CN109792082A - A kind of secondary cell electrolyte and the secondary cell including it - Google Patents
A kind of secondary cell electrolyte and the secondary cell including it Download PDFInfo
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- CN109792082A CN109792082A CN201780055867.9A CN201780055867A CN109792082A CN 109792082 A CN109792082 A CN 109792082A CN 201780055867 A CN201780055867 A CN 201780055867A CN 109792082 A CN109792082 A CN 109792082A
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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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- 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
- H01M10/0568—Liquid materials characterised by the solutes
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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
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of secondary cell electrolyte including glyoxal sulfate and fluorinated ethylene carbonate and including its secondary cell, the secondary cell at any temperature can stable for extended periods of time and excellent capacity and output characteristics, therefore be suitable for requiring the field of high output.
Description
Technical field
The present invention relates to a kind of secondary cell electrolyte and packet including glyoxal sulfate and fluorinated ethylene carbonate
Include its secondary cell.The secondary cell at any temperature can stable for extended periods of time, excellent capacity and output characteristics,
Therefore it is suitable for requiring the high field exported.
Background technique
With the increase of technological development and demand to mobile device, the demand to the secondary cell as the energy sharply increases
Add.In the secondary battery, the lithium secondary battery with high-energy density, excellent life characteristic and low self-discharge rate obtains commercialization
And it is widely used.
In recent years, environmental problem is increasingly paid close attention to people, causes the main of air pollution to can replace
The electric car and mixed power electric car of the fossil fuels automobile such as gasoline car and diesel vehicle of one of reason are largely ground
Study carefully.It is used as the power source of these electric vehicles and hybrid-power electric vehicle with high-energy currently, energetically carrying out
The research of the lithium secondary battery of density, high discharge voltage and output stability, and some have realized commercialization.
This lithium secondary battery is made of cathode, anode and nonaqueous electrolytic solution, wherein the cathode is by insertion and removal lithium embedded
The formation such as carbon material of ion, the anode are formed by lithium-containing oxides etc., and the nonaqueous electrolytic solution is by dissolving appropriate lithium salts
It is formed in mixed organic solvents.Additionally, it is known that having the output stability for improving the nonaqueous electrolytic solution and adding
Various additives and electrolyte composition technology.
For example, U.S.'s registered patent the 6th, 506,524 disclose it is a kind of by using including fluorinated ethylene carbonate
Electrolyte forms stable film on lithium battery to improve the technology of battery efficiency and long-term behaviour.In addition, Japanese Registered Patent
No. 5239119 discloses a kind of such technology: by secondary cell with adding fluorinated ethylene carbonate in electrolyte,
The film with high ionic conductivity is formed on cathode, to prevent the direct contact of active material of cathode and electrolyte, inhibits electricity
Solve decomposition and the cell degradation of liquid.In addition, Japanese Registered Patent the 5192237th disclose one kind can by using include fluoro
The electrolyte of ethylene carbonate inhibits the increased technology of resistance of inside battery.
However, although the registered patent shows raising by using the electrolyte for including fluorinated ethylene carbonate
The effect of battery life characteristics, but without it is manifestly intended that requiring life characteristic in the high battery exported and at high temperature
Battery output and capacitance effect when long-term preservation, it is therefore necessary to improve.In addition, fluorinated ethylene carbonate is on cathode
Although the film of formation has high ionic conductivity and shows the excellent service life at normal temperature, at high temperature, the film is deposited
The problem of duration reduces.
Summary of the invention
(the technical issues of to be solved)
Therefore, it is necessary to research and develop out a kind of electrolyte, improves the characteristic of the battery from low temperature to high temperature, especially change
The characteristic of secondary cell after kind high output and long-term preservation.
Therefore, the secondary cell use of the high output characteristic of battery can be kept for a long time the purpose of the present invention is to provide one kind
Electrolyte and secondary cell including it.
(means solved the problems, such as)
In order to realize the purpose, the present invention provides a kind of secondary cell electrolyte, comprising:
Carbonate-based solvent；
Lithium salts；
The compound of following chemical formula 1；And
The compound of following chemical formula 2,
[chemical formula 1]
[chemical formula 2]
In addition, the present invention provides a kind of secondary cell including the secondary cell electrolyte.
(The effect of invention)
Secondary cell electrolyte of the invention forms ionic conductance height on the cathode surface of secondary cell and in height
Stable film under temperature, to reduce because electrolyte and electrode directly contact with the side reaction that may occur.In addition, including described
The secondary cell of secondary cell electrolyte all stable for extended periods of time, excellent capacity and output characteristics at any temperature, are fitted
Close the field for being applied to require high output.
Specific embodiment
Hereinafter, the present invention is described in detail.
Secondary cell electrolyte according to the present invention includes: carbonate-based solvent；Lithium salts；The chemical combination of following chemical formula 1
Object；And the compound of following chemical formula 2,
[chemical formula 1]
[chemical formula 2]
The compound of the chemical formula 1 is known compound (CAS No.496-45-7), referred to as bicyclic glyoxal sulphur
Hydrochlorate (bicyclo-glyoxal sulfate), glyoxal sulfate (glyoxal sulfate) or 3a, 6a- dihydro-[1,3,
2] dioxa bicyclic [4,5-d] [1,3,2] dioxane thiophene 2,2,5,5- tetroxide (3a, 6a-dihydro- [1,3,2]
Dioxathiolo [4,5-d] [1,3,2] dioxathiole 2,2,5,5-tetraoxide) etc. titles, can purchase on the market
It buys.In addition, the compound of the chemical formula 1 can be prepared by known synthetic method, for example, with 1,1,2,2- tetrachloroethanes
As starting material, reacted with sulfuric acid etc. (with reference to U.S.'s registered patent the 1st, 999,995 and U.S.'s registered patent the 2nd,
No. 415,397).
The compound of the chemical formula 2 is known compound (CAS No.114435-02-8), commonly known as fluoro
Ethylene carbonate (fluoroethylene carbonate), it is commercially available, or use known synthetic method system
It is standby.
The electrolyte may include the compound relative to the chemical formula 1 of 0.1 to 10 weight percent of total weight
With the compound of the chemical formula 2 of 0.05 to 10 weight percent.Specifically, the electrolyte may include relative to gross weight
Measure the compound of the chemical formula 1 of 0.1 to 8 weight percent, 0.2 to 5 weight percent or 0.5 to 3 weight percent；
And the compound of the chemical formula 2 of 0.05 to 9 weight percent, 0.1 to 8 weight percent or 0.5 to 5 weight percent.
When including the compound of the chemical formula 1 in the content range, has and inhibit the resistance of battery increased under high temperature environment
Effect and prevent the effect that initial resistance is excessively increased under room temperature.In addition, including the chemical formula 2 in the content range
When compound, the electrolyte is coated on the surface of electrode with thickness appropriate, to prevent the resistance of secondary cell from increasing
Add.
Preferably, the carbonate-based solvent (adds the compound of the lithium salts and chemical formula 1, the compound of chemical formula 2
Add agent) there is high-dissolvability.Specifically, the carbonate-based solvent may include selected from by diethyl carbonate (diethyl
Carbonate), methyl ethyl carbonate (ethylmethyl carbonate), dimethyl carbonate (dimethyl carbonate),
Dipropyl carbonate (dipropyl carbonate), methyl propyl carbonate (methylpropyl carbonate), carbonic acid ethyl third
Ester (ethylpropyl carbonate), ethylene carbonate (ethylene carbonate), propylene carbonate (propylene
Carbonate), butylene carbonate (butylene carbonate) and gamma-butyrolacton (gamma-butyrolactone) composition
Group more than one.More specifically, the carbonate-based solvent may include selected from by diethyl carbonate, methyl ethyl carbonate,
More than one linear carbonates of the group of dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate and carbonic acid ethylpropyl composition
Class solvent；And more than one selected from the group being made of ethylene carbonate, propylene carbonate, butylene carbonate and gamma-butyrolacton
Cyclic carbonates solvent.
The solvent by dehydration can be used in the carbonate-based solvent, and specifically, carbonate-based solvent can contain 30
Weight ppm moisture below.
The lithium salts is not particularly limited, as long as being commonly used in secondary cell electrolyte.Specifically, described
Lithium salts may include selected from by LiPF6、LiBF4、LiBF6、LiSbF6、LiAsF6、LiClO4、LiSO3CF3、LiN(CF3SO2)2、
LiN(C2F5SO2)2、LiN(SO2F)2With LiC (CF3SO2)3The group of composition more than one.
The electrolyte may include 0.05 to 5.0 mole of the carbonate-based solvent of the lithium salts relative to 1L.Specifically
Ground, the electrolyte may include 0.1 to 5.0 mole of the carbonate-based solvent, 0.1 to 3.0 mole, 0.1 relative to 1L
To 2.5 moles or 0.5 to 3.0 mole of lithium salts.When including the lithium salts in the range, it can be ensured that reasonable electrolyte
Ionic conductance, and relative to added lithium salt, the ionic conductance promotion effect of obtainable electrolyte is obvious,
So very economical.
Secondary cell according to the present invention can be by simply mixing and stirring carbonate-based solvent, lithium with electrolyte
It salt, the glyoxal sulfate indicated by the chemical formula 1 and is made by fluorinated ethylene carbonate that the chemical formula 2 indicates
It is standby.
The present invention provides a kind of secondary cell including the secondary cell electrolyte.Specifically, the secondary cell
It may include: anode, including active material of positive electrode；Cathode, including active material of cathode；Separation membrane, setting to the anode and
Between cathode；And the secondary cell electrolyte.
The anode includes the active material of positive electrode that can be reversibly embedded in deintercalate lithium ions.The active material of positive electrode
It may include more than one metals selected from the group being made of cobalt, manganese and nickel；And the metal composite oxide containing lithium.Metal it
Between Solid soluble Nb be not quite similar, other than metal as described above, the active material of positive electrode can also include selected from by Mg,
More than one yuan of the group of Al, K, Na, Ca, Si, Ti, Sn, V, Ge, Ga, B, As, Zr, Cr, Fe, Sr and rare earth element composition
Element.
The cathode includes the active material of cathode that can be embedded in deintercalate lithium ions.The active material of cathode can be
The carbons active material of cathode (carbon, coke, the graphite of thermal decomposition) of crystallization or unbodied carbon or carbon complex；That is burnt into is organic
High-molecular compound；Carbon fiber；Tin oxide compound；Lithium metal；Or lithium alloy.For example, the amorphous carbon can be hard
Carbon, coke, carbonaceous mesophase spherules (the mesocarbon microbead being burnt under 1500 DEG C of following temperature；MCMB), intermediate
Asphalt phase base carbon fibre (mesophase pitch-based carbon fiber；MPCF) etc..The crystalline carbon can be stone
Black based material, such as natural graphite, artificial graphite, graphitized coke, graphitized intermediate-phase carbosphere, graphitized intermediate-phase pitch
Base carbon fibre etc..In the lithium alloy, with lithium constitute alloy other elements can for aluminium, zinc, bismuth, cadmium, antimony, silicon, lead, tin,
Gallium or indium.
The separation membrane be used for it is short-circuit caused by preventing because of the direct contact between anode and cathode, such as polyolefin,
The polymer films such as polypropylene or polyethylene or its multilayer film；Microporous membrane；Shuttle-woven fabric；And non-woven fabrics etc..The separation membrane can
With single or double coated metal oxide.
<embodiment>
Hereinafter, will be by specific embodiment and comparative example, the present invention will be described in detail.Following embodiment is for more having
Illustrate the present invention to body, is not intended to limit the scope of the present invention.
It is known compound in the compound of the chemical formula 1 and chemical formula 2 that use in the following examples and comparative examples,
Its structural formula, chemical name and No. CAS are as follows:
(1) compound of chemical formula 1: glyoxal sulfate, bicyclic glyoxal sulfate, No. CAS is 496-45-7,
[chemical formula 1]
(2) compound of chemical formula 2: fluorinated ethylene carbonate (fluoroethylene carbonate), No. CAS is
114435-02-8,
[chemical formula 2]
Prepare the preparation of 1. glyoxal sulfate of embodiment
The compound of the chemical formula 1 can be prepared by following known synthetic method.
Firstly, 1000mL three-necked flask and condenser are connected on 60 DEG C of oil bath pan.Add in the three-necked flask
Add 1,1,2,2- tetrachloroethanes 70g, and temperature is stablized after 60 DEG C, addition sulfuric acid (60%fuming grade) 320g starts
Reaction.Reaction solution, which is initially shown, is clear to beige viscosity, and forms crystalline solid after reaction starts 4 hours.It will
Oil bath pan is cooled to room temperature, and is in addition stirred at low speed 3 hours.Then, it is changed to 5~7 DEG C of cryostat pot, and separately low beam stirring
2 hours.When not continuously forming crystalline solid, reaction was completed.It is separated by solid-liquid separation using pulp solution of the filter to acquisition
Afterwards, it is dried in vacuo 12 hours at 20Torr.It (is produced as a result, obtaining by the glyoxal sulfate 72.8g that the chemical formula 1 indicates
Rate: 84.4%).
The preparation of 1. electrolyte solution of embodiment
Ethylene carbonate (EC), methyl ethyl carbonate (EMC) and diethyl carbonate (DEC) is mixed with the volume ratio of 25:35:40
Conjunction prepares mixed solution, and dissolves LiPF in the mixed solution with the concentration of 1 mole/L6, and add relative to electrolyte
The glyoxal sulfate indicated by the chemical formula 1 of 1 weight percent of total weight and 1 weight percent by the chemical formula
2 fluorinated ethylene carbonates indicated are mixed, and prepare secondary cell electrolyte (electrolyte solution) with this.
The preparation of 2. electrolyte solution of embodiment
The glyoxal sulfate and 1.5 weight percent indicated by the chemical formula 1 in addition to adding 1.5 weight percent
The fluorinated ethylene carbonate indicated by the chemical formula 2 other than, electrolyte is prepared by method same as Example 1.
The preparation of 3. electrolyte solution of embodiment
In addition to addition 2 weight percent the glyoxal sulfate indicated by the chemical formula 1 and 2 weight percent by
Other than the fluorinated ethylene carbonate that the chemical formula 2 indicates, electrolyte is prepared by method same as Example 1.
The preparation of 4. electrolyte solution of embodiment
In addition to addition 1 weight percent the glyoxal sulfate indicated by the chemical formula 1 and 2 weight percent by
Other than the fluorinated ethylene carbonate that the chemical formula 2 indicates, electrolyte is prepared by method same as Example 1.
The preparation of 1. electrolyte solution of comparative example
In addition to not adding the glyoxal sulfate indicated by the chemical formula 1, and 3 weight percent of addition by institute
Other than the fluorinated ethylene carbonate for stating the expression of chemical formula 2, electrolyte is prepared by method same as Example 1.
The preparation of 2. electrolyte solution of comparative example
Other than not adding the glyoxal sulfate indicated by the chemical formula 1, pass through side same as Example 4
Method prepares electrolyte.
The preparation of 3. electrolyte solution of comparative example
Other than not adding the glyoxal sulfate indicated by the chemical formula 1, pass through side same as Example 1
Method prepares electrolyte.
The preparation of 4. electrolyte solution of comparative example
In addition to the fluoro for not adding the glyoxal sulfate indicated by the chemical formula 1 and being indicated by the chemical formula 2
Other than ethylene carbonate, electrolyte is prepared by method same as Example 1.
The low temperature life and output characteristics of 1. lithium secondary battery of experimental example
LiNi is used using as active material of positive electrode1/3Co1/3Mn1/3Anode material, and make according to 1:1 weight ratio
It is used as the artificial graphite of active material of cathode and the cathode material of natural graphite, 1.4Ah Soft Roll is assembled according to usual way
Battery, and it is injected separately into the electrolyte of embodiment 1 to embodiment 4 described in 6.5g and comparative example 1 to comparative example 4, prepare secondary electricity
Pond.The 1.4Ah soft-package battery that will be obtained by the battery moulding process, in 25 DEG C of constant current/constant voltage (CC/CV)
Under the conditions of 4.2V/140mA is charged to 1C (coulomb) after, 3V is discharged to 1C under the conditions of constant current (CC), and use
PNE-0506 device for charge/discharge (manufacturer: (strain) PNE solution) measures initial capacity.In addition, keeping relative to complete
The voltage of the charged state of charging 60% with 3C electric discharge 10 seconds, and calculates initial resistance according to the voltage difference generated at this time.
In addition, by the battery it is fully charged after, with 1C under the conditions of -10 DEG C of constant current/constant voltage (CC/CV)
After charging to 4.2V/140mA, 3V is discharged to 1C under the conditions of constant current (CC), is repeated after implementing 10 times, using with it is as above
The identical device for charge/discharge of the device for charge/discharge measures discharge capacity.In addition, keeping relative to fully charged
The voltage of 60% charged state, and resistance is calculated according to the voltage measured while electric discharge 10 seconds with 3C.According to thus measuring
Discharge capacity calculate capacity maintenance rate relative to battery design capacity (1.4Ah), and according to resistance calculations relative to benchmark
The resistance percentage of resistance (initial resistance of comparative example 4) is simultaneously shown in Table 1.
[table 1]
(capacity maintenance rate and resistance percentage after discharging 10 times at -10 DEG C)
As shown in table 1, with no addition additive (comparative example 4) or only use a kind of additive of fluorinated ethylene carbonate
(comparative example 1 to comparative example 3) is compared, and capacity of the electrolyte of embodiment 1 to embodiment 4 in low temperature is in phase same level, and
It is more excellent in terms of battery internal resistance at low temperature when the content of additive is identical.This is because having used includes institute
The combined electrolyte of the compound of chemical formula 1 and the chemical formula 2 is stated, even if so low temperature ring declined in ionic conductance
Also excellent capacity level is shown under border, and resistance does not dramatically increase.In particular, in embodiment 2 into embodiment 4,
The resistance of embodiment 3 is minimum, by this point, can be confirmed that glyoxal sulfate generates very big shadow to the output for improving battery
It rings.
The room temperature service life of 2. lithium secondary battery of experimental example and output characteristics
Battery moulding process is carried out according to method identical with the experimental example 1 and obtains secondary cell (1.4Ah Soft Roll electricity
Pond) after, 4.2V/140mA is charged to 1C under the conditions of 25 DEG C of constant current/constant voltage (CC/CV).Then, at 25 DEG C
Constant current (CC) under the conditions of 3V is discharged to 1C, and (manufacturer: (strain) PNE is solved using PNE-0506 device for charge/discharge
Certainly scheme) measurement initial discharge capacity.In addition, keeping the voltage of the charged state relative to fully charged 60%, discharged with 3C
10 seconds, and initial resistance is calculated according to the voltage difference generated at this time.
In addition, the battery is charged under the conditions of 25 DEG C of constant current/constant voltage (CC/CV) with 0.5C
After 4.2V/140mA, 3V is discharged to 0.5C under the conditions of constant current (CC), is repeated after implementing 20 times, using with it is as described above
The identical device for charge/discharge of device for charge/discharge measure discharge capacity.Then, the constant electricity by the battery at 25 DEG C
4.2V/140mA is charged to 2C under the conditions of stream/constant voltage (CC/CV), and is discharged under the conditions of constant current (CC) with 2C
3V is repeated after implementing 20 times, is measured electric discharge using device for charge/discharge identical with device for charge/discharge as described above and is held
Amount.Then, the battery is discharged to 4.2V/140mA under the conditions of 25 DEG C of constant current/constant voltage (CC/CV) with 3C,
And 3V is discharged to 3C under the conditions of constant current (CC), it repeats after implementing 20 times, is filled using with charge/discharge as described above
Set identical device for charge/discharge measurement discharge capacity.Then, constant current/constant voltage by the battery at 25 DEG C
(CC/CV) 4.2V/140mA is charged to 4C under the conditions of, and 3V is discharged to 4C under the conditions of constant current (CC), repeats to implement
After 20 times, discharge capacity is measured using device for charge/discharge identical with device for charge/discharge as described above.Then, it keeps
Electricity is calculated relative to the voltage of fully charged 60% charged state, and according to the voltage measured while electric discharge 10 seconds with 3C
Resistance.The capacity maintenance rate relative to battery design capacity (1.4Ah) is calculated according to the 100th discharge capacity thus measured, and
It relative to the resistance percentage of reference resistance (initial resistance of comparative example 4) and is shown in Table 2 according to resistance calculations.
[table 2]
(capacity maintenance rate and resistance percentage after discharging 100 times at 25 DEG C)
As shown in table 2, with no addition additive (comparative example 4) or only use a kind of additive of fluorinated ethylene carbonate
(comparative example 1 to comparative example 3) is compared, even if the electrolyte of embodiment 1 to embodiment 4 battery charging and discharging speed very
In the case where fast, it may have excellent capacity maintains and resistance maintains performance.This is because having used includes 1 He of chemical formula
The combined electrolyte of the compound of the chemical formula 2, so the output characteristics of battery is improved.It is possible thereby to confirm,
The combined electrolyte of compound including the chemical formula 1 and the chemical formula 2 also can in rapid charge and high rate discharge
Keep excellent battery behavior.
The life characteristics at high temperature of 3. lithium secondary battery of experimental example
Battery moulding process is carried out according to method identical with the experimental example 1 and obtains secondary cell (1.4Ah Soft Roll electricity
Pond) after, 4.2V/140mA is charged to 1C under the conditions of initial 45 DEG C of constant current/constant voltage (CC/CV).Then, exist
3V is discharged to 1C under the conditions of constant current (CC), and (manufacturer: (strain) PNE is solved using PNE-0506 device for charge/discharge
Scheme) measurement initial discharge capacity.In addition, the voltage of the charged state relative to fully charged 60% is kept, with 3C electric discharge 10
Second, and initial resistance is calculated according to the voltage difference generated at this time.Then, repeat 300 discharge processes as described above with
Afterwards, the 300th discharge capacity is measured using device for charge/discharge identical with device for charge/discharge as described above.According to
Thus the 300th discharge capacity measured calculates the capacity maintenance rate relative to battery design capacity (1.4Ah), and is shown in table 3
In.
[table 3]
(capacity maintenance rate after discharging 300 times at 45 DEG C)
As shown in table 3, with no addition additive (comparative example 4) or only use a kind of additive of fluorinated ethylene carbonate
(comparative example 1 to comparative example 3) is compared, and the life characteristics at high temperature of the battery of the electrolyte of embodiment 1 to embodiment 4 is changed
It is kind.This is because the combined electrolyte of the compound including the chemical formula 1 and the chemical formula 2 has been used, so reducing
The side reaction between electrolyte and electrode occurred when battery is used continuously at high temperature, and prevent cell degradation.It is possible thereby to
Confirmation, the combined electrolyte of the compound including the chemical formula 1 and the chemical formula 2 can also be shown for a long time at high temperature
, excellent life characteristic.
Capacity and output characteristics of 4. lithium secondary battery of experimental example in High temperature storage
Battery moulding process is carried out according to method identical with the experimental example 1 and obtains secondary cell (1.4Ah Soft Roll electricity
Pond) after, 4.2V/140mA is charged to 1C under the conditions of 25 DEG C of constant current/constant voltage (CC/CV).Then, at 25 DEG C
Constant current (CC) under the conditions of 3V is discharged to 1C, and (manufacturer: (strain) PNE is solved using PNE-0506 device for charge/discharge
Certainly scheme) measurement initial discharge capacity.In addition, keeping the voltage of the charged state relative to fully charged 60%, discharged with 3C
10 seconds, and initial resistance is calculated according to the voltage difference generated at this time.
In addition, by the battery at 25 DEG C it is fully charged after, 4 weeks are saved in 50 DEG C of baking oven, then using as above
The method measures discharge capacity and resistance after 4 weeks.It is set according to the calculation of capacity thus measured relative to battery
Count the capacity maintenance rate of capacity (1.4Ah), and the electricity according to resistance calculations relative to reference resistance (initial resistance of comparative example 4)
Resistance percentage is simultaneously shown in Table 4.
[table 4]
(capacity maintenance rate and resistance percentage after being saved 4 weeks at 70 DEG C)
As shown in table 4, with no addition additive (comparative example 4) or only use a kind of additive of fluorinated ethylene carbonate
(comparative example 1 to comparative example 3) is compared, can be confirmed the electrolyte of embodiment 1 to embodiment 4 at high temperature long-term preservation when
The capacity and resistance characteristic of battery are improved.This is because having used the chemical combination including the chemical formula 1 and the chemical formula 2
The combined electrolyte of object, the pair between electrolyte and electrode occurred when so reducing long-term placing battery at high temperature are anti-
It answers, and prevents cell degradation.In particular, embodiment 3 maintains the performance of capacity and resistance most in embodiment 2 into embodiment 4
To be excellent, by this point, it can be confirmed that glyoxal sulfate produces a very large impact capacity and output at a high temperature of long-term.
Claims (7)
1. a kind of secondary cell electrolyte, comprising:
Carbonate-based solvent；
Lithium salts；
The compound of following chemical formula 1；And
The compound of following chemical formula 2,
[chemical formula 1]
[chemical formula 2]
2. secondary cell electrolyte according to claim 1, it is characterised in that:
The carbonate-based solvent includes selected from by diethyl carbonate (diethyl carbonate), methyl ethyl carbonate
(ethylmethyl carbonate), dimethyl carbonate (dimethyl carbonate), dipropyl carbonate (dipropyl
Carbonate), methyl propyl carbonate (methylpropyl carbonate), carbonic acid ethylpropyl (ethylpropyl
Carbonate), ethylene carbonate (ethylene carbonate), propylene carbonate (propylene carbonate), carbon
The group of sour butylene (butylene carbonate) and gamma-butyrolacton (gamma-butyrolactone) composition it is a kind of with
On.
3. secondary cell electrolyte according to claim 2, it is characterised in that:
The carbonate-based solvent includes selected from by diethyl carbonate, methyl ethyl carbonate, dimethyl carbonate, dipropyl carbonate, carbon
More than one linear carbonates class solvent of the group of sour first propyl ester and carbonic acid ethylpropyl composition；And
More than one cyclic annular carbon selected from the group being made of ethylene carbonate, propylene carbonate, butylene carbonate and gamma-butyrolacton
Esters of gallic acid solvent.
4. secondary cell electrolyte according to claim 1, it is characterised in that:
The lithium salts includes selected from by LiPF6、LiBF4、LiBF6、LiSbF6、LiAsF6、LiClO4、LiSO3CF3、LiN
(CF3SO2)2、LiN(C2F5SO2)2、LiN(SO2F)2With LiC (CF3SO2)3The group of composition more than one.
5. secondary cell electrolyte according to claim 1, it is characterised in that:
The electrolyte includes the compound and 0.05 of the chemical formula 1 of 0.1 to 10 weight percent relative to total weight
To the compound of the chemical formula 2 of 10 weight percent.
6. secondary cell electrolyte according to claim 1, it is characterised in that:
The electrolyte includes 0.05 to 5.0 mole of the carbonate-based solvent of the lithium salts relative to 1L.
7. a kind of including secondary to the secondary cell electrolyte described in any one of claim 6 according to claim 1
Battery.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160156441A KR20180057944A (en) | 2016-11-23 | 2016-11-23 | Electrolyte for secondary battery and secondary battery comprising same |
| KR10-2016-0156441 | 2016-11-23 | ||
| PCT/KR2017/012650 WO2018097519A1 (en) | 2016-11-23 | 2017-11-09 | Electrolyte solution for secondary battery and secondary battery comprising same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109792082A true CN109792082A (en) | 2019-05-21 |
Family
ID=62195264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780055867.9A Pending CN109792082A (en) | 2016-11-23 | 2017-11-09 | A kind of secondary cell electrolyte and the secondary cell including it |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20180057944A (en) |
| CN (1) | CN109792082A (en) |
| WO (1) | WO2018097519A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111261939A (en) * | 2020-01-20 | 2020-06-09 | 宁德新能源科技有限公司 | Electrolyte solution and electrochemical device using the same |
| WO2022042373A1 (en) * | 2020-08-31 | 2022-03-03 | 深圳新宙邦科技股份有限公司 | Lithium ion battery |
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| JP2015149234A (en) * | 2014-02-07 | 2015-08-20 | 三井化学株式会社 | Nonaqueous electrolyte for battery and lithium secondary battery |
| CN105428713A (en) * | 2014-09-11 | 2016-03-23 | Sk新技术株式会社 | Electrolyte for Lithium Secondary Battery and Lithium Secondary Battery Containing the Same |
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| KR102030347B1 (en) * | 2012-06-19 | 2019-11-18 | 에스케이이노베이션 주식회사 | Electrolyte for lithium secondary battery including additives,and lithium secondary battery |
| KR101620214B1 (en) * | 2013-10-31 | 2016-05-12 | 주식회사 엘지화학 | Additive for non-aqueous liquid electrolyte, non-aqueous liquid electrolyte and lithium secondary battery comprising the same |
| CN103779604B (en) * | 2014-02-21 | 2016-10-19 | 宁德新能源科技有限公司 | Lithium rechargeable battery and electrolyte thereof |
| JP6735777B2 (en) * | 2015-07-16 | 2020-08-05 | エスケー ケミカルズ カンパニー リミテッド | Electrolyte additive for secondary battery, electrolyte containing the same, and secondary battery |
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2016
- 2016-11-23 KR KR1020160156441A patent/KR20180057944A/en unknown
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2017
- 2017-11-09 CN CN201780055867.9A patent/CN109792082A/en active Pending
- 2017-11-09 WO PCT/KR2017/012650 patent/WO2018097519A1/en active Application Filing
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| JP2013229307A (en) * | 2012-03-27 | 2013-11-07 | Tdk Corp | Nonaqueous electrolyte solution and lithium ion secondary battery |
| US20160211551A1 (en) * | 2013-09-25 | 2016-07-21 | Mitsui Chemicals, Inc. | Non-aqueous electrolyte solution for battery and lithium secondary battery |
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| CN103985906A (en) * | 2014-06-06 | 2014-08-13 | 东莞市杉杉电池材料有限公司 | Lithium ion battery electrolyte with both high and low temperature performances |
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| CN111261939A (en) * | 2020-01-20 | 2020-06-09 | 宁德新能源科技有限公司 | Electrolyte solution and electrochemical device using the same |
| WO2022042373A1 (en) * | 2020-08-31 | 2022-03-03 | 深圳新宙邦科技股份有限公司 | Lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018097519A1 (en) | 2018-05-31 |
| KR20180057944A (en) | 2018-05-31 |
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