CN116826200A - Aqueous zinc metal battery electrolyte and application thereof - Google Patents

Aqueous zinc metal battery electrolyte and application thereof Download PDF

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Publication number
CN116826200A
CN116826200A CN202310413648.0A CN202310413648A CN116826200A CN 116826200 A CN116826200 A CN 116826200A CN 202310413648 A CN202310413648 A CN 202310413648A CN 116826200 A CN116826200 A CN 116826200A
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zinc
zinc metal
metal battery
battery electrolyte
aqueous
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周亮君
姜汝衡
娜仁托雅
余灏
王维豪
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Central South University
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Central South University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • 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
    • H01M2300/0005—Acid electrolytes
    • H01M2300/0011—Sulfuric acid-based
    • 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

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  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention belongs to the field of electrochemical energy storage and new energy materials, relates to a water-based zinc metal battery, and in particular relates to a water-based zinc metal battery electrolyte and application thereof. The aqueous zinc metal battery electrolyte contains water, zinc ions and additives; the additive is 1,4,7, 10-tetraazacyclododecane, and the concentration of the additive in the electrolyte is 0.02-0.1 mol/L. According to the invention, 1,4,7, 10-tetraazacyclododecane is added into the zinc ion-containing electrolyte according to a certain molar ratio to protect the zinc metal cathode, the electrolyte additive can be complexed with zinc ions, the solvation structure of the zinc ions and water is changed, various side reactions of the zinc cathode are inhibited, dendrite growth and corrosion on the surface of the zinc cathode can be effectively prevented, and long-acting circulation of the zinc metal battery is realized.

Description

Aqueous zinc metal battery electrolyte and application thereof
Technical Field
The invention belongs to the field of electrochemical energy storage and new energy materials, relates to a water-based zinc metal battery, and in particular relates to a water-based zinc ion electrolyte and application thereof.
Background
With the development of human society, the energy source utilized by people is changed in stages, because of the invention of the internal combustion engine in the beginning of the 20 th century, petroleum is used as a high-efficiency fuel all the time, but the wide use of petroleum causes a plurality of negative effects, such as the generation of a large amount of carbon dioxide, carbon monoxide, sulfur dioxide and other polluted air during combustion, which seriously affects the life quality of people, and meanwhile, the fuel such as petroleum, coal and the like is used as non-renewable resources to have the crisis of energy shortage, so people begin to explore the utilization of renewable energy sources seriously.
The wide application of the electric energy brings convenience for people, hydraulic power, firepower and atomic energy provide guarantee for large-scale power supply, and the wind energy and solar energy of the novel energy production means have great prospect and have remarkable research results in recent years. Nowadays, the storage carrier for electric energy is mainly a battery, and the secondary battery can be recycled, so that the method is more friendly to the environment and has wider application range. Among various batteries, lithium ion batteries are successfully commercialized for mass production due to the advantages of high energy density, small cycle loss, long service life and the like, but on the other hand, lithium ion batteries have more defects, such as the adoption of flammable and volatile organic electrolyte, poor use safety performance, harsh conditions required for manufacturing the lithium ion batteries, and the requirement of lithium resource shortage under an anaerobic and anhydrous environment and the current gradual facing condition, so that the cost of the lithium batteries is always high, and the problem of battery safety is solved and the cost is reduced.
Compared with a lithium ion battery, the zinc metal battery has the characteristics of more environmental protection and safety, the water-based electrolyte is adopted to replace organic electrolyte, so that the safety problem is solved, the ionic conductivity of the electrolyte is improved, meanwhile, the zinc metal with high natural abundance is adopted as an anode, the safety is higher, the cost is obviously reduced, and the zinc metal battery has higher volume energy density (5851 mA h cm) -3 ). Similar to the working principle of lithium ion batteries, zinc metal batteries also use Zn 2+ The method has the advantages of large capacity, high charge and discharge speed, high long-cycle reversibility and the like, and has wide development prospect.
However, with the rapid development of zinc metal batteries in recent years, problems have also been exposed. In the process of charging and discharging cycles of the zinc metal battery, zinc is deposited in a dendrite form preferentially due to the point discharging effect on the surface of the zinc metal, and dendrite grows gradually along with the increase of the cycle number of the battery, so that the battery is finally short-circuited due to the fact that the dendrite penetrates through a diaphragm. In addition, because of the special solvation structure of zinc ions and water, a plurality of side reactions occur on the zinc metal negative electrode, such as hydrogen generation by hydrogen evolution reaction, battery swelling and oxidation reaction of zinc to generate insulated zinc hydroxide. At present, the optimization of the zinc metal negative electrode has been primarily developed, namely, the surface of the zinc negative electrode is directly modified, for example, an organic/electrodeless layer is coated on the zinc negative electrode, so that the effects of inhibiting corrosion and promoting nucleation are achieved, and the growth of zinc dendrites is inhibited; the second is modification of the zinc metal structure, for example alloying the zinc metal, with the use of a larger electrochemically active area of the current collector, allowing the Zn to exfoliate/grow in a planar fashion. However, both of these methods are generally accompanied by complicated process steps and negative effects of changing the structure of the battery, and thus, the final electrolyte additive improvement method is most realistic.
The conventional electrolyte additive mainly adopts two modes, namely, transition metal or heavy metal ions are added, and the transition metal or heavy metal ions can be firstly adsorbed at the tip of a zinc negative electrode by utilizing a more negative oxidation-reduction potential to form a protective layer so as to inhibit crazy growth of dendrites, but when the electrolyte additive is used in a large scale, the heavy metal ions can pollute the environment and have higher price; and the second is to add a small amount of organic additive, which can be adsorbed on the surface of the zinc cathode to induce zinc ions to carry out plane deposition, and can change the solvation structure of the zinc ions to inhibit hydrogen evolution corrosion, so that the zinc metal battery can carry out long-term circulation.
Search and find: as an electrolyte additive, a related report has been made on a nitrogen-containing heterocyclic compound in a lithium battery electrolyte, for example, patent CN201910230659.9 reports that 0.1-10wt% of a nitrogen-containing heterocyclic compound substituted by an electricity-absorbing substituent (for example, 1,4,7, 10-tetramethylenesulfonyl-1, 4,7, 10-tetraazacyclododecane) is added in an organic solvent system, and the compound has a higher oxidation potential by utilizing the electron-absorbing substituent in the nitrogen-containing heterocyclic compound, so that the designed lithium battery is not oxidized in the cycle, and thus the complexation effect can be exerted; the nitrogenous heterocyclic compound substituted by the electricity-absorbing substituent has good compatibility with the carbonic ester electrolyte, and the physical properties of the electrolyte are not affected; the electron-withdrawing substituent group can also carry out complexation reaction with high-valence nickel ions, thereby improving the complexation efficiency and the stability of the complex. However, reports on nitrogen-containing heterocyclic compounds as additives for aqueous zinc metal battery electrolytes have been made in a very limited number.
Disclosure of Invention
Based on the defects in the prior art, the invention firstly tries to protect the zinc cathode of the zinc metal battery by using 1,4,7, 10-tetraazacyclododecane (cyclen) as an additive of the aqueous zinc metal battery electrolyte in an aqueous system and dissolving the additive in the prepared zinc ion aqueous electrolyte according to a certain molar ratio. The additive can be adsorbed on the surface of a zinc negative electrode, zinc ions are induced to be deposited according to planar diffusion, and meanwhile, the solvation structure of the zinc ions can be improved, and hydrogen evolution corrosion of a zinc metal battery and various side reactions on the surface of the negative electrode can be greatly inhibited.
In order to achieve the above object, the technical scheme of the present invention is as follows:
the invention relates to a water-based zinc metal battery electrolyte, which contains water, zinc ions and additives; the additive is 1,4,7, 10-tetraazacyclododecane (cyclen); the concentration of the additive in the electrolyte is 0.02-0.1 mol/L.
The chemical general formula of the 1,4,7, 10-tetraazacyclododecane (cyclen) in the invention is as follows:
preferably, the concentration of the additive in the aqueous zinc metal battery electrolyte is 0.04 to 0.08mol/L and the molar ratio of the additive to zinc ions is 0.025 to 0.05:1, more preferably 0.028 to 0.032:1. still more preferably 0.03:1.
Preferably, the concentration of zinc ions in the aqueous zinc metal battery electrolyte is 1.5-3mol/L; preferably 1.9 to 2.1mol/L.
Preferably, in the aqueous zinc metal battery electrolyte, zinc ions are formed from ZnSO 4 、Zn(CF 3 SO 3 ) 2 、ZnSO 4 +Zn(CF 3 SO 3 ) 2 Providing. Preferably ZnSO 4 Providing.
Preferably, in the aqueous zinc metal battery electrolyte, zinc ions are formed from ZnSO 4 Providing and zinc concentration of 1.95-2.05mol/L; the concentration of the additive 1,4,7, 10-tetraazacyclododecane is 0.055-0.065mol/L.
The aqueous zinc metal battery electrolyte of the invention is prepared as follows: and (3) distributing water-soluble zinc salt and an additive according to the designed components, adding the water-soluble zinc salt and the additive into water, and uniformly stirring to obtain the water-based zinc metal battery electrolyte.
The invention relates to an application of an aqueous zinc metal battery electrolyte, which comprises the steps of using the aqueous zinc metal battery electrolyte for a zinc metal battery; the aqueous zinc metal battery comprises a positive electrode, a negative electrode, a diaphragm and a battery electrolyte.
The invention relates to application of an aqueous zinc metal battery electrolyte, wherein the negative electrode is zinc metal.
The invention relates to application of an aqueous zinc metal battery electrolyte, wherein the battery comprises a Zn symmetric battery and a zinc metal full battery.
The invention relates to an application of an aqueous zinc metal battery electrolyte, wherein the positive electrode is selected from zinc metal and vanadium-based oxide (V) 2 O 5 、V x O y 、M x V y O z Vanadate, V x O y ·nH 2 O、M x V y O z ·H 2 O, etc.), manganese-based oxides (alpha-MnO 2 、β-MnO 2 、δ-MnO 2 、ZnMn 2 O 4 Etc.), prussian blue analogues (PBAs, znHCF, cuHCF, coFe (CN) 6 Etc.), organic materials (PANI, PANI/CFs, PANI-GO/CNTs, PANI-CNTs-PEDOT, PANI-CNTs-TPU, CC-PANI-FeCN, PANI/Graphene, PANI/Carbon Fiber, PANI/Cellulose paper, etc.); the negative electrode is zinc metal;
the membrane is at least one selected from glass fiber, single-layer PP, single-layer PE, PP+ceramic coating, PE+ceramic coating, double-layer PP/PE, double-layer PP/PP, three-layer PP/PE/PP, nafion, PVDF, porous polymer membrane, non-woven membrane and inorganic composite membrane.
The invention relates to application of a water-based zinc metal battery electrolyte, wherein the battery comprises all zinc metal batteries including but not limited to Zn symmetrical batteries, zn Cu half batteries, zn Ti half batteries and Zn V 2 O 5 Full cell, zn MnO 2 And (3) a full battery.
The invention relates to an application of a water-based zinc metal battery electrolyte, and the obtained Zn symmetric battery; the cycle life is more than or equal to 320h. After optimization, the time can be more than or equal to 1500 hours. After further optimization, the cycle life is more than or equal to 2400h;
in the invention, the designed and prepared zinc metal full cell; the cyclic capacity retention rate is more than 21.4% under the condition of high current. After optimization, the capacity retention rate can be more than or equal to 51.0%, and after further optimization, the capacity retention rate can be more than or equal to 89.8%. The capacity retention rate after further optimization can be more than or equal to 90.9%. The high current condition refers to a current density of 3-3A g -1 Is the case in (a).
When the obtained Zn V 2 O 5 The full cell takes zinc metal as a negative electrode, glass fiber as a diaphragm, V 2 O 5 Is positive electrode, 2mol/LZn (CF) 3 SO 3 ) 2 And the aqueous solution containing 0.06 mol/L1, 4,7, 10-tetraazacyclododecane (cycloen) is used as electrolyte, and after the electrolyte circulates for 2000 circles, the capacity retention rate is more than or equal to 90 percent.
When the 1,4,7, 10-tetraazacyclododecane (cycloen) is used as the additive of the aqueous zinc metal battery electrolyte, the four nitrogen atoms in the cyclododecane additive can be coordinated and complexed with zinc ions, so that the solvation structure of the zinc ions in the electrolyte is changed, water molecules which are coordinated and combined with the zinc ions are discharged, the zinc ions are sent to the surface of the zinc metal negative electrode more quickly, and hydrogen evolution corrosion and insulating hydroxide generation of the zinc metal negative electrode are greatly inhibited. In addition, the cycloalkyl of the outer layer has a hydrophobic effect, can isolate water outside, protects zinc ions, and greatly reduces hydrogen evolution corrosion of the zinc metal anode and the generation of hydroxide byproducts.
Drawings
FIG. 1 is a chemical structure diagram of 1,4,7, 10-tetraazacyclododecane (cyclen);
fig. 2 is a graph of cycle life testing of zinc symmetrical cells of comparative example 1 and examples 1-3.
Fig. 3 is a battery performance chart of example 4.
Fig. 4 is a linear voltammetric scan test chart of comparative example 1 and example 2.
FIG. 5 is a graph of cycle life testing of zinc symmetrical cells of comparative example 2 and example 4; wherein a is a scanning electron microscope picture of a zinc sheet after the symmetric battery circulates for 100 circles when the electrolyte is zinc sulfate; and b is a scanning electron microscope picture of a zinc sheet after the symmetric battery circulates for 100 circles when the electrolyte is zinc sulfate and an additive is added.
Fig. 6 is a Zn Ti half cell LSV hydrogen evolution test curve of comparative example 1 and examples 1, 2, 3.
FIG. 7 shows Zn V of comparative example 4 and examples 8, 9 and 10 2 O 5 Full cell charge-discharge cycle diagram.
FIG. 8 shows Zn V of comparative example 4 and examples 8, 9 and 10 2 O 5 A full cell magnification plot.
Detailed Description
The invention adopts 1,4,7, 10-tetraazacyclododecane (cycloen) as the additive of the water-based zinc metal battery, and the structural formula of the additive is shown in figure 1, so that the long-acting circulation of the zinc metal battery can be realized.
In the invention, the conditions of battery detection cycle life are as follows:
zn symmetric cells, zn V, prepared in the following comparative examples were tested using a New Wei cell test System 2 O 5 Full battery charge-discharge cycle test and use of the IviumStat electrochemical workstation to perform zn||tThe half-cell was subjected to electrochemical performance testing.
The experimental conditions of constant temperature charge and discharge are as follows: the products of the comparative example and the example were tested at 30 ℃ for symmetrical batteries, and the current density of the Zn symmetrical batteries was 1 mAcm when charged and discharged -2 The method comprises the steps of carrying out a first treatment on the surface of the The charging time and the discharging time are all 1 hour; zn V 2 O 5 Full cell at 0.1A g -1 Activation is carried out 3A g after 20 circles of current circulation -1 And (5) high-current charge and discharge cycles.
The experimental conditions for hydrogen evolution potential test were: the assembled Zn Ti half cell was placed on an IviemStat electrochemical workstation at 1mV s -1 The test was performed starting from 0.1V to-0.5V.
1. Preparing an additive modified aqueous zinc metal battery electrolyte:
(1) 20mmol of ZnSO 4 Dissolving in 10ml deionized water, magnetically stirring to obtain clear solution to obtain 2mol/L ZnSO 4 An aqueous electrolyte.
(2) 20mmol of Zn (CF) 3 SO 3 ) 2 Dissolving in 10ml deionized water, magnetically stirring to obtain clear solution, and preparing into 2mol/L Zn (CF) 3 SO 3 ) 2 An aqueous electrolyte.
(3) 10mmol of ZnSO 4 And 10mmol of Zn (CF) 3 SO 3 ) 2 Dissolving in 10ml deionized water, magnetically stirring to obtain clear solution to obtain 1mol/LZnSO 4 +1mol/LZn
(CF 3 SO 3 ) 2 An aqueous electrolyte.
(4) And (3) respectively adding 0.02-0.1mol of 1,4,7, 10-tetraazacyclododecane (cyclen) into the prepared electrolyte, and magnetically stirring until the solution is completely dissolved to prepare the additive modified aqueous zinc metal battery electrolyte.
2. Assembling a water-based zinc metal battery:
zinc metal is used as a negative electrode, glass fiber is used as a diaphragm, zinc metal is used as a positive electrode, and 2mol/L ZnSO is used as a negative electrode 4 、Zn(CF 3 SO 3 ) 2 And contains 0.02-0.1 mol/L1, 4,7, 10-tetraazacyclododecane (cyclen)) The water solution of (2) is electrolyte, and the Zn symmetric battery is assembled.
Comparative example 1: zinc metal is used as a negative electrode, glass fiber is used as a diaphragm, zinc metal is used as a positive electrode, and 2mol/L ZnSO is used as a negative electrode 4 The aqueous solution is electrolyte, and the Zn symmetric battery is assembled and named ZS Zn.
Comparative example 2: zinc metal is used as a negative electrode, glass fiber is used as a diaphragm, zinc metal is used as a positive electrode, and 2mol/L Zn (CF 3 SO 3 ) 2 The water solution is electrolyte, and the Zn symmetric battery is assembled and named as ZF Zn.
Comparative example 3: zinc metal is used as a negative electrode, glass fiber is used as a diaphragm, zinc metal is used as a positive electrode, and 1mol/LZnSO is used as a negative electrode 4 +1mol/L Zn(CF 3 SO 3 ) 2 The aqueous solution is electrolyte, and the Zn symmetric battery is assembled and named as 1ZS+1ZFZn.
Comparative example 4: zinc metal is used as a negative electrode, glass fiber is used as a diaphragm, vanadium pentoxide is used as a positive electrode, 2mol/LZn (CF) 3 SO 3 ) 2 The aqueous solution is electrolyte, and Zn V is assembled 2 O 5 Full cell, named ZFZn V 2 O 5 。
Example 1: zinc metal is used as a negative electrode, glass fiber is used as a diaphragm, zinc metal is used as a positive electrode, and 2mol/L ZnSO is used as a negative electrode 4 And an aqueous solution containing 0.02 mol/L1, 4,7, 10-tetraazacyclododecane (cycloen) is used as an electrolyte to assemble the Zn symmetric battery. The cell was named ZS1C Zn. The battery performance is shown in fig. 2.
Example 2: zinc metal is used as a negative electrode, glass fiber is used as a diaphragm, zinc metal is used as a positive electrode, and 2mol/L ZnSO is used as a negative electrode 4 And an aqueous solution containing 0.06 mol/L1, 4,7, 10-tetraazacyclododecane (cycloen) is used as an electrolyte to assemble the Zn symmetric battery. The cell was named ZS3 czn Zn. The battery performance is shown in fig. 2.
Example 3: zinc metal is used as a negative electrode, glass fiber is used as a diaphragm, zinc metal is used as a positive electrode, and 2mol/L ZnSO is used as a negative electrode 4 And an aqueous solution containing 0.1 mol/L1, 4,7, 10-tetraazacyclododecane (cycloen) is used as an electrolyte to assemble the Zn symmetric battery. The cell was named ZS5C Zn. The battery performance is shown in fig. 2.
Example 4: zinc metal is used as a negative electrode,glass fiber is used as diaphragm, zinc metal is used as positive electrode, 2mol/L Zn (CF 3 SO 3 ) 2 And an aqueous solution containing 0.06 mol/L1, 4,7, 10-tetraazacyclododecane (cycloen) is used as an electrolyte to assemble the Zn symmetric battery. The cell was named ZF3 czn Zn. The battery performance is shown in fig. 3.
Example 5: zinc metal is used as a negative electrode, glass fiber is used as a diaphragm, zinc metal is used as a positive electrode, and 1mol/LZnSO is used as a negative electrode 4 +1mol/L Zn(CF 3 SO 3 ) 2 And an aqueous solution containing 0.02 mol/L1, 4,7, 10-tetraazacyclododecane (cycloen) is used as an electrolyte to assemble the Zn symmetric battery. The battery is named as 1zs+1zf1czn||zn. The battery performance is shown in fig. 4.
Example 6: zinc metal is used as a negative electrode, glass fiber is used as a diaphragm, zinc metal is used as a positive electrode, and 1mol/LZnSO is used as a negative electrode 4 +1mol/L Zn(CF 3 SO 3 ) 2 And an aqueous solution containing 0.06 mol/L1, 4,7, 10-tetraazacyclododecane (cycloen) is used as an electrolyte to assemble the Zn symmetric battery. The battery is named as 1zs+1zf3c Zn is Zn. The battery performance is shown in fig. 4.
Example 7: zinc metal is used as a negative electrode, glass fiber is used as a diaphragm, zinc metal is used as a positive electrode, and 1mol/LZnSO is used as a negative electrode 4 +1mol/L Zn(CF 3 SO 3 ) 2 And an aqueous solution containing 0.1 mol/L1, 4,7, 10-tetraazacyclododecane (cycloen) is used as an electrolyte to assemble the Zn symmetric battery. The battery is named as 1zs+1zf5c Zn is Zn. The battery performance is shown in fig. 4.
Example 8: zinc metal is used as a cathode, glass fiber is used as a diaphragm, V 2 O 5 Is positive electrode, 2mol/LZn (CF) 3 SO 3 ) 2 And an aqueous solution containing 0.02 mol/L1, 4,7, 10-tetraazacyclododecane (cycloen) is used as an electrolyte to assemble Zn V 2 O 5 And (3) a full battery. The cell was named ZF1C Zn V 2 O 5 . The battery performance is shown in fig. 7 and 8.
Example 9: zinc metal is used as a cathode, glass fiber is used as a diaphragm, V 2 O 5 Is positive electrode, 2mol/LZn (CF) 3 SO 3 ) 2 And an aqueous solution containing 0.06 mol/L1, 4,7, 10-tetraazacyclododecane (cycloen) is used as an electrolyte to assemble Zn V 2 O 5 And (3) a full battery. Electric powerThe pool is named ZF3C Zn V 2 O 5 . The battery performance is shown in fig. 7 and 8.
Example 10: zinc metal is used as a cathode, glass fiber is used as a diaphragm, V 2 O 5 Is positive electrode, 2mol/LZn (CF) 3 SO 3 ) 2 And an aqueous solution containing 0.1 mol/L1, 4,7, 10-tetraazacyclododecane (cycloen) is used as an electrolyte to assemble Zn V 2 O 5 And (3) a full battery. The cell was named ZF5 CZn V 2 O 5 . The battery performance is shown in fig. 7 and 8.
The above comparative example 1 was compared with the Zn symmetric battery charge-discharge cycles of examples 1 to 3 in the group diagram as shown in fig. 2. The battery cycle life of comparative example 1 was around 80 hours, whereas the cycle life of example 1 reached 400 hours, the cycle life of example 2 reached 2400 hours, and the cycle life of example 3 reached 1700 hours.
The comparative example 1 and example 2 were simultaneously cycled for 100 cycles, the battery was disassembled, and the morphology of the zinc anode was observed by a scanning electron microscope, as shown in fig. 5 (a) (b). By comparison, it can be found that after 100 circles of circulation in electrolyte without additives, as shown in fig. 5 (a), zinc deposition on the surface of the zinc negative electrode shows a trend of growing perpendicular to the surface, and upright zinc, namely zinc dendrites, easily puncture the diaphragm to cause short circuit of the battery, and also corresponds to the problem of short cycle life of the symmetrical battery; and after the zinc is circulated in the electrolyte with the additive for 100 circles, as shown in fig. 5 (b), zinc deposition on the surface of the zinc cathode presents a flat and uniform state, zinc is deposited in a two-dimensional plane manner, and ordered layer-by-layer stacking is presented.
The results of the comparative example and the example are tested by using a linear volt-ampere scanning method through an electrochemical workstation, and the strength of the hydrogen evolution corrosion trend of the surface of the zinc cathode can be judged. As shown in FIG. 6, a more negative potential means that hydrogen evolution reaction is more difficult to occur, and the potential of example 1 drops from-0.102 to-0.115V, the potential of example 2 drops to-0.126V, and the potential of example 3 drops to-0.131V, indicating ZnSO, as compared with comparative example 1 4 The 1,4,7, 10-tetraazacyclododecane (cyclen) additive in the electrolyte successfully inhibits hydrogen evolution corrosion reactions.
The above comparative example 2 was compared with the Zn symmetric battery charge-discharge cycle of example 4 in the group diagram as shown in fig. 3. The battery cycle life of comparative example 2 was around 80 hours, whereas example 4 cycle life reached 820 hours, and the different electrolyte systems were equally effective, demonstrating the general applicability of the 1,4,7, 10-tetraazacyclododecane (cycloen) additive.
The above comparative example 3 was compared with the Zn symmetric battery charge-discharge cycles of examples 5 to 7 in the group diagram as shown in fig. 4. The battery cycle life of comparative example 3 was around 84 hours, whereas the cycle life of example 5 reached 640 hours, the cycle life of example 6 reached 380 hours, and the cycle life of example 7 reached 320 hours.
Zn V of the above comparative example 4 and examples 8 to 10 2 O 5 The full cell charge-discharge cycle is compared in the group diagram as shown in fig. 7. At 3A g -1 Under the condition of large current, the capacity retention rate of the battery of comparative example 4 after 2000 cycles is only 21.4%, and the capacity retention rates of the batteries obtained in examples 8-10 after 2000 cycles are respectively 51.0%, 90.9% and 89.8%, and the addition of the additive greatly improves the cycle stability of the zinc metal full battery and prolongs the service life of the full battery.
Zn V of the above comparative example 4 and examples 8 to 10 2 O 5 Full cell rate performance was compared as shown in fig. 8. The batteries of examples 8-10 each had a higher specific capacity than comparative example 4 under different current conditions.

Claims (10)

1. An aqueous zinc metal battery electrolyte, characterized in that: the aqueous zinc metal battery electrolyte contains water, zinc ions and additives; the additive is 1,4,7, 10-tetraazacyclododecane; the concentration of the additive in the electrolyte is 0.02-0.1 mol/L.
2. The aqueous zinc metal battery electrolyte according to claim 1, wherein: the concentration of the additive in the aqueous zinc metal battery electrolyte is 0.04-0.08 mol/L and the mol ratio of the additive to zinc ions is 0.025-0.05:1.
3. The aqueous zinc metal battery electrolyte according to claim 2, wherein: in the zinc metal battery electrolyte, the mol ratio of the additive to zinc ions is 0.028-0.032: 1.
4. the aqueous zinc metal battery electrolyte according to claim 1, wherein: the concentration of zinc ions in the aqueous zinc metal battery electrolyte is 1.5-3mol/L.
5. The aqueous zinc-metal battery electrolyte according to claim 4, wherein: the concentration of zinc ions in the aqueous zinc metal battery electrolyte is 1.9-2.1mol/L.
6. The aqueous zinc metal battery electrolyte according to claim 1, wherein: in the aqueous zinc metal battery electrolyte, zinc ions are formed by ZnSO 4 、Zn(CF 3 SO 3 ) 2 、ZnSO 4 +Zn(CF 3 SO 3 ) 2 、Zn(Cl) 2 And the like. Preferably by ZnSO 4 Providing.
7. The aqueous zinc-metal battery electrolyte according to claim 6, wherein: in the aqueous zinc metal battery electrolyte, zinc ions are formed by ZnSO 4 Providing and zinc concentration of 1.95-2.05mol/L; the concentration of the additive 1,4,7, 10-tetraazacyclododecane is 0.055-0.065mol/L.
8. Use of an aqueous zinc-metal battery electrolyte according to any one of claims 1 to 6, characterized in that: the application includes applying an aqueous zinc metal battery electrolyte to a zinc metal battery; the water-based zinc metal battery comprises a positive electrode, a negative electrode, a diaphragm and battery electrolyte; the negative electrode is zinc.
9. The use of an aqueous zinc-metal battery electrolyte according to claim 8, characterized in that: the positive electrode is at least one selected from zinc metal, vanadium-based oxide, manganese-based oxide, prussian blue analogues and organic materials; the negative electrode is zinc metal;
the membrane is at least one selected from a glass fiber membrane, a single-layer PP membrane, a single-layer PE membrane, a PP+ ceramic coating membrane, a PE+ ceramic coating membrane, a double-layer PP/PE membrane, a double-layer PP/PP and a three-layer PP/PE/PP membrane, a Nafion membrane, a PVDF membrane, a porous polymer membrane, a non-woven membrane and an inorganic composite membrane.
10. The use of an aqueous zinc-metal battery electrolyte according to claim 7, characterized in that:
the battery comprises all zinc metal batteries including but not limited to Zn symmetric batteries, zn Cu half batteries, zn Ti half batteries, zn V 2 O 5 Full cell, zn MnO 2 A full cell;
the Zn symmetric battery is obtained; the cycle life is more than or equal to 320h. After optimization, the time can be more than or equal to 1500 hours. After further optimization, the cycle life is more than or equal to 2400h;
when the obtained zinc metal full cell is Zn V 2 O 5 When the battery is full, the cycle capacity retention rate is more than 21.4% under the condition of high current; after optimization, the capacity retention rate can be more than or equal to 51.0%, and after further optimization, the capacity retention rate can be more than or equal to 89.8%. The capacity retention rate of the alloy after further optimization can be more than or equal to 90.9%;
the high current condition refers to a current density of 3-3A g -1 Is the case in (a).
CN202310413648.0A 2023-04-18 2023-04-18 Aqueous zinc metal battery electrolyte and application thereof Pending CN116826200A (en)

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