CN105845971A - Non-aqueous electrolyte containing high-voltage protective agent - Google Patents
Non-aqueous electrolyte containing high-voltage protective agent Download PDFInfo
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- CN105845971A CN105845971A CN201610331511.0A CN201610331511A CN105845971A CN 105845971 A CN105845971 A CN 105845971A CN 201610331511 A CN201610331511 A CN 201610331511A CN 105845971 A CN105845971 A CN 105845971A
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- electrolytic solution
- carbonate
- high voltage
- containing high
- nonaqueous electrolytic
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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
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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
- H01M10/056—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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- 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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- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the chemical engineering field, and particularly to a non-aqueous electrolyte containing a high-voltage protective agent. The non-aqueous electrolyte comprises the following materials in parts by weight: 0.5-20 parts of 5-fluoride thiophene-2-formonitrile, 0.1-15 parts of electrolyte lithium salt, 60-90 parts of organic solvent and 0.1-5 parts of functional additive, wherein the organic solvent is a high-purity carbonic ester organic solvent. Research findings prove that the high-voltage protective agent is decomposed in the surface of a negative electrode material in preference to the solvent under a high-voltage condition to form an SEI membrane to resist electrolyte decomposition and restrain battery expansion caused by electrolyte decomposition, so as to prolong the cycle life and improve the safety of the battery, so that the requirements of high-voltage cells can be satisfied.
Description
Technical field
The present invention relates to chemical field, relate to battery electrolyte research field, particularly relate to one
Nonaqueous electrolytic solution containing high voltage protection agent.
Background technology
Along with the marketization of lithium ion battery, the range of application of lithium ion battery is increasingly wider, people
More and more higher to the pursuit of lithium ion battery.High voltage, high specific energy, long circulation life are
The main target that people pursue.
Thickness is generally there is in more than 4.35V high-voltage battery during circulation for a long time and storage
Degree expansion, internal resistance increase, problem that capability retention is low.Under high voltages, positive-active material
The oxidation activity of material is higher so that the reactive increase between itself and electrolyte, adds at high temperature
Under, the reaction between high-voltage anode and electrolyte is further exacerbated by, and causes the oxidation of electrolyte
Catabolite constantly deposits at positive electrode surface, deteriorates positive electrode surface characteristic, causes the interior of battery
Resistance and thickness constantly increase.The digestion of metallic ion of positive active material and reduction.On the one hand,
At high temperature, the LiPF in electrolyte6As easy as rolling off a log decomposition, produces HF and PF5.Wherein HF
Positive pole can be corroded, cause the dissolution of metal ion, thus destroy cathode material structure, cause holding
Amount runs off；On the other hand, under high voltages, electrolyte is easily oxidized at positive pole, just causes
The metal ion of pole active material is easily reduced and dissolution is in electrolyte, thus destroys positive pole
Material structure, causes capacitance loss.Meanwhile, the metal ion of dissolution to electrolyte, easily wear
Cross SEI to arrive negative pole acquisition electronics and be reduced into metal simple-substance, thus destroy the knot of SEI
Structure, causes cathode impedance constantly to increase, and self-discharge of battery aggravates, and irreversible capacity increases, property
Can deteriorate.
Therefore, for being effectively improved lithium ion battery energy density, it is badly in need of developing electrode/electro solution
The high voltage nonaqueous electrolytic solution that liquid interface compatibility is good, have extended cycle life, high-temperature behavior is excellent.
Summary of the invention
The present invention is directed to prior art not enough, it is provided that a kind of non-water power containing high voltage protection agent
Solve liquid.In order to achieve the above object, the technical scheme is that
A kind of nonaqueous electrolytic solution containing high voltage protection agent, includes following material according to weight fraction:
Described organic solvent is high-purity carbonate based organic solvent.
As preferably, described electrolyte lithium salt is LiBF4 (LiBF4), lithium hexafluoro phosphate
(LiPF6), double fluorine sulfonamide lithium (LiFSI) or TFMS lithium (LiSO3CF3)
In at least one.
As preferably, described high-purity carbonate based organic solvent is cyclic carbonates or chain carbon
At least one in acid esters compound；Described cyclic carbonate compounds is ethylene carbonate
At least one in ester, propene carbonate, gamma-butyrolacton；Described linear carbonate class chemical combination
Thing be dimethyl carbonate, diethyl carbonate, methyl ethyl ester and carbon number be the straight of 3-8
At least one in the carbonic acid ester derivative of chain or Branched fatty single methanol and carbonic acid synthesis.
As preferably, described functional additive is biphenyl, vinylene carbonate, fluoro ethylene
At least one in alkene ester or 1,3-(1-propylene) sultone.
As preferably, the described nonaqueous electrolytic solution containing high voltage protection agent is applied to lithium secondary electricity
Chi Zhong.
Compared with prior art, advantages of the present invention and good effect are, it has been investigated that,
Under the conditions of high-tension, high voltage protection agent has precedence over solvolysis in the formation of cathode material surface
One layer of SEI film, stops electrolyte decomposition, suppresses to cause cell expansion problem because of electrolyte decomposition
Generation, improve the cycle life of battery and security performance, it is possible to meet the need of high voltage battery core
Ask.
Accompanying drawing explanation
In order to be illustrated more clearly that the technical scheme of the embodiment of the present invention, embodiment will be retouched below
In stating, the required accompanying drawing used is briefly described, it should be apparent that, in describing below
Accompanying drawing is some embodiments of the present invention, for those of ordinary skill in the art, is not paying
On the premise of going out creative work, it is also possible to obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is that the nonaqueous electrolytic solution containing high voltage protection agent using embodiment 13 to prepare is with right
The cycle performance of 3.0-4.5V under the 0.2C multiplying power of the graphite/cobalt acid lithium battery of ratio 4 electrolyte.
Detailed description of the invention
In order to be more clearly understood that the above-mentioned purpose of the present invention, feature and advantage, knot below
The present invention will be further described to close specific embodiment.It should be noted that in the feelings do not conflicted
Under condition, the feature in embodiments herein and embodiment can be mutually combined.
Elaborate a lot of detail in the following description so that fully understanding the present invention, but
It is that the present invention can be different from other modes described here with employing and implement, therefore, this
Invention is not limited to the restriction of the specific embodiment of specification described below.
Embodiment 1, the present embodiment provides a kind of nonaqueous electrolytic solution containing high voltage protection agent, each component
And content is as follows: lithium salts is LiPF6, concentration in the electrolytic solution is 1.0mol/L, and solvent is EC:DMC:
EMC=1:1:1 (volume ratio), 5-fluorine thiophene-2-formonitrile HCN addition accounts for the 1% of electrolyte gross mass, function
Additive is PS, and concentration in the electrolytic solution is 0.1mol/L.
Embodiment 2, the present embodiment provide a kind of nonaqueous electrolytic solution containing high voltage protection agent, each component and
Its content is as follows: lithium salts is LiPF6, concentration in the electrolytic solution is 2.0mol/L, and solvent is EC:DMC:
EMC=1:1:1 (volume ratio), 5-fluorine thiophene-2-formonitrile HCN addition accounts for the 1% of electrolyte gross mass, function
Additive is PS, and concentration in the electrolytic solution is 0.1mol/L.
Embodiment 3, the present embodiment provides a kind of nonaqueous electrolytic solution containing high voltage protection agent, each component
And content is as follows: lithium salts is LiPF6, concentration in the electrolytic solution is 3.0mol/L, and solvent is EC:DMC:
EMC=1:1:1 (volume ratio), 5-fluorine thiophene-2-formonitrile HCN addition accounts for the 1% of electrolyte gross mass, function
Additive is PS, and concentration in the electrolytic solution is 0.1mol/L.
Embodiment 4, the present embodiment provides a kind of nonaqueous electrolytic solution containing high voltage protection agent, each component
And content is as follows: lithium salts is LiPF6, concentration in the electrolytic solution is 5.0mol/L, and solvent is EC:DMC:
EMC=1:1:1 (volume ratio), 5-fluorine thiophene-2-formonitrile HCN addition accounts for the 1% of electrolyte gross mass, function
Additive is PS, and concentration in the electrolytic solution is 0.1mol/L.
Embodiment 5, the present embodiment provides a kind of nonaqueous electrolytic solution containing high voltage protection agent, each component
And content is as follows: lithium salts is LiPF4, concentration in the electrolytic solution is 1.0mol/L, and solvent is PC:
DMC=1:2 (volume ratio), 5-fluorine thiophene-2-formonitrile HCN addition accounts for the 1% of electrolyte gross mass, and function adds
Adding agent is VC and VEC, and concentration in the electrolytic solution is respectively 0.1mol/L and 0.2mol/L.
Embodiment 6, the present embodiment provides a kind of nonaqueous electrolytic solution containing high voltage protection agent, each component
And content is as follows: lithium salts is LiPF4, concentration in the electrolytic solution is 2.0mol/L, and solvent is PC:
DMC=1:2 (volume ratio), 5-fluorine thiophene-2-formonitrile HCN addition accounts for the 1% of electrolyte gross mass, and function adds
Adding agent is VC and VEC, and concentration in the electrolytic solution is respectively 0.1mol/L and 0.2mol/L.
Embodiment 7, the present embodiment provides a kind of nonaqueous electrolytic solution containing high voltage protection agent, each component
And content is as follows: lithium salts is LiPF4, concentration in the electrolytic solution is 3.0mol/L, and solvent is PC:
DMC=1:2 (volume ratio), 5-fluorine thiophene-2-formonitrile HCN addition accounts for the 1% of electrolyte gross mass, and function adds
Adding agent is VC and VEC, and concentration in the electrolytic solution is respectively 0.1mol/L and 0.2mol/L.
Embodiment 8, the present embodiment provides a kind of nonaqueous electrolytic solution containing high voltage protection agent, each component
And content is as follows: lithium salts is LiPF4, concentration in the electrolytic solution is 5.0mol/L, and solvent is PC:
DMC=1:2 (volume ratio), 5-fluorine thiophene-2-formonitrile HCN addition accounts for the 1% of electrolyte gross mass, and function adds
Adding agent is VC and VEC, and concentration in the electrolytic solution is respectively 0.1mol/L and 0.2mol/L.
Embodiment 9, the present embodiment provides a kind of nonaqueous electrolytic solution containing high voltage protection agent, each component
And content is as follows: lithium salts is LiPF6, concentration in the electrolytic solution is 1.0mol/L, and solvent is EC:DEC:
EMC=1:1:1 (volume ratio), 5-fluorine thiophene-2-formonitrile HCN addition accounts for the 1% of electrolyte gross mass, function
Additive is VC and BP, and concentration in the electrolytic solution is 0.2mol/L.
Embodiment 10, the present embodiment a kind of nonaqueous electrolytic solution containing high voltage protection agent of offer, each group
Divide and content is as follows: lithium salts is LiPF6, concentration in the electrolytic solution is 1.0mol/L, and solvent is EC:
DEC:EMC=1:1:1 (volume ratio), 5-fluorine thiophene-2-formonitrile HCN addition accounts for the 1% of electrolyte gross mass,
Functional additive is VC and BP, and concentration in the electrolytic solution is 0.2mol/L.
Embodiment 11, the present embodiment a kind of nonaqueous electrolytic solution containing high voltage protection agent of offer, each group
Divide and content is as follows: lithium salts is LiPF6, concentration in the electrolytic solution is 1.0mol/L, and solvent is EC:
DEC:EMC=1:1:1 (volume ratio), 5-fluorine thiophene-2-formonitrile HCN addition accounts for the 1% of electrolyte gross mass,
Functional additive is VC and BP, and concentration in the electrolytic solution is 0.2mol/L.
Embodiment 12, the present embodiment a kind of nonaqueous electrolytic solution containing high voltage protection agent of offer, each group
Divide and content is as follows: lithium salts is LiPF6, concentration in the electrolytic solution is 1.0mol/L, and solvent is EC:
DEC:EMC=1:1:1 (volume ratio), 5-fluorine thiophene-2-formonitrile HCN addition accounts for the 1% of electrolyte gross mass,
Functional additive is VC and BP, and concentration in the electrolytic solution is 0.2mol/L.
Comparative example 1, this comparative example provides a kind of nonaqueous electrolytic solution, and each component and content thereof are as follows: lithium salts
For LiPF6, concentration in the electrolytic solution is 1.0mol/L, and solvent is EC:DMC:EMC=1:1:1 (body
Long-pending ratio), functional additive is PS, and concentration in the electrolytic solution is 0.1mol/L.
Comparative example 2, this comparative example provides a kind of nonaqueous electrolytic solution, and each component and content thereof are as follows: lithium salts is
LiPF4, concentration in the electrolytic solution is 1.0mol/L, and solvent is PC:DMC=1:2 (volume ratio), 5-
Fluorine thiophene-2-formonitrile HCN addition accounts for the 1% of electrolyte gross mass, and functional additive is VC and VEC, in electrolysis
Concentration in liquid is respectively 0.1mol/L and 0.2mol/L.
Comparative example 3, this comparative example provides a kind of nonaqueous electrolytic solution, and each component and content thereof are as follows: lithium salts is
LiPF6, concentration in the electrolytic solution is 1.0mol/L, and solvent is EC:DEC:EMC=1:1:1 (body
Long-pending ratio), 5-fluorine thiophene-2-formonitrile HCN addition accounts for the 1% of electrolyte gross mass, and functional additive is VC and BP,
Concentration in the electrolytic solution is 0.2mol/L.
The electrolyte solution that embodiment 1-12 and comparative example 1-3 prepare respectively is applied in cobalt acid lithium battery,
The expansion status test data of battery after circulating under the conditions of 0.2C, 4.5-3.0V 100 weeks.
Table 1 uses the nonaqueous electrolytic solution containing high voltage protection agent and comparative example 1-3 that embodiment 1-12 prepares
In prepare electrolyte time cell expansion situation detection comparing result
Embodiment 13, the present embodiment provides a kind of nonaqueous electrolytic solution containing high voltage protection agent, is containing
There are the ethylene carbonate of volume ratio 1:1:1 of 1M LiPF6, dimethyl carbonate and methyl ethyl carbonate
Electrolyte in add 3%5-fluorine thiophene-2-formonitrile HCN, 0.5%VC and 1%PS.
Comparative example 4, the present embodiment provides a kind of nonaqueous electrolytic solution, at the body containing 1M LiPF6
The electrolyte of long-pending ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate than 1:1:1 adds
0.5%VC and 1%PS.
Fig. 1 is the nonaqueous electrolytic solution containing high voltage protection agent and contrast using embodiment 13 to prepare
The cycle performance of 3.0-4.5V under the 0.2C multiplying power of the graphite/cobalt acid lithium battery of example 4 electrolyte.
It can be seen that after 100 times circulate, blank battery capacity conservation rate drastically drops to
84.7%, and use the battery capacity decay of this electrolyte to be seldom maintained at more than 96.2%, thus
It can be seen that use the electrolyte of this kind of high voltage additive substantially can improve the circulation of battery
Performance, reaches to improve the purpose of battery life then.
The above, be only presently preferred embodiments of the present invention, is not that the present invention is made it
The restriction of its form, any those skilled in the art are possibly also with the technology of the disclosure above
Content is changed or is modified as the Equivalent embodiments of equivalent variations is applied to other field, but
Every without departing from technical solution of the present invention content, implement above according to the technical spirit of the present invention
Any simple modification, equivalent variations and the remodeling that example is made, still falls within technical solution of the present invention
Protection domain.
Claims (5)
1. the nonaqueous electrolytic solution containing high voltage protection agent, it is characterised in that according to weight fraction include with
Lower material:
Described organic solvent is high-purity carbonate based organic solvent.
A kind of nonaqueous electrolytic solution containing high voltage protection agent the most according to claim 1, it is characterised in that
Described electrolyte lithium salt is LiBF4, lithium hexafluoro phosphate, double fluorine sulfonamide lithium or TFMS
At least one in lithium.
A kind of nonaqueous electrolytic solution containing high voltage protection agent the most according to claim 1, it is characterised in that
Described high-purity carbonate based organic solvent be in cyclic carbonates or linear carbonate compounds extremely
Few one；Described cyclic carbonate compounds is ethylene carbonate, propene carbonate, gamma-butyrolacton
In at least one；Described linear carbonate compounds be dimethyl carbonate, diethyl carbonate,
The carbonic acid that methyl ethyl ester and the straight or branched aliphatic monool that carbon number is 3-8 synthesize with carbonic acid
At least one in ester derivant.
A kind of nonaqueous electrolytic solution containing high voltage protection agent the most according to claim 1, it is characterised in that
Described functional additive is biphenyl, vinylene carbonate, fluorinated ethylene carbonate or 1,3-(1-propylene) sulphur
At least one in lactone.
5. according to a kind of nonaqueous electrolytic solution containing high voltage protection agent described in claim 1-4 any one, its
Being characterised by, the described nonaqueous electrolytic solution containing high voltage protection agent is applied in lithium secondary battery.
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| CN201610331511.0A CN105845971A (en) | 2016-05-17 | 2016-05-17 | Non-aqueous electrolyte containing high-voltage protective agent |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113381066A (en) * | 2020-03-09 | 2021-09-10 | 多氟多新材料股份有限公司 | High-performance lithium ion battery electrolyte, preparation method thereof and lithium ion battery |
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| CN103515096A (en) * | 2012-06-28 | 2014-01-15 | 海洋王照明科技股份有限公司 | Capacitor electrolyte |
| CN103633368A (en) * | 2013-10-28 | 2014-03-12 | 山东海容电源材料有限公司 | Flame-retardant additive for electrolyte and flame-retardant lithium ion battery electrolyte |
| KR20150075495A (en) * | 2013-12-26 | 2015-07-06 | 동우 화인켐 주식회사 | Electrolyte solution for lithium secondary battery and lithium secondary battery comprising the same |
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2016
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Patent Citations (4)
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| CN103426636A (en) * | 2012-05-14 | 2013-12-04 | 海洋王照明科技股份有限公司 | Capacitor electrolyte solution and preparing method thereof |
| CN103515096A (en) * | 2012-06-28 | 2014-01-15 | 海洋王照明科技股份有限公司 | Capacitor electrolyte |
| CN103633368A (en) * | 2013-10-28 | 2014-03-12 | 山东海容电源材料有限公司 | Flame-retardant additive for electrolyte and flame-retardant lithium ion battery electrolyte |
| KR20150075495A (en) * | 2013-12-26 | 2015-07-06 | 동우 화인켐 주식회사 | Electrolyte solution for lithium secondary battery and lithium secondary battery comprising the same |
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| CN113381066A (en) * | 2020-03-09 | 2021-09-10 | 多氟多新材料股份有限公司 | High-performance lithium ion battery electrolyte, preparation method thereof and lithium ion battery |
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