阅读说明：本技术 一种湿度和压力双重响应的金属-水电池及其制备方法 (Metal-water battery with dual responses of humidity and pressure and preparation method thereof ) 是由 余丁山 方正松 冯江珊 付新龙 于 2020-04-10 设计创作，主要内容包括：本发明公开了一种湿度和压力双重响应的金属-水电池及其制备方法。本发明首先提供了一种金属-水电池用的湿度和压力双重响应的泡沫正极,将带有含氮官能团的半导体聚合物通过化学氧化聚合反应负载到泡沫上即得。该泡沫正极具有良好的多孔性,实现了多种功能如作为水分载体、析氢催化剂和压力、湿度双响应单元在单一电极上的集成；在无额外添加电解质和隔膜的情况下,将该泡沫正极直接与活泼金属负极组装成了一种金属-水电池,该金属-水电池能够在外界湿度变化和压力刺激下自发控制输出电流的大小,对湿度和压力产生双重响应；因此,本发明制备得到的金属-水电池在智能电子领域中具有良好的应用前景。(The invention discloses a metal-water battery with dual responses of humidity and pressure and a preparation method thereof. The invention firstly provides a foam anode with dual responses of humidity and pressure for a metal-water battery, and the foam anode is obtained by loading a semiconductor polymer with a nitrogen-containing functional group on foam through chemical oxidative polymerization. The foam anode has good porosity, and realizes multiple functions such as integration of a moisture carrier, a hydrogen evolution catalyst and a pressure and humidity double-response unit on a single electrode; under the condition of no extra electrolyte and diaphragm, the foam anode and the active metal cathode are directly assembled into a metal-water battery, and the metal-water battery can spontaneously control the magnitude of output current under the external humidity change and pressure stimulation and generate double responses to humidity and pressure; therefore, the metal-water battery prepared by the method has good application prospect in the field of intelligent electronics.)

1. A foam anode with dual responses of humidity and pressure for a metal-water battery is characterized in that a semiconductor polymer with a nitrogen-containing functional group is loaded on foam through chemical oxidative polymerization reaction to obtain the foam anode.

2. The foam positive electrode according to claim 1, wherein the semiconducting polymer with nitrogen-containing functional groups is polypyrrole or polyaniline; when the semiconductor polymer with the nitrogen-containing functional group is polypyrrole, the time of the chemical oxidation polymerization reaction is 10-14 h; when the semiconductor polymer with the nitrogen-containing functional group is polyaniline, the time of the chemical oxidation polymerization reaction is 0.5-2 h.

3. The foam positive electrode according to claim 1, wherein the foam is a polyurethane foam.

4. The foam positive electrode according to claim 1, characterized in that it is prepared by a method comprising: and fully immersing the foam into a pyrrole monomer solution or an aniline monomer solution, refrigerating, adding a corresponding oxidant to perform chemical oxidative polymerization, cleaning, and drying to obtain the foam anode.

5. The foam positive electrode of claim 4, wherein the oxidizing agent is FeCl when the foam is immersed in the pyrrole monomer solution₃(ii) a When the foam is immersed in the aniline monomer solution, the oxidant is ammonium persulfate.

6. Use of the foam positive electrode according to any one of claims 1 to 5 for the preparation of stimuli-responsive smart devices.

7. The use according to claim 6, wherein the stimuli-responsive smart device is a metal-water battery that responds dual to humidity and pressure.

8. A metal-water battery with dual response of humidity and pressure, which is characterized by being prepared from the foam positive electrode of any one of claims 1 to 5.

9. The metal-water battery of claim 8, characterized in that it is prepared by: the foam positive electrode and negative electrode metal sheet as claimed in any one of claims 1 to 5 is placed in a battery case with air holes for assembly.

10. The metal-water battery of claim 9, wherein the negative electrode metal sheet is Zn or Mg.

Technical Field

The invention belongs to the technical field of energy storage batteries. And more particularly, to a metal-water battery with dual responses of humidity and pressure and a method for manufacturing the same.

Background

With the rapid development of intelligent electronics and sensor technology, electrochemical energy storage devices with special functions are becoming increasingly important in human production and life. The intelligent stimulus response device, especially a device with the capability of sensing various environmental changes, has great attraction and application potential in multiple fields such as sensors, robots, bionic devices and the like. Some important progress has been made in the research field of introducing compressibility, photo-thermal and photoelectric effects or electrochromism and the like into super capacitors or batteries. However, most of these devices are limited to a single stimulus response capability; in addition, the disadvantages of lower energy density, complex fabrication processes and device assembly, leakage of liquid electrolyte and flammability remain important challenges reported to exist in battery systems.

In recent years, an active metal-water battery (MWB) based on a simple substitution reaction has been widely used in various fields due to its high specific energy and low cost. MWB involves an oxidation reaction of the metallic negative electrode and a hydrogen evolution reduction reaction of the cathode. The battery can utilize water molecules in the air as a cathode material, and provides possibility for battery design without electrolyte. The characteristic not only greatly simplifies the assembly process of the device, but also avoids the safety problem of the electrolyte and reduces the cost. Therefore, the MWB provides a good research platform for the design of the intelligent battery.

At present, an MWB Battery is prepared by respectively researching Pu Xie and the like (metal Battery Formed by Direct Contact of magnesium with parameter polyurethane, 2015) and Minghui Ye and the like (A humidity-protective graphene oxide/lithium Battery, 2016). However, the above prior arts are all used for preparing MWB batteries with single humidity response capability, and are limited by single stimulus response capability, and in addition, the too active metal lithium is dangerous in daily use, needs additional inert gas protection, and increases the danger and cost of devices.

Therefore, the research on the safe MWB battery integrating dual or multiple response capabilities has important significance for widening the application field of the MWB battery and meeting the intelligent requirement of the market on the MWB battery.

Disclosure of Invention

The invention aims to overcome the defects and shortcomings of the existing MWB battery and provide a metal-water battery with dual responses of humidity and pressure and a preparation method thereof.

The invention aims to provide a foam anode with double response of humidity and pressure for a metal-water battery.

The invention also aims to provide application of the foam anode in preparing a stimulus-responsive intelligent device.

It is a further object of the present invention to provide a metal-water battery that responds doubly to humidity and pressure.

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

the invention firstly provides a foam anode with dual responses of humidity and pressure for a metal-water battery, and the foam anode is obtained by loading a semiconductor polymer with a nitrogen-containing functional group on foam through chemical oxidative polymerization.

Preferably, the semiconductor polymer with a nitrogen-containing functional group is polypyrrole or polyaniline.

More preferably, the semiconducting polymer with a nitrogen-containing functional group is polypyrrole.

Preferably, when the semiconductor polymer with the nitrogen-containing functional group is polypyrrole, the time of the chemical oxidative polymerization reaction is 10-14 h.

When the time of the chemical oxidative polymerization reaction is less than 10 hours, polypyrrole can not completely cover the surface of the skeleton of the foam, so that the loading capacity of the polypyrrole and the activity of the finally prepared metal-water battery are reduced; when the time of the chemical oxidative polymerization reaction is longer than 14 hours, excessive polypyrrole can agglomerate on the surface of the foam framework to cause pore blocking of foam, and a powder falling phenomenon can be formed in the using process to influence the performance of the whole foam anode.

More preferably, when the semiconducting polymer bearing a nitrogen-containing functional group is polypyrrole, the chemical oxidative polymerization reaction time is 12 hours.

When the semiconductor polymer with the nitrogen-containing functional group is polyaniline, the time of the chemical oxidation polymerization reaction is 0.5-2 h.

When the time of the chemical oxidative polymerization reaction is less than 0.5h, polyaniline can not completely cover the surface of the skeleton of the foam, so that the loading capacity of the polyaniline and the activity of the finally prepared metal-water battery are reduced; when the time of the chemical oxidative polymerization reaction is more than 2 hours, excessive polyaniline can agglomerate on the surface of the foam framework to cause pore blocking of foam, and a powder falling phenomenon can be formed in the using process to influence the performance of the whole foam anode.

More preferably, when the semiconducting polymer with nitrogen-containing functional groups is polyaniline, the chemical oxidative polymerization reaction time is 1 h.

Preferably, the foam is a polyurethane foam. The foam has a porous three-dimensional skeletal structure and good compressibility.

Preferably, the preparation method of the foam positive electrode comprises the following steps: and fully immersing the foam into a pyrrole monomer solution or an aniline monomer solution, refrigerating, adding a corresponding oxidant to perform chemical oxidative polymerization, cleaning, and drying to obtain the foam anode.

Preferably, the oxidizing agent is FeCl when the foam is immersed in the pyrrole monomer solution₃(ii) a When the foam is immersed in the aniline monomer solution, the oxidant is ammonium persulfate.

Preferably, the concentration of the pyrrole monomer solution is 0.02-0.04M.

More preferably, the concentration of the pyrrole monomer solution is 0.03M.

Preferably, the concentration of the aniline monomer solution is 0.6-1M.

More preferably, the concentration of the aniline monomer solution is 0.8M.

In addition, the application of the foam anode in the preparation of the intelligent stimulation response device also falls within the protection scope of the invention.

Preferably, the stimuli-responsive smart device is a metal-water battery that responds to both humidity and pressure.

The invention also provides a metal-water battery with dual responses of humidity and pressure, which is prepared from the foam anode.

Preferably, the preparation method of the metal-water battery comprises the following steps: and placing the foam positive and negative metal sheets into a battery shell with air holes for assembly.

Preferably, the battery case with the air holes is a CR2032 battery case which comprises a negative electrode case and a positive electrode case with the air holes.

More preferably, the preparation method of the metal-water battery comprises the following steps: and (3) placing the negative electrode metal sheet into a negative electrode shell, placing the foam positive electrode on the negative electrode metal sheet, covering the positive electrode shell with the air holes, and pressing to obtain the metal-water battery.

Preferably, the negative electrode metal sheet is Zn or Mg.

More preferably, the anode metal sheet is Mg.

The invention has the following beneficial effects:

(1) the invention provides a metal-water battery with dual responses of humidity and pressure and a preparation method thereof. The semiconductor polymer with the nitrogen-containing functional group can be uniformly deposited on a skeleton of foam, the prepared foam anode with dual response of humidity and pressure for the metal-water battery has good porosity, multiple functions such as integration of a moisture carrier, a hydrogen evolution catalyst and a pressure and humidity dual response unit on a single electrode are realized, and the prepared foam anode has good application potential in preparation of stimulus-responsive intelligent devices;

(2) under the condition of no extra electrolyte and diaphragm, the foam anode and the active metal cathode are directly assembled into a multifunctional metal-water battery, and the metal-water battery can generate double responses to humidity and pressure under the external humidity change (such as human respiration) and pressure stimulation, so that the effect of monitoring the humidity or the pressure is achieved;

(3) the preparation methods of the foam anode and the metal-water battery are simple, and the used materials are cheap, low in cost and good in safety; therefore, the invention widens the application field of the MWB battery, meets the intelligent requirement of the market on the MWB battery, and the prepared metal-water battery has good application prospect in the field of intelligent electronics.

Drawings

Fig. 1 is an SEM image of a humidity and pressure dual-responsive foam positive electrode for a metal-water battery prepared in example 1; wherein, the picture (A) is a 250um SEM picture; (B) the figure is a 1um SEM image.

Fig. 2 is a graph comparing hydrophilicity of a foam positive electrode with a raw polyurethane foam having dual response of humidity and pressure for the metal-water battery prepared in example 1; wherein, the figure (A) is a hydrophilicity figure of the original polyurethane foam; (B) the figure is a graph of the hydrophilicity of the foam positive electrode.

FIG. 3 is a plot of Linear Sweep Voltammetry (LSV) for catalyzed hydrogen production reactions for polypyrrole powder samples and other control samples; wherein the abscissa is the electrode potential, the ordinate is the current density, "GC" represents the control sample (glassy carbon electrode substrate), "Super P" represents a conductive carbon black, "PANI" represents the polyaniline powder sample, and "PPy" represents the polypyrrole powder sample.

FIG. 4 is a graph showing the result of the change of current output when a human body breathes in a constant pressure condition of the humidity and pressure dual-response metal-water battery prepared in example 1; wherein, the abscissa is time, the ordinate is relative current change, "Exhale" represents expiration, and "Inhale" represents inspiration.

FIG. 5 is a graph showing the results of current output changes at constant compression and different compression rates of a humidity and pressure dual-response metal-water battery prepared in example 1; wherein the abscissa is time, the ordinate is output current density, and the compression speeds from left to right are respectively 20mm min^-1、30mm min^-1And 40mmmin^-1。

Detailed Description

The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.

Unless otherwise indicated, reagents and materials used in the following examples are commercially available.