CN108390098A - A kind of high-voltage lithium-ion battery electrolyte and high-voltage lithium ion batteries - Google Patents
A kind of high-voltage lithium-ion battery electrolyte and high-voltage lithium ion batteries Download PDFInfo
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- CN108390098A CN108390098A CN201810276759.0A CN201810276759A CN108390098A CN 108390098 A CN108390098 A CN 108390098A CN 201810276759 A CN201810276759 A CN 201810276759A CN 108390098 A CN108390098 A CN 108390098A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
To overcome the problems, such as that the height of high-voltage electrolyte impedance in the prior art, high temperature performance can not be taken into account, a kind of high-voltage lithium-ion battery electrolyte is provided, the present invention provides a kind of high-voltage lithium-ion battery electrolytes, including lithium salts, solvent and additive, above-mentioned additive includes cyclic annular sultones, fluoric cyclic carbonate, double fluorine sulfimide lithiums and such as 1 compound represented A of following formula：Formula 1：Wherein, R1、R2、R3、R4、R5Separately it is selected from OR6、‑CN、‑NO2、‑F、‑CF3、‑SO3、‑COR7、‑COOR8, alkyl that carbon atom number is 1 30, also, the R6、R7、R8Separately it is selected from the alkyl that carbon atom number is 1 30.Meanwhile the invention also discloses the lithium ion batteries using above-mentioned high-voltage lithium-ion battery electrolyte.High-voltage lithium-ion battery electrolyte provided by the invention can be substantially reduced the impedance of battery, improve the cryogenic property of battery, improve the high temperature cyclic performance of battery.
Description
Technical field
The present invention relates to the high-voltage lithium ion batteries of a kind of high-voltage lithium-ion battery electrolyte and the use electrolyte.
Background technology
Lithium ion battery has high voltage, and energy and power density are high, cycle life, and self discharge is small and environmentally friendly
Etc. series of advantages, have become current most efficient energy storage device, be widely used in mobile electronic device, and will be
Wider array of development is obtained on electric vehicle and hybrid vehicle.With the continuous development of scientific and technological progress and market, lithium battery is promoted
Energy density increasingly seems important and urgent.Other than the manufacture craft of current material and battery is improved, high-voltage anode material
Material is popular one of the research direction of comparison, it is to realize the high energy of battery by promoting the depth of charge of positive electrode active materials
Metric density.So far, a variety of high-voltage anode materials such as binary material LiNiMnO4, ternary material LiNixCoyMnzO2(x+y+z=
1), vanadium system oxide LiMxV2-xO4With phosphoric acid salt material LiMPO4Successfully researched and developed.
However the impedance that the esters electrolyte of traditional lithium-ion battery is susceptible to lithium ion battery in high-temperature electric pressure increases
Add, the problem of efficiency for charge-discharge is greatly reduced, high temperature performance can not be taken into account, constrain the further of high-voltage lithium ion batteries
Development.
Invention content
The technical problem to be solved by the present invention is to be directed to, high-voltage electrolyte impedance in the prior art is high, high and low temperature
The problem of capable of can not taking into account, provide a kind of high-voltage lithium-ion battery electrolyte.
Technical solution is as follows used by the present invention solves above-mentioned technical problem：
A kind of high-voltage lithium-ion battery electrolyte, including lithium salts, solvent and additive are provided, above-mentioned additive includes ring
Shape sultones, fluoric cyclic carbonate, double fluorine sulfimide lithiums and such as 1 compound represented A of following formula：
Formula 1：
Wherein, R1、R2、R3、R4、R5Separately it is selected from-OR6、-CN、-NO2、-F、-CF3、-SO3、-COR7、-COOR8、
Carbon atom number is the alkyl of 1-30, also, the R6、R7、R8Separately it is selected from the alkyl that carbon atom number is 1-30.
Meanwhile the present invention also provides a kind of high-voltage lithium ion batteries, including anode, cathode, setting are in the anode
Diaphragm between the cathode and electrolyte, wherein the electrolyte is foregoing high-voltage lithium ion batteries electricity
Solve liquid.
For the impedance easily occurred when high-voltage lithium ion batteries being overcome to be used under higher charging/discharging voltage (>=4.25V)
Height, high temperature performance is poor, the low problem of capacity retention ratio, the present invention by the electrolytic solution simultaneously using cyclic annular sultones,
1 compound represented A of fluoric cyclic carbonate, double fluorine sulfimide lithiums and above-mentioned formula, is being electrolysed by above-mentioned four substance
Synergistic effect in liquid system significantly reduces the impedance of electrolyte, while electrolyte being made to have good high temperature performance.
Specific implementation mode
In order to make the technical problems, technical solutions and beneficial effects solved by the present invention be more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
High-voltage lithium-ion battery electrolyte provided by the invention includes lithium salts, solvent and additive, above-mentioned additive packet
Include cyclic annular sultones, fluoric cyclic carbonate, double fluorine sulfimide lithiums and such as 1 compound represented A of following formula：
Formula 1：
Wherein, R1、R2、R3、R4、R5Separately it is selected from-OR6、-CN、-NO2、-F、-CF3、-SO3、-COR7、-COOR8、
Carbon atom number is the alkyl of 1-30, also, the R6、R7、R8Separately it is selected from the alkyl that carbon atom number is 1-30.
In above-mentioned electrolyte, cyclic annular sultones is well known in the art, for example, 1 is specifically can be used, in 3- propane sulphurs
At least one of ester, Isosorbide-5-Nitrae-butane sultone, propenyl-1,3-sulfonic acid lactone, it is preferred to use 1,3-propane sultone.
In electrolyte provided by the invention, the additive amount of cyclic annular sultones can adjust in wide range, preferably feelings
Under condition, the content of the ring-type sultones is 0.01%-5%.
Fluorinated ethylene carbonate, trifluoromethyl ethylene carbonate, double fluoro specifically can be used in above-mentioned fluoric cyclic carbonate
It is one or more in ethylene carbonate.Under preferable case, in above-mentioned electrolyte, the content of the fluoric cyclic carbonate is
0.01%-30%, more preferably 0.1%-3%.
Double fluorine sulfimide lithiums (LiFSI) substance well known in the art, high-voltage lithium ion electricity provided by the invention
In the electrolyte of pond, the content of double fluorine sulfimide lithiums is 0.01%-15%.
In the present invention, for above compound A, theoretically, the compound of structure shown in meeting formula 1 can realize the present invention
Purpose, as particularly preferred, the compound A is 1- methyl-benzotriazole.
On the basis of the total weight of the electrolyte, the content of the compound A is 0.01%-5%, preferably
0.05%-3%, more preferably 0.1%-0.8%.
It, can be with cyclic annular sultones above-mentioned, fluoric cyclic carbonate, double fluorine sulfimide lithiums for above compound A
Collective effect forms a film in the positive and negative anodes of battery, to reduce battery impedance, improves the high temperature performance of battery under high voltages.
When the additive amount of compound A is too small, film-formation result is deteriorated, and declines to battery impedance and high temperature performance improvement, and works as
Battery impedance, deterioration can seriously be increased when the adding too much of compound A.
In high-voltage lithium-ion battery electrolyte provided by the invention, in cyclic annular sultones, fluoric cyclic carbonate, double
In the presence of fluorine sulfimide lithium is common, after compound A is added, compound A can occur with the mentioned component in electrolyte
Synergistic effect, in the case where equally improving battery high temperature performance, the unexpected resistance for considerably reducing battery
It is anti-.Also, in electrolyte system provided by the invention, the influence of double fluorine sulfimide lithiums is equally notable, even if using structure
Similar bis- (trimethyl fluoride sulfonyl) imine lithiums (LiTFSI) also cannot achieve the purpose of the present invention, if the present invention provides excessive electricity
The cycle performance under high temperature will be caused to be deteriorated using LiTFSI in solution liquid.
According to the present invention, to realize better resultant effect, the high-voltage lithium-ion battery electrolyte further includes insatiable hunger
And cyclic carbonate.The unsaturated cyclic carbonic ester is selected from least one of vinylene carbonate, vinylethylene carbonate；
On the basis of the total weight of the electrolyte, the content of the unsaturated cyclic carbonic ester is 0.01%-5%.
Further include solvent, lithium salts in high-voltage lithium-ion battery electrolyte provided by the invention.As people in the art
Member well known to, wherein the specific substance of solvent can be used it is conventional, for example, the lithium salts be selected from LiPF6、LiBF4、LiBOB、
LiDFOB、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiC(SO2CF3)3In it is one or more.The lithium ion battery is non-aqueous
In electrolyte, the content of lithium salts is 0.1-15%.The non-aqueous organic solvent is selected from ethylene carbonate, propene carbonate, carbonic acid
At least one of butene esters, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and methyl propyl carbonate.The content of solvent can
It adjusts in wide range, can be specifically adaptively adjusted according to the content of foregoing various additives and lithium salts.
The present invention also provides a kind of high-voltage lithium ion batteries, including anode, cathode, setting are described positive and described
Diaphragm between cathode and electrolyte, the electrolyte are foregoing high-voltage lithium-ion battery electrolyte.
Preferably, the anode includes positive electrode active materials, and the active material of the anode is LiNixCoyMnzL(1-x-y-z)
O2、LiCox’L(1-x’)O2、LiNix”L’y’Mn(2-x”-y’)O4、Liz’MPO4At least one of, wherein L Al, Sr, Mg, Ti,
At least one of Ca, Zr, Zn, Si or Fe, 0≤x≤1,0≤y≤1,0≤z≤1,0 ＜ x+y+z≤1,0<X '≤1,0.3≤
X "≤0.6,0.01≤y '≤0.2, L ' it is at least one of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si, Fe；0.5≤z’≤
At least one of 1, M Fe, Mn, Co.
Electrolyte provided by the invention is more suitable in high-voltage lithium ion batteries, it is preferred that the lithium ion battery
Charge cutoff voltage >=4.25V.
The anode, cathode, diaphragm do not limit clearly, and the anode, cathode, diaphragm of this field routine can be used.
The present invention is further detailed by the following examples.
Embodiment 1-2, comparative example 1-7
The present embodiment is for illustrating high-voltage lithium-ion battery electrolyte disclosed by the invention.
With LiNi0.5Co0.2Mn0.3O2The electrode material system of/artificial graphite prepares 4.35V high-voltage lithium ion batteries, packet
Include anode, cathode, the diaphragm and electrolyte being arranged between the anode and the cathode, wherein the electrolyte it is total
Weight is 100% meter, contains additive composition and mass percentage, remaining group shown in 1 embodiment 1-2 of table, comparative example 1-7
It is divided into LiPF6And Conventional solvents.
1 electrolysis additive of table forms
The battery that above-described embodiment and comparative example are prepared carries out following performance test, and by the test result of gained
Insert table 2：
(1) high temperature cyclic performance is tested：At 45 DEG C, the battery after chemical conversion is charged to 4.35V with 1C constant current constant voltages, then
With 1C constant-current discharges to 3.0V.After 300 cycles of charge/discharge, the conservation rate of the 300th circulation volume is calculated, to assess its height
Warm cycle performance.
It is as follows that 45 DEG C of 1C recycle 300 capacity retention ratio calculation formula：
300th circulation volume conservation rate (%)=(the 300th cyclic discharge capacity/first time cyclic discharge capacity) ×
100%.
(2) low temperature performance is tested：At 25 DEG C, the battery after chemical conversion is charged to 4.35V with 1C constant current constant voltages, then
With 0.5C constant-current discharges to 3.0V, discharge capacity is recorded.Then 1C constant current constant voltages are full of, and are placed in -20 DEG C of environment and are shelved 12h
Afterwards, 0.5C constant-current discharges record discharge capacitance to 3.0V.
- 20 DEG C of low temperature discharge capacity conservation rate=0.5C discharge capacities (- 20 DEG C)/0.5C discharge capacities (25 DEG C)
(3) often low temperature direct impedance (DCR) performance test：At 25 DEG C, the battery 1C after chemical conversion is charged to half electric shape
State uses 0.1C, 0.2C, 0.5C, 1C and 2C charge and discharges ten seconds to record charge and discharge blanking voltage respectively respectively.Then, with different multiplying
Charging and discharging currents be abscissa (unit：A), using the blanking voltage corresponding to charging and discharging currents as ordinate, linear relationship is done
Scheme (unit：mV).
The slope value for the DCR values=difference charging current and the linear graph of corresponding blanking voltage of charging.
The slope value of electric discharge DCR values=difference discharge current and the linear graph of corresponding blanking voltage.
Table 2
The test result of comparative example 1 and comparative example 5 can be seen that in the electrolyte system containing PS, FEC, LiFIS
Middle addition 1- methyl-benzotriazole can significantly reduce DCR while improving high temperature performance.And compare comparative example 4 and right
Although ratio 1-3 and the test result of comparative example 7 and comparative example 6 can be seen that is added 1- in PS, FEC or PS, VC systems
Methyl-benzotriazole can improve high temperature performance and can reduce DCR, but the reduction amplitude of DCR is very small.
The effect of comparative example 1 and embodiment 2 can be seen that the content of 1- methyl-additives such as benzotriazole and FEC
Increase battery high-temperature behavior will be caused to decline, especially DCR is sharply increased, but performance be still slightly stronger than not simultaneously contain PS, FEC,
The electrolyte of LiFIS and 1- methyl-benzotriazole.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (10)
1. a kind of high-voltage lithium-ion battery electrolyte, which is characterized in that including lithium salts, solvent and additive, above-mentioned additive
Including cyclic annular sultones, fluoric cyclic carbonate, double fluorine sulfimide lithiums and such as 1 compound represented A of following formula：
Formula 1：
Wherein, R1、R2、R3、R4、R5Separately it is selected from-OR6、-CN、-NO2、-F、-CF3、-SO3、-COR7、-COOR8, carbon it is former
Subnumber is the alkyl of 1-30, also, the R6、R7、R8Separately it is selected from the alkyl that carbon atom number is 1-30.
2. high-voltage lithium-ion battery electrolyte according to claim 1, which is characterized in that the compound A is 1- first
Base-benzotriazole.
3. high-voltage lithium-ion battery electrolyte according to claim 1, which is characterized in that the ring-type sultones choosing
From at least one of 1,3- propane sultones, 1,4- butane sultones, acrylic -1,3- sultones.
4. high-voltage lithium-ion battery electrolyte according to claim 1, which is characterized in that the fluoric cyclic carbonate
Selected from least one of fluorinated ethylene carbonate, trifluoromethyl ethylene carbonate, difluoroethylene carbonate.
5. according to the high-voltage lithium-ion battery electrolyte described in any one of claim 1-4, which is characterized in that with described
On the basis of the total weight of electrolyte, the content of the compound A is 0.01%-5%；It is described ring-type sultones content be
0.01%-5%；The content of the fluoric cyclic carbonate is 0.01%-30%；The content of double fluorine sulfimide lithiums is
0.01%-15%.
6. high-voltage lithium-ion battery electrolyte according to claim 1, which is characterized in that the high-voltage lithium ion electricity
Pond electrolyte further includes unsaturated cyclic carbonic ester.
7. high-voltage lithium-ion battery electrolyte according to claim 6, which is characterized in that the unsaturated cyclic carbonic acid
Ester is selected from least one of vinylene carbonate, vinylethylene carbonate；It is described on the basis of the total weight of the electrolyte
The content of unsaturated cyclic carbonic ester is 0.01%-5%.
8. a kind of high-voltage lithium ion batteries, including anode, cathode, the diaphragm being arranged between the anode and the cathode,
And electrolyte, which is characterized in that the electrolyte is the high-voltage lithium ion batteries described in any one of claim 1-7
Electrolyte.
9. high-voltage lithium ion batteries according to claim 8, which is characterized in that the anode includes positive-active material
The active material of material, the anode is LiNixCoyMnzL(1-x-y-z)O2、LiCox’L(1-x’)O2、LiNix”L’y’Mn(2-x”-y’)O4、
Liz’MPO4At least one of, wherein at least one of L Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe, 0≤x≤1,0
≤ y≤1,0≤z≤1,0 ＜ x+y+z≤1,0<X '≤1,0.3≤x "≤0.6,0.01≤y '≤0.2, L ' be Co, Al, Sr,
At least one of Mg, Ti, Ca, Zr, Zn, Si, Fe；At least one of 0.5≤z '≤1, M Fe, Mn, Co.
10. high-voltage lithium ion batteries according to claim 8 or claim 9, which is characterized in that the high-voltage lithium ion batteries
Charge cutoff voltage >=4.25V.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111916826A (en) * | 2020-07-22 | 2020-11-10 | 梅州市量能新能源科技有限公司 | Electrolyte and preparation method thereof, and lithium ion battery and preparation method thereof |
| CN112290095A (en) * | 2020-10-26 | 2021-01-29 | 合肥国轩高科动力能源有限公司 | Lithium ion battery electrolyte suitable for high-nickel material system and preparation method thereof |
| CN112310473A (en) * | 2019-07-30 | 2021-02-02 | 东莞市杉杉电池材料有限公司 | High-low temperature lithium ion battery electrolyte and lithium ion battery |
| CN113871715A (en) * | 2020-06-30 | 2021-12-31 | 诺莱特电池材料(苏州)有限公司 | Lithium iron phosphate battery |
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