Hydrogen isotope-based electrolyte and manganese ion battery

Abstract

The invention discloses a hydrogen isotope-based electrolyte and a manganese ion battery, and belongs to the field of batteries. The electrolyte comprises soluble manganese salt and a hydrogen isotope deuterated solvent. According to the invention, the hydrogen isotope effect is utilized to improve the dynamics of various manganese electrochemical reaction paths and the stability of an electrode-electrolyte interface, so that the manganese ion battery with high performance, high safety and wide voltage window is constructed, and the problems of dynamic hysteresis, poor reaction selectivity, poor stability and the like caused by the solvation effect of Mn < 2 + > in the existing manganese ion battery are solved. And an electrolyte solvent is easy to generate a decomposition side reaction on an electrode interface.

Description

Technical Field

[0001] This invention relates to the field of batteries, and more particularly to an electrolyte based on hydrogen isotopes and a manganese-ion battery. Background Technology

[0002] With the increasing scarcity of traditional lithium resources, the development of energy storage systems with high safety and low cost has become a research focus. Against this backdrop, alkali metal ion batteries have attracted widespread attention, among which manganese ion batteries show significant potential due to the abundant reserves of manganese (Mn) and its high theoretical energy density. On the one hand, the electronic configuration of manganese ([Ar]3d...) 5 4s 2 ) enables it to have Mn 0 To Mn 7+ Mn exhibits multivalent state characteristics and possesses diverse redox pathways; on the other hand, Mn... 2+ The low reduction potential and high oxidation potential enable it to maintain a stable ionic state over a wide voltage window. These characteristics provide rich possibilities for the design of manganese-ion batteries, thus enabling energy storage mechanisms based on the redox reactions of Mn species and Mn... 2+ Embedded / de-embedded energy storage mechanisms have attracted much attention in recent years. For example, those based on MnO2 / Mn 2+ Liquid-solid phase transformation reactions involving two-electron transfer during deposition / stripping are widely used as positive electrodes in many energy storage batteries due to their high redox potential and theoretical capacity; another example is the Mn2+240 ... 3+ / Mn 2+ The single-electron conversion positive electrode can couple with various negative electrode redox reactions to construct a high-rate full-cell system; in addition, Mn 2+ The reversible insertion / extraction reaction in the lattice of the embedded electrode material also provides an energy storage method based on the diffusion of ions in the solid lattice, which has good cycle stability.

[0003] However, the actual performance of manganese-ion batteries is limited by three key scientific issues related to the electrolyte: First, in the electrolyte, the Mn... 2+ It typically coordinates with multiple solvent molecules to form a solvation shell, resulting in a large solvation ionic radius and slow desolvation kinetics, which severely restricts the electrode reaction rate and battery rate performance; secondly, Mn 2+ The diverse oxidation / reduction products of Mn make highly selective directional conversion at the interface difficult, thus affecting the coulombic efficiency of the electrode reaction. Third, electrolyte solvent molecules are prone to decomposition side reactions at the electrode interface, which significantly limits the battery's operating voltage window and lifespan. Currently, there is a lack of methods to directly control the interaction between the solvent molecules and Mn, starting from the solvent molecules themselves. 2+ Related studies on the interaction between the two and their own electrochemical stability.

[0004] Therefore, existing technologies still need to be improved and developed. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the purpose of this invention is to provide a hydrogen isotope-based electrolyte and its manganese-ion battery. By utilizing the hydrogen isotope effect, the kinetics of various manganese electrochemical reaction pathways and the stability of the electrode-electrolyte interface are improved, thereby constructing a manganese-ion battery with high performance, high safety, and a wide voltage window. This aims to solve the problem of the limitations of existing manganese-ion batteries due to the influence of Mn... 2+ The solvation effect leads to kinetic stagnation, poor reaction selectivity, and the problem that the electrolyte solvent is prone to decomposition side reactions at the electrode interface.

[0006] First, it should be noted that the manganese-based energy storage mechanism involved in this invention mainly includes the following two pathways, both of which use Mn. 2+ As a core charge carrier: (1) Based on Mn 2+ Redox reaction: refers to Mn 2+ The electrode surface undergoes reversible gain and loss of electrons, transforming into other valence states of manganese (such as MnO2 / Mn²). + Energy storage is achieved through changes in valence state.

[0007] (2) Based on Mn 2+ Intercalation / extraction reaction: refers to Mn 2+ As a stable divalent cation, Mn can reversibly insert into and extract from the lattice channels of electrode materials (such as Prussian blue analogues, layered oxides, etc.) during charge and discharge. During this process, Mn... 2+ The valence state remains unchanged, and the charge balance is achieved by the redox reactions of other variable valence elements in the electrode material (or the redox reactions of the material as a whole).

[0008] Regardless of the mechanism described above, the Mn dissolved in the electrolyte 2+ Before reaching the electrode interface to react, they must overcome the constraints of their solvation shell, that is, undergo the "desolvation" step.

[0009] The core innovation of this invention lies in utilizing the hydrogen isotope effect to effectively reduce Mn 2+ The desolvation energy barrier enhances the reaction kinetics of the Mn energy storage pathway.

[0010] The technical solution of the present invention is as follows: In a first aspect, the present invention provides a hydrogen isotope-based electrolyte, wherein the electrolyte comprises a soluble manganese salt and a hydrogen isotope deuterated solvent.

[0011] Optionally, the soluble manganese salt includes one or more of MnSO4, MnCl2, Mn(NO3)2, Mn(ClO4)2, Mn(CH3COO)2, and Mn(CF3SO3)2; the electrolyte contains Mn 2+ The concentration is 0.01~5.0 mol L. -1 .

[0012] Optionally, the electrolyte further includes additives, which include one or more of aminopolycarboxylic acid compounds and polyphosphonic acid compounds; the concentration of the additives in the electrolyte is 0.01~1.0 mol L. -1 .

[0013] Optionally, the hydrogen isotope deuterated solvent includes at least one of deuterated inorganic solvents and deuterated organic solvents; The deuterated inorganic solvent includes one or more of deuterated water, deuterated sulfuric acid, deuterated hydrochloric acid, deuterated nitric acid, deuterated hydrofluoric acid, and deuterated phosphoric acid; The deuterated organic solvents include one or more of the following: deuterated alcohols, deuterated aromatic hydrocarbons, deuterated aliphatic hydrocarbons, deuterated amines, deuterated carbonates, deuterated ethers, deuterated carboxylic acid esters, deuterated nitriles, deuterated sulfur-containing solvents, deuterated amides, deuterated ketones, deuterated haloalkanes, deuterated ionic liquids, and deuterated phosphorus-containing solvents. The deuterated alcohol solvent is selected from one or more of deuterated aliphatic alcohols or deuterated alicyclic alcohols, such as deuterated methanol, deuterated ethanol, deuterated isopropanol, deuterated ethylene glycol, and deuterated cyclohexanol. The deuterated aromatic hydrocarbon solvent is selected from optionally substituted deuterated aromatic hydrocarbons, wherein the substituents are independently selected from alkyl, halogen, cyano or combinations thereof, such as one or more of deuterated benzene, deuterated toluene, deuterated chlorobenzene, deuterated naphthalene, and deuterated mesitylene. The deuterated aliphatic hydrocarbon solvent is selected from one or more deuterated chain or cyclic alkanes or alkenes, such as deuterated cyclohexane, deuterated n-hexane, deuterated n-heptane, deuterated cyclopentane, and deuterated hexene. The deuterated amine solvent is selected from deuterated aliphatic amines, deuterated alicyclic amines, or deuterated aromatic amines, such as one or more of deuterated triethylamine, deuterated pyridine, deuterated piperidine, deuterated N,N-diisopropylethylamine, and deuterated aniline; The deuterated carbonate solvent is selected from one or more of deuterated chain carbonates or cyclic carbonates, such as dimethyl deuterated carbonate, diethyl deuterated carbonate, methyl ethyl deuterated carbonate, ethylene deuterated carbonate, and propylene deuterated carbonate. The deuterated ether solvent is selected from one or more of deuterated chain ethers, cyclic ethers, or crown ethers, such as deuterated diethyl ether, deuterated tetrahydrofuran, deuterated 1,3-dioxolane, deuterated 1,4-dioxane, deuterated ethylene glycol dimethyl ether, and deuterated methyl nonafluorobutyl ether. The deuterated carboxylic acid ester solvent is selected from esters formed by deuterated carboxylic acids and deuterated alcohols, such as one or more of methyl deuterated acetate, ethyl deuterated acetate, ethyl deuterated propionate, and ethyl deuterated benzoate. The deuterated nitrile solvent is selected from one or more of deuterated aliphatic nitrile, such as deuterated acetonitrile, deuterated propionitrile, deuterated butyronitrile, deuterated glutaronitrile, and deuterated adiponitrile; The deuterated sulfur-containing solvent is selected from one or more of deuterated sulfoxides, sulfones, cyclic sulfonates or sulfates, such as deuterated dimethyl sulfoxide, deuterated sulfolane, deuterated vinyl sulfite, and deuterated vinyl sulfate. The deuterated amide solvent is selected from deuterated carboxylic acid amides, such as deuterated formamide, deuterated N-methylformamide, deuterated N,N-dimethylformamide, deuterated N-methylpyrrolidone, and deuterated N-ethylpyrrolidone, or one or more of these. The deuterated ketone solvent is selected from one or more of deuterated aliphatic ketones or deuterated alicyclic ketones, such as deuterated acetone, deuterated cyclohexanone, and deuterated methyl isobutyl ketone. The deuterated haloalkanes solvent is selected from deuterated haloalkanes or halocycloalkanes, wherein the halogen is fluorine, chlorine, bromine or iodine, such as deuterated dichloromethane, deuterated 1,2-dichloroethane, deuterated fluoroethylene carbonate, deuterated trifluoromethanesulfonate, deuterated 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, and deuterated trifluoromethylcyclohexane, or one or more of these. The deuterated ionic liquid includes one or more of the following: the cation is deuterated imidazolium, deuterated pyrrolidineonium, deuterated quaternary ammonium salt or deuterated quaternary phosphonium salt; and the anion is deuterated bis(trifluorosulfonyl)imide, deuterated hexafluorophosphate, deuterated tetrafluoroborate or deuterated trifluoromethanesulfonate, for example, deuterated 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide; The deuterated phosphorus-containing solvent is selected from deuterated phosphates, phosphites, or phosphonates, such as one or more of deuterated trimethyl phosphate, deuterated triethyl phosphate, deuterated triethyl phosphite, and deuterated dimethyl phosphonate.

[0014] A second aspect of the present invention provides a manganese-ion battery comprising an electrolyte and two electrodes disposed in the electrolyte, the two electrodes comprising a positive electrode and a negative electrode, wherein the electrolyte is the hydrogen isotope-based electrolyte of the present invention.

[0015] Optionally, the positive and negative electrodes are independently selected from Mn-based materials. 2+ Rapid and reversible redox reactions or based on rapid and reversible Mn2+ Intercalation / extraction reaction.

[0016] Optionally, when the electrode is based on Mn 2+ When operating in a rapid and reversible redox reaction, the electrode is a conductive substrate without active material, Mn 2+ A redox reaction occurs on the electrode surface, the reaction including Mn 2+ / Mn、MnO2 / Mn 2+ Mn 3+ / Mn 2 + Mn2O3 / Mn 2+ Mn3O4 / Mn 2+ One of them.

[0017] Optionally, when the electrode is based on Mn 2+ During rapid and reversible insertion / extraction reactions, the electrode is a conductive substrate containing active material, Mn. 2+ As charge carriers, they undergo reversible insertion and extraction within the lattice structure of this active material.

[0018] Optionally, the active material is an intercalation material having an ion-accommodating space or capable of undergoing ion intercalation / deintercalation reactions, including one of inorganic host materials and organic host materials.

[0019] Optionally, the inorganic host material includes one of layered compounds, Prussian blue analogs, polyanionic compounds, and carbon-based materials; The layered compounds include one of the following: inorganic silicates, phosphates, titanates, arsenates, cobaltates, layered bimetallic hydroxides, transition metal sulfides, vanadium oxides, and molybdenum oxides; The Prussian blue analogues include one of the cyanide coordination polymers of transition metals, with the general chemical formula A. x M1[M2(CN)6]y·nH2O (where M1 and M2 represent Co) 2+ Fe 2+ Mn 2+ Cu 2+ Zn 2+ Ni 2+ (e.g., A is an alkali metal, alkaline earth metal, or other monovalent cation). The polyanionic compound can be represented by the general chemical formula A. x M y (XO4) n Where A is an alkali metal ion such as Na + Li +In the series XO4, M is one or more transition metals with variable oxidation states, such as Fe, Mn, V, Ni, Cu, etc., and XO4 is a polyanionic group, where X is usually an element such as P, S, Si, Mo, etc. that can form a stable tetrahedral structure. The carbon-based material includes one of graphite, carbon nanotubes, carbon black, and diamond.

[0020] Optionally, the organic host material includes one of organic molecular crystals, porous organic polymers, and metal-organic framework materials; The organic molecular crystals are organic crystal materials assembled from aromatic compounds through supramolecular interactions such as hydrogen bonding, π-π stacking, and van der Waals forces, such as hexaazatrinaphthalene, quinoline, tetracarboxylic acid diimide, 9,10-phenanthroline, 3,4,9,10-pyrene tetracarboxylic anhydride, 5,7,12,14-pentaphenyltetraone, 2,5-dichloro-p-benzoquinone, etc. The porous organic polymer is a covalent organic framework material, a covalent triazine skeleton, a conjugated microporous polymer, a hypercrosslinked polymer, a porous aromatic polymer, etc. The metal-organic framework material is a coordination polymer with a porous structure, which is constructed by orderly connection of metal ions / clusters and organic ligands through coordination bonds, such as network metal-organic framework materials, rare earth-polymer framework materials, zeolite imidazole framework compounds, etc.

[0021] Optionally, the conductive substrate includes one of the following: carbon felt, carbon paper, carbon cloth, tantalum sheet, titanium sheet, titanium mesh, etc.

[0022] Compared with the prior art, the beneficial effects of the present invention include: (1) By introducing hydrogen isotopes, the kinetics of various manganese electrochemical reaction pathways and the stability of the electrode-electrolyte interface were improved, and a high-performance, high-safety and wide-voltage-window manganese-ion battery was constructed. (2) Based on the abundant manganese resources, it provides a feasible technical alternative to alleviate the current energy storage technology’s dependence on scarce lithium resources, which is of great strategic significance for promoting the sustainable development of battery systems; (3) For the first time, isotopes were applied to the design of manganese-ion batteries, which not only improved the dynamics and interface stability, but also provided a universal principle for the rational design of other metal-ion batteries. Attached Figure Description

[0023] Figure 1 This provides spectroscopic evidence for the influence of hydrogen isotope effects on solvated structures and hydrogen bond networks.

[0024] Figure 2 This represents the electrochemical stability window of the electrolyte.

[0025] Figure 3This is a schematic diagram of the operation of a three-electrode battery system.

[0026] Figure 4 The MnO2 / Mn assembled in Example 1 2+ Charge and discharge curves of the battery system.

[0027] Figure 5 Mn assembled in Example 2 3+ / Mn 2+ Charge and discharge curves of the battery system.

[0028] Figure 6 Mn assembled in Example 3 2+ Charge-discharge curves of the embedded / deactivated battery system.

[0029] Figure 7 Mn assembled in Example 4 2+ Charge-discharge curves of the embedded / de-embedded battery system.

[0030] Figure 8 MnO2 / Mn assembled in Comparative Example 1 2+ Charge and discharge curves of the battery system.

[0031] Figure 9 Mn assembled in Comparative Example 2 3+ / Mn 2+ Charge and discharge curves of the battery system.

[0032] Figure 10 Mn assembled in Comparative Example 3 2+ Charge-discharge curves of the embedded / deactivated battery system.

[0033] Figure 11 Mn assembled in Comparative Example 4 2+ Charge-discharge curves of the embedded / de-embedded battery system.

[0034] Figure 12 This is a schematic diagram of the operation of the all-manganese-ion battery assembled in Application Example 1.

[0035] Figure 13 The charge / discharge curves and rate performance diagrams of the all-manganese-ion battery assembled in Application Example 1 are shown. Detailed Implementation

[0036] This invention provides a hydrogen isotope-based electrolyte and its manganese-ion battery. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0037] The actual performance of manganese-ion batteries is limited by three key scientific issues related to the electrolyte: First, the composition of Mn in the electrolyte... 2+ It typically coordinates with multiple solvent molecules to form a solvation shell, resulting in a large solvation ionic radius and slow desolvation kinetics, which severely restricts the electrode reaction rate and battery rate performance; secondly, Mn 2+ The diverse oxidation / reduction products of Mn make highly selective directional conversion at the interface difficult, thus affecting the coulombic efficiency of the electrode reaction. Third, electrolyte solvent molecules are prone to decomposition side reactions at the electrode interface, significantly limiting the battery's operating voltage window and lifetime. Currently, there is a lack of methods to directly control the interaction between the solvent molecules and Mn, starting from the solvent molecules themselves. 2+ Related studies on the interaction between the two and their own electrochemical stability.

[0038] Therefore, improving the electrochemical reaction kinetics of manganese and the stability of the electrode-electrolyte interface, and constructing high-performance, high-safety manganese-ion batteries with a wide voltage window, is of great practical significance.

[0039] This invention utilizes deuterium ( 2 H) replaces hydrogen in the electrolyte solvent ( 1 H), optimizing Mn through hydrogen isotope effects 2+ Improving the coordination environment, reducing the desolvation energy barrier, and enhancing the electrochemical stability of the electrolyte provide a core direction for achieving rapid ion transport and widening the voltage window, which is of great significance for promoting the development of high-performance manganese-ion batteries.

[0040] Specifically, this embodiment of the invention provides a hydrogen isotope-based electrolyte, wherein the electrolyte comprises a soluble manganese salt and a hydrogen isotope deuterated solvent.

[0041] In this embodiment, the hydrogen isotope-based electrolyte is prepared using a soluble manganese salt and a hydrogen isotope deuterated solvent. The manganese-ion battery using this electrolyte is based on Mn. 2+ Reversible electrochemical reaction operation. This is achieved by utilizing deuterium (… 2 H) replaces hydrogen in the electrolyte solvent ( 1 H) has achieved improvements in the kinetics of multiple manganese electrochemical reaction pathways and enhanced electrode-electrolyte interface stability, providing an innovative electrolyte design strategy for the development of high-performance, high-safety, and wide-voltage-window manganese-ion battery technology.

[0042] Its core mechanism is as follows: hydrogen isotopes ( 1 H and 2 The difference in nuclear quantum effects between H) 1 H and 2 Significant differences in atomic mass of H ( 2 The mass of H is approximately 1(twice the amount of H), resulting in C / N / O- 2 H bonds and C / N / O- 1 Hydrogen bonds exhibit differences in fundamental properties such as vibrational frequency, bond length, and hydrogen bond strength. These microscopic differences further influence the dielectric properties, intermolecular interactions, and ion-solvent interactions of the solvent system.

[0043] like Figure 1 As shown, by comparing electron paramagnetic resonance spectra (left), Mn in the deuterated electrolyte can be observed. 2+ The coordination environment of the electrolyte undergoes significant changes; simultaneously, the O- in the electrolyte is observed in the infrared spectrum (right). 1 H and O- 2 Differences in H vibrational frequencies directly reflect changes in the hydrogen bond network and solvation structure. For example... Figure 2 As shown, linear sweep voltammetry tests indicate that the deuterated electrolyte has a wider and more stable electrochemical stability window.

[0044] Based on this, through 2 H substitute 1 H, this invention achieves the following two key controls: firstly, optimizing Mn 2+ The first is to improve the solvation structure, reduce the desolvation energy barrier, and enhance ion migration and reaction kinetics; the second is to reconstruct the hydrogen bond network in the electrolyte, thereby enhancing the chemical and electrochemical stability of the solvent molecules themselves and the electrode-electrolyte interface.

[0045] In one embodiment, the soluble manganese salt includes, but is not limited to, various Mn compounds such as MnSO4, MnCl2, Mn(NO3)2, Mn(ClO4)2, Mn(CH3COO)2, and Mn(CF3SO3)2. 2+ One or more of the salts; Mn in the electrolyte 2+ The concentration is 0.01~5.0 mol L. -1 For example, 0.5 mol L -1 1.0 mol L -1 1.5 mol L -1 2.5 mol L -1 3.0 mol L -1 4.5 mol L -1 5.0 mol L -1 Other specific point values ​​within the above range can also be selected, and will not be elaborated on here.

[0046] In one embodiment, the main component of the solute in the electrolyte is a soluble manganese salt, and it may also contain additives; the additives include, but are not limited to, one or more of aminopolycarboxylic acid compounds and polyphosphonic acid compounds; the concentration of the additives in the electrolyte is 0.01~1.0 mol L. -1 For example, 0.01 mol L -1 0.03 mol L -1 0.05 mol / L -1 0.1 mol L -1 0.5 mol L -1 0.8 mol L -1 1.0 mol L -1 Other specific point values ​​within the above range can also be selected, and will not be elaborated on here.

[0047] In one embodiment, the hydrogen isotope deuterated ( 2H) The solvent is a deuterated solvent that can improve the electrochemical performance of the battery through the deuterium isotope effect, including at least one of deuterated inorganic solvents and deuterated organic solvents: (1) The deuterated inorganic solvent includes one or more of deuterated water, deuterated sulfuric acid, deuterated hydrochloric acid, deuterated nitric acid, deuterated hydrofluoric acid, and deuterated phosphoric acid; (2) The deuterated organic solvent includes one or more of deuterated alcohol solvents, deuterated aromatic hydrocarbon solvents, deuterated aliphatic hydrocarbon solvents, deuterated amine solvents, deuterated carbonate solvents, deuterated ether solvents, deuterated carboxylic acid ester solvents, deuterated nitrile solvents, deuterated sulfur-containing solvents, deuterated amide solvents, deuterated ketone solvents, deuterated halocarbon solvents, deuterated ionic liquids, and deuterated phosphorus-containing solvents; the deuterated alcohol solvent is selected from deuterated aliphatic hydrocarbons. The solvent is a tricyclic alcohol or a deuterated alicyclic alcohol, such as one or more of deuterated methanol, deuterated ethanol, deuterated isopropanol, deuterated ethylene glycol, and deuterated cyclohexanol; the deuterated aromatic hydrocarbon solvent is selected from optionally substituted deuterated aromatic hydrocarbons, wherein the substituents are independently selected from alkyl, halogen, cyano, or combinations thereof, such as deuterated benzene, deuterated toluene, deuterated chlorobenzene, deuterated naphthalene, and deuterated trimethylbenzene. One or more; the deuterated aliphatic hydrocarbon solvent is selected from deuterated chain or cyclic alkanes or alkenes, such as one or more of deuterated cyclohexane, deuterated n-hexane, deuterated n-heptane, deuterated cyclopentane, and deuterated hexene; the deuterated amine solvent is selected from deuterated aliphatic amines, deuterated alicyclic amines, or deuterated aromatic amines, such as deuterated triethylamine, deuterated pyridine, deuterated piperidine, and deuterated N,N-didiamine. One or more of isopropyl ethylamine and deuterated aniline; the deuterated carbonate solvent is selected from deuterated chain carbonates or cyclic carbonates, such as one or more of deuterated dimethyl carbonate, deuterated diethyl carbonate, deuterated methyl ethyl carbonate, deuterated ethylene carbonate, and deuterated propylene carbonate; the deuterated ether solvent is selected from deuterated chain ethers, cyclic ethers, or crown ethers, such as one or more of deuterated diethyl ether, deuterated tetrahydrofuran, deuterated 1,3-dioxolane, deuterated 1,4-dioxane, deuterated ethylene glycol dimethyl ether, and deuterated methyl nonafluorobutyl ether; the deuterated carboxylic acid ester solvent is selected from esters formed by deuterated carboxylic acids and deuterated alcohols, such as one or more of deuterated methyl acetate, deuterated ethyl acetate, deuterated ethyl propionate, and deuterated ethyl benzoate; the deuterated... The nitrile solvents are selected from deuterated aliphatic nitrile, such as one or more of deuterated acetonitrile, deuterated propionitrile, deuterated butyronitrile, deuterated glutaronitrile, and deuterated adiponitrile; the deuterated sulfur-containing solvents are selected from deuterated sulfoxides, sulfones, cyclic sulfonates, or sulfates, such as one or more of deuterated dimethyl sulfoxide, deuterated sulfolane, deuterated vinyl sulfite, and deuterated vinyl sulfate; the deuterated amide solvents are selected from deuterated carboxylic amides, such as one or more of deuterated formamide, deuterated N-methylformamide, deuterated N,N-dimethylformamide, deuterated N-methylpyrrolidone, and deuterated N-ethylpyrrolidone; the deuterated ketone solvents are selected from one or more of deuterated aliphatic ketones or deuterated alicyclic ketones, such as one or more of deuterated acetone, deuterated cyclohexanone, and deuterated methyl isobutyl ketone.The deuterated haloalkanes solvent is selected from deuterated haloalkanes or halocycloalkanes, wherein the halogen is fluorine, chlorine, bromine, or iodine, such as deuterated dichloromethane, deuterated 1,2-dichloroethane, deuterated fluoroethylene carbonate, deuterated trifluoromethanesulfonate, deuterated 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, and deuterated trifluoromethylcyclohexane; the deuterated ionic liquid includes cations of deuterated imidazolium, deuterated pyrrolidineonium, deuterated quaternary ammonium salts, or... A deuterated quaternary phosphonium salt, wherein the anion is one or more of deuterated ionic liquids containing deuterated bis(trifluorosulfonyl)imide, deuterated hexafluorophosphate, deuterated tetrafluoroborate, or deuterated trifluoromethanesulfonate, such as deuterated 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide; the deuterated phosphorus-containing solvent is selected from deuterated phosphates, phosphites, or phosphonates, such as one or more of deuterated trimethyl phosphate, deuterated triethyl phosphate, deuterated triethyl phosphite, and deuterated dimethylphosphonate.

[0048] In this embodiment, the manganese ion battery includes an electrolyte and two electrodes placed in the electrolyte. The two electrodes include a positive electrode and a negative electrode. The electrolyte is the hydrogen isotope-based electrolyte of the present invention.

[0049] In one implementation, the positive and negative electrodes are independently selected from Mn-based electrodes. 2+ Rapid and reversible redox reactions or based on Mn 2+ Rapid and reversible insertion / extraction reaction.

[0050] In one implementation, the Mn-based 2+ Rapid and reversible redox reactions refer to those involving Mn. 2+ Manganese multivalent redox reactions centered on Mn, including but not limited to Mn 2+ / Mn、MnO2 / Mn 2+ Mn 3+ / Mn 2+ Mn2O3 / Mn 2+ Mn3O4 / Mn 2+ wait.

[0051] In one implementation, the Mn-based 2+ The fast and reversible insertion / extraction reaction is Mn 2+Ion insertion / extraction occurs in ion-intercalated materials; wherein, the ion-intercalated materials are intercalated materials with ion-accommodating space or capable of ion insertion / extraction reactions, specifically divided into inorganic host materials and organic host materials: (1) The inorganic host materials include layered compounds, Prussian blue analogs, polyanionic compounds, carbon-based materials, etc. The layered compounds include inorganic silicates, phosphates, titanates, arsenates, cobaltates, layered bimetallic hydroxides, transition metal sulfides, vanadium oxides, molybdenum oxides, etc.; the Prussian blue analogs are cyanide coordination polymers of transition metals, whose general chemical formula is A x M1[M2(CN)6] y ·nH2O (where M1 and M2 represent Co) 2+ Fe 2+ Mn 2+ Cu 2+ Zn 2+ Ni 2+ (where A is an alkali metal, alkaline earth metal, or other monovalent cation); the polyanionic compound can be represented by the general chemical formula A. x M y (XO4) n Where A is an alkali metal ion such as Na + Li + M is one or more transition metals with variable oxidation states, such as Fe, Mn, V, Ni, Cu, etc., and XO4 is a polyanionic group, wherein X is usually an element such as P, S, Si, Mo, etc. that can form a stable tetrahedral structure; the carbon-based materials include graphite, carbon nanotubes, carbon black, diamond, etc.; (2) the organic host materials include organic molecular crystals, porous organic polymers, metal-organic framework materials, etc. The organic molecular crystals are organic crystal materials assembled from aromatic compounds through supramolecular interactions such as hydrogen bonding, π-π stacking, and van der Waals forces, such as hexaazatrinaphthalene, quinoline, tetracarboxylic acid diimide, 9,10-phenanthroline, 3,4,9,10-pyrene tetracarboxylic anhydride, 5,7,12,14-pentaphenyltetrazine, and 2,5-dichloro-p-benzoquinone; the porous organic polymers are covalent organic framework materials, covalent triazine skeletons, conjugated microporous polymers, hypercrosslinked polymers, and porous aromatic polymers; the metal-organic framework materials are coordination polymers with porous structures constructed by the orderly connection of metal ions / clusters and organic ligands through coordination bonds, such as network metal-organic framework materials, rare earth-polymer framework materials, and zeolite imidazole framework compounds.

[0052] In this embodiment, the electrochemical performance test of the manganese ion battery is carried out in a standard three-electrode system to accurately study the reaction process on the working electrode.

[0053] In one embodiment, the three-electrode system includes an electrolyte and three electrodes placed in the electrolyte: a working electrode, a counter electrode, and a reference electrode, such as... Figure 3 As shown. The working electrode is an electrode sheet without active material or an electrode sheet containing active material. The conductive substrate of the electrode sheet includes, but is not limited to, one of the following: carbon felt, carbon paper, carbon cloth, tantalum sheet, titanium sheet, titanium mesh, etc. The counter electrode includes, but is not limited to, one of the following: platinum sheet, platinum wire, graphite rod, activated carbon, graphite sheet, glassy carbon, carbon paper, carbon cloth, nickel mesh, nickel sheet, etc. The reference electrode includes, but is not limited to, one of the following: Ag / AgCl reference electrode, Hg / Hg2SO4 reference electrode, Hg / Hg2Cl2 reference electrode, activated carbon reference electrode, etc.

[0054] Compared with the prior art, this embodiment has the following beneficial effects: (1) By introducing hydrogen isotopes, the kinetics of various manganese electrochemical reaction pathways and the stability of the electrode-electrolyte interface were improved, and a high-performance, high-safety and wide-voltage-window manganese-ion battery was constructed. (2) Based on the abundant manganese resources, it provides a feasible technical alternative to alleviate the current energy storage technology’s dependence on scarce lithium resources, which is of great strategic significance for promoting the sustainable development of battery systems; (3) For the first time, isotopes were applied to the design of manganese-ion batteries, which not only improved the dynamics and interface stability, but also provided a universal principle for the rational design of other metal-ion batteries.

[0055] The present invention will be described in detail below through several specific embodiments.

[0056] Example 1: Construction of MnO2 / Mn using deuterated water as solvent 2+ Battery System Using pretreated carbon felt as the working electrode, a platinum sheet as the counter electrode, and Ag / AgCl as the reference electrode, a concentration of 1.0 mol L⁻¹ was used. -1 A three-electrode battery system was assembled using a MnCl2 solution (with deuterated water as the solvent) and its performance was tested.

[0057] (1) Pretreatment of conductive substrate: The carbon felt was successively cleaned with anhydrous ethanol, ultrasonically treated for 30 min and dried to obtain a clean carbon felt substrate. (2) Preparation of electrolyte: Add a certain mass of MnCl2 to a certain mass of deuterated water, stir thoroughly to dissolve, and obtain the electrolyte; (3) Assembly of the three-electrode battery system: The carbon felt substrate was immersed in the electrolyte, and the adsorbed gas on the carbon felt was removed by vacuum degassing to ensure full contact between the electrode and the electrolyte; the carbon felt working electrode, the platinum sheet counter electrode, and the Ag / AgCl reference electrode were installed in the electrolytic cell; after adding the electrolyte, the electrochemical performance was tested, and its charge-discharge curves are shown in the figure. Figure 4 As shown.

[0058] Example 2: Construction of Mn using deuterated water as solvent 3+ / Mn 2+ Battery System Using pretreated carbon felt as the working electrode, a platinum sheet as the counter electrode, and Ag / AgCl as the reference electrode, a concentration of 2.0 mol L⁻¹ was used. -1 MnCl2, 0.05 mol L -1 Na4EDTA, 0.05 mol L -1 A three-electrode battery system was assembled using a Na2MnEDTA mixed system as the electrolyte (with deuterated water as the solvent) and its performance was tested.

[0059] (1) Pretreatment of conductive substrate: The carbon felt was successively cleaned with anhydrous ethanol, ultrasonically treated for 30 min and dried to obtain a clean carbon felt substrate. (2) Preparation of electrolyte: Add a certain mass of MnCl2, Na4EDTA and Na2MnEDTA to a certain mass of deuterated water, stir thoroughly to dissolve, and obtain electrolyte; (3) Assembly of the three-electrode battery system: The carbon felt substrate was immersed in the electrolyte, and the adsorbed gas on the carbon felt was removed by vacuum degassing to ensure full contact between the electrode and the electrolyte; the carbon felt working electrode, the platinum sheet counter electrode, and the Ag / AgCl reference electrode were installed in the electrolytic cell; after adding the electrolyte, the electrochemical performance was tested, and its charge-discharge curves are shown in the figure. Figure 5 As shown.

[0060] Example 3: Construction of Mn using deuterated water as solvent 2+ Battery systems involving insertion / extraction of hexaazatrinaphthalene Using an electrode containing hexaazatrinaphthalene as the working electrode, a platinum sheet as the counter electrode, and Ag / AgCl as the reference electrode, a concentration of 1.0 mol / L was used. -1 A three-electrode battery system was assembled using a MnCl2 solution (with deuterated water as the solvent) and its performance was tested.

[0061] Electrode preparation: Carbon cloth was used as the conductive current collector. Its surface was cleaned with anhydrous ethanol, and then treated with 30% hydrogen peroxide to obtain a hydrophilic carbon cloth current collector. Hexaazatrinaphthalene powder, Ketjen black, single-walled carbon nanotubes, and PTFE binder were uniformly mixed in a mass ratio of 6:2:1:1. Then, N-methylpyrrolidone (NMP) solvent was added and the mixture was thoroughly ground and stirred to obtain a slurry. The prepared slurry was uniformly coated onto the surface of the hydrophilic carbon cloth current collector, and the NMP solvent was slowly evaporated on a 60℃ hot plate. The slurry was then transferred to a vacuum oven for drying at 100℃ for 24 hours to obtain the hexaazatrinaphthalene electrode.

[0062] (2) Preparation of electrolyte: Add a certain mass of MnCl2 to a certain mass of deuterated water, stir thoroughly to dissolve, and obtain the electrolyte; (3) Assembly of the three-electrode battery system: The hexaazatrinaphthalene electrode was immersed in the electrolyte, and the adsorbed gas on the electrode was removed by vacuum degassing to ensure full contact between the electrode and the electrolyte; the hexaazatrinaphthalene electrode, the platinum counter electrode, and the Ag / AgCl reference electrode were installed in the electrolytic cell; after adding the electrolyte, the electrochemical performance was tested, and its charge-discharge curves are shown in the figure. Figure 6 As shown.

[0063] Example 4: Construction of Mn using deuterated water and deuterated dimethyl sulfoxide as cosolvents 2+ Battery systems involving insertion / extraction of hexaazatrinaphthalene Using an electrode containing hexaazatrinaphthalene as the working electrode, a platinum sheet as the counter electrode, and Ag / AgCl as the reference electrode, a concentration of 1.0 mol / L was used. -1 A three-electrode battery system was assembled using a MnCl2 solution as the electrolyte (with deuterated water and deuterated dimethyl sulfoxide as co-solvents) and its performance was tested.

[0064] Electrode preparation: Carbon cloth was used as the conductive current collector. Its surface was cleaned with anhydrous ethanol, and then treated with 30% hydrogen peroxide to obtain a hydrophilic carbon cloth current collector. Hexaazatrinaphthalene powder, Ketjen black, single-walled carbon nanotubes, and PTFE binder were uniformly mixed in a mass ratio of 6:2:1:1. Then, N-methylpyrrolidone (NMP) solvent was added and the mixture was thoroughly ground and stirred to obtain a slurry. The prepared slurry was uniformly coated onto the surface of the hydrophilic carbon cloth current collector, and the NMP solvent was slowly evaporated on a 60℃ hot plate. The slurry was then transferred to a vacuum oven for drying at 100℃ for 24 hours to obtain the hexaazatrinaphthalene electrode.

[0065] (2) Preparation of electrolyte: Add a certain mass of MnCl2 to a certain mass of deuterated water-deuterated dimethyl sulfoxide cosolvent (where the volume fraction of deuterated dimethyl sulfoxide is 15%), stir thoroughly to dissolve, and obtain the electrolyte; (3) Assembly of the three-electrode battery system: The hexaazatrinaphthalene electrode was immersed in the electrolyte, and the adsorbed gas on the electrode was removed by vacuum degassing to ensure full contact between the electrode and the electrolyte; the hexaazatrinaphthalene electrode, the platinum counter electrode, and the Ag / AgCl reference electrode were installed in the electrolytic cell; after adding the electrolyte, the electrochemical performance was tested, and its charge-discharge curves are shown in the figure. Figure 7 As shown.

[0066] Comparative Example 1: Construction of MnO2 / Mn using ordinary deionized water as solvent 2+ Battery System Using pretreated carbon felt as the working electrode, a platinum sheet as the counter electrode, and Ag / AgCl as the reference electrode, a concentration of 1.0 mol L⁻¹ was used. -1 A three-electrode battery system was assembled using a MnCl2 solution as the electrolyte (with ordinary deionized water as the solvent) and its performance was tested.

[0067] (1) Pretreatment of conductive substrate: The carbon felt was successively cleaned with anhydrous ethanol, ultrasonically treated for 30 min and dried to obtain a clean carbon felt substrate. (2) Preparation of electrolyte: Add a certain mass of MnCl2 to a certain mass of deionized water, stir thoroughly to dissolve, and obtain the electrolyte; (3) Assembly of the three-electrode battery system: The carbon felt substrate was immersed in the electrolyte, and the adsorbed gas on the carbon felt was removed by vacuum degassing to ensure full contact between the electrode and the electrolyte; the carbon felt working electrode, the platinum sheet counter electrode, and the Ag / AgCl reference electrode were installed in the electrolytic cell; after adding the electrolyte, the electrochemical performance was tested, and its charge-discharge curves are shown in the figure. Figure 8 As shown.

[0068] Comparative Example 2: Construction of Mn using ordinary deionized water as solvent 3+ / Mn 2+ Battery System Using pretreated carbon felt as the working electrode, a platinum sheet as the counter electrode, and Ag / AgCl as the reference electrode, a concentration of 2.0 mol L⁻¹ was used. -1 MnCl2, 0.05 mol L -1 Na4EDTA, 0.05 mol L -1 A three-electrode battery system was assembled using a mixture of Na2MnEDTA as the electrolyte (with ordinary deionized water as the solvent) and its performance was tested.

[0069] (1) Pretreatment of conductive substrate: The carbon felt was successively cleaned with anhydrous ethanol, ultrasonically treated for 30 min and dried to obtain a clean carbon felt substrate. (2) Preparation of electrolyte: Add a certain mass of MnCl2, Na4EDTA and Na2MnEDTA to a certain mass of deionized water, stir thoroughly to dissolve, and obtain electrolyte; (3) Assembly of the three-electrode battery system: The carbon felt substrate was immersed in the electrolyte, and the adsorbed gas on the carbon felt was removed by vacuum degassing to ensure full contact between the electrode and the electrolyte; the carbon felt working electrode, the platinum sheet counter electrode, and the Ag / AgCl reference electrode were installed in the electrolytic cell; after adding the electrolyte, the electrochemical performance was tested, and its charge-discharge curves are shown in the figure. Figure 9 As shown.

[0070] Comparative Example 3: Construction of Mn using ordinary deionized water as solvent 2+ Battery systems involving insertion / extraction of hexaazatrinaphthalene Using an electrode containing hexaazatrinaphthalene as the working electrode, a platinum sheet as the counter electrode, and Ag / AgCl as the reference electrode, a concentration of 1.0 mol / L was used. -1 A three-electrode battery system was assembled using a MnCl2 solution as the electrolyte (with ordinary deionized water as the solvent) and its performance was tested.

[0071] (1) Electrode preparation: Carbon cloth was used as the conductive current collector. Its surface was cleaned with anhydrous ethanol and hydrophilic treatment was performed on the surface of the carbon cloth with 30% hydrogen peroxide by volume to obtain a hydrophilic carbon cloth current collector. Hexaazatrinaphthalene powder, Ketjen black, single-walled carbon nanotubes and binder PTFE were mixed uniformly in a mass ratio of 6:2:1:1. Then N-methylpyrrolidone (NMP) solvent was added and the mixture was thoroughly ground and stirred to obtain a slurry for later use. The prepared slurry was uniformly coated on the surface of the hydrophilic carbon cloth current collector and placed on a 60℃ hot plate to slowly evaporate the NMP solvent. Then it was transferred to a vacuum oven for drying treatment at a baking temperature of 100℃ for 24 hours to obtain a hexaazatrinaphthalene electrode. (2) Preparation of electrolyte: Add a certain mass of MnCl2 to a certain mass of ordinary deionized water, stir thoroughly to dissolve, and obtain the electrolyte; (3) Assembly of the three-electrode battery system: The hexaazatrinaphthalene electrode was immersed in the electrolyte, and the adsorbed gas on the electrode was removed by vacuum degassing to ensure full contact between the electrode and the electrolyte; the hexaazatrinaphthalene electrode, the platinum counter electrode, and the Ag / AgCl reference electrode were installed in the electrolytic cell; after adding the electrolyte, the electrochemical performance was tested, and its charge-discharge curves are shown in the figure. Figure 10 As shown.

[0072] Comparative Example 4: Construction of Mn using ordinary deionized water and dimethyl sulfoxide as cosolvents 2+Battery systems involving insertion / extraction of hexaazatrinaphthalene Using an electrode containing hexaazatrinaphthalene as the working electrode, a platinum sheet as the counter electrode, and Ag / AgCl as the reference electrode, a concentration of 1.0 mol / L was used. -1 A three-electrode battery system was assembled using a MnCl2 solution as the electrolyte (with ordinary deionized water and dimethyl sulfoxide as co-solvents) and its performance was tested.

[0073] (1) Electrode preparation: Carbon cloth was used as the conductive current collector. Its surface was cleaned with anhydrous ethanol and hydrophilic treatment was performed on the surface of the carbon cloth with 30% hydrogen peroxide by volume to obtain a hydrophilic carbon cloth current collector. Hexaazatrinaphthalene powder, Ketjen black, single-walled carbon nanotubes and binder PTFE were mixed uniformly in a mass ratio of 6:2:1:1. Then, N-methylpyrrolidone (NMP) solvent was added and the mixture was thoroughly ground and stirred to obtain a slurry for later use. The prepared slurry was uniformly coated on the surface of the hydrophilic carbon cloth current collector and placed on a 60℃ hot plate to slowly evaporate the NMP solvent. Then, it was transferred to a vacuum oven for drying at 100℃ for 24 hours to obtain a hexaazatrinaphthalene electrode.

[0074] (2) Preparation of electrolyte: Add a certain mass of MnCl2 to a certain mass of deionized water-dimethyl sulfoxide cosolvent (where the volume fraction of dimethyl sulfoxide is 15%), stir thoroughly to dissolve, and obtain the electrolyte; (3) Assembly of the three-electrode battery system: The hexaazatrinaphthalene electrode was immersed in the electrolyte, and the adsorbed gas on the electrode was removed by vacuum degassing to ensure full contact between the electrode and the electrolyte; the hexaazatrinaphthalene electrode, the platinum counter electrode, and the Ag / AgCl reference electrode were installed in the electrolytic cell; after adding the electrolyte, the electrochemical performance was tested, and its charge-discharge curves are shown in the figure. Figure 11 As shown.

[0075] Application Example 1: Assembling an all-manganese-ion battery using deuterated water as a solvent. Using pretreated carbon felt as the positive electrode and hexaazatrinaphthalene (HATN) as the negative electrode active material, with a concentration of 1.0 mol / L... -1 Using MnCl2 solution as the electrolyte (with deuterated water as the solvent), an all-manganese ion battery (HATN-Mn) was assembled. 2+ ||MnO2 / Mn 2+ ).

[0076] (1) Negative electrode preparation: Carbon cloth was used as the conductive current collector. Its surface was cleaned with anhydrous ethanol and hydrophilic treatment was performed on the surface of the carbon cloth with 30% hydrogen peroxide by volume to obtain a hydrophilic carbon cloth current collector. Hexaazatrinaphthalene powder, Ketjen black, single-walled carbon nanotubes and binder PTFE were mixed uniformly in a mass ratio of 6:2:1:1. Then N-methylpyrrolidone (NMP) solvent was added and the mixture was thoroughly ground and stirred to obtain a slurry for later use. The prepared slurry was uniformly coated on the surface of the hydrophilic carbon cloth current collector and placed on a 60℃ hot plate to slowly evaporate the NMP solvent. Then it was transferred to a vacuum oven for drying treatment at a baking temperature of 100℃ for 24 hours to obtain a hexaazatrinaphthalene electrode sheet. (2) Pretreatment of positive conductive substrate: The carbon felt was successively cleaned with anhydrous ethanol, ultrasonically treated for 30 min and dried to obtain a clean carbon felt substrate. (3) Preparation of electrolyte: Add a certain mass of MnCl2 to a certain mass of deuterated water, stir thoroughly to dissolve, and obtain the electrolyte; (4) Assembly of all-manganese ion battery: The carbon felt substrate and the negative electrode are submerged in the electrolyte. The adsorbed gas on the carbon felt is removed by vacuum degassing to ensure full contact between the electrode and the electrolyte. The carbon felt substrate and the negative electrode are assembled into a two-electrode beaker battery. MnO2 / M ... 2+ Deposition / exfoliation reaction, HATN electron delocalization and redox state change occur at the negative end (corresponding to Mn). 2+ Embedding / Extraction (e.g.) Figure 12 As shown in the figure), electrochemical performance was tested after adding electrolyte, and the test results are as follows. Figure 13 As shown.

[0077] In summary, this invention provides an electrolyte based on hydrogen isotopes and a manganese-ion battery. By utilizing deuterium (… 2 H) replaces hydrogen in the electrolyte solvent ( 1 H), which improves the performance of manganese-ion batteries. Its core mechanism is as follows: hydrogen isotopes ( 1 H and 2 The difference in nuclear quantum effects between H) 1 H and 2 Significant differences in atomic mass of H ( 2 The mass of H is approximately 1 (twice the amount of H), resulting in C / N / O- 2 H bonds and C / N / O- 1 Hydrogen bonds differ in fundamental properties such as vibrational frequency, bond length, and hydrogen bond strength. These microscopic differences further influence the dielectric properties, intermolecular interactions, and ion-solvent interactions of the solvent system. Specifically, through… 2 H substitute 1H, this invention achieves the following two key controls: firstly, optimizing Mn 2+ The first is to improve the solvation structure, reduce the desolvation energy barrier, and enhance ion migration and reaction kinetics; the second is to reconstruct the hydrogen bond network in the electrolyte, thereby enhancing the chemical and electrochemical stability of the solvent molecules themselves and the electrode-electrolyte interface.

[0078] Based on the above regulation, the present invention exhibits a significant positive hydrogen isotope effect in various manganese conversion battery systems (as shown in Table 1 below), specifically: (1) in MnO2 / Mn 2+ In a battery system with a two-electron redox reaction, deuterated electrolytes significantly improve the reversibility of charge-discharge and coulombic efficiency; (2) in Mn-based 3+ / Mn 2+ In a battery system based on a single-electron redox reaction, the deuterated electrolyte improves the discharge capacity and coulombic efficiency of the redox reaction; (3) in the Mn-based 2+ In battery systems involving insertion / extraction reactions, deuterated electrolytes significantly accelerate the Mn extraction process. 2+ The diffusion rate in the solid-state electrode is improved, thereby enhancing the rate performance and discharge capacity of the battery. Furthermore, the deuterated electrolyte exhibits higher reductive decomposition stability over a wider voltage range, indicating a significant broadening of its electrochemical stability window. This lays the foundation for the development of high-voltage manganese-based battery systems.

[0079] Table 1. Comparison of battery performance in Examples 1-4 and Comparative Examples 1-4

[0080] Therefore, by utilizing the hydrogen isotope effect, the kinetics of various manganese electrochemical reaction pathways and the stability of the electrode-electrolyte interface were improved, and a manganese-ion battery with high performance, high safety and wide voltage window was successfully constructed.

[0081] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.

Claims

1. An electrolyte based on hydrogen isotopes, characterized in that, The electrolyte comprises a soluble manganese salt and a hydrogen isotope deuterated solvent.

2. The hydrogen isotope-based electrolyte according to claim 1, characterized in that, The soluble manganese salt includes one or more of MnSO4, MnCl2, Mn(NO3)2, Mn(ClO4)2, Mn(CH3COO)2, and Mn(CF3SO3)2; the electrolyte contains Mn 2+ The concentration is 0.01~5.0 mol L. -1 .

3. The hydrogen isotope-based electrolyte according to claim 1, characterized in that, The electrolyte further includes additives, which include one or more of aminopolycarboxylic acid compounds and polyphosphonic acid compounds; the concentration of the additives in the electrolyte is 0.01~1.0 mol L. -1 .

4. The hydrogen isotope-based electrolyte according to claim 1, characterized in that, The hydrogen isotope deuterated solvent includes at least one of deuterated inorganic solvents and deuterated organic solvents.

5. A manganese-ion battery, comprising an electrolyte and two electrodes disposed in the electrolyte, the two electrodes comprising a positive electrode and a negative electrode, characterized in that, The electrolyte is the hydrogen isotope-based electrolyte according to any one of claims 1-4.

6. The manganese-ion battery according to claim 5, characterized in that, The reaction of the electrode is based on Mn 2+ Reversible redox reaction, Mn 2+ At least one of the reversible insertion / extraction reactions.

7. The manganese-ion battery according to claim 6, characterized in that, When the electrode is based on Mn 2+ During reversible redox reaction operation, the electrode is a conductive substrate without active material, Mn 2+ A reversible redox reaction occurs on the electrode surface, the reaction comprising Mn 2+ / Mn、MnO2 / Mn 2+ Mn 3+ / Mn 2+ Mn2O3 / Mn 2+ Mn3O4 / Mn 2+ One of them.

8. The manganese-ion battery according to claim 6, characterized in that, When the electrode is based on Mn 2+ During the reversible insertion / extraction reaction, the electrode is a conductive substrate containing active material, Mn 2+ As charge carriers, they undergo reversible insertion and extraction within the lattice structure of the active material.

9. The manganese-ion battery according to claim 8, characterized in that, The active material is an intercalation material with ion-accommodating space or capable of ion insertion / extraction reactions, including one of inorganic host materials and organic host materials.

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