阅读说明：本技术 一种用于氢同位素分离的石墨烯固体电解池装置 (Graphene solid electrolytic cell device for hydrogen isotope separation ) 是由 柳伟平 刘玉昆 郑明杰 周勋 冯宇钦 于 2021-08-30 设计创作，主要内容包括：本发明提供了一种用于氢同位素分离的石墨烯固体电解池装置,包括电解池以及设置在所述电解池内的石墨烯复合膜电极；其中,所述石墨烯复合膜电极由析氢催化层、石墨烯层、阴离子交换层和析氧催化层依次叠加构成；并且,所述析氢催化层所在面朝向所述电解池的阴极端,析氧催化层所在面朝向所述电解池的阳极端。本发明采用石墨烯层与阴离子交换层形成石墨烯复合膜固体电解质,实现氢离子的选择性分离；这种石墨烯复合膜能有效增加固体电解质的氢同位素的筛分能力,提高氢同位素的分离系数,降低电解法氢同位素分离的能耗。本发明有效提高了氢同位素分离系数,为氢同位素生产以及含氚废水处理提供更佳解决方案。(The invention provides a graphene solid electrolytic cell device for hydrogen isotope separation, which comprises an electrolytic cell and a graphene composite membrane electrode arranged in the electrolytic cell; the graphene composite membrane electrode is formed by sequentially overlapping a hydrogen evolution catalyst layer, a graphene layer, an anion exchange layer and an oxygen evolution catalyst layer; and the hydrogen evolution catalysis layer is positioned to face the cathode end of the electrolytic cell, and the oxygen evolution catalysis layer is positioned to face the anode end of the electrolytic cell. The graphene composite membrane solid electrolyte is formed by the graphene layer and the anion exchange layer, so that the selective separation of hydrogen ions is realized; the graphene composite membrane can effectively increase the sieving capacity of the hydrogen isotopes of the solid electrolyte, improve the separation coefficient of the hydrogen isotopes and reduce the energy consumption of hydrogen isotope separation by an electrolytic method. The invention effectively improves the separation coefficient of hydrogen isotopes, and provides a better solution for hydrogen isotope production and tritium-containing wastewater treatment.)

1. A graphene solid electrolytic cell device for hydrogen isotope separation is characterized by comprising an electrolytic cell and a graphene composite membrane electrode arranged in the electrolytic cell; the graphene composite membrane electrode is formed by sequentially overlapping a hydrogen evolution catalyst layer, a graphene layer, an anion exchange layer and an oxygen evolution catalyst layer; and the hydrogen evolution catalysis layer is positioned to face the cathode end of the electrolytic cell, and the oxygen evolution catalysis layer is positioned to face the anode end of the electrolytic cell.

2. The graphene solid electrolytic cell device for hydrogen isotope separation according to claim 1, wherein the electrolytic cell includes an electrolytic cell housing, a cathode plate, an anode plate, an insulating sealing gasket, a sealing gasket, and a gas diffusion layer; the electrolytic cell shell comprises a cathode shell and an anode shell; the cathode shell and the anode shell are respectively arranged at a cathode end and an anode end of the electrolytic cell, the inner side of the cathode shell is sequentially connected with a first insulating sealing gasket, a cathode plate, a first sealing gasket and a first gas diffusion layer, and the inner side of the anode shell is sequentially connected with a second insulating sealing gasket, an anode plate, a second sealing gasket and a second gas diffusion layer; the first gas diffusion layer is connected with the hydrogen evolution catalyst layer of the graphene composite membrane electrode, and the second gas diffusion layer is connected with the oxygen evolution catalyst layer of the graphene composite membrane electrode.

3. The graphene solid electrolytic cell device for hydrogen isotope separation according to claim 1, wherein in the graphene composite membrane electrode, the hydrogen evolution catalyst layer, the graphene layer, the anion exchange layer and the oxygen evolution catalyst layer are sequentially stacked and assembled into a sandwich structure of hydrogen evolution catalyst layer-graphene layer-anion exchange layer-oxygen evolution catalyst layer by a hot pressing or spraying process.

4. The graphene solid electrolytic cell device for hydrogen isotope separation according to claim 1, wherein the overall thickness of the graphene composite membrane electrode is less than one millimeter, and the thickness of the graphene layer in the graphene composite membrane electrode is less than one nanometer.

5. The graphene solid electrolytic cell device for hydrogen isotope separation according to claim 1, wherein the hydrogen evolution catalyst layer is made of a noble metal material, an alloy material of a noble metal, a noble metal compound material, a transition metal material, or a hydrogen evolution catalyst;

the oxygen evolution catalyst layer is made of a noble metal material, a noble metal alloy material, a metal oxide material, a spinel structure oxide material or a nano material catalyst.

6. The graphene solid electrolytic cell device for hydrogen isotope separation according to claim 5, wherein in the hydrogen evolution catalytic layer: the noble metal material is one of Pd and Pt; the noble metal compound material is platinum carbon; the transition metal material is one of nickel and iron; the hydrogen evolution catalyst is a nonmetal amorphous molybdenum trisulfide hydrogen evolution catalyst;

in the oxygen evolution catalytic layer: the noble metal material is one of Ru and Ir; the metal oxide material is IrO₂、RuO₂NiO and CoO; the spinel-structured oxide material is CuCo₂O₄、NiCo₂O₄One of (1); the nano material catalyst is one of an iron-based nano material, a silver-based nano material and a gold-based nano material.

7. The graphene solid electrolytic cell device for hydrogen isotope separation according to claim 1, wherein the graphene layer is made of graphene or a graphene derivative.

8. The graphene solid electrolytic cell device for hydrogen isotope separation according to claim 1, wherein the anion exchange layer employs a chitosan-based anion exchange membrane, a polysulfone-based anion exchange membrane, a phenylene ether-based anion exchange membrane, or a polyvinyl fluoride-based anion exchange membrane.

9. The graphene solid electrolytic cell device for hydrogen isotope separation according to claim 2, wherein the electrolytic cell housing is made of a metal material or an oxidation-resistant polymer material; the negative plate and the positive plate are made of anti-oxidation conductive materials; the insulating sealing gasket and the sealing washer are made of polytetrafluoroethylene films or silica gel materials; the gas diffusion layer is made of carbon materials or metal materials.

10. The graphene solid electrolytic cell device for hydrogen isotope separation according to claim 9, wherein in the electrolytic cell housing: the metal material is one of stainless steel and an aluminum plate; the oxidation resistant polymer material is a polytetrafluoroethylene plate;

in the cathode plate and the anode plate: the anti-oxidation conductive material is one of a pure titanium plate, a gold-plated copper plate and a gold-plated stainless steel plate;

in the gas diffusion layer: the carbon material is one of carbon cloth and carbon paper; the metal material is one of titanium fiber felt and foamed nickel.

Technical Field

The invention belongs to the field of hydrogen isotope electrolysis separation, relates to a solid electrolyte electrolysis separation device, and particularly relates to a graphene solid electrolytic cell device for hydrogen isotope separation.

Background

The hydrogen isotope electrolysis separation is to utilize electric energy to electrolyze water molecules to generate three hydrogen isotope ions of protium, deuterium and tritium, and due to the isotope effect caused by the difference of the protium, deuterium and tritium quality, the three isotopes are dissociated into hydrogen ions from the water molecules in different orders, thereby realizing the separation of protium, deuterium and tritium. The separation of hydrogen isotopes by means of the isotope effect of electrolytic dissociation alone has low efficiency and high energy consumption. At present, research is carried out to combine an electrolysis device with a hydrogen isotope separation material to construct a solid electrolyte hydrogen isotope electrolysis separation device. Under the action of an external electric field, three hydrogen isotope ions of protium, deuterium and tritium directionally move to pass through the hydrogen isotope separation material, and under the combined action of the electrolytic hydrogen isotope effect and the separation material screening, the hydrogen isotope separation coefficient and the electrolytic energy utilization efficiency are improved.

The traditional water electrolysis separation device adopts alkaline electrolyte, the separation coefficient is small (1-3), and the electrolysis efficiency is low. Meanwhile, the conventional alkaline electrolyte also exhibits the following disadvantages when applied: (1) the corrosive effects of the alkaline electrolyte further increase the equipment maintenance cost; (2) CO 2₂The deterioration of the alkaline electrolyte caused by absorption leads to the reduction of the conductivity of the electrolyte, thereby seriously affecting the production efficiency of the hydrogen isotope thereof; (3) the waste liquid generated by electrolysis seriously pollutes the environment and needs to be effectively treated. An Alkaline Solid Electrolytic Cell (ASEC) constructed by using an anion exchange membrane is a novel Electrolytic cell, compared with the prior Electrolytic cellIn a traditional alkaline electrolytic cell, the ASEC has higher electrolytic efficiency, can be suitable for alkaline and neutral environments, and has wider application scenes. Meanwhile, with a proton exchange membrane solid electrolytic cell, the ASEC does not adopt an expensive proton exchange membrane and can apply a non-noble metal catalyst, and has the advantage of low cost. In addition, the ASEC also has the advantages of simple and compact equipment structure and easy operation. Therefore, the ASEC is a promising high-efficiency production apparatus for hydrogen fuel production, but the hydrogen isotope separation coefficient is relatively low as a hydrogen isotope separation apparatus, and is not sufficient for a large amount of hydrogen isotope separation processing. Thus, there is still a need for improvement in current ASEC.

According to related literature, graphene has subatomic selectivity, and hydrogen isotope ions (protons, deuterons and tritium nuclei) pass through a graphene hexagonal lattice and are a thermal activation process. Under the action of an external electric field, protons are activated and can penetrate through the graphene hexagonal lattice barrier. Meanwhile, due to the large mass difference of hydrogen isotope ions, protons with higher zero energy preferentially penetrate through graphene, then deuterons and then tritions, and the difference enables the graphene to have excellent hydrogen isotope selectivity. Theoretical calculation shows that the separation coefficient of protium deuterium can reach as high as 10, and the separation coefficient of protium tritium can reach as high as 30, which is far higher than the hydrogen isotope separation process in the current industrial application. Therefore, the separation of hydrogen isotopes by using graphene to construct an ASEC electrolytic cell, in particular the treatment of tritium-containing wastewater, is an efficient process with a great application prospect.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a graphene solid electrolytic cell device for hydrogen isotope separation, which is used for separating hydrogen isotopes through OH of an anion exchange membrane^-1The separation coefficient of the hydrogen isotopes is effectively improved through the conduction and the screening effect of the graphene; at the same time, it is beneficial to isolate CO by setting up a compact structure₂The negative influence on the alkaline electrolyte, effectively reduces the energy consumption of other parts of the separation device, and improves the utilization efficiency of the hydrogen isotope electrolysis separation energy.

The invention adopts the following technical scheme to solve the technical problems:

a graphene solid electrolytic cell device for hydrogen isotope separation comprises an electrolytic cell and a graphene composite membrane electrode arranged in the electrolytic cell; the graphene composite membrane electrode is formed by sequentially overlapping a hydrogen evolution catalyst layer, a graphene layer, an anion exchange layer and an oxygen evolution catalyst layer; and the hydrogen evolution catalysis layer is positioned to face the cathode end of the electrolytic cell, and the oxygen evolution catalysis layer is positioned to face the anode end of the electrolytic cell.

As one of the preferable modes of the invention, the electrolytic cell comprises an electrolytic cell shell, a cathode plate, an anode plate, an insulating sealing gasket, a sealing gasket and a gas diffusion layer; the electrolytic cell shell comprises a cathode shell and an anode shell; the cathode shell and the anode shell are respectively arranged at a cathode end and an anode end of the electrolytic cell, the inner side of the cathode shell is sequentially connected with a first insulating sealing gasket, a cathode plate, a first sealing gasket and a first gas diffusion layer, and the inner side of the anode shell is sequentially connected with a second insulating sealing gasket, an anode plate, a second sealing gasket and a second gas diffusion layer; the first gas diffusion layer is connected with the hydrogen evolution catalyst layer of the graphene composite membrane electrode, and the second gas diffusion layer is connected with the oxygen evolution catalyst layer of the graphene composite membrane electrode.

In a preferred embodiment of the present invention, in the graphene composite membrane electrode, the hydrogen evolution catalyst layer, the graphene layer, the anion exchange layer, and the oxygen evolution catalyst layer are sequentially stacked by a hot pressing or spraying process, and assembled into a sandwich structure of "hydrogen evolution catalyst layer-graphene layer-anion exchange layer-oxygen evolution catalyst layer".

In a preferred embodiment of the present invention, the overall thickness of the graphene composite membrane electrode is less than one millimeter, and the thickness of the graphene layer in the graphene composite membrane electrode is less than one nanometer.

In a preferred embodiment of the present invention, the hydrogen evolution catalyst layer is made of a noble metal material, a noble metal alloy material, a noble metal compound material, a transition metal material, or a hydrogen evolution catalyst;

the oxygen evolution catalyst layer is made of a noble metal material, a noble metal alloy material, a metal oxide material, a spinel structure oxide material or a nano material catalyst.

In a preferred embodiment of the present invention, the hydrogen evolution catalyst layer includes: the noble metal material is one of Pd and Pt; the noble metal compound material is platinum carbon; the transition metal material is one of nickel and iron; the hydrogen evolution catalyst is a nonmetal amorphous molybdenum trisulfide hydrogen evolution catalyst;

in the oxygen evolution catalytic layer: the noble metal material is one of Ru and Ir; the metal oxide material is IrO₂、RuO₂NiO and CoO; the spinel-structured oxide material is CuCo₂O₄、NiCo₂O₄One of (1); the nano material catalyst is one of an iron-based nano material, a silver-based nano material and a gold-based nano material.

In a preferred embodiment of the present invention, the graphene layer is made of graphene or a graphene derivative.

In a preferred embodiment of the present invention, the anion exchange layer is a chitosan anion exchange membrane, a polysulfone anion exchange membrane, a phenylene ether anion exchange membrane, or a polyvinyl fluoride anion exchange membrane.

In a preferred embodiment of the present invention, the electrolytic cell case is made of a metal material or an oxidation-resistant polymer material; the negative plate and the positive plate are made of anti-oxidation conductive materials; the insulating sealing gasket and the sealing washer are made of polytetrafluoroethylene films or silica gel materials; the gas diffusion layer is made of carbon materials or metal materials.

In a preferred embodiment of the present invention, the electrolytic cell casing includes: the metal material is one of stainless steel and an aluminum plate; the oxidation resistant polymer material is a polytetrafluoroethylene plate;

in the cathode plate and the anode plate: the anti-oxidation conductive material is one of a pure titanium plate, a gold-plated copper plate and a gold-plated stainless steel plate;

in the gas diffusion layer: the carbon material is one of carbon cloth and carbon paper; the metal material is one of titanium fiber felt and foamed nickel.

Compared with the prior art, the invention has the advantages that: OH of the invention Via anion exchange Membrane^-1The separation coefficient of the hydrogen isotopes is effectively improved through the conduction and the screening effect of the graphene; at the same time, it is beneficial to isolate CO by setting up a compact structure₂The method has the advantages of having adverse effects on the alkaline electrolyte, effectively reducing the energy consumption of other parts of the separation device, and improving the utilization efficiency of the hydrogen isotope electrolysis separation energy, and specifically comprising the following steps:

(1) according to the invention, the graphene composite membrane electrode is formed by assembling all materials into a sandwich structure in a hot pressing or spraying manner, the thickness of the graphene layer used as a hydrogen isotope screening material is less than one nanometer, and the loss of resistance to electric energy caused by the separation material is greatly reduced; meanwhile, the graphene sub-atom selective permeability has strong screening capacity on hydrogen isotopes, provides a separation coefficient higher than that of a hydrogen isotope separation process applied to all industries, and greatly improves the hydrogen isotope separation efficiency, especially the treatment efficiency of tritium-containing wastewater;

(2) in the invention, the whole thickness of the graphene composite membrane electrode is far less than one millimeter, and the electrolytic cell cavity can have extremely flexible remodelability according to the needs; the electrolysis device can improve the production efficiency through multiple stages of parallel connection and improve the purity of the hydrogen isotope in a serial connection mode;

(3) the invention has simple structure and small volume, can be flexibly combined according to different working environments, and expands the application range of the device.

Drawings

Fig. 1 is a schematic view of a disassembled structure of a graphene solid electrolytic cell device for hydrogen isotope separation in example 1;

fig. 2 is a schematic structural view of a graphene composite membrane electrode in example 1.

In the figure: the electrolytic cell comprises an electrolytic cell 1, an electrolytic cell shell 11, a cathode shell 111, an anode shell 112, a cathode plate 12, an anode plate 13, an insulating sealing gasket 14, a first insulating sealing gasket 141, a second insulating sealing gasket 142, a sealing gasket 15, a first sealing gasket 151, a second sealing gasket 152, a gas diffusion layer 16, a first gas diffusion layer 161, a second gas diffusion layer 162, a graphene composite membrane electrode 2, a hydrogen evolution catalytic layer 21, a graphene layer 22, an anion exchange layer 23 and an oxygen evolution catalytic layer 24.

Detailed Description

The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.

Example 1

As shown in fig. 1 to 2, the graphene solid electrolytic cell device for hydrogen isotope separation of the present embodiment includes an electrolytic cell 1 and a graphene composite membrane electrode 2 disposed in the electrolytic cell 1. The graphene composite membrane electrode 2 is formed by sequentially overlapping a hydrogen evolution catalyst layer 21, a graphene layer 22, an anion exchange layer 23 and an oxygen evolution catalyst layer 24; the hydrogen evolution catalyst layer 21 faces the cathode end of the electrolytic cell 1, and the oxygen evolution catalyst layer 24 faces the anode end of the electrolytic cell 2. The electrolytic cell 1 is a classical solid electrolytic cell structure and comprises an electrolytic cell shell 11, a cathode plate 12, an anode plate 13, an insulating sealing gasket 14, a sealing washer 15 and a gas diffusion layer 16; the cell housing 11 comprises a cathode housing 111, an anode housing 112; the cathode shell 111 and the anode shell 112 are respectively disposed at the cathode end and the anode end of the electrolytic cell 1, the inner side of the cathode shell 111 is sequentially connected with a first insulating sealing gasket 141, a cathode plate 12, a first sealing gasket 151 and a first gas diffusion layer 161, and the inner side of the anode shell 112 is sequentially connected with a second insulating sealing gasket 142, an anode plate 13, a second sealing gasket 152 and a second gas diffusion layer 162. The first gas diffusion layer 161 is connected to the hydrogen evolution catalyst layer 21 of the graphene composite membrane electrode 2, and the second gas diffusion layer 162 is connected to the oxygen evolution catalyst layer 24 of the graphene composite membrane electrode 2.

Further, in the graphene composite membrane electrode 2 of the present embodiment, the hydrogen evolution catalyst layer 21, the graphene layer 22, the anion exchange layer 23, and the oxygen evolution catalyst layer 24 are sequentially stacked and assembled into a "sandwich structure of hydrogen evolution catalyst layer-graphene-anion exchange layer-oxygen evolution catalyst layer" by a hot pressing or spraying process. Moreover, the overall thickness of the graphene composite membrane electrode 2 is far less than one millimeter, and the thickness of the graphene layer 22 is less than one nanometer.

Further, in the graphene composite membrane electrode 2 of the present embodiment, regarding the preparation materials of the respective structural parts:

the hydrogen evolution catalyst layer 21 can adopt Pd, Pt or other noble metals and alloy materials; alternatively, platinum carbon or other noble metal compound materials; alternatively, nickel, iron or other transition metal materials; or a non-metallic amorphous molybdenum trisulfide hydrogen evolution catalyst or other hydrogen evolution catalysts.

The oxygen evolution catalyst layer 24 can be made of Ru, Ir or other noble metals and alloy materials; alternatively, IrO₂、RuO₂Or other noble metal oxide materials; alternatively, NiO, CoO, or other non-noble metal oxide materials; alternatively, CuCo₂O₄、NiCo₂O₄Or other spinel structure oxide materials; or iron-based nanomaterials, silver-based nanomaterials, gold-based nanomaterials, or other nanomaterial catalysts.

The graphene layer 22 may be single-layer graphene, double-layer graphene, three or more layers of graphene, or a graphene derivative.

The anion exchange layer 23 adopts chitosan anion exchange membrane, polysulfone anion exchange membrane, phenylate anion exchange membrane, polyvinyl fluoride anion exchange membrane or other anion exchange polymer materials.

Further, in the electrolytic cell 1 of the present example, regarding the preparation materials of the respective structural portions:

the electrolytic cell shell 11 can be made of stainless steel, aluminum plate or other metal materials; alternatively, a polytetrafluoroethylene sheet or other oxidation resistant polymer material.

The cathode plate 12 and the anode plate 13 are made of pure titanium plates, gold-plated copper plates, gold-plated stainless steel plates or other oxidation-resistant conductive materials.

The insulating sealing gasket 14 and the sealing gasket 15 are made of polytetrafluoroethylene films or silica gel materials.

The gas diffusion layer 16 is made of carbon cloth, carbon paper or other carbon materials; alternatively, titanium fiber felt, nickel foam, or other metallic materials.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.