WO2014114068A1 - Électrolyte organique non aqueux, procédé de préparation de celui-ci et batterie secondaire au lithium-ion - Google Patents

Électrolyte organique non aqueux, procédé de préparation de celui-ci et batterie secondaire au lithium-ion Download PDF

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WO2014114068A1
WO2014114068A1 PCT/CN2013/080350 CN2013080350W WO2014114068A1 WO 2014114068 A1 WO2014114068 A1 WO 2014114068A1 CN 2013080350 W CN2013080350 W CN 2013080350W WO 2014114068 A1 WO2014114068 A1 WO 2014114068A1
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aqueous organic
organic electrolyte
formula
lithium
ion secondary
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PCT/CN2013/080350
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Chinese (zh)
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王圣
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华为技术有限公司
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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
    • 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
    • H01M10/052—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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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

  • Non-aqueous organic electrolyte and preparation method thereof and lithium ion secondary battery The present application claims to be submitted to the Chinese Patent Office on January 28, 2013, the application number 201310031863.0, the invention name is "a non-aqueous organic electrolyte and The priority of the preparation method and the Chinese patent application of the lithium ion secondary battery is hereby incorporated by reference in its entirety.
  • the present invention relates to the field of lithium ion secondary batteries, and more particularly to a nonaqueous organic electrolyte and a method of preparing the same, and a lithium ion secondary battery. Background technique
  • the high-voltage positive electrode material has been reported to have a lithium-rich solid solution xLi 2 Mn0 3 ( lx)LiM0 2 and a spinel LiNio.sMn C ⁇ , etc., and the charging voltage is close to or higher than 5 V, but the matching non-aqueous organic electrolyte Existing reports.
  • a first aspect of embodiments of the present invention is directed to a non-aqueous organic electrolyte for solving a non-aqueous organic electrolyte in a prior art battery at a full charge high voltage (voltage greater than 4.5V).
  • the side reaction of the positive electrode active material is liable to cause a problem of a decrease in cycle performance, volume expansion, and discharge capacity of the lithium ion secondary battery.
  • the non-aqueous organic electrolyte still exhibits in a high voltage working environment of about 4.9V. Good cycle performance.
  • a second aspect of the embodiment of the present invention is to provide a method for producing the above nonaqueous organic electrolyte.
  • a third aspect of the embodiment of the invention is directed to a lithium ion secondary battery comprising the above nonaqueous organic electrolyte, which has a high energy density.
  • an embodiment of the present invention provides a non-aqueous organic electrolyte, comprising: a lithium salt; a non-aqueous organic solvent; and a non-aqueous organic electrolyte additive, wherein the non-aqueous organic electrolyte additive is of the formula (I) a non-aqueous organic electrolyte additive as shown and/or a non-aqueous organic electrolyte additive as shown in formula (II),
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are a straight or branched alkyl group of Cr ⁇ do, C ⁇ do Alkenyl group, Cr ⁇ do alkyne group or C 6 -C 14 aromatic group, or Ri, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are halogen-containing: Cr ⁇ a linear or branched alkyl group of do, an alkene group of Cu), an alkyne group of Cr ⁇ do or an aromatic group of C 6 to C 14 .
  • the non-aqueous organic electrolyte additive represented by the formula (I) in the embodiment of the present invention is a derivative of pyrophosphate, and the non-aqueous organic electrolyte additive represented by the formula (II) is pyrophosphite. derivative.
  • R 2 , R 3 and R 4 may be the same structure or different.
  • R 5 , R 6 , R 7 and R 8 may be the same structure or different.
  • R 2 , R 3 and R 4 are a mercapto group, an ethyl group, an ethyl trifluoromethyl group, a trifluoroethyl group, a perfluoroethyl group, a phenyl group, Benzyl, partially or perfluoro substituted phenyl.
  • R 2 , R 3 and R 4 may be the same structure or different.
  • R 5 , R 6 , R 7 and R 8 are an indenyl group, an ethyl group, a trifluoromethyl group, a trifluoroethyl group, a perfluoroethyl group. , phenyl, benzyl, partially or perfluoro substituted phenyl.
  • R 5 , R 6 , R 7 and R 8 may be the same structure or different.
  • Lithium salt is used as a carrier to ensure the basic operation of lithium ions in lithium ion secondary batteries, including but not limited to lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiC10 4 ), lithium tetrafluoroborate (LiBF 4 ), hexafluoride Lithium arsenate (LiAsF 6 ), lithium hexafluorosilicate (LiSiF 6 ), lithium tetraphenylborate (LiB(C 6 3 ⁇ 4 ) 4 ), lithium chloride (LiCl), lithium bromide (LiBr), lithium chloroaluminate ( LiAlCl 4 ), lithium bis(oxalate)borate (LiBOB), lithium trifluoromethanesulfonate (LiCF 3 S0 3 ), lithium perfluorobutyl sulfonate (LiC 4 F 9 S0 3 ), lithium fluorosulfonimide (
  • the final concentration of the lithium salt in the non-aqueous organic electrolyte is not limited and is usually from 0.5 to 2.0 mol/L.
  • the final concentration of the lithium salt in the non-aqueous organic electrolyte is from 0.7 to 1.6 mol/L.
  • the non-aqueous organic electrolyte of the embodiment of the present invention can simultaneously provide better lithium ion conductivity and lithium ion mobility.
  • the non-aqueous organic solvent is selected from solvents conventional in the art and may be one or more of aliphatic or cyclic carbonates, ethers, sulfones, nitriles, ionic liquids, and derivatives thereof, including but not limited to Y-butyl Lactone (GBL), ethylene carbonate (EC), diethyl carbonate (DEC), dinonyl carbonate (DMC), vinylene carbonate (VC), ethyl cerium carbonate (EMC), dipropyl carbonate ( DPC), propyl propyl carbonate (MPC), propylene carbonate (PC), decyl decanoate (MF), decyl acrylate (MA), decyl butyrate (MB) ethyl acetate (EP), ethylene sulfite Ester (ES), propylene sulfite (PS), sulfonium sulfide (DMS), diethyl sulfite (DES), tetra
  • the non-aqueous organic solvent accounts for 85% to 99.5% of the non-aqueous organic electrolyte
  • the non-aqueous organic electrolyte additive accounts for 0.5% to 15% of the non-aqueous organic electrolyte
  • the non-aqueous organic solvent accounts for 92% to 99% of the non-aqueous organic electrolyte
  • the non-aqueous organic electrolyte additive accounts for 1% to 8% of the non-aqueous organic electrolyte
  • the non-aqueous organic electrolyte further includes a functional auxiliary agent selected from the group consisting of a cyclic additive, a high temperature additive, a flame retardant additive, and an overcharge additive.
  • a functional auxiliaries include, but are not limited to, vinylene carbonate (VC), biphenyl, cyclohexylbenzene, 2,52 di-tert-butyl 21,42-dimethoxybenzene (DDB), thiophene, .
  • Dithiazine lithium carbonate, carbon dioxide, 1,3-propane sultone (PS), ethylene carbonate (FEC) and lithium tetrafluoroborate (LiBF 4 ), tridecyl phosphate, triethyl phosphate, triphenyl phosphate Ester, tributyl phosphate and phosphazene compounds.
  • the functional additive accounts for 0.1% to 15% of the non-aqueous organic electrolyte by mass fraction.
  • the non-aqueous organic electrolyte provided by the first aspect of the present invention can be used in a working environment of full charge high voltage (voltage above 4.5V), has excellent chemical stability and electrochemical stability, and can avoid high voltage.
  • the phenomenon of gas expansion under the lithium ion secondary battery, and the improvement of lithium ion II under high voltage The cycle performance and discharge capacity of the secondary battery.
  • non-aqueous organic electrolyte additive as shown in formula (I) and/or a non-aqueous one as shown in formula (II)
  • Part of the phosphorus-oxygen bond of the organic electrolyte additive is broken, and part of the phosphorus-containing fraction interacts with a product formed by oxidative decomposition of a non-aqueous organic solvent or a lithium salt to form an electron-conducting, ion-conducting phosphorus-containing element on the surface of the positive electrode active material.
  • the surface film covers the active site on the surface of the positive active material, blocks the direct contact between the active site on the surface of the positive active material and the non-aqueous organic electrolyte, and reduces the oxidation of the positive active material on the non-aqueous organic electrolyte, thereby improving The cycle performance of a lithium ion secondary battery at a high voltage, and the case where the volume expansion of the lithium ion secondary battery and the discharge capacity are prevented.
  • an embodiment of the present invention provides a method for preparing a non-aqueous organic electrolyte, comprising the steps of: dissolving a lithium salt in a non-aqueous organic solvent, and adding a non-aqueous organic electrolyte as shown in formula (I) Adding an additive and/or a non-aqueous organic electrolyte additive as shown in formula (II) to a non-aqueous organic electrolyte,
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are a straight or branched alkyl group of Cr ⁇ do, an alkene group of C ⁇ do, an alkyne group of Cr ⁇ do or C
  • R 7 and R 8 are halogen-containing: a straight or branched alkyl group of Cr ⁇ do, an alkene group of Cu), an alkyne group of CH ⁇ o or an aromatic group of C 6 to C 14 .
  • R 2 , R 3 and R 4 are a mercapto group, an ethyl group, an ethyl trifluoromethyl group, a trifluoroethyl group, a perfluoroethyl group, a phenyl group, Benzyl, partially or perfluoro substituted phenyl.
  • R 2 , R 3 and R 4 may be the same structure or different.
  • R 5 , R 6 , R 7 and R 8 are an indenyl group, an ethyl group, a trifluoromethyl group, a trifluoroethyl group, a perfluoroethyl group. , phenyl, benzyl, partially or perfluoro substituted phenyl.
  • R 5 , R 6 , R 7 and R 8 may be the same structure or different.
  • the preparation method of the non-aqueous organic electrolyte is carried out in an argon-filled glove box.
  • the lithium salt is dissolved in a non-aqueous organic solvent for a controlled temperature of 20 to 35 °C.
  • a non-aqueous organic solvent for a controlled temperature of 20 to 35 °C.
  • Lithium salt is used as a carrier to ensure the basic operation of lithium ions in lithium ion secondary batteries, including but not limited to lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiC10 4 ), lithium tetrafluoroborate (LiBF 4 ), hexafluoride Lithium arsenate (LiAsF 6 ), lithium hexafluorosilicate (LiSiF 6 ), lithium tetraphenylborate (LiB(C 6 3 ⁇ 4 ) 4 ), lithium chloride (LiCl), lithium bromide (LiBr), lithium chloroaluminate ( LiAlCl 4 ), lithium bis(oxalate)borate (LiBOB), lithium trifluoromethanesulfonate (LiCF 3 S0 3 ), lithium perfluorobutyl sulfonate (LiC 4 F 9 S0 3 ), lithium fluorosulfonimide (
  • the final concentration of the lithium salt in the non-aqueous organic electrolyte is not limited and is usually 0.5 to 2.0 mol/L.
  • the final concentration of the lithium salt in the non-aqueous organic electrolyte is from 0.7 to 1.6 mol/L.
  • the non-aqueous organic electrolyte of the embodiment of the present invention can simultaneously provide better lithium ion conductivity and lithium ion mobility.
  • the non-aqueous organic solvent is selected from solvents conventional in the art and may be one or more of aliphatic or cyclic carbonates, ethers, sulfones, nitriles, ionic liquids, and derivatives thereof, including but not limited to Y-butyl Lactone (GBL), ethylene carbonate (EC), diethyl carbonate (DEC), dinonyl carbonate (DMC), vinylene carbonate (VC), Ethyl carbonate (EMC), dipropyl carbonate (DPC), propyl propyl carbonate (MPC), propylene carbonate (PC), decyl decanoate (MF), decyl acrylate (MA), decyl butyrate (MB) ethyl acetate (EP), vinyl sulfite (ES), propylene sulfite (PS), sulfonium sulfide (DMS), diethyl sulfite (DES), tetrahydrofuran, an
  • the non-aqueous organic solvent accounts for 85% to 99.5% of the non-aqueous organic electrolyte
  • the non-aqueous organic electrolyte additive accounts for 0.5% to 15% of the non-aqueous organic electrolyte
  • the non-aqueous organic solvent accounts for 92% to 99% of the non-aqueous organic electrolyte
  • the non-aqueous organic electrolyte additive accounts for 1% to 8% of the non-aqueous organic electrolyte
  • non-aqueous organic compound as shown in formula (I) it is preferable to add a non-aqueous organic compound as shown in formula (I) to the preparation method of the non-aqueous organic electrolyte provided by the second aspect of the present invention.
  • a functional auxiliary agent selected from the group consisting of a cyclic additive, a high temperature additive, a flame retardant additive, and an overcharge additive
  • the functional auxiliaries include, but are not limited to, vinylene carbonate (VC), biphenyl, cyclohexylbenzene, 2, 52 di-tert-butyl 21,42 didecyloxybenzene (DDB), Thiophene, phenothiazine, lithium carbonate, carbon dioxide, 1,3-propane sultone, ethylene carbonate (FEC) and lithium tetrafluoroborate (LiBF 4 ), tridecyl phosphate, triethyl phosphate, triphenyl phosphat
  • the functional additive accounts for 0.1% to 15% of the non-aqueous organic electrolyte by mass fraction.
  • a method for preparing a non-aqueous organic electrolyte provided by a second aspect of the present invention provides a novel non-aqueous organic electrolyte, and the preparation method is simple.
  • an embodiment of the present invention provides a lithium ion secondary battery, including: a positive electrode, a negative electrode, a separator, a casing, and a non-aqueous organic electrolyte, the non-aqueous organic electrolyte, including: lithium salt, non-aqueous Have a solvent, and a non-aqueous organic electrolyte additive as shown in formula (I) and/or a non-aqueous organic electrolyte additive as shown in formula (II),
  • R 2 , R 3 , R 5 , R 6 , R 7 and R 8 are a straight or branched alkyl group of Cr ⁇ o, an alkene group of C ⁇ do, an alkyne group of Cr ⁇ do or C 6 ⁇
  • R 7 and R 8 are halogen-containing: a straight or branched alkyl group of Cr ⁇ do, an alkene group of Cu), an alkyne group of CH ⁇ o or an aromatic group of C 6 to C 14 .
  • the non-aqueous organic electrolyte is as described in the first aspect of the embodiment of the present invention, and details are not described herein again.
  • the positive electrode includes a positive active material capable of inserting or extracting lithium ions.
  • the positive active material has a high deintercalation lithium platform at a voltage of 4.5 V and above and above at the time of charge and discharge deintercalation of lithium ions.
  • the positive active material is LiM x Mn x )0 4 , wherein M is selected from one or more of transition metals Ni, Co and Fe, 0 X 2 .
  • the positive active material is xLi 2 Mn0 3 ( 1 -x)LiM0 2 , wherein ruthenium is selected from one or more of transition metals Ni, Co and Mn, 0 x 1.
  • the lithium ion secondary battery provided in the third aspect of the embodiment of the present invention is not limited in form, and may be a square, cylindrical or soft pack battery, and the lithium ion secondary battery has high energy whether it is wound or laminated. Density, good cycle performance and discharge capacity.
  • the lithium ion secondary battery is prepared by forming a positive electrode, a negative electrode and a separator into a battery core, placing the same in a casing, injecting the non-aqueous organic electrolyte, and sealing to obtain a lithium ion secondary battery.
  • Lithium ion The preparation method of the secondary battery is simple and feasible.
  • the first aspect of the present invention provides a non-aqueous organic electrolyte for solving the problem that the non-aqueous organic electrolyte in the prior art is easily generated with the positive active material in a fully charged high voltage (voltage above 4.5V) battery system.
  • the side reaction causes a problem of a decrease in cycle performance, volume expansion, and discharge capacity of the lithium ion secondary battery, and the non-aqueous organic electrolyte exhibits good cycle performance in a high-voltage working environment of about 4.9V.
  • a second aspect of the embodiment of the present invention provides a method of producing the above nonaqueous organic electrolyte.
  • a third aspect of the present invention provides a lithium ion secondary battery comprising the above nonaqueous organic electrolyte, the lithium ion secondary battery having a high energy density.
  • an embodiment of the present invention provides a non-aqueous organic electrolyte, comprising:
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are a linear or branched alkyl group of C ⁇ do, an alkene group of C ⁇ do, an alkyne group of Cr ⁇ do or C
  • R 7 and R 8 are halogen-containing: a straight or branched alkyl group of Cr ⁇ do, an olefin group of Cu), an alkyne group of Cr ⁇ do or an aromatic group of C 6 to C 14 .
  • the non-aqueous organic electrolyte additive represented by the formula (I) in the embodiment of the present invention is a derivative of pyrophosphate, and the non-aqueous organic electrolyte additive represented by the formula (II) is pyrophosphite. derivative.
  • R 2 , R 3 and R 4 may be the same structure or different.
  • R 5 , R 6 , R 7 and R 8 may be the same structure or different.
  • R 2 , R 3 and R 4 are a mercapto group, an ethyl group, a trifluoromethyl group, a trifluoroethyl group, a perfluoroethyl group, a phenyl group, a benzyl group. , partial or perfluoro substituted phenyl.
  • R 2 , R 3 and R 4 may be the same structure or different.
  • R 5 , R 6 , R 7 and R 8 are an indenyl group, an ethyl group, an ethyl trifluoromethyl group, a trifluoroethyl group, a perfluoroethyl group, a phenyl group. , benzyl, partially or perfluoro substituted phenyl.
  • R 5 , R 6 , R 7 and R 8 may be the same structure or different.
  • Lithium salt is used as a carrier to ensure the basic operation of lithium ions in lithium ion secondary batteries, including but not limited to lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiC10 4 ), lithium tetrafluoroborate (LiBF 4 ), hexafluoride Lithium arsenate (LiAsF 6 ), lithium hexafluorosilicate (LiSiF 6 ), lithium tetraphenylborate (LiB(C 6 3 ⁇ 4 ) 4 ), lithium chloride (LiCl), lithium bromide (LiBr), lithium chloroaluminate ( LiAlCl 4 ), lithium bis(oxalate)borate (LiBOB), lithium trifluoromethanesulfonate (LiCF 3 S0 3 ), lithium perfluorobutyl sulfonate (LiC 4 F 9 S0 3 ), lithium fluorosulfonimide (
  • the final concentration of the lithium salt in the non-aqueous organic electrolyte is not limited and is usually from 0.5 to 2.0 mol/L. Specifically, The final concentration of the lithium salt in the non-aqueous organic electrolyte is 0.7 to 1.6 mol/L. When the final concentration of the lithium salt is preferably within this range, the non-aqueous organic electrolyte of the embodiment of the present invention can simultaneously provide better lithium ion conductivity and lithium ion mobility.
  • the non-aqueous organic solvent is selected from solvents conventional in the art and may be one or more of aliphatic or cyclic carbonates, ethers, sulfones, nitriles, ionic liquids, and derivatives thereof, including but not limited to Y-butyl Lactone (GBL), ethylene carbonate (EC), diethyl carbonate (DEC), dinonyl carbonate (DMC), vinylene carbonate (VC), ethyl cerium carbonate (EMC), dipropyl carbonate ( DPC), propyl propyl carbonate (MPC), propylene carbonate (PC), decyl decanoate (MF), decyl acrylate (MA), decyl butyrate (MB) ethyl acetate (EP), ethylene sulfite Ester (ES), propylene sulfite (PS), sulfonium sulfide (DMS), diethyl sulfite (DES), tetra
  • the non-aqueous organic solvent accounts for 85% to 99.5% of the non-aqueous organic electrolyte
  • the non-aqueous organic electrolyte additive accounts for 0.5% to 15% of the non-aqueous organic electrolyte.
  • the non-aqueous organic solvent accounts for 92% to 99% of the non-aqueous organic electrolyte
  • the non-aqueous organic electrolyte additive accounts for 1% to 8% of the non-aqueous organic electrolytic solution.
  • the non-aqueous organic electrolyte may further include a functional auxiliary agent selected from the group consisting of a cyclic additive, a high-temperature additive, a flame retardant additive, and an overcharge additive. kind or several.
  • the functional auxiliaries include, but are not limited to, vinylene carbonate (VC), biphenyl, cyclohexylbenzene, 2, 52 di-tert-butyl 21,42 didecyloxybenzene (DDB), thiophene, phenothiazine, carbonic acid Lithium, carbon dioxide, 1,3 propane lactone (PS), ethylene carbonate (FEC) and lithium tetrafluoroborate (LiBF 4 ), tridecyl phosphate, triethyl phosphate, triphenyl phosphate, tributyl phosphate Ester and phosphazene compounds.
  • VC vinylene carbonate
  • DDB didecyloxybenzene
  • thiophene phenothiazine
  • carbonic acid Lithium carbon dioxide
  • PS 1,3 propane lactone
  • FEC ethylene carbonate
  • LiBF 4 lithium tetrafluoroborate
  • tridecyl phosphate triethy
  • the functional additives account for 0.1% to 15% of the non-aqueous organic electrolyte.
  • the non-aqueous organic electrolyte provided by the first aspect of the present invention can be used in a working environment of full charge high voltage (voltage above 4.5V), has excellent chemical stability and electrochemical stability, and can avoid high voltage.
  • OR ——I Lithium_, the phenomenon of gas expansion of ion secondary batteries, and the increase of lithium ion at high voltage
  • the cycle performance and discharge capacity of the secondary battery is operated at a high voltage of about 4.9V.
  • the non-aqueous organic electrolyte additive and/or the non-aqueous organic electrolyte additive as shown in formula (II) are partially broken by phosphorus-oxygen bonds, and some of the phosphorus-containing fragments are formed by oxidative decomposition of a non-aqueous organic solvent or a lithium salt.
  • the product interacts to form an electron-conducting, ion-conducting surface film containing phosphorus on the surface of the positive electrode active material, covering the active site on the surface of the positive electrode active material, blocking the active site on the surface of the positive electrode active material and non-aqueous organic electrolysis
  • the direct contact of the liquid reduces the oxidation of the positive electrode active material to the non-aqueous organic electrolyte, thereby improving the cycle performance of the lithium ion secondary battery at a high voltage, and avoiding the volume expansion of the lithium ion secondary battery and the decrease in the discharge capacity.
  • an embodiment of the present invention provides a method for preparing a non-aqueous organic electrolyte, comprising the steps of: dissolving a lithium salt in a non-aqueous organic solvent, and adding a non-aqueous organic electrolyte as shown in formula (I) Adding an additive and/or a non-aqueous organic electrolyte additive as shown in formula (II) to a non-aqueous organic electrolyte,
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are a straight or branched alkyl group of Cr ⁇ do, C ⁇ do Alkenyl group, Cr ⁇ do alkyne group or C 6 -C 14 aromatic group, or Ri, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are halogen-containing: Cr ⁇ a linear or branched alkyl group of do, an alkene group of Cu), an alkyne group of Cr ⁇ do or an aromatic group of C 6 to C 14 .
  • R 2 , R 3 and R 4 are a mercapto group, an ethyl group, a trifluoromethyl group, a trifluoroethyl group, a perfluoroethyl group, a phenyl group, a benzyl group. , partial or perfluoro substituted phenyl.
  • R 2 , R 3 and R 4 may be the same structure or different.
  • R 5 , R 6 , R 7 and R 8 are an indenyl group, an ethyl group, an ethyl trifluoromethyl group, a trifluoroethyl group, a perfluoroethyl group, a phenyl group. , benzyl, partially or perfluoro substituted phenyl.
  • R 5 , R 6 , R 7 and R 8 may be the same structure or different.
  • the preparation method of the non-aqueous organic electrolyte is carried out in an argon-filled glove box.
  • the lithium salt is dissolved in a non-aqueous organic solvent and the temperature is controlled at 20 to 35 °C. In this preferred temperature range, it is possible to avoid the volatilization of the non-aqueous organic solvent and to avoid the decomposition of the lithium salt, and to prevent the dissolution of the lithium salt due to the freezing of the non-aqueous organic solvent due to the low temperature.
  • Lithium salt is used as a carrier to ensure the basic operation of lithium ions in lithium ion secondary batteries, including but not limited to lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiC10 4 ), lithium tetrafluoroborate (LiBF 4 ), hexafluoride Lithium arsenate (LiAsF 6 ), lithium hexafluorosilicate (LiSiF 6 ), lithium tetraphenylborate (LiB(C 6 3 ⁇ 4 ) 4 ), lithium chloride (LiCl), lithium bromide (LiBr), lithium chloroaluminate ( LiAlCl 4 ), lithium bis(oxalate)borate (LiBOB), lithium trifluoromethanesulfonate (LiCF 3 S0 3 ), lithium perfluorobutyl sulfonate (LiC 4 F 9 S0 3 ), lithium fluorosulfonimide (
  • the final concentration of the lithium salt in the non-aqueous organic electrolyte is not limited and is usually from 0.5 to 2.0 mol/L. Specifically, the final concentration of the lithium salt in the non-aqueous organic electrolyte is 0.7 to 1.6 mol/L. When the final concentration of the lithium salt is preferably within this range, the non-aqueous organic electrolyte of the embodiment of the present invention can simultaneously provide better lithium ion conductivity and lithium ion mobility.
  • the non-aqueous organic solvent is selected from solvents conventional in the art and may be one or more of aliphatic or cyclic carbonates, ethers, sulfones, nitriles, ionic liquids, and derivatives thereof, including but not limited to Y-butyl Lactone (GBL), ethylene carbonate (EC), diethyl carbonate (DEC), dinonyl carbonate (DMC), vinylene carbonate (VC), ethyl cerium carbonate (EMC), dipropyl carbonate ( DPC), propyl propyl carbonate (MPC), propylene carbonate (PC), decyl decanoate (MF), decyl acrylate (MA), decyl butyrate (MB) ethyl acetate (EP), ethylene sulfite Ester (ES), propylene sulfite (PS), sulfonium sulfide (DMS), diethyl sulfite (DES), tetra
  • the non-aqueous organic solvent accounts for 85% to 99.5% of the non-aqueous organic electrolyte
  • the non-aqueous organic electrolyte additive accounts for 0.5% to 15% of the non-aqueous organic electrolyte.
  • the non-aqueous organic solvent accounts for 92% to 99% of the non-aqueous organic electrolyte
  • the non-aqueous organic electrolyte additive accounts for 1% to 8% of the non-aqueous organic electrolytic solution.
  • the non-aqueous organic electrolyte additive represented by the formula (I) is added to the preparation method of the non-aqueous organic electrolyte provided by the second aspect of the present invention. And/or after the non-aqueous organic electrolyte additive as shown in formula (II), further comprising adding a functional auxiliary agent selected from the group consisting of a cyclic additive, a high temperature additive, a flame retardant additive, and an overcharge additive.
  • the functional auxiliaries include, but are not limited to, vinylene carbonate (VC), biphenyl, cyclohexylbenzene, 2, 52 di-tert-butyl 21,42 didecyloxybenzene (DDB), thiophene, .
  • Dithiazine lithium carbonate, carbon dioxide, 1,3-propane sultone, ethylene carbonate (FEC) and lithium tetrafluoroborate (LiBF 4 ), tridecyl phosphate, triethyl phosphate, triphenyl phosphate, phosphoric acid Tributyl ester and phosphazene compounds.
  • the functional additives account for 0.1% to 15% of the non-aqueous organic electrolyte.
  • a method for preparing a non-aqueous organic electrolyte provided by a second aspect of the present invention provides a method
  • the new non-aqueous organic electrolyte has a simple process.
  • an embodiment of the present invention provides a lithium ion secondary battery, including: a positive electrode, a negative electrode, and o
  • R 2 , R 3 , R 5 , R 6 , R 7 and R 8 are a linear or branched alkyl group of C ⁇ Q, an alkene group of C ⁇ do, an alkyne group of Cr ⁇ do or C 6 ⁇
  • R 7 and R 8 are halogen-containing: a straight or branched alkyl group of Cr ⁇ do, an alkene group of Cu), an alkyne group of CH ⁇ o or an aromatic group of C 6 to C 14 .
  • the non-aqueous organic electrolyte is as described in the first aspect of the embodiment of the present invention, and details are not described herein again.
  • the positive electrode includes a positive active material capable of inserting or extracting lithium ions.
  • the positive active material has a high deintercalation lithium platform at a voltage of 4.5 V and 4.5 V or higher during charge and discharge deintercalation of lithium ions.
  • the positive active material may be LiM x Mn ⁇ x )0 4 , wherein M is selected from one or more of transition metals Ni, Co, and Fe.
  • the positive active material may be xLi 2 Mn0 3 ( 1 -x)LiM0 2 , wherein ruthenium is selected from one or more of transition metals Ni, Co, and Mn, 0 ⁇ 1.
  • the lithium ion secondary battery provided in the third aspect of the embodiment of the present invention is not limited in form, and may be a square, cylindrical or soft pack battery, and the lithium ion secondary battery has high energy whether it is wound or laminated. Density, good cycle performance and discharge capacity.
  • the lithium ion secondary battery is prepared by forming a positive electrode, a negative electrode and a separator into a battery core, placing the same in a casing, injecting the non-aqueous organic electrolyte, and sealing to obtain a lithium ion secondary battery.
  • the preparation method of the lithium ion secondary battery is simple and feasible.
  • a method for preparing a non-aqueous organic electrolyte comprising the steps of:
  • the positive active material LiNi sMn C conductive agent acetylene black and the binder PVDF powder material were mixed at a mass ratio of 80:10:10, and then N-decylpyrrolidone (NMP) solution was added and stirred in a vacuum mixer for 2 hours to prepare a solution.
  • NMP N-decylpyrrolidone
  • the oil-based slurry is finally coated on both sides of the aluminum current collector, dried at 110 ° C, and rolled to form a positive electrode sheet of a lithium ion secondary battery.
  • CMC carboxymethyl cellulose
  • SBR styrene-butadiene rubber
  • the non-aqueous organic electrolyte As the non-aqueous organic electrolyte, the non-aqueous organic electrolyte A obtained in the present example was used.
  • a composite separator composed of polypropylene and polyethylene is placed between the positive electrode tab and the negative electrode tab prepared above, such as a sandwich structure, and then rolled together into a 423450 square battery pole core, and finally a square-wound soft pack battery is completed. Finally, the nonaqueous organic electrolyte A was injected to obtain a lithium ion secondary battery A.
  • the same effect can be obtained by the above-described lithium ion secondary battery preparation method.
  • a method for preparing a non-aqueous organic electrolyte comprising the steps of:
  • ethylene carbonate (EC), 1000 g of dinonyl carbonate (DMC) and 500 g of diethyl carbonate (DEC) were added to the stirrer to form a non-aqueous organic solvent, and 250 g of lithium salt LiC10 4 was dissolved.
  • stirring temperature is 20 ° C;
  • non-aqueous organic electrolyte additive as shown in Formula Ib, obtained from Beijing Jiashengyang Pharmaceutical Technology Co., Ltd., and stirring, to obtain a non-aqueous organic electrolyte B,
  • the mass fraction, the non-aqueous organic electrolyte additive lb accounts for 1% of the non-aqueous organic electrolyte.
  • the following is a square-wound lithium ion secondary soft pack battery (model number is 423450-800mAh). As an example, a method of preparing a lithium ion secondary battery according to an embodiment of the present invention will be described.
  • the positive active material LiNi sMn C conductive agent carbon black powder and the binder PVDF powder material were mixed at a mass ratio of 85:10:5, and then N-decylpyrrolidone (NMP) solution was added and stirred in a vacuum mixer for 2 hours.
  • NMP N-decylpyrrolidone
  • the oil-based slurry is finally coated on both sides of the aluminum current collector, dried at 110 ° C, and rolled to form a positive electrode sheet of a lithium ion secondary battery.
  • the non-aqueous organic electrolyte B was prepared by using the non-aqueous organic electrolyte B obtained in the present example, and the lithium ion secondary battery B was obtained by the same method as the lithium ion secondary battery of the first embodiment.
  • a method for preparing a non-aqueous organic electrolyte comprising the steps of:
  • non-aqueous organic electrolyte additive as shown in Formula Ic, obtained from Beijing Swanda Kangkee Co., Ltd., and stirring, to obtain a non-aqueous organic electrolyte C
  • the non-aqueous organic electrolyte additive I c accounts for 8% of the non-aqueous organic electrolyte by mass fraction.
  • Positive electrode active material 0.5 (Li 2 MnO 3 ) 0.5 (LiNi 1 / 3 Co 1 / 3 Mn 1/3 O 2 ), conductive agent carbon black powder and sticky
  • the cement PVDF powder material was mixed at a mass ratio of 85:10:5, then a solution of N-decylpyrrolidone (NMP) was added, and stirred in a vacuum mixer for 2 hours to prepare an oil-based slurry, and finally the slurry was coated on aluminum.
  • the two sides of the current collector are dried at 110 ° C and rolled to form a positive electrode of a lithium ion secondary battery.
  • the non-aqueous organic electrolyte C obtained in the present example was used, and another lithium ion secondary battery C was produced in the same manner as in the production method of the lithium ion secondary battery of the first embodiment.
  • a method for preparing a non-aqueous organic electrolyte comprising the steps of:
  • EC ethylene carbonate
  • DMC dinonyl carbonate
  • LiCF 3 S0 3 lithium salt trifluorosulfonylsulfonate
  • non-aqueous organic electrolyte additive as shown in Formula Ib, obtained from Beijing Jiashengyang Pharmaceutical Technology Co., Ltd., and stirring, to obtain a non-aqueous organic electrolyte D, According to the mass fraction, the non-aqueous organic electro-hydraulic additive lb accounts for 15% of the non-aqueous organic electrolyte.
  • the positive electrode active material 0.7 (Li 2 MnO 3 ) 0.3 (LiNi 1 / 3 Co 1 / 3 Mn 1/3 O 2 ), the conductive agent carbon black powder, and the binder PVDF powder material were subjected to a mass ratio of 85:10:5. Mixing, then adding N-decylpyrrolidone (NMP) solution, stirring in a vacuum mixer for 2 h, preparing an oil-based slurry, and finally coating the slurry in The aluminum current collector is coated on both sides, dried at 110 ° C, and rolled to form a positive electrode of a lithium ion secondary battery.
  • NMP N-decylpyrrolidone
  • the non-aqueous organic electrolyte D obtained in the present embodiment was used, and other lithium ion secondary batteries of the same manner as in the first embodiment were used to produce a lithium ion secondary battery D.
  • a method for preparing a non-aqueous organic electrolyte comprising the steps of:
  • EC ethylene carbonate
  • DMC dinonyl carbonate
  • EMC cesium carbonate
  • non-aqueous organic electrolyte additive as shown in Formula Ib, 22.73 g of tetrabenzyl pyrophosphate and 2.27 g of vinylene carbonate (VC), stirring, A non-aqueous organic electrolyte E is obtained.
  • the non-aqueous organic electrolyte additive lb accounts for 1% of the non-aqueous organic electrolyte
  • the functional additive vinylene carbonate (VC) accounts for 0.1% of the non-aqueous organic electrolyte. .
  • the positive active material LiNi sMn C conductive agent carbon black powder and the binder PVDF powder material were mixed at a mass ratio of 85:10:5, and then N-decylpyrrolidone (NMP) solution was added and stirred in a vacuum mixer for 2 hours.
  • NMP N-decylpyrrolidone
  • the oil-based slurry is finally coated on both sides of the aluminum current collector, dried at 110 ° C, and rolled to form a positive electrode sheet of a lithium ion secondary battery.
  • the non-aqueous organic electrolyte solution was the non-aqueous organic electrolyte E obtained in the present example, and the lithium ion secondary battery E was produced in the same manner as in the production method of the lithium ion secondary battery of the first embodiment.
  • a method for preparing a non-aqueous organic electrolyte comprising the steps of:
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • the positive active material LiNi sMn C conductive agent carbon black powder and the binder PVDF powder material were mixed at a mass ratio of 85:10:5, and then N-decylpyrrolidone (NMP) solution was added and stirred in a vacuum mixer for 2 hours.
  • NMP N-decylpyrrolidone
  • the oil-based slurry is finally coated on both sides of the aluminum current collector, dried at 110 ° C, and rolled to form a positive electrode sheet of a lithium ion secondary battery.
  • the non-aqueous organic electrolyte solution was the non-aqueous organic electrolyte solution F obtained in the present example, and the lithium ion secondary battery F was produced in the same manner as in the production method of the lithium ion secondary battery of the first embodiment.
  • Example 7 A method for preparing a non-aqueous organic electrolyte, comprising the steps of:
  • ethylene carbonate (EC), 1000 g of dinonyl carbonate (DMC) and 500 g of diethyl carbonate (DEC) were added to the stirrer to form a non-aqueous organic solvent, and 250 g of lithium salt LiB (C 6 ) was added. 3 ⁇ 4 ) 4 in a non-aqueous organic solvent, stirring, stirring temperature is 25 ° C;
  • non-aqueous organic electrolyte additive lib accounts for 8% of the non-aqueous organic electrolyte.
  • the positive electrode active material 0.4 (Li 2 MnO 3 ) 0.6 (LiNi 1 / 3 Co 1 / 3 Mn 1/3 O 2 ), the conductive agent carbon black powder, and the binder PVDF powder material were subjected to a mass ratio of 85:10:5. Mixing, then adding N-decylpyrrolidone (NMP) solution, stirring in a vacuum mixer for 2 h to prepare an oil-based slurry, and finally coating the slurry on both sides of the aluminum current collector, drying at 110 ° C, rolling, A positive electrode of a lithium ion secondary battery was fabricated.
  • NMP N-decylpyrrolidone
  • the non-aqueous organic electrolyte G obtained in the present example was used, and other lithium ion secondary batteries of the same manner as in the first embodiment were used to produce a lithium ion secondary battery G.
  • a method for preparing a non-aqueous organic electrolyte comprising the steps of:
  • the non-aqueous organic electrolyte additive li b accounts for 2% of the non-aqueous organic electrolyte
  • the functional additive triethyl phosphate (TEP) It accounts for 15% of the non-aqueous organic electrolyte.
  • the positive active material LiNi sMn C conductive agent carbon black powder and the binder PVDF powder material were mixed at a mass ratio of 85:10:5, and then N-decylpyrrolidone (NMP) solution was added and stirred in a vacuum mixer for 2 hours.
  • NMP N-decylpyrrolidone
  • the oil-based slurry is finally coated on both sides of the aluminum current collector, dried at 110 ° C, and rolled to form a positive electrode sheet of a lithium ion secondary battery.
  • the non-aqueous organic electrolyte H obtained in the present example was used, and other lithium ion secondary batteries of the same manner as in the first embodiment were used to produce a lithium ion secondary battery H. Comparative example one
  • Non Water organic electrolyte I Adding 500 g of ethylene carbonate (EC) and 500 g of cesium carbonate (EMC) to the stirrer to form a non-aqueous organic solvent, and dissolving 125 g of lithium salt LiPF 6 in a non-aqueous organic solvent, stirring, and obtaining Non Water organic electrolyte I.
  • EC ethylene carbonate
  • EMC cesium carbonate
  • the positive active material LiNi sMn C conductive agent carbon black powder and the binder PVDF powder material were mixed at a mass ratio of 85:10:5, and then N-decylpyrrolidone (NMP) solution was added and stirred in a vacuum mixer for 2 hours.
  • NMP N-decylpyrrolidone
  • the oil-based slurry is finally coated on both sides of the aluminum current collector, dried at 110 ° C, and rolled to form a positive electrode sheet of a lithium ion secondary battery.
  • the non-aqueous organic electrolyte I used the non-aqueous organic electrolyte I obtained in the comparative example, and other lithium ion secondary batteries of the same manner as in the first embodiment were used to produce a lithium ion secondary battery I.
  • the positive electrode active material 0.5 (Li 2 MnO 3 ) 0.5 (LiNi 1 / 3 Co 1 / 3 Mn 1/3 O 2 ), the conductive agent carbon black powder, and the binder PVDF powder material were subjected to a mass ratio of 85:10:5. Mixing, then adding N-decylpyrrolidone (NMP) solution, stirring in a vacuum mixer for 2 h to prepare an oil-based slurry, and finally coating the slurry on both sides of the aluminum current collector, drying at 110 ° C, rolling, A positive electrode of a lithium ion secondary battery was fabricated.
  • NMP N-decylpyrrolidone
  • the non-aqueous organic electrolyte solution is the non-aqueous organic electrolyte J prepared in the comparative example, and the others are implemented in the same manner.
  • a lithium ion secondary battery J was obtained. Effect embodiment
  • the first and second examples were subjected to cyclic voltammetry using a three-electrode system.
  • the working electrode was glassy carbon
  • the counter electrode and the reference electrode were lithium electrodes
  • the scanning range was 0 to 5.5 V
  • the scanning speed was 10 mV/ S o
  • the non-aqueous organic electrolytes provided in Examples 1 to 8 of the present invention have an oxidative decomposition potential of 5.0 V or more, and No pyrophosphate or pyrophosphite in Comparative Examples 1 and 2.
  • the oxidative decomposition potential of the non-aqueous organic electrolyte of the additive-like additive is only 4.4 V, which is much lower than the decomposition potential of the non-aqueous organic electrolyte provided in Examples 1 to 8 of the present invention.
  • the lithium ion secondary batteries prepared according to the above Examples 1 to 8 and Comparative Examples 1 and 2 were subjected to cycle performance tests.
  • the test method is as follows: The lithium ion secondary battery is loaded into the secondary battery performance test in the correct way to BS-9300, first charged to 4.9V with constant current constant voltage of 1C (for spinel LiM x Mn x ) 0 4 , Wherein M is selected from one or more of transition metals Ni, Co and Fe, 0 x 2 ) or 4.6 V (for lithium-rich solid solution cathode material xLi 2 Mn0 3 (lx)LiM0 2 , wherein M is selected from transition metal Ni , one or more of Co and Mn, 0 ⁇ 1 ), set aside for 5 minutes, discharge to 3.0V with 1C, and then charge to 4.9V with constant current at 1C (for spinel LiM x Mn x )0 4 , wherein M is selected from one or more of transition metals Ni, Co and Fe,
  • the lithium ion secondary battery provided by Examples 1 to 8 of the present invention has a capacity retention rate of up to 95% and a minimum of 89% after 100 cycles, and is prepared in Comparative Examples 1 and 2.
  • the capacity retention of the lithium ion secondary battery after only 100 cycles is only 56% and 43%, and it can be seen that the nonaqueous organic electrolyte provided in the first to eighth embodiments of the present invention has good high pressure resistance.
  • the cycle performance of the lithium ion secondary battery provided by the first to eighth embodiments of the present invention is improved.

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Abstract

L'invention concerne un électrolyte organique non aqueux, un procédé de préparation de celui-ci et une batterie secondaire au lithium-ion contenant l'électrolyte organique non aqueux. L'électrolyte organique non aqueux comprend : un sel de lithium, un solvant organique non aqueux et un additif d'électrolyte organique non aqueux. L'additif d'électrolyte organique non aqueux est un additif d'électrolyte organique non aqueux tel que représenté dans la formule (I) et/ou un additif d'électrolyte organique non aqueux tel que représenté dans la formule (II). La présente invention résout le problème rencontré dans l'art antérieur consistant en la réaction parallèle qui se produit facilement entre l'électrolyte organique non aqueux et un matériau actif d'électrode positive dans un système de batterie entièrement chargé et à tension élevée (une tension supérieure à 4,5 V), laquelle entraîne une dégradation des performances de cycle, une augmentation du volume et une diminution de la capacité de décharge de la batterie secondaire au lithium-ion. L'électrolyte organique non aqueux présente toujours de bonnes performances de cycle dans un environnement de fonctionnement avec une tension élevée d'environ 4,9 V.
PCT/CN2013/080350 2013-01-28 2013-07-29 Électrolyte organique non aqueux, procédé de préparation de celui-ci et batterie secondaire au lithium-ion WO2014114068A1 (fr)

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CN111540952A (zh) * 2020-05-12 2020-08-14 上海纳米技术及应用国家工程研究中心有限公司 一种改善锂离子电池高温存储性能的高电压电解液
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CN111540952A (zh) * 2020-05-12 2020-08-14 上海纳米技术及应用国家工程研究中心有限公司 一种改善锂离子电池高温存储性能的高电压电解液

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