Modification method and application of aqueous zinc ion battery electrolyte based on glutathione as additive

Abstract

The invention discloses a modification method and application of an aqueous zinc ion battery electrolyte based on glutathione as an additive. The electrolyte additive is used for solving the corrosion problem caused by dissolved oxygen (DO) and protons. The coexisting glutathione / oxidized glutathione redox pair can spontaneously capture DO and eliminate generated H2. In addition, the GSH destroys an original hydrogen bond network, the freezing point of the electrolyte is reduced, and the phenomena of serious corrosion and electrolyte evaporation at high temperature are slowed down. In the operation process of the battery, a self-healing organic-inorganic hybrid solid electrolyte interfacial film (SEI) can be formed, and dendritic crystal growth is inhibited. And a dynamic chemical self-deoxidation / self-dehydrogenation strategy is adopted, so that the cycling stability of the metal negative electrode is effectively improved, and meanwhile, the environmental adaptability of the aqueous zinc ion battery in a relatively wide temperature range is remarkably improved.

Description

Technical Field

[0001] The present invention relates to the technical field of batteries, and in particular to a method for modifying a wide-temperature-range aqueous zinc ion battery electrolyte based on a glutathione (GSH) additive and its application. Background Art

[0002] The large-scale application of lithium (Li)-based batteries is restricted by limited lithium reserves and safety issues. To address these issues, rechargeable aqueous zinc-ion batteries (AZIBs) have been developed due to the inherent advantages of metallic zinc anodes, such as 820 mAh g -1 The gravimetric capacity is as high as 5854 mAh cm -3 AZIBs, with their high volumetric capacity, low redox potential (-0.762 V vs. SHE), and high safety, have become promising candidates. As energy storage needs continue to diversify, there is a growing demand for AZIBs to remain stable at extreme temperatures. Applications such as polar exploration, military operations, and desert photovoltaics require wide-temperature tolerance. However, the practical application of AZIBs faces significant challenges stemming from the temperature sensitivity of aqueous electrolytes. Conventional aqueous electrolytes readily freeze at subzero temperatures, resulting in reduced interfacial wettability and slower ion transport kinetics. Furthermore, while high temperatures accelerate reaction kinetics, they also accelerate water evaporation and exacerbate side reactions at the electrode-electrolyte interface by increasing water activity. Significant progress has been made in addressing the temperature sensitivity of aqueous electrolytes through electrolyte modification and anode interface engineering. However, the long-standing challenge of interfacial electrochemical instability caused by dissolved oxygen (DO) over a wide temperature range has often been overlooked.

[0003] It is generally believed that severe zinc corrosion is primarily caused by proton corrosion, a spontaneous reaction between the zinc anode and water. However, it is worth noting that aqueous electrolytes are typically prepared in an air environment, which inevitably introduces dissolved oxygen into the electrolyte. The strong oxidizing property of dissolved oxygen (DO) can trigger oxygen-induced corrosion, forming byproducts such as ZnO or Zn(OH)2. It has been reported that in aqueous electrolytes, oxygen has a much stronger oxidizing power than protons. This means that over a wide temperature range, the zinc anode in aqueous electrolytes is theoretically more susceptible to corrosion by dissolved oxygen (DO) than by protons. Furthermore, unlike conventional aqueous lithium / sodium batteries, simply removing O2 does not improve the performance of AZIBs because it exacerbates the competing hydrogen evolution reaction (HER). Against this backdrop, dynamically and compatibly regulating dissolved oxygen and proton corrosion of the zinc anode over a wide temperature range has become a pressing challenge for the development of high-performance aqueous zinc-ion batteries. Summary of the Invention

[0004] The purpose of the present invention is to address the problems existing in the above-mentioned prior art and to propose a protective preparation method and application based on a reduced glutathione / oxidized glutathione redox pair for synergistically inhibiting dissolved oxygen and proton corrosion on a zinc metal negative electrode over a wide temperature range.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is: a method for preparing an electrolyte based on glutathione to synergistically alleviate dissolved oxygen and proton corrosion of zinc negative electrode, characterized in that the specific steps of the method are as follows:

[0006] Step 1: Prepare electrolyte control solutions dominated by dissolved oxygen corrosion and proton corrosion respectively: pump argon into a 2-mol Zn(OTF)2 electrolyte for 1 hour to completely remove DO in the electrolyte, and then seal it to prepare a proton corrosion-dominated electrolyte control solution for standby use; pump oxygen into a 2-mol Zn(OTF)2 electrolyte for 1 hour to obtain a dissolved oxygen corrosion-dominated electrolyte control solution containing saturated dissolved oxygen, and then seal it for standby use;

[0007] Step 2: Prepare an electrolyte containing glutathione additive: Under continuous magnetic stirring, dissolve 2 mol of Zn(OTF)2 in 1 L of deionized water to prepare a 2 mol Zn(OTF)2 aqueous electrolyte, recorded as ZF; add glutathione to the above 2 mol Zn(OTF)2 electrolyte to prepare a control electrolyte, recorded as GSH-ZF.

[0008] This electrolyte is used in aqueous batteries, and synergistically eliminates dissolved oxygen and proton corrosion through self-deoxygenation and self-dehydrogenation reactions to extend the battery life and cycle stability under a wide temperature range.

[0009] The principle behind this invention is that glutathione (GSH), a thiol with strong antioxidant properties, has been widely used to dynamically maintain redox balance through the GSH / GSSG cycle in mammalian cells, regulate environmental stress in plants by scavenging reactive oxygen species, and monitor dissolved oxygen levels in rivers. Inspired by this, we introduced GSH as an oxygen scavenging additive into a 2 M Zn(OTF)2 electrolyte. By utilizing the reversible dynamic chemical reaction between GSH and oxidized glutathione (GSSG), we simultaneously eliminated corrosion caused by both dissolved oxygen and protons.

[0010] GSH effectively eliminates dissolved oxygen (DO) in the electrolyte through self-deoxygenation, and the generated oxidized glutathione (GSSG) subsequently removes hydrogen (H2) through self-dehydrogenation. Based on the redox-mediated cycle between GSH and GSSG, a synergistic inhibition of dissolved oxygen corrosion and proton corrosion in the electrolyte is achieved. In the temperature range of -10°C to 40°C, the dissolved oxygen concentration in the electrolyte is significantly reduced, and GSH can also achieve a high continuous deoxygenation efficiency, which is beneficial to alleviate dissolved oxygen corrosion. On the other hand, GSH can destroy the original hydrogen bond network, lower the freezing point, and weaken the hydrogen evolution corrosion caused by water molecules. In addition, GSH and OTF - A hybrid organic-inorganic solid electrolyte interface (SEI) is formed, with an inner ZnF2 / ZnS-rich inorganic layer and an outer amide-rich organic layer. The addition of a bio-based antioxidant, GSH, is beneficial for inhibiting dissolved oxygen and hydrogen evolution corrosion, promoting uniform zinc deposition, and stabilizing the solid-liquid interface of the zinc metal anode.

[0011] The beneficial effects of the present invention are: the present invention abandons the traditional complex and energy-consuming physical deoxygenation method, adopts a dynamic chemical self-deoxygenation / self-dehydrogenation strategy, effectively inhibits dissolved oxygen corrosion and proton corrosion in the long term, effectively enhances the cycle stability of the zinc metal negative electrode, and significantly improves the environmental adaptability of the aqueous battery in a wide temperature range. Through the synergistic elimination of dissolved oxygen and hydrogen by the GSH / GSSG redox pair in a wide temperature range, dissolved oxygen and hydrogen evolution corrosion are alleviated. In addition, GSH can destroy the original hydrogen bond network, lowering the freezing point to below -55°C, further inhibiting hydrogen evolution corrosion. In addition, GSH and OTF - Together, they form an organic-inorganic hybrid SEI and promote the preferential orientation of the (002) crystal plane, making the Zn deposition uniform. As a result, the Zn||Zn symmetric battery using the GSH-modified electrolyte has a service life of up to 5000 h at -10°C, up to 1700 h at 25°C, and up to 2500 h at 40°C, showing excellent cycling stability. At the same time, the average CE of 98.83% over 1000 cycles at 25°C, close to 100% over 3400 cycles at -10°C, and 98.68% over 900 cycles at 40°C, revealing high reversibility at various temperatures. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 is a SEM image of the original Zn foil of the present invention.

[0013] Figure 2 The zinc foil of the present invention is immersed in DO corrosion electrolyte, (a) SEM image, (b) particle size analysis diagram.

[0014] Figure 3 The zinc foil of the present invention immersed in a proton corrosion electrolyte, (a) SEM image, (b) particle size analysis diagram.

[0015] Figure 4 It is the XRD pattern of Zn foil immersed in DO corrosion and proton corrosion electrolyte.

[0016] Figure 5 The Zn||Zn symmetric battery using DO corrosion and proton corrosion electrolytes at 25°C showed a high current density of 0.5 mA cm after 7 days of standing. -2 , areal capacity of 0.25 mAh cm -2 Cycle life graph.

[0017] Figure 6 The Zn||Zn symmetric battery using DO corrosion and proton corrosion electrolytes at 40°C after 7 days of standing still is shown in (a) at a current density of 0.5 mA cm -2 , areal capacity of 0.25 mAh cm -2 Cycle life diagram, (b) SEM image.

[0018] Figure 7 The Zn||Zn symmetric battery using DO corrosion and proton corrosion electrolytes at -10°C after 7 days of standing still is (a) at a current density of 0.5 mA cm -2 , areal capacity of 0.25 mAh cm -2 Cycle life diagram, (b) SEM image.

[0019] Figure 8 is the dissolved oxygen concentration in different electrolytes, (a) in the range of -10°C to 40°C, and (b) at different exposure times in air at 25°C.

[0020] Figure 9 The zinc foil of the present invention is immersed in ZF electrolyte, (a) SEM image, (b) particle size analysis diagram.

[0021] Figure 10 This is a SEM image of the zinc foil immersed in the GSH-ZF electrolyte of the present invention.

[0022] Figure 11 The Zn||Zn symmetric battery using ZF and GSH-ZF electrolytes at 25°C showed a high current density of 0.5 mA cm after 7 days of standing. -2, areal capacity of 0.25 mAh cm -2 Cycle life graph.

[0023] Figure 12 These are the Tafel curves of different electrolytes at 25°C and 40°C.

[0024] Figure 13 Comparison of (a) Raman spectra and (b) hydrogen bond formation of different electrolytes.

[0025] Figure 14 It is the DSC test of different electrolytes.

[0026] Figure 15 This is a study on the electrolyte volatility of different electrolytes at 40°C within 24 h.

[0027] Figure 16 The Zn||Zn symmetric battery uses different electrolytes at 1 mA cm -2 -1 mAh cm -2 EDS spectrum after 20 cycles.

[0028] Figure 17 The results are shown in (a) ZF and (b) GSH-ZF electrolytes at 2 mA cm -2 -1 mAh cm -2 XPS pattern of Zn anode after 20 cycles.

[0029] Figure 18 Schematic diagram of the performance improvement of GSH additive from -10°C to 40°C.

[0030] Figure 19 The Zn||Zn symmetric battery with different electrolytes at 1 mA cm at 25°C -2 and 0.5 mAh cm -2 Cycling performance under .

[0031] Figure 20 The Zn||Zn symmetric battery with different electrolytes at 1 mA cm -2 and 0.25 mAh cm -2 Cycling performance under .

[0032] Figure 21 The Zn||Zn symmetric battery with different electrolytes at 1 mA cm at 40°C -2 and 1 mAh cm -2 Cycling performance under .

[0033] Figure 22 The cycling performance of the present invention is compared with that of a recently reported modification strategy. DETAILED DESCRIPTION

[0034] The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments cannot be understood as limiting the present invention.

[0035] The modification method of the aqueous zinc ion battery electrolyte based on glutathione as an additive in this embodiment has the following specific steps:

[0036] Step 1: Prepare electrolytes dominated by dissolved oxygen corrosion and proton corrosion: Pump argon (Ar) into the prepared 2 M Zn (OTF) 2 electrolyte for 1 hour to completely remove DO (O2 content is about 1 ppm) in the electrolyte, and then seal it to further study proton-dominated corrosion (referred to as proton corrosion electrolyte); set aside. Pump oxygen (O2) into the prepared 2 M Zn (OTF) 2 electrolyte for 1 hour to obtain an electrolyte saturated with dissolved oxygen (DO), and then seal it to further study DO-dominated corrosion (referred to as DO corrosion electrolyte); set aside;

[0037] Step 2: Prepare the electrolyte containing glutathione additive: Dissolve 2 mol Zn(OTF)2 (brand: Macklin, 98%) in deionized water under continuous magnetic stirring to prepare 2 M (molar concentration, mol L -1 ) Zn(OTF)2 aqueous electrolyte (denoted as ZF), and then 1 L solution was obtained in air at room temperature. Different amounts (5 mM, 10 mM, 15 mM and 20 mM) of glutathione (C 10 H 17 N3OS, brand: Aladdin, 98%) was used to prepare the control electrolyte.

[0038] The following tests were performed on the electrolyte systems prepared in this embodiment:

[0039] Test 1: Due to the highly reactive thermodynamic corrosion characteristics of dissolved oxygen and water molecules on zinc, the surface of the zinc negative electrode is continuously corroded by the aqueous electrolyte, resulting in a significant decrease in the stability of the electrolyte / zinc metal negative electrode solid-liquid interface in a wide temperature range. Alleviating dissolved oxygen corrosion and parasitic water decomposition on the zinc negative electrode at different temperatures is one of the most severe challenges currently facing aqueous zinc-ion batteries. First, in order to systematically study the effect of DO corrosion on the zinc negative electrode, pure O2 was added to the ZF electrolyte, and by controlling the gas purge, a DO-dominated corrosion system (denoted as DO corrosion electrolyte) and a proton-dominated corrosion system (denoted as proton corrosion electrolyte) were obtained. Subsequently, the polished zinc foil was immersed in different electrolytes for one week, and scanning electron microscopy (SEM) analysis showed that the zinc foil had obvious morphological differences. Compared with the smooth surface morphology of the original Zn foil ( Figure 1 ), zinc foil immersed in DO corrosion electrolyte generated a large amount of flaky byproducts with a particle size of 5.91±1.47µm ( Figure 2 ), while Zn foil immersed in proton corrosion electrolyte showed only sparse flake-like byproducts with a particle size of 0.82±0.18µm ( Figure 3 ). XRD analysis shows that Zn foil immersed in DO corrosion and proton corrosion electrolytes exhibits a by-product Zn (OTF) y (OH) 2x-y The zinc foil immersed in DO corrosion electrolyte shows a stronger peak intensity than that in proton corrosion electrolyte ( Figure 4 ). At a current density of 0.5 mA cm -2 , areal capacity of 0.25 mAh cm -2 In the case of DO corrosion electrolyte, the Zn||Zn symmetric battery in the proton corrosion electrolyte showed a sudden cell polarization failure after 7 days of standing and 2 h of cycling. In contrast, the Zn||Zn symmetric battery in the proton corrosion electrolyte showed better stability and 130 h of zinc plating / stripping reversibility after 7 days of standing ( Figure 5 ), which proves that DO corrosion is more harmful than proton corrosion for long-term cycling stability including the rest process.

[0040] Test 2: In addition, the effect of DO corrosion on the cycling stability of Zn||Zn symmetric cells in a wide temperature range (-10°C-40°C) was also studied. Figure 6 As shown in a, DO corrosion is severe at 40°C. After standing for 7 days, the circuit fails due to severe voltage polarization after only 2 hours of cycling. SEM image ( Figure 6b) shows that this failure is due to the accumulation of a large amount of byproducts on the electrode surface caused by dissolved oxygen corrosion at high temperature, which blocks the Zn 2+ transmission channel. In contrast, at -10°C, the corrosion reaction was significantly reduced. Electrochemical cycling tests showed that the symmetrical battery operated stably for 140 hours after standing for 7 days and eventually failed due to short circuit ( Figure 7 a). SEM image ( Figure 7 b) It is proved that this is because DO corrosion forms small-sized byproducts at low temperatures, which are unevenly distributed, resulting in limited active sites on the electrode surface. 2+ The aggregation and deposition of Zn triggered the growth of Zn dendrites, which eventually led to short-circuit failure after 140 h of subsequent cycling. In contrast, the battery with proton-corrosion electrolyte showed better cycling stability over a wider temperature range. However, it is worth noting that the battery in the proton-corrosion electrolyte also failed after cycling for 130 h (40°C) and 290 h (-10°C), indicating that the performance of batteries using physically deoxygenated electrolytes is difficult to be satisfactory.

[0041] Test 3: GSH / GSSG dynamically eliminates dissolved oxygen and hydrogen through redox cycle reactions (Equations 4.1 and 4.2), stabilizing the Zn negative electrode. The ability of GSH to eliminate DO in the electrolyte over a wide temperature range (-10°C-40°C) was quantitatively tested using a dissolved oxygen meter. Figure 8 As shown in a, the O2 concentration in the GSH-ZF electrolyte was significantly reduced in the range of -10°C to 40°C compared with the ZF electrolyte. At the same time, the DO concentrations in the ZF electrolyte and the GSH-ZF electrolyte at different exposure times at 25°C were further evaluated ( Figure 8 b). It is clear that the addition of GSH significantly suppresses the DO concentration in the ZF electrolyte with increasing exposure time. To further investigate the anti-corrosion effect of glutathione (GSH) on dissolved oxygen (DO) and protons at the Zn anode, the polished Zn foil was immersed in ZF and GSH-ZF electrolytes for one week. SEM images show that the Zn foil immersed in the ZF electrolyte produces byproducts ( Figure 9 a), Statistical particle size analysis of corrosion byproducts shows a size of approximately 1.99µm ( Figure 9 b). In the GSH-ZF electrolyte, even after soaking for a week, there is still no by-product on the surface of the zinc foil ( Figure 10 ).like Figure 11 As shown in Figure 3, the Zn||Zn symmetric cell using the GSH-ZF electrolyte maintained excellent cycling stability and electrochemical reversibility during the plating / stripping process, maintaining stable cycling for more than 1300 h after 7 days of rest. In contrast, the cell using the ZF electrolyte exhibited failure in just 100 h, which was attributed to severe DO and proton corrosion.

[0042] (4.1)

[0043] (4.2)

[0044] Test 4: GSH disrupts the original hydrogen bond network, thereby lowering the freezing point and slowing corrosion and electrolyte evaporation at high temperatures. A systematic study of the corrosion kinetics of the zinc anode is shown by Tafel plots. In the GSH-ZF electrolyte, the corrosion current (icorr) in the Tafel plot decreases (from 49.28 to 1 mA cm-1) at different temperatures. -2 , 40°C; decreased from 9.66 to 0.3 mA cm -2 , 25°C) ( Figure 12 a and 12b). At the same time, the corrosion potential increased (from -0.006 to -0.001 V at 40°C and from 0.0006 to 0.0026 V at 25°C). These results indicate that GSH has a significant protective effect against corrosion over a wide temperature range. Subsequently, Raman analysis also showed that the GSH additive can break the original hydrogen bond network, thereby weakening the activity of water. Due to the intermolecular hydrogen bonding (HO:H) interactions between water molecules, the GSH-containing ions at 3000-3700 cm -1 The OH vibration peak is mainly composed of three groups of Raman scattering peaks: strong HO:H (3230 cm -1 ), weak HO:H (3450 cm -1 ) and no HO:H (3620 cm -1 As the Raman analysis results of ZF electrolyte ( Figure 13 a and Figure 13 As shown in b), the OH with lower bond energy (3230 cm -1 ) still occupies a large area ratio (29.1%), which indicates that due to the strong hydrogen bonding interaction, there are still a large number of water molecules in the ZF electrolyte and they show high reactivity. Glutathione (GSH) triggered a change in the hydrogen bond network through obvious spectral shifts: the high-intensity HO:H configuration (12.1%) blue-shifted, while the low-intensity corresponding configuration (87.4%) red-shifted, which together indicated a dynamic redistribution of hydrogen bonding interactions. This structural evolution is manifested as a decay of the high-intensity HO:H configuration and a corresponding enhancement of the low-intensity corresponding configuration, which together highlight the GSH-induced changes in the hydrogen bond network and the reduction in water activity. These changes help to reduce the evaporation of the electrolyte at high temperatures and lower the freezing point of the electrolyte, thereby helping to enhance the wide temperature stability. To verify this, differential scanning calorimetry (DSC) and electrolyte volatility studies were carried out. Figure 14As shown in the figure, the GSH-induced change in the hydrogen bond network leads to a decrease in the freezing point to approximately -55°C. Compared with the ZF electrolyte, this modification gives it excellent antifreeze properties and shows enhanced low-temperature stability. At the same time, due to the destruction of the hydrogen bond network, the thermal stability of the electrolyte at high temperatures is greatly improved. After standing at 40°C for 24 hours, the volume of the ZF electrolyte was significantly reduced to 75%. In sharp contrast, GSH-ZF retained 95% of its original volume under the same conditions ( Figure 15 ).

[0045] Test 5: It is worth noting that GSH and OTF - Actively participate in the formation of solid electrolyte interface film (SEI). After 20 cycles of Zn||Zn symmetric battery using aqueous ZF electrolyte with / without GSH additive, the EDS spectrum of the electrode sheet shows that the distribution of Zn, C, S, O and F elements in ZF electrolyte is uneven ( Figure 16 ). For batteries using GSH-ZF electrolyte, the uniform distribution of Zn, C, S, O, F, and N elements on the surface of the zinc negative electrode was also confirmed, among which the SEI component containing N came from the GSH additive. Therefore, the composition of SEI was studied by XPS. Figure 17 As shown in a, an inorganic SEI layer composed of ZnF2 / ZnS was detected on the surface of the Zn anode cycled in the ZF electrolyte. In contrast, organic species derived from GSH additives, CO (286.17 eV in C1s), C=O (289.56 eV in C1s), and Zn-N (398.8 eV in N1s), were detected on the surface of the Zn anode cycled in the GSH-ZF electrolyte. Figure 17 b). At the same time, it was also found that - Anion-derived ZnF2 (684.4 eV in F1s) and ZnS (161.5 eV in S2p) inorganics. In addition, with the Ar + As sputtering proceeds, the content of CO / C=O species decreases with increasing SEI depth, while the content of ZnF2 / ZnS increases with increasing SEI depth, which means that the SEI formed in the GSH-ZF electrolyte has the characteristics of an organic-inorganic hybrid double-layer structure with an inner ZnF2 / ZnS (inorganic-rich) layer and an outer CON (organic-rich) layer. As shown in previous studies, the organic-inorganic hybrid SEI interface can not only inhibit dendrite growth but also suppress side reactions.

[0046] The above experimental results were integrated and it was proposed that after adding GSH electrolyte additive, Figure 18As shown, the coexisting glutathione / oxidized glutathione redox couple can spontaneously capture DO and eliminate the generated H2, destroying the inherent hydrogen bond network, thereby helping to enhance the wide-temperature performance and form a self-healing hybrid solid electrolyte interface. It alleviates dissolved oxygen and proton corrosion and inhibits dendrite growth over a wide temperature range. On the contrary, since the electrolyte easily freezes under low temperature conditions, it leads to reduced interfacial wettability, reduced ionic conductivity and delayed ion transport kinetics. At the same time, high temperature conditions accelerate water evaporation and aggravate the side reaction interface of the electrode electrolyte. In addition, dissolved oxygen (DO) induces severe interfacial electrochemical instability over a wide temperature range, making the battery face the dilemma of rapid failure over a wide temperature range.

[0047] In this study, symmetrical cells were assembled using ZF and GSH-ZF as electrolytes to investigate the potential of GSH additives in regulating the solid-liquid interface stability of zinc metal anodes. Figure 19 As shown, at 1 mA cm -2 and 0.5 mAh cm -2 Under the same conditions, Zn||Zn batteries using conventional ZF aqueous electrolyte encountered random voltage fluctuations and irreversible polarization voltage increase after only 213 h. The main reason for the poor stability of Zn||Zn batteries in ZF electrolyte is that the presence of O2 accelerates the corrosion of the zinc anode during electrochemical cycling. In sharp contrast, under the same conditions, the battery containing GSH showed stable plating / stripping reversibility for more than 1674 h. The significant improvement of the cycle life stability of Zn||Zn batteries in GSH-ZF electrolyte is due to the dynamic elimination of DO and H2 in the electrolyte by GSH. In addition, we also evaluated the stability of zinc in GSH-ZF at different temperatures. Even at -10°C, at a current density of 1 mA cm -2 and a capacity of 0.25 mAh cm -2 Under the condition of high stability, 5000 h of galvanizing / stripping can be achieved ( Figure 20 When the temperature was increased to 40 °C, GSH-ZF was -2 and a capacity of 1 mAh cm -2 Good galvanizing / stripping reversibility is shown over 2500 h ( Figure 21 ). This indicates that GSH-ZF electrolyte batteries have the potential to meet applications in a wide temperature range.

[0048] The cycle life of Zn||Zn symmetric cells using GSH-ZF electrolyte at different current densities is compared with the recently reported modification strategy. Figure 22and the table below. Encouragingly, the Zn||Zn symmetric battery using the GSH-ZF electrolyte in this work significantly outperforms some previously reported representative works in terms of cycle life. This is primarily due to the fact that GSH molecules eliminate dissolved oxygen in the electrolyte through an oxidative dehydrogenation reaction. The resulting oxidized glutathione (GSSG) reacts with H2 from the hydrogen evolution reaction, promoting GSH regeneration through a redox-mediated cycle. The dynamic reversible reaction between GSH and GSSG effectively eliminates DO. Without causing irreversible GSH consumption, side reactions such as the HER and zinc anode passivation are significantly suppressed. Furthermore, a self-healing organic-inorganic hybrid SEI layer forms during battery operation, significantly suppressing DO corrosion, proton corrosion, and Zn dendrite growth.

[0049] Electrode Electrolyte <![CDATA[Current density, capacity (mAcm -2 , mAh cm -2 )]]> Lifespan (h) Ref. Zn foil <![CDATA[2 M ZnSO4 +10 mM GSH]]> 1, 0.50.5, 0.252, 11, 0.25 1700140014001200 This work <![CDATA[Sb2Оз@Zn]]> <![CDATA[2 M ZnSO4]]> 1, 0.5 1000 Angew. Chem. Int. Ed. 2023, 62, e202309765. Zn@Sb <![CDATA[2 M ZnSO4]]> 1, 1 800 Adv. Sci. 2022, 9, 2104866. Zn foil ZIG-20wt% 0.1, 0.1 900 Nat. Commun. 2023, 14, 3890. Zn@t-KTN <![CDATA[1 M ZnSO4]]> 2, 1 800 Adv. Sci. 2022, 9, 2105980. Sn@Zn-IP <![CDATA[2 M ZnSO4]]> 2, 1 700 Adv. Funct. Mater. 2022, 32, 2205771. Zn foil <![CDATA[2 M ZnSO4+1 mM Z10]]> 1, 1 600 Energy Storage Mater. 2023, 63, 102981. <![CDATA[ Zn@Sn-ZnF2]]> <![CDATA[2 M ZnSO4+1 mM I - ]]> 1, 1 500 Adv. Energy Mater. 2024, 14, 2303221.

[0050] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

Claims

1. A method for modifying an aqueous zinc ion battery electrolyte using glutathione as an additive, characterized in that: The specific steps of the method are as follows: Step 1: Prepare electrolyte control solutions dominated by dissolved oxygen corrosion and proton corrosion respectively: pump argon into a 2-mol Zn(OTF)2 electrolyte for 1 hour to completely remove DO in the electrolyte, and then seal it to prepare a proton corrosion-dominated electrolyte control solution for standby use; pump oxygen into a 2-mol Zn(OTF)2 electrolyte for 1 hour to obtain a dissolved oxygen corrosion-dominated electrolyte control solution containing saturated dissolved oxygen, and then seal it for standby use; Step 2: Prepare an electrolyte containing glutathione additive: Under continuous magnetic stirring, dissolve 2 mol of Zn(OTF)2 in 1 L of deionized water to prepare a 2 mol Zn(OTF)2 aqueous electrolyte, recorded as ZF; add glutathione to the above 2 mol Zn(OTF)2 electrolyte to prepare a control electrolyte, recorded as GSH-ZF.

2. An application of the wide-temperature-range aqueous zinc ion battery electrolyte based on glutathione as an additive as prepared as claimed in claim 1 in an aqueous battery, wherein the electrolyte prepared by this method is applied to an aqueous battery to extend the battery life and cycle stability.

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