CN103531845A - Lithium-ion battery electrolyte taking LiBF2SO4 as basic lithium salt - Google Patents

Lithium-ion battery electrolyte taking LiBF2SO4 as basic lithium salt Download PDF

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Publication number
CN103531845A
CN103531845A CN201310507642.6A CN201310507642A CN103531845A CN 103531845 A CN103531845 A CN 103531845A CN 201310507642 A CN201310507642 A CN 201310507642A CN 103531845 A CN103531845 A CN 103531845A
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lithium
electrolyte
lithium salts
mol
ion battery
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Inventor
李世友
张宏明
崔孝玲
赵伟
李永立
李晓鹏
刘金良
净洁
李玲霞
薛宇宙
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Lanzhou University of Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • H01M10/0568Liquid materials characterised by the solutes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • H01M10/0569Liquid materials characterised by the solvents
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a lithium-ion battery electrolyte taking LiBF2SO4 as basic lithium salt. The electrolyte comprises the following components: electrolyte lithium salt and an aprotic solvent, wherein the electrolyte lithium salt can be unitary LiBF2SO4 and also can be a mixture of LiBF2SO4 and other common lithium salts; the aprotic solvent is one or a mixture of some of common carbonic ester, sulphite, sulfone compounds and the like. Through the lithium-ion battery electrolyte, disclosed by the invention, the compatibility between the electrolyte and the electrode materials can be improved; meanwhile, the rate performance, the high-temperature performance and the cycle performance of the lithium-ion battery can be effectively improved.

Description

With LiBF 2sO 4lithium-ion battery electrolytes for basic lithium salts
Technical field
The present invention relates to the technical field of lithium-ion battery electrolytes, specifically disclose a kind of with LiBF 2sO 4new type lithium ion battery electrolyte for basic lithium salts.
Background technology
It is high that lithium ion battery has operating voltage, and specific energy is high, security performance good, memory-less effect, self discharge are little, have extended cycle life, advantages of environment protection, has been widely used in Portable mobile phone, notebook computer and electric automobile.Electrolyte is one of important component part of battery, and it plays the effect of transmission ion between the both positive and negative polarity of battery, and the characteristics such as the capacity of battery, cycle performance and security performance are had to material impact.Electrolyte used in the market, its solvent mostly is the mixture of carbonic ester, and electrolyte lithium salt is mainly lithium hexafluoro phosphate (LiPF 6) (Li Z D, Zhang Y C, Xiang H F, et al. J. Power Sources, 2013,240:471-475).Although this class electrolyte has higher conductivity and anti-oxidant current potential, due to LiPF 6easily with electrolyte in the water of trace react, generation HF, damages electrode material, has reduced the cycle performance of battery.In addition, LiPF 6heat decomposition temperature lower, limited the high-temperature behavior of battery.
Summary of the invention
the object of this invention is to provide a kind ofwith LiBF 2sO 4lithium-ion battery electrolytes for basic lithium salts.
The present invention is with LiBF 2sO 4for the lithium-ion battery electrolytes of basic lithium salts, this electrolyte contains electrolyte lithium salt and aprotic solvent, and described electrolyte lithium salt can be lithium salts A, can be also the mixture of lithium salts A and lithium salts B; Wherein lithium salts A is LiBF 2sO 4, lithium salts B is one or more the mixture in lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, lithium trifluoromethanesulp,onylimide, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium.
usefulness of the present invention is:electrochemical window is wide, and solubility and conductivity in common aprotic solvent are high; Heat decomposition temperature high (being about 100 ℃), can improve the high-temperature behavior of battery; Similar with LiBOB and LiODFB, also can participate in the film forming procedure on positive electrode surface to improve the high voltage performance of battery; Similar with LiBOB and LiODFB, the preferential reduction that also can negative terminal surface occur in 1.7 V left and right is to form stable SEI film (even in pure carbonic allyl ester solution), this has greatly widened selectable range and the building mode of dicyandiamide solution, has broken away from the dependence of traditional electrolyte to ethylene carbonate; Similar with PS, sulfite, its reduzate contains relatively large sulfur-containing compound, is conducive to reduce the impedance of the SEI film that forms, and then improves high rate performance and the cycle performance of battery.Therefore, LiBF 2sO 4well combine the two advantage of LiBOB or LiODFB and sulfur-containing compound solvent, can improve the compatibility of electrolyte and electrode material, and can effectively improve high rate performance, high-temperature behavior and the cycle performance of lithium ion battery.
Embodiment
the present invention iswith LiBF 2sO 4for the lithium-ion battery electrolytes of basic lithium salts, this electrolyte contains electrolyte lithium salt and aprotic solvent, and described electrolyte lithium salt can be lithium salts A, can be also the mixture of lithium salts A and lithium salts B; Wherein lithium salts A is LiBF 2sO 4, lithium salts B is lithium hexafluoro phosphate (LiPF 6), LiBF4 (LiBF 4), lithium perchlorate (LiClO 4), hexafluoroarsenate lithium (LiAsF 6), lithium trifluoromethanesulp,onylimide (Li (CF 3sO 2) 2n), the mixture of one or more in di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiODFB).
The concentration of described lithium salts A in electrolyte is 0.15-1.2 mol/L, and the concentration of described lithium salts B in electrolyte is 0-0.8 mol/L, and the total concentration of described mixing lithium salts in electrolyte is 0.15-1.5 mol/L.
The concentration of described lithium salts A in electrolyte is 0.7-1.2 mol/L, and the concentration of described lithium salts B in electrolyte is 0.05-0.5 mol/L, and the total concentration of described mixing lithium salts in electrolyte is 0.7-1.5 mol/L.
Described aprotic solvent is ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, propylene carbonate, Ethyl formate, methyl acetate, ethyl acetate, ethylene sulfite, propylene sulfite, dimethyl sulfite, sulfurous acid diethyl ester, methyl-sulfoxide, dimethyl sulfone, sulfolane, second methyl sulfoxide, 3, the mixture of one or several in 3,3-trifluoro propyl methyl sulfone, acetonitrile, gamma-butyrolacton.
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Prepare respectively novel electrolyte involved in the present invention, traditional electrolyte, and utilize their assembling test half-cells.Under identical condition, the high rate performance of battery, high-temperature behavior and cycle performance are contrasted.Comparing result is in Table 1~2.From test result, under electrode material and the identical condition of test condition, with novel electrolyte involved in the present invention, substitute traditional electrolyte, can obviously improve high rate performance, high-temperature behavior and the cycle performance of lithium ion battery.Concrete case study on implementation is as follows:
the assembling of test half-cell
embodiment 1:
(1) preparation of electrolyte:
Under room temperature, in being full of the glove box of argon gas, ethylene carbonate (EC), dimethyl carbonate (DMC), by volume for the ratio of 1:2 mixes, and are added to the LiBF of respective quality 2sO 4, mix, be mixed with the LiBF that amount of substance concentration is 1.0 mol/L 2sO 4electrolyte;
(2) preparation of anode pole piece:
First by LiFePO 4, acetylene black and polyvinylidene fluoride (PVDF) be fully uniformly mixed with the mass ratio of 84:8:8, then the mixture obtaining evenly mixed according to the mass ratio of 1.5:1 with 1-METHYLPYRROLIDONE (NMP), makes anode sizing agent.Adopt coating machine that gained anode sizing agent is coated in aluminum foil current collector equably, with 120 ℃ at dry, after cutting, rolling, obtain anode pole piece;
(3) assembling of battery:
Above-mentioned anode pole piece, metal lithium sheet and polypropylene diaphragm are assembled into button lithium ion battery, and in glove box, (in ar gas environment) injects electrolyte, and then sealing, compressing tablet, make 2032 type lithium ion test half-cell (LiFePO 4/ Li half-cell).
embodiment 2:
Adopt the mode identical with embodiment 1 to prepare 2032 type LiFePO 4/ Li tests half-cell.Aprotic organic solvent in electrolyte is the mixture that propene carbonate (PC) and DMC form according to volume ratio 1:1, and electrolyte lithium salt is LiBF 2sO 4(amount of substance concentration is 0.7 mol/L).
embodiment 3:
Adopt the mode identical with embodiment 1 to prepare 2032 type LiFePO 4/ Li tests half-cell.Aprotic organic solvent in electrolyte is the mixture that EC and DMC form according to volume ratio 3:7, and electrolyte lithium salt is LiBF 2sO 4(amount of substance concentration is 1.0 mol/L).
embodiment 4:
Adopt the mode identical with embodiment 1 to prepare 2032 type LiMn 2o 4/ Li tests half-cell.Aprotic organic solvent in electrolyte is the mixture that EC, PC, DMC form according to volume ratio 1:1:1, and electrolyte lithium salt is LiBF 2sO 4(amount of substance concentration is 1.2 mol/L).
embodiment 5:
Adopt the mode identical with embodiment 1 to prepare 2032 type LiFePO 4/ Li tests half-cell.Aprotic organic solvent in electrolyte is the mixture that EC and DMC form according to volume ratio 1:1, and electrolyte lithium salt is 1.0 mol/L LiBF 2sO 4the mixture that forms of the LiBOB with 0.1 mol/L.
embodiment 6:
Adopt the mode identical with embodiment 1 to prepare 2032 type LiFePO 4/ Li tests half-cell.Aprotic organic solvent in electrolyte is the mixture that EC and DMC form according to volume ratio 1:1, and electrolyte lithium salt is the LiBF of 0.15 mol/L 2sO 4the mixture forming with the LiBOB of 0.8 mol/L.
embodiment 7:
Adopt the mode identical with embodiment 1 to prepare 2032 type LiFePO 4/ Li tests half-cell.Aprotic organic solvent in electrolyte is the mixture that EC and DMC form according to volume ratio 1:1, and electrolyte lithium salt is the LiBF of 0.8 mol/L 2sO 4the mixture forming with the LiODFB of 0.3 mol/L.
embodiment 8:
Adopt the mode identical with embodiment 1 to prepare 2032 type LiCoO 2/ Li tests half-cell.Aprotic organic solvent in electrolyte is the mixture that EC and diethyl carbonate (DEC) form according to volume ratio 1:1, and electrolyte lithium salt is the LiBF of 0.5 mol/L 2sO 4liPF with 0.5 mol/L 6the mixture forming.
embodiment 9:
Adopt the mode identical with embodiment 1 to prepare 2032 type LiFePO 4/ Li tests half-cell.Aprotic organic solvent in electrolyte is the mixture that sulfolane (SL) and DEC form according to volume ratio 1:1, and electrolyte lithium salt is the LiBF of 0.3 mol/L 2sO 4liBF with 0.8 mol/L 4the mixture forming.
embodiment 10:
Adopt the mode identical with embodiment 1 to prepare 2032 type LiMn 2o 4/ Li tests half-cell.Aprotic organic solvent in electrolyte is the mixture that SL, dimethyl sulfite (DMS), methyl ethyl carbonate (EMC) form according to volume ratio 1:1:2, and electrolyte lithium salt is the LiBF of 0.6 mol/L 2sO 4, the LiBOB of 0.2 mol/L is, the LiPF of 0.2 mol/L 6three's mixture.
embodiment 11:
Adopt the mode identical with embodiment 1 to prepare 2032 type LiFePO 4/ Li tests half-cell.Aprotic organic solvent in electrolyte is the mixture that sulfolane (SL), gamma-butyrolacton (GBL), DEC form according to volume ratio 1:1:1, and electrolyte lithium salt is the LiBF of 0.3 mol/L 2sO 4the mixture forming with the LiBOB of 0.8 mol/L.
embodiment 12:
Adopt the mode identical with embodiment 1 to prepare 2032 type LiFePO 4/ Li tests half-cell.Aprotic organic solvent in electrolyte is the mixture that SL, GBL, DMS form according to volume ratio 1:1:1, and electrolyte lithium salt is the LiBF of 1.0 mol/L 2sO 4li (CF with 0.15 mol/L 3sO 2) 2the mixture that N forms.
comparative example 1-3:
Adopt the mode identical with embodiment 1, prepare respectively 2032 type LiFePO 4/ Li(comparative example 1), LiMn 2o 4/ Li(comparative example 2), LiCoO 2/ Li(comparative example 3) test half-cell.Aprotic organic solvent in electrolyte is the mixture that EC and DMC form according to volume ratio 1:1, and electrolyte lithium salt is LiPF 6(amount of substance concentration is 1.0 mol/L).
battery performance test
1, room temperature and high temperature cyclic performance
Room temperature (approximately 25 oc) and under high temperature (60 ℃), the battery to embodiment 1-12 and comparative example 1-3 with the charge-discharge magnification of 0.5 C, carries out 100 circulations respectively.Discharge capacitance after 100 circulations=(discharge capacity of discharge capacity/first of the 100th circulation) * 100%.At room temperature and 60 ℃, the test result of the discharge capacitance after 100 circulations is in Table 1.
2, the test of the discharge capacitance under different multiplying
Room temperature (approximately 25 oc), under condition, the charge-discharge magnification with 0.2 C, 1 C, 3 C discharges and recharges the battery of embodiment 1-12 and comparative example 1-3 respectively.Capability retention=(discharge capacity of discharge capacity/0.2 C of 3 C) * 100% under capability retention under 1 C=(discharge capacity of discharge capacity/0.2 C of 1 C) * 100%, 3 C.The capability retention discharging under different multiplying is in Table 2.
 
Discharge capacitance after table 1.100 time circulation
Figure 495842DEST_PATH_IMAGE001
The capability retention of battery under table 2. different multiplying
Figure 337896DEST_PATH_IMAGE002

Claims (4)

1. with LiBF 2sO 4for the lithium-ion battery electrolytes of basic lithium salts, this electrolyte contains electrolyte lithium salt and aprotic solvent, it is characterized in that: described electrolyte lithium salt can be lithium salts A, can be also the mixture of lithium salts A and lithium salts B; Wherein lithium salts A is LiBF 2sO 4, lithium salts B is one or more the mixture in lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, lithium trifluoromethanesulp,onylimide, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium.
According to described in claims 1 with LiBF 2sO 4lithium-ion battery electrolytes for basic lithium salts, it is characterized in that: the concentration of described lithium salts A in electrolyte is 0.15-1.2 mol/L, the concentration of described lithium salts B in electrolyte is 0-0.8 mol/L, and the total concentration of described mixing lithium salts in electrolyte is 0.15-1.5 mol/L.
According to described in claims 2 with LiBF 2sO 4lithium-ion battery electrolytes for basic lithium salts, it is characterized in that: the concentration of described lithium salts A in electrolyte is 0.7-1.2 mol/L, the concentration of described lithium salts B in electrolyte is 0.05-0.5 mol/L, and the total concentration of described mixing lithium salts in electrolyte is 0.7-1.5 mol/L.
According to described in claims 1 with LiBF 2sO 4lithium-ion battery electrolytes for basic lithium salts, it is characterized in that: described aprotic solvent is ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, propylene carbonate, Ethyl formate, methyl acetate, ethyl acetate, ethylene sulfite, propylene sulfite, dimethyl sulfite, sulfurous acid diethyl ester, methyl-sulfoxide, dimethyl sulfone, sulfolane, second methyl sulfoxide, 3, the mixture of one or several in 3,3-trifluoro propyl methyl sulfone, acetonitrile, gamma-butyrolacton.
CN201310507642.6A 2013-10-24 2013-10-24 Lithium-ion battery electrolyte taking LiBF2SO4 as basic lithium salt Pending CN103531845A (en)

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CN107004905A (en) * 2014-12-16 2017-08-01 索尼公司 Secondary cell electrolyte, secondary cell, battery pack, electric vehicle, accumulating system, electric tool and electronic installation
KR20190005389A (en) * 2017-07-06 2019-01-16 임광민 New lithium phosphate derivatives and New lithium borate derivatives, the method of preparing the same and electrolyte solution and lithium secondary battery containing the same
CN110247118A (en) * 2019-07-11 2019-09-17 兰州理工大学 A kind of superelevation warm type lithium-ion battery electrolytes for taking into account cryogenic property
CN112086685A (en) * 2020-10-26 2020-12-15 长兴中俄新能源材料技术研究院 Three-lithium salt-quaternary solvent system performance complementary type 5V lithium ion battery electrolyte
CN112670568A (en) * 2020-12-23 2021-04-16 远景动力技术(江苏)有限公司 Non-aqueous electrolyte and lithium ion battery with low impedance and low gas production performance
CN112713309A (en) * 2021-01-11 2021-04-27 天津市捷威动力工业有限公司 Safety lithium ion battery electrolyte and lithium ion battery thereof
CN114520372A (en) * 2022-02-21 2022-05-20 蜂巢能源科技股份有限公司 Oxidation-resistant electrolyte, lithium ion battery and preparation method

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CN107004905A (en) * 2014-12-16 2017-08-01 索尼公司 Secondary cell electrolyte, secondary cell, battery pack, electric vehicle, accumulating system, electric tool and electronic installation
US10326167B2 (en) 2014-12-16 2019-06-18 Murata Manufacturing Inc. Secondary battery-use electrolytic solution, secondary battery, battery pack, electric vehicle, electric power storage system, electric power tool, and electronic apparatus
CN107004905B (en) * 2014-12-16 2019-12-06 株式会社村田制作所 Electrolyte for secondary battery, battery pack, electric vehicle, power storage system, electric power tool, and electronic device
US10665903B2 (en) * 2015-02-13 2020-05-26 Murata Manufacturing Co., Ltd. Secondary battery, battery pack, electric vehicle, electric power storage system, electric power tool, and electronic apparatus
CN107210488A (en) * 2015-02-13 2017-09-26 索尼公司 Secondary cell, battery pack, electric vehicle, power storage system, electric tool and electronic equipment
US20170365884A1 (en) * 2015-02-13 2017-12-21 Sony Corporation Secondary battery, battery pack, electric vehicle, electric power storage system, electric power tool, and electronic apparatus
WO2016129384A1 (en) * 2015-02-13 2016-08-18 ソニー株式会社 Secondary battery, battery pack, electric vehicle, power storage system, electric tool, and electronic apparatus
CN107210488B (en) * 2015-02-13 2020-07-17 株式会社村田制作所 Secondary battery, battery pack, electric vehicle, electric power storage system, electric power tool, and electronic device
KR20190005389A (en) * 2017-07-06 2019-01-16 임광민 New lithium phosphate derivatives and New lithium borate derivatives, the method of preparing the same and electrolyte solution and lithium secondary battery containing the same
KR102272371B1 (en) 2017-07-06 2021-07-02 임광민 New lithium phosphate derivatives and New lithium borate derivatives, the method of preparing the same and electrolyte solution and lithium secondary battery containing the same
CN110247118A (en) * 2019-07-11 2019-09-17 兰州理工大学 A kind of superelevation warm type lithium-ion battery electrolytes for taking into account cryogenic property
CN112086685A (en) * 2020-10-26 2020-12-15 长兴中俄新能源材料技术研究院 Three-lithium salt-quaternary solvent system performance complementary type 5V lithium ion battery electrolyte
CN112086685B (en) * 2020-10-26 2024-03-08 长兴中俄新能源材料技术研究院 Trilithium salt-quaternary solvent system performance complementary type 5V lithium ion battery electrolyte
CN112670568A (en) * 2020-12-23 2021-04-16 远景动力技术(江苏)有限公司 Non-aqueous electrolyte and lithium ion battery with low impedance and low gas production performance
CN112713309A (en) * 2021-01-11 2021-04-27 天津市捷威动力工业有限公司 Safety lithium ion battery electrolyte and lithium ion battery thereof
CN114520372A (en) * 2022-02-21 2022-05-20 蜂巢能源科技股份有限公司 Oxidation-resistant electrolyte, lithium ion battery and preparation method
CN114520372B (en) * 2022-02-21 2024-01-26 蜂巢能源科技股份有限公司 Oxidation-resistant electrolyte, lithium ion battery and preparation method

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Application publication date: 20140122