阅读说明：本技术 一种绿色环保的淀粉基压敏电池的制备和应用 (Preparation and application of green and environment-friendly starch-based pressure-sensitive battery ) 是由 刘鹏 马聪 陆雨 韦林洁 郑楚燕 吴培源 黄世宽 张奔腾 于 2021-07-15 设计创作，主要内容包括：本发明属于电池制造领域,公开了一种淀粉基压敏电池的制备及应用方法。该方法包括以下步骤：将一定量的盐与水混合形成盐溶液,然后将高直链淀粉均匀分散在其中,加热糊化。之后加入金属粉末和甘油,待其冷却后,与金属片贴合,即可得到淀粉基压敏电池。本发明制备的淀粉基压敏电池相较于其他电池,具有生产工艺绿色环保,无三废产生,不会对环境产生污染等优势；且工艺流程简单,能够适用于工业化生产,无需额外的新设备,工艺迅速,制作速度快；且电池具有压力敏感性,可随环境压力的变化而产生线性响应。(The invention belongs to the field of battery manufacturing, and discloses a preparation and application method of a starch-based pressure-sensitive battery. The method comprises the following steps: mixing a certain amount of salt with water to form a salt solution, uniformly dispersing high amylose starch in the salt solution, and heating to gelatinize. And then adding metal powder and glycerol, cooling, and attaching the metal powder and glycerol to a metal sheet to obtain the starch-based pressure-sensitive battery. Compared with other batteries, the starch-based pressure-sensitive battery prepared by the invention has the advantages of green and environment-friendly production process, no generation of three wastes, no pollution to the environment and the like; the process flow is simple, the method can be suitable for industrial production, additional new equipment is not needed, the process is rapid, and the manufacturing speed is high; and the battery has pressure sensitivity and can generate linear response along with the change of the environmental pressure.)

1. A preparation method of a starch-based pressure-sensitive battery is characterized by comprising the following steps:

(1) mixing high amylose starch with a calcium chloride solution and uniformly stirring to obtain a starch emulsion;

(2) heating and pasting the starch emulsion in the step (1) to enable high amylose starch to be pasted to obtain a pasted solution;

(3) continuously adding glycerol and metal powder into the gelatinized liquid in the step (2), preserving heat, stirring, pouring into a mold after uniformly mixing, and cooling;

(4) and (4) taking out the material obtained in the step (3), recovering to room temperature, and attaching to a metal sheet to obtain the starch-based pressure-sensitive battery.

2. The method for preparing a starch-based pressure-sensitive battery according to claim 1, wherein the starch selected in step (1) is a high amylose starch having an amylose content of 50% or more.

3. The method of making a starch-based pressure sensitive battery of claim 1, wherein: in the calcium chloride solution in the step (1), the mass ratio of calcium chloride to water is 1: 1-1: 5, preferably 1: 2; in the step (1), the mass ratio of the high amylose starch to the calcium chloride solution is 1: 2-1: 12, and preferably 1: 6.

4. The method of making a starch-based pressure sensitive battery of claim 1, wherein: the heating gelatinization in the step (2) refers to heating to 30-100 ℃ for gelatinization for 10-100min under the condition of stirring, and preferably heating to 70 ℃ for gelatinization for 60 min.

5. The method of making a starch-based pressure sensitive battery of claim 1, wherein: the using amount of the glycerol in the step (3) is 1: 0-1: 1, preferably 1:0.2, of the volume ratio of the gelatinized liquid to the glycerol.

6. The method of making a starch-based pressure sensitive battery of claim 1, wherein: the metal powder in the step (3) comprises at least one of magnesium powder, aluminum powder, zinc powder, iron powder, tin powder, lead powder, copper powder, silver powder, platinum powder and gold powder; the amount of the metal powder satisfies the following conditions: the mass ratio of the metal powder to the pasting liquid is 1: 2-1: 12, and preferably 1: 7.

7. The method of making a starch-based pressure sensitive battery of claim 1, wherein:

the cooling in the step (3) means cooling at 0-20 ℃ for 12-60h, the cooling time is preferably 4 ℃, and the cooling time is preferably 24 h.

8. The method of making a starch-based pressure sensitive battery of claim 1, wherein:

the metal sheet in the step (4) is one of a magnesium sheet, an aluminum sheet, a zinc sheet, an iron sheet, a tin sheet, a lead sheet, a copper sheet, a silver sheet, a platinum sheet and a gold sheet; preferably a copper sheet.

9. A starch-based flexible pressure sensitive battery prepared according to the method of any one of claims 1 to 8.

10. Use of the starch-based flexible pressure sensitive battery according to claim 9 in the field of wearable devices, pressure monitoring devices, pressure-triggered devices.

Technical Field

The invention belongs to the field of battery manufacturing, and particularly relates to preparation and application of a starch-based pressure-sensitive battery.

Background

Pollution of waste batteries is always one of the major global environmental problems, and the heavy metals such as lead, mercury, cadmium and the like contained in the waste batteries generally pollute water and soil. Research has shown that a common battery, after being thrown into the nature, can contaminate 60 thousand liters of water, which is equivalent to the water consumption of a single person for a lifetime. Dry batteries, which are the most widely used batteries for consumer use, have disadvantages such as random properties, dispersibility, and difficulty in recycling. With the rapid growth of mobile equipment, the output of dry batteries in China has reached 1200 hundred million/year. Therefore, how to manufacture green and environment-friendly batteries becomes a problem to be solved urgently.

A dry cell is a disposable cell based on the principle of a primary cell and is called a dry cell because its electrolyte is an immobile paste. Common dry batteries in the current market are mainly: the zinc-manganese dry cell, magnesium-manganese dry cell, zinc-air cell, zinc-mercury oxide cell, etc., take the most widely used zinc-manganese cell as an example, the outermost layer of the zinc-manganese dry cell is wrapped by a zinc cylinder, and the electrode and the pasty electrolyte are filled in the zinc-manganese dry cell. The raw materials are relatively expensive in the production process, and are difficult to recover after use, so that the environment is polluted. Because of the widespread use and irreplaceability of dry cells, it is necessary to pick up the waste dry cells from the raw materials in order to reduce their contamination. Therefore, the green and environment-friendly battery is manufactured, and the development prospect is very considerable.

A pressure sensitive element is a type of material that outputs a different signal by sensing external pressure information. At present, piezoresistors and piezocapacitors are mainly applied in the market, and the piezoresistors and the piezocapacitors are applied to the aspects of measuring pressure, displacement, acceleration, air pressure and the like. Besides the application, the voltage-sensitive battery can supply power to external equipment in a sectional type voltage mode according to different voltages output by different pressures, so that the functionality and the application range of the mobile equipment can be further developed, and the potential is huge.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a preparation method of a starch-based pressure-sensitive battery, so that the battery can stably supply power, has certain pressure-sensitive characteristics and can generate the change of a current signal according to the change of environmental pressure.

The invention also aims to provide the starch-based pressure-sensitive battery prepared by the method.

The invention also aims to provide application of the starch-based pressure-sensitive battery.

The purpose of the invention is realized by the following scheme:

a preparation method of a starch-based pressure-sensitive battery comprises the following steps:

(1) mixing high amylose starch with a calcium chloride solution and uniformly stirring to obtain a starch emulsion;

(2) heating and pasting the starch emulsion in the step (1) to enable high amylose starch to be pasted to obtain a pasted solution;

(3) continuously adding glycerol and metal powder into the gelatinized liquid in the step (2), preserving heat, stirring, pouring into a mold after uniformly mixing, and cooling;

(4) and (4) taking out the material obtained in the step (3), recovering to room temperature, and attaching to a metal sheet to obtain the starch-based pressure-sensitive battery.

The high amylose starch in the step (1) refers to starch with the amylose content of more than 50% in starch granules;

the mass ratio of the calcium chloride solid (CAS:22691-02-7) to the water in the calcium chloride solution selected in the step (1) is 1: 1-1: 5, preferably 1: 2;

the mass ratio of the high amylose starch to the calcium chloride solution in the step (1) is 1: 2-1: 12, and preferably 1: 6;

the heating gelatinization in the step (2) refers to heating to 30-100 ℃ for gelatinization for 10-100min under the condition of stirring, and preferably heating to 70 ℃ for gelatinization for 60 min;

the using amount of the glycerol in the step (3) meets the condition that the volume ratio of the gelatinized liquid to the glycerol is 1: 0-1: 1, preferably 1:0.2-1, and more preferably 1: 0.2;

the metal powder in the step (3) comprises at least one of magnesium powder, aluminum powder, zinc powder, iron powder, tin powder, lead powder, copper powder, silver powder, platinum powder and gold powder; preferably zinc powder;

the dosage of the metal powder in the step (3) meets the following requirements: the mass ratio of the metal powder to the pasting liquid is 1: 2-1: 12, preferably 1: 7;

the heat preservation and stirring time in the step (3) is 20-100 min;

the cooling in the step (3) means cooling at 0-20 ℃ for 12-60h, the cooling time is preferably 4 ℃, and the cooling time is preferably 24 h.

The metal sheet in the step (4) is one of a magnesium sheet, an aluminum sheet, a zinc sheet, an iron sheet, a tin sheet, a lead sheet, a copper sheet, a silver sheet, a platinum sheet and a gold sheet; preferably a copper sheet;

a starch-based pressure-sensitive battery can be prepared by the method.

The starch-based pressure-sensitive battery can be applied to the fields of wearable equipment, pressure monitoring equipment, pressure triggering equipment and the like.

The mechanism of the invention is as follows:

calcium chloride solution with certain concentration can deconstruct high amylose starch granules, so that amylose in the high amylose starch granules is dissociated in the solution, and after cooling and solidification, starch molecular chains are intertwined to form a gel electrolyte network. The glycerin is added into the gel electrolyte, so that the mutual movement of starch molecular chains can be promoted, the flexibility of a gel system is improved, and the gel system can bear larger deformation. After the metal powder is added to the gel electrolyte, the powder will disperse in the gel network. The whole system forms a primary battery by virtue of the replacement reaction of metal powder on hydrogen ions, namely, the metal powder is used as the negative electrode of the battery, electrons are lost to form metal ions, and the electrons enter a metal sheet current collector through an external circuit and are dissolved in H in gel⁺Reacting to generate hydrogen. The reaction formula is as follows:

negative electrode: m-2e ═ M²⁺(M represents a metal powder)

Positive electrode：2H⁺+2e-＝H₂

Since the gel system is flexible and compressible, the resistance inside the gel is reduced after compression, and thus although the voltage of the chemical reaction is unchanged, the output current can change along with the deformation of the gel caused by pressure, thereby showing the stimulation response of the current to the external pressure.

Compared with the prior art, the invention has the following advantages

(1) The production process of the product is green and environment-friendly, no three wastes are generated, and no pollution is caused to the environment; the method has simple process flow, can be suitable for industrial production, does not need additional new equipment, and has rapid process and high manufacturing speed.

(2) The product has pressure sensitivity, and the output current can generate linear response along with the change of the environmental pressure.

Drawings

Fig. 1 is a voltage test chart of the battery product obtained in example 1.

Fig. 2 is a graph of the output current of the battery products obtained in examples 1, 2 and 3, which were cycled 100 times under different compression deformation amounts.

Fig. 3 is a graph of the output current of the battery product obtained in example 2 at 30% compression deformation after 1000 cycles.

Detailed Description

The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.

The reagents used in the examples are commercially available without specific reference.

Example 1

(1) Weighing 50g of calcium chloride solid, adding the calcium chloride solid into 100mL of water, stirring and dissolving the calcium chloride solid until a clear solution is obtained, and cooling the solution to room temperature;

(2) weighing 25g of high amylose starch, adding the solution in the step (1), and stirring to form starch emulsion;

(3) heating the emulsion in the step (2) at 70 ℃ and stirring for 1 h;

(4) adding 20mL of glycerin and 25g of zinc powder into the mixed solution in the step (3);

(5) continuously heating the mixed solution in the step (4) at 70 ℃ and stirring for 1 h;

(6) pouring the mixed liquid obtained in the step (5) into a cylindrical mold;

(7) standing the die in the step (6) at 4 ℃ for 24h, taking out, and standing at room temperature for 2h for later use;

(8) and (5) bonding the material obtained in the step (7) with a copper sheet to obtain a battery product.

The above product voltage test result was 0.59 ± 0.01V, as shown in fig. 1.

The battery obtained by the above steps can see that the output current generates regular fluctuation when the battery is subjected to compression-rebound-compression cycles (see fig. 2).

Example 2

(1) Weighing 100g of calcium chloride solid, adding the calcium chloride solid into 100mL of water, stirring and dissolving the calcium chloride solid until a clear solution is obtained, and cooling the solution to room temperature;

(2) weighing 25g of high amylose starch, adding the solution in the step (1), and stirring to form a starch mixed solution;

(3) heating the mixed solution in the step (2) at 70 ℃ and stirring for 1 h;

(4) adding 100mL of glycerin and 50g of zinc powder into the mixed solution in the step (3);

(5) continuously heating the mixed solution in the step (4) at 70 ℃ and stirring for 11 h;

(6) pouring the mixed liquid obtained in the step (5) into a cylindrical mold;

(7) standing the die in the step (6) at 4 ℃ for 24h, taking out, and standing at room temperature for 2h for later use;

(8) and (5) bonding the material obtained in the step (7) with a copper sheet to obtain a battery product.

The voltage test result of the product is 0.59V +/-0.01V.

When the battery prepared by the steps is subjected to compression-rebound-compression circulation, the output current can be seen to generate regular fluctuation change along with the compression, and the current signal is obviously enhanced along with the increase of the compression deformation (shown in figure 2). And the amount of compression deformation of 30% was maintained, and the compression-rebound-compression cycle was extended to 1000 times, and it was observed that the output current of the battery was still stable and varied (see fig. 3).

Example 3

(1) Weighing 50g of calcium chloride solid, adding the calcium chloride solid into 100mL of water, stirring and dissolving the calcium chloride solid until a clear solution is obtained, and cooling the solution to room temperature;

(2) weighing 25g of high amylose starch, adding the solution in the step (1), and stirring to form starch emulsion;

(3) heating the emulsion in the step (2) at 70 ℃ and stirring for 1 h;

(4) adding 20mL of glycerol and 25g of iron powder into the mixed solution in the step (3);

(5) continuously heating the mixed solution in the step (4) at 70 ℃ and stirring for 1 h;

(6) pouring the mixed liquid obtained in the step (5) into a cylindrical mold;

(7) standing the die in the step (6) at 4 ℃ for 24h, taking out, and standing at room temperature for 2h for later use;

(8) and (5) bonding the material obtained in the step (7) with a copper sheet to obtain a battery product.

The voltage test result of the product is 0.42 +/-0.01V.

The battery obtained by the above steps can see that the output current generates regular fluctuation when the battery is subjected to compression-rebound-compression cycles (see fig. 2).

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.