JP3728791B2 - Electrolyte for lithium secondary batteries - Google Patents
Electrolyte for lithium secondary batteries Download PDFInfo
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- JP3728791B2 JP3728791B2 JP05608596A JP5608596A JP3728791B2 JP 3728791 B2 JP3728791 B2 JP 3728791B2 JP 05608596 A JP05608596 A JP 05608596A JP 5608596 A JP5608596 A JP 5608596A JP 3728791 B2 JP3728791 B2 JP 3728791B2
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- Prior art keywords
- electrolyte
- lithium secondary
- methanesulfonate
- electrolytic solution
- secondary battery
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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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Description
【０００１】
【発明の属する技術分野】
本発明はリチウム二次電池用の電解液に関するものであり、リチウム二次電池用の有機溶媒電解液のサイクル特性の改良に関するものである。
【０００２】
【従来の技術】
近年、電子機器の小型化、携帯化にともない、高エネルギー密度の電池の開発が求められている。その有力候補として、コークス、黒鉛等の炭素材料が、デンドライト状の電析リチウムの成長による内部短絡の危険性がないため、以前から提案されていた金属リチウム負極を用いたリチウム二次電池に変わる新しい負極材料として注目されている。
【０００３】
【発明が解決しようとする課題】
しかしながら、このような炭素材料を負極に用いた場合でも、充放電サイクルの進行とともに炭素負極上で電解液が分解して電池容量が次第に低下するという問題があった。また、炭素材料の黒鉛化度が高くなると、容量が大きくなる反面、電解液を分解しやすくなり、サイクル特性が悪くなるという傾向がある。
本発明は、以上の課題を解決するものであり、充放電サイクルの進行にともなう炭素電極上の分解が少ないリチウム二次電池用電解液を提供するものである。
【０００４】
【課題を解決するための手段】
本発明は、リチウム塩を溶質とし、これを溶解する有機溶媒および下式（Ｉ）で示されるメタンスルホン酸アルキル
【０００５】
【化２】
〔ただし、式中のＲ１ はメチル基、Ｒ２は炭素数１〜６のアルキル基を表す。〕
を含有するリチウム二次電池用電解液であって、電解液中に占める前式（Ｉ）で示されるメタンスルホン酸アルキルの濃度が０．１〜５０重量％であるリチウム二次電池用電解液を提供するものである。
【０００７】
【作用】
本発明においては、黒鉛等の炭素材料を電極材料として用いた場合に問題となる電解液の分解劣化を、当該電解液にメタンスルホン酸アルキルを所定量含有させ、電極表面上に皮膜を生成させて、電解液の分解を抑制し、サイクル特性の改善が実現できる。
【０００８】
【発明の実施の形態】
メタンスルホン酸アルキル：
本発明において、リチウム二次電池用電解液は、前記式（Ｉ）で示されるメタンスルホン酸アルキルを０．１〜５０重量％、好ましくは０．３〜１０重量％含有しており、このメタンスルホン酸アルキルが炭素負極と反応して、リチウムイオン透過性の高い皮膜を炭素電極表面に形成し、この皮膜が電解液の分解を抑制する。
かかるメタンスルホン酸アルキルとしては、メタンスルホン酸メチル、メタンスルホン酸エチル、メタンスルホン酸プロピル、メタンスルホン酸ブチルが例示される。
【０００９】
本発明において、メタンスルホン酸アルキルの電解液中に占める含有量が０．１〜５０重量％と限定されるのは、同含有量が０．１重量％未満の場合は、十分な厚さの皮膜が形成されないため、炭素電極表面上における電解液の分解を抑制できず、サイクル特性が十分に改善できないためである。一方、同含有量が５０重量％を越えた場合は、皮膜が厚くなりすぎてリチウムイオン透過性が悪くなるため、極板の反応抵抗が増大し、サイクル特性が低下するためである。
【００１０】
有機溶媒と溶質：
電解液の溶質及び溶媒については従来二次電池用電解液として提案及び使用されている種々の材料を用いることが可能である。
（有機溶媒）
有機溶媒としては、炭酸エチレン、炭酸プロピレン、炭酸ブチレン、炭酸ジメチル、炭酸エチルメチル、炭酸ジエチル、酢酸メチル、酢酸エチル、プロピオン酸メチル、プロピオン酸エチル、γ−ブチロラクトン、１，２−ジメトキシエタン、１，２−ジエトキシエタンから選ばれた単一溶媒あるいはこれらの複数の混合溶液が使用される。
（溶質）
溶質のリチウム塩としては、ＬｉＰＦ６、ＬｉＣｌＯ４、ＬｉＢＦ４、ＣＦ３ＳＯ３Ｌｉ、（ＣＦ３ＳＯ２）２ＮＬｉ、ＬｉＡｓＦ６などが利用できる。リチウム塩は、前記有機溶媒に溶解される。このリチウム塩よりなる溶質の電解液中の濃度は０．５〜１．５Ｍ（モル／リットル）である。
【００１１】
リチウム二次電池：
図１は、実施例及び比較例において作製した炭素電極を正極とするリチウム二次電池（コイン型；直径２０ｍｍ、厚さ１６ｍｍ）の断面図である。このコイン型セルは、ステンレス製ケース１、ステンレス製封口板２、天然黒鉛を銅シートに敷いた正極３、金属リチウムシートの負極４、有機溶媒電解液に浸された多孔性ポリプロピレンフィルムのセパレータ５、絶縁ガスケット６とから構成されている。
【００１２】
【実施例】
以下、本発明を実施例により詳細に説明する。
実施例１
図１に示すコイン型セル（リチウム二次電池）を作製した。
ここで、有機溶媒電解液は、炭酸エチレン（ＥＣ）２２．９ｇと炭酸プロピレン（ＰＣ）２１．０ｇを体積比５：５で混合した混合溶媒に、ＬｉＰＦ６ ５．６ｇを電解質として溶解させ、さらにメタンスルホン酸メチルを電解液中に０．５ｇ含有させたものを用いた。
電解液中のＬｉＰＦ６濃度は、１．０Ｍ（モル／リットル）で、メタンスルホン酸メチルの濃度は１重量％である。
【００１３】
実施例２
メタンスルホン酸アルキルとしてメタンスルホン酸エチルを用いたこと以外は実施例１と同様にしてコイン型セルを作製した。
比較例１
メタンスルホン酸アルキルを含有しない電解液として炭酸エチレン（ＥＣ）２３．１ｇと炭酸プロピレン（ＰＣ）２１．２ｇを体積比５：５で混合した混合溶媒に、ＬｉＰＦ６ ５．７ｇを溶解させたものを用いた外は、実施例１と同様にしてコイン型セルを作製した。
【００１４】
（サイクル特性の測定）
実施例１〜２および比較例１で得たコイン型セルについて、０．６１３ｍＡで放電終止電圧０．０Ｖまで放電した後、０．６１３ｍＡで充電終止電圧１．０Ｖまで充電して、各電解液を用いたコイン型セルのサイクル特性を調べた。その結果を図２に示す。
図２には、各電解液を用いたコイン型セルのサイクル特性を、縦軸に炭素材料１ｇ当たりの容量である炭素負極容量（ｍＡｈ／ｇ）を、横軸にサイクル数（回）をとったグラフを示した。同図が示すように本発明の電解液を用いたコイン型セルの炭素電極容量は、比較電解液を用いた場合と比べ、初期サイクルから大きい。
【００１５】
また図３で示すように、本発明の電解液を用いたコイン型セルの容量維持率（実施例１：９７％、実施例２：９９％）は、比較用の電解液を用いた場合の容量維持率（８５％）と比較して小さい。このことから、電解液に添加したメタンスルホン酸アルキルにより、炭素電極表面にリチウムイオン透過性の高い皮膜が生成し、充放電時の電解液の分解による容量低下が抑制されることがわかる。
上記実施例では、メタンスルホン酸アルキルとしてメタンスルホン酸メチル及びメタンスルホン酸エチルを用いた場合を例に説明したが、メタンスルホン酸プロピル、メタンスルホン酸ブチルなどの他のメタンスルホン酸アルキルを用いた場合にも同様な優れたサイクル特性を示す電解液を得ることができる。
【００１６】
【発明の効果】
リチウム二次電池用電解液に含まれるメタンスルホン酸アルキルが炭素電極の表面で反応し、リチウムイオン透過性の高い皮膜（保護膜）が形成され、電極表面における電解液の分解劣化が抑制される。そのため本発明の電解液を用いたコイン型セルは、充放電サイクルの進行と共に起きる容量劣化が小さいなど、優れた特有の効果を発現する。
【図面の簡単な説明】
【図１】 コイン型セルの断面図である。
【図２】 コイン型セルのサイクル特性を示すグラフである。
【図３】 コイン型セルの容量維持率を示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrolyte for a lithium secondary battery, and more particularly to an improvement in cycle characteristics of an organic solvent electrolyte for a lithium secondary battery.
[0002]
[Prior art]
2. Description of the Related Art In recent years, with the miniaturization and portability of electronic devices, development of batteries with high energy density has been required. As a promising candidate, carbon materials such as coke and graphite have no risk of internal short circuit due to the growth of dendritic electrodeposited lithium, so they have been replaced with lithium secondary batteries using metal lithium negative electrodes that have been proposed previously. It attracts attention as a new negative electrode material.
[0003]
[Problems to be solved by the invention]
However, even when such a carbon material is used for the negative electrode, there is a problem that the battery capacity gradually decreases due to decomposition of the electrolyte solution on the carbon negative electrode as the charge / discharge cycle progresses. In addition, when the degree of graphitization of the carbon material increases, the capacity increases, but the electrolyte solution is easily decomposed, and the cycle characteristics tend to deteriorate.
The present invention has been made to solve the above problems, and provides an electrolyte for a lithium secondary battery in which decomposition on a carbon electrode is small with progress of a charge / discharge cycle.
[0004]
[Means for Solving the Problems]
The present invention is a lithium salt as a solute, an organic solvent and the following equation which is dissolved alkyl methanesulfonate [0005] represented by the formula (I)
[Chemical 2]
Wherein R 1 represents a methyl group, and R 2 represents an alkyl group having 1 to 6 carbon atoms. ]
A electrolytic solution for lithium secondary batteries containing a lithium secondary battery electrolyte concentration of methanesulfonic acid alkyl is from 0.1 to 50% by weight of the formula before occupying in the electrolyte (I) Is to provide.
[0007]
[Action]
In the present invention, the decomposition deterioration of the electrolyte becomes a problem when using a carbon material such as graphite as the electrode material, it is contained a predetermined amount of methanesulfonic acid alkyl to the electrolyte solution, to produce a coating on the electrode surface Thus, decomposition of the electrolytic solution can be suppressed and cycle characteristics can be improved.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Methane sulfonic acid alkyl:
In the present invention, a lithium secondary battery electrolyte, 0.1 to 50 wt% of methanesulfonic acid alkyl represented by the formula (I), preferably are contained 0.3 to 10% by weight, the methane The alkyl sulfonate reacts with the carbon anode to form a film having high lithium ion permeability on the surface of the carbon electrode, and this film suppresses the decomposition of the electrolytic solution.
Such methanesulfonate alkyl, methyl methanesulfonate, ethyl methanesulfonate, methanesulfonic acid propyl, butyl methanesulfonate acid.
[0009]
In the present invention, the content of occupying in the electrolytic solution of methanesulfonic acid alkyl is limited 0.1 to 50% by weight, if the content is less than 0.1 wt%, a sufficient thickness This is because, since no film is formed, the decomposition of the electrolytic solution on the carbon electrode surface cannot be suppressed, and the cycle characteristics cannot be sufficiently improved. On the other hand, when the content exceeds 50% by weight, the film becomes too thick and the lithium ion permeability is deteriorated, so that the reaction resistance of the electrode plate is increased and the cycle characteristics are deteriorated.
[0010]
Organic solvents and solutes:
As for the solute and the solvent of the electrolytic solution, various materials conventionally proposed and used as the electrolytic solution for a secondary battery can be used.
(Organic solvent)
Examples of the organic solvent include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, 1,2-dimethoxyethane, 1 , 2-diethoxyethane, or a mixed solution of these.
(Solute)
As the solute lithium salt, LiPF 6 , LiClO 4 , LiBF 4 , CF 3 SO 3 Li, (CF 3 SO 2 ) 2 NLi, LiAsF 6 and the like can be used. The lithium salt is dissolved in the organic solvent. The concentration of the solute composed of this lithium salt in the electrolytic solution is 0.5 to 1.5 M (mol / liter).
[0011]
Lithium secondary battery:
FIG. 1 is a cross-sectional view of a lithium secondary battery (coin type; diameter: 20 mm, thickness: 16 mm) having a carbon electrode as a positive electrode manufactured in Examples and Comparative Examples. The coin-type cell includes a stainless steel case 1, a stainless
[0012]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples.
Example 1
A coin-type cell (lithium secondary battery) shown in FIG. 1 was produced.
Here, the organic solvent electrolyte was prepared by dissolving 5.6 g of LiPF 6 as an electrolyte in a mixed solvent in which 22.9 g of ethylene carbonate (EC) and 21.0 g of propylene carbonate (PC) were mixed at a volume ratio of 5: 5. Further, an electrolyte containing 0.5 g of methyl methanesulfonate was used.
The concentration of LiPF 6 in the electrolyte is 1.0 M (mol / liter), and the concentration of methyl methanesulfonate is 1% by weight.
[0013]
Example 2
A coin-type cell was produced in the same manner as in Example 1 except that ethyl methanesulfonate was used as the alkyl methanesulfonate.
Comparative Example 1
A solution obtained by dissolving 5.7 g of LiPF 6 in a mixed solvent in which 23.1 g of ethylene carbonate (EC) and 21.2 g of propylene carbonate (PC) are mixed at a volume ratio of 5: 5 as an electrolytic solution not containing alkyl methanesulfonate. A coin-shaped cell was produced in the same manner as in Example 1 except for using.
[0014]
(Measurement of cycle characteristics)
For the coin-type cells obtained in Examples 1 and 2 and Comparative Example 1, each of the electrolytes was discharged at 0.613 mA to a final discharge voltage of 0.0 V and then charged to a final charge voltage of 1.0 V at 0.613 mA. The cycle characteristics of a coin-shaped cell using the above were examined. The result is shown in FIG.
FIG. 2 shows the cycle characteristics of a coin-type cell using each electrolyte, the carbon negative electrode capacity (mAh / g) as the capacity per gram of carbon material on the vertical axis, and the number of cycles (times) on the horizontal axis. The graph is shown. As shown in the figure, the carbon electrode capacity of the coin cell using the electrolyte of the present invention is larger from the initial cycle than in the case of using the comparative electrolyte.
[0015]
Further, as shown in FIG. 3, the capacity retention rate (Example 1: 97%, Example 2: 99%) of the coin-type cell using the electrolytic solution of the present invention is the same as that when the comparative electrolytic solution is used. It is smaller than the capacity maintenance rate (85%). Therefore, the methanesulfonic acid alkyl added to the electrolytic solution, the lithium ion permeability high coating is produced on the carbon electrode surface, the capacity reduction due to decomposition of the electrolyte solution during charging and discharging is understood to be inhibited.
In the above embodiment, a case has been described with methyl methanesulfonate and ethyl methanesulfonate as methanesulfonic acid alkyl as an example, methanesulfonic acid propyl, another methanesulfonic acid alkyl such as methane sulfonic acid butyl using In such a case, an electrolytic solution having the same excellent cycle characteristics can be obtained.
[0016]
【The invention's effect】
Methanesulfonic acid alkyl contained in the electrolytic solution for lithium secondary battery reacts with the surface of the carbon electrode is a lithium-ion permeable high film (protective film) is formed, the decomposition deterioration of the electrolytic solution in the electrode surface can be suppressed . Therefore, the coin-type cell using the electrolytic solution of the present invention exhibits excellent unique effects such as a small capacity deterioration that occurs with the progress of the charge / discharge cycle.
[Brief description of the drawings]
FIG. 1 is a sectional view of a coin cell.
FIG. 2 is a graph showing cycle characteristics of a coin cell.
FIG. 3 is a graph showing a capacity retention ratio of a coin cell.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05608596A JP3728791B2 (en) | 1996-03-13 | 1996-03-13 | Electrolyte for lithium secondary batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05608596A JP3728791B2 (en) | 1996-03-13 | 1996-03-13 | Electrolyte for lithium secondary batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09245834A JPH09245834A (en) | 1997-09-19 |
| JP3728791B2 true JP3728791B2 (en) | 2005-12-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05608596A Expired - Fee Related JP3728791B2 (en) | 1996-03-13 | 1996-03-13 | Electrolyte for lithium secondary batteries |
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Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4448275B2 (en) | 2001-05-11 | 2010-04-07 | 三星エスディアイ株式会社 | ELECTROLYTE SOLUTION FOR LITHIUM SECONDARY BATTERY AND LITHIUM SECONDARY BATTERY CONTAINING THE SAME |
| KR100450199B1 (en) * | 2001-05-11 | 2004-09-24 | 삼성에스디아이 주식회사 | A non-aqueous electrolyte and a lithium secondary battery comprising the same |
| JP4863572B2 (en) * | 2001-05-22 | 2012-01-25 | 三井化学株式会社 | Non-aqueous electrolyte and secondary battery using the same |
| CN100385727C (en) | 2002-03-08 | 2008-04-30 | 三菱化学株式会社 | Nonaqueous electrolyte and lithium secondary battery employing the same |
| CN100585935C (en) | 2002-07-15 | 2010-01-27 | 宇部兴产株式会社 | Non-aqueous electrolyte and lithium cell |
| JP4449907B2 (en) | 2003-12-15 | 2010-04-14 | 日本電気株式会社 | Secondary battery electrolyte and secondary battery using the same |
| JP4725728B2 (en) | 2003-12-15 | 2011-07-13 | 日本電気株式会社 | Secondary battery |
| KR101347671B1 (en) | 2005-06-07 | 2014-01-03 | 히다치 막셀 가부시키가이샤 | A secondary battery with nonaqueous electrolyte |
| JP4876495B2 (en) * | 2005-09-13 | 2012-02-15 | ソニー株式会社 | Electrolyte for lithium ion secondary battery and lithium ion secondary battery |
| JP4951913B2 (en) * | 2005-09-27 | 2012-06-13 | ソニー株式会社 | Lithium ion secondary battery |
| JP5290819B2 (en) * | 2009-03-18 | 2013-09-18 | 日立マクセル株式会社 | Non-aqueous secondary battery |
| WO2011152534A1 (en) | 2010-06-04 | 2011-12-08 | 宇部興産株式会社 | Nonaqueous electrolyte solution and electrochemical element using same |
| JP6036298B2 (en) | 2010-10-18 | 2016-11-30 | 三菱化学株式会社 | Nonaqueous electrolyte for secondary battery and nonaqueous electrolyte battery using the same |
| CN108069884B (en) * | 2016-11-10 | 2020-01-17 | 宁德时代新能源科技股份有限公司 | Cyanovinyl sulfonate and synthesis method thereof |
| JP6518734B2 (en) * | 2017-08-03 | 2019-05-22 | 株式会社パワーフォー | Secondary battery |
| CN114846669A (en) | 2019-12-17 | 2022-08-02 | 三菱化学株式会社 | Nonaqueous electrolyte solution and energy device |
| CN113979454B (en) * | 2021-11-23 | 2023-09-26 | 山东永浩新材料科技有限公司 | Preparation method of alkali metal fluorosulfonate |
-
1996
- 1996-03-13 JP JP05608596A patent/JP3728791B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JPH09245834A (en) | 1997-09-19 |
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