WO2013149073A1 - Additif d'électrolyte à longévité améliorée - Google Patents

Additif d'électrolyte à longévité améliorée Download PDF

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WO2013149073A1
WO2013149073A1 PCT/US2013/034463 US2013034463W WO2013149073A1 WO 2013149073 A1 WO2013149073 A1 WO 2013149073A1 US 2013034463 W US2013034463 W US 2013034463W WO 2013149073 A1 WO2013149073 A1 WO 2013149073A1
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sulfur trioxide
electrolyte
battery according
complex
group
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PCT/US2013/034463
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English (en)
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Jeong Ju CHO
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A123 Systems, LLC
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Publication of WO2013149073A1 publication Critical patent/WO2013149073A1/fr

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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • 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
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • 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
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the field of the invention is batteries, and especially battery electrolytes.
  • Battery power is considered one of the more convenient and better performing choices as a power supply in many applications, including portable-power, transportation, grid and backup applications. Advantages to utilizing battery power include portability, isolation from power lines and from earth ground, minimization of heat management, and
  • Batteries comprise two major components: (1) electrodes, specifically an anode and a cathode, and (2) an electrolyte.
  • the electrode is a phase through which charge is carried by electronic movement. Electrodes can be metals or semiconductors, and they can be solid or liquid. The electrolyte is generally defined as a phase through which charge is carried by the movement of ions. Electrolytes may be any phase on the continuum of liquid to solid, including gels, pastes, fused salts, or ionically conducting solids, such as, sodium. P-alumina, which has mobile sodium ions. (Bard, Allen J. and Larry R. Faulkner, Electrochemical Methods: Fundamentals and Applications, John Wiley & Sons (New York), 1980).
  • the electrolyte is generally the most unstable component of a battery or cell, particularly because it can be compromised or decomposed much faster than the electrodes. When the electrolyte is subject to decomposition, its ability to cycle from charge to discharge becomes compromised. In an attempt to improve cycle life of batteries a variety of electrolyte additives have been proposed. However, the proposed additives either cause an increased impedance of the electrolyte or are detrimental to cell capacity. SUMMARY OF THE INVENTION
  • a lithium ion battery with excellent cycle life and characteristics was obtained including an alkali transition metal oxoanion material as a cathode material and an electrolyte containing a sulfur trioxide amine complex additive.
  • the electrolyte additive delays thermal decomposition of the electrolyte and is particularly suited to non-aqueous electrolytes.
  • Materials for the cathode are selected alkali transition metal oxoanion materials, including composite oxide materials of lithium and transition metal such as lithium metal phosphates, chosen for their high lithium-insertion potential, high theoretical capacity, low cost, ease of synthesis, and stability when used with common organic electrolyte systems.
  • a battery in one aspect, includes an anode, a cathode, and an electrolyte comprising a lithium salt and a sulfur trioxide amine complex that suppresses electrolyte decomposition, wherein, the cathode includes an alkali transition metal oxoanion electroactive material.
  • the alkali transition metal oxoanion material is selected from the group consisting of: (i) a composition Ax(M'l-aM"a)y(XD4)z,
  • Ax(M'l-aM”a)y(DXD4)z, or Ax(M'l-aM”a)y(X2D7)z wherein A is at least one of an alkali metal, M is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, boron, aluminum, silicon, vanadium, molybdenum and tungsten, M" is any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is oxygen, 0.00014, X2D7, or DXD4 group; (ii)a composition (Al-aM"a)xM'y(XD4)z, (Al-aM"a)xM'y(DXD4)z, or (Al-aM"a)xM'y(X2D7)z, wherein A is at least one of an alkali metal, M
  • the compound has a conductivity at 27° C of at least about 10-8 S/c; and (iii) a composition (Ab-aM"a)xM'y(XD4)z, (Ab-aM"a)xM'y(DXD4)z, or
  • (Ab-aM"a)xM'y(X2D7)z wherein A is at least one of an alkali metal, M is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, boron, aluminum, silicon, vanadium, molybdenum and tungsten, M" any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is oxygen, 0.0001 ⁇ A ⁇ 0.1, z x, that such values have and than greater are zero y, (b-a)x plus the quantity ax times the formal valence or valences of M" plus y times the formal valence or valences of M is equal to z times the formal valence of the XD4, X2D7 or DXD4 group.
  • the alkali transition metal oxoanion includes lithium metal phosphate.
  • the sulfur trioxide amine complex is selected from the group comprising: sulfur trioxide trimethylamine complex; sulfur trioxide pyridine complex; sulfur trioxide triethylamine complex; sulfur trioxide ⁇ , ⁇ -dimethylfromide complex, or mixtures thereof.
  • the sulfur trioxide amine complex comprises a sulfur trioxide pyridine complex.
  • the electrolyte contains from 0.01%(wt) to 3%(wt) of said sulfur trioxide amine complex.
  • the electrolyte contains from 0.1% (wt) to l%(wt) of said sulfur trioxide amine complex.
  • the molar concentration of the lithium salt is between 0.5 amd 2.0 mol/l.
  • the lithium salt is selected from the group consisting of LiC104, LiPF6, LiBF4, LiCF3 S03, LiN (CF3 S02)2, LiN (CF3 CF2 S02)2, LiN (CF3 S02) (C4 F9 S02) and LiC (CF3 S02)3.
  • the electrolyte further includes aprotic solvents.
  • the solvent includes at least one of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate, ⁇ -butyrolactone, ⁇ -valerolactone, methyl acetate, methyl propionate, tetrahydrofuran, 2-methyl tetrahydrofuran, tetrahydropyran, dimethoxy ethane,
  • dimethoxymethane ethylene methyl phosphate, ethyl ethylene phosphate, trimethyl phosphate, triethyl phosphate, halides thereof, vinyl ethylene carbonate and
  • fluoroethylenecarbonate poly(ethylene glycol), diacrylate, and combinations thereof.
  • the solvent includes a mixture of ethylene carbonate, propylene carbonate, ethylmethyl carbonate, and diethyl carbonate.
  • the anode comprises graphite.
  • a battery in another aspect, includes an anode, a cathode, and an electrolyte comprising a lithium salt, a sulfur trioxide amine complex that suppresses electrolyte decomposition, and a nitrile compound
  • the cathode includes a alkali transition metal oxoanion electroactive material selected from the group consisting of: (i) a composition Ax(M * l-aM"a)y(XD4)z, Ax(M * l-aM"a)y(DXD4)z, or Ax(M * l-aM"a)y(X2D7)z, wherein A is at least one of an alkali metal, M is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, boron, aluminum, silicon, vanadium, molybdenum and tungsten, M" is any of a Group IIA, A, IVA, VA, VIA, VII
  • Al-aM"a)xM * y(XD4)z, (Al-aM”a)xM * y(DXD4)z, or (Al-aM”a)xM * y(X2D7)z wherein A is at least one of an alkali metal or hydrogen, M is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, boron, aluminum, silicon, vanadium, molybdenum and tungsten, M" any of a Group IIA, A, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is oxygen, 0.00014, X2D7 or DXD4 group.
  • the compound has a conductivity at 27° C of at least about 10-8 S/c; and (iii) a composition (Ab-aM"a)xM * y(XD4)z, (Ab-aM”a)xM * y(DXD4)z, or (Ab-aM”a)xM * y(X2D7)z, wherein A is at least one of an alkali metal or hydrogen, M is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, boron, aluminum, silicon, vanadium, molybdenum and tungsten, M" any of a Group IIA, A, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is oxygen, 0.0001 ⁇ A ⁇ 0.1, z x, that such values have and than greater are zero y, (b-a)x plus the quantity ax times the formal val
  • the sulfur trioxide amine complex is selected from the group comprising: sulfur trioxide trimethylamine complex; sulfur trioxide pyridine complex; sulfur trioxide triethylamine complex; sulfur trioxide ⁇ , ⁇ -dimethylfromide complex, or mixtures thereof, and the nitrile compound is selected from succinonitrile, cyanobenzene, or mixtures thereof.
  • the sulfur trioxide amine complex is a sulfur trioxide pyridine complex.
  • the electrolyte contains from 0.01%(wt) to 3%(wt) of said sulfur trioxide amine complex.
  • the electrolyte contains from 0.1%(wt) to l%(wt) of said sulfur trioxide amine complex.
  • the electrolyte contains from 0.01%(wt) to 3%(wt) of said nitrile compound.
  • the electrolyte contains from l%(wt) to 2%(wt) of said nitrile compound.
  • Figure 1 shows a photograph of two electrolyte samples after 2 months of storage at 55°C, according to one or more embodiments.
  • Figures 2A-2C show plots of the retained and recovered capacities of batteries after 1 month storage at 55°C, with and without a sulfur trioxide pyridine additive, according to one or more embodiments.
  • Figures 3A-3C show plots of the DC resistance of batteries before and after 1 month storage at 55°C, with and without a sulfur trioxide pyridine additive, according to one or more embodiments.
  • Figure 4 shows a plot of capacity versus cycle number for batteries with an without the sulfur trioxide additive, according to one or more embodiments. The cycles were performed at 1C/-1C rates at 35°C.
  • An electrochemical lithium ion battery with excellent cycle life and characteristics was obtained with alkali transition metal oxoanion as a cathode material and an electrolyte containing a sulfur trioxide amine complex additive.
  • the cell includes cathodes of selected transition metal polyanion compounds, which are the materials of choice for applications requiring their high lithium-insertion potential, high capacity, low cost, ease of synthesis, and stability when used with common organic electrolyte systems.
  • the electrolyte is chosen to be stable within the electrochemical cell comprising such cathode materials.
  • the sulfur trioxide amine complex electrolyte additive delays thermal decomposition of the electrolyte and is particularly suited to non-aqueous electrolytes. The additive also contributes to an
  • Sulfur trioxide is a chemical compound with the formula S0 3 .
  • a sulfur trioxide amine complex is selected from the group comprising: sulfur trioxide trimethylamine complex; sulfur trioxide pyridine complex; sulfur trioxide
  • sulfur trioxide amine complex compounds according to one or more embodiment are defined as follows: Sulfur trioxide trimethylamine complex:
  • Electrodes can be metals or semiconductors, and they can be solid or liquid.
  • electrolytes is generally defined as a phase through which charge is carried by the movement of ions. Electrolytes may be any phase on the continuum of liquid to solid, including gels, pastes, fused salts, or ionically conducting solids, such as sodium P-alumina, which has mobile sodium ions.
  • anode material and “anode” are used interchangeably, except where the context clearly indicates otherwise.
  • cathode material and “cathode” are used interchangeably. These definitions are intended to eliminate confusion over the exact point at which the respective electrode material(s) is/are incorporated into, and thus becomes an electrode.
  • the battery according to one or more embodiments includes electrodes (cathode and anode), a separator, and an electrolyte.
  • Materials for the cathode are alkali transition metal oxoanions, including selected composite oxide materials of lithium and transition metal such as lithium metal phosphates or combinations of lithium metal phosphates and lithium oxides.
  • the cathode (i.e. positive electrode) material used in the nonaqueous electrolytic solution cell of the present invention properly be selected from those capable of occluding and liberating lithium, which are exemplified as alkali transition metal oxoanions such as composite oxide materials of lithium and transition metal such as lithium metal phosphates or combinations of lithium metal phosphates and lithium oxides.
  • Oxoanion are anion moieties that include one or more elements, one of which is oxygen, such as phosphates, sulfates, silicates and the like.
  • Oxoanions may include moieties such as X 2 O 7 and OXO 4 , where X may be at least one of phosphorus, sulfur, arsenic, boron, aluminum, silicon, vanadium, molybdenum and tungsten.
  • X may be at least one of phosphorus, sulfur, arsenic, boron, aluminum, silicon, vanadium, molybdenum and tungsten.
  • a preferred oxoanion is phosphate.
  • a cathode material comprises a composition A x (M'i_ a M" a ) y (XD4) z ,
  • the compound has a conductivity at 27° C. of at least about 10 "8 S/cm. In some of these embodiments, the compound has a specific surface area of at least 15 m 2 /g. In some of these embodiments, the compound crystallizes in an ordered or partially disordered structure of the olivine (A x MX0 4 ), NASICON (A ⁇ MM ⁇ iXO ⁇ ), VOP0 4 , LiFe(P 2 0 7 ) or Fe 4 (P 2 0 7 ) 3 structure-types, and has a molar concentration of the metals (M'+M") relative to the concentration of the elements X that exceeds the ideal stoichiometric ratio y/z of the prototype compounds by at least 0.0001.
  • a x MX0 4 ordered or partially disordered structure of the olivine
  • NASICON A ⁇ MM ⁇ iXO ⁇
  • VOP0 4 LiFe(P 2 0 7 ) or Fe 4 (P 2 0 7 ) 3 structure
  • the cathode compound can also comprise a composition (Ai_ a M" a ) x M ' y (XD 4 ) z , (Ai_ a M" a ) x M y (DXD 4 ) z , or (Ai_ a M" a ) x M ' y (X 2 D 7 ) z , wherein A is at least one of an alkali metal or hydrogen, M' is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, boron, aluminum, silicon, vanadium, molybdenum and tungsten, M" any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is at least one of oxygen, nitrogen, carbon, or a halogen, 0.00014, X 2 D 7 , or DXD 4 group.
  • the compound has a conductivity at 27° C. of at least about 10 "8 S/cm. In some of these embodiments, the compound has a specific surface area of at least 15 m 2 /g. In some of these embodiments, the compound crystallizes in an ordered or partially disordered structure of the olivine (A x MX0 4 ), NASICON (A x ,(M',M") 2 (X0 4 ) 3 ), VOP0 4 , LiFe(P 2 0 7 ) or Fe 4 P 2 0 7 ) 3 structure-types, and has a molar concentration of the metals (M'+M”) relative to the concentration of the elements X that exceeds the ideal stoichiometric ratio y/z of the prototype compounds by at least 0.0001.
  • a x MX0 4 ordered or partially disordered structure of the olivine
  • NASICON A x ,(M',M" 2 (X0 4 ) 3
  • VOP0 4 LiF
  • the cathode compound comprise a composition (Ab_ a M" a ) x M ' y (XD 4 ) z , (A b - a M " a )xM y (DXD 4 ) z , or (A b _ a M " a ) x M ' y (X 2 D 7 ) z , wherein A is at least one of an alkali metal or hydrogen, M' is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, boron, aluminum, silicon, vanadium, molybdenum and tungsten, M" any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is at least one of oxygen, nitrogen, carbon, or a halogen, 0.0001 ⁇ A ⁇ 0.1, z x, that such
  • the compound has a conductivity at 27° C. of at least about 10 ⁇ 8 S/cm. In some of these embodiments, the compound has a specific surface area of at least 15 m 2 /g. In some of these embodiments, the compound crystallizes in an ordered or partially disordered structure of the olivine (A x MX0 4 ), NASICON
  • Preferred cathode compounds are described in US Patent No. 7338734 and US Published application no. 2009/0123813, both incorporated herein by reference.
  • the preferred blended cathode materials are described in USSN 61/524532, filed 8/17/11, and USSN 61/511,280, filed 7/25/11, also incorporated herein by reference.
  • the cathode material is preferably a lithiated metal phosphate.
  • the lithiated metal phosphate is lithiated iron phosphate.
  • the cathode material may also be affixed to a support using a suitable binder.
  • suitable binder for this purpose are aluminum, aluminum alloys, titanium, stainless steel, and the like.
  • Acetylene black may also be included in the cathode.
  • the anode is preferably fabricated using a material capable of intercalating lithium.
  • Various metal phosphates, metal oxides and chalcogenides satisfy this requirement, including especially iron phosphate, tin oxide, molybdenum oxide, tungsten oxide, and titanium disulfide.
  • Any suitable form of carbon may alternatively be used for the anode, include coke, synthetic or natural graphite, mesophase microbeads, a soft or hard disordered carbon, and the like.
  • anode material comprises at least 15%, 25%, 50%>, 75%> or 90% of a compound selected from the group comprising at least one metal oxide, at least one chalcogenide, and at least one form of carbon, and at least of silicone or Si/C composites
  • the electrodes are formed by mixing a polymeric binder with the cathode and anode materials in an appropriate liquid medium such as an organic solvent. This forms a paste or slurry, which is then coated onto a current collector grid, foil or mesh. The resulting intermediates are then pressed into a sheet form, dried and cut to appropriate dimensions.
  • Types of the binder used for the fabrication of the electrode is not particularly limited as far as it is stable to the solvent and electrolytic solution used in the fabrication of the electrode.
  • the binder include resinous polymers such as polyethylene, polypropylene, polyethylene terephthalate, aromatic polyamide, and cellulose; rubbery polymers such as styrene-butadiene rubber, isoprene rubber, butadiene rubber, and ethylene -propylene rubber; thermoplastic elastomeric polymers such as
  • styrene-ethylene-butadiene-styrene block copolymer and its hydrogenated product and styrene-isoprene-styrene block copolymer and its hydrogenated product
  • flexible resinous polymers such as syndiotactic 1 ,2-polybutadiene, ethylene-vinyl acetate copolymer, and propylene-a-olefm (having 2 to 12 carbon atoms) copolymer
  • fluorocarbon polymers such as polyvinylidene fluoride, polytetrafluoroethylene, and polytetrafluoroethylene-ethylene copolymer.
  • Separator materials in battery cells are, in some instances, formed from bodies of porous polymer materials. In other instances, separator materials are formed from bodies of fibrous or particulate material, and such materials can include glass fibers, mineral fibers such as asbestos, ceramics, synthetic polymeric fibers as well as natural polymeric fibers such as cellulose.
  • An electrolyte may occur in any form, including liquid, semi-solid, or even solid.
  • the electrolyte must cooperate with the active electrode material(s) to provide chemical reactions that store and release electrical energy, and many such chemistries are already known.
  • Non-aqueous electrolyte solvents are preferred in certain embodiments, and may include cyclic carbonates such as ethylene carbonate, propylene carbonate and butylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate; cyclic esters such as ⁇ -butyrolactone and ⁇ -valerolactone; chain esters such as methyl acetate and methyl propionate; cyclic ethers such as tetrahydrofuran, 2-methyl tetrahydrofuran and tetrahydropyran; chain ethers such as dimethoxyethane and
  • cyclic phosphoric acid esters such as ethylene methyl phosphate and ethyl ethylene phosphate; chain phosphoric acid esters such as trimethyl phosphate and triethyl phosphate; halides thereof; sulfur-containing organic solvents, Vinyl ethylene carbonate (VEC) and Fluoroethylenecarbonate (FEC), Poly(ethylene glycol) diacrylate.
  • the organic solvent may be used singly, or two or more of such solvents may be used in combination.
  • Examples of the solute used for the nonaqueous electrolytic solution are inorganic lithium salts such as LiC10 4 , LiPF 6 , LiBF 4 ; and fluorine-containing organic lithium salts such as LiCF 3 S0 3 , LiN (CF 3 S0 2)2 , LiN (CF 3 CF 2 S0 2)2 , LiN (CF 3 S0 2) (C 4 F 9 S0 2) and LiC (CF 3 S0 2)3 . These solutes may be used singly or in combination of two or more. Molar concentration of the lithium salt as a solute in the electrolytic solution is preferably within a range from 0.5 to 2.0 mol/1. In a preferred embodiment, LiPF6 is used.
  • a general electrolyte may be stable or unstable on the electrode, e.g. the anode.
  • Many known electrolytes having desirable characteristics such as low volatility, high flash point, low freezing point, or high dielectric constant, for example, are unstable on the electrodes and will ultimately affect the formation of the solid electrolyte interface (SEI).
  • SEI solid electrolyte interface
  • the sulfur trioxide amine complex is present in the electrolyte solution in an amount effective to retard electrolyte degradation and provide improved cycle life of the battery
  • the electrolyte contains from 0.01%(wt) to 3%(wt) of the sulfur trioxide trimethylamine complex.
  • the electrolyte contains from 0.1%(wt) to l%(wt) of the sulfur trioxide trimethylamine complex.
  • the additive promotes the formation of SEI that is highly conductive to lithium ions, thus leading to an improvement in battery capacity retention and decreased cell impedance after storage.
  • the formed SEI allows for high Li + ion conductivity while isolating electronic transport.
  • the additive suppresses the reduction and decomposition of the electrolyte solvent at the electrode (e.g., anode), reducing gas formation.
  • the electrolyte is chosen to be stable within the electrochemical cell comprising cathodes of selected transition metal polyanion compounds.
  • nonaqueous electrolytic solution cell using such nonaqueous electrolytic solution, negative electrode (anode), positive electrode (cathode), outer container and separator, is of no specific limitation, and can properly be selected from those being generally employed.
  • the nonaqueous electrolytic solution cell of the present invention may include, if necessary, a gasket, a sealing plate and a cell case besides such nonaqueous electrolytic solution, negative electrode, positive electrode, outer can or pouch material and separator.
  • composition with the additive consisted of:
  • composition without the additive consisted of:
  • EC denotes ethylene carbonate
  • PC denotes propylene carbonate
  • EMC denotes ethylmethyl carbonate
  • DEC diethyl carbonate
  • Figure 1 shows a photograph of two electrolyte samples after 2 month storage at 55C .
  • the sample on the left 110 labeled "Electrolyte + Additive” is an electrolyte containing the sulfur trioxide pyridine complex.
  • the sample on the right 120 is the composition without the additive.
  • the photograph shows a smaller color change (e.g., darkening) of electrolyte with the additive 110 as compared to that without the additive 120.
  • the color change is due to the thermal decomposition of electrolyte.
  • the reduced color change indicates that the sulfur trioxide amine complex additive improves the thermal stability of electrolyte, leading to better result for calendar life.
  • PS propane sultone
  • Propane sultone is a known anti-gassing agent in electrolytes. It is known to deleteriously increase cell impedance.
  • the siloxane material includes, for example aminopropyl triethoxysilane.
  • Siloxane is another conventional additive used to trap HF from electrolyte solution. Siloxane is not effective in promoting cell life and or preventing electrolyte decomposition, as shown below.
  • Figures 2A-C show boxplots of retained and recovered capacity for batteries fabricated with the three electrolyte compositions above.
  • Figure 2A show the % retained capacity after 1 month storage at 55°C. Retained capacity is measured as a first discharge of the cell after storage. Retained capacity is lower than initial capacity and includes some reversible and some irreversible capacity loss.
  • Figure 2B show the % recovered capacity after 1 month storage at 55°C, recovered at a low discharge rate. Recovered capacity is measured after an initial discharge of the cell is used to measure retained capacity. Recovered capacity is typically higher than retained capacity as some reversible loss capacity has been recovered upon cycling.
  • Figure 2C show the % recovered capacity after 1 month storage at 55°C, recovered at a high discharge rate of 6.5C. The plots show a clear advantage of the sulfur trioxide additive over the other electrolyte compositions in terms of retained and recovered charge capacities. This difference is most noticeable at high discharge rates, especially in comparison to the electrolyte composition with the siloxane additive.
  • Figures 3A-C show boxplots of DC resistance for batteries fabricated with the three electrolyte compositions above.
  • Figure 3 A shows the resistance of each cell before storage
  • Figure 3B shows the resistance of each cell after storage for 1 month at 55°C
  • Figure 3C shows the % change in resistance before and after storage for the three batteries.
  • only the battery with the sulfur trioxide additive showed a decrease in cell impedance after storage.
  • FIG. 4 shows a plot of capacity versus cycle number for batteries with an without the sulfur trioxide additive.
  • the cycles were performed at 1C/-1C rates at 35°C.
  • the electrolyte compositions consisted of (1) a control composition that included no additives, (2) a composition that included a siloxane additive, (3) a composition that included a sulfur trioxide pyridine additive, and (4) a composition that included ⁇ -butyrolactone (GBL). It is clear that discharge capacity is not deleteriously affected by the presence of the additive.
  • Typical cells can be cycled at least 500 times, preferably more than 1000 times and most preferably more than 2000 times.
  • the additive improves electrolyte stability at elevated temperatures and helps prevent decomposition in the presence of water and HF.
  • the combined effects of the sulfur trioxide pyridine complex result in improvement of electrolyte calendar life and cycle life.
  • LiF Water contaminants are known to produce LiF in electrolyte using LiPF 6 salt. Water reacts with the PF 5 present in solution to produce fluoride ions (Reaction 1) or HF. These fluoride ions react with the Li + ions present in solution, leading to the precipitation of LiF. Precipitated LiF highly impedes lithium ion transport through SEI layer on the electrode surface (e.g., anode). Additionally, HF can readily decompose to form hydrogen gas, which can lead to unwater swelling of the battery cell.
  • Reaction 1 fluoride ions
  • HF can readily decompose to form hydrogen gas, which can lead to unwater swelling of the battery cell.
  • the sulfur trioxide pyridine complex acts as a salt-stabilizer and water-getter.
  • the SO 3 group in the sulfur trioxide pyridine complex is a dehydrated form of sulfuric acid, H 2 SO 4 .
  • SO 3 readily produces H 2 SO 4 in the presence of water impurities in electrolyte.
  • the sulfur trioxide functions as a water-getter, suppressing formation of HF.
  • the resulting H 2 SO 4 leads to precipitation of L1 2 SO 4 instead of LiF, which is more ionically conductive than LiF. (Reaction 2).
  • L1 2 SO 4 precipitates as part of the SEI, hindering electronic transport and promoting ionic transport.
  • the pyridine group of the additive acts as a salt stabilizer. It forms quaternary amonium salt with HF, preventing it from decomposing in the electrolyte.
  • the pyridine group also stabilizes PF 5 as Lewis base, further suppressing the decomposition of the LiPF 6 salt in electrolyte (Reaction 1).
  • An excess of H 2 SO 4 formation to the sulfur trioxide additive may lead to corrosion metallic component, especially a Cu foil, which is a common anode current collector.
  • the corrosion reaction is suppressed by adding nitrile compounds such as succinonitrile or phenylnitirle into the electrolyte solution.

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Abstract

La batterie lithium ion selon l'invention à longévité et caractéristiques excellentes a été obtenue en ajoutant un matériau d'oxoanion d'alcalin et de métal de transition comme matériau de cathode et un électrolyte contenant un additif complexe trioxyde de soufre-amine. L'additif d'électrolyte retarde la décomposition thermique de l'électrolyte et convient particulièrement aux électrolytes non aqueux. De plus, l'additif permet une amélioration dans la rétention de capacité de la batterie et une impédance de cellules décrue après entreposage. Les matériaux pour la cathode sont des matériaux d'oxoanions d'alcalin et de métal de transition sélectionnés, compris des matériaux d'oxyde composite de lithium et de métal de transition par exemple des phosphates de lithium et de métal, choisis pour leur fort potentiel d'insertion de lithium, leur capacité théorique élevée, leur faible coût, leur facilité de synthèse, et leur stabilité lorsqu'on les utilise avec des systèmes d'électrolyte organique communs.
PCT/US2013/034463 2012-03-28 2013-03-28 Additif d'électrolyte à longévité améliorée WO2013149073A1 (fr)

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WO2018127492A1 (fr) 2017-01-03 2018-07-12 Basf Se Complexes de trioxyde de soufre de pyridine en tant que composant d'électrolyte pour batteries haute tension
CN108390099A (zh) * 2018-05-03 2018-08-10 诺莱特电池材料(苏州)有限公司 一种锂离子电池电解液及锂离子电池
CN111048839A (zh) * 2019-12-25 2020-04-21 湖州昆仑动力电池材料有限公司 具有良好低温放电特性的锂离子电池电解液和锂离子电池
CN111584930A (zh) * 2020-05-18 2020-08-25 湖南大学 一种锂离子电池电解液及锂离子电池
CN112993289A (zh) * 2019-12-12 2021-06-18 中国科学院大连化学物理研究所 锂/氟化碳电池及其电解液与使用方法

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US4714664A (en) * 1985-06-17 1987-12-22 A/S Hellesens Electrical battery
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018127492A1 (fr) 2017-01-03 2018-07-12 Basf Se Complexes de trioxyde de soufre de pyridine en tant que composant d'électrolyte pour batteries haute tension
CN110291673A (zh) * 2017-01-03 2019-09-27 巴斯夫欧洲公司 作为高压电池组的电解质组分的吡啶三氧化硫络合物
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JP6991471B2 (ja) 2017-01-03 2022-02-03 ビーエーエスエフ ソシエタス・ヨーロピア 高電圧電池用の電解質成分としてのピリジン三酸化硫黄錯体
CN108390099A (zh) * 2018-05-03 2018-08-10 诺莱特电池材料(苏州)有限公司 一种锂离子电池电解液及锂离子电池
CN112993289A (zh) * 2019-12-12 2021-06-18 中国科学院大连化学物理研究所 锂/氟化碳电池及其电解液与使用方法
CN111048839A (zh) * 2019-12-25 2020-04-21 湖州昆仑动力电池材料有限公司 具有良好低温放电特性的锂离子电池电解液和锂离子电池
CN111584930A (zh) * 2020-05-18 2020-08-25 湖南大学 一种锂离子电池电解液及锂离子电池

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