WO2015042850A1 - 一种锂电池用电解液及使用该电解液的锂电池 - Google Patents

一种锂电池用电解液及使用该电解液的锂电池 Download PDF

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Publication number
WO2015042850A1
WO2015042850A1 PCT/CN2013/084405 CN2013084405W WO2015042850A1 WO 2015042850 A1 WO2015042850 A1 WO 2015042850A1 CN 2013084405 W CN2013084405 W CN 2013084405W WO 2015042850 A1 WO2015042850 A1 WO 2015042850A1
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lithium
electrolyte
battery
quaternary ammonium
anions
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French (fr)
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曹浪
袁中直
刘金成
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Eve Energy Co Ltd
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Eve Energy Co Ltd
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Priority to CN201380002468.8A priority patent/CN103858268A/zh
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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
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
    • 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
    • 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
    • H01M2300/0045—Room temperature molten salts comprising at least one organic ion
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a lithium battery electrolyte gas using a read electrolyte, especially a lithium/thionyl chloride battery or a lithium/manganese dioxide battery or a lithium/fluorene fluoride battery electrolyte and Use a lithium battery for clock electrolysis.
  • a lithium battery electrolyte gas using a read electrolyte, especially a lithium/thionyl chloride battery or a lithium/manganese dioxide battery or a lithium/fluorene fluoride battery electrolyte and Use a lithium battery for clock electrolysis.
  • Lithium batteries are widely used in the fields of instrumentation, memory power, military and petroleum drilling due to their high energy, low self-discharge rate, long storage life and environmental protection.
  • the lithium/male acid chloride battery is inverted.
  • the commonly designed 4 spirit/sulphuric acid chlorine battery is usually used at a temperature range of -4 (TC to +85), and is used in high-temperature lithium/sulfuric acid chlorine batteries in the field of petroleum 4* ⁇ . It can reach a temperature of 150 °C, 180 or even 200. In the design of such a temperature battery, the ability to achieve high temperature is reduced by reducing the amount of active substances based on the design of ordinary batteries. During the discharge process, there will be a large difference in discharge capacity between normal temperature and high temperature, and even the phenomenon of unstable discharge and tailing of the discharge voltage at high temperature will seriously affect the performance of the lithium battery in the temperature.
  • the technical solution adopted by the present invention is: an electrolyte for a lithium battery, the electrolyte containing a quaternary ammonium salt-based ionic liquid, the quaternary ammonium salt-based ionic liquid comprising a cation and an anion; N-alkyl quaternary ammonium salt;
  • the anion is a halide salt, a tetrafluoroborate anion, a hexafluorophosphate anion, a bis(trifluorodecylsulfonyl)imide anion, a lactate anion, a p-nonylbenzenesulfonate anion, an acetylsulfonimide anion,
  • a saccharin anion an amino acid anion, a sulfate anion, a diisooctyl succinate anion, a 4,5-dinitroimidazolium anion, and a 5-nitrotetrazole anion.
  • the electrolyte of the invention proposes a new method for improving the wide temperature performance of the lithium battery, that is, adding a quaternary ammonium salt ionic liquid to the electrolyte, and the added quaternary ammonium salt ionic liquid can be used as a kind of wide temperature battery reaction catalyst.
  • the quaternary ammonium salt-based ionic liquid contains a cation and an anion, the cation is an N-sulfonium quaternary ammonium salt, and the anion is a halogenated salt ion, a tetrafluoroborate anion, a hexafluorophosphate anion, or a bis(trifluoromethyl) group.
  • T bismuth sulphate bismuth sulphate sulphate sulphate ionic ion ionic liquid has a wide liquid range, strong solubility, low vapor pressure, suitable viscosity, The characteristics of high conductivity, wide electrochemical window, etc., make it have broad application prospects.
  • the addition of the quaternary ammonium salt ionic liquid in the electrolyte In can function as a wide-temperature catalyst, that is, it has high battery reaction catalysis in the range from normal temperature to high temperature, so that the battery has consistent high-performance discharge capability in a wide temperature range, and at the same time, significant The growth of the passivation film layer on the surface of the metal lithium negative electrode is suppressed, and the storage performance is improved.
  • the cation is a tetraalkyl quaternary ammonium salt.
  • the cation is tetradecylammonium.
  • the formed quaternary ammonium salt ionic liquid can better exert the function of the wide temperature battery reaction catalyst; when the cation selects tetradecyl ammonium, the quaternary ammonium salt ion is formed
  • the liquid can best function as a wide temperature battery reaction catalyst.
  • the anion is a surface salt ion.
  • the anion is a tetrachloroaluminate ion.
  • the anion selects a halogenated salt ion
  • the formed quaternary ammonium salt ionic liquid can better exert the function of the wide temperature battery reaction catalyst; the anion selects the aluminum tetrachloride ion
  • the formed quaternary ammonium salt-based ionic liquid can best function as a wide-temperature battery reaction catalyst.
  • the quaternary ammonium salt in the electrolyte The volume percentage of the salt ionic liquid is 0.1 to 50%.
  • the volume percentage of the quaternary ammonium salt ionic liquid in the electrolyte is 1 ⁇ 15%.
  • the volume fraction of the quaternary ammonium salt-based ionic liquid in the electrolyte is 5%.
  • the quaternary ammonium salt-based ionic liquid in the electrolyte When the volume percentage is 1-15%, the lithium battery prepared by the electrolyte has a more consistent high-performance discharge capability in a range from low temperature to high temperature; the volume of the quaternary ammonium salt-based ionic liquid in the electrolyte When the percentage is 5%, the lithium battery prepared by the electrolyte has the most consistent high-performance discharge capability in the range from low temperature to high temperature. Meanwhile, the present invention also provides preparation of the electrolyte for lithium battery as described above. Method, institute The method comprises the steps of:
  • Pre-electrolysis high-purity aluminum sheet for positive and negative electrodes in a waterless environment, connected to a regulated power supply, voltage 1.08V, electrolysis for 24 hours, removing moisture in the quaternary ammonium salt ionic liquid;
  • the quaternary ammonium salt-based ionic liquid is in the absence of water. Pre-electrolysis is carried out under the environment (moisture content ⁇ 0.1%), the moisture in the quaternary ammonium salt-based ionic liquid is removed, and then the quaternary ammonium salt-based ionic liquid is added to the conventional electrolyte according to the volume ratio, and the mixture is mixed. The electrolyte of the invention is obtained, and the operation is convenient.
  • the quaternary ammonium salt ionic liquid is preferably pre-electrolyzed to remove the water therein and then added to the conventional electrolyte.
  • the quaternary ammonium salt ionic liquid may be pre-electrolyzed without being directly added to the conventional electrolyte.
  • the present invention provides a lithium battery comprising the electrolytic solution for a lithium battery as described above. According to the lithium battery of the lithium battery electrolyte as described above, since the quaternary ammonium salt-based ionic liquid contained in the electrolyte can be used as a wide-temperature battery reaction catalyst, the lithium battery of the present invention is provided. Consistent high-performance discharge capability over a wide temperature range from low to high temperatures.
  • the lithium battery is a lithium/alloy acid chloride battery, and the electrolyte further contains thionyl chloride and lithium tetrachloroaluminate.
  • the electrolyte commonly used in the prior art lithium/thionyl chloride battery is LiAlCl 4 -SOCl 2 lithium/thionyl chloride electrolyte, wherein the LiAlC concentration is in the range of 0.7M to 2.5M, and the cylinder is called "conventional electrolyte".
  • the quaternary ammonium salt-based ionic liquid additive described above is added to the "conventional electrolyte" and uniformly mixed to serve as an electrolyte solution for the lithium/thionyl chloride battery of the present invention.
  • the lithium battery is a lithium/manganese dioxide battery, and the electrolyte further contains propylene carbonate, 1,3-dioxolane, diterpene ether and high chlorine. Lithium acid.
  • the electrolyte commonly used in the prior art lithium/manganese dioxide battery is a mixture of propylene carbonate (PC), diterpene ether (DME) and carbon 1,3-dioxolane (DOL) in a certain ratio.
  • Lithium perchlorate (LiC104) is used as the electrolyte salt, and the concentration of lithium perchlorate (LiC104) is generally 0.5 to 1.5 mol/L, which is formulated into a common electrolyte.
  • the above quaternary ammonium salt-based ionic liquid is added as an additive to the usual electrolytic solution prepared above, and uniformly mixed, and can be used as an electrolyte solution of the lithium/manganese dioxide battery of the present invention.
  • the cation of the quaternary ammonium salt ionic liquid is selected from a tetraalkyl quaternary ammonium salt, an anion selected bis(trifluoromethylsulfonyl)imide anion, and the quaternary ammonium salt is in the final lithium/manganese dioxide
  • the volume percentage of the battery electrolyte is 15%, the obtained lithium/manganese dioxide lithium battery can have a more uniform discharge capacity at different temperatures.
  • the lithium battery is a lithium/carbon fluoride battery
  • the electrolyte further contains propylene carbonate, diterpene ether or Y-butyl propionate, and lithium tetrafluoroborate.
  • the commonly used motor for lithium/carbon fluoride batteries is also propylene carbonate (PC) and diterpene ether (DME) (or gamma
  • PC propylene carbonate
  • DME diterpene ether
  • the propyl ester is mixed as a solvent
  • lithium tetrafluoroborate (LIBF4) is used as an electrolyte salt
  • the concentration of lithium tetrafluoroborate (LIBF4) is generally 0.5 to 1.5 mol/L, which is formulated into a common electrolyte.
  • the above quaternary ammonium salt-based ionic liquid is added as an additive to the above-mentioned conventional electrolytic solution, and is uniformly mixed, and can be used as an electrolyte solution of the lithium/carbon fluoride battery of the present invention.
  • the cation of the quaternary ammonium salt ionic liquid is selected from a tetraalkyl quaternary ammonium salt
  • an anion is selected from a bis(trifluoroindolyl acyl) anion anion, and a quaternary ammonium salt is obtained in the final lithium/fluorinated carbon
  • the volume percentage of the battery electrolyte is 15%, the obtained lithium/carbon fluoride lithium battery can have a more uniform discharge capacity at different temperatures.
  • the electrolyte for a lithium battery of the present invention wherein a quaternary ammonium salt ionic liquid is added as an additive, is a novel electrolyte system, wherein the added quaternary ammonium salt ionic liquid can function as a wide temperature catalyst. It has high battery reaction catalysis from low temperature to high temperature, which makes the battery have high performance discharge capability in a wide temperature range. Since the lithium battery of the present invention employs the electrolytic solution of the present invention, it has a high-performance discharge capability which is uniform from a normal temperature to a high temperature range. BRIEF DESCRIPTION OF THE DRAWINGS FIG.
  • Constant resistance 10 ⁇ discharge capacity curve. 2 is a 10 ⁇ discharge of a lithium/thionyl chloride battery fabricated by using the electrolyte of the present invention at 25° C., 50° C., 70° C., 80° C., 100° C., 120° C., and 140° C., respectively. Capability curve. Fig.
  • FIG. 3 is a graph showing the discharge capacity of a constant current 350 mA at 0 ° C, 25 ° C and 60 ° C for a lithium/manganese dioxide battery fabricated using a blank group electrolyte.
  • Fig. 4 is a graph showing the discharge capacity of a constant current 350 mA at 0 ° C, 25 ° C and 60 ° C for a lithium/manganese dioxide battery fabricated by using the electrolyte of the present invention.
  • Fig. 5 is a graph showing the resistance lkQ discharge capacity of a lithium/carbon fluoride battery fabricated by using a blank group electrolyte at 0 ° C, 25 ° C and 60 ° C, respectively.
  • Fig. 4 is a graph showing the discharge capacity of a constant current 350 mA at 0 ° C, 25 ° C and 60 ° C for a lithium/manganese dioxide battery fabricated by using the electrolyte of the present invention.
  • FIG. 6 is a graph showing the resistance of lkQ discharge of a lithium/carbon fluoride battery fabricated by using the electrolyte of the present invention at 0 ° C, 25 ° C and 60 ° C, respectively.
  • Embodiment 1 An embodiment of an electrolyte for a lithium battery of the present invention, the electrolyte according to the embodiment is used for a lithium/saltyl chloride battery, and the electrolyte contains a conventional electrolyte and a quaternary ammonium salt ionic liquid,
  • the quaternary ammonium salt ionic liquid comprises a cation and an anion, the cation is tetradecylammonium, the anion is a halogenated salt ion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/thionyl chloride conventional electrolyte having a concentration of 1.5M. .
  • the volume percentage of the quaternary ammonium salt-based ionic liquid is 1%.
  • the electrolyte of this embodiment was prepared by the following method:
  • Embodiment 2 An embodiment of an electrolyte solution for a lithium battery of the present invention, the electrolyte solution used in the embodiment is used for a lithium/slate A acid chloride battery, and the electrolyte solution comprises a conventional electrolyte solution and a quaternary ammonium salt type ionic liquid.
  • the quaternary ammonium salt ionic liquid comprises a cation and an anion, the cation is tetraethylammonium, the anion is a tetrachloroaluminate ion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/sulfurous solution having a concentration of 1.5M. Acid chloride conventional electrolyte.
  • the quaternary ammonium salt-based ionic liquid has a volume percentage of 5%.
  • the electrolytic solution of this embodiment was prepared in the same manner as in Example 1.
  • Embodiment 3 An embodiment of an electrolyte solution for a lithium battery of the present invention, the electrolyte solution used in the embodiment is used for a lithium/slate A acid chloride battery, and the electrolyte solution comprises a conventional electrolyte solution and a quaternary ammonium salt type ionic liquid.
  • the quaternary ammonium salt ionic liquid comprises a cation and an anion, the cation is tetrapropylammonium, the anion is a tetrafluoroborate anion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/thionyl chloride having a concentration of 1.5 M. Electrolyte.
  • the quaternary ammonium salt-based ionic liquid had a volume percentage of 10%.
  • the electrolytic solution of this embodiment was prepared in the same manner as in Example 1.
  • Embodiment 4 An embodiment of the electrolyte solution for a lithium battery of the present invention, the electrolyte solution of the embodiment is used for a lithium/saltyl chloride battery, and the electrolyte solution comprises a conventional electrolyte solution and a quaternary ammonium salt type ionic liquid,
  • the quaternary ammonium salt ionic liquid comprises a cation and an anion, the cation is tetrabutylammonium, the anion is a hexafluorophosphate anion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/thionyl chloride conventional electrolysis having a concentration of 1.5M.
  • Embodiment 5 An embodiment of an electrolyte solution for a lithium battery of the present invention, the electrolyte solution used in the embodiment is used for a lithium/slate A acid chloride battery, and the electrolyte solution comprises a conventional electrolyte solution and a quaternary ammonium salt type ionic liquid.
  • the quaternary ammonium salt ionic liquid comprises a cation and an anion, the cation is dimercaptodiethylammonium, the anion is a bis(trifluoromethyl decanoyl)imide anion, and the conventional electrolyte has a concentration of 1.5M.
  • LiAlCl 4 -SOCl 2 Lithium / thionyl chloride conventional electrolyte.
  • the volume percentage of the quaternary ammonium salt-based ionic liquid is 50%.
  • the electrolytic solution of this embodiment was prepared in the same manner as in Example 1.
  • Embodiment 6 An embodiment of an electrolyte solution for a lithium battery of the present invention, the electrolyte solution used in the embodiment is used for a lithium/slate A acid chloride battery, and the electrolyte solution comprises a conventional electrolyte solution and a quaternary ammonium salt type ionic liquid.
  • the quaternary ammonium salt-based ionic liquid comprises a cation and an anion, the cation is dodecyltrimethylammonium, the anion is a milk S-stem anion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium having a concentration of 1.5M. /Thionyl chloride conventional electrolyte.
  • Embodiment 7 An embodiment of an electrolyte for a lithium battery of the present invention, the electrolyte according to the embodiment is used for a lithium/slate A acid chloride battery, and the electrolyte contains a conventional electrolyte and a quaternary ammonium salt ionic liquid.
  • Quaternary ammonium salt The liquid comprises a cation and an anion, the cation is dodecyldimercaptobenzylammonium, the anion is a p-nonylbenzenesulfonate anion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/Asia at a concentration of 1.5M. Sulphuryl chloride conventional electrolyte.
  • the volume percentage of the quaternary ammonium salt-based ionic liquid is 6%.
  • the electrolytic solution of this embodiment was prepared in the same manner as in Example 1.
  • Embodiment 8 An embodiment of an electrolyte solution for a lithium battery of the present invention, the electrolyte solution used in the embodiment is used for a lithium/slate A acid chloride battery, and the electrolyte solution comprises a conventional electrolyte solution and a quaternary ammonium salt type ionic liquid.
  • the quaternary ammonium salt-based ionic liquid contains a cation and an anion, the cation is tetradecylammonium, the anion is an acetyltrans-imide anion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/sulfurous solution having a concentration of 1.5M. Acid chloride conventional electrolyte.
  • Embodiment 9 An embodiment of an electrolyte solution for a lithium battery of the present invention, the electrolyte solution used in the embodiment is used for a lithium/slate A acid chloride battery, and the electrolyte solution comprises a conventional electrolyte solution and a quaternary ammonium salt type ionic liquid.
  • the quaternary ammonium salt ionic liquid comprises a cation and an anion, the cation is dimercaptodibutylammonium, the anion is a saccharin anion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/thionyl chloride having a concentration of 1.5M. Conventional electrolyte.
  • the volume percentage of the quaternary ammonium salt-based ionic liquid was 18%.
  • the electrolytic solution of this embodiment was prepared in the same manner as in Example 1.
  • Embodiment 10 An embodiment of an electrolyte solution for a lithium battery of the present invention, the electrolyte solution used in the embodiment is used for a lithium/slate A acid chloride battery, and the electrolyte solution comprises a conventional electrolyte solution and a quaternary ammonium salt type ionic liquid.
  • the quaternary ammonium salt ionic liquid comprises a cation and an anion, the cation is tetraethylammonium, the anion is an amino acid anion, and the conventional electrolyte is LiAlCl 4 -SOCl 2 lithium / thionyl chloride conventional electrolysis at a concentration of 1.5M liquid.
  • the volume percentage of the quaternary ammonium salt-based ionic liquid is 20%.
  • the electrolytic solution of this embodiment was prepared in the same manner as in Example 1.
  • Example 11 An embodiment of the electrolyte for a lithium battery of the present invention, the electrolyte according to the embodiment is used for a lithium/thartite chloride battery, the electrolyte containing a conventional electrolyte and a quaternary ammonium salt ionic liquid, the quaternary ammonium salt
  • the ionic liquid contains a cation and an anion, the cation is tetrabutylammonium, the anion is a sulfate anion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/thionyl chloride conventional electrolyte having a concentration of 1.5M.
  • the volume percentage of the quaternary ammonium salt-based ionic liquid is 25%.
  • the electrolytic solution of this embodiment was prepared in the same manner as in Example 1.
  • Embodiment 12 An embodiment of an electrolyte solution for a lithium battery of the present invention, the electrolyte solution used in the embodiment is used for a lithium/slate A acid chloride battery, and the electrolyte solution comprises a conventional electrolyte solution and a quaternary ammonium salt type ionic liquid.
  • the quaternary ammonium salt ionic liquid comprises a cation and an anion, the cation is dodecyltriethylammonium, the anion is a diisooctyl succinate sulfonate anion, and the conventional electrolyte is a LiAlCl having a concentration of 1.5M. 4- SOCl 2 Lithium/thionyl chloride conventional electrolyte.
  • the volume percentage of the quaternary ammonium salt-based ionic liquid was 35%.
  • the electrolytic solution of this embodiment was prepared in the same manner as in Example 1.
  • Embodiment 13 An embodiment of an electrolyte solution for a lithium battery of the present invention, the electrolyte solution used in the embodiment is used for a lithium/slate A acid chloride battery, and the electrolyte solution comprises a conventional electrolyte solution and a quaternary ammonium salt type ionic liquid.
  • the quaternary ammonium salt ionic liquid comprises a cation and an anion, the cation is dodecyltributylammonium, the anion is a 4,5-dinitroimidazolium anion, and the conventional electrolyte is a LiAlCl 4 having a concentration of 1.5M. - SOCl 2 lithium / thionyl chloride conventional electrolyte.
  • the volume percentage of the quaternary ammonium salt-based ionic liquid is 40%.
  • the electrolytic solution of this embodiment was prepared in the same manner as in Example 1.
  • Embodiment 14 An embodiment of an electrolyte solution for a lithium battery of the present invention, the electrolyte solution used in the embodiment is used for a lithium/slate A acid chloride battery, and the electrolyte solution comprises a conventional electrolyte solution and a quaternary ammonium salt type ionic liquid.
  • the quaternary ammonium salt ionic liquid comprises a cation and an anion, the cation is dodecyldiethylbenzylammonium, the anion is a 5-nitrotetrazole anion, and the conventional electrolyte is a LiAlCl 4 having a concentration of 1.5M. - SOCl 2 lithium / thionyl chloride conventional electrolyte.
  • the volume percentage of the quaternary ammonium salt-based ionic liquid was 45%.
  • the electrolytic solution of this embodiment was prepared in the same manner as in Example 1.
  • Example 15 The test for the discharge capacity of a lithium/thionyl chloride battery containing a quaternary ammonium salt-based ionic liquid for a battery from a normal temperature to a high temperature range was carried out by using an experimental group and a blank group, and the experimental group included an experiment.
  • Groups 1-14, Experimental Groups 1-14 used the electrolytes prepared in Examples 1-14, respectively, while the blank group used an electrolyte of LiAlCl 4 -SOCl 2 lithium/thionyl chloride conventional electrolyte at a concentration of 1.5M. That is, the electrolyte of the blank group does not contain the quaternary ammonium salt-based ionic liquid in the experimental group.
  • the ER26102S-150 high-temperature lithium/arteite A acid chloride battery was prepared by using the electrolyte of the experimental group and the blank group, respectively, and then the lithium/cristotal acid chloride battery fabricated by the blank group was tested at 25 ° C, 50 ° C, 70 ° C respectively.
  • the lithium/thionyl chloride battery prepared by the blank group electrolyte containing no quaternary ammonium salt ionic liquid has a higher discharge capacity in the temperature range of 25 ° C to 140 ° C.
  • the lithium/cartazyl chloride battery produced by the experimental group electrolyte containing large quaternary ammonium salt ionic liquid has little difference in discharge capacity from 25 ° C to 140 ° 0 .
  • the electrolyte for lithium/thionyl chloride batteries containing a quaternary ammonium salt-based ionic liquid has high battery catalytic ability in a range from normal temperature to high temperature, so that lithium containing the electrolyte is obtained.
  • /Thionyl chloride batteries have consistent high-performance discharge capability from ambient temperature to high temperature.
  • Embodiment 16 An embodiment of an electrolyte for a lithium/manganese dioxide battery containing a conventional electrolyte and a quaternary ammonium salt-based ionic liquid; the conventional electrolyte is propylene carbonate (PC), Dimethyl ether (DME) and carbon 1,3-dioxolane (DOL) are mixed as a solvent in a certain ratio, and lithium perchlorate (LiC104) is used as an electrolyte salt.
  • the concentration of lithium perchlorate (LiC104) is 0.5. ⁇ 1.5 mol/L; the quaternary ammonium salt-based ionic liquid contains a cation and an anion.
  • the electrolytic solution was prepared in the same manner as in Example 1.
  • the quaternary ammonium salt ionic liquid Specific choice of ions and volume of quaternary ammonium salt ionic liquid in the electrolyte
  • the volume percentage of the quaternary ammonium salt-based ionic liquid in the electrolytic solution is 15%, and The quaternary ammonium salt-based ionic liquid in which a specific cation and an anion are combined, and the lithium/manganese dioxide battery produced by the electrolytic solution of the present embodiment have the most uniform discharge ability at different temperatures.
  • Embodiment 30 The test for the effect of the electrolyte for a lithium/manganese dioxide battery containing a quaternary ammonium salt-based ionic liquid on the discharge capacity of the battery from a normal temperature to a high temperature range is carried out by using an experimental group and a blank group, and the experimental group includes an experiment.
  • Electrolyte used in the blank group was a common electrolyte for lithium/manganese dioxide lithium batteries, and propylene carbonate (PC), Dimethyl ether (DME) and carbon 1,3-dioxolane (DOL) are mixed as a solvent in a certain ratio, and lithium perchlorate (LiC104) is used as an electrolyte salt.
  • concentration of lithium perchlorate (LiC104) is 0.5. ⁇ 1.5mol/L, that is, the electrolyte of the blank group does not contain the quaternary ammonium salt ionic liquid in the experimental group.
  • the CR17335 lithium/manganese dioxide battery was fabricated using the electrolyte of the experimental group and the blank group, respectively, and then the lithium/manganese dioxide battery fabricated by the blank group was tested at 350 °C at 0 °C, 25 °C, and 60 °C, respectively. Constant current discharge capacity (the results are shown in Figure 3); The lithium/manganese dioxide battery produced by the test group was subjected to 350 mA constant current discharge at 0 °C, 25 °C and 60 °C (results see the attached drawing 4)).
  • the discharge capacity of the lithium/manganese dioxide lithium battery of the experimental group was taken as the average value of the discharge capacity of the lithium/manganese dioxide battery fabricated in the experimental group 1-14.
  • the lithium/manganese dioxide battery made of the blank group electrolyte containing no quaternary ammonium salt ionic liquid has a higher discharge capacity in the temperature range of 0 ° C to 60 ° C.
  • the lithium/manganese dioxide battery produced by the experimental group electrolyte containing the quaternary ammonium salt ionic liquid has little difference in discharge ability in the temperature range from 0 ° C to 60 ° C.
  • Example 31 An embodiment of the present invention for an electrolyte of a lithium/carbon fluoride battery, the electrolyte containing a conventional electrolyte and a quaternary ammonium salt ionic liquid; the conventional electrolyte is propylene carbonate (PC), diterpene ether (DME) (or Y-butyl propyl ester) is mixed as a solvent in a certain ratio, using lithium tetrafluoroborate (LIBF4) as an electrolyte salt, and the concentration of lithium tetrafluoroborate (LIBF4) is 0.5 to 1.5 mol/L;
  • the quaternary ammonium salt ionic liquid contains a cation and an anion.
  • the electrolytic solution was prepared in the same manner as in Example 1.
  • the specific selection of cations and anions in the quaternary ammonium salt ionic liquid and the volume percentage of the quaternary ammonium salt ionic liquid in the electrolyte The content is shown in the following table:
  • Embodiment 45 The test for the effect of the electrolyte for a lithium/carbon fluoride battery containing a quaternary ammonium salt-based ionic liquid on the discharge capacity of the battery from a normal temperature to a high temperature range is carried out by using an experimental group and a blank group, and the experimental group includes an experiment.
  • Electrolytes prepared in Examples 31-44 were a common electrolyte for lithium/carbon fluoride lithium batteries, and propylene carbonate (PC), Dimethyl ether (DME) (or Y-butyl propyl ester) is mixed as a solvent in a certain ratio, and lithium tetrafluoroborate (LIBF4) is used as an electrolyte salt, and the concentration of lithium tetrafluoroborate (LIBF4) is 0.5 to 1.5 mol/L. That is, the electrolyte of the blank group does not contain the quaternary ammonium salt ionic liquid in the experimental group.
  • PC propylene carbonate
  • DME Dimethyl ether
  • LIBF4 lithium tetrafluoroborate
  • concentration of lithium tetrafluoroborate (LIBF4) is 0.5 to 1.5 mol/L. That is, the electrolyte of the blank group does not contain the quaternary ammonium salt ionic liquid in the experimental group.
  • the lithium/fluorinated carbon battery of BR17335 type was prepared by using the electrolyte of the experimental group and the blank group, respectively, and then the lithium/carbon fluoride battery fabricated by the blank group was subjected to 10 kQ at 0 ° C, 25 ° C and 60 ° C, respectively. Constant resistance discharge capacity (results shown in Figure 5); Lithium/carbon fluoride batteries produced by the test group were subjected to 10kQ constant resistance discharge at 0 °C, 25 °C and 60 °C (results see the attached drawing 6)).
  • the discharge capacity of the lithium/carbon fluoride lithium battery of the experimental group was taken as the average value of the discharge capacities of the lithium/carbon fluoride batteries fabricated in the experimental groups 1-14.
  • the lithium/carbon fluoride battery made of the blank group electrolyte containing no quaternary ammonium salt ionic liquid has a higher discharge capacity in the temperature range of 0 ° C to 60 ° C.
  • the lithium/carbon fluoride battery produced by the experimental group electrolyte containing the quaternary ammonium salt ionic liquid has little difference in discharge ability in the temperature range from 0 ° C to 60 ° C.
  • the lithium/fluorinated carbon battery fabricated by the electrolyte containing the quaternary ammonium salt ionic liquid has a relatively uniform discharge capacity at different temperatures. It should be noted that the above embodiments are only intended to illustrate the technical solutions of the present invention, and are not intended to limit the scope of the present invention. The technical solutions of the present invention may be modified or equivalently substituted without departing from the spirit and scope of the technical solutions of the present invention.

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Abstract

本发明公开一种锂电池用电解液，所述电解液含有季铵盐类离子液体，所述季铵盐类离子液体包含阳离子和阴离子；所述阳离子为N-烷基季铵盐；所述阴离子为卤化盐离子、四氟硼酸阴离子、六氟磷酸阴离子、二（三氟甲基磺酰）亚胺阴离子、乳酸根阴离子、对甲基苯磺酸根阴离子、乙酰磺酰亚胺阴离子、糖精阴离子、氨基酸类阴离子、硫酸酯类阴离子，丁二酸二异辛酯磺酸根阴离子、4，5-二硝基咪唑阴离子、5-硝基四唑阴离子中的一种。本发明所述电解液中含有的季铵盐类离子液体可作为宽温电池反应催化剂，能够使高温锂电池在从常温到高温范围内具有一致的高性能放电能力。同时，本发明还公开了含有该电解液的锂电池。

Description

说 明 书
—种锂电池用电解激氣使用该电解激的锂电 *
歡术领域 本发明涉及一种锂电池用电解液氣使用读电解液的裡电 ， 尤其是一种锂 / 亚硫酰氯电池或锂 /二氧化锰电池或锂 /氟化瓖电池用电解液及使用鍾电解 的 锂电池。 背景技术 锂电池以其高能、 低自放电率、 长储存寿命以及绿色环保等特性被广泛应 用于仪器仪表、 记忆电源以及军事、 石油钻探等领域。 以锂 /亚蔬酰氯电池为倒， 普通设计的 4靈 /业硫酸氯电池其使用温度范围通常 在 -4(TC到 +85 ，而应用于石油 4*丼领域的高温锂 /亚硫酸氯电池则可以达到 150 °C、 180 甚至 200 的髙温。 在这类髙温电池的设计中 , 以往只是在普通电池 的设计基础上通过减少活性物质的量来达到高温使用的能力 , 这在实际的放电 过程中， 会出现常温和高温下放电能力相差较大的情况 , 甚至出现高温下放电 电压平台不稳、 拖尾等现象, 严重影响了髙温锂电池的性能。 同祥在其他体系的锂电池中 (如锂 /二氣化锰、 锂 /氣化碳电池）， 也存在不 同温区放电性能不一致的问题， 表现在低温 ( 0 C )和高温 ( +60 Ό )放电时容 量和负栽电压较正常放电偏离较大， 这会影响以这类电池为电源的仪器仪表的 使用。 发明内容 本发明的目的在于克服现有技术的不足之处而提供一种使锂电池从低温到 高温的宽温范围内具有一致的高性能放电能力的电解液; 同时, 本发明还提供 一种含有所述电解液的锂电池。 为实现上述目的， 本发明采取的技术方案为： 一种锂电池用电解液， 所述 电解液含有季铵盐类离子液体， 所述季铵盐类离子液体包含阳离子和阴离子； 所述阳离子为 N-烷基季铵盐；
所述阴离子为卤化盐离子、 四氟硼酸阴离子、 六氟磷酸阴离子、 二（三氟 曱基磺酰） 亚胺阴离子、 乳酸根阴离子、 对曱基苯磺酸根阴离子、 乙酰磺酰亚 胺阴离子、 糖精阴离子、 氨基酸类阴离子、 硫酸酯类阴离子、 丁二酸二异辛酯 磺酸根阴离子、 4,5-二硝基咪唑阴离子、 5-硝基四唑阴离子中的一种。 本发明的电解液提出了一种提高锂电池宽温性能的新方法， 即在电解液中 添加季铵盐类离子液体， 所添加的季铵盐类离子液体可作为一类宽温电池反应 催化剂， 所述季铵盐类离子液体包含阳离子和阴离子， 所述阳离子为 N-綻基季 铵盐， 所述阴离子为卤化盐离子、 四氟硼酸阴离子、 六氟磷酸阴离子、 二（三 氟曱基磺酰） 亚胺阴离子、 乳酸根阴离子、 对曱基苯磺酸根阴离子、 乙酰磺酰 亚胺阴离子、 糖精阴离子、 氨基酸类阴离子、 硫酸酯类阴离子、 丁二酸二异辛 酯磺酸根阴离子、 4,5-二硝基咪唑阴离子、 5-硝基四唑阴离子中的一种； 其中所 述阴离子中， 除面化盐阴离子外的其他阴离子的分子结构式如下所示：
Figure imgf000004_0001
T二酸 狰華囀緣酸锒 »离子 4 二第 睐噠,离子 所述季铵盐类离子液体具有较宽的液体范围、 较强的溶解能力、 较低的蒸 汽压、 较合适的黏度、 较高的导电性、 较宽的电化学窗口等特点， 这些特点使 其存在广阔的应用前景。 本所述电解液中， 季铵盐类离子液体在电解液中的加 入， 可以起到宽温催化剂的效果， 即在从常温到高温的范围内都具备较高的电 池反应催化能力， 使得电池在宽温范围内都具备一致的高性能放电能力， 同时 还能显著抑制金属锂负极表面钝化膜层的增长， 提高其存储性能。 作为本发明所述锂电池用电解液的优选实施方式， 所述阳离子为四烷基季 铵盐。 作为本发明所述锂电池用电解液的更优选实施方式， 所述阳离子为四曱 基铵。 所述阳离子选择四烷基季铵盐时， 形成的季铵盐类离子液体能够更好的 发挥宽温电池反应催化剂的作用； 所述阳离子选择四曱基铵时， 形成的季铵盐 类离子液体能够最好的发挥宽温电池反应催化剂的作用。 作为本发明所述锂电池用电解液的优选实施方式， 所述阴离子为面化盐离 子。 作为本发明所述锂电池用电解液的更优选实施方式， 所述阴离子为四氯化 铝酸根离子。 所述阴离子选择卤化盐离子时， 形成的季铵盐类离子液体能够更 好的发挥宽温电池反应催化剂的作用； 所述阴离子选择四氯化铝酸根离子
( A1C14" )时， 形成的季铵盐类离子液体能够最好的发挥宽温电池反应催化剂的 作用。 作为本发明所述锂电池用电解液的优选实施方式， 所述电解液中季铵盐类 离子液体的体积百分含量为 0.1~50%。作为本发明所述锂电池用电解液的更优选 实施方式， 所述电解液中季铵盐类离子液体的体积百分含量为 1~15%。 作为本 发明所述锂电池用电解液的最优选实施方式， 所述电解液中季铵盐类离子液体 的体积百分含量为 5%。 所述电解液中季铵盐类离子液体的体积百分含量为 1~15%时，所述电解液制备的锂电池在从低温到高温的范围内具有更一致的高性 能放电能力； 所述电解液中季铵盐类离子液体的体积百分含量为 5%时， 所述电 解液制备的锂电池在从低温到高温的范围内具有最一致的高性能放电能力。 同时， 本发明还提供了如上所述锂电池用电解液的制备方法， 所述方法包 括以下步骤：
( 1 )预电解：在无水环境下正负极用高纯铝片，接通稳压电源，电压 1.08V, 电解 24小时， 除去季铵盐类离子液体中的水分；
( 2 )将季铵盐类离子液体加入到常规电解液中， 混合均匀即可。
上述所述锂电池用电解液的制备方法中， 首先将季铵盐类离子液体在无水 环境（水分含量 < 0.1% ) 下进行预电解， 除去季铵盐类离子液体中的水分， 然 后再将季铵盐类离子液体按照所述的体积比加入到常规电解液中， 混合均与即 得本发明的电解液， 操作方便筒单。 实践中， 优选地将季铵盐类离子液体进行 预电解除去其中的水分后再加入到常规电解液中， 当然也可以不对季铵盐类离 子液体进行预电解， 而直接加入到常规电解液中。 另外， 本发明还提供了一种含有如上所述锂电池用电解液的锂电池。 本发 明所述提供的含有如上所述锂电池用电解液的锂电池， 由于所述电解液中含有 的季铵盐类离子液体可作为一类宽温电池反应催化剂， 因此本发明的锂电池具 备从低温到高温的宽温范围内一致的高性能放电能力。 作为本发明所述锂电池的优选实施方式， 所述锂电池为锂 /亚^ L酰氯电池， 所述电解液中还含有亚硫酰氯和四氯铝酸锂。 现有技术中锂 /亚硫酰氯电池常用 的电解液为 LiAlCl4-SOCl2锂 /亚硫酰氯电解液， 其中 LiAlC 浓度为 0.7M~2.5M 范围，筒称为 "常规电解液"。将上述所述季铵盐类离子液体添加剂加入到该 "常 规电解液" 中， 混合均匀， 即可作为本发明所述锂 /亚硫酰氯电池的电解液。 作为本发明所述锂电池的优选实施方式， 所述锂电池为锂 /二氧化锰电池， 所述电解液中还含有碳酸丙烯酯、 1,3-二氧戊环、 二曱醚和高氯酸锂。 现有技术 中锂 /二氧化锰电池常用的电解液是将碳酸丙烯酯 （PC )、 二曱醚（DME )和碳 1,3-二氧戊环（DOL )以一定的比例混合作为溶剂， 以高氯酸锂 ( LiC104 )为电 解质盐， 高氯酸锂（LiC104 ) 的浓度一般为 0.5~1.5mol/L, 配制成常用电解液。 将上述季铵盐类离子液体作为添加剂加入到上述配制的常用电解液中， 混合均 匀， 即可作为本发明所述锂 /二氧化锰电池的电解液。 尤其是当所述季铵盐类离 子液体的阳离子选择四烷基季铵盐、 阴离子选择二（三氟曱基磺酰） 亚胺阴离 子， 且季铵盐类离子在最终所得锂 /二氧化锰电池电解液中的体积百分含量为 15%时， 能够使制得的锂 /二氧化锰锂电池在不同温度下具有更加一致的放电能 力。 作为本发明所述锂电池的优选实施方式， 所述锂电池为锂 /氟化碳电池， 所 述电解液中还含有碳酸丙烯酯、 二曱醚或 Y -丁丙酯、 四氟硼酸锂。 现有技术中， 锂 /氟化碳电池常用的电机也是将碳酸丙烯酯（PC )和二曱醚（DME ) (或 γ丁 丙酯）混合作为溶剂， 以四氟硼酸锂 ( LIBF4 )为电解质盐， 四氟硼酸锂 ( LIBF4 ) 的浓度一般为 0.5~1.5mol/L, 配制成常用电解液。 将上述季铵盐类离子液体作为 添加剂加入到上述配制的常用电解液中， 混合均匀, 即可作为本发明所述锂 /氟 化碳电池的电解液。 尤其是当所述季铵盐类离子液体的阳离子选择四烷基季铵 盐、 阴离子选择二（三氟曱基橫酰） 亚胺阴离子， 且季铵盐类离子在最终所得 锂 /氟化碳电池电解液中的体积百分含量为 15%时， 能够使制得的锂 /氟化碳锂电 池在不同温度下具有更加一致的放电能力。 本发明所述锂电池用电解液， 其中添加了季铵盐类离子液体作为添加剂， 是一种新型的电解液体系， 其中添加的季铵盐类离子液体可以起到宽温催化剂 的效果， 在从低温到高温的范围内都具备较高的电池反应催化能力， 使得电池 在宽温范围内都具备一定的高性能放电能力。 本发明所述的锂电池， 因为采用 本发明的电解液， 因此具备从常温到高温范围内一致的高性能放电能力。 附图说明 图 1为采用空白组电解液制作成的锂 /亚硫酰氯电池分别在 25°C、 50°C、 70 °C、 80°C、 100°C、 120°C和 140°C的恒阻 10Ω放电能力曲线图。 图 2为采用本发明电解液制作的锂 /亚硫酰氯电池分别在 25°C、 50°C、 70°C、 80°C、 100°C、 120°C和 140°C的恒阻 10Ω放电能力曲线图。 图 3为采用空白组电解液制作成的锂 /二氧化锰电池分别在 0°C、 25°C和 60 °C的恒流 350mA放电能力曲线图。 图 4为采用本发明电解液制作成的锂 /二氧化锰电池分别在 0°C、 25°C和 60 °C的恒流 350mA放电能力曲线图。 图 5为采用空白组电解液制作成的锂 /氟化碳电池分别在 0°C、 25°C和 60°C 的恒阻 lkQ放电能力曲线图。 图 6为采用本发明电解液制作成的锂 /氟化碳电池分别在 0°C、 25°C和 60°C 的恒阻 lkQ放电能力曲线图。 具体实施方式 为更好的说明本发明的目的、 技术方案和优点， 下面将结合附图和具体实 施方式对本发明作进一步说明。 实施例 1 本发明锂电池用电解液的一种实施例， 本实施例所述电解液用于锂 /亚石 酰 氯电池， 所述电解液含有常规电解液和季铵盐类离子液体， 所述季铵盐类离子 液体包含阳离子和阴离子， 所述阳离子为四曱基铵， 所述阴离子为卤化盐离子， 常规电解液为浓度为 1.5M的 LiAlCl4-SOCl2锂 /亚硫酰氯常规电解液。 本实施例 中的电解液中， 季铵盐类离子液体的体积百分含量为 1%。 本实施例的电解液采 用以下方法制备而成：
( 1 )预电解： 在无水环境下（水分含量 < 0.1% )正负极用高纯铝片， 接通 稳压电源， 电压为 1.08V, 电解 24小时， 除去季铵盐类离子液体中的水分；
( 2 )将季铵盐类离子液体加入常规电解液中， 混合均匀即得本实施例的电 解液。 实施例 2 本发明锂电池用电解液的一种实施例， 本实施例所述电解液用于锂 /亚石 A酰 氯电池， 所述电解液含有常规电解液和季铵盐类离子液体， 所述季铵盐类离子 液体包含阳离子和阴离子， 所述阳离子为四乙基铵， 所述阴离子为四氯化铝酸 根离子， 常规电解液为浓度为 1.5M的 LiAlCl4-SOCl2锂 /亚硫酰氯常规电解液。 本实施例中的电解液中， 季铵盐类离子液体的体积百分含量为 5%。 本实施例的 电解液的制备方法同实施例 1。 实施例 3 本发明锂电池用电解液的一种实施例， 本实施例所述电解液用于锂 /亚石 A酰 氯电池， 所述电解液含有常规电解液和季铵盐类离子液体， 所述季铵盐类离子 液体包含阳离子和阴离子， 所述阳离子为四丙基铵， 所述阴离子为四氟硼酸阴 离子， 常规电解液为浓度为 1.5M的 LiAlCl4-SOCl2锂 /亚硫酰氯常规电解液。 本 实施例中的电解液中， 季铵盐类离子液体的体积百分含量为 10%。 本实施例的 电解液的制备方法同实施例 1。 实施例 4 本发明锂电池用电解液的一种实施例， 本实施例所述电解液用于锂 /亚石 酰 氯电池， 所述电解液含有常规电解液和季铵盐类离子液体， 所述季铵盐类离子 液体包含阳离子和阴离子， 所述阳离子为四丁基铵， 所述阴离子为六氟磷酸阴 离子， 常规电解液为浓度为 1.5M的 LiAlCl4-SOCl2锂 /亚硫酰氯常规电解液。 本 实施例中的电解液中， 季铵盐类离子液体的体积百分含量为 30%。 本实施例的 电解液的制备方法同实施例 1。 实施例 5 本发明锂电池用电解液的一种实施例， 本实施例所述电解液用于锂 /亚石 A酰 氯电池， 所述电解液含有常规电解液和季铵盐类离子液体， 所述季铵盐类离子 液体包含阳离子和阴离子， 所述阳离子为二曱基二乙基铵， 所述阴离子为二（三 氟曱基礒酰）亚胺阴离子， 常规电解液为浓度为 1.5M的 LiAlCl4-SOCl2锂 /亚硫 酰氯常规电解液。 本实施例中的电解液中， 季铵盐类离子液体的体积百分含量 为 50%。 本实施例的电解液的制备方法同实施例 1。 实施例 6 本发明锂电池用电解液的一种实施例， 本实施例所述电解液用于锂 /亚石 A酰 氯电池， 所述电解液含有常规电解液和季铵盐类离子液体， 所述季铵盐类离子 液体包含阳离子和阴离子， 所述阳离子为十二烷基三曱基铵， 所述阴离子为乳 S史根阴离子， 常规电解液为浓度为 1.5M的 LiAlCl4-SOCl2锂 /亚硫酰氯常规电解 液。 本实施例中的电解液中， 季铵盐类离子液体的体积百分含量为 3%。 本实施 例的电解液的制备方法同实施例 1。 实施例 7 本发明锂电池用电解液的一种实施例， 本实施例所述电解液用于锂 /亚石 A酰 氯电池， 所述电解液含有常规电解液和季铵盐类离子液体， 所述季铵盐类离子 液体包含阳离子和阴离子， 所述阳离子为十二烷基二曱基苄基铵， 所述阴离子 为对曱基苯磺酸根阴离子， 常规电解液为浓度为 1.5M的 LiAlCl4-SOCl2锂 /亚硫 酰氯常规电解液。 本实施例中的电解液中， 季铵盐类离子液体的体积百分含量 为 6%。 本实施例的电解液的制备方法同实施例 1。 实施例 8 本发明锂电池用电解液的一种实施例， 本实施例所述电解液用于锂 /亚石 A酰 氯电池， 所述电解液含有常规电解液和季铵盐类离子液体， 所述季铵盐类离子 液体包含阳离子和阴离子， 所述阳离子为四曱基铵， 所述阴离子为乙酰橫酰亚 胺阴离子，常规电解液为浓度为 1.5M的 LiAlCl4-SOCl2锂 /亚硫酰氯常规电解液。 本实施例中的电解液中， 季铵盐类离子液体的体积百分含量为 15%。 本实施例 的电解液的制备方法同实施例 1。 实施例 9 本发明锂电池用电解液的一种实施例， 本实施例所述电解液用于锂 /亚石 A酰 氯电池， 所述电解液含有常规电解液和季铵盐类离子液体， 所述季铵盐类离子 液体包含阳离子和阴离子， 所述阳离子为二曱基二丁基铵， 所述阴离子为糖精 阴离子， 常规电解液为浓度为 1.5M的 LiAlCl4-SOCl2锂 /亚硫酰氯常规电解液。 本实施例中的电解液中， 季铵盐类离子液体的体积百分含量为 18%。 本实施例 的电解液的制备方法同实施例 1。 实施例 10 本发明锂电池用电解液的一种实施例， 本实施例所述电解液用于锂 /亚石 A酰 氯电池， 所述电解液含有常规电解液和季铵盐类离子液体， 所述季铵盐类离子 液体包含阳离子和阴离子， 所述阳离子为四乙基铵， 所述阴离子为氨基酸类阴 离子， 常规电解液为浓度为 1.5M的 LiAlCl4-SOCl2锂 /亚硫酰氯常规电解液。 本 实施例中的电解液中， 季铵盐类离子液体的体积百分含量为 20%。 本实施例的 电解液的制备方法同实施例 1。 实施例 11 本发明锂电池用电解液的一种实施例， 本实施例所述电解液用于锂 /亚石 酰 氯电池， 所述电解液含有常规电解液和季铵盐类离子液体， 所述季铵盐类离子 液体包含阳离子和阴离子， 所述阳离子为四丁基铵， 所述阴离子为硫酸酯类阴 离子， 常规电解液为浓度为 1.5M的 LiAlCl4-SOCl2锂 /亚硫酰氯常规电解液。 本 实施例中的电解液中， 季铵盐类离子液体的体积百分含量为 25%。 本实施例的 电解液的制备方法同实施例 1。 实施例 12 本发明锂电池用电解液的一种实施例， 本实施例所述电解液用于锂 /亚石 A酰 氯电池， 所述电解液含有常规电解液和季铵盐类离子液体， 所述季铵盐类离子 液体包含阳离子和阴离子， 所述阳离子为十二烷基三乙基铵， 所述阴离子为丁 二酸二异辛酯磺酸根阴离子， 常规电解液为浓度为 1.5M的 LiAlCl4-SOCl2锂 /亚 硫酰氯常规电解液。 本实施例中的电解液中， 季铵盐类离子液体的体积百分含 量为 35%。 本实施例的电解液的制备方法同实施例 1。 实施例 13 本发明锂电池用电解液的一种实施例， 本实施例所述电解液用于锂 /亚石 A酰 氯电池， 所述电解液含有常规电解液和季铵盐类离子液体， 所述季铵盐类离子 液体包含阳离子和阴离子， 所述阳离子为十二烷基三丁基铵，所述阴离子为 4,5- 二硝基咪唑阴离子， 常规电解液为浓度为 1.5M的 LiAlCl4-SOCl2锂 /亚硫酰氯常 规电解液。 本实施例中的电解液中， 季铵盐类离子液体的体积百分含量为 40%。 本实施例的电解液的制备方法同实施例 1。 实施例 14 本发明锂电池用电解液的一种实施例， 本实施例所述电解液用于锂 /亚石 A酰 氯电池， 所述电解液含有常规电解液和季铵盐类离子液体， 所述季铵盐类离子 液体包含阳离子和阴离子， 所述阳离子为十二烷基二乙基苄基铵， 所述阴离子 为 5-硝基四唑阴离子， 常规电解液为浓度为 1.5M的 LiAlCl4-SOCl2锂 /亚硫酰氯 常规电解液。 本实施例中的电解液中， 季铵盐类离子液体的体积百分含量为 45%。 本实施例的电解液的制备方法同实施例 1。 实施例 15 本发明含有季铵盐类离子液体的锂 /亚硫酰氯电池用电解液对电池从常温到 高温范围内放电能力作用的试验 采用实验组和空白组的方式进行试验，实验组包括实验组 1-14,实验组 1-14 分别采用实施例 1-14制备得到的电解液，而空白组采用的电解液为浓度为 1.5M 的 LiAlCl4-SOCl2锂 /亚硫酰氯常规电解液，即空白组的电解液不含有实验组中的 季铵盐类离子液体。分别采用实验组和空白组的电解液制作 ER26102S-150型高 温锂 /亚石 A酰氯电池， 然后检测空白组制作的锂 /亚石 Α酰氯电池分别在 25 °C、 50 °C、 70°C、 80°C、 100°C、 120°C和 140°C的恒阻 10Ω放电能力 （结果见附图 1 所示）； 检测实验组制作的锂 /亚硫酰氯电池分别在 25°C、 50°C、 70°C、 80°C、 100°C、 120°C和 140°C的恒阻 10Ω放电能力 （结果见附图 2所示）。 其中， 所述 实验组的锂电池的放电能力取实验组 1 - 14制作的锂 /亚硫酰氯电池的放电能力的 平均值。 由附图 1和 2对比可看出， 不含有季铵盐类离子液体的空白组电解液制作 的锂 /亚硫酰氯电池， 在 25°C到 140°C的温度范围内， 放电能力差别较大、 而含 有季铵盐类离子液体的实验组电解液制作的锂 /亚石 υ酰氯电池， 在从 25°C到 140 °0的范围内放电能力差别不大。 由此可证明， 本发明含有季铵盐类离子液体的 锂 /亚硫酰氯电池用电解液， 在从常温到高温的范围内都具备较高的电池催化能 力， 使得含有所述电解液的锂 /亚硫酰氯电池从常温到高温的范围内都具备一致 的高性能放电能力。 实施例 16 本发明用于锂 /二氧化锰电池的电解液的实施例， 所述电解液含有常规电解 液和季铵盐类离子液体；所述常规电解液为将碳酸丙烯酯（PC )、二曱醚（DME ) 和碳 1,3-二氧戊环（DOL ) 以一定的比例混合作为溶剂， 以高氯酸锂 ( LiC104 ) 为电解质盐， 高氯酸锂（LiC104 )的浓度为 0.5~1.5mol/L; 所述季铵盐类离子液 体含有阳离子和阴离子。 所述电解液的制备方法同实施例 1。 本发明用于锂 /二氧化锰电池的电解液的各实施例中， 所述季铵盐类离子液 离子的具体选择以及所述电解液中季铵盐类离子液体的体积百
Figure imgf000013_0001
实施例 季铵盐类离子液体 阳离子 阴离子
序号 的体积百分含量 二曱基二乙基
16 卤化盐离子 1%
铵
17 四乙基铵 四氯化铝酸根离子 5%
18 四丙基铥- 四氟硼酸阴离子 10%
19 四丁基镇- 六氟磚酸阴离子 30%
20 四曱基铵 二（三氟曱基礒酰）亚胺阴离子 15% 十二烷基三曱
21 乳酸根阴离子 3%
基铵 十二烷基二曱
22 对曱基苯橫酸根阴离子 6%
基苄基铵
23 四曱基铵 乙酰礒酰亚胺阴离子 50% 二曱基二丁基
24 糖精阴离子 18%
铵
25 四乙基铵 氨基酸类阴离子 20%
26 四丁基镇- 硫酸酯类阴离子 25% 十二烷基三乙
27 丁二酸二异辛酯磺酸根阴离子 35%
基铵 十二烷基三丁
28 4,5-二硝基咪唑阴离子 40%
基铵 十二烷基二乙
29 5-硝基四唑阴离子 45%
基苄基铵 上述实施例的锂 /二氧化锰电池用电解液中， 实施例 20的电解液中， 由于季 铵盐类离子液体在电解液中的体积百分含量为 15%, 且选择所述特定阳离子和 阴离子组合而成的季铵盐类离子液体， 本实施例的电解液制作成的锂 /二氧化锰 电池中， 在不同温度下具有最为一致的放电能力。 实施例 30 本发明含有季铵盐类离子液体的锂 /二氧化锰电池用电解液对电池从常温到 高温范围内放电能力作用的试验 采用实验组和空白组的方式进行试验，实验组包括实验组 1-14,实验组 1-14 分别采用实施例 16-29制备得到的电解液， 而空白组采用的电解液为锂 /二氧化 锰锂电池常用电解液， 将碳酸丙烯酯（PC )、 二曱醚（DME )和碳 1,3-二氧戊环 ( DOL ) 以一定的比例混合作为溶剂， 以高氯酸锂 ( LiC104 ) 为电解质盐， 高 氯酸锂（LiC104 )的浓度为 0.5~1.5mol/L, 即空白组的电解液不含实验组中的季 铵盐类离子液体。分别采用实验组和空白组的电解液制作成 CR17335型号的锂 / 二氧化锰电池， 然后检测空白组制作的锂 /二氧化锰电池分别在 0°C、 25 °C和 60 °C下进行 350mA恒流放电能力 （结果见附图 3所示）； 检测实验组制作的锂 /二 氧化锰电池分别在 0°C、 25 °C和 60°C下进行 350mA恒流放电能力 （结果见附图 4所示）。其中，所述实验组的锂 /二氧化锰锂电池的放电能力取实验组 1-14制作 的锂 /二氧化锰电池的放电能力的平均值。 由附图 3和 4对比可看出， 不含有季铵盐类离子液体的空白组电解液制成 的锂 /二氧化锰电池， 在 0°C到 60°C的温度范围， 放电能力差别较大； 而含有季 铵盐类离子液体的实验组电解液制作的锂 /二氧化锰电池， 在从 0°C到 60°C的温 度范围放电能力差别不大。 由此可证明， 本发明含有季铵盐类离子液体的电解 液制作成的锂 /二氧化锰电池， 在不同温度下具有较为一致的放电能力。 实施例 31 本发明用于锂 /氟化碳电池的电解液的实施例， 所述电解液含有常规电解液 和季铵盐类离子液体； 所述常规电解液为将碳酸丙烯酯（PC )、 二曱醚（DME ) (或 Y -丁丙酯） 以一定的比例混合作为溶剂， 以四氟硼酸锂 ( LIBF4 ) 为电解 质盐， 四氟硼酸锂（LIBF4 ) 的浓度为 0.5~1.5mol/L; 所述季铵盐类离子液体含 有阳离子和阴离子。 所述电解液的制备方法同实施例 1。 本发明用于锂 /氟化碳电池的电解液的各实施例中， 所述季铵盐类离子液体 中阳离子和阴离子的具体选择以及所述电解液中季铵盐类离子液体的体积百分 含量见下表： 实施例 季铵盐类离子液体 阳离子 阴离子
序号 的体积百分含量 二曱基二乙基
31 卤化盐离子 1%
铵
32 四乙基铵 四氯化铝酸根离子 5%
33 四丙基铥- 四氟硼酸阴离子 10%
34 四丁基镇- 六氟磚酸阴离子 30%
35 四曱基铵 二（三氟曱基礒酰）亚胺阴离子 15% 十二烷基三曱
36 乳酸根阴离子 3%
基铵 十二烷基二曱
37 对曱基苯橫酸根阴离子 6%
基苄基铵
38 四曱基铵 乙酰礒酰亚胺阴离子 50% 二曱基二丁基
39 糖精阴离子 18%
铵
40 四乙基铵 氨基酸类阴离子 20% 41 四丁基镇- 硫酸酯类阴离子 25% 十二烷基三乙
42 丁二酸二异辛酯磺酸根阴离子 35%
基铵 十二烷基三丁
43 4,5-二硝基咪唑阴离子 40%
基铵 十二烷基二乙
44 5-硝基四唑阴离子 45%
基苄基铵 上述实施例的锂 /氟化碳电池用电解液中， 实施例 35的电解液中， 由于季铵 益类离子液体在电解液中的体积百分含量为 15%, 且选择所述特定阳离子和阴 离子组合而成的季铵盐类离子液体， 本实施例的电解液制作成的锂 /氟化碳电池 中， 在不同温度下具有最为一致的放电能力。 实施例 45 本发明含有季铵盐类离子液体的锂 /氟化碳电池用电解液对电池从常温到高 温范围内放电能力作用的试验 采用实验组和空白组的方式进行试验，实验组包括实验组 1-14,实验组 1-14 分别采用实施例 31-44制备得到的电解液， 而空白组采用的电解液为锂 /氟化碳 锂电池常用电解液， 将碳酸丙烯酯（PC )、 二曱醚（DME ) (或 Y -丁丙酯）以一 定的比例混合作为溶剂，以四氟硼酸锂（ LIBF4 )为电解质盐，四氟硼酸锂（ LIBF4 ) 的浓度为 0.5~1.5mol/L, 即空白组的电解液不含实验组中的季铵盐类离子液体。 分别采用实验组和空白组的电解液制作成 BR17335型号的锂 /氟化碳电池， 然后 检测空白组制作的锂 /氟化碳电池分别在 0°C、 25°C和 60°C下进行 10kQ恒阻放 电能力 （结果见附图 5所示）； 检测实验组制作的锂 /氟化碳电池分别在 0°C、 25 °C和 60°C下进行 10kQ恒阻放电能力 （结果见附图 6所示）。 其中， 所述实验组 的锂 /氟化碳锂电池的放电能力取实验组 1-14制作的锂 /氟化碳电池的放电能力 的平均值。 由附图 5和 6对比可看出， 不含有季铵盐类离子液体的空白组电解液制成 的锂 /氟化碳电池， 在 0°C到 60°C的温度范围， 放电能力差别较大； 而含有季铵 盐类离子液体的实验组电解液制作的锂 /氟化碳电池， 在从 0°C到 60°C的温度范 围放电能力差别不大。 由此可证明， 本发明含有季铵盐类离子液体的电解液制 作成的锂 /氟化碳电池， 在不同温度下具有较为一致的放电能力。 最后所应当说明的是， 以上实施例仅用以说明本发明的技术方案而非对本 发明保护范围的限制， 尽管参照较佳实施例对本发明作了详细说明， 本领域的 普通技术人员应当理解， 可以对本发明的技术方案进行修改或者等同替换， 而 不脱离本发明技术方案的实质和范围。

Claims

1、一种锂电池用电解液，其特征在于，所述电解 含有季 藍类离子 ¾·， 述季铵盈类离子 体包含阳离子和]1月离子；
所迷阳离子为 N-烷基季 &;
所途围离子为 ¾化盐离子、 氟硼酸網离子、 六氟磷酸阴离子、 二（三氟 甲基續 ） 駿阴离子、 L 艮阴离子、 对甲基 «酸根阴离子、 乙酰磺 亚 胺阴离子、 耱精阴离子、 酸类 M离子、 酸西 I类蘭离子、 丁二酸二弄辛画旨 續 阴离子、 4,5-二硝基味嗤围离子、 5-硝基 W唑調离子中的一种。
2、 如权利要求 1所途的锂电池用电解波， 其特粗在于， 所逹阳离子为 基季 。
3、 如权利要求 1所述的锂电池用电解液， 其特征在于， 所迷阳离子为四甲 基鲁 e
4、 如权利要求 1或 2或 3所述的锂电池用电解轰， 其特征在于， 所述 离 子为卤化盐离子。
5、 如权利要求 4 途的锂电 用电解褒， 其特輕在于， 所述 离子为 氯 化铝酸根离子，
6、 如权利要求 1至 5任一 述的锂电池用电解翁， 其特粗在于， 所迷电解 浪中季铵藍类离子褒体的体积、百分含量为 0.1〜50%β
7、 如权利要求 6所述的锂电池用电解液， 其特征在于， 所迷电解 中季镂 类离子褒体的体 百分含量为 1~15%
8、 如权利要求 7所述的锂电池用电解液， 其特粗在于， 所迷电解激中季 盐类离子液体的体积百分含量为 5%。
9、 如权利要求 1-8任一所述锂电池用电解液的制备方法， 其特 在于， 所 述方法包括以下步猓：
( 1 )预电解：在兌水环境下正负极用高純铝片，接通稳压电 ，电压 1.08V, 电解 24小时， 除去季铵盐类离子液体中的水分；
( 2 )将季铵盐类离子液体直接加入到电解液中， 混合均匀即可。
10、 一种锂电池， 其特征在于， 所述锂电池含有如权利要求 1-8任一所述的 锂电池用电解液。
11、 如权利要求 10所述的锂电池， 其特征在于， 所述锂电池为锂 /亚硫酰氯 电池， 所述电解液中还含有亚石 A酰氯和四氯铝酸锂。
12、 如权利要求 10所述的锂电池， 其特征在于， 所述锂电池为锂 /二氧化锰 电池， 所述电解液中还含有碳酸丙烯酯、 二曱醚、 1,3-二氧戊环和高氯酸锂。
13、 如权利要求 10所述的锂电池， 其特征在于， 所述锂电池为锂 /氟化碳电 池， 所述电解液中还含有碳酸丙烯酯、 二曱醚或 Υ -丁丙酯、 四氟硼酸锂。
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