A preparation method of zinc-MnO2 full battery and zinc-MnO2 full battery

Abstract

The present invention provides a high-conductivity electrolyte membrane, a preparation method thereof, and a battery. The method comprises the following steps: dissolving a certain amount of silk peptide powder and zinc salt in water to form solution A; dissolving water-based polyurethane in an organic solvent to form solution B; adding solution A to solution B, stirring and blending, pouring the mixture into a container, and drying to obtain the high-conductivity electrolyte membrane. The silk peptide powder not only blends well with zinc trifluoromethanesulfonate but also has a hydrophilic gene. The electrolyte membrane prepared using the silk peptide powder has a dense texture, a certain degree of moisture retention, and excellent conductivity (3.2*10 ‑4 S cm ‑1 The assembled Zn-MnO2 full battery has a good energy density (0.1 A g ‑1 At a current density of 1.5 GHz, its mass specific capacity is 70 mAh g ‑1 The solid electrolyte membrane is simple to prepare, has good hydrophilicity and high ionic conductivity, and can be widely used in solid-state zinc batteries.

Description

Technical Field

[0001] The present invention relates to the technical field of batteries, and in particular to a preparation method of a zinc-MnO2 full battery and a zinc-MnO2 full battery. Background Art

[0002] Aqueous zinc-ion battery systems have recently seen rapid development due to their advantages, including high energy density, high power density, low cost, environmental friendliness, and safety. However, their drawbacks include severe zinc dendrite growth during the electrochemical reaction, unstable electrochemical performance, and poor cycling performance. Recently, zinc-ion solid electrolytes have attracted significant attention due to their ability to mitigate zinc dendrite growth. However, the electrical conductivity of solid electrolytes rarely reaches the application level of liquid electrolytes. Therefore, developing new zinc-ion solid electrolytes to improve their ionic conductivity has become one of the greatest challenges in the development of solid-state battery technology and holds enormous technical potential and application value. Summary of the Invention

[0003] An embodiment of the present invention provides a method for preparing a high-conductivity electrolyte membrane, the method comprising the following steps:

[0004] Dissolve a certain amount of silk peptide powder and zinc salt in water to form solution A;

[0005] dissolving waterborne polyurethane in an organic solvent to form solution B;

[0006] Solution A is added to solution B, stirred and blended, then poured into a container and dried to obtain the high conductivity electrolyte membrane.

[0007] Preferably, the mass ratio of the silk peptide powder to the zinc salt is 1:3 to 1:5;

[0008] Preferably, the zinc salt comprises zinc trifluoromethanesulfonate.

[0009] Preferably, the mass ratio of solution A to solution B is 1:1 to 1:2;

[0010] Preferably, the container comprises a culture dish covered with Ecoflex film;

[0011] Preferably, the organic solvent comprises anhydrous ethanol;

[0012] Preferably, the drying step comprises: placing in an oven for drying, and then continuing to dry at room temperature to form a film to obtain the high conductivity electrolyte membrane;

[0013] Preferably, the temperature of the drying in the oven is 50-60°C and the time is 5-10 hours;

[0014] Preferably, the drying time at room temperature is 2-5 hours;

[0015] Preferably, a certain amount of silk peptide powder and zinc salt are dissolved in water by ultrasonic dissolution to form solution A;

[0016] Preferably, the stirring and fusion is carried out at room temperature.

[0017] Preferably, the silk peptide powder is an albumin product that can be obtained by hydrolysis of silk.

[0018] Preferably, based on the total mass of the high-conductivity electrolyte membrane being 100%, the mass percentage of the aqueous polyurethane is 10-15%.

[0019] The present invention also provides a high-conductivity electrolyte membrane, which is prepared by any of the above methods.

[0020] The present invention also provides a method for preparing a zinc-MnO2 full battery, the method comprising the following steps:

[0021] First, place the negative electrode shell, place the zinc negative electrode on the negative electrode shell, place the above-mentioned high-conductivity electrolyte membrane on the zinc negative electrode, then place the MnO2 positive electrode sheet on top of the electrolyte membrane, and cover it with a gasket, spring, and positive electrode shell, and use a battery packaging machine to package it to obtain a zinc-MnO2 full battery.

[0022] The present invention also provides a high-conductivity electrolyte membrane, which uses silk peptide powder as a matrix, zinc salt as a salt body, and aqueous polyurethane as a film-forming agent. The mass ratio of the silk peptide powder to the zinc salt is 1:3 to 1:5; based on the total mass of the high-conductivity electrolyte membrane as 100%, the mass percentage of the aqueous polyurethane is 10-15%.

[0023] Preferably, the zinc salt comprises zinc trifluoromethanesulfonate;

[0024] Preferably, the conductivity of the electrolyte membrane at room temperature can reach 2.0~3.2*10 -4 S cm -1 .

[0025] The present invention also provides a zinc-MnO2 battery, which comprises any one of the above-mentioned electrolyte membranes.

[0026] Preferably, the battery further comprises: a zinc negative electrode and a MnO2 positive electrode sheet respectively arranged on both sides of the electrolyte membrane.

[0027] The purpose of this invention is to develop a high-conductivity zinc ion solid electrolyte membrane. Silk peptide powder (Silkpeptide) and zinc trifluoromethanesulfonate (Zn(CF3SO3)2) were selected as electrolyte materials, and water-based polyurethane (Water Polyurethane) was used as a film-forming agent to prepare a high-conductivity zinc ion battery solid electrolyte membrane at room temperature. This solid electrolyte membrane contains a high concentration of zinc salt and a certain amount of water. At room temperature, it exhibits excellent conductivity (up to 3.2*10 -4 Scm -1 ), the all-solid-state zinc-MnO2 full battery assembled with it shows good energy density and has excellent application prospects in solid-state zinc-ion batteries. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The features and advantages of the present invention will be more clearly understood by referring to the accompanying drawings, which are schematic and

[0029] It should not be understood that any limitation is imposed on the present invention. In the accompanying drawings:

[0030] FIG1 is a physical picture of the solid electrolyte membrane prepared by the present invention.

[0031] Figure 2 shows the conductivity of the all-solid-state electrolyte membrane at different temperatures.

[0032] Figure 3 is a diagram of the cycling stability of the Zn-MnO2 full battery. DETAILED DESCRIPTION

[0033] To make the purpose, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without making any creative efforts shall fall within the scope of protection of the present invention.

[0034] The purpose of this invention is to develop a high-conductivity zinc ion solid electrolyte membrane. Silk peptide powder and zinc trifluoromethanesulfonate (Zn(CF3SO3)2) are selected as electrolyte materials, and water-based polyurethane is used as a film-forming agent to prepare a high-conductivity zinc ion battery solid electrolyte membrane at room temperature. The solid electrolyte membrane contains a high concentration of zinc salt and a certain amount of water. At room temperature, it exhibits excellent conductivity (3.2*10 -4 S cm -1 ), the zinc-MnO2 full battery assembled with it shows good energy density and has excellent application prospects in solid-state zinc-ion batteries.

[0035] Specifically, the present invention uses silk peptide powder, water-based polyurethane, and zinc trifluoromethanesulfonate as raw materials to prepare a high-conductivity solid-state zinc ion electrolyte membrane at room temperature. In water and anhydrous ethanol solvents, the silk peptide powder and zinc trifluoromethanesulfonate are cross-linked, and water-based polyurethane is added as a film-forming agent to prepare the high-conductivity solid electrolyte membrane.

[0036] Example 1:

[0037] (1) Add 0.5 g of silk peptide powder and 1.5 g of zinc trifluoromethanesulfonate to 10 ml of water and dissolve them by ultrasonication for 1 h to obtain a transparent solution A.

[0038] (2) Disperse 0.2 g of aqueous polyurethane in 20 ml of anhydrous ethanol to obtain a transparent solution B.

[0039] (3) Slowly add solution A to solution B and continue stirring at room temperature for 5 to 8 hours.

[0040] (4) The mixed solution was poured into a culture dish covered with Ecoflex film, dried in an oven at 60°C for 8 h, and then dried at room temperature for 2 h to form a film.

[0041] The Ecoflex film in the above-mentioned culture dish was prepared by mixing solution A and solution B in a mass ratio of 1:1, pouring the mixture into the culture dish, and drying at 50 degrees for 2 h.

[0042] (5) The conductivity of the dried electrolyte membrane measured at room temperature is 2.0*10 -4 S cm -1 The test uses a symmetrical blocked cell and uses the AC impedance method to measure its resistance, from which its conductivity can be calculated.

[0043] Example 2:

[0044] (1) Add 0.5 g of silk peptide powder and 2.0 g of zinc trifluoromethanesulfonate to 10 ml of water and dissolve them by ultrasonication for 1 h to obtain a transparent solution A.

[0045] (2) Disperse 0.25 g of aqueous polyurethane in 20 ml of anhydrous ethanol to obtain a transparent solution B.

[0046] (3) Slowly add solution A to solution B and continue stirring at room temperature for 5 to 8 hours.

[0047] (4) The mixed solution was poured into a culture dish covered with Ecoflex film, dried in an oven at 60 degrees for 9 hours, and then dried at room temperature for 2 hours to form a film, as shown in Figure 1.

[0048] (5) The conductivity of the dried electrolyte membranes of different thicknesses was measured at room temperature to be 2.2~3.2*10 -4 S cm -1 ,like Figure 2 .

[0049] (6) The electrochemical performance test adopts zinc-MnO2 full battery. The preparation method of zinc-MnO2 full battery includes the following steps: first, the negative electrode shell is placed, the zinc negative electrode is placed on the negative electrode shell, the above-mentioned high conductivity electrolyte membrane is placed on the zinc negative electrode, and then the MnO2 positive electrode sheet is placed on the electrolyte membrane, and covered with a gasket, a spring, and a positive electrode shell, and the zinc-MnO2 full battery is encapsulated by a battery encapsulation machine. The single cell assembled with this electrolyte membrane is 0.1Ag -1 At a current density of 1.5 GHz, its mass specific capacity is 94 mAhg -1 (calculated based on the positive electrode active material), it can be cycled 200 times, see Figure 3.

[0050] Example 3:

[0051] (1) Add 0.5 g of silk peptide powder and 2.5 g of zinc trifluoromethanesulfonate to 10 ml of water and dissolve them by ultrasonication for 1 h to obtain a transparent solution A.

[0052] (2) Disperse 0.3 g of aqueous polyurethane in 20 ml of anhydrous ethanol to obtain a transparent solution B.

[0053] (3) Slowly add solution A to solution B and continue stirring at room temperature for 5 to 8 hours.

[0054] (4) The mixed solution was poured into a culture dish covered with Ecoflex film, dried in an oven at 60°C for 10 h, and then dried at room temperature for 2 h to form a film.

[0055] (5) The conductivity of the dried electrolyte membrane was measured to be 2.2*10 -4 S cm -1 .

[0056] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the present invention. Those skilled in the art may make various modifications and variations without departing from the spirit and scope of the present invention. Such modifications and variations shall fall within the scope defined by the appended claims.

Claims

1. A method for preparing a zinc-MnO2 full battery, characterized in that: The method comprises the following steps: First, place the negative electrode shell, place the zinc negative electrode on the negative electrode shell, place a high-conductivity electrolyte membrane on the zinc negative electrode, then place the MnO2 positive electrode sheet on top of the electrolyte membrane, and cover it with a gasket, spring, and positive electrode shell, and use a battery packaging machine to package it to obtain a zinc-MnO2 full battery; The method for preparing the high conductivity electrolyte membrane comprises: Dissolving a certain amount of silk peptide powder and zinc salt in water to form solution A, wherein the silk peptide powder is obtained by hydrolyzing silk, and the zinc salt includes zinc trifluoromethanesulfonate; Dissolving aqueous polyurethane in an organic solvent to form a solution B, wherein the mass percentage of the aqueous polyurethane is 10-15% based on the total mass of the high-conductivity electrolyte membrane being 100%; Solution A is added to solution B, stirred and blended, then poured into a container and dried to obtain the high-conductivity electrolyte membrane.

2. The preparation method according to claim 1, characterized in that The electrolyte membrane uses silk peptide powder as a matrix, zinc salt as a salt body, and water-based polyurethane as a film-forming agent. The mass ratio of the silk peptide powder to the zinc salt is 1:3-1:

5.

3. The preparation method according to claim 2, characterized in that The conductivity of the electrolyte membrane at room temperature is 2.0~3.2*10 -4 S cm -1 .

4. The preparation method according to claim 1, characterized in that The mass ratio of solution A to solution B is 1:1 to 1:2; The container includes a culture dish covered with Ecoflex film; The organic solvent includes anhydrous ethanol; The drying step includes: placing in an oven for drying, and then continuing to dry at room temperature to form a film to obtain the high conductivity electrolyte membrane; The drying temperature in the oven is 50-60°C and the drying time is 5-10 hours; The drying time at room temperature is 2-5 hours; A certain amount of silk peptide powder and zinc salt were dissolved in water by ultrasonic dissolution to form solution A; The stirring fusion was carried out at room temperature.

5. A zinc-MnO2 full battery, characterized in that The zinc-MnO2 full battery is prepared by the preparation method described in any one of claims 1 to 4. The zinc-MnO2 full battery includes a high-conductivity electrolyte membrane and also includes a zinc negative electrode and a MnO2 positive electrode sheet respectively arranged on both sides of the high-conductivity electrolyte membrane.

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