CN109309250A - Electrolyte and secondary lithium battery - Google Patents

Electrolyte and secondary lithium battery Download PDF

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Publication number
CN109309250A
CN109309250A CN201710625262.0A CN201710625262A CN109309250A CN 109309250 A CN109309250 A CN 109309250A CN 201710625262 A CN201710625262 A CN 201710625262A CN 109309250 A CN109309250 A CN 109309250A
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electrolyte
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substituted
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quaternary ammonium
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王小梅
付成华
韩昌隆
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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

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  • 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)

Abstract

The application provides an electrolyte and a secondary lithium battery, wherein the electrolyte comprises electrolyte salt and an additive. The additive comprises sulfonic ester cyclic quaternary ammonium salt and lithium difluorobis (oxalato) phosphate. The two are matched for use, so that a compact and firm passivation film can be formed on the surfaces of the anode and the cathode of the secondary lithium battery, and the contact between the anode and the cathode and the electrolyte is reduced, so that the continuous oxidation and reduction reaction of the electrolyte on the surfaces of the anode and the cathode is avoided, the decomposition of the electrolyte and the increase of the internal resistance of the secondary lithium battery are weakened, and the secondary lithium battery has better high-temperature storage performance.

Description

Electrolyte and serondary lithium battery
Technical field
This application involves field of batteries more particularly to a kind of electrolyte and serondary lithium battery.
Background technique
As increasingly depleted and environmental pollution the pressure of fossil energy is increasing, there is an urgent need to a kind of new for automobile industry The type energy provides driving for it, and lithium ion battery is due to having the characteristics that energy density height, memory-less effect, operating voltage are high de- Grain husk and go out, making it currently becomes the preferred option of new-energy automobile electrical source of power.However as the expansion of electronics market demand Big and power, energy storage device development, requirement of the people to lithium ion battery are continuously improved, and exploitation has high-energy density and full The lithium ion battery of sufficient fast charging and discharging becomes the task of top priority.Currently, effective method be improve the voltage of electrode active material, Compacted density and the suitable electrolyte of selection.
Currently, widely applied electrolyte is usually using lithium hexafluoro phosphate as electrolytic salt and with ring in lithium ion battery Shape carbonic ester and the mixture of linear carbonate are the electrolyte of organic solvent, however above-mentioned electrolyte is there are many deficiencies, Specifically under high voltages, the high-temperature storage performance of lithium ion battery is poor, wherein weight of the electrolyte as lithium ion battery Component part is wanted, there is great influence to the chemical property of lithium ion battery, the composition by improving electrolyte can Improve the high-temperature storage performance of lithium ion battery to a certain extent.
Summary of the invention
In view of the problems in the background art, the application is designed to provide a kind of electrolyte and serondary lithium battery, The serondary lithium battery has preferable high-temperature storage performance.
In order to achieve the above object, in the one side of the application, this application provides a kind of electrolyte comprising electrolyte Salt and additive.The additive includes sulphonic acid ester cyclic quaternary ammonium salts and the double oxalic acid lithium phosphates of difluoro.
In the another aspect of the application, this application provides a kind of serondary lithium batteries comprising the electricity of the application one side Solve liquid.
Compared with the existing technology, the application has the beneficial effect that
The electrolysis additive of the application includes sulphonic acid ester cyclic quaternary ammonium salts and the double oxalic acid lithium phosphates of difluoro, the two collocation Using positive and negative electrode and electrolyte can be reduced in one layer of densification of positive and negative anodes Surface Creation of serondary lithium battery and firm passivating film Contact, to avoid electrolyte that continued oxidation and reduction reaction occurs on positive and negative electrode surface, and then reduce point of electrolyte The internal resistance of solution and serondary lithium battery rises, and serondary lithium battery is made to have preferable high-temperature storage performance.
Specific embodiment
The following detailed description of the electrolyte and serondary lithium battery according to the application.
Illustrate the electrolyte according to the application first aspect first.
Electrolyte according to the application first aspect includes electrolytic salt and additive.The additive includes sulphonic acid ester Cyclic quaternary ammonium salts and the double oxalic acid lithium phosphates of difluoro.
In the electrolyte according to the application first aspect, the sulphonic acid ester cyclic quaternary ammonium salts are selected from shown in formula 1 One or more of compound；In formula 1, R11Alkyl selected from-CN, substituted or unsubstituted C1~12 replaces or does not take The alkenyl of C2~12 in generation, the alkynyl of substituted or unsubstituted C2~12, the alkoxy of substituted or unsubstituted C1~12, substitution Or one of acyloxy of unsubstituted C1~12；R12Alkylidene selected from substituted or unsubstituted C1~12 replaces or not The alkenylene of substituted C2~12, the alkynylene of substituted or unsubstituted C2~12, substituted or unsubstituted C1~12 alkylene One of acyl group；R13The alkenyl of alkyl, substituted or unsubstituted C2~12 selected from substituted or unsubstituted C1~12 replaces Or the alkynyl of unsubstituted C2~12, the alkoxy of substituted or unsubstituted C1~12, substituted or unsubstituted C1~12 acyl One of oxygroup, the aryl of substituted or unsubstituted C6~22, heterocyclic base of substituted or unsubstituted C5~22；R14Selected from taking The alkylidene of generation or unsubstituted C1~3；Substituent group is selected from one or more of-CN, halogen atom.
In formula 1,Indicate anion,Selected from F-、NO3 -、SO4 2-、PF6 -、PF4 -、AsF6 -、(FSO2)2N-、 One of.
In the electrolyte according to the application first aspect, the structural formula such as formula 2 of the double oxalic acid lithium phosphates of the difluoro It is shown.
In the electrolyte according to the application first aspect, the electrolyte can be poly- for liquid electrolyte, solid-state Polymer electrolyte or gel polymer electrolytes can be selected according to actual needs.Due to liquid electrolyte and solid-state polymerization Object electrolyte, the mechanism of action of gel polymer electrolytes are similar, therefore are only illustrated carry out with liquid electrolyte in this application Explanation.
In the electrolyte according to the application first aspect, the sulphonic acid ester cyclic quaternary ammonium salts and the double oxalic acid phosphorus of difluoro The collocation of sour lithium is using can reduce positive and negative electrode and electrolyte in the one layer of densification of positive and negative anodes Surface Creation and firm passivating film Contact to avoid electrolyte that continued oxidation and reduction reaction occurs on positive and negative electrode surface, and then reduces the decomposition of electrolyte Internal resistance with serondary lithium battery rises, and improves the high-temperature storage performance of serondary lithium battery.The reason is that for sulphonic acid ester ring For shape quaternary ammonium salt, special construction (the cation group portion of the i.e. described sulphonic acid ester cyclic quaternary ammonium salts that cation group has Divide and intermediate organic carbon chain link is passed through by the cyclic quaternary head of tape unit positive charge and functional sulphonic acid ester tail portion At), the cyclic quaternary head of tape unit positive charge can be made in reduction potential 1.5V, be able to drive entire cation group It is actively broken close to cathode by preferential reduction decomposition, and releases functional sulphonic acid ester tail portion, it can be in negative terminal surface One layer of SEI film by material compositions such as Lithium perchlorates preferentially is established, since Lithium perchlorate intrinsic ion with higher passes Conductance, and have very high thermal stability, therefore thus negative terminal surface formed SEI film have internal structure cause it is dense and uniform, The internal resistance of the features such as impedance low and high temperature is had excellent performance, the decomposition and serondary lithium battery that can weaken electrolyte rises.The double grass of difluoro Acid phosphoric acid lithium can be then oxidized in anode, thus positive electrode surface formed compact structure and uniformly, impedance low and high temperature has excellent performance Passivating film, can further improve the high-temperature storage performance of serondary lithium battery, especially inhibition high temperature storage volume expansion.Cause This, when oxalic acid lithium phosphates double containing sulphonic acid ester cyclic quaternary ammonium salts and difluoro simultaneously in electrolyte, serondary lithium battery it is positive and negative Pole surface is respectively formed fine and close, uniform and low impedance passivating film, can effectively prevent oxygen lasting between positive and negative electrode and electrolyte Change reduction reaction, and then reduce the decomposition of electrolyte and the internal resistance rising of serondary lithium battery, so as to improve serondary lithium battery High-temperature storage performance.
In the electrolyte according to the application first aspect, in formula 1, it is preferable that R11Selected from substituted or unsubstituted C1~6 alkyl or one of halogenated alkyl, R12One of alkylidene selected from substituted or unsubstituted C1~12, R13One of alkyl or halogenated alkyl selected from substituted or unsubstituted C1~6, R14Selected from substituted or unsubstituted C1~2 One of alkylidene.
In the electrolyte according to the application first aspect, the cation group of the sulphonic acid ester cyclic quaternary ammonium salts is selected From
One of.
In the electrolyte according to the application first aspect, specifically, the sulphonic acid ester cyclic quaternary ammonium salts are selected from down State one or more of compound；But the application is without being limited thereto；
In the electrolyte according to the application first aspect, the content of the sulphonic acid ester cyclic quaternary ammonium salts is the electricity Solve the 0.05%~10% of liquid gross mass.When content is very few, the positive and negative anodes passivating film of formation be not sufficient to prevent electrolyte into Single step reaction, it is also unobvious to the improvement of serondary lithium battery performance.And when too high levels, then its impedance on positive and negative anodes increases Add, deteriorates serondary lithium battery performance instead.Preferably, the content of the sulphonic acid ester cyclic quaternary ammonium salts is the electrolyte gross mass 0.1%~5%.
In the electrolyte according to the application first aspect, the content of the double oxalic acid lithium phosphates of the difluoro is the electricity Solve the 0.05%~8% of liquid gross mass.If the content of the double oxalic acid lithium phosphates of difluoro is too low, electrolyte is applied to serondary lithium battery In after, the storage life of serondary lithium battery and storage flatulence are not improved.If the too high levels of the double oxalic acid lithium phosphates of difluoro, It can be since the increase of impedance be to deteriorate storage performance.Preferably, the content of the double oxalic acid lithium phosphates of the difluoro is the electrolysis The 0.15%~6% of liquid gross mass.It is further preferred that the content of the double oxalic acid lithium phosphates of the difluoro is the total matter of the electrolyte The 0.2%~2.5% of amount.
In the electrolyte according to the application first aspect, the concentration of the electrolytic salt is not limited specifically, It can be selected according to actual needs.Specifically, the content of the electrolytic salt be the electrolyte gross mass 6%~ 25%.Preferably, the content of the electrolytic salt is the 6%~20% of the gross mass of the electrolyte.It is further preferred that institute State electrolytic salt content be the electrolyte gross mass 10%~15%.
In the electrolyte according to the application first aspect, the electrolytic salt can be lithium salts, the kind of the lithium salts Class does not limit specifically, can be selected according to actual needs.Preferably, the electrolytic salt includes at least LiPF6, described Electrolytic salt can further include LiBF4、LiClO4、LiAsF6、LiSbF6、LiBOB、LiDFOB、LiFSI、LiTFSI、 LiPO2F2、LiTFOP、LiN(SO2RF)2、LiN(SO2F)(SO2One or more of RF).
In the electrolyte according to the application first aspect, the electrolyte further includes organic solvent, described organic The type of solvent can be selected according to actual needs there is no specific limitation.Preferably, using non-aqueous organic solvent.Institute State the carbonic ester and/or carboxylate that non-aqueous organic solvent may include any kind.For example, the carbonic ester may include cyclic carbonate The mixture of ester and linear carbonate.The non-aqueous organic solvent may also include the halogenated compound of carbonic ester.Specifically, institute Stating organic solvent can be selected from ethylene carbonate, propylene carbonate, butylene carbonate, pentylene, fluoroethylene carbonate, carbon Dimethyl phthalate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl formate, Ethyl formate, ethyl acetate, propionic acid third One or more of ester, ethyl propionate, gamma-butyrolacton, tetrahydrofuran.
Secondly illustrate the serondary lithium battery according to the application second aspect.
It include the electrolyte according to the application first aspect according to serondary lithium battery described in the application second aspect.
In the serondary lithium battery according to the application second aspect, the serondary lithium battery further includes positive plate, bears Pole piece, isolation film and pack case etc..
In the serondary lithium battery according to the application second aspect, it should be noted that the serondary lithium battery can It can also be lithium metal battery for lithium ion battery.In embodiments herein, only showing serondary lithium battery is lithium ion battery Embodiment, but the application is without being limited thereto.
In the serondary lithium battery according to the application second aspect, positive plate includes plus plate current-collecting body and is set to just Positive diaphragm on the collector of pole.It is described anode diaphragm include positive electrode active materials, it is described anode diaphragm may also include conductive agent, Binder.Positive electrode active materials can be selected from cobalt acid lithium (LiCoO2), lithium nickelate (LiNiO2), the LiMn2O4 of spinel-type (LiMn2O4), the LiMPO of olivine-type4, ternary material LiaNixAyB(1-x-y)O2One or more of.Wherein, in olivine The LiMPO of type4In, M is selected from one or more of Co, Ni, Fe, Mn, V；In ternary material LiaNixAyB(1-x-y)O2In, A, B It is each independently selected from one of Co, Al, Mn, and A and B be not identical, 0.95≤a≤1.2,0 < x < 1,0 < y < 1, and x+y < 1. The not specific limitation of the type of conductive agent and binder, can be selected according to actual needs.
In the serondary lithium battery according to the application second aspect, negative electrode tab includes negative current collector and is set to negative Cathode membrane on the collector of pole.The cathode membrane includes negative electrode active material, the cathode membrane may also include conductive agent, Binder.The negative electrode active material can be selected from voltage < 2V (vs.Li/Li+) when can be embedded in the material of lithium, specifically Ground, it is multiple that the negative electrode active material can be selected from the micro- carbon ball of natural graphite, artificial graphite, interphase, hard carbon, soft carbon, silicon, silico-carbo Close object, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO, SnO2、TiO2-Li4Ti5O12, one or more of Li-Al alloy. The not specific limitation of the type of conductive agent and binder, can be selected according to actual needs.The negative electrode tab can also be selected directly From metal lithium sheet.
In the serondary lithium battery according to the application second aspect, the type of the isolation film is not specifically limited, It can be selected according to actual needs, specifically, the isolation film can be selected from polyethylene film, polypropylene screen, polyvinylidene fluoride film And their multilayer complex films.
Below with reference to embodiment, the application is further described.It should be understood that these embodiments be merely to illustrate the application without For limiting scope of the present application.
In the following embodiments, reagent, material and the instrument used such as not special explanation, it is commercially available to obtain , used sulphonic acid ester cyclic quaternary ammonium salts can refer to Chinese patent CN105845981A disclosed on August 10th, 2016.
Lithium ion battery in embodiment 1-15 and comparative example 1-7 is prepared by the following method:
(1) preparation of positive plate
By positive electrode active materials LiNi0.6Co0.2Mn0.2O2, conductive agent acetylene black, binder polyvinylidene fluoride press quality Than for LiNi0.6Co0.2Mn0.2O2: acetylene black: polyvinylidene fluoride=98:1:1 is mixed, and Solvents N-methyl pyrrolidines is added Ketone, stirring obtains anode sizing agent to system at transparent and homogeneous shape under de-airing mixer effect；Anode sizing agent is evenly applied to With a thickness of on 12 μm of plus plate current-collecting body aluminium foil；Aluminium foil is transferred to 120 DEG C of oven drying 1h after room temperature is dried, is then passed through Cold pressing, cutting obtain positive plate.
(2) preparation of negative electrode tab
By negative electrode active material artificial graphite, thickener sodium carboxymethylcellulose (CMC), binder butadiene-styrene rubber according to matter Amount is mixed than 98:1:1, and deionized water is added, and obtains negative electrode slurry under de-airing mixer effect；Negative electrode slurry is uniform Coated on the negative current collector copper foil with a thickness of 8 μm；Copper foil is transferred to 120 DEG C of oven drying 1h after room temperature is dried, so Afterwards by being cold-pressed, cutting to obtain negative electrode tab.
(3) preparation of electrolyte
In water content < 10ppm argon atmosphere glove box, by ethylene carbonate (EC), methyl ethyl carbonate (EMC), carbon Diethyl phthalate (DEC) is that EC:EMC:DEC=1:1:1 is mixed according to volume ratio, then by sufficiently dry lithium salts LiPF6 It is dissolved in mixed organic solvents, the double oxalic acid lithium phosphates of sulphonic acid ester cyclic quaternary ammonium salts, difluoro is added later, obtain after mixing Electrolyte.Wherein, LiPF6Content be electrolyte gross mass 12.5%.Used sulphonic acid ester cyclic annular season in electrolyte The specific type and content of ammonium salt and the double oxalic acid lithium phosphates of difluoro are as shown in table 1, and in table 1, sulphonic acid ester cyclic quaternary ammonium salts Content with the double oxalic acid lithium phosphates of difluoro is the mass percent that the gross mass based on electrolyte is calculated.
(4) preparation of isolation film
Select the polypropylene isolation film of 16 μ m-thicks (model A273 is provided by Celgard company).
(5) preparation of lithium ion battery
Positive plate, isolation film, negative electrode tab are folded in order, isolation film is between positive and negative plate and plays isolation Effect, then winding obtains naked battery core；Naked battery core is placed in outer packing shell, the above-mentioned electrolyte prepared is injected into drying In naked battery core afterwards, by processes such as Vacuum Package, standing, chemical conversion, shapings, lithium ion battery is obtained.
The parameter of table 1 embodiment 1~15 and comparative example 1~7
The test process of lithium ion battery will be illustrated next.
(1) the high temperature storage capacity retention ratio test of lithium ion battery
It with 1C constant current charge to voltage is 4.4V by lithium ion battery, then extremely with 4.4V constant-voltage charge at 25 DEG C Electric current is less than 0.05C, is later 3.0V with 0.5C constant-current discharge to voltage；It is again 4.4V with 1C constant-current charge to voltage, then It is less than 0.05C with 4.4V constant-voltage charge to electric current, test the discharge capacity of lithium ion battery at this time and is denoted as D0；Then by lithium from Sub- battery is placed at 60 DEG C and stores 30 days, is 3.0V with 1C constant-current discharge to voltage after storing；Again with 1C constant-current charge It is 4.4V to voltage, 0.05C is then less than with 4.4V constant-voltage charge to electric current, is with 0.5C constant-current discharge to voltage later 3.0V tests the discharge capacity of lithium ion battery at this time and is denoted as D1.15 lithium ion batteries of every group of test, are averaged.
Capacity retention ratio (%)=[D1/D0] × 100% behind 60 DEG C of storages 30 days of lithium ion battery.
(2) high temperature storage of lithium ion battery produces gas test
It with 0.5C constant-current charge to voltage is 4.2V by lithium ion battery, extremely with 4.2V constant-voltage charge later at 25 DEG C Electric current is 0.05C, and the initial volume of lithium ion battery at this time is tested using drainage, and is denoted as V0, then by lithium ion battery It is put into 70 DEG C of insulating box storage 360h, after taking out after storage, the volume of lithium ion battery at this time is tested using drainage, And it is denoted as V1.15 lithium ion secondary batteries of every group of test, are averaged.
Cubical expansivity (%)=(V1-V0)/V0 × 100% after 70 DEG C of lithium ion battery storage 360h.
The performance test results of table 2 embodiment 1~15 and comparative example 1~7
From the Correlative data analysis of table 2 it is found that sulphonic acid ester cyclic quaternary ammonium salts and difluoro is added in lithium ion battery at the same time When double oxalic acid lithium phosphates, there can be preferable high-temperature storage performance under the collective effect of the two.
The analysis in comparative example 1~3 is it is found that sulphonic acid ester cyclic quaternary ammonium salts and the double oxalic acid of difluoro are not added in comparative example 1 When lithium phosphate, the high temperature storage capacity retention ratio and high temperature storage cubical expansivity of lithium ion battery are poor；When in electrolyte When only containing sulphonic acid ester cyclic quaternary ammonium salts (comparative example 2), the high temperature storage capacity retention ratio and high temperature storage body of lithium ion battery Product expansion rate can obtain a degree of improvement, and however, the high temperature storage cubical expansivity of lithium ion battery is still It is old larger, it is difficult to meet actual use demand；When only oxalic acid lithium phosphate (comparative examples 3) double containing difluoro in electrolyte, lithium The also available a degree of improvement of the high temperature storage capacity retention ratio and high temperature storage cubical expansivity of ion battery, but it is same Its improvement degree of sample is also difficult to meet actual use demand.
The analysis in embodiment 1~15 and comparative example 4~7 it is found that when containing sulphonic acid ester cyclic quaternary simultaneously in electrolyte When the double oxalic acid lithium phosphates of salt and difluoro, can make lithium ion battery simultaneously high temperature storage circulation volume conservation rate with higher and The high-temperature storage performance performance of lower high temperature storage cubical expansivity, lithium ion battery is good, expires lithium ion battery Full border use demand.But it is understood that the specific type of sulphonic acid ester cyclic quaternary ammonium salts and the double oxalic acid lithium phosphates of difluoro And dosage variation necessarily directly influences the performance of electrolyte, to influence the improvement to performance of lithium ion battery.
In comparative example 4, the content of sulphonic acid ester cyclic quaternary ammonium salts is insufficient, keeps to the high temperature storage capacity of lithium ion battery The improvement of rate and high temperature storage cubical expansivity is limited.In Examples 1 to 5, with the increasing of sulphonic acid ester cyclic quaternary salt content More, the high temperature storage cubical expansivity of lithium ion battery gradually improves, while the high temperature storage capacity retention ratio of lithium ion battery Also improved to a certain extent.When the too high levels of sulphonic acid ester cyclic quaternary ammonium salts, such as in comparative example 5, can significantly deteriorate The high temperature storage capacity retention ratio of lithium ion battery.
In comparative example 6, the content of the double oxalic acid lithium phosphates of difluoro is insufficient, the high-temperature storage volume expansion to lithium ion battery Rate improves weaker.In embodiment 6~12, with increasing for the double oxalic acid phosphoric acid lithium contents of difluoro, the height of lithium ion battery is gentle Storage cubical expansivity gradually reduces, while the high temperature storage capacity retention ratio of lithium ion battery is also changed to a certain extent It is kind.When the too high levels of the double oxalic acid lithium phosphates of difluoro, such as in comparative example 7, the high temperature storage of lithium ion battery can be deteriorated Capacity retention ratio.
Therefore, the content of sulphonic acid ester cyclic quaternary ammonium salts and the double oxalic acid lithium phosphates of difluoro is too little or too much is unfavorable for from totality The upper performance for improving lithium ion battery.But it is required in relatively low or more secondary use demand for some, it equally can be with Improve the high-temperature storage performance of lithium ion battery to a certain extent.
The announcement of book according to the above description, the application those skilled in the art can also carry out above embodiment Change and modification appropriate.Therefore, the application is not limited to specific embodiment disclosed and described above, to the application's Some modifications and changes should also be as falling into the protection scope of claims hereof.

Claims (10)

1. a kind of electrolyte, comprising:
Electrolytic salt；And
Additive；
It is characterized in that,
The additive includes sulphonic acid ester cyclic quaternary ammonium salts and the double oxalic acid lithium phosphates of difluoro.
2. electrolyte according to claim 1, which is characterized in that the sulphonic acid ester cyclic quaternary ammonium salts are selected from shown in formula 1 One or more of compound；
In formula 1, R11The alkenyl of alkyl, substituted or unsubstituted C2~12 selected from-CN, substituted or unsubstituted C1~12, The alkynyl of substituted or unsubstituted C2~12, the alkoxy of substituted or unsubstituted C1~12, substituted or unsubstituted C1~12 One of acyloxy；
R12The alkenylene of alkylidene, substituted or unsubstituted C2~12 selected from substituted or unsubstituted C1~12 replaces or not One of the alkynylene of substituted C2~12, alkylene acyl group of substituted or unsubstituted C1~12；
R13It is the alkenyl of alkyl, substituted or unsubstituted C2~12 selected from substituted or unsubstituted C1~12, substituted or unsubstituted The alkynyl of C2~12, the alkoxy of substituted or unsubstituted C1~12, substituted or unsubstituted C1~12 acyloxy, replace Or one of the aryl of unsubstituted C6~22, heterocyclic base of substituted or unsubstituted C5~22；
R14Alkylidene selected from substituted or unsubstituted C1~3；
Substituent group is selected from one or more of-CN, halogen atom；
Indicate anion,Selected from F-、NO3 -、SO4 2-、PF6 -、PF4 -、AsF6 -、(FSO2)2N-、 One of.
3. electrolyte according to claim 2, which is characterized in that the cation group of the sulphonic acid ester cyclic quaternary ammonium salts is selected from
One of.
4. electrolyte according to claim 3, which is characterized in that the sulphonic acid ester cyclic quaternary ammonium salts are selected from following compounds One or more of:
5. electrolyte according to claim 1, which is characterized in that
The content of the sulphonic acid ester cyclic quaternary ammonium salts is the 0.05%~10% of the electrolyte gross mass, it is preferable that the sulphur The content of acid esters cyclic quaternary ammonium salts is the 0.1%~5% of the electrolyte gross mass.
6. electrolyte according to claim 1, which is characterized in that
The content of the double oxalic acid lithium phosphates of the difluoro is the 0.05%~8% of the electrolyte gross mass, it is preferable that the difluoro The content of double oxalic acid lithium phosphates is the 0.15%~6% of the electrolyte gross mass, it is further preferred that the double oxalic acid of the difluoro The content of lithium phosphate is the 0.2%~2.5% of the electrolyte gross mass.
7. electrolyte according to claim 1, which is characterized in that the electrolyte is liquid electrolyte, solid polymer Electrolyte or gel polymer electrolytes.
8. electrolyte according to claim 1, which is characterized in that
The electrolytic salt is selected from LiPF6、LiBF4、LiFSI、LiTFSI、LiClO4、LiAsF6、LiBOB、LiDFOB、 LiPO2F2、LiTFOP、LiN(SO2RF)2、LiN(SO2F)(SO2One or more of RF), wherein RF=CnF2n+1, indicate full And perfluoroalkyl, n are the integer in 1~10.
9. electrolyte according to claim 1, which is characterized in that the content of the electrolytic salt is the total matter of the electrolyte The 6%~25% of amount, it is preferable that the content of the electrolytic salt is the 6%~20% of the electrolyte gross mass, further excellent Selection of land, the content of the electrolytic salt are the 10%~15% of the electrolyte gross mass.
10. a kind of serondary lithium battery, which is characterized in that including electrolyte according to claim 1 to 9.
CN201710625262.0A 2017-07-27 2017-07-27 Electrolyte and secondary lithium battery Pending CN109309250A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114142087A (en) * 2021-10-14 2022-03-04 合肥国轩高科动力能源有限公司 Electrolyte for improving high-temperature performance of lithium ion battery and lithium ion battery

Citations (3)

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CN105098240A (en) * 2014-05-21 2015-11-25 株式会社杰士汤浅国际 Method for producing energy storage device and energy storage device
CN106025359A (en) * 2016-07-08 2016-10-12 珠海市赛纬电子材料股份有限公司 Lithium ion power battery non-water electrolyte
CN106099184A (en) * 2016-06-28 2016-11-09 宁德新能源科技有限公司 A kind of electrolyte and use the lithium ion battery of this electrolyte

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CN105098240A (en) * 2014-05-21 2015-11-25 株式会社杰士汤浅国际 Method for producing energy storage device and energy storage device
CN106099184A (en) * 2016-06-28 2016-11-09 宁德新能源科技有限公司 A kind of electrolyte and use the lithium ion battery of this electrolyte
CN106025359A (en) * 2016-07-08 2016-10-12 珠海市赛纬电子材料股份有限公司 Lithium ion power battery non-water electrolyte

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Publication number Priority date Publication date Assignee Title
CN114142087A (en) * 2021-10-14 2022-03-04 合肥国轩高科动力能源有限公司 Electrolyte for improving high-temperature performance of lithium ion battery and lithium ion battery

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Application publication date: 20190205