CN103985923A - Quasi-solid electrolyte PVA-zinc-air battery - Google Patents
Quasi-solid electrolyte PVA-zinc-air battery Download PDFInfo
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- CN103985923A CN103985923A CN201410171564.1A CN201410171564A CN103985923A CN 103985923 A CN103985923 A CN 103985923A CN 201410171564 A CN201410171564 A CN 201410171564A CN 103985923 A CN103985923 A CN 103985923A
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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
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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Abstract
The invention discloses a quasi-solid electrolyte PVA(Polyvinyl Alcohol)-zinc-air battery, which comprises an air electrode taking reduction action, a zinc electrode taking oxidation reaction, electrolyte and a battery case, wherein the air electrode, the zinc electrode and the electrolyte are accommodated in the battery case, the electrolyte is jelly solid PVA-KOH-H2O alkaline polymers (PVA quasi-solid electrolyte), and a battery diaphragm is arranged between the air electrode and the zinc electrode. The quasi-solid electrolyte PVA-zinc-air battery has the beneficial effects that 1, the adopted solid electrolyte is jelly solid and has a certain toughness, the growth of zinc dendrite can be obstructed, the battery internal short circuit caused by diaphragm piercing due to formation of zinc dendrite thorns is prevented, the service life of the battery is prolonged, and the integral performance of the battery is improved; 2, the occurrence of battery electrolyte leakage can be obviously prevented through the solid electrolyte, so the integral performance of the battery is improved.
Description
Technical field
The present invention relates to a kind of battery, be specially a kind of quasi-solid electrolyte-PVA zinc-air battery, belong to technical field of new energies.
Background technology
People for a long time; the mankind in productive life always taking oil and coal as the energy; along with the continuous increase of demand for energy in recent years; non-renewable energy resources reserves but reduce gradually; energy crisis starts to flash; energy security becomes the problem that each country is highly absorbed in, and is also the huge challenge that we face simultaneously.Under this background, energy-saving and emission-reduction, Green Development are inevitable choices, seek new forms of energy and substitute fossil energy with aobvious urgent, and the continuous increase of portable type electronic product development and zero discharge electric motor car demand, people meet the demands at the battery of seeking a kind of high-energy system.Zinc-air cell is as new technology efficient, clean, green energy resource, have that capacity is large, specific energy is high, cost is low, discharge performance is stable, safe, zero pollute, the feature such as high-power and material is renewable, having become current world energy sources field focus, is a kind of chemical energy source with great market prospect.
Since 1879, Maiche has produced first and has done negative pole with zinc metal sheet, the porous carbon of employing platinum is made air electrode and is done after the neutral electrolyte zinc-air cell of anode, through constantly development, after the sixties in 20th century, zinc air disposable battery has had significant progress, and slim air electrode is incorporated into zinc-air cell, greatly improve the discharge performance of battery, make zinc-air cell development have important breakthrough.At the end of the sixties, high efficiency zinc-air cell has entered into the industrial production stage, and is extensively applied.In recent years along with the improvement of battery structure and manufacturing process, the development of gas-diffusion electrode manufacturing process, the raising of zinc negative pole utilance, makes the combination property of battery have further raising.But be all below that chargeable secondary cell does not have tremendous development for zinc air primary cell.
Zinc-air cell negative electrode active material is encapsulated in inside battery, has the feature of storage battery; Secondly, positive active material, from airborne oxygen, has limitless volumes in theory, has the characteristic of fuel cell.Zinc-air cell also has following advantage in addition: 1, specific energy is high, because positive active material is from the outside of battery, without the space that takies battery, the in the situation that of same volume, weight, in zinc-air cell, can pack more negative electrode active material into, zinc-air cell is exceeded much than the capacity of common batteries, and theoretical specific energy reaches 1350Whkg
-1, actual specific energy has 220-300Whkg
-1, belong to large capacity high-energy chemistry power supply.2, cost is low, and cathode active material is oxygen in air, inexhaustible, and anode active material is metallic zinc, and its resource is also to enrich very much.3, stable performance, electric discharge steadily, because air electrode itself does not change when battery operated, adds zinc electrode voltage stabilization, so change in voltage can be very little while electric discharge.4, environmental protection, safe and reliable, from producing to use, from new product to waste recovery, all materials are all safe, not polluting the environment also not can combustion explosion, can deserve to be called green energy resource.
But current zinc-air cell substantially all belongs to disposable battery, do not have chargeable zinc air secondary battery.Because zinc-air cell adopts porous electrode, add that the self-characteristic of zinc electrode has caused the bottleneck of zinc-air cell development.Main problem have following some:
1, the growth of zinc dendrite.Due to the self character of zinc electrode, its self discharge reaction meeting, and in to the process of its charging, the zinc that has dendritic crystalline grows out, and its shape is very sharp, when being charged to a certain degree, dendritic growth can puncture the barrier film of battery, thereby causes short circuit, seriously reduces battery performance.
2, the direct oxidation of zinc electrode.Because airborne oxygen is dissolved in electrolyte, in course of reaction, form HO2
-if, HO2
-undecomposed, can be in air electrode accumulation, zinc electrode meeting direct oxidation, causes current potential to bear and moves, zinc electrode passivation, the activity of reduction zinc.
3, battery leakage problem.Because air electrode adopts loose structure, oxygen circulates from pore, thereby electrolyte also can be flowed out from hole, if can not carefully solve leakage problem, brings very large problem also can to the performance of zinc-air cell, has a strong impact on its performance and life-span.
Summary of the invention
Object of the present invention is for a kind of quasi-solid electrolyte PVA-zinc-air battery is provided, to solve the problems referred to above of prior art.
Object of the present invention can be achieved through the following technical solutions.
A kind of quasi-solid electrolyte PVA-zinc-air battery, it comprises zinc electrode, the electrolyte of air electrode, oxidation reaction that reduction reaction occurs and accommodates the battery case of air electrode, zinc electrode and electrolyte; Described electrolyte is to freeze the solid-state PVA-KOH-H of shape
2o alkaline polymer (PVA quasi-solid electrolyte) is provided with battery diaphragm between air electrode and zinc electrode.
Described air electrode is layer structure, is followed successively by from left to right waterproof ventilative layer, afflux layer (nickel foam) and Catalytic Layer; Above make some holes with pore creating material, be oxygen infusion passage for every layer.
The preparation method of above-mentioned air electrode, its step is as follows:
1) prepare waterproof ventilative layer: get 1:1:1.5 (quality) the uniform stirring mixing in proportion of acetylene black, active carbon, pore creating material, then dropwise adding 40%～60% (accounting for total amount) mass fraction is 60%PTFE emulsion, and uniform stirring is stand-by;
2) prepare Catalytic Layer: get 1:9:15:10 (quality) the uniform stirring mixing in proportion of acetylene black, active carbon, pore creating material and manganese dioxide, then dropwise adding 40%～60% (accounting for total amount) mass fraction is 60%PTFE emulsion, and uniform stirring is stand-by;
3) then respectively in the even smearing step 1 in the both sides of nickel foam) and step 2) prepared product, after treating to be evenly coated with and wiping, 120～150 DEG C of heat treatment 30～60 minutes in vacuum drying chamber or on hot platform;
4) use powder compressing machine compression molding, thickness is 1～2mm, is air electrode; Prepare be placed in thermostatic drying chamber after air electrode for subsequent use.
Described pore creating material is sodium acid carbonate or anhydrous sodium sulfate.If pore creating material is anhydrous sodium sulfate, need put into the water pore-creating of 60 DEG C.
The outside of described Catalytic Layer can add appropriate carbon nano-tube, to improve contacting of air electrode and PVA, reduces the internal resistance of battery.
Above-mentioned PVA-KOH-H
2the manufacture method of O alkaline polymer, comprises the following steps:
1) take certain mass weight northylen alcohol particle, mix with water by 1:40-1:50, heating water bath stirs, and bath temperature is 88-95 DEG C, stirs 50-70 minute, and polyvinyl alcohol transparent grain fades away, and water becomes thickness gradually simultaneously;
2) treat that transparent grain dissolves completely, then continue heating water bath 8-20 minute, evaporate unnecessary moisture, making PVA water content is 60%-70%;
3) dropwise add the KOH of 40%～50% 6-7mol/L preparing in advance; Obtain PVA solution;
4) by step 3) PVA solution be positioned under room temperature and make it naturally cooling, PVA solution becomes gradually and freezes shape solid, does not become completely while freezing shape solid at it, and it is splashed in battery case, carries out last follow-up encapsulation.
The preparation method of above-mentioned zinc electrode, the steps include:
1), taking zinc powder as material, add 2% binding agent and pore creating material, and add 3% corrosion inhibiter to reduce the corrosion certainly of zinc.
2) compression molding after uniform stirring, then compressing tablet thickness is about 1～1.5mm.Be placed on hermetically drying place.
The porous zinc electrodes that has adopted zinc powder to make has replaced traditional calamine cream, in order to reduce the internal resistance of battery, in cell package process, has added a small amount of carbon nano-tube to improve the contact resistance of zinc electrode and PVA.In discharge process, first surface is oxidized to ZnO with the zinc of lateral edges and adopts this loose structure, the ZnO generating can not block surface texture, can allow the zinc of inner side continue reaction, maximum using zinc electrode active material, a small amount of carbon nano-tube can be improved contacting of zinc electrode and PVA in addition, reduce contact resistance, also increase the conductivity of self simultaneously.So it is more complete that so a kind of porous zinc electrodes can react in battery charging and discharging, voltage is more steady, and the lifting of zinc-air cell performance is had to better effect.
The solid-state PVA zinc-air secondary battery of the preparation-obtained standard of the present invention can be applied to hearing aids, electronic watch, the fields such as portable electric appts and electric automobile such as mobile phone, zinc-air cell is after improving, stable performance is good, can obviously solve the formation of zinc dendrite in battery leakage and charging process, solve repeatedly zinc dendrite in charge and discharge process and punctured the phenomenon that battery diaphragm causes short circuit, extend it and discharged and recharged useful life.
The present invention adopts PVA-KOH-H2O alkaline polymer to replace traditional KOH electrolyte, and between them, maximum difference is exactly that this PVA adopting is present in inside battery with solid-state form, can bring thus following obvious advantage:
1, the growth of restriction zinc dendrite.This solid-state electrolytic solution of making is present in inside battery with the form of freezing shape, and itself is a kind of polymer, has good toughness.In the process of charging, ZnO can be reduced into deposit in the process that Zn regrows in zinc electrode and inhomogeneous again, so having the zinc of dendritic crystalline grows out, traditional liquid electrolyte or gluey electrolyte can not limit the growth of this zinc dendrite, so this solid-state electrolytic solution adopting is to freeze the solid of shape and have certain toughness, can hinder the growth of zinc dendrite, prevent from causing internal short-circuit of battery because the formation of zinc dendrite spine punctures barrier film, increase the useful life of battery, improved cell integrated performance.
2, stop battery leakage.Especially in this zinc-air cell structure, air anode has pore, traditional electrolyte can flow out very easily from pore, and for air electrode, it itself is a kind of structure of porous, in order to ensure its allomeric function, when battery operated, should guarantee its infiltrate and non-leakage, this PVA electrolyte surface of freezing shape shape just had good contact originally with Catalytic Layer, we add carbon nano-tube better to reduce their contact resistance in Catalytic Layer, fine in Catalytic Layer surface infiltration effect, and the solid-state structure of itself can ensure that electrolyte can not leak in the middle of air electrode pore, this has improved again the performance of zinc-air cell undoubtedly.So solid-state electrolyte obviously stops the generation of battery leakage, improve the overall performance of battery.
Brief description of the drawings
Fig. 1 is 2000 times of lower SEM figure of zinc electrode;
Fig. 2 uses liquid electrolyte to discharge and recharge SEM figure later;
Fig. 3 uses PVA quasi-solid electrolyte to discharge and recharge SEM figure later;
Fig. 4 is the graph of a relation that uses liquid electrolyte and PVA quasi-solid electrolyte electric discharge final pressure and cycle-index;
Fig. 5 is the CV curve that uses PVA quasi-solid electrolyte zinc-air cell to record;
Fig. 6 is the charge and discharge cycles resolution chart of liquid electrolyte;
Fig. 7 is the charge and discharge cycles resolution chart of PVA quasi-solid electrolyte.
Embodiment
Further set forth technical characterstic of the present invention below in conjunction with accompanying drawing and specific embodiment.
Preparation PVA quasi-solid electrolyte:
Embodiment 1:1) take a certain amount of granule of polyvinyl alcohol, mix with water by 0.5:32, heating water bath stirs, and bath temperature is 90 DEG C, stirs 60 minutes, and polyvinyl alcohol transparent grain fades away, and water becomes thickness gradually simultaneously; 2) treat that transparent grain dissolves completely, then continue heating water bath 10 minutes, evaporate unnecessary moisture, making PVA water content is 60%-70%; 3) dropwise add the KOH of 40%～50% 5～6mol/L preparing in advance; Obtain PVA solution; 4) by step 3) PVA solution be positioned under room temperature and make it naturally cooling, PVA solution becomes gradually and freezes shape solid, does not become completely while freezing shape solid at it, and it is splashed in battery case, carries out last follow-up encapsulation.
Embodiment 2: identical with above-mentioned steps, difference is: 1) mixed proportion of granule of polyvinyl alcohol and water is: 1:40, bath temperature is 88 DEG C, stirs 70 minutes; 2) treat grain dissolution, continue heating water bath 20 minutes; 3) dropwise add the KOH of 40% pre-configured 7mol/L.
Embodiment 3: step is identical with embodiment 1, and difference is: 1) mixed proportion of granule of polyvinyl alcohol and water is: 1:30, bath temperature is 95 DEG C, stirs 50 minutes; 2) treat grain dissolution, continue heating water bath 20 minutes; 3) dropwise add the KOH of 50% pre-configured 7mol/L.
Preparation zinc electrode:
Embodiment 4:1) taking zinc powder as material, add 2% binding agent and pore creating material, and add 3% corrosion inhibiter to reduce the corrosion certainly of zinc.2) compression molding after uniform stirring, then compressing tablet thickness is about 1～1.5mm.Be placed on hermetically drying place for subsequent use.
The SEM of prepared zinc electrode under 2000 times schemes as shown in Figure 1.
Prepare air electrode:
Embodiment 5:1) prepare waterproof ventilative layer: get the 1:1:1.5 uniform stirring mixing in proportion of acetylene black, active carbon, pore creating material, then dropwise adding 50% mass fraction is 60%PTFE emulsion, and uniform stirring is stand-by; 2) prepare Catalytic Layer: get the 1:9:15:10 uniform stirring mixing in proportion of acetylene black, active carbon, pore creating material and manganese dioxide, then dropwise adding 40% mass fraction is 60%PTFE emulsion, and uniform stirring is stand-by; 3) then respectively in the even smearing step 1 in the both sides of nickel foam) and step 2) prepared product, after treating to be evenly coated with and wiping, 150 DEG C of heat treatment 30 minutes in vacuum drying chamber or on hot platform; 4) use powder compressing machine compression molding, thickness is 1～2mm, is air electrode; Prepare be placed in thermostatic drying chamber after air electrode for subsequent use.
Embodiment 6:1) prepare waterproof ventilative layer: get the 1:1:1.5 uniform stirring mixing in proportion of acetylene black, active carbon, pore creating material, then dropwise adding 60% mass fraction is 60%PTFE emulsion, and uniform stirring is stand-by; 2) prepare Catalytic Layer: get the 1:9:15:10 uniform stirring mixing in proportion of acetylene black, active carbon, pore creating material and manganese dioxide, then dropwise adding 50% mass fraction is 60%PTFE emulsion, and uniform stirring is stand-by; 3) then respectively in the even smearing step 1 in the both sides of nickel foam) and step 2) prepared product, after treating to be evenly coated with and wiping, 150 DEG C of heat treatment 30 minutes in vacuum drying chamber or on hot platform; 4) use powder compressing machine compression molding, thickness is 1～2mm, is air electrode; Prepare be placed in thermostatic drying chamber after air electrode for subsequent use.
Encapsulation:
Embodiment 6: successively the zinc electrode preparing (embodiment 4), PVA solid-state electrolytic solution (embodiment 1-3 any one), battery diaphragm and air electrode (embodiment 5) are put into inside battery.Should be noted that PVA solid-state electrolytic solution need to not become completely while freezing shape solid and splash at it.The part contacting with PVA with zinc electrode in the Catalytic Layer of air electrode in addition adds a small amount of carbon nano-tube, thereby makes electrode have better contact with this PVA solid electrolyte, to reduce the internal resistance of battery.Afterwards to its encapsulation process.Packaged battery is tested by following:
Fig. 2 and Fig. 3 are respectively and use liquid electrolyte and PVA quasi-solid electrolyte to discharge and recharge SEM figure later.Can find out that electrode, using PVA to discharge and recharge the surface smoothing of surface ratio use liquid electrolyte later, has limited the growth of corner angle and zinc dendrite, to a great extent so be very beneficial for repeatedly periodic duty of battery.
Fig. 4 is the relation that uses liquid electrolyte and PVA quasi-solid electrolyte electric discharge final pressure and cycle-index, can find out, in electric discharge, press and be more or less the same, but after 100 circulations, use the sample voltage of liquid electrolyte to decline rapidly, and the sample voltage attenuation that uses PVA is little a lot, the performance after obviously battery repeatedly being circulated has certain maintenance.Improve to a certain extent battery life.
Fig. 5 is the CV curve that uses PVA quasi-solid electrolyte-zinc-air battery to record.
Fig. 6 and Fig. 7 are respectively the charge and discharge cycles test of liquid electrolyte and PVA quasi-solid electrolyte, can obviously find out, in Fig. 6 battery three be circulated throughout after basic inefficacy just, though fall short of discharge time and use PVA-zinc-air battery to circulate in the first two, but can keep stable discharging and recharging, 20 cycles keep good.
Claims (7)
1. a quasi-solid electrolyte PVA-zinc-air battery, is characterized in that: it comprises zinc electrode, the electrolyte of air electrode, oxidation reaction that reduction reaction occurs and accommodates the battery case of air electrode, zinc electrode and electrolyte; Described electrolyte is to freeze the solid-state PVA-KOH-H of shape
2o alkaline polymer is provided with battery diaphragm between air electrode and zinc electrode.
2. a kind of quasi-solid electrolyte PVA-zinc-air battery according to claim 1, is characterized in that: described air electrode is layer structure, is followed successively by from left to right waterproof ventilative layer, afflux layer (nickel foam) and Catalytic Layer; Above make some holes with pore creating material, be oxygen infusion passage for every layer; Its preparation process is as follows:
1) prepare waterproof ventilative layer: get the 1:1:1.5 uniform stirring mixing in proportion of acetylene black, active carbon, pore creating material, then dropwise adding 40%～60% mass fraction is 60%PTFE emulsion, and uniform stirring is stand-by;
2) prepare Catalytic Layer: get the 1:9:15:10 uniform stirring mixing in proportion of acetylene black, active carbon, pore creating material and manganese dioxide, then dropwise adding 40%～60% mass fraction is 60%PTFE emulsion, and uniform stirring is stand-by;
3) then respectively in the even smearing step 1 in the both sides of nickel foam) and step 2) prepared product, after treating to be evenly coated with and wiping, 120～150 DEG C of heat treatment 30～60 minutes in vacuum drying chamber or on hot platform;
4) use powder compressing machine compression molding, thickness is 1～2mm, is air electrode; Prepare be placed in thermostatic drying chamber after air electrode for subsequent use.
3. a kind of quasi-solid electrolyte PVA-zinc-air battery according to claim 2, is characterized in that: described pore creating material is sodium acid carbonate or anhydrous sodium sulfate.
4. a kind of quasi-solid electrolyte PVA-zinc-air battery according to claim 3, it is characterized in that: when described pore creating material is anhydrous sodium sulfate, need put into the water pore-creating of 40～60 DEG C, when pore creating material is carbonic hydroammonium, 120～150 DEG C of heat treatment pore-creating in 30～60 minutes on hot platform.
5. a kind of quasi-solid electrolyte PVA-zinc-air battery according to claim 2, is characterized in that: the outside of described Catalytic Layer can add appropriate carbon nano-tube.
6. a kind of quasi-solid electrolyte PVA-zinc-air battery according to claim 1, is characterized in that: described PVA-KOH-H
2the manufacture method of O alkaline polymer, comprises the following steps:
1) take a certain amount of granule of polyvinyl alcohol, mix with water by 1:40-1:50, heating water bath stirs, and bath temperature is 88-95 DEG C, stirs 50-70 minute, and polyvinyl alcohol transparent grain fades away, and water becomes transparent and thickness gradually simultaneously;
2) treat that transparent grain dissolves completely, then continue heating water bath 8-20 minute, evaporate unnecessary moisture, making PVA water content is 60%-70%;
3) dropwise add the KOH of 40%～60% 6-7mol/L preparing in advance; Obtain PVA solution;
4) by step 3) PVA solution be positioned under room temperature and make it naturally cooling, PVA solution becomes gradually and freezes shape solid, does not become completely while freezing shape solid at it, and it is splashed in battery case, carries out last follow-up encapsulation.
7. a kind of quasi-solid electrolyte PVA-zinc-air battery according to claim 1, is characterized in that: the preparation method of described zinc electrode, the steps include:
1), taking zinc powder as material, add 2%～5% binding agent and pore creating material, and add 3%～5% corrosion inhibiter to reduce the corrosion certainly of zinc;
2) compression molding after uniform stirring, then compressing tablet thickness is about 1～1.5mm; Be placed on hermetically drying place for subsequent use.
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Cited By (7)
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|---|---|---|---|---|
| CN105742760A (en) * | 2014-12-08 | 2016-07-06 | 中国科学院大连化学物理研究所 | Zinc/air fuel cell stack and operation method thereof |
| CN106898843A (en) * | 2015-12-17 | 2017-06-27 | 中国科学院大连化学物理研究所 | A kind of metal-air batteries electrolyte and its preparation and application |
| CN109921154A (en) * | 2019-03-08 | 2019-06-21 | 天津大学 | A kind of flexible zinc-air battery based on polymer dielectric |
| CN110197904A (en) * | 2019-06-13 | 2019-09-03 | 北京化工大学 | Structure and preparation method of positive electrode of zinc-nickel air flow battery |
| CN114883703A (en) * | 2022-05-08 | 2022-08-09 | 肖雨 | Preparation method and application of quasi-solid zinc-based battery with breathing gas as positive electrode reaction environment |
| CN115036518A (en) * | 2022-06-29 | 2022-09-09 | 河北工业大学 | Miniature all-solid-state zinc-air battery and preparation method thereof |
| CN115295930A (en) * | 2021-10-15 | 2022-11-04 | 青岛大学 | Integrated solid zinc-air battery with hollow structure |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105742760A (en) * | 2014-12-08 | 2016-07-06 | 中国科学院大连化学物理研究所 | Zinc/air fuel cell stack and operation method thereof |
| CN106898843A (en) * | 2015-12-17 | 2017-06-27 | 中国科学院大连化学物理研究所 | A kind of metal-air batteries electrolyte and its preparation and application |
| CN109921154A (en) * | 2019-03-08 | 2019-06-21 | 天津大学 | A kind of flexible zinc-air battery based on polymer dielectric |
| CN109921154B (en) * | 2019-03-08 | 2022-03-22 | 天津大学 | Flexible zinc-air battery based on polymer electrolyte |
| CN110197904A (en) * | 2019-06-13 | 2019-09-03 | 北京化工大学 | Structure and preparation method of positive electrode of zinc-nickel air flow battery |
| CN115295930A (en) * | 2021-10-15 | 2022-11-04 | 青岛大学 | Integrated solid zinc-air battery with hollow structure |
| CN114883703A (en) * | 2022-05-08 | 2022-08-09 | 肖雨 | Preparation method and application of quasi-solid zinc-based battery with breathing gas as positive electrode reaction environment |
| CN115036518A (en) * | 2022-06-29 | 2022-09-09 | 河北工业大学 | Miniature all-solid-state zinc-air battery and preparation method thereof |
| CN115036518B (en) * | 2022-06-29 | 2023-11-03 | 河北工业大学 | Miniature all-solid-state zinc-air battery and preparation method thereof |
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| CN103985923B (en) | 2017-02-15 |
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