CN115172946A - Electrolyte, secondary zinc-air battery and preparation method - Google Patents

Electrolyte, secondary zinc-air battery and preparation method Download PDF

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CN115172946A
CN115172946A CN202211095524.4A CN202211095524A CN115172946A CN 115172946 A CN115172946 A CN 115172946A CN 202211095524 A CN202211095524 A CN 202211095524A CN 115172946 A CN115172946 A CN 115172946A
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zinc
electrolyte
air
battery
air battery
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CN115172946B (en
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赵思原
倪萌
刘通
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Shenzhen Research Institute HKPU
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Shenzhen Research Institute HKPU
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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
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • 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
    • 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 relates to the technical field of zinc-air batteries, in particular to an electrolyte, a secondary zinc-air battery and a preparation method. The electrolyte includes: 15-25 wt% of potassium hydroxide, 25-35wt% of potassium iodide, 0.5-2wt% of zinc oxide and the balance of water. According to the invention, potassium iodide is added into the traditional potassium hydroxide electrolyte, and an oxidation reaction (IOR) of iodide ions replaces an Oxygen Evolution Reaction (OER) in the charging process of the battery, so that no bubble is generated, the battery has no risk of bulging and liquid leakage, and the battery is safer and more reliable. The invention can realize lower charging voltage, effectively relieve the inactivation of the catalyst and prolong the service life of the zinc-air battery. The catalyst adopts Vulcan XC72R carbon black as an ORR/IOR bifunctional catalyst, has lower price compared with the traditional ORR catalyst manganese dioxide, and can effectively reduce the cost of the battery. The rechargeable zinc-air battery has longer service time than a disposable zinc-air battery, and is more environment-friendly.

Description

Electrolyte, secondary zinc-air battery and preparation method
Technical Field
The invention relates to the technical field of zinc-air batteries, in particular to a zinc-air battery which is low in electrolyte and charging voltage and does not contain oxygen bubbles during charging and a preparation method thereof.
Background
The zinc-air battery has the advantages of low price, high energy density, stable discharge and the like, and is considered as a new energy technology capable of replacing the lithium ion battery. However, only disposable zinc-air batteries are sold in the market at present and are discarded after use, so that the zinc-air batteries are not environment-friendly. The main reasons for restricting the development and commercial application of the rechargeable zinc-air battery can be summarized as follows: 1. oxygen Evolution Reactions (OERs) during the charging of zinc air cells produce oxygen bubbles. The positive electrode undergoes an Oxygen Reduction Reaction (ORR) to consume oxygen in the air when the zinc-air battery is discharged, whereas oxygen is generated during charging. However, the air holes on the air electrode can prevent the air bubbles generated during the charging of the battery from being discharged in time, so that the battery is not only swelled and loses efficacy, but also the leakage danger can occur; 2. the charging voltage of the zinc-air battery is relatively high, and is usually 2V. This is mainly due to the intrinsic slow activity of OER, which has a high oxidation potential. However, under high voltage, the catalyst on one side of the air electrode is oxidized and gradually deactivated, and the catalyst falls off due to continuously generated oxygen bubbles, which finally leads to the performance attenuation and even failure of the battery; 3. there is a lack of a bifunctional catalyst capable of catalyzing both the cell charge and discharge processes. The prepared bifunctional catalyst has low yield, high cost, complex preparation process and poor stability, and cannot be used for a rechargeable zinc-air battery.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention is directed to a zinc-air battery with an electrolyte, a low charging voltage and no oxygen bubbles generated during charging and a method for preparing the same, which aims to solve the problems of the conventional zinc-air battery that the charging voltage is high and oxygen bubbles are generated during charging.
The technical scheme of the invention is as follows:
in a first aspect, the present invention provides an electrolyte for a zinc-air battery having a low charge voltage and no generation of oxygen bubbles during charging, wherein the electrolyte comprises the following components:
potassium hydroxide: 15-25 wt%, potassium iodide: 25-35wt%, zinc oxide: 0.5-2wt%, and the balance of water.
In a second aspect, the present invention provides a method for preparing the electrolyte for a zinc-air battery having a low charging voltage and no generation of oxygen bubbles during charging, as described above, wherein the method comprises the steps of:
dissolving potassium hydroxide and zinc oxide in water, and stirring until the potassium hydroxide and the zinc oxide are completely dissolved to obtain a first mixed solution;
dissolving potassium iodide in the first mixed solution, and stirring until the potassium iodide is completely dissolved to obtain a second mixed solution;
and standing and cooling the second mixed solution at room temperature to obtain the electrolyte.
In a third aspect, the invention provides a zinc-air battery with low charging voltage and no oxygen bubbles generated during charging, which comprises an electrolyte, wherein the electrolyte is the electrolyte provided by the invention.
Optionally, the zinc-air battery further comprises a negative electrode and a positive electrode respectively located on two sides of the electrolyte, the negative electrode is a zinc sheet, and the positive electrode is an air electrode.
Optionally, the air electrode comprises an air electrode conductive substrate and a bifunctional oxygen catalyst bound to a surface of the air electrode conductive substrate, the bifunctional oxygen catalyst selected from Vulcan XC72R carbon black.
In a fourth aspect, the present invention provides a method for preparing a zinc-air battery with low charging voltage and no generation of oxygen bubbles during charging, comprising the steps of:
providing a negative electrode and a positive electrode, wherein the negative electrode is a zinc sheet, and the positive electrode is an air electrode;
providing an electrolyte, wherein the electrolyte is the electrolyte provided by the invention;
and respectively assembling the negative electrode and the positive electrode on two sides of the electrolyte to obtain the zinc-air battery.
Optionally, the preparation method of the air electrode comprises the following steps:
providing an air electrode conductive substrate;
providing a solution containing a bifunctional oxygen catalyst and a binder;
and coating the solution containing the bifunctional oxygen catalyst and the adhesive on the air electrode conductive substrate, and drying to obtain the air electrode.
Optionally, the air electrode conductive substrate is selected from carbon paper.
Optionally, the bifunctional oxygen catalyst is selected from Vulcan XC72R carbon black.
Optionally, the adhesive is Nafion perfluoro resin, and the amount of the adhesive is 80-120 wt% of the mass of the bifunctional oxygen catalyst.
Has the advantages that: the invention provides an electrolyte of a zinc-air battery, which is characterized in that potassium iodide is added into the traditional potassium hydroxide electrolyte, the potassium iodide has a lower oxidation potential than an Oxygen Evolution Reaction (OER), and the oxidation reaction (IOR) of iodide ions can replace the OER in the charging process of the battery, so that the generation of oxygen bubbles is avoided and a lower charging voltage is obtained during the charging of the battery, the battery has no risk of swelling and liquid leakage, and is safer and more reliable, thereby greatly prolonging the service life of the battery. The invention can realize lower charging voltage (the charging voltage can be reduced to 1.8V) which is lower than the commonly reported 2V charging voltage at present, thereby effectively relieving the inactivation of the catalyst and prolonging the service life of the rechargeable zinc-air battery by 50 percent.
Drawings
FIG. 1 is a photomicrograph of one side of an air electrode during charging of a zinc-air cell; wherein, FIG. 1 (a) is a microphotograph of the air electrode side at the time of charging in example 1 of the present invention; FIG. 1 (b) is a photomicrograph of the air electrode side when comparative example 1 was charged;
FIG. 2 is a graph of the charge and discharge cycle of a zinc-air battery; wherein, fig. 2 (a) is a graph of the cycle charge and discharge of the embodiment 1 of the present invention; FIG. 2 (b) is a graph showing the charge and discharge cycles of comparative example 1;
fig. 3 is an SEM image of the air electrode after zinc-air battery cycling; wherein, fig. 3 (a) is an SEM image of the air electrode after the circulation of the example 1 of the present invention; fig. 3 (b) is an SEM image of the air electrode after the circulation of comparative example 1.
Detailed Description
The invention provides an electrolyte, a zinc-air battery with low charging voltage and no oxygen bubbles generated during charging and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides electrolyte for a zinc-air battery which has low charging voltage and is free of oxygen bubbles during charging, wherein the electrolyte comprises the following components:
potassium hydroxide: 15-25 wt%, potassium iodide: 25-35wt%, zinc oxide: 0.5-2wt%, and the balance of water.
The embodiment of the invention provides an electrolyte of a zinc-air battery, potassium iodide is added into a traditional potassium hydroxide electrolyte, the potassium iodide has a lower oxidation potential than an Oxygen Evolution Reaction (OER), and an oxidation reaction (IOR) of iodide ions can replace the OER in the charging process of the battery, so that the generation of oxygen bubbles is avoided during charging of the battery, a lower charging voltage is obtained, the battery has no risk of bulging and liquid leakage, and the electrolyte is safer and more reliable, so that the service life of the battery is greatly prolonged. The embodiment of the invention can realize lower charging voltage (the charging voltage can be reduced to 1.8V) which is lower than the currently reported 2V charging voltage, thereby effectively relieving the catalyst deactivation and prolonging the service life of the rechargeable zinc-air battery by 50%.
The embodiment of the invention provides a preparation method of the electrolyte for the zinc-air battery which is low in charging voltage and does not generate oxygen bubbles during charging, wherein the preparation method comprises the following steps:
s10, dissolving potassium hydroxide and zinc oxide in water, and stirring until the potassium hydroxide and the zinc oxide are completely dissolved to obtain a first mixed solution;
s11, dissolving potassium iodide in the first mixed solution, and stirring until the potassium iodide is completely dissolved to obtain a second mixed solution;
s12, standing and cooling the second mixed solution at room temperature to obtain the electrolyte.
In step S10, in an embodiment, the step of stirring until the potassium hydroxide and the zinc oxide are completely dissolved to obtain a first mixed solution specifically includes: stirring for 10-20 min until the potassium hydroxide and zinc oxide are completely dissolved to obtain a clear and transparent first mixed solution.
In one embodiment, the water may be deionized water.
In step S11, in an embodiment, the step of stirring until potassium iodide is completely dissolved to obtain a second mixed solution specifically includes: stirring for 10-20 min until potassium iodide is completely dissolved to obtain a clear and transparent second mixed solution.
In step S12, in one embodiment, the standing and cooling time is 1-2 hours.
The embodiment of the invention provides a zinc-air battery which is low in charging voltage and does not generate oxygen bubbles during charging.
The zinc-air battery provided by the embodiment of the invention is a rechargeable zinc-air battery, has longer service life than disposable zinc-air batteries sold in the market, and is more environment-friendly.
In one embodiment, the zinc-air battery further comprises a negative electrode and a positive electrode respectively located on two sides of the electrolyte, the negative electrode is a zinc sheet, and the positive electrode is an air electrode.
In one embodiment, the air electrode comprises an air electrode conductive substrate and a bifunctional oxygen catalyst selected from Vulcan XC72R carbon black bound to a surface of the air electrode conductive substrate. The embodiment selects the air electrode bifunctional catalyst which has high ORR catalytic activity and can efficiently catalyze potassium iodide to be oxidized. The commercial Vulcan XC72R carbon black is used as an ORR/IOR dual-function catalyst for the first time, and compared with the traditional ORR catalyst manganese dioxide, the price is lower, so that the cost of the battery can be effectively reduced.
In one embodiment, the bifunctional oxygen catalyst is bound to the surface of the air electrode conductive substrate by an adhesive. Furthermore, the adhesive is Nafion perfluoro resin, and the using amount of the adhesive is 80-120 wt% of the mass of the bifunctional oxygen catalyst. If the dosage of the adhesive is too low, the catalyst is easy to fall off when the battery works, and if the loading capacity is too high, the catalytic activity area is covered.
The embodiment of the invention provides a preparation method of a zinc-air battery with low charging voltage and no oxygen bubbles generated during charging, which comprises the following steps:
s20, providing a negative electrode and a positive electrode, wherein the negative electrode is a zinc sheet, and the positive electrode is an air electrode;
s21, providing an electrolyte, wherein the electrolyte is the electrolyte provided by the embodiment of the invention;
and S22, respectively assembling the negative electrode and the positive electrode on two sides of the electrolyte to obtain the zinc-air battery.
In step S20, in one embodiment, the method for manufacturing the air electrode includes the steps of:
providing an air electrode conductive substrate;
providing a solution containing a bifunctional oxygen catalyst and a binder;
and coating the solution containing the bifunctional oxygen catalyst and the adhesive on the air electrode conductive substrate, and drying to obtain the air electrode.
In one embodiment, the air electrode conductive substrate is selected from carbon paper.
In one embodiment, the dual-function oxygen catalyst is selected from Vulcan XC72R carbon black, available from cabot corporation, usa. The embodiment selects an air electrode bifunctional catalyst which has high ORR catalytic activity and can efficiently catalyze potassium iodide to oxidize. The commercial Vulcan XC72R carbon black is used as the ORR/IOR dual-function catalyst for the first time, and compared with the traditional ORR catalyst manganese dioxide, the cost is lower, and the battery cost can be effectively reduced.
In one embodiment, the surface loading of the bifunctional oxygen catalyst on the surface of the air electrode conductive substrate is 1-2 mg/cm 2 . If the surface loading of the catalyst is too low, the catalytic effect is poor, and if the surface loading is too lowIf the amount is too high, it is difficult to sufficiently utilize the active material.
In one embodiment, the adhesive is Nafion perfluoro resin, and the amount of the adhesive is 80-120 wt% of the mass of the bifunctional oxygen catalyst. If the dosage of the adhesive is too low, the catalyst is easy to fall off when the battery works, and if the loading capacity is too high, the catalytic activity area is covered.
In one embodiment, the solution containing the bifunctional oxygen catalyst and the binder is prepared by: mixing the bifunctional oxygen catalyst and the binder in a solvent (such as absolute ethyl alcohol) to obtain the solution containing the bifunctional oxygen catalyst and the binder.
In a specific embodiment, the preparation method of the air electrode comprises the following steps:
cutting carbon paper with a certain size, soaking the carbon paper in 1M hydrochloric acid solution for 5-15 minutes to remove oxides on the surface, then sequentially cleaning the carbon paper with ethanol and deionized water, and finally drying the carbon paper for 24 hours at the temperature of 50-80 ℃;
mixing weighed Vulcan XC72R carbon black and Nafion perfluoro resin solution in a mortar filled with absolute ethyl alcohol, and grinding for 20-30 minutes to obtain a mixture;
uniformly spraying the ground mixture on carbon paper by using a spray gun, wherein the surface loading amount is 1-2 mg/cm 2 ；
And drying the carbon paper carrying the mixture for 30-40 minutes at the temperature of 50-80 ℃ to obtain the air electrode.
The invention is further illustrated by the following examples.
Example 1
The embodiment provides a zinc-air battery with low charging voltage and no oxygen bubbles generated during charging and a preparation method thereof, and the preparation method comprises the following specific steps:
1. a preparation method of electrolyte of zinc-air battery for low charging voltage and no oxygen bubble generation during charging comprises the following steps:
the first step is as follows: dissolving 3.3g of potassium hydroxide and 0.16g of zinc oxide in 7mL of deionized water, and stirring for 15 minutes until the potassium hydroxide and the zinc oxide are completely dissolved, wherein the solution becomes clear and transparent, so as to obtain a first mixed solution;
the second step is that: dissolving 4.8g of potassium iodide in the first mixed solution obtained in the first step, and stirring for 15 minutes until the potassium iodide is completely dissolved, so that the solution becomes clear and transparent, and a second mixed solution is obtained;
the third step: the second mixed solution obtained in the second step was allowed to stand at room temperature for 1 hour to be cooled, to obtain an electrolytic solution of the present example.
2. A preparation method of an air electrode of a zinc-air battery used for low charging voltage and no oxygen bubble generation during charging comprises the following specific steps:
the first step is as follows: cutting 10cm-10cm carbon paper, soaking the paper in 1M hydrochloric acid solution for 10 minutes to remove oxides on the surface, then sequentially washing the paper by using ethanol and deionized water, and finally drying the paper for 24 hours at the temperature of 60 ℃;
the second step: 300mg of Vulcan XC72R carbon black and 0.3mL of Nafion perfluororesin solution are mixed in a mortar containing 20mL of absolute ethyl alcohol and ground for 30 minutes to obtain a mixture;
the third step: the mixture ground in the second step was uniformly sprayed on carbon paper using a spray gun, considering that the amount of catalyst lost during the spraying process was usually half of the weight of the catalyst weighed, and the final catalyst loading was 1.5mg/cm 2 ；
The fourth step: the catalyst-loaded carbon paper obtained in the third step was dried at a temperature of 50 degrees celsius for 30 minutes to obtain an air electrode of this example.
3. Assembly of zinc-air battery with low charging voltage and no generation of oxygen bubbles during charging:
a zinc sheet of 10cm to 12cm in thickness of 0.2mm was polished to obtain a negative electrode, and the air electrode was used as a positive electrode, and the negative electrode and the air electrode were separated by the electrolyte. The three components are assembled to form the zinc-air battery with low charging voltage and no oxygen bubbles generated during charging.
A photomicrograph of the zinc-air cell of this example taken on the air electrode side during charging is shown in FIG. 1 (a)It can be seen that the charging current density is 20mA/cm 2 No bubble is generated under the condition (1), which shows that the embodiment can effectively solve the problem of generating oxygen bubbles during the charging of the zinc-air battery; the charge-discharge cycle performance chart of this example is shown in FIG. 2 (a), and it can be seen that the current example is 5mA/cm 2 The voltage of the charging current is only 1.79V, and the charging current can be cycled for more than 120 hours, thereby showing excellent charging and discharging cycle stability; in the air electrode after the charge and discharge cycles of this example, as shown in fig. 3 (a), it can be seen that the Vulcan XC72R carbon black is still in the form of fine particles and uniformly distributed, which proves that it is not corroded.
Example 2
The embodiment provides a zinc-air battery with low charging voltage and no oxygen bubbles generated during charging and a preparation method thereof, and the preparation method comprises the following specific steps:
1. a preparation method of electrolyte for zinc-air battery with low charging voltage and no oxygen bubble generation during charging comprises the following steps:
the first step is as follows: dissolving 3.4g of potassium hydroxide and 0.18g of zinc oxide in 7mL of deionized water, and stirring for 15 minutes until the potassium hydroxide and the zinc oxide are completely dissolved, so that the solution becomes clear and transparent, and a first mixed solution is obtained;
the second step: dissolving 4.5g of potassium iodide in the first mixed solution obtained in the first step, and stirring for 15 minutes until the potassium iodide is completely dissolved, and the solution becomes clear and transparent to obtain a second mixed solution;
the third step: the second mixed solution obtained in the second step was allowed to stand at room temperature for 1 hour to be cooled, to obtain an electrolytic solution of the present example.
2. A preparation method of an air electrode of a zinc-air battery used for low charging voltage and no oxygen bubble generation during charging comprises the following specific steps:
the first step is as follows: cutting 12cm-12cm carbon paper, soaking the paper in 1M hydrochloric acid solution for 10 minutes to remove oxides on the surface, then sequentially washing the paper with ethanol and deionized water, and finally drying the paper for 24 hours at the temperature of 60 ℃;
the second step: 288mg of Vulcan XC72R carbon black and 0.28mL of Nafion perfluororesin solution are mixed in a mortar containing 25mL of absolute ethyl alcohol and ground for 30 minutes to obtain a mixture;
the third step: the mixture obtained by grinding in the second step was uniformly sprayed on carbon paper using a spray gun, considering that the amount of catalyst lost during the spraying process was usually half of the weight of the catalyst weighed, and the final catalyst loading was 1mg/cm 2 ；
The fourth step: the catalyst-loaded carbon paper obtained in the third step was dried at a temperature of 50 degrees celsius for 30 minutes to obtain an air electrode of this example.
3. Assembly of zinc-air battery with low charging voltage and no generation of oxygen bubbles during charging:
a zinc sheet of 10cm to 10cm and 0.2mm in thickness was polished to obtain a negative electrode and the air electrode was used as a positive electrode, and the negative electrode and the air electrode were separated by the electrolyte. The three components are assembled to form the zinc-air battery with low charging voltage and no oxygen bubbles generated during charging.
The zinc-air cell of this example was at 5mA/cm 2 The voltage at the charging current of (1.82V) is 1.82V, and the cycle time of the battery can be 110 hours or more, and the battery shows excellent charge-discharge cycle stability.
Example 3
The embodiment provides a zinc-air battery with low charging voltage and no oxygen bubbles generated during charging and a preparation method thereof, and the preparation method comprises the following specific steps:
1. a preparation method of electrolyte for zinc-air battery with low charging voltage and no oxygen bubble generation during charging comprises the following steps:
the first step is as follows: dissolving 3.5g of potassium hydroxide and 0.2g of zinc oxide in 7mL of deionized water, and stirring for 15 minutes until the potassium hydroxide and the zinc oxide are completely dissolved, so that the solution becomes clear and transparent, and a first mixed solution is obtained;
the second step is that: dissolving 5g of potassium iodide in the first mixed solution obtained in the first step, and stirring for 15 minutes until the potassium iodide is completely dissolved, so that the solution becomes clear and transparent, and a second mixed solution is obtained;
the third step: the second mixed solution obtained in the second step was allowed to stand at room temperature for 1 hour to cool, and the electrolytic solution of the present example was obtained.
2. A preparation method of an air electrode of a zinc-air battery used for low charging voltage and no oxygen bubble generation during charging comprises the following specific steps:
the first step is as follows: cutting 10cm-10cm carbon paper, soaking the paper in 1M hydrochloric acid solution for 10 minutes to remove oxides on the surface, then sequentially washing the paper by using ethanol and deionized water, and finally drying the paper for 24 hours at the temperature of 60 ℃;
the second step: mixing 400mg of Vulcan XC72R carbon black and 0.4mL of Nafion perfluoro resin solution in a mortar containing 30mL of absolute ethyl alcohol, and grinding for 30 minutes to obtain a mixture;
the third step: the mixture obtained by grinding in the second step was uniformly sprayed on carbon paper using a spray gun, considering that the amount of catalyst lost during the spraying process was usually half of the weight of the catalyst weighed, and the final catalyst loading was 2mg/cm 2 ；
The fourth step: the catalyst-loaded carbon paper obtained in the third step was dried at a temperature of 50 degrees celsius for 30 minutes to obtain an air electrode of this example.
3. Assembly of zinc-air battery with low charging voltage and no generation of oxygen bubbles during charging:
a zinc sheet of 10cm to 12cm in thickness of 0.2mm was polished to obtain a negative electrode, and the air electrode was used as a positive electrode, and the negative electrode and the air electrode were separated by the electrolyte. The three components are assembled to form the zinc-air battery with low charging voltage and no oxygen bubbles generated during charging.
The zinc-air cell of this example was at 5mA/cm 2 The voltage under the charging current of (1.79V) is more than 120 hours of circulation, and the excellent charging and discharging circulation stability is shown;
comparative example 1
The comparative example provides a traditional zinc-air battery with high charging voltage and oxygen bubbles generated during charging and a preparation method thereof, and the preparation method comprises the following specific steps:
1. a traditional preparation method of electrolyte comprises the following specific steps:
the first step is as follows: dissolving 3.5g of potassium hydroxide and 0.2g of zinc oxide in 8mL of deionized water, and stirring for 15 minutes until the potassium hydroxide and the zinc oxide are completely dissolved, so that the solution becomes clear and transparent;
the second step is that: the solution obtained in the first step was allowed to stand at room temperature and cooled for 1 hour to obtain an electrolyte of this comparative example.
2. A preparation method of an air electrode for a traditional zinc-air battery comprises the following specific steps:
the first step is as follows: cutting 10cm-10cm carbon paper, soaking the paper in 1M hydrochloric acid solution for 10 minutes to remove oxides on the surface, then sequentially washing the paper by using ethanol and deionized water, and finally drying the paper for 24 hours at the temperature of 60 ℃;
the second step is that: 300mg of Vulcan XC72R carbon black and 0.3mL of Nafion perfluoro resin solution are mixed in a mortar containing 20mL of absolute ethyl alcohol and ground for 30 minutes to obtain a mixture;
the third step: the mixture ground in the second step was uniformly sprayed on carbon paper using a spray gun, considering that the amount of catalyst lost during the spraying process was usually half of the weight of the catalyst weighed, and the final catalyst loading was 1.5mg/cm 2 ；
The fourth step: the catalyst-loaded carbon paper obtained in the third step was dried at a temperature of 50 ℃ for 30 minutes to obtain an air electrode of the present comparative example.
3. High charging voltage and the equipment of traditional zinc-air battery that occasionally oxygen bubble produced during charging:
a zinc sheet of 10cm to 10cm and 0.2mm in thickness was polished to obtain a negative electrode and the air electrode was used as a positive electrode, and the negative electrode and the air electrode were separated by the electrolyte. The three components are assembled to obtain the zinc-air battery of the comparative example 1.
Comparative example 1 photomicrograph of the air electrode side during charging shown in FIG. 1 (b), it can be seen that the current density at charging is 20mA/cm 2 The condition (2) shows that a large amount of bubbles are generated when the battery is charged under the condition without potassium iodide; the charge-discharge cycle characteristics of comparative example 1 are shown in FIG. 2 (b), and it can be seen that the current density is 5mA/cm 2 The charging current of (2) is up to 2.1V, and the cycle is not stable, and only needs to workThe operation is carried out for 80 hours; comparative example 1 air electrode after charge and discharge cycles as shown in fig. 3 (b), it can be seen that Vulcan XC72R carbon black had agglomerated, the active area was greatly reduced, and severe corrosion was suffered.
In summary, the invention provides an electrolyte, a zinc-air battery with low charging voltage and no oxygen bubbles generated during charging and a preparation method thereof. The invention has the advantages that: (1) According to the invention, potassium iodide is added into the traditional potassium hydroxide electrolyte, and an oxidation reaction (IOR) of iodide ions replaces an OER in the charging process of the battery, so that no bubble is generated, the battery has no risk of swelling and leakage, and the battery is safer and more reliable. (2) The invention can realize lower charging voltage (for example, the charging voltage can be as low as 1.8V) which is lower than the currently reported 2V charging voltage, can effectively relieve the catalyst deactivation and prolong the service life of the rechargeable zinc-air battery by 50 percent. (3) The invention adopts commercial Vulcan XC72R carbon black as an ORR/IOR bifunctional catalyst for the first time, has lower price compared with the traditional ORR catalyst manganese dioxide, and can effectively reduce the cost of the battery. (4) The rechargeable zinc-air battery has longer service life than disposable zinc-air batteries sold in the market, and is more environment-friendly.
It will be understood that the invention is not limited to the examples described above, but that modifications and variations will occur to those skilled in the art in light of the above teachings, and that all such modifications and variations are considered to be within the scope of the invention as defined by the appended claims.

Claims (9)

1. An electrolyte for a zinc-air battery having a low charge voltage and free of oxygen bubble generation during charging, the electrolyte comprising the following components:
potassium hydroxide: 15-25 wt%, potassium iodide: 25-35wt%, zinc oxide: 0.5-2wt%, and the balance of water.
2. A method for preparing the electrolyte for a zinc-air battery according to claim 1, wherein the electrolyte is used for a zinc-air battery having a low charging voltage and no oxygen bubble generation during charging, and the method comprises the following steps:
dissolving potassium hydroxide and zinc oxide in water, and stirring until the potassium hydroxide and the zinc oxide are completely dissolved to obtain a first mixed solution;
dissolving potassium iodide in the first mixed solution, and stirring until the potassium iodide is completely dissolved to obtain a second mixed solution;
and standing and cooling the second mixed solution at room temperature to obtain the electrolyte.
3. A zinc-air battery having a low charging voltage and free of oxygen bubble generation during charging, said zinc-air battery comprising an electrolyte, wherein said electrolyte is the electrolyte of claim 1.
4. The zinc-air battery with low charging voltage and no oxygen bubbles generation during charging as claimed in claim 3, further comprising a negative electrode and a positive electrode respectively located at two sides of the electrolyte, wherein the negative electrode is a zinc sheet, and the positive electrode is an air electrode.
5. The low charge voltage, oxygen bubble generation oxygen-free on charge zinc-air cell of claim 4 wherein said air electrode comprises an air electrode conductive substrate and a bifunctional oxygen catalyst bound to the surface of said air electrode conductive substrate, said bifunctional oxygen catalyst selected from Vulcan XC72R carbon black.
6. A method for preparing a zinc-air battery having a low charging voltage and no oxygen bubble generation during charging according to any one of claims 3 to 5, comprising the steps of:
providing a negative electrode and a positive electrode, wherein the negative electrode is a zinc sheet, and the positive electrode is an air electrode;
providing an electrolyte, the electrolyte being the electrolyte of claim 1;
and respectively assembling the negative electrode and the positive electrode on two sides of the electrolyte to obtain the zinc-air battery.
7. The method for manufacturing a zinc-air battery with a low charging voltage and no oxygen bubble generation during charging according to claim 6, wherein the method for manufacturing the air electrode comprises the steps of:
providing an air electrode conductive substrate;
providing a solution containing a bifunctional oxygen catalyst and a binder;
and coating the solution containing the bifunctional oxygen catalyst and the adhesive on the air electrode conductive substrate, and drying to obtain the air electrode.
8. The method for manufacturing a zinc-air battery with low charging voltage and no oxygen bubble generation during charging according to claim 7, wherein the air electrode conductive substrate is selected from carbon paper.
9. The method for preparing a zinc-air battery with low charging voltage and no oxygen bubble generation during charging according to claim 7, wherein the adhesive is selected from Nafion perfluoro resin, and the amount of the adhesive used is 80-120 wt% of the mass of the bifunctional oxygen catalyst.
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