CN113707951A - Zinc gluconate electrolyte for zinc ion battery and application method thereof - Google Patents
Zinc gluconate electrolyte for zinc ion battery and application method thereof Download PDFInfo
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- CN113707951A CN113707951A CN202110768518.XA CN202110768518A CN113707951A CN 113707951 A CN113707951 A CN 113707951A CN 202110768518 A CN202110768518 A CN 202110768518A CN 113707951 A CN113707951 A CN 113707951A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 114
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 title claims abstract description 80
- 229960000306 zinc gluconate Drugs 0.000 title claims abstract description 80
- 235000011478 zinc gluconate Nutrition 0.000 title claims abstract description 80
- 239000011670 zinc gluconate Substances 0.000 title claims abstract description 80
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 98
- 239000011701 zinc Substances 0.000 claims abstract description 83
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 79
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 13
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 13
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000011592 zinc chloride Substances 0.000 claims abstract description 6
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 19
- 239000001257 hydrogen Substances 0.000 abstract description 19
- 210000001787 dendrite Anatomy 0.000 abstract description 18
- 238000005260 corrosion Methods 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 12
- 238000007086 side reaction Methods 0.000 abstract description 5
- 229940091251 zinc supplement Drugs 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 210000002784 stomach Anatomy 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 description 10
- 238000001000 micrograph Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 235000012208 gluconic acid Nutrition 0.000 description 4
- 239000000174 gluconic acid Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- ALAZBPVYKYPJEN-UHFFFAOYSA-K S(=O)(=O)([O-])[O-].O[Zn+2] Chemical compound S(=O)(=O)([O-])[O-].O[Zn+2] ALAZBPVYKYPJEN-UHFFFAOYSA-K 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002496 gastric effect Effects 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- VCPQWWKLNIMKND-UHFFFAOYSA-L zinc hydroxy sulfate Chemical compound [Zn++].OOS([O-])(=O)=O.OOS([O-])(=O)=O VCPQWWKLNIMKND-UHFFFAOYSA-L 0.000 description 1
Images
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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/01—Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
- C07C59/10—Polyhydroxy carboxylic acids
- C07C59/105—Polyhydroxy carboxylic acids having five or more carbon atoms, e.g. aldonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
-
- 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
Abstract
The invention discloses a zinc gluconate electrolyte for a zinc ion battery and an application method thereof, and discloses the zinc gluconate electrolyte for simultaneously improving the performance and the safety of the zinc ion battery, the electrolyte can avoid the growth of dendrites of a zinc cathode, avoid hydrogen evolution side reaction and prevent zinc corrosion so as to improve the performance of the battery, the problems of stomach corrosion and the like can not be caused by children eating the zinc gluconate by mistake, and the zinc gluconate can be used as a zinc supplement agent for children, has high safety, is a non-toxic high-safety zinc gluconate electrolyte for improving the performance of the zinc ion battery, has low cost and high safety performance, is expected to replace more currently used electrolytes such as zinc sulfate and zinc chloride, and has wide popularization and application prospects.
Description
Technical Field
The invention relates to the field of batteries, in particular to a zinc gluconate electrolyte for a zinc ion battery and an application method thereof.
Background
The zinc ion battery is widely concerned by people due to the advantages of high safety, low cost and the like, and the electrolyte used by the zinc ion battery at present has more solutes, wherein ZnSO is4Due to the comprehensive performance and low cost, the use is the most. However, zinc sulfate is used as electrolyte in zinc ion batteries, and zinc dendrite growth inevitably occurs on the zinc metal negative electrode, and meanwhile, the problems of hydrogen evolution side reaction, zinc corrosion and the like are caused, and the performance of the battery, particularly the service life of the battery is influenced.
(1) Mechanism of dendrite formation
Zinc dendrites are a common problem in alkaline zinc-based cells due to the high electrochemical activity of zinc metal, i.e., its thermodynamic instability in alkaline media. In alkaline electrolyte, the movement of zincate on the surface of the negative electrode is controlled by diffusion, and the zincate preferentially nucleates at favorable charge sites to form small tips, so that more zincate is attracted to aggregate in the subsequent charge and discharge processes, and finally zinc dendrites are formed. Zinc dendrites have a similar mechanism of formation in neutral and weakly acidic electrolytes. The zinc ions adsorbed on the surface of the electrode can be diffused along the surface in two dimensions, and the priority is given toThe nucleation sites accumulate nucleation and the initial protrusions further exacerbate the non-uniform distribution of the electric field in conventional liquid electrolytes. To reduce the surface energy and the area of the exposed region, the subsequent carriers (Zn)2+) There is a tendency to reduce the deposition at the existing protrusions, resulting in the growth of the protrusions and the eventual formation of dendrites. As can be seen from the above principle, the formation of dendrites is mainly attributed to the non-uniform electric field distribution on the surface of the negative electrode and the unrestricted two-dimensional diffusion of zinc ions.
(2) Mechanism of corrosion
Corrosion in zinc-based cells mainly includes self-corrosion and electrochemical corrosion, the former being mainly present in alkaline zinc-ion cells. Electrochemical corrosion as used herein refers to the irreversible consumption of zinc metal during charge and discharge cycles, and primarily includes zinc metal falling from the electrode into the electrolyte and inert byproducts. This section of the authors mainly teaches inert by-products. H different from hydroxyl zinc sulfate formed on the surface of the positive electrode+/Zn2+The co-intercalation mechanism, the formation of zinc hydroxy sulphate at the surface of the negative electrode is mainly due to electrostatic interactions and its limited solubility. During discharge, the zinc cathode is converted from zinc metal to zinc ions, which are charged with a net positive charge near its surface, which attracts SO4 in the electrolyte2-And OH-The complexation reaction occurs, and the formed hydroxyl zinc sulfate has very limited solubility, and will deposit on the surface of the negative electrode when the hydroxyl zinc sulfate is supersaturated in the electrolyte. The formation of these by-products can reduce the zinc deposition/stripping coulombic efficiency to some extent at the expense of continued consumption of electrolyte and active zinc ions. Therefore, the excess zinc needs to be provided to maintain the circulation in the actual energy storage process, which affects the full utilization of the theoretical capacity; inert by-products covering the electrode surface can hinder ion transport, thereby adversely affecting the reversibility of the zinc cathode.
(3) Mechanism of hydrogen evolution
In an aqueous battery, a hydrogen evolution reaction from a liquid phase to a gas phase occurs at an electrode/electrolyte interface, which increases the internal pressure of the battery, causing gradual swelling of the interior and damage to the sealed battery system. Moreover, hydrogen evolution inevitably affects the deposition of zinc, not only reducing CE, but also reducing the deposition of zincDue to OH-The concentration increases to cause local pH fluctuations, OH is generated-Which in turn promotes the production of ZSH by-products at the anode surface. In the alkaline electrolyte, the standard reduction potential (-1.26Vvs. SHE) of Zn/ZnO is lower than the hydrogen evolution potential (-0.83Vvs. SHE), and from the thermodynamic point of view, the hydrogen evolution reaction preferentially occurs in the reduction reaction of zinc oxide. Severe hydrogen evolution reactions can severely affect the cycle life, shelf life and capacity retention of the cell, limiting the practical application of alkaline zinc-based cells. In contrast, in a neutral electrolyte, Zn/Zn2+The standard reduction potential (-0.76vvs. she) is higher than the hydrogen evolution potential, and the hydrogen evolution reaction does not occur prior to the zinc ion deposition reaction from the thermodynamic perspective. In a weakly acidic environment, however, Zn/Zn2+Is lower than the hydrogen evolution potential (0vvs. she), a vigorous hydrogen evolution reaction tends to occur. However, in practice, the hydrogen evolution reaction on the metal surface of zinc can be suppressed and is not so severe because zinc has a high hydrogen evolution overpotential in a water system environment. However, in practice the hydrogen evolution overpotential is influenced by the electrode surface roughness, the operating temperature and the zinc ion concentration, among other kinetic factors. Therefore, hydrogen evolution is observed in weakly acidic electrolytes in some cases, resulting in poor cycle performance.
In addition, in view of the safety of batteries, such as gastric corrosion caused by children's improper feeding, it is also important to find a suitable high-safety electrolyte, such as ZnSO, which is currently used4、ZnCl2Is a strong corrosive agent, has stimulation to gastrointestinal tracts and is still not safe enough. Therefore, the invention discloses the zinc gluconate electrolyte for simultaneously improving the performance and the safety of the zinc ion battery. Researches find that the electrolyte can avoid dendritic growth of a zinc cathode, avoid hydrogen evolution side reaction and zinc corrosion, and further improve the performance of the battery. Meanwhile, the zinc gluconate is used as a zinc supplement for children, and has high safety.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a zinc gluconate electrolyte for a zinc ion battery and an application method thereof, and discloses the zinc gluconate electrolyte for simultaneously improving the performance and the safety of the zinc ion battery.
In order to realize the technical effects, the following technical scheme is adopted:
a zinc gluconate electrolyte for a zinc ion battery has a structural formula as follows:
further, the concentration of the zinc gluconate electrolyte is 0.1-0.3 mol/L;
further, the zinc gluconate electrolyte can be mixed with zinc sulfate or zinc chloride for use.
Further, the zinc gluconate electrolyte can be used as an electrolyte of a zinc ion battery;
further, the zinc gluconate electrolyte can be applied to zinc/carbon felt asymmetric battery electrolytes;
furthermore, the zinc gluconate electrolyte can be applied to zinc/zinc symmetrical battery electrolytes.
The invention has the beneficial effects that:
the invention discloses a zinc gluconate electrolyte capable of simultaneously improving the performance and safety of a zinc ion battery, which can avoid the growth of dendritic crystals of a zinc cathode, avoid hydrogen evolution side reaction and prevent zinc corrosion, further improve the performance of the battery, prevent the problems of stomach corrosion and the like caused by children eating by mistake, can be used as a zinc supplement agent for children, has high safety, is a non-toxic high-safety zinc gluconate electrolyte capable of improving the performance of the zinc ion battery, has low cost and high safety, is expected to replace more currently used electrolytes such as zinc sulfate and zinc chloride, and has wide popularization and application prospects.
Drawings
FIG. 1 is a micrograph of the original zinc foil from different electrolyte immersion experiments of zinc sheets in the examples of the present application
FIG. 2 is a micrograph of zinc foil soaked with 0.3mol/L zinc gluconate electrolyte for different electrolyte soaking experiments of zinc plate in the example of the application;
FIG. 3 is a micrograph of zinc foil soaked with 0.3mol/L zinc sulfate electrolyte for different electrolyte soaking experiments of zinc sheets in the example of the application;
FIG. 4 is a micrograph of a zinc foil soaked with 0.1mol/L zinc gluconate electrolyte in an example of the present application;
FIG. 5 is a micrograph of a zinc foil soaked with 0.2mol/L zinc gluconate electrolyte according to an embodiment of the present application;
FIG. 6 is a charge/discharge test chart of an asymmetric zinc/carbon felt battery with zinc gluconate electrolyte according to an embodiment of the present application;
FIG. 7 shows the current of 0.1mA cm in the present example-2A coulomb efficiency test chart of the zinc gluconate electrolyte zinc/carbon felt asymmetric battery;
FIG. 8 shows the current of 0.25mA cm in the present example-2A coulomb efficiency test chart of the zinc gluconate electrolyte zinc/carbon felt asymmetric battery;
FIG. 9 shows the current of 0.1mA cm in the present example-2A test chart of the cycle life of the zinc/zinc symmetrical battery with zinc gluconate electrolyte;
FIG. 10 shows the current of 0.25mA cm in the present example-2A test chart of the cycle life of the zinc/zinc symmetrical battery with zinc gluconate electrolyte;
FIG. 11 shows the current of 0.5mA cm in the present example-2A test chart of the cycle life of the zinc/zinc symmetrical battery with zinc gluconate electrolyte;
FIG. 12 shows 0.3mol/L ZnSO in the examples of the present application4SEM image of zinc foil after 10 cycles of electrolyte circulation;
FIG. 13 is an SEM image of a zinc foil after 10 cycles of 0.1mol/L zinc gluconate electrolyte in an example of the present application;
FIG. 14 is an SEM image of a zinc foil after 10 cycles of 0.2mol/L zinc gluconate electrolyte in an example of the present application;
FIG. 15 is an SEM image of a zinc foil after 10 cycles of 0.3mol/L zinc gluconate electrolyte in an example of the present application;
FIG. 16 shows the zinc foil density at 0.5mAh cm after 0.3mol/L zinc gluconate electrolyte in the example of the present application-2SEM images after amount of deposition;
FIG. 17 shows the zinc foil density at 0.1mAh cm after 0.3mol/L zinc gluconate electrolyte in the example of the present application-2SEM images after amount of deposition;
FIG. 18 shows the zinc foil concentration at 0.5mA cm after 0.3mol/L zinc gluconate electrolyte in the examples of the present application-2SEM pictures at current density;
FIG. 19 shows the results of the zinc foil concentration at 0.1mA cm after 0.3mol/L zinc gluconate electrolyte in the examples of the present application-2SEM pictures at current density;
FIG. 20 is a micrograph of a zinc foil after 3 cycles of zinc foil cycling after 0.3mol/L zinc gluconate electrolyte in an example of the present application;
FIG. 21 is a micrograph of zinc foil after 30 cycles of zinc foil cycling after 0.3mol/L zinc gluconate electrolyte in an example of the present application;
Detailed Description
The invention will be further described with reference to the accompanying drawings, without limiting the scope of the invention to the following:
example 1:
1. immersion experiment of zinc sheet with different electrolytes
The zinc sheet is respectively soaked in zinc gluconate and zinc sulfate solutions with the same concentration (0.3mol/L), as shown in fig. 1-3, fig. 1 is a micrograph of an original zinc foil, fig. 2 is a micrograph of the zinc foil soaked by the zinc gluconate solution with the concentration of 0.3mol/L, and fig. 3 is a micrograph of the zinc foil soaked by the zinc sulfate solution with the concentration of 0.3mol/L, it is found that the surface of the zinc sheet soaked by the traditional zinc sulfate solution is obviously corroded, but the surface of the zinc sheet soaked by the zinc gluconate is basically not corroded, which indicates that the zinc gluconate is used as the zinc ion battery electrolyte and is really beneficial to the stability of a zinc cathode.
2. Zinc tablet soaking experiment with zinc gluconate electrolyte solution with different concentrations
And respectively carrying out soaking experiments on zinc gluconate electrolyte zinc sheets with different concentrations, wherein the concentrations of the zinc gluconate electrolyte are respectively 0.1mol/L, 0.2mol/L and 0.3 mol/L. As shown in FIGS. 4-5, the zinc sheet soaked with 0.1mol/L and 0.2mol/L zinc gluconate has no corrosion on the surface, and the effect of 0.3mol/L concentration is the best.
3. Test of charge-discharge efficiency of zinc/carbon felt asymmetric battery using zinc gluconate with different concentrations as electrolyte
The zinc gluconate electrolyte with the concentration of 0.1mol/L, 0.2mol/L and 0.3mol/L is respectively used as the electrolyte to assemble the zinc/carbon felt asymmetric battery for charge and discharge tests, the experimental result is shown in figure 6, and the charge and discharge curve graph shows that the charge and discharge efficiency of the battery is the highest when the zinc gluconate electrolyte with the concentration of 0.3mol/L is used as the electrolyte.
4. Zinc gluconate with different concentrations as electrolyte-zinc/carbon felt asymmetric battery coulombic efficiency test
The zinc gluconate electrolyte with the concentration of 0.1mol/L, 0.2mol/L and 0.3mol/L is respectively used as the electrolyte to assemble the zinc/carbon felt asymmetric battery, and the zinc/carbon felt asymmetric battery is arranged under different currents (0.1mA cm)-2,1h，0.25mA cm-2And 1h) repeating the coulombic efficiency curve of charging and discharging for 1 hour, wherein the coulombic efficiency curve shows that the coulombic efficiency of the battery is highest when the gluconic acid with the concentration of 0.3mol/L is used as the electrolyte, as shown in figures 7-8.
5. Zinc/zinc symmetrical battery cycle life test with zinc gluconate with different concentrations as electrolyte
The zinc gluconate electrolyte with the concentration of 0.1mol/L, 0.2mol/L and 0.3mol/L is respectively used as the electrolyte to assemble the zinc/zinc symmetrical battery with the concentration of 0.1mA cm-2As shown in fig. 9, the cycle life graph of the battery in which charging and discharging were repeated for 1 hour under current showed that the cycle life of the battery was the longest when gluconic acid with a concentration of 0.3mol/L was used as the electrolyte.
The concentrations of the zinc gluconate electrolyte are respectively 0.1mol/L, 0.2mol/L and 0.3mol/L of the electrolyte is used as the electrolyte to assemble the zinc/zinc symmetrical battery at 0.25mA cm-2As shown in fig. 10, the cycle life graph of the battery in which charging and discharging were repeated for 1 hour under current showed that the cycle life of the battery was the longest when gluconic acid with a concentration of 0.3mol/L was used as the electrolyte.
The zinc gluconate electrolyte with the concentration of 0.1mol/L, 0.2mol/L and 0.3mol/L is respectively used as the electrolyte to assemble the zinc/zinc symmetrical battery with the concentration of 0.5mA cm-2As shown in fig. 11, the cycle life graph of the battery in which charging and discharging were repeated for 1 hour under current showed that the cycle life of the battery was the longest when gluconic acid with a concentration of 0.3mol/L was used as the electrolyte.
6. Comparison of dendrite conditions on the surface of negative electrode after circulation of different electrolyte deposition amounts
Zinc sulfate solutions with zinc gluconate electrolyte concentrations of 0.1mol/L, 0.2mol/L, 0.3mol/L and 0.3mol/L are respectively used as electrolyte, and 0.25mA cm-2At current density (0.25mAh cm-2Deposition amount) was cycled for 10 cycles, and as shown in fig. 12-15, the surface of the zinc cathode was relatively uniform without obvious dendrites when zinc gluconate was used as the electrolyte, while a large number of dendrites were generated on the surface of the zinc cathode in the zinc sulfate solution. Thus, the zinc gluconate is really beneficial to inhibiting the growth of zinc dendrites.
7. Comparison of zinc gluconate as electrolyte with different deposition amounts, different current densities and different cycle times of zinc cathode surface dendrite conditions
The concentration of zinc gluconate electrolyte is 0.3mol/L and is compared with 0.5mAh cm-2Amount of deposit, 0.1mAh cm-2Amount of deposition, 0.5mA cm-2Current density, 0.1mA cm-2Comparing the current density and the dendrite situation on the surface of the zinc negative electrode after 3 cycles and 30 cycles, as shown in fig. 16-21, the surface of the zinc negative electrode is relatively uniform, and no dendrite morphology product on the surface of zinc sulfate appears. Further, zinc gluconate is indeed beneficial to inhibit zinc dendrite growth.
8. Action mechanism for improving advantages and performance of zinc gluconate as electrolyte
1) Low cost, safety and no toxicity;
2)OH-CH2-(CHOH)4-COO-with Zn2+Interaction, regulation of Zn2+The diffusion behavior of the zinc is reduced, and the nucleation activation energy of the zinc is reduced;
3)OH-CH2-(CHOH)4-COO-the zinc is distributed on the zinc surface, so that the water content on the surface is reduced;
4) construction of Zn2+Solvated structure Zn-OH-CH2-(CHOH)4-COO+；
5) The electrolyte does not need additives, can be used as electrolyte to provide zinc ions, and the organic anions can play a role in inhibiting zinc dendrites.
The invention discloses a zinc gluconate electrolyte for a zinc ion battery and an application method thereof, and discloses the zinc gluconate electrolyte for simultaneously improving the performance and the safety of the zinc ion battery, the electrolyte can avoid the growth of dendrite of a zinc cathode, avoid the hydrogen evolution side reaction and prevent the corrosion of zinc, thereby improving the performance of the battery, the problems of stomach corrosion and the like can not be caused by the mistaken eating of children, the zinc gluconate can be used as a zinc supplement agent for children, has high safety, is a non-toxic high-safety zinc gluconate electrolyte for improving the performance of the zinc ion battery, has low cost and high safety, is expected to replace the currently used electrolytes such as zinc sulfate, zinc chloride and the like, and has wide popularization and application prospects
Thus, it will be appreciated by those skilled in the art that while embodiments of the invention have been illustrated and described in detail herein, many other variations or modifications can be made which conform to the principles of the invention, as may be directly determined or derived from the disclosure herein, without departing from the spirit and scope of the invention. Accordingly, the scope of the invention should be understood and interpreted to cover all such other variations or modifications.
Claims (7)
1. A zinc gluconate electrolyte for a zinc ion battery is characterized in that the structural formula of the zinc gluconate electrolyte is as follows:
2. the zinc gluconate electrolyte for a zinc-ion battery according to claim 1, wherein the zinc gluconate electrolyte is used at a concentration of 0.1mol/L to 0.3 mol/L.
3. The zinc gluconate electrolyte for a zinc-ion battery according to claim 1, wherein the zinc gluconate electrolyte is used at a concentration of 0.3 mol/L.
4. The zinc gluconate electrolyte for a zinc-ion battery according to claim 1, wherein said zinc gluconate electrolyte is further used in combination with zinc sulfate or zinc chloride.
5. The application method of the zinc gluconate electrolyte for the zinc ion battery is characterized in that the zinc gluconate electrolyte can be used as the electrolyte of the zinc ion battery.
6. The application method of the zinc gluconate electrolyte for the zinc ion battery is characterized in that the zinc gluconate electrolyte can be applied to zinc/carbon felt asymmetric battery electrolyte.
7. The application method of the zinc gluconate electrolyte for the zinc ion battery is characterized in that the zinc gluconate electrolyte can be applied to zinc/zinc symmetrical battery electrolyte.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115275399A (en) * | 2022-08-30 | 2022-11-01 | 北京理工大学长三角研究院(嘉兴) | Electrolyte solution and aqueous zinc ion battery using same |
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| CN111900497A (en) * | 2020-06-12 | 2020-11-06 | 北京大学深圳研究生院 | Aqueous zinc ion battery electrolyte and application thereof |
| CN111900496A (en) * | 2020-06-12 | 2020-11-06 | 北京大学深圳研究生院 | Electrolyte for water-based zinc ion battery and application thereof |
| CN112803083A (en) * | 2021-02-08 | 2021-05-14 | 江苏师范大学 | Zinc ion battery containing zinc complex |
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| US20160344056A1 (en) * | 2015-05-22 | 2016-11-24 | General Electric Company | Zinc-based electrolyte compositions, and related electrochemical processes and articles |
| CN111900497A (en) * | 2020-06-12 | 2020-11-06 | 北京大学深圳研究生院 | Aqueous zinc ion battery electrolyte and application thereof |
| CN111900496A (en) * | 2020-06-12 | 2020-11-06 | 北京大学深圳研究生院 | Electrolyte for water-based zinc ion battery and application thereof |
| CN112803083A (en) * | 2021-02-08 | 2021-05-14 | 江苏师范大学 | Zinc ion battery containing zinc complex |
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| CN115275399A (en) * | 2022-08-30 | 2022-11-01 | 北京理工大学长三角研究院(嘉兴) | Electrolyte solution and aqueous zinc ion battery using same |
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