CN108428950B - Aqueous solution electrolyte with wide decomposition voltage - Google Patents

Aqueous solution electrolyte with wide decomposition voltage Download PDF

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CN108428950B
CN108428950B CN201810459165.3A CN201810459165A CN108428950B CN 108428950 B CN108428950 B CN 108428950B CN 201810459165 A CN201810459165 A CN 201810459165A CN 108428950 B CN108428950 B CN 108428950B
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zinc
aqueous
sodium
electrolyte
decomposition voltage
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CN108428950A (en
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蒋凯
李威
王康丽
程时杰
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • 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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  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention belongs to the technical field of aqueous solution batteries, and discloses an aqueous solution electrolyte with wide decomposition voltage, wherein the concentration of sodium ions in the aqueous solution electrolyte is not lower than 5 mol/L, and the decomposition voltage is higher than 1.23V.

Description

Aqueous solution electrolyte with wide decomposition voltage
Technical Field
The invention belongs to the technical field of aqueous solution batteries, and particularly relates to an aqueous solution electrolyte with wide decomposition voltage.
Background
The rechargeable aqueous battery uses a cheap, non-flammable and green aqueous solution as an electrolyte, and has obvious cost and safety advantages in the field of large-scale energy storage compared with a non-aqueous battery. However, limited by the low decomposition voltage of water (theoretical decomposition voltage 1.23V), the energy density and cycle performance of the water-based battery are far from satisfactory. Therefore, broadening the decomposition voltage of the aqueous electrolyte and reducing the solubility of the electrode material in the aqueous solution are key to improving the energy density and cycle performance of the aqueous battery. The aqueous electrolyte reported at present basically cannot give consideration to the widening of the decomposition voltage of the electrolyte and the improvement of the stability of an electrode in the electrolyte. The common method, such as adjusting the pH value of the aqueous solution, can achieve the purpose of reducing the solubility of the electrode material in the aqueous solution, but cannot widen the decomposition voltage of the aqueous solution; the addition of a certain amount of surfactant to the electrolyte can increase the overpotential for hydrogen or oxygen evolution to some extent, but cannot reduce the solubility of the electrode material in an aqueous solution. Therefore, the development of high performance aqueous electrolytes is a serious challenge for current aqueous batteries.
Disclosure of Invention
Aiming at the problems existing in the prior art in widening the decomposition voltage of an electrolyte or improving the stability of an electrode in an aqueous solution, the invention aims to provide an aqueous solution electrolyte with wide decomposition voltage, wherein the electrolyte contains high-concentration sodium ions by controlling the concentration of the sodium ions in the aqueous solution electrolyte, the decomposition voltage of the aqueous solution electrolyte can be simultaneously widened, and the solubility of an electrode material in the aqueous solution is reduced, and the electrolyte can be particularly used as an aqueous zinc-based battery, so that the energy density and the cycle performance of the aqueous battery are finally improved, and the electrolyte has the characteristics of simple preparation, high stability, low cost, environmental protection, safety and no harm.
To achieve the above object, according to one aspect of the present invention, there is provided a wide decomposition voltage aqueous electrolyte, characterized in that the concentration of sodium ions in the aqueous electrolyte is not less than 5 mol/L and the decomposition voltage thereof is higher than 1.23V.
As a further preference of the present invention, the concentration of sodium ions in the aqueous electrolyte is preferably 5 mol/L to 25 mol/L.
As a further preferred aspect of the present invention, the sodium ions in the aqueous electrolyte are derived from sodium salts, and the sodium salts are preferably one or more of sodium perchlorate, sodium sulfate, sodium nitrate, sodium trifluoromethanesulfonate, and sodium bis-fluorosulfonylimide.
In a further preferred embodiment of the present invention, the aqueous electrolyte further contains zinc ions, and the concentration of the zinc ions in the aqueous electrolyte is preferably 0 to 4 mol/L.
As a further preferred aspect of the present invention, the zinc ion in the aqueous electrolyte is derived from a zinc salt, and the zinc salt is preferably one or more of zinc trifluoromethanesulfonate, zinc perchlorate, zinc sulfate, zinc acetate, and zinc nitrate.
According to another aspect of the present invention, there is provided an aqueous zinc-based battery using an aqueous electrolyte having the above-described wide decomposition voltage.
Through the technical scheme, compared with the prior art, the electrolyte always has high-concentration sodium salt (the concentration of sodium ions is not lower than 5 mol/L, for example, 5 mol/L-25 mol/L), can be hybridized with free water molecules, reduces the activity of the free water molecules, and improves the overpotential of hydrogen evolution and oxygen evolution, so that the decomposition voltage of the aqueous solution is widened (the decomposition voltage is higher than the theoretical decomposition voltage of pure water by 1.23V, for example, up to 2.5V).
The invention preferably uses highly soluble sodium salts, i.e. sodium salts having a solubility in water at ambient temperature of not less than 5 mol/L, such as sodium bis-fluorosulfonylimide which has a very high solubility in water, up to 26 mol/L, while other sodium salts having a lower solubility in aqueous solutions at ambient temperature (especially less than 5 mol/L) are not suitable for use in the invention-1) However, the aqueous solution with high sodium ion concentration (20 mol/L sodium bis (fluorosulfonyl) imide or 10 mol/L sodium perchlorate) of the invention has higher sodium ion conductivity (more than 80mS cm)-1). Furthermore, the sodium salt generally exhibits acidity (pH) when dissolved in water<5) To a certain extent, other parts of the cell are corroded, while the aqueous electrolyte according to the invention (e.g. 10 mol/L sodium perchlorate) is more neutral (pH 6-7), reducing the risk of corrosion.
The electrolyte has the characteristics of simple preparation method, such as capability of directly dissolving water-soluble sodium salt (or simultaneously comprising water-soluble zinc salt) in solvent water, and capability of forming the water-soluble electrolyte with the wide decomposition voltage of sodium ion concentration of not less than 5 mol/L by controlling the sodium ion concentration (the sodium salt selected by the invention can also be weak acid salt, and the pH value of the water solution after being dissolved in water is between 5 and 7), wide material source, low cost, environmental friendliness, safety and harmlessness, and is a water-based electrolyte with very high application potential.
Drawings
FIG. 1 is a graph showing cyclic voltammograms in an aqueous electrolyte prepared in example 1 according to the present invention.
FIG. 2 is a graph showing the phenomenon of dissolution of the positive electrode material in the aqueous electrolyte prepared in example 1 according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
Weigh 80mmol of NaClO4And 4mmol Zn (CF)3SO3)2Dissolved in deionized water, and then the solution is prepared into 8 mol/L NaClO by a volumetric flask4+0.4mol/L Zn(CF3SO3)2To obtain an aqueous electrolyte having a wide decomposition voltage as described in example 1, 8 mol/L NaClO obtained4+0.4mol/L Zn(CF3SO3)2The water solution is electrolyte, the titanium net is a working electrode, the zinc sheet is a reference electrolysis and counter electrode, a button cell is assembled to test the electrochemical performance of the button cell, and the cyclic voltammetry curve is shown in figure 1. Fig. 1 shows that the prepared aqueous electrolyte has a decomposition voltage of 2.5V. Adding positive electrode material (such as Na)3V2(PO4)2F3Material) was charged and discharged to a certain voltage (e.g., to 1.7V and 1.9V, and then to 1.6V and 0.8V), and then placed in the electrolyte, and the change of the electrolyte was observed, as shown in fig. 2. The positive electrode material in FIG. 2 is Na3V2(PO4)2F3Materials, in particular to the positive electrode materialsCharging to 1.7V and 1.9V, and discharging to 1.6V and 0.8V, respectively, wherein the left graph in FIG. 2 corresponds to low-concentration electrolyte and Na ion concentration is 1 mol/L (sodium salts are NaClO4) The Zn ion concentration is 0.4 mol/L (Zn (CF) is adopted as the zinc salt3SO3)2) The four test tubes in the left figure correspond to different charging voltage and/or discharging voltage respectively, the right figure in figure 2 corresponds to high-concentration electrolyte, the Na ion concentration is 8 mol/L (sodium salts adopt NaClO4) The Zn ion concentration is 0.4 mol/L (Zn (CF) is adopted as the zinc salt3SO3)2) The four test tubes in the right diagram also correspond to different charging voltages and/or discharging voltages, respectively. As shown in fig. 2, the prepared aqueous electrolyte can inhibit the dissolution of the electrode material; and the common electrolyte with low-concentration sodium salt shows obvious dissolution phenomenon.
Example 2
Weighing 90mmol of NaCF3SO3And 1.8mmol Zn (CF)3SO3)2Dissolved in deionized water and then the solution was made up to 9 mol/L NaCF using a volumetric flask3SO3+0.18mol/L Zn(CF3SO3)2To obtain an aqueous electrolyte having a wide decomposition voltage of 2.7V as described in example 2.
Example 3
Weigh 80mmol of NaClO4And 2mmol Zn (ClO)4)2Dissolved in deionized water, and then the solution is prepared into 8 mol/L NaClO by a volumetric flask4+0.2mol/L Zn(ClO4)2To obtain an aqueous electrolyte having a wide decomposition voltage of 2.6V as described in example 3.
Example 4
Weigh 200mmol Na (FSO)2)2N and 4mmol Zn (CF)3SO3)2Dissolved in deionized water and then the solution was made up to 20 mol/L Na (FSO) using a volumetric flask2)2N+0.4mol/L Zn(CF3SO3)2To obtain an aqueous electrolyte having a wide decomposition voltage as described in example 4, and decomposing the electrolyteThe pressure can reach 2.8V.
Example 5
250mmol of Na (FSO) are weighed2)2N and 2mmol Zn (CF)3SO3)2Dissolved in deionized water and then the solution was made up to 25 mol/L Na (FSO) using a volumetric flask2)2N+0.2mol/L Zn(CF3SO3)2The aqueous electrolyte of example 5 was obtained with a wide decomposition voltage of 3.0V.
In addition to the sodium salt and the zinc salt used in the above embodiments, the sodium ion in the present invention can be derived from other water soluble sodium salt and zinc salt, such as inorganic sodium salt, etc. for example, the sodium salt is not limited to the above embodiments, and can be sodium nitrate, sodium bis-fluorosulfonylimide or other forms of sodium salt.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (5)

1. An aqueous zinc-based battery is characterized in that an electrolyte adopted by the aqueous zinc-based battery is an aqueous electrolyte with wide decomposition voltage, the concentration of sodium ions in the aqueous electrolyte with wide decomposition voltage is not lower than 5 mol/L, and the decomposition voltage of the aqueous electrolyte is higher than 1.23V, wherein the aqueous electrolyte also contains zinc ions;
the aqueous electrolyte can broaden the decomposition voltage of the aqueous electrolyte, and can reduce the solubility of the positive electrode material in the aqueous electrolyte.
2. The aqueous zinc-based battery according to claim 1, wherein the concentration of sodium ions in the electrolyte of the aqueous solution is 5 mol/L-25 mol/L.
3. The aqueous zinc-based battery according to claim 1, wherein the sodium ions in the aqueous electrolyte are derived from sodium salts, and the sodium salts are one or more of sodium perchlorate, sodium sulfate, sodium nitrate, sodium triflate, and sodium bis-fluorosulfonylimide.
4. The aqueous zinc-based battery according to claim 1, wherein the concentration of the zinc ions in the aqueous electrolyte is not higher than 4 mol/L.
5. The aqueous zinc-based battery according to claim 1, wherein the zinc ions in the aqueous electrolyte are derived from zinc salts, and the zinc salts are one or more of zinc trifluoromethanesulfonate, zinc perchlorate, zinc sulfate, zinc acetate and zinc nitrate.
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US20230039527A1 (en) * 2020-02-10 2023-02-09 King Abdullah University Of Science And Technology Cathode and electrolyte chemistry for scalable zinc ion battery
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103219542A (en) * 2012-01-19 2013-07-24 中国科学院物理研究所 High-salinity non-aqueous electrolyte and use thereof
CN103413979A (en) * 2013-07-30 2013-11-27 复旦大学 Charge-discharge battery using zinc as negative electrode
CN107768741A (en) * 2017-09-18 2018-03-06 中国科学院青岛生物能源与过程研究所 Eutectic electrolyte and its application in secondary zinc battery

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JP5431452B2 (en) * 2008-04-07 2014-03-05 カーネギー メロン ユニバーシティ Aqueous electrolyte-based electrochemical secondary energy storage device using sodium ions
CN101840784A (en) * 2010-04-19 2010-09-22 中国科学院长春应用化学研究所 Electrolyte for super capacitor and super capacitor
JP5881587B2 (en) * 2012-11-29 2016-03-09 日本電信電話株式会社 Sodium secondary battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103219542A (en) * 2012-01-19 2013-07-24 中国科学院物理研究所 High-salinity non-aqueous electrolyte and use thereof
CN103413979A (en) * 2013-07-30 2013-11-27 复旦大学 Charge-discharge battery using zinc as negative electrode
CN107768741A (en) * 2017-09-18 2018-03-06 中国科学院青岛生物能源与过程研究所 Eutectic electrolyte and its application in secondary zinc battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Water-in-Salt" Electrolyte Makes Aqueous Sodium-Ion;Liumin Suo;《ADWANCED ENERGY MATERIALS》;20170731;第1-10页 *

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