CN116864713A - Thermal regeneration cascade battery and preparation method thereof - Google Patents
Thermal regeneration cascade battery and preparation method thereof Download PDFInfo
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- CN116864713A CN116864713A CN202310946907.6A CN202310946907A CN116864713A CN 116864713 A CN116864713 A CN 116864713A CN 202310946907 A CN202310946907 A CN 202310946907A CN 116864713 A CN116864713 A CN 116864713A
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- 230000008929 regeneration Effects 0.000 title abstract description 40
- 238000011069 regeneration method Methods 0.000 title abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 31
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 claims abstract description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 230000001172 regenerating effect Effects 0.000 claims description 18
- 238000002347 injection Methods 0.000 claims description 14
- 239000007924 injection Substances 0.000 claims description 14
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 8
- 229910001431 copper ion Inorganic materials 0.000 claims description 8
- 239000006260 foam Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000004378 air conditioning Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 238000003487 electrochemical reaction Methods 0.000 abstract description 7
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 5
- 238000010248 power generation Methods 0.000 abstract description 4
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 16
- 239000002131 composite material Substances 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 102100026964 M1-specific T cell receptor beta chain Human genes 0.000 description 8
- 230000005611 electricity Effects 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000003011 anion exchange membrane Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- AQEDFGUKQJUMBV-UHFFFAOYSA-N copper;ethane-1,2-diamine Chemical compound [Cu].NCCN AQEDFGUKQJUMBV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/182—Regeneration by thermal means
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
Abstract
The invention discloses a thermal regeneration cascade battery and a preparation method thereof. The ion exchange membrane is arranged in the reactor to separate the reactor into an anode chamber and a cathode chamber. The cathode electrode is arranged in the cathode chamber and comprises a carbon material and sulfur arranged on the carbon material. The anode electrode is arranged in the anode cavity and comprises a carbon material and cuprous sulfide and copper arranged on the carbon material. According to the thermal regeneration cascade battery and the preparation method thereof, the cathode electrode and the anode electrode both adopt carbon structures which do not react with electrolyte as electrode substrates, so that non-electrochemical corrosion of the anode is successfully relieved, the conversion efficiency of the electrode is improved, and the stability of the electrode is effectively improved. Meanwhile, the heat regeneration cascade battery of the two-stage electrochemical reaction is coupled, so that the power generation quantity of the battery is effectively improved.
Description
Technical Field
The invention relates to the technical field of thermal regeneration batteries, in particular to a thermal regeneration cascade battery and a preparation method thereof.
Background
The thermal regenerative battery (Thermally Regenerative Battery, TRB) is a novel thermoelectric conversion device that recovers low-grade waste heat and converts it into electric energy. The TRB system is a low-temperature thermoelectric conversion technology indirectly using low-temperature heat energy, and is mainly divided into an electricity generation part using an electrochemical cell and a heat regeneration part using low-temperature heat energy.
In the electricity generating part of the battery, the TRB principle is similar to that of a redox battery, potential difference is generated by means of redox couples of a cathode (Cu < 2+ >/Cu, S/Cu < 2+ > S and the like) and an anode (Cu (NH 3) 42+/Cu, cu (en) 22+/Cu and the like), electricity generating current is formed through an external circuit, the anode and the cathode are separated by an ion exchange membrane, mixing of anode active substances and cathode active substances is prevented, and ion transmission of supporting electrolyte is guaranteed, so that the electric neutrality of the solution is guaranteed. Unlike redox cells, the product of the anode is typically present in the form of a complex in order to enable thermoelectric conversion of the system. In the thermal regeneration part, the reacted anolyte is heated by low-temperature heat energy, ligands (ammonia, ethylenediamine, acetonitrile and the like) in the anolyte are separated to become new catholyte, and simultaneously the separated ligands are added into the reacted catholyte to obtain new anolyte which is respectively introduced into a previous anode chamber and a cathode chamber to start the next batch of electricity generation.
There are currently thermal regenerative batteries, including conventional thermal regenerative ammonia batteries, full-water TRBs, and non-water TRBs. The key problem is that the final product on the anode electrode is the initial material of the cathode electrode, whereas the final product on the cathode electrode is the initial material of the anode. However, the thermal regeneration process is only a separation process from the ligand in the electrolyte. The conversion efficiency of the electrode determines the cycling stability and lifetime of the TRB.
In the prior researches, metallic copper is mostly adopted as an electrode in the TRB power generation process, the reaction occurs on the surface of the metallic electrode, and the battery anode coulomb efficiency is low and the battery cyclicity and stability are poor due to the non-electrochemical corrosion of the anode electrode. Meanwhile, the capacity of the battery is directly determined by the loading of the active material on the electrode, and higher energy density and heat energy utilization efficiency of TRB are facilitated by higher loading of the active material.
Disclosure of Invention
Based on the above, it is necessary to provide a thermal regeneration cascade battery and a preparation method thereof, aiming at the problems of low coulombic efficiency of the battery anode and poor battery circularity and stability caused by non-electrochemical corrosion of the anode electrode of the existing thermal regeneration battery.
A thermally regenerative tandem cell comprising:
a reactor;
the ion exchange membrane is arranged in the reactor and divides the reactor into an anode chamber and a cathode chamber;
the cathode electrode is arranged in the cathode chamber and suspended in the catholyte, and comprises a carbon material and sulfur arranged on the carbon material; a kind of electronic device with high-pressure air-conditioning system
And the anode electrode is arranged in the anode cavity and suspended in the anolyte, and comprises a carbon material, and cuprous sulfide and copper arranged on the carbon material.
In one embodiment, the reactor is provided with an anolyte injection hole for the anolyte to enter the anode chamber and a catholyte injection hole for the catholyte to enter the cathode chamber.
In one embodiment, the anolyte is a mixed solution of sulfate and ethylenediamine.
In one embodiment, the catholyte is a mixed solution of copper salt and sulfate.
In one embodiment, the catholyte is CuSO 4 And Li (lithium) 2 SO 4 Is a mixed solution of (a) and (b).
In one embodiment, the carbon material is carbon felt, carbon paper or carbon cloth.
In one embodiment, the reactor further comprises one or more seals, one or more of which are used to prevent electrolyte from leaking out of the reactor.
A method for preparing a thermal regenerative tandem cell, which is used for preparing the thermal regenerative tandem cell according to any one of the above, comprising the following steps:
preparing a cathode electrode, wherein the cathode electrode comprises a carbon material and sulfur arranged on the carbon material;
preparing an anode electrode, wherein the anode electrode comprises a carbon material and cuprous sulfide and copper which are arranged on the carbon material;
providing a reactor, embedding the cathode electrode into a cathode chamber and suspending in a catholyte, and embedding the anode electrode into an anode chamber and suspending in the anolyte.
In one embodiment, the step of preparing the cathode electrode specifically includes:
mixing sulfur powder, conductive carbon powder and polyvinylidene fluoride, adding N-methyl pyrrolidone, grinding to obtain slurry, uniformly coating the slurry on a carbon material substrate by using a scraper, and finally drying to obtain the cathode electrode.
In one embodiment, the step of preparing the anode electrode specifically includes:
the cathode electrode is used as a working electrode, the foam copper electrode is used as a counter electrode and a reference electrode, the cathode electrode and the foam copper electrode are placed in an electrolytic cell, catholyte is added to submerge the cathode electrode, and an electrochemical workstation is externally connected;
and reducing sulfur on the cathode electrode and copper ions in the electrolyte into cuprous sulfide by using current in the catholyte to obtain a carbon material-carried cuprous sulfide electrode, and further electrodepositing copper on the surface of the carbon material-carried cuprous sulfide electrode to obtain the anode electrode.
The thermal regeneration cascade battery and the preparation method thereof have at least the following advantages:
the cathode electrode and the anode electrode both adopt carbon structures which do not react with electrolyte as electrode substrates, so that the electrode structure is prevented from being damaged along with the reaction, the electrode can still keep a stable structure after multiple reactions, the non-electrochemical corrosion of the anode is successfully relieved, the conversion efficiency of the electrode is improved, and the stability of the electrode is effectively improved. The anode electrode has cuprous sulfide/copper, and the cuprous sulfide has promotion effect on the stripping process of copper in the anode electrolyte, so that copper can be stripped rapidly, thereby reducing side reaction and effectively improving anode coulomb efficiency. Meanwhile, the heat regeneration cascade battery of the two-stage electrochemical reaction is coupled, so that the power generation quantity of the battery is effectively improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described. Throughout the drawings, the elements or portions are not necessarily drawn to actual scale.
FIG. 1 is a schematic diagram of a thermal regeneration cascade cell according to an embodiment;
FIG. 2 is a flow chart of a method of making a thermally regenerated cascade battery in accordance with an embodiment;
FIG. 3 is a schematic illustration of the preparation of a cathode electrode;
FIG. 4 is a comparison of the electrical performance of a thermal regeneration cascade cell employing a sulfur carbon composite electrode, a thermal regeneration cell employing a sulfur carbon composite electrode, and a thermal regeneration ammonia cell employing a foam copper electrode;
FIG. 5 is a graph showing a comparison of the discharge performance of a thermally regenerated tandem cell employing a sulfur-carbon composite electrode versus a thermally regenerated cell employing a sulfur-carbon composite electrode;
fig. 6 is a cycle discharge curve of a thermally regenerated tandem cell employing a sulfur-carbon composite electrode.
Reference numerals:
10-reactor, 11-cathode chamber, 12-anode chamber, 13-catholyte injection hole, 14-anolyte injection hole, 15-cathode chamber, 16-cathode end plate, 17-anode chamber, 18-anode end plate, 20-ion exchange membrane, 30-cathode electrode, 40-anode electrode, 50-external circuit, 60-working electrode, 70-counter electrode, 80-electrolytic cell.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.
It will be understood that when an element is referred to as being "fixed 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 are used herein for illustrative purposes only and are not meant to be the only 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 herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Referring to fig. 1, a thermal regenerative tandem cell in one embodiment includes a reactor 10, an ion exchange membrane 20, a cathode electrode 30, and an anode electrode 40.
The reactor 10 is used for providing a space for electrochemical reaction, the ion exchange membrane 20 is arranged in the reactor 10, and the ion exchange membrane 20 divides the cavity of the reactor 10 into a cathode cavity 11 and an anode cavity 12. Wherein, the anode chamber 12 has an anolyte therein, and the cathode chamber 11 has a catholyte therein. A cathode electrode 30 is disposed in the cathode chamber 11 and suspended in the catholyte, the cathode electrode 30 comprising a carbon material and sulfur disposed on the carbon material. An anode electrode 40 is disposed in the anode chamber 12 and suspended in the anolyte, the anode electrode 40 comprising a carbon material and copper and cuprous sulfide disposed on the carbon material.
In the above-mentioned thermal regeneration cascade battery, electrons are reduced to cuprous sulfide by sulfur on the cathode electrode 30, and then copper ions in the solution further capture electrons to generate electrodeposition reaction on the surface of cuprous sulfide. The copper on the anode electrode 40 loses electrons and is oxidized to form a complex with ethylenediamine in the anolyte, and then cuprous sulfide continues to lose electrons and is oxidized to copper ions and elemental sulfur. During the electrochemical reaction, electrons migrate from anode electrode 40 to cathode electrode 30 through external circuit 50, forming a stable current.
In one embodiment, the reactor 10 is provided with a catholyte injection hole 13 and an anolyte injection hole 14, wherein anolyte is injected into the anode chamber 12 through the anolyte injection hole 14 and catholyte is injected into the cathode chamber 11 through the catholyte injection hole 13.
In one embodiment, the reactor 10 includes a cathode housing 15, a cathode end plate 16, an anode housing 17, and an anode end plate 18. Wherein an ion exchange membrane 20 separates the cathode housing 15 and the anode housing 17, a cathode end plate 16 encloses the cathode chamber 11, and an anode end plate 18 encloses the anode chamber 12. Wherein, the cathode electrolyte injection hole 13 is opened on the cathode casing 15, and the anode electrolyte injection hole 14 is opened on the anode casing 17.
In one embodiment, the reactor 10 body further includes one or more seals for preventing electrolyte from leaking out of the reactor 10. Specifically, the sealing members are sealing gaskets, and the sealing gaskets are arranged between the cathode end plate 16 and the cathode shell 15, between the anode end plate 18 and the anode shell 17, between the ion exchange membrane 20 and the cathode shell 15 and between the ion exchange membrane 20 and the anode shell 17, so that leakage of electrolyte is prevented.
In one embodiment, the anolyte is a mixed solution of sulfate and ethylenediamine. Specifically, the anolyte is Li 2 SO 4 And ethylenediamine. In one embodiment, the catholyte is a mixed solution of copper salt and sulfate. Specifically, the catholyte is CuSO 4 And Li (lithium) 2 SO 4 Is a mixed solution of (a) and (b). Of course, it will be appreciated that in other embodiments, the particular type of sulfate and copper salt may be flexibly selected as desired.
In one embodiment, the carbon material may be ground carbon paper, carbon cloth, carbon felt, carbon cotton, carbon foam, carbon black, carbon mesh, activated carbon, graphite, porous graphite, graphite powder, graphite particles, graphite fibers, or the like. Specifically, in the present embodiment, the carbon material is carbon cloth. The ion exchange membrane 20 is an anion exchange membrane AEM.
The working principle of the thermal regeneration cascade battery is as follows:
the cathode chamber 11 and the anode chamber 12 are separated by the ion exchange membrane 20, and because ethylenediamine is contained in the anolyte, the metallic copper plating layer on the surface of the anode electrode 40 is firstly subjected to complexation reaction with ethylenediamine to generate electrons and copper-ethylenediamine complex ions, and then cuprous sulfide loses electrons again and reacts with ethylenediamine to generate copper-ethylenediamine complex and elemental sulfur. The generated electrons are transferred to the cathode electrode 30 through the external circuit 50, sulfur on the cathode electrode 30 is reduced into cuprous sulfide by the electrons, then copper ions in the solution further capture the electrons, reduction reaction occurs, and a copper simple substance is generated and deposited on the surface of the cathode electrode 30. Anions in the cathode and anode migrate through the anion exchange membrane 20 to form an ionic current, forming a circuit loop. The cathode and anode reactions of the battery are as follows:
anode reaction:
①Cu(s)+2en(l)–2e – →Cu(en) 2 2+ (l)
②Cu 2 S(s)+4en(l)–4e – →2Cu(en) 2 2+ (l)+S(s)
cathode reaction:
①S(s)+2Cu 2+ +4e – →Cu 2 S(s)
②Cu 2+ +2e – →Cu(s)
by reacting the cathode electrode 30 with the anode electrode 40, the cell can continue to produce electricity, and the cell can stop producing electricity only when ethylenediamine in the anolyte or copper ions in the catholyte 30 are depleted. During the reaction, the concentration of copper ammonia complex in the anolyte increases and copper ions in the catholyte are continuously reduced on the cathode electrode 30. In addition, the total loading of copper sulfide and copper on anode electrode 40 also affects cell power production, and when both copper and copper are depleted, the cell stops generating power.
Referring to fig. 2, the invention also provides a method for preparing the thermal regeneration cascade battery, which is used for preparing the thermal regeneration cascade battery. Specifically, the preparation method comprises the following steps:
step S110: cathode electrode 30 is prepared, cathode electrode 30 comprising a carbon material and sulfur disposed on the carbon material.
Specifically, sulfur powder, conductive carbon powder and polyvinylidene fluoride are mixed, an appropriate amount of N-methyl pyrrolidone NMP is added for grinding, the mixture is made into a slurry state, then a scraper is used for uniformly coating the slurry on a carbon cloth substrate, and finally the cathode electrode 30 is obtained by drying. In one embodiment, the mass ratio of the sulfur powder, the conductive carbon powder and the polyvinylidene fluoride is 7:2:1.
Step S120: anode electrode 40 was prepared, anode electrode 40 comprising a carbon material and copper sulfide disposed on the carbon material.
Referring to fig. 3, specifically, the cathode electrode 30 is used as the working electrode 60, the copper foam electrode is used as the counter electrode 70 and the reference electrode, and is placed in the electrolytic cell 80, and the catholyte is added to submerge the electrodes, and an electrochemical workstation is externally connected. Sulfur on the cathode electrode 30 and copper ions in the electrolyte are reduced to cuprous sulfide in the catholyte by using small current to obtain a carbon cloth-carried cuprous sulfide electrode, and copper is further electrodeposited on the surface of the carbon cloth-carried cuprous sulfide electrode to obtain the anode electrode 40.
Step S130: the reactor 10 is provided with the cathode electrode 30 embedded in the cathode chamber 11 and suspended in the catholyte and the anode electrode 40 embedded in the anode chamber 12 and suspended in the anolyte.
Specifically, the reactor 10 includes a cathode casing 15, a cathode end plate 16, an anode casing 17, and an anode end plate 18, the cathode casing 15 and the anode casing 17 are disposed on the left and right sides of the ion exchange membrane 20, respectively, and the cathode chamber 11 and the anode chamber 12 are provided with a catholyte and an anolyte, respectively. The cathode casing 15 is provided at an upper side thereof with a cathode electrolyte injection hole 13, and the cathode electrode 30 is inserted into the cathode chamber 11 and is closely attached to the anion exchange membrane 20. An anolyte injection hole 14 is provided on the upper side of the anode casing 17, and an anode electrode 40 is inserted into the anode chamber 12 and is in close contact with the anion exchange membrane 20. The cathode end plate 16 and the anode end plate 18 are respectively arranged outside the cathode chamber 11 and the anode chamber 12, and the establishment of the thermal regeneration cascade battery is completed.
According to the thermal regeneration cascade battery and the preparation method thereof, the cathode electrode 30 and the anode electrode 40 both adopt carbon structures which do not react with electrolyte as electrode substrates, so that the electrode structures are prevented from being damaged along with the progress of the reaction, the electrode can still keep a stable structure after multiple reactions, the non-electrochemical corrosion of the anode is successfully relieved, the conversion efficiency of the electrode is improved, and the stability of the electrode is effectively improved. The anode electrode 40 has cuprous sulfide/copper, and the cuprous sulfide has promotion effect on the stripping process of copper in the anolyte, so that copper can be stripped rapidly, thereby reducing side reaction and effectively improving anode coulomb efficiency. Meanwhile, the cathode electrode 30 and the anode electrode 40 both generate two-stage electrochemical reaction, and the heat regeneration cascade battery of the two-stage electrochemical reaction is coupled, so that the power generation quantity of the battery is effectively improved.
The following is a comparison of the advantages of the thermal regeneration cascade battery according to the invention by means of thermal regeneration batteries under three working conditions:
as can be seen by comparing the working conditions in fig. 4, the maximum performance of the thermal regeneration cascade battery using the sulfur-carbon composite electrode and the thermal regeneration battery using the sulfur-carbon composite electrode is higher than that of the thermal regeneration ammonia battery using the foam copper electrode by 77% and 27%, respectively, and the open circuit voltages of the thermal regeneration cascade battery using the sulfur-carbon composite electrode and the thermal regeneration battery using the sulfur-carbon composite electrode are 890mV and 650mV, respectively, which are higher than that of the thermal regeneration ammonia battery using the foam copper electrode. The open circuit voltage of the thermal regeneration cascade battery adopting the sulfur-carbon composite electrode and the thermal regeneration battery adopting the sulfur-carbon composite electrode is higher, and the maximum power output is higher.
Fig. 5 shows the comparison of the electricity generation performance of the thermal regeneration cascade battery using the sulfur-carbon composite electrode and the thermal regeneration battery using the sulfur-carbon composite electrode, because the anode electrode 40 of the thermal regeneration cascade battery using the sulfur-carbon composite electrode is plated with a certain amount of metallic copper on the surface of the cuprous sulfide carried by carbon cloth, the primary electrochemical reaction is increased, so that the capacity and the energy density of the battery are obviously improved. Meanwhile, according to fig. 6, the capacity and the current density of the thermal regeneration cascade battery adopting the sulfur-carbon composite electrode do not have obvious attenuation in 20 cycles, which indicates that the thermal regeneration cascade battery adopting the sulfur-carbon composite electrode has good electricity generation stability.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention, and are intended to be included within the scope of the appended claims and description.
Claims (10)
1. A thermally regenerative tandem cell comprising:
a reactor;
the ion exchange membrane is arranged in the reactor and divides the reactor into an anode chamber and a cathode chamber;
the cathode electrode is arranged in the cathode chamber and suspended in the catholyte, and comprises a carbon material and sulfur arranged on the carbon material; a kind of electronic device with high-pressure air-conditioning system
And the anode electrode is arranged in the anode cavity and suspended in the anolyte, and comprises a carbon material, and cuprous sulfide and copper arranged on the carbon material.
2. The thermally regenerative tandem cell according to claim 1, wherein said reactor is provided with an anolyte injection hole for said anolyte to enter said anode chamber and a catholyte injection hole for said catholyte to be injected into said cathode chamber.
3. The thermally regenerative tandem cell of claim 1 wherein said anolyte is a mixed solution of sulfate and ethylenediamine.
4. The thermal regenerative tandem cell of claim 1, wherein said catholyte is a mixed solution of copper salt and sulfate.
5. The thermal regenerative tandem cell of claim 4, wherein said catholyte is CuSO 4 And Li (lithium) 2 SO 4 Is a mixed solution of (a) and (b).
6. The thermal regenerative tandem cell of claim 1, wherein said carbon material is carbon felt, carbon paper or carbon cloth.
7. The thermal regenerative tandem cell of claim 1, wherein said reactor further comprises one or more seals, one or more of said seals being configured to prevent electrolyte from leaking out of said reactor.
8. A method for producing a thermally regenerative tandem cell according to any one of claims 1 to 7, comprising the steps of:
preparing a cathode electrode, wherein the cathode electrode comprises a carbon material and sulfur arranged on the carbon material;
preparing an anode electrode, wherein the anode electrode comprises a carbon material and cuprous sulfide and copper which are arranged on the carbon material;
providing a reactor, embedding the cathode electrode into a cathode chamber and suspending in a catholyte, and embedding the anode electrode into an anode chamber and suspending in the anolyte.
9. The method for manufacturing a thermally regenerative tandem cell according to claim 8, wherein said step of manufacturing said cathode electrode is specifically:
mixing sulfur powder, conductive carbon powder and polyvinylidene fluoride, adding N-methyl pyrrolidone, grinding to obtain slurry, uniformly coating the slurry on a carbon material substrate by using a scraper, and finally drying to obtain the cathode electrode.
10. The method for producing a thermally regenerative tandem cell according to claim 8, wherein said step of producing said anode electrode is specifically:
the cathode electrode is used as a working electrode, the foam copper electrode is used as a counter electrode and a reference electrode, the cathode electrode and the foam copper electrode are placed in an electrolytic cell, catholyte is added to submerge the cathode electrode, and an electrochemical workstation is externally connected;
and reducing sulfur on the cathode electrode and copper ions in the electrolyte into cuprous sulfide by using current in the catholyte to obtain a carbon material-carried cuprous sulfide electrode, and further electrodepositing copper on the surface of the carbon material-carried cuprous sulfide electrode to obtain the anode electrode.
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