CN105428701B - A kind of electrolyte and the lithium ion battery including the electrolyte - Google Patents
A kind of electrolyte and the lithium ion battery including the electrolyte Download PDFInfo
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- CN105428701B CN105428701B CN201510973386.9A CN201510973386A CN105428701B CN 105428701 B CN105428701 B CN 105428701B CN 201510973386 A CN201510973386 A CN 201510973386A CN 105428701 B CN105428701 B CN 105428701B
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to technical field of lithium ion, specifically, is related to a kind of electrolyte and the lithium ion battery including the electrolyte.The electrolysis of the present invention includes lithium salts, organic solvent and additive A, additive A includes the silane compound containing cyano group and the dinitrile compound with ehter bond, additive A can improve the high rate performance and low temperature performance of battery under high voltages, improve the service life of lithium ion battery.Also contain additive B, one or more of the additive B in ether compound, nitrile compound, the cyclic ester compounds containing sulfur-to-oxygen double bond, the cyclic carbonate compound containing unsaturated carbon carbon bond, the compound containing imido grpup in the electrolyte of the present invention.High-tension target can be realized using the lithium ion battery of electrolyte of the present invention, highest normal working voltage can bring up to 4.4V~5.0V and the cycle performance of lithium ion battery is good, and discharge and recharge has higher capability retention.
Description
Technical field
The present invention relates to technical field of lithium ion, specifically, is related to a kind of electrolyte and including the electrolyte
Lithium ion battery.
Background technology
In recent years, with the fast development of smart electronicses product, the endurance of lithium ion battery is proposed higher
It is required that.In order to improve the energy density of lithium ion battery, exploitation high-voltage lithium ion batteries are one of effective ways.
At present, operating voltage has turned into the heat of numerous R＆D institutions and business research in more than 4.4V lithium ion battery
Point.But under high voltages, the oxidation activity rise of positive electrode, stability decline, and cause nonaqueous electrolytic solution easily in positive pole
Electrochemical oxidation reactions occur for surface, and then decompose and produce gas.Meanwhile the transition metal in positive electrode active materials, example
Reduction reaction can occur for such as nickel, cobalt, manganese and dissolution, so as to cause lithium ion battery chemical property further to deteriorate.At present
Main solution method is that film for additive is added into electrolyte.These additives can be in positive pole film forming, but can cause boundary
Face impedance increase, causes lithium ion mobility kinetics of diffusion performance in battery to reduce, and then cause the multiplying power and cyclicity of battery
Can decay.Prior art disclose a kind of silicon nitrile compounds containing oligomeric ethylene oxide unit as electrolysis additive or
Cosolvent, the electrolyte material for having the advantages that oxidation resistance is strong, dielectric constant is big, thermal safety is high is developed, although this
Class compound can form SEI films in graphite surface, prevent destructions of the PC to graphite electrode, but contain oligo-ether in its structure
Chain, in cell reaction, ether chain easily disconnects, and influences the stability of SEI films, so as to cause battery to reduce.
Therefore, a kind of remain to make lithium ion battery to keep cycle performance, multiplying power and low under high voltages it is necessory to develop
The electrolyte of warm excellent performance.
The content of the invention
In order to solve the above problems, the applicant is studied with keen determination, is as a result found：Include the silanization containing cyano group
The electrolyte of compound and dinitrile compound with ehter bond, after being applied in lithium ion battery, can improve battery in high electricity
The high rate performance and low temperature performance of pressure, the service life of lithium ion battery is improved, so as to complete the application.
The purpose of the application is to provide a kind of electrolyte, including lithium salts, organic solvent, additive, wherein, the addition
Agent A includes the silane compound containing cyano group and the dinitrile compound with ehter bond；
The silane compound structural formula containing cyano group is as shown in formula I：
Wherein, R1、R2、R3It is each independently selected from cyano group, halogen, C1~10Alkyl, C1~10Alkoxy, the halogen are selected from
F、Cl、Br；N is selected from 0~5 integer.
The dinitrile compound structural formula with ehter bond is as shown in formula II：
Wherein, R4、R5、R6It is each independently the alkylidene for being 1~5 selected from carbon number, the Asia that carbon number is 2~5
Alkenyl, m are 1~5 integer.
Also contain additive B in the electrolyte, the additive B is selected from ether compound, nitrile compound, containing sulphur oxygen pair
The cyclic ester compounds of key, the cyclic carbonate compound containing carbon-to-carbon unsaturated bond, one in the compound containing imido grpup
Kind is a variety of.
The another object of the application is to provide a kind of lithium ion battery, including the positive plate containing positive electrode active materials,
The electrolyte provided containing negative active core-shell material negative plate, lithium battery diaphragm and the application.
The electrolysis of the present invention includes lithium salts, organic solvent and additive A, and additive A includes the silane chemical combination containing cyano group
Thing and the dinitrile compound with ehter bond, additive A can improve the high rate performance and low temperature discharge of battery under high voltages
Performance, improve the service life of lithium ion battery.Also contain additive B in the electrolyte of the present invention, additive B is selected from etherificate and closed
Thing, nitrile compound, the cyclic ester compounds containing sulfur-to-oxygen double bond, the cyclic carbonate compound containing carbon-to-carbon unsaturated bond, contain
There are the one or more in the compound of imido grpup, additive B can further improve the cycle performance of lithium ion battery.Using
The lithium ion battery of electrolyte of the present invention can realize high-tension target, highest normal working voltage can bring up to 4.4V~
The cycle performance of 5.0V and lithium ion battery is good, and discharge and recharge has higher capability retention.
Embodiment
It is described in detail below by the application, will becomes more with these explanations with advantage the characteristics of the application
To be clear, clear and definite.
The present invention proposes a kind of electrolyte, including lithium salts, organic solvent and additive A.The additive A includes containing
The silane compound of cyano group and the dinitrile compound with ehter bond；
In above-mentioned electrolyte, the silane compound structural formula containing cyano group is as shown in formula I：
Wherein, R1、R2、R3It is each independently selected from cyano group, halogen, C1~10Alkyl, C1~10Alkoxy, the halogen are selected from
F、Cl、Br；N is selected from 0~5 integer.
Preferably, R1、R2、R3In at least one be cyano group.
Preferably, R1、R2、R3In at least one C1~6Alkoxy.
The preferred upper limit value of the carbon number of abovementioned alkyl is once 8,6,4,3；For example, the higher limit in carbon number is
In the case of 8, the carbon atom number range of alkyl refers to 1~8；The most preferably carbon number of alkyl is 1~6, and further preferred 1
~3.Alkyl can be alkyl group or cycloalkyl：Alkyl group includes straight chained alkyl and the alkyl with side chain；Cycloalkyl is to contain fat
The saturated alkyl of ring structure, substituent can be contained or not contain on alicyclic ring.
Wherein, C1-6Straight or branched alkyl include but is not limited to：-CH3,-CH2CH3,-(CH2)2CH3,-CH (CH3)2,-
(CH2)3CH3,-CH2CH(CH3)2,-CH (CH3)CH2CH3,-CH2CH(CH3)2,-C (CH3)3,-(CH2)4CH3,-CH2CH2CH
(CH3)2,-CH (CH3)CH2CH2CH3,-CH2CH(CH3)CH2CH3,-CH2C(CH3)3,-(CH2)5CH3；
C1~6Alkoxy includes but is not limited to：-OCH3,-OCH2CH3,-O (CH2)2CH3,-OCH (CH3)2,-O (CH2)3CH3,-OCH2CH(CH3)2,-OCH (CH3)CH2CH3,-OCH2CH(CH3)2,-OC (CH3)3,-O (CH2)4CH3,-OCH2CH2CH
(CH3)2,-OCH (CH3)CH2CH2CH3,-OCH2CH(CH3)CH2CH3,-OCH2C(CH3)3,-O (CH2)5CH3。
As the example of the silane compound containing cyano group, referring specifically to following structural formula：
Trimethylsilyl cyanide (AS1)；
The silicon fluoride (AS2) of 2- cyano ethyls methyl two；
Dicyano dimethylsilane (AS3)；
2- cyano ethyls triethoxysilane (AS4).
The dinitrile compound structural formula with ehter bond is as shown in formula II：
Wherein, R4、R5、R6It is each independently and is selected from C1~5Alkylidene, C2~5Alkenylene, m are 1~5 integer；Further
Preferably C1~4Alkylidene, m are 1 or 2.
Preferably, the dinitrile compound with ehter bond is selected from least one of following material：3,5- dioxas-heptan
Dintrile (AM1), 1,4- bis- (cyanoethoxy) butane (AM2), ethylene glycol two (2- cyano ethyls) ether (AM3), diethylene glycol two
(2- cyano ethyls) ether, triethylene glycol two (2- cyano ethyls) ether, tetraethylene glycol two (2- cyano ethyls) ether, (the 2- cyanogen of 1,3- bis-
Base oxethyl) propane (AM4), 1,4- bis- (2- cyanoethoxies) butane, (2- cyanoethoxies) pentanes of 1,5- bis- and ethylene glycol
Two (4- cyanobutyls) ethers.Preferably, the dinitrile compound with ehter bond is ethylene glycol two (2- cyano ethyls) ether.
As the example of the dinitrile compound with ehter bond, referring specifically to following structural formula：
3,5- dioxas-pimelic dinitrile (AM1)
1,4- bis- (cyanoethoxy) butane (AM2)
Ethylene glycol two (2- cyano ethyls) ether (AM3)
1,3- bis- (2- cyanoethoxies) propane (AM4)
It has been investigated that because the electrolyte of the present invention includes the silane compound containing cyano group and has ehter bond
Dinitrile compound, the silane compound containing cyano group preferentially form diaphragm on positive active material surface, due to it and had
Substantial amounts of intermolecular hydrogen bonding effect between the dinitrile compound of ehter bond be present so that the silane compound containing cyano group will not film forming
It is blocked up, and the dinitrile compound with ehter bond is also with positive active material surface with stronger chelation, therefore have
On the one hand the dinitrile compound of ehter bond can slow down film-forming region film forming, on the other hand can promote again non-film-forming region into
Film.Due to good synergy between the two, the composite S EI films formed are fine and close, uniform, and impedance is small, by the electrolyte
After being applied in lithium ion battery, the high rate performance and low temperature performance of battery under high voltages can be improved, improve lithium from
The service life of sub- battery.
In the silane compound containing cyano group shown in above-mentioned formula I, when R contains at least two cyano group, one can be entered
Step improves high rate performance, low temperature performance and the cycle performance of lithium ion battery.
In the present invention, the silane compound containing cyano group can obtain according to the synthetic method of routine, such as can join
See CN201480003489.6, can also be by commercially available；Dinitrile compound with ehter bond can pass through existing synthesis side
Method obtains, reference can be made to CN201280006888.9, can also be by commercially available, its source is not exposed to specific limitation.
In above-mentioned electrolyte, it is preferable that the silane compound containing cyano group and the dinitrile compound with ehter bond combine
Additive level is the 0.01%~10% of the gross weight of electrolyte.It has been investigated that when the combined additive is being electrolysed
When content in liquid is less than 0.01%, electrolyte is not effectively form stable passivating film, the cryogenic property of lithium ion battery
It cannot improve substantially with high rate performance；When the content of the combined additive is more than 10%, the film formed is thicker, and impedance increases
Add, reduce the cycle performance of lithium ion battery.It is further preferred that the total content of the combined additive is the gross weight of electrolyte
1~8%.Wherein, in combined additive, the content of the silane compound containing cyano group and the dinitrile compound with ehter bond
Ratio is unrestricted.
It is further preferred that additive also includes additive B, additive B is selected from ether compound, nitrile compound, contained
The cyclic ester compounds of sulfur-to-oxygen double bond, the cyclic carbonate compound containing carbon-to-carbon unsaturated bond, the compound containing imido grpup
In one or more.
Ether compound is selected from least one of substituted or unsubstituted ether, and substituent is halogen atom, preferably fluorine；Make
For the specific example of ether compound, can enumerate：1- ethyoxyls-propane (EPE), 2- trifluoromethyl -3- methoxyl group perflenapents
(TMMP), fluoro ethyl -2', 2', 3', 3'- the tetrafluoro propyl ethers (F-EPE) of 1,1,2,2- tetra-.In above-mentioned electrolyte, it is preferable that
The content of ether compound is the 0.01~5% of the gross weight of electrolyte, it is further preferred that the content of ether compound is electrolyte
Gross weight 0.1~3%.
The one kind or more of nitrile compound in mono-nitrile compound, double nitrile compounds, three nitrile compounds and four nitrile compounds
Kind, the nitrile compound also includes the nitrile containing unsaturated carbon-carbon double bond；The number of cyano group in nitrile compound can be 1,2
It is individual, 3,4 or 5, such as comprise only the mono-nitrile compound of a cyano group, double nitrile compounds containing two cyano group, contain
Three nitrile compounds of three cyano group, four nitrile compounds containing four cyano group.
As the specific example of nitrile compound, can enumerate：Acetonitrile, propionitrile, butyronitrile, isobutyronitrile, valeronitrile, isobutyl cyanide, 2- first
Base butyronitrile, trimethylacetonitrile, own nitrile, ring valeronitrile, cyclohexanenitrile, acrylonitrile, methacrylonitrile, butene nitrile, 3- methyl butenes nitrile, 2-
Methyl-2-butene nitrile, 2- allyl acetonitriles, 2- methyl -2- allyl acetonitriles, 3- methyl -2- allyl acetonitriles, 2- hexenes nitrile, fluoride acetonitrile, difluoro second
Nitrile, trifluoro acetonitrile, 2- fluorine propionitrile, 3- fluorine propionitrile, 2,2- difluoros propionitrile, 2,3- difluoros propionitrile, 3,3- difluoros propionitrile, 2,2,3- tri-
The mono-nitrile compounds such as fluorine propionitrile, 3,3,3- trifluoros propionitrile, five fluorine propionitrile；Malononitrile, succinonitrile, 2- methyl succinonitrile, tetramethyl
Double nitrile compounds such as succinonitrile, glutaronitrile, 2- methyl cellosolve acetate glutaronitriles, adiponitrile, rich horse dintrile, 2- methylene glutaronitriles；1,3,5-
Three nitrile compounds such as penta trimethylsilyl nitrile, the trimethylsilyl nitriles of 1,2,3- third, the nitrile of 1,3,6- hexanes three；Nitrile compound of TCNE etc. four etc..
Wherein, preferably：Acetonitrile, propionitrile, butyronitrile, valeronitrile, butene nitrile, 3- methyl butenes nitrile, malononitrile, succinonitrile, glutaronitrile, adiponitrile
(ADN), rich horse dintrile, more preferably malononitrile, succinonitrile, glutaronitrile, adiponitrile, rich horse dintrile, the nitrile of 1,3,6- hexane three etc..
In above-mentioned electrolyte, it is preferable that the content containing nitrile compounds is the 0.01~5% of the gross weight of electrolyte, further excellent
Selection of land, the content containing nitrile compounds are the 0.1~3% of the gross weight of electrolyte.
Cyclic ester compounds containing sulfur-to-oxygen double bond can be cyclic sulfates, cyclic sulfite, saturated sultone, contain
The unsaturated sultone of carbon-to-carbon double bond.Such as sulfuric acid vinyl ester, sulfuric acid propylene, propylene sulfite, 1,3- propane sultones
(PS), 1,4- butyl sultones, acrylic -1,3- sultones.In above-mentioned electrolyte, it is preferable that contain sulfur-to-oxygen double bond
The content of cyclic ester compounds is the 0.01~5% of the gross weight of electrolyte, it is further preferred that the ring-type containing sulfur-to-oxygen double bond
The content of ester compounds is the 0.1~3% of the gross weight of electrolyte.
In the cyclic carbonate compound containing carbon-to-carbon unsaturated bond, the carbon-to-carbon unsaturated bond is preferably double bond,
The double bond can be located on ring, can not also be located on ring.Preferably, the cyclic carbonate esterification containing carbon-to-carbon unsaturated bond
Compound is selected from vinylene carbonate (VC), fluorinated ethylene carbonate, fluoro vinylene carbonate, the fluoro vinylene carbonates of 1,2- bis-
One or more in ester, vinylethylene carbonate.In above-mentioned electrolyte, it is preferable that the ring-type containing carbon-to-carbon unsaturated bond
The content of carbonate products is the 0.01~5% of the gross weight of electrolyte, it is further preferred that described contain carbon-to-carbon insatiable hunger
Content with the cyclic carbonates compound of key is the 0.1~3% of the gross weight of electrolyte.
Compound containing imido grpup be selected from containing imine group, carbodiimide groups compound in one kind or
It is a variety of.The imine group is expressed asThe carbodiimide groups are expressed as-N=C=N-, such as：Two hexamethylenes
Base carbodiimide (DCC)；In above-mentioned electrolyte, it is preferable that the content of the compound containing imido grpup is electrolyte
The 0.01~5% of gross weight, it is further preferred that the content of the compound containing imido grpup is the gross weight of electrolyte
0.1~3%.
When also including additive B in additive, the cycle performance of lithium ion battery can be further improved, such as
Under more than 4.45V high pressure after repeatedly circulation, further such that lithium ion battery has higher capability retention, separately
Outside, additionally it is possible to further improve the discharge performance under lithium ion battery multiplying power and low temperature.
In above-mentioned electrolyte, particularly, organic solvent selects non-aqueous organic solvent, it is preferable that carbon number can be selected
For 1~8 and contain at least one ester group compound as non-aqueous organic solvent.
Preferably, the organic solvent is selected from ethylene carbonate, propene carbonate, butylene, fluoro ethylene
Alkene ester, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, 1,4- fourths
At least one of lactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate and ethyl butyrate.Certain not merely office
It is limited to the halogenated compound of the above-mentioned specific compound being previously mentioned or above-mentioned specific compound.
In above-mentioned electrolyte, the lithium salts is optionally from least one of organic lithium salt or inorganic lithium salt.Especially, institute
State in lithium salts containing at least one of fluorine element, boron element, P elements.
As the example of lithium salts, can specifically enumerate：Lithium hexafluoro phosphate LiPF6, difluorophosphate LiPO2F2, tetrafluoro boric acid
Lithium LiBF4, double trifluoromethanesulfonimide lithium LiN (CF3SO2)2(being abbreviated as LiTFSI), double (fluorine sulphonyl) imine lithium Li (N
(SO2F)2) (being abbreviated as LiFSI), di-oxalate lithium borate LiB (C2O4)2(being abbreviated as LiBOB), difluorine oxalic acid boracic acid lithium LiBF2
(C2O4) (being abbreviated as LiDFOB).
In above-mentioned electrolyte, it is preferable that lithium salts may be selected from lithium hexafluoro phosphate, difluorophosphate, LiBF4, hexafluoro
Arsenic acid lithium, lithium perchlorate, trifluoro sulphonyl lithium, two (trimethyl fluoride sulfonyl) imine lithiums, double (fluorine sulphonyl) imine lithiums and three (trifluoros
At least one of sulfonyloxy methyl) lithium methide.
Particularly, the concentration of lithium salts can be 0.5mol/L~3mol/L.
In the present invention, electrolyte is prepared using conventional method, such as each material in electrolyte is mixed
It is even.
Another object of the present invention is to provide a kind of lithium ion battery, including positive plate, negative plate, lithium battery diaphragm and
Electrolyte, wherein, electrolyte is electrolyte of the invention.
In above-mentioned lithium ion battery, positive plate includes positive electrode active materials；The negative plate includes negative active core-shell material,
Wherein, positive electrode active materials, the specific species of negative active core-shell material are not limited specifically, can be selected according to demand
Select.
Preferably, positive electrode active materials are selected from cobalt acid lithium (LiCoO2), lithium-nickel-manganese-cobalt ternary material, LiFePO 4
(LiFePO4), LiMn2O4 (LiMn2O4At least one of).
Preferably, negative active core-shell material is graphite and/or silicon, such as the micro- carbon ball of native graphite, Delanium, interphase
(referred to as MCMB), hard carbon, soft carbon, silicon, silico-carbo compound, Li-Sn alloys, Li-Sn-O alloys, Sn, SnO, SnO2, point it is brilliant
The lithiumation TiO of stone structure2-Li4Ti5O12, Li-Al alloys can be used as negative active core-shell material.
Beneficial effects of the present invention are as follows：
The present invention lithium-ion battery electrolytes by the silane compound containing cyano group and with ehter bond dinitrile compound
Be applied in combination, can reduce thickness and the impedance of positive electrode surface SEI films, improve positive electrode surface formed SEI films homogeneity and
Stability, so as to improve the high rate performance of lithium ion battery and low temperature performance.The lithium ion battery of the present invention can be realized
High-tension target, highest normal working voltage can bring up to 4.4V~5.0V and the cycle performance of lithium ion battery is good, fill
Electric discharge has higher capability retention, improves the service life of lithium ion battery.When also including additive B in additive
When, the cycle performance of lithium ion battery can be further improved, such as circulated under more than 4.45V high pressure by multiple
Afterwards, further such that lithium ion battery has higher capability retention, in addition it is possible to further improve lithium ion battery times
Discharge performance under rate and low temperature.
The application is further described below by way of instantiation.But these examples are only exemplary, not to this
The protection domain of application forms any restrictions.
In following embodiments, comparative example and experimental example, reagent, material and the instrument used be not such as special
Explanation, it is commercially available, wherein used reagent can also be obtained by conventional synthesis process.
Embodiment 1~10
In following embodiments, comparative example and experimental example, used material is as follows：
Organic solvent：Ethylene carbonate (EC), propene carbonate (PC), diethyl carbonate (DEC)；Lithium salts：LiPF6；
Additive A：
Silane compound AS1, AS2, AS3 or AS4 containing cyano group；
Dinitrile compound AM1, AM2, AM3 or AM4 with ehter bond；
The additive S used in comparative example is the silicon nitrile containing oligomeric ethylene oxide unit disclosed in CN104072533A
Compound, i.e., 2- propyl group nitrile ethyoxyl-trimethicone shown in embodiment 1；
Additive B：Fluoro ethyl -2', 2', 3', 3'- the tetrafluoro propyl ethers (F-EPE) of 1,1,2,2- tetra-, vinylene carbonate
(VC), 1,3- propane sultones (PS), adiponitrile (ADN), dicyclohexylcarbodiimide (DCC)；Lithium battery diaphragm：16 microns of thickness
Polypropylene barrier film (model A273, being provided by Celgard companies).
Lithium ion battery (hereinafter referred to as battery) 1~10 is prepared by the following method：
(1) preparation of positive plate
By cobalt acid lithium (LiCoO2), binding agent (Kynoar), conductive agent (acetylene black) according to weight ratio be LiCoO2：
Kynoar：Acetylene black=96:2:2 are mixed, and add 1-METHYLPYRROLIDONE (NMP), under de-airing mixer effect
Stirring obtains anode sizing agent to system into transparent and homogeneous shape；Anode sizing agent is evenly applied on the aluminium foil that thickness is 12 μm；Will
Aluminium foil is transferred to 120 DEG C of oven drying 1h after room temperature is dried, and then obtains positive plate by cold pressing, cutting.
(2) preparation of negative plate
According to weight ratio it is stone by graphite, acetylene black, thickener sodium carboxymethylcellulose (CMC), binding agent butadiene-styrene rubber
Ink：Acetylene black：Binding agent butadiene-styrene rubber：Thickener sodium carboxymethylcellulose (CMC)=95:2:2:1 is mixed, and is added to
After ionized water, under the stirring action of de-airing mixer, cathode size is obtained；Cathode size is coated uniformly on copper foil；Will
Copper foil is transferred to 120 DEG C of oven drying 1h after room temperature is dried, and then obtains negative plate by cold pressing, cutting.
(3) preparation of electrolyte
Electrolyte 1~10 is prepared by the following method：
In water content<In 10ppm argon gas atmosphere glove box, EC, PC and DEC are well mixed and form organic solvent, will
Fully dry lithium salts is dissolved in above-mentioned organic solvent, is then added and is added according to content shown in table 1 respectively in organic solvent
Add agent A (AS1, AS2, AS3, AS4, AM1, AM2, AM3, AM4) and additive B (F-EPE, VC, PS, ADN, DCC), mixing is
It is even, obtain electrolyte.Wherein, the concentration of lithium salts is 1mol/L, and EC, PC, DEC weight ratio are EC：PC：DEC=1:1:2.
(4) preparation of lithium ion battery
Positive plate, lithium battery isolation membrane, negative plate are folded in order, make lithium battery isolation membrane be in positive and negative plate it
Between play a part of isolation, then winding obtain naked battery core；Naked battery core is placed in outer packing paper tinsel, by the above-mentioned electrolysis prepared
Liquid is injected into dried battery, by processes such as Vacuum Package, standing, chemical conversion, shapings, obtains battery.
In the preparation process of above-mentioned battery, used in the electrolyte, each electrolyte selected by each battery
The specific species and its content of silane compound and its content and additive B containing cyano substituent, such as institute in table 1 below
Show.
In table 1, the content of the silane compound containing cyano group is what the gross weight based on electrolyte was calculated
Percetage by weight, the content of other additives are the percetage by weight that the gross weight based on electrolyte is calculated.
Table 1：Comparative example 1-8 and embodiment 1-10 electrolysis additive relevant parameter
Performance test methods：
(1) the cycle performance test of battery
At a temperature of 45 DEG C, embodiment 1-10 and comparative example 1-8 lithium ion battery are filled with 0.5C multiplying power constant current
For electricity to 4.45V, then constant-voltage charge to electric current is 0.05C, then with 0.5C constant current discharges to 3.0V, is so repeated and fills
Electricity and electric discharge, the capability retention after lithium ion battery circulates 50 times, 100 times and 300 times is calculated respectively.
The n capability retention circulated=(discharge capacity of n-th circulation/discharge capacity circulated first) × 100%.
Related data is referring to table 2.
(2) lithium ion battery high rate performance is tested
Embodiment 1-10 and comparative example 1-8 battery are respectively subjected to following tests：By battery with 0.5C constant-current discharges
To 3.0V, 5min is shelved, then with 0.5C constant-current charges to 4.45V, and constant-voltage charge, it is 0.05C by electric current, stands
5min, then respectively with 0.2C, 1C, 1.5C, 2C constant-current discharge to by voltage 3.0V.Under the conditions of record 0.2C, 1C, 1.5C, 2C
Discharge capacity D1, based on the discharge capacity D0 under 0.2C, the discharge capacitance being calculated under different multiplying (surveys 15
Battery, take its average value).Related data is referring to table 3.
The wherein high rate performance of battery=[(D1-D0)/D0] × 100%.
(3) lithium ion battery low temperature performance is tested
At a temperature of 25 DEG C, by each 5 of embodiment 1-10 and comparative example 1-8 lithium ion battery, with 1C/4.45V's
Constant current and constant voltage start to charge up, and charge cutoff electric current is 0.1C, and end electric discharge in 0.5C/3.0V, measure lithium
The initial capacity of ion battery, the lithium ion battery of each Charging state is then respectively put into temperature as -10 DEG C and -20 DEG C of low temperature
In case, place 120 minutes, then with 1C constant-current discharges to 3.0V, record discharge capacity at different temperatures and terminate internal resistance,
The discharge capacity ratio of lithium ion battery under the conditions of calculating Different hypothermia.Related data is referring to table 4.
0.2C discharge capacities at 0.5C discharge capacity/25 DEG C under low temperature discharge capacity ratio=low temperature
Table 2：Comparative example 1-8 and embodiment 1-10 correlated performance test result
Table 3：Comparative example 1-8 and embodiment 1-10 correlated performance test result
Table 4：Comparative example 1-8 and embodiment 1-10 correlated performance test result
Related data in above-mentioned table 2~4 is it is known that compared comparative example 1-8, and comparative example 5-8 is only containing addition
In agent A during a kind of in the silane compound containing cyano group or the dinitrile compound with ehter bond, due to larger into membrane impedance, lead
Capability retention and high rate performance is caused to decline.And in embodiment 1-10, the silane compound containing cyano group and with ehter bond
Dinitrile compound is applied in combination, and can reduce thickness and the impedance of positive electrode surface SEI films, improves positive electrode surface and forms SEI films
Homogeneity and stability, so as to improve the high rate performance of lithium ion battery and low temperature performance.After being circulated at 45 DEG C
Capability retention, high rate performance and low temperature performance are better than comparative example 1-8.
When also including additive B in additive, the cycle performance of lithium ion battery can be further improved, such as
Under more than 4.45V high pressure after repeatedly circulation, further such that lithium ion battery has higher capability retention, separately
Outside, additionally it is possible to further improve the discharge performance under lithium ion battery multiplying power and low temperature.
The announcement of book according to the above description, the application those skilled in the art can also be carried out to above-mentioned embodiment
Appropriate change and modification.Therefore, the application is not limited to embodiment disclosed and described above, to the application's
Some modifications and changes should also be as falling into the protection domain of claims hereof.
Claims (10)
1. a kind of electrolyte, it is characterised in that including lithium salts, organic solvent and additive A, the additive A includes containing cyanogen
The silane compound of base and the dinitrile compound with ehter bond；
The silane compound structural formula containing cyano group is as shown in formula I：
Wherein, R1、R2、R3It is each independently selected from cyano group, halogen, C1~10Alkyl, C1~10Alkoxy, the halogen be selected from F, Cl,
Br；N is selected from 0~5 integer；
The dinitrile compound structural formula with ehter bond is as shown in formula II：
Wherein, R4、R5、R6It is each independently and is selected from C1~5Alkylidene, C2~5Alkenylene, m are 1~5 integer.
2. electrolyte according to claim 1, it is characterised in that in formula I, R1、R2、R3In at least one substituent
For cyano group.
3. electrolyte according to claim 2, it is characterised in that in formula I, R1、R2、R3In at least one substituent
For C1~6Alkoxy.
4. electrolyte according to claim 2, it is characterised in that the silane compound containing cyano group is selected from trimethyl
At least one of cyanogen silane, dicyano dimethylsilane, 2- cyano ethyl triethoxysilanes.
5. electrolyte according to claim 1, it is characterised in that the dinitrile compound with ehter bond is selected from following thing
At least one of matter：3,5- dioxas-pimelic dinitrile, 1,4- bis- (cyanoethoxy) butane, ethylene glycol two (2- cyano ethyls)
Ether, diethylene glycol two (2- cyano ethyls) ether, triethylene glycol two (2- cyano ethyls) ether, tetraethylene glycol two (2- cyano ethyls)
Ether, 1,3- bis- (2- cyanoethoxies) propane, 1,4- bis- (2- cyanoethoxies) butane, 1,5- bis- (2- cyanoethoxies) pentane
With ethylene glycol two (4- cyanobutyls) ether.
6. electrolyte according to claim 1, it is characterised in that the silane compound containing cyano group in the additive A
Total content with the dinitrile compound with ehter bond is the 0.01%~10% of the gross weight of electrolyte.
7. electrolyte according to claim 1, it is characterised in that also contain additive B, the addition in the electrolyte
Agent B is selected from ether compound, nitrile compound, the cyclic ester compounds containing sulfur-to-oxygen double bond, the ring-type carbon containing carbon-to-carbon unsaturated bond
One or more in ester compound, the compound containing imido grpup.
8. electrolyte according to claim 7, it is characterised in that the ether compound is in substituted or unsubstituted ether
At least one, substituent is the substituent containing halogen atom, halogen atom F, Cl, Br；
The one kind or more of the nitrile compound in mono-nitrile compound, double nitrile compounds, three nitrile compounds and four nitrile compounds
Kind；
The cyclic ester compounds containing sulfur-to-oxygen double bond are selected from cyclic sulfates, cyclic sulfite, saturated sultone and contained
There are the one or more in the unsaturated sultone of carbon-to-carbon double bond；
The cyclic carbonate compound containing carbon-to-carbon unsaturated bond is selected from the cyclic carbonates containing carbon-to-carbon double bond
One or more in compound；
The compound containing imido grpup selected from containing imine group, carbodiimide groups compound in one kind or more
Kind.
9. electrolyte according to claim 1, it is characterised in that
The organic solvent is selected from ethylene carbonate, propene carbonate, butylene, fluorinated ethylene carbonate, carbonic acid diformazan
Ester, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, 1,4- butyrolactone, propionic acid first
At least one of ester, methyl butyrate, ethyl acetate, ethyl propionate and ethyl butyrate；
The lithium salts is selected from lithium hexafluoro phosphate, difluorophosphate, LiBF4, double trifluoromethanesulfonimide lithiums, double (fluorine sulphurs
At least one of acyl) imine lithium, di-oxalate lithium borate and difluorine oxalic acid boracic acid lithium.
10. a kind of lithium ion battery, it is characterised in that including the positive plate containing positive electrode active materials, contain negative electrode active material
Negative plate, lithium battery diaphragm and the electrolyte according to any one of claims 1 to 9 of material.
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Families Citing this family (34)
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| CN111682264B (en) * | 2020-06-05 | 2022-04-01 | 惠州锂威新能源科技有限公司 | Electrolyte additive, electrolyte and lithium ion battery |
| WO2022032583A1 (en) * | 2020-08-13 | 2022-02-17 | 宁德新能源科技有限公司 | Electrolyte, electrochemical device comprising same, and electronic device |
| CN112271336B (en) * | 2020-11-25 | 2021-08-27 | 广州天赐高新材料股份有限公司 | Electrolyte and lithium secondary battery |
| CN112670578B (en) * | 2020-12-23 | 2022-11-25 | 东莞新能源科技有限公司 | Electrolyte solution, electrochemical device, and electronic device |
| CN115579522B (en) * | 2022-11-10 | 2023-03-17 | 合肥国轩高科动力能源有限公司 | Electrolyte and lithium ion battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103401021A (en) * | 2013-08-23 | 2013-11-20 | 轻工业化学电源研究所 | Non-aqueous electrolyte and lithium titanate battery |
| CN103858269A (en) * | 2011-07-28 | 2014-06-11 | 和光纯药工业株式会社 | Electrolyte solution for electrochemical devices |
| CN104752769A (en) * | 2015-04-10 | 2015-07-01 | 宁德新能源科技有限公司 | Non-aqueous electrolyte and lithium ion battery utilizing same |
| CN104837850A (en) * | 2013-06-04 | 2015-08-12 | 塞勒创尼克斯公司 | Nitrile-substituted silanes and electrolyte compositions and electrochemical devices containing them |
| CN104956536A (en) * | 2013-09-30 | 2015-09-30 | 株式会社Lg化学 | Lithium secondary battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050106470A1 (en) * | 2003-01-22 | 2005-05-19 | Yoon Sang Y. | Battery having electrolyte including one or more additives |
-
2015
- 2015-12-21 CN CN201510973386.9A patent/CN105428701B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103858269A (en) * | 2011-07-28 | 2014-06-11 | 和光纯药工业株式会社 | Electrolyte solution for electrochemical devices |
| CN104837850A (en) * | 2013-06-04 | 2015-08-12 | 塞勒创尼克斯公司 | Nitrile-substituted silanes and electrolyte compositions and electrochemical devices containing them |
| CN103401021A (en) * | 2013-08-23 | 2013-11-20 | 轻工业化学电源研究所 | Non-aqueous electrolyte and lithium titanate battery |
| CN104956536A (en) * | 2013-09-30 | 2015-09-30 | 株式会社Lg化学 | Lithium secondary battery |
| CN104752769A (en) * | 2015-04-10 | 2015-07-01 | 宁德新能源科技有限公司 | Non-aqueous electrolyte and lithium ion battery utilizing same |
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