CN109309256A - Electrolyte and battery - Google Patents

Electrolyte and battery Download PDF

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Publication number
CN109309256A
CN109309256A CN201710627925.2A CN201710627925A CN109309256A CN 109309256 A CN109309256 A CN 109309256A CN 201710627925 A CN201710627925 A CN 201710627925A CN 109309256 A CN109309256 A CN 109309256A
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China
Prior art keywords
electrolyte
compound
battery
acid
ester
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CN201710627925.2A
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Inventor
湛英杰
史松君
王小梅
张昌明
刘文浩
付成华
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Priority to CN201710627925.2A priority Critical patent/CN109309256A/en
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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
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • 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
    • 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 application relates to the field of energy storage materials, in particular to electrolyte and a battery using the electrolyte. The electrolyte contains an electrolyte, an organic solvent and an additive, wherein the organic solvent contains methyl sec-butyl carbonate, so that the discharging capacity of the battery at low temperature and the storage performance of the battery at high temperature can be improved. In a preferred embodiment, the electrolyte solution of the present application may further include at least one compound having an S ═ O group, and the compound having an S ═ O group acts synergistically with sec-butyl methyl carbonate as an additive, thereby further improving the low-temperature cycle performance of the battery.

Description

A kind of electrolyte and battery
Technical field
This application involves energy storage material fields, in particular, being related to a kind of electrolyte and battery.
Background technique
In the information age of rapid development, the demand to electronic products such as mobile phone, notebook, cameras increases year by year.Two Working power of the primary cell especially lithium ion secondary battery as electronic product has energy density height, memory-less effect, work Make the features such as voltage is high, just gradually replaces traditional Ni-Cd, MH-Ni battery.However as the expansion of electronics market demand And the development of power, energy storage device, requirement of the people to secondary cell are continuously improved, exploitation has high-energy density and meets fast The secondary cell of fast charge and discharge becomes the task of top priority.Currently, effective method is that improve the voltage of electrode active material, compacting close Spend and select suitable electrolyte.
Currently, in a lithium ion secondary battery widely applied electrolyte include using lithium hexafluoro phosphate as electrolytic salt and with Cyclic carbonate and the mixture of linear carbonate are the electrolyte of organic solvent, however above-mentioned electrolyte there are it is many not Foot, specifically at low ambient temperatures, the charge-discharge performance rapid attenuation and high-temperature storage performance of secondary cell are poor.Wherein, Important component of the nonaqueous electrolytic solution as lithium ion battery, there is great influence to it.It can by nonaqueous electrolytic solution Improve the low temperature performance and high-temperature storage performance of battery.
Summary of the invention
In consideration of it, the application provides a kind of electrolyte and the battery using the electrolyte.
In a first aspect, the application provides a kind of electrolyte, it is described organic molten containing electrolyte, organic solvent and additive Agent contains the secondary butyl ester of carbonic acid first.
Optionally, the additive includes at least one of the compound with S=O group.
Optionally, the compound with S=O group is selected from Formulas I, Formula II, formula III, formula IV, Formula V, Formula IV, formula At least one of compound shown in VII, Formula VIII:
Wherein, R11、R12、R21、R22、R31、R32、R41、R42It is independently selected from substituted or unsubstituted C1~C6Alkyl, Substituted or unsubstituted C2~C6Alkenyl, substituted or unsubstituted C2~C6Alkynyl, substituted or unsubstituted C6~C12Aryl；
R5、R6、R7、R8It is independently selected from substituted or unsubstituted C1~C6Alkylidene, substituted or unsubstituted C2~C6 Alkenylene；
Substituent group is selected from halogen, C1~C6Alkyl, C2~C6Alkenyl.
Optionally, the compound with S=O group selects dimethyl sulfite, sulfurous acid diethyl ester, dimethyl sulfone, two Second sulfone, the first and second sulfones, divinyl sulfone, Loprazolam methyl esters, Loprazolam ethyl ester, Loprazolam alkynes propyl ester, methyl benzene sulfonate, sulfuric acid Dimethyl ester, dithyl sulfate, sulfolane, 1,3- propane sultone, 1,4- butyl sultone, acrylic -1,3- sultone, sulfuric acid Vinyl acetate, sulfuric acid acrylic ester, glycol sulfite, sulfurous acid Asia propyl ester, sulfurous acid vinylene.
Optionally, the volume of the secondary butyl ester of carbonic acid first is the 5%~70% of the total volume of the organic solvent；Preferably The 10%~40% of the total volume of the organic solvent.
Optionally, it is described have mass percentage content of the S=O group compound in the electrolyte be 0.001% ~10%, preferably 0.01%~5%, more preferable 0.1%~3%.
Optionally, fluorophosphate salt compound is also contained in the additive.
Optionally, the fluorophosphate salt compound is selected from the double oxalic acid phosphoric acid of single lithium fluophosphate, difluorophosphate, two fluoro At least one of lithium, four fluoro list oxalic acid lithium phosphates.
Optionally, mass percentage content of the fluorophosphate salt compound in the electrolyte be 0.001%~ 3%, preferably 0.01%~1%.
Second aspect, the application provide a kind of battery, including anode pole piece, cathode pole piece, be placed in the anode pole piece and The electrolyte of cathode pole piece the application first aspect.
The technical solution of the application at least has following beneficial effect:
The application is by using the secondary butyl ester of carbonic acid first as organic solvent, so as to improve battery low temperature discharge ability and high temperature Storge quality.
In the preferred technical solution of the application, there is S=O group compound can improve low-temperature circulating performance for addition.
In the preferred technical solution of the application, the additive with S=O group cooperates with work with fluorophosphate salt compound With can further improve the low temperature discharge ability of battery, and further increase the low-temperature circulating performance and high temperature storage of battery Energy.
Specific embodiment
In order to be more clear present invention purpose, technical solution and advantageous effects, with reference to embodiments, The application is further elaborated.It should be understood that embodiment described in this specification is just for the sake of explanation The application, be not intended to limit the application, formula, ratio of embodiment etc. can adaptation to local conditions make a choice and reality had no to result Matter influences.
The following detailed description of the electrolyte and battery according to the embodiment of the present application.
Illustrate the electrolyte according to the embodiment of the present application first aspect first.
In order to achieve the above-mentioned object of the invention, the first aspect of the embodiment of the present application provides a kind of electrolyte, including organic Solvent, electrolytic salt and additive.Wherein, organic solvent contains carbonic ester, especially the secondary butyl ester of carbonic acid first, so as to improve electricity Pond is in low temperature discharge ability and high-temperature storage performance.
(organic solvent)
In the electrolyte according to the embodiment of the present application first aspect, organic solvent contains carbonic ester, especially carbon The sour secondary butyl ester of first；The secondary butyl ester of carbonic acid first has structure below:
The secondary butyl ester of carbonic acid first has wider liquid journey (- 73 DEG C of freezing point, 138.5 DEG C of boiling point), lower viscosity (at 40 DEG C Viscosity 0.74mPas), higher dielectric constant (dielectric constant 2.92c/vn), can be used for improving the cycle performance of battery, Cryogenic property and high-temperature storage performance.
As a kind of improvement of the embodiment of the present application electrolyte, the volume of the secondary butyl ester of carbonic acid first is the total volume of organic solvent 5%~70%.If the content of the secondary butyl ester of carbonic acid first is too low, the liquid journey range of electrolyte solution not can effectively improve, electricity Solving liquid, poor fluidity is volatile at high temperature at low temperature, is unfavorable for battery and works at low or elevated temperatures；If carbonic acid first is secondary The too high levels of butyl ester, then electrolyte dissolution lithium salts is less able, conductivity decline.
The upper limit of the volume percent range of the volume of the secondary butyl ester of the embodiment of the present application carbonic acid first in organic solvent is optional From 70%, 60%, 55%, 50%, 45%, 40%, 35%, 32%, 30%, 28%, 25%, lower limit optionally from 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%.It is further preferred that the volume of the secondary butyl ester compound of first is organic solvent The 10%~40% of total volume.
As a kind of improvement of the embodiment of the present application electrolyte, in organic solvent in addition to the above-mentioned secondary butyl ester of carbonic acid first, may be used also Contain at least one of linear ester, lactone and ether.It wherein, does not include the secondary butyl ester of carbonic acid first in linear ester.
Specific optional, linear ester includes other linear carbonates, straight-chain carboxylic acid's ester；Wherein, other linear carbonates Meaning refer to do not include the secondary butyl ester of carbonic acid first linear carbonate.
Further alternative, linear ester is selected from C1~C8Linear carbonate, C1~C8Straight-chain carboxylic acid's ester.
Specific optional, linear carbonate is selected from dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, dipropyl carbonate At least one of with dibutyl carbonate.
Specific optional, straight-chain carboxylic acid's ester is selected from methyl acetate, ethyl acetate, propyl acetate, methyl propionate, propionic acid second The compound that ester, propyl propionate and above-mentioned carboxylate are replaced or all replaced by the part one or more of F, Cl, Br, I One or more of.
Specific optional, lactone can be selected from gamma-butyrolacton, gamma-valerolactone, alpha-angelica lactone etc.；And gamma-butyrolacton.
It is specific optional, ether can be selected from tetrahydrofuran, 2- methyltetrahydrofuran, Isosorbide-5-Nitrae-dioxanes, 1,2- dimethoxy, 1,2- diethyl oxidative ethane and 1, at least one of bis- fourth oxidative ethane of 2-.
(compound with S=O group)
In the electrolyte according to the embodiment of the present application first aspect, it can add in additive with S=O group At least one of compound.When the secondary butyl ester of carbonic acid first is applied to the secondary cell of high voltage system, it is oxidized easily decomposition, It is unfavorable to the dynamic performance of secondary cell under high temperature environment in use, cathode film formation is thicker.The embodiment of the present application is by adding The additive for entering the group containing S=O can effectively be passivated positive electrode surface, reduce decomposition of the active material to solvent of high oxidation state Effect, so that the chemical property of battery under the high temperature conditions can be improved, such as can be improved the high-temperature storage performance of battery, and can Further improve low-temperature circulating performance.
As a kind of improvement of the embodiment of the present application electrolyte, the compound with S=O group is selected from Formulas I, Formula II, formula At least one of III, formula IV, Formula V, Formula IV, Formula VII, compound shown in Formula VIII:
Wherein, R11、R12、R21、R22、R31、R32、R41、R42It is independently selected from substituted or unsubstituted C1~C6Alkyl, Substituted or unsubstituted C2~C6Alkenyl, substituted or unsubstituted C2~C6Alkynyl, substituted or unsubstituted C6~C12Aryl；
R5、R6、R7、R8It is independently selected from substituted or unsubstituted C1~C6Alkylidene, substituted or unsubstituted C2~C6 Alkenylene；
Substituent group is selected from halogen, C1~C6Alkyl, C2~C6Alkenyl.
As a kind of improvement of the embodiment of the present application electrolyte, R11、R12、R21、R22、R31、R32、R41、R42It is independent Selected from substituted or unsubstituted C1~C3Alkyl, substituted or unsubstituted C2~C4Alkenyl, substituted or unsubstituted C2~C4Alkynyl, Substituted or unsubstituted phenyl；
R5、R6、R7、R8It is independently selected from substituted or unsubstituted C1~C3Alkylidene, substituted or unsubstituted C2~C4 Alkenylene；
Substituent group is selected from halogen, C1~C3Alkyl, C2~C4Alkenyl.
The compound in the embodiment of the present application with S=O group is illustrated separately below:
1, compound shown in Formulas I is straight chain sulfite compounds:
Wherein, R11、R12It is independently selected from C1~C6Alkyl, preferably C1~C3Alkyl.
Specifically, straight chain sulfite compounds can be selected from dimethyl sulfite, sulfurous acid diethyl ester, sulfurous acid dipropyl Ester, dibutyl sulfite, sulfurous acid methyl ethyl ester, however it is not limited to this；
It is preferred that dimethyl sulfite, sulfurous acid diethyl ester.
2, compound straight-chain sulfate compound shown in Formula II:
Wherein, R21、R22It is independently selected from C1~C6Alkyl, preferably C1~C3Alkyl.
Specifically, straight chain sulfate compound can be selected from dimethyl suflfate, dithyl sulfate, dipropyl sulfate, sulfuric acid two Butyl ester, sulfuric acid methyl ethyl ester, however it is not limited to this；
Preferably dimethyl suflfate, dithyl sulfate.
3, compound shown in formula III is sulfonate compound:
Wherein, R31Selected from C1~C6Alkyl, phenyl, preferably C1~C3Alkyl, phenyl；
R32Selected from C1~C6Alkyl, C2~C6Alkenyl, C2~C6Alkynyl, preferably C1~C3Alkyl, C2~C4Alkynyl；
Work as R31When for methyl, Loprazolam methyl esters, Loprazolam ethyl ester, Loprazolam alkynes propyl ester, methane specifically can be selected from Sulfonic acid butyl ester, Loprazolam alkene butyl ester, however it is not limited to this；
Work as R31When for phenyl, methyl benzene sulfonate, ethyl benzenesulfonat, benzene sulfonic acid propyl ester specifically can be selected from, however it is not limited to this；
Preferably Loprazolam methyl esters, Loprazolam ethyl ester, Loprazolam alkynes propyl ester, methyl benzene sulfonate.
4, compound shown in formula IV is straight chain sulfone:
Wherein, R41、R42It is independently selected from C1~C6Alkyl, C2~C6Alkenyl, preferably C1~C3Alkyl, C2~C4Alkene Base.
Specifically, straight chain sulfone can be selected from dimethyl sulfone, diethyl sulfone, dipropyl sulfone, the first and second sulfones, the third sulfone of second, divinyl sulfone, two propylene Sulfone, however it is not limited to this；
Preferably dimethyl sulfone, diethyl sulfone, the first and second sulfones, divinyl sulfone.
5, compound shown in Formula V is cyclic sulfones:
Wherein, R5Selected from C1~C6Alkylidene, preferably C2~C4Alkylidene.
Specifically, cyclic sulfones can be selected from sulfolane, however it is not limited to this.
6, compound shown in Formula IV is sultone:
Wherein, R6Selected from C1~C6Alkylidene, C2~C6Alkenylene, preferably C3~C6Alkylidene, C3~C6Alkenylene；
Specifically, sultone can be selected from 1,3-propane sultone, Isosorbide-5-Nitrae-butyl sultone, acrylic -1,3- sultone, and It is without being limited thereto.
7, compound shown in Formula VII is cyclic sulfates:
Wherein, R7Selected from C1~C6Alkylidene, preferably C2~C5Alkylidene；
Specifically, cyclic sulfates can be selected from sulfuric acid vinyl ester, sulfuric acid acrylic ester, however it is not limited to this.
8, compound shown in Formula VII is cyclic sulfite:
Wherein, R8Selected from C1~C6Alkylidene, preferably C2~C5Alkylidene；
Specifically, cyclic sulfite can be selected from ethylene sulfite, sulfurous acid 1,3- acrylic ester, sulfurous acid 1,2- propylene Ester, however it is not limited to this.
As a kind of improvement of the embodiment of the present application electrolyte, the compound with S=O group is in the electrolyte Mass percentage is 0.001%~10%.If the compounds content with S=O group is too low, electrolyte is changed Kind effect is unobvious, if the compounds content with S=O group is excessively high, the passivation film thickness formed is excessive, and then makes Positive and negative anodes impedance is substantially increased, and battery performance is deteriorated.
As a kind of improvement of the embodiment of the present application electrolyte, the embodiment of the present application has the compound of S=O group in electricity Solve the upper limit of the mass percentage range in liquid optionally from 10%, 9%, 8%, 7%, 6%, 5%, 4.5%, 4%, 3.5%, 3%, 2.5%, 2%, 1.5%, lower limit optionally from 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.3%, 0.5%, 0.6%, 0.8%, 1%, 1.2%.It is further preferred that with S=O group compound in the electrolytic solution hundred Dividing content is 0.01%~5%, more preferable 0.1%~3%.
In above-mentioned general formula:
The alkyl that carbon atom number is 1~6, alkyl can be chain-like alkyl, can also be naphthenic base, on the ring of naphthenic base Hydrogen can be replaced by alkyl, and the preferred lower limit value of carbon atom number is 1,2,3 in the alkyl, and preferred upper limit value is 5,6.It is preferred that Ground, select carbon atom number for 1~4 chain-like alkyl.As the example of alkyl, can specifically enumerate: methyl, ethyl, n-propyl, Isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, 2- Methyl pentyl, 3- first Base-amyl, 1,1,2- trimethyl-propyl, 3,3- dimethyl-butyl.
The alkenyl that carbon atom number is 2~6 can be cyclic alkenyl radical, can also be chain alkenyl.In addition, in alkenyl double bond number Preferably 1.The preferred lower limit value of carbon atom number is 3,4 in the alkenyl, and preferred upper limit value is 5,6.Preferably, carbon is selected Atomicity be 2~5 alkenyl, it is further preferred that select carbon atom number for 2~4 alkenyl.It can specifically enumerate: vinyl, Allyl, isopropenyl, pentenyl.
The alkynyl that carbon atom number is 2~6 can be cyclic alkyne, can also be chain alkynyl.In addition, in alkynyl three keys number Preferably 1.The preferred lower limit value of carbon atom number is 3,4 in the alkynyl, and preferred upper limit value is 5,6.Preferably, carbon is selected Atomicity be 2~5 alkynyl, it is further preferred that select carbon atom number for 2~4 alkynyl.It can specifically enumerate: acetenyl, Propargyl, isopropynyl, pentynyl.
Carbon atom number be 6~12 aryl, such as phenyl, benzene alkyl, such as xenyl of the aryl at least containing a phenyl, Condensed-nuclei aromatics base such as naphthalene, xenyl and condensed-nuclei aromatics base can also be replaced alkyl or alkenyl.Preferably, carbon atom number is selected It can specifically be enumerated for 6~9 aryl: phenyl, benzyl, xenyl, p-methylphenyl, o-tolyl, tolyl.
The alkylidene that carbon atom number is 1~6 is linear chain or branched chain alkylidene, in the alkylidene carbon atom number preferably under Limit value is 2,3, and preferred upper limit value is 4,5,6.Preferably, select carbon atom number for 1~4 alkylidene.Reality as alkyl Example, can specifically enumerate: methylene, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, sub- sec-butyl, Asia penta Base, hexylidene.
The alkenylene that carbon atom number is 2~6 is linear chain or branched chain alkenylene, and the number of double bond is preferably 1 in alkenyl.Institute Stating the preferred lower limit value of carbon atom number in alkenylene is 3,4, and preferred upper limit value is 3,4,5,6.Preferably, carbon atom number is selected For 2~5 alkenylene.It as the example of alkenylene, can specifically enumerate: ethenylidene, acrol, sub- isopropenyl, Asia Alkene butyl, sub- alkene amyl.
Halogen is selected from fluorine, chlorine, bromine, and preferred fluorine.
(fluorophosphate salt compound)
In the electrolyte according to the embodiment of the present application first aspect, fluorophosphates chemical combination can be added in additive Object.
The reaction that positive and negative anodes interface can be participated in by the way that fluorophosphate salt compound is added generates lower solid-state interface film, Especially protection cathode makes carbonate solvent be unlikely to generate thicker SEI with cathode sustained response, can further improve battery Low temperature discharge ability, and further increase the low-temperature circulating performance and high-temperature storage performance of battery.
Particularly, the compound with S=O group is shared with fluorophosphate salt compound, it can be simultaneously positive and negative Pole surface film forming, the synergistic effect of the two make to generate thin, fine and close SEI and CEI in the positive and negative anodes of battery, and then promote electricity The long-term cycle performance and discharge capability in pond.
As a kind of improvement of the embodiment of the present application electrolyte, the metal ion in fluorophosphate salt compound be lithium from Son, as fluorophosphate lithium compound, lithium salts used by the electrolyte in electrolyte is different from fluorophosphate lithium compound Compound.
As a kind of improvement of the embodiment of the present application electrolyte, fluorophosphate lithium compound can be selected from single lithium fluophosphate (Li2PO2F), difluorophosphate (LiPO2F2), two fluoro double oxalic acid lithium phosphates (formula 1), four fluoro list oxalic acid lithium phosphates (formula 2), It is not limited to this.
As a kind of improvement of the embodiment of the present application electrolyte, quality of the fluorophosphate salt compound in the electrolyte Percentage composition is 0.001%~3%.If fluorophosphates compounds content is too low, not to the improvement of electrolyte Obviously, if fluorophosphates compounds content is excessively high, it may appear that the less soluble situation of lithium salts, improvement is limited, simultaneously It also will increase the cost of electrolyte.
As a kind of improvement of the embodiment of the present application electrolyte, the embodiment of the present application fluorophosphate salt compound is in electrolyte In mass percentage range the upper limit optionally from 10%, 9%, 8%, 7%, 6%, 5%, 4.5%, 4%, 3.5%, 3%, 2%, 1.5%, 1.2%, 1%, lower limit optionally from 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.3%, 0.5%, 0.6%, 0.8%.It is further preferred that the percentage composition of fluorophosphate salt compound in the electrolytic solution is 0.01% ~1%.
(electrolytic salt)
As electrolyte used in the embodiment of the present application, following lithium salts can be suitably enumerated.(- 1 class of Li salt)
It can suitably enumerate selected from LiPF6、LiBF4、LiAsF6、LiSbF6、LiPF4(CF3)2、LiPF3(C2F5)3、 LiPF3(CF3)3、LiPF3(iso- C3F7)3And LiPF5(iso- C3F7) one of or two kinds or more " lewis acid and LiF's Complex salt ", wherein it is preferred that LiPF6、LiBF4、LiAsF6, more preferable LiPF6、LiBF4。
(- 2 class of Li salt)
It can suitably enumerate selected from LiN (SO2F)2、LiN(SO2CF3)2、LiN(SO2C2F5)2、(CF2)2(SO2)2NLi (ring-type), (CF2)3(SO2)2NLi (ring-type) and LiC (SO2CF3)3One of or two kinds or more " imines or methylation lithium Salt ", wherein it is preferred that LiN (SO2F)2、LiN(SO2CF3)2Or LiN (SO2C2F5)2, more preferable LiN (SO2F)2Or LiN (SO2CF3)2。
(- 3 class of Li salt)
It can suitably enumerate selected from LiSO3F、LiCF3SO3、CH3SO4Li、C2H5SO4Li、C3H7SO4Li, trifluoro ((first Sulphonyl) oxygroup) one of lithium borate (LiTFMSB) or two kinds or more " contain S (=O)2The lithium salts of O structure ", wherein more It is preferred that LiSO3F、CH3SO4Li、C2H5SO4Li or LiTFMSB.
(- 4 class of Li salt)
It can suitably enumerate and be selected from bis- [oxalate-O, O '] lithium borates (LiBOB), difluoro [oxalate-O, O '] boron " using the oxalates ligand as the lithium salts of anion " of one of sour lithium or two kinds or more, wherein more preferable LiBOB.It can mix One of they or two kinds or more are closed to use.
Wherein, it is preferably selected from LiPF6、LiBF4、LiSO3F, trifluoro ((methylsulfonyl) oxygroup) lithium borate (LiTFMSB), LiN(SO2F)2、LiN(SO2CF3)2、LiN(SO2C2F5)2, one of bis- [oxalate-O, O '] lithium borates (LiBOB) or two kinds More than, more preferably it is selected from LiPF6、LiBF4、LiSO3F, trifluoro ((methylsulfonyl) oxygroup) lithium borate (LiTFMSB), LiN (SO2CF3)2、LiN(SO2F)2With bis- [oxalate-O, O '] lithium borates (LiBOB) and one of or two kinds or more, further it is excellent It is selected as LiPF6。
(manufacture of electrolyte)
The electrolyte of the embodiment of the present application can for example be obtained by following methods: mix above-mentioned organic solvent, thereto Add electrolyte.And the above-mentioned at least one with S=O group compound can be also added thereto, and continue to add thereto In addition stating at least one of fluorophosphate salt compound.
Illustrate the battery according to the embodiment of the present application second aspect below.
According to the battery of the embodiment of the present application, including anode pole piece, cathode pole piece, be placed in anode pole piece and cathode pole piece it Between isolation film and electrolyte.After the electrolyte of the embodiment of the present application is applied in battery, the low temperature of battery can be improved Discharge capability, cycle performance and high-temperature storage performance.It should be noted that the battery of the embodiment of the present application can be lithium ion secondary Battery, sodium ion secondary battery or magnesium ion secondary cell.
When battery is lithium ion secondary battery, positive electrode active materials of the anode comprising that can deviate from, be embedded in lithium ion, cathode Negative electrode active material comprising that can be embedded in, deviate from lithium ion.
Specifically, positive electrode active materials can be selected from cobalt acid lithium (LiCoO when battery is lithium ion secondary battery2), nickel acid Lithium (LiNiO2), the LiMn2O4 (LiMn of spinel-type2O4), the LiMPO of olivine-type4(M in Co, Ni, Fe, Mn, V one Kind or it is several), LiaNixAyB(1-x-y)O2(A, B are each independently selected from one of Co, Al, Mn, and A and B be not identical, and 0.95 ≤ a≤1.2,0 < x < 1,0 < y < 1, and x+y < 1.One or more of).Negative electrode active material can be selected lithium metal, lithium alloy, Carbonaceous material with graphite type crystal structure, the crystal structure can be absorbed and discharge lithium ion or compound tin-oxide. The example of carbonaceous material includes thermally decomposed carbon material, and coke, graphite (for example, electrographite and natural graphite) are burned Organic polymer and carbon fiber.It is preferred that the carbonaceous material with graphite type crystal structure.
When battery is sodium ion secondary battery, positive electrode active materials of the anode comprising that can deviate from, be embedded in sodium ion, cathode Negative electrode active material comprising that can be embedded in, deviate from sodium ion.For example, positive electrode active materials can be selected from sodium iron compound oxide (NaFeO2), sodium cobalt composite oxide (NaCoO2), sodium chromium composite oxides (NaCrO2), sodium manganese composite oxide (NaMnO2)、 Sodium ni compound oxide (NaNiO2), sodium NiTi composite oxides (NaNi1/2Ti1/2O2), sodium nickel manganese composite oxide (NaNi1/ 2Mn1/2O2), sodium ferro manganese composite oxides (Na2/3Fe1/3Mn2/3O2), sodium cobalt-nickel-manganese oxide compound (NaNi1/3Co1/3Mn1/ 3O2), sodium iron phosphate cpd (NaFePO4), sodium manganese phosphate cpd (NaMnPO4), sodium cobalt phosphate cpd (NaCoPO4) etc.. But these materials are not limited to, the conventional known material for being used as sodium-ion battery positive active material can be used. One kind can be only used alone in these positive active materials, can also be used in combination of two or more.Negative electrode active material can be with Selected from carbon materials such as hard carbon, natural graphite, artificial graphite, soft carbon, carbon black, acetylene black, carbon nanotube, graphene, carbon nano-fibers Material.In addition, such as Si, Ge, Pb, In, Zn, H, Ca, Sr, Ba, Ru, Rh can also be enumerated as other negative electrode active materials Deng simple substance, the oxide containing these elements and the carbide of element etc. with sodium generation alloying.But it is not limited to these The conventional known material for being used as sodium ion battery negative can be used in material.These negative electrode active materials One kind can only be used alone, can also be used in combination of two or more.
When battery is magnesium ion secondary cell, positive electrode active materials of the anode comprising that can deviate from, be embedded in magnesium ion, cathode Negative electrode active material comprising that can be embedded in, deviate from magnesium ion.For example, positive electrode active materials can be selected from V2O5、MoO3、MnO2、 TiS2、MoS2It can be selected from magnesium metal, magnesium alloy, graphite etc. Deng, negative electrode active material.But these materials are not limited to, it can be with Use the conventional known material for being used as Magnesium ion battery positive and negative anodes active material.These positive and negative anodes active materials can be only One kind is used alone, can also be used in combination of two or more.
In above-mentioned battery, the specific type of diaphragm is not exposed to specific limitation, can be used in existing battery Any diaphragm material, such as polyethylene, polypropylene, Kynoar and their multilayer complex films, but it is not limited only to these.
Electrolyte is electrolyte described in above-mentioned first aspect.
Among the above, it will include positive electrode active materials, binder and conduction that positive plate, which further includes binder and conductive agent, The anode sizing agent of agent is coated on plus plate current-collecting body, obtains positive plate after anode sizing agent is dry.Likewise, will include cathode The negative electrode slurry of active material, binder and conductive agent is coated on negative current collector, obtains cathode after negative electrode slurry is dry Piece.
By following non-limiting embodiments, the embodiment of the present application is further described.
For ease of description, the additive used in the following embodiments is write a Chinese character in simplified form as follows:
A: the secondary butyl ester of carbonic acid first；
B1:1,3- propane sultone；
B2: sulfuric acid vinyl ester；
C1: difluorophosphate；
The double oxalic acid lithium phosphates of C2: two fluoro.
(1) prepared by positive electrode
By weight it is NCM523 by positive electrode active materials NCM523, conductive agent acetylene black, binder polyvinylidene fluoride: Acetylene black: polyvinylidene fluoride=97:1:2 is mixed, and solvent N-methyl pyrilidone is added, under de-airing mixer effect Stirring, at transparent and homogeneous shape, obtains anode sizing agent to system；Anode sizing agent is evenly applied to the anode collection with a thickness of 12 μm On body aluminium foil；Aluminium foil is transferred to 120 DEG C of oven drying 1h after room temperature is dried, then obtains positive plate by cold pressing, cutting.
(2) preparation of negative electrode material
By negative electrode active material artificial graphite, thickener sodium carboxymethylcellulose (CMC), bonding agent butadiene-styrene rubber according to weight Amount is mixed than 97:1:2, is add to deionized water, is obtained negative electrode slurry under the stirring action of de-airing mixer；It will bear Pole slurry is coated uniformly on the negative current collector copper foil with a thickness of 8 μm；Copper foil is transferred to 120 DEG C of baking ovens after room temperature is dried Then dry 1h obtains negative electrode tab by cold pressing, cutting.
(3) preparation of electrolyte
In water content < 10ppm argon atmosphere glove box, by EC and EMC and the secondary butyl ester of carbonic acid first or DEC according to one Fixed ratio is mixed, and specific ratio is as shown in table 1.Then by sufficiently dry lithium salts LiPF6It is organic to be dissolved in mixing In solvent, additive, LiPF are added later6Concentration remain 1mol/L.The specific type of remaining component and content such as 1 institute of table Show.
(4) preparation of isolation film
Select the polypropylene isolation film of 16 μ m-thicks (model C210 is provided by Celgard company).
(5) preparation of lithium ion secondary battery
Positive plate, isolation film, negative electrode tab are folded in order, isolation film is between positive and negative plate and plays isolation Effect, then winding obtains naked battery core；Naked battery core is placed in outer packing foil, the above-mentioned electrolyte prepared is injected into drying In naked battery core afterwards, by processes such as Vacuum Package, standing, chemical conversion, shapings, lithium ion secondary battery is obtained.
In table 1, the content of organic solvent is the percentage by volume being calculated based on organic solvent total volume, additive Content be the weight percent that is calculated of the total weight based on electrolyte.
1 embodiment of table and comparative example electrolyte composition
Note: "/" expression is not added.
The test process of lithium ion secondary battery will be illustrated next.
(1) the low temperature discharge aptitude tests of lithium ion secondary battery
At 25 DEG C, lithium ion secondary battery is charged into 4.3V and constant-voltage charge to 0.05C according to nominal capacity 0.5C, it is quiet It sets after five minutes, 2.8V is discharged to nominal 0.5C, capacity is denoted as D0 at this time；Standing continues to charge to 4.3V with 0.5C after five minutes And constant-voltage charge discharges by battery core as 0 DEG C according to nominal capacity 0.5C to 0.05C, is discharged to 2.8V, at this time capacity It is denoted as D1；According to identical program, battery core is placed in -20 DEG C and is discharged, discharge capacity at this time is denoted as D2；With Dn/D0's Ratio measures the low temperature discharge ability of low temperature battery core, and value is bigger, and the discharge capability of battery core is stronger.
Four Duplicate Samples are averaged.Experimental result is as shown in table 2.
(2) the low-temperature circulating aptitude tests of lithium ion secondary battery
It with 1C constant-current charge to voltage is 4.3V by lithium ion secondary battery, further with 4.3V constant-voltage charge at 0 DEG C It is 0.05C to electric current, is then 2.8V with 1C constant-current discharge to voltage, is at this time a charge and discharge cycles process, this is put Capacitance is the discharge capacity recycled for the first time.Lithium ion secondary battery is carried out to 300 cycle charging/electric discharges according to the method described above Test, detection obtain the discharge capacity of the 300th circulation.
0 DEG C of lithium ion secondary battery circulation 300 times after capacity retention ratio (%)=(lithium ion secondary battery circulation 300 The discharge capacity that secondary discharge capacity/lithium ion secondary battery recycles for the first time) × 100%.
Every group of the above-mentioned test process lithium ion secondary battery of test four, is averaged.Experimental result is as shown in table 3.
(3) high-temperature storage performance of lithium ion secondary battery
At 25 DEG C, with 0.5C constant-current charge to voltage it is 4.3V by lithium ion secondary battery, is then filled with 4.3V constant pressure Electricity to electric current is 0.05C, tests the volume of lithium ion secondary battery at this time and is denoted as V0；Later by the lithium ion secondary completely filled electricity Pond is put into 70 DEG C of insulating box, and storage is taken out after 30 days, tests the thickness of lithium ion secondary battery at this time and is denoted as V1.Lithium ion 70 DEG C of secondary cell storage 30 days after thickness swelling=[(V1-V0)/V0] × 100%.
Every group of the above-mentioned test process lithium ion secondary battery of test four, is averaged.Experimental result is as shown in table 3.
The low temperature discharge ability of 2 embodiment of table and comparative example
The low-temperature circulating and high-temperature storage performance of 3 embodiment of table and comparative example
It can be learnt from the data of table 2: after the electrolyte of the embodiment of the present application is applied in lithium ion battery, make lithium ion Battery has preferable low temperature discharge ability.
According to the experimental data of embodiment 1-6 it is found that system is in low temperature when increasing the amount of carbonic acid Shuzhong butyl ester to 40% Under dynamics gradually improve, shown preferable discharge capability；The carbonic acid Shuzhong butyl ester for continuing to increase to 70%, because of carbon The viscosity of sour Shuzhong butyl ester is higher than methyl ethyl carbonate, so system does not show dynamic (dynamical) to continue to improve.Comparative example 1-3 Too little or too much without using the secondary butyl ester of carbonic acid first or use, there is biggish downward trend in low temperature discharge ability.
According to the experimental data of embodiment 7-23 it is found that after S=O additive and fluorophosphates share, battery low temperature Discharge capability is further enhanced.Fluorophosphates can form the lower interfacial film of impedance, optimum quantum of utilization in positive and negative anodes 1% or so.The possible reason of the above results is S=O additive impedance with higher itself, for protecting carbonic acid Shuzhong fourth Ester is not oxidized or restores, and low temperature discharge is not helped, but influences low-temperature circulating performance and high-temperature storage performance, in low temperature The combination of lower and fluorophosphates can overcome its disadvantage.It is low when usage amount increase since S=O additive has biggish impedance Warm discharge capability is deteriorated, and as shown in comparative example 4, when the amount of S=O additive is increased to 15wt%, battery is at low temperature almost It can not discharge.Sulfuric acid vinyl ester is lower compared with the third sultone of 1,3- at membrane impedance, so embodiment 14 is compared with 11 discharge capability of embodiment It is slightly good.
It can be learnt from the data of table 3: after the electrolyte of the embodiment of the present application is applied in lithium ion battery, make lithium ion Battery has preferable low-temperature circulating and high-temperature storage performance.
According to the experimental data of embodiment 1-6 it is found that also having very since the secondary butyl ester liquid journey of carbonic acid first is wider in low temperature Good mobility does not easily lead to loop attenuation when battery core polarization increases and leads to low temperature, when increasing usage amount to 40%, not yet See that low-temperature circulating performance significantly deteriorates, and in comparative example when all EMC and EC of solvent or when the secondary butyl ester of a small amount of carbonic acid first is added Dicyandiamide solution has viscosity to increase sharply, and easily polarizes, so loop attenuation is rapid.
According to the experimental data of embodiment 7-14 it is found that S=O additive, which is added, can protect carbonate solvent not in electrode Surface oxidation to guarantee that electrolyte has preferable low-temperature circulating performance, while also avoiding big volume production gas when high temperature storage, mentions The high-temperature storage performance of high battery.But it produces gas to circulation and storage when excessive or very few all to adversely affect, preferably adding proportion It is 0.01 to 3wt.%.
According to the experimental data of embodiment 15-23 it is found that in the electrolyte the secondary butyl ester of first containing carbonic acid and S=O structure simultaneously Additive when, can make secondary cell that there is better low temperature discharge ability and circulation ability, while also have good height Warm storage performance, to promote effect further, fluorophosphates, which are added, in the electrolyte can reduce the impedance of battery core, So that improved effect becomes apparent.This is because fluorophosphates can generate low-impedance SEI film in cathode, which has Good lithium ion conduction ability guarantees that electrolyte is anti-in cathode when cathode is not in analysis lithium and leads to loop attenuation or high temperature Flatulence should be stored.The adding proportion of fluorophosphates is preferably 0.01%~1wt%, and effect is unobvious when very little, too many timeliness Fruit, which improves, to be not obvious, and increases the cost of electrolyte instead.
Other embodiments
Continue to prepare lithium ion secondary battery using the method for above-described embodiment, the composition of electrolyte is as shown in table 4.
In table 4, the content of organic solvent is the percentage by volume being calculated based on organic solvent total volume, additive Content be the weight percent that is calculated of the total weight based on electrolyte.
4 other embodiments electrolyte of table composition
Using low temperature discharge ability, low-temperature circulating performance and the high temperature storage of the battery 11,12 of electrolyte shown in table 4 Can be similar with battery 19, it repeats no more as space is limited.
It is not for limiting claim, any this field skill although the application is disclosed as above with preferred embodiment Art personnel without departing from the concept of this application, can make several possible variations and modification, therefore the application Protection scope should be subject to the range that the claim of this application is defined.

Claims (10)

1. a kind of electrolyte contains electrolyte, organic solvent and additive, which is characterized in that
The organic solvent contains the secondary butyl ester of carbonic acid first.
2. electrolyte according to claim 1, which is characterized in that the additive includes the compound with S=O group At least one of.
3. electrolyte according to claim 2, which is characterized in that the compound with S=O group is selected from Formulas I, formula At least one of II, formula III, formula IV, Formula V, Formula IV, Formula VII, compound shown in Formula VIII:
Wherein, R11、R12、R21、R22、R31、R32、R41、R42It is independently selected from substituted or unsubstituted C1~C6Alkyl, substitution Or unsubstituted C2~C6Alkenyl, substituted or unsubstituted C2~C6Alkynyl, substituted or unsubstituted C6~C12Aryl；
R5、R6、R7、R8It is independently selected from substituted or unsubstituted C1~C6Alkylidene, substituted or unsubstituted C2~C6Sub- alkene Base；
Substituent group is selected from halogen, C1~C6Alkyl, C2~C6Alkenyl.
4. electrolyte according to claim 2, which is characterized in that the compound with S=O group selects sulfurous acid two Methyl esters, sulfurous acid diethyl ester, dimethyl sulfone, diethyl sulfone, the first and second sulfones, divinyl sulfone, Loprazolam methyl esters, Loprazolam ethyl ester, first Alkyl sulfonic acid alkynes propyl ester, methyl benzene sulfonate, dimethyl suflfate, dithyl sulfate, sulfolane, 1,3- propane sultone, 1,4- fourth sulphur Acid lactone, acrylic -1,3- sultone, sulfuric acid vinyl ester, sulfuric acid acrylic ester, glycol sulfite, sulfurous acid Asia propyl ester, sulfurous Sour vinylene.
5. electrolyte according to claim 1, which is characterized in that the volume of the secondary butyl ester of carbonic acid first is described organic molten The 5%~70% of the total volume of agent；The 10%~40% of the total volume of the preferably described organic solvent.
6. electrolyte according to claim 2, which is characterized in that described to have S=O group compound in the electrolyte In mass percentage content be 0.001%~10%, preferably 0.01%~5%, more preferable 0.1%~3%.
7. electrolyte according to claim 1 or 2, which is characterized in that also contain fluorophosphate salinization in the additive Close object.
8. electrolyte according to claim 7, which is characterized in that the fluorophosphate salt compound is selected from single fluorophosphoric acid At least one of the double oxalic acid lithium phosphates of lithium, difluorophosphate, two fluoro, four fluoro list oxalic acid lithium phosphates.
9. electrolyte according to claim 7, which is characterized in that the fluorophosphate salt compound is in the electrolyte Mass percentage content be 0.001%~3%, preferably 0.01%~1%.
10. a kind of battery, including anode pole piece, cathode pole piece, be placed between the anode pole piece and the cathode pole piece every From film and electrolyte, which is characterized in that the electrolyte is electrolyte described in claim 1~9 any claim.
CN201710627925.2A 2017-07-28 2017-07-28 Electrolyte and battery Pending CN109309256A (en)

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CN110556580A (en) * 2019-10-15 2019-12-10 骆驼集团武汉光谷研发中心有限公司 Start-stop battery electrolyte and lithium ion battery
CN110911752A (en) * 2019-12-06 2020-03-24 广州天赐高新材料股份有限公司 Low-internal-resistance lithium secondary battery electrolyte and lithium secondary battery
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CN116259827A (en) * 2021-12-10 2023-06-13 张家港市国泰华荣化工新材料有限公司 Sodium-manganese primary cell
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CN115513528A (en) * 2022-11-21 2022-12-23 广州天赐高新材料股份有限公司 Nonaqueous electrolyte solution and secondary battery
CN115513528B (en) * 2022-11-21 2023-05-05 广州天赐高新材料股份有限公司 Nonaqueous electrolyte and secondary battery

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Application publication date: 20190205