WO2015042851A1 - Electrolyte for lithium battery and lithium battery using same - Google Patents

Electrolyte for lithium battery and lithium battery using same Download PDF

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Publication number
WO2015042851A1
WO2015042851A1 PCT/CN2013/084412 CN2013084412W WO2015042851A1 WO 2015042851 A1 WO2015042851 A1 WO 2015042851A1 CN 2013084412 W CN2013084412 W CN 2013084412W WO 2015042851 A1 WO2015042851 A1 WO 2015042851A1
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Prior art keywords
electrolyte
lithium
anion
battery
ionic liquid
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PCT/CN2013/084412
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French (fr)
Chinese (zh)
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曹浪
袁中直
刘金成
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惠州亿纬锂能股份有限公司
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Priority to PCT/CN2013/084412 priority Critical patent/WO2015042851A1/en
Priority to CN201380002472.4A priority patent/CN103814468B/en
Publication of WO2015042851A1 publication Critical patent/WO2015042851A1/en

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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
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • 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

Definitions

  • the present invention relates to an electrolyte for a lithium battery and a lithium battery containing the same, particularly for a lithium/thionyl chloride battery or a lithium/manganese dioxide battery or a lithium/carbon fluoride battery.
  • 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.
  • SEI film passivation layer
  • This passivation film hinders further reaction of the metal lithium and the electrolyte, so that the lithium battery has a low self Discharge rate and long shelf life.
  • this passivation film tends to overgrow, causing severe passivation of the battery and high self-discharge rate, causing battery failure.
  • a common method such as adding a certain amount of the dioxide A S0 2 to the electrolyte, or adding a transition metal macrocyclic compound, an organic polymer additive, an anodic coating treatment or the like.
  • a new electrolyte solution for a lithium battery containing a pyridine-based ionic liquid in addition, the present invention also provides a lithium battery using the electrolyte.
  • the technical solution adopted by the present invention is: an electrolyte for a lithium battery, the electrolyte containing a pyridine ionic liquid, the pyridine ionic liquid comprising a cation and an anion;
  • the cation is an N-alkylpyridine
  • the anion is a tetrachloroaluminate ion, a gallium tetrachloride ion, an tetrafluoroborate anion, Hexafluorophosphate anion, bis(trifluoromethylsulfonyl) imide anion, lactate anion, p-nonylbenzenesulfonate anion, acetyltrans-imide anion, saccharin anion, amino acid anion, sulfate anion, butyl One of diisooctyl sulfonate disulfate, 4,5-dinitroimidazolium anion, 5-nitrotetrazole anion.
  • the pyridine ion liquid contains an cation and an anion, the cation is an N-alkyl pyridine, and the anion is a tetrachloroaluminate ion, and the pyridine ionic liquid is added as an additive to the electrolyte for a lithium battery of the present invention.
  • the structural formulas outside the aluminosilicate ion (A1C1 4 - ) and the gallium chloride ion (GaC) are as follows:
  • the pyridine ionic liquid has a wide liquid range, a strong solvency, a low vapor pressure, a relatively suitable viscosity, a high electrical conductivity, a wide electrochemical window, etc., and these advantages make it exist Broad application prospects.
  • the application of pyridine ionic liquid in lithium battery can change the composition and structure of the passivation film to form a relatively stable passivation film.
  • the passivation film of this layer is suppressed with the increase of storage time, and the lithium battery can be significantly improved. High temperature discharge performance.
  • the principle of the pyridine ionic liquid affecting the passivation film layer is as follows: It is generally believed that the SEI film layer structure formed on the anode surface of the lithium battery is divided into two layers, which are a close layer close to the lithium sheet and a loose layer close to the electrolyte.
  • the tight layer has the ability of electronic insulation and good ion conductivity, while the loose layer is loosely porous due to its structure, and the electronic conductivity is poor, which is the main reason for the voltage lag in the initial stage of battery discharge.
  • a pyridine ionic liquid When a pyridine ionic liquid is added, its strongly polar cationic group (such as n-butylpyridine) can be effectively adsorbed in the SEI film layer.
  • the high conductivity of the ionic liquid enhances the ionic conductivity of the SEI film layer.
  • the migration of lithium ions is relatively suppressed, and the growth of the loose layer is suppressed.
  • the two functions play a role in reducing the passivation of the lithium battery.
  • the cation is N-butylpyridine.
  • the cation is N-butylpyridine.
  • the cation may be N-mercaptopyridine such as N-mercaptopyridine or N-ethylpyridine, and when the cation is selected from N-butylpyridine, the passivation phenomenon of the lithium battery can be more effectively alleviated; more preferably When the cation is selected from N-n-butylpyridine, the passivation of the lithium battery can be minimized.
  • the anion is aluminum chloride S sigma ion or gallium sulphate ion.
  • the anion is selected from a tetrachloroaluminate ion or a gallium tetrachloride ion
  • the passivation of the lithium/thionyl chloride battery can be more effectively alleviated.
  • the anion is a bis(trifluoromethyl decanoyl)imide anion.
  • the anion is selected from the bis(trifluoromethylnonanoyl)imide anion, the passivation of the lithium/carbon fluoride battery and the storage of the lithium/manganese dioxide battery can be more effectively mitigated.
  • the volume percentage of the pyridine ionic liquid in the electrolytic solution is 0.1 to 50%. In a more preferred embodiment of the electrolytic solution for a lithium battery of the present invention, the volume percentage of the pyridine ionic liquid in the electrolytic solution is 5 to 15%. As a most preferred embodiment of the electrolytic solution for a lithium battery of the present invention, the volume percentage of the pyridine-based ionic liquid in the electrolytic solution is 5%. When the volume content of the pyridine ionic liquid in the electrolyte is 5 to 15%, the electrolyte can suppress the growth of the passivation film and improve the storage performance of the battery.
  • the present invention also provides a method for preparing an electrolyte for a lithium battery as described above, the method comprising the steps of:
  • the regulated power supply is turned on, the voltage is 1.08V, and the electrolysis is performed for 24 hours to remove the moisture in the pyridine liquid.
  • the pyridine ionic liquid is directly added to the electrolyte, and the mixture is uniformly mixed.
  • a pyridine-based ionic liquid is pre-electrolyzed in an anhydrous environment (water content ⁇ 0.1%) to remove moisture in the pyridine-based ionic liquid, and then the pyridine-based liquid is further removed.
  • the sub-liquid is added to the conventional electrolyte according to the volume ratio described above, and the mixture is obtained in the same manner as the electrolyte of the present invention, and the operation is convenient.
  • the pyridine ionic liquid is preferably pre-electrolyzed to remove the water therein and then added to the conventional electrolyte.
  • the pyridine-based liquid may be pre-electrolyzed without being directly electrolyzed into the conventional electrolyte.
  • the present invention provides a lithium battery comprising the electrolytic solution for a lithium battery as described above. Since the lithium battery contains the electrolyte solution for a lithium battery containing the pyridine-based ionic liquid, the passivation film of the lithium battery is effectively suppressed as the storage time is prolonged, thereby having high storage performance and Longer storage life.
  • the lithium battery is a lithium/alloy acid chloride battery, and the electrolyte further contains thionyl chloride and lithium tetrachloroaluminate.
  • the electrolyte commonly used for lithium/thionyl chloride batteries is LiAlCl 4 -SOCl 2 lithium/thionyl chloride electrolyte, wherein the concentration of LiAlCl 4 is in the range of 0.7M to 2.5M, and the above pyridine ionic liquid additive is added to The electrolyte solution is uniformly mixed and can be used as an electrolyte solution of the lithium/thionyl chloride battery of the present invention.
  • the SEI film layer formed on the anode surface of the lithium/thionyl chloride battery is divided into two layers, which are a close layer close to the lithium sheet and a loose layer close to the electrolyte.
  • the tight layer has the ability of electronic insulation and good ion conductivity, while the loose layer is loosely porous due to its structure, and the ion conductivity is poor, which is the main reason for the voltage lag in the initial stage of battery discharge.
  • a pyridine ionic liquid When a pyridine ionic liquid is added, its strongly polar cationic group (such as n-butylpyridine) can be effectively adsorbed in the SEI film layer.
  • the high conductivity of the ionic liquid enhances the ionic conductivity of the SEI film layer.
  • the migration of lithium ions is relatively suppressed, and the growth of the loose layer is suppressed.
  • the two functions play a role in alleviating the passivation phenomenon of the lithium/thionyl chloride battery.
  • the lithium battery is a lithium/manganese dioxide battery,
  • the electrolyte also contains propylene carbonate, 1,3-dioxolane, didecyl ether and lithium perchlorate.
  • 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 pyridine ionic liquid is added as an additive to the usual electrolyte 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 pyridine ionic liquid is selected from N-butylpyridine
  • an anion is selected from a di(trifluoroindolyl succinyl)imide anion
  • the pyridine ion is in the finally obtained lithium/manganese dioxide battery electrolyte.
  • the volume percentage is 15%, the SEI film growth on the surface of metallic lithium can be more effectively suppressed, and the self-discharge rate is lowered.
  • the self-discharge rate is still low after storage at 60 ° C for 200 days (corresponding to storage at normal temperature for 10 years). .
  • the lithium battery is a lithium/carbon fluoride battery
  • the electrolyte further contains propylene carbonate, diterpene ether or Y-butyl propionate, and lithium tetrafluoroborate.
  • a common motor for a lithium/carbon fluoride battery is also a mixture of propylene carbonate (PC) and diterpene ether (DME) (or ⁇ -butyl propyl ester) as a solvent, and lithium tetrafluoroborate (LIBF4) as an electrolyte.
  • PC propylene carbonate
  • DME diterpene ether
  • LIBF4 lithium tetrafluoroborate
  • the concentration of the salt, lithium tetrafluoroborate (LIBF4) is generally 0.5 to 1.5 mol/L, and is formulated into a common electrolyte.
  • the above pyridine ionic liquid is added as an additive to the above-mentioned conventional electrolyte solution, and mixed and hooked, and can be used as an electrolyte solution of the lithium/carbon fluoride battery of the present invention.
  • an anion is selected from a bis(trifluoroindolyl succinyl)imide anion, and the pyridine ion is in the finally obtained lithium/carbon fluoride battery electrolyte.
  • the electrolyte for a lithium battery of the present invention is added to a conventional electrolyte by using a pyridine ionic liquid as an additive, and a highly polar cationic group in the pyridine ionic liquid can be effectively adsorbed in the SEI film layer.
  • the high conductivity of the ionic liquid enhances the ionic conductivity of the SEI film layer. On the other hand, it inhibits the migration of lithium ions and inhibits the growth of the loose layer.
  • the addition of a pyridine ionic liquid in a lithium battery can change the composition and structure of the passivation film to form a relatively stable passivation film, which is suppressed by the prolonged storage time, thereby significantly improving the lithium battery.
  • the lithium battery containing the above electrolyte solution of the present invention has a long storage life and high storage performance.
  • 1 is a diagram showing the results of an AC impedance test of a lithium/ succinyl chloride lithium battery fabricated by using an electrolyte solution prepared by the electrolyte of the present invention and a lithium/ succinyl chloride lithium battery produced by a blank group electrolyte.
  • 2 is a graph showing the results of an AC impedance test after a one-time storage of a lithium/ succinyl chloride lithium battery made of a lithium-lithium/succinyl chloride lithium battery produced by the electrolytic solution of the present invention at 70 ° C for one week.
  • 3 is a comparison diagram of the new electricity of the lithium/manganese dioxide lithium battery fabricated by the electrolyte of the present invention and the lithium/manganese dioxide lithium battery fabricated by the blank group electrolyte and the discharge after storage at 60 ° C for 200 days.
  • 4 is a comparison diagram of initial voltages of a lithium/carbon fluoride lithium battery fabricated from a lithium/carbon fluoride lithium battery fabricated by the electrolytic solution of the present invention and a blank group electrolyte.
  • Embodiment 1 An embodiment of an electrolyte solution for a lithium battery of the present invention, wherein the electrolyte solution is used for a lithium/saltyl chloride battery, the electrolyte solution contains a conventional electrolyte solution and a pyridine ionic liquid, and the pyridine compound
  • the ionic liquid comprises a cation and an anion
  • the cation is cerium-butyl pyridine
  • the anion is a tetrachloroaluminate ion
  • 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 pyridine ionic liquid in the electrolyte is 1%.
  • the electrolyte of this embodiment was prepared by the following method:
  • Pre-electrolysis In the anhydrous environment, the high-purity aluminum sheet is used for the positive and negative electrodes, the regulated power supply is turned on, the voltage is 1.08V, and the electrolysis is performed for 24 hours to remove the moisture in the pyridine-based ionic liquid;
  • Example 2 An embodiment of the electrolyte for a lithium battery of the present invention, the electrolyte according to the embodiment is used for a lithium/saltyl chloride battery, the electrolyte contains a conventional electrolyte and a pyridine ionic liquid, and the pyridine ionic liquid comprises a cation and an anion, the cation is ruthenium-n-butyl pyridine, the anion is a gallium tetrachloride ion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/thionyl chloride conventional electrolyte having a concentration of 1.5 M, electrolysis The volume fraction of the pyridine ionic liquid in the liquid is 5%.
  • Embodiment 3 An embodiment of an electrolyte solution for a lithium battery of the present invention, the electrolyte solution of the embodiment is used for a lithium/slate A acid chloride battery, the electrolyte solution comprising a conventional electrolyte solution and a pyridine ionic liquid, the pyridine
  • the ionic liquid contains a cation and an anion, the cation is ruthenium-hydrazinopyridine, the anion is a bis(trifluoromethylsulfonyl)imide anion, and the conventional electrolyte is LiAlCl 4 -SOCl 2 lithium at a concentration of 1.5M.
  • Embodiment 4 An embodiment of an electrolyte solution for a lithium battery of the present invention, the electrolyte solution of the present embodiment is used for a lithium/slate A acid chloride battery, the electrolyte solution comprising a conventional electrolyte solution and a pyridine ionic liquid, the pyridine
  • the ionic liquid contains a cation and an anion, the cation is ⁇ -ethyl pyridine, the anion is a 4,5-dinitroimidazolium anion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/sulfurous solution having a concentration of 1.5M.
  • the electrolytic solution of this embodiment was prepared in the same manner as in Example 1.
  • Embodiment 5 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, the electrolyte containing a conventional electrolyte and a pyridine ionic liquid, the pyridine
  • the ionic liquid contains a cation and an anion, the cation is ⁇ -propyl pyridine, the anion is a diisooctyl succinate sulfonate anion, and the conventional electrolyte is LiAlCl 4 -SOCl 2 lithium/Asia at a concentration of 1.5M.
  • Embodiment 6 An embodiment of an electrolyte solution for a lithium battery of the present invention, the electrolyte solution of the embodiment is used for a lithium/saltyl chloride battery, the electrolyte solution comprising a conventional electrolyte solution and a pyridine ionic liquid, the pyridine
  • the ionic liquid comprises a cation and an anion, the cation is ⁇ -isopropylpyridine, the anion is a tetrafluoroborate anion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/thionyl chloride conventional electrolyte having a concentration of 1.5M.
  • 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, the electrolyte containing a conventional electrolyte and a pyridine ionic liquid, the pyridine
  • the ionic liquid comprises a cation and an anion, the cation is cerium-isobutyl pyridine, the anion is a hexafluoroarabate anion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/thionyl chloride conventional electrolysis having a concentration of 1.5M.
  • Embodiment 8 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, the electrolyte containing a conventional electrolyte and a pyridine ionic liquid, the pyridine
  • the ionic liquid comprises a cation and an anion, the cation is cerium-sec-butylpyridine, the anion is a lactate anion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/thionyl chloride conventional electrolyte having a concentration of 1.5M.
  • Embodiment 9 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, the electrolyte containing a conventional electrolyte and a pyridine ionic liquid, the pyridine
  • the ionic liquid contains a cation and an anion, the cation is ⁇ -tert-butyl pyridine, the anion is a s-based benzene S-root anion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/Asia at a concentration of 1.5M.
  • Embodiment 10 An embodiment of the electrolyte for lithium of the present invention, the electrolyte according to the embodiment is used for a lithium/saltyl chloride battery, the electrolyte containing a conventional electrolyte and a pyridine ionic liquid, the pyridine ion
  • the liquid comprises a cation and an anion, the cation is ⁇ -n-butyl pyridine, the anion is an acetyl phthalimide 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 pyridine ionic liquid in the electrolyte is 20%.
  • the electrolytic solution of this embodiment was prepared in the same manner as in Example 1.
  • Embodiment 11 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, the electrolyte containing a conventional electrolyte and a pyridine ionic liquid, the pyridine
  • the ionic liquid comprises a cation and an anion, the cation is ruthenium-mercaptopyridine, the anion is a saccharin anion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/thionyl chloride conventional electrolyte having a concentration of 1.5 M, and an electrolyte
  • the volume fraction of the pyridine ionic liquid is 25%.
  • Embodiment 12 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, the electrolyte containing a conventional electrolyte and a pyridine ionic liquid, the pyridine
  • the ionic liquid contains a cation and an anion, the cation is ⁇ -ethyl pyridine, the anion is an amino acid anion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/thionyl chloride conventional electrolyte having a concentration of 1.5 M, and electrolysis
  • the volume fraction of the pyridine ionic liquid in the 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 of the present embodiment is used for a lithium/slate A acid chloride battery, the electrolyte solution comprising a conventional electrolyte solution and a pyridine ionic liquid, the pyridine Ionic liquid Containing a cation and an anion, the cation is N-propyl pyridine, 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 1.5 M, in an electrolyte
  • the pyridine ionic liquid has a volume percentage of 40%.
  • Embodiment 14 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, the electrolyte containing a conventional electrolyte and a pyridine ionic liquid, the pyridine
  • the ionic liquid contains a cation and an anion, the cation is ⁇ -isopropylpyridine, the anion is a 5-nitrotetrazole anion, and the conventional electrolyte is LiAlCl 4 -SOCl 2 lithium/thionyl chloride at a concentration of 1.5M.
  • Example 15 The storage performance of the electrolyte for lithium/thionyl chloride lithium battery of the present invention was tested by the experimental group and the blank group.
  • the experimental group included the experimental group 1-14, and the experimental group 1-14 used the examples respectively. 1-14 to prepare the obtained electrolyte, and the electrolyte used in the blank group is a LiAlCl 4 -SOCl 2 lithium/thionyl chloride conventional electrolyte having a concentration of 1.5 M, that is, the electrolyte of the blank group does not contain the pyridine in the experimental group.
  • Ionic liquid is a LiAlCl 4 -SOCl 2 lithium/thionyl chloride conventional electrolyte having a concentration of 1.5 M, that is, the electrolyte of the blank group does not contain the pyridine in the experimental group.
  • Lithium batteries were fabricated using the electrolytes of the experimental group and the blank group, respectively, and then the AC impedances of the lithium batteries just prepared by the experimental group and the blank group were respectively detected (the results are shown in Fig. 1); the experimental group and the blank group were fabricated. After the lithium battery was stored at 70 ° C for one week, the AC impedances of the lithium batteries of the experimental group and the blank group were separately detected (the results are shown in Fig. 2). The AC impedance of the lithium battery of the experimental group was taken as the average value of the AC impedance of the lithium battery fabricated in the experimental group 1-14. As can be seen from Fig.
  • the lithium battery of the experimental group still has good performance after being stored at 70 ° C for one week, and the lithium battery of the blank group has a battery failure phenomenon after one week of storage at 70 ° C.
  • the electrolyte for lithium/thionyl chloride battery of the present invention can change the composition of the passivation film of the lithium/thionyl chloride battery due to the addition of the pyridine ionic liquid, and effectively suppress the growth of the passivation film, thereby effectively improving
  • the storage performance of lithium/thionyl chloride batteries allows lithium/thionyl chloride batteries to have a longer shelf life.
  • Embodiment 16 An embodiment of an electrolyte for a lithium/manganese dioxide battery containing a conventional electrolyte and a pyridine-based ionic liquid; the conventional electrolyte is propylene carbonate (PC), bismuth 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 pyridine 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 the cation and anion and the volume percent of the pyridine ionic liquid in the electrolyte are as follows:
  • Example 30 The test of the storage performance of the electrolyte for the lithium/manganese dioxide battery of the present invention was carried out by using an experimental group and a blank group.
  • the experimental group included the experimental group 1-14, and the experimental group 1-14 used the embodiment 16 respectively.
  • -29 The prepared electrolyte is prepared, and the electrolyte used in the blank group is a common electrolyte for a lithium/manganese dioxide lithium battery, and propylene carbonate (PC), diterpene ether (DME) and carbon 1,3-dioxane are used.
  • PC propylene carbonate
  • DME diterpene ether
  • carbon 1,3-dioxane carbon 1,3-dioxane
  • the ring (DOL) is mixed as a solvent in a certain ratio, and lithium perchlorate (LiC104) is used as an electrolyte salt, and the concentration of lithium perchlorate (LiC104) is 0.5 to 1.5 mol/L, that is, the electrolyte of the blank group does not contain an experiment.
  • the CR17335 lithium/manganese dioxide battery was prepared by using the electrolyte of the experimental group and the blank group respectively, and the new power of the experimental group and the blank group was measured. The test results are shown in Fig. 3; then the experimental group and the blank group were respectively tested.
  • each data of the lithium battery of the experimental group is the average value of each data of the lithium battery fabricated in the experimental group 1-14. As can be seen from the comparison of FIG.
  • the electrolyte of the lithium/manganese dioxide battery of the experimental group contains a pyridine-based ionic liquid, and after the same storage time, the blank group has a self-discharge rate of about 4.5%, and the experimental group has With a self-discharge rate of about 1.2%, it is known that the lithium/manganese dioxide battery of the experimental group has a lower self-discharge rate.
  • Embodiment 31 An embodiment of an electrolyte for a lithium/carbon fluoride battery of the present invention, the electrolyte containing a conventional electrolyte And a pyridine-based ionic liquid;
  • the conventional electrolyte is a mixture of propylene carbonate (PC), diterpene ether (DME) (or Y-butyl propyl ester) in a certain ratio as a solvent, and lithium tetrafluoroborate (LIBF4)
  • the concentration of lithium tetrafluoroborate (LIBF4) is 0.5 to 1.5 mol/L;
  • the pyridine-based 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 the cation and anion and the volume percent of the pyridine ionic liquid in the electrolyte are as follows:
  • the experimental group included the experimental group 1-14, and the experimental group 1-14 used the example 31 respectively.
  • -44 to prepare the obtained electrolyte and the electrolyte used in the blank group is a common electrolyte for lithium/carbon fluoride batteries, and propylene carbonate (PC), diterpene ether (DME) (or Y-butyl propyl ester) is fixed.
  • PC propylene carbonate
  • DME diterpene ether
  • Y-butyl propyl ester Y-butyl propyl ester
  • the ratio is mixed as a solvent, and lithium tetrafluoroborate (LIBF4) is used as the 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 pyridine ion in the experimental group. liquid.
  • the lithium/fluorinated carbon battery of BR17335 model was prepared by using the electrolyte of the experimental group and the blank group respectively, and the initial voltage of the discharge battery of the experimental group and the blank group was determined, wherein the initial voltage of the experimental group was the lithium battery fabricated by the experimental group 1-14.
  • the average of the initial voltages, the test results are shown in Figure 4.
  • the lithium/carbon fluoride battery produced by the blank group has a voltage lag phenomenon
  • the electrolyte of the lithium/fluorinated carbon battery of the experimental group contains substantially no voltage hysteresis due to the inclusion of the pyridine-based ionic liquid.

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Abstract

Disclosed is an electrolyte for a lithium battery. The electrolyte contains a pyridinium ionic liquid, and the pyridinium ionic liquid contains cations and anions, wherein the cations are N-alkyl pyridines; and the anions are one of terachloroaluminate ions, tetrachlorogallate ions, tetrafluoroborate anions, hexafluorophosphate anions, bis(trifluoromethylsulfonyl)imide anions, lactate anions, p-toluene sulfonate anions, acetyl sulfonimide anions, saccharin anions, amino acid anions, sulphate anions, diisooctyl sulfosuccinate anions, 4,5-dinitroimidazole anions and 5-nitrotetrazole anions. The electrolyte of the present invention can effectively suppress the growth of a passivation layer (an SEI film) on the lithium metal surface in a lithium battery, thereby significantly improving the storage performance of the battery. Additionally, also disclosed are a preparation method for the electrolyte and a lithium battery containing the electrolyte.

Description

一种锂电池用电解液及使用该电解液的锂电池  Electrolyte for lithium battery and lithium battery using the same
技术领域 本发明涉及一种用于锂电池的电解液及含有该电解液的锂电池， 尤其是一 种用于锂 /亚硫酰氯电池或锂 /二氧化锰电池或锂 /氟化碳电池的电解液及使用该 电解液的锂电池。 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。 在锂电池中，金属锂和电解质接触后，会在锂金属表面形成一层钝化层（ SEI 膜）， 这层钝化膜阻碍了金属锂和电解液的进一步反应， 使得锂电池具备低自放 电率和长储存寿命。 但在一些情况下， 如常温长期存储、 高温存储后， 这层钝 化膜往往会出现过度生长的现象， 造成电池严重钝化和高自放电率， 引起电池 失效。 为了提高锂电池的存储性能， 常用方法如在电解液中添加一定量的二氧 化石 A S02、或加入过渡金属大环化合物、有机高分子添加剂、阳极涂层处理等等。 发明内容 TECHNICAL FIELD The present invention relates to an electrolyte for a lithium battery and a lithium battery containing the same, particularly for a lithium/thionyl chloride battery or a lithium/manganese dioxide battery or a lithium/carbon fluoride battery. An electrolyte and a lithium battery using the same. BACKGROUND OF THE INVENTION 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. In a lithium battery, after contact with the lithium metal and the electrolyte, a passivation layer (SEI film) is formed on the surface of the lithium metal. This passivation film hinders further reaction of the metal lithium and the electrolyte, so that the lithium battery has a low self Discharge rate and long shelf life. However, in some cases, such as long-term storage at room temperature and high-temperature storage, this passivation film tends to overgrow, causing severe passivation of the battery and high self-discharge rate, causing battery failure. In order to improve the storage performance of the lithium battery, a common method such as adding a certain amount of the dioxide A S0 2 to the electrolyte, or adding a transition metal macrocyclic compound, an organic polymer additive, an anodic coating treatment or the like. Summary of the invention
性能的新的含有吡啶类离子液体的锂电池用电解液； 另外， 本发明还提供了使 用该电解液的锂电池。 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 电解液含有吡啶类离子液体， 所述吡啶类离子液体包含阳离子和阴离子； A new electrolyte solution for a lithium battery containing a pyridine-based ionic liquid; in addition, the present invention also provides a lithium battery using the electrolyte. In order to achieve the above object, the technical solution adopted by the present invention is: an electrolyte for a lithium battery, the electrolyte containing a pyridine ionic liquid, the pyridine ionic liquid comprising a cation and an anion;
所述阳离子为 N-烷基吡啶；  The cation is an N-alkylpyridine;
所述阴离子为四氯化铝酸根离子、 四氯化镓酸根离子、 四氟硼酸阴离子、 六氟磷酸阴离子、 二（三氟曱基礒酰） 亚胺阴离子、 乳酸根阴离子、 对曱基苯 磺酸根阴离子、 乙酰橫酰亚胺阴离子、 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。 本发明所述锂电池用电解液中添加吡啶类离子液体作为添加剂， 所述吡啶 类离子液体包含阳离子和阴离子， 所述阳离子为 N-烷基吡啶， 所述阴离子为四 氯化铝酸根离子、 四氯化镓酸根离子、 四氟硼酸阴离子、 六氟磷酸阴离子、 二 (三氟曱基橫酰） 亚胺阴离子、 乳酸根阴离子、 对曱基苯橫酸根阴离子、 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， 上 述阴离子中， 除四氯化铝酸根离子（ A1C14- )和四氯化镓酸根离子 （ GaC )外 的结构式分别如下： The anion is a tetrachloroaluminate ion, a gallium tetrachloride ion, an tetrafluoroborate anion, Hexafluorophosphate anion, bis(trifluoromethylsulfonyl) imide anion, lactate anion, p-nonylbenzenesulfonate anion, acetyltrans-imide anion, saccharin anion, amino acid anion, sulfate anion, butyl One of diisooctyl sulfonate disulfate, 4,5-dinitroimidazolium anion, 5-nitrotetrazole anion. The pyridine ion liquid contains an cation and an anion, the cation is an N-alkyl pyridine, and the anion is a tetrachloroaluminate ion, and the pyridine ionic liquid is added as an additive to the electrolyte for a lithium battery of the present invention. Gallium tetrachloride ion, tetrafluoroborate anion, hexafluorophosphate anion, bis(trifluorodecyl succinyl) imide anion, lactate anion, p-nonyl benzene phosphinate anion, acetyl sulfonimide anion, saccharin An anion, an amino acid anion, a sulfate anion, a diisooctyl succinate anion, a 4,5-dinitroimidazolium anion, a 5-nitrotetrazole anion, among the above anions, except for four The structural formulas outside the aluminosilicate ion (A1C1 4 - ) and the gallium chloride ion (GaC) are as follows:
Figure imgf000004_0001
所述吡啶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、 较高的导电性和较宽的电化学窗口等等， 这些优点使其存 在广阔的应用前景。 吡啶类离子液体在锂电池中的应用， 可以改变钝化膜组成 和结构， 形成较为稳定的钝化膜， 该层钝化膜随着存储时间延长的增长得到抑 制， 同时还能显著提高锂电池的高温放电性能。 吡啶类离子液体影响钝化膜层的原理为： 一般认为， 锂电池阳极表面形成 的 SEI膜层结构分为两层， 分别为贴近锂片的紧密层和靠近电解液的疏松层。 紧密层具备电子绝缘能力和良好的离子导电能力， 而疏松层则由于其结构疏松 多孔， 电子导电能力较差， 是导致电池放电初期电压滞后的主要原因。 吡啶类 离子液体的加入， 其强极性的阳离子基团（如正丁基吡啶）能够有效吸附于 SEI 膜层中， 一方面离子液体的高导电率增强了 SEI膜层的离子导电能力， 一方面 也相对抑制了锂离子的迁移， 起到抑制疏松层生长的作用。 两方面同时作用， 起到减轻锂电池钝化现象的作用。 作为本发明所述锂电池用电解液的优选实施方式， 所述阳离子为 N-丁基吡 啶。 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 N-丁基 吡啶。 所述阳离子可为 N-曱基吡啶、 N-乙基吡啶等 N-綻基吡啶， 当所述阳离子 选择 N-丁基吡啶时， 能够更有效的减轻锂电池的钝化现象； 更优选地， 当所述 阳离子选择 N-正丁基吡啶时， 能够最大程度的减轻锂电池的钝化现象。 作为本发明所述锂电池用电解液的优选实施方式， 所述阴离子为四氯化铝 S史根离子或四氯化镓酸根离子。 当所述阴离子选择四氯化铝酸根离子或四氯化 镓酸根离子时， 能够更有效的减轻锂 /亚硫酰氯电池的钝化现象。 作为本发明所述锂电池用电解液的优选实施方式， 所述阴离子为二（三氟 曱基礒酰）亚胺阴离子。 当所述阴离子选择二（三氟曱基礒酰）亚胺阴离子时， 能够更有效的减轻锂 /氟化碳电池的钝化现象和提高锂 /二氧化锰电池的存储性 h
Figure imgf000004_0001
The pyridine ionic liquid has a wide liquid range, a strong solvency, a low vapor pressure, a relatively suitable viscosity, a high electrical conductivity, a wide electrochemical window, etc., and these advantages make it exist Broad application prospects. The application of pyridine ionic liquid in lithium battery can change the composition and structure of the passivation film to form a relatively stable passivation film. The passivation film of this layer is suppressed with the increase of storage time, and the lithium battery can be significantly improved. High temperature discharge performance. The principle of the pyridine ionic liquid affecting the passivation film layer is as follows: It is generally believed that the SEI film layer structure formed on the anode surface of the lithium battery is divided into two layers, which are a close layer close to the lithium sheet and a loose layer close to the electrolyte. The tight layer has the ability of electronic insulation and good ion conductivity, while the loose layer is loosely porous due to its structure, and the electronic conductivity is poor, which is the main reason for the voltage lag in the initial stage of battery discharge. When a pyridine ionic liquid is added, its strongly polar cationic group (such as n-butylpyridine) can be effectively adsorbed in the SEI film layer. On the one hand, the high conductivity of the ionic liquid enhances the ionic conductivity of the SEI film layer. In addition, the migration of lithium ions is relatively suppressed, and the growth of the loose layer is suppressed. At the same time, the two functions play a role in reducing the passivation of the lithium battery. In a preferred embodiment of the electrolyte solution for a lithium battery of the present invention, the cation is N-butylpyridine. In a more preferred embodiment of the electrolyte solution for a lithium battery of the present invention, the cation is N-butylpyridine. The cation may be N-mercaptopyridine such as N-mercaptopyridine or N-ethylpyridine, and when the cation is selected from N-butylpyridine, the passivation phenomenon of the lithium battery can be more effectively alleviated; more preferably When the cation is selected from N-n-butylpyridine, the passivation of the lithium battery can be minimized. In a preferred embodiment of the electrolyte solution for a lithium battery of the present invention, the anion is aluminum chloride S sigma ion or gallium sulphate ion. When the anion is selected from a tetrachloroaluminate ion or a gallium tetrachloride ion, the passivation of the lithium/thionyl chloride battery can be more effectively alleviated. In a preferred embodiment of the electrolyte solution for a lithium battery of the present invention, the anion is a bis(trifluoromethyl decanoyl)imide anion. When the anion is selected from the bis(trifluoromethylnonanoyl)imide anion, the passivation of the lithium/carbon fluoride battery and the storage of the lithium/manganese dioxide battery can be more effectively mitigated.
匕。 作为本发明所述锂电池用电解液的优选实施方式， 所述电解液中吡啶类离 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， 所述电解液中吡啶类离子液体的体积百分含量为 5~15%。 作为本发明 所述锂电池用电解液的最优选实施方式， 所述电解液中吡啶类离子液体的体积 百分含量为 5%。 当所述电解液中吡啶类离子液体的体积含量为 5~15%时， 所述 电解液能够较好的抑制钝化膜的生长， 提高电池的存储性能。 当所述电解液中 吡啶类离子液体的体积含量为 5%时， 所述电解液最有效的抑制钝化膜的生长， 最大程度上提高电池的存储性能。 本发明还提供了一种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： dagger. As a preferred embodiment of the electrolyte solution for a lithium battery of the present invention, the volume percentage of the pyridine ionic liquid in the electrolytic solution is 0.1 to 50%. In a more preferred embodiment of the electrolytic solution for a lithium battery of the present invention, the volume percentage of the pyridine ionic liquid in the electrolytic solution is 5 to 15%. As a most preferred embodiment of the electrolytic solution for a lithium battery of the present invention, the volume percentage of the pyridine-based ionic liquid in the electrolytic solution is 5%. When the volume content of the pyridine ionic liquid in the electrolyte is 5 to 15%, the electrolyte can suppress the growth of the passivation film and improve the storage performance of the battery. When the volume content of the pyridine ionic liquid in the electrolytic solution is 5%, the electrolytic solution most effectively suppresses the growth of the passivation film, and maximizes the storage performance of the battery. The present invention also provides a method for preparing an electrolyte for a lithium battery as described above, the method comprising the steps of:
( 1 )在无水环境下正负极用高纯铝片， 接通稳压电源， 电压为 1.08V, 电 解 24小时， 除去吡啶类萬子液体中的水分；  (1) Using a high-purity aluminum sheet for the positive and negative electrodes in a waterless environment, the regulated power supply is turned on, the voltage is 1.08V, and the electrolysis is performed for 24 hours to remove the moisture in the pyridine liquid.
( 2 )将吡啶类离子液体直接加入到电解液中， 混合均匀即可。 上述所述锂电池用电解液的制备方法中， 首先将吡啶类离子液体在无水环 境（水分含量 < 0.1% ) 下进行预电解， 除去吡啶类离子液体中的水分， 然后再 将吡啶类萬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， 优选地将吡啶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， 当然也可以不对吡啶类萬子液体进行 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。 所述 锂电池由于含有上述所述含有吡啶类离子液体的锂电池用电解液， 因此所述锂 电池的钝化膜随着存储时间的延长的增长得到有效抑制， 从而具有较高的存储 性能和较长的存储寿命。 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 LiAlCl4浓度为 0.7M~2.5M 范围， 将上述吡啶类离子液体添加剂加入到该电解液中， 混合均匀, 即可作为 本发明所述锂 /亚硫酰氯电池的电解液。 一般认为， 锂 /亚硫酰氯电池阳极表面形 成的 SEI膜层结构分为两层， 分别为贴近锂片的紧密层和靠近电解液的疏松层。 紧密层具备电子绝缘能力和良好的离子导电能力， 而疏松层则由于其结构疏松 多孔， 离子导电能力较差， 是导致电池放电初期电压滞后的主要原因。 吡啶类 离子液体的加入， 其强极性的阳离子基团（如正丁基吡啶）能够有效吸附于 SEI 膜层中， 一方面离子液体的高导电率增强了 SEI膜层的离子导电能力， 一方面 也相对抑制了锂离子的迁移， 起到抑制疏松层生长的作用。 两方面同时作用， 起到减轻锂 /亚硫酰氯电池钝化现象的作用。 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。 将上述吡啶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。 尤其是当所述吡啶类离子液体 的阳离子选择 N-丁基吡啶、 阴离子选择二（三氟曱基橫酰） 亚胺阴离子， 且吡 啶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 更加有效抑制金属锂表面的 SEI膜生长， 降低其自放电率， 在 60°C下储存 200 天（相当于常温存储 10年） 的自放电率仍然较低。 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。 将上述吡啶类离子液体作为添 加剂加入到上述配制的常用电解液中， 混合均勾， 即可作为本发明所述锂 /氟化 碳电池的电解液。 尤其是当所述吡啶类离子液体的阳离子选择 N-丁基吡啶、 阴 离子选择二（三氟曱基橫酰）亚胺阴离子， 且吡啶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， 能够更有效的抑制金属锂表面 SEI膜 生长， 显著改善锂 /氟化碳电池放电初期电压滞后的现象。 本发明所述锂电池用电解液， 采用吡啶类离子液体作为添加剂加入到常规 电解液中， 所述吡啶类离子液体中的强极性的阳离子基团能够有效吸附于 SEI 膜层中， 一方面离子液体的高导电率增强了 SEI膜层的离子导电能力， 另一方 面相对抑制了锂离子的迁移， 起到抑制疏松层生长的作用， 两方面同时作用， 起到减轻锂电池钝化现象的作用。 吡啶类离子液体在锂电池中的添加， 可以起 到改变钝化膜组成和结构， 形成较为稳定的钝化膜， 该层钝化膜随存储时间延 长的增长得到抑制， 从而显著提高锂电池的存储性能和存储寿命。 本发明所述 含有上述所述电解液的锂电池， 具有较长的存储寿命和较高的存储性能。 附图说明 图 1为本发明所述电解液制作的锂 /亚石 酰氯锂电池与空白组电解液制作的 锂 /亚石 酰氯锂电池在刚制作好后的交流阻抗测试结果图。 图 2为本发明所述电解液制作的锂 /亚石 酰氯锂电池与空白组电解液制作的 锂 /亚石 酰氯锂电池在 70°C下存储一周后的交流阻抗测试结果图。 图 3为本发明所述电解液制作的锂 /二氧化锰锂电池与空白组电解液制作的 锂 /二氧化锰锂电池的新电及在 60°C下存储 200天后的放电对比图。 图 4为本发明所述电解液制作的锂 /氟化碳锂电池与空白组电解液制作的锂 / 氟化碳锂电池的初始电压对比图。 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 施例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吡啶类离子液体， 所述吡啶类离子液体 包含阳离子和阴离子， 所述阳离子为 Ν-丁基吡啶， 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， 电 解液中吡啶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： (2) The pyridine ionic liquid is directly added to the electrolyte, and the mixture is uniformly mixed. In the above method for preparing an electrolyte solution for a lithium battery, first, a pyridine-based ionic liquid is pre-electrolyzed in an anhydrous environment (water content < 0.1%) to remove moisture in the pyridine-based ionic liquid, and then the pyridine-based liquid is further removed. The sub-liquid is added to the conventional electrolyte according to the volume ratio described above, and the mixture is obtained in the same manner as the electrolyte of the present invention, and the operation is convenient. In practice, the pyridine ionic liquid is preferably pre-electrolyzed to remove the water therein and then added to the conventional electrolyte. Of course, the pyridine-based liquid may be pre-electrolyzed without being directly electrolyzed into the conventional electrolyte. Further, the present invention provides a lithium battery comprising the electrolytic solution for a lithium battery as described above. Since the lithium battery contains the electrolyte solution for a lithium battery containing the pyridine-based ionic liquid, the passivation film of the lithium battery is effectively suppressed as the storage time is prolonged, thereby having high storage performance and Longer storage life. In a preferred embodiment of the lithium battery of the present invention, the lithium battery is a lithium/alloy acid chloride battery, and the electrolyte further contains thionyl chloride and lithium tetrachloroaluminate. In the prior art, the electrolyte commonly used for lithium/thionyl chloride batteries is LiAlCl 4 -SOCl 2 lithium/thionyl chloride electrolyte, wherein the concentration of LiAlCl 4 is in the range of 0.7M to 2.5M, and the above pyridine ionic liquid additive is added to The electrolyte solution is uniformly mixed and can be used as an electrolyte solution of the lithium/thionyl chloride battery of the present invention. It is generally believed that the SEI film layer formed on the anode surface of the lithium/thionyl chloride battery is divided into two layers, which are a close layer close to the lithium sheet and a loose layer close to the electrolyte. The tight layer has the ability of electronic insulation and good ion conductivity, while the loose layer is loosely porous due to its structure, and the ion conductivity is poor, which is the main reason for the voltage lag in the initial stage of battery discharge. When a pyridine ionic liquid is added, its strongly polar cationic group (such as n-butylpyridine) can be effectively adsorbed in the SEI film layer. On the one hand, the high conductivity of the ionic liquid enhances the ionic conductivity of the SEI film layer. In addition, the migration of lithium ions is relatively suppressed, and the growth of the loose layer is suppressed. At the same time, the two functions play a role in alleviating the passivation phenomenon of the lithium/thionyl chloride battery. As a preferred embodiment of the lithium battery of the present invention, the lithium battery is a lithium/manganese dioxide battery, The electrolyte also contains propylene carbonate, 1,3-dioxolane, didecyl ether and lithium perchlorate. 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 pyridine ionic liquid is added as an additive to the usual electrolyte solution prepared above, and uniformly mixed, and can be used as an electrolyte solution of the lithium/manganese dioxide battery of the present invention. In particular, when the cation of the pyridine ionic liquid is selected from N-butylpyridine, an anion is selected from a di(trifluoroindolyl succinyl)imide anion, and the pyridine ion is in the finally obtained lithium/manganese dioxide battery electrolyte. When the volume percentage is 15%, the SEI film growth on the surface of metallic lithium can be more effectively suppressed, and the self-discharge rate is lowered. The self-discharge rate is still low after storage at 60 ° C for 200 days (corresponding to storage at normal temperature for 10 years). . In a preferred embodiment of the lithium battery of the present invention, the lithium battery is a lithium/carbon fluoride battery, and the electrolyte further contains propylene carbonate, diterpene ether or Y-butyl propionate, and lithium tetrafluoroborate. In the prior art, a common motor for a lithium/carbon fluoride battery is also a mixture of propylene carbonate (PC) and diterpene ether (DME) (or γ-butyl propyl ester) as a solvent, and lithium tetrafluoroborate (LIBF4) as an electrolyte. The concentration of the salt, lithium tetrafluoroborate (LIBF4) is generally 0.5 to 1.5 mol/L, and is formulated into a common electrolyte. The above pyridine ionic liquid is added as an additive to the above-mentioned conventional electrolyte solution, and mixed and hooked, and can be used as an electrolyte solution of the lithium/carbon fluoride battery of the present invention. In particular, when the cation of the pyridine ionic liquid is selected from N-butylpyridine, an anion is selected from a bis(trifluoroindolyl succinyl)imide anion, and the pyridine ion is in the finally obtained lithium/carbon fluoride battery electrolyte. When the volume percentage is 15%, the growth of the SEI film on the surface of the metallic lithium can be more effectively suppressed, and the phenomenon of voltage hysteresis at the initial stage of discharge of the lithium/carbon fluoride battery can be remarkably improved. The electrolyte for a lithium battery of the present invention is added to a conventional electrolyte by using a pyridine ionic liquid as an additive, and a highly polar cationic group in the pyridine ionic liquid can be effectively adsorbed in the SEI film layer. The high conductivity of the ionic liquid enhances the ionic conductivity of the SEI film layer. On the other hand, it inhibits the migration of lithium ions and inhibits the growth of the loose layer. At the same time, it plays a role in reducing the passivation of the lithium battery. effect. The addition of a pyridine ionic liquid in a lithium battery can change the composition and structure of the passivation film to form a relatively stable passivation film, which is suppressed by the prolonged storage time, thereby significantly improving the lithium battery. Storage performance and storage life. The lithium battery containing the above electrolyte solution of the present invention has a long storage life and high storage performance. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing the results of an AC impedance test of a lithium/ succinyl chloride lithium battery fabricated by using an electrolyte solution prepared by the electrolyte of the present invention and a lithium/ succinyl chloride lithium battery produced by a blank group electrolyte. 2 is a graph showing the results of an AC impedance test after a one-time storage of a lithium/ succinyl chloride lithium battery made of a lithium-lithium/succinyl chloride lithium battery produced by the electrolytic solution of the present invention at 70 ° C for one week. 3 is a comparison diagram of the new electricity of the lithium/manganese dioxide lithium battery fabricated by the electrolyte of the present invention and the lithium/manganese dioxide lithium battery fabricated by the blank group electrolyte and the discharge after storage at 60 ° C for 200 days. 4 is a comparison diagram of initial voltages of a lithium/carbon fluoride lithium battery fabricated from a lithium/carbon fluoride lithium battery fabricated by the electrolytic solution of the present invention and a blank group electrolyte. DETAILED DESCRIPTION OF THE INVENTION The present invention will be further described with reference to the accompanying drawings and specific embodiments. Embodiment 1 An embodiment of an electrolyte solution for a lithium battery of the present invention, wherein the electrolyte solution is used for a lithium/saltyl chloride battery, the electrolyte solution contains a conventional electrolyte solution and a pyridine ionic liquid, and the pyridine compound The ionic liquid comprises a cation and an anion, the cation is cerium-butyl pyridine, the anion is a tetrachloroaluminate 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 pyridine ionic liquid in the electrolyte is 1%. The electrolyte of this embodiment was prepared by the following method:
( 1 )预电解： 在无水环境下正负极用高纯铝片， 接通稳压电源， 电压为 1.08V, 电解 24小时， 除去吡啶类离子液体中的水分；  (1) Pre-electrolysis: In the anhydrous environment, the high-purity aluminum sheet is used for the positive and negative electrodes, the regulated power supply is turned on, the voltage is 1.08V, and the electrolysis is performed for 24 hours to remove the moisture in the pyridine-based ionic liquid;
( 2 )将吡啶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 酰 氯电池， 所述电解液含有常规电解液和吡啶类离子液体， 所述吡啶类离子液体 包含阳离子和阴离子， 所述阳离子为 Ν-正丁基吡啶， 所述阴离子为四氯化镓酸 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， 电解液中吡啶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吡啶类离子液体， 所述吡啶类离子液体 包含阳离子和阴离子， 所述阳离子为 Ν-曱基吡啶， 所述阴离子为二（三氟曱基 磺酰）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， 电解液中吡啶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 A酰 氯电池， 所述电解液含有常规电解液和吡啶类离子液体， 所述吡啶类离子液体 包含阳离子和阴离子， 所述阳离子为 Ν-乙基吡啶， 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， 电解液中吡啶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吡啶类离子液体， 所述吡啶类离子液体 包含阳离子和阴离子， 所述阳离子为 Ν-丙基吡啶， 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， 电解液中吡啶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 酰 氯电池， 所述电解液含有常规电解液和吡啶类离子液体， 所述吡啶类离子液体 包含阳离子和阴离子， 所述阳离子为 Ν-异丙基吡啶， 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， 电 解液中吡啶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吡啶类离子液体， 所述吡啶类离子液体 包含阳离子和阴离子， 所述阳离子为 Ν-异丁基吡啶， 所述阴离子为六氟磚酸阴 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， 电 解液中吡啶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吡啶类离子液体， 所述吡啶类离子液体 包含阳离子和阴离子， 所述阳离子为 Ν-仲丁基吡啶， 所述阴离子为乳酸根阴离 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， 电解 液中吡啶类离子液体的体积百分含量为 8%。 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吡啶类离子液体， 所述吡啶类离子液体 包含阳离子和阴离子， 所述阳离子为 Ν-叔丁基吡啶， 所述阴离子为对曱基苯橫 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， 电解液中吡啶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 10 本发明锂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吡啶类离子液体， 所述吡啶类离子液体包含 阳离子和阴离子， 所述阳离子为 Ν-正丁基吡啶， 所述阴离子为乙酰礒酰亚胺阴 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， 电 解液中吡啶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 A酰 氯电池， 所述电解液含有常规电解液和吡啶类离子液体， 所述吡啶类离子液体 包含阳离子和阴离子， 所述阳离子为 Ν-曱基吡啶， 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， 电解液中 吡啶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吡啶类离子液体， 所述吡啶类离子液体 包含阳离子和阴离子， 所述阳离子为 Ν-乙基吡啶， 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， 电解 液中吡啶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吡啶类离子液体， 所述吡啶类离子液体 包含阳离子和阴离子， 所述阳离子为 N-丙基吡啶， 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， 电解 液中吡啶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吡啶类离子液体， 所述吡啶类离子液体 包含阳离子和阴离子， 所述阳离子为 Ν-异丙基吡啶， 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， 电解液中吡啶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 本发明锂 /亚硫酰氯锂电池用电解液对电池存储性能的试验 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 吡啶类离子液体。 分别采用实验组和空白组的电解液制作锂电池， 然后分别检 测实验组和空白组刚制作成的锂电池的交流阻抗（结果如附图 1所示）； 将实验 组和空白组制作成的锂电池在 70°C下存储一周后， 再分别检测实验组和空白组 的锂电池的交流阻抗（结果如附图 2所示）。 其中， 所述实验组的锂电池的交流 阻抗取实验组 1-14制作的锂电池的交流阻抗的平均值。 由附图 1和附图 可看出， 实验组的锂电池在 70°C下存储一周后仍然具有 较好的性能， 而空白组的锂电池在 70°C存储一周后出现电池失效的现象。 由此 可证明， 本发明的锂 /亚硫酰氯电池用电解液由于吡啶类离子液体的加入， 能够 改变锂 /亚硫酰氯电池钝化膜的构成， 有效抑制钝化膜的增长， 从而有效提高锂 / 亚硫酰氯电池的存储性能， 使得锂 /亚硫酰氯电池具有更长的存储寿命。 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 液和吡啶类离子液体； 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; 所述吡啶类离子液体 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， 所述阳离子和阴离子 的具体选择以及所述电解液中吡啶类离子液体的体积百分含量见下表： 实施例 吡啶类离子液体的 阳离子 阴离子 (2) The pyridine-based ionic liquid is added to a conventional electrolytic solution, and the mixture is uniformly mixed to obtain the electrolytic solution of the present embodiment. Example 2 An embodiment of the electrolyte for a lithium battery of the present invention, the electrolyte according to the embodiment is used for a lithium/saltyl chloride battery, the electrolyte contains a conventional electrolyte and a pyridine ionic liquid, and the pyridine ionic liquid comprises a cation and an anion, the cation is ruthenium-n-butyl pyridine, the anion is a gallium tetrachloride ion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/thionyl chloride conventional electrolyte having a concentration of 1.5 M, electrolysis The volume fraction of the pyridine ionic liquid in the liquid is 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 of the embodiment is used for a lithium/slate A acid chloride battery, the electrolyte solution comprising a conventional electrolyte solution and a pyridine ionic liquid, the pyridine The ionic liquid contains a cation and an anion, the cation is ruthenium-hydrazinopyridine, the anion is a bis(trifluoromethylsulfonyl)imide anion, and the conventional electrolyte is LiAlCl 4 -SOCl 2 lithium at a concentration of 1.5M. /Thionyl chloride conventional electrolyte, the volume percentage of the pyridine ionic liquid in the electrolyte is 10%. The electrolytic solution of this embodiment was prepared in the same manner as in Example 1. Embodiment 4 An embodiment of an electrolyte solution for a lithium battery of the present invention, the electrolyte solution of the present embodiment is used for a lithium/slate A acid chloride battery, the electrolyte solution comprising a conventional electrolyte solution and a pyridine ionic liquid, the pyridine The ionic liquid contains a cation and an anion, the cation is Ν-ethyl pyridine, the anion is a 4,5-dinitroimidazolium anion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/sulfurous solution having a concentration of 1.5M. The conventional electrolyte of acid chloride, the volume percentage of the pyridine ionic liquid in the electrolyte is 30%. The electrolytic solution of this embodiment was prepared in the same manner as in Example 1. Embodiment 5 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, the electrolyte containing a conventional electrolyte and a pyridine ionic liquid, the pyridine The ionic liquid contains a cation and an anion, the cation is Ν-propyl pyridine, the anion is a diisooctyl succinate sulfonate anion, and the conventional electrolyte is LiAlCl 4 -SOCl 2 lithium/Asia at a concentration of 1.5M. Sulfuryl chloride conventional electrolyte, the volume percentage of the pyridine ionic liquid in the electrolyte 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 of the embodiment is used for a lithium/saltyl chloride battery, the electrolyte solution comprising a conventional electrolyte solution and a pyridine ionic liquid, the pyridine The ionic liquid comprises a cation and an anion, the cation is Ν-isopropylpyridine, the anion is a tetrafluoroborate 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 pyridine ionic liquid in the electrolytic solution was 3%. The electrolytic solution of this embodiment was prepared in the same manner as in Example 1. 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, the electrolyte containing a conventional electrolyte and a pyridine ionic liquid, the pyridine The ionic liquid comprises a cation and an anion, the cation is cerium-isobutyl pyridine, the anion is a hexafluoroarabate anion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/thionyl chloride conventional electrolysis having a concentration of 1.5M. The volume fraction of the pyridine ionic liquid in the electrolyte 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 for a lithium battery of the present invention, the electrolyte according to the embodiment is used for a lithium/slate A acid chloride battery, the electrolyte containing a conventional electrolyte and a pyridine ionic liquid, the pyridine The ionic liquid comprises a cation and an anion, the cation is cerium-sec-butylpyridine, the anion is a lactate anion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/thionyl chloride conventional electrolyte having a concentration of 1.5M. The volume fraction of the pyridine ionic liquid in the electrolyte was 8%. The electrolytic solution of this embodiment was prepared in the same manner as in Example 1. Embodiment 9 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, the electrolyte containing a conventional electrolyte and a pyridine ionic liquid, the pyridine The ionic liquid contains a cation and an anion, the cation is Ν-tert-butyl pyridine, the anion is a s-based benzene S-root anion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/Asia at a concentration of 1.5M. Sulfuryl chloride conventional electrolysis The volume percentage of the pyridine ionic liquid in the electrolyte is 15%. The electrolytic solution of this embodiment was prepared in the same manner as in Example 1. Embodiment 10 An embodiment of the electrolyte for lithium of the present invention, the electrolyte according to the embodiment is used for a lithium/saltyl chloride battery, the electrolyte containing a conventional electrolyte and a pyridine ionic liquid, the pyridine ion The liquid comprises a cation and an anion, the cation is Ν-n-butyl pyridine, the anion is an acetyl phthalimide 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 pyridine ionic liquid in the electrolyte is 20%. The electrolytic solution of this embodiment was prepared in the same manner as in Example 1. Embodiment 11 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, the electrolyte containing a conventional electrolyte and a pyridine ionic liquid, the pyridine The ionic liquid comprises a cation and an anion, the cation is ruthenium-mercaptopyridine, the anion is a saccharin anion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/thionyl chloride conventional electrolyte having a concentration of 1.5 M, and an electrolyte The volume fraction of the pyridine 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 for a lithium battery of the present invention, the electrolyte according to the embodiment is used for a lithium/slate A acid chloride battery, the electrolyte containing a conventional electrolyte and a pyridine ionic liquid, the pyridine The ionic liquid contains a cation and an anion, the cation is Ν-ethyl pyridine, the anion is an amino acid anion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/thionyl chloride conventional electrolyte having a concentration of 1.5 M, and electrolysis The volume fraction of the pyridine ionic liquid in the 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 of the present embodiment is used for a lithium/slate A acid chloride battery, the electrolyte solution comprising a conventional electrolyte solution and a pyridine ionic liquid, the pyridine Ionic liquid Containing a cation and an anion, the cation is N-propyl pyridine, 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 1.5 M, in an electrolyte The pyridine ionic liquid has a volume percentage of 40%. The electrolytic solution of this embodiment was prepared in the same manner as in Example 1. Embodiment 14 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, the electrolyte containing a conventional electrolyte and a pyridine ionic liquid, the pyridine The ionic liquid contains a cation and an anion, the cation is Ν-isopropylpyridine, the anion is a 5-nitrotetrazole anion, and the conventional electrolyte is LiAlCl 4 -SOCl 2 lithium/thionyl chloride at a concentration of 1.5M. For a conventional electrolyte, the volume percentage of the pyridine ionic liquid in the electrolyte is 45%. The electrolytic solution of this embodiment was prepared in the same manner as in Example 1. Example 15 The storage performance of the electrolyte for lithium/thionyl chloride lithium battery of the present invention was tested by the experimental group and the blank group. The experimental group included the experimental group 1-14, and the experimental group 1-14 used the examples respectively. 1-14 to prepare the obtained electrolyte, and the electrolyte used in the blank group is a LiAlCl 4 -SOCl 2 lithium/thionyl chloride conventional electrolyte having a concentration of 1.5 M, that is, the electrolyte of the blank group does not contain the pyridine in the experimental group. Ionic liquid. Lithium batteries were fabricated using the electrolytes of the experimental group and the blank group, respectively, and then the AC impedances of the lithium batteries just prepared by the experimental group and the blank group were respectively detected (the results are shown in Fig. 1); the experimental group and the blank group were fabricated. After the lithium battery was stored at 70 ° C for one week, the AC impedances of the lithium batteries of the experimental group and the blank group were separately detected (the results are shown in Fig. 2). The AC impedance of the lithium battery of the experimental group was taken as the average value of the AC impedance of the lithium battery fabricated in the experimental group 1-14. As can be seen from Fig. 1 and the accompanying drawings, the lithium battery of the experimental group still has good performance after being stored at 70 ° C for one week, and the lithium battery of the blank group has a battery failure phenomenon after one week of storage at 70 ° C. It can be confirmed that the electrolyte for lithium/thionyl chloride battery of the present invention can change the composition of the passivation film of the lithium/thionyl chloride battery due to the addition of the pyridine ionic liquid, and effectively suppress the growth of the passivation film, thereby effectively improving The storage performance of lithium/thionyl chloride batteries allows lithium/thionyl chloride batteries to have a longer shelf life. Embodiment 16 An embodiment of an electrolyte for a lithium/manganese dioxide battery containing a conventional electrolyte and a pyridine-based ionic liquid; the conventional electrolyte is propylene carbonate (PC), bismuth 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 pyridine ionic liquid contains a cation and an anion. The electrolytic solution was prepared in the same manner as in Example 1. In various embodiments of the electrolyte for use in a lithium/manganese dioxide battery of the present invention, the specific selection of the cation and anion and the volume percent of the pyridine ionic liquid in the electrolyte are as follows: Example pyridine Cationic anion of ionic liquid
序号 体积百分含量  Serial number
16 N-曱基吡啶 四氯化铝酸根离子 1% 16 N-mercaptopyridine tetrachloride aluminate 1%
17 N-乙基吡啶 四氯化镓酸根离子 5% 17 N-ethylpyridine tetraammonium chloride ion 5%
18 N-丁基吡啶 二（三氟曱基礒酰）亚胺阴离子 15% 18 N-butylpyridine bis(trifluoromethyl decanoyl)imide anion 15%
19 N-正丁基吡啶 4,5-二硝基咪唑阴离子 30% 19 N-n-butylpyridine 4,5-dinitroimidazolium anion 30%
20 N-丙基吡啶 丁二酸二异辛酯磺酸根阴离子 50% 20 N-propylpyridine diisooctyl sulfonate sulfonate anion 50%
21 N-异丙基吡啶 四氟硼酸阴离子 3% 21 N-isopropylpyridine tetrafluoroborate anion 3%
22 N-异丁基吡啶 六氟磚酸阴离子 6% 22 N-isobutylpyridine hexafluorosilicate anion 6%
23 N-仲丁基吡啶 乳酸根阴离子 8% 23 N-sec-butylpyridine lactate anion 8%
24 N-叔丁基吡啶 对曱基苯橫酸根阴离子 10% 24 N-tert-butylpyridine p-nonylbenzene cross-acid anion 10%
25 N-正丁基吡啶 乙酰礒酰亚胺阴离子 20% 25 N-n-butylpyridine Acetylphthalimide anion 20%
26 N-曱基吡啶 糖精阴离子 25% 26 N-mercaptopyridine saccharin anion 25%
27 N-乙基吡啶 氨基酸类阴离子 35% 28 N-丙基吡啶 硫酸酯类阴离子 40% 27 N-ethylpyridine amino acid anion 35% 28 N-propyl pyridine sulfate anion 40%
29 N-异丙基吡啶 5-硝基四唑阴离子 45% 上述实施例的锂 /二氧化锰电池用电解液中， 实施例 18的电解液中， 由于吡 啶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 离子组合而成的吡啶类萬子液体， 本实施例的电解液制作成的锂 /二氧化锰电池 中， 电解液中的吡啶类离子液体能够更有效的抑制金属锂表面 SEI膜生长， 显 著降低其自放电率。 实施例 30 本发明锂 /二氧化锰电池用电解液对电池存储性能的试验 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吡 啶类离子液体。 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， 测定实验组和空白组的新电， 测试结果如附图 3 所示； 然后分 别检测实验组和空白组的锂 /二氧化锰电池在 60 °C下储存 200天（相当于常温存 储 10年）后的放电情况， 测试结果如附图 3所示。 所述附图 3中， 实验组的锂 电池的各数据为实验组 1-14制作的锂电池的各数据的平均值。 由附图 3的对比可知， 实验组的锂 /二氧化锰电池的电解液由于含有吡啶类 离子液体， 在经过同样的存储时间后， 空白组具有约 4.5%的自放电率， 而实验 组具有约 1.2%的自放电率， 由此可知实验组的锂 /二氧化锰电池具有更低的自放 电率。 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 和吡啶类离子液体； 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; 所述吡啶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， 所述阳离子和阴离子的 具体选择以及所述电解液中吡啶类离子液体的体积百分含量见下表： 实施例 吡啶类离子液体的 阳离子 阴离子 29 N-isopropylpyridine 5-nitrotetrazole anion 45% In the electrolytic solution for a lithium/manganese dioxide battery of the above embodiment, in the electrolytic solution of Example 18, the volume of the pyridine-based ionic liquid in the electrolytic solution a pyridine-based ionic liquid in an electrolyte, in a lithium/manganese dioxide battery prepared by the electrolyte of the present embodiment, having a percentage of 15%, and selecting a pyridine-based liquid in which the specific cation and anion are combined. It can more effectively inhibit the growth of SEI film on the surface of metallic lithium, and significantly reduce its self-discharge rate. Example 30 The test of the storage performance of the electrolyte for the lithium/manganese dioxide battery of the present invention was carried out by using an experimental group and a blank group. The experimental group included the experimental group 1-14, and the experimental group 1-14 used the embodiment 16 respectively. -29 The prepared electrolyte is prepared, and the electrolyte used in the blank group is a common electrolyte for a lithium/manganese dioxide lithium battery, and propylene carbonate (PC), diterpene ether (DME) and carbon 1,3-dioxane are used. The ring (DOL) is mixed as a solvent in a certain ratio, and lithium perchlorate (LiC104) is used as an electrolyte salt, and the concentration of lithium perchlorate (LiC104) is 0.5 to 1.5 mol/L, that is, the electrolyte of the blank group does not contain an experiment. A pyridine-based ionic liquid in the group. The CR17335 lithium/manganese dioxide battery was prepared by using the electrolyte of the experimental group and the blank group respectively, and the new power of the experimental group and the blank group was measured. The test results are shown in Fig. 3; then the experimental group and the blank group were respectively tested. The lithium/manganese dioxide battery was stored at 60 ° C for 200 days (corresponding to storage at normal temperature for 10 years), and the test results are shown in Fig. 3. In the above FIG. 3, each data of the lithium battery of the experimental group is the average value of each data of the lithium battery fabricated in the experimental group 1-14. As can be seen from the comparison of FIG. 3, the electrolyte of the lithium/manganese dioxide battery of the experimental group contains a pyridine-based ionic liquid, and after the same storage time, the blank group has a self-discharge rate of about 4.5%, and the experimental group has With a self-discharge rate of about 1.2%, it is known that the lithium/manganese dioxide battery of the experimental group has a lower self-discharge rate. Embodiment 31 An embodiment of an electrolyte for a lithium/carbon fluoride battery of the present invention, the electrolyte containing a conventional electrolyte And a pyridine-based ionic liquid; the conventional electrolyte is a mixture of propylene carbonate (PC), diterpene ether (DME) (or Y-butyl propyl ester) in a certain ratio as a solvent, and lithium tetrafluoroborate (LIBF4) As the electrolyte salt, the concentration of lithium tetrafluoroborate (LIBF4) is 0.5 to 1.5 mol/L; the pyridine-based ionic liquid contains a cation and an anion. The electrolytic solution was prepared in the same manner as in Example 1. In various embodiments of the electrolyte for use in a lithium/carbon fluoride battery of the present invention, the specific selection of the cation and anion and the volume percent of the pyridine ionic liquid in the electrolyte are as follows: Example pyridine Cationic anion of ionic liquid
序号 体积百分含量  Serial number
31 N-曱基吡啶 四氯化铝酸根离子 1% 31 N-Mercaptopyridine Tetrachloride Aluminate Ion 1%
32 N-乙基吡啶 四氯化镓酸根离子 5% 32 N-ethylpyridine tetraammonium chloride ion 5%
33 N-丁基吡啶 二（三氟曱基礒酰）亚胺阴离子 15% 33 N-butylpyridine bis(trifluoromethyl decanoyl)imide anion 15%
34 N-正丁基吡啶 4,5-二硝基咪唑阴离子 30% 34 N-n-butylpyridine 4,5-dinitroimidazolium anion 30%
35 N-丙基吡啶 丁二酸二异辛酯磺酸根阴离子 50% 35 N-propylpyridine diisooctyl sulfonate sulfonate anion 50%
36 N-异丙基吡啶 四氟硼酸阴离子 3% 36 N-isopropylpyridine tetrafluoroborate anion 3%
37 N-异丁基吡啶 六氟磚酸阴离子 6% 37 N-isobutylpyridine hexafluorosilicate anion 6%
38 N-仲丁基吡啶 乳酸根阴离子 8% 38 N-sec-butylpyridine lactate anion 8%
39 N-叔丁基吡啶 对曱基苯橫酸根阴离子 10% 39 N-tert-butylpyridine p-nonylbenzene cross-acid anion 10%
40 N-正丁基吡啶 乙酰礒酰亚胺阴离子 20% 40 N-n-butylpyridine Acetylphthalimide anion 20%
41 N-曱基吡啶 糖精阴离子 25% 41 N-mercaptopyridine saccharin anion 25%
42 N-乙基吡啶 氨基酸类阴离子 35% 42 N-ethylpyridine Amino acid anion 35%
43 N-丙基吡啶 硫酸酯类阴离子 40% 43 N-propyl pyridine sulfate anion 40%
44 N-异丙基吡啶 5-硝基四唑阴离子 45% 上述实施例的锂 /氟化碳电池用电解液中， 实施例 33的电解液中， 由于吡啶 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 子的组合而成的吡啶类离子液体，本实施例的电解液制作成的锂 /氟化碳电池中， 电解液中的吡啶类离子液体能够更有效的抑制金属锂表面 SEI膜生长， 显著改 善其放电初期电压滞后的现象。 实施例 45 本发明锂 /氟化碳电池用电解液对电池存储性能的试验 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 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吡啶类离子液体。 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， 测定实 验组和空白组的放电池初始电压， 其中实验组的初始电压为实验组 1-14制作的 锂电池的初始电压的平均值， 测试结果见附图 4所示。 由附图 4的可知， 空白组制作的锂 /氟化碳电池存在电压滞后的现象， 而实 验组的锂 /氟化碳电池的电解液由于含有吡啶类离子液体，基本无电压滞后现象。 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。 44 N-isopropylpyridine 5-nitrotetrazole anion 45% In the electrolytic solution for a lithium/carbon fluoride battery of the above embodiment, in the electrolytic solution of Example 33, since the volume percentage of the pyridine-based ionic liquid in the electrolytic solution is 15%, and the specific cation and anion are selected In the lithium/fluorinated carbon battery prepared by the electrolyte of the present embodiment, the pyridine-based ionic liquid in the electrolyte can more effectively inhibit the growth of the SEI film on the surface of the metallic lithium, and significantly improve the discharge thereof. The phenomenon of initial voltage lag. Example 45 The storage performance of the electrolyte for lithium/carbon fluoride battery of the present invention was tested by the experimental group and the blank group. The experimental group included the experimental group 1-14, and the experimental group 1-14 used the example 31 respectively. -44 to prepare the obtained electrolyte, and the electrolyte used in the blank group is a common electrolyte for lithium/carbon fluoride batteries, and propylene carbonate (PC), diterpene ether (DME) (or Y-butyl propyl ester) is fixed. The ratio is mixed as a solvent, and lithium tetrafluoroborate (LIBF4) is used as the 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 pyridine ion in the experimental group. liquid. The lithium/fluorinated carbon battery of BR17335 model was prepared by using the electrolyte of the experimental group and the blank group respectively, and the initial voltage of the discharge battery of the experimental group and the blank group was determined, wherein the initial voltage of the experimental group was the lithium battery fabricated by the experimental group 1-14. The average of the initial voltages, the test results are shown in Figure 4. As can be seen from FIG. 4, the lithium/carbon fluoride battery produced by the blank group has a voltage lag phenomenon, and the electrolyte of the lithium/fluorinated carbon battery of the experimental group contains substantially no voltage hysteresis due to the inclusion of the pyridine-based ionic liquid. 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.

Claims

权 1111利 1111要 1111求 1111书 1 Rights1111Benefits1111Requirements1111Book 1
1、 一种锂电池用电解液， 其特征在于， 所述电解液含有吡啶类离子液体， 所述吡啶类离子液体包含阳离子和阴离子； 1. An electrolyte for lithium batteries, characterized in that the electrolyte contains a pyridine ionic liquid, and the pyridine ionic liquid contains cations and anions;
所述阳离子为 N-烷基吡啶； The cation is N-alkylpyridine;
所述阴离子为四氯化铝酸根离子、 四氯化镓酸根离子、 四氟硼酸阴离子、 六氟磷酸阴离子、 二（三氟曱基礒酰） 亚胺阴离子、 乳酸根阴离子、 对曱基苯 磺酸根阴离子、 乙酰橫酰亚胺阴离子、 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。 The anions are aluminum tetrachloride ion, gallate tetrachloride ion, tetrafluoroborate anion, hexafluorophosphate anion, bis(trifluoromethylacryl)imide anion, lactate anion, p-methylbenzenesulfonate Acid anion, acetyl sulfonimide anion, saccharin anion, amino acid anion, sulfate anion, diisooctyl sulfonate anion, 4,5-dinitroimidazole anion, 5-nitrotetrazolium anion one of them.
2、 如权利要求 1 所述的锂电池用电解液， 其特征在于， 所述阳离子为 N- 丁基吡 1定。 2. The electrolyte for lithium batteries according to claim 1, wherein the cation is N- butylpyridine .
3、 如权利要求 2所述的锂电池用电解液， 其特征在于， 所述阳离子为 N- 正丁基吡1定。 3. The electrolyte for lithium batteries according to claim 2, wherein the cation is N-n- butylpyridine .
4、 如权利要求 1或 2或 3所述的锂电池用电解液， 其特征在于， 所述阴离 子为四氯化铝酸根离子或四氯化镓酸根离子。 4. The electrolyte for lithium batteries according to claim 1 or 2 or 3, characterized in that the anion is an aluminate tetrachloride ion or a gallate tetrachloride ion.
5、 如权利要求 1或 2或 3所述的锂电池用电解液， 其特征在于， 所述阴离 子为二（三氟曱基礒酰） 亚胺阴离子。 5. The electrolyte for lithium batteries according to claim 1 or 2 or 3, characterized in that the anion is bis(trifluoromethylacryl)imide anion.
6、 如权利要求 1至 5任一所述的锂电池用电解液， 其特征在于， 所述电解 液中吡啶类离子液体的体积百分含量为 0.1~50%。 6. The electrolyte for lithium batteries according to any one of claims 1 to 5, characterized in that the volume percentage of pyridine ionic liquid in the electrolyte is 0.1 to 50%.
7、 如权利要求 6所述的锂电池用电解液， 其特征在于， 所述电解液中吡啶 类离子液体的体积百分含量为 5~15%。 7. The electrolyte for lithium batteries according to claim 6, wherein the volume percentage of the pyridine ionic liquid in the electrolyte is 5 to 15%.
8、 如权利要求 7所述的锂电池用电解液， 其特征在于， 所述电解液中吡啶 类离子液体的体积百分含量为 5%。 8. The electrolyte for lithium batteries according to claim 7, wherein the volume percentage of pyridine ionic liquid in the electrolyte is 5%.
9、一种如权利要求 1-8任一所述锂电池用电解液的制备方法， 其特征在于， 包括以下步骤： ( 1 )在无水环境下正负极用高纯铝片， 接通稳压电源， 电压为 1.08V, 电 解 24小时， 除去吡啶类萬子液体中的水分； 9. A method for preparing the electrolyte for lithium batteries according to any one of claims 1 to 8, characterized in that it includes the following steps: (1) In an anhydrous environment, use high-purity aluminum sheets for the positive and negative electrodes, connect to a regulated power supply, the voltage is 1.08V, electrolyze for 24 hours, and remove the moisture in the pyridine-based liquid;
( 2 )将吡啶类离子液体直接加入到电解液中， 混合均匀即可。 (2) Add the pyridine ionic liquid directly to the electrolyte and mix evenly.
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。 10. A lithium battery, characterized in that the lithium battery contains the electrolyte for lithium batteries as described in any one of claims 1-8.
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。 11. The lithium battery according to claim 10, wherein the lithium battery is a lithium/thionyl chloride battery, and the electrolyte further contains lithium A chloride and lithium tetrachloroaluminate.
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。 12. The lithium battery according to claim 10, wherein the lithium battery is a lithium/manganese dioxide battery, and the electrolyte also contains propylene carbonate, dimethyl ether, and 1,3-dioxopentane. Cyclic and lithium perchlorate.
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。 13. The lithium battery according to claim 10, characterized in that the lithium battery is a lithium/fluorocarbon battery, and the electrolyte also contains propylene carbonate, dimethyl ether or γ-butylpropyl ester, tetrahydrofuran Lithium Fluoborate.
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