CN108054431A - A kind of lithium ion cylinder battery suitable for the electrolyte of fast charge system and comprising the electrolyte - Google Patents
A kind of lithium ion cylinder battery suitable for the electrolyte of fast charge system and comprising the electrolyte Download PDFInfo
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- CN108054431A CN108054431A CN201711485907.1A CN201711485907A CN108054431A CN 108054431 A CN108054431 A CN 108054431A CN 201711485907 A CN201711485907 A CN 201711485907A CN 108054431 A CN108054431 A CN 108054431A
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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
- 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
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Abstract
The invention discloses a kind of electrolyte suitable for fast charge system and the lithium ion cylinder batteries comprising the electrolyte.The additive of the electrolyte of the present invention includes film for additive, high temperature additive and low temperature additive;Wherein, the film for additive includes the combination of fluorinated ethylene carbonate FEC, vinylene carbonate VC, succinonitrile SN and methane-disulfonic acid methylene ester MMDS;The high temperature additive is any one in 1,3 sultones PST of 1,3 propane sultone PS or acrylic;The low temperature additive is sulfuric acid vinyl ester DTD.The electrolyte of the present invention is suitable for the lithium ion cylinder battery of fast charge system, can significantly improve the fast charge cycle performance under battery high magnification, while have both good high temperature performance.
Description
Technical field
The invention belongs to technical field of lithium ion, are related to a kind of electrolyte and the lithium-ion electric comprising the electrolyte
Pond more particularly to a kind of lithium ion cylinder battery suitable for the electrolyte of fast charge system and comprising the electrolyte.
Background technology
Lithium ion battery due to operating voltage is high, energy density is high, have extended cycle life and be environmentally friendly the advantages that, it is wide
It is general to be used for the fields such as 3C digital products, electric vehicle and military aerospace.With the popularization of intelligent digital product and application, new energy
The extensive use of automobile, people are more urgent to the demand of the rapid charge characteristic of battery.The factor for influencing quick charge is more
Aspect, design including positive and negative pole material and electrolyte etc., wherein, the performance of electrolyte has fast charging and discharging crucial shadow
It rings.
At present, the lithium ion cylinder battery electrolyte of the system of fast charge system is suitble to have the following problems:1. circulating battery
During short life, particularly high rate charge-discharge Xun Huan, easily occur the situation of analysis lithium, the lithium metal meeting of enrichment on negative plate surface
Electrolyte is further consumed, so that the life time decay aggravation of battery.2. high-temperature storage performance has much room for improvement.
Forthright battery can only achieve 1C or 2C chargings to cylinder again in the market at present, and can reach 3C, 4C charge and discharge
The circulating system of electricity is almost invisible.With market to the demand of rapid charging performance, it is necessary to develop more 3C charge either it is higher
Meet the cylindrical electrical core of fast charge Xun Huan.
105845984 A of CN disclose a kind of lithium-ion battery electrolytes and the lithium ion battery using the electrolyte.It should
Electrolyte includes lithium salts, Non-aqueous Organic Solvents and additive, and the additive includes fluorinated ethylene carbonate, nitrile compounds
It is formed with the compound with specific structure, which under elevated pressure conditions, has that effect of impregnation is good, rapid charging performance is excellent
It is different, and have both the comprehensive performance low with high temperature storage expansion rate that have extended cycle life, but it is after 85 DEG C store 6h, residual capacity
Below 90%, high-temperature storage performance needs to be further improved.
Therefore, it is necessary to develop a kind of fast charge cyclicity that can be significantly improved under lithium ion cylinder battery high magnification and simultaneous
Has the electrolyte of high temperature performance.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of suitable for fast charge system
Electrolyte and the lithium ion cylinder battery comprising the electrolyte.The electrolyte of the present invention can be significantly improved under battery high magnification
Fast charge cycle performance, while have both the good high temperature performance of electrolyte.
In a first aspect, the present invention provides a kind of electrolyte, the additive of the electrolyte adds including film for additive, high temperature
Add agent and low temperature additive;
Wherein, the film for additive includes fluorinated ethylene carbonate (FEC), the vinylene carbonate of following additive types
The combination of ester (VC), succinonitrile (SN) and methane-disulfonic acid methylene ester (MMDS);
The high temperature additive is arbitrary in 1,3- propane sultones (PS) or acrylic -1,3- sultones (PST)
It is a kind of;
The low temperature additive is sulfuric acid vinyl ester (DTD).
Below as currently preferred technical solution, but not as the limitation to technical solution provided by the invention, lead to
Following preferred technical solution is crossed, can preferably reach and realize the technical purpose and advantageous effect of the present invention.
Preferably, the additive of the electrolyte is made of film for additive, high temperature additive and low temperature additive.This is excellent
Selecting technology scheme is enclosed composition, i.e., film for additive of the present invention, high temperature addition are contained only in described electrolyte
Agent and low temperature additive are more advantageous to promoting electrolyte property of the present invention under these conditions, improve lithium ion battery
Fast charge cycle performance and high temperature performance.
Preferably, using the gross mass of the electrolyte as 100%, the mass fraction of the additive is 3%~10%, example
Such as 3%, 4%, 5%, 6%, 6.5%, 7%, 8%, 9% or 10%.
As the optimal technical scheme of electrolyte of the present invention, counted using the gross mass of the electrolyte as 100%, it is described
The mass fraction of each component is as follows in film for additive:
In this optimal technical scheme, the mass fraction of fluorinated ethylene carbonate is 2%~6%, such as 2%, 3%, 4%,
5% or 6% etc.;The mass fraction of vinylene carbonate is 0.5%~3%, such as 0.5%, 1%, 2%, 2.5% or 3% etc.;
The mass fraction of succinonitrile is 0.5%~3%, such as 0.5%, 1%, 1.5%, 2.5% or 3% etc.;Methane-disulfonic acid methylene
The mass fraction of ester is 0.5%~2%, such as 0.5%, 1%, 1.5% or 2% etc..
Preferably, counted using the gross mass of the electrolyte as 100%, the high temperature additive is the 1,3- of 0.5%~3%
Propane sultone.
Preferably, to be counted using the gross mass of the electrolyte as 100%, the high temperature additive is 0.2% acrylic -1,
3- sultones.
In this optimal technical scheme, the mass fraction of 1,3-propane sultone is 0.5%~3%, such as 0.5%, 1%,
1.5%th, 2%, 2.5% or 3% etc..
Preferably, counted using the gross mass of the electrolyte as 100%, the mass fraction of the sulfuric acid vinyl ester DTD is
0.5%~2%.
As the optimal technical scheme of electrolyte of the present invention, the electrolyte lithium salt of the electrolyte is LiClO4、
LiPF6、LiCF3SO3、LiBOB、LiTFSI、LiFSI、LiBF4、LiAsF6, LiFOB or LiPO2F2In any one or at least
Two kinds of combination.
Preferably, counted using the gross mass of the electrolyte as 100%, the mass fraction of the electrolyte lithium salt for 13%~
20%, such as 13%, 14%, 15%, 16%, 18%, 19% or 20% etc..
As the optimal technical scheme of electrolyte of the present invention, the solvent of the electrolyte is by dimethyl carbonate DMC, carbon
Sour methyl ethyl ester EMC, ethylene carbonate EC, ethyl acetate EA, the binary of ethyl propionate EP and propyl propionate PP, ternary, quaternary or
Person's five-tuple is grouped into.
" binary, ternary, quaternary or the five-tuple point " refers to:Two kinds, three kinds, four kinds or five in the above-mentioned solvent enumerated
The combination of kind.
Preferably, counted using the total volume of the solvent as 100%, the volume fraction of the DMC is 40%~80%, EMC
Volume fraction be 10%~30%, EC volume fraction be 10%~30%, PC volume fraction be 1%~10%, EA's
Volume fraction is 1%~20%;The volume fraction that the volume fraction of EP is 1%~20%, PP is 1%~20%.It is described herein
The volume fraction range of DMC, EMC, EC, PC, EA, EP and PP are not to limit that this six kinds of substances must be contained simultaneously, and solvent can
To be above-mentioned binary, ternary, quaternary or five-tuple point, and each component is applied in combination according to above-mentioned volume fraction.It illustrates:
By taking the solvent for the binary composition that EC and DMC are formed as an example, the volume fraction that can make EC is 30% and the volume fraction of DMC is
70%.
Second aspect, the present invention provide a kind of lithium ion cylinder battery, and the lithium ion cylinder battery includes first aspect
The electrolyte.
The electrolyte of the present invention is suitable for the lithium ion cylinder battery of fast charge system, and the fast charge that can significantly improve battery is followed
Ring performance (can the quick charge under the conditions of high current high magnification, and to be had excellent performance during big multiplying power discharging), while have both electrolysis
The good high temperature performance of liquid.
Preferably, the lithium ion cylinder battery includes the electrolyte described in anode, cathode, membrane and first aspect.
In the lithium ion battery of the present invention, membrane is set between a positive electrode and a negative electrode.
Compared with the prior art, the present invention has the advantages that:
(1) present invention works in coordination by selecting particular kind of additive, and with solvent and lithium salts, and collaboration improves electricity
Solve the fast charge cycle performance and high temperature performance of the comprehensive performance, especially battery of liquid.
(2) electrolyte of the invention is suitable for the lithium ion cylinder battery of fast charge system, can significantly improve battery high power
Fast charge cycle performance under rate, while have both the good high temperature performance of electrolyte.
(3) electrolyte using the present invention is made lithium ion cylinder battery and carries out electrochemical property test, 2C chargings 10C
Discharge cycles 600 weeks, capacity retention ratio > 80% illustrate that its fast charge cycle performance is good.
(4) electrolyte of the invention is in 60 DEG C of high temperature storages 30 days, capacity surplus ratio > 90%, capacity restoration rate >
95%, illustrate that its high-temperature storage performance is good.
(5) electrolyte using the present invention is made lithium ion cylinder battery and detects the big multiplying power discharging property of low temperature, battery
After 2C is fully charged at normal temperatures, 20H is stored under conditions of -20 DEG C, 10C electric discharges, battery core moment are carried out under conditions of -20 DEG C
Voltage value still in more than 2.7V, illustrates that its low temperature performance is good.
Description of the drawings
Fig. 1 is to be assembled into lithium ion cylinder battery using the electrolyte of embodiment 1-3, and carries out 2C chargings 10C and discharge
The cycle performance curve arrived.
Fig. 2 is to be assembled into lithium ion cylinder battery using the electrolyte of embodiment 1-3, and 10C is carried out under conditions of -20 DEG C
The low temperature discharge curve of electric discharge.
Fig. 3 is to be assembled into lithium ion cylinder battery using the electrolyte of embodiment 1-3, and carries out (60 DEG C 30 of high temperature storage
My god) after obtained block diagram.
Specific embodiment
Technical solution to further illustrate the present invention below with reference to the accompanying drawings and specific embodiments.
" wt% " arrived involved in the embodiment of the present invention is mass percent, using the gross mass of electrolyte as 100wt%
Meter.
Embodiment 1
The present embodiment provides a kind of electrolyte, and electrolyte is by 60%DMC, 15%EMC, 20%EC and 5%EA (volume basis
Than) solvent that is grouped into of four-tuple, then with by 6wt%LiPF6, 10wt%LiFSI, 10wt%LiTFSI and 0.5wt%LiFOB
Composition electrolytic salt mixing, add in by 3wt%FEC, 1.5wt%SN, 0.5%VC, 1wt%PS, 0.5wt%DTD,
The organic electrolyte of 0.5wt%MMDS compositions.
The present embodiment also provides a kind of lithium ion cylinder battery, in the lithium ion cylinder battery comprising anode, cathode, every
The electrolyte of film and the present embodiment.
The preparation process of the lithium ion cylinder battery is:Anode uses nickel-cobalt-manganese ternary material, and cathode uses graphite-like material
Material.By adding conductive agent, binding agent, solvent is prepared into anode sizing agent and negative electrode slurry respectively, and anode sizing agent and cathode are starched
Material is respectively coated on aluminium foil and copper foil, is dried in dry environments, is cold-pressed, is cut and film-making, obtains positive plate and negative plate.
According to membrane, cathode, membrane, anode order, be superimposed and be wound into column pole group, be then placed in box hat, injection it is suitable
Electrolyte, then sealed, cylindrical battery is obtained after forming and capacity dividing.
Electrochemical property test is carried out to lithium ion cylinder battery made of the electrolyte using the present embodiment, 2C charges
10C discharge cycles 600 weeks, capacity retention ratio > 80%, test result is shown in Fig. 1.
Electrolyte using the present invention is made lithium ion cylinder battery and detects the big multiplying power discharging property of low temperature, and battery is normal
After the lower 3C of temperature is fully charged, 20H is stored under conditions of -20 DEG C, 10C electric discharges, battery core transient voltage are carried out under conditions of -20 DEG C
Value illustrates that its low temperature performance is good, test result is shown in Fig. 2 still in more than 2.7V.
To the electrolyte of the present embodiment in 60 DEG C of high temperature storages 30 days, test result is shown in Fig. 3.
Embodiment 2
The present embodiment provides a kind of electrolyte, and electrolyte is by 60%DMC, 15%EMC, 20%EC and 5%PC (volume basis
Than) solvent that is grouped into of four-tuple, then with by 5wt%LiCF3SO3, 5wt%LiPF6, 5wt%LiFSI and 1wt%LiFOB groups
Into electrolytic salt mixing, add in by 0.5wt%VC, 4.0wt%FEC, 2wt%SN, 2wt%PS, 0.5wt%MMDS,
The organic solution electrolyte of 1.0wt%DTD compositions.
The present embodiment also provides a kind of lithium ion cylinder battery, in the lithium ion cylinder battery comprising anode, cathode, every
The electrolyte of film and the present embodiment.
The preparation process of the lithium ion cylinder battery is:Anode uses nickel-cobalt-manganese ternary material, and cathode uses graphite-like material
Material.By adding conductive agent, binding agent, solvent is prepared into anode sizing agent and negative electrode slurry respectively, and anode sizing agent and cathode are starched
Material is respectively coated on aluminium foil and copper foil, is dried in dry environments, is cold-pressed, is cut and film-making, obtains positive plate and negative plate.
According to membrane, cathode, membrane, anode order, be superimposed and be wound into column pole group, be then placed in box hat, injection it is suitable
Electrolyte, then sealed, cylindrical battery is obtained after forming and capacity dividing.
Test:
Electrochemical property test is carried out to lithium ion cylinder battery made of the electrolyte using the present embodiment, 2C charges
10C discharge cycles 600 weeks, capacity retention ratio > 80%, test result is shown in Fig. 1.
Electrolyte using the present invention is made lithium ion cylinder battery and detects the big multiplying power discharging property of low temperature, and battery is normal
After the lower 3C of temperature is fully charged, 20H is stored under conditions of -20 DEG C, 10C electric discharges, battery core transient voltage are carried out under conditions of -20 DEG C
Value illustrates that its low temperature performance is good, test result is shown in Fig. 2 still in more than 2.7V.
To the electrolyte of the present embodiment in 60 DEG C of high temperature storages 30 days, test result is shown in Fig. 3.
Embodiment 3
The present embodiment provides a kind of electrolyte, and electrolyte is by 58%DMC, 20%EMC and 22%EC (percent by volume) three
The solvent that tuple is grouped into, then with by 5wt%LiTFSI, 5wt%LiFSI, 5wt%LiPF6,1wt%LiFOB, 1wt%
LiPO2F2Composition electrolytic salt mixing, add in by 0.5wt%VC, 4wt%FEC, 1.75wt%SN, 1.0wt%PS,
The organic solution electrolyte of 1.0wt%MMDS and 0.5wt%DTD compositions.
The present embodiment also provides a kind of lithium ion cylinder battery, in the lithium ion cylinder battery comprising anode, cathode, every
The electrolyte of film and the present embodiment.
The preparation process of the lithium ion cylinder battery is:Anode uses nickel-cobalt-manganese ternary material, and cathode uses graphite-like material
Material, by adding conductive agent, binding agent, solvent is prepared into anode sizing agent and negative electrode slurry respectively, and anode sizing agent and cathode are starched
Material is respectively coated on aluminium foil and copper foil, is dried in dry environments, is cold-pressed, is cut and film-making, obtains positive plate and negative plate.
According to membrane, cathode, membrane, anode order, be superimposed and be wound into column pole group, be then placed in box hat, injection it is suitable
Electrolyte, then sealed, cylindrical battery is obtained after forming and capacity dividing.
Test:
Electrochemical property test is carried out to lithium ion cylinder battery made of the electrolyte using the present embodiment, 2C charges
10C discharge cycles 600 weeks, capacity retention ratio > 80%, test result is shown in Fig. 1.
Electrolyte using the present invention is made lithium ion cylinder battery and detects the big multiplying power discharging property of low temperature, and battery is normal
After the lower 3C of temperature is fully charged, 20H is stored under conditions of -20 DEG C, 10C electric discharges, battery core transient voltage are carried out under conditions of -20 DEG C
Value illustrates that its low temperature performance is good, test result is shown in Fig. 2 still in more than 2.7V.
To the electrolyte of the present embodiment in 60 DEG C of high temperature storages 30 days, test result is shown in Fig. 3.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all fall within protection scope of the present invention and the open scope.
Claims (10)
1. a kind of electrolyte, which is characterized in that the additive of the electrolyte includes film for additive, high temperature additive and low temperature
Additive;
Wherein, the film for additive includes fluorinated ethylene carbonate FEC, vinylene carbonate VC, succinonitrile SN and methane two
The combination of sulfonic acid methylene ester MMDS;
The high temperature additive is any one in 1,3- propane sultones PS or acrylic -1,3- sultones PST;
The low temperature additive is sulfuric acid vinyl ester DTD.
2. electrolyte according to claim 1, which is characterized in that the additive of the electrolyte is by film for additive, height
Warm additive and low temperature additive composition;
Preferably, using the gross mass of the electrolyte as 100%, the mass fraction of the additive is 3%~10%.
3. electrolyte according to claim 1 or 2, which is characterized in that it is counted using the gross mass of the electrolyte as 100%,
The mass fraction of each component is as follows in the film for additive:
4. according to claim 1-3 any one of them electrolyte, which is characterized in that using the gross mass of the electrolyte as
100% meter, the high temperature additive are 0.5%~3% 1,3-propane sultone;
Preferably, counted using the gross mass of the electrolyte as 100%, the high temperature additive is 0.2% acrylic -1,3- sulphur
Acid lactone.
5. according to claim 1-4 any one of them electrolyte, which is characterized in that using the gross mass of the electrolyte as
100% meter, the mass fraction of the sulfuric acid vinyl ester DTD is 0.5%~2%.
6. according to claim 1-5 any one of them electrolyte, which is characterized in that the electrolyte lithium salt of the electrolyte is
LiClO4、LiPF6、LiCF3SO3、LiBOB、LiTFSI、LiFSI、LiBF4、LiAsF6, LiFOB or LiPO2F2In any one
Or at least two combination;
Preferably, counted using the gross mass of the electrolyte as 100%, the mass fraction of the electrolyte lithium salt for 13%~
20%.
7. according to claim 1-6 any one of them electrolyte, which is characterized in that the solvent of the electrolyte is by carbonic acid diformazan
Ester DMC, methyl ethyl carbonate EMC, ethylene carbonate EC, ethyl acetate EA, the binary of ethyl propionate EP and propyl propionate PP, three
Member, quaternary or five-tuple are grouped into;
Preferably, counted using the total volume of the solvent as 100%, the volume fraction of DMC is 40%~80%;The volume integral of EMC
The volume fraction that number is 10%~30%, EC is that the volume fraction of 10%~30%, PC is the volume fraction of 1%~10%, EA
For 1%~20%;The volume fraction that the volume fraction of EP is 1%~20%, PP is 1%~20%.
8. a kind of lithium ion cylinder battery, which is characterized in that the lithium ion cylinder battery includes any one of claim 1-7 institute
The electrolyte stated.
9. lithium ion cylinder battery according to claim 8, which is characterized in that the lithium ion cylinder battery is included just
Pole, cathode, membrane and claim 1-7 any one of them electrolyte.
10. lithium ion cylinder battery according to claim 9, which is characterized in that the membrane be arranged on the anode and
Between cathode.
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CN108808090A (en) * | 2018-07-16 | 2018-11-13 | 昆山兴能能源科技有限公司 | A kind of lithium battery electrolytes and lithium battery blocked certainly with high security |
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CN113422111A (en) * | 2021-06-23 | 2021-09-21 | 吉安谊盛电子材料有限公司 | Electrolyte and lithium ion battery containing same |
US20230246186A1 (en) * | 2018-05-11 | 2023-08-03 | Lg Energy Solution, Ltd. | Lithium Secondary Battery |
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