CN103985923B - Quasi-solid electrolyte PVA-zinc-air battery - Google Patents
Quasi-solid electrolyte PVA-zinc-air battery Download PDFInfo
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- CN103985923B CN103985923B CN201410171564.1A CN201410171564A CN103985923B CN 103985923 B CN103985923 B CN 103985923B CN 201410171564 A CN201410171564 A CN 201410171564A CN 103985923 B CN103985923 B CN 103985923B
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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, specially a kind of quasi-solid electrolyte-PVA zinc-air battery, belong to new forms of energy skill
Art field.
Background technology
People for a long time, the mankind always with oil and coal as the energy, need with the energy in recent years in productive life
Being continuously increased of the amount of asking, non-renewable energy resources reserves but gradually decrease, and energy crisis starts to flash, and energy security becomes each state
The problem that family is highly absorbed in, is also the huge challenge that we face simultaneously.In this context, energy-saving and emission-reduction, green
Development is inevitable choice, seeks new forms of energy and substitutes fossil energy with aobvious urgent, and portable type electronic product constantly development and zero
Discharge being continuously increased of electric motor car demand, people meet requirement in the battery seeking a kind of high energy system.Zinc-air battery
As efficient, clean, green energy resource new technology, have that capacity is big, specific energy is high, low cost, discharge performance are stable, safe,
No pollution, the features such as high-power and material is renewable, it has also become world energy sources field focus at present, it is huge to be that one kind has
The chemical energy source of market prospects.
Since 1879, Maiche produced first and has done negative pole with zinc metal sheet, and air made by the porous carbon using platinum
After electrode makees the neutral electrolyte zinc-air battery of anode, develop through constantly, after the sixties in 20th century, zinc air
Disposable battery has significant progress, and slim air electrode is incorporated into zinc-air battery, is greatly enhanced putting of battery
Electrical property, so that zinc-air battery is developed important breakthrough.At the end of the sixties, efficient zinc-air battery has been introduced into industry
The productionization stage, and it is widely available application.Recently as the improvement of battery structure and manufacturing process, gas-diffusion electrode manufacture
The development of technique, the raising of zinc load utilization rate is so that the combination property of battery has further raising.But below it is all right
In zinc air one-shot battery, chargeable secondary cell does not have tremendous development.
Zinc-air battery negative electrode active material is encapsulated in inside battery, has the characteristics that battery；Secondly, positive electrode active material
Matter is derived from the oxygen of in the air, has limitless volumes in theory, has the characteristic of fuel cell.In addition zinc-air battery also have following excellent
Point：1st, specific energy is high, because positive active material is derived from the outside of battery, need not take the space of battery, in same volume, weight
In the case of amount, in zinc-air battery, more negative electrode active materials can be loaded so that zinc-air battery is than common batteries
Capacity exceeds a lot, and theoretical specific energy reaches 1350Wh kg-1, actual specific energy has 220-300Wh kg-1, belong to great Rong
Amount high-energy chemistry power supply.2nd, low cost, cathode active material be in the air oxygen it may be said that inexhaustible, and anode active material
For metallic zinc, its resource is also to enrich very much.3rd, stable performance, electric discharge steadily, due to air electrode when battery operated itself
Do not change, add zinc electrode voltage stabilization, so voltage change can very little during electric discharge.4th, environmental protection, safe and reliable, from
Produce use, from new product to waste recovery, all of material is all safe, not polluting the environment, it is quick-fried also will not to burn
Fried, green energy resource can be deserved to be called.
But current zinc-air battery broadly falls into disposable battery substantially, not chargeable zinc air secondary electricity
Pond.Because zinc-air battery adopts porous electrode, add that the self-characteristic of zinc electrode causes the bottleneck of zinc-air battery development.
Main problem have following some：
1st, the growth of zinc dendrite.Due to the self character of zinc electrode, meeting is reacted in its self discharge, and in the mistake that it is charged
Cheng Zhong, the zinc having dendritic crystalline grows out, and its shape is very sharp, and when charging to a certain extent, dendritic growth can puncture battery
Barrier film, thus causing short circuit, seriously reduce battery performance.
2nd, the direct oxidation of zinc electrode.Because the oxygen of in the air is dissolved in electrolyte, form HO2 during the course of the reaction-If,
HO2-Undecomposed, can be in air electrode accumulation, zinc electrode meeting direct oxidation, causes current potential to bear and moves, zinc electrode is passivated, reduce zinc
Activity.
3rd, battery leakage problem.Because air electrode adopts loose structure, oxygen circulates from pore, so that electrolyte
Also can flow out from hole, if leakage can not be solved the problems, such as carefully, bring very big problem, sternly also can to the performance of zinc-air battery
Ghost image rings its performance and life-span.
Content of the invention
The purpose of the present invention in order to provide a kind of quasi-solid electrolyte PVA- zinc-air battery, to solve prior art
The problems referred to above.
The purpose of the present invention can be achieved through the following technical solutions.
A kind of quasi-solid electrolyte PVA- zinc-air battery, it includes air electrode, the oxidation reaction that reduction reaction occurs
Zinc electrode, electrolyte and the battery case housing air electrode, zinc electrode and electrolyte；Described electrolyte is to freeze shape solid-state
PVA-KOH-H2O alkaline polymer (PVA quasi-solid electrolyte), be provided between air electrode and zinc electrode battery every
Film.
Described air electrode is layer structure, is followed successively by waterproof ventilative layer, current collector layer (nickel foam) from left to right and urges
Change layer；Make some holes with pore creating material on every layer, be oxygen transfer passage.
The preparation method of above-mentioned air electrode, its step is as follows：
1) prepare waterproof ventilative layer：Take acetylene black, activated carbon, pore creating material in proportion 1:1:1.5 (quality) uniform stirring mixes
Close, being then added dropwise over 40%～60% (accounting for total amount) mass fraction is 60%PTFE emulsion, and uniform stirring is stand-by；
2) prepare Catalytic Layer：Take acetylene black, activated carbon, pore creating material and manganese dioxide in proportion 1:9:15:10 (quality)
Uniform stirring mixes, and being then added dropwise over 40%～60% (accounting for total amount) mass fraction is 60%PTFE emulsion, and uniform stirring is treated
With；
3) and then respectively in the both sides uniform application step 1 of nickel foam) and step 2) obtained by product, treat uniform application
After good, in vacuum drying chamber or in thermal station, 120～150 DEG C are heat-treated 30～60 minutes；
4) use powder compressing machine compression molding, thickness is 1～2mm, as air electrode；It is placed on after preparing air electrode
Standby in thermostatic drying chamber.
Described pore creating material is sodium acid carbonate or anhydrous sodium sulfate.If pore creating material is anhydrous sodium sulfate, 60 DEG C need to be put into
Water in pore-creating.
The outside of described Catalytic Layer can add appropriate CNT, to improve the contact that air electrode is with PVA, reduces electricity
The internal resistance in pond.
Above-mentioned PVA-KOH-H2The preparation method of O alkaline polymer, comprises the following steps：
1) weigh certain mass weight northylen alcohol particle, by 1:40-1:50 are mixed with water, and heating water bath stirs, water-bath temperature
Spend for 88-95 DEG C, stir 50-70 minute, polyvinyl alcohol transparent grain fades away, and water gradually becomes sticky simultaneously；
2) treat that transparent grain is completely dissolved, be further continued for heating water bath 8-20 minute, evaporate unnecessary moisture, so that PVA is contained
The water yield is 60%-70%；
3) it is added dropwise over the KOH of 40%～50% 6-7mol/L preparing in advance；Obtain PVA solution；
4) by step 3) PVA solution place and allow its natural cooling at room temperature, PVA solution gradually becomes jelly shape solid,
When it does not become gelation shape solid completely, it is added dropwise in battery case, carries out finally follow-up encapsulation.
The preparation method of above-mentioned zinc electrode, its step is：
1) with zinc powder as material, add 2% binding agent and pore creating material, and add 3% corrosion inhibiter to reduce certainly corroding of zinc.
2) compression molding after uniform stirring, then sheeting thickness about 1～1.5mm.It is placed at hermetically drying.
Employ the porous zinc electrodes that zinc powder makes and instead of traditional calamine cream, in order to reduce the internal resistance of battery, in battery
In encapsulation process, add a small amount of CNT to improve the contact resistance of zinc electrode and PVA.Surface and side in discharge process
The zinc at edge is oxidized to ZnO first and adopts this loose structure, and the ZnO of generation will not block surface texture, can allow inner side
Zinc continues reaction, maximally utilizes zinc electrode active material, and in addition a small amount of CNT can improve connecing of zinc electrode and PVA
Touch, reduce contact resistance, also increase the electric conductivity of itself simultaneously.So such a porous zinc electrodes can be in battery charging and discharging
Reaction is more complete, and voltage is more steady, and the lifting to zinc-air battery performance has more preferable effect.
The preparation-obtained quasi- solid-state PVA zinc-air secondary battery of the present invention can apply to audiphone, electronic watch,
The field such as the portable electric appts such as mobile phone and electric automobile, after zinc-air battery is improved, stable performance is good, can
Substantially solve the formation of zinc dendrite in battery leakage and charging process, solve zinc dendrite in multiple charge and discharge process and puncture electricity
Pond barrier film leads to the phenomenon of short circuit, extends its discharge and recharge service life.
The present invention adopts PVA-KOH-H2O alkaline polymer to replace traditional KOH electrolyte, maximum difference between them
Be exactly this PVA adopting be in inside battery presented in solid-state, thus can bring following clear advantage：
1st, limit the growth of zinc dendrite.This solid-state electrolytic solution made is present in inside battery with the form freezing shape, it
Itself it is a kind of polymer, have good toughness.During charging, ZnO can be reduced into Zn in zinc electrode again again
During growth deposit and uneven, so the zinc having dendritic crystalline grows out, traditional liquid electrolyte or glue
The electrolyte of shape can not limit the growth of this zinc dendrite, thus adopt this solid-state electrolytic solution be freeze shape solid and
There is certain toughness, the growth of zinc dendrite can be hindered, prevent from puncturing barrier film and leading to inside battery because of the formation of zinc dendrite spine
Short circuit, increased the service life of battery, improves battery overall performance.
2nd, stop battery leakage.Especially in this zinc-air battery structure, air anode has a pore, traditional electrolysis
Liquid easily can flow out from pore very much, and for air electrode, itself is a kind of structure of porous, in order to ensure it
Allomeric function, it is ensured that it infiltrates and non-leakage when battery operated, this PVA electrolyte surface and the Catalytic Layer freezing shape shape this
Just there is good contact, we add CNT preferably to reduce their contact resistance in Catalytic Layer, in catalysis
Layer surface effect of impregnation is fine, and the solid-state structure of itself can ensure that electrolyte will not leak into air electrode pore and work as
In, this undoubtedly improves the performance of zinc-air battery again.So the electrolyte of solid-state substantially stops the generation of battery leakage, improve
The overall performance of battery.
Brief description
Fig. 1 is that the lower SEM of 2000 times of zinc electrode schemes；
Fig. 2 be using liquid electrolyte discharge and recharge after SEM figure；
Fig. 3 be using PVA quasi-solid electrolyte discharge and recharge after SEM figure；
Fig. 4 is the graph of a relation using liquid electrolyte and PVA quasi-solid electrolyte electric discharge final pressure and cycle-index；
Fig. 5 is the CV curve being recorded using PVA quasi-solid electrolyte zinc-air battery；
Fig. 6 is the charge and discharge cycles test chart of liquid electrolyte；
Fig. 7 is the charge and discharge cycles test chart of PVA quasi-solid electrolyte.
Specific embodiment
The technical characterstic of the present invention is expanded on further below in conjunction with the accompanying drawings with specific embodiment.
Preparation PVA quasi-solid electrolyte：
Embodiment 1：1) weigh a certain amount of granule of polyvinyl alcohol, by 0.5:32 are mixed with water, and heating water bath stirs, water-bath temperature
Spend for 90 DEG C, stir 60 minutes, polyvinyl alcohol transparent grain fades away, and water gradually becomes sticky simultaneously；2) treat transparent grain
It is completely dissolved, is further continued for heating water bath 10 minutes, evaporate unnecessary moisture, make PVA water content be 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 place
Allow its natural cooling at room temperature, PVA solution gradually becomes jelly shape solid, when it does not become gelation shape solid completely, it
It is added dropwise in battery case, carry out finally follow-up encapsulation.
Embodiment 2：Identical with above-mentioned steps, different is：1) granule of polyvinyl alcohol and the mixed proportion of water are：1:
40, bath temperature is 88 DEG C, stirs 70 minutes；2) treat grain dissolution, continue heating water bath 20 minutes；3) it is added dropwise over 40% pre-
The KOH of the 7mol/L first configuring.
Embodiment 3：Step is same as Example 1, and different is：1) mixed proportion of granule of polyvinyl alcohol and water
For：1:30, bath temperature is 95 DEG C, stirs 50 minutes；2) treat grain dissolution, continue heating water bath 20 minutes；3) it is added dropwise over
The KOH of 50% pre-configured 7mol/L.
Preparation zinc electrode：
Embodiment 4：1) with zinc powder as material, add 2% binding agent and pore creating material, and add 3% corrosion inhibiter to reduce zinc
From corrode.2) compression molding after uniform stirring, then sheeting thickness about 1～1.5mm.It is placed on standby at hermetically drying.
SEM figure under 2000 times for the prepared zinc electrode is as shown in Figure 1.
Prepare air electrode：
Embodiment 5：1) prepare waterproof ventilative layer：Take acetylene black, activated carbon, pore creating material in proportion 1:1:1.5 uniform stirring
Mixing, being then added dropwise over 50% mass fraction is 60%PTFE emulsion, and uniform stirring is stand-by；2) prepare Catalytic Layer：Take acetylene
Black, activated carbon, pore creating material and manganese dioxide in proportion 1:9:15:10 uniform stirring mixing, are then added dropwise over 40% mass
Fraction is 60%PTFE emulsion, and uniform stirring is stand-by；3) and then respectively in the both sides uniform application step 1 of nickel foam) and step
2) product obtained by, after treating uniform application well, in vacuum drying chamber or in thermal station, 150 DEG C are heat-treated 30 minutes；4) use
Powder compressing machine compression molding, thickness is 1～2mm, as air electrode；It is placed in thermostatic drying chamber after preparing air electrode
Standby.
Embodiment 6：1) prepare waterproof ventilative layer：Take acetylene black, activated carbon, pore creating material in proportion 1:1:1.5 uniform stirring
Mixing, being then added dropwise over 60% mass fraction is 60%PTFE emulsion, and uniform stirring is stand-by；2) prepare Catalytic Layer：Take acetylene
Black, activated carbon, pore creating material and manganese dioxide in proportion 1:9:15:10 uniform stirring mixing, are then added dropwise over 50% mass
Fraction is 60%PTFE emulsion, and uniform stirring is stand-by；3) and then respectively in the both sides uniform application step 1 of nickel foam) and step
2) product obtained by, after treating uniform application well, in vacuum drying chamber or in thermal station, 150 DEG C are heat-treated 30 minutes；4) use
Powder compressing machine compression molding, thickness is 1～2mm, as air electrode；It is placed in thermostatic drying chamber after preparing air electrode
Standby.
Encapsulation：
Embodiment 6：Successively by the zinc electrode preparing (embodiment 4), (embodiment 1-3 is any one for PVA solid-state electrolytic solution
Kind), battery diaphragm and air electrode (embodiment 5) put into inside battery.Should be noted that PVA solid-state electrolytic solution needs not complete at it
Instill when entirely being changed into freezing shape solid.In addition the part contacting with PVA with zinc electrode in the Catalytic Layer of air electrode adds a small amount of carbon
Nanotube, so that electrode is had with this PVA solid electrolyte preferably contact, to reduce the internal resistance of battery.Afterwards to its envelope
Dress is processed.By packaged battery by following test：
SEM after Fig. 2 and Fig. 3 is respectively using liquid electrolyte and PVA quasi-solid electrolyte discharge and recharge schemes.Can be seen that
Surface after using PVA discharge and recharge for the electrode smooths than the surface using liquid electrolyte, largely limits corner angle
With the growth of zinc dendrite, so be very beneficial for battery over multiple cycles work.
Fig. 4 is using liquid electrolyte and PVA quasi-solid electrolyte electric discharge final pressure and the relation of cycle-index, can see
Go out, in electric discharge, pressure is more or less the same, but after 100 circulations, the sample voltage using liquid electrolyte declines rapidly, and uses
PVA sample voltage decay much smaller hence it is evident that having certain holding to the performance after battery over multiple cycles.Carry to a certain extent
High battery life.
Fig. 5 is the CV curve being recorded using PVA quasi-solid electrolyte-zinc-air battery.
Fig. 6 and Fig. 7 is respectively the charge and discharge cycles test of liquid electrolyte and PVA quasi-solid electrolyte, it will be evident that
Just basic inefficacy after battery is circulated throughout at three in Fig. 6, though and use PVA- zinc-air battery to circulate discharge time in the first two
Fall short of, but stable discharge and recharge can be kept, 20 cycles keep good.
Claims (6)
1. a kind of quasi-solid electrolyte PVA- zinc-air battery it is characterised in that：It includes the air electricity that reduction reaction occurs
Pole, the zinc electrode of oxidation reaction, electrolyte and the battery case housing air electrode, zinc electrode and electrolyte；Described electrolysis
Liquid is the PVA-KOH-H freezing shape solid-state2O alkaline polymer, is provided with battery diaphragm between air electrode and zinc electrode；
Described PVA-KOH-H2The preparation method of O alkaline polymer, comprises the following steps：
1) weigh a certain amount of granule of polyvinyl alcohol, by 1:40-1:50 are mixed with water, and heating water bath stirs, and bath temperature is 88-95
DEG C, stir 50-70 minute, polyvinyl alcohol transparent grain fades away, and water gradually becomes transparent and sticky simultaneously；
2) treat that transparent grain is completely dissolved, be further continued for heating water bath 8-20 minute, evaporate unnecessary moisture, make PVA water content
For 60%-70%；
3) it is added dropwise over the KOH of 40%～60% 6-7mol/L preparing in advance；Obtain PVA solution；
4) by step 3) PVA solution place and allow its natural cooling at room temperature, PVA solution gradually becomes jelly shape solid, at it
When not becoming gelation shape solid completely, it is added dropwise in battery case, carries out finally follow-up encapsulation.
2. a kind of quasi-solid electrolyte PVA- zinc-air battery according to claim 1 it is characterised in that：Described sky
Pneumoelectric extremely layer structure, is followed successively by waterproof ventilative layer, current collector layer and Catalytic Layer from left to right；If making of pore creating material on every layer
Dry hole gap, is oxygen transfer passage；Its preparation process is as follows：
1) prepare waterproof ventilative layer：Take acetylene black, activated carbon, pore creating material in proportion 1:1:1.5 uniform stirring mixing, then dropwise
Addition 40%～60% mass fraction is 60%PTFE emulsion, and uniform stirring is stand-by；
2) prepare Catalytic Layer：Take acetylene black, activated carbon, pore creating material and manganese dioxide in proportion 1:9:15:10 uniform stirrings mix
Close, being then added dropwise over 40%～60% mass fraction is 60%PTFE emulsion, and uniform stirring is stand-by；
3) and then respectively in the both sides uniform application step 1 of nickel foam) and step 2) obtained by product, treat uniform application good it
Afterwards, in vacuum drying chamber or in thermal station 120～150 DEG C be heat-treated 30～60 minutes；
4) use powder compressing machine compression molding, thickness is 1～2mm, as air electrode；It is placed on constant temperature after preparing air electrode
Standby in drying box.
3. a kind of quasi-solid electrolyte PVA- zinc-air battery according to claim 2 it is characterised in that：Described makes
Hole agent 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 characterised in that：Described makes
When hole agent is anhydrous sodium sulfate, pore-creating in 40～60 DEG C of water need to be put into, when pore creating material is ammonium hydrogen carbonate, 120 in thermal station～
150 DEG C of heat treatment pore-creating in 30～60 minutes.
5. a kind of quasi-solid electrolyte PVA- zinc-air battery according to claim 2 it is characterised in that：Described urges
The outside changing layer can add appropriate CNT.
6. a kind of quasi-solid electrolyte PVA- zinc-air battery according to claim 1 it is characterised in that：Described zinc electricity
The preparation method of pole, its step is：
1) with zinc powder as material, add 2%～5% binding agent and pore creating material, and add 3%～5% corrosion inhibiter to reduce zinc
From corrosion；
2) compression molding after uniform stirring, then sheeting thickness about 1～1.5mm；It is placed on standby at hermetically drying.
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Families Citing this family (6)
| 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 |
| CN109921154B (en) * | 2019-03-08 | 2022-03-22 | 天津大学 | Flexible zinc-air battery based on polymer electrolyte |
| CN110197904B (en) * | 2019-06-13 | 2020-09-22 | 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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101132084A (en) * | 2006-08-24 | 2008-02-27 | 比亚迪股份有限公司 | Zinc-air battery |
| CN101683613A (en) * | 2008-09-22 | 2010-03-31 | 北京长力联合能源技术有限公司 | Catalytic agent for air electrode and novel air electrode manufactured by catalytic agent and manufacturing method of air electrode |
| CN102509774A (en) * | 2011-10-27 | 2012-06-20 | 北京中航长力能源科技有限公司 | Preparation method of zinc electrode used for zinc-air battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1715536A3 (en) * | 2005-04-20 | 2007-10-10 | ReVolt Technology AS | Zinc electrode comprising an organic gelling agent and an organic binder. |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101132084A (en) * | 2006-08-24 | 2008-02-27 | 比亚迪股份有限公司 | Zinc-air battery |
| CN101683613A (en) * | 2008-09-22 | 2010-03-31 | 北京长力联合能源技术有限公司 | Catalytic agent for air electrode and novel air electrode manufactured by catalytic agent and manufacturing method of air electrode |
| CN102509774A (en) * | 2011-10-27 | 2012-06-20 | 北京中航长力能源科技有限公司 | Preparation method of zinc electrode used for zinc-air battery |
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| Title |
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| "Preparation of alkaline PVA-based polymer electrolytes for Ni-MH and Zn-air batteries";C-C.YANG等;《Journal of Applied Electrochemistry》;20030930;第33卷(第9期);第777-784页 * |
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