JP2940706B2 - Non-aqueous electrolyte secondary battery - Google Patents
Non-aqueous electrolyte secondary batteryInfo
- Publication number
- JP2940706B2 JP2940706B2 JP2284631A JP28463190A JP2940706B2 JP 2940706 B2 JP2940706 B2 JP 2940706B2 JP 2284631 A JP2284631 A JP 2284631A JP 28463190 A JP28463190 A JP 28463190A JP 2940706 B2 JP2940706 B2 JP 2940706B2
- Authority
- JP
- Japan
- Prior art keywords
- aqueous electrolyte
- triflate
- lithium
- secondary battery
- electrolyte secondary
- 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 - Fee Related
Links
Classifications
-
- 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
Description
【発明の詳細な説明】 （イ） 産業上の利用分野 本発明は、マンガン酸化物、三酸化モリブデン、五酸
化バナジウム、チタン或いはニオブの硫化物やセレン化
物などを活物質とする再充電可能な正極と、リチウム或
いはリチウム合金を活物質とする負極と、非水電解液と
を備えた非水電解液二次電池に係り、特に電解液の改良
に関するものである。DETAILED DESCRIPTION OF THE INVENTION (a) Industrial Field of the Invention The present invention relates to a rechargeable battery using manganese oxide, molybdenum trioxide, vanadium pentoxide, titanium or niobium sulfide or selenide as an active material. The present invention relates to a non-aqueous electrolyte secondary battery including a positive electrode, a negative electrode using lithium or a lithium alloy as an active material, and a non-aqueous electrolyte, and particularly relates to improvement of an electrolyte.
（ロ） 従来の技術 この種二次電池では、放電時にイオンとなって溶出し
たリチウムが充電時に金属リチウムとして負極表面に電
析するのであるが、この電析リチウムは表面積の大なる
微粒子状であるため活性度が高く、そのため非水電解液
を構成する有機溶媒と反応して溶媒を分解し電解液を劣
化させたり、又、充放電をくり返すことにより負極表面
に電析リチウムがデンドライト状に生長し、これがセパ
レータをつきやぶり正極に接して内部短絡を引起こし、
それ故この種電池は充放電サイクル特性が悪いという問
題があった。(B) Conventional technology In this type of secondary battery, lithium eluted as ions during discharging is deposited on the negative electrode surface as metallic lithium during charging. The deposited lithium is in the form of fine particles having a large surface area. Due to its high activity, it reacts with the organic solvent that constitutes the non-aqueous electrolyte to decompose the solvent and degrade the electrolyte.Also, by repeating charge and discharge, the deposited lithium is dendritic on the negative electrode surface. This causes the separator to come into contact with the positive electrode, causing an internal short circuit,
Therefore, this type of battery has a problem that the charge / discharge cycle characteristics are poor.
（ハ） 発明が解決しようとする課題 本発明は上述せる従来技術の問題点に鑑み、非水電解
液を改良して充放電サイクル特性に優れた非水電解液二
次電池を提供しようとするものである。(C) Problems to be Solved by the Invention In view of the above-mentioned problems of the prior art, the present invention seeks to provide a nonaqueous electrolyte secondary battery having improved charge / discharge cycle characteristics by improving the nonaqueous electrolyte. Things.
（ニ） 課題を解決するための手段 本発明は再充電可能な正極と、リチウム或いはリチウ
ム合金からなる負極と、少なくとも一種の有機溶媒及び
少なくとも一種の溶質からなる非水電解液とを備えた非
水電解液二次電池において、前記非水電解液に共役基を
含む置換基を持つトリフラートを添加することを特徴と
する。ここで、前記共役基を含む置換基を持つトリフラ
ートとして、Ｎ−フルオロピリジニウムフラートとその
誘導体、或いはベンゼントリフラートとその誘導体より
選択された少なくとも１つを用いることができる。(D) Means for Solving the Problems The present invention provides a non-aqueous electrolyte comprising a rechargeable positive electrode, a negative electrode made of lithium or a lithium alloy, and a non-aqueous electrolytic solution made of at least one organic solvent and at least one solute. The aqueous electrolyte secondary battery is characterized in that a triflate having a substituent containing a conjugate group is added to the non-aqueous electrolyte. Here, as the triflate having a substituent containing a conjugate group, at least one selected from N-fluoropyridinium furate and its derivative, or benzene triflate and its derivative can be used.
（ホ） 作用 非水電解液に共役基を含む置換基を持つトリフラート
を添加すると、共役基を含む置換基を持つトリフラート
と負極活物質であるリチウムとが反応して、リチウム負
極表面にリチウムイオン導電性の高い被膜が生成し、充
電時に生成する活性な電析リチウムと非水電解液を構成
する有機溶媒との反応や、デンドライト状の電析リチウ
ムの発生による内部短絡が抑制される。この結果、非水
電解液の劣化や内部短絡が抑えられ充放電サイクル特性
の向上が図れる。(E) Action When a triflate having a substituent containing a conjugate group is added to the nonaqueous electrolyte, the triflate having a substituent containing the conjugate group reacts with lithium, which is a negative electrode active material, and lithium ion is formed on the surface of the lithium negative electrode. A highly conductive film is formed, and a reaction between active electrodeposited lithium generated at the time of charging and an organic solvent constituting the non-aqueous electrolyte and an internal short circuit due to generation of dendritic electrodeposited lithium are suppressed. As a result, the deterioration of the non-aqueous electrolyte and the internal short circuit are suppressed, and the charge / discharge cycle characteristics can be improved.
（ヘ） 実施例 以下に本発明の実施例につき詳述する。(F) Examples Hereinafter, examples of the present invention will be described in detail.
（実施例１〜12） 第１図は本発明の一実施例としての扁平型非水電解液
二次電池の半断面図を示す。１はリチウムよりなる負極
であり、負極缶２の内底面に固着せる負極集電体３に圧
着されている。４は正極であって、活物質であるマンガ
ン酸化物85重量％に導電剤としてアセチレンブラック10
重量％及び結着剤としてフッ素樹脂５重量％の割合で加
え、十分混合した後成型したものであり、正極缶５の内
底面に固着せる正極集電体６に圧着されている。７はポ
リプロピレン製多孔性膜よりなるセパレータであり、こ
れに第１表に示すような各種の混合有機溶媒と溶質との
組み合わせに、Ｎ−フルオロピリジニウムトリフラート
を1,000ppm添加した電解液が含浸されている。８は絶縁
パッキングであり、電池寸法は直径24.0mm、高さ3.0mm
である。そしてこの電池を本発明電池Ａ〜Ｌとした。(Examples 1 to 12) FIG. 1 is a half sectional view of a flat type nonaqueous electrolyte secondary battery as one example of the present invention. Reference numeral 1 denotes a negative electrode made of lithium, which is pressed to a negative electrode current collector 3 that is fixed to the inner bottom surface of a negative electrode can 2. Reference numeral 4 denotes a positive electrode, which is composed of 85% by weight of manganese oxide as an active material and acetylene black 10 as a conductive agent.
It is formed by adding and mixing the mixture at a ratio of 5% by weight of a fluororesin as a binder and 5% by weight of a fluororesin, and is pressed to a positive electrode current collector 6 fixed to the inner bottom surface of the positive electrode can 5. Reference numeral 7 denotes a separator made of a polypropylene porous membrane, which is impregnated with an electrolytic solution obtained by adding 1,000 ppm of N-fluoropyridinium triflate to a combination of various mixed organic solvents and solutes as shown in Table 1. I have. 8 is an insulating packing, the battery size is 24.0mm in diameter and 3.0mm in height
It is. These batteries were designated as batteries A to L of the present invention.
（比較例１〜12） 電解液にＮ−フルオロピリジニウムトリフラートを添
加しない以外は実施例１〜12と同様の比較電池ａ〜ｌを
作製した。 (Comparative Examples 1 to 12) Comparative batteries a to l were produced in the same manner as in Examples 1 to 12, except that N-fluoropyridinium triflate was not added to the electrolytic solution.
（実施例13） 非水電解液としてECとBCとDMEを1:1:2で混合した混合
溶媒に、溶質としてLiPF6を１モル／溶解したものを
用い、且つ添加剤としてＮ−フルオロピリジニウムトリ
フラートの代わりにＮ−フルオロ−2,4,6−トリメチル
ピリジニウムトリフラートを1,000ppm用いることを除い
て他は前記実施例と同様の電池を作製した。この電池を
Ｍとする。(Example 13) As a non-aqueous electrolyte, a mixture of EC, BC, and DME in a ratio of 1: 1: 2, in which 1 mol / dissolved LiPF 6 was used as a solute, and N-fluoropyridinium was used as an additive. A battery was manufactured in the same manner as in the above example except that 1,000 ppm of N-fluoro-2,4,6-trimethylpyridinium triflate was used instead of triflate. This battery is designated as M.
（実施例14） 非水電解液としてECとBCとDMEを1:1:2で混合した混合
溶媒に、容質としてLiPF6を１モル／溶解したものを
用い、且つ添加剤としてＮ−フルオロピリジニウムトリ
フラートの代わりにＮ−フルオロ−3,5−ジクロロピリ
ジニウムトリフラートを1,000ppm用いることを除いて他
は前記実施例１〜12と同様の電池を作製した。この電池
をＮとする。(Example 14) A mixture of EC, BC, and DME at a ratio of 1: 1: 2 as a non-aqueous electrolyte was prepared by dissolving LiPF 6 at a concentration of 1 mol / mol, and N-fluoro was used as an additive. Except that 1,000 ppm of N-fluoro-3,5-dichloropyridinium triflate was used in place of pyridinium triflate, batteries similar to those of Examples 1 to 12 were made except that 1,000 ppm of N-fluoro-3,5-dichloropyridinium triflate was used. This battery is designated as N.
第２表はこれら電池のサイクル数を示す。 Table 2 shows the number of cycles for these batteries.
尚、サイクル条件は充放電電流を2mA、充放電時間を
３時間とし、放電時間内に電池電圧が2.0Vに達した電池
を寿命とした。 Note that the cycle conditions were a charge / discharge current of 2 mA, a charge / discharge time of 3 hours, and a battery whose battery voltage reached 2.0 V within the discharge time.
第２表より明白なるように、本発明電池は比較電池に
比してサイクル特性が向上しているのがわかる。As is apparent from Table 2, the battery of the present invention has improved cycle characteristics as compared with the comparative battery.
尚、使用する共役基を含む置換基を持つトリフラート
の濃度は、100ppm以上であればその効果が得られるが、
特に500ppm〜3,000ppmの範囲で使用することが望まし
い。又、非水電解液を構成する有機溶媒或いは溶質につ
いては何ら制約されない。更に、本発明の骨子とする共
役系置換基を持つトリフラートとしては本実施例で示し
たＮ−フルオロピリジニウムトリフラート系以外に、例
えばベンゼントリフラート、キシレントリフラートのよ
うなベンゼン系置換基を含むものなどでも良い。Incidentally, the concentration of the triflate having a substituent containing a conjugate group to be used, if the concentration is 100 ppm or more, the effect can be obtained,
In particular, it is desirable to use it in the range of 500 ppm to 3,000 ppm. Further, the organic solvent or solute constituting the non-aqueous electrolyte is not limited at all. Further, as the triflate having a conjugated substituent as a framework of the present invention, in addition to the N-fluoropyridinium triflate shown in the present example, for example, benzene triflate, those containing a benzene-based substituent such as xylentriflate, etc. good.
（ト） 発明の効果 再充電可能な正極と、リチウム或いはリチウム合金を
活物質とする負極と、有機溶媒に少なくとも一つの溶質
を混合した非水電解液とを備える非水電解液二次電池に
おいて、非水電解液に共役基を含む置換基を持つトリフ
ラートを添加することにより、負極活物質であるリチウ
ムと共役基を含む置換基を持つトリフラートとが反応し
て、リチウム負極表面に被膜が生成し、活性な電析リチ
ウムと非水電解液を構成する有機溶媒との反応が抑制さ
れ、非水電解液の劣化を抑えることができるとともに、
充放電による負極表面における活性リチウムのデンドラ
イト状生長をも抑制でき、充放電サイクル特性の向上が
図れるものであり、この種電池の用途拡大に資するとこ
ろ極めて大である。(G) Effect of the Invention In a non-aqueous electrolyte secondary battery including a rechargeable positive electrode, a negative electrode using lithium or a lithium alloy as an active material, and a non-aqueous electrolyte obtained by mixing at least one solute in an organic solvent. By adding a triflate having a conjugate-containing substituent to the non-aqueous electrolyte, lithium as the negative electrode active material reacts with a triflate having a conjugate-containing substituent to form a film on the surface of the lithium negative electrode. The reaction between the active electrodeposited lithium and the organic solvent constituting the non-aqueous electrolyte is suppressed, and the deterioration of the non-aqueous electrolyte can be suppressed,
It can also suppress the dendrite-like growth of active lithium on the surface of the negative electrode due to charge / discharge, and can improve the charge / discharge cycle characteristics.
図は本発明の一実施例を示す扁平型非水系電解液二次電
池の半断面図を示す。 （１）……負極、（２）……負極缶、（３）……負極集
電体、（４）……正極、（５）……正極缶、（６）……
正極集電体、（７）……セパレータ、（８）……絶縁パ
ッキング。FIG. 1 is a half sectional view of a flat nonaqueous electrolyte secondary battery showing one embodiment of the present invention. (1) Negative electrode, (2) Negative electrode can, (3) Negative current collector, (4) Positive electrode, (5) Positive electrode can, (6)
Positive electrode current collector, (7) ... separator, (8) ... insulating packing.
Claims (2)
ム合金からなる負極と、少なくとも一種の有機溶媒及び
少なくとも一種の溶質からなる非水電解液とを備えた非
水電解液二次電池において、前記非水電解液に共役基を
含む置換基を持つトリフラートを添加したことを特徴と
する非水電解液二次電池。A non-aqueous electrolyte secondary battery comprising a chargeable positive electrode, a negative electrode made of lithium or a lithium alloy, and a non-aqueous electrolyte made of at least one organic solvent and at least one solute. A non-aqueous electrolyte secondary battery characterized in that a triflate having a substituent containing a conjugate group is added to the non-aqueous electrolyte.
トが、Ｎ−フルオロピリジニウムトリフラートとその誘
導体、或いはベンゼントリフラートとその誘導体より選
択された少なくとも１つであることを特徴とする請求項
記載の非水電解液二次電池。2. The method according to claim 1, wherein the triflate having a substituent containing a conjugate group is at least one selected from N-fluoropyridinium triflate and a derivative thereof, or benzene triflate and a derivative thereof. Non-aqueous electrolyte secondary battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2284631A JP2940706B2 (en) | 1990-10-22 | 1990-10-22 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2284631A JP2940706B2 (en) | 1990-10-22 | 1990-10-22 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04160766A JPH04160766A (en) | 1992-06-04 |
| JP2940706B2 true JP2940706B2 (en) | 1999-08-25 |
Family
ID=17680973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2284631A Expired - Fee Related JP2940706B2 (en) | 1990-10-22 | 1990-10-22 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2940706B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3760474B2 (en) * | 1993-04-22 | 2006-03-29 | ダイキン工業株式会社 | Method and apparatus for generating electric energy, and compound having NF bond used therefor |
| FR2767969B1 (en) * | 1997-08-29 | 1999-10-15 | Alsthom Cge Alcatel | LITHIUM RECHARGEABLE GENERATOR WITH ORGANIC ELECTROLYTE AND CARBON ANODE |
| KR101528375B1 (en) * | 2007-03-06 | 2015-06-11 | 우베 고산 가부시키가이샤 | tert-BUTYLPHENYL SULFONATE COMPOUND, NONAQUEOUS ELECTROLYTE SOLUTION FOR LITHIUM SECONDARY BATTERY USING THE SAME, AND LITHIUM SECONDARY BATTERY USING THE SAME |
-
1990
- 1990-10-22 JP JP2284631A patent/JP2940706B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04160766A (en) | 1992-06-04 |
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