CN114784424B - Non-alkaline zinc air battery based on zinc peroxide anode - Google Patents
Non-alkaline zinc air battery based on zinc peroxide anode Download PDFInfo
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- 239000011701 zinc Substances 0.000 title claims abstract description 112
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229940105296 zinc peroxide Drugs 0.000 title claims abstract description 85
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 55
- 239000003792 electrolyte Substances 0.000 claims abstract description 63
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 150000003751 zinc Chemical class 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000007599 discharging Methods 0.000 abstract description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 5
- 239000001569 carbon dioxide Substances 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
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- 230000000694 effects Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
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- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
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- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 238000007086 side reaction Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- 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
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-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
-
- 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Inorganic Chemistry (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses a non-alkaline zinc-air battery based on a zinc peroxide anode, and belongs to the technical field of batteries. The non-alkaline zinc-air battery sequentially comprises a metal zinc negative electrode, a non-alkaline electrolyte and a zinc peroxide positive electrode from the negative electrode to the positive electrode. The non-alkaline zinc-air battery disclosed by the invention has the following advantages: the discharging and charging cycle life of the battery is greatly prolonged; the device can perform stable discharge and charge cycle operation in air, has the operation capability of high current density and low current density, and has higher charge and discharge energy efficiency; the battery has a simple structure, and an additional oxygen supply and carbon dioxide removal device is not needed; the corrosion resistance requirement of the battery assembly is low, and the battery assembly is easy to realize low-cost mass production and application.
Description
Technical Field
The invention relates to a non-alkaline zinc-air battery based on a zinc peroxide anode, and belongs to the technical field of batteries.
Background
The development of world energy is faced with the climate and environmental crisis caused by shortage of fossil fuel resources and the traditional energy utilization mode, and the development of efficient clean utilization technology of fossil energy and the development of renewable energy are fundamental ways for solving the energy problem, wherein the electrochemical energy technology plays an important role. The lithium ion battery system is an important representative of electrochemical energy technology and is widely applied to the scenes of portable electronic equipment, electric automobiles, small-sized power grid energy storage and the like. However, with the popularization and application of megawatt-level and gigawatt-level large-scale energy storage technologies, the demand for lithium is greatly increased, and the development of lithium ion batteries has a raw material resource crisis. Therefore, the development of a novel secondary battery technology with rich raw material resources is a great demand for the current socioeconomic development.
The zinc-air battery is generally composed of a zinc metal negative electrode, an alkaline electrolyte and an air positive electrode, has the safety characteristics of rich resources of electrode and electrolyte raw materials and nonflammability, has higher theoretical energy density (1353 Wh/kg), and is a battery technology with potential to meet the electrochemical energy storage requirement. However, the alkaline zinc-air battery still faces serious problems in application, such as poor cycle stability, low energy conversion efficiency, low power density and the like.
The structure of the alkaline air battery is shown in fig. 23, and the main reason for the above-mentioned problems is alkaline electrolysis which is widely used thereinAnd (3) liquid: (1) Zinc metal negative electrode side is easy to generate zinc oxide byproducts in the discharging and charging cycle process, and the byproducts have poor conductivity and are adhered to the surface of the zinc negative electrode, so that the electrochemical reversibility of the zinc negative electrode side is poor, and the effective utilization rate is low; (2) The reaction at the positive electrode side is a four-electron reaction of oxygen, the reaction involves multi-step electron transfer with complex process, and has the problems of poor reversibility, high overpotential, slow dynamics and the like, and a catalyst with complex structure and high price is usually required to be loaded at the positive electrode side; (3) The alkaline electrolyte is liable to undergo side reaction with carbon dioxide in the air to produce carbonate (such as K) 2 CO 3 ) The byproducts are easy to block the air transmission channel of the porous anode, the circulation stability of the battery is seriously affected, and an additional carbon dioxide removal or pure oxygen supply device is also required for ensuring the long-term operation of the battery, so that the cost and the complexity of the battery device are greatly increased. In addition, the alkaline electrolyte also has strong corrosiveness, so that the alkaline electrolyte has serious corrosion effects on zinc metal cathodes, air anodes, battery components and the like, and the service life of the zinc-air battery is greatly shortened.
The prior art journal of Science, pages 371, 46 to 51, reports the use of Zn (CF) at a concentration of 1mol/L,2mol/L,3mol/L 3 SO 3 ) 2 The zinc-air secondary battery based on zinc peroxide is prepared by zinc salt electrolyte, which is a technology developed by the team and belongs to the preliminary stage. The type and concentration of the electrolyte reported in the document are simply explored, and the prepared zinc-air secondary battery can only be used for a current density of 0.1-4.0 mA/cm 2 The operation is performed in the interval, and indexes such as charge and discharge time, cycle times, energy efficiency and the like are still to be improved so as to meet the requirements of different application scenes. In addition, the air battery reported in the document not only requires an additional oxygen supply device, but also has the problem of evaporation of the electrolyte in an open system, and has limited application.
As described above, the conventional alkaline zinc-air battery has problems of electrochemical irreversibility and poor chemical stability due to the highly corrosive high-concentration alkaline electrolyte, and 1mol/L,2mol/L and 3mol/L Zn (CF) has been used in the prior art 3 SO 3 ) 2 Zinc air battery technology of zinc salt electrolyte also has the problem of limited application. Thus, the present inventionThe invention provides more non-alkaline electrolyte types, and defines the corresponding concentration range, so that key indexes such as charge and discharge time, cycle times, energy efficiency and the like of the zinc-air secondary battery under the condition of wider charge and discharge current density can be effectively improved. On the basis, the invention can use the chemically synthesized zinc peroxide anode, thereby needing no additional oxygen supply device, being capable of using a closed battery system to avoid the difficult problem of evaporation of electrolyte and being capable of promoting the effective application of the zinc-air secondary battery in different scenes.
Disclosure of Invention
Aiming at the problems of the existing zinc-air battery technology, the invention provides a non-alkaline zinc-air battery based on a zinc peroxide anode.
As shown in the attached figure 1 of the specification, the technical scheme of the invention is as follows: a non-alkaline zinc air battery based on a zinc peroxide anode, which sequentially comprises a metal zinc anode, a non-alkaline electrolyte and a zinc peroxide anode from the anode to the cathode; the zinc peroxide positive electrode sequentially comprises zinc peroxide, a conductive layer and a breathable current collector.
The metal zinc cathode is made of zinc foil or zinc powder; the zinc foil has a thickness of 20 to 1000 microns, preferably 50 microns. The zinc powder electrode consists of zinc powder with the particle size of 0.02-200 microns, preferably 0.05 microns and a binder, wherein the binder is Polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVDF), preferably PTFE.
The non-alkaline electrolyte consists of an aqueous solution of an inorganic zinc salt, wherein the inorganic zinc salt is Zn [ N (CF) 3 SO 2 ) 2 ] 2 ,Zn(CF 3 SO 3 ) 2 ,Zn(CF 3 CO 2 ) 2 ,Zn(PF 6 ) 2 ,Zn(BF 4 ) 2 ,ZnSO 4 ,Zn(CH 3 CO 2 ) 2 ,Zn(ClO 4 ) 2 ,Zn(NO 3 ) 2 ,ZnCl 2 ,ZnBr 2 Preferably Zn [ N (CF) 3 SO 2 ) 2 ] 2 Or Zn (CF) 3 SO 3 ) 2 Or Zn [ N (CF) 3 SO 2 ) 2 ] 2 And Zn (CF) 3 SO 3 ) 2 Is a mixed solution of (a) and (b); the concentration of the electrolyte is 0.1 to 4mol/L, preferably 1.5mol/L.
Further, the non-alkaline electrolyte has a ph of 1< 7.
The zinc peroxide can be generated by in-situ electrochemical reaction in a discharging process, and the metal zinc cathode, the non-alkaline electrolyte and the breathable current collector covered with the conductive layer are assembled into the non-alkaline zinc-air battery. The breathable current collector covered with the conductive layer is prepared by uniformly mixing a conductive agent and a binder and coating the mixture on the breathable current collector.
Further, the conductive agent comprises one or more of carbon black, carbon nanotubes and graphene, preferably carbon black; the binder comprises one or more of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), nafion solution, preferably PTFE. The breathable current collector layer is one or more of carbon paper, carbon cloth, stainless steel mesh, metal mesh and foam metal, and is preferably carbon paper.
The discharge condition of the non-alkaline zinc-air battery for generating zinc peroxide in situ comprises that the current density is 0.01-30 mA/cm 2 Preferably 0.2mA/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The discharge time is 0.05 to 70 hours, preferably 5 hours. The characteristic reaction process is 2e - /O 2 (i.e., 2 electron transfers per 1 oxygen molecule reduced) oxygen reduction reactions. The zinc peroxide contained in the positive electrode is decomposed in the charging reaction process (namely, the electrochemical oxygen precipitation reaction process), and the characteristic reaction process is 2e - /O 2 (i.e. 2 electron transfer per 1 oxygen molecule is oxidized and separated out) oxygen precipitation reaction. After the discharge is finished, zinc peroxide is formed on the surface of the positive electrode conducting layer at the side contacting the electrolyte, and the non-alkaline zinc air battery based on the zinc peroxide positive electrode can be manufactured.
The zinc peroxide can be synthesized by chemical reaction, and the precipitation product obtained by uniformly mixing and stirring the saline solution containing divalent zinc ions with hydrogen peroxide, heating and finally standing is the zinc peroxide. The aqueous solution of divalent zinc ion salt can be selected from inorganic zinc salt as Zn [ N (CF) 3 SO 2 ) 2 ] 2 ,Zn(CF 3 SO 3 ) 2 ,Zn(CF 3 CO 2 ) 2 ,Zn(PF 6 ) 2 ,Zn(BF 4 ) 2 ,ZnSO 4 ,Zn(CH 3 CO 2 ) 2 ,Zn(ClO 4 ) 2 ,Zn(NO 3 ) 2 ,ZnCl 2 ,ZnBr 2 Preferably Zn (OAC) 2 The concentration is 0.01 to 3mol/L, preferably 0.1mol/L. The mass percentage of the hydrogen peroxide is 10-50%, preferably 30%. The mixed heating reaction condition of the reaction is that the temperature is 50-80 ℃ and the temperature is constant and heated for 2-48 hours, preferably 12 hours.
And uniformly mixing the chemically synthesized zinc peroxide with a conductive agent and a binder, and coating the mixture on a breathable current collector to obtain the zinc peroxide anode. The conductive agent comprises one or more of carbon black, carbon nano tube and graphene, preferably carbon black; the binder comprises one or more of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), nafion solution, preferably PTFE. The breathable current collector layer is one or more of carbon paper, carbon cloth, stainless steel mesh, metal mesh and foam metal, and is preferably carbon paper.
Further, the non-alkaline zinc air battery based on the zinc peroxide anode can be prepared by assembling the chemically synthesized zinc peroxide anode with the metal zinc cathode and the non-alkaline electrolyte.
The non-alkaline zinc-air battery based on the zinc peroxide anode provided by the invention has the following advantages and characteristics:
(1) The zinc peroxide anode has better electrochemical reversibility, so that the battery has the multiplying power performance of discharging with smaller current density and larger current density, longer charge and discharge time, more charge and discharge times and higher energy efficiency;
(2) The chemical synthesis zinc peroxide anode is used, no additional oxygen supply is needed, the closed operation can be realized, and the adverse effect caused by evaporation of an electrolyte water solvent in an open battery system is reduced;
(3) The non-alkaline electrolyte greatly improves the electrochemical reversibility of the zinc cathode, so that the battery has higher cycling stability;
(4) The non-alkaline electrolyte does not react with carbon dioxide in the air, and can stably run in the air without an additional carbon dioxide removing device;
(5) The corrosion resistance requirement of the battery assembly is low, and the battery assembly is easy to realize low-cost mass production and application.
Drawings
Fig. 1 is a schematic view of a non-alkaline zinc-air cell structure according to the present invention.
Fig. 2 is a schematic view of a zinc peroxide positive electrode structure according to the present invention.
Fig. 3 is a graph showing charge-discharge cycle performance of a non-alkaline zinc-air battery based on a zinc peroxide positive electrode according to example 1 of the present invention and a conventional alkaline zinc-air battery of comparative example.
Fig. 4 is a charge-discharge cycle performance chart according to example 2 of the present invention.
Fig. 5 is a charge-discharge cycle performance chart according to example 3 of the present invention.
Fig. 6 is a charge-discharge cycle performance chart according to example 4 of the present invention.
Fig. 7 is a charge-discharge cycle performance chart according to example 5 of the present invention.
Fig. 8 is a charge-discharge cycle performance chart according to example 6 of the present invention.
Fig. 9 is a charge-discharge cycle performance chart according to example 7 of the present invention.
Fig. 10 is a charge-discharge cycle performance chart according to example 8 of the present invention.
Fig. 11 is a charge-discharge cycle performance chart according to example 9 of the present invention.
Fig. 12 is a charge-discharge cycle performance chart according to embodiment 10 of the present invention.
Fig. 13 is a charge-discharge cycle performance chart according to example 11 of the present invention.
Fig. 14 is a charge-discharge cycle performance chart according to example 12 of the present invention.
Fig. 15 is a charge-discharge cycle performance chart according to example 13 of the present invention.
Fig. 16 is a charge-discharge cycle performance chart according to example 14 of the present invention.
Fig. 17 is a charge-discharge cycle performance chart according to example 15 of the present invention.
Fig. 18 is a charge-discharge cycle performance chart according to example 16 of the present invention.
Fig. 19 is a charge-discharge cycle performance chart according to example 17 of the present invention.
Fig. 20 is a charge-discharge cycle performance chart according to example 18 of the present invention.
Fig. 21 is a charge-discharge cycle performance chart according to example 19 of the present invention.
Fig. 22 is a charge-discharge cycle performance chart according to embodiment 20 of the present invention.
Fig. 23 is a schematic view of a conventional alkaline zinc-air cell structure.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
Example 1: and fully mixing the conductive agent carbon black and the adhesive PTFE, and uniformly coating the mixture on the breathable current collector carbon paper to prepare the anode coated with the conductive layer. The inorganic zinc salt Zn [ N (CF) with certain quality 3 SO 2 ) 2 ] 2 Adding the electrolyte into an aqueous solvent to prepare 1.5mol/L non-alkaline electrolyte. The positive electrode, the non-alkaline electrolyte and the metallic zinc negative electrode are assembled into a battery, wherein the metallic zinc negative electrode is a metallic zinc foil, and the thickness is 50 micrometers. The prepared battery is subjected to discharging and charging tests under the following conditions: the current density was 0.2mA/cm 2 The discharge and charge time was 5 hours. The characteristic reaction process is 2e - /O 2 (2 electrons are transferred to each 1 oxygen molecule to be reduced) and then zinc peroxide is formed on the surface of the positive electrode conducting layer on the side contacted with the electrolyte after discharging, so that the non-alkaline zinc-air battery based on the zinc peroxide positive electrode can be manufactured. The zinc peroxide positive electrode is shown in figure 2 of the specification. The cycle performance of the prepared non-alkaline zinc-air battery based on zinc peroxide is shown in fig. 3, and compared with the prior alkaline zinc-air battery technology (shown in a comparative example), the cycle times of the non-alkaline zinc-air battery shown in the embodiment 1 can be obviously improved from fig. 3.
Example 2: this example differs from example 1 in that the electrolyte used was 0.1mol/L Zn [ N (CF) 3 SO 2 ) 2 ] 2 The water solution adopts a metal zinc foil with the thickness of 20 microns as a negative electrode, and adopts cyclic discharge and charging current density of 0.01mA/cm 2 The discharging and charging time is 70 hours, and the prepared non-alkaline zinc air battery based on zinc peroxide can be operated for 140 hours in an air stable discharging and charging cycle. The cycle performance of the prepared non-alkaline zinc-air battery based on zinc peroxide is shown in figure 4, compared with the prior art using 1mol/L,2mol/L and 3mol/L Zn (CF 3 SO 3 ) 2 The zinc-air battery technology of zinc salt electrolyte, the non-alkaline zinc-air battery shown in the embodiment 2 can be operated by long-time discharging and charging under lower electrolyte concentration and smaller current density, and has higher application range and value.
Example 3: this example differs from example 1 in that the electrolyte used was 4mol/L Zn [ N (CF) 3 SO 2 ) 2 ] 2 The water solution adopts a metal zinc foil with the thickness of 200 micrometers as the cathode, and adopts cyclic discharge and charge current density of 0.1mA/cm 2 The discharging and charging time is 10 hours, and the prepared non-alkaline zinc air battery based on zinc peroxide can be operated for 100 hours in an air stable discharging and charging cycle. The cycle performance of the prepared non-alkaline zinc-air battery based on zinc peroxide is shown in FIG. 5, compared with the prior art using 1mol/L,2mol/L and 3mol/L Zn (CF) 3 SO 3 ) 2 The zinc-air battery technology of zinc salt electrolyte, the non-alkaline zinc-air battery shown in the embodiment 3 can be operated in a long-time discharging and charging mode under the condition of higher electrolyte concentration, and has higher application range and value.
Example 4: the difference between this example and example 1 is that the cyclic discharge and charge current densities used were 30mA/cm 2 The discharging and charging time is 0.05 hour, and the prepared non-alkaline zinc air battery based on zinc peroxide can stably discharge and charge in the air for 5 hours. The cycle performance of the prepared non-alkaline zinc-air battery based on zinc peroxide is shown in FIG. 6, compared with the prior art using 1mol/L,2mol/L and 3mol/L Zn (CF 3 SO 3 ) 2 Zinc air battery of zinc salt electrolyteThe technology, the non-alkaline zinc-air battery shown in the embodiment 4 can be operated in a long-time discharging and charging mode under higher current density, and has higher application range and value.
Example 5: this example differs from example 1 in that the electrolyte used was 1.4mol/L Zn (CF) 3 SO 3 ) 2 The aqueous solution adopts cyclic discharge and charging current density of 1mA/cm 2 The prepared non-alkaline zinc air battery based on zinc peroxide can be operated for 100 hours in air through stable discharge charging cycle, the cycle performance is shown in figure 7 of the specification, and compared with the prior art that Zn (CF) with the concentration of 1mol/L,2mol/L and 3mol/L is used 3 SO 3 ) 2 Zinc air cell technology of Zinc salt electrolyte, non-alkaline Zinc air cell shown in example 5 at 1mA/cm 2 The average charging voltage is about 1.75V under the current density, the average discharging voltage is 0.95V, the energy efficiency is improved by about 5%, and the application range and the value are higher.
Example 6: this example differs from example 1 in that the electrolyte used was 1.5mol/L Zn (CF) 3 SO 3 ) 2 The aqueous solution adopts cyclic discharge and charging current density of 1mA/cm 2 The prepared non-alkaline zinc air battery based on zinc peroxide can be operated for 100 hours in air through stable discharge charging cycle, the cycle performance is shown in figure 8 of the specification, and compared with the prior art that Zn (CF) with the concentration of 1mol/L,2mol/L and 3mol/L is used 3 SO 3 ) 2 Zinc air cell technology of Zinc salt electrolyte, non-alkaline Zinc air cell of example 6 at 1mA/cm 2 The average charging voltage is about 1.72V under the current density, the average discharging voltage is 1.05V, the energy efficiency is improved by about 8%, and the application range and the value are higher.
Example 7: this example differs from example 1 in that the electrolyte used was 1.6mol/L Zn (CF) 3 SO 3 ) 2 The aqueous solution adopts cyclic discharge and charging current density of 1mA/cm 2 The prepared non-alkaline zinc-air battery based on zinc peroxide can be operated for 100 hours in air through stable discharge and charge cycles, and the cyclicity of the battery is goodAs shown in FIG. 9 of the specification, the catalyst composition can be prepared by using 1mol/L,2mol/L and 3mol/L of Zn (CF 3 SO 3 ) 2 Zinc air cell technology of Zinc salt electrolyte, non-alkaline Zinc air cell of example 7 at 1mA/cm 2 The average charging voltage is about 1.73V under the current density, the average discharging voltage is 1.02V, the energy efficiency is improved by about 7%, and the application range and the value are higher.
Example 8: this example differs from example 1 in that the electrolyte used was 1.5mol/L Zn (CF) 3 CO 2 ) 2 The aqueous solution can be used for running the prepared non-alkaline zinc air battery based on zinc peroxide in air for 100 hours in a stable discharge charging cycle, the cycle performance of the non-alkaline zinc air battery is shown as a figure 10 in the specification, and the non-alkaline zinc air battery shown in the embodiment 8 widens the selection range of the salt types of the electrolyte and has higher application range and value.
Example 9: this example differs from example 1 in that the electrolyte used was 1.5mol/L Zn (PF 6 ) 2 The aqueous solution can be used for running the prepared non-alkaline zinc air battery based on zinc peroxide in air for 100 hours in a stable discharge charging cycle, the cycle performance of the non-alkaline zinc air battery is shown in an attached drawing 11 of an instruction, and the non-alkaline zinc air battery shown in the embodiment 9 widens the selection range of the salt types of the electrolyte and has higher application range and value.
Example 10: this example differs from example 1 in that the electrolyte used was 1.5mol/L Zn (BF) 4 The aqueous solution can be used for running the prepared non-alkaline zinc air battery based on zinc peroxide in air for 100 hours in a stable discharge charging cycle, the cycle performance of the non-alkaline zinc air battery is shown in an attached drawing 12 of an instruction book, and the non-alkaline zinc air battery shown in the embodiment 10 widens the selection range of electrolyte salt types and has higher application range and value.
Example 11: this example differs from example 1 in that the electrolyte used was 1.5mol/L Zn (NO) 3 ) 2 The aqueous solution can be used for running the prepared non-alkaline zinc-air battery based on zinc peroxide in air for 100 hours in a stable discharge charging cycle, and the cycle performance of the battery is as followsThe non-alkaline zinc-air battery shown in the specification and attached to fig. 13 and in the embodiment 11 widens the selection range of electrolyte salt types, and has higher application range and value.
Example 12: this example differs from example 1 in that the electrolyte used was 1.5mol/L Zn (CH) 3 CO 2 ) 2 The aqueous solution can be used for running the prepared non-alkaline zinc-air battery based on zinc peroxide in air for 100 hours in a stable discharge charging cycle, the cycle performance of the non-alkaline zinc-air battery is shown in the attached chart 14 of the specification, and the non-alkaline zinc-air battery shown in the embodiment 12 widens the selection range of electrolyte salt types and has higher application range and value.
Example 13: this example differs from example 1 in that the electrolyte used was 1.5mol/L Zn (ClO) 4 ) 2 The aqueous solution can be used for running the prepared non-alkaline zinc air battery based on zinc peroxide in air for 100 hours in a stable discharge charging cycle, the cycle performance of the non-alkaline zinc air battery is shown in the specification and the figure 15, and the non-alkaline zinc air battery shown in the embodiment 13 widens the selection range of the salt types of the electrolyte and has higher application range and value.
Example 14: this example differs from example 1 in that the electrolyte used is ZnCl at 1.5mol/L 2 The aqueous solution can be used for running the prepared non-alkaline zinc-air battery based on zinc peroxide in air for 100 hours in a stable discharge charging cycle, the cycle performance of the non-alkaline zinc-air battery is shown in a figure 16 of the specification, and the non-alkaline zinc-air battery shown in the embodiment 14 widens the selection range of electrolyte salt types and has higher application range and value.
Example 15: this example differs from example 1 in that the electrolyte used was ZnBr at 1.5mol/L 2 The aqueous solution can be used for running the prepared non-alkaline zinc-air battery based on zinc peroxide in air for 100 hours in a stable discharge charging cycle, the cycle performance of the non-alkaline zinc-air battery is shown in figure 17 of the specification, and the non-alkaline zinc-air battery shown in the embodiment 15 widens the selection range of electrolyte salt types and has higher application range and value.
The zinc peroxide positive electrode of the above non-alkaline zinc-air cell can also be prepared by chemical reaction as in examples 16-24 below.
Example 16: the inorganic zinc salt Zn (CH) with certain quality 3 CO 2 ) 2 Adding into water to prepare zinc salt water solution with the concentration of 0.1mol/L. Mixing and stirring 30% hydrogen peroxide and zinc salt aqueous solution uniformly, heating to 60 ℃ and preserving heat for 12 hours to obtain the precipitate zinc peroxide. Uniformly mixing zinc peroxide with conductive agent carbon black and binder PTFE, and coating the mixture on the breathable current collector carbon paper to obtain the zinc peroxide anode. The chemically synthesized zinc peroxide positive electrode was combined with the metallic zinc negative electrode of example 1 and 1.5mol/L Zn [ N (CF) 3 SO 2 ) 2 ] 2 And assembling the non-alkaline electrolyte to obtain the non-alkaline zinc-air battery based on the zinc peroxide anode. The prepared battery is subjected to discharging and charging tests under the following conditions: the current density was 0.2mA/cm 2 The discharge and charge time was 5 hours. The cycle performance of the alkaline zinc-air battery is shown in the attached figure 18 of the specification, and the alkaline zinc-air battery in the embodiment 16 uses a chemical synthesized zinc peroxide positive electrode, so that no additional oxygen supply is needed, the closed operation can be realized, the adverse effect caused by evaporation of an electrolyte water solvent in an open battery system is reduced, and the alkaline zinc-air battery has a higher application range and value.
Example 17: this example differs from example 8 in that the non-alkaline electrolyte was 1.5mol/L Zn (CF 3 SO 3 ) 2 The aqueous solution can be used for running the prepared non-alkaline zinc air battery based on zinc peroxide in air for 200 hours in a stable discharge charging cycle, and the cycle performance of the battery is shown in figure 19 of the specification.
Example 18: this example differs from example 8 in that the non-alkaline electrolyte was 1.5mol/L Zn (ClO 4 ) 2 The aqueous solution can be used for running the prepared non-alkaline zinc air battery based on zinc peroxide in air for 100 hours in a stable discharge charging cycle, and the cycle performance of the non-alkaline zinc air battery is shown in figure 20 of the specification.
Example 19: this example differs from example 8 in that the reactant inorganic zinc salt of zinc peroxide, zn (CH 3 CO 2 ) 2 The concentration of the aqueous solution is 0.01mThe battery test discharge and charge time is 10 hours, and the prepared non-alkaline zinc air battery based on zinc peroxide can be operated for 100 hours in an air stable discharge charge cycle, and the cycle performance is shown in figure 21 of the specification.
Example 20: this example differs from example 8 in that the reactant inorganic zinc salt of zinc peroxide, zn (CH 3 CO 2 ) 2 The concentration of the aqueous solution is 3mol/L, the discharge and charge time of the battery is 10 hours, and the prepared non-alkaline zinc air battery based on zinc peroxide can be stably discharged in the air, charged and circulated for 100 hours, and the circulation performance of the battery is shown in figure 22 of the specification.
Example 21: this example differs from example 8 in that the chemical reaction produces the reactant inorganic zinc salt of zinc peroxide Zn (OTF) 2 The concentration of the aqueous solution is 0.1mol/L, and the prepared non-alkaline zinc-air battery based on zinc peroxide can be operated for 100 hours in an air stable discharge charging cycle.
Example 22: this example differs from example 8 in that the reactant inorganic zinc salt of zinc peroxide Zn (BF 4 ) 2 The concentration of the aqueous solution is 0.1mol/L, and the prepared non-alkaline zinc-air battery based on zinc peroxide can be operated for 100 hours in an air stable discharge charging cycle.
Example 23: this example differs from example 8 in that the reactant inorganic zinc salt of zinc peroxide, zn (CF 3 CO 2 ) 2 The concentration of the aqueous solution is 0.1mol/L, and the prepared non-alkaline zinc-air battery based on zinc peroxide can be operated for 100 hours in an air stable discharge charging cycle.
Example 24: this example differs from example 8 in that the reactant inorganic zinc salt of zinc peroxide, zn [ N (CF) 3 SO 2 ) 2 ] 2 The concentration of the aqueous solution is 0.1mol/L, and the prepared non-alkaline zinc-air battery based on zinc peroxide can be operated for 100 hours in an air stable discharge charging cycle.
Comparative example 25: this comparative example differs from example 1 in that the electrolyte used was an aqueous alkaline electrolyte of 6.0mol/L KOH. The prepared alkaline zinc-air battery is invalid after only circulating in the air for 20 hours. The cycle performance is shown in figure 3 of the specification. As can be seen from the comparison of the cycle performance of comparative example and example 1, the zinc peroxide-based non-alkaline zinc air battery has a significant advantage of stable cycle performance over the alkaline zinc air battery.
Claims (6)
1. A non-alkaline zinc air battery based on a zinc peroxide positive electrode is characterized in that a metal zinc negative electrode, a non-alkaline electrolyte and a zinc peroxide positive electrode are sequentially arranged from the negative electrode to the positive electrode, wherein a solute of the non-alkaline electrolyte is an inorganic zinc salt, a solvent is water, and the inorganic zinc salt is Zn (CF 3 SO 3 ) 2 The concentration is 1.4-1.6mol/L; or the inorganic zinc salt is Zn [ N (CF) 3 SO 2 ) 2 ] 2 The concentration is 0.1mol/L; the zinc peroxide positive electrode sequentially comprises: zinc peroxide, a conductive layer and a gas permeable current collector.
2. A non-alkaline zinc-air cell based on a zinc-peroxide anode according to claim 1, wherein the zinc-peroxide contained in the anode is generated during discharge of the zinc-air cell.
3. The non-alkaline zinc-air battery based on the zinc peroxide anode according to claim 1, wherein the zinc peroxide contained in the anode is synthesized in advance before the battery is assembled, and the synthesis process is that an inorganic zinc salt aqueous solution is mixed with hydrogen peroxide, heated and reacted, and then the mixture is kept stand for precipitating a product.
4. A non-alkaline zinc air battery based on a zinc peroxide positive electrode according to claim 3, characterized in that the zinc peroxide contained in the positive electrode is synthesized by chemical reaction, the reactant inorganic zinc salt of the reaction is Zn (CH 3 CO 2 ) 2 ,Zn(CF 3 SO 3 ) 2 ,Zn[N(CF 3 SO 2 ) 2 ] 2 ,Zn(CF 3 CO 2 ) 2 ,Zn(PF 6 ) 2 ,Zn(BF 4 ) 2 ,ZnSO 4 ,Zn(ClO 4 ) 2 ,Zn(NO 3 ) 2 ,ZnCl 2 ,ZnBr 2 The solvent is water, and the concentration is 0.01-3 mol/L.
5. The non-alkaline zinc-air battery based on the zinc peroxide anode according to claim 4, wherein the zinc peroxide contained in the anode is synthesized by chemical reaction, and the mass percentage of the reactant hydrogen peroxide of the reaction is 10-50%.
6. A non-alkaline zinc air battery based on a zinc peroxide anode according to claim 5, wherein the zinc peroxide contained in the anode is synthesized by chemical reaction, and the mixed heating reaction condition of the reaction is that the temperature is kept between 50 and 80 ℃ for 2 to 48 hours.
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