WO2020155190A1 - 高电压可充电的锌锰电池 - Google Patents

高电压可充电的锌锰电池 Download PDF

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WO2020155190A1
WO2020155190A1 PCT/CN2019/074801 CN2019074801W WO2020155190A1 WO 2020155190 A1 WO2020155190 A1 WO 2020155190A1 CN 2019074801 W CN2019074801 W CN 2019074801W WO 2020155190 A1 WO2020155190 A1 WO 2020155190A1
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zinc
electrolyte
manganese
exchange membrane
acid
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PCT/CN2019/074801
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English (en)
French (fr)
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胡文彬
钟澄
刘斌
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天津大学
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Priority to US16/627,284 priority Critical patent/US11444335B2/en
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • 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
    • H01M10/24—Alkaline accumulators
    • H01M10/26—Selection of materials as electrolytes
    • 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
    • H01M4/24—Electrodes for alkaline accumulators
    • 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
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/244—Zinc electrodes
    • 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
    • H01M4/42—Alloys based on zinc
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to a zinc-manganese battery, in particular to a high-voltage rechargeable zinc-manganese battery.
  • Zinc-manganese batteries have been widely used in society since they were invented in the 1860s because of their reasonable structural design and low raw material prices.
  • the zinc-manganese batteries currently on the market are mainly divided into carbon batteries and alkaline zinc-manganese batteries.
  • the working principles are:
  • Negative electrode: Zn+2NH 4 Cl Zn(NH 3 ) 2 Cl 2 +2H + +2e
  • the Zn electrode potential is stable 0.8V, and the electrode potential of manganese dioxide is between 0.7V and 1.0V, so the open circuit voltage of the carbon battery is between 1.5V and 1.8V.
  • the open circuit voltage of the battery is about 1.55V.
  • the open circuit voltage is between 1.5V and 1.8V.
  • the working voltage is 1.25V ⁇ 1.55V.
  • the valence state of the manganese dioxide electrode in the existing zinc-manganese battery changes from +4 to +3, which means that a single manganese dioxide molecule can only emit one electron.
  • the manganese dioxide electrode undergoes a solid-state transformation during operation, and the generated basic manganese oxide will cover the surface of the electrode and affect further reactions.
  • lead dioxide electrode in lead-acid batteries is converted into solid lead sulfate during discharge and covers the lead dioxide electrode.
  • the lead dioxide electrode in lead-acid batteries is converted into solid lead sulfate during discharge and covers the lead dioxide electrode.
  • the solid lead sulfate produced can be oxidized to lead dioxide.
  • lead-acid batteries will undergo electrode sulfation during operation, which limits the performance and life of lead-acid batteries.
  • the purpose of the present invention is to overcome the problems of low voltage, capacity and reversibility of the existing zinc-manganese battery, and to provide a high-voltage rechargeable zinc-manganese battery.
  • the present invention relates to a high-voltage rechargeable zinc-manganese battery.
  • the structure of the zinc-manganese battery includes zinc electrode/alkaline electrolyte/ion exchange membrane/acid electrolyte/manganese dioxide electrode
  • the zinc electrode is prepared by using zinc foil, zinc paste or zinc powder.
  • the alkaline electrolyte includes an alkaline liquid electrolyte, an alkaline solid electrolyte, an alkaline polymer electrolyte or an alkaline gel electrolyte.
  • the alkaline liquid electrolyte includes potassium hydroxide solution, lithium hydroxide solution or sodium hydroxide solution with or without additives; the additives include but are not limited to zinc chloride, zinc sulfate, zinc nitrate, and zinc acetate ,Zinc oxide.
  • the concentration of alkali metal hydroxide in the alkaline liquid electrolyte is 200 g/L to 600 g/L. Since the potential of the zinc electrode is related to the pH value, in the system of the present invention, when the alkali metal hydroxide concentration is lower than this range, the battery voltage is low and is not conducive to the dissolution of the zinc electrode reaction product; when the alkali metal hydroxide When the concentration is higher than this range, the electrolyte concentration is too large, which is not conducive to ion diffusion and conduction in the solution, and will accelerate electrode corrosion. From the perspective of both battery voltage and electrolyte ion conductivity, it is more preferable that the concentration of alkali metal hydroxide in the alkaline liquid electrolyte is 300 g/L to 400 g/L.
  • the electrolyte in the alkaline gel electrolyte is one or more of potassium hydroxide, sodium hydroxide, and lithium hydroxide; the gel skeleton is polyvinyl alcohol, polyacrylic acid, potassium polyacrylate, and polyepoxy. One or a mixture of two or more of ethane.
  • the electrolyte is added to the alkaline gel electrolyte in the form of a solution as a raw material.
  • the content of the alkali metal hydroxide in the liquid phase portion of the alkaline gel electrolyte is 100 g/L to 300 g/L.
  • the alkali metal hydroxide concentration is lower than this range, the resulting alkaline gel electrolyte has a lower pH and the resulting battery voltage is lower.
  • the alkali metal hydroxide concentration is higher than this range, the alkaline gel electrolyte cannot be shaped.
  • the alkali metal hydroxide in the liquid phase part of the alkaline gel electrolyte is 250g/L ⁇ 300g/L.
  • the alkaline electrolyte is an aqueous solution of 300g/L ⁇ 400g/L potassium hydroxide+40g ⁇ 60g/L zinc acetate, or 250g/L ⁇ 300g/L potassium hydroxide+40g ⁇ 60g/L zinc acetate , Polyacrylic acid-polyvinyl alcohol-potassium hydroxide-zinc acetate gel electrolyte with a mass ratio of acrylic acid to polyvinyl alcohol of 5:1 to 20:1.
  • the alkaline electrolyte of the composition can simultaneously take into account high ion conductivity, high hydroxide concentration and high reversibility of the zinc electrode.
  • the ion exchange membrane includes a cation exchange membrane, an anion exchange membrane or a proton exchange membrane.
  • an ion exchange membrane is added between the acidic electrolyte and the alkaline electrolyte to limit the contact between hydrogen ions and hydroxide ions, thereby ensuring the normal operation of the battery.
  • the ion exchange membrane can choose a proton exchange membrane or an anion exchange membrane to allow hydroxide ions to pass through, or a cation exchange membrane; the choice of the specific cation exchange membrane is related to the type of alkali metal ions in the alkaline liquid electrolyte
  • the cation exchange membrane is a cation exchange membrane that allows the alkali metal ions in the alkaline liquid electrolyte to permeate.
  • the electrolyte in the alkaline gel electrolyte contains lithium hydroxide
  • the alkaline electrolyte neutralizes to ensure the normal operation of the battery.
  • the acid electrolyte includes an acid liquid electrolyte, an acid solid electrolyte, an acid polymer electrolyte or an acid gel electrolyte.
  • the acidic liquid electrolyte includes sulfuric acid solution, phosphoric acid solution, hydrochloric acid solution, and nitric acid solution with or without additives;
  • the additives include, but are not limited to, manganese sulfate, manganese nitrate, manganese chloride, and manganese acetate.
  • the acid concentration in the acidic liquid electrolyte is 50 g/L to 300 g/L.
  • the voltage of the manganese dioxide electrode terminal is too low; when the acid concentration is higher than this range, the manganese dioxide has a dissolution problem and the electrolyte conductivity is low.
  • the acid concentration is 50 g/L to 100 g/L.
  • the acid gel electrolyte includes polyvinyl alcohol-sulfuric acid electrolyte or polyvinyl alcohol-phosphoric acid electrolyte.
  • the acid content in the liquid phase part of the acid gel electrolyte is 100 g/L to 200 g/L.
  • the acidic electrolyte is an aqueous solution of 50g/L-100g/L sulfuric acid + 150g-200g/L manganese sulfate, or a polyvinyl alcohol condensate of 100g/L-200g/L sulfuric acid + 50g-100g/L manganese sulfate Gel electrolyte.
  • the acid electrolyte of the composition can simultaneously take into account high ion conductivity, high hydrogen ion concentration, and high reversibility of the manganese dioxide electrode.
  • the manganese dioxide electrode includes a manganese dioxide powder electrode or an electrodeposited manganese dioxide electrode.
  • the manganese dioxide electrode is completely converted into divalent manganese ion form and separated from the electrode after discharge. There is no such thing as a conventional chemical battery where solid substances are formed to cover the electrode surface and affect further discharge.
  • an ion exchange is added between the acidic electrolyte and the alkaline electrolyte.
  • the membrane restricts the contact between hydrogen ions and hydroxide ions (take a proton exchange membrane as an example.
  • the neutralization rate of hydrogen ions and hydroxide ions is determined by the discharge current, which can maintain the stable operation of the battery ;
  • the discharge current which can maintain the stable operation of the battery ;
  • lithium ion exchange membrane as an example, only allow lithium ions to penetrate, and can also avoid acid and alkali electrolyte neutralization when it is conductive, so as to ensure the normal operation of the battery.
  • the present invention has the following beneficial effects:
  • the invention greatly improves the discharge voltage, power density, energy density and reversibility of the zinc-manganese battery by introducing the two-electron reaction of manganese dioxide into the battery and using a composite electrolyte of alkaline electrolyte/ion exchange membrane/acid electrolyte. Solve the major problems that plagued chemical batteries.
  • Figure 1 is a schematic structural diagram of the high-voltage rechargeable zinc-manganese battery of the present invention
  • FIG. 2 is a schematic diagram showing the comparison of discharge curves between the high-voltage rechargeable zinc-manganese battery and the traditional alkaline zinc-manganese battery of Example 4;
  • Example 3 is a charging and discharging curve of the high-voltage rechargeable zinc-manganese battery of Example 4;
  • 1 is a manganese dioxide electrode
  • 2 is an acidic electrolyte
  • 3 is an ion exchange membrane
  • 4 is an alkaline electrolyte
  • 5 is a zinc electrode.
  • the high-voltage rechargeable zinc-manganese battery of the present invention has a structure of zinc electrode/alkaline electrolyte/ion exchange membrane/acid electrolyte/manganese dioxide electrode; the specific preparation steps are as follows:
  • Alkaline electrolyte preparation Alkaline electrolyte or alkaline gel electrolyte can be used directly.
  • the alkaline electrolyte includes, but is not limited to, potassium hydroxide solution, lithium hydroxide solution or sodium hydroxide solution with or without additives; the concentration of the alkali metal hydroxide solution is 10 g/L to 1000 g/L.
  • the additives include but are not limited to zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, zinc oxide and the like.
  • the electrolyte in the alkaline gel electrolyte is one or more of potassium hydroxide, sodium hydroxide, and lithium hydroxide; the gel skeleton is polyvinyl alcohol, polyacrylic acid, potassium polyacrylate, and polyethylene oxide. One or a mixture of two or more.
  • the electrolyte is added to the alkaline gel electrolyte in the form of a solution as a raw material.
  • Ion exchange membrane including but not limited to the following: cation exchange membrane, anion exchange membrane, proton exchange membrane.
  • acid electrolyte or acid gel electrolyte can be used directly.
  • the acid electrolyte includes, but is not limited to, sulfuric acid solution, phosphoric acid solution, hydrochloric acid solution, nitric acid solution, etc. with or without additives; the acid concentration is between 5 g/L and 1000 g/L.
  • the additives include but are not limited to manganese sulfate, manganese nitrate, manganese chloride, manganese acetate and the like.
  • the acid gel electrolyte includes but is not limited to the following: polyvinyl alcohol-sulfuric acid (PVA-H 2 SO 4 ) electrolyte. Polyvinyl alcohol-phosphoric acid (PVA-H 3 PO 4 ) electrolyte.
  • Manganese dioxide electrode mix manganese dioxide powder with conductive agent and additives.
  • This embodiment relates to a high-voltage rechargeable zinc-manganese battery whose structure is zinc electrode/alkaline electrolyte/ion exchange membrane/acid electrolyte/manganese dioxide electrode; the specific preparation steps are as follows:
  • alkaline electrolyte Heat 3g polyvinyl alcohol and dissolve it in 24mL water to form a uniform and stable solution, then pour into 6mL 500g/L potassium hydroxide solution + 200g/L zinc acetate solution. After continuing to stir evenly, place the resulting solution in the freezer. Then take it out for melting and use; obtain polyvinyl alcohol-potassium hydroxide-zinc acetate alkaline gel electrolyte, in which the concentration of potassium hydroxide in the liquid phase is 100g/L and the concentration of zinc acetate is 40g/L.
  • Ion exchange membrane in the high-voltage zinc-manganese battery system of this embodiment can be selected from proton exchange membrane, anion exchange membrane, cation exchange membrane, etc. Specific to this embodiment, sulfonic acid-based cation exchange membrane is used .
  • Battery assembly The battery is formed according to the structure combination of zinc electrode/alkaline electrolyte/ion exchange membrane/acid electrolyte/manganese dioxide electrode; its structure diagram is shown in Figure 1.
  • the obtained battery open circuit voltage is above 2.6V, and the working platform voltage is above 2.5V.
  • the obtained battery can be charged and discharged, the charging voltage is within 3V, and the number of stable cycles is more than 50 times.
  • This embodiment relates to a high-voltage rechargeable zinc-manganese battery whose structure is zinc electrode/alkaline electrolyte/ion exchange membrane/acid electrolyte/manganese dioxide electrode; the specific preparation steps are as follows:
  • alkaline liquid electrolyte 20 g of lithium hydroxide and 4 g of zinc oxide are dissolved in 100 mL of deionized water to obtain an alkaline liquid electrolyte.
  • the ion exchange membrane in the high-voltage zinc-manganese battery system of this embodiment can be a proton exchange membrane, an anion exchange membrane, a cation exchange membrane, etc. Specifically, in this embodiment, a quaternary ammonium-based anion exchange membrane is used.
  • Battery assembly The battery is formed according to the structure combination of zinc electrode/alkaline electrolyte/ion exchange membrane/acid electrolyte/manganese dioxide electrode.
  • the obtained battery open circuit voltage is above 2.6V, and the working platform voltage is above 2.4V.
  • the obtained battery can be charged and discharged, the charging voltage is within 3V, and the number of stable cycles is more than 1000 times.
  • This embodiment relates to a high-voltage rechargeable zinc-manganese battery whose structure is zinc electrode/alkaline electrolyte/ion exchange membrane/acid electrolyte/manganese dioxide electrode; the specific preparation steps are as follows:
  • Ion exchange membrane in the high-voltage zinc-manganese battery system of this embodiment can be proton exchange membrane, anion exchange membrane, cation exchange membrane, etc. Specifically, in this embodiment, a sulfonic acid matrix proton exchange membrane is used .
  • Battery assembly The battery is formed according to the structure combination of zinc electrode/alkaline electrolyte/ion exchange membrane/acid electrolyte/manganese dioxide electrode.
  • the obtained battery open circuit voltage is above 2.6V, and the working platform voltage is above 2.4V.
  • the obtained battery can be charged and discharged, the charging voltage is within 3V, and the number of stable cycles is more than 100 times.
  • This embodiment relates to a high-voltage rechargeable zinc-manganese battery whose structure is zinc electrode/alkaline electrolyte/ion exchange membrane/acid electrolyte/manganese dioxide electrode; the specific preparation steps are as follows:
  • alkaline liquid electrolyte 35 g of potassium hydroxide and 4 g of zinc acetate are dissolved in 100 mL of deionized water to obtain an alkaline liquid electrolyte.
  • Ion exchange membrane in the high-voltage zinc-manganese battery system of this embodiment can be proton exchange membrane, anion exchange membrane, cation exchange membrane, etc. Specifically, in this embodiment, a sulfonic acid matrix proton exchange membrane is used .
  • Battery assembly The battery is formed according to the structure combination of zinc electrode/alkaline electrolyte/ion exchange membrane/acid electrolyte/manganese dioxide electrode.
  • the open circuit voltage of the obtained battery is above 2.7V, and the working platform voltage is above 2.65V.
  • the obtained battery can be charged and discharged, the charging voltage is within 3V, and the number of stable cycles is greater than 1000 times.
  • This embodiment relates to a high-voltage rechargeable zinc-manganese battery whose structure is zinc electrode/alkaline electrolyte/ion exchange membrane/acid electrolyte/manganese dioxide electrode; the specific preparation steps are as follows:
  • Ion exchange membrane in the high-voltage zinc-manganese battery system of this embodiment can be proton exchange membrane, anion exchange membrane, cation exchange membrane, etc. Specifically, in this embodiment, a sulfonic acid matrix proton exchange membrane is used .
  • Battery assembly The battery is formed according to the structure combination of zinc electrode/alkaline electrolyte/ion exchange membrane/acid electrolyte/manganese dioxide electrode.
  • the obtained battery open circuit voltage is above 2.7V, and the working platform voltage is above 2.6V.
  • the obtained battery can be charged and discharged, the charging voltage is within 3V, and the number of stable cycles is more than 50 times.
  • This embodiment relates to a high-voltage rechargeable zinc-manganese battery whose structure is zinc electrode/alkaline electrolyte/ion exchange membrane/acid electrolyte/manganese dioxide electrode; the specific preparation steps are as follows:
  • Ion exchange membrane in the high-voltage zinc-manganese battery system of this embodiment can be proton exchange membrane, anion exchange membrane, cation exchange membrane, etc. Specifically, in this embodiment, a sulfonic acid matrix proton exchange membrane is used .
  • Battery assembly The battery is formed according to the structure combination of zinc electrode/alkaline electrolyte/ion exchange membrane/acid electrolyte/manganese dioxide electrode.
  • the obtained battery open circuit voltage is above 2.7V, and the working platform voltage is above 2.6V.
  • the obtained battery can be charged and discharged, the charging voltage is within 3V, and the number of stable cycles is more than 100 times.
  • This embodiment relates to a high-voltage rechargeable zinc-manganese battery whose structure is zinc electrode/alkaline electrolyte/ion exchange membrane/acid electrolyte/manganese dioxide electrode; the specific preparation steps are as follows:
  • alkaline liquid electrolyte 35 g of potassium hydroxide and 4 g of zinc acetate are dissolved in 100 mL of deionized water to obtain an alkaline liquid electrolyte.
  • Ion exchange membrane in the high-voltage zinc-manganese battery system of this embodiment can be proton exchange membrane, anion exchange membrane, cation exchange membrane, etc. Specifically, in this embodiment, a sulfonic acid matrix proton exchange membrane is used .
  • Battery assembly The battery is formed according to the structure combination of zinc electrode/alkaline electrolyte/ion exchange membrane/acid electrolyte/manganese dioxide electrode.
  • the obtained battery open circuit voltage is above 2.7V, and the working platform voltage is above 2.6V.
  • the obtained battery can be charged and discharged, the charging voltage is within 3V, and the number of stable cycles is more than 100 times.

Abstract

本发明公开了一种高电压可充电的锌锰电池；所述锌锰电池的结构包含锌电极/碱性电解质/离子交换膜/酸性电解质/二氧化锰电极；所述离子交换膜包括阳离子交换膜、阴离子交换膜或质子交换膜。本发明通过使用复合电解质体系(碱性电解质/离子交换膜/酸性电解质)，获得了高电压可充电的锌锰电池；本发明可以获得高达2.7V的开路电压，大大提升了放电电压，同时可提升放电容量并进行循环充放电。本发明具有极大的科研价值、社会效益和经济效益。

Description

高电压可充电的锌锰电池 技术领域
本发明涉及锌锰电池，具体涉及一种高电压可充电的锌锰电池。
背景技术
锌锰电池因其结构设计合理，原材料价格低，自19世纪60年代发明以来，在社会上一直受到了广泛的应用。
目前市场上的锌锰电池主要分为碳性电池与碱性锌锰电池。其工作原理分别为：
碳性电池的工作原理：
总反应：Zn+2MnO 2+2NH 4Cl＝Zn(NH 3) 2Cl 2+2MnOOH
负极：Zn+2NH 4Cl＝Zn(NH 3) 2Cl 2+2H ++2e
正极：2MnO 2+2H 2O+2e＝2MnOOH+2OH -
在碳性电池中，Zn电极电势为稳定的0.8V，二氧化锰的电极电势在0.7V～1.0V之间，因此碳性电池的开路电压在1.5V～1.8V。
碱性锌锰电池的工作原理：
总反应：Zn+2MnO 2+H 2O＝2MnOOH+ZnO
负极：Zn+2OH -＝ZnO+H 2O+2e
正极：2MnO 2+2H 2O+2e＝2MnOOH+2OH -
在碱性锌锰电池中，电池的开路电压为1.55V左右。
可见，不管是最早的以氯化铵，氯化锌作为电解质的碳性电池，还是之后出现的以氢氧化钾作为电解质的碱性锌锰电池，其开路电压均处于1.5V～1.8V之间，工作电压在1.25V～1.55V。且现有锌锰电池中二氧化锰电极在放电过程中发生的价态变化为+4价变化为+3价，意味着单个二氧化锰分子仅可放出一个电子。且二氧化锰电极在工作中发生的为固态转变，生成的碱式氧化锰会覆盖在电极表面影响进一步反应，所引起的电极极化效应会大大降低反应电压，同时降低了电池可逆性。这些问题使得锌锰电池只能被应用于一些小功率电子产品比如手电筒，MP3，收音机等，无法满足消费者日益增长的需求。
锌锰电池所出现的问题在许多化学电池均有出现，如铅酸电池中的二氧化铅电极在 放电过程中转化为固体硫酸铅覆盖在二氧化铅电极上。充电时，生成的固体硫酸铅中只有部分可以被氧化为二氧化铅。由此使得铅酸电池在工作中会发生电极硫酸盐化，限制了铅酸电池的性能与寿命。
为了解决锌锰电池，乃至化学电池的这些弊端，需要从根本上改变锌锰电池的充放电机制，寻找全新的电化学反应并引入到电池中。然而，目前的研究均是在现有的电池反应内部进行改进，没有从根本上改变问题。
发明内容
本发明的目的在于克服现有锌锰电池电压、容量、可逆性较低的问题，提供一种高电压可充电的锌锰电池。
本发明的目的是通过以下技术方案来实现的：
本发明涉及一种高电压可充电的锌锰电池，所述锌锰电池的结构包含锌电极/碱性电解质/离子交换膜/酸性电解质/二氧化锰电极
优选的，所述锌电极采用锌箔、锌膏或锌粉制备而得。
优选的，所述碱性电解质包括碱性液体电解质、碱性固态电解质、碱性聚合物电解质或碱性凝胶电解质。
优选的，所述碱性液体电解质包括含有或不含添加剂的氢氧化钾溶液、氢氧化锂溶液或氢氧化钠溶液；所述添加剂包括且不限于氯化锌、硫酸锌、硝酸锌、醋酸锌、氧化锌。
优选的，所述碱性液体电解质中碱金属氢氧化物浓度为200g/L～600g/L。由于锌电极电位与pH值有关，在本发明的体系中，当碱金属氢氧化物浓度低于该范围时，电池电压较低且不利于锌电极反应生成物的溶解；当碱金属氢氧化物浓度高于该范围时，电解液浓度过大，不利于溶液中离子扩散与传导，且会加速电极腐蚀。从兼顾电池电压与电解质离子传导性能的角度出发，更优选的，所述碱性液体电解质中碱金属氢氧化物浓度为300g/L～400g/L。
优选的，所述碱性凝胶电解质中电解质为氢氧化钾、氢氧化钠、氢氧化锂中的一种或几种；凝胶骨架为聚乙烯醇、聚丙烯酸、聚丙烯酸钾、聚环氧乙烷中的一种或两种以上的混合物。所述电解质是以溶液形式作为原料加入到碱性凝胶电解质中。
优选的，所述碱性凝胶电解质中液相部分中的碱金属氢氧化物的含量为100g/L～300g/L。当碱金属氢氧化物浓度低于该范围时，所得碱性凝胶电解质pH较低，所得电池电压较低。当碱金属氢氧化物浓度高于该范围时，碱性凝胶电解质无法成型。
为了使碱性凝胶电解质中液相部分中的碱金属氢氧化物浓度最大化并保证凝胶电解质成型性，更优选的，所述碱性凝胶电解质中液相部分中的碱金属氢氧化物的含量为250g/L～300g/L。
更优选的，所述碱性电解质为300g/L～400g/L氢氧化钾+40g～60g/L醋酸锌的水溶液，或250g/L～300g/L氢氧化钾+40g～60g/L醋酸锌，丙烯酸与聚乙烯醇质量比为5:1～20:1的聚丙烯酸–聚乙烯醇–氢氧化钾–醋酸锌凝胶电解质。所述组成的碱性电解质可同时兼顾高离子传导率、高氢氧化物浓度以及锌电极的高可逆性。
优选的，所述离子交换膜包括阳离子交换膜、阴离子交换膜或质子交换膜。本发明的体系是在酸性电解质与碱性电解质之间添加了离子交换膜以限制氢离子与氢氧根离子的接触，从而保证电池的正常工作。该离子交换膜可选择质子交换膜，也可选择阴离子交换膜，供氢氧根离子透过，还可选择阳离子交换膜；具体阳离子交换膜的选择与碱性液体电解质中碱金属离子的类型相关，也就是说，该阳离子交换膜为允许碱性液体电解质中碱金属离子透过的阳离子交换膜。如，当碱性凝胶电解质中电解质含氢氧化锂时，可选择在酸性电解质与碱性电解质之间添加锂离子交换膜，仅允许锂离子透过，从而在达到导电的情况下，避免酸，碱电解质中和，保证电池的正常工作。
优选的，所述酸性电解质包括酸性液体电解质、酸性固态电解质、酸性聚合物电解质或酸性凝胶电解质。
优选的，所述酸性液体电解质包括含有或不含添加剂的硫酸溶液、磷酸溶液、盐酸溶液、硝酸溶液；所述添加剂包括且不限于硫酸锰、硝酸锰、氯化锰、醋酸锰。
优选的，所述酸性液体电解质中酸浓度为50g/L～300g/L。在本发明的体系中，当酸浓度低于该范围时，二氧化锰电极端电压过低；当酸浓度高于该范围时，二氧化锰存在溶解问题，且电解液传导率较低。
从兼顾溶液中氢离子浓度与离子传导率的角度出发，更优选的，酸浓度为50g/L～100g/L。
优选的，所述酸性凝胶电解质包括聚乙烯醇-硫酸电解质或聚乙烯醇-磷酸电解质。
为了使酸性凝胶电解质中氢离子浓度最大化并保证凝胶电解质成型性，优选的，所述酸性凝胶电解质液相部分中的酸含量为100g/L～200g/L。
更优选的，所述酸性电解质为50g/L～100g/L硫酸+150g～200g/L硫酸锰的水溶液，或100g/L～200g/L硫酸+50g～100g/L硫酸锰的聚乙烯醇凝胶电解质。所述组成的酸性电解质可同时兼顾高离子传导率、高氢离子浓度以及二氧化锰电极的高可逆性。
优选的，所述二氧化锰电极包括二氧化锰粉末电极或电沉积二氧化锰电极。
在本发明的高电压可充电的锌锰电池体系中，二氧化锰电极在酸性电解质中，发生的电极反应为：正极反应：MnO 2+4H ++2e -＝Mn 2++2H 2O，该电极反应的标准电极电势为1.224V。该电极反应中二氧化锰电极在放电后全部转化为二价锰离子形式从电极中脱离，不存在传统化学电池中，由于生成固态物质覆盖电极表面，影响进一步放电的情况。此外，放电反应中二氧化锰从+4价转化为+2价，单个二氧化锰分子可释放2个电子，大大提升了二氧化锰电极的能量密度。该电极反应未见于各类电池体系中。而在碱性电解质中，负极反应：Zn+2OH -＝ZnO+H 2O+2e -，Zn电极的标准电极电势为-1.215V，因此，采用碱性电解质与酸性电解质的复合电解质可以实现2.45V以上的开路电压。同时，由于酸性电解质与碱性电解质不可直接接触(如直接接触会中和成中性电解质导致电池无法工作)，因此，在本发明的体系中在酸性电解质与碱性电解质之间添加了离子交换膜以限制氢离子与氢氧根离子的接触(以质子交换膜为例，使用质子交换膜后，氢离子与氢氧根的中和速率是由放电电流决定的，由此可维持电池稳定工作；以使用锂离子交换膜为例，仅允许锂离子透过，亦可在达到导电的情况下，避免酸，碱电解质中和)，从而保证电池的正常工作。
与现有技术相比，本发明具有如下有益效果：
本发明通过在电池中引入二氧化锰的二电子反应，并使用碱性电解质/离子交换膜/酸性电解质的复合电解质，大大提升了锌锰电池的放电电压，功率密度，能量密度以及可逆性，解决了困扰化学电池的重大问题。
附图说明
通过阅读参照以下附图对非限制性实施例所作的详细描述，本发明的其它特征、目的和优点将会变得更明显：
图1为本发明的高电压可充电的锌锰电池的结构示意图；
图2为实施例4的高电压可充电的锌锰电池和传统碱性锌锰电池的放电曲线对比示意图；
图3为实施例4的高电压可充电的锌锰电池充放电曲线；
其中，1为二氧化锰电极，2为酸性电解质，3为离子交换膜，4为碱性电解质，5为锌电极。
具体实施方式
下面结合具体实施例和附图对本发明进行详细说明。以下实施例将有助于本领域的 技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
本发明的高电压可充电的锌锰电池，其结构为锌电极/碱性电解质/离子交换膜/酸性电解质/二氧化锰电极；具体制备步骤如下：
1、锌电极制备：可直接使用锌箔或者锌膏。
2、碱性电解质制备：可直接使用碱性电解液或碱性凝胶电解质。
碱性电解液包括且不限于含有或不含添加剂的氢氧化钾溶液、氢氧化锂溶液或氢氧化钠溶液；所述碱金属氢氧化物溶液浓度在10g/L～1000g/L。该添加剂包括且不限于氯化锌，硫酸锌，硝酸锌，醋酸锌，氧化锌等。
所述碱性凝胶电解质中电解质为氢氧化钾、氢氧化钠、氢氧化锂中的一种或几种；凝胶骨架为聚乙烯醇，聚丙烯酸，聚丙烯酸钾，聚环氧乙烷中的一种或两种以上的混合物。所述电解质是以溶液形式作为原料加入到碱性凝胶电解质中。
3、离子交换膜：包括且不限于以下几种：阳离子交换膜、阴离子交换膜、质子交换膜。
4、酸性电解质制备：可直接使用酸性电解液或酸性凝胶电解质。
酸性电解液包括且不限于含有或不含添加剂的硫酸溶液、磷酸溶液、盐酸溶液、硝酸溶液等；所述酸浓度在5g/L～1000g/L。该添加剂包括且不限于硫酸锰，硝酸锰，氯化锰，醋酸锰等。
酸性凝胶电解质包括且不限于以下几种：聚乙烯醇-硫酸(PVA-H 2SO 4)电解质。聚乙烯醇-磷酸(PVA-H 3PO 4)电解质。
5、二氧化锰电极：将二氧化锰粉末与导电剂，添加剂混合。
具体见以下各实施例。
实施例1
本实施例涉及一种高电压可充电的锌锰电池，其结构为锌电极/碱性电解质/离子交换膜/酸性电解质/二氧化锰电极；具体制备步骤如下：
1)锌电极制备：取锌片作为锌电极。
2)制备碱性电解质：将3g聚乙烯醇加热溶解于24mL水中，形成均一、稳定溶液后，倒入6mL 500g/L氢氧化钾溶液+200g/L醋酸锌溶液。继续搅拌均匀后，将所得溶液放置于冷冻室中。随后取出融化使用；得到聚乙烯醇–氢氧化钾–醋酸锌碱性凝胶电解 质，其中液相部分中的氢氧化钾浓度为100g/L，醋酸锌浓度为40g/L。
3)离子交换膜：本实施例的高电压锌锰电池体系中离子交换膜可以选用质子交换膜、阴离子交换膜，阳离子交换膜等等，具体到本实施例，采用了磺酸基阳离子交换膜。
4)酸性电解质制备：将3g聚乙烯醇加热溶解于24mL水中，形成均一、稳定溶液后，倒入6mL 500g/L硫酸溶液。继续搅拌均匀后，将所得溶液放置于冷冻室中。随后取出融化使用。得到液相部分中的硫酸浓度为100g/L的聚乙烯醇–硫酸酸性凝胶电解质。
5)二氧化锰电极制备：将8g二氧化锰粉末与1g石墨粉末，1g聚偏氟乙烯混合均匀，再加入0.4g 100g/L硫酸溶液后搅拌，烘干后作为二氧化锰电极。
6)电池组装：按照锌电极/碱性电解质/离子交换膜/酸性电解质/二氧化锰电极的结构组合形成电池；其结构示意图如图1所示。
所得电池开路电压在2.6V以上，工作平台电压在2.5V以上。所得电池可进行充放电，充电电压在3V以内，稳定循环次数大于50次。
实施例2
本实施例涉及一种高电压可充电的锌锰电池，其结构为锌电极/碱性电解质/离子交换膜/酸性电解质/二氧化锰电极；具体制备步骤如下：
1)锌电极制备：取10g锌粉，加入4g质量分数为20wt％氢氧化锂溶液，0.04g聚丙烯酸钠粘合剂，搅拌均匀后室温放置12小时便得锌膏电极。
2)制备碱性液体电解质：将20g氢氧化锂与4g氧化锌溶解于100mL去离子水中，获得碱性液体电解质。
3)离子交换膜：本实施例的高电压锌锰电池体系中离子交换膜可以选用质子交换膜、阴离子交换膜，阳离子交换膜等等，具体到本实施例，采用了季铵基阴离子交换膜。
4)酸性液体电解质制备：将10g磷酸与20g一水合硫酸锰溶解于100mL水中，获得酸性液体电解质。
5)电沉积二氧化锰电极制备：将20g一水合硫酸锰，20g硫酸溶解于100mL水中，使用石墨片为工作电极与对电极。使用直流电源在1.8V下沉积3600秒，将电解池中阳极片取出，冲洗烘干。便获得电沉积二氧化锰电极。
6)电池组装：按照锌电极/碱性电解质/离子交换膜/酸性电解质/二氧化锰电极的结构组合形成电池。
所得电池开路电压在2.6V以上，工作平台电压在2.4V以上。所得电池可进行充放电，充电电压在3V以内，稳定循环次数大于1000次。
实施例3
本实施例涉及一种高电压可充电的锌锰电池，其结构为锌电极/碱性电解质/离子交换膜/酸性电解质/二氧化锰电极；具体制备步骤如下：
1)锌电极制备：取80g锌粉，10g石墨，10g聚偏氟乙烯，4mL N-甲基吡咯烷酮混合均匀，烘干后得锌粉电极。
2)制备碱性凝胶电解质：取1g聚乙烯醇粉末溶解于30mL水中，95度加热搅拌3小时，随后加入0.05g过硫酸钾粉末，65度保温15分钟得溶液1。
另取10g丙烯酸与10g质量分数为40wt％氢氧化钠溶液混合，并加入0.05g NN’-亚甲基双丙烯酰胺混合均匀得溶液2。
将溶液1，2混合均匀，75℃水浴保温3小时得凝胶。随后将该凝胶于质量分数为10wt％氢氧化锂溶液中浸泡24小时，得氢氧化锂浓度为100g/L的聚丙烯酸–聚乙烯醇–氢氧化锂电解质。
3)离子交换膜：本实施例的高电压锌锰电池体系中离子交换膜可以选用质子交换膜、阴离子交换膜，阳离子交换膜等等，具体到本实施例，采用了磺酸基质子交换膜。
4)酸性液体电解质制备：将10g硫酸与15g一水合硫酸锰溶解于100mL水中，获得酸性液体电解质。
5)二氧化锰电极制备：将8g二氧化锰粉末与1g石墨粉末，1g聚偏氟乙烯混合均匀，再加入0.4g 100g/L硫酸溶液后搅拌，烘干后作为二氧化锰电极。
6)电池组装：按照锌电极/碱性电解质/离子交换膜/酸性电解质/二氧化锰电极的结构组合形成电池。
所得电池开路电压在2.6V以上，工作平台电压在2.4V以上。所得电池可进行充放电，充电电压在3V以内，稳定循环次数大于100次。
实施例4
本实施例涉及一种高电压可充电的锌锰电池，其结构为锌电极/碱性电解质/离子交换膜/酸性电解质/二氧化锰电极；具体制备步骤如下：
1)锌电极制备：取10g锌粉，加入4g质量分数为40wt％氢氧化钾溶液，0.04g聚丙烯酸钠粘合剂，搅拌均匀后室温放置12小时便得锌膏电极。
2)制备碱性液体电解质：将35g氢氧化钾与4g醋酸锌溶解于100mL去离子水中，获得碱性液体电解质。
3)离子交换膜：本实施例的高电压锌锰电池体系中离子交换膜可以选用质子交换 膜、阴离子交换膜，阳离子交换膜等等，具体到本实施例，采用了磺酸基质子交换膜。
4)酸性液体电解质制备：将10g硫酸与15g一水合硫酸锰溶解于100mL水中，获得酸性液体电解质。
5)电沉积二氧化锰电极制备：将20g一水合硫酸锰，20g硫酸溶解于100mL水中，使用石墨片为工作电极与对电极。使用直流电源在1.8V下沉积3600秒，将电解池中阳极片取出，冲洗烘干。便获得电沉积二氧化锰电极。
6)电池组装：按照锌电极/碱性电解质/离子交换膜/酸性电解质/二氧化锰电极的结构组合形成电池。
如图2所示，所得电池开路电压在2.7V以上，工作平台电压为2.65V以上。如图3所示，所得电池可进行充放电，充电电压在3V以内，稳定循环次数大于1000次。
实施例5
本实施例涉及一种高电压可充电的锌锰电池，其结构为锌电极/碱性电解质/离子交换膜/酸性电解质/二氧化锰电极；具体制备步骤如下：
1)锌电极制备：取10g锌粉，加入4g质量分数为40wt％氢氧化钾溶液，0.04g聚丙烯酸钠粘合剂，搅拌均匀后室温放置12小时便得锌膏电极。
2)取1g聚乙烯醇粉末溶解于30mL水中，95度加热搅拌3小时，随后加入0.05g过硫酸钾粉末，65度保温15分钟得溶液1。
另取10g丙烯酸与10g质量分数为40wt％氢氧化钠溶液混合，并加入0.05g NN’-亚甲基双丙烯酰胺混合均匀得溶液2。
将溶液1，2混合均匀，75℃水浴保温3小时得凝胶。随后将该凝胶于250g/L氢氧化钾+40g/L醋酸锌溶液中浸泡24小时，得聚丙烯酸–聚乙烯醇–氢氧化钾–醋酸锌电解质。
3)离子交换膜：本实施例的高电压锌锰电池体系中离子交换膜可以选用质子交换膜、阴离子交换膜，阳离子交换膜等等，具体到本实施例，采用了磺酸基质子交换膜。
4)酸性凝胶电解质制备：将3g聚乙烯醇加热溶解于24mL水中，形成均一、稳定溶液后，倒入6mL 500g/L硫酸+250g/L一水合硫酸锰溶液。继续搅拌均匀后，将所得溶液放置于冷冻室中。随后取出融化使用。得聚乙烯醇–硫酸–硫酸锰电解质，其中液相部分中的硫酸浓度为100g/L，硫酸锰浓度为50g/L。
5)二氧化锰电极制备：将8g二氧化锰粉末与1g石墨粉末，1g聚偏氟乙烯混合均匀，再加入0.4g 100g/L硫酸溶液后搅拌，烘干后作为二氧化锰电极。
6)电池组装：按照锌电极/碱性电解质/离子交换膜/酸性电解质/二氧化锰电极的结 构组合形成电池。
所得电池开路电压在2.7V以上，工作平台电压在2.6V以上。所得电池可进行充放电，充电电压在3V以内，稳定循环次数大于50次。
实施例6
本实施例涉及一种高电压可充电的锌锰电池，其结构为锌电极/碱性电解质/离子交换膜/酸性电解质/二氧化锰电极；具体制备步骤如下：
1)锌电极制备：取80g锌粉，10g石墨，10g聚偏氟乙烯，4mL N-甲基吡咯烷酮混合均匀，烘干后得锌粉电极。
2)碱性凝胶电解质制备：取1g聚乙烯醇粉末溶解于30mL水中，95度加热搅拌3小时，随后加入0.05g过硫酸钾粉末，65度保温15分钟得溶液1。
另取10g丙烯酸与10g质量分数为40wt％氢氧化钠溶液混合，并加入0.05g NN’-亚甲基双丙烯酰胺混合均匀得溶液2。
将溶液1，2混合均匀，75℃水浴保温3小时得凝胶。随后将该凝胶于250g/L氢氧化钾+40g/L醋酸锌溶液中浸泡24小时，得聚丙烯酸–聚乙烯醇–氢氧化钾–醋酸锌电解质。
3)离子交换膜：本实施例的高电压锌锰电池体系中离子交换膜可以选用质子交换膜、阴离子交换膜，阳离子交换膜等等，具体到本实施例，采用了磺酸基质子交换膜。
4)酸性液体电解质制备：将10g硫酸与15g一水合硫酸锰溶解于100mL水中，获得酸性液体电解质。
5)二氧化锰电极制备：将8g二氧化锰粉末与1g石墨粉末，1g聚偏氟乙烯混合均匀，再加入0.4g 100g/L硫酸溶液后搅拌，烘干后作为二氧化锰电极。
6)电池组装：按照锌电极/碱性电解质/离子交换膜/酸性电解质/二氧化锰电极的结构组合形成电池。
所得电池开路电压在2.7V以上，工作平台电压为2.6V以上。所得电池可进行充放电，充电电压在3V以内，稳定循环次数大于100次。
实施例7
本实施例涉及一种高电压可充电的锌锰电池，其结构为锌电极/碱性电解质/离子交换膜/酸性电解质/二氧化锰电极；具体制备步骤如下：
1)锌电极制备：取10g锌粉，加入4g质量分数为40wt％氢氧化钾溶液，0.04g聚丙烯酸钠粘合剂，搅拌均匀后室温放置12小时便得锌膏电极。
2)制备碱性液体电解质：将35g氢氧化钾与4g醋酸锌溶解于100mL去离子水中， 获得碱性液体电解质。
3)离子交换膜：本实施例的高电压锌锰电池体系中离子交换膜可以选用质子交换膜、阴离子交换膜，阳离子交换膜等等，具体到本实施例，采用了磺酸基质子交换膜。
4)酸性凝胶电解质制备：将3g聚乙烯醇加热溶解于24mL水中，形成均一、稳定溶液后，倒入6mL 500g/L硫酸+250g/L一水合硫酸锰溶液。继续搅拌均匀后，将所得溶液放置于冷冻室中。随后取出融化使用。得聚乙烯醇–硫酸–硫酸锰电解质，其中液相部分中的硫酸浓度为100g/L，硫酸锰浓度为50g/L。
5)二氧化锰电极制备：将8g二氧化锰粉末与1g石墨粉末，1g聚偏氟乙烯混合均匀，再加入0.4g 100g/L硫酸溶液后搅拌，烘干后作为二氧化锰电极。
6)电池组装：按照锌电极/碱性电解质/离子交换膜/酸性电解质/二氧化锰电极的结构组合形成电池。
所得电池开路电压在2.7V以上，工作平台电压为2.6V以上。所得电池可进行充放电，充电电压在3V以内，稳定循环次数大于100次。
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。

Claims (10)

  1. 一种高电压可充电的锌锰电池，其特征在于，所述锌锰电池的结构包含锌电极/碱性电解质/离子交换膜/酸性电解质/二氧化锰电极。
  2. 如权利要求1所述的高电压可充电的锌锰电池，其特征在于，所述锌电极采用锌箔、锌膏或锌粉制备而得。
  3. 如权利要求1所述的高电压可充电的锌锰电池，其特征在于，所述碱性电解质包括碱性液体电解质、碱性固态电解质、碱性聚合物电解质或碱性凝胶电解质。
  4. 如权利要求3所述的高电压可充电的锌锰电池，其特征在于，所述碱性液体电解质包括含有或不含添加剂的氢氧化钾溶液、氢氧化锂溶液或氢氧化钠溶液；所述添加剂包括氯化锌、硫酸锌、硝酸锌、醋酸锌或氧化锌。
  5. 如权利要求3所述的高电压可充电的锌锰电池，其特征在于，所述碱性凝胶电解质中电解质为氢氧化钾、氢氧化钠、氢氧化锂中的一种或几种；凝胶骨架为聚乙烯醇、聚丙烯酸、聚丙烯酸钾、聚环氧乙烷中的一种或两种以上的混合物。
  6. 如权利要求1所述的高电压可充电的锌锰电池，其特征在于，所述离子交换膜包括阳离子交换膜、阴离子交换膜或质子交换膜。
  7. 如权利要求1所述的高电压可充电的锌锰电池，其特征在于，所述酸性电解质包括酸性液体电解质、酸性固态电解质、酸性聚合物电解质或酸性凝胶电解质。
  8. 如权利要求7所述的高电压可充电的锌锰电池，其特征在于，所述酸性液体电解质包括含有或不含添加剂的硫酸溶液、磷酸溶液、盐酸溶液或硝酸溶液；所述添加剂包括硫酸锰、硝酸锰、氯化锰、醋酸锰。
  9. 如权利要求7所述的高电压可充电的锌锰电池，其特征在于，所述酸性凝胶电解质包括聚乙烯醇-硫酸电解质或聚乙烯醇-磷酸电解质。
  10. 如权利要求1所述的高电压可充电的锌锰电池，其特征在于，所述二氧化锰电极包括二氧化锰粉末电极或电沉积二氧化锰电极。
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