JP2020501314A - Battery based on organic sulfur species - Google Patents

Abstract

Metal-sulfur batteries, such as lithium-sulfur batteries, convert one or more organic sulfur species, such as organic polysulfides and organic polythiolates, as part of a liquid or gel electrolyte solution, as part of a cathode, It is prepared as part (or used to treat the anode) and / or as part of a functionalized porous polymer that provides an intermediate separator element.

Description

  The invention relates to an anode made from sodium, lithium, potassium, magnesium or mixtures thereof, or an alloy or composite of sodium, lithium, potassium and / or magnesium and one or more other metals, and an elemental sulfur. A liquid or gel electrolyte solution of a conductive salt in a non-aqueous polar aprotic solvent or polymer having a cathode made of a mixture of selenium, selenium, or elemental chalcogen, the anode and cathode separated by a separator element Relate to batteries in contact with these electrodes.

  Electrochemical cells are the primary means for storing and supplying electrical energy. With the increasing demand for energy in electronics, transportation, and grid storage applications, the need for batteries with greater power storage and supply capabilities will continue for a long time into the future.

  Lithium-ion batteries have been widely used in portable electronic device applications since the early 1990s due to their light weight and high energy storage capacity compared to other types of batteries. However, current Li-ion battery technology meets high power and energy needs for large applications such as grid storage or electric vehicles that have a competitive driving range for vehicles powered by internal combustion engines. Absent. Therefore, due to the extensive efforts of the scientific and technical communities, batteries with higher energy densities and capacities continue to be sought.

Sodium-sulfur and lithium-sulfur electrochemical cells offer much higher theoretical energy capacities than Li-ion cells and have therefore continued to be of interest as "next generation" battery systems. Electrochemical conversion of elemental sulfur to monomeric sulfide (S ²⁻ ) gives a theoretical capacity of 1675 mAh / g compared to less than 300 mAh / g for a Li ion cell.

  Sodium-sulfur batteries have been developed and sold as commercial systems. Unfortunately, sodium-sulfur cells generally require high temperatures (above 300 ° C.) to function and are therefore only suitable for large stationary applications.

  Lithium-sulfur electrochemical cells first proposed in the late 1950's and 1960's are now being developed for the first time as commercial battery systems. These cells provide a theoretical specific energy density of more than 2500 Wh / kg (2800 Wh / L) compared to 624 Wh / g of lithium ions. The demonstrated specific energy densities of Li-S cells are in the range of 250-350 Wh / kg when compared to 100 Wh / g of Li-ion cells, and the lower values indicate the electrochemical of these systems during charge and discharge. It is the result of a special mechanism of the strategic process. Considering that the practical specific energy of a lithium battery is generally 25 to 35% of the theoretical value, the optimum practical specific energy of the Li-S system is about 780 Wh / g (30% of the theoretical value). (VS Kolosnitsyn and E. Karaseva US 2008/0100624 A1).

  Lithium-sulfur chemistry presents several technical challenges that have impeded the development of these electrochemical cells, specifically poor discharge-charge cyclability. Nevertheless, there is great interest in improving the performance of lithium-sulfur systems due to the inherent light weight, low cost, and high power capacity of lithium-sulfur cells, and to address these challenges in the last two decades. Extensive research is being conducted by many researchers worldwide. [C. Liang, et al. , Handbook of Battery Materials 2nd Ed. , Chapter 14, pp. 811 to 840 (2011); S. Kolosnitsyn, et al. , J. et al. Power Sources 2011, 196, 1478-82, and references therein. ]

Lithium-sulfur based cell designs generally include:
An anode made of lithium metal, a lithium alloy, or a lithium-containing composite material;
A non-reactive but porous separator between the anode and the cathode (often polypropylene or α-alumina). The presence of this separator results in separate anolyte and catholyte compartments.
A porous cathode carrying sulfur incorporating a binder (often polyvinylidene difluoride) and a conductivity enhancing substance (often graphite, mesoporous graphite, multi-walled carbon nanotubes, graphene).
A polar aprotic solvent and one or more conductive Li salts ((CF ₃ SO ₂ ) ₂ N ⁻ , CF ₃ SO ₃ ⁻ , CH ₃ SO ₃ ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , halogen, etc.). Solvents used in these cells include basic (cation complexed) aprotic polar solvents such as sulfolane, dimethylsulfoxide, dimethylacetamide, tetramethylurea, N-methylpyrrolidinone, tetraethylsulfamide, tetrahydrofuran, Methyl-THF, 1,3-dioxolan, diglyme, and tetraglyme. Less polar solvents are unsuitable due to poor conductivity and poor ability to solvate Li ⁺ species, and protic solvents can react with Li metal. In the solid version of the lithium-sulfur cell, the liquid solvent is replaced with a polymeric material such as polyethylene oxide.
Current collectors and appropriate casing materials.

US Patent Application Publication No. 2008 / 0100624A1

C. 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

  The present invention provides compositions and uses of organic polysulfides, organic thiolates and organic polythiolates for use in metal-sulfur batteries, specifically lithium-sulfur batteries. The organic polysulfide, organic thiolate, and organic polythiolate species (hereinafter sometimes referred to as "organic sulfur species") may enhance the performance of such electrochemical cells during repeated discharge and charge cycles. work.

  Accordingly, the present invention relates to a chemical source of energy including a cell or battery having one or more positive electrodes (cathodes), one or more negative electrodes (anodes), and an electrolyte medium. The effective chemical reaction involves the reduction of sulfur or polysulfide species and the oxidation of 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 organic sulfur. It contains a chemical species and / or has been treated with at least one organic sulfur species. The positive electrode comprises elemental sulfur and / or selenium, and in some embodiments of the present invention, organic polysulfide species and / or organic sulfur species, such as metal organic polysulfide salts, and a matrix containing these species. . In certain embodiments, the electrolyte matrix comprises a mixture of an organic solvent or polymer, an inorganic or organic polysulfide species, a carrier of the active metal in ionic form, and other components for optimizing electrochemical performance. including.

Specifically, the present invention relates to organic sulfides and polysulfides as components of cathode and electrolyte matrices, and their organic lithium thiolates (or sodium, potassium, magnesium, quaternary ammonium or quaternary phosphonium) or organic polysulfides. It relates to the use of thiolate analogs. The organic sulfur species chemically combines with the sulfur and anionic mono- or polysulfide species to form an organic polythiolate species. It has a high affinity of the positive and catholyte phases for non-polar sulfur components. The organosulfur species can also react with a reactive metal or a metal present in the anode to form a metal salt of the organosulfur species on the anode surface, which can be a negative electrode treated with such organosulfur species. Helps increase the performance of electrochemical cells containing. Without wishing to be bound by theory, the organosulfur species chemically binds to the reactive metal of the anode to form dissolved Li ₂ S that is often present in the electrolyte solutions used in metal-sulfur batteries. It is believed to prevent LiS ₂ from accumulating on the anode as a result of reactions between _n (n ≧ 1) species. Thus, the presence of or treatment of the anode with the organic sulfur species causes the translational flow of sulfur atoms or anions from the cathode to the anode by forming a protective layer on the anode surface that can conduct metal cations. Can help prevent. The electrolyte becomes saturated in the metal polysulfide species, resulting in less sulfur loss from the cathode, increasing battery capacity, and extending the overall cycle life of the battery.

One aspect of the present invention provides a battery, wherein the battery comprises:
a) an anode active material comprising sodium, lithium, potassium, magnesium or an alloy or complex of at least one of sodium, lithium, potassium or magnesium with at least one other metal to provide ions; Including anode,
b) a cathode comprising a cathode active material comprising a mixture of elemental sulfur, elemental selenium, or elemental chalcogen; and c) a liquid or gel electrolyte solution located between and in contact with the anode and the cathode. An intermediate separator element that acts to separate the metal ions and their counter-ions from moving between the anode and cathode during battery charge and discharge cycles.
Including
The liquid or gel electrolyte solution comprises a non-aqueous polar aprotic solvent or polymer and a conductive salt, and conditions (i), (ii), (iii) or (iv):
(I) at least one of the liquid or gel electrolyte solutions further comprises at least one organic sulfur species;
(Ii) the cathode is further comprised of at least one organic sulfur species;
(Iii) the intermediate separator element comprises a functionalized porous polymer containing at least one organic sulfur species;
(Iv) the anode is further comprised of or treated with at least one organic sulfur species;
Satisfy at least one of
The organic sulfur species, at least one and at least one organic moiety -S-S _n - and a bond (n is 0 or an integer of 1 or more).

  In one embodiment, only one of 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 these conditions, such as (i) and (ii), (i) and (iii), (ii) and (iii), (i) and (ii) (Iii), (ii) and (iii) and (iv), (i) and (iii) and (iv), or (i) and (ii) and (iv) are satisfied.

The present invention in another aspect, at least one polar aprotic solvent or polymer non-aqueous, and at least one conductive salt, at least one organic moiety and at least one -S-S _n - bond (Where n is an integer of 1 or more) and at least one organic sulfur chemical species.

Another aspect of the invention is that a) a mixture of elemental sulfur, elemental selenium, or elemental chalcogen; b) at least one conductive additive; c) at least one organic moiety and at least one-. S-S _n - bond (wherein, n is 0 or an integer of 1 or more) to provide a cathode comprising at least one organic sulfur species including.

A further aspect of the present invention provides an alloy or composite of sodium, lithium, potassium, magnesium, or at least one of sodium, lithium, potassium or magnesium and at least one other metal to provide ions. an anode including an anode active material comprising, at least one and at least one organic moiety -S-S _n - bond (n is 0 or an integer of 1 or more) at least one organic sulfur-containing chemical species Or has been treated with the organic sulfur species. Such treatment results in increased battery life and reduced capacity loss in subsequent cycles.

For example, organic sulfur species are organic polysulfides, organic thiolates ｛n = 0, for example, the general formula RSM (where R is an organic moiety, M is Li, Na, K, Mg, quaternary ammonium Or cations such as quaternary phosphoniums) and / or metal organic polythiolates. In some embodiments of the present invention, the organosulfur species is 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. It contains one or more sulfur-containing functional groups selected from the group consisting of: In other embodiments, the organosulfur species can be selected from the group consisting of aromatic polysulfides, polyether-polysulfides, polysulfide-acid salts, and mixtures thereof.

1, n-C ₁₂ lithium H ₂₅ SLi was added to the cathode - a diagram showing the discharge profile for 3 times to 63 times of repeated charge / discharge cycles of sulfur batteries. FIG. 2 shows that the anode was treated with 3,6-dioxaoctane-1,8-dithiol dilithium salt (LiS—C ₂ H ₄ —O—C ₂ H ₄ —O—C ₂ H ₄ —SLi). FIG. 3 shows a comparison of the cycle performance of cells prepared without treatment.

  An electroactive substance processed into a structure used for a battery is called an electrode. For a pair of electrodes used in a battery that acts as a chemical source of electrical energy, the electrode with the higher electrochemical potential is called the positive electrode or cathode, while the electrode with the lower electrochemical potential is called the positive electrode or cathode. The electrode is called a negative electrode or an anode. Conventional nomenclature for batteries is used herein, and the terms "cathode" or "positive electrode" and "anode" or "negative electrode" refer to the electrical potential of the electrodes during discharge of the cell to provide electrical energy. Refers to chemical function. During the charging portion of the cycle, the actual electrochemical function of the electrodes is reversed with respect to what occurs during discharging, but the indication of each electrode remains the same as for discharging.

  Electrochemical cells are generally combined in series, and the collection of such cells is called a battery. Based on the effective chemical reaction of the cell, the primary battery is designed for simple discharge, which supplies power to external devices. Secondary batteries are rechargeable using electrical energy from an external source, thus achieving long-term use with multiple discharge and charge cycles.

  The electrochemically active material used for the cathode, ie, the positive electrode, is hereinafter referred to as the cathode active material. The electrochemically active material used for the anode or negative electrode is hereinafter referred to as the anode active material. A multi-component composition having electrochemical activity and comprising an electrochemically active material, optional conductive additives and binders, and other optional additives is hereinafter referred to as an electrode composition. A battery comprising a cathode having a cathode active material in an oxidized state and an anode having an anode active material in a reduced state is said to be in a charged state. Thus, a battery comprising a cathode having a cathode active material in a reduced state and an anode having an anode active material in an oxidized state is said to be in a discharged state.

Without wishing to be bound by theory, the following are some possible advantages or features of the present invention. Organic sulfur species can be partitioned into a sulfur-rich catholyte phase. In addition to the sulfur extrusion / reinsertion chemistry common to polysulfides and polythiolates, divalent anionic sulfides or polysulfides (eg, Li ₂ S _x , x = 1, 2, 3,...) And organic polysulfides, organic The chemical exchange reaction between a thiolate or an organic polythiolate (eg, R—S _x —R ′ or R—S _x —Li, R and R ′ = organic moiety, x is 0 or an integer greater than or equal to 1) Advantageously, it minimizes the amount of divalent anionic polysulfide in the catholyte and also favors redeposition of sulfur and sulfur-containing species at the cathode. The net removal of the divalent anionic polysulfide will reduce the viscosity of the electrolyte, thus minimizing the detrimental effect of the high viscosity on the conductivity of the electrolyte. Organic sulfur species also increase the dissolution of insoluble low-rank lithium sulfide species (specifically, Li ₂ S and Li ₂ S ₂ ) in both the catholyte and anolyte phases, and thus reduce their emissions. And thus minimize the loss of reactive lithium species during repeated charge / discharge cycles. The performance of an organic sulfur species can be "tuned" by the choice of its organic functionality. For example, short-chain alkyl groups or alkyl groups with more polar functionality will partition more into the anolyte phase, while longer-chain or less polar homologs will distribute more into the catholyte phase. Will be distributed. Adjusting the relative ratio of long / non-polar organic species to short / polar organic species will provide a means to control the distribution of sulfur-containing species to the cathode / catholyte. In addition, the presence of some amount of polysulfide or polythiolate in the anolyte is a convenient means of controlling lithium dendrite growth on the anode during charging, so the selection of appropriate organic moieties and their relative proportions Will provide greater control of dendrite growth.

Organic sulfur species useful in the present invention, at least one and at least one organic moiety -S-S _n - comprises a binding (here, n is 0 or integer of at least 1). Organic sulfur species in one embodiment, -S-S _n - (wherein, n represents an integer of 1 or more and is) (polysulfide) coupled with two organic portions (these mutually identical per molecule bound by also And may be different). The -S-S _n - bond, a larger linking group, for example, ^{-Y 1 -C (Y 2 Y 3} ) -S-S n - bond or ^{-Y 1 -C (= Y 4)} -S-S n A bond (where Y ¹ is O or S, Y ² and Y ³ are independently an organic moiety or —S—S _o —Z (where o is 1 or more, and Z is an organic moiety or Li, Na, K, Mg, a quaternary ammonium or a quaternary phosphonium), and Y ⁴ is O or S). In another embodiment, the organosulfur species comprises a monovalent organic moiety and a species selected from Na, Li, K, Mg, quaternary ammonium, and quaternary phosphonium, wherein the -S -S _n - bond (in which, for example, ^{-Y 1 -C (Y 2 Y 3} ) -S-S n - bond or ^{-Y 1 -C (= Y 4)} -S-S n - bond (wherein , N is 0 or an integer of 1 or more). In yet another embodiment -S-S _n - bond may also appear on both sides of the organic portion. For example, the organic moiety can be a divalent, optionally substituted aromatic moiety, C (R ³ ) _2, wherein each R ³ is independently H or an organic moiety, such as a C ₁ -C ₂₀ organic moiety. ), Carbonyl (C = O), or thiocarbonyl (C = S).

For example, organic sulfur species include organic polysulfides, organic thiolates, organic polythiolates, such as those having sulfur-containing functional groups, such as dithioacetals, dithioketals, trithio-orthocarbonates, aromatic polysulfides, polyether-polysulfides, polysulfide-acids. Salt, thiosulfonate [-S (O) ₂ -S-], thiosulfinate [-S (O) -S-], thiocarboxylate [-C (O) -S-], dithiocarboxylate [- RC (S) -S-], thiophosphate or thiophosphonate functional groups, or mono-, di- or trithiocarbonate functional groups; organometallic polysulfides containing these or similar functional groups; Selected from the group consisting of mixtures thereof.

Suitable organic moieties include, for example, monovalent, divalent, and multivalent organic moieties, which can include branched, linear, and / or cyclic hydrocarbyl groups. As used herein, the term "organic moiety" includes one or more heteroatoms such as oxygen, nitrogen, sulfur, halogen, phosphorus, selenium, silicon, metal, such as tin, in addition to carbon and hydrogen. And the like that can include the like. Heteroatoms can be present in the form of functional groups in the organic moiety. Thus, hydrocarbyl groups and functionalized hydrocarbyl groups are considered organic moieties within the context of the present invention. The organic moiety in one embodiment is a C ₁ -C ₂₀ organic moiety. In another embodiment, the organic moiety contains two or more carbon atoms. Thus the organic moiety may be a C ₂ -C ₂₀ organic moiety.

The organic sulfur species may be monomeric, oligomeric, or polymeric in nature. For example -S-S _n - functional groups can have hanging on two or more of the main chain of the oligomer or polymer species containing repeating units of a monomer in its main chain. Oligomer or polymer backbone of the plurality -S-S _n - to contain binding, -S-S _n - functional groups can be incorporated into the backbone of such oligomers or polymers.

Organic sulfur species are, for example, of the formula R ¹ —S—S _n —R ^2, where R ¹ and R ² independently represent a C ₁ -C ₂₀ organic moiety, and n is an integer of 1 or greater. )) Or a mixture of organic polysulfides. The C ₁ -C ₂₀ organic moiety is a monovalent branched, may be linear or cyclic hydrocarbyl group. R ¹ and R ² are each independently a C ₉ -C ₁₄ hydrocarbyl group, and n may be 1 (a disulfide such as tert-dodecyl disulfide is obtained). In another embodiment, R ¹ and R ² are each independently a C ₉ -C ₁₄ hydrocarbyl group and n = 2-5 (giving a polysulfide). Examples of such compounds include TPS-32 and TPS-20 sold by Arkema. In another embodiment, R ¹ and R ² are each independently a C ₇ -C ₁₁ hydrocarbyl group, and n = 2-5. TPS-37LS sold by Arkema is an example of a suitable polysulfide of this type. Another type of suitable polysulfide would be a polysulfide wherein R ¹ and R ² are both tert-butyl and n = 2-5, or a mixture of those polysulfides. Examples of such organic sulfur compounds include TPS-44 and TPS-54 sold by Arkema.

The organosulfur species can also be of the formula R ¹ —S—S _n —M, where R ¹ is a C ₁ -C ₂₀ organic moiety and M is lithium, sodium, potassium, magnesium, quaternary ammonium or a quaternary phosphonium, n represents organic Porichiorato of 1 or more is an integer), or formula R ² -S-M (wherein, R ² is C ₁ -C ₂₀ organic moiety, M is lithium, Organic thiolates that are sodium, potassium, magnesium, quaternary ammonium or quaternary phosphonium).

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).
Wherein each R ³ is H or C ₁ -C ₂₀ organic moiety independently, o, p, and q are each an integer of 1 or more independently, each Z is independently C ₁ ~ C ₂₀ organic moiety, Li, Na, K, Mg, quaternary ammonium or a quaternary phosphonium. Examples of such organosulfur species include 1,2,4,5-tetrathiane (Formula I, R ³ = H, o = p = 1), tetramethyl-1,2,4,5-tetrathiane ( formula _{^{I, R 3 = CH 3,}} o = p = 1), and their oligomers or polymers chemical species.

Another embodiment of the invention is an aromatic polysulfide of formula (IV), a polyether-polysulfide of formula (V), a salt of a polysulfide-acid of formula (VI), or a salt of a polysulfide-acid of formula (VII) Utilizing organic sulfur species.
Here, R ⁴ in the formula (IV) is independently tert-butyl or tert-amyl, R ⁵ is independently OH, OLi, or ONa, and r is 0 or more (eg, 0 to 10). Wherein the aromatic ring is optionally substituted at one or more other positions with a substituent other than hydrogen; R ⁶ in formula (VI) is a divalent organic moiety; R ⁷ is a divalent organic moiety, each Z is independently a C ₁ -C ₂₀ organic moiety, Li, Na, K, Mg, quaternary ammonium or quaternary phosphonium, and each M is independently And 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 are the aromatic polysulfides sold by Arkema under the trade name Vultac® (Formula IV, R ⁴ = tert-butyl or tert-amyl, R ⁵ = OH). Derived from a mercapto acid, such as mercaptoacetic acid, mercaptopropionic acid, mercaptoethanesulfonic acid, mercaptopropanesulfonic acid, or from an olefin-containing acid, such as vinylsulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid. And the salts of polysulfide-acids corresponding to Formulas VI and VII.

In yet another embodiment, the organosulfur species is an organic polysulfide or organometallic polysulfide containing a trithiocarbonate functionality of formula (IX), an organic polysulfide or organometallic polysulfide containing a dithiocarbonate functionality of formula (X) Or an organic polysulfide or organometallic polysulfide containing a monothiocarbonate functional group of formula (XI)
(Where Z is a C ₁ -C ₂₀ organic moiety, Na, Li, K, Mg, quaternary ammonium, or quaternary phosphonium, and o and p are independently integers of 1 or more)
It is.

The liquid or gel electrolyte solution may further comprise a compound of the formula MS—S _n —M, wherein each M is independently Li, Na, K, Mg, quaternary ammonium, or quaternary phosphonium; Is an integer of 1 or more). Thus, such species, unlike the organic sulfur species described above, do not contain an organic moiety.

  The intermediate separator element can serve as a divider between compartments in the electrochemical cell. Certain compartments may include an electrolyte in contact with the cathode (the electrolyte in such a compartment may be referred to as a catholyte). Another compartment may include an electrolyte in contact with the anode (the electrolyte in such a compartment may be referred to as an anolyte). The anolyte and catholyte may be the same or different. One or both of the anolyte and catholyte can contain one or more organic sulfur species according to the present invention. The intermediate separator element allows ions from the anolyte to pass through the intermediate separator element and into the catholyte (and vice versa, whether the electrochemical cell is operating in charge mode or in discharge mode). (Depending on what is being done) can be positioned between such compartments.

In a further embodiment of the invention, the intermediate separator element is composed of a porous polymer. The porous polymer may be composed of, for example, polypropylene, polyethylene, or fluorinated polymer. Porous polymers can be functionalized with organic sulfur species of the type described herein. The organosulfur species may be depending on the backbone of the porous polymer and / or may be present in cross-links between the backbones of the individual polymer chains and / or may be present on the porous backbone. It can also be incorporated into the main chain of the chain. Therefore the backbone of the porous polymer is one or more of -S-S _n - can contain binding, and / or -S-S _n - bond may have pendent to the main chain of the polymer . Such -S-S _n - bond can also be present in the crosslinking.

  Suitable solvents for use in the electrochemical cell according to the present invention include the basic or (cationically complexed) aprotic polar solvents known or commonly used in lithium-sulfur batteries, such as sulfolane, dimethylsulfoxide, dimethyl Acetamide, tetramethylurea, N-methylpyrrolidinone, tetraethylsulfamide; ethers such as tetrahydrofuran, methyl-THF, 1,3-dioxolan, 1,2-dimethoxyethane (glyme), diglyme and tetraglyme, and these Mixtures; carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate and the like; and esters such as methyl acetate, ethyl acetate, propyl acetate, and γ-butyrol Tons, and the like. The electrolyte can include such a solvent alone or a mixture of such solvents. Any polar aprotic polymer known in the battery art can also be used. The electrolyte may include a polymeric material and may take the form of a gel. Suitable polymers for use in the electrolyte include, for example, polyethylene oxide, polyethersulfone, polyvinyl alcohol, or polyimide. The electrolyte may be in the form of a gel, which may be a three-dimensional network composed of a liquid and a binder component. The liquid may be a monomer solvent entrained within the polymer, such as a crosslinked polymer.

One or more conductive salts are present in the electrolyte in combination with the non-aqueous polar aprotic solvent and / or polymer. Conducting salts are well known in the battery arts and include, for example, (CF ₃ SO ₂ ) ₂ N ⁻ , CF ₃ SO ₃ ⁻ , CH ₃ SO ₃ ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ^−. , Nitric acid, halogens and the like. Salts of sodium and other alkali metals and mixtures thereof can also be used.

  The anode active material can include 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, alloys of lithium, metal sodium, sodium alloys, alkali metals or their alloys, metal powders, alloys of lithium with aluminum, magnesium, silicon, and / or tin, alkali metals Carbon and alkali metal-graphite intercalation materials, compounds that can be reversibly oxidized and reduced with alkali metal ions, and mixtures thereof. The metal or metal alloy (eg, metallic lithium) may be included as one membrane or as several membranes in the battery, optionally separated by a ceramic material. Suitable ceramic materials include, for example, silica, alumina, or lithium-containing glassy materials, such as lithium phosphate, lithium aluminate, lithium silicate, lithium nitride phosphate, tantalum oxide, lithium aluminosilicate, lithium titanium oxide, lithium. Examples include silicosulfide, lithium germanosulfide, lithium aluminosulfide, lithium borosulfide, lithium phosphosulfide, and mixtures thereof.

  The anode can be in any suitable form, such as a foil, composite or other type of current collector.

  In one embodiment of the invention, the anode is treated with at least one organic sulfur species. Such treatment can be performed by contacting the surface of the anode with at least one organic sulfur species. The organic sulfur species can be in the form of a solution, for example, during such a contacting step. Any solvent or combination of solvents for the organic sulfur species can be used to form such a solution. For example, the solvent can be any of the aprotic polar solvents described above. In one embodiment, the anode is treated with an organic sulfur chemical prior to assembly of the electrochemical cell, such as by spraying a solution of the organic sulfur species on the anode or dipping the anode in the solution of the organic sulfur species. Treated with seeds. In another embodiment, the organic sulfur species is incorporated as a component of the electrolyte used in the electrochemical cell, and the electrolyte containing the organic sulfur species contacts the anode on the electrochemical cell assembly.

  In another embodiment, the anode comprises at least one organic sulfur 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 organic sulfur species can be deposited on the surface of the anode.

  The cathode comprises elemental sulfur, elemental selenium, or a mixture of elemental chalcogens. In one embodiment, the cathode is additionally comprised of one or more organosulfur species as described in detail hereinabove. The cathode may additionally and / or alternatively be composed of a binder and / or a conductive additive. Suitable binders include, for example, polyvinyl alcohol, polyacrylonitrile, polyvinylidene fluoride (PVDF), polyvinyl fluoride, polytetrafluoroethylene (PTFE), copolymers of tetrafluoroethylene and hexafluoropropylene, and copolymers of vinylidene fluoride and hexafluoropropylene. Copolymers, copolymers of vinylidene fluoride and tetrafluoroethylene, ethylene-propylene-diene monomer rubber (EPDM), and polymers such as polyvinyl chloride (PVC). The conductive additive may be a conductive form of carbon such as, for example, graphite, graphene, carbon fiber, carbon nanotubes, carbon black, or soot (eg, lamp or furnace soot). This cathode may be present in the battery or electrochemical cell in combination with any of the current collectors, for example, those known in the art of batteries or electrochemical cells. For example, the cathode can be applied to the surface of a metal current collector.

  Aspects of the invention include:

1. a) an anode comprising an anode active material comprising sodium, lithium, or an alloy or composite of at least one of sodium or lithium and at least one metal to provide ions;
b) a cathode comprising a cathode active material comprising elemental sulfur, elemental selenium, or a mixture of elemental chalcogens;
c) an intermediate separator element located between the anode and the cathode and acting to separate the liquid or gel electrolyte solution in contact with the anode and the cathode, through which the metal ions and their A battery comprising: an intermediate separator element, wherein counter ions move between the anode and the cathode during a charge and discharge cycle of the battery;
The liquid or gel electrolyte solution comprises a non-aqueous polar aprotic solvent or polymer and a conductive salt, and conditions (i), (ii), (iii) or (iv):
(I) at least one of the liquid or gel electrolyte solutions further comprises at least one organic sulfur species;
(Ii) the cathode is further comprised of at least one organic sulfur species;
(Iii) the intermediate separator element comprises a functionalized porous polymer containing at least one organic sulfur species;
(Iv) the anode is further comprised of or treated with at least one organic sulfur species;
Satisfy at least one of
The organic sulfur species, at least one and at least one organic moiety -S-S _n - comprises a binding (n is 0 or an integer of 1 or more), the battery.

2. The battery of aspect 1, wherein said organic sulfur species is selected from the group consisting of organic polysulfides, organic thiolates and organic polythiolates and mixtures thereof.

3. The organic sulfur species is dithioacetal, dithioketal, trithio-orthocarbonate, thiosulfonate [—S (O) ₂ —S—], thiosulfinate [—S (O) —S—], thiocarboxylate [ -C (O) -S-], one selected from the group consisting of dithiocarboxylate [-C (S) -S-], thiophosphate, thiophosphonate, monothiocarbonate, dithiocarbonate and trithiocarbonate. The battery of aspect 1 or 2, wherein the battery comprises a plurality of sulfur-containing functional groups.

4. The battery of any of aspects 1 to 3, wherein the organic sulfur species is selected from the group consisting of aromatic polysulfides, polyether-polysulfides, polysulfide-acid salts, and mixtures thereof.

5. The organic sulfur species is an organic polysulfide of the formula R ¹ —S—S _n —R ² , wherein R ¹ and R ² are independently linear, branched or cyclic aliphatic or aromatic. C ₁ -C ₂₀ organic moiety lying can, and optionally N, O, which may include P, S, Se, Si, Sn, one or more functional groups containing halogen and / or metal Wherein n is an integer of 1 or more.

6. The organic sulfur species is an organic thiolate of the formula R ¹ -S-M or an organic polythiolate of the formula R ¹ -S-S _n -M, wherein R ¹ is linear, branched or cyclic. C, which can be aliphatic or aromatic and can optionally include one or more functional groups containing N, O, P, S, Se, Si, Sn, halogen and / or metal ₁ -C represents ₂₀ organic moiety, M is lithium, sodium, potassium, magnesium, quaternary ammonium, or a quaternary phosphonium, n represents an integer of 1 or more, the aspect 1-5 either battery.

7. The organic sulfur species is a dithioacetal or dithioketal of formula (I) or (II), or a trithio-orthocarboxylate of formula (III)
And
Wherein each R ³ can independently be H, or a linear, branched or cyclic aliphatic or aromatic, and optionally N, O, P, S, Se, Si, Sn, a C ₁ -C ₂₀ organic moiety that may contain one or more functional groups containing halogen and / or metal, o, p and q are each an integer of 1 or more independently and each Z can be independently linear, branched or cyclic, aliphatic or aromatic, and optionally contains N, O, P, S, Se, Si, Sn, halogen and / or metal C ₁ -C ₂₀ organic moiety that may contain one or more functional groups, Li, Na, K, Mg, quaternary ammonium or quaternary phosphonium, any battery aspects 1-6.

8. The organic sulfur species is an aromatic polysulfide of formula (IV), a polyether-polysulfide of formula (V), a salt of a polysulfide-acid of formula (VI), or a salt of a polysulfide-acid of formula (VII)
And
Here, R ⁴ in the formula (IV) is independently tert-butyl or tert-amyl, R ⁵ is independently OH, OLi, or ONa, r is 0 or more, and the aromatic ring is Is optionally substituted at one or more positions with a substituent other than hydrogen, wherein R ⁶ in formula (VI) is a divalent organic moiety and R ⁵ in formula (VII) is , and the respective Z is C ₁ -C ₂₀ organic moiety independently, Li, Na, or quaternary ammonium, each M is independently Li, Na, K, Mg, quaternary ammonium, or a The battery of any of aspects 1 to 7, wherein the battery is a quaternary phosphonium and o and p are each independently an integer of 1 or more.

9. Wherein the organosulfur species is an organic polysulfide or organometallic polysulfide containing a trithiocarbonate functional group of formula (IX), an organic polysulfide or organometallic polysulfide containing a dithiocarbonate functional group of formula (X), or formula (XI) Organic polysulfides or organometallic polysulfides containing monothiocarbonate functional groups
And
Wherein Z is a C ₁ -C ₂₀ organic moiety, Na, Li, quaternary ammonium, or quaternary phosphonium, and o and p are independently integers of 1 or more. 8. The battery according to any of 8.

10. The liquid or gel electrolyte solution further comprises a polythiolate bimetallic species of the formula MS—S _n —M, wherein each M is independently Li, Na, K, Mg, quaternary. The battery according to any one of aspects 1 to 9, wherein the battery is ammonium or a quaternary phosphonium, and n is an integer of 1 or more.

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

12. The battery of any of aspects 1-11, wherein the organic sulfur species is dependent on the backbone of the functionalized porous polymer.

13. The battery of any of aspects 1-12, wherein the organosulfur species crosslinks into the backbone of the functionalized porous polymer or forms part of the backbone of the functionalized porous polymer. .

14． 14. The battery of any of aspects 1-13, wherein the organic moiety contains at least two carbon atoms.

15. The intermediate porous separator partitions the battery to provide an anolyte portion associated with the anode and a catholyte portion associated with the cathode, and wherein the organic sulfur species is the anolyte portion or the anolyte portion. 15. The battery of any of aspects 1-14, wherein the battery is present on at least one of the catholyte portions.

16. Wherein the polar aprotic solvent or polymer non-aqueous, ether, carbonyl, ester, carbonate, amino, amido, Surufijiru [-S-], sulfinyl [-S (O) -], or a sulfonyl [-SO ₂ -] 16. The battery according to any one of aspects 1 to 15, comprising one or more functional groups selected from the group consisting of:

17． The conductive salt corresponds to the formula MX, wherein M is Li, Na or quaternary ammonium, and X is (CF ₃ SO ₂ ) ₂ N, CF ₃ SO ₃ , CH ₃ SO ₃ , ClO _4, PF _6, NO is _3, AsF ₆ or halogen, one of the battery aspects 1-16.

18. Aspects 1 to 17, wherein the organic moiety is an oligomer or polymer and the organosulfur species comprises at least one -S-S- bond depending on the backbone of the organic moiety of the oligomer or polymer. One of the batteries.

19. Any of aspects 1-18, wherein the organic moiety is an oligomer or polymer and the organic sulfur species comprises at least one -SS- bond incorporated into the backbone of the organic moiety of the oligomer or polymer. Battery.

20. And at least one non-aqueous polar aprotic solvents or polymers, at least one conductive salt, at least one organic moiety and at least one -S-S _n - bond (wherein, n represents 0 or And at least one organic sulfur species.

21. a) elemental sulfur, and a mixture of elemental selenium, or elemental chalcogen, b) at least one electrically conductive additive, c) at least one organic moiety and at least one -S-S _n - bond (wherein Wherein n is 0 or an integer greater than or equal to 1).

22. The cathode of aspect 21, combined with a current collector.

23. The cathode of aspect 21 or 22, wherein the at least one conductive additive comprises graphite, carbon nanotubes, carbon nanofibers, graphene, carbon black or soot.

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

25. An anode comprising an anode active material comprising sodium, lithium, potassium or magnesium, or an alloy or complex of at least one of sodium, lithium, potassium or magnesium with at least one other metal to provide ions And
At least one organic moiety and at least one -S-S _n - bond (n is 0 or 1 or more is an integer) and at least one or more comprising an organic sulfur species or organic sulfur containing chemical species The anode being processed.

  Although the embodiments have been described herein in a manner that allows clear and concise specifications to be written, the embodiments may be combined or separated in various ways without departing from the invention. It is intended and understood to be good. For example, it is understood that all of the preferred features described herein are applicable to all of the aspects of the invention described herein.

  In some embodiments, the invention herein can be construed as excluding any element or method step that does not substantially affect the basic and novel properties of the composition or method. Further, in some embodiments, the present invention can be construed as excluding any elements or method steps not embodied herein.

Cathode preparation, battery preparation, and battery testing

Example 1

A positive electrode comprising 70% by weight of sublimable elemental sulfur powder, 20% by weight of polyethylene oxide (PEO, MW 4 × 10 ⁶ ), and 10% by weight of carbon black (Super P® Conductive, Alfa Aesar) was prepared as follows. Created by the procedure.

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

Example 2

A positive cathode containing lithium n-dodecyl mercaptide (10% by weight sulfur) was prepared according to the procedure described in Example 1. The resulting coating contained 3.4 mg of sulfur per cm ² .

Example 3

  This positive cathode from Example 2 was used in a PTFE Swagelok cell with two stainless steel rods, or a coin cell assembly (CR2032) made of stainless steel. The battery cells were assembled as follows in a glove box (Mbraun) filled with argon. That is, the cathode electrode was placed on the bottom can, followed by the separator. Next, the electrolytic solution was added to the separator. A lithium electrode was placed on the separator. A spacer and a spring were placed on top of the lithium electrode. The battery core was sealed with a stainless steel rod or a crimping machine.

Example 4

  After the procedure described in Example 3, the cathode from Example 2 (7/16 ″ diameter) and 0.5 M LiTFSI solution in tetraethylene glycol dimethyl ether (TEGDME): 1,3-dioxolane (DOL) = 1: 1 A battery cell consisting of 20 μL of No. 1, a separator and a lithium electrode (thickness 0.38 mm, diameter 7/16 ″) was tested for charge-discharge cycles at 0.1 mA. The test was performed using a Gamry potentiometer (Gamry Instruments) at room temperature against cut-off voltages of 1.5V and 3.2V. FIG. 1 shows the profile of the discharge cycle.

Synthesis of lithium alkyl mercaptide

Example 5-Synthesis of lithium n-dodecylmercaptide using hexyllithium

  N-Hexyllithium (33% by weight in hexane, 1.1 equivalents) was added to n-dodecylmercaptan (9.98g, 1 equivalent) dissolved in hexane (100mL) at -30 ° C, and the mixture temperature was below -20 ° C. Was added dropwise to keep The solvent was removed under reduced pressure and a white solid was obtained in quantitative yield.

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

  A mixture of n-dodecyl mercaptan (2.0 g, 1 eq) and lithium hydroxide monohydrate (0.41 g, 1 eq) dispersed in acetonitrile (8 mL) was heated to 75 ° C and Stirred for hours. After cooling to room temperature, the reaction mixture was filtered. The filter cake was rinsed with acetonitrile and dried in a vacuum oven at 50 ° C. 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 using lithium hexyl

  Following the procedure described in Example 6, the dilithium salt of 3,6-dioxaoctane-1,8-dithiol was synthesized from dimercaptan as a white solid in quantitative yield.

Synthesis of lithium alkyl polythiolate

Example 8-Synthesis of lithium n-dodecyl polythiolate using lithium hydroxide

To a solution of n-dodecylmercaptan (2.00 g, 1 eq.) Dissolved in 1,3-dioxolane (25 mL) degassed with nitrogen was added lithium hydroxide monohydrate (0.41 g, 1 eq.) And sulfur ( 1.27 g, 4 eq.). The mixture was stirred at room temperature under nitrogen for 30 minutes. Lithium n-dodecyl polythiolate dissolved in 1,3-dioxolane was obtained as a dark red solution. Complete conversion of the mercaptan to lithium n-dodecyl polythiolate was confirmed by ¹³ C-NMR and LCMS.

Example 9-Synthesis of lithium 3,6-dioxaoctane-1,8-polythiolate using lithium hydroxide and sulfur

  According to the procedure described in Example 8, 3,6-dioxaoctane-1,8-dithiol (0.72 g, 1 eq.), Lithium hydroxide monohydrate (0 mL) in 1,3-dioxolane (10 mL). .33 g, 2 equiv.) And sulfur (1.02 g, 8 equiv.) Gave a dark red solution of lithium 3,6-dioxaoctane-1,8-polythiolate in 1,3-dioxolane. Obtained.

Example 10-Synthesis of lithium n-dodecyl polythiolate from lithium alkyl mercaptide

  To a nitrogen degassed slurry of lithium n-dodecyl mercaptide (0.21 g, 1 eq) dispersed in 1,3-dioxolane (5 mL) was added sulfur (0.13 g, 4 eq). The mixture was stirred at room temperature under nitrogen for 16 hours. The insoluble solid was removed by filtration. The dark red filtrate contained 63% lithium n-dodecyl polythiolate and 37% mixture of bis (n-dodecyl) polysulfide as determined by LCMS.

Example 11-Synthesis of lithium n-dodecyl polythiolate using lithium metal and sulfur

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

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

According to the procedure of Example 11, 3,6-dioxaoctane-1,8-dithiol (1.97 g, 1 eq), lithium metal (0.15 g, 2 eq) in 1,3-dioxolane (11 mL), And sulfur (2.77 g, 8 eq) gave a dark red solution of lithium 3,6-dioxaoctane-1,8-polythiolate in 1,3-dioxolane. Complete conversion of the starting di-mercaptan was confirmed by ¹³ C-NMR.

Example 13 Dissolution of Li ₂ S with lithium n- dodecyl poly thiolate was added

To determine the solubility of lithium sulfide in the electrolyte in the presence of lithium n-dodecyl polythiolate, a saturated solution of lithium sulfide was prepared as follows. That is, a 0.4 M solution of lithium n-dodecyl polythiolate dissolved in 1,3-dioxolane was prepared according to the procedure described in Example 10. The solution was then diluted to 0.2 M with tetraethylene glycol dimethyl ether, and then diluted 1: 1 (= v / v) with a 1 M solution of LiTFSI in 1: 1 tetraethylene glycol dimethyl ether: 1,3-dioxolane. v). Lithium sulfide was added to the resulting solution until a saturated mixture was obtained. The mixture was then filtered and the filtrate was analyzed for dissolved lithium by ICP-MS (Agilent 7700x ICP-MS). The solubility of lithium sulfide was calculated based on its lithium level. In 0.5 M LiTFSI with 0.1 M lithium n-dodecyl polythiolate dissolved in 1: 1 tetraethylene glycol dimethyl ether: 1,3-dioxolane, the solubility of lithium sulfide was determined to be 0.33% by weight. Was. In contrast, without lithium n-dodecyl polythiolate, the solubility of lithium sulfide in 0.5M LiTFSI was only 0.13% by weight. This clearly demonstrated that the presence of the organic sulfur of the present invention enhanced the solubility of Li ₂ S in the electrolyte matrix of the battery.

Example 14-Preparation of a cell containing an organosulfur species-treated anode

This example illustrates the preparation of a battery cell having an anode exposed to an electrolyte containing an organic sulfur species according to one aspect of the present invention. Elemental sulfur, conductive carbon and polyethylene (as a binder) were combined in a mass ratio (sulfur: carbon: polyethylene) of 75: 20: 5 and ball-milled with chloroform to form a slurry. The slurry was then blade cast on a carbon coated aluminum foil and air dried to a sulfur loading of about 0.5 mg / cm ² . The resulting cathode was then assembled into a CR2032 coin cell using a polypropylene separator and a lithium foil anode in an argon-filled glove box. The electrolyte used was 0.38M lithium bis (trifluoromethane) sulfonamide and 0.38M lithium nitrate in a 1: 1 (v / v) mixture of 1,3-dioxolane and 1,2-dimethoxyethane, respectively. It did contain. One electrolyte (according to the invention) additionally has 100 mM 3,6-dioxaoctane-1,8-dithiol dilithium salt (LiS—C ₂ H ₄ —O—C ₂ H ₄ —O—C ₂ H). ₄ -SLi) (whereby the lithium foil anode was contacted with 3,6-dioxaoctane-1,8-dithiol dilithium salt) while the other electrolyte (control) Did not contain organic sulfur species. Battery cycles were performed for battery tests at 1.7-2.6 V, 40, C / 2 for active sulfur. The observed results are shown in FIG.

Claims (25)

a) an anode comprising an anode active material comprising sodium, lithium, or an alloy or composite of at least one of sodium or lithium and at least one metal to provide ions;
b) a cathode comprising a cathode active material comprising elemental sulfur, elemental selenium, or a mixture of elemental chalcogens;
c) an intermediate separator element located between the anode and the cathode and acting to separate the liquid or gel electrolyte solution in contact with the anode and the cathode, through which the metal ions and their A battery comprising: an intermediate separator element, wherein counter ions move between the anode and the cathode during a charge and discharge cycle of the battery;
The liquid or gel electrolyte solution comprises a non-aqueous polar aprotic solvent or polymer and a conductive salt, and conditions (i), (ii), (iii) or (iv):
(I) at least one of the liquid or gel electrolyte solutions further comprises at least one organic sulfur species;
(Ii) the cathode is further comprised of at least one organic sulfur species;
(Iii) the intermediate separator element comprises a functionalized porous polymer containing at least one organic sulfur species;
(Iv) the anode is further comprised of or treated with at least one organic sulfur species;
Satisfy at least one of
The organic sulfur species, at least one and at least one organic moiety -S-S _n - comprises a binding (n is 0 or an integer of 1 or more), the battery.   The battery of claim 1, wherein the organic sulfur species is selected from the group consisting of organic polysulfides, organic thiolates and organic polythiolates and mixtures thereof. The organic sulfur species is dithioacetal, dithioketal, trithio-orthocarbonate, thiosulfonate [—S (O) ₂ —S—], thiosulfinate [—S (O) —S—], thiocarboxylate [ -C (O) -S-], one selected from the group consisting of dithiocarboxylate [-C (S) -S-], thiophosphate, thiophosphonate, monothiocarbonate, dithiocarbonate and trithiocarbonate. The battery according to claim 1, wherein the battery contains a plurality of sulfur-containing functional groups.   The battery of claim 1, wherein the organic sulfur species is selected from the group consisting of aromatic polysulfides, polyether-polysulfides, polysulfide-acid salts, and mixtures thereof. The organic sulfur species is an organic polysulfide of the formula R ¹ —S—S _n —R ² , wherein R ¹ and R ² are independently linear, branched or cyclic aliphatic or aromatic. C ₁ -C ₂₀ organic moiety lying can, and optionally N, O, which may include P, S, Se, Si, Sn, one or more functional groups containing halogen and / or metal The battery according to claim 1, wherein n is an integer of 1 or more. The organic sulfur species is an organic thiolate of the formula R ¹ -S-M or an organic polythiolate of the formula R ¹ -S-S _n -M, wherein R ¹ is linear, branched or cyclic. C, which can be aliphatic or aromatic and can optionally include one or more functional groups containing N, O, P, S, Se, Si, Sn, halogen and / or metal ₁ -C represents ₂₀ organic moiety, M is lithium, sodium, potassium, magnesium, quaternary ammonium, or a quaternary phosphonium, n represents an integer of 1 or more, battery according to claim 1. The organic sulfur species is a dithioacetal or dithioketal of formula (I) or (II), or a trithio-orthocarboxylate of formula (III)
And
Wherein each R ³ can independently be H, or a linear, branched or cyclic aliphatic or aromatic, and optionally N, O, P, S, Se, Si, Sn, a C ₁ -C ₂₀ organic moiety that may contain one or more functional groups containing halogen and / or metal, o, p and q are each an integer of 1 or more independently and each Z can be independently linear, branched or cyclic, aliphatic or aromatic, and optionally contains N, O, P, S, Se, Si, Sn, halogen and / or metal The battery of claim 1, wherein the battery is a C ₁ -C ₂₀ organic moiety, which can include one or more functional groups, Li, Na, K, Mg, quaternary ammonium, or quaternary phosphonium. The organic sulfur species is an aromatic polysulfide of formula (IV), a polyether-polysulfide of formula (V), a salt of a polysulfide-acid of formula (VI), or a salt of a polysulfide-acid of formula (VII)
And
Here, R ⁴ in the formula (IV) is independently tert-butyl or tert-amyl, R ⁵ is independently OH, OLi, or ONa, and r is 0 or more; The ring is optionally substituted at one or more positions with a substituent other than hydrogen, wherein R ⁶ in formula (VI) is a divalent organic moiety and R ⁵ in formula (VII) is a portion, each Z is C ₁ -C ₂₀ organic moiety independently, Li, Na, or quaternary ammonium, each M is independently Li, Na, K, Mg, quaternary ammonium, or The battery according to claim 1, wherein the battery is a quaternary phosphonium, and o and p are each independently an integer of 1 or more. Wherein the organosulfur species is an organic polysulfide or organometallic polysulfide containing a trithiocarbonate functional group of formula (IX), an organic polysulfide or organometallic polysulfide containing a dithiocarbonate functional group of formula (X), or formula (XI) Organic polysulfides or organometallic polysulfides containing monothiocarbonate functional groups
And
Here, Z is, C ₁ -C ₂₀ organic moiety is Na, Li, quaternary ammonium, or quaternary phosphonium, and o and p is an integer of 1 or more independently, claim 1 The battery according to 1. The liquid or gel electrolyte solution further comprises a polythiolate bimetallic species of the formula MS—S _n —M, wherein each M is independently Li, Na, K, Mg, quaternary. The battery according to claim 1, wherein the battery is ammonium or quaternary phosphonium, and n is an integer of 1 or more.   The battery of claim 1, wherein the cathode is further comprised of at least one conductive additive and / or at least one binder.   The battery of claim 1, wherein the organosulfur species is dependent on the backbone of the functionalized porous polymer.   The battery of claim 1, wherein the organosulfur species crosslinks into the backbone of the functionalized porous polymer or forms part of the backbone of the functionalized porous polymer.   The battery according to claim 1, wherein the organic moiety contains at least two carbon atoms.   The intermediate porous separator partitions the battery to provide an anolyte portion associated with the anode and a catholyte portion associated with the cathode, and wherein the organic sulfur species is the anolyte portion or the anolyte portion. 2. The battery of claim 1, wherein the battery is present on at least one of the catholyte portions. Wherein the polar aprotic solvent or polymer non-aqueous, ether, carbonyl, ester, carbonate, amino, amido, Surufijiru [-S-], sulfinyl [-S (O) -], or a sulfonyl [-SO ₂ -] The battery according to claim 1, comprising one or more kinds of functional groups selected from the group consisting of: The conductive salt corresponds to the formula MX, wherein M is Li, Na, or quaternary ammonium, and X is (CF ₃ SO ₂ ) ₂ N, CF ₃ SO ₃ , CH ₃ SO _{3, ClO 4, PF 6,} NO 3, AsF 6, or a halogen, battery according to claim 1.   2. The organic moiety of claim 1, wherein the organic moiety is an oligomer or polymer, and wherein the organosulfur species comprises at least one -SS- bond depending on the backbone of the organic moiety of the oligomer or polymer. Batteries.   The organic moiety of claim 1, wherein the organic moiety is an oligomer or polymer, and wherein the organic sulfur species comprises at least one —S—S— bond incorporated into the backbone of the organic moiety of the oligomer or polymer. battery. And at least one non-aqueous polar aprotic solvents or polymers, at least one conductive salt, at least one organic moiety and at least one -S-S _n - bond (wherein, n represents 0 or And at least one organic sulfur species. a) elemental sulfur, and a mixture of elemental selenium, or elemental chalcogen, b) at least one electrically conductive additive, c) at least one organic moiety and at least one -S-S _n - bond (wherein Wherein n is 0 or an integer greater than or equal to 1).   22. The cathode of claim 21 in combination with a current collector.   22. The cathode of claim 21, wherein the at least one conductive additive comprises at least one of graphite, carbon nanotubes, carbon nanofibers, graphene, carbon black or soot.   22. The cathode of claim 21, further comprising at least one binder. An anode comprising an anode active material comprising sodium, lithium, potassium or magnesium, or an alloy or complex of at least one of sodium, lithium, potassium or magnesium with at least one other metal to provide ions And
At least one organic moiety and at least one -S-S _n - bond (n is 0 or 1 or more is an integer) and at least one or more comprising an organic sulfur species or organic sulfur containing chemical species The anode being processed.