CN117038350A - Application of multifunctional chelating agent as additive of aqueous zinc ion mixed capacitor electrolyte - Google Patents
Application of multifunctional chelating agent as additive of aqueous zinc ion mixed capacitor electrolyte Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 83
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000003990 capacitor Substances 0.000 title claims abstract description 53
- 239000000654 additive Substances 0.000 title claims abstract description 28
- 230000000996 additive effect Effects 0.000 title claims abstract description 26
- 239000002738 chelating agent Substances 0.000 title claims abstract description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 52
- WDLRUFUQRNWCPK-UHFFFAOYSA-N Tetraxetan Chemical compound OC(=O)CN1CCN(CC(O)=O)CCN(CC(O)=O)CCN(CC(O)=O)CC1 WDLRUFUQRNWCPK-UHFFFAOYSA-N 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002000 Electrolyte additive Substances 0.000 claims abstract description 11
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 14
- 229960001763 zinc sulfate Drugs 0.000 claims description 13
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 150000003751 zinc Chemical class 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 abstract description 73
- 229910052725 zinc Inorganic materials 0.000 abstract description 47
- 230000008021 deposition Effects 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000009792 diffusion process Methods 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 6
- 239000012466 permeate Substances 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 230000009920 chelation Effects 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 12
- 210000004027 cell Anatomy 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 210000001787 dendrite Anatomy 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 230000006911 nucleation Effects 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000011152 fibreglass Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- -1 zinc hydrate ions Chemical class 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses an application of a multifunctional chelating agent as an electrolyte additive of a water-based zinc ion mixed capacitor, wherein the multifunctional chelating agent DOTA is used as the additive to prepare the electrolyte of the water-based zinc ion mixed capacitor, DOTA molecules preferentially adsorb the surface of a negative electrode, refine deposited grains, guide (002) texture to preferentially grow, and promote compact and uniform zinc deposition; meanwhile, DOTA is used as a molecular regulating layer to inhibit Zn 2+ Two-dimensional diffusion of Zn at the interface is eliminated 2+ Is a concentration gradient of (c). In addition, the rich carboxyl functionality in DOTA is achieved by reaction with Zn 2+ Chelation between the two components can permeate into solvated shell layers of zinc, change coordination environment of zinc and inhibit side reaction. Therefore, by adding a trace amount of DOTA into the electrolyte, the deposition/stripping efficiency of zinc can be remarkably improved, and the cycle life of a Zn// Zn symmetric battery and a zinc ion mixed capacitor can be prolonged.
Description
Technical Field
The invention relates to application of a multifunctional chelating agent as an additive of an aqueous zinc ion mixed capacitor electrolyte, belonging to the field of modification of aqueous zinc ion mixed capacitor electrolytes.
Background
With the problems of energy exhaustion, environmental pollution and the like, a large number of efficient novel energy storage devices gradually enter the field of view of the public. Among the various novel energy storage devices, the high safety of the aqueous zinc ion mixed capacitor due to the aqueous electrolyteZinc resources, which are abundant and inexpensive in nature and reserves, are receiving a great deal of attention in the field of advanced energy storage technology. The zinc ion mixed capacitor is composed of electrolyte, a capacitive positive electrode (such as active carbon) and a battery type zinc negative electrode, so that the zinc ion mixed capacitor not only has the high energy density of a battery, but also has the high power output characteristic of the capacitor. Although aqueous zinc ion hybrid capacitors offer many attractive advantages, they still face a number of problems in the development process. For example: (1) The water molecules generate competitive hydrogen evolution reaction on the surface of the zinc cathode, and the produced hydrogen can increase the internal pressure of the sealed battery, so that the potential safety hazard of the battery is caused. In addition, hydrogen evolution reactions can lead to local OH at the surface of the anode - The concentration is increased, the generation of by-product basic zinc sulfate is induced, and the coulomb efficiency and the cycle life of the zinc ion mixed capacitor are seriously affected. (2) Zinc dendrites are generated on the surface of a zinc cathode in the zinc deposition/stripping process due to the randomness of zinc deposition and the influence of a tip effect, and the growth of dendrites can increase local current so as to exacerbate side reactions. At the same time, uncontrolled dendrite growth tends to puncture the separator, eventually leading to shorting of the cell. The problems are related and mutually influenced, so that the full play of the performance of the zinc ion mixed capacitor is further limited.
In the charge and discharge process, zinc ions migrate between the positive electrode and the negative electrode with the electrolyte as a medium. Therefore, the electrolyte is an important component of the zinc ion mixed capacitor, and has important influence on electrochemical behavior and reaction mechanism. At present, as a performance optimization strategy of an efficient, economical and simple water system zinc ion mixed capacitor, an electrolyte additive has attracted attention of scientific researchers. The action mechanism of the electrolyte additive is mainly divided into two aspects: (1) And a part of the additive is dissociated in the electrolyte body, permeates into the solvated shell by virtue of the self functional group of the additive, and damages the solvated structure of zinc ions, so that hydrogen evolution reaction and corrosion passivation of zinc are inhibited. (2) The other part of additive is adsorbed on the surface of the zinc cathode, so that the interface environment of the cathode/electrolyte is changed, the deposition behavior of zinc is regulated, and the growth of zinc dendrite is inhibited. However, in view of the complexity of the problems faced by the aqueous zinc ion mixed capacitor, development of a multifunctional electrolyte additive capable of inhibiting hydrogen evolution reaction and promoting uniform deposition of zinc is still one of the important difficulties in the development of the high-performance aqueous zinc ion mixed capacitor at present.
Disclosure of Invention
Zinc cathodes in aqueous zinc ion hybrid capacitors often suffer from a series of problems, such as zinc dendrites grown in the first order can puncture the separator and cause shorting of the cell; hydrogen evolution reactions at the anode/electrolyte interface result in excessive internal pressure, eventually battery explosion, etc. Based on the problems, the invention provides application of a multifunctional chelating agent as an additive of an aqueous zinc ion mixed capacitor electrolyte.
The multifunctional chelating agent is 1,4,7, 10-tetraazacyclododecane-1, 4,7, 10-tetraacetic acid (DOTA). Firstly, DOTA can be preferentially adsorbed on the surface of a zinc anode, a zinc deposition layer with (002) texture characteristics is induced to be formed, deposited grains are thinned, and finally the formation of a smooth and compact zinc deposition layer is promoted; secondly, rich carboxyl functional groups in DOTA permeate into a solvated shell layer of zinc through chelation, thereby inhibiting side reaction and preventing the generation of byproducts. And finally, the deposition/stripping efficiency of zinc is effectively improved, and the cycle life of the zinc ion mixed capacitor is prolonged.
The application of the multifunctional chelating agent as the additive of the electrolyte of the water-based zinc ion mixed capacitor is to prepare the electrolyte of the water-based zinc ion mixed capacitor by taking the multifunctional chelating agent as the additive.
The aqueous zinc ion mixed capacitor electrolyte formula comprises electrolyte additive DOTA, soluble zinc salt and deionized water.
Further, the molar concentration of the additive DOTA in the electrolyte is in the range of 2.5-7.5 mmol/L. For example, in the electrolyte, the molar concentration of DOTA in the electrolyte is 2.5mmol/L, 3.0mmol/L, 3.5mmol/L, 4.0mmol/L, 4.5mmol/L, 5.0mmol/L, 5.5mmol/L, 6.0mmol/L, 6.5mmol/L, 7.0mmol/L, 7.5mmol/L.
Further, the soluble zinc salt is one or more than two of zinc sulfate and zinc chloride; the concentration of the soluble zinc salt is 2mol/L.
And matching the aqueous zinc ion mixed capacitor electrolyte with the anode, the cathode and the diaphragm to assemble the aqueous rechargeable zinc ion mixed capacitor. The positive electrode material used in the water-based zinc ion mixed capacitor is commercial Active Carbon (AC), the negative electrode is commercial zinc foil (Zn), and the battery diaphragm is glass fiber diaphragm (GF/D).
The technical scheme of the invention has the following action mechanism and advantages:
(1) The chelating agent DOTA additive is introduced into the electrolyte to regulate and control the deposition behavior of zinc. DOTA is preferentially adsorbed on the surface of a zinc cathode, and the larger nucleation overpotential can reduce the nucleation radius of zinc and refine deposited grains; in addition, DOTA can induce the formation of a (002) texture grown zinc deposit, ultimately leading to the formation of a dense, planar zinc deposit, thereby inhibiting dendrite growth.
(2) The chelating agent DOTA additive is introduced into the electrolyte to adjust the solvation structure of the zinc hydrate ions. DOTA has rich carboxyl functional groups, and DOTA and Zn 2+ The chelation between the two makes carboxylate groups easily permeate into solvated shell layers of zinc, thereby changing coordination environment of zinc, inhibiting side reaction and preventing by-product.
(3) DOTA is used as a molecular regulating layer, and the diffusion path of zinc ions is effectively regulated and controlled by virtue of unique molecular structure and steric hindrance effect, so that Zn is inhibited 2+ Two-dimensional diffusion of Zn at the interface is eliminated 2+ Is a concentration gradient of (c).
(4) The electrolyte prepared by the invention is used for the water-based zinc ion mixed capacitor, can effectively regulate and control the interface environment of a zinc cathode, inhibit hydrogen evolution reaction and side reaction, promote uniform zinc deposition, and remarkably prolong the cycle life of the zinc ion mixed capacitor.
(5) The electrolyte additive DOTA is safe, nontoxic and environment-friendly; meanwhile, the use of a trace amount of additive (5 mmol/L) can play a great role. Therefore, the electrolyte additive DOTA has great potential in the field of modification of zinc ion mixed capacitor electrolyte.
Drawings
Fig. 1 is an XRD test after immersing zinc anodes in the electrolyte prepared in example 2 and comparative example 1 for 3 days. As shown in the figure, zn is detected on the surface of a zinc anode immersed in a zinc sulfate electrolyte 4 (OH) 6 SO 4 ·5H 2 The diffraction peak of O shows that by-products are generated on the surface of the zinc cathode; when DOTA electrolyte additive was introduced, little Zn was detected in XRD 4 (OH) 6 SO 4 ·5H 2 Diffraction peaks of O. Analysis showed that the use of DOTA can inhibit the formation of byproducts.
Fig. 2 is an LSV test of zinc anodes in the electrolyte prepared in example 2 and comparative example 1. As shown, when the additive DOTA was introduced, a significant negative shift in hydrogen evolution overpotential occurred. Analysis shows that the use of the electrolyte additive DOTA can inhibit the occurrence of side reactions.
Fig. 3 is an ex situ Atomic Force Microscope (AFM) of the zinc anode after cycling in example 2 and comparative example 1, respectively. As shown in the figure, the surface of the zinc cathode using the original zinc sulfate electrolyte presents an irregular and rugged deposition morphology; after DOTA is introduced, the surface of the zinc cathode presents a smooth and compact deposition morphology, and the promotion effect of DOTA on uniform deposition of zinc is proved.
Fig. 4 is a CV test of zinc anodes in the electrolyte prepared in example 2 and comparative example 1. As shown, when the additive DOTA is introduced, the reduction potential of the zinc ions shifts negatively from point M to point L, meaning that the nucleation overpotential increases. The larger nucleation overpotential can reduce the nucleation radius of zinc and refine zinc deposition grains, thereby promoting uniform and compact zinc deposition.
Fig. 5 is a CA test performed on zinc anodes in the electrolyte formulations of example 2 and comparative example 1. As shown, at a constant overpotential of-150 mV, the current in the zinc sulfate solution increased continuously over 150s, representing Zn 2+ Uncontrolled two-dimensional diffusion; the current value remains stable all the time after the introduction of the additive DOTA. This suggests that in DOTA/zinc sulphate solutions, three-dimensional diffusion dominates and two-dimensional diffusion of zinc ions is limited, thus effectively suppressingDendrite growth is produced.
FIG. 6 is a graph of the cycling performance of Zn// Zn symmetric cells in the electrolytes formulated in example 2 and comparative example 1. As shown in the figure, at 5mA/cm -2 、5mAh/cm -2 Under test conditions of (2) mol/LZnSO 4 The symmetrical battery of the electrolyte has a short circuit phenomenon after 80 hours of circulation; in the use of 2mol/LZnSO 4 Under the condition of +5.0mmol/LDOTA electrolyte, the stable cycle time of the symmetrical battery is up to 1800h, which is far longer than the cycle life of the symmetrical battery without additives, indicating that the use of the additives can greatly improve the cycle stability of the zinc cathode.
FIG. 7 is a graph of the cycling performance of Zn// Zn symmetric cells in the electrolytes prepared in example 1 and comparative example 1. As shown in the figure, at 5mA/cm -2 、5mAh/cm -2 Under test conditions of (2) mol/LZnSO 4 In the case of +2.5mmol/LDOTA electrolyte, the cycle time of the symmetrical cell was 900h.
FIG. 8 is a graph of the cycling performance of Zn// Zn symmetric cells in the electrolytes formulated in example 3 and comparative example 1. As shown in the figure, at 5mA/cm -2 、5mAh/cm -2 Under test conditions of (2) mol/LZnSO 4 In the case of +7.5mmol/LDOTA electrolyte, the cycle time of the symmetrical cell was 1160h.
Fig. 9 is a graph of coulombic efficiency of Ti// Zn asymmetric cells in the electrolyte formulated in example 2 and comparative example 1. At 10mA cm -2 、5mAh cm -2 For the original 2mol/LZnSO under the test conditions of (2) 4 The electrolyte, the coulomb efficiency, began to fluctuate drastically at about 30 cycles, confirming its poor plating/stripping reversibility. In sharp contrast, 2mol/LZnSO is used 4 The coulombic efficiency of the Ti// Zn battery with +5.0mmol/LDOTA electrolyte is always stable in 580 cycles, which proves the improvement of the electroplating/stripping reversibility of DOTA on zinc.
FIG. 10 is a graph showing the cycle performance of the zinc ion mixed capacitor in the electrolyte prepared in example 2 and comparative example 1, and the test current density was 5A/g. As shown, 2mol/LZnSO was used 4 The zinc ion hybrid capacitor as an electrolyte had a sudden decrease in capacity after about 3000 cycles. In contrast to this, the process is performed,using 2mol/LZnSO 4 The +5.0mmol/LDOTA zinc ion mixed capacitor as electrolyte can be stably circulated for 40000 times, and the capacity retention rate is close to 100%. The result shows that DOTA can be used as an electrolyte additive to remarkably improve the cycle performance of the water-based zinc ion mixed capacitor.
Detailed description of the preferred embodiments
The following examples are intended to illustrate this content in further detail; the scope of the claims is not limited by the examples.
Example 1:2mol/LZnSO 4 Preparation of +2.5mmol/L DOTA electrolyte
In this example, an electrolyte was prepared using DOTA as an additive and applied to an aqueous zinc ion hybrid capacitor. The electrolyte formulation includes DOTA, soluble zinc salt and deionized water. The zinc salt is zinc sulfate (ZnSO) 4 ) The solvent is deionized water.
The preparation method of the electrolyte comprises the following steps: under the air atmosphere, zinc sulfate heptahydrate is taken as a solute, deionized water is taken as a solvent, and zinc sulfate electrolyte with the concentration of 2mol/L is prepared first. Next, 2.5mmol/L of DOTA white crystal powder was added and stirred until it was completely dissolved to obtain the electrolyte described in example 1. The electrolyte is applied to an aqueous zinc ion mixed capacitor, and comprises the following steps:
(1) Assembly and testing of Zn// Zn symmetric cells
A zinc foil having a thickness of 80 μm was subjected to ultrasonic treatment in absolute ethanol, washed, dried, and then punched into a circular sheet having a diameter of 12mm, which was used as a positive/negative electrode sheet for a zinc ion-mix capacitor. The commercial CR2032 type electrode was used with a 16mm diameter fiberglass separator and 150 μl of electrolyte was used, and the battery was assembled in the order of "negative electrode case-negative electrode sheet-separator-electrolyte-positive electrode sheet-stainless steel sheet-dome-positive electrode case". And after the assembly, the Zn// Zn symmetrical battery is manufactured through pressurized encapsulation of 750 psi. Constant current charge and discharge test is carried out on the assembled battery at 25 ℃, and the test conditions are set as follows: 5mAh/cm -2 ，5mAh/cm -2 。
(2) Assembly and testing of Ti// Zn asymmetric cells
Wiping titanium foil with the thickness of 10 mu m with absolute ethyl alcohol, and then stamping the titanium foil into a round piece with the diameter of 12mm to serve as a positive electrode piece; a zinc foil with the thickness of 80 μm is subjected to ultrasonic treatment in absolute ethyl alcohol, washing and drying, and then is punched into a round piece disc with the diameter of 12mm to be used as a negative electrode piece. The commercial CR2032 type electrode was used with a 16mm diameter fiberglass separator and 150 μl of electrolyte was used, and the battery was assembled in the order of "negative electrode case-negative electrode sheet-separator-electrolyte-positive electrode sheet-stainless steel sheet-dome-positive electrode case". And after the assembly, the Ti// Zn asymmetric battery is manufactured through pressurized encapsulation at 750 psi. Constant current charge and discharge test is carried out on the assembled battery at 25 ℃, and the test conditions are set as follows: 10mAh/cm -2 ，5mAh/cm -2 The cut-off voltage was set to 0.2V.
(3) Assembly and test of active carbon// Zn zinc ion mixed capacitor
Dissolving polyvinylidene fluoride (PVDF) in N-methyl pyrrolidone (NMP), grinding active carbon anode material and acetylene black uniformly, adding the mixture (the mass ratio of the active carbon to the acetylene black to the polyvinylidene fluoride is 7:2:1), mixing uniformly to form slurry, and coating the slurry on a titanium foil with the thickness of 10 mu m (the coating thickness is 400 mu m, and the density of active substances is approximately 5 mg/cm) 2 ) Drying and stamping into a round sheet with the diameter of 12mm to be used as a positive electrode sheet; a zinc foil with a thickness of 80 μm was subjected to ultrasonic treatment in absolute ethanol, washed, dried, and then punched into a wafer (diameter: 16 mm) as a negative electrode sheet. The commercial CR2032 type electrode was used with a 16mm diameter fiberglass separator and 150 μl of electrolyte was used, and the battery was assembled in the order of "negative electrode case-negative electrode sheet-separator-electrolyte-positive electrode sheet-stainless steel sheet-dome-positive electrode case". After the assembly, the zinc ion mixed capacitor is manufactured by pressurizing and packaging at 750 psi. Constant-current charge and discharge tests are carried out on the assembled zinc ion mixed capacitor at 25 ℃, and the test conditions are set as follows: 5A/g.
Example 2:2mol/LZnSO 4 Preparation of +5.0mmol/L DOTA electrolyte
In this example, an electrolyte was prepared using DOTA as an additive and applied to an aqueous zinc ion hybrid capacitor. The electrolyte formulation comprisesDOTA, soluble zinc salts, and deionized water. The zinc salt is zinc sulfate (ZnSO) 4 ) The solvent is deionized water.
The preparation method of the electrolyte comprises the following steps: under the air atmosphere, zinc sulfate heptahydrate is taken as a solute, deionized water is taken as a solvent, and zinc sulfate electrolyte with the concentration of 2mol/L is prepared first. Next, 5.0mmol/L of DOTA white crystal powder was added and stirred until it was completely dissolved to obtain the electrolyte described in example 2. The electrolyte is applied to an aqueous zinc ion mixed capacitor, and comprises the following steps:
the battery and capacitor assembly sequence and test conditions were the same as in example 1, except that the additive concentration in the electrolyte was different from example 1.
Example 3:2mol/LZnSO 4 Preparation of +7.5mmol/L DOTA electrolyte
In this example, an electrolyte was prepared using DOTA as an additive and applied to an aqueous zinc ion hybrid capacitor. The electrolyte formulation includes DOTA, soluble zinc salt and deionized water. The zinc salt is zinc sulfate (ZnSO) 4 ) The solvent is deionized water.
The preparation method of the electrolyte comprises the following steps: under the air atmosphere, zinc sulfate heptahydrate is taken as a solute, deionized water is taken as a solvent, and zinc sulfate electrolyte with the concentration of 2mol/L is prepared first. Next, 7.5mmol/L of DOTA white crystal powder was added and stirred until it was completely dissolved to obtain the electrolyte described in example 3. The electrolyte is applied to an aqueous zinc ion mixed capacitor, and comprises the following steps:
the battery and capacitor assembly sequence and test conditions were the same as in example 1, except that the additive concentration in the electrolyte was different from example 1.
Comparative example 1:2mol/L ZnSO 4 Preparation of electrolyte
The preparation method of the electrolyte comprises the following steps: under the air atmosphere, zinc sulfate heptahydrate is used as a solute, deionized water is used as a solvent, and zinc sulfate electrolyte with the concentration of 2mol/L is prepared, so that the electrolyte prepared in the comparative example 1 is obtained. The electrolyte is applied to an aqueous zinc ion mixed capacitor, and comprises the following steps:
the battery and capacitor assembly sequence and test conditions were the same as in example 1, except that the additive concentration in the electrolyte was different from example 1.
The present invention is not described in detail in part as being well known to those skilled in the art. The above examples are merely illustrative of preferred embodiments of the invention, which are not exhaustive of all details, nor are they intended to limit the invention to the particular embodiments disclosed. Various modifications and improvements of the technical scheme of the present invention will fall within the protection scope of the present invention as defined in the claims without departing from the design spirit of the present invention.
Claims (7)
1. The application of the multifunctional chelating agent as the additive of the aqueous zinc ion mixed capacitor electrolyte is characterized in that:
preparing an electrolyte of the water-based zinc ion mixed capacitor by taking a multifunctional chelating agent as an additive; the multifunctional chelating agent is 1,4,7, 10-tetraazacyclododecane-1, 4,7, 10-tetraacetic acid, which is called DOTA for short.
2. The use according to claim 1, characterized in that:
the aqueous zinc ion mixed capacitor electrolyte formula comprises electrolyte additive DOTA, soluble zinc salt and deionized water.
3. The use according to claim 2, characterized in that:
the molar concentration of the additive DOTA in the electrolyte is 2.5-7.5 mmol/L.
4. The use according to claim 2, characterized in that:
the soluble zinc salt is one or more than two of zinc sulfate and zinc chloride.
5. The use according to claim 4, characterized in that:
the concentration of the soluble zinc salt is 2mol/L.
6. The use according to any one of claims 1-5, characterized in that:
and matching the aqueous zinc ion mixed capacitor electrolyte with the anode, the cathode and the diaphragm to assemble the aqueous rechargeable zinc ion mixed capacitor.
7. The use according to claim 6, characterized in that:
the positive electrode material is commercial active carbon, the negative electrode is commercial zinc foil, and the battery diaphragm is a glass fiber diaphragm.
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