CN103887559B - High-voltage electrolyte, high voltage nonaqueous electrolytic solution and lithium ion battery thereof - Google Patents

High-voltage electrolyte, high voltage nonaqueous electrolytic solution and lithium ion battery thereof Download PDF

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CN103887559B
CN103887559B CN201210556839.4A CN201210556839A CN103887559B CN 103887559 B CN103887559 B CN 103887559B CN 201210556839 A CN201210556839 A CN 201210556839A CN 103887559 B CN103887559 B CN 103887559B
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high voltage
electrolytic solution
nonaqueous electrolytic
additive
electrolyte
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CN103887559A (en
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杨同勇
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Honor Device Co Ltd
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Huawei Technologies Co Ltd
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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
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides a kind of high-voltage electrolyte and high voltage nonaqueous electrolytic solution thereof.High voltage nonaqueous electrolytic solution includes solute, solvent and high voltage additive, and high voltage additive structure is one or both in following formula:

Description

High-voltage electrolyte, high voltage nonaqueous electrolytic solution and lithium ion battery thereof
Technical field
The present invention relates to the lithium ion battery of a kind of high-voltage electrolyte, high voltage nonaqueous electrolytic solution and its composition.
Background technology
Lithium ion battery, compared with other batteries, has light weight, volume is little, operating voltage is high, energy is close Degree is high, power output is big, charge efficiency is high, memory-less effect, the advantage such as have extended cycle life, not only at hand The field such as machine, notebook computer is widely used, and is also considered as electric motor car, large-scale energy storage One of optimal selection of device.But current smart mobile phone, the energy to battery for the electronic digital products such as panel computer Metric density requires more and more higher so that commercial li-ion battery is difficult to meet requirement.Use high power capacity positive pole material Material or high-voltage anode material are an up the most effective approach of lithium ion battery energy density.
The research of current high-voltage anode material focuses primarily on LiNi0.5Mn1.5O4、LiCoPO4、LiNiPO4 Deng material, its discharge platform is respectively 4.7V, 4.8V and 5.1V, and charge cutoff voltage is above 4.5V. High power capacity positive electrode is with lithium-rich solid-solution material as study hotspot, and the premise of its release high power capacity is for wanting Material is charged to more than 4.5V.The operating voltage of current commercial electrolyte liquid is below 4.3V, as at 4.5V Application under above voltage can be oxidized, and this drawback causes penalty, seriously limits high-performance lithium ion battery Development.As can be seen here, high-voltage electrolyte technology is developed imperative.Current researcher focuses on employing High voltage additive or high voltage solvent two approach, promote electrolyte operating voltage.
Prior art one: use the sulfone class, nitrile, ionic liquid class material that anti-oxidant current potential is high as electrolysis The solvent of liquid, the operating voltage that can be obviously improved electrolyte reaches more than 5V.
But, the prior art have the disadvantage that sulfone class, nitrile, ionic liquid kind solvent as lithium from Sub-battery electrolyte solvent, is respectively provided with application drawback.Their electrical conductivity is less than commercial electrolyte liquid carbonates Solvent, damages battery large current density power；Their viscosity is more than the viscosity of commercial electrolyte liquid, not only Reduce the transfer rate of lithium ion, and the wettability to electrode and barrier film can be reduced.Above deficiency, Compromise the chemical property of lithium ion battery, limit application.
Prior art two: add high voltage additive in commercial electrolyte liquid.In cyclic process for several times originally In, additive reacts, and participates in the formation of positive electrode surface protective layer, barrier material and electrolyte direct Contact, and then the side reaction that suppression electrolyte is oxidized, promote lithium battery high-voltage applications performance.The program Advantage is that the high-voltage electrolyte adding additive is almost identical with the physico-chemical property of its parent.Document (Electrochemical Communications 18 (2012) 123-126) reports a kind of high voltage and adds Agent, this additive is obviously improved performance under the conditions of high voltage applications for the 4.3V electrolyte.The difficult point of this technology It is to find the additive molecule being suitable for.
Content of the invention
In view of the foregoing, it is necessary to the non-aqueous high voltage electrolysis of a kind of high voltage additive and composition thereof is provided Liquid, it can keep lithium ion transmission dynamic performance and electrode interface/barrier film wettability, and add high voltage The nonaqueous electrolytic solution of additive can be applied under more than 4.5V voltage.
A kind of high-voltage electrolyte, containing the high electricity that mass percent is 0.1%～10% in described high-voltage electrolyte Pressure additive, the structure of described high pressure additive is one or both in having structure:
Wherein R1, R2, R3 are halogen, hydrogen, hydroxyl, the metal compound of oxygen, alkyl, oxyalkyl, halogen Replace one or more in alkyl or oxyalkyl.
A kind of high voltage nonaqueous electrolytic solution, including solute, solvent and high voltage additive, described high voltage adds Add that agent structure is in having structure one or both:
Wherein, R1, R2, R3 be halogen, hydrogen, hydroxyl, the metal compound of oxygen, alkyl, oxyalkyl, Halogen replaces one or more in alkyl or oxyalkyl.
Preferably, mass percent in this high voltage nonaqueous electrolytic solution for the described high voltage additive is 0.1%～10%；More preferably mass percent is 0.5%～5%.
Preferably, described halogen replaces alkyl or oxyalkyl is CF3、C2F5、CH2CF3、CHC2F6、C(CF3)3、 C(CH3)(CF3)2、C(CH3)2CF3、CHCHCF3、OCF3、OC2F5、OCH2CF3、OCHC2F6、 OC(CF3)3、OC(CH3)(CF3)2, or OC (CH3)2CF3。
Preferably, the solvent of described high voltage nonaqueous electrolytic solution be fatty or ring-type carbonic ester, ether, sulfone, One or more in nitrile, ionic liquid and derivative thereof.
Preferably, the solvent of described high voltage nonaqueous electrolytic solution can for EC, PC, VC, DMC, DEC, EMC, FEC, inner butyl ester, methyl inner butyl ester, ethyl inner butyl ester, diethylformamide, methyl ethyl ether, Oxolane, sulfolane, acetonitrile or 1-methyl-3-ethyl imidazol(e) two (trimethyl fluoride sulfonyl) imines etc..
Preferably, the solute of described high voltage nonaqueous electrolytic solution is one or more lithium salts.
Preferably, described lithium salts is lithium hexafluoro phosphate, hexafluoroarsenate lithium, LiBF4, trifluoromethyl sulphur Acid lithium, two (trimethyl fluoride sulfonyl) imine lithium, lithium perchlorate, LiBOB or LiBF2C2O4。
Preferably, the solvent of described high voltage nonaqueous electrolytic solution also includes for meeting high-voltage electrolyte application need The functional additive asked, described functional additive includes flame-retardant additive, high temperature additive, low temperature additive Or circulation additive.
A kind of high-voltage lithium ion batteries, it includes positive pole, negative pole and electrolyte, this lithium ion battery Electrolyte comprises electrolyte as above.
Compared with prior art, the invention have the advantages that the high-tension electricity comprising that there is high voltage additive Solve liquid, high voltage nonaqueous electrolytic solution lithium ion battery in use, high voltage additive reacts, Participate in the formation of positive electrode surface protective layer, the oxidation of solvent can be suppressed, it is achieved more than 4.5V high voltage applications； And the preparation of high voltage nonaqueous electrolytic solution is simple, technical maturity is high；It only need to add height in commercial electrolyte liquid Voltage additive.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with being embodied as Example, is further elaborated to the present invention.Only it should be appreciated that specific embodiment described herein It in order to explain the present invention, is not intended to limit the present invention.
The invention provides a kind of high voltage additive, and the non-water power of high voltage comprising this high voltage additive Solve liquid.
High voltage nonaqueous electrolytic solution is with traditional lithium-ion battery electrolyte as parent, is added by adding high voltage Add obtained from agent.Electrolyte parent is by lithium salts solute, solvent and other functional additives by a certain percentage Constitute.Wherein the molar concentration of lithium salts is 0.1～1.5mol/L, for providing in the electrolytic salt of lithium ion One or more, can for lithium hexafluoro phosphate, hexafluoroarsenate lithium, LiBF4, trifluoromethyl sulfonic acid lithium, Two (trimethyl fluoride sulfonyl) imine lithium, lithium perchlorate, LiBOB, LiBF2C2O4, or other lithium can be provided The salt of ion.
Solvent is the main body of electrolyte, for the solvent of the electrolyte lithium salt that can dissociate, can be fatty or ring-type carbon One or more in acid esters, ether, sulfone, nitrile, ionic liquid and their derivative, such as EC, PC, VC, DMC, DEC, EMC, FEC, inner butyl ester, methyl inner butyl ester, ethyl inner butyl ester, diethyl Diamides, methyl ethyl ether, oxolane, sulfolane, acetonitrile, 1-methyl-3-ethyl imidazol(e) two (trifluoro Sulfonyloxy methyl) imines etc..
The mass percent of functional additive is 0%～15%, is to be added by meeting electrolyte application-specific demand The material adding, such as high temperature additive, low temperature additive, flame-retardant additive, overcharging additive etc..
Functional additive in the high voltage nonaqueous electrolytic solution of the present invention comprises high voltage additive, and high voltage adds Adding weight/mass percentage composition in high voltage nonaqueous electrolytic solution for the agent is 0.1%～10%.The knot of high voltage additive Structure is one or both in having structure:
Wherein, R1, R2, R3 be halogen, hydrogen, hydroxyl, the metal compound of oxygen, alkyl, oxyalkyl, Halogen replaces one or more in alkyl or oxyalkyl.Halogen replace alkyl or oxyalkyl can be replace completely or Part replaces, and for example, R1, R2, R3 can be CF3、C2F5、CH2CF3、CHC2F6、C(CF3)3、 C(CH3)(CF3)2、C(CH3)2CF3、CHCHCF3、OCF3、OC2F5、OCH2CF3、OCHC2F6、 OC(CF3)3、OC(CH3)(CF3)2、OC(CH3)2CF3；Halogen can be F, Cl, Br, I；Alkyl and oxygen Alkyl can be straight or branched.
Use described high-voltage electrolyte, use traditional lithium-ion battery assembly and preparation technology, height can be prepared Voltage lithium ion battery.
Embodiment one:
According to conventional battery preparation method assembling test battery.With LiNi0.5Mn1.5O4For positive pole, lithium metal For negative pole, both positive and negative polarity collector is respectively aluminium foil and Copper Foil, and electrolyte component is EC/EMC(30:70) The LiPF of 1mol/L6Solution, high voltage additive is three (isopropyl) arsenate, and its mass percent is 1%.Battery circulates with 0.2C rate charge-discharge in 3～4.9V voltage range.
Embodiment two:
Using the method identical with embodiment one prepare battery and test, difference is high voltage additive Being three (1,1,1,3,3,3-hexafluoro isopropyl) arsenate, its mass percent is 1%.
Embodiment three:
Using the method identical with embodiment one prepare battery and test, difference is high voltage additive It is three (1,1,1,3,3,3-hexafluoro isopropyl) arsenates and the mixture of three (isopropyl) arsenate, its matter Amount ratio is 1:1, and gross mass percentage is 1%.
Comparative example:
Using the method identical with embodiment one prepare battery and test, difference is to be not added with high voltage Additive.
Table 1
Battery Capability retention (%) after 150 circulations
Comparative example 61
Embodiment one 70
Embodiment two 78
The present invention relates to lithium ion battery high voltage nonaqueous electrolytic solution, possess following beneficial effect:
1st, the preparation of high voltage nonaqueous electrolytic solution is simple, technical maturity is high；It only need to add in commercial electrolyte liquid High voltage additive.
2nd, in application process, additive reacts, and participates in the formation of positive electrode surface protective layer, can suppress The oxidation of solvent, it is achieved more than 4.5V high voltage applications.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all at this Any modification, equivalent and the improvement etc. made within bright spirit and principle, should be included in the present invention Protection domain within.

Claims (11)

1. a high-voltage electrolyte, it is characterized in that, described high-voltage electrolyte is in lithium ion battery, and containing the high voltage additive that mass percent is 0.1%～10% in described high-voltage electrolyte, the structure of described high voltage additive is one or both in having structure:
Wherein R1, R2, R3 are that halogen, hydrogen, hydroxyl, oxyalkyl, halogen replace one or more in oxyalkyl.
2. a high voltage nonaqueous electrolytic solution, described high-voltage electrolyte is used in lithium ion battery, including solute, solvent and high voltage additive, it is characterised in that: described high voltage additive structure is one or both in having structure:
Wherein R1, R2, R3 are that halogen, hydrogen, hydroxyl, oxyalkyl, halogen replace one or more in oxyalkyl.
3. such as claim 2 high voltage nonaqueous electrolytic solution, it is characterised in that: mass percent in this high voltage nonaqueous electrolytic solution for the described high voltage additive is 0.1%～10%.
4. high voltage nonaqueous electrolytic solution as claimed in claim 3, it is characterised in that: mass percent in described high voltage nonaqueous electrolytic solution for the described high voltage additive is 0.5%～5%.
5. high voltage nonaqueous electrolytic solution as claimed in claim 2, it is characterised in that: described oxyalkyl is OCF3、OC2F5、OCH2CF3、OCHC2F6、OC(CF3)3、OC(CH3)(CF3)2Or OC (CH3)2CF3。
6. high voltage nonaqueous electrolytic solution as claimed in claim 2, it is characterised in that: the solvent of described high voltage nonaqueous electrolytic solution is one or more in the derivative of ring-type carbonic ester, ether, sulfone, nitrile, ionic liquid and described carbonic ester, ether, sulfone, nitrile, ionic liquid.
7. high voltage nonaqueous electrolytic solution as claimed in claim 6, it is characterised in that: the solvent of described high voltage nonaqueous electrolytic solution is EC, PC, VC, DMC, DEC, EMC, FEC, inner butyl ester, methyl inner butyl ester, ethyl inner butyl ester, methyl ethyl ether, oxolane, sulfolane or acetonitrile.
8. high voltage nonaqueous electrolytic solution as claimed in claim 2, it is characterised in that: the solute of described high voltage nonaqueous electrolytic solution is one or more lithium salts.
9. high voltage nonaqueous electrolytic solution as claimed in claim 8, it is characterised in that: described lithium salts is lithium hexafluoro phosphate, hexafluoroarsenate lithium, LiBF4, trifluoromethyl sulfonic acid lithium, two (trimethyl fluoride sulfonyl) imine lithium, lithium perchlorate, LiBOB or LiBF2C2O4。
10. high voltage nonaqueous electrolytic solution as claimed in claim 2, it is characterized in that: the solvent of described nonaqueous electrolytic solution also includes the functional additive for meeting high-voltage electrolyte application demand, described functional additive includes flame-retardant additive, high temperature additive, low temperature additive or circulation additive.
11. 1 kinds of high-voltage lithium ion batteries, it includes positive pole, negative pole and electrolyte, it is characterised in that: the electrolyte of this lithium ion battery comprises the electrolyte as according to any one of claim 1 to 10.
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CN108155362A (en) * 2017-12-25 2018-06-12 北京国能电池科技有限公司 High-voltage lithium-battery cathode material, lithium ion battery and preparation method thereof
CN114725509A (en) * 2022-04-25 2022-07-08 西安交通大学 Sulfone-based lithium battery electrolyte and lithium battery

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Electrolyte additive trimethyl phosphate for improving electrochemical performance and thermal stability of LiCoO2 cathode;H.Y.Xu等;《Electrochimica Acta》;20060705;第52卷;第636-642页 *

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