Bamboo-joint tubular solid oxide fuel cell / electrolytic cell, preparation method, and battery / electrolytic cell stack and preparation method

Abstract

Provided in the present invention are a bamboo-joint tubular solid oxide fuel cell / electrolytic cell, a preparation method, and a battery / electrolytic cell stack and a preparation method. The bamboo-joint tubular solid oxide fuel cell / electrolytic cell comprises a ceramic support, a porous insulating layer on the surface of the ceramic support, and a cell assembly, wherein the cell assembly is formed by a first single cell and several other single cells distributed on the surface of the porous insulating layer in series in a fuel gas flowing direction; and a first insulating layer is provided between adjacent fuel electrodes in the cell assembly, a first connector and a second insulating layer are provided in sequence between adjacent electrolyte layers in a fuel flowing direction, and a third insulating layer is provided between adjacent air electrodes. The arrangement of the insulating layers can keep the single cells independent of one another, thereby improving the sealing performance of the single cells, and avoiding short circuits; and the first connector can longitudinally overlap with the fuel electrode and the air electrode of adjacent cell units, so as to vertically transmit the current from the fuel electrode of a cell unit to the air electrode of the adjacent cell unit by means of the connector, thus enabling the current between the cell units to be longitudinally transmitted by means of the connector, reducing the current transmission loss, and improving the battery performance.

Description

A segmented-tube solid oxide fuel cell / electrolyser, a method of manufacture, and a cell / electrolyser stack, a method of manufacture

[0001] Cross-reference to Related Applications

[0002] The present disclosure claims priority from Chinese Patent Application No. 202410449708.9, filed on April 15, 2024, entitled “A Self-sealing Segmented-tube Solid Oxide Fuel Cell / Electrolyser and a Method of Manufacture of a Cell / Electrolyser Stack Thereof”, Chinese Patent Application No. 202410449707.4, filed on April 15, 2024, entitled “A Self-sealing Segmented-tube Solid Oxide Fuel Cell / Electrolyser and a Cell / Electrolyser Stack Thereof”, Chinese Patent Application No. 202410449710.6, filed on April 15, 2024, entitled “A Segmented-tube Solid Oxide Fuel Cell / Electrolyser and a Method of Manufacture of a Cell / Electrolyser Stack Thereof”, and Chinese Patent Application No. 202410449711.0, filed on April 15, 2024, entitled “A Segmented-tube Solid Oxide Fuel Cell / Electrolyser and a Cell / Electrolyser Stack Thereof”, the entire contents of which are incorporated herein by reference. TECHNICAL FIELD

[0003] The present invention relates to the technical field of solid oxide fuel cell technology, and in particular to a segmented-tube solid oxide fuel cell / electrolyser, a method of manufacture, and a cell / electrolyser stack, a method of manufacture. BACKGROUND

[0004] A solid oxide fuel cell (SOFC) is a full solid-state chemical power generation device that directly converts chemical energy stored in fuels and oxidants into electrical energy at medium-high temperatures with high efficiency and environmental friendliness. It is considered to be the most promising energy conversion and storage technology for carbon neutralization in the future. A tubular solid oxide fuel cell is considered to be an ideal prime mover for distributed power systems because it can be easily assembled into a high-power stack and can be operated under pressure.

[0005] Traditional tubular SOFCs collect current in the circumferential direction, resulting in a large ohmic loss and low power density of single-tube cells. A multi-segmented-tube SOFC developed in accordance with this principle integrates multiple tubular SOFCs in series on the same support tube, while changing the internal current flow direction of the cell, eliminating circumferential current flow, and is expected to significantly reduce ohmic loss and significantly increase single-tube output power.

[0006] But the improved multi-tube SOFC still has the problem of long current transmission path in the connector (current transverse conduction in the connector), and the problem of insufficient sealing between multiple cell units, which causes the fuel electrode to be oxidized, and the resulting short circuit of the battery, causing leakage and other problems.

[0007] In addition, the existing tube SOFC preparation method mostly uses screen printing technology to prepare the battery group on the surface of the support tube. During the preparation of each functional layer in the battery group, the coating part is usually in a state of completely leaking out and being completely shielded at the periphery. Therefore, the functional layer of the prepared cell unit is perpendicular to the surface of the substrate tube, resulting in a step in the end of the functional layer of the cell unit. For example, when there is a step in the end of the fuel electrode, it is difficult for the slurry to reach the bottom or fully cover the fuel electrode from the steep end of the fuel electrode during the preparation of the electrolyte and the connector between the fuel electrode units, which is prone to crack at the step. If cracks occur in the electrolyte layer or the connector layer, the oxidizing gas reaches the fuel electrode through the cracks during the operation of the battery, which causes the fuel electrode to be oxidized and reduces the power generation performance of the battery. Due to the close distance between the functional layers of the cell units, misregistration or misprinting, missing printing, and printing difficulties are prone to occur during printing; for example, the connector not only connects the fuel electrode and the air electrode of the adjacent cell units, but also connects the electrolyte of the adjacent cell units, which destroys the independent structure of each cell unit and may cause short circuit of the battery, resulting in leakage current and limiting the further improvement of the battery performance.

[0008] SUMMARY

[0009] In view of the above problems in the prior art, the present application provides a bamboo joint tube solid oxide fuel cell / electrolysis cell, a preparation method, and a cell / electrolysis cell stack and a preparation method.

[0010] The specific application contents are as follows:

[0011] In a first aspect, the present application provides a bamboo joint tube solid oxide fuel cell / electrolysis cell, comprising a ceramic support body, a porous insulating layer distributed on the surface of the ceramic support body, and a battery group distributed on the surface of the porous insulating layer, wherein the battery group is composed of a first single cell and a plurality of single cells distributed in series on the surface of the porous insulating layer along the fuel gas flow direction.

[0012] In the battery group, a first insulating layer is arranged between the fuel electrodes of each adjacent two single cells, a first connector and a second insulating layer are arranged in sequence along the fuel gas flow direction between the electrolyte layers of each adjacent two single cells, and a third insulating layer is arranged between the air electrodes of each adjacent two single cells.

[0013] Each first connector covers the first insulating layer located thereunder and partially overlaps the fuel electrode located thereunder.

[0014] The third insulation layer is vertically arranged above the second insulation layer;

[0015] The ceramic support is a ceramic support with both ends open, or a ceramic support with one end open and one end closed.

[0016] Optionally, in the first single cell, the fuel electrode, the electrolyte layer and the air electrode are arranged in layers based on the porous insulation layer.

[0017] Optionally, the fuel electrode is arranged based on the porous insulation layer to be recessed by 1-5mm;

[0018] The electrolyte layer is arranged based on the fuel electrode to be recessed by 0.4-2mm;

[0019] The air electrode is arranged based on the electrolyte layer to be recessed by 0.4-2mm.

[0020] Optionally, between the fuel electrodes of two adjacent single cells, electrolyte end heads are further arranged, and each electrolyte end head is located on the side close to the fuel gas inlet end of the ceramic support.

[0021] Optionally, each electrolyte end head is partially or entirely covered by the electrolyte layer located above it.

[0022] Optionally, the overlap length of each first connector with the fuel electrode located below it is 0.2-2mm.

[0023] Optionally, when the ceramic support is a ceramic support with both ends open, in the battery pack, the last single cell is arranged on the side close to the fuel gas outlet of the ceramic support, a second connector is arranged, the second connector is in contact with the ceramic support and is covered by the air electrode of the last single cell, and an electrolyte end head is arranged between the fuel electrode in the last single cell and the second connector.

[0024] When the ceramic support is a ceramic support with one end open and one end closed, an electrolyte coating layer is arranged on the closed end of the ceramic support, a second connector is arranged between the electrolyte coating layer and the last single cell close to the closed end, the second connector is in contact with the ceramic support and is covered by the air electrode of the last single cell, and an electrolyte end head is arranged between the fuel electrode in the last single cell and the second connector.

[0025] Optionally, the first insulation layer is in the same height as the fuel electrode.

[0026] The first connector and the second insulation layer are in the same height as the electrolyte layer.

[0027] The third insulation layer is in the same height as the air electrode.

[0028] Optionally, the thickness of the porous insulation layer is 100-300 μm.

[0029] The thickness of the fuel electrode is 50-250 μm.

[0030] The thickness of the electrolyte layer is 10-100 μm.

[0031] The thickness of the air electrode is 500-1500 μm.

[0032] In a second aspect, the present application provides a preparation method of a bamboo joint pipe type solid oxide fuel cell / electrolytic cell, the bamboo joint pipe type solid oxide fuel cell / electrolytic cell comprising a ceramic support with both ends open, a porous insulation layer distributed on the surface of the ceramic support, and a cell group distributed on the surface of the porous insulation layer, the cell group comprising a first single cell and other single cells distributed in series on the surface of the porous insulation layer in the fuel gas flow direction, the preparation method comprising:

[0033] S101: taking a hollow cylindrical ceramic pipe with both ends open as a base pipe, and printing a first insulation layer slurry on the annular pipe wall, to form a first plane after drying;

[0034] S102: printing fuel electrode slurry above the middle region of the first plane with intervals; after drying, a plurality of fuel electrode film layers in the same height and a plurality of first intervals are formed;

[0035] S103: printing electrolyte slurry and second insulation layer slurry respectively at each of the first intervals in the fuel gas flow direction, until the same height as the fuel electrode film layer, to obtain a second plane composed of a plurality of first insulation film layers, a plurality of first electrolyte end film layers, and a plurality of fuel electrode film layers after drying;

[0036] S104: printing electrolyte slurry above the end region of the first plane close to the fuel gas outlet end, until the same height as the second plane, to form a second electrolyte end film layer;

[0037] S105: printing electrolyte slurry above the second plane with intervals, so that the electrolyte slurry partially covers the fuel electrode film layer below, and covers the first electrolyte end film layer and / or the second electrolyte end film layer adjacent to the fuel electrode film layer below, to form a plurality of electrolyte film layers in the same height and a plurality of second intervals after drying;

[0038] S106: At each of the second intervals, print the connecting body paste and the second insulation layer paste respectively along the fuel gas flow direction until the same height as the electrolyte membrane layer; the connecting body paste covers the first insulation membrane layer below and partially covers the fuel electrode membrane layer below adjacent to the first insulation membrane layer, and after drying, a third plane formed by the first connecting body membrane layer, the second insulation membrane layer and the electrolyte membrane layer is obtained;

[0039] S107: Print the connecting body paste on the side of the first plane close to the fuel gas outlet end until the same height as the third plane to form a second connecting body membrane layer;

[0040] S108: Continue to print the second insulation layer paste on the top of the second insulation membrane layer until the insulation layer reaches the set thickness, and after drying, a first cell / electrolytic cell precursor with the same height of the third insulation membrane layer and the third interval is obtained;

[0041] S109: Perform the first firing process on the first cell / electrolytic cell precursor to obtain a second cell / electrolytic cell precursor;

[0042] S110: Print the air electrode paste at each of the third intervals and on the top of the second connecting body until the same height as the third insulation membrane layer, and after drying, a fourth plane formed by a plurality of air electrode membrane layers and a plurality of third insulation membrane layers is obtained to obtain a third cell precursor;

[0043] S111: After the second firing process on the third cell / electrolytic cell precursor, a bamboo joint tubular solid oxide fuel cell / electrolytic cell is prepared.

[0044] Optionally, on the side close to the fuel gas inlet end, the second plane is setback based on the first plane by 0.5-1 times the length of the first interval; the third plane is setback based on the second plane by 0.5-1 times the length of the second interval; and the fourth plane is setback based on the third plane by 0.5-1 times the length of the third interval.

[0045] Optionally, the length of the first interval is 0.3-2 mm;

[0046] The length of the second interval is 0.4-3 mm;

[0047] The length of the third interval is 0.2-2 mm.

[0048] Optionally, the length of the first connecting body membrane layer is not less than half the length of the second interval.

[0049] Optionally, the covered length of the fuel electrode membrane layer partially covered by the first connecting body membrane layer is 0.2-2 mm.

[0050] Optionally, the first firing temperature is 1250-1500℃, and the first firing time is 4-6h.

[0051] Optionally, the second firing temperature is 1100-1500℃, and the second firing time is 2-4h.

[0052] Optionally, the first insulation layer slurry forms a porous insulation layer after firing, and the second insulation layer slurry forms a dense insulation layer after firing.

[0053] Optionally, the first plane has a thickness of 100-300μm.

[0054] Optionally, the second plane has a thickness of 50-250μm.

[0055] Optionally, the third plane has a thickness of 10-100μm.

[0056] Optionally, the fourth plane has a thickness of 500-1500μm.

[0057] In a third aspect, the present application provides a preparation method of a bamboo joint pipe type solid oxide fuel cell / electrolytic cell, the bamboo joint pipe type solid oxide fuel cell / electrolytic cell comprising a ceramic support with an open end and a closed end, a porous insulation layer distributed on the surface of the ceramic support, and a cell group distributed on the surface of the porous insulation layer, the cell group comprising a first single cell and other single cells distributed in series on the surface of the porous insulation layer along the fuel gas flow direction, the preparation method comprising:

[0058] S201: taking a hollow cylindrical ceramic tube with an open end and a closed end as a base tube, and printing a first insulation layer slurry on the annular tube wall to form a first plane after drying;

[0059] S202: printing fuel electrode slurry on the middle region of the first plane in intervals; after drying, a plurality of fuel electrode film layers and a plurality of first intervals are formed;

[0060] S203: printing electrolyte slurry and second insulation layer slurry in each first interval along the fuel gas flow direction, respectively, until the same height as the fuel electrode film layer, and drying to obtain a second plane composed of a plurality of first insulation film layers, a plurality of first electrolyte end film layers, and a plurality of fuel electrode film layers;

[0061] S204: printing electrolyte slurry on the end region of the first plane close to the closed end until the same height as the second plane to form a second electrolyte end film layer;

[0062] S205: printing electrolyte paste above the second plane, so that the electrolyte paste partially covers the fuel electrode film layer below and covers the first electrolyte end film layer and / or the second electrolyte end film layer adjacent to the fuel electrode film layer below, and forms a plurality of electrolyte film layers and a plurality of second intervals after drying;

[0063] S206: printing the connector paste and the second insulation layer paste respectively at each of the second intervals in the fuel gas flow direction until the same height as the electrolyte film layer; the connector paste covers the first insulation film layer below and partially covers the fuel electrode film layer adjacent to the first insulation film layer below, and forms a third plane composed of the first connector film layer, the second insulation film layer and the electrolyte film layer after drying;

[0064] S207: printing the connector paste on the side of the first plane close to the closed end until the same height as the third plane to form a second connector film layer;

[0065] S208: continuing to print the second insulation layer paste above the second insulation film layer until the insulation layer reaches the set thickness, and forming a third insulation film layer and a third interval after drying;

[0066] S209: using electrolyte solution to immerse the closed end for multiple times, and forming an electrolyte coating film layer on the closed end after drying, thereby obtaining a first battery / electrolysis cell precursor;

[0067] S210: performing a first firing process on the first battery / electrolysis cell precursor, thereby obtaining a second battery / electrolysis cell precursor;

[0068] S211: printing the air electrode paste at each of the third intervals and above the second connector until the same height as the third insulation film layer, and obtaining a third battery / electrolysis cell precursor after drying, wherein the third battery / electrolysis cell precursor is composed of a plurality of air electrode film layers and a plurality of third insulation film layers;

[0069] S212: after performing a second firing process on the third battery / electrolysis cell precursor, a self-sealing bamboo joint tube type solid oxide fuel cell / electrolysis cell is prepared.

[0070] Optionally, on the side close to the open end, the second plane is setback based on the first plane by 0.5-1 times the length of the first interval; the third plane is setback based on the second plane by 0.5-1 times the length of the second interval; and the fourth plane is setback based on the third plane by 0.5-1 times the length of the third interval.

[0071] Optionally, the length of the first interval is 0.3-2 mm;

[0072] The length of the second interval is 0.4-3mm;

[0073] The length of the third interval is 0.2-2mm.

[0074] Optionally, the length of the first connector film layer is not less than half of the length of the second interval.

[0075] Optionally, the covered length of the fuel electrode film layer partially covered by the first connector film layer is 0.2-2mm.

[0076] Optionally, the temperature of the first firing is 1250-1500℃, and the time of the first firing is 4-6h.

[0077] Optionally, the temperature of the second firing is 1100-1500℃, and the time of the second firing is 2-4h.

[0078] Optionally, the first insulating layer paste forms a porous insulating layer after firing treatment, and the second insulating layer paste forms a dense insulating layer after firing treatment.

[0079] Optionally, the thickness of the first plane is 100-300μm;

[0080] The thickness of the second plane is 50-250μm;

[0081] The thickness of the third plane is 10-100μm;

[0082] The thickness of the fourth plane is 500-1500μm.

[0083] In a fourth aspect, the present application provides a bamboo joint pipe type solid oxide fuel cell / electrolytic cell stack, comprising: a plurality of the bamboo joint pipe type solid oxide fuel cell / electrolytic cell stack structure of the first aspect.

[0084] In a fifth aspect, the present application provides a preparation method of the bamboo joint pipe type solid oxide fuel cell / electrolytic cell stack of the fourth aspect, the preparation method comprising:

[0085] Placing a plurality of fuel gas inlet ends of the bamboo joint pipe type solid oxide fuel cell / electrolytic cell of the first aspect in a fuel gas channel base in a certain arrangement to form the bamboo joint pipe type solid oxide fuel cell / electrolytic cell stack integrated by a plurality of the bamboo joint pipe type solid oxide fuel cell / electrolytic cells.

[0086] Compared with the prior art, the present application has the following advantages:

[0087] The bamboo joint pipe type solid oxide fuel cell / electrolytic cell provided by the application adopts a ceramic round pipe as a support structure, and the series cell groups are distributed on the surface of the round pipe, and the insulating layers are arranged between the cell groups and the support and between the functional layers of each cell unit in the cell group, so that the structure of the cell units is independent, the sealing of the cell units is improved, and the short circuit or leakage current of the cell / electrolytic cell is avoided.

[0088] In the bamboo joint pipe type solid oxide fuel cell / electrolytic cell provided by the application, the first connecting body is arranged at the same plane position as the electrolyte layer and longitudinally overlaps the fuel electrode and the air electrode of the adjacent cell units, the current is vertically transmitted from the fuel electrode of one cell unit to the air electrode of the adjacent cell unit through the connecting body, the current between the cell units is longitudinally transmitted through the connecting body, the loss of the current in the transmission is reduced, and the performance of the cell / electrolytic cell is improved.

[0089] In the bamboo joint pipe type solid oxide fuel cell / electrolytic cell provided by the application, the composition of the ceramic support can be inert component ceramic (in the working state, the component cannot be reduced to metal ceramic by hydrogen) or ceramic composition capable of being reduced to metal ceramic by hydrogen in the working state, for the inert component ceramic support, the second connecting body can seal the porous insulating layer to avoid oxidation of the fuel electrode, and for the support capable of being reduced to metal ceramic by hydrogen in the working state, the current collected by the cell group is introduced into the ceramic support with conductivity through the second connecting body connected with the support, and the current collection problem of the multi-joint pipe type solid oxide fuel cell / electrolytic cell is solved.

[0090] In the bamboo joint pipe type solid oxide fuel cell / electrolytic cell provided by the application, each functional layer of the cell unit is prepared by the silk screen printing method, the film forming speed is improved, the preparation efficiency is effectively improved, the preparation method is simplified, the preparation cost is saved, and the commercialization popularization of the solid oxide fuel cell is facilitated.

[0091] In the bamboo joint pipe type solid oxide fuel cell / electrolytic cell provided by the application, the cell groups are prepared on the surface of the ceramic base pipe in the structural layer unit by the silk screen printing technology, the problems of misprinting and missing printing in the printing of each functional layer of the cell unit are effectively avoided, the first connecting body film layer formed by printing the connecting body paste in the second interval is in contact with the electrolyte film layer and the second insulating film layer in the horizontal direction and longitudinally overlaps the fuel electrode film layer and the air electrode film layer of the adjacent cell units in the vertical direction, the current is vertically transmitted from the fuel electrode of one cell unit to the air electrode of the adjacent cell unit through the connecting body, the current between the cell units is longitudinally transmitted through the connecting body, the loss of the current in the transmission is reduced, and the performance of the cell / electrolytic cell is improved. BRIEF DESCRIPTION OF DRAWINGS

[0092] In order to make the technical solutions in the embodiments of the present disclosure or the related art clearer, the accompanying drawings needed to be used in the embodiments or the related art description will be briefly introduced. Obviously, the accompanying drawings in the following description are some embodiments of the present disclosure, and for those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0093] Fig. 1 shows a partial cross-sectional schematic view of a bamboo tube type solid oxide fuel cell / electrolytic cell according to an embodiment of the present disclosure;

[0094] Fig. 2 shows a structural schematic view of a ceramic matrix tube according to an embodiment of the present disclosure;

[0095] Fig. 3 shows a flow chart of a preparation method of a bamboo tube type solid oxide fuel cell / electrolytic cell according to an embodiment of the present disclosure;

[0096] Fig. 4 shows a partial cross-sectional schematic view of another bamboo tube type solid oxide fuel cell / electrolytic cell according to an embodiment of the present disclosure;

[0097] Fig. 5 shows a structural schematic view of another ceramic matrix tube according to an embodiment of the present disclosure;

[0098] Fig. 6 shows a flow chart of another preparation method of a bamboo tube type solid oxide fuel cell / electrolytic cell according to an embodiment of the present disclosure. Specific embodiments

[0099] The following embodiments are provided to better further understand the present disclosure, and are not limited to the best mode, and do not limit the content and protection scope of the present disclosure. Any person under the inspiration of the present disclosure or the combination of the present disclosure with other prior art features can obtain any product same or similar to the present disclosure, which falls within the protection scope of the present disclosure.

[0100] The specific experimental steps or conditions not mentioned in the embodiments can be operated according to the conventional experimental steps described in the prior art in the field. The reagents and other instruments not mentioned by the manufacturer are all conventional reagent products that can be obtained by purchase.

[0101] The application provides a bamboo joint pipe type solid oxide fuel cell / electrolytic cell, and Figure 1 shows a partial cross-sectional schematic view of the bamboo joint pipe type solid oxide fuel cell / electrolytic cell provided by the embodiment of the application, as shown in Figure 1, the bamboo joint pipe type solid oxide fuel cell / electrolytic cell comprises a ceramic support body 1 with two open ends, a porous insulating layer 2 distributed on the surface of the ceramic support body, and a cell group distributed on the surface of the porous insulating layer with a thickness of 100-300 μm, and the cell group is specifically composed of a first single cell and other single cells which are distributed on the surface of the porous insulating layer in series along the fuel gas flow direction; the single cell is specifically composed of a fuel electrode 3, an electrolyte layer 6 and an air electrode 9; in the cell group, a first insulating layer 4 is arranged between the fuel electrodes 3 of every two adjacent single cells, and the first insulating layer 4 is in the same height as the fuel electrode 3; a first connecting body 7 and a second insulating layer 8 are sequentially arranged between the electrolyte layers 6 of every two adjacent single cells along the fuel gas flow direction, and the first connecting body 7 and the second insulating layer 8 are in the same height as the electrolyte layer 6; a third insulating layer 10 is arranged between the air electrodes 9 of every two adjacent single cells, and the third insulating layer 10 is in the same height as the air electrode 9; each first connecting body 7 covers the first insulating layer 4 below it and partially overlaps the fuel electrode 3 of the adjacent single cell below it; and the third insulating layer 10 is vertically arranged above the second insulating layer 8.

[0102] Figure 2 shows a structural schematic view of the ceramic base pipe provided by the embodiment of the application, as shown in Figure 2, the ceramic base pipe is divided into an A region, a B region and a C region, wherein the A region corresponds to the fuel gas outlet end of the ceramic base pipe, the B region corresponds to the working region of the ceramic base pipe, and the C region corresponds to the fuel gas inlet end of the ceramic base pipe; it is to be noted that the first single cell, i.e. the first single cell unit closest to the fuel gas inlet end of the ceramic support body, in the first single cell, the functional layers (the fuel electrode 3, the electrolyte layer 6 and the air electrode 9) are arranged in layers and recessed step by step based on the porous insulating layer 2; specifically, the fuel electrode 3 is arranged to be recessed by 1-5 mm based on the porous insulating layer 2; the electrolyte layer 6 is arranged to be recessed by 0.4-2 mm based on the fuel electrode 3; and the air electrode 9 is arranged to be recessed by 0.4-2 mm based on the electrolyte layer 6. Other single cells connected in series with the first single cell are affected by the recessed arrangement of the functional layers of the first single cell, and the functional layers of the other single cells present the same arrangement trend.

[0103] In the implementation, due to the retreat arrangement of each functional layer, it can be understood that there is a gap between two adjacent single cell unit functional layers, such as between the fuel poles 3 of two adjacent single cell units, between the electrolyte layers 6 of two adjacent single cell units, and between the air poles 9 of two adjacent single cell units. The first insulating layer 4 is arranged at the gap between the fuel poles of each adjacent two single cell units to block the passage between the fuel poles 3. The second insulating layer 8 is arranged at the gap between the electrolyte layers 6 of each adjacent two single cell units to block the passage between the electrolyte layers 6. The third insulating layer 10 is arranged at the gap between the air poles 9 of each adjacent two single cell units to block the passage between the air poles 9. The arrangement of the first insulating layer 4, the second insulating layer 8 and the third insulating layer 10 realizes the sealing of the battery cell and the mutual independence between the battery cells, avoiding the problems of battery short circuit leakage current caused by close distance between the battery cells. It should be noted that the first insulating layer 4, the second insulating layer 8 and the third insulating layer 10 are composed of the same insulating layer material.

[0104] Further, the first connecting body 7 is arranged at the gap between the electrolyte layers of each adjacent two single cell units, that is, the first connecting body 7 and the second insulating layer 8 are arranged at the gap between the electrolyte layers 6 of each adjacent two single cell units, and the first connecting body 7 and the second insulating layer 8 are arranged at the gap in sequence along the fuel gas flow direction. Based on the retreat arrangement of the functional layer, the position of each first connecting body 7 can cover the first insulating layer 4 below it and partially overlap the fuel pole 3 of the adjacent single cell below it. Since the electrolyte layer 6 and the first connecting body 7 are arranged on the same plane and longitudinally overlap the fuel pole 3 and the air pole 9 of the adjacent battery cell, it is not only conducive to the realization of the connecting body preparation process, but also changes the current collection mode between the battery cells in the existing solid oxide fuel cell, so that the current is vertically transmitted from the fuel pole of one battery cell to the air pole of the adjacent battery cell through the first connecting body, so that the current between the battery cells is longitudinally transmitted through the connecting body, reducing the loss of current in transmission and improving the performance of the battery.

[0105] As an example, the overlap length of each first connecting body 7 and the fuel pole 3 below it is 0.2-2mm.

[0106] In some embodiments, an electrolyte end head 5 is also arranged at the interval between every two adjacent fuel electrodes 3, and the material of the electrolyte end head 5 is the same as that of the electrolyte layer 6; see FIG. 1, that is, the interval between every two adjacent fuel electrodes 3 is provided with both the electrolyte end head 5 and the first insulation layer 4, and the electrolyte end head 5 and the first insulation layer 4 are sequentially arranged at the interval (each electrolyte end head 5 is located at the side close to the fuel gas inlet end of the ceramic support 1) along the fuel gas flow direction, and each electrolyte end head 5 is covered or partially covered by the electrolyte layer 6, so that there is no connecting interface between each first insulation layer 4 and the electrolyte layer 5. Since the electrolyte end head 5 and the electrolyte layer 6 are made of the same material and have the same thermal expansion coefficient, the contact surfaces of the electrolyte end head 5 and the electrolyte layer 6 have the same shrinkage behavior in the subsequent sintering or battery operation process. This arrangement avoids the problem that, when only the first insulation layer is arranged between the fuel electrodes, the contact surface between the first insulation layer and the electrolyte layer above the first insulation layer has different thermal expansion coefficients due to the difference in the material composition, which causes the shrinkage mismatch between the first insulation layer and the electrolyte layer above the first insulation layer in the subsequent sintering or battery operation process, resulting in micro-cracks in the electrolyte layer, which affects the performance and service life of the battery.

[0107] It should be noted that the last single cell is the first single cell unit closest to the fuel gas outlet end of the ceramic support 1, or the single cell unit farthest from the first single cell. It should also be noted that in the embodiment of the present application, the ceramic support can be made of inert ceramic components (which will not be reduced to metal ceramic in the working state), or ceramic components that can be reduced to metal ceramic in the working state; the second connecting body 12 is located at the side of the last single cell close to the fuel gas outlet of the ceramic support, in contact with the ceramic support 1 and covered by the air electrode 9 of the last single cell. In this way, on the one hand, the sealing of the battery unit can be ensured by sealing the porous insulation layer, and on the other hand, when the ceramic matrix tube is selected to have a metal ceramic composition in the working state (such as nickel oxide NiO reduced to metal nickel), the current collected in the last single cell unit is introduced into the ceramic support by the second connecting body, solving the problem of current convergence.

[0108] In some embodiments, an electrolyte end head is arranged between the fuel electrode 3 and the second connecting body 12 in the last single cell to prevent the fuel electrode of the last single cell from being in conduction with the second connecting body.

[0109] It should be noted that in the bamboo tube solid oxide fuel cell / electrolysis cell provided by the present application, each functional layer of the cell unit and the structure for keeping the cell unit independent can be prepared by the screen printing method, which can improve the film forming speed, effectively improve the preparation efficiency, simplify the preparation method, save the preparation cost, and be beneficial to the commercialization of the solid oxide fuel cell / electrolysis cell.

[0110] FIG. 3 shows a flow chart of the preparation method of the bamboo tube solid oxide fuel cell / electrolysis cell provided by the embodiment of the present application, which is used for preparing the two-end-open bamboo tube solid oxide fuel cell / electrolysis cell shown in FIG. 1. As shown in FIG. 3, the preparation method comprises the following steps:

[0111] S101: taking a two-end-open hollow cylindrical ceramic tube as a base tube, and printing a first insulation layer slurry on the annular tube wall of the base tube, to form a first plane after drying;

[0112] S102: printing fuel electrode slurry on the middle region of the first plane in intervals, to form a plurality of fuel electrode film layers and a plurality of first intervals after drying;

[0113] S103: printing electrolyte slurry and second insulation layer slurry on each of the first intervals in the fuel gas flow direction respectively, until the same height as the fuel electrode film layer, to obtain a second plane formed by a plurality of first insulation film layers, a plurality of first electrolyte end film layers and a plurality of fuel electrode film layers after drying;

[0114] S104: printing electrolyte slurry on the end region of the first plane close to the fuel gas outlet end, until the same height as the second plane, to form a second electrolyte end film layer;

[0115] S105: printing electrolyte slurry on the second plane in intervals, so that the electrolyte slurry partially covers the fuel electrode film layer below and covers the first electrolyte end film layer and / or the second electrolyte end film layer adjacent to the fuel electrode film layer below, to form a plurality of electrolyte film layers and a plurality of second intervals after drying;

[0116] S106: printing connector slurry and second insulation layer slurry on each of the second intervals in the fuel gas flow direction respectively, until the same height as the electrolyte film layer; the connector slurry covers the first insulation film layer below and partially covers the fuel electrode film layer adjacent to the first insulation film layer below, to form a third plane formed by a first connector film layer, a second insulation film layer and an electrolyte film layer after drying;

[0117] S107: printing connector slurry on the first plane close to the fuel gas outlet end, until the same height as the third plane, to form a second connector film layer;

[0118] S108: Continue printing the second insulation layer paste above the second insulation film layer until the insulation layer reaches the set thickness, and after drying, obtain a first cell / electrolytic cell precursor with a third insulation film layer and a third interval of equal height;

[0119] S109: Perform a first firing process on the first cell / electrolytic cell precursor, thereby obtaining a second cell / electrolytic cell precursor;

[0120] S110: Print air electrode paste at each of the third intervals and above the second connecting body until the same height as the third insulation film layer, and after drying, obtain a fourth plane formed by a plurality of air electrode film layers and a plurality of third insulation film layers, thereby obtaining a third cell precursor;

[0121] S111: After a second firing process on the third cell / electrolytic cell precursor, a tubular solid oxide fuel cell / electrolyzer is prepared.

[0122] The preparation step S101 prints the first insulation layer paste above the working area. The first plane formed is a ring-shaped plane covering the surface of the annular pipe wall of the base pipe, and the thickness of the first plane is 100-300 μm; the first plane obtained in this step forms a porous insulation layer structure covering the surface of the annular pipe wall (working area) of the base pipe after subsequent firing process.

[0123] The preparation step S102 prints the fuel electrode film layer in intervals without covering the two end regions of the first plane, wherein the length of the end region near the fuel gas inlet end of the ceramic base pipe can be 0.5-1 times the length of the first interval, and the length of the end region near the fuel gas outlet end of the ceramic base pipe can be 0.5-1 times the length of the first interval. The fuel electrode film layer forms a fuel electrode after subsequent sintering process.

[0124] The preparation step S103 prints electrolyte paste and second insulation layer paste between every two fuel electrodes (at the first interval), the electrolyte paste is filled near the fuel gas inlet end of the base pipe at each first interval, and the second insulation layer paste is filled near the fuel gas outlet end of the base pipe at each first interval. After drying, the electrolyte end head and the second insulation film layer are formed. Thus, a second plane with a thickness of 50-250 μm is formed. The first insulation film layer formed by the second insulation paste after drying forms a first insulation layer after subsequent sintering process; the first electrolyte end head film layer formed by the electrolyte paste after drying forms a first electrolyte end head after subsequent sintering process.

[0125] Further, the first plane is not covered by the fuel electrode paste on the end region near the fuel gas outlet end side of the substrate tube, and the electrolyte paste is printed in the region to form a second electrolyte end head film layer until the same height as the second plane in the preparation step S104.

[0126] In the preparation step S105, the electrolyte paste is printed on the second plane, and the printing is pushed forward in the fuel gas flow direction from the side near the fuel gas inlet end of the substrate tube to the fuel gas outlet end of the substrate tube at the second interval length, and the end region of 0.5-1 times the length of the second interval near the fuel gas inlet end of the substrate tube is left without printing. After drying, each electrolyte film layer partially covers the fuel electrode film layer below it and covers the first electrolyte end head film layer or the second electrolyte end head film layer adjacent to the fuel electrode film layer below it. After the electrolyte film layer is subjected to subsequent calcination, an electrolyte layer is formed, and the interval between every two electrolyte layers is the second interval.

[0127] Further, the step S106 prints the connector paste and the second insulating layer paste at each second interval, the connector paste is filled near the fuel gas inlet end of the substrate tube at each second interval, and the second insulating layer paste is filled near the fuel gas outlet end of the substrate tube at each second interval. After drying, the first connector film layer and the second insulating film layer are formed, and the third plane formed by the first connector film layer and the second insulating film layer has a thickness of 10-100 μm. The length of the first connector film layer is not less than the length of the second insulating film layer, and the fuel electrode film layer partially covered by the first connector film layer has a covered length of 0.2-2 mm.

[0128] In the preparation step S107, the connector paste is printed on the first plane near the fuel gas outlet end of the substrate tube to form a second connector film layer, and after subsequent calcination, a second connector is formed.

[0129] Further, the second insulating layer paste is printed on the second insulating film layer to form a third insulating film layer, and the height of the third insulating film layer after the first calcination is consistent with the height of the subsequently printed air electrode film layer, so that a first cell / electrolytic cell precursor is obtained. The obtained structure (first cell / electrolytic cell precursor) is subjected to a first calcination at a temperature of 1250-1500 °C for 4-6 h. The first calcination converts the first plane printed on the surface of the substrate tube into a porous insulating layer, and the first insulating film layer, the second insulating film layer, and the third insulating film layer are converted into a dense insulating layer.

[0130] Further, the embodiment of the present application continues to print the air electrode paste at the third interval and above the second connector, and, near the open end side, an end region of 0.5-1 times the length of the third interval is left unprinted. After drying, several air electrode film layers are formed, the air electrode film layers are at the same height as the third insulating film layer, and together form a fourth plane, the thickness of the fourth plane is 500-1500 μm. Then the obtained structure is subjected to a second firing, the temperature of the second firing is 1100-1500 °C, the time of the second firing is 2-4 h, and finally a segmented tubular solid oxide fuel cell / electrolysis cell is obtained.

[0131] In some embodiments, the length of the first interval is 0.3-2 mm; the length of the second interval is 0.4-3 mm; and the length of the third interval is 0.2-2 mm.

[0132] Figure 4 shows a partial cross-sectional schematic view of another segmented tubular solid oxide fuel cell / electrolysis cell provided by the embodiment of the present application. As shown in Figure 4, the ceramic support 1 of the (self-sealing type) segmented tubular solid oxide fuel cell / electrolysis cell is a ceramic support with one open end and one closed end; the arrangement of the cell stack is the same as that of the segmented tubular solid oxide fuel cell / electrolysis cell shown in Figure 1, and will not be described again.

[0133] Figure 5 shows a structural schematic view of another ceramic matrix tube provided by the embodiment of the present application. Referring to Figures 4 and 5, the ceramic matrix tube is divided into an A1 region, a B1 region and a C1 region, wherein the A1 region corresponds to the closed end of the ceramic matrix tube, the B1 region corresponds to the working region of the ceramic matrix tube, and the C1 region corresponds to the open end of the ceramic matrix tube. Based on the different ceramic supports 1, in the segmented tubular solid oxide fuel cell / electrolysis cell shown in Figure 4, the first single cell, i.e. the first single cell unit closest to the open end of the ceramic support; the last single cell, i.e. the first single cell unit closest to the closed end of the ceramic support, or the single cell unit farthest from the first single cell, is the last single cell. In addition, the closed end of the ceramic support 1 shown in Figure 4 is provided with an electrolyte coating layer 11; to solve the high-temperature sealing problem of the multi-segmented tubular solid oxide fuel cell; the electrolyte coating layer 11 is between the last single cell closest to the closed end and the second connector 12; the second connector 12 is in contact with the ceramic support 1 and is covered by the air electrode 9 of the last single cell; in this way, for a ceramic support composed of inert ingredients, the second connector 12 can seal the porous insulating layer, preventing the fuel electrode from being oxidized; for a support that can be reduced to a metal ceramic by hydrogen in the working state, the second connector leads the current collected in the last single cell unit to the ceramic support, solving the current collection problem.

[0134] Figure 6 shows a flow chart of another method for preparing a bamboo-tube solid oxide fuel cell / electrolyser according to an embodiment of the present application, which is used to prepare the self-sealing bamboo-tube solid oxide fuel cell / electrolyser shown in Figure 4. As shown in Figure 6, the method comprises the following steps:

[0135] S201: Taking a hollow cylindrical ceramic tube with an open end and a closed end as a base tube, and printing a first insulation layer slurry on the annular wall of the tube, and after drying, a first plane is formed;

[0136] S202: Above the middle region of the first plane, the fuel electrode slurry is printed in intervals; after drying, a plurality of fuel electrode film layers and a plurality of first intervals are formed;

[0137] S203: At each of the first intervals, the electrolyte slurry and the second insulation layer slurry are printed in the fuel gas flow direction respectively, until the same height as the fuel electrode film layer, and after drying, a second plane composed of a plurality of first insulation film layers, a plurality of first electrolyte end film layers and a plurality of fuel electrode film layers is obtained;

[0138] S204: Above the end region of the first plane close to the closed end, the electrolyte slurry is additionally printed until the same height as the second plane, forming a second electrolyte end film layer;

[0139] S205: Above the second plane, the electrolyte slurry is printed in intervals, so that the electrolyte slurry partially covers the fuel electrode film layer below and covers the first electrolyte end film layer and / or the second electrolyte end film layer adjacent to the fuel electrode film layer below, and after drying, a plurality of electrolyte film layers and a plurality of second intervals are formed;

[0140] S206: At each of the second intervals, the connector slurry and the second insulation layer slurry are printed in the fuel gas flow direction respectively, until the same height as the electrolyte film layer; the connector slurry covers the first insulation film layer below and partially covers the fuel electrode film layer adjacent to the first insulation film layer below, and after drying, a third plane formed by the first connector film layer, the second insulation film layer and the electrolyte film layer is obtained;

[0141] S207: On the side of the first plane close to the closed end, the connector slurry is printed until the same height as the third plane, forming a second connector film layer;

[0142] S208: The second insulation layer slurry is continuously printed above the second insulation film layer until the insulation layer reaches the set thickness, and after drying, a third insulation film layer and a third interval are formed;

[0143] S209: The closed end is immersed multiple times with an electrolyte solution, and after drying, an electrolyte coating film layer is formed on the closed end, thereby obtaining a first cell / electrolyser precursor;

[0144] S210: performing a first baking process on the first battery / electrolyzer precursor, thereby obtaining a second battery / electrolyzer precursor;

[0145] S211: printing air electrode paste at each of the third intervals and above the second connector, until the same height as the third insulating film layer, and after drying, obtaining a fourth plane formed by a plurality of air electrode film layers and a plurality of third insulating film layers, thereby obtaining a third battery / electrolyzer precursor;

[0146] S212: after performing a second baking process on the third battery / electrolyzer precursor, a self-sealing bamboo joint tube type solid oxide fuel cell / electrolyzer is prepared.

[0147] The preparation step S201 prints the first insulating layer paste above the working area to form a first plane which is a ring-shaped plane covering the surface of the annular tube wall of the base tube. The thickness of the first plane is 100-300 μm. The first plane obtained in this step forms a porous insulating layer structure covering the surface of the annular tube wall (working area) after subsequent baking process.

[0148] The preparation step S202 prints the fuel electrode film layer at intervals without covering the two end regions of the first plane. The length of the end region near the opening end of the ceramic base tube can be 0.5-1 times the length of the first interval. The length of the end region near the closed end of the ceramic base tube can be 0.5-1 times the length of the first interval. The fuel electrode film layer forms a fuel electrode after subsequent sintering process.

[0149] The preparation step S203 prints the electrolyte paste and the second insulating layer paste between every two fuel electrodes (at the first intervals). The electrolyte paste is filled near the opening end of the base tube at each first interval, and the second insulating layer paste is filled near the closed end of the base tube at each first interval. After drying, the electrolyte end head and the second insulating film layer are formed, thereby forming a second plane with a thickness of 50-250 μm. The first insulating film layer formed by the second insulating paste after drying forms a first insulating layer after subsequent sintering process. The first electrolyte end head film layer formed by the electrolyte paste after drying forms a first electrolyte end head after subsequent sintering process.

[0150] Further, the end region near the closed end of the base tube is not covered by the fuel electrode paste. The preparation step S204 prints the electrolyte paste in this region to form a second electrolyte end head film layer until the same height as the second plane.

[0151] In the preparation step S205, the printing of the electrolyte slurry is performed above the second plane, and the end area of the second interval of 0.5-1 times the length is left without printing near the opening end side of the base tube, and after drying, each electrolyte film layer partially covers the fuel electrode film layer below it and covers the first electrolyte end film layer or the second electrolyte end film layer adjacent to the fuel electrode film layer below it. After the electrolyte film layer is subjected to subsequent calcination treatment, the electrolyte layer is formed, and the interval between every two electrolyte layers is the second interval.

[0152] Further, the step S206 prints the connecting body slurry and the second insulation layer slurry at each second interval, the connecting body slurry is filled in each second interval near the opening end side of the base tube, and the second insulation layer slurry is filled in each second interval near the closed end side of the base tube, and after drying, the first connecting body film layer and the second insulation film layer are formed, and the thickness of the third plane formed by the two is 10-100 μm. The length of the first connecting body film layer is not less than the second insulation film layer, and the covered length of the fuel electrode film layer partially covered by the first connecting body film layer is 0.2-2 mm.

[0153] In the preparation step S207, the connecting body slurry is printed on the first plane near the closed end side of the base tube to form the second connecting body film layer, which is subjected to subsequent calcination treatment to form the second connecting body.

[0154] It should be noted that in the embodiment of the present application, the composition of the ceramic support body can be inert ceramic (in the working state, the composition cannot be reduced to metal ceramic by hydrogen), or ceramic composition that can be reduced to metal ceramic by hydrogen in the working state; the second connecting body is in contact with the ceramic support body and is covered by the air electrode of the last single cell; in this way, for the ceramic support body composed of inert components, the second connecting body can seal the porous insulation layer to prevent the fuel electrode from being oxidized; for the support body that can be reduced to metal ceramic by hydrogen in the working state, the second connecting body leads the current collected in the last single cell unit to the ceramic support body, solving the problem of current convergence.

[0155] Further, the embodiment of the present application continues to print the second insulation layer slurry above the second insulation film layer to form the third insulation film layer, and the height of the third insulation film layer after the first calcination is consistent with the height of the subsequently printed air electrode film layer.

[0156] After the third insulating film layer is formed, the closed end of the base tube is sealed, and the closed end is immersed in an electrolyte solution multiple times, and then dried to form an electrolyte coating film layer on the closed end. After the electrolyte coating film layer is formed, the resulting structure (first battery / electrolytic cell precursor) is subjected to a first firing process at a temperature of 1250°C to 1500°C for 4 to 6 hours. The first firing process converts the first plane printed on the surface of the base tube into a porous insulating layer, and the first, second, and third insulating film layers are converted into a dense insulating layer.

[0157] Further, the embodiment of the present application continues to print the air electrode paste at the third interval and above the second connector, and leaves an end region of the third interval with a length of 0.5 to 1 times the length of the opening end side without printing. After drying, a plurality of air electrode film layers are formed, the air electrode film layers are at the same height as the third insulating film layer, and together form a fourth plane, and the thickness of the fourth plane is 500 μm to 1500 μm. The resulting structure is then subjected to a second firing process at a temperature of 1100°C to 1500°C for 2 to 4 hours, and a bamboo-structured tubular solid oxide fuel cell / electrolytic cell is finally obtained.

[0158] In some embodiments, the length of the first interval is 0.3 to 2 mm; the length of the second interval is 0.4 to 3 mm; and the length of the third interval is 0.2 to 2 mm.

[0159] In order for those skilled in the art to better understand the present application, the following describes a bamboo-structured tubular solid oxide fuel cell / electrolytic cell, a preparation method, and a battery / electrolytic cell stack, and a preparation method, through a plurality of specific embodiments.

[0160] Embodiments 1 to 4 prepare the bamboo-structured tubular solid oxide fuel cell / electrolytic cell shown in FIG. 1, and the bamboo-structured tubular solid oxide fuel cell / electrolytic cell stack, and embodiments 5 to 8 prepare the bamboo-structured tubular solid oxide fuel cell / electrolytic cell shown in FIG. 4, and the bamboo-structured tubular solid oxide fuel cell / electrolytic cell stack.

[0161] Embodiment 1

[0162] Step 1: Take a hollow cylindrical ceramic tube with both ends open as the base tube, the base tube is composed of 3 mol% calcium oxide stabilized zirconia (3CSZ) and nickel oxide (NiO) with a mass ratio of 55:45, the outer diameter is 15-25 mm, the wall thickness is 1.5-3 mm, and the porosity is 25%-35%. The base tube becomes a cermet structure with electrical conductivity after hydrogen reduction in the working state. A first insulating layer slurry is printed on the surface of the base tube by screen printing method, the composition of the insulating layer slurry is strontium zirconate (SrZrO3) and 2 mol% aluminum oxide (Al2O3), the thickness is 100 um, and the first plane (porous insulating film layer) is formed after drying at 40-80°C after screen printing.

[0163] Step 2: A fuel electrode slurry is printed on the above-mentioned first plane by screen printing method, the composition of the fuel electrode slurry is 8 mol% yttrium oxide stabilized zirconia (8YSZ) and nickel oxide (NiO) with a mass ratio of 60:40, the thickness is 50 um, the width of the fuel electrode unit is 5 mm, and the interval between adjacent fuel electrodes is 2 mm, and the fuel electrode film layer is formed after drying at 40-80°C after screen printing.

[0164] Step 3: Between the above-mentioned fuel electrode film layer, along the direction of fuel gas flow, respectively print electrolyte slurry and second insulating layer slurry, the composition of the electrolyte slurry is 8 mol% yttrium oxide stabilized zirconia (8YSZ), the printing thickness is 50 um, and the width is 1 mm, forming the first electrolyte end film layer; the composition of the insulating layer slurry is strontium zirconate (SrZrO3) and 6 mol% aluminum oxide (Al2O3), the screen printing thickness is 50 um, and the width is 1 mm, forming the first insulating film layer.

[0165] Step 4: Above the first plane end region near the fuel gas outlet end of the base tube, print the electrolyte slurry at the same height as the fuel electrode, forming the second electrolyte end film layer; the composition of the electrolyte slurry is 8 mol% yttrium oxide stabilized zirconia (8YSZ), the printing thickness is 50 um, and the width is 1 mm; and the second electrolyte end film layer is formed after drying at 40-80°C after screen printing.

[0166] Step 5: Print the electrolyte slurry above the fuel electrode film layer in intervals, so that it partially covers the fuel electrode film layer below and covers the first electrolyte end film below; the composition of the electrolyte slurry is 8 mol% yttrium oxide stabilized zirconia (8YSZ), the printing thickness is 20 um, and the width is 4 mm; and the electrolyte film layer is formed after drying at 40-80°C after screen printing.

[0167] Step 6: Between the above-mentioned electrolyte film layer, along the direction of fuel gas flow, respectively print the connector slurry and the second insulating layer slurry; the composition of the connector slurry is strontium lanthanum titanate (La 0.3 Sr0.7 SrZr03, LST) with a printing thickness of 20 um and a width of 2 mm, partially covering the fuel electrode film below and covering a width of 1 mm, and covering the first insulating film layer below; the second insulating layer paste is composed of strontium zirconate (SrZr03) and 6 mol% alumina (Al203), with a printing thickness of 20 um and a width of 1 mm; after screen printing, drying is performed at 40-80°C, to form the first connecting body film layer and the second insulating film layer, respectively.

[0168] Step 7: printing a connecting body paste on the first plane near the side of the base tube fuel gas outlet end, to form a second connecting body film layer; the connecting body paste is composed of lanthanum-doped strontium titanate (La 0.3 Sr 0.7 Ti03, LST) with a printing thickness of 170 um and a width of 2 mm.

[0169] Step 8: continuing to print a second insulating layer paste on top of the second insulating film layer, to form a third insulating film layer; the insulating layer paste is composed of strontium zirconate (SrZr03) and 6 mol% alumina (Al203), with a printing thickness of 500 um and a width of 1 mm, and after screen printing, drying is performed at 40-80°C.

[0170] Step 9: the battery / electrolytic cell precursor obtained in the above step 8 is heated at a heating rate of 1°C / min to 400°C, degassed in air for 6 h, then degassed at a heating rate of 1°C / min from 400°C to 600°C for 8 h, and then sintered and formed at a heating rate of 2°C / min at 1400°C in air for 6 h.

[0171] Step 10: printing an air electrode paste on the intervals of the above third insulating film layer, and on top of the connecting body; the air electrode paste is composed of 8 mol yttria-stabilized zirconia (8YSZ) and strontium-doped lanthanum manganate (La 0.8 Sr 0.2 Mn03, LSM) with a printing thickness of 500 um and a width of 6 mm, and after screen printing, drying is performed at 40-80°C.

[0172] Step 11: the above battery / electrolytic cell precursor is sintered and formed at a heating rate of 2°C / min at 1200°C in air for 4 h, to obtain a bamboo-tube solid oxide fuel cell / electrolytic cell.

[0173] The fuel gas inlet ends of 10 of the above bamboo-tube solid oxide fuel cell / electrolytic cells are placed in a fuel gas channel base in a certain arrangement, to obtain a bamboo-tube solid oxide fuel cell / electrolytic cell stack.

[0174] Example 2

[0175] Step 1: Take a hollow cylindrical ceramic tube with both ends open as the base tube, the base tube is composed of 3 mol yttria-stabilized zirconia (3YSZ) and nickel oxide (NiO) with a mass ratio of 50:50, the outer diameter is 15-25 mm, the wall thickness is 1.5-3 mm, and the porosity is 25%-35%. The base tube becomes a conductive cermet support structure after hydrogen reduction in the working state. A first insulating layer slurry is printed on the surface of the base tube by screen printing, the insulating layer slurry is composed of magnesium aluminate spinel (MgAl2O4) and 30 mol% magnesium oxide (MgO), the thickness is 50 um, and the screen printing is dried at 40-80°C after completion, forming a first plane (porous insulating film layer).

[0176] Step 2: The fuel electrode slurry is printed on the above-mentioned first plane by screen printing, the fuel electrode slurry is composed of 8 mol yttria-stabilized zirconia (8YSZ) and nickel oxide (NiO) with a mass ratio of 60:40, the thickness is 100 um, the width of the fuel electrode unit is 5 mm, and the interval between adjacent fuel electrodes is 2 mm, and the screen printing is dried at 40-80°C after completion, forming a fuel electrode film layer.

[0177] Step 3: Between the above-mentioned fuel electrode film layer, along the fuel gas flow direction, respectively print the electrolyte slurry and the second insulating layer slurry, the electrolyte slurry is composed of 8 mol yttria-stabilized zirconia (8YSZ), the printing thickness is 100 um, and the width is 1 mm, forming a first electrolyte end film layer; the insulating layer slurry is composed of magnesium aluminate spinel (MgAl2O4) and 30 mol% magnesium oxide (MgO) and 10 mol% zirconia (ZrO2), the screen printing thickness is 100 um, and the width is 1 mm, forming a first insulating film layer.

[0178] Step 4: Above the first plane end region near the fuel gas outlet end, print the electrolyte slurry, which is the same height as the fuel electrode, forming a second electrolyte end film layer; the electrolyte slurry is composed of 8 mol yttria-stabilized zirconia (8YSZ), the printing thickness is 100 um, and the width is 1 mm; and the screen printing is dried at 40-80°C after completion.

[0179] Step 5: Print the electrolyte slurry above the fuel electrode film layer, so that it partially covers the fuel electrode film layer below and covers the first electrolyte end film below; the electrolyte slurry is composed of 8 mol yttria-stabilized zirconia (8YSZ), the printing thickness is 20 um, and the width is 4 mm; and the screen printing is dried at 40-80°C after completion, forming an electrolyte film layer.

[0180] Step 6: Print the connecting body paste and the second insulating layer paste between the above-mentioned electrolyte membrane layers along the fuel gas flow direction respectively; wherein the connecting body paste is composed of lanthanum-doped strontium titanate (La 0.3 Sr 0.7 TiO3, LST), with a printing thickness of 20 um and a width of 2 mm, partially covering the fuel electrode membrane below and covering a width of 1 mm, and covering the first insulating layer membrane below; the insulating layer paste is composed of magnesium aluminum spinel (MgAl2O4), 30 mol% magnesium oxide (MgO) and 10 mol% zirconium oxide (ZrO2), with a printing thickness of 20 um and a width of 1 mm; after silk printing, dry at 40-80°C to form the first connecting body membrane layer and the second insulating membrane layer respectively.

[0181] Step 7: Print the connecting body paste on the first plane near the substrate tube fuel gas outlet end side to form the second connecting body membrane layer; the connecting body paste is composed of lanthanum-doped strontium titanate (La 0.3 Sr 0.7 TiO3, LST), with a printing thickness of 220 um and a width of 2 mm.

[0182] Step 8: Continue to print the second insulating layer paste on top of the second insulating membrane layer to form the third insulating membrane layer, the insulating layer paste is composed of magnesium aluminum spinel (MgAl2O4), 30 mol% magnesium oxide (MgO) and 10 mol% zirconium oxide (ZrO2), with a printing thickness of 500 um and a width of 1 mm, and dry at 40-80°C after silk printing.

[0183] Step 9: The battery / electrolytic cell precursor obtained in the above-mentioned step 8 is heated to 400°C at a heating rate of 1°C / min, degassed in air for 6h, then degassed from 400°C to 600°C at a heating rate of 1°C / min for 8h, and then sintered at 1450°C in air for 6h at a heating rate of 2°C / min.

[0184] Step 10: Print the air electrode paste at intervals on the above-mentioned third insulating membrane layer and on top of the connecting body; the air electrode paste is composed of 8 mol yttria-stabilized zirconia (8YSZ) and strontium-doped lanthanum manganate (La 0.8 Sr 0.2 MnO3, LSM) with a mass ratio of 50:50, with a printing thickness of 500 um and a width of 6 mm, and dry at 40-80°C after silk printing.

[0185] Step 11: The battery / electrolytic cell precursor obtained in the above-mentioned step 10 is sintered at 1200°C in air for 4h at a heating rate of 2°C / min to obtain a tubular solid oxide fuel cell / electrolytic cell.

[0186] Twenty fuel gas inlet ends of the above-described segmented-tube solid oxide fuel cell / electrolysis cell were placed in a fuel gas passage base in a certain arrangement, thereby obtaining a segmented-tube solid oxide fuel cell / electrolysis cell stack.

[0187] Example 3:

[0188] This example uses a hollow cylindrical ceramic tube with open ends as a base tube, the base tube is composed of 3 mol calcia-stabilized zirconia (CSZ) containing 10 wt% MgO, and the remaining steps are the same as example 2.

[0189] Example 4: This example uses a hollow cylindrical ceramic tube with open ends as a base tube, the base tube is composed of magnesium aluminate spinel (MgAl2O4) and 30 mol% magnesium oxide (MgO), and the remaining steps are the same as example 2.

[0190] Example 5

[0191] Step 1: A hollow cylindrical ceramic tube with open ends and closed ends is used as a base tube, the base tube is composed of 3 mol calcia-stabilized zirconia (3CSZ) and nickel oxide (NiO) with a mass ratio of 55:45, the outer diameter is 15-25 mm, the wall thickness is 1.5-3 mm, and the porosity is 25%-35%. The base tube becomes a cermet structure with electrical conductivity after hydrogen reduction in the working state. A first insulating layer slurry is printed on the surface of the base tube by screen printing, the insulating layer slurry is composed of strontium zirconate (SrZrO3) and 2 mol% aluminum oxide (Al2O3), the thickness is 100 um, and the first plane is formed after drying at 40-80°C after screen printing.

[0192] Step 2: A fuel electrode slurry is printed on the above-mentioned first plane (porous insulating film layer) by screen printing, the fuel electrode slurry is composed of 8 mol yttria-stabilized zirconia (8YSZ) and nickel oxide (NiO) with a mass ratio of 60:40, the thickness is 50 um, the width of the fuel electrode unit is 5 mm, and the interval between adjacent fuel electrodes is 2 mm. The fuel electrode film layer is formed after drying at 40-80°C after screen printing.

[0193] Step 3: Between the above-mentioned fuel electrode film layers, electrolyte slurry and second insulating layer slurry are printed in the direction of fuel gas flow, respectively. The electrolyte slurry is composed of 8 mol yttria-stabilized zirconia (8YSZ), the printing thickness is 50 um, and the width is 1 mm to form the first electrolyte end film layer. The insulating layer slurry is composed of strontium zirconate (SrZrO3) and 6 mol% aluminum oxide (Al2O3), the screen printing thickness is 50 um, and the width is 1 mm to form the first insulating film layer.

[0194] Step 4: Print the electrolyte paste above the first planar end region near the closed end, with the fuel electrode at the same height, to form a second electrolyte end head film layer; the electrolyte paste is composed of 8 mol yttria-stabilized zirconia (8YSZ), with a printing thickness of 50 um and a width of 1 mm; after printing, dry at 40-80°C.

[0195] Step 5: Print the electrolyte paste above the fuel electrode film layer, partially covering the fuel electrode film layer below and covering the first electrolyte end head film layer below; the electrolyte paste is composed of 8 mol yttria-stabilized zirconia (8YSZ), with a printing thickness of 20 um and a width of 4 mm; after printing, dry at 40-80°C to form an electrolyte film layer.

[0196] Step 6: Print the connector paste and the second insulating layer paste between the above-mentioned electrolyte film layers in the direction of fuel gas flow; the connector paste is composed of lanthanum-doped strontium titanate (La 0.3 Sr 0.7 TiO3, LST), with a printing thickness of 20 um and a width of 2 mm, partially covering the fuel electrode film below with a width of 1 mm, and covering the first insulating film layer below; the insulating layer paste is composed of strontium zirconate (SrZrO3) and 6 mol% aluminum oxide (Al2O3), with a printing thickness of 20 um and a width of 1 mm; after printing, dry at 40-80°C to form a first connector film layer and a second insulating film layer, respectively.

[0197] Step 7: Print the connector paste on the first planar side near the closed end; the connector paste is composed of lanthanum-doped strontium titanate (La 0.3 Sr 0.7 TiO3, LST), with a printing thickness of 170 um and a width of 2 mm.

[0198] Step 8: Continue printing the second insulating layer paste above the second insulating film layer; the insulating layer paste is composed of strontium zirconate (SrZrO3) and 6 mol% aluminum oxide (Al2O3), with a printing thickness of 500 um and a width of 1 mm; after printing, dry at 40-80°C to form a third insulating film layer.

[0199] Step 9: Use a 3 mol% zirconium oxychloride solution to impregnate the closed end, and after drying, form an electrolyte coating film layer.

[0200] Step 10: Heat the above-mentioned battery / electrolytic cell precursor to 400°C at a heating rate of 1°C / min in air for 6h, then from 400°C to 600°C at a heating rate of 1°C / min for 8h, and then sinter at 1400°C at a heating rate of 2°C / min in air for 6h.

[0201] Step 11: Print air electrode paste on the space between the third insulation layer and above the connecting body; the composition of the air electrode paste is 8 mol yttria-stabilized zirconia (8YSZ) and strontium-doped lanthanum manganate (La 0.8 Sr 0.2 MnO3, LSM) with a mass ratio of 50:50, the printing thickness is 500 um, and the width is 6 mm. After printing, dry at 40-80°C.

[0202] Step 12: Sinter the above battery / electrolytic cell precursor at 1200°C for 4h in air at a heating rate of 2°C / min to form a tubular solid oxide fuel cell / electrolytic cell.

[0203] Example 6

[0204] Step 1: Use a hollow cylindrical ceramic tube with an open end and a closed end as the base tube. The composition of the base tube is 3 mol yttria-stabilized zirconia (3YSZ) and nickel oxide (NiO) with a mass ratio of 50:50, the outer diameter is 15-25 mm, the wall thickness is 1.5-3 mm, and the porosity is 25%-35%. After reduction by hydrogen gas in the working state, the base tube becomes a conductive cermet support structure. Print the first insulation layer paste on the surface of the base tube by screen printing. The composition of the insulation layer paste is magnesium aluminate spinel (MgAl2O4) and 30 mol% magnesium oxide (MgO), the thickness is 50 um, and dry at 40-80°C after printing to form a first plane.

[0205] Step 2: Print the fuel electrode paste on the above first plane (porous insulation film layer) at intervals by screen printing. The composition of the fuel electrode paste is 8 mol yttria-stabilized zirconia (8YSZ) and nickel oxide (NiO) with a mass ratio of 60:40, the thickness is 100 um, the width of the fuel electrode unit is 5 mm, and the interval between adjacent fuel electrodes is 2 mm. Dry at 40-80°C after printing.

[0206] Step 3: Print the electrolyte paste and the second insulation layer paste between the above fuel electrodes along the direction of fuel gas flow. The composition of the electrolyte paste is 8 mol yttria-stabilized zirconia (8YSZ), the printing thickness is 100 um, and the width is 1 mm to form a first electrolyte end film layer. The composition of the insulation layer paste is magnesium aluminate spinel (MgAl2O4), 30 mol% magnesium oxide (MgO), and 10 mol% zirconia (ZrO2), the screen printing thickness is 100 um, and the width is 1 mm to form a first insulation film layer.

[0207] Step 4: Print the electrolyte paste above the first planar end region near the fuel gas outlet end, with the fuel electrode in the same height, to form the second electrolyte end head film layer; the electrolyte paste is composed of 8 mol yttria-stabilized zirconia (8YSZ), with a printing thickness of 100 um and a width of 1 mm; after screen printing, dry at 40-80°C.

[0208] Step 5: Print the electrolyte paste above the fuel electrode film layer, so that it partially covers the fuel electrode film layer below and covers the first electrolyte end head film layer below; the electrolyte paste is composed of 8 mol yttria-stabilized zirconia (8YSZ), with a printing thickness of 20 um and a width of 4 mm; after screen printing, dry at 40-80°C to form the electrolyte film layer.

[0209] Step 6: Print the connector paste and the second insulating layer paste between the above-mentioned electrolyte film layers in the direction of fuel gas flow; the connector paste is composed of lanthanum-doped strontium titanate (La 0.3 Sr 0.7 TiO3, LST), with a printing thickness of 20 um and a width of 2 mm, partially covering the fuel electrode film below with a width of 1 mm, and covering the first insulating layer film below; the insulating layer paste is composed of magnesium aluminum spinel (MgAl2O4), 30 mol% magnesium oxide (MgO), and 10 mol% zirconium oxide (ZrO2), with a printing thickness of 20 um and a width of 1 mm; after screen printing, dry at 40-80°C to form the first connector film layer and the second insulating film layer, respectively.

[0210] Step 7: Print the connector paste on the first planar side near the fuel gas outlet end; the connector paste is composed of lanthanum-doped strontium titanate (La 0.3 Sr 0.7 TiO3, LST), with a printing thickness of 220 um and a width of 2 mm.

[0211] Step 8: Continue to print the second insulating layer paste above the second insulating film layer; the insulating layer paste is composed of magnesium aluminum spinel (MgAl2O4), 30 mol% magnesium oxide (MgO), and 10 mol% zirconium oxide (ZrO2), with a printing thickness of 500 um and a width of 1 mm; after screen printing, dry at 40-80°C to form the third insulating film layer.

[0212] Step 9: Use a 3 mol% zirconium oxychloride solution to impregnate the closed end, and after drying, form the electrolyte coating film layer.

[0213] Step 10: The above cell / electrolytic cell precursor was heated to 400 °C at a heating rate of 1 °C / min for 6 h to remove the binder in air, then heated from 400 °C to 600 °C at a heating rate of 1 °C / min for 8 h, and then sintered at 1450 °C for 6 h at a heating rate of 2 °C / min in air.

[0214] Step 11: The air electrode paste was printed on the space between the above third insulation layer and the top of the connector; the composition of the air electrode paste was 8 mol yttria-stabilized zirconia (8YSZ) and strontium-doped lanthanum manganate (La 0.8 Sr 0.2 Mn03, LSM) with a mass ratio of 50:50, the printing thickness was 500 um, and the width was 6 mm. After printing, it was dried at 40-80 °C.

[0215] Step 12: The above (obtained in step 11) cell / electrolytic cell precursor was sintered at 1200 °C for 4 h at a heating rate of 2 °C / min in air to form a tubular solid oxide fuel cell / electrolytic cell.

[0216] Example 7:

[0217] In this example, a hollow cylindrical ceramic tube with an open end and a closed end was used as the substrate tube, and the composition of the substrate tube was 3 mol calcium-stabilized zirconia (CSZ) containing 10 wt% MgO. The remaining steps were the same as those in Example 6.

[0218] Example 8: In this example, a hollow cylindrical ceramic tube with an open end and a closed end was used as the substrate tube, and the composition of the substrate tube was magnesium aluminate spinel (MgAl204) and 30 mol% magnesium oxide (MgO). The remaining steps were the same as those in Example 6.

[0219] As used herein, the term "one embodiment," "an embodiment,” or "one or more embodiments,” means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the disclosure. The appearances of the phrase "in one embodiment” in various places in the specification are not necessarily all referring to the same embodiment.

[0220] In the description provided herein, numerous specific details are set forth. However, it is understood that embodiments of the disclosure can be practiced without these specific details. In some instances, well-known methods, structures and techniques have not been shown in detail in order not to obscure an understanding of this description.

[0221] In the claims, any reference signs placed between parentheses shall not be construed as limiting the claim. The word comprising does not exclude the presence of elements or steps other than those listed in a claim. The word "a" or "an" preceding an element does not exclude the presence of a plurality of such elements. The disclosure can be implemented by means of both hardware and software, and any combination thereof. In a unitary claim, several devices, apparatuses or means can be listed, comprising means for carrying out a certain task. The use of the term "means" does not limit the scope of the claim to only a device or apparatus. The word "comprising" does not exclude other elements or steps than those listed in a claim. The word "a" or "an" preceding an element does not exclude the presence of a plurality of such elements. The word "first", "second", "third", etc. does not imply any order or precedence. The use of the terms "first", "second", "third", etc. does not limit the scope of the claims to only three elements. The use of the terms "first", "second", "third", etc. does not require the presence of three elements, but it does not exclude the presence of three elements.

[0222] Finally, it should be noted that the above-mentioned embodiments are merely intended for describing and illustrating, not limiting the technical solutions of the present disclosure; even if the present disclosure has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacements for part of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present disclosure.

Claims

1. A bamboo-tube type solid oxide fuel cell / electrolysis cell, characterized by, The battery group is distributed on the surface of the porous insulating layer by a first single cell and other single cells in series along the fuel gas flow direction. A first insulating layer is arranged between the fuel electrodes of every two adjacent single cells, a first connector and a second insulating layer are arranged in sequence along the fuel gas flow direction between the electrolyte layers of every two adjacent single cells, and a third insulating layer is arranged between the air electrodes of every two adjacent single cells. Each first connector covers the first insulating layer thereunder and partially overlaps the fuel electrode thereunder. The third insulating layer is vertically arranged above the second insulating layer. The ceramic support is a ceramic support with both ends open or a ceramic support with one end open and one end closed.

2. The bamboo-tube type solid oxide fuel cell / electrolysis cell according to claim 1, wherein In the first single cell, the fuel electrode, the electrolyte layer and the air electrode are arranged in layers in recess from the porous insulating layer.

3. The bamboo-tube type solid oxide fuel cell / electrolysis cell according to claim 2, wherein The fuel electrode is arranged in recess by 1-5 mm from the porous insulating layer. The electrolyte layer is arranged in recess by 0.4-2 mm from the fuel electrode. The air electrode is arranged in recess by 0.4-2 mm from the electrolyte layer.

4. The bamboo-tube type solid oxide fuel cell / electrolysis cell according to claim 1, wherein An electrolyte end head is further arranged between the fuel electrodes of two adjacent single cells, and each electrolyte end head is located close to the fuel gas inlet end of the ceramic support.

5. The bamboo-tube type solid oxide fuel cell / electrolysis cell according to claim 4, wherein Each electrolyte end head is partially or completely covered by the electrolyte layer thereover.

6. The bamboo-tube type solid oxide fuel cell / electrolysis cell according to claim 1, wherein The overlapping length of each first connector with the fuel electrode thereunder is 0.2-2 mm.

7. The bamboo-tube type solid oxide fuel cell / electrolysis cell according to claim 1, wherein When the ceramic support is a ceramic support with both ends open, a second connector is arranged close to the fuel gas outlet end of the ceramic support in the last single cell in the battery group, the second connector is in contact with the ceramic support and is covered by the air electrode of the last single cell, and an electrolyte end head is arranged between the fuel electrode of the last single cell and the second connector. When the ceramic support is a ceramic support with one end open and one end closed, an electrolyte coating layer is arranged at the closed end of the ceramic support, a second connector is arranged between the electrolyte coating layer and the last single cell close to the closed end, the second connector is in contact with the ceramic support and is covered by the air electrode of the last single cell, and an electrolyte end head is arranged between the fuel electrode of the last single cell and the second connector.

8. The bamboo-tube type solid oxide fuel cell / electrolysis cell according to claim 1, wherein The first insulating layer is in the same height as the fuel electrode. The first connector and the second insulating layer are in the same height as the electrolyte layer. The third insulating layer is in the same height as the air electrode.

9. The bamboo-tube type solid oxide fuel cell / electrolysis cell according to claim 1, wherein The thickness of the porous insulating layer is 100-300 μm. The thickness of the fuel electrode is 50-250 μm. The thickness of the electrolyte layer is 10-100 μm. The thickness of the air electrode is 500-1500 μm. (Whether to add a space between numbers and units, you uniformly) 10. A method for producing a bamboo-tube type solid oxide fuel cell / electrolytic cell, characterized by, The bamboo joint pipe type solid oxide fuel cell / electrolysis cell comprises a ceramic support body with both ends open, a porous insulating layer distributed on the surface of the ceramic support body, and a cell group distributed on the surface of the porous insulating layer, wherein the cell group is composed of a first single cell and a plurality of single cells distributed in series on the surface of the porous insulating layer along the fuel gas flow direction, and the preparation method comprises the following steps: S101: taking a hollow cylindrical ceramic pipe with both ends open as a base pipe, and printing first insulating layer slurry on the annular pipe wall, and forming a first plane after drying; S102: printing fuel electrode slurry on the middle area of the first plane in intervals; after drying, a plurality of fuel electrode film layers and a plurality of first intervals are formed; S103: printing electrolyte slurry and second insulating layer slurry on each of the first intervals in the fuel gas flow direction respectively, until the height of the fuel electrode film layer, and after drying, a second plane composed of a plurality of first insulating film layers, a plurality of first electrolyte end film layers and a plurality of fuel electrode film layers is obtained; S104: printing electrolyte slurry on the end area of the first plane close to the fuel gas outlet end, until the height of the second plane, to form a second electrolyte end film layer; S105: printing electrolyte slurry on the second plane in intervals, so that the electrolyte slurry partially covers the fuel electrode film layer below and covers the first electrolyte end film layer and / or the second electrolyte end film layer adjacent to the fuel electrode film layer below, and after drying, a plurality of electrolyte film layers and a plurality of second intervals are formed; S106: printing connector slurry and second insulating layer slurry on each of the second intervals in the fuel gas flow direction respectively, until the height of the electrolyte film layer; the connector slurry covers the first insulating film layer below and partially covers the fuel electrode film layer adjacent to the first insulating film layer below, and after drying, a third plane formed by the first connector film layer, the second insulating film layer and the electrolyte film layer is obtained; S107: printing connector slurry on the side of the first plane close to the fuel gas outlet end, until the height of the third plane, to form a second connector film layer; S108: continuing to print second insulating layer slurry on the second insulating film layer until the insulating layer reaches the set thickness, and after drying, a first cell / electrolysis cell precursor with equal height of the third insulating film layer and the third interval is obtained; S109: performing a first firing process on the first cell / electrolysis cell precursor, thereby obtaining a second cell / electrolysis cell precursor; S110: printing air electrode slurry on each of the third intervals and above the second connector, until the height of the third insulating film layer, and after drying, a fourth plane formed by a plurality of air electrode film layers and a plurality of third insulating film layers is obtained, thereby obtaining a third cell precursor; S111: after performing a second firing process on the third cell / electrolysis cell precursor, a bamboo joint pipe type solid oxide fuel cell / electrolysis cell is prepared. ​ 11. The method for producing the bamboo-tube type solid oxide fuel cell / electrolytic cell according to claim 10, wherein The second plane is arranged in a stepped manner based on the first plane on the side close to the fuel gas inlet end, with the first interval length being 0.5-1 times; the third plane is arranged in a stepped manner based on the second plane, with the second interval length being 0.5-1 times; and the fourth plane is arranged in a stepped manner based on the third plane, with the third interval length being 0.5-1 times.

12. The method of claim 10, wherein the method further comprises the step of: The first interval length is 0.3-2 mm. ​ The second interval length is 0.4-3 mm. The third interval length is 0.2-2 mm.

13. The method of claim 10, wherein the method further comprises the step of: The length of the first connecting film layer is not less than half of the second interval length. ​ 14. The method of claim 10, wherein the method further comprises the step of: 5 forming the porous ceramic tube by extruding a ceramic slurry through a die having a 6 plurality of grooves, and drying and sintering the extruded tube. 7 The covering length of the fuel electrode film layer partially covered by the first connecting film layer is 0.2-2 mm.

15. The method of claim 10, wherein the method further comprises the step of: 5 forming the porous ceramic tube by extruding a ceramic slurry through a die having a plurality of protrusions on the surface of the die. The first firing temperature is 1250-1500 DEG C, and the first firing time is 4-6 h.

16. The method of claim 10, wherein the bamboo pipe type solid oxide fuel cell / electrolysis cell is prepared by the steps of: The second firing temperature is 1100-1500 DEG C, and the second firing time is 2-4 h.

17. The method of claim 10, wherein the method further comprises the step of: 5 forming the porous ceramic tube by extruding a ceramic slurry through a die having a plurality of protrusions on the surface of the die. 10 The first insulation layer slurry forms a porous insulation layer after firing treatment, and the second insulation layer slurry forms a dense insulation layer after firing treatment.

18. The method of claim 10, wherein the method further comprises the step of: 5 forming the porous ceramic tube by extruding a ceramic slurry through a die having a plurality of protrusions on the surface of the die. 10 The thickness of the first plane is 100-300 μm. The thickness of the second plane is 50-250 μm. The thickness of the third plane is 10-100 μm. The thickness of the fourth plane is 500-1500 μm.

19. A method of making a bamboo-tube solid oxide fuel cell / electrolysis cell, characterized by, The bamboo joint pipe type solid oxide fuel cell / electrolytic cell comprises a ceramic support with an open end and a closed end, a porous insulation layer distributed on the surface of the ceramic support, and a cell group distributed on the surface of the porous insulation layer, wherein the cell group is formed by a first single cell and other single cells distributed in series on the surface of the porous insulation layer along the fuel gas flow direction, and the preparation method comprises the following steps: S201: taking a hollow cylindrical ceramic tube with an open end and a closed end as a base tube, and printing a first insulation layer slurry on the annular tube wall to form a first plane after drying; S202: printing fuel electrode slurry on the first plane in the middle region and at intervals; after drying, a plurality of fuel electrode film layers and a plurality of first intervals are formed; S203: printing electrolyte slurry and second insulation layer slurry at each first interval along the fuel gas flow direction, until the height of the electrolyte slurry and the second insulation layer slurry is equal to that of the fuel electrode film layer, to obtain a second plane formed by a plurality of first insulation film layers, a plurality of first electrolyte end film layers, and a plurality of fuel electrode film layers after drying; S204: printing electrolyte slurry on the end region of the first plane close to the closed end to form a second electrolyte end film layer until the height of the electrolyte slurry is equal to that of the second plane; S205: printing electrolyte slurry on the second plane at intervals, so that the electrolyte slurry partially covers the fuel electrode film layer below and covers the first electrolyte end film layer and / or the second electrolyte end film layer adjacent to the fuel electrode film layer below, to form a plurality of electrolyte film layers and a plurality of second intervals after drying. S206: At each of the second intervals, print the connecting body paste and the second insulation layer paste respectively along the fuel gas flow direction until the same height as the electrolyte membrane layer; the connecting body paste covers the first insulation film layer below and partially covers the fuel electrode film layer below adjacent to the first insulation film layer, and after drying, a third plane formed by the first connecting body film layer, the second insulation film layer and the electrolyte membrane layer is obtained; S207: Print the connecting body paste on the side of the first plane close to the closed end until the same height as the third plane to form the second connecting body film layer; S208: Continue to print the second insulation layer paste on the top of the second insulation film layer until the insulation layer reaches the set thickness, and after drying, the third insulation film layer and the third interval of the same height are formed; S209: Use the electrolyte solution to immerse the closed end for multiple times, and after drying, the electrolyte coating film layer is formed on the closed end, thereby obtaining the first battery / electrolytic cell precursor; S210: Perform the first firing treatment on the first battery / electrolytic cell precursor, thereby obtaining the second battery / electrolytic cell precursor; S211: Print the air electrode paste at each of the third intervals and on the top of the second connecting body to the same height as the third insulation film layer, and after drying, a fourth plane formed by a plurality of air electrode film layers and a plurality of third insulation film layers is obtained, thereby obtaining the third battery / electrolytic cell precursor; S212: After the second firing treatment on the third battery / electrolytic cell precursor, the self-sealing bamboo joint tubular solid oxide fuel cell / electrolytic cell is prepared.

20. The method of claim 19, wherein the self-sealing bellows tube solid oxide fuel cell / electrolysis cell is prepared by the steps of: On the side close to the open end, the second plane is setback based on the first plane by 0.5-1 times the length of the first interval; the third plane is setback based on the second plane by 0.5-1 times the length of the second interval; and the fourth plane is setback based on the third plane by 0.5-1 times the length of the third interval.

21. The method of making a self-sealing bellows tube solid oxide fuel cell / electrolytic cell of claim 19, wherein, The length of the first interval is 0.3-2 mm; The length of the second interval is 0.4-3 mm; The length of the third interval is 0.2-2 mm.

22. The method of making a self-sealing bellows tube solid oxide fuel cell / electrolytic cell of claim 19, wherein, The length of the first connecting body film layer is not less than half of the length of the second interval.

23. The method of making a self-sealing bellows tube solid oxide fuel cell / electrolytic cell of claim 19, wherein, The covering length of the fuel electrode film layer partially covered by the first connecting body film layer is 0.2-2 mm.

24. The method of making a self-sealing bellows tube solid oxide fuel cell / electrolytic cell of claim 19, wherein, The temperature of the first firing is 1250℃-1500℃, and the time of the first firing is 4h-6h.

25. The method of making a self-sealing bellows tube solid oxide fuel cell / electrolytic cell of claim 19, wherein, The temperature of the second firing is 1100℃-1500℃, and the time of the second firing is 2h-4h.

26. The method of making a self-sealing bellows tube solid oxide fuel cell / electrolytic cell of claim 19, wherein, The first insulation layer paste forms a porous insulation layer after firing treatment, and the second insulation layer paste forms a dense insulation layer after firing treatment.

27. The method of making a self-sealing bellows tube solid oxide fuel cell / electrolytic cell of claim 19, wherein, The thickness of the first plane is 100μm-300μm; The thickness of the second plane is 50μm-250μm; The thickness of the third plane is 10μm-100μm; The thickness of the fourth plane is 500μm-1500μm.

28. A bamboo-tube type solid oxide fuel cell / electrolysis cell stack, characterized by The application further provides a solid oxide fuel cell / electrolytic cell stack structure comprising a plurality of the bamboo joint tubular solid oxide fuel cell / electrolytic cell structures according to any one of the preceding claims 1-9. ​ 29. A method of making a bamboo-tube solid oxide fuel cell / electrolysis cell stack according to claim 28, wherein, The preparation method comprises: Placing a plurality of fuel gas inlet ends of the segmented pipe type solid oxide fuel cell / electrolysis cell according to any one of claims 1-9 in a fuel gas passage base in a certain arrangement to form the segmented pipe type solid oxide fuel cell / electrolysis cell stack integrated by a plurality of the segmented pipe type solid oxide fuel cell / electrolysis cells.

Images