CN109860647A - Alkaline flexible electrolyte film of zinc-manganese battery and preparation method thereof - Google Patents
Alkaline flexible electrolyte film of zinc-manganese battery and preparation method thereof Download PDFInfo
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- CN109860647A CN109860647A CN201811556302.1A CN201811556302A CN109860647A CN 109860647 A CN109860647 A CN 109860647A CN 201811556302 A CN201811556302 A CN 201811556302A CN 109860647 A CN109860647 A CN 109860647A
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Abstract
The alkaline flexible electrolyte film of the zinc-manganese battery is prepared by the following method: polyvinyl alcohol PVA and silicon dioxide SiO 2 Dissolving in deionized water to obtain a solution A; dropwise adding a potassium hydroxide solution, and stirring to obtain a solution B; dropwise adding the dissolved hydroxypropyl methyl cellulose solution into the solution B, uniformly stirring, and finally adding a UV cross-linking agent; and finally, pouring the solution into a mold, and drying to form a film under the irradiation of ultraviolet light.
Description
Technical Field
The invention belongs to the field of battery material processing, and particularly relates to a preparation method of an alkaline flexible electrolyte film for a zinc-manganese dioxide battery.
Background
In recent years, the introduction of concepts of flexible portable electronic products such as a roll-up display, a flexible liquid crystal display, and a fully flexible wearable electronic device has not only attracted the interest and expectation of consumers, but also triggered the research of researchers on flexible electronic technology. The flexible power supply part in the flexible electronic technology is used as a main power supply source of electronic products, and comprises a zinc-manganese primary battery, a zinc-lithium primary battery, a lithium ion secondary battery, a silver-zinc secondary battery and a super capacitor.
At present, a commercially available temperature patch for children is composed of a zinc-manganese primary battery, zinc as a negative electrode, manganese dioxide as a positive electrode, a diaphragm and an electrolyte. In order to improve the capacity of zinc-manganese battery products, researchers prepare alkaline electrolyte films by a method of mixing a polymer and an alkaline solution for gelation and then forming the films.
The polymer electrolyte is a high molecular complex compound which is generated by high polymer and inorganic salt and has the ionic conductivity, and has the advantages of good mechanical property and volume strain property, light weight, high specific energy, liquid leakage elimination and the like. The alkaline solid electrolyte has the advantages of good mechanical property, high specific energy, stable conductivity, elimination of leakage, low price and the like, and is gradually a research hotspot in the field of alkaline secondary batteries. The polymer film at present has three kinds of PVA (polyvinyl alcohol), PEO (polyethylene oxide) and PAA (polyacrylic acid), and compared with PEO and PAA, the PVA film has relatively moderate ionic conductivity and mechanical strength and is cheap.
Disclosure of Invention
The invention aims to provide an alkaline flexible electrolyte film and a preparation method thereof by adopting PVA as a main film forming material and enhancing the mechanical property and the discharge property of the film by adding additives and improving the preparation process.
In order to solve the above technical problems, a technical solution of a first aspect of the present invention is: the alkaline flexible electrolyte film of the zinc-manganese battery is prepared by the following method:
(1) Polyvinyl alcohol PVA and silicon dioxide SiO 2 Dissolving in deionized water, and stirring uniformly to obtain a solution A;
(2) Dropwise adding a potassium hydroxide solution KOH into the solution A, and stirring at the same time to obtain a solution B;
(3) Dissolving hydroxypropyl methylcellulose (HPMC) in a deionized water solution to obtain a solution C, slowly dropwise adding the solution C into the solution B, uniformly stirring, and finally adding a UV cross-linking agent;
(4) And (4) pouring the solution obtained in the step (3) into a mould, and drying to form a film under the irradiation of ultraviolet light.
In the preferred technical scheme of the invention, the mass ratio of the polyvinyl alcohol to the silicon dioxide is 1.0-1.5: 0.05-0.1.
In the preferred technical scheme of the invention, the mass ratio of the polyvinyl alcohol to the potassium hydroxide is 1.0-1.3: 1.96-5.6.
In the preferable technical scheme of the invention, in the step (1), the solution A is kept at 70-90 ℃ to obtain a semitransparent solution, and then a potassium hydroxide solution KOH is dropwise added.
In the preferable technical scheme of the invention, in the step (2), the potassium hydroxide solution K OH contains 1-2% by mass of zinc oxide ZnO.
In the preferable technical scheme of the invention, in the step (3), the temperature of the solution B is kept between 50 and 65 ℃.
In the preferred technical scheme of the invention, in the step (4), after vacuumizing for 10-20min in a vacuum environment, the film is placed for 10-30s under the irradiation of ultraviolet light, and then the film is placed in an environment with the temperature of 10-30 ℃ and the humidity of 50-80% to obtain the alkaline film.
In the preferred technical scheme of the invention, the mass ratio of the polyvinyl alcohol to the hydroxypropyl methyl cellulose HPMC is 1.0-1.5: 0.02-0.07.
Preferably, the alkaline flexible electrolyte film of the zinc-manganese battery is prepared by the following method: weighing 1.0-1.5g of PVA and 0.05-0.1g of SiO2 in 10-20mL of deionized water, stirring at normal temperature for 15-30min, and slowly heating to 70-90 ℃ to obtain a semitransparent solution. Then increasing the stirring speed, dropwise adding 5-10mL of KOH solution with the concentration of 7-10mol/L and the concentration of 1% -2% of ZnO, stirring for 20-40min, and cooling to 50-65 ℃. And additionally weighing 0.02-0.07g of HPMC (hydroxy propyl methyl cellulose) to be dissolved in 5-15mL of deionized water solution, slowly dripping into the solution after complete ultrasonic dissolution, stirring for 30-60min, then dripping 10-40 mu L of UV cross-linking agent, continuously stirring for 10-30min, and pouring the solution into a PP die. Placing in vacuum environment, vacuumizing for 10-20min, standing under ultraviolet irradiation for 10-30s, and standing at 10-30 deg.C and 50-80% humidity for 10-18h to obtain alkaline film.
The technical scheme of the second aspect of the invention is as follows: the preparation method of the alkaline flexible electrolyte film of the zinc-manganese battery comprises the following steps:
(1) Polyvinyl alcohol PVA and silicon dioxide SiO 2 Dissolving in deionized water, and stirring uniformly to obtain a solution A;
(2) Dropwise adding a potassium hydroxide solution KOH into the solution A, and stirring simultaneously to obtain a solution B;
(3) Dissolving hydroxypropyl methylcellulose HPMC in deionized water solution to obtain solution C, slowly dropwise adding the solution C into the solution B, stirring uniformly, and finally adding UV cross-linking agent;
(4) And (4) pouring the solution obtained in the step (3) into a mould, and drying to form a film under the irradiation of ultraviolet light.
SiO for selection in the process of the invention 2 Is fumed silica, is a powdery porous substance, and is made of SiO 2 ·nH 2 O form exists, wherein nH 2 O exists in the form of surface hydroxyl, can form hydrogen bonds with water, strengthens the network structure of the film, absorbs more KOH solution and increases the reaction capacity of the battery. ZnO is added to form in the electrolyteCan reduce corrosion of zinc when the battery is laid aside, promote early precipitation of ZnO when the battery is discharged for a long time, and is in liquid stateConversion to solid ZnO and OH-to form Zn 2+ Binding more OH - Thereby prolonging the battery discharge time. In the method, the HPMC is added because the aqueous solution of the HPMC has excellent film-forming property, the formed film is transparent, tough and difficult to adhere, is non-toxic, harmless and pollution-free, and is environment-friendly, and the HPMC also is an excellent water-retaining agent with certain thickening property, so that the aims of shortening the film-forming time and improving the water content and the discharge performance of the film can be achieved. The vacuum pumping is used for eliminating air bubbles generated when the electrolyte is poured into the film and preventing large air holes from being formed in the film after the film is formed to cause electrode short circuit, and then the film is easy to dry and form after the vacuum pumping, so that the electrolyte cannot be spread due to overlarge surface tension. Adding intoThe UV cross-linking agent is used to shorten the cross-linking time and film-forming time of PVA. In the method, PVA is selected as a main film forming material, and the PVA-based alkaline polymer electrolyte has higher room-temperature conductivity which can reach 10-2S/cm order of magnitude.
Drawings
FIG. 1 is a graph showing AC impedance of the film obtained in example 1 and a pure PVA film measured with a stainless steel foil.
FIG. 2 is a graph showing the discharge curves of the batteries tested using the home-made positive and negative electrodes, the film obtained in example 1 and the PVA film.
Detailed Description
The technical solutions in the present invention are clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1.2g of PVA and 0.07g of SiO2 were weighed out and stirred in 15mL of deionized water at room temperature for 15 minutes, and then slowly heated to 80 ℃ to obtain a translucent solution. Then 7mL of 8mol/L KOH solution containing 1.5 percent of ZnO is added dropwise with increasing stirring speed, and the mixture is cooled after being stirred for 40 min. And additionally weighing 0.04g of HPMC (hydroxy propyl methyl cellulose) to dissolve in 8mL of deionized water solution, slowly dripping into the solution after complete ultrasonic dissolution, stirring for 30min, then dripping 10 mu L of UV cross-linking agent, continuously stirring for 15min, and pouring the solution into a PP (polypropylene) mold. Placing in vacuum environment, vacuumizing for 15min, standing under ultraviolet irradiation for 60s, and standing at 15 deg.C and 70% humidity for 13h to obtain alkaline film.
From FIG. 1, the experimental film and the pure PVA film obtained in example 1 were tested to have Rb values of 1.65. Omega. And 2.70. Omega. Respectively, and stainless steel was usedThe area of the steel foil is 0.785cm2, and the thickness of the film is 0.5mm. The conductivities of the experimental film and the pure PVA film are respectively 3.86 multiplied by 10, which is obtained by the formula sigma = l/(Rb.A) -2 S·cm -1 And 2.35X 10 -2 S·cm -1 。
Example 2
1.0g of PVA and 0.05g of SiO2 were weighed out and placed in 15mL of deionized water, and after stirring at room temperature for 20min, the mixture was slowly heated to 70 ℃ to obtain a translucent solution. Then 5mL of 7mol/L KOH solution containing 1 percent of ZnO is added dropwise at an increased stirring speed, and the mixture is stirred for 20min and then cooled to 50 ℃. And additionally weighing 0.02g of HPMC (hydroxy propyl methyl cellulose) to dissolve in 5mL of deionized water solution, slowly dripping into the solution after complete ultrasonic dissolution, stirring for 30min, then dripping 10-40 mu L of UV cross-linking agent, continuously stirring for 10min, and pouring the solution into a PP (polypropylene) mold. Placing in vacuum environment, vacuumizing for 10min, standing for 30s under ultraviolet irradiation with wavelength of 300nm, and then placing in environment with temperature of 30 deg.C and humidity of 50% for 10h to obtain the alkaline film.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited by the foregoing examples, which are provided to illustrate the principles of the invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention, which is also intended to be covered by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. An alkaline flexible electrolyte film of a zinc-manganese battery is characterized by being prepared by the following method:
(1) Polyvinyl alcohol PVA and silicon dioxide SiO 2 Dissolving in deionized water, and stirring uniformly to obtain a solution A;
(2) Dropwise adding a potassium hydroxide solution KOH into the solution A, and stirring simultaneously to obtain a solution B;
(3) Dissolving hydroxypropyl methyl cellulose in a deionized water solution to obtain a solution C, slowly dropwise adding the solution C into the solution B, uniformly stirring, and finally adding a UV cross-linking agent;
(4) And (4) pouring the solution obtained in the step (3) into a mould, and drying to form a film under the irradiation of ultraviolet light.
2. The alkaline flexible electrolyte membrane for a zinc-manganese battery according to claim 1, wherein the mass ratio of polyvinyl alcohol to silica is 1.0 to 1.5: 0.05 to 0.1.
3. The alkaline flexible electrolyte membrane for a zinc-manganese battery according to claim 1, wherein the mass ratio of the polyvinyl alcohol to the potassium hydroxide is 1.0 to 1.3: 1.96 to 5.6.
4. The alkaline flexible electrolyte membrane for a zinc-manganese battery according to claim 1, wherein in the step (1), the solution a is maintained at 70 to 90 ℃ to obtain a translucent solution, and then a potassium hydroxide solution is added dropwise.
5. The alkaline flexible electrolyte membrane for a zinc-manganese battery according to claim 1, wherein in the step (2), the zinc oxide is contained in the potassium hydroxide solution in a mass percentage of 1-2%.
6. The alkaline flexible electrolyte membrane for a zinc-manganese battery according to claim 1, wherein in step (3), the solution B is maintained at a temperature of 50 to 65 ℃.
7. The alkaline flexible electrolyte membrane for a zinc-manganese battery according to claim 1, wherein in the step (4), after evacuation is performed in a vacuum environment for 10-20min, the membrane is left to stand under ultraviolet irradiation for 10-30s, and then the membrane is left to stand in an environment with a temperature of 10-30 ℃ and a humidity of 50-80% to obtain the alkaline membrane.
8. The alkaline flexible electrolyte membrane for zinc-manganese dioxide battery according to claim 1, wherein the mass ratio of polyvinyl alcohol to hydroxypropylmethylcellulose is 1.0-1.5: 0.02-0.07.
9. The preparation method of the alkaline flexible electrolyte film of the zinc-manganese battery comprises the following steps:
(1) Polyvinyl alcohol PVA and silicon dioxide SiO 2 Dissolving in deionized water, and stirring uniformly to obtain a solution A;
(2) Dropwise adding a potassium hydroxide solution KOH into the solution A, and stirring at the same time to obtain a solution B;
(3) Dissolving hydroxypropyl methyl cellulose in a deionized water solution to obtain a solution C, slowly dropwise adding the solution C into the solution B, uniformly stirring, and finally adding a UV cross-linking agent;
(4) And (4) pouring the solution obtained in the step (3) into a mould, and drying to form a film under the irradiation of ultraviolet light.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115732770A (en) * | 2022-12-07 | 2023-03-03 | 北京理工大学 | Flexible self-healing electrolyte membrane, preparation method thereof and battery |
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| CN1691396A (en) * | 2004-04-30 | 2005-11-02 | 比亚迪股份有限公司 | Alkaline storage battery and preparation method thereof |
| CN1918732A (en) * | 2004-04-23 | 2007-02-21 | 松下电器产业株式会社 | Alkaline battery |
| US20070105020A1 (en) * | 2005-11-08 | 2007-05-10 | Gwo-Mei Wu | Fabrication method of a basic polymer electrolyte film of blended polyvinyl alcohol and quaternary amine |
| CN101515655A (en) * | 2009-03-16 | 2009-08-26 | 清华大学 | Three dimensional structure micro zinc-nickel battery applying to microsystems and preparation method thereof |
| WO2013000584A1 (en) * | 2011-06-30 | 2013-01-03 | Hochschule Mannheim | Method for producing alkaline polymer electrolyte membranes |
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- 2018-12-19 CN CN201811556302.1A patent/CN109860647A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1581567A (en) * | 2003-08-06 | 2005-02-16 | 明志技术学院 | Solid polymer Zinc-air cell preparing method |
| CN1918732A (en) * | 2004-04-23 | 2007-02-21 | 松下电器产业株式会社 | Alkaline battery |
| CN1691396A (en) * | 2004-04-30 | 2005-11-02 | 比亚迪股份有限公司 | Alkaline storage battery and preparation method thereof |
| US20070105020A1 (en) * | 2005-11-08 | 2007-05-10 | Gwo-Mei Wu | Fabrication method of a basic polymer electrolyte film of blended polyvinyl alcohol and quaternary amine |
| CN101515655A (en) * | 2009-03-16 | 2009-08-26 | 清华大学 | Three dimensional structure micro zinc-nickel battery applying to microsystems and preparation method thereof |
| WO2013000584A1 (en) * | 2011-06-30 | 2013-01-03 | Hochschule Mannheim | Method for producing alkaline polymer electrolyte membranes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115732770A (en) * | 2022-12-07 | 2023-03-03 | 北京理工大学 | Flexible self-healing electrolyte membrane, preparation method thereof and battery |
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Application publication date: 20190607 |