CN117080584A - Maltitol-containing aqueous zinc ion electrolyte additive and application thereof - Google Patents
Maltitol-containing aqueous zinc ion electrolyte additive and application thereof Download PDFInfo
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- CN117080584A CN117080584A CN202311229646.2A CN202311229646A CN117080584A CN 117080584 A CN117080584 A CN 117080584A CN 202311229646 A CN202311229646 A CN 202311229646A CN 117080584 A CN117080584 A CN 117080584A
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- 239000000845 maltitol Substances 0.000 title claims abstract description 77
- VQHSOMBJVWLPSR-WUJBLJFYSA-N maltitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-WUJBLJFYSA-N 0.000 title claims abstract description 77
- 235000010449 maltitol Nutrition 0.000 title claims abstract description 77
- 229940035436 maltitol Drugs 0.000 title claims abstract description 77
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims description 65
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical group O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000012983 electrochemical energy storage Methods 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 abstract description 73
- 229910052725 zinc Inorganic materials 0.000 abstract description 48
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 13
- 230000008021 deposition Effects 0.000 abstract description 12
- 230000006911 nucleation Effects 0.000 abstract description 11
- 238000010899 nucleation Methods 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 210000001787 dendrite Anatomy 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 230000002829 reductive effect Effects 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 5
- 230000002401 inhibitory effect Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 2
- 238000005137 deposition process Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 20
- 210000004027 cell Anatomy 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229960001763 zinc sulfate Drugs 0.000 description 8
- 229910000368 zinc sulfate Inorganic materials 0.000 description 8
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 6
- 239000000811 xylitol Substances 0.000 description 6
- 235000010447 xylitol Nutrition 0.000 description 6
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 6
- 229960002675 xylitol Drugs 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
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- 239000006258 conductive agent Substances 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
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- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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- 238000007086 side reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 150000005846 sugar alcohols Chemical class 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 208000012868 Overgrowth Diseases 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
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- 230000005684 electric field Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
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- 229920000620 organic polymer Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
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Classifications
-
- 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
- H01M10/38—Construction or manufacture
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a maltitol-containing aqueous zinc ion electrolyte additive and application thereof, belonging to the technical field of aqueous batteries, wherein the additive is maltitol, and maltitol molecules can be preferentially attached to the surface of a zinc metal anode through chemical adsorption in the zinc deposition process, so that direct contact between free water and the surface of the zinc metal is reduced, hydrogen evolution reaction of the free water and the surface of the zinc metal is reduced, generation of byproduct sulfate is inhibited, in addition, the maltitol-containing zinc ion battery can generate larger nucleation overpotential, the larger nucleation overpotential can promote formation of a finer grain zinc deposition layer, and meanwhile, the increase of nucleation sites and the reduction of nucleation speed can be caused, thereby inhibiting growth of zinc dendrites, and facilitating uniform deposition of zinc ions on the surface of the zinc metal anode.
Description
Technical Field
The invention belongs to the technical field of water-based batteries, and particularly relates to a maltitol-containing water-based zinc ion electrolyte additive and application thereof.
Background
Aqueous Zinc Ion Batteries (ZIBs) are considered to be very potential energy storage systems due to the characteristics of good safety, low cost, environmental friendliness and the like, and have been widely studied, and at present, although rapid progress is made in the research of high-performance cathode materials, the research on zinc cathodes has been insufficient. For example, a zinc anode with high thermodynamic activity is extremely easy to react with aqueous electrolyte to generate hydrogen evolution reaction, so that the corrosion rate is accelerated, and irreversible byproducts are formed. In most alkaline electrolytes, zinc can spontaneously form corrosive microcells to produce severe dendrites and non-conductive passivation byproducts, such as Zn (OH), due to the fact that zinc is below the redox potential of hydrogen 2 Resulting in a degradation of battery capacity and a decrease in coulombic efficiency.
In order to address the inherent shortcomings of zinc cathodes, many strategies have been proposed by those skilled in the art to improve zinc cathode performance and cathode protection. The current method for solving the problems of corrosion and dendrite of the water-based zinc ion battery is mainly divided into two categories, namely zinc cathode modification and electrolyte optimization. Among these, electrolyte optimization is a simple, effective and easily implemented method of inhibiting dendrite formation and growth. The electrolyte additive commonly used at present is mainly an organic polymer electrolyte additive, can be selectively adsorbed at a zinc deposition site, induces the ion concentration and the electric field near a zinc cathode to be uniformly distributed, further improves the interface environment between the zinc cathode and the electrolyte, and avoids overgrowth of zinc dendrites, but has the defect of poor circulation stability.
Disclosure of Invention
In order to solve the technical problems, the invention provides the aqueous zinc ion electrolyte additive containing maltitol and the application thereof, wherein the electrolyte additive can be attached to the surface of a zinc metal anode through chemical adsorption, so that zinc deposition is more uniform and slower, a larger nucleation overpotential can promote the formation of a finer grain zinc deposition layer, and simultaneously, nucleation sites and nucleation speed can be reduced, thereby inhibiting the growth of zinc dendrites, and finally improving the electrochemical stability and the cycle life of the aqueous zinc ion battery. The invention has the characteristics of simple process, low cost, green environmental protection and the like, and has great significance for promoting the improvement of the cycle life of the water system zinc ion battery and commercialization.
In order to achieve the above object, the present invention provides an aqueous zinc ion electrolyte additive containing maltitol, wherein the additive in the aqueous zinc ion electrolyte is maltitol.
The action mechanism of xylitol and maltitol is different, xylitol molecules directionally reconstruct an electrolyte hydrogen bond network through hydrogen bonds, and expel active water molecules to regulate and control zinc ion transmission and deposition, and after maltitol is added into a water system zinc ion electrolyte, the maltitol is adsorbed on the surface of a zinc electrode through chemical action, so that water in the electrolyte is prevented from directly contacting with the zinc electrode to form a protective film, thereby inhibiting side reactions related to the zinc electrode and water, and further slowing down the growth of zinc dendrites. Compared with xylitol which is a common additive in the prior art, the maltitol has great advantages in performance compared with xylitol, and the battery added with the maltitol can stably circulate for more than 2000 hours, while the battery added with the xylitol can only stably circulate for about 1100 hours.
Further, the concentration of maltitol in the aqueous zinc ion electrolyte is 0.01mol/L to 0.1mol/L (i.e., 10mM to 100 mM).
The application of the maltitol-containing aqueous zinc ion electrolyte additive in an aqueous zinc ion battery or a zinc ion electrochemical energy storage device.
The aqueous zinc ion electrolyte comprises a solvent, an electrolyte and the maltitol-containing aqueous zinc ion electrolyte additive.
Further, in the aqueous zinc ion electrolyte, the solvent is deionized water; the electrolyte is zinc sulfate heptahydrate and/or manganese sulfate monohydrate.
Further, the concentration of the zinc sulfate heptahydrate in the water-based zinc ion battery electrolyte is 1 mol/L-3 mol/L.
Further, the concentration of the manganese sulfate monohydrate in the aqueous zinc ion battery electrolyte is 0.01mol/L to 0.3mol/L, and the manganese sulfate monohydrate supplements Mn consumed in the working process of the full battery 2+ 。
The aqueous zinc ion battery electrolyte is applied to an aqueous zinc ion battery or a zinc ion electrochemical energy storage device.
A water-based zinc ion battery consists of a positive electrode, a negative electrode, a diaphragm and the water-based zinc ion electrolyte.
Further, the positive electrode active material in the water-based zinc ion battery is MnO 2 The negative electrode material is zinc foil, and the separator material is glass fiber.
Further, the positive electrode active material MnO 2 The hydrothermal synthesis method is adopted to prepare: firstly, taking 5mmol K 2 MnO 4 Dissolved in 70mL H 2 In O, stirring clockwise by using a glass rod, adding 1.75mL of concentrated HCl (with the concentration of 12 mol/L) after dissolving, stirring at room temperature (25+/-2 ℃) for 30min, respectively transferring the mixture into 200mL of reaction kettles, and heating the reaction kettles in a drying box at 100 ℃ for 6h to obtain the anode active material MnO 2 。
Further, the positive electrode active material is MnO 2 The preparation method of the positive electrode comprises the following steps: mnO is firstly put into 2 Grinding conductive agent (Keqin black) with mortar, grinding, and adding MnO 2 Mixing conductive agent (Ketjen black) and binder (PVDF) at a mass ratio of 7:2:1, taking N-methyl pyrrolidone as a solvent, grinding uniformly in a mortar to obtain slurry, uniformly coating the ground slurry on a PE (polyethylene) film by using a 200 μm scraper on a coating infrared dryer, drying in a vacuum drying box, and cutting into positive electrode with a diameter of 12mm by using a cutting machineThe sheet is the positive electrode.
Compared with the prior art, the invention has the following advantages and technical effects:
the maltitol is used as the additive of the aqueous zinc ion battery electrolyte, preferably 1.8M ZnSO is used 4 As a basic electrolyte, maltitol molecules can be preferentially attached to the surface of a zinc metal anode through chemical adsorption in the zinc deposition process, so that direct contact between free water and the surface of the zinc metal is reduced, hydrogen evolution reaction of the free water and the surface of the zinc metal is reduced, generation of byproduct sulfate is inhibited, in addition, a zinc ion battery containing maltitol can generate larger nucleation overpotential, the larger nucleation overpotential can promote formation of a finer grain zinc deposition layer, and simultaneously, nucleation sites and nucleation speed are reduced, thereby inhibiting growth of zinc dendrites, and facilitating uniform deposition of zinc ions on the surface of the zinc metal anode.
In a word, the maltitol is used as an electrolyte additive, so that electrochemical side reaction and uncontrollable solid-liquid interface reaction on the surface of the zinc negative electrode can be effectively inhibited, and the problems of zinc corrosion and passivation of the zinc negative electrode are relieved. The maltitol has wide sources, low price, green environmental protection and large-scale production, and has important significance for constructing the water-based zinc ion battery with high performance, safety, environmental protection and low cost.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is a graph showing contact angle measurements of the electrolyte used in example 1 (a) and comparative example 1 (b).
Fig. 2 is an SEM topography after 50 turns of zinc electrodes in example 1 and comparative example 1 were deposited in the electrolyte, wherein (a), (c) are example 1, (b), (d) are comparative example 1, (a), (b) are SEM topography at 200 and 2000 magnifications, respectively, and (c), (d) are SEM topography at 200 and 2000 magnifications, respectively.
FIG. 3 is a schematic diagram of example 1 (1.8M ZnSO 4 +30mM maltiol) and comparative example 1 (1.8M ZnSO 4 ) The rate performance of Zn// Zn symmetric cells.
FIG. 4 is a schematic diagram of example 1 (1.8M ZnSO 4 +30mM maltitol) and comparative example 1 (1.8M ZnSO 4 ) The cycle performance of Zn// Zn symmetric cells.
FIG. 5 is a schematic diagram of example 2 (1.8M ZnSO 4 +30mM maltitol) and comparative example 2 (1.8M ZnSO 4 ) Tafel plot of assembled aqueous zinc ion three electrode cell.
FIG. 6 is a schematic diagram of example 3 (1.8M ZnSO 4 +30mM maltitol) and comparative example 3 (1.8M ZnSO 4 ) Assembled water-based zinc ion battery Zn// MnO 2 Is a graph of the rate performance of (2).
FIG. 7 is a schematic diagram of example 3 (1.8M ZnSO 4 +30mM maltitol) and comparative example 3 (1.8M ZnSO 4 ) Assembled water-based zinc ion battery Zn// MnO 2 Long cycle performance diagram of (2), wherein ZnSO 4 CE is comparative example 3 (1.8M ZnSO 4 ) Assembled water-based zinc ion battery Zn// MnO 2 Coulombic efficiency, znSO 4 +30mM Maltol-CE as example 3 (1.8M ZnSO 4 +30mM maltitol) assembled aqueous zinc ion cell Zn// MnO 2 Is a coulomb efficiency of (c).
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, 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. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The room temperature in the examples of the present invention is 25.+ -. 2 ℃ unless otherwise indicated.
Example 1
(1) Dispersing 2.588g zinc sulfate in deionized water, preparing 5mL solution at constant volume, magnetically stirring at room temperature until zinc sulfate is completely dissolved, and standing to obtain 1.8M ZnSO 4 And (3) an electrolyte.
(2) Taking 5mL of the ZnSO 4 To the electrolyte, 0.0516g of maltitol was added, and the mixture was magnetically stirred at room temperature until the maltitol was completely dissolved, and then allowed to stand to obtain an aqueous zinc ion electrolyte containing 30mM maltitol.
Example 2
25.88g of zinc sulfate and 0.2582g of maltitol are dispersed in deionized water, 25mL of solution is prepared by constant volume, then the solution is magnetically stirred at room temperature until the zinc sulfate and the maltitol are completely dissolved, an aqueous zinc ion electrolyte containing 30mM of maltitol is obtained, and then the electrolyte is transferred to a 25mL three-electrode reaction tank. Cutting two areas of 1cm 2 *1cm 2 The zinc sheet is used as a working electrode and a reference electrode, agCl is used as the reference electrode to form a three-electrode system, and the Tafel test is carried out on the three-electrode system by using a Chen Hua electrochemical workstation.
Example 3
The present example differs from example 1 only in that 0.1M MnSO is also added to the electrolyte 4 。
Example 4
(1) Dispersing 4.313g of zinc sulfate in deionized water, preparing 5mL of solution at constant volume, magnetically stirring at room temperature until the zinc sulfate is completely dissolved, and standing to obtain 3M ZnSO 4 And (3) an electrolyte.
(2) Taking 5mL of the ZnSO 4 To the electrolyte, 0.086g of maltitol was added, and the mixture was magnetically stirred at room temperature until maltitol was completely dissolved, and then allowed to stand to obtain an aqueous zinc ion electrolyte containing 10mM maltitol.
Example 5
(1) Dispersing 1.438g zinc sulfate in deionized water, preparing 5mL solution at constant volume, magnetically stirring at room temperature until the zinc sulfate is completely dissolved, and standing to obtain 1M ZnSO 4 And (3) an electrolyte.
(2) Taking 5mL of the ZnSO 4 To the electrolyte, 0.43g of maltitol was added, and the mixture was magnetically stirred at room temperature until maltitol was completely dissolved, and then allowed to stand to obtain an aqueous zinc ion electrolyte containing 50mM maltitol.
Example 6
ZnSO 4 The preparation process of the electrolyte is the same as in example 1, 5mL of ZnSO is taken 4 To the electrolyte, 0.86g of maltitol was added, and the mixture was magnetically stirred at room temperature until maltitol was completely dissolved, and then left to stand, whereby an aqueous zinc ion electrolyte containing 100mM maltitol was obtained.
Example 7
The present example differs from example 1 only in that 0.01M MnSO is also added to the electrolyte 4 。
Example 8
The present example differs from example 1 only in that 0.3M MnSO is also added to the electrolyte 4 。
Comparative example 1
In comparison with example 1, only 1.8M ZnSO free of maltitol was prepared without maltitol addition 4 And (3) an electrolyte.
Comparative example 2
The only difference compared to example 2 is that all zinc ion electrolytes in the three-electrode system do not contain maltitol additives.
Comparative example 3
In comparison with example 3, only the maltitol was not added, 1.8M ZnSO free of maltitol was prepared 4 And 0.1M MnSO 4 And (3) an electrolyte.
The electrolyte prepared above is assembled into Zn// Zn symmetric cell and Zn// MnO 2 Full cell and charge and discharge tests were performed on a blue cell test system.
The zinc ion electrolytes prepared in example 1 and comparative example 1 were subjected to contact angle measurement with a contact angle meter, respectively, as shown in fig. 1 (a) and (b), and contact angles thereof were 57 ° and 96 °, respectively. The contact angle of the electrolyte added with maltitol on the zinc foil becomes smaller, which shows that the water-based zinc ion electrolyte containing maltitol has larger adsorption energy on the zinc foil, and maltitol molecules are easier to adsorb on the surface of the zinc foil than water molecules in a battery, so that the direct contact of the water molecules and the zinc metal anode can be blocked, and the hydrogen evolution corrosion reaction at the interface of the zinc metal anode and the electrolyte is relieved.
FIG. 2 shows the Zn// Zn symmetry cells of example 1 and comparative example 1 at a current density of 1mA/cm 2 Deposition capacity of 1mAh/cm 2 SEM images after 50 cycles of the test conditions of (a) and (b) are Zn// Zn symmetrical cells assembled from the electrolyte of example 1, and (c) and (d) are Zn// Zn symmetrical cells assembled from the electrolyte of comparative example 1. As can be seen from (a) and (c), the surface of the zinc anode containing maltitol is smoother than that of the zinc anode not containing maltitol, zinc ions are deposited on the surface of the zinc anode in a large proportion, and (c) is remarkableThe obtained zinc ions are randomly deposited on the surface of the zinc anode, and the further enlarged (b) and (d) show that the surface of the zinc anode without maltitol has cellular byproducts.
FIG. 3 shows the Zn// Zn symmetry cells of example 1 and comparative example 1 at a current density of 1mA/cm 2 、3mA/cm 2 、5mA/cm 2 、10mA/cm 2 Deposition capacity of 1mAh/cm 2 Rate performance plot under test conditions. It can be seen that the battery containing maltitol shows a more stable voltage distribution than the battery without maltitol, and furthermore, when the current density was restored to 10mA/cm 2 When the battery containing maltitol is still working properly, but the battery without maltitol has already been short-circuited, which proves that the maltitol additive contributes to the improvement of the rate performance of the zinc ion battery.
FIG. 4 shows the Zn// Zn symmetry cells of example 1 and comparative example 1 at a current density of 1mA/cm 2 Deposition capacity of 1mAh/cm 2 Is a graph of cycle performance under test conditions. It can be seen that the cycle life of the battery containing maltitol can reach more than 2500 hours, and the battery without maltitol is short-circuited only about 160 hours, which proves that the maltitol additive can remarkably improve the cycle life of the zinc ion battery.
FIG. 5 is Tafel curves of aqueous zinc ion three-electrode cells measured in example 2 and comparative example 2, and it can be seen that the corrosion current of the maltitol-containing three-electrode cell is 8.750X 10 -4 mA/cm 2 Is far less than 4.830 ×10 in corrosion current of a three-electrode battery without maltitol -3 mA/cm 2 . This demonstrates that the maltitol additive can slow down the corrosion of aqueous zinc ion electrolyte to battery pole pieces. Other sugar alcohol additives such as xylitol are mainly prepared by adjusting Zn in the shell layer of the main solvent 2+ And H is 2 O molecules and SO 4 2- Ion interactions and directional reconstruction through hydrogen bonding to enhance ion movement and inhibit HER; however, maltitol is chemically adsorbed on the surface of zinc foil to prevent water molecules from directly contacting with zinc metal anode, thereby relieving the interface between zinc metal anode and electrolyteThe hydrogen evolution corrosion reaction at the face, which is not achieved by other kinds of sugar alcohols.
FIG. 6 is an illustration of the assembly of Zn// MnO with aqueous zinc ion electrolytes prepared in example 3 and comparative example 3 2 Full cell with a current density of 0.2A/g, 0.5A/g, 1A/g, 2A/g, 4A/g and a deposition capacity of 1mAh/cm 2 Rate performance under test conditions. It can be seen that the battery containing maltitol has higher specific capacity, and the stable specific capacity can be maintained after the current density is recovered to 0.2A/g, and the battery has better reversibility than the battery without maltitol, which indicates that the electrochemical performance of the battery can be improved by adding maltitol.
FIG. 7 is an illustration of the assembly of Zn// MnO by aqueous zinc ion electrolytes prepared in example 3 and comparative example 3 2 And (3) a full battery. It can be seen that the battery capacity with maltitol decays more slowly than the battery capacity without maltitol and has higher coulombic efficiency and capacity retention.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (10)
1. The aqueous zinc ion electrolyte additive containing maltitol is characterized in that the additive in the aqueous zinc ion electrolyte is maltitol.
2. The maltitol-containing aqueous zinc ion electrolyte additive according to claim 1, wherein the concentration of maltitol in the aqueous zinc ion electrolyte is 0.01mol/L to 0.1mol/L.
3. Use of the maltitol-containing aqueous zinc ion electrolyte additive according to any one of claims 1 to 2 in an aqueous zinc ion battery or a zinc ion electrochemical energy storage device.
4. An aqueous zinc ion electrolyte, characterized in that the aqueous zinc ion battery electrolyte consists of a solvent, an electrolyte and the maltitol-containing aqueous zinc ion electrolyte additive according to claim 1 or 2.
5. The aqueous zinc ion electrolyte according to claim 4, wherein the solvent is deionized water; the electrolyte is zinc sulfate heptahydrate and/or manganese sulfate monohydrate.
6. The aqueous zinc ion electrolyte according to claim 5, wherein the concentration of zinc sulfate heptahydrate in the aqueous zinc ion electrolyte is 1mol/L to 3mol/L.
7. The aqueous zinc ion electrolyte according to claim 5, wherein the concentration of manganese sulfate monohydrate in the aqueous zinc ion electrolyte is 0.01mol/L to 0.3mol/L.
8. Use of the aqueous zinc ion electrolyte according to any one of claims 4 to 7 in an aqueous zinc ion battery or a zinc ion electrochemical energy storage device.
9. An aqueous zinc ion battery comprising a positive electrode, a negative electrode, a separator and the aqueous zinc ion electrolyte according to any one of claims 4 to 7.
10. The aqueous zinc-ion battery according to claim 9, wherein the positive electrode active material is MnO 2 The negative electrode material is zinc foil, and the separator material is glass fiber.
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