CN100583545C - Novel lithium ion battery electrolyte - Google Patents
Novel lithium ion battery electrolyte Download PDFInfo
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- CN100583545C CN100583545C CN200810026705A CN200810026705A CN100583545C CN 100583545 C CN100583545 C CN 100583545C CN 200810026705 A CN200810026705 A CN 200810026705A CN 200810026705 A CN200810026705 A CN 200810026705A CN 100583545 C CN100583545 C CN 100583545C
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- lithium
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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
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Abstract
The invention relates to field of cell electrolyte, concretely discloses a novel lithium ion cell concretely which is characterized in that: additive containing fluorinated organic compound is added into normal lithium ion cell electrolyte, and addition quantity of the additive is 5%-10% of whole quantity of lithium ion cell electrolyte. Advantages of the lithium ion cell concretely of present invention are that: discharge capacity and platform efficiency of the cell is obviously increased, internal resistance of the cell is reduced for a certain extent, measured cell data has good consistency, and discharging performance of the cell at high and low temperature is obviously increased.
Description
Technical field:
The present invention relates to the battery electrolyte technical field, particularly contain a kind of novel lithium-ion battery electrolytes of additive.
Background technology:
The employed electrolyte of lithium ion battery mainly contains three parts to be formed, and is respectively organic solvent, lithium salts, additive.Common organic solvent is generally: vinyl carbonate (EC), this kind organic solvent is used in electrolyte widely because of it can become skin covering of the surface and higher dielectric constant, propylene carbonate (PC), has the good low-temperature performance, but the methyl on the circulus can destroy the layer structure of carbon negative pole, in the use of reality, need to cooperate other organic solvent and additive to use, dimethyl carbonate (DMC), the organic solvent of diethyl carbonate (DEC) and Methylethyl carbonic ester straight chain shapes such as (EMC) is because of its satisfied feasible cosolvent that become organic solvent such as viscosity, r-butyrolactone (GBL), ethyl acetate (EA) waits some carboxylates that preferable performance is also arranged, and usually uses as cosolvent.Lithium salts can be lithium hexafluoro phosphate, LiBF4, lithium perchlorate etc., and wherein the performance with lithium hexafluoro phosphate is the most excellent especially, also is the normal lithium salts that uses of commercialization lithium ion battery.Organic solvent and lithium salts can satisfy the basic need of battery, when still using under mal-conditions such as abuse, must add the both positive and negative polarity that additive is protected lithium ion battery.Some common additives are as vinylene carbonate (VC), cyclohexyl benzene (CHB), propane sultone (PS) etc.VC can become good SEI film in the carbon negative terminal surface; but might be dissolved under hot conditions; CHB is good over-charge protective additive; but can make battery capacity attenuation in cyclic process; PS can become good SEI mould; has resistance and high temperature resistance property; also have many other miscellaneous additives; because of it can not have both all functions aspect battery performance; therefore in use according to the environment for use of battery and service condition and autotelic selectivity adds, but only depend on present additive still can not satisfy the various performance demands of lithium ion battery.
Summary of the invention:
One object of the present invention is exactly on preferred existing organic solvent basis, the fluorinated organic compound that adds one or more improves the effect of impregnation may of electrolyte to lithium ion battery separator as additive, another object of the present invention be exactly on the basis of original additive preferred again fluorinated organic compound mix the multiple performance of improving lithium ion battery as multifunction additive with its arbitrary proportion.
For achieving the above object, the following raw materials by weight percent of employing of the present invention prepares lithium-ion battery electrolytes:
Organic solvent 75%～85%
Lithium salts 10%～15%
Additive 5%～10%
Wherein employed organic solvent includes any one or two or more mixture of vinyl carbonate (EC), propylene carbonate (PC) dimethyl carbonate (DMC), diethyl carbonate (DEC), Methylethyl carbonic ester (EMC), ethyl acetate (EA);
Lithium salts can be lithium hexafluoro phosphate, LiBF4, lithium perchlorate etc., and wherein the performance with lithium hexafluoro phosphate is the most excellent especially, also is the normal lithium salts that uses of commercialization lithium ion battery, therefore, is preferably lithium hexafluoro phosphate;
Because functional fluoropolymer group has the status that can't replace for the improvement of lithium-ion battery electrolytes performance, therefore, using the fluorinated organic compound that adds one or more on one or both the basis of original additive vinylene carbonate (VC), cyclohexyl benzene (CHB), propane sultone (PS) again to give full play to the performance of electrolyte.
The skeleton symbol of above-mentioned fluorinated organic compound is expressed as:
R in the following formula
1And R
2Can be hydrogen atom, phenyl, alkyl, halogenophenyl, haloalkyl or carbon number 10 with interior linear paraffin, and the hydrogen atom on the alkane can be by all or part of replacement of F atom.The length of carbochain can be between 2～14, but is optimum value between can thinking 2～6 according to result of use.
(H in the glove box of applying argon gas
2O＜10ppm), with the ratio of each organic solvent in 1: 1: 1, concentration is the lithium salts lithium hexafluoro phosphate (LiPF of 1M in above-mentioned amount
6), additive is vinylene carbonate (VC), propane sultone (PS), and fluorinated organic compound is pressed arbitrary proportion and is mixed, and above-mentioned each raw material is added successively, stirs, and promptly obtains lithium-ion battery electrolytes of the present invention.
Advantage of the present invention and good effect are: add the additive that contains fluorinated organic compound in common lithium-ion battery electrolytes, and the addition that contains the organic compound additive of fluoro is 5%～10% of a lithium-ion battery electrolytes total amount, use lithium-ion battery electrolytes of the present invention, the discharge capacity of battery and platform efficient can both be significantly improved, the also decrease to some degree of internal resistance of battery self simultaneously, the battery data of being measured can both have good consistency.In addition, use this lithium-ion battery electrolytes can make the battery low temperature performance be significantly improved, also can take into account the raising of the high temperature discharge performance of battery simultaneously.
Embodiment:
In order better to describe the present invention, specify below by embodiment:
Embodiment 1
(H in the glove box of applying argon gas
2O＜10ppm) is with each organic solvent EC: DEC: DMC=1 in proportion: 1: 1, account for 77.5% of total weight; Lithium salts is lithium hexafluoro phosphate (LiPF
6), its concentration is 1M, accounts for 12.5% of total weight; Additive is vinylene carbonate (VC), accounts for 4% of total weight, and propane sultone (PS) accounts for 5% of total weight, to methyl fluoride benzene, accounts for 1% of total weight; Above-mentioned each raw material is added successively, stir, promptly obtain lithium-ion battery electrolytes of the present invention.
Embodiment 2
(H in the glove box of applying argon gas
2O＜10ppm) is with each organic solvent EC: DEC: EA=1 in proportion: 1: 1, account for 82.5% of total weight; Lithium salts is lithium hexafluoro phosphate (LiPF
6), its concentration is 1M, accounts for 12.5% of total weight; Additive is vinylene carbonate (VC), accounts for 4% of total weight, and trifluoroethyl benzene accounts for 1% of total weight, and above-mentioned each raw material is added successively, stirs, and promptly obtains lithium-ion battery electrolytes of the present invention.
Embodiment 3
(H in the glove box of applying argon gas
2O＜10ppm) is with each organic solvent EC: DEC: EMC=1 in proportion: 1: 1, account for 81.5% of total weight; Lithium salts is lithium hexafluoro phosphate (LiPF
6), its concentration is 1M, accounts for 12.5% of total weight; Additive is vinylene carbonate (VC), accounts for 2% of total weight, hexafluoroethane, account for 3% of total weight, propane sultone (PS) accounts for 1% of total weight, each raw material of above-mentioned amount is added successively, stir, promptly obtain lithium-ion battery electrolytes of the present invention.
Result's contrast:
A, B are respectively taken by weighing 100 grams places two to fluoridize bottle respectively, wherein A adds the not battery electrolyte contrast sample of fluorochemical additive, B adds the battery electrolyte of 3% hexafluoroethane for the present invention, be prepared into the box hat battery with two kinds of electrolyte respectively, according to certain battery preliminary filling, change into system, obtain following data:
Table 1: contain the electrolyte of fluoride additive and the not comparison between the measured capacity of fluorochemical additive electrolyte
Table 2: it is as follows to carry out the data that variance analysis obtains for capacity data in the table 1:
| Numbering | Standard deviation | Mean value |
| A | 24.67 | 715.30 |
| B | 8.90 | 731.73 |
Table 3: contain the electrolyte of fluoride additive and the not comparison between the measured capacity of fluorochemical additive electrolyte:
Table 4: it is as follows to carry out the data that variance analysis obtains for internal resistance data in the table 3:
| Numbering | Standard deviation | Mean value |
| A | 5.03 | 62.37 |
| B | 2.65 | 54.96 |
Table 5: contain the electrolyte of fluoride additive and the not comparison between the measured capacity of fluorochemical additive electrolyte:
Table 6: it is as follows to carry out the data that variance analysis obtains for platform efficiency data in the table 5:
| Numbering | Standard deviation | Mean value |
| A | 4.64 | 77.019 |
| B | 3.06 | 82.44 |
Claims (3)
1, a kind of lithium-ion battery electrolytes is characterized in that: following row raw materials by weight percent is made:
Organic solvent 75%～85%
Lithium salts 10%～15%
Additive 5%～10%
Wherein employed organic solvent includes any one or two or more mixture of vinyl carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, Methylethyl carbonic ester, ethyl acetate;
Lithium salts is lithium hexafluoro phosphate, LiBF4, lithium perchlorate;
Additive is one or both in vinylene carbonate, cyclohexyl benzene, the propane sultone, and then adds one or more fluorinated organic compound;
The skeleton symbol of above-mentioned fluorinated organic compound is expressed as:
R in the following formula
1And R
2Can be hydrogen atom, phenyl, alkyl, halogenophenyl, haloalkyl or carbon number 10 with interior linear paraffin, and the hydrogen atom on the alkane can be by all or part of replacement of F atom, the length of carbochain be between 2～14.
2, a kind of lithium-ion battery electrolytes according to claim 1, it is characterized in that: the carbon chain lengths of the fluorinated organic compound that adds in the described additive is between 2～6.
3, a kind of lithium-ion battery electrolytes according to claim 1, it is characterized in that: in the glove box of applying argon gas, wherein, moisture in the argon gas is less than 10ppm, with each compound of containing in organic solvent ratio in 1: 1: 1, concentration is the lithium salts lithium hexafluoro phosphate of 1M in the described amount of claim 1; Additive vinylene carbonate, propane sultone, fluorinated organic compound, press arbitrary proportion and mix; Above-mentioned each raw material is added successively, stir, promptly obtain lithium-ion battery electrolytes.
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| CN200810026705A CN100583545C (en) | 2008-03-07 | 2008-03-07 | Novel lithium ion battery electrolyte |
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| CN200810026705A CN100583545C (en) | 2008-03-07 | 2008-03-07 | Novel lithium ion battery electrolyte |
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| CN101281986A CN101281986A (en) | 2008-10-08 |
| CN100583545C true CN100583545C (en) | 2010-01-20 |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101841061A (en) * | 2010-05-10 | 2010-09-22 | 陈韵吉 | Low-temperature electrolyte of lithium iron phosphate power battery and preparation method thereof |
| CN102064343B (en) * | 2010-12-21 | 2012-09-26 | 东莞市杉杉电池材料有限公司 | Novel lithium ion battery electrolyte |
| CN102790236A (en) * | 2011-05-18 | 2012-11-21 | 张家港市国泰华荣化工新材料有限公司 | Non-aqueous electrolyte solution of fluorine-containing compound |
| CN102593515A (en) * | 2012-03-20 | 2012-07-18 | 惠州市赛能电池有限公司 | Electrolyte of lithium ion battery |
| CN103035947A (en) * | 2013-01-09 | 2013-04-10 | 东莞市凯欣电池材料有限公司 | Novel electrolyte of lithium-ion battery and preparation method thereof |
| CN103078141A (en) * | 2013-01-25 | 2013-05-01 | 宁德新能源科技有限公司 | Lithium-ion secondary battery and electrolyte thereof |
| CN104282942A (en) * | 2013-11-14 | 2015-01-14 | 上海图尔实业发展有限公司 | High-performance electrolyte and application of high-performance electrolyte in secondary battery |
| CN104409767B (en) * | 2014-11-25 | 2017-05-24 | 上海动力储能电池系统工程技术有限公司 | Low-temperature type lithium ion secondary battery |
| CN106328938A (en) * | 2015-06-17 | 2017-01-11 | 深圳市沃特玛电池有限公司 | Low-temperature lithium iron phosphate battery and preparation method |
| US10249449B2 (en) | 2016-03-01 | 2019-04-02 | Maxwell Technologies, Inc. | Electrolyte formulations for energy storage devices |
| CN108832201B (en) * | 2018-06-06 | 2020-09-11 | 天津科技大学 | Electrolyte additive, electrolyte and lithium ion battery using electrolyte additive |
| CN110911754B (en) * | 2019-12-27 | 2020-11-20 | 江西壹金新能源科技有限公司 | Lithium ion battery electrolyte and preparation method thereof |
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Assignee: SHENZHEN HONGDE BATTERY Co.,Ltd. Assignor: DONGGUAN SHANSHAN BATTERY MATERIALS Co.,Ltd. Contract record no.: 2010440020133 Denomination of invention: Novel electrolyte of lithium-ion battery and preparation method thereof Granted publication date: 20100120 License type: Exclusive License Open date: 20081008 Record date: 20100811 |
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Effective date of registration: 20230922 Address after: No.62 Huayin North Road, Kecheng District, Quzhou City, Zhejiang Province Patentee after: New Asia Shanshan New Material Technology (Quzhou) Co.,Ltd. Address before: Five the 523000 Guangdong province Dongguan Nancheng district water Lianpeng Dong Industrial Zone of Dongguan City Shanshan battery materials Co. Ltd. Patentee before: DONGGUAN SHANSHAN BATTERY MATERIALS Co.,Ltd. |