CN115172835A

CN115172835A - Density-induced self-layering film-free thermal regeneration battery

Info

Publication number: CN115172835A
Application number: CN202210854268.6A
Authority: CN
Inventors: 张亮; 李俊; 石雨; 付乾; 廖强; 朱恂
Original assignee: Chongqing University
Current assignee: Chongqing University
Priority date: 2022-07-14
Filing date: 2022-07-14
Publication date: 2022-10-11

Abstract

The invention discloses a density-induced self-layering membraneless thermal regeneration battery which comprises a reactor shell, an inlet end, a liquid inlet end and an outlet end. A cathode chamber and an anode chamber are arranged in the reactor shell, a cathode electrode is arranged in the cathode chamber, and an anode electrode is arranged in the anode chamber. The cathode electrolyte is introduced into the cathode chamber through the inlet end, an intermediate solution capable of electrochemically reacting with the anode is introduced into the liquid inlet end, the intermediate solution and the cathode electrolyte are mixed to form the anode electrolyte, and the anode electrolyte flows out through the outlet end. The density of the intermediate solution is less than the density of the catholyte so that the catholyte and anolyte form an interface through a density difference. According to the density-induced self-layering membraneless thermal regeneration battery, the interface formed by the catholyte and the anolyte is a virtual membrane due to density difference so as to replace an expensive ion exchange membrane, the construction cost of the battery is remarkably reduced, and the membraneless thermal regeneration battery can rapidly realize cathode and anode conversion through inversion.

Description

Density-induced self-layering film-free thermal regeneration battery

Technical Field

The invention relates to the technical field of thermal regeneration batteries, in particular to a density-induced self-layering membraneless thermal regeneration battery.

Background

The low grade waste heat (< 130 ℃) produced in industrial processes is considered a thermal pollutant and also a huge energy loss. The utilization of efficient waste heat recovery is crucial to reducing greenhouse gas emissions and is expected to bring potential economic and environmental benefits.

In order to realize effective waste heat recovery, some electrochemical-based thermoelectric conversion system technologies have been developed in recent years, and among them, a Thermal Regenerative Battery (TRB) is an efficient energy conversion technology, and compared with other thermoelectric conversion systems, the TRB has a higher output capacity, which brings a hope for its practical application in the future. The TRB in the existing research is mainly composed of an electrode end plate, a cathode chamber, a cathode electrode, an anion exchange membrane, an anode chamber and an anode electrode.

Although this technology is rapidly developing, it still faces some challenges. The main function of the anion exchange membrane in the TRB is to prevent Cu2+ and NH3 in the anolyte from entering catholyte. However, during long periods of electricity production, ion selective membranes (AEMs) have difficulty preventing NH3 permeation during long periods of operation. The larger ammonia concentration gradient on both sides of the anion exchange membrane will exacerbate ammonia crossover. The crossover of ammonia from anode to cathode results in a decrease in ammonia concentration in the anode and results in a mixed cathode potential, resulting in significant performance degradation. And the anion exchange membrane is expensive, which directly causes the construction cost of the battery to be obviously increased, and hinders the further development and application of TRB.

Disclosure of Invention

Based on this, there is a need to provide a membrane-free thermal regeneration battery with density-induced self-delamination, which is aimed at the problems of the existing thermal regeneration battery that the ion-selective membrane is difficult to prevent NH3 from permeating, resulting in significant performance degradation, and the cost is high.

A density-induced self-layering film-free thermal regeneration battery comprising:

the reactor comprises a reactor shell, a reactor shell and a reactor shell, wherein a cathode chamber and an anode chamber are arranged in the reactor shell, the anode chamber is positioned at the upper part of the cathode chamber, a cathode electrode is arranged in the cathode chamber, and an anode electrode is arranged in the anode chamber;

the inlet end is communicated with the cathode chamber, and cathode electrolyte is introduced into the cathode chamber through the inlet end;

the liquid inlet end is connected between the cathode chamber and the anode chamber, an intermediate solution capable of electrochemically reacting with the anode electrode is introduced into the liquid inlet end, and the intermediate solution and the catholyte are mixed to form anolyte; and

the outlet end is communicated with the anode chamber, and the mixed anolyte flows out through the outlet end;

wherein the density of the intermediate solution is less than the density of the catholyte such that the catholyte and the anolyte form an interface through a density difference.

In one embodiment, the cathode electrode and the anode electrode are metal electrodes; or

The cathode electrode and the anode electrode each include a carbon electrode and a metal supported thereon.

In one embodiment, the metal used for the anode electrode and the anode electrode is copper, zinc, silver, nickel or cobalt.

In one embodiment, the intermediate solution is ammonia, ethylenediamine, ethylenediaminetetraacetic acid, or acetonitrile.

In one embodiment, the reactor shell comprises a first shell and a second shell, the cathode chamber is arranged in the first shell, the anode chamber is arranged in the second shell, and the second shell and the first shell are spliced with each other up and down.

In one embodiment, the first housing is provided with a first mounting plate, the second housing is provided with a second mounting plate, and the connecting structure connects the first mounting plate and the second mounting plate.

In one embodiment, the cathode electrode and the anode electrode are symmetrically and parallelly arranged along the liquid inlet end.

In one embodiment, the catholyte is a mixed solution of CuSO4 and (NH 4) 2SO 4.

In one embodiment, the inlet end, the outlet end and the inlet end are provided with a flow dividing channel.

In one of them embodiment, the reposition of redundant personnel runner includes annular flow channel and reposition of redundant personnel mouth, the entry end, the exit end with the feed liquor end is with corresponding annular flow channel connects, the reposition of redundant personnel mouth is located annular flow channel's inboard, and is a plurality of the reposition of redundant personnel mouth is followed annular flow channel's circumferential direction interval is evenly arranged.

According to the density-induced self-layering membraneless thermal regeneration battery, the density of the intermediate solution is smaller than that of the catholyte, so that the density of the anolyte formed by mixing is also smaller than that of the catholyte, the catholyte and the anolyte form a clear and stable interface at the mixing position due to density difference, the catholyte and the anolyte form a virtual membrane by self-layering, an expensive ion exchange membrane is replaced, the problems of ammonia permeation, membrane aging and the like are avoided, stable power generation of the thermal regeneration battery is realized, the construction cost of the battery is remarkably reduced, and the membraneless thermal regeneration battery can quickly realize cathode-anode conversion through inversion.

Drawings

In order to more clearly illustrate the embodiments of the present invention, the drawings, which are required to be used in the embodiments, will be briefly described below. The elements or parts are not necessarily drawn to scale in all figures.

FIG. 1 is a schematic diagram of a film-free thermal regenerative cell with density-induced self-delamination in one embodiment;

FIG. 2 is a schematic diagram of the power generation performance of a thermal regeneration battery;

FIG. 3 is a schematic diagram of the power generation curve of the thermal regeneration battery;

fig. 4 is a schematic diagram of the electrogenesis performance of the cathode and anode of the switching cell.

Reference numerals:

10-reactor shell, 12-cathode cavity, 14-anode cavity, 16-cathode electrode, 18-anode electrode, 110-first shell, 120-second shell, 130-first mounting plate, 140-second mounting plate, 150-connecting structure, 20-inlet end, 30-liquid inlet end, 40-outlet end, 42-annular flow channel, and 44-shunt port.

Detailed Description

In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.

It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "left," "right," and the like as used herein are for illustrative purposes only and do not denote a single embodiment.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

Referring to fig. 1, a density-induced self-layering membraneless thermal regeneration cell according to an embodiment includes a reactor housing 10, an inlet end 20, an inlet end 30, and an outlet end 40.

A cathode chamber 12 and an anode chamber 14 are arranged in the reactor shell 10, the anode chamber 14 is located at the upper part of the cathode chamber 12, and the anode chamber 14 and the cathode chamber 12 are communicated with each other. A cathode electrode 16 is disposed within the cathode chamber 12 and an anode electrode 18 is disposed within the anode chamber 14. The shape of the reactor shell 10 may be specifically configured as desired, such as cylindrical or polygonal, etc.

In one embodiment, the reactor housing 10 includes a first housing 110 and a second housing 120, the cathode chamber 12 is disposed in the first housing 110, the anode chamber 14 is disposed in the second housing 120, and the second housing 120 is stacked on the first housing 110, so that the second housing 120 and the first housing 110 are vertically connected to each other. The reactor shell 10 is formed by splicing two parts, so that the cathode electrode 16 and the anode electrode 18 can be conveniently disassembled and replaced.

On the basis of the above embodiment, further, the first housing 110 is externally provided with the first mounting plate 130, the second housing 120 is externally provided with the second mounting plate 140, and the connecting structure 150 connects the first mounting plate 130 and the second mounting plate 140, so that the sealing effect at the joint of the first housing 110 and the second housing 120 is maintained, and the sealing is ensured against liquid leakage. Specifically, the connection structure 150 may be a claw bolt. Of course, in other embodiments, the connecting structure 150 may also adopt other structures using connection, such as a connecting screw rod, etc.

It is understood that in other embodiments, the reactor shell 10 may be a unitary structure with the cathode electrode 16 and the anode electrode 18 pre-installed within the reactor shell 10.

In one embodiment, the cathode electrode 16 and the anode electrode 18 are identical in structure, and the anode electrode 18 and the cathode electrode 18 may be metal electrodes. In other embodiments, the cathode electrode 16 and the anode electrode 18 may not be all made of metal, and the cathode electrode 16 and the anode electrode 18 may include carbon electrodes and metal loaded thereon, so that the material consumption of the metal can be reduced. Specifically, the metal used for the cathode electrode 16 and the anode electrode 18 may be copper, zinc, silver, nickel, or cobalt. In the present embodiment, the metal used for the cathode electrode 16 and the anode electrode 18 is copper.

An inlet port 20 communicates with the cathode chamber 12 and catholyte passes into the cathode chamber 12 through the inlet port 20. The liquid inlet end 30 is connected between the cathode chamber 12 and the anode chamber 14, an intermediate solution capable of electrochemically reacting with the anode electrode 18 is introduced into the liquid inlet end 30, and after the cathode chamber 12 is filled with the catholyte, the catholyte and the intermediate solution flowing into the liquid inlet end 30 are mixed to form the anolyte. The water outlet end is in communication with the anode chamber 14 and the mixed anolyte exits through the outlet end 40. Wherein the intermediate solution has a density less than that of the catholyte such that the catholyte and anolyte form an interface through a seal differential.

In one embodiment, the inlet end 20 is located at the bottom of the reactor shell 10, and the inlet end 20 is connected to the first shell 110. The outlet end 40 is located at the top of the reactor shell 10, and the outlet end 40 is connected to the second shell 120. The cathode electrode 16 and the anode electrode 18 are symmetrically and parallelly arranged along the liquid inlet end 30, so that the power generation performance of the thermal regeneration battery can be ensured, and the inversion can be facilitated to realize the conversion between the cathode and the anode.

In one embodiment, the intermediate solution is a solution with a low density, the intermediate solution may be ammonia, ethylenediamine tetraacetic acid, or acetonitrile, and the catholyte is a mixed solution of CuSO4 and (NH 4) 2SO 4. Specifically, in the present embodiment, the intermediate solution is ammonia water, the mass fraction of the ammonia water solution is 25%, and the catholyte is a mixed solution of 0.2m CuSO4 and 1M (NH 4) 2SO 4.

In one embodiment, the inlet end 20, the outlet end 40 and the inlet end 30 are provided with split flow channels, which can make the electrolyte flow uniform, and the split design of the inlet end 30 can help to form the cathode-anode electrolyte interface. Specifically, the flow dividing channels include annular flow channels 42 and flow dividing ports 44, the inlet end 20, the outlet end and the inlet end 30 are connected to the corresponding annular flow channels 42, the flow dividing ports 44 are located on the inner side of the annular flow channels 42, the flow dividing ports 44 are designed in multiple numbers, and the flow dividing ports 44 are uniformly arranged at intervals along the circumferential direction of the annular flow channels 42.

The working principle of the density-induced self-layering membraneless thermal regeneration battery is as follows:

catholyte enters from the lower inlet port 20, mixes with ammonia entering from the intermediate inlet port 30 after the cathode chamber 12 is filled with catholyte, mixes with ammonia water to form anolyte, and flows out from the upper outlet port 40. The density of the ammonia water is smaller than that of the catholyte, so that the density of the anolyte formed by mixing is reduced, and the catholyte and the anolyte can form a stable electrolyte interface in the middle due to density difference, so that mutual separation is realized.

Because ammonia water exists in the liquid of the anode electrode 18, the ammonia water and the anode electrode 18 generate corrosion reaction to generate metal ammonia complexes and electrons, the electrons flow to the cathode electrode 16 from an external circuit, cu < 2+ > in the cathode electrolyte is combined with the electrons to generate electroplating reaction, the electroplating reaction is deposited on the surface of the cathode electrode 16, and anions in the electrolyte migrate to form ionic current to form a current loop.

The cell can continuously generate electricity through the reaction of the cathode and anode electrodes 18, the polarization curve and the power density curve of the cell are shown in figure 2, and the maximum power density of the cell reaches 5.3mW/cm < 2 >. And because the self-layering cathode and anode electrolyte formed based on the density difference can effectively eliminate ammonia permeation, a stable electricity generation platform can be realized in the long-time electricity generation process, and as shown in fig. 3, the output voltage of the battery is stabilized above 180 mV.

In the reaction process, the concentration of the copper ammonia complex in the catholyte is continuously increased, the reaction metal on the anode electrode 18 is continuously reduced, and the two electrodes are required to be divided into the cathode electrode 16 and the anode electrode 18 in turn, so that the quality of the cathode electrode 18 and the anode electrode 18 can be effectively balanced, and the stability of the electrodes can be improved. The structure of the battery can be inverted, the switching between the cathode and the anode can be realized rapidly, and the corresponding switching time is related to the flow of the electrolyte.

As shown in fig. 4, when the electrolyte flow rate is 6mL/min, the switching response time is about 40s, as shown in (1) and (2) in fig. 4, while by increasing the electrolyte flow rate to 12mL/min, the switching response time can be shortened to 20s, as shown in (3) and (4) in fig. 4.

And finally, after the electricity generation is finished, the electrolyte enters a thermal reactor device to be thermally regenerated by using low-temperature heat energy, ammonia and copper ion solution are generated, and the electrolyte returns to the reactor again to generate electricity. Therefore, the density difference-induced self-layering film-free thermal regeneration battery can effectively convert low-temperature heat energy into electric energy and realize thermoelectric conversion with high power output.

According to the density-induced self-layering membraneless thermal regeneration battery, the catholyte and the anolyte form a clear and stable interface at a mixed position due to density difference, the cathode and the anolyte form a virtual membrane by self layering so as to replace an expensive ion exchange membrane, the problems of ammonia permeation, membrane aging and the like are avoided, the stable power generation of the thermal regeneration battery is realized, the construction cost of the battery is remarkably reduced, and the conversion of the cathode and the anode can be quickly realized by inversion of the membraneless thermal regeneration battery.

The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description.

Claims

1. A density-induced self-layering film-free thermal regeneration battery, comprising:

the reactor comprises a reactor shell, a reactor core and a reactor core, wherein a cathode chamber and an anode chamber are arranged in the reactor shell, the anode chamber is positioned at the upper part of the cathode chamber, a cathode electrode is arranged in the cathode chamber, and an anode electrode is arranged in the anode chamber;

the inlet end is communicated with the cathode chamber, and the catholyte is introduced into the cathode chamber through the inlet end;

2. The density-induced self-layering film-free thermal regeneration battery of claim 1, wherein the cathode electrode and the anode electrode are metal electrodes; or

3. The density-induced self-layering film-free thermal regeneration battery according to claim 2, wherein the metal used for the cathode electrode and the anode electrode is copper, zinc, silver, nickel or cobalt.

4. The density-induced self-layering membraneless thermal regeneration battery according to claim 3, wherein the intermediate solution is ammonia, ethylenediamine, ethylenediaminetetraacetic acid or acetonitrile.

5. The density-induced self-delamination membrane-less thermal regeneration cell of claim 1 wherein the reactor housing comprises a first housing and a second housing, the cathode chamber being disposed within the first housing, the anode chamber being disposed within the second housing, the second housing and the first housing being joined to one another above one another.

6. The density-induced self-layering membraneless thermal regeneration battery according to claim 5, wherein a first mounting plate is disposed outside the first case, a second mounting plate is disposed outside the second case, and a connecting structure connects the first mounting plate and the second mounting plate.

7. The density-induced self-layering membraneless thermal regeneration cell according to claim 1, wherein the cathode electrode and the anode electrode are arranged symmetrically and in parallel along the inlet end.

8. The density-induced self-delamination film-free thermal regeneration battery as claimed in claim 1 wherein the catholyte is a mixed solution of CuSO4 and (NH 4) 2SO 4.

9. The density-induced self-layering membraneless thermal regeneration battery according to claim 1, wherein the inlet end, the outlet end and the inlet end are provided with flow dividing channels.

10. The density-induced self-layering membraneless thermal regeneration battery according to claim 9, wherein the flow dividing channel comprises an annular flow channel and flow dividing ports, the inlet end, the outlet end and the liquid inlet end are connected with the corresponding annular flow channel, the flow dividing ports are located on the inner side of the annular flow channel, and the flow dividing ports are uniformly arranged at intervals in the circumferential direction of the annular flow channel.