CN106571461B - A kind of long-life, can charge and discharge Zn-MnO2 battery and its application - Google Patents

A kind of long-life, can charge and discharge Zn-MnO2 battery and its application Download PDF

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CN106571461B
CN106571461B CN201610871177.8A CN201610871177A CN106571461B CN 106571461 B CN106571461 B CN 106571461B CN 201610871177 A CN201610871177 A CN 201610871177A CN 106571461 B CN106571461 B CN 106571461B
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mno
battery
nano material
pedot
aqueous solution
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CN106571461A (en
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卢锡洪
曾银香
于明浩
张熙悦
韩奕
王成胜
童叶翔
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National Sun Yat Sen University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to electrochemical energy storage cell technical field, specifically disclose a kind of long-life, can charge and discharge Zn-MnO2Battery, the Zn-MnO2The just extremely MnO of battery2@PEDOT nano material, cathode are Zn nano material, and electrolyte is 2 M ZnCl2, 3 M LiCl and 0.1 ~ 0.8 M MnSO4Mixed aqueous solution；The MnO2@PEDOT nano material is that MnO first is prepared using constant voltage electrodeposition process2Nanometer film, then by EDOT in-situ oxidation, in MnO2Compound PEDOT obtains MnO in nanometer film2@PEDOT nano material；The Zn nano material is prepared using constant current electrodeposition process.The present invention, which passes through first in electrolyte, is added appropriate MnSO4To inhibit MnO2The dissolution of electrode in aqueous solution, to realize Zn-MnO2The cycle life of battery is substantially improved.Meanwhile in MnO2The conducting high polymers object PEDOT of electrode surface cladding high stability further promotes Zn-MnO2The cyclical stability of battery finally obtains with high-energy density, large current density electrical characteristics, long-life, repeats charge and discharge flexibility Zn-MnO2Battery has great application prospect in terms of energy storage.

Description

A kind of long-life, can charge and discharge Zn-MnO2Battery and its application
Technical field
The invention belongs to electrochemical energy storage cell technical field, more particularly, to a kind of long-life, can charge and discharge Zn- MnO2Battery and its application.
Background technique
With the sharp increase of world population and the continuous development of human society, people increasingly increase the various demands of the energy Long, traditional fossil energy cannot obviously meet future society to the various demands of the energy for a long time.In addition, along with fossil energy The development and utilization in source, greenhouse effects are got worse, and ecological environment is worsening, and renewable environmentally friendly green energy resource is As today's society question of common concern.However, a series of novel green such as wind energy, solar energy, geothermal energy, ocean energy Often there is the unbalanced problems of Area distribution for the color energy, it usually needs is translated into electric energy and is just easy to use, therefore needs It wants an energy storage system by extra energy storage, releases in demand and be utilized again.It is achieved that new The deep development of the energy and efficiently utilization, the electrical energy storage device that development of new is efficient, stable are crucial.
Zn-MnO2Battery is a kind of efficient, practical energy storage device, has at low cost, energy density height, safe nothing Poison, advantages of environment protection.Traditional Zn-MnO2Battery positive electrode active material is natural MnO2, battery diaphragm be starch paste every Absciss layer, electrolyte are with NH4Based on Cl, contain a small amount of ZnCl2Aqueous solution, cathode is zinc cylinder.Because electrolyte is not flow , therefore also known as dry cell.But the performance of this battery is poor, specific energy is very low.Pass through utilization the 1960s Electrolytic manganese dioxide replaces natural manganese dioxide as positive electrode, and specific energy is promoted to original 1.5 times or so.The seventies opens Begin, electrolyte is changed to ZnCl by people2Based on plus a small amount of NH4The aqueous solution of Cl, makes Zn-MnO2The discharge performance core of battery is anti- Leakage performance is substantially improved, and discharge time is about doubled again, and can be large current discharge, and specific energy is further promoted. Since 1965 so far, alkaline Zn-MnO2Battery grows up, and Zn-MnO before2Battery is compared, and cathode has changed mercury into Neatization zinc powder, electrolyte have changed KOH aqueous solution into.This cell reaction mechanism and battery structure and above-mentioned three classes battery are completely not Together, discharge time and specific energy further increase, and can be made into chargeable battery.Although Zn-MnO2Battery is applied to very early In market, but presently, there are most of Zn-MnO2Battery is all disposable battery, can not realize multiple charge and discharge, therefore It will be discarded after being finished, lead to the waste of resource.On the other hand, although the Zn-MnO of charge-discharge type in recent years2Battery is got over Come more, but most battery life is very poor, can hardly just use less than 50 circles, therefore developing a kind of long-life can charge and discharge Zn-MnO2Battery is still current a major challenge.
Summary of the invention
It is an object of the invention to according to deficiency in the prior art, provide a kind of long-life, can charge and discharge Zn- MnO2Battery.
Another object of the present invention is to provide above-mentioned Zn-MnO2Battery is preparing the application in energy storage material.
The purpose of the present invention is achieved through the following technical solutions:
A kind of long-life, can charge and discharge Zn-MnO2Battery, the Zn-MnO2The just extremely MnO of battery2PEDOT nanometers of@ Material, cathode are Zn nano material, and electrolyte is (1~3) M ZnCl2, the mixing of (2~4) M LiCl and (0.1~0.8) M Aqueous solution；
The MnO2@PEDOT nano material is that MnO first is prepared using constant voltage electrodeposition process in substrate2Nanometer Film, then by EDOT in-situ oxidation, in MnO2Compound PEDOT obtains MnO in nanometer film2@PEDOT nano material；
The Zn nano material is prepared using constant current electrodeposition process.
Preferably, the electrolyte is 2M ZnCl2, 3M LiCl and 0.4M MnSO4Mixed aqueous solution.
Preferably, using the mixed aqueous solution of 0.05~0.15M manganese acetate and 0.05~0.15M as electric depositing solution, Voltage deposits 2~20min under the conditions of being 1V, up to MnO after the substance calcining that electro-deposition is obtained2Nanometer film.
Preferably, using the mixed aqueous solution of 0.1M manganese acetate and 0.1M sodium sulphate as electric depositing solution.
Preferably, calcination temperature is 200~500 DEG C, and calcination time is 0.5~1.5h.
Preferably, EDOT (3,4-rthylene dioxythiophene) in-situ oxidation is carried out using constant voltage electrodeposition process, concrete operations Are as follows: by (0.05~0.15) M lithium perchlorate, (0.02~0.04) M EDOT and (0.06~0.08) M lauryl sodium sulfate Mixed aqueous solution deposits 10~20min as electric depositing solution under the conditions of voltage is 1V.
Preferably, by 0.1M lithium perchlorate, the mixed aqueous solution conduct of 0.03M EDOT and 0.07M lauryl sodium sulfate Electric depositing solution.
Preferably, the constant current electro-deposition method of the Zn nano material are as follows: with 125g/L zinc sulfate, 125g/L sulfuric acid Sodium, for the aqueous solution of 20g/L boric acid as electric depositing solution, electro-deposition current density is 40mA cm-2, sedimentation time 20min.
In technical solution of the present invention, by regulating and controlling electro-deposition MnO2Voltage and the time, thus in flexible carbon cloth substrate One layer of uniform MnO of upper growth2Nanometer film；By setting suitable calcination temperature, a kind of high crystalline is obtained, performance is excellent Different MnO2Electrode material；By setting voltage and the time of electro-deposition PEDOT, in MnO2Surface coats one layer of suitable thickness High molecular polymer PEDOT, to make MnO2The stability of electrode gets a promotion；Pass through suitable concentration in setting electrolyte again MnSO4, to make Zn-MnO2The cyclical stability of battery is best.On the other hand, pass through the electric current of control electro-deposition (plating) Zn The Zn of one layer of uniform nano-chip arrays has been electroplated in flexible carbon cloth substrate, has improved its specific surface for density and electroplating time Long-pending and active site.
It preferably, is to electrode with carbon-point in the electro-deposition of anode and cathode, saturated calomel electrode is reference electrode, flexible Carbon cloth is working electrode.
Compared with prior art, the present invention has the following advantages and beneficial effects:
Nano-electrode material MnO has directly been synthesized in the present invention on flexible carrier2@PEDOT anode and Zn cathode, not only The specific surface area of electrode material is improved, to be effectively increased Zn-MnO2The performance of battery can be applied to flexible Zn-MnO2 Battery assembly.Meanwhile controlling MnSO in electrolyte4Concentration greatly inhibits MnO2The dissolution of electrode, so as to improve Zn- MnO2The cyclical stability of battery.In addition, in MnO2Electrode surface coats the conducting polymer PEDOT of one layer of suitable thickness, can be into One step promotes Zn-MnO2The cyclical stability of battery.
Detailed description of the invention
Fig. 1: being (a) MnO in embodiment 12Scanning electron microscope (SEM) picture of electrode is (b) MnO in embodiment 12@ Scanning electron microscope (SEM) picture of PEDOT electrode；
Fig. 2: being (a) low range scanning electron microscope (SEM) picture of Zn electrode in embodiment 1, is (b) Zn electricity in embodiment 1 High magnification scanning electron microscope (SEM) picture of pole；
Fig. 3: being (a) MnO in embodiment 12The X-ray powder diffraction figure of@PEDOT electrode is (b) Zn electricity in embodiment 1 The X-ray powder diffraction figure of pole；
Fig. 4: being (a) Zn-MnO in embodiment 12The discharge curve of battery is (b) Zn-MnO in embodiment 12Battery follows Ring life test curve.
Specific embodiment
Further illustrate the present invention below in conjunction with specific embodiments and the drawings, but embodiment the present invention is not done it is any The restriction of form.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method And equipment.
Unless stated otherwise, agents useful for same and material of the present invention are commercially available.
Embodiment 1:
MnO2The method that is synthesized by constant voltage electro-deposition of the@PEDOT positive electrode on flexible carbon cloth is realized.With Commercial carbon cloth (1cm × 2cm) after ten minutes is ultrasonically treated in dehydrated alcohol as flexible substrates, MnO2Electric depositing solution Aqueous solution comprising 0.1M manganese acetate and 0.1M sodium sulphate, electro-deposition voltage are 1V, and the time is 15 minutes.PEDOT polymer is It is obtained by EDOT in-situ oxidation.Electric depositing solution includes 0.1M lithium perchlorate, 0.03M EDOT, 0.07M dodecyl sulphur Sour sodium, electro-deposition are carried out on CHI electrochemical workstation, electroplating voltage 1V, and the time is 15 minutes.
The method that is synthesized by constant current electro-deposition of the Zn negative electrode material on flexible carbon cloth is realized.In anhydrous second Commercial carbon cloth (1cm × 2cm) after ten minutes is ultrasonically treated in alcohol as flexible substrates, the electric depositing solution of Zn includes 125g/L Zinc sulfate, 125g/L sodium sulphate, the aqueous solution of 20g/L boric acid, electro-deposition current density are 40 mA cm-2, the time is 20 minutes. The electrolyte of battery is 2M ZnCl2, 3M LiCl, 0.4M MnSO4Mixed aqueous solution.
Performance test: to the MnO of preparation2And MnO2@PEDOT electrode has carried out the test of Flied emission scanning electron microscopy Electronic Speculum, As a result as shown in Figure 1, scanning electron microscope diagram is shown grown on flexible carbon cloth fiber one layer it is uniform smooth MnO2Nanometer film, after one layer of PEDOT of electro-deposition, surface becomes coarse.Fig. 2 shows the scanning electricity of electro-deposition Zn on flexible carbon cloth Sub- microscope figure, as seen from the figure, carbon cloth surfaces have coated one layer of uniform nano-chip arrays.Fig. 3 uses X-ray powder diffraction Test, test result show to test resulting MnO2The crystallization degree of@PEDOT anode and Zn cathode is higher.Fig. 4 a uses electricity Constant current charge-discharge in chemical method is tested to study Zn-MnO2The energy-storage property of battery, by discharge curve as can be seen that This Zn-MnO2Battery has the voltage close to 1.8V, and has longer discharge platform, and also has under high current density higher Capacity.By calculating it is found that specific capacity is up to 366.6mAh/g.In addition, this Zn-MnO it can be seen from Fig. 4 b2Battery Still there is 83.7% capacity retention ratio after continuous charge and discharge 300 times, shows its good cyclical stability.In conclusion this Zn-MnO2Battery has high capacity, large current density electrical characteristics, and the long-life repeats charge and discharge, has in terms of energy storage Very big application prospect.
Embodiment 2-10
The preparation method of embodiment 2-10 is same as Example 1, and difference is electro-deposition MnO2With when PEDOT MnSO in time and electrolyte4Concentration.
The preparation method of comparative example 1~4 is same as Example 1, the difference is that the current density and time tune of electro-deposition Zn Control is to zinc-plated influence.
Specific electroplating time, current density and MnSO4Concentration and the result of each embodiment be listed in table 1~4.
1. electro-deposition MnO of table2Time-controllable
The time-controllable of 2. electro-deposition PEDOT of table
Table 3.MnSO4The time-controllable of concentration
The current density and time-controllable of 4. electro-deposition Zn of table

Claims (9)

1. a kind of long-life, can charge and discharge Zn-MnO2Battery, which is characterized in that the Zn-MnO2The just extremely MnO of battery2@ PEDOT nano material, cathode are Zn nano material, and electrolyte is (1~3) MZnCl2, (2~4) M LiCl and (0.1~0.8) M MnSO4Mixed aqueous solution；
The MnO2@PEDOT nano material is that MnO first is prepared using constant voltage electrodeposition process in substrate2Nanometer film, so Afterwards by EDOT in-situ oxidation, in MnO2Compound PEDOT obtains MnO in nanometer film2@PEDOT nano material；
The Zn nano material is prepared using constant current electrodeposition process；
The EDOT in-situ oxidation is carried out using constant voltage electrodeposition process, concrete operations are as follows: by (0.05~0.15) M perchloric acid The mixed aqueous solution of lithium, (0.02~0.04) M EDOT and (0.06~0.08) M lauryl sodium sulfate as electric depositing solution, 5~20min is deposited under the conditions of voltage is 1V.
2. Zn-MnO according to claim 12Battery, which is characterized in that the electrolyte is 2MZnCl2, 3M LiCl and 0.4M MnSO4Mixed aqueous solution.
3. Zn-MnO according to claim 12Battery, which is characterized in that by 0.05~0.15M manganese acetate and 0.05~ The mixed aqueous solution of 0.15M sodium sulphate deposits 5~20min under the conditions of voltage is 1V, electro-deposition is obtained as electric depositing solution Up to MnO after the substance calcining arrived2Nanometer film.
4. Zn-MnO according to claim 32Battery, which is characterized in that by the mixing of 0.1M manganese acetate and 0.1M sodium sulphate Aqueous solution is as electric depositing solution.
5. Zn-MnO according to claim 32Battery, which is characterized in that calcination temperature is 200~500 DEG C, calcination time For 0.5~1.5h.
6. Zn-MnO according to claim 12Battery, which is characterized in that by 0.1M lithium perchlorate, 0.03M EDOT and The mixed aqueous solution of 0.07M lauryl sodium sulfate is as electric depositing solution.
7. Zn-MnO according to claim 12Battery, which is characterized in that the constant current electro-deposition side of the Zn nano material Method are as follows: with 125g/L zinc sulfate, 125g/L sodium sulphate, for the aqueous solution of 20g/L boric acid as electric depositing solution, electro-deposition electric current is close Degree is 40mA cm-2, sedimentation time 20min.
8. Zn-MnO according to claim 12Battery, which is characterized in that anode and cathode electro-deposition in carbon-point be pair Electrode, saturated calomel electrode are reference electrode, and flexible carbon cloth is working electrode.
9. any Zn-MnO of claim 1 to 82Battery is preparing the application in energy storage field.
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CN109390559A (en) * 2018-10-22 2019-02-26 常州晞贝电子科技有限公司 A kind of preparation of flexible electrode and flexible energy storage device based on the electrode
CN109698318B (en) * 2018-12-27 2021-07-06 清远佳致新材料研究院有限公司 Based on MnO2Positive plate of lithium ion battery of PEDOT and preparation method
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CN110828795B (en) * 2019-10-29 2022-06-03 陈璞 Zinc-manganese-oxygen cathode material and preparation method and application thereof
CN111653778A (en) * 2020-05-20 2020-09-11 佛山科学技术学院 Positive electrode composite material for lithium-manganese battery and preparation method thereof
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