CN119419385A - Ammonium/phosphorus-based electrolyte, preparation method and application thereof in preparation of water-based zinc-iodine battery - Google Patents
Ammonium/phosphorus-based electrolyte, preparation method and application thereof in preparation of water-based zinc-iodine battery Download PDFInfo
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Abstract
The invention provides an ammonium/phosphorus-based electrolyte, which belongs to the technical field of water-based zinc ion batteries, wherein the electrolyte comprises zinc salt, water, an organic solvent and an organic salt additive, the zinc salt comprises zinc sulfate, the organic solvent comprises ethylene glycol and/or N, N-dimethylformamide, the organic salt additive comprises at least one of 3-bromopropyl trimethyl ammonium bromide, tetrapropyl ammonium bromide and methyltriphenyl phosphorus bromide, the concentration of the zinc salt in the electrolyte is 1-3 mol/L, and the concentration of the organic salt additive is 0.1-0.3 mol/L. The electrolyte can successfully excite and stabilize the highly reversible four-electron redox reaction of the zinc-iodine battery from I ‑ to I +, and further remarkably improve the specific capacity, electrode potential, energy density and cycle performance of the zinc-iodine battery. The invention also provides a preparation method of the ammonium/phosphorus-based electrolyte and application of the ammonium/phosphorus-based electrolyte in preparation of a water-based zinc-iodine battery.
Description
Technical Field
The invention belongs to the technical field of water-based zinc ion batteries, and particularly relates to an ammonium/phosphorus-based electrolyte, a preparation method and application thereof in preparing a water-based zinc-iodine battery.
Background
Aqueous zinc ion batteries have received great attention for their excellent safety and higher energy density and show great potential for use in future energy storage systems. However, the specific capacity of the current zinc battery positive electrode only reaches 1/3 of that of the zinc metal negative electrode, which limits the energy density of the zinc-based battery to a certain extent. The iodine-based positive electrode material is a key for improving the performance of the zinc-based battery because of the characteristics of rich resources, multiple valence states, high capacity, high oxidation-reduction potential and the like.
The reaction of the iodine-based anode generally involves a two-electron redox reaction of the elements I -/I3 - to I 2 with a theoretical capacity of 211 mAh g -1 and a potential of about 1.3V (vs. Zn 2+/Zn). Notably, the novel four-electron zinc-iodine battery exhibits superior performance, employing a continuous I −/I2/I+ redox couple, enabling higher redox potentials (1.07V/0.54V vs. SHE) and doubling of theoretical capacity (422 mAh g -1). This not only increases the specific capacity significantly, but also increases the energy density further with a theoretical potential of 1.75V (vs. Zn/Zn 2+) from I 0 to I +.
However, the reversible redox reaction between I 2 and I + has a high potential barrier, and I + is difficult to independently and stably exist, and in addition, the shuttle effect of the iodine species causes problems of serious capacity decay, poor cycle life and the like of the iodine-based positive electrode. To solve these problems, researchers are making a series of searches and attempts. For example, stability and cycle performance of the iodine-based positive electrode are improved by optimizing electrode materials and structures, potential barriers of oxidation-reduction reactions between I 2 and I + are reduced by introducing a catalyst, reversibility of the reactions is improved, shuttle effects of iodine substances are inhibited by designing novel diaphragms and electrolyte, and overall performance of the battery is improved.
Disclosure of Invention
In order to obtain a high-performance water-based zinc-iodine battery, the invention provides an ammonium/phosphorus-based electrolyte which can successfully excite and stabilize the highly reversible four-electron redox reaction of the zinc-iodine battery from I - to I +, thereby remarkably improving the specific capacity, electrode potential, energy density and cycle performance of the zinc-iodine battery.
The invention also provides a preparation method of the ammonium/phosphorus-based electrolyte and application of the ammonium/phosphorus-based electrolyte in preparation of a water-based zinc-iodine battery.
The invention is realized by the following technical scheme:
The invention provides an ammonium/phosphorus-based electrolyte, which comprises zinc salt, water, an organic solvent and an organic salt additive, wherein the zinc salt comprises zinc sulfate, the organic solvent comprises ethylene glycol and/or N, N-dimethylformamide, and the organic salt additive comprises at least one of 3-bromopropyl trimethyl ammonium bromide, tetrapropyl ammonium bromide and methyl triphenyl phosphorus bromide;
In the electrolyte, the concentration of the zinc salt is 1-3 mol/L, and the concentration of the organic salt additive is 0.1-0.3 mol/L.
In the electrolyte, the volume ratio of the organic solvent to water is (30-70): 100.
Optionally, in the electrolyte, the organic solvent is ethylene glycol, and the organic salt additive is 3-bromopropyl trimethyl ammonium bromide.
Optionally, in the electrolyte, the organic solvent is N, N-dimethylformamide, and the organic salt additive is tetrapropylammonium bromide.
Optionally, in the electrolyte, the organic solvent is N, N-dimethylformamide, and the organic salt additive is methyltriphenyl phosphorus bromide.
Based on the same inventive concept, the present invention provides a preparation method of an ammonium/phosphorus-based electrolyte, the preparation method comprising:
The zinc sulfate and the organic salt additive are dissolved in a mixed solution of water and an organic solvent together to obtain an ammonium/phosphorus-based electrolyte;
in the mixed solution, the volume ratio of the organic solvent to the water is (30-70): 100;
In the ammonium/phosphorus-based electrolyte, the concentration of zinc sulfate is 1-3 mol/L, and the concentration of the organic salt additive is 0.1-0.3 mol/L.
Based on the same inventive concept, the invention provides an application of an ammonium/phosphorus-based electrolyte in preparing a water-based zinc-iodine battery.
Based on the same inventive concept, the invention provides a water-based zinc-iodine battery, which contains the ammonium/phosphorus-based electrolyte.
Based on the same inventive concept, the invention provides a water-based zinc-iodine battery, which takes an I 2 -containing composite material as a positive electrode, zinc metal as a negative electrode, glass fiber as a diaphragm, and the ammonium/phosphorus-based electrolyte as electrolyte.
Preferably, the preparation raw materials of the composite material containing I 2 comprise active carbon, iodine and carbon nanotubes, and the mass ratio of the active carbon to the iodine to the carbon nanotubes is 10:1:1.
Based on the same inventive concept, the invention also provides a symmetrical zinc battery, wherein zinc metal is used as a positive electrode and a negative electrode, glass fiber is used as a diaphragm, and one of the ammonium/phosphorus-based electrolytes is used as electrolyte.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
1. The invention relates to an ammonium/phosphorus-based electrolyte, which comprises zinc salt, deionized water, an organic solvent and an organic salt additive, wherein the organic salt additive comprises at least one of 3-bromopropyl trimethyl ammonium bromide, tetrapropyl ammonium bromide and methyl triphenyl phosphorus bromide, the organic salt additive can introduce iso-halogen conversion chemistry into a zinc-iodine battery, successfully excite and stabilize the highly reversible four-electron redox reaction of the zinc-iodine battery from I - to I + through a high-efficiency inter-halogen activation strategy, greatly improve the specific capacity, electrode potential and cycle performance of the zinc-iodine battery, promote the four-electron reaction from I - to I + by taking Br - as an activator through the interaction between halogens, effectively lighten kinetic obstruction, provide high capacity and energy density, and provide an effective strategy for improving the performance of the water-based zinc-ion battery.
2. The zinc salt and the organic salt additive added in the electrolyte are conventional chemicals, the raw materials used are cheap and easy to obtain, the electrolyte is prepared by a simple method, and the electrolyte can be obtained by a simple dissolution method and can show better reversibility, high safety and excellent electrochemical performance when being applied to a water-based zinc ion battery.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph of charge and discharge at 1C current density for a Zn// I 2 full cell assembled from a zinc sulfate electrolyte containing 3-bromopropyl trimethylammonium bromide and ethylene glycol in example 1;
FIG. 2 is a graph of charge and discharge at 1C current density for a Zn// I 2 full cell assembled from the zinc sulfate electrolyte containing methyltriphenylphosphorous bromide and N, N-dimethylformamide of example 2;
FIG. 3 is a graph of charge and discharge at 1C current density for a Zn// I 2 full cell assembled from the zinc sulfate electrolyte containing tetrapropylammonium bromide and N, N-dimethylformamide of example 3;
FIG. 4 is a graph of charge and discharge at 1C current density for a Zn// I 2 full cell assembled from a zinc sulfate electrolyte containing zinc bromide and N, N-dimethylformamide in comparative example 2;
FIG. 5 is a charge and discharge plot at 1C current density for a Zn// I 2 full cell assembled from a zinc sulfate electrolyte containing zinc bromide and ethylene glycol of comparative example 3;
FIG. 6 is a long cycle comparison plot at room temperature of 25℃for a symmetric zinc cell assembled using the zinc sulfate electrolyte containing methyltriphenylphosphorous bromide and N, N-dimethylformamide of example 2 and the zinc sulfate electrolyte containing zinc bromide of comparative example 1;
FIG. 7 is a long cycle comparison plot at room temperature of 25℃for a symmetric zinc cell assembled using the zinc sulfate electrolyte containing tetrapropylammonium bromide and N, N-dimethylformamide of example 3 and the zinc sulfate electrolyte containing zinc bromide of comparative example 1;
FIG. 8 is a long cycle plot of a Zn// I 2 full cell at 1C current density for a zinc sulfate electrolyte containing 3-bromopropyl trimethylammonium bromide and ethylene glycol in example 1 of the present invention assembled with a zinc sulfate electrolyte containing zinc bromide in comparative example 1.
FIG. 9 is a long cycle plot of a Zn// I 2 full cell assembled from the zinc sulfate electrolyte containing methyltriphenylphosphorous bromide and N, N-dimethylformamide of example 2 of the present invention and the zinc sulfate electrolyte containing zinc bromide of comparative example 1 at a current density of 1C.
FIG. 10 is a long cycle plot of a Zn// I 2 full cell assembled from the zinc sulfate electrolyte containing tetrapropylammonium bromide and N, N-dimethylformamide of example 3 of the present invention and the zinc sulfate electrolyte containing zinc bromide of comparative example 1 at a current density of 1C.
Detailed Description
The advantages and various effects of the present invention will be more clearly apparent from the following detailed description and examples. It will be understood by those skilled in the art that these specific embodiments and examples are intended to illustrate the invention, not to limit the invention.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification will control.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
The experimental methods used in the examples below are conventional, unless otherwise specified.
The technical principle of the invention is as follows:
The invention relates to an ammonium/phosphorus-based electrolyte, which comprises zinc salt, water, an organic solvent and an organic salt additive, wherein the zinc salt comprises zinc sulfate, the organic solvent comprises ethylene glycol and/or N, N-dimethylformamide, and the organic salt additive comprises at least one of 3-bromopropyl trimethyl ammonium bromide, tetrapropyl ammonium bromide and methyl triphenyl phosphorus bromide;
In the electrolyte, the concentration of the zinc salt is 1-3 mol/L, and the concentration of the organic salt additive is 0.1-0.3 mol/L.
In the electrolyte, the organic solvent plays a role in optimizing the composition of the organic electrolyte, improving the conductivity of the organic electrolyte, reducing polarization, improving the coulomb efficiency of the battery and increasing the reversibility of the battery circulation.
The organic solvent adopts glycol or N, N-dimethylformamide, and the glycol and the N, N-Dimethylformamide (DMF) are all important organic chemical raw materials, have respective unique advantages, the glycol has good water solubility and high boiling point, the DMF is a multifunctional solvent, has good solubility, high boiling point, thermal stability and chemical stability, and the two solvents have low price and wide application range and are common organic solvents.
The organic salt additive adopts 3-bromopropyl trimethyl ammonium bromide, tetrapropyl ammonium bromide and methyl triphenyl phosphonium bromide, and has the advantages that the three components contain bromine, and the voltage range is 0.5-1.85V, so that four-electron reaction can be excited.
In the electrolyte, the concentration of zinc salt is 1-3 mol/L, if the concentration of zinc salt is too high, although the conductivity of the electrolyte can be improved, the migration rate of zinc ions is enhanced, and thus the charge and discharge efficiency of a battery is improved, the viscosity of electrolyte is increased due to the too high concentration of zinc salt, so that ion transmission becomes more difficult, and the performance of the battery is reduced, and in addition, the growth of zinc dendrite is possibly aggravated by high concentration of electrolyte, so that the internal short circuit and the cycle life of the battery are shortened. If the zinc salt concentration is too low, although the zinc salt concentration is favorable for reducing the growth of zinc dendrite and reducing the internal resistance of the battery, thereby improving the cycle stability and the safety of the battery, the conductivity of the electrolyte is reduced, the migration rate of zinc ions is slowed down, and the charge and discharge performance and the energy density of the battery are affected.
In the electrolyte, the concentration of the organic salt additive is 0.1-0.3 mol/L, and if the concentration of the organic salt additive is less than 0.1mol/L, the battery performance is not obviously improved, and if the concentration of the organic salt additive is more than 0.3mol/L, the organic salt additive is possibly insoluble.
In the electrolyte, the volume ratio of the organic solvent to water is (30-70): 100.
In the invention, the volume ratio of the organic solvent to the water is (30-70): 100, and the influence of the concentration of the organic solvent is too low:
1. ion conductivity decreases, which is one of the key properties of the electrolyte, and too low a concentration results in a decrease in the number of ions in the electrolyte, thereby decreasing ion conductivity and affecting the charge and discharge properties of the battery.
2. The internal resistance of the battery is increased, the internal impedance of the battery is increased due to insufficient concentration of electrolyte, so that more heat is generated in the charging and discharging processes of the battery, and the energy efficiency is reduced.
3. The cycle performance is deteriorated, and the insufficient concentration of the electrolyte may accelerate the aging of the battery and reduce the cycle life of the battery.
4. The electrochemical window narrows, which may be caused by low electrolyte concentration, thereby limiting the operating voltage range of the cell.
Effect of too high an organic solvent concentration:
1. Interface stability problems-excessive concentrations may form unstable layers at the electrode and electrolyte interface, affecting the long-term stability of the battery.
2. Ion migration number is reduced, and a high concentration of the organic solvent may reduce ion migration number, thereby affecting the dynamic performance of the battery.
3. The viscosity of the electrolyte is increased, and the concentration is too high, so that the viscosity of the electrolyte is increased, the rapid movement of ions is not facilitated, and the rate performance of the battery is further affected.
4. Safety problems high concentrations of organic solvents may increase the safety risk of the battery under extreme conditions, such as thermal runaway, etc.
5. Film forming properties affect the properties of a Solid Electrolyte Interface (SEI) film formed on the surface of an electrode, and thus stability and lifetime of a battery, may be affected by an excessively high or excessively low concentration of an organic solvent in an electrolyte.
Furthermore, too high a concentration of organic additives may increase the cost of the electrolyte and adverse side reactions may occur at high potentials. If the concentration of the organic additive is too low, although the cost of the electrolyte can be reduced, the viscosity of the electrolyte can be reduced, and the ionic transport is facilitated, the electrolyte can be insufficiently protected, and the decomposition of the electrolyte and the side reaction of the electrode can not be effectively inhibited, so that the cycle life of the battery is shortened, the coulombic efficiency is reduced and the safety is reduced.
The following will describe in detail an ammonium/phosphorus-based electrolyte, a preparation method and application thereof in preparing an aqueous zinc-iodine battery according to the present invention with reference to examples and experimental data.
The battery performance test in the following examples and comparative examples was carried out using a new battery test system. To measure the long cycle time of the symmetrical cell, two polished zinc foils were used as two electrode sheets, and the electrolyte prepared in the following examples and comparative examples was used, glass fiber was used as a separator, and a 2032 button symmetrical cell was assembled and tested at constant current density and constant time. To investigate the application feasibility of the additive in a practical full cell, we uniformly mixed active carbon (purchased from colali (Kuraray China Co)), iodine (I812016, 99.8%, purchased from michelin (Macklin)) with carbon nanotubes (G991390, > 95%, diameter: 20-40nm, length: 1-2 μm, purchased from michelin (Macklin)) according to a mass ratio of 10:1:1, added with 1-2 ml of bacterial cellulose dispersion, dissolved in an aqueous solution to prepare a mixed solution, and then suction filtered and dried to prepare a working electrode (positive electrode), using the electrolytes prepared in the following examples and comparative examples, using glass fibers as a separator, zinc foil as a negative electrode to assemble 2032 button cell, and testing voltage range of 0.5V-1.85V vs. Zn/Zn 2+.
Example 1
The embodiment provides a preparation method of an ammonium/phosphorus-based electrolyte, which specifically comprises the following steps:
(1) Weighing 1.4378 g zinc sulfate heptahydrate and 0.1305 g 3-bromopropyl trimethyl ammonium bromide powder, dissolving in a mixed solution of deionized water and ethanol, adding deionized water to fix the volume to prepare 5 ml mixed liquid, and stirring by a magnet to accelerate dissolution and dispersion uniformly;
(2) And (3) carrying out suction filtration on the solution obtained in the step (1) through a micro-pore filtration membrane (with the pore diameter of 0.45 μm) to remove insoluble impurities in the solution, thereby obtaining the ammonium/phosphorus-based electrolyte.
In the ammonium/phosphorus-based electrolyte, the volume ratio of deionized water to ethanol is 100:30.
Example 2
The embodiment provides a preparation method of an ammonium/phosphorus-based electrolyte, which specifically comprises the following steps:
(1) Weighing 1.4378 g zinc sulfate heptahydrate and 0.3572 g methyl triphenyl phosphonium bromide powder, dissolving in a mixed solution of deionized water and N, N-dimethylformamide, adding deionized water to fix the volume to prepare 5 ml mixed liquid, and stirring by a magnet to accelerate dissolution and dispersion uniformly;
(2) And (3) carrying out suction filtration on the solution obtained in the step (1) through a micro-pore filtration membrane (with the pore diameter of 0.45 μm) to remove insoluble impurities in the solution, thereby obtaining the ammonium/phosphorus-based electrolyte.
In the ammonium/phosphorus-based electrolyte, the volume ratio of deionized water to N, N-dimethylformamide is 100:30.
Example 3
The embodiment provides a preparation method of an ammonium/phosphorus-based electrolyte, which specifically comprises the following steps:
(1) Weighing 1.4378 g zinc sulfate heptahydrate and 0.3993 g tetrapropylammonium bromide powder, dissolving in a mixed solution of deionized water and N, N-dimethylformamide, adding deionized water to fix the volume to prepare 5ml mixed liquid, and stirring by a magnet to accelerate dissolution and dispersion uniformly;
(2) And (3) carrying out suction filtration on the solution obtained in the step (1) through a micro-pore filtration membrane (with the pore diameter of 0.45 μm) to remove insoluble impurities in the solution, thereby obtaining the ammonium/phosphorus-based electrolyte.
In the ammonium/phosphorus-based electrolyte, the volume ratio of deionized water to N, N-dimethylformamide is 100:30.
Comparative example 1
The embodiment provides a preparation method of an electrolyte, which specifically comprises the following steps:
1) 0.3378 g zinc bromide and 1.4378 g zinc sulfate heptahydrate are dissolved in deionized water, deionized water is added to fix the volume to prepare 5 ml mixed liquid, and the solution and the dispersion are accelerated and evenly dispersed through magnetic stirring;
2) And (3) carrying out suction filtration on the solution obtained in the step (1) through a micro-pore filtration membrane (with the pore diameter of 0.45 mu m) to remove insoluble impurities in the solution, thereby obtaining the zinc sulfate electrolyte containing zinc bromide.
Comparative example 2
The embodiment provides a preparation method of an electrolyte, which specifically comprises the following steps:
1) 0.1126 g zinc bromide and 1.4378 g zinc sulfate heptahydrate are dissolved in a mixed solution of deionized water and N, N-dimethylformamide, 5 ml mixed liquid is prepared by adding deionized water to a fixed volume, and the solution is accelerated to be dissolved and dispersed uniformly through magnetic stirring;
2) And (3) carrying out suction filtration on the solution obtained in the step (1) through a micro-pore filtration membrane (with the pore diameter of 0.45 mu m) to remove insoluble impurities in the solution, thereby obtaining the zinc sulfate electrolyte.
In the zinc sulfate electrolyte, the volume ratio of deionized water to N, N-dimethylformamide is 100:30.
Comparative example 3
The embodiment provides a preparation method of an electrolyte, which specifically comprises the following steps:
1) 0.1126 g zinc bromide and 1.4378 g zinc sulfate heptahydrate are dissolved in a mixed solution of deionized water and ethylene glycol, 5 ml mixed liquid is prepared by adding deionized water to a fixed volume, and the solution is accelerated to be dissolved and dispersed uniformly through magnetic stirring;
2) And (3) carrying out suction filtration on the solution obtained in the step (1) through a micro-pore filtration membrane (with the pore diameter of 0.45 mu m) to remove insoluble impurities in the solution, thereby obtaining the zinc sulfate electrolyte.
In the zinc sulfate electrolyte, the volume ratio of deionized water to ethylene glycol is 100:30.
FIG. 1 is a charge and discharge plot at 1C current density for a Zn// I 2 full cell assembled from a zinc sulfate electrolyte containing 3-bromopropyl trimethylammonium bromide and ethylene glycol in example 1. From FIG. 1, it is clear that the added organic additive 3-bromopropyl trimethyl ammonium bromide can excite the four-electron reaction of the zinc-iodine battery, and the capacity can reach about 630mAh/g, and the performance of the battery assembled by the zinc sulfate electrolyte added with zinc bromide and ethylene glycol is obviously improved.
FIG. 2 is a charge and discharge plot of a Zn// I 2 full cell assembled from example 2 zinc sulfate electrolyte containing methyltriphenyl phosphorus bromide and N, N-dimethylformamide at a current density of 1C. From fig. 2, it can be seen that the added organic additive methyltriphenyl phosphorus bromide can excite the four-electron reaction of the zinc-iodine battery, and the capacity can reach about 500mAh/g, and compared with the battery assembled by adding zinc bromide, the performance of the battery is obviously improved.
FIG. 3 is a charge and discharge plot of a Zn// I 2 full cell assembled from the zinc sulfate electrolyte containing tetrapropylammonium bromide and N, N-dimethylformamide of example 3 at a current density of 1C. From fig. 3, it can be seen that the added organic additive tetrapropylammonium bromide can excite the four-electron reaction of the zinc-iodine battery, and the capacity can reach about 580mAh/g, and the performance of the battery assembled by the zinc bromide is obviously improved compared with that of the battery assembled by the zinc bromide.
FIG. 4 is a charge and discharge plot at 1C current density for a Zn// I 2 full cell assembled from a zinc sulfate electrolyte containing zinc bromide and N, N-dimethylformamide in comparative example 2. From fig. 4, it can be seen that the battery assembled by the added organic additive zinc bromide has the performance of not exciting the four-electron reaction of the zinc-iodine battery.
Fig. 5 is a charge and discharge plot at 1C current density for a Zn// I 2 full cell assembled from a zinc sulfate electrolyte containing zinc bromide and ethylene glycol in comparative example 3. From fig. 5, it can be seen that the battery assembled by the added organic additive zinc bromide has the performance of not exciting the four-electron reaction of the zinc-iodine battery.
Fig. 6 is a long cycle comparison plot at room temperature of 25 ℃ for a symmetric zinc cell assembled using the zinc sulfate electrolyte containing methyltriphenylphosphorous bromide and N, N-dimethylformamide of example 2 and the zinc sulfate electrolyte containing zinc bromide of comparative example 1. As can be seen from the figure, the cycle life of the battery is significantly prolonged after the addition of the additive compared to when it is not added.
Fig. 7 is a long cycle comparison plot of a symmetric zinc cell assembled using the zinc sulfate electrolyte containing tetrapropylammonium bromide and N, N-dimethylformamide of example 3 and the zinc sulfate electrolyte containing zinc bromide of comparative example 1 at room temperature of 25 ℃. As can be seen from the figure, the cycle life of the battery is significantly prolonged after the addition of the additive compared to when it is not added.
FIG. 8 is a long cycle plot of a Zn// I 2 full cell at 1C current density for a zinc sulfate electrolyte containing 3-bromopropyl trimethylammonium bromide and ethylene glycol in example 1 of the present invention assembled with a zinc sulfate electrolyte containing zinc bromide in comparative example 1. It is clear from the above that in the zinc sulfate electrolyte containing 3-bromopropyl trimethylammonium bromide and ethylene glycol, the assembled full cell exhibits a higher reversible capacity, and after 700 charge and discharge cycles, the discharge capacity can still reach 600mAh g -1, and the cycle stability thereof exhibits a more remarkable advantage.
FIG. 9 is a long cycle plot of a Zn// I 2 full cell assembled from the zinc sulfate electrolyte containing methyltriphenylphosphorous bromide and N, N-dimethylformamide of example 2 of the present invention and the zinc sulfate electrolyte containing zinc bromide of comparative example 1 at a current density of 1C. It is clear from the above that in the zinc sulfate electrolyte containing methyltriphenyl phosphorus bromide and N, N-dimethylformamide, the assembled full cell exhibited a higher reversible capacity, and after 1000 charge and discharge cycles, the discharge capacity still reached 500mAh g -1, and the cycle stability exhibited a more remarkable advantage.
FIG. 10 is a long cycle plot of a Zn// I 2 full cell assembled from the zinc sulfate electrolyte containing tetrapropylammonium bromide and N, N-dimethylformamide of example 3 of the present invention and the zinc sulfate electrolyte containing zinc bromide of comparative example 1 at a current density of 1C. It is clear from the above that in the zinc sulfate electrolyte containing tetrapropylammonium bromide and N, N-dimethylformamide, the assembled full cell exhibited a higher reversible capacity, and after 1000 charge and discharge cycles, the discharge capacity could still reach 550mAh g -1, and the cycle stability exhibited a more remarkable advantage.
In conclusion, the ammonium/phosphorus-based electrolyte prepared by the invention introduces an isohalogen conversion chemistry into a zinc-iodine battery, and successfully excites and stabilizes the highly reversible four-electron redox reaction of the zinc-iodine battery from I - to I + through a high-efficiency halogen-to-halogen activation strategy. Based on the above, the zinc-iodine battery has greatly improved specific capacity, electrode potential and cycle performance. Br - is used as an activator, the four-electron reaction from I - to I + is promoted through the interaction between halogens, the kinetic obstruction can be effectively lightened, high capacity and energy density are provided, and an effective strategy is provided for improving the performance of the water-based zinc ion battery. The method has important significance for promoting the industrial mass production of the water-based zinc ion battery.
Finally, it is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
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| CN117594788A (en) * | 2023-11-22 | 2024-02-23 | 济南大学 | A zinc-iodine battery using bromide ions as activators and Ni-Fe-I LDH nanoflowers as electrode materials |
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