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CN110023275B - Battery based on organic sulfur substances - Google Patents

Battery based on organic sulfur substances Download PDF

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CN110023275B
CN110023275B CN201780074924.8A CN201780074924A CN110023275B CN 110023275 B CN110023275 B CN 110023275B CN 201780074924 A CN201780074924 A CN 201780074924A CN 110023275 B CN110023275 B CN 110023275B
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formula
battery
organic moiety
organic
lithium
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CN110023275A (en
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G·S·史密斯
L·王
G·C·福特曼
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Arkema Inc
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Arkema Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/12—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms
    • C07C321/14—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/12—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
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    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
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    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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Abstract

Metal-sulfur batteries, such as lithium-sulfur batteries, are made using one or more organosulfur species, such as organic polysulfides and organic polythiolates, as part of a liquid or gel electrolyte solution, as part of a cathode, as part of an anode (or for treating an anode), and/or as part of a functionalized porous polymer that provides an intermediate separator element.

Description

Battery based on organic sulfur substances
Technical Field
The invention relates to cells having an anode based on sodium, lithium, potassium, magnesium or mixtures thereof or alloys or composites of sodium, lithium, potassium and/or magnesium with one or more other metals, and a cathode based on elemental sulphur, selenium or elemental chalcogen mixtures, the anode and cathode being separated by a separator element, a liquid or gel electrolyte solution of an electrically conductive salt in a non-aqueous polar aprotic solvent or polymer being in contact with the electrodes.
Background
Electrochemical cells are the primary means for storing and providing electrical energy. As the demand for energy for electronic, transportation and grid storage applications continues to increase, the demand for batteries with greater storage and delivery capabilities will continue to persist in the future.
Since lithium ion batteries are lightweight and have a strong energy storage capacity compared to other types of batteries, they have been widely used in portable electronic applications since the early 90 s of the 20 th century. However, current lithium ion battery technology does not meet the high power and energy requirements of large applications, such as electric vehicles where grid storage or distance traveled may compete with internal combustion engine vehicles. Therefore, the scientific community continues to make great efforts to search for batteries with higher energy density and capacity.
Sodium-sulfur and lithium-sulfur electrochemical cells provide even higher theoretical energy capacity than lithium-ion batteries, and thus continue to be of interest as "next generation" battery systems. Elemental sulfur to elemental sulfide (S) compared to less than 300mAh/g of theoretical capacity provided by lithium ion batteries 2- ) Provides a theoretical capacity of 1675 mAh/g.
Sodium-sulfur batteries have been developed and introduced as commercial systems. Unfortunately, sodium-sulfur batteries typically require high temperatures (above 300 ℃) to function and are therefore only suitable for large stationary applications.
Lithium-sulfur electrochemical cells (originally introduced in the late 50 s and 60 s of the 20 th century) are now being developed as commercial battery systems. These batteries provide theoretical specific energy densities in excess of 2500Wh/kg (2800 Wh/L), while lithium ion batteries have theoretical specific energy densities of 624Wh/g. The specific energy density exhibited by Li-S batteries is in the range 250-350Wh/kg (compared to 100Wh/g for lithium ion batteries), the lower values being a result of the specific characteristics of the electrochemical processes of these systems during charging and discharging. Considering that the actual specific energy of a lithium ion battery is typically 25-35% of theoretical, the best practical specific energy of a Li-S system is about 780Wh/g (30% of theoretical). [ V.S.Kolosnidisyn, E.Karaseva, U.S. patent application 2008/0100624 A1]
Lithium-sulfur chemistry provides a barrier to these electrochemical cellsA number of technical challenges for cell development, particularly poor discharge-charge cycle performance. However, due to the inherent low weight, low cost and high capacity of lithium-sulfur batteries, there is great interest in improving the performance of the lithium-sulfur system, and a great deal of work has been done by many researchers around the world over the last 20 years to address these problems. Liang et al, handbook of Battery Materials 2 nd Ed. [ handbook of Battery materials 2 nd edition]Chapter 14, pages 811-840 (2011); V.S.Kolossmitsyn et al, J.Power Sources]2011,196,1478-82; and references therein.]
The cell design for lithium-sulfur systems typically includes:
an anode consisting of lithium metal, a lithium alloy or a lithium-containing composite.
A non-reactive but porous separator (typically polypropylene or alpha-alumina) between the anode and the cathode. The presence of this membrane results in separate anolyte and catholyte compartments.
Porous sulfur-containing cathodes incorporated in a binder (often polyvinylidene fluoride) and a conductivity enhancing material (typically graphite, mesoporous graphite, multi-walled carbon nanotubes, graphene).
From a polar aprotic solvent and one or more lithium salts [ (CF) 3 SO 2 ) 2 N - 、CF 3 SO 3 - 、CH 3 SO 3 - 、ClO 4 - 、PF 6 - 、AsF 6 - ]The electrolyte is composed. Solvents used in these cells include basic (cation complexing) aprotic polar solvents such as sulfolane, dimethyl sulfoxide, dimethylacetamide, tetramethylurea, N-methylpyrrolidone, tetraethylsulfonamide, tetrahydrofuran, methyl-THF, 1, 3-dioxolane, diglyme, and tetraglyme. Low polarity solvents are not suitable because of their poor conductivity, solvated Li + The material has poor capacity and the protic solvent reacts with Li metal. In the solid state form of the lithium-sulphur battery, the liquid solvent is replaced by a polymeric material, such as polyethylene oxide.
Universal current collectors and appropriate housing materials.
Summary of The Invention
The present invention provides compositions and uses of organic polysulfides, organothiolates and organopolythiolates for use in metal-sulfur batteries, particularly lithium-sulfur batteries. The organic polysulfides, organothiolates and organopolythiolate materials (hereinafter sometimes referred to as "organosulfur materials") are used to improve the performance of the electrochemical cell during repeated charge and discharge cycles.
The invention thus relates to a chemical energy source comprising a single cell (cell) or battery (battery) having one or more positive electrodes (cathode), one or more negative electrodes (anode) and an electrolyte medium, wherein the chemical reactions carried out involve the reduction of sulphur or polysulphide species and the oxidation of reactive metal species. The negative electrode includes a reactive metal such as lithium, sodium, potassium, magnesium or alloys/composites of these metals with other materials. In some embodiments, the anode further comprises and/or has been treated with at least one organosulfur species. The positive electrode includes elemental sulfur and/or selenium, and in certain embodiments of the invention includes organosulfur species (such as organic polysulfide species and/or metal organic polysulfide salts) and a matrix that holds 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 ionic form of the active metal, and other components intended to optimize electrochemical performance.
In particular, the invention relates to the use of organic sulfides and polysulfides and their lithium (or sodium, potassium, magnesium, quaternary ammonium or quaternary phosphonium) organothiolates or organopolythiolate analogs as components in cathode and electrolyte matrices. The organosulfur species chemically combines with sulfur and anionic mono-or polysulfide species to form an organic polythiolate species having increased affinity for the nonpolar sulfur component of the positive electrode material and the catholyte liquid phase. The organosulfur species can also react with one or more reactive metals present in the negative electrode to form a metal salt of the organosulfur species on the surface of the negative electrodeWhich contributes to the improvement of the performance of an electrochemical cell containing such an organosulfur material-treated negative electrode. Without wishing to be bound by theory, it is believed that the organosulfur species chemically bonds with the reactive metal of the anode, preventing LiS 2 Build up on the anode, which build up is dissolved Li 2 S n (n.gtoreq.1) as a result of a reaction between the substances, and dissolved Li 2 S n (n.gtoreq.1) substances are often present in electrolyte solutions used in metal-sulfur batteries. Thus, the presence of organosulfur species or treatment of the anode with organosulfur species can help prevent the formation of a protective layer on the surface of the anode that can conduct metal cations, thereby preventing the translational flow of sulfur atoms or anions from the cathode to the anode. The metal polysulfide species in the electrolyte becomes saturated, resulting in less sulfur loss from the cathode, higher cell capacity, and increased overall cycle life of the cell.
One aspect of the present invention provides a battery including:
a) An anode comprising an anode active material for providing ions, the anode active material comprising sodium, lithium, potassium, magnesium, or an alloy or composite of at least one of sodium, lithium, potassium, and magnesium with at least one other metal;
b) A cathode comprising a cathode active material comprising elemental sulfur, elemental selenium, or a mixture of elemental chalcogens; and
c) An intermediate membrane element disposed between the anode and the cathode and operative to isolate a liquid or gel electrolyte solution in contact with the anode and the cathode, metal ions and counterions thereof moving between the anode and the cathode through the intermediate membrane element during charge and discharge cycles of the battery;
wherein the liquid or gel electrolyte solution comprises a non-aqueous polar aprotic solvent or polymer and a conductive salt, and at least one of conditions (i), (ii), (iii) and (iv) is satisfied:
(i) At least one of the liquid or gel electrolyte solutions additionally comprises at least one organosulfur species;
(ii) The cathode additionally comprises at least one organosulfur species;
(iii) The middle membrane element comprises a functionalized porous polymer containing at least one organosulfur species;
(iv) The anode further comprises or has been treated with at least one organosulfur species;
wherein the organosulfur species comprises at least one organic moiety and at least one-S n -a bond, n being 0 or an integer greater than or equal to 1.
In one embodiment, only one of conditions (i), (ii), (iii), and (iv) is satisfied. In another embodiment, all four conditions are satisfied. In yet another embodiment, only two or three conditions are met, such as (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).
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 comprising at least one organic moiety and at least one-S n -a bond, wherein n is 0 or an integer greater than or equal to 1.
Yet another aspect of the invention provides a cathode comprising a) elemental sulfur, elemental selenium, or a mixture of elemental chalcogens, b) at least one conductive additive, and c) at least one organosulfur species comprising at least one organic moiety and at least one-S n -a bond, wherein n is 0 or an integer greater than or equal to 1.
Yet another aspect of the present 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 and magnesium with at least one other metal for providing ions, wherein said anode additionally comprises or has been treated with at least one organosulfur species comprising at least one organic moiety and at least one-S n -a bond, wherein n is 0 or an integer greater than or equal to 1. This treatment results in increased battery life and reduced cyclingCapacity fading.
For example, the organosulfur species can be selected from the group consisting of an organic polysulfide, an organosulfur alkoxide (corresponding, for example, to the general formula R-S-M when n =0, where R is an organic moiety and M is a cation such as Li, na, K, mg, quaternary ammonium, or quaternary phosphonium), and/or an organic polythiol metal salt. In certain embodiments of the present invention, the organosulfur species contains one or more sulfur-containing functional groups selected from the group consisting of: dithioacetals, dithioketals, trithio-primary carbonates, thiosulfonates [ -S (O) 2 -S-]Thiosulfinate [ -S (O) -S-]Thiocarboxylate [ -C (O) -S-]Dithiocarboxylates [ -C (S) -S-]Thiophosphate, thiophosphonate, monothiocarbonate, dithiocarbonate and trithiocarbonate. In other embodiments, the organosulfur species can be selected from the group consisting of aromatic polysulfides, polyether-polysulfides, polysulfide-acid salts, and mixtures thereof.
Brief Description of Drawings
FIG. 1 shows that 12 H 25 The lithium-sulfur battery with SLi added to the cathode repeated charge/discharge cycles 3 to 63 times for the discharge characteristic curve.
FIG. 2 shows the reaction of a mixture of dilithium salt (LiS-C) with and without 3, 6-dioxaoctane-1, 8-dithiol 2 H 4 -O-C 2 H 4 -O-C 2 H 4 SLi) cycling performance comparison of the cells prepared from the treated anodes.
Detailed Description
Electroactive materials that have been processed into structures for use in batteries are referred to as electrodes. Of a pair of electrodes used in a battery as a chemical electric energy source, the electrode on the side having a higher electrochemical potential is referred to as a positive electrode or a cathode, and the electrode on the side having a lower electrochemical potential is referred to as a negative electrode or an anode. As used herein, conventional cell nomenclature is used, wherein the terms "cathode" or "anode" and "anode" or "negative electrode" refer to the electrochemical functions of the electrodes in the process of discharging the cell to provide electrical energy. During the charge portion of the cycle, the actual electrochemical function of the electrodes is exactly the opposite of what occurs during discharge, but the name of each electrode remains the same as that at discharge.
Electrochemical cells are typically combined in series, and the collection of such cells is referred to as a battery. The primary battery is designed to be discharged once to supply power to an external device based on chemical reactions performed in the unit cells. Secondary batteries can be recharged with electrical energy from an external source for longer periods of use through multiple discharge and charge cycles.
The electrochemically active material used at the cathode or positive electrode is hereinafter referred to as a cathode active material. The electrochemically active material used at the anode or negative electrode is hereinafter referred to as an anode active material. A multi-component composition that is electrochemically active and comprises an electrochemically active material and optionally 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. Accordingly, 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 intending to be limited by theory, the following are some of the possible advantages or features of the present invention. The organosulfur species can partition to the sulfur-rich catholyte liquid phase. Dianionic sulfides or polysulfides (e.g. Li) 2 S x X =1,2,3 \8230;) and an organic polysulfide, organic thiolate or organic polythiolate (e.g., R-S) x -R' or R-S x -Li, R and R' = organic moieties x =0 or integers equal to or greater than 1), as well as polysulphides and polythiolates common sulphur extrusion/reinsertion chemistry, is beneficial to minimize the amount of dianionic polysulphides in the catholyte solution and to redeposition of sulphur and sulphur-containing species at the cathode. The net removal of dianionic polysulfides reduces the viscosity of the electrolyte solution, thereby minimizing the detrimental effect of high viscosity on electrolyte conductivity. The organosulfur species can also increase catholyte and anolyte phaseInsoluble lower lithium sulfide species (especially Li) in the liquid phase of the electrolyte 2 S and Li 2 S 2 ) And thus scavenged, thereby minimizing the loss of active lithium species upon repeated charge/discharge cycles. The properties of organosulfur species can be "tailored" by the choice of organofunctional groups. For example, short chain alkyl groups or alkyl groups with more polar functional groups will partition more to the anolyte liquid phase, while long chain or less polar analogues will partition more to the catholyte liquid phase. Adjusting the relative proportions of long/nonpolar and short/polar chain organic species will provide a means of controlling the partitioning of sulfur-containing species into the cathode/catholyte solution. Furthermore, since the presence of an amount of polysulphide or polythiol salt in the anolyte liquid is advantageous as a means of controlling lithium dendrite growth on the anode during charging, selecting the appropriate organic moieties and their relative proportions will provide better control of dendrite growth.
The organosulfur species used in the present invention comprise at least one organic moiety and at least one-S n -a bond, wherein n is 0 or an integer greater than or equal to 1. In one embodiment, the organosulfur species contains two organic moieties (which can be the same or different from each other) per molecule that are composed of-S n Linked by a- (polysulfide) bond (where n is an integer of 1 or greater). the-S n The bond may form part of a larger linking group, e.g. -Y 1 -C(Y 2 Y 3 )-S-S n -a bond or-Y 1 -C(＝Y 4 )-S-S n -a bond, wherein Y 1 Is O or S, Y 2 And Y 3 Is a separate organic moiety or-S o -Z, wherein o is 1 or greater and Z is an organic moiety or a material selected from Li, na, K, mg, quaternary ammonium or 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 the group consisting of Na, li, K, mg, quaternary ammonium, and quaternary phosphonium, the species consisting of-S-S n Key linked (e.g. comprising-Y) 1 -C(Y 2 Y 3 )-S-S n -a bond or-Y 1 -C(＝Y 4 )-S-S n A bond, n is 0 or greaterAn integer of 1 or less). In yet another embodiment, -S n The bonds may occur on either side of the organic moiety. For example, the organic moiety may be a divalent, optionally substituted, aromatic moiety C (R) 3 ) 2 (each R) 3 Independently H or an organic moiety such as C 1 -C 20 Organic moiety), carbonyl (C = O) or thiocarbonyl (C = S).
For example, the organosulfur species can be selected from the group consisting of organic polysulfides, organic thiolates, organic polythiolates, including those having sulfur-containing functional groups such as dithioacetals, dithioketals, trithiocarbonates, aromatic polysulfides, polyether-polysulfides, polysulfide-acid salts, thiosulfonates [ -S (O) 2 -S-]Thiosulfinate [ -S (O) -S-]Thiocarboxylate [ -C (O) -S-]Dithiocarboxylates [ -RC (S) -S-]Phosphorothioate or phosphorothioate functional groups, monothiocarbonate, dithiocarbonate or trithiocarbonate functional groups; organo-metal polysulfides containing these or similar functional groups; and mixtures thereof.
Suitable organic moieties include, by way of example, monovalent, divalent, and polyvalent organic moieties, which may comprise branched, straight-chain, and/or cyclic hydrocarbon groups. As used herein, the term "organic moiety" includes moieties that, in addition to including carbon and hydrogen, may include one or more heteroatoms such as oxygen, nitrogen, sulfur, halogens, phosphorus, selenium, silicon, metals such as tin, and the like. One or more heteroatoms may be present in the organic moiety in the form of functional groups. Thus, hydrocarbyl and functionalized hydrocarbyl groups are considered to be organic moieties within the context of the present invention. In one embodiment, the organic moiety is C 1 -C 20 An organic moiety. In another embodiment, the organic moiety comprises two or more carbon atoms. Thus, the organic moiety may be C 2 -C 20 An organic moiety.
The organosulfur species can be monomeric, oligomeric, or polymeric in nature. For example, -S n The functional groups may be pendant to the main chain of an oligomeric or polymeric substance containing two or more atoms in the main chainA plurality of monomeric repeating units. the-S n The functional groups can be incorporated into the main chain of the oligomer or polymer so that the oligomer or polymer contains a plurality of-S-S groups in the main chain n -a bond.
For example, the organosulfur species can be of the formula R 1 -S-S n -R 2 Of an organic polysulfide or of a mixture of organic polysulfides, in which R is 1 And R 2 Independently represent C 1 -C 20 An organic moiety, and n is an integer of 1 or more. The C is 1 -C 20 The organic moiety may be a monovalent branched, straight chain or cyclic hydrocarbon group. R 1 And R 2 May each independently be C 9 -C 14 Hydrocarbyl, wherein n =1 (a disulfide, such as t-dodecyl disulfide, is provided). In another embodiment, R 1 And R 2 Each independently is C 9 -C 14 Hydrocarbyl, wherein n =2-5 (polysulfide provided). Examples of such compounds include TPS-32 and TPS-20, sold by Achima. In another embodiment, R 1 And R 2 Independently is C 7 -C 11 Hydrocarbyl, wherein n =2-5. TPS-37LS, sold by the company Akema, is an example of a suitable polysulfide of this type. Another type of suitable polysulfide is the polysulfide or a mixture of multiple polysulfides, where R is 1 And R 2 Are all tert-butyl and n =2-5. Examples of such organosulfur compounds include TPS-44 and TPS-54, sold by Arkema.
The organosulfur species can also be of the formula R 1 -S-S n Organic polythionates of formula (I) -M, wherein R 1 Is C 1 -C 20 An organic moiety, M is lithium, sodium, potassium, magnesium, quaternary ammonium, or quaternary phosphonium, and n is an integer of 1 or more; or may be of the formula R 2 Organic mercaptides of-S-M, wherein R 2 Is C 1 -C 20 An organic moiety, M is lithium, 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 ester of formula (III):
Figure BDA0002082597390000081
wherein each R 3 Independently is H or C 1 -C 20 An organic moiety, o, p and q are each independently an integer of 1 or more, and each Z is independently C 1 -C 20 An organic moiety, li, na, K, mg, quaternary ammonium or 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 oligomeric or polymeric species thereof.
Another embodiment of the present invention utilizes an organic sulfur species that is an aromatic polysulfide of formula (IV), a polyether-polysulfide of formula (V), a polysulfide-acid salt of formula (VI), or a polysulfide-acid salt of formula (VII):
Figure BDA0002082597390000091
wherein in formula (IV), R 4 Independently is tert-butyl or tert-pentyl, R 5 Independently is OH, OLi or ONa, r is 0 or greater (e.g. 0 to 10) and the aromatic ring is optionally substituted at one or more other positions with a substituent other than hydrogen; in the formula (VI), R 6 Is a divalent organic moiety; in the formula (VII), R 7 Is a divalent organic moiety, each Z is independently C 1 -C 20 An organic moiety, li, na, K, mg, a quaternary ammonium or quaternary phosphonium, each M is independently Li, na, K, mg, a quaternary ammonium or quaternary phosphonium, and o and p are each independently an integer of 1 or greater. Examples of such organosulfur materials include those sold under the trade name Achima
Figure BDA0002082597390000093
Aromatic polysulfides sold (formula IV, R) 4 = tButyl or tert-amyl, R 5 = OH); and polysulfide acid salts corresponding to formulas VI and VII derived from mercaptoacids such as mercaptoacetic acid, mercaptopropionic acid, mercaptoethanesulfonic acid, mercaptopropanesulfonic acid, or from alkene-containing acids such as vinylsulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid.
In yet another embodiment, the organosulfur species is an organic polysulfide or organo-metal polysulfide that contains trithiocarbonate functional groups of formula (IX), an organic polysulfide or organo-metal polysulfide that contains dithiocarbonate functional groups of formula (X), or an organic polysulfide or organo-metal polysulfide that contains monothiocarbonate functional groups of formula (XI):
Figure BDA0002082597390000092
wherein Z is C 1 -C 20 An organic moiety, na, li, K, mg, quaternary ammonium, or quaternary phosphonium, and o and p are each independently integers of 1 or greater.
The liquid or gel electrolyte solution may additionally comprise a compound having the formula M-S n A bimetallic polythiol salt species of-M, wherein each M is independently Li, na, K, mg, quaternary ammonium, or quaternary phosphonium, and n is an integer of 1 or more. Thus, such materials do not contain any organic moieties, unlike the organosulfur materials described above.
The middle separator membrane element may serve as a separator between compartments within an electrochemical cell. One compartment may contain an electrolyte solution in contact with the cathode (the electrolyte solution in this compartment may be referred to as the catholyte solution). The other compartment may contain an electrolyte solution in contact with the anode (the electrolyte solution in this compartment may be referred to as the anolyte solution). The anolyte solution and the catholyte solution may be the same or different from each other. One or both of the anolyte and catholyte liquids may comprise one or more organosulfur species according to the invention. The intermediate membrane element may be arranged between the compartments in such a way as to allow ions to pass from the anolyte solution through the intermediate membrane element into the catholyte solution and vice versa, depending on whether the electrochemical cell is in a charging or discharging mode of operation.
In another embodiment of the invention, the intermediate membrane element comprises a porous polymer. The porous polymer may comprise, for example, polypropylene, polyethylene, or a fluoropolymer. The porous polymer can be functionalized using organosulfur species of the type described herein. The organosulfur species can be pendant to the backbone of the porous polymer, can be present in cross-linking moieties between the backbones of the individual polymer chains, and/or can be incorporated into the backbone of the porous backbone. Thus, the backbone of the porous polymer may comprise one or more-S-S n -a bond and/or-S n The linkage may be pendant to the polymer backbone. This is-S-S n Bonds may also be present in the cross-linking moiety.
Suitable solvents for use in electrochemical cells according to the invention include any basic (cation complexing) aprotic polar solvent known or commonly used in lithium-sulfur batteries, such as sulfolane, dimethyl sulfoxide, dimethylacetamide, tetramethylurea, N-methylpyrrolidone, tetraethyl sulfonamide; 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, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl ethyl carbonate, etc.; and esters such as methyl acetate, ethyl acetate, propyl acetate, and γ -butyrolactone. The electrolyte may comprise a single one of these solvents or a mixture of these solvents. Any polar aprotic polymer known in the art of battery technology may also be used. The electrolyte solution may include a polymer material, and may be in the form of a gel. Suitable polymers for the electrolyte solution may include, for example, polyethylene oxide, polyethersulfone, polyvinyl alcohol, or polyimide. The electrolyte solution may be in the form of a gel, which may be a three-dimensional network comprising a liquid and a binder component. The liquid may be a monomer solvent entrained in a polymer, such as a crosslinked polymer.
One or more conducting salts are present in the electrolyte solution in combination with the non-aqueous polar aprotic solvent and/or the polymer. Conductive salts well known in the battery art include, for example, (CF) 3 SO 2 ) 2 N - 、CF 3 SO 3 - 、CH 3 SO 3 - 、ClO 4 - 、PF 6 - 、AsF 6 - Lithium salts of nitrates, halogens, and the like. Salts of sodium and other alkali metals and mixtures thereof may also be used.
The anode active material may include an alkali metal (e.g., lithium, sodium, potassium) and/or magnesium or another active material or composition. Particularly preferred anode active materials include metallic lithium, lithium alloys, metallic sodium, sodium alloys, alkali metals or alloys thereof, metal powders, alloys of lithium with aluminum, magnesium, silicon and/or tin, alkali metal-carbon and alkali metal-graphite intercalation materials, compounds capable of reversible oxidation and reduction with alkali metal ions, and mixtures thereof. The metal or metal alloy (e.g., lithium metal) may also be contained within the cell in the form of a single film or multiple films optionally separated by a ceramic material. Suitable ceramic materials include, for example, silica, alumina, or lithium-containing glass materials, such as lithium phosphate, lithium aluminate, lithium silicate, lithium phospho-oxynitride, lithium tantalum oxide, lithium aluminosilicate, lithium titanium oxide, lithium silicosulfide, lithium germanosulfide, lithium aluminosulfide, lithium borosulfide, lithium phosphosulfide, and mixtures thereof.
The anode may have any suitable form, such as a foil type, composite type, or other type of current collector.
In one embodiment of the invention, the anode is treated with at least one organosulfur species. This treatment may be carried out by contacting the anode surface with the at least one organosulfur species. For example, in such a contacting step, the organosulfur species can be in the form of a solution. Any solvent or combination of solvents suitable for organosulfur species can be used to form such a solution. For example, the solvent may be any aprotic polar solvent previously described. In one embodiment, the anode is treated with the organosulfur species, such as by spraying a solution of the organosulfur species onto the anode or dipping the anode into a solution of the organosulfur species, prior to assembly of the electrochemical cell. In another embodiment, the organosulfur species is incorporated as a component into an electrolyte solution for an electrochemical cell, wherein the electrolyte solution containing the organosulfur species is in contact with an anode when the electrochemical cell is assembled.
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 organosulfur species can be deposited on the surface of the anode.
The cathode includes elemental sulfur, elemental selenium, or a mixture of elemental chalcogens. In one embodiment, the cathode additionally comprises one or more of those organosulfur species described in detail previously herein. The cathode may additionally and/or alternatively comprise a binder and/or a conductive additive. Suitable binders include polymers such as polyvinyl alcohol, polyacrylonitrile, polyvinylidene fluoride (PVDF), polyvinyl fluoride, polytetrafluoroethylene (PTFE), copolymers of tetrafluoroethylene and hexafluoropropylene, copolymers of vinylidene fluoride and tetrafluoroethylene, ethylene-propylene-diene monomer rubber (EPDM), polyvinyl chloride (PVC). For example, the conductive additive may be a conductive carbon, such as graphite, graphene, carbon fiber, carbon nanotubes, carbon black, or soot (e.g., lamp or furnace ash). The cathode may be present in a battery or electrochemical cell that incorporates a current collector, such as any known in the battery or electrochemical cell art. For example, the cathode may be coated on the surface of a metal current collector.
Various aspects of the invention include:
1. a battery, comprising:
a) An anode comprising an anode active material for providing ions, the anode active material comprising sodium, comprising lithium, or an alloy or composite comprising at least one of sodium and lithium with at least one other metal;
b) A cathode comprising a cathode active material comprising elemental sulfur, elemental selenium, or a mixture of elemental chalcogens; and
c) An intermediate membrane element disposed between the anode and the cathode and operative to isolate a liquid or gel electrolyte solution in contact with the anode and the cathode, the metal ions and their counterions moving between the anode and the cathode through the intermediate membrane element during charge and discharge cycles of the battery;
wherein the liquid or gel electrolyte solution comprises a non-aqueous polar aprotic solvent or polymer and a conductive salt, and satisfies at least one of conditions (i), (ii), (iii) and (iv):
(i) At least one of the liquid or gel electrolyte solutions additionally comprises at least one organosulfur species;
(ii) The cathode additionally comprises at least one organosulfur species;
(iii) The middle separator element comprises a functionalized porous polymer containing at least one organosulfur species;
(iv) The anode further comprises or has been treated with at least one organosulfur species;
wherein the organosulfur species comprises at least one organic moiety and at least one-S n -a bond, n being 0 or an integer greater than or equal to 1.
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.
3. The battery according to any one of aspects 1 and 2, wherein the organosulfur species contains one or more sulfur-containing functional groups selected from the group consisting of: dithioacetals, dithioketals, trithiocarbonates, thiosulfonates [ -S (O) 2 -S-]Thiosulfinate [ -S (O) -S-]Thiocarboxylate [ -C (O) -S-]Dithiocarboxylates [ -C (S) -S-]Thiophosphate, thiophosphonate, monothiocarbonate, dithiocarbonate and trithiocarbonate.
4. The battery according to any one of aspects 1-3, wherein the organosulfur species is selected from the group consisting of aromatic polysulfides, polyether-polysulfides, polysulfide-acid salts, and mixtures thereof.
5. The battery according to any one of aspects 1 to 5, wherein the organosulfur species is of the formula R 1 -S-S n -R 2 Of (3), wherein R is 1 And R 2 Independently represent C 1 -C 20 An 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 a metal, and N is an integer of 1 or more.
6. The battery according to any one of aspects 1 to 5, wherein the organosulfur species is of the formula R 1 Organic mercaptides of-S-M or of formula R 1 -S-S n Organic polythiolates of formula (I) -M, wherein R 1 Is C 1 -C 20 An organic moiety, which may be linear, branched or cyclic aliphatic or aromatic and 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.
7. The battery of any one of aspects 1-6, wherein the organosulfur species is a dithioacetal or dithioketal of formula (I) or (II), or a trithio-orthocarboxylate of formula (III):
Figure BDA0002082597390000141
wherein each R 3 Independently is H or C 1 -C 20 Organic moiety of the formula C 1 -C 20 The organic moiety may be linear, branched or cyclic aliphatic or aromatic and may optionally comprise one or more functional groups containing N, O, P, S, se, si, sn, halogens and/or metals, O, P and q are each independently integers of 1 or more, and each Z is independently: c 1 -C 20 An organic moiety, li, na, K, mg, a quaternary ammonium or quaternary phosphonium, the processThe organic moiety may be linear, branched or cyclic aliphatic or aromatic and may optionally comprise one or more functional groups containing N, O, P, S, se, si, sn, halogens and/or metals.
8. The battery according to any one of aspects 1-7, wherein the organosulfur species is an aromatic polysulfide of formula (IV), a polyether-polysulfide of formula (V), a polysulfide-acid salt of formula (VI), or a polysulfide-acid salt of formula (VII):
Figure BDA0002082597390000142
wherein in formula (IV), R 4 Independently is tert-butyl or tert-amyl, R 5 Independently is OH, OLi or ONa, r is 0 or greater and the aromatic ring is optionally substituted at one or more positions with a substituent other than hydrogen; in the formula (VI), R 6 Is a divalent organic moiety; in formula (VII), R 5 Is a divalent organic moiety, each Z is independently C 1 -C 20 An organic moiety, 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 integers of 1 or greater.
9. The battery of any one of aspects 1-8, wherein the organosulfur species is an organic polysulfide or organo-metal polysulfide comprising trithiocarbonate functional groups of formula (IX), an organic polysulfide or organo-metal polysulfide comprising dithiocarbonate functional groups of formula (X), or an organic polysulfide or organo-metal polysulfide comprising monothiocarbonate functional groups of formula (XI):
Figure BDA0002082597390000151
wherein Z is C 1 -C 20 An organic moiety, na, li, quaternary ammonium, or quaternary phosphonium, and o and p are each independently an integer of 1 or greater.
10. The battery according to any one of aspects 1 to 9, wherein the liquid or gel electrolyte solution further comprises a polymer having a chemical formula of M-S n A bimetallic polythiol salt species of-M, wherein each M is independently Li, na, K, mg, quaternary ammonium, or quaternary phosphonium, and n is an integer of 1 or more.
11. The battery according to any one of aspects 1-10, wherein the cathode further comprises at least one conductive additive and/or at least one binder.
12. The battery of any of aspects 1-11, wherein the organosulfur species is pendant to the backbone chain of the functionalized porous polymer.
13. The battery of any of aspects 1-12, wherein the organosulfur species is crosslinked into or constitutes a portion of the backbone chain of the functionalized porous polymer.
14. The battery of any one of aspects 1-13, wherein the organic moiety contains at least two carbon atoms.
15. The battery of any of aspects 1-14, wherein the intermediate porous separator separates the battery to provide an anolyte liquid portion associated with the anode and a catholyte liquid portion associated with the cathode, and wherein the organosulfur species is present in at least one of the anolyte liquid portion and the catholyte liquid portion.
16. The battery according to any one of aspects 1 to 15, wherein the non-aqueous polar aprotic solvent or polymer comprises a solvent selected from the group consisting of ether, carbonyl, ester, carbonate, amino, amido, thio [ -S-]Sulfinyl [ -S (O) -]Or sulfonyl [ -SO ] 2 -]One or more functional groups of (a).
17. The battery according to any one of aspects 1-16, wherein the conductive salt corresponds to formula MX, wherein M is Li, na, or a 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.
18. The battery of any of aspects 1-17, wherein the organic moiety is an oligomeric or polymeric organic moiety and the organosulfur species comprises at least one-S-linkage pendant to a backbone of the oligomeric or polymeric organic moiety.
19. The battery of any of aspects 1-18, wherein the organic moiety is an oligomeric or polymeric organic moiety and the organosulfur species comprises at least one-S-linkage incorporated into the backbone of the oligomeric or polymeric organic moiety.
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 comprising at least one organic moiety and at least one-S n -a bond, wherein n is 0 or an integer greater than or equal to 1.
21. A cathode comprising a) elemental sulfur, elemental selenium, or a mixture of elemental chalcogens, b) at least one conductive additive, and c) at least one organosulfur species comprising at least one organic moiety and at least one-S n -a bond, wherein n is 0 or an integer greater than or equal to 1.
22. The cathode of aspect 21 in combination with a current collector.
23. The cathode according to any one of aspects 21 and 22, wherein the at least one conductive additive comprises at least one of graphite, carbon nanotubes, carbon nanofibers, graphene, carbon black, and soot.
24. The cathode of any one 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 composite of sodium, lithium, potassium or magnesium with at least one other metal, for providing ions, wherein said anode additionally comprises or has been treated with at least one organosulfur species comprising at least one organic moiety and at least one-S n -a bond, wherein n is 0 or an integer greater than or equal to 1.
In this specification, various embodiments have been described in a manner that enables them to be clearly and concisely written, but it should be understood that it is intended that the various embodiments can be combined in various ways without departing from the invention. For example, it should be understood that all of the preferred features described herein apply to the various aspects of the invention described herein.
In some embodiments, the invention described herein can be construed as excluding any element or method step that does not materially affect the basic novel characteristics of the composition or method. Furthermore, in some embodiments, the invention may be construed as excluding any element or method step not specified herein.
Examples
Cathode manufacture, cell preparation, and cell testing
Example 1
Comprising 70% by weight of sublimed elemental sulphur powder, 20% by weight of polyethylene oxide (PEO, molecular weight 4X 10) 6 ) 10% by weight of carbon black [ Super%
Figure BDA0002082597390000171
Conductive, alpha Aisha (Alfa Aesar)]The positive electrode of (a) is prepared by the following steps:
the mixture of these components was mechanically milled in N-methyl-2-pyrrolidone (NMP) in a planetary mill. Acetonitrile was added to dilute the mixture. The resulting suspension was applied to an automatic film coater [ Mathis)]Coated onto aluminum foil (76 μm thick). The coating was dried in a vacuum oven at 50 ℃ for 18 hours. The resulting coating contained 3.10mg/cm 2 The cathode mixture of (1).
Example 2
A positive electrode containing lithium n-dodecylmercaptide (10 wt% sulfur) was prepared according to the procedure described in example 1. The resulting coating contained 3.4mg of sulfur/cm 2 。
Example 3
The positive electrode from example 2 was used in a PTFE wiggle (Swaglok) cell having two stainless steel rods or coin cell modules made of stainless steel (CR 2032). The cell units were assembled in an argon filled glove box [ braun (MBraun) ] as follows: the cathode was placed on the bottom can, followed by the separator. The electrolyte solution is then added to the separator. A lithium electrode is placed on the separator. On top of the lithium electrode a spacer and a spring are placed. The cell core was sealed with stainless steel bars or with a crimping machine.
Example 4
A charge-discharge cycle test was performed at a current of 0.1mA according to the procedure described in example 3, for a cell having the composition of the cathode (diameter 7/16 ") from example 2, a solution of 20 μ L of 0.5M LiTFSI in Tetraglyme (TEGDME): 1, 3-Dioxolane (DOL) =1, separator, and lithium electrode (thickness 0.38mm, diameter 7/16"). The test was performed using a domer potentiometer (Gamry) with cutoff voltages of 1.5V and 3.2V at room temperature. The discharge cycle curve is shown in fig. 1.
Synthesis of lithium alkyl mercaptides
Example 5 Synthesis of lithium n-dodecyl mercaptan Using hexyl lithium
To a solution of n-dodecyl mercaptan (9.98g, 1 equiv) in hexane (100 mL) was added n-hexyllithium (33 wt% in hexane, 1.1 equiv) dropwise at-30 ℃ to maintain the temperature of the mixture below-20 ℃. The solvent was removed under reduced pressure to give a white solid in a certain yield.
Example 6 Synthesis of lithium n-dodecyl mercaptan from lithium hydroxide
A solution of a mixture of n-dodecylmercaptan (2.0 g,1 equiv.) and lithium hydroxide monohydrate (0.41g, 1 equiv.) in acetonitrile (8 mL) was heated to 75 deg.C and stirred at 75 deg.C for 16 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 ℃ overnight. Lithium n-dodecylmercaptide was obtained as a white solid in 93.5% yield (1.93 g).
Example 7 Synthesis of lithium n-dodecylmercaptan Using hexyl lithium
Figure BDA0002082597390000191
The 3, 6-dioxaoctane-1, 8-dithiol dilithium salt was synthesized as a white solid from dithiol in a certain amount of yield by the procedure described in example 6.
Synthesis of lithium alkyl polythiols
EXAMPLE 8 Synthesis of lithium n-dodecyl polythiol Using lithium hydroxide
Figure BDA0002082597390000192
To a nitrogen degassed solution of n-dodecyl mercaptan (2.00g, 1 eq.) in 1, 3-dioxolane (25 ml) was added lithium hydroxide monohydrate (0.41g, 1 eq.) and sulfur (1.27g, 4 eq.). The mixture was stirred at room temperature under nitrogen for 30 minutes to give a dark red solution of lithium n-dodecyl polythiol dissolved in 1, 3-dioxolane. Complete conversion of mercaptans to lithium n-dodecylpolythiol 13 C-NMR and LCMS.
Example 9 Synthesis of lithium 3, 6-dioxaoctane-1, 8-polythiol Using lithium hydroxide and Sulfur
Figure BDA0002082597390000193
A deep red solution of lithium 3, 6-dioxaoctane-1, 8-polythiol in 1, 3-dioxolane according to the procedure described in example 8 was obtained from the reaction of 3, 6-dioxaoctane-1, 8-dithiol (0.72g, 1 eq.), lithium hydroxide monohydrate (0.33g, 2 eq.), and sulfur (1.02g, 8 eq.) in 1, 3-dioxolane (10 mL).
EXAMPLE 10 Synthesis of lithium n-dodecyl polythiol from lithium alkyl mercaptide
To a nitrogen degassed slurry of lithium n-dodecylmercaptide (0.21g, 1 eq) dissolved in 1, 3-dioxolane (5 mL) was added sulfur (0.13g, 4 eq). The mixture was stirred at room temperature under nitrogen for 16 hours. Insoluble solids were removed by filtration. The dark red filtrate contained 63% lithium n-dodecyl polythiol and 37% of a mixture of bis (n-dodecyl) polysulfide as determined by LCMS.
EXAMPLE 11 Synthesis of lithium n-dodecyl polythiol Using lithium Metal and Sulfur
To a nitrogen degassed solution of n-dodecyl mercaptan (2.23g, 1 eq) in 1, 3-dioxolane (25 mL) was added sulfur (1.41g, 4 eq.) and lithium (76.5 mg). The mixture was heated to 60 ℃ and stirred under nitrogen at 60 ℃ for 1 hour. A deep red solution of lithium n-dodecyl polythiol dissolved in 1, 3-dioxolane was obtained. Complete conversion of n-dodecylmercaptan from 13 C-NMR confirmed.
Example 12 Synthesis of lithium 3, 6-dioxaoctane-1, 8-polythiol from lithium Metal and Sulfur
Following the procedure described in example 11, 3, 6-dioxaoctane-1, 8-dithiol (1.97g, 1 equiv.), lithium metal (0.15g, 2 equiv.), and sulfur (2.77g, 8 equiv.) were reacted in 1, 3-dioxolane (11 mL) to give a deep red solution of lithium 3, 6-dioxaoctane-1, 8-polythiol in 1, 3-dioxolane. Complete conversion of the starting dithiol from 13 C-NMR confirmed.
Example 13 dissolution of Li by addition of lithium n-dodecyl polythiol 2 S
To determine the solubility of lithium sulfide in an electrolyte solution containing lithium n-dodecyl polythiol, a saturated solution of lithium sulfide was prepared as follows:
A0.4M solution of lithium n-dodecyl polythiol in 1, 3-dioxolane was prepared by the procedure described in example 10. The solution was then diluted to 0.2M with tetraglyme and then added to a 1M solution of LiTFSI in 1. Lithium sulfide was added to the resulting solution until a saturated mixture was obtained. The mixture was then filtered and washed with ICP-MS [ Agilent (Agilent) 7700X ICP-MS]The filtrate was analyzed for dissolved lithium. The solubility of lithium sulfide was calculated based on the level of lithium. In a solution of 0.5M LiTFSI and 0.1M lithium n-dodecyl polythiolate in 1,1 tetraglyme 1, 3-dioxolane, the solubility of lithium sulfide was determined to be 0.33% by weight. In contrast, the solubility of lithium sulfide in 0.5M LiTFSI was only 0.13% by weight in the absence of lithium n-dodecyl polythiolate. This clearly shows that Li when the organosulfur of the invention is present 2 The solubility of S in the electrolyte matrix of the cell is improved.
Example 14 preparation of a Battery containing an Anode treated with an organosulfur substance
This example illustrates the preparation of a cell whose anode has been contacted with an electrolyte solution 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 of 75. The slurry was then drawn down onto carbon-coated aluminum foil and air-dried to yield about 0.5mg/cm 2 Sulfur loading of (d). The resulting cathode was then assembled into CR2032 coin cells in an argon-filled glove box, along with a polypropylene separator and a lithium foil anode. The electrolyte solutions used each contained 0.38M bis (trifluoromethane) sulfonamide and 0.38M lithium nitrate in a 1. An electrolyte solution (according to the invention) additionally contains 100mM 3, 6-dioxaoctane-1, 8-dithioldithium salt (LiS-C) 2 H 4 -O-C 2 H 4 -O-C 2 H 4 SLi) (thus the lithium foil anode was in contact with 3, 6-dioxaoctane-1, 8-dithiol dilithium salt), while the other electrolyte solution (control) did not contain any organosulfur species. Battery cycling was performed in a 1.7-2.6V battery test. At C/2 relative to active sulfur, 40. The observed results are shown in fig. 2.

Claims (18)

1. A battery, comprising:
a) An anode comprising an anode active material for providing ions, the anode active material comprising sodium, comprising lithium, or an alloy or composite comprising at least one of sodium and lithium and at least one other metal;
b) A cathode comprising a cathode active material comprising elemental sulfur, comprising elemental selenium, or comprising a mixture thereof; and
c) An intermediate membrane element disposed between the anode and the cathode and operative to isolate a liquid or gel electrolyte solution in contact with the anode and the cathode, metal ions and counterions thereof moving between the anode and the cathode through the intermediate membrane element during charge and discharge cycles of the battery;
wherein the liquid or gel electrolyte solution comprises a non-aqueous polar aprotic solvent or polymer and a conductive salt, and satisfies the following conditions:
the anode further comprises or has been treated with at least one organosulfur species;
wherein the organosulfur species comprises at least one organic moiety and at least one-S n A bond, n is 0 or an integer greater than or equal to 1,
wherein the organosulfur species is of the formula R 1 -S-S n -R 2 Of an organic polysulfide of (1), wherein R 1 And R 2 Independently represent C 1 -C 20 An organic moiety that is linear, branched or cyclic aliphatic or aromatic and optionally comprises 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; or the organosulfur species is of the formula R 1 Organic mercaptides of-S-M or of formula R 1 -S-S n Organic polythiolates of formula (I) -M, wherein R 1 Is C 1 -C 20 An organic moiety that is linear, branched or cyclic aliphatic or aromatic and optionally comprises 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. The battery of claim 1, wherein the organosulfur species is selected from the group consisting of organic polysulfides, organic thiolates, and organic polythiolates, and mixtures thereof.
3. The battery of claim 1, 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-]Thiocarboxylates [ -C (O) -S-]Dithiocarboxylates [ -C (S) -S-]Thiophosphates, thiophosphonates, monothiocarbonates, dithiocarbonates, and trithiocarbonates.
4. The battery of claim 1, wherein the organosulfur species is selected from the group consisting of aromatic polysulfides, polyether-polysulfides, polysulfide-acid salts, and mixtures thereof.
5. The battery of claim 1, wherein the organosulfur species is a dithioacetal or dithioketal of formula (I) or (II), or a trithio-orthocarboxylate of formula (III):
Figure FDA0003808562380000021
wherein each R 3 Independently is H or C 1 -C 20 Organic moiety of the formula C 1 -C 20 The organic moiety is linear, branched or cyclic aliphatic or aromatic and optionally comprises one or more functional groups containing N, O, P, S, se, si, sn, halogens and/or metals, O, P and q are each independently integers of 1 or more, and each Z is independently: c 1 -C 20 An organic moiety, li, na, K, mg, quaternary ammonium or quaternary phosphonium, the organic moiety being linear, branched or cyclic aliphatic or aromatic and optionally comprising one or more functional groups containing N, O, P, S, se, si, sn, halogen and/or metal.
6. The battery of claim 1, wherein the organosulfur species is an aromatic polysulfide of formula (IV), a polyether-polysulfide of formula (V), a polysulfide-acid salt of formula (VI), or a polysulfide-acid salt of formula (VII):
Figure FDA0003808562380000022
wherein in formula (IV), R 4 Independently is tert-butyl or tert-amyl, R 5 Independently is OH, OLi or ONa, r is 0 or greater and the aromatic ring is optionally substituted at one or more positions with a substituent other than hydrogen; in the formula (VI), R 6 Is a divalent organic moiety; in formula (VII), R 5 Is a divalent organic moiety, each Z is independently C 1 -C 20 An organic moiety, 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 greater.
7. The battery of claim 1, wherein the organosulfur species is an organic polysulfide or organo-metal polysulfide comprising trithiocarbonate functional groups of formula (IX), an organic polysulfide or organo-metal polysulfide comprising dithiocarbonate functional groups of formula (X), or an organic polysulfide or organo-metal polysulfide comprising monothiocarbonate functional groups of formula (XI):
Figure FDA0003808562380000031
wherein Z is C 1 -C 20 An organic moiety, na, li, quaternary ammonium, or quaternary phosphonium, and o and p are each independently an integer of 1 or greater.
8. The battery of claim 1, wherein the liquid or gel electrolyte solution further comprises a polymer having the formula M-S n A bimetallic polythiol salt species of-M, wherein each M is independently Li, na, K, mg, quaternary ammonium, or quaternary phosphonium, and n is an integer of 1 or more.
9. The battery according to claim 1, wherein the cathode additionally comprises at least one conductive additive and/or at least one binder.
10. The battery of claim 1, wherein the organosulfur species is pendant to the backbone of the functionalized porous polymer.
11. The battery of claim 1, wherein the organosulfur species is crosslinked into or constitutes a portion of the backbone of the functionalized porous polymer.
12. The battery of claim 1, wherein the organic moiety contains at least two carbon atoms.
13. The battery of claim 1, wherein the intermediate porous separator separates the battery to provide an anolyte portion associated with the anode and a catholyte portion associated with the cathode, and wherein the organosulfur species is present in at least one of the anolyte portion and the catholyte portion.
14. The cell according to claim 1, wherein the non-aqueous polar aprotic solvent or polymer comprises a solvent selected from the group consisting of ether, carbonyl, ester, carbonate, amino, amido, thio [ -S-]Sulfinyl [ -S (O) -]Or sulfonyl [ -SO 2 -]One or more functional groups.
15. The battery according to claim 1, wherein the conductive salt corresponds to the formula MX, wherein M is Li, na, or a 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.
16. The battery of claim 1, wherein the organic moiety is an oligomeric or polymeric organic moiety and the organosulfur species comprises at least one-S-linkage pendant to the backbone of the oligomeric or polymeric organic moiety.
17. The battery of claim 1, wherein the organic moiety is an oligomeric or polymeric organic moiety and the organosulfur species comprises at least one-S-bond incorporated into the backbone of the oligomeric or polymeric organic moiety.
18. An anode comprising an anode active material comprising sodium, lithium, potassium or magnesium, or an alloy or composite of at least one of sodium, lithium, potassium and magnesium with at least one other metal, for providing ions, wherein said anode additionally comprises or has been treated with at least one organosulfur species comprising at least one organic moiety and at least one-S n -a bond, wherein n is 0 or an integer greater than or equal to 1.
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