CN103762384A - Safe non-aqueous electrolyte for battery - Google Patents

Safe non-aqueous electrolyte for battery Download PDF

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Publication number
CN103762384A
CN103762384A CN201410035305.6A CN201410035305A CN103762384A CN 103762384 A CN103762384 A CN 103762384A CN 201410035305 A CN201410035305 A CN 201410035305A CN 103762384 A CN103762384 A CN 103762384A
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electrolyte
battery
carbonate
safety
electrolytic solution
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CN103762384B (en
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卞锋菊
张忠如
刘新平
杨勇
祖利洲
闫春凤
黄当睦
吴茂祥
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Fujian Shaowu Chuangxin New Material Co.,Ltd.
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FUJIAN CHUANGXIN SCIENCE AND TECHNOLOGY DEVELOPMENT Co Ltd
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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
    • H01M10/0569Liquid 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

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses safe non-aqueous electrolyte for a battery. The electrolyte comprises a lithium salt, an organic solvent and an additive, wherein the organic solvent comprises a cyclic compound and chain carbonate; the cyclic compound comprises propylene carbonate and a cyclic phosphonitrile compound. The electrolyte takes a flame-retardant compound as a solvent, has high safety performance, low-temperature performance and high-temperature cycle performance and is safe electrolyte which can be used in a wide temperature range. Meanwhile, due to a matched synergistic effect of the solvent and the additive, the battery has high electrochemical performance, the capacity of a lithium ion battery using the electrolyte can be fully exerted, and the battery has excellent safety performance, high-temperature resistance, low-temperature performance and long cycle life.

Description

A kind of battery safety-type nonaqueous electrolytic solution
Technical field
The present invention relates to the electrolyte technical field of battery, be specifically related to a kind of battery safety-type nonaqueous electrolytic solution.
Background technology
Lithium ion battery, with advantages such as its high-energy-density, high voltage, memory-less effect, environmental protection and life-span length, has been widely used in portable type electronic product as the reliable energy, as the power supply of mobile phone, notebook computer and Miniature Power Unit driving arrangement.But in recent years, all there are a lot of cell safety accidents in each state, this is mainly that particularly, in large capacity power source application aspect such as electric motor cars, safety problem is even more important because battery causes the safety issue that thermal runaway causes under abuse (thermal shock, overcharge, short circuit etc.) state.At present, the electrolyte of lithium ion battery is mostly liquid organic electrolyte, organic solvent and electric conducting lithium salt, consists of.Conventional organic solvent is alkyl carbonate compounds, as ethylene carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) etc.Because the flash-point of these organic solvents is all very low, the electrolyte solution (electrolyte) of lithium ion battery is very easily burnt.When the safety problems such as battery is short-circuited, overcharges, battery abnormal heating, gasification or decomposition produce a large amount of gas and cause cell fracture on fire.Although battery is furnished with protective circuit, safety valve and semistor (PTC) etc., can not avoid these organic solvents to occur the situation of leaking, burning is even exploded completely.The research discovery of at present relevant electrolyte combustibility, though alkyl phosphate has certain flame retardant effect, but severe exacerbation battery performance; And nitrogen-containing compound is little on battery performance impact, but their flame retarding efficiency is not high, and toxicity is larger.In addition, along with the development of the key areas such as electric motor car, space technology, the serviceability temperature scope of lithium ion battery also becomes one of Important Problems of battery researcher concern.Ethylene carbonate (EC) is current the most frequently used cyclic carbonate ester solvent.But the solidifying point of ethylene carbonate high (39 ℃), is solid-state under normal temperature, under low temperature, electrolyte solidifies, and conductivity reduces, and greatly affects the cryogenic property of battery.
As mentioned above, improve the fail safe of battery, giving electrolyte noninflammability is important with the serviceability temperature scope of widening electrolyte.
For the problems referred to above, phosphazene compound is added in nonaqueous electrolytic solution, give nonaqueous electrolytic solution from putting out characteristic, significantly reduce battery short circuit, cell fracture danger on fire while overcharging.The solidifying point of phosphazene compound, below-5 ℃, can be improved the cryogenic property of battery.Simultaneously preferably propene carbonate (PC), as one of solvent composition of electrolyte, further improves the cryogenic property of battery.
Summary of the invention
The object of the present invention is to provide the safety-type electrolysis liquid that a kind of serviceability temperature scope is wide, short circuit, the hazard of catch fire that breaks while overcharging are little, and high temperature cyclic performance is good, and low temperature performance is good, has the nonaqueous electrolytic solution of good battery performance.
For achieving the above object, the present invention adopts following technical scheme:
A battery safety-type nonaqueous electrolytic solution, described electrolyte contains lithium salts, organic solvent and additive; Described organic solvent comprises cyclic compound and linear carbonate, and described cyclic compound comprises propene carbonate and cyclic phosphazene compound; The structural formula of described cyclic phosphazene compound is:
Figure 2014100353056100002DEST_PATH_IMAGE001
, wherein, R 1~ R 6in optional two groups be a kind of in fluorine, alkyl, alkoxyl, aryl, aryloxy group, all the other four groups are fluorine.
Described propene carbonate consumption accounts for 10% ~ 70% of organic solvent gross mass in electrolyte.
Described cyclic phosphazene compound consumption accounts for 5% ~ 50% of organic solvent gross mass in electrolyte.
Described lithium salts is selected from one or more in lithium hexafluoro phosphate, LiBF4, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium; The mass concentration of described lithium salts in electrolyte is 0.8~1.3 molL -1.
Described lithium salts is lithium hexafluoro phosphate.
Described linear carbonate solvent is selected from one or more in dimethyl carbonate, diethyl carbonate, Methylethyl carbonic ester, methyl-propyl carbonic ester, butylene.
Described additive is selected from one or more in vinylene carbonate, fluorinated ethylene carbonate, vinyl vinylene carbonate, ethylene sulfite, vinyl ethylene sulfite, propylene sulfite, dimethyl suflfate, sulfuric acid propylene; Described additive amount is 0.5~10% of electrolyte gross mass.
The mass ratio that described organic solvent consists of cyclic compound and linear carbonate is 30:70~75:25.
Beneficial effect of the present invention is:
In electrolyte, use phosphonitrile analog derivative as one of electrolyte organic solvent component, because phosphonitrile analog derivative has flame retardant effect, can solve the safety problem of battery under abuse state (overcharge, short circuit etc.); Use propene carbonate as electrolyte organic solvent component simultaneously, because the fusing point of propene carbonate is lower, improved the cryogenic property of battery; Use film for additive to form SEI film in the surface of active material of battery, suppress electrolyte in the decomposition of surface of active material, improve the stability of battery.The cooperation of solvent and additive synergy, makes battery have good chemical property simultaneously, uses the lithium ion battery of electrolyte of the present invention can give full play to capacity, has excellent security performance, high-temperature behavior, cryogenic property and cycle life.
Embodiment
The present invention further illustrates the present invention with the following example, but protection scope of the present invention is not limited to the following example.
In specific embodiments of the invention, affiliated linear carbonate is selected from and well known to a person skilled in the art organic solvent, and in order to facilitate elaboration of the present invention, linear carbonate is selected diethyl carbonate (DEC).
Embodiment 1
Electrolyte is composed as follows: lithium salts LiPF 6mass concentration 1.0molL -1, the cyclic phosphazene compound that organic solvent propene carbonate, structural formula (I) represent (R wherein 1~ R 5for fluorine, R 6for ethyoxyl) and diethyl carbonate (mass ratio 20:20:60), additive vinyl ethylene sulfite (VES) accounts for 3% of electrolyte gross mass, and additive VC accounts for 2% of electrolyte gross mass.
The electrolyte preparing, according to conventional cell making process, is injected just very cobalt acid lithium, in the negative pole flexible-packed battery that is graphite.Battery design capacity is 1000mAh.Battery changes into according to following flow process: 0.02C constant current charge is to 2.8V, and 0.05C constant current charge extremely 3.3v, 0.1C constant current charge extremely 4.2v, 4.2v constant voltage charge, cut-off current 0.033c.Battery vacuum-pumping after changing into seals again, according to following flow process, carries out partial volume: 0.2C constant-current discharge extremely 2.5v, 0.2C constant current charge extremely 4.2v, 4.2v constant voltage charge, cut-off current 0.05c, charge and discharge cycles 2 times.
(1) electrolyte flame-retardant is evaluated
According to the UL94 horizontal firing method of UL standard, measure burning length and the burning time of the flame of lighting in atmospheric environment, and evaluate.Particularly, based on UL94HB experimental standard, the long glass fibre of 13cm is soaked in the electrolyte of configuration at least 24h, then take out and be placed in combustion test instrument, with gas lamp, it is executed to flame 15s, then remove gas lamp, record the residual flame time, be self-extinguishing time.
(2) over-charging of battery evaluation
willdetect battery core and shelve 24h.Connect constant current constant voltage source and set output voltage 10V, output current 0.5C charging 5.5 hours, battery should not explode, not on fire.
(3) battery short circuit evaluation
Battery core full charging, to 4.2V, is shelved to 24h.By circuit all-in resistance, be not more than the short-circuiting device of 50m Ω, short circuit battery core both positive and negative polarity, finishes test when battery temperature drops to than low approximately 10 ℃ of peak value.In process of the test battery should be not on fire, do not explode, the external temperature of battery must not be higher than 150 ℃.
(4) battery low temperature performance is evaluated
Battery in room temperature with 0.5C multiplying power constant-current constant-voltage charging, cut-ff voltage 4.2v.Battery is shelved in cryogenic box, and controlling temperature is-30 ℃, shelves time 120min.With 0.2C multiplying power discharging to voltage 2.5v cut-off.Record charge/discharge capacity.
(5) 50 ℃ of cycle performance evaluations of battery
Battery is shelved in insulating box, and controlling temperature is 50 ℃, shelves time 120min.With 1C multiplying power constant-current constant-voltage charging, cut-ff voltage 4.2v; Again with 1C multiplying power discharging to voltage 2.75v cut-off.Circulate 300 times.Record charge/discharge capacity.
The test result of electrolyte and battery is in Table 1.
Embodiment 2
Electrolyte is composed as follows: lithium salts LiPF 6concentration 1.0 molL -1, the cyclic phosphazene compound that organic solvent propene carbonate, general formula (I) represent (R wherein 1~ R 5for fluorine, R 6for methoxyl group) and diethyl carbonate (mass ratio 25:5:70), the quality percentage composition that additive vinyl ethylene sulfite (VES) accounts for electrolyte total amount is 3%, the quality percentage composition that additive VC accounts for electrolyte total amount is 2%.
Embodiment 3
Electrolyte is composed as follows: lithium salts LiPF 6concentration 0.8molL -1, the cyclic phosphazene compound that organic solvent propene carbonate, general formula (I) represent (R wherein 1~ R 6for fluorine) and diethyl carbonate (mass ratio 20:10:70), the quality percentage composition that additive vinyl ethylene sulfite (VES) accounts for electrolyte total amount is 3%, the quality percentage composition that additive VC accounts for electrolyte total amount is 2%.
Embodiment 4
Electrolyte is composed as follows: lithium salts LiPF 6concentration 1.3molL -1, the cyclic phosphazene compound that organic solvent propene carbonate, general formula (I) represent (R wherein 1~ R 5for fluorine, R 6for trifluoro ethoxy) and diethyl carbonate (mass ratio 45:15:40), the quality percentage composition that additive vinyl ethylene sulfite (VES) accounts for electrolyte total amount is 3%, the quality percentage composition that additive VC accounts for electrolyte total amount is 2%.
Embodiment 5
Electrolyte is composed as follows: lithium salts LiPF 6concentration 1.0molL -1, the cyclic phosphazene compound that organic solvent propene carbonate, general formula (I) represent (R wherein 1~ R 5for fluorine, R 6for ethyoxyl) and diethyl carbonate (mass ratio 70:5:25), the quality percentage composition that additive vinyl ethylene sulfite (VES) accounts for electrolyte total amount is 3%, the quality percentage composition that additive VC accounts for electrolyte total amount is 2%.
Embodiment 6
Electrolyte is composed as follows: lithium salts LiPF 6concentration 1.0molL -1, the cyclic phosphazene compound that organic solvent propene carbonate, general formula (I) represent (R wherein 1~ R 5for fluorine, R 6for ethyoxyl) and diethyl carbonate (mass ratio 10:50:40), the quality percentage composition that additive vinyl ethylene sulfite (VES) accounts for electrolyte total amount is 3%, the quality percentage composition that additive VC accounts for electrolyte total amount is 2%.
Embodiment 7
As a comparison, the present embodiment does not add cyclic phosphazene compound, and electrolyte is composed as follows: lithium salts LiPF 6concentration 1.0molL -1, organic solvent propene carbonate and diethyl carbonate (mass ratio 30:70), the quality percentage composition that additive vinyl ethylene sulfite (VES) accounts for electrolyte total amount is 3%, the quality percentage composition that additive VC accounts for electrolyte total amount is 2%.
Embodiment 8
As a comparison, the present embodiment does not add propene carbonate, and electrolyte is composed as follows: lithium salts LiPF 6concentration 1.0molL -1, the cyclic phosphazene compound that general formula (I) represents (R wherein 1~ R 5for fluorine, R 6for ethyoxyl) and diethyl carbonate (mass ratio 30:70), the quality percentage composition that additive vinyl ethylene sulfite (VES) accounts for electrolyte total amount is 3%, the quality percentage composition that additive VC accounts for electrolyte total amount is 2%.
Table 1 electrolyte and battery performance evaluation
Figure 306942DEST_PATH_IMAGE002
According to the data in table 1, the electrolyte of embodiment 7 is long burning time, does not possess fire resistance, phosphonitrile analog derivative add the anti-flammability that can significantly improve electrolyte.Meanwhile, the over-charging of battery short circuit of being made by the electrolyte of embodiment 7 does not all pass a test, and phosphazene derivative can significantly improve the security performance of battery.The battery of being made by the electrolyte of embodiment 8, low temperature discharge capacity is lower, and the cryogenic property that can improve electrolyte that adds of PC is described.By the relatively discovery of embodiment 1 ~ 6 and embodiment 7, phosphonitrile analog derivative is improved the high temperature circulation of battery.The electrolyte of the present invention's design has good security performance, cryogenic property and high temperature cyclic performance, is a kind of safety-type electrolysis liquid that can use in wide temperature range.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.

Claims (8)

1. a battery safety-type nonaqueous electrolytic solution, is characterized in that: described electrolyte contains lithium salts, organic solvent and additive; Described organic solvent comprises cyclic compound and linear carbonate, and described cyclic compound comprises propene carbonate and cyclic phosphazene compound; The structural formula of described cyclic phosphazene compound is:
Figure 434667DEST_PATH_IMAGE001
, wherein, R 1~ R 6in optional two groups be a kind of in fluorine, alkyl, alkoxyl, aryl, aryloxy group, all the other four groups are fluorine.
2. battery according to claim 1 safety-type nonaqueous electrolytic solution, is characterized in that: described propene carbonate consumption accounts for 10% ~ 70% of organic solvent gross mass in electrolyte.
3. battery according to claim 1 safety-type nonaqueous electrolytic solution, is characterized in that: described cyclic phosphazene compound consumption accounts for 5% ~ 50% of organic solvent gross mass in electrolyte.
4. battery according to claim 1 safety-type nonaqueous electrolytic solution, is characterized in that: described lithium salts is selected from one or more in lithium hexafluoro phosphate, LiBF4, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium; The mass concentration of described lithium salts in electrolyte is 0.8~1.3 molL -1.
5. battery according to claim 4 safety-type nonaqueous electrolytic solution, is characterized in that: described lithium salts is lithium hexafluoro phosphate.
6. battery according to claim 1 safety-type nonaqueous electrolytic solution, is characterized in that: described linear carbonate solvent is selected from one or more in dimethyl carbonate, diethyl carbonate, Methylethyl carbonic ester, methyl-propyl carbonic ester, butylene.
7. battery according to claim 1 safety-type nonaqueous electrolytic solution, is characterized in that: described additive is selected from one or more in vinylene carbonate, fluorinated ethylene carbonate, vinyl vinylene carbonate, ethylene sulfite, vinyl ethylene sulfite, propylene sulfite, dimethyl suflfate, sulfuric acid propylene; Described additive amount is 0.5~10% of electrolyte gross mass.
8. battery according to claim 1 safety-type nonaqueous electrolytic solution, is characterized in that: the mass ratio that described organic solvent consists of cyclic compound and linear carbonate is 30:70~75:25.
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Cited By (11)

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CN104218258A (en) * 2014-09-17 2014-12-17 宜春金晖新能源材料有限公司 Over-charging prevention flame-retardant battery electrolyte
CN104900879A (en) * 2015-06-01 2015-09-09 山东大学 Flame retardant sodium-ion battery electrolytic solution and application thereof
CN105789683A (en) * 2016-03-22 2016-07-20 山东大学 Non-combustible lithium-sulfur or sodium-sulfur cell electrolyte solution and preparation method therefor
CN106207263A (en) * 2015-05-25 2016-12-07 松下知识产权经营株式会社 Electrolyte and battery
CN106450454A (en) * 2016-10-19 2017-02-22 中航锂电(洛阳)有限公司 Electrolyte and lithium ion battery using electrolyte
CN106935909A (en) * 2017-05-08 2017-07-07 山东大学 A kind of flame retardant type kalium ion battery electrolyte and preparation method thereof
CN107305963A (en) * 2016-04-25 2017-10-31 上海交通大学 Electrolyte for lithium-sulfur cell and preparation method thereof
WO2018214313A1 (en) * 2017-05-26 2018-11-29 宁德时代新能源科技股份有限公司 Lithium ion battery and electrolyte thereof
CN111082146A (en) * 2020-01-21 2020-04-28 大同新成新材料股份有限公司 Electrolyte taking propylene carbonate as main solvent
CN111433965A (en) * 2018-07-04 2020-07-17 株式会社Lg化学 Electrolyte for lithium secondary battery and lithium secondary battery comprising the same
CN111943219A (en) * 2020-08-24 2020-11-17 厦门大学 Inorganic salt and preparation method thereof, lithium ion battery electrolyte additive, lithium ion battery electrolyte and lithium ion battery

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Publication number Priority date Publication date Assignee Title
CN104218258A (en) * 2014-09-17 2014-12-17 宜春金晖新能源材料有限公司 Over-charging prevention flame-retardant battery electrolyte
CN106207263A (en) * 2015-05-25 2016-12-07 松下知识产权经营株式会社 Electrolyte and battery
CN104900879A (en) * 2015-06-01 2015-09-09 山东大学 Flame retardant sodium-ion battery electrolytic solution and application thereof
CN104900879B (en) * 2015-06-01 2018-02-23 山东大学 A kind of flame retardant type sodium-ion battery electrolyte and its application
CN105789683A (en) * 2016-03-22 2016-07-20 山东大学 Non-combustible lithium-sulfur or sodium-sulfur cell electrolyte solution and preparation method therefor
CN107305963A (en) * 2016-04-25 2017-10-31 上海交通大学 Electrolyte for lithium-sulfur cell and preparation method thereof
CN106450454A (en) * 2016-10-19 2017-02-22 中航锂电(洛阳)有限公司 Electrolyte and lithium ion battery using electrolyte
CN106935909A (en) * 2017-05-08 2017-07-07 山东大学 A kind of flame retardant type kalium ion battery electrolyte and preparation method thereof
WO2018214313A1 (en) * 2017-05-26 2018-11-29 宁德时代新能源科技股份有限公司 Lithium ion battery and electrolyte thereof
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CN111433965A (en) * 2018-07-04 2020-07-17 株式会社Lg化学 Electrolyte for lithium secondary battery and lithium secondary battery comprising the same
CN111433965B (en) * 2018-07-04 2023-08-08 株式会社Lg新能源 Electrolyte for lithium secondary battery and lithium secondary battery comprising same
CN111082146A (en) * 2020-01-21 2020-04-28 大同新成新材料股份有限公司 Electrolyte taking propylene carbonate as main solvent
CN111943219A (en) * 2020-08-24 2020-11-17 厦门大学 Inorganic salt and preparation method thereof, lithium ion battery electrolyte additive, lithium ion battery electrolyte and lithium ion battery
CN111943219B (en) * 2020-08-24 2021-11-16 厦门大学 Inorganic salt and preparation method thereof, lithium ion battery electrolyte additive, lithium ion battery electrolyte and lithium ion battery

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