WO2014067891A1 - Batterie rechargeable au lithium-ion qui comprend du lithium cobalt phosphate comme matériau actif de cathode - Google Patents

Batterie rechargeable au lithium-ion qui comprend du lithium cobalt phosphate comme matériau actif de cathode Download PDF

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WO2014067891A1
WO2014067891A1 PCT/EP2013/072485 EP2013072485W WO2014067891A1 WO 2014067891 A1 WO2014067891 A1 WO 2014067891A1 EP 2013072485 W EP2013072485 W EP 2013072485W WO 2014067891 A1 WO2014067891 A1 WO 2014067891A1
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electrolyte
fluorinated
carbonate
battery
active material
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PCT/EP2013/072485
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Elena Markevich
Ronit SHARABI
Katia FRIDMAN
Gregory Salitra
Doron Aurbach
Ran Elazari
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Basf Se
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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
    • H01M10/05—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
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0034—Fluorinated solvents
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 present invention relates to a lithium ion secondary battery with improved capacity retention property, faradaic efficiency and durability. 2. BACKGROUND
  • Lithium cobalt phosphate with an olivine structure possesses high operating voltage (red-ox potential of 4.8 V vs. Li/Li + ), flat voltage profile, and a high theoretical capacity of about 170 mAh/g (Phadhi et al., J. Electrochem. Soc, 1997, 144, 1 188).
  • L1C0PO4 has shown a fast fading of discharge capacity upon charge-discharge cycling (Wolfenstine et al., J. Power Sources, 2005, 144, 226; Bramnik et al., J.
  • FEC fluorinated ethylene carbonate
  • US 201 1/0143216 discloses lithium secondary batteries which include a positive electrode containing a lithium transition-metal oxyanion compound of the formula LiFeP04 as a positive electrode active material, a negative electrode and a non-aqueous electrolyte solution, which con- tains vinylene carbonate, such as fluoroethylene carbonate, and a solvent and/or a solute that decomposes at a potential more positive than that of vinylene carbonate.
  • different transition-metal oxyanion compound in which some of the Fe is replaced by other transition metals such as Co, Ni, Mn or mixtures thereof may be used; however, such cathodes are not exemplified.
  • US 201 1/0223490 discloses nonaqueous electrolyte secondary battery comprising a positive electrode, a negative electrode, a non-aqueous electrolyte and a separator, wherein the positive electrode active material is composed of a mixture of a lithium-cobalt composite oxide containing at least both zirconium and magnesium, and a lithium-manganese-nickel composite oxide containing at least both manganese and nickel; and the nonaqueous electrolyte includes fluoro- ethylene carbonate and dimethyl carbonate and further includes an additive such as 2-propynyl 2-(methane sulfonyloxy)propionate (PMP) or 2-propynyl methane sulfonate (MSP).
  • PMP 2-propynyl 2-(methane sulfonyloxy)propionate
  • MSP 2-propynyl methane sulfonate
  • An object of the present invention was to provide an electrolyte for high voltage Li-ion second- ary batteries comprising LiCoP0 4 as cathode active material which allows long operation of the batteries and high voltage Li-ion secondary batteries comprising LiCoP0 4 as cathode active material with prolonged cycle stability and life time.
  • the present invention thus provides a lithium ion secondary battery comprising:
  • a cathode comprising a cathode active material selected from LiCoP0 4 ;
  • an anode comprising an anode active material that can reversibly occlude and release lithium ions
  • a non-aqueous electrolyte comprising at least one lithium salt and at least one nonaqueous organic solvent selected from fluorinated carbonates.
  • the present invention relates to the use of electrolyte (iii) in lithium ion secondary batteries comprising a cathode active material selected from LiCoP0 4 .
  • the present invention relates to a non-aqueous electrolyte comprising at least one lithium salt, at least one non-aqueous organic solvent selected from fluorinated carbonates and at least one optionally fluorinated boroxine of formula (I) as defined below and to the use of said electrolyte in lithium ion secondary batteries comprising a cathode active material selected from LiCoP0 4 .
  • Figs. 1 A-1 B show SEM image (1 A) and XRD pattern (1 B) of carbon-coated LiCoP0 4 olivine powder.
  • the LiCoP0 4 powder consists of rods having a diameter of 50-200 nm and a length of about 1 ⁇ .
  • the material has an orthorhombic, olivine-like structure as described in X-ray Powder Diffraction Data Files 00-032-0552.
  • Figs. 2A-2B show curves of discharge capacity (2A) and irreversible capacity (2B) vs. cycle number obtained upon galvanostatic cycling (C/8 h rates) of LiCoP0 4 electrodes (30°C).
  • 1 M LiPFe/FEC-DMC 1 :4 solution taken in amount of 15 ⁇ /mg (open circles) or 5 ⁇ /mg (full circles) of active electrode mass
  • Fig. 3 shows the discharge capacity vs. cycle number obtained upon galvanostatic cycling (C/2 h rate) of LiCoP0 4 electrodes (30°C) with the electrolyte composition comprising 1 wt.-% of TMB in 1 M LiPFe/FEC-DMC 1 :4 taken in amount of 5 ⁇ /mg of active electrode mass.
  • Fig. 4. shows XPS spectra of LiCoP0 4 electrodes cycled for an equal period of time in EC- based electrolyte solution (panel A); FEC-based electrolyte solution (panel B); and said FEC- based electrolyte with the addition of 0.5 wt.-% of TMB (panel C).
  • Fig. 5 shows the charge and discharge capacity vs. cycle number obtained upon galvanostatic cycling (C/8 h rate) at 30 °C of LiCoPC /Li cells comprising the electrolyte composition containing 1 wt.-% TMB in 1 M UPF6/EC-DMC 1 :1 (full and open triangles, comparative) and of LiCoPC /Li cells comprising the electrolyte composition containing 1wt.-% of TMB in 1 M
  • Fig. 6 shows the discharge capacity vs. cycle number obtained upon galvanostatic cycling (C/8 rate) of LiCoPC cathode against Si-anodes at 30°C.
  • Electrolyte solution compositions were 1 M LiPFe/FEC-DMC 1 :4 without TMB (open circles) and with the addition of 1 wt.-% TMB (full circles).
  • the present invention relates to a lithium ion secondary battery comprising:
  • a cathode comprising a cathode active material selected from LiCoP0 4 ;
  • an anode comprising an anode active material that can reversibly occlude and release lithium ions
  • a non-aqueous electrolyte comprising at least one lithium salt and at least one nonaqueous organic solvent selected from fluorinated carbonates.
  • electrolyte (iii) in lithium ion secondary batteries comprising a cathode active material selected from LiCoP0 4 .
  • Another object of the pre- sent invention is a non-aqueous electrolyte comprising at least one lithium salt, at least one non-aqueous organic solvent selected from fluorinated carbonates and at least one optionally fluorinated boroxine of formula (I) as defined below and its use in lithium ion secondary batteries comprising a cathode active material selected from LiCoP0 4 .
  • the inventive secondary lithium ion batteries comprising LiCoP0 4 as cathode active material and fluorinated carbonate-based electrolyte solutions show a significantly better capacity retention and higher coulomb efficiency, compared with those of secondary lithium ion batteries comprising only the non-fluorinated carbonate-based electrolyte solution as shown in the experiments.
  • the stability of the LiCoP0 4 cathode in a lithium ion secondary battery in the delithiated state is significantly improved by the addition of a fluorinated carbonate to the electrolyte solution, due to the fact that the fluorinated carbonate forms a surface protective film on the
  • inventive lithium ion secondary batteries A further improvement of the capacity retention and coulomb efficiency of the inventive lithium ion secondary batteries is achieved by addition of an optionally fluorinated boroxine of formula (I) as defined below.
  • inventive electrolyte comprising at least one lithium salt, at least one non-aqueous organic solvent selected from fluorinated carbonates and at least one optionally fluorinated boroxine of formula (I) in lithium ion batteries comprising a cathode active material selected from LiCoP0 4 leads to better capacity retention of such batteries.
  • Example 1 the capacity retention and coulomb efficiency of the LiCoP0 4 /Li cells were further improved by increasing the active cathode mass : electrolyte vol- ume ratio, i.e. decreasing the volume of the electrolyte solution in the cells.
  • a similar increase of the active cathode mass : electrolyte volume ratio of the non-fluorinated carbonate- based electrolyte solution resulted in a modest improvement only in the capacity retention of the cells, along with a decrease of the irreversible capacity of those cells.
  • the invention is described in detail.
  • lithium ion battery means a rechargeable electrochemical cell wherein during discharge lithium ions move from the negative electrode (anode) to the positive electrode (cathode) and during charge the lithium ions move from the positive electrode to the negative electrode, i.e. the charge transfer is performed by lithium ions.
  • lithium ion batteries comprise a cathode containing as cathode active material a lithium ion- containing transition metal compound, for example transition metal oxide compounds with layer structure like UC0O2, LiNi02, and LiMn02, or transition metal phosphates having olivine structure like LiFeP0 4 and LiMnP0 4 , or lithium-manganese spinels which are known to the person skilled in the art in lithium ion battery technology.
  • transition metal oxide compounds with layer structure like UC0O2, LiNi02, and LiMn02 transition metal phosphates having olivine structure like LiFeP0 4 and LiMnP0 4
  • lithium-manganese spinels which are known to the person skilled in the art in lithium ion battery technology.
  • cathode active material denotes the electrochemically active material in the cathode, e.g. the transition metal oxide intercalating/deintercalating the lithium ions during
  • the cathode active material contains more or less lithium ions.
  • anode active material denotes the electrochemically active material in the anode, e.g. carbon intercalating/deintercalating the lithium ions during charge/discharge of the battery.
  • the cathode active material is selected from LiCoP0 4 .
  • the cathode may also be referred to as LiCoP0 4 cathode.
  • the LiCoP0 4 may be doped with Fe, Mn, Ni, V, Mg, Al, Zr, Nb, Tl, Ti, K, Na, Ca, Si, Sn, Ge, Ga, B, As, Cr, Sr, or rare earth elements, i.e., a lanthanide, scandium and yttrium.
  • LiCoP0 4 with olivine structure is particularly suited according the present invention due to its high operating voltage (red-ox potential of 4.8 V vs.
  • the LiCoP0 4 does not contain further cations and anions in significant amounts. Many elements are ubiquitous. For example, sodium, potassium and chloride are detectable in certain very small proportions in virtually all inorganic materials. In the context of the present invention, proportions of less than 0.5 % by weight of cations or anions are disregarded, i.e. amounts of cations or anions below 0.5 % by weight are regarded as nonsignificant. Any LiCoPC comprising less than 0.5 % by weight of sodium is thus considered to be sodium-free in the context of the present invention. Correspondingly, any LiCoPC compris- ing less than 0.5% by weight of sulfate ions is considered to be sulfate-free in the context of the present invention.
  • the cathode may further comprise electrically conductive materials like electrically conductive carbon and may further comprise usual components like binders.
  • electrically conductive materials like electrically conductive carbon
  • binders Compounds suited as electri- cally conductive materials and binders are known to the person skilled in the art.
  • the cathode may comprise carbon in a conductive polymorph, for example selected from graphite, carbon black, carbon nanotubes, graphene or mixtures of at least two of the aforementioned substances.
  • the cathode may comprise one or more binders, for example one or more organic polymers like polyethylene, polyacrylonitrile, polybutadiene, polypropylene, poly- styrene, polyacrylates, polyvinyl alcohol, polyisoprene and copolymers of at least two comono- mers selected from ethylene, propylene, styrene, (meth)acrylonitrile and 1 ,3-butadiene, especially styrene-butadiene copolymers, and halogenated (co)polymers like polyvinlyidene chloride, polyvinly chloride, polyvinyl fluoride, polyvinylidene fluoride (PVdF), polytetrafluoroethylene, copolymers of tetrafluoroethylene and hexafluoropropylene, copolymers of tetrafluoroethylene and vinylidene fluoride and polyacrylnitrile.
  • binders for
  • the cathode comprises a LiCoPC /C composite material.
  • the preparation of a suited cathode comprising a LiCoPC /C composite material is described in Markevich et al., Electrochem. Comm., 2012, 15, 22-25.
  • the cathode may comprise a current collector which may be a metal wire, a metal grid, a metal web, a metal sheet, a metal foil or a metal plate.
  • a suited metal foil is aluminum foil.
  • the cathode has a thickness of from 25 to 200 ⁇ , preferably of from 30 to 100 ⁇ , based on the whole thickness of the cathode with- out the thickness of the current collector.
  • electrolyte (iii) functions as a medium that transfers lithium ions participated in the electrochemical reaction taking place in the battery.
  • the lithium salt(s) present in the electrolyte are usually solvated in the non-aqueous organic solvent.
  • Electrolyte (iii) is also referred to as electrolyte solution according to the present invention.
  • Organic solvents used in lithium ion secondary batteries, in general, and in the secondary battery of the present invention and in the inventive electrolyte in particular have a high dielectric constants and a low viscosity, and therefore increase ionic dissociation by promoting ionic conductance.
  • Electrolyte (iii) comprises at least one fluorinated carbonate.
  • the at least one fluorinated carbonate is usually selected from cyclic and linear carbonates which are partially or fully fluorinated and mixtures thereof.
  • linear fluorinated carbonates are partially or fully fluori- nated dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate and ethylmethyl carbonate.
  • cyclic fluorinated carbonates are partially or fully fluorinated ethylene carbonate and propylene carbonate.
  • Partially fluorinated means, that only a part of the substitutable hydrogen atoms of the carbonate is substituted by F, totally fluorinated means, that all substitutable hydrogen atoms of the carbonate are substituted by F.
  • the partially or fully fluorinated dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, and ethylmethyl carbonate, ethylene carbonate, or propylene carbonate may be substituted with 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, or 14 fluorine atoms.
  • the fluorinated carbonates are selected from mono-, di-, tri-, tetra-, penta-, or hexa- fluorinated dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, ethylmethyl carbonate, ethylene carbonate, propylene carbonate, and mixtures thereof.
  • fluorinated dimethyl carbonates are fluoromethyl methyl carbonate, difluoromethyl methyl carbonate, trifluoromethyl methyl carbonate, bis(fluoromethyl) carbonate, bis(difluoro)methyl carbonate, and bis(trifluoro)methyl carbonate.
  • fluorinated ethylmethyl carbonates are 2-fluoroethylmethyl carbonate, ethylfluoromethyl carbonate, 2,2-difluoroethylmethyl carbonate, 2-fluoroethylfluoromethyl carbonate, ethyldifluoromethyl carbonate, 2,2,2-trifluoroethylmethyl carbonate, 2,2- difluoroethylfluoromethyl carbonate, 2-fluoroethyldifluoromethyl carbonate, and ethyltrifluorome- thyl carbonate.
  • fluorinated diethyl carbonates are ethyl-(2-fluoroethyl) carbonate, ethyl- (2,2-difluoroethyl) carbonate, bis(2-fluoroethyl) carbonate, ethyl-(2,2,2-trifluoroethyl) carbonate, 2,2-difluoroethyl-2'-fluoroethyl carbonate, bis(2,2-difluoroethyl) carbonate, 2,2,2-trifluoroethyl-2'- fluoroethyl carbonate, 2,2,2-trifluoroethyl-2',2'-difluoroethyl carbonate, and bis(2,2,2- trifluoroethyl) carbonate.
  • fluorinated ethylene carbonates are monofluorinated ethylene carbonate, 4,4-difluoroethylene carbonate, and 4,5-difluoroethylene carbonate.
  • fluorinated propylene carbonates are monofluorinated propylene carbonate, 5,5-difluoropropylene carbonate, and 4,5-difluoropropylene carbonate.
  • the cyclic fluorinated carbonate is monofluorinated ethylene carbonate.
  • the non-aqueous organic solvent composing the electrolyte solution in the lithium ion secondary battery of the present invention comprises a mixture of a linear fluorinated carbonate and a cyclic fluorinated carbonate.
  • the electrolyte (iii) further comprises at least one nonaqueous organic solvent selected from non-fluorinated carbonates.
  • the non-fluorinated carbonates may be selected from cyclic and linear carbonates and mixtures thereof.
  • linear carbonates are dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate and ethylmethyl carbonate.
  • cyclic carbonates are ethylene carbonate, propylene carbonate, butylene carbonate and pentylene carbonate.
  • the at least one non-fluorinated carbonate is selected from dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, ethylene carbonate, propylene carbonate and mixtures thereof.
  • the weight ratio between the fluorinated carbonates and the non-fluorinated carbonates present in said electrolyte (iii) as described above may be in the range of 1 :200 to 1 :1 , preferably 1 :100 to 1 :2, more preferably 1 :50 to 1 :2, most preferably 1 :25 to 1 :3, in particular in the range of from more than 1 :9 up to 1 :3 by weight, respectively.
  • a mixture of at least two carbonates is usually used, wherein one of said carbonates has a high dielectric constant and viscosity, and another one of said at least one solvent has a low dielectric constant and viscosity.
  • such mixtures consist of a cyclic carbonate(s) and a linear carbonate(s), wherein the ratio between the cyclic and linear carbonates in the mixture is determined so as to obtain a desired dielectric constant and viscosity.
  • Preferred cyclic carbonate ⁇ ) : linear carbonate(s) ratios are in a range of 1 :1 to 1 :9, e.g., 1 :1 , 1 ;2, 1 :3, 1 :4, 1 :5, 1 :6, 1 :7, 1 :8 and 1 :9, respectively, by volume.
  • a sole fluorinated cyclic carbonate such as a fluorinated propylene carbonate may be used.
  • electrolyte (iii) in the lithium ion secondary battery of the present invention comprises (a) a mixture of a linear fluorinated carbonate and a cyclic fluorinated carbonate.
  • said non-aqueous organic solvent comprises (b) a mixture of a linear fluorinated carbonate and a cyclic non-fluorinated carbonate, and in further embodiments, said non-aqueous organic solvent comprises (c) a mixture of a linear non-fluorinated carbonate and a cyclic fluorinated carbonate.
  • the electrolyte (iii) in the lithium ion secondary battery of the present invention comprises a mixture of a linear non-fluorinated carbonate and a cyclic fluorinated carbonate
  • the ratio be- tween the cyclic fluorinated carbonate and the linear non-fluorinated carbonate in the electrolyte (iii) may be in a range of 1 :200 to 1 :1 by weight, preferably 1 :100 to 1 :2 by weight, more preferably 1 :50 to 1 :2 by weight, most preferably 1 :25 to 1 :3 by weight, even more preferred in the range of from more than 1 :9 up to 1 :3, respectively.
  • said cyclic fluorinated carbonate is fluoroethylene carbonate or fluoropropylene carbonate, preferably fluo- roethylene carbonate.
  • the electrolyte (iii) of the inventive lithium ion secondary battery comprises at least one optionally fluorinated boroxine of formula (I)
  • R 1 , R 2 , and R 3 are independently from each other are selected from (Ci-C6)alkyl, (Ci- C6)alkoxy, (C5-C7)aryl, and (C5-C7)aryloxy, and wherein alkyl, alkyloxy, aryl and aryloxy may be independently from each other substituted by one or more substituents selected from F, (Ci- C6)alkyl, (Ci-Ce)alkoxy, (C5-C7)aryl, and (C5-C7) aryloxy and each alkyl, alkoxy, aryl, and aryloxy may be substituted by one or more F.
  • (Ci-C6)alkyl typically means a straight or branched hydrocarbon radical having 1 -6 carbon atoms and includes, e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec- butyl, isobutyl, tert-butyl, n-pentyl, iso-pentyl, 2,2-dimethylpropyl, n-hexyl, iso-hexyl and the like.
  • (Ci-C6)alkoxy refers to a group of the general formula -0-(Ci- C6)alkyl. Preferred are -0-(Ci-C3)alkyl groups, more preferred are methoxy or ethoxy.
  • (C5-C7)aryl denotes a 5- to 7-membered aromatic cycle.
  • a preferred (C5-C7)aryl is phenyl.
  • (C5-C7) aryloxy as used herein means a group of the general formula -0-(C5-C7)aryl like phenoxy.
  • Examples of (Ci-Ce)alkyl substituted by one or more F are CH2F, CHF2, CF3, CH2CH2F, CH2CHF2, CH2CF3, CHFCH2F, CHFCHF2, CHFCFs, CF2CH2F, CF2CHF2, CF2CF3, and so on.
  • Examples of (Ci-Ce)alkyloxy substituted by one or more F are OCH2CH2F, OCH2CHF2,
  • (C 5 -C 7 )aryl substituted by one or more F are 2-, 3- and 4-mono-F-phenyl, 2,3-di-F-phenyl, 2,4-di-F-phenyl and 2,4,6-tri-F-phenyl.
  • Examples of (C5-C7) aryloxy substituted by one or more F are 2-, 3- and 4-mono-F-phenoxy, 2,3-di-F-phenoxy, 2,4-di-F-phenoxy and 2,4,6-tri-F-phenoxy.
  • boroxine of formula (I) may be substituted by one or more F. If the boroxine is substituted by one or more F, the boroxine may be partially or fully substituted by F, i.e. partially or fully fluorinated. For example, the boroxine may be substituted with 1 to 39 F, in particular with 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14 or 15 F.
  • Non-limiting examples of optionally fluorinated boroxines of formula (I) are optionally fluorinated tri(Ci-C6)alkyl-boroxines, optionally fluorinated tri(Ci-C6)alkoxy-boroxines, optionally fluorinated tri(C5-C7)aryl-boroxines, and optionally fluorinated tri(C5-C7)aryloxy-boroxines.
  • Non-limiting examples of non-fluorinated tri(Ci-C6)alkyl-boroxine according to the invention include, without being limited to, trimethylboroxine (TMB), triethylboroxine, tripropylboroxine, triisopropylboroxine, tributylboroxine, triisobutylboroxine, tripentylboroxine, triisopentylboroxine, trihexylboroxine, and triisohexylboroxine; and non-limiting examples of non-fluorinated tri(Ci- C6)alkoxy-boroxine according to the invention include trimethoxyboroxine, triethyxoboroxine, tripropyloxyboroxine, triisopropyloxy boroxine, tributoxyboroxine, triisobutoxyboroxine, tripen- tyloxyboroxine, triisopentyloxyboroxine, trihexyloxyboroxine or triisohe
  • Non- limiting examples of fluorinated tri(Ci-C6)alkyl-boroxines are the fluorinated derivatives of the non-fluorinated tri(Ci-C6)alkyl-boroxines mentioned above which are substituted by 1 , 2, 3, 4, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, or 15 F like tri(monofluoromethyl)boroxine,
  • fluorinated (Ci-C6)alkoxy-boroxines are the fluorinated derivatives of the above mentioned non-fluorinated (Ci-C6)alkoxy-boroxines which are substituted by 1 , 2, 3, 4, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, or 15 F like
  • Non-limiting examples of non-fluorinated tri(C5-C7)aryl-boroxines and of tri(C5-C7)aryloxy- boroxines are triphenylboroxine and triphenoxyboroxine, respectively.
  • Non-limiting examples of fluorinated tri(C5-C7)aryl-boroxines are tri(2-F-phenyl)boroxine, tri(3-F-phenyl)boroxine, tri(4-F- phenyl)boroxine, tri(2,3-di-F-phenyl)boroxine, tri(2,4-di-F-phenyl)boroxine, and tri(2,4,6-tri-F- phenyl)boroxine
  • non-limiting examples of tri(C5-C7)aryloxy-boroxines are, tri(2-F- phenoxy)boroxine, tri(3-F-phenoxy)boroxine, tri(4-F-phenoxy)boroxine, tri(2,3-di-F-
  • the concentration of the optionally fluorinated boroxine of formula (I) in electrolyte (iii) com- prised in the inventive lithium ion secondary battery is usually 0.1 % to 5% by weight, based on the total wheight of the electrolyte solution, preferably 0.1 % to 2% by weight and most preferred 0.25% to 2% by weight.
  • electrolyte (iii) further comprises trimethylboroxine.
  • electrolyte (iii) comprises at least one compound of general formula (II)
  • R 4 is cyclohexyl or (hetero)aryl, which may be substituted by one or more substituent selected independently from each other from F, CI, Br, I, and (C1-C6) alkyl, wherein (C1-C6) alkyl may be substituted by one or more substituent selected independently from each other from F, CI, Br and I; and
  • R 5 , R 6 , R 7 , R 8 , and R 9 may be same or different and are independently from each other selected from H, F, CI, Br, I, (Ci-Ce) alkyl, wherein (Ci-Ce) alkyl may be substituted by one or more substituent selected independently from each other from F, CI, Br and I.
  • (Ci-Ce) is defined as above.
  • (Hetero)aryl means (C5-C7) aryl or (C5-C7) heteroaryl.
  • Heteroaryl means aryl wherein 1 to 3 C atoms are replaced independently by N, S or O.
  • Aryl may be phenyl, heteroaryl may be furanyl or pyridyl.
  • Preferred compounds of formula (I) are biphenyl and cyclohexylphenyl.
  • a compound of general formula (II) is present in electrolyte (iii)
  • its concentration is usually 0.01 to 5 wt.-%, based on the total weight of the electrolyte, preferably 0.1 to 2 wt.-% and most preferred 0.1 to 0.5 wt.-%.
  • electrolyte (iii) contains at least one optionally fluorinated boroxine of formula (I) and at least one compound of general formula (II).
  • the con- centration of the at least one optionally fluorinated boroxine of formula (I) is usually 0.1 % to 5% by weight, based on the total weight of the electrolyte solution, preferably 0.1 % to 2% by weight and most preferred 0.25% to 2% by weight and the concentration of the at least one compound of general formula (II) is usually 0.01 to 5 wt.-%, based on the total weight of the electrolyte, preferably 0.1 to 2 wt-% and most preferred 0.1 to 0.5 wt.-%.
  • Electrolyte (iii) comprises at least one lithium salt.
  • the lithium salt functions as a source of lithium ions, enabling basic operations of the lithium ion secondary battery and promoting movement of lithium ions between the cathode and anode.
  • Suited lithium salts are for example of LiPF 6 , LiBF 4 , LiSbFe, LiAsF 6 , UCIO4, UCF3SO3 or UC4F9SO3 and mixtures thereof.
  • the lithium salt in electrolyte (iii) is LiPF6.
  • said lithium salt is a mixture of LiPFewith one or more of L1BF4, LiSbF6, LiAsF6, UCIO4, UCF3SO3 or UC4F9SO3 or mixtures thereof.
  • the concentration of the lithium salt should preferably be in the range of 0.1 to 2.0 M.
  • concentration less than 0.1 M the conductivity of the electrolyte solution is decreased and the performance thereof may thus be degraded.
  • a lithium salt in a concentration higher than 2.0 M the viscosity of the electrolyte solution is increased and the movement of the lithium ions within said solution may thus be reduced.
  • the lithium ion secondary battery of the present invention in any of the configurations defined above, comprises an electrolyte comprising a solution of LiPF6 in a non- aqueous organic solvent comprising dimethyl carbonate and mono-fluorinated ethylene carbonate.
  • said electrolyte solution further comprises TMB, preferably wherein the amount of the TMB in said solution is 0.5% to 2% by weight.
  • the ratio between the mono-fluorinated ethylene carbonate and the dimethyl carbonate in said organic solvent is 1 :4, by weight, respectively. More particular such embodiments are those wherein the ratio between the mono-fluorinated ethylene carbonate and the dimethyl carbonate in said organic solvent is 1 :4, by weight, and the amount of TMB in the electrolyte solution is about 0.5% to 1 % by weight.
  • inventive lithium ion secondary batteries and inventive electrolyte (iii) show improved properties without the presence of vinylene carbonate.
  • electrolyte (iii) does not contain vinylene carbonate. This means in particular no vinylene carbonate is added to electrolyte (iii).
  • the concentration of vinylene carbonate in electrolyte (iii) of the inventive batteries is below the detection limit of vinylene carbonate.
  • the anode comprised within the lithium ion secondary battery of the present invention compris- es an anode active material that can reversibly occlude and release lithium ions.
  • Particular anode active materials that can be used include, without being limited to, carbonaceous material that can reversibly occlude and release lithium ions.
  • Carbonaceous materials suited are crystalline carbon such as a graphite material, more particularly, natural graphite, graphitized cokes, graphitized MCMB, and graphitized MPCF; amorphous carbon such as coke, mesocarbon mi- crobeads (MCMB) fired below 1500°C, and mesophase pitch-based carbon fiber (MPCF); hard carbon and carbonic anode active material (thermally decomposed carbon, coke, graphite) such as a carbon composite, combusted organic polymer, and carbon fiber.
  • Further anode active materials are lithium metal, lithium alloys and materials containing an element capable of forming an alloy with lithium.
  • Non-limiting examples of materials containing an element capable of forming an alloy with lithium include a metal, a semimetal, or an alloy thereof. It should be understood that the term "alloy” as used herein refers to both alloys of two or more metals as well as alloys of one or more metals together with one or more semimetals. If an alloy has metallic properties as a whole, the alloy may contain a nonmetal element. In the texture of the alloy, a solid solution, a eutectic (eutectic mixture), an intermetallic compound or two or more thereof coexist.
  • metal or semimetal elements examples include, without being limited to, titanium (Ti), tin (Sn), lead (Pb), aluminum, indium (In), zinc (Zn), antimony (Sb), bis- muth (Bi), gallium (Ga), germanium (Ge), arsenic (As), silver (Ag), hafnium (Hf), zirconium (Zr) yttrium (Y), and silicon (Si).
  • Metal and semimetal elements of Group 4 or 14 in the long-form periodic table of the elements are preferable, and especially preferable are titanium, silicon and tin, in particular silicon.
  • tin alloys include ones having, as a second constituent element other than tin, one or more elements selected from the group consisting of silicon, magnesium (Mg), nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium (Ti), germanium, bismuth, antimony and chromium (Cr).
  • silicon alloys include ones having, as a second constituent element other than silicon, one or more elements selected from the group consisting of tin, magnesium, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony and chromium.
  • Silicon as anode active material that can reversibly occlude and release lithium ions may be used in different forms, e.g. in the form of nanowires, nanotubes, nanoparticles, films, nanopo- rous silicon or silicon nanotubes.
  • the silicon may be deposited on a current collector.
  • the current collector may be a metal wire, a metal grid, a metal web, a metal sheet, a metal foil or a metal plate.
  • Preferred the current collector is a metal foil, e.g. a copper foil.
  • Thin films of silicon may be deposited on metal foils by any technique known to the person skilled in the art, e.g. by sputtering techniques.
  • the surface densitiy of the silicon in the thin films is in the region ranging from 0.2 mg/cm 2 to 2 mg/cm 2 .
  • the thickness of the silicon thin films is preferably 0.5 ⁇ up to 50 ⁇ , more preferred 1 ⁇ up to 20 ⁇ and most preferred 1 ⁇ up to 10 ⁇ .
  • One method for preparing anodes having a thin film of silicon is explicitly described in the examples.
  • the anode comprises a thin film of silicon. It is also possible to use a silicon/carbon composite as anode active material according to the present invention.
  • the anode active material present in the inventive lithium ion secondary battery is selected from carbonaceous material that can reversibly occlude and release lithium ions, particularly preferred the carbonaceous material that can reversibly occlude and release lithium ions is selected from crystalline carbon, hard carbon and amorphous carbon. In another preferred embodiment the anode active material present in the inventive lithium ion secondary battery is selected from silicon that can reversibly occlude and release lithium ions.
  • the anode and cathode may be made by preparing an electrode slurry composition by dispersing the electrode active material, a binder, a conductive material and a thickener, if desired, in a solvent and coating the slurry composition onto a current collector.
  • the current collector may be a metal wire, a metal grid, a metal web, a metal sheet, a metal foil or a metal plate.
  • Preferred the current collector is a metal foil, e.g. a copper foil or aluminum foil.
  • the capacity retention and coulomb effi- ciency of the LiCoP0 4 /Li cells were further improved.
  • the volume of electrolyte (iii) in the lithium ion secondary battery of the present invention in any one of the configurations defined above, is 10 ⁇ or less per 1 mg of the cathode active material, preferably about 5 ⁇ or less per 1 mg of the cathode active material and in particular about 1 ⁇ or less per 1 mg of the cathode active material.
  • the term "about” as used herein means within an accepta- ble error range for a particular value as determined by one of ordinary skill in the art, which will depend in part on how the value is measured or determined, i.e., the limitations of the measurement system.
  • “about” can mean a range of up to 20%, preferably up to 10%, more preferably up to 5%, and still more preferably up to 1 % of a given value.
  • “about” meaning within an acceptable error range for the particular value should be assumed.
  • the lithium ion secondary battery of the present invention usually includes a separator that prevents a short between the cathode and anode.
  • a separator may be made of a polymer membrane such as a polyolefin, polypropylene or polyethylene membrane, a multi-membrane thereof, a micro-porous film, or a woven or non-woven fabric.
  • the lithium secondary battery of the present invention may be configured in various types, such as a cylindrical, pouch or rectangular shaped battery.
  • a unit battery having a structure of cathode/separator/anode, a bi-cell having a structure of cathode/separator/anode/separator/cathode, or a battery stack including a plurality of unit batteries may be formed using above-described lithium secondary battery including the electrolyte, cathode, anode and separator.
  • the lithium ion secondary battery of the present invention has significantly improved properties, more particularly, improved capacity retention property and faradaic efficiency.
  • the capacity retention of a lithium ion secondary battery is the fraction of the full capacity avail- able from a battery under specified conditions of discharge after it has been cycled for a particular number of cycles.
  • the faradaic/coulomb efficiency of a lithium ion secondary battery is the ratio of discharge capacity: charge capacity, expressed in percents and calculated according to the formula measured as [(discharge capacity/charge capacity)* 100].
  • the term "improving the capacity retention property and faradaic efficiency of a lithium ion secondary battery" as used herein thus means that during the cycling the battery retains more portion of its discharge (faradaic) capacity and, at the same time, less charge is expended in parasitic reactions.
  • the present invention refers to a non-aqueous electrolyte comprising at least one lithium salt, at least one fluorinated carbonate and comprising at least one optionally fluori- nated boroxine of formula (I).
  • inventive electrolyte are the same as described above for electrolyte (iii) and may be used in the amounts as given for electrolyte (iii).
  • inventive electrolyte may contain further additives as described above for electrolyte (iii) and may have any one of the features as described above for the electrolyte (iii) comprised in the inventive Li ion secondary battery provided that the electrolyte contains at least one optionally fluorinated boroxine of formula (I), at least one lithium salt, and at least one fluorinated carbonate.
  • inventive electrolyte may for example further comprise at least one non- aqueous organic solvent selected from non-fluorinated carbonates as described above and/or may further comprise at least one compound of formula (II) as described above.
  • the inventive electrolyte is especially useful as electrolyte for lithium ion batteries comprising L1C0PO4 as cathode active material.
  • Lithium ion secondary batteries comprising L1C0PO4 as cathode active material and comprising the inventive electrolyte show improved capacity retention properties and faradaic efficiencies in comparison with such lithium ion secondary batteries comprising an electrolyte containing only a partially fluorinated carbonate or only boroxine.
  • inventive electrolyte comprising at least one lithium salt, at least one fluorinated carbonate and comprising at least one optionally fluorinated boroxine of formula (I) as electrolyte for lithium ion batteries comprising UC0PO4 as cathode active material
  • inventive electrolyte in lithium ion batteries comprising UC0PO4 as cathode active material wherein the anode active material is selected from group consisting of carbonaceous material that can reversibly occlude and release lithium ions and from silicon that can reversibly occlude and release lithium ions is especially preferred.
  • the present invention thus relates to a method of using the inventive electrolyte and improving the capacity retention property and faradaic efficiency of a lithium ion secondary battery, said method comprising placing the inventive electrolyte comprising at least one lithium salt, at least one fluorinated carbonate and comprising at least one optionally fluorinated boroxine of formula (I), into a lithium ion secondary battery comprising a cathode comprising a cathode active material selected from L1C0PO4 and an anode comprising an anode active material that can reversibly occlude and release lithium ions.
  • the inventive electrolyte placed into the lithium ion secondary battery may comprise further additives and features as described above.
  • the present invention relates to a method of improving the capacity retention property and faradaic efficiency of a lithium ion secondary battery, said method comprising placing the electrolyte as described above into a lithium ion secondary battery comprising a cathode comprising a cathode active material selected from L1C0PO4; and an anode comprising an an- ode active material that can reversibly occlude and release lithium ions.
  • plating the electrolyte into a lithium ion secondary battery is intended to include all techniques to place, insert or apply the electrolyte in or to the lithium secondary battery known to the person skilled in the art like injecting the electrolyte into the assembled battery or immersing one or more components of the cell like anode, cathode or separator in the electrolyte solution before assembling of the battery.
  • Carbon-coated LiCoPC powder was prepared by hydrothermal synthesis as described in Markevich et al., Electrochem. Comm., 2012, 15, 22-25, and had an orthorhombic, olivine-like structure as described in X-ray Powder Diffraction Data Files 00-032-0552 (X-ray Powder Diffraction Data Files 00-032-0552, American Society for Testing Materials).
  • the carbon content in the powder was determined by an Eager, Inc. Model 200 analyzer and comprised 1 .53 % by weight.
  • the surface area of a sample of the powder prepared was calculated using the Brunau- er-Emmett-Teller (BET) equation from the adsorption isotherm of N2 gas at 77 K using an Auto- sorb-1 -MP apparatus (Quantachrome Corporation), and was equal to 1 1.7 m 2 /g.
  • High-resolution scanning electron microscopy (HRSEM) images and energy-dispersive X-ray spectroscopy (EDS) data were obtained using a FEI xHR- SEM Magellan 400L microscope, equipped with the Oxford Industries INCAx-sight energy dispersive spectrometer.
  • X-ray diffraction (XRD) patterns were recorded with a BRUKER-AXS, D8-Advance diffractometer using Cu ⁇ radiation.
  • Fig. 1 shows SEM image and XRD pattern of the carbon-coated LiCoPC olivine powder prepared, consisting of rods having a diameter of 50 to 200 nm and a length of about 1 ⁇ .
  • the cathode sheets were fabricated by spreading a slurry (a suspension of LiCoPC powder and carbon black in a PVdF/N-methylpyrrolidon-solution) on an aluminum foil current collector with a doctor blade device.
  • a slurry a suspension of LiCoPC powder and carbon black in a PVdF/N-methylpyrrolidon-solution
  • the electrodes contained 2-3 mg of active mass.
  • the electrolyte solutions were 1 M of LiPF6 in either ethylenecarbonate (EC)+dimethylcarbonate (DMC) 1 :1 (EC-based) or fluoroethylenecarbonate (FEC)+DMC 1 :4 (FEC-based) mixtures (both Li-battery grade from Merck, KGaA).
  • Trimethyl boroxine (TMB, 99%) was purchased from Al- drich.
  • Silicon thin film electrodes were prepared by DC magnetron sputtering (Angstrom Sciences Inc., USA) of n-type silicon (99.999%, Kurt J. Lesker, USA), at a pressure of about 5x10-3 Torr of argon (99.9995%) onto the roughened copper foil (Oxygenfree, SE-Cu58, Schlenk Metallfolien GmbH & Co. KG) as described in R. Elazari, et al.; Electrochem. Comm. 2012, 14 , 21 -24.
  • the surface density of the obtained a-Si film was 0.39 mg/cm 2 ( ⁇ 1 .8 ⁇ thick).
  • the film Si electrodes Before the use of the film Si electrodes as anodes in full cells, they were galvanostatically pre-passivated and partially pre-lithiated in two electrode coin type cells containing Li counter electrodes. Two-electrode cells comprising silicon film electrodes, PE separator (Setela Tonen, Japan), an electrolyte solution, and Li counter electrodes were assembled in a glove box filled with pure argon and sealed in 2032 coin-cells (NRC, Canada). After that five galvanostatic cycles of Si electrodes were performed with the voltage cut-off limits of 10mV and 1 .2V and current density of 120 mA/g in the first cycle and 600 mA g in four subsequent cycles.
  • the Si electrodes were discharged galvanostatically down to 50 mV vs. Li/Li+, withdrawn from Si/Li cells in the glove box and used for the preparation of the complete cells.
  • a Raman spectrum of the Si anode was measured using a Raman microscope spectrometer (Labram, HR-800/Jobin Yvon Horiba) with a 632.8 nm line of a He-Ne laser with a power attenuated to O.l mWat the samples' surface. The result is shown in Fig. 1 b revealing the absence of the peak at 520 cm- 1 , which is characteristic of crystalline silicon. Thus, it may be concluded that the Si film is totally amorphous.
  • Two-electrode cells comprising LiCoPC electrodes, polyethylene (PE) separator (Setela Tonen, Japan), an electrolyte solution and Li foil negative electrodes or preliminary passivated and partially lithiated silicon film negative electrodes were assembled in a glove box filled with pure argon and sealed in 2032 coin-cells (NRC, Canada). Galvanostatic cycling of Si/Li cells (pre- passivation procedure), LiCoPC /Li and LiCoPC /Si cells was carried out at 30°C using an Arbin model BT2000 battery tester (Arbin Instruments, USA).
  • X-ray photoelectron spectroscopy (XPS) measurements of the cycled and thoroughly washed with DMC electrodes were performed using the AXIS-HS system (Kratos Analytical, Inc., England) using monochromatic Al Ka radiation. All binding energies (BE) were corrected with re- spect to the binding energy value of the C 1 s at 285 eV.
  • XPS X-ray photoelectron spectroscopy
  • Example 1 The cycling of LiCoPC /Li cells in EC-based vs. FEC-based electrolyte solution
  • Example 2 Characterization of LiCoPC /C cathodes cycled for an equal period of time in EC- and FEC-based electrolyte solutions
  • XPS spectra of LiCoPC /C cathodes cycled for an equal period of time in EC- and FEC-based electrolyte solutions, as well as in the FEC-based electrolyte with the addition of 0.5 wt.-% of TMB are shown in Fig. 4, and the surface chemical compositions of these electrodes are com- pared in Table 1.
  • the volume of the electrolyte solution was 5 ⁇ /mg of electrode active mass.
  • the better was the performance of the cell the higher content of fluorine atoms was found on the surface of the cathode.
  • the atomic ratio F:0 equal to 0.35 in the case of the EC-based electrolyte grows up to 0.6 for the FEC-based solution and reaches 0.7 for the TMB-containing electrolyte.
  • the content of fluorine on the surface increases the content of cobalt reduces, indicating the formation of more perfect or thick surface film.
  • the lowest content of carbon on the surface of the electrode cycled in the EC-based solution may be explained by an exfoliation of the carbon coating film due to the dissolution of the underlying layer of the active LiCoPC material as was shown in Markevich et al., Electrochem. Comm., 2012, 15, 22-25.
  • Example 3 The cycling of LiCoPC /Li cells in EC-based and FEC-based electrolyte with TMB (comparative and inventive examples)
  • Electrolyte solution (e) (1 wt.-% TMB in 1 M LiPF 6 /EC-DMC 1 :1 ) is shown with full (charge) and open (discharge) triangles (comparative example).
  • Electrolyte solution (d) (1 wt.-% TMB in 1 M LiPFe/FEC-DMC 1 :1 ) is shown with full (charge) and open (discharge) circles (inventive example).
  • the addition of TMB to an EC-based electrolyte solution not containing FEC yields a lower discharge capacity of the LiCoPC /Li cell than the addition of TMB to the FEC-based electrolyte solution.
  • Example 4 The cycling of LiCoPC /Si cells in FEC-based electrolyte with and without TMB (inventive examples)
  • Electrolyte solution compositions were 1 M LiPFe/FEC-DMC 1 :4 without TMB (open circles) and with the addition of 1 % TMB (full circles). As can be seen the addition of TMB to an FEC-based electrolyte solution leads to a higher capacity of the cell.

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Abstract

La présente invention se rapporte à une batterie rechargeable au lithium-ion qui comprend du LiCoPO4. Une batterie rechargeable au lithium-ion comprend : (i) une cathode qui comprend un matériau actif de cathode sélectionné parmi le LiCoPO4; (ii) une anode qui comprend un matériau actif d'anode qui peut, de manière réversible, occlure et libérer des ions de lithium; et (iii) un électrolyte non aqueux qui comprend au moins un sel de lithium, au moins un solvant organique non aqueux sélectionné parmi les carbonates fluorés et au moins une boroxine facultativement fluorée.
PCT/EP2013/072485 2012-10-30 2013-10-28 Batterie rechargeable au lithium-ion qui comprend du lithium cobalt phosphate comme matériau actif de cathode WO2014067891A1 (fr)

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CN110034332B (zh) * 2019-03-20 2021-12-21 欣旺达电动汽车电池有限公司 一种低阻抗、循环寿命长的锂离子电池电解液及其制备方法
CN111883830A (zh) * 2020-07-24 2020-11-03 香河昆仑化学制品有限公司 一种锂离子电池电解液以及电池负极和电化学储能器件
CN111883830B (zh) * 2020-07-24 2023-05-12 香河昆仑新能源材料股份有限公司 一种锂离子电池电解液以及电池负极和电化学储能器件

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