CN106571461A - Chargeable-dischargeable Zn-MnO2 battery with long service life and applications thereof - Google Patents

Chargeable-dischargeable Zn-MnO2 battery with long service life and applications thereof Download PDF

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Publication number
CN106571461A
CN106571461A CN201610871177.8A CN201610871177A CN106571461A CN 106571461 A CN106571461 A CN 106571461A CN 201610871177 A CN201610871177 A CN 201610871177A CN 106571461 A CN106571461 A CN 106571461A
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battery
mno
mno2
pedot
electro
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CN106571461B (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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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 the technical field of electrochemical energy storage battery, and specifically discloses a chargeable-dischargeable Zn-MnO2 battery with a long service life. The positive electrode of the Zn-MnO2 battery is made of a MnO2@PEDOT nano material, and the negative electrode is made of a Zn nano material. The electrolyte is a mixed water solution of ZnCl2 (2M), LiCl (3M), and MnSO4 (0.1-0.8M). The MnO2@PEDOT nano material is prepared by the following steps: preparing a MnO2 nano membrane by a constant voltage electro-deposition method and then compounding PEDOT on the MnO2 nano membrane through EDOT in-situ oxidation so as to obtain the MnO2@PEDOT nano material. The Zn nano material is prepared by a constant current electro-deposition method. At first, a proper amount of MnSO4 is added into the electrolyte to inhibit the dissolution of MnO2 electrode in the water solution so as to greatly prolong the cycle life of the Zn-MnO2 battery. At the same time, high stability conductive high molecular polymer (PEDOT) is wrapped on the surface of the MnO2 electrode to further improve the cycle stability of the Zn-MnO2 battery. The obtained flexible Zn-MnO2 battery has a high energy density, a large current charging-discharging characteristic, and a long service life, is capable of repeatedly charging and discharging, and has a great application prospect on 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 technology
With the sharp increase and the continuous development of human society of world population, people increasingly increase to the various demands of the energy Long, traditional fossil energy substantially can not meet various demands of the Future Society to the energy for a long time.In addition, being accompanied by fossil energy The development and utilization in source, greenhouse effect are increasingly serious, and ecological environment goes from bad to worse, and renewable environmentally friendly green energy resource is Become today's society question of common concern.However, such as wind energy, solar energy, geothermal energy, ocean energy etc. are a series of new green The color energy often has that Area distribution is unbalanced, it usually needs is translated into electric energy ability convenient use, therefore needs Want an energy storage system by unnecessary energy storage, discharge in demand and be utilized again.It is achieved that new The deep development and efficient utilization of the energy, efficient, the stable electrical energy storage device of development of new are crucial.
Zn-MnO2Battery is a kind of energy storing device efficiently, practical, and with low cost, energy density is high, 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, containing a small amount of ZnCl2Aqueous solution, negative pole is zinc cylinder.Because electrolyte is not flow , therefore it is also called aneroid battery.But the poor-performing of this battery, specific energy are very low.The sixties in 20th century, by using Electrolytic manganese dioxide replaces natural manganese dioxide as positive electrode, and specific energy lifts original 1.5 times or so.The seventies opens Begin, people are changed to electrolyte with ZnCl2Based on plus a small amount of NH4The aqueous solution of Cl, makes Zn-MnO2The discharge performance core of battery is prevented Leakage performance is substantially improved, and discharge time is about doubled again, and can further be lifted with heavy-current discharge, specific energy. Start so far from nineteen sixty-five, alkaline Zn-MnO2Battery grows up, and Zn-MnO before2Battery is compared, and negative pole has changed hydrargyrum into Neatization zinc powder, electrolyte have changed KOH aqueous solutions into.This cell reaction mechanism and battery structure are with above-mentioned three classes battery 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 the most of Zn-MnO that presently, there are2Battery, is all disposable battery, is not capable of achieving multiple discharge and recharge, therefore Will be discarded after being finished, caused 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 a kind of exploitation long-life can charge and discharge Zn-MnO2Battery remains current a major challenge.
The content of the invention
It is an object of the invention to according to deficiency of the prior art, there is provided a kind of long-life, can charge and discharge Zn-MnO2 Battery.
Another object of the present invention is to provide above-mentioned Zn-MnO2Application of the battery in energy storage material is prepared.
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 battery2@PEDOT nanometer materials Material, negative pole are Zn nano materials, and electrolyte is (1～3) M ZnCl2, the mixing of (2～4) M LiCl and (0.1～0.8) M is water-soluble Liquid；
The MnO2@PEDOT nano materials prepare MnO using constant voltage electrodeposition process for first in substrate2Nanometer Film, then by EDOT in-situ oxidations, in MnO2PEDOT is combined in nanometer film and obtains MnO2@PEDOT nano materials；
The Zn nano materials are 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 acetates and 0.05～0.15M as electric depositing solution, Voltage is 2～20min of deposition under the conditions of 1V, obtains final product MnO after the material calcining that electro-deposition is obtained2Nanometer film.
Preferably, using the mixed aqueous solution of 0.1M manganese acetates and 0.1M sodium sulfate as electric depositing solution.
Preferably, calcining heat is 200～500 DEG C, and calcination time is 0.5～1.5h.
Preferably, EDOT (3,4-rthylene dioxythiophene) in-situ oxidations are carried out using constant voltage electrodeposition process, concrete operations For：By (0.05～0.15) M lithium perchlorates, (0.02～0.04) M EDOT and (0.06～0.08) M sodium lauryl sulphates Mixed aqueous solution deposits 10～20min as electric depositing solution under the conditions of voltage is 1V.
Preferably, by 0.1M lithium perchlorates, the mixed aqueous solution conduct of 0.03M EDOT and 0.07M sodium lauryl sulphates Electric depositing solution.
Preferably, the constant current electro-deposition method of the Zn nano materials is：With 125g/L zinc sulfate, 125g/L sulphuric acid Sodium, used as electric depositing solution, electro-deposition electric current density is 40mA cm to 20g/L boron aqueous acid-2, sedimentation time is 20min.
In technical scheme, by regulating and controlling electro-deposition MnO2Voltage and the time, so as in flexible carbon cloth substrate One layer of uniform MnO of upper growth2Nanometer film；By setting suitable calcining heat, a kind of high crystalline is obtained, performance is excellent Different MnO2Electrode material；By the voltage and the time that set electro-deposition PEDOT, in MnO2One layer of suitable thickness of Surface coating High molecular polymer PEDOT, so that MnO2The stability of electrode gets a promotion；Again by setting suitable concn in electrolyte MnSO4, so that Zn-MnO2The cyclical stability of battery is best.On the other hand, by the electric current of control electro-deposition (plating) Zn Density and electroplating time, have electroplated the Zn of one layer of uniform nano-chip arrays in flexible carbon cloth substrate, have improve its specific surface Product and avtive spot.
Preferably, it is that, to electrode, saturated calomel electrode is reference electrode with carbon-point in the electro-deposition of positive pole and negative pole, it is flexible Carbon cloth is working electrode.
Compared with prior art, the present invention has advantages below and beneficial effect：
Directly nano-electrode material MnO is synthesized on flexible carrier in the present invention2@PEDOT positive poles and Zn negative poles, not only The specific surface area of electrode material is improve, so as to be effectively increased Zn-MnO2The performance of battery, can be applicable to flexible Zn-MnO2 Battery is assembled.Meanwhile, MnSO in control electrolyte4Concentration, greatly inhibits MnO2The dissolving of electrode, so as to improve Zn- MnO2The cyclical stability of battery.Additionally, in MnO2Electrode surface coats the conducting polymer PEDOT of one layer of suitable thickness, can enter One step lifts Zn-MnO2The cyclical stability of battery.
Description of the drawings
Fig. 1：A () is MnO in embodiment 12Scanning electron microscope (SEM) picture of electrode, is (b) MnO in embodiment 12@PEDOT Scanning electron microscope (SEM) picture of electrode；
Fig. 2：Low range scanning electron microscope (SEM) picture of (a) for Zn electrodes in embodiment 1, it is (b) electric for Zn in embodiment 1 High magnification scanning electron microscope (SEM) picture of pole；
Fig. 3：A () is MnO in embodiment 12The X-ray powder diffraction figure of@PEDOT electrodes, it is (b) electric for Zn in embodiment 1 The X-ray powder diffraction figure of pole；
Fig. 4：A () is Zn-MnO in embodiment 12The discharge curve of battery, is (b) Zn-MnO in embodiment 12Battery is followed Ring life test curve.
Specific embodiment
The present invention is further illustrated below in conjunction with specific embodiments and the drawings, but embodiment does not do any to the present invention The restriction of form.Unless stated otherwise, the reagent for adopting of the invention, method and apparatus are for the art conventional reagent, method And equipment.
Unless stated otherwise, agents useful for same of the present invention and material are commercial.
Embodiment 1：
MnO2The method that be synthesized by constant voltage electro-deposition of the@PEDOT positive electrodes on flexible carbon cloth is realized.With In dehydrated alcohol, commercial carbon cloth (1cm × 2cm) of the supersound process after 10 minutes is used as flexible substrates, MnO2Electric depositing solution Aqueous solution comprising 0.1M manganese acetates and 0.1M sodium sulfate, electro-deposition voltage are 1V, and the time is 15 minutes.PEDOT polymer is Obtained by EDOT in-situ oxidations.Electric depositing solution includes 0.1M lithium perchlorates, 0.03M EDOT, 0.07M dodecyl sulfur Sour sodium, electro-deposition are carried out on CHI electrochemical workstations, and electroplating voltage is 1V, and the time is 15 minutes.
The method that be synthesized by constant current electro-deposition of the Zn negative materials on flexible carbon cloth is realized.With in anhydrous second In alcohol, used as flexible substrates, the electric depositing solution of Zn includes 125g/L to commercial carbon cloth (1cm × 2cm) of the supersound process after 10 minutes Zinc sulfate, 125g/L sodium sulfate, 20g/L boron aqueous acids, electro-deposition electric current density are 40mA 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 for preparing2And MnO2@PEDOT electrodes have carried out the test of Flied emission scanning electron microscopy Electronic Speculum, As a result as shown in figure 1, scanning electron microscope diagram shows that one layer is grown on flexible carbon cloth fiber 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 employs X-ray powder diffraction Test, test result show the MnO for testing gained2The crystallization degree of@PEDOT positive poles and Zn negative poles is higher.Fig. 4 a employ 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 for being close to 1.8V, and has longer discharge platform, and also has under high current density higher Capacity.By calculating, specific capacity is up to 366.6mAh/g.Additionally, can be seen that this Zn-MnO by Fig. 4 b2Battery connects Still there is 83.7% capability retention after continuous discharge and recharge 300 times, show its good cyclical stability.In sum, this Zn- MnO2Battery has high power capacity, and large current density electrical characteristics the long-life, repeat discharge and recharge, have very in terms of energy storage Big application prospect.
Embodiment 2-10
The preparation method of embodiment 2-10 is same as Example 1, and difference is electro-deposition MnO2With during PEDOT when Between and electrolyte in MnSO4Concentration.
The preparation method of comparative example 1～4 is same as Example 1, except for the difference that the electric current density of electro-deposition Zn and time tune Control is to zinc-plated impact.
Concrete electroplating time, electric 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 electric current density and time-controllable of 4. electro-deposition Zn of table

Claims (10)

1. a kind of long-life, can charge and discharge Zn-MnO2Battery, it is characterised in that the Zn-MnO2The just extremely MnO of battery2@ PEDOT nano materials, negative pole are Zn nano materials, and electrolyte is（1~3） M ZnCl2,（2~4）M LiCl and（0.1~0.8）M MnSO4Mixed aqueous solution；
The MnO2@PEDOT nano materials prepare MnO using constant voltage electrodeposition process for first in substrate2Nanometer film, so Afterwards by EDOT in-situ oxidations, in MnO2PEDOT is combined in nanometer film and obtains MnO2@PEDOT nano materials；
The Zn nano materials are prepared using constant current electrodeposition process.
2. Zn-MnO according to claim 12Battery, it is characterised in that the electrolyte is 2 M ZnCl2, 3 M LiCl With 0.4 M MnSO4Mixed aqueous solution.
3. Zn-MnO according to claim 12Battery, it is characterised in that by 0.05 ~ 0.15 M manganese acetates and 0.05 ~ 0.15 The mixed aqueous solution of M sodium sulfate under the conditions of voltage is 1V deposits 5 ~ 20 min, electro-deposition is obtained as electric depositing solution MnO is obtained final product after material calcining2Nanometer film.
4. Zn-MnO according to claim 32Battery, it is characterised in that by 0.1 M manganese acetates and 0.1 M
The mixed aqueous solution of sodium sulfate is used as electric depositing solution.
5. Zn-MnO according to claim 32Battery, it is characterised in that calcining heat is 200 ~ 500 DEG C, calcination time is 0.5~1.5h。
6. Zn-MnO according to claim 12Battery, it is characterised in that EDOT in-situ oxidations adopt constant voltage electrodeposition process Carry out, concrete operations are：Will（0.05~0.15）M lithium perchlorates,（0.02~0.04）M EDOT and（0.06~0.08）M 12 The mixed aqueous solution of alkyl sodium sulfate deposits 5 ~ 20min as electric depositing solution under the conditions of voltage is 1 V.
7. Zn-MnO according to claim 62Battery, it is characterised in that by 0.1 M lithium perchlorates, 0.03 M EDOT and The mixed aqueous solution of 0.07 M sodium lauryl sulphates is used as electric depositing solution.
8. Zn-MnO according to claim 12Battery, it is characterised in that the constant current electro-deposition side of the Zn nano materials Method is：With 125 g/L zinc sulfate, 125 g/L sodium sulfate, 20 g/L boron aqueous acids are used as electric depositing solution, electro-deposition electricity Current density is 40mA cm-2, sedimentation time is 20min.
9. Zn-MnO according to claim 12Battery, it is characterised in that be right with carbon-point in the electro-deposition of positive pole and negative pole Electrode, saturated calomel electrode are reference electrode, and flexible carbon cloth is working electrode.
10. the arbitrary described Zn-MnO of claim 1 to 92Application of the battery in energy storage material is prepared.
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CN107221648A (en) * 2017-04-26 2017-09-29 苏州浏宸新材料科技有限公司 A kind of preparation method of flexible battery
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
CN109698318A (en) * 2018-12-27 2019-04-30 清远佳致新材料研究院有限公司 One kind being based on MnO2The positive plate and preparation method of the lithium ion battery of-PEDOT
CN110061311A (en) * 2019-05-08 2019-07-26 瑞海泊有限公司 A kind of preparation method of the solid-state electrolyte layer for water system zinc battery
CN110828795A (en) * 2019-10-29 2020-02-21 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
CN112467233A (en) * 2020-12-01 2021-03-09 中山市华舜科技有限责任公司 High-performance aqueous electrolyte for chargeable and dischargeable zinc-manganese battery
CN113036096A (en) * 2021-02-01 2021-06-25 复旦大学 Water system zinc-manganese battery fiber with double-functional protective layer and preparation method thereof
CN113328060A (en) * 2021-06-11 2021-08-31 电子科技大学 Method for preparing flexible electrode on nano needle cone nickel substrate
CN114122416A (en) * 2021-11-29 2022-03-01 东莞理工学院 Three-dimensional porous cobalt nitride-poly (3, 4-ethylenedioxythiophene) flexible composite electrode and preparation method thereof
CN114220939A (en) * 2021-12-15 2022-03-22 南京信息工程大学 Preparation method and application of secondary water system zinc ion battery positive electrode
CN114744153A (en) * 2022-04-20 2022-07-12 吉林大学 Conductive polymer with energy storage and biodegradation properties, preparation method, flexible electrode and degradable zinc ion battery
WO2023003834A1 (en) * 2021-07-19 2023-01-26 Grotthuss, Inc. Rechargeable zinc metal battery

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CN107221648A (en) * 2017-04-26 2017-09-29 苏州浏宸新材料科技有限公司 A kind of preparation method of flexible battery
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
CN109698318A (en) * 2018-12-27 2019-04-30 清远佳致新材料研究院有限公司 One kind being based on MnO2The positive plate and preparation method of the lithium ion battery of-PEDOT
CN110061311A (en) * 2019-05-08 2019-07-26 瑞海泊有限公司 A kind of preparation method of the solid-state electrolyte layer for water system zinc battery
CN110061311B (en) * 2019-05-08 2022-08-16 瑞海泊有限公司 Preparation method of solid electrolyte layer for water-based zinc battery
CN110828795A (en) * 2019-10-29 2020-02-21 陈璞 Zinc-manganese-oxygen cathode material and preparation method and application thereof
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
CN112467233A (en) * 2020-12-01 2021-03-09 中山市华舜科技有限责任公司 High-performance aqueous electrolyte for chargeable and dischargeable zinc-manganese battery
CN113036096A (en) * 2021-02-01 2021-06-25 复旦大学 Water system zinc-manganese battery fiber with double-functional protective layer and preparation method thereof
CN113036096B (en) * 2021-02-01 2022-05-20 复旦大学 Water system zinc-manganese battery fiber with double-function protective layer and preparation method thereof
CN113328060A (en) * 2021-06-11 2021-08-31 电子科技大学 Method for preparing flexible electrode on nano needle cone nickel substrate
WO2023003834A1 (en) * 2021-07-19 2023-01-26 Grotthuss, Inc. Rechargeable zinc metal battery
CN114122416A (en) * 2021-11-29 2022-03-01 东莞理工学院 Three-dimensional porous cobalt nitride-poly (3, 4-ethylenedioxythiophene) flexible composite electrode and preparation method thereof
CN114220939A (en) * 2021-12-15 2022-03-22 南京信息工程大学 Preparation method and application of secondary water system zinc ion battery positive electrode
CN114744153A (en) * 2022-04-20 2022-07-12 吉林大学 Conductive polymer with energy storage and biodegradation properties, preparation method, flexible electrode and degradable zinc ion battery
CN114744153B (en) * 2022-04-20 2023-07-25 吉林大学 Conductive polymer with energy storage and biodegradation properties, preparation method, flexible electrode and degradable zinc ion battery

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