JP2019046746A5 - - Google Patents
Download PDFInfo
- Publication number
- JP2019046746A5 JP2019046746A5 JP2017171369A JP2017171369A JP2019046746A5 JP 2019046746 A5 JP2019046746 A5 JP 2019046746A5 JP 2017171369 A JP2017171369 A JP 2017171369A JP 2017171369 A JP2017171369 A JP 2017171369A JP 2019046746 A5 JP2019046746 A5 JP 2019046746A5
- Authority
- JP
- Japan
- Prior art keywords
- electrolytic solution
- lithium
- lithium salt
- mol
- storage device
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000008151 electrolyte solution Substances 0.000 claims description 17
- 229910003002 lithium salt Inorganic materials 0.000 claims description 11
- 159000000002 lithium salts Chemical class 0.000 claims description 11
- 239000002608 ionic liquid Substances 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-O pyrrolidinium Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium Ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims 2
- -1 fluorosulfonyl Chemical group 0.000 claims 2
- 229910052744 lithium Inorganic materials 0.000 claims 2
- 239000003990 capacitor Substances 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 229910010941 LiFSI Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000002427 irreversible Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Description
すなわち、本イオン液体としては、アニオンとしてのＦＳＩ−と、カチオンとしてのイミダゾリウムまたはピロリジニウムとの塩が好ましく、具体的には、ＥＭＩｍＦＳＩ、およびＭＰＰｙｒＦＳＩ等が挙げられる。 That is, as the ionic liquid, a salt of FSI − as an anion and imidazolium or pyrrolidinium as a cation is preferable, and specific examples thereof include EMImFSI and MPPyr FSI.
中でも、（１）得られた電解液におけるイオン伝導性ならびに化学的および電気化学的な安定性が優れること、ならびに（２）当該電解液を有する蓄電デバイスにおける電気化学的特性が優れることから、ＬｉＦＳＩが好ましい。 Among them, LiFS is excellent because (1) the ionic conductivity and chemical and electrochemical stability of the obtained electrolytic solution are excellent, and (2) the electrochemical characteristics of the power storage device having the electrolytic solution are excellent. I is preferred .
これに対して、発明者らは、電解液中に一定濃度のＦＳＩアニオンが含まれる場合には、電解液中のリチウム塩の濃度を１．６ｍｏｌ／ｄｍ３以上としたとき、イオン伝導度が低下せず、むしろ上昇することを見出した。さらに、発明者らは、電解液中に一定濃度以上（具体的には蓄電に利用されるリチウムイオン量よりも過剰量）のリチウムイオンが存在する場合には、特異的な電池特性を示すことを見出した（Ｙａｍａｇａｔａ ｅｔ ａｌ．，Ｅｌｅｃｔｒｏｃｈｉｍ．Ａｃｔａ，１１０，１８１−１９０（２０１３））。 On the other hand, the inventors have stated that when the electrolytic solution contains a constant concentration of FSI anions, the ionic conductivity when the concentration of the lithium salt in the electrolytic solution is 1.6 mol / dm 3 or more. We found that did not decrease, but rather increased. Furthermore, the inventors show specific battery characteristics when a certain concentration or more (specifically, an excess amount of lithium ions is larger than the amount of lithium ions used for storage) is present in the electrolytic solution. Was found (Yamagata et al., Electrochim. Acta, 110, 181-190 (2013)).
最初に、イオン液体をＥＭＩｍＦＳＩ、リチウム塩をＬｉＦＳＩとした電解液中における、グラファイト負極の出力特性について、比較する。リチウム塩の濃度が本発明にて特定した濃度の範囲内である、実施例１および２は、一般的な有機電解液系を用いた比較例１、ならびにリチウム塩濃度が本発明の範囲外である、比較例２および３と比較して、高い出力特性が得られている。上述したように、一般的に、電解液に溶解するリチウム塩濃度が高いほど電解液のイオン伝導性が低下し、かつ、高粘性となる。そのため、電池性能（出力特性）はリチウム塩濃度の増加とともに低下する（よって通常、リチウム塩濃度は０．５〜１．５ｍｏｌ／ｄｍ３となっている）。表２を見ると、比較例２の方が実施例１、２よりも出力特性が高い場合があるが、不可逆容量成分を含み、かつ、大電流にすると出力特性が低下するために良い特性とは言えない。 First, the output characteristics of the graphite negative electrode in the electrolytic solution in which the ionic liquid is EMImFSI and the lithium salt is LiFSI are compared. Examples 1 and 2 in which the concentration of the lithium salt is within the range of the concentration specified in the present invention are Comparative Example 1 using a general organic electrolyte system, and the lithium salt concentration is outside the range of the present invention. Higher output characteristics are obtained as compared with certain Comparative Examples 2 and 3. As described above, in general, the higher the concentration of the lithium salt dissolved in the electrolytic solution, the lower the ionic conductivity of the electrolytic solution and the higher the viscosity. Therefore, the battery performance (output characteristics) decreases as the lithium salt concentration increases (therefore, the lithium salt concentration is usually 0.5 to 1.5 mol / dm 3 ). Looking at Table 2, Comparative Example 2 may have higher output characteristics than Examples 1 and 2, but it has good characteristics because it contains an irreversible capacitance component and the output characteristics deteriorate when a large current is applied. I can't say.
具体的には、ＴＦＳＩ系のイオン液体としてＭＰＰｙｒＴＦＳＩを採用し、これにＬｉＦＳＩを所定の濃度溶解させた電解液（ＬｉＦＳＩ／ＭＰＰｙｒＴＦＳＩ）を採用して評価した。充電および放電を１．０Ｃで行った場合の放電容量値は、電解液としてＬｉＦＳＩ／ＭＰＰｙｒＴＦＳＩを採用した実施例６、比較例１１および１２の中で、実施例６が圧倒的に高い。よって、電解液中のリチウム塩を、本発明において特定されている濃度の範囲内とすることによってもたらされる電池特性の特異性は、リチウム塩を溶解させるイオン液体を限定するものではないといえる。 Specifically, MPPyrTFSI was adopted as the TFSI-based ionic liquid, and an electrolytic solution (LiFSI / MPPyrTFSI ) in which LiFSI was dissolved at a predetermined concentration was adopted for evaluation. The discharge capacity value when charging and discharging are performed at 1.0 C is overwhelmingly higher in Example 6 among Examples 6 and Comparative Examples 11 and 12 in which LiFSI / MPPyrTFSI is adopted as the electrolytic solution. Therefore, it can be said that the specificity of the battery characteristics brought about by setting the lithium salt in the electrolytic solution within the concentration range specified in the present invention does not limit the ionic liquid that dissolves the lithium salt.
Claims (4)
上記電解液の総体積を基準として、上記リチウム塩を、１．６ｍｏｌ／ｄｍ３ 以上、３．０ｍｏｌ／ｄｍ３ 以下含み、
上記電解液の総体積を基準として、ビス（フルオロスルホニル）イミドアニオンを、１．６ｍｏｌ／ｄｍ３以上含むことを特徴とする、電解液。 An electrolytic solution containing an ionic liquid and a lithium salt.
Based on the total volume of the electrolytic solution contains the lithium salt, 1.6 mol / dm 3 or more, 3.0 mol / dm 3 or less,
An electrolytic solution containing 1.6 mol / dm 3 or more of bis (fluorosulfonyl) imide anion based on the total volume of the electrolytic solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017171369A JP6980256B2 (en) | 2017-09-06 | 2017-09-06 | Electrolyte and storage device using the electrolytic solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017171369A JP6980256B2 (en) | 2017-09-06 | 2017-09-06 | Electrolyte and storage device using the electrolytic solution |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2019046746A JP2019046746A (en) | 2019-03-22 |
| JP2019046746A5 true JP2019046746A5 (en) | 2020-10-08 |
| JP6980256B2 JP6980256B2 (en) | 2021-12-15 |
Family
ID=65814588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017171369A Active JP6980256B2 (en) | 2017-09-06 | 2017-09-06 | Electrolyte and storage device using the electrolytic solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6980256B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7099311B2 (en) * | 2018-12-26 | 2022-07-12 | Tdk株式会社 | Electrolyte for lithium secondary battery and lithium secondary battery |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010150679A1 (en) * | 2009-06-23 | 2010-12-29 | 株式会社 村田製作所 | Nonaqueous electrolyte secondary battery |
| US9225037B2 (en) * | 2010-03-19 | 2015-12-29 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Lithium secondary battery using ionic liquid |
| JP5994966B2 (en) * | 2011-09-07 | 2016-09-21 | 学校法人 関西大学 | Non-aqueous gel electrolyte, production method thereof, and use thereof |
| JP2015011823A (en) * | 2013-06-27 | 2015-01-19 | 住友電気工業株式会社 | Lithium battery |
| JP2015037024A (en) * | 2013-08-12 | 2015-02-23 | 住友電気工業株式会社 | Lithium ion secondary battery, charge-discharge system, and method for charge and discharge |
| US20160268064A1 (en) * | 2015-03-09 | 2016-09-15 | Semiconductor Energy Laboratory Co., Ltd. | Power storage device and electronic device |
| EP3150747A1 (en) * | 2015-09-29 | 2017-04-05 | Universite De Nantes | Functionalized current collector for electrochemical devices, with increased resistance to corrosion |
-
2017
- 2017-09-06 JP JP2017171369A patent/JP6980256B2/en active Active
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Mogensen et al. | Solubility of the solid electrolyte interphase (SEI) in sodium ion batteries | |
| JP6195236B2 (en) | Aluminum secondary battery | |
| JP7103376B2 (en) | Lithium ion capacitor | |
| JP6827232B2 (en) | Water-based secondary battery | |
| JP6765857B2 (en) | Lithium ion capacitor | |
| JP4684006B2 (en) | Fluorine-containing organic sulfonylimide salt electrolyte, electrolytic solution and electrochemical element using the same | |
| JP6271275B2 (en) | Non-aqueous organic electrolyte for lithium primary battery and lithium primary battery | |
| CN108933293B (en) | Phosphonium-based ionic liquids for lithium metal-based batteries | |
| WO2016111151A1 (en) | Non-aqueous electrolytic solution and power storage device using the same | |
| US7824800B1 (en) | Lithium-ion cell with a wide operating temperature range | |
| Kondo et al. | Concentrated sodium bis (fluorosulfonyl) amide aqueous electrolyte solutions for electric double-layer capacitors | |
| JP2019133914A (en) | Aqueous electrolyte with bis(fluorosulfonyl)imide salt electrolyte and ionic liquid system, and battery using the electrolyte system | |
| JP2019046746A5 (en) | ||
| JP2004134165A (en) | Nonaqueous electrolyte, and electrochemical device | |
| KR101628555B1 (en) | An anode of litium-air battery | |
| JP5987303B2 (en) | Electrochemical device using negative electrode containing magnesium element | |
| JP2016167476A (en) | Power storage device | |
| JP6449732B2 (en) | Electric double layer capacitor | |
| JP4678122B2 (en) | Nonaqueous electrolytes and electrochemical devices | |
| JP2016178199A (en) | Nonaqueous electrolyte solution and power storage device | |
| KR20160071200A (en) | Glyme liquid electrolyte composition for lithium air rechargeable | |
| Egashira | Capacitance Degradation in Hydrogel Electrolyte Containing Magnesium-ion Conducting Water-in-Salt Solution | |
| JP2002175948A (en) | Electric double-layer capacitor and nonaqueous electrolytic solution | |
| JP2016086153A (en) | Electrochemical device | |
| CN104701032A (en) | Preparation method of boron ionic liquid containing super capacitor |