CN109411813B - Electrolyte and electrochemical energy storage device - Google Patents

Electrolyte and electrochemical energy storage device Download PDF

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CN109411813B
CN109411813B CN201710706665.8A CN201710706665A CN109411813B CN 109411813 B CN109411813 B CN 109411813B CN 201710706665 A CN201710706665 A CN 201710706665A CN 109411813 B CN109411813 B CN 109411813B
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electrolyte
quaternary ammonium
formula
energy storage
storage device
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CN109411813A (en
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王小梅
史松君
湛英杰
刘文浩
付成华
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Contemporary Amperex Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M10/42—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • 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 provides an electrolyte and an electrochemical energy storage device. The electrolyte includes an electrolyte salt and an additive. The additive comprises phosphate ester quaternary ammonium salt and cyclic sulfate ester. The synergistic effect of the two can enable the surfaces of the anode and the cathode of the electrochemical energy storage device to generate a layer of compact, uniform and stable passive film, especially a low-impedance and compact solid electrolyte interface film can be formed on the surface of the cathode, so that the contact between the anode and the cathode and the electrolyte can be reduced, the continuous oxidation and reduction reactions of the electrolyte on the surfaces of the anode and the cathode can be avoided, the decomposition of the electrolyte and the increase of the internal resistance of the electrochemical energy storage device can be further weakened, and the electrochemical energy storage device still has better high-temperature cycle performance and lower direct current resistance under high-pressure, solid and thick coating.

Description

Electrolyte and electrochemical energy storage device
Technical Field
The application relates to the field of energy storage devices, in particular to electrolyte and an electrochemical energy storage device.
Background
In recent years, with the increasing problems of global environmental deterioration and energy shortage, the lithium ion battery using the non-aqueous electrolyte has a dramatically increased use demand, and particularly has a dominant position in the high-end consumer electronics field and the electric transportation vehicle field, which have high requirements for energy density, due to higher specific energy density, better cycle performance, wider operating temperature and more friendly environmental compatibility, compared with the conventional nickel-hydrogen, nickel-cadmium and lead-acid batteries.
In order to meet the requirements of people on higher energy density, a positive and negative electrode plate treatment process adopting high compaction and thick coating is a general strategy for improving the energy density of the lithium ion battery in the industry. However, the problem that the nonaqueous electrolyte is difficult to completely infiltrate gaps between active material particles on a highly compacted and thick coated positive and negative electrode plates is caused, and the improvement of the coating weight of the active material on a unit current collector leads to the serious deterioration of the dynamic performance of the lithium ion battery, so that the lithium ion battery has large ohmic polarization during charging and discharging (particularly in a low-temperature environment), and finally, various performances of the lithium ion battery are rapidly deteriorated, for example, the mobility of lithium ions is seriously influenced, so that the lithium ion battery has the phenomena of poor rate capability, poor low-temperature performance and the like.
Therefore, it is desirable to provide an electrolyte solution that can improve the performance of a lithium ion battery after being applied to a lithium ion battery with high compaction and thick coating.
Disclosure of Invention
In view of the problems in the background art, the present invention is directed to an electrolyte and an electrochemical energy storage device having good high temperature cycle performance and low direct current resistance even under high-pressure thick coating.
In order to achieve the above object, in one aspect of the present invention, there is provided an electrolyte solution including an electrolyte salt and an additive. The additive comprises phosphate ester quaternary ammonium salt and cyclic sulfate ester.
In another aspect of the invention, an electrochemical energy storage device is provided that includes an electrolyte as described in one aspect of the present application.
Compared with the prior art, the invention has the beneficial effects that:
the electrolyte additive comprises phosphate quaternary ammonium salt and cyclic sulfate, and the synergistic effect of the phosphate quaternary ammonium salt and the cyclic sulfate can enable the positive and negative electrode surfaces of the electrochemical energy storage device to generate a layer of compact, uniform and stable passive film, especially can form a low-impedance and compact solid electrolyte interface film on the negative electrode surface, so that the contact between the positive electrode and the negative electrode and the electrolyte can be reduced, the continuous oxidation and reduction reaction of the electrolyte on the positive and negative electrode surfaces can be avoided, the decomposition of the electrolyte and the increase of the internal resistance of the electrochemical energy storage device can be further weakened, and the electrochemical energy storage device still has good high-temperature cycle performance and low direct-current resistance under high-pressure solid-thickness coating.
Detailed Description
The electrolyte and electrochemical energy storage device according to the present invention are described in detail below.
First, the electrolytic solution according to the first aspect of the invention is explained.
The electrolyte according to the first aspect of the present application includes an electrolyte salt and an additive. The additive comprises phosphate ester quaternary ammonium salt and cyclic sulfate ester.
In the electrolyte according to the first aspect of the present application, the quaternary ammonium phosphate salt is selected from one or more compounds represented by formula 1; in formula 1, R11、R12Each independently selected from one of substituted or unsubstituted C1-C6 alkyl and substituted or unsubstituted C6-C16 monocyclic aryl; r13One selected from substituted or unsubstituted C1-C12 alkylene; r14One selected from substituted or unsubstituted C1-C6 alkyl; r15One selected from substituted or unsubstituted C1-C3 alkylene; at R11、R12、R13、R14、R15In the formula, the substituent is selected from one or more of C1-C3 alkyl and halogen.
Figure BDA0001381654750000021
In the formula 1, the first and second groups,
Figure BDA0001381654750000022
it is meant an anion, and it is meant,
Figure BDA0001381654750000023
is selected from F-、[PF6]-、[AsF6]-、[BF4]-、[NO3]-、[ClO4]-、
Figure BDA0001381654750000031
Figure BDA0001381654750000032
Figure BDA0001381654750000033
One kind of (1).
In the electrolyte solution according to the first aspect of the present application, the cyclic sulfate ester contains-O-SO2-O-group cyclic compound, preferably, said-O-SO2the-O-group is located on the ring of the cyclic compound. Specifically, the cyclic sulfate may be one of a five-membered cyclic compound, a six-membered cyclic compound, a seven-membered cyclic compound, and an eight-membered cyclic compound. Preferably, the compound can be one of a five-membered cyclic compound, a six-membered cyclic compound and an eight-membered cyclic compound. Further preferably, the compound is one of a five-membered cyclic compound and a six-membered cyclic compound. Where there are several atoms in the ring, the ring is referred to as a "several-membered ring". Specifically, the cyclic sulfate can be selected from one or more compounds shown in formula 2 and formula 3; in formula 2, n is an integer of 1 to 3, R21、R22、R23、R24Each independently selected from one of H, F, Cl, Br, I, cyano-group, carboxyl, sulfonic group, alkane or halogenated alkane of C1-C20, unsaturated alkyl or halogenated unsaturated alkyl of C2-C20; in formula 3, m is an integer of 0 to 3, R31、R32、R33、R34Each independently selected from one of H, F, Cl, Br, I, cyano-group, carboxyl group, sulfonic group, alkane or halogenated alkane of C1-C20, and unsaturated hydrocarbon or halogenated unsaturated hydrocarbon of C2-C20.
Figure BDA0001381654750000041
In the electrolyte according to the first aspect of the present application, the electrolyte may be a liquid electrolyte, a solid polymer electrolyte, or a gel polymer electrolyte. Since the liquid electrolyte has a similar action mechanism to that of the solid polymer electrolyte and the gel polymer electrolyte, the liquid electrolyte is merely exemplified in the present application.
In the electrolyte according to the first aspect of the present application, the phosphate quaternary ammonium salt and the cyclic sulfate ester cooperate to form a layer of compact, uniform and stable anode and cathode surfaces of the electrochemical energy storage deviceThe passivation film, especially the solid electrolyte interface film (SEI film) with low impedance and compactness can be formed on the surface of the negative electrode, so that the contact between the positive electrode and the negative electrode and the electrolyte can be reduced, the continuous oxidation and reduction reaction of the electrolyte on the surfaces of the positive electrode and the negative electrode can be avoided, the decomposition of the electrolyte and the internal resistance rise of the electrochemical energy storage device can be weakened, and the electrochemical energy storage device has better high-temperature cycle performance and lower direct-current resistance. The reason is that when the electrochemical energy storage device is formed, a passivation film can be formed on the surfaces of the positive electrode and the negative electrode, and when the electrolyte contains the phosphate ester quaternary ammonium salt, the phosphate ester quaternary ammonium salt has a special cationic structure, namely, the phosphate ester quaternary ammonium salt is formed by connecting a cyclic quaternary ammonium head with unit positive charge and a functional phosphate ester tail through an organic carbon chain in the middle. The tail part of the phosphate is hydrophilic, and the head part of the annular quaternary ammonium is lipophilic, so that the amphiphilic structures of the head and the tail are respectively oleophylic and hydrophilic, which is favorable for reducing the surface tension of the electrolyte, and the electrolyte can quickly and uniformly permeate into each gap position among porous electrode active material particles on the positive electrode sheet and the negative electrode sheet. The head of the cyclic quaternary ammonium with unit positive charge can drive the whole cation to actively approach the negative electrode to be preferentially reduced, decomposed and broken under the action of an internal electric field formed during formation of the electrochemical energy storage device, and release a functional phosphate tail part to establish a layer of phosphate salt XOP (O) (OR) on the surface of the negative electrode2The SEI film formed by substances such as (X represents metal) and the like has the characteristics of compact internal structure, low impedance, uniform compactness, excellent high and low temperature performance and the like due to the fact that alkyl phosphate has high intrinsic ionic conductivity and high thermal stability, and is very suitable for designing electrode plates with high compaction and thick coating, so that the purposes of improving the high-temperature cycle performance and the direct current resistance of an electrochemical energy storage device can be achieved; the cyclic sulfate can form a film on the surface of the anode, and the formed passivation film can avoid the oxidation reaction between the electrolyte and the anode, so that the high-temperature cycle performance of the electrochemical energy storage device is further improved. Therefore, when the quaternary ammonium salt of phosphate ester and the cyclic sulfate ester are added into the electrolyte at the same time, the electrochemical energy storage device has better high-temperature storage cycle performance under the synergistic action of the quaternary ammonium salt of phosphate ester and the cyclic sulfate ester, particularly the electrochemical energy storage device has better high-temperature storage cycle performanceThe electrochemical energy storage device has cycle performance at 40-60 ℃, and simultaneously has lower direct current impedance under high-compaction-thickness coating.
In the electrolyte according to the first aspect of the present application, in formula 1, preferably, R11Selected from one of substituted or unsubstituted C1-C6 alkyl or halogenated alkyl, R12One kind selected from substituted or unsubstituted C1-C12 alkylene, R13Selected from one of substituted or unsubstituted C1-C6 alkyl or halogenated alkyl, R14One selected from substituted or unsubstituted C1-C2 alkylene.
In the electrolyte according to the first aspect of the present application, in formula 1, the cationic group of the quaternary ammonium salt of phosphoric acid ester may be selected from
Figure BDA0001381654750000051
Figure BDA0001381654750000052
One kind of (1).
In the electrolyte according to the first aspect of the present application, specifically, the phosphate ester quaternary ammonium salt may be selected from one or more of the following compounds, but the present application is not limited thereto;
Figure BDA0001381654750000061
1-1 part of,
Figure BDA0001381654750000062
1-2 of a compound,
Figure BDA0001381654750000063
1-3 of the compound,
Figure BDA0001381654750000064
1-4 of compound,
Figure BDA0001381654750000065
1-5 parts of compound,
Figure BDA0001381654750000066
1-6 parts of compound,
Figure BDA0001381654750000067
1 to 7 of compound,
Figure BDA0001381654750000068
Compounds 1-8.
In the electrolyte according to the first aspect of the present application, in formula 2, n is preferably an integer within 1 to 2.
In the electrolyte according to the first aspect of the present application, in formula 2, R21、R22、R23、R24May be different from each other or completely the same, or R21、R22、R23、R24Are the same or are R21、R22、R23、R24Any three of them are the same.
In the electrolyte according to the first aspect of the present application, in formula 2, when n is an integer of 2 or more, R is not bonded to the substituent21、R22The substituents on the remaining carbon atoms other than the carbon atoms in (b) may be the same or different, or two or more substituents may be the same, and are not limited by specific reference numerals. For example, when n is 2, except that the substituent R is attached21、R22The four substituents on the remaining two carbon atoms other than the carbon atom(s) in (b) may be completely the same or different, or two or more of the four substituents may be the same.
In the electrolyte according to the first aspect of the present application, in formula 3, m is preferably an integer of 0 to 1.
In the electrolyte according to the first aspect of the present application, in formula 3, R31、R23、R33、R34May be different from each other or completely the same, or R31、R23、R33、R34Any two ofIs the same as or R31、R23、R33、R34Any three of them are the same.
In the electrolyte according to the first aspect of the present application, in formula 3, when m is an integer of 2 or more, R is not bonded to the substituent31、R32The substituents on the remaining carbon atoms other than the carbon atoms in (b) may be the same or different, or two or more substituents may be the same, and are not limited by specific reference numerals. For example, when m is 2, except that a substituent R is attached31、R32The four substituents on the remaining two carbon atoms other than the carbon atom(s) in (b) may be completely the same or different, or two or more of the four substituents may be the same.
In the electrolyte solution according to the first aspect of the present application, in formulas 2 and 3, specific types of the alkane group having from C1 to C20 are not particularly limited, and may be, for example, a chain alkane group or a cyclic alkane group. Among them, the chain alkyl group includes a straight chain alkyl group and a branched chain alkyl group. Preferably, the C1-C20 alkane is selected from straight-chain alkane. More preferably, an alkyl group having 1 to 10 carbon atoms is selected, still more preferably, an alkyl group having 1 to 5 carbon atoms is selected, and yet more preferably, an alkyl group having 1 to 3 carbon atoms is selected. Specifically, the C1 to C20 alkyl group may be one selected from methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, heptyl, cycloheptyl, octyl, cyclooctyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl groups.
In the electrolyte according to the first aspect of the present application, in the formula 2 and the formula 3, the number of halogen atoms in the halogenated alkyl group having C1 to C20 and the position thereof are not particularly limited, and a part of or all of the hydrogen atoms in the alkyl group having C1 to C20 may be substituted according to actual requirements. For example, the number of halogen atoms on the C1-C20 alkane group may be 1,2, 3 or 4. Preferably, the halogen atoms are selected from one or two of F, Cl. When the number of halogen atoms is 2 or more, the halogen atoms may be the same or different from each other, or may be partially the same. Preferably, the C1-C20 haloalkyl group can be selected from
Figure BDA0001381654750000081
One kind of (1).
In the electrolyte according to the first aspect of the present invention, the specific type of the unsaturated hydrocarbon group having C2-C20 in formula 2 and formula 3 is not particularly limited, and may be selected according to actual needs. Preferably, a chain unsaturated hydrocarbon group is selected. Further preferably, alkenyl and alkynyl groups are selected. The number of unsaturated bonds in the unsaturated hydrocarbon group and the position of the unsaturated bond are not particularly limited and may be selected according to the actual circumstances. For example, the number of unsaturated bonds may be 1,2, 3, or 4. Preferably, the unsaturated bond is located at the terminal of the unsaturated hydrocarbon group, wherein the terminal is a position away from the attachment of the unsaturated hydrocarbon group to the ring. For example, when the number of unsaturated bonds is 1, the unsaturated bonds are located at the terminal of the unsaturated hydrocarbon group, and when the number of carbon atoms of the unsaturated hydrocarbon group is 3 or more, the carbon atoms of the unsaturated bonds are not bonded to the ring. Preferably, an unsaturated hydrocarbon group having 2 to 10 carbon atoms is selected, more preferably, an unsaturated hydrocarbon group having 2 to 5 carbon atoms is selected, and still more preferably, an unsaturated hydrocarbon group having 2 to 3 carbon atoms is selected. Specifically, the unsaturated hydrocarbon group may be-CH ═ CH2、-CH2-CH＝CH2、-CH2CH2CH＝CH2、-CH2CH2CH2CH＝CH2、-C≡CH、-CH2-C≡CH、-CH2CH2-C≡CH、-CH2CH2CH2C≡CH、-CH＝CH-CH＝CH2One kind of (1).
In the electrolyte solution according to the first aspect of the present invention, the number and position of halogen atoms in the halogenated unsaturated hydrocarbon group of C2-C20 in the formulas 2 and 3 are not particularly limitedFurther, the unsaturated hydrocarbon group having 2 to 20 carbon atoms may be partially or entirely substituted with hydrogen atoms according to actual requirements. For example, the number of halogen atoms may be 1,2, 3 or 4. Preferably, the halogen atoms are one or two of F, Cl. When the number of halogen atoms is 2 or more, the halogen atoms may be the same or different from each other, or may be partially the same. Preferably, the halogenated unsaturated hydrocarbon radical of C2-C20 is chosen from-C.ident.C-X, -CH2—C≡C—X、—CH2CH2—C≡C—X、—CH2CH2CH2—C≡C—X、
Figure BDA0001381654750000091
Figure BDA0001381654750000092
Wherein, X is one of F, Cl, Br and I.
In the electrolyte according to the first aspect of the present application, in formulae 2 and 3, R is preferably21、R22、R23、R24、R31、R32、R33、R34Each independently is one of alkyl or halogenated alkyl selected from H, F, Cl, C1-C10, unsaturated alkyl or halogenated unsaturated alkyl selected from C2-C10, wherein halogen atoms are selected from F or Cl. Further preferably, R21、R22、R23、R24、R31、R32、R33、R34Each independently is one of alkyl or halogenated alkyl selected from H, C1-C5, unsaturated alkyl or halogenated unsaturated alkyl selected from C2-C5, wherein halogen atoms are selected from F or Cl. Even more preferably, R21、R22、R23、R24、R31、R32、R33、R34Each independently is one selected from the group consisting of an alkane group of H, C1 to C3 and an unsaturated hydrocarbon group of C2 to C3, and further preferably R21、R22、R23、R24、R31、R32、R33、R34Each independently selected from one of alkyl groups of H, C1-C3, alkenyl groups of C2-C3 and alkynyl groups of C2-C3.
In the electrolyte according to the first aspect of the present application, specifically, the cyclic sulfate may be selected from one or more of the following compounds;
Figure BDA0001381654750000093
a compound 2-1,
Figure BDA0001381654750000094
A compound 2-2,
Figure BDA0001381654750000095
2-3 of the compound,
Figure BDA0001381654750000096
2-4 of the compound,
Figure BDA0001381654750000097
2-5 parts of compound,
Figure BDA0001381654750000098
2-6 of the compound,
Figure BDA0001381654750000101
2 to 7 of the compound,
Figure BDA0001381654750000102
2 to 8 portions of compound,
Figure BDA0001381654750000103
2 to 9 of the compound,
Figure BDA0001381654750000104
2 to 10 portions of compound,
Figure BDA0001381654750000105
2 to 11 of the compound,
Figure BDA0001381654750000106
2 to 12 portions of compound,
Figure BDA0001381654750000107
2-13 of the compound,
Figure BDA0001381654750000108
2 to 14 portions of compound,
Figure BDA0001381654750000109
2 to 15 portions of compound,
Figure BDA00013816547500001010
2-16 parts of compound,
Figure BDA00013816547500001011
2 to 17 of compound,
Figure BDA00013816547500001012
2 to 18 portions of compound,
Figure BDA00013816547500001013
2 to 19 portions of compound,
Figure BDA00013816547500001014
2 to 20 portions of compound,
Figure BDA00013816547500001015
2-21 parts of compound,
Figure BDA00013816547500001016
2 to 22 portions of compound,
Figure BDA00013816547500001017
2 to 23 of the compound,
Figure BDA00013816547500001018
2 to 24 portions of compound,
Figure BDA0001381654750000111
2 to 25 portions of compound,
Figure BDA0001381654750000112
2 to 26 of compound,
Figure BDA0001381654750000113
Compounds 2-27,
Figure BDA0001381654750000114
2 to 28 portions of compound,
Figure BDA0001381654750000115
2 to 29 of compounds,
Figure BDA0001381654750000116
2 to 30 portions of compound,
Figure BDA0001381654750000117
2 to 31 portions of compound,
Figure BDA0001381654750000118
2 to 32 portions of compound,
Figure BDA0001381654750000119
2 to 33 portions of compound,
Figure BDA00013816547500001110
2 to 34 portions of compound,
Figure BDA00013816547500001111
2 to 35 portions of compound,
Figure BDA00013816547500001112
2 to 36 portions of compound,
Figure BDA00013816547500001113
2-37 parts of compound,
Figure BDA00013816547500001114
Compounds 2-38,
Figure BDA00013816547500001115
Compounds 2-39,
Figure BDA00013816547500001116
And 2-40.
In the electrolyte according to the first aspect of the present disclosure, the content of the quaternary ammonium phosphate is too small, which may not significantly improve the wettability of the electrolyte and the film-forming effect on the surface of the negative electrode; and the excessive content of the electrolyte can cause the viscosity of the electrolyte to be remarkably increased and the ionic conductivity to be remarkably reduced, thereby sharply deteriorating various dynamic properties of the electrochemical energy storage device. Preferably, the content of the phosphate ester quaternary ammonium salt is 0.01-10% of the total mass of the electrolyte.
In the electrolyte according to the first aspect of the present application, the content of the cyclic sulfate is not particularly limited, and may be selected according to actual needs, and preferably, the content of the cyclic sulfate is 0.01% to 3% of the total mass of the electrolyte.
In the electrolytic solution according to the first aspect of the present application, the electrolytic solution further includes a non-aqueous organic solvent, and the kind of the non-aqueous organic solvent is not particularly limited as long as it satisfies that it does not contain active hydrogen and is polar. Specifically, the non-aqueous organic solvent may be selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, γ -butyrolactone, -valerolactone, methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, ethyl propionate, methyl butyrate, butyl formate, propyl propionate, ethyl butyrate, butyl acetate, methyl valerate, pentyl formate, one or more of dimethyl sulfate, methylethyl sulfate, diethyl sulfate, tetrahydrofuran, 1, 3-dioxolane, 1, 3-dioxane, dimethoxymethane, diethoxymethane, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, sulfolane, cyclopentylsulfone, dimethylsulfone, methylethylsulfone, diethylsulfone, cyclobutane sulfoxide, cyclopentylsulfone, dimethylsulfoxide, methylethylsulfoxide and diethylsulfoxide. From a practical and commercial point of view, it is preferred that the non-aqueous organic solvent is selected from a carbonate ester, or a mixture of a carbonate ester and a carboxylic acid ester.
In the electrolyte according to the first aspect of the present application, the concentration of the electrolyte salt is not particularly limited, and may be selected according to actual requirements, and if the concentration of the electrolyte salt is too low, the ion conductivity of the corresponding electrolyte is too low, and if the concentration of the electrolyte salt is too high, the viscosity of the corresponding electrolyte is increased, which may also result in the ion conductivity of the electrolyte being too low. Preferably, the concentration of the electrolyte salt is 0.05mol/L to 2.5mol/L, more preferably, the concentration of the electrolyte salt is 0.9mol/L to 2mol/L, and even more preferably, the concentration of the electrolyte salt is 0.7mol/L to 1.5 mol/L.
Next, an electrochemical energy storage device according to the second aspect of the invention will be described.
An electrochemical energy storage device according to the second aspect of the present application comprises a positive plate, a negative plate and an electrolyte according to the first aspect of the present application. The positive plate comprises a positive current collector and a positive active material layer which is arranged on the positive current collector and comprises a positive active material. The negative plate comprises a negative current collector and a negative active material layer which is arranged on the negative current collector and comprises a negative active material.
The electrochemical energy storage device may be a lithium ion battery, a sodium ion battery, a zinc ion battery, or a super capacitor. In the embodiments of the present application, only the embodiment in which the electrochemical energy storage device is a lithium ion battery is shown, but the present application is not limited thereto.
In the lithium ion battery, the type of the positive active material is not particularly limited and may be selected according to actual needs, and preferably, the positive active material may be selected from LiFePO4、LiCoO2、LiNiO2、LiMn2O4、LiCo1-aMaO2(0＜a＜1)、LiNi1-bMbO2(0＜b＜1)、LiMn2-cMcO4(0＜c＜2)、LiNixCoyMnzM1-x-y-zO2Wherein M is selected from one or more of Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti, y is more than or equal to 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x + y + z is less than or equal to 1. Preferably, the positive active material is selected from LiCoO2Lithium nickel cobalt manganese oxide ternary material and LiFePO4、LiMnO2Wherein the lithium nickel cobalt manganese oxide ternary material can be selected from LiNi1/3Co1/3Mn1/ 3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.5Co0.25Mn0.25O2One or more of them.
In the lithium ion battery, the kind of the negative active material is not particularly limited and may be selected according to actual needs, and preferably, the negative active material is selected from metallic lithium, natural graphite, artificial graphite, mesophase micro carbon spheres, hard carbon, soft carbon, silicon-carbon composite, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO2Spinel-structured lithiated TiO2-Li4Ti5O12And one or more of Li-Al alloy.
In the lithium ion battery, the electrolyte salt may be selected from lithium salts, the kind of the lithium salt is not particularly limited, and may be selected according to actual needs as long as it can provide a suitable lithium ion conductivity, and specifically, the lithium salt may be selected from LiPF6、LiBF4、LiClO4、LiAsF6、LiSbF6、LiBOB、LiDFOB、LiFSI、LiN(SO2CF3)2LiTFSI、LiPO2F2、LiPF2(C2O4)2、LiPF4(C2O4). From a practical and commercial point of view, preferably, the lithium salt is selected from LiPF6。
The present application is further illustrated below with reference to examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application. In the embodiments, only the case where the electrochemical energy storage device is a lithium ion battery is shown, but the present application is not limited thereto.
In the following examples, reagents, materials and instruments used are commercially available unless otherwise specified.
In the examples and comparative examples, the quaternary ammonium salts of phosphoric acid esters used were prepared as follows:
synthesis of Compound 1-1:
Figure BDA0001381654750000141
the first step of reaction:
Figure BDA0001381654750000142
the second step of reaction:
Figure BDA0001381654750000143
the third step of reaction:
Figure BDA0001381654750000144
and a fourth step of reaction:
Figure BDA0001381654750000145
the method comprises the following operation steps:
2-Bromoethanol (3g, 24mmol) was added to a two-necked flask containing anhydrous acetonitrile (80mL), cooled to 0 deg.C, piperidine (2.04g, 24mmol) and potassium carbonate (13g, 96mmol) were added, and the mixture was refluxed at elevated temperature for 8 hours. Cooled to room temperature, filtered under vacuum, and the organic solvent removed using a rotary evaporator. The residue was purified by flash chromatography on silica gel column (chloroform: methanol 10:1) to give a colorless oil (0.9g, yield 30%). Wherein the compound has structure identification data of1H-NMR(400MHz,CDCl3)：＝3.55(dd,J＝13.1,5.4Hz,2H)；＝2.48-2.27(m,6H)；＝1.58-1.46(m,4H)；＝1.38(t,2H)。
The above compound (6.45g, 50mmol) and triethylamine (12.6g, 2.5eq) were dissolved in 50mL of dichloromethane and slowly added dropwise to dichloromethane (40mL) containing dimethylphosphoryl chloride (2.1mL) at-20 ℃. The mixture is heated to room temperature and stirred for 5 hours, then cooled to 0 ℃ and filtered, and the organic solvent is removed from the filtrate by a rotary evaporator. The residue was purified by flash chromatography on a silica gel column (chloroform: methanol 10:1) to give a brown oily liquid (7.1g, yield 60%). Wherein the structural identification data of the compound is 1H-NMR (400MHz, CDCl 3): 4.19-4.08(m, 2H); 3.76(s, 3H); 3.73(s, 3H); 2.61(t, J ═ 6.0Hz,2H), ═ 2.42(t,4H), ═ 1.55(dt, J ═ 11.1,5.6Hz, 4H); 1.40(dd, J ═ 10.8,5.9Hz, 2H).
The above compound (2.37g, 10mmol) was dissolved in anhydrous ether (30mL), excess methyl iodide was added and stirred overnight to give the iodide salt, which was filtered and recrystallized to give 3.4g of material in 90% yield. Wherein the compound has structure identification data of1H-NMR(400MHz,D2O)：＝4.49(t,2H)；＝3.75(s,3H)；＝3.72(s,3H)；＝3.68(t,J＝3.0Hz,2H)；＝3.34(t,J＝5.4Hz,4H)；＝3.05(s,3H)；＝1.80(dt,4H)；＝1.62-1.52(dd,2H)。
The compound (1g, 2.635mmol) obtained in the above step was added to anhydrous acetone (10mL), and KPF was slowly added6(1.9g, 10.5mmol) in acetone. Stirring is carried out for 30 hours at 40 ℃ under the protection of nitrogen. The organic solvent was removed using a rotary evaporator, the residue was dissolved in dichloromethane, the insolubles were removed by filtration, the dichloromethane was removed in vacuo, and the solid product was rinsed with ethyl acetate and ether to give compound 1(0.1g, 10% yield).
Process for preparation of Compound 11H-NMR and19F-NMR nuclear magnetic identification data:
1H-NMR(400MHz,CDCl3):＝4.55(dd,J＝9.0,6.9Hz,2H)；＝4.07-4.02(m,2H)；＝3.83(s,3H)；＝3.81(s,3H)；＝3.71-3.63(m,4H)；＝3.35(s,3H)；＝1.96(dd,J＝11.3,5.7Hz,4H)；＝1.83-1.73(m,2H)。
19F-NMR(376MHz,CDCl3)；＝-70.57；＝-72.46。
the synthesis of the rest compounds is similar to that of the compound 1, and only the raw materials (such as reaction substrate salts and the like) and reaction parameters need to be changed, so that the details are not repeated.
The lithium ion batteries of examples 1 to 19 and comparative examples 1 to 5 were prepared as follows:
(1) preparation of positive plate
LiNi serving as a positive electrode active material0.5Co0.2Mn0.3O2The conductive agent Super P and the adhesive polyvinylidene fluoride (PVDF) are fully mixed in N-methyl pyrrolidone (NMP) to prepare positive electrode slurry, wherein the solid content in the positive electrode slurry is 77 wt%, and LiNi0.5Co0.2Mn0.3O2The mass ratio of Super P to PVDF is 97:1.4: 1.6. Uniformly coating the positive electrode slurry on a positive electrode current collector aluminum foil with the thickness of 12 mu m; drying at 85 ℃, and then carrying out cold pressing; then, after edge cutting, piece cutting and strip splitting, drying for 4h under the vacuum condition of 85 ℃ to prepare the positive plate, wherein the coating weight of the positive slurry is 270mg/1540.25mm2。
(2) Preparation of negative plate
Uniformly mixing the negative active material graphite, a conductive agent Super P, a thickening agent carboxymethylcellulose sodium (CMC) and a binding agent Styrene Butadiene Rubber (SBR) in deionized water to prepare negative slurry. Wherein the solid content in the negative electrode slurry is 54 wt%, and the mass ratio of the graphite, the Super P, the CMC and the SBR is 96.4:1.5:0.5: 1.6. Uniformly coating the negative electrode slurry on a negative electrode current collector copper foil with the thickness of 8 mu m, and drying at 85 ℃; then, after edge cutting, piece cutting and strip splitting, drying for 12h under the vacuum condition of 120 ℃ to prepare the negative plate, wherein the coating weight of the negative electrode slurry is 165mg/1540.25mm2。
(3) Preparation of the electrolyte
And (2) mixing ethylene carbonate, diethyl carbonate and methyl ethyl carbonate in a glove box filled with argon according to the mass ratio of EC: DEC: EMC of 3:2:5, slowly adding 1.0mol/L lithium hexafluorophosphate into the mixed solution, finally adding phosphate quaternary ammonium salt and cyclic sulfate serving as additives, and uniformly stirring to obtain the electrolyte. Specific kinds and contents of the quaternary ammonium phosphate and cyclic sulfate used in the electrolyte are shown in table 1. In table 1, the phosphate quaternary ammonium salt, the cyclic sulfuric acid content are mass percentages calculated based on the total mass of the electrolyte.
(4) Preparation of the separator
A polyethylene film (PE) of 12 μm was used as a separator.
(5) Preparation of lithium ion battery
Stacking the positive plate, the isolating film and the negative plate in sequence to enable the isolating film to be positioned between the positive plate and the negative plate, and winding to obtain a bare cell; welding a tab; placing the bare cell in an outer package, injecting the prepared electrolyte into the dried lithium ion battery, packaging, standing, forming (charging to 3.3V at a constant current of 0.02C and then charging to 3.6V at a constant current of 0.1C), shaping, and testing capacity to complete the preparation of the lithium ion battery.
TABLE 1 parameters of examples 1-19 and comparative examples 1-5
Figure BDA0001381654750000161
Figure BDA0001381654750000171
Next, a test procedure of the lithium ion battery is explained.
(1) Cycle performance testing of lithium ion batteries
Charging the lithium ion battery to 4.3V at a constant current of 1C at 45 ℃, then charging the lithium ion battery to a current of 0.05C at a constant voltage of 4.3V, and then discharging the lithium ion battery to 2.8V at a constant current of 1C, wherein the discharge capacity is a charge-discharge cycle, the discharge capacity is the first discharge capacity of the lithium ion battery, and the lithium ion battery is subjected to a 200-cycle charge/discharge test according to the method, and the discharge capacity of the 200 th cycle is obtained through detection.
The capacity retention (%) after 200 cycles at 45 ℃ of the lithium ion battery was equal to the discharge capacity/first discharge capacity of the 200 th cycle × 100%.
(2) Direct current resistance testing of lithium ion batteries
Discharging the lithium ion battery to 2.8V at a constant current of 1C, and standing for 5 minutes; fully charging to 4.3V at a constant current of 1C, then charging to 0.05C at a constant voltage of 4.3V, standing for 5 minutes, and then discharging to 2.8V at a constant current of 1C, wherein the discharge electric quantity at the moment is the actual discharge capacity of the lithium ion battery; fully charging the lithium ion battery to 4.3V at a constant current of 1C, then keeping the voltage constant to 0.05C at 4.3V, then discharging for 30s at a constant current of 4C, reading the voltage value of the lithium ion battery at the moment, and recording the voltage value as U1。
Direct Current Resistance (DCR) of lithium ion battery at 100% SOC is 4.3V-U1/I1。
In the same way, fully charging the lithium ion battery to 4.3V at a constant current of 1C, then discharging for 1 hour at a constant current of 0.5C to adjust the lithium ion battery to 50% SOC, then discharging for 30S at a constant current of 4C, reading the voltage value of the lithium ion battery at the moment, and recording the voltage value as U2。
Direct Current Resistance (DCR) of lithium ion battery at 50% SOC of 4.3V-U2/I2。
TABLE 2 results of Performance test of examples 1 to 19 and comparative examples 1 to 5
Figure BDA0001381654750000181
Figure BDA0001381654750000191
As can be seen from the analysis of the relevant data in table 2, in comparative examples 1 to 3, the addition of the quaternary ammonium salt phosphate and the cyclic sulfate to comparative example 1 resulted in poor high-temperature cycle performance and a large Direct Current Resistance (DCR) of the lithium ion battery. When either electrolyte is added (comparative examples 2 and 3), the high-temperature cycle performance and the direct-current resistance of the lithium ion battery can be improved to a certain extent, but the use requirements of the high-temperature cycle performance and the high-power performance of the lithium ion battery under high-compaction thick coating can not be met.
In examples 1 to 10, it is found that, although the quaternary ammonium phosphate and the cyclic sulfate are different in kind, uniform, dense and low-impedance passivation films can be formed on the surfaces of the positive electrode and the negative electrode of the lithium ion battery, so that the lithium ion battery coated in a high-compaction and thick manner has good high-temperature cycle performance and low direct-current resistance. Particularly, when the electrolyte contains the phosphate quaternary ammonium salt, on one hand, the phosphate quaternary ammonium salt can directionally migrate to the negative electrode when the lithium ion battery is formed, a low-impedance and compact SEI film is generated on the negative electrode before a non-aqueous organic solvent, and when the phosphate quaternary ammonium salt is used together with cyclic sulfate, the mutual synergistic effect of the phosphate quaternary ammonium salt and the cyclic sulfate can improve the impedance of a generated passivation film and reduce the DCR of the lithium ion battery; on the other hand, the phosphate quaternary ammonium salt has both hydrophilicity and lipophilicity, so that the electrolyte can be quickly soaked into the high-compaction-density thick coating pole piece, the generated SEI film is more uniform, the high-temperature-cycle capacity retention rate of the lithium ion battery can be improved, the direct-current resistance of the lithium ion battery can be reduced, and the discharge power of the lithium ion battery can be improved.
It is found that the film forming condition of the lithium ion battery can be effectively improved by combining a small amount of quaternary ammonium phosphate with cyclic sulfate in examples 11 to 19 and comparative examples 4 to 5, so that the lithium ion battery has better high-temperature cycle performance and the direct current resistance of the lithium ion battery is reduced, but if the content of the quaternary ammonium phosphate is too large (comparative example 4), the effect is not proportionally improved. Also, as the content of the cyclic sulfate ester gradually increases, the high temperature cycle performance and the direct current resistance of the lithium ion battery may be improved, but if the content of the cyclic sulfate ester is too large (comparative example 5), the improvement effect on the lithium ion battery may be weakened, which may be associated with too much additives, poor kinetics of the electrolyte, and too thick film formation.
In summary, when the electrolyte containing the quaternary ammonium phosphate and the cyclic sulfate is applied to the lithium ion battery with high compaction and thick coating, a passivation film can be formed on the surfaces of the positive electrode and the negative electrode due to the synergistic effect of the quaternary ammonium phosphate and the cyclic sulfate, and particularly, a layer mainly composed of lithium alkyl phosphate LiOP (═ O) (OR) can be established on the surface of the negative electrode2The SEI film formed by the substances has low impedance and is more compact, so that the high-temperature cycle performance and the direct current resistance of the lithium ion battery can be obviously improved.
Those skilled in the art to which the present application pertains can also make appropriate changes and modifications to the above-described embodiments, based on the disclosure of the above description. Therefore, the present application is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present application should fall within the scope of the claims of the present application.

Claims (9)

1. An electrolyte, comprising:
an electrolyte salt; and
an additive agent is added to the mixture,
it is characterized in that the preparation method is characterized in that,
the additive comprises phosphate ester quaternary ammonium salt and cyclic sulfate ester;
the phosphate quaternary ammonium salt is selected from one or more compounds shown in a formula 1;
Figure FDA0002625612360000011
in formula 1, R11、R12Each independently selected from methyl, R13One kind selected from substituted or unsubstituted C1-C12 alkylene, R14One selected from substituted or unsubstituted C1-C6 alkyl, R15One selected from substituted or unsubstituted C1-C3 alkylene;
at R13、R14、R15In the formula, the substituent is selected from one or more of C1-C3 alkyl and halogen;
Figure FDA0002625612360000013
it is meant an anion, and it is meant,
Figure FDA0002625612360000014
is selected from F-、[PF6]-、[AsF6]-、[BF4]-、[NO3]-、[ClO4]-、
Figure FDA0002625612360000012
Figure FDA0002625612360000021
One kind of (1).
2. The electrolyte of claim 1, wherein the cationic group of the quaternary ammonium salt of a phosphate ester is selected from the group consisting of
Figure FDA0002625612360000022
Figure FDA0002625612360000023
One kind of (1).
3. The electrolyte of claim 2, wherein the quaternary ammonium phosphate salt is selected from one or more of the following compounds;
Figure FDA0002625612360000031
4. the electrolyte of claim 1, wherein the cyclic sulfate is selected from one or more compounds shown in formula 2 and formula 3;
Figure FDA0002625612360000041
in formula 2, n is an integer of 1 to 3, R21、R22、R23、R24Each independently selected from H, F, Cl, Br, I, cyano, carboxyl, sulfonic group, alkyl or halogenated alkyl of C1-C20, unsaturated alkyl or halogenated unsaturated alkyl of C2-C20One kind of the material is selected;
in formula 3, m is an integer of 0 to 3, R31、R32、R33、R34Each independently selected from one of H, F, Cl, Br, I, cyano-group, carboxyl group, sulfonic group, alkane or halogenated alkane of C1-C20, and unsaturated hydrocarbon or halogenated unsaturated hydrocarbon of C2-C20.
5. The electrolyte as claimed in claim 4, wherein the cyclic sulfate is selected from one or more of the following compounds;
Figure FDA0002625612360000042
Figure FDA0002625612360000051
Figure FDA0002625612360000061
6. the electrolyte of claim 1,
the content of the phosphate ester quaternary ammonium salt is 0.01-10% of the total mass of the electrolyte;
the content of the cyclic sulfate is 0.01-3% of the total mass of the electrolyte.
7. The electrolyte of claim 1, wherein the electrolyte is a liquid electrolyte, a solid polymer electrolyte, or a gel polymer electrolyte.
8. The electrolyte of claim 1, wherein the concentration of the electrolyte salt is 0.05mol/L to 2.5 mol/L.
9. An electrochemical energy storage device, comprising:
the positive plate comprises a positive current collector and a positive active material layer which is arranged on the positive current collector and comprises a positive active material;
a negative electrode sheet including a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector and including a negative electrode active material; and an electrolyte as claimed in any one of claims 1 to 8.
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