CN101859913B - Cyano-containing high dielectric constant organic silicon electrolyte materials - Google Patents
Cyano-containing high dielectric constant organic silicon electrolyte materials Download PDFInfo
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- CN101859913B CN101859913B CN2010101829786A CN201010182978A CN101859913B CN 101859913 B CN101859913 B CN 101859913B CN 2010101829786 A CN2010101829786 A CN 2010101829786A CN 201010182978 A CN201010182978 A CN 201010182978A CN 101859913 B CN101859913 B CN 101859913B
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Abstract
The cyano-containing high dielectric constant organic silicon electrolyte materials that the present invention provides one kind safely, effectively, has a wide range of application. Its chemical structural formula such as Formulas I. Wherein R1, R2, R3 are selected from identical or different C1-C10 alkyl or alkoxy, and wherein at least one group is the alkoxy grp such as (CH2) nO (CH2CH2O) mCH3 structure, and n, m are the integer of 0-10; R4 is C1-C20 methylene. Cyano-containing high dielectric constant organic silicon electrolyte materials of the present invention can be used as electrolyte or additive application lithium ion battery, furthermore be also used as electrolyte applied to other electrochemical energy storing devices (such as electrolytic capacitor and super capacitor) and other photoelectric devices (such as organic solar batteries).
Description
Technical field:
The present invention relates to technical field of chemistry, relate in particular to the kind of cyanic high dielectric constant organic silicon electrolyte materials.
Technical background
At present, employed electrolyte mainly is organic carbonate ester type compound and LiPF in the lithium ion battery industry
6The lithium salts system; Still there is fail safe hidden danger technically in the mode of operation of system; Its main cause is that carbonates organic electrolysis material has very high combustibility; Therefore there is huge hidden danger in fail safe, and especially in hybrid power that requires high security, big capacity and high-multiplying power discharge and full electric car application, safety issue is the key factor that these materials of restriction are used.Therefore, all researching and developing safe, effective and eco-friendly organic electrolysis material of new generation energetically both at home and abroad.
Polyethylene glycol oxide (PEO) is the polymer electrolyte of developing the earliest and be applied to lithium grain ion battery, yet the ionic conductivity of PEO is lower, has limited its application.For solving the low conductivity problem of PEO; People such as West disclose the liquid and polymer electrolyte (US2006035154-A1 of one type of carbonated ester group organosilicon in patent; US2004248014-A1); High-k group carbonate group improves the high-k of material, helps the disassociation of ion, thereby improves the ionic conductivity of material.Egashira (J.Power Sources, 18 (2004) 240-244) has reported the representative examples of saturated aliphatic quaternary ammonium salt ionic liquid of cyano-containing, finds that cyanic acid helps the disassociation of ion.International monopoly WO200519185 discloses a kind of five yuan or hexa-atomic aromatic heterocycle ionic liquid of cyano-containing, Chinese patent CN101085762A disclose a kind of cyano-containing based on the cationic ion liquid compound of morpholine.Organic silicon electrolyte materials and ionic liquid material all have high security, but these material synthesis method are complicated, and cost is higher.
Summary of the invention:
The cyano-containing high dielectric constant organic silicon electrolyte materials that the purpose of this invention is to provide a kind of safe, effective, applied range.
The chemical structural formula of the cyano-containing high dielectric constant organic silicon electrolyte materials that the present invention relates to is as shown in the formula I:
R wherein
1, R
2, R
3Be selected from identical or different C1-C10 alkyl or alkoxyl, wherein have at least a group to be as (CH
2)
nO (CH
2CH
2O)
mCH
3The alkoxy grp of structure, n, m are the integer of 0-10; R
4Be the C1-C20 methylene.
Principle of the present invention is, in organic silica-based material structure that contains the EO unit, introduces strong polarity cyanic acid, and the high-k improving material keeps the fail safe of organosilicon material simultaneously.
Cyano-containing high dielectric constant organic silicon electrolyte materials of the present invention can be used as electrolyte or additive and uses lithium ion battery, can be used as electrolyte in addition and is applied to other electrochemical energy storing device (like electrochemical capacitor and super capacitor) and other photoelectric device (like organic solar cell etc.).
Description of drawings
Fig. 1 is the glass transition temperature curve of embodiment of the invention 1-3 cyano-containing high dielectric constant organic silicon electrolyte materials.
Fig. 2 is that the ionic conductivity of embodiment of the invention 1-3 cyano-containing high dielectric constant organic silicon electrolyte materials is with temperature variation curve (1MLiTFSI).
Embodiment:
Below in conjunction with accompanying drawing and embodiment content of the present invention is described further.
The synthetic reaction formula of embodiment is following:
Shown in above-mentioned reaction equation, the first step of following examples is synthetic 3-propyl group nitrile-dimethylchlorosilanes, and process is following:
Under 0 ℃, dimethylchlorosilane (6.7g, 71mmol) slowly splash into acrylonitrile (4.8g, 71.6mmol) with the 5mol% platinum catalyst in, 50 ℃ the heating 16h, directly obtain colorless liquid product, b.p.42 ℃/0.2Torr through decompression distillation.
1H-NMR(600MHz，CDCl
3)：δ＝0.536(s，6H，SiCH
3)，1.074(m，2H，SiCH
2)，1.892(m，2H，SiCH
2CH
2)，2.51(t，2H，J＝7.2，CH
2CN)；
13C?NMR(600MHz，CDCl3)：-0.001，16.688，18.195，18.635，117.889.
Synthesizing of embodiment 1:3-propyl group nitrile-methoxy ethoxy-dimethylsilane (EO1SiC3CN)
3-propyl group nitrile-dimethylchlorosilane (10g, 61.8mmol) slowly splash into glycol monoethyl ether (4.8g, 63.1mmol) with the oxolane of equivalent triethylamine in; Reflux 18h; Filter the back rotary evaporation except that desolvating, obtain colorless liquid product through decompression distillation, b.p.55 ℃/0.2Torr.
1H-NMR(600MHz，CDCl
3)：δ＝0.145(s，6H，SiCH
3)，0.764(m，2H，SiCH
2)，1.738(m，2H，SiCH
2CH
2)，2.382(t，2H，J＝7.0，CH
2CN)，3.378(s，3H，OCH
3)，3.433(J＝4.8Hz，，2H，CH
3OCH
2CH
2)，3.738(t，J＝4.8Hz，2H，CH
2CH
2OS?i)，3.74(t，2H，J＝7.0Hz，CH
2OSi)；、
13C?NMR(600MHz，CDCl3)：0.001，18.159，22.108，22.654，61.170，64.368，76.136，121.959；
29Si(600MHz，CDCl3)：15.647ppm。
Synthesizing of embodiment 2:3-propyl group nitrile-methoxyl group diethoxy-dimethylsilane (EO2SiC3CN)
Use diethylene glycol monomethyl ether to be reactant, adopt the identical synthetic method of embodiment 1, product obtains colourless liquid through decompression distillation, b.p.108-110 ℃/0.2Torr.
1H-NMR(600MHz，CDCl
3)：δ＝0.114(s，6H，SiCH
3)，0.732(m，2H，SiCH
2)，1.713(m，2H，SiCH
2CH
2)，2.358(t，2H，J＝7.0，CH
2CN)，3.65(s，3H，OCH
3)，3.53(m，4H，CH
3OCH
2CH
2)，3.62(m，2H，CH
2CH
2OSi)，3.74(t，2H，J＝7.0Hz，CH
2OSi)；
13C?NMR(600MHz，CDCl3)：-0.001，18.195，18.065，22.082，22.311，60.898，64.404，72.597，74.072，74.666，121.842；
29Si(600MHz，CDCl3)：15.9ppm。
Synthesizing of embodiment 3:3-propyl group nitrile-methoxyl group triethoxy-dimethylsilane (EO3SiCSCN)
Use triethylene glycol monomethyl ether to be reactant, adopt the identical synthetic method of embodiment 1, product obtains colourless liquid through decompression distillation, b.p.125-127 ℃/0.2Torr.
1H-NMR(600MHz，CDCl3)：δ＝0.108(s，6H，SiCH
3)，0.726(m，2H，SiCH
2)，1.71(m，2H，SiCH
2CH
2)，2.356(t，2H，J＝7.0，CH
2CN)，3.57(s，3H，OCH
3)，3.526(m，4H，CH
3OCH
2CH
2)，3.618(m，4H，CH
2CH
2OSi)，3.16(t，2H，J＝5.2Hz，CH
2OSi)；
13C?NMR(600MHz，CDCl3)：0.018，18.114，22.071，22.534，61.067，64.407，72.623，72.658，72.730，74.078，74.665，121.942；
29Si(600MHz，CDCl3)：15.6ppm。
The physicochemical properties data of the cyano-containing high dielectric constant organic silicon electrolyte materials of embodiment 1-3 gained are as shown in table 1:
Table 1
From accompanying drawing and table 1, can find out; Cyano-containing organic silicon electrolyte materials of the present invention has higher high-k (reach～12) and ionic conductivity; And the high-k that has similar structures and do not have a cyanic acid organosilicon material is 4-5 (J.Mater.Chem., 18 (2008), 3713).
Claims (2)
1. cyano-containing high dielectric constant organic silicon electrolyte materials is characterized in that its structural formula is as shown in the formula I:
Wherein, R
1, R
2, R
3Be selected from identical or different C1-C10 alkyl or alkoxyl, wherein having a group at least is (CH
2)
nO (CH
2CH
2O)
mCH
3The alkoxy grp of structure, n, m are the integer of 0-10; R
4Be the C1-C20 methylene.
2. cyano-containing high dielectric constant organic silicon electrolyte materials as claimed in claim 1 is characterized in that said R
1, R
2Be methyl.
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|---|---|---|---|---|
| CN103122008B (en) * | 2011-12-13 | 2016-02-24 | 曹坚林 | Silane coupling agent of a kind of cyano-containing and preparation method thereof |
| CN109336917A (en) * | 2013-06-04 | 2019-02-15 | 塞勒创尼克斯公司 | The substituted silane of nitrile-and electrolyte composition and the electrochemical appliance comprising them |
| CN104072533B (en) * | 2014-06-10 | 2016-05-11 | 中国科学院广州能源研究所 | One class is containing silicon nitrile compounds of low polyoxyethylene units and preparation method thereof, application in lithium battery |
| US10355313B2 (en) | 2014-10-03 | 2019-07-16 | Silatronix, Inc. | Functionalized silanes and electrolyte compositions and electrochemical devices containing them |
| CN105514487A (en) * | 2015-12-30 | 2016-04-20 | 中国科学院广州能源研究所 | Method for matching organic silicon electrolyte with silicon-based electrode material for use |
| CN106025358B (en) * | 2016-06-27 | 2018-12-07 | 中国科学院广州能源研究所 | A kind of organic silicon amine electrolyte of dicyanogen methyl isophorone functionalization |
| CN111293364B (en) * | 2018-12-10 | 2021-03-30 | 张家港市国泰华荣化工新材料有限公司 | Non-aqueous electrolyte and lithium ion battery |
| CN112018442B (en) * | 2019-05-29 | 2022-02-08 | 比亚迪股份有限公司 | Lithium ion battery electrolyte and lithium ion battery |
| CN113717211A (en) * | 2021-08-31 | 2021-11-30 | 石家庄圣泰化工有限公司 | Synthesis method of nitrile-group functionalized organic silicon compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4505997A (en) * | 1982-06-01 | 1985-03-19 | Agence Nationale De Valorisation De La Recherche (Anvar) | Bis perhalogenoacyl -or sulfonyl-imides of alkali metals, their solid solutions with plastic materials and their use to the constitution of conductor elements for electrochemical generators |
| CN1449069A (en) * | 2002-04-02 | 2003-10-15 | 株式会社日本触媒 | Material for electrolyte solution and uses thereof |
| CN101548425A (en) * | 2006-12-06 | 2009-09-30 | 三菱化学株式会社 | Nonaqueous electrolyte solution and nonaqueous electrolyte secondary battery |
-
2010
- 2010-05-19 CN CN2010101829786A patent/CN101859913B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4505997A (en) * | 1982-06-01 | 1985-03-19 | Agence Nationale De Valorisation De La Recherche (Anvar) | Bis perhalogenoacyl -or sulfonyl-imides of alkali metals, their solid solutions with plastic materials and their use to the constitution of conductor elements for electrochemical generators |
| CN1449069A (en) * | 2002-04-02 | 2003-10-15 | 株式会社日本触媒 | Material for electrolyte solution and uses thereof |
| CN101548425A (en) * | 2006-12-06 | 2009-09-30 | 三菱化学株式会社 | Nonaqueous electrolyte solution and nonaqueous electrolyte secondary battery |
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