CN115395010A - Aqueous dual-ion battery - Google Patents

Aqueous dual-ion battery Download PDF

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CN115395010A
CN115395010A CN202110564940.3A CN202110564940A CN115395010A CN 115395010 A CN115395010 A CN 115395010A CN 202110564940 A CN202110564940 A CN 202110564940A CN 115395010 A CN115395010 A CN 115395010A
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aqueous
ion battery
electrolyte
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positive electrode
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吕力
孙建国
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Chongqing New National University Research Institute
National University of Singapore
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/582—Halogenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

An aqueous bi-ion battery includes a negative electrode, a positive electrode, and an electrolyte interposed between the negative electrode and the positive electrode. The cathode is a metal oxyhalide capable of storing halogen anions, and the anode is a material capable of storing sodium ions. The metal oxyhalide of the negative electrode may be one of oxychloride, oxybromide, oxyiodide and oxyfluoride. The positive electrode capable of storing sodium ions and having reversible redox can be one of sodium vanadium phosphate, sodium titanium phosphate, oxide, prussian blue, iron-based prussian blue and other prussian blue derivatives. The electrolyte is sodium halide aqueous solution. The halogen element of the electrolytic solution is the same as the halogen element of the metal oxyhalide constituting the negative electrode. The electrolyte is preferably an aqueous sodium chloride solution, and the negative electrode is preferably bismuth oxychloride. The electrolyte solution may contain an additive, and the additive may form a solid electrolyte membrane on the surface of at least one of the negative electrode and the positive electrode. The additive may include urea and/or vinylene carbonate.

Description

Aqueous dual-ion battery
Technical Field
The invention relates to the field of batteries, in particular to a water system double-ion battery.
Background
The lithium ion battery widely used at present faces the problems of resource exhaustion, high cost and the like. In contrast, sodium ion batteries have gained attention. At present, the electrolyte of the sodium ion-based bi-ion battery has flammable characteristics and high cost, so the application and development of the bi-ion battery are hindered. The aqueous bi-ion battery also has problems of rapid capacity fading and battery failure due to dissolution of electrode materials, and the voltage window is limited by the decomposition voltage of water.
Accordingly, it is desirable to provide an aqueous bi-ion battery capable of solving the above problems.
Disclosure of Invention
According to one embodiment, the present invention provides an aqueous bi-ion battery including: the battery comprises a negative electrode, a positive electrode and electrolyte between the negative electrode and the positive electrode. The negative electrode is a metal oxyhalide capable of storing halogen anions; the positive electrode is a material capable of storing sodium ions.
Preferably, the metal oxyhalide is one of oxychloride, oxybromide, oxyiodide and oxyfluoride; the positive electrode material capable of storing sodium ions and having reversible redox is one of sodium vanadium phosphate, sodium titanium phosphate, oxide, prussian blue, iron-based Prussian blue and other Prussian blue derivatives; the electrolyte is sodium halide aqueous solution.
Preferably, the halogen element constituting the electrolytic solution is the same as the halogen element constituting the metal oxyhalide of the negative electrode.
Preferably, the electrolyte is a sodium chloride aqueous solution, and the metal oxyhalide is bismuth oxychloride.
Preferably, the aqueous dual-ion battery according to the present embodiment further includes an additive added to the electrolyte solution, and the additive may form a solid electrolyte membrane on a surface of at least one of the negative electrode and the positive electrode.
Preferably, the additive comprises urea. Further preferably, the concentration of the urea is 10mol/L.
Preferably, the additive further comprises vinylene carbonate. More preferably, the concentration of the urea is 10mol/L, and the addition ratio of the vinylene carbonate is 2vt%.
Preferably, the urea and the vinylene carbonate participate in a reaction and decomposition during a first cycle of charge and discharge of the bi-ion battery, so that a solid electrolyte membrane is formed on the surface of at least one of the negative electrode and the positive electrode.
Brief description of the drawings
Features of embodiments will be more fully understood in conjunction with the accompanying drawings, in which:
fig. 1 is a schematic diagram of a positive-negative cyclic voltammetry curve and a stability window of an electrolyte of a water-based bi-ion battery according to an embodiment of the present invention.
Fig. 2 is a schematic view of a cyclic voltammogram of a water-based bi-ion battery according to an embodiment of the present invention.
Fig. 3A is a schematic graph of a cycle profile of a water-based bi-ion battery in a saturated sodium chloride solution according to one embodiment of the invention.
Fig. 3B is a schematic diagram of the cycle curve of an aqueous bi-ion battery in an electrolyte solution with saturated sodium chloride solution and urea solution as additives according to an embodiment of the invention.
Fig. 3C is a schematic diagram of the cycling profile of an aqueous bi-ion battery according to an embodiment of the invention in an electrolyte solution of saturated sodium chloride solution urea solution and vinylene carbonate as an additive.
Fig. 4 is a graphical representation of long cycle test results for a water system bi-ion cell according to one embodiment.
Fig. 5A is a graphical comparison of cyclic voltammograms of a sodium vanadium phosphate anode of a water-based bi-ion battery in an electrolyte of a saturated sodium chloride solution in accordance with one embodiment.
Fig. 5B is a comparison graph of cyclic voltammetry curves for a vanadium sodium phosphate positive electrode of a water-based bi-ion battery in an electrolyte with a saturated sodium chloride solution and a urea solution as additives, according to an embodiment.
Fig. 5C is a comparison graph of cyclic voltammograms of a sodium vanadium phosphate anode of an aqueous bi-ion battery in an electrolyte of saturated sodium chloride solution and urea solution with vinylene carbonate as an additive, according to an example.
Fig. 6 is a graphical representation of redox peak intensity ratios of vanadium sodium phosphate positive electrodes of an aqueous bi-ion battery in different electrolytes according to an example.
Fig. 7 is a schematic view of cyclic voltammograms of a water-based bi-ion battery according to another embodiment.
Fig. 8 is a schematic view of a charge-discharge curve of a water system bi-ion battery according to another embodiment.
Fig. 9 is a schematic diagram of a long cycle test curve of a water system bi-ion cell according to another embodiment.
Detailed Description
The present invention relates to an aqueous bi-ion battery. According to one embodiment, the water-based dual-ion battery of the present invention includes a negative electrode made of a material that can store halogen anions, a positive electrode made of a material that can store sodium ions, and an electrolyte interposed between the negative electrode and the positive electrode. The negative electrode is made of a metal oxyhalide that can store halogen anions and has reversible redox characteristics. The metal oxyhalide may be, for example, a metal oxychloride, a metal oxybromide, a metal iodoxide, or a metal oxyfluoride. Specifically, the metal oxychloride can be bismuth oxychloride (BiOCl). The positive electrode is made of a material having reversible redox properties, including, for example, sodium vanadium phosphate (NaV) 2 (PO 4 ) 3 ) Titanium sodium phosphate, oxide, prussian blue, iron-based Prussian blue and other Prussian blue derivatives.
The halogen element in the electrolytic solution is the same as that of the metal oxyhalide constituting the negative electrode. For example, if the negative electrode is an oxychloride, the electrolyte is an aqueous sodium chloride solution; if the cathode of the double-ion battery is iodine oxide, the electrolyte is sodium iodide aqueous solution.
The electrolyte of the water-based bi-ion battery according to the present embodiment further includes an additive. The additive may form a solid electrolyte membrane on a surface of at least one of the negative electrode and the positive electrode. For example, urea and/or vinylene carbonate are/is used as an additive of the electrolyte of the water-based dual-ion battery, and the urea and the vinylene carbonate participate in reaction and decomposition in the first charge-discharge cycle process of the water-based dual-ion battery, so that a solid electrolyte membrane is formed on the surface of at least one electrode of a negative electrode and a positive electrode, and the effect of improving the electrical property of the water-based dual-ion battery is achieved.
According to one embodiment, the present invention provides an aqueous bi-ion battery in which the positive electrode of the battery is made of a material that can store sodium ions, such as sodium vanadium phosphate. The negative electrode of the cell is made of a material that can store halogen anions, such as bismuth oxychloride, and the electrolyte of the cell includes an aqueous sodium halide solution, such as an aqueous sodium chloride solution. The electrolyte of the aqueous double-ion battery may be a saturated sodium chloride aqueous solution, and a saturated urea solution, or a saturated sodium chloride aqueous solution, a saturated urea solution, and vinylene carbonate.
The manufacturing method of the bi-ion battery according to one example of the invention comprises the steps of uniformly stirring bismuth oxychloride, acetylene black and polyvinylidene fluoride in a solution of N-methyl pyrrolidone in a mass ratio of 7: 1, coating the mixture on a graphite paper substrate, drying the graphite paper substrate for 12 hours in vacuum at 120 ℃, and cutting the graphite paper substrate into a negative electrode wafer with the diameter of 12 mm. Simultaneously or sequentially, the manufacturing method further comprises the steps of uniformly stirring sodium vanadium phosphate and acetylene black, polyvinylidene fluoride in an N-methyl pyrrolidone solution in a mass ratio of 7. The manufacturing method further includes interposing an electrolyte between the negative electrode and the positive electrode to produce the aqueous bipolar battery according to the embodiment of the invention. The electrolyte may be a saturated aqueous sodium chloride solution. Preferably, the manufacturing method further comprises adding the additive to an aqueous sodium chloride solution. The additive may be urea and/or vinylene carbonate. The urea can be added in an amount of, for example, 10mol per liter. The vinylene carbonate may be added in a dose of, for example, 2% by volume (2 vt%).
Fig. 1 is a schematic diagram of a positive-negative cyclic voltammetry curve of a water-based bi-ion battery and a stable window of an electrolyte, specifically a cyclic voltammetry curve of a bismuth oxychloride negative electrode and a vanadium sodium phosphate positive electrode tested at a scan rate of 5 millivolts per second (mV/s) tested by a three-electrode system set at room temperature (23.5 ℃), with silver/silver chloride (Ag/AgCl) as a reference electrode and the electrolyte being a saturated sodium chloride (NaCl) aqueous solution, according to an embodiment of the present invention.
As shown in FIG. 1, the sodium vanadium phosphate positive electrode exhibited a strong pair of redox peaks (0.46V/0.56V) during cycling, which correspond to sodium ions (Na) + ) In the presence of sodium vanadium phosphate (Na) 3 V 2 (PO 4 ) 3 ) And embedding and extracting the positive electrode. The cathode of bismuth oxychloride (BiOCl) respectively presents two reduction peaks at-0.23V and-0.92V, and the two reduction peaks correspond to Bi in the BiOCl 3+ /Bi 0 With chloride ion (Cl) - ) Release from BiOCl negative electrode. During the forward scan, two oxidation peaks corresponding to the reduction peaks occur at-0.48 volts and-0.12 volts, respectively, corresponding to Bi in BiOCl 0 /Bi 3+ Is accompanied by the formation of BiOCl on the side of the negative electrode and thus to Cl - And storing. The above results demonstrate that BiOCl negative electrode and Na 3 V 2 (PO 4 ) 3 The positive electrodes can respectively store Cl - And Na + . At the same time, the redox potentials of the positive and negative electrodes are within the decomposition voltage window of the electrolyte.
Fig. 2 is a schematic view of a cyclic voltammogram of an aqueous bi-ion cell, specifically a cyclic voltammogram measured at a scan rate of 5 millivolts per second (mV/s) for a cell with bismuth oxychloride as the negative electrode and sodium vanadium phosphate as the positive electrode, at room temperature (23.5 ℃), with a voltage range of 0 to 1.5 volts, and the electrolyte being a saturated aqueous solution of sodium chloride, according to an embodiment of the present invention.
As shown in FIG. 2, a strong oxidation peak corresponding to Cl appears at 1.41V during charging - Release from BiOCl cathode and Na + From Na 3 V 2 (PO 4 ) 3 The release process of the positive electrode, the specific redox reaction of which is shown by the following formula:
negative electrode:
Figure BDA0003080363120000051
and (3) positive electrode:
Figure BDA0003080363120000052
during discharge, one reduction peak was present at 0.61 volts and the other at 0.93 volts. These two reduction peaks correspond to Cl - Storage in BiOCl cathode and Na + In Na 3 V 2 (PO 4 ) 3 The process of positive electrode storage, the specific redox reaction, is shown as the following formula:
negative electrode:
Figure BDA0003080363120000061
and (3) positive electrode:
Figure BDA0003080363120000062
fig. 3A is a schematic diagram of a cycle curve of a water system bi-ion battery in a saturated sodium chloride solution, specifically a battery with bismuth oxychloride as a negative electrode and sodium vanadium phosphate as a positive electrode at 200 milliamperes per gram (mA g) -1 ) And testing the obtained charge-discharge curve under the current density. Fig. 3B is a schematic diagram of a cycle curve of an aqueous bi-ion battery in an electrolyte of a saturated sodium chloride solution and a 10mol per liter (mol/L) urea solution, specifically a battery with bismuth oxychloride as a negative electrode and sodium vanadium phosphate as a positive electrode at 200 milliamperes per gram (mA g) according to an embodiment -1 ) And testing the obtained charge-discharge curve under the current density. FIG. 3C is a schematic graph showing the cycling profile of a water-based bi-ion battery at 200 milliamps per gram (mA g) for a battery having bismuth oxychloride as the negative electrode and sodium vanadium phosphate as the positive electrode in an electrolyte of a saturated sodium chloride solution, a 10 mole per liter (mol/L) urea solution, and 2vt% vinylene carbonate, according to one embodiment -1 ) And testing the obtained charge-discharge curve under the current density.
As shown in fig. 3A, 3B and 3C, when only the saturated sodium chloride solution is used as the electrolyte, the battery exhibits a pair of distinct voltage platforms at 0.65 v and 1.4 v during charging and discharging, which is consistent with the cyclic voltammetry test results, and the pair of charging and discharging platforms are almost unchanged in different electrolytes, but the specific capacity of the battery gradually increases with the addition of the electrolyte additive.
As shown in FIG. 3A, the cell was operated at 200 milliamps per gram (mA g) for a saturated sodium chloride solution as electrolyte -1 ) 53 mAh per gram (mAh g) can be obtained under the current density -1 ) The initial specific capacity (calculated as the amount of the positive electrode active material). As shown in FIG. 3B, the cell was operated at 200 milliamps per gram (mA g) with saturated NaCl and 10 moles per liter urea as electrolyte -1 ) 86 mAh per gram (mAh g) can be obtained under the current density -1 ) Initial specific capacity (calculated as the mass of the positive electrode). As shown in FIG. 3C, the cell was operated at 200 milliamps per gram (mA g), with saturated NaCl, 10 moles per liter urea, and 2vt% ethylene carbonate as electrolyte -1 ) 172 mAh per gram (mAh g) can be obtained under the current density -1 ) The initial specific capacity (calculated as the mass of the positive electrode). The initial specific capacity of the aqueous bi-ion battery according to this example was significantly higher than Na 3 V 2 (PO 4 ) 3 /NaV 2 (PO 4 ) 3 The theoretical capacity of the corresponding two electron conversions (-118 milliampere-hours per gram). The increase of the initial specific capacity is related to the reaction and decomposition of urea and vinylene carbonate in the Electrolyte and the formation of a Solid Electrolyte membrane (Solid Electrolyte membrane) on the surface of the electrode material in the first process.
FIG. 4 is a graphical representation of long cycle test results for a water system bi-ion battery, specifically a battery with bismuth oxychloride as the negative electrode and sodium vanadium phosphate as the positive electrode at 200 milliamps per gram (mA g), according to one embodiment -1 ) And (3) a charge-discharge cycle performance diagram under current density.
As shown in FIG. 4, the battery using saturated sodium chloride, 10mol/L urea and 2vt% ethylene carbonate as electrolyte can be at 200 milliamperes per gram (mA g) after the first 30 cycles of charging and discharging -1 ) A relatively stable 43.78 milliampere-hours per gram (mAh g) was obtained at the current density -1 ) Specific discharge capacity of (2). Through 200 times of charging and dischargingAfter electrical cycling, the cell can still attain 33.78 milliampere-hours per gram (mAh g) -1 ) The specific capacity of (a). The performance of the battery taking saturated sodium chloride, 10mol per liter of urea and 2vt percent of ethylene carbonate as electrolyte is far higher than that of the battery taking only saturated sodium chloride solution as electrolyte or taking saturated sodium chloride and 10mol per liter of urea as electrolyte.
Fig. 5A is a graphical comparison of cyclic voltammograms of a sodium vanadium phosphate anode in an electrolyte of a saturated sodium chloride solution, specifically different number of cycles of a sodium vanadium phosphate anode tested in a three electrode system set at 5 millivolts per second (mV/s) scan rate at room temperature (23.5 ℃) with silver/silver chloride (Ag/AgCl) as a reference electrode, according to an embodiment. Fig. 5B is a comparison graph of cyclic voltammograms of a sodium vanadium phosphate anode in an electrolyte of a saturated sodium chloride solution and 10 moles per liter (mol/L) urea solution, according to an embodiment. Specifically, the vanadium sodium phosphate positive electrode tested by the three-electrode system group at room temperature (23.5 ℃) is tested on cyclic voltammetry curves of different circles at a scanning rate of 5 millivolts per second (mV/s), and silver/silver chloride (Ag/AgCl) is used as a reference electrode. Fig. 5℃ is a comparative graph of cyclic voltammetry curves for a sodium vanadium phosphate anode in an electrolyte of a saturated sodium chloride solution, 10 moles per liter (mol/L) urea solution, and 2vt% vinylene carbonate, in particular for a sodium vanadium phosphate anode tested in a three-electrode system set at room temperature (23.5 ℃) for different cycles at a scan rate of 5 millivolts per second (mV/s), with silver/silver chloride (Ag/AgCl) as a reference electrode, according to an embodiment.
As shown in FIGS. 5A, 5B and 5C, na was added to a saturated sodium chloride electrolyte 3 V 2 (PO 4 ) 3 Structural failure after multiple cycles (e.g., 20 charge-discharge cycles), which in turn leads to Na 3 V 2 (PO 4 ) 3 Na in positive electrode + The degradation of storage capacity. However, when urea and vinylene carbonate are added to the electrolyte, na 3 V 2 (PO 4 ) 3 The structural damage condition of the catalyst is obviously improved, and the oxidation-reduction kinetic performance is obviously improved.
Fig. 6 is a graph showing the redox peak intensity ratios of the vanadium sodium phosphate positive electrode in different electrolytes, specifically, the redox peak intensity ratios of the forty th time/twentieth time and the sixty th time/twentieth time in electrolytes of (1) a saturated sodium chloride solution, (2) a saturated sodium chloride solution and 10 moles per liter (mol/L) of urea solution, (3) a saturated sodium chloride solution, 10 moles per liter (mol/L) of urea solution, and 2vt% of vinylene carbonate, respectively, according to an embodiment.
As shown in FIG. 6, after urea and vinylene carbonate were added to a saturated sodium chloride electrolyte, na was added 3 V 2 (PO 4 ) 3 Compared to Na in a saturated sodium chloride electrolyte with only urea added and in a saturated sodium chloride (without additives) electrolyte 3 V 2 (PO 4 ) 3 There is a significant enhancement. Therefore, the cycle stability of the aqueous double-ion battery with the saturated sodium chloride electrolyte added with urea and vinylene carbonate is obviously improved.
According to another embodiment, the present invention provides an aqueous bi-ion battery, wherein the positive electrode of the battery is iron-based prussian blue (Na) 2 FeFe(CN) 6 ) The cathode of the battery is bismuth oxychloride, and a saturated sodium chloride aqueous solution, a 10mol/L urea solution and 2vt% vinylene carbonate are used as electrolyte of the double-ion battery.
Preparing a battery: uniformly stirring bismuth oxychloride, acetylene black and polyvinylidene fluoride in an N-methyl pyrrolidone solution according to the mass ratio of 7. The iron-based prussian blue, acetylene black and polyvinylidene fluoride are uniformly stirred in an N-methyl pyrrolidone solution according to the mass ratio of 7. Saturated sodium chloride aqueous solution is used as electrolyte, and 10mol/L of urea and 2vt% of vinylene carbonate are added for modification.
Fig. 7 is a schematic view of cyclic voltammograms of a water-based diionic battery according to this example, specifically a cyclic voltammogram tested at room temperature (23.5 ℃) for a battery with bismuth oxychloride as the negative electrode and iron-based prussian blue as the positive electrode at a scan rate of 5 millivolts per second (mV/s), with a voltage interval of 0 to 1.5 volts, the electrolyte being a saturated aqueous sodium chloride solution, 10 moles per liter (mol/L) of urea solution, and 2vt% vinylene carbonate.
As shown in FIG. 7, two strong oxidation peaks appear at 0.33 volts and 1.14 volts during charging, which correspond to Cl - Liberation of Na from BiOCl cathode + From iron-based Prussian blue (Na) 2 FeFe(CN) 6 ) The release process at the positive electrode, the specific redox reaction of which is shown by the following formula:
negative electrode:
Figure BDA0003080363120000091
and (3) positive electrode:
Figure BDA0003080363120000092
during discharge, one reduction peak occurred at 0.19 volts and another reduction peak occurred at 0.63 volts. These two reduction peaks correspond to Cl - Storage in BiOCl cathode and Na + In Na 2 FeFe(CN) 6 The storage process of the positive electrode, the specific oxidation-reduction reaction, is shown as the following formula:
negative electrode:
Figure BDA0003080363120000093
and (3) positive electrode:
Figure BDA0003080363120000094
FIG. 8 is a schematic view showing a charge/discharge curve of an aqueous bi-ion battery according to another embodiment, specifically, a bismuth oxychloride electrode, an iron-based Prussian blue electrode, a saturated sodium chloride aqueous solution, a 10mol/L (mol/L) urea solution, and 2vt% of a vinylene carbonate electrodeThe electrolyte cell was operated at 200 milliamps per gram (mA g) -1 ) And testing the obtained charge-discharge curve under the current density.
As shown in fig. 8, the initial specific capacity per gram (calculated as the amount of positive electrode active material) of 17.86 milliamps per gram was obtained at a current density of 200 milliamps per gram for the cell with saturated sodium chloride, 10 moles per liter urea, and 2vt% ethylene carbonate as the electrolyte.
FIG. 9 is a schematic diagram of a long cycle test curve for a water-based bi-ion battery according to one embodiment, specifically a battery with bismuth oxychloride as the negative electrode, iron-based Prussian blue as the positive electrode, a saturated aqueous solution of sodium chloride, 10 moles per liter (mol/L) of urea solution, and 2vt% ethylene carbonate as the electrolyte at 200 milliamperes (mA g) -1 ) Charge and discharge cycle performance at current density.
As shown in fig. 9, when a saturated sodium chloride aqueous solution, 10mol/l urea and 2vt% ethylene carbonate are used as an electrolyte, the battery can obtain a relatively stable specific discharge capacity of 15.69 ma/g at a current density of 200 ma/g after the first 80 times of charging and discharging.
The foregoing has presented embodiments, specific examples and application scenarios of the present invention for purposes of illustration and description, but is not intended to be exhaustive or limiting. Many modifications and variations will be apparent to practitioners skilled in this art. The examples and embodiments were chosen and described in order to explain the principles of the invention and its practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.
Thus, although the illustrative example embodiments have been described herein with reference to the accompanying drawings, it is to be understood that such description is not limiting, and that various other changes and modifications may be affected therein by one skilled in the art without departing from the scope or spirit of the invention.

Claims (10)

1. An aqueous bi-ion battery, characterized in that the aqueous bi-ion battery comprises:
a negative electrode which is a metal oxyhalide capable of storing a halogen anion;
the positive electrode is a material capable of storing sodium ions;
an electrolyte interposed between the negative electrode and the positive electrode.
2. The aqueous bi-ion battery of claim 1, wherein the metal oxyhalide is one of oxychloride, oxybromide, oxyiodide, and oxyfluoride; the positive electrode material capable of storing sodium ions and having reversible redox is one of sodium vanadium phosphate, sodium titanium phosphate, oxide, prussian blue, iron-based Prussian blue and other Prussian blue derivatives; the electrolyte is sodium halide aqueous solution.
3. The aqueous bi-ion battery of claim 2, wherein a halogen element constituting the electrolyte solution is the same as a halogen element constituting the metal oxyhalide of the negative electrode.
4. The aqueous bi-ion battery of claim 3, wherein the electrolyte is an aqueous sodium chloride solution and the metal oxyhalide is bismuth oxychloride.
5. The aqueous bipolar battery according to claim 1, further comprising an additive added to the electrolyte solution, wherein the additive is capable of forming a solid electrolyte film on a surface of at least one of the negative electrode and the positive electrode.
6. The aqueous bi-ion battery of claim 5, wherein the additive comprises urea.
7. The aqueous bi-ion battery of claim 6, wherein the concentration of urea is 10mol/L.
8. The aqueous bi-ion battery of claim 6 or 7, wherein the additive further comprises vinylene carbonate.
9. The aqueous diionic battery according to claim 8, wherein the concentration of urea is 10mol/L and the addition ratio of vinylene carbonate is 2vt%.
10. The aqueous bi-ion battery according to claim 9, wherein the urea and the vinylene carbonate react and decompose during a first cycle of charge and discharge of the aqueous bi-ion battery, thereby forming a solid electrolyte film on a surface of at least one of the negative electrode and the positive electrode.
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