WO2015042845A1 - 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
WO2015042845A1
WO2015042845A1 PCT/CN2013/084386 CN2013084386W WO2015042845A1 WO 2015042845 A1 WO2015042845 A1 WO 2015042845A1 CN 2013084386 W CN2013084386 W CN 2013084386W WO 2015042845 A1 WO2015042845 A1 WO 2015042845A1
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electrolyte
lithium
anions
battery
ionic liquid
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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 CN201380002469.2A priority Critical patent/CN103814473A/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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • 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 an electrolyte for a lithium battery and a lithium battery using the same, in particular, a lithium/thionyl chloride battery or a lithium/manganese dioxide battery or an electrolyte for a lithium/carbon fluoride battery and use thereof
  • the lithium battery of the electrolyte is 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. At present, the lithium batteries seen in the market can be generally divided into two types: capacity type and power type.
  • the former has a high capacity density but its large current discharge capability is poor, and is generally applied to a long-time working mode with a small current.
  • the latter has the ability to discharge relatively large currents, but its capacity density is relatively low.
  • Common methods for improving the high-current discharge capability of lithium batteries include: From the perspective of improving the battery reaction, adding a transition metal macrocyclic compound catalyst, changing the reduction reaction mechanism of the electrolyte, and increasing the rate of reduction reaction, thereby accelerating the entire battery reaction and improving The purpose of the discharge capacity.
  • the increase is limited because the battery reaction rate is also controlled by the mass transfer rate of the electrolyte.
  • the electrolyte for lithium battery can effectively increase the load voltage of the battery;
  • a lithium battery using the electrolyte is also provided.
  • the technical solution adopted by the present invention is: an electrolyte for a lithium battery, the electrolyte containing an imidazole-based ionic liquid, the imidazole-based ionic liquid comprising a cation and an anion;
  • the cation is a sulfonylimidazole
  • the anion is a halide ion, a tetrafluoroborate anion, a hexafluorophosphate anion, a bis(trifluorodecylsulfonyl)imide anion, a lacto-p-phenylbenzenesulfonate anion, an acetylsulfonimide anion, a saccharin anion, One of an amino acid anion, a sulfate anion, a diisooctyl succinate anion, a 4,5-dinitroimidazolium anion, and a 5-nitrotetrazole anion.
  • the electrolyte for a lithium battery of the present invention is added with an imidazole-based ionic liquid as an electrolyte additive, and the imidazole-based liquid contains a cation and an anion, and the molecular structure of the anion other than the face acid radical is as follows:
  • Imidazole ionic liquids have the advantages of wide liquid range, strong solubility, low vapor pressure, suitable viscosity, high electrical conductivity, wide electrochemical window, etc. Application prospects.
  • the electrolyte for lithium battery of the present invention is added with an imidazole ionic liquid as an additive.
  • the imidazole ionic liquid can change the reaction history of the battery, increase the reduction rate of the cathode active material, and increase the electrolyte solution.
  • Conductivity increase the mass transfer rate of the electrolyte, and at the same time, the formed electrolyte can effectively increase the discharge voltage of the lithium battery, and at the same time High-temperature discharge performance of high-lithium batteries.
  • the cation is a 1-alkyl-3-alkylimidazole. In a more preferred embodiment of the electrolyte solution for a lithium battery of the present invention, the cation is 1-mercapto-3-ethylimidazole.
  • the reduction rate of the cathode active material can be better, the conductivity of the electrolyte can be increased, and lithium can be more effectively improved.
  • the discharge voltage of the thionyl chloride battery when the cation is selected from 1-alkyl-3 alkylimidazole, the reduction rate of the cathode active material can be better, the conductivity of the electrolyte can be increased, and lithium can be more effectively improved.
  • the discharge voltage of the thionyl chloride battery when the cation is selected from 1-alkyl-3 alkylimidazole, the reduction rate of the cathode active material can be better, the conductivity of the electrolyte can be increased, and lithium can be more effectively improved.
  • the cation is selected from 1-mercapto-3-ethylimidazole, the reduction rate of the cathode active material can be most effectively increased, the electrical conductivity of the electrolyte can be increased, and the discharge voltage of the lithium/thionyl chloride battery can be most effectively improved.
  • the electrolyte is used in other kinds of lithium batteries, such as lithium/manganese dioxide batteries and lithium/carbon fluoride batteries
  • the cation is also preferably 1-mercapto-3-ethylimidazole;
  • the load voltage and capacity of the lithium/manganese dioxide battery and the lithium/carbon fluoride battery can be remarkably improved.
  • the anion when applied to a lithium/cartrite chloride battery, is a surface acid ion.
  • the anion is a tetrachloroaluminate ion (AlCl 4 - ).
  • the anion is selected as the halide ion, the reduction rate of the cathode active material can be further improved, and the electrical conductivity of the electrolyte can be increased, thereby effectively increasing the discharge voltage of the lithium/thionyl chloride battery.
  • the reduction rate of the cathode active material can be most effectively increased, the electrical conductivity of the electrolyte can be increased, and the discharge voltage of the lithium/thionyl chloride battery can be most effectively improved.
  • the anion is preferably an bis(trifluorodecylsulfonyl)imide anion;
  • the anion is selected from the bis(trifluoroindolyl acyl amide) anion anion, the load voltage and capacity of the lithium/manganese dioxide battery and the lithium/carbon fluoride battery can be remarkably improved.
  • the volume percentage of the imidazole-based ionic liquid in the electrolytic solution is 0.1 to 50%.
  • the volume percentage of the imidazole-based ionic liquid in the electrolytic solution is 1 to 15%.
  • the volume percentage of the imidazole-based ionic liquid in the electrolytic solution is 5%.
  • the electrical conductivity of the electrolyte can be better increased; when the volume percentage of the imidazole ionic liquid is 5%, the volume can be significantly increased.
  • the conductivity of the electrolyte also provides a method for preparing an electrolyte for a lithium battery as described above, the method comprising 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, to remove moisture in the imidazole ionic liquid;
  • the present invention provides a lithium battery comprising the electrolytic solution for a lithium battery as described above.
  • the lithium battery containing the electrolyte for a lithium battery as described above according to the present invention can change the reaction history of the battery, increase the conductivity of the electrolyte, and improve the mass transfer of the electrolyte because the electrolyte contains an imidazole-based ionic liquid. Rate, therefore the lithium battery has better load voltage and capacity.
  • the lithium battery is a lithium/slate A 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 above-mentioned imidazole-based ionic liquid additive is added to the "conventional electrolyte" and uniformly mixed to serve as an electrolyte of the lithium/thionyl chloride battery of the present invention.
  • the electrolyte solution contains an imidazole ionic liquid
  • the addition of the imidazole ionic liquid can change the reaction history of the battery, increase the reduction rate of the cathode active material, and increase the conductance of the electrolyte.
  • the rate, which increases the mass transfer rate of the electrolyte can simultaneously increase the discharge voltage of the lithium/thionyl chloride battery.
  • 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 imidazole-based ionic liquid is added as an additive to the above-mentioned conventional electrolytic solution, and uniformly mixed, and can be used as an electrolyte solution of the lithium/manganese dioxide battery of the present invention.
  • 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.
  • 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 imidazole-based 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.
  • the electrolyte for lithium battery of the invention adds the imidazole ionic liquid as an additive, and the addition of the imidazole ionic liquid can change the reaction history of the battery, increase the reduction rate of the cathode active material, and increase the conductivity of the electrolyte, thereby increasing the conductivity of the electrolyte.
  • the mass transfer rate of the electrolyte can simultaneously increase the discharge voltage of the lithium battery.
  • the lithium battery containing the electrolyte of the invention has a high load voltage without changing the structure of the battery, and the structure of the battery is not changed, thereby avoiding the cost increase and safety hazard caused by changing the battery design.
  • FIG. 1 is a normal temperature constant resistance of a lithium/cartazyl chloride battery fabricated by a blank group electrolyte and an electrolyte of the present invention
  • Comparison chart of 330 ⁇ discharge curve. 2 is a comparison diagram of a 100 mA discharge curve of a lithium/manganese dioxide battery produced by a blank group electrolyte and an electrolyte of the present invention at a constant temperature.
  • Fig. 3 is a comparison diagram of a discharge curve of a constant-current constant current of 10 mA for a lithium/fluorinated carbon battery fabricated by a blank group electrolyte and an electrolyte of the present invention.
  • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In order to better illustrate the objects, technical solutions and advantages of the present invention, the following will be described in conjunction with the accompanying drawings. The invention is further illustrated by the examples.
  • Embodiment 1 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/saltyl chloride battery, the electrolyte solution comprising a conventional electrolyte solution and an imidazole-based ionic liquid, the imidazole
  • the ionic liquid comprises a cation and an anion, the cation is 1-mercapto-3-ethylimidazole, the anion is a tetrachloroaluminate ion (AICU-), and the conventional electrolyte is a LiAlCl 4 -SOCl having a concentration of 1.5M. 2 lithium / thionyl chloride conventional electrolyte.
  • the volume percentage of the imidazole-based ionic liquid is 5%.
  • the electrolyte of this embodiment was prepared by the following method:
  • Pre-electrolysis In the anhydrous environment (moisture content ⁇ 0.1%), 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 imidazole ionic liquid. ;
  • Embodiment 2 An embodiment of the electrolytic solution for a lithium battery of the present invention, the electrolytic solution of the present embodiment is used for a lithium/saltyl chloride battery, the electrolytic solution containing a conventional electrolytic solution and an imidazole-based ionic liquid, the imidazole
  • the ionic liquid comprises a cation and an anion, the cation is 1-mercapto-3-propylimidazole, the anion is a tetrafluoroborate anion, and the conventional electrolyte is LiAlCl 4 -SOCl 2 lithium/thionyl chloride at a concentration of 1.5M.
  • Embodiment 3 An embodiment of the 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, the electrolyte solution containing a conventional electrolyte solution and an imidazole-based ionic liquid, the imidazole
  • the ionic liquid comprises a cation and an anion, the cation is 1-mercapto-3-butylimidazole, the anion is a hexafluorophosphate anion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/sulfurous solution having a concentration of 1.5M.
  • Acid chloride conventional electrolyte In the electrolytic solution in this embodiment, the volume percentage of the imidazole-based ionic liquid is 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, the electrolyte solution comprising a conventional electrolyte solution and an imidazole-based ionic liquid, the imidazole
  • the ionic liquid comprises a cation and an anion, the cation is 1-ethyl-3-propylimidazole, the anion is a bis(trifluoromethyl decanoyl)imide anion, and the conventional electrolyte is LiAlCl 4 at a concentration of 1.5M.
  • Embodiment 5 An embodiment of the 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 an imidazole-based ionic liquid, the imidazole
  • the ionic liquid contains a cation and an anion, the cation is 1-ethyl-3-butylimidazole, the anion is a lactate anion, and the conventional electrolyte is LiAlCl 4 -SOCl 2 lithium/thionyl chloride at a concentration of 1.5M.
  • Conventional electrolyte Conventional electrolyte.
  • the volume percentage of the imidazole-based ionic liquid was 20%.
  • the electrolytic solution of this embodiment was prepared in the same manner as in Example 1.
  • Embodiment 6 An embodiment of the 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 an imidazole-based ionic liquid, the imidazole
  • the ionic liquid contains a cation and an anion, the cation is 1-propyl-3-mercaptoimidazole, the anion is a p-nonyl benzoate anion, and the conventional electrolyte is LiAlCl 4 -SOCl 2 lithium at a concentration of 1.5M.
  • Embodiment 7 An embodiment of the 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 an imidazole-based ionic liquid, the imidazole
  • the ionic liquid contains a cation and an anion, the cation is 1-propyl-3-ethylimidazole, the anion is an acetyl transverse imide, and the conventional electrolyte is LiAlCl 4 -SOCl 2 lithium at a concentration of 1.5M.
  • the volume percentage of the imidazole-based ionic liquid was 30%.
  • 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 of the present embodiment is used for a lithium/saltyl chloride battery, the electrolyte solution comprising a conventional electrolyte solution and an imidazole-based ionic liquid, the imidazoles
  • the ionic liquid comprises a cation and an anion, the cation is 1-propyl-3-butylimidazole, the anion is a saccharin anion, and the conventional electrolyte is LiAlCl 4 -SOCl 2 lithium/thionyl chloride at a concentration of 1.5 M.
  • Embodiment 9 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 an imidazole-based ionic liquid, the imidazole
  • the ionic liquid contains a cation and an anion, the cation is 1,3-dimercaptoimidazole, 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.
  • Embodiment 10 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 an imidazole-based ionic liquid, the imidazole
  • the ionic liquid contains a cation and an anion, the cation is 1-butyl-3-ethylimidazole, the anion is a sulfate anion, and the conventional electrolyte is a LiAlCl 4 -SOCl 2 lithium/sulfurous solution having a concentration of 1.5M.
  • Acid chloride conventional electrolyte In the electrolytic solution in the present embodiment, the volume percentage of the imidazole-based ionic liquid was 45%. 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 an imidazole-based ionic liquid, the imidazole Ionic liquid Containing a cation and an anion, the cation is 1-butyl-3-propylimidazole, the anion is diisooctyl succinate sulfonate anion, and the conventional electrolyte is LiAlCl 4 -SOCl 2 lithium at a concentration of 1.5M.
  • Embodiment 12 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 an imidazole-based ionic liquid, the imidazole
  • the ionic liquid contains a cation and an anion, the cation is 1,3-diethylimidazole, the anion is a 4,5-dinitroimidazolium anion, and the conventional electrolyte is LiAlCl 4 -SOCl 2 lithium at a concentration of 1.5M.
  • 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 an imidazole-based ionic liquid, the imidazole
  • the ionic liquid contains a cation and an anion, the cation is 1-butyl-3-mercaptoimidazole, the anion is a 5-nitrotetrazole anion, and the conventional electrolyte is LiAlCl 4 -SOCl 2 lithium at a concentration of 1.5M.
  • Example 14 Electrolyte Conductivity Test The blank group and the control group were set.
  • the electrolyte of the blank group was a LiAlCl 4 -SOCl 2 lithium/thionyl chloride conventional electrolyte having a concentration of 1.5 M, and the electrolytes used in the experimental groups 1-13 were respectively The resulting electrolyte was prepared for Examples 1-13.
  • the conductivity of the electrolyte in the blank and experimental groups were tested separately. The test results are as follows: Conductivity (ms/cm) Blank group 16.0
  • Example 15 electrolyte lithium / ethylene chloride charging battery discharge capability stone impact test group and the control group set, the concentration of the control group using the embodiment of LiAlCl 4 -SOCl 2 1.5 ⁇ lithium / thionyl chloride electrolyte made into a conventional carbon coated Formula ER14250 type battery, the experimental group includes the experimental group 1-13, and the experimental group 1-13 is made into the carbon-packed type ER14250 type battery by using the electrolyte of the embodiment 1-13.
  • the discharge capacity of the battery in the blank group and the experimental group was measured at room temperature with a constant resistance of 330 ⁇ , wherein the battery discharge capacity of the experimental group was taken as the average value of the discharge capacity of the experimental group 1-13, and the discharge capacity of the blank group and the experimental group was plotted.
  • Figure 1 It can be seen from Fig. 1 that the experimental group has obvious discharge capacity compared with the battery of the blank group. Improvement.
  • the experimental group using the electrolytic solution of the present invention has an imidazole-based ionic liquid contained in the electrolytic solution, and the electrolytic solution can effectively increase the discharge voltage of the lithium/thionyl chloride battery and improve the discharge capacity of the battery.
  • Embodiment 16 An embodiment of an electrolyte for a lithium/manganese dioxide battery containing a conventional electrolyte and an imidazole-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 imidazole-based ionic liquid contains a cation and an anion. The electrolytic solution was prepared in the same manner as in Example 1.
  • PC propylene carbonate
  • DME bismuth Ether
  • DOL carbon 1,3-dioxolane
  • LiC104 lithium perchlorate
  • the concentration of lithium perchlorate (LiC104) is 0.5-1.5. Mol/L
  • the lithium/manganese dioxide battery prepared by the electrolyte of the present embodiment has the highest Load voltage and discharge capacity.
  • Example 29 The effect of the electrolyte of the present invention on the discharge capacity of a lithium/manganese dioxide battery was set in a blank group and an experimental group, the experimental group including the experimental group 1-13, and the experimental group 1-13 using the electrolytic solutions prepared in the examples 16-28, respectively.
  • Liquid, and the electrolyte used in the blank group is a common electrolyte for lithium/manganese dioxide lithium batteries, and propylene carbonate (PC), diterpene ether (DME) and carbon 1,3-dioxolane (DOL) are The predetermined ratio is mixed as a solvent, and lithium perchlorate (LiC104) is used as an electrolyte salt.
  • Liquid, and the electrolyte used in the blank group is a common electrolyte for lithium/manganese dioxide lithium batteries, and propylene carbonate (PC), diterpene ether (DME) and carbon 1,3-dioxolane (DOL) are The predetermined ratio
  • 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 the imidazole in the experimental group.
  • Ionic liquid A lithium/manganese dioxide battery of CR15270 type was prepared by using the electrolyte of the experimental group and the blank group, respectively, and then the discharge capacity of the battery of the blank group and the experimental group at a normal temperature constant current of 100 mA was respectively measured.
  • the battery discharge capacity of the experimental group is taken as the average value of the discharge capacity of the experimental group 1-13, and the discharge capacity of the blank group and the experimental group is plotted as shown in FIG. 2 . As can be seen from Fig.
  • the experimental group has a significant increase in the load voltage and discharge capacity of the experimental group compared with the lithium/manganese dioxide battery of the blank group. It is thus proved that the experimental group using the electrolyte of the present invention, since the electrolyte therein contains an imidazole-based ionic liquid, the electrolyte containing the imidazole-based ionic liquid can effectively increase the discharge voltage of the lithium/manganese dioxide battery, and improve the battery. Discharge capacity.
  • Embodiment 30 An embodiment of an electrolyte for a lithium/carbon fluoride battery containing a conventional electrolyte and an imidazole-based 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, 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;
  • the imidazole-based ionic liquid contains a cation and an anion.
  • the electrolytic solution was prepared in the same manner as in Example 1.
  • the lithium/carbon fluoride battery produced by the electrolyte of the present embodiment has the highest Load voltage and discharge capacitance the amount.
  • Example 43 The effect of the electrolyte of the present invention on the discharge capacity of a lithium/carbon fluoride battery was set in a blank group and an experimental group, and the experimental group included the experimental groups 1-13, and the experimental groups 1-13 were respectively prepared by using the electrolytic solutions prepared in Examples 30-42.
  • Liquid, and the electrolyte used in the blank group is a common electrolyte for lithium/carbon fluoride lithium batteries, and propylene carbonate (PC), diterpene ether (DME) (or Y-butyl propyl ester) is mixed as a solvent in a certain ratio.
  • PC propylene carbonate
  • DME diterpene ether
  • Y-butyl propyl ester Y-butyl propyl ester
  • Lithium tetrafluoroborate (LIBF4) is used as the electrolyte salt, and the concentration of lithium tetrafluoroborate (LIBF4) is 0.5 ⁇ 1.5mol/L, that is, the electrolyte of the blank group does not contain the imidazole ionic liquid in the experimental group.
  • a 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 discharge capacity of the blank group and the experimental group of the battery at a normal temperature constant current of 10 mA was respectively measured.
  • the battery discharge capacity of the experimental group is taken as the average value of the discharge capacity of the experimental group 1-13, and the discharge capacity of the blank group and the experimental group is plotted as shown in FIG.
  • the experimental group has a significant increase in the load voltage and discharge capacity of the experimental group compared with the blank group of lithium/carbon fluoride batteries. It is thus proved that the experimental group using the electrolyte of the present invention, since the electrolyte therein contains an imidazole-based ionic liquid, the electrolyte containing the imidazole-based ionic liquid can effectively increase the discharge voltage of the lithium/carbon fluoride battery, and improve the battery. Discharge capacity.

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Abstract

本发明公开一种锂电池用电解液，所述电解液含有咪唑类离子液体，所述咪唑类离子液体包含阳离子和阴离子；所述阳离子为烷基咪唑；所述阴离子为卤酸根离子、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。本发明所述电解液可改变电池的反应历程，提高阴极活性物质的还原速率，增大电解液的电导率，提高电解液的传质速率，从而提高锂电池的放电电压。同时，本发明还公开了所述电解液的制备方法以及含有所述电解液的锂电池。

Description

一种锂电池用电解液及使用该电解液的锂电池
技术领域 本发明涉及一种锂电池用电解液及使用该电解液的锂电池， 尤其是一种锂 / 亚硫酰氯电池或锂 /二氧化锰电池或锂 /氟化碳电池用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。 目前， 市面上所见锂电池一般可分为容量型和功率型两种， 前者具备较高 的容量密度但其大电流放电能力较差， 一般应用于以小电流长时间的工作模式。 而后者则具备相对较大电流放电的能力， 但其容量密度相对则较低。 随着现代 仪器仪表的不断发展， 对电池的要求也越来越高， 所以提高锂电池的高电流放 电能力， 就变得越来越重要。 常见的提高锂电池大电流放电能力的做法有： 从改善电池反应角度， 加入 过渡金属大环化合物催化剂， 改变电解液的还原反应机理， 提高其还原反应速 率， 从而使整个电池反应加速， 达到提高放电能力的目的。 但是提高幅度有限， 因为电池反应速率还受到电解液传质速率控制。 还有从电池结构设计角度提高 电极反应面积， 采用更薄更长的极片来提高电池放电电压， 但这会埋下严重的 安全隐患。 发明内容
设计的前提下， 能够有效提高电池的负载电压的锂电池用电解液； 同时， 本发 明还提供一种采用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 电解液含有咪唑类离子液体， 所述咪唑类离子液体包含阳离子和阴离子；
所述阳离子为綻基咪唑；
所述阴离子为卤酸根离子、 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 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。 本发明所述锂电池用电解液中添加咪唑类离子液体作为电解液添加剂， 所 述咪唑类萬子液体包含阳离子和阴离子， 所述阴离子中除面酸根萬子外其余阴 离子的分子结构式如下：
Figure imgf000004_0001
咪唑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优点， 这些优点使其具有 广阔的应用前景。 本发明所述锂电池用电解液， 将咪唑类离子液体作为添加剂 加入， 所形成的电解液中， 咪唑类离子液体可改变电池反应历程， 提高阴极活 性物质的还原速率， 同时增大电解液的电导率， 提高电解液的传质速率， 两方 面同时作用， 所形成的电解液可有效提高锂电池的放电电压， 同时还能显著提 高锂电池的高温放电性能。 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 1-烷基 -3- 烷基咪唑。 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 1-曱基 -3-乙基咪唑。 应用于锂 /亚硫酰氯电池中， 当所述阳离子选择 1-烷基 -3烷 基咪唑时， 能够更好提高阴极活性物质的还原速率、 增大电解液的电导率， 从 而更有效提高锂亚硫酰氯电池的放电电压。 当所述阳离子选择 1-曱基 -3-乙基咪 唑时， 能够最有效提高阴极活性物质的还原速率、 增大电解液的电导率， 最有 效地提高锂 /亚硫酰氯电池的放电电压。 当然， 当所述电解液用于其他种类的锂 电池时， 例如锂 /二氧化锰电池和锂 /氟化碳电池时， 所述阳离子也优选为 1-曱基 -3-乙基咪唑； 当所述阳离子选择 1-曱基 -3-乙基咪唑时， 能够显著提高锂 /二氧化 锰电池和锂 /氟化碳电池的负载电压和容量。 作为本发明所述锂电池用电解液的优选实施方式， 应用于锂 /亚石 υ酰氯电池 时， 所述阴离子为面酸根离子。 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 （ AlCl4- )。 所述阴离子选择卤酸根离子 时， 能够更好提高阴极活性物质的还原速率、 增大电解液的电导率， 从而更有 效提高锂 /亚硫酰氯电池的放电电压。所述阴离子选择四氯化铝酸根离子（ A1C14- ) 时， 能够最有效提高阴极活性物质的还原速率、 增大电解液的电导率， 最有效 地提高锂 /亚硫酰氯电池的放电电压。 当然， 当所述电解液用于其他种类的锂电 池时， 例如锂 /二氧化锰电池和锂 /氟化碳电池时， 所述阴离子优选二（三氟曱基 磺酰） 亚胺阴离子； 当所述阴离子选择二（三氟曱基橫酰） 亚胺阴离子时， 能 够显著提高锂 /二氧化锰电池和锂 /氟化碳电池的负载电压和容量。 作为本发明所述锂电池用电解液的优选实施方式， 所述电解液中咪唑类离 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， 所述电解液中咪唑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， 所述电解液中咪唑类离子液体的体积 百分含量为 5%。 所述咪唑类离子液体的体积百分含量为 1~15%时， 能够更好的 增大电解液的电导率； 所述咪唑类离子液体的体积百分含量为 5%时， 能够显著 增大电解液的电导率。 本发明还提供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：
( 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， 除去咪唑类离子液体中的水分；
( 2 )将咪唑类离子液体加入到常规电解液中， 混合均匀即可。 另外， 本发明还提供一种含有如上所述锂电池用电解液的锂电池。 本发明 所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咪唑 类离子液体， 可以改变电池反应历程， 增大电解液的电导率， 提高电解液的传 质速率， 因此所述锂电池具有较好的负载电压和容量。 作为本发明所述锂电池的优选实施方式， 所述锂电池为锂 /亚石 A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"。 将上述所述咪唑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。 本 发明所述锂 /亚石 A酰氯电池， 由于其中的电解液含有咪唑类离子液体， 咪唑类离 子液体的加入可改变电池反应历程， 提高阴极活性物质的还原速率， 同时增大 电解液的电导率， 提高电解液的传质速率， 两方面同时作用可提高锂 /亚硫酰氯 电池的放电电压。 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。 将上述咪唑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。 尤其是当所述咪唑类萬子液体 的阳离子选择 1-曱基 -3-乙基咪唑、 阴离子选择二（三氟曱基橫酰）亚胺阴离子， 且咪唑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， 能够最有效的提高锂 /二氧化锰电池的负载电压和容量。 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。 将上述咪唑类离子液体作为添 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。 尤其是当所述咪唑类离子液体的阳离子选择 1-曱基 -3-乙基咪 唑、 阴离子选择二（三氟曱基礒酰） 亚胺阴离子， 且咪唑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， 能够最有效的提高锂 /氟化碳电 池的负载电压和容量。 本发明所述锂电池用电解液， 将咪唑类离子液体作为添加剂加入其中， 咪 唑类离子液体的加入可改变电池反应历程， 提高阴极活性物质的还原速率， 同 时增大电解液的电导率， 提高电解液的传质速率， 两方面同时作用可提高锂电 池的放电电压。 本发明含有所述电解液的锂电池， 在不改变电池结构的基础上， 具有较高的负载电压， 由于电池的结构不改变， 从而避免了因改变电池设计带 来的成本上升和安全隐患。 附图说明 图 1 为空白组电解液和本发明电解液制作的锂 /亚石 υ酰氯电池在常温恒阻
330Ω放电曲线对比图。 图 2 为空白组电解液和本发明电解液制作的锂 /二氧化锰电池在常温恒流 100mA放电曲线对比图。 图 3 为空白组电解液和本发明电解液制作的锂 /氟化碳电池在常温恒流 10mA放电曲线对比图。 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咪唑类离子液体， 所述咪唑类离子液体 包含阳离子和阴离子， 所述阳离子为 1-曱基 -3-乙基咪唑， 所述阴离子为四氯化 铝酸根离子 （ AICU—), 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， 咪唑类离子液体的体积百分含量为 5%。 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， 除去咪唑类离子液体中的水分；
( 2 )将咪唑类萬子液体加入常规电解液中， 混合均勾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咪唑类离子液体， 所述咪唑类离子液体 包含阳离子和阴离子， 所述阳离子为 1-曱基 -3-丙基咪唑， 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， 咪唑类离子液体的体积百分含量为 1%。 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咪唑类离子液体， 所述咪唑类离子液体 包含阳离子和阴离子， 所述阳离子为 1-曱基 -3-丁基咪唑， 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， 咪唑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咪唑类离子液体， 所述咪唑类离子液体 包含阳离子和阴离子， 所述阳离子为 1-乙基 -3-丙基咪唑， 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， 咪唑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 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咪唑类离子液体， 所述咪唑类离子液体 包含阳离子和阴离子， 所述阳离子为 1-乙基 -3-丁基咪唑， 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。 本实施例中的电解液中， 咪唑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 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咪唑类离子液体， 所述咪唑类离子液体 包含阳离子和阴离子， 所述阳离子为 1-丙基 -3-曱基咪唑， 所述阴离子为对曱基 苯礒酸根阴离子， 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， 咪唑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 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咪唑类离子液体， 所述咪唑类离子液体 包含阳离子和阴离子， 所述阳离子为 1-丙基 -3-乙基咪唑， 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， 咪唑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 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 酰 氯电池， 所述电解液含有常规电解液和咪唑类离子液体， 所述咪唑类离子液体 包含阳离子和阴离子， 所述阳离子为 1-丙基 -3-丁基咪唑， 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， 咪唑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 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咪唑类离子液体， 所述咪唑类离子液体 包含阳离子和阴离子， 所述阳离子为 1 , 3-二曱基咪唑， 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， 咪唑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 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咪唑类离子液体， 所述咪唑类离子液体 包含阳离子和阴离子， 所述阳离子为 1-丁基 -3-乙基咪唑， 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， 咪唑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 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^和咪唑类离子液体， 所述咪唑类离子液体 包含阳离子和阴离子， 所述阳离子为 1-丁基 -3-丙基咪唑， 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， 咪唑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 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咪唑类离子液体， 所述咪唑类离子液体 包含阳离子和阴离子， 所述阳离子为 1,3-二乙基咪唑， 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， 咪唑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 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咪唑类离子液体， 所述咪唑类离子液体 包含阳离子和阴离子， 所述阳离子为 1-丁基 -3-曱基咪唑， 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， 咪唑类离子液体的体积百分含量为 12%。 本实施 例的电解液的制备方法同实施例 1。 实施例 14 电解液电导率试验 设置空白组和对照组， 空白组的电解液采用浓度为 1.5M的 LiAlCl4-SOCl2 锂 /亚硫酰氯常规电解液， 实验组 1-13采用的电解液分别为实施例 1-13制备得 到的电解液。 分别检测空白组和实验组的电解液电导率， 测试结果如下所示： 电导率 ( ms/cm ) 空白组 16.0
实验组 1 19.8
实验组 2 16.6
实验组 3 16.4
实验组 4 16.3
实验组 5 18.0
实验组 6 18.2
实验组 7 18.4
实验组 8 18.7
实验组 9 18.5
实验组 10 18.9
实验组 11 18.1
实验组 12 18.0
实验组 13 18.5 由上表的检测结果对比可看出， 实验组的电解液的电导率与空白组相比， 有明显的提高， 尤其是实验组 1 的电解液的电导率有显著提高。 由此可证明， 本发明的锂 /亚石 υ酰氯电池用电解液中由于添加了咪唑类离子液体， 可有效增大 电解液的电导率， 提高电解液的传质速率。 实施例 15 电解液对锂 /亚石充酰氯电池放电能力的影响 设置空白组和实验组， 空白组采用浓度为 1.5Μ的 LiAlCl4-SOCl2锂 /亚硫酰 氯常规电解液制作成碳包式 ER14250型电池， 实验组包括实验组 1-13, 实验组 1-13分别采用实施例 1-13的电解液制作成碳包式 ER14250型电池。分别检测空 白组和实验组的电池在常温恒阻 330Ω的放电能力，其中所述实验组的电池放电 能力取实验组 1-13放电能力的平均值， 将空白组和实验组的放电能力作曲线对 比如附图 1所示。 由附图 1 可看出， 实验组与空白组的电池相比， 实验组的放电能力有明显 的提高。 由此证明， 采用了本发明电解液的实验组， 由于其中的电解液中含有 咪唑类离子液体， 所述电解液能够有效提高锂 /亚硫酰氯电池的放电电压， 提高 电池的放电能力。 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 液和咪唑类离子液体； 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; 所述咪唑类离子液体 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， 所述咪唑类离子液体 中阳离子和阴离子的具体选择以及所述电解液中咪唑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
1-曱基 -3-乙基
16 四氯化铝酸根离子 5%
咪坐
1—曱基—3—丙基
17 四氟硼酸阴离子 1%
咪坐
1-曱基 -3-丁基
18 六氟磚酸阴离子 10%
咪坐
1-曱基 -3-乙基
19 二（三氟曱基礒酰）亚胺阴离子 15%
咪坐
1-乙基 -3-丁基
20 乳酸根阴离子 20%
咪坐
21 1—丙基—3—曱基 对曱基苯橫酸根阴离子 25% 咪坐
1-丙基 -3-乙基
22 乙酰礒酰亚胺阴离子 30%
咪坐
1-丙基 -3-丁基
23 糖精阴离子 35%
咪坐
1 , 3-二曱基咪
24 氨基酸类阴离子 40%
坐
1-丁基 -3-乙基
25 硫酸酯类阴离子 45%
咪坐
1-丁基 -3-丙基
26 丁二酸二异辛酯磺酸根阴离子 50%
咪坐
27 1,3-二乙基咪唑 4,5-二硝基咪唑阴离子 6%
1-丁基 -3-曱基
28 5-硝基四唑阴离子 12%
咪坐 上述实施例的锂 /二氧化锰电池用电解液中， 实施例 19的电解液中， 由于咪 唑类离子液体在电解液中的体积百分含量为 15%, 且选择所述特定的阳离子 1- 曱基 -3-乙基咪唑和阴离子二（三氟曱基橫酰） 亚胺阴离子组合而成的咪唑类离 子液体， 本实施例的电解液制作成的锂 /二氧化锰电池具有最高的负载电压和放 电容量。 实施例 29 本发明电解液对锂 /二氧化锰电池放电能力的影响 设置空白组和实验组， 实验组包括实验组 1-13 , 实验组 1-13分别采用实施 例 16-28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咪唑类离子液体。 分 别采用实验组和空白组的电解液制作成 CR15270型号的锂 /二氧化锰电池， 然后 分别检测空白组和实验组的电池在常温恒流 100mA的放电能力。 其中， 所述实 验组的电池放电能力取实验组 1-13放电能力的平均值， 将空白组和实验组的放 电能力作曲线对比如附图 2所示。 由附图 2可看出， 实验组与空白组的锂 /二氧化锰电池相比， 实验组的负载 电压和放电容量有明显的提高。 由此证明， 采用了本发明电解液的实验组， 由 于其中的电解液含有咪唑类离子液体， 所述含有咪唑类离子液体的电解液能够 有效提高锂 /二氧化锰电池的放电电压， 提高电池的放电能力。 实施例 30 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 和咪唑类离子液体； 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; 所述咪唑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， 所述咪唑类离子液体中 阳离子和阴离子的具体选择以及所述电解液中咪唑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
1-曱基 -3-乙基
30 四氯化铝酸根离子 5%
咪坐
1—曱基—3—丙基
31 四氟硼酸阴离子 1%
咪坐
32 1-曱基 -3-丁基 六氟磚酸阴离子 10% 咪坐
1-曱基 -3-乙基
33 二（三氟曱基礒酰）亚胺阴离子 15%
咪坐
1-乙基 -3-丁基
34 乳酸根阴离子 20%
咪坐
1—丙基—3—曱基
35 对曱基苯橫酸根阴离子 25%
咪坐
1-丙基 -3-乙基
36 乙酰礒酰亚胺阴离子 30%
咪坐
1-丙基 -3-丁基
37 糖精阴离子 35%
咪坐
1 , 3-二曱基咪
38 氨基酸类阴离子 40%
坐
1-丁基 -3-乙基
39 硫酸酯类阴离子 45%
咪坐
1-丁基 -3-丙基
40 丁二酸二异辛酯磺酸根阴离子 50%
咪坐
41 1,3-二乙基咪唑 4,5-二硝基咪唑阴离子 6%
1-丁基 -3-曱基
42 5-硝基四唑阴离子 12%
咪坐 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， 由于咪唑 类离子液体在电解液中的体积百分含量为 15%, 且选择所述特定的阳离子 1-曱 基 -3-乙基咪唑和阴离子二（三氟曱基橫酰） 亚胺阴离子组合而成的咪唑类离子 液体， 本实施例的电解液制作成的锂 /氟化碳电池具有最高的负载电压和放电容 量。 实施例 43 本发明电解液对锂 /氟化碳电池放电能力的影响 设置空白组和实验组， 实验组包括实验组 1-13, 实验组 1-13分别采用实施 例 30-42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咪唑类离子液体。 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， 然后分别检测 空白组和实验组的电池在常温恒流 10mA 的放电能力。 其中， 所述实验组的电 池放电能力取实验组 1-13放电能力的平均值， 将空白组和实验组的放电能力作 曲线对比如附图 3所示。 由附图 3可看出， 实验组与空白组的锂 /氟化碳电池相比， 实验组的负载电 压和放电容量有明显的提高。 由此证明， 采用了本发明电解液的实验组， 由于 其中的电解液含有咪唑类离子液体， 所述含有咪唑类离子液体的电解液能够有 效提高锂 /氟化碳电池的放电电压， 提高电池的放电能力。 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

权、、、、利、、、、要、、、、求、、、、书、
1、 一种锂电池用电解液， 其特征在于， 所述电解液含有咪唑类离子液体， 所述咪唑类离子液体包含阳离子和阴离子；
所述阳离子为綻基咪唑；
所述阴离子为卤酸根离子、 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。
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 1-烷 基 -3烷基咪唑。
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 1-曱 基 -3-乙基咪唑。
4、 如权利要求 1所述的锂电池用电解液， 其特征在于， 所述阴离子为卤酸 根离子。
5、 如权利要求 4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。
6、 如权利要求 1-5任一所述的锂电池用电解液， 其特征在于， 所述电解液 中咪唑类离子液体的体积百分含量为 0.1~50%。
7、 如权利要求 6所述的锂电池用电解液， 其特征在于， 所述电解液中咪唑 类离子液体的体积百分含量为 1~15%。
8、 如权利要求 7所述的锂电池用电解液， 其特征在于， 所述电解液中咪唑 类离子液体的体积百分含量为 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， 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， 除去咪唑类离子液体中的水分；
( 2 )将咪唑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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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116731228A (zh) * 2023-06-21 2023-09-12 江苏天合储能有限公司 锂电池及其粘结剂、电极片、电芯及粘结剂的制备方法

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104162342B (zh) * 2014-08-18 2016-04-20 南京信息工程大学 一种复式离子液体脱硫脱碳剂及其制备方法和应用
CN106450509A (zh) * 2015-08-05 2017-02-22 苏州宝时得电动工具有限公司 电解液和电池
CN108232292B (zh) * 2016-12-15 2021-02-26 东莞东阳光科研发有限公司 一种锂离子电池用电解液
CN107321137A (zh) * 2017-08-10 2017-11-07 清华大学 一种一体化捕集分离h2s和/或co2的复合型离子溶剂
CN110071329B (zh) * 2018-11-27 2021-06-22 欣旺达电子股份有限公司 锂电池及其电解液
CN112687954B (zh) * 2020-12-24 2022-04-26 宁德新能源科技有限公司 电解液、电化学装置及电子装置
CN113270644A (zh) * 2021-05-17 2021-08-17 惠州亿纬锂能股份有限公司 一种电解液及其制备方法和应用
CN115172880B (zh) * 2022-08-22 2026-03-10 河南省鹏辉电源有限公司 一种非水电解液及锂离子电池
CN116404256B (zh) * 2023-05-31 2023-10-27 宁德时代新能源科技股份有限公司 电解液、电池单体、电池和用电设备
CN117936893B (zh) * 2023-11-21 2025-07-04 珠海市裕洲环保科技有限公司 一种电解液及其制备方法和应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1412882A (zh) * 2001-10-15 2003-04-23 三星Sdi株式会社 用于锂－硫电池的电解质和含有该电解质的锂－硫电池
CN1482701A (zh) * 2002-09-10 2004-03-17 ����Sdi��ʽ���� 锂硫电池的电解液及锂硫电池
CN1564805A (zh) * 2002-04-24 2005-01-12 日清纺织株式会社 离子性液体与脱水方法及双层电容器与二次电池
CN1677740A (zh) * 2004-03-31 2005-10-05 株式会社东芝 非水电解质电池
WO2008153045A1 (ja) * 2007-06-12 2008-12-18 Nippoh Chemicals Co., Ltd. イオン液体およびその製造方法
CN101440188A (zh) * 2008-12-30 2009-05-27 哈尔滨工业大学 锂离子电池凝胶型离子液体/聚合物电解质及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1412882A (zh) * 2001-10-15 2003-04-23 三星Sdi株式会社 用于锂－硫电池的电解质和含有该电解质的锂－硫电池
CN1564805A (zh) * 2002-04-24 2005-01-12 日清纺织株式会社 离子性液体与脱水方法及双层电容器与二次电池
CN1482701A (zh) * 2002-09-10 2004-03-17 ����Sdi��ʽ���� 锂硫电池的电解液及锂硫电池
CN1677740A (zh) * 2004-03-31 2005-10-05 株式会社东芝 非水电解质电池
WO2008153045A1 (ja) * 2007-06-12 2008-12-18 Nippoh Chemicals Co., Ltd. イオン液体およびその製造方法
CN101440188A (zh) * 2008-12-30 2009-05-27 哈尔滨工业大学 锂离子电池凝胶型离子液体/聚合物电解质及其制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116731228A (zh) * 2023-06-21 2023-09-12 江苏天合储能有限公司 锂电池及其粘结剂、电极片、电芯及粘结剂的制备方法

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