CN107732290A - A kind of high stability lithium-ion battery electrolytes and preparation method and application - Google Patents

A kind of high stability lithium-ion battery electrolytes and preparation method and application Download PDF

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Publication number
CN107732290A
CN107732290A CN201711082311.7A CN201711082311A CN107732290A CN 107732290 A CN107732290 A CN 107732290A CN 201711082311 A CN201711082311 A CN 201711082311A CN 107732290 A CN107732290 A CN 107732290A
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lithium
ion battery
high stability
battery electrolytes
ion
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CN107732290B (en
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邢丽丹
蓝广源
李伟善
廖友好
许梦清
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South China Normal University
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South China Normal University
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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
    • 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
    • H01M10/05—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
    • 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)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • 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 present invention discloses a kind of high stability lithium-ion battery electrolytes and preparation method and application, belongs to technical field of lithium ion.Described electrolyte includes electric conducting lithium salt, organic solvent and Mn (II) ion stabilizer；Described Mn (II) ion stabilizer：Mn[(CF3SO2)2N]2.Mn (II) ion stabilizer of the present invention can be deposited on negative pole SEI films surface in charge and discharge process, playing modification close to lithium titanate surface, stabilizing lithium ion diffusion, so as to effectively slow down the decline of cycle performance.Cycle performance of the lithium ion battery containing this electrolyte stabilizer under 0.005~2.5V be improved significantly.

Description

A kind of high stability lithium-ion battery electrolytes and preparation method and application
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of high stability lithium-ion battery electrolytes and its Preparation method and application.
Background technology
Lithium ion battery has high-energy-density, high output voltage, long circulation life in secondary cell is commercialized, from Discharge small and memory-less effect the characteristics of, because its electrode material selection diversity, in mobile phone, portable notebook, electricity It is used widely in the electronic equipments such as motor-car industry.
At present, with the negative material of lithium ion battery it is mainly commercially graphite, lithium titanate.Flexible wearable device apply, Under the conditions of fast charging and discharging, the application of graphite receives some limitations.And lithium titanate possesses high magnification, flexible excellent characteristic, The field is widely used.With the progress of science and technology and the development in market, the energy density for lifting lithium battery becomes more and more important It is and urgent.To a certain extent, the multiplying power compatibility that the negative material of lithium ion battery and positive electrode match is improved, and it is negative The energy density of pole carrying, is also research emphasis instantly.
Lithium titanate is as zero strain spinel, the theoretical releasable 175mAh/g under 1.0~2.5V voltage ranges, its Voltage platform is about in 1.55V.It is worth noting that, when lithium titanate is discharged to close to 0V, its theoretical specific capacity is about 293~ 296mAh/g, this is attributed to covalent bond stronger between titanium and oxygen.Under normal circumstances, cross and put to 0V, lithium titanate circle when voltage Surface resistance increase, lithium ion diffusion reduce, and polarization increase, ultimately result in cycle performance variation.
It is to be effectively increased lithium ion battery energy rationally using capacity/energy of this voltage range of 0~1.0V of lithium titanate Density, realize that its flexible and fast charging and discharging field obtains one of broader applications approach.In consideration of it, exploitation one kind can possess it is applicable The excellent electrolyte of lithium titanate low potential stability inferior, and then the excellent performance of lithium battery performance is realized, improve lithium battery and follow The ring life-span.
The content of the invention
The shortcomings that in order to overcome prior art and deficiency, primary and foremost purpose of the invention be to provide a kind of high stability lithium from Sub- battery electrolyte.The electrolyte when applied to lithium ion battery, is optimized negative by adding a certain amount of Mn (II) ion Pole/electrolyte interface, lithium titanate is improved as circulation of the negative material under low potential and high rate performance.
Another object of the present invention is to provide the preparation method of above-mentioned high stability lithium-ion battery electrolytes.
It is still another object of the present invention to provide the application of above-mentioned high stability lithium-ion battery electrolytes.
The purpose of the present invention is achieved through the following technical solutions：
A kind of high stability lithium-ion battery electrolytes, described electrolyte include electric conducting lithium salt, organic solvent and Mn (II) ion stabilizer；
Described Mn (II) ion stabilizer：Mn[(CF3SO2)2N]2(Mn[(TFSI)]2)。
Described electric conducting lithium salt is selected from bis trifluoromethyl sulfimide lithium (Li (CF3SO2)2N, LITFSI)；
Described organic solvent is made up of cyclic carbonate solvents and linear carbonate solvent；Cyclic carbonate solvents and line The mass ratio of type carbonate solvent is 1:1~2；Preferably 1：1.
Described cyclic carbonate solvents are preferably ethylene carbonate (EC)；Described linear carbonate solvent is preferably carbon Dimethyl phthalate (DMC).
Preferably, the concentration of described electric conducting lithium salt in the electrolytic solution is 1.0~1.2mol/L；Preferably 1.0mol/L.
Preferably, the content of described Mn (II) ion stabilizer is 0.2~0.6mol/L；Preferably 0.3mol/L.
The preparation method of above-mentioned high stability lithium-ion battery electrolytes, comprises the following steps：
(1) organic solvent, removal of impurities, water removal are configured；
(2) at ambient temperature, by the organic solvent obtained by electric conducting lithium salt addition step (1), stir, obtain Standard electrolytic liquid；
(3) Mn (II) ion stabilizer is added in the standard electrolytic liquid that step (2) obtains, obtains the electrolyte.
Removal of impurities, water removal phase described in step (1) are：By molecular sieve (Type,Type orType), activated carbon, Any one in calcium hydride, lithium hydride, anhydrous calcium oxide, calcium chloride, phosphorus pentoxide, alkali metal or alkaline-earth metal or two kinds Handled above.
Application of the above-mentioned high stability lithium-ion battery electrolytes in lithium ion battery is manufactured.
The present invention is had the following advantages relative to prior art and effect：
The present invention uses Mn (II) ions as the stabilizer under lithium-ion electrolyte low potential, because Mn (II) ion exists Negative pole SEI films surface can be deposited in charge and discharge process, modification is being played close to lithium titanate surface, is stabilizing lithium ion Diffusion, so as to effectively slow down the decline of cycle performance.Lithium ion battery containing this electrolyte stabilizer 0.005~ Cycle performance under 2.5V be improved significantly.
Brief description of the drawings
Fig. 1 is that the electric discharge of battery under the stable electrolyte that embodiment 1~3 is prepared and the gained electrolyte of comparative example 1 follows Ring the performance test results figure.
Fig. 2 is that the high rate performance of battery under the stable electrolyte that embodiment 1 is prepared and the gained electrolyte of comparative example 1 is surveyed Test result figure.
Fig. 3 is the XRD result figures of battery under the stable electrolyte that embodiment 1 is prepared and the gained electrolyte of comparative example 1.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited In this.
Embodiment 1
(1) cyclic carbonate solvents ethylene carbonate (EC) and linear carbonate solvent dimethyl carbonate (DMC) are pressed into matter Amount compares EC：DMC=1：1 mixing, and using molecular sieve, calcium hydride, lithium hydride clarification, water removal；
(2) at ambient temperature, electric conducting lithium salt LiTFSI is dissolved in the solvent that step (1) obtains, it is final concentration of 1.0mol/L, stir, obtain standard electrolytic liquid；
(3) the standard electrolytic liquid prepared in step (2) configures the Mn [(TFSI)] containing 0.3mol/L2, obtain be used for lithium from The stable type electrolyte of sub- battery.
Embodiment 2
(1) cyclic carbonate solvents ethylene carbonate (EC) and linear carbonate solvent dimethyl carbonate (DMC) are pressed into matter Amount compares EC：DMC=1：1 mixing, and using molecular sieve, calcium hydride, lithium hydride clarification, water removal；
(2) at ambient temperature, electric conducting lithium salt LiTFSI is dissolved in the solvent that step (1) obtains, it is final concentration of 1.0mol/L, stir, obtain standard electrolytic liquid；
(3) the standard electrolytic liquid prepared in step (2) configures the Mn [(TFSI)] containing 0.15mol/L2, obtain be used for lithium from The stable type electrolyte of sub- battery.
Embodiment 3
(1) cyclic carbonate solvents ethylene carbonate (EC) and linear carbonate solvent dimethyl carbonate (DMC) are pressed into matter Amount compares EC：DMC=1：1 mixing, and using molecular sieve, calcium hydride, lithium hydride clarification, water removal；
(2) at ambient temperature, electric conducting lithium salt LiTFSI is dissolved in the solvent that step (1) obtains, it is final concentration of 1.3mol/L, stir, obtain lithium-ion battery electrolytes.
Comparative example 1
Mn [(TFSI)] is not added in electrolyte2, other are same as Example 1.
Effect compares：
1. the electrolyte and the gained of comparative example 1 of the lithium ion battery that embodiment 1, embodiment 2, embodiment 3 are prepared Electrolyte carries out discharge cycle performance comparison, as a result as shown in Figure 1.As shown in Figure 1：Embodiment 1, embodiment 2 are in 0.6C (1C= 175mAh g-1) carry out 150 circle after can keep respectively 100%, 87.2% capability retention, and the electrolyte of comparative example 1 carry out 76.6% capability retention can only be kept after 130 circles.In addition, the result of embodiment 3 illustrates, the raising of cycle performance is not from Anion radical TFSI-Influence.
2. same, Fig. 2 multiplying power test result finds that the high rate performance of embodiment 1 is better than comparative example 1；After multiplying power test XRD results show (Fig. 3), after test, lithium titanate crystal formation does not change, but peak intensity dies down, and the XRD peaks of embodiment 1 It is better than comparative example 1 by force, this is consistent with multiplying power result.
More than, its cyclicity under low potential can be improved for lithium ion battery by adding the electrolyte of Mn (II) ion Can, there is inspiration effect in utilization flexibility and fast charging and discharging field.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (10)

  1. A kind of 1. high stability lithium-ion battery electrolytes, it is characterised in that：Described electrolyte includes electric conducting lithium salt, You Jirong Agent and Mn (II) ion stabilizer；
    Described Mn (II) ion stabilizer：Mn[(CF3SO2)2N]2。
  2. 2. high stability lithium-ion battery electrolytes according to claim 1, it is characterised in that：
    Described electric conducting lithium salt is selected from bis trifluoromethyl sulfimide lithium.
  3. 3. high stability lithium-ion battery electrolytes according to claim 1, it is characterised in that：
    Described organic solvent is made up of cyclic carbonate solvents and linear carbonate solvent；Cyclic carbonate solvents and Linear carbon The mass ratio of acid esters solvent is 1:1~2.
  4. 4. high stability lithium-ion battery electrolytes according to claim 1, it is characterised in that：
    Described cyclic carbonate solvents are ethylene carbonate；Described linear carbonate solvent is dimethyl carbonate.
  5. 5. high stability lithium-ion battery electrolytes according to claim 1, it is characterised in that：
    The concentration of described electric conducting lithium salt in the electrolytic solution is 1.0~1.2mol/L.
  6. 6. high stability lithium-ion battery electrolytes according to claim 1, it is characterised in that：
    The content of described Mn (II) ion stabilizer is 0.2~0.6mol/L.
  7. 7. the preparation method of the high stability lithium-ion battery electrolytes described in any one of claim 1~6, it is characterised in that bag Include following steps：
    (1) organic solvent, removal of impurities, water removal are configured；
    (2) at ambient temperature, by the organic solvent obtained by electric conducting lithium salt addition step (1), stir, obtain standard Electrolyte；
    (3) Mn (II) ion stabilizer is added in the standard electrolytic liquid that step (2) obtains, obtains the electrolyte.
  8. 8. the preparation method of high stability lithium-ion battery electrolytes according to claim 7, it is characterised in that：
    Removal of impurities, water removal phase described in step (1) are：Pass through molecular sieve, activated carbon, calcium hydride, lithium hydride, dry oxidation In calcium, calcium chloride, phosphorus pentoxide, alkali metal or alkaline-earth metal any one or two or more handled.
  9. 9. the preparation method of high stability lithium-ion battery electrolytes according to claim 8, it is characterised in that：
    Described molecular sieve isType,Type orType.
  10. 10. the answering in lithium ion battery is manufactured of the high stability lithium-ion battery electrolytes described in any one of claim 1~6 With.
CN201711082311.7A 2017-11-07 2017-11-07 High-stability lithium ion battery electrolyte and preparation method and application thereof Active CN107732290B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103413968A (en) * 2012-11-20 2013-11-27 浙江普耐德新能源科技有限公司 Lithium battery electrolyte and lithium battery comprising same
CN103943883A (en) * 2014-04-23 2014-07-23 华南师范大学 Application of borate compound serving as additive for high-voltage lithium-ion battery electrolyte
KR20150051557A (en) * 2013-11-04 2015-05-13 주식회사 엘지화학 A lithium secondary battery with enhanced performance
CN105762412A (en) * 2016-05-17 2016-07-13 华南师范大学 High-voltage electrolyte and lithium ion battery containing electrolyte

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103413968A (en) * 2012-11-20 2013-11-27 浙江普耐德新能源科技有限公司 Lithium battery electrolyte and lithium battery comprising same
KR20150051557A (en) * 2013-11-04 2015-05-13 주식회사 엘지화학 A lithium secondary battery with enhanced performance
CN103943883A (en) * 2014-04-23 2014-07-23 华南师范大学 Application of borate compound serving as additive for high-voltage lithium-ion battery electrolyte
CN105762412A (en) * 2016-05-17 2016-07-13 华南师范大学 High-voltage electrolyte and lithium ion battery containing electrolyte

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ANJAN BANERJEE ETC: "On the Oxidation State of Manganese Ions in Li-Ion Battery Electrolyte Solutions", 《J. AM. CHEM. SOC》 *
HOSOP SHIN, JONGHYUN PARK, ANN MARIE SASTRY, WEI LU: "Degradation of the solid electrolyte interphase induced by the deposition of manganese ions", 《JOURNAL OF POWER SOURCES》 *

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