• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a composition comprising at least one electrolyte based on lithium imidazolate salts and the use of nitrile or dinitrile solvents for increasing the ionic conductivity of electrolyte based on lithium imidazolate salts. It also relates to the use of the electrolytic composition in Li-ion batteries.
    公开号:FR3018519A1
    申请号:FR1454902
    申请日:2014-05-30
    公开日:2015-09-18
    发明作者:Gregory Schmidt
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION The present invention relates to a composition comprising at least one electrolyte based on lithium imidazolate salts and the use of nitrile solvents or dinitriles for increasing the ionic conductivity of electrolyte based on lithium imidazolate salts. It also relates to the use of the electrolytic composition in Li-ion batteries. TECHNICAL BACKGROUND A lithium-ion battery comprises at least one negative electrode (anode), a positive electrode (cathode), a separator and an electrolyte. The electrolyte generally consists of a lithium salt dissolved in a solvent which is generally a mixture of organic carbonates, in order to have a good compromise between the viscosity and the dielectric constant. Additives can then be added to improve the stability of the electrolyte salts. Among the most used salts is lithium hexafluorophosphate (LiPF6), which has many of the required qualities but has the disadvantage of degrading in the form of hydrofluoric acid gas by reaction with water. This poses safety problems, particularly in the context of the forthcoming use of lithium-ion batteries for private vehicles. Recently, other salts have been developed, such as lithium LiTDI (1-trifluoromethyl-4,5-dicarbonitrile-imidazolate) and lithium LiPDI (1-pentafluoroethyl-4,5-dicarbonitrile-imidazolate). These salts have the advantages of having fewer fluorine atoms and having strong carbon-fluorine bonds instead of the lower phosphorus-fluorine LiPF6 bonds. Moreover, the patent WO2010023413 shows that these salts have conductivities of the order of 6 mS / cm, a very good dissociation between the imidazolate anion and the lithium cation and their use as a battery electrolyte salt. ion. But this ionic conductivity measured in so-called conventional solvents of electrolytes that are carbonate mixtures is too low for use in so-called power type batteries. The applicant has discovered that the use of solvent having at least one nitrile function makes it possible to improve the ionic conductivity of these lithium salts. DESCRIPTION The invention relates first of all to an electrolytic composition comprising one or more lithium salts of formula (A) in a solvent comprising at least one nitrile function or a solvent mixture of which at least one comprises a nitrile function. The invention also relates to the use of said electrolyte as electrolyte Li-ion batteries. The invention furthermore relates to the use of a solvent comprising at least one nitrile function to improve the ionic conductivity of electrolyte based on lithium imidazolate salts. The lithium salts of formula (A) are represented below NCNN> NCVN (A) with Rf representing a fluorine atom, a nitrile group, an optionally fluorinated or perfluorinated alkyl group having 1 and 5 carbons, an optionally alkoxy group fluorinated or perfluorinated having 1 to 5 carbons or an optionally fluorinated or perfluorinated oxa-alkoxy having 1 to 5 carbons.
    [0002] By way of examples, there may be mentioned in particular the following Rf groups: F, CF3, CHF2, CH2F, C2HF4, C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C4F9, C41-12F7, C41-14F5, C5F11, C3F5OCF3. , C2F4OCF3, C2H2F2OCF3, CF2OCF3, C5F110CH3, CF2OC2H5, CF20C2F140CF13, CF20C2F140C2F15, CF2OCH2OCF3, CF (CF3) OCH3, CF (CF3) OC2H5, CF (CF3) OC2H4OCH3 or CF (CF3) OC2H2F3.
    [0003] Preferably, Rf is CF3. The present invention makes it possible to overcome the disadvantages of the salts previously described. Indeed, although these salts are particularly interesting Rf due to their chemical and electrochemical stability and the strong separation between the anion and the lithium cation, however their low ionic conductivity limits their performance in terms of power. This low conductivity can be attributed not only to a low dissociation of the salt in conventional electrolyte solvents, especially carbonates, but also to a high viscosity due to the size of the anion. As carbonates conventionally used, there may be mentioned in particular ethylene carbonate, dimethylcarbonate, ethylmethylcarbonate, diethylcarbonate, propylene carbonate. The applicant has discovered that the use of solvent comprising at least one nitrile function in the presence or absence of co-solvent (s) greatly improves the ionic conductivity of electrolytes made from lithium salts of formula (A). Without being bound by any explanation, the applicant thinks that the nitrile function by its flatness and its affinity with the nitrile functions of the anion of the salt of formula (A) allows a better dissociation of the lithium salt. solvents having at least one nitrile function have advantages over conventional solvents. Thus, the low viscosity and the wide temperature range at which solvents having at least one nitrile function are in the liquid state provide a wider operating temperature range of the battery.
    [0004] The solvents comprising at least one nitrile function according to the present invention may be represented by the general formula R (CN) X where x is a number between 1 and 3 and R represents an optionally fluorinated or perfluorinated alkyl group having 1 and 5 carbons , an optionally fluorinated or perfluorinated alkoxy group having 1 to 5 carbons or an optionally fluorinated or perfluorinated oxa-alkoxy having 1 to 5 carbons. According to one embodiment x is equal to 2 and R has the same meaning as above. As solvents comprising at least one nitrile function, there may be mentioned especially acetonitrile, pyruvonitrile, propionitrile, methoxypropionitrile, dimethylaminopropionitrile, butyronitrile, isobutyronitrile, valeronitrile, pivalonitrile, isovaleronitrile, glutaronitrile, methoxyglutaronitrile, 2-methylglutaronitrile, 3-methylglutaronitrile, adiponitrile and malononitrile. The nitrile solvent can be used alone or in admixture with one or five cosolvents.
    [0005] As co-solvents, there may be mentioned in particular the nitriles of formula R (CN) X mentioned above, carbonates such as ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate or glymes such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether and diethylene glycol t-butyl methyl ether.
    [0006] Preferably, the solvent (s) comprising at least one nitrile function represents (s) between 1% and 100% by volume of all the solvents in the electrolytic composition, advantageously between 10 and 90% by volume. More particularly, in the presence of solvents of formula R (CN) X in which x is equal to 2 or 3, the cosolvent (s) is (are) preferably chosen from dimethylcarbonate, ethylmethylcarbonate, diethylcarbonate, propylene carbonate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol diethyl ether and triethylene glycol dimethyl ether. According to this embodiment (ie when x = 2 or 3), the volume proportion of solvent (s) comprising at least one nitrile function R (CN) X in the solvent mixture is preferably comprised between 1% and 50% and the proportion by volume of the sum of the co-solvents is preferably between 50% and 99% of the total volume of the mixture. According to another embodiment, in the presence of solvents of formula R (CN) X in which x is equal to 1, the co-solvent (s) is (are) preferably chosen from ethylene carbonate, propylene carbonate, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether and diethylene glycol t-butyl methyl ether. According to this embodiment (ie when x = 1), the volume proportion of solvent (s) comprising at least one nitrile function R (CN) X in the solvent mixture is preferably between 50 and 99% and the volume proportion of the sum of the cosolvents is preferably between 1% and 50% of the total volume of the mixture. The amount of lithium salt of formula (A) dissolved in the solvent mixture described above may vary between 0.01 and 10 mol / l, more preferably between 0.05 and 2 mol / l. The amount of lithium salt of formula (A) present in the electrolytic composition according to the present invention may vary between 0.01 and 10 mol / l, preferably between 0.05 and 2 mol / l. Preferably, the lithium salt (s) of formula (A) represents (s) between 2% and 100% by weight of all the salts present in the electrolytic composition, advantageously between 25 and 100% by weight. .
    [0007] The present invention also relates to the use of at least one solvent comprising at least one nitrile function for improving the ionic conductivity of electrolyte based on lithium imidazolate salts, preferably of formula (A).
    [0008] The amount of solvent comprising at least one nitrile function involved is preferably that indicated above. The nitrile solvent is preferably chosen from the list described above. The present invention further relates to the use of the above compositions as electrolyte Li-ion batteries. EXAMPLES The following examples illustrate the invention without limiting it. In the following examples the ionic conductivities were measured by impedance spectroscopy using a conductivity cell provided with 2 platinum platinum plates.
    [0009] Example 1: An electrolyte containing 1 mol / l of a salt of formula (A) wherein Rf = CF3 (LiTDI) in propionitrile is prepared. The ionic conductivity of this electrolyte is measured using the technique described above. The value obtained is 12 mS / cm. Example 2: An electrolyte containing 0.9 mol / L of a salt of formula (A) wherein Rf = CF3 (LiTDI) in an ethylene carbonate / propionitrile mixture with different proportions by volume is prepared. The ionic conductivities of these electrolytes are measured using the technique previously described. The values obtained are summarized in the following table. Report. in volume Conductiv e ionic Efi D ronitrile 10:90 1 -1-1. 20: 811 E C.
    [0010] 70 4L-1: bc; J 54 50:50 35
    权利要求:
    Claims (10)
    [0001]
    REVENDICATIONS1. Electrolytic composition comprising at least one lithium salt of formula (A) Rf NC (A) in which Rf represents a fluorine atom, a nitrile group, an optionally fluorinated or perfluorinated alkyl group having 1 and 5 carbons, an optionally alkoxy group fluorinated or perfluorinated compound having 1 to 5 carbons or an optionally fluorinated or perfluorinated oxa-alkoxy having 1 to 5 carbons, in a solvent comprising at least one nitrile function or a solvent mixture of which at least one comprises a nitrile function. 20
    [0002]
    2. Composition according to claim 1 characterized in that the solvent comprising at least one nitrile function is represented by the general formula R (CN) X where x is a number between 1 and 3 and R represents an optionally fluorinated or perfluorinated alkyl group having 1 and 5 carbons, an optionally fluorinated or perfluorinated alkoxy group having 1 to 5 carbons or an optionally fluorinated or perfluorinated oxa-alkoxy having 1 to 5 carbons.
    [0003]
    3. Composition according to claim 1 or 2 characterized in that Rf represents F, CF3, CHF2, CH2F, C2HF4, C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C4F9, C4H2F7, C4H4F5, C5F11, C3F5OCF3, C2F40CF3, C2H2F20CF3, CF20CF3, C5F11OCH3, CF20C2H5, CF20C2H4OCH3, CF20C2H40C2H5, CF2OCH2OCF3, CF (CF3) OCH3, CF (CF3) OC2H5, CF (CF3) OC2H4OCH3 or CF (CF3) OC2H2F3. 35
    [0004]
    4. Composition according to claim 3 characterized in that Rf represents CF3. 10
    [0005]
    5. Composition according to any one of the preceding claims, characterized in that the amount of lithium salt of formula (A) present in the electrolytic composition according to the present invention may vary between 0.01 and 10 mol / l, preferably between 0.05 and 2 mol / I.
    [0006]
    6. Composition according to any one of the preceding claims, characterized in that the solvent (s) comprising at least one nitrile function represents (s) between 1% and 100% by volume of all the solvents in the electrolytic composition. .
    [0007]
    7. Composition according to any one of claims 2 to 6 characterized in that x is equal to 2.
    [0008]
    8. Use of a composition according to any one of the preceding claims in a Li-on battery.
    [0009]
    9. Use of a solvent comprising at least one nitrile function or a mixture of solvents, at least one of which comprises a nitrile function for improving the ionic conductivity of electrolyte based on lithium imidazolate salts, preferably of the formula ( AT).
    [0010]
    10
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    同族专利:
    公开号 | 公开日
    CA2942197A1|2015-09-17|
    EP3557677A1|2019-10-23|
    FR3018635A1|2015-09-18|
    WO2015136201A1|2015-09-17|
    FR3018519B1|2019-07-05|
    KR20160132961A|2016-11-21|
    EP3117479B1|2019-04-24|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2010023413A1|2008-08-29|2010-03-04|Centre National De La Recherche Scientifique|Pentacyclic anion salt and use thereof as an electrolyte|
    US20110229769A1|2010-03-17|2011-09-22|Sony Corporation|Lithium secondary battery, electrolytic solution for lithium secondary battery, electric power tool, electrical vehicle, and electric power storage system|
    WO2013182767A1|2012-06-04|2013-12-12|Arkema France|Salt of bicyclic aromatic anions for li-ion batteries|
    KR100816592B1|2006-03-24|2008-03-24|마쯔시다덴기산교 가부시키가이샤|Non-aqueous electrolyte secondary battery|
    FR2983466B1|2011-12-06|2014-08-08|Arkema France|USE OF MIXTURES OF LITHIUM SALTS AS ELECTROLYTES OF LI-ION BATTERIES|PL412729A1|2015-06-15|2016-12-19|Politechnika Warszawska|Electrolyte for ion batteries|
    CN106571486A|2015-10-11|2017-04-19|深圳市沃特玛电池有限公司|High temperature circulation type power battery electrolyte|
    FR3059835B1|2016-12-02|2020-01-24|Arkema France|IMPROVED ION CONDUCTIVITY OF IMIDAZOLATE LITHIUM SALT ELECTROLYTE|
    CN108172900B|2017-12-18|2019-08-16|中节能万润股份有限公司|A kind of new lithium salts and its preparation method and application|
    法律状态:
    2016-04-12| PLFP| Fee payment|Year of fee payment: 3 |
    2017-04-13| PLFP| Fee payment|Year of fee payment: 4 |
    2018-04-11| PLFP| Fee payment|Year of fee payment: 5 |
    2020-04-14| PLFP| Fee payment|Year of fee payment: 7 |
    2022-02-11| ST| Notification of lapse|Effective date: 20220105 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1452145|2014-03-14|
    FR1452145A|FR3018635A1|2014-03-14|2014-03-14|IMPROVING IONIC ELECTROLYTE CONDUCTIVITY BASED ON IMIDAZOLATE LITHIUM SALTS|
    FR1454902A|FR3018519B1|2014-03-14|2014-05-30|IMPROVING IONIC ELECTROLYTE CONDUCTIVITY BASED ON IMIDAZOLATE LITHIUM SALTS|FR1454902A| FR3018519B1|2014-03-14|2014-05-30|IMPROVING IONIC ELECTROLYTE CONDUCTIVITY BASED ON IMIDAZOLATE LITHIUM SALTS|
    EP19170564.9A| EP3557677A1|2014-03-14|2015-03-09|Improving the ion conductivity of electrolyte based on lithium imidazolate salts|
    PCT/FR2015/050574| WO2015136201A1|2014-03-14|2015-03-09|Improving the ion conductivity of an electrolyte based on lithium imidazolate salts|
    KR1020167028387A| KR20160132961A|2014-03-14|2015-03-09|Improving the ion conductivity of an electrolyte based on lithium imidazolate salts|
    EP15713996.5A| EP3117479B1|2014-03-14|2015-03-09|Improving the ion conductivity of an electrolyte based on lithium imidazolate salts|
    CN201580014081.3A| CN106104894A|2014-03-14|2015-03-09|Improve the ionic conductance of electrolyte based on imidazoles lithium salts|
    JP2016574501A| JP2017510963A|2014-03-14|2015-03-09|Improvement of ionic conductivity of electrolytes based on lithium imidazolate salt|
    US15/125,793| US20170025709A1|2014-03-14|2015-03-09|Improving the ion conductivity of an electrolyte based on lithium imidazolate salts|
    CA2942197A| CA2942197A1|2014-03-14|2015-03-09|Improving the ion conductivity of an electrolyte based on lithium imidazolate salts|
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