Catholyte for solid-state batteries

Abstract

Provided herein are compositions useful as electrolytes and / or catholytes in electrochemical cells containing a solid separator and a lithium metal anode.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and benefit of U.S. Provisional Patent Application No. 63 / 264,693, filed November 30, 2021, entitled CATHOLYTES FOR A SOLID-STATE BATTERY, the entire contents of which are incorporated herein by reference for all purposes.

[0002] Field

[0002] This disclosure relates to solid state batteries and electrolytes and catholytes used in solid state batteries. [Background technology]

[0003] background

[0003] Solid-state batteries containing lithium metal anodes require a special solid electrolyte separator placed between the cathode and the anode. The solid electrolyte separator is solid and stable in contact with lithium metal, and Li + It must be capable of conducting ions but not electrons at any appreciable rate. Liquid-based batteries containing carbon-based (e.g., graphite) anodes (i.e., negative electrodes) do not use such solid electrolytes. Instead, a liquid electrolyte is present between the cathode and anode in these liquid-based batteries. These liquid electrolytes are typically carbonate-based in that they use a carbonate solvent, such as diethyl carbonate or dimethyl carbonate, to dissolve a lithium salt, such as LiPF6. Summary of the Invention [Problem to be solved by the invention]

[0004]

[0004] Several publications have used ethylene sulfite as an additive to carbonate-based solvent electrolytes. These compositions were optimized for graphite-based anodes. See, for example, https: / / doi.org / 10.1149 / 1.1391630; https: / / doi.org / 10.1021 / la015553h; https: / / doi.org / 10.1016 / j.jpowsour.2010.08.092; https: / / doi.org / 10.1016 / j.jpowsour.2005.02.007; and https: / / doi.org / 10.1039 / C5CP04221F. New electrolytes and catholytes compatible with solid-state battery electrolyte separators are needed. [Means for solving the problem]

[0005] In one embodiment, a lithium salt and at least two aprotic C groups, each independently in each instance, containing at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents. 3-10 Provided herein is a catholyte solution comprising a heterocyclic molecule.

[0006] In a second embodiment, a lithium salt is provided; and an aprotic C cation having at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents. 3-10 Provided herein is a catholyte solution comprising a heterocyclic molecule.

[0007] In a third embodiment, a cathode, a lithium metal anode, and a solid electrolyte comprising a lithium-loaded garnet and a catholyte, the catholyte comprising: a lithium salt; and at least two C groups, each independently in each instance, containing at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents. 3-10 and a solid electrolyte comprising a heterocyclic molecule.

[0008] In a fourth embodiment, a cathode, a lithium metal anode, and a solid electrolyte comprising a lithium-loaded garnet and a catholyte, the catholyte comprising: a lithium salt; and an aprotic C ion having at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents. 3-10 and a solid electrolyte comprising a heterocyclic molecule.

[0009]

[0009] In a fifth embodiment, a method for preparing a catholyte solution comprises: a lithium salt and, each independently, at least two C groups, in each case containing at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents. 3-10 Provided herein are methods of making the compound, comprising mixing a heterocyclic molecule with a compound of formula (I).

[0010]

[0010] In a sixth embodiment, a method for preparing a catholyte solution comprises: a lithium salt and an aprotic C cation containing at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents. 3-10 Provided herein are methods of making the compound, comprising mixing a heterocyclic molecule with a compound of formula (I).

[0011] In a seventh embodiment, there is provided a method for producing an electrochemical cell, comprising: providing a catholyte in a positive electrode, the catholyte comprising a lithium salt; and at least two C groups, each independently, in each instance, containing at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents. 3-10 and contacting the positive electrode with a solid electrolyte separator comprising a lithium-loaded garnet.

[0012] In an eighth embodiment, a method for manufacturing an electrochemical cell includes: providing a catholyte in a positive electrode, the catholyte comprising: a lithium salt; and an aprotic C cation having at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents. 3-10and contacting the positive electrode with a solid electrolyte separator comprising a lithium-loaded garnet.

[0013] In a ninth embodiment, a catholyte solution is provided comprising: a lithium salt; and, each independently, at least two aprotic C groups, in each instance containing at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents. 3-10 heterocyclic molecules, and at least one C 3-10 Provided herein is a catholyte solution wherein the heterocyclic molecule is selected from the group consisting of ethylene sulfite; 4-methyl-1,3,2-dioxathiolane 2-oxide; 1,3-propane sultone; sulfolane; thiophene; thiazole; 1,2-oxathiolane; thiepine; 1,4-thiazepine; 6-H-1,2,5-thiadiazine; 2H,6H-1,5,2-dithiazine; methylenemethane disulfonate; ethylene sulfate; thiopyran; thiocin, derivatives thereof, and combinations thereof.

[0014] In a tenth embodiment, there is provided herein a storage battery comprising the catholyte disclosed herein.

[0015]

[0015] In an eleventh embodiment, provided herein is an electric vehicle including a battery as disclosed herein. [Brief explanation of the drawings]

[0016] BRIEF DESCRIPTION OF THE DRAWINGS [Figure 1] 1 is a plot of C-rate as a function of cycle time. [Figure 2]

[0017] 1 is a plot of state of charge (SOC) as a function of cycle time (seconds). [Figure 3]

[0018] Figure 1 shows a plot of median charge area-specific direct current resistance (ASRDC) (Ω-cm) for two catholytes: a 70:30 (v / v) mixture of ethylene sulfite (ESI) and sulfolane (SLF) with 1.4 M LiPF (designated 70:30 ESI:SLF); and a 45:55 (v / v) mixture of ethylene carbonate and sulfolane with 1.4 M LiPF (designated ECS45.4). The ".4" in "ECS45.4" refers to a 1.4 M concentration of Li+ ions. "ECS45" refers to a 45:55 v / v ratio. [Figure 4]

[0019] 1 is a plot of SOC (%) as a function of run time (seconds). [Figure 5]

[0020] FIG. 1 is a plot of the active mass-specific discharge capacity (mAh / g) for five catholyte mixtures: (a) 0.5 wt% ethylene sulfite; (b) 1 wt% ethylene sulfite; (c) 2 wt% ethylene sulfite; (d) 4 wt% ethylene sulfite; and (e) 8 wt% ethylene sulfite. [Figure 6]

[0021] FIG. 1 is a plot of median charge area-specific resistance (ASR, Ωcm) DC for five catholyte mixtures: (a) 0.5 wt% ethylene sulfite; (b) 1 wt% ethylene sulfite; (c) 2 wt% ethylene sulfite; (d) 4 wt% ethylene sulfite; and (e) 8 wt% ethylene sulfite. [Figure 7]

[0022] Plot of the median area-specific resistance of charge (ASR, Ωcm) measured at direct current for two catholyte mixtures: (a) 1.4 M LiPF / ESS; (b) ECS45.4, where ESS refers to a combination of ethylene sulfite and sulfolane; and (b) ECS refers to a combination of ethylene carbonate and sulfolane. [Figure 8]

[0023] Figure 8 shows a plot (top) of the activity specific discharge capacity (mAh / g) as a function of cumulative cycle index for two catholyte mixtures: (a) 1.4 M LiPF / ESS; (b) ECS45.4. Figure 8 also shows a plot (bottom) of the median charge area specific resistance (ASR, Ωcm) DC as a function of cumulative cycle index for two catholyte mixtures: (a) 1.4 M LiPF / ESS; and (b) ECS45.4. [Figure 9]

[0024]

[0033] Figure 1 shows the time (minutes) to 80% SOC for two electrochemical cells using catholytes with different ratios of ethylene sulfite and sulfolane in a 4C fast charge test at 25°C. These results are related to Example 2 herein. These results are described in Example 2 herein. [Figure 10]

[0025] Figure 1 shows the time (minutes) to 80% SOC for two electrochemical cells using catholytes, one of which contains a third co-solvent, methyl acetate (denoted as MA), in a 4C fast charge test at 25°C. These results are described in Example 2 herein. [Figure 11]

[0026] Figure 1 shows the time (min) to 80% SOC for two catholytes, one containing a 70:30 volume ratio of ethylene sulfite to sulfolane and 1.4 M LiBF4; the other containing 1.2 M 10% LiFSi, in a 4 C fast charge test at 25° C. These results are described in Example 2 herein. [Figure 12]

[0027] 1 shows the results of a one-month ASR measurement at catholyte molarity skews from 0.5 M to 5 M. These results are described in Example 3 herein. DETAILED DESCRIPTION OF THE INVENTION

[0017] Detailed Description

[0028] The following description is provided to enable those skilled in the art to make and use the present disclosure and adapt it to particular application contexts. Various modifications and variations on applications will be readily apparent to those skilled in the art, and the general principles defined herein are applicable to a wide range of embodiments. Thus, the present disclosure is not intended to be limited to the embodiments provided but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

[0018]

[0029] In the following detailed description, numerous specific details are set forth in order to provide a more thorough understanding of the present disclosure. However, it will be apparent to one skilled in the art that the disclosure herein may be practiced without necessarily being limited to these specific details.

[0019]

[0030] Unless expressly stated otherwise, every feature disclosed in this specification (including any accompanying claims, abstract, and drawings) may be replaced by an alternative feature serving the same, equivalent, or similar purpose. Thus, unless expressly stated otherwise, each feature disclosed is only an example of a generic series of equivalent or similar features.

[0020]

[0031] Described herein are catholytes containing solvents or additives such as ethylene sulfite and sulfolane. In some embodiments, ethylene sulfite, sulfolane, or both are used as additives. As additives, ethylene sulfite, sulfolane, or both are present at less than 10% w / w, and in some embodiments, less than 9% w / w, less than 8% w / w, less than 7% w / w, less than 6% w / w, less than 5% w / w, less than 4% w / w, less than 3% w / w, less than 2% w / w, less than 1% w / w, or less than 0.5% w / w. As solvents, ethylene sulfite, sulfolane, or both are present at greater than 10% w / w.

[0021]

[0032] In some embodiments, the % w / w is calculated based on the weight of the cathode. In some other embodiments, unless otherwise specified, the % w / w is calculated based on the weight of the catholyte introduced into the cathode. Unless otherwise specified, the % w / w is calculated based on the weight of the catholyte introduced into the cathode.

[0022]

[0033] The catholytes herein, when used in lithium batteries having a lithium-loaded garnet solid electrolyte separator, improve high-voltage stability and reduce charge transfer at the lithium-loaded garnet interface. Charge transfer at the lithium-loaded garnet interface can increase area-specific resistance (ASR). In some embodiments, including any of the above, these catholytes enable fast charging to 80% capacity in 15 minutes or less in cathodes with high energy density. In some embodiments, including any of the above, the cathode with high energy density is a cathode with a volumetric energy density of 2000 Wh / L. In some embodiments, including any of the above, these catholytes exhibit high continuous discharge capacity and pulse power at -30°C. In some embodiments, including any of the above, these catholytes improve calendar life (e.g., calendar life performance at 4.4 V and 60°C). In some embodiments, including any of the above, the catholytes herein have improved accelerated storage tests at 4.4 V and 60°C.

[0023]

[0034] In some embodiments, described herein is a solution that is an electrolyte comprising ethylene sulfite, sulfolane, and a lithium salt, where ethylene sulfite is synonymous with 1,3,2-dioxathiolane-2-oxide, cyclic ethylene sulfite, ES, and glycol sulfite.

[0024]

[0035] In some embodiments, ethylene sulfite is mixed with sulfolane to obtain a deep eutectic solution, which in some embodiments has a freezing point depression of even -50°C.

[0025]

[0036] In some embodiments, the solution includes ethylene carbonate and sulfolane (ECS). Some known combinations of ECSs have insufficient low-temperature conductivity to function well at low temperatures. Replacing ethylene carbonate with ethylene sulfite, optionally using a coated cathode active material, can improve calendar life by two orders of magnitude. Replacing ethylene carbonate with ethylene sulfite, optionally using a coated cathode active material, can improve low-temperature performance (e.g., low-temperature power).

[0026] definition

[0037] As used herein, the term "about" when modifying a number, e.g., about 15% w / w, refers to the modified number and, optionally, a number within a range related to the modified number, including ±10% of that number. For example, about 15% w / w includes 15% w / w, 13.5%, 14%, 14.5%, 15.5%, 16%, or 16.5% w / w. For example, "about 75°C" includes 75°C, 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, or 83°C.

[0027]

[0038] As used herein, "selected from the group consisting of" means one member from the group, two or more members from the group, or a combination of members from the group. For example, members selected from the group consisting of A, B, and C include A alone, B alone, or C alone, as well as A and B, A and C, B and C, and A, B, and C.

[0028]

[0039] As used herein, the term "ECS" is an acronym for a mixture or solution of ethylene carbonate and sulfolane.

[0029]

[0040] As used herein, the phrase "solid separator" refers to a Li ion separator that is substantially insulating to electrons. + Ionically conductive materials (e.g., lithium) whose ionic conductivity is at least 10 times that of their electronic conductivity. 3 times, often 10 6 ), which acts as a physical barrier or spacer between the positive and negative electrodes in an electrochemical cell. + It means an ionically conductive material.

[0030]

[0041] As used herein, area specific resistance (ASR) is measured by electrochemical cycling using an Arbin, Maccor, or Biologic instrument unless specified to the contrary.

[0031]

[0042] As used herein, ionic conductivity is measured by electrical impedance spectroscopy, which is well known in the art.

[0032]

[0043] As used herein, the phrase "deep eutectic solution" is a solution or mixture of two or more chemicals that has a freezing point at least 30° C. lower than the lowest freezing point component of the deep eutectic solution. For example, if one chemical has a freezing point of −30° C. and another chemical has a freezing point of −60° C., and a 50:50 v / v mixture of these chemicals has a freezing point of −90° C., the mixture is considered a deep eutectic solution.

[0033]

[0044] As used herein, the phrase "film" or "thin film" refers to a thin film having a thickness of less than 0.5 mm and a thickness of more than 10 nm. A thin film may have a lateral dimension of more than 5 mm. A "film" or "thin film" can be produced by a continuous process such as tape casting, slip casting, or screen printing.

[0034]

[0045] As used herein, the phrase "film thickness" refers to the distance between the top and bottom surfaces of the film, or the median measured distance. As used herein, top and bottom surfaces refer to the surfaces of the film having the largest geometric surface area, where the largest geometric surface area is calculated by multiplying the length of the surface by its width. As used herein, thickness is measured by cross-sectional scanning electron microscopy.

[0035]

[0046] As used herein, "binder" refers to a polymer capable of increasing the adhesion and / or cohesion of materials, such as solids in a green tape. Suitable binders include, but are not limited to, PVDF, PVDF-HFP, SBR, and ethylene alpha-olefin copolymers. "Binder" refers to a material that promotes adhesion of another material. For example, as used herein, polyvinyl butyral is a binder because it is useful for adhering garnet materials. Other binders can include polycarbonates. Other binders can include polyacrylates and polymethacrylates. These examples of binders are not intended to be limiting on the overall scope of binders contemplated herein, but rather serve merely as examples. Binders useful in the present disclosure include polypropylene (PP), polyethylene, atactic polypropylene (aPP), isotactic polypropylene (iPP), ethylene propylene rubber (EPR), ethylene pentene copolymer (EPC), polyisobutylene (PIB), styrene butadiene rubber (SBR), polyolefins, polyethylene-co-poly-1-octene (PE-co-PO), polyethylene-co-poly(methylenecyclopentane) (PE-co-PMCP), poly(methyl methacrylate) (PMMA), acrylic, polyvinylacetacetal resin, Polyvinyl butyral resin, PVB, stereoblock polypropylene, polypropylene polymethylpentene copolymer, polyethylene oxide (PEO), PEO block copolymer, silicone, polyacrylonitrile (PAN), polyvinyl chloride (PVC), polyvinylpyrrolidone (PVP), polyethylene oxide poly(allyl glycidyl ether) PEO-AGE, polyethylene oxide 2-methoxyethoxyethyl glycidyl ether (PEO-MEEGE), These include, but are not limited to, polyethylene oxide 2-methoxyethoxyethyl glycidyl poly(allyl glycidyl ether) (PEO-MEEGE-AGE), polysiloxane, polyvinylidene fluoride (PVDF), polyvinylidene hexafluoropropylene fluoride (PVDF-HFP), nitrile rubber (NPR), polybutadiene polymer, polybutadiene rubber (PB), polyisobutadiene rubber (PIB), polyolefin, alpha-polyolefin, ethylene alpha-polyolefin, polyisoprene rubber (PI), polychloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), and polyethyl acrylate (PEA).

[0036]

[0047] As used herein, the term "Lewis acid" refers to a molecule or functional group that has a tendency to withdraw electrons (or electron density) from a basic molecule. Examples of Lewis acids include, but are not limited to, tris(trimethysilyl) phosphite (TTSPi), tris(trimethysilyl) phosphate (TTSPa), tris(2,2,2-trifluoroethyl) phosphite, tris(2,2,2-trifluoroethyl) phosphate (TTFEP), tris(2,2,2-trifluoroethyl) borate (TTFEB), trimethoxyboroxine (C3H9B3O6, TMOBX), triallyl phosphate (TAP), tris(trimethylsilyl) borate (TMSB), tris(pentafluorophenyl)borane (TPFPB), and combinations thereof.

[0037]

[0048] Examples of non-Lewis acids used herein include vinylene carbonate (VC), vinyl ethylene carbonate (VEC), methylene methane disulfonate (MMDS), ethylene sulfate, 1,3 propylene sulfate, prop-1-ene-1,3 sultone (PES), propylene sulfite, 1,4 butane sultone, fluoroethylene carbonate (FEC), LiTFSi, LiBOB, 3-sulfolene, succinonitrile, glutaronitrile, trimethylene sulfate (TMS), and combinations thereof.

[0038]

[0049] As used herein, the term "alkyl" by itself or as part of another substituent means a saturated branched or straight-chain monovalent terminal or divalent bridging group, a hydrocarbon radical derived by removing at least one hydrogen atom from a single carbon atom of a parent alkane. Alkyl groups of interest include methyl, ethyl, Examples of alkyl groups include, but are not limited to, n-propyl, i-propyl, n-butyl, i-butyl, and t-butyl. In some embodiments, an alkyl group contains 1 to 20 carbon atoms. In some embodiments, an alkyl group contains 1 to 10 carbon atoms. In some embodiments, an alkyl group contains 1 to 6 carbon atoms, for example, 1 to 4 carbon atoms. This term includes, by way of example, linear and branched hydrocarbyl groups, such as methyl (CH3-), ethyl (CH3CH2-), n-propyl (CH3CH2CH2-), isopropyl ((CH3)2CH-), These include n-butyl (CHCHCHCHCH-), isobutyl ((CH)CHCH-), sec-butyl ((CH)(CHCH)CH-), t-butyl ((CH)C-), n-pentyl (CHCHCHCHCHCH-), and neopentyl ((CH)CCH-). The alkyl substituent may be further substituted with 1 to 6 unsubstituted substituents.

[0039]

[0050] "Heteroalkyl" refers to a straight- or branched-chain alkyl group preferably having 2 to 14 carbon atoms, more preferably 2 to 10 carbon atoms, in the chain, one or more of which are replaced with a heteroatom selected from S, O, P, and N. Representative heteroalkyl groups include alkyl ethers (i.e., alkoxyls), secondary and tertiary alkyl amines, amides, alkyl sulfides (i.e., thiols), and the like. Heteroalkyl substituents may be further substituted with 1 to 6 unsubstituted substituents. The group may be a monovalent terminal group or a divalent bridging group.

[0040]

[0051] As used herein, "a C ring containing at least one sulfur (S) ring atom" means a C ring containing at least one sulfur (S) ring atom. 3-10 The term "heterocyclic molecule" refers to a cyclic alkyl, alkenyl, or alkynyl ring in which at least one carbon atom is replaced with a sulfur (S) atom. 3-10 Heterocyclic molecules are molecules containing 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms in a continuous ring structure.

[0041]

[0052] As used herein, the phrase "optionally substituted with 1 to 6 substituents" refers to the condition that a group may or may not have substituents. When substituents are present, only 1, 2, 3, 4, 5, or 6 substituents may be present. Substituents include polyethylene glycol (PEG), ═O, SO, —CF, —CHF, CHF, —NO, —NO, —NH, —CH, PO, PO, BO, 3、 These include, but are not limited to, -CN, F, Cl, Br, I, and combinations thereof. Unless otherwise specified herein, these substituents are not further substituted. Unless otherwise specified herein, these substituents are not protic.

[0042]

[0053] As used herein, "a C ring atom containing at least one sulfur (S) ring atom and one oxygen (O) ring atom" means a C ring atom containing at least one sulfur (S) ring atom and one oxygen (O) ring atom. 3-10The term "heterocyclic molecule" refers to a cyclic alkyl, alkenyl, or alkynyl ring in which at least one carbon atom is replaced with a sulfur (S) atom and at least one carbon atom is replaced with an oxygen (O) atom. 3-10 Heterocyclic molecules are molecules that contain 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms in a continuous ring structure.

[0043]

[0054] As used herein, the phrase "electrochemical cell" or "battery cell" refers to a cell that includes a positive electrode and a negative electrode, with the two in ionic communication using an electrolyte. In some embodiments, the same battery cell includes multiple positive electrodes and / or multiple negative electrodes sealed in a single container.

[0044]

[0055] As used herein, the phrase "electrochemical stack" refers to a stack of at least one negative electrode (e.g., Li, LiC) and a positive electrode (e.g., FeF, NiF x (wherein x is 2 or 3), nickel cobalt aluminum oxide (NCA), lithium iron phosphate (LFP), LiNi x Mn y Co z O2, [NMC], or LiNi x Al y Co z O2[NCA] (where x+y+z=1; 0≦x≦1; 0≦y≦1; and 0≦z≦1), optionally combined with a solid electrolyte or a gel electrolyte), and a solid electrolyte (e.g., lithium-filled garnet (Li7La3Zr2O 12) (an oxide electrolyte as described herein, such as a fluorine-containing oxide electrolyte). In some embodiments, including any of the above, there is an additional layer between the solid electrolyte and the positive electrode that includes a compliant material (e.g., a gel electrolyte). An electrochemical stack can include one of these aforementioned units. An electrochemical stack can include several of these aforementioned units arranged in electrical communication (e.g., electrical connection in series or parallel). In some embodiments, including any of the above, when the electrochemical stack includes several units, the units are layered or stacked on top of each other in a line. In some embodiments, including any of the above, when the electrochemical stack includes several units, the units are layered or stacked on top of each other in an array. In some embodiments, including any of the above, when the electrochemical stack includes several units, the stack is arranged such that one negative electrode is shared by two or more positive electrodes. Alternatively, in some embodiments, including any of the above, when the electrochemical stack includes several units, the stack is arranged such that one positive electrode is shared by two or more negative electrodes. Unless otherwise specified, an electrochemical stack includes one positive electrode, one solid electrolyte, and one negative electrode, and optionally includes an adhesive layer between the positive electrode and the solid electrolyte.

[0045]

[0056] As used herein, the term "positive electrode" refers to a positive electrode that has cations, e.g., Li, moving towards it during discharge of the battery. + means an electrode in a secondary battery where current conducts, flows, or moves.

[0046]

[0057] As used herein, the term "negative electrode" refers to the electrode from which cations, such as Li, are released during discharge of the battery. + refers to an electrode in a secondary battery in which the charge flows or moves. A negative electrode containing lithium metal is referred to herein as a lithium metal negative electrode.

[0047]

[0058] In a battery constructed with a Li metal electrode and an electrode (i.e., cathode active material) containing a conversion chemistry, an intercalation chemistry, or a combination of conversion / intercalation chemistry, the electrode with the material of the conversion chemistry, the intercalation chemistry, or the combination of conversion / intercalation chemistry is called the positive electrode. In some applications, a cathode is used instead of the positive electrode, and an anode is used instead of the negative electrode. When a Li secondary battery is charged, Li ions are transported to the positive electrode (e.g., NiF x , NMC, NCA) toward the negative electrode (e.g., Li metal). When a Li secondary battery is discharged, Li ions move from the negative electrode toward the positive electrode. When a Li secondary battery is discharged, Li ions move from the negative electrode toward the positive electrode.

[0048]

[0059] As used herein, the phrase "positive electrode terminal" refers to an electrical connection to a positive electrode. The positive electrode terminal may also be referred to as a positive electrode current collector.

[0049]

[0060] As used herein, the phrase "negative electrode terminal" refers to an electrical connection to a negative electrode. The negative electrode terminal may also be referred to as a negative electrode current collector.

[0050]

[0061] As used herein, the phrase "cathode active material" means a material capable of intercalating with or reacting with lithium ions in a reversible manner. Examples include LiMPO4 (M=Fe, Ni, Co, Mn); Li x Ti y O z (wherein x is 0 to 8, y is 1 to 12, and z is 1 to 24); LiMn 2a Ni a O4 (wherein a is 0 to 2); nickel cobalt aluminum oxide; LiNi x Mn y Co z O2 (x+y+z=1, 0≦x≦1, 0≦y≦1, and 0≦z≦1); and LiNi x Co y Al zO2, where x+y+z=1, and 0≦x≦1, 0≦y≦1, and 0≦z≦1. In these formulas, x, y, and z are selected so that the formula is charge-neutral.

[0051]

[0062] As used herein, the phrase "solid cathode" refers to a cathode that does not contain a liquid-phase electrolyte. As used herein, the terms "cathode" and "anode" refer to the electrodes of a battery. Cathode and anode are often referred to in the art as positive and negative electrodes, respectively.

[0052]

[0063] As used herein, the term "electrolyte" refers to a compound containing ions, such as Li + An electrolyte is a material through which ions can move but electrons cannot be conducted. An electrolyte is an ionically conductive and electrically insulating material; it is useful for electrically insulating the cathode and anode of a secondary battery, while at the same time transporting ions, such as Li + can be transmitted through the electrolyte.

[0053]

[0064] As used herein, unless otherwise specified, the term "gel electrolyte" refers to a suitable Li + It refers to an ionically conductive gel or liquid-based electrolyte, such as that described in U.S. Pat. No. 5,296,318, entitled "RECHARGEABLE LITHIUM INTERCALATION BATTERY WITH HYBRID POLYMERIC ELECTROLYTE," which is incorporated herein by reference in its entirety for all purposes. A gel electrolyte is one that has a conductivity of 10 .mu.m at room temperature. -5 The gel has a lithium ion conductivity greater than 100 S / cm, a lithium transference number between 0.05 and 0.95, and a storage modulus greater than the loss modulus at a certain temperature. The gel is formed by at least partially dissociating the polymer matrix and the solvent that gels the polymer, resulting in the formation of Li. + The gel electrolyte may include a lithium-containing salt that provides ions and anions, where in some instances the gel electrolyte is used as the bonding layer.

[0054]

[0065] As used herein, the term "catholyte" means a liquid or gel lithium ion conductor intimately mixed with or surrounded by a cathode (i.e., positive electrode) active material. A liquid electrolyte becomes a catholyte when mixed with a cathode.

[0055]

[0066] As used herein, the phrases "solid electrolyte separator" or "solid separator" or "solid separator" are used interchangeably with the phrase "solid separator" and are intended to mean a separator that does not contain carbon and is free of atomic ions (e.g., Li + ) refers to a material that conducts carbon but not electrons. A solid electrolyte separator is a solid material suitable for electrically insulating the positive and negative electrodes of a lithium secondary battery while also providing a conduction path for lithium ions. Examples of inorganic solid electrolytes include oxide electrolytes and sulfide electrolytes, which are further defined below. Non-limiting examples of sulfide electrolytes can be found, for example, in U.S. Patent No. 9,172,114, issued October 27, 2015, and U.S. Patent Application Publication No. 2017-0162901 A1, published June 8, 2017, the entire contents of which are incorporated herein by reference for all purposes. Non-limiting examples of oxide electrolytes can be found, for example, in U.S. Patent Application Publication No. 2015-0200420 A1, published July 16, 2015, the entire contents of which are incorporated herein by reference for all purposes. In some examples, the inorganic solid electrolyte also includes a polymer, referred to as a composite electrolyte. Composite electrolytes can be found, for example, in US Pat. No. 9,666,870, the entire contents of which are incorporated herein by reference for all purposes.

[0056]

[0067] As used herein, "separator" and "Li + The terms "ion-conducting separator" are used interchangeably and unless clearly stated otherwise, the separator is +As used herein, the phrase "solid electrolyte separator" refers to a separator that is substantially insulating to electrons (e.g., lithium ion conductivity is at least 10 times that of the electronic conductivity). 3 times, often 10 6 ), which acts as a physical barrier or spacer between the positive and negative electrodes in an electrochemical cell. + It means a conductive material.

[0057]

[0068] Unless specified to the contrary, the separators used herein are stable when in contact with lithium metal.

[0058]

[0069] As used herein, the phrase "thickness" or "film thickness" refers to the distance or median measured distance between the top and bottom faces or surfaces. As used herein, top and bottom faces refer to the faces having the largest geometric surface area.

[0059]

[0070] As used herein, "thin" refers to a thickness dimension of less than 200 μm, sometimes less than 100 μm, in some cases between 0.1 and 60 μm, in other cases between about 10 μm and about 100 μm, and in other cases about 1 μm, 10 μm, or 50 μm thick, when modifying a solid electrolyte.

[0060]

[0071] As used herein, "sintered thin film" means a thin film that has been sintered, e.g., heated to temperatures above 1000°C, to densify its structure without changing its chemical composition.

[0061]

[0072] As used herein, the term "lithium-filled garnet" means an oxide characterized by a crystal structure related to the garnet crystal structure. Examples of lithium-filled garnet electrolytes include those described in U.S. Patent Application Publication No. 2015 / 0099190, filed Oct. 7, 2014, titled GARNET MATERIALS FOR LI SECONDARY BATTERIES AND METHODS OF MAKING AND USING GARNET MATERIALS, and published Apr. 9, 2015 (the entire contents of which are incorporated by reference). Li A La B M’ C M’’ D Zr E O F 、Li A La B M’ C M’’ D Ta E O F 、or Li A La B M’ C M’’ D Nb E O F (where 4 < A < 8.5, 1.5 < B < 4, 0 ≦ C ≦ 2.5, 0 ≦ D ≦ 2.5; 0 ≦ E < 2.3, 10 < F < 13, and M’ and M’ are each independently, in each case, selected from Al, Mo, W, Ga, Gd, Y, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta), or Li a La b Zr c Al d Me’’ e O f(where 5 < a < 8.5; 2 < b < 4; 0 < c ≤ 2.5; 0 ≤ d < 2; 0 ≤ e < 2, and 10 < f < 13, and Me’’ is a metal selected from Nb, Ta, V, W, Mo, or Sb), and as another, a Li-filled garnet generally having a composition according to that described in US Patent Application Publication No. 2015 / 0099190. In some embodiments, A may be about 6.0 or about 6.1 or about 6.2 or about 6.3 or about 6.4 or about 6.5 or about 6.6 or about 6.7 or about 6.8 or about 6.9 or about 7.0 or about 7.1 or about 7.2 or about 7.3 or about 7.4. In some embodiments, B may be about 2.8 or about 2.9 or about 3.0 or about 3.1 or about 3.2. In some embodiments, C may be about 0 or about 0.1 or about 0.2 or about 0.3 or about 0.4 or about 0.5 or about 0.6 or about 0.7 or about 0.8 or about 0.9 or about 1.0 or about 1.1 or about 1.2 or about 1.3 or about 1.4 or about 1.5 or about 1.6 or about 1.7 or about 1.8 or about 1.9 or about 2.0. In some embodiments, D may be about 0 or about 0.1 or about 0.2 or about 0.3 or about 0.4 or about 0.5 or about 0.6 or about 0.7 or about 0.8 or about 0.9 or about 1.0 or about 1.1 or about 1.2 or about 1.3 or about 1.4 or about 1.5 or about 1.6 or about 1.7 or about 1.8 or about 1.9 or about 2.0. In some embodiments, E may be about 1.4 or about 1.5 or about 1.6 or about 1.7 or about 1.8 or about 1.9 or about 2.0 or about 2.1 or about 2.2. In some embodiments, F may be about 11.0 or about 11.1 or about 11.2 or about 11.3 or about 11.4 or about 11.5 or about 11.6 or about 11.7 or about 11.8 or about 11.9 or about 12.0 or about 12.1 or about 12.2 or about 12.3 or about 12.4 or about 12.5 or about 12.6 or about 12.7 or about 12.8 or about 12.9 or about 13.0. Here, the values of the subscripts and the values of the coefficients are selected such that the compound is charge-neutral unless the contrary is stated. As used herein, lithium-filled garnets, and garnets generally, but not limited to, Li 7.0 La3(Zr t1 +Nb t2 +Tat3 )O 12 +0.35Al2O3; where (subscript t1 + t2 + t3 = subscript 2), so the ratio of La:(Zr / Nb / Ta) is 3:2. Garnets as used herein also include, but are not limited to, Li x La3Zr2O F+yAl2O3, where x ranges from 5.5 to 9; and y ranges from 0 to 1. In these embodiments, the subscripts x, y, and F are selected so that the garnet is charge neutral. In some embodiments, x is 7 and y is 1.0. In some embodiments, x is 5 and y is 1.0. In some embodiments, x is 6 and y is 1.0. In some embodiments, x is 8 and y is 1.0. In some embodiments, x is 9 and y is 1.0. In some embodiments, x is 7 and y is 0.35. In some embodiments, x is 5 and y is 0.35. In some embodiments, x is 6 and y is 0.35. In some embodiments, x is 8 and y is 0.35. In some embodiments, x is 9 and y is 0.35. In some embodiments, x is 7 and y is 0.7. In some embodiments, x is 5 and y is 0.7. In some embodiments, x is 6 and y is 0.7. In some embodiments, x is 8 and y is 0.7. In some embodiments, x is 9 and y is 0.7. In some embodiments, x is 7 and y is 0.75. In some embodiments, x is 5 and y is 0.75. In some embodiments, x is 6 and y is 0.75. In some embodiments, x is 8 and y is 0.75. In some embodiments, x is 9 and y is 0.75. In some embodiments, x is 7 and y is 0.8. In some embodiments, x is 5 and y is 0.8. In some embodiments, x is 6 and y is 0.8. In some embodiments, x is 8 and y is 0.8. In some embodiments, x is 9 and y is 0.8. In some embodiments, x is 7 and y is 0.5. In some embodiments, x is 5 and y is 0.5. In some embodiments, x is 6 and y is 0.5. In some embodiments, x is 8 and y is 0.5. In some embodiments, x is 9 and y is 0.5. In some embodiments, x is 7 and y is 0.4. In some embodiments, x is 5 and y is 0.4. In some embodiments, x is 6 and y is 0.4.In some embodiments, x is 8 and y is 0.4. In some embodiments, x is 9 and y is 0.4. In some embodiments, x is 7 and y is 0.3. In some embodiments, x is 5 and y is 0.3. In some embodiments, x is 6 and y is 0.3. In some embodiments, x is 8 and y is 0.3. In some embodiments, x is 9 and y is 0.3. In some embodiments, x is 7 and y is 0.22. In some embodiments, x is 5 and y is 0.22. In some embodiments, x is 6 and y is 0.22. In some embodiments, x is 8 and y is 0.22. In some embodiments, x is 9 and y is 0.22. Also, as used herein, garnet includes Li. x La3Zr2O 12 In one embodiment, the Li-filled garnets herein include, but are not limited to, LiLiZrO 12 In another embodiment, the Li-filled garnet herein has a composition of Li7Li3Zr2O 12 In yet another embodiment, the Li-filled garnet herein has a composition of LiLiZrO 12 In yet another embodiment, the Li-filled garnet herein has a composition of LiLiZrO 12 In another embodiment, the Li-filled garnet herein has a composition of LiLiZrO 12 In another embodiment, the Li-filled garnet herein has a composition of LiLiZrO 12 ·It has a composition of 0.75Al2O3.

[0062]

[0073] As used herein, lithium-filled garnets and / or garnets include YAG garnets (i.e., yttrium aluminum garnets, i.e., YAlO 12As used herein, garnet does not include silicate-based garnets such as pyrope, almandine, spessartine, grossular, hessonite, or cinnamon, tsavorite, uvarovite, and andradite, and the solid solutions pyrope-almandine-spessarite and uvarovite-grossular-andradite. Garnet, as used herein, does not include nesosilicates having the general formula X3Y2(SiO4)3, where X is Ca, Mg, Fe, and / or Mn; and Y is Al, Fe, and / or Cr.

[0063]

[0074] As used herein, the phrases "garnet precursor chemicals," "chemical precursors of garnet-type electrolytes," "garnet precursors," and "garnet precursor materials" refer to chemicals that react to form the lithium-filled garnet materials described herein. These chemical precursors include, but are not limited to, lithium hydroxide (e.g., LiOH), lithium oxide (e.g., LiO), lithium carbonate (e.g., LiCO), zirconium oxide (e.g., ZrO), zirconium hydroxide, zirconium acetate, zirconium nitrate, zirconium acetylacetonate, zirconium nitrate x-hydrate, lanthanum oxide (e.g., LaO), lanthanum hydroxide (e.g., La(OH)), lanthanum nitrate, lanthanum acetate, lanthanum acetylacetonate, aluminum oxide (e.g., AlO), aluminum hydroxide (e.g., Al(OH)), aluminum (e.g., Al), aluminum nitrate (e.g., Al(NO)), aluminum nitrate nonahydrate, boehmite, gibbsite, corundum, aluminum oxyhydroxide, niobium oxide (e.g., NbO), gallium oxide (GaO), and tantalum oxide (e.g., TaO). Other precursors of garnet materials may be suitable for use in the methods described herein.

[0064]

[0075] As used herein, the term "garnet-type electrolyte" refers to a Li +It refers to an electrolyte comprising the lithium-filled garnet material described herein as an ionic conductor.

[0065]

[0076] As used herein, the phrase "doped with alumina" means that Al2O3 is used to replace a component of another material, e.g., a garnet. A lithium-filled garnet doped with Li-Al2O3 refers to a garnet in which aluminum (Al) replaces an element in the chemical formula of the lithium-filled garnet, which may be, for example, Li or Zr.

[0066]

[0077] As used herein, area specific resistance (ASR) is measured by electrochemical cycling using an Arbin or Biologic instrument unless specified to the contrary.

[0067] electrochemical cell

[0078] In one embodiment, there is provided an electrochemical cell comprising a positive electrode, a lithium metal negative electrode, a solid electrolyte comprising a lithium-loaded garnet, and a catholyte, wherein the catholyte comprises: a lithium salt; and at least two C groups, each independently in each instance, containing at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents. 3-10 and a heterocyclic molecule.

[0068]

[0079] In another embodiment, there is provided an electrochemical cell comprising a positive electrode, a lithium metal negative electrode, a solid electrolyte comprising a lithium-loaded garnet, and a catholyte, wherein the catholyte comprises: a lithium salt; and at least two C groups each containing at least one sulfur (S) ring atom, each independently in each instance containing at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents. 3-10 and a heterocyclic molecule.

[0069]

[0080] In another embodiment, there is provided an electrochemical cell comprising a positive electrode, a lithium metal negative electrode, a solid electrolyte comprising a lithium-loaded garnet, and a catholyte, wherein the catholyte comprises: a lithium salt; and at least two C groups comprising at least one sulfur (S) ring atom and one oxygen (O) ring atom, each independently in each instance comprising at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents. 3-10 and a heterocyclic molecule.

[0070]

[0081] In certain embodiments, including any of the foregoing, the substitutions are selected from polyethylene glycol (PEG), ═O, SO 2 , —CF 3 , —CH 2 F, CHF 2 , —NO 2 , —NO 3 , —NH 3 , —CH 3 , PO 4 , PO 3 , BO 3 , and —CN.

[0071] Catholyte solution

[0082] In one embodiment, including any of the foregoing, a lithium salt; and, each independently, at least two C rings, in each instance, containing at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents. 3-10 Provided herein is a catholyte solution comprising a heterocyclic molecule.

[0072]

[0083] In another embodiment, including any of the foregoing, a lithium salt is provided, comprising: at least two C rings each containing at least one sulfur (S) ring atom and each independently, in each instance, optionally substituted with 1 to 6 substituents and optionally containing at least one sulfur (S) ring atom. 3-10 Provided herein is a catholyte solution comprising a heterocyclic molecule.

[0073]

[0084] In certain embodiments, including any of the foregoing, the substitutions are selected from polyethylene glycol (PEG), ═O, SO 2 , —CF 3 , —CH 2 F, CHF 2 , —NO 2 , —NO 3 , —NH 3 , —CH 3 , PO 4 , PO 3 , BO 3 , and —CN.

[0074]

[0085] In some embodiments, including any of the foregoing, C3-10 The heterocyclic molecule has the formula (I): [ka] (In the formula, R 1 is selected from the group consisting of polyethylene glycol (PEG), ═O, SO, —CF, —CHF, CHF, —NO, —NO, —NH, —CH, PO, PO, BO, —CN, and combinations thereof; R 2 is =O or absent; R 3 is =O or absent; and the subscript n is an integer from 0 to 8. is the molecule.

[0075]

[0086] In some embodiments, including any of the foregoing, C 3-10 The heterocyclic molecule has the formula (II): [ka] (In the formula, R 1 is selected from the group consisting of polyethylene glycol (PEG), ═O, SO, —CF, —CHF, CHF, —NO, —NO, —NH, —CH, PO, PO, BO, —CN, and combinations thereof; R 2 is =O or absent; R 3 is =O or absent; and the subscript n is an integer from 0 to 8. is the molecule.

[0076]

[0087] In some embodiments, including any of the foregoing, C 3-10 Heterocyclic molecules have the formula [ka] (In the formula, R 1 is selected from the group consisting of polyethylene glycol (PEG), ═O, SO, —CF, —CHF, CHF, —NO, —NO, —NH, —CH, PO, PO, BO, —CN, and combinations thereof; and the subscript n is an integer from 0 to 8. is the molecule.

[0077]

[0088] In some embodiments, including any of the foregoing, C 3-10 The heterocyclic molecule has the formula (IIb): [ka] (In the formula, R 1 is selected from the group consisting of polyethylene glycol (PEG), ═O, SO, —CF, —CHF, CHF, —NO, —NO, —NH, —CH, PO, PO, BO, —CN, and combinations thereof; and the subscript n is an integer from 0 to 8. is the molecule.

[0078]

[0089] In some embodiments, including any of the foregoing, C 3-10 The heterocyclic molecule has the formula (III): [ka] is the molecule.

[0079]

[0090] In some embodiments, including any of the foregoing, C 3-10 The heterocyclic molecule has the formula (VII): [ka] is the molecule.

[0080]

[0091] In some embodiments, including any of the foregoing, C 3-10 The heterocyclic molecule has the formula (IV): [ka] (In the formula, R 1 is selected from the group consisting of polyethylene glycol (PEG), ═O, SO, —CF, —CHF, CHF, —NO, —NO, —NH, —CH, PO, PO, BO, —CN, and combinations thereof; and the subscript n is an integer from 0 to 8. is the molecule.

[0081]

[0092] In some embodiments, including any of the foregoing, C 3-10 A heterocyclic molecule contains at least one sulfur (S) ring atom.

[0082]

[0093] In some embodiments, including any of the foregoing, C 3-10 A heterocyclic molecule contains at least one sulfur (S) ring atom and one oxygen (O) ring atom.

[0083]

[0094] In some embodiments, including any of the foregoing, C 3-10 The heterocyclic molecule has the formula (V): [ka] (In the formula, R 1 is selected from the group consisting of polyethylene glycol (PEG), ═O, SO2, —CF3, —CH2F, CHF2, —NO2, —NO3, —NH3, —CH3, PO4, PO3, BO3, —CN, and combinations thereof. The superscript n is an integer from 0 to 8. is the molecule.

[0084]

[0095] In some embodiments, including any of the foregoing, C 3-10 The heterocyclic molecule has the formula (VI): [ka] is the molecule.

[0085]

[0096] In some embodiments, including any of the foregoing, R 1is PEG. In certain embodiments, including any of the above, subscript n is 1. In certain other embodiments, including any of the above, subscript n is 2. In some embodiments, including any of the above, subscript n is 3. In some other embodiments, including any of the above, subscript n is 4. In some embodiments, including any of the above, subscript n is 5. In still other embodiments, including any of the above, subscript n is 6. In some embodiments, including any of the above, subscript n is 7. In some other embodiments, including any of the above, subscript n is 8.

[0086]

[0097] In certain embodiments, including any of the above, subscript n is 0. In certain embodiments, including any of the above, subscript n is 1. In certain other embodiments, including any of the above, subscript n is 2. In some embodiments, including any of the above, subscript n is 3. In some other embodiments, including any of the above, subscript n is 4. In some embodiments, including any of the above, subscript n is 5. In still other embodiments, including any of the above, subscript n is 6. In some embodiments, including any of the above, subscript n is 7. In some other embodiments, including any of the above, subscript n is 8.

[0087]

[0098] In some embodiments, including any of the foregoing, R 1 is =O. In some embodiments, subscript n is 1. In some other embodiments, subscript n is 2. In some embodiments, subscript n is 3. In some other embodiments, subscript n is 4. In some embodiments, subscript n is 5. In still other embodiments, subscript n is 6. In some embodiments, subscript n is 7. In some other embodiments, subscript n is 8.

[0088]

[0099] In some embodiments, including any of the foregoing, R 1is SO2. In certain embodiments, subscript n is 1. In certain other embodiments, subscript n is 2. In some embodiments, subscript n is 3. In certain other embodiments, subscript n is 4. In certain embodiments, subscript n is 5. In still other embodiments, subscript n is 6. In certain embodiments, subscript n is 7. In certain other embodiments, subscript n is 8.

[0089]

[0100] In some embodiments, including any of the foregoing, R 1 is -CF3. In some embodiments, subscript n is 1. In some other embodiments, subscript n is 2. In some embodiments, subscript n is 3. In some other embodiments, subscript n is 4. In some embodiments, subscript n is 5. In still other embodiments, subscript n is 6. In some embodiments, subscript n is 7. In some other embodiments, subscript n is 8.

[0090]

[0101] In some embodiments, including any of the foregoing, R 1 is -CHF. In certain embodiments, subscript n is 1. In certain other embodiments, subscript n is 2. In some embodiments, subscript n is 3. In certain other embodiments, subscript n is 4. In certain embodiments, subscript n is 5. In still other embodiments, subscript n is 6. In certain embodiments, subscript n is 7. In certain other embodiments, subscript n is 8.

[0091]

[0102] In some embodiments, including any of the foregoing, R 1is CHF2. In certain embodiments, subscript n is 1. In certain other embodiments, subscript n is 2. In some embodiments, subscript n is 3. In certain other embodiments, subscript n is 4. In certain embodiments, subscript n is 5. In still other embodiments, subscript n is 6. In certain embodiments, subscript n is 7. In certain other embodiments, subscript n is 8. In certain embodiments, including any of the foregoing, R 1 is -NO2.

[0092]

[0103] In some embodiments, including any of the foregoing, R 1 is -NO3. In certain embodiments, the subscript n is 1. In certain other embodiments, the subscript n is 2. In some embodiments, the subscript n is 3. In some other embodiments, the subscript n is 4. In certain embodiments, the subscript n is 5. In still other embodiments, the subscript n is 6. In some embodiments, the subscript n is 7. In some other embodiments, the subscript n is 8. In some embodiments, including any of the foregoing, R 1 is -NH3.

[0093]

[0104] In some embodiments, including any of the foregoing, R 1 is -CH3. In certain embodiments, the subscript n is 1. In certain other embodiments, the subscript n is 2. In some embodiments, the subscript n is 3. In certain other embodiments, the subscript n is 4. In certain embodiments, the subscript n is 5. In still other embodiments, the subscript n is 6. In certain embodiments, the subscript n is 7. In certain other embodiments, the subscript n is 8.

[0094]

[0105] In some embodiments, including any of the foregoing, R 1is PO4. In some embodiments, subscript n is 1. In some other embodiments, subscript n is 2. In some embodiments, subscript n is 3. In some other embodiments, subscript n is 4. In some embodiments, subscript n is 5. In still other embodiments, subscript n is 6. In some embodiments, subscript n is 7. In some other embodiments, subscript n is 8.

[0095]

[0106] In some embodiments, including any of the foregoing, R 1 is PO3. In some embodiments, subscript n is 1. In some other embodiments, subscript n is 2. In some embodiments, subscript n is 3. In some other embodiments, subscript n is 4. In some embodiments, subscript n is 5. In yet other embodiments, subscript n is 6. In some embodiments, subscript n is 7. In some other embodiments, subscript n is 8.

[0096]

[0107] In some embodiments, including any of the foregoing, R 1 is BO3. In some embodiments, subscript n is 1. In some other embodiments, subscript n is 2. In some embodiments, subscript n is 3. In some other embodiments, subscript n is 4. In some embodiments, subscript n is 5. In yet other embodiments, subscript n is 6. In some embodiments, subscript n is 7. In some other embodiments, subscript n is 8.

[0097]

[0108] In some embodiments, including any of the foregoing, R 1 is -CN. In certain embodiments, subscript n is 1. In certain other embodiments, subscript n is 2. In some embodiments, subscript n is 3. In certain other embodiments, subscript n is 4. In certain embodiments, subscript n is 5. In still other embodiments, subscript n is 6. In certain embodiments, subscript n is 7. In certain other embodiments, subscript n is 8.

[0098]

[0109] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is selected from the group consisting of ethylene sulfite, propylene glycol sulfite, sulfolane; 1,3-propane sultone; sulfolane; thiophene, thiazole, 1,2-oxathiolane, thiepine, 1,4-thiazepine, 6-H-1,2,5-thiadiazine, 2H,6H-1,5,2-dithiazine, thiopyran, thiepine, thiocin, derivatives thereof, and combinations thereof.

[0099]

[0110] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is selected from ethylene sulfite.

[0100]

[0111] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is selected from propylene glycol sulfites.

[0101]

[0112] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is selected from sulfolane.

[0102]

[0113] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is selected from 1,3-propane sultone.

[0103]

[0114] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is selected from sulfolane.

[0104]

[0115] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is selected from thiophenes.

[0105]

[0116] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is selected from thiazoles.

[0106]

[0117] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is selected from 1,2-oxathiolanes.

[0107]

[0118] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is selected from thiepins.

[0108]

[0119] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is selected from 1,4-thiazepines.

[0109]

[0120] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is selected from 6-H-1,2,5-thiadiazines.

[0110]

[0121] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is selected from 2H,6H-1,5,2-dithiazines.

[0111]

[0122] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is selected from thiopyrans.

[0112]

[0123] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is selected from thiepins.

[0113]

[0124] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is selected from thiocines.

[0114]

[0125] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is selected from the group consisting of ethylene sulfite and propylene glycol sulfite.

[0115]

[0126] In some embodiments, including any of the foregoing, at least one C 3-10 Derivatives of heterocyclic molecules include -CH 3、 -CF3 or derivatives containing F substituents.

[0116]

[0127] In some embodiments, including any of the foregoing, the solid electrolyte is a thin film.

[0117]

[0128] In some embodiments, including any of the foregoing, the solid electrolyte is a sintered thin film.

[0118]

[0129] In some embodiments, including any of the foregoing, the solid electrolyte is a sintered thin film comprising a lithium-filled garnet.

[0119]

[0130] In some embodiments, including any of the foregoing, the lithium salt is selected from the group consisting of LiPF, lithium bis(oxalato)borate (LiBOB), lithium bis(perfluoroethanesulfonyl)imide (LIBETI), bis(trifluoromethane)sulfonimide (LiTFSI), LiBF, LiClO, LiAsF, lithium bis(fluorosulfonyl)imide (LiFSI), LiI, and combinations thereof.

[0120]

[0131] In some embodiments, including any of the foregoing, the LIPF6 formulation includes 30:70 sulfolane:ethylene sulfite v / v + 1.4M LiPF6.

[0121]

[0132] In some embodiments, including any of the foregoing, the LiBF4 formulation includes 30:70 sulfolane:ethylene sulfite v / v + 1.4M LiBF4.

[0122]

[0133] In some embodiments, including any of the foregoing, the catholyte comprises 30:70 sulfolane:ethylene sulfite v / v + 1.4M LiPF6.

[0123]

[0134] In some embodiments, including any of the foregoing, the catholyte comprises 30:70 sulfolane:ethylene sulfite v / v + 1.4M LiPF6.

[0124]

[0135] In some embodiments, including any of the foregoing, the catholyte comprises 30:70 sulfolane:ethylene sulfite v / v + 1.4M LiBF4.

[0125]

[0136] In some embodiments, including any of the foregoing, the catholyte comprises 30:70 sulfolane:ethylene sulfite v / v + 1.4M LiPF6.

[0126]

[0137] In some embodiments, including any of the above, the lithium salt is present at a concentration of about 0.5 M to about 2.5 M. In some other embodiments, including any of the above, the lithium salt is present at a concentration of about 0.5 M to about 2.0 M. In some embodiments, the lithium salt is present at a concentration of about 0.5 M. In some other embodiments, the lithium salt is present at a concentration of about 0.6 M. In some embodiments, the lithium salt is present at a concentration of about 0.7 M. In some other embodiments, the lithium salt is present at a concentration of about 0.8 M. In other embodiments, the lithium salt is present at a concentration of about 0.9 M. In still other embodiments, the lithium salt is present at a concentration of about 1.0 M. In some embodiments, the lithium salt is present at a concentration of about 1.1 M. In some embodiments, the lithium salt is present at a concentration of about 1.2 M. In some embodiments, the lithium salt is present at a concentration of about 1.3 M. In some embodiments, the lithium salt is present at a concentration of about 1.4 M. In some embodiments, the lithium salt is present at a concentration of about 1.5 M. In some embodiments, the lithium salt is present at a concentration of about 1.6 M. In some embodiments, the lithium salt is present at a concentration of about 1.7 M. In some embodiments, the lithium salt is present at a concentration of about 1.8 M. In some embodiments, the lithium salt is present at a concentration of about 1.9 M. In some embodiments, the lithium salt is present at a concentration of about 2.0 M. In some embodiments, the lithium salt is present at a concentration of about 2.1 M. In some embodiments, the lithium salt is present at a concentration of about 2.2 M. In some embodiments, the lithium salt is present at a concentration of about 2.3 M. In some embodiments, the lithium salt is present at a concentration of about 2.4 M. In some embodiments, the lithium salt is present at a concentration of about 2.5 M. In some embodiments, the lithium salt is present at a concentration of about 2.6 M.

[0127]

[0138] In some embodiments, including any of the foregoing, the lithium salt is present at a concentration of about 0.5M to about 5M. In some embodiments, the lithium salt is present at a concentration of about 0.5M. In some other embodiments, the lithium salt is present at a concentration of about 0.6M. In some embodiments, the lithium salt is present at a concentration of about 0.7M. In some other embodiments, the lithium salt is present at a concentration of about 0.8M. In other embodiments, the lithium salt is present at a concentration of about 0.9M. In still other embodiments, the lithium salt is present at a concentration of about 1.0M. In some embodiments, the lithium salt is present at a concentration of about 1.1M. In some embodiments, the lithium salt is present at a concentration of about 1.2M. In some embodiments, the lithium salt is present at a concentration of about 1.3M. In some embodiments, the lithium salt is present at a concentration of about 1.4M. In some embodiments, the lithium salt is present at a concentration of about 1.5M. In some embodiments, the lithium salt is present at a concentration of about 1.6M. In some embodiments, the lithium salt is present at a concentration of about 1.7M. In some embodiments, the lithium salt is present at a concentration of about 1.8M. In some embodiments, the lithium salt is present at a concentration of about 1.9 M. In some embodiments, the lithium salt is present at a concentration of about 2.0 M. In some embodiments, the lithium salt is present at a concentration of about 2.1 M. In some embodiments, the lithium salt is present at a concentration of about 2.2 M. In some embodiments, the lithium salt is present at a concentration of about 2.3 M. In some embodiments, the lithium salt is present at a concentration of about 2.4 M. In some embodiments, the lithium salt is present at a concentration of about 2.5 M. In some embodiments, the lithium salt is present at a concentration of about 2.6 M. In some embodiments, the lithium salt is present at a concentration of about 2.7 M. In some embodiments, the lithium salt is present at a concentration of about 2.8 M. In some embodiments, the lithium salt is present at a concentration of about 2.9 M. In some embodiments, the lithium salt is present at a concentration of about 3.0 M. In some embodiments, the lithium salt is present at a concentration of about 3.1 M. In some embodiments, the lithium salt is present at a concentration of about 3.2 M. In some embodiments, the lithium salt is present at a concentration of about 3.3 M. In some embodiments, the lithium salt is present at a concentration of about 3.4 M. In some embodiments, the lithium salt is present at a concentration of about 3.5 M. In some embodiments, the lithium salt is present at a concentration of about 3.6 M.In some embodiments, the lithium salt is present at a concentration of about 3.7 M. In some embodiments, the lithium salt is present at a concentration of about 3.8 M. In some embodiments, the lithium salt is present at a concentration of about 3.9 M. In some embodiments, the lithium salt is present at a concentration of about 4.0 M. In some embodiments, the lithium salt is present at a concentration of about 4.1 M. In some embodiments, the lithium salt is present at a concentration of about 4.2 M. In some embodiments, the lithium salt is present at a concentration of about 4.3 M. In some embodiments, the lithium salt is present at a concentration of about 4.4 M. In some embodiments, the lithium salt is present at a concentration of about 4.5 M. In some embodiments, the lithium salt is present at a concentration of about 4.6 M. In some embodiments, the lithium salt is present at a concentration of about 4.7 M. In some embodiments, the lithium salt is present at a concentration of about 4.8 M. In some embodiments, the lithium salt is present at a concentration of about 4.9 M. In some embodiments, the lithium salt is present at a concentration of about 5.0 M.

[0128]

[0139] In some embodiments, including any of the above, the lithium salt is present at a concentration of 0.5M to 2.5M. In some other embodiments, including any of the above, the lithium salt is present at a concentration of 0.5M to 2.0M. In some embodiments, the lithium salt is present at a concentration of 0.5M. In some other embodiments, the lithium salt is present at a concentration of 0.6M. In some embodiments, the lithium salt is present at a concentration of 0.7M. In some other embodiments, the lithium salt is present at a concentration of 0.8M. In other embodiments, the lithium salt is present at a concentration of 0.9M. In still other embodiments, the lithium salt is present at a concentration of 1.0M. In some embodiments, the lithium salt is present at a concentration of 1.1M. In some embodiments, the lithium salt is present at a concentration of 1.2M. In some embodiments, the lithium salt is present at a concentration of 1.3M. In some embodiments, the lithium salt is present at a concentration of 1.4M. In some embodiments, the lithium salt is present at a concentration of 1.5M. In some embodiments, the lithium salt is present at a concentration of 1.6M. In some embodiments, the lithium salt is present at a concentration of 1.7M. In some embodiments, the lithium salt is present at a concentration of 1.8M. In some embodiments, the lithium salt is present at a concentration of 1.9M. In some embodiments, the lithium salt is present at a concentration of 2.0M. In some embodiments, the lithium salt is present at a concentration of 2.1M. In some embodiments, the lithium salt is present at a concentration of 2.2M. In some embodiments, the lithium salt is present at a concentration of 2.3M. In some embodiments, the lithium salt is present at a concentration of 2.4M. In some embodiments, the lithium salt is present at a concentration of 2.5M. In some embodiments, the lithium salt is present at a concentration of 2.6M. In some embodiments, the lithium salt is present at a concentration of 2.7M. In some embodiments, the lithium salt is present at a concentration of 2.8M. In some embodiments, the lithium salt is present at a concentration of 2.9M. In some embodiments, the lithium salt is present at a concentration of 3.0M. In some embodiments, the lithium salt is present at a concentration of 3.1M. In some embodiments, the lithium salt is present at a concentration of 3.2M. In some embodiments, the lithium salt is present at a concentration of 3.3 M. In some embodiments, the lithium salt is present at a concentration of 3.4 M. In some embodiments, the lithium salt is present at a concentration of 3.5 M. In some embodiments, the lithium salt is present at a concentration of 3.6 M.In some embodiments, the lithium salt is present at a concentration of 3.7M. In some embodiments, the lithium salt is present at a concentration of 3.8M. In some embodiments, the lithium salt is present at a concentration of 3.9M. In some embodiments, the lithium salt is present at a concentration of 4.0M. In some embodiments, the lithium salt is present at a concentration of 4.1M. In some embodiments, the lithium salt is present at a concentration of 4.2M. In some embodiments, the lithium salt is present at a concentration of 4.3M. In some embodiments, the lithium salt is present at a concentration of 4.4M. In some embodiments, the lithium salt is present at a concentration of 4.5M. In some embodiments, the lithium salt is present at a concentration of 4.6M. In some embodiments, the lithium salt is present at a concentration of 4.7M. In some embodiments, the lithium salt is present at a concentration of 4.8M. In some embodiments, the lithium salt is present at a concentration of 4.9M. In some embodiments, the lithium salt is present at a concentration of 5.0M.

[0129]

[0140] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is sulfolane.

[0130]

[0141] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is 1,3-propane sultone.

[0131]

[0142] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is sulfolene.

[0132]

[0143] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is a thiophene.

[0133]

[0144] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is ethylene sulfite.

[0134]

[0145] In some embodiments, including any of the foregoing, the catholyte comprises ethylene sulfite and sulfolane.

[0135]

[0146] In some embodiments, including any of the foregoing, the catholyte consists essentially of ethylene sulfite and sulfolane.

[0136]

[0147] In some embodiments, including any of the foregoing, the catholyte consists essentially of ethylene sulfite and sulfolane in a volume ratio of 70:30.

[0137]

[0148] In some embodiments, including any of the foregoing, the catholyte consists of ethylene sulfite and sulfolane.

[0138]

[0149] In some embodiments, including any of the foregoing, the catholyte consists of ethylene sulfite and sulfolane in a volume ratio of 70:30.

[0139]

[0150] In some embodiments, including any of the foregoing, the catholyte comprises two C 3-10 Heterocyclic molecules include one C 3-10 The other C of the heterocyclic molecule 3-10 The ratio for heterocyclic molecules is 20:80 vol / vol (v / v) to 80:20 v / v.

[0140]

[0151] In some embodiments, including any of the above, one C 3-10 The other C of the heterocyclic molecule 3-10 The ratio for heterocyclic molecules is 15:85 vol / vol (v / v) to 85:15 v / v.

[0141]

[0152] In some embodiments, including any of the above, one C 3-10 The other C of the heterocyclic molecule 3-10 The ratio for heterocyclic molecules is 20:80 vol / vol (v / v) to 80:20 v / v.

[0142]

[0153] In some embodiments, including any of the above, one C 3-10 The other C of the heterocyclic molecule 3-10 The ratio for heterocyclic molecules is 25:75 vol / vol (v / v) to 75:25 v / v.

[0143]

[0154] In some embodiments, including any of the above, one C 3-10 The other C of the heterocyclic molecule 3-10 The ratio for heterocyclic molecules is 30:70 vol / vol (v / v) to 70:30 v / v.

[0144]

[0155] In some embodiments, including any of the above, one C 3-10 The other C of the heterocyclic molecule 3-10 The ratio for heterocyclic molecules is 35:65 vol / vol (v / v) to 65:35 v / v.

[0145]

[0156] In some embodiments, including any of the above, one C 3-10 The other C of the heterocyclic molecule 3-10 The ratio for heterocyclic molecules is 40:60 vol / vol (v / v) to 60:40 v / v.

[0146]

[0157] In some embodiments, including any of the above, one C 3-10 The other C of the heterocyclic molecule 3-10 The ratio for heterocyclic molecules is 45:55 vol / vol (v / v) to 55:45 v / v.

[0147]

[0158] In some embodiments, including any of the above, one C 3-10 The other C of the heterocyclic molecule 3-10 The ratio for heterocyclic molecules is 50:50 vol / vol (v / v).

[0148]

[0159] In some embodiments, including any of the foregoing, the ratio of sulfolane:(ethylene sulfite) is from 30:70 v / v to 50:50 v / v.

[0149]

[0160] In some embodiments, including any of the foregoing, the ratio of sulfolane:(ethylene sulfite) is 30:70 v / v.

[0150]

[0161] In some embodiments, including any of the foregoing, the ratio of sulfolane:(ethylene sulfite) is 50:50 v / v.

[0151]

[0162] In some embodiments, including any of the foregoing, the catholyte also includes an additive selected from the group consisting of tris(trimethysilyl) phosphite (TTSPi), tris(trimethysilyl) phosphate (TTSPa), trimethoxyboroxine (C3H9B3O6, TMOBX), vinylene carbonate (VC), vinylethylene carbonate (VEC), methylenemethane disulfonate (MMDS), prop-1-ene-1,3 sultone (PES), fluoroethylene carbonate (FEC), LiTFSi, LiBOB, succinonitrile, trimethylene sulfate (TMS), triallyl phosphate (TAP), tris(trimethylsilyl) borate (TMSB), tris(pentafluorophenyl)borane (TPFPB), and combinations thereof.

[0152]

[0163] In some embodiments, including any of the foregoing, the additive is a TTSPi.

[0153]

[0164] In some embodiments, including any of the foregoing, the additive is TTSPa.

[0154]

[0165] In some embodiments, including any of the foregoing, the additive is a combination of TTSPi and TTSPa.

[0155]

[0166] In some embodiments, including any of the foregoing, the lithium-filled garnet is Li A La B M' C M” D Zr E O F , Li A La B M'C M’’ D Ta E O F 、 and Li A La B M’ C M” D Nb E O F (where 4 < A < 8.5, 1.5 < B < 4, 0 ≤ C < 2, 0 ≤ D < 2; 0 < E < 2, 10 < F < 14, and M’ and M” are each independently selected from the group consisting of Al, Mo, W, Nb, Ga, Y, Gd, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta). It is characterized by a formula selected from the group consisting of

[0156]

[0167] In some embodiments including any of the above, Li A La B M’ C M” D Zr E O F Li A La B M’ C M’’ D Ta E O F and Li A La B M’ C M” D Nb E O F (where 4 < A < 8.5, 1.5 < B < 4, 0 ≤ C < 2.5, 0 ≤ D < 2.5; 0 < E < 2.5, 10 < F < 14, and M’ and M” are each independently selected from the group consisting of Al, Mo, W, Nb, Ga, Y, Gd, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta). It is characterized by a formula selected from the group consisting of a lithium-filled garnet

[0157]

[0168] In some embodiments including any of the above, the lithium-filled garnet is Li a La b Zr c Al d Me”<src= e O f(where 5 < a < 7.7; 2 < b < 4; 0 < c < 2.5; 0 < d < 2.5; 0 ≤ e < 2.5, 10 < f < 14, and Me” is a metal selected from the group consisting of Nb, Ta, V, W, Mo, and Sb). It is characterized by a formula selected from the group consisting of

[0158]

[0169] In some embodiments including any of the foregoing, the lithium-filled garnet is Li a La b Zr c Al d O f (where 5 < a < 7.7; 2 < b < 4; 0 < c < 2.5; 0 < d < 2.5; 10 < f < 14). It is characterized by a formula selected from the group consisting of

[0159]

[0170] In some embodiments including any of the foregoing, an electrochemical cell including the catholite described herein is described herein.

[0160]

[0171] In some embodiments including any of the foregoing, a storage battery including the electrochemical cell described herein is described herein.

[0161]

[0172] In some embodiments including any of the foregoing, an electric vehicle including the storage battery described herein is described herein.

[0162]

[0173] In certain embodiments including any of the foregoing, the substitution is selected from polyethylene glycol (PEG), =O, SO2, -CF3, -CH2F, CHF2, -NO2, -NO3, -NH3, -CH3, PO4, PO3, BO3, and -CN.

[0163] Manufacturing method

[0174] In another example, a method for manufacturing an electrochemical cell, comprising: providing catholite in a positive electrode, wherein the catholite is a lithium salt and; each independently, in each case, at least two Cs containing at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents 3-10and contacting the positive electrode with a solid electrolyte comprising a lithium-loaded garnet.

[0164]

[0175] In another example, a method for preparing a catholyte solution includes independently adding at least two C groups, each group containing at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents. 3-10 A method of preparation is provided herein that includes mixing a heterocyclic molecule with a lithium salt, thereby obtaining a catholyte solution.

[0165]

[0176] In some embodiments, including any of the foregoing, the method further comprises contacting a solid electrolyte comprising a lithium-loaded garnet with the catholyte solution.

[0166]

[0177] In some embodiments, including any of the foregoing, described herein are electrochemical cells produced by the methods described herein.

[0167]

[0178] In some embodiments, including any of the foregoing, described herein are batteries that include the electrochemical cells described herein.

[0168]

[0179] In some embodiments, including any of the foregoing, described herein is an electric vehicle that includes a battery as described herein.

[0169]

[0180] In some embodiments, including any of the foregoing, methods for making catholytes are described herein. In some embodiments, a 70:30 ES:S mixture is prepared from a 50:50 ethylene sulfite:sulfolane by volume. In some embodiments, a 40:60 ethylene sulfite:sulfolane by volume mixture is prepared. In some embodiments, a 60:40 ethylene sulfite:sulfolane ES:S mixture is prepared by volume. In some embodiments, an 80:20 ethylene sulfite:sulfolane by volume mixture is prepared. In some embodiments, a 20:80 ethylene sulfite:sulfolane by volume mixture is prepared.

[0170]

[0181] In some embodiments, including any of the foregoing, propylene glycol sulfite is used in place of ethylene sulfite.

[0171]

[0182] In some embodiments, including any of the foregoing, another additive is used, such as TTSPi (tristrimethylsilyl phosphite).

[0172]

[0183] After drying, lithium salt is added at a salt concentration of 0.8M to 2M.

[0173]

[0184] In some embodiments, including any of the foregoing, the salt is selected from the group consisting of LiPF, lithium bis(oxalato)borate (LiBOB), lithium bis(perfluoroethanesulfonyl)imide (LIBETI), bis(trifluoromethane)sulfonimide (LiTFSI), LiBF, LiClO, LiAsF, lithium bis(fluorosulfonyl)imide (LiFSI), LiI, and combinations thereof.

[0174]

[0185] In some embodiments, including any of the foregoing, the salt is LiPF6 or LiBF4.

[0175]

[0186] In some embodiments, including any of the foregoing, the salt is LiPF6.

[0176]

[0187] In some embodiments, including any of the foregoing, the salt is LiBF4.

[0177]

[0188] In some embodiments, including any of the foregoing, other anion mixtures are used, such as, but not limited to, LiFSi, LiTFSi, e.g., 1.4M Li and 80:20 LiBF to LiFSi.

[0178]

[0189] In some embodiments, including any of the foregoing, 1,2-propylene glycol sulfite (CAS 1469-73-4) is used as an additive with the ESS.

[0179]

[0190] In some embodiments, including any of the foregoing, 1,3,2-dioxathiolane 2,2-dioxide (CAS 1072-53-3) is used as an additive with the ESS.

[0180]

[0191] In some embodiments, including any of the foregoing, C 3-10 A heterocyclic molecule contains at least one sulfur (S) ring atom.

[0181]

[0192] In some embodiments, including any of the foregoing, C 3-10 A heterocyclic molecule contains at least one sulfur (S) ring atom and one oxygen (O) ring atom.

[0182]

[0193] In some embodiments, a lithium salt and at least two aprotic C rings, each independently in each instance, containing at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents. 3-10 A catholyte solution containing heterocyclic molecules; and at least one C 3-101,4-thiazepine; 6-H-1,2,5-thiadiazine; 2H,6H-1,5,2-dithiazine; methylenemethane disulfonate; ethylene sulfate; thiopyran; thiocin, derivatives thereof, and combinations thereof.

[0183]

[0194] In some embodiments, including any of the foregoing, at least one aprotic C 3-10 The heterocyclic molecule is selected from the group consisting of ethylene sulfite and propylene glycol sulfite.

[0184]

[0195] In some embodiments, including any of the foregoing, the catholyte solution contacts a solid electrolyte comprising a lithium-loaded garnet, wherein the solid electrolyte is a thin film.

[0185]

[0196] In some embodiments, including any of the foregoing, the solid electrolyte comprising the lithium-filled garnet is a sintered thin film.

[0186]

[0197] In some embodiments, including any of the foregoing, the lithium salt is selected from the group consisting of LiPF, lithium bis(oxalato)borate (LiBOB), lithium bis(perfluoroethanesulfonyl)imide (LIBETI), bis(trifluoromethane)sulfonimide (LiTFSI), LiBF, LiClO, LiAsF, lithium bis(fluorosulfonyl)imide (LiFSI), LiI, and combinations thereof.

[0187]

[0198] In some embodiments, including any of the foregoing, the lithium salt is present in a concentration of about 0.5M to about 2.0M.

[0188]

[0199] In some embodiments, including any of the foregoing, at least one C 3-10The heterocyclic molecule is sulfolane.

[0189]

[0200] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is 1,3-propane sultone.

[0190]

[0201] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is sulfolene.

[0191]

[0202] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is a thiophene.

[0192]

[0203] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is ethylene sulfite.

[0193]

[0204] In some embodiments, including any of the foregoing, the catholyte solution comprises two C 3-10 Heterocyclic molecules include one C 3-10 The other C of the heterocyclic molecule 3-10 The ratio for heterocyclic molecules is 10:90 vol / vol (v / v) to 90:10 v / v.

[0194]

[0205] In some embodiments, including any of the foregoing, the catholyte solution comprises two C 3-10 Heterocyclic molecules include one C 3-10 The other C of the heterocyclic molecule 3-10 The ratio for heterocyclic molecules is 20:80 vol / vol (v / v) to 80:20 v / v.

[0195]

[0206] In some embodiments, including any of the foregoing, the catholyte solution comprises sulfolane and ethylene sulfite, wherein the ratio of sulfolane:(ethylene sulfite) is from 30:70 v / v to 50:50 v / v.

[0196]

[0207] In some embodiments, including any of the foregoing, the catholyte solution comprises sulfolane and ethylene sulfite, wherein the ratio of sulfolane:(ethylene sulfite) is 30:70 v / v.

[0197]

[0208] In some embodiments, including any of the foregoing, the catholyte solution comprises sulfolane and ethylene sulfite, wherein the ratio of sulfolane:(ethylene sulfite) is 50:50 v / v.

[0198]

[0209] In some embodiments, including any of the foregoing, the catholyte solution may comprise any of the following: tris(trimethysilyl) phosphite (TTSPi); tris(trimethysilyl) phosphate (TTSPa); trimethoxyboroxine (C3H9B3O6, TMOBX); vinylene carbonate (VC); vinylethylene carbonate (VEC); methylenemethane disulfonate (MMDS); prop-1-ene-1,3 sultone (PES); 1,3-propane sultone; fluoroethylene carbonate (FEC); LiTFSi; LiBOB; succinonitrile, trimethylene sulfate (TMS); triphosphate The Lewis acid is selected from the group consisting of allyl (TAP); tris(trimethylsilyl)borate (TMSB); tris(pentafluorophenyl)borane (TPFPB); tris(pentafluorophenyl)borane (TPFPB); methyl acetate (MA); tris(trimethylsilyl) acetate (TMSA); tris(trimethylsilyl)pyridine; tris(trimethylsilyl) methacrylate (TMSMA); tris(2,2,2-trifluoroethyl)phosphite (TTFEP); tris(2,2,2-trifluoroethyl)borate (TTFEB); and combinations thereof.

[0199]

[0210] In some embodiments, including any of the foregoing, the additive is a TTSPi.

[0200]

[0211] In some embodiments, including any of the foregoing, the additive is TTSPa.

[0201]

[0212] In some embodiments including any of the foregoing, the additive is a combination of TTSPi and TTSPa.

[0202]

[0213] In some embodiments including any of the foregoing, the solid electrolyte is Li A La B M’ C M” D Zr E O F 、Li A La B M’ C M’’ D Ta E O F 、及びLi A La B M’ C M” D Nb E O F (where 4 < A < 8.5, 1.5 < B < 4, 0 ≤ C < 2.5, 0 ≤ D < 2.5; 0 < E < 2.5, 10 < F < 14, and M’ and M” are each independently selected from the group consisting of Al, Mo, W, Nb, Ga, Y, Gd, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta) and is a lithium-filled garnet characterized by a formula selected from the group consisting of.

[0203]

[0214] In some embodiments including any of the foregoing, the catholyte solution has a boiling point within the range of 60°C to 100°C.

[0204]

[0215] In some embodiments including any of the foregoing, the catholyte solution has a melting point within the range of -60°C to -40°C.

[0205]

[0216] In some embodiments including any of the foregoing, the catholyte solution has a lithium ion conductivity within the range of 2000 μS / cm to 3200 μS / cm.

[0206]

[0217] In some embodiments including any of the foregoing, the catholyte solution has a viscosity within the range of 1 centipoise (cP) to 10 cP.

[0207]

[0218] In some embodiments, including any of the foregoing, the lithium salt is 1.4 M LiPF6; 1.4 M LiBF4; or 1.6 M LiBF4.

[0208]

[0219] In some embodiments, including any of the foregoing, the catholyte solution comprises 70:30 v / v% ethylene sulfite:sulfolane.

[0209] Further embodiments

[0220] In some embodiments, a lithium salt and at least two aprotic C rings, each independently in each instance, containing at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents. 3-10 Described herein are catholyte solutions that include heterocyclic molecules.

[0210]

[0221] In some embodiments, a lithium salt and an aprotic C 3-10 Described herein are catholyte solutions that include heterocyclic molecules.

[0211]

[0222] In some embodiments, including any of the foregoing, the catholyte comprises an organic carbonate solvent.

[0212]

[0223] In some embodiments, including any of the foregoing, the catholyte comprises ethylene carbonate.

[0213]

[0224] In some embodiments, including any of the foregoing, the catholyte comprises diethyl carbonate, dimethyl carbonate, or a combination thereof.

[0214]

[0225] In some embodiments, including any of the foregoing, the catholyte comprises methyl acetate.

[0215]

[0226] In some embodiments, including any of the foregoing, the catholyte comprises at least one aprotic C 3-10The heterocyclic molecule is selected from the group consisting of ethylene sulfite; 4-methyl-1,3,2-dioxathiolane 2-oxide; 1,3-propane sultone; sulfolane; thiophene, thiazole, 1,2-oxathiolane, thiepine, 1,4-thiazepine, 6-H-1,2,5-thiadiazine, 2H,6H-1,5,2-dithiazine; methylenemethane disulfonate; ethylene sulfate; thiopyran, thiepine, thiocin, derivatives thereof, and combinations thereof.

[0216]

[0227] In some embodiments, including any of the foregoing, the catholyte comprises at least one aprotic C 3-10 It comprises a heterocyclic molecule and is selected from the group consisting of ethylene sulfite and propylene glycol sulfite.

[0217]

[0228] In some embodiments, including any of the foregoing, the catholyte comprises at least one aprotic C 3-10 It comprises a heterocyclic molecule and is selected from the group consisting of ethylene sulfite and sulfolane.

[0218]

[0229] In some embodiments, including any of the foregoing, the catholyte is in contact with a solid electrolyte comprising a lithium-loaded garnet, and the solid electrolyte is a thin film.

[0219]

[0230] In some embodiments, including any of the foregoing, the solid electrolyte comprising the lithium-filled garnet is a sintered thin film.

[0220]

[0231] In some embodiments, including any of the foregoing, the lithium salt is selected from the group consisting of LiPF, lithium bis(oxalato)borate (LiBOB), lithium bis(perfluoroethanesulfonyl)imide (LIBETI), bis(trifluoromethane)sulfonimide (LiTFSI), LiBF, LiClO, LiAsF, lithium bis(fluorosulfonyl)imide (LiFSI), LiI, LiBr, LiCl, and combinations thereof.

[0221]

[0232] In some embodiments, including any of the foregoing, the lithium salt is present at a concentration of about 0.5M to about 5.0M.

[0222]

[0233] In some embodiments, including any of the foregoing, the lithium salt is LiPF6; LiBF4; or LiBF4.

[0223]

[0234] In some embodiments, including any of the foregoing, the lithium salt is 1.4 M LiPF6; 1.4 M LiBF4; or 1.6 M LiBF4.

[0224]

[0235] In some embodiments, including any of the foregoing, the lithium salt is LiBF4.

[0225]

[0236] In some embodiments, including any of the foregoing, the lithium salt is 1.4 M LiBF4 or 1.6 M LiBF4.

[0226]

[0237] In some embodiments, including any of the foregoing, the catholyte comprises 70:30 v / v% ethylene sulfite:sulfolane.

[0227]

[0238] In some embodiments, including any of the foregoing, at least one aprotic C 3-10 The heterocyclic molecule is sulfolane.

[0228]

[0239] In some embodiments, including any of the foregoing, at least one aprotic C 3-10 The heterocyclic molecule is 1,3-propane sultone.

[0229]

[0240] In some embodiments, including any of the foregoing, at least one aprotic C 3-10 The heterocyclic molecule is sulfolene.

[0230]

[0241] In some embodiments, including any of the foregoing, at least one aprotic C 3-10 The heterocyclic molecule is a thiophene.

[0231]

[0242] In some embodiments, including any of the foregoing, at least one aprotic C 3-10 The heterocyclic molecule is ethylene sulfite.

[0232]

[0243] In some embodiments, including any of the foregoing, the catholyte comprises ethylene sulfite and sulfolane.

[0233]

[0244] In some embodiments, including any of the foregoing, the catholyte consists essentially of ethylene sulfite and sulfolane.

[0234]

[0245] In some embodiments, including any of the foregoing, the catholyte comprises two C 3-10 Heterocyclic molecules include one C 3-10 The other C of the heterocyclic molecule 3-10 The ratio for heterocyclic molecules is 10:90 vol / vol (v / v) to 90:10 v / v.

[0235]

[0246] In some embodiments, including any of the foregoing, the catholyte comprises two C 3-10 Heterocyclic molecules include one C 3-10 The other C of the heterocyclic molecule 3-10 The ratio for heterocyclic molecules is 20:80 vol / vol (v / v) to 80:20 v / v.

[0236]

[0247] In some embodiments, including any of the foregoing, catholyte is included and the ratio is 30:70 vol / vol (v / v).

[0237]

[0248] In some embodiments, including any of the foregoing, the catholyte comprises sulfolane:ethylene sulfite at 30:70 v / v.

[0238]

[0249] In some embodiments, including any of the foregoing, the catholyte comprises sulfolane and ethylene sulfite, wherein the ratio of sulfolane:(ethylene sulfite) is from 30:70 v / v to 50:50 v / v.

[0239]

[0250] In some embodiments, including any of the foregoing, the catholyte comprises sulfolane and ethylene sulfite, wherein the ratio of sulfolane:(ethylene sulfite) is 30:70 v / v.

[0240]

[0251] In some embodiments, including any of the foregoing, the catholyte comprises sulfolane and ethylene sulfite, wherein the ratio of sulfolane:(ethylene sulfite) is 50:50 v / v.

[0241]

[0252] In some embodiments, including any of the foregoing, the catholyte comprises sulfolane and ethylene sulfite, and the concentration of the lithium salt is from 0.5 molar (M) to 5M.

[0242]

[0253] In some embodiments, including any of the foregoing, the catholyte comprises sulfolane and ethylene sulfite, and the concentration of LiBF4 is between 0.5 molar (M) and 5M.

[0243]

[0254] In some embodiments, including any of the foregoing, the catholyte is selected from the group consisting of tris(trimethysilyl) phosphite (TTSPi); tris(trimethysilyl) phosphate; trimethoxyboroxine (C3H9B3O6, TMOBX); vinylene carbonate (VC); vinylethylene carbonate (VEC); methylenemethane disulfonate (MMDS); prop-1-ene-1,3 sultone (PES); 1,3-propane sultone; fluoroethylene carbonate (FEC); LiTFSi; LiBOB; succinonitrile; trimethylene sulfate (TMS); triallyl phosphate (TAP); tris borate tris(trimethylsilyl) (TMSB); tris(pentafluorophenyl)borane (TPFPB); tris(trimethylsilyl) borate (TMSB); tris(pentafluorophenyl)borane (TPFPB); methyl acetate (MA); tris(trimethylsilyl) acetate (TMSA); tris(trimethylsilyl)pyridine; tris(trimethylsilyl) methacrylate (TMSMA); tris(2,2,2-trifluoroethyl) phosphite (TTFEP); tris(2,2,2-trifluoroethyl) borate (TTFEB), and combinations thereof.

[0244]

[0255] In some embodiments, including any of the foregoing, the additive is a TTSPi.

[0245]

[0256] In some embodiments, including any of the foregoing, the additive is TTSPa.

[0246]

[0257] In some embodiments, including any of the foregoing, the additive is a combination of TTSPi and TTSPa.

[0247]

[0258] In some embodiments, including any of the foregoing, the solid electrolyte is Li A La B M' C M” D Zr E O F , Li A La B M' C M''D Ta E O F and Li A La B M’ C M” D Nb E O F (where 4 < A < 8.5, 1.5 < B < 4, 0 ≤ C < 2.5, 0 ≤ D < 2.5; 0 < E < 2.5, 10 < F < 14, and M’ and M” are each independently selected from the group consisting of Al, Mo, W, Nb, Ga, Y, Gd, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta) and is a lithium-filled garnet characterized by a formula selected from the group consisting of.

[0248]

[0259] In some embodiments including any of the foregoing, the lithium-filled garnet is Li a La b Zr c Al d Me” e O f (5 < a < 7.7; 2 < b < 4; 0 < c < 2.5; 0 < d < 2.5; 0 ≤ e < 2.5, 10 < f < 14, and Me” is a metal selected from the group consisting of Nb, Ta, V, W, Mo, and Sb) and is characterized by a formula selected from the group consisting of.

[0249]

[0260] In some embodiments including any of the foregoing, the lithium-filled garnet is Li a La b Zr c Al d O f (where 5 < a < 7.7; 2 < b < 4; 0 < c < 2.5; 0 < d < 2.5; 10 < f < 14) and is characterized by a formula selected from the group consisting of.

[0250]

[0261] [[ID=5ed=54]] In some embodiments including any of the foregoing, the catholite solution is disposed in an electrochemical cell including a positive electrode, a lithium metal negative electrode, and a solid electrolyte including a lithium-filled garnet.

[0251]

[0262] In some embodiments, including any of the foregoing, the catholyte comprises an aprotic C 12 hydroxybenzoate containing at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents. 3-10 It contains a third component that is not a heterocyclic molecule.

[0252]

[0263] In some embodiments, including any of the foregoing, the third component is selected from the group consisting of gamma butyrolactone, gamma valerolactone, gamma octalactone, ethyl cyanoacetate, trimethyl phosphate, adiponitrile, glutaronitrile, malononitrile, methyl acetate, ethyl cyanoacrylate, malononitrile, methyl cyanoacetate, ethyl cyanoacrylate, methyl cyanoacrylate, methoxyacetonitrile, acetonitrile, succinonitrile, malononitrile, methyl cyanoacetate, ethyl cyanoacrylate, methyl cyanoacrylate, and combinations thereof.

[0253]

[0264] In some embodiments, including any of the foregoing, the third component is methyl acetate.

[0254]

[0265] In some embodiments, a method for preparing a catholyte solution includes independently selecting at least two C groups, each group containing at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents. 3-10 A method of preparation is described herein that involves mixing a heterocyclic molecule with a lithium salt, thereby obtaining a catholyte solution.

[0255]

[0266] In some embodiments, including any of the foregoing, the method includes contacting a solid electrolyte including a lithium-loaded garnet with a catholyte solution.

[0256]

[0267] In some embodiments, a method for manufacturing an electrochemical cell includes: providing a catholyte in a positive electrode, the catholyte comprising: a lithium salt; and at least two C groups, each independently, in each instance containing at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents. 3-10and contacting the positive electrode with a solid electrolyte comprising a lithium-loaded garnet.

[0257]

[0268] In some embodiments, described herein are electrochemical cells fabricated by the methods disclosed herein.

[0258]

[0269] In some embodiments, described herein are batteries that include the electrochemical cells disclosed herein.

[0259]

[0270] In some embodiments, described herein are electric vehicles that include the batteries disclosed herein.

[0260]

[0271] In some embodiments, a lithium salt and at least two aprotic C rings, each independently in each instance, containing at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents. 3-10 A catholyte solution containing heterocyclic molecules; and at least one C 3-10 1,4-thiazepine; 6-H-1,2,5-thiadiazine; 2H,6H-1,5,2-dithiazine; methylenemethane disulfonate; ethylene sulfate; thiopyran; thiocin, derivatives thereof, and combinations thereof.

[0261]

[0272] In some embodiments, including any of the foregoing, at least one aprotic C 3-10 The heterocyclic molecule is selected from the group consisting of ethylene sulfite and propylene glycol sulfite.

[0262]

[0273] In some embodiments, including any of the foregoing, the catholyte solution contacts a solid electrolyte comprising a lithium-loaded garnet, and the solid electrolyte is a thin film.

[0263]

[0274] In some embodiments, including any of the foregoing, the solid electrolyte comprising the lithium-filled garnet is a sintered thin film.

[0264]

[0275] In some embodiments, including any of the foregoing, the lithium salt is selected from the group consisting of LiPF, lithium bis(oxalato)borate (LiBOB), lithium bis(perfluoroethanesulfonyl)imide (LIBETI), bis(trifluoromethane)sulfonimide (LiTFSI), LiBF, LiClO, LiAsF, lithium bis(fluorosulfonyl)imide (LiFSI), LiF, LiCl, LiBr, LiI, and combinations thereof.

[0265]

[0276] In some embodiments, including any of the foregoing, the lithium salt is LiBF4.

[0266]

[0277] In some embodiments, including any of the foregoing, the lithium salt is present in a concentration of about 0.5M to about 2.0M.

[0267]

[0278] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is sulfolane.

[0268]

[0279] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is 1,3-propane sultone.

[0269]

[0280] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is sulfolene.

[0270]

[0281] In some embodiments, including any of the foregoing, at least one C3-10 The heterocyclic molecule is a thiophene.

[0271]

[0282] In some embodiments, including any of the foregoing, at least one C 3-10 The heterocyclic molecule is ethylene sulfite.

[0272]

[0283] In some embodiments, including any of the above, one C 3-10 The other C of the heterocyclic molecule 3-10 The ratio for heterocyclic molecules is 10:90 vol / vol (v / v) to 90:10 v / v.

[0273]

[0284] In some embodiments, including any of the above, one C 3-10 The other C of the heterocyclic molecule 3-10 The ratio for heterocyclic molecules is 20:80 vol / vol (v / v) to 80:20 v / v.

[0274]

[0285] In some embodiments, including any of the foregoing, the catholyte comprises sulfolane and ethylene sulfite, wherein the ratio of sulfolane:(ethylene sulfite) is from 30:70 v / v to 50:50 v / v.

[0275]

[0286] In some embodiments, including any of the foregoing, the catholyte comprises sulfolane and ethylene sulfite, wherein the ratio of sulfolane:(ethylene sulfite) is 30:70 v / v.

[0276]

[0287] In some embodiments, including any of the foregoing, the catholyte comprises sulfolane and ethylene sulfite, wherein the ratio of sulfolane:(ethylene sulfite) is 50:50 v / v.

[0277]

[0288] In some embodiments, including any of the foregoing, the catholyte is selected from the group consisting of tris(trimethysilyl) phosphite (TTSPi); tris(trimethysilyl) phosphate (TTSPa); trimethoxyboroxine (C3H9B3O6, TMOBX); vinylene carbonate (VC); vinylethylene carbonate (VEC); methylenemethane disulfonate (MMDS); prop-1-ene-1,3 sultone (PES); 1,3-propane sultone; fluoroethylene carbonate (FEC); LiTFSi; LiBOB; succinonitrile, trimethylene sulfate (TMS); trimethylsilyl phosphate tris(pentafluorophenyl)borane (TPFPB); tris(pentafluorophenyl)borane (TPFPB); methyl acetate (MA); tris(trimethylsilyl) acetate (TMSA); tris(trimethylsilyl)pyridine; tris(trimethylsilyl) methacrylate (TMSMA); tris(2,2,2-trifluoroethyl) phosphite (TTFEP); tris(2,2,2-trifluoroethyl)borate (TTFEB); and combinations thereof.

[0278]

[0289] In some embodiments, including any of the foregoing, the additive is a TTSPi.

[0279]

[0290] In some embodiments, including any of the foregoing, the additive is TTSPa.

[0280]

[0291] In some embodiments, including any of the foregoing, the additive is a combination of TTSPi and TTSPa.

[0281]

[0292] In some embodiments, including any of the foregoing, the solid electrolyte is Li A La B M' C M” D Zr E O F , Li A La B M' C M'' D TaE O F 、 and Li A La B M’ C M” D Nb E O F (where 4 < A < 8.5, 1.5 < B < 4, 0 ≦ C < 2.5, 0 ≦ D < 2.5; 0 < E < 2.5, 10 < F < 14, and M’ and M” are each independently selected from the group consisting of Al, Mo, W, Nb, Ga, Y, Gd, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta) and is a lithium-filled garnet characterized by a formula selected from the group consisting of.

[0282]

[0293] In some embodiments including any of the foregoing, the catholite solution has a boiling point within the range of 60°C to 100°C.

[0283]

[0294] In some embodiments including any of the foregoing, the catholite solution has a melting point within the range of -60°C to -40°C.

[0284]

[0295] In some embodiments including any of the foregoing, the catholite solution has a lithium ion conductivity within the range of 2000 μS / cm to 3200 μS / cm.

[0285]

[0296] In some embodiments including any of the foregoing, the catholite solution has a viscosity within the range of 1 cP to 10 cP.

[0286]

[0297] In some embodiments including any of the foregoing, the lithium salt is 1.4 M LiPF6; 1.4 M LiBF4; or 1.6 M LiBF4.

[0287]

[0298] In some embodiments including any of the foregoing, the catholite contains 70:30 v / v% ethylene sulfite: sulfolane.

[0288]

[0299] In some embodiments including any of the foregoing, the lithium salt is 1.4 M LiPF6.

[0289]

[0300] In some embodiments, including any of the foregoing, the lithium salt is 1.4 M LiBF4.

[0290]

[0301] In some embodiments, including any of the foregoing, the lithium salt is 1.6 M LiBF4. [Example]

[0291] Example

[0302] The equipment used for the electrochemical measurements was a potentiostat manufactured by Bio-Logic, a battery cycler manufactured by Arbin Instruments, and a battery cycler manufactured by Maccor.

[0292]

[0303] Unless stated to the contrary, reagents, chemicals, and materials were purchased commercially.

[0293]

[0304] Pouch cell containers were purchased from Showa Denko.

[0294]

[0305] The electrochemical potentiostat used was an Arbin potentiostat.

[0295]

[0306] Electrical impedance spectroscopy (EIS) was performed using a Biologic VMP3, VSP, VSP-300, SP-150, or SP-200.

[0296]

[0307] Mixing was performed using a Fischer Scientific vortex mixer, a Flaktek speed mixer, or a Primix filmix homogenizer.

[0297]

[0308] Casting was carried out on a TQC drawdown table. Calendering was carried out on an IMC calender.

[0298]

[0309] Light scattering was performed on a laser scattering particle size distribution analyzer, Horiba, Model: Partica, Model Number: LA-950V2.

[0299]

[0310] Unless otherwise specified, the lithium nickel cobalt manganese oxide (NMC) used in the examples is LiNi 0.8 Co 0.1 Mn 0.1 It was O2.

[0300] Example 1: Low temperature output

[0311] 3% Super C65, 1% Ketjenblack, 5% Kynar HSV, and 91% by weight LiNi 0.8 Co 0.1 Mn 0.1 A cathode electrode slurry was prepared by mixing O2 (also known as NMC811) in N-methylpyrrolidone (NMP). After mixing and degassing, 28 mg / cm 2 The slurry was cast onto aluminum foil using a doctor blade to a thickness that would yield a dry material of 1000 .mu.m. The electrode was dried in NMP at 120°C for 8 hours. The electrode was calendered to a thickness that resulted in a porosity of 35% by volume as measured by scanning electron microscopy. 8 mm diameter cathode electrode disks were punched from the cathode electrode sheet.

[0301]

[0312] An electrochemical cell was assembled using a lithium-loaded garnet separator, a lithium-free lithium metal anode, and the above-described cathode electrode. "Lithium-free" refers to the cell assembled in a discharged state. Prior to cell assembly, the cathode electrode was immersed in an ESS catholyte mixture (70:30 v / v% ethylene sulfite:sulfolane + 1.4 M LiBF4). Here, "ESS" refers to the combination of ethylene sulfite and sulfolane. After immersion, excess electrolyte was removed by dabbing, and then 0.5–3 μL of excess catholyte mixture was pipetted onto the cathode-separator interface. An anode current collector foil with a tab was placed in contact with the anode side of the separator, and a cathode current collector foil with a tab was placed in contact with the Al foil on the backside of the cathode electrode. A pouch was sealed around the cell, allowing the tabs to protrude from the cell to form electrical connections to each electrode.

[0302]

[0313] The electrochemical cell was charged and discharged at a C / 10 rate, which is the current required to charge (or discharge) the battery from 3.4 V to 4.4 V in 10 hours at 25°C. Figure 1 shows the results of a low-temperature power test. The cell was charged to 4.4 V at 25°C and then cooled to -30°C. The cell was discharged for 30 seconds by applying a constant voltage of 2 V, and the current was monitored during that 30-second period. After 30 seconds, the cell was allowed to rest for 10 minutes at open circuit, and then a C / 10 discharge current was applied for 6 minutes. The 2 V discharge, rest, and C / 10 discharge cycles were repeated until the cell voltage dropped below 2 V during the C / 10 discharge step. Figure 1 shows the C-rate obtained during the 2 V fast discharge as a function of the state of charge. The cell was capable of delivering a current of over 1 C for 30 seconds at -30°C when the state of charge was greater than approximately 60%, and a current of over 0.5 C for 30 seconds when the state of charge was greater than approximately 10%. 1C is the current that discharges (or charges) a battery in 1 hour. 0.5C is the current that discharges (or charges) a battery in 2 hours.

[0303] Example 2: Fast charging

[0314] Electrochemical cells were assembled and fabricated as described in Example 1. The cells were heated to 25°C and a 4C charging current was applied until the cell reached 4.4V, at which point a constant voltage of 4.4V was applied until the current fell below C / 20 or until 15 minutes had elapsed, whichever came first. Figure 2 shows the state of charge plotted against time; the cell was charged from 0 to 80% state of charge (SOC) in 12.5 minutes. In Figure 2, "ESS7.4" represents a 1.4M Li + "ESS+1.6M LiBF4" is synonymous with a 70:30 v / v mixture of ethylene sulfite and sulfolane with a concentration of 1.6M Li + It is a 70:30 v / v mixture of ethylene sulfite and sulfolane having a concentration of

[0304]

[0315] Figure 4 shows a comparison of the charge rates of cells with three different catholytes: a 45:55 mixture of ethylene carbonate:sulfolane with 1.4 M LiPF (ECS), denoted ECS45.4; a 70:30 mixture of ethylene sulfite:sulfolane with 1.6 M LiBF (ESS1); and a 70:30 mixture of ethylene sulfite:sulfolane with 1.4 M LiPF (ESS2). Cells with ESS1 and ESS2 catholytes could be charged from 0 to 80% state of charge in 12–15 minutes, while cells with ECS charged in 15–20 minutes.

[0305]

[0316] Further electrochemical cells were assembled and formed as described in Example 1. The cells were brought to 25°C and a 4C charging current was applied until the cells reached 4.4V, at which point a constant voltage of 4.4V was applied until the current fell below C / 20 or until 15 minutes had elapsed, whichever occurred first.

[0306]

[0317] Figure 9 shows a comparison of the charge rates of cells containing two catholytes: a 70:30 volumetric mixture of ethylene sulfite:sulfolane and 1.4M LiBF4 and a 50:50 volumetric mixture of ethylene sulfite:sulfolane and 1.4M LiBF4. The cell containing the 70:30 volumetric mixture of ethylene sulfite:sulfolane and 1.4M LiBF4 catholyte charged from 0 to 80% state of charge in 15-22 minutes, while the cell containing the 50:50 volumetric mixture of ethylene sulfite:sulfolane and 1.4M LiBF4 charged in 23-30 minutes. The ratio of ethylene sulfite to sulfolane is indicated on the x-axis; for example, "70-30" in 70-30 ESS refers to a 70:30 volumetric ratio of ethylene sulfite to sulfolane. The "50-50" in 50-50 ESS refers to a 50:50 volume ratio of ethylene sulfite to sulfolane.

[0307]

[0318] Figure 10 shows a comparison of the charge rates of cells with different catholytes indicated on the x-axis. These results are described in Example 2 herein. The ratio of ethylene sulfite to sulfolane is indicated in the legend on the x-axis; for example, "70-30" in 70-30 ESS refers to a 70:30 volume ratio of ethylene sulfite to sulfolane. "70-30" in 70-30MA-S refers to a 70:30 volume ratio of methyl acetate to sulfolane.

[0308]

[0319] Figure 11 shows a comparison of the charge rates of cells with different catholytes shown on the x-axis. In "70-30 ESS + 1.2M 10% LiFSi," "1.2M" represents the amount of Li in the LiFSi solution. + The concentrations are shown. "10%" means that the catholyte contained 10% by volume of LiFSi solution and 90% by volume of the aforementioned 70-30 ESS 1.4 M LiBF solution. "70-30 ESS + 1.2M 10% LiFSi" is a mixture containing 90% by volume of a 70-30 v / v solution of ethylene sulfite and sulfolane. "70-30 ESS + 1.2M 10% LiFSi" is a mixture containing 10% by volume of a 1.2 M LiFSi solution.

[0309] Example 3: Calender life

[0320] Cells were fabricated and formed according to Example 1. The cells were charged and discharged between 3.4 and 4.4 V at a C / 3 rate to measure the initial ASR (area specific resistance), and then charged to 4.4 V at C / 3. C / 3 is the current at which a battery is charged or discharged in 3 hours. The cells were maintained at open circuit voltage for 7 days in a 60°C chamber and then discharged to 3.4 V at a C / 3 rate at 25°C. The cells were then charged and discharged between 3.4 and 4.4 V at a C / 3 rate at 25°C to measure the final ASR. The initial and final ASR were used as indicators of the cell's calendar life. The cells preferably have a low ASR, with only a small increase in ASR up to the final ASR value.

[0310]

[0321] Ωcm 2 The area specific resistance (ASR) in units of cm is calculated by current interruption technique at a state of charge of around 50% during the charging cycle and multiplied this resistance in ohms by the square root of ... 2 The final ASR was calculated by multiplying the cell area in units of 1 / 2. In this measurement, the cell is observed after the current is turned off (i.e., during relaxation). Figure 3 shows the final ASR for cells with two different catholytes: a 70:30 v / v mixture of ethylene sulfite:sulfolane (ESS, denoted as 70:30 ESI:SLF) and a 45:55 v / v mixture of ethylene carbonate:sulfolane (ECS, denoted as ECS 45.4). As shown in Figure 3, there is a statistically significant difference in the final ASR, with the cell with ESS having a lower final ASR.

[0311]

[0322] Figure 5 shows the discharge capacity of cells with different additive amounts of 0.5%, 1%, 2%, 4%, and 8 wt% ethylene sulfite additive in ECS after 1 week of storage at 60°C. Cells with up to 8% ethylene sulfite exhibit high discharge capacity after storage.

[0312]

[0323] Experiments were conducted to obtain the following data in Table 1 below. Cells were fabricated and formed according to Example 1. The cells were then charged and discharged at a C / 3 rate between 3.4 and 4.35 V to measure the initial ASR (area specific resistance), and then charged to 4.35 V at C / 3. C / 3 is the current at which the battery is charged or discharged in 3 hours. These cells were maintained at open circuit voltage for 7 days in a 60°C chamber and then discharged at a C / 3 rate to 3.4 V at 25°C. The cells were then charged and discharged at a C / 3 rate between 3.4 and 4.35 V at 25°C to measure the ASR for 1 week. An additional 3 weeks of storage at 60°C was performed. A final ASR check was performed at 25°C. All ASR measurements were performed at 25°C. Storage conditions included 4.35 V and 60°C.

[0313] [Table 1]

[0314] [Table 2]

[0315] [Table 3]

[0316] [Table 4]

[0317]

[0324] In Table 1, A is 0 Ω-cm 2 ~59 Ω-cm 2 and B is 60 Ω-cm 2 ~100Ω-cm 2 and C is 60 Ω-cm 2 ~100Ω-cm 2 is.

[0318]

[0325] A one-month ASR study for catholyte molarity skew from 0.5M to 5M is shown in Figure 12, where molarity skew refers to the concentration of LiBF4 salt in a catholyte of 70:30 v / v ethylene sulfite and sulfolane.

[0319]

[0326] Figure 6 shows the charge ASR after 1 week of storage at 60°C with different amounts of ethylene sulfite additive in ECS: 0.5%, 1%, 2%, 4%, and 8% by weight. Cells with up to 8% ethylene sulfite exhibit lower charge ASR after storage.

[0320]

[0327] Figure 7 shows the charge ASR after 1 week of storage at 60°C using two different catholytes: a 70:30 mixture of ethylene sulfite:sulfolane and 1.4 M LiPF (ESS, denoted 1.4 M LiPF / ESS) versus a 45:55 mixture of ethylene carbonate:sulfolane and 1.4 M LiPF (ECS, denoted ECS45.4). The charge ASR is lower for the cells with ESS than for the cells with ECS after storage.

[0321]

[0328] Figure 12 shows the charge ASR after one month of storage at 60°C using three different mixtures: 0.5M LiBF4, 1.4M LiBF4, or a 70:30 mixture of ethylene sulfite and sulfolane with 5M LiBF4. The cells were then charged and discharged at a C / 3 rate between 3.4 and 4.35 V to measure the initial ASR (area-specific resistance). They were then charged to 4.35 V at C / 3. C / 3 is the current at which the battery is charged or discharged over a three-hour period. These cells were maintained at open circuit voltage for seven days in a 60°C chamber and then discharged at a C / 3 rate to 3.4 V at 25°C. The cells were then charged and discharged at a C / 3 rate between 3.4 and 4.35 V at 25°C to measure the ASR for one week. An additional three weeks of storage at 60°C was performed. A final ASR check was performed at 25°C. All ASR measurements were performed at 25°C. Storage conditions included 4.35V and 60°C.

[0322] Example 4

[0329] Cells were fabricated according to Example 1. The cycle life of cells fabricated with ESS (70:30 ethylene sulfite:sulfolane and 1.4M LiPF) and ECS (45:55 ethylene carbonate:sulfolane and 1.4M LiPF) was tested by cycling the cells between 3 and 4.4 V at 45°C at a rate of C / 3. Figure 8 shows that the cycle life of the cell with the ESS catholyte is superior to that of the cell with the ECS catholyte.

[0323] Example 5

[0330] Catholyte solutions were prepared by mixing ethylene sulfite (Sigma Aldrich 774251) and sulfolane (Sigma Aldrich T22209) in various ratios of 4:6 to 8:2 by volume, for example, 1:1 and 7:3.

[0324]

[0331] After mixing the ethylene sulfite and sulfolane, the resulting mixture was dried over molecular sieves until the solution contained less than 10 parts per million (ppm) of HO. The molecular sieves were removed by decanting the mixture.

[0325]

[0332] Lithium salts (LiPF6 or LiBF4) were added at concentrations ranging from 0.8 M to 2 M. The salts were added slowly to reduce the temperature rise.

[0326]

[0333] The above embodiments and examples are intended to be merely illustrative and not limiting. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific compounds, materials, and procedures. All such equivalents are considered to be within the scope and encompassed by the appended claims.

Claims

1. a lithium salt; an aprotic C containing at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents; ３－１０ a heterocyclic molecule, Said C ３－１０ the heterocyclic molecule is ethylene sulfite; The lithium salt is LiPF ６ , lithium bis(oxalato)borate (LiBOB), lithium bis(perfluoroethanesulfonyl)imide (LIBETI), bis(trifluoromethane)sulfonimide (LiTFSI), LiBF ４ , LiClO ４ , LiAsF ６ , lithium bis(fluorosulfonyl)imide (LiFSI), LiF, LiCl, LiBr, LiI, and combinations thereof; the lithium salt is present at a concentration of about 0.5 M to about 5.0 M; Catholyte solution.

2. the catholyte solution contacts a solid electrolyte comprising a lithium-loaded garnet, the solid electrolyte being a thin film; The catholyte solution according to claim 1.

3. the lithium salt is present at a concentration of about 0.5 M to about 2.0 M; The catholyte solution according to claim 1.

4. The lithium salt is LiTFSI, LiBF ４ or a combination thereof, The catholyte solution according to claim 1.

5. The lithium salts are LiTFSI and LiBF ４ It is a combination of The catholyte solution according to claim 4.

6. The lithium salt is LiPF ６ , LiFSI, or a combination thereof; The catholyte solution according to claim 1.

7. The lithium salt is LiPF ６ and LiFSI, The catholyte solution according to claim 6.

8. LiTFSI is present at a concentration of about 0.5 M; The catholyte solution according to claim 4.

9. LiBF ４ is present at a concentration of about 1.2 M to about 1.4 M; The catholyte solution according to claim 4.

10. LiFSI is present at a concentration of about 0.5M; The catholyte solution according to claim 6.

11. LiPF ６ is present at a concentration of about 1.2 M to about 1.4 M; The catholyte solution according to claim 6.

12. further comprising 1,3-propane sultone; The catholyte solution according to claim 1.

13. further comprising thiophene; The catholyte solution according to claim 1.

14. Tris(trimethysilyl) phosphite (TTSPi); Tris(trimethysilyl) phosphate (TTSPa); Trimethoxyboroxine (C ３ H ９ B ３ O ６ ); vinylene carbonate (VC); vinylethylene carbonate (VEC); methylenemethane disulfonate (MMDS); prop-1-ene-1,3 sultone (PES); 1,3-propane sultone; fluoroethylene carbonate (FEC); LiTFSi; LiBOB; succinonitrile; trimethylene sulfate (TMS); triallyl phosphate tris(trimethylsilyl) methacrylate (TMSMA); tris(2,2,2-trifluoroethyl) phosphite (TTFEP); tris(2,2,2-trifluoroethyl) borate (TTFEB), and combinations thereof. The catholyte solution according to claim 1.

15. The additive is a TTSPi.

15. The catholyte solution of claim 14.

16. The additive is TTSPa.

15. The catholyte solution of claim 14.

17. The additive is TTFEP.

15. The catholyte solution of claim 14.

18. The solid electrolyte is Li Ａ La Ｂ M' Ｃ M” Ｄ Zr Ｅ O Ｆ , Li Ａ La Ｂ M' Ｃ M” Ｄ Ta Ｅ O Ｆ , and Li Ａ La Ｂ M' Ｃ M” Ｄ Nb Ｅ O Ｆ wherein 4<A<8.5, 1.5<B<4, 0≦C<2.5, 0≦D<2.5; 0<E<2.5, 10<F<14; and M′ and M″ are each independently selected from the group consisting of Al, Mo, W, Nb, Ga, Y, Gd, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta. The catholyte solution according to claim 2.

19. 3. An electrochemical cell comprising the catholyte solution of claim 2.

20. A method for producing a catholyte solution, comprising the steps of: an aprotic C containing at least one sulfur (S) ring atom and optionally substituted with 1 to 6 substituents; ３－１０ A heterocyclic molecule, ３－１０ The heterocyclic molecule is ethylene sulfite. ３－１０ a heterocyclic molecule; A lithium salt, wherein the lithium salt is LiPF ６ , lithium bis(oxalato)borate (LiBOB), lithium bis(perfluoroethanesulfonyl)imide (LIBETI), bis(trifluoromethane)sulfonimide (LiTFSI), LiBF ４ , LiClO ４ , LiAsF ６ a lithium salt selected from the group consisting of lithium bis(fluorosulfonyl)imide (LiFSI), LiF, LiCl, LiBr, LiI, and combinations thereof, wherein the lithium salt is present at a concentration of about 0.5 M to about 5.0 M; and mixing the above to obtain the catholyte solution.

Images