CN110534808B - Flame-retardant organic electrolyte for rechargeable zinc battery and rechargeable zinc battery - Google Patents

Flame-retardant organic electrolyte for rechargeable zinc battery and rechargeable zinc battery Download PDF

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CN110534808B
CN110534808B CN201910722823.8A CN201910722823A CN110534808B CN 110534808 B CN110534808 B CN 110534808B CN 201910722823 A CN201910722823 A CN 201910722823A CN 110534808 B CN110534808 B CN 110534808B
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sodium
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张宁
董阳
王元媛
徐建中
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Heibei University
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Abstract

The invention provides a flame-retardant organic electrolyte for a rechargeable zinc battery and the rechargeable zinc battery, wherein the flame-retardant organic electrolyte for the rechargeable zinc battery comprises soluble zinc salt, sodium salt electrolyte salt and a flame-retardant organic solvent, the concentration of the soluble zinc salt is 0.1-2 mol/L, and the concentration of the sodium salt electrolyte salt is 0.1-2.5 mol/L. The flame-retardant organic electrolyte has proper conductivity, viscosity, cation migration rate, high voltage window and excellent flame retardance, can realize uniform deposition of metal zinc, improves Zn deposition/precipitation coulombic efficiency and atomic utilization rate, and shows good electrochemical reversibility and anode and cathode material compatibility. The flame-retardant organic electrolyte is applied to Zn// Na3V2(PO4)2O2In the F rechargeable zinc battery system, the safety of the battery can be obviously improved, and the zinc battery system has the advantages of high discharge voltage platform, good cycle stability and wide application prospect.

Description

Flame-retardant organic electrolyte for rechargeable zinc battery and rechargeable zinc battery
Technical Field
The invention relates to a battery electrolyte, in particular to a flame-retardant organic electrolyte for a rechargeable zinc battery and the rechargeable zinc battery.
Background
In order to meet the increasing energy demand, the problems of rapid consumption of fossil fuel energy and environmental deterioration are solved. Renewable energy sources such as solar energy, wind energy, tidal energy and the like are developed, the energy utilization rate is improved, and the solar energy generation device is widely concerned by people. However, renewable energy sources are usually intermittent and greatly affected by time, climate and other factors, and if the renewable energy sources are directly incorporated into a power grid for use, the power grid is greatly impacted. The secondary battery technology can realize the storage and release of energy by utilizing the interconversion between chemical energy and electric energy, has the function of peak clipping and valley filling, and is particularly important for the development and the utilization of available renewable energy sources.
At present, lithium ion batteries have been greatly successful in portable electronic devices and gradually developed into the fields of new energy automobiles, smart power grids and the like, however, the application of lithium ion batteries in the field of large-scale energy storage is limited by the factors of lithium resource shortage, low safety, high price and the like. The zinc resource is rich, the price is low, the zinc battery is safe and environment-friendly, the stability of the metal zinc cathode in a water system and an organic system is high, the metal zinc cathode can be directly used as a cathode material, and the theoretical capacity of the metal zinc cathode reaches 820 mAh/g, so that the rechargeable zinc battery is considered as an ideal choice in a large-scale energy storage system.
Currently, research on rechargeable zinc batteries is mainly based on an aqueous electrolyte system, which has the advantages of high safety, high conductivity, low cost, environmental friendliness and the like, but the voltage window of an aqueous solution is narrow (about 1.23V), so that some high-voltage positive electrode materials cannot normally work in the aqueous zinc batteries, and the energy density and the selection range of the positive electrode materials of the rechargeable zinc batteries are limited to a certain extent; in addition, the zinc cathode also faces the problems of zinc dendrite growth, serious side reaction (such as generation of inactive ZnO), low Zn deposition/precipitation coulombic efficiency, hydrogen precipitation and the like in an aqueous electrolyte, and the reversibility of the zinc cathode needs to be improved. In response to this, researchers have recently turned their attention to organic rechargeable zinc battery electrolytes, but related research is still in the beginning. At present, solvents used by an organic zinc battery electrolyte system are mainly acetonitrile and esters (such as ethylene carbonate), although the organic electrolytes can widen a voltage window and improve the cycling stability of a zinc cathode, the organic electrolytes are flammable, volatile and high in toxicity, and have serious potential safety hazards. Therefore, the development of a novel flame-retardant and high-performance electrolyte system is of great significance to the development and application of rechargeable zinc batteries.
Disclosure of Invention
The invention aims to provide a flame-retardant organic electrolyte for a rechargeable zinc battery, which solves the problems of flammability, volatility and high toxicity of the conventional organic zinc battery electrolyte.
The invention also aims to provide a preparation method of the flame-retardant organic electrolyte for the rechargeable zinc battery, so as to prepare the flame-retardant high-performance electrolyte.
It is a further object of the present invention to provide a rechargeable zinc battery.
One of the objects of the invention is achieved by:
the flame-retardant organic electrolyte for the rechargeable zinc battery comprises soluble zinc salt, sodium salt electrolyte salt and a flame-retardant organic solvent, wherein the concentration of the soluble zinc salt is 0.1-2 mol/L, and the concentration of the sodium salt electrolyte salt is 0.1-2.5 mol/L.
Preferably, the concentration of the soluble zinc salt is 0.2-1 mol/L.
Preferably, the concentration of the sodium salt electrolyte salt is 0.2-2.5 mol/L.
The flame-retardant organic solvent is a mixed solvent formed by mixing one or more of trimethyl phosphate (TMP), triethyl phosphate (TEP), dimethyl methyl phosphate (DMMP) and diethyl ethyl phosphate (DEEP); preferably, the flame retardant organic solvent is trimethyl phosphate (TMP) or triethyl phosphate (TEP).
The soluble zinc salt is zinc hexafluorophosphate (Zn (PF)6)2) Zinc perchlorate (Zn (ClO)4)2) Zinc trifluoromethanesulfonate (Zn (CF)3SO3)2) Or zinc bis (trifluoromethanesulfonyl) imide (Zn (TFSI)2) Any one or more of them; preferably, the soluble zinc salt is zinc perchlorate (Zn (ClO)4)2) Zinc trifluoromethanesulfonate (Zn (CF)3SO3)2) Or zinc bis (trifluoromethanesulfonyl) imide (Zn (TFSI)2）。
The sodium salt electrolyte salt is sodium bistrifluoromethanesulfonylimide (NaTFSI), sodium bistrifluoromethanesulfonylimide (NaFSI), sodium perchlorate (NaClO)4) Or sodium trifluoromethanesulfonate (NaCF)3SO3) Any one or more of them.
The preparation method of the flame-retardant organic electrolyte for the rechargeable zinc battery comprises the following steps: dissolving specific amounts of the soluble zinc salt and the sodium salt electrolyte salt in a flame-retardant organic solvent in a high-purity argon environment to enable the concentration of the soluble zinc salt to be 0.1-2 mol/L and the concentration of the sodium salt electrolyte salt to be 0.1-2.5 mol/L, oscillating, and carrying out ultrasonic treatment at room temperature to enable the soluble zinc salt and the sodium salt electrolyte salt to be completely dissolved, thus obtaining the flame-retardant zinc-sodium-zinc alloy.
The second purpose of the invention is realized by the following steps:
a preparation method of a flame-retardant organic electrolyte for a rechargeable zinc battery comprises the steps of dissolving specific amounts of soluble zinc salt and sodium salt electrolyte salt in a flame-retardant organic solvent in a high-purity argon environment to enable the concentration of the soluble zinc salt to be 0.1-2 mol/L and the concentration of the sodium salt electrolyte salt to be 0.1-2.5 mol/L, vibrating, and carrying out ultrasonic treatment at room temperature to enable the soluble zinc salt and the sodium salt electrolyte salt to be completely dissolved, so that the rechargeable zinc battery is obtained.
Preferably, the concentration of the soluble zinc salt is 0.2-1 mol/L.
Preferably, the concentration of the sodium salt electrolyte salt is 0.2-2.5 mol/L.
The flame-retardant organic solvent is a mixed solvent formed by mixing one or more of trimethyl phosphate (TMP), triethyl phosphate (TEP), dimethyl methyl phosphate (DMMP) and diethyl ethyl phosphate (DEEP).
The soluble zinc salt is zinc hexafluorophosphate (Zn (PF)6)2) Zinc perchlorate (Zn (ClO)4)2) Zinc trifluoromethanesulfonate (Zn (CF)3SO3)2) Or zinc bis (trifluoromethanesulfonyl) imide (Zn (TFSI)2) Any one or more of them.
The sodium salt electrolyte salt is sodium bistrifluoromethanesulfonylimide (NaTFSI), sodium bistrifluoromethanesulfonylimide (NaFSI), sodium perchlorate (NaClO)4) Or sodium trifluoromethanesulfonate (NaCF)3SO3) Any one or more of them.
The third purpose of the invention is realized by the following steps:
a rechargeable zinc battery comprises a positive electrode, a negative electrode, a diaphragm and the flame-retardant organic electrolyte for the rechargeable zinc battery.
The anode is sodium vanadium oxyfluoride phosphate (Na)3V2(PO4)2O2F) The preparation method comprises the following steps: mixing Na3V2(PO4)2O2F. The conductive carbon and the binder are mixed according to the mass ratio of 7:2:1, dispersed in water to prepare slurry, uniformly coated on a titanium foil with the thickness of 10-30 mu m, and dried in vacuum to obtain the positive plate.
The binder is sodium carboxymethyl cellulose (CMC).
The conductive carbon material is conductive carbon black, activated carbon, porous carbon, BP-2000, Vulcan XC-72, Super P or carbon nano tube.
The negative electrode is made of metal zinc foil or spherical zinc powder.
The negative electrode is made of metal zinc foil: the metallic zinc foil was cut to a specific size and used as a negative electrode sheet.
The negative electrode is 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 10-30 mu m, and drying the coated layer with the thickness of 20-50 mu m in vacuum at 80 ℃ for 12 hours to obtain a negative plate.
The diaphragm is a glass fiber film, a polyethylene non-woven fabric or microporous filter paper.
The flame-retardant organic electrolyte for the rechargeable zinc battery comprises soluble zinc salt, sodium salt electrolyte salt and a flame-retardant organic solvent, wherein the concentration of the soluble zinc salt is 0.1-2 mol/L, and the concentration of the sodium salt electrolyte salt is 0.1-2.5 mol/L; the flame-retardant organic solvent is a mixed solvent formed by mixing one or more of trimethyl phosphate (TMP), triethyl phosphate (TEP), dimethyl methyl phosphate (DMMP) and diethyl ethyl phosphate (DEEP); the soluble zinc salt is zinc hexafluorophosphate (Zn (PF)6)2) Zinc perchlorate (Zn (ClO)4)2) Zinc trifluoromethanesulfonate (Zn (CF)3SO3)2) Or zinc bis (trifluoromethanesulfonyl) imide (Zn (TFSI)2) Any one or more of them; the sodium salt electrolyte salt is sodium bistrifluoromethanesulfonylimide (NaTFSI), sodium bistrifluoromethanesulfonylimide (NaFSI), sodium perchlorate (NaClO)4) Or sodium trifluoromethanesulfonate (NaCF)3SO3) Any one or more of them.
The organic phosphate flame retardant is used as a solvent, and the zinc salt and the sodium salt with specific concentrations are used as electrolyte salts to form a flame-retardant organic electrolyte system which takes sodium ions and zinc ions as cations and is used for the rechargeable zinc battery, so that the organic phosphate flame retardant has the characteristics of excellent flame-retardant property, low viscosity, high conductivity (2.9 mS/cm), high cation migration rate and the like; the anions and cations in the electrolyte and solvent molecules form a stable solvation structure, so that the decomposition of the electrolyte under high and low potentials can be effectively inhibited, and the voltage window (3.2V vs. Zn) is improved2+and/Zn), guiding the uniform deposition of metal zinc, reducing the growth of zinc dendrites, and improving the coulombic efficiency (-100%) and the atomic utilization rate of Zn deposition/precipitation.
The high-stability electrolyte can expand the selection range of the positive electrode material of the zinc battery, and is used for Zn// Na3V2(PO4)2O2In the F rechargeable zinc battery system, the safety of the battery can be improved, and the rechargeable zinc battery has a high discharge voltage platform and good cycle stability, and shows wide application prospects.
Drawings
FIG. 1 is a graph comparing the flame retardant properties of electrolytes, in which a is 1 mol/L NaClO in the flame retardant organic electrolyte prepared in example 14 + 0.7 mol/L Zn(CF3SO3)2Ignition test result of TMP, b is 1 mol/L NaClO for the electrolyte prepared in comparative example 54 + 0.7 mol/L Zn(CF3SO3)2-the result of the ignition test of AN.
Fig. 2 is a thermogravimetric plot of the flame retardant organic electrolyte prepared in example 1.
Fig. 3 is a graph of voltage window test CV of the flame-retardant organic electrolyte prepared in example 1.
FIG. 4 is a graph of cycle stability test of the flame retardant organic electrolyte prepared in example 1 in a Zn/Zn symmetrical battery.
Fig. 5 is an SEM image of the surface of a zinc negative electrode after cycling of a Zn/Zn battery using the flame retardant organic electrolyte prepared in example 1.
FIG. 6 is a graph of the cycle performance of the flame retardant organic electrolyte Zn/Ti battery prepared in example 1.
FIG. 7 is Zn// Na of flame retardant organic electrolyte prepared using example 13V2(PO4)2O2And F, charge and discharge curve of the battery.
FIG. 8 is Zn// Na of flame retardant organic electrolyte prepared using example 13V2(PO4)2O2F cycle performance diagram of the cell.
FIG. 9 shows Zn// Na values of aqueous electrolytes prepared in comparative example 43V2(PO4)2O2And F, charge and discharge curve 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 examples below are conventional methods well known in the art, and the reagents used in the examples are all battery grade and are either commercially available or prepared by methods well known to those of ordinary skill in the art.
In the following examples, a rechargeable zinc battery comprising a positive electrode, a negative electrode, a separator and the electrolyte prepared in each example or comparative example, wherein sodium vanadium oxyfluorophosphate (Na) was used3V2(PO4)2O2F) As the positive electrode, a metal zinc foil was used as the negative electrode, and a glass fiber film was used as the separator.
The preparation method of the sodium vanadium fluorophosphate positive plate comprises the following steps: mixing Na3V2(PO4)2O2F. Mixing conductive carbon Super P and binder carboxymethylcellulose sodium (CMC) according to a mass ratio of 7:2:1, and dispersing in waterAnd (3) preparing slurry, uniformly coating the slurry on a titanium foil with the thickness of 10-30 mu m, and drying the titanium foil for 12 hours in vacuum at 100 ℃ to obtain the positive plate.
Example 1
In a high-purity argon atmosphere, 0.25 g of NaClO4Sodium salt and 0.51 g Zn (CF)3SO3)2Dissolving zinc salt in 2 mL TMP flame-retardant organic solvent, sufficiently shaking, performing ultrasonic treatment at room temperature for 10 minutes to completely dissolve the salt, and preparing into 1 mol/L NaClO4+ 0.7 mol/L Zn(CF3SO3)2-a TMP electrolyte.
The electrolyte obtained was subjected to the following performance tests:
(1) flame retardant properties
And (3) ignition test: the refractory wool soaked with the electrolyte prepared in this example was ignited with a fire gun and the combustion was observed.
The ignition test result of fig. 1a shows that the flame-retardant organic electrolyte prepared in this example can not be ignited by open fire at all, and has a good flame-retardant effect.
And (3) testing thermal stability: for the flame-retardant organic electrolyte (1 mol/L NaClO) prepared in this example4 + 0.7 mol/L Zn(CF3SO3)2-TMP) was subjected to thermogravimetric analysis, and the TGA curve obtained was as shown in FIG. 2.
(2) Electrical conductivity of
The conductivity of the flame-retardant organic electrolyte prepared in this example was measured by the ac impedance method, and the experimental data were recorded in the electrochemical workstation model CHI 660E. The results show that the electrolyte prepared in this example has a conductivity of 2.9 mS/cm.
(3) Electrolyte voltage window
The voltage window of the electrolyte passes the Zn/Ti cell test. In a high-purity argon glove box, a standard CR2032 button cell was prepared by dropping 80. mu.L of the electrolyte prepared in this example with titanium foil (Ti) as the working electrode, zinc foil (Zn) as the counter electrode and the reference electrode, and glass fiber as the separator. And testing the battery by adopting a cyclic sweep voltammetry (CV), wherein the sweep speed is set to be 0.5 mV/s, and the test voltage interval is-0.5-3V. Data were recorded using a model CHI660E electrochemical workstation.
The results are shown in FIG. 3, and show that the flame-retardant organic electrolyte prepared in this example is 1 mol/L NaClO4+ 0.7 mol/L Zn(CF3SO3)2TMP shows stable zinc deposition/precipitation at low potential, decomposition only after 2.7V at high potential, broadening the voltage window to above 3.2V (vs. Zn)2+/Zn）。
(4) Stability of electrolyte to zinc cathode
And (3) testing the cycling stability of the Zn/Zn symmetrical battery: in a high-purity argon glove box, zinc foils are used for the anode and the cathode. And (3) between the two zinc foils, using glass fiber as a diaphragm, dropwise adding 80 mu L of electrolyte to assemble the Zn/Zn symmetrical battery, and testing the stability of the electrolyte in the long-time circulation process. The test was carried out with a CT2001A model blue cell test system at 0.5 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. 4, which shows that the flame-retardant organic electrolyte prepared by the present example can stably circulate for more than 200 hours in a Zn/Zn symmetrical battery.
Characterization of a zinc cathode: and (4) disassembling the Zn/Zn battery after circulation for 200 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 topography of the zinc negative electrode after the cycle is shown in fig. 5, and it can be seen that no zinc dendrite grows on the surface of the zinc negative electrode.
(5) Cycling stability of electrolyte to zinc cathode
In a high-purity argon glove box, a titanium foil is used as a working electrode, a zinc foil is used as a counter electrode and a reference electrode, glass fiber is used as a diaphragm, 80 mu L of electrolyte with different proportions is dripped to assemble a Zn/Ti battery, and the circulation stability of the electrolyte and 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 1V (corresponding to the Zn deposition process)Out of process). The test current density is 0.2 mA/cm2。
Cycling stability of the resulting electrolyte and Zn2+The coulombic efficiency results of deposition/precipitation are shown in fig. 6, from which it can be seen that the metallic zinc negative electrode has excellent cycle stability in the electrolyte prepared in this example, and Zn2+The deposition/precipitation coulombic efficiency of/Zn is close to 100%, and the utilization rate of Zn atoms is obviously improved.
The electrolyte in this example was applied to a rechargeable zinc cell. The preparation method of the rechargeable zinc battery comprises the following steps: in a pure argon environment, the prepared positive plate is used as a positive electrode, the zinc foil with the diameter of 12 mm is used as a negative electrode, the glass fiber membrane is used as a diaphragm, 80 mu L of the flame-retardant organic electrolyte prepared in the embodiment is dripped, the battery is packaged, and the rechargeable zinc battery is prepared and tested for electrochemical performance.
And (3) testing the cycling stability: zn// Na assembled by using the electrolyte of the embodiment3V2(PO4)2O2The F zinc-based battery is 1-2.2V (vs. Zn)2+/Zn) was measured and the current density was 0.2C (1C = 130 mAh/g).
Prepared Zn// Na3V2(PO4)2O2The charge-discharge curve obtained for the F cell is shown in fig. 7, with an average discharge voltage of 1.8V; the cycle performance is shown in fig. 8, and it can be seen that the capacity retention rate is as high as 81% after 200 cycles, showing good long cycle stability.
Example 2
In a high-purity argon atmosphere, 0.49 g of NaClO4Sodium salt and 0.51 g Zn (CF)3SO3)2Dissolving zinc salt in 2 mL TMP flame-retardant organic solvent, fully shaking, performing ultrasonic treatment at room temperature for 1 hour to completely dissolve the salt, and preparing into 2 mol/L NaClO4+ 0.7 mol/L Zn(CF3SO3)2-a TMP electrolyte. And testing the flame retardance, the thermal stability, the conductivity and the electrochemical performance of the electrolyte.
The electrolyte in the embodiment is applied to a rechargeable zinc battery, and the preparation method comprises the following steps: in a pure argon ringIn the environment, prepared Na is used3V2(PO4)2O2And (3) taking the positive plate F as a positive electrode, taking the zinc foil with the diameter of 12 mm as a negative electrode, taking the glass fiber membrane as a diaphragm, dropwise adding 80 mu L of the electrolyte in the embodiment, packaging the battery to obtain the rechargeable zinc battery, and testing the electrochemical performance of the rechargeable zinc battery.
The test result shows that: the electrolyte is non-combustible, and the stable voltage window is from-0.5V to 2.7V. The salt concentration in the electrolyte is increased, and the conductivity is reduced (1.4 mS/cm); the initial coulombic efficiency of the deposition/precipitation of zinc ions in the electrolyte on the zinc cathode is 76%, and after 25 cycles of circulation, the coulombic efficiency of the zinc deposition/precipitation is gradually increased to about 94%. The electrolyte prepared in the example was applied to Zn// Na3V2(PO4)2O2In the F rechargeable zinc battery, after 200 cycles, the capacity retention rate is 62%.
Example 3
In a high purity argon atmosphere, 0.085 g of NaClO4Sodium salt and 0.363 g Zn (CF)3SO3)2Dissolving zinc salt in 1 mL TMP flame-retardant organic solvent, sufficiently shaking, performing ultrasonic treatment at room temperature for 15 minutes to completely dissolve the salt, and preparing into 0.7 mol/L NaClO4 + 1 mol/L Zn(CF3SO3)2-a TMP electrolyte. And testing the flame retardance, the thermal stability, the conductivity and the electrochemical performance of the electrolyte.
The electrolyte in the embodiment is applied to a rechargeable zinc battery, and the preparation method comprises the following steps: in a pure argon environment, prepared Na is used3V2(PO4)2O2And (3) taking the positive plate F as a positive electrode, taking the zinc foil with the diameter of 12 mm as a negative electrode, taking the glass fiber membrane as a diaphragm, dropwise adding 80 mu L of the electrolyte in the embodiment, packaging the battery to obtain the rechargeable zinc battery, and testing the electrochemical performance of the rechargeable zinc battery.
The test result shows that: the electrolyte is non-combustible, the stable voltage window is from-0.5V to 2.7V, and the conductivity is smaller than that of the electrolyte in the embodiment 1 (1.9 mS/cm); the deposition and precipitation coulomb efficiency of zinc ions in the electrolyte on a zinc cathode is gradually increased from initial 87 percent to 97 percent (20-30 circles), and then is reduced to 88 percent (50 circles). This is because the electrolyte of the present embodimentIn the middle, zinc salt, sodium salt and Zn2+The solvation binding force of ions and TMP solvent molecules is strong, and compared with the flame-retardant organic electrolyte in example 1, Zn is reduced2+The migration rate of (2) affects the deposition and precipitation behavior of zinc; meanwhile, the conductivity of the electrolyte becomes small, which affects the migration rate of two cations in the electrolyte. The electrolyte prepared in the example was applied to Zn// Na3V2(PO4)2O2In the F rechargeable zinc battery, after 200 cycles, the capacity retention rate is 73%.
Example 4
In a high purity argon atmosphere, 0.122 g of NaClO4Sodium salt and 0.073 g Zn (CF)3SO3)2Dissolving zinc salt in 1 mL TMP flame-retardant organic solvent, sufficiently shaking, performing ultrasonic treatment at room temperature for 10 minutes to completely dissolve the salt, and preparing into 1 mol/L NaClO4+ 0.2 mol/L Zn(CF3SO3)2-a TMP electrolyte. And testing the flame retardance, the thermal stability, the conductivity and the electrochemical performance of the electrolyte.
The electrolyte in the embodiment is applied to a rechargeable zinc battery, and the preparation method comprises the following steps: in a pure argon environment, prepared Na is used3V2(PO4)2O2And (3) taking the positive plate F as a positive electrode, taking the zinc foil with the diameter of 12 mm as a negative electrode, taking the glass fiber membrane as a diaphragm, dropwise adding 80 mu L of the electrolyte in the embodiment, packaging the battery to obtain the rechargeable zinc battery, and testing the electrochemical performance of the rechargeable zinc battery.
The test result shows that: the electrolyte is non-combustible, the stable voltage window is from-0.5V to 2.5V, and the conductivity is 4.9 mS/cm; the deposition and precipitation coulomb efficiency of zinc ions in the electrolyte at the zinc cathode is gradually increased from 86% initially to 98% (20-30 circles), and is gradually reduced along with the circulation (after 100 circles). This is because the electrolyte of this example contains a small amount of zinc salt and Zn2+The ions are not sufficient to support 100% of the precipitation behavior. The electrolyte prepared in the example was applied to Zn// Na3V2(PO4)2O2In the F rechargeable zinc battery, the first coulombic efficiency of the battery is 87 percent, and the subsequent cycle is low (95-98 percent) in coulombic efficiencyThe capacity is low (103 mAh/g), and after 100 cycles, the capacity retention rate is 74%.
Example 5
In a high-purity argon atmosphere, 0.022 g of NaClO4Sodium salt and 0.363 g Zn (CF)3SO3)2Dissolving zinc salt in 1 mL TMP flame-retardant organic solvent, sufficiently shaking, performing ultrasonic treatment at room temperature for 15 minutes to completely dissolve the salt, and preparing into 0.2 mol/L NaClO4 + 1 mol/L Zn(CF3SO3)2-a TMP electrolyte. And testing the flame retardance, the thermal stability, the conductivity and the electrochemical performance of the electrolyte.
The electrolyte in the embodiment is applied to a rechargeable zinc battery, and the preparation method comprises the following steps: in a pure argon environment, prepared Na is used3V2(PO4)2O2And (3) taking the positive plate F as a positive electrode, taking the zinc foil with the diameter of 12 mm as a negative electrode, taking the glass fiber membrane as a diaphragm, dropwise adding 80 mu L of the electrolyte in the embodiment, packaging the battery to obtain the rechargeable zinc battery, and testing the electrochemical performance of the rechargeable zinc battery.
The test result shows that: the electrolyte is non-combustible, the stable voltage window is from-0.5V to 2.6V, and the conductivity is 2.5 mS/cm; the deposition and precipitation coulombic efficiency of zinc ions in the electrolyte on a zinc cathode is approximate to 100 percent. However, the electrolyte prepared in this example was applied to Zn// Na3V2(PO4)2O2In the F rechargeable zinc battery, the first coulombic efficiency of the battery is 87%, the subsequent coulombic efficiency in circulation is only 97%, the reversible capacity is low (90 mAh/g), and the capacity retention rate is 78% after 65-circle circulation.
Example 6
In a high purity argon atmosphere, 0.306 g NaClO4Sodium salt and 0.073 g Zn (CF)3SO3)2Dissolving zinc salt in 1 mL TMP flame-retardant organic solvent, sufficiently shaking, performing ultrasonic treatment at room temperature for 10 minutes to completely dissolve the salt, and preparing into 2.5 mol/L NaClO4 + 0.2 mol/L Zn(CF3SO3)2-a TMP electrolyte. And testing the flame retardance, the thermal stability, the conductivity and the electrochemical performance of the electrolyte.
Example 7
In a high-purity argon atmosphere, 0.120 g of NaCF is taken3SO3Sodium salt and 0.625 g Zn (TFSI)2Dissolving zinc salt in 1 mL TEP flame-retardant organic solvent, sufficiently shaking, performing ultrasonic treatment at room temperature to completely dissolve the salt, and preparing into 0.7 mol/L NaCF3SO3+ 1 mol/L Zn(TFSI)2-a TEP electrolyte. And testing the flame retardance, the thermal stability, the conductivity and the electrochemical performance of the electrolyte.
Example 8
In a high purity argon atmosphere, 0.120 g of NaCF3SO3Sodium salt and 0.264 g Zn (ClO)4)2Dissolving zinc salt in 1 mL TMP flame retardant organic solvent, fully shaking, performing ultrasonic treatment at room temperature to completely dissolve the salt, and preparing into 0.7 mol/L NaCF3SO3 + 1 mol/L Zn(ClO4)2-a TMP electrolyte. And testing the flame retardance, the thermal stability, the conductivity and the electrochemical performance of the electrolyte.
Example 9
In a high purity argon atmosphere, 0.020 g of NaFSI sodium salt and 0.711 g of Zn (PF)6)2Dissolving zinc salt in 1 mL of DEEP flame-retardant organic solvent, fully shaking, performing ultrasonic treatment at room temperature to completely dissolve the salt, and preparing into 0.1 mol/L NaFSI + 2 mol/L Zn (PF)6)2-DEEP electrolyte. And testing the flame retardance, the thermal stability, the conductivity and the electrochemical performance of the electrolyte.
Example 10
In a high purity argon atmosphere, 0.151 g NaTFSI sodium salt and 0.063 g Zn (TFSI)2Dissolving zinc salt in 1 mL of DMMP flame retardant organic solvent, shaking sufficiently, performing ultrasonic treatment at room temperature to completely dissolve the salt, and preparing into 0.5 mol/L NaTFSI + 0.1 mol/L Zn (TFSI)2-a DMMP electrolyte. And testing the flame retardance, the thermal stability, the conductivity and the electrochemical performance of the electrolyte.
Comparative example 1
In a high-purity argon atmosphere, 0.122 g of NaClO is taken4Dissolving sodium salt in 1 mL TMP flame-retardant organic solvent, sufficiently shaking to completely dissolve the salt, and preparing into 1 mol/L NaClO4-a TMP electrolyte. For the obtained electrolyteAnd testing the flame retardance, the thermal stability, the conductivity and the electrochemical performance.
The electrolyte is applied to a rechargeable zinc battery, and the preparation method comprises the following steps: in a pure argon environment, prepared Na is used3V2(PO4)2O2And (3) taking the F positive plate as a positive electrode, taking the zinc foil with the diameter of 12 mm as a negative electrode, taking the glass fiber membrane as a diaphragm, dropwise adding 80 mu L of electrolyte, packaging the battery to obtain the rechargeable zinc battery, and testing the electrochemical performance of the rechargeable zinc battery. The results show that the prepared electrolyte containing only sodium salt can not support the operation of the zinc battery.
Comparative example 2
In a high purity argon atmosphere, 0.25 g Zn (CF)3SO3)2Dissolving zinc salt in 1 mL TMP flame retardant organic solvent, shaking sufficiently to dissolve salt completely, and preparing into 0.7 mol/L Zn (CF)3SO3)2-a TMP electrolyte. And testing the flame retardance, the thermal stability, the conductivity and the electrochemical performance of the electrolyte.
The electrolyte is applied to a rechargeable zinc battery, and the preparation method comprises the following steps: in a pure argon environment, prepared Na is used3V2(PO4)2O2And (3) taking the F positive plate as a positive electrode, taking the zinc foil with the diameter of 12 mm as a negative electrode, taking the glass fiber membrane as a diaphragm, dropwise adding 80 mu L of electrolyte, packaging the battery to obtain the rechargeable zinc battery, and testing the electrochemical performance of the rechargeable zinc battery.
The results show that: the electrolyte is incombustible, and although the electrolyte has high conductivity (5.4 mS/cm), the electrolyte has decomposition phenomenon at high potential, and the stable voltage window is only from-0.5V to 1.5V. The electrolyte prepared by the comparative example was applied to Zn// Na3V2(PO4)2O2In F rechargeable zinc cells, the first coulombic efficiency was only 71.7% due to side reactions between the electrolyte and the electrodes. The capacity is attenuated in the subsequent cycle (the capacity retention rate is 66% after 100 circles), the coulombic efficiency is between 80 and 90%, and the poor cycle stability is shown.
Comparative example 3
In a high purity argon atmosphere, 0.73 g Zn (CF)3SO3)2Dissolving zinc salt in 1 mL TMP flame retardant organic solvent, vibrating sufficiently, and performing ultrasonic treatment at room temperature for 1 hour to completely dissolve the salt to prepare 2.0 mol/L Zn (CF)3SO3)2-a TMP electrolyte. And testing the flame retardance, the thermal stability, the conductivity and the electrochemical performance of the electrolyte.
The electrolyte is applied to a rechargeable zinc battery, and the preparation method comprises the following steps: in a pure argon environment, prepared Na is used3V2(PO4)2O2And (3) taking the F positive plate as a positive electrode, taking the zinc foil with the diameter of 12 mm as a negative electrode, taking the glass fiber membrane as a diaphragm, dropwise adding 80 mu L of electrolyte, packaging the battery to obtain the rechargeable zinc battery, and testing the electrochemical performance of the rechargeable zinc battery.
The electrolyte prepared by the comparative example is non-combustible and has a stable electrochemical window. However, the salt concentration in the electrolyte is increased, so that the viscosity of the electrolyte is increased, the conductivity is reduced, and the deposition and precipitation efficiency (-85%) of zinc ions of the electrolyte on a zinc cathode is influenced. When the prepared electrolyte is applied to a battery system, the charge-discharge curve polarization is large, the coulombic efficiency is low, and the cycle performance is poor (see table 1 for details).
Comparative example 4
In air, 0.25 g of NaClO4Sodium salt and 0.51 g Zn (CF)3SO3)2Dissolving zinc salt in 2 mL of water, fully shaking to completely dissolve the salt, and preparing into 1 mol/L NaClO4 + 0.7 mol/L Zn(CF3SO3)2The aqueous electrolyte of (1). And testing the flame retardance, the thermal stability, the conductivity and the electrochemical performance of the electrolyte.
The electrolyte in the comparative example is applied to a rechargeable zinc battery, and the preparation method comprises the following steps: in air environment, using prepared Na3V2(PO4)2O2And (3) taking the F positive plate as a positive electrode, taking the zinc foil with the diameter of 12 mm as a negative electrode, taking the glass fiber membrane as a diaphragm, dropwise adding 80 mu L of electrolyte, packaging the battery to obtain the rechargeable water-based zinc battery, and testing the electrochemical performance of the rechargeable water-based zinc battery.
And (3) testing the cycling stability: will be assembled Zn// Na3V2(PO4)2O2The F zinc-based battery is 1-2.2V (vs. Zn)2+/Zn) was tested for charge and discharge in the voltage range, the current density was 0.2C.
The results are shown in FIG. 9, where it can be seen that Zn// Na3V2(PO4)2O2The F zinc-based battery cannot perform reversible charge and discharge in the aqueous electrolyte prepared in the present comparative example, and side reactions such as electrolyte decomposition may occur at high voltage.
Comparative example 5
In a high-purity argon atmosphere, 0.25 g of NaClO4Sodium salt and 0.51 g Zn (CF)3SO3)2Dissolving zinc salt in 2 mL acetonitrile solution, fully shaking, performing ultrasonic treatment at room temperature to completely dissolve the salt, and preparing into 1 mol/L NaClO4 + 0.7 mol/L Zn(CF3SO3)2-AN electrolyte. And testing the flame retardance, the thermal stability, the conductivity and the electrochemical performance of the electrolyte.
And (3) flame retardant test: the refractory wool soaked with the electrolyte prepared in this comparative example was ignited with a fire gun, and the combustion condition was observed.
The obtained results are shown in fig. 1b, and the results show that the refractory cotton soaked in the electrolyte prepared by the comparative example burns vigorously and does not have flame retardant capability.
The electrolyte prepared in this comparative example was applied to a rechargeable zinc battery. The preparation method of the rechargeable zinc battery comprises the following steps: in a pure argon environment, prepared Na is used3V2(PO4)2O2And (3) taking the F positive plate as a positive electrode, taking the zinc foil with the diameter of 12 mm as a negative electrode, taking the glass fiber membrane as a diaphragm, dropwise adding 80 mu L of the electrolyte prepared according to the comparative example, packaging the battery to obtain the rechargeable zinc battery, and testing the electrochemical performance of the rechargeable zinc battery.
The electrolyte prepared in examples 1 to 5 and comparative examples 1 to 5 and Zn// Na when used in rechargeable zinc batteries3V2(PO4)2O2The electrochemical performance test results of the F cell are shown in table 1 below.
TABLE 1
Figure DEST_PATH_IMAGE002

Claims (6)

1. A rechargeable zinc battery comprises a positive electrode, a negative electrode, a diaphragm and a flame-retardant organic electrolyte for the rechargeable zinc battery; the flame-retardant organic electrolyte for the rechargeable zinc battery comprises soluble zinc salt, sodium salt electrolyte salt and a flame-retardant organic solvent, wherein the concentration of the soluble zinc salt is 0.1-2 mol/L, and the concentration of the sodium salt electrolyte salt is 0.1-2.5 mol/L; the zinc ions in the soluble zinc salt and the sodium ions in the sodium salt electrolyte salt jointly act as cations to participate in electrochemical reaction; the anode is a sodium vanadium phosphate oxyfluoride anode plate, and the cathode is a cathode plate made of metal zinc foil or a cathode plate made of zinc powder.
2. The rechargeable zinc battery according to claim 1, wherein the flame retardant organic solvent is a mixed solvent formed by mixing one or more of trimethyl phosphate, triethyl phosphate, dimethyl methyl phosphate and diethyl ethyl phosphate.
3. The rechargeable zinc battery according to claim 1, wherein the soluble zinc salt is any one or more of zinc hexafluorophosphate, zinc perchlorate, zinc trifluoromethanesulfonate or zinc bistrifluoromethanesulfonylimide.
4. The rechargeable zinc battery according to claim 1, wherein the sodium salt electrolyte salt is any one or more of sodium bistrifluoromethanesulfonylimide, sodium bis (fluorosulfonyl) imide, sodium perchlorate or sodium trifluoromethanesulfonate.
5. The rechargeable zinc battery of claim 1, wherein the preparation method of the flame-retardant organic electrolyte for the rechargeable zinc battery comprises the following steps: dissolving soluble zinc salt and sodium salt electrolyte salt in a flame-retardant organic solvent in a high-purity argon environment to enable the concentration of the soluble zinc salt to be 0.1-2 mol/L and the concentration of the sodium salt electrolyte salt to be 0.1-2.5 mol/L, oscillating, and carrying out ultrasonic treatment at room temperature to enable the soluble zinc salt and the sodium salt electrolyte salt to be completely dissolved.
6. The rechargeable zinc battery according to claim 1, wherein the preparation method of the positive plate comprises the steps of mixing sodium vanadium oxyfluorophosphate, conductive carbon and a binder according to a mass ratio of 7:2:1, dispersing the mixture in water to prepare slurry, uniformly coating the slurry on a titanium foil with the thickness of 10-30 mu m, and drying the slurry in vacuum to obtain the rechargeable zinc battery; the binder is sodium carboxymethyl cellulose; the conductive carbon material is conductive carbon black, activated carbon, porous carbon, BP-2000, Vulcan XC-72, Super P or carbon nano tube.
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