CN117650293A - Aqueous zinc ion battery electrolyte and application thereof - Google Patents
Aqueous zinc ion battery electrolyte and application thereof Download PDFInfo
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- CN117650293A CN117650293A CN202311641640.6A CN202311641640A CN117650293A CN 117650293 A CN117650293 A CN 117650293A CN 202311641640 A CN202311641640 A CN 202311641640A CN 117650293 A CN117650293 A CN 117650293A
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- 239000003792 electrolyte Substances 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 41
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000011664 nicotinic acid Substances 0.000 claims abstract description 46
- 229960003512 nicotinic acid Drugs 0.000 claims abstract description 46
- 235000001968 nicotinic acid Nutrition 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 239000002000 Electrolyte additive Substances 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 125000000627 niacin group Chemical group 0.000 claims 1
- 239000011701 zinc Substances 0.000 abstract description 67
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052725 zinc Inorganic materials 0.000 abstract description 12
- 239000000654 additive Substances 0.000 abstract description 7
- 230000000996 additive effect Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 210000001787 dendrite Anatomy 0.000 abstract description 5
- 230000012010 growth Effects 0.000 abstract description 5
- 230000014759 maintenance of location Effects 0.000 abstract description 5
- 230000006911 nucleation Effects 0.000 abstract description 3
- 238000010899 nucleation Methods 0.000 abstract description 3
- 230000002829 reductive effect Effects 0.000 abstract description 3
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 31
- 238000011056 performance test Methods 0.000 description 20
- 239000012528 membrane Substances 0.000 description 16
- 238000001035 drying Methods 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 235000012431 wafers Nutrition 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000005520 cutting process Methods 0.000 description 10
- 239000003365 glass fiber Substances 0.000 description 10
- 238000005498 polishing Methods 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000007614 solvation Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000002156 mixing 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
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to the technical field of electrochemical energy storage, and discloses a water-based zinc ion battery electrolyte and application thereof in a water-based zinc ion battery. The concentration of Nicotinic Acid (NA) is preferably 0.1-0.5 g.L ‑1 The concentration of zinc sulfate is preferably 1 to 3 mol.L ‑1 . The trace additive NA is added into the zinc ion electrolyte, so that the nucleation overpotential can be reduced, the kinetics performance of zinc deposition/dissolution is improved, the corrosion of a metal zinc negative electrode and uncontrollable dendrite growth are effectively inhibited, and the problems of poor battery cycle performance, low coulomb efficiency and the like are solved. Experiments prove that the water system zinc ion battery prepared by adopting the electrolyte of the invention is 1.0mA.cm ‑2 At current density (area capacity 1.0 mAh.cm) ‑2 ) Can stably circulate for 5200h, and the capacity retention rate of the full battery can be effectively improved, thereby having important significance for promoting the commercialization application of the future water system zinc ion battery.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a water-based zinc ion battery electrolyte and application thereof in a water-based zinc ion battery.
Background
With the increasing global environmental pollution and energy crisis, energy has severely restricted the development of the economic society. Currently, in terms of energy storage, lithium Ion Batteries (LIBs) have been widely used in various aspects of life due to their high energy density, long life span and good cycle performance. However, problems of high manufacturing cost, low safety, environmental pollution, resource limitation, and the like of lithium ion batteries pose challenges to their market predominance. Therefore, the development of safe and inexpensive aqueous batteries is critical to the upgrading of the energy storage industry.
Rechargeable Aqueous Zinc Ion Batteries (AZIBs) have received great attention in large energy storage systems because of their inherent safety, low cost, and relatively high theoretical energy density. However, zinc anodes face challenges such as poor cycling and low coulombic efficiency due to dendrite growth, corrosion, and formation of irreversible byproducts, greatly impeding commercial production of aqueous zinc ions. The electrolyte is an important component of the battery, and the composition, concentration and performance of the battery are all of critical influence. Zinc anodic protection is one of the simplest and most effective methods starting from an electrolyte. At present, there are two main methods: firstly, electrolyte additives are used, and secondly, novel anhydrous or low-water electrolyte is selected. The low-water or anhydrous electrolyte is mainly eutectic electrolyte, high-concentration electrolyte and gel electrolyte, and can improve the electrochemical performance of the zinc ion battery to a certain extent, but the practical application is difficult due to the factors of high cost, difficult material acquisition and the like. In contrast, the introduction of electrolyte additives appears to be the most efficient, convenient, economical, and efficient method. However, the most possible industrialized production is realized at present, and the low-cost and high-functionality additive is still in the primary stage, so the development of the electrolyte which is easy to realize industrialized production is an urgent need for practical application of the water-based zinc ion battery.
Disclosure of Invention
Aiming at the limitations of the prior art, the invention provides an aqueous zinc ion battery electrolyte and application thereof in an aqueous zinc ion battery; the additive Nicotinic Acid (NA) molecules contained in the electrolyte can effectively overcome the problems of poor battery cycle performance, low coulomb efficiency, safety and the like caused by corrosion, hydrogen evolution and uncontrollable dendrite growth of a metal zinc anode under the condition of changing a solvation structure and interfacial adsorption of zinc ions, and has great significance for promoting the commercialization development of water-based zinc ions.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
according to one aspect of the present invention, there is provided an aqueous zinc ion battery electrolyte comprising a soluble zinc salt, an electrolyte additive and deionized water, the electrolyte additive being niacin.
Preferably, the soluble zinc salt is one of zinc sulfate and zinc chloride.
Preferably, the zinc ion concentration of the soluble zinc salt is 1 to 3 mol.L -1 。
Preferably, the concentration of the nicotinic acid is 0.1-0.5g.L -1 。
According to another aspect of the invention, the preparation method of the aqueous zinc ion battery electrolyte is provided, wherein the electrolyte with a certain zinc ion concentration is prepared by adopting deionized water serving as a solvent, and NA is added and mixed until the electrolyte is completely dissolved.
According to another aspect of the invention, the application of the aqueous zinc ion battery electrolyte in an aqueous zinc ion battery is provided.
The beneficial effects of the invention are as follows:
the water-based zinc ion battery electrolyte is prepared by adding a trace amount of NA into the traditional zinc sulfate electrolyte, and has the advantages of simple preparation method, low cost and suitability for mass industrial production.
The water-based zinc ion battery electrolyte disclosed by the invention not only changes the solvation structure of zinc ions through electrolyte additives, but also avoids higher desolvation energy barriers, and realizes quick dynamics; the zinc ion-containing electrode can be electrostatically adsorbed on the surface of the electrode, so that the nucleation overpotential is reduced, the electric field distribution is uniform, and zinc ions are uniformly deposited; thereby effectively inhibiting the formation and growth of dendrites and solving the problems of corrosion, hydrogen evolution and other side reactions.
The aqueous zinc ion battery electrolyte is applied to Zn symmetric batteries, can realize ultra-high stable cycle performance (5200 h) and is applied to Zn MnO 2 The full battery has remarkable improvement effect on the capacity retention rate, and is more beneficial to actual production.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments of the present application will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a long cycle performance graph of a symmetrical battery in example 1 of the present invention.
Fig. 2 is a graph showing the long cycle performance of the symmetrical battery in example 2 of the present invention.
Fig. 3 is a graph showing the long cycle performance of the symmetrical battery in example 3 of the present invention.
Fig. 4 is a graph showing the long cycle performance of the symmetrical battery in example 4 of the present invention.
Fig. 5 is a graph showing the long cycle performance of the symmetrical battery in example 5 of the present invention.
Fig. 6 is a graph showing the cycle performance of the full cells in comparative example 4 and example 6 of the present invention.
Fig. 7 is a long cycle performance graph of the symmetrical cell of comparative example 1 of the present invention.
Fig. 8 is a long cycle performance graph of the symmetrical cell of comparative example 2 of the present invention.
Fig. 9 is a graph showing the long cycle performance of the symmetrical cell of comparative example 3 of the present invention.
Detailed Description
The present invention will be further described in detail with reference to the following examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Example 1
Assembling 2 mol.L -1 ZnSO 4 +0.1g·L -1 And carrying out battery test on the Zn symmetric battery with NA being Zn of the electrolyte.
(1) Preparing electrolyte
287.58g ZnSO was weighed out 4 ·7H 2 O is dissolved in 500mL deionized water to prepare 2 mol.L -1 ZnSO 4 Solution, then 0.01g NA was dissolved in 100mL of ZnSO as described above 4 A solution of 2 mol.L -1 ZnSO 4 +0.1g·L -1 NA solution.
(2) Preparation of electrodes
Polishing the surface of zinc foil with the thickness of 0.1mm, cutting out a wafer with the diameter of 12mm, ultrasonically treating with absolute ethyl alcohol for 15min, washing cleanly, and drying in vacuum.
(3) Symmetrical battery assembly
Two Zn sheets are respectively used as the positive electrode and the negative electrode of the battery, a glass fiber filter membrane is used as a membrane, and the concentration of the Zn sheets is 2 mol.L -1 ZnSO 4 +0.1g·L -1 And the NA solution is electrolyte, and the buckle CR2032 symmetrical battery is assembled.
(4) Symmetrical battery performance test
Testing the normal temperature cycle performance, setting the charge-discharge current at 25 ℃ to be 1.0 mA.cm -2 The fixed charge-discharge capacity was 1.0mAh cm -2 Long cycle performance testing was performed under the conditions.
The results of the performance test of the battery are shown in fig. 1. At 1.0 mA.cm -2 At current density (area capacity 1.0 mAh.cm) -2 ) 2 mol.L is used -1 ZnSO 4 +0.1g·L -1 The Zn of NA electrolyte realizes long cycle life of 1200 h.
Example 2
Assembling 2 mol.L -1 ZnSO 4 +0.3g·L -1 And carrying out battery test on the Zn symmetric battery with NA being Zn of the electrolyte.
(1) Preparing electrolyte
287.58g ZnSO was weighed out 4 ·7H 2 O is dissolved in 500mL deionized water to prepare 2 mol.L -1 ZnSO 4 The solution was then dissolved with 0.03g NA in 100mL of ZnSO as described above 4 A solution of 2 mol.L -1 ZnSO 4 +0.3g·L -1 NA solution.
(2) Preparation of electrodes
Polishing the surface of zinc foil with the thickness of 0.1mm, cutting out a wafer with the diameter of 12mm, ultrasonically treating with absolute ethyl alcohol for 15min, washing cleanly, and drying in vacuum.
(3) Symmetrical battery assembly
Two Zn sheets are respectively used as the positive electrode and the negative electrode of the battery, a glass fiber filter membrane is used as a membrane, and the concentration of the Zn sheets is 2 mol.L -1 ZnSO 4 +0.3g·L -1 And the NA solution is electrolyte, and the buckle CR2032 symmetrical battery is assembled.
(4) Symmetrical battery performance test
Testing the normal temperature cycle performance, setting the charge-discharge current at 25 ℃ to be 1.0 mA.cm -2 The fixed charge-discharge capacity was 1.0mAh cm -2 Long cycle performance testing was performed under the conditions.
The results of the performance test of the battery are shown in fig. 2. At 1.0 mA.cm -2 At current density (area capacity 1.0 mAh.cm) -2 ) 2 mol.L is used -1 ZnSO 4 +0.3g·L -1 The Zn of NA electrolyte is Zn battery realizes 5200h of ultra-long cycle life.
Example 3
Assembling 2 mol.L -1 ZnSO 4 +0.5g·L -1 And carrying out battery test on the Zn symmetric battery with NA being Zn of the electrolyte.
(1) Preparing electrolyte
287.58g ZnSO was weighed out 4 ·7H 2 O is dissolved in 500mL deionized water to prepare 2 mol.L -1 ZnSO 4 Solution, then 0.05g NA was dissolved in 100mL ZnSO as described above 4 A solution of 2 mol.L -1 ZnSO 4 +0.5g·L -1 NA solution.
(2) Preparation of electrodes
Polishing the surface of zinc foil with the thickness of 0.1mm, cutting out a wafer with the diameter of 12mm, ultrasonically treating with absolute ethyl alcohol for 15min, washing cleanly, and drying in vacuum.
(3) Symmetrical battery assembly
Two Zn sheets are respectively used as the positive electrode and the negative electrode of the battery, a glass fiber filter membrane is used as a membrane, and the concentration of the Zn sheets is 2 mol.L -1 ZnSO 4 +0.5g·L -1 And the NA solution is electrolyte, and the buckle CR2032 symmetrical battery is assembled.
(4) Symmetrical battery performance test
Testing the normal temperature cycle performance, setting the charge-discharge current at 25 ℃ to be 1.0 mA.cm -2 The fixed charge-discharge capacity was 1.0mAh cm -2 Long cycle performance testing was performed under the conditions.
The results of the performance test of the battery are shown in fig. 3. At 1.0 mA.cm -2 At current density (area capacity 1.0 mAh.cm) -2 ) 2 mol.L is used -1 ZnSO 4 +0.5g·L -1 The Zn of NA electrolyte realizes a long cycle life of 900 hours.
Example 4
Assembling 1 mol.L -1 ZnCl 2 +0.3g·L -1 And carrying out battery test on the Zn symmetric battery with NA being Zn of the electrolyte.
(1) Preparing electrolyte
68.16g ZnCl is weighed 2 Dissolving in 500mL deionized water to obtain a solution of 1 mol.L -1 ZnCl 2 Solution, then 0.03g NA was dissolved in 100mL ZnCl as described above 2 Solution of 1 mol.L -1 ZnCl 2 +0.3g·L -1 NA solution.
(2) Preparation of electrodes
Polishing the surface of zinc foil with the thickness of 0.1mm, cutting out a wafer with the diameter of 12mm, ultrasonically treating with absolute ethyl alcohol for 15min, washing cleanly, and drying in vacuum.
(3) Symmetrical battery assembly
Two Zn sheets are respectively used as the positive electrode and the negative electrode of the battery, a glass fiber filter membrane is used as a membrane, and the concentration of the Zn sheets is 1 mol.L -1 ZnCl 2 +0.3g·L -1 And the NA solution is electrolyte, and the buckle CR2032 symmetrical battery is assembled.
(4) Symmetrical battery performance test
Testing the normal temperature cycle performance, setting the charge-discharge current at 25 ℃ to be 1.0 mA.cm -2 The fixed charge-discharge capacity was 1.0mAh cm -2 Long cycle performance testing was performed under the conditions.
The results of the performance test of the battery are shown in fig. 4. At 1.0 mA.cm -2 At current density (area capacity 1.0 mAh.cm) -2 ) 1 mol.L was used -1 ZnCl 2 +0.3g·L -1 The Zn of NA electrolyte realizes the ultra-long cycle life of 480 h.
Example 5
Assembling 3 mol.L -1 ZnCl 2 +0.3g·L -1 And carrying out battery test on the Zn symmetric battery with NA being Zn of the electrolyte.
(1) Preparing electrolyte
204.47g ZnCl is weighed 2 Dissolving in 500mL deionized water to obtain a solution of 3mol.L -1 ZnCl 2 Solution, then 0.03g NA was dissolved in 100mL ZnCl as described above 2 Solution of 3 mol.L -1 ZnCl 2 +0.3g·L -1 NA solution.
(2) Preparation of electrodes
Polishing the surface of zinc foil with the thickness of 0.1mm, cutting out a wafer with the diameter of 12mm, ultrasonically treating with absolute ethyl alcohol for 15min, washing cleanly, and drying in vacuum.
(3) Symmetrical battery assembly
Two Zn sheets are respectively used as the positive electrode and the negative electrode of the battery, a glass fiber filter membrane is used as a membrane, and 3 mol.L -1 ZnCl 2 +0.3g·L -1 And the NA solution is electrolyte, and the buckle CR2032 symmetrical battery is assembled.
(4) Symmetrical battery performance test
Testing the normal temperature cycle performance, setting the charge-discharge current at 25 ℃ to be 1.0 mA.cm -2 The fixed charge-discharge capacity was 1.0mAh cm -2 Long cycle performance testing was performed under the conditions.
The results of the performance test of the battery are shown in fig. 5. At 1.0 mA.cm -2 At current density (area capacity 1.0 mAh.cm) -2 ) 3 mol.L was used -1 ZnCl 2 +0.3g·L -1 The Zn of NA electrolyte realizes a long cycle life of 1300 h.
Example 6
Assembling 2 mol.L -1 ZnSO 4 +0.3g·L -1 NA is Zn MnO of electrolyte 2 And (5) full battery, and performing battery test.
(1) Preparing electrolyte
287.58g ZnSO was weighed out 4 ·7H 2 O is dissolved in 500mL deionized water to prepare 2 mol.L -1 ZnSO 4 The solution was then dissolved with 0.03g NA in 100mL of ZnSO as described above 4 A solution of 2 mol.L -1 ZnSO 4 +0.3g·L -1 NA solution.
(2) Preparation of electrodes
Zinc negative electrode: polishing the surface of zinc foil with the thickness of 0.1mm, cutting into wafers with the diameter of 12mm, carrying out ultrasonic treatment on the wafers for 15min by absolute ethyl alcohol, washing, cleaning and drying in vacuum.
MnO 2 And (3) a positive electrode: solution a: 0.768g of MnSO 4 ·H 2 O is dissolved in 15mL of deionized water and stirred uniformly;
solution B: 0.477g KMnO 4 Dissolving in 15mL deionized water, and stirring uniformly;
pouring the solution B into the solution A, stirring for 30min, quickly transferring to a hydrothermal high-pressure reaction kettle, and putting into an oven to be hydrothermal for 12h at 160 ℃. And after the reaction is finished, centrifugally separating the product, washing the product with water for 3 times, and finally drying the product in a baking oven at 60 ℃ to obtain the manganese dioxide material. Manganese dioxide, acetylene black and polyvinylidene fluoride are placed in an agate mortar according to the mass ratio of 7:2:1, and after being ground uniformly, a proper amount of N-methyl pyrrolidone is added, and grinding and mixing are continued until the slurry is obtained. Then coating the anode plate on a stainless steel current collector with the diameter of 12mm, and finally drying the anode plate in an oven at the temperature of 60 ℃ to obtain the anode plate.
(3) Symmetrical battery assembly
Zinc cathode, mnO 2 Positive electrode, glass fiber diaphragm, 2 mol.L -1 ZnSO 4 +0.3g·L -1 And the NA solution is electrolyte, and the button CR2032 full battery is assembled.
(4) Full cell performance test
Testing the normal temperature cycle performance, setting the charge-discharge current at 25 ℃ to be 0.2 A.g -1 Long cycle performance testing was performed.
The results of the performance test of the battery are shown in fig. 6. At 0.2 A.g -1 At a current density of 2 mol.L -1 ZnSO 4 +0.3g·L -1 Zn MnO of NA electrolyte 2 The initial capacity of the battery is 240 mAh.g -1 Can stably circulate for 500 circlesThe capacity retention was 79.5%.
Comparative example 1
Assembling 2 mol.L -1 ZnSO 4 And (5) performing battery test on the Zn symmetric battery of the electrolyte.
(1) Preparing electrolyte
287.58g ZnSO was weighed out 4 ·7H 2 O is dissolved in 500mL deionized water to prepare 2 mol.L -1 ZnSO 4 A solution.
(2) Preparation of electrodes
Polishing the surface of zinc foil with the thickness of 0.1mm, cutting out a wafer with the diameter of 12mm, ultrasonically treating with absolute ethyl alcohol for 15min, washing cleanly, and drying in vacuum.
(3) Symmetrical battery assembly
Two Zn sheets are respectively used as the positive electrode and the negative electrode of the battery, a glass fiber filter membrane is used as a membrane, and the concentration of the Zn sheets is 2 mol.L -1 ZnSO 4 The solution is electrolyte, and the button CR2032 symmetrical battery is assembled.
(4) Symmetrical battery performance test
Testing the normal temperature cycle performance, setting the charge-discharge current at 25 ℃ to be 1.0 mA.cm -2 The fixed charge-discharge capacity was 1.0mAh cm -2 Long cycle performance testing was performed under the conditions.
The results of the performance test of the battery are shown in fig. 7. At 1.0 mA.cm -2 At current density (area capacity 1.0 mAh.cm) -2 ) 2 mol.L is used -1 ZnSO 4 The cycle life of the Zn battery of the electrolyte is only 89h.
Comparative example 2
Assembling 1 mol.L -1 ZnSO 4 And (5) performing battery test on the Zn symmetric battery of the electrolyte.
(1) Preparing electrolyte
143.79g ZnSO was weighed out 4 ·7H 2 O is dissolved in 500mL deionized water to prepare 1 mol.L -1 ZnSO 4 A solution.
(2) Preparation of electrodes
Polishing the surface of zinc foil with the thickness of 0.1mm, cutting out a wafer with the diameter of 12mm, ultrasonically treating with absolute ethyl alcohol for 15min, washing cleanly, and drying in vacuum.
(3) Symmetrical battery assembly
Two Zn sheets are respectively used as the positive electrode and the negative electrode of the battery, a glass fiber filter membrane is used as a membrane, and the concentration of the Zn sheets is 1 mol.L -1 ZnSO 4 The solution is electrolyte, and the button CR2032 symmetrical battery is assembled.
(4) Symmetrical battery performance test
Testing the normal temperature cycle performance, setting the charge-discharge current at 25 ℃ to be 1.0 mA.cm -2 The fixed charge-discharge capacity was 1.0mAh cm -2 Long cycle performance testing was performed under the conditions.
The results of the performance test of the battery are shown in fig. 8. At 1.0 mA.cm -2 At current density (area capacity 1.0 mAh.cm) -2 ) 1 mol.L was used -1 ZnSO 4 The cycle life of the Zn battery of Zn of electrolyte is only 160 hours.
Comparative example 3
Assembling 3 mol.L -1 ZnSO 4 And (5) performing battery test on the Zn symmetric battery of the electrolyte.
(1) Preparing electrolyte
431.37g ZnSO was weighed out 4 ·7H 2 O is dissolved in 500mL deionized water to prepare 3 mol.L -1 ZnSO 4 A solution.
(2) Preparation of electrodes
Polishing the surface of zinc foil with the thickness of 0.1mm, cutting out a wafer with the diameter of 12mm, ultrasonically treating with absolute ethyl alcohol for 15min, washing cleanly, and drying in vacuum.
(3) Symmetrical battery assembly
Two Zn sheets are respectively used as the positive electrode and the negative electrode of the battery, a glass fiber filter membrane is used as a membrane, and 3 mol.L -1 ZnSO 4 The solution is electrolyte, and the button CR2032 symmetrical battery is assembled.
(4) Symmetrical battery performance test
Testing the normal temperature cycle performance, setting the charge-discharge current at 25 ℃ to be 1.0 mA.cm -2 The fixed charge-discharge capacity was 1.0mAh cm -2 Long cycle performance testing was performed under the conditions.
The results of the performance test of the battery are shown in fig. 9. At 1.0 mA.cm -2 Electric currentAt density (area capacity 1.0 mAh.cm) -2 ) 3 mol.L was used -1 ZnSO 4 The cycle life of the Zn battery of Zn of electrolyte is only 93 hours.
Comparative example 4
Assembling 2 mol.L -1 ZnSO 4 Is Zn MnO of electrolyte 2 And (5) full battery, and performing battery test.
(1) Preparing electrolyte
287.58g ZnSO was weighed out 4 ·7H 2 O is dissolved in 500mL deionized water to prepare 2 mol.L -1 ZnSO 4 A solution.
(2) Preparation of electrodes
Zinc negative electrode: polishing the surface of zinc foil with the thickness of 0.1mm, cutting out a wafer with the diameter of 12mm, ultrasonically treating with absolute ethyl alcohol for 15min, washing cleanly, and drying in vacuum.
MnO 2 And (3) a positive electrode: solution a: 0.768g of MnSO 4 ·H 2 O is dissolved in 15mL of deionized water and stirred uniformly;
solution B: 0.477g KMnO 4 Dissolving in 15mL deionized water, and stirring uniformly;
pouring the solution B into the solution A, stirring for 30min, quickly transferring to a hydrothermal high-pressure reaction kettle, and putting into an oven to be hydrothermal for 12h at 160 ℃. And after the reaction is finished, centrifugally separating the product, washing the product with water for 3 times, and finally drying the product in a baking oven at 60 ℃ to obtain the manganese dioxide material. Manganese dioxide, acetylene black and polyvinylidene fluoride are placed in an agate mortar according to the mass ratio of 7:2:1, and after being ground uniformly, a proper amount of N-methyl pyrrolidone is added, and grinding and mixing are continued until the slurry is obtained. Then coating the anode plate on a stainless steel current collector with the diameter of 12mm, and finally drying the anode plate in an oven at the temperature of 60 ℃ to obtain the anode plate.
(3) Symmetrical battery assembly
Zinc cathode, mnO 2 Positive electrode, glass fiber diaphragm, 2 mol.L -1 ZnSO 4 The solution is electrolyte, and the button CR2032 full battery is assembled.
(4) Full cell performance test
Testing the normal temperature cycle performance, setting the charge-discharge current at 25 ℃ to be 0.2 A.g -1 Long cycle performance testing was performed.
The results of the performance test of the battery are shown in fig. 6. At 0.2 A.g -1 At a current density of 2 mol.L -1 ZnSO 4 Zn MnO of electrolyte 2 The initial capacity of the battery is 231.50 mAh.g -1 After 380 cycles, a short circuit occurred, and the capacity retention was 46.5%.
The results of the above examples and comparative examples were analyzed as follows:
in FIG. 7, it can be seen from a long-cycle test chart of a Zn symmetric battery, that is, a battery having a Zn symmetry of 1.0 mA.cm -2 At current density (area capacity 1.0 mAh.cm) -2 ) Comparative example 1 uses 2 mol.L -1 ZnSO 4 The cell of the electrolyte suddenly drops in voltage around 89h because the "tip effect" of the zinc anode surface causes the separator to be pierced, and a short circuit occurs. Similarly, when the electrolyte is 1 mol.L -1 ZnSO 4 、3mol·L -1 ZnSO 4 In this case, the lifetime of the Zn symmetric battery was only 160h (fig. 8) and 93h (fig. 9). Whereas in examples 1, 2 and 3, 2 mol.L -1 ZnSO 4 Adding 0.1 g.L into electrolyte -1 、0.3g·L -1 、0.5g·L -1 After the nicotinic acid additive is added, the Zn symmetric battery respectively realizes long cycle life of 1200h (figure 1), 5200h (figure 2) and 900h (figure 3), which are better than the use of 2 mol.L -1 ZnSO 4 And the Zn of the electrolyte is Zn symmetrical battery. This is mainly due to the fact that the additive NA molecules can change the solvation and adsorption of zinc ions on the surface of the zinc anode, so that the zinc anode has lower nucleation overpotential, excellent dynamics performance, inhibition of dendrite growth and reduction of corrosion and side reactions. Wherein when the NA concentration is 0.3 g.L -1 When the cycle performance is most outstanding, the cycle life problem of the zinc ion battery can be almost solved. Similarly, at 1 mol.L -1 Zn 2+ 、3mol·L -1 Zn 2+ Adding 0.3 g.L of additive into the electrolyte -1 After NA, the service lives of Zn symmetric batteries were 480h (FIG. 4) and 1300h (FIG. 5). It is demonstrated that zinc ion electrolytes containing NA additives can extend the cycle life of aqueous zinc ion batteries. The cycle performance of the full cell in example 6 is shown in FIG. 6, which shows that the cycle performance is 0.2A.g -1 Zn MnO under current density 2 The first-turn capacity of the full battery reaches 240 mAh.g -1 And after 500 cycles, the capacity retention was 79.5%. Comparative example 4 uses 2 mol.L -1 ZnSO 4 Zn MnO of electrolyte 2 The capacity of the full battery is rapidly reduced, and a short circuit state occurs at about 380 turns. The zinc ion battery using the electrolyte of the invention has excellent electrochemical performance.
The above description is only an example of the present invention and is not intended to limit the scope of the present application, and various modifications and variations may be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.
Claims (5)
1. The aqueous zinc ion battery electrolyte is characterized by comprising soluble zinc salt, an electrolyte additive and deionized water, wherein the electrolyte additive is nicotinic acid.
2. The aqueous zinc-ion battery electrolyte of claim 1, wherein the soluble zinc salt is one of zinc sulfate and zinc chloride.
3. The aqueous zinc-ion battery electrolyte according to claim 1, wherein the soluble zinc salt has a zinc ion concentration of 1 to 3 mol/L -1 。
4. The aqueous zinc-ion battery electrolyte according to claim 1, wherein the concentration of the nicotinic acid is 0.1 to 0.5 g.l -1 。
5. Use of the aqueous zinc-ion battery electrolyte according to any one of claims 1 to 4 in an aqueous zinc-ion battery.
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