阅读说明：本技术 一种酸碱非对称电解液锌-醌电池 (Acid-base asymmetric electrolyte zinc-quinone battery ) 是由 蔡平伟 温珍海 于 2019-01-04 设计创作，主要内容包括：本申请公开了一种锌-醌电池,包括阳极、阴极、隔膜、阳极电解液和阴极电解液；其中,所述阴极含有阴极催化剂,所述阴极催化剂选自醌可逆还原氧化反应催化剂中的至少一种；所述阳极为金属锌；所述阳极电解液为碱性溶液,所述阴极电解液为含有醌的酸性溶液；所述阳极电解液和所述阴极电解液由所述隔膜隔开。该锌-醌电池的开路电压为1.95V,最大功率密度为315mW cm<Sup>-2</Sup>,以10mA cm<Sup>-2</Sup>的电流密度充放电的电压差值为200mV,解决了传统锌-醌电池的可逆性差和稳定性不佳的问题,提高了电池的开路电压和功率密度,在提高能量存储与转换设备性能的发展方面具备极大的潜力和良好的应用前景。(The application discloses a zinc-quinone battery, which comprises an anode, a cathode, a diaphragm, an anolyte and a catholyte; wherein the cathode contains a cathode catalyst selected from at least one of quinone reversible redox reaction catalysts; the anode is metallic zinc; the anolyte is an alkaline solution, and the catholyte is an acidic solution containing quinone; the anolyte and the catholyte are separated by the membrane. The open-circuit voltage of the zinc-quinone battery is 1.95V, and the maximum power density is 315mW cm ‑2 At 10mA cm ‑2 The voltage difference value of current density charging and discharging is 200mV, the problems of poor reversibility and poor stability of the traditional zinc-quinone battery are solved, the open-circuit voltage and the power density of the battery are improved, and the development of improving the performance of energy storage and conversion equipment is realizedThe method has great potential and good application prospect.)

1. A zinc-quinone battery comprising an anode, a cathode, a separator, an anolyte, and a catholyte;

wherein the cathode contains a cathode catalyst selected from at least one of quinone reversible redox reaction catalysts;

the anode is metallic zinc;

the anolyte is an alkaline solution, and the catholyte is an acidic solution containing quinone;

the anolyte and the catholyte are separated by the membrane.

2. The zinc-quinone battery of claim 1, wherein the anolyte comprises at least one of a base; the alkali is at least one of sodium hydroxide and potassium hydroxide;

the catholyte is an acid solution containing quinone; the acid in the catholyte is at least one selected from sulfuric acid and hydrochloric acid.

3. The zinc-quinone battery of claim 2, wherein the concentration of base in the anolyte is 3.0 mol/L-5.0 mol/L;

the concentration of the quinone in the catholyte is 0.01 mol/L-0.1 mol/L, and the concentration of the acid in the catholyte is 1.0 mol/L-3.0 mol/L.

4. The zinc-quinone cell of claim 1, wherein the anolyte is a 4.0 mol/L sodium hydroxide solution in concentration;

the catholyte is a 2.0 mol/L sulfuric acid solution containing 0.1 mol/L benzoquinone or a 2.0 mol/L sulfuric acid solution containing 0.1 mol/L benzoquinone.

5. The fuel cell of claim 1, wherein the quinone reversible redox reaction catalyst is selected from at least one of an ultrathin carbon nanosheet-supported hollow nickel trisulfide composite, a carbon nanosheet-supported nickel trisulfide composite, or a carbon nanosheet.

6. The zinc-quinone battery of claim 1, wherein the separator is a bipolar membrane;

preferably, the anion exchange membrane face of the membrane is opposite to the anolyte, and the cation exchange membrane face is opposite to the catholyte.

7. The zinc-quinone cell of claim 1, wherein the cathode is a carbon paper loaded with a cathode catalyst.

8. The zinc-quinone cell of claim 7, wherein the carbon paper has a size of 4cm × 4cm to 4cm × 5 cm;

preferably, the size of the carbon paper is 4cm × 4cm, and the area of the carbon paper coated with the cathode catalyst is 1cm × 1 cm.

9. The Zn-quinone cell of claim 7, wherein the loading amount of the cathode catalyst on the carbon paper of the cathode is 0.5 to 1.5mg/cm²；

Preferably, the loading amount of the cathode catalyst on the carbon paper of the cathode is 1.0mg/cm²。

10. Use of a zinc-quinone cell as claimed in any one of claims 1 to 9 in an electrochemical energy storage and conversion system.

Technical Field

The application relates to a zinc-quinone battery, and belongs to the field of chargeable and dischargeable batteries.

Background

The energy crisis and environmental pollution problems caused by excessive consumption of fossil energy have greatly promoted the development of new environmentally friendly renewable energy sources including wind, tidal, and solar energy. Recently, zinc-based batteries, particularly zinc ion batteries, zinc flow batteries, and zinc-air batteries have attracted considerable research interest to scientific researchers. Because of low price, safety, high efficiency and environmental protection, the zinc-air battery has strong competitiveness in the development of new energy in the future. However, in a zinc-air cellThere are a number of problems that need to be addressed. The first thing is that the dynamics of the cathode of the battery is slow and the reversibility of the battery is poor. When the battery is discharged, the cathode generates oxygen reduction reaction; when the battery is charged, the battery undergoes an oxygen evolution reaction. Therefore, researchers are working on developing high-activity and high-stability cathode catalysts to reduce the voltage difference during the charge and discharge process and enhance the reversibility of the battery. Although the current density is improved to a certain extent, the result is not satisfactory, and the current density is 10mA cm^-2The voltage difference between charging and discharging is still 0.7V.

Therefore, some alternative reactions are used in zinc-air batteries to enhance the reversibility and energy efficiency of zinc-air batteries. The quinone compound has good reversibility, high specific capacity, rich source and wide application foreground in zinc-base cell. The zinc-quinone battery solves the reversibility problem of the traditional zinc-air battery to a certain extent, but the further improvement of the performance of the zinc-quinone battery is still a challenge. First, the voltage ratio of zinc-quinone cells is low; second, in zinc-quinone batteries, the development of catalysts for the reversible redox reaction of quinones remains challenging, resulting in limited overall cell performance. In addition, zinc anodes operate stably under alkaline conditions, while quinones react more rapidly under acidic conditions. Electrolyte mismatch between the zinc anode and the quinone cathode will impair cell performance.

Disclosure of Invention

According to one aspect of the application, the zinc-quinone battery constructed by the acid-base asymmetric electrolyte is provided, the open-circuit voltage of the zinc-quinone battery is 1.95V, and the maximum power density of the zinc-quinone battery is 315mW cm^-2At 10mA cm^-2The voltage difference value of current density charge and discharge is 200mV, so that the problems of reversibility and stable stability of the traditional zinc-quinone battery are solved, the open circuit and power density of the battery are improved, the practicability and durability of the device are improved, and the device has great potential and good application prospect in the aspect of promoting the development of energy storage and conversion equipment.

The zinc-quinone battery is characterized by comprising an anode, a cathode, a diaphragm, an anolyte and a catholyte;

wherein the cathode contains a cathode catalyst selected from at least one of quinone reversible redox reaction catalysts;

the anode is metallic zinc;

the anolyte is an alkaline solution, and the catholyte is an acidic solution containing quinone;

the anolyte and the catholyte are separated by the membrane.

Specifically, the zinc-quinone cell comprises an anode, a cathode, a diaphragm, an anode compartment electrolyte and a cathode compartment electrolyte; wherein the cathode is carbon paper loaded with a catalyst with excellent catalytic performance on quinone reversible reduction oxidation reaction; the anode is metallic zinc;

the anolyte is an alkaline solution, and the catholyte is an acidic solution;

the anolyte and the catholyte are separated by the membrane.

Optionally, the anolyte contains at least one of the bases; the alkali is at least one of sodium hydroxide and potassium hydroxide;

the catholyte is an acid solution containing quinone; the acid in the catholyte is at least one selected from sulfuric acid and hydrochloric acid.

Optionally, the concentration of the alkali in the anolyte is 3.0 mol/L-5.0 mol/L;

optionally, the concentration of the quinone in the catholyte is 0.01 mol/L-0.1 mol/L, and the concentration of the acid in the catholyte is 1.0 mol/L-3.0 mol/L.

Optionally, the anolyte is a concentration of 4.0 mol/L sodium hydroxide solution;

the catholyte is a 2.0 mol/L sulfuric acid solution containing 0.1 mol/L benzoquinone or a 4.0 mol/L sulfuric acid solution containing 0.1 mol/L benzoquinone.

Specifically, the electrolyte in the anode chamber contains at least one of sodium hydroxide and potassium hydroxide; the electrolyte in the cathode chamber contains sulfuric acid.

Specifically, the electrolyte of the anode chamber is a sodium hydroxide solution, and the electrolyte of the cathode chamber is a sulfuric acid solution containing 0.1 mol/L benzoquinone.

Specifically, the concentration of the sodium hydroxide solution is 3.0 mol/L-5.0 mol/L, and the concentration of the sulfuric acid solution is 1.0 mol/L-3.0 mol/L.

Specifically, the concentration of the sodium hydroxide solution is 4.0 mol/L, and the concentration of the sulfuric acid solution is 2.0 mol/L.

Optionally, the quinone reversible reduction oxidation reaction catalyst is selected from at least one of an ultrathin carbon nanosheet-supported hollow nickel trisulfide composite material, a carbon nanosheet-supported nickel trisulfide composite material or a carbon nanosheet.

Specifically, the quinone catalyst is selected from at least one of an ultrathin carbon nanosheet-supported hollow nickel trisulfide composite material, a carbon nanosheet-supported nickel trisulfide composite material or a carbon nanosheet.

Optionally, the membrane is a bipolar membrane.

Optionally, the anion exchange membrane surface of the membrane is opposite to the anolyte, and the cation exchange membrane surface is opposite to the catholyte.

Specifically, the anion exchange membrane of the bipolar membrane faces the anolyte, and the cation exchange membrane faces the catholyte.

Optionally, the cathode is a carbon paper loaded with a cathode catalyst.

Optionally, the size of the carbon paper is 4cm × 4cm to 4cm × 5 cm.

Alternatively, the carbon paper has a size of 4cm × 4cm, and the area of cathode catalyst coated on the carbon paper is 1cm × 1 cm.

Optionally, the load capacity of the catalyst with catalytic activity for the p-quinone reversible reduction oxidation reaction on the carbon paper of the cathode is 0.5-1.5 mg/cm²。

Optionally, the load of the catalyst with catalytic activity for the quinone reversible reduction oxidation reaction on the carbon paper of the cathode is 1.0mg/cm²。

Specifically, the cathode is formed by supporting the quinone catalyst on carbon paper; the diaphragm is a bipolar membrane.

Specifically, the size of the carbon paper is 4cm × 4cm, and the area of the catalyst is 1cm × 1 cm.

As a specific embodiment, the specific process of forming the cathode electrode by supporting the quinone catalyst on the carbon paper is as follows:

and dispersing the quinone catalyst in a water/ethanol/sodium perfluorosulfonate (Nafion) mixed solution, fully performing ultrasonic treatment, dripping the mixture on carbon paper, and removing the solvent to obtain the cathode electrode.

According to another aspect of the present application, there is provided a use of the zinc-quinone battery in an electrochemical energy storage and conversion system.

The beneficial effects that this application can produce include at least:

1) the zinc-quinone battery is a cheap, safe and efficient electrochemical energy storage and conversion device, and has the advantages of high efficiency, high power, good reversibility, strong stability and the like.

2) The zinc-quinone battery provided by the application is simple to assemble, high in practical value and easy for industrial production.

Drawings

Fig. 1 is a morphology of a zinc-quinone battery cathode catalyst prepared in the present application, wherein (a) is a scanning electron microscope image of an ultrathin carbon nanosheet-supported hollow nickel trisulfide composite material, and (b) is a transmission electron microscope image of an ultrathin carbon nanosheet-supported hollow nickel trisulfide composite material.

Fig. 2 is a schematic diagram of a zinc-quinone cell of the present application.

FIG. 3 shows a zinc-quinone cell 1 in examples 1 and 2 of the present application^#，2^#Open circuit voltage versus time.

FIG. 4 shows a zinc-quinone battery 1 in examples 1 and 2 of the present application^#、2^#Polarization curve and power density test results.

FIG. 5 shows a zinc-quinone cell 1 of example 1 of the present application^#The stability test results of (1).

FIG. 6 shows the electrocatalytic redox activity of p-benzoquinone with different catalysts in example 4 of the present application.

Detailed Description

The present application will be described in detail with reference to examples, but the present application is not limited to these examples.

Unless otherwise specified, the raw materials in the examples of the present application were purchased commercially and used without treatment; the test conditions of the instrument all adopt the parameters recommended by the manufacturer.