CN109904471A - A kind of preparation method of all-solid-state flexible metal-air battery - Google Patents
A kind of preparation method of all-solid-state flexible metal-air battery Download PDFInfo
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- CN109904471A CN109904471A CN201910091032.XA CN201910091032A CN109904471A CN 109904471 A CN109904471 A CN 109904471A CN 201910091032 A CN201910091032 A CN 201910091032A CN 109904471 A CN109904471 A CN 109904471A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention relates to a kind of preparation methods of all-solid-state flexible metal-air battery, the following steps are included: transition metal phosphide is distributed in the mixed solution of Nafion solution and dehydrated alcohol, dispersion liquid is obtained, dispersant liquid drop is coated onto the anode dried at room temperature on carbon cloth as flexible all solid state metal-air battery；A certain amount of sodium hydrate aqueous solution is slowly dripped in acrylic acid aqueous solution and is stirred evenly, a certain amount of ammonium persulfate aqueous solution is slowly dripped in above-mentioned solution；Then it seals after above-mentioned solution being vacuumized deoxygenation and solidifies in 50 DEG C -60 DEG C of baking oven, the film after solidification takes out after sufficiently impregnating in potassium hydroxide and zinc chloride mixed solution, and the preparation of Sodium Polyacrylate electrolyte flexible solid zinc and air cell is made.
Description
Technical field
The present invention relates to a kind of positive electrodes for using transition metal phosphide as metal-air battery, belong to metal sky
Gas battery technology field.
Background technique
With the growing demand of moveable flexible electronic devices, matched flexible energy storage and conversion
Equipment is also required to develop.Metal-air battery due to energy density with higher, low cost, it is environmental-friendly the features such as and have
Prestige leads clean energy resource.However the slow kinetics and high overpotential of positive redox reactions and oxygen evolution reaction
Hinder the raising of energy efficiency and power capacity.Although noble metal platinum, ruthenium-oxide show fabulous performance, disappear greatly
Consumption, the stability of difference and scarcity of resources hinder its large-scale application.Therefore need to develop the catalysis of low cost, high stability
Agent replaces noble metal catalyst.
Transition metal phosphide is a kind of elctro-catalyst with fine electrocatalysis characteristic, has rich reserves, price low
The advantages that honest and clean, it is possible to be used as the positive electrode of metal-air battery.It can be used for being prepared into flexible all solid state metal-
Air cell.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of metal-air battery with performance.Technology of the invention
Scheme by following steps realize,
A kind of preparation method of all-solid-state flexible metal-air battery, comprising the following steps:
(1) transition metal phosphide is distributed in the mixed solution of Nafion solution and dehydrated alcohol, obtains dispersion liquid,
Dispersant liquid drop is coated onto the anode dried at room temperature on carbon cloth as flexible all solid state metal-air battery.
(2) a certain amount of sodium hydrate aqueous solution is slowly dripped in acrylic acid aqueous solution and is stirred evenly, it will be a certain amount of
Ammonium persulfate aqueous solution slowly drip in above-mentioned solution；Then it is sealed after above-mentioned solution being vacuumized deoxygenation and at 50 DEG C -60
DEG C baking oven in solidify, the film after solidification in potassium hydroxide and zinc chloride mixed solution sufficiently impregnate after take out, be made poly- third
Olefin(e) acid sodium electrolyte.
(3) it clip sheet metal and polishes as metal negative electrode, by the sheet metal and flexible all solid state metal-air after polishing
The anode of battery is respectively placed in the two sides of Sodium Polyacrylate electrolyte, is flexible solid zinc and air cell.
Preferably, the transition metal phosphide is two cobalt of phosphatization.
(1) in, volume ratio 0.1:25~5:25 of Nafion solution and dehydrated alcohol.
(2) in, sodium hydroxide: acrylic acid: the molar ratio of ammonium persulfate is 3:1:1.4~1:1:0.5；Potassium hydroxide and chlorine
Change zinc mixed solution, the concentration of the two is respectively 5-7M and 0.15-25M.
The present invention prepares metal-air battery using raw material cheap and easy to get, and preparation process is simple, controllability is strong, has
Good power-performance, specific capacity and stability.
Detailed description of the invention
Fig. 1 is the stable charge/discharge for all solid state zinc and air cell of flexibility that the embodiment of the present invention 1 obtains.Obviously from the figure
The battery has stable charge-discharge performance out.
Fig. 2 is the discharge curve and power density curve for all solid state zinc and air cell of flexibility that the embodiment of the present invention 1 obtains.From
The figure can be seen that the battery has very high power density.
Fig. 3 is the specific capacity for all solid state zinc and air cell of flexibility that the embodiment of the present invention 1 obtains.From this view it is apparent that the electricity
Pond has very high specific capacity.
Specific embodiment
The present invention uses transition metal phosphide as air cathode to prepare metal-air battery.It is closed by one-step calcination
At transition metal phosphide, is then loaded to and be used as air cathode on collector.
The present invention is described as follows combined with specific embodiments below:
Embodiment 1:
(1) two cobalt of 1mg phosphatization is distributed to the mixed of 200 μ LNafion solution (No. CAS: 31175-20-9) and dehydrated alcohol
It closes in solution (volume ratio 1:25), ultrasonic 20min obtains uniform dispersion liquid, then by its drop coating to 1 × 1cm2Carbon cloth on
The anode as flexible all solid state metal-air battery is dried at room temperature.
(2) a certain amount of (1g/mL) sodium hydrate aqueous solution is slowly dripped into acrylic acid aqueous solution (33wt%) stirring
Uniformly.A certain amount of ammonium persulfate (37wt%) aqueous solution slowly drips in above-mentioned solution (sodium hydroxide: acrylic acid: persulfuric acid
The molar ratio of ammonium is 3:1:1.4).Then above-mentioned solution is vacuumized and pours into square plate sealing after deoxygenation and in 60 DEG C of baking oven
Solidification one day.The film after solidifying is taken out to be immersed in the potassium hydroxide of 6M and the liquor zinci chloridi of 0.2M one week or so.
(3) one piece of 1 × 3cm of clip2Zinc metal sheet and polish as metal negative electrode.By the zinc metal sheet and drop coating catalyst after polishing
Carbon cloth afterwards is individually placed to the two sides of Sodium Polyacrylate electrolyte, is flexible solid zinc and air cell.
Embodiment 2:
(1) two cobalt of 2mg phosphatization is distributed to the mixed of 200 μ LNafion solution (No. CAS: 31175-20-9) and dehydrated alcohol
It closes in solution (volume ratio 1:25), ultrasonic 20min obtains uniform dispersion liquid, then by its drop coating to 1 × 1cm2Carbon cloth or
The anode as flexible all solid state metal-air battery is dried on carbon paper at room temperature.
(2) a certain amount of (1g/mL) sodium hydrate aqueous solution is slowly dripped into acrylic acid aqueous solution (33wt%) stirring
Uniformly.A certain amount of ammonium persulfate (37wt%) aqueous solution slowly drips in above-mentioned solution (sodium hydroxide: acrylic acid: persulfuric acid
The molar ratio of ammonium is 1:1:1.4).Then above-mentioned solution is vacuumized and pours into square plate sealing after deoxygenation and in 60 DEG C of baking oven
Solidification one day.The film after solidifying is taken out to be immersed in the potassium hydroxide of 6M and the liquor zinci chloridi of 0.2M one week or so.
(3) one piece of 1 × 3cm of clip2Zinc metal sheet and polish as metal negative electrode.By after polishing sheet metal and drop coating catalysis
Carbon cloth after agent is individually placed to the two sides of Sodium Polyacrylate electrolyte, is flexible solid zinc and air cell.
Embodiment 3:
(1) two cobalt of 1-5mg phosphatization is distributed to 200 μ LNafion solution (No. CAS: 31175-20-9) and dehydrated alcohol
In mixed solution (volume ratio 1:25), ultrasonic 20min obtains uniform dispersion liquid, then by its drop coating to 1 × 1cm2Carbon cloth
Or anode as flexible all solid state metal-air battery is dried on carbon paper at room temperature.
(2) a certain amount of (1g/mL) sodium hydrate aqueous solution is slowly dripped into acrylic acid aqueous solution (33wt%) stirring
Uniformly.A certain amount of ammonium persulfate (37wt%) aqueous solution slowly drips in above-mentioned solution (sodium hydroxide: acrylic acid: persulfuric acid
The molar ratio of ammonium is 3:1:0.4).Then above-mentioned solution is vacuumized and pours into square plate sealing after deoxygenation and in 60 DEG C of baking oven
Solidification one day.The film after solidifying is taken out to be immersed in the potassium hydroxide of 6M and the liquor zinci chloridi of 0.2M one week or so.
(3) one piece of 1 × 3cm of clip2Zinc metal sheet and polish as metal negative electrode.By after polishing sheet metal and drop coating catalysis
Carbon cloth after agent is individually placed to the two sides of Sodium Polyacrylate electrolyte, and is sealed (air electrode side bundle with plastic packaging film
Eye), it is flexible solid zinc and air cell.
Claims (4)
1. a kind of preparation method of all-solid-state flexible metal-air battery, comprising the following steps:
(1) transition metal phosphide is distributed in the mixed solution of Nafion solution and dehydrated alcohol, obtains dispersion liquid, will divided
The anode as flexible all solid state metal-air battery is dried in dispersion liquid drop coating to carbon cloth at room temperature.
(2) a certain amount of sodium hydrate aqueous solution is slowly dripped in acrylic acid aqueous solution and is stirred evenly, by a certain amount of mistake
Ammonium sulfate solution slowly drips in above-mentioned solution；Then it is sealed after above-mentioned solution being vacuumized deoxygenation and at 50 DEG C -60 DEG C
Solidify in baking oven, the film after solidification takes out after sufficiently impregnating in potassium hydroxide and zinc chloride mixed solution, and polyacrylic acid is made
Sodium electrolyte.
(3) it clip sheet metal and polishes as metal negative electrode, by the sheet metal and flexible all solid state metal-air battery after polishing
Anode be respectively placed in the two sides of Sodium Polyacrylate electrolyte, be flexible solid zinc and air cell.
2. preparation method according to claim 1, which is characterized in that the transition metal phosphide is two cobalt of phosphatization.
3. preparation method according to claim 1, which is characterized in that (1) in, the volume of Nafion solution and dehydrated alcohol
Than 0.1:25~5:25.
4. preparation method according to claim 1, which is characterized in that (2) in, sodium hydroxide: acrylic acid: ammonium persulfate
Molar ratio is 3:1:1.4~1:1:0.5；Potassium hydroxide and zinc chloride mixed solution, the concentration of the two are respectively 5-7M and 0.15-
25M。
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| CN201910091032.XA CN109904471A (en) | 2019-01-30 | 2019-01-30 | A kind of preparation method of all-solid-state flexible metal-air battery |
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| CN201910091032.XA CN109904471A (en) | 2019-01-30 | 2019-01-30 | A kind of preparation method of all-solid-state flexible metal-air battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110492111A (en) * | 2019-08-09 | 2019-11-22 | 安徽理工大学 | A kind of chargeable zinc-air battery based on cobalt-base catalyst, preparation method and application |
| CN116145425A (en) * | 2023-04-23 | 2023-05-23 | 江苏恒力化纤股份有限公司 | Semi-interpenetrating network gel electrolyte membrane and preparation method and application thereof |
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| CN105403606A (en) * | 2015-11-10 | 2016-03-16 | 西安建筑科技大学 | Preparation method for carbon cloth electrode based on cobalt phosphide/hemoglobin modification |
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2019
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| CN103923259A (en) * | 2014-04-29 | 2014-07-16 | 青岛科技大学 | Polyethylene amine amphoteric polyelectrolyte and preparation method thereof |
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| CN105403606A (en) * | 2015-11-10 | 2016-03-16 | 西安建筑科技大学 | Preparation method for carbon cloth electrode based on cobalt phosphide/hemoglobin modification |
| CN108365230A (en) * | 2018-01-04 | 2018-08-03 | 中国科学院大学 | A kind of universality preparation method and application for the air electrode that active site is combined with electrode structure |
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| YAN HUANG ET AL.: "Solid-State Rechargeable Zn//NiCo and Zn-Air Batteries with Ultralong Lifetime and High Capacity: The Role of a Sodium Polyacrylate Hydrogel Electrolyte", 《ADVANCED ENERGY MATERIALS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110492111A (en) * | 2019-08-09 | 2019-11-22 | 安徽理工大学 | A kind of chargeable zinc-air battery based on cobalt-base catalyst, preparation method and application |
| CN110492111B (en) * | 2019-08-09 | 2021-08-06 | 安徽理工大学 | Rechargeable zinc-air battery based on cobalt-based catalyst, preparation method and application |
| CN116145425A (en) * | 2023-04-23 | 2023-05-23 | 江苏恒力化纤股份有限公司 | Semi-interpenetrating network gel electrolyte membrane and preparation method and application thereof |
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Application publication date: 20190618 |