CN102035022B - Method for preparing electrolyte for 5V lithium ion battery - Google Patents

Method for preparing electrolyte for 5V lithium ion battery Download PDF

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Publication number
CN102035022B
CN102035022B CN2010105610636A CN201010561063A CN102035022B CN 102035022 B CN102035022 B CN 102035022B CN 2010105610636 A CN2010105610636 A CN 2010105610636A CN 201010561063 A CN201010561063 A CN 201010561063A CN 102035022 B CN102035022 B CN 102035022B
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electrolyte
additive
ion battery
sulfone
lithium ion
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CN102035022A (en
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魏进平
胡梦
周震
邢丽英
秦杏
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Nankai University
Delta Optoelectronics Inc
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Nankai University
Delta Optoelectronics Inc
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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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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a method for preparing electrolyte for a 5V lithium ion battery. The method comprises the following steps of: 1) purifying and dehydrating sulfone and carbonic ester respectively and mixing to obtain a mixed solvent; 2) dissolving a lithium salt in the mixed solvent to obtain additive-free electrolyte; and 3) dissolving an additive in the additive-free electrolyte to obtain the electrolyte for the 5V lithium ion battery, wherein the additive is lithium difluoro(oxalato)borate (LiDFOB). The method has the advantages that: the electrolyte can improve the compatibility of the electrolyte and a high-voltage positive electrode, decomposition of the electrolyte on the surface of a high-voltage positive electrode material in a charging process can be reduced and a stable solid electrolyte interface (SEI) film on the surfaces of the positive electrode and a negative electrode is formed, so that charge and discharge capacity and cyclical stability of the positive electrode material are obviously improved; and the method is simple, easy to implement and low in raw material cost, has broad application prospect and is suitable for industrial production.

Description

A kind of is the preparation method of the electrolyte of 5V lithium ion battery for voltage
Technical field
The present invention relates to a kind of electrolyte of lithium ion battery, particularly a kind of preparation that is suitable for high voltage (5V) lithium-ion battery electrolytes.
Background technology
Lithium ion battery has been widely used in the portable electric appts such as mobile phone, notebook computer at present.The operating voltage of commercial li-ion battery is 3.7 V, and energy density is low, can not satisfy the growth requirement of portable electric appts, and the operating voltage of raising lithium ion battery is one of effective ways that improve energy density.The high-voltage anode material of having reported has LiCoPO 4, LiNiPO 4, Li 3V 2PO 4, LiNi 0.5Mn 1.5O 4Deng, its charging voltage platform is close to or higher than 5V, but the electrolyte that matches rarely has report.The electrolyte of lithium ion battery commonly used is mainly 1M LiPF at present 6Be dissolved in the carbonates solvent.But its electrochemical window is narrow, easily decomposes under high voltage, can not satisfy high-voltage anode material (such as LiCoPO 4Deng) requirement.
The electrochemical window of sulfone is wide, and (electrochemical window of sulfolane TMS is 0-6 V vs. Li +/ Li), it is anodal lithium ion battery that the people such as Abouimrane [Electrochem. Commun. 11 (2009) 1073-1076] are used for LiMn2O4 with pure sulfone class, battery has good cycle performance.The people such as Amine [Electrochemical and Solid-State Letters, 3 (2000) 178-179] are used for high-voltage anode material LiCoPO with pure sulfolane 4But the positive electrode chemical property improves little.
Difluorine oxalic acid boracic acid lithium (LiDFOB) has dioxalic acid lithium borate LiBOB and LiBF concurrently as a kind of novel lithium salts and additive 4Advantage, solubility is high, can form more effective SEI film, significantly improves rate capability and the high low temperature cycle performance of battery.The people such as Yang Peng disclose a kind of lithium-ion battery electrolytes, contain the difluorine oxalic acid boracic acid lithium that accounts for gross mass 1-5 wt% and the alkylene unsaturates of 1-10 wt% in its electrolyte, can effectively improve high-temperature storage performance and the cycle performance (CN 101656332A) of lithium ion battery.The people such as Yin Zhenguo disclose a kind of LiMn2O4 that improves and have been the electrolyte of anodal performance of lithium ion battery, wherein contain the difluorine oxalic acid boracic acid lithium of 0.1-0.5 mol/L as film for additive, can the establishment anode and the reaction of electrolyte, slow down the decay of battery capacity in cyclic process, but do not study difluorine oxalic acid boracic acid lithium to the impact (CN 101350430A) of high-voltage anode material performance.The people such as Lee's Jie disclose a kind of Difunctional electrolyte, be dissolved in LiDFOB and difluoro oxalate boric acid tetraethyl amine TEADFOB in the carbonate solvent that contains PC with certain mol ratio, added simultaneously the oxolane of 0.1-6 wt%, diethylene glycol dimethyl ether, in methyl-sulfoxide or the sulfolane one or more can satisfy lithium ion battery and rely on Li +The requirement of chemical energy storage can be satisfied again the requirement (CN 101587777A) of ultracapacitor electric double layer capacitance energy storage.
Summary of the invention
The objective of the invention is according to above-mentioned technical Analysis, providing a kind of is the preparation method of the electrolyte of 5V lithium ion battery for voltage, and the method technique is simple, easy to implement, cost of material is cheap, is suitable for suitability for industrialized production.
Technical scheme of the present invention:
A kind of is the preparation method of the electrolyte of 5V lithium ion battery for voltage, it is characterized in that comprising the steps:
1) with the respectively purifying rear mixing that dewaters of sulfone and carbonic ester, obtains mixed solvent;
2) lithium salts is dissolved in the above-mentioned mixed solvent, is not contained the electrolyte of additive;
3) additive is dissolved in the above-mentioned electrolyte that does not contain additive, obtaining for voltage is the electrolyte of 5V lithium ion battery.
Described sulfone is ethylmethane sulfonate (EMS), sulfolane (TMS), positive fourth sulfone (BS), methoxy sulfone (MEMS), ethyl vinyl sulfone (EVS), ethyl methoxyethyl sulfone (EMES) and 1-fluoro-2-(methyl sulphonyl) mixture of one or more arbitrary proportions in the benzene (FS).
Described carbonic ester comprises cyclic carbonate and linear carbonate, cyclic carbonate is the mixture of one or more arbitrary proportions in ethylene carbonate (EC), propene carbonate (PC) and the gamma-butyrolacton (BL), and linear carbonate is the mixture of one or more arbitrary proportions in dimethyl carbonate (DMC), Methylethyl carbonic ester (EMC), methyl formate, Ethyl formate and the methyl acetate.
The volume ratio of sulfone and carbonic ester is (0.5-2) in the described mixed solvent: 1.
Described lithium salts is LiPF 6, LiBF 4, LiTFSI, LiClO 4With the mixture of one or more arbitrary proportions among the LiBOB, the concentration of lithium salts in carbonic ester and sulfone mixed solvent is 0.5-2 mol/L.
Described additive is difluorine oxalic acid boracic acid lithium (LiDFOB), and molecular formula is LiBF 2C 2O 4, the consumption of additive is 1-10% with the mass ratio that does not contain the electrolyte of additive.
Advantage of the present invention is: this electrolyte can improve the compatibility of electrolyte and high-voltage anode, electrolyte is in the decomposition on high-voltage anode material surface in the minimizing charging process, and can form stable SEI film on the both positive and negative polarity surface, so that the charge/discharge capacity of positive electrode and cyclical stability significantly improve; And technique is simple, easy to implement, cost of material is cheap, be suitable for suitability for industrialized production, has a extensive future.
Description of drawings
Fig. 1 is LiCoPO 4The charge and discharge circulation life figure (solvent EC-EMC-DMC) of positive electrode in different electrolytes.
Fig. 2 is LiCoPO 4The charge and discharge circulation life figure (solvent EC-PC-EMC) of positive electrode in different electrolytes.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited to this.
Embodiment 1:
A kind of is the preparation method of the electrolyte of 5V lithium ion battery for voltage, comprises the steps:
1) with the respectively purifying rear mixing that dewaters of ethylene carbonate (EC), Methylethyl carbonic ester (EMC), dimethyl carbonate (DMC), volume ratio is 1:1:1, stirs; Above-mentioned carbonic ester mixed solvent is mixed with sulfolane, and volume ratio is 1:1, and stirring obtains mixed solvent;
2) with LiPF 6Add in the above-mentioned mixed solvent LiPF 6Concentration in mixed solvent stirs for being 1 mol/L, is not contained the electrolyte of additive;
3) add the additive difluorine oxalic acid boracic acid lithium, its percentage consumption is 5% of electrolyte quality, makes it dissolving, stirs, and obtaining for voltage is the electrolyte of 5V lithium ion battery.
Effect detects:
With LiCoPO 4Be positive electrode, the anodal batching according to active material: the weight of acetylene black: binding agent=75:20:5 is carried out mixed slurry, the compressing tablet post-drying.Adopt lithium metal as negative pole, aluminium foil and Copper Foil are respectively the both positive and negative polarity collector, and used barrier film is Celgard-2400.
Adopt in the contrast test three kinds of different electrolyte: A-for the electrolyte that do not contain sulfolane and difluorine oxalic acid boracic acid lithium, B-for electrolyte, the C that does not contain additive be the present invention make to be used for voltage be the electrolyte of 5V lithium ion battery.
Fig. 1 is LiCoPO 4The charge and discharge circulation life figure of positive electrode in different electrolytes.Charging/discharging voltage is 3-5.1 V, and charging and discharging currents is 0.1 C.Testing result shows: when adopting respectively electrolyte A, B, C, and LiCoPO 4Positive electrode initial discharge specific capacity is respectively 88.2,107.9,116.6 mAh/g; Charge and discharge cycles is after 21 weeks, specific discharge capacity is respectively 22.9,36.9,66.3 mAh/g, its capability retention is respectively 26.0,34.2,56.9%, after illustrating that employing contains the electrolyte of additive, discharge capacity and the charge-discharge performance of lithium ion anode material under high voltage obtains larger raising.
Embodiment 2:
A kind of is the preparation method of the electrolyte of 5V lithium ion battery for voltage, comprises the steps:
1) with the respectively purifying rear mixing that dewaters of ethylene carbonate (EC), propene carbonate (PC), Methylethyl carbonic ester (EMC), volume ratio is 1:1:3, stirs; Above-mentioned carbonic ester mixed solvent is mixed with sulfolane, and volume ratio is 1:1, and stirring obtains mixed solvent;
2) with LiPF 6Add in the above-mentioned mixed solvent LiPF 6Concentration in mixed solvent stirs for being 1 mol/L, is not contained the electrolyte of additive;
3) add the additive difluorine oxalic acid boracic acid lithium, its percentage consumption is 5% of electrolyte quality, makes it dissolving, stirs, and obtaining for voltage is the electrolyte of 5V lithium ion battery.
Effect detects:
With LiCoPO 4Be positive electrode, the anodal batching according to active material: the weight of acetylene black: binding agent=75:20:5 is carried out mixed slurry, the compressing tablet post-drying.Adopt lithium metal as negative pole, aluminium foil and Copper Foil are respectively the both positive and negative polarity collector, and used barrier film is Celgard-2400.
Adopt in the contrast test two kinds of different electrolyte: A-for electrolyte, the B-that does not contain sulfolane and additive be the present invention make to be used for voltage be the electrolyte of 5V lithium ion battery.
Fig. 2 is LiCoPO 4The charge and discharge circulation life figure of positive electrode in different electrolytes.Charging/discharging voltage is 3-5.1 V, and charging and discharging currents is 0.1 C.Contain under the condition of additive LiCoPO at electrolyte 4Positive electrode initial discharge specific capacity is 137.6 mAh/g, and after 40 weeks of 0.1 C charge and discharge cycles, specific capacity is 97.2 mAh/g, and capability retention is 70.6%.And under equal conditions do not adopt the pure LiPF of additive 6In-EC-PC-EMC the electrolyte, LiCoPO 4Positive electrode initial discharge specific capacity is 119.4 mAh/g, and after 40 weeks of 0.1 C charge and discharge cycles, specific capacity is 10.3 mAh/g, and capability retention is 8.6% only, illustrates to adopt the electrolyte that contains additive, LiCoPO 4Positive electrode discharge capacity and cycle performance under high voltage all are significantly improved.

Claims (3)

1. one kind is the preparation method of the electrolyte of 5V lithium ion battery for voltage, it is characterized in that comprising the steps:
1) with the respectively purifying rear mixing that dewaters of sulfone and carbonic ester, obtains mixed solvent;
2) lithium salts is dissolved in the above-mentioned mixed solvent, is not contained the electrolyte of additive;
3) additive is dissolved in the above-mentioned electrolyte that does not contain additive, obtaining for voltage is the electrolyte of 5V lithium ion battery;
Described additive is difluorine oxalic acid boracic acid lithium, and molecular formula is LiBF 2C 2O 4, the consumption of additive is 1-10% with the mass ratio that does not contain the electrolyte of additive;
Described sulfone is the mixture of one or more arbitrary proportions in sulfolane, positive fourth sulfone, ethyl vinyl sulfone and the ethyl methoxyethyl sulfone;
The volume ratio of sulfone and carbonic ester is 0.5-2:1 in the described mixed solvent.
2. described according to claim 1 is the preparation method of the electrolyte of 5V lithium ion battery for voltage, it is characterized in that: described carbonic ester comprises cyclic carbonate and linear carbonate, cyclic carbonate is the mixture of one or more arbitrary proportions in ethylene carbonate, propene carbonate and the gamma-butyrolacton, and linear carbonate is the mixture of one or more arbitrary proportions in dimethyl carbonate, Methylethyl carbonic ester, methyl formate, Ethyl formate and the methyl acetate.
3. described according to claim 1 is the preparation method of the electrolyte of 5V lithium ion battery for voltage, and it is characterized in that: described lithium salts is LiPF 6, LiBF 4, LiTFSI, LiClO 4With the mixture of one or more arbitrary proportions among the LiBOB, the concentration of lithium salts in carbonic ester and sulfone mixed solvent is 0.5-2mol/L.
CN2010105610636A 2010-11-26 2010-11-26 Method for preparing electrolyte for 5V lithium ion battery Expired - Fee Related CN102035022B (en)

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CN102340030A (en) * 2011-08-22 2012-02-01 刘春蕾 Electrolyte of lithium ion battery
CN102403535A (en) * 2011-12-01 2012-04-04 香河昆仑化学制品有限公司 Non-water electrolyte for high-voltage lithium ion battery and preparation method
WO2014034043A1 (en) * 2012-08-27 2014-03-06 三洋電機株式会社 Nonaqueous electrolyte secondary battery
CN102881941A (en) * 2012-10-13 2013-01-16 兰州理工大学 Electrolyte of lithium ion battery
CN103545552B (en) * 2013-10-14 2016-03-09 合肥国轩高科动力能源有限公司 Be suitable for the electrolyte of high-voltage lithium ion batteries
CN103531843A (en) * 2013-10-24 2014-01-22 兰州理工大学 Electrolytic solution for high-temperature high-magnification type lithium ion battery
CN104752770A (en) * 2013-12-30 2015-07-01 天津金牛电源材料有限责任公司 Preparation method of high voltage electrolyte used for lithium ion battery
DE102014108254A1 (en) * 2014-06-12 2015-12-17 Karlsruher Institut für Technologie Innovationsmanagement Electrolyte, cell and battery comprising the electrolyte and its use
CN104409772B (en) * 2014-12-04 2017-02-22 张家港市国泰华荣化工新材料有限公司 Lithium-ion battery electrolyte and lithium-ion battery
CN105742703A (en) * 2016-03-09 2016-07-06 华南师范大学 High-voltage functional electrolyte containing LiDFOB additive and preparation and application thereof
CN106025357A (en) * 2016-06-24 2016-10-12 张家港市国泰华荣化工新材料有限公司 Electrolyte for lithium ion battery and lithium ion battery
CN107959050A (en) * 2017-11-07 2018-04-24 华南师范大学 A kind of high-energy-density highly secure lithium ion battery sulfone-based electrolyte and preparation method thereof
CN108134138B (en) * 2017-11-29 2019-10-25 清远佳致新材料研究院有限公司 A kind of high voltage bearing lithium-ion battery electrolytes and lithium ion battery
CN114039088A (en) * 2021-09-30 2022-02-11 国联汽车动力电池研究院有限责任公司 Composition for preparing solid polymer electrolyte and application thereof
CN114725509A (en) * 2022-04-25 2022-07-08 西安交通大学 Sulfone-based lithium battery electrolyte and lithium battery
CN117239138B (en) * 2023-11-15 2024-01-23 华北电力大学 Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery

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