BR112019011107B1 - BATTERY BASED ON ORGANO SULFUR, ELECTROLYTE AND ANODE - Google Patents

Abstract

Sulfur-metal batteries, such as lithium-sulfur batteries, are prepared using one or more organosulfur species, such as organic polysulfides and organic polythiolates, as part of the liquid or gel electrolyte solution, as part of the cathode, as part of the anode (or used to treat the anode), and/or with part of a functionalized porous polymer that provides an intermediate separating element.

Description

Field of Invention

[0001] The invention relates to batteries with an anode based on sodium, lithium, potassium, magnesium, or a mixture thereof, or alloy or composite of sodium, lithium, potassium and/or magnesium with one or more other metals, and a cathode based on elemental sulfur, selenium, or a mixture of elemental chalcogens, the anode and cathode being separated by a separating element with a liquid electrolyte or gel solution of a conductive salt in a non-aqueous polar aprotic solvent or polymer in contact with the electrodes.

Fundamentals of the Invention

[0002] Electrochemical batteries are a primary means of storing and delivering electrical energy. Because of the ever-increasing demands on energy for electronic applications, transportation, and the storage network, the need for batteries capable of storing and delivering more and more energy will continue for a long time to come.

[0003] Due to their low weight and high energy storage capacity compared to other types of batteries, lithium-ion batteries have been widely used since the early 1990s for portable electronic applications. However, current Li-ion battery technology does not meet the high power and energy needs for large applications such as grid storage or self-driving electric vehicles that are competitive with vehicles powered by internal combustion engines. Thus, extensive efforts in the scientific and technical communities continue to identify batteries with higher energy density and capacity.

[0004] Sodium-sulfur and lithium-sulfur electrochemical cells offer even greater theoretical energy capacity than Li-ion cells and thus have continued to elicit interest as “next generation” battery systems. Electrochemical conversion of elemental sulfur to monomeric sulfide (S2-) gives a theoretical capacity of 1675 mAh/g, compared to less than 300 mAh/g for Li-ion cells.

[0005] Sodium-sulfur batteries were developed and released as commercial systems. Unfortunately, the sodium-sulfur cell typically requires high temperatures (over 300°C) to be functional, and thus is only suitable for large stationary applications.

[0006] Lithium-sulfur electrochemical cells, initially proposed in the late 1950s and 1960s, are just now being developed as commercial battery systems. These cells offer theoretical specific energy densities above 2500 Wh/kg (2800 Wh/L) vs. 624 Wh/g for lithium ions. The specific energy densities demonstrated for Li-S cells are in the range of 250350 Wh/kg, compared to 100 Wh/g for Li-ion cells, the lower values being the result of specific features of the electrochemical processes for these systems during charging. and unloading. Given that the practical specific energies of lithium batteries are typically 25-35% of the theoretical value, the ideal practical specific energy for a Li-S system could be around 780 Wh/g (30% theoretical). [V.S. Kolosnitsyn, E. Karaseva, US Patent Application 2008/0100624 A1].

[0007] Lithium-sulfur chemistry offers numerous technical challenges that hampered the development of these electrochemical cells, particularly the low charge-discharge cycle capability. However, because of the low weight, low cost, high power capacity inherent in the lithium-sulfur cell, there is great interest in improving the performance of the lithium-sulfur system and extensive work has been carried out in the last 20 years by many researchers in around the world to address these problems. [Ç. Liang, et al. in Handbook of Battery Materials 2nd Ed., Chapter 14, pp. 811-840 (2011); V.S. Kolosnitsyn, et al., J. Power Sources 2011, 196, 1478-82; and references in it]

[0008] A cell design for a lithium-sulfur system typically includes: • An anode consisting of lithium metal, lithium alloy, or lithium-containing composite materials. • A non-reactive but porous separator between the anode and cathode (often polypropylene or α-alumina). The presence of this separator results in separate anolyte and catholyte compartments. • A porous sulfur-bearing cathode that incorporates a binder (often poly(vinylidene difluoride)) and a conductivity enhancing material (often graphite, mesoporous graphite, multi-walled carbon nanotubes, graphene), • An electrolyte consisting of a polar aprotic solvent and one or more conductive Li salts [(CF3SO2)2N“, CFβSOβ-, CHeSOs", ClO4-, PFβ", AsF6-, halogens, etc.]. Solvents used in these cells included basic aprotic polar solvents (cation-complexing) such as sulfolane, dimethyl sulfoxide, dimethylacetamide, tetramethyl urea, N-methyl pyrrolidinone, tetraethyl sulfamide, tetrahydrofuran, methyl-THF, 1,3-dioxolane, diglyme, and tetraglyme. are suitable because of the low conductivity and low ability to solvate Li+ species, and protic solvents can react with metallic Li. In solid-state versions of the lithium-sulfur cell, liquid solvents are substituted with in a polymeric material such as polyethylene oxide. • Current collectors and appropriate coating materials. Summary of the Invention

[0009] Compositions and applications of organic polysulfide, organic thiolate and organic polythiolate for use in sulfur-metal batteries, particularly lithium-sulfur batteries, are provided by the present invention. Organic polysulfide, organic thiolate, and organopolythiolate species (hereinafter sometimes referred to as “organosulfur species”) act to improve the performance of such electrochemical cells during repeated discharge and charge cycles.

[0010] The present invention thus relates to chemical sources of energy comprising a cell or battery with one or more positive electrodes (cathodes), one or more negative electrodes (anodes) and an electrolyte medium, wherein the operative chemistry involves reduction sulfur or polysulfide species, and oxidation of the reactive metal species. The negative electrode comprises a reactive metal such as lithium, sodium, potassium, magnesium or alloys/composites of these metals with other materials; in certain embodiments, the negative electrode additionally comprises at least one organosulfur species and/or has been treated with at least one organosulfur species. The positive electrode comprises sulfur and/or elemental selenium and, in certain embodiments of the invention, organosulfide species such as organic polysulfide species and/or organic polysulfide metal salts, and matrices containing such species. Electrolyte matrices, in certain embodiments, comprise mixtures of organic solvents or polymers, inorganic or organic polysulfide species, carriers for the ionic form of the active metal, and other components intended to optimize electrochemical performance.

[0011] Specifically, this invention relates to the use of organic sulfides and polysulfides, and their lithium organothiolate or organopolythiolate analogues (or sodium, potassium, magnesium, quaternary ammonium or quaternary phosphonium), as components in the cathode and electrolyte matrices. Said organosulfide species chemically combines with sulfur and the anionic mono- or polysulfide species to form organopolythiolate species which have greater affinity for the non-polar sulfur components of the positive cathode and catholyte phase. The organosulfur species is also capable of reacting with the reactive metal or metals present in the negative electrode to form metallic salts of the organosulfur species on the surface of the negative electrode which help to enhance the performance of an electrochemical cell containing such negative electrodes treated with species of organosulfur. Without being bound by any theory, it is believed that the organosulfur species chemically combines with the reactive metal(s) of the anode and prevents the accumulation of LiS2 in the anode as a result of a reaction between dissolved Li2Sn species. (n>1) often present in electrolyte solutions used in sulfur-metal batteries. In this way, the presence of an organosulfur species or the treatment of an anode with an organosulfur species can help to prevent the translational flow of sulfur atoms or anions from the cathode to the anode by forming a protective layer on the anode surface that is capable of to conduct metal cations. The electrolyte becomes saturated in a polysulfide metal species, resulting in less sulfur loss from the cathode, greater battery capacities, and greater total cycle time for the battery.

[0012] One aspect of the invention provides a battery, the battery comprising: a) an anode comprising an active anode material comprising sodium, lithium, potassium, magnesium or an alloy or composite of at least one of sodium, lithium, potassium or magnesium with at least one other metal to provide ions; b) A cathode comprising a cathode active material comprising elemental sulfur, elemental selenium or a mixture of elemental chalcogens; and c) an intermediate separator element positioned between the anode and cathode acting to separate liquid electrolyte solutions or gels in contact with the anode and cathode, through which metal ions and their counterions move between the anode and cathode during charge and discharge cycles. of the battery;

[0013] wherein the liquid electrolyte solutions or gels comprise a non-aqueous polar aprotic solvent or polymer and a conductive salt and at least one of conditions (i), (ii), (iii) or (iv) is satisfied: ( i) at least one of the liquid electrolyte solutions or gels additionally comprises at least one organosulfur species; (ii) the cathode is further comprised of at least one organosulfur species; (iii) the intermediate separating element comprises a functionalized porous polymer containing at least one organosulfur species; (iv) the anode is further comprised of, or has been treated with, at least one organosulfur species;

[0014] wherein the organosulfur species comprises at least one organic moiety and at least one -S-Sn- bond, with n being 0 or an integer of 1 or more.

[0015] In one modality, only one of the conditions (i), (ii), (iii) or (iv) is satisfied. In another embodiment, all four conditions are satisfied. In yet another embodiment, only two or three of the conditions are satisfied, for example, (i) and (ii), (i) and (iii), (ii) and (iii), (i), (ii) and (iii), (ii), (iii) and (iv), (i), (iii) and (iv), or (i), (ii) and (iv).

[0016] In another aspect, the invention provides an electrolyte comprising at least one non-aqueous polar aprotic solvent or polymer, at least one conductive salt, and at least one organosulfur species comprised of at least one organic moiety and at least one bond. of -S-Sn- where n is an integer of 1 or more.

[0017] Another aspect of the invention provides a cathode comprising a) elemental sulfur, elemental selenium or a mixture of elemental chalcogens, b) at least one electrically conductive additive, c) and at least one organosulfur species comprising at least one organic fraction and at least one bond of -S-Sn-, n being 0 or an integer of 1 or more.

[0018] A further aspect of the invention provides an anode comprising an anode active material comprising sodium, lithium, potassium, magnesium or an alloy or composite of at least one of sodium, lithium, potassium or magnesium with at least one other metal to provide ions, wherein the anode further comprises or has been treated with at least one organosulfur species comprising at least one organic moiety and at least one -S-Sn- bond, n being 0 or an integer of 1 or more. Such treatment results in longer battery life and less ability to weaken in subsequent cycles.

[0019] The species of organosulfur, for example, can be selected from the group consisting of organic polysulfides, organic thiolates (where n = 0, corresponding, for example, to the general formula R-S-M, where R is an organic fraction and M is a cation such as Li, Na, K, Mg, quaternary ammonium, or quaternary phosphonium) and/or metallic organic polythiolates. In certain embodiments of the invention, the organosulfur species contains one or more sulfur-containing functional groups selected from the group consisting of dithioacetal, dithioketal, trithio-orthocarbonate, thiosulfonate [-S(O)2-S-], thiosulfinate [-S( O)-S-], thiocarboxylate [-C(O)-S-], dithiocarboxylate [-C(S)-S-], thiophosphate, thiophosphonate, monothiocarbonate, dithiocarbonate, and trithiocarbonate. In other embodiments, the organosulfur species may be selected from the group consisting of aromatic polysulfides, polysulfides and polyethers, polysulfide acid salts and mixtures thereof.

Brief Description of Drawings

[0020] Figure 1 shows lithium-sulfur battery discharge profiles with n-C12H25SLi added to the cathode for repeated charge/discharge cycles 3 to 63.

[0021] Figure 2 shows comparison of cycling performance of a cell prepared with and without the anode being treated with 3,6-dioxaoctane-1,8-dithiol di-lithium salt (LiS-C2H4-O-C2H4- O-C2H4-SLi).

Detailed Description of the Invention

[0022] An electroactive material that has been fabricated into a structure for use in a battery is referred to as an electrode. Of a pair of electrodes used in a battery, which serves as a chemical source of electrical energy, the electrode on the side with a higher electrochemical potential is referred to as the positive electrode, or the cathode, while the electrode on the side with a lower electrochemical potential is referred to as the negative electrode, or the anode. As used herein, conventional nomenclature for batteries is employed where the expressions "cathode" or "positive electrode" and "anode" or "negative electrode" refer to the electrochemical functions of the electrodes during cell discharge to provide electrical energy. During the charging portion of the cycle, the actual electrochemical functions of an electrode are reversed from those that occur during discharge, but the designation of the respective electrodes remains the same for discharge.

[0023] Electrochemical cells are commonly combined in series, the aggregate of such cells being referred to as a battery. Based on the operating chemistry of cells, primary batteries are designed for a single discharge to provide energy to an external device. Secondary batteries are rechargeable, using electrical energy from an external source, and thus provide extended use through multiple discharge and charge cycles.

[0024] An electrochemically active material used in the cathode or positive electrode is referred to below as an active cathode material. An electrochemically active material used in the anode or negative electrode is hereinafter referred to as an active anode material. Multi-component compositions having electrochemical activity and comprising an electrochemically active material and optional electrically conductive additive and binder, as well as other optional additives, are hereinafter referred to as electrode compositions. A battery comprising a cathode with the active cathode material in an oxidized state and an anode with the active anode material in a reduced state is referred to as being in a charged state. Thus, a battery comprising a cathode with the active cathode material in a reduced state, and an anode with the active anode material in an oxidized state, is referred to as being in a discharged state.

[0025] Without wishing to be bound by any theory, the following are certain possible advantages or features of the present invention. The organosulfur species can partition into the sulfur-rich catholyte phase. Chemical exchange reactions between dianion sulfides or polysulfides (e.g. LÍ2Sx, x = 1, 2, 3...) and organopolysulfides, organothiolates or organopolythiolates (e.g. R-Sx-R' or R-Sx-Li , R and R' = organic fractions, x = 0 or an integer of 1 or more), together with extrusion/reinsertion chemistries of sulfur common to polysulfides and polythiolates, favor minimization of the amount of dianionic polysulfides in the catholyte and favor redeposition of sulfur and sulfur-containing species on the cathode. The net removal of dianionic polysulfides could reduce the viscosity of the electrolyte and thus minimize the deleterious effects of high viscosity on electrolyte conductivity. The organosulfur species can also enhance the dissolution, and thus the removal, of low grade insoluble lithium sulfide species (particularly Li2S and Li2S and Li2S2) in both the catholyte and anolyte phases, thus minimizing loss of reactive lithium species upon repeated charge/discharge cycles. The performance of the organosulfur species can be “tuned” by selection of organic functionality. For example, short-chain alkyl or alkyl groups with more polar functionality would partition more in the anolyte phase, while the less polar long-chain analogues or analogues would partition more in the catholyte phase. Adjustment of the relative ratios of long-chain/non-polar and short-chain/polar organic species could provide a means of controlling the partition of sulfur-containing species at the cathode/catholyte. Furthermore, since the presence of some amount of polysulfide or polythiolate in the anolyte is advantageous as a means of controlling lithium dendritic growth on the anode during charging, selection of appropriate organic fractions and their relative ratios could provide greater growth control. dendritic.

[0026] Organosulfur species useful in the present invention comprise at least one organic moiety and at least one -S-Sn- bond, where n is 0 or an integer of at least 1. In one embodiment, the organosulfur species comprises two organic moieties per molecule (which may be the same or different from each other) which are linked by an -S-Sn - (polysulfide) bond (where n is an integer of 1 or more). The -S-Sn- bond may form part of a larger linking group such as a -Y1-C(Y2Y3)-S-Sn- bond or a -Y1-C(=Y4)-S-Sn- bond -, where Y1 is O or S, Y2 and Y3 are independently an organic fraction or -S-So-Z, where o is 1 or more and Z is an organic fraction or a selected species of Li, Na, K, Mg , quaternary ammonium, or quaternary phosphonium, and Y4 is O or S. In another embodiment, the organosulfur species contains a monovalent organic fraction and a selected species of Na, Li, K, Mg, quaternary ammonium, and quaternary phosphonium that are bonded by a -S-Sn- bond (including, for example, a -Y1-C(Y2Y3)-S-Sn- bond or -Y1-C(=Y4)-S-Sn- bond, where n = 0 or an integer of 1 or more). In yet another embodiment, a -S-Sn- bond may appear on either side of an organic moiety. For example, the organic fraction may be an optionally substituted C(R3)2 divalent aromatic moiety (with each R3 independently being H or an organic moiety such as a C1-C20 organic moiety), carbonyl (C=O) or thiocarbonyl (C =S).

[0027] The organosulfide species can, for example, be selected from the group consisting of organic polysulfides, organic thiolates, organic polythiolates, including those with sulfur-containing functional groups such as dithioacetal, dithioketal, trithio-orthocarbonate, aromatic polysulfide, polysulfide and polyether, polysulfide acid salt, thiosulfonate [-S(O) 2-S-], thiosulfinate [-S(O)-S-], thiocarboxylate [-C(O)-S-], dithiocarboxylate [-RC(S) -S-], thiophosphate or thiophosphonate functionality, or mono-, di- or trithiocarbonate functionality; organometallic polysulfides containing these or similar functionalities; and mixtures thereof.

[0028] Suitable organic moieties include, for example, mono-, di- and polyvalent organic moieties which may comprise branched, linear and/or cyclic hydrocarbyl groups. As used herein, the term "organic fraction" includes a fraction which may, in addition to carbon and hydrogen, comprise one or more heteroatoms such as oxygen, nitrogen, sulfur, halogen, phosphorus, selenium, silicon, a metal such as tin and the like. . The heteroatom(s) may be present in the organic fraction in the form of a functional group. Thus, hydrocarbyl as well as functionalized hydrocarbyl groups are considered in the context of the present invention to be organic moieties. In one embodiment, the organic fraction is a C1-C20 organic fraction. In another embodiment, the organic fraction contains two or more carbon atoms. The organic fraction thus may be a C2-C20 organic fraction.

[0029] The species of organosulfur can be monomeric, oligomeric or polymeric in character. For example, -S-Sn- functionality may be pendant on the backbone of an oligomeric or polymeric species containing two or more monomer repeat units in its backbone. The -S-Sn- functionality may be incorporated into the backbone of such an oligomer or polymer such that the oligomer or polymer backbone contains a plurality of -S-Sn- bonds.

[0030] The organosulfur species may, for example, be an organic polysulfide or mixture of organic polysulfides of the formula R1-S-Sn-R2, wherein R1 and R2 independently represent a C1-C20 organic fraction. and n is an integer of 1 or more. The organic fraction C1-C20. it may be a branched, linear or cyclic monovalent hydrocarbyl group. R1 and R2 may each independently be a C9-C14 hydrocarbyl group, with n = 1 (providing a disulfide, such as tertiary dodecyl disulfide). In another embodiment, R1 and R2 are each independently a C9-C14 hydrocarbyl group, with n = 2-5 (providing a polysulfide). Examples of such compounds include TPS-32 and TPS-20, available from Arkema. In another embodiment, R1 and R2 are independently C7-C11 hydrocarbyl groups, with n = 2-5. TPS-37LS, available from Arkema, is an example of such a suitable polysulfide. Another suitable type of polysulfide could be a polysulfide or mixture of polysulfides wherein R1 and R2 are either tert-butyl or n = 2-5. Examples of such organosulfur compounds include TPS-44 and TPS-54, available from Arkema.

[0031] The organosulfur species could also be an organic polythiolate of the formula R1-S-Sn-M, where R1 is a C1-C20 organic moiety, M is lithium, sodium, potassium, magnesium, quaternary ammonium, or quaternary phosphonium and n is an integer of 1 or more or an organic thiolate of the formula R2-S-M, wherein R2 is a C1-C20 organic moiety, M is lithium, sodium, potassium, magnesium, quaternary ammonium, or quaternary phosphonium.

[0032] In another embodiment, the organosulfur species may be a dithioacetal or dithioketal such as those corresponding to formulas (I) and (II), or a trithio-orthocarboxylate of formula (III):

[0033] wherein each R3 is independently H or a C1-C20 organic fraction, o, p and q are each independently an integer of 1 or more, and each Z is independently a C1-C20 organic fraction, Li, Na, K , Mg, quaternary ammonium, or quaternary phosphonium. Examples of such organosulfur species include 1,2,4,5-tetrathiane (formula I, R3 = H, o = p = 1), tetramethyl-1,2,4,5-tetrathian (formula I, R3 = C H3 , o=p=1), and oligo or polymeric species thereof.

[0034] Another embodiment of the invention utilizes an organosulfide species which is an aromatic polysulfide of formula (IV), a polysulfide and polyether of formula (V), a polysulfide acid salt of formula (VI), or a polysulfide acid salt of formula (VII):

[0035] wherein R4 independently is tert-butyl or tert-amyl, R5 independently is OH, OLi or ONa, and r is 0 or more (e.g. 0-10) in formula (IV) with the aromatic rings being optionally substituted at one or more other positions with substituents other than hydrogen, R6 is a divalent organic moiety in formula (VI), R7 is a divalent organic moiety in formula (VII), each Z is independently a C1-C20 organic moiety, Li, Na , K, Mg, quaternary ammonium, or quaternary phosphonium, each M is independently Li, Na, K, Mg, quaternary ammonium, or quaternary phosphonium, and o and p are each independently an integer of 1 or more. Examples of such organosulfur species include the aromatic polysulfides marketed by Arkema under the trade name Vultac® (formula IV, R4 = tert-butyl or tert-amyl, R5 = OH); and polysulfide acid salts corresponding to formulas VI and VII derived from mercapto acids such as mercaptoacetic acid, mercaptopropionic acid, mercaptoethanesulfonic acid, mercaptopropanesulfonic acid, or from olefin-containing acids such as vinylsulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid.

[0036] In yet another embodiment, the organosulfide species is an organo- or organometallic polysulfide containing trithiocarbonate functionality of formula (IX), an organo- or organometallic polysulfide containing dithiocarbonate functionality of formula (X), or an organo polysulfide - or organometallic containing monothiocarbonate functionality of the formula (XI):

[0037] where Z is a C1-C20 organic moiety, Na, Li, K, Mg, quaternary ammonium, or quaternary phosphonium, and o and p are independently an integer of 1 or more.

[0038] The liquid or gel electrolyte solution may additionally be comprised of a dimetal polythiolate species of the formula M-S-Sn-M, wherein each M is independently Li, Na, K, Mg, quaternary ammonium, or quaternary phosphonium and n is an integer of 1 or more. A species like this does not contain any organic fraction, unlike the organosulfur species described above.

[0039] The intermediate separator element can function as a divider between compartments in an electrochemical cell. A compartment may comprise an electrolyte in contact with a cathode (the electrolyte in such a compartment may be referred to as a catholyte). Another compartment may comprise an electrolyte in contact with an anode (the electrolyte in such a compartment may be referred to as an anolyte). The anolyte and catholyte can be the same or different from each other. One or both of the anolyte and the catholyte may contain one or more organosulfur species in accordance with the present invention. The intermediate separator element can be positioned between such compartments in such a way as to allow ions from the anolyte to pass through the intermediate separator element to the catholyte and vice versa, depending on whether the electrochemical cell is being operated in charge or discharge mode.

[0040] In a further embodiment of the invention, the intermediate separating element is comprised of a porous polymer. The porous polymer may, for example, be comprised of polypropylene, polyethylene, or a fluorinated polymer. The porous polymer can be functionalized with an organosulfur species of the type described herein. The organosulfur species may be pendant on the backbone of the porous polymer, may be present in crosslinks between the backbones of the individual polymer chain, and/or may be incorporated into the backbone of the porous backbone. Thus, the porous polymer backbone may contain one or more -S-Sn- bonds and/or -S-Sn- bonds may be dangling from the polymer backbone. Such -S-Sn- bonds may also be present in crosslinks.

[0041] Suitable solvents for use in electrochemical cells according to the invention include any of the basic aprotic polar solvents (cation complexer) known or used for lithium-sulfur batteries generally such as sulfolane, dimethyl sulfoxide, dimethylacetamide, tetramethyl urea , N-methyl pyrrolidinone, tetraethyl sulfamide; ethers such as tetrahydrofuran, methyl-THF, 1,3-dioxolane, 1,2-dimethoxyethane (glyme), diglyme, and tetraglyme, and mixtures thereof; carbonates such as ethylene carbonate, propylene carbonate, dimethylcarbonate, diethylcarbonate, ethylmethylcarbonate, methylpropylcarbonate, ethylpropylcarbonate and the like; as well as esters such as methylacetate, ethyl acetate, propylacetate, and gamma-butyrolactone. The electrolyte may comprise such a single solvent or a mixture of such solvents. Any of the polar aprotic polymers known in the battery art may also be employed. The electrolyte may comprise a polymeric material and may take the form of a gel. Polymers suitable for use in the electrolyte may include, for example, polyethylene oxide, a polyethersulfone, a polyvinylalcohol, or a polyimide. The electrolyte may be in the form of a gel, which may be a three-dimensional network comprised of a liquid and a binder component. The liquid may be a monomeric solvent which is entrained in a polymer, such as a cross-linked polymer.

[0042] One or more salt conductors are present in the electrolyte in combination with the solvent and/or non-aqueous polar aprotic polymer. Salt conductors are well known in the battery art and include, for example, lithium salts of (CF3SO2)2N- CF3SO3-, CH3SO3-, CIO4-, PF6_, AsF6-nitrate, halogen or the like. Sodium and other alkali metal salts and mixtures thereof may also be used.

[0043] The anode active material may comprise an alkali metal such as lithium, sodium, potassium and/or magnesium or another active material or composition. Particularly preferred anode active materials include lithium metal, lithium alloys, sodium metal, sodium alloys, alkali metals or alloys thereof, metal powders, lithium aluminum alloys, magnesium, silicon, and/or tin, alkali metal. carbon and alkali metal-graphite intercalated, compounds capable of reversibly oxidizing and reducing with an alkali metal ion, and mixtures thereof. The metal or metal alloy (e.g. lithium metal) can be contained as a film in a battery or as several films, optionally separated by a ceramic material. Suitable ceramic materials include, for example, silica, alumina, or lithium-containing glassy materials such as lithium, lithium phosphates, lithium aluminates, silicates, lithium phosphorus oxynitrides, lithium tantalum oxide, lithium aluminosilicates, lithium oxides, and titanium , lithium siliculphides, lithium germanesulphides, lithium aluminosulphides, lithium borosulphides, lithium phosphosulphides and mixtures thereof.

[0044] The anode may be in any suitable form, such as, for example, a film, composite or other type of current collector.

[0045] In one embodiment of the invention, the anode is treated with at least one species of organosulfur. Such treatment may be carried out by bringing an anode surface into contact with at least one organosulfur species. The organosulfur species may, for example, be in the form of a solution during such a contacting step. Any suitable solvent or combination of solvents for the organosulfur species can be used to form such a solution. For example, the solvent(s) may be any of the previously described polar aprotic solvents. In one embodiment, the anode is treated with the organosulfur species prior to assembly of an electrochemical cell, such as by spraying a solution of the organosulfur species on the anode or dipping the anode in a solution of the organosulfur species. In another embodiment, the organosulfur species is incorporated with an electrolyte component to be used in the electrochemical cell, in which the electrolyte containing the organosulfur species is in contact with the anode by mounting the electrochemical cell.

[0046] In another embodiment, the anode comprises at least one organosulfur species in addition to at least one reactive metal selected from the group consisting of lithium, sodium, potassium and magnesium. For example, at least one species of organosulfur can be deposited on an anode surface.

[0047] The cathode comprises elemental sulfur, elemental selenium or a mixture of elemental chalcogens. In one embodiment, the cathode is further comprised of one or more organosulfur species in accordance with those previously described in detail herein. The cathode may additionally and/or alternatively be comprised of a binder and/or an electrically conductive additive. Suitable binders include polymers such as, for example, polyvinyl alcohol, polyacrylonitrile, poly(vinylidene fluoride) (PVDF), poly(vinyl fluoride), polytetrafluoroethylene (PTFE), copolymers of tetrafluoroethylene and hexafluoropropylene, copolymers of vinylidene fluoride and hexafluorpropylene , copolymers of vinylidene fluoride and tetrafluoroethylene, ethylene-propylene-diene monomer (EPDM) rubber, and poly(vinyl chloride) (PVC). The electrically conductive additive can be, for example, carbon in electrically conductive form such as graphite, graphene, carbon fibers, carbon nanotubes, carbon black, or soot (e.g., lamp or oven soot). The cathode may be present in a battery or electrochemical cell in combination with a current collector, such as any of the current collectors known in the battery or electrochemical cell art. For example, the cathode can be coated onto the surface of a metallic current collector. Aspects of the invention include:

[0048] 1. A battery, comprising:

[0049] an anode comprising an active anode material comprising sodium, lithium or an alloy or composite of at least one of sodium or lithium with at least one other metal to provide ions;

[0050] a cathode comprising a cathode active material comprising elemental sulfur, elemental selenium or a mixture of elemental chalcogens; and

[0051] An intermediate separator element positioned between the anode and cathode acting to separate liquid electrolyte solutions or gels in contact with the anode and cathode, through which metal ions and their counterions move between the anode and cathode during charge and battery discharge;

[0052] wherein the liquid electrolyte solutions or gels comprise a non-aqueous polar aprotic solvent or polymer and a conductive salt and at least one of conditions (i), (ii), (iii) or (iv) is satisfied: ( i) at least one of the liquid electrolyte solutions or gels additionally comprises at least one organosulfur species; (ii) the cathode is further comprised of at least one organosulfur species; (iii) the intermediate separating element comprises a functionalized porous polymer containing at least one organosulfur species; (iv) the anode is further comprised of or has been treated with at least one organosulfur species;

[0053] wherein the organosulfur species comprises at least one organic moiety and at least one -S-Sn- bond, n being 0 or an integer of 1 or more.

[0054] 2. The battery of aspect 1, wherein the organosulfur species is selected from the group consisting of organic polysulfides, organic thiolates and organic polythiolates and mixtures thereof.

[0055] 3. The battery of any of aspects 1 and 2, wherein the organosulfur species contains one or more sulfur-containing functional groups selected from the group consisting of dithioacetal, dithioketal, trithio-orthocarbonate, thiosulfonate [- S(O )2-S-], thiosulfinate [-S(O)-S-], thiocarboxylate [-C(O)-S-], dithiocarboxylate [-C(S)-S-], thiophosphate, thiophosphonate, monothiocarbonate, dithiocarbonate , and trithiocarbonate.

[0056] 4. The battery of any of aspects 1-3, wherein the organosulfur species is selected from the group consisting of aromatic polysulfides, polysulfides and polyethers, polysulfide acid salts and mixtures thereof.

[0057] 5. The battery of any of aspects 1-5, wherein the organosulfur species is an organic polysulfide of the formula R1-S-Sn-R2, wherein R1 and R2 independently represent a C1-C20 organic fraction that may be linear, branched, or cyclic or aromatic aliphatic and which may optionally comprise one or more functional groups containing N, O, P, S, Se, Si, Sn, halogen and/or metal, and n is an integer of 1 or most.

[0058] 6. The battery of any of aspects 1-5, wherein the organosulfur species is an organic thiolate of the formula R1-S-M or an organic polythiolate of the formula R1-S-Sn-M, wherein R1 is a fraction organic C1-C20 which may be linear, branched, or cyclic or aromatic aliphatic and which may optionally comprise one or more functional groups containing N, O, P, S, Se, Si, Sn, halogen and/or metal, M is lithium , sodium, potassium, magnesium, quaternary ammonium, or quaternary phosphonium, and n is an integer of 1 or more.

[0059] 7. The battery of any of aspects 1-6, wherein the organosulfur species is a dithioacetal or dithioketal of formulas (I) or (II), or a trithio-orthocarboxylate of formula (III):

[0060] wherein each R3 is independently H or a C1-C20 organic moiety which may be linear, branched, or cyclic or aromatic aliphatic and which may optionally comprise one or more functional groups containing N, O, P, S, Se, Si, Sn, halogen and/or metal, o, p and q are each independently an integer of 1 or more, and each Z is independently: a C1-C20 organic fraction which may be linear, branched, or cyclic or aromatic aliphatic and which may optionally comprise one or more functional groups containing N, O, P, S, Se, Si, Sn, halogen and/or metal; read; At; K; mg; quaternary ammonium; or quaternary phosphonium.

[0061] 8. The battery of any of aspects 1-7, wherein the organosulfide species is an aromatic polysulfide of formula (IV), a polysulfide and polyether of formula (V), a polysulfide acid salt of formula (VI). ), or a polysulfide acid salt of formula (VII):

[0062] wherein R4 independently is tert-butyl or tert-amyl, R5 independently is OH, OLi or ONa, and r is 0 or more in formula (IV) with the aromatic rings being optionally substituted at one or more positions with substituents without be hydrogen, R6 is a divalent organic fraction in formula (VI), R5 is a divalent organic fraction in formula (VII), each Z is independently a C1-C20 organic fraction, Li, Na or quaternary ammonium, each M is independently Li , Na, K, Mg, quaternary ammonium, or quaternary phosphonium, and o and p are each independently an integer of 1 or more.

[0063] 9. The battery of any of aspects 1-8, wherein the organosulfide species is an organo- or organometallic polysulfide containing trithiocarbonate functionality of formula (IX), an organo- or organometallic polysulfide containing dithiocarbonate functionality of the formula (X), or an organo- or organometallic polysulfide containing monothiocarbonate functionality of formula (XI):

[0064] wherein Z is a C1-C20 organic moiety, Na, Li, quaternary ammonium or quaternary phosphonium, and o and p are each independently an integer of 1 or more.

[0065] 10. The battery of any of aspects 1-9, wherein the liquid or gel electrolyte solution is further comprised of a dimetal polythiolate species of the formula M-S-Sn-M, wherein each M is independently Li , Na, K, Mg, quaternary ammonium, or quaternary phosphonium, and n is an integer of 1 or more.

[0066] 11. The battery of any one of aspects 1-10, wherein the cathode is further comprised of at least one electrically conductive additive and/or at least one binder.

[0067] 12. The battery of any of aspects 1-11, wherein the organosulfur species is pendant on the backbone of the functionalized porous polymer.

[0068] 13. The battery of any one of aspects 1-12, wherein the organosulfur species is cross-linked into or forms part of the backbone of the functionalized porous polymer.

[0069] 14. The battery of any of aspect 1-13, wherein the organic fraction contains at least two carbon atoms.

[0070] 15. The battery of any of aspects 1-14, wherein the intermediate porous separator separates the battery to provide an anode section associated with the anode and a catholyte section associated with the cathode and wherein the species of organosulfur is present in at least one of the anolyte section or the catholyte section.

[0071] 16. The battery of any of aspects 1-15, wherein the non-aqueous polar aprotic solvent or polymer contains one or more functional groups selected from ether, carbonyl, ester, carbonate, amino, amido, sulfidyl [-S -], sulfinyl [-S(O)-], or sulfonyl [-SO2-].

[0072] 17. The battery of any of aspects 1-16, wherein the conducting salt corresponds to the formula MX where M is Li, Na or quaternary ammonium and X is (CF3SO2)2N, CF3SO3, CH3SO3, ClO4, PF6 , NO3, AsF6 or halogen.

[0073] 18. The battery of any of aspects 1-17, wherein the organic fraction is oligomeric or polymeric and the organosulfur species comprises at least one -S-S- bond which is pendant on the backbone of the oligomeric or polymeric.

[0074] 19. The battery of any of aspects 1-18, wherein the organic fraction is oligomeric or polymeric and the organosulfur species comprises at least one -S-S- bond which is incorporated into the backbone of the oligomeric or organic fraction polymeric.

[0075] 20. An electrolyte, comprising at least one non-aqueous polar aprotic solvent or polymer, at least one conductive salt, and at least one organosulfur species comprised of at least one organic moiety and at least one -S-Sn bond - where n is 0 or an integer of 1 or more.

[0076] 21. A cathode comprising a) elemental sulfur, elemental selenium or a mixture of elemental chalcogens, b) at least one electrically conductive additive, c) and at least one organosulfur species comprising at least one organic fraction and at least one bond of -S-Sn-, n being 0 or an integer of 1 or more.

[0077] 22. The cathode of aspect 21, in combination with a current collector.

[0078] 23. The cathode of any one of aspects 21 and 22, wherein the at least one electrically conductive additive includes at least one of graphite, carbon nanotubes, carbon nanofibers, graphene, carbon black or soot.

[0079] 24. The cathode of any one of aspects 21-23, further comprising at least one binder.

[0080] 25. An anode comprising an active anode material comprising sodium, lithium, potassium or magnesium or an alloy or composite of at least one of sodium, lithium, potassium or magnesium with at least one other metal to provide ions, wherein the anode further comprises or has been treated with at least one organosulfur species comprising at least one organic moiety and at least one -S-Sn- bond, n being 0 or an integer of 1 or more.

[0081] In this specification the modalities have been described in a way that allows a clear and concise specification to be written, but it is intended and understood that the modalities can be combined or separated in various ways without departing from the invention. For example, it should be understood that all preferred features described herein are applicable to all aspects of the invention described herein.

[0082] In some embodiments, the invention here can be understood excluding any element or process step that does not materially affect the basic and unprecedented characteristics of the composition or process. Additionally, in some embodiments, the invention may be understood to exclude any element or process step not specified herein.

EXAMPLES Cathode Fabrication, Battery Preparation, and Battery Testing Example 1

[0083] A positive electrode comprising 70% by weight of sublimated elemental sulfur powder, 20% by weight of polyethylene oxide (PEO, MW 4*106), 10% by weight of carbon black (Super P® Conductor , Alfa Aesar) was produced by the following procedure:

[0084] The mixture of these components in N-methyl-2-pyrrolidone (NMP) was mechanically milled in a planetary milling machine. Acetonitrile was added to dilute the mixture. The resulting suspension was applied to aluminum foil (76 μm thick) with an automatic film coater (Mathis). The coating was dried at 50 °C in a vacuum oven for 18 hours. The resulting coating contained 3.10 mg/cm 2 of cathode mixture.

Example 2

[0085] A positive cathode containing lithium n-dodecyl mercaptide (10% by weight sulfur) was prepared following the procedure described in Example 1. The resulting coating contained 3.4 mg of sulfur/cm2

Example 3

[0086] The positive cathode of Example 2 was used in a Swaglok PTFE cell with two stainless steel rods or coin cell assembly made of stainless steel (CR2032). The battery cell was mounted in an argon filled glove box (MBraun) as follows: the cathode electrode was placed in the lower container followed by the separator. Then electrolyte was added to the separator. A lithium electrode was placed inside the separator. A spacer and spring were placed on top of the lithium electrode. The battery core was sealed with stainless steel rods or a crimping machine.

Example 4

[0087] Following the procedure described in Example 3, a battery cell consisting of the cathode from Example 2 (7/16" in diameter), 20 μL of 0.5 M LiTFSI solution in tetraethylene glycol dimethyl ether (TEGDME): 1,3-dioxolane (DOL)=1:1, separator, and lithium electrode (thickness 0.38 mm, diameter 7/16”) was tested for charge-discharge cycling at a current of 0.1 mA . The test was performed using Gamry potentiometer (Gamry Instruments) to cut voltage of 1.5 V and 3.2 V at room temperature. The discharge cycle profile is illustrated in Figure 1.

Lithium alkylmercaptide synthesis Example 5 - Synthesis of lithium n-dodecyl mercaptide with lithium hexyl

[0088] To n-dodecyl mercaptan (9.98 g, 1 eq.) in hexanes (100 mL) at -30 °C was added n-hexyllithium (33 wt% in hexane, 1.1 eq.) dropwise to keep the temperature of the mixture below -20 °C. The solvent was removed under low pressure to yield a white solid in quantitative yield.

Example 6 - Synthesis of lithium n-dodecyl mercaptide with lithium hydroxide

[0089] A mixture of n-dodecyl mercaptan (2.0 g, 1 eq.) and lithium hydroxide monohydrate (0.41 g, 1 eq.) in acetonitrile (8 mL) was heated to 75 °C and stirred. at 75 °C for 16 hours. After cooling to room temperature, the reaction mixture was filtered. The filter cake was washed with acetonitrile and dried at 50 °C in a vacuum oven overnight. Lithium n-dodecyl mercaptide was obtained as a white solid in 93.5% yield (1.93 g) Example 7 - Synthesis of lithium n-dodecyl mercaptide with hexyl lithium

[0090] Following the procedure described in Example 6, 3,6-dioxaoctane-1,8-dithiol di-lithium salt was synthesized from dimercaptan as a white solid in quantitative yield.

[0091] Synthesis of lithium alkyl polythiolates Example 8 - Synthesis of lithium n-dodecylpolythiolate with lithium hydroxide

[0092] To a nitrogen-degassed solution of n-dodecyl mercaptan (2.00 g, 1 eq.) in 1,3-dioxolane (25 mL) was added lithium hydroxide monohydrate (0.41 g, 1 eq.) and sulfur (1.27 g, 4 eq.). The mixture was stirred under nitrogen at room temperature for 30 min. Lithium N-dodecyl polythiolate in 1,3-dioxolane was obtained as a dark red solution. Complete conversion of mercaptan to lithium n-dodecyl polythiolate was confirmed by NMR13C and LCMS.Example 9 - Synthesis of lithium 3,6-dioxaoctane-1,8-polythiolate with lithium sulfur hydroxide

[0093] Following the procedure described in Example 8, dark red solution of lithium 3,6-dioxaoctane-1,8-polythiolate in 1,3-dioxolane by the reaction of 3,6-dioxaoctane-1,8-dithiol (0 .72 g, 1 eq.), lithium hydroxide monohydrate (0.33 g, 2 eq.), and sulfur (1.02 g, 8 eq.) in 1,3-dioxolane (10 mL).

Example 10 - Synthesis of lithium n-dodecylpolythiolate from lithium alkyl mercaptide

[0094] To a nitrogen-degassed slurry of lithium n-dodecyl mercaptide (0.21 g, 1 eq.) in 1,3 dioxolane (5 mL) was added sulfur (0.13 g, 4 eq.). The mixture was stirred under nitrogen at room temperature for 16 hours. Insoluble solids were removed by filtration. The dark red filtrate contained 63% of lithium n-dodecyl polythiolates and 37% of a mixture of poly(bis(n-dodecyl) sulfides) as determined by LCMS.

Example 11 - Synthesis of lithium n-dodecylpolythiolate with lithium metal and sulfur

[0095] To a nitrogen-degassed solution of n-dodecyl mercaptan (2.23 g, 1 eq.) in 1,3-dioxolane (25 mL) were added sulfur (1.41 g, 4 eq.), and lithium (76.5 mg). The mixture was heated to 60 °C and stirred under nitrogen at 60 °C for 1 h. Lithium N-dodecyl polythiolate in 1,3-dioxolane was obtained as a dark red solution. Complete conversion of n-dodecyl mercaptan was confirmed by 13C-NMR.

Example 12 - Synthesis of lithium 3,6-dioxaoctane-1,8-polythiolate with lithium metal and sulfur

[0096] Following the procedure in Example 11, a dark red solution of lithium 3,6-dioxaoctane-1,8-polythiolate in 1,3-dioxolane was obtained by reacting 3,6-dioxaoctane-1,8-dithiol (1.97 g, 1 eq.), lithium metal (0.15 g, 2 eq.), and sulfur (2.77 g, 8 eq.) in 1,3-dioxolane (11 mL). Complete conversion of starting dimercaptan was confirmed by NMR13C

Example 13 - Dissolution of Li2S by added lithium n-dodecylpolythiolate

[0097] To determine the solubility of lithium sulfide in electrolyte with lithium n-dodecylpolythiolate, a saturated solution of lithium sulfide was prepared as follows:

[0098] A 0.4M solution of lithium n-dodecylpolythiolate in 1,3-dioxolane was prepared following the procedure described in Example 10. The solution was then diluted to 0.2M with tetraethylene glycol dimethyl ether, then added to the solution. of 1M LiTFSI in 1:1 tetraethylene glycol dimethylether:1,3-dioxolane 1:1 = v/v. To the resulting solution, lithium sulfide was added until a saturated mixture was obtained. The mixture was then filtered and the filtrate analyzed for dissolved lithium by ICP-MS (Agilent 7700x ICP-MS). Lithium sulfide solubility was calculated based on lithium level. In 0.5M LiTFSI with 0.1M lithium n-dodecylpolythiolate in 1:1 tetraethylene glycol dimethylether:1,3-dioxolane, solubility of lithium sulfide was determined to be 0.33% by weight. In contrast, without lithium n-dodecylpolythiolate, the solubility of lithium sulfide in 0.5M LiTFSI was only 0.13% by weight. This clearly demonstrated the improved solubility of Li2S in the battery electrolyte matrix when the organosulfurs of this invention are present.

Example 14 - Preparation of Battery Containing Organosulfur Treated Anode Species

[0099] This example demonstrates the preparation of a battery cell having an anode that has been exposed to an electrolyte containing an organosulfur species in accordance with one aspect of the invention. Elemental sulfur was combined with conductive carbon and polyethylene (as a binder) in a mass ratio (sulfur:carbon:polyethylene) of 75:20:5 and ball milled into a chloroform slurry. The slurry was then foiled onto carbon coated aluminum foil and air dried, resulting in a sulfur loading of approximately 0.5 mg/cm2. The resulting cathode was then mounted in CR2032 coin cells with a polypropylene separator and a lithium foil anode in an argon-filled glove box. The electrolytes used each contained 0.38 M lithium bis(trifluoromethane)sulfonamide and 0.38 M lithium nitrate in a 1:1 v/v mixture of 1,3-dioxolane and 1,2-dimethoxyethane. An electrolyte (according to the present invention) additionally contained 100 mM 3,6-dioxaoctane-1,8-dithiol di-lithium salt (LiS-C2H4-O-C2H4-O-C2H4-SLi) (thereby placing the lithium film anode in contact with 3,6-dioxaoctane-1,8-dithiol di-lithium salt), while the other electrolyte (control) did not contain any organosulfur species. Battery cycling was done in a battery test of 1.7 to 2.6 V. 40 to C/2 with respect to active sulfur. The observed results are shown in Figure 2.

Claims (12)

1. Battery, characterized in that it comprises: a) an anode comprising an anode active material comprising sodium, lithium or an alloy or composite of at least one of sodium or lithium with at least one other metal to provide ions; b) a cathode comprising a cathode active material comprising elemental sulfur and optionally elemental selenium or a mixture of elemental chalcogens; and c) an intermediate separator element positioned between the anode and cathode acting to separate liquid electrolyte solutions or gels in contact with the anode and cathode, through which metal ions and their counterions move between the anode and cathode during charge and discharge cycles. of the battery; wherein the liquid electrolyte solutions or gels comprise a non-aqueous polar aprotic solvent or polymer and the anode is further comprised of or has been treated with at least one organosulfur species; wherein the organosulfur species is selected from the group consisting of organic polysulfide of the formula R1-S-Sn-R2, wherein R1 and R2 independently represent a C1-C20 organic fraction which may be linear, branched, or cyclic or aromatic aliphatic and which may optionally comprise one or more functional groups containing N, O, P, S, Se, Si, Sn, halogen and/or metal, and n is an integer of 1 or more and an organic thiolate of the formula R1-S-M or polythiolate of the formula R1-S-Sn-M, wherein R1 is a C1-C20 organic moiety which may be linear, branched, or cyclic or aromatic aliphatic and which may optionally comprise one or more functional groups containing N, O, P, S, Se, Si, Sn, halogen and/or metal, M is lithium, sodium, potassium, magnesium, quaternary ammonium, or quaternary phosphonium, and n is an integer of 1 or more. 2. Battery, according to claim 1, characterized in that the organosulfur species is a dithioacetal or dithioketal of formulas (I) or (II), or a trithio-orthocarboxylate of formula (III):

wherein each R3 is independently H or a C1-C20 organic moiety which may be linear, branched, or cyclic aliphatic or aromatic and which may optionally comprise one or more functional groups containing N, O, P, S, Se, Si, Sn , halogen and/or metal, o, p and q are each independently an integer of 1 or more, and each Z is independently: a C1-C20 organic fraction which may be linear, branched, or cyclic or aromatic aliphatic and which may comprise optionally one or more functional groups containing N, O, P, S, Se, Si, Sn, halogen and/or metal; read; At; K; mg; quaternary ammonium; or quaternary phosphonium. 3. Battery according to claim 1, characterized in that the organosulfide species is an aromatic polysulfide of formula (IV), a polysulfide and polyether of formula (V), an acid salt polysulfide of formula (VI), or a polysulfide acid salt of formula (VII):

wherein R4 independently is tert-butyl or tert-amyl, R5 independently is OH, OLi or ONa, and r is 0 or more in formula (IV) with the aromatic rings being optionally substituted at one or more positions with substituents other than hydrogen, R6 is a divalent organic fraction in formula (VI), R5 is a divalent organic fraction in formula (VII), each Z is independently a C1-C20 organic fraction, Li, Na or quaternary ammonium, each M is independently Li, Na, K, Mg, quaternary ammonium, or quaternary phosphonium, and eep are each independently an integer of 1 or more. 4. Battery according to claim 1, characterized in that the organosulfide species is an organo- or organometallic polysulfide containing trithiocarbonate functionality of the formula (IX), an organo- or organometallic polysulfide containing dithiocarbonate functionality of the formula ( X), or an organo- or organometallic polysulfide containing monothiocarbonate functionality of the formula (XI):

where Z is a C1-C20 organic moiety, Na, Li, quaternary ammonium or quaternary phosphonium, and p and p are each independently an integer of 1 or more. 5. Battery according to claim 1, characterized in that the liquid or gel electrolyte solution is additionally comprised of a dimetal polythiolate species of the formula M-S-Sn-M, where each M is independently Li, Na , K, Mg, quaternary ammonium, or quaternary phosphonium, and n is an integer of 1 or more. 6. Battery, according to claim 1, characterized in that the organic fraction contains at least two carbon atoms. 7. Battery according to claim 1, characterized in that the non-aqueous polar aprotic solvent or polymer contains one or more functional groups selected from ether, carbonyl, ester, carbonate, amino, amido, sulfidyl [S-], sulfinyl [-S(O)-], or sulfonyl [-SO2-]. 8. Battery according to claim 1, characterized in that the conductive salt corresponds to the formula MX in which M is Li, Na or quaternary ammonium and X is (CF3SO2)2N, CF3SO3, CH3SO3, ClO4, PF6, NO3 , AsF6 or halogen. 9. Battery according to claim 1, characterized in that the organic fraction is oligomeric or polymeric and the organosulfur species comprises at least one -S-S- bond that is pendant on the backbone of the oligomeric or polymeric organic fraction. 10. Battery, according to claim 1, characterized in that the organic fraction is oligomeric or polymeric and the organosulfur species comprises at least one -S-S- bond that is incorporated into the backbone of the oligomeric or polymeric organic fraction. 11. Electrolyte, characterized in that it comprises at least one non-aqueous polar aprotic solvent or polymer, at least one conductive salt, and at least one organosulfur species comprising at least one organic fraction and at least one -S- bond Sn- where n is 0 or an integer of 1 or more. 12. Anode, characterized in that it comprises an anode active material comprising sodium, lithium, potassium or magnesium or an alloy or composite of at least one of sodium, lithium, potassium or magnesium with at least one other metal to provide ions, wherein the anode additionally comprises or has been treated with at least one organosulfur species selected from the group consisting of an organic polysulfide of the formula R1-S-Sn-R2, wherein R1 and R2 independently represent a C1-C20 organic fraction which may be linear, branched, or cyclic or aromatic aliphatic and which may optionally comprise one or more functional groups containing N, O, P, S, Se, Si, Sn, halogen and/or metal, and n is an integer of 1 or more and an organic thiolate of the formula R1-S-M and an organic polythiolate of the formula R1-S-Sn-M, wherein R1 is a C1-C20 organic moiety which may be linear, branched, or cyclic or aromatic aliphatic and which may optionally comprise one or more functional groups count Where N, O, P, S, Se, Si, Sn, halogen and/or metal, M is lithium, sodium, potassium, magnesium, quaternary ammonium, or quaternary phosphonium, and n is an integer of 1 or more.

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