Positive electrode material for alkali metal ion batteries and method for producing same

Abstract

An exemplary embodiment of the present disclosure provides a positive electrode for use in an alkali metal ion battery, the positive electrode comprising a crystal lattice of a metal halide. The metal halide is represented by the formula: (Fe 1-z M a )(Cl y X 3-y ) where M is a metal, X is a halogen, a is between 0 and 2.9, z is between 1 and 0, and y is between 0 and 3.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of U.S. Provisional Application No. 63 / 363,875, filed April 29, 2022, which is incorporated by reference in its entirety as if fully set forth below.

[0002] (Application for Federally Funded Research) This invention was made with Government support under Grant / Award No. 2004878 awarded by the National Science Foundation. The Government has certain rights in this invention.

[0003] (Technical field) Various embodiments of the present disclosure relate generally to alkali metal ion batteries, and more particularly to positive electrode materials including iron chloride. [Background technology]

[0004] High capacity and high performance electroactive materials are essential for the adoption of new battery technologies such as smart Internet of Things (IoT) devices and electric vehicles (EVs). Solid-state lithium-ion batteries (LIBs) are considered a promising battery technology for the next generation of electrochemical energy storage. Current electrochemical cells are fabricated using traditional cathode materials such as LiCoO2, LiMn2O4, LiFePO4, and nickel-manganese-cobalt (NMC) materials. These cells also utilize liquid electrolytes to move ions through the cell to generate voltage. To achieve this, typical commercial LIBs contain flammable liquid organic electrolytes, which can cause fires and explosions in harsh or abused environments. The volume required for battery packs using liquid electrolytes is significant, making such LIBs bulky, dense, and difficult to use. These issues make LIBs difficult to scale up and potentially dangerous to consumers under harsh conditions.

[0005] Increasing demand for electrified transportation and grid storage has led to a demand for electrochemical energy storage devices with higher energy density than current LIBs, especially at lower cost. Most LIBs are layered oxides made from expensive semi-precious minerals such as Co, and require high-temperature sintering. Fe is an attractive redox-active element due to its low cost and low toxicity, but unfortunately LiFeO2 is not cycled in LIBs. LiFePO4 is less expensive than the layered oxides in the raw materials, but it generally requires carbon coating and nanosizing, which increases the manufacturing cost.

[0006] Besides layered oxides, most binary compounds, such as fluorides, have been used as conversion-type cathodes / anodes in LIBs, but only small intercalation capacities have been observed for fluorides such as FeF2, CuF2, and FeF3. The reported Li-intercalation plateau of FeF3 varies from 3.0 V to 3.3 V, which is usually associated with large voltage hysteresis and low energy efficiency, limiting its practical application. - Cl, which is larger in size than - In principle, chlorides should be better hosts for Li-intercalation than fluorides, since the lattice may allow better diffusion channels. However, most metal chlorides are soluble in commonly used organic liquid electrolytes (LEs), which has greatly limited the exploration of chlorides as cathodes. Previously, only a limited number of studies have reported on chloride cathodes, most of which operate via a conversion mechanism and suffer from dissolution issues. Very recently, Li intercalation-deintercalation reactions have been reported in VCl3 when used in saturated concentrated electrolytes.

[0007] The new trend of replacing liquid electrolytes with solid electrolytes aims to enable Li metal anodes and increase energy density. The advent of solid electrolytes (SEs) has eliminated the issues regarding the dissolution of chlorides and possibly other compounds with similar problems. In particular, recent reports of high-performance halide SEs imply that halide SEs, with their good ionic conductivity and compatibility with high-voltage cathode materials, could provide an excellent testbed for novel cathode families. Therefore, there is a need for highly reversible Li insertion / extraction in the cathode with halide SEs, while keeping the overall market price of LIBs low. Summary of the Invention

[0008] The present disclosure relates to an alkali metal ion battery having a positive electrode material comprising a metal halide crystal lattice, and a method for making the same. Exemplary embodiments of the present disclosure include an alkali metal ion battery having a positive electrode material comprising a metal halide crystal lattice of the formula (Fe 1-z M a )(Cl y X 3-y wherein M is a metal, X is a halogen, a is between 0 and 2.9, z is between 1 and 0, and y is between 0 and 3.

[0009] In any of the embodiments disclosed herein, M can be a metal selected from the group consisting of titanium, chromium, manganese, cobalt, nickel, copper, zinc, molybdenum, technetium, ruthenium, vanadium, tungsten, rhenium, osmium, lithium, sodium, potassium, rubidium, or cesium.

[0010] In some embodiments, X can be a halogen selected from fluorine, bromine, or iodine.

[0011] In some embodiments, the metal halide can include FeF3, FeCl3, FeBr3, FeI3, CrCl3, CrBr3, MnCl3, or CrI3.

[0012] In some embodiments, the energy density of the metal halide may be approximately 600 Wh / kg.

[0013] In some embodiments, the metal halide can be configured to be reversibly lithiated and delithiated upon exposure to lithium ions.

[0014] In some embodiments, the metal halide can be configured to be reversibly sodiated and desodiated upon exposure to sodium ions.

[0015] Exemplary embodiments of the present disclosure include a compound of formula (Fe 1-z M a )(Cl y X 3-y wherein M is a metal, X is a halogen, a is between 0 and 2.9, z is between 1 and 0, and y is between 0 and 3. The battery is provided with a positive electrode comprising a metal halide represented by the formula: + The operating voltage for the / Li redox couple can be configured to be greater than about 3V.

[0016] In some embodiments, the battery comprises a Li + The operating voltage for the / Li redox couple can be configured to be greater than about 3.3V.

[0017] In some embodiments, the battery comprises a Li + The operating voltage for the / Li redox couple can be configured to be greater than about 3.6V.

[0018] In some embodiments, the battery is further configured to have an operating voltage of approximately 3.6V at a charge / discharge cycling capacity rate of approximately 0.1C at 25°C.

[0019] In some embodiments, the battery is further configured to have an operating voltage of approximately 3.6V with a charge / discharge cycle capacity of approximately 0.1C at 60°C.

[0020] In some embodiments, the battery comprises 2+ / Fe 3+ Reversible specific capacity for redox couple is 150mAh g -1 It can be configured to exceed

[0021] In some embodiments, the battery has a positive electrode energy density of approximately 541 Wh kg, based on the total weight of the metal halide. -1 The above configuration can be achieved.

[0022] In some embodiments, the battery has a positive electrode energy density of about 594 Wh kg, based on the total weight of the metal halide. -1 It can be configured so that:

[0023] An exemplary embodiment of the present disclosure provides a method for producing a solid electrolyte comprising the steps of: 1-z M a )(Cl y X 3-y and a metal halide positive electrode represented by the formula: wherein M can be a metal, X can be a halogen, a can be between 0 and 2.9, z can be between 1 and 0, and y can be between 0 and 3.

[0024] In some embodiments, the battery comprises a Li + The operating voltage for the / Li redox couple can be configured to be greater than about 3V.

[0025] In some embodiments, the battery comprises a Li + The operating voltage for the / Li redox couple can be configured to be greater than about 3.3V.

[0026] In some embodiments, the battery comprises a Li + The operating voltage for the / Li redox couple can be configured to be about 3.6 V or greater.

[0027] In some embodiments, the battery can be configured to have an operating voltage of approximately 3.6 V at 25° C. with a charge / discharge cycling capacity rate of approximately 0.1.

[0028] In some embodiments, the battery can be configured to have an operating voltage of approximately 3.6 V with a charge / discharge cycle capacity of approximately 0.1 at 60° C.

[0029] In some embodiments, the battery comprises 2+ / Fe 3+ Reversible specific capacity for redox couple is 150mAh g -1 It can be configured to exceed

[0030] In some embodiments, the battery has a positive electrode energy density of approximately 540 Wh kg, based on the total weight of the metal halide. -1 It can be configured to exceed

[0031] In some embodiments, the battery has a positive electrode energy density of about 594 Wh kg, based on the total weight of the metal halide. -1 It can be configured so that:

[0032] In some embodiments, the metal halide has a positive electrode energy density of approximately 600 Wh kg based on the total weight of the metal halide. -1 It can be said that:

[0033] In some embodiments, the metal halide can include a metal selected from the group consisting of titanium, chromium, manganese, cobalt, nickel, copper, zinc, molybdenum, technetium, ruthenium, vanadium, tungsten, rhenium, osmium, lithium, sodium, potassium, rubidium, and cesium.

[0034] In some embodiments, the metal halide can include a halogen selected from fluorine, bromine, and iodine.

[0035] In some embodiments, the metal halide can include FeF3, FeCl3, FeBr3, FeI3, CrCl3, CrBr3, MnCl3, or CrI3.

[0036] In some embodiments, the solid electrolyte has the formula: a (M E1 ) b (M E2 ) c (X E ) d where A can be one or more cations selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, silver, gold, titanium, or combinations thereof; M E1 can be one or more cations selected from the group consisting of iron, titanium, chromium, manganese, cobalt, nickel, copper, zinc, molybdenum, technetium, ruthenium, vanadium, tungsten, niobium, tantalum, lanthanum, boron, aluminum, scandium, gallium, yttrium, zirconium, indium, silicon, germanium, tin, arsenic, antimony, tellurium, thallium, lead, bismuth, polonium, or combinations thereof; M E2may be one or more cations selected from the group consisting of boron, aluminum, scandium, gallium, yttrium, zirconium, indium, silicon, germanium, tin, arsenic, antimony, tellurium, thallium, lead, bismuth, polonium, or combinations thereof; M E1 and M. E2 can contain different cations, X E can be one or more anions selected from the group consisting of fluorine, chlorine, bromine, iodine, or oxygen; a can be 1 to 10; b and c are each independently less than 6; and d can be 0 to 18.

[0037] In some embodiments, the solid electrolyte has the formula: a (M E1 S4) b (PS4) 4-b (X E )3, where A can be one or more cations selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, silver, gold, titanium, or combinations thereof; M E1 can be one or more cations selected from the group consisting of boron, aluminum, scandium, gallium, yttrium, zirconium, indium, silicon, germanium, tin, arsenic, antimony, tellurium, thallium, lead, bismuth, polonium, or combinations thereof; X E may be selected from the group consisting of fluorine, chlorine, bromine, or iodine, a may be 1 to 27, and b may be less than 4.

[0038] An exemplary embodiment of the present disclosure provides a method for producing a solid-state battery. The method can include combining a cathode material with at least one solid electrolyte and an anode, and compressing the solid mixture in an anhydrous container at a pressure ranging from about 200 MPa to about 400 MPa to obtain the solid-state battery. The cathode material can include at least one compound selected from FeF3, FeCl3, FeBr3, FeI3, CrCl3, CrBr3, MnCl3, or CrI3.

[0039] In some embodiments, the solid electrolyte is Li3YCl6, Li2ZrCl6, Li3ScCl6, Li3YbCl6, Li3FeCl6, Li 2.75 In 0.75 Zr 0.25 Cl6, Li 15 P4S 16 Cl3, Li 15.5 Ge 0.5 P 3.5 S 15 Cl3, Li 16 (SiS4)(PS4)3Cl3, Na 16 (GeS4)(PS4)3Br3, Li 19 (GaS4)2(PS4)2Cl3, Li 16 (GeS4)(PS4)3Cl3, Li 2-x+2y ZrCl 6-x O y (wherein x can be between 0 and 2 and y can be between 0 and 1), or combinations thereof.

[0040] In some embodiments, the method can further include charging and discharging the solid-state battery in the presence of lithium ions.

[0041] In some embodiments, the method can further include charging and discharging the solid-state battery in the presence of sodium ions.

[0042] In some embodiments, the method further comprises: +The method may include a step of ensuring that the operating voltage for the / Li redox couple is greater than about 3V.

[0043] In some embodiments, the method further comprises: + The method may include the step of: ensuring that the operating voltage for the / Li redox couple is greater than about 3.3V.

[0044] In some embodiments, the method further comprises: + The method may include providing an operating voltage for the / Li redox couple of about 3.6 V or greater.

[0045] In some embodiments, the method can further include the step of achieving an operating voltage of approximately 3.6 V at a charge-discharge cycle capacity rate of approximately 0.1 at 25°C.

[0046] In some embodiments, the method can further include the step of achieving an operating voltage of approximately 3.6 V with a charge-discharge cycle capacity of approximately 0.1 at 60° C.

[0047] In some embodiments, the method further comprises the step of: 2+ / Fe 3+ Reversible specific capacity for redox couple is 150mAh g -1 The method may include a step of causing the

[0048] In some embodiments, the method further comprises determining whether the positive electrode energy density is approximately 540 Wh kg based on the total weight of the metal halide. -1 The method may include a step of causing the

[0049] In some embodiments, the method further comprises determining that the positive electrode energy density is approximately 594 Wh kg based on the total weight of the metal halide. -1 The method may include a step of making the

[0050] These and other aspects of the disclosure are described below in the Detailed Description of the Invention and in the accompanying drawings. Other aspects and features of the embodiments will become apparent to those skilled in the art upon review of the following description of certain exemplary embodiments in conjunction with the drawings. Although features of the disclosure may be described in conjunction with certain embodiments and drawings, all embodiments of the disclosure may include one or more of the features described herein. Furthermore, although one or more embodiments may be described as having certain advantageous features, one or more of such features may be used with various embodiments described herein. Similarly, although exemplary embodiments may be described below as device, system, or method embodiments, it should be understood that such exemplary embodiments may be implemented in various devices, systems, and methods of the disclosure. [Brief description of the drawings]

[0051] The following detailed description of certain embodiments of the present disclosure will be better understood when read in conjunction with the accompanying drawings. For the purpose of illustrating the present disclosure, certain embodiments are shown in the drawings. It should be understood, however, that the disclosure is not limited to the precise arrangements and instrumentalities of the embodiments shown in the drawings.

[0052] [Figure 1] FIG. 1 shows a schematic diagram of an example alkali metal ion battery including a metal halide positive electrode material, according to an exemplary embodiment of the present invention.

[0053] [Figure 2A] FIG. 2A shows a synchrotron X-ray diffraction (XRD) pattern of an example of a delithiated metal halide cathode material, FeCl 3 , according to an exemplary embodiment of the present invention.

[0054] [Figure 2B] FIG. 2B shows an X-ray crystallographic structure of the metal halide positive electrode material of FIG. 2A, according to an exemplary embodiment of the present invention.

[0055] [Figure 3A] FIG. 3A shows a synchrotron X-ray diffraction (XRD) pattern of Li0.8FeCl3, an example lithiated metal halide positive electrode material, according to an exemplary embodiment of the present invention.

[0056] [Figure 3B] FIG. 3B shows an X-ray crystallographic structure of the metal halide positive electrode material of FIG. 3A, according to an exemplary embodiment of the present invention.

[0057] [Figure 4A] 4A and 4B show reversible lithium ion insertion and desorption in an example positive electrode comprising a metal halide crystal lattice according to an exemplary embodiment of the present invention. Fig. 4A shows the charge-discharge profile of FeCl3 at room temperature and 0.1C. [Figure 4B] FIG. 4B shows the CV curve of FeCl3 at room temperature at a scan rate of 0.01 mV / s.

[0058] [Figure 5A] FIG. 5A shows the X-ray absorption near edge structure (XANES) of an example positive electrode comprising a metal halide crystal lattice in various charged and discharged states according to an exemplary embodiment of the present invention. [Figure 5B] FIG. 5B shows the X-ray absorption near edge structure (XANES) of an example positive electrode comprising a metal halide crystal lattice in various charged and discharged states according to an exemplary embodiment of the present invention.

[0059] [Figure 6] FIG. 6 shows a schematic illustration of an operando energy dispersive X-ray diffraction (EDXRD) apparatus according to an exemplary embodiment of the present invention.

[0060] [Figure 7]FIG. 7 shows a schematic depiction of an example positive electrode comprising a metal halide crystal lattice and an energy dispersive X-ray diffraction (EDXRD) contour plot between approximately 1.5 angstroms (Å) and 4.5 angstroms (Å) of the cell before cycling, according to an exemplary embodiment of the present invention.

[0061] [Figure 8] FIG. 8 shows a zoomed-in EDXRD contour plot of layer 5 (in an example cathode comprising a metal halide crystal lattice) between 2 Å and 3.5 Å during the phase change during the first discharge / charge process and the corresponding galvanostatic discharge / charge voltage profiles according to an exemplary embodiment of the present invention.

[0062] [Figure 9] FIG. 9 shows energy dispersive diffraction data between 2 Å and 3.5 Å for the phase change during the first discharge / charge process and the corresponding galvanostatic discharge / charge voltage profiles according to an exemplary embodiment of the present invention.

[0063] [Figure 10A] 10A and 10B show the electrochemical performance of an example positive electrode including a metal halide crystal lattice according to an exemplary embodiment of the present invention: Fig. 10A shows the cycling performance of an example positive electrode including a metal halide crystal lattice with LYC electrolyte at room temperature and 0.1 charge rate (C); [Figure 10B] FIG. 10B shows the rate performance of an example of a positive electrode containing a metal halide crystal lattice with LIZC / LYBC electrolyte at varying charge rates (0.1C, 0.3C, 1C, 2C, 3C, and 5C) at 60° C.

[0064] [Figure 11A] FIG. 11A shows the cycling performance of an example positive electrode comprising a metal halide crystal lattice with a LIZC / LYBC electrolyte at 0.5 charge rate at 60° C. according to an exemplary embodiment of the present invention.

[0065] [Figure 11B]FIG. 11B shows a comparison of the specific capacity of an example cathode including a metal halide crystal lattice (denoted by an asterisk) compared to a lithium metal oxide cathode and a nickel manganese cobalt oxide cathode, according to an exemplary embodiment of the present invention.

[0066] [Figure 12A] FIG. 12A shows a synchrotron X-ray diffraction (XRD) pattern of a ball-milled electrolyte material Li3YCl6 used with an example cathode material comprising a metal halide crystal lattice, according to an exemplary embodiment of the present invention.

[0067] [Figure 12B] FIG. 12B illustrates an Arrhenius plot of the ball-milled electrolyte material Li3YCl6 used with an example cathode material comprising a metal halide crystal lattice, in accordance with an exemplary embodiment of the present invention.

[0068] [Figure 13A] FIG. 13A shows a Rietveld refinement of the optimized and observed XRD patterns of electrolyte material Li2.75In0.75Zr0.25Cl6 used with an example cathode material comprising a metal halide crystal lattice in accordance with an exemplary embodiment of the present invention.

[0069] [Figure 13B] FIG. 13B illustrates an Arrhenius plot of the ball-milled electrolyte material Li2.75In0.75Zr0.25Cl6 used with an example cathode material comprising a metal halide crystal lattice, in accordance with an exemplary embodiment of the present invention.

[0070] [Figure 14A] FIG. 14A shows a comparison of energy density and cost of different cathode materials according to an exemplary embodiment of the present invention. [Figure 14B] FIG. 14B shows a comparison of energy density and cost of different cathode materials, according to an exemplary embodiment of the present invention.

[0071] [Figure 15] FIG. 15 shows a flow chart of a method for manufacturing a solid-state battery including an example cathode material comprising a metal halide crystal lattice in accordance with the disclosed technology. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0072] In order to facilitate the understanding of the principles and features of the present disclosure, various illustrative embodiments are described below. The components, steps, and materials described below as constituting various elements of the embodiments disclosed herein are intended to be illustrative and not limiting. Many suitable components, steps, and materials that will perform the same or similar functions as the components, steps, and materials described herein are intended to be encompassed within the scope of the present disclosure. Such other components, steps, and materials not described herein include, but are not limited to, similar components or steps developed after the development of the embodiments disclosed herein.

[0073] As used herein, the use of words such as "having," "has," "including," or "includes" is intended to be open-ended and to have the same meaning as words such as "comprising" or "comprises," and is not intended to exclude the presence of other structures, materials, or acts. Similarly, the use of words such as "can" or "may" is intended to be open-ended and to indicate that a structure, material, or act is not required, but the absence of such words is not intended to indicate that a structure, material, or act is essential. Structures, materials, or acts are recognized as such to the extent that they are currently considered to be essential.

[0074] The phrases "comprising" or "containing" or "including" mean that at least the referenced compound, element, particle, or method step is present in the composition, article, or method, but do not exclude the presence of other compounds, substances, particles, or method steps, even if they have the same function as the one referenced.

[0075] It should also be understood that the reference to one or more method steps does not exclude the existence of additional or intermediate method steps between those steps expressly identified.

[0076] The components described below as constituting various elements of the present disclosure are intended to be illustrative and not limiting. Many suitable components that will perform the same or similar functions as the components described herein are intended to be encompassed within the scope of the present disclosure. Such other components not described herein include, but are not limited to, similar components developed after the development of the embodiments disclosed herein.

[0077] As mentioned above, the problem with current electrochemical cells is the expense associated with the use of rare metals in the cathode and the market price of such materials. It is desirable to power transportation vehicles and home appliances primarily with electrochemical cells that have high specific capacity performance and very low market prices. Furthermore, many of the organic electrolytes used in current electrochemical cells are flammable, dangerous under extreme conditions, and cannot be used in combination with certain cathode materials. Eliminating the need for rare cathode materials and liquid electrolytes and resulting in smaller, lighter batteries would greatly expand the design space in many industries, including automotive, electric vehicles, photovoltaics, renewable energy, IoT devices, smart homes, smart devices, solar cells, green packaging, magnetic devices, sensors, microelectronics, solid-state lighting, home appliances, in vivo electronics, aircraft, aeronautics, and power generation. Compared to commercial electrochemical cells, solid-state electrochemical cells with non-flammable solid electrolytes (SEs) not only have better safety characteristics, but also potentially higher energy density if lithium metal anodes can be enabled. Such embodiments provide safer, lighter and smaller batteries, an example of which can be seen in FIG.

[0078] The present disclosure includes a cathode material that has excellent performance and a very low market price (e.g., about 4% of the price of LiFePO4 and 1% of the price of LiCoO2), which is a very common industrial product. The cathode material dissolves in organic electrolytes. Therefore, the cathode material has not yet been investigated for use in high density batteries. In the present disclosure, the cathode material is used in combination with a solid electrolyte. In such a configuration, the cathode material can obtain a flat voltage plateau averaging 3.6 V, a high initial capacity of 152 mAh / g, and very stable long-term cycling, as described in more detail herein. Neutron diffraction and XANES have shown that in an example alkali metal ion battery, Li intercalation-deintercalation reactions occur during cycling, and the active redox couple is replaced by M 2+ / M 3+(wherein M is a metal as described below).

[0079] As shown in FIG. 1, an exemplary embodiment of the present invention provides an alkali metal-ion battery 100 including a positive electrode 102, at least one solid electrolyte 104a in contact with the positive electrode 102, a negative electrode 106, and at least one electrolyte 104b in contact with the negative electrode 106. The positive electrode 102 and the negative electrode 106 may also be in contact with current collectors 108a, 108b, respectively, such as wires or other conductors between the electrodes and an external circuit. A variety of current collectors may be used, such as, for example, aluminum, copper, nickel, titanium, stainless steel, etc. The alkali metal-ion battery 100 may be partially or completely enclosed in a housing 110, such as a PMMA sleeve, a PVC heat shrink sleeve, a plastic tube, or other insulating material.

[0080] Although FIG. 1 illustrates a stacked cell unit, the alkali metal-ion battery 100 can be constructed in any suitable orientation such that the positive electrode 102 is in contact with at least one electrolyte 104b.

[0081] The positive electrode 102 can include a metal halide crystal lattice 202. The metal halide can have a composition according to Formula 1:

[0082] (Fe 1-z M a )(Cl y X 3-y ) (Formula 1)

[0083] In some embodiments, M can be an element selected from the group consisting of post-transition metals and metalloids, such as titanium, chromium, manganese, cobalt, nickel, copper, zinc, molybdenum, technetium, ruthenium, vanadium, tungsten, rhenium, osmium, lithium, sodium, potassium, rubidium, or cesium, preferably an element selected from lithium, manganese, cobalt, and nickel. X can be a halogen selected from fluorine, bromine, or iodine. In some embodiments, a can be a number between 0 and 2.9, z can be a number between 1 and 0, and y can be a number between 0 and 3. Examples of metal halides can include, but are not limited to, FeF3, FeCl3, FeBr3, FeI3, CrCl3, CrBr3, MnCl3, CrI3, FeMnCl3.

[0084] Under battery conditions, the metal halide 202 can be configured to become lithiated as lithium ions 204 flow from the solid electrolyte 104a to the cathode 102, as shown in Figure 1. Alternatively, or in addition, the metal halide can reversibly donate or accept ions, such as sodium or potassium, depending on the composition of the solid electrolyte.

[0085] Figures 2A and 3A show the XRD patterns of the metal halide cathode before (Figure 2A) and after (Figure 3B) exposure to lithium ions. Figures 2B and 3B show the X-ray crystal structure analysis of the metal halide cathode before (Figure 2B) and after (Figure 3B) introduction of ions into the lattice.

[0086] In some embodiments, lithium ions, sodium ions, or potassium ions are transferred from the solid electrolyte to the positive electrode material, e.g., Li 0.8 FeCl3, Na 0.2 FeCl3, K 2.4An ion-bearing metal halide positive electrode, such as FeCl3, may be formed. The amount of ions per unit cell can vary from about 0.1 to about 4 (e.g., Li 0.1 FeCl3, Li 0.2 FeCl3, Li 0.3 FeCl3, Li 0.4 FeCl3, Li 0.5 FeCl3, Li 0.6 FeCl3, Li 0.7 FeCl3, Li 0.8 FeCl3, Li 0.9 FeCl3, Li 1.0 FeCl3, Li 1.1 FeCl3, Li 1.2 FeCl3, Li 1.3 FeCl3, Li 1.4 FeCl3, Li 1.5 FeCl3, Li 1.6 FeCl3, Li 1.7 FeCl3, Li 1.8 FeCl3, Li 1.9 FeCl3, Li 2.0 FeCl3, Li 3.0 FeCl3, Li 4.0 FeCl3, and any value in between, e.g., Li 1.12 FeCl3 or Li 3.63 FeCl3, etc.).

[0087] In some embodiments, the first solid electrolyte 104a and the second solid electrolyte 104b each independently have the formula A a (M E1 ) b (M E2 ) c (X E ) d (In the formula, A, M E1 , and M. E2 is one or more cations, and X E In some embodiments, M may be one or more anions. E1 and M. E2 may each independently be an element selected from the group consisting of post-transition metals and metalloids.E1 and M. E2 Suitable examples of may include, but are not limited to, iron, titanium, chromium, manganese, cobalt, nickel, copper, zinc, molybdenum, technetium, ruthenium, vanadium, tungsten, niobium, tantalum, lanthanum, boron, aluminum, scandium, gallium, yttrium, zirconium, indium, silicon, germanium, tin, arsenic, antimony, tellurium, thallium, lead, bismuth, polonium, or combinations thereof. For example, M may be an element having a structure in which the solid electrolyte has the formula Li 15.5 Ge 0.5 P 3.5 S 15 In another example where M is a plurality of cations, M can include gallium and germanium. In such an embodiment, A a (GeS4) b (PS4) 4-b (X E )3 and A a (GaS4) b (PS4) 4-b (X E Some examples of the above solid electrolytes include Li3YCl6, Li2ZrCl6, Li3ScCl6, Li3YbCl6, Li3FeCl6, Li 2.75 In 0.75 Zr 0.25 Cl6, Li 15 P4S 16 Cl3, Li 15.5 Ge 0.5 P 3.5 S 15 Cl3, Li 16 (SiS4)(PS4)3Cl3, Na 16 (GeS4)(PS4)3Br3, Li 19 (GaS4)2(PS4)2Cl3, Li 16 (GeS4)(PS4)3Cl3, Li 2-x+2y ZrCl 6-x O y (where x is between 0 and 2 and y is between 0 and 1).

[0088] In some embodiments, the first solid electrolyte 104a and the second solid electrolyte 104b each independently have an ionic conductivity of 1.0×10 -7 S / cm or more (e.g., 1.5×10 -7 S / cm or more, 2.0×10 -7 S / cm or more, 3.0×10 -7 S / cm or more, 4.0×10 -7 S / cm or more, 5.0×10 -7 S / cm or more, 6.0×10 -7 S / cm or more, 7.0×10 -7 S / cm or more, 8.0×10 -7 S / cm or more, 9.0×10 -7 S / cm or more, 1.0×10 -6 S / cm or more, 2.0×10 -6 S / cm or more, 3.0×10 -6 S / cm or more, 4.0×10 -6 S / cm or more, 5.0×10 -6 S / cm or more, 6.0×10 -6 S / cm or more, 7.0×10 -6 S / cm or more, 8.0×10 -6 S / cm or more, 9.0×10 -6 S / cm or more, 1.0×10 -5 S / cm or more, 2.0×10 -5 S / cm or more, 3.0×10 -5 S / cm or more, 4.0×10 -5 S / cm or more, 5.0×10 -5 S / cm or more, 6.0×10 -5 S / cm or more, 7.0×10 -5 S / cm or more, 8.0×10 -5 S / cm or more, 9.0×10 -5 S / cm or more, 1.0×10 -4 S / cm or more, 2.0×10 -4 S / cm or more, 3.0×10 -4 S / cm or more, 4.0×10 -4 S / cm or more, 5.0×10 -4 S / cm or more, 6.0×10 -4 S / cm or more, 7.0×10 -4 S / cm or more, 8.0×10-4 S / cm or more, 9.0×10 -4 S / cm or more, or 1.0×10 -3 S / cm or more).

[0089] In some embodiments, the first solid electrolyte 104a and the second solid electrolyte 104b each independently have an ionic conductivity of 1.0×10 at room temperature or greater. -3 S / cm or less (e.g., 1.0×10 -7 S / cm or less, 1.5×10 -7 S / cm or less, 2.0×10 -7 S / cm or less, 3.0×10 -7 S / cm or less, 4.0×10 -7 S / cm or less, 5.0×10 -7 S / cm or less, 6.0×10 -7 S / cm or less, 7.0×10 -7 S / cm or less, 8.0×10 -7 S / cm or less, 9.0×10 -7 S / cm or less, 1.0×10 -6 S / cm or less, 2.0×10 -6 S / cm or less, 3.0×10 -6 S / cm or less, 4.0×10 -6 S / cm or less, 5.0×10 -6 S / cm or less, 6.0×10 -6 S / cm or less, 7.0×10 -6 S / cm or less, 8.0×10 -6 S / cm or less, 9.0×10 -6 S / cm or less, 1.0×10 -5 S / cm or less, 2.0×10 -5 S / cm or less, 3.0×10 -5 S / cm or less, 4.0×10 -5 S / cm or less, 5.0×10 -5 S / cm or less, 6.0×10 -5 S / cm or less, 7.0×10 -5 S / cm or less, 8.0×10 -5 S / cm or less, 9.0×10 -5 S / cm or less, 1.0×10 -4 S / cm or less, 2.0×10 -4S / cm or less, 3.0×10 -4 S / cm or less, 4.0×10 -4 S / cm or less, 5.0×10 -4 S / cm or less, 6.0×10 -4 S / cm or less, 7.0×10 -4 S / cm or less, 8.0×10 -4 S / cm or less, or 9.0 x 10 -4 S / cm or less).

[0090] Referring again to FIG. 1, when a battery includes a positive electrode 102 including a metal halide material according to the present disclosure and a solid electrolyte, high capacity performance can be achieved that exceeds that of a typical lithium ion battery.

[0091] Figure 4A shows the charge-discharge voltage profile of the metal halide cathode FeCl3 at room temperature at a rate of 0.1 C (voltage is plotted versus Li / Li+ for better comparison with other cathodes). -1 A reversible specific capacity exceeding the theoretical capacity (Fe 2+ / Fe 3+ 165 mAh g, calculated based on redox couple -1 ) at 91% of the intercalation potential. Two distinct and very flat plateaus are observed around 3.6 V, implying a possible two-phase intercalation process. This voltage is significantly higher than that of lithium iron oxide (about 2 V to 3 V) and even higher than LiFePO4 (3.42 V) and FeF3. Without wishing to be bound by theory, the high intercalation voltage may be due to the combination of the highly electronegative chlorine atoms and the crystal structure.

[0092] The cyclic voltammetry (CV) curves in FIG. 4B also show two positive and two negative peaks (Li for the positive peaks). + / Li 3.65V / 3.55V, negative peak for Li + / Li), which corresponds to two plateaus in the voltage profile. With such high voltage and capacity, for example FeCl3, the theoretical cathode energy density of metal halide materials approaches about 600 Wh / kg, exceeding that of LiFePO4.

[0093] Generally, the specific capacity and energy density are calculated based on the mass of the active material. For solid-state batteries, the mass of the electrolyte and the negative electrode are included, but when reviewing the specific capacity and energy density due to the positive electrode alone, the energy density is equal to the product of the voltage and the weight of the metal halide positive electrode alone. In some embodiments, the average voltage of FeCl3 is 100% of the mass of Li + The voltage at the electrode is 3.65 V vs. Li and the specific capacity (volume / weight) of FeCl3 is 165 mAh / g. Substituting the values ​​into the equation, the energy density of FeCl3 is calculated to be 602 Wh / kg based on the weight of FeCl3.

[0094] Those skilled in the art will appreciate that the cathode energy density can be further increased by adjusting the metal halide material and the solid electrolyte. In some embodiments, the cathode energy density of the battery is increased to about 600 Wh / kg (e.g., about 599 Wh / kg, about 598 Wh / kg, about 597 Wh / kg, about 596 Wh / kg, about 595 Wh / kg, about 594 Wh / kg, about 593 Wh / kg, about 592 Wh / kg, about 591 Wh / kg, about 590 Wh / kg, about 585 Wh / kg, about 580 Wh / kg, about 575 Wh / kg, about 570 Wh / kg, about 565 Wh / kg, about 56 ...75 Wh / kg, about 570 Wh / kg, about 575 Wh / kg, about 570 Wh / kg, about 575 Wh / kg, about 570 Wh / kg, about 575 Wh / kg, about 57 500Wh / kg, approximately 490Wh / kg, approximately 480Wh / kg, and any value therebetween, such as approximately 523.82Wh / kg or approximately 599.99Wh / kg.

[0095] FIG. 15 is a flow chart of a method 1500 of manufacturing a solid-state battery according to the disclosed technology. The method 1500 can include, in step 1502, combining a cathode material with at least one solid electrolyte and an anode. Here, the cathode material includes at least one compound selected from FeF3, FeCl3, FeBr3, FeI3, CrCl3, CrBr3, MnCl3, or CrI3. The method 1500 can include, in step 1504, compressing the solid mixture in an anhydrous container at a pressure ranging from about 200 MPa to about 400 MPa to obtain a solid-state battery. Compressing the solid mixture can also be performed in a container filled with dry air. The method 1500 can optionally include charging and discharging the solid-state battery in the presence of lithium ions, sodium ions, or potassium ions, as shown in step 1506. The method 1500 can optionally include obtaining an operating voltage greater than about 3.4 V relative to the Li+ / Li redox couple, as shown in step 1508. It will be appreciated that the method 1500 can include any of the above examples described herein.

[0096] Aspects of the present disclosure are further illustrated by the following examples, which, however, do not limit the teachings or disclosure of the present disclosure described herein. EXAMPLES

[0097] Reversible insertion / extraction of lithium in FeCl3 in ALSOLIB

[0098] Anhydrous FeCl3 was tested as received from the commercial supplier without further treatment. The particles are flake-like with lengths of 1 μm to 2 μm and thicknesses of several hundred nm (e.g., 100 nm to 200 nm, 200 nm to 300 nm, 300 nm to 400 nm, 400 nm to 500 nm, etc.). Ball-milled Li3YCl6 (LYC) was synthesized and used as the solid electrolyte to fabricate ALSOLIB cells due to its high oxidative stability. The X-ray diffraction (XRD) pattern and electrochemical impedance spectroscopy (EIS) measurements of LYC are shown in Figure 12A, and Li 2.75 In 0.75 Zr 0.25 The XRD pattern and EIS measurements of Cl6 are shown in Figure 13 A. The cell containing the FeCl3 composite cathode, LYC electrolyte, and Li-In anode was cycled at room temperature.

[0099] Ex situ X-ray absorption near edge structure (XANES) data were collected to characterize the change in the oxidation state of Fe during the charge-discharge process. FeCl2 was used as the reference compound. As shown in Figure 5A and Figure 5B, starting from the initial state of FeCl3, as more Li is inserted, the position of the Fe K absorption edge shifts to lower energies, which is due to the Fe 3+ Fe 2+ When discharged to 1.9 V, with 0.9 Li per formula unit of FeCl3 inserted, the Fe K edge shifts to a position where it almost overlaps with the Fe K edge of FeCl2. When recharged to 3.5 V, the edge shifts again to higher energies and very close to the edge of pristine FeCl3, which is due to the Fe 3+ / Fe 2+ This shows that the pair is highly reversibly oxidized and reduced.

[0100] To explain the Li storage mechanism in FeCl3 during the discharge / charge process, we performed operando energy dispersive X-ray diffraction (EDXRD) measurements to obtain structural information from a controlled diffraction gauge volume of tens of microns. A schematic diagram of the EDXRD setup is shown in Extended Data, Fig. 6. The ionic conductivity at room temperature was 1.9 mS cm-1 Li 2.75 In 0.75 Zr 0.25 Cl6 (LIZC) was used as the solid electrolyte instead of LYC. The crystal structure of LIZC was determined by Rietveld refinement for neutron diffraction (shown in FIG. 13A). The ionic conductivity and activation energy were determined by EIS tests at various temperatures (shown in FIG. 13B). A thin layer of Li3YCl3Br3 (LYCB) was used as a protective layer between LIZC and the negative electrode layer. Scans were performed layer-by-layer in the vertical direction with 20 μm increments. FIG. 7 shows the contour map of the EDXRD measurement of the whole cell before cycling. The span between the two stainless steel (SS) rods is about 780 μm, and the thickness of the positive electrode is about 100 μm. FIG. 8 shows the contour map between 2 Å and 3.5 Å in the positive electrode layer during the first discharge / charge process. The corresponding diffraction pattern is plotted in FIG. 9. The reflections at 2.60 Å, 3.02 Å, and 3.15 Å are from the electrolyte LIZC in the positive electrode layer. FeCl3 is It crystallizes in the TIFF2025514294000002.tif6151 structure, and the strong reflections at 2.69 Å and 2.91 Å are due to the (113) and (006) lattice planes, respectively. Since they do not overlap with the reflections from LIZC, they are used to trace the phase change of FeCl3 during the lithium insertion / extraction process.

[0101] During the discharge process, two biphasic intercalation processes can be observed, which are similar to the lithiation process of VCl3 in supersaturated electrolytes. As more Li is inserted, the reflections from the initial FeCl3 become weaker and the reflections from the Li 0.2 An intermediate phase (known as phase α) appears with a reflection at 2.72 Å in the composition FeCl3. 0.35 In the FeCl3 composition, the (113) reflection from FeCl3 disappears, and the Li + Phase α is shown in FIG. 2B and has a larger lattice parameter than FeCl3. The structure can be indexed to TIFF2025514294000003.tif6151. Further Li insertion leads to a transformation of phase α into a more Li-rich phase (known as phase β and shown in Figure 3B), which gives rise to a reflection closer to the LIZC at the end of the discharge, implying that a very similar anionic framework is shared.

[0102] During the charging process, phase β does not undergo the reverse lithiation pathway to transform back into FeCl3. Instead, Li 0.76 FeCl3 and Li 0.53 A solid-liquid delithiation process is observed with FeCl3, with the reflections at 2.60 Å, 3.02 Å, and 3.15 Å shifting monotonically to smaller d-space. Further desorption of Li ions leads to the formation of a new phase (known as phase γ) with reflections at 2.53 Å and 2.91 Å. At the end of the charging process, the EDXRD pattern of the fully delithiated phase (known as phase δ) differs from that of the initial FeCl3, with no obvious reflection at 2.69 Å. Instead, a new reflection appears at a lower d-space position (2.50 Å).

[0103] Synchrotron XRD and neutron powder diffraction (NPD) experiments were performed to solve the crystal structures of examples of metal halide materials in their most lithiated form (phase β). The diffraction patterns of phase β can be indexed to the C2 / m space group, in which the chlorine atoms are stacked in the fcc form. The three space groups C2 / m, C2, and Cm have the same systematic forbidden reflections caused by C-centering (h+k=2n+1). Other symmetry elements in the three space groups, such as the two-fold axis (2) and mirror planes (m) in the C2 / m space group, do not cause forbidden reflections. Alternatively, or in addition, the metal halide positive electrode materials may form a variety of unit cells, such as a cubic unit cell (simple, body-centered, face-centered, etc.), a tetragonal unit cell (simple, body-centered, etc.), a monoclinic unit cell (simple, base-centered, etc.), an orthorhombic unit cell (simple, body-centered, face-centered, base-centered, etc.), a trigonal unit cell, a hexagonal unit cell, or a triclinic unit cell.

[0104] The difference Fourier map generated from the neutron diffraction pattern clearly shows that the Li ions are located at octahedral / tetrahedral positions between the FeCl3 layers (Figure 3B). Figure 4d shows the synchrotron XRD pattern of phase 4, which can be indexed to the C2 / m space group. Compared to the pristine FeCl3, the fully delithiated FeCl3 has a spinel-like structure, with the chlorine atoms retaining the fcc stacking morphology.

[0105] FIG. 10A shows the cycling performance of an example battery containing the metal halide cathode material FeCl3 with an LYC electrolyte at room temperature and 0.1 C. The specific capacity of this cell was initially 157 mAh g -1 After 100 cycles, the battery maintained 78.8% of its capacity, indicating very good long-term cycling stability. The specific capacity of the battery containing the metal halide cathode material was 130 mAh g -1 or more (for example, about 135mAh g -1 Approximately 140mAh g -1 Approximately 145mAh g -1 Approximately 150mAh g -1 Approximately 155mAh g -1 Approximately 160mAh g -1 Approximately 165mAh g -1 Approximately 170mAh g -1 Approximately 175mAh g -1 Approximately 180mAh g -1 or greater, or any value in between, e.g., about 157 mAh g -1 or about 172.4mAh g -1 ).

[0106] To test the rate capability of the metal halide cathode FeCl3, an ionic conductivity of 2 mS cm at room temperature was used. -1 Li 2.75 In 0.75 Zr 0.25Cl6(LIZC) was used as the solid electrolyte instead of LYC. At 60 °C, the rate performance of the FeCl3 cell was very good, with a specific capacity of 135 mAh g at 1 C, as shown in Figure 10B. -1 and the specific capacity at a rate of 5C is 70mAh g -1 Figure 11A shows the long-term cycling performance of FeCl3 at 0.5C and 60°C. The initial specific capacity was 121 mAh g -1 After 500 cycles, it is 70mAh g -1 In some embodiments, a battery including a metal halide positive electrode maintains a capacity of 70 mAh g for more than 500 cycles (e.g., about 550 cycles, about 600 cycles, about 650 cycles, about 700 cycles, about 750 cycles, about 800 cycles, about 850 cycles, about 900 cycles, about 950 cycles, about 1000 cycles, and any number of cycles in between, e.g., 523 cycles). -1 In the above electrochemical tests, FeCl3 showed excellent capacity and very good cycling stability.

[0107] In Figure 11B, the energy density of FeCl3 is compared with some of the typical intercalation cathodes commonly used in commercial lithium-ion batteries. FeCl3 has a higher voltage than LiFePO4 (3.4 V vs. 3.6 V) and a similar theoretical capacity (170 mAh g -1 165mAh g -1 ), LiFePO4(540Wh kg -1 ) and LiMn2O4 (480Wh kg -1 ) has a higher overall energy density (594Wh kg -1 ) Beyond its excellent electrochemical performance, the most attractive feature of FeCl3 is its low cost.

[0108] Figures 14A and 14B summarize the market prices of LiCoO2, NMC811, LiMn2O4, and FeCl3 in November 2021. The prices of lithium metal oxide cathodes range from US$10,787 (LiMn2O4) to US$63,386 (LiCoO2) per ton. The price of LiFePO4 is also over US$10,000 per ton. In contrast, the market price of FeCl3 is only US$600 per ton, and if layered oxides are replaced with FeCl3, the cost of the cathode material could drop from US$22.47-99.04 per kWh to US$1.35 per kWh (Figure 6c). As a result, the cost of LIB cells is expected to drop from about US$200 per kWh to US$50-100 per kWh in the future.

[0109] Reversible lithium insertion / extraction in FeCl3 was realized by using a solid electrolyte, and the phase change mechanism during the charge / discharge process was elucidated by using EDXRD, ex situ synchrotron, and neutron diffraction techniques. As a new kind of cathode material, FeCl3 exhibits satisfactory energy density and cycle stability at both room temperature and high temperature (60 °C) in ALSOLIB. High energy density (540 Wh kg -1 ) and lower market prices make FeCl3 a promising candidate, which may pave the way for further development of ALSOLIB.

[0110] Material Synthesis

[0111] For the synthesis of Li3YCl6, stoichiometric LiCl (Sigma-Aldrich) and YCl3 (Sigma-Aldrich) were mechanically ground in a planar ball mill (PM200, Recce) with a zirconia jar under argon atmosphere at 500 rpm for 5 h.

[0112] Li by high-energy ball milling 2.75 In 0.75 Zr 0.25LiCl (Sigma-Aldrich), InCl3(), and ZrCl4() were weighed in the desired ratio and ball milled at 500 rpm for 5 h. The ball milled mixture was pelletized and placed in a sealed quartz tube. The pellet was heated at 425 °C for 5 h and cooled to room temperature in a furnace.

[0113] Following the same synthesis protocol, Li3YCl3Br3 was prepared. LiBr (Sigma-Aldrich) and YCl3 (Sigma-Aldrich) were ball-milled for 5 h, followed by sintering. All processing was carried out under an argon atmosphere.

[0114] Ex situ synchrotron and neutron powder diffraction

[0115] Synchrotron X-ray diffraction patterns were collected at the synchrotron X-ray source at beamline 17-BM (Advanced Photon Source (APS)). Neutron powder diffraction (NPD) data for high-quality powders were collected at room temperature at POWGEN and NOMAD at the Spallation Neutron Source (SNS) at Oak Ridge National Laboratory (ORNL) with a central wavelength of 1.5 Å. Rietveld refinement was performed on the XRD and ND data using GSAS II and TOPAS. For data analysis using neutron diffraction data, the time-of-flight (TOF) data were converted to d-space data using the polynomial TOF=ZERO+DIFC*d+DIFA*d2+DIFB / d, where ZERO is a constant, DIFC is the diffractometer constant, and DIFA and DIFB are empirical terms to correct for sample displacement and absorption due to peak shift. During refinement, ZERO, DIFC, and DIFB were determined by refinement with the standard NIST Si 640d, while DIFA was varied to account for the displacement of the sample. A continuous exponential function convolved with a symmetric Gaussian function was used to describe the peak profiles.

[0116] Electrochemical measurements

[0117] Ionic conductivity was measured by EIS using an electrochemical impedance analyzer (VMP3, Bio-Logic) and a homemade electrochemical cell. Typically, 0.5 g to 1 g of electrolyte powder was cold pressed at 294 MPa pressure into a pellet with a diameter of 1 / 2 inch. Two sheets of Al foil were used as current collectors, and EIS data were collected at various temperatures with an AC amplitude of 50 mV and a frequency range of 1 MHz to 1 Hz.

[0118] The positive electrode of the all-solid-state cell is made of FeCl3 (98% purity, Spectrum Chemical Co.), a synthetic solid electrolyte (Li3YCl6 or Li 2.75 In 0.75 Zr 0.25 The cathode mixture consisted of 10 mg FeCl3 / LYC / AB composite cathode mixture at 294 MPa and 10 mg FeCl3 / LYC / AB composite anode mixture at 294 MPa. The cathode mixture was mixed by hand in a mortar in a ratio of 55:40:5 (wt%). InLi alloy was used as the anode material in the all-solid-state cells. In and Li metals were pressed together at 294 MPa to prepare an InLi alloy with the formula InLi, and then mixed with LYCB by hand in a mortar in a weight ratio of 70:30. Solid electrolyte powder was used as the separator. To fabricate the all-solid-state cells with LYC electrolyte, 120 mg LYC powder was placed in a PMMA sleeve and pressed at 294 MPa, and then 10 mg FeCl3 / LYC / AB composite anode mixture was pressed at 294 MPa on one side of the LYC pellet. 25 mg composite anode mixture was pressed on the other side of the LYC pellet. The procedure to fabricate the all-solid-state cells with LIZC electrolyte follows a similar method, with 80 mg LYBC as a protective layer between the LIZC and anode layers. The all-solid-state cells for operando EDXRD measurements utilized LIZC electrolyte with a composite positive electrode mass loading of 25 mg and a composite negative electrode mass loading of 50 mg. Cycling tests were performed in galvanostatic mode between 1.9 V and 3.5 V at room temperature and 60 °C.

[0119] Cyclic voltammetry (CV) was performed on the all-solid-state cell containing the LIZC electrolyte. CV was performed from 1.9 V to 3.5 V at 0.01 mV s using an electrochemical impedance analyzer (VMP3, Bio-Logic).-1 Data was collected at a scan rate of 100 s.

[0120] Operando energy dispersive X-ray diffraction

[0121] Operando EDXRD measurements were performed at the 6-BM-A beamline at the Advanced Synchrotron Radiation Facility at Argonne National Laboratory. The incident beam size was 2.00 mm × 0.020 mm, and the receiving slit size was 4.00 mm × 0.20 mm. The germanium detector was fixed at 2.301084° to measure the intensity of the diffracted beam. The vertical length of the all-solid-state cell was scanned layer by layer with 20 μm intervals. The data acquisition time was 30 s, and the data were smoothed using a Savitzky-Golay filter.

[0122] X-ray absorption near edge structure

[0123] The change in oxidation state of Fe during discharge / charge was investigated by synchrotron Fe K-edge X-ray absorption spectroscopy (XAS) performed at beamline 12-BM-B at the Advanced Synchrotron Radiation Facility (APS) at Argonne National Laboratory (Lemont, IL, USA). Sample solids were loaded into epoxy-sealed Kapton capillary tubes in an Ar atmosphere. XANES (near-edge structure) data were collected and energy calibrated using Fe foil. Multiple scans (4 to 6) were performed for each sample, averaged, and normalized. Fe XANES data were analyzed using Athena.

[0124] It is to be understood that the embodiments and claims disclosed herein are not limited in their application to the details of construction and arrangement of the components described herein and illustrated in the drawings. Rather, the specification and drawings provide examples of possible embodiments. The embodiments and claims disclosed herein are capable of further embodiments and can be practiced and carried out in various ways. It is also to be understood that the phraseology and terminology employed herein are for the purpose of description and should not be construed as limiting the scope of the claims.

[0125] As such, those skilled in the art will appreciate that the conception underlying the present application and claims may be readily utilized as a basis for the designing of other structures, methods and systems for carrying out the purposes of the embodiments and claims presented herein, and it is important that the claims be regarded as including such equivalent constructions.

[0126] Furthermore, the purpose of the Abstract is to enable the U.S. Patent and Trademark Office and the general public, including those not familiar with patent and legal terminology and phraseology, to quickly grasp the content and gist of the technical disclosure of the application upon a single reading. The Abstract does not define the scope of the claims of the application, nor does it limit the scope of the claims in any way.

Claims

1. A positive electrode used in an alkali metal ion battery, comprising a metal halide.

2. The aforementioned metal halide is given by the following formula: (Fe １－ｚ M ａ )(Cl ｙ X ３－ｙ ) (In the formula, M is a metal, X is a halogen, a is between 0 and 2.9, z is between 1 and 0, and y is between 0 and 3.) The positive electrode according to claim 1, represented by [the specified symbol].

3. The positive electrode according to claim 2, wherein M is selected from the group consisting of titanium, chromium, manganese, cobalt, nickel, copper, zinc, molybdenum, technetium, ruthenium, vanadium, tungsten, rhenium, osmium, lithium, sodium, potassium, rubidium, or cesium.

4. The positive electrode according to claim 2, wherein X is selected from the group consisting of fluorine, bromine, and iodine.

5. where the metal halide is FeF ３ , FeCl ３ , FeBr ３ , FeI ３ , CrCl ３ , CrBr ３ , MnCl ３ , and CrI ３ The positive electrode according to claim 1, selected from the group consisting of.

6. The positive electrode according to claim 1, wherein the energy density of the metal halide is approximately 600 Wh / kg.

7. The positive electrode according to claim 1, wherein the metal halide is configured to be reversibly lithiated and delithiated when exposed to lithium ions.

8. The positive electrode according to claim 1, wherein the metal halide is configured to be reversibly sodium-modified and desodium-modified upon exposure to sodium ions.

9. A solid-state battery comprising a positive electrode according to any one of claims 1 to 8, The aforementioned battery is Li ＋ A solid-state battery configured to have an operating voltage of approximately 3V or more for the Li oxidation-reduction pair.

10. The aforementioned battery further contains Li ＋ The battery according to claim 9, wherein the operating voltage for the Li redox pair is configured to exceed approximately 3.3V.

11. The aforementioned battery further contains Li ＋ The battery according to claim 9, wherein the operating voltage for the Li redox pair is configured to exceed approximately 3.6V.

12. The battery according to claim 11, wherein the battery is further configured such that the operating voltage is approximately 3.6V when the charge-discharge cycle capacity rate at 25°C is approximately 0.1C.

13. The battery according to claim 11, wherein the battery is further configured such that the operating voltage is approximately 3.6V when the charge-discharge cycle capacity rate at 60°C is approximately 0.1C.

14. The aforementioned battery further contains Fe ２＋ / Fe ３＋ The reversible ratio capacity for redox pairs is 150 mAh·g. －１ The battery according to claim 9, configured to exceed [a certain value].

15. The aforementioned battery, based on the total weight of the metal halide, has a positive electrode energy density of approximately 541 Wh·kg. －１ The battery according to claim 9, configured as described above.

16. Based on the total weight of the metal halide, the aforementioned battery has a positive electrode energy density of approximately 594 Wh·kg. －１ The battery according to claim 9, configured to be such as...

17. The solid battery according to claim 9, further comprising a solid electrolyte.

18. The solid electrolyte is given by the following formula: A ａ (M Ｅ１ ) ｂ (M Ｅ２ ) ｃ (X Ｅ ) ｄ (In the formula, A is one or more cations selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, silver, gold, titanium, and combinations thereof. M Ｅ１ This is one or more cations selected from the group consisting of iron, titanium, chromium, manganese, cobalt, nickel, copper, zinc, molybdenum, technetium, ruthenium, vanadium, tungsten, niobium, tantalum, lanthanum, boron, aluminum, scandium, gallium, yttrium, zirconium, indium, silicon, germanium, tin, arsenic, antimony, tellurium, thallium, lead, bismuth, polonium, and combinations thereof. M Ｅ２ This is one or more cations selected from the group consisting of boron, aluminum, scandium, gallium, yttrium, zirconium, indium, silicon, germanium, tin, arsenic, antimony, tellurium, thallium, lead, bismuth, polonium, and combinations thereof. M Ｅ１ and M Ｅ２ It contains different cations, X Ｅ is one or more anions selected from the group consisting of fluorine, chlorine, bromine, iodine, and oxygen. a is between 1 and 10, b and c are each independently less than 6, (d is between 0 and 18) A solid battery according to claim 17, comprising a compound represented by [the compound name].

19. The solid electrolyte is given by the following formula: A ａ (M Ｅ１ S ４ ) ｂ (PS ４ ) ４－ｂ (X Ｅ ) ３ (In the formula, A is one or more cations selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, silver, gold, titanium, and combinations thereof. M Ｅ１ This is one or more cations selected from the group consisting of boron, aluminum, scandium, gallium, yttrium, zirconium, indium, silicon, germanium, tin, arsenic, antimony, tellurium, thallium, lead, bismuth, polonium, and combinations thereof. X Ｅ It is selected from the group consisting of fluorine, chlorine, bromine, and iodine. a ranges from 1 to 27. b is less than 4. A solid battery according to claim 17, comprising a compound represented by [the compound name].

20. A method for manufacturing a solid-state battery, A step of forming a solid mixture by combining the positive electrode material according to any one of claims 1 to 8 with at least one solid electrolyte and a negative electrode, A method comprising the step of compressing the solid mixture in an anhydrous container at a pressure ranging from about 200 MPa to about 400 MPa to obtain the solid battery.

21. The solid electrolyte is Li ３ YCl ６ Li ２ ZrCl ６ Li ３ ScCl ６ Li ３ YbCl ６ Li ３ FeCl ６ Li ２．７５ In ０．７５ Zr ０．２５ Cl ６ Li １５ P ４ S １６ Cl ３ Li １５．５ Ge ０．５ P ３．５ S １５ Cl ３ Li １６ (SiS ４ ) (PS ４ ) ３ Cl ３ Na １６ (GeS ４ ) (PS ４ ) ３ Br ３ Li １９ (GaS ４ ) ２ (PS ４ ) ２ Cl ３ Li １６ (GeS ４ ) (PS ４ ) ３ Cl ３ Li ２－ｘ＋２ｙ ZrCl ６－ｘ O ｙ The method according to claim 20, comprising at least one compound selected from the group consisting of, and combinations thereof.

22. A step of charging and discharging the solid battery in the presence of lithium ions, A step of charging and discharging the solid battery in the presence of sodium ions, The method according to claim 20, further comprising at least one of the following.

23. Li ＋ A step of making the operating voltage for the Li / Li redox pair exceed about 3 V, A process to make the operating voltage for the Li+ / Li redox pair exceed approximately 3.3V. A process to ensure that the operating voltage for the Li+ / Li redox pair is approximately 3.6V or higher. The method according to claim 20, further comprising at least one of the following.

24. A step of making the operating voltage approximately 3.6V when the charge / discharge cycle capacity rate at 25°C is approximately 0.1C, A process to ensure that the operating voltage is approximately 3.6V when the charge / discharge cycle capacity rate at 60°C is approximately 0.1C. The method according to claim 23, further comprising at least one of the following.

25. Furthermore, Fe ２＋ / Fe ３＋ The reversible ratio capacity for redox pairs is 150 mAh·g. －１ The method according to claim 20, comprising the step of making it exceed a certain value.

26. Based on the total weight of the metal halide, the positive electrode energy density is approximately 540 Wh·kg －１ A process to make it exceed, A process to ensure that the positive electrode energy density is approximately 594 Wh·kg⁻¹ based on the total weight of the metal halide. The method according to claim 20, further comprising at least one of the following.

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