Thiocarbonate compositions for lithium-sulfur batteries

Abstract

The present disclosure provides compounds useful as electrolyte materials, and lithium-sulfur batteries containing the same. It is an object of the present disclosure to improve the performance of electrochemical cells by including the disclosed binders, additives, and electrolytes in the electrochemical cells. For example, without wishing to be bound by any theory, the disclosed binders, additives, and electrolytes containing thiocarbonyl functional groups interact with polysulfides in the cell and improve the stability of the SEI when included in an electrochemical cell by effectively reducing the diffusion rate. Thus, the present disclosure provides, among other things, improved performance characteristics (e.g., coulombic efficiency) of electrochemical cells having the disclosed binders, additives, and / or electrolytes containing thiocarbonyl functional groups.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 63 / 344,213, filed May 20, 2022, which is incorporated by reference in its entirety. [Background technology]

[0002] Considerable research is being conducted to develop high energy density, long cycle life, low cost lithium ion batteries, particularly for use in electric vehicles and consumer electronics.

[0003] Sulfur is a low-cost, high-specific-energy material that is a by-product of the oil and gas industry. Sulfur-based battery cathodes have been studied for a long time. As a high-energy-density cathode material, sulfur is expected to eliminate the need for cobalt and nickel in lithium batteries. Cobalt is expensive and toxic, and its mining in certain regions is prone to loose regulation and unethical practices. Nickel has high energy density, but there are long-term nickel supply concerns, which, for example, have recently driven Tesla to move away from nickel-containing batteries (Lambert, Fred, “Elon Musk says Tesla is shifting more electric cars to LFP batteries over nickel supply concerns,” Feb. 26, 2021, Electrek). However, the creation of a practical lithium-sulfur battery has been an elusive goal. Among the many challenges surrounding sulfur cathodes, one of the most serious is the lack of a 8 From Li 2 This is due to the requirement for multi-step conversion to lithium S. Although both sulfur and lithium are highly insoluble, their interconversion leads to the formation of the highly soluble intermediate lithium polysulfide Li. 2 S xIn typical sulfur batteries with liquid electrolytes, the formation and interconversion of lithium polysulfides occurs in the solution phase. Aliphatic carbonates, the workhorse liquid electrolytes for current generation lithium-ion batteries, are not stable in lithium-sulfur systems. This is the main obstacle in the development of sulfur cathodes. Most sulfur systems use polyethers and cyclic ethers as electrolytes because they do not react significantly with sulfide nucleophiles. Unfortunately, ethers interact with the lithium anode and / or do not form a stable SEI (solid electrolyte interface). Therefore, there is a strong need for sulfide-stable electrolytes that are also stable with lithium anodes. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Lambert, Fred, “Elon Musk says Tesla is shifting more electric cars to LFP batteries over nickel supply concerns,” Feb. 26, 2021, Electrek Summary of the Invention

[0005] Provided herein are binders, additives for electrolytes, and compositions and compounds for electrolytes that contain thiocarbonyl functional groups, as well as batteries that include such binders, additives, and electrolytes.

[0006] It is an object of the present disclosure to improve the performance of electrochemical cells by including the disclosed binders, additives, and electrolytes in the electrochemical cells. For example, without wishing to be bound by any theory, the disclosed binders, additives, and electrolytes containing thiocarbonyl functional groups interact with polysulfides in the cell and improve the stability of the SEI when included in an electrochemical cell by effectively reducing the diffusion rate. Thus, the present disclosure provides, among other things, improved performance characteristics (e.g., coulombic efficiency) of electrochemical cells having the disclosed binders, additives, and / or electrolytes containing thiocarbonyl functional groups.

[0007] In one aspect, the present disclosure relates to a binder for a sulfur positive electrode that includes a thiocarbonyl functional group.

[0008] In some embodiments, the binding agent has formula X y The thiocarbonyl functional group C=S, wherein each X is independently selected from oxygen, nitrogen, sulfur, or carbon, and y is 1 or 2, provided that one X may form a ring with the other X and the intervening atom, and when y is 1, X is connected to the thiocarbonyl carbon through a double bond. In some embodiments, y is 2. In some embodiments, each X is independently selected from nitrogen, sulfur, or carbon. In some embodiments, each X is independently selected from sulfur or carbon. In some embodiments, y is 1. In some embodiments, when y is 1, the linking agent comprises an isothiocyanate functional group.

[0009] In some embodiments, the binding agent is not cycled.

[0010] In another aspect, the present disclosure relates to an additive for lithium-sulfur battery electrolytes that includes a thiocarbonyl functional group.

[0011] In some embodiments, the additive has formula X yThe additive comprises a thiocarbonyl functional group of C=S, where each X is independently selected from oxygen, nitrogen, sulfur, or carbon, and y is 1 or 2, provided that one X may form a ring with the other X and the intervening atom, and when y is 1, X is connected to the thiocarbonyl carbon through a double bond. In some embodiments, y is 2. In some embodiments, each X is independently selected from nitrogen, sulfur, or carbon. In some embodiments, each X is independently selected from sulfur or carbon. In some embodiments, Y is 1. In some embodiments, when y is 1, the additive comprises an isothiocyanate functional group.

[0012] In some embodiments, the additive is not cycled.

[0013] In another aspect, the present disclosure relates to a lithium-sulfur battery electrolyte that includes a thiocarbonyl functional group.

[0014] In some embodiments, the electrolyte has formula X y The electrolyte comprises a thiocarbonyl functional group of C=S, where each X is independently selected from oxygen, nitrogen, sulfur, or carbon, and y is 1 or 2, provided that one X may form a ring with the other X and the intervening atom, and when y is 1, X is connected to the thiocarbonyl carbon through a double bond. In some embodiments, y is 2. In some embodiments, each X is independently selected from nitrogen, sulfur, or carbon. In some embodiments, each X is independently selected from sulfur or carbon. In some embodiments, Y is 1. In some embodiments, when y is 1, the electrolyte comprises an isothiocyanate functional group.

[0015] In some embodiments, the electrolyte is not cycled.

[0016] In another aspect, the disclosure relates to compounds of formula I′ (e.g., for use in electrochemical cells, e.g., for use as an additive in an electrolyte for an electrochemical cell, for use as a functional binder, e.g., for use as a binder for an electrochemical cell): [ka] In the formula, R 1 and R 2 are each independently hydrogen or C 1~15 an optionally substituted group selected from aliphatic, 3-7 membered saturated or partially saturated monocyclic carbocyclyl, 4-10 membered saturated or partially unsaturated bicyclic carbocyclyl, 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, 7-10 membered saturated or partially unsaturated bicyclic heterocyclyl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, phenyl, 8-10 membered bicyclic aryl, 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or 8-10 membered bicyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur; or R 1 and R 2 together with the intervening atoms form an optionally substituted ring; Each X is absent or independently O, S, NR z , and C.R. 3 R 4 is selected from Each R z are independently hydrogen or optionally substituted C 1~12 It is aliphatic, Each R 3 and R 4 are independently hydrogen, halogen, -CN, -NO 2 , -N(R) 2 , -OR, -SR, or C 1~12an optionally substituted group selected from aliphatic, 3-7 membered saturated or partially saturated monocyclic carbocyclyl, 4-10 membered saturated or partially unsaturated bicyclic carbocyclyl, 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, 7-10 membered saturated or partially unsaturated bicyclic heterocyclyl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, phenyl, 8-10 membered bicyclic aryl, 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or 8-10 membered bicyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur; Each R is independently hydrogen, optionally substituted C 1~6 an aliphatic, optionally substituted 3- to 7-membered saturated or partially unsaturated carbocyclyl, or an optionally substituted 3- to 7-membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or two R's, when attached to the same nitrogen atom, together form an optionally substituted 3- to 7-membered saturated or partially unsaturated monocyclic carbocyclyl having 0-2 additional heteroatoms independently selected from nitrogen, oxygen, and sulfur. In some embodiments, R 1 and R 2 represents, together with the intervening atoms, a 3- to 7-membered saturated or partially unsaturated monocyclic carbocyclyl; forming an optionally substituted ring selected from a 4-10 membered saturated or partially unsaturated bicyclic carbocyclyl, a 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, a 7-10 membered saturated or partially unsaturated bicyclic heterocyclyl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, a phenyl, an 8-10 membered bicyclic aryl, a 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or an 8-10 membered bicyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0017] In some embodiments, R 1 and R 2 together with the intervening atoms form an optionally substituted 3- to 7-membered saturated or partially unsaturated monocyclic heterocyclyl having 1 to 3 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0018] In some embodiments, R 1 and R 2 together with the intervening atoms form an optionally substituted 5-membered saturated or partially unsaturated monocyclic heterocyclyl having two sulfur heteroatoms.

[0019] In some embodiments, R 1 and R 2 together with the intervening atoms form an optionally substituted 5-6 membered monocyclic heteroaryl having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0020] In some embodiments, one X is NR z and the other X is independently O, S, or NR z , and C.R. 3 R 4 Selected from R z , R 1 , R 2 , R 3 , and R 4Each of is hydrogen.

[0021] In some embodiments, each X is independently NR z and R z , R 1 , and R 2 Each of 1~6 It is aliphatic.

[0022] In some embodiments, each X is independently NR z and R z , R 1 , and R2 Each of is hydrogen.

[0023] In some embodiments, R 1 and R 2 together with the intervening atoms form a ring A as in formula II: [ka] wherein ring A is an optionally substituted ring selected from a 3-7 membered saturated or partially unsaturated monocyclic carbocyclyl, a 4-10 membered saturated or partially unsaturated bicyclic carbocyclyl, a 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, a 7-10 membered saturated or partially unsaturated bicyclic heterocyclyl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, a phenyl, an 8-10 membered bicyclic aryl, a 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or an 8-10 membered bicyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0024] In some embodiments, Ring A is an optionally substituted 5-membered saturated or partially unsaturated monocyclic heterocyclyl having two sulfur heteroatoms.

[0025] In some embodiments, Ring A is an optionally substituted 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0026] In some embodiments, both X are absent.

[0027] In some embodiments, both X are S.

[0028] In some embodiments, both X are NR 2 It is.

[0029] In some embodiments, the compound is trithiocyanuric acid.

[0030] In some embodiments, the binder, additive for the electrolyte, or electrolyte comprises a compound of any of the embodiments disclosed herein.

[0031] In some embodiments, the binder, additive, or electrolyte comprises a compound selected from the group consisting of 3H-1,2-benzodithiol-3-one, phenylacetyl disulfide, tetramethylthiourea, thioacetamide, thiourea, trithiocyanuric acid, vinylene trithiocarbonate, zinc dimethyldithiocarbamate, and dimethyltrithiocarbonate.

[0032] In some embodiments, the binder, additive for the electrolyte, or electrolyte comprises a compound of Table 1 disclosed herein.

[0033] In some embodiments, the electrolyte composition comprises a compound selected from the group consisting of 3H-1,2-benzodithiol-3-one, phenylacetyl disulfide, tetramethylthiourea, thioacetamide, thiourea, trithiocyanuric acid, vinylene trithiocarbonate, zinc dimethyldithiocarbamate, and dimethyltrithiocarbonate.

[0034] In some embodiments, the electrolyte composition comprises a compound of Table 1 disclosed herein.

[0035] In some embodiments, the electrolyte composition comprises a compound of any of the embodiments disclosed herein.

[0036] In some embodiments, the electrolyte composition comprises a compound of formula III: [ka] In the formula, n is 3, 4, 5, 6, 7, or 8.

[0037] In some embodiments, the electrolyte composition comprises a compound of formula IV: [ka] In the formula, n is 3, 4, 5, 6, 7, or 8.

[0038] In some embodiments, the electrolyte composition comprises Li(S). n R 1 Includes.

[0039] In some embodiments, the electrolyte composition comprises Li(S). n R 2 Includes.

[0040] In some embodiments, X is S.

[0041] In some embodiments, lithium trithiocarbonate is the predominant (eg, highest weight or volume percentage) lithium salt in the electrolyte composition.

[0042] In some embodiments, the electrolyte composition has not been cycled.

[0043] In some embodiments, a lithium-sulfur battery includes the binder, electrolyte additive, or electrolyte of any of the embodiments disclosed herein.

[0044] In some embodiments, the lithium-sulfur battery comprises a compound of any of the embodiments disclosed herein.

[0045] In some embodiments, a lithium-sulfur battery comprises the electrolyte composition of any of the embodiments disclosed herein.

[0046] In some embodiments, the battery is not cycled.

[0047] In another aspect, the present disclosure relates to a method of making a lithium-sulfur battery comprising adding a binder of any of the disclosed embodiments, an additive for the electrolyte, or an electrolyte, a compound of any of the disclosed embodiments, or an electrolyte composition of any of the disclosed embodiments to a battery case, said step occurring prior to charging or discharging.

[0048] Any two or more of the features described herein, including the features described in this Summary section, may be combined to form an implementation not specifically and explicitly described herein.

[0049] definition In order that this disclosure may be more readily understood, certain terms used herein are defined below. Additional definitions for the following terms and other terms may be found throughout the specification.

[0050] For the purposes of this invention, chemical elements are defined as defined in the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75 th In addition, the general principles of organic chemistry are identified in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausalito: 1999, and "March's Advanced Organic Chemistry", 5 thEd., Ed.: Smith, M. B. and March, J., John Wiley & Sons, New York: 2001, the entire contents of which are incorporated herein by reference.

[0051] Unless otherwise specified, a structure depicted herein is intended to include all stereoisomeric (e.g., enantiomeric or diastereomeric) forms of the structure, and all geometric or conformational isomeric forms of the structure. For example, the R and S configurations of each stereocenter are contemplated as part of the present disclosure. Thus, single stereochemical isomers, as well as enantiomeric, diastereomeric, and geometric (or conformational) mixtures of the provided compounds are within the scope of the present disclosure. Unless otherwise specified, all tautomeric forms of the provided compounds are within the scope of the present disclosure.

[0052] Unless otherwise stated, structures depicted herein are also meant to include compounds that differ only in the presence of one or more isotopically enriched atoms. For example, the replacement of hydrogen by deuterium or tritium, or 13 C-enriched carbon or 14 Compounds having the subject structures including the replacement of carbons with C-enriched carbons are within the scope of this disclosure.

[0053] About / Approximately: The term "about" or "approximately" when used herein with respect to a value refers to a value that is similar to the value referred to in the context. In general, a person skilled in the art who understands the context will recognize the appropriate degree of variation that is encompassed by "about" or "approximately" in that context. For example, in some embodiments, as provided herein, the term "about" can encompass a range of values ​​that is within 25%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, or less of the value referred to.

[0054] Aliphatic: The term "aliphatic" refers to a linear (i.e., unbranched) or branched, optionally substituted hydrocarbon chain that is fully saturated or contains one or more units of unsaturation, or a monocyclic or bicyclic hydrocarbon (also referred to herein as "carbocyclic" or "cycloaliphatic") that is fully saturated or contains one or more units of unsaturation, but is not aromatic, and has one point of attachment to the remainder of the molecule. Unless otherwise specified, an aliphatic group contains 1-12 aliphatic carbon atoms. In some embodiments, an aliphatic group contains 1-6 aliphatic carbon atoms (e.g., C 1-6 In some embodiments, the aliphatic group contains 1-5 aliphatic carbon atoms (e.g., C 1-5 In other embodiments, aliphatic groups contain 1-4 aliphatic carbon atoms (e.g., C 1-4 In yet other embodiments, the aliphatic group contains 1-3 aliphatic carbon atoms (e.g., C 1-3 ), in yet other embodiments, aliphatic groups contain 1-2 aliphatic carbon atoms (e.g., C 1-2 ). Suitable aliphatic groups include, but are not limited to, linear or branched, substituted or unsubstituted alkyl, alkenyl, alkynyl groups, and hybrids thereof. In some embodiments, "aliphatic" refers to a linear (i.e., unbranched) or branched, optionally substituted hydrocarbon chain that is fully saturated or contains one or more units of unsaturation and has one point of attachment to the remainder of the molecule.

[0055] Alkyl: The term “alkyl” used alone or as part of a larger moiety means an alkyl group having 1 to 12, 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3, or 1 to 2 carbon atoms (unless otherwise specified) (e.g., C 1-12 , C 1-10 , C 1-8 , C 1-6 , C 1-4 , C 1-3 , or C 1-2), a saturated, optionally substituted, straight-chain or branched hydrocarbon group. Exemplary alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl.

[0056] Carbocyclyl: As used herein, the terms "carbocyclyl", "carbocycle", and "carbocyclic ring" refer to a saturated or partially unsaturated cycloaliphatic monocyclic, bicyclic, or polycyclic ring system having 3 to 14 members, which is optionally substituted as described herein. Carbocyclic groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, norbornyl, adamantyl, and cyclooctadienyl. In some embodiments, "carbocyclyl" (or "cycloaliphatic") refers to an optionally substituted monocyclic C ring that is fully saturated or contains one or more units of unsaturation, but is not aromatic, and has one point of attachment to the remainder of the molecule. 3 -C 8 Hydrocarbon or optionally substituted C 7 -C 10 means a bicyclic hydrocarbon. The term "cycloalkyl" means an optionally substituted saturated ring system of about 3 to about 10 ring carbon atoms. In some embodiments, the cycloalkyl group has 3 to 6 carbons. Exemplary monocyclic cycloalkyl rings include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. The term "cycloalkenyl" means an optionally substituted non-aromatic monocyclic or polycyclic ring system containing at least one carbon-carbon double bond and having about 3 to about 10 carbon atoms. Exemplary monocyclic cycloalkenyl rings include cyclopentenyl, cyclohexenyl, and cycloheptenyl.

[0057] Alkenyl: The term “alkenyl” used alone or as part of a larger moiety refers to an alkyl group having at least one double bond and having 2 to 12, 2 to 10, 2 to 8, 2 to 6, 2 to 4, or 2 to 3 carbon atoms (unless otherwise specified) (e.g., C 2-12 , C 2-10 , C 2-8 , C 2-6 , C 2-4 , or C 2-3 ), an optionally substituted straight or branched hydrocarbon chain. Exemplary alkenyl groups include ethenyl, propenyl, butenyl, pentenyl, hexenyl, and heptenyl.

[0058] Alkynyl: The term “alkynyl” used alone or as part of a larger moiety refers to an alkynyl group having at least one triple bond and having 2 to 12, 2 to 10, 2 to 8, 2 to 6, 2 to 4, or 2 to 3 carbon atoms (unless otherwise specified) (e.g., C 2-12 , C 2-10 , C 2-8 , C 2-6 , C 2-4 , or C 2-3 ), an optionally substituted straight or branched chain hydrocarbon group. Exemplary alkynyl groups include ethynyl, propynyl, butynyl, pentynyl, hexynyl, and heptynyl.

[0059] Aryl: The term "aryl" refers to an aryl group having a total of 6 to 14 ring members (e.g., C 6-14 ) refers to monocyclic and bicyclic ring systems in which at least one ring in the system is aromatic and each ring in the system contains from 3 to 7 ring members. The term "aryl" may be used synonymously with the term "aryl ring." In some embodiments, "aryl" refers to an aromatic ring system, including, but not limited to, phenyl, naphthyl, anthracyl, and the like, which may bear one or more substituents. Unless otherwise specified, "aryl" groups are hydrocarbons.

[0060] Heteroaryl: The terms "heteroaryl" and "heteroar-" used alone or as part of a larger moiety such as "heteroaralkyl" or "heteroaralkoxy" refer to a monocyclic or bicyclic ring group having 5 to 10 ring atoms, having 6, 10, or 14 pi-electrons shared in a cyclic arrangement, and having 1 to 5 heteroatoms in addition to the carbon atoms (e.g., a 5- to 6-membered monocyclic heteroaryl or a 9- to 10-membered bicyclic heteroaryl). Exemplary heteroaryl groups include, but are not limited to, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyridyl, pyridonyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl, purinyl, naphthyridinyl, pteridinyl, imidazo[1,2-a]pyrimidinyl, imidazo[1,2-a]pyridinyl, thienopyrimidinyl, triazolopyridinyl, and benzisoxazolyl. As used herein, the terms "heteroaryl" and "heteroara" also include groups in which a heteroaromatic ring is fused to one or more aryl, cycloaliphatic, or heterocyclyl rings, with the radical or point of attachment being on the heteroaromatic ring (i.e., bicyclic heteroaryl rings having 1 to 3 heteroatoms). Non-limiting examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzothiazolyl, benzothiadiazolyl, benzoxazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, pyrido[2,3-b]-1,4-oxazin-3(4H)-one, and benzisoxazolyl. The term "heteroaryl" may be used interchangeably with the terms "heteroaryl ring," "heteroaryl group," or "heteroaromatic," all of which include optionally substituted rings.

[0061] Heteroatom: As used herein, the term "heteroatom" means nitrogen, oxygen, or sulfur, and includes any oxidized form of nitrogen or sulfur, and any quaternized form of a basic nitrogen.

[0062] Heterocycle: As used herein, the terms "heterocycle", "heterocyclyl" and "heterocyclic ring" are used interchangeably and refer to a stable 3-7 membered monocyclic or 7-10 membered bicyclic heterocyclic moiety that is saturated or partially unsaturated and has, in addition to carbon atoms, one or more, e.g., one to four, heteroatoms as defined above. When used in reference to a ring atom of a heterocycle, the term "nitrogen" includes substituted nitrogen. As an example, in a saturated or partially unsaturated ring having 0-3 heteroatoms selected from oxygen, sulfur, or nitrogen, the nitrogen can be N (as in 3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl), or NR + (in the case of N-substituted pyrrolidinyl). A heterocyclic ring may be attached to its pendant group at any heteroatom or carbon atom that results in a stable structure, and any of the ring atoms may be optionally substituted. Examples of such saturated or partially unsaturated heterocyclic radicals include, but are not limited to, tetrahydrofuranyl, tetrahydrothienyl, piperidinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl, dioxanyl, dioxolanyl, diazepinyl, oxazepinyl, thiazepinyl, morpholinyl, and thiamorpholinyl. A heterocyclyl group may be monocyclic, bicyclic, tricyclic, or polycyclic, preferably monocyclic, bicyclic, or tricyclic, more preferably monocyclic or bicyclic. Bicyclic heterocyclic rings also include groups in which a heterocyclic ring is fused to one or more aryl, heteroaryl, or cycloaliphatic rings. Exemplary bicyclic heterocyclic groups include indolinyl, isoindolinyl, benzodioxolyl, 1,3-dihydroisobenzofuranyl, 2,3-dihydrobenzofuranyl, and tetrahydroquinolinyl. The bicyclic heterocyclic ring may be a spirocyclic ring system (e.g., a 7-11 membered spirocyclic fused heterocyclic ring having, in addition to carbon atoms, one or more heteroatoms as defined above (e.g., 1, 2, 3, or 4 heteroatoms).

[0063] Partially unsaturated: As used herein, the term "partially unsaturated" with respect to a ring moiety means a ring moiety that contains at least one double or triple bond between ring atoms. The term "partially unsaturated," as defined herein, is intended to encompass rings having multiple sites of unsaturation, but is not intended to include aromatic (e.g., aryl or heteroaryl) moieties.

[0064] Substituted or Optionally Substituted: As described herein, compounds of the present disclosure may include "optionally substituted" moieties. In general, the term "substituted," whether preceded by the term "optionally," means that one or more hydrogens of the specified moiety are replaced with a suitable substituent (i.e., as described below for optionally substituted groups). "Substitution" applies to one or more hydrogens that are explicit or implicit from the structure (e.g., [ka] At least [ka] means, [ka] At least [ka] (meaning that the substituents are the same or different at all positions). Unless otherwise stated, an "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and when multiple positions in a given structure may be substituted with multiple substituents selected from a specified group, the substituents may be the same or different at all positions. The combinations of substituents envisioned by the present invention are preferably those that result in the formation of stable or chemically feasible compounds. As used herein, the term "stable" refers to a compound that is substantially unchanged when subjected to conditions that allow for the production, detection, and, in certain embodiments, recovery, purification, and use of the compound for one or more of the purposes provided herein. Groups described as "substituted" preferably have 1-4 substituents, more preferably 1 or 2 substituents. Groups described as "optionally substituted" may be unsubstituted or "substituted" as described above.

[0065] Suitable monovalent substituents on a substitutable carbon atom of an "optionally substituted" group are independently halogen; -(CH 2 ) 0-4 R 。 ;-(CH 2 ) 0-4 OR 。 ;-O(CH 2 ) 0-4 R o , -O-(CH 2 ) 0-4 C(O)OR 。 ;-(CH 2 ) 0-4 CH(OR 。 ) 2 ;-(CH 2 ) 0-4 S.R. 。 ;R 。 may be substituted with -(CH 2 ) 0-4 Ph; optionally substituted with R° -(CH 2 ) 0-4 O(CH 2 ) 0-1 Ph; -CH=CH, optionally substituted with R°; -(CH 2 )0-4 O(CH 2 ) 0-1 -ピリジル;-NO 2 ;-CN;-N 3 ;-(CH 2 ) 0-4 N(R 。 ) 2 ;-(CH 2 ) 0-4 N(R 。 )C(O)R 。 ;-N(R 。 )C(S)R 。 ;-(CH 2 ) 0-4 N(R 。 )C(O)NR 。 2 ;-N(R 。 )C(S)NR 。 2 ;-(CH 2 ) 0-4 N(R 。 )C(O)OR 。 ;-N(R 。 )N(R 。 )C(O)R 。 ;-N(R 。 )N(R 。 )C(O)NR 。 2 ;-N(R 。 )N(R 。 )C(O)OR 。 ;-(CH 2 ) 0-4 C(O)R 。 ;-C(S)R 。 ;-(CH 2 ) 0-4 C(O)OR 。 ;-(CH 2 ) 0-4 C(O)SR 。 ;-(CH 2 ) 0-4 C(O)OSiR 。 3 ;-(CH 2 ) 0-4 OC(O)R 。 ;-OC(O)(CH 2 ) 0-4 SR°;-(CH 2 ) 0-4 SC(O)R。 ;-(CH 2 ) 0-4 C(O)NR 。 2 ;-C(S)NR 。 2 ;-C(S)SR°;-SC(S)SR°、-(CH 2 ) 0-4 OC(O)NR 。 2 ;-C(O)N(OR 。 )R 。 ;-C(O)C(O)R 。 ;-C(O)CH 2 C(O)R 。 ;-C(NOR 。 )R 。 ;-(CH 2 ) 0-4 SSR 。 ;-(CH 2 ) 0-4 S(O) 2 R 。 ;-(CH 2 ) 0-4 S(O) 2 OR 。 ;-(CH 2 ) 0-4 OS(O) 2 R 。 ;-S(O) 2 NR 。 2 ;-(CH 2 ) 0-4 S(O)R 。 ;-N(R 。 )S(O) 2 NR 。 2 ;-N(R 。 )S(O) 2 R 。 ;-N(OR 。 )R 。 ;-C(NH)NR 。 2 ;-P(O) 2 R 。 ;-P(O)R 。 2 ;-OP(O)R 。 2 ;-OP(O)(OR 。 ) 2 ;-SiR 。3 ;-(C 1-4 Linear or branched alkylene)ON(R 。 ) 2 ; or -(C 1-4 Linear or branched alkylene)C(O)ON(R 。 ) 2 where each R 。 are optionally substituted as defined below and independently represent hydrogen, C 1-6 Aliphatic, -CH 2 Ph, -O(CH 2 ) 0-1 Ph, -CH 2 -(5-6 membered heteroaryl ring), or a 3-6 membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or, regardless of the above definition, two independent R 。 The occurrences, together with the intervening atom(s), form a 3-12 membered saturated, partially unsaturated, or aryl monocyclic or bicyclic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, which may be optionally substituted as defined below.

[0066] R 。 (or two separate R 。 Preferred monovalent substituents on the ring formed by the presence of -(CH) together with the intervening atoms are independently halogen, -(CH 2 ) 0-2 R . , -(Halo R . ), -(CH 2 ) 0-2 OH, -(CH 2 ) 0-2 OR . , -(CH 2 ) 0-2 CH(OR . ) 2 , -O(HaloR . ), -CN, -N 3 , -(CH 2 ) 0-2 C(O)R . , -(CH 2 ) 0-2C(O)OH, -(CH 2 ) 0-2 C(O)OR . , -(CH 2 ) 0-2 S.R. . , -(CH 2 ) 0-2 SH, -(CH 2 ) 0-2 NH 2 , -(CH 2 ) 0-2 NHR . , -(CH 2 ) 0-2 NR . 2 , -NO 2 , -SiR . 3 , -OSiR . 3 , -C(O)SR . , -(C 1-4 Linear or branched alkylene)C(O)OR . , or -SSR . where each R . is unsubstituted or, if preceded by "halo", is substituted only with one or more halogens; and C 1-4 Aliphatic, -CH 2 Ph, -O(CH 2 ) 0-1 R is independently selected from Ph, or a 3-6 membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur. 。 Suitable divalent substituents on a saturated carbon atom of include ═O and ═S.

[0067] Suitable divalent substituents on a saturated carbon atom of an "optionally substituted" group include ═O ("oxo"), ═S, ═NNR * 2 , =NNHC(O)R * , =NNHC(O)OR * , =NNHS(O) 2 R * , =NR * , =NOR * , -O(C(R * 2)) 2-3 O-, or -S(C(R * 2 )) 2-3 S-, wherein each R * Each occurrence of is hydrogen, optionally substituted as defined below, 1-6 The "optionally substituted" group is preferably a divalent substituent attached to adjacent substitutable carbon atoms, such as -O(CR * 2 ) 2-3 O-, wherein each R * Each occurrence of is hydrogen, optionally substituted as defined below, 1-6 It is selected from an aliphatic or unsubstituted 5-6 membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.

[0068] R * Suitable substituents on the aliphatic group include halogen, -R . , -(Halo R . ), -OH, -OR . , -O(HaloR . ), -CN, -C(O)OH, -C(O)OR . , -NH 2 , -NHR . , -NR . 2 , or -NO 2 In the formula, each R . is unsubstituted or, if preceded by "halo", is substituted only with one or more halogens, and independently, C 1-4 Aliphatic, -CH 2 Ph, -O(CH 2 ) 0-1 Ph, or a 3-6 membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.

[0069] Suitable substituents on a substitutable nitrogen of an "optionally substituted" group include -R † , -NR † 2 , -C(O)R † , -C(O)OR † , -C(O)C(O)R † , -C(O)CH 2 C(O)R † , -S(O) 2 R † , -S(O) 2 NR † 2 , -C(S)NR † 2 , -C(NH)NR † 2 , or -N(R † )S(O) 2 R † In the formula, each R † are independently hydrogen, optionally substituted as defined below, 1-6 an unsubstituted 3-6 membered saturated, partially unsaturated, or aryl ring having an aliphatic or 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or, notwithstanding the above definitions, two independent R † The occurrences, together with the intervening atom(s), form an unsubstituted 3-12 membered saturated, partially unsaturated, or aryl monocyclic or bicyclic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.

[0070] R † Suitable substituents on the aliphatic group are independently halogen, -R . , -(Halo R . ), -OH, -OR . , -O(HaloR . ), -CN, -C(O)OH, -C(O)OR . , -NH 2 , -NHR . , -NR . 2 , or -NO 2 where each R .is unsubstituted or, if preceded by "halo", is substituted with only one or more halogens, and independently, C 1~4 Aliphatic, -CH 2 Ph, -O(CH 2 ) 0~1 Ph, or a 3-6 membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.

[0071] The drawings are presented herein for purposes of illustration and not limitation. The above and other objects, aspects, features, and advantages of the present disclosure will become more apparent and may be better understood by referring to the following description in conjunction with the accompanying drawings, in which: [Brief description of the drawings]

[0072] [Figure 1] FIG. 1 is a cross-sectional depiction of an electrochemical cell according to certain embodiments of the present disclosure.

[0073] [Diagram 2] FIG. 1 is a pictorial representation of a cylindrical battery according to certain embodiments of the present disclosure.

[0074] [Diagram 3] 1 is a graph showing discharge specific capacity performance characteristics (eg, at 0.1c) of a battery according to certain embodiments of the present disclosure.

[0075] [Figure 4] 1 is a graph showing discharge specific capacity performance characteristics (eg, at 0.333c) of a battery according to certain embodiments of the present disclosure.

[0076] [Diagram 5] 1 is a graph illustrating the discharge average voltage performance characteristics of a battery according to certain embodiments of the present disclosure.

[0077] [Figure 6] 1 is a graph illustrating pulse average efficiency performance characteristics of batteries according to certain embodiments of the present disclosure.

[0078] [Figure 7] 1 is a graph illustrating pulse end of first plateau efficiency performance characteristics of a battery according to certain embodiments of the present disclosure.

[0079] [Figure 8] 1 is a graph illustrating pulse end of discharge efficiency performance characteristics of a cell according to certain embodiments of the present disclosure.

[0080] [Figure 9] 1 is a graph illustrating coulombic efficiency performance characteristics of a battery according to certain embodiments of the present disclosure.

[0081] [Figure 10] 1 is a graph illustrating thermal efficiency performance characteristics of a battery according to certain embodiments of the present disclosure.

[0082] [Figure 11] 1 is a graph illustrating voltage efficiency performance characteristics of a battery according to certain embodiments of the present disclosure.

[0083] [Figure 12] FIG. 1 is a depiction of a coin cell assembly in accordance with one or more embodiments of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0084] Elements of different embodiments described herein may be combined to form other embodiments not specifically described above. Elements may be omitted from the devices described herein if they do not adversely affect the operation of the devices. Various separate elements may be combined into one or more individual elements to perform the functions described herein.

[0085] The claimed objects, devices, compositions, systems, methods, and processes are intended to encompass variations and modifications developed using information from the embodiments described herein. It is contemplated herein that variations and / or modifications of the objects, devices, compositions, systems, methods, and processes described herein may be made.

[0086] Throughout this specification, when objects, devices, compositions, and systems are described as having, including, or comprising particular elements, or processes and methods are described as having, including, or comprising particular steps, it is intended that there are additional objects, devices, compositions, and systems of the invention that consist essentially of or consist of the recited elements, and that there are additional processes and methods of the invention that consist essentially of or consist of the recited process steps.

[0087] It should be understood that the order of steps or order for performing certain actions is not essential so long as the invention remains operable. Moreover, two or more steps or actions may be conducted simultaneously.

[0088] The citation of any publication in this specification is not an admission that such publication is prior art with respect to any claim presented in this application. The "Background" section is provided for clarity and is not intended as a description of prior art with respect to any claim.

[0089] Headings are provided for the convenience of the reader, and the presence and / or placement of headings is not intended to limit the scope of the subject matter described herein. compound

[0090] The present disclosure encompasses the recognition that aliphatic carbonates (e.g., ROC(O)OR') and aliphatic polycarbonates are useful components of electrolyte compositions for lithium-ion batteries that have many desirable properties. However, such carbonates are not suitable for lithium-sulfur batteries, in part because nucleophilic lithium sulfide intermediates tend to react with the carbonate moieties, leading to irreversible formation of lithium alkoxides and the formation of carbon-sulfur covalent bonds. Thus, the present disclosure encompasses the recognition of a previously unidentified source of problems in the application of conventional electrolytes to lithium-sulfur batteries.

[0091] This disclosure describes, among other things, the use of thiocarbonates (e.g., trithiocarbonates or RSC(S)SR') as electrolytes in lithium-sulfur cells in place of traditional aliphatic carbonates. Without wishing to be bound by any particular theory, it is believed that because trithiocarbonates do not form alkoxides upon reaction with nucleophilic sulfides, the reaction may be reversible, which should pose less of a hindrance to the operation of the electrochemical cell.

[0092] As an example, the first product of attack of a polysulfide on a trithiocarbonate is a tetrahedral intermediate resulting from attack of the sulfide at the thiocarbonyl carbon: [ka] In the formula, for example, 8>n>3.

[0093] The resulting intermediate decays to reform the original starting material (i.e., [LiS n ] - In some cases, [SR] - , or [SR'] - and lithiated polysulfide (RSC(S)S) n Li) may be produced: [ka]

[0094] The released LiSR species is a strong nucleophile that can react with another trithiocarbonate, so that at equilibrium, the composition will be 2- As the trithiocarbonates are further reduced to , they return to the starting trithiocarbonate mixture (including scrambling of the substituents in the asymmetrically substituted trithiocarbonates). It will be appreciated that the electrolyte composition in a working or cycled battery may differ from the starting electrolyte composition due to potential scrambling of the starting trithiocarbonates. Furthermore, the presence of polysulfide-substituted trithiocarbonates may vary depending on the state of charge of the battery. In this regard, both the relative abundance of these molecules and the average value of n therein (i.e., the length of the polysulfide chains) may be dynamic.

[0095] Since irreversible side reactions may occur during each cycle of an electrochemical cell, one or more performance advantages of an electrochemical cell comprising an electrolyte, additive, or binder disclosed herein may be greater during the latter part of the cycle life. For example, an electrochemical cell comprising an electrolyte, additive, or binder disclosed herein may exhibit improved properties after at least 25, at least 50, at least 75, at least 100, at least 200, at least 300, or at least 500 charge cycles. For example, polysulfide migration may be mitigated by using thiocarbonyl-containing species (e.g., in the binder and / or electrolyte), and the effect of such mitigation may be more pronounced after many cycles than after only a few cycles. Reduction of polysulfide migration may also be improved when an electrochemical cell comprises a binder comprising a thiocarbonyl functional group.

[0096] According to one aspect of the present disclosure, thiocarbonyl compounds are provided for use as binders, electrolytes, or additives for electrolytes in lithium-sulfur batteries (e.g., sulfur cathodes). In some embodiments, the present disclosure provides binders for sulfur cathodes that include a thiocarbonyl functional group (i.e., -C(S)-). In some embodiments, the present disclosure provides additives for electrolytes in lithium-sulfur batteries that include a thiocarbonyl functional group. In some embodiments, the present disclosure provides electrolytes for lithium-sulfur batteries that include a thiocarbonyl functional group.

[0097] In some embodiments, the provided binder, additive, or electrolyte has the formula X2C = S (i.e., XC(S)-X), where each X is independently selected from oxygen, nitrogen, sulfur, or carbon. In some embodiments, the binder, additive, or electrolyte provided comprises a thiocarbonyl functional group of formula X y

[0033] The binder, additive, or electrolyte may include a thiocarbonyl functional group of formula C=S, where each X is independently selected from oxygen, nitrogen, sulfur, or carbon, and y is 1 or 2, provided that when one X forms a ring with the other X and an intervening atom, and y is 1, then X is connected to the thiocarbonyl carbon through a double bond. In some embodiments, y is 2, and the binder, additive, or electrolyte provided has the formula X 2 In some embodiments, the binder, additive, or electrolyte comprises a thiocarbonyl functional group of C=S. In some embodiments, the binder, additive, or electrolyte comprises a thiocarbonate, a thiourea, a thiocarbamate, or a thioketone functional group. In some embodiments, y is 1. In some embodiments, the binder, additive, or electrolyte comprises an isothiocyanate functional group. In some embodiments, the binder, additive, or electrolyte comprises carbon disulfide.

[0098] In some embodiments, the binder, additive, or electrolyte provided is represented by the formula X yIn some embodiments, the binder, additive, or electrolyte provided comprises a thiocarbonyl functional group of formula X y In some embodiments, the binder, additive, or electrolyte provided comprises a thiocarbonyl functional group of formula X y It contains a thiocarbonyl functional group of C=S, where both X's are nitrogen and y is 2.

[0099] It will be appreciated that certain compounds useful as binders, additives, or electrolytes described herein may not contain thiocarbonyl functional groups prior to the first cycle of a secondary battery containing such compounds, but may form thiocarbonyl groups in situ as reaction products or intermediates during cycling of the battery.

[0100] In some embodiments, compounds containing a thiocarbonyl functional group that can be used in accordance with the present disclosure are shown in Formulae I', I, II, III, and IV below, as well as classes and subclasses thereof described herein including species (collectively, "Provided Compounds").

[0101] In some embodiments, the disclosure provides a compound of formula I': [ka] In the formula, R 1 and R 2 are each independently hydrogen or C 1~15an optionally substituted group selected from aliphatic, 3-7 membered saturated or partially saturated monocyclic carbocyclyl, 4-10 membered saturated or partially unsaturated bicyclic carbocyclyl, 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, 7-10 membered saturated or partially unsaturated bicyclic heterocyclyl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, phenyl, 8-10 membered bicyclic aryl, 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or 8-10 membered bicyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur; 1 and R 2 together with the intervening atoms form an optionally substituted ring, Each X is absent or independently O, S, NR z , and C.R. 3 R 4 is selected from Each R z are independently hydrogen or optionally substituted C 1~12 It is aliphatic, Each R 3 and R 4 are independently hydrogen, halogen, -CN, -NO 2 , -N(R) 2 , -OR, -SR, or C 1~12an optionally substituted group selected from aliphatic, 3-7 membered saturated or partially saturated monocyclic carbocyclyl, 4-10 membered saturated or partially unsaturated bicyclic carbocyclyl, 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, 7-10 membered saturated or partially unsaturated bicyclic heterocyclyl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, phenyl, 8-10 membered bicyclic aryl, 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or 8-10 membered bicyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur; Each R is independently hydrogen, optionally substituted C 1~6 an aliphatic, optionally substituted 3-7 membered saturated or partially unsaturated carbocyclyl, or an optionally substituted 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or two R's, when attached to the same nitrogen atom, together form an optionally substituted 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 0-2 additional heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0102] In some embodiments, the disclosure provides a compound of formula I: [ka] In the formula, R 1 and R 2 are each independently or C 1~15an optionally substituted group selected from aliphatic, 3-7 membered saturated or partially saturated monocyclic carbocyclyl, 4-10 membered saturated or partially unsaturated bicyclic carbocyclyl, 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, 7-10 membered saturated or partially unsaturated bicyclic heterocyclyl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, phenyl, 8-10 membered bicyclic aryl, 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or 8-10 membered bicyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur; 1 and R 2 together with the intervening atoms form an optionally substituted ring, Each X is absent or independently O, S, NR z , and C.R. 3 R 4 is selected from Each R z are independently hydrogen or optionally substituted C 1~12 It is aliphatic, Each R 3 and R 4 are independently hydrogen, halogen, -CN, -NO 2 , -N(R) 2 , -OR, -SR, or C 1~12an optionally substituted group selected from aliphatic, 3-7 membered saturated or partially saturated monocyclic carbocyclyl, 4-10 membered saturated or partially unsaturated bicyclic carbocyclyl, 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, 7-10 membered saturated or partially unsaturated bicyclic heterocyclyl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, phenyl, 8-10 membered bicyclic aryl, 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or 8-10 membered bicyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur; Each R is independently hydrogen, optionally substituted C 1~6 an aliphatic, optionally substituted 3-7 membered saturated or partially unsaturated carbocyclyl, or an optionally substituted 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or two R's, when attached to the same nitrogen atom, together form an optionally substituted 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 0-2 additional heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0103] In some embodiments, R 1 and R 2 are each independently hydrogen or C 1~12an optionally substituted group selected from aliphatic, 3-7 membered saturated or partially saturated monocyclic carbocyclyl, 4-10 membered saturated or partially unsaturated bicyclic carbocyclyl, 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, 7-10 membered saturated or partially unsaturated bicyclic heterocyclyl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, phenyl, 8-10 membered bicyclic aryl, 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or 8-10 membered bicyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0104] In some embodiments, R 1 and R 2 are each independently 1~12 an optionally substituted group selected from aliphatic, 3-7 membered saturated or partially saturated monocyclic carbocyclyl, 4-10 membered saturated or partially unsaturated bicyclic carbocyclyl, 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, 7-10 membered saturated or partially unsaturated bicyclic heterocyclyl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, phenyl, 8-10 membered bicyclic aryl, 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or 8-10 membered bicyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0105] In some embodiments, R 1 and R 2 are each independently 1~12 In some embodiments, R is an optionally substituted group selected from aliphatic. 1 and R 2 are each independently 1~6In some embodiments, R is an optionally substituted group selected from aliphatic. 1 and R 2 are each independently 1~6 In some embodiments, R is an optionally substituted group selected from alkyl. 1 and R 2 are each independently 1~4 In some embodiments, R is an optionally substituted group selected from alkyl. 1 and R 2 are each independently methyl, ethyl, propyl, or butyl. In some embodiments, R 1 and R 2 are each independently substituted methyl. In some embodiments, R 1 and R 2 Each is benzyl. In some embodiments, R 1 and R 2 are hydrogen.

[0106] In some embodiments, R 1 and R 2 are each independently 1~12 is an optionally substituted group selected from aliphatic or 3-7 membered saturated or partially unsaturated monocyclic carbocyclyl. In some embodiments, R 1 and R 2 are each independently 1~6 It is an optionally substituted group selected from aliphatic or 3-4 membered saturated monocyclic carbocyclyl.

[0107] In some embodiments, R 1 and R 2together with the intervening atoms form an optionally substituted ring selected from a 3-7 membered saturated or partially unsaturated monocyclic carbocyclyl, a 4-10 membered saturated or partially unsaturated bicyclic carbocyclyl, a 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, a 7-10 membered saturated or partially unsaturated bicyclic heterocyclyl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, a phenyl, an 8-10 membered bicyclic aryl, a 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or an 8-10 membered bicyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0108] In some embodiments, R 1 and R 2 together with the intervening atoms form an optionally substituted 3- to 7-membered saturated or partially unsaturated monocyclic carbocyclyl. In some embodiments, R 1 and R 2 together with the intervening atoms form an optionally substituted 4-10 membered saturated or partially unsaturated bicyclic carbocyclyl. In some embodiments, R 1 and R 2 together with the intervening atoms form an optionally substituted 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur. In some embodiments, R 1 and R 2 together with the intervening atoms form an optionally substituted 7-10 membered saturated or partially unsaturated bicyclic heterocyclyl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. In some embodiments, R 1 and R 2 together with the intervening atoms form an optionally substituted phenyl. In some embodiments, R 1 and R 2 together with the intervening atoms form an optionally substituted 8-10 membered bicyclic aryl. In some embodiments, R1 and R 2 together with the intervening atoms form an optionally substituted 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. In some embodiments, R 1 and R 2 together with the intervening atoms form an optionally substituted 8-10 membered bicyclic heteroaryl having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0109] In some embodiments, R 1 and R 2 together with the intervening atoms form an optionally substituted 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur. In some embodiments, R 1 and R 2 together with the intervening atoms form an optionally substituted 5-membered saturated or partially unsaturated monocyclic heterocyclyl having 1 to 3 heteroatoms independently selected from nitrogen, oxygen, and sulfur. In some embodiments, R 1 and R 2 together with the intervening atoms form an optionally substituted 5-membered saturated or partially unsaturated monocyclic heterocyclyl having two heteroatoms independently selected from nitrogen, oxygen, and sulfur. In some embodiments, R 1 and R 2 together with the intervening atoms form an optionally substituted 5-membered saturated or partially unsaturated monocyclic heterocyclyl having two sulfur heteroatoms.

[0110] In some embodiments, R 1 and R 2 together with the intervening atoms form an optionally substituted 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. In some embodiments, R 1 and R 2together with the intervening atoms form an optionally substituted 5-membered monocyclic heteroaryl having 2-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur. In some embodiments, R 1 and R 2 together with the intervening atoms form an optionally substituted 6-membered monocyclic heteroaryl having 2-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur. 1 and R 2 together with the intervening atoms form an optionally substituted 6-membered monocyclic heteroaryl having three nitrogen heteroatoms. In some embodiments, R 1 and R 2 together with the intervening atoms form an optionally substituted triazine. In some embodiments, R 1 and R 2 together with the intervening atoms form an optionally substituted 1,3,5-triazine.

[0111] In some embodiments, R 1 and R 2 together with the intervening atoms form a ring A as in formula II: [ka] wherein X, alone or in combination, is as defined above for formula I and as described in classes and subclasses herein; Ring A is a 3- to 7-membered saturated or partially unsaturated monocyclic carbocyclyl; an optionally substituted ring selected from a 4-10 membered saturated or partially unsaturated bicyclic carbocyclyl, a 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, a 7-10 membered saturated or partially unsaturated bicyclic heterocyclyl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, a phenyl, an 8-10 membered bicyclic aryl, a 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or an 8-10 membered bicyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0112] In some embodiments, ring A is an optionally substituted 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur. In some embodiments, ring A is an optionally substituted 5 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur. In some embodiments, ring A is an optionally substituted 5 membered saturated or partially unsaturated monocyclic heterocyclyl having 2 heteroatoms independently selected from nitrogen, oxygen, and sulfur. In some embodiments, ring A is an optionally substituted 5 membered saturated or partially unsaturated monocyclic heterocyclyl having 2 sulfur heteroatoms.

[0113] In some embodiments, ring A is an optionally substituted 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. In some embodiments, ring A is an optionally substituted 5 membered monocyclic heteroaryl having 2-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur. In some embodiments, ring A is an optionally substituted 6 membered monocyclic heteroaryl having 2-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur. In some embodiments, ring A is a 6 membered monocyclic heteroaryl having 3 nitrogen heteroatoms. In some embodiments, ring A is an optionally substituted triazine. In some embodiments, ring A is an optionally substituted 1,3,5-triazine.

[0114] As stated above, all tautomeric forms of the provided compounds are within the scope of this disclosure. Thus, it will be understood that a particular compound that contains a thiol (i.e., -SH) functional group is within the scope of the provided compounds, and within the genus when the thiocarbonyl functional group is a tautomer. For example, the tautomer of trithiocyanuric acid contains a thiocarbonyl (e.g., thiourea) functional group as shown below: [ka]

[0115] In some embodiments, both X are absent. In some embodiments, one X is absent. In some embodiments, each X is independently O, S, NR 2 , and C.R. 3 R 4 In some embodiments, both X are selected from the group consisting of S, R, R, and R. In some embodiments, both X are selected from the group consisting of NR, R, R, and R. 2 In some embodiments, both X are O. In some embodiments, both X are CR 3 R 4In some embodiments, one X is S and the other X is O. In some embodiments, one X is S and the other X is NR 2 In some embodiments, one X is S and the other X is CR 3 R 4 In some embodiments, one X is S and the other X is absent.

[0116] In some embodiments, one X is O and the other X is NR 2 In some embodiments, one X is O and the other X is CR 3 R 4 In some embodiments, one X is O and the other X is absent.

[0117] In some embodiments, one X is NR 2 and the other X is CR 3 R 4 In some embodiments, one X is NR 2 and the other X is absent. In some embodiments, one X is CR 3 R 4 and the other X does not exist.

[0118] In some embodiments, R z is hydrogen. In some embodiments, R z is an optionally substituted C 1~12 In some embodiments, R z is methyl.

[0119] In some embodiments, R 3 is hydrogen, halogen, -CN, -NO 2 , -N(R) 2 , -OR, -SR, or C 1~12 In some embodiments, R is an optionally substituted group selected from aliphatic. 4 is hydrogen, halogen, -CN, -NO 2 , -N(R) 2 , -OR, -SR, or C1~12 is an optionally substituted group selected from aliphatic.

[0120] In some embodiments, each R is independently hydrogen, optionally substituted C 1~6 When attached to the same nitrogen atom, or when two R are joined together, they form an optionally substituted 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 0-2 additional heteroatoms independently selected from nitrogen, oxygen, and sulfur. In some embodiments, each R is hydrogen, or C 1~6 It is aliphatic.

[0121] In some embodiments, one X is NR z and the other X is independently O, S, or NR z , and C.R. 3 R 4 In some embodiments, one X is selected from NR z and the other X is independently O, S, or NR z , and C.R. 3 R 4 Selected from R z , R 1 , R 2 , R 3 , and R 4 Each of 1~6 In some embodiments, one X is NR z and the other X is independently O, S, or NR z , and C.R. 3 R 4 Selected from R z , R 1 , R 2 , R 3 , and R 4 Each of is hydrogen.

[0122] In some embodiments, each X is independently NR z and R z , R 1 , and R 2 Each of 1~6In some embodiments, each X is independently NR z and R z , R 1 , and R2 Each of is hydrogen.

[0123] In some embodiments, the compound provided is selected from ethylene trithiocarbonate and trithiocyanuric acid. In some embodiments, the compound provided is ethylene trithiocarbonate. In some embodiments, the compound provided is trithiocyanuric acid.

[0124] In some embodiments, a provided compound is 3H-1,2-benzodithiol-3-one. In some embodiments, a provided compound is phenylacetyl disulfide. In some embodiments, a provided compound is tetramethylthiourea. In some embodiments, a provided compound is thioacetamide. In some embodiments, a provided compound is thiourea. In some embodiments, a provided compound is trithiocyanuric acid. In some embodiments, a provided compound is vinylene trithiocarbonate. In some embodiments, a provided compound is zinc dimethyldithiocarbamate. In some embodiments, a provided compound is dimethyltrithiocarbonate.

[0125] In some embodiments, provided compounds are or include disulfide moieties that form thiocarbonyl moieties as reaction products or intermediates upon cycling of secondary batteries that contain such compounds as binders, additives, or electrolytes.

[0126] In some embodiments, the compound provided is selected from Table 1.

[0127] [Table 1-1] [Table 1-2] [Table 1-3]

[0128] In some embodiments, provided compounds are other than dimethyltrithiocarbonate. In some embodiments, provided compounds are other than ethylenetrithiocarbonate.

[0129] In some embodiments, the binder, additive, or electrolyte comprises a moiety that includes a thiocarbonyl functional group and a carbon atom bonded to both a nitrogen atom and a sulfur atom (an "NCS moiety"). In some embodiments, the NCS moiety comprises at least a portion of the thiocarbonyl functional group (e.g., the carbon bonded to the sulfur is a thiocarbonyl group). electrolyte composition

[0130] As noted above, the electrolytes of the present disclosure can include a thiocarbonyl functional group containing compound of any one of formulas I', I, II, III, or IV.

[0131] Without wishing to be bound by any particular theory, it is believed that upon cycling of a secondary battery containing an electrolyte of Formula I, the polysulfide attacks the thiocarbonyl group, converting the electrolyte compound to a thiocarbonyl-containing compound that includes a lithiated polysulfide as lithium-X (e.g., lithium thiolate) species is released. Thus, in certain embodiments, provided electrolyte compositions include a compound of Formula III: [ka] In the formula, n is 3, 4, 5, 6, 7, or 8.

[0132] Additionally, in the case of unsymmetrical thiocarbonyl compounds, other lithiated polysulfide compounds may be formed depending on which group(s) are released after polysulfide attack. Thus, in certain embodiments, provided electrolyte compositions include a compound of formula IV: [ka] In the formula, n is 3, 4, 5, 6, 7, or 8.

[0133] In some embodiments, when at least one X is sulfur, the electrolyte composition comprises Li(S) n R 1 and / or Li(S) n R 2 Further includes:

[0134] In some embodiments, the electrolyte compositions provided are "uncycled," meaning that they have not yet been charged and / or discharged.

[0135] The electrolyte compositions of the present disclosure may also include other electrolytes or components, including those described below.

[0136] In certain embodiments, the secondary sulfur battery includes an electrolyte that includes an electrolyte salt, such as, for example, lithium trifluoromethanesulfonimide, lithium triflate, lithium perchlorate, LiPF 6 , LiBF 4 , tetraalkylammonium salts (e.g., tetrabutylammonium tetrafluoroborate, TBABF 4 ), salts that are liquid at room temperature (e.g., imidazolium salts such as 1-ethyl-3-methylimidazolium bis-(perfluoroethylsulfonyl)imide, EMIBeti, etc. In some embodiments, lithium trithiocarbonate(s) is the predominant lithium salt in the electrolyte composition.

[0137] In certain embodiments, the electrolyte comprises one or more alkali metal salts. In certain embodiments, such salts include lithium salts (e.g., LiCF 3 SO 3 , LiClO 4 , LiNO 3 , LiPF 6, LiBr, LiTDI, LiFSI, and LiTFSI, or combinations thereof. In certain embodiments, the electrolyte comprises an ionic liquid (e.g., 1-ethyl-3-methylimidazolium-TFSI, N-butyl-N-methyl-piperidinium-TFSI, N-methyl-n-butylpyrrolidinium-TFSI, and N-methyl-N-propylpiperidinium-TFSI, or combinations thereof). In certain embodiments, the electrolyte comprises a superionic conductor (e.g., a sulfide, an oxide, and a phosphate (e.g., phosphorus pentasulfide), or combinations thereof).

[0138] In certain embodiments, the electrolyte is a liquid. For example, in certain embodiments, the electrolyte comprises an organic solvent. In certain embodiments, the electrolyte comprises only one organic solvent. In some embodiments, the electrolyte comprises a mixture of two or more organic solvents. In certain embodiments, the mixture of organic solvents comprises one or more of a weakly polar solvent, a strongly polar solvent, and a lithium-protecting solvent.

[0139] As used herein, the term "weakly polar solvent" is defined as a solvent capable of dissolving elemental sulfur and having a dielectric constant less than 15. Weakly polar solvents are selected from aryl compounds, bicyclic ethers, and acyclic carbonate compounds. Examples of weakly polar solvents include xylene, dimethoxyethane, 2-methyltetrahydrofuran, diethyl carbonate, dimethyl carbonate, toluene, dimethyl ether, diethyl ether, diglyme, tetraglyme, and the like. As used herein, the term "strongly polar solvent" is defined as a solvent capable of dissolving lithium polysulfide and having a dielectric constant greater than 15. Strongly polar solvents are selected from bicyclic carbonate compounds, sulfoxide compounds, lactone compounds, ketone compounds, ester compounds, sulfate compounds, and sulfite compounds. Examples of strong polar solvents include hexamethylphosphoric triamide, γ-butyrolactone, acetonitrile, ethylene carbonate, propylene carbonate, N-methylpyrrolidone, 3-methyl-2-oxazolidone, dimethylformamide, sulfolane, dimethylacetamide, dimethylsulfoxide, dimethyl sulfate, ethylene glycol diacetate, dimethyl sulfite, ethylene glycol sulfite, and the like. As used herein, the term "lithium protection solvent" is defined as a solvent that forms a good protection layer, i.e., a stable solid electrolyte interface (SEI) layer, on the lithium surface and exhibits at least 50% cycle efficiency. The lithium protection solvent is selected from saturated ether compounds, unsaturated ether compounds, and heterocyclic compounds containing one or more heteroatoms selected from the group consisting of N, O, and / or S. Examples of lithium protection solvents include tetrahydrofuran, 1,3-dioxolane, 3,5-dimethylisoxazole, 2,5-dimethylfuran, furan, 2-methylfuran, 1,4-oxane, 4-methyldioxolane, and the like.

[0140] In certain embodiments, the electrolyte is a liquid (e.g., an organic solvent). In some embodiments, the liquid is selected from the group consisting of an organic carbonate, an ether, a sulfone, water, an alcohol, a fluorocarbon, or any combination thereof. In certain embodiments, the electrolyte comprises an ether solvent.

[0141] In certain embodiments, the organic solvent comprises an ether. In certain embodiments, the organic solvent is selected from the group consisting of 1,3-dioxolane, dimethoxyethane, diglyme, triglyme, γ-butyrolactone, γ-valerolactone, and combinations thereof. In certain embodiments, the organic solvent comprises a mixture of 1,3-dioxolane and dimethoxyethane. In certain embodiments, the organic solvent comprises a 1:1 (v / v) mixture of 1,3-dioxolane and dimethoxyethane. In certain embodiments, the organic solvent is selected from the group consisting of diglyme, triglyme, γ-butyrolactone, γ-valerolactone, and combinations thereof. In certain embodiments, the electrolyte comprises sulfolane, sulfolene, dimethyl sulfone, methyl ethyl sulfone, or combinations thereof. In some embodiments, the electrolyte comprises ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, or combinations thereof.

[0142] In certain embodiments, the electrolyte is solid. In certain embodiments, the solid electrolyte comprises a polymer. In certain embodiments, the solid electrolyte comprises a glass, a ceramic, an inorganic composite, or a combination thereof. In certain embodiments, the solid electrolyte comprises a polymer composite containing a glass, a ceramic, an inorganic composite, or a combination thereof. In certain embodiments, such solid electrolytes include one or more liquid components as plasticizers or to form a "gel electrolyte". positive electrode

[0143] The cathode materials of the present disclosure are useful in the manufacture of electrochemical devices. The cathode materials may be porous or non-porous. Certain compositions disclosed herein may be deposited on a current collector to form a cathode of a secondary sulfur battery. The cathode compositions provided may include one or more additives (e.g., conductive particles, binders, and other functional additives commonly found in battery cathode mixtures). In general, the compositions provided include sufficient conductive particles to enhance the conductivity of the cathode and provide a low resistance path for electrons to access the cathode so produced. In various embodiments, other additives are included in the composition to modify or enhance the cathode produced according to the principles described herein. Other cathode components include, for example, a current collector, a connection tab, and the like.

[0144] In certain embodiments, the positive electrode composition comprises a sulfur electroactive material (e.g., the S 8 Sulfur in the form of cyclic octaatomic molecules) and / or lithium sulfide (e.g., Li 2 S 2 and / or Li 2 S) and / or in the form of an electroactive organosulfur compound or an electroactive sulfur-containing polymer. In certain embodiments, the electroactive material is an intercalation material structured to insert lithium ions. In certain embodiments, the electroactive material is S 8 →Li 2 Discharge voltage range of S (conversion of sulfur to lithium sulfide) (e.g., about 1.8 V to about 2.6 V vs. Li 0 For example, about 2.0V to about 2.4V vs. Li 0 ) and operates over a voltage range that overlaps with

[0145] In certain embodiments, the positive electrode composition includes a conductive material and a binder. In certain embodiments, the conductive material includes a conductive material that facilitates the movement of electrons within the composite. For example, in certain embodiments, the conductive material is selected from the group consisting of carbon-based materials, graphite-based materials, conductive polymers, metals, semiconductors, metal oxides, metal sulfides, and combinations thereof. In certain embodiments, the conductive material includes a carbon-based material. In certain embodiments, the conductive material includes a graphite-based material. In certain embodiments, the positive electrode composition is carbon-free or has a low carbon content (e.g., 5.0 wt.% or less, 3.0 wt.% or less, 2.0 wt.% or less, 1.0 wt.% or less, or 0.5 wt.% or less).

[0146] In certain embodiments, the conductive material is selected from the group consisting of carbon black, Super P®, C-NERGY™ SuperC65, Ensaco® black, Ketjenblack®, acetylene black, synthetic graphite such as Timrex® SFG-6, Timrex® SFG-15, Timrex® SFG-44, Timrex® KS-6, Timrex® KS-15, Timrex® KS-44, natural flake graphite, carbon nanotubes, fullerenes, hard carbon, mesocarbon microbeads, and other conductive carbon powders. In certain embodiments, the conductive material comprises one or more conductive polymers. For example, in certain embodiments, the conductive polymer is selected from the group consisting of polyaniline, polythiophene, polyacetylene, polypyrrole, and the like. In some embodiments, the conductive polymer is a cationic polymer. In some embodiments, the cationic polymer is a quaternary ammonium polymer. In certain embodiments, the cationic polymer is selected from the group consisting of polydiallyldimethylammonium salts, poly[(3-chloro-2-hydroxypropyl)methacryloxyethyldimethyl-ammonium salts, poly(butylacrylate-methacryloxyethyltrimethylammonium) salts, poly(1-methyl-4-vinylpyridinium) salts, poly(1-methyl-2-vinylpyridinium) salts, and poly(methacryloxyethyltriethylammonium) salts. In certain embodiments, the cationic polymer is selected from polydiallyldimethylammonium chloride (polyDADMAC), polybrene, epichlorohydrin-dimethylamine (epi-DMA), poly[(3-chloro-2-hydroxypropyl)methacryloxyethyldimethyl-ammonium chloride), poly(acrylamide-methacryloxyethyltrimethylammonium bromide), poly(butylacrylate-methacryloxyethyltrimethylammonium bromide), poly(1-methyl-4-vinylpyridinium bromide), poly(1-methyl-2-vinylpyridinium bromide), and poly(methylacryloxyethyltriethylammonium bromide).In certain embodiments, the conductive material comprises one or more metal oxides or metal sulfides. For example, in certain embodiments, the conductive material comprises one or more oxides or sulfides of a first row transition metal, such as titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, or combinations thereof. For example, in certain embodiments, the conductive material comprises one or more oxides or sulfides of a second row transition metal, such as zirconium, indium, tin, antimony, or combinations thereof. In certain embodiments, the conductive material is used alone. In other embodiments, the conductive material is used as a mixture of two or more of the above conductive materials.

[0147] In certain embodiments, a binder is included in the provided cathode composition material. Binders are generally polymeric materials that help to bond the individual particles that make up the cathode mixture together to form a stable composite. Exemplary binders include polyvinylidene fluoride, poly(vinylidene fluoride-co-hexafluoropropene) (PVDF / HFP), polytetrafluoroethylene (PTFE), Kynar Flex® 2801, Kynar® Powerflex LBG, Kynar® HSV 900, Teflon®, carboxymethyl cellulose, styrene-butadiene rubber (SBR), polyethylene oxide, polypropylene oxide, polyethylene, polypropylene, polyacrylate, polyvinylpyrrolidone, poly(methyl methacrylate), polyethyl acrylate, polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, polycaprolactam, polyethylene terephthalate, polybutadiene, polyisoprene, or polyacrylic acid, or any derivative, mixture, or copolymer thereof. In some embodiments, the binder is a water-soluble binder such as sodium alginate, carrageenan, or carboxymethylcellulose. In general, the binder holds the active material in contact with the current collector (e.g., a metal foil such as aluminum, stainless steel, copper, or a sheet of conductive carbon) together. In certain embodiments, the binder is selected from the group consisting of poly(vinyl acetate), polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, alkylated polyethylene oxide, crosslinked polyethylene oxide, polyvinyl ether, poly(methyl methacrylate), polyvinylidene fluoride, copolymers of polyhexafluoropropylene and polyvinylidene fluoride, polyethyl acrylate, polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, polyvinylpyridine, polystyrene, and derivatives, mixtures, and copolymers thereof. In some embodiments, the binder is a cationic polymer. In some embodiments, the binder is a quaternary ammonium polymer. In some embodiments, the binder is a cationic polymer as described above.

[0148] In some embodiments, the positive electrode composition further comprises a binder comprising a thiocarbonyl group (e.g., a compound provided). In some embodiments, the positive electrode composition further comprises a binder comprising a compound of any one of formulas I, II, III, or IV.

[0149] In certain embodiments, the positive electrode further comprises a coating layer, for example, in certain embodiments, the coating layer comprises a polymer, an organic material, an inorganic material, or a mixture thereof, which is not an integral part of the porous composite or the current collector. In certain such embodiments, the polymer is selected from the group consisting of polyvinylidene fluoride, copolymers of polyvinylidene fluoride and hexafluoropropylene, poly(vinyl acetate), poly(vinyl butyral-co-vinyl alcohol-co-vinyl acetate), poly(methyl methacrylate-co-ethyl acrylate), polyacrylonitrile, polyvinyl chloride-co-vinyl acetate, polyvinyl alcohol, poly(l-vinyl pyrrolidone-co-vinyl acetate), cellulose acetate, polyvinyl pyrrolidone, polyacrylates, polymethacrylates, polyolefins, polyurethanes, polyvinyl ethers, acrylonitrile-butadiene rubber, styrene butadiene rubber, acrylonitrile-butadiene styrene, sulfonated styrene / ethylene-butylene / styrene triblock copolymers, polyethylene oxide, and derivatives, mixtures, and copolymers thereof. In some embodiments, the coating layer comprises a cationic polymer. In some embodiments, the coating layer comprises a quaternary ammonium polymer. In some embodiments, the coating layer comprises a cationic polymer as described above. In certain such embodiments, the inorganic material is, for example, colloidal silica, amorphous silica, surface-treated silica, colloidal alumina, amorphous alumina, tin oxide, titanium oxide, titanium sulfide (TiS 2 ), vanadium oxide, zirconium oxide (ZrO 2 ), iron oxide, iron sulfide (FeS), iron titanate (FeTiO 3 ), barium titanate (BaTiO 3), and combinations thereof. In certain embodiments, the organic material comprises conductive carbon.

[0150] Materials suitable for use in the positive electrode mixture are disclosed in Cathode Materials for Lithium Sulfur Batteries: Design, Synthesis, and Electrochemical Performance, Lianfeng, et al., Interchopen.com, published June 1, 2016, and The strategies of advanced cathode composites for lithium-sulfur batteries, Zhou et al., SCIENCE CHINA Technological Sciences, Volume 60, Issue 2:175-185 (2017), the entire disclosures of each of which are incorporated herein by reference.

[0151] In certain embodiments, the positive electrode comprises one or more of the following features (a)-(l): (a) a "stack" of multifunctional materials (e.g., the stack comprises particles with gradient structures that balance ion and electron transport for improved power capability, energy density, and lifetime; comprises bifunctional positive electrode additives that store Li and simultaneously conduct electrons, replacing expensive and bulky carbons; comprises binding molecules that spatially confine the electrochemical reaction that stores energy, thereby extending lifetime; comprises electrolyte components that improve the basic efficiency of the electrolyte and improve energy density; and / or comprises electrolyte components that provide improved safety and energy density). (b) tight electrode layers; (c) tight tertiary structures; (d) porosity control; (e) core-shell structures; (f) crosslinked polymer shells; (g) self-doped polymer shells; (h) ionically conductive binders; (i) bilayer hybrid cathodes; (j) polysulfide-trapping polymers; (k) three-dimensional structures with high surface area (e.g., retaining (e.g., intercalating) both carbon and lithium); and (l) three-dimensional structures where carbon is substituted with metal disulfides (e.g., the battery contains a polymer electrolyte for sulfur). negative electrode

[0152] In certain embodiments, the secondary sulfur battery includes a lithium anode. Lithium anodes suitable for use in lithium-sulfur cells can be used. In certain embodiments, the anode of the secondary sulfur battery includes an anode active material selected from a material in which lithium intercalation occurs reversibly, a material that reacts with lithium ions to form a lithium-containing compound, metallic lithium, a lithium alloy, and combinations thereof. In certain embodiments, the anode includes metallic lithium. In certain embodiments, the lithium-containing anode composition includes a carbon-based compound. In certain embodiments, the carbon-based compound is selected from the group consisting of crystalline carbon, amorphous carbon, graphite, and mixtures thereof. In certain embodiments, the anode is carbon-free or has a low carbon content (e.g., 5.0 wt.% or less, 3.0 wt.% or less, 2.0 wt.% or less, 1.0 wt.% or less, or 0.5 wt.% or less). In certain embodiments, the material that reacts with lithium ions to form a lithium-containing compound is tin oxide (SnO 2 ), titanium nitrate, and silicon. In certain embodiments, the lithium alloy comprises an alloy of lithium with another alkali metal (e.g., sodium, potassium, rubidium, or cesium). In certain embodiments, the lithium alloy comprises an alloy of lithium with a transition metal. In certain embodiments, the lithium alloy comprises an alloy of lithium with a metal selected from the group consisting of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Al, Sn, In, Zn, Sm, La, and combinations thereof. In certain embodiments, the lithium alloy comprises an alloy of lithium with indium. In certain embodiments, the lithium alloy comprises an alloy of lithium with aluminum. In certain embodiments, the lithium alloy comprises an alloy of lithium with zinc. In certain embodiments, the negative electrode comprises a lithium-silicon alloy. Examples of suitable lithium-silicon alloys include Li 15 S 4 , Li 12 S 7 , Li 7 S 3 , Li 13 S4 , and Li 21 S 5 / Li 22 S 5 In certain embodiments, the lithium metal or lithium alloy is present as a composite with another material. In certain embodiments, such a composite includes a material such as graphite, graphene, a metal sulfide or oxide, or a conductive polymer.

[0153] In some embodiments, the negative electrode is protected from redox shuttling reactions and dangerous runway reactions by any of the methods reported in the art (e.g., by chemical passivation or by deposition or polymerization to generate a protective layer on the surface of the negative electrode). For example, in certain embodiments, the negative electrode comprises an inorganic protective layer, an organic protective layer, or a mixture thereof, on the surface of the lithium metal. In certain embodiments, the inorganic protective layer comprises Mg, Al, B, Sn, Pb, Cd, Si, In, Ga, lithium silicate, lithium borate, lithium phosphate, lithium phosphorus nitride, lithium silicosulfide, lithium borosulfide, lithium aluminosulfide, lithium phosphorus sulfide, lithium fluoride, or a combination thereof. In certain embodiments, the organic protective layer comprises a conductive monomer, oligomer, or polymer. In certain embodiments, such polymers are selected from poly(p-phenylene), polyacetylene, poly(p-phenylenevinylene), polyaniline, polypyrrole, polythiophene, poly(2,5-ethylenevinylene), acetylene, poly(perinaphthalene), polyacene, and poly(naphthalene-2,6-di-yl), or combinations thereof.

[0154] Furthermore, in certain embodiments, during charging and discharging of the secondary sulfur battery, inert sulfur material generated from the electroactive sulfur material of the positive electrode is deposited on the negative electrode surface. As used herein, the term "inert sulfur" refers to sulfur that cannot participate in the electrochemical reaction of the positive electrode and therefore does not contribute capacity upon repeated charge / discharge cycles. In certain embodiments, the inert sulfur on the negative electrode surface acts as a protective layer on such negative electrode. In certain embodiments, the inert sulfur is present in the form of lithium sulfide.

[0155] It is further believed that the concepts of the present disclosure may be adapted for use in sodium-sulfur batteries, which include a sodium-based negative electrode and an intercalation or conversion material capable of inserting or reacting with sodium ions. Such systems are encompassed within the embodiments of the present disclosure.

[0156] It is further contemplated that the present disclosure may be adapted for use in batteries assembled in a configuration that does not include an anode. In certain embodiments, the battery or battery component manufactured has a configuration that does not include an anode and includes an anode current collector (e.g., copper) and one or more of the following (a)-(e): (a) a thin layer of garnet; (b) a structure (e.g., a composite 3D structure) having a coating deposited by atomic layer deposition (ALD) (e.g., the ALD coating may be LiPON, garnet, oxide, perovskite, sulfide, Li, 3 BO 3 -Li 2 CO 3 (b) a polymer (e.g., polyethylene oxide (PEO) or a block copolymer); (c) a solid electrolyte interface (SEI) layer (e.g., an artificial SEI layer formed in situ); (d) a lithium phosphorus oxynitride (LiPON); and (e) a solid electrolyte interface (SEI) layer (e.g., an artificial SEI layer formed in situ).

[0157] 1. Preparation of Electrodes There are various methods for producing electrodes for use in secondary sulfur batteries. One such process, commonly referred to as the "wet process," involves adding solid cathode material to a liquid to prepare a slurry composition. Such slurries are usually in the form of viscous liquids formulated to facilitate downstream coating operations. Thorough mixing of the slurry can be important for coating and drying operations that affect the performance and quality of the electrode. Suitable mixing equipment includes ball mills, magnetic stirrers, ultrasonication, planetary mixers, high speed mixers, homogenizers, universal type mixers, and static mixers. The liquid used to prepare the slurry can be any that can uniformly disperse the active material, binder, conductive material, and any additives, and can also be evaporated. Suitable slurry liquids include, for example, N-methylpyrrolidone, acetonitrile, methanol, ethanol, propanol, butanol, tetrahydrofuran, water, isopropyl alcohol, dimethylpyrrolidone, propylene carbonate, gamma butyrolactone, and the like.

[0158] In some embodiments, the prepared composition is coated onto a current collector and dried to form an electrode. Specifically, the electrode is formed by coating a conductor with the slurry and spreading the slurry evenly over the conductor, and then, in certain embodiments, the electrode is roll pressed (e.g., calendered) and / or heated as needed, as known in the art. Generally, the matrix of active material and conductive material is held together on the conductor by a binder. In certain embodiments, the matrix comprises a polymer binder, such as polyvinylidene fluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropene) (PVDF / HFP), polytetrafluoroethylene (PTFE), Kynar Flex® 2801, Kynar® Powerflex LBG, Kynar® HSV900, Teflon®, styrene butadiene rubber (SBR), polyethylene oxide (PEO), or polytetrafluoroethylene (PTFE). In certain embodiments, additional carbon particles, carbon nanofibers, carbon nanotubes are dispersed in the matrix to improve electrical conductivity. Alternatively or additionally, in certain embodiments, a lithium salt is dispersed in the matrix to improve lithium conductivity.

[0159] In certain embodiments, the current collector is selected from the group consisting of aluminum foil, copper foil, nickel foil, stainless steel foil, titanium foil, zirconium foil, molybdenum foil, nickel foam, copper foam, carbon paper or carbon fiber sheet, a polymer substrate coated with a conductive metal, and / or combinations thereof.

[0160] PCT Publication Nos. WO2015 / 003184, WO2014 / 074150, and WO2013 / 040067, the disclosures of which are incorporated herein by reference in their entireties, describe various methods of manufacturing electrodes and electrochemical cells. Separator

[0161] In certain embodiments, the secondary sulfur battery includes a separator. The separator divides the negative and positive electrodes and prevents direct electronic conduction between them. In certain embodiments, the separator has high lithium ion permeability. In certain embodiments, the separator is relatively impermeable to polysulfide ions dissolved in the electrolyte. In certain such embodiments, the separator as a whole inhibits or limits the passage of electrolyte-soluble sulfides between the negative and positive electrode portions of the battery. In certain embodiments, the separator of impermeable material is configured to allow lithium ion transport between the negative and positive electrodes of the battery during charging and discharging of the cell. In some such embodiments, the separator is porous. One or more electrolyte-permeable channels can be provided that bypass or penetrate the impermeable surface of the separator to allow sufficient lithium ion flow between the negative and positive electrode portions of the battery.

[0162] As will be apparent to those skilled in the art, the optimum dimensions of the separator require a balance between the competing concerns of maximizing impedance to polysulfide migration while allowing sufficient lithium ion flow. Apart from this consideration, the shape and orientation of the separator is not particularly limited and will depend in part on the battery configuration. For example, in some embodiments, the separator is substantially circular in a coin-type cell and substantially rectangular in a pouch-type cell. In some embodiments, the separator is substantially flat. However, curved or other non-planar shapes are not precluded from being used.

[0163] The separator can be of any suitable thickness. To maximize the energy density of the battery, it is generally preferred that the separator be as thin and lightweight as possible. However, the separator should be thick enough to provide sufficient mechanical robustness and ensure adequate electrical isolation of the electrodes. In certain embodiments, the separator has a thickness of about 1 μm to about 200 μm, preferably about 5 μm to about 100 μm, and more preferably about 10 μm to about 30 μm. Secondary Sulfur Battery

[0164] Described herein is a secondary sulfur battery comprising the above-mentioned positive electrode composition. For example, in certain embodiments, such a battery comprises a provided positive electrode composition and a lithium-containing negative electrode composition combined therewith by a lithium conductive electrolyte. In some embodiments, such a battery also comprises additional components (e.g., a separator between the negative and positive electrodes, a negative and positive current collectors, terminals that can connect the cell to an external load, and packaging such as a flexible pouch or a rigid metal container). As further contemplated, the present disclosure regarding secondary sulfur batteries can be adapted for use in sodium-sulfur batteries, and such batteries are also considered to be within the scope of certain embodiments of the present disclosure.

[0165] 1 illustrates a cross-section of an electrochemical cell 800 according to an exemplary embodiment of the present disclosure. The electrochemical cell 800 includes a negative electrode 802, a positive electrode 804, a separator 806 interposed between the negative electrode 802 and the positive electrode 804, a container 810, and a fluid electrolyte 812 in contact with the negative electrode 802 and the positive electrode 804. Such a cell optionally includes additional layers of electrodes and separators 802a, 802b, 804a, 804b, 806a, and 806b.

[0166] The negative electrode 802 (sometimes referred to herein as the anode) comprises an active negative electrode material capable of accepting cations. Non-limiting examples of active negative electrode materials for lithium-based electrochemical cells include Li metal, Li alloys (e.g., Li alloys such as Si, Sn, Bi, In, and / or Al alloys), Li 4 Ti 5 O 12 , hard carbon, graphitic carbon, metal chalcogenides, and / or amorphous carbon. According to some embodiments of the present disclosure, most (e.g., greater than 90% by weight) of the negative electrode active material may be initially contained in the discharged positive electrode 804 (sometimes referred to herein as the positive electrode) when the electrochemical cell 800 is first fabricated, and thus the electrode active material forms part of the first electrode 802 during the initial charging of the electrochemical cell 800.

[0167] Methods for depositing an electroactive material onto a portion of the negative electrode 802 are described in U.S. Patent Publication Nos. 2016 / 0172660 and 2016 / 0172661 (applicant Fischer et al.), the contents of each of which are incorporated herein by reference to the extent that the content thereof is not inconsistent with this disclosure.

[0168] The positive electrode 804 (also referred to herein as the positive electrode) comprises a positive electrode composition as described herein. In certain embodiments, the positive electrode composition comprises about 30 to about 70 weight percent electroactive sulfur. In certain embodiments, the positive electrode comprises at least about 70% of the total sulfur present in the electrochemical cell. In certain embodiments, the positive electrode comprises at least about 80% of the total sulfur present in the electrochemical cell. In certain embodiments, the positive electrode comprises at least about 90% of the total sulfur present in the electrochemical cell. In certain embodiments, the positive electrode comprises at least about 95% of the total sulfur present in the electrochemical cell. In certain embodiments, the positive electrode comprises at least about 99% of the total sulfur present in the electrochemical cell. In certain embodiments, the positive electrode comprises substantially all of the total sulfur present in the electrochemical cell.

[0169] The negative electrode 802 and the positive electrode 804 can further include one or more conductive additives, as described above. According to some embodiments of the present disclosure, the negative electrode 802 and / or the positive electrode 804 further include one or more polymer binders, as described above.

[0170] FIG. 2 shows an example of a battery according to various embodiments described herein. A cylindrical battery is shown here for illustrative purposes, but other types of configurations, such as prismatic or pouch (laminated type) batteries, can also be used. The exemplary Li battery 901 includes a negative electrode 902, a positive electrode 904, a separator 906 interposed between the negative electrode 902 and the positive electrode 904, an electrolyte (not shown) impregnated in the separator 906, a battery case 905, and a sealing member 908 that seals the battery case 905. Of course, the exemplary battery 901 may simultaneously embody multiple aspects of the present disclosure in various designs.

[0171] The secondary sulfur battery of the present disclosure includes a lithium anode, a porous sulfur-based cathode, and an electrolyte that allows for the transport of lithium ions between the anode and cathode. In certain embodiments described herein, the anode portion of the battery includes the anode and a portion of the electrolyte in contact with the anode. Similarly, in certain embodiments described herein, the cathode portion of the battery includes the cathode and a portion of the electrolyte in contact with the cathode. In certain embodiments, the battery includes a lithium-ion permeable separator that forms an interface between the anode portion and the cathode portion. In certain embodiments, the battery includes a case that encapsulates both the anode portion and the cathode portion. In certain embodiments, the battery case includes a conductive anode end cover in electrical communication with the anode and a conductive cathode end cover in electrical communication with the cathode to facilitate charging and discharging via an external circuit.

[0172] In certain embodiments, the secondary sulfur battery of the present disclosure is specified in terms of its ratio of electrolyte to electroactive sulfur. The volume of the electrolyte and the ratio of electrolyte to sulfur in the positive electrode (volume / weight) correlate with the energy density of the sulfur battery. The electrolyte may be distributed among different parts of the volume in the cell, for example, the electrolyte may be included in the pores of the positive electrode, in the separator, and in contact with the negative electrode or between the negative electrode solid electrolyte phases. The electrolyte may also be included in other spaces in the battery that are not in direct contact with the negative electrode active material or the positive electrode active material, for example, the electrolyte may be left in the annular volume at the edge of a coin cell. In certain embodiments, the present disclosure provides a battery in which the entire or majority of the electrolyte is included in the positive electrode. Preferably, substantially all of the electrolyte is included in the positive electrode, and only the minimum amount of electrolyte required to wet the separator and negative electrode surface or SEI is outside the positive electrode. The electrolyte included in the positive electrode is called the "contained electrolyte" and its volume V CE can be estimated as the theoretical pore volume or as the porosity multiplied by the geometric volume of the positive electrode film. V CE =P% x area x thickness 陽極

[0173] In certain embodiments, the provided secondary sulfur battery has a total electrolyte content (V全体 ) is in the positive electrode (e.g., V CE / V 全体 In certain embodiments, the provided secondary sulfur battery is characterized by a total electrolyte content (V 全体 ) is in the positive electrode (e.g., V CE / V 全体 >0.8). In certain embodiments, the secondary sulfur battery has at least 60%, at least 65%, or at least 70% of the electrolyte contained in the positive electrode porous material. In certain embodiments, the secondary sulfur battery has at least 80%, at least 85%, or at least 90% of the electrolyte contained in the positive electrode porous material. In certain embodiments, the secondary sulfur battery has at least 92%, at least 94%, at least 95%, at least 96%, or at least 97% of the electrolyte contained in the positive electrode porous material.

[0174] The total electrolyte to sulfur ratio (E / S) is another parameter that affects the energy density of the battery. The E / S ratio is proportional to the total volume of electrolyte, V 全体 and the mass of electroactive sulfur (m 硫黄 ) is calculated based on

number

[0175] In certain embodiments, the secondary sulfur battery has an electrolyte to sulfur ratio of about 6 microliters or less per milligram of electroactive sulfur. In certain embodiments, the secondary sulfur battery has an electrolyte to sulfur ratio of about 5 microliters or less per milligram of electroactive sulfur. In certain embodiments, the secondary sulfur battery has an electrolyte to sulfur ratio of about 4.5 microliters or less per milligram of electroactive sulfur. In certain embodiments, the secondary sulfur battery has an electrolyte to sulfur ratio of about 3.5 microliters or less per milligram of electroactive sulfur, or an electrolyte to sulfur ratio of less than about 3.0 microliters per milligram of electroactive sulfur. In certain embodiments, the secondary sulfur battery has an electrolyte to sulfur ratio of about 3.5 microliters or less per milligram of electroactive sulfur. In certain embodiments, the secondary sulfur battery has an electrolyte to sulfur ratio of about 3 microliters or less per milligram of electroactive sulfur. In certain embodiments, the secondary sulfur battery has an electrolyte to sulfur ratio of about 1.8 to about 3.5 μL / mgS. In certain embodiments, the secondary sulfur battery has an electrolyte to sulfur ratio of about 1.8 to about 2.5 μL / mg S. In certain embodiments, the secondary sulfur battery has an electrolyte to sulfur ratio of about 1.0 to about 2.0 μL / mg S. In certain embodiments, the secondary sulfur battery has an electrolyte to sulfur ratio of about 1.5 to about 2.0 μL / mg S.

[0176] The additives disclosed herein do not necessarily have to be used as a replacement for the electrolyte solvent. In some embodiments, the additives are used in conjunction with an ether-based solvent in the electrolyte. In some embodiments, the additives are present in the electrolyte at a concentration ranging from 3 mM to 0.5 M, e.g., 10 mM to 0.5 M, 3 mM to 0.2 M, 10 mM to 0.2 M, 50 mM to 0.5 M, 50 mM to 0.2 M.

[0177] In some embodiments, the lithium-sulfur battery of the present disclosure includes a lithium anode, a sulfur-based cathode, and an electrolyte that allows for ion transport between the anode and cathode. In certain embodiments described herein, the anode portion of the battery includes the anode and a portion of the electrolyte in contact with the anode. Similarly, in certain embodiments described herein, the cathode portion of the battery includes the cathode and a portion of the electrolyte in contact with the cathode. In certain embodiments, the battery includes a lithium-ion permeable separator that forms a boundary between the anode portion and the cathode portion. In certain embodiments, the battery includes a case that encapsulates both the anode portion and the cathode portion. In certain embodiments, the battery case includes a conductive anode end cover in electrical communication with the anode and a conductive cathode end cover in electrical communication with the cathode to facilitate charging and discharging via an external circuit. EXAMPLES

[0178] The following examples embody certain methods of the present disclosure and illustrate the manufacture of porous cathode composite materials, and secondary sulfur batteries including such composite materials, according to certain embodiments described herein. Additionally, the following examples are included to illustrate the principles of the disclosed compositions and methods, and are not intended to be limiting.

[0179] Example 1 Preparation and Characterization of Electrochemical Cells Containing Electrolyte Additives This example illustrates various characteristics of an exemplary electrochemical cell according to embodiments disclosed herein. The exemplary electrochemical cell includes a sulfur-containing positive electrode, a lithium-containing negative electrode, an electrolyte, and a separator.

[0180] Electroactive materials for use in sulfur-containing positive electrodes were prepared by thermal melt diffusion of sulfur and carbon black at 130 °C for 3.5 h and then at 170 °C for 16 h. The active material was then cooled, ground, and processed using a 60 μm sieve. Positive electrodes were prepared by mixing the solvent, active material, PVDF binder, and carbon black using a high-speed bladeless mixer. The mixture was mixed to approximately 5-6 mg sulfur / cm2. cm2The cathodes were cast onto carbon coated aluminum collectors with target loadings ranging from 0.1 to 1.0 μg / cm2. The cast cathodes were dried at 60° C. in vacuum with a gas sweep.

[0181] 1,2-Dimethoxyethane, 1,3 Dioxolane, Lithium salt, LiNO 3 The electrolyte was prepared by mixing 1,2-benzodithiol-3-one with one of 3H-1,2-benzodithiol-3-one, phenylacetyl disulfide, tetramethylthiourea, thioacetamide, thiourea, trithiocyanuric acid, vinylene trithiocarbonate, zinc dimethyldithiocarbamate, and dimethyltrithiocarbonate.

[0182] These electrochemical cells containing electrolytes with additives were tested against control electrochemical cells prepared in a similar manner except for the electrolyte composition, which consisted of 1,2-dimethoxyethane, 1,3 dioxolane, lithium salt, and LiNO. 3 The control cell is designated "Beta" throughout Figures 3-13 and their corresponding data.

[0183] 0.1c Discharge Specific Capacity: Figure 3 shows the 0.1c discharge specific capacity data for the electrochemical cells tested. Without wishing to be bound by any particular theory, the 0.1c discharge specific capacity is useful in understanding the utilization and / or energy of the cell. As shown in Figure 3, the cells containing electrolytes containing ziram gave the highest performance in terms of 0.1c discharge specific capacity compared to the other additives.

[0184] Discharge Specific Capacity at 0.333c: FIG. 4 shows the discharge specific capacity data at 0.333c for the electrochemical cells tested. Without wishing to be bound by any particular theory, the discharge specific capacity at 0.333c is useful in understanding the rated and / or power performance of the cell. As shown in FIG. 4, the cells containing electrolytes containing one of tetramethyl, thiourea, thioacetamide, thiourea, and ziram performed best compared to the other cells. One common feature of each compound is that each contains an NCS moiety. Furthermore, trithiocyanuric acid, which has an aromatic core containing an NCS moiety, performed similarly to tetramethyl, thiourea, thioacetamide, thiourea, and ziram. Without wishing to be bound by any particular theory, it is believed that the improved performance of each of the above additives is due to each compound having an NCS moiety and a thiocarbonyl group.

[0185] Average Discharge Voltage: Figure 5 shows the average discharge voltage data, where the discharge voltage is normalized to the capacity. Without being bound by any theory, improved cell performance is usually associated with a higher average discharge voltage, which may indicate lower resistance. As seen in Figure 5, tetramethylthiourea, thioacetamide, thiourea, vinylene trithiocarbonate, and ziram showed higher performance compared to other additives.

[0186] Pulse average efficiency: Figure 6 shows the pulse average efficiency, which was determined as the average of each of the pulse efficiencies over the discharge, where the pulse efficiency was determined as the integrated area at C / 10 voltage divided by the integrated area at 1 C voltage during the 5 second pulse. As can be seen in Figure 6, tetramethylthiourea, thioacetamide, and thiourea showed high performance compared to other additives.

[0187] First plateau efficiency at end of pulse: Figure 7 shows data for the first plateau efficiency at end of pulse, determined as the pulse efficiency for the first pulse above 300 mAh / gS and at 25% depth of discharge. As seen in Figure 7, tetramethylthiourea, thioacetamide, and thiourea showed high performance compared to other additives.

[0188] Pulse end of discharge efficiency: Figure 8 shows the data for pulse end of discharge efficiency, determined as the pulse efficiency averaged over each pulse above 600 mAh / gS and 75% depth of discharge. As seen in Figure 8, tetramethylthiourea, thioacetamide, and thiourea showed high performance compared to other additives.

[0189] Without being bound to any particular theory, the strong performance of tetramethylthiourea, thioacetamide, and thiourea observed throughout the testing shown in Figures 6-8 was significant as this indicates consistent cell performance throughout cell discharge.

[0190] Coulombic efficiency: Figure 9 shows the data for coulombic efficiency, determined as the ratio of discharge capacity divided by charge capacity. Without being bound to any theory, the coulombic efficiency represents the maximum limit of the cycle life performance of the cell. As shown in Figure 10, each additive performed similarly to each other.

[0191] Thermal Efficiency: Figure 10 shows data for thermal efficiency, determined as the ratio of discharge energy divided by charge energy over one complete cycle of an electrochemical cell. Without being bound by any theory, a high thermal efficiency value indicates good thermal management within the cell. As shown in Figure 10, each additive performed similarly to each other.

[0192] Voltage Efficiency: Figure 11 shows the data for voltage efficiency, determined as the ratio of the average discharge voltage divided by the average charge voltage over one complete cycle of the electrochemical cell. As shown in Figure 11, each additive performed similarly to each other.

[0193] Example 2 Preparation and Characterization of Electrochemical Cells Containing Functional Binders Electroactive materials for use in sulfur-containing positive electrodes can be prepared by thermal melt diffusion of sulfur and carbon black at 130°C for 3.5 hours, followed by 170°C for 16 hours. The active material can then be cooled, ground, and processed using a 60 μm sieve. A high-speed bladeless mixer can be used to prepare positive electrodes in which the solvent, active material, binder containing thiocarbonyl functional groups, and carbon black are mixed. The mixture is mixed to obtain approximately 5-6 mg sulfur / cm2. cm2 The cathode can be cast onto a carbon coated aluminum collector with a target loading ranging from 0.1 to 1.0 μg / cm2. The cast cathode can then be dried at 60° C. in vacuum with a gas sweep.

[0194] Example 3 Electrochemical characteristics of cells containing electrolytes containing the disclosed additives To evaluate the effect of the additives of the present disclosure on the performance of lithium-sulfur secondary batteries, coin cells can be constructed. The positive electrode material can be prepared as described in Example 1. For example, the positive electrode material can be prepared by mixing the active material (e.g., 75 wt. % active material containing a mixture of about 80 wt. % elemental sulfur and about 20 wt. % polyaniline), a conductive carbon additive (e.g., 14 wt. % C65 (registered trademark) and a 100% ethylenediaminetetraacetate (EDA)). 商標 A mixture of sulfur, sulphur dioxide, ammonium phosphate, ammonium nitrate, ammonium phosphate diluent, and a binder (e.g., 11 wt % PVDF) can be prepared. These ingredients are combined in a minimum amount of solvent (e.g., NMP) and mixed to form a homogenous slurry. The resulting slurry is applied to a carbon-coated Al foil and allowed to dry overnight prior to use. Disks are punched (e.g., 1.27 cm diameter) from the cathode film. The final sulfur loading for each cathode is approximately 3 g / cm. 2 It can be said that: The positive electrode punch can be used in combination with the following components to construct a CR2032 coin cell: A negative electrode, e.g., a 0.2 mm thick Li metal disk with a 9 / 16 inch diameter Separator, e.g. Celgard-0325 Electrolytes: Add a sufficient amount of electrolyte (e.g., 1 M LiTFSI and 0.2 M LiNO in a 1:1 volumetric mixture of DME:DOL).3 ) to each coin cell to bring the E:S ratio of the cells to the desired ratio. For example, if the E:S is approximately 3, 13 μL of electrolyte can be used in each coin cell. Electrochemical testing can be performed at room temperature using a Maccor 4000 battery tester. The cycling protocol can include the following steps: 1. An initial 3-hour rest period 2. Initial discharge at rate C / 20 – label this as cycle 0 3. Charge / discharge cycle at rate C / 20 – labelled as cycle 1 4. Charge / discharge cycle at rate C / 10 – labelled as cycle 2 5. 9 charge / discharge cycles at rate C / 3 6. Charge / discharge cycle at rate C / 10 7. Repeat steps 4 and 5 30 times (300 cycles in total). A 10 minute rest period may be applied after completion of each charge and discharge cycle. The appropriate voltage cutoff upper limit is 2.8V vs Li + / Li The appropriate voltage cutoff lower limit is 1.7V vs Li + / Li The discharge capacity of the electrochemical cell is measured using the cycling protocol described above.

[0195] Example 4 Preparation of thiocarbonyl during discharge This example shows the preparation of thiocarbonyl additives during battery cycling. A slurry can be prepared by mixing 3H-1,2-benzodithiol-3-one with phenylacetyl disulfide, and the slurry can be included in an electrochemical cell with a lithium polythioacrylate binder (e.g., the polythioacrylate binder is included in a proportion of 20% by weight or less). Without being bound by any theory, during operation of an electrochemical cell containing the above components, the disulfide bonds of the slurry components are reduced at the negative or positive electrode of the electrochemical cell at the beginning of discharge to produce polyacrylic acid thiocarboxylate analogs, which have a resonance form containing thiocarbonyl.

[0196] Exemplary Numbered Embodiments The following numbered embodiments illustrate, but are not limiting, certain aspects of the present disclosure. 1. A binder for sulfur positive electrodes, containing thiocarbonyl functional groups. 2. An additive for the electrolyte of lithium-sulfur batteries, containing thiocarbonyl functional groups. 3. An electrolyte for lithium-sulfur batteries containing thiocarbonyl functional groups. 4.Formula X y 3. The binder, additive, or electrolyte of any one of the preceding embodiments, comprising a thiocarbonyl functional group of C=S, where each X is independently selected from oxygen, nitrogen, sulfur, or carbon, and y is 1 or 2, with the proviso that one X may form a ring with the other X and an intervening atom, and when y is 1, X is connected to the thiocarbonyl carbon through a double bond. 5. The binder, additive, or electrolyte of embodiment 4, wherein y is 2. 6. The binder, additive, or electrolyte of embodiment 4 or 5, wherein each X is independently selected from nitrogen, sulfur, or carbon. 7. The binder, additive, or electrolyte of embodiment 4 or 5, wherein each X is independently selected from sulfur or carbon. 8. The binder, additive, or electrolyte of embodiment 4, wherein y is 1. 9. The binder, additive, or electrolyte of embodiment 8, comprising an isothiocyanate functional group. 10. The binder, additive, or electrolyte of any one of the preceding embodiments, wherein the binder, additive, or electrolyte has not been cycled. 11. Compound of formula I': [ka] In the formula, R 1 and R 2 are each independently hydrogen or C 1~15 an optionally substituted group selected from aliphatic, 3-7 membered saturated or partially saturated monocyclic carbocyclyl, 4-10 membered saturated or partially unsaturated bicyclic carbocyclyl, 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, 7-10 membered saturated or partially unsaturated bicyclic heterocyclyl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, phenyl, 8-10 membered bicyclic aryl, 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or 8-10 membered bicyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur; or R 1 and R 2 together with the intervening atoms form an optionally substituted ring; Each X is absent or independently O, S, NR z , and C.R. 3 R 4 is selected from Each R z are independently hydrogen or optionally substituted C 1~12 It is aliphatic, Each R 3 and R 4 are independently hydrogen, halogen, -CN, -NO 2 , -N(R) 2 , -OR, -SR, or C 1~12an optionally substituted group selected from aliphatic, 3-7 membered saturated or partially saturated monocyclic carbocyclyl, 4-10 membered saturated or partially unsaturated bicyclic carbocyclyl, 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, 7-10 membered saturated or partially unsaturated bicyclic heterocyclyl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, phenyl, 8-10 membered bicyclic aryl, 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or 8-10 membered bicyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur; Each R is independently hydrogen, optionally substituted C 1~6 an aliphatic, optionally substituted 3-7 membered saturated or partially unsaturated carbocyclyl, or an optionally substituted 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or two R's, when attached to the same nitrogen atom, together form an optionally substituted 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 0-2 additional heteroatoms independently selected from nitrogen, oxygen, and sulfur. 12. Compounds of formula I: [ka] [In the formula, R 1 and R 2 are each independently 1~15an optionally substituted group selected from aliphatic, 3-7 membered saturated or partially saturated monocyclic carbocyclyl, 4-10 membered saturated or partially unsaturated bicyclic carbocyclyl, 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, 7-10 membered saturated or partially unsaturated bicyclic heterocyclyl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, phenyl, 8-10 membered bicyclic aryl, 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or 8-10 membered bicyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur; or R 1 and R 2 together with the intervening atoms form an optionally substituted ring; Each X is absent or independently O, S, NR z , and C.R. 3 R 4 is selected from Each R z are independently hydrogen or optionally substituted C 1~12 It is aliphatic, Each R 3 and R 4 are independently hydrogen, halogen, -CN, -NO 2 , -N(R) 2 , -OR, -SR, or C 1~12an optionally substituted group selected from aliphatic, 3-7 membered saturated or partially saturated monocyclic carbocyclyl, 4-10 membered saturated or partially unsaturated bicyclic carbocyclyl, 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, 7-10 membered saturated or partially unsaturated bicyclic heterocyclyl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, phenyl, 8-10 membered bicyclic aryl, 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or 8-10 membered bicyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur; Each R is independently hydrogen, optionally substituted C 1~6 an aliphatic, optionally substituted 3-7 membered saturated or partially unsaturated carbocyclyl, or an optionally substituted 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or two R, when attached to the same nitrogen atom, together form an optionally substituted 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 0-2 additional heteroatoms independently selected from nitrogen, oxygen, and sulfur. 13.R 1 and R 2 together with the intervening atoms, a 3- to 7-membered saturated or partially unsaturated monocyclic carbocyclyl; Compounds according to embodiments 11 or 12, which form an optionally substituted ring selected from a 4-10 membered saturated or partially unsaturated bicyclic carbocyclyl, a 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, a 7-10 membered saturated or partially unsaturated bicyclic heterocyclyl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, a phenyl, an 8-10 membered bicyclic aryl, a 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or an 8-10 membered bicyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. 14.R 1 and R 2 together with the intervening atoms form an optionally substituted 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1 to 3 heteroatoms independently selected from nitrogen, oxygen, and sulfur. 15.R 1 and R 2 The compound of embodiment 14, wherein together with intervening atoms, form an optionally substituted 5-membered saturated or partially unsaturated monocyclic heterocyclyl having two sulfur heteroatoms. 16.R 1 and R 2 14. The compound of claim 13, wherein, together with the intervening atoms, forms an optionally substituted 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. 17.R 1 and R 2 together with the intervening atoms form a ring A as in formula II: [ka] Ring A is an optionally substituted ring selected from a 3-7 membered saturated or partially unsaturated monocyclic carbocyclyl, a 4-10 membered saturated or partially unsaturated bicyclic carbocyclyl, a 3-7 membered saturated or partially unsaturated monocyclic heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, a 7-10 membered saturated or partially unsaturated bicyclic heterocyclyl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, a phenyl, an 8-10 membered bicyclic aryl, a 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or an 8-10 membered bicyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. 18. Compounds according to embodiment 17, wherein Ring A is an optionally substituted 5-membered saturated or partially unsaturated monocyclic heterocyclyl having two sulfur heteroatoms. 19. The compound according to embodiment 17, wherein Ring A is an optionally substituted 5-6 membered monocyclic heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. 20. The compound according to any one of embodiments 11-19, wherein both X are absent. 21. The compound according to any one of embodiments 11-19, wherein both X's are S. 22. Both X's are NR 2 20. The compound of any one of embodiments 11-19, wherein 23. The compound according to embodiment 11 or 12, wherein the compound is trithiocyanuric acid. 24. A binder, additive, or electrolyte comprising a compound according to any one of embodiments 11 to 23. 25. A binder, additive, or electrolyte comprising a compound selected from the group consisting of 3H-1,2-benzodithiol-3-one, phenylacetyl disulfide, tetramethylthiourea, thioacetamide, thiourea, trithiocyanuric acid, vinylene trithiocarbonate, zinc dimethyldithiocarbamate, and dimethyltrithiocarbonate. 26. [ka] [ka] [ka] A binder, additive, or electrolyte comprising a compound selected from the group consisting of: 27. An electrolyte composition comprising a compound selected from the group consisting of 3H-1,2-benzodithiol-3-one, phenylacetyl disulfide, tetramethylthiourea, thioacetamide, thiourea, trithiocyanuric acid, vinylene trithiocarbonate, zinc dimethyldithiocarbamate, and dimethyltrithiocarbonate. 28. [ka] [ka] [ka] 1. An electrolyte composition comprising a compound selected from the group consisting of: 29. One X is NR z and the other X is independently O, S, or NR z , and C.R. 3 R 4 Selected from R z , R 1 , R 2 , R 3 , and R 4 The compound of embodiment 11 or 12, wherein each of is hydrogen. 30. Each X is independently NR z and R z , R 1 , and R 2 each independently is hydrogen or C 1~6 The compound of embodiment 11 or 12, which is aliphatic. 31. Each X is independently NR z and R z , R1 , and R2 The compound of embodiment 11 or 12, wherein each of is hydrogen. 32. An electrolyte composition comprising a compound according to any one of embodiments 11 to 23 or 29 to 31. 33. Compound of formula III: [ka] 33. The electrolyte composition of embodiment 32, further comprising: wherein n is 3, 4, 5, 6, 7, or 8. 34. Compound of formula IV: [ka] 34. The electrolyte composition of embodiment 32 or 33, further comprising: wherein n is 3, 4, 5, 6, 7, or 8. 35. Li (S) n R 1 The electrolyte composition according to any one of embodiments 32 to 34, further comprising: 36. Li (S) n R 2 36. The electrolyte composition of any one of embodiments 32 to 35, further comprising: 37. The electrolyte composition of any one of embodiments 32-36, wherein X is S. 38. The electrolyte composition of any one of embodiments 32-37, wherein lithium trithiocarbonate is the predominant (e.g., highest weight or volume percentage) lithium salt in the composition. 39. The electrolyte composition of any one of embodiments 32-38, wherein the electrolyte composition has not been cycled. 40. A lithium-sulfur battery comprising a binder, additive, or electrolyte according to any one of embodiments 1-10, or 24-28, or 32-39. 41. A lithium-sulfur battery comprising a compound according to any one of embodiments 11 to 22. 42. A lithium-sulfur battery comprising an electrolyte composition according to any one of embodiments 32 to 39. 43. A lithium-sulfur battery according to any one of embodiments 40-42, which has not been cycled. 44. A method for producing a lithium-sulfur battery, comprising the step of adding a binder, additive, or electrolyte according to any one of embodiments 1-10 or 24-28, a compound according to any one of embodiments 11-23, or an electrolyte composition according to any one of embodiments 32-39 to a battery case, said step being performed before charging or discharging.

[0197] While a number of embodiments of the present invention have been described, it will be apparent that the basic examples of the invention can be modified to provide other embodiments that utilize the compounds and methods of the present invention. It will therefore be understood that the scope of the invention is to be defined by the appended claims rather than by the specific embodiments that have been represented by way of example.

Claims

1. An additive for the electrolyte of a lithium-sulfur battery, wherein the additive contains a thiocarbonyl functional group.

2. The thiocarbonyl functional group is of formula X ｙ The additive according to claim 1, wherein C=S, and in the formula, each X is independently selected from oxygen, nitrogen, sulfur, and carbon, and y is 1 or 2, provided that one X may form a ring with the other X and intervening atoms, and when y is 1, X is connected to the thiocarbonyl carbon via a double bond.

3. The additive according to claim 2, wherein y is 2.

4. The additive according to claim 2, wherein each X is independently selected from nitrogen, sulfur, and carbon.

5. The additive according to claim 2, wherein each X is nitrogen.

6. The additive according to claim 2, wherein the additive comprises a thiocarbonate, thiourea, thiocarbamate, thioketone, trithiocarbonate, thioamide, dithiocarbamate, or isothiocyanate functional group.

7. The additive is 3H-1,2-benzodithiol-3-one, phenylacetyl disulfide, tetramethylthiourea, thioacetamide, thiourea, trithiocyanuric acid, vinylenthrithiocarbonate, zinc dimethyldithiocarbamate, dimethyltrithiocarbonate, and Table 1-1 Table 1-2 Table 1-3 The additive according to claim 1, comprising a compound selected from the group consisting of the compounds shown in [reference].

8. An electrolyte composition for a lithium-sulfur battery, wherein the electrolyte composition comprises the additive described in any one of claims 1 to 7.

9. The electrolyte composition according to claim 8, wherein the electrolyte composition is not cyclic.

10. The electrolyte composition according to claim 8, further comprising a lithium salt, lithium nitrate, and an ether solvent.

11. The electrolyte composition according to claim 10, wherein the lithium salt comprises lithium bis(trifluoromethanesulfonyl)imide, and the ether solvent comprises 1,2-dimethoxyethane, 1,3-dioxolane, or both.

12. A lithium sulfur battery, sulfur-containing positive electrode, Lithium-containing anode, A separator between the sulfur-containing positive electrode and the lithium-containing negative electrode, and Electrolyte composition according to claim 8 Lithium sulfur batteries, including those containing lithium sulfur.

13. The lithium sulfur battery according to claim 12, wherein the lithium sulfur battery is not cycled.

14. The lithium sulfur battery according to claim 12, wherein the lithium sulfur battery is cyclic, and the electrolyte composition comprises a thiocarbonyl-containing compound having a lithiated polysulfide substituent containing (S)nLi, wherein n is 3, 4, 5, 6, 7, or 8.

15. The lithium sulfur battery according to claim 14, wherein the thiocarbonyl-containing compound having a lithiated polysulfide substituent is a reaction product of lithium polysulfide and the additive.

16. The electrolyte composition is a compound of formula III: R 1 -X-C(=S)-(S) n Li [In the formula, n is 3, 4, 5, 6, 7, or 8. R1 is hydrogen, or C １～１５ A optionally substituted group selected from aliphatic, 3-7 member saturated or partially unsaturated monocyclic carbocyclyls, 4-10 member saturated or partially unsaturated bicyclic carbocyclyls, 3-7 member saturated or partially unsaturated monocyclic heterocyclyls having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, 7-10 member saturated or partially unsaturated bicyclic heterocyclyls having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, phenyl, 8-10 member bicyclic aryls, 5-6 member monocyclic heteroaryls having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, and 8-10 member bicyclic heteroaryls having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. X does not exist, or O, S, NR ｚ , and CR ３ R ４ Selected from, Each R ｚ C is independently substituted with hydrogen, or optionally substituted with C １～１２ It is aliphatic, Each R ３ and R ４ are independently hydrogen, halogen, -CN, -NO ２ , -N(R) ２ , -OR, -SR, or C １～１２ an optionally substituted group selected from aliphatic, 3- to 7-membered saturated or partially unsaturated monocyclic carbocyclyl, 4- to 10-membered saturated or partially unsaturated bicyclic carbocyclyl, 3- to 7-membered saturated or partially unsaturated monocyclic heterocyclyl having 1 to 3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, 7- to 10-membered saturated or partially unsaturated bicyclic heterocyclyl having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, phenyl, 8- to 10-membered bicyclic aryl, 5- to 6-membered monocyclic heteroaryl having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, and 8- to 10-membered bicyclic heteroaryl having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, and sulfur Each R is independently substituted with hydrogen, and optionally with C. １～６ [These are aliphatic, optionally substituted 3-7 member saturated or partially unsaturated carbocyclils, or optionally substituted 3-7 member saturated or partially unsaturated monocyclic heterocyclils having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or the two R groups, when bonded to the same nitrogen atom, together form optionally substituted 3-7 member saturated or partially unsaturated monocyclic heterocyclils having 0-2 additional heteroatoms independently selected from nitrogen, oxygen, and sulfur.] A lithium sulfur battery according to claim 14, including the following:

17. The electrolyte composition is a compound of formula IV: R 2 -X-C(=S)-(S) n Li [In the formula, n is 3, 4, 5, 6, 7, or 8. R ２ is hydrogen, or C １～１５ A optionally substituted group selected from aliphatic, 3-7 member saturated or partially unsaturated monocyclic carbocyclyls, 4-10 member saturated or partially unsaturated bicyclic carbocyclyls, 3-7 member saturated or partially unsaturated monocyclic heterocyclyls having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, 7-10 member saturated or partially unsaturated bicyclic heterocyclyls having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, phenyl, 8-10 member bicyclic aryls, 5-6 member monocyclic heteroaryls having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, and 8-10 member bicyclic heteroaryls having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. X does not exist, or O, S, NR ｚ , and CR ３ R ４ Selected from, Each R ｚ C is independently substituted with hydrogen, or optionally substituted with C １～１２ It is aliphatic, Each R ３ and R ４ These are independently hydrogen, halogen, -CN, and -NO ２ , -N(R) ２ -OR, -SR, or C １～１２ A optionally substituted group selected from aliphatic, 3-7 member saturated or partially unsaturated monocyclic carbocyclyls, 4-10 member saturated or partially unsaturated bicyclic carbocyclyls, 3-7 member saturated or partially unsaturated monocyclic heterocyclyls having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, 7-10 member saturated or partially unsaturated bicyclic heterocyclyls having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, phenyl, 8-10 member bicyclic aryls, 5-6 member monocyclic heteroaryls having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, and 8-10 member bicyclic heteroaryls having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. Each R is independently substituted with hydrogen, and optionally with C. １～６ [These are aliphatic, optionally substituted 3-7 member saturated or partially unsaturated carbocyclils, or optionally substituted 3-7 member saturated or partially unsaturated monocyclic heterocyclils having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or the two R groups, when bonded to the same nitrogen atom, together form optionally substituted 3-7 member saturated or partially unsaturated monocyclic heterocyclils having 0-2 additional heteroatoms independently selected from nitrogen, oxygen, and sulfur.] A lithium sulfur battery according to claim 14, including the following:

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