CN110336075A - Electrolyte and electrochemical appliance and electronic device comprising it - Google Patents
Electrolyte and electrochemical appliance and electronic device comprising it Download PDFInfo
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- CN110336075A CN110336075A CN201910554050.7A CN201910554050A CN110336075A CN 110336075 A CN110336075 A CN 110336075A CN 201910554050 A CN201910554050 A CN 201910554050A CN 110336075 A CN110336075 A CN 110336075A
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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
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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
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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
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- 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
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Abstract
This application involves electrolyte and include its electrochemical appliance and electronic device.This application provides a kind of electrolyte comprising: sulfonic acid ester quat and nitrile compound.The electrolyte can form stable solid electrolyte interface film by sulfonic acid ester quat in positive electrode and negative electrode, and act synergistically with nitrile compound, can further promote protection of the electrolyte to positive electrode and negative electrode surface.When the electrochemical appliance of the application is stored and is recycled at high temperature, the problem of which can be effectively improved electrochemical appliance high-temperature expansion, and then promote the high temperature storage cycle performance and high-temperature storage performance of the electrochemical appliance.
Description
Technical field
This application involves technical field of energy storage more particularly to electrolyte and the electrochemical appliance including the electrolyte.
Background technique
With consumer electronics product for example laptop, mobile phone, handheld device, tablet computer, mobile power source and
Unmanned plane etc. is popularized, and requirement of the people to electrochemical appliance therein (for example, lithium ion battery) is increasingly stringenter.For example,
People do not require nothing more than electrochemical appliance and possess high capacity and long working life, it is further proposed that wanting for property specification
It asks such as: storage and circulation under high-temperature operation.In numerous electrochemical appliances, lithium ion battery is close with energy by it
Spend outstanding advantages of high, highly-safe, self discharge is low, memory-less effect, long working life with having occupied mainstream on the market
Position.Therefore, the cycle performance after lithium ion battery stores at high temperature (high temperature storage cycle performance) and storage how to be improved
Performance, which has become one of them, research direction to be solved.
The cycle life of lithium ion battery is related with its positive electrode, negative electrode material, electrolyte.In order to promote lithium-ion electric
The cycle performance and security performance in pond, in addition to seeking novel positive and negative pole material, it is also a kind of heavy for developing new electrolyte prescription
The solution wanted.
Summary of the invention
The application provides a kind of electrolyte to attempt to be present in related fields at least solving at least one in a way
The problems in.
According to a first aspect of the present application, this application provides a kind of electrolyte, the electrolyte includes: sulphonic acid ester quaternary ammonium
Salt and nitrile compound.
In some embodiments of the present application, the sulfonic acid ester quat includes at least one in the compound that formula 1 indicates
Kind,
Wherein, R11Selected from substituted or unsubstituted C1To C12Alkyl, substituted or unsubstituted C2To C12Alkenyl, substitution or not
Substituted C1To C12Alkoxy, substituted or unsubstituted C1To C12Acyloxy；R12Selected from substituted or unsubstituted C1To C12Alkylene
Base, substituted or unsubstituted C2To C12Alkenylene, substituted or unsubstituted C2To C12Alkynylene, substituted or unsubstituted C1To C12
Alkylene acyl group；R13Selected from substituted or unsubstituted C1To C12Alkyl, substituted or unsubstituted C2To C12It is alkenyl, substituted or unsubstituted
C2To C12Alkynyl, substituted or unsubstituted C1To C12Alkoxy, substituted or unsubstituted C1To C12Acyloxy, substitution do not take
The C in generation6To C22Aryl, substituted or unsubstituted C5To C22Heterocyclic base；R14Selected from substituted or unsubstituted C1To C3Alkylidene；It takes
Dai Ji is selected from cyano, halogen；And X- indicates anionic group.
In some embodiments of the present application, the cation group of the sulfonic acid ester quat be selected from by
And combinations thereof composed by group.
In some embodiments of the present application, the anionic group of the sulfonic acid ester quat is selected from by F-、NO3 -、PF6 -、
BF4 -、AsF6 -、(FSO2)2N-、 And combinations thereof composed by group.
In some embodiments of the present application, the nitrile compound includes in the compound that formula 2, formula 3, formula 4 and formula 5 indicate
At least one,
NC-R21- CN formula 2, Wherein R21Selected from substituted or unsubstituted C1Extremely
C5Alkylidene, substituted or unsubstituted C1To C5Alkylene oxide group；R31And R32It is each independently selected from covalent bond, substituted or unsubstituted
C1To C5Alkylidene；R41、R42And R43It is each independently selected from covalent bond, substituted or unsubstituted C1To C5Alkylidene, substitution
Or unsubstituted C1To C5Alkylene oxide group；Wherein, R51Selected from substituted or unsubstituted C1To C5It is alkylidene, substituted or unsubstituted
C2To C10Alkenylene, substituted or unsubstituted C6To C10Arlydene, substituted or unsubstituted C1To C6Heterocycle；And wherein, replace
Base is selected from group composed by halogen, nitro, cyano, carboxyl, sulfate and combinations thereof.
In some embodiments of the present application, the nitrile compound be selected from by
And combinations thereof institute's group
At group.
In some embodiments of the present application, the nitrile compound be selected from by
And combinations thereof institute's group
At group.
In some embodiments of the present application, the electrolyte further comprise selected from by
And combinations thereof composed by group change
Close object.
In some embodiments of the present application, the electrolyte further comprises phosphonitrile, and the phosphonitrile is selected from what formula 6 indicated
At least one of compound,
Wherein, R61It can be selected from substituted or unsubstituted C1To C12Alkyl, substituted or unsubstituted C3To C12Naphthenic base, substitution
Or unsubstituted C2To C12Alkenyl, substituted or unsubstituted C6To C22Aryl, substituted or unsubstituted C5To C22Heterocyclic base；And it takes
Dai Ji is selected from cyano, halogen.
In some embodiments of the present application, the phosphonitrile be selected from by
And combinations thereof composed by group.
In some embodiments of the present application, with the total weight of the electrolyte, the content of the sulfonic acid ester quat
Content for 0.1% to 10% and the nitrile compound is 0.5% to 12%.
According to a second aspect of the present application, this application provides a kind of electrochemical appliances comprising: anode, cathode, isolation
Electrolyte described in film and above-described embodiment.
According to the third aspect of the application, this application provides a kind of electronic devices, and it includes the electricity in above-described embodiment
Chemical devices.
According to one or more embodiments, electrochemical appliance can be effectively improved using the application electrolyte and is deposited at high temperature
High-temperature expansion problem when storage and circulation, and then promote the high temperature storage cycle performance and high temperature storage of the electrochemical appliance
Energy.
The additional level and advantage of the embodiment of the present application will be described partly in subsequent instruction, be shown or via this
Apply for the implementation of embodiment and illustrates.
Specific embodiment
Embodiments herein will be shown hereinafter by detailed retouch.
As used herein, term " substantially ", " generally ", " essence " and " about " is to describe and illustrate small change
Change.When being used in combination with event or situation, the term can be referred to the example that wherein event or situation accurately occur and its
The example that middle event or situation pole approximatively occur.For example, when combination numerical value is in use, term can be referred to be less than or equal to
± 10% variation range of the numerical value, e.g., less than or equal to ± 5%, be less than or equal to ± 4%, be less than or equal to ±
3%, it is less than or equal to ± 2%, is less than or equal to ± 1%, is less than or equal to ± 0.5%, is less than or equal to ± 0.1% or small
In or equal to ± 0.05%.For example, if difference between two values be less than or equal to the average value of described value ±
10% (e.g., less than or equal to ± 5%, be less than or equal to ± 4%, be less than or equal to ± 3%, be less than or equal to ± 2%, be less than
Or be equal to ± 1%, be less than or equal to ± 0.5%, be less than or equal to ± 0.1% or less than or equal to ± 0.05%), then can
Think that described two numerical value " generally " are identical.
In addition, sometimes herein with range format presentation amount, ratio and other numerical value.It should be understood that such range format
It is that and should neatly understand for convenient and for purpose of brevity, not only comprising being expressly specified as the numerical value of scope limitation, but also wraps
Containing all individual numbers or the subrange being covered by the range, as explicitly specifying each numerical value and subrange.
In specific embodiment and claims, by term " one of ", " in one ", " one of " or
The list for the project that other term similars are connected may imply that any one of listed item.For example, if list project A and
B, then phrase " one of A and B " means only A or only B.In another example, short if listing project A, B and C
Language " one of A, B and C " means only A；Only B；Or only C.Project A may include discrete component or multiple element.Project B can be wrapped
Containing discrete component or multiple element.Project C may include discrete component or multiple element.
In specific embodiment and claims, by term at least one of at least one of " ", " ", " in
At least one " or the list of project that is connected of other term similars may imply that any combination of listed item.For example, such as
Fruit lists project A and B, then phrase " at least one of A and B " means only A；Only B；Or A and B.In another example, such as
Fruit lists project A, B and C, then phrase " at least one of A, B and C " means only A；Or only B；Only C；A and B (excluding C)；
A and C (excluding B)；B and C (excluding A)；Or the whole of A, B and C.Project A may include discrete component or multiple element.Project B can
Include discrete component or multiple element.Project C may include discrete component or multiple element.
Unless otherwise explicitly indicated, following terms used herein have the meaning hereafter pointed out.
Term " Cx" refer to containing the carbon atom with x quantity.For example, C1To C10Alkyl is with 1 to 10 carbon atom
Alkyl group.
Term " alkyl " covers alkyl, alkenyl, alkynyl, naphthenic base, aryl.For example, alkyl is contemplated to be with 1 to 20 carbon
Atom linear chain hydrocarbon structure." alkyl " is it is also contemplated that be branch or cyclic hydrocarbon structures with 3 to 20 carbon atoms.There is tool when specified
When the alkyl of body carbon number, it is contemplated that cover all geometric isomers with the carbon number.Alkyl herein can also be C1To C15Hydrocarbon
Base, C1To C10Alkyl, C1To C5A alkyl, C5To C20Alkyl, C5To C15Alkyl or C5To C10Alkyl.Appoint in addition, alkyl can be
Selection of land is substituted.For example, alkyl can be replaced by halogen, alkyl, aryl or the heteroaryl including fluorine, chlorine, bromine and iodine.
Term " certain oxygroup " refers to L-O- group, and wherein L is alkyl, alkenyl, alkynyl, naphthenic base, aryl or acyl group.For example,
When L group is alkyl, " certain oxygroup " can be referred to as " alkoxy "；When L group is naphthenic base, " certain oxygroup " can be referred to as
" cycloalkyloxy "；When L group is acyl group, " certain oxygroup " can be referred to as " acyloxy ".Alkoxy herein can be C1To C20Alkane
Oxygroup can also be C1To C12Alkoxy, C1To C10Alkoxy, C1To C5Alkoxy, C5To C20Alkoxy, C5To C15Alkoxy
Or C5To C10Alkoxy.
Term " certain sub- base " refers to that organic group both ends respectively remove a hydrogen-based and link from different keys, i.e. finger-R- group,
Wherein R is alkyl, alkenyl, alkynyl, naphthenic base, aryl, alkanoyl.For example, " certain sub- base " can claim when R group is alkyl
Do " alkylidene "；When R group is alkanoyl, " certain sub- base " can be referred to as " alkylene acyl group ".Alkylidene herein can be C1Extremely
C20Alkylidene can also be C1To C12Alkylidene, C1To C10Alkylidene, C1To C5Alkylidene, C5To C20Alkylidene, C5To C15It is sub-
Alkyl or C5To C10Alkylidene.
Term " alkyl " is contemplated to be with 1 to 20 linear saturation hydrocarbon structure." alkyl " is it is also contemplated that be to have 3 to 20 carbon
The branch or cyclic hydrocarbon structures of atom.For example, alkyl can be C1To C20Alkyl, C1To C10Alkyl, C1To C5Alkyl, C5To C20Alkane
Base, C5To C15Alkyl or C5To C10Alkyl.When the specified alkyl with specific carbon number, it is contemplated that cover all with the carbon number
Geometric isomer；Thus, for example, " butyl " is meant including normal-butyl, sec-butyl, isobutyl group, tert-butyl and cyclobutyl；" third
Base " includes n-propyl, isopropyl and cyclopropyl.Examples of alkyl includes, but are not limited to methyl, ethyl, n-propyl, isopropyl, ring
Propyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, cyclopenta, methyl ring penta
Base, ethylcyclopentyl, n-hexyl, isohesyl, cyclohexyl, n-heptyl, octyl, cyclopropyl, cyclobutyl, norborny etc..In addition,
Alkyl, which can be, to be optionally substituted.
Term " naphthenic base " covers cyclic alkyl.Naphthenic base can be C3To C20Naphthenic base, C6To C20Naphthenic base, C3To C10Ring
Alkyl, C3To C6Naphthenic base.For example, naphthenic base can be cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl etc..In addition, naphthenic base can be with
It is optionally substituted.
Term " alkenyl ", which refers to, can be straight chain or tool branch and have at least one and usual 1,2 or 3 carbon carbon pair
The monovalent unsaturated hydrocarbon group of key.Unless otherwise defined, the alkenyl usually contains 2-20 carbon atom, such as can be
C2To C20Alkenyl, C6To C20Alkenyl, C2To C12Alkenyl or C2To C6Alkenyl.Representative alkenyl includes (for example) vinyl, positive propylene
Base, isopropenyl, n- but-2-ene base, butyl- 3- alkenyl, n- hex- 3- alkenyl etc..It is optionally substituted in addition, alkenyl can be
's.
Term " alkynyl " refers to can be for straight chain or tool branch and at least one and usually with 1,2 or 3 carbon
The monovalent unsaturated hydrocarbon group of three key of carbon.Unless otherwise defined, the alkynyl usually contains 2 to 20 carbon atoms, example
It such as can be C2To C20Alkynyl, C6To C20Alkynyl, C2To C10Alkynyl or C2To C6Alkynyl.Representative alkynyl includes (for example) acetylene
Base, Propargyl (n- propinyl), n- butyl- 2- alkynyl, n- hex- 3- alkynyl etc..It is optionally taken in addition, alkynyl can be
Generation.
Term " acyl group " refers to that organic or inorganic oxyacid removes remaining atomic group after hydroxyl (- OH group), that is, refers to R-M
(O)-group, wherein M is carbon atom, and R is alkyl, alkenyl, alkynyl, naphthenic base, aryl or other common substituent groups.For example,
When R is alkyl, " acyl group " is " alkanoyl ".Alkanoyl herein can be C1To C20A alkanoyl can also be C1To C12It is a
Alkanoyl, C1To C10A alkylidene, C1To C5A alkanoyl, C5To C20A alkanoyl, C5To C15A alkylidene or C5To C10Alkane acyl
Base.
Term " aryl " covers single loop system and multi-loop system.The polycyclic two of them carbon that can have is two adjacent rings
Two or more shared rings of (ring is " condensed "), wherein at least one of described ring is aromatic, such as
Other rings can be naphthenic base, cycloalkenyl, aryl, heterocycle and/or heteroaryl.For example, aryl can be C6To C50Aryl, C6To C40
Aryl, C6To C30Aryl, C6To C20Aryl or C6To C10Aryl.Representative aryl includes (for example) phenyl, aminomethyl phenyl, propyl
Phenyl, isopropyl phenyl, benzyl and naphthalene -1- base, naphthalene -2- base etc..In addition, aryl can be and be optionally substituted.
Term " heterocycle " covers aromatic series and non-aromatic cyclic group.Heteroaromatic ring-type group still means that virtue is miscellaneous
Base.In some embodiments, heteroaromatic ring-type group and miscellaneous non-aromatic cyclic group be include that at least one is heteroatomic
C1To C50Heterocycle, C1To C40Heterocycle, C1To C30Heterocycle, C1To C20Heterocycle, C1To C10Heterocycle, C1To C6Heterocycle.
Representative heterocycle includes (for example) morpholinyl, piperidyl, pyrrolidinyl etc. and cyclic ethers, such as tetrahydrofuran, oxinane
Deng.In addition, heterocycle can be and be optionally substituted.
As used herein, it may include one to three heteroatomic monocyclic heteroaromatic groups that term " heteroaryl ", which is covered,
Such as pyrroles, furans, thiophene, imidazoles, oxazole, thiazole, triazole, pyrazoles, pyridine, pyrazine and pyrimidine etc..Term heteroaryl also wraps
Including with two of them atom is the polycyclic miscellaneous of two or more shared rings of two adjacent rings (ring is " condensed ")
Aromatic systems, wherein at least one of described ring is heteroaryl, other rings can be naphthenic base, cycloalkenyl, aryl, heterocycle
And/or heteroaryl.Such as heteroaryl can be C6To C50Heteroaryl, C6To C40Heteroaryl, C6To C30Heteroaryl, C6To C20Heteroaryl
Or C6To C10Heteroaryl.In addition, heteroaryl can be and be optionally substituted.
As used herein, term " halogen " can be F, Cl, Br or I.
As used herein, term " itrile group " covers the organic matter of-CN containing organic group.
When above-mentioned substituent group is substituted, substituent group can be selected from the group being made up of: halogen, alkyl, naphthenic base, alkene
Base, aryl and heteroaryl.
One, electrolyte
According to a first aspect of the present application, this application provides a kind of electrolyte, the electrolyte includes sulphonic acid ester quaternary ammonium
Salt and nitrile compound.The sulfonic acid ester quat can form stable solid electrolyte interface film on positive electrode and negative electrode surface
(Solid Electrolyte Interface, SEI), which can be effectively reduced the incompatible spy of nitrile compound and cathode
Property, and inhibit oxidation side reaction of the electrolyte on positive electrode surface and the reduction side reaction in negative terminal surface.The application is logical
It crosses using sulfonic acid ester quat and nitrile compound as being added in combination in electrolyte, electrolyte can be effectively reduced under high temperature just
Oxidation side reaction in pole surface, thus be effectively improved the high temperature storage cycle performance of the electrochemical appliance comprising the electrolyte with
And storage performance.
According to some embodiments of the present application, the sulfonic acid ester quat includes at least one in the compound that formula 1 indicates
Kind,
Wherein, R11Selected from substituted or unsubstituted C1To C12Alkyl, substituted or unsubstituted C2To C12Alkenyl, substitution or not
Substituted C1To C12Alkoxy, substituted or unsubstituted C1To C12One of acyloxy；
R12Selected from substituted or unsubstituted C1To C12Alkylidene, substituted or unsubstituted C2To C12Alkenylene, substitution or not
Substituted C2To C12Alkynylene, substituted or unsubstituted C1To C12One of alkylene acyl group；
R13Selected from substituted or unsubstituted C1To C12Alkyl, substituted or unsubstituted C2To C12It is alkenyl, substituted or unsubstituted
C2To C12Alkynyl, substituted or unsubstituted C1To C12Alkoxy, substituted or unsubstituted C1To C12Acyloxy, substitution do not take
The C in generation6To C22Aryl, substituted or unsubstituted C5To C22One of heterocyclic base；
R14Selected from substituted or unsubstituted C1To C3One of alkylidene；
Substituent group is selected from one of cyano, halogen；And
X-Indicate anionic group.
In some embodiments of the present application, the cation group of the sulfonic acid ester quat be selected from by
And combinations thereof composed by group.
In some embodiments of the present application, the anionic group of the sulfonic acid ester quat is selected from by F-、NO3 -、PF6 -、
BF4 -、AsF6 -、(FSO2)2N-、
And combinations thereof composed by group.
In some embodiments of the present application, the sulfonic acid ester quat is in the compound that following structural formula indicates
It is at least one:
According to some embodiments of the present application, the nitrile compound includes the chemical combination that following formula 2, formula 3, formula 4 and formula 5 indicate
At least one of object,
NC-R21- CN formula 2,
Wherein R21Selected from substituted or unsubstituted C1To C5Alkylidene, substituted or unsubstituted C1To C5In alkylene oxide group
One；
R31And R32It is each independently selected from covalent bond, substituted or unsubstituted C1To C5One of alkylidene；
R41、R42And R43It is each independently selected from covalent bond, substituted or unsubstituted C1To C5It is alkylidene, substituted or unsubstituted
C1To C5One of alkylene oxide group；
Wherein, R51Selected from substituted or unsubstituted C1To C5Alkylidene, substituted or unsubstituted C2To C10Alkenylene, substitution
Or unsubstituted C6To C10Arlydene, substituted or unsubstituted C1To C6One of heterocycle；And
Substituent group is selected from group composed by halogen, nitro, cyano, carboxyl, sulfate and combinations thereof.
In some embodiments of the present application, the nitrile compound in the compound that following structural formula indicates at least
One kind,
It should be understood that in above-described embodiment, the nitrile compound of different structure formula due to its Absorptive complex wave active force not
Together, so that it also generates different isolation effects from positive electrode surface to electrolyte.In some embodiments, with the nitrile compound
In " itrile group " (- CN) group number increase, can play more significant to the isolation effect of electrolyte and positive electrode surface.Together
When, the molecular size range of the nitrile compound, which has, also has a certain impact to its isolation effect, and molecular weight is too small will be electrolysed
Oxidizable component is effectively spaced apart with positive electrode surface in liquid, and molecular weight is excessive, and oxidizable component can pass through the nitrile in electrolyte
The molecular gap of compound is in contact with positive electrode surface.
In some embodiments of the present application, the nitrile compound is to contain chemical combination more than at least three nitrile groups
Object, selected from by
And combinations thereof composed by group.
According to some embodiments of the present application, in the electrolyte, with the total weight of the electrolyte, the sulfonic acid
The content of ester quat be about 0.1% to the content of about 10% and the nitrile compound be about 0.5% to about 12%.In this Shen
In some embodiments please, with the total weight of the electrolyte, the content of the sulfonic acid ester quat is about 1% to about 6%,
And the content of the nitrile compound is about 0.5% to about 12%.In some embodiments of the present application, the sulfonic acid ester quat
Weight percentage (with the total weight of the electrolyte) in the electrolytic solution is, for example, 0.1%, 0.2%, 0.5%,
1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% and nitrile compound weight percent in the electrolytic solution contain
Amount (with the total weight of the electrolyte) be, for example, 0.5%, 0.75%, 1%, 2%, 3%, 4%, 5%, 6%, 7%,
8%, 9%, 10%, 11%, 12%.
It should be understood that with the total weight of the electrolyte, when the content of the sulfonic acid ester quat is higher than 0.1%, institute
Electrolyte can effectively be improved and exist in positive electrode and negative electrode Surface Creation solid electrolyte interface film by stating sulfonic acid ester quat
Stability under high temperature.In addition, with the total weight of the electrolyte, when the content of the sulfonic acid ester quat is lower than 10%
When, the thickness for the solid electrolyte interface film that the sulfonic acid ester quat generates and impedance are smaller, less likely fill to electrochemistry
The cycle performance set impacts.
With the total weight of the electrolyte, when the content of the nitrile compound is higher than 0.5%, the nitrile compound energy
It is enough to be effectively isolated to from the oxidizable component in the transition metal and electrolyte that positive electrode surface dissolves out, effectively reduce electrolysis
Liquid is at high temperature in the oxidation side reaction on positive electrode surface.In addition, with the total weight of the electrolyte, the nitrile compound
When content is lower than 12%, the bad shadow that the nitrile compound may cause the cycle performance of electrochemical appliance can be reduced
It rings, for example, the reduction of energy density, the rising of electrolyte viscosity.
In some embodiments of the present application, with the total weight of the electrolyte, the content of the sulfonic acid ester quat
It is about 0.5% to about 3%, and the content weight of the nitrile compound is about 0.5% to about 3%.
In some embodiments of the present application, with the total weight of the electrolyte, the sulfonic acid ester quat and described
The combined aggregation content of nitrile compound is about 0.6% to about 22%.
In some embodiments of the present application, with the total weight of the electrolyte, the sulfonic acid ester quat and described
The combined aggregation content of nitrile compound is about 1.5% to about 14%.
According to some embodiments of the present application, the electrolyte also may include one of following compound or a variety of:
1,3- dioxolanes (cyclic ethers 1),1,3- dioxane (cyclic ethers 2),1,4- dioxane
(cyclic ethers 3),1,3,2- dioxazole thiophene -2,2- dioxide (DTD),
Group composed by methane-disulfonic acid methylene ester (MMDS) and combinations thereof.
In some embodiments of the present application, with the total weight of the electrolyte, 1,3-dioxolane, 1,3- dioxy oneself
The content of at least one of ring and 1,4- dioxane in the electrolyte is about 0.01% to about 4%.The application's
In some embodiments, with the total weight of the electrolyte, in 1,3-dioxolane, 1,3- dioxane and Isosorbide-5-Nitrae-dioxane
At least one content in the electrolyte be about 0.1% to about 3%.In some embodiments of the present application, with described
The total weight of electrolyte, at least one of 1,3-dioxolane, 1,3- dioxane and Isosorbide-5-Nitrae-dioxane are in the electricity
The content solved in liquid is about 0.1% to about 2%.In some embodiments of the present application, with the total weight of the electrolyte, 1,
The content of at least one of 3,2- dioxazole thiophene -2,2- dioxide and methane-disulfonic acid methylene ester is about 0.05% to about
4%.In some embodiments of the present application, with the total weight of the electrolyte, 1,3,2- dioxazole thiophene -2,2- titanium dioxide
The content of at least one of object and methane-disulfonic acid methylene ester is about 0.05% to about 3%.In some embodiments of the present application,
With the total weight of the electrolyte, in 1,3,2- dioxazole thiophene -2,2- dioxide and methane-disulfonic acid methylene ester at least
The content of one is about 0.1% to about 2%.
In some embodiments of the present application, the additive can also include phosphazene compound, the phosphazene compound
At least one of compound including the expression of following formula 6,
Wherein, R61It can be selected from substituted or unsubstituted C1To C12Alkyl, substituted or unsubstituted C3To C12Naphthenic base, substitution
Or unsubstituted C2To C12Alkenyl, substituted or unsubstituted C6To C22Aryl, substituted or unsubstituted C5To C22Heterocyclic base；With take
Dai Ji is selected from cyano, halogen.
In some embodiments of the present application, the phosphazene compound in the compound that following structural formula indicates extremely
Few one kind:
In some embodiments of the present application, with the total weight of the electrolyte, the phosphazene compound is in the electricity
The content solved in liquid is about 0.1% to about 20%.In some embodiments of the present application, with the total weight of the electrolyte,
Content of the phosphazene compound in the electrolyte is about 0.5% to about 15%.In some embodiments of the present application, with
The total weight of the electrolyte, content of the phosphazene compound in the electrolyte are about 1% to about 13%.The phosphorus
After the combination of nitrile compound and above-mentioned sulfonic acid ester quat and nitrile compound is added in electrolyte, it can be promoted high gentle
Cycle performance is stored up, while the security performance of its electrochemical appliance can also be improved.
In some embodiments of the present application, the electrolyte also includes acid anhydrides, and the acid anhydrides includes, but are not limited to ring
One of shape phosphoric anhydride, carboxylic acid anhydrides and carboxylic acid sulphonic acid anhydride are a variety of.In some embodiments, the cyclic phosphate acid anhydride includes,
But it is not limited to, one of trimethyl phosphoric acid cyclic anhydride, triethyl group phosphoric acid cyclic anhydride and tripropyl phosphoric acid cyclic anhydride or a variety of.In some realities
It applies in example, the carboxylic acid anhydrides includes, but are not limited to one of succinic anhydride, glutaric anhydride and maleic anhydride or a variety of.One
In a little embodiments, the carboxylic acid sulphonic acid anhydride includes, but are not limited in sulfosalicylic acid acid anhydride, Sulfo propionic acid acid anhydride and sulfo group butyric anhydride
It is one or more.
In some embodiments of the present application, with the total weight of the electrolyte, the acid anhydrides is in the electrolyte
Content be about 0.1% to about 10%.In some embodiments of the present application, with the total weight of the electrolyte, the acid
Content of the acid anhydride in the electrolyte is about 0.5% to about 8%.In some embodiments of the present application, with the electrolyte
Total weight, content of the acid anhydrides in the electrolyte are about 0.5% to about 7%.
In some embodiments, the electrolyte also includes phosphorus-containing compound, and the phosphorus-containing compound includes, but unlimited
In: trimethyl phosphate, triethyl phosphate, phosphoric acid dimethylethyl esters, phosphoric acid methyl diethylester, phosphoric acid ethylidene methyl esters, phosphoric acid are sub-
Diethyl acetamidomalonate, triphenyl phosphate, Trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tricresyl phosphate (2,2,2- trifluoro
Ethyl) one of ester and tricresyl phosphate (2,2,3,3,3- pentafluoropropyl group) ester or a variety of.
In some embodiments of the present application, with the total weight of the electrolyte, the phosphorus-containing compound is in the electricity
The content solved in liquid is about 0.1% to about 20%.In some embodiments of the present application, with the total weight of the electrolyte,
Content of the phosphorus-containing compound in the electrolyte is about 0.5% to about 15%.In some embodiments of the present application, with
The total weight of the electrolyte, content of the phosphorus-containing compound in the electrolyte are about 0.5% to about 10%.
In some embodiments, the electrolyte also includes additive containing lithium, and the additive containing lithium includes, but unlimited
In: lithium perchlorate (LiClO4), hexafluoroarsenate lithium (LiAsF6), LiBF4 (LiBF4), tetraphenyl borate lithium (LiB
(C6H5)4), methanesulfonic acid lithium (LiCH3SO3), hexafluoro-antimonic acid lithium (LiSbF6), trifluoromethyl sulfonic acid lithium (LiCF3SO3), bis- (trifluoros
Sulfonyloxy methyl) imine lithium (LiN (SO2CF3)2), three (trifluoromethane sulfonic acid) lithium methide (LiC (SO2CF3)3), hexafluorosilicic acid lithium
(LiSiF6), difluorophosphate (LiPO2F2), difluorine oxalic acid boracic acid lithium (LiODFB), one in dioxalic acid lithium borate (LiBOB)
Kind is a variety of.
In some embodiments of the present application, with the total weight of the electrolyte, the additive level containing lithium is about
0.01% to about 25%.In some embodiments, with the total weight of the electrolyte, the additive level containing lithium is about
0.05% to about 22wt%.In some embodiments, with the total weight of the electrolyte, the additive level containing lithium is about
0.5%, about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10% or about 18%.
In some embodiments, the electrolyte also includes lithium hexafluoro phosphate (LiPF6)。
In some embodiments of the present application, the content of the lithium hexafluoro phosphate is about 0.5mol/L to 2.5mol/L.?
In some embodiments of the present application, the content of the lithium hexafluoro phosphate is about 0.8mol/L to 2.0mol/L.The one of the application
In a little embodiments, the content of the lithium hexafluoro phosphate is about 0.8mol/L to 1.8mol/L.In some embodiments of the present application,
The content of the lithium hexafluoro phosphate is about 0.5mol/L to 1.5mol/L.
According to some embodiments of the present application, the electrolyte also may include nonaqueous solvents.
In some embodiments of the present application, the nonaqueous solvents is comprising in carbonate products, carboxylate compound
It is at least one.
It should be understood that the carbonic ester can be the carbonic ester of any kind, the carbonate products can be chain carbonic acid
Ester compounds, cyclic carbonate compound, fluoro carbonic ester compound or combinations thereof.
The example of the linear carbonate compound is dimethyl carbonate (DMC), diethyl carbonate (DEC), carbonic acid dipropyl
Ester (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonic acid ester (EPC), methyl ethyl carbonate (MEC) and combinations thereof.The cyclic carbonate
The example of ester compounds is ethylene carbonate (EC), propene carbonate (PC), butylene carbonate (BC), vinyl ethylene carbonate
(VEC) and combinations thereof.The example of the fluoro carbonic ester compound is bis- fluoroethylene of carbonic acid 1,2-, carbonic acid 1,1- difluoro Asia second
Ester, tri- fluoroethylene of carbonic acid 1,1,2-, tetra- fluoroethylene of carbonic acid 1,1,2,2-, the fluoro- 2- methyl ethyl of carbonic acid 1-, carbonic acid 1-
Fluoro- 1- methyl ethyl, the fluoro- 1- methyl ethyl of carbonic acid 1,2- bis-, the fluoro- 2- methyl ethyl of carbonic acid 1,1,2- tri-, carbonic acid three
Methyl fluoride ethyl and combinations thereof.
The example of the carboxylate compound is methyl formate, methyl acetate, ethyl acetate, propyl propionate, acetic acid positive third
Ester, tert-butyl acetate, methyl propionate, ethyl propionate, gamma-butyrolacton (BL), decalactone, valerolactone, mevalonolactone, in oneself
Ester and combinations thereof.
It will be understood by those skilled in the art that the electrolyte of the embodiment of the present application can be any according to practical preparation demand selection
Suitable known method manufacture, and be not limited except as.
Two, electrochemical appliance
According to a second aspect of the present application, present invention also provides the electrochemistry for the electrolyte for including the embodiment of the present application dresses
It sets.In some embodiments of the present application, the electrochemical appliance is lithium ion battery.The lithium ion battery include anode,
The electrolyte of cathode, isolation film and the application.
Anode
According to some embodiments of the present application, the anode includes plus plate current-collecting body and the positive electrode active material on its surface
Matter layer, wherein positive electrode active material layer contains positive electrode active materials and conductive agent.In some embodiments, the anode collection
Body includes, but are not limited to aluminium foil or nickel foil.
In some embodiments of the present application, the positive electrode active materials are the positive material that can absorb and release lithium (Li)
Expect (hereinafter, sometimes referred to as " positive electrode that can absorb/discharge lithium Li ").The example of the positive electrode active materials can wrap
Include cobalt acid lithium, LiFePO4, iron manganese phosphate for lithium, phosphoric acid ferrisodium, phosphoric acid vanadium lithium, vanadium phosphate sodium, vanadium phosphate oxygen lithium, vanadium phosphate oxygen
At least one in sodium, lithium vanadate, LiMn2O4, lithium nickelate, nickle cobalt lithium manganate, lithium-rich manganese base material, nickel cobalt lithium aluminate and lithium titanate
Kind.
In some embodiments of the present application, the positive electrode active materials include nickel-cobalt-manganese ternary material, the nickel cobalt manganese
The example of ternary material may include, but be not limited to, by the oxide packet of any one or more of element of Al, Mg, Ti, Zr, B
The LiNi coveredaCobMncO2Or Li (LidNieCofMng)O2At least one of, wherein a+b+c=1,1d+2e+3f+4g=3, d >
0.In some embodiments, the positive electrode active materials include LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、
LiNi0.4Co0.2Mn0.4O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.6Co0.2Mn0.2O2At least one of.
In some embodiments of the present application, the positive electrode active materials include cobalt acid lithium and nickel-cobalt-manganese ternary material.
In some embodiments of the present application, the mixing of cobalt acid lithium and nickel-cobalt-manganese ternary material in the positive electrode active materials
Ratio is 1:9 to 9:1.In other embodiments of the application, cobalt acid lithium and nickle cobalt lithium manganate in the positive electrode active materials
Mixed proportion be 2:8 to 4:6.
The positive electrode is the combination of cobalt acid lithium and nickel-cobalt-manganese ternary material, and the safety of positive electrode active materials can be improved
Performance.Simultaneously because increasing the quantity of transition metal after mixing, transition metal plays the film forming in electrolyte certain
Catalytic action can allow the combination of above-mentioned sulfonic acid ester quat and nitrile compound to play significantly more efficient isolation effect.
In some embodiments, the conductive agent includes conductive carbon black, carbon fiber, acetylene black, Ketjen black, graphene, carbon
At least one of nanotube.For those skilled in the art when that can understand, the various anodes for being widely used in lithium ion battery are all suitable
For the application, and it is not limited except as.
Cathode
According to some embodiments of the present application, the cathode includes negative current collector and on the negative current collector
Anode active material layer.In some embodiments, negative current collector includes, but are not limited to: copper foil, nickel foil, stainless steel foil, titanium
Foil, nickel foam, foam copper, the polymeric substrates for being covered with conductive metal and their any combination.
In some embodiments of the present application, the anode active material layer is living including the cathode for absorbing and releasing lithium (Li)
Property material (hereinafter, sometimes referred to as " negative electrode material that can absorb/discharge lithium Li ").In some embodiments it is possible to absorb/
The example for discharging the negative electrode material of lithium (Li) may include that carbon material, metallic compound, oxide, sulfide, silicon, silico-carbo are multiple
Close the nitride such as LiN of object, lithium3, lithium metal, one of alloy material and polymer material or a variety of.
In some embodiments of the present application, the negative electrode material of cathode used in the lithium ion battery of the application is constituted
It may include technology disclosed in any prior art with its manufacturing method.The cathode of the embodiment of the present application can pass through this field public affairs
The preparation method preparation known.In some embodiments of itself, the preparation method of cathode the following steps are included: will bear in a solvent
Pole active material, conductive agent and adhesive mixing, to prepare negative electrode active material feed composition, and combine the negative electrode active material
Object is coated on negative current collector.In some embodiments, the solvent may include water, but not limited to this.
Isolation film
In some embodiments of the present application, the lithium ion battery of the application between positive electrode and negative electrode be equipped with isolation film with
Prevent short circuit.The material and shape of isolation film used in the lithium ion battery of the application are not particularly limited, and can be any
Technology disclosed in the prior art.In some embodiments of the present application, the isolation film includes by the electrolyte to the application
Polymer or inorganic matter that stable material is formed etc..
In some embodiments of the present application, the preparation method of above-mentioned lithium ion battery includes: will be in above-described embodiment
Anode, isolation film and cathode wind or stack in order, are fitted into such as aluminum plastic film, and inject the electrolyte of the application, then
The processes such as Vacuum Package, standing, chemical conversion, shaping are carried out, to obtain lithium ion battery.It will be understood by those skilled in the art that described
The preparation method of lithium ion battery can be according to the manufacturing method and required performance of final products, in the system of lithium ion battery
During making process, the electrolyte of the application can be injected in suitable step.In other words, can assembling lithium ion battery it
Preceding or during assembling lithium ion battery final step injects the electrolyte of the application, and is not limited except as
It will be apparent to one skilled in the art that the preparation method of lithium ion battery described above is only embodiment.Not
On the basis of present disclosure, other methods commonly used in the art can be used.Although in addition, above with lithium from
Sub- battery has carried out for example, still those skilled in the art are after reading the application, alternatively it is conceivable to the electrolysis of the application
Liquid can be used for other suitable electrochemical appliances.Such electrochemical appliance includes any device that electrochemical reaction occurs,
Its specific example includes one-shot battery, secondary cell, fuel cell, solar battery or the capacitor of all kinds.Especially
Ground, the electrochemical appliance are lithium secondary battery, including the secondary electricity of lithium metal secondary cell, lithium ion secondary battery, lighium polymer
Pond or lithium ion polymer secondary cell.
Three, electronic device
According to the third aspect of the application, the application further provides a kind of electronic device, and the electronic device includes
The electrochemical appliance of the application.
The electronic device of the embodiment of the present application is not particularly limited, and can be for any electricity well known in the prior art
Sub-device.In some embodiments of the present application, the electronic device may include, but be not limited to, laptop, pen input
Type computer, removable computer, e-book player, portable phone, portable facsimile printer, portable copier, Portable hitting
Print machine, wear-type stereophone, video recorder, LCD TV, Portable cleaning machine, portable CD player, Mini Disk, transceiver,
Electronic notebook, calculator, storage card, portable recorder, radio, backup power source, motor, automobile, motorcycle, power-assisted are certainly
Driving, bicycle, luminaire, toy, game machine, clock and watch, electric tool, flash lamp, camera, home-use large-scale battery
With lithium-ion capacitor etc..
Four, specific embodiment
Some specific embodiments and comparative example are hereinafter listed, and carries out high temperature storage cycle performance survey to it respectively
At least one of examination, high temperature storage test test, cycle performance test and hot tank test, preferably to the technology of the application
The beneficial effect of scheme is illustrated.
(1) test method
The test of high temperature storage cycle performance
(1) the lithium ion battery finished product of following embodiment or comparative example is placed in 45 DEG C of insulating box, with constant charging
Rate 0.5C charges to 4.4V, and constant-voltage charge is subsequently placed with to 0.05C up to 19 hours at 4.4V, then with constant discharge speed
Rate 0.5C is discharged to 3.0V, and records its discharge capacity as discharge capacity for the first time.
(2) it repeats aforesaid way (1) and carries out 23 charge and discharge cycles.
(3) the lithium ion battery finished product is placed in 45 DEG C of insulating box, is charged to constant charge rate 0.5C
4.35V, and constant-voltage charge is subsequently placed with to 0.05C up to 19 hours at 4.35V, then is discharged to constant discharge rate 0.5C
3.0V。
(4) aforesaid way (3) are repeated and carries out 113 charge and discharge cycles.
(5) then electric discharge records discharge capacity each time, calculates lithium ion battery as circuiting sequentially using after charging
Battery capacity conservation rate after high temperature storage circulation；
Discharge capacity (mAh)/electric discharge for the first time after n-th circulation after battery capacity conservation rate (%)=n-th circulation is held
It measures (mAh) × 100%.
High-temperature storage performance test
The lithium ion battery finished product of following embodiment or comparative example is placed in 25 DEG C of insulating box, with constant charge rate
0.5C charges to 4.40V, then constant-voltage charge to charge rate be 0.05C, record its lithium ion battery with a thickness of h0；Then
Lithium ion battery is placed in 85 DEG C of insulating box and is stored 6 hours；Record its lithium ion battery with a thickness of h1, and calculated thickness
Growth rate:
Thickness growth rate (%)=(h1-h0)/h0 × 100%.
Cycle performance test
The lithium ion battery finished product of following embodiment or comparative example is placed in 45 DEG C of insulating box and stands 30 minutes, with perseverance
Determine charge rate 1.0C and charge to 4.40V, then constant-voltage charge to charge rate is 0.05C, then with constant discharge rate
1.0C is discharged to 3.0V, as a charge and discharge cycles, and records discharge capacity for the first time.After then continuing 300 circulations, meter
Calculate its battery capacity conservation rate.
Drift bolt test
The lithium ion battery finished product of following embodiment or comparative example is placed in 25 DEG C of insulating box and stands 30 minutes, with perseverance
Determine charge rate 0.5C and charge to 4.4V, then constant-voltage charge to charge rate is 0.025C at 4.4V.Then by the lithium from
Sub- battery is placed in drift bolt test machine, and under 25 DEG C of isoperibol, the steel nail for being 4mm with diameter is even with the speed of 30mm/s
Speed passes through lithium ion battery center, and lithium ion battery is not on fire not to explode as passing through.20 pieces of batteries of test every time, by wearing
Follow closely index of the lithium ion battery quantity of test as evaluation lithium ion battery safety performance.
Hot tank test
The lithium ion battery finished product of following embodiment or comparative example is placed in 25 DEG C of insulating box, with constant charge rate
0.5C charges to 4.25V, and then constant-voltage charge to charge rate is 0.05C at 4.25V.Then the lithium ion battery is put into
In high-temperature cabinet, 140 DEG C are warming up to, and is kept for 1 hour at 140 DEG C.Monitor lithium ion battery during hot tank test, lithium from
As long as sub- battery during it is not on fire and do not explode i.e. indicate pass through test.10 pieces of batteries of test every time, to be surveyed by hot tank
Index of the lithium ion battery quantity of examination as evaluation lithium ion battery hot tank performance.
(2) preparation of lithium ion battery
The preparation of anode
By cobalt acid lithium (LiCoO2), carbon nanotube (CNTs) and polyvinylidene fluoride (PVDF) according to about 96:2:2 weight
Than being blended in solvent N-methyl pyrilidone, stirs evenly, obtain anode sizing agent.It, will using aluminium foil as plus plate current-collecting body
The plus plate current-collecting body of coating cobalt acid lithium slurry toasts 1 hour at 120 DEG C, and is then cold-pressed, cut-parts, cutting, with preparation
Obtain anode.
The preparation of cathode
Artificial graphite, sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR) are mixed according to the weight ratio of about 96:2:2
In deionized water, it stirs evenly, obtains negative electrode slurry.Using copper foil as negative current collector, the negative of negative electrode slurry will be coated
Pole collector toasts 1 hour at 120 DEG C, and is then cold-pressed, cut-parts, cutting, cathode is prepared.
The preparation of electrolyte
Under ar gas environment, by ethylene carbonate (EC), diethyl carbonate (DEC) and propene carbonate (PC) according to weight
It is mixed than 3:4:3, LiPF is then added6, basis of formation electrolyte, wherein LiPF6Concentration be 1.15mol/L.It is electrolysed on basis
The substance that different content shown in following each table is added in liquid obtains the electrolyte of different embodiment and comparative examples.
The assembling of lithium ion battery
Using polyethylene film as isolation film, above-mentioned anode, isolation film and cathode are folded in order, made at isolation film
Play the role of isolation among positive and negative anodes, then wind, be fitted into aluminum plastic film, and it is dry at 80 DEG C after prepared by injection
Electrolyte completes the preparation of lithium ion battery by processes such as Vacuum Package, standing, chemical conversion, shapings.
After the completion of the lithium ion battery finished product of above embodiments and comparative example, the capacity, thickness, width of its finished product are recorded
Degree, length are to determine the volume energy density of lithium ion battery.And to the lithium ion battery of embodiment 1-27 and comparative example 1-3 into
The test of row high temperature storage cycle performance and high temperature storage test.
The electrolyte allotment ratio and composition of embodiment 1-27 and comparative example 1-3 and its pass through high temperature storage cycle performance
Test result is as follows shown in table 1 for test and high temperature storage test.
Table 1
By data in table 1 it is found that compared with comparative example 1-3, the application is by being added to the sulfonic acid ester quat and institute
Being combined in electrolyte for nitrile compound is stated, after the lithium ion battery provided can effectively promote high temperature storage loop test
Capacity retention ratio and reduce high temperature storage test after thickness growth rate.Wherein, compared to complete all without described in addition
The comparative example 1 of sulfonic acid ester quat and the nitrile compound is only added in the sulfonic acid ester quat and the nitrile compound
One of comparative example 2 and 3 pair its lithium ion battery high temperature storage cycle performance and high-temperature expansion have certain improvement, but change
It is kind not significant.
By comparing embodiment 7-13 it is found that the structural formula containing content 2% is the structural formula of (formula 2-2) and content 1%
For the nitrile compound of (formula 4-3), while when adding content between 2% to 12% sulfonic acid ester quat, the height of lithium ion battery
Gentle storage circulation and high-temperature expansion problem can be obviously improved.
In addition, by comparing embodiment 1-6 it is found that embodiment 2-3 and 5-6 due to its nitrile compound structural formula (formula 4-
3) and (formula 5-2) have at least three or more nitrile group, compared in embodiment 1 and 4 containing only there are two nitrile groups
Structural formula be (formula 2-2) nitrile compound, more can effectively reduce its high temperature storage test thickness growth rate.
By above-mentioned comparison it is known that the electrochemical appliance of the application is by being added to the sulfonic acid ester quat and institute
Being combined in electrolyte for nitrile compound is stated, effectively improves its high temperature storage cycle efficieny, while inhibiting in high temperature storage
When thickness increase.Adding for sulfonic acid ester quat can be in the stable SEI of positive electrode and negative electrode formation in the electrolytic solution by the application
Film, and the addition of the application nitrile compound in the electrolytic solution can carry out complex reaction in positive electrode surface and transition metal.The application
By combining both sulfonic acid ester quat and nitrile compound, sulfonic acid ester quat can reduce the incompatible of nitrile compound and cathode
Property, the side reaction that electrolyte occurs with positive electrode and negative electrode interface at high temperature is further decreased, so as to improve high temperature storage circulation
Performance and high temperature thickness growth rate.
In some embodiments of the present application, the electrolyte of the application can further include other additives, with into one
Step promotes the cycle performance of the lithium ion battery comprising the electrolyte.In following example 28 to 39, preparation method with
Embodiment 8 is identical, and different places is further to add following structural formula in the preparation of the electrolyte of embodiment 28 to 39 to indicate
At least one of compound:
1,3- dioxolanes (cyclic ethers 1),1,3- dioxane (cyclic ethers 2),1,4- dioxy oneself
Ring (cyclic ethers 3),1,3,2- dioxazole thiophene -2,2- dioxide (DTD),Methane-disulfonic acid methylene
Into the combined electrolyte containing the sulfonic acid ester quat and the nitrile compound (embodiment 8), other add ester (MMDS)
Add specific ingredient and the content of agent as shown in table 2.And high temperature storage circulation is carried out to the lithium ion battery of embodiment 8 and 28 to 39
Performance test and cycle performance test, to further illustrate its advantages.
The ingredient and content of embodiment 8 and other additives in 28-39 and its by high temperature storage cycle performance survey
Test result is as follows shown in table 2 for examination and cycle performance test.
Table 2
The data from table 2 are it is found that the combined electrolyte that the sulfonic acid ester quat Yu the nitrile compound has been added
In further add other additives, can further promote the high temperature storage cycle performance of its lithium ion battery and follow
Ring performance.Wherein, by comparing embodiment 8 and 28-39 it is found that the lithium ion battery in embodiment 28-39 passes through cyclicity
The battery capacity conservation rate that can be tested can achieve 80.9% to 83.9%, and the battery tested by high temperature energy-storage cycle performance
Capacity retention ratio then can achieve 63.3% to 71.2%.
In other embodiments of the application, electrolyte further adds phosphazene compound.In following example 4 0-45
In, preparation method is same as Example 8, different places be the electrolyte of embodiment 40-45 preparation in further add
One of the compound that following structural formula indicates:
To the group for containing the sulfonic acid ester quat and the nitrile compound
In the electrolyte of conjunction (embodiment 8), the specific ingredient and content of the phosphazene compound of addition are as shown in table 3.To embodiment 8 and
The lithium ion battery of 40-45 carries out the test of high temperature storage cycle performance and drift bolt test, to further illustrate its advantages.
The ingredient and content of embodiment 8 and the phosphazene compound in 40-45 and its by high temperature storage cycle performance survey
Test result is as follows shown in table 3 for examination and drift bolt test.
Table 3
The data from table 3 are it is found that the combined electrolyte that the sulfonic acid ester quat Yu the nitrile compound has been added
In further add the phosphazene compound, can further be promoted the high temperature storage cycle performance of its lithium ion battery with
And drift bolt percent of pass.Wherein, by comparing embodiment 8 and 40-45 it is found that lithium ion battery in embodiment 40-45 into
Gone after the test of 20 drift bolts by number much higher than the embodiment 8 for being not added with the phosphazene compound, i.e., effectively improve
The security performance of lithium ion battery.Meanwhile the lithium ion battery added in the embodiment 40-45 of the phosphazene compound passes through height
The battery capacity conservation rate of warm energy storage cycle performance test then can slightly be promoted to 63.0% to 64.1%.
In other embodiments of the application, the anode of the application includes nickel-cobalt-manganese ternary material, due to self-characteristic,
Easily there is a phenomenon where transiting metal nickel, manganese, cobalt dissolution, the transition metal of dissolution can further catalytic electrolysis liquid side reaction,
To bring security risk to lithium ion battery.The application by the nitrile compound in the electrolytic solution and transiting metal nickel,
The complexing of manganese, cobalt, can preferably stable transition metal, reduce its dissolution, meanwhile, can be by sulfonic acid ester quat
Anode forms SEI film and reduces the dissolution of transition metal, while stable SEI film is also formed in cathode, prevents transition metal to negative
The destruction of SEI film on extremely, improves the security performance of lithium ion battery.In following example 4 6-62 and comparative example 4-6,
Preparation method is same as Example 1, different places be in embodiment 46-62 and comparative example 4-6 anode preparation in, be by
Nickel-cobalt-manganese ternary material (molecular formula LiNi0.8Co0.1Mn0.1O2), conductive agent acetylene black, binder polyvinylidene fluoride (write a Chinese character in simplified form
It is thoroughly mixed in suitable N-Methyl pyrrolidone (being abbreviated as NMP) solvent for PVDF) by weight 96:2:2, makes it
Form uniform anode sizing agent；Then anode sizing agent is coated on plus plate current-collecting body and is toasted 1 hour at 120 DEG C, and with
After be cold-pressed, cut-parts, cutting, anode is prepared.And to the lithium ion battery of embodiment 46-62 and comparative example 4-6 into
Row hot tank test, to further illustrate its advantages.
The electrolyte allotment ratio and composition of embodiment 46-62 and comparative example 4-6 and its test for passing through hot tank test
As a result as shown in table 4 below.
Table 4
According to the test result in table 4 it is found that compared with comparative example 4-6, the embodiment of the present application 46-62 is by being added to
Being combined in electrolyte for sulfonic acid ester quat and the nitrile compound is stated, the lithium ion battery provided can effectively reduce
The dissolution of nickel-cobalt-manganese ternary material at high temperature, and then its percent of pass in hot tank test is improved, improve lithium ion battery
Security property.
By the explanation of the above embodiments of the present application and comparative example it should be appreciated that this application provides a kind of electrolyte and packets
Containing its electrochemical appliance, the electrolyte includes the combination of the sulfonic acid ester quat and the nitrile compound, can be dropped
The generation of low electrolyte side reaction in positive electrode and negative electrode, and then effectively promote cycle performance and height after storage at high temperatures
Warm storage performance.In addition, by by further included in the electrolyte improve circulation additive and phosphazene compound in one
Kind, it can be further improved the circulation performance of the electrochemical appliance at high temperature.
In the whole instruction to " some embodiments ", " section Example ", " one embodiment ", " other embodiments ",
The reference of " citing ", " concrete example " or " some examples ", representated by mean in this application at least one implementation
Example or citing contain special characteristic, structure, material or characteristic described in the embodiment or citing.Therefore, it is entirely saying
The description occurred everywhere in bright book, such as: " in some embodiments ", " in embodiment ", " in one embodiment ",
" in another citing ", " in a citing ", " in particular examples " or " citing ", is not necessarily in reference the application
Identical embodiment or example.In addition, special characteristic herein, structure, material or characteristic can be with any suitable sides
Formula combines in one or more embodiments or citing.
Although having demonstrated and having described illustrative embodiments, those skilled in the art should understand that above-described embodiment cannot
It is interpreted the limitation to the application, and can be in the case where not departing from spirit herein, principle and range to implementation
Example is changed, alternatives and modifications.
Claims (12)
1. a kind of electrolyte comprising:
Sulfonic acid ester quat and nitrile compound.
2. electrolyte according to claim 1, wherein the sulfonic acid ester quat includes in the compound that formula 1 indicates
At least one,
Wherein, R11Selected from substituted or unsubstituted C1To C12Alkyl, substituted or unsubstituted C2To C12It is alkenyl, substituted or unsubstituted
C1To C12Alkoxy, substituted or unsubstituted C1To C12Acyloxy；
R12Selected from substituted or unsubstituted C1To C12Alkylidene, substituted or unsubstituted C2To C12It is alkenylene, substituted or unsubstituted
C2To C12Alkynylene, substituted or unsubstituted C1To C12Alkylene acyl group；
R13Selected from substituted or unsubstituted C1To C12Alkyl, substituted or unsubstituted C2To C12Alkenyl, substituted or unsubstituted C2
To C12Alkynyl, substituted or unsubstituted C1To C12Alkoxy, substituted or unsubstituted C1To C12It is acyloxy, substituted or unsubstituted
C6To C22Aryl, substituted or unsubstituted C5To C22Heterocyclic base；
R14Selected from substituted or unsubstituted C1To C3Alkylidene；
Substituent group is selected from cyano, halogen；
X-Indicate anionic group.
3. electrolyte according to claim 1, wherein the cation group of the sulfonic acid ester quat be selected from by
And combinations thereof composed by group.
4. electrolyte according to claim 1, wherein the anionic group of the sulfonic acid ester quat is selected from by F-、
NO3 -、PF6 -、BF4 -、AsF6 -、(FSO2)2N-、
And combinations thereof composed by group.
5. electrolyte according to claim 1, wherein the nitrile compound includes the change that formula 2, formula 3, formula 4 and formula 5 indicate
Close at least one of object
Wherein R21Selected from substituted or unsubstituted C1To C5Alkylidene, substituted or unsubstituted C1To C5Alkylene oxide group；
R31And R32It is each independently selected from covalent bond, substituted or unsubstituted C1To C5Alkylidene；
R41、R42And R43It is each independently selected from covalent bond, substituted or unsubstituted C1To C5Alkylidene, substituted or unsubstituted C1
To C5Alkylene oxide group；
Wherein, R51Selected from substituted or unsubstituted C1To C5Alkylidene, substituted or unsubstituted C2To C10Alkenylene, substitution or not
Substituted C6To C10Arlydene, substituted or unsubstituted C1To C6Heterocycle；
Wherein, substituent group is selected from group composed by halogen, nitro, cyano, carboxyl, sulfate and combinations thereof.
6. electrolyte according to claim 1, wherein the nitrile compound is selected from
And combinations thereof composed by group.
7. electrolyte according to claim 1, further comprisesAnd combinations thereof composed by group compound.
8. electrolyte according to claim 1 further comprises phosphonitrile, the phosphonitrile is selected from the compound that formula 6 indicates
At least one of,
Wherein, R61It can be selected from substituted or unsubstituted C1To C12Alkyl, substituted or unsubstituted C3To C12Naphthenic base, substitution or not
Substituted C2To C12Alkenyl, substituted or unsubstituted C6To C22Aryl, substituted or unsubstituted C5To C22Heterocyclic base；With
Substituent group is selected from cyano, halogen.
9. electrolyte according to claim 8, wherein the phosphonitrile be selected from by
And combinations thereof composed by group.
10. electrolyte according to claim 1, wherein with the total weight of the electrolyte, the sulfonic acid ester quat
Content be 0.1% to 10%, the content of the nitrile compound is 0.5% to 12%.
11. a kind of electrochemical appliance comprising:
Anode；
Cathode；
Isolation film；And according to claim 1 to electrolyte described in any claim in 10.
12. a kind of electronic device, it includes the electrochemical appliances described in claim 11.
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