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    • 专利摘要:
    battery based on organo-sulfur species. Metal-sulfur batteries, such as lithium-sulfur batteries, are prepared using one or more species of organo-sulfur such as organic polysulphides and organic polythiolates as part of the liquid or gel electrolyte solution, as part of the cathode, and / or as part of a functionalized porous polymer providing an intermediate separating element.
    公开号:BR112014025312B1
    申请号:R112014025312-9
    申请日:2013-04-09
    公开日:2021-04-06
    发明作者:Gary S. Smith；Lijuan Wang
    申请人:Arkema Inc.；
    IPC主号:
    专利说明:

    [0001] [001] The invention relates to batteries having an anode based on sodium, lithium or its mixture or alloy or composite of sodium and / or lithium with one or more other metals and a cathode based on elemental sulfur, selenium, or mixture of elemental chalcogens, the anode and cathode being separated by a separating element with a liquid or gel electrolyte solution of a conductive salt in a non-aqueous polar aprotic polymer or solvent in contact with the electrodes. BACKGROUND OF THE INVENTION
    [0002] [002] Electrochemical batteries are a primary means of storage and distribution of electrical energy. Due to increasing demand for energy for electronic, transport and network storage applications, the need for batteries with increasing storage and power distribution capacity will continue for a long time to come.
    [0003] [003] Due to their light weight and high energy storage capacity compared to other types of batteries, lithium ion batteries have been widely used since the early 1990s for portable electronic applications. However, current Li-ion battery technology does not meet the high power and energy requirements for large applications such as grid storage or electric vehicles with driving ranges that are competitive with vehicles powered by internal combustion engines. As such, extensive efforts in the scientific and technical communities continue to identify batteries with a higher energy density and capacity.
    [0004] [004] Electrochemical sodium-sulfur and lithium-sulfur electrochemical cells offer even higher theoretical energy capacity than Li ion cells and thus have continued to arouse interest as "next generation" battery systems. The electrochemical conversion of elemental sulfur to monomeric sulfides (S2-) offers a theoretical capacity of 1675 mAh / g compared to less than 300 mAh / g for Li ion cells.
    [0005] [005] Sodium-sulfur batteries have been developed and launched as commercial systems. Unfortunately, the sodium-sulfur cell typically requires high temperatures (above 300 ° C) to be functional, and thus is only suitable for large stationary applications.
    [0006] [006] Electrochemical lithium-sulfur cells, initially proposed in the late 1950s and 1960s, are only now being developed as commercial battery systems. These cells offer theoretical specific energy densities above 2500 Wh / kg (2800 Wh / L) vs. 624 Wh / g for lithium ion. The specific energy densities demonstrated for Li-S cells are in the range of 250-350 Wh / kg, compared to 100 Wh / g for Li ion cells, the lowest values being the result of specific characteristics of the electrochemical processes for these systems during loading and unloading. Given that the practical specific energies of lithium batteries are typically 25-35% of the theoretical value, the optimal practical specific energy for a Li-S system would be around 780 Wh / g (30% of theory). [V.S. Kolosnitsyn, E. Karaseva, US Patent Application 2008/0100624 A1].
    [0007] [007] Lithium-sulfur chemistry offers a number of technical challenges that have hampered the development of these electrochemical cells, particularly poor discharge-charge cycling. Nevertheless, due to the inherent low weight, low cost, high power capacity of the lithium-sulfur cell, there is great interest in improving the performance of the lithium-sulfur system and extensive work has been carried out in the last 20 years by many researchers in around the world to address these issues [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, 147882; and references there.]
    [0008] • Um ânodo consistindo em metal de lítio, liga de lítio ou materiais compósitos contendo lítio. • Um separador não reativo mas poroso entre o ânodo e o cátodo (frequentemente polipropileno ou -alumina). A presença deste separador resulta em compartimentos de anólito e católito separados. • Um cátodo poroso transportando enxofre que incorpora um ligante (frequentemente difluoreto de polivinilideno) e um material intensificador da condutividade (frequentemente grafite, grafite mesoporosa, nanotubos de carbono multiparedes, grafeno). • Um eletrólito consistindo em um solvente aprótico polar e um ou mais sais condutores de Li [(CF3SO2)2N , CF3SO3 , CH3SO3 , ClO4 , PF6 , AsF6 , halogênios, etc.]. Os solventes usados em estas células têm incluído solventes polares apróticos básicos (complexantes com cátions) tais como sulfolano, sulfóxido de dimetila, dimetilacetamida, ureia de tetrametila, pirrolidinona de Ν-metila, sulfamida de tetraetila, tetraidrofurano, metil-THF, 1,3-dioxolano, diglima, e tetraglima. Solventes com polaridade mais baixa não são adequados devido a fraca condutividade e fraca capacidade de solvatar espécies de Li+, e os solventes próticos podem reagir com metal de Li. Em versões de estado sólido da célula de lítio-enxofre, os solventes líquidos são substituídos por um material polimérico tal como óxido de polietileno. • Coletores correntes e materiais de cobertura apropriados. [008] A cell design for a lithium-sulfur system typically includes: • An anode consisting of lithium metal, lithium alloy or composite materials containing lithium. • A non-reactive but porous separator between the anode and the cathode (often polypropylene or -alumina). The presence of this separator results in separate anolyte and catholyte compartments. • A porous cathode carrying sulfur that incorporates a binder (often polyvinylidene difluoride) and a conductivity enhancing material (often graphite, mesoporous graphite, multi-walled carbon nanotubes, graphene). • An electrolyte consisting of a polar aprotic solvent and one or more conductive salts of Li [(CF3SO2) 2N, CF3SO3, CH3SO3, ClO4, PF6, AsF6, halogens, etc.]. The solvents used in these cells have included basic aprotic polar solvents (complexing with cations) such as sulfolane, dimethyl sulfoxide, dimethylacetamide, tetramethyl urea, Ν-methyl pyrrolidinone, tetraethyl sulfamide, tetrahydrofuran, methyl-THF, 1,3 -dioxolane, diglyme, and tetraglyme. Lower polarity solvents are not suitable due to poor conductivity and weak capacity to solvate Li + species, and protic solvents can react with Li metal. In solid-state versions of the lithium-sulfur cell, liquid solvents are replaced with a polymeric material such as polyethylene oxide. • Current collectors and appropriate roofing materials.
    [0009] [009] Compositions and applications of organic polysulfides and organic polythiolates for use in metal-sulfur batteries, particularly lithium-sulfur batteries, are provided by the present invention. The species of organic polysulfide and organopolitiolate act to improve the performance of such electrochemical cells during repeated cycles of discharge and loading.
    [0010] [0010] The present invention thus relates to chemical sources of energy comprising a cell or battery with one or more positive electrodes (cathodes), one or more negative electrodes (anodes) and an electrolyte medium, in which the operational chemistry involves reducing the sulfur or polysulfide species and oxidation of reactive metal species. The negative electrode comprises a reactive metal such as lithium, sodium, potassium or alloys / composites of these metals with other materials. The positive electrode comprises sulfur, organic polysulfide species, and / or salts of organic metal polysulfides, and matrices containing these species. Electrolyte arrays comprise mixtures of organic solvents or polymers, species of inorganic or organic polysulfide, carriers for the ionic form of the active metal, and other components designed to optimize electrochemical performance.
    [0011] [0011] Specifically, this invention relates to the use of organic polysulfides, and their organothiolate or lithium organopolitiolate analogs (or sodium, quaternary ammonia or quaternary phosphonium), as components in the cathode and electrolyte matrices. Said organo-sulfur species chemically combine with sulfur and anionic mono- or polysulfide species to form organopolitiolate species that have increased affinity for the non-polar sulfur components of the positive cathode and catholyte phase.
    [0012] a) um ânodo compreendendo um material ativo do ânodo compreendendo sódio, lítio ou uma liga ou compósito de pelo menos um de sódio ou lítio com pelo menos um outro metal para proporcionar íons; b) um cátodo compreendendo um material ativo do cátodo compreendendo enxofre elementar, selênio elementar ou uma mistura de calcogênios elementares; e c) um elemento separador intermediário posicionado entre o ânodo e o cátodo atuando para separar soluções eletrólitas líquidas ou em gel em contato com o ânodo e o cátodo, através do qual os íons de metal e seus contraíons se movem entre o ânodo e o cátodo durante os ciclos de carga e descarga da bateria; em que as soluções eletrólitas líquidas ou em gel compreendem um solvente ou polímero aprótico polar não aquoso e um sal condutor e pelo menos uma das condições (i), (ii) ou (iii) é cumprida: (i) pelo menos uma das soluções eletrólitas líquidas ou em gel compreende adicionalmente pelo menos uma espécie de organoenxofre; (ii) o cátodo é adicionalmente compreendido por pelo menos uma espécie de organoenxofre; (iii) o elemento separador intermediário compreende um polímero poroso funcionalizado contendo pelo menos uma espécie de organoenxofre; em que a espécie de organoenxofre compreende pelo menos uma fração orgânica e pelo menos uma ligação -S-Sn-, com n sendo um inteiro de 1 ou mais.[0012] One aspect of the invention provides a battery, the battery comprising: a) an anode comprising an active material of the anode comprising sodium, lithium or an alloy or composite of at least one of sodium or lithium with at least one other metal to provide ions; b) a cathode comprising an active cathode material comprising elemental sulfur, elemental selenium or a mixture of elementary chalcogens; and c) an intermediate separating element positioned between the anode and the cathode acting to separate liquid or gel electrolyte solutions in contact with the anode and the cathode, through which the metal ions and their counterions move between the anode and the cathode during battery charging and discharging cycles; wherein the liquid or gel electrolyte solutions comprise a non-aqueous polar aprotic polymer or solvent and a conductive salt and at least one of the conditions (i), (ii) or (iii) is met: (i) at least one of the liquid or gel electrolyte solutions additionally comprises at least one type of organo-sulfur; (ii) the cathode is additionally comprised of at least one species of organo-sulfur; (iii) the intermediate separator element comprises a functionalized porous polymer containing at least one species of organo-sulfur; wherein the organo-sulfur species comprises at least one organic fraction and at least one -S-Sn- bond, with n being an integer of 1 or more.
    [0013] [0013] In one embodiment, only one of conditions (i), (ii) or (iii) is met. In another embodiment, all three conditions are met. In yet another embodiment, only two of the conditions are met, eg, (i) and (ii), (i) and (iii), or (ii) and (iii).
    [0014] [0014] In another aspect, the invention provides an electrolyte comprising at least one non-aqueous polar aprotic polymer or solvent, at least one conductive salt, and at least one species of organo-sulfur comprising at least one organic fraction and at least one bond - S-Sn- where n is an integer of 1 or more.
    [0015] [0015] Another aspect of the invention provides a cathode comprising a) elemental sulfur, elemental selenium or a mixture of elementary chalcogens, b) at least one electrically conductive additive, c) and at least one species of organo sulfur comprising at least an organic fraction and at least one -S-Sn- bond, n being an integer of 1 or more.
    [0016] [0016] The organo-sulfur species, for example, can be selected from the group consisting of organic polysulfides and / or organic metal polythiolates. In certain embodiments of the invention, the organo-sulfur species contains one or more sulfur-containing functional groups selected from the group consisting of dithioacetal, dithiocetal, trithio-orthocarbonate, thiosulfonate [-S (O) 2-S-], thiosulfinate [-S (O) -S-], thiocarboxylate [-C (O) -S-], dithiocarboxylate [-C (S) -S-], thiophosphate, thiophosphonate, monothiocarbonate, dithiocarbonate, and tritiocarbonate. In other embodiments, the organo-sulfur species can be selected from the group consisting of aromatic polysulfides, polyether polysulfides, acid polysulfide salts and mixtures thereof. BRIEF DESCRIPTION OF THE DRAWINGS
    [0017] [0017] Figure 1 shows discharge profiles of lithium-sulfur bacteria with n-C12H25SLi added to the cathode for repeated charge / discharge cycles 3 to 63. DETAILED DESCRIPTION OF THE INVENTION
    [0018] [0018] An electroactive material that was manufactured in a structure for use in a bacterium is referred to as an electrode. Of a pair of electrodes used in a battery, which serves as a chemical source of electrical energy, the electrode on the side having a higher electrochemical potential is referred to as the positive electrode, or the cathode, while the electrode on the side having an electrochemical potential the lower one is referred to as the negative electrode, or the anode. As used here, conventional battery nomenclature is used in which the terms "cathode" or "positive electrode" and "anode" or "negative electrode" refer to the electrochemical functions of the electrodes during cell discharge to provide electrical energy. During the charge portion of the cycle, the actual electrochemical functions of an electrode are reversed versus those that occur during discharge, but the designation of the respective electrodes remains the same as for discharge.
    [0019] [0019] Electrochemical cells are commonly combined in series, the aggregate of such cells being referred to as a battery. Based on the operating chemistry of the cells, primary batteries are designed for a single discharge to provide power to an external device. Secondary batteries are rechargeable, using electricity from an external source, and thus offer extended use over multiple discharge and charge cycles.
    [0020] [0020] An electrochemically active material used in the cathode or positive electrode is hereinafter referred to as an active cathode material. An electrochemically active material used in the negative anode or electrode is hereinafter referred to as an active anode material. Multicomponent compositions having electrochemical activity and comprising an electrochemically active and additive material or optional electrically conductive binder, as well as other optional additives, are referred to hereinafter as electrode compositions. A battery comprising a cathode with the active material of the cathode in an oxidized state and an anode with the active material of the anode in a reduced state is referred to as being in a charged state. Accordingly, a battery comprising a cathode with the active material of the cathode in a reduced state, and an anode with the active material of the anode in an oxidized state is referred to as being in a discharged state.
    [0021] [0021] Without wishing to be limited by theory, the following are certain possible advantages or features of the present invention. The organo-sulfur species can partition into the sulfur-rich catholyte phase. Chemical exchange reactions between dianionic sulfides or polysulfides (eg Li2Sx, x = 1, 2, 3 ...) and organopolysulfides or organopolitiolates (eg, R-Sx-R 'or R-Sx -Li, R and R '= organic fractions), together with extrusion / reinsertion chemicals common to polysulfides and polythiolates, favor the minimization of the amount of dianionic polysulfides in the catholyte and favor the redeposition of sulfur and sulfur-containing species in the cathode. The liquid removal of the dianionic polysulfides would reduce the viscosity of the electrolyte and thus minimize the detrimental effects of the high viscosity on the conductivity of the electrolyte. The organo-sulfur species can also increase the dissolution, and thus removal, of insoluble low-grade lithium sulfide species (particularly Li2S and Li2S2) in both the catholyte and anolyte phases, thus minimizing the loss of reactive lithium species after cycles repeated loading / unloading. The performance of organo-sulfur species can be "tuned" by selecting organic functionality. For example, alkyl or lower alkyl groups with more polar functionality would partition more for the anolyte phase, while longer or less polar analogues would partition more for the catholyte phase. Adjusting the relative ratios of long / non-polar and short / polar organic species would provide a means of controlling the partition of sulfur-containing species into the cathode / catholyte. Furthermore, since the presence of some amount of polysulfide or polyolate in the anolyte is advantageous as a means of controlling the growth of lithium dendrites at the anode during loading, the selection of appropriate organic fractions and their relative ratios would provide better control of dendrite growth.
    [0022] [0022] The organo-sulfur species useful in the present invention comprise at least one organic fraction and at least one -S-Sn- bond, where n is an integer of at least 1. In one embodiment, the organo-sulfur species comprises two organic fractions per molecule (which may be the same or different from each other) that are connected by a -S-Sn- (polysulfide) bond (where n is an integer of 1 or more). The -S-Sn- bond can form part of a larger bonding group such as a -Y1-C (Y2Y3) -S-Sn- bond or a -Y1-C (= Y4) -S-Sn- bond, in that Y1 is O or S, Y2 and Y3 are independently an organic fraction or -S-So-Z, where o is 1 or more and Z is an organic fraction or a selected species of Li, Na, quaternary ammonia, or quaternary phosphonium , and Y4 is O or S. In another embodiment, the organo-sulfur species contains a monovalent organic fraction and a selected species of Na, Li, quaternary ammonia and quaternary phosphonium that are linked by an -S-Sn- bond (including , for example, a -Y1-C (Y2Y3) -S-Sn- bond or -Y1-C (= Y4) -S-Sn- bond). In yet another embodiment, an -S-Sn- bond can appear on either side of an organic fraction. For example, the organic fraction can be a divalent aromatic fraction, optionally substituted, C (R3) 2 (with each R3 being independently H or an organic fraction such as a C1-C20 organic fraction), carbonyl (C = O) or thiocarbonyl (C = S).
    [0023] [0023] The organo-sulfur species can, for example, be selected from the group consisting of organic polysulfides, organic polythiolates, including those with sulfur-containing functional groups such as dithioacetal, dithocetal, trithio-orthocarbonate, aromatic polysulfide, polyether-polysulfide functionality, polysulfide-acid salt, thiosulfonate [-S (O) 2-S-], thiosulfinate [-S (O) -S-], thiocarboxylate [-C (O) -S-], dithiocarboxylate [-RC (S) - S-], thiophosphate or thiophosphonate, or mono-, di- or trithiocarbonate functionality; organo-metal polysulfides containing these or similar functionalities; and their mixtures.
    [0024] Suitable organic fractions include, for example, mono-, di- and polyvalent organic fractions which may comprise branched, linear and / or cyclic hydrocarbyl groups. As used herein, the term "organic fraction" includes a fraction that can, in addition to carbon and hydrogen, comprise one or more heteroatoms such as oxygen, nitrogen, sulfur, halogen, phosphorus, selenium, silicon, a metal such as tin and the like . The heteroatom (s) may be present in the organic fraction in the form of a functional group. Therefore, hydrocarbyl as well as functionalized hydrocarbyl groups are considered within the context of the present invention to be organic fractions. In one embodiment, the organic fraction is a C1-C20 organic fraction. In another embodiment, the organic fraction contains two or more carbon atoms. The organic fraction can thus be a C2-C20 organic fraction.
    [0025] [0025] The organo-sulfur species can have a monomeric, oligomeric or polymeric character. For example, the -S-Sn- functionality may be pending from the main structure of an oligomeric or polymeric species containing two or more repeating units of the monomer in its main structure. The -S-Sn- functionality can be incorporated into the main structure of such an oligomer or polymer, such that the main structure of the oligomer or polymer contains a plurality of -S-Sn- bonds.
    [0026] [0026] The organo-sulfur species can, for example, be an organic polysulfide or mixture of organic polysulfides of the formula R1-S-Sn-R2, where R1 and R2 independently represent an organic fraction C1-C20 and n is an integer of 1 or more. The organic fraction C1-C20 can be a branched, linear or cyclic hydrocarbyl group. R1 and R2 can each be independently a C9-C14 hydrocarbyl group, with n = 1 (providing a disulfide, such as tertiary dodecyl disulfide). In another embodiment, R1 and R2 are each independently a C9-C14 hydrocarbyl group, with n = 2-5 (providing a polysulfide). Examples of such compounds include TPS-32 and TPS-20, sold by Arkema. In another embodiment, R1 and R2 are independently C7-C11 hydrocarbyl groups, with n = 2-5. TPS-37LS, sold by Arkema, is an example of a suitable polysulfide of this type. Another suitable type of polysulfide would be a polysulfide or mixture of polysulfides in which R1 and R2 are both tert-butyl and n = 25. Examples of such organo-sulfur compounds include TPS-44 and TPS-54, sold by Arkema.
    [0027] [0027] The organo-sulfur species could also be an organic polyoliolate of the formula R1-S-Sn-M, where R1 is a C1-C20 organic fraction, M is lithium, sodium, quaternary ammonia, or quaternary phosphonium and en is an integer of 1 or more.
    [0028] [0028] In another embodiment, the organo-sulfur species can be a dithioacetal or dithiocetal such as those corresponding to formulas (I) and (II), or a tritio-orthocarboxylate of formula (III):
    [0029] [0029] where each R3 is independently H or a C1-C20 organic fraction, o, p and q are each independently an integer of 1 or more, and each Z is independently a C1-C20 organic fraction, Li, Na, quaternary ammonia , or quaternary phosphonium. Examples of such organo-sulfur species include 1,2,4,5-tetratian (formula I, R3 = H, o = p = 1), tetramethyl-1,2,4,5-tetratian (formula I, R3 = CH3, o = p = 1), and its oligo or polymeric species.
    [0030] [0030] Another embodiment of the invention uses a kind of organo-sulfur which 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):
    [0031] [0031] where R4 is independently tert-butyl or tert-amyl, R5 is independently OH, OLi or ONa, er is 0 or more (eg, 0-10) in formula (IV) with the aromatic rings being optionally substituted at one or more other positions by substituents other than hydrogen, R6 is a divalent organic fraction in formula (VI), R7 is a divalent organic fraction in formula (VII), each Z is independently a C1-C20 organic fraction, Li , Na, quaternary ammonia or quaternary phosphonium, eoep are each independently an integer of 1 or more. Examples of such an organo-sulfur species include aromatic polysulfides sold by Arkema under the trade name Vultac® (formula IV, R4 = tert-butyl or tert-amyl, R5 = OH); and polysulfide-acid salt corresponding to formulas VI and VII derived from mercaptoacids such as mercaptoacetic acid, mercaptopropionic acid, mercaptoethanesulfonic acid, mercaptopropanesulfonic acid, or olefin-containing acids such as vinylsulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid.
    [0032] [0032] In yet another embodiment, the organo-sulfur species is an organo-polysulfide or organo-metal containing trithiocarbonate functionality of the formula (IX), an organo-polysulfide or organo-metal containing dithiocarbonate functionality of the formula ( X), or an organo-polysulfide or organo-metal containing monothiocarbonate functionality of the formula (XI):
    [0033] [0033] where Z is a C1 -C20 organic fraction, Na, Li, quaternary ammonia, or quaternary phosphonium, and o and p are independently an integer of 1 or more.
    [0034] [0034] The liquid or gel electrolyte solution can additionally be comprised of a kind of dimetal polythiolate of the formula MS-Sn-M, in which each M is independently Li, Na, quaternary ammonia, or quaternary phosphonium en is an integer of 1 or more. Such a species therefore does not contain any organic fraction, unlike the organo-sulfur species described above.
    [0035] [0035] The intermediate separator element can act as a partition between compartments in an electrochemical cell. A compartment can comprise an electrolyte in contact with a cathode (the electrolyte in such a compartment can be referred to as a catholyte). Another compartment can comprise an electrolyte in contact with an anode (the electrolyte in such an compartment can be referred to as an anolyte). The anolyte and the catholyte can be the same, or different, from each other. One or both anolyte and catholyte may contain one or more species of organo-sulfur according to the invention. The intermediate separator element can be positioned between such compartments in a way that allows the anolyte ions to pass through the intermediate separator element to the catholyte and vice versa, depending on whether the electrochemical cell is being operated in the charge or discharge mode.
    [0036] [0036] In a further embodiment of the invention, the intermediate separating element is comprised of a porous polymer. The porous polymer can, for example, be comprised of polypropylene, polyethylene, or a fluorinated polymer. The porous polymer can be functionalized with an organo-sulfur species of the type described here. The organo-sulfur species can be pendent from the main structure of the porous polymer, can be present in crosslinking between the main structures of individual polymer chains and / or can be incorporated in the main structure of the porous main structure. Accordingly, the main structure of the porous polymer may contain one or more -S-Sn- bonds and / or the -S-Sn- bonds may be pending from the main polymer structure. Such -S-Sn- bonds can also be present in crosslinks.
    [0037] [0037] Suitable solvents to be used in electrochemical cells according to the invention include any of the basic aprotic polar solvents (complexing with cations) known or used for lithium-sulfur batteries in general such as sulfolane, dimethyl sulfoxide, dimethylacetamide, tetramethyl urea, Ν-methyl pyrrolidinone, tetraethyl sulfamide; ethers such as tetrahydrofuran, methyl-THF, 1,3-dioxolane, diglyme, and tetraglyme, and mixtures thereof; carbonates such as ethylene carbonate, propylene carbonate, dimethylcarbonate, diethylcarbonate, ethylmethylcarbonate, methylpropylcarbonate, ethylpropylcarbonate and the like; as well as esters such as methylacetate, ethyl acetate, propylacetate, and gamma-butyrolactone. The electrolyte can comprise a single such solvent or a mixture of such solvents. Any of the polar aprotic polymers known in the battery art could also be employed. The electrolyte can comprise a polymeric material and can take the form of a gel. Polymers suitable for use in the electrolyte may include, for example, polyethylene oxide, a polyethersulfone, a polyvinyl alcohol, or a polyimide. The electrolyte can be in the form of a gel, which can be a three-dimensional network comprised of a liquid and a binding component. The liquid can be a monomeric solvent that is trapped within a polymer, such as a crosslinked polymer.
    [0038] [0038] One or more conductive salts are present in the electrolyte in combination with the solvent and / or non-aqueous polar aprotic polymer. Conductive salts are well known in the battery art and include, for example, lithium salts of (CF3SO2) 2N_, CF3SO3-, CH3SO3-, ClO4_, PF6_, AsF6, halogen or the like. Sodium salts and other alkali metals and mixtures thereof can also be used.
    [0039] [0039] The active material of the anode can comprise an alkali metal such as lithium or sodium or other active material or composition. Particularly preferred active anode materials include lithium metal, lithium alloys, metallic sodium, sodium alloys, alkali metals or their alloys, metal powders, lithium and aluminum alloys, magnesium, silicon, and / or tin, alkali metal intercalates -carbon and metal-alkali-graphite, compounds capable of oxidizing and reversibly reducing with an alkali metal ion, and mixtures thereof. The metal or metal alloy (eg metallic lithium) can be contained as a film inside a battery or as several films, optionally separated by a ceramic material. Suitable ceramic materials include, for example, silica, alumina, or glassy materials containing lithium such as lithium phosphates, lithium aluminates, lithium silicates, phosphorus and lithium oxynitrides, tantalum and lithium oxides, lithium aluminosilicates, titanium oxides and lithium, lithium silicosulfides, lithium germanosulphides, lithium aluminosulphides, lithium borosulphides, lithium phosphosulphides and mixtures thereof.
    [0040] [0040] The cathode comprises elemental sulfur, elemental selenium or a mixture of elementary chalcogens. In one embodiment, the cathode is further comprised of one or more species of organo-sulfur according to those previously described in detail here. The cathode can additionally and / or alternatively be comprised of a binder and / or an electrically conductive additive. Suitable binders include polymers such as, for example, polyvinyl alcohol, polyacrylonitrile, polyvinylidene fluoride (PVDF), polyvinyl fluoride, polytetrafluoroethylene (PTFE), tetrafluoroethylene and hexafluoropropylene copolymers, fluoride and hexafluoroprene copolymers, fluoride and fluoride vinyl copolymers vinylidene and tetrafluoroethylene, ethylene-propylene-diene monomer rubber (EPDM), and polyvinyl chloride (PVC). The electrically conductive additive can be, for example, an electrically conductive carbon such as graphite, graphene, carbon fibers, carbon nanotubes, carbon black, or soot (e.g., lamp or oven soot). The cathode can be present in a battery or electrochemical cell in combination with a current collector, such as any of the current collectors known in the battery or electrochemical cell art. For example, the cathode may be coated on the surface of a metal current collector. EXAMPLES Cathode Fabrication, Battery Preparation, and Battery Testing Example 1
    [0041] [0041] A positive electrode comprising 70% by weight sublimated elemental sulfur powder, 20% by weight polyethylene oxide (PEO, MW 4 × 106), 10% by weight carbon black (Super P® Conductive, Alfa Aesar) was produced by the following procedure:
    [0042] [0042] The mixture of these components in N-methyl-2-pyrrolidone (NMP) was mechanically ground in a planetary milling machine. Acetonitrile was added to dilute the mixture. The resulting suspension was applied on aluminum foil (76 μm thick) with an automatic film coating (Mathis). The coating was dried at 50 ° C in a vacuum oven for 18 hrs. The resulting coating contained 3.10 mg / cm2 of cathode mixture. Example 2
    [0043] [0043] A positive cathode containing lithium n-dodecyl mercaptide (10% by weight of sulfur) was prepared following the procedure described in Example 1. The resulting coating contained 3.4 mg of sulfur / cm2. Example 3
    [0044] [0044] The positive cathode of Example 2 was used in a Swaglok PTFE cell with two stainless steel rods or coin cell assembly made of stainless steel (CR2032). The battery cell was mounted in an argon-filled glove box (MBraun) as follows: the cathode electrode was placed on the can bottom followed by the separator. Then electrolyte 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 stainless steel rods or with the crimping machine. Example 4
    [0045] [0045] Following the procedure described in Example 3, a battery cell consisting of the cathode of Example 2 (7/16 "diameter), 20 μL of 0.5 M LiTFSI solution in tetraethylene glycol dimethyl ether (TEGDME ): 1,3-dioxolane (DOL) = 1: 1, separator, and lithium electrode (thickness 0.38 mm, diameter 7/16 ") was tested for a charge-discharge cycle at a current of 0 , 1 mA. The test was carried out using a Gamry potentiometer (Gamry Instruments) up to a voltage cut of 1.5 V and 3.2 V at room temperature. The profile of the discharge cycle is shown in Figure 1. Synthesis of lithium alkylmercaptes Example 5 - Synthesis of lithium n-dodecyl mercaptide with hexyl lithium
    [0046] [0046] N-dodecyl mercaptan (9.98 g, 1 eq.) In hexanes (100 mL) at -30 ° C n-hexillithium (33% by weight in hexane, 1.1 eq.) Was added dropwise the drop to keep the temperature of the mixture below -20 ° C. The solvent was removed under reduced pressure to give a white solid in quantitative yield. Example 6 - Synthesis of lithium n-dodecyl mercaptide with lithium hydroxide
    [0047] [0047] A mixture of n-dodecyl mercaptan (2.0 g, 1 eq.) And lithium hydroxide monohydrate (0.41 g, 1 eq.) In acetonitrile (8 ml) was heated to 75 ° C and stirred at 75 ° C ° C for 16 hrs. After cooling to room temperature, the reaction mixture was filtered. The filter cake was rinsed with acetonitrile and dried at 50 ° C in a vacuum oven overnight. The lithium n-dodecylmercapte was obtained as a white solid in 93.5% yield (1.93 g). Example 7 - Synthesis of lithium n-dodecyl mercaptide with hexyl lithium
    [0048] [0048] Following the procedure described in Example 6, 3,6-dioxaoctane-1,8-dithiol salt and dilithium was synthesized from dimercaptan as a white solid in quantitative yield. Synthesis of lithium alkyl polythiolates Example 8 - Synthesis of lithium n-dodecylpolithiolate with lithium hydroxide
    [0049] [0049] To a solution degassed in nitrogen of n-dodecyl mercaptan (2.00 g, 1 eq.) In 1,3-dioxolane (25 ml) were added lithium hydroxide monohydrate (0.41 g, 1 eq. ) and sulfur (1.27 g, 4 eq.). The mixture was stirred under nitrogen at room temperature for 30 min. Lithium n-dodecyl polyolate in 1,3-dioxolane was obtained as a dark red solution. The complete conversion of mercaptan to lithium n-dodecyl polythiolate was confirmed by 13C-NMR and LCMS. Example 9 - Synthesis of lithium 3,6-dioxaoctane-1,8-polythiolate with lithium hydroxide and sulfur
    [0050] [0050] Following the procedure described in Example 8, a dark red solution of 3,6-dioxaoctane-1,8-polythiolate in lithium-1,3-dioxolane from the 3,6-dioxaoctane-1,8- reaction dithiol (0.72 g, 1 eq.), lithium hydroxide monohydrate (0.33 g, 2 eq.), and sulfur (1.02 g, 8 eq.) in 1,3-dioxolane (10 ml). Example 10 - Synthesis of lithium n-dodecylpolithiolate from lithium alkyl mercaptide
    [0051] [0051] To a nitrogen degassed suspension of lithium n-dodecyl mercaptide (0.21 g, 1 eq.) In 1,3-dioxolane (5 ml) was added sulfur (0.13 g, 4 eq.) . The mixture was stirred under nitrogen at room temperature for 16 hrs. Insoluble solids were removed by filtration. The dark red filtrate contained 63% lithium n-dodecyl polythiolates and 37% a mixture of bis (n-dodecyl) polysulfides as determined by LCMS. Example 11 - Synthesis of lithium n-dodecylpolithiolate with lithium metal and sulfur
    [0052] [0052] To a degassed solution of n-dodecyl mercaptan nitrogen (2.23 g, 1 eq.) In 1,3-dioxolane (25 ml) was added sulfur (1.41 g, 4 eq.), And lithium (76.5 mg). The mixture was heated to 60 ° C and stirred under nitrogen at 60 ° C for 1 hr. Lithium n-dodecyl polyolate in 1,3-dioxolane was obtained as a dark red solution. The complete conversion of the n-dodecyl mercaptan was confirmed by 13C-NMR. Example 12 - Synthesis of lithium 3,6-dioxaoctane-1,8-polyothiolate with lithium metal and sulfur
    [0053] [0053] Following the procedure in Example 11, a dark red solution of 3,6-dioxaoctane-1,8-polythiolate of lithium in 1,3-dioxolane was obtained by reaction of 3,6-dioxaoctane-1,8- dithiol (1.97 g, 1 eq.), lithium metal (0.15 g, 2 eq.), and sulfur (2.77 g, 8 eq.) in 1,3-dioxolane (11 ml). The complete conversion of onset dimercaptan was confirmed by 13C-NMR Example 13 - Dissolution of Li2S by added lithium n-dodecylpolitiolate
    [0054] [0054] To determine the solubility of lithium sulfide in electrolyte with lithium n-dodecylpolithiolate, a saturated solution of lithium sulfide was prepared as follows: A solution of 0.4 M lithium n-dodecylpolithiolate in 1.3 -dioxolane was prepared following procedures described in Example 10. The solution was then diluted to 0.2 M with tetraethylene glycol dimethyl ether, then the 1 M LiTFSI solution in 1: 1 tetraethylene glycol: 1,3-dioxolane dimethyl ether was added. to 1: 1 = v / v. To the resulting solution, sodium sulfide was added until a saturated mixture was obtained. The mixture was then filtered and the filtrate was analyzed for lithium dissolved by ICP-MS (7700x ICP-MS from Agilent). The solubility of lithium sulfide was calculated based on the level of lithium. In 0.5 M LiTFSI with 0.1 M lithium n-dodecylpolithiolate in 1: 1 tetraethylene glycol dimethyl ether: 1,3-dioxolane, the solubility of lithium sulfide was determined to be 0.33% by weight. In contrast, without lithium n-dodecylpolithiolate, the solubility of lithium sulfide in 0.5 M LiTFSI was only 0.13% by weight. This clearly demonstrated the improved solubility of Li2S in the battery's electrolyte matrix when the organo-sulfates of this invention are present.
    权利要求:
    Claims (11)
    [0001]
    Battery characterized by comprising: a) an anode comprising an active material of the anode comprising sodium, lithium or an alloy or composite of at least one of sodium or lithium with at least one other metal to provide ions; b) a cathode comprising an active cathode material comprising elemental sulfur, elemental selenium or a mixture of elementary chalcogens; and c) an intermediate separating element positioned between the anode and the cathode acting to separate liquid or gel electrolyte solutions in contact with the anode and the cathode, through which the metal ions and their counterions move between the anode and the cathode during battery charging and discharging cycles; wherein the liquid or gel electrolyte solutions comprise a non-aqueous polar aprotic polymer or solvent and a conductive salt and at least one of the conditions (i) or (ii) is met: (i) at least one of the liquid or gel electrolyte solutions additionally comprises at least one type of organo-sulfur; (ii) the intermediate separator element comprises a functionalized porous polymer containing at least one species of organo-sulfur; wherein the organo-sulfur species is selected from the group consisting of an organic polysulfide of the formula R1-S-Sn-R2, where R1 and R2 independently represent a C1-C20 organic fraction which can be linear, branched, or cyclic aliphatic or aromatic and which 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, and an organic polythiolate of the formula RS-Sn-M, where R1 is a C1-C20 organic fraction that can be linear, branched, or cyclic aliphatic or aromatic and comprising one or more functional groups containing N, O, P, S, Se, Si, Sn, halogen and / or metal , M is lithium, sodium, quaternary ammonium or quaternary phosphonium, and n is an integer of 1 or more.
    [0002]
    Battery according to claim 1, characterized in that the organo-sulfur species is a dithioacetal or dithiocetal of formula (I) or (II) or a tritio-orthocarboxylate of formula (III):
    [0003]
    Battery according to claim 1, characterized in that the organo-sulfur species is an aromatic polysulfide of formula (IV), a polyether polysulfide of formula (V), an acid polysulfide-salt of formula (VI) or a polysulfide-salt acid of formula (VII):
    [0004]
    Battery according to claim 1, characterized in that the organo-sulfur species is an organo-polysulfide or an organo-metal-polysulfide containing trithiocarbonate functionality of the formula (IX), an organo-polysulfide or an organo-metal-polysulfide containing functionality of dithiocarbonate of the formula (X), or an organo-polysulfide or an organo-metal-polysulfide containing the monothiocarbonate functionality of the formula (XI):
    [0005]
    Battery according to claim 1, characterized in that the liquid or gel electrolyte solution is additionally comprised of a kind of dimetal polythiolate of the formula MS-Sn-M, in which each M is independently Li, Na, quaternary ammonium, or quaternary phosphonium, en is an integer of 1 or more.
    [0006]
    Battery according to claim 1, characterized in that the organic fraction contains at least two carbon atoms.
    [0007]
    Battery according to claim 1, characterized in that the non-aqueous polar aprotic solvent or the polymer contains one or more functional groups selected from ether, carbonyl, ester, carbonate, amino, starch, sulfidyl [-S-], sulfinyl [- S (O) -] or sulfonyl [-SO2-].
    [0008]
    Battery according to claim 1, characterized in that the conductive salt corresponds to the formula MX in which M is Li, Na or quaternary ammonium and X is (CF3SO2) 2N, CF3SO3, CH3SO3, ClO4, PF6, NO3, AsF6 or halogen.
    [0009]
    Battery according to claim 1, characterized in that the organic fraction is oligomeric or polymeric and the organo-sulfur species comprises at least one -S-S- bond that is hung from the main structure of the oligomeric or polymeric organic fraction.
    [0010]
    Battery according to claim 1, characterized in that the organic fraction is oligomeric or polymeric and the organo-sulfur species comprises at least one -S-S- bond which is incorporated in the main structure of the oligomeric or polymeric organic fraction.
    [0011]
    Electrolyte characterized by comprising at least one non-aqueous polar aprotic solvent or polymer, at least one conducting salt, and at least one species of organo-sulfur comprising at least one organic fraction and at least one -S-Sn- bond where n is a integer of 1 or more.
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    同族专利:
    公开号 | 公开日
    RU2018128294A3|2019-03-20|
    RU2702115C2|2019-10-04|
    CN109360925A|2019-02-19|
    WO2013155038A1|2013-10-17|
    JP2018113265A|2018-07-19|
    RU2702337C2|2019-10-08|
    CN104221196B|2019-02-22|
    RU2018128295A3|2019-03-20|
    RU2014144995A|2016-06-10|
    SG10201604045YA|2016-07-28|
    CN109449356B|2021-07-13|
    SG11201406445WA|2014-11-27|
    US20150118535A1|2015-04-30|
    EP2837052A4|2015-10-07|
    RU2018128294A|2019-03-20|
    JP6766089B2|2020-10-07|
    CN109449356A|2019-03-08|
    EP2837052A1|2015-02-18|
    EP2837052B1|2019-01-09|
    TWI678013B|2019-11-21|
    KR102035010B1|2019-10-22|
    US10079405B2|2018-09-18|
    RU2669362C2|2018-10-11|
    SG10201604043WA|2016-07-28|
    TW201817073A|2018-05-01|
    CA2869969A1|2013-10-17|
    CN104221196A|2014-12-17|
    RU2018128295A|2019-03-20|
    JP2015513206A|2015-04-30|
    CN109360925B|2021-10-26|
    KR20150008079A|2015-01-21|
    TWI624978B|2018-05-21|
    IN2014DN08302A|2015-05-15|
    TW201342694A|2013-10-16|
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    法律状态:
    2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-10-27| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-02-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-04-06| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 09/04/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
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