CN107195966A - The high voltage tertiary cathode material system lithium-ion battery electrolytes that a kind of high/low temperature performance is taken into account - Google Patents
The high voltage tertiary cathode material system lithium-ion battery electrolytes that a kind of high/low temperature performance is taken into account Download PDFInfo
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- CN107195966A CN107195966A CN201710282942.7A CN201710282942A CN107195966A CN 107195966 A CN107195966 A CN 107195966A CN 201710282942 A CN201710282942 A CN 201710282942A CN 107195966 A CN107195966 A CN 107195966A
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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
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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 lithium-ion battery electrolytes, the electrolyte includes Non-aqueous Organic Solvents, lithium salts, film forming agent and additive;Fluorobenzonitrile, fluorobenzene, oxalic acid phosphoric acid lithium salts, four kinds of additives of fluorophosphate lithium salts are added in the lithium-ion battery electrolytes simultaneously, use can produce cooperative effect while above-mentioned additive, so that tertiary cathode material battery has the advantages that excellent cycle performance, high-temperature storage performance, low temperature performance and security performance under the conditions of high voltage (4.3~4.5V), solve that prior art high voltage appearance ternary battery electrolyte cycle performance, high-temperature behavior are good and cryogenic property can not be while the problem of taking into account very well.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to the high voltage ternary that a kind of high/low temperature performance is taken into account
The lithium-ion battery electrolytes of positive electrode system and the high-voltage lithium ion batteries for including the electrolyte.
Background technology
High voltage tertiary cathode material lithium ion battery because energy density is high, environment-friendly, the advantages of have extended cycle life,
Extensive use is obtained in the portable electric appts such as mobile phone, notebook computer, and is also considered as electric car, large-scale energy storage
One of optimal selection of device.Current electric tool, electric car, large-scale energy storage device are required increasingly the energy density of battery
It is high so that commercial tertiary cathode material lithium ion battery (operating voltage 4.2V), which is difficult to meet, to be required.Existing research shows to carry
The operating voltage of high battery is one of lifting maximally effective approach of tertiary cathode material lithium ion battery energy density, is developed higher
The ternary electrokinetic cell of voltage is the trend of battery technology development, is also new-energy automobile development inevitable requirement.But ternary is dynamic
After power battery operating voltage is improved, the oxidation Decomposition of conventional electrolysis liquid can be accelerated, so as to cause battery high-temperature storge quality poor, high
The problems such as warm cycle performance is poor, low temperature performance poor and security is poor, therefore, research and development are adapted to high voltage ternary material system lithium
The electrolyte of ion battery is extremely urgent.
At present, the conventional electrolysis liquid of ternary electrokinetic cell is mainly made up of Non-aqueous Organic Solvents, lithium salts, film forming agent.
Improve its performance under high voltages frequently with adding additive in conventional electrolysis liquid at this stage.Publication No.
CN104332650 A Chinese patent is prepared for using " methane-disulfonic acid methylene ester+fluorinated ethylene carbonate " as additive
A kind of high-voltage electrolyte of nickelic tertiary cathode material system lithium ion battery, it can effectively improve cycle performance of battery, still
Its unstability under the high temperature conditions, it is easy to cause battery inflatable and battery reversible capacity to lose serious;Publication No.
CN105140546 A Chinese patent uses " methane-disulfonic acid methylene ester+lithium salts type additive+cyclic anhydride compound " conduct
Additive is prepared for a kind of high voltage tertiary cathode material system lithium-ion battery electrolytes, and it is effectively improved cycle performance of battery
And high-temperature behavior, but do not provide the low temperature performance and security performance of the electrolyte;Publication No. CN104269577
A Chinese patent is prepared for one kind using " fluorinated ethylene carbonate+dinitrile compound+2- methyl maleic anhydrides " as additive
High-voltage lithium-ion battery electrolyte and high-voltage lithium ion batteries, are also effectively improved cycle performance of battery and high-temperature behavior;Together
Sample, it does not refer to the electrolyte low temperature performance and security performance yet;Publication No. CN104051786 A Chinese patent
Using halogeno-benzene nitrile compounds a kind of high-voltage lithium ion batteries are prepared for as additive, but the halogeno-benzene nitrile
The addition of compound is only the performance for improving lithium ion battery under high voltage, and cryogenic property, the normal temperature of battery are not referred to
Energy and security performance;Publication No. CN103943884 A Chinese patent is used as additive, institute using the lithium salts of oxalate group
Although stating adding for the lithium salts of oxalate group not say while improve the high-temperature behavior and cryogenic property of electrolyte
The bright lithium ion battery prepared, which can be used under high voltage condition (4.3~4.5V), also has high-temperature behavior and cryogenic property,
The performance parameters such as the recovery rate of battery capacity are not provided simultaneously yet.
The content of the invention
In order to solve the deficiencies in the prior art, it is an object of the invention to provide the height electricity that a kind of high/low temperature performance is taken into account
Tertiary cathode material system lithium-ion battery electrolytes are pressed, the electrolyte can be effectively improved tertiary cathode material battery simultaneously
Cycle performance, high-temperature storage performance, low temperature performance and security performance under the conditions of high voltage (4.3~4.5V), very well
Solve the cycle performances of prior art high voltage appearance tertiary cathode material system lithium-ion battery electrolytes, high-temperature behavior and low
The problem of warm nature be able to not can be taken into account simultaneously.
In the present invention, described " high/low temperature performance " refers to lithium-ion battery electrolytes of the present invention at high temperature
With preferable storage performance, at low temperature with preferable discharge performance.
To achieve these goals, the present invention is adopted the following technical scheme that:
A kind of lithium-ion battery electrolytes, the electrolyte includes Non-aqueous Organic Solvents, lithium salts, film forming agent and addition
Agent;The additive includes fluorobenzonitrile, fluorobenzene, many fluoro oxalic acid phosphoric acid lithium salts and fluorophosphate lithium salts.
Preferably, the consumption of the fluorobenzonitrile account for the electrolyte gross mass 0.3~1%, more preferably 0.4~
0.6%, also preferably 0.5%;The fluorobenzonitrile be selected from 3,4- difluorobenzonilyiles, 2,4,5- trifluorobenzonitriles, 2,4 difluorobenzene acetonitrile,
At least one of nitrile HTCN of 1,3,6- propane three.
Preferably, the consumption of the fluorobenzene accounts for the 0.5~5%, more preferably 3~5% of the electrolyte gross mass, also excellent
Elect 4.0% as;The fluorobenzene is selected from 1,2,3- trifluoro-benzenes, 1,2,4- trifluoro-benzenes, 1,2- difluorobenzenes, 1,3- difluorobenzenes, 1,4- bis-
At least one of fluorobenzene, p-fluorotoluene, DfBP.
Preferably, the consumption of many fluoro oxalic acid phosphoric acid lithium salts accounts for the 0.3~1.0% of the electrolyte gross mass, more
Preferably 0.4~0.6%, also preferably 0.5%;Many fluoro oxalic acid phosphoric acid lithium salts are selected from oxalic acid difluorophosphate
LiPF2C2O4, the lithium fluophosphate LiPF of oxalic acid four4C2O4At least one of.
Preferably, the consumption of the fluorophosphate lithium salts accounts for the 0.3~1.0% of the electrolyte gross mass, more preferably
0.4~0.6%, also preferably 0.5%;The fluorophosphates are selected from two fluoro lithium phosphate LiPO2F2;
Preferably, the Non-aqueous Organic Solvents are selected from cyclic carbonate, linear carbonate, or above-mentioned solvent arbitrary proportion
The mixture of mixing;The Non-aqueous Organic Solvents account for the 50~90% of the electrolyte gross mass, more preferably 65~85%.
Preferably, the cyclic carbonate be selected from ethylene carbonate EC, propene carbonate PC, butylene BC and γ-
At least one of butyrolactone.
Preferably, the linear carbonate is selected from diethyl carbonate DEC, methyl ethyl carbonate EMC, dimethyl carbonate DMC, carbon
At least one of sour first propyl ester MPC, ethyl propyl carbonic acid ester EPC, propyl acetate PA, ethyl propionate EP and propyl propionate PP.
Preferably, the lithium salts is selected from lithium hexafluoro phosphate LiPF6, LiBF4 LiBF4, di-oxalate lithium borate LiBOB,
Single LiODFB LiODFB, trimethyl fluoride sulfonyl lithium (LiCF3SO2), double fluorine sulfimide lithium (F2NO4S2.Li it is), double
(trifluoromethyl sulfonyl) imide li (LiN (CF3SO2)2At least one of);The lithium salts accounts for the electrolyte gross mass
5~25%, more preferably 10~15%.
Preferably, the film forming agent is selected from vinylene carbonate VC, vinylethylene carbonate VEC, fluorinated ethylene carbonate
FEC, succinonitrile SN, adiponitrile, nitrile HTCN, 1,3- propane sultone PS, 1,4- butane sultones 1 of 1,3,6- propane three,
At least one of 4-BS and 1,3- propene sultones RPS;The film forming agent account for the electrolyte gross mass 0.1~
15%, more preferably 0.5~10%.
Present invention also offers the purposes of above-mentioned lithium-ion battery electrolytes, it is used in lithium ion battery, particularly height
In the lithium ion battery of voltage tertiary cathode material system.It can improve the high/low temperature performance of the battery simultaneously.
The present invention also provides a kind of lithium ion battery, and it includes lithium-ion battery electrolytes of the present invention.
According to the present invention, the lithium ion battery also includes positive pole, negative pole and the barrier film being placed between positive pole and negative pole.Institute
State positive pole preferably tertiary cathode material.For example, LiMn1-x-yNixCoyO2, wherein the < y < 1 of 0 < x < 1,0, and x+y < 1.
Preferably, the charging upper limit voltage of the high-voltage lithium ion batteries is more than or equal to 4.3V and less than or equal to 4.5V.
Beneficial effects of the present invention:
Fluorobenzonitrile, fluorobenzene, oxalic acid phosphoric acid lithium salts, fluorophosphate are added in lithium-ion battery electrolytes of the present invention simultaneously
Four kinds of additives of lithium salts, use can produce cooperative effect while above-mentioned additive so that tertiary cathode material battery is in high electricity
Have excellent cycle performance, high-temperature storage performance, low temperature performance and security performance etc. excellent under the conditions of pressure (4.3~4.5V)
Point, solves prior art high voltage appearance ternary battery electrolyte cycle performance, high-temperature behavior is good and cryogenic property can not very well
The problem of taking into account simultaneously.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.Furthermore, it is to be understood that after described content of the invention has been read, this area skill
Art personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within limited range of the present invention.
The preparation condition of electrolyte of the present invention is to be operated in the nitrogen glove box for being 99.999% full of purity,
Moisture is less than 5ppm in glove box, and temperature is room temperature.
Embodiment 1
The preparation of electrolyte:
By ethylene carbonate, methyl ethyl carbonate and diethyl carbonate with mass ratio 1:1:1 is mixed to join the six of 1mol/L
Lithium fluophosphate (LiPF6), obtain electrolyte after uniform mixing.Then add electrolyte quality meter 1% vinylene carbonate, 1%
1,3- propane sultones, 0.5% succinonitrile film forming agent, uniform mixing.It is eventually adding 1,2,3- trifluoro-benzenes, 2,4,5- tri-
Fluorobenzonitrile, LiPF2C2O4And LiPO2F2Additive, as described electrolyte;The specific percentage of each component contains in the additive
Amount refers to table 1.
Comparative example 1-5
The preparation of electrolyte:
By ethylene carbonate, methyl ethyl carbonate and diethyl carbonate with mass ratio 1:1:1 is mixed to join the six of 1mol/L
Lithium fluophosphate (LiPF6), obtain electrolyte after uniform mixing.Then add electrolyte quality meter 1% vinylene carbonate, 1%
1,3- propane sultones, 0.5% succinonitrile film forming agent, uniform mixing is eventually adding 1,2,3- trifluoro-benzenes, 2,4,5- tri-
Fluorobenzonitrile, LiPF2C2O4Or LiPO2F2Additive, as described electrolyte;The specific percentage of each component contains in the additive
Amount refers to table 1.
The embodiment 1 of table 1 and the electrolyte prescription described in comparative example 1-5
Lithium-ion battery electrolytes prepared by above-mentioned table 1, are injected separately into positive electrode active material for nickle cobalt lithium manganate (LiMn1/ 3Ni1/3Co1/3O2), negative electrode active material in the soft bag lithium ionic cell of graphite, battery after fluid injection is encapsulated, shelve, be melted into,
The processes such as aging, secondary encapsulation, partial volume, obtain tertiary cathode material lithium ion battery to be tested.
High voltage cycle performance test is carried out to the lithium ion battery of preparation:
By the lithium ion battery prepared respectively under the conditions of 25 DEG C and 55 DEG C, with 1C constant-current charges to 4.4V, then
Constant-voltage charge to electric current drops to 0.1C, then with 1C electric currents constant-current discharge to 3.0V, is circulated 200 weeks with this, test battery
In first week and the capability retention of the 200th week, the capability retention of normal temperature circulation is calculated by following formula:
Discharge capacity × 100% of the discharge capacity of capability retention=200th week/1st week
High-temperature storage performance test is carried out to the lithium ion battery of preparation:
By the lithium ion battery prepared under the conditions of 25 DEG C, with 1C constant-current charges to 4.4V, then constant-voltage charge is extremely
Electric current drops to 0.1C, measures the initial discharge capacity of battery, after 85 DEG C/6h of high temperature storages with 1C electric currents constant-current discharge extremely
3.0V, measures the holding capacity of battery and recovers capacity, cell thickness is measured after battery is cooled to normal temperature, by following formula meter
Calculate the high-temperature storage performance of battery:
Holding capacity/initial discharge capacity × 100% of battery after capability retention=high-temperature storage
Recovery capacity/initial discharge capacity × 100% of battery after capacity restoration rate=high-temperature storage
Low temperature discharge test is carried out to the lithium ion battery of preparation:
By the lithium ion battery prepared, with 1C constant-current charges to 4.4V under the conditions of 25 DEG C of normal temperature, then constant pressure is filled
Electricity to electric current drops to 0.1C, measures the initial discharge capacity of battery, and after being placed 24 hours under the conditions of -20 DEG C, -20 DEG C with 1C
Electric current constant-current discharge calculates discharge capacity to 2.4V.
Discharge capacity/initial discharge capacity × 100% of battery after capability retention=low-temperature storage
The test result of the high voltage tertiary cathode material lithium ion battery prepared is shown in Table 2.
The embodiment 1 of table 2 and the battery performance test result described in comparative example 1-5
Hot tank performance test is carried out to the lithium ion battery of preparation:
By the lithium ion battery prepared, at 25 DEG C, each 5 of the battery of correspondence of table 2 is taken respectively, it is permanent with 0.5C multiplying power
Current charge is to 4.5V, and then constant-voltage charge to electric current is 0.05C, and then battery is put into hot tank.Hot tank rises since normal temperature
Temperature, 5 DEG C/min is warming up to 150 DEG C, and constant 30min observes the state of battery after test, as a result as shown in table 3.
The embodiment 1 of table 3 and the lithium ion battery over-charging test result described in comparative example 1-5
Battery status after test | |
Embodiment 1 | 5 batteries are intact |
Comparative example 1 | 5 batteries are on fire |
Comparative example 2 | 5 batteries are intact |
Comparative example 3 | 5 batteries are intact |
Comparative example 4 | 5 batteries are intact |
Comparative example 5 | 5 batteries are on fire |
From Table 2, it can be seen that additive fluorobenzonitrile, fluorobenzene, oxalic acid phosphoric acid lithium salts, fluorophosphate lithium salts are in high voltage three
There is synergistic function in first electrolyte system.For example, for normal temperature capability retention, the electricity of oxalic acid phosphoric acid lithium salts is not added
The normal temperature circulation capability retention for solving liquid (comparative example 2) or not adding the electrolyte (comparative example 4) of fluorophosphate lithium salts is relatively low,
And when above two component is added simultaneously, its normal temperature circulation capability retention is then higher.Kept for low temperature discharge capacity
Rate, when the electrolyte (comparative example 2) for not adding oxalic acid phosphoric acid lithium salts or the low temperature for the electrolyte (comparative example 3) for not adding fluorobenzonitrile
Discharge capacity rate is all relatively low, and when above two component is added simultaneously, its low temperature discharge capacity rate can be improved.
For fluorobenzene, as can be seen that adding after fluorobenzene, 85 DEG C/6h of high temperature capability retentions, 85 DEG C/6h of high temperature in table 2
Capacity restoration rate, 55 DEG C/1C of high temperature circulate 200 weeks capability retentions and slightly improved, and normal temperature 1C circulates 200 weeks capacity and kept
Rate, -20 DEG C of discharge capacitances of low temperature are slightly reduced.But, from table 3 it is observed that electricity can be prevented by adding fluorobenzene
Pond is on fire, and it is a kind of excellent additives for overcharge protection additive to illustrate fluorobenzene.
In summary experiment shows, fluorobenzonitrile, fluorobenzene, oxalic acid phosphoric acid are added in conventional three-way high-voltage electrolyte system
Lithium salts, fluorophosphate lithium salts, there is obvious synergy, are conducive to being lifted the performance of ternary high-voltage battery, in non-aqueous ternary
There is obvious advantage in high-voltage electrolyte.
More than, embodiments of the present invention are illustrated.But, the present invention is not limited to above-mentioned embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc., should be included in the guarantor of the present invention
Within the scope of shield.
Claims (10)
1. a kind of lithium-ion battery electrolytes, it is characterised in that the electrolyte includes Non-aqueous Organic Solvents, lithium salts, film forming
Agent and additive;The additive includes fluorobenzonitrile, fluorobenzene, many fluoro oxalic acid phosphoric acid lithium salts and fluorophosphate lithium salts.
2. electrolyte according to claim 1, it is characterised in that the consumption of the fluorobenzonitrile accounts for the electrolyte gross mass
0.3~1%, more preferably 0.4~0.6%, also preferably 0.5%;The fluorobenzonitrile is selected from 3,4- difluorobenzonilyiles, 2,4,5-
At least one of trifluorobenzonitrile, 2,4 difluorobenzene acetonitrile, the nitrile HTCN of 1,3,6- propane three.
3. electrolyte according to claim 1 or 2, it is characterised in that the consumption of the fluorobenzene accounts for the total matter of the electrolyte
The 0.5~5% of amount, more preferably 3~5%, also preferably 4.0%;The fluorobenzene is selected from 1,2,3- trifluoro-benzenes, 1,2,4- trifluoros
At least one of benzene, 1,2- difluorobenzenes, 1,3- difluorobenzenes, 1,4- difluorobenzenes, p-fluorotoluene, DfBP.
4. the electrolyte according to claim 1-3, it is characterised in that the consumption of many fluoro oxalic acid phosphoric acid lithium salts accounts for institute
State the 0.3~1.0% of electrolyte gross mass, more preferably 0.4~0.6%, also preferably 0.5%;Many fluoro oxalic acid phosphorus
Sour lithium salts is selected from oxalic acid difluorophosphate LiPF2C2O4, the lithium fluophosphate LiPF of oxalic acid four4C2O4At least one of.
5. the electrolyte according to claim 1-4, it is characterised in that the consumption of the fluorophosphate lithium salts accounts for the electrolysis
The 0.3~1.0% of liquid gross mass, more preferably 0.4~0.6%, also preferably 0.5%;The fluorophosphates are selected from difluoro
For lithium phosphate LiPO2F2。
6. the electrolyte according to claim 1-5, it is characterised in that the Non-aqueous Organic Solvents are selected from cyclic carbonate
Ester, linear carbonate, or the mixture that above-mentioned solvent arbitrary proportion is mixed;It is total that the Non-aqueous Organic Solvents account for the electrolyte
The 50~90% of quality, more preferably 65~85%;
Preferably, the cyclic carbonate is selected from ethylene carbonate EC, propene carbonate PC, butylene BC and γ-Ding Nei
At least one of ester;
Preferably, the linear carbonate is selected from diethyl carbonate DEC, methyl ethyl carbonate EMC, dimethyl carbonate DMC, carbonic acid first
At least one of propyl ester MPC, ethyl propyl carbonic acid ester EPC, propyl acetate PA, ethyl propionate EP and propyl propionate PP.
7. the electrolyte according to claim 1-6, it is characterised in that the lithium salts is selected from lithium hexafluoro phosphate LiPF6, tetrafluoro
Lithium borate LiBF4, di-oxalate lithium borate LiBOB, single LiODFB LiODFB, trimethyl fluoride sulfonyl lithium (LiCF3SO2)、
Double fluorine sulfimide lithium (F2NO4S2.Li), double (trifluoromethyl sulfonyl) imide li (LiN (CF3SO2)2) at least one
Kind;The lithium salts accounts for the 5~25% of the electrolyte gross mass, more preferably 10~15%;
Preferably, the film forming agent be selected from vinylene carbonate VC, vinylethylene carbonate VEC, fluorinated ethylene carbonate FEC,
Succinonitrile SN, adiponitrile, nitrile HTCN, 1,3- propane sultone PS, 1,4- butane sultones 1,4-BS of 1,3,6- propane three
At least one of and 1,3- propene sultones RPS;The film forming agent accounts for the 0.1~15% of the electrolyte gross mass, more
Preferably 0.5~10%.
8. the purposes of the lithium-ion battery electrolytes described in claim 1-7, it is used in lithium ion battery, particularly high voltage
In the lithium ion battery of tertiary cathode material system.
9. a kind of lithium ion battery, it includes the lithium-ion battery electrolytes described in claim 1-7.
10. lithium ion battery according to claim 9, it is characterised in that the lithium ion battery also includes positive pole, negative pole
And the barrier film being placed between positive pole and negative pole;
Preferably, the positive pole is preferably tertiary cathode material;
Preferably, the tertiary cathode material is LiMn1-x-yNixCoyO2, wherein the < y < 1 of 0 < x < 1,0, and x+y < 1;
Preferably, the charging upper limit voltage of the high-voltage lithium ion batteries is more than or equal to 4.3V and less than or equal to 4.5V.
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CN113871717A (en) * | 2021-10-29 | 2021-12-31 | 湖南法恩莱特新能源科技有限公司 | Electrolyte for lithium secondary battery and preparation method and application thereof |
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