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CN110289449A - A kind of electrolyte and its application on low temperature lithium battery - Google Patents

A kind of electrolyte and its application on low temperature lithium battery Download PDF

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Publication number
CN110289449A
CN110289449A CN201910480398.6A CN201910480398A CN110289449A CN 110289449 A CN110289449 A CN 110289449A CN 201910480398 A CN201910480398 A CN 201910480398A CN 110289449 A CN110289449 A CN 110289449A
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electrolyte
lithium battery
lithium
battery
charge
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侯伟
侯民
郭农庆
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Jiangxi Lineng New Energy Technology Co Ltd
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Jiangxi Lineng New Energy Technology Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • H01M10/0567Liquid materials characterised by the additives
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • H01M10/0569Liquid materials characterised by the solvents
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0017Non-aqueous electrolytes
    • H01M2300/0025Organic electrolyte
    • H01M2300/0028Organic electrolyte characterised by the solvent
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • 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)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides a kind of electrolytes of lithium battery, including 1- hexyl -3- methy limidazolium father-in-law or 1- ethyl-3-methylimidazole dicyan methylene salt or 1- butyl -1- crassitude chloride and MgB2Or Mg3N2.Prepare can in -60 DEG C of low temperature environments normal use high-capacity lithium battery, charge/discharge capacity is maintained at 75% or more when room temperature, solve the problems, such as low temperature cause battery at all can not normal use, preparation method is simple, is conducive to industrialize steady production.

Description

A kind of electrolyte and its application on low temperature lithium battery
Technical field
The invention belongs to field of lithium, in particular to a kind of electrolyte and its application on low temperature lithium battery.
Background technique
In the past decade, the extensive use of lithium battery has proved to be a kind of very reliable battery technology.Lithium battery It is widely used in electric car, mobile phone, camera, laptop and other mobile devices.Lithium battery is even used in power grid Energy stores.Lithium battery voltage is high, light-weight.One single battery average voltage can reach 3.7V or 3.2V, relatively etc. In the series voltage of 2-4 nickel-metal hydride battery or nickel separation cell.The energy and density bullet of lithium battery are also very high to other batteries, lithium electricity Pond has high energy storage metric density, and it is the 5-7 of lead-acid accumulator that currently used lithium battery density, which can reach 450-620Wh/kg, Times, it is compared for battery weight, the weight of a lithium battery is about 5-6 times of lead-acid accumulator.Lithium battery uses the time Service life is very long, if a lithium battery service life does not occur to can be used in unexpected situation 6 years or more, up to 9 years, normally Access times at 1000 times or more, if number is not accidentally used can achieve 1500 times or more.Self discharge is low, and nothing Memory effect produces the effect for adding protection board that lithium battery can be made to have a super-charge super-discharge with it toward lithium battery in lithium battery, lithium electricity Pond itself has high power endurance, and the lithium battery that electric car is selected can achieve the high effect capability of 15-30C charge and discharge, So as to the high-intensitive Acceleration of starting on automobile.Turn around time efficiency shows battery in the effect being completely charged and discharged in the period Rate, for lead storage battery, this is usually about 75%, it means that charges, can only obtain if it is the lead storage battery of 1000Wh The electricity of 750Wh actually powers for your equipment, and therefore, only battery will lose 25% system effectiveness, in sun energy circuit In the case where lamp (or any other solar energy system), it means that at least more 25% solar panel is needed to be identical Load supplying, under these conditions, system will inevitably become costly (or to show more under same configuration Difference).However, turn around time efficiency is about 98% for lithium battery.The power consumption depth of battery in depth of discharge and each period Related, battery discharge is deeper, and discharge cycle is fewer, therefore the service life of battery is shorter, and lithium battery can be easily discharged to 95%, and lead battery can then be limited in 50% or less.If we want using about 2000, battery the period (2000/365 day =5,5 years), can only discharge lead battery 25-35%, and lithium battery can only then discharge 80% or so.This means that needing at least 4 Lithium battery capacity again could obtain the same battery service life of lead battery, or, in other words, if 80% battery is used to hold Amount can only use lead battery 250-500 times circulation rather than the 2000 of lithium battery circulations, and lead storage battery must be than lithium battery more Change 4-8 times.
Lithium battery and lead battery can all lose useful energy capacity in cold weather conditions, -20 DEG C at a temperature of, The useful energy of lead battery is reduced to 30%, and the energy capacity of lithium battery is reduced to 70% hereinafter, will lead if temperature is lower Sending a telegraph pond at all can not normal use.Low temperature environment can mainly have an impact lithium cell electrolyte, and the variation of electrolyte states of matter is led It causes the energy capacity of lithium battery to greatly reduce in low temperature environment, therefore, invents a kind of lithium cell electrolyte that can be low temperature resistant It is market in urgent need.
Summary of the invention
The present invention provides a kind of electrolyte and its applications on low temperature lithium battery, to solve above-mentioned background technique The middle problem.
To achieve the above object, the invention provides the following technical scheme: a kind of electrolyte of lithium battery, including it is following The raw material of mass fraction: 64-80 parts of ionic liquid, 0.5-8 parts of additive, 12-27 parts of lithium salts, the ionic liquid includes following It is at least one: butyl pyridinium bromide, 1- hexyl -3- methy limidazolium father-in-law, 1- butyl -3- methylimidazole tosilate, 1- ethyl -3- methy limidazolium 1- octyl -3- methylimidazole dintrile amine salt, 1- octyl -3- methylimidazolium hydrogen sulphate salt, 1- second Base pyridinium bromide, 1- methyl-3- hexyl imidazolium perchlorate salt, 1- (2- ethoxy)-3- methylimidazolium chloride, 3- methyl-1- Octylimidazole nitrate, 1- ethyl-3-methylimidazole nitrate, 1- butyl -2,3- dimethyl limidazolium, 1- butyl -3- first Base imidazoles dicyan amine salt, 1- butyl -2,3- methylimidazole sulfate, 1- ethyl-3-methylimidazole dicyan methylene salt, 1- fourth Base -1- crassitude chloride.The special performance as possessed by ionic liquid, it is widely used in each of chemical research In a field, ionic liquid has been applied in multiple types reaction as the solvent of reaction, is not waved since ionic liquid has The ionic liquid of the characteristics such as hair property, high-fire resistance, noninflammability, high ion-conductivity, wide electrochemical window, special construction is received by addition Rice conductive particle and the lithium cell electrolyte conductivity prepared of lithium salts are higher, and it is not low temperature resistant to solve traditional lithium battery, It is not available under lower temperature or the problem of capacitance substantially reduces.
Further, the additive comprises at least one of the following: MgB2、Mg3N2、MgCl2、Mg2C3、Mg2Si、Mg3P2、 MgO、MgF2.It adds special nanoparticle and enables electrolyte normal use at a lower temperature, battery capacity is higher.
Further, the lithium salts comprises at least one of the following LiBF4、LiPF6、LiClO4、LiTFSI、LiAsF6、LiSbF6。 It adds special lithium salts and enables electrolyte normal use at a lower temperature, battery capacity is higher.
Further, the ionic liquid is 1- hexyl -3- methy limidazolium father-in-law and/or 1- ethyl-3-methylimidazole two Cyanogen methylene salt and/or 1- butyl -1- crassitude chloride.The ionic liquid of special construction enables electrolyte lower At a temperature of normal use, battery capacity is higher.
Further, the additive is MgB2And/or Mg3N2.Add special nanoparticle enable electrolyte compared with Normal use under low temperature, battery capacity are higher.
Further, the ionic liquid is 1- hexyl -3- methy limidazolium father-in-law, and the additive is MgB2.Special knot The ionic liquid of structure adds special nanoparticle and enables electrolyte normal use at a lower temperature, battery capacity compared with It is high.
Further, the ionic liquid content is 70-73 parts.Enable electrolyte normal use at a lower temperature, Battery capacity is higher.
Further, the additive level is 5-8 parts.Enable electrolyte normal use at a lower temperature, battery Capacitance is higher.
Further, the lithium salt content is 20-25 parts.Enable electrolyte normal use at a lower temperature, battery Capacitance is higher.
A kind of low temperature lithium battery, electrolyte used are the electrolyte of described in any item lithium batteries.It prepares Can in -60 DEG C of low temperature environments normal use high-capacity lithium battery.
Compared with the prior art, the invention has the following advantages:
(1) with prior art electrolyte phase ratio, conductivity is higher, while prepared battery charging and discharging capacitance is larger, Reach 160mAh/g or more.
(2) normal use, charge/discharge capacity it can be maintained at 75% or more when room temperature under at least -60 DEG C of low temperature, solved Low temperature cause battery at all can not normal use the problem of.
(3) biggish bump stress, superior performance can be born.
(4) preparation method is simple, is conducive to industrialize steady production, breakthrough is achieved in terms of low temperature lithium cell electrolyte Property progress, have very big industrial production prospect.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, and make features described above of the invention, Purpose and advantage are more clear understandable, are further explained explanation to the present invention now in conjunction with embodiment, it is noted that herein All embodiments listed are merely illustrative, are not meant to be defined the scope of the invention.
Embodiment 1
First 1L is added in 72g1- hexyl -3- methy limidazolium father-in-law's ionic liquid by a kind of electrolyte of lithium battery It in beaker, is stirred with magnetic stirring apparatus, then at the uniform velocity adds 21g LiClO4, at the uniform velocity it is added after stirring to the state of dissolving each other MgB27g is followed by stirring for 2 hours, and ultrasound 30min, the complete preparation completion after followed by stirring 3h of ultrasound obtain electrolysis material later Material, whole process are completed in the absence of air conditions, prevent from absorbing the moisture content in air.
Test the conductivity of electrolyte made from the present embodiment using AC impedence method, retest 5 times simultaneously calculates average Value, measuring conductivity is 8.16 × 10-3S/cm.Electrolyte made from the present embodiment is placed in lithium battery system, lithium battery is made Positive electrode is lithium-nickel-manganese-cobalt oxide (LiNi0.5Mn0.3Co0.2O2), negative electrode material be lithium, charge and discharge is carried out at 25 DEG C Electrical testing, measuring charging capacitor amount is 183mAh/g, discharge capacity 166mAh/g, measures electrochemical window and is greater than 4.5V, Cycle charge-discharge 100 times, capacity is maintained at 95% or more.Charge and discharge 10 times under the conditions of -40 DEG C, battery does not deform or electricity Solve 80% or more when matter leakage phenomenon charge/discharge capacity keeps room temperature.Charge and discharge 10 times under the conditions of -60 DEG C, battery do not occur Deformation or electrolyte leakage phenomenon, charge/discharge capacity keep 75% or more when room temperature, carry out 10 at room temperature4The bump stress of N Test, no leakage occur.
Embodiment 2
First 1L is added in 70g1- hexyl -3- methy limidazolium father-in-law's ionic liquid by a kind of electrolyte of lithium battery It in beaker, is stirred with magnetic stirring apparatus, then at the uniform velocity adds 25g LiClO4, at the uniform velocity it is added after stirring to the state of dissolving each other MgB25g is followed by stirring for 2 hours, and ultrasound 30min, the complete preparation completion after followed by stirring 3h of ultrasound obtain electrolysis material later Material, whole process are completed in the absence of air conditions, prevent from absorbing the moisture content in air.
Test the conductivity of electrolyte made from the present embodiment using AC impedence method, retest 5 times simultaneously calculates average Value, measuring conductivity is 8.04 × 10-3S/cm.Electrolyte made from the present embodiment is placed in lithium battery system, lithium battery is made Positive electrode is lithium-nickel-manganese-cobalt oxide (LiNi0.5Mn0.3Co0.2O2), negative electrode material be lithium, charge and discharge is carried out at 25 DEG C Electrical testing, measuring charging capacitor amount is 184mAh/g, discharge capacity 168mAh/g, measures electrochemical window and is greater than 4.5V, Cycle charge-discharge 100 times, capacity is maintained at 95% or more.Charge and discharge 10 times under the conditions of -40 DEG C, battery does not deform or electricity Solve 80% or more when matter leakage phenomenon charge/discharge capacity keeps room temperature.Charge and discharge 10 times under the conditions of -60 DEG C, battery do not occur Deformation or electrolyte leakage phenomenon, charge/discharge capacity keep 75% or more when room temperature, carry out 10 at room temperature4The bump stress of N Test, no leakage occur.
Embodiment 3
First 1L is added in 73g1- hexyl -3- methy limidazolium father-in-law's ionic liquid by a kind of electrolyte of lithium battery It in beaker, is stirred with magnetic stirring apparatus, then at the uniform velocity adds 20g LiClO4, at the uniform velocity it is added after stirring to the state of dissolving each other MgB27g is followed by stirring for 2 hours, and ultrasound 30min, the complete preparation completion after followed by stirring 3h of ultrasound obtain electrolysis material later Material, whole process are completed in the absence of air conditions, prevent from absorbing the moisture content in air.
Test the conductivity of electrolyte made from the present embodiment using AC impedence method, retest 5 times simultaneously calculates average Value, measuring conductivity is 8.11 × 10-3S/cm.Electrolyte made from the present embodiment is placed in lithium battery system, lithium battery is made Positive electrode is lithium-nickel-manganese-cobalt oxide (LiNi0.5Mn0.3Co0.2O2), negative electrode material be lithium, charge and discharge is carried out at 25 DEG C Electrical testing, measuring charging capacitor amount is 182mAh/g, discharge capacity 164mAh/g, measures electrochemical window and is greater than 4.5V, Cycle charge-discharge 100 times, capacity is maintained at 95% or more.Charge and discharge 10 times under the conditions of -40 DEG C, battery does not deform or electricity Solve 80% or more when matter leakage phenomenon charge/discharge capacity keeps room temperature.Charge and discharge 10 times under the conditions of -60 DEG C, battery do not occur Deformation or electrolyte leakage phenomenon, charge/discharge capacity keep 75% or more when room temperature, carry out 10 at room temperature4The bump stress of N Test, no leakage occur.
Embodiment 4
First 1L is added in 72g1- hexyl -3- methy limidazolium father-in-law's ionic liquid by a kind of electrolyte of lithium battery It in beaker, is stirred with magnetic stirring apparatus, then at the uniform velocity adds 21g LiClO4, at the uniform velocity it is added after stirring to the state of dissolving each other Mg3N27g is followed by stirring for 2 hours, and ultrasound 30min, the complete preparation completion after followed by stirring 3h of ultrasound obtain electrolysis material later Material, whole process are completed in the absence of air conditions, prevent from absorbing the moisture content in air.
Test the conductivity of electrolyte made from the present embodiment using AC impedence method, retest 5 times simultaneously calculates average Value, measuring conductivity is 8.23 × 10-3S/cm.Electrolyte made from the present embodiment is placed in lithium battery system, lithium battery is made Positive electrode is lithium-nickel-manganese-cobalt oxide (LiNi0.5Mn0.3Co0.2O2), negative electrode material be lithium, charge and discharge is carried out at 25 DEG C Electrical testing, measuring charging capacitor amount is 181mAh/g, discharge capacity 167mAh/g, measures electrochemical window and is greater than 4.5V, Cycle charge-discharge 100 times, capacity is maintained at 95% or more.Charge and discharge 10 times under the conditions of -40 DEG C, battery does not deform or electricity Solve 80% or more when matter leakage phenomenon charge/discharge capacity keeps room temperature.Charge and discharge 10 times under the conditions of -60 DEG C, battery do not occur Deformation or electrolyte leakage phenomenon, charge/discharge capacity keep 75% or more when room temperature, carry out 10 at room temperature4The bump stress of N Test, no leakage occur.
Embodiment 5
First 1L is added in 72g1- hexyl -3- methy limidazolium father-in-law's ionic liquid by a kind of electrolyte of lithium battery It in beaker, is stirred with magnetic stirring apparatus, then at the uniform velocity adds 21g LiClO4, at the uniform velocity it is added after stirring to the state of dissolving each other Mg2C37g is followed by stirring for 2 hours, and ultrasound 30min, the complete preparation completion after followed by stirring 3h of ultrasound obtain electrolysis material later Material, whole process are completed in the absence of air conditions, prevent from absorbing the moisture content in air.
Test the conductivity of electrolyte made from the present embodiment using AC impedence method, retest 5 times simultaneously calculates average Value, measuring conductivity is 8.04 × 10-3S/cm.Electrolyte made from the present embodiment is placed in lithium battery system, lithium battery is made Positive electrode is lithium-nickel-manganese-cobalt oxide (LiNi0.5Mn0.3Co0.2O2), negative electrode material be lithium, charge and discharge is carried out at 25 DEG C Electrical testing, measuring charging capacitor amount is 175mAh/g, discharge capacity 158mAh/g, measures electrochemical window and is greater than 4.5V, Cycle charge-discharge 100 times, capacity is maintained at 95% or more.Charge and discharge 10 times under the conditions of -40 DEG C, battery does not deform or electricity Solve 80% or more when matter leakage phenomenon charge/discharge capacity keeps room temperature.Charge and discharge 10 times under the conditions of -60 DEG C, battery do not occur Deformation or electrolyte leakage phenomenon, charge/discharge capacity keep 75% or more when room temperature, carry out 10 at room temperature4The bump stress of N Test, no leakage occur.
Embodiment 6
First 1L is added in 72g1- hexyl -3- methy limidazolium father-in-law's ionic liquid by a kind of electrolyte of lithium battery It in beaker, is stirred with magnetic stirring apparatus, then at the uniform velocity adds 21g LiClO4, at the uniform velocity it is added after stirring to the state of dissolving each other MgF27g is followed by stirring for 2 hours, and ultrasound 30min, the complete preparation completion after followed by stirring 3h of ultrasound obtain electrolysis material later Material, whole process are completed in the absence of air conditions, prevent from absorbing the moisture content in air.
Test the conductivity of electrolyte made from the present embodiment using AC impedence method, retest 5 times simultaneously calculates average Value, measuring conductivity is 8.37 × 10-3S/cm.Electrolyte made from the present embodiment is placed in lithium battery system, lithium battery is made Positive electrode is lithium-nickel-manganese-cobalt oxide (LiNi0.5Mn0.3Co0.2O2), negative electrode material be lithium, charge and discharge is carried out at 25 DEG C Electrical testing, measuring charging capacitor amount is 185mAh/g, discharge capacity 164mAh/g, measures electrochemical window and is greater than 4.5V, Cycle charge-discharge 100 times, capacity is maintained at 95% or more.Charge and discharge 10 times under the conditions of -40 DEG C, battery does not deform or electricity Solve 80% or more when matter leakage phenomenon charge/discharge capacity keeps room temperature.Charge and discharge 10 times under the conditions of -60 DEG C, battery do not occur Deformation or electrolyte leakage phenomenon, charge/discharge capacity keep 75% or more when room temperature, carry out 10 at room temperature4The bump stress of N Test, no leakage occur.
Embodiment 7
A kind of electrolyte of lithium battery first adds 72g1- ethyl-3-methylimidazole dicyan methylene ionic liquid Enter in 1L beaker, be stirred with magnetic stirring apparatus, then at the uniform velocity adds 21g LiClO4, at the uniform velocity add after stirring to the state of dissolving each other Enter MgB27g is followed by stirring for 2 hours, and ultrasound 30min, the complete preparation completion after followed by stirring 3h of ultrasound obtain electrolyte later Material, whole process are completed in the absence of air conditions, prevent from absorbing the moisture content in air.
Test the conductivity of electrolyte made from the present embodiment using AC impedence method, retest 5 times simultaneously calculates average Value, measuring conductivity is 7.98 × 10-3S/cm.Electrolyte made from the present embodiment is placed in lithium battery system, lithium battery is made Positive electrode is lithium-nickel-manganese-cobalt oxide (LiNi0.5Mn0.3Co0.2O2), negative electrode material be lithium, charge and discharge is carried out at 25 DEG C Electrical testing, measuring charging capacitor amount is 179mAh/g, discharge capacity 166mAh/g, measures electrochemical window and is greater than 4.5V, Cycle charge-discharge 100 times, capacity is maintained at 95% or more.Charge and discharge 10 times under the conditions of -40 DEG C, battery does not deform or electricity Solve 80% or more when matter leakage phenomenon charge/discharge capacity keeps room temperature.Charge and discharge 10 times under the conditions of -60 DEG C, battery do not occur Deformation or electrolyte leakage phenomenon, charge/discharge capacity keep 75% or more when room temperature, carry out 10 at room temperature4The bump stress of N Test, no leakage occur.
Embodiment 8
A kind of electrolyte of lithium battery first adds 72g1- ethyl-3-methylimidazole dicyan methylene ionic liquid Enter in 1L beaker, be stirred with magnetic stirring apparatus, then at the uniform velocity adds 21g LiClO4, at the uniform velocity add after stirring to the state of dissolving each other Enter MgB27g is followed by stirring for 2 hours, and ultrasound 30min, the complete preparation completion after followed by stirring 3h of ultrasound obtain electrolyte later Material, whole process are completed in the absence of air conditions, prevent from absorbing the moisture content in air.
Test the conductivity of electrolyte made from the present embodiment using AC impedence method, retest 5 times simultaneously calculates average Value, measuring conductivity is 8.14 × 10-3S/cm.Electrolyte made from the present embodiment is placed in lithium battery system, lithium battery is made Positive electrode is lithium-nickel-manganese-cobalt oxide (LiNi0.5Mn0.3Co0.2O2), negative electrode material be lithium, charge and discharge is carried out at 25 DEG C Electrical testing, measuring charging capacitor amount is 182mAh/g, discharge capacity 163mAh/g, measures electrochemical window and is greater than 4.5V, Cycle charge-discharge 100 times, capacity is maintained at 95% or more.Charge and discharge 10 times under the conditions of -40 DEG C, battery does not deform or electricity Solve 80% or more when matter leakage phenomenon charge/discharge capacity keeps room temperature.Charge and discharge 10 times under the conditions of -60 DEG C, battery do not occur Deformation or electrolyte leakage phenomenon, charge/discharge capacity keep 75% or more when room temperature, carry out 10 at room temperature4The bump stress of N Test, no leakage occur.
Embodiment 9
First 1L is added in 72g1- hexyl -3- methy limidazolium father-in-law's ionic liquid by a kind of electrolyte of lithium battery It in beaker, is stirred with magnetic stirring apparatus, then at the uniform velocity adds 21g LiBF4, at the uniform velocity it is added after stirring to the state of dissolving each other MgB27g is followed by stirring for 2 hours, and ultrasound 30min, the complete preparation completion after followed by stirring 3h of ultrasound obtain electrolysis material later Material, whole process are completed in the absence of air conditions, prevent from absorbing the moisture content in air.
Test the conductivity of electrolyte made from the present embodiment using AC impedence method, retest 5 times simultaneously calculates average Value, measuring conductivity is 8.31 × 10-3S/cm.Electrolyte made from the present embodiment is placed in lithium battery system, lithium battery is made Positive electrode is lithium-nickel-manganese-cobalt oxide (LiNi0.5Mn0.3Co0.2O2), negative electrode material be lithium, charge and discharge is carried out at 25 DEG C Electrical testing, measuring charging capacitor amount is 184mAh/g, discharge capacity 162mAh/g, measures electrochemical window and is greater than 4.5V, Cycle charge-discharge 100 times, capacity is maintained at 95% or more.Charge and discharge 10 times under the conditions of -40 DEG C, battery does not deform or electricity Solve 80% or more when matter leakage phenomenon charge/discharge capacity keeps room temperature.Charge and discharge 10 times under the conditions of -60 DEG C, battery do not occur Deformation or electrolyte leakage phenomenon, charge/discharge capacity keep 75% or more when room temperature, carry out 10 at room temperature4The bump stress of N Test, no leakage occur.
Embodiment 10
First 1L is added in 72g1- hexyl -3- methy limidazolium father-in-law's ionic liquid by a kind of electrolyte of lithium battery It in beaker, is stirred with magnetic stirring apparatus, then at the uniform velocity adds 21g LiPF6, at the uniform velocity it is added after stirring to the state of dissolving each other MgB27g is followed by stirring for 2 hours, and ultrasound 30min, the complete preparation completion after followed by stirring 3h of ultrasound obtain electrolysis material later Material, whole process are completed in the absence of air conditions, prevent from absorbing the moisture content in air.
Test the conductivity of electrolyte made from the present embodiment using AC impedence method, retest 5 times simultaneously calculates average Value, measuring conductivity is 7.89 × 10-3S/cm.Electrolyte made from the present embodiment is placed in lithium battery system, lithium battery is made Positive electrode is lithium-nickel-manganese-cobalt oxide (LiNi0.5Mn0.3Co0.2O2), negative electrode material be lithium, charge and discharge is carried out at 25 DEG C Electrical testing, measuring charging capacitor amount is 181mAh/g, discharge capacity 163mAh/g, measures electrochemical window and is greater than 4.5V, Cycle charge-discharge 100 times, capacity is maintained at 95% or more.Charge and discharge 10 times under the conditions of -40 DEG C, battery does not deform or electricity Solve 80% or more when matter leakage phenomenon charge/discharge capacity keeps room temperature.Charge and discharge 10 times under the conditions of -60 DEG C, battery do not occur Deformation or electrolyte leakage phenomenon, charge/discharge capacity keep 75% or more when room temperature, carry out 10 at room temperature4The bump stress of N Test, no leakage occur.
Embodiment 11
The present embodiment is comparative example, using common LiPF6Add divinyl carbonic ester (EC) plus dimethyl carbonate (DMC) it is used as electrolyte.It is compared under the same conditions with the embodiment of the present invention.
Test the conductivity of electrolyte made from the present embodiment using AC impedence method, retest 5 times simultaneously calculates average Value, measuring conductivity is 2.25 × 10-3S/cm.Electrolyte made from the present embodiment is placed in lithium battery system, lithium battery is made Positive electrode is lithium-nickel-manganese-cobalt oxide (LiNi0.5Mn0.3Co0.2O2), negative electrode material be lithium, charge and discharge is carried out at 25 DEG C Electrical testing, measuring charging capacitor amount is 112mAh/g, discharge capacity 73mAh/g, measures electrochemical window less than 4.5V, follows Ring charge and discharge 100 times, capacity drops to 90% or less.Charge and discharge under the conditions of -40 DEG C, capacity drop to 50% or less when room temperature. When charge and discharge under the conditions of -60 DEG C, capacity drop to room temperature 40% hereinafter, there is a situation where cannot normal charge and discharge.At 25 DEG C Carry out 104The bump stress of N is tested, and electrolyte is revealed.
It can analyze and find out, electrolyte product of the embodiment of the present invention and prior art electrolyte phase ratio, conductivity is higher, together When prepared battery charging and discharging capacitance it is larger, reach 180mAh/g, can normal use, charge and discharge under at least -60 DEG C of low temperature Capacitance is maintained at 75% or more when room temperature, can bear biggish bump stress, superior performance, solving low temperature leads to electricity Pond at all can not normal use the problem of, achieve breakthrough in terms of low temperature lithium cell electrolyte, there is very big industrialization Prospect of production.
It is above-mentioned that only several specific embodiments in the present invention are illustrated, but can not be as protection model of the invention Enclose, it is all according to the present invention in design spirit made by equivalent change or modification or equal proportion zoom in or out, should all Think to fall into protection scope of the present invention.

Claims (10)

1. a kind of electrolyte of lithium battery, it is characterised in that: the raw material including following mass fraction: ionic liquid 64-80 Part, 0.5-8 parts of additive, 12-27 parts of lithium salts, the ionic liquid comprises at least one of the following: butyl pyridinium bromide, 1- oneself Base -3- methy limidazolium father-in-law, 1- butyl -3- methylimidazole tosilate, 1- ethyl -3- methy limidazolium 1- are pungent Base -3- methylimidazole dintrile amine salt, 1- octyl -3- methylimidazolium hydrogen sulphate salt, 1- ethyl pyridinium bromide, 1- methyl -3- hexyl Imidazoles perchlorate salt, 1- (2- ethoxy)-3- methylimidazolium chloride, 3- methyl-1-octylimidazole nitrate, 1- ethyl-3- Methylimidazolium nitrate, 1- butyl -2,3- dimethyl limidazolium, 1- butyl -3- methylimidazole dicyan amine salt, butyl -2 1-, 3- methylimidazole sulfate, 1- ethyl-3-methylimidazole dicyan methylene salt, 1- butyl -1- crassitude chloride.
2. a kind of electrolyte of lithium battery according to claim 1, it is characterised in that: the additive includes following It is at least one: MgB2、Mg3N2、MgCl2、Mg2C3、Mg2Si、Mg3P2、MgO、MgF2
3. a kind of electrolyte of lithium battery according to claim 1 or 2, it is characterised in that: the lithium salts include with Lower at least one LiBF4、LiPF6、LiClO4、LiTFSI、LiAsF6、LiSbF6
4. a kind of electrolyte of lithium battery according to claim 3, it is characterised in that: the ionic liquid be 1- oneself Base -3- methy limidazolium father-in-law and/or 1- ethyl-3-methylimidazole dicyan methylene salt and/or 1- butyl -1- crassitude chlorine Compound.
5. a kind of electrolyte of lithium battery according to claim 4, it is characterised in that: the additive is MgB2With/ Or Mg3N2
6. a kind of electrolyte of lithium battery according to claim 5, it is characterised in that: the ionic liquid be 1- oneself Base -3- methy limidazolium father-in-law, the additive are MgB2
7. according to a kind of described in any item electrolytes of lithium battery of claim 4-6, it is characterised in that: the ionic liquid Body content is 70-73 parts.
8. a kind of electrolyte of lithium battery according to claim 7, it is characterised in that: the additive level is 5- 8 parts.
9. a kind of electrolyte of lithium battery according to claim 8, it is characterised in that: the lithium salt content is 20- 25 parts.
10. a kind of low temperature lithium battery, electrolyte used is the electrolysis material of the described in any item lithium batteries of claim 1-9 Material.
CN201910480398.6A 2019-06-04 2019-06-04 A kind of electrolyte and its application on low temperature lithium battery Pending CN110289449A (en)

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