CN115646191A - Hydrogen separation device and method of use based on nickel-BZNY proton conductor - Google Patents

Abstract

The invention discloses hydrogen separation equipment based on a nickel-BZNY proton conductor and a using method thereof, wherein the equipment comprises the following steps: a BZNY proton conductor; the first metal nickel electrode and the second metal nickel electrode are respectively arranged on two sides of the BZNY proton conductor; the conductive end of the first lead is connected with the first metal nickel electrode; the conductive end of the second lead is connected with the second metal nickel electrode; the access end of the first lead and the access end of the second lead are both connected with external electric signal input equipment; a first insulating sleeve having a hydrogen gas extraction space formed therein; the second insulating sleeve is sleeved outside the first insulating sleeve, and a hydrogen-containing mixed gas providing space is formed between the second insulating sleeve and the first insulating sleeve. The invention adopts metal nickel as an electrode, the voltage required by the operation under the ultra-low concentration can be less than 10V, the precipitation phenomenon of nickel can not be induced almost, and meanwhile, the cathode and the anode adopt the same material, thereby simplifying the processing technology of the diaphragm.

Description

Hydrogen separation device and method of use based on nickel-BZNY proton conductor

technical field

The invention relates to the field of hydrogen separation, in particular to a nickel-BZNY proton conductor-based hydrogen separation device and usage method.

Background technique

Nuclear fusion is generally considered to be the ultimate solution to human energy. Its basic principle is that fusion reactions occur at high temperatures, and hydrogen isotopes deuterium and tritium combine to form heavier nuclei such as helium, and at the same time release huge energy. There will be a certain amount of hydrogen isotope mixed in the helium of the fusion reaction product, which needs to be separated and purified from the fusion product helium. In addition, in order to ensure the self-sustainability of tritium in the fuel cycle system of the fusion reactor, it is necessary to use helium as the carrier gas, and use the neutrons generated by the fusion reaction to bombard the lithium nuclei in the cladding to produce tritium, and the tritium produced needs to be taken out for further Tritium recovery is carried out, which also involves the separation of hydrogen isotopes and helium.

The existing solution to the separation of hydrogen isotopes and helium mainly adopts the separation technology of raw and cold, that is, the separation process is completed by utilizing the different characteristics of the boiling points of hydrogen and helium (about 77K and 4K respectively), that is, when the temperature drops below 77K, the hydrogen isotope gas begins to It condenses into a liquid phase and is adsorbed on a special adsorption column, while the helium is still above the boiling point temperature, only a small condensation occurs, thereby realizing the separation of hydrogen isotopes and helium. The disadvantages of the above method are high energy consumption, complex system, and low adsorption efficiency. Other mixed gases may also undergo condensation and adsorption, resulting in low purity of the separated hydrogen isotope gas, and multiple subsequent purification processes. When the separation and extraction of hydrogen isotopes is carried out using raw-cooling separation technology, due to the high temperature of the fusion reaction product and the carrier gas, the carrier gas needs to be reheated from below 77K to a high temperature. The temperature difference between the front and rear systems is large, which brings certain difficulties to the structural design and the selection of structural materials.

In order to improve the energy consumption economy of the separation of hydrogen isotopes and helium, based on the hydrogen permeability characteristics of barium zirconium oxide (BZ) and barium zirconium yttrium oxide (BZY) in recent years, BaZr _x Ce _y Y _{1 -xy} O _3-δ or BaZr _x Y _1-x O _3-δ is the proton conductor electrolyte, using oxide electrodes (NiO-NiO-BaZr _x Y _1-x O _3-δ or NiO-BaZr _x Ce _y Y _{1 -xy} O _3-δ as the anode, La _x Sr _{1- x} Co _y Fe _1-y O _3-δ or La _x Sr _1-x MnO _3-δ as the cathode) hydrogen-helium separation equipment and its preparation process, for example The invention patent with application number CN201910919469.8 and the invention patent with application number CN201910919470.0.

In the actual use research process, when using the oxide electrode as shown above, it is necessary to provide a voltage of more than 100 volts to complete the hydrogen-helium separation process at an ultra-low hydrogen concentration (the hydrogen content of the hydrogen-containing mixed gas is less than 0.001%) , which greatly limits its subsequent engineering application.

At the same time, due to the different cathode materials and anode materials, in the actual processing technology of the cathode and anode, it is necessary to balance the technology and performance according to the sintering characteristics of their respective materials: if it is for the sake of technology, it is difficult to use the sintering temperature to achieve a stable combination with the proton conductor. When the difference is large, it will lead to obvious interface weak bonding between the oxide electrode and the proton conductor, and the phenomenon of film layer peeling will easily occur; otherwise, the processing technology will be very complicated.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies of the prior art, and provide hydrogen separation equipment and using methods based on nickel-BZNY proton conductors.

The purpose of the present invention is achieved through the following technical solutions:

The first aspect of the present invention provides a kind of hydrogen separation equipment based on nickel-BZNY proton conductor, comprising:

BZNY proton conductor;

The first metal nickel electrode and the second metal nickel electrode are respectively arranged on both sides of the BZNY proton conductor;

The first lead wire, the conductive end is connected to the first metal nickel electrode; the second lead wire, the conductive end is connected to the second metal nickel electrode; the access end of the first lead wire and the access end of the second lead wire are connected to the external electrical signal input device connect;

The first insulating sleeve is connected to the side of the BZNY proton conductor located on the first metal nickel electrode and sleeved on the periphery of the first metal nickel electrode, and a hydrogen extraction space is formed inside the first insulating sleeve;

The second insulating sleeve is sleeved on the outside of the first insulating sleeve, and forms a hydrogen-containing mixed gas supply space with the first insulating sleeve.

Further, the conductive end of the first lead is connected to the first metal nickel electrode by sintering, welding, deposition, hot pressing or cold pressing, and the conductive end of the second lead is connected by sintering, welding, deposition, hot pressing or cold pressing. The way is connected with the second metal nickel electrode.

Further, the first insulating sleeve is a high temperature resistant ceramic tube, and the second insulating sleeve is a high temperature resistant glass tube.

Further, the hydrogen content of the hydrogen-containing mixed gas is lower than 0.001%.

Further, for the electrical signal input by the external electrical signal input device, the variable voltage of the input curve ranges from -10V to 10V, and the constant voltage ranges from 1-10V.

Further, the final sintering temperature range of the BZNY proton conductor is 1200-1600 degrees Celsius.

Further, both the first lead wire and the second lead wire are high-purity silver wires.

Further, the method of making metal nickel electrodes includes electroplating method, sputtering method, reduction method and vapor phase deposition method.

Further, the thickness of the first metal nickel electrode and the second metal nickel electrode is 10-1000 nm, and the diameter of the first lead wire and the second lead wire is 0.2-0.6 mm.

A second aspect of the present invention provides the method for using the hydrogen separation device based on the nickel-BZNY proton conductor, comprising the following steps:

Pass the hydrogen-containing mixed gas into the second insulating sleeve;

The first metal nickel electrode receives an external electrical signal through the first lead, while the second metal nickel electrode receives the external signal through the second lead;

The hydrogen isotope of the hydrogen-containing mixed gas is extracted to the hydrogen extraction space of the first insulating sleeve through the BZNY proton conductor under the control of the electric signal.

The beneficial effects of the present invention are:

(1) In an exemplary embodiment of the present invention, metal nickel is used as the electrode, because hydrogen has a certain solubility in nickel, and the nickel electrode is conducive to the infiltration of ultra-low concentration hydrogen to complete the subsequent hydrogen separation process, and adopts Metal electrodes can reduce the operating voltage required for a given electrical signal input to the hydrogen separation process. The voltage required for the nickel metal electrode to work at an ultra-low concentration can be less than 10V and hardly induce the precipitation of nickel. At the same time, it presents a central symmetrical structure of the diaphragm, and the cathode and anode are made of the same material, which simplifies the diaphragm processing technology and avoids the use of oxide electrodes in the prior art due to the different materials of the cathode and anode. Difficulties in the trade-off between process and performance of sintering characteristics. The BZNY material is used as the proton conductor, and the addition of nickel element is beneficial to the densification of the proton conductor and the reduction of the sintering temperature, which further reduces the energy consumption cost and the requirements for the sintering furnace equipment. In addition, because the BZNY proton conductor contains some nickel in its composition, it has better compatibility and interfacial bonding with the metal nickel electrode, which solves the problem that the oxide electrode film is easy to fall off from the proton conductor layer.

(2) In another exemplary embodiment of the present invention, when the magnetron sputtering process adopted in the method for making the metal nickel electrode, compared with the coating + sintering process adopted by the oxide electrode, the interface bonding force can be improved, Improve the uniformity of the film layer of the electrode and the mature reliability of the process. Because the oxide electrode adopts coating technology, its interfacial bonding force is low, and the film layer separation and shedding are prone to occur after dozens of hours of actual work. The experiment did not find the membrane layer separation and phenomenon of the electrode and the electrolyte, and the hydrogen separation performance of the nickel-BZNY proton conductor element under long-term work did not find obvious fluctuations.

(3) In yet another exemplary embodiment of the present invention, nickel metal electrodes are used, which are more suitable for connection with silver leads than oxide electrodes, so as to improve the reliability of the device-level lead packaging interconnection process.

Description of drawings

Fig. 1 is the structural representation of the hydrogen separation equipment based on nickel-BZNY proton conductor provided by an exemplary embodiment of the present invention;

Fig. 2 a is the X-ray diffraction pattern of the metal nickel electrode grown using radio frequency magnetron sputtering technology provided in an exemplary embodiment of the present invention;

Figure 2b is an X-ray diffraction pattern of the BZNY proton conductor provided in an exemplary embodiment of the present invention;

Fig. 3 a is the scanning electron micrograph of the metal nickel electrode section of the radio frequency magnetron sputtering provided in an exemplary embodiment of the present invention;

Figure 3b is a scanning electron microscope image of the BZNY proton conductor section provided in an exemplary embodiment of the present invention;

Fig. 4 is a kind of sample figure based on nickel-BZNY proton conductor element provided in an exemplary embodiment of the present invention;

5 is a schematic diagram of the relationship between a given electrical signal input in the form of voltage and hydrogen transmission rate when extracting hydrogen from a hydrogen-helium mixed gas with a hydrogen content of 0.001% provided in an exemplary embodiment of the present invention.

In the figure, 1-BZNY proton conductor, 201-first metal nickel electrode, 202-second metal nickel electrode, 301-first lead wire, 302-second lead wire, 4-external electrical signal input device, 501-first insulation Sleeve, 50101-hydrogen extraction space, 502-second insulating sleeve, 50201-hydrogen-containing mixed gas supply space, 6-connection point.

Detailed ways

The technical solutions of the present invention will be clearly and completely described below in conjunction with the accompanying drawings. Apparently, the described embodiments are part of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

In the description of the present invention, it should be noted that the terms belonging to "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer" etc. The indicated direction or positional relationship is based on the direction or positional relationship described in the drawings, and is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, or in a specific orientation. construction and operation, therefore, should not be construed as limiting the invention. In addition, belonging to "first" and "second" is only for descriptive purposes, and should not be understood as indicating or implying relative importance.

In the description of the present invention, it should be noted that, unless otherwise specified and limited, "installation", "connection" and "connection" should be understood in a broad sense, for example, it can be a fixed connection or a detachable connection. Connected, or integrally connected; it may be mechanically connected or electrically connected; it may be directly connected or indirectly connected through an intermediary, and it may be the internal communication of two components. Those of ordinary skill in the art can understand the specific meanings of the above terms in the present invention in specific situations.

In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as there is no conflict with each other.

The following content will first explain the technical terms:

Proton conductor: A proton conductor refers to a solid electrolyte that can conduct hydrogen ions, also known as a hydrogen ion conductor. The conduction of protons in solids can be divided into two categories: one is conduction in compounds with hydrogen bonds; the other is conduction in compounds without hydrogen bonds. Most of the known proton conductors have hydrogen bonds, and their conduction mechanism is through the transition of hydrogen ions accompanied by the rotation of molecules.

BZNY proton conductor: The proton conductor BaZrO (BZ) and y-doped BaZrO ₃ (BZY) as a dense sintered body are obtained by adding NiO as a sintering accelerator and sintering at 1800°C-2000°C for a short time of 5 hours. The BZNY proton conductor is obtained by sintering BaZrO ₃ co-doped with Ni and Y, and the sintering temperature is 1300°C-1600°C.

Hydrogen separation: It is mainly suitable for purifying single-component pure gas of hydrogen and hydrogen isotopes from gases containing at least two components of helium, argon, nitrogen, protium, deuterium and tritium. However, in this exemplary embodiment, it is especially aimed at separating pure hydrogen from a multi-component mixed gas containing low concentration hydrogen (the hydrogen content of the hydrogen-containing mixed gas is lower than 0.001%) in the nuclear fusion environment, that is, the reverse concentration gradient Enrich and purify hydrogen.

Referring to Fig. 1, Fig. 1 shows the structural representation of the hydrogen separation device based on nickel-BZNY proton conductor provided in an exemplary embodiment of the present invention, including:

BZNY Proton Conductor 1;

The first metal nickel electrode 201 and the second metal nickel electrode 202 are respectively arranged on both sides of the BZNY proton conductor 1;

The first lead 301, the conductive end is connected with the first metallic nickel electrode 201; the second lead 302, the conductive end is connected with the second metallic nickel electrode 202; the access end of the first lead 301 and the access end of the second lead 302 are both Connect with external electrical signal input device 4;

The first insulating sleeve 501 is connected to the side of the BZNY proton conductor 1 located on the first metal nickel electrode 201 and is sleeved on the periphery of the first metal nickel electrode 201. A hydrogen extraction space 50101 is formed inside the first insulating sleeve 501;

The second insulating sleeve 502 is sleeved on the outside of the first insulating sleeve 501 , and forms a hydrogen-containing mixed gas supply space 50201 between the first insulating sleeve 501 .

Specifically, in this exemplary embodiment, the second insulating sleeve 502 contains hydrogen-containing mixed gas, and the first insulating sleeve 501 contains pure hydrogen gas, including the BZNY proton conductor 1, the first metal nickel electrode 201 and the second The proton conductor diaphragm formed by the two metal nickel electrodes 202 is connected to the first insulating sleeve 501 in a closed manner, so as to isolate pure hydrogen gas and hydrogen-containing mixed gas. In the hydrogen-containing mixed gas supply space 50201, the hydrogen isotopes in the hydrogen-containing mixed gas 5 are extracted through the BZNY proton conductor 1 to the hydrogen extraction system containing pure hydrogen gas 1 under the control of the electrical signal output by the external electrical signal input device 4 Space 50101.

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

(1) In the actual use research process, when using the oxide electrodes in the prior art (NiO-NiO-BaZr _x Y _1-x O _3-δ or NiO-BaZr _x Ce _y Y _1-xy O _{3- δ} as the anode, La _x Sr _1-x Co _y Fe _1-y O _3-δ or La _x Sr _1-x MnO _3-δ as the cathode), not only the oxide electrode has a certain hindering effect on the infiltration of hydrogen , and the oxide electrode needs a voltage of about 100V to separate hydrogen when the hydrogen concentration is ultra-low (the hydrogen content of the hydrogen-containing mixed gas is lower than 0.001%). Under this high hydrogen separation voltage, it not only greatly limits its subsequent engineering application, but also induces a large amount of nickel to be precipitated from BZNY to form metal bands, which leads to the failure of proton conduction.

However, in this exemplary embodiment, metal nickel is used as the electrode. Because hydrogen has a certain solubility in nickel, the nickel electrode is conducive to the infiltration of ultra-low concentration hydrogen to complete the subsequent hydrogen separation process, and the use of metal electrodes can reduce the hydrogen concentration. The operating voltage for a given electrical signal input required for the separation process. The voltage required for the nickel metal electrode to work at an ultra-low concentration can be less than 10V and hardly induce the precipitation of nickel.

(2) In the actual use research process, when using the oxide electrodes in the prior art (NiO-NiO-BaZr _x Y _1-x O _3-δ or NiO-BaZr _x Ce _y Y _1-xy O _{3- δ} as the anode, and La _x Sr _1-x Co _y Fe _1-y O _3-δ or La _x Sr _1-x MnO _3-δ as the cathode), due to the different materials of the cathode and anode, the two stages of yin and yang are practically In terms of processing technology, it is necessary to balance the technology and performance according to the sintering characteristics of the respective materials: if there is a large difference in the sintering temperature for achieving a stable combination with the proton conductor for the sake of technology, it will lead to an obvious interface between the oxide electrode and the proton conductor The problem of weak bonding is prone to film peeling; otherwise, the processing technology will be very complicated.

In this exemplary embodiment, the central symmetrical structure of the diaphragm is presented, and the same material is used for the cathode and the anode, which simplifies the diaphragm processing technology and avoids the fact that the oxide electrode used in the prior art is different in the actual processing technology due to the different materials of the cathode and anode. On the surface, it is necessary to make a trade-off between process and performance according to the sintering characteristics of the respective materials.

(3) In this exemplary embodiment, the BZNY material is used as the proton conductor. Compared with BZY (BaZr _x Y _{1- x} O _3-δ ), the addition of nickel element is beneficial to the densification of the proton conductor and the improvement of the sintering temperature. Reduce, and further reduce energy consumption costs and requirements for sintering furnace equipment. The densification of BZY requires a sintering temperature of nearly 2000 degrees. At present, there is an order of magnitude difference in the price of a sintering furnace with a maximum temperature of 1600 degrees and a sintering furnace of 1800 degrees.

(4) In the actual use research process, when using the oxide electrodes in the prior art (NiO-NiO-BaZr _x Y _1-x O _3-δ or NiO-BaZr _x Ce _y Y _1-xy O _{3- δ} as the anode, and La _x Sr _1-x Co _y Fe _1-y O _3-δ or La _x Sr _1-x MnO _3-δ as the cathode), because the oxide electrode adopts coating technology, its interfacial binding force is low , after dozens of hours of actual work, the phenomenon of film layer separation and shedding is prone to occur.

(At the same time, it can be compared with BZCY (BaZr _x Ce _y Y _1-xy O _3-δ )) In this exemplary embodiment, the BZNY proton conductor 1 has a better relationship with the metal nickel electrode due to the part of nickel contained in the composition. Compatibility and interface binding force solve the problem that the oxide electrode film is easy to fall off from the proton conductor layer.

Each part will be described separately as follows:

More preferably, in an exemplary embodiment, the BZNY proton conductor 1 serves as a space for the transfer and movement of hydrogen ions during the hydrogen separation process, and has a specific component structure and good working performance. BZNY proton conductor 1 includes but not limited to cylinder, cuboid, and cube centrosymmetric geometric structures with uniform thickness, and has a specific composition of BaZr _0.8 Ni _0.04 Y _0.16 O _3-δ (BZNY). The BZNY proton conductor 1 has good proton conductivity and can maintain good stability at medium and high temperatures of 500-800 degrees Celsius, that is, the subsequent working temperature is 500-800 degrees Celsius. At the same time, the final sintering temperature range of BZNY proton conductor 1 is 1200-1600 degrees Celsius. The grain size of BZNY proton conductor 1 is maintained at the millimeter or nanometer level.

More preferably, in an exemplary embodiment, the metal nickel electrode is deposited or connected to the BZNY proton conductor 1, and serves as an input terminal for electrical signals. The methods for making metal nickel electrodes include but are not limited to electroplating, sputtering, reduction, and vapor deposition. The thickness of the first metal nickel electrode 201 and the second metal nickel electrode 202 is 10-1000nm, and the microstructure of the metal nickel electrode is dense and its crystal grains are evenly distributed, and the metal nickel electrode is fully or partially connected to the BZNY proton conductor 1 Tight, no obvious layering macroscopically.

Among them, it should be noted that when the magnetron sputtering process is used in the method of making the metal nickel electrode, compared with the coating + sintering process used in the oxide electrode, the interface bonding force can be improved, and the film layer uniformity of the electrode can be improved. The proven reliability of the process. Because the oxide electrode adopts coating technology, its interfacial bonding force is low, and the film layer separation and shedding are prone to occur after dozens of hours of actual work. The experiment did not find the membrane layer separation and phenomenon of the electrode and the electrolyte, and the hydrogen separation performance of the nickel-BZNY proton conductor 1 element under long-term work did not find obvious fluctuations.

More preferably, in an exemplary embodiment, the external electrical signal input device 4 inputs an electrical signal in the form of voltage or current to act on the metal nickel electrode. Wherein, the variable voltage involved in the electric signal input curve ranges from -10V to 10V, and the constant voltage ranges from 1-10V. The amount of hydrogen permeation can be characterized and controlled by tracking and observing the voltage or current signal applied to both sides of the element.

More preferably, in an exemplary embodiment, the electrical signal input of the external electrical signal input device 4 is connected to the metal nickel electrode through a high-purity silver wire, that is, the first lead 301 and the second lead 302 are both High-purity silver wire, the diameter of the high-purity silver wire is 0.2-0.6mm. More specifically, the conductive end of the first lead 301 is connected to the first metal nickel electrode 201 by sintering, welding, deposition, hot pressing or cold pressing, and the conductive end of the second lead 302 is connected by sintering, welding, deposition, heat It is connected to the second metal nickel electrode 202 by pressing or cold pressing. The electrical signal input includes direct or indirect connection in three ways: point, line and surface through the high-purity silver wire and the metal nickel electrode.

Among them, it should be noted that the use of nickel metal electrodes is more suitable for connection with silver leads than oxide electrodes, which improves the reliability of the device-level lead packaging interconnection process.

A plurality of nickel-proton conductor elements (BZNY proton conductor 1; and the first metal nickel electrode 201 and the second metal nickel electrode 202, respectively arranged on both sides of BZNY proton conductor 1) for hydrogen separation can be formed by cascading A system for hydrogen separation, which realizes the function of separating and recovering hydrogen isotopes from nuclear reaction waste gas for recycling

More preferably, in an exemplary embodiment, the first insulating sleeve is a high-temperature-resistant ceramic tube, and the second insulating sleeve is a high-temperature-resistant glass tube.

Having the same inventive concept as the above exemplary embodiment, another exemplary embodiment of the present invention provides a method for using the nickel-BZNY proton conductor-based hydrogen separation device, including the following steps:

Pass the hydrogen-containing mixed gas into the second insulating sleeve 502;

The first metal nickel electrode 201 receives an external electrical signal through the first lead wire 301, while the second metal nickel electrode 202 receives an external signal through the second lead wire 302;

The hydrogen isotope of the hydrogen-containing mixed gas is extracted to the hydrogen extraction space 50101 of the first insulating sleeve 501 through the BZNY proton conductor 1 under the control of the electric signal.

The following will describe the preparation process of several parts:

The composition of BZNY proton conductor 1 is BaZr _0.8 Ni _0.04 Y _0.16 O _3-δ , the powder is synthesized using self-propagating combustion method, using ethylenediaminetetraacetic acid and citric acid as sintering aids, and the final sheet of BZNY proton conductor 1 The sintering temperature is 1350±5 degrees Celsius, and the obtained BZNY proton conductor 1 maintains a stable phase structure (as shown in Figure 2b). 3b), BZNY proton conductor 1 is a disc with a diameter of 22±2mm (as shown in Figure 4), without obvious bending phenomenon, smooth surface without obvious particles, and its thickness is in the range of 3-10mm.

The preparation method of the double-sided metal nickel electrode is radio frequency magnetron sputtering nickel technology. The radio frequency magnetron sputtering nickel target used is a nickel target with a diameter of 25mm, a thickness of 6mm, and a nickel purity >99.99%. The atmosphere used is pure argon Gas, the vacuum degree is in the range of 15-35mtorr, the sputtering power is in the range of 30-180w, the pre-sputtering is in the range of 10-30mins, the growth sputtering time is in the range of 5-20mins, and the metal nickel electrode obtained by magnetron sputtering Maintain a good metallic nickel phase (as shown in Figure 2a), its thickness is in the range of 500±150mm (as shown in Figure 3a), its shape is a relatively standard circle, its diameter is 10-20mm (as shown in the silvery white part in Figure 4), the metal There is no obvious delamination at the interface between the nickel electrode and the BZNY proton conductor 1 (as shown in Figure 3a).

Fig. 2 is the X-ray diffraction pattern of the metal nickel electrode (a) and BZNY proton conductor 1 (b) grown by radio frequency magnetron sputtering technology provided by the present invention, illustrating the nickel electrode prepared by this process and the phase of BZNY proton conductor 1 Single structure, high phase purity. Fig. 3 is a scanning electron micrograph of the radio frequency magnetron sputtering metal nickel electrode section (a) and the BZNY proton conductor 1 section (b) provided by the present invention. It shows that the interface between the nickel electrode and the BZNY proton conductor 1 is closely combined, and the crystallinity of the proton conductor 1 is high.

Use DAD-87 conductive silver glue at the silver wire connection to connect the BZNY proton conductor 1 with a high-purity (purity>99.99%) silver wire with a diameter of 0.2mm. The method is point connection, and the connection point 6 is located at the center of the circle of the element prepared in the embodiment.

The given electrical signal input acts directly on the high-purity silver wire and indirectly on the metal nickel electrode. The preset curve of the given electrical signal input is a voltage signal. The input voltage range of the curve is 0-5V, the step voltage is 5mv, and the actual monitoring points are 1000 points. The detected data includes basic electrical performance parameters such as current, voltage, power, and resistance. Among them, Fig. 5 shows the relationship between the given electrical signal input in the form of voltage and the hydrogen transmission rate when hydrogen is extracted from the hydrogen-helium mixed gas with a hydrogen content of 0.001%.

Apparently, the above-mentioned embodiment is only an example for clearly explaining, rather than limiting the implementation. For those of ordinary skill in the art, other changes or changes in different forms can be made on the basis of the above-mentioned description. . It is not necessary and impossible to exhaustively list all the implementation manners here. However, the obvious changes or changes derived therefrom are still within the scope of protection of the present invention.

Claims (10)

1. A hydrogen separation apparatus based on a nickel-BZNY proton conductor, characterized in that: the method comprises the following steps:

a BZNY proton conductor;

the first metal nickel electrode and the second metal nickel electrode are respectively arranged on two sides of the BZNY proton conductor;

the conductive end of the first lead is connected with the first metal nickel electrode; the conductive end of the second lead is connected with the second metal nickel electrode; the access end of the first lead and the access end of the second lead are both connected with external electric signal input equipment;

the first insulating sleeve is connected to one side, located on the first metal nickel electrode, of the BZNY proton conductor and sleeved on the periphery of the first metal nickel electrode, and a hydrogen extraction space is formed inside the first insulating sleeve;

the second insulating sleeve is sleeved outside the first insulating sleeve, and a hydrogen-containing mixed gas providing space is formed between the second insulating sleeve and the first insulating sleeve.

2. A nickel-BZNY proton conductor based hydrogen separation apparatus as claimed in claim 1, wherein: the conductive end of the first lead is connected with the first metal nickel electrode in a sintering, welding, depositing, hot pressing or cold pressing mode, and the conductive end of the second lead is connected with the second metal nickel electrode in a sintering, welding, depositing, hot pressing or cold pressing mode.

3. A nickel-BZNY proton conductor based hydrogen separation apparatus as claimed in claim 1, wherein: the first insulating sleeve is a high-temperature-resistant ceramic tube, and the second insulating sleeve is a high-temperature-resistant glass tube.

4. A nickel-BZNY proton conductor-based hydrogen separation apparatus as claimed in claim 1, wherein: the hydrogen content of the hydrogen-containing mixed gas is less than 0.001%.

5. A nickel-BZNY proton conductor-based hydrogen separation apparatus as claimed in claim 1, wherein: the variable voltage range of the input curve of the electric signal input by the external electric signal input equipment is between-10V and 10V, and the constant voltage range is between 1V and 10V.

6. A nickel-BZNY proton conductor-based hydrogen separation apparatus as claimed in claim 1, wherein: the final sintering temperature range of the BZNY proton conductor is 1200-1600 ℃.

7. A nickel-BZNY proton conductor-based hydrogen separation apparatus as claimed in claim 1 or 2, wherein: the first lead and the second lead are both high-purity silver wires.

8. A nickel-BZNY proton conductor-based hydrogen separation apparatus as claimed in claim 1, wherein: the method for manufacturing the metal nickel electrode comprises an electroplating method, a sputtering method, a reduction method and a vapor deposition method.

9. A nickel-BZNY proton conductor-based hydrogen separation apparatus as claimed in claim 1, wherein: the thickness of the first metal nickel electrode and the second metal nickel electrode is 10-1000nm, and the diameter of the first lead and the diameter of the second lead are 0.2-0.6mm.

10. A method of using a nickel-BZNY proton conductor based hydrogen separation apparatus as claimed in any one of claims 1 to 9, wherein: the method comprises the following steps:

introducing a hydrogen-containing mixed gas into the second insulating sleeve;

the first metal nickel electrode receives an external electric signal through a first lead, and the second metal nickel electrode receives an external signal through a second lead;

the hydrogen isotope of the hydrogen-containing mixed gas is extracted to the hydrogen extraction space of the first insulating sleeve through the BZNY proton conductor under the control of an electric signal.

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