JP2654552B2 - Electrolyte for lithium secondary battery - Google Patents
Electrolyte for lithium secondary batteryInfo
- Publication number
- JP2654552B2 JP2654552B2 JP63116410A JP11641088A JP2654552B2 JP 2654552 B2 JP2654552 B2 JP 2654552B2 JP 63116410 A JP63116410 A JP 63116410A JP 11641088 A JP11641088 A JP 11641088A JP 2654552 B2 JP2654552 B2 JP 2654552B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- electrolyte
- secondary battery
- lithium secondary
- electrolytic solution
- 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.)
- Expired - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Description
【発明の詳細な説明】 〔産業上利用分野〕 本発明はリチウム二次電池用電解液、さらに詳細には
リチウム金属及びリチウム合金を負極活物質とする電池
に用いられる非水電解液に関するものである。Description: TECHNICAL FIELD The present invention relates to an electrolyte for a lithium secondary battery, and more particularly to a non-aqueous electrolyte used for a battery using lithium metal and a lithium alloy as a negative electrode active material. is there.
リチウム金属或いはリチウム合金を負極活物質として
用いる電池では、LiClO4、LiBF4、LiAsF6、LiPF6、LiCF
3SO3等のリチウム塩を、非水溶媒（例えば、プロピレン
カーボネート、γ−ブチロラクトン、テトラヒドロフラ
ン及びその誘導体、1,3ジオキソラン及びその誘導体、
ジアルコキシエタン類、さらにはSOCl2等）に溶解させ
た電解液が用いられている。For batteries using lithium metal or lithium alloy as the negative electrode active material, LiClO 4 , LiBF 4 , LiAsF 6 , LiPF 6 , LiCF
A lithium salt such as 3 SO 3 is converted to a non-aqueous solvent (for example, propylene carbonate, γ-butyrolactone, tetrahydrofuran and its derivatives, 1,3 dioxolane and its derivatives,
An electrolytic solution dissolved in dialkoxyethanes, and further, SOCl 2 or the like is used.
しかしこれらのリチウム塩は、合成の段階や保存中の
分解反応により酸性不純物を含む場合があり、この酸性
不純物はリチウム二次電池の充放電サイクル特性を劣化
させる要因となることが知られている。また、溶質を溶
媒に溶解させる際に発生する熱による分解でも、この酸
性不純物が生成することが知られており、電解液の調製
には注意が必要である。However, these lithium salts sometimes contain acidic impurities due to a decomposition reaction during the synthesis stage or during storage, and these acidic impurities are known to be a factor that deteriorates the charge / discharge cycle characteristics of the lithium secondary battery. . In addition, it is known that this acidic impurity is also generated by decomposition caused by heat generated when a solute is dissolved in a solvent, and thus care must be taken in preparing an electrolytic solution.
電解液中の酸性不純物を除去する方法としては、Li2C
O3,LiF等のリチウム塩を電解液に混入する方法や、アミ
ン類を添加剤として電解液に加える方法などが知られて
いる。しかし前者は電解液に対する溶解度が極めて低い
ため、効果が少なく、後者はアミン類とリチウムの反応
が起こるため好ましくないという欠点があった。As a method for removing acidic impurities in the electrolytic solution, Li 2 C
There are known a method of mixing a lithium salt such as O 3 and LiF into an electrolytic solution, and a method of adding an amine as an additive to an electrolytic solution. However, the former has a drawback that the solubility is very low in the electrolytic solution, and thus the effect is small, and the latter has a disadvantage that the reaction between amines and lithium occurs, which is not preferable.
本発明は、上述の問題点に鑑みなされたものであり、
電解液中に含まれる酸性不純物を有機リチウム化合物を
添加して反応させることによって除去し、特性の優れた
リチウム二次電池用電解液を供することにある。The present invention has been made in view of the above problems,
An object of the present invention is to provide an electrolyte solution for a lithium secondary battery having excellent characteristics by removing acidic impurities contained in the electrolyte solution by adding and reacting an organic lithium compound.
上述の問題点を解決するため、本発明によるリチウム
二次電池用電解液は、リチウム塩を有機溶媒に溶解させ
たリチウム二次電池用電解液において、Ｒ−Lixで表さ
れる有機リチウム化合物（Ｒはアルキル、アリル、アリ
ール、ベンジル、ベンゾイル基、ｘは１以上）を添加す
ることを特徴としている。In order to solve the above-mentioned problems, an electrolyte for a lithium secondary battery according to the present invention is an electrolyte for a lithium secondary battery in which a lithium salt is dissolved in an organic solvent, and an organic lithium compound represented by R-Lix ( R is an alkyl, allyl, aryl, benzyl, benzoyl group, and x is 1 or more).
本発明によるリチウム二次電池用電解液によれば、電
解液中に含まれる酸性不純物を有機リチウム化合物によ
り除去するため、特性の優れたリチウム二次電池用電解
液とすることができるという利点がある。ADVANTAGE OF THE INVENTION According to the electrolyte solution for a lithium secondary battery according to the present invention, since an acidic impurity contained in the electrolyte solution is removed by an organic lithium compound, there is an advantage that an electrolyte solution for a lithium secondary battery having excellent characteristics can be obtained. is there.
本発明をさらに詳しく説明する。 The present invention will be described in more detail.
本発明によれば、Ｒ−Lixで表される有機リチウム化
合物（Ｒはアルキル、アリル、アリール、ベンジル、ベ
ンゾイル等の基、ｘは１以上）を電解液に添加して、電
解液中に存在する酸性不純物と反応させ、これを除去す
ることを特徴としている。According to the present invention, an organic lithium compound represented by R-Lix (R is a group such as alkyl, allyl, aryl, benzyl, benzoyl, etc., and x is 1 or more) is added to the electrolytic solution to be present in the electrolytic solution. It is characterized by reacting with acidic impurities and removing it.
これらの有機リチウム化合物は、電解液中の酸性不純
物（A+）と次のような反応を行い、 Ｒ−Li＋A+→Ｒ−Ａ＋Li+ 酸性不純物が電解液を劣化させたり、電池作製時にリチ
ウム金属と反応することを防げると期待される。These organolithium compounds, acidic impurities in the electrolyte solution (A +) perform following reaction, R-Li + A + → R-A + or Li + acidic impurities degrade the electrolytic solution, a lithium metal during battery production It is expected to be able to prevent reacting with.
前述の式において、Ｒはアルキル、アリル、アリー
ル、ベンジル、ベンゾイル基である。これらの基を有す
る有機リチウム化合物は、上述のように酸と反応すると
ともに、リチウムとは余り反応せず、かつリチウム二次
電池に使用される溶媒に溶解するからである。In the above formula, R is an alkyl, allyl, aryl, benzyl, benzoyl group. This is because the organolithium compound having these groups reacts with an acid as described above, does not significantly react with lithium, and is dissolved in a solvent used for a lithium secondary battery.
従来の方法と異なり、有機リチウム化合物は電解液に
よく溶け、かつ正極活物質と反応してこれを劣化させる
ことがないため、電解液中の酸性不純物を除去する方法
としては優れている。従って、有機リチウム化合物とし
ては、常温で液体または固体であり、リチウムに対する
電位がリチウム電池の実用上の終始電圧よりも低いこと
が望ましい。Unlike the conventional method, the organic lithium compound is well-dissolved in the electrolytic solution and does not react with the positive electrode active material to deteriorate it, so that it is an excellent method for removing acidic impurities in the electrolytic solution. Therefore, it is desirable that the organic lithium compound is liquid or solid at room temperature, and that the potential with respect to lithium is lower than the practical voltage of the lithium battery.
このような有機リチウム化合物の添加量は、電解液の
作製条件や材料の純度などによって左右されるが、酸性
不純物の２倍当量以下の量であることが好ましい。２倍
当量を越えると、粘度が上昇したり、好ましくない副反
応を生じて、電気的特性を悪化させる恐れを生じるから
である。The amount of the organic lithium compound to be added depends on the conditions for preparing the electrolytic solution, the purity of the material, and the like, but is preferably equal to or less than twice the equivalent of the acidic impurity. If the equivalent is more than twice, the viscosity may increase or an undesired side reaction may occur, which may deteriorate the electrical characteristics.
以下実施例について説明する。 Hereinafter, embodiments will be described.
〔実施例１〕 ２−メチルテトラヒドロフラン（以下、2MeTHFと略
す）とエチレンカーボネート（以下、ECと略す）の1:1
混合溶媒に６フッ化ヒ酸リチウム（LiAsF6）を溶解さ
せ、1M溶液とした。これにペンタフルオロフェニルリチ
ウム（Li−PFP）をそれぞれ0.001,0.01,0.1,1M溶かして
電解液試料とした。これらの電解液の特性は第１図に示
すコイン型電池における充放電サイクルの効率から評価
した。[Example 1] 1: 1 of 2-methyltetrahydrofuran (hereinafter abbreviated as 2MeTHF) and ethylene carbonate (hereinafter abbreviated as EC)
Lithium hexafluoroarsenate (LiAsF 6 ) was dissolved in the mixed solvent to obtain a 1M solution. Into this, 0.001, 0.01, 0.1, and 1M of pentafluorophenyllithium (Li-PFP) were dissolved to prepare electrolyte samples. The characteristics of these electrolytes were evaluated from the efficiency of the charge / discharge cycle in the coin-type battery shown in FIG.
すなわち、負極ケース１内にリチウム負極２を取り付
けるとともにセパレータ３および電解液５を介してSUS
板７を設け、これを電池ケース６と前記負極ケース１と
でガスケット４を介して一体化した電池である。That is, the lithium negative electrode 2 is mounted in the negative electrode case 1 and the SUS is inserted through the separator 3 and the electrolyte 5.
This is a battery in which a plate 7 is provided, and this is integrated with a battery case 6 and the negative electrode case 1 via a gasket 4.
結果を第２図に示す。 The results are shown in FIG.
図から判るように、充放電の効率は0.001Mで最大値を
示した。これは電解液からLi−PFPと反応する酸性の不
純物が除去されることにより充放電効率は向上するが、
未反応のLi−PFPが多くなるに従って、電解液の粘度が
大きくなり見かけ上充放電効率が減少するものと考えら
れる。従って、Li−PFPの最適量は電解液の作製条件や
材料の純度に依存し、本実施例で規定されるものではな
い。As can be seen from the figure, the charge / discharge efficiency showed the maximum value at 0.001M. This is because the removal of acidic impurities that react with Li-PFP from the electrolyte improves the charge and discharge efficiency,
It is considered that as the amount of unreacted Li-PFP increases, the viscosity of the electrolytic solution increases and the charge / discharge efficiency apparently decreases. Therefore, the optimum amount of Li-PFP depends on the preparation conditions of the electrolytic solution and the purity of the material, and is not specified in this embodiment.
〔実施例２〕 実施例１で示した1.5MのLiAsF6を含むECと2MeTHFの混
合溶媒系電解液に、各々0.001,0.01,0,1,1Mの１−リチ
ウムナフタレン（Li−Naph）を添加してリチウム充放電
効率の測定を行った。結果は、実施例１と同様に0.001M
添加による特性が最も良かった。A mixed solvent electrolyte of Example 2 EC and 2MeTHF including LiAsF 6 of 1.5M shown in Example 1, each 0.001,0.01,0,1,1M 1-lithium naphthalene (Li-Naph) The lithium charge / discharge efficiency was measured after addition. The result was 0.001M as in Example 1.
The characteristics by addition were the best.
〔実施例３〕 実施例１で示した1.5MのLiAsF6を含むECと2MeTHFの混
合溶媒系電解液に、各々0.001,0.01,0.1,1Mのベンジル
リチウム（Li−Bz）を添加して、リチウム充放電効率の
測定を行った。結果は、実施例１と同様に0.001M添加に
よる特性が最も良かった。Example 3 0.001, 0.01, 0.1, and 1 M benzyllithium (Li-Bz) were added to the mixed solvent-based electrolyte of EC and 2MeTHF containing 1.5 M LiAsF 6 shown in Example 1, respectively. Lithium charge / discharge efficiency was measured. As a result, as in Example 1, the characteristics obtained by adding 0.001M were the best.
〔実施例４〕 ２−MeTHF,ECの混合溶媒を10℃に冷却し、６フッ化リ
ン酸リチウム（LiPF6）の1.5M溶液を作製する。これにL
i−PFPをそれぞれ0.001,0.01,0.1,1M溶解して電解液を
作製し、その特性を評価した。結果は、第３図に示す様
に、0.01M Li−PFPを添加したもので特性が最も良かっ
た。Example 4 A mixed solvent of 2-MeTHF and EC was cooled to 10 ° C. to prepare a 1.5 M solution of lithium hexafluorophosphate (LiPF 6 ). L
Electrolytic solutions were prepared by dissolving 0.001, 0.01, 0.1, and 1 M of i-PFP, respectively, and their characteristics were evaluated. As a result, as shown in FIG. 3, the characteristics were the best when 0.01M Li-PFP was added.
以上説明したように、有機リチウム化合物を電解液に
添加することにより、電解液中に存在する酸性不純物を
除去でき、リチウム二次電池の充放電効率を向上させる
ことができる。As described above, by adding the organic lithium compound to the electrolytic solution, acidic impurities present in the electrolytic solution can be removed, and the charge and discharge efficiency of the lithium secondary battery can be improved.
第１図は特性試験に用いたコイン型電池の構造、第２図
はLiAsF6/EC,2MeTHFにLi−PFPを添加した時の電解液特
性、第３図はLiPF6/EC,2MeTHFにLi−PFPを添加した時の
電解液特性である。Structure of the coin-type battery using the first figure in characteristic test, the electrolyte characteristics when FIG. 2 with the addition of Li-PFP LiAsF 6 / EC, in 2MeTHF, FIG. 3 is LiPF 6 / EC, Li in 2MeTHF -It is an electrolyte solution characteristic when PFP is added.
Claims (1)
ム二次電池用電解液において、Ｒ−Lixで表される有機
リチウム化合物（Ｒはアルキル、アリル、アリール、ベ
ンジル、ベンゾイルで示される基、ｘは１以上）を添加
することを特徴とするリチウム二次電池用電解液。An organic lithium compound represented by R-Lix (R is a group represented by alkyl, allyl, aryl, benzyl, benzoyl, etc.) in a lithium secondary battery electrolyte obtained by dissolving a lithium salt in an organic solvent. wherein x is 1 or more).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63116410A JP2654552B2 (en) | 1988-05-13 | 1988-05-13 | Electrolyte for lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63116410A JP2654552B2 (en) | 1988-05-13 | 1988-05-13 | Electrolyte for lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01286262A JPH01286262A (en) | 1989-11-17 |
| JP2654552B2 true JP2654552B2 (en) | 1997-09-17 |
Family
ID=14686375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63116410A Expired - Lifetime JP2654552B2 (en) | 1988-05-13 | 1988-05-13 | Electrolyte for lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2654552B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5846673A (en) * | 1996-12-09 | 1998-12-08 | Valence Technology, Inc. | Additive to stabilize electrochemical cell |
| US6383688B1 (en) * | 1997-12-26 | 2002-05-07 | Tonen Corporation | Electrolyte for lithium cells and method of producing the same |
| AUPQ253099A0 (en) * | 1999-08-30 | 1999-09-23 | Energy Storage Systems Pty Ltd | A charge storage device |
| CN102005607B (en) | 2009-08-28 | 2014-02-05 | 夏普株式会社 | Non-aqueous electrolyte battery |
| JP5862853B2 (en) | 2011-05-11 | 2016-02-16 | ソニー株式会社 | Lithium ion secondary battery, electronic equipment, electric tool, electric vehicle, and power storage system |
| JP7303156B2 (en) * | 2019-09-12 | 2023-07-04 | トヨタ自動車株式会社 | Capacity recovery method for non-aqueous electrolyte secondary battery |
| JP7655668B2 (en) * | 2020-12-04 | 2025-04-02 | トヨタ自動車株式会社 | Electrolyte-containing liquid composition, method for producing electrolyte-containing liquid composition, and method for restoring capacity of non-aqueous electrolyte secondary battery |
| JP7569719B2 (en) * | 2021-03-12 | 2024-10-18 | 株式会社豊田中央研究所 | Recovery agent, recovery method for non-aqueous electrolyte secondary battery, and manufacturing method for non-aqueous electrolyte secondary battery |
-
1988
- 1988-05-13 JP JP63116410A patent/JP2654552B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01286262A (en) | 1989-11-17 |
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| EXPY | Cancellation because of completion of term |