CN102403534A - High-temperature lithium-ion battery electrolyte and preparation method - Google Patents
High-temperature lithium-ion battery electrolyte and preparation method Download PDFInfo
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- CN102403534A CN102403534A CN2011103933914A CN201110393391A CN102403534A CN 102403534 A CN102403534 A CN 102403534A CN 2011103933914 A CN2011103933914 A CN 2011103933914A CN 201110393391 A CN201110393391 A CN 201110393391A CN 102403534 A CN102403534 A CN 102403534A
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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
- 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
Abstract
The invention relates to high-temperature lithium-ion battery electrolyte and a preparation method. The high-temperature lithium-ion battery electrolyte is characterized by comprising electrolyte, an organic solvent and additives. The preparation method comprises the following steps: refining and purifying the organic solvent with the weight being 70-88 percent in a closed environment with the water content less than or equal to 10ppm, adding the electrolyte of 7.5-22.5 percent, mixing uniformly, adding the additives with the weight being 4-10 percent, and mixing for 30 minutes to obtain the high-temperature lithium-ion battery electrolyte. The invention has the advantages and effects that the electrolyte has excellent high-temperature performance and good cycle performance and can be stored for 7 days at 60 DEG C, no flatulence can be caused, and the capacity retention rate is more than or equal to 90 percent, the electrolyte can be stored for 4h in environments of 85 DEG C, the thickness variation is less than or equal to 5 percent, the capacity retention rate is more than or equal to 85 percent, the cycle capacity retention rate is more than or equal to 85 percent within 300 weeks.
Description
Technical field
The present invention relates to a kind of electrolyte of lithium ion battery, particularly a kind of electrolyte of high temperature lithium ion battery belongs to the battery material field.
The invention still further relates to the preparation method of this electrolyte.
Background technology
Lithium ion battery after commercial applications; But it is high with voltage, specific energy big, have extended cycle life, security performance is good, the advantage of the little fast charging and discharging of self discharge and developing rapidly; At present; Lithium ion battery has been widely used in mobile phone, notebook computer, digital camera electronic product; Also be applied on electric tool, electric bicycle and the electric automobile as motive-power battery, in order to make the lithium ion battery better application in life is produced, people more and more pay close attention to the basic research and the application study of lithium ion battery.
Lithium-ion battery electrolytes is as the important component part of lithium ion battery; Various performance important influence to lithium ion battery; At present; The lithium ion battery that with the LiMn2O4 is positive electrode is an important directions of power-type lithium ion battery, and LiMn2O4 exists capacity attenuation very fast when high temperature, is prone to the shortcoming of flatulence.
Summary of the invention
The object of the invention provides a kind of electrolyte of high temperature lithium ion battery just with deficiency for the shortcoming that overcomes above-mentioned prior art existence; Can effectively improve the high-temperature behavior and the excellent cycle performance of lithium ion battery, thereby quality assurance is provided for the use of lithium ion battery.
The present invention also provides the preparation method of this electrolyte.
The objective of the invention is to realize through following technical proposal:
A kind of high temperature lithium-ion battery electrolytes, it is made up of following weight percentages:
Electrolyte 7.5%～22.5%, organic solvent 70%～88% and additive 4%～10%,
Said electrolyte is the combination of one or both or three kinds in lithium hexafluoro phosphate, biethyl diacid lithium borate or two (trifluoromethyl sulphonyl) the imines lithium;
Said organic solvent is one or both or the two or more combination in ethylene carbonate and gamma-butyrolacton, methyl ethyl carbonate, diethyl carbonate or the propene carbonate; The percentage by weight of all kinds of solvents is: ethylene carbonate is 20%～50%, one or both in gamma-butyrolacton, methyl ethyl carbonate, diethyl carbonate or the propene carbonate or two or morely be combined as 50～80%;
Said additive is made up of LiBF4, tricresyl phosphate methyl silicon and vinylene carbonate, and its percentage by weight is: tetrafluoro lithium phosphate 15%～25%, tricresyl phosphate methyl silicon 10%～20% and vinylene carbonate 60%～75%.
The preparation method of described high temperature lithium-ion battery electrolytes, it is undertaken by following step:
Under the enclosed environment condition of moisture≤10ppm; The organic solvent of 70%～88% weight (down together) is made with extra care purification, add 7.5%～22.5% electrolyte, stir; The additive that adds 4%～10% weight again stirs and obtained the high temperature lithium-ion battery electrolytes in 30 minutes.
The electrolyte that the present invention selects for use is lithium hexafluoro phosphate, molecular formula LiPF
6, biethyl diacid lithium borate, molecular formula LiBOB or two (trifluoromethyl sulphonyl) imines lithium, molecular formula LiN (CF
3SO
2)
2
The ethylene carbonate that the present invention selects for use, english abbreviation EC, gamma-butyrolacton, english abbreviation GBL, propene carbonate; English abbreviation PC, methyl ethyl carbonate, english abbreviation EMC, diethyl carbonate, english abbreviation DEC; Be high boiling organic solvent; Can improve the whole boiling point of lithium-ion battery electrolytes, thereby improve the stability of lithium-ion battery electrolytes under hot environment, improve the high-temperature behavior of lithium ion battery.
The additive that the present invention selects is a LiBF4, english abbreviation LiBF4, tricresyl phosphate methyl silicon; English abbreviation is TMSP, vinylene carbonate; English abbreviation is VC, and the additive vinylene carbonate can be assisted the formation of SEI film, adds tricresyl phosphate methyl silicon and LiBF4 and can in hot environment, slow down the degraded of SEI film and the generation once more of auxiliary SEI film; Thereby improve the stability of lithium-ion battery electrolytes under hot environment, improved the high-temperature behavior of lithium ion battery.
It is anodal that electrolyte of the present invention is injected with the LiMn2O4, and Delanium is a negative pole, carries out performance test in the aluminum-shell battery of nominal capacity 600mAh, mainly detects its cycle performance and high-temperature behavior.Testing result shows that the electrolyte by the said preparation of this patent requirement has excellent high-temperature behavior, excellent cycle performance in battery.60 ℃ of storages in 7 days, flatulence not, capability retention>=90% is stored 4h in 85 ℃ environment, varied in thickness≤5%, all circulation volume conservation rates in capability retention>=85%, 300>=85%.
Can make battery have excellent high-temperature behavior, excellent cycle performance owing to take technique scheme that nonaqueous electrolytic solution of the present invention is had; 60 ℃ of storages in 7 days, flatulence not, capability retention>=90%; In 85 ℃ environment, store 4h; Varied in thickness≤5%, the advantage and the effect of all circulation volume conservation rates in capability retention>=85%, 300>=85%.
Embodiment
Embodiment 1
Under the enclosed environment condition of moisture≤10ppm; 20g ethylene carbonate, 80g methyl ethyl carbonate are made with extra care the purification mixed solvent; Get above-mentioned mixed solvent 80g; Add the 16g lithium hexafluoro phosphate, stir, get 4g adding back stirring after again 15g LiBF4,10g tricresyl phosphate methyl silicon and 75g vinylene carbonate being mixed and obtained the high temperature lithium-ion battery electrolytes in 30 minutes.
Embodiment 2
Under the enclosed environment condition of moisture≤10ppm; 25g ethylene carbonate, 25g methyl ethyl carbonate, 25g diethyl carbonate and 25g propene carbonate are made with extra care the purification mixed solvent; Get above-mentioned mixed solvent 88g; Add 4.5g lithium hexafluoro phosphate and 3g biethyl diacid lithium borate, stir, get 4.5g adding back stirring after again 20g LiBF4,10g tricresyl phosphate methyl silicon and 70g vinylene carbonate being mixed and obtained the high temperature lithium-ion battery electrolytes in 30 minutes.
Embodiment 3
Under the enclosed environment condition of moisture≤10ppm; 40g ethylene carbonate, 60g diethyl carbonate are made with extra care the purification mixed solvent; Get above-mentioned mixed solvent 71.5g; Add 20g lithium hexafluoro phosphate and 2.5g two (trifluoromethyl sulphonyl) imines lithium lithium and stir, get 6g adding back stirring after again 20g LiBF4,20g tricresyl phosphate methyl silicon and 60g vinylene carbonate being mixed and obtained the high temperature lithium-ion battery electrolytes in 30 minutes.
Embodiment 4
Under the enclosed environment condition of moisture≤10ppm; 40g ethylene carbonate, 30g methyl ethyl carbonate, 30g propene carbonate are made with extra care the purification mixed solvent; Get above-mentioned mixed solvent 70g; Add 15g lithium hexafluoro phosphate, 2.5g two (trifluoromethyl sulphonyl) imines lithium and 2.5g biethyl diacid lithium borate, stir, get 10g adding back stirring after again 25g LiBF4,15g tricresyl phosphate methyl silicon and 60g vinylene carbonate being mixed and obtained the high temperature lithium-ion battery electrolytes in 30 minutes.
Embodiment 5
Under the enclosed environment condition of moisture≤10ppm; 50g ethylene carbonate, 30g methyl ethyl carbonate and 20g gamma-butyrolacton are made with extra care the purification mixed solvent; Get above-mentioned mixed solvent 80g; Add 9g lithium hexafluoro phosphate, 2g two (trifluoromethyl sulphonyl) imines lithium and 2g biethyl diacid lithium borate and stir, get 7g adding back stirring after again 15g LiBF4,20g tricresyl phosphate methyl silicon and 65g vinylene carbonate being mixed and obtained the high temperature lithium-ion battery electrolytes in 30 minutes.
Testing result is seen table 1
Table 1 testing result
The result shows that electrolyte of the present invention has the good high-temperature performance, deposits not flatulence, 60 ℃ of 7 days storage back capacity in 7 days for 60 ℃ and keeps>=90%%, 85 ℃ of 4h memory capacity conservation rate>=85%, 85 ℃ 4h storage varied in thickness≤5%, 300 all circulation volume conservation rates>=85%.
Claims (2)
1. high temperature lithium-ion battery electrolytes, it is characterized in that: it is made up of following weight percentages:
Electrolyte 7.5% ~ 22.5%, organic solvent 70% ~ 88% and additive 4% ~ 10%,
Said electrolyte is the combination of one or both or three kinds in lithium hexafluoro phosphate, biethyl diacid lithium borate or two (trifluoromethyl sulphonyl) the imines lithium,
Said organic solvent is one or both or the two or more combination in ethylene carbonate and gamma-butyrolacton, methyl ethyl carbonate, diethyl carbonate or the propene carbonate; The percentage by weight of all kinds of solvents is: ethylene carbonate is 20% ~ 50%; In gamma-butyrolacton, methyl ethyl carbonate, diethyl carbonate or the propene carbonate one or both or two or morely be combined as 50 ~ 80%
Said additive is made up of LiBF4, tricresyl phosphate methyl silicon and vinylene carbonate, and its percentage by weight is: tetrafluoro lithium phosphate 15% ~ 25%, tricresyl phosphate methyl silicon 10% ~ 20% and vinylene carbonate 60% ~ 75%.
2. the preparation method of high temperature lithium-ion battery electrolytes according to claim 1 is characterized in that it is undertaken by following step:
Under the enclosed environment condition of moisture≤10ppm; The organic solvent of 70% ~ 88% weight (down together) is made with extra care purification, add 7.5% ~ 22.5% electrolyte, stir; The additive that adds 4% ~ 10% weight again stirs and obtained the high temperature lithium-ion battery electrolytes in 30 minutes.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103000945A (en) * | 2012-11-29 | 2013-03-27 | 惠州Tcl金能电池有限公司 | Electrolyte and application thereof |
| CN103515648A (en) * | 2012-06-20 | 2014-01-15 | 万向电动汽车有限公司 | Lithium manganate battery electrolyte |
| CN104412425A (en) * | 2012-09-06 | 2015-03-11 | 株式会社吴羽 | Carbonaceous material for negative electrodes of nonaqueous electrolyte secondary batteries, and method for producing same |
| CN104412426A (en) * | 2012-09-06 | 2015-03-11 | 株式会社吴羽 | Carbonaceous material for negative electrode of nonaqueous-electrolyte secondary battery, process for producing same, and negative electrode and nonaqueous-electrolyte secondary battery obtained using said carbonaceous material |
| WO2015070447A1 (en) * | 2013-11-18 | 2015-05-21 | 中国科学院物理研究所 | High-voltage non-aqueous electrolyte solution and high-voltage non-aqueous electrolyte solution secondary battery |
| CN105098241A (en) * | 2015-07-13 | 2015-11-25 | 新余学院 | Electrolyte solution compatible with lithium-ion battery anode material lithium titanate |
| CN108134133A (en) * | 2017-11-30 | 2018-06-08 | 深圳市沃特玛电池有限公司 | A kind of lithium battery electrolytes and preparation method thereof |
| CN108713272A (en) * | 2017-01-12 | 2018-10-26 | 株式会社Lg化学 | Non-aqueous electrolytic solution and the lithium secondary battery for including the non-aqueous electrolytic solution |
| US10862167B2 (en) | 2016-04-29 | 2020-12-08 | Huawei Technologies Co., Ltd. | High-temperature lithium-ion battery electrolyte and production method thereof, and high-temperature lithium-ion battery |
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| CN101572331A (en) * | 2009-06-09 | 2009-11-04 | 东莞市杉杉电池材料有限公司 | Lithium ion battery electrolyte applicable to high-temperature environment and preparation method thereof |
| CN101939874A (en) * | 2008-03-05 | 2011-01-05 | 株式会社杰士汤浅国际 | Non-aqueous electrolyte battery |
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| CN101939874A (en) * | 2008-03-05 | 2011-01-05 | 株式会社杰士汤浅国际 | Non-aqueous electrolyte battery |
| CN101572331A (en) * | 2009-06-09 | 2009-11-04 | 东莞市杉杉电池材料有限公司 | Lithium ion battery electrolyte applicable to high-temperature environment and preparation method thereof |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103515648B (en) * | 2012-06-20 | 2016-09-14 | 万向电动汽车有限公司 | A kind of lithium manganate battery electrolyte |
| CN103515648A (en) * | 2012-06-20 | 2014-01-15 | 万向电动汽车有限公司 | Lithium manganate battery electrolyte |
| CN104412426A (en) * | 2012-09-06 | 2015-03-11 | 株式会社吴羽 | Carbonaceous material for negative electrode of nonaqueous-electrolyte secondary battery, process for producing same, and negative electrode and nonaqueous-electrolyte secondary battery obtained using said carbonaceous material |
| CN104412425A (en) * | 2012-09-06 | 2015-03-11 | 株式会社吴羽 | Carbonaceous material for negative electrodes of nonaqueous electrolyte secondary batteries, and method for producing same |
| CN104412425B (en) * | 2012-09-06 | 2017-07-21 | 株式会社吴羽 | Non-aqueous electrolyte secondary cell negative electrode carbonaceous material and its manufacture method |
| TWI641178B (en) * | 2012-09-06 | 2018-11-11 | 吳羽股份有限公司 | Carbonaceous material for negative electrode of secondary battery of nonaqueous electrolyte and manufacturing method thereof |
| CN103000945A (en) * | 2012-11-29 | 2013-03-27 | 惠州Tcl金能电池有限公司 | Electrolyte and application thereof |
| WO2015070447A1 (en) * | 2013-11-18 | 2015-05-21 | 中国科学院物理研究所 | High-voltage non-aqueous electrolyte solution and high-voltage non-aqueous electrolyte solution secondary battery |
| CN105098241A (en) * | 2015-07-13 | 2015-11-25 | 新余学院 | Electrolyte solution compatible with lithium-ion battery anode material lithium titanate |
| US10862167B2 (en) | 2016-04-29 | 2020-12-08 | Huawei Technologies Co., Ltd. | High-temperature lithium-ion battery electrolyte and production method thereof, and high-temperature lithium-ion battery |
| CN108713272A (en) * | 2017-01-12 | 2018-10-26 | 株式会社Lg化学 | Non-aqueous electrolytic solution and the lithium secondary battery for including the non-aqueous electrolytic solution |
| US10862166B2 (en) | 2017-01-12 | 2020-12-08 | Lg Chem, Ltd. | Non-aqueous electrolyte solution and lithium secondary battery including the same |
| CN108713272B (en) * | 2017-01-12 | 2021-05-18 | 株式会社Lg化学 | Nonaqueous electrolyte solution and lithium secondary battery including the same |
| CN108134133A (en) * | 2017-11-30 | 2018-06-08 | 深圳市沃特玛电池有限公司 | A kind of lithium battery electrolytes and preparation method thereof |
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Application publication date: 20120404 |