CN117374483A - Hydrogen-manganese electricity-changing type alkaline semi-fuel cell - Google Patents
Hydrogen-manganese electricity-changing type alkaline semi-fuel cell Download PDFInfo
- Publication number
- CN117374483A CN117374483A CN202311476789.3A CN202311476789A CN117374483A CN 117374483 A CN117374483 A CN 117374483A CN 202311476789 A CN202311476789 A CN 202311476789A CN 117374483 A CN117374483 A CN 117374483A
- Authority
- CN
- China
- Prior art keywords
- manganese
- hydrogen
- fuel cell
- electricity
- noble metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 117
- 239000011572 manganese Substances 0.000 title claims abstract description 117
- 239000000446 fuel Substances 0.000 title claims abstract description 49
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 50
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 39
- 239000001257 hydrogen Substances 0.000 claims abstract description 39
- 239000003792 electrolyte Substances 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000005611 electricity Effects 0.000 claims abstract 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 40
- 239000003054 catalyst Substances 0.000 claims description 26
- 238000009792 diffusion process Methods 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 23
- 239000012528 membrane Substances 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 230000003197 catalytic effect Effects 0.000 claims description 17
- 150000002697 manganese compounds Chemical class 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 230000002209 hydrophobic effect Effects 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000006258 conductive agent Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000002562 thickening agent Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 8
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910000765 intermetallic Inorganic materials 0.000 claims description 5
- 239000004745 nonwoven fabric Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000010425 asbestos Substances 0.000 claims description 4
- 229910052895 riebeckite Inorganic materials 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 7
- 229910003174 MnOOH Inorganic materials 0.000 description 6
- 239000007868 Raney catalyst Substances 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- -1 but not limited to Chemical class 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000003068 static effect Effects 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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
Abstract
The invention discloses a hydrogen-manganese electricity-exchanging type alkaline semi-fuel cell, which relates to the technical field of hydrogen energy and fuel cells and comprises an electricity-exchanging type manganese cathode and two diaphragms arranged on two sides of the electricity-exchanging type manganese cathode, wherein a non-noble metal hydrogen anode is arranged on the outer side of each diaphragm, alkaline aqueous electrolyte is filled in each diaphragm, and the electricity-exchanging type manganese cathode is detachably arranged between the two diaphragms. The hydrogen-manganese electricity-exchanging type alkaline semi-fuel cell can utilize hydrogen energy at low cost, and an electricity-exchanging type manganese cathode is arranged between two diaphragms and can be taken out or put in a movable mode, so that electricity exchanging or mechanical recharging of the cell is realized. The battery can be removed from the battery after the electricity-changing manganese cathode is discharged and replaced by a full-electricity manganese cathode, so that sustainable discharge of the battery is realized; the dismantled and discharged electricity-changing manganese cathode can be recovered and oxidized to a full-electricity state in a concentrated manner, so that recycling is realized.
Description
Technical Field
The invention relates to the technical field of hydrogen energy and fuel cells, in particular to the technical field of hydrogen-manganese electricity-exchanging type alkaline semi-fuel cells.
Background
In the context of "two carbons", hydrogen energy is considered as the best energy carrier for solving the national energy safety and environmental problems, while proton exchange membrane fuel cells are currently the terminal for hydrogen energy realizationThe mainstream technology used. Proton exchange membrane fuel cells have the advantages of high energy efficiency (not limited by Carnot cycle), zero emission, no noise, short time filling and the like, but outstanding cost (stack cost: about 3500 yuan/kW) severely limits the market-oriented overall development. In proton exchange membrane fuel cells, either the hydrogen oxidation reaction at the anode or the oxygen reduction reaction at the cathode, an electrocatalyst is required, but the cell is an acidic system, and only expensive noble metal-based catalysts such as Pt can be used as the catalyst. In addition, anode discharge product H + (or H) 3 O + ) Must pass through the perfluorosulfonic acid proton membrane to reach the cathode and react with O 2- The process for preparing the perfluorosulfonic acid membrane is complex and mainly depends on import (DuPont Nafion membrane, golgi select membrane and the like), and the price is also quite low. Typically, only noble metal catalysts and proton exchange membranes account for about 50% of the total stack cost. Obviously, if a novel fuel cell without a noble metal catalyst and a proton exchange membrane can be developed, hydrogen energy can be applied more cheaply, and positive influence is exerted on the hydrogen energy and fuel cell industry.
Disclosure of Invention
The invention aims at: in order to solve the technical problems, the invention provides a hydrogen-manganese electricity-changing type alkaline semi-fuel cell.
The invention adopts the following technical scheme for realizing the purposes:
the utility model provides a hydrogen manganese trades electric alkaline semi-fuel cell, includes electric core structure, electric core structure is including trading electric manganese cathode, setting is in two diaphragms of trading electric manganese cathode both sides, each the diaphragm outside all is provided with non-noble metal hydrogen positive pole, each the diaphragm is inside all to be filled with alkaline aqueous electrolyte, trade electric manganese cathode detachable setting is between two the diaphragm.
Specifically, the battery-changing manganese cathode is arranged between two diaphragms and can be movably taken out or put in, so that the battery cell can be changed or recharged mechanically. The battery can be removed from the battery after the electricity-changing manganese cathode is discharged and replaced by a full-electricity manganese cathode, so that sustainable discharge of the battery is realized; the dismantled and discharged manganese cathode can be recovered and oxidized to a full state in a concentrated manner, so that recycling is realized.
In one embodiment, the battery-changing manganese cathode comprises a movable manganese paste box, a cathode tab arranged on the top of the movable manganese paste box and manganese paste filled in the movable manganese paste box, wherein the movable manganese paste box is a porous metal current collector, so that the alkaline aqueous solution electrolyte can flow between the movable manganese paste box and the diaphragm.
Specifically, the movable manganese paste box shell adopts porous metal current collectors such as foam nickel, perforated nickel foil or perforated nickel plated steel belt, and the like, so that alkaline aqueous solution electrolyte can flow between the movable manganese paste box and the diaphragm.
In one embodiment, the manganese paste comprises the following components: 96-98wt% of high valence manganese compound, 1-2wt% of conductive agent, 1-2wt% of thickener and alkaline aqueous solution electrolyte.
In one embodiment, the high valence manganese compound is a compound having a valence state of manganese not lower than tetravalent, and upon discharge, the high valence manganese compound is reduced to a low valence manganese compound, which is a compound having a valence state of manganese lower than tetravalent.
Specifically, the manganese paste (electrode material) of the anode structure is a high valence manganese (+4, +6 or +7 valence) compound including, but not limited to, mnO 2 、K 2 MnO 4 、Na 2 MnO 4 、KMnO 4 、NaMnO 4 Upon discharge, the high valence manganese compound will be reduced to a low valence manganese (+2 or +3 valence) compound.
In one embodiment, the conductive agent is a carbon material; the thickening agent is polyacrylamide or sodium carboxymethyl cellulose.
Specifically, the conductive agent is a carbon material such as natural graphite, synthetic graphite, expanded graphite, acetylene black, ketjen black, etc.; the thickener may be polyacrylamide or sodium carboxymethyl cellulose. The composition of the alkaline aqueous electrolyte in the manganese paste is consistent with that in the separator.
In one embodiment, each non-noble metal hydrogen anode comprises a non-noble metal catalytic layer, a gas diffusion layer and an anode tab, wherein the non-noble metal catalytic layer and the gas diffusion layer are connected in a pasting mode, the anode tab is arranged at the top of the gas diffusion layer, and the non-noble metal catalytic layer is attached to the diaphragm contact on the corresponding side.
Specifically, the gas diffusion layer is arranged at the outermost side of the cell and uses a hydrophobic current collector; the non-noble metal catalytic layer is in close proximity to the gas diffusion layer. The gas diffusion layer and the non-noble metal catalytic layer together form a non-noble metal hydrogen anode.
In one embodiment, the material of the gas diffusion layer is hydrophobic carbon paper, foam nickel loaded with a hydrophobic and breathable material or nickel plated steel strip loaded with a hydrophobic and breathable material.
Specifically, the material of the gas diffusion layer includes, but is not limited to, hydrophobic carbon paper or foam nickel loaded with hydrophobic and breathable materials, nickel plated steel strips, and the like, and has the functions of both a hydrogen diffusion channel and a current collecting.
In one embodiment, the non-noble metal catalyst layer is internally filled with a non-noble metal catalyst, and the non-noble metal catalyst is one or more of an elementary substance of Ni, an elementary substance of Co, an alloy and an intermetallic compound.
Specifically, the non-noble metal catalyst is a non-noble metal catalyst, and the non-noble metal catalyst comprises one or more of N i simple substance, co simple substance, alloy and intermetallic compound, and the non-noble metal catalyst promotes the electrochemical oxidation reaction of hydrogen when discharging.
In one embodiment, each diaphragm is arranged between the corresponding non-noble metal catalytic layer and the movable manganese paste box, and the diaphragm is made of asbestos or PP/PE non-woven fabrics.
Specifically, the separator prevents shorting of the cells while storing sufficient alkaline aqueous electrolyte.
In one embodiment, the solute of the alkaline aqueous electrolyte in the membrane is a combination of alkali metal hydroxides, the solvent is water, and the membrane contains 3-4wt% of PEG-200 water retention agent.
Specifically, the solute of the alkaline aqueous solution electrolyte is a combination of alkali metal (such as potassium, sodium and lithium) hydroxides, the solvent is water, the concentration is 4-8wt% and the aqueous solution electrolyte can contain 3-4wt% of PEG-200 water retention agent.
The beneficial effects of the invention are as follows:
1. the hydrogen-manganese electricity-changing type alkaline semi-fuel cell can utilize hydrogen energy at low cost, and is suitable for large-scale static hydrogen energy power generation. Compared with a proton exchange membrane fuel cell, the hydrogen-manganese electricity-exchanging type alkaline semi-fuel cell has the following beneficial effects:
1) The electrolyte of the proton exchange membrane fuel cell is acidic, and only the noble metal catalyst can work stably; the electrolyte of the hydrogen-manganese semi-fuel cell is alkaline, and the non-noble metal catalyst can also work stably, so that the cost of the cell is greatly reduced.
2) The carrier of the proton exchange membrane fuel cell is H + Specific proton transfer can be realized only by proton membranes such as perfluorosulfonic acid membranes, and the membrane has high technical barriers and strict patent protection; the carrier of the hydrogen/manganese semi-fuel cell is OH - The battery cost can be further reduced by using an extremely low-cost common separator such as asbestos and PP/PE nonwoven fabric.
2. Compared with an alkaline fuel cell, the hydrogen-manganese electricity-changing type alkaline semi-fuel cell has the following beneficial effects:
1) Alkaline fuel cells employ an alkaline aqueous electrolyte without the need for precious metal catalysts and proton exchange membranes, but the oxygen cathode of the cell is operated in the atmosphere, which makes the alkaline electrolyte susceptible to CO 2 Poisoning and resulting in increased internal resistance and deteriorated performance of the battery; the manganese cathode of the hydrogen-manganese semi-fuel cell is not exposed to the atmosphere, and the problem of electrolyte carbonation is avoided.
2) The oxygen cathode of the alkaline fuel cell adopts Ag, N i and other metal micro-nano catalysts, and the manganese cathode of the hydrogen/manganese semi-fuel cell adopts high-valence manganese compounds (such as MnO 2 ) The latter has extremely obvious cost advantages over the former.
3. Compared with an alkaline zinc/manganese cell, the hydrogen-manganese electricity-changing alkaline semi-fuel cell has the following beneficial effects:
the zinc/manganese battery is used as a primary battery, and the endurance of the battery is determined by the batteryZn and MnO contained therein 2 Is determined by the amount of (2); the hydrogen-manganese semi-fuel cell belongs to a power generation device, and can realize continuous discharge as long as a hydrogen anode and a manganese cathode are continuously filled with fuel.
Drawings
FIG. 1 is a schematic diagram of the cell structure of a hydrogen-manganese power conversion type alkaline half-fuel cell;
FIG. 2 is a view of manganese hydrogen (H) 2 /MnO 2 ) Schematic diagram of reaction mechanism of a power-conversion type alkaline semi-fuel cell;
FIG. 3 is a view of manganese hydrogen (H) 2 /MnO 2 ) A discharge curve of the power-change alkaline half-fuel cell;
reference numerals: 1-gas diffusion, 2-non-noble metal catalytic layer, 3-diaphragm, 4-movable manganese paste box, 5-cathode tab and 6-anode tab.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures. Furthermore, the terms "first," "second," and the like, are used merely to distinguish between descriptions and should not be construed as indicating or implying relative importance.
In describing embodiments of the present invention, it should be noted that the directions or positional relationships indicated by the terms "inner", "outer", "upper", etc. are directions or positional relationships based on those shown in the drawings, or those that are conventionally put in place when the inventive product is used, are merely for convenience of description and simplification of description, and are not indicative or implying that the apparatus or element in question must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
Example 1
As shown in fig. 1, this embodiment provides a hydrogen-manganese electricity-exchanging alkaline semi-fuel cell, which comprises a cell structure, wherein the cell structure comprises an electricity-exchanging manganese cathode, and two diaphragms 3 arranged on two sides of the electricity-exchanging manganese cathode, the outer sides of the diaphragms 3 are all provided with non-noble metal hydrogen anodes, alkaline aqueous electrolyte is filled in the diaphragms 3, and the electricity-exchanging manganese cathode is detachably arranged between the two diaphragms 3.
Specifically, the battery-changing manganese cathode is arranged between two diaphragms 3 and can be movably taken out or put in, so that the battery cell can be changed or recharged mechanically. The battery can be removed from the battery after the electricity-changing manganese cathode is discharged and replaced by a full-electricity manganese cathode, so that sustainable discharge of the battery is realized; the dismantled and discharged manganese cathode can be recovered and oxidized to a full state in a concentrated manner, so that recycling is realized.
Example 2
The embodiment is further optimized based on the embodiment 1, specifically:
the electricity-changing manganese cathode comprises a movable manganese paste box 4, a cathode lug 5 arranged at the top of the movable manganese paste box 4 and manganese paste filled in the movable manganese paste box 4, wherein the movable manganese paste box 4 is a porous metal current collector, so that an alkaline aqueous solution electrolyte can circulate between the movable manganese paste box 4 and a diaphragm 3.
Specifically, the shell of the movable manganese paste box 4 adopts porous metal current collectors such as foam nickel, perforated nickel foil or perforated nickel plated steel belt, and the like, so that alkaline aqueous solution electrolyte can flow between the movable manganese paste box 4 and the diaphragm 3.
Example 3
This example was further optimized on the basis of example 2, specifically:
the manganese paste comprises the following components: 96-98wt% of high valence manganese compound, 1-2wt% of conductive agent, 1-2wt% of thickener and alkaline aqueous solution electrolyte.
The high valence manganese compound is a compound with the valence state of manganese not lower than tetravalent, and when the discharge is carried out, the high valence manganese compound is reduced to be a low valence manganese compound, and the low valence manganese compound is a compound with the valence state of manganese lower than tetravalent.
Specifically, the manganese paste (electrode material) of the anode is a high valence manganese (+4, +6 or +7 valence) compound including, but not limited to, mnO 2 、K 2 MnO 4 、Na 2 MnO 4 、KMnO 4 、NaMnO 4 Upon discharge, the high valence manganese compound will be reduced to a low valence manganese (+2 or +3 valence) compound.
The conductive agent is a carbon material; the thickening agent is polyacrylamide or sodium carboxymethyl cellulose.
Specifically, the conductive agent is a carbon material such as natural graphite, synthetic graphite, expanded graphite, acetylene black, ketjen black, etc.; the thickener may be polyacrylamide or sodium carboxymethyl cellulose. The composition of the alkaline aqueous electrolyte in the manganese paste is consistent with that in the separator.
The conductive agent is a carbon material; the thickener is polyacrylamide or sodium carboxymethyl cellulose.
Specifically, the conductive agent is a carbon material such as natural graphite, synthetic graphite, expanded graphite, acetylene black, ketjen black, etc.; the thickener may be polyacrylamide or sodium carboxymethyl cellulose. The composition of the alkaline aqueous electrolyte in the manganese paste is consistent with that in separator 3.
Example 4
This embodiment is further optimized based on any one of embodiments 1 to 3, specifically:
each non-noble metal hydrogen anode structure comprises a non-noble metal catalytic layer 2, a gas diffusion layer 1 and an anode lug 6, wherein the non-noble metal catalytic layer 2 and the gas diffusion layer 1 are connected in a pasting mode, the anode lug 6 is arranged at the top of the gas diffusion layer 1, and the non-noble metal catalytic layer 2 is attached to the contact of the diaphragm 3 at the corresponding side.
Specifically, the gas diffusion layer 1 is arranged at the outermost side of the cell, and a hydrophobic current collector is used; the non-noble metal catalytic layer 2 is in close proximity to the gas diffusion layer 1. The gas diffusion layer 1 and the non-noble metal catalytic layer 2 together constitute a non-noble metal hydrogen anode.
Example 5
This example was further optimized on the basis of example 4, and specifically:
the gas diffusion layer 1 is made of hydrophobic carbon paper, foam nickel loaded with hydrophobic and breathable materials or nickel-plated steel strip loaded with hydrophobic and breathable materials.
Specifically, the material of the gas diffusion layer 1 includes, but is not limited to, hydrophobic carbon paper or foam nickel loaded with hydrophobic and breathable materials, nickel plated steel strips, and the like, and has the functions of both a hydrogen diffusion channel and a current collecting.
The non-noble metal catalyst layer 2 is filled with a non-noble metal catalyst, and the non-noble metal catalyst is one or more of an Ni simple substance, a Co simple substance, an alloy and an intermetallic compound.
Specifically, the non-noble metal catalyst is a non-noble metal catalyst, and the non-noble metal catalyst comprises one or more of an Ni simple substance, a Co simple substance, an alloy and an intermetallic compound, and the non-noble metal catalyst promotes the electrochemical oxidation reaction of hydrogen when discharging.
Each diaphragm 3 is arranged between the corresponding non-noble metal catalytic layer 2 and the movable manganese paste box 4, and the diaphragm 3 is made of asbestos or PP/PE non-woven fabrics.
Specifically, the separator 3 prevents the cell from being short-circuited while storing sufficient alkaline aqueous electrolyte.
The solute of the alkaline aqueous solution electrolyte in the diaphragm 3 is a combination of alkali metal hydroxides, the solvent is water, and the water-retaining agent contains 3-4wt% of PEG-200 water-retaining agent.
Specifically, the solute of the alkaline aqueous solution electrolyte is a combination of alkali metal (such as potassium, sodium and lithium) hydroxides, the solvent is water, the concentration is 4-8wt% and the aqueous solution electrolyte can contain 3-4wt% of PEG-200 water retention agent.
Example 6
The present example provides manganese (H) 2 /MnO 2 ) The electricity-changing type alkaline semi-fuel cell comprises the following specific components:
as shown in FIG. 2, in MnO 2 As an example of a hydrogen-manganese electro-change type alkaline semi-fuel cell with a cathode material and Raney nickel as a non-noble metal catalyst, the discharge reaction is as follows:
and (3) cathode: mnO (MnO) 2 +H 2 O+e - →MnOOH+OH - ；
Anode: 1/2H 2 +OH - →H 2 O+e - ；
A battery: mnO (MnO) 2 +1/2H 2 →MnOOH；
MnO in the movable manganese paste case 4 during discharge 2 Is reduced to MnOOH and generates OH - ，OH - The hydrogen migrates to the surface of the Raney nickel catalyst of the hydrogen anode through the alkaline electrolyte aqueous solution, and simultaneously the hydrogen diffuses to the surface of the Raney nickel of the hydrogen anode through the gas diffusion layer 1. And hydrogen is subjected to hydrogen oxidation reaction and reacts with OH under the promotion of Raney nickel - The combination forms water. MnO in the movable manganese paste case 4 2 After being reduced to MnOOH (i.e. after the capacity of the manganese cathode is exhausted), the discharging movable manganese paste box 4 is taken out, and a new full-electric movable manganese paste box 4 is filled, so that the cathode is replaced or mechanically recharged, and the battery can be discharged continuously. In addition, the discharge product MnOOH in the discharge-state mobile manganese paste case 4 can be regenerated by oxidation:
MnOOH+1/4O 2 →MnO 2 +1/2H 2 O。
example 7
FIG. 3 is a schematic diagram of an embodiment of the present disclosure of manganese (H) 2 /MnO 2 ) Discharge curve of a battery-replaceable alkaline half-fuel cell. The embodiment uses H 2 /MnO 2 For example, the H is an electricity-exchanging type alkaline semi-fuel cell 2 /MnO 2 The non-noble metal catalyst of the non-noble metal hydrogen anode of the electricity-changing type alkaline semi-fuel cell is Raney nickel, the catalytic layer is composed of 90wt% of Raney nickel and 10wt% of demulsified PTFE, and the Raney nickel is loaded with about 50mg cm -2 The method comprises the steps of carrying out a first treatment on the surface of the The gas diffusion layer 1/current collector is PTFE water-blocking breathable film/nickel screen. Movable manganese pasteThe casing of the box 4 adopts a perforated nickel-plated steel belt, and the manganese paste is prepared by uniformly mixing 97wt% of electrolytic manganese dioxide, 2wt% of acetylene black and 1wt% of sodium carboxymethylcellulose by using 7M KOH aqueous solution, and the rated capacity is 800mAh. The diaphragm 3 adopts a PE non-woven fabric diaphragm, and the electrolyte of the alkaline aqueous solution is 7M KOH aqueous solution. The anode end of the battery is connected with hydrogen, the hydrogen pressure is 1.5bar, once the electric quantity of the cathode end of the battery is exhausted, the new movable manganese paste box 4 is replaced, the battery is discharged all the time, and the output voltage is more than or equal to 1V (current 160 mA).
Claims (10)
1. The utility model provides a hydrogen manganese trades electric alkaline semi-fuel cell which characterized in that, includes electric core structure, electric core structure includes trading electric manganese negative pole, sets up two diaphragms (3) of trading electric manganese negative pole both sides, each diaphragm (3) outside all is provided with non-noble metal hydrogen positive pole, and each diaphragm (3) are inside all to be filled with alkaline aqueous electrolyte, trading electric manganese negative pole structure detachably and setting up between two diaphragm (3).
2. The hydrogen-manganese power conversion alkaline semi-fuel cell according to claim 1, wherein the power conversion type manganese cathode comprises a movable manganese paste box (4), a cathode lug (5) arranged on the top of the movable manganese paste box (4), and manganese paste filled in the movable manganese paste box (4), wherein the movable manganese paste box (4) is a porous metal current collector, so that an alkaline aqueous solution electrolyte can flow between the movable manganese paste box (4) and the diaphragm (3).
3. The hydrogen-manganese refuelable alkaline semi-fuel cell of claim 2, the manganese paste comprising the following components: 96-98wt% of high valence manganese compound, 1-2wt% of conductive agent, 1-2wt% of thickener and alkaline aqueous solution electrolyte.
4. A hydrogen-manganese refuelable alkaline half fuel cell as claimed in claim 3, characterized in that the higher manganese compound is a compound having a valence of manganese not lower than four, and that upon discharge the higher manganese compound is reduced to a lower manganese compound, which is a compound having a valence of manganese lower than four.
5. A hydrogen-manganese refuelable alkaline semi-fuel cell as in claim 3, wherein the conductive agent is a carbon material; the thickening agent is polyacrylamide or sodium carboxymethyl cellulose.
6. The hydrogen-manganese power conversion type alkaline semi-fuel cell according to claim 1, wherein each non-noble metal hydrogen anode comprises a non-noble metal catalytic layer (2), a gas diffusion layer (1) and an anode tab (6), the non-noble metal catalytic layer (2) and the gas diffusion layer (1) are connected in a pasting mode, the anode tab (6) is arranged on the top of the gas diffusion layer (1), and the non-noble metal catalytic layer (2) is attached to the separator (3) on the corresponding side in contact.
7. The hydrogen-manganese electricity exchanging type alkaline semi-fuel cell according to claim 6, wherein the gas diffusion layer (1) is made of hydrophobic carbon paper, foam nickel loaded with a hydrophobic and air permeable material or nickel plated steel strip loaded with a hydrophobic and air permeable material.
8. A hydrogen-manganese refuelable alkaline semi-fuel cell as in claim 6, wherein,
the non-noble metal catalyst layer (2) is internally filled with a non-noble metal catalyst, and the non-noble metal catalyst is one or more of an Ni simple substance, a Co simple substance, an alloy and an intermetallic compound.
9. The hydrogen-manganese electricity exchanging type alkaline semi-fuel cell according to claim 1, wherein the material of the diaphragm (3) is asbestos or PP/PE non-woven fabric.
10. The hydrogen-manganese electricity exchanging type alkaline semi-fuel cell according to claim 9, wherein the solute of the alkaline aqueous electrolyte in the membrane (3) is an alkali metal hydroxide combination, the solvent is water, and the water-retaining agent of PEG-200 is contained in an amount of 3-4 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311476789.3A CN117374483A (en) | 2023-11-07 | 2023-11-07 | Hydrogen-manganese electricity-changing type alkaline semi-fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311476789.3A CN117374483A (en) | 2023-11-07 | 2023-11-07 | Hydrogen-manganese electricity-changing type alkaline semi-fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117374483A true CN117374483A (en) | 2024-01-09 |
Family
ID=89392790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311476789.3A Pending CN117374483A (en) | 2023-11-07 | 2023-11-07 | Hydrogen-manganese electricity-changing type alkaline semi-fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117374483A (en) |
-
2023
- 2023-11-07 CN CN202311476789.3A patent/CN117374483A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5207407B2 (en) | Air electrode | |
| JP2008539328A (en) | Electrochemical method for producing and storing hydrogen by redox of zinc and water | |
| Zhang et al. | An overview of non-noble metal electrocatalysts and their associated air cathodes for Mg-air batteries | |
| JP3959749B2 (en) | Metal hydride secondary battery with solid polymer electrolyte | |
| CN101165964A (en) | Asymmetric secondary air fuel battery | |
| Zhou et al. | Fe-Co dual atomic doublets on N, P codoped carbon as active sites in the framework of heterostructured hollow fibers towards high-performance flexible Zn-Air battery | |
| CN109428138A (en) | The preparation method and lithium-air battery of lithium-air battery | |
| CN102437348B (en) | Non-noble metal-catalyzed polymer fibrous membrane hydroborate fuel cell | |
| CN101752629A (en) | Rechargeable metal hydride air battery with auxiliary electrode | |
| US5480741A (en) | Cell provided with gaseous diffusion electrode, and method of charging and discharging the same | |
| CN100593877C (en) | Composite membrane electrode of direct borohydride fuel cell | |
| JP2017112036A (en) | Fuel battery | |
| CN113363629A (en) | Aqueous carbon-hydrogen secondary battery | |
| CN108365238A (en) | A kind of liquid-metal fuel cell | |
| CN115228474B (en) | Metal colloid catalyst for oxygen evolution reaction under alkaline condition and preparation method and application thereof | |
| CN116387532A (en) | Hydrogen electrode and preparation method and application thereof | |
| CN200941417Y (en) | Zn-air cell | |
| JP3746047B2 (en) | Liquid fuel cell and power generator using the same | |
| CN113363411B (en) | Positive electrode for nickel-hydrogen secondary battery, preparation method of positive electrode and nickel-hydrogen secondary battery | |
| CN117374483A (en) | Hydrogen-manganese electricity-changing type alkaline semi-fuel cell | |
| JP3846727B2 (en) | Liquid fuel cell and power generator using the same | |
| CN206364157U (en) | A kind of lithium-oxygen battery | |
| CN214570758U (en) | Nickel cobalt selenide material, preparation device, electrode and NiCo-Zn alkaline battery | |
| US20060078764A1 (en) | Dissolved fuel alkaline fuel cell | |
| CN113948798A (en) | Alkaline tin air battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |