Electrolyte compositions for rechargeable metal halide batteries

Abstract

Rechargeable metal halide batteries using an optimized electrolyte formulation exhibit high capacity at fast charging rates. The optimized electrolyte comprises a metal halide, an oxidizing gas, and a mixed solvent solution containing an ethylene glycol dimethyl ether-based compound at a volume fraction of 20% to 70% by volume of the mixed solvent solution. The mixed solvent solution may also contain a nitrile compound and / or a heterocyclic compound.

Description

Technical Field

[0001] The present invention relates generally to rechargeable batteries and, more particularly, to electrolyte compositions for rechargeable metal halide batteries. Background Art

[0002] Rechargeable batteries are used in a wide range of applications and are in high demand, from small batteries for industrial and medical devices to large batteries for electric vehicles and grid energy storage systems. Each application requires a range of electrochemical properties, yet current battery performance is still considered a limiting factor in meeting customers' demanding requirements.

[0003] There are two types of rechargeable batteries: those that operate through the electrochemical intercalation / deintercalation of active ions, such as lithium-ion batteries; and those that operate through conversion reactions of active electrode / electrolyte materials, such as nickel metal hydride (NiMH) batteries. The most well-known and widely used rechargeable battery is the lithium-ion battery, which uses an intercalated lithium compound as an electrode material, allowing lithium ions to move back and forth in the electrolyte pool. NiMH batteries use nickel hydroxide as the positive electrode, a hydrogen-absorbing alloy as the negative electrode, and an alkaline electrolyte (for example, potassium hydroxide).

[0004] Lithium-ion and NiMH batteries have drawbacks that have hindered their wider adoption. These include slow charging speeds and the high cost of the heavy metal cathode materials needed to make the batteries. Summary of the Invention

[0005] The present invention overcomes the shortcomings of the prior art by providing a rechargeable metal halide battery having an optimized electrolyte formulation.

[0006] In one embodiment, the present invention relates to a battery comprising: an anode; an electrolyte; and a cathode current collector in contact with the electrolyte, wherein the electrolyte facilitates ion transport between the anode and cathode current collector, and wherein the electrolyte comprises: (i) a mixed solvent comprising at least two organic liquid compounds, wherein at least one organic liquid compound is a compound having the chemical formula R 1 O-(CR 2 2CR 2 2O) n -CR 1 A compound based on ethylene glycol dimethyl ether, wherein n is an integer greater than 0, R 1 and R 2 The invention relates to a method for preparing an ethylene glycol dimethyl ether-based compound comprising: (i) a metal halide serving as an active cathode material, wherein the metal halide is dissolved in the mixed solvent; and (ii) an oxidizing gas dissolved in the mixed solvent.

[0007] In one embodiment, the present invention relates to an electrolyte for a rechargeable battery, comprising: (i) a mixed solvent containing at least two organic liquid compounds, wherein at least one organic liquid compound has a chemical formula R 1 O-(CR 2 2CR 2 2O) n -CR 1 A compound based on ethylene glycol dimethyl ether, wherein n is an integer greater than 0, R 1 and R 2 The invention relates to a method for preparing an ethylene glycol dimethyl ether-based compound comprising: (i) a metal halide dissolved in the mixed solvent; and (ii) an oxidizing gas dissolved in the mixed solvent. The method comprises the following steps:

[0008] In yet another embodiment, the present invention is directed to a rechargeable battery comprising: an anode; a cathode current collector; and an electrolyte that facilitates ion transport between the anode and the cathode current collector, wherein the cathode current collector is in contact with the electrolyte, and the electrolyte comprises: (i) lithium iodide dissolved in a mixed solvent and an oxidizing gas dissolved in the mixed solvent, wherein the mixed solvent comprises 1,2-dimethoxyethane, and (ii) at least one additional organic compound.

[0009] In one embodiment, the anode includes one or more than one alkali metal and / or one or more than one alkaline earth metal.

[0010] In one embodiment, the cathode current collector comprises a porous carbon material and / or a metal.

[0011] In one embodiment, the porous carbon material is selected from the group consisting of carbon cloth, carbon nanoparticles, polymer binders, and combinations thereof.

[0012] In one aspect, the present invention relates to a method for preparing an electrolyte for a metal halide rechargeable battery, the method comprising: dissolving a metal halide in a mixed solvent solution; and introducing an oxidizing gas into the mixed solvent solution, wherein the mixed solvent solution comprises at least two organic liquid compounds, wherein at least one of the at least two organic liquid compounds is a metal halide having a chemical formula R 1 O-(CR 2 2CR 2 2O) n -CR 1 A compound based on ethylene glycol dimethyl ether, wherein n is an integer greater than 0, R 1 and R 2The ethylene glycol dimethyl ether-based compound is independently a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or alkylaryl group, and has a volume fraction of 20 volume % to 70 volume % of the mixed solvent solution.

[0013] In another aspect, the present invention relates to a method for making a metal halide rechargeable battery, the method comprising: dissolving a metal halide in a mixed solvent solution to form an electrolyte solution; forming an impregnated separator by immersing the separator in the electrolyte solution; forming a stack comprising an anode, the impregnated separator, and a cathode current collector, wherein the impregnated separator is positioned between the anode and the cathode current collector, the cathode current collector being in contact with the electrolyte, and the electrolyte promoting ion transport between the anode and the cathode current collector; introducing an oxidizing gas into the stack, wherein the mixed solvent solution comprises at least two organic liquid compounds, wherein at least one of the at least two organic liquid compounds is a compound having the chemical formula R 1 O-(CR 2 2CR 2 2O) n -CR 1 A compound based on ethylene glycol dimethyl ether, wherein n is an integer greater than 0, R 1 and R 2 The ethylene glycol dimethyl ether-based compound is independently a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or alkylaryl group, and has a volume fraction of 20 volume % to 70 volume % of the mixed solvent solution.

[0014] In another aspect, the present invention relates to a method for preparing an electrolyte for a metal halide rechargeable battery, the method comprising: mixing a metal halide, an oxidizing gas, and components of a mixed solvent solution, wherein the mixed solvent solution comprises at least two organic liquid compounds, wherein at least one of the at least two organic liquid compounds has a chemical formula, R 1 O-(CR 2 2CR 2 2O) n -CR 1 A compound based on ethylene glycol dimethyl ether, wherein n is an integer greater than 0, R 1 and R 2 The ethylene glycol dimethyl ether-based compound is independently a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or alkylaryl group, and has a volume fraction of 20 volume % to 70 volume % of the mixed solvent solution.

[0015] In another aspect, the present invention relates to a method for making a metal halide rechargeable battery, the method comprising: mixing a metal halide, an oxidizing gas, and components of a mixed solvent solution to form an electrolyte solution; forming an impregnated separator by immersing the separator in the electrolyte solution; forming a stack comprising an anode, the impregnated separator, and a cathode current collector, wherein the impregnated separator is placed between the anode and the cathode current collector, the cathode current collector being placed in contact with the electrolyte solution, and the metal halide serving as the active cathode material; wherein the mixed solvent solution comprises at least two organic liquid compounds, wherein at least one of the at least two organic liquid compounds is a compound having the chemical formula R 1 O-(CR 2 2CR 2 2O) n -CR 1 A compound based on ethylene glycol dimethyl ether, wherein n is an integer greater than 0, R 1 and R 2 The compound is independently a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or alkylaryl group, and the ethylene glycol dimethyl ether-based compound has a volume fraction of 20 volume % to 70 volume % of the mixed solvent solution.

[0016] In other embodiments and aspects, each R 1 and each R 2 Independently selected from C1-C 10 Straight chain alkyl, C3-C 10 Branched alkyl, C3-C 10 Cyclic alkyl, C2-C 10 Straight chain alkenyl, C3-C 10 Branched alkenyl, C3-C 10 Cyclic alkenyl and C5-C 10 Aryl.

[0017] In yet other embodiments and aspects, each R 1 and each R 2 Independently selected from C1-C 10 Straight chain alkyl halide groups, C3-C 10 Branched alkyl halide groups, C3-C 10 Cyclic alkyl halide groups, C2-C 10 Straight chain alkenyl halide groups, C3-C 10 Branched alkenyl halide groups, C3-C 10 Cyclic alkenyl halide groups and C5-C 10 Aryl halide group.

[0018] In other embodiments and aspects, each R 1 and each R 2 Independently selected from X1-X10 Straight chain alkyl, X3-X 10 Branched alkyl, X3-X 10 Cyclic alkyl, X2-X 10 Straight-chain alkenyl, X3-X 10 Branched alkenyl, X3-X 10 Cyclic alkenyl and X5-X 10 Aryl groups, wherein each X is a carbon atom, a nitrogen atom, an oxygen atom, or a silicon atom.

[0019] In yet other embodiments and aspects, R is a linear, branched or cyclic alkyl, alkenyl or aryl group. 1 and / or R 2 At least one hydrogen atom in the group is substituted by a halogen atom.

[0020] In other embodiments and aspects, R is a linear, branched or cyclic alkyl, alkenyl and aryl group. 1 and / or R 2 At least one carbon atom in the group is replaced by a nitrogen atom, an oxygen atom or a silicon atom.

[0021] In still further embodiments and aspects, the ethylene glycol dimethyl ether-based compound is 1,2-dimethoxyethane.

[0022] In other embodiments and aspects, the metal halide is lithium iodide.

[0023] In yet other embodiments and aspects, the mixed solvent / organic compound comprises a nitrile compound and / or a heterocyclic compound.

[0024] In other embodiments and aspects, the nitrile is methoxypropionitrile and / or ethylene glycol bis(propionitrile).

[0025] In still further embodiments and aspects, the heterocyclic compound is 1,3-dioxolane.

[0026] In other embodiments and aspects, the electrolyte further comprises other lithium salts selected from lithium nitrate (LiNO3), lithium fluoride (LiF), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI; LiC2F6NO4S2), lithium trifluoromethanesulfonate (LiCF3SO3), lithium hexafluorophosphate (LiPF6), lithium hexafluoroarsenate (LiAsF6), lithium perchlorate (LiClO4), and lithium tetrafluoroborate (LiBF4).

[0027] In still further embodiments and aspects, the oxidizing gas is selected from the group consisting of oxygen, air, nitric oxide, nitrogen dioxide, and mixtures and combinations thereof.

[0028] In other embodiments and aspects, the metal halide is present at >25 mg / cm 2The cathode loading of (metal halide / cathode surface area) is dissolved in the mixed solvent.

[0029] In yet other embodiments and aspects, the metal halide is at 24 mg / cm 2 Up to 31 mg / cm 2 The cathode loading of (metal halide / cathode surface area) is dissolved in the mixed solvent.

[0030] In other embodiments and aspects, the metal halide is present at a concentration of at least 28 mg / cm 2 The cathode loading of (metal halide / cathode surface area) is dissolved in the mixed solvent.

[0031] In yet other embodiments and aspects, the metal halide is present at a concentration of at least 31 mg / cm 2 The cathode loading of (metal halide / cathode surface area) is dissolved in the mixed solvent.

[0032] Other aspects and embodiments of the present invention are provided in the detailed description of the invention set forth below, but are not limited thereto. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 is a graph showing the operating range and optimal performance range of the volume fraction of ethylene glycol dimethyl ether-based solvent for the metal halide battery electrolytes described herein versus the metal halide loading concentration.

[0034] Figure 2A and Figure 2B The results show that the metal halide battery cells with different volume fractions of 1,2-dimethoxyethane (DME) and methoxypropionitrile (MPN) have a high conductivity at about 10 mg / cm 2 performance under lithium iodide (LiI) loading. Figure 2A is shown at 5mA / cm 2 The charge-discharge curve at the current density is shown in FIG. Figure 2B The discharge capacity is shown relative to the Figure 2A Column chart of DME volume fraction shown in .

[0035] Figure 3A and Figure 3B The results show that the metal halide battery cells with different volume fractions of DME and MPN are about 37 mg / cm 2 Performance under LiI loading. Figure 3A is shown at 1mA / cm 2 The charge-discharge curve at the current density is shown in FIG. Figure 3B The discharge capacity is shown relative to the Figure 3A Column chart of DME volume fraction shown in .

[0036] Figure 4 is a graph showing the normalized capacity of different volume fractions of DME with respect to different LiI loadings.

[0037] Figure 5A and Figure 5B Shown with about 10mg / cm 2 LiI loaded metal halide battery cell at 5mA / cm 2 performance at current density. Figure 5A is a graph showing the cycle life as a function of different volume fractions of ethylene glycol bis(propionitrile) (EGBP) solvent in a 0.5 volume fraction of ethylene glycol dimethyl ether-based compound mixed electrolyte. Figure 5B is a graph showing a comparison of the cycle life of MPN:DME (volume ratio 50:50) alone and MPN:DME (volume ratio 50:50) containing 10 vol% EGBP.

[0038] Figure 6 It is shown that at about 10 mg / cm 2 LiI loading and 3mA / cm 2 Plot of the cycle life as a function of the volume fraction of DME with 1,3-dioxolane (DOL) at current densities of 1,3-dioxolane (DOL). DETAILED DESCRIPTION

[0039] The following sets forth a description of preferred aspects and / or embodiments of the invention that are presently considered to be claimed. The appended claims are intended to cover any substitution or modification of function, purpose, or structure. As used in the specification and appended claims, unless the context clearly indicates otherwise, an element without a quantifier includes "one or more than one". As used in the specification and appended claims, the term "comprising" specifies the presence of the components, elements, features, and / or steps explicitly stated, but does not exclude the presence or addition of one or more other components, elements, features, and / or steps.

[0040] As used herein, the term "anode" refers to the negative or reducing electrode of a battery cell, which releases electrons to an external circuit and oxidizes in an electrochemical process.

[0041] As used herein, the term "cathode" refers to the positive or oxidized electrode of a battery cell, which receives electrons from an external circuit and is reduced in an electrochemical process.

[0042] As used herein, the term "electrolyte" refers to a material that provides ion transport between the anode and cathode of a battery cell. The electrolyte acts as a catalyst for the battery's electrical conductivity through its interaction with the anode and cathode. The electrolyte facilitates the movement of ions from the cathode to the anode during charging and from the anode to the cathode during discharging.

[0043] As used herein, the term "oxidizing gas" refers to a gas that initiates a reduction-oxidation (redox) reaction in a redox cell. Examples of oxidizing gases include, but are not limited to, oxygen, air, nitric oxide, nitrogen dioxide, and mixtures and combinations thereof. As known to those skilled in the art, a redox reaction is a reaction in which electrons are transferred between (i) a reducing agent that is oxidized by losing electrons and (ii) an oxidizing agent that is reduced by gaining electrons. A redox cell is a rechargeable electrochemical cell in which chemical energy is provided by two electrolytes separated by an ion exchange membrane. In operation, ion exchange occurs through the ion exchange membrane accompanied by the flow of current, while the electrolytes circulate in their respective spaces.

[0044] As used herein, the term "metal halide" refers to a compound having a metal and a halogen. The metal of the metal halide can be any metal from Groups 1 to 16 of the periodic table, but is typically an alkali metal from Group 1. The halogen of the metal halide will be any halogen from Group 17 of the periodic table. One metal halide used in the rechargeable batteries described herein is "lithium iodide" or "LiI," a compound of lithium and iodine used as a cathode material and dissolved in the electrolyte.

[0045] As used herein, the term "ethylene glycol dimethyl ether" refers to a glycol ether solvent that does not have free hydroxyl groups. Due to the lack of functional groups, ethylene glycol dimethyl ether solvents are chemically inert and aprotic (lacking H atoms / cannot undergo hydrogen bonding) polar solvents. The general chemical formula of ethylene glycol dimethyl ether is: R 1 O-(CR 2 2CR 2 2O) n -CR 1 Examples of glycol dimethyl ether solvents include, but are not limited to, 1,2-dimethoxyethane (DME), 1,2-diethoxyethane, 2-methoxyethyl ether (diethylene glycol dimethyl ether), 1,2-bis(2-methoxyethoxy)ethane (triethylene glycol dimethyl ether), and bis[2-(2-methoxyethoxy)ethyl]ether (tetraethylene glycol dimethyl ether). Glyme is less volatile and less toxic than most organic solvents used in conventional battery manufacturing methods.

[0046] As used herein, the term "nitrile" refers to an organic chemical containing at least one cyano functional group, wherein the carbon and nitrogen atoms have a triple bond, i.e., C≡N -Examples of nitriles include, but are not limited to, acetonitrile, acrylonitrile, propionitrile, methoxyacetonitrile, methoxypropionitrile (MPN), propyl nitrile, cyclopentanenitrile, 4-cyanobenzaldehyde, and ethylene glycol bis(propionitrile) (EGBP). Like ethylene glycol dimethyl ether, nitriles are chemically inert aprotic polar solvents.

[0047] As used herein, the term "heterocyclic compound" is used in its conventional sense to refer to a cyclic structure compound having at least two different elements as its ring members. As known to those skilled in the art, the list of heterocyclic compounds is too long to list; therefore, for the purposes of this disclosure, the following list provides three examples of saturated and unsaturated heterocyclic compounds having nitrogen, oxygen and sulfur as heteroatoms. It should be understood that the list of heterocyclic compounds is illustrative and non-restrictive. Examples of saturated 3-atom rings include, but are not limited to, aziridine, oxirane and thiirane. Examples of unsaturated 3-atom rings include, but are not limited to, aziridine, oxetane and thiirane. Examples of saturated 4-atom rings include, but are not limited to, azetidine, oxetane and thiirane. Examples of unsaturated 4-atom rings include, but are not limited to, azetidine, oxetane and thiirane. Examples of saturated 5-atom rings include, but are not limited to, pyrrolidine, oxolane and dithiolane. Examples of unsaturated 5-atom rings include, but are not limited to, pyrrole, furan and thiophene. Examples of saturated 6-atom rings include, but are not limited to, piperidine, Examples of unsaturated 6-atom rings include, but are not limited to, pyridine, pyran, and thiopyran. Examples of saturated 7-atom rings include, but are not limited to, azepane, oxepane, and thiepane. Examples of unsaturated 7-atom rings include, but are not limited to, azepane, oxepane, and thiepane. Examples of saturated 8-atom rings include, but are not limited to, azacyclooctane, oxoctane, and thiepane. Examples of unsaturated 8-atom rings include, but are not limited to, azacyclooctenes, oxoctenes, and thiepanes. Examples of saturated 9-atom rings include, but are not limited to, azacyclononane, oxoctenane, and thiepane. Examples of unsaturated 9-atom rings include, but are not limited to, azacyclononene, oxoctenene, and thiepane.

[0048] Metal halide batteries are redox batteries that use a metal halide as the cathode in the presence of an oxidizing gas. Unlike lithium-ion and NiMH batteries, metal halide batteries are not manufactured with heavy metals; therefore, metal halide batteries can have lower manufacturing costs than conventional lithium-ion or NiMH batteries. To become a suitable replacement for lithium-ion and NiMH batteries, metal halide batteries need to be optimized.

[0049] Described herein is a rechargeable battery comprising an anode, an electrolyte, and a metal halide cathode current collector in contact with the electrolyte, wherein the electrolyte comprises (i) a mixed solvent comprising at least two different organic liquid compounds, wherein at least one of the organic liquid compounds is a compound having the chemical formula R 1 O-(CR 2 2CR 2 2O) n -CR 1 A compound based on ethylene glycol dimethyl ether, n is an integer greater than 0, R 1 and R 2 (i) a metal halide serving as an active cathode material, wherein the metal halide is dissolved in the mixed solvent; and (ii) an oxidizing gas also dissolved in the mixed solvent.

[0050] In one embodiment, the metal halide is dissolved in the mixed solvent prior to the introduction of the oxidizing gas. In another embodiment, the metal halide and the oxidizing gas are introduced into the mixed solvent together. In yet another embodiment, the mixed solvent solution is premixed and added to the metal halide and the oxidizing gas to form the electrolyte solution. In another embodiment, the individual components of the mixed solvent solution are added to the metal halide or the metal halide and the oxidizing gas in no particular order or sequence to form the electrolyte solution.

[0051] In another embodiment, each independent R of the ethylene glycol dimethyl ether-based compound 1 and R 2 Independently selected from C1-C 10 Straight chain alkyl, C3-C 10 Branched alkyl, C3-C 10 Cyclic alkyl, C2-C 10 Straight chain alkenyl, C3-C 10 Branched alkenyl, C3-C 10 Cyclic alkenyl and C5-C 10 Aryl group.

[0052] In yet another embodiment, R of the ethylene glycol dimethyl ether-based compound 1 and R 2 The alkyl, alkenyl and / or aryl groups are substituted by halogen atoms. 1 and each R 2 Can be independently selected from C1-C 10 Straight chain alkyl halide groups, C3-C 10 Branched alkyl halide groups, C3-C10 Cyclic alkyl halide groups, C2-C 10 Straight chain alkenyl halide groups, C3-C 10 Branched alkenyl halide groups, C3-C 10 Cyclic alkenyl halide groups and C5-C 10 Aryl halide group.

[0053] In another embodiment, R of the ethylene glycol dimethyl ether-based compound 1 and R 2 Some or all of the carbon atoms of the alkyl, alkenyl and / or aryl groups are replaced by elements selected from nitrogen atoms, oxygen atoms and silicon atoms. 1 and each R 2 Can be independently selected from X1-X 10 Straight chain alkyl, X3-X 10 Branched alkyl, X3-X 10 Cyclic alkyl, X2-X 10 Straight-chain alkenyl, X3-X 10 Branched alkenyl, X3-X 10 Cyclic alkenyl and X5-X 10 Aryl groups, wherein each X is a carbon atom, a nitrogen atom, an oxygen atom, or a silicon atom.

[0054] Adding a glycol dimethyl ether-based solvent to the electrolyte solution improves the performance of the metal halide battery within a certain volume fraction range. The amount of glycol dimethyl ether-based solvent added to the electrolyte solution is about 20% to about 70% of the total volume of the solution. The remaining 20% ​​to 70% by volume of the solution is a metal halide (e.g., LiI in solid form) and one or more other solvents that form a mixed solvent electrolyte solution. Such other solvents include, but are not limited to, nitriles and / or heterocyclic compounds. Example 1 describes a general procedure for manufacturing a metal halide battery cell using lithium iodide (LiI) as an active cathode material, carbon nanoparticles as a conductive additive for the cathode, a lithium metal foil anode, a glycol dimethyl ether-based solvent, a nitrile-based solvent, and a heterocyclic compound.

[0055] The metal halides that can be used to prepare the electrolyte formulations described herein include any metal halide comprising a salt that dissociates into: (i) a metal halide selected from the group consisting of - Br - 、Cl - and F - ions; and (ii) selected from Li + Mg 2+ 、Al 3+ and Na + ions.

[0056] In one embodiment, the active cathode material may include one or more than one of Li, Mg, Al, and Na. For purposes of illustration only, and not limitation, metal halide LiI is described herein as an exemplary metal halide for the active cathode material.

[0057] In another embodiment, the electrolyte may include one or more lithium salts (in addition to LiI). Examples of such other lithium salts include, but are not limited to, lithium nitrate (LiNO3), lithium fluoride (LiF), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI; LiC2F6NO4S2), lithium trifluoromethanesulfonate (LiCF3SO3), lithium hexafluorophosphate (LiPF6), lithium hexafluoroarsenate (LiAsF6), lithium perchlorate (LiClO4), and lithium tetrafluoroborate (LiBF4).

[0058] Oxidizing gases that may be used in the electrolyte include, but are not limited to, oxygen, air, nitric oxide, nitrogen dioxide, and mixtures and combinations thereof.

[0059] Examples of rechargeable battery anode materials that can be used herein include, but are not limited to, one or more than one alkali metal and / or one or more than one alkaline earth metal.

[0060] Examples of materials that can be used for the cathode current collector of a rechargeable battery include, but are not limited to, porous carbon materials and compatible metals. Examples of porous carbon materials include, but are not limited to, carbon cloth, carbon nanoparticles, polymer binders, and combinations thereof. Examples of compatible metals include, but are not limited to, stainless steel, copper, nickel, titanium, aluminum, and combinations and alloys thereof.

[0061] As known to those skilled in the art, the batteries described herein will be manufactured into battery packs for sale. Examples of battery packs include, but are not limited to, soft pack batteries, cylindrical batteries, square batteries, button batteries, and Batteries (Swagelok Company, Solon, Ohio, USA).

[0062] The operating range and performance of metal halide batteries made with ethylene glycol dimethyl ether-based electrolytes depend on the amount of metal halide loaded in the battery. In the case where the metal halide battery has both the optimal LiI loading and the amount of ethylene glycol dimethyl ether-based solvent, the resulting metal halide battery has a high capacity at fast charging rates. Figure 1 In the range of about 8mg / cm 2 Up to 12 mg / cm 2 The cells were operated with ethylene glycol dimethyl ether-based electrolytes (e.g., DME:MPN; Example 2) at LiI loadings of 0.0 to 0.7 volume fractions. Within this LiI loading and electrolyte volume fraction, the metal halide cells performed well at LiI loadings of about 10 mg / cm 2The best performance is shown when the electrolyte volume fraction is about 0.5. In contrast, the electrolyte volume fraction is about 35 g / cm 2 Up to 38g / cm 2 At a LiI loading of about 37 mg / cm2, the cell was operated using a mixed solvent electrolyte based on ethylene glycol dimethyl ether with a volume fraction of 0.25 to 0.4. Within this LiI loading and electrolyte volume fraction, the metal halide cell 2 and the electrolyte volume fraction is about 0.3, which shows the best performance.

[0063] Example 2 describes the procedure for preparing a mixed solvent electrolyte solution based on ethylene glycol dimethyl ether, which has a concentration of about 10 mg / cm 2 Several electrolyte solutions were prepared with seven different DME:MPN volume ratios: 90:1, 80:20, 70:30, 50:50, 30:70, 10:90, and 0:100. Figure 2A and Figure 2B shows that metal halide batteries have a 2 Performance of LiI at different volume fractions. Figure 2A The battery is shown at 5 mA / cm 2 The charge-discharge curves at current density of Figure 2B The relationship between the discharge specific capacity of the battery and the volume fraction of DME is shown. Figure 2A and Figure 2B It shows that among seven different mixed solvent electrolyte solutions, the electrolyte solution with DME:MPN of 50:50 exhibits a high performance of 1.65 mAh / cm 2 The highest specific capacity.

[0064] Example 3 repeats the experiment of Example 2, but with a density of about 37 mg / cm 2 The DME:MPN volume ratios in the electrolyte solutions were 50:50, 40:60, 30:70, 20:80, 10:90 and 0:100. Figure 3A and Figure 3B shows that the metal halide battery has a 2 Performance of LiI under different volume fractions. Figure 3A The battery is shown at 1 mA / cm 2 The charge-discharge curves at current density of Figure 3B The relationship between the discharge specific capacity of the battery and the volume fraction of DME is shown. Figure 3A and Figure 3BIt shows that among the six different mixed solvent electrolyte solutions, the electrolyte solution with DME:MPN of 30:70 exhibits a high capacity of 10.6 mAh / cm 2 In Example 4, different volume fractions of DME:MPN (from 0:100 to 90:10, with a step of 10) and five different LiI loadings (10 mA-hour / cm 2 , 18mA-hour / cm 2 , 24mA-hour / cm 2 , 31mA-hour / cm 2 and 27 mA-hours / cm 2 ) Test the performance of metal halide batteries. Figure 4 Various volume fractions of the ethylene glycol dimethyl ether-based solvent DME are shown in relation to various LiI loadings. Figure 4 The discharge capacity and voltage efficiency of the battery are shown to vary with the volume fraction of DME. For example, at about 10 mg / cm 2 LiI loading, 5mA / cm 2 At a current density of 0 to 0.8, the normalized discharge capacity of DME with a volume fraction of 0 to 0.8 is about 75% to 100% (i.e., greater than 1 mAh / cm 2 ), the volume fraction of DME is 0.5 (i.e., 1.6 mAh / cm 2 ) has the highest value. Figure 4 As shown, 25mg / cm 2 is the metal halide loading limit in the absence of the glyme-based additives described herein. With the addition of the glyme-based additives, the effective cathode loading of metal halide / cathode surface area increases to greater than 25 mg / cm 2 In one embodiment, the cathode loading of metal halide / cathode surface area is 24 mg / cm 2 Up to 31 mg / cm 2 In other embodiments, the cathode loading of metal halide / cathode surface area is at least 28 mg / cm 2 In another embodiment, the cathode loading of metal halide / cathode surface area is 31 mg / cm 2 .

[0065] Examples 2, 3, and 4 demonstrate that at higher LiI loadings, the performance of metal halide batteries can be affected by increased shuttle effects during charging, resulting in reduced specific discharge capacity. However, the reduced capacity of metal halide batteries can be improved by adjusting the composition of the solvent in the electrolyte. For example, the cycle life of the rechargeable metal halide batteries described herein can be improved by including nitrile or heterocyclic compounds in the mixed solvent electrolyte.

[0066] Example 5 describes the addition of the ethereal dinitrile, ethylene glycol bis(propionitrile) (EGBP), to an ethylene glycol dimethyl ether based electrolyte solution. Figure 5A As shown in Figure 2, the addition of EGBP to an ethylene glycol dimethyl ether-based electrolyte solution containing DME and MPN improves the cycle life of metal halide batteries. Figure 5A In the embodiment of the present invention, the cycle life improvement is observed in the range of 6.5% to 12.5% ​​by volume fraction of EGBP, and the highest cycle life improvement of about 100% is observed when the volume fraction of EGBP is 10%. Figure 5B It was shown that the inclusion of EGBP in an ethylene glycol dimethyl ether-based electrolyte doubles the cycle life of metal halide batteries without causing a significant decrease in the specific capacity of the battery. Figure 5B In about 10mg / cm 2 LiI loading and 5mA / cm 2 At a current density of 1.5 Å, the specific capacity of the electrolyte solution with EGBP shows that the specific capacity of the metal halide battery cell is reduced by about 0.2 mAh / cm 2 Although the electrolyte solution without EGBP has a higher total specific gravity (about 1.3 mAh / cm 2 ), but the cycle life of metal halide batteries stops at about 200 cycles, while the cycle life of batteries containing EGBP exceeds 400 cycles.

[0067] Example 6 describes the addition of the heterocyclic compound 1,3-dioxolane (DOL) to an electrolyte solution based on ethylene glycol dimethyl ether. Figure 6 As shown, the addition of DOL to the DME electrolyte solution increased the capacity retention compared to the electrolyte solution containing only DME.

[0068] The description of the various aspects and / or embodiments of the present invention is for illustrative purposes only and is not intended to be exhaustive or to limit the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the embodiments. The terminology used herein is selected to best explain the principles of the embodiments, practical applications, or technical improvements over commercially available technologies, or to enable others skilled in the art to understand the aspects and / or embodiments disclosed herein.

[0069] experiment

[0070] The following examples are set forth to provide a complete disclosure of how to make and use the aspects and / or embodiments of the invention set forth herein to those of ordinary skill in the art. While striving to ensure the accuracy of variables such as amounts, temperatures, etc., experimental errors and deviations should be considered. Unless otherwise stated, parts are by weight, temperatures are degrees Celsius, and pressures are at or near atmospheric pressure. Unless otherwise stated, all components are commercially available.

[0071] Example 1

[0072] General procedure for manufacturing batteries

[0073] LiI was used as the active cathode material for the battery. LiI was placed in a vial and dried on a hot plate in an argon-filled glove box (<0.1 ppm H2O, O2) at 120°C for more than 12 hours. The glycol dimethyl ether-based compounds, nitrile-based compounds, and heterocyclic compounds were stored in a 20 mg molecular sieve Next, mixed solvent electrolyte solutions were prepared using the following compounds in volume ratios of 90:10, 80:20, 70:30, 50:50, 30:70 and 10:90: (i) a compound based on ethylene glycol dimethyl ether and a nitrile-based compound, or (ii) a compound based on ethylene glycol dimethyl ether and a heterocyclic compound. Each mixed solvent electrolyte solution was used to soak a quartz filter membrane on top of a lithium metal anode. Carbon nanoparticles were used as a conductive additive for the cathode material. LiI was dissolved in the mixed solvent electrolyte solution. All battery assembly was performed in a glove box. The lithium metal foil anode, electrolyte-wetted diaphragm and carbon cathode were placed in sequence in a Swagelok-type cell equipped with an oxygen flow inlet and outlet tubes. Oxygen was introduced from the inlet tube, purged, and completely replaced the argon in the cell.

[0074] Example 2

[0075] At relatively low LiI loading (about 10 mg / cm 2 ) Capacity changes with different volume fractions of ethylene glycol dimethyl ether-based solvents in the electrolyte solution

[0076] The performance of metal halide batteries with a lithium metal anode, a carbon cathode, and a mixed solvent electrolyte solution of LiI dissolved in DME and MPN was tested using different volume fractions of DME and MPN in the electrolyte solution. The specific capacity (mAh / cm2) of the battery cell normalized by the electrode area was measured using the following seven DME:MPN volume ratios: 2): 90:10, 80:20, 70:30, 50:50, 30:70, 10:90, 0:100. The weight ratio of carbon nanoparticles to LiI was fixed at 30:70, and the amount of LiI loaded as part of the cathode material was fixed at about 10±1 mg / cm 2 Among the seven different DME:MPN volume ratios, the 50:50 volume ratio showed a significant difference at 5 mA / cm 2 The current density was 1.65 mAh / cm 2 The best specific capacity ( Figure 2A and Figure 2B ). Based on an applied current of 2.5 mA and a 0.5 cm 2 The current density is calculated based on the electrode area (the anode and cathode have the same area).

[0077] Example 3

[0078] At relatively high LiI loading (about 37 mg / cm 2 ) Capacity changes with different volume fractions of ethylene glycol dimethyl ether-based solvents in the electrolyte solution

[0079] The performance of metal halide batteries with a lithium metal anode, a carbon cathode, and a mixed solvent electrolyte solution of LiI dissolved in DME and MPN was tested using different volume fractions of DME and MPN in the electrolyte solution. The specific capacity (mAh / cm2) of the battery cell normalized by the electrode area was measured using the following six DME:MPN volume ratios: 2 ): 50:50, 40:60, 30:70, 20:80, 10:90, 0:100. The weight ratio of carbon nanoparticles to LiI was fixed at 30:70, and the amount of LiI loaded as part of the cathode material was fixed at about 37±3 mg / cm 2 Among the six different DME:MPN volume ratios, the volume ratio of 30:70 at 1 mA / cm 2 The current density was 10.6 mAh / cm 2 The best specific capacity ( Figure 3A and Figure 3B ).

[0080] Example 4

[0081] Normalized capacity variation at different LiI loadings with different volume fractions of ethylene glycol dimethyl ether-based solvents in the electrolyte solution

[0082] The performance of metal halide batteries with lithium metal anode, carbon cathode and mixed solvent electrolyte solution of LiI dissolved in DME and MPN was tested using different volume fractions of DME and MPN and different concentrations of dissolved LiI in the mixed solvent electrolyte solution of DME and MPN. 2 、18mg / cm 2 , 24mg / cm 2 、31mg / cm 2 and 37 mg / cm 2 ) were tested with ten different DME:MPN ratios ranging from 0:100 to 90:10. At each load, the capacity data were normalized to the capacity of the best performing volume ratio ( Figure 4 Among all the LiI loadings tested, the best performing DME:MPN volume ratios were 70:30 and 20:80.

[0083] Example 5

[0084] Cycle life changes with different volume fractions of ethylene glycol dimethyl ether-based solvents and ether dinitrile in the electrolyte solution

[0085] The performance of metal halide batteries with a lithium metal anode, a carbon cathode, and a mixed solvent electrolyte solution of LiI dissolved in DME, MPN, and different volume fractions of the ether dinitrile, ethylene glycol bis(propionitrile) (EGBP) was tested. The cycle life of the battery cells was measured using the following volume percentages of EGBP in a 1:1 DME:MPN ratio: 0%, 2.5%, 5%, 7.5%, 10%, 12.5%, and 15%. The loading of LiI was fixed at approximately 20 ± 1 mg / cm 2 Among the DME:MPN:EGBP mixed solvent electrolyte solutions with different volume ratios, the volume ratio of 45:45:10 (EGBP volume fraction of 0.1) showed the best cycle life behavior and the highest capacity retention rate over 450 cycles ( Figure 5A ), which shows that the cycle life is increased by nearly 100% compared to the 1:1 DME:MPN alone ( Figure 5B ).

[0086] Example 6

[0087] Cycle life changes with different volume fractions of ethylene glycol dimethyl ether-based solvents and heterocyclic compounds in the electrolyte solution

[0088] Metal halide cells were tested with different volume fractions of DME and DOL in the electrolyte solution. The cells had a lithium metal anode, a carbon cathode, and a mixed solvent electrolyte solution of LiI dissolved in DME and the heterocyclic compound 1,3-dioxolane (DOL). The specific capacity (mAh / cm2) of the battery cells normalized by the electrode area was measured using the following three DME:DOL volume ratios. 2 The weight ratio of carbon nanoparticles to LiI was fixed at 30:70, and the amount of LiI loaded as part of the cathode material was fixed at about 10 ± 1 mg / cm 2 Among the three DME:DOL mixed solvent electrolyte solutions with different volume ratios, the 50:50 volume ratio (0.5 DME volume fraction) exhibited the best cycle life behavior, with the highest capacity retention over 500 cycles ( Figure 6 ).

Claims

1. A battery comprising: anode; electrolytes; and a cathode current collector in contact with an electrolyte, wherein the electrolyte facilitates ion transport between the anode and cathode current collectors, The electrolytes include: (i) a mixed solvent containing at least two organic liquid compounds, wherein at least one organic liquid compound has a chemical formula R 1 O-(CR 2 2CR 2 2O) n -CR 1 A compound based on ethylene glycol dimethyl ether, wherein n is an integer greater than 0, R 1 and R 2 are independently substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl or alkylaryl, and The ethylene glycol dimethyl ether-based compound has a volume fraction of 20 to 70 volume % of the mixed solvent, (ii) a metal halide used as an active cathode material, wherein the metal halide is dissolved in a mixed solvent, and (iii) Oxidizing gas dissolved in the mixed solvent.

2. The battery according to claim 1, wherein each R 1 and each R 2 Independently selected from C1-C 10 Straight chain alkyl, C3-C 10 Branched alkyl, C3-C 10 Cyclic alkyl, C2-C 10 Straight chain alkenyl, C3-C 10 Branched alkenyl, C3-C 10 Cyclic alkenyl and C5-C 10 Aryl.

3. The battery according to claim 2, wherein R is a linear, branched or cyclic alkyl, alkenyl or aryl group. 1 and / or R 2 At least one hydrogen atom in the group is substituted by a halogen atom.

4. The battery according to claim 2, wherein R is a linear, branched or cyclic alkyl, alkenyl or aryl group. 1 and / or R 2 At least one carbon atom in the group is replaced by a nitrogen atom, an oxygen atom or a silicon atom. The battery according to claim 1 , wherein the ethylene glycol dimethyl ether-based compound is 1,2-dimethoxyethane. The battery according to claim 1 , wherein the metal halide is lithium iodide.

7. The battery according to claim 1, wherein the mixed solvent contains a nitrile compound.

8. The battery according to claim 7, wherein the nitrile is methoxypropionitrile and / or ethylene glycol bis(propionitrile).

9. The battery according to claim 1, wherein the mixed solvent contains a heterocyclic compound. 10 . The battery according to claim 9 , wherein the heterocyclic compound is 1,3-dioxolane.

11. The battery of claim 1 , wherein the electrolyte further comprises: (iv) other lithium salts selected from lithium nitrate (LiNO3), lithium fluoride (LiF), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI; LiC2F6NO4S2), lithium trifluoromethanesulfonate (LiCF3SO3), lithium hexafluorophosphate (LiPF6), lithium hexafluoroarsenate (LiAsF6), lithium perchlorate (LiClO4) and lithium tetrafluoroborate (LiBF4).

12. The battery of claim 1, wherein the anode comprises one or more than one alkali metal and / or one or more than one alkaline earth metal.

13. The battery of claim 1, wherein the cathode current collector comprises a porous carbon material and / or a metal.

14. The battery of claim 1, wherein the porous carbon material is selected from the group consisting of carbon cloth, carbon nanoparticles, polymer binders, and combinations thereof.

15. The battery of claim 1, wherein the oxidizing gas is selected from the group consisting of oxygen, air, nitric oxide, nitrogen dioxide, and mixtures and combinations thereof.

16. The battery according to claim 1, wherein the metal halide is >25 mg / cm 2 The cathode loading of (metal halide / cathode surface area) is dissolved in the mixed solvent.

17. The battery according to claim 1, wherein the metal halide is 24 mg / cm 2 Up to 31 mg / cm 2 The cathode loading of (metal halide / cathode surface area) is dissolved in the mixed solvent.

18. The battery of claim 1, wherein the metal halide is present at a concentration of at least 28 mg / cm 2 The cathode loading of (metal halide / cathode surface area) is dissolved in the mixed solvent.

19. The battery of claim 1, wherein the metal halide is present at a concentration of at least 31 mg / cm 2 The cathode loading of (metal halide / cathode surface area) is dissolved in the mixed solvent.

20. An electrolyte for a rechargeable battery, comprising: (i) a mixed solvent containing at least two organic liquid compounds, wherein at least one organic liquid compound has a chemical formula R 1 O-(CR 2 2CR 2 2O) n -CR 1 A compound based on ethylene glycol dimethyl ether, wherein n is an integer greater than 0, R 1 and R 2 are independently substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl or alkylaryl, and The ethylene glycol dimethyl ether-based compound has a volume fraction of 20 to 70 volume % of the mixed solvent, (ii) a metal halide dissolved in a mixed solvent, and (iii) Oxidizing gas dissolved in the mixed solvent.

21. The electrolyte according to claim 20, wherein each R 1 and each R 2 Independently selected from C1-C 10 Straight chain alkyl, C3-C 10 Branched alkyl, C3-C 10 Cyclic alkyl, C2-C 10 Straight chain alkenyl, C3-C 10 Branched alkenyl, C3-C 10 Cyclic alkenyl and C5-C 10 Aryl.

22. The electrolyte according to claim 20, wherein each R 1 and each R 2 Independently selected from C1-C 10 Straight chain alkyl halide groups, C3-C 10 Branched alkyl halide groups, C3-C 10 Cyclic alkyl halide groups, C2-C 10 Straight chain alkenyl halide groups, C3-C 10 Branched alkenyl halide groups, C3-C 10 Cyclic alkenyl halide groups and C5-C 10 Aryl halide group.

23. The electrolyte according to claim 20, wherein each R 1 and each R 2 Independently selected from X1-X 10 Straight chain alkyl, X3-X 10 Branched alkyl, X3-X 10 Cyclic alkyl, X2-X 10 Straight-chain alkenyl, X3-X 10 Branched alkenyl, X3-X 10 Cyclic alkenyl and X5-X 10 Aryl groups, wherein each X is a carbon atom, a nitrogen atom, an oxygen atom, or a silicon atom.

24. The electrolyte according to claim 20, wherein the mixed solvent comprises a nitrile compound and / or a heterocyclic compound.

25. The electrolyte of claim 20, further comprising: (iv) a lithium salt selected from lithium nitrate (LiNO3), lithium fluoride (LiF), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI; LiC2F6NO4S2), lithium trifluoromethanesulfonate (LiCF3SO3), lithium hexafluorophosphate (LiPF6), lithium hexafluoroarsenate (LiAsF6), lithium perchlorate (LiClO4), and lithium tetrafluoroborate (LiBF4).

26. The electrolyte of claim 20, wherein the oxidizing gas is selected from the group consisting of oxygen, air, nitric oxide, nitrogen dioxide, and mixtures and combinations thereof.

27. A rechargeable battery comprising: anode; a cathode current collector; and An electrolyte that promotes ion transport between an anode and a cathode current collector, wherein the cathode current collector is in contact with the electrolyte, and the electrolyte comprises: (i) lithium iodide dissolved in a mixed solvent and (ii) an oxidizing gas dissolved in the mixed solvent, wherein the mixed solvent comprises 1,2-dimethoxyethane and at least one other organic compound, and wherein the 1,2-dimethoxyethane has a volume fraction of 20 volume % to 70 volume % of the mixed solvent.

28. The rechargeable battery according to claim 27, wherein the at least one other organic compound is a nitrile compound and / or a heterocyclic compound.

29. The rechargeable battery of claim 27, wherein the electrolyte comprises another lithium salt selected from the group consisting of lithium nitrate (LiNO3), lithium fluoride (LiF), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI; LiC2F6NO4S2), lithium trifluoromethanesulfonate (LiCF3SO3), lithium hexafluorophosphate (LiPF6), lithium hexafluoroarsenate (LiAsF6), lithium perchlorate (LiClO4), and lithium tetrafluoroborate (LiBF4).

30. The rechargeable battery of claim 27, wherein the anode comprises one or more than one alkali metal and / or one or more than one alkaline earth metal.

31. The rechargeable battery of claim 27, wherein the cathode current collector comprises a porous carbon material and / or a metal.

32. The rechargeable battery of claim 27, wherein the oxidizing gas is selected from the group consisting of oxygen, air, nitric oxide, nitrogen dioxide, and mixtures and combinations thereof.

33. The rechargeable battery of claim 27, wherein the lithium iodide is >25 mg / cm 2 A cathode loading of (lithium iodide / cathode surface area) was dissolved in the mixed solvent.

34. The rechargeable battery according to claim 27, wherein the lithium iodide is 24 mg / cm 2 Up to 31 mg / cm 2 A cathode loading of (lithium iodide / cathode surface area) was dissolved in the mixed solvent.

35. The rechargeable battery of claim 27, wherein the lithium iodide is present at a concentration of at least 28 mg / cm 2 A cathode loading of (lithium iodide / cathode surface area) was dissolved in the mixed solvent.

36. The rechargeable battery of claim 27, wherein the lithium iodide is present at a concentration of at least 31 mg / cm 2 A cathode loading of (lithium iodide / cathode surface area) was dissolved in the mixed solvent.

37. A method for preparing an electrolyte for a metal halide rechargeable battery, the method comprising: dissolving a metal halide in a mixed solvent solution; and The oxidizing gas is introduced into the mixed solvent solution. The mixed solvent solution comprises at least two organic liquid compounds, wherein at least one of the at least two organic liquid compounds has a chemical formula R 1 O-(CR 2 2CR 2 2O) n -CR 1 A compound based on ethylene glycol dimethyl ether, wherein n is an integer greater than 0, R 1 and R 2 are independently substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl or alkylaryl, and The ethylene glycol dimethyl ether-based compound has a volume fraction of 20 volume % to 70 volume % of the mixed solvent solution.

38. The method of claim 37, wherein each R 1 and each R 2 Independently selected from C1-C 10 Straight chain alkyl, C3-C 10 Branched alkyl, C3-C 10 Cyclic alkyl, C2-C 10 Straight chain alkenyl, C3-C 10 Branched alkenyl, C3-C 10 Cyclic alkenyl and C5-C 10 Aryl.

39. The method according to claim 37, wherein R is a linear, branched or cyclic alkyl, alkenyl or aryl group. 1 and / or R 2 At least one hydrogen atom in the group is substituted by a halogen atom.

40. The method according to claim 37, wherein R is a linear, branched or cyclic alkyl, alkenyl or aryl group. 1 and / or R 2 At least one carbon atom in the group is replaced by a nitrogen atom, an oxygen atom or a silicon atom.

41. The method of claim 37, wherein the mixed solvent solution comprises a nitrile compound and / or a heterocyclic compound.

42. A method for manufacturing a metal halide rechargeable battery, the method comprising: dissolving a metal halide in a mixed solvent solution to form an electrolyte solution; forming a soaked separator by soaking the separator in an electrolyte solution; forming a stack comprising an anode, an impregnated separator, and a cathode current collector, wherein the impregnated separator is placed between the anode and the cathode current collector, the cathode current collector being placed in contact with the electrolyte solution, and the metal halide serving as the active cathode material; introducing an oxidizing gas into the stack, The mixed solvent solution comprises at least two organic liquid compounds, wherein at least one of the at least two organic liquid compounds has a chemical formula R 1 O-(CR 2 2CR 2 2O) n -CR 1 A compound based on ethylene glycol dimethyl ether, wherein n is an integer greater than 0, R 1 and R 2 are independently substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl or alkylaryl, and The ethylene glycol dimethyl ether-based compound has a volume fraction of 20 volume % to 70 volume % of the mixed solvent solution.

43. The method of claim 42, wherein each R 1 and each R 2 Independently selected from C1-C 10 Straight chain alkyl, C3-C 10 Branched alkyl, C3-C 10 Cyclic alkyl, C2-C 10 Straight chain alkenyl, C3-C 10 Branched alkenyl, C3-C 10 Cyclic alkenyl and C5-C 10 Aryl.

44. The method according to claim 42, wherein R is a linear, branched or cyclic alkyl, alkenyl or aryl group. 1 and / or R 2 At least one hydrogen atom in the group is substituted by a halogen atom.

45. The method according to claim 42, wherein R is a linear, branched or cyclic alkyl, alkenyl or aryl group. 1 and / or R 2 At least one carbon atom in the group is replaced by a nitrogen atom, an oxygen atom or a silicon atom.

46. ​​The method of claim 42, wherein the mixed solvent solution comprises a nitrile compound and / or a heterocyclic compound.

47. The method of claim 42, wherein the metal halide is present at a concentration of >25 mg / cm 2 The cathode loading of (metal halide / cathode surface area) is dissolved in the mixed solvent solution.

48. The method of claim 42, wherein the metal halide is added at a concentration of 24 mg / cm 2 Up to 31 mg / cm 2 The cathode loading of (metal halide / cathode surface area) is dissolved in the mixed solvent solution.

49. The method of claim 42, wherein the metal halide is present at a concentration of at least 28 mg / cm 2 The cathode loading of (metal halide / cathode surface area) is dissolved in the mixed solvent solution.

50. The method of claim 42, wherein the metal halide is present at a concentration of at least 31 mg / cm 2 The cathode loading of (metal halide / cathode surface area) is dissolved in the mixed solvent solution.

51. A method for preparing an electrolyte for a metal halide rechargeable battery, the method comprising: The metal halide, the oxidizing gas and the components of the mixed solvent solution are combined, wherein the mixed solvent solution comprises at least two organic liquid compounds, wherein at least one of the at least two organic liquid compounds has a chemical formula R 1 O-(CR 2 2CR 2 2O) n -CR 1 A compound based on ethylene glycol dimethyl ether, wherein n is an integer greater than 0, R 1 and R 2 are independently substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl or alkylaryl, and The ethylene glycol dimethyl ether-based compound has a volume fraction of 20 volume % to 70 volume % of the mixed solvent solution.

52. A method of manufacturing a metal halide rechargeable battery, the method comprising: forming an electrolyte solution comprising components of a metal halide, an oxidizing gas, and a mixed solvent solution; forming a soaked separator by soaking the separator in an electrolyte solution; and forming a stack comprising an anode, an impregnated separator, and a cathode current collector, wherein the impregnated separator is placed between the anode and the cathode current collector, the cathode current collector is placed in contact with an electrolyte solution, and the metal halide serves as the active cathode material; wherein the mixed solvent solution comprises at least two organic liquid compounds, wherein at least one of the at least two organic liquid compounds is a metal halide having the chemical formula R 1 O-(CR 2 2CR 2 2O) n -CR 1 A compound based on ethylene glycol dimethyl ether, wherein n is an integer greater than 0, R 1 and R 2 are independently substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl or alkylaryl, and The ethylene glycol dimethyl ether-based compound has a volume fraction of 20 volume % to 70 volume % of the mixed solvent solution.

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