CN110289387B - All-solid-state neutral zinc-air battery - Google Patents
All-solid-state neutral zinc-air battery Download PDFInfo
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- CN110289387B CN110289387B CN201910411399.5A CN201910411399A CN110289387B CN 110289387 B CN110289387 B CN 110289387B CN 201910411399 A CN201910411399 A CN 201910411399A CN 110289387 B CN110289387 B CN 110289387B
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- 239000011701 zinc Substances 0.000 claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 claims abstract description 57
- 239000002184 metal Substances 0.000 claims abstract description 57
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000003792 electrolyte Substances 0.000 claims abstract description 33
- 239000011245 gel electrolyte Substances 0.000 claims abstract description 24
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- 238000002347 injection Methods 0.000 claims abstract description 19
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 10
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- 239000006259 organic additive Substances 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
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- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
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- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 229920005614 potassium polyacrylate Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
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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
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Hybrid Cells (AREA)
Abstract
The invention relates to the field of zinc-air batteries, in particular to a neutral electrolyte all-solid-state zinc-air battery and a battery preparation method thereof. The invention provides an all-solid-state zinc-air battery, which comprises: the battery comprises a neutral gel electrolyte, an air anode, a metal zinc cathode, a battery supporting frame and a threaded upper cover. The organic gel wraps the neutral electrolyte to form the neutral gel electrolyte. The air anode consists of a current collecting layer, a hydrophobic breathable layer and a catalytic layer. The battery support frame and the threaded upper cover provide protective support. The metal zinc tube or rod is fitted in the groove of the cell frame. The side of the air anode coated with the catalyst faces inwards and is fixed in the clamping groove of the battery frame. Injecting the prepared neutral electrolyte into the gap between the air anode and the metal zinc cathode through the liquid injection hole of the threaded upper cover, standing and gelling. And assembling to obtain the neutral all-solid-state zinc-air battery. After the battery loses water, fresh electrolyte can be supplemented through the liquid injection hole of the thread upper cover, so that the performance of the battery is recovered.
Description
Technical Field
The invention relates to the field of zinc-air batteries, in particular to a neutral electrolyte all-solid-state zinc-air battery and a battery preparation method thereof.
Background
An all-solid-state zinc-air battery is an all-solid-state metal-air battery which takes oxygen in the air as a positive electrode, metal zinc as a negative electrode and organic gel as electrolyte. The all-solid-state zinc-air battery has the characteristics of high energy density, stable working voltage, no pollution, low cost and the like, and is widely applied to various portable mobile power supplies or power supplies of wearable electronic equipment.
At present, most of all-solid-state zinc-air batteries are alkaline organogel electrolytes, and the principle of the alkaline organogel electrolytes is to wrap alkaline aqueous solutions in organogels. Since the zinc-air battery is a semi-open system, the organic gel electrolyte can be directly contacted with air, and acid gases in the air, such as CO2And reacts with alkaline substances in the organogel electrolyte to form carbonate, resulting in a decrease in the conductivity of the electrolyte and a decrease in the performance of the battery. Alkaline substances in the organic gel can also react with the metal zinc electrode to cause self-discharge of the battery, the metal zinc electrode is corroded and consumed, and the capacity and the service life of the battery are greatly shortened. In addition, the organic gel electrolyte contains a large amount of alkaline aqueous solution, and the humidity of the working environment of the battery is low, so that organic coagulation can be caused in the long-term storage or working process of the batteryThe gel electrolyte dries up due to water loss, the battery deforms, the contact area between the electrolyte and the zinc cathode and the air anode is reduced, the ionic conductivity of the electrolyte is reduced, the performance of the battery is deteriorated, and the service life of the battery is shortened. More importantly, when the all-solid-state zinc-air battery is applied to wearable electronic equipment, the battery can be directly or indirectly contacted with the skin of a human body, and the alkaline electrolyte can form potential danger to the human body. Therefore, the all-solid-state zinc-air battery with the neutral electrolyte can avoid the potential dangers, and has wider market prospect when being applied to the field of wearable electronic equipment.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a neutral long-life all-solid-state zinc-air battery. The all-solid-state zinc-air battery structure designed by the invention can reduce the water loss of the organogel electrolyte, and meanwhile, the water absorption characteristic of the organogel is utilized, so that the electrolyte can be timely supplemented to the dehydrated organogel electrolyte in the later stage, and the battery performance is recovered. Therefore, the all-solid-state zinc-air battery provided by the invention has longer service life. In addition, the neutral electrolyte replaces the alkaline electrolyte, so that the influence of acid gas in the air is reduced, the self-discharge of the battery is inhibited, the service life of the battery is prolonged, and the potential danger is reduced.
The invention provides a brand new neutral long-life all-solid-state zinc-air battery structure (figure 1), which comprises: the battery comprises a threaded upper cover, a metal zinc cathode, a battery supporting frame, an air anode and a neutral gel electrolyte.
The threaded upper cover (fig. 3) is preferably made of organic glass, polyethylene, polypropylene, polyvinyl chloride or ABS plastic. And the upper screw cover is provided with a liquid injection hole and an exhaust hole for injecting the initial electrolyte and replenishing the later electrolyte.
The metal zinc cathode is preferably a polished zinc rod or a polished zinc tube.
The air anode consists of a current collecting layer, a hydrophobic breathable layer and a catalytic layer.
The current collecting layer is preferably one or more of nickel foam, nickel mesh, copper foam and copper mesh.
The hydrophobic breathable layer is preferably hydrophobic breathable carbon paper, hydrophobic breathable carbon cloth, porous carbon felt and the like.
The catalyst layer is composed of a conductive carbon material, a binder and a catalyst material. The mass percentage of the catalyst to the conductive carbon material is preferably 0.5-1.5. The catalyst material is preferably one or more of platinum, metal oxide, a metal-free carbon material and a carbon-based composite material. The conductive carbon material is preferably one or more of conductive carbon black, activated carbon, graphene and a carbon nanotube. The mass ratio of the binder to the catalyst material is preferably 0.01-0.1. The binder is preferably one or more of silica sol, Nafion solution, PVP emulsion and PTFE emulsion.
The battery supporting frame (figure 2) is preferably one or more of organic glass, polyethylene, polypropylene, polyvinyl chloride and ABS plastic. The contact area between the air anode and the surrounding environment is increased by the pores around the battery supporting frame, and the groove at the bottom is used for fixing the metal zinc cathode and the air anode.
The neutral gel electrolyte includes an organogel and an organic additive.
The mass percentage of the organogel to the organic additive is preferably 0.05-1. The organic gel is preferably one or more of PANA (sodium polyacrylate), PAK (potassium polyacrylate) and PAM (polyacrylamide). The organic additive is preferably one or more of organic substances containing hydroxyl groups such as ethanol, isopropanol, ethylene glycol, glycerol, etc.
The preparation method of the all-solid-state neutral zinc-air battery comprises the following steps:
preparation of air cathode: the conductive carbon material and the catalyst material are weighed according to the mass ratio of 0.5-2, mixed with 10-200 ml of ethanol, dropwise added with 50-500 ul of 5 wt% Nafion solution, and subjected to ultrasonic treatment for 0.5-4 hours to form uniformly dispersed catalyst slurry. Coating the prepared catalyst slurry on one side of hydrophobic and air-permeable carbon cloth by taking the hydrophobic and air-permeable carbon cloth as a matrix in a spraying or dropping mode, and heating the hydrophobic and air-permeable carbon cloth on a heating table at the temperature of 60-150 ℃ for 1-5 hours to form the catalyst loading amount of 0.5-5 mg cm-2The air positive electrode of (1). Respectively carrying out air anode and foam nickel on a roller pressRolling to form an integral structure.
Preparing a zinc cathode:
selecting a zinc rod or a zinc tube with one end diameter of 6-8 mm, length of 41-45 mm, the other end diameter of 4-6 mm and length of 6-7 mm. The surface was polished with sandpaper to remove an oxide layer on the surface.
Fixing the zinc cathode and the air cathode with the frame:
the air anode is rolled into a cylinder shape, the catalyst layer faces inwards, and the air anode is fixed in a clamping groove of the battery frame. One end of the zinc cathode is assembled into a groove of the battery frame, positioned and screwed to the threaded upper cover.
Injecting and replenishing electrolyte:
electrolyte preparation: and weighing the organic additive and distilled water according to the mass ratio of 0.2-2, and uniformly mixing to form a No. 1 solution. Weighing one or more of sodium acrylate (ANa), potassium Acrylate (AK) and Acrylamide (AM) solution, adding the solution and N, N' -Methylene Bisacrylamide (MBAM) into the No. 1 solution according to the mass ratio of 2-10, and uniformly mixing to form the No. 2 mixed solution. Adding an initiator potassium persulfate into the 2# mixed solution according to the mass ratio of 0.001-0.05, and uniformly stirring to form a neutral gel electrolyte mixed solution for later use.
Electrolyte injection: injecting the prepared neutral gel electrolyte mixed solution into a gap between the air anode and the zinc cathode through a liquid injection hole of the battery thread upper cover by using a syringe or a liquid-transferring gun, standing, and screwing bolts of the liquid injection hole and the exhaust hole to realize sealing after gelling.
Electrolyte replenishment: and screwing off the bolts of the liquid injection hole and the exhaust hole, injecting electrolyte or distilled water into a gap between the air anode and the zinc cathode through the liquid injection hole of the battery thread upper cover by using an injector or a liquid-moving gun until the gel is recovered, screwing the bolts of the liquid injection hole and the exhaust hole, and sealing.
The cell self-discharge test results (fig. 4(a)) show that the voltage of the all-solid-state neutral zinc-air cell (using glycerol as the electrolyte) provided by the invention is reduced by 0.04V in 300 hours, while the voltage of the all-solid-state alkaline zinc-air cell (using KOH as the electrolyte) prepared by the same method is reduced by 0.4V. The charge-discharge cycle test result (fig. 4(b)) of the battery shows that the method for replenishing the electrolyte provided by the invention can recover the performance of the battery and prolong the service life of the battery.
Drawings
FIG. 1 is a structural view of an all-solid-state neutral zinc-air battery of the present invention
FIG. 2 is an all solid state neutral zinc-air cell frame of the present invention
FIG. 3 is a planer view of the threaded overcap of the present invention
FIG. 4(a) is a test curve of the self-discharge performance of a neutral long-life all-solid-state zinc-air cell and a KOH alkaline cell of the present invention; FIG. 4(b) is a test curve of the cycle charge and discharge performance of the neutral long-life all-solid-state zinc-air battery of the invention
The first embodiment is as follows:
support frame of battery: the cell support frame is an open structure with sufficient apertures to allow air to enter the air cathode. Grooves are reserved on the upper screw cover and the bottom of the upper screw cover and are used for fixing the metal electrode and limiting the horizontal movement of the metal zinc cathode. The metal zinc cathode can be fastened by screwing the threaded upper cover, and the axial movement of the metal zinc cathode is limited. The braced frame still sets up the anodal fixed slot of air, prevents that the anodal deformation of air or removal.
Preparing a metal zinc cathode: the metal zinc negative electrode is a high-purity metal zinc bar polished by fine sand paper. One end of the metal zinc cathode is 5mm in diameter and 40mm in length, and the other end of the metal zinc cathode is 3mm in diameter and 5mm in length.
Preparing an air positive electrode: 24mg of conductive carbon black (VXC-72) and 24mg of La were weighed out0.8Sr0.2Co0.6Fe0.4O3The catalyst was stirred in 30ml of ethanol, 100ul of 5 wt% Nafion binder was added dropwise, and the mixture was sonicated for 2 hours to form a uniformly dispersed catalyst slurry. Coating the prepared catalyst slurry on one side of a hydrophobic and air-permeable carbon cloth by taking the hydrophobic and air-permeable carbon cloth of 6cm multiplied by 4cm as a matrix in a spraying or dropping mode, and heating the hydrophobic and air-permeable carbon cloth on a heating table at the temperature of 80 ℃ for 1 hour to form the catalyst loading amount of 1mg cm-2The air positive electrode of (1). The air anode and the foam nickel are respectively rolled on a roller press to form an integral structure for standby. Air anodeIs 1.3 mm.
Preparation of gel electrolyte: 15g of glycerol and 30g of distilled water are mixed uniformly to form a No. 1 solution. 4g of potassium acrylate solution and 1g N, N' -methylene bisacrylamide are weighed respectively, added into the solution 1 and uniformly mixed to form a mixed solution 2. 0.5g of potassium persulfate is weighed and added into the No. 2 mixed solution, and the mixture is stirred uniformly to form a neutral gel electrolyte mixed solution for later use.
Preparing and testing an all-solid-state zinc-air battery:
the catalyst layer of the air anode faces inwards and is fixed in a clamping groove of the cell frame. And (3) assembling the metal zinc cathode into a groove of a battery frame, positioning, and screwing the threaded upper cover. And injecting the prepared gel electrolyte mixed solution into a gap between the air anode and the metal zinc cathode through a liquid injection hole of the battery thread upper cover, standing, gelling and sealing. The neutral long-life all-solid-state zinc-air battery is formed by assembling. And in the later stage, the injector is utilized to supplement electrolyte for the battery through the liquid injection hole.
The self-discharge test result of the battery shows that the voltage of the all-solid-state neutral zinc-air battery provided by the invention is reduced by 0.045V in 300 hours.
The second embodiment is as follows:
support frame of battery: grooves are reserved on the upper screw cover and the bottom of the upper screw cover and are used for fixing the metal electrode and limiting the horizontal movement of the metal zinc cathode. The metal zinc cathode can be fastened by screwing the threaded upper cover, and the axial movement of the metal zinc cathode is limited. The braced frame still sets up the anodal fixed slot of air, prevents that the anodal deformation of air or removal.
Preparing a metal zinc cathode: the metal zinc negative electrode is a high-purity metal zinc bar polished by fine sand paper. One end of the metal zinc cathode is 5mm in diameter and 40mm in length, and the other end of the metal zinc cathode is 3mm in diameter and 5mm in length.
Preparing an air positive electrode: 24mg of conductive carbon black (VXC-72) and 24mg of La were weighed out0.8Sr0.2Co0.6Fe0.4O3The catalyst was stirred in 30ml of ethanol, 100ul of 5 wt% Nafion binder was added dropwise, and the mixture was sonicated for 2 hours to form a uniformly dispersed catalyst slurry. Hydrophobic and air-permeable carbon cloth of 6cm multiplied by 4cm is taken as a matrix to passCoating the prepared catalyst slurry on one side of hydrophobic air-permeable carbon cloth by spraying or dripping, and heating on a heating table at 80 ℃ for 1 hour to form the catalyst loading amount of 1mg cm-2The air positive electrode of (1). The air anode and the foam nickel are respectively rolled on a roller press to form an integral structure for standby. The thickness of the air positive electrode was 1.3 mm.
Preparation of gel electrolyte: 30g of ethylene glycol and 30g of distilled water were uniformly mixed to form a # 1 solution. 6g of sodium acrylate solution and 1g N, N' -methylene bisacrylamide are weighed respectively, added into the solution No. 1 and uniformly mixed to form a mixed solution No. 2. 0.5g of potassium persulfate is weighed and added into the No. 2 mixed solution, and the mixture is stirred uniformly to form a neutral gel electrolyte mixed solution for later use.
Preparing and testing an all-solid-state zinc-air battery:
the catalyst layer of the air anode faces inwards and is fixed in a clamping groove of the cell frame. And (3) assembling the metal zinc cathode into a groove of a battery frame, positioning, and screwing the threaded upper cover. And injecting the prepared gel electrolyte mixed solution into a gap between the air anode and the metal zinc cathode through a liquid injection hole of the battery thread upper cover, standing, gelling and sealing. The neutral long-life all-solid-state zinc-air battery is formed by assembling. And in the later stage, the injector is used for supplementing water to the battery through the liquid injection hole.
The self-discharge test result of the battery shows that the voltage of the all-solid-state neutral zinc-air battery provided by the invention is reduced by 0.049V in 300 hours.
The third concrete implementation mode:
support frame of battery: grooves are reserved on the upper screw cover and the bottom of the upper screw cover and are used for fixing the metal electrode and limiting the horizontal movement of the metal zinc cathode. The metal zinc cathode can be fastened by screwing the threaded upper cover, and the axial movement of the metal zinc cathode is limited. The braced frame still sets up the anodal fixed slot of air, prevents that the anodal deformation of air or removal.
Preparing a metal zinc cathode: the metal zinc negative electrode is a high-purity metal zinc bar polished by fine sand paper. One end of the metal zinc cathode is 5mm in diameter and 40mm in length, and the other end of the metal zinc cathode is 3mm in diameter and 5mm in length.
Air positivePreparing a pole: 24mg of conductive carbon black (VXC-72) and 24mg of La were weighed out0.8Sr0.2Co0.6Fe0.4O3The catalyst was stirred in 30ml of ethanol, 100ul of 5 wt% Nafion binder was added dropwise, and the mixture was sonicated for 2 hours to form a uniformly dispersed catalyst slurry. Coating the prepared catalyst slurry on one side of a hydrophobic and air-permeable carbon cloth by taking the hydrophobic and air-permeable carbon cloth of 6cm multiplied by 4cm as a matrix in a spraying or dropping mode, and heating the hydrophobic and air-permeable carbon cloth on a heating table at the temperature of 80 ℃ for 1 hour to form the catalyst loading amount of 1mg cm-2The air positive electrode of (1). The air anode and the foam nickel are respectively rolled on a roller press to form an integral structure for standby. The thickness of the air positive electrode was 1.3 mm.
Preparation of gel electrolyte: 25g of ethanol and 30g of distilled water are mixed uniformly to form a No. 1 solution. 4g of acrylamide and 1g N, N' -methylene bisacrylamide are weighed respectively and added into the solution 1 to be uniformly mixed to form a mixed solution 2. 0.5g of potassium persulfate is weighed and added into the No. 2 mixed solution, and the mixture is stirred uniformly to form a neutral gel electrolyte mixed solution for later use.
Preparing and testing an all-solid-state zinc-air battery:
the catalyst layer of the air anode faces inwards and is fixed in a clamping groove of the cell frame. And (3) assembling the metal zinc cathode into a groove of a battery frame, positioning, and screwing the threaded upper cover. And injecting the prepared gel electrolyte mixed solution into a gap between the air anode and the metal zinc cathode through a liquid injection hole of the battery thread upper cover, standing, gelling and sealing. The neutral long-life all-solid-state zinc-air battery is formed by assembling. And in the later stage, the injector is used for supplementing water to the battery through the liquid injection hole.
The self-discharge test result of the battery shows that the voltage of the all-solid-state neutral zinc-air battery provided by the invention is reduced by 0.039V in 300 hours.
The fourth concrete implementation mode:
support frame of battery: grooves are reserved on the upper screw cover and the bottom of the upper screw cover and are used for fixing the metal electrode and limiting the horizontal movement of the metal zinc cathode. The metal zinc cathode can be fastened by screwing the threaded upper cover, and the axial movement of the metal zinc cathode is limited. The braced frame still sets up the anodal fixed slot of air, prevents that the anodal deformation of air or removal.
Preparing a metal zinc cathode: the metal zinc negative electrode is a high-purity metal zinc bar polished by fine sand paper. One end of the metal zinc cathode is 5mm in diameter and 40mm in length, and the other end of the metal zinc cathode is 3mm in diameter and 5mm in length.
Preparing an air positive electrode: 24mg of conductive carbon black (VXC-72) and 24mg of La were weighed out0.8Sr0.2Co0.6Fe0.4O3The catalyst was stirred in 30ml of ethanol, 100ul of 5 wt% Nafion binder was added dropwise, and the mixture was sonicated for 2 hours to form a uniformly dispersed catalyst slurry. Coating the prepared catalyst slurry on one side of a hydrophobic and air-permeable carbon cloth by taking the hydrophobic and air-permeable carbon cloth of 6cm multiplied by 4cm as a matrix in a spraying or dropping mode, and heating the hydrophobic and air-permeable carbon cloth on a heating table at the temperature of 80 ℃ for 1 hour to form the catalyst loading amount of 1mg cm-2The air positive electrode of (1). The air anode and the foam nickel are respectively rolled on a roller press to form an integral structure for standby. The thickness of the air positive electrode was 1.3 mm.
Preparation of gel electrolyte: 15g of glycerol and 30g of distilled water are mixed uniformly to form a No. 1 solution. 4g of potassium acrylate solution and 1g N, N' -methylene bisacrylamide are weighed respectively, added into the solution 1 and uniformly mixed to form a mixed solution 2. 0.5g of potassium persulfate is weighed and added into the No. 2 mixed solution, and the mixture is stirred uniformly to form a neutral gel electrolyte mixed solution for later use.
Preparing and testing an all-solid-state zinc-air battery:
the catalyst layer of the air anode faces inwards and is fixed in a clamping groove of the cell frame. And (3) assembling the metal zinc cathode into a groove of a battery frame, positioning, and screwing the threaded upper cover. And injecting the prepared gel electrolyte mixed solution into a gap between the air anode and the metal zinc cathode through a liquid injection hole of the battery thread upper cover, standing, gelling and sealing. The neutral long-life all-solid-state zinc-air battery is formed by assembling. And (4) supplementing the battery with the No. 1 solution through the liquid injection hole by using a syringe at the later stage.
The self-discharge test result of the battery shows that the voltage of the all-solid-state neutral zinc-air battery provided by the invention is reduced by 0.036V in 300 hours.
Claims (6)
1. An all-solid-state neutral zinc-air cell, comprising: the battery comprises a gel electrolyte, an air anode, a metal zinc cathode, a battery supporting frame and a threaded upper cover; the preparation steps are as follows: (1) weighing an organic additive and distilled water according to a mass ratio of 0.2-2, and uniformly mixing to form a No. 1 solution, wherein the organic additive is one or more of ethylene glycol, isopropanol, ethanol and glycerol; weighing one or more of sodium acrylate, potassium acrylate and acrylamide solution, adding the sodium acrylate, potassium acrylate and acrylamide solution and N, N' -methylene bisacrylamide into the No. 1 solution according to the mass ratio of 2-10, and uniformly mixing to form a No. 2 mixed solution; adding an initiator potassium persulfate into the 2# mixed solution according to the mass ratio of 0.001-0.05, and uniformly stirring to form a neutral gel electrolyte mixed solution; (2) fixing a metal zinc cathode and an air anode in a battery supporting frame, wherein the air anode consists of a current collecting layer, a hydrophobic breathable layer and a catalytic layer; (3) injecting the prepared neutral gel electrolyte mixed solution into a gap between an air anode and a metal zinc cathode through a liquid injection hole of a threaded upper cover of the battery, standing, gelling, and assembling into an all-solid-state zinc-air battery; (4) after the battery operates or is placed for a period of time, replenishing electrolyte to the battery through the electrolyte injection hole so as to recover the performance of the battery; the supplementary electrolyte is one or more of ethylene glycol, ethanol, glycerol or isopropanol solution.
2. The all-solid-state neutral zinc-air battery according to claim 1, wherein the hydrophobic air-permeable layer is a hydrophobic air-permeable carbon cloth or a hydrophobic air-permeable carbon paper.
3. The all-solid-state neutral zinc-air battery according to claim 1, wherein the catalytic layer is composed of a conductive carbon material and a catalyst material; the mass ratio of the conductive carbon material to the catalyst material is 0.5-1.5; the conductive carbon material is one or more of conductive carbon black, activated carbon and graphene; the catalyst material is one or more of platinum, transition metal oxide, metal-free carbon material and carbon-based composite material.
4. The all-solid-state neutral zinc-air cell of claim 1, wherein the active zinc negative electrode is a high purity zinc metal rod or tube.
5. The all-solid-state neutral zinc-air cell of claim 1, wherein the cell support frame is one of plexiglass, polyethylene, polypropylene, polyvinyl chloride, or ABS plastic.
6. The all-solid-state neutral zinc-air cell of claim 1, wherein the threaded upper cover is one of plexiglass, polyethylene, polypropylene, polyvinyl chloride, or ABS plastic.
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| CN113675506A (en) * | 2021-09-17 | 2021-11-19 | 安徽朔代科技有限公司 | Cell unit structure and metal fuel cell |
| CN113937304B (en) * | 2021-09-30 | 2023-04-21 | 华中科技大学 | Flexible neutral zinc-air battery and preparation method thereof |
| CN114204167A (en) * | 2021-12-10 | 2022-03-18 | 辽宁大学 | Preparation method of rechargeable iron or zinc-air battery based on hydrogel electrolyte |
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| CN103794812A (en) * | 2014-01-02 | 2014-05-14 | 河南科技大学 | Gel polymer electrolyte, preparation method of gel polymer electrolyte and silicon air battery using gel polymer electrolyte |
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