CN112599864A - High-magnification long-service-life water-based zinc-based battery based on double electronic reactions - Google Patents
High-magnification long-service-life water-based zinc-based battery based on double electronic reactions Download PDFInfo
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Abstract
The invention relates to a high-magnification long-life aqueous zinc-based battery based on double electron reaction, wherein aqueous electrolyte of the battery is electrolyte taking organic carboxylic acid zinc/manganese salt as solute, and the battery also comprises a halogen-based ion enhanced additive; the anode is manganese oxide, and the cathode is metal zinc or zinc alloy. During discharging, the manganese oxide of the positive electrode obtains electrons, reduces the electrons into manganese ions, and dissolves the manganese ions in the electrolyte; at the same time, the zinc/zinc alloy of the cathode gives out electrons to generate zinc ions into the solution. During charging, manganese ions in the positive electrode area lose electrons and are oxidized into manganese oxide and deposited on the positive electrode current collector, and zinc ions in the negative electrode are reduced into metal zinc/zinc alloy by obtaining electrons. The charging and discharging processes are alternately performed. The invention has the beneficial effects that: the weakly acidic water system zinc-based battery reaction system provided by the invention utilizes the double-electron transfer reaction of manganese oxide, and compared with the traditional single-electron transfer reaction, the specific capacity is doubled, and higher energy density is shown.
Description
Technical Field
The invention relates to the field of zinc batteries, in particular to a high-rate long-life water-based zinc-based battery based on double electron reaction.
Background
Under the background of increasingly serious environmental pollution and energy crisis, the exploration of a clean and renewable energy storage technology is very important for the sustainable development of human society. In various energy storage technologies, the commercial organic lithium ion battery has limited large-scale application due to high cost, flammability and explosiveness. The water system zinc-based battery based on the neutral water system electrolyte adopts a metal zinc cathode, has the advantages of low cost and high capacity, and simultaneously has good safety performance, so the water system zinc-based battery has good application prospect in the field of large-scale energy storage. In particular, the manganese oxide-based cathode aqueous zinc-manganese battery system is considered as an ideal energy storage battery system of the next generation due to the low cost and high theoretical capacity of the full battery. However, the energy density and cycle life of the current zinc-manganese battery system still can not meet the commercial requirements.
At present, aiming at the problems of capacity attenuation and poor rate capability caused by the dissolution of zinc-manganese system materials, the solution method mainly focuses on the modification of manganese dioxide anode materials, including the modification with high specific surfaceThe product design improves the reaction activity, the carbon material composite improves the material conductivity, the ion doping improves the structure stability of the anode material, and the like. Liuyun et al (CN 110364693A) prepared a nano three-dimensional conductive skeleton @ MnO 2 The composite structure material effectively improves the conductivity and the electrochemical stability of the material. La is prepared by Luxihong et al (CN 110600728A) 3+ Doped MnO 2 The material improves the charge and discharge rate performance of the battery. With the development of the research, the performance improvement of the material only by means of material modification has reached a bottleneck, the reaction is limited to a single electron reaction process, and as the charging and discharging process proceeds, the manganese dioxide is easy to collapse in structure, so that the cycle life of the battery faces a serious challenge, and therefore, the design of a new system is required to further improve the electrochemical performance of the battery.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a high-magnification long-service-life aqueous zinc-based secondary battery based on double-electron reaction.
The high-multiplying-power long-life aqueous zinc-based battery based on the two-electron reaction has the aqueous electrolyte of the battery, which takes organic carboxylic acid-based zinc/manganese salt as a solute, and also comprises a halogen-based ion enhancement additive.
Preferably, the method comprises the following steps: the anode is manganese (IV) oxide, and the cathode is metal zinc or zinc alloy. During discharging, manganese (IV) oxide of the positive electrode obtains electrons, is reduced into manganese (II) ions, and is dissolved in the electrolyte; at the same time, the zinc/zinc alloy of the cathode gives out electrons to generate zinc (II) ions into the solution. During charging, manganese (II) ions in the positive electrode area lose electrons and are oxidized into manganese (IV) oxide and deposited on the positive electrode current collector, and zinc (II) ions in the negative electrode obtain electrons and are reduced into metal zinc/zinc alloy. The charging and discharging processes are alternately performed. Wherein (II) and (IV) represent valence, and respectively represent +2 valence and +4 valence.
Preferably, the method comprises the following steps: the positive electrode manganese (IV) oxide active material is a self-supporting manganese oxide electrode structure prepared by a constant-voltage electrodeposition method, eliminates the influence of a binder and improves the utilization rate of the positive electrode material.
Preferably, the method comprises the following steps: the electrolyte taking organic carboxylic acid group zinc/manganese salt as solute contains zinc (II) ions and manganese (II) ions; wherein, the concentration of zinc ions is between 0.1 and 2.0mol/L, the concentration of manganese ions is between 0.1 and 2.0mol/L, and the concentration of organic carboxylic acid is between 0.01 and 1 mol/L.
Preferably, the method comprises the following steps: the pH value of the prepared electrolyte is between 3 and 6, the prepared electrolyte can be compatible with a metal zinc cathode, and an expensive diaphragm does not need to be introduced.
Preferably, the method comprises the following steps: the organic carboxylic acid includes one or more of formic acid, acetic acid, maleic acid, tartaric acid, phthalic acid, and the like.
Preferably, the method comprises the following steps: in order to improve the ion migration rate, a halogen-based ion enhancement additive is introduced, wherein the halogen-based ion enhancement additive comprises one or more of alkali metal-based halides such as potassium chloride, potassium bromide and potassium iodide, ammonium chloride, ammonium bromide, ammonium iodide, tetraethylammonium bromide, tetraethylammonium chloride and tetrabutylammonium bromide, and the corresponding ion concentration is 0.01-10 mol/L.
Preferably, the method comprises the following steps: the positive current collector is one or a compound of more of conductive carbon cloth, carbon paper, carbon felt, carbon plate, graphite felt, graphite plate, titanium mesh and nickel mesh.
Preferably, the method comprises the following steps: the negative electrode is metal zinc or zinc alloy, and the shape of the negative electrode is foil, foam or powder. The preparation process of the powdery zinc electrode comprises the following steps: zinc powder, a conductive agent and a binder are mixed and coated on the surface of the current collector to prepare the negative electrode. The conductive agent comprises one or more of acetylene black, carbon nano tubes and carbon fibers, and the mass content of the conductive agent is 10-20%; the adhesive is PVDF, and the mass content is between 10 and 20 percent.
Preferably, the method comprises the following steps: the electrolyte is statically stored in a cavity between the anode and the cathode of the battery, or circularly flows through an additional pump body.
The beneficial effects of the invention are:
1) The reaction system of the weakly acidic water system zinc-based battery provided by the invention utilizes the double-electron transfer reaction of manganese oxide, and compared with the traditional single-electron transfer reaction, the specific capacity is doubled, and higher energy density is shown. Meanwhile, the double electron transfer reaction is a dissolution deposition type reaction, the reaction type avoids the problems of material structure damage, collapse and the like caused by the traditional ion de-intercalation type reaction, and the excellent cycle life is shown.
2) According to the invention, the halogen-based ion enhanced additive is introduced, so that the ion migration speed is accelerated, and the ultrahigh rate performance is shown.
3) The organic carboxylate electrolyte is weak-acid electrolyte, can be well compatible with a metal zinc cathode, improves the reaction rate of zinc, inhibits the growth of zinc dendrites, does not need an expensive diaphragm, can be assembled into a flow battery system, and further improves the rate capability and cycle life of the battery. Therefore, the battery system is very suitable for application in large-scale energy storage systems.
Drawings
Fig. 1 is a cycle diagram of a full cell according to example 1 of the present invention.
Fig. 2 is a cycle diagram of a full cell of example 2 of the present invention.
Fig. 3 is a cycle diagram of a full cell of example 3 of the present invention.
Fig. 4 is a cycle diagram of a full cell of example 4 of the present invention.
Fig. 5 is a cycle diagram of a full cell of example 5 of the present invention.
Fig. 6 is a cycle diagram of a full cell according to example 6 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are set forth merely to aid in the understanding of the invention. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, it is possible to make various improvements and modifications to the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The invention provides a high-magnification long-life aqueous zinc-based battery system based on a double-electron reaction between solution manganese (II) ions and solid manganese (IV) oxide, which adopts organic carboxylic acid group zinc/manganese salt as an electrolyte system and particularly also comprises a halogen-based ion enhanced additive. In the electrolyte system, the anode reaction is the dissolution deposition reaction of a manganese (IV) oxide active material, so that the problem of structural collapse in the traditional de-intercalation reaction is avoided, and the battery has long service life; meanwhile, the reaction is a double-electron transfer reaction, and compared with a single-electron reaction, the reaction shows higher theoretical specific capacity (616 mAh/g) and energy density. The negative electrode is the dissolution deposition reaction from the metal zinc/zinc alloy to zinc (II) ions, and the organic carboxylate electrolyte is weakly acidic, so that the reaction rate of zinc can be obviously improved, the problem of dendritic crystal growth is effectively solved, and the cycling stability of the negative electrode is improved. Meanwhile, the halogen-based ion enhanced additive is introduced, so that the ion migration rate in the electrolyte is improved, and the ultrahigh rate performance is shown. Compared with the traditional neutral and alkaline zinc-manganese batteries, the invention has high cycle stability and power density, and can be widely applied to the fields of large-scale energy storage systems and the like.
Example 1:
the water system zinc-based secondary battery based on the double electronic reaction has a negative electrode of zinc foil and a positive electrode of graphite felt containing electrodeposited manganese (IV) oxide.
The organic zinc carboxylate/manganese carboxylate electrolyte contains 1mol/L zinc acetate and 0.5mol/L manganese acetate. Charging to 0.5mAh/cm at 1.8V constant voltage 2 Then at 5mA/cm 2 Discharging to 1V under constant current at current density. The battery test result is shown in figure 1, the coulombic efficiency of the first circle is 68.35%, but the coulombic efficiency is stabilized at 88.37% after 100 cycles, which indicates that the water-based zinc-based secondary battery with double electron reaction has better reversibility and cycling stability.
Example 2:
the water system zinc-based secondary battery based on the double electronic reaction is characterized in that a negative current collector is a zinc foil, and a positive electrode is a graphite felt containing electrodeposited manganese (IV) oxide.
Organic zinc/manganese carboxylate electrolyteComprises 1mol/L of zinc acetate, 0.5mol/L of manganese acetate and 0.3mol/L of acetic acid. Charging to 0.5mAh/cm at 1.8V constant voltage 2 Then at 5mA/cm 2 The constant current is discharged to 1V under the current density. The battery test result is shown in figure 2, the first turn coulombic efficiency is 95.28%, and the coulombic efficiency is stabilized at 97.04% after 100 cycles. Therefore, the introduction of the organic carboxylic acid into the electrolyte can improve the coulomb efficiency and the cycle life of the aqueous zinc-based secondary battery with two electron reactions.
Example 3:
the water system zinc-based secondary battery based on double electron reaction has a negative electrode current collector of zinc foil and a positive electrode of graphite felt containing electrodeposited manganese (IV) oxide.
The electrolyte contains 1mol/L zinc acetate, 0.5mol/L manganese acetate and 0.5mol/L acetic acid. Charging to 0.5mAh/cm at 1.8V constant voltage 2 Then at 5mA/cm 2 Discharging to 1V under constant current at current density. The battery test result is shown in figure 3, the first-turn coulombic efficiency is 98.15%, and the coulombic efficiency is stabilized at 97.99% after 100 cycles. Therefore, the coulomb efficiency and the cycle life of the aqueous zinc-based secondary battery with two electron reactions can be improved by increasing the concentration of the organic carboxylic acid.
Example 4:
the water system zinc-based secondary battery based on the double electronic reaction is characterized in that a negative current collector is a zinc foil, and a positive electrode is a graphite felt containing electrodeposited manganese (IV) oxide.
The electrolyte contains 1mol/L zinc acetate, 0.5mol/L manganese acetate and 0.7mol/L acetic acid. Charging to 0.5mAh/cm at 1.8V constant voltage 2 ，5mA/cm 2 Discharging to 1V under constant current at current density. The battery test results are shown in fig. 4, the first-turn coulombic efficiency is 96.07%, and the coulombic efficiency is stabilized at 98.26% after 100 cycles.
Example 5:
the long-life water system zinc-based secondary battery based on double electronic reaction has zinc foil as negative current collector and graphite felt containing electrodeposited manganese (IV) oxide as positive electrode.
The electrolyte comprises 1mol/L zinc acetate, 0.5mol/L manganese acetate, 0.5mol/L acetic acid and 1mol/L potassium bromide, and is charged to 0.5mAh/cm at a constant voltage of 1.8V 2 Then at 5mA/cm 2 The constant current is discharged to 1V under the current density, the battery test result is shown in figure 5, the cycle 2500 circles have no obvious attenuation, and the result shows that the cycle life of the aqueous zinc-based secondary battery with the double electron reaction can be prolonged by introducing the halogen ion enhanced additive on the basis of improving the concentration of the organic carboxylic acid.
Example 6:
the large-multiplying-power long-life aqueous zinc-based secondary battery based on the double-electron reaction is characterized in that a negative current collector is a zinc foil, and a positive electrode is a graphite felt containing electrodeposited manganese (IV) oxide.
The electrolyte comprises 1mol/L zinc acetate, 0.5mol/L manganese acetate, 0.5mol/L acetic acid, 1mol/L potassium bromide and 0.5mol/L tetraethylammonium bromide. Charging to 0.5mAh/cm at 1.8V constant voltage 2 Then at 20mA/cm 2 The constant current is discharged to 1V under the heavy current density, the battery test result is shown in figure 6, and the circulation is not obviously attenuated after 3000 circles, which shows that the halogen ion enhanced additive is introduced on the basis of improving the concentration of the organic carboxylic acid, so that the circulation service life of the aqueous zinc-based secondary battery with two electron reactions can be prolonged, and the battery can be circulated under the heavy current density condition, thereby showing that the aqueous zinc-based secondary battery has excellent rate performance.
Claims (10)
1. A high-rate long-life aqueous zinc-based battery based on double electronic reactions is characterized in that: the aqueous electrolyte of the battery is an electrolyte taking organic carboxylic acid-based zinc/manganese salt as a solute, and also comprises a halogen-based ion enhancement additive.
2. The dual electron reaction-based high-rate long-life aqueous zinc-based battery according to claim 1, wherein: the anode is manganese oxide, and the cathode is metal zinc or zinc alloy.
3. The dual electron reaction-based high-rate long-life aqueous zinc-based battery according to claim 2, characterized in that: the positive manganese oxide is a self-supporting manganese oxide electrode structure prepared by a constant-voltage electrodeposition method.
4. The dual electron reaction-based high-rate long-life aqueous zinc-based battery according to claim 1, wherein: the electrolyte taking organic carboxylic acid group zinc/manganese salt as solute contains zinc ions and manganese ions; wherein, the concentration of zinc ions is between 0.1 and 2.0mol/L, the concentration of manganese ions is between 0.1 and 2.0mol/L, and the concentration of organic carboxylic acid is between 0.01 and 1 mol/L.
5. The dual electron reaction-based high-rate long-life aqueous zinc-based battery according to claim 1, wherein: the pH value of the prepared electrolyte is between 3 and 6.
6. The dual electron reaction-based high-rate long-life aqueous zinc-based battery according to claim 1, wherein: the organic carboxylic acid comprises one or more of formic acid, acetic acid, maleic acid, tartaric acid or phthalic acid.
7. The dual electron reaction-based high-rate long-life aqueous zinc-based battery according to claim 1, wherein: the halogen-based ion enhancement additive comprises one or more of potassium chloride, potassium bromide, potassium iodide, ammonium chloride, ammonium bromide, ammonium iodide, tetraethylammonium bromide, tetraethylammonium chloride or tetrabutylammonium bromide, and the corresponding ion concentration of the halogen-based ion enhancement additive is 0.01-10 mol/L.
8. The dual electron reaction-based high-rate long-life aqueous zinc-based battery according to claim 2, characterized in that: the positive current collector is a composite of one or more of conductive carbon cloth, carbon paper, carbon felt, carbon plate, graphite felt, graphite plate, titanium mesh or nickel mesh.
9. The dual electron reaction-based high-rate long-life aqueous zinc-based battery according to claim 1, wherein: the negative electrode is metal zinc or zinc alloy, and the shape of the negative electrode is foil, foam or powder.
10. The dual electron reaction-based high-rate long-life aqueous zinc-based battery according to claim 1, wherein: the electrolyte is statically stored in a cavity between the anode and the cathode of the battery, or circularly flows through an additional pump body.
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| CN113054264A (en) * | 2021-05-18 | 2021-06-29 | 中国科学技术大学 | Aqueous electrolyte and aqueous electrolytic MnO2-Zn battery |
| CN113224395A (en) * | 2021-05-18 | 2021-08-06 | 中国科学技术大学 | Aqueous acidic zinc-manganese battery |
| CN113381081A (en) * | 2021-05-31 | 2021-09-10 | 天津大学 | Water-system zinc ion energy storage device |
| CN113471550A (en) * | 2021-07-06 | 2021-10-01 | 浙江恒威电池股份有限公司 | Double-active-ion-enhanced chargeable and dischargeable hybrid zinc ion battery energy storage device |
| CN113644326A (en) * | 2021-10-18 | 2021-11-12 | 北京金羽新能科技有限公司 | Water-based zinc ion battery and formation method |
| CN114220939A (en) * | 2021-12-15 | 2022-03-22 | 南京信息工程大学 | Preparation method and application of secondary water system zinc ion battery positive electrode |
| CN114725536A (en) * | 2022-04-21 | 2022-07-08 | 中南大学 | Aqueous zinc-manganese battery electrolyte and application thereof |
| CN117039207A (en) * | 2023-08-10 | 2023-11-10 | 广东工业大学 | Battery, iodine electrode material and preparation method of electrolyte |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113054264A (en) * | 2021-05-18 | 2021-06-29 | 中国科学技术大学 | Aqueous electrolyte and aqueous electrolytic MnO2-Zn battery |
| CN113224395A (en) * | 2021-05-18 | 2021-08-06 | 中国科学技术大学 | Aqueous acidic zinc-manganese battery |
| CN113381081A (en) * | 2021-05-31 | 2021-09-10 | 天津大学 | Water-system zinc ion energy storage device |
| CN113471550A (en) * | 2021-07-06 | 2021-10-01 | 浙江恒威电池股份有限公司 | Double-active-ion-enhanced chargeable and dischargeable hybrid zinc ion battery energy storage device |
| CN113644326A (en) * | 2021-10-18 | 2021-11-12 | 北京金羽新能科技有限公司 | Water-based zinc ion battery and formation method |
| CN114220939A (en) * | 2021-12-15 | 2022-03-22 | 南京信息工程大学 | Preparation method and application of secondary water system zinc ion battery positive electrode |
| CN114725536A (en) * | 2022-04-21 | 2022-07-08 | 中南大学 | Aqueous zinc-manganese battery electrolyte and application thereof |
| CN114725536B (en) * | 2022-04-21 | 2024-05-28 | 中南大学 | Water-based zinc-manganese battery electrolyte and application thereof |
| CN117039207A (en) * | 2023-08-10 | 2023-11-10 | 广东工业大学 | Battery, iodine electrode material and preparation method of electrolyte |
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