WO2015042850A1 - Électrolyte pour pile au lithium et pile au lithium utilisant ce dernier - Google Patents

Électrolyte pour pile au lithium et pile au lithium utilisant ce dernier Download PDF

Info

Publication number
WO2015042850A1
WO2015042850A1 PCT/CN2013/084405 CN2013084405W WO2015042850A1 WO 2015042850 A1 WO2015042850 A1 WO 2015042850A1 CN 2013084405 W CN2013084405 W CN 2013084405W WO 2015042850 A1 WO2015042850 A1 WO 2015042850A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
electrolyte
battery
quaternary ammonium
anions
Prior art date
Application number
PCT/CN2013/084405
Other languages
English (en)
Chinese (zh)
Inventor
曹浪
袁中直
刘金成
Original Assignee
惠州亿纬锂能股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 惠州亿纬锂能股份有限公司 filed Critical 惠州亿纬锂能股份有限公司
Priority to PCT/CN2013/084405 priority Critical patent/WO2015042850A1/fr
Priority to CN201380002468.8A priority patent/CN103858268A/zh
Publication of WO2015042850A1 publication Critical patent/WO2015042850A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0045—Room temperature molten salts comprising at least one organic ion
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Primary Cells (AREA)

Abstract

L'invention porte sur un électrolyte pour une pile au lithium. L'électrolyte contient un liquide ionique d'ammonium quaternaire, ce dernier contenant des cations et des anions, les cations étant de l'ammonium quaternaire N-alkyle; les anions étant des ions d'halogénure, des anions de tétrafluoroborate, des anions d'hexafluorophosphate, des anions de bis(trifluorométhylsulfonyl)imide, des anions de lactate, des anions de sulfonate de toluène p, 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 ou des anions de 5-nitrotétrazole. Le liquide ionique d'ammonium quaternaire contenu dans l'électrolyte de la présente invention peut être utilisé en tant que catalyseur de réaction pour une pile haute température et peut permettre à une pile au lithium haute température d'avoir une capacité de décharge de grande efficacité et constante dans les limites d'une plage allant d'une température ambiante à des températures élevées. L'invention porte également sur une pile au lithium contenant l'électrolyte.
PCT/CN2013/084405 2013-09-27 2013-09-27 Électrolyte pour pile au lithium et pile au lithium utilisant ce dernier WO2015042850A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CN2013/084405 WO2015042850A1 (fr) 2013-09-27 2013-09-27 Électrolyte pour pile au lithium et pile au lithium utilisant ce dernier
CN201380002468.8A CN103858268A (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

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2013/084405 WO2015042850A1 (fr) 2013-09-27 2013-09-27 Électrolyte pour pile au lithium et pile au lithium utilisant ce dernier

Publications (1)

Publication Number Publication Date
WO2015042850A1 true WO2015042850A1 (fr) 2015-04-02

Family

ID=50864340

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2013/084405 WO2015042850A1 (fr) 2013-09-27 2013-09-27 Électrolyte pour pile au lithium et pile au lithium utilisant ce dernier

Country Status (2)

Country Link
CN (1) CN103858268A (fr)
WO (1) WO2015042850A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107586959B (zh) * 2017-09-11 2018-11-30 陕西科技大学 利用超声波强化功能性离子液体萃取水中重金属的方法
CN110400970B (zh) * 2019-06-04 2023-09-05 江西力能新能源科技有限公司 一种电解质材料及其在高温锂电池上的应用
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
CN118073652B (zh) * 2024-04-18 2024-06-28 浙江钠创新能源有限公司 钠离子电池电解液及钠离子二次电池

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101764253A (zh) * 2009-11-20 2010-06-30 无锡欧力达新能源电力科技有限公司 二次铝电池及其制备方法
CN102089924A (zh) * 2008-07-11 2011-06-08 法国原子能及替代能源委员会 包括阴离子表面活性剂的离子液体电解质及包括其的电化学装置如蓄电池
CN102124599A (zh) * 2008-05-29 2011-07-13 莱登能源公司 具有离子液体电解质的电化学电池
CN102138235A (zh) * 2008-08-29 2011-07-27 法国原子能及替代能源委员会 包含离子液体电解质的锂离子可再充电蓄电池
JP2012056897A (ja) * 2010-09-09 2012-03-22 Otsuka Chem Co Ltd 環状第４級アンモニウム塩、それを用いた電解質組成物、及び該電解質組成物を用いた電気化学デバイス
CN102731435A (zh) * 2005-01-12 2012-10-17 大塚化学株式会社 季铵盐、电解质、电解液以及电化学装置

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2454305A1 (fr) * 2002-04-24 2003-11-06 Nisshinbo Industries, Inc. Liquide ionique, procede de deshydratation, condensateur electrique a couche double et batterie secondaire

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102731435A (zh) * 2005-01-12 2012-10-17 大塚化学株式会社 季铵盐、电解质、电解液以及电化学装置
CN102124599A (zh) * 2008-05-29 2011-07-13 莱登能源公司 具有离子液体电解质的电化学电池
CN102089924A (zh) * 2008-07-11 2011-06-08 法国原子能及替代能源委员会 包括阴离子表面活性剂的离子液体电解质及包括其的电化学装置如蓄电池
CN102138235A (zh) * 2008-08-29 2011-07-27 法国原子能及替代能源委员会 包含离子液体电解质的锂离子可再充电蓄电池
CN101764253A (zh) * 2009-11-20 2010-06-30 无锡欧力达新能源电力科技有限公司 二次铝电池及其制备方法
JP2012056897A (ja) * 2010-09-09 2012-03-22 Otsuka Chem Co Ltd 環状第４級アンモニウム塩、それを用いた電解質組成物、及び該電解質組成物を用いた電気化学デバイス

Also Published As

Publication number Publication date
CN103858268A (zh) 2014-06-11

Similar Documents

Publication Publication Date Title
CN103972588B (zh) 非水电解液与锂离子电池
WO2015042851A1 (fr) Électrolyte pour batterie au lithium, et batterie au lithium l'utilisant
WO2015042845A1 (fr) Électrolyte pour une batterie au lithium et batterie au lithium utilisant ce dernier
Wu et al. A diisocyanate/sulfone binary electrolyte based on lithium difluoro (oxalate) borate for lithium batteries
CN111697264A (zh) 一种高电压锂离子电池电解液
CN106169611A (zh) 一种以乙酸乙酯为溶剂的低温电解液
JP4684006B2 (ja) 含フッ素有機スルホニルイミド塩電解質とそれを用いた電解液および電気化学素子
WO2023044969A1 (fr) Dispositif de stockage d'énergie électrochimique à base de zinc
CN114171796B (zh) 一种电解液及其在锂离子电池中的应用方法、锂离子电池
WO2015042850A1 (fr) Électrolyte pour pile au lithium et pile au lithium utilisant ce dernier
CN103928707A (zh) 一种高电压锂离子电池功能电解液及制备方法与应用
JP2007141489A (ja) 非水電解質電池
CN105762410B (zh) 一种非水电解液及使用该非水电解液的锂离子电池
CN108281700A (zh) 一种电解液及制备方法与使用该电解液的二次锂硫电池
CN103996873B (zh) 匹配btr918石墨负极的锂离子电池用非水电解液
CN105428086A (zh) 锂离子超级电容器电解液
CN110148783A (zh) 一种改善石墨电极表面sei膜性能的电解液及其制备方法和应用
CN105977535A (zh) 一种新型锂离子电池电解液组合物
Lalia et al. Electrochemical performance of nonflammable polymeric gel electrolyte containing triethylphosphate
CN108987811A (zh) 一种全离子液体电解液及含有该电解液的锂电池
CN107171023A (zh) 一种锂离子电池低温电解液
CN112164825A (zh) 一种高压磷酸酯电解液添加剂及含该添加剂的锂离子电池电解液
CN116315156A (zh) 一种有机/水杂化电解质的制备方法、电池及应用
CN113113671B (zh) 一种聚偏氟乙烯基固态电解质、其制备方法及锂离子电池
Wang et al. A partial-molar volume study of electrolytes in propylene carbonate-based lithium battery electrolyte solutions at 298.15 K

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13894127

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13894127

Country of ref document: EP

Kind code of ref document: A1