CN113161631B - Additive-containing aqueous zinc ion battery electrolyte, preparation method thereof and battery - Google Patents

Additive-containing aqueous zinc ion battery electrolyte, preparation method thereof and battery Download PDF

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CN113161631B
CN113161631B CN202110663229.3A CN202110663229A CN113161631B CN 113161631 B CN113161631 B CN 113161631B CN 202110663229 A CN202110663229 A CN 202110663229A CN 113161631 B CN113161631 B CN 113161631B
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zinc ion
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CN113161631A (en
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孙旦
李翼虎
王海燕
唐有根
钟威
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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
    • H01M10/36—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
    • 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
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Abstract

The invention discloses an additive-containing aqueous zinc ion battery electrolyte, a preparation method thereof and a battery. The electrolyte additive is a lanthanum-containing compound (such as lanthanum sulfate, lanthanum nitrate, lanthanum chloride, lanthanum acetate and hydrate thereof). The electrolyte additive can form a protective layer on the surface of zinc metal through adsorption or deposition in the zinc metal deposition process, the protective layer can adjust the deposition behavior of zinc ions, and effectively inhibit the generation of zinc dendrites, thereby improving the energy utilization rate and the cycling stability of the battery. The combination of the high-performance anode material is helpful for promoting the industrialization process of the water-based zinc ion battery.

Description

Additive-containing aqueous zinc ion battery electrolyte, preparation method thereof and battery
Technical Field
The invention belongs to the technical field of aqueous zinc ion batteries, and particularly relates to an additive-containing aqueous zinc ion battery electrolyte, a preparation method thereof and a battery.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, high reversibility and the like, is widely applied to the fields of portable electronic devices, electric automobiles, aerospace and the like, and also has good application prospect in the fields of large-scale energy storage and the like. However, the lithium ion battery has high cost, short lithium resources and poor safety, and further development of the lithium ion battery is limited. Compared with the traditional organic lithium ion battery, the water system zinc ion battery has the advantages of high safety, low cost, high ionic conductivity and the like, and has good application prospect in the field of large-scale energy storage. At present, most of research on zinc ion batteries focuses on development and modification of high-performance cathode materials, and research on cathodes is less concerned. However, studies have shown that zinc tends to deposit in dendritic form during deposition to form zinc dendrites, which undesirably grow to a certain extent to detach and form dead zinc, resulting in loss of active material, lower coulombic efficiency, and even penetration of the separator to cause internal short circuits. Dendrite-free zinc deposition is therefore an important way to improve the electrochemical performance of zinc ion batteries. The modification of the electrolyte is a simple, feasible and effective method for inhibiting the growth of dendritic crystals. The electrolyte additive can obviously improve the interfacial properties of the electrode/electrolyte, such as inducing the uniform distribution of the current density on the surface of the electrode, reducing the increase of local polarization and the like, thereby regulating and controlling the deposition behavior of zinc, inhibiting the generation of dendritic crystals, improving the electrochemical performance of the water system zinc ion battery, and improving the cycle life and the coulombic efficiency of the water system zinc ion battery.
Disclosure of Invention
In view of the defects of the prior art, the primary object of the present invention is to provide an aqueous zinc ion battery electrolyte containing an additive, wherein the additive can effectively improve the properties of charge distribution, nucleation, etc. at the interface of an electrode/electrolyte, thereby inducing uniform deposition of zinc ions, reducing polarization voltage, avoiding the generation of zinc dendrites, and finally improving the electrochemical performance of a zinc ion battery. The method has the characteristics of simple process, low cost and the like, and has great significance for promoting the improvement and commercialization of the stability of the zinc ion battery.
An aqueous zinc ion battery electrolyte containing additive is prepared by adding La capable of being electrolyzed into aqueous zinc ion battery electrolyte 3+ The compound of (1).
Preferably, the La can be electrolyzed 3+ The compound (b) comprises: at least one of lanthanum sulfate, lanthanum nitrate, lanthanum chloride, lanthanum acetate and their hydrates. Lanthanum sulfate is more preferable.
Preferably, the La can be electrolyzed 3+ The concentration of the compound (B) in the electrolyte is 0.01 to 1mol/L, preferably 0.01 to 0.3mol/L. Further preferably 0.01 to 0.05mol/L, most preferably 0.03mol/L.
Preferably, the working current range of the aqueous zinc ion battery electrolyte containing the additive is 0.1mA cm -2 -20mA·cm -2 . More preferably 1mA · cm -2 -5mA·cm -2 。
Preferably, the additive-containing aqueous zinc ion battery electrolyte contains ZnSO 4 、Zn(NO 3 ) 2 、ZnCl 2 And Zn (CF) 3 SO 3 ) 2 At least one of (1). Further preferably ZnSO 4 。
Preferably, the cathode of the battery prepared by the additive-containing aqueous zinc ion battery electrolyte is metallic zinc, and the anode is at least one of manganese-based oxide, prussian blue derivatives, vanadium-based materials, polyanion compounds, chevrel phase compounds and organic anode materials.
Preferably, the positive electrode is a manganese-based oxide (including MnO) 2 、Mn 2 O 3 、Mn 3 O 4 And MnO), prussian blue derivatives (including: KCu [ Fe ] 3+ (CN) 6 ]At least one of CuHCF and ZnHCF), vanadium-based materials (including NaV) 3 O 8 、V 2 O 5 、VO 2 And VS 2 At least one of), polyanionic compounds (including: na (Na) 3 V 2 (PO 4 ) 3 、VOPO 4 ·xH 2 O and Li 3 V 2 (PO 4 ) 3 At least one of (a), chevrel phase compounds (including: mo 6 S 8 、Mo 6 Se 8 And Mo 6 Te 8 At least one of) and an organic positive electrode material (including: p-chloro-ranil, calix [4 ]]At least one of quinone and TAPQ).
Preferably, the separator used in the battery prepared from the additive-containing aqueous zinc ion battery electrolyte comprises: glass fiber, polyethylene, polypropylene polyolefin microporous membrane, porous polymer membrane, non-woven fabric diaphragm or filter membrane. More preferably, a glass fiber separator.
The second purpose of the invention is to provide a preparation method of the water-system zinc ion battery electrolyte containing the additive, namely La can be electrolyzed 3+ The compound (c) is added to an aqueous zinc ion battery electrolyte.
The third object of the invention is to provide an aqueous zinc-ion battery prepared from the aqueous zinc-ion battery electrolyte containing the additive.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) The electrolyte additive disclosed by the invention induces zinc ions to be uniformly deposited by properties such as charge distribution, nucleation and the like which are adsorbed on the surface of a zinc metal cathode to remold an electrode/electrolyte interface, so that the generation of zinc dendrites is avoided, the polarization voltage is obviously reduced, and the service life of a water system zinc ion battery is prolonged.
(2) The inventionLa in the proposed aqueous zinc ion battery 3+ The method for regulating and controlling the zinc deposition behavior as the electrolyte additive has the advantages of simple process, easily obtained raw materials and low cost. The generation of zinc dendrites can be effectively inhibited, and the cycle life of the aqueous zinc metal battery is prolonged; the coulomb efficiency of the water system zinc ion battery is improved to more than 99 percent. The high-capacity anode material is matched, so that the practical energy density, the cycle life and the safety of the water system zinc ion battery can be improved, and the industrialization process of the water system zinc ion battery can be promoted.
Drawings
FIG. 1 shows the current density of 5mA/cm for the water-based zinc ion symmetric batteries prepared in example 1 and comparative example 1 2 The discharge capacity was a time-voltage curve at 1mA · h.
FIG. 2 is a graph showing the current density of 5mA/cm in the water-based zinc ion symmetric cell prepared in example 2 and comparative example 1 2 The discharge capacity was a time-voltage curve at 1mA · h.
FIG. 3 shows the current density of 5mA/cm for the water-based zinc ion symmetric batteries prepared in example 4 and comparative example 1 2 The discharge capacity was a time-voltage curve at 1mA · h.
Fig. 4 is an electrochemical impedance curve of the aqueous zinc ion symmetric cell prepared in example 1, example 2 and comparative example 1.
Fig. 5 is an anode X-ray diffraction curve of the aqueous zinc ion symmetric batteries prepared in example 1, example 2 and comparative example 1.
Fig. 6 is a graph of open circuit voltage versus time obtained using the assembled three-electrode system of example 1 and comparative example 1.
Fig. 7 is a scanning electron micrograph of the anode of the water-based zinc ion symmetric cell prepared in example 1, example 2 and comparative example 1.
FIG. 8 shows the current density of 1mA cm of the aqueous zinc ion full cell prepared in example 1 and comparative example 1 -2 Cycle performance curve below.
FIG. 9 shows the current density of 1mA cm of the aqueous zinc ion full cell prepared in example 3 and comparative example 1 -2 Cycle performance curve below.
Fig. 10 is an electrochemical impedance curve of the aqueous zinc ion full cell prepared in example 1, example 3 and comparative example 1.
FIG. 11 shows La of the present invention 3+ Schematic diagram of mechanism for inhibiting zinc dendrite.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Comparative example 1
At room temperature, 14.38g of zinc sulfate heptahydrate is completely dissolved in 50mL of deionized water, and the solution is uniformly dissolved for later use. The water system zinc ion symmetrical battery is assembled by adopting zinc foils as positive and negative electrodes and glass fibers as a diaphragm. Sodium vanadate and manganese dioxide are respectively used as positive electrodes, zinc foil is used as a negative electrode, and glass fiber is used as a diaphragm to assemble the water-based zinc ion full battery.
The preparation process of sodium vanadate comprises the following steps: preparing 2M NaCl solution, weighing 3g V by using an electronic balance 2 O 5 And adding the mixture into 40mL of 2M NaCl solution, and uniformly mixing. And (3) placing the mixed liquid in a water bath kettle at the temperature of 30 ℃ and stirring for 72 hours at constant temperature. After reacting for 3 days, respectively centrifugally washing the product by using ethanol and deionized water, and freeze-drying to obtain the cathode material NaV 3 O 8 ·1.5H 2 O。
NaV 3 O 8 ·1.5H 2 O anode preparation flow: respectively weighing NaV according to the mass ratio of 7 3 O 8 ·1.5H 2 Stirring uniformly in a mortar of 70mg of O, 20mg of acetylene black and 10mg of PVDF to agate, then dripping NMP to stir the slurry, grinding for 10 minutes to uniform slurry, uniformly coating the slurry on the surface of zinc foil by using a scraper, then placing the zinc foil in a vacuum drying oven for standing for 12 hours at 80 ℃, and then taking out the cut pieces.
MnO 2 The anode preparation process comprises the following steps: respectively weighing MnO according to the mass ratio of 7 2 Stirring uniformly in a mortar of 70mg, 20mg of acetylene black, 10mg of PVDF and agate, then dripping NMP to stir the mixture, grinding the mixture for 10 minutes to uniform slurry, uniformly coating the mixture on the surface of zinc foil by using a scraper, then placing the zinc foil in a vacuum drying oven for standing for 12 hours at 80 ℃, and then taking out the cut pieces.
And (3) a negative electrode preparation process: and adding ethanol into the zinc foil cut pieces, ultrasonically cleaning, drying in an oven, and taking out for later use.
Assembling a button type CR2032 symmetrical battery and a full battery flow: firstly, placing the elastic sheet on the side of a negative electrode shell, sequentially placing a gasket, a zinc sheet and a diaphragm, dropwise adding electrolyte to the wetted diaphragm, sequentially placing the zinc sheet (symmetrical battery), a positive electrode sheet (full battery) and a positive electrode shell, then placing the positive electrode sheet (full battery) and the positive electrode shell into a static pressure machine for static pressure sealing, and placing the assembled battery into a vacuum drying oven (25 ℃) for standing for 4 hours for later use. Followed by using the assembled symmetrical battery and NaV 3 O 8 ·1.5H 2 O// Zn and MnO 2 The full cell of/Zn was subjected to electrochemical impedance test and cycle performance test. Electrochemical test results are shown in Table 1, and the water-based zinc ion symmetric cell is at 5mA cm -2 The cycle life is only 278h, and the polarization voltage is 118mV; aqueous zinc ion MnO 2 // Zn full cell at 1 A.g -1 Next, the coulombic efficiency was only 95% and the capacity retention after 100 cycles was also only 60%; aqueous zinc ion NaV 3 O 8 ·1.5H 2 The total battery of O// Zn is 1 A.g -1 Next, the coulombic efficiency was only 94% and the capacity retention after 100 cycles was also only 58%.
An X-ray diffraction (XRD) sample preparation process: the solution prepared above was used as an electrolyte to assemble a symmetrical cell at 5 mA-cm -2 Under the current density, constant current charging is carried out for 12min, then constant current discharging is carried out for 12min, and the zinc anode is taken for XRD test. The test results are shown in fig. 5.
Open circuit voltage testing process: the prepared negative electrode zinc foil is used as a working electrode, the platinum mesh is used as a counter electrode, the saturated calomel electrode is used as a reference electrode, a three-electrode system is assembled, the prepared solution electrolyte is connected with a circuit, then current is introduced, the electrode is placed in the air for 30s, the electrode is rapidly inserted into the electrolyte at 30s and placed for 570s, open-circuit voltages of the battery in two different electrolytes in 600s can be measured, and changes of the open-circuit voltages can be observed. The test results are shown in fig. 6.
Scanning Electron Microscope (SEM) sample preparation procedure: at 5 mA-cm -2 At current density, using the above preparationThe solution is used as an electrolyte to assemble a symmetrical battery, constant current charging is carried out for 12min, then constant current discharging is carried out for 2min, 6min and 12min respectively, and a scanning sample is prepared. The test results are shown in fig. 7.
Example 1
At room temperature, 14.38g of zinc sulfate heptahydrate is completely dissolved in 50mL of deionized water, and then 0.283g of lanthanum sulfate (0.01 mol/L) is added and uniformly dissolved for later use. The water system zinc ion symmetrical battery is assembled by adopting zinc foils as positive and negative electrodes and glass fibers as a diaphragm. The water system zinc ion full cell is assembled by adopting sodium vanadate as an anode, zinc foil as a cathode and glass fiber as a diaphragm. Preparation and assembly of anode and cathode for button-type CR2032 symmetrical battery and NaV 3 O 8 ·1.5H 2 The O// Zn full cell and XRD, SEM sample preparation, and open circuit voltage test procedures were the same as in comparative example 1. FIG. 5XRD pattern showed that all characteristic peaks matched well with the standard phase of metallic Zn (PDF # 04-0831), and no impurity peak was observed, demonstrating that La 3+ Will be stably present in the electrolyte; as can be seen from FIG. 6, la was added 2 (SO 4 ) 3 The positive shift of open-circuit voltage after the additive is combined with Coulomb's law to indicate that La exists in the deposition process of zinc 3+ Adsorption of (2). The working mechanism of the zinc dendrite inhibitor is shown in fig. 11, namely, the cation electrostatic shielding function is used to force the zinc ions to be uniformly deposited. La can be illustrated by comparing FIGS. 7a-c with FIGS. 7d-f 3+ The addition of the zinc oxide can increase nucleation sites and improve the growth conditions of the zinc oxide, thereby regulating and controlling the zinc deposition behavior to lead the zinc deposition behavior to tend to be deposited uniformly, and further inhibiting the generation of dendritic crystals. In addition, electrochemical test results are shown in table 1 and fig. 1 and 8, and the water-based zinc ion symmetric cell is 5mA · cm -2 The cycle life is 830h, and the polarization voltage is 102mV; 1 A.g of aqueous zinc ion full cell -1 Next, the coulombic efficiency was 98% and the capacity retention rate after 100 cycles was 70%, and fig. 10 also shows a smaller impedance, which is advantageous for reducing the full cell polarization voltage.
Example 2
At room temperature, 14.38g of zinc sulfate heptahydrate is completely dissolved in 50mL of deionized water to serve as electrolyte, then 0.849g of lanthanum sulfate (0.03 mol/L) is added, after uniform dissolution,and (5) standby. The water system zinc ion symmetrical battery is assembled by adopting zinc foils as positive and negative electrodes and glass fibers as a diaphragm. Manganese dioxide is used as a positive electrode, zinc foil is used as a negative electrode, and glass fiber is used as a diaphragm to assemble the water-based zinc ion full cell. Preparation and assembly of positive electrode and negative electrode of button type CR2032 symmetrical battery and MnO 2 The procedure of XRD, SEM sample preparation and open circuit voltage test is the same as that of comparative example 1. Electrochemical test results are shown in Table 1, with water-based zinc ion symmetric cells at 1, 5 and 10mA cm -2 The cycle life is respectively as high as 308, 602 and 586h, and the polarization voltage is respectively 42, 90 and 115mV; the water-based zinc ion full cell is 0.5, 1 and 5 A.g -1 The coulombic efficiencies are all stabilized at 99% and the capacity retention rates after 100 cycles of circulation can reach 85%, 88% and 83% respectively. As can be seen from Table 1, la 3+ Can also improve the capacity retention rate of the battery after long circulation in the full battery, which shows that La is added in the circulation process 3+ The addition of (2) can reduce the generation of dead zinc, thereby reducing unnecessary capacity loss, and also can obviously reduce dendritic crystals. In addition, la can be seen from FIGS. 2 and 4 3+ The added zinc oxide can transfer resistance, improve the kinetics of zinc deposition reaction and obviously prolong the cycle life of the battery; as can also be seen from FIGS. 7a-c and g-i, la 3+ The addition of (2) can increase nucleation sites and improve growth conditions thereof, thereby regulating zinc deposition behavior to tend to be uniform, thereby inhibiting dendrite formation, which can also explain the longer cycle life of the cell shown in fig. 1.
Example 3
At room temperature, 14.38g of zinc sulfate heptahydrate is completely dissolved in 50mL of deionized water, and then 0.849g of lanthanum sulfate (0.03 mol/L) is added and uniformly dissolved for later use. The water system zinc ion full cell is assembled by adopting sodium vanadate as an anode, zinc foil as a cathode and glass fiber as a diaphragm. Preparation of positive electrode and negative electrode and NaV 3 O 8 ·1.5H 2 O// Zn full cell assembly the same as in comparative example 1. The electrochemical test results are shown in Table 1 and FIG. 9, where the total cell density of the aqueous zinc ion is 1A g -1 Next, the coulombic efficiency was 99% and the capacity retention after 100 cycles was 92%, and fig. 10 also shows a smaller impedanceAnd the polarization voltage of the whole battery is reduced.
Example 4
At room temperature, 14.38g of zinc sulfate heptahydrate is completely dissolved in 50mL of deionized water, and then 1.415g of lanthanum sulfate (0.05 mol/L) is added and uniformly dissolved for later use. The water system zinc ion symmetrical battery is assembled by adopting zinc foils as positive and negative electrodes and glass fibers as a diaphragm. Manganese dioxide is used as a positive electrode, zinc foil is used as a negative electrode, and glass fiber is used as a diaphragm to assemble the water-based zinc ion full cell. Preparation and assembly of positive electrode and negative electrode of button type CR2032 symmetrical battery and MnO 2 The procedure of the/Zn full cell was the same as in comparative example 1. Electrochemical test results are shown in Table 1, and the water-based zinc ion symmetric cell is at 5mA cm -2 The cycle life is 500h, and the polarization voltage is 85mV; 1 A.g of aqueous zinc ion full cell -1 Next, the coulombic efficiency was 99% and the capacity retention rate after 100 cycles was 86%.
Example 5
At room temperature, 14.38g of zinc sulfate heptahydrate is completely dissolved in 50mL of deionized water, and then 0.487g of lanthanum nitrate (0.03 mol/L) is added and uniformly dissolved for later use. The water system zinc ion symmetrical battery is assembled by adopting zinc foils as positive and negative electrodes and glass fibers as a diaphragm. Manganese dioxide is used as a positive electrode, zinc foil is used as a negative electrode, and glass fiber is used as a diaphragm to assemble the water-based zinc ion full cell. Preparation and assembly of positive electrode and negative electrode of button type CR2032 symmetrical battery and MnO 2 The procedure of the/Zn full cell was the same as in comparative example 1. Electrochemical test results are shown in Table 1, and the water-based zinc ion symmetric cell is at 5mA cm -2 The cycle life is 682h, and the polarization voltage is 92mV; 1 A.g of aqueous zinc ion full cell -1 Next, the coulombic efficiency was 98% and the capacity retention rate after 100 cycles was 85%.
Example 6
At room temperature, 14.38g of zinc sulfate heptahydrate is completely dissolved in 50mL of deionized water, and then 0.368g of lanthanum chloride (0.03 mol/L) is added and uniformly dissolved for later use. The water system zinc ion symmetrical battery is assembled by adopting zinc foils as positive and negative electrodes and glass fibers as a diaphragm. Manganese dioxide is used as a positive electrode, zinc foil is used as a negative electrode, and glass fiber is used as a diaphragm to assemble the water-based zinc ion full cell. Preparation and assembly buckle of positive electrode and negative electrodeCR2032 symmetric battery and MnO 2 The procedure of the/Zn full cell was the same as in comparative example 1. The electrochemical test results are shown in Table 1, and the water system zinc ion symmetrical battery is at 5 mA-cm -2 The cycle life is 583h, and the polarization voltage is 96mV; 1 A.g of aqueous zinc ion full cell -1 Next, the coulombic efficiency was 99% and the capacity retention rate after 100 cycles was 82%.
Example 7
At room temperature, 14.38g of zinc sulfate heptahydrate is completely dissolved in 50mL of deionized water, and then 0.474g of lanthanum acetate (0.03 mol/L) is added and uniformly dissolved for later use. The water system zinc ion symmetrical battery is assembled by adopting zinc foils as positive and negative electrodes and glass fibers as a diaphragm. Manganese dioxide is used as a positive electrode, zinc foil is used as a negative electrode, and glass fiber is used as a diaphragm to assemble the water-based zinc ion full cell. Preparation and assembly of positive electrode and negative electrode of button type CR2032 symmetrical battery and MnO 2 The procedure of the/Zn full cell was the same as in comparative example 1. Electrochemical test results are shown in Table 1, and the water-based zinc ion symmetric cell is at 5mA cm -2 The cycle life is 546h, and the polarization voltage is 98mV; 1 A.g of aqueous zinc ion full cell -1 Next, the coulombic efficiency was 98% and the capacity retention after 100 cycles was 86%.
Example 8
At room temperature, 18.18g of zinc trifluoromethanesulfonate was completely dissolved in 50mL of deionized water, and then 0.849g of lanthanum sulfate (0.03 mol/L) was added and dissolved uniformly for later use. The water system zinc ion symmetrical battery is assembled by adopting zinc foils as positive and negative electrodes and glass fibers as a diaphragm. Manganese dioxide is used as a positive electrode, zinc foil is used as a negative electrode, and glass fiber is used as a diaphragm to assemble the water-based zinc ion full cell. Preparation and assembly of positive electrode and negative electrode of button type CR2032 symmetrical battery and MnO 2 The procedure of the/Zn full cell was the same as in comparative example 1. Electrochemical test results are shown in Table 1, and the water-based zinc ion symmetric cell is at 5mA cm -2 The cycle life is 815h, and the polarization voltage is 86mV; 1 A.g of aqueous zinc ion full cell -1 Next, the coulombic efficiency was 99% and the capacity retention rate after 100 cycles was 86%.
The above description is only exemplary of the present invention and should not be taken as limiting, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Table 1 shows cycle performance parameters of the aqueous zinc ion symmetric batteries assembled in examples 1 to 8 and comparative example 1.
Figure BDA0003116133120000091
* Note: capacity retention refers to retention relative to the first cycle after 100 cycles.

Claims (1)

1. An aqueous zinc ion battery, characterized in that the electrolyte preparation method is any one of the following:
(1) At room temperature, completely dissolving 14.38g of zinc sulfate heptahydrate in 50mL of deionized water, and then adding 0.283g of lanthanum sulfate to uniformly dissolve;
(2) At room temperature, completely dissolving 14.38g of zinc sulfate heptahydrate in 50mL of deionized water, and then adding 0.849g of lanthanum sulfate to uniformly dissolve;
(3) At room temperature, completely dissolving 14.38g of zinc sulfate heptahydrate in 50mL of deionized water, and then adding 1.415g of lanthanum sulfate for uniform dissolution;
(4) At room temperature, completely dissolving 14.38g of zinc sulfate heptahydrate in 50mL of deionized water, and then adding 0.487g of lanthanum nitrate to dissolve uniformly;
(5) At room temperature, completely dissolving 14.38g of zinc sulfate heptahydrate in 50mL of deionized water, and then adding 0.368g of lanthanum chloride for uniform dissolution;
(6) At room temperature, completely dissolving 14.38g of zinc sulfate heptahydrate in 50mL of deionized water, and then adding 0.474g of lanthanum acetate for uniform dissolution;
(7) At room temperature, 18.18g of zinc trifluoromethanesulfonate was completely dissolved in 50mL of deionized water, and then 0.849g of lanthanum sulfate was added and dissolved uniformly.
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