CN216870446U - Membrane-free flow cell equipment for electro-catalysis hydrogen production - Google Patents

Abstract

The utility model provides a membraneless flow cell device for electrocatalytic hydrogen production, which comprises an electrochemical flow module, an electrode chamber module detachably arranged on the electrochemical flow module, a pair of external conductive modules tightly attached to two sides of the electrochemical flow module, and an insulating fixing piece for clamping the external conductive modules; the electrode chamber module is tightly clamped between a pair of external conductive modules and is assembled in sequence according to an internal conductive module-an electrode-a separation block-an electrode-an internal conductive module, the two electrodes are separated by the separation block, the opposite surfaces of the two electrodes are exposed out of the gap of the separation block, the gap area is used as a reaction channel, and the two electrodes and a liquid inlet and outlet channel in the electrochemical flow moving module form a through sealed electrolyte channel. The utility model can avoid the contact of the two electrodes, the gas mixing of the products, the slow ion exchange between the electrodes and other adverse factors, and realizes safe, high-efficiency and stable low-energy-consumption industrial electro-catalytic hydrogen production.

Description

Membrane-free flow cell equipment for electro-catalysis hydrogen production

Technical Field

The utility model relates to the field of electrochemical tests, in particular to a membrane-free flow cell device for electro-catalysis hydrogen production.

Background

In the field of electrocatalytic water decomposition hydrogen production energy conversion, a test system of a flow cell is one of important indexes for judging whether a material can reach commercial application. In the electro-catalytic flow cell test system, the electrolyte can weaken the thickness of an adsorption layer on the surface of an electrode in time through the rapid movement on the surface of an electrode catalyst, so that the contact distance between the catalyst and a reactant is shortened, and meanwhile, a product can be rapidly separated from the surface of the catalyst to release more reaction catalytic sites, so that the reaction rate is accelerated, the hydrogen production capacity is improved, and the purpose of saving energy and producing hydrogen is realized.

At present, a diaphragm in the design of a commercial electrocatalytic hydrogen production flow cell device is an indispensable important part (such as anion exchange, cation exchange membrane, bipolar membrane, etc.), and the purpose of the device is to prevent the occurrence of short circuit danger caused by direct contact between a cathode and an anode, to avoid the occurrence of danger that gas products (hydrogen and oxygen) generated by catalytic reaction of the two electrodes meet each other, and to ensure the reaction to proceed through ion exchange. Although the diaphragm of the flow cell avoids the danger of short circuit and the danger of gas mixing caused by direct contact between two electrodes, the diaphragm also greatly hinders the ion exchange rate between the two electrodes, and further the electrocatalytic hydrogen production performance cannot be further broken through. In addition, the membranes are expensive, complex in process, limited in lifetime, and cumbersome in assembly and disassembly procedures in the flow cell.

SUMMERY OF THE UTILITY MODEL

The present invention aims to solve the above technical problem at least to some extent. Therefore, the utility model provides the membrane-free flow cell equipment for the electro-catalytic hydrogen production, which can avoid the contact of two electrodes, the gas mixing of products, the slow ion exchange between the electrodes and other adverse factors, can be combined with the organic small molecule electro-oxidation coupling catalytic water decomposition hydrogen production technology, and provides an effective and feasible technical scheme for realizing safe, efficient and stable low-energy consumption industrial electro-catalytic hydrogen production.

In order to achieve the purpose, the utility model adopts the following technical scheme:

a membraneless flow cell device for electrocatalytic hydrogen production is structurally characterized in that:

the electrochemical flow module comprises an electrochemical flow module, an electrode chamber module detachably mounted on the electrochemical flow module, a pair of external conductive modules tightly attached to two sides of the electrochemical flow module, and an insulating fixing piece;

the pair of external conductive modules are respectively provided with pins exposed outside the equipment, the overall dimension of the insulation firmware is larger than that of the external conductive modules, and the pair of external conductive modules are tightly attached and detachably clamped inside the insulation firmware;

the electrode cavity module is tightly clamped between a pair of external conductive modules and is assembled in sequence according to an internal conductive module-electrode-separation block-electrode-internal conductive module, two adjacent components are tightly attached to each other, the exposed surfaces of the two internal conductive modules are tightly attached to the inner sides of the pair of external conductive modules respectively, the separation block is provided with two separation blocks, a through gap is formed between the two separation blocks at intervals, the two electrodes are arranged oppositely and tightly attached to the two sides of the separation block respectively and are used as a cathode electrode and an anode electrode respectively, the opposite surfaces of the two electrodes are exposed out of the gap area, the gap area is used as a reaction channel, the two ends of the gap are respectively used as a liquid inlet and a liquid outlet of the reaction channel, and the reaction channel in a working state is vertically arranged;

and a liquid inlet channel and a liquid outlet channel which are respectively matched and communicated are correspondingly formed in the electrochemical flow module according to a liquid inlet and a liquid outlet of the electrode cavity module, the liquid inlet channel and the liquid outlet channel are respectively and correspondingly provided with a liquid inlet pipe and a liquid outlet pipe which are exposed out of the equipment, and a through sealed electrolyte channel is formed by the liquid inlet pipe and the liquid outlet pipe and the reaction channel.

The utility model is also characterized in that:

the electrochemical flow module is arranged at the joint of the external conducting module and the electrochemical flow module, and the electrochemical flow module is arranged at the joint of the external conducting module and the electrode cavity module and is used for sealing the electrolyte channel.

The middle part of the electrochemical flow module is provided with a mounting through hole, the electrode cavity module is embedded in the mounting through hole, the exposed surfaces of the two internal conductive modules are respectively flush with the outer surface of the electrochemical flow module at the side of the mounting through hole, and a sealing ring is mounted at each side hole edge of the mounting through hole and between the internal conductive module and the external conductive module.

The insulating firmware is provided with a pair of, is equipped with the adaptation in the inboard and is in the mounting groove of outside conductive module appearance, outside conductive module inlays to be adorned in the mounting groove to flush in the medial surface of insulating firmware.

In the electrode chamber module, the outer edge of the separating block is flush with the outer edge of the internal conductive module, and the whole electrode is arranged between the separating block and the internal conductive module.

In the electrode cavity module, the internal conductive module is a circular conductive carbon cake, the separation blocks are of an arched block structure, and the pair of separation blocks are opposite to each other in straight edges and are arranged at intervals and are connected with the pair of internal conductive modules in a penetrating mode through the insulating columns.

The external conductive module comprises a conductive copper module with a sheet structure and conductive module hard carbon, the conductive copper module and the conductive module hard carbon are connected in a bonding mode, and the conductive module hard carbon is tightly attached to the internal conductive module.

Compared with the prior art, the utility model has the beneficial effects that:

1. the membrane-free flow cell equipment for the electro-catalytic hydrogen production is used in the field of the electro-catalytic hydrogen production, realizes the separation of a positive electrode and a negative electrode without a diaphragm, can avoid danger caused by the contact of the positive electrode and the negative electrode, and can be combined with an organic small molecule electro-oxidation coupling electrolysis hydrogen production technology, effectively avoids the possibility of oxygen production by the oxidation of electrolysis water, further realizes the completion of catalytic reaction of the positive electrode and the negative electrode in one chamber, achieves the aim of safe, efficient and stable low-energy-consumption hydrogen production, solves the problem of slow ion transmission caused in the diaphragm test process, and can achieve the aim of safe, efficient and low-energy-consumption industrial-level hydrogen production;

2. the device has sensitive electrochemical response signals and reasonable fluid dynamics characteristics, has reasonable and simple structural design, small volume, convenient carrying, convenient and quick assembly and disassembly, is easy to replace electrodes, can be used for electrochemical detection and analysis under different systems, and has wide application prospect.

Drawings

FIG. 1 is a schematic structural view of the present invention;

FIG. 2 is a schematic view of an exploded structure of the present invention;

FIG. 3 is a schematic diagram of the structure of an electrochemical flow module of the utility model;

FIG. 4 is an exploded view of an electrode chamber module according to the present invention;

FIG. 5 is a schematic view of an assembly process of an electrode chamber module according to the present invention;

FIG. 6 is three graphs obtained from the relationship between current density (A) and voltage (V) for tests conducted by a linear cyclic scanning procedure using a conventional electrolytic cell, a flow cell with a membrane, and a flow cell without a membrane, respectively, in a 1.0M potassium hydroxide electrolyte containing 0.1M hydrazine hydrate.

In the figure, the position of the upper end of the main shaft,

1 insulating firmware; 11, mounting a groove; 12 stainless steel screws;

2 an external conductive module; 21 a conductive copper module; a 22 pin; 23 conductive modular hard carbon;

3, sealing rings;

4 an electrochemical flow module; 41 liquid inlet channels; 42 a liquid inlet pipe; 43 liquid outlet channel; 44 a liquid outlet pipe; 45 installing a through hole;

5 an electrode chamber module; 51 an internal conductive module; 52 dividing blocks; 53 electrodes; 54 insulating columns; 55 reaction channel.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Referring to fig. 1 to 5, the membraneless flow cell device for electrocatalytic hydrogen production of the present embodiment includes an electrochemical flow module 4, an electrode 53 chamber module 5 detachably mounted on the electrochemical flow module 4, a pair of external conductive modules 2 closely attached to both sides of the electrochemical flow module 4, and an insulating fixture 1;

the pair of external conductive modules 2 are respectively provided with pins 22 exposed outside the equipment, the external dimension of the insulating fixing piece 1 is larger than that of the external conductive modules 2, and the pair of external conductive modules 2 are tightly attached and detachably clamped in the insulating fixing piece;

the electrode 53 cavity module 5 is tightly clamped between a pair of external conductive modules 2, and is assembled in sequence according to 'internal conductive module 51-electrode 53-separating block 52-electrode 53-internal conductive module 51', two adjacent components are tightly attached to each other, the exposed surfaces of the two internal conductive modules 51 are tightly attached to the inner sides of the pair of external conductive modules 2, the separating block 52 is provided with two electrodes, a through gap is formed between the two electrodes at intervals, the two electrodes 53 are arranged oppositely and tightly attached to the two sides of the separating block 52 respectively and used as a cathode electrode 53 and an anode electrode 53, the opposite surfaces of the two electrodes 53 are exposed in the gap area, the gap area is used as a reaction channel 55, the two ends of the gap are used as a liquid inlet and a liquid outlet of the reaction channel 55 respectively, and the reaction channel 55 in a working state is arranged vertically;

in the electrochemical flow module 4, a liquid inlet channel 41 and a liquid outlet channel 43 are correspondingly formed and respectively matched with and communicated with a liquid inlet and a liquid outlet of the electrode 53 cavity module 5, the liquid inlet channel 41 and the liquid outlet channel 43 are respectively and correspondingly provided with a liquid inlet pipe 42 and a liquid outlet pipe 44 exposed outside the device, and a through and sealed electrolyte channel (shown by a dotted line in fig. 3) is formed with the reaction channel 55.

The corresponding structural arrangement of the device also comprises:

and a sealing structure provided at the junction of the external conductive module 2, the electrochemical flow module 4 and the electrode 53 chamber module 5 for sealing the electrolyte passage.

The electrochemical flow module 4 is formed by processing polymethyl methacrylate material, the middle part is opened there is installation through-hole 45, electrode 53 cavity module 5 is embedded in installation through-hole 45, the exposed surface of two inside conductive modules 51 flushes with the surface of the side electrochemical flow module 4 at place respectively, every side hole edge department at installation through-hole 45, be located the sealing washer 3 of installation hydrogenated nitrile rubber material between inside conductive module 51 and the outside conductive module 2, form the sealed of electrolyte passageway, prevent that electrolyte from flowing out from the gap between electrode 53 cavity module 5 and the outside conductive module 2, and then avoid the corruption of electrolyte to the conductive copper module 21 in the outside conductive module 2.

The insulating fixing member 1 is made of polymethyl methacrylate material, and is provided with a pair of mounting grooves 11 which are matched with the appearance of the external conductive module 2, the external conductive module 2 is embedded in the mounting grooves 11 and is flush with the inner side surface of the insulating fixing member 1, and the pins 22 are arranged along the mounting grooves 11 and are exposed out of the equipment. In this embodiment, the depth of the mounting groove 11 is 2mm, and the pair of insulating fixing members 1 and the electrochemical flow module 4 are both square structures, and have adaptive outer dimensions, and are fixed at four corners by stainless steel screws 12.

In the electrode 53 chamber module 5, the outer edge of the separating block 52 is flush with the outer edge of the internal conductive module 51, and the electrode 53 is entirely embedded between the separating block 52 and the internal conductive module 51.

In the electrode 53 chamber module 5, the internal conductive module 51 is a circular conductive carbon cake, the separation blocks 52 are arch-shaped block structures and are made of polymethyl methacrylate materials, and the pair of separation blocks 52 are arranged opposite to each other at intervals by straight edges and are connected with the pair of internal conductive modules 51 in a penetrating manner through the insulating columns 54 made of polytetrafluoroethylene materials. The arrangement of the pair of spacers 52 is used to prevent the danger of short circuit when the cathode 53 and the anode 53 are in contact, and to fix and selectively expose the electrodes 53 with specific areas, so that the electrolyte flows between the pair of spacers 52 and contacts the surfaces of the cathode 53 to generate electrocatalytic reaction.

In specific implementation, arch blocks with various thickness specifications can be configured, and the distance between the cathode and anode 53 can be adjusted by exchanging the arch blocks with different thicknesses.

The external conductive module 2 comprises a conductive copper module 21 with a sheet structure and a square conductive module hard carbon 23, which are connected by a mixed conductive adhesive, and the conductive module hard carbon 23 is closely attached to the internal conductive module 51 (i.e. a round conductive carbon cake). The conductive copper module 21 is made of pure copper, the main body of the conductive copper module is square and is adaptive to the size of the conductive module hard carbon 23, a rectangular strip pin 22 is led out from one corner of the square, and the tail end of the pin 22 is rounded.

The order of assembly of the device may be:

placing an insulating fixing piece 1 on the bottom layer, embedding a conductive copper module 21 into a mounting groove 11 of the insulating fixing piece 1, adhering a conductive module hard carbon 23 to the surface of the conductive copper module 21 through mixed conductive adhesive, embedding into the mounting groove 11 of the insulating fixing piece 1, placing a sealing ring 3 on the conductive module hard carbon 23, aligning an electrochemical flowing module 4 through a side mounting through hole 45 edge, embedding onto the sealing ring 3, simultaneously ensuring that screw holes at four corners of the sealing ring are aligned with screw holes of the insulating fixing piece 1, embedding an assembled electrode 53 cavity module 5 into a mounting through hole 45 of the electrochemical flowing module 4, placing another sealing ring 3 on the mounting through hole 45 edge at the other side of the electrochemical flowing module 4, aligning the insulating fixing piece 1 provided with the conductive module hard carbon 23 and the conductive copper module 21 at the other side with the side sealing ring 3, and simultaneously ensuring that the screw holes are aligned, finally, four stainless steel screws 12 are passed through the screw holes to clamp and fix.

Wherein, the assembly process of the electrode 53 chamber module 5 can be performed with reference to fig. 5.

The working principle is as follows:

electrolyte enters from the liquid inlet pipe 42 of the electrochemical flow module 4, flows into the electrode 53 cavity module 5 through the L-shaped liquid inlet channel 41 shown in the figure, contacts with the electrode 53 in the reaction channel 55 to generate catalytic reaction, and reaction products flow out from the liquid outlet pipe 44 of the electrochemical flow cell module along with the electrolyte through the L-shaped liquid outlet channel 43 shown in the figure.

FIG. 6 shows the formulation molar concentration of 1.0M KOH (containing 0.5M KOH)M hydrazine hydrate), the same material of the negative and positive electrodes 53 in three different electrolytic cells (conventional static electrolytic cell, membrane flow cell, non-membrane flow cell) through the electrochemical workstation using linear sweep voltammetry program to obtain three current density versus voltage relationship diagram, it can be seen with different electrolytic cell test performance differences: performance of membraneless flow cell>Performance of a membrane flow cell>Conventional static electrolysis cells. When the current density (500mA cm) required by the industrial grade is reached^-2) The voltage required for the membrane-free flow cell was 0.61V, 220mV less than that required for the membrane-flow cell, and 460mV less than that required for the conventional static flow cell. The test result shows that the electrocatalytic hydrogen production membraneless flow cell device combines the technology of coupling the electro-oxidation of organic micromolecules with the electrolysis of water to produce hydrogen, can safely, efficiently and low-energy-consumption reach the index required by industrial-grade hydrogen production, and has a promising application prospect.

While embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the utility model, the scope of which is defined by the claims and their equivalents.

Claims (7)

1. A membraneless flow cell device for electrocatalysis hydrogen production is characterized in that:

the electrochemical flow module comprises an electrochemical flow module, an electrode chamber module detachably mounted on the electrochemical flow module, a pair of external conductive modules tightly attached to two sides of the electrochemical flow module, and an insulating fixing piece;

the pair of external conductive modules are respectively provided with pins exposed outside the equipment, the overall dimension of the insulation firmware is larger than that of the external conductive modules, and the pair of external conductive modules are tightly attached and detachably clamped inside the insulation firmware;

the electrode cavity module is tightly clamped between a pair of external conductive modules and is assembled in sequence according to an internal conductive module-electrode-separation block-electrode-internal conductive module, two adjacent components are tightly attached to each other, the exposed surfaces of the two internal conductive modules are tightly attached to the inner sides of the pair of external conductive modules respectively, the separation block is provided with two separation blocks, a through gap is formed between the two separation blocks at intervals, the two electrodes are arranged oppositely and tightly attached to the two sides of the separation block respectively and are used as a cathode electrode and an anode electrode respectively, the opposite surfaces of the two electrodes are exposed out of the gap area, the gap area is used as a reaction channel, the two ends of the gap are respectively used as a liquid inlet and a liquid outlet of the reaction channel, and the reaction channel in a working state is vertically arranged;

and a liquid inlet channel and a liquid outlet channel which are respectively matched and communicated are correspondingly formed in the electrochemical flow module according to a liquid inlet and a liquid outlet of the electrode cavity module, the liquid inlet channel and the liquid outlet channel are respectively and correspondingly provided with a liquid inlet pipe and a liquid outlet pipe which are exposed out of the equipment, and a through sealed electrolyte channel is formed by the liquid inlet pipe and the liquid outlet pipe and the reaction channel.

2. The membraneless flow cell device for electrocatalytic hydrogen production according to claim 1, characterized in that: the electrochemical flow module is arranged at the joint of the external conducting module and the electrochemical flow module, and the electrochemical flow module is arranged at the joint of the external conducting module and the electrode cavity module and is used for sealing the electrolyte channel.

3. The membraneless flow cell device for electrocatalytic hydrogen production according to claim 1, characterized in that: the middle part of the electrochemical flow module is provided with a mounting through hole, the electrode cavity module is embedded in the mounting through hole, the exposed surfaces of the two internal conductive modules are respectively flush with the outer surface of the electrochemical flow module at the side of the mounting through hole, and a sealing ring is mounted at each side hole edge of the mounting through hole and between the internal conductive module and the external conductive module.

4. The membraneless flow cell device for electrocatalytic hydrogen production according to claim 1, characterized in that: the insulating firmware is provided with a pair of, is equipped with the adaptation in the inboard and is in the mounting groove of outside conductive module appearance, outside conductive module inlays to be adorned in the mounting groove to flush in the medial surface of insulating firmware.

5. The membraneless flow cell device for electrocatalytic hydrogen production according to claim 1, characterized in that: in the electrode chamber module, the outer edge of the separating block is flush with the outer edge of the internal conductive module, and the whole electrode is arranged between the separating block and the internal conductive module.

6. The membraneless flow cell device for electrocatalytic hydrogen production according to claim 1, characterized in that: in the electrode cavity module, the internal conductive module is a circular conductive carbon cake, the separation blocks are of an arched block structure, and the pair of separation blocks are opposite to each other in straight edges and are arranged at intervals and are connected with the pair of internal conductive modules in a penetrating mode through the insulating columns.

7. The membraneless flow cell device for electrocatalytic hydrogen production according to claim 1, characterized in that: the external conductive module comprises a conductive copper module with a sheet structure and conductive module hard carbon, the conductive copper module and the conductive module hard carbon are connected in a bonding mode, and the conductive module hard carbon is tightly attached to the internal conductive module.

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