CN113224395B - Aqueous acidic zinc-manganese battery - Google Patents

Aqueous acidic zinc-manganese battery Download PDF

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Publication number
CN113224395B
CN113224395B CN202110542918.9A CN202110542918A CN113224395B CN 113224395 B CN113224395 B CN 113224395B CN 202110542918 A CN202110542918 A CN 202110542918A CN 113224395 B CN113224395 B CN 113224395B
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zinc
negative electrode
alloy
acid
battery
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CN113224395A (en
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陈维
孙继飞
袁园
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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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
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • 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 discloses a water system acidic zinc-manganese dioxide battery, which comprises a positive electrode, a negative electrode and an anion exchange membrane for separating the positive electrode and the negative electrode; the anode comprises an anode current collector and an anode electrolyte, wherein the anode electrolyte comprises an aqueous solution containing manganese salt and inorganic acid; the negative electrode comprises a negative electrode current collector and a negative electrode electrolyte, wherein the negative electrode current collector comprises a zinc alloy, and the negative electrode electrolyte comprises an aqueous solution containing a weak acid zinc salt.

Description

Aqueous acidic zinc-manganese battery
Technical Field
The invention relates to the technical field of electrochemical energy storage, in particular to a water-based acidic zinc-manganese battery.
Background
With the rapid development of new green energy sources such as solar energy, wind energy and the like, electric vehicles and consumer electronics, the demand for energy storage devices is increasing, and therefore, the development of safe, low-cost and high-energy-density batteries is one of the important targets in energy development strategies of various countries. Although the organic lithium ion battery has mature technology and high energy density, the organic electrolyte is flammable, and the preparation cost is high. Compared with the water-based battery, the water-based battery has the advantages of nonflammable electrolyte, low preparation cost and the like, thereby attracting attention. The acidic water system zinc-manganese battery (pH is less than 1.5) with high discharge voltage (more than or equal to 1.95V) developed based on Mn2+/MnO2 deposition-dissolution reaction has the advantages of low price, high safety, high theoretical capacity (Mn: 606mAh g-1, zn:820mAh g-1/5851mAh mL-1) and the like, so that the acidic water system zinc-manganese battery has great application potential.
Despite the above advantages of acid zinc manganese batteries, the practical use of metallic zinc cathodes has several problems, of which hydrogen evolution corrosion is one of the major problems. In an acid zinc-manganese battery system, because the pH value of the electrolyte is less than 1.5, the polarization of hydrogen evolution reaction is seriously eliminated, so that the hydrogen evolution corrosion is aggravated, and the development of the acid zinc-manganese battery with high discharge voltage is limited.
Disclosure of Invention
In view of the above, the present invention provides an aqueous acidic zinc-manganese dioxide battery, which is intended to at least partially solve the above technical problems.
As one aspect of the present invention, the present invention provides an aqueous acidic zinc-manganese dioxide battery comprising a positive electrode, a negative electrode, and an anion exchange membrane separating the positive electrode from the negative electrode; the anode comprises an anode current collector and an anode electrolyte, wherein the anode electrolyte comprises an aqueous solution containing manganese salt and inorganic acid; the negative electrode comprises a negative electrode current collector and a negative electrode electrolyte, wherein the negative electrode current collector comprises a zinc alloy, and the negative electrode electrolyte comprises an aqueous solution containing a weak acid zinc salt.
According to the embodiment of the invention, the positive electrode current collector comprises one or more of carbon felt, carbon cloth, carbon paper and titanium foil.
According to an embodiment of the invention, the molar concentration of the manganese salt comprises 0.5 to 3mol/L.
According to an embodiment of the invention, the manganese salt comprises MnSO 4 、MnCl 2 、Mn(NO 3 ) 2 One or more of (a).
According to an embodiment of the present invention, the molar concentration of the inorganic acid includes 0.05 to 2mol/L.
According to an embodiment of the invention, the inorganic acid comprises one or more of sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid.
According to an embodiment of the present invention, the molar concentration of the zinc salt of a weak acid comprises 0.1 to 2mol/L.
According to an embodiment of the present invention, the weak acid zinc salt comprises one or more of zinc oxalate, zinc acetate, zinc borate, zinc fluoroborate, zinc citrate, zinc carbonate, zinc fluoride.
According to an embodiment of the invention, the atomic percentage of zinc in the zinc alloy comprises 50 to 90%.
According to an embodiment of the invention, the zinc alloy comprises one or more of a zinc-aluminium alloy, a zinc-niobium alloy, a zinc-silicon alloy, a zinc-aluminium-silicon alloy, a zinc-silicon-niobium alloy, a zinc-aluminium-silicon alloy.
According to the invention, weak acid radical ions in the weak acid zinc salt are used for capturing hydrogen ions which shuttle from the anode to the cathode side electrode liquid, so that the contact reaction of the hydrogen ions and the zinc cathode is prevented. Meanwhile, the zinc alloy is used as a negative electrode material to replace metal zinc, so that the potential of the hydrogen evolution electrode can be further improved, the corrosion rate of the zinc negative electrode is reduced, and the purpose of effectively preventing the hydrogen evolution corrosion reaction from occurring and prolonging the service life is achieved.
Drawings
FIG. 1 schematically shows a schematic diagram of a structure of an aqueous acidic zinc-manganese dioxide cell according to an embodiment of the invention;
FIG. 2 schematically illustrates a schematic diagram of the principle of suppressing the hydrogen evolution corrosion reaction of the negative electrode according to an embodiment of the present invention;
FIG. 3 is a graph schematically showing the comparison of constant current charging and discharging voltage time curves of an aqueous acidic zinc-manganese dioxide battery with pure zinc and zinc-aluminum-silicon alloy as negative electrodes respectively;
FIG. 4 is a graph schematically showing a comparison of constant current charge and discharge voltage time curves for an aqueous acidic zinc-manganese battery with pure zinc and zinc alloy (directional solidification) as negative electrodes, respectively;
FIG. 5a schematically shows the negative electrolyte as Zn (Ac) 2 -full cell long cycle time voltage curve of aqueous acidic zinc manganese cell a of NaCl;
FIG. 5b schematically shows the negative electrolyte as ZnSO 4 Aqueous acidic zinc manganese battery B with NaCl full cell long cycle time voltage curve.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
Fig. 1 schematically shows a structural diagram of an aqueous acidic zinc-manganese dioxide battery, and the invention provides an aqueous acidic zinc-manganese dioxide battery, which comprises a positive electrode, a negative electrode and an anion exchange membrane 5 for separating the positive electrode and the negative electrode; the anode comprises an anode current collector 1 and an anode electrolyte 3, wherein the anode electrolyte 3 comprises an aqueous solution containing manganese salt and inorganic acid; the negative electrode comprises a negative current collector 2 and a negative electrolyte 4, wherein the negative current collector 2 comprises a zinc alloy, and the negative electrolyte 4 comprises an aqueous solution containing a zinc salt of a weak acid.
In the embodiment of the present invention, as shown in fig. 2, weak acid radical ions in the weak acid zinc salt are used to capture hydrogen ions that are shuttled from the positive electrode to the negative electrode side electrode solution, so as to prevent the hydrogen ions from contacting and reacting with the zinc negative electrode. Meanwhile, the zinc alloy is used as a negative electrode material to replace metal zinc, so that the potential of the hydrogen evolution electrode can be further improved, the corrosion rate of the zinc negative electrode is reduced, and the purpose of effectively preventing the hydrogen evolution corrosion reaction from occurring and prolonging the service life is achieved.
According to an embodiment of the present invention, the positive electrode current collector 1 includes one or more of a carbon felt, a carbon cloth, a carbon paper, and a titanium foil.
According to an embodiment of the invention, the molar concentration of the manganese salt comprises 0.5 to 3mol/L, such as 0.5mol/L, 1mol/L, 2mol/L, 3mol/L.
According to an embodiment of the invention, the manganese salt comprises MnSO 4 、MnCl 2 、Mn(NO 3 ) 2 One or more of (a).
In embodiments of the invention, manganese salts include, but are not limited to, mnSO 4 、MnCl 2 、Mn(NO 3 ) 2 Soluble inorganic manganese salts that provide divalent manganese ions may also be used.
According to an embodiment of the present invention, the molar concentration of the inorganic acid comprises 0.05 to 2mol/L, such as 0.05mol/L, 0.1mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L.
According to an embodiment of the invention, the inorganic acid comprises one or more of sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid.
In the present embodiment, the inorganic acid includes, but is not limited to, sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, and other inorganic acids capable of providing an acidic environment with a pH < 1 can be used.
According to an embodiment of the present invention, the molar concentration of the zinc salt of the weak acid comprises 0.1 to 2mol/L, such as 0.1mol/L, 0.3mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L.
According to an embodiment of the present invention, the weak acid zinc salt includes one or more of zinc oxalate, zinc acetate, zinc borate, zinc fluoroborate, zinc citrate, zinc carbonate, and zinc fluoride.
In the embodiment of the invention, the weak acid zinc salt provides weak acid radical ions, and the weak acid radical ions can capture hydrogen ions which shuttle from the anode to the cathode side electrode solution, so that the hydrogen ions are prevented from contact reaction with the zinc cathode.
According to an embodiment of the invention, the atomic percentage of zinc in the zinc alloy comprises 50-90%, such as 50%, 60%, 70%, 80%, 90%.
According to an embodiment of the invention, the zinc alloy comprises one or more of a zinc-aluminium alloy, a zinc-niobium alloy, a zinc-silicon alloy, a zinc-aluminium-silicon alloy, a zinc-silicon-niobium alloy, a zinc-aluminium-silicon alloy.
In the embodiment of the invention, the zinc alloy is used as the cathode material, so that the potential of the hydrogen evolution electrode can be increased, and the corrosion rate of the cathode can be reduced, thereby achieving the purpose of effectively hindering the hydrogen evolution corrosion reaction.
The performance of the aqueous acid battery provided by the present invention is further illustrated below in conjunction with electrochemical tests.
Respectively putting the zinc-aluminum-silicon alloy foil and the metal zinc foil into 1mol/L1Ml ZnSO 4 -0.1MH 2 SO 4 Carrying out symmetrical battery test in the electrolyte with the test parameter of 2mAh cm -1 -4mA cm -1 And the test result is shown in figure 3, under the acid environment, the metal zinc foil is completely corroded after 90 hours of circulation, and the battery fails. The cycle time of the zinc-aluminum-silicon alloy foil can reach 160h. Compared with a metal zinc foil, the zinc-silicon-aluminum alloy foil has longer cycle time, which shows that the zinc-silicon-aluminum alloy foil has better hydrogen evolution and corrosion resistance, so that the service life of the acid zinc-manganese battery can be effectively prolonged by adopting the zinc-aluminum-silicon alloy foil as a negative electrode.
Putting zinc-aluminum alloy foil and metal zinc foil into 30mL 1mol/L ZnSO 4 -0.1M H 2 SO 4 Symmetric battery test is carried out in the electrolyte, and the test parameter is 0.25mAh cm -1 -1mA cm -1 The test results are shown in fig. 4, the metallic zinc foil is completely corroded after 20h of cycling, and the cell fails. The cycle time of the zinc-aluminum alloy foil can reach more than 120h, which shows that the cycle life of the zinc-aluminum alloy foil is improved by 5 to 6 times than that of the metal zinc foil. Under acid environment, compared with metal zinc foil, the zinc-aluminum alloy foil has better hydrogen evolution corrosion resistance.
The carbon felt is used as a positive current collector, and the positive electrolyte adopts H 2 SO 4 -MnSO 4 Aqueous solution, carbon felt area of 1cm immersed in positive electrolyte 2 . Taking zinc-aluminum alloy foil as a negative current collector, and respectively adopting Zn (Ac) as negative electrolyte 2 Aqueous NaCl solution, znSO 4 Aqueous NaCl solution, the area of the negative current collector immersed in the negative electrolyte being 1cm 2 Aqueous acid zinc-manganese batteries A and B were prepared as shown in FIG. 1, and the prepared aqueous acid zinc-manganese batteries A and B were measured at 1mAh cm -1 2.2V constant voltage charging and 1C constant current discharging, the test results are shown in FIG. 5a and FIG. 5b, using Zn (Ac) 2 The aqueous zinc-manganese battery A using NaCl solution as electrolyte can still operate after 660h circulation (as shown in FIG. 5 a), and ZnSO is adopted 4 The aqueous zinc-manganese cell B with aqueous NaCl solution as electrolyte was no longer operational after 160h of cycling (see FIG. 5B). The comparison shows that the cycle life of the aqueous acidic zinc-manganese battery A containing the weak acid zinc salt is greatly prolonged.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. An aqueous acidic zinc-manganese dioxide battery comprises a positive electrode, a negative electrode and an anion exchange membrane for separating the positive electrode from the negative electrode; wherein the content of the first and second substances,
the positive electrode comprises a positive electrode current collector and a positive electrode electrolyte, wherein the positive electrode electrolyte comprises an aqueous solution containing a manganese salt and an inorganic acid;
the negative electrode comprises a negative electrode current collector and a negative electrode electrolyte, wherein the negative electrode current collector comprises zinc alloy, and the negative electrode electrolyte comprises an aqueous solution containing zinc salts of weak acids;
wherein the molar concentration of the inorganic acid is 0.05-2 mol/L, and the inorganic acid is used for providing an acidic environment with pH less than 1;
the manganese salt comprises MnSO 4 、MnCl 2 、Mn(NO 3 ) 2 One or more of;
the atomic percentage of zinc in the zinc alloy is 50-90%;
the zinc alloy comprises one or more of zinc-aluminum alloy, zinc-niobium alloy, zinc-silicon alloy, zinc-aluminum-silicon alloy, zinc-silicon-niobium alloy and zinc-aluminum-silicon alloy.
2. The battery of claim 1, the positive electrode current collector comprising one or more of carbon felt, carbon cloth, carbon paper, titanium foil.
3. The battery of claim 1, wherein the manganese salt has a molar concentration of 0.5 to 3mol/L.
4. The battery of claim 1, the inorganic acid comprising one or more of sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid.
5. The battery according to claim 1, wherein the molar concentration of the zinc salt of a weak acid comprises 0.1 to 2mol/L.
6. The battery of claim 1 or 5, the weak acid zinc salt comprising one or more of zinc oxalate, zinc acetate, zinc borate, zinc fluoroborate, zinc citrate, zinc carbonate, zinc fluoride.
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CN1462080A (en) * 2002-05-30 2003-12-17 江苏海四达集团有限公司 Novel corrosion-resistant zinc-based rare earth aluminum magnesium alloy negative electrode material
CN101540417B (en) * 2009-04-15 2011-01-26 清华大学深圳研究生院 Rechargeable zinc ion battery
EP3583641B1 (en) * 2017-02-17 2023-08-02 Medtrum Technologies Inc. A pulp paper for flexible batteries and the preparation method thereof
KR20200015309A (en) * 2018-08-03 2020-02-12 한국전력공사 Weak acid electrolytes containing separator Zinc-Manganese dioxide(Zn-MnO2) secondary battery system
CN112086694A (en) * 2020-09-18 2020-12-15 浙江浙能中科储能科技有限公司 Aqueous electrolyte for improving reversibility of neutral zinc-manganese battery and preparation method thereof
CN112599864A (en) * 2020-12-10 2021-04-02 浙江浙能中科储能科技有限公司 High-magnification long-service-life water-based zinc-based battery based on double electronic reactions

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