CN110176630A - Electrolyte and the electrochemical appliance for using it - Google Patents
Electrolyte and the electrochemical appliance for using it Download PDFInfo
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- CN110176630A CN110176630A CN201910468643.1A CN201910468643A CN110176630A CN 110176630 A CN110176630 A CN 110176630A CN 201910468643 A CN201910468643 A CN 201910468643A CN 110176630 A CN110176630 A CN 110176630A
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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
- H01M10/052—Li-accumulators
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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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- 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
- H01M10/058—Construction or manufacture
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
- Y02E60/10—Energy storage using batteries
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
This application involves electrolyte and use its electrochemical appliance.The electrolyte includes sulphones, phosphorus-containing compound and additive A, and the additive A includes at least one of following compound: the compound containing phenyl ring, fluorine ether compound, fluoro ketone compound and fluorosilicone compounds.Electrolyte conductivity with higher provided by the present application and preferable electrochemical stability and security performance, the cycle performance of battery can be significantly improved and meet the needs of lithium metal battery big multiplying power discharging, there is very big application value in lithium metal battery.
Description
Technical field
This application involves electrochemical appliance technical fields, and more particularly to a kind of electrolyte and the electrification using it
Learn device.
Background technique
Lithium ion battery is due to having many advantages, such as that environmental-friendly, operating voltage is high, specific capacity is big and has extended cycle life and obtains
To extensive use, become the most potential novel green electrochmical power source in the world today.Wherein packaging thickness is small, light weight
Soft-package battery has been favored by people.Then as the fast development of lithium electricity industry, people propose lithium ion battery higher
Requirement: more frivolous, smaller and higher energy density.With further increasing for lithium ion battery energy density, lithium metal
Battery receives extensive attention.
Lithium metal have minimum chemical potential (- 3.04V) and very high reactivity, common liquid electrolyte and
The reactivity of lithium metal is high.If the reactivity of electrolyte and metal lithium electrode is high or electric in the solid of electrode surface formation
Solution matter interfacial film (SEI) is unstable, and coulombic efficiency can be very low in cyclic process for lithium metal battery, and Li dendrite pierces through diaphragm
Cause short circuit that can also bring security risk.
Therefore, exploitation can satisfy long circulating, high rate charge-discharge demand lithium metal battery liquid electrolyte to close
It is important.
Summary of the invention
The application provide a kind of electrolyte and using its electrochemical appliance with attempt at least solve in a way to
Few one kind is present in the problems in related fields.
According to some embodiments, the application provides a kind of electrolyte, and the electrolyte includes sulphones, phosphorus-containing compound
And additive A, the additive A include at least one of following compound: the compound containing phenyl ring, fluorine etherificate are closed
Object, fluoro ketone compound and fluorosilicone compounds.
According to some embodiments, when the electrolyte includes the compound containing phenyl ring, based on the total of the electrolyte
Weight, the weight percent of the compound containing phenyl ring are 6wt%-60wt%.
According to some embodiments, based on the total weight of the electrolyte, the sulphones and the phosphorus-containing compound
Weight percent and be X, the weight percent of the additive A is Y, and wherein X and Y meets following condition: 0.25≤Y/X≤
3.5。
According to some embodiments, the sulphones include at least one of Formulas I or Formula II compound:
Wherein:
R1And R2It is each independently selected from C6-C26Aryl, halogen, C1-C12Alkyl, C2-C12Alkenyl and C1-C12Halogenated alkyl；
R3Selected from hydrogen, C6-C26Aryl, halogen, C1-C12Alkyl and C1-C12Halogenated alkyl；And
Wherein n is selected from the integer of 1-6.
According to some embodiments, the sulphones include one of following compound or a variety of: dimethyl sulfone, ethylene
Sulfone, diethyl sulfone, ethylene methacrylic sulfone, Methylethyl sulfone, sulfolane, Thietane -1,1- dioxide or 3- bromine thia ring fourth
Alkane -1,1- dioxide.
According to some embodiments, the phosphorus-containing compound includes formula III compound:
Wherein:
R4、R5And R6It is each independently selected from C1-C12Alkyl, C2-C12Alkenyl, C2-C12Alkynyl, C1-C12Halogenated alkyl, C2-
C12Halogenated alkenyl, C6-C26Aryl, C6-C26Halogenated aryl and C1-C12Alkoxy.
According to some embodiments, the phosphorus-containing compound includes one of following compound or a variety of: trimethyl phosphate,
Triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate (chloroethyl) ester, tricresyl phosphate (1,3- dichloro
Propyl) ester or tricresyl phosphate (trifluoroethyl) ester.
According to some embodiments, the compound containing phenyl ring includes formula IV compound:
Wherein R7Selected from C1-C20Alkyl or C1-C20Alkoxy；And
Wherein q is selected from the integer of 1-6.
According to some embodiments, the fluoro ketone compound includes Formula V compound:
Wherein R10、R11It is each independently selected from C1-C12Fluoro-alkyl or C2-C12Fluoro alkenyl.
According to some embodiments, wherein the fluoro ketones compound includes one of following compound or a variety of:
Perfluor hexanone, bis- (the trifluoromethy)-propiones of 1,1,1,2,4,5,5,5- octafluoro generation -2,4- or 1,1,1,3,4,
4,4- seven fluoro- 3- (trifluoromethyl) -2- butanone.
According to some embodiments, the fluorosilicone compounds include Formula IV compound:
Wherein R12、R13、R14、R15、R16、R17It is each independently selected from C1-C12Alkyl, C1-C12Fluoro-alkyl, C1-C12Alkene
Base or C2-C12Fluoro alkenyl, and R12、R13、R14、R15、R16、R17At least one of be C1-C12Fluoro-alkyl or C2-C12Fluorine
For alkenyl.
According to some embodiments, the fluorosilicone compounds include bis- (trifluoro propyl) -1 1,3-, 1,3,3- tetramethyl
Base disiloxane, two (13 fluoro- 1,1,2,2- tetrahydro octyl) tetramethyl disiloxanes or combinations thereof.
According to some embodiments, the fluorine ether compound include in the compound of Formula VII, Formula VIII, Formula IX, Formula X extremely
Few one:
Rf1-O-Rf2 VII,
Rf1-O-R VIII,
Rf1–O–(R'–O)n- Rf2 IX,
Rf1–O–(R'–O)n- R X,
Wherein in Formula VII, Formula VIII, Formula IX, Formula X, Rf1 and Rf2 are each independently selected from least one hydrogen atom quilt
The C of fluorine-based substituted linear chain or branched chain1-C12Fluoro-alkyl, R are the C of linear chain or branched chain1-C12Alkyl, R' are linear chain or branched chain
C1-C5Alkylidene, and the integer that n is 1 to 5.
According to some embodiments, wherein Rf1 or Rf2 is each independently selected from one of the group being made up of:
HCF2-、CF3-、HCF2CF2-、CH3CF2-、CF3CH2-、CF3CF2-、(CF3)2CH-、HCF2CF2CH2-、CF3CH2CH2-、
HCF2CF2CF2CH2-、HCF2CF2CF2CF2CH2-、CF3CF2CH2-、CF3CFHCF2CH2-、HCF2CF(CF3)CH2And
CF3CF2CH2CH2-。
According to some embodiments, the fluorine ether compound includes one of following compound or a variety of:
HCF2CF2CH2OCF2CF2H、(CF3)2CFCF(CF2CF3)(OCH3)、CF3CHFCF2CH(CH3)OCF2CHFCF3、
HCF2CF2CH2OCF2CF2CF2CF2H、HCF2CF2OCH2CF3、HCF2CF2OCH2CH2OCF2CF2H、
HCF2CF2OCH2CH2CH2OCF2CF2H、HCF2CF2CH2OCF2CF2CF2H、HCF2CF2OCH2CH2OCF2CF2CF2H、
HCF2CF2OCH2CH2CH2OCF2CF2CF2H、CH3OCH2CH2OCH2CH2F、CH3OCH2CH2OCH2CF3、CH3OCH2CH(CH3)
OCH2CH2F、CH3OCH2CH(CH3)OCH2CF3、FCH2CH2OCH2CH2OCH2CH2F、FCH2CH2OCH2CH(CH3)OCH2CH2F、
CF3CH2O(CH2CH2O)2CH2CF3And CF3CH2OCH2CH(CH3)OCH2CF3。
According to some embodiments, the electrolyte further comprises additive B, wherein the additive B includes followingization
Close at least one of object:
Vinylethylene carbonate, vinylene carbonate, fluorinated ethylene carbonate, 4- trifluoromethy ethylene carbonate, two
Lithium bis (oxalate) borate, difluorine oxalic acid boracic acid lithium, LiBF4, lithium nitrate, methane-disulfonic acid methylene ester, sulfuric acid vinyl ester, sulfurous
Sour ethyl, succinic anhydride, propylene sulfite, acrylic -1,3- sultones, bis- (trimethyl silicon substrate) sulfuric esters, bis- (three
Methylsilyl) sulfuric ester, N- methyl, butyl pyrrolidine bis-trifluoromethylsulfoandimide salt, N- methyl, the double trifluoro methylsulphurs of propylpiperdine
It is bis- (cyanoethoxyl) ethane of imide salts, 1,3- dioxanes, 1,4- dioxane, 1,2-, adiponitrile, anti-maleic nitrile, cis-
Maleonitrile, succinonitrile, 1,3,5- penta trimethylsilyl nitriles, 1,3,6- own trimethylsilyl nitriles, 2,5- diethyl tetrahydrofuran, trimethylsilyl
2- (fluorosulfonyl) difluoro acetate or trifluoroacetic acid allyl ester.
According to some embodiments, based on the total weight of the electrolyte, the weight percent of the additive B is
0.05wt%-10wt%.
Other embodiments of the application provide a kind of electrochemical appliance, wherein the electrochemical appliance includes above-mentioned
The electrolyte of one embodiment of anticipating.
Other embodiments of the application provide a kind of electronic device, wherein the electronic device includes above-mentioned any one
The electronic device of a embodiment.
Electrolyte conductivity with higher provided by the present application and preferable electrochemical stability and security performance, can
To significantly improve the cycle performance of battery and meet the needs of lithium metal battery big multiplying power discharging, have in lithium metal battery non-
Often big application value.
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.Embodiments herein is not construed as pair
The limitation of the application.
As used in this application, term " about " is to describe and illustrate small variation.Make when in conjunction with event or situation
Used time, the term can be referred to the example that wherein event or situation accurately occur and wherein event or situation pole approximatively occurs
Example.For example, when in conjunction with numerical value in use, term can be referred to ± 10% variation model less than or equal to the numerical value
Enclose, 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
Equal to ± 1%, it is less than or equal to ± 0.5%, is less than or equal to ± 0.1% or is less than or equal to ± 0.05%.
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.
In specific embodiment and claims, in statement, that is, capitalization " C " subsequent number about carbon number,
Such as " C1-C20”、“C3-C20" etc. in, digital such as " 1 ", " 3 " or " 20 " after " c " indicates the carbon in specific functional group
Number.That is, functional group may include 1-20 carbon atom and 3-20 carbon atom respectively.For example, " C1-C4Alkyl " refers to 1-4
The alkyl of carbon atom, such as CH3-、CH3CH2-、CH3CH2CH2-、(CH3)2CH-、CH3CH2CH2CH2-、CH3CH2CH(CH3)-or
(CH3)3C-。
As used herein, " alkyl " is contemplated to be the linear saturation hydrocarbon structure with 1 to 20 carbon atom." alkyl " it is also contemplated that
It is branch or cyclic hydrocarbon structures with 3 to 20 carbon atoms.For example, alkyl can be a for alkyl, the 1-10 of 1-20 carbon atom
The alkyl of carbon atom, the alkyl of 1-5 carbon atom, the alkyl of 5-20 carbon atom, the alkyl of 5-15 carbon atom or 5-10
The alkyl of carbon atom.When the specified alkyl with specific carbon number, it is contemplated that cover all geometric isomers with the carbon number；Cause
This, for example, " butyl " is meant including normal-butyl, sec-butyl, isobutyl group, tert-butyl and cyclobutyl；" propyl " include n-propyl,
Isopropyl and cyclopropyl.Examples of alkyl includes, but are not limited to methyl, ethyl, n-propyl, isopropyl, cyclopropyl, normal-butyl, different
Butyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, cyclopenta, methylcyclopentyl, ethylcyclopentyl,
N-hexyl, isohesyl, cyclohexyl, n-heptyl, octyl, cyclopropyl, cyclobutyl, norborny etc..In addition, alkyl can be optionally
Ground is substituted.
As used herein, term " alkylidene " covers straight chain and branched alkylidene.For example, alkylidene can be C1-C50Alkylene
Base, C1-C40Alkylidene, C1-C30Alkylidene, C1-C20Alkylidene, C1-C10Alkylidene, C1-C6Alkylidene, C2-C6Alkylidene, C2-
C5Alkylidene.In addition, alkylidene can be and be optionally substituted.
As used herein, term " aryl " covers single loop system and multi-loop system.The polycyclic two of them carbon that can have is
Two or more shared rings of two adjacent rings (ring is " condensed "), wherein at least one of described ring is fragrance
Race, such as other rings can be naphthenic base, cycloalkenyl, aryl, heterocycle and/or heteroaryl.For example, aryl can be C6-C50Virtue
Base, C6-C40Aryl, C6-C30Aryl, C6-C20Aryl or C6-C10Aryl.Representative aryl includes (for example) phenyl, methylbenzene
Base, propyl phenyl, isopropyl phenyl, benzyl and naphthalene -1- base, naphthalene -2- base etc..
As used herein, term " alkenyl " refer to can for straight chain or tool branch and have at least one and it is 1,2 usual
Or the monovalent unsaturated hydrocarbon group of 3 carbon-to-carbon double bonds.Unless otherwise defined, the alkenyl usually contains 2-20 carbon original
Son, such as can be a for the alkenyl of 2-20 carbon atom, the alkenyl of 6-20 carbon atom, the alkenyl of 2-12 carbon atom or 2-6
The alkenyl of carbon atom.Representative alkenyl includes (for example) vinyl, positive acrylic, isopropenyl, n- but-2-ene base, butyl- 3-
Alkenyl, n- hex- 3- alkenyl etc..In addition, alkenyl can be and be optionally substituted.
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
Such as can for the alkynyl of 2-20 carbon atom, the alkynyl of 6-20 carbon atom, 2-10 carbon atom alkynyl or 2~6 carbon originals
The alkynyl of son.Representative alkynyl includes (for example) acetenyl, Propargyl (n- propinyl), n- butyl- 2- alkynyl, n- hex-
3- alkynyl etc..In addition, alkynyl can be and be optionally substituted.
As used herein, " alkoxy " covers alkoxy, the 1-5 of the alkoxy of 1-20 carbon atom, 1-10 carbon atom
The alkoxy of a carbon atom, the alkoxy of 5-20 carbon atom, the alkoxy of 5-15 carbon atom or 5-10 carbon atom alkane
Oxygroup.In addition, alkoxy can be and be optionally substituted.
When above-mentioned substituent group is substituted, their substituent group can be each independently selected from the group being made up of: halogen
Element, alkyl, alkenyl, alkynyl, aryl.
As used herein, term " halogen " covers F, Cl, Br, I.
One, electrolyte
The embodiment of the present application provides a kind of electrolyte, and the electrolyte includes sulphones, phosphorus-containing compound and adds
Add agent A, the additive A includes at least one of following compound: the compound containing phenyl ring, fluorine ether compound, fluoro
Ketone compound and fluorosilicone compounds.The conductivity that can effectively improve electrolyte using above-mentioned electrolyte, in cathode shape
At the stability for improving anode while stablizing SEI film, to improve the cycle life of lithium metal battery.
In some embodiments, when electrolyte includes the compound containing phenyl ring, based on the total weight of the electrolyte,
The weight percent of the compound containing phenyl ring is about 6wt%-60wt%.In some embodiments, when electrolyte includes containing
When having the compound of phenyl ring, based on the total weight of the electrolyte, the weight percent of the compound containing phenyl ring is about
10wt%-50wt%.In some embodiments, when electrolyte includes the compound containing phenyl ring, based on the total of the electrolyte
Weight, the weight percent of the compound containing phenyl ring are about 20wt%-40wt%.In some embodiments, work as electrolyte
When including compound containing phenyl ring, based on the total weight of the electrolyte, the weight percent of the compound containing phenyl ring
Than for about 15wt%, about 25wt%, about 30wt%, about 35wt%, about 45wt% or about 55wt%.
In some embodiments, the total weight based on the electrolyte, the sulphones and the phosphorus-containing compound
Weight percent and be X, the weight percent of the additive A is Y, and wherein X and Y meets following condition: about 0.25≤Y/X
≤ about 3.5.
In some embodiments, X and Y meets following condition: about 0.5≤Y/X≤about 3.5.In some embodiments, X and Y
Meet following condition: about 1≤Y/X≤about 3.In some embodiments, X and Y meets following condition: about 1.5≤Y/X≤about 2.5.
When X and Y meet above-mentioned condition, the conductivity of electrolyte is improved, and the SEI film on lithium metal surface is more stable, thus further
Improve the cycle performance of battery.
In some embodiments, the sulphones include at least one of Formulas I or Formula II compound:
Wherein:
R1And R2It is each independently selected from C6-C50Aryl, C6-C26Aryl, C6-C12Aryl, halogen, C1-C20Alkyl, C1-C12
Alkyl, C1-C6Alkyl, C2-C20Alkenyl, C2-C12Alkenyl, C2-C6Alkenyl, C1-C20Halogenated alkyl, C1-C12Halogenated alkyl, C1-C6
Halogenated alkyl；
R3Selected from hydrogen, C6-C50Aryl, C6-C26Aryl, C6-C12Aryl, halogen, C1-C20Alkyl, C1-C12Alkyl, C1-C6
Alkyl and C1-C20Halogenated alkyl, C1-C12Halogenated alkyl, C1-C6Halogenated alkyl；And
Wherein n is selected from the integer of 1-6.
In some embodiments, the sulphones include one of following compound or a variety of: dimethyl sulfone, ethylene
Sulfone, diethyl sulfone, ethylene methacrylic sulfone, Methylethyl sulfone, sulfolane, Thietane -1,1- dioxide or 3- bromine thia ring fourth
Alkane -1,1- dioxide.
In some embodiments, the total weight based on the electrolyte, the weight percent of the sulphones are about
1wt%-60wt%.In some embodiments, the total weight based on the electrolyte, the weight percent of the sulphones are
About 1wt%-40wt%.In some embodiments, the total weight based on the electrolyte, the weight percent of the sulphones
It is about 10wt%-30wt%.In some embodiments, the total weight based on the electrolyte, the weight hundred of the sulphones
Point than be about 5wt%, about 15wt%, about 20wt%, about 25wt%, about 35wt%, about 45wt% or about 55wt%.
In some embodiments, the phosphorus-containing compound includes formula III compound:
Wherein:
R4、R5And R6It is each independently selected from C1-C20Alkyl, C1-C12Alkyl, C1-C6Alkyl, C2-C20Alkenyl, C2-C12Alkene
Base, C2-C6Alkenyl, C2-C20Alkynyl, C2-C12Alkynyl, C2-C6Alkynyl, C1-C20Halogenated alkyl, C1-C12Halogenated alkyl, C1-C6Halogen
Substituted alkyl, C2-C20Halogenated alkenyl, C2-C12Halogenated alkenyl, C2-C6Halogenated alkenyl, C6-C50Aryl, C6-C26Aryl, C6-C12Virtue
Base, C6-C50Halogenated aryl, C6-C26Halogenated aryl, C6-C12Halogenated aryl, C1-C20Alkoxy, C1-C12Alkoxy and C1-C6Alkane
Oxygroup.
In some embodiments, the phosphorus-containing compound includes one of following compound or a variety of: trimethyl phosphate,
Triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate (chloroethyl) ester, tricresyl phosphate (1,3- dichloro
Propyl) ester or tricresyl phosphate (trifluoroethyl) ester.
In some embodiments, the total weight based on the electrolyte, the weight percent of the phosphorus-containing compound are about
1wt%-60wt%.In some embodiments, the total weight based on the electrolyte, the weight percent of the phosphorus-containing compound
It is about 1wt%-40wt%.In some embodiments, the total weight based on the electrolyte, the weight hundred of the phosphorus-containing compound
Dividing ratio is about 10wt%-30wt%.In some embodiments, the total weight based on the electrolyte, the phosphorus-containing compound
Weight percent is about 5wt%, about 15wt%, about 20wt%, about 25wt%, about 35wt%, about 45wt% or about 55wt%.When
The content of phosphate within this range when, can guarantee leaching of the electrolyte to diaphragm and positive and negative anodes while improving lithium salts meltage
Lubricant nature energy further increases the cycle performance of battery.
In some embodiments, the compound containing phenyl ring includes formula IV compound:
Wherein R7Selected from C1-C20Alkyl, C1-C12Alkyl, C1-C6Alkyl, C1-C20Alkoxy, C1-C12Alkoxy or C1-C6
Alkoxy；And
Wherein q is selected from the integer of 1-6.
Sulphones, the phenyl ring that phosphorus-containing compound and substituent group are electron donating group is used in combination can improve lithium metal battery
Cycle performance, this may be because three's collective effect can reduce reduction reaction energy barrier, be easier to be reduced in cathode, and
The SEI film more dense uniform of formation can effectively prevent reacting for cathode and electrolyte.
In some embodiments, the fluoro ketone compound includes Formula V compound:
Wherein R10、R11It is each independently selected from C1-C20Fluoro-alkyl, C1-C12Fluoro-alkyl, C1-C6Fluoro-alkyl, C2-
C20Fluoro alkenyl, C2-C12Fluoro alkenyl, C2-C6Fluoro alkenyl.
In some embodiments, the fluoro ketone compound includes one of following compound or a variety of:
Perfluor hexanone, bis- (the trifluoromethy)-propiones of 1,1,1,2,4,5,5,5- octafluoro generation -2,4- or 1,1,1,3,4,
4,4- seven fluoro- 3- (trifluoromethyl) -2- butanone.
In some embodiments, the weight percent of the total weight based on the electrolyte, the fluoro ketone compound is
About 1wt%-70wt%.In some embodiments, the total weight based on the electrolyte, the weight hundred of the fluoro ketone compound
Dividing ratio is about 10wt%-60wt%.In some embodiments, the total weight based on the electrolyte, the fluoro ketone compound
Weight percent be about 10wt%-50wt%.In some embodiments, the total weight based on the electrolyte, the fluoro
The weight percent of ketone compound is about 5wt%, about 15wt%, about 20wt%, about 25wt%, about 30wt%, about 40wt% or
About 50wt%.
In some embodiments, the fluorosilicone compounds include Formula IV compound:
Wherein R12、R13、R14、R15、R16、R17It is each independently selected from C1-C20Alkyl, C1-C12Alkyl, C1-C6Alkyl, C1-
C20Fluoro-alkyl, C1-C12Fluoro-alkyl, C1-C6Fluoro-alkyl, C1-C20Alkenyl, C1-C12Alkenyl, C1-C6Alkenyl, C2-C20Fluoro
Alkenyl, C2-C12Fluoro alkenyl or C2-C6Fluoro alkenyl, and R12、R13、R14、R15、R16、R17At least one of be C1-C20Fluoro
Alkyl, C1-C12Fluoro-alkyl, C1-C6Fluoro-alkyl, C2-C20Fluoro alkenyl, C2-C12Fluoro alkenyl or C2-C6Fluoro alkenyl.
In some embodiments, the fluorosilicone compounds include bis- (trifluoro propyl) -1 1,3-, 1,3,3- tetramethyl
Base disiloxane, two (13 fluoro- 1,1,2,2- tetrahydro octyl) tetramethyl disiloxanes or combinations thereof.
In some embodiments, the total weight based on the electrolyte, the weight percent of the fluorosilicone compounds
Than for about 10wt%-60wt%.In some embodiments, the total weight based on the electrolyte, the fluorosilicone chemical combination
The weight percent of object is about 10wt%-50wt%.In some embodiments, the total weight based on the electrolyte, the fluorine
Weight percent for silicone compounds is about 15wt%-50wt%.In some embodiments, based on the total of the electrolyte
Weight, the weight percent of the fluorosilicone compounds is about 15wt%, about 20wt%, about 25wt%, about 30wt%
Or about 40wt%.
In some embodiments, the fluorine ether compound include in the compound of Formula VII, Formula VIII, Formula IX, Formula X extremely
Few one:
Rf1-O-Rf2 VII,
Rf1-O-R VIII,
Rf1–O–(R'–O)n- Rf2 IX,
Rf1–O–(R'–O)n- R X,
Wherein in Formula VII, Formula VIII, Formula IX, Formula X, Rf1 and Rf2 are each independently selected from least one hydrogen atom quilt
The C of fluorine-based substituted linear chain or branched chain1-C20Fluoro-alkyl, at least one hydrogen atom are by the C of fluorine-based substituted linear chain or branched chain1-
C12Fluoro-alkyl, at least one hydrogen atom are by the C of fluorine-based substituted linear chain or branched chain1-C6Fluoro-alkyl, R are linear chain or branched chain
C1-C20The C of alkyl, linear chain or branched chain1-C12The C of alkyl, linear chain or branched chain1-C6Alkyl, R' are the C of linear chain or branched chain1-C20
The C of alkylidene, linear chain or branched chain1-C12The C of alkylidene, linear chain or branched chain1-C5Alkylidene, and the integer that n is 1 to 5.
In some embodiments, wherein Rf1 or Rf2 is each independently selected from one of the group being made up of:
HCF2-、CF3-、HCF2CF2-、CH3CF2-、CF3CH2-、CF3CF2-、(CF3)2CH-、HCF2CF2CH2-、CF3CH2CH2-、
HCF2CF2CF2CH2-、HCF2CF2CF2CF2CH2-、CF3CF2CH2-、CF3CFHCF2CH2-、HCF2CF(CF3)CH2And
CF3CF2CH2CH2-。
In some embodiments, the fluorine ether compound includes one of following compound or a variety of:
HCF2CF2CH2OCF2CF2H、(CF3)2CFCF(CF2CF3)(OCH3)、CF3CHFCF2CH(CH3)OCF2CHFCF3、
HCF2CF2CH2OCF2CF2CF2CF2H、HCF2CF2OCH2CF3、HCF2CF2OCH2CH2OCF2CF2H、
HCF2CF2OCH2CH2CH2OCF2CF2H、HCF2CF2CH2OCF2CF2CF2H、HCF2CF2OCH2CH2OCF2CF2CF2H、
HCF2CF2OCH2CH2CH2OCF2CF2CF2H、CH3OCH2CH2OCH2CH2F、CH3OCH2CH2OCH2CF3、CH3OCH2CH(CH3)
OCH2CH2F、CH3OCH2CH(CH3)OCH2CF3、FCH2CH2OCH2CH2OCH2CH2F、FCH2CH2OCH2CH(CH3)OCH2CH2F、
CF3CH2O(CH2CH2O)2CH2CF3And CF3CH2OCH2CH(CH3)OCH2CF3。
In some embodiments, the weight percent of the total weight based on the electrolyte, the fluorine ether compound is about
1wt%-70wt%.In some embodiments, the total weight based on the electrolyte, the weight percent of the fluorine ether compound
It is about 10wt%-70wt%.In some embodiments, the total weight based on the electrolyte, the weight of the fluorine ether compound
Percentage is about 10wt%-60wt%.In some embodiments, the total weight based on the electrolyte, the fluorine ether compound
Weight percent be about 5wt%, about 15wt%, about 20wt%, about 25wt%, about 30wt%, about 40wt% or about 50wt%.
In some embodiments, the electrolyte further comprises additive B, wherein the additive B includes followingization
Close one of object or a variety of:
Vinylethylene carbonate, vinylene carbonate, fluorinated ethylene carbonate, 4- trifluoromethy ethylene carbonate, two
Lithium bis (oxalate) borate, difluorine oxalic acid boracic acid lithium, LiBF4, lithium nitrate, methane-disulfonic acid methylene ester, sulfuric acid vinyl ester, sulfurous
Sour ethyl, succinic anhydride, propylene sulfite, acrylic -1,3- sultones, bis- (trimethyl silicon substrate) sulfuric esters, bis- (three
Methylsilyl) sulfuric ester, N- methyl, butyl pyrrolidine bis-trifluoromethylsulfoandimide salt, N- methyl, the double trifluoro methylsulphurs of propylpiperdine
It is bis- (cyanoethoxyl) ethane of imide salts, 1,3- dioxanes, 1,4- dioxane, 1,2-, adiponitrile, anti-maleic nitrile, cis-
Maleonitrile, succinonitrile, penta trimethylsilyl nitrile of 1,3,5-, the own trimethylsilyl nitrile of 1,3,6-, 2,5- diethyl tetrahydrofuran, trimethylsilyl
2- (fluorosulfonyl) difluoro acetate or trifluoroacetic acid allyl ester.Sulphones, phosphorus-containing compound, additive A and additive B
It is used in combination, uniform protective film can be respectively formed in anode and cathode, to effectively improve the cycle life of battery.
In some embodiments, the total weight based on the electrolyte, the weight percent of the additive B are about
0.05wt%-10wt%.In some embodiments, the total weight based on the electrolyte, the weight percent of the additive B
It is about 0.05wt%-5wt%.In some embodiments, the total weight based on the electrolyte, the weight hundred of the additive B
Point than be about 1wt%, about 2wt%, about 3wt% or about 4wt%.
Two, electrolyte
The electrolyte that the electrolyte of the embodiment of the present application uses can be electrolyte well known in the prior art, electrolyte packet
It includes but is not limited to: inorganic lithium salt, such as LiClO4、LiAsF6、LiPF6、LiBF4、LiSbF6、LiSO3F、LiN(FSO2)2Deng；Contain
Fluorine organic lithium salt, such as LiCF3SO3、LiN(FSO2)(CF3SO2)、LiN(CF3SO2)2、LiN(C2F5SO2)2, ring-type 1,3- hexafluoro
Propane di-sulfonyl imides lithium, ring-type 1,2- tetrafluoroethane di-sulfonyl imides lithium, LiN (CF3SO2)(C4F9SO2)、LiC(CF3SO2)3、
LiPF4(CF3)2、LiPF4(C2F5)2、LiPF4(CF3SO2)2、LiPF4(C2F5SO2)2、LiBF2(CF3)2、LiBF2(C2F5)2、
LiBF2(CF3SO2)2、LiBF2(C2F5SO2)2；The lithium salts of complex containing dicarboxylic acids, such as bis- (oxalate conjunction) lithium borates, difluoro grass
Acid group closes lithium borate, three (oxalate conjunction) lithium phosphates, bis- (oxalate conjunction) lithium phosphates of difluoro, tetrafluoro (oxalate conjunction) lithium phosphate
Deng.In addition, above-mentioned electrolyte can be used alone, two or more can also be used simultaneously.For example, in some realities
It applies in example, electrolyte includes LiPF6And LiBF4Combination.In some embodiments, electrolyte includes LiPF6Or LiBF4Etc. nothings
Machine lithium salts and LiCF3SO3、LiN(CF3SO2)2、LiN(C2F5SO2)2Etc. the combination of fluorine-containing organic lithium salt.In some embodiments,
The concentration of electrolyte in the range of about 0.5- about 4mol/L, in the range of for example, about 0.8- about 3mol/L, about 0.8- about
In the range of 2.5mol/L, in the range of about 0.8- about 2mol/L, in the range of about 1- about 2mol/L, about 0.5- about 1.5mol/
L, about 0.8- about 1.3mol/L, about 0.5- about 1.2mol/L, in another example be about 1mol/L, about 1.15mol/L, about 1.2mol/L,
About 1.5mol/L, about 2mol/L or about 2.5mol/L.
Three, electrochemical appliance
The electrochemical appliance of the application includes any device that electrochemical reaction occurs, its specific example includes all kinds
One-shot battery, secondary cell, fuel cell, solar battery or the capacitor of class.In some embodiments, the electrochemical appliance
It is lithium metal battery.In some embodiments, which is lithium secondary battery, including lithium ion secondary battery, lithium gather
Close object secondary cell or lithium ion polymer secondary cell.In some embodiments, the electrochemical appliance of the application is that have
There is the anode for the positive active material that can occlude, release metal ion and with can occlude, release the negative of metal ion
The electrochemical appliance of the cathode of pole active material, which is characterized in that above-mentioned any electrolyte comprising the application.
1, electrolyte
Electrolyte used in the electrochemical appliance of the application is above-mentioned any electrolyte of the application.In addition, the application
Electrochemical appliance used in electrolyte also may include other electrolyte in the range of the purport for not departing from the application.
2, cathode
It can include any public in the prior art with the material of cathode in the case of this application, composition and its manufacturing method
The technology opened.
In some embodiments, negative electrode active material is lithium metal material.In some embodiments, the negative electrode active material
Material is selected from lithium metals correlation negative electrode materials such as lithium metal, the lithium metal of structuring, the lithium metals of protective layer modification.The lithium of structuring
Slurry can be made by the way that structuring material therefor, thickener, conductive material, packing material etc. is added in metal correlation negative electrode material
Material, which is coated on collector, and lithium metal is formed knot with certain pressure pressing structure material again after dry
The lithium an- ode material of structure.The lithium metal associated materials of protective layer modification can be by covering on lithium copper foil certain thickness
It is dried to obtain after armor coated.In some embodiments, lithium an- ode includes conducting matrix grain and is dispersed in conducting matrix grain
Metallic particles.Matcoveredn on conducting matrix grain in some embodiments, protective layer with a thickness of 1nm-10 μm.
3, positive
It can include any public in the prior art with material positive in the case of this application, composition and its manufacturing method
The technology opened.In some embodiments, the anode recorded in just extremely U.S. Patent application US9812739B, to be cited in full text
Mode be incorporated herein.
In some embodiments, anode includes collector and the anode active material layer on the collector.Anode is living
Property material include reversibly be embedded in and deintercalation lithium metal at least one lithiumation intercalation compound.In some embodiments, positive
Active material includes composite oxides.In some embodiments, which contains lithium and selects from cobalt, manganese and nickel
At least one element.
In some embodiments, positive electrode active materials include, but are not limited to:
LiaA1-bXbD2(0.90≤a≤1.8,0≤b≤0.5),
LiaE1-bXbO2-cDc(0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05),
LiaE2-bXbD4(0.90≤a≤1.8,0≤b≤0.5),
LiaE2-bXbO4-cDc (0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05),
LiaNi1-b-cCobXcDα(0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05,0 < α≤2),
LiaNi1-b-cCobXcO2-αTα(0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05,0 < α < 2),
LiaNi1-b-cCobXcO2-αT2(0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05,0 < α < 2),
LiaNi1-b-cMnbXcDα(0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05,0 < α≤2),
LiaNi1-b-cMnbXcO2-αTα(0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05,0 < α < 2),
LiaNi1-b-cMnbXcO2-αT2(0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05,0 < α < 2),
LiaNibEcGdO2(0.90≤a≤1.8,0≤b≤0.9,0≤c≤0.5,0.001≤d≤0.1),
LiaNibCocMndGeO2(0.90≤a≤1.8,0≤b≤0.9,0≤c≤0.5,0≤d≤0.5,0.001≤e≤
0.1)、
LiaNiGbO2(0.90≤a≤1.8,0.001≤b≤0.1),
LiaCoGbO2(0.90≤a≤1.8,0.001≤b≤0.1),
LiaMnGbO2(0.90≤a≤1.8,0.001≤b≤0.1),
LiaMn2GbO4(0.90≤a≤1.8,0.001≤b≤0.1),
QO2、QS2、LiQS2、V2O5、LiV2O5、LiIO2、LiNiVO4、Li(3-f)J2(PO4)3(0≤f≤2)、Li(3-f)Fe2
(PO4)3(0≤f≤2) or LiFePO4,
Wherein, A is selected from Ni, Co, Mn and their any combination；X selected from Al, Ni, Co, Mn, Cr, Fe, Mg, Sr,
V, rare earth element and their any combination；D is selected from O, F, S, P and their any combination；E is selected from Co, Mn and they
Any combination；T is selected from F, S, P and their any combination；G is selected from Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V and it
Any combination；Q is selected from Ti, Mo, Mn and their any combination；I is selected from Cr, V, Fe, Sc, Y and theirs is any
Combination；And J is selected from by V, Cr, Mn, Co, Ni, Cu and their any combination.
In some embodiments, positive electrode active materials are selected from cobalt acid lithium (LiCoO2), lithium nickel cobalt manganese (NCM) ternary material,
LiFePO 4 (LiFePO4), LiMn2O4 (LiMn2O4), nickel ion doped (LiNi0.5Mn1.5O4) or their any combination.
In some embodiments, positive electrode active materials can have a coating on the surface thereof, or can with coating
Another compound mixing.The coating may include from the oxide of coating element, the hydroxide for coating element, coating element
Oxyhydroxide, coat the carbonic acid oxonium salt of element and coat at least one coating element selected in the hydroxyl carbonate of element
Compound.Compound for coating can be amorphous or crystallization.
In some embodiments, the coating element contained in the coating may include Mg, Al, Co, K, Na, Ca, Si, Ti,
V, Sn, Ge, Ga, B, As, Zr or their any combination.Coating can be applied by any method, as long as this method is not right
The performance of positive electrode active materials has an adverse effect.For example, this method may include to any coating well known in the art
Method, such as spraying, impregnating.
Anode active material layer further includes adhesive, and optionally includes conductive material.Adhesive improves positive-active
The combination of material granule to each other, and also improve the combination of positive electrode active materials and collector.
In some embodiments, adhesive includes, but are not limited to: polyvinyl alcohol, hydroxypropyl cellulose, diacetyl fiber
Element, polyvinyl chloride, the polyvinyl chloride of carboxylation, polyvinyl fluoride, the polymer of the oxygen containing ethylidene, polyvinylpyrrolidone, polyurethane,
Butadiene-styrene rubber, the ring that polytetrafluoroethylene (PTFE), poly(vinylidene fluoride), polyethylene, polypropylene, butadiene-styrene rubber, acrylic acid (ester) are changed
Oxygen resin, nylon etc..
In some embodiments, conductive material includes, but are not limited to: the material based on carbon, the material based on metal, conduction
The mixture of polymer and they.In some embodiments, the material based on carbon is selected from natural graphite, artificial graphite, carbon black, second
Acetylene black, Ketjen black, carbon fiber or any combination thereof.In some embodiments, it is fine to be selected from metal powder, metal for the material based on metal
Dimension, copper, nickel, aluminium, silver.In some embodiments, conducting polymer is polyphenylene derivatives.
In some embodiments, collector can be aluminium, but not limited to this.
Anode can be prepared by preparation method well known in the art.For example, anode can obtain by the following method:
Active material, conductive material and adhesive are mixed in solvent, to prepare active material composite, and combined the active material
Object coats on a current collector.In some embodiments, solvent may include N-Methyl pyrrolidone etc., but not limited to this.
4, diaphragm
In some embodiments, the electrochemical appliance of the application is equipped with diaphragm between positive electrode and negative electrode to prevent short circuit.
The material and shape of diaphragm used in the electrochemical appliance of the application are not particularly limited, and can be any public in the prior art
The technology opened.In some embodiments, diaphragm includes the polymer formed by the stable material of the electrolyte to the application or nothing
Machine object etc..
Such as diaphragm may include substrate layer and surface-treated layer.Substrate layer is non-woven fabrics, film or multiple with porous structure
Close film, the material of substrate layer in polyethylene, polypropylene, polyethylene terephthalate and polyimides at least one
Kind.Specifically, polypropylene porous film, polyethylene porous membrane, polypropylene non-woven fabric, polyethylene nonwoven or polypropylene-can be selected
Polyethylene-polypropylene porous composite film.
Surface-treated layer is provided at least one surface of substrate layer, surface-treated layer can be polymeric layer or inorganic
Nitride layer, is also possible to mixed polymer and inorganic matter is formed by layer.
Inorganic layer includes inorganic particle and binder, inorganic particle be selected from aluminium oxide, silica, magnesia, titanium oxide,
Hafnium oxide, tin oxide, ceria, nickel oxide, zinc oxide, calcium oxide, zirconium oxide, yttrium oxide, silicon carbide, boehmite, hydrogen
The combination of one or more of aluminium oxide, magnesium hydroxide, calcium hydroxide and barium sulfate.Binder be selected from Kynoar, partially
Vinyl fluoride-hexafluoropropene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyethylene
Give a tongue-lashing the group of one or more of pyrrolidone, polyvinylether, polymethyl methacrylate, polytetrafluoroethylene (PTFE) and polyhexafluoropropylene
It closes.It include polymer in polymeric layer, the material of polymer includes polyamide, polyacrylonitrile, acrylate polymer, polypropylene
Acid, polyacrylate, polyethylene give a tongue-lashing pyrrolidone, polyvinylether, in Kynoar or poly- (biasfluoroethylene-hexafluoropropylene) extremely
Few one kind.
Four, it applies
According to the electrolyte of the embodiment of the present application, can be used in improving the high rate performance of battery, the holding of room temperature memory capacity
Rate and circulation and high-temperature storage performance are adapted for use in the electronic equipment comprising electrochemical appliance.
The purposes of the electrochemical appliance of the application is not particularly limited, and can be used for well known various uses.Such as it takes down notes
It is this computer, pen input computer, removable computer, e-book player, portable phone, portable facsimile printer, portable multiple
It is print machine, portable printer, wear-type stereophone, video recorder, LCD TV, Portable cleaning machine, portable CD player, mini
CD, transceiver, electronic notebook, calculator, storage card, portable recorder, radio, backup power source, motor, automobile,
Motorcycle, moped, bicycle, luminaire, toy, game machine, clock and watch, electric tool, flash lamp, camera, family
Front yard large-scale battery or lithium-ion capacitor etc..
Illustrate the preparation of lithium metal battery by taking lithium metal battery as an example and in conjunction with specific embodiments below, this field
The skilled person will understand that preparation method described in this application is only example, other any suitable preparation methods are in this Shen
Please in the range of.
Embodiment
Illustrate to carry out Performance Evaluation according to the embodiment and comparative example of the lithium metal battery of the application below.
1, the preparation of lithium metal battery
(1) positive preparation
By positive electrode active materials lithium nickel cobalt manganese (NCM811), conductive agent (SuperConductive carbon), binder gather inclined difluoro
Ethylene is mixed according to weight ratio about 97:1.4:1.6, is added N-Methyl pyrrolidone (NMP), under de-airing mixer effect
Stirring is uniform to system, obtains anode sizing agent, wherein the solid content of anode sizing agent is about 72wt%；Anode sizing agent is uniformly coated
In on plus plate current-collecting body aluminium foil；Drying is dried about under about 85 DEG C of vacuum condition then after cold pressing, cut-parts, cutting
4h obtains anode.
(2) preparation of cathode
By the way of physics roll-in, lithium metal is combined on about 12 μm of negative current collector copper foils of thickness, adjusting is passed through
The pressure of roller makes single side on copper current collector cover lithium, and thickness control is about 50 μm.Then after cut-parts, cutting, it is placed on drying
Argon atmosphere glove box in store it is spare.
(3) preparation of isolation film
Isolation film is used as using with a thickness of about 15 μm of polyethylene (PE).
(4) preparation of electrolyte
In dry argon atmosphere, by each material mixing shown in table 1, formula then is added into obtained mixed solution
Lithium salts shown in M dissolves uniform to get the electrolyte.
Sulphones in electrolyte are selected from formula A or B:
Phosphorus-containing compound in electrolyte is selected from formula C or D:
The compound containing phenyl ring in electrolyte is selected from formula E, F or fluorobenzene:
Fluorine ether compound in electrolyte is selected from formula G or H:
Fluoro ketone compound in electrolyte is selected from Formulas I or J:
Fluorosilicone compounds in electrolyte are selected from formula K:
Additive B in electrolyte is selected from formula L:
Lithium salts in electrolyte is selected from formula M:
Table 1 shows the composition of the electrolyte in each embodiment and comparative example, wherein in electrolyte each substance content
It is calculated for the total weight based on electrolyte.Wherein the weight percent of sulphones and phosphorus-containing compound and be X, addition
The weight percent of agent A is Y.
(5) preparation of lithium metal battery
Anode, isolation film, lithium anode are folded in order, are then superimposed；Soldering polar ear is placed on outer packing plastic-aluminum
In film, by Vacuum Package, standing, chemical conversion (0.02C constant-current charge to 3.3V, then with 0.1C constant-current charge to 3.6V), shaping,
The processes such as volume test obtain Soft Roll lamination lithium metal battery.
Table 1
Wherein "-" expression is not added with the substance.
2, lithium metal battery performance test process
(1) lithium metal battery cycle performance is tested
Lithium metal battery is placed in 45 DEG C of insulating boxs, 30 minutes is stood, lithium metal battery is made to reach constant temperature.It is up to perseverance
The lithium metal battery of temperature is 4.25V with 0.1C constant-current charge to voltage, is then 0.05C with 4.25V constant-voltage charge to electric current, connects
With 0.5C constant-current discharge to voltage 2.8V, this is a charge and discharge cycles.With the capacity that discharges for the first time for 100%, repeatedly into
Row charge and discharge cycles record circulating ring number until stopping test when discharge capacity decays to 80%, as evaluation lithium metal battery
The index of cycle performance.
(2) the big multiplying power of lithium metal battery (1C) discharge performance is tested
At room temperature, lithium metal battery is charged into 4.25V with 0.1C, is then with 4.25V constant-voltage charge to electric current
0.05C, stand 5 minutes, be 2.8V with 0.2C constant-current discharge to voltage, record discharge capacity, using the discharge capacity of 0.2C as
Benchmark.The capacity of test 1C electric discharge: lithium metal battery is charged into 4.25V with 0.1C, then with 4.25V constant-voltage charge to electric current
For 0.05C, 5 minutes are stood, is 2.8V with 1C constant-current discharge to voltage, records discharge capacity.And it calculates capacity according to the following formula and protects
Holdup:
Capacity retention ratio=1C discharge capacity/0.2C discharge capacity × 100%.
(3) lithium metal battery low temperature performance is tested
Furnace temperature is adjusted to 25 DEG C, 5 minutes is stood, lithium metal battery is charged into 4.25V with 0.1C, then with 4.25V perseverance
It is 0.05C that pressure, which charges to electric current, stands 5 minutes, is 2.8V with 0.2C constant-current discharge to voltage, discharge capacity is recorded, by 0.2C
Discharge capacity as benchmark.Lithium metal battery is charged into 4.25V with 0.1C again, then with 4.25V constant-voltage charge to electric current
For 0.05C.Adjusting furnace temperature stands 60 minutes, is 2.8V with 0.2C constant-current discharge to voltage to -10 DEG C, records discharge capacity.And
Capacity retention ratio is calculated according to the following formula:
Discharge capacity × 100% of 0.2C when discharge capacity/25 DEG C of 0.2C when capacity retention ratio=- 10 DEG C.
Table 2 shows the test result of the lithium metal battery of embodiment 1-30 and comparative example 1-2.
Table 2
When in the electricity containing sulphones and phosphorus-containing compound it can be seen from the test result of embodiment 1 and comparative example 1
When the compound containing phenyl ring is added in solution liquid, the cycle performance of lithium metal battery can significantly improve, and can improve lithium gold
Belong to the big multiplying power discharging property and low temperature performance of battery.Equally may be used by the test result of embodiment 2-6,20,21 and 24-30
It, can be significant when the compound containing phenyl ring is added in the electrolyte containing sulphones and phosphorus-containing compound to find out
Improve the cycle performance of lithium metal battery, and the big multiplying power discharging property and low temperature performance of lithium metal battery can be improved.
When in the electricity containing sulphones and phosphorus-containing compound it can be seen from the test result of embodiment 1 and comparative example 2
When solving the compound in liquid on addition phenyl ring containing electron donating group, since the electron cloud that electron donating group improves phenyl ring is close
Degree, can reduce the energy barrier of reduction reaction, the compound containing phenyl ring is made to be more prone to be reduced in cathode.Change containing phenyl ring
It closes object and lithium salts forms a film jointly in negative terminal surface, the SEI of formation more dense uniform, can effectively prevent other solvents and lithium gold
Belong to cathode to react, to improve the cycle life of lithium metal battery.And with the fluorobenzene of electron-withdrawing group on phenyl ring
It is unstable to lithium to close object, coulombic efficiency can be greatly reduced, lithium metal battery can not be applied to as solvent.By embodiment 2-6,
20, the test result of 21 and 24-30 in the electrolyte containing sulphones and phosphorus-containing compound again it can be seen that when being added
When compound on phenyl ring containing electron donating group, the coulombic efficiency and cyclical stability of lithium metal battery can be improved.
It can be seen from the test result of embodiment 7-9 in the electrolyte containing sulphones and phosphorus-containing compound
When fluorine ether compound, fluoro ketone compound or fluorosilicone compounds are added, lithium metal battery equally can significantly improve
Cycle performance, and the big multiplying power discharging property and low temperature performance of lithium metal battery can be improved.
Work as it can be seen from the test result of embodiment 10-19 and 22 and is containing sulphones, phosphorus-containing compound and benzene
Fluorine ether compound, fluoro ketone compound or fluorosilicone are added in the electrolyte of compound on ring containing electron donating group
When compound, when the weight percent of sulphones and phosphorus-containing compound and (X) and the compound containing phenyl ring, fluorine etherificate close
Object, fluoro ketone compound and fluorosilicone compounds weight percent and (Y) meet as follows when requiring: 0.25≤Y/X
≤ 3.5, the viscosity of electrolyte can be effectively reduced in fluorine ether compound, fluoro ketone compound and fluorosilicone compounds, improves
Lithium metal battery dynamic performance.These compounds will not dissolve lithium salts, will not influence lithium salts and sulphones or containing phosphatization
Close object coordination, so reduce be electrolysed fluid viscosity while, will not the circulation coulombic efficiency to lithium metal battery cause
It influences.
It can be seen from the test result of embodiment 3 and embodiment 23 when containing sulphones, phosphorus-containing compound and
After suitable anode additive is added in the electrolyte of compound on phenyl ring containing electron donating group, electrolyte can be in lithium metal
One layer of cathode formation is SEI layers close, can effectively inhibit the growth of Li dendrite, and lithium can be made to deposit more uniform cause
It is close, to improve the circulation coulombic efficiency of battery.
In the whole instruction to " embodiment ", " section Example ", " one embodiment ", " another citing ", " citing ",
The reference of " concrete example " or " some examples ", representated by mean at least one embodiment or citing in this application
Contain special characteristic, structure, material or characteristic described in the embodiment or citing.Therefore, throughout the specification
The description that each place occurs, such as: " in some embodiments ", " in embodiment ", " in one embodiment ", " another
In a citing ", " in a citing ", " in particular examples " or " citing " are not necessarily identical in reference the application
Embodiment or example.In addition, special characteristic herein, structure, material or characteristic can be in any suitable manner one
It is combined in a or multiple 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 (17)
1. a kind of electrolyte, the electrolyte includes sulphones, phosphorus-containing compound and additive A, and the additive A includes
At least one of following compound: the compound containing phenyl ring, fluorine ether compound, fluoro ketone compound and fluorosilicone
Close object.
2. electrolyte according to claim 1, wherein being based on institute when the electrolyte includes the compound containing phenyl ring
The total weight of electrolyte is stated, the weight percent of the compound containing phenyl ring is 6wt%-60wt%.
3. electrolyte according to claim 1, wherein the total weight based on the electrolyte, sulphones and described
The weight percent of phosphorus-containing compound and be X, the weight percent of the additive A is Y, and wherein X and Y meets following item
Part: 0.25≤Y/X≤3.5.
4. electrolyte according to claim 1, wherein the sulphones include at least one in Formulas I or Formula II compound
Kind:
Wherein:
R1And R2It is each independently selected from C6-C26Aryl, halogen, C1-C12Alkyl, C2-C12Alkenyl and C1-C12Halogenated alkyl；
R3Selected from hydrogen, C6-C26Aryl, halogen, C1-C12Alkyl and C1-C12Halogenated alkyl；And
Wherein integer of the n in 1-6.
5. electrolyte according to claim 1, wherein the sulphones include one of following compound or a variety of:
Dimethyl sulfone, vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan), diethyl sulfone, ethylene methacrylic sulfone, Methylethyl sulfone, sulfolane, Thietane -1,1- dioxide or
3- bromine Thietane -1,1- dioxide.
6. electrolyte according to claim 1, wherein the phosphorus-containing compound includes formula III compound:
Wherein:
R4、R5And R6It is each independently selected from C1-C12Alkyl, C2-C12Alkenyl, C2-C12Alkynyl, C1-C12Halogenated alkyl, C2-C12Halogen
For alkenyl, C6-C26Aryl, C6-C26Halogenated aryl and C1-C12Alkoxy.
7. electrolyte according to claim 1, wherein the phosphorus-containing compound includes one of following compound or more
Kind: trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate (chloroethyl) ester, phosphorus
Sour three (bis- chloropropyl of 1,3-) esters or tricresyl phosphate (trifluoroethyl) ester.
8. electrolyte according to claim 1, wherein the compound containing phenyl ring includes formula IV compound:
Wherein R7Selected from C1-C20Alkyl or C1-C20Alkoxy；And
Wherein q is selected from the integer of 1-6.
9. electrolyte according to claim 1, wherein the fluorine ether compound includes one of following compound or more
Kind: HCF2CF2CH2OCF2CF2H、(CF3)2CFCF(CF2CF3)(OCH3)、CF3CHFCF2CH(CH3)OCF2CHFCF3、
HCF2CF2CH2OCF2CF2CF2CF2H、HCF2CF2OCH2CF3、HCF2CF2OCH2CH2OCF2CF2H、
HCF2CF2OCH2CH2CH2OCF2CF2H、HCF2CF2CH2OCF2CF2CF2H、HCF2CF2OCH2CH2OCF2CF2CF2H、
HCF2CF2OCH2CH2CH2OCF2CF2CF2H、CH3OCH2CH2OCH2CH2F、CH3OCH2CH2OCH2CF3、CH3OCH2CH(CH3)
OCH2CH2F、CH3OCH2CH(CH3)OCH2CF3、FCH2CH2OCH2CH2OCH2CH2F、FCH2CH2OCH2CH(CH3)OCH2CH2F、
CF3CH2O(CH2CH2O)2CH2CF3And CF3CH2OCH2CH(CH3)OCH2CF3。
10. electrolyte according to claim 1, wherein the fluoro ketones compound includes Formula V compound:
Wherein R10、R11It is each independently selected from C1-C12Fluoro-alkyl or C2-C12Fluoro alkenyl.
11. electrolyte according to claim 1, wherein the fluoro ketones compound include one of following compound or
It is a variety of: perfluor hexanone, bis- (the trifluoromethy)-propiones of 1,1,1,2,4,5,5,5- octafluoro generation -2,4- or 1,1,1,3,4,4,
4- seven fluoro- 3- (trifluoromethyl) -2- butanone.
12. electrolyte according to claim 1, wherein the fluorosilicone compounds include Formula IV compound:
Wherein R12、R13、R14、R15、R16、R17It is each independently selected from C1-C12Alkyl, C1-C12Fluoro-alkyl, C1-C12Alkenyl or
C2-C12Fluoro alkenyl, and R12、R13、R14、R15、R16、R17At least one of be C1-C12Fluoro-alkyl or C2-C12Fluoro alkene
Base.
13. electrolyte according to claim 1, wherein the fluorosilicone compounds include the bis- (trifluoropropyls of 1,3-
Base) -1,1,3,3- tetramethyl disiloxane, two (13 fluoro- 1,1,2,2- tetrahydro octyl) tetramethyl disiloxanes or combinations thereof.
14. electrolyte according to claim 1 further comprises additive B, wherein the additive B includes as follows
At least one of compound:
Vinylethylene carbonate, vinylene carbonate, fluorinated ethylene carbonate, 4- trifluoromethy ethylene carbonate, dioxalic acid
Lithium borate, difluorine oxalic acid boracic acid lithium, LiBF4, lithium nitrate, methane-disulfonic acid methylene ester, sulfuric acid vinyl ester, sulfurous acid are sub-
Ethyl ester, succinic anhydride, propylene sulfite, acrylic -1,3- sultones, bis- (trimethyl silicon substrate) sulfuric esters, bis- (trimethyls
Silicon substrate) sulfuric ester, N- methyl, butyl pyrrolidine bis-trifluoromethylsulfoandimide salt, N- methyl, the double trifluoro methylsulfonyls Asias of propylpiperdine
Bis- (cyanoethoxyl) ethane of amine salt, 1,3- dioxanes, 1,4- dioxane, 1,2-, adiponitrile, anti-maleic nitrile, cis-butene
Dintrile, succinonitrile, 1,3,5- penta trimethylsilyl nitriles, 1,3,6- own trimethylsilyl nitriles, 2,5- diethyl tetrahydrofuran, trimethylsilyl 2-
(fluorosulfonyl) difluoro acetate or trifluoroacetic acid allyl ester.
15. electrolyte according to claim 14, wherein the total weight based on the electrolyte, the weight of the additive B
Amount percentage is 0.05wt%-10wt%.
16. a kind of electrochemical appliance, wherein the electrochemical appliance includes electricity described in any one of -15 according to claim 1
Solve liquid.
17. a kind of electronic device, wherein the electronic device includes electrochemical appliance according to claim 16.
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