Method for growing carbon nanotubes on Ni-8YSZ anode of micro-tubular solid oxide fuel cell

Abstract

The invention relates to a method for growing carbon nanotubes on a Ni-8YSZ anode of a micro-tubular solid oxide fuel cell. The method comprises the following steps: step 1, placing a Ni-8YSZ anode tube of a micro-tubular solid oxide fuel cell in a crucible, placing the tube furnace, evacuating the tube furnace, using hydrogen as a reducing atmosphere, uniformly heating the tube furnace to 600-800 DEG C at a heating rate of 2-10 DEG C / min, and keeping the temperature for 2-5 hours; step 2, after step 1, stopping the introduction of hydrogen, introducing an inert gas and a carbon source gas, so that the tube furnace is a mixed atmosphere of the inert gas and the carbon source; step 3, after step 2, keeping the tube furnace at a temperature of 600-1000 DEG C for 1-3 hours and continuously introducing the carbon source gas; step 4, after step 3, stopping the introduction of the carbon source gas, cooling the tube furnace to room temperature in an inert gas atmosphere, and obtaining a Ni-8YSZ / CNTs anode. It has the advantages of nickel catalyzing the growth of carbon nanotubes, improving the stability and conductivity inside Ni‑8YSZ, and improving its current collection performance and battery stability when applied to electrode materials.

Description

Technical Field

[0001] The invention relates to a method for growing carbon nanotubes on a Ni-8YSZ anode of a micro-tubular solid oxide fuel cell. Background Art

[0002] The application of electrochemical energy storage technology effectively solves the problems of storage, utilization and conversion of clean energy, and has broad development prospects in the future. In the process of developing clean new energy, hydrogen energy will occupy a dominant position, and solid oxide fuel cells are a new medium that integrates hydrogen energy with human economic and social development. The use of solid oxide fuel cells and a wide range of fuel sources can greatly reduce human society's dependence on fossil energy. Compared with fossil fuels such as coal and oil, hydrogen energy is the clean energy and green energy we have been looking for. At the same time, hydrogen energy has always been considered a new energy source with many advantages such as cleanliness, high efficiency and recyclability. However, since the research on solid oxide fuel cells is not yet mature, its application still faces great challenges.

[0003] Carbon nanotubes are a common carbon material. They have a good graphitized structure and excellent electrical conductivity. More importantly, they can act as ion channels. At the same time, carbon nanotubes have high thermal conductivity. As long as a small amount of carbon nanotubes is introduced into the composite material, its thermal conductivity will be greatly improved. All of these are conducive to improving the performance of SOFC. Summary of the invention

[0004] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a method for growing carbon nanotubes on the Ni-8YSZ anode of a microtubular solid oxide fuel cell. Nickel catalyzes the growth of carbon nanotubes, improves the stability and conductivity inside Ni-8YSZ, and improves its current collection performance and battery stability when applied to electrode materials.

[0005] In order to achieve the above object, the technical solution of the present invention is implemented as follows: it is a method for growing carbon nanotubes on a Ni-8YSZ anode of a micro-tubular solid oxide fuel cell, characterized in that it includes the following steps:

[0006] Step 1

[0007] After placing a Ni-8YSZ anode tube of a micro-tubular solid oxide fuel cell in a crucible, the tube furnace is placed, vacuumized, and hydrogen is used as a reducing atmosphere. The temperature is uniformly increased to 600-800°C at a heating rate of 2-10°C / min, and the temperature is kept for 2-5 hours;

[0008] Step 2

[0009] After step 1, the introduction of hydrogen is stopped, and an inert gas and a carbon source gas are introduced to make the tubular furnace a mixed atmosphere of the inert gas and the carbon source;

[0010] Step 3

[0011] After step 2, the tube furnace is kept at 600-1000° C. for 1-3 hours and the carbon source gas is continuously introduced;

[0012] Step 4

[0013] After step three, the introduction of the carbon source gas is stopped, and the furnace is cooled to room temperature under an inert gas atmosphere to obtain a Ni-8YSZ / CNTs anode.

[0014] In the present technical solution, the Ni-8YSZ includes 8YSZ, NiO and a pore former, and the mass ratio of 8YSZ: NiO: pore former is 33:60:7.

[0015] In the present technical scheme, the microtubular solid oxide fuel cell Ni-8YSZ anode tube is formed by a piston-cylinder extruder, dried at 25-80°C for 2-5h, and sintered at 1150-1350°C for 5-10h. The electrolyte is coated on the outer surface of the anode tube. The thickness of the electrolyte is 5-10 um. The material of the electrolyte is YSZ. Then it is sintered at 1200-1400°C for 2-5h. Then, a cathode intermediate layer is coated on the outer surface of the electrolyte. The thickness of the cathode intermediate layer is 1-3μm. The material of the cathode intermediate layer is deposited GDC (Gd0.1Ce0.9O1.95). Then, the cathode layer is sintered at 850-1150°C for 1-3 h.

[0016] In the present technical solution, the inert gas includes nitrogen or argon or other inert gases.

[0017] In the present technical solution, the carbon source gas is propane, acetylene or other hydrocarbon gases.

[0018] In the technical solution, the crucible is a quartz crucible or an alumina crucible.

[0019] Compared with the prior art, the advantages of the present invention are as follows: nickel catalyzes the growth of carbon nanotubes, improves the stability and conductivity inside Ni-8YSZ, and improves its current collection performance and battery stability when applied to electrode materials. DETAILED DESCRIPTION

[0020] The specific embodiments of the present invention are further described below. It should be noted that the description of these embodiments is used to help understand the present invention, but does not constitute a limitation of the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other. Example

[0021] The invention discloses a method for growing carbon nanotubes on a Ni-8YSZ anode of a micro-tubular solid oxide fuel cell, which is characterized by comprising the following steps:

[0022] Step 1

[0023] A Ni-8YSZ anode tube of a micro-tubular solid oxide fuel cell was placed in a crucible, and then placed in a tubular furnace, evacuated, and heated to 600°C at a rate of 2°C / min with hydrogen as a reducing atmosphere, and kept at this temperature for 2 hours;

[0024] Step 2

[0025] After step 1, the introduction of hydrogen is stopped, and an inert gas and a carbon source gas are introduced to make the tubular furnace a mixed atmosphere of the inert gas and the carbon source;

[0026] Step 3

[0027] After step 2, the tube furnace is kept at 600° C. for 1 hour and the carbon source gas is continuously introduced;

[0028] Step 4

[0029] After step three, the introduction of the carbon source gas is stopped, and the furnace is cooled to room temperature under an inert gas atmosphere to obtain a Ni-8YSZ / CNTs anode.

[0030] The reaction formula of step one during operation is NiO+H 2 →Ni+H 2 O, the reaction formula in step 3 is C x H y →C(s)+H 2 , C(s)→C(NT).

[0031] In this embodiment, the Ni-8YSZ includes 8YSZ, NiO and a pore former, and the mass ratio of 8YSZ: NiO: pore former is 33:60:7.

[0032] In this embodiment, the microtubular solid oxide fuel cell Ni-8YSZ anode tube is formed by a piston-cylinder extruder, dried at 25°C for 2 hours, and sintered at 1150°C for 5 hours. The electrolyte is coated on the outer surface of the anode tube. The thickness of the electrolyte is 5um. The material of the electrolyte is YSZ. Then it is sintered at 1200°C for 2 hours. Then, the cathode middle layer is coated on the outer surface of the electrolyte. The thickness of the cathode middle layer is 1μm. The material of the cathode middle layer is deposited GDC (Gd0.1Ce0.9O1.95). Then, the cathode layer is sintered at 850°C for 1 hour.

[0033] In this embodiment, the inert gas includes nitrogen or argon or other inert gases.

[0034] In this embodiment, the carbon source gas is propane, acetylene or other hydrocarbon gases.

[0035] In this embodiment, the crucible is a quartz crucible or an alumina crucible. Example

[0036] A method for growing carbon nanotubes on a Ni-8YSZ anode of a micro-tubular solid oxide fuel cell, characterized by comprising the following steps:

[0037] Step 1

[0038] A Ni-8YSZ anode tube of a micro-tubular solid oxide fuel cell was placed in a crucible, and then placed in a tubular furnace, evacuated, and heated to 700°C at a uniform rate of 6°C / min with hydrogen as a reducing atmosphere, and kept at this temperature for 3.5 hours;

[0039] Step 2

[0040] After step 1, the introduction of hydrogen is stopped, and an inert gas and a carbon source gas are introduced to make the tubular furnace a mixed atmosphere of the inert gas and the carbon source;

[0041] Step 3

[0042] After step 2, the tube furnace is kept at 800° C. for 2 hours and the carbon source gas is continuously introduced;

[0043] Step 4

[0044] After step three, the introduction of the carbon source gas is stopped, and the furnace is cooled to room temperature under an inert gas atmosphere to obtain a Ni-8YSZ / CNTs anode.

[0045] In this embodiment, the Ni-8YSZ includes 8YSZ, NiO and a pore former, and the mass ratio of 8YSZ: NiO: pore former is 33:60:7.

[0046] In this embodiment, the microtubular solid oxide fuel cell Ni-8YSZ anode tube is formed by a piston-cylinder extruder, dried at 52.5°C for 3.5 hours, and sintered at 1250°C for 7.5 hours. The electrolyte is coated on the outer surface of the anode tube. The thickness of the electrolyte is 7.5um. The material of the electrolyte is YSZ. Then it is sintered at 1300°C for 3.5 hours. Then, a cathode intermediate layer is coated on the outer surface of the electrolyte. The thickness of the cathode intermediate layer is 2μm. The material of the cathode intermediate layer is deposited GDC (Gd0.1Ce0.9O1.95). Then, the cathode layer is sintered at 1000°C for 2 hours.

[0047] In this embodiment, the inert gas includes nitrogen or argon or other inert gases.

[0048] In this embodiment, the carbon source gas is propane, acetylene or other hydrocarbon gases.

[0049] In this embodiment, the crucible is a quartz crucible or an alumina crucible. Example

[0050] A method for growing carbon nanotubes on a Ni-8YSZ anode of a micro-tubular solid oxide fuel cell, characterized by comprising the following steps:

[0051] Step 1

[0052] A Ni-8YSZ anode tube of a micro-tubular solid oxide fuel cell was placed in a crucible, and then placed in a tubular furnace, evacuated, and heated to 800°C at a rate of 10°C / min with hydrogen as a reducing atmosphere, and kept at this temperature for 5 hours;

[0053] Step 2

[0054] After step 1, the introduction of hydrogen is stopped, and an inert gas and a carbon source gas are introduced to make the tubular furnace a mixed atmosphere of the inert gas and the carbon source;

[0055] Step 3

[0056] After step 2, the tube furnace is kept at 1000° C. for 3 hours and the carbon source gas is continuously introduced;

[0057] Step 4

[0058] After step three, the introduction of the carbon source gas is stopped, and the furnace is cooled to room temperature under an inert gas atmosphere to obtain a Ni-8YSZ / CNTs anode.

[0059] In this embodiment, the Ni-8YSZ includes 8YSZ, NiO and a pore former, and the mass ratio of 8YSZ: NiO: pore former is 33:60:7.

[0060] In this embodiment, the microtubular solid oxide fuel cell Ni-8YSZ anode tube is formed by a piston-cylinder extruder, dried at 80°C for 5 hours, and sintered at 1350°C for 10 hours. The electrolyte is coated on the outer surface of the anode tube. The thickness of the electrolyte is 10 um. The material of the electrolyte is YSZ. Then it is sintered at 1400°C for 5 hours. Then, the cathode intermediate layer is coated on the outer surface of the electrolyte. The thickness of the cathode intermediate layer is 3 μm. The material of the cathode intermediate layer is deposited GDC (Gd0.1Ce0.9O1.95). Then, the cathode layer is sintered at 1150°C for 3 hours.

[0061] In this embodiment, the inert gas includes nitrogen or argon or other inert gases.

[0062] In this embodiment, the carbon source gas is propane, acetylene or other hydrocarbon gases.

[0063] In this embodiment, the crucible is a quartz crucible or an alumina crucible.

[0064] In the technical solution, the embodiments of the present invention are described in detail above in conjunction with the accompanying drawings, but the present invention is not limited to the described embodiments. For ordinary technicians in the field, various changes, modifications, substitutions and deformations of these embodiments without departing from the principles and purpose of the present invention still fall within the scope of protection of the present invention.

Claims

1. A method for growing carbon nanotubes on a Ni-8YSZ anode of a micro-tubular solid oxide fuel cell, characterized in that The following steps are involved: Step 1 After placing a Ni-8YSZ anode tube of a micro-tubular solid oxide fuel cell in a crucible, the tube furnace is placed, vacuumized, and hydrogen is used as a reducing atmosphere. The temperature is uniformly increased to 600-800°C at a heating rate of 2-10°C / min, and the temperature is kept for 2-5 hours; Step 2 After step 1, the introduction of hydrogen is stopped, and an inert gas and a carbon source gas are introduced to make the tubular furnace a mixed atmosphere of the inert gas and the carbon source; Step 3 After step 2, the tube furnace is kept at 600-1000° C. for 1-3 hours and the carbon source gas is continuously introduced; Step 4 After step 3, the introduction of the carbon source gas is stopped, and the furnace is cooled to room temperature under an inert gas atmosphere to obtain a Ni-8YSZ / CNTs anode; The micro-tubular solid oxide fuel cell Ni-8YSZ anode tube is formed by a piston-cylinder extruder, dried at 25-80° C. for 2-5 hours, and sintered at 1150-1350° C. for 5-10 hours. The Ni-8YSZ comprises 8YSZ, NiO and a pore former, and the mass ratio of 8YSZ: NiO: pore former is 33:60:

7.

2. The method for growing carbon nanotubes on a Ni-8YSZ anode of a micro-tubular solid oxide fuel cell according to claim 1, characterized in that The inert gas includes nitrogen, argon or other inert gases.

3. The method for growing carbon nanotubes on a Ni-8YSZ anode of a micro-tubular solid oxide fuel cell according to claim 1, characterized in that The carbon source gas is propane, acetylene or other hydrocarbon gases.

4. The method for growing carbon nanotubes on a Ni-8YSZ anode of a micro-tubular solid oxide fuel cell according to claim 1, characterized in that The crucible is a quartz crucible or an alumina crucible.