WO2015042851A1 - Électrolyte pour batterie au lithium, et batterie au lithium l'utilisant - Google Patents

Électrolyte pour batterie au lithium, et batterie au lithium l'utilisant Download PDF

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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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electrolyte
lithium
anion
battery
ionic liquid
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PCT/CN2013/084412
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English (en)
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/fr
Priority to CN201380002472.4A priority patent/CN103814468B/zh
Publication of WO2015042851A1 publication Critical patent/WO2015042851A1/fr

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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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  • Secondary Cells (AREA)
  • Primary Cells (AREA)

Abstract

L'invention concerne un électrolyte pour une batterie au lithium. L'électrolyte contient un liquide ionique à base de pyridinium, et le liquide ionique à base de pyridinium contient des cations et des anions, les cations étant des pyridines de N-alkyle ; et les anions étant un élément parmi des ions de tétrachloroaluminate, des ions de tétrachlorogallate, des anions de tétrafluoroborate, des anions d'hexafluorophosphate, des anions de bis(trifluorométhylsulfonyl)imide, des anions de lactate, des anions de p-toluène sulfonate, des anions de sulfonimide d'acétyle, des anions de saccharine, des anions d'acide aminé, des anions de sulfate, des anions de sulfosuccinate de diisooctyle, des anions de 4,5-dinitroimidazole et des anions de 5-nitrotétrazole. L'électrolyte selon la présente invention peut supprimer efficacement la croissance d'une couche de passivation (un film SEI) sur la surface du métal lithium dans une batterie au lithium, ce qui améliore ainsi significativement la capacité de stockage de la batterie. De plus, l'invention concerne également un procédé de préparation pour l'électrolyte et une batterie au lithium contenant l'électrolyte.
PCT/CN2013/084412 2013-09-27 2013-09-27 Électrolyte pour batterie au lithium, et batterie au lithium l'utilisant WO2015042851A1 (fr)

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PCT/CN2013/084412 WO2015042851A1 (fr) 2013-09-27 2013-09-27 Électrolyte pour batterie au lithium, et batterie au lithium l'utilisant
CN201380002472.4A CN103814468B (zh) 2013-09-27 2013-09-27 一种锂电池用电解液及使用该电解液的锂电池

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