.
Preferably, the sealing material is glass or epoxy.
A preparation method of a flat tube structure solid oxide electrochemical device comprises the following steps:
1) preparing slurry: respectively adding fine powder of an isolation structure material, fine powder of a lean oxygen/oxygen-enriched electrode material, fine powder of an inner/outer electrode connecting wire material, fine powder of an insulating layer, fine powder of a heater, fine powder of an electrode pin, fine powder of the heater pin and fine powder of graphite or starch into an organic assistant, and respectively preparing stable slurry of the isolation structure material, lean oxygen/oxygen-enriched electrode slurry, slurry of the inner/outer electrode connecting wire, slurry of the insulating layer, slurry of the heater, slurry of the electrode pin, slurry of the heater pin and slurry of graphite or starch after ball milling;
2) casting: preparing the isolating structure material slurry into a film by using a casting machine, and then cutting the film into casting sheets with certain sizes;
3) thickening the casting sheet: laminating and thickening a plurality of casting sheets together, vacuumizing, and performing hot pressing to fuse the casting sheets into a thicker base sheet;
4) printing inner and outer electrodes: taking 1 base sheet, adopting lean oxygen/rich oxygen electrode slurry and inner/outer electrode connecting wire slurry, and printing inner electrode/outer electrode and inner/outer electrode connecting wires on two surfaces of the base sheet by using a screen printer respectively;
the printed inner electrode, outer electrode and bond wire pastes may be the same, e.g., a paste of Pt: YSZ =4:1 or different, e.g., Pt:8YSZ =1:1 in the inner and outer electrode pastes, while the bond wire paste composition is Pt:8YSZ =9: 1.
5) Forming an air flue wall: cutting the casting sheet or the base sheet into strips according to the size, then taking 1 piece of the base sheet, marking as a base sheet a, and attaching the strips on the base sheet a to form an airway wall of the isolation structure;
6) air flue forming: filling the graphite or starch slurry into the air channel position in the base sheet a, and drying to ensure that the dried graphite or starch slurry is consistent with the air channel wall in thickness;
the method for realizing the air passage can be that graphite or starch and other pore-forming agents (prepared into proper slurry) are deposited at the position of the air passage by various methods such as filling, silk-screen printing and the like. In the subsequent heat treatment process, the pore-forming agent is heated to decompose and disappear to leave an air channel structure.
7) Preparing a heater: taking 1 piece of the base sheet, marking as a base sheet b, punching a through hole by using a punching machine to prepare a substrate, sequentially printing a first insulating layer, a heater and a second insulating layer on one surface of the substrate, and printing a heater pin on the other surface of the substrate; in the printing process, when the slurry is coated on the via hole, the slurry flows along the hole wall for coating, and after heat treatment, the cross-substrate conduction of the circuit is realized;
8) laminating: sequentially attaching the base pieces prepared in the steps 4), 6) and 7), vacuumizing, and hot-pressing to fuse the base pieces into a biscuit with a complete flat tube structure;
9) and (3) sintering: placing the biscuit in a box type high-temperature furnace for sintering, wherein in the sintering process, the strength of the biscuit is improved, and meanwhile, graphite or starch is decomposed and gasified, so that regular and uniform air passages are left in an isolation structure;
preferably, in the step 1), the organic auxiliary agent is PVB, triethanolamine or ethanol; in the step 2), the thickness of the film is 80-140 μm; in the step 3) and the step 8), the hot pressing process comprises the following steps: applying pressure of 5-40MPa at 70-95 deg.C and maintaining for 8-12 min; in the step 9), the sintering temperature is 1300-1500 ℃, and the sintering time is 1-3 hours.
Preferably, in step 7), negative pressure suction is applied to the via hole position of the base sheet while printing to enhance the effect of the paste coating the via hole.
Preferably, after the step 9), the method further comprises the step 10) of strengthening the electrodes: sm (NO) firstly3)3Or Gd (NO)3），Ce(NO3)4Dissolving in water solution or dilute nitric acid with pH =4-6, coating the solution on inner and outer electrodes, and heating to obtain Sm (NO)3)3Or Gd (NO)3），Ce(NO3)4Decomposition to the stable compound SDC or GDC; the above process was repeated 3-5 times to increase the SDC or GDC loading.
The flat tube battery after sintering can be used for practical application, and can be subjected to electrode strengthening treatment for further improving the electrical property of the battery and reducing the electrode impedance. SDC is an oxide with good catalytic activity and mixed ion/electron conductance. After impregnation treatment, the SDC can be dispersed into the electrode in a very fine nano-scale manner, so that the reaction region in the electrode process, namely TPB (Triple Phase Boundary, namely a gas-solid electrochemical field), is greatly expanded, the resistance in the electrode process is remarkably reduced, and the internal resistance of the flat tube battery is reduced.
Preferably, the electrolyte, separator, and gas channel walls forming the separation structure are all composed of zirconia-based material.
Preferably, the material of the oxygen-deficient electrode is composed of a compound containing one or more of Pt, YSZ, SDC or CGO; or a precursor material containing NiO, and before the electrochemical device is used, the NiO is reduced into metal Ni by hydrogen so as to enable the actual component of the electrode to contain Ni.
Preferably, the material of the oxygen-enriched electrode is composed of a composite containing one or more of Pt, YSZ, LSCF, LNF, BSCF, SDC or CGO.
Preferably, the materials of the inner electrode connecting wire, the inner electrode pin, the outer electrode connecting wire and the outer electrode pin are composed of high-temperature oxidation resistant noble metal, zirconium oxide-based composite material, high-temperature oxidation resistant noble metal or silver.
Preferably, the material of the heater is a composite material containing high-temperature oxidation resistant noble metal and zirconia or pure high-temperature oxidation resistant noble metal.
Preferably, the high temperature oxidation resistant noble metal is selected from platinum, palladium, ruthenium.
Compared with the prior art, the invention has the beneficial effects that:
1. when the invention is used, the electrode area is in a hot area, and the tail ends and the through holes of the connecting wires of the inner electrode and the outer electrode are sealed or all pins are in a cold area. The isolation of the oxygen-depleted gas and the oxygen-enriched gas in the cold zone is achieved by sealing the through holes or other means. Because the temperature of the tail ends of the connecting wires of the inner electrode and the outer electrode, the via hole seal or the pins is lower, such as lower than the temperature of an electrode area by 300 ℃, usually lower than the temperature by 200 ℃, the choice of the sealing material is large, and meanwhile, the thermal expansion matching and the chemical compatibility of the battery piece and the sealing material are relatively easy to meet in a low temperature range, the reliability of the cold end seal is very high. The isolation of the oxygen-poor gas and the oxygen-rich gas at high temperature is realized through the isolation structure of the air passage and the electrolyte, and as the isolation structure of the air passage and the electrolyte are close to each other and even identical (if 5YSZ or 8YSZ is adopted), the problems of chemical incompatibility, thermal expansion mismatching and the like do not exist between the isolation structure of the air passage and the electrolyte (even if the isolation structure and the electrolyte exist, the high-temperature sealing reliability is not influenced), the sealing reliability of a high-temperature area is also very high, and therefore the whole flat tube structure has very high reliability. Meanwhile, because the flat tube structure electrode is flat, the conductive material is easy to be tightly attached to the electrode, and therefore, the contact resistance is small. The components of the whole battery are in a planar layered structure, so that the residual stress among the components in the preparation process is small, the yield of the battery is high, and the mass production is easy.
2. When the single batteries are stacked, the connection between the single batteries is realized at the cold end, namely, the leads of the electrodes of the single batteries can flexibly realize the series connection or the parallel connection according to the requirements of stacking. Because the connection, disconnection and close contact of the cold-end electrode connection can be easily realized or ensured, the electrochemical device adopting the invention can flexibly realize the stack mode adjustment at the cold end, and simultaneously supports the replacement (namely 'hot replacement') operation of the failed battery under the high-temperature condition. When a single cell in the stack fails, the electrical and gas connections can be disconnected at the cold end, the failed cell is drawn out, a replacement cell is inserted again, and finally the electrode and the gas pipe of the replacement cell are connected to the original stack at the cold end as required. In this manner, failure of a single cell does not result in failure of the entire stack of cells. The flexible stacking and hot replacement supporting features of the cell of the present invention can significantly extend the useful life of the SOC stack, enhance operational flexibility and reduce operating costs.
3. The heater of the present invention is formed by depositing a specially designed conductive heating trace on a substrate that is integrated with the other structure of the cell via lamination or pressing processes. The heating circuit can also reach the pins through the hole structure, and connection with other external equipment is realized. As a further refinement, the conductive heating track may also not be deposited directly on the substrate, but instead a layer of insulating material, for example Al, is first deposited on the substrate2O3And then depositing on the insulating layer to prepare the heater. The heater interlayer in the insulating material is possible to avoid interference on other pins of the flat tube SOC battery when the current of the heater changes, such as when the heating current is switched off.
4. The main shell of the electrochemical device is integrally formed during production and processing, so that the production period can be effectively shortened, the production efficiency can be improved, and the strength of the electrochemical device can be effectively enhanced.
5. The cell of the present invention may also be used for oxidation/reduction operations of other oxides, such as NOx (nitrogen oxides) and SOx (sulfur oxides). When these oxides are subjected to electrolytic treatment, environmental pollution can be reduced or eliminated. For example, the electrolysis of nitrogen oxides (NOx):
oxygen-deficient electrode (cathode, anode): NOx+2x e-→ 1/2 N2+ x O2-
Oxygen-enriched electrode (anode, positive electrode): x O2-→ x/2 O2+ 2x e-
And (3) total reaction: NOx→ 1/2 N2+ x/2 O2
After the treatment of the flat tube battery, the environmental pollutant NOx is completely or partially converted into non-polluting nitrogen and oxygen.
Similarly, when sulfur oxides are treated, electrolysis is performed on sulfur oxides (SOx):
oxygen-deficient electrode (cathode, anode): SO (SO)x+2x e-→ S + x O2-
Oxygen-enriched electrode (anode, positive electrode): x O2-→ x/2 O2+ 2x e-
And (3) total reaction: SO (SO)x→ S + x/2 O2
After the treatment of the flat tube battery, S in the environmental pollutant SOx is completely or partially fixed on the electrode, so that the centralized treatment is easy, and the environment is not polluted any more.
Drawings
FIG. 1 is a schematic structural view of embodiment 1 of the present invention;
FIG. 2 is a schematic structural view of embodiment 2 of the present invention;
FIG. 3 is a schematic structural view of embodiment 3 of the present invention;
FIG. 4 is a graph of potential sweep test results for cells made in example 6;
FIG. 5 is a microstructure diagram of an impregnated electrode of a battery made in example 6;
FIG. 6 is a schematic view of the structure of example 9.
The reference signs are: the structure comprises an outer electrode 1, an outer electrode connecting wire 2, an electrolyte 3, an inner electrode 4, an inner electrode connecting wire 5, an isolation structure 6, a heater 7, a substrate 8, an air channel wall 9, a partition plate 10, an air channel 11, a first insulating layer 12, a second insulating layer 13, an inner electrode pin 14, an outer electrode pin 15, a heater pin 16, a through hole 17 and a lead 18.
Detailed Description
The present invention will be further described with reference to the following examples. The devices, connections, and methods referred to in this disclosure are those known in the art, unless otherwise indicated.
Example 1
As shown in fig. 1: a solid oxide electrochemical device with a flat tube structure comprises an outer electrode 1, an outer electrode connecting wire 2, an electrolyte 3, an inner electrode 4, an inner electrode connecting wire 5, an isolation structure 6, a heater 7 and a substrate 8. Wherein the outer and inner electrodes are in a planar form; and the outer electrode and the inner electrode are respectively an oxygen-enriched electrode and an oxygen-deficient electrode.
The outer electrode and the outer electrode connecting wire are connected and arranged on the outer side face of the electrolyte, and the inner electrode connecting wire are connected and arranged on the inner side face of the electrolyte.
The isolation structure is formed by enclosing electrolyte, two gas channel walls 9 and a partition plate 10; an air passage 11 with two open ends is arranged in the isolation structure, and gas enters from one end opening of the air passage, flows through the inner electrode and exits from the other end opening; the cross section of the electrochemical device is rectangular, and the cross section of the air passage is rectangular.
The heater is integrated on the inner side surface of the substrate, and the heater is a conductive heating circuit deposited on the substrate. The inner side surface of the substrate is connected with the outer side surface of the isolation structure in an opposite mode, and the substrate is integrated with the isolation structure through a lamination process.
When the electrochemical device works, the tail ends of the connecting lines of the inner electrode and the outer electrode on the electrochemical device are positioned at the cold ends, and the temperature of the cold ends is lower than the highest temperature in the middle area of the electrochemical device by more than 50 ℃.
Wherein the electrolyte, separator, and gas channel walls forming the separation structure are all comprised of a zirconia-based material. The material of the oxygen-deficient electrode is composed of a Pt-containing composite. The material of the oxygen-rich electrode is composed of a Pt-containing composite. The inner electrode connecting wire, the inner electrode pin, the outer electrode connecting wire and the outer electrode pin are made of composite materials containing Pt-YSZ. The material of the heater is Pt.
Example 2
As shown in fig. 2: a solid oxide electrochemical device with a flat tube structure comprises an outer electrode 1, an outer electrode connecting wire 2, an electrolyte 3, an inner electrode 4, an inner electrode connecting wire 5, an isolation structure 6, a heater 7, an inner electrode pin 14, an outer electrode pin 15, a heater pin 16 and a substrate 8. Wherein the outer and inner electrodes are in a planar form; and the outer electrode and the inner electrode are respectively an oxygen-deficient electrode and an oxygen-enriched electrode.
The outer electrode and the outer electrode connecting wire are connected and arranged on the outer side face of the electrolyte, and the inner electrode connecting wire are connected and arranged on the inner side face of the electrolyte. The outer electrode pin is arranged on the outer side surface of the electrolyte and is connected with the outer electrode connecting wire; the inner electrode pin is arranged on the outer side surface of the electrolyte and is far away from the edge of one end of the outer electrode pin, and the inner electrode connecting wire penetrates through a through hole 17 formed in the electrolyte and is connected with the inner electrode pin. The outer electrode lead and the inner electrode lead are connected with a lead wire 18, respectively. The outer electrode, the outer electrode connecting wire, the outer electrode pin and the inner electrode pin are positioned on the same plane. The inner and outer electrode pins and/or the inner and outer electrode connecting wires are covered by the sealing material.
The isolation structure is formed by enclosing electrolyte, two gas channel walls 9 and a partition plate 10; an air passage 11 with two open ends is arranged in the isolation structure, and gas enters from one end opening of the air passage, flows through the inner electrode and exits from the other end opening; the cross section of the electrochemical device is rectangular, and the cross section of the air passage is rectangular.
The heater is integrated on the inner side surface of the substrate, and the heater is a conductive heating circuit deposited on the substrate. The heater is connected with a heater pin arranged on the outer side surface of the substrate through a through hole 17 arranged on the substrate; and the gaps at the through holes are respectively filled with sealing materials. The inner side surface of the substrate is connected with the outer side surface of the isolation structure in an opposite mode, and the substrate is integrated with the isolation structure through a pressing process.
When the device works, the pins of the inner electrode and the outer electrode on the electrochemical device are positioned at the cold ends, and the temperature of the cold ends is more than 200 ℃ lower than the highest temperature in the middle area of the electrochemical device.
Wherein the sealing material is an epoxy resin high-temperature resistant sealing material. The electrolyte, separator and gas channel walls forming the isolation structure are all comprised of yttria-doped stabilized zirconia. The material of the oxygen-deficient electrode is composed of a YSZ-containing composite; the material of the oxygen-rich electrode is composed of a YSZ-containing composite. The materials of the inner electrode connecting wire, the inner electrode pin, the outer electrode connecting wire and the outer electrode pin are pure Pt. The material of the heater is Pt.
Example 3
As shown in fig. 3: a solid oxide electrochemical device with a flat tube structure comprises an outer electrode 1, an outer electrode connecting wire 2, an electrolyte 3, an inner electrode 4, an inner electrode connecting wire 5, an isolation structure 6, a heater 7, an inner electrode pin 14, an outer electrode pin 15, a heater pin 16 and a substrate 8. Wherein the outer and inner electrodes are in a planar form; and the outer electrode and the inner electrode are respectively an oxygen-deficient electrode and an oxygen-enriched electrode.
The outer electrode and the outer electrode connecting wire are connected and arranged on the outer side face of the electrolyte, and the inner electrode connecting wire are connected and arranged on the inner side face of the electrolyte. The outer electrode pin is arranged on the outer side surface of the electrolyte and is connected with the outer electrode connecting wire; the inner electrode pin is arranged on the outer side surface of the electrolyte and is far away from the edge of one end of the outer electrode pin, and the inner electrode connecting wire penetrates through a through hole 17 formed in the electrolyte and is connected with the inner electrode pin. The outer electrode lead and the inner electrode lead are connected with a lead wire 18, respectively. The outer electrode, the outer electrode connecting wire, the outer electrode pin and the inner electrode pin are positioned on the same plane. The inner and outer electrode pins and/or the inner and outer electrode connecting wires are covered by the sealing material.
The isolation structure is formed by enclosing electrolyte, two gas channel walls 9 and a partition plate 10; an air passage 11 with two open ends is arranged in the isolation structure, and gas enters from one end opening of the air passage, flows through the inner electrode and exits from the other end opening; the cross section of the electrochemical device is rectangular, and the cross section of the air passage is rectangular.
A first insulating layer 12 is deposited on the inner side of the substrate, a conductive heating line as a heater is deposited on the first insulating layer, and a second insulating layer 13 is deposited on the outer side of the isolation structure. The heater is connected with a heater pin arranged on the outer side surface of the substrate through a through hole 17 arranged on the substrate; and the gaps at the through holes are respectively filled with sealing materials. The inner side surface of the substrate is connected with the outer side surface of the isolation structure in an opposite mode, and the substrate is integrated with the isolation structure through a pressing process.
When the device works, the pins of the upper electrode or the inner electrode and the outer electrode of the electrochemical device are positioned at the cold ends, and the temperature of the cold ends is lower than the highest temperature in the middle area of the electrochemical device by more than 300 ℃.
Wherein, the material of the first and second insulating layers is alumina. The sealing material is a glass high-temperature resistant sealing material. The electrolyte, separator, and gas channel walls forming the separation structure are all composed of zirconia-based material. The material of the oxygen-deficient electrode is composed of a CGO-containing composite; the material of the oxygen-rich electrode is composed of a LSCF-containing composite. The inner electrode connecting wire, the inner electrode pin, the outer electrode connecting wire and the outer electrode pin are made of platinum, and the heater is made of platinum.
Example 4
The present embodiment is different from embodiment 3 in that: the material of the oxygen-deficient electrode is composed of a compound containing Pt, YSZ and CGO; the material of the oxygen-rich electrode is composed of a composition containing LNF.
Example 5
The present embodiment is different from embodiment 3 in that: the material of the oxygen-deficient electrode is composed of a precursor material containing NiO, and NiO is reduced into metal Ni through hydrogen before the electrochemical device is used, so that the actual component of the electrode contains Ni; the material of the oxygen-rich electrode is composed of a BSCF-containing composite.
Example 6
A preparation method of a flat tube structure solid oxide electrochemical device comprises the following steps:
1) preparing slurry: respectively adding fine powder of an isolation structure material (5 YSZ), fine powder of a lean oxygen/oxygen-enriched electrode material (Pt: YSZ =4: 1), fine powder of an inner/outer electrode connecting wire material (Ru: YSZ =4: 1), fine powder of an insulating layer, fine powder of a heater (YSZ), fine powder of an electrode pin (Ru: YSZ =4: 1), fine powder of a heater pin (YSZ) and fine graphite powder into organic auxiliary agent PVB, and respectively preparing stable slurry of the isolation structure material, lean oxygen/oxygen-enriched electrode slurry, slurry of the inner/outer electrode connecting wire, slurry of the insulating layer, slurry of the heater, slurry of the electrode pin, slurry of the heater pin and slurry of the graphite after ball milling;
2) casting: preparing the isolation structure material slurry into a film with the thickness of 120 mu m by using a casting machine, and then cutting the film into casting sheets;
3) thickening the casting sheet: 4 layers of casting sheets are adhered together, laminated and thickened, and after vacuum pumping, 5MPa of pressure is applied at 90 ℃ for 10 minutes, so that the casting sheets are fused into a thicker base sheet;
4) printing inner and outer electrodes: taking 1 base sheet, adopting lean oxygen/rich oxygen electrode slurry and inner/outer electrode connecting wire slurry, and printing inner electrode/outer electrode and inner/outer electrode connecting wires on two surfaces of the base sheet by using a screen printer respectively;
5) forming an air flue wall: cutting the casting sheet or the base sheet into strips according to the size, then taking 1 piece of the base sheet, marking as a base sheet a, and attaching the strips on the base sheet a to form an airway wall of the isolation structure;
6) air flue forming: filling the graphite slurry to the air channel position in the base sheet a, and drying to ensure that the dried graphite or starch slurry is consistent with the thickness of the air channel wall;
7) preparing a heater: taking 1 piece of the basic sheet, and placing the basic sheet,marking as a base sheet b, punching a via hole with a punch to obtain a substrate, and sequentially printing a first insulating layer (Al) on one surface thereof2O3Paste), heater (Pt/YSZ paste (9: 1)), second insulating layer (Al)2O3Paste), printing heater pins (Pt/YSZ paste (9: 1)) on the other side; in the printing process, when the slurry is coated on the via hole, the slurry flows along the hole wall for coating, and after heat treatment, the conduction of the circuit across the basic piece is realized; while printing, negative pressure suction is applied to the via hole position of the base sheet to enhance the effect of the paste coating the via hole.
8) Laminating: sequentially attaching the base pieces prepared in the steps 4), 6) and 7), vacuumizing, and applying 5MPa pressure at 90 ℃ for 10 minutes to fuse the base pieces into a plain blank with a complete flat tube structure;
9) and (3) sintering: and sintering the biscuit in a box-type high-temperature furnace at 1400 ℃ for 2 hours. In the sintering process, the strength of the biscuit is improved, and meanwhile, the graphite is decomposed and gasified, so that regular and uniform air passages are left in the isolation structure;
10) strengthening the electrode: sm (NO) firstly3)3，Ce(NO3)4According to a certain Sm2O3:CeO2(e.g., Sm in a molar ratio of 20: 802O3:CeO2) Dissolving in water solution, coating the solution on internal and external electrodes, and heating to 500 deg.C for 20 min to obtain Sm (NO)3)3，Ce(NO3)4Will decompose to form Sm with a certain proportion2O3:CeO2Doping the stable compound SDC. This process was repeated 3-5 times to increase the SDC loading.
Fig. 4 shows the structure of the inner electrode after the impregnation electrode strengthening treatment, and it can be seen that the impregnated SDC particles have reached deep to the electrolyte/electrode interface, and the dimension can be below 100 nm.
The flat tube cell prepared according to the above method was practically operable. Fig. 5 is a potential scan test result of a semi-closed cell prepared according to the above method. The testing temperature is 800 ℃, the outer electrode is connected with the anode of the testing power supply, the inner electrode is connected with the cathode of the testing power supply, the mixed gas of hydrogen and water vapor flows through the inner electrode (oxygen-deficient electrode) through the gas channel, and the outer electrode (oxygen-enriched electrode) is exposed in the air atmosphere. As can be seen, the open circuit voltage of the cell (i.e., the cell voltage at which the current is zero) is about 0.9V, which is close to the theoretical voltage, indicating that the sealing structure of the entire cell is good. During potential sweep, the cell underwent electrolysis (sweep current greater than 0) and cell (sweep current less than 0) modes, both working properly.
Example 7
A preparation method of a flat tube structure solid oxide electrochemical device comprises the following steps:
1) preparing slurry: adding fine powder of an isolation structure material (5 YSZ), fine powder of an oxygen-poor/oxygen-rich electrode material (such as Pt:8YSZ =1: 1), fine powder of an inner/outer electrode connecting wire material (Pt: 8YSZ =9: 1), fine powder of an insulating layer, fine powder of a heater (YSZ), fine powder of an electrode pin (Pt: 8YSZ =9: 1), fine powder of a heater pin (YSZ) and fine powder of starch into triethanolamine serving as an organic auxiliary agent, and performing ball milling to respectively prepare stable slurry of the isolation structure material, the oxygen-poor/oxygen-rich electrode slurry, the slurry of the inner/outer electrode connecting wire, the slurry of the insulating layer, the slurry of the heater, the slurry of the electrode pin, the slurry of the heater pin and the slurry of the starch;
2) casting: preparing the isolation structure material slurry into a film with the thickness of 120 mu m by using a casting machine, and then cutting the film into casting sheets;
3) thickening the casting sheet: 4 layers of casting sheets are adhered together, laminated and thickened, and after vacuum pumping, 20MPa of pressure is applied at 75 ℃ for 12 minutes, so that the casting sheets are fused into a thicker base sheet;
4) printing inner and outer electrodes: taking 1 base sheet, adopting lean oxygen/rich oxygen electrode slurry and inner/outer electrode connecting wire slurry, and printing inner electrode/outer electrode and inner/outer electrode connecting wires on two surfaces of the base sheet by using a screen printer respectively;
5) forming an air flue wall: cutting the casting sheet or the base sheet into strips according to the size, then taking 1 piece of the base sheet, marking as a base sheet a, and attaching the strips on the base sheet a to form an airway wall of the isolation structure;
6) air flue forming: filling the graphite or starch slurry into the air channel position in the base sheet a, and drying to ensure that the dried graphite or starch slurry is consistent with the air channel wall in thickness;
7) preparing a heater: taking 1 base sheet, marking as base sheet b, punching via holes with punching machine to obtain substrate, and sequentially printing first insulating layer (Al) on one surface of the substrate2O3Paste), heater (Pt/YSZ paste (9: 1)), second insulating layer (Al)2O3Paste), printing heater pins (Pt/YSZ paste (9: 1)) on the other side; in the printing process, when the slurry is coated on the via hole, the slurry flows along the hole wall for coating, and after heat treatment, the conduction of the circuit across the basic piece is realized; while printing, negative pressure suction is applied to the via hole position of the base sheet to enhance the effect of the paste coating the via hole.
8) Laminating: sequentially attaching the base pieces prepared in the steps 4), 6) and 7), vacuumizing, and applying a pressure of 20MPa at 75 ℃ for 12 minutes to fuse the base pieces into a plain blank with a complete flat tube structure;
9) and (3) sintering: and sintering the biscuit in a box-type high-temperature furnace at 1300 ℃ for 3 hours. In the sintering process, the strength of the biscuit is improved, and meanwhile, starch is decomposed and gasified, so that regular and uniform air passages are left in the isolation structure;
10) strengthening the electrode: sm (NO) firstly3)3，Ce(NO3)4According to a certain Sm2O3:CeO2(e.g., Sm in a molar ratio of 20: 802O3:CeO2) Dissolving in water solution, coating the solution on internal and external electrodes, and heating to 300 deg.C for 20 min to obtain Sm (NO)3)3，Ce(NO3)4Will decompose to form Sm with a certain proportion2O3:CeO2Doping the stable compound SDC. This process was repeated 5 times to increase the SDC loading.
Example 8
A preparation method of a flat tube structure solid oxide electrochemical device comprises the following steps:
1) preparing slurry: respectively adding fine powder of an isolation structure material (5 YSZ), fine powder of an oxygen-poor/oxygen-rich electrode material (such as Pt:8YSZ =1: 1), fine powder of an inner/outer electrode connecting wire material (Pd: 8YSZ =9: 1), fine powder of an insulating layer, fine powder of a heater (YSZ), fine powder of an electrode pin (Pd: 8YSZ =9: 1), fine powder of a heater pin (YSZ) and fine powder of starch into organic auxiliary agent ethanol, and respectively preparing stable slurry of the isolation structure material, slurry of the oxygen-poor/oxygen-rich electrode, slurry of the inner/outer electrode connecting wire, slurry of the insulating layer, slurry of the heater, slurry of the electrode pin, slurry of the heater pin and slurry of the starch after ball milling;
2) casting: preparing the isolation structure material slurry into a film with the thickness of 120 mu m by using a casting machine, and then cutting the film into casting sheets;
3) thickening the casting sheet: 4 layers of casting sheets are adhered together, laminated and thickened, and after vacuum pumping, 40MPa pressure is applied at 95 ℃ for 8 minutes, so that the casting sheets are fused into a thicker base sheet;
4) printing inner and outer electrodes: taking 1 base sheet, adopting lean oxygen/rich oxygen electrode slurry and inner/outer electrode connecting wire slurry, and printing inner electrode/outer electrode and inner/outer electrode connecting wires on two surfaces of the base sheet by using a screen printer respectively;
5) forming an air flue wall: cutting the casting sheet or the base sheet into strips according to the size, then taking 1 piece of the base sheet, marking as a base sheet a, and attaching the strips on the base sheet a to form an airway wall of the isolation structure;
6) air flue forming: filling the graphite or starch slurry into the air channel position in the base sheet a, and drying to ensure that the dried graphite or starch slurry is consistent with the air channel wall in thickness;
7) preparing a heater: taking 1 base sheet, marking as base sheet b, punching via holes with punching machine to obtain substrate, and sequentially printing first insulating layer (Al) on one surface of the substrate2O3Paste), heater (Pt/YSZ paste (9: 1)), second insulating layer (Al)2O3Paste) on the other side, printing heater leads on the other sideFoot (Pt/YSZ slurry (9: 1)); in the printing process, when the slurry is coated on the via hole, the slurry flows along the hole wall for coating, and after heat treatment, the conduction of the circuit across the basic piece is realized; while printing, negative pressure suction is applied to the via hole position of the base sheet to enhance the effect of the paste coating the via hole.
8) Laminating: sequentially attaching the base pieces prepared in the steps 4), 6) and 7), vacuumizing, and applying 40MPa pressure at 95 ℃ for 8 minutes to fuse the base pieces into a plain blank with a complete flat tube structure;
9) and (3) sintering: and (3) sintering the biscuit in a box-type high-temperature furnace at 1500 ℃ for 1 hour. In the sintering process, the strength of the biscuit is improved, and meanwhile, starch is decomposed and gasified, so that regular and uniform air passages are left in the isolation structure;
10) strengthening the electrode: gd (NO) first3），Ce(NO3)4Dissolving in water solution, coating the solution on inner and outer electrodes, and performing temperature-rising heat treatment (such as 500 deg.C heat treatment for 20 min), Gd (NO)3），Ce(NO3)4Will decompose to form the compound GDC. This process was repeated 3 times to increase the loading of GDCs.
Example 9
As shown in fig. 6, the present embodiment is different from embodiment 2 in that: the air flue of this embodiment is crooked form to can prolong the time of gas in the air flue, increase gaseous utilization ratio.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still belong to the protection scope of the technical solution of the present invention.

Claims (10)

1. The utility model provides a flat tubular construction solid oxide electrochemical device which characterized in that: comprises an outer electrode (1), an outer electrode connecting wire (2), an electrolyte (3), an inner electrode (4), an inner electrode connecting wire (5) and an isolation structure (6); wherein the outer and inner electrodes are in a planar form; the outer electrode and the inner electrode are respectively an oxygen-enriched electrode and an oxygen-deficient electrode or respectively an oxygen-deficient electrode and an oxygen-enriched electrode;
the outer electrode and the outer electrode connecting wire are connected and arranged on the outer side surface of the electrolyte, and the inner electrode connecting wire are connected and arranged on the inner side surface of the electrolyte;
the isolating structure is formed by surrounding an electrolyte, two gas channel walls (9) and a partition plate (10), and the electrolyte, the two gas channel walls and the partition plate are made of zirconia-based materials; an air channel (11) with two open ends is arranged in the isolation structure, and gas enters from one end opening of the air channel, flows through the inner electrode and exits from the other end opening; the air passage is in a straight path shape or a bent shape;
the flat tube structure solid oxide electrochemical device further comprises an inner electrode pin (14) and an outer electrode pin (15); the outer electrode pin is arranged on the outer side surface of the electrolyte and is connected with the outer electrode connecting wire; the inner electrode pin is arranged on the outer side surface of the electrolyte and is far away from the edge of one end of the outer electrode pin, and the inner electrode connecting wire passes through a through hole (17) arranged on the electrolyte and is connected with the inner electrode pin;
at least one gap at the through hole is filled with a sealing material;
when the device works, the tail ends of the inner electrode connecting wire and the outer electrode connecting wire on the electrochemical device or the inner electrode pin and the outer electrode pin are positioned at the cold ends, and the temperature of the cold ends is lower than the highest temperature in the middle area of the electrochemical device by more than 50 ℃.
2. The flat tube structure solid oxide electrochemical device according to claim 1, further comprising a heater (7) and a substrate (8); the heater is integrated on the inner side surface of the substrate, and the inner side surface of the substrate is connected with the outer side surface of the isolation structure in an opposite mode.
3. The flat tube structure solid oxide electrochemical device according to claim 2, wherein a first insulating layer (12) is deposited on the inner side of the substrate, a conductive heating line as a heater is deposited on the first insulating layer, and a second insulating layer (13) is deposited on the outer side of the isolation structure.
4. The flat tube structure solid oxide electrochemical device according to claim 3, further comprising a heater pin (16); the heater is connected with the heater pins arranged on the outer side surface of the substrate through via holes (17) arranged on the substrate.
5. The flat tube structure solid oxide electrochemical device of claim 1 wherein, in operation, the cold side temperature is greater than 200 ℃ below the maximum temperature in the middle region of the electrochemical device.
6. A method for preparing a flat tube structure solid oxide electrochemical device according to claim 2, characterized by comprising the following steps:
1) preparing slurry: respectively adding fine powder of an isolation structure material, fine powder of a lean oxygen/oxygen-enriched electrode material, fine powder of an inner/outer electrode connecting wire material, fine powder of an insulating layer, fine powder of a heater, fine powder of an electrode pin, fine powder of the heater pin and fine powder of graphite or starch into an organic assistant, and respectively preparing stable slurry of the isolation structure material, lean oxygen/oxygen-enriched electrode slurry, slurry of the inner/outer electrode connecting wire, slurry of the insulating layer, slurry of the heater, slurry of the electrode pin, slurry of the heater pin and slurry of graphite or starch after ball milling;
2) casting: preparing the isolating structure material slurry into a film by using a casting machine, and then cutting the film into casting sheets with certain sizes;
3) thickening the casting sheet: laminating and thickening a plurality of casting sheets together, vacuumizing, and performing hot pressing to fuse the casting sheets into a thicker base sheet;
4) printing inner and outer electrodes: taking 1 base sheet, adopting lean oxygen/rich oxygen electrode slurry and inner/outer electrode connecting wire slurry, and printing inner electrode/outer electrode and inner/outer electrode connecting wires on two surfaces of the base sheet by using a screen printer respectively;
5) forming an air flue wall: cutting the casting sheet or the base sheet into strips according to the size, then taking 1 piece of the base sheet, marking as a base sheet a, and attaching the strips on the base sheet a to form an airway wall of the isolation structure;
6) air flue forming: filling the graphite or starch slurry into the air channel position in the base sheet a, and drying to ensure that the dried graphite or starch slurry is consistent with the air channel wall in thickness;
7) preparing a heater: taking 1 piece of the base sheet, marking as a base sheet b, punching a through hole by using a punching machine to prepare a substrate, sequentially printing a first insulating layer, a heater and a second insulating layer on one surface of the substrate, and printing a heater pin on the other surface of the substrate; in the printing process, when the slurry is coated on the via hole, the slurry flows along the hole wall for coating, and after heat treatment, the conduction of the circuit across the basic piece is realized;
8) laminating: sequentially attaching the base pieces prepared in the steps 4), 6) and 7), vacuumizing, and hot-pressing to fuse the base pieces into a biscuit with a complete flat tube structure;
9) and (3) sintering: and (3) sintering the biscuit in a box-type high-temperature furnace, wherein in the sintering process, the strength of the biscuit is improved, and meanwhile, graphite or starch is decomposed and gasified, so that regular and uniform air passages are left in the isolation structure.
7. The method for preparing the solid oxide electrochemical device with the flat tube structure according to claim 6, wherein in the step 1), the organic auxiliary agent is PVB, triethanolamine or ethanol; in the step 2), the thickness of the film is 80-140 μm; in the step 3) and the step 8), the hot pressing process comprises the following steps: applying pressure of 5-40MPa at 70-95 deg.C and maintaining for 8-12 min; in the step 9), the sintering temperature is 1300-1500 ℃, and the sintering time is 1-3 hours.
8. The method for preparing a solid oxide electrochemical device with a flat tube structure according to claim 6, wherein in the step 7), negative pressure suction is applied to the via hole position of the base sheet while printing to enhance the effect of coating the via hole with the slurry.
9. The method for preparing a solid oxide electrochemical device with a flat tube structure according to claim 6, further comprising, after the step 9), a step 10) of electrode strengthening:sm (NO) firstly3)3Or Gd (NO)3)，Ce(NO3)4Dissolving in aqueous solution or dilute nitric acid with pH 4-6, coating the solution on inner and outer electrodes, and heating to obtain Sm (NO)3)3Or Gd (NO)3)，Ce(NO3)4Decomposition to the stable compound SDC or GDC; the above process was repeated 3-5 times to increase the SDC or GDC loading.
10. The method of manufacturing a flat tube structure solid oxide electrochemical device according to claim 6,
the material of the oxygen-deficient electrode is composed of a compound containing one or more of Pt, YSZ, SDC or CGO; or a precursor material containing NiO, and before the electrochemical device is used, the NiO is reduced into metal Ni through hydrogen so that the actual component of the electrode contains Ni;
the oxygen-enriched electrode is made of a compound containing one or more of Pt, YSZ, LSCF, LNF, BSCF, CGO and SDC;
the inner electrode connecting wire, the inner electrode pin, the outer electrode connecting wire and the outer electrode pin are made of high-temperature oxidation resistant noble metal, zirconium oxide-based composite material and high-temperature oxidation resistant noble metal or silver;
the heater is made of a composite material or pure high-temperature oxidation resistant noble metal containing high-temperature oxidation resistant noble metal and zirconia;
the high temperature oxidation resistant noble metal is selected from platinum, palladium and ruthenium.
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