CN115836419A - Liquid cathode formulation for rechargeable metal halide cells - Google Patents
Liquid cathode formulation for rechargeable metal halide cells Download PDFInfo
- Publication number
- CN115836419A CN115836419A CN202180045640.2A CN202180045640A CN115836419A CN 115836419 A CN115836419 A CN 115836419A CN 202180045640 A CN202180045640 A CN 202180045640A CN 115836419 A CN115836419 A CN 115836419A
- Authority
- CN
- China
- Prior art keywords
- metal halide
- based compound
- solvent
- electrolyte
- halogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Rechargeable metal halide cells with optimized active catholyte solutions have high energy densities and do not require charging after manufacture. An optimized active catholyte solution comprises (i) a mixture of a metal halide and its corresponding halogen dissolved in an organic solvent at a concentration ratio greater than 0.5 and (ii) an oxidizing gas. The organic solvent is a nitrile-based compound and/or a heterocyclic compound. Ethylene glycol dimethyl ether may be added to the organic solvent to improve battery performance.
Description
Technical Field
The present invention relates generally to rechargeable batteries, and more particularly to active catholyte formulations for use in rechargeable metal halide batteries.
Background
Rechargeable batteries are in great demand in a wide range of applications, 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 performance, but today battery performance is still the limiting factor in meeting high standards for consumers.
There are currently two types of rechargeable batteries: batteries that operate by electrochemical insertion/extraction of active ions, such as lithium ion batteries; and batteries that operate by conversion reactions of the active electrode/electrolyte material, such as nickel metal hydride (NiMH) batteries. The most well known and most widely used rechargeable battery is the lithium ion battery, which uses an intercalated lithium compound as the electrode material, allowing lithium ions to move around in the electrolyte cell. NiMH batteries use nickel hydroxide as the positive electrode, a hydrogen absorbing alloy as the negative electrode, and an alkaline electrolyte (e.g., potassium hydroxide).
The disadvantages of lithium ion batteries and NiMH batteries have prevented their use in a wider range of applications. These disadvantages include slow charging rates and the high cost of the heavy metal cathode materials required to make the battery.
Disclosure of Invention
The present invention overcomes the disadvantages of the art by providing a rechargeable metal halide battery with an optimized active catholyte solution.
In one embodiment, the present invention relates to a battery comprising: an anode; a cathode current collector; and an electrolyte that facilitates transport of ions between the anode and cathode current collectors, wherein the electrolyte comprises: a solvent comprising one or more than one organic liquid compound, an active cathode material comprising a mixture of a metal halide and its corresponding halogen, wherein the molar concentration ratio of metal halide to halogen is greater than 0.5, the mixture is dissolved in the solvent, the active cathode material is in contact with a cathode current collector, and an oxidizing gas dissolved in the solvent.
In another embodiment, the invention relates to an electrolyte for a rechargeable metal halide cell comprising: a solvent comprising one or more than one organic liquid compound, an active cathode material comprising a mixture of a metal halide and its corresponding halogen, wherein the molar concentration ratio of metal halide to halogen is greater than 0.5, the mixture is dissolved in the solvent, the active cathode material is in contact with a cathode current collector, and an oxidizing gas dissolved in the solvent.
In other embodiments, the invention relates to a rechargeable battery comprising: an anode; a cathode current collector; and an electrolyte that facilitates transport of ions between the anode and cathode current collectors, wherein the electrolyte comprises: mixed solvent solution containing nitrile-based compound and/or heterocyclic-based compound, mixed solvent solution containing lithium iodide (LiI) and iodine (I) 2 ) Activity of the mixture ofCathode material in which the mixture is dissolved in a mixed solvent solution of LiI and I 2 Is 0.5 to 8, the active cathode material is in contact with a cathode current collector, and an oxidizing gas dissolved in a solvent.
In other aspects, the invention relates to a method of preparing an electrolyte for a metal halide rechargeable battery, the method comprising: dissolving a mixture of a metal halide and its corresponding halogen in a solvent comprising a nitrile-based compound and/or a heterocyclic-based compound, wherein the molar concentration ratio of metal halide to halogen is greater than 0.5; and introducing an oxidizing gas into the mixed solvent.
In another aspect, the present invention relates to a method of making a metal halide rechargeable battery, the method comprising: mixing LiI and I 2 In a solvent to form an electrolyte solution, wherein the solvent comprises a nitrile-based compound and/or a heterocyclic-based compound, and LiI and I 2 In a molar ratio of from 0.5 to 8; forming a soaked separator by soaking the separator in an electrolyte solution; forming a stack comprising an anode, a soaked separator, and a cathode current collector, wherein the soaked separator is placed between the anode and the cathode current collector; and introducing an oxidizing gas into the heap.
In other aspects, the invention relates to a method of preparing an electrolyte for a metal halide rechargeable battery, the method comprising: combining a metal halide, a corresponding halogen of the metal halide, an oxidizing gas, and a solvent, wherein the solvent comprises a nitrile-based compound and/or a heterocyclic-based compound, and the molar concentration ratio of the metal halide to the halogen is greater than 0.5.
In another aspect, the present invention relates to a method of making a metal halide rechargeable battery, the method comprising: form a composition comprising LiI, I 2 An oxidizing gas and a solvent, wherein the solvent comprises a nitrile-based compound and/or a heterocyclic-based compound, and LiI and I 2 In a molar ratio of 0.5 to 8; soaking the diaphragm in an electrolyte solution; and forming a stack comprising an anode, a soaked separator and a cathode current collector, wherein the soaked separator is placed on the anodeBetween the pole and the cathode current collector.
In other embodiments and aspects, the metal halide comprises a metal halide that dissociates into (I) a group selected from I - 、Br - 、Cl - And F - And (ii) is selected from Li + 、Mg 2+ 、Al 3+ And Na + A salt of the ion of (a).
In other embodiments and aspects, halo is a group comprising I 2 、Br 2 、Cl 2 And F 2 Molecular halogen of (a).
In other embodiments and aspects, the molar concentration ratio of metal halide to halogen is greater than 0.5.
In other embodiments and aspects, the molar concentration ratio of metal halide to halogen is from 0.5 to 8.
In other embodiments and aspects, the organic liquid compound/solvent comprises a nitrile-based compound and/or a heterocyclic-based compound.
In other embodiments and aspects, the nitrile-based compound is Methoxypropionitrile (MPN).
In other embodiments and aspects, the heterocycle-based compound is 1,3-Dioxolane (DOL).
In other embodiments and aspects, the organic liquid compound/solvent further comprises an ethylene glycol dimethyl ether-based compound.
In other embodiments and aspects, the glyme-based compound is 1,2-Dimethoxyethane (DME).
In other embodiments and aspects, the oxidizing gas is selected from the group consisting of oxygen, air, nitric oxide, nitrogen dioxide, and mixtures and combinations thereof.
In other embodiments and aspects, the electrolyte comprises a material selected from lithium nitrate (LiNO) 3 ) Lithium fluoride (LiF), lithium bis (trifluoromethanesulfonyl) imide (LiTFSl; liC 2 F 6 NO 4 S 2 ) Lithium trifluoromethanesulfonate (LiCF) 3 SO 3 ) Lithium hexafluorophosphate (LiPF 6), lithium hexafluoroarsenate (LiAsF) 6 ) Lithium perchlorate (LiClO) 4 ) And lithium tetrafluoroborate (LiBF) 4 ) Other lithium salts of (1).
In other embodiments and aspects, the anode comprises one or more than one alkali metal and/or one or more than one alkaline earth metal.
In other embodiments and aspects, the anode comprises at least one of Li, mg, al, and Na.
In other embodiments and aspects, the cathode current collector includes a porous carbon material and/or a metal.
In other embodiments and aspects, the porous carbon material is selected from the group consisting of carbon cloth, carbon nanoparticles, polymeric binders, and combinations thereof.
In other embodiments and aspects, the metal is selected from stainless steel, copper, nickel, titanium, aluminum, and combinations and alloys thereof.
Other embodiments and aspects of the invention are provided in the detailed description set forth below, but are not limited thereto.
Drawings
FIGS. 1A-1C are comparative plots of cell capacity after 10 cycles for a cell having an effective LiI (lithium iodide) concentration of 3M in a fully discharged state, in the following operating electrolyte (MPN: DME (methoxypropionitrile: 1,2-dimethoxyethane) in 1:1 in a solvent mixture) and operating conditions: liI-only based electrolyte solutions (fig. 1A); liI + iodine (I) operating with first cycle as charge cycle 2 ) An electrolyte solution (fig. 1B); and LiI + I with the first cycle as the discharge cycle 2 Electrolyte solution (fig. 1C).
FIG. 2 compares DOL DME (1,3-dioxolane: methoxypropionitrile) with LiI and I at 1:1 2 Of the solvent mixture of five different electrolyte solutions prepared in the solvent mixture of different mixtures of (a) a graph of the battery charge capacity (dashed line) and discharge capacity (solid line) over 400 cycles.
Detailed Description
The following sets forth a description of what are presently considered to be the preferred embodiments of the claimed invention. Any substitution or modification in function, purpose, or structure is intended to be included in the appended claims. As used in this specification and the appended claims, no element preceding a quantity is intended to be exhaustive unless the context clearly dictates otherwise. The term "comprising" as used in the specification and appended claims, is intended to specify the presence of stated components, elements, features and/or steps, but does not exclude the presence or addition of one or more other components, elements and/or steps.
As used herein, the term "anode" refers to the negative electrode or reducing electrode of a battery that releases electrons to an external circuit and is oxidized in an electrochemical process.
As used herein, the term "cathode" refers to the positive or oxidizing electrode of a battery that takes electrons from an external circuit and is reduced in an electrochemical process.
As used herein, the term "electrolyte" refers to a material that provides ionic transport between the anode and cathode of a battery. The electrolyte acts as a catalyst for the conductivity of the cell through interaction with the anode and cathode. The electrolyte facilitates the movement of ions from the cathode to the anode during charging of the battery, and from the anode to the cathode during discharging.
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, and nitrogen dioxide. As known to those skilled in the art, a redox reaction is a reaction that transfers electrons between (i) a reducing agent that undergoes oxidation by electron loss and (ii) an oxidizing agent that undergoes reduction by electron gain. Redox batteries are rechargeable electrochemical cells in which the chemical energy is provided by two electrolytes separated by an ion exchange membrane. In operation, with the flow of electric current, ion exchange occurs through the ion exchange membranes while the electrolytes circulate in their respective spaces.
As used herein, the term "metal halide" refers to a compound having a metal and a halogen. The metal of the metal halide generally includes any of the metals in groups 1 to 16 of the periodic table, but is generally a group 1 alkali metal. The halide of the metal halide will be any halogen in group 17 of the periodic table.
As used herein, the terms "nitrile" and "nitrile-based compound" refer to an organic chemical species containing at least one cyano functionality 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), propylnitrile, cyclopentanenitrile, 4-cyanobenzaldehyde, and ethylene glycol bis (propionitrile) Ether (EGBP). Nitriles, like ethylene glycol dimethyl ether, are chemically inert aprotic polar solvents.
As used herein, the term "heterocyclic compound" in its conventional sense refers to a compound having a ring structure with at least two different elements as its ring members. As known to those skilled in the art, the heterocyclic compounds are too numerous to list; thus, 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 is to be understood that this list of heterocyclic compounds is intended to be illustrative and not limiting. Examples of saturated 3-atom rings include, but are not limited to, aziridine, oxirane, and thietane. Examples of unsaturated 3-atom rings include, but are not limited to, aziridine, oxetane and thienylene. Examples of saturated 4-atom rings include, but are not limited to, azetidine, oxetane, thietane. Examples of unsaturated 4-atom rings include, but are not limited to, azetidine, oxetane and thietane. Examples of saturated 5-atom rings include, but are not limited to, pyrrolidine, oxolane, and thiacyclopentane. 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, dioxane, and thiane. 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, oxepin, and thiepin. Examples of saturated 8-atom rings include, but are not limited to, azocane, oxacyclooctane, and thiacyclooctane. Examples of unsaturated 8-atom rings include, but are not limited to, azacyclooctene, oxocyclooctene, and thietane. Examples of saturated 9-atom rings include, but are not limited to, azacyclononane, oxacyclononane, and thiacyclononane. Examples of unsaturated 9-atom rings include, but are not limited to, azacyclononene, oxacyclononene, and thiacyclononene. An exemplary but non-limiting heterocycle for use herein is 1,3-Dioxolane (DOL).
Metal halide cells are redox cells that use metal halides as the active cathode material in the presence of an oxidizing gas. Unlike lithium ion batteries and NiMH batteries, metal halide batteries are made without heavy metals; thus, metal halide batteries have potentially lower manufacturing costs than conventional lithium ion batteries or NiMH batteries. In order to be a suitable alternative to lithium ion batteries and NiMH batteries, metal halide batteries need to be optimized.
As used herein, the terms "glyme" and "glyme-based compound" refer to glycol ether-based solvents that do not carry free hydroxyl groups. Due to the lack of functional groups, glyme solvents are chemically inert and aprotic (lack of H atoms/inability to hydrogen bond) polar solvents. The chemical formula of the glycol dimethyl ethers is as follows: r 1 O-(CR 2 2 CR 2 2 O)n-CR 1 . Examples of ethylene glycol dimethyl ether solvents include, but are not limited to, 1,2-dimethoxyethane, 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 ] ethane]Ether (tetraglyme).
Described herein is a battery comprising an anode, an electrolyte, and a cathode current collector in contact with an active cathode material, wherein the electrolyte comprises (i) a solvent comprising one or more than one organic liquid compound; (ii) (ii) a mixture of metal halides and their corresponding halogens, wherein the mixture is used as an active cathode material and the mixture is dissolved in a solvent, and (iii) an oxidizing gas also dissolved in the solvent.
In one embodiment, the metal halide and its corresponding halogen are dissolved in a solvent prior to introduction of the oxidizing gas. In another embodiment, the metal halide, its corresponding halogen, and the oxidizing gas are introduced together into the solvent. In another embodiment, the metal halide, its corresponding halogen, the oxidizing gas, and the solvent are combined together to form an electrolyte solution.
Solvents that may be used to prepare the electrolyte formulations described herein include, but are not limited to, nitriles, heterocyclic compounds, and ethylene glycol dimethyl ether. In one embodiment, the solvent includes a nitrile and ethylene glycol dimethyl ether. In another embodiment, the solvent comprises a heterocyclic compound with ethylene glycol dimethyl ether. In another embodiment, the solvent includes a nitrile and a heterocyclic compound. In another embodiment, the solvent includes a nitrile, a heterocyclic compound, and ethylene glycol dimethyl ether.
Metal halides useful in preparing the electrolyte formulations described herein include any metal halide, including salts, that can dissociate into: (i) Is selected from I - 、Br - 、Cl - And F - The ion of (2); and (ii) is selected from Li + 、Mg 2+ 、Al 3+ And Na + The ion of (2). Halogen may be a halogen containing I 2 、Br 2 、CI 2 And F 2 Any molecular halogen of at least one of (a). In one embodiment, the molar concentration ratio of metal halide to halogen is greater than 0.5. In another embodiment, the molar concentration ratio is from 0.5 to 8. In other embodiments, the molar concentration ratio is about 1. For purposes of illustration only, and not intended to be limiting, the metal halides LiI and halogens I 2 Will be described herein as an exemplary mixture of active cathode materials.
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.
In another embodiment, the electrolyte may include one or more than one lithium salt (in addition to LiI). Examples of other lithium salts include, but are not limited to, lithium nitrate (LiNO) 3 ) Lithium fluoride (LiF), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI; liC 2 F 6 NO 4 S 2 ) Lithium trifluoromethanesulfonate (LiCF) 3 SO 3 ) Lithium hexafluorophosphate (LiPF) 6 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium perchlorate (LiClO) 4 ) And lithium tetrafluoroborate (LiBF) 4 )。
Examples of materials that may be used for the anode of the rechargeable batteries described herein include, but are not limited to, one or more than one alkali metal and/or one or more than one alkaline earth metal. In one embodiment, the anode comprises at least one of Li, mg, al, and Na.
Examples of materials for the cathode current collector of the 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, polymeric 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.
As will be understood by those skilled in the art, the batteries described herein will be manufactured for sale in the form of a battery assembly. Examples of such battery packs include, but are not limited to, pouch batteries, cylindrical batteries, prismatic batteries, coin batteries, and SWAGELOK (RTM) Batteries (SWAGELOK, solon, OH, USA).
The liquid active cathode materials described herein increase the solubility of metal halides without significantly increasing the viscosity of the electrolyte, resulting in a metal halide cell with improved energy density compared to conventional metal halide cells. This high energy density of metal halide cells is achieved by the formulation of active cathode materials comprising a mixture of a metal halide and the corresponding halogen of the metal halide in the presence of an oxidizing gas. The combination of molecular halogen and metal halide as active cathode materials reduces the cost of manufacturing the high energy density metal halide cells described herein because molecular halogen is a lower cost material than metal halide salts.
Example 1 describes the general procedure for making a cell using an active catholyte solution comprising (I) a mixed solvent solution of 1:1 volume ratio of nitrile, methoxypropionitrile (MPN) and ethylene glycol dimethyl ether, 1,2-Dimethoxyethane (DME), and (ii) LiI or LiI + I 2 As an active cathode material. FIGS. 1A to 1C and Table 1 show a production method according to the method in example 1The discharge capacity performance of three metal halide cells was constructed after ten cycles, where the effective molar concentrations of the active cathode materials and the discharge conditions were as follows: only 3M LiI (fig. 1A); 1M LiI +1M I 2 First cycle charging (fig. 1B); and 1M LiI +1M I 2 Discharge was first cycled (fig. 1C). Fig. 1B and 1C also include discharge conditions for the test, where fig. 1B shows the discharge capacity performance of the battery charged after manufacture, and fig. 1C shows the discharge capacity performance of the battery discharged without initial charge after manufacture. All the batteries are at 1mA/cm 2 The test was performed at current density. As shown in FIGS. 1A to 1C and Table 1, with Li + I 2 Cells made with the active cathode material performed better than cells made with LiI alone. The data also show that when the first cycle is a discharge cycle, liI + I is used 2 The cell made with the active cathode material was cycled ten times (5.67 mA-hr/cm) 2 ) Shows a charge cycle (4.71 mA-hr/cm) more than the first cycle 2 ) Higher discharge capacity. These data indicate that, unlike conventional metal halide batteries, batteries manufactured using active cathode formulations comprising a metal halide and its corresponding molecular halogen can be discharged immediately after manufacture without the need for an initial charge cycle.
TABLE 1
Example 2 describes the procedure used to test the viscosity of the metal halide/molecular halogen active cathode materials described herein in a mixed solvent solution. As shown in table 2, when LiI is the only active cathode material in the organic electrolyte solution, the viscosity of the electrolyte solution increases with the increase in the amount of LiI (test 1 and test 2). When the test contains LiI + I 2 When comparing the viscosity of the electrolyte solution, liI + I 2 The electrolyte solution had the same viscosity as the LiI only electrolyte solution (test 5 and test 6). The results in table 2 show that the incorporation of the corresponding molecular halogen into the metal halide active catholyte formulation has no effect on the viscosity of the electrolyte solution. Due to metal halides and molecular halogensThe difference in molecular mass between, replacing some of the metal halides in the cell with molecular halogens can result in an increase in the amount of active cathode material that can be loaded in the cell during the manufacturing process. The resulting increase in active cathode material without a corresponding increase in viscosity results in a battery having improved volumetric energy density and increased charge transport kinetics over conventional metal halide batteries.
TABLE 2
| Test # | Iodine (I) 2 ，M) | Lithium iodide (LiI, M) | Viscosity (CP) |
| 1 | 0 | 0.5 | 1.32 |
| 2 | 0 | 1 | 2.06 |
| 3 | 0.5 | 0 | 0.95 |
| 4 | 1 | 0 | 1.07 |
| 5 | 0.5 | 0.5 | 1.36 |
| 6 | 1 | 1 | 2.06 |
FIG. 2 illustrates the use of the following LiI + I 2 Active cathode formulation charge/discharge capacity of metal halide cell made in 400 cycles: 0.8M LiI +0.1M I 2 ；0.5M LiI+0.25M I 2 ；0.33M LiI+0.33M I 2 ；0.2M LiI+0.4M I 2 (ii) a And 1M LiI as a control. As shown in fig. 2, with LiI and I at equimolar concentrations 2 (0.33M LiI+0.33M I 2 ) The metal halide cell made with the LiI cathode formulation of (a) maintained the same discharge capacity after 250 cycles as the control cell (1M LiI). Table 3 provides LiI and I data based on FIG. 2 2 Molar concentration range ratio of (a). As shown in table 3, the cells described herein were operated at a molar concentration ratio of metal halide to halogen of 0.5 to infinity. LiI + I in Table 3 2 In the context of batteries, I 2 Is greater than 0. More generally, for the metal halide/halogen cells described herein, the halogen molar concentration may be close to, but not equal to, zero (halogen > 0). Since the commercial cost of metal halide salts is much higher than molecular halogens, batteries made with active catholyte formulations with metal halides and molecular halogens provide cost savings over conventional metal halide batteries.
TABLE 3
| LiI and I 2 Molarity of the solution | LiI/I 2 |
| 1MLiI | ∞ |
| 0.8M LiI+0.1M I 2 | 8 |
| 0.5M LiI+0.25 |
2 |
| 0.33MLiI+0.33MI 2 (Charge first) | 1 |
| 0.33MLiI+0.33MI 2 (first discharge) | 1 |
| 0.2MLiI+0.4MI 2 | 0.5 |
Example 3 describes a procedure for testing the solubility of the metal halide/molecular halogen active cathode materials described herein in a mixed solvent solution. As shown in Table 4, the maximum solubility of LiI alone in a 1:1 MNP DME solvent solution is 5M; however, when I is added to the solution 2 When the maximum solubility of LiI increased to 7M, indicating that LiI and I were present in the mixed solvent electrolyte solution 2 There is a synergistic effect between them.
TABLE 4
Reference tableIodine ion (I) effective in the cell in the fully discharged state - ) At a concentration of I - ＝LiI+2I 2 . When 7M LiI and 3M I 2 When used as an active cathode material, the concentration of iodide ions in the electrolyte is 13M I in the fully discharged state - The effective iodide ion concentration is determined by having only LiI or I 2 The battery of active cathode material achieved more than twice the concentration of iodide ions. 7M LiI and 3M I 2 The intermediate product of the reaction is 3M triiodide (I) 3 - (ii) a Charged product) and 4M I - (discharge product). The chemical species contributing to the high discharge capacity of metal halide cells are charge products (i.e., I) in the electrolyte solution 3 - ) Is present. Thus, for the use of LiI + I in electrolyte solutions 2 Of the electrolyte solution of 3 - The presence of ions results in a battery that does not require charging prior to use. The results in table 4 show that formulating the electrolyte solution with stoichiometric amounts of metal halides and their corresponding halogens in organic solvent solutions allows for optimization of the solubility of chemicals in the electrolyte that contribute to the discharge capacity.
The metal halide/molecular halogen active catholyte materials described herein have the following improvements over conventional metal halide batteries: lower manufacturing costs, higher loading capacity, higher energy density, higher charge transport kinetics, and the ability to discharge immediately after manufacture.
The description of various embodiments of the present invention has been presented for purposes of illustration but is not intended to be exhaustive or limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope of the described embodiments. The terminology used herein is selected to best explain the principles of the embodiments, the practical application or technical improvements to the technology found in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Experiment of
The following examples are set forth so as to provide those of ordinary skill in the art with a complete disclosure of how to make and use the aspects and embodiments of the invention set forth herein. While efforts have been made to ensure accuracy with respect to variables such as amounts, temperature, etc., experimental errors and deviations should be accounted for. Unless otherwise indicated, parts are parts by weight, temperature is in degrees Celsius, and pressure is at or near atmospheric. All components were obtained commercially unless otherwise indicated.
Example 1
General procedure for Battery preparation
With LiI and I 2 A battery was prepared for the active cathode material. LiI was placed in a vial and placed in an argon filled glove box (< 0.1ppm H) at 120 deg.C 2 O，O 2 ) Dried on an inner hot plate for 12 hours. Status usage as in arrival I 2 . Mixing ethylene glycol dimethyl ether-based compound (DME), nitrile-based compound (MPN) and heterocyclic compound (1,3-dioxolane) with 20mg of molecular sieve
Stored in different vials overnight. Then, the ratio of 1:1 volume ratio a mixed solvent solution was prepared with the following compounds: (i) DME and MPN, and (ii) DME and 1,3-dioxolane. For testing, liI alone, I alone 2 Or LiI and I 2 Is dissolved in the mixed solvent solution at a predetermined molar ratio to form an active catholyte solution. Each electrolyte solution was then used to wet the quartz filter separator and the cathode current collector, which consisted of carbon cloth, carbon nanoparticles, and a polymer binder. The active cathode material is placed in constant contact with a carbon cathode current collector and an electrolyte solution. The assembly of all cells was performed in a glove box. A lithium metal foil anode, an electrolyte-wetted separator, and a wetted carbon current collector were placed in sequence in a Swagelok cell equipped with an oxygen inlet and outlet tube. Oxygen is introduced from the inlet tube, purged, and completely replaced with argon gas in the cell.
Example 2
Effect of iodine active Material formulation on electrolyte viscosity
The viscosities of six different liquid cathode formulations were tested according to the cell fabrication procedure of example 1. As shown in Table 2In a 30mL solvent mixture of 1:1 MPN DME (v/v) was prepared the following six LiI, I 2 And LiI + I 2 A mixture of (a); (1) 0.5M I 2 ；(2)1M I 2 ；(3)0.5M LiI；(4)1M LiI；(5)0.5M I 2 +0.5M LiI; and (6) 1M I 2 +1M LiI. Using SEKONIC (RTM) VM-100A-L torsional shaker (Kabushiki Kaisha Sekonic Co., tokyo, JP) measures the viscosity of the solution for six tests.
Example 3
Effect of iodine active Material formulation on Total Mass Loading
A MPN of 50: DME (v/v) in mixed solvent and separated into three 1mL volumes. To test the solubility of the active cathode materials, the following three active cathode materials were added to three 1mL volumes of mixed solvent solutions, respectively: 5mM LiI;3mM I 2 (ii) a And 7mM LiI +3mM I 2 . Table 4 shows the results of the solubility test.
Claims (38)
1. A battery, comprising:
an anode;
a cathode current collector; and
an electrolyte that facilitates transport of ions between an anode and a cathode, wherein the electrolyte comprises:
a solvent comprising one or more than one organic liquid compound,
an active cathode material comprising a mixture of a metal halide and its corresponding halogen, wherein the molar concentration ratio of metal halide to halogen is greater than 0.5, the mixture is dissolved in a solvent, and the active cathode material is in contact with a cathode current collector, an
An oxidizing gas dissolved in the solvent.
2. The battery of claim 1, wherein the metal halide comprises a metal halide that dissociates into (I) a group selected from I - 、Br - 、Cl - And F - And (ii) is selected from Li + 、Mg 2+ 、Al 3+ And Na + A salt of the ion of (a).
3. The battery of claim 1, wherein halogen is I 2 、Br 2 、Cl 2 And F 2 Molecular halogen of at least one of (1).
4. The battery of claim 1, wherein the one or more than one organic liquid compound comprises a nitrile and/or a heterocyclic compound.
5. The battery of claim 4, wherein the one or more than one organic liquid compound comprises ethylene glycol dimethyl ether.
6. The battery of claim 1, wherein the molar concentration ratio of metal halide to halogen is from 0.5 to 8.
7. 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.
8. The battery of claim 2, wherein the anode comprises at least one of Li, mg, al, and Na.
9. The battery of claim 1, wherein the cathode current collector comprises a porous carbon material and/or a metal.
10. 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.
11. An electrolyte for a rechargeable metal halide battery, comprising:
a solvent comprising one or more than one organic liquid compound,
an active cathode material comprising a mixture of a metal halide and its corresponding halogen, wherein the molar concentration ratio of metal halide to halogen is greater than 0.5, and the mixture is dissolved in a solvent; and
an oxidizing gas dissolved in the solvent.
12. The electrolyte of claim 11, wherein the metal halide comprises a metal halide that dissociates into (I) a group selected from I - 、Br - 、Cl - And F - And (ii) is selected from Li + 、Mg 2+ 、Al 3+ And Na + A salt of the ion of (a).
13. The electrolyte of claim 11, wherein halogen is I 2 、Br 2 、Cl 2 And F 2 Molecular halogen of at least one of (1).
14. The electrolyte of claim 11, wherein the organic solvent comprises a nitrile and/or a heterocyclic compound.
15. The electrolyte of claim 14, wherein the organic liquid compound comprises glyme.
16. The electrolyte of claim 11, wherein the molar concentration ratio of metal halide to halogen is 0.5 to 8.
17. The electrolyte of claim 11, wherein the oxidizing gas is selected from the group consisting of oxygen, air, nitric oxide, nitrogen dioxide, and mixtures and combinations thereof.
18. A rechargeable battery, comprising:
an anode;
a cathode current collector; and
an electrolyte that facilitates transport of ions between an anode and a cathode current collector, wherein the electrolyte comprises:
a mixed solvent solution containing a nitrile-based compound and/or a heterocyclic-based compound,
comprising LiI and I 2 Active cathode material of the mixture ofThe compound is dissolved in a mixed solvent solution of LiI and I 2 Is in the range of 0.5 to 8, and the active cathode material is in contact with a cathode current collector, an
An oxidizing gas dissolved in the solvent.
19. The rechargeable battery according to claim 18, wherein the nitrile-based compound is methoxypropionitrile and the heterocycle-based compound is 1,3-dioxolane.
20. The rechargeable battery according to claim 18, wherein the mixed solvent solution comprises an ethylene glycol dimethyl ether-based compound.
21. The rechargeable battery according to claim 20, wherein the ethylene glycol dimethyl ether-based compound is 1,2-dimethoxyethane.
22. The rechargeable battery of claim 18, wherein electrolyte comprises a material selected from lithium nitrate (LiNO) 3 ) Lithium fluoride (LiF), lithium bis (trifluoromethanesulfonyl) imide (LiTFSl; liC 2 F 6 NO 4 S 2 ) Lithium trifluoromethanesulfonate (LiCF) 3 SO 3 ) Lithium hexafluorophosphate (LiPF) 6 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium perchlorate (LiClO) 4 ) And lithium tetrafluoroborate (LiBF) 4 ) Other lithium salts of (a).
23. The rechargeable battery of claim 18, wherein the anode comprises Li.
24. A rechargeable battery according to claim 18, wherein the cathode current collector comprises a porous carbon material and/or a metal.
25. The rechargeable battery according to claim 18, wherein the oxidizing gas is selected from the group consisting of oxygen, air, nitric oxide, nitrogen dioxide, and mixtures and combinations thereof.
26. A method of preparing an electrolyte for a metal halide rechargeable battery, the method comprising:
dissolving a metal halide and its corresponding halogen in a solvent comprising a nitrile-based compound and/or a heterocyclic-based compound, wherein the molar concentration ratio of metal halide to halogen is greater than 0.5; and
an oxidizing gas is introduced into the solvent.
27. The method of claim 26, wherein the metal halide comprises a dissociation into (I) a metal halide selected from I - 、Br - 、Cl - And F - And (ii) is selected from Li + 、Mg 2+ 、Al 3+ And Na + A salt of the ion of (1).
28. The method of claim 26, wherein halogen comprises I 2 、Br 2 、Cl 2 And F 2 Molecular halogen of at least one of (1).
29. The method of claim 26 wherein the nitrile-based compound is methoxypropionitrile and the heterocycle-based compound is 1,3-dioxolane.
30. The method of claim 26, wherein the mixed solvent solution comprises an ethylene glycol dimethyl ether-based compound.
31. The method of claim 26, wherein the glyme-based compound is 1,2-dimethoxyethane.
32. The method of claim 26, wherein the oxidizing gas is selected from the group consisting of oxygen, air, nitric oxide, nitrogen dioxide, and mixtures and combinations thereof.
33. A method of making a metal halide rechargeable battery, the method comprising:
mixing LiI and I 2 Dissolving in a solvent to form an electrolyte solution, wherein the solvent comprises a nitrile-based compound and/or a heterocyclic-based compound, and LiI and I 2 In a molar ratio of 0.5 to 8;
soaking the diaphragm in an electrolyte solution;
forming a stack comprising an anode, a soaked separator, and a cathode current collector, wherein the soaked separator is placed between the anode and the cathode current collector; and
an oxidizing gas is introduced into the stack.
34. The method of claim 33 wherein the nitrile-based compound is methoxypropionitrile and the heterocycle-based compound is 1,3-dioxolane.
35. The method of claim 33, wherein the solvent comprises an ethylene glycol dimethyl ether-based compound.
36. The method of claim 35, wherein the glyme-based compound is 1,2-dimethoxyethane.
37. A method of preparing an electrolyte for a metal halide rechargeable battery, the method comprising:
combining a metal halide, a corresponding halogen of the metal halide, an oxidizing gas, and a solvent, wherein the solvent comprises a nitrile-based compound and/or a heterocyclic-based compound, and the molar concentration ratio of the metal halide to the halogen is greater than 0.5.
38. A method of making a metal halide rechargeable battery, the method comprising:
form a composition comprising LiI, I 2 An oxidizing gas and a solvent, wherein the solvent comprises a nitrile-based compound and/or a heterocyclic-based compound, and LiI and I 2 In a molar ratio of 0.5 to 8;
soaking the diaphragm in an electrolyte solution; and
a stack is formed that includes an anode, a soaked separator, and a cathode current collector, wherein the soaked separator is placed between the anode and cathode current collectors.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US16/858,665 US20210336296A1 (en) | 2020-04-26 | 2020-04-26 | Electrolyte compositions for rechargeable metal halide battery |
| US16/858,671 | 2020-04-26 | ||
| US16/858,671 US11515566B2 (en) | 2020-04-26 | 2020-04-26 | Liquid cathode formulation for rechargeable metal halide battery |
| US16/858,665 | 2020-04-26 | ||
| PCT/EP2021/058451 WO2021219320A1 (en) | 2020-04-26 | 2021-03-31 | Liquid cathode formulation for rechargeable metal halide battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115836419A true CN115836419A (en) | 2023-03-21 |
Family
ID=75396756
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202180045640.2A Pending CN115836419A (en) | 2020-04-26 | 2021-03-31 | Liquid cathode formulation for rechargeable metal halide cells |
| CN202180045657.8A Pending CN115836416A (en) | 2020-04-26 | 2021-03-31 | Electrolyte composition for rechargeable metal halide batteries |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202180045657.8A Pending CN115836416A (en) | 2020-04-26 | 2021-03-31 | Electrolyte composition for rechargeable metal halide batteries |
Country Status (4)
| Country | Link |
|---|---|
| EP (2) | EP4143911A1 (en) |
| CN (2) | CN115836419A (en) |
| AU (2) | AU2021263028B2 (en) |
| WO (2) | WO2021219319A1 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030190527A1 (en) * | 2002-04-03 | 2003-10-09 | James Pugh | Batteries comprising alkali-transition metal phosphates and preferred electrolytes |
| US7923153B2 (en) * | 2008-04-29 | 2011-04-12 | Eveready Battery Company, Inc. | Linear ether electrolyte with asymmetric end groups for use in lithium batteries |
| US11316199B2 (en) * | 2018-01-16 | 2022-04-26 | International Business Machines Corporation | Rechargeable metal halide battery |
-
2021
- 2021-03-31 EP EP21716674.3A patent/EP4143911A1/en active Pending
- 2021-03-31 EP EP21716673.5A patent/EP4143908A1/en active Pending
- 2021-03-31 AU AU2021263028A patent/AU2021263028B2/en active Active
- 2021-03-31 CN CN202180045640.2A patent/CN115836419A/en active Pending
- 2021-03-31 WO PCT/EP2021/058446 patent/WO2021219319A1/en unknown
- 2021-03-31 WO PCT/EP2021/058451 patent/WO2021219320A1/en unknown
- 2021-03-31 CN CN202180045657.8A patent/CN115836416A/en active Pending
- 2021-03-31 AU AU2021265012A patent/AU2021265012B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| WO2021219320A1 (en) | 2021-11-04 |
| AU2021265012A1 (en) | 2022-07-21 |
| AU2021263028B2 (en) | 2024-06-06 |
| AU2021263028A1 (en) | 2022-07-28 |
| EP4143908A1 (en) | 2023-03-08 |
| EP4143911A1 (en) | 2023-03-08 |
| CN115836416A (en) | 2023-03-21 |
| AU2021265012B2 (en) | 2023-06-22 |
| WO2021219319A1 (en) | 2021-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7216734B2 (en) | rechargeable metal halide battery | |
| JP5273256B2 (en) | Non-aqueous electrolyte and metal-air battery | |
| EP2765645A1 (en) | Electrolytic solution for lithium air cell | |
| US11335908B2 (en) | Rechargeable metal halide battery | |
| JP7499780B2 (en) | Rechargeable Metal Halide Batteries | |
| CN108075113A (en) | Active material for positive electrode for battery and the battery using the active material for positive electrode for battery | |
| US20140295262A1 (en) | Electrolyte solution for lithium metal battery, and lithium metal battery | |
| JP3287376B2 (en) | Lithium secondary battery and method of manufacturing the same | |
| CN115836419A (en) | Liquid cathode formulation for rechargeable metal halide cells | |
| US11515566B2 (en) | Liquid cathode formulation for rechargeable metal halide battery | |
| US20220013778A1 (en) | Rechargeable metal halide battery with intercalation anode | |
| US20210336296A1 (en) | Electrolyte compositions for rechargeable metal halide battery | |
| JP3132671B2 (en) | Method for producing positive electrode active material for non-aqueous electrolyte secondary battery | |
| Lau et al. | Lipophilic additives for highly concentrated electrolytes in lithium-sulfur batteries | |
| US20220255134A1 (en) | Stable electrolyte based on a fluorinated ionic liquid and its use in high current rate lithium-air batteries | |
| US11824199B2 (en) | Metal halide cathode with enriched conductive additive | |
| JP7092644B2 (en) | Method for manufacturing electrolytic solution, fluoride ion battery and electrolytic solution | |
| KR20100098038A (en) | Additives of electrode active materials for enhancement of battery capacity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |