CN117317401A - Electrolyte for improving battery performance through biphase stabilization strategy and application thereof - Google Patents
Electrolyte for improving battery performance through biphase stabilization strategy and application thereof Download PDFInfo
- Publication number
- CN117317401A CN117317401A CN202311496224.1A CN202311496224A CN117317401A CN 117317401 A CN117317401 A CN 117317401A CN 202311496224 A CN202311496224 A CN 202311496224A CN 117317401 A CN117317401 A CN 117317401A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- zinc
- battery
- biphase
- performance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 104
- 230000006641 stabilisation Effects 0.000 title claims abstract description 21
- 238000011105 stabilization Methods 0.000 title claims abstract description 21
- 239000011701 zinc Substances 0.000 claims abstract description 106
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 104
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 104
- 239000000654 additive Substances 0.000 claims abstract description 43
- 230000000996 additive effect Effects 0.000 claims abstract description 41
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 230000002829 reductive effect Effects 0.000 claims abstract description 5
- 230000008021 deposition Effects 0.000 claims description 19
- 230000007797 corrosion Effects 0.000 claims description 11
- 238000005260 corrosion Methods 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 9
- 230000009977 dual effect Effects 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 claims description 5
- 229960000282 metronidazole Drugs 0.000 claims description 5
- YZEUHQHUFTYLPH-UHFFFAOYSA-N 2-nitroimidazole Chemical compound [O-][N+](=O)C1=NC=CN1 YZEUHQHUFTYLPH-UHFFFAOYSA-N 0.000 claims description 3
- AXRKIZCFYZBBPX-UHFFFAOYSA-N 3-bromo-5-nitrobenzoic acid Chemical compound OC(=O)C1=CC(Br)=CC([N+]([O-])=O)=C1 AXRKIZCFYZBBPX-UHFFFAOYSA-N 0.000 claims description 3
- WSYOWIMKNNMEMZ-UHFFFAOYSA-N 5-methyl-4-nitro-1h-imidazole Chemical compound CC=1NC=NC=1[N+]([O-])=O WSYOWIMKNNMEMZ-UHFFFAOYSA-N 0.000 claims description 3
- AEHPOYAOLCAMIU-UHFFFAOYSA-N Metronidazole-OH Chemical compound OCCN1C(CO)=NC=C1[N+]([O-])=O AEHPOYAOLCAMIU-UHFFFAOYSA-N 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims 1
- 238000012986 modification Methods 0.000 abstract description 16
- 230000004048 modification Effects 0.000 abstract description 16
- 210000001787 dendrite Anatomy 0.000 abstract description 10
- 238000004146 energy storage Methods 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000004458 analytical method Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 239000011241 protective layer Substances 0.000 abstract description 2
- 239000002000 Electrolyte additive Substances 0.000 abstract 1
- 230000005764 inhibitory process Effects 0.000 abstract 1
- 238000000151 deposition Methods 0.000 description 18
- 230000002051 biphasic effect Effects 0.000 description 13
- 210000004027 cell Anatomy 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 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
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 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
- 230000001351 cycling effect Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 229940102001 zinc bromide Drugs 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 description 2
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses an electrolyte for improving battery performance through a biphase stabilization strategy and application thereof, and belongs to a battery electrolyte preparation technology. Unlike traditional electrode modification and common electrolyte additives, the present invention proposes to introduce a biphase stabilizing additive into the battery electrolyte, which can pre-stabilize zinc cathode to construct three-dimensional porous grid substrate protective layer on the surface of the zinc cathode, and induce zinc to deposit and peel in the inner limit region of the zinc cathode. Meanwhile, after the grid is constructed, the functional groups of the double-phase stabilizing additive are dynamically changed and dispersed in the electrolyte to stabilize the electrolyte, so that the possibility of hydrogen analysis by the water of the electrolyte is reduced. Based on the two-phase stabilization strategy, the cycle stability and dendrite inhibition capability of the zinc-based battery are both remarkably improved. The method is convenient and efficient, provides a new strategy for preparing the high-performance electrolyte and improving the battery performance, and promotes the application of the zinc-based battery in the energy storage field.
Description
Technical Field
The invention belongs to the technical field of battery electrolyte preparation, relates to a novel electrolyte design and a zinc-based battery comprising the electrolyte, and particularly relates to an electrolyte for improving battery performance through a biphase stabilization strategy and application of the electrolyte.
Background
Green clean energy sources (such as wind, solar and tidal energy) have attracted worldwide attention based on the increasing demand for energy. However, their effective use is limited to a large extent by the inherent intermittence and non-diffusivity of renewable energy sources. These intermittent Electrical Energy Storage (EES) are a promising approach to ensure stability and sustainability at energy output. In the existing EES technology, rechargeable Lithium Ion Batteries (LIBs) have certainly become the dominant energy market, particularly in portable electronics and electric vehicles. However, their use as large-scale EES systems suffers from several problems, including limited lithium reserves, high raw material costs, and safety issues associated with flammable organic solvents. This dilemma has prompted researchers to seek advanced battery systems with environmental protection, economic benefits, safety, and excellent cycling stability/rate performance.
Aqueous batteries are considered to be the most promising energy storage system in large-scale applications in terms of safety, productivity, economy and ecology. Due to the advantages of the aqueous electrolyte, there is no safety problem such as fire or explosion even if the battery is short-circuited. The insensitivity of the electrolyte to moisture and oxygen also ensures easy assembly of the battery, which can be performed in an ambient atmosphere, significantly improving the efficiency of battery manufacturing. Zinc metal is relatively stable in a humid environment, and has high safety, low cost, and high theoretical capacity (820 mAh g -1 ,5851mAh cm -3 ) The aqueous zinc-based battery is therefore the most competitive candidate in the large-scale energy storage field. The zinc anode not only greatly simplifies the manufacturing process of the battery, but also improves the work of the water-based batteryWindows, which make aqueous zinc-based batteries a promising option for grid scale energy storage.
However, despite the widespread attention of aqueous zinc-based batteries, serious problems remain between zinc metal anodes and aqueous electrolytes, which make current battery performance far from satisfactory for practical use. Among them, zinc dendrite growth and hydrogen evolution corrosion and side reactions caused by aqueous electrolytes present two challenges for aqueous zinc-based batteries. Ideally, the zinc anode interface should remain smooth and dense in morphology, thereby achieving highly reversible zinc metal deposition and exfoliation. However, in practical applications, the zinc anode interface electric field and zinc ion flux are not uniform, so that zinc tends to form non-uniform dendritic zinc metal during the deposition process. The protrusions on the surface of the zinc negative electrode have a higher curvature than elsewhere, resulting in a relatively high electric field due to the "tip effect" to attract Zn 2+ The protrusions eventually evolve into zinc dendrites over a long period of time. These zinc dendrites may puncture the separator to cause internal short circuit failure of the cell on the one hand, and may peel off from the substrate to cause rapid decay in coulombic efficiency and cell capacity on the other hand.
Previous strategies for zinc cell research have focused on modification of the negative electrode and modification of the electrolyte. The negative electrode modification is mainly to manually coat a modification material or grow the modification material in situ on a zinc negative electrode interface. And the electrolyte modification mainly improves the electrolyte property and optimizes the zinc ion hydrate structure. In summary, the previous research is often focused on the study of the negative electrode or the electrolyte. The invention takes the two phases of the battery electrolyte and the electrode as a systematic unit, and synchronously realizes the in-situ optimization of the electrolyte and the electrode by introducing the biphase stabilizing additive into the electrolyte, so that the research work of the related content is not yet available.
Compared with the prior research work, the invention systematically solves the serious problems faced by the zinc battery through a biphase stabilization strategy. According to the invention, the circulation stability of the zinc cathode can be effectively improved by using the electrolyte containing the biphasic stabilizing additive, and the reversibility and stability of zinc deposition stripping in the operation process are greatly improved by synchronously stabilizing the zinc cathode and the electrolyte and obviously inhibiting zinc dendrites and dead zinc. In addition, the preparation method provided by the invention is simple and efficient, is easy to realize commercial production and implementation, provides a new thought for improving the electrochemical performance of the zinc battery, and has important significance for the development of high-performance zinc-based batteries.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the electrolyte for improving the battery performance through the biphase stabilization strategy and the application thereof, and the electrolyte can be particularly used for zinc-based batteries, can obviously improve the battery cycle stability, solve the problems of zinc dendrite growth and hydrogen evolution, and can optimize and modify the batteries. The dual-phase stabilization strategy provided by the invention plays a role in multiple optimization and high efficiency, and synchronously solves the problems of serious hydrogen evolution corrosion and the like caused by poor reversibility of zinc deposition stripping at a zinc cathode interface and high activity of electrolyte. The cycle stability of the zinc-based battery using the electrolyte is obviously improved, and the reversibility of zinc deposition stripping is obviously enhanced. Meanwhile, the strategy has low cost, simple process and remarkable effect, is beneficial to mass production, and further promotes the practical application process of the zinc-based battery in the energy storage field.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
an electrolyte for improving the performance of a battery through a dual-phase stabilization strategy comprises deionized water, a main electrolyte and a dual-phase stabilization additive.
Taking electrolyte of a zinc-based battery as an example, deionized water is firstly adopted as solvent to ultrasonically dissolve main electrolyte to be used as basic electrolyte. Wherein the main electrolyte component is at least one of zinc salts such as zinc sulfate, zinc trifluoromethane sulfonate, zinc chloride, zinc bromide, etc. To prepare a biphasic stabilised high performance electrolyte, it is necessary to further add a trace amount of biphasic stabilising additive to the base electrolyte and sonicate until complete dissolution. The adopted biphase stabilizing additive is at least one of 3-bromo-5-nitrobenzoic acid, metronidazole, hydroxymetronidazole, 2-nitroimidazole and 4-methyl-5-nitroimidazole.
These biphasic stabilizing additives have highly oxidative nitro groups capable of forming a three-dimensional porous lattice interface at the interface of the zinc oxide anode upon contact with the zinc anode. The grid interfaces can protect the zinc cathode from corrosion interference, and can be used as a zinc deposition stripping substrate to realize limited-area deposition and stripping of zinc metal. After the two-phase stabilizing additive reacts, the nitro group on the additive is reduced into amino groups to be dispersed in the electrolyte, so that the effect of stabilizing the electrolyte to reduce the activity of the electrolyte is achieved, and the occurrence of hydrogen evolution corrosion is further inhibited. Compared with the traditional interface modification and electrolyte modification, the scheme is more efficient and convenient, achieves dual-phase stability synchronously, provides new insight for constructing high-performance zinc-based batteries, and plays an important role in promoting the development of the zinc-based batteries.
The electrolyte containing the biphase stabilizing additive for the zinc-based battery is deionized water as a solvent, and the resistance is 16-25 MΩ.
Further, the main electrolyte of the electrolyte is at least one of zinc salts such as zinc sulfate, zinc trifluoromethane sulfonate, zinc chloride, zinc bromide and the like, and the concentration is 0.5mol L -1 ～3mol L -1 。
Further, the biphase stabilizing additive of the electrolyte is at least one of 3-bromo-5-nitrobenzoic acid, metronidazole, hydroxymetronidazole, 2-nitroimidazole and 4-methyl-5-nitroimidazole, and the concentration is 0.1g L -1 ～10g L -1 。
The electrolyte containing the biphase stabilizing additive can be applied to zinc-based batteries. The zinc-based battery comprises a zinc anode, a separator, a positive electrode containing an active ingredient and the electrolyte containing the biphasic stabilizing additive. The electrolyte can also be used in other batteries.
Compared with the prior art, the invention has the following remarkable advantages: (1) The traditional modification strategy is often concentrated on one side of electrode modification and electrolyte modification, and the electrode modification and the electrolyte modification are often considered out of the same. According to the scheme, the electrolyte containing the biphase stabilizing additive is adopted, the cathode and the electrolyte can be stabilized synchronously through a biphase stabilizing strategy, and the electrochemical performance of the battery is improved. (2) The biphase stabilizing additive in the electrolyte can induce the zinc cathode to form a specific three-dimensional grid interface, induce zinc metal to deposit and peel in the inner limit area of the zinc cathode, and remarkably improve the reversibility of zinc deposition and peeling. (3) After the interface between the biphasic stabilizing additive and the negative electrode in the electrolyte, the nitro group on the interface is converted into an amino group, so that the pH of the electrolyte is reduced, the activity of the electrolyte is weakened, the hydrogen evolution corrosion is inhibited, and the zinc ion flux is homogenized. (4) Compared with the prior art, the strategy is more convenient and fast, and is beneficial to industrialized application and production. (5) The electrolyte containing the biphase stabilizing additive can synchronously solve the problems faced by the zinc cathode and the electrolyte, and improves the cycling stability of the zinc-based battery.
Drawings
FIG. 1 is a field emission Scanning Electron Microscope (SEM) image of a three-dimensional porous grid interface induced by using a baseline electrolyte to cause corrosion of a zinc anode and using an electrolyte containing a biphasic stabilizing additive in example 2; (a) a zinc anode surface immersed in a reference electrolyte; (b) And immersing the zinc anode interface into electrolyte containing a biphasic stabilizing additive to generate a three-dimensional porous grid interface.
Fig. 2 is a comparison of charge and discharge test performance of a symmetric cell using a reference electrolyte and an electrolyte containing a dual phase stabilizing additive in example 3.
Fig. 3 is a comparison of coulombic efficiency performance of half-cells using the baseline electrolyte and electrolyte containing the dual phase stabilizing additive in example 4.
FIG. 4 is an SEM image of zinc deposition after using the baseline electrolyte with electrolyte containing a dual phase stabilizing additive in example 5; (a) Zinc deposition morphology on a zinc anode using a reference electrolyte; (b) The morphology of zinc deposition on the zinc cathode using electrolyte containing a biphasic stabilizing additive.
Detailed Description
The present invention will be described in further detail with reference to the drawings and 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.
The electrolyte for improving the battery performance through the biphase stabilization strategy is different from the traditional unilateral electrode modification and the unilateral electrolyte modification, and the biphase stabilization additive introduced by the invention can cooperatively stabilize the two phases of the cathode and the electrolyte. Taking zinc-based batteries as an example, on one hand, the biphase stabilizing additive can pre-stabilize a zinc cathode to construct a three-dimensional porous grid substrate protective layer on the surface of the zinc cathode, and induce zinc to deposit and peel in the inner limit region of the zinc cathode. Meanwhile, after the grid is constructed, the functional groups of the double-phase stabilizing additive are dynamically changed and dispersed in the electrolyte to stabilize the electrolyte, so that the possibility of hydrogen analysis by the water of the electrolyte is reduced. Based on the strategy, the cycle stability of the zinc-based battery using the electrolyte is obviously improved, and dendrite, dead zinc and hydrogen evolution corrosion phenomena are greatly improved.
Example 1:
(1) Adding 28.8g of zinc sulfate heptahydrate into a beaker, adding a proper amount of deionized water, and carrying out ultrasonic treatment to fully dissolve the zinc sulfate heptahydrate and the beaker to prepare 50ml of 2M ZnSO 4 The solution was used as a reference electrolyte.
(2) 45mg of metronidazole is weighed and added into the standard electrolyte in the step (1), and the solution is evenly dissolved by ultrasonic to obtain 50ml of 2M ZnSO 4 A +5mM metronidazole solution was used as the active electrolyte with a biphasic stabilizing additive.
Example 2:
(1) Zinc metal electrodes were placed in the electrolytes of examples 1 (1) and (2) for 2 hours, and were washed with deionized water, observed with a field emission Scanning Electron Microscope (SEM), and compared with the surface interface formation.
Fig. 1 is a comparison of SEM observations. It can be seen that the reference electrolyte does not modify the zinc anode, but rather corrodes the zinc anode to form corrosion spots and holes. The surface of the zinc cathode immersed in the biphasic stabilizing additive forms a compact three-dimensional porous grid interface, and the compact interface provides protection for the zinc cathode below the compact interface on one hand, so that the zinc cathode is prevented from corrosion, and provides space sites for zinc deposition on the other hand, so that zinc limited-area deposition stripping is induced.
Example 3:
(1) The electrolyte solutions (1) and (2) in example 1 were used to prepare symmetrical batteries for charge and discharge testingThe comparative cycle stability improves. The charge and discharge test conditions were 10mA cm -2 -5mAh cm -2 。
As shown in fig. 2, the cell using the electrolyte containing the dual phase stabilizing additive exhibited significantly improved electrochemical performance. For a cell using the reference electrolyte, it can only run for less than 20 hours, after which the sharp increase in polarization voltage is completely disabled, indicating severe hydrogen evolution corrosion and passivation inside the cell. The use of zinc cells containing a biphasic stabilizing additive electrolyte significantly solves this problem, increasing cycle life to over 1100 hours and maintaining stable electrochemical polarization. The use of the biphasic stabilizing additive is shown to be effective in inhibiting hydrogen evolution and zinc dendrite formation.
Example 4:
(1) The coulombic efficiency test was performed by taking the electrolyte solutions (1) and (2) in example 1 to prepare Zn Cu batteries respectively, and comparing the reversibility and stability improvement of zinc deposition stripping. The charge and discharge test conditions were 1mAcm -2 -1mAh cm -2 。
As shown in fig. 3, the superior effect of the dual phase stabilizing additive to improve the reversibility of zinc deposition strip was further demonstrated. The coulomb efficiency of the zinc-copper half cell using the reference electrolyte is extremely unstable, the reversibility of surface zinc deposition stripping is extremely poor, and the zinc-copper half cell can not be practically applied at all. While zinc-copper half cells using electrolyte with dual phase stabilizing additives can maintain coulombic efficiencies as high as 99.7% and run stably for over 500 cycles. This shows that the use of the two-phase stabilizing additive electrolyte can significantly enhance the reversibility of zinc metal deposition stripping, and fully exert the commercial application potential thereof.
Example 5:
(1) Taking the battery disassembled after the test in the embodiment 3, and observing the zinc deposition morphology of the zinc cathode interface by using a scanning electron microscope.
As shown in fig. 4, the zinc coating on the surface of the zinc negative electrode using the reference electrolyte appears to be very loose and irregular, and poor in connection with the substrate, which results in rampant growth of zinc dendrites, accelerating the failure of the zinc battery. The zinc at the zinc cathode interface containing the electrolyte of the dual-phase stabilizing additive can be uniformly and compactly deposited in the three-dimensional porous grid interface induced by the dual-phase stabilizing additive to form a good uniform zinc deposition coating, so that the reversibility of zinc deposition stripping is greatly enhanced.
In summary, the invention innovatively provides a biphase stabilizing strategy, the circulating stability of the zinc cathode can be effectively improved by using the electrolyte containing the biphase stabilizing additive, and the reversibility and stability of zinc deposition stripping in the operation process are greatly improved by synchronously stabilizing the zinc cathode and the electrolyte and obviously inhibiting zinc dendrite and dead zinc. In addition, the preparation method provided by the invention is simple and efficient, and is easy to realize commercial production. The invention creates an electrolyte containing the biphase stabilizing additive, provides a new thought for improving the electrochemical performance of the zinc battery, and has important significance for the development of high-performance zinc-based batteries.
Claims (5)
1. An electrolyte for improving the performance of a battery through a two-phase stabilization strategy, which is characterized by comprising deionized water, a main electrolyte and a two-phase stabilization additive.
2. The electrolyte for improving battery performance through a bi-phase stabilization strategy according to claim 1, wherein the bi-phase stabilization additive comprises at least one of 3-bromo-5-nitrobenzoic acid, metronidazole, hydroxymetronidazole, 2-nitroimidazole, 4-methyl-5-nitroimidazole.
3. The electrolyte for improving battery performance through a dual phase stabilization strategy according to claim 1, further characterized in that the dual phase stabilization additive is contained in an extremely trace amount of 0.1gL in the electrolyte -1 ～10g L -1 。
4. The electrolyte for improving battery performance through a bi-phase stabilization strategy according to claim 1, wherein the bi-phase stabilization additive is capable of achieving a bi-phase stabilization effect, in particular by: on one hand, a three-dimensional porous grid substrate can be formed on the surface of the battery cathode, and the finite field deposition stripping in the porous grid is realized; on one hand, the two-phase stabilizer groups after the reaction are changed to play a role in stabilizing the electrolyte, so that the activity of the electrolyte is reduced, and the hydrogen evolution corrosion is inhibited.
5. A zinc-based battery, characterized in that the battery contains the electrolyte according to any one of claims 1-4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311496224.1A CN117317401A (en) | 2023-11-10 | 2023-11-10 | Electrolyte for improving battery performance through biphase stabilization strategy and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311496224.1A CN117317401A (en) | 2023-11-10 | 2023-11-10 | Electrolyte for improving battery performance through biphase stabilization strategy and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117317401A true CN117317401A (en) | 2023-12-29 |
Family
ID=89284967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311496224.1A Pending CN117317401A (en) | 2023-11-10 | 2023-11-10 | Electrolyte for improving battery performance through biphase stabilization strategy and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117317401A (en) |
-
2023
- 2023-11-10 CN CN202311496224.1A patent/CN117317401A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111916744B (en) | Liquid metal composite cathode of zinc ion battery and preparation method and application thereof | |
| CN113410453B (en) | Preparation method of metal-organic coordination film modified zinc cathode | |
| CN112635698B (en) | Negative pole piece of zinc secondary battery and preparation method and application thereof | |
| CN108123141A (en) | A kind of three-dimensional porous foams grapheme material and its application | |
| CN114447446A (en) | Aqueous zinc ion battery additive, electrolyte prepared from same and application of electrolyte | |
| CN112928343B (en) | Water system copper ion battery suitable for large-scale energy storage application | |
| CN117293422A (en) | Method for inducing uniform deposition of zinc cathode of water-based zinc ion battery | |
| CN113314773A (en) | Aqueous zinc ion battery electrolyte and preparation method and application thereof | |
| CN117080584A (en) | Maltitol-containing aqueous zinc ion electrolyte additive and application thereof | |
| WO2023240891A1 (en) | Cyano group-modified zr-fe mof, preparation method therefor, and zinc-based flow battery zinc negative electrode material | |
| CN114628644B (en) | In-situ preparation method of TCNQ-based protective layer for zinc battery cathode | |
| CN116315158A (en) | Application of carboxylic ester compound as aqueous electrolyte additive, electrolyte containing aqueous electrolyte additive and zinc ion battery | |
| CN115863799A (en) | Electrolyte additive for zinc battery and application thereof | |
| CN117317401A (en) | Electrolyte for improving battery performance through biphase stabilization strategy and application thereof | |
| CN114927772A (en) | Electrolyte additive, application thereof, electrolyte and water-based zinc ion battery | |
| CN114447445A (en) | Preparation and application of aqueous zinc ion battery electrolyte | |
| CN114243019A (en) | Zinc cathode material with double modification layers on surface, preparation method thereof and application of zinc cathode material in water-based zinc ion battery | |
| CN115084636B (en) | Composite modified electrolyte for improving stability of water-based zinc ion battery and preparation method thereof | |
| CN117317414A (en) | Low-cost electrolyte additive, electrolyte and zinc battery | |
| CN116072866A (en) | Cyanation composite interface for stabilizing negative electrode of zinc-based battery and preparation method thereof | |
| CN116565346A (en) | Electrolyte for water-based zinc-based battery and preparation and application thereof | |
| CN116722232A (en) | Electrolyte modified based on taurine or derivative thereof, soft-package water-based zinc ion battery and preparation method | |
| CN117374427A (en) | Electrolyte for aqueous zinc ion battery and application thereof | |
| CN117712518A (en) | Water-based zinc ion battery electrolyte containing trace amino acid additive and application thereof | |
| CN117096465A (en) | Wide Wen Yuxin-base eutectic electrolyte and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |