CN209981378U

CN209981378U - Solid oxide ammonia fuel cell

Info

Publication number: CN209981378U
Application number: CN201920940757.7U
Authority: CN
Inventors: 江莉龙; 罗宇; 陈崇启; 詹瑛瑛
Original assignee: Fuzhou University; Beijing SJ Environmental Protection and New Material Co Ltd
Current assignee: Fuda Zijin Hydrogen Energy Technology Co., Ltd.
Priority date: 2019-06-21
Filing date: 2019-06-21
Publication date: 2020-01-21
Anticipated expiration: 2029-06-21

Abstract

The utility model discloses a solid oxide ammonia fuel cell, including the casing, supply the ammonia pipe, fuel cell part and air passage, pack ammonia decomposition catalyst in order to form ammonia decomposition catalyst layer in supplying the ammonia pipe. The utility model discloses put into ammonia decomposition catalyst in supplying the ammonia trachea, ammonia decomposes the heat absorption at ammonia decomposition catalyst layer, produces 3: 1's hydrogen nitrogen mixture, and hydrogen and surplus ammonia react at the positive pole, and it is easier to carry out with pure ammonia to react, especially has better electrochemical performance under the lower temperature (<600 ℃). The utility model discloses fuel gas and air take place exothermic after the electrochemical reaction, tail gas is exothermic after the afterburning simultaneously, and when getting rid of remaining ammonia in the tail gas, preheat the ammonia and the air of treating the reaction, promote electrochemical reaction, realize the self-sustaining of temperature, need not external heat source, only can guarantee the steady operation of battery through the heat transfer.

Description

Solid oxide ammonia fuel cell

Technical Field

The utility model relates to a solid fuel cell technical field, concretely relates to solid oxide ammonia fuel cell.

Background

A solid oxide ammonia fuel cell (SOFC) is a brand new solid-state energy conversion device, converts chemical energy stored in fuel into electric energy through high-temperature electrochemical reaction, and has the characteristics of high efficiency, no pollution, full solid-state structure, wide adaptability to various fuel gases and the like; meanwhile, compared with renewable energy sources such as wind energy, solar energy and the like, the solid oxide ammonia fuel cell is not limited by regional environment and has stronger reliability and adaptability.

The solid oxide ammonia fuel cell mainly comprises a flat plate type solid oxide ammonia fuel cell and a tubular type solid oxide ammonia fuel cell in the current research direction, wherein the flat plate type solid oxide ammonia fuel cell has higher volume power density and is suitable for being used as a large-scale distributed power station, and the tubular type solid oxide ammonia fuel cell has the advantages of quick starting time and good thermal shock resistance and is suitable for being used as a portable power source.

The ammonia gas is one of the optional fuels of the solid oxide ammonia fuel cell, the hydrogen content of the ammonia gas can reach 17.6 wt%, and the ammonia gas has the advantages of easy liquefaction, high energy density, no carbon emission, high safety and combustionLow material cost, and the like, and can liquefy ammonia into the ammonia with the volume energy density as high as 13 MJ.L only by 2MPa^-1The liquid of (2) is 3-4 times higher than the compressed hydrogen storage. In the prior art, ammonia gas only depends on anode Ni^-The catalytic decomposition of the ion conductor electrode obviously reduces the ammonia decomposition activity below 600 ℃, reduces the electrochemical performance and reduces the power generation efficiency.

SUMMERY OF THE UTILITY MODEL

Therefore, the technical problem to be solved by the present invention is to overcome the defects of the prior art that the decomposition performance of ammonia gas is obviously reduced below 600 ℃, and the electrochemical performance is reduced, thereby providing a tubular solid oxide ammonia fuel cell.

The utility model adopts the following technical scheme:

the utility model provides a solid oxide ammonia fuel cell, including the casing, still include:

the ammonia supply pipe is arranged in the shell along the axial direction of the shell and is filled with an ammonia decomposition catalyst to form an ammonia decomposition catalyst layer;

a fuel cell component comprising a cell body having an open end, said cell body having an inner cavity adapted for insertion of said ammonia supply tube into said cell body from said open end, said cell body comprising in sequence, in a direction away from said inner cavity, an anode layer, an electrolyte layer and a cathode layer such that ammonia gas enters said inner cavity from an outlet end of said ammonia supply tube and contacts said anode layer;

and the air channel is arranged in the shell so as to supply air into the shell and enable the air to be in contact with the cathode layer.

Preferably, the outlet end of the ammonia supply pipe is arranged close to the bottom of the inner cavity;

the air channel is arranged close to the inner wall of the shell, and an air outlet of the air channel is arranged at the bottom of the shell so as to enable air to be in contact with the cathode layer in the ascending process;

the battery body is tubular in shape.

Preferably, the solid oxide ammonia fuel cell is of an anode-supported type in which the electrolyte layer has a thickness of 10 to 30 μm; the thickness of the anode layer is 300-1000 μm; the thickness of the cathode layer is 10-50 μm;

or the solid oxide ammonia fuel cell is an electrolyte supporting type, wherein the thickness of an electrolyte layer in the electrolyte supporting type is 300-1000 mu m; the thickness of the anode layer is 10-50 μm; the thickness of the cathode layer is 10-50 μm.

Preferably, a horizontal partition board is arranged in the shell to divide the interior of the shell into a combustion chamber and a reaction chamber from top to bottom, a plurality of through holes for tail gas in the reaction chamber to enter the combustion chamber are formed in the horizontal partition board, and a burner is arranged in the combustion chamber and used for burning combustible components in additional fuel and/or the tail gas.

Preferably, the fuel cell component is disposed within the reaction chamber;

the ammonia supply pipe penetrates through the horizontal partition plate and sequentially comprises a first ammonia supply pipe positioned in the reaction chamber and a second ammonia supply pipe positioned in the combustion chamber.

Preferably, the first ammonia supply pipe is filled with an ammonia decomposition catalyst to form a first ammonia decomposition catalyst layer;

the second ammonia supply pipe is filled with an ammonia decomposition catalyst to form a second ammonia decomposition catalyst layer, the second ammonia decomposition catalyst layer being close to the first ammonia decomposition catalyst layer and the thickness of the second ammonia decomposition catalyst layer being smaller than the length of the second ammonia supply pipe.

Preferably, a gap exists between the outlet end of the ammonia supply pipe and the bottom of the inner cavity;

a gap is formed between the outer wall of the ammonia supply pipe and the inner wall of the battery body;

and a gap exists between the outer wall of the air channel and the outer wall of the battery body.

Preferably, the air outlet of the air channel is arranged opposite to the bottom end of the battery body, so that the air flowing out of the air outlet of the air channel flows to the bottom end of the battery body and is divided.

The utility model discloses ammonia decomposition catalyst main part is Ru base, Ni base catalyst, and the carrier includes and is not limited to carbon carrier, perovskite, rare earth metal oxide and hydrotalcite. The combustor is a catalyst combustor or a porous medium combustor.

The utility model discloses total reaction equation: 2NH₃+3/2O₂＝N₂+3H₂O, the half reaction of the cathode and anode varies depending on the electrolyte.

If an oxygen ion conductor is used as the electrolyte layer, the electrolyte layer material includes, but is not limited to, one of YSZ (yttria stabilized zirconia), ScSZ (scandia stabilized zirconia), GDC (gadolinium doped ceria), SDC (strontium doped ceria), or LSGM (strontium and magnesium doped lanthanum gallate), with the specific half-reaction being:

anode: 2NH₃+3O^2-＝N₂+3H₂O+6e^-And 3H₂+3O^2-＝3H₂O+6e^-

Cathode: 3/2O₂+6e^-＝3O^2-；

The anode layer is made of a material formed by mixing Ni and a material used by the oxygen ion conductor electrolyte layer, and the cathode layer is made of a conductor material formed by mixing a first material and a second material: the first material includes, but is not limited to, one of LSM (lanthanum strontium manganese) or LSCF (lanthanum strontium cobalt iron), and the second material is a material used for the oxygen ion conductor electrolyte layer.

If a proton conductor is used as the electrolyte layer, the electrolyte layer material includes, but is not limited to, barium cerate or barium zirconate-based perovskite material (zirconium and yttrium doped barium cerate, zirconium yttrium ytterbium doped barium cerate, yttrium doped barium zirconate), and the specific half-reactions are as follows:

anode: 2NH₃＝N₂+6H⁺+6e^-And 3H₂＝6H⁺+6e^-

Cathode: 3/2O₂+6e^-+6H⁺＝3H₂O；

The anode layer is made of a material formed by mixing Ni and the used material of the proton conductor electrolyte layer, and the cathode layer comprises but is not limited to one of BSCF (barium strontium cobalt iron), LSCF (lanthanum strontium cobalt iron), PSCF (praseodymium strontium cobalt iron), SSC (samarium strontium cobalt), LSN (lanthanum strontium nickel), PSN (praseodymium strontium nickel) or PBC (praseodymium barium cobalt).

The material of the ammonia supply pipe of the utility model is copper, which is convenient for heat transfer.

The outer wall of the shell of the utility model is made of heat-insulating material.

The utility model has the advantages of as follows:

1. the utility model discloses put into ammonia decomposition catalyst in supplying the ammonia trachea, ammonia decomposes the heat absorption at ammonia decomposition catalyst layer, produces 3: 1's hydrogen nitrogen mixture, and hydrogen and surplus ammonia react at the positive pole, and it is easier to carry out with pure ammonia to react, especially has better electrochemical performance under the lower temperature (<600 ℃).

2. The utility model discloses fuel gas and air are exothermic after taking place electrochemical reaction in the reacting chamber, preheat the ammonia that supplies in the ammonia pipe and the air in the air duct, realize the self-sustaining of temperature, reduce the loss and the waste of heat energy.

3. The utility model discloses after tail gas in the reaction chamber got into the combustion chamber through horizontal baffle, combustor department afterburning in the combustion chamber was exothermic, got rid of remaining ammonia in the tail gas, also can preheat the air in ammonia and the air duct that supplies the ammonia pipe simultaneously, further reduced the heat energy loss for the reaction need not outer heat source, only can guarantee the steady operation of battery through the heat transfer.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the technical solutions in the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

Fig. 1 is a schematic structural diagram of a solid oxide ammonia fuel cell provided in embodiment 1 of the present invention;

fig. 2 is a schematic structural diagram of a solid oxide ammonia fuel cell provided in embodiment 2 of the present invention;

fig. 3 is a graph showing the performance of the solid oxide ammonia fuel cell provided in example 1 of the present invention and a comparative example.

Description of reference numerals:

1-a fuel cell component; 2-a shell; 3-ammonia supply pipe; 4-an ammonia decomposition catalyst layer;

11-an electrolyte layer; 12-an anode layer; 13-a cathode layer; 14-lumen;

21-air channel; 22-a combustion chamber; 23-a reaction chamber; 24-a burner; 25-horizontal partition plate;

31-a first ammonia supply pipe; 32-a second ammonia supply pipe;

41-first ammonia decomposition catalyst layer; 42-second ammonia decomposition catalyst layer.

Detailed Description

The technical solution of the present invention will be described clearly and completely with reference to the accompanying drawings, and obviously, the described embodiments are some, but not all embodiments of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative work belong to the protection scope of the present invention.

In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplification of description, but do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.

In the description of the present invention, it is to be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood in specific cases to those skilled in the art.

Furthermore, the technical features mentioned in the different embodiments of the invention described below can be combined with each other as long as they do not conflict with each other.

Example 1

This example provides a solid oxide ammonia fuel cell, having a structure as shown in figure 1,

comprises a shell 2;

an ammonia supply pipe 3 disposed in the housing 2 along an axial direction of the housing 2, the ammonia supply pipe 3 being filled with an ammonia decomposition catalyst to form an ammonia decomposition catalyst layer 4;

a fuel cell component 1 comprising a tubular cell body having an open end, said cell body having an inner cavity 14 adapted for insertion of said ammonia supply tube 3 into the interior of said cell body from said open end, said cell body comprising, in order, in a direction away from said inner cavity 14, an anode layer 12, an electrolyte layer 11 and a cathode layer 13, such that ammonia gas enters said inner cavity 14 from the outlet end of said ammonia supply tube 3 and is in contact with said anode layer 12;

and an air passage 21 provided in the housing 2 to supply air into the housing 2 and to contact the cathode layer 13.

The present example uses an anode-supported type in which the electrolyte layer 11 is 15 μm thick, the anode layer 12 is 700 μm thick, and the cathode layer 13 is 20 μm thick; the ammonia decomposition catalyst layer 4 is made of Ru simple substance, and the carrier is alumina; the electrolyte layer 11 is made of oxygen ion conductor electrolyte, specifically YSZ, and the anode layer 12 is made of: Ni-YSZ, cathode layer 13 material is: LSM-YSZ.

The outlet end of the ammonia supply pipe 3 is arranged close to the bottom of the inner cavity 14;

the air channel 21 is arranged close to the inner wall of the casing 2, and the air outlet of the air channel 21 is arranged at the bottom of the casing 2, so that the air is in contact with the cathode layer 13 in the ascending process.

The internal part of the shell 2 is provided with a horizontal clapboard 25 to divide the internal part of the shell 2 into a combustion chamber 22 and a reaction chamber 23 from top to bottom, the horizontal clapboard 25 is provided with a plurality of through holes for tail gas in the reaction chamber 23 to enter the combustion chamber 22, and the combustion chamber 22 is internally provided with a combustor 24 for combusting additional fuel and/or combustible components in the tail gas.

The fuel cell component 1 is disposed in the reaction chamber 23;

the ammonia supply pipe 3 penetrates through the horizontal partition plate 25 and sequentially comprises a first ammonia supply pipe 31 positioned in the reaction chamber 23 and a second ammonia supply pipe 32 positioned in the combustion chamber 22.

The first ammonia supply pipe 31 is filled with the ammonia decomposition catalyst 4 to form a first ammonia decomposition catalyst layer 41;

second ammonia supply pipe 32 is filled with ammonia decomposition catalyst 4 to form second ammonia decomposition catalyst layer 42, second ammonia decomposition catalyst layer 42 is adjacent to first ammonia decomposition catalyst layer 41 and the thickness of second ammonia decomposition catalyst layer 42 is smaller than the length of second ammonia supply pipe 32.

A gap is formed between the outlet end of the ammonia supply pipe 3 and the bottom of the inner cavity 14; the outer wall of the ammonia supply pipe 3 is separated from the anode layer 12; the outer wall of the air channel is spaced from the cathode layer 13. The air outlet of the air channel 21 is arranged opposite to the bottom end of the battery body, so that the air flowing out of the air outlet of the air channel 21 flows to the bottom end of the battery body and is divided.

Example 2

This example provides a solid oxide ammonia fuel cell, which differs from example 1 in that the electrolyte layer used is a proton conductor electrolyte, and the structure is shown in figure 2,

comprises a shell 2;

This example uses an electrolyte-supported type in which the electrolyte layer 13 is 700 μm thick, the anode layer 14 is 20 μm thick, and the cathode layer 15 is 20 μm thick; the ammonia decomposition catalyst layer 12 is made of Ru simple substance, and the carrier is alumina; the electrolyte layer 13 is made of proton conductor electrolyte, specifically barium cerate, and the anode layer 14 is made of: the Ni-barium cerate, cathode layer 15 material is: LSCF.

The fuel cell component 1 is disposed in the reaction chamber 23;

Example 3

This example provides the operation of the solid fuel cell provided in example 1 and example 2.

Ammonia gas enters the ammonia decomposition catalyst layer 4 from the ammonia supply pipe 3, is decomposed into 3:1 hydrogen-nitrogen mixed gas and enters the inner cavity 14; air enters the reaction chamber 23 from the opening at the bottom of the housing 2 through the air passage 21; when a certain temperature is reached in the reaction chamber 23, the following reactions take place at the anode layer 14 and at the cathode layer 15 of the fuel cell component 1:

example 1 using an oxygen ion conductor as the electrolyte layer, the specific half-reactions were:

anode: 2NH₃+3O^2-＝N₂+3H₂O+6e^-And 3H₂+3O^2-＝3H₂O+6e^-

Cathode: 3/2O₂+6e^-＝3O^2-；

Example 2 using a proton conductor as the electrolyte layer, the specific half-reactions were:

anode: 2NH₃＝N₂+6H⁺+6e^-And 3H₂＝6H⁺+6e^-

Cathode: 3/2O₂+6e^-+6H⁺＝3H₂O。

The reaction chamber 23 releases heat after electrochemical reaction, ammonia gas in the ammonia supply pipe 11 and air in the air channel 21 are preheated, tail gas in the reaction chamber 23 enters the combustion chamber 22 through the horizontal partition plate 25, heat is released by afterburning at the combustor 24 in the combustion chamber 22, residual ammonia gas and hydrogen gas in the tail gas are removed, and meanwhile, ammonia gas in the ammonia supply pipe 3 and air in the air channel 21 are further preheated.

Comparative example

This comparative example provides a solid oxide ammonia fuel cell, which differs from example 1 in that there is no ammonia decomposition catalyst layer in the ammonia supply pipe.

Test examples

The solid oxide ammonia fuel cells of example 1 and comparative example were subjected to an operation test, and the electrochemical properties of both were measured, and the results are shown in fig. 2.

As can be seen from fig. 2, the ratio of the electrochemical performances (ratio of maximum power density) of the comparative example and example 1 is significantly reduced as the temperature is lowered, and the electrochemical performance of example 1 is about 2.2 times that of the comparative example at 600 ℃.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications can be made without departing from the scope of the invention.

Claims

1. A solid oxide ammonia fuel cell comprising a housing, further comprising:

2. The solid oxide ammonia fuel cell of claim 1, wherein the outlet end of the ammonia supply tube is disposed proximate the bottom of the internal cavity;

the battery body is tubular in shape.

3. The solid oxide ammonia fuel cell according to claim 1 or 2, wherein the solid oxide ammonia fuel cell is of an anode-supported type in which an electrolyte layer has a thickness of 10 to 30 μm; the thickness of the anode layer is 300-1000 μm; the thickness of the cathode layer is 10-50 μm.

4. The solid oxide ammonia fuel cell according to claim 1 or 2, wherein the solid oxide ammonia fuel cell is of an electrolyte-supported type in which the electrolyte layer has a thickness of 300-1000 μm; the thickness of the anode layer is 10-50 μm; the thickness of the cathode layer is 10-50 μm.

5. The solid oxide ammonia fuel cell according to claim 1 or 2, wherein a horizontal partition is disposed inside the casing to divide the inside of the casing into a combustion chamber and a reaction chamber from top to bottom, the horizontal partition is provided with a plurality of through holes for allowing tail gas in the reaction chamber to enter the combustion chamber, and a burner is disposed in the combustion chamber for burning combustible components in the added fuel and/or the tail gas.

6. The solid oxide ammonia fuel cell of claim 5, wherein the fuel cell component is disposed within the reaction chamber;

7. The solid oxide ammonia fuel cell of claim 6, wherein the first ammonia supply tube is filled with an ammonia decomposition catalyst to form a first ammonia decomposition catalyst layer;

8. The solid oxide ammonia fuel cell according to claim 1 or 2, wherein a gap exists between the outlet end of the ammonia supply pipe and the bottom of the inner cavity;

9. The solid oxide ammonia fuel cell according to claim 1 or 2, wherein the air outlet of the air channel is disposed opposite to the bottom end of the cell body so that the air coming out of the air outlet of the air channel flows toward the bottom end of the cell body and is branched.