CN106159324A - Nonaqueous electrolytic solution and the lithium secondary battery using this nonaqueous electrolytic solution - Google Patents
Nonaqueous electrolytic solution and the lithium secondary battery using this nonaqueous electrolytic solution Download PDFInfo
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- CN106159324A CN106159324A CN201610523100.1A CN201610523100A CN106159324A CN 106159324 A CN106159324 A CN 106159324A CN 201610523100 A CN201610523100 A CN 201610523100A CN 106159324 A CN106159324 A CN 106159324A
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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
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of nonaqueous electrolytic solution and use the lithium secondary battery of this nonaqueous electrolytic solution；Described nonaqueous electrolytic solution contains electrolyte lithium salt, non-aqueous organic solvent, cesium salt compound additive and film for additive, and described cesium salt compound additive accounts for 0.01%～20% mass fraction of described non-aqueous organic solvent total amount.In nonaqueous electrolytic solution provided by the present invention, cesium salt compound additive can increase ionic conductivity in charge and discharge process for the electrode surface, reduce the impedance of the SEI film that conventional film for additive is formed at electrode surface, maintain the cyclical stability of good lithium secondary battery, significantly improve cryogenic property and high rate performance simultaneously.
Description
Technical field
The invention belongs to lithium secondary battery field, relate to a kind of nonaqueous electrolytic solution and use the lithium secondary of this nonaqueous electrolytic solution
Battery.While the nonaqueous electrolytic solution that the present invention relates to can improve the long-term cycle performance of lithium secondary battery, significantly improve low
Warm nature energy and high rate performance.
Background technology
Lithium secondary battery has the advantage that specific energy is high, specific power is high and has extended cycle life, and is widely used to portable
Electronic equipment.With becoming increasingly conspicuous of the energy and environmental problem, lithium secondary battery is applied electric automobile and energy storage field
To developing rapidly.Lithium secondary battery used for electric vehicle needs longer cycle life, in lithium battery electrolytes, adds film forming
Additive can suppress electrolyte decomposition, improve cycle life, but also can increase the impedance of electrode surface simultaneously；Particularly exist
Under cryogenic conditions, owing to interface impedance dramatically increases, battery charging and discharging capacity, high rate performance can be substantially reduced, be also possible to simultaneously
Battery can be caused to generate heat in a large number, bring potential safety hazard, limit the application in electric automobile field for the lithium secondary battery.
In lithium secondary cell electrolyte field, more researcher takes to add the relatively low film for additive of interface impedance value and subtracts
The increase of few SEI membrane impedance value, but stable SEI film, interface impedance value is often higher, therefore finds one and improves SEI film
The electrolysis additive of interface impedance is very necessary.
Content of the invention
After it is an object of the invention to overcome the conventional film for additive of interpolation, electrode material surface SEI membrane impedance increases, greatly
Rate charge-discharge impaired performance, cryogenic property weaken, make battery use the limited defect of environment, provide a kind of new can changing
The nonaqueous electrolytic solution of kind SEI membrane interface impedance and the lithium secondary battery using this nonaqueous electrolytic solution.Relative to conventional electrolysis liquid, should
Nonaqueous electrolytic solution can maintain good lithium secondary battery cyclical stability, significantly improve cryogenic property and forthright again simultaneously
Energy.
It is an object of the invention to be achieved through the following technical solutions:
The present invention relates to one (secondary lithium batteries) nonaqueous electrolytic solution, described nonaqueous electrolytic solution contain electrolyte lithium salt,
Non-aqueous organic solvent, cesium salt compound additive.
Preferably, described cesium salt compound additive is selected from: caesium halide CsX (X=F, Cl, Br, I), Cs2CO3、CsPF6、
CsBF4、CsClO4、CsAsF6、CsTFSI、CsFSI、HCOOCs、CH3COOCs、CH3(CH2)16One or more in COOCs.
Preferably, described cesium salt compound additive accounts for 0.01%～20% mass of described non-aqueous organic solvent total amount and divides
Number.
Preferably, described nonaqueous electrolytic solution is possibly together with film for additive.
Preferably, described film for additive include vinylene carbonate, PS, Isosorbide-5-Nitrae-butyl sultone,
Vinylethylene carbonate, N, one or more in N-dimethyl trifluoroacetamide, adiponitrile.
Preferably, described film for additive accounts for the 0.01%～10% of described non-aqueous organic solvent gross mass.
Preferably, described electrolyte lithium salt includes: LiTFSI, LiPF6、LiBF4、LIFSI、LiBOB、LiODFB、
LiClO4、LiAsF6In one or more.
Preferably, described non-aqueous organic solvent includes: cyclic carbonate, linear carbonate, sulfurous esters organic solvent,
Chain carboxylic acid esters organic solvent, diethylene glycol dimethyl ether, dioxolanes, dimethoxy-ethane, diethoxyethane, ethylene glycol two
One or more in methyl ether, dimethyl sulfoxide (DMSO), sulfolane.
Preferably, described cyclic carbonate includes: ethylene carbonate, propene carbonate, butylene, fluoro ethylene
Alkene ester, gamma-butyrolacton.
Preferably, described linear carbonate includes: dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, carbonic acid first third
Ester.
Preferably, described sulfurous esters organic solvent includes: ethylene sulfite, propylene sulfite, sulfurous acid two
Methyl esters, sulfurous acid diethyl ester.
Preferably, described chain carboxylic acid esters organic solvent includes: methyl formate, Ethyl formate, methyl acetate, acetic acid second
Ester, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, butyl propionate, ethyl butyrate.
Diethylene glycol dimethyl ether, dioxolanes, dimethoxy-ethane, diethoxyethane, glycol dimethyl ether, dimethyl are sub-
Sulfone, sulfolane are other organic solvents being not belonging to above-mentioned classification.
The invention still further relates to a kind of lithium secondary battery, including above-mentioned nonaqueous electrolytic solution, have and can embed and deviate from lithium
The positive pole of the positive electrode active materials of ion and negative pole.
Preferably, described positive electrode active materials is selected from lithium-transition metal composite oxide, sulphur simple substance, sulphur carbon complex, sulphur
One in polymer complex.
Preferably, the active material that described negative pole uses is material with carbon element, the lithium elemental metals with graphite mould crystal structure
And alloy, elemental metals containing silicon, alloy and compound thereof, elemental metals containing tin, alloy and compound, metatitanic acid
One in lithium compound.
Compared with prior art, there is advantages that
1st, the cesium salt compound additive comprising in nonaqueous electrolytic solution provided by the present invention can improve the resistance of SEI membrane interface
Anti-, significantly improve cryogenic property and high rate performance.
2nd, in nonaqueous electrolytic solution provided by the present invention, the cesium salt compound additive of suitable consumption adds with other film forming
Agent is with the use of not only making lithium secondary battery have excellent cyclical stability, also have excellent high rate performance, cryogenic property
And security performance.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.Following example will assist in those skilled in the art
It is further appreciated by the present invention, but do not limit the present invention in any form.It should be pointed out that, to those of ordinary skill in the art
For, without departing from the inventive concept of the premise, can also make certain adjustments and improvements.These broadly fall into the guarantor of the present invention
Protect scope.
Embodiment 1
The preparation of electrolyte
It in the argon atmosphere glove box being dried (water and oxygen content are less than 1ppm), by non-aqueous organic solvent is in mass ratio
Ethylene carbonate (EC): dimethyl carbonate (DMC): methyl ethyl carbonate (EMC) 1:1:1 prepares mixed solvent；According to mixed solvent,
LiPF6、CsPF6And vinylene carbonate (VC) mass ratio is that 85:12:1:2 mixes, obtain lithium secondary of the present invention
Battery electrolyte.
Prepared by positive pole
LiCoO by 92% mass percent2, the conductive black of 4% mass percent and gathering partially of 4% mass percent
PVF (PVDF) mixes, and adds N methyl 2 pyrrolidones to stir, makes anode sizing agent, be coated uniformly on aluminium
Paper tinsel two sides, is dried, suppresses and shears and obtain anode pole piece.
Prepared by negative pole
The SBR binding agent of 4% mass percent and the CMC thickener of 2% mass percent are added to the water, add
The Delanium of 94% mass percent, is sufficiently stirred for, and mixes and obtains cathode size, and cathode size is coated to Copper Foil two
Face, is dried, suppresses and shears and obtain cathode pole piece.
The preparation of lithium secondary battery
Successively stacked on state cathode pole piece, anode pole piece and polyethylene diagrams according to negative pole, barrier film, positive pole, the order of negative pole
Make rectangular cell element, insert this element in laminated aluminum film bag, and make positive pole and negative lug highlight, inject in bag
Above-mentioned electrolyte, then carries out vacuum sealing, the 2Ah flexible-packed battery of system after shelving and being melted into.The battery preparing is carried out
The performance evaluation of following items.
The evaluation method of the lithium secondary battery of preparation is listed below.
Initial capacity is tested
At 25 DEG C, carry out constant-current charge, blanking voltage 4.2V with 0.3C electric current, carry out constant-voltage charge at 4.2v, cut
Only electric current 0.03C；Then carrying out constant-current discharge with 0.3C, blanking voltage is 3V.Circulating battery 5 times make battery stable, with
The discharge capacity of the 5th circulation is as the initial discharge capacity of battery.
Normal-temperature circulating performance is tested
Carry out the battery finishing initial capacity evaluation experimental at 25 DEG C, carry out constant-current charge with 1C electric current, cut-off
Voltage 4.2V, carries out constant-voltage charge, cut-off current 0.05C at 4.2v；Then carrying out constant-current discharge with 1C, blanking voltage is 3V
Circulation experiment.Obtain the 1st cyclic discharge capacity as the discharge capacity (%) of the when 100 the 500th time.
Low-temperature circulating is tested
Carry out the battery finishing initial capacity evaluation experimental at 0 DEG C, carry out constant-current charge, cut-off electricity with 1C electric current
Pressure 4.2V, carries out constant-voltage charge, cut-off current 0.05C at 4.2v；Then carrying out constant-current discharge with 1C, blanking voltage is 3V's
Circulation experiment.Obtain the 1st cyclic discharge capacity as the discharge capacity (%) of the when 100 the 200th time.
Embodiment 2
By the CsPF in embodiment 16Mass fraction change 0.01% into, in addition similarly to Example 1 operation preparation
Electrolyte, prepare lithium secondary battery and carry out relevant evaluation.Table 1 shows evaluation result.
Embodiment 3
By the CsPF in embodiment 16Mass fraction change 0.5% into, in addition similarly to Example 1 operation preparation electricity
Solve liquid, prepare lithium secondary battery and carry out relevant evaluation.Table 1 shows evaluation result.
Embodiment 4
By the CsPF in embodiment 16Mass fraction change 2% into, in addition similarly to Example 1 operation preparation electrolysis
Liquid, prepare lithium secondary battery and carry out relevant evaluation.Table 1 shows evaluation result.
Embodiment 5
By the CsPF in embodiment 16Mass fraction change 5% into, in addition similarly to Example 1 operation preparation electrolysis
Liquid, prepare lithium secondary battery and carry out relevant evaluation.Table 1 shows evaluation result.
Embodiment 6
By the CsPF in embodiment 16Mass fraction change 20% into, in addition similarly to Example 1 operation preparation electricity
Solve liquid, prepare lithium secondary battery and carry out relevant evaluation.Table 1 shows evaluation result.
Embodiment 7
Change the mass fraction of the film for additive vinylene carbonate in embodiment 1 into 0.01%, in addition with reality
Execute example 1 to operate preparation electrolyte equally, prepare lithium secondary battery and carry out relevant evaluation.Table 1 shows evaluation result.
Embodiment 8
Change the mass fraction of the film for additive vinylene carbonate in embodiment 1 into 10%, in addition with enforcement
Example 1 operates preparation electrolyte equally, prepares lithium secondary battery and carry out relevant evaluation.Table 1 shows evaluation result.
Embodiment 9
By the cesium salt compound CsPF in embodiment 16Change CH into3COOCs, in addition operation preparation similarly to Example 1
Electrolyte, prepare lithium secondary battery and carry out relevant evaluation.Table 1 shows evaluation result.
Embodiment 10
By the cesium salt compound CsPF in embodiment 16Change CsAsF into6, and film for additive vinylene carbonate is changed into
N, N-dimethyl trifluoroacetamide, in addition operation is prepared electrolyte, is prepared lithium secondary battery and carry out similarly to Example 1
Relevant evaluation.Table 1 shows evaluation result.
Embodiment 11
By the cesium salt compound CsPF in embodiment 16Changing CsTFSI into, film for additive vinylene carbonate changes 1,3-into
Propane sultone (the 1st, 3-PS), in addition operation is prepared electrolyte, is prepared lithium secondary battery and carry out phase similarly to Example 1
Close and evaluate.Table 1 shows evaluation result.
Comparative example 1
It in the argon atmosphere glove box being dried (water and oxygen content are less than 1ppm), by non-aqueous organic solvent is in mass ratio
Ethylene carbonate (EC): dimethyl carbonate (DMC): methyl ethyl carbonate (EMC) 1:1:1 prepares mixed solvent；According to mixed solvent,
LiPF6, and vinylene carbonate (VC) mass ratio be that 86:12:2 mixes, obtain lithium secondary battery of the present invention electricity
Solve liquid.
In addition operation is prepared electrolyte, is prepared lithium secondary battery and carry out relevant evaluation similarly to Example 1.Table 1
Display evaluation result.
Comparative example 2
It in the argon atmosphere glove box being dried (water and oxygen content are less than 1ppm), by non-aqueous organic solvent is in mass ratio
Ethylene carbonate (EC): dimethyl carbonate (DMC): methyl ethyl carbonate (EMC) 1:1:1 prepares mixed solvent；According to mixed solvent,
LiPF6, and CsPF6Mass ratio is that 87:12:1 mixes, and obtains lithium secondary cell electrolyte of the present invention.
In addition operation is prepared electrolyte, is prepared lithium secondary battery and carry out relevant evaluation similarly to Example 1.Table 1
Display evaluation result.
Comparative example 3
It in the argon atmosphere glove box being dried (water and oxygen content are less than 1ppm), by non-aqueous organic solvent is in mass ratio
Ethylene carbonate (EC): dimethyl carbonate (DMC): methyl ethyl carbonate (EMC) 1:1:1 prepares mixed solvent；According to mixed solvent,
LiPF6, and CsPF6Mass ratio is that 88:12 mixes, and obtains lithium secondary cell electrolyte of the present invention.Obtain the present invention
Described lithium secondary cell electrolyte.
In addition operation is prepared electrolyte, is prepared lithium secondary battery and carry out relevant evaluation similarly to Example 1.Table 1
Display evaluation result.
Morphology observation
By in embodiment 1 and comparative example 3, the battery after 200 circulations of low temperature is at the argon atmosphere gloves being dried
In case, (water and oxygen content are less than 1ppm) disassembles, and carries out paired observation to the pattern of cathode pole piece.
Table 1 lithium secondary battery test evaluation result
Electrolyte adds suitable CsPF as can be seen from Table 16Lithium secondary after interpolation film for additive will not be reduced
The normal-temperature circulating performance of battery, but cryogenic property can be significantly improved.Can be seen that the amount mistake that film for additive adds simultaneously
How can significantly reduce cryogenic property, and normal-temperature circulating performance be promoted little.Cesium salt compound and film for additive with the use of
Preferable normal-temperature circulating performance can be kept, lithium battery cryogenic property can be significantly improved simultaneously.The more preferably use of cesium salt compound
Amount is 0.01%～5%, with film for additive 0.01%～2% with the use of.
By the pattern comparative analysis of the negative pole piece of battery after 200 circulations of low temperature, add suitable CsPF6After
Through 200 circulations of low temperature, cathode pole piece is still fine and close smooth, without adding CsPF6Battery low temperature 200 times circulation after negative
There is out-of-flatness in pole surface, even the phenomenon of efflorescence.Therefore conclude that CsPF6Addition advantageously reduce cryogenic conditions interface resistance
Anti-, even if making lithium battery at a lower temperature, also can be stable carry out discharge and recharge.
Embodiment 11
Replace the positive active material in embodiment 1, use LiNi1/3Co1/3Mn1/3O2Tertiary cathode material replaces LiCoO2
Positive electrode, in addition operation is prepared electrolyte, is prepared lithium secondary battery similarly to Example 1, and carries out in embodiment 1
Initial capacity is tested, normal-temperature circulating performance test and low temperature capacity test.Table 2 shows evaluation result.
Comparative example 4
Replace the positive active material in comparative example 1, use LiNi1/3Co1/3Mn1/3O2Tertiary cathode material replaces LiCoO2
Positive electrode, in addition operation is prepared electrolyte, is prepared lithium secondary battery as comparative example 2, and carries out in embodiment 1
Initial capacity test, normal-temperature circulating performance test and low temperature capacity test.Table 2 shows evaluation result.
Table 2 tertiary cathode material lithium secondary battery evaluation test result
From Table 2, it can be seen that positive electrode is changed into tertiary cathode material, CsPF6The effect that additive plays is phase
As.
Embodiment 12
Replace the negative active core-shell material in embodiment 1, use Si negative active core-shell material to make negative active core-shell material.By 75%
The Si active material of mass percent, the conductive black of 15% mass percent, the SBR binding agent and 5% of 5% mass percent
The CMC binding agent of mass percent mixes, and adds deionized water to stir, makes cathode size.In addition with reality
Executing example 1 to operate preparation electrolyte equally, prepare lithium secondary battery, and carrying out the performance evaluation of project, table 3 shows evaluation result.
Initial capacity is tested
At 25 DEG C, carry out constant-current charge, blanking voltage 4.2V with 0.3C electric current, carry out constant-voltage charge at 4.2v, cut
Only electric current 0.03C；Then carrying out constant-current discharge with 0.3C, blanking voltage is 2.5V.Circulating battery 5 times make battery stable,
Using the discharge capacity of the 5th circulation as the initial discharge capacity of battery.
Normal-temperature circulating performance is tested
Carry out the battery finishing initial capacity evaluation experimental at 25 DEG C, carry out constant-current charge with 1C electric current, cut-off
Voltage 4.2V, carries out constant-voltage charge, cut-off current 0.05C at 4.2v；Then carrying out constant-current discharge with 1C, blanking voltage is
The circulation experiment of 2.5V.Obtain the 1st cyclic discharge capacity as the discharge capacity (%) of the when 100 the 100th time.
Comparative example 5
Replace the negative active core-shell material in comparative example 1, use Si negative active core-shell material to make negative active core-shell material.By 75%
The Si active material of mass percent, the conductive black of 15% mass percent and the Kynoar of 10% mass percent
(PVDF) mix, add N methyl 2 pyrrolidones to stir, make cathode size.In addition with comparative example 2
Same operation is prepared electrolyte, is prepared lithium secondary battery, and the initial capacity test carrying out in embodiment 1 is surveyed with low temperature capacity
Examination, table 3 shows evaluation result.
Initial capacity is tested
At 25 DEG C, carry out constant-current charge, blanking voltage 4.2V with 0.3C electric current, carry out constant-voltage charge at 4.2v, cut
Only electric current 0.03C；Battery is put into standing more than 4h in-20 DEG C of environment storehouses, then carries out constant-current discharge, blanking voltage with 0.3C
For 2V, electric discharge capacity, the numerical value of low temperature discharge capacity, divided by the numerical value of initial discharge capacity, is low temperature discharge capacity and protects
Holdup.
Table 3 lithium secondary battery evaluation test result (Si active material does negative pole)
It is found that CsPF from table 36Addition in the case of negative pole is employed containing Si active material, Ke Yiti
High temperature performance.
Embodiment 13
The preparation of electrolyte
It in the argon atmosphere glove box being dried (water and oxygen content are less than 1ppm), is diethylene glycol (DEG) two in mass ratio by solvent
Methyl ether (DGM): dimethoxy-ethane (DME): the 1st, 3 dioxolanes (DOX) 3:3:4 mixes and prepares mixed solvent, adds
The LiTFSI of 1mol/L, mixes, and adds the CsPF of 1% mass percent6Fluoro ethylene carbonate with 5% mass percent
Ester (FEC) is sufficiently stirred for, and obtains lithium secondary cell electrolyte of the present invention.CsPF6, the mass fraction of FEC refers to account for
The mass percent of non-aqueous organic solvent gross mass.
Prepared by positive pole
By the sulphur of 65% mass percent, the Ketjen black of 15% mass percent and the polycyclic oxygen second of 20% mass percent
Alkane (PEO) mixes, and adds acetonitrile to stir, makes anode sizing agent, be coated uniformly on aluminium foil, be dried, suppress
And shearing obtains anode pole piece.
The preparation of button cell
In the argon atmosphere glove box being dried (water and oxygen content be less than 1ppm), according to anode cover, positive plate, barrier film,
Lithium piece, nickel screen, negative electrode casing order successively stack, and drip appropriate above-mentioned electrolyte, and through press compacting, prepared model is
The button cell of 2016, carries out the performance evaluation of following items after shelving and being melted into.Table 4 shows evaluation result.
Normal-temperature circulating performance is tested
The battery finishing initial capacity evaluation experimental is carried out, at 25 DEG C, carrying out constant-current charge with 0.2C electric current, cuts
Only voltage 3V；Then carrying out constant-current discharge with 0.2C, blanking voltage is the circulation experiment of 1V.Obtain and the 1st circulation electric discharge is held
Measure the discharge capacity (%) as the when 100 the 100th time.
Comparative example 6
It in the argon atmosphere glove box being dried (water and oxygen content are less than 1ppm), is diethylene glycol (DEG) two in mass ratio by solvent
Methyl ether (DGM): dimethoxy-ethane (DME): the 1st, 3 dioxolanes (DOX) 3:3:4 mixes and prepares mixed solvent, adds
The LiTFSI of 1mol/L, mixes, and adds the fluorinated ethylene carbonate (FEC) of 5% mass fraction, abundant without CsPF6
Stirring, obtains lithium secondary cell electrolyte of the present invention.The mass fraction of FEC refers to account for non-aqueous organic solvent gross mass
Mass percent.
In addition operation is prepared electrolyte, is prepared button cell and carry out relevant evaluation similarly to Example 13.Table 4 shows
Show evaluation result.
Table 4 button cell evaluation test result (lithium piece is negative pole)
It is found that CsPF from table 46Add to the low temperature performance significantly improving lithium-sulfur cell.
Above the specific embodiment of the present invention is described.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformation or modification, this not shadow within the scope of the claims
Ring the flesh and blood of the present invention.
Claims (10)
1. a nonaqueous electrolytic solution, it is characterised in that described nonaqueous electrolytic solution contains electrolyte lithium salt, non-aqueous organic solvent, caesium
Salt compound additive.
2. nonaqueous electrolytic solution as claimed in claim 1, it is characterised in that described cesium salt compound additive is selected from:
Caesium halide CsX, Cs2CO3、CsPF6、CsBF4、CsClO4、CsAsF6、CsTFSI、CsFSI、HCOOCs、CH3COOCs、CH3
(CH2)16One or more in COOCs.
3. nonaqueous electrolytic solution as claimed in claim 1 or 2, it is characterised in that described cesium salt compound additive accounts for described non-
The 0.01%～20% of water organic solvent gross mass.
4. nonaqueous electrolytic solution as claimed in claim 1, it is characterised in that described nonaqueous electrolytic solution is possibly together with film for additive.
5. nonaqueous electrolytic solution as claimed in claim 4, it is characterised in that described film for additive include vinylene carbonate,
PS, Isosorbide-5-Nitrae-butyl sultone, vinylethylene carbonate, N, in N-dimethyl trifluoroacetamide, adiponitrile
One or more.
6. nonaqueous electrolytic solution as claimed in claim 4, it is characterised in that described film for additive accounts for described non-aqueous organic solvent
The 0.01%～10% of gross mass.
7. nonaqueous electrolytic solution as claimed in claim 1, it is characterised in that described electrolyte lithium salt includes LiTFSI, LiPF6、
LiBF4、LIFSI、LiBOB、LiODFB、LiClO4、LiAsF6In one or more.
8. nonaqueous electrolytic solution as claimed in claim 1, it is characterised in that described non-aqueous organic solvent include cyclic carbonate,
Linear carbonate, sulfurous esters organic solvent, chain carboxylic acid esters organic solvent, diethylene glycol dimethyl ether, dioxolanes, diformazan
One or more in epoxide ethane, diethoxyethane, glycol dimethyl ether, dimethyl sulfoxide (DMSO), sulfolane.
9. nonaqueous electrolytic solution as claimed in claim 8, it is characterised in that described cyclic carbonate includes ethylene carbonate, carbon
Acid propylene ester, butylene, fluorinated ethylene carbonate, gamma-butyrolacton；Described linear carbonate includes dimethyl carbonate, carbon
Diethyl phthalate, methyl ethyl carbonate, methyl propyl carbonate；Described sulfurous esters organic solvent includes ethylene sulfite, sulfurous acid
Propylene, dimethyl sulfite, sulfurous acid diethyl ester；Described chain carboxylic acid esters organic solvent includes methyl formate, formic acid second
Ester, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, butyl propionate, ethyl butyrate.
10. a lithium secondary battery, it is characterised in that include nonaqueous electrolytic solution as claimed in claim 1, have and can embed
Positive pole and negative pole with the positive electrode active materials deviating from lithium ion.
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| CN201610523100.1A Pending CN106159324A (en) | 2016-07-05 | 2016-07-05 | Nonaqueous electrolytic solution and the lithium secondary battery using this nonaqueous electrolytic solution |
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| CN108878980A (en) * | 2018-08-03 | 2018-11-23 | 浙江长兴中俄新能源材料技术研究院有限公司 | Long-life lithium-ion-power cell function type eletrolysis solution and preparation method thereof |
| CN109860703A (en) * | 2019-01-25 | 2019-06-07 | 宁德新能源科技有限公司 | A kind of electrolyte and electrochemical appliance |
| WO2020121258A1 (en) * | 2018-12-14 | 2020-06-18 | Ses Holdings Pte. Ltd. | Eutectic mixtures containing alkali-metal sulfonimide salts, and electrochemical devices utilizing same |
| CN111710911A (en) * | 2020-07-04 | 2020-09-25 | 湖南大学 | Electrolyte and lithium ion battery |
| CN111900472A (en) * | 2020-06-30 | 2020-11-06 | 远景动力技术(江苏)有限公司 | Non-aqueous electrolyte of lithium ion battery |
| CN111952668A (en) * | 2020-08-13 | 2020-11-17 | 梅州市量能新能源科技有限公司 | Electrolyte, lithium ion battery and preparation method thereof |
| WO2020233234A1 (en) * | 2019-05-23 | 2020-11-26 | Ningde Amperex Technology Limited | Electrolytic solution and electrochemical device using the same |
| CN112086684A (en) * | 2020-09-16 | 2020-12-15 | 松山湖材料实验室 | Cesium-containing high-voltage lithium ion battery electrolyte composite additive, electrolyte and battery thereof |
| CN112271328A (en) * | 2020-09-21 | 2021-01-26 | 东莞市创明电池技术有限公司 | Lithium ion battery electrolyte and lithium ion battery |
| CN113013488A (en) * | 2021-02-25 | 2021-06-22 | 珠海冠宇电池股份有限公司 | Electrolyte and lithium ion battery comprising same |
| CN114335722A (en) * | 2021-12-23 | 2022-04-12 | 惠州锂威新能源科技有限公司 | Lithium ion battery, electrolyte and additive thereof |
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| CN108878980A (en) * | 2018-08-03 | 2018-11-23 | 浙江长兴中俄新能源材料技术研究院有限公司 | Long-life lithium-ion-power cell function type eletrolysis solution and preparation method thereof |
| WO2020121258A1 (en) * | 2018-12-14 | 2020-06-18 | Ses Holdings Pte. Ltd. | Eutectic mixtures containing alkali-metal sulfonimide salts, and electrochemical devices utilizing same |
| CN109860703B (en) * | 2019-01-25 | 2021-04-06 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device |
| CN109860703A (en) * | 2019-01-25 | 2019-06-07 | 宁德新能源科技有限公司 | A kind of electrolyte and electrochemical appliance |
| US11646447B2 (en) | 2019-01-25 | 2023-05-09 | Ningde Amperex Technology Limited | Electrolyte and electrochemical device |
| EP3915166A4 (en) * | 2019-01-25 | 2023-01-18 | Ningde Amperex Technology Ltd. | Electrolyte and electrochemical device |
| WO2020233234A1 (en) * | 2019-05-23 | 2020-11-26 | Ningde Amperex Technology Limited | Electrolytic solution and electrochemical device using the same |
| US11444330B2 (en) | 2019-05-23 | 2022-09-13 | Ningde Amperex Technology Limited | Electrolytic solution and electrochemical device using the same |
| CN111900472A (en) * | 2020-06-30 | 2020-11-06 | 远景动力技术(江苏)有限公司 | Non-aqueous electrolyte of lithium ion battery |
| CN111710911A (en) * | 2020-07-04 | 2020-09-25 | 湖南大学 | Electrolyte and lithium ion battery |
| CN111952668A (en) * | 2020-08-13 | 2020-11-17 | 梅州市量能新能源科技有限公司 | Electrolyte, lithium ion battery and preparation method thereof |
| CN112086684A (en) * | 2020-09-16 | 2020-12-15 | 松山湖材料实验室 | Cesium-containing high-voltage lithium ion battery electrolyte composite additive, electrolyte and battery thereof |
| CN112271328A (en) * | 2020-09-21 | 2021-01-26 | 东莞市创明电池技术有限公司 | Lithium ion battery electrolyte and lithium ion battery |
| CN113013488A (en) * | 2021-02-25 | 2021-06-22 | 珠海冠宇电池股份有限公司 | Electrolyte and lithium ion battery comprising same |
| CN114335722A (en) * | 2021-12-23 | 2022-04-12 | 惠州锂威新能源科技有限公司 | Lithium ion battery, electrolyte and additive thereof |
| EP4391138A1 (en) * | 2022-12-19 | 2024-06-26 | Samsung SDI Co., Ltd. | Rechargeable lithium batteries |
| CN117276657A (en) * | 2023-05-19 | 2023-12-22 | 深圳市固易能科技有限责任公司 | Electrolyte and battery |
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