CN111509306A - Electrolyte for rechargeable zinc ion battery, preparation method of electrolyte and rechargeable zinc ion battery - Google Patents
Electrolyte for rechargeable zinc ion battery, preparation method of electrolyte and rechargeable zinc ion battery Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- Y02E60/10—Energy storage using batteries
Abstract
The invention provides an electrolyte for a rechargeable zinc ion battery, a preparation method of the electrolyte and the rechargeable zinc ion battery, wherein the electrolyte uses water and an organic carbonate solvent as an electrolyte solvent, zinc salt is electrolyte salt, the volume of the carbonate solvent is 30-70% of the volume of the solvent, and the concentration of the zinc salt is 1-4 mol/kg. The electrolyte has high conductivity, good safety and good electrochemical stability, and anions and cations in the electrolyte have strong interaction with carbonate molecules and water molecules, so that the activity of the water molecules is effectively inhibited, the voltage window is improved, and the Zn deposition/precipitation coulomb efficiency is improved. The electrolyte has good compatibility with a zinc cathode, effectively solves the problems of dendritic crystal growth, hydrogen evolution, corrosion and the like of the zinc cathode in the traditional aqueous electrolyte, can obviously improve the cycle stability and the rate capability of a battery when being used for a rechargeable zinc ion battery system, has high safety, low cost and good electrochemical performance of the formed battery system, meets the requirement of large-scale energy storage, and has good application prospect.
Description
Technical Field
The invention relates to a battery electrolyte, in particular to an electrolyte for a rechargeable zinc ion battery, a preparation method of the electrolyte and the rechargeable zinc ion battery.
Background
Lithium ion batteries have enjoyed great success in portable electronic devices and have been rapidly developed gradually into the fields of new energy vehicles, renewable resource storage, and the like. However, lithium is in shortage, unevenly distributed and expensive, and the use of flammable organic electrolyte easily causes serious safety problems, which limits the application of the lithium in large-scale energy storage systems to a certain extent. Therefore, the development of alternative electrochemical energy storage technologies is imperative.
Rechargeable zinc ion batteries are considered to be one of the ideal choices for large-scale energy storage because of their high safety and low cost, and have recently received much attention from researchers. The advantages of abundant zinc (Zn) resources, environmental protection, no toxicity, low price, easy obtainment, high chemical stability, high theoretical capacity (820 mAh/g), safe and environmental protection of the water system electrolyte, low price, high conductivity and the like are mainly benefited.
In a rechargeable battery, an electrolyte is a key component, and its physical and chemical properties have an important influence on the service life, electrochemical properties, and the like of the battery. Traditional aqueous zinc ion battery electrolytes (e.g. 1M ZnSO)4Aqueous solution) has a narrow electrochemical window (less than 2V vs. Zn), and hydrogen/oxygen evolution side reactions are liable to occur, which not only causes consumption of the electrolyte, but also limits the selection range of the high-voltage positive electrode material. Meanwhile, the metal zinc cathode has the problems of zinc dendrite growth, uneven Zn deposition/precipitation, low coulombic efficiency, zinc corrosion, zinc passivation and the like in the traditional aqueous electrolyte, and the atom utilization rate and the cycling stability of the zinc cathode can be reduced. A common solution to this problem is to design an ultra-high salt concentration aqueous electrolyte, such as 3M Zn (OTf)2、1 m Zn(TFSI)2+20 m LiTFSI、30 m ZnCl2. Although the high salt concentration can reduce the activity of free water molecules and improve the voltage window and the electrochemical stability of the electrolyte, the ultrahigh salt concentration can cause the viscosity and the density of the electrolyte to be increased and the conductivity to be reduced, thereby seriously influencing the rate capability of the battery. In addition, the conductivity of an organic system or a solid electrolyte is poor, the processing conditions are harsh, the process is complex, the price cost is increased, the economic benefit of the battery is reduced, and the application range of the battery is limited. Therefore, develop a new and efficient electrolyte system forThe construction and the practical process of the high-performance rechargeable water system zinc ion battery have important scientific significance and application value.
Disclosure of Invention
One of the purposes of the invention is to provide an electrolyte for a rechargeable zinc ion battery, so as to solve the problems of poor compatibility of a zinc cathode and a traditional water-based electrolyte, growth, corrosion and passivation of dendrites of the zinc cathode, low voltage window of the electrolyte, easiness in hydrogen evolution/oxygen evolution, low zinc deposition/coulomb precipitation efficiency, poor rate capability and the like in the conventional zinc ion battery.
The invention also aims to provide a preparation method of the electrolyte for the rechargeable zinc ion battery, so as to prepare the electrolyte with high safety, wide voltage window and high performance.
The invention also aims to provide a rechargeable zinc ion battery to solve the problems of low coulombic efficiency, fast capacity attenuation, short cycle life and the like of the conventional zinc ion battery.
One of the objects of the invention is achieved by:
the electrolyte for the rechargeable zinc ion battery comprises a solvent and zinc salt electrolyte salt, wherein the solvent comprises water and an organic carbonate solvent, the organic carbonate solvent is immiscible with water, and the volume of the organic carbonate solvent is 30-70% of that of the solvent; the concentration of the zinc salt electrolyte salt is 1-4 mol/kg.
Preferably, the organic carbonate solvent is at least one of dimethyl carbonate, diethyl carbonate and propylene carbonate; more preferably, the organic carbonate solvent is dimethyl carbonate, diethyl carbonate or propylene carbonate.
The zinc salt electrolyte salt is soluble in water, slightly soluble or insoluble in organic carbonate solvents. Preferably, the zinc salt electrolyte salt is zinc tetrafluoroborate (Zn (BF)4)2) Zinc hexafluorophosphate (Zn (PF)6)2) Zinc trifluoromethanesulfonate (Zn (OTf)2) Or zinc bis (trifluoromethanesulfonyl) imide (Zn (TFSI)2) Any one or more of them; more preferably, the zinc salt electrolyte salt is zinc trifluoromethanesulfonate (Zn (OTf)2) Or bistrifluoromethaneZinc methane sulfonyl imide (Zn (TFSI)2）。
Preferably, the concentration of the zinc salt electrolyte salt is 1-3 mol/kg, and more preferably 2 mol/kg.
More preferably, the zinc salt electrolyte salt is zinc trifluoromethanesulfonate (Zn (OTf)2) The concentration thereof was 2 mol/kg.
Preferably, the water is deionized water.
The second purpose of the invention is realized by the following steps:
a preparation method of electrolyte for rechargeable zinc ion battery comprises adding zinc salt electrolyte into solvent, and mixing; the solvent comprises water and an organic carbonate solvent, the organic carbonate solvent is immiscible with water, and the volume of the organic carbonate solvent is 30-70% of that of the solvent; the concentration of the zinc salt electrolyte salt is 1-4 mol/kg.
Preferably, the organic carbonate solvent is at least one of dimethyl carbonate, diethyl carbonate and propylene carbonate; more preferably, the organic carbonate solvent is dimethyl carbonate, diethyl carbonate or propylene carbonate.
The zinc salt electrolyte salt is soluble in water, slightly soluble or insoluble in organic carbonate solvents. Preferably, the zinc salt electrolyte salt is zinc tetrafluoroborate (Zn (BF)4)2) Zinc hexafluorophosphate (Zn (PF)6)2) Zinc trifluoromethanesulfonate (Zn (OTf)2) Or zinc bis (trifluoromethanesulfonyl) imide (Zn (TFSI)2) Any one or more of them; more preferably, the soluble zinc salt is zinc trifluoromethanesulfonate (Zn (OTf)2) Or zinc bis (trifluoromethanesulfonyl) imide (Zn (TFSI)2）。
Preferably, the concentration of the zinc salt electrolyte salt is 1-3 mol/kg.
More preferably, the zinc salt electrolyte salt is zinc trifluoromethanesulfonate (Zn (OTf)2) The concentration thereof was 2 mol/kg.
Preferably, the water is deionized water.
The third purpose of the invention is realized by the following steps:
a rechargeable zinc ion battery comprises a positive electrode, a negative electrode, a diaphragm and the electrolyte for the rechargeable zinc ion battery.
Preferably, the positive electrode is vanadium pentoxide (V)2O5) And (4) a positive electrode. The vanadium pentoxide positive electrode is prepared by the following method: will commercialize V2O5And ball-milling the powder and graphite according to the mass ratio of 8:2 for 3h at the rotating speed of 400 r/min. Ball-milled V2O5And mixing the conductive carbon and the binder according to the mass ratio of 8:1, dispersing the mixture in an electrode material dispersion solvent to prepare slurry, uniformly coating the slurry on a titanium foil with the thickness of 10-30 mu m, and drying in vacuum to obtain the titanium-doped anode material. The binder is polyvinylidene fluoride (PVDF). The conductive carbon material is conductive carbon black, activated carbon, porous carbon, BP-2000, Vulcan XC-72, Super P or carbon nano tube. The electrode material dispersion solvent is N, N-dimethyl pyrrolidone.
The negative electrode is a zinc negative electrode; it can be made of metal zinc foil or spherical zinc powder. The negative electrode can be made of metal zinc foil: the metallic zinc foil was cut to a specific size and used as a negative electrode. The negative electrode can be made of spherical zinc powder, and the preparation method comprises the following steps: uniformly mixing spherical zinc powder and water-based adhesive polyoxyethylene according to the weight ratio of 98: 2 to obtain a mixture; adding water accounting for 3% of the weight of the mixture into the mixture, grinding the mixture into slurry, coating the slurry on a stainless steel foil with the thickness of 30 mu m, and drying the coated layer for 12 hours in vacuum at 80 ℃.
The diaphragm is a glass fiber film, a polyethylene non-woven fabric or microporous filter paper.
The electrolyte for the rechargeable zinc ion battery takes water and organic carbonate as solvents and zinc salt as electrolyte salt to form a novel electrolyte system under the combined action of the zinc salt, the water and the organic carbonate solvent. The strong interaction between the anions and cations in the system and carbonate molecules and water molecules effectively inhibits the activity of the water molecules and improves the voltage window of the electrolyte. The electrolyte and the zinc cathode interface have high stability, can guide the uniform deposition of zinc, prevent dendritic crystal growth, inhibit side reactions such as hydrogen precipitation, zinc corrosion, passivation and the like, and improve the coulombic efficiency (-100%) and the atomic utilization rate of Zn deposition/precipitation.
The electrolyte has good compatibility with common anode materials and zinc cathodes, and has high conductivity and good safety. Use of it for Zn// V2O5In a rechargeable water system zinc ion battery system, the dissolution of a positive electrode material can be effectively inhibited, the hydrogen evolution and corrosion reaction of a zinc negative electrode are controlled, the cycle life of the battery is remarkably prolonged, the cost of the battery is low, the cycle rate performance is good, the large-scale energy storage requirement is met, and the rechargeable water system zinc ion battery system has a good application prospect.
Drawings
FIG. 1 shows 2 mol/kg Zn (OTf) prepared in example 12-H2O/DEC (1:1) electrolyte (FIG. 1 a) and 1 mol/kg Zn (OTf) prepared in comparative example 22Flammability comparison of AN organic electrolyte (FIG. 1 b).
Fig. 2 is a graph of voltage window test CV of the electrolyte prepared in example 1.
FIG. 3 is a graph showing the cycle stability test of the electrolyte prepared in example 1 in a Zn/Zn symmetrical battery.
FIG. 4 is 2 mol/kg Zn (OTf) prepared in comparative example 12-H2And (3) a cycle stability test chart of the O water system electrolyte in the Zn/Zn symmetrical battery.
Fig. 5 is an SEM topography of the zinc negative electrode surface after cycling in a Zn/Zn symmetric cell using the electrolyte prepared in example 1 (fig. 5 a) and the aqueous electrolyte prepared in comparative example 1 (fig. 5 b).
Fig. 6 is a graph comparing the cycle performance of Zn/Ti batteries of the electrolyte prepared in example 1 and the aqueous electrolyte in comparative example 1.
FIG. 7 shows Zn// V using the electrolyte of example 12O5The charge and discharge curve of the battery.
FIG. 8 shows Zn// V using the electrolyte of example 12O5Cycle performance diagram of the battery.
FIG. 9 shows Zn// V of the aqueous electrolyte prepared in comparative example 12O5Cycle performance diagram of the battery.
Detailed Description
The invention is further illustrated by the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention in any way.
Procedures and methods not described in detail in the following examples are conventional methods well known in the art, and the reagents used in the examples are either analytically or chemically pure and are either commercially available or prepared by methods well known to those of ordinary skill in the art. The following examples all achieve the objects of the present invention.
In the following examples, a rechargeable zinc-ion battery comprises a positive electrode, a negative electrode, a separator and an electrolyte prepared in each example or comparative example, wherein vanadium pentoxide (V) was used2O5) As the positive electrode, a metal zinc foil (zinc sheet) was used as the negative electrode, and a glass fiber film was used as the separator.
V2O5The preparation method of the anode comprises the following steps: will commercialize V2O5And ball-milling the powder and graphite according to the proportion of 8:2 for 3h at the rotating speed of 400 r/min. Ball-milled V2O5Mixing conductive carbon black (Super P) and PVDF (polyvinylidene fluoride) binder according to a mass ratio of 8:1:1, dispersing the mixture in NMP to prepare slurry, uniformly coating the slurry on a titanium foil with the thickness of 10-30 mu m, and coating the titanium foil on a substrate of 100 mu moAnd C, drying for 12 hours in vacuum to obtain the product.
Example 1
0.5 m L deionized water and 0.5 m L DEC solvent were mixed, and 0.73 g Zn (OTf) was added to the mixed solution2Fully shaking zinc salt, performing ultrasonic treatment at room temperature for 10 minutes to completely dissolve the zinc salt, and completely mixing the two solvents to obtain 2 mol/kg Zn (OTf)2-H2O/DEC (1:1) electrolyte.
The electrolyte obtained was subjected to the following performance tests:
(1) flame retardant properties
And (3) ignition test: the electrolyte prepared in this example was ignited with a flame gun, and the combustion was observed. The obtained results are shown in fig. 1a, which shows that the electrolyte prepared in the embodiment can not be ignited by open fire at all, and has good flame retardant effect.
(2) Electrical conductivity of
The conductivity of the electrolyte prepared in this example was measured by the AC impedance method and the experimental data were recorded in an electrochemical workstation model CHI 660E. The results show that the electrolyte prepared in this example has a conductivity of 28.2 mS/cm.
(3) Electrolyte voltage window
The voltage window of the electrolyte passes a Zn/Ti battery test, a titanium foil (Ti) is used as a working electrode, a zinc foil (Zn) is used as a counter electrode and a reference electrode, glass fiber is used as a diaphragm, 80 mu L of the electrolyte prepared in the embodiment is dripped to prepare a standard CR2032 type button battery, the battery is tested by adopting a cyclic sweep voltammetry (CV), the sweep speed is set to be 0.5 mV/s, the test voltage interval is-0.3-2.8V, and data is recorded by a CHI660E type electrochemical workstation.
The results are shown in FIG. 2, and show that the electrolyte prepared in this example is 2 mol/kg Zn (OTf)2-H2O/DEC (1:1) shows stable zinc deposition/precipitation at low potential, decomposition only after 2.6V at high potential, broadening the voltage window to above 2.9V (vs. Zn)2+/Zn）。
(4) Stability of electrolyte to zinc cathode
The Zn/Zn symmetrical battery cycling stability test comprises that zinc foils are used as electrodes for the anode and the cathode, glass fiber is used as a diaphragm between the two zinc foils, 85 mu L electrolyte is dripped into the zinc/Zn symmetrical battery to test the stability of the electrolyte in the long-time cycling process, and the test is carried out by using a CT2001A type blue battery test system at 1 mA/cm2The current density of the battery is measured, and in each cycle, constant current discharge is carried out for 30 minutes first, and then constant current charge is carried out for 30 minutes.
The results are shown in fig. 3, which shows that the electrolyte prepared by the embodiment can stably circulate for more than 500 hours in a Zn/Zn symmetrical battery.
Characterization of a zinc cathode: and (4) disassembling the Zn/Zn battery which is circulated for 500 hours, taking out the zinc negative plate, and cleaning and preparing a sample. And (5) characterizing the micro-morphology of the surface of the zinc cathode after circulation by using a Scanning Electron Microscope (SEM).
The surface appearance of the zinc cathode after circulation is shown in fig. 5a, and it can be seen from the figure that the zinc sheet of the cathode is well preserved, the surface is flat, and no corrosion phenomenon occurs.
(5) Cycling stability of electrolyte to zinc cathode
Titanium foil (Ti) is used as a working electrode, zinc foil (Zn) is used as a counter electrode and a reference electrode, glass fiber is used as a diaphragm, electrolyte with different proportions of 85 mu L is dripped to assemble a Zn/Ti battery, and the electrochemical stability of the electrolyte and a Zn cathode and the Zn in the electrolyte are tested2+Coulombic efficiency of deposition/precipitation. The test is carried out by using a CT2001A type blue battery test system, and the cycle procedure is that constant current discharge is carried out for 1 hour (corresponding to the Zn deposition process), and then constant current charging is carried out to 0.5V (corresponding to the Zn precipitation process). The test current density is 2 mA/cm2。
Cycling stability of the resulting electrolyte and Zn2+The coulombic efficiency results of the deposition/precipitation are shown in fig. 6, and it can be seen from the graph that the metallic zinc cathode can stably circulate in the electrolyte prepared in the embodiment, and Zn2+The deposition/precipitation coulombic efficiency of/Zn is close to 100%, no side reaction occurs, and the utilization rate of Zn atoms is improved to a great extent.
The electrolyte in the embodiment is applied to a rechargeable zinc ion battery. The preparation method of the full cell comprises the following steps: in a dry environment, using prepared V2O5The positive plate is used as the positive electrode, the zinc plate with the diameter of 10 mm is used as the negative electrode, the glass fiber membrane is used as the diaphragm, the electrolyte prepared in the embodiment with the diameter of 85 mu L is dripped, the battery is packaged, and Zn/V is prepared2O5The electrochemical performance of the rechargeable zinc ion full cell is tested.
And (3) testing the cycling stability: zn// V assembled by using the electrolyte of the embodiment2O5The total battery voltage is 0.3-1.6V (vs. Zn)2+/Zn) was tested for charge and discharge in the voltage range with a current density of 2C.
Prepared Zn// V2O5The charge-discharge curve obtained for the full cell is shown in fig. 7, and the average discharge voltage is 0.7V; the cycle performance chart is shown in fig. 8, and it can be seen from the chart that after 200 cycles, the capacity retention rate is as high as 97%, and good long-cycle stability is shown.
Example 2
0.7 m L deionized water and 0.3 m L DEC solvent were mixed, and 0.73 g Zn (OTf) was added to the mixed solution2Fully shaking zinc salt, performing ultrasonic treatment at room temperature for 2 minutes to completely dissolve the zinc salt, and completely mixing the two solvents to obtain 2 mol/kg Zn (OTf)2-H2O/DEC (7:3) electrolyte.
And testing the flame retardance, the thermal stability, the conductivity and the electrochemical performance of the electrolyte. The test result shows that: the electrolyte is non-combustible, the conductivity is higher than 40 mS/cm, and the voltage window is stabilized from-0.3V to 2.2V. The initial coulombic efficiency of the deposition/precipitation of zinc ions in the electrolyte on the zinc cathode is 87 percent, and the initial coulombic efficiency is immediately stabilized to about 96 percent and can be 1 mA/cm2Stably circulating for more than 30 circles under the current density.
Example 3
0.5 m L deionized water and 1 m L DEC solvent were mixed, and 1.1 g Zn (OTf) was added to the mixed solution2Fully shaking zinc salt, performing ultrasonic treatment at room temperature for 10 minutes to completely dissolve the zinc salt, and completely mixing the two solvents to obtain 2 mol/kg Zn (OTf)2-H2O/DEC (1:2) electrolyte.
And testing the flame retardance, the thermal stability, the conductivity and the electrochemical performance of the electrolyte. The test result shows that: the electrolyte is non-combustible, the conductivity of the electrolyte is reduced to 14 mS/cm due to the increase of the content of the carbonate solvent, and the voltage window is stabilized from-0.3V to 2.6V. The initial coulombic efficiency of the deposition/precipitation of zinc ions in the electrolyte on the zinc cathode is 75%, the coulombic efficiency of the first 30 circles is lower than 85-90%, and then the coulombic efficiency is stabilized to about 98%.
Example 4
0.7 m L deionized water and 0.3 m L PC solvent were mixed, and 1.45 g Zn (OTf) was added to the mixed solution2Fully shaking zinc salt, performing ultrasonic treatment at room temperature for 10 minutes to completely dissolve the zinc salt, and completely mixing the two solvents to obtain 4 mol/kg Zn (OTf)2-H2O/PC (7:3) electrolyte.
Example 5
0.5 m L deionized water and 0.5 m L DMC solvent were mixed, and the mixture was added to0.36 g Zn(OTf)2Fully shaking zinc salt, performing ultrasonic treatment at room temperature for 10 minutes to completely dissolve the zinc salt, and completely mixing the two solvents to obtain 1 mol/kg Zn (OTf)2-H2O/DMC (1:1) electrolyte.
Example 6
0.5 m L deionized water and 0.5 m L DMC solvent were mixed, and 0.28 g Zn (BF) was added to the mixed solution4)2Fully shaking zinc salt, performing ultrasonic treatment at room temperature for 10 minutes to completely dissolve the zinc salt, and completely mixing the two solvents to obtain 1 mol/kg Zn (BF)4)2-H2O/DMC (1:1) electrolyte.
Example 7
0.5 m L deionized water and 0.5 m L DEC solvent were mixed, and 0.36 g Zn (PF) (total of 0.36 g Zn and Na) was added to the mixed solution6)2Fully shaking zinc salt, performing ultrasonic treatment at room temperature for 10 minutes to completely dissolve the zinc salt, and completely mixing the two solvents to obtain 1 mol/kg Zn (PF)6)2-H2O/DEC (1:1) electrolyte.
Example 8
0.5 m L deionized water and 0.5 m L DEC solvent were mixed, and 1.25 g Zn (TFSI) was added to the mixed solution2Fully shaking zinc salt, performing ultrasonic treatment at room temperature for 10 minutes to completely dissolve the zinc salt, and completely mixing the two solvents to obtain 2 mol/kg Zn (TFSI)2-H2O/DEC (1:1) electrolyte.
Comparative example 1
0.72 g Zn (OTf) was added to 1 m L deionized water2Fully shaking zinc salt, and performing ultrasonic treatment at room temperature for 10 minutes to completely dissolve the zinc salt to obtain 2 mol/kg Zn (OTf)2-H2An O aqueous electrolyte. And carrying out electrochemical performance test on the obtained electrolyte.
The results show that the aqueous electrolyte cannot support reversible deposition/precipitation of the zinc negative electrode (fig. 4), the coulombic efficiency is low (fig. 6), and obvious side reactions exist (fig. 5 b); applying it to Zn// V2O5In the full cell (fig. 9), the capacity fade was severe, and the capacity retention rate was 54% after 120 cycles.
Comparative example 2
At a high levelIn a pure argon atmosphere, 0.36 g Zn (OTf)2Adding zinc salt into 1 m L AN, shaking sufficiently, and performing ultrasonic treatment at room temperature for 10 minutes to completely dissolve the zinc salt to obtain 1 mol/kg Zn (OTf)2-AN organic electrolyte. And testing the flame retardant property of the obtained electrolyte. The results show that the organic system electrolyte is extremely flammable (fig. 1 b).
Comparative example 3
0.2 m L deionized water and 0.8 m L DEC solvent were mixed, and 0.36 g Zn (OTf) was added to the mixed solution2Fully shaking zinc salt, performing ultrasonic treatment at room temperature for 20 minutes to completely dissolve the zinc salt, and completely mixing the two solvents to obtain 2 mol/kg Zn (OTf)2-H2O/DEC (1:4) electrolyte.
And carrying out electrochemical performance test on the obtained electrolyte. The test result shows that: the electrolyte is flammable, and the voltage window can be stabilized from-0.3V to 2.65V due to the fact that the carbonate solvent in the system is excessive, and the conductivity of the electrolyte is only 6 mS/cm. The initial coulombic efficiency of the deposition/precipitation of zinc ions in the electrolyte on the zinc cathode is 70%, and the zinc ions can be stabilized for 35 cycles at higher coulombic efficiency (-100%).
Comparative example 4
0.9 m L deionized water and 0.1 m L DEC solvent were mixed, and 0.36 g Zn (OTf) was added to the mixed solution2Fully shaking zinc salt, performing ultrasonic treatment at room temperature for 5 minutes to completely dissolve the zinc salt, and completely mixing the two solvents to obtain 2 mol/kg Zn (OTf)2-H2O/DEC (9:1) electrolyte.
And testing the flame retardance, the thermal stability, the conductivity and the electrochemical performance of the electrolyte. The test result shows that: the water system electrolyte can not support reversible deposition/precipitation of a zinc cathode, and is applied to Zn// V (zinc/zinc) unless the initial two circles of coulombic efficiency are higher and the subsequent coulombic efficiency is similar to that of a pure water system and fluctuates around 70 percent2O5There is also a severe capacity fade in the full cell.
Comparative example 5
0.15 g of Zn (OTf)2The zinc salt was added to 0.5 m L deionized water and 0.5 m L DEC solvent, the water and DEC being in a phase separated state.
Comparative example 6
0.5 m L deionized water and 0.5 m L AN solvent were mixed, and 0.73 g Zn (OTf) was added to the mixed solution2Fully shaking zinc salt, performing ultrasonic treatment at room temperature for 10 minutes to completely dissolve the zinc salt, and completely mixing the two solvents to obtain 2 mol/kg Zn (OTf)2-H2O/AN (1:1) electrolyte.
And carrying out electrochemical performance test on the obtained electrolyte. The test result shows that: the coulombic efficiency of the Zn-Ti battery using the electrolyte fluctuates around 90 percent, and a system cannot support stable and reversible deposition/precipitation of zinc ions.
Comparative example 7
In a high purity argon atmosphere, 0.36 g Zn (OTf)2The zinc salt was added to 1 m L DEC, and the electrolyte salt was almost insoluble.
Comparative example 8
In a high purity argon atmosphere, 0.36 g Zn (OTf)2The zinc salt was added to 1 m L DMC, and the electrolyte salt was almost insoluble.
Comparative example 9
In a high purity argon atmosphere, 0.36 g Zn (OTf)2The zinc salt was added to 1 m L PC, and the electrolyte salt was almost insoluble.
Comparative example 10
0.57 g of ZnSO4The zinc salt was added to 0.5 m L deionized water and 0.5 m L DEC solvent, the water and DEC being in a phase separated state.
Claims (10)
1. An electrolyte for a rechargeable zinc ion battery, which is characterized by comprising a solvent and a zinc salt electrolyte salt; the solvent comprises water and an organic carbonate solvent, the organic carbonate solvent is immiscible with water, and the volume of the organic carbonate solvent is 30-70% of the volume of the solvent; the concentration of the zinc salt electrolyte salt is 1-4 mol/kg.
2. The electrolyte for a rechargeable zinc-ion battery according to claim 1, wherein the organic carbonate solvent is at least one of dimethyl carbonate, diethyl carbonate and propylene carbonate.
3. The electrolyte for a rechargeable zinc-ion battery according to claim 1, wherein the zinc salt electrolyte salt is at least one of zinc tetrafluoroborate, zinc hexafluorophosphate, zinc trifluoromethanesulfonate, and zinc bistrifluoromethanesulfonylimide.
4. The electrolyte for a rechargeable zinc-ion battery according to claim 1, wherein the zinc salt electrolyte salt is zinc trifluoromethanesulfonate with a concentration of 2 mol/kg.
5. The method for preparing the electrolyte of the rechargeable zinc-ion battery according to claim 1, wherein the electrolyte salt of the zinc salt is added into the solvent and uniformly mixed to obtain the electrolyte.
6. The method of claim 5, wherein the organic carbonate solvent is at least one of dimethyl carbonate, diethyl carbonate, and propylene carbonate.
7. The method for preparing the electrolyte for the rechargeable zinc-ion battery according to claim 5, wherein the zinc salt electrolyte salt is at least one of zinc tetrafluoroborate, zinc hexafluorophosphate, zinc trifluoromethanesulfonate and zinc bistrifluoromethanesulfonylimide.
8. A rechargeable zinc ion battery, which comprises a positive electrode, a negative electrode, a separator and an electrolyte, and is characterized in that the electrolyte is the electrolyte for the rechargeable zinc ion battery as claimed in any one of claims 1 to 4.
9. The rechargeable zinc-ion battery of claim 8, wherein the positive electrode is a vanadium pentoxide positive electrode and the negative electrode is a zinc negative electrode.
10. The rechargeable zinc-ion battery of claim 8, wherein the separator is a glass fiber membrane, a polyethylene non-woven fabric or a microporous filter paper.
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Cited By (8)
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|---|---|---|---|---|
| CN112751086A (en) * | 2020-12-28 | 2021-05-04 | 陈璞 | Zinc ion battery |
| CN113097576A (en) * | 2021-03-30 | 2021-07-09 | 广东工业大学 | Water-based zinc ion battery electrolysis for protecting vanadium-containing compound positive electrode and application thereof |
| CN113471551A (en) * | 2021-07-09 | 2021-10-01 | 南开大学 | Electrolyte additive for inhibiting dissolution of vanadium-based water-based battery electrode material and electrolyte |
| CN113725500A (en) * | 2021-09-03 | 2021-11-30 | 中南大学 | Mixed electrolyte of water-based zinc ion battery |
| CN114695974A (en) * | 2022-04-21 | 2022-07-01 | 南开大学 | Low-temperature aqueous ion battery electrolyte and application thereof in aqueous ion battery |
| CN114695973A (en) * | 2022-03-21 | 2022-07-01 | 电子科技大学 | Preparation method of low-temperature zinc ion battery |
| WO2023003834A1 (en) * | 2021-07-19 | 2023-01-26 | Grotthuss, Inc. | Rechargeable zinc metal battery |
| CN115911592A (en) * | 2022-12-15 | 2023-04-04 | 中南大学 | Zinc ion battery electrolyte containing carbon dots and preparation method and application thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103401030A (en) * | 2013-07-09 | 2013-11-20 | 哈尔滨工程大学 | Aqueous rechargeable magnesium/zinc ion capacitor battery |
| JP2015028895A (en) * | 2013-06-25 | 2015-02-12 | 一徳 清家 | Electrolyte for secondary battery using semiconductor and method for manufacturing electrolyte for secondary battery using semiconductor |
| JP2015191782A (en) * | 2014-03-28 | 2015-11-02 | 日産自動車株式会社 | Electrolyte for zinc secondary batteries and zinc secondary battery |
| CN105206879A (en) * | 2015-10-29 | 2015-12-30 | 中国科学院青岛生物能源与过程研究所 | Alkaline zinc secondary battery and preparation method thereof |
| US20160204441A1 (en) * | 2014-09-02 | 2016-07-14 | Panisolar, Inc. | Wall Mounted Zinc Batteries |
| CN107634266A (en) * | 2017-08-18 | 2018-01-26 | 上海交通大学 | A kind of MH secondary battery flame-retardant electrolyte |
| CN108574085A (en) * | 2018-03-22 | 2018-09-25 | 复旦大学 | A kind of low temperature Zinc ion battery |
| CN109004192A (en) * | 2018-07-16 | 2018-12-14 | 郑州大学 | Combination electrode, the battery and preparation method thereof of graphene/graphene oxide cladding |
| CN109037794A (en) * | 2017-10-20 | 2018-12-18 | 南京蔚速科技有限公司 | Rechargeable battery |
| CN109994785A (en) * | 2018-12-30 | 2019-07-09 | 华中科技大学 | A kind of zinc organic battery and application |
| WO2019183224A1 (en) * | 2018-03-20 | 2019-09-26 | University Of Maryland, College Park | Electrolytes for rechargeable zn-metal battery |
-
2020
- 2020-04-26 CN CN202010339469.3A patent/CN111509306B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015028895A (en) * | 2013-06-25 | 2015-02-12 | 一徳 清家 | Electrolyte for secondary battery using semiconductor and method for manufacturing electrolyte for secondary battery using semiconductor |
| CN103401030A (en) * | 2013-07-09 | 2013-11-20 | 哈尔滨工程大学 | Aqueous rechargeable magnesium/zinc ion capacitor battery |
| JP2015191782A (en) * | 2014-03-28 | 2015-11-02 | 日産自動車株式会社 | Electrolyte for zinc secondary batteries and zinc secondary battery |
| US20160204441A1 (en) * | 2014-09-02 | 2016-07-14 | Panisolar, Inc. | Wall Mounted Zinc Batteries |
| CN105206879A (en) * | 2015-10-29 | 2015-12-30 | 中国科学院青岛生物能源与过程研究所 | Alkaline zinc secondary battery and preparation method thereof |
| CN107634266A (en) * | 2017-08-18 | 2018-01-26 | 上海交通大学 | A kind of MH secondary battery flame-retardant electrolyte |
| CN109037794A (en) * | 2017-10-20 | 2018-12-18 | 南京蔚速科技有限公司 | Rechargeable battery |
| WO2019183224A1 (en) * | 2018-03-20 | 2019-09-26 | University Of Maryland, College Park | Electrolytes for rechargeable zn-metal battery |
| CN108574085A (en) * | 2018-03-22 | 2018-09-25 | 复旦大学 | A kind of low temperature Zinc ion battery |
| CN109004192A (en) * | 2018-07-16 | 2018-12-14 | 郑州大学 | Combination electrode, the battery and preparation method thereof of graphene/graphene oxide cladding |
| CN109994785A (en) * | 2018-12-30 | 2019-07-09 | 华中科技大学 | A kind of zinc organic battery and application |
Non-Patent Citations (3)
| Title |
|---|
| AHMAD NAVEED等: "Highly Reversible and Rechargeable Safe Zn Batteries Based on a Triethyl Phosphate Electrolyte", 《ANGEWANDTE CHEMIE》 * |
| FEI WANG等: "Hybrid Aqueous/Non-aqueous Electrolyte for Safe and High-Energy Li-ion Barreries", 《JOULE》 * |
| 熊小琳等: "尖晶石锰酸锂正极在Water-in-Salt电解液中的电化学性能", 《储能科学与技术》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112751086A (en) * | 2020-12-28 | 2021-05-04 | 陈璞 | Zinc ion battery |
| CN113097576A (en) * | 2021-03-30 | 2021-07-09 | 广东工业大学 | Water-based zinc ion battery electrolysis for protecting vanadium-containing compound positive electrode and application thereof |
| CN113471551A (en) * | 2021-07-09 | 2021-10-01 | 南开大学 | Electrolyte additive for inhibiting dissolution of vanadium-based water-based battery electrode material and electrolyte |
| WO2023003834A1 (en) * | 2021-07-19 | 2023-01-26 | Grotthuss, Inc. | Rechargeable zinc metal battery |
| CN113725500A (en) * | 2021-09-03 | 2021-11-30 | 中南大学 | Mixed electrolyte of water-based zinc ion battery |
| CN114695973A (en) * | 2022-03-21 | 2022-07-01 | 电子科技大学 | Preparation method of low-temperature zinc ion battery |
| CN114695974A (en) * | 2022-04-21 | 2022-07-01 | 南开大学 | Low-temperature aqueous ion battery electrolyte and application thereof in aqueous ion battery |
| CN115911592A (en) * | 2022-12-15 | 2023-04-04 | 中南大学 | Zinc ion battery electrolyte containing carbon dots and preparation method and application thereof |
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