JP2000077098A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JP2000077098A JP2000077098A JP10242729A JP24272998A JP2000077098A JP 2000077098 A JP2000077098 A JP 2000077098A JP 10242729 A JP10242729 A JP 10242729A JP 24272998 A JP24272998 A JP 24272998A JP 2000077098 A JP2000077098 A JP 2000077098A
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- electrolyte
- sulfolane
- formula
- battery
- 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.)
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Classifications
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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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、リチウム電池、リ
チウムイオン電池等の非水電解質電池に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte battery such as a lithium battery and a lithium ion battery.
【０００２】[0002]
【従来の技術】近年の携帯用電子機器の小型化に伴い、
高エネルギー密度を有するリチウム二次電池の需要が増
大している。また、電気自動車用等の大型電池への応用
も期待されており、これらの研究開発において、高エネ
ルギー密度化や大容量化の技術や安全性向上の技術の確
立は不可欠である。現在、新しい支持電解質の開発がリ
チウム二次電池の安全性および信頼性の観点から必要に
なってきている。なぜならば、リチウム二次電池の支持
電解質として最も多く用いられているＬｉＰＦ6は熱的
および化学的に安定であるとはいえず、新規支持電解質
を用いることにより、リチウム二次電池における安全性
および信頼性の改善、さらに充放電特性の改善が期待さ
れるからである。2. Description of the Related Art With the recent miniaturization of portable electronic devices,
Demand for lithium secondary batteries having high energy density is increasing. In addition, application to large batteries for electric vehicles and the like is also expected, and in these research and development, establishment of technologies for increasing energy density and capacity and for improving safety are indispensable. At present, development of a new supporting electrolyte is required from the viewpoint of safety and reliability of a lithium secondary battery. This is because LiPF 6, which is most frequently used as a supporting electrolyte for lithium secondary batteries, is not thermally and chemically stable, and by using a new supporting electrolyte, safety and safety in lithium secondary batteries can be improved. This is because improvement in reliability and further improvement in charge / discharge characteristics are expected.
【０００３】[0003]
【発明が解決しようとする課題】ＬｉＰＦ6 に変わる支
持電解質として、ＬｉＣＦ3 ＳＯ3 やＬｉＮ( ＳＯ2 Ｃ
Ｆ3 ）2 （ＬｉＴＦＳＩ）に代表される含フッ素有機物
アニオンからなる支持電解質が期待されている。ＬｉＣ
Ｆ3 ＳＯ3 やＬｉＴＦＳＩはＬｉＰＦ6 に比較して熱的
および化学的に安定であり、リチウム二次電池において
優れた特性を示すと考えられる。しかしながら、これら
含フッ素有機物アニオンを含む支持電解質を用いた場合
の問題点として、アルミニウム（Ａｌ）集電体の溶出が
挙げられる。例えば、プロピレンカーボネートやエチレ
ンカーボネートとジメチルカーボネート等の低粘度溶媒
との混合溶媒にＬｉＰＦ6 を溶解した電解液中において
Ａｌ金属は、リチウムの標準電極電位に対して４Ｖの電
位を印加した場合においても安定に存在する。しかしな
がら、前記混合溶媒にＬｉＣＦ3 ＳＯ3 やＬｉＴＦＳＩ
を溶解した電解液中においてＡｌ金属は、リチウムの標
準電極電位に対し４Ｖの電位を印加すると酸化電流が観
測され、Ａｌが溶出していると考えられる。Ａｌ金属は
非常に軽量であり、かつ安価であるため、広くリチウム
二次電池の集電体として用いられてきており、Ａｌの溶
出を抑制することがこれら含フッ素有機物アニオンから
なる支持電解質実用化における最大の課題である。As supporting electrolytes replacing LiPF 6 , LiCF 3 SO 3 and LiN (SO 2 C
A supporting electrolyte comprising a fluorine-containing organic anion represented by F 3 ) 2 (LiTFSI) is expected. LiC
F 3 SO 3 and LiTFSI are thermally and chemically stable compared to LiPF 6 , and are considered to exhibit excellent characteristics in a lithium secondary battery. However, a problem when using a supporting electrolyte containing these fluorine-containing organic anions is elution of an aluminum (Al) current collector. For example, in an electrolytic solution in which LiPF 6 is dissolved in a mixed solvent of propylene carbonate or ethylene carbonate and a low-viscosity solvent such as dimethyl carbonate, Al metal is applied even when a potential of 4 V is applied to a standard electrode potential of lithium. Present stably. However, the mixed solvent may be LiCF 3 SO 3 or LiTFSI
When an electric potential of 4 V with respect to the standard electrode potential of lithium is applied to the Al metal in the electrolytic solution in which is dissolved, an oxidation current is observed, and it is considered that Al is eluted. Since Al metal is extremely lightweight and inexpensive, it has been widely used as a current collector for lithium secondary batteries, and it is important to suppress the elution of Al to use a supporting electrolyte composed of these fluorine-containing organic anions. Is the biggest challenge in
【０００４】電解液中のＡｌの溶出において支持電解質
の及ぼす影響については明確ではないが、金村らによっ
て支持電解質の安定性が指摘されている（第２８回新電
池構想部会講演会予稿集ｐ．１）。ＬｉＰＦ6 を用いた
電解液中において５Ｖ（ｖｓ．Ｌｉ／Ｌｉ+ ）でアノー
ド分極した後のＡｌ電極表面には酸化物やフッ化物の存
在が確認され、ＸＰＳ（光電子分光）による深さ分析の
プロファイルから被膜の主成分がＡｌＦ3 に変化してい
るのに対し、ＬｉＣＦ3 ＳＯ3 を用いた場合においては
Ｏ元素が多く、比較的Ｆ元素が少ない。また、アノード
酸化処理を行う前と同様のスペクトルが処理後に観測さ
れていることから、Ａｌ金属表面に生成する酸化物およ
びフッ化物の不働態被膜の有無あるいは性質がＡｌ電極
の安定性に関係すると報告されている。ＬｉＣＦ3 ＳＯ
3 は安定であるためにＡｌ表面に不働態被膜を生成せ
ず、ＬｉＰＦ6 は分解することによりＡｌ表面に不働態
被膜を生成し、Ａｌ金属を安定化していると考えられ
る。Although the effect of the supporting electrolyte on the elution of Al in the electrolytic solution is not clear, Kanamura et al. Pointed out the stability of the supporting electrolyte (see p. 1). After anodic polarization at 5 V (vs. Li / Li + ) in an electrolyte using LiPF 6 , the presence of oxides and fluorides was confirmed on the surface of the Al electrode, and depth analysis by XPS (photoelectron spectroscopy) was performed. While the main component of the film changes from the profile to AlF 3 , when LiCF 3 SO 3 is used, the O element is large and the F element is relatively small. Further, since the same spectrum as before the anodic oxidation treatment was observed after the treatment, it was concluded that the presence or nature of the passive film of oxide and fluoride formed on the Al metal surface is related to the stability of the Al electrode. It has been reported. LiCF 3 SO
It is considered that No. 3 is stable and does not generate a passive film on the Al surface, and LiPF 6 decomposes to form a passive film on the Al surface to stabilize the Al metal.
【０００５】ＬｉＣＦ3 ＳＯ3 やＬｉＴＦＳＩ等の支持
電解質を用いた場合におけるＡｌの溶出は、Ｆの供給が
なく、Ａｌ金属表面に不働態被膜が生成されないためで
あるとの見解より、添加剤の検討が行われている。一例
として、ＨＦ水溶液の添加が挙げられ、十分ではないが
Ａｌの溶出が若干、抑制されることが確認されている。
しかしながら、このようなフッ素被膜を形成するような
添加剤は電池における充放電特性への影響が懸念され
る。[0005] The elution of Al when using a supporting electrolyte such as LiCF 3 SO 3 or LiTFSI is based on the view that no F is supplied and no passive film is formed on the Al metal surface. Considerations are being made. One example is the addition of an aqueous HF solution, and although not sufficient, it has been confirmed that the elution of Al is slightly suppressed.
However, there is a concern that an additive that forms such a fluorine film may affect the charge and discharge characteristics of the battery.
【０００６】そこで、含フッ素有機物アニオンを改良し
たＬｉＮ( ＳＯ2 Ｃ2 Ｆ5 ）2 やＬｉＮ( ＳＯ2 Ｃ
Ｆ3 ）( ＳＯ2 Ｃ4 Ｆ9 ）等の支持電解質が提案されて
いる。これらの支持電解質は被膜形成による安定化とは
異なるメカニズムによってＡｌの溶出を抑制していると
考えられる。このメカニズムについては明確ではない
が、アニオンのサイズが影響している可能性がある。Ｌ
ｉＣＦ3 ＳＯ3 やＬｉＴＦＳＩに比較して、これらの支
持電解質におけるアニオンのサイズは大きく、電荷密度
が低いと予想される。これによりＡｌを溶出する能力が
低下すると考えられる。あるいは、フルオロアルキル鎖
が長くなることにより立体障害的効果が現れている可能
性もある。しかしながら、アニオンのサイズが大きいほ
どＡｌの溶出抑制効果が大きいが、アニオンのサイズが
大きくなることにより移動度の低下が起こり、イオン伝
導度が低下するという問題点が残されている。Therefore, LiN (SO 2 C 2 F 5 ) 2 and LiN (SO 2 C
Supporting electrolytes such as F 3 ) (SO 2 C 4 F 9 ) have been proposed. It is considered that these supporting electrolytes suppress the elution of Al by a mechanism different from the stabilization by film formation. Although the mechanism is not clear, the size of the anion may have an effect. L
Compared to iCF 3 SO 3 and LiTFSI, it is expected that the size of the anion in these supporting electrolytes is large and the charge density is low. It is considered that this reduces the ability to elute Al. Alternatively, the steric hindrance effect may have appeared due to the longer fluoroalkyl chain. However, as the size of the anion is larger, the effect of suppressing the elution of Al is greater. However, there is a problem that the mobility of the anion increases due to the increase in the size of the anion, and the ion conductivity decreases.
【０００７】[0007]
【課題を解決するための手段】本発明では上述の含フッ
素有機物アニオンを含む支持電解質を含む電解液あるい
は高分子ゲル電解質にアクセプター数が１８．３よりも
大きな値を示す溶媒、具体的にはスルホラン又はスルト
ンに類似する構造を有する溶媒を加えることにより、Ａ
ｌの溶出を抑制することが可能となる。よって、熱的お
よび化学的に安定な支持電解質を用いることにより、安
全性および信頼性の高いリチウム二次電池を得ることが
できる。In the present invention, a solvent having an acceptor number larger than 18.3 in an electrolyte solution containing a supporting electrolyte containing a fluorine-containing organic anion or a polymer gel electrolyte, specifically, By adding a solvent having a structure similar to sulfolane or sultone, A
1 can be suppressed. Therefore, by using a thermally and chemically stable supporting electrolyte, a highly safe and reliable lithium secondary battery can be obtained.
【０００８】アクセプター数はV.GultmannによってThe
Donor-Acceptor Approch to Molecular Interactions,
Plenum Press(1978)で報告されている。Gultmannはアク
セプター数を１，２−ジクロロエタン中でその溶媒とト
リエチルホスフィンオキシドによって形成された付加物
の31Ｐ−ＮＭＲの化学シフトを用いて示しており、（Ｃ
2 Ｈ5 ）ＰＯ：ＳｂＣｌ5 の化学シフトを１００として
他の（Ｃ2 Ｈ5 ）ＰＯ：アクセプター溶媒の化学シフト
をアクセプター数（ＡＮ）と定義した。よって、ＡＮの
値が大きい溶媒ほど強くアニオンに配位すると予想され
る。即ち、電解液あるいは高分子ゲル電解質中で、溶媒
が含フッ素有機物アニオンに強く配位することによりＡ
ｌの溶出を抑制する効果があると考えられる。The number of acceptors was determined by V. Gultmann
Donor-Acceptor Approch to Molecular Interactions,
Plenum Press (1978). Gultmann shows the acceptor number using 31 P-NMR chemical shifts of the adduct formed by the solvent and triethylphosphine oxide in 1,2-dichloroethane, (C
2 H 5) PO: SbCl other chemical shifts of 5 as 100 (C 2 H 5) PO : defines the chemical shift of the acceptor solvent acceptor number and (AN). Therefore, it is expected that a solvent having a larger value of AN is more strongly coordinated to the anion. That is, in the electrolytic solution or the polymer gel electrolyte, the solvent is strongly coordinated to the fluorine-containing organic anion, so that A
It is considered that there is an effect of suppressing the elution of l.
【０００９】アクセプター数が１８．３より大きな値を
示す溶媒としてはジメチルホルムアミドなどのアミド
類、アセトニトリルなどのニトリル類等が挙げられる
が、リチウム二次電池に使用できる溶媒は多くなく、こ
れらのうちスルホラン又はスルトンに類似する構造を有
する溶媒において良好な電池特性が得られた。Examples of the solvent having an acceptor number larger than 18.3 include amides such as dimethylformamide and nitriles such as acetonitrile. However, there are not many solvents which can be used for lithium secondary batteries. Good battery characteristics were obtained in a solvent having a structure similar to sulfolane or sultone.
【００１０】[0010]
【発明の実施の形態】以下、本発明における非水電解質
電池について説明する。図１はＡｌの腐食を評価するた
めに用いたサイクリックボルタンメトリー用の評価セル
である。ａは作用極であり、１ｃｍ2 のＡｌ箔を用い
る。ｂおよびｃはそれぞれ対極、参照極であり、共にニ
ッケル板にリチウムを圧着したものである。ｄは非水電
解質であり、非水溶媒にリチウム塩を溶解した非水電解
液、あるいは非水溶媒、リチウム塩および高分子の複合
材料である高分子ゲル電解質を用いる。評価条件は３０
℃雰囲気、電位掃引速度０．１ｍＶ／ｓで行う。 （実施例１）非水電解液として、ＬｉＴＦＳＩを１ｍｏ
ｌ／ｌの濃度で溶解したスルホランを用いた。図１のセ
ルを用いてこの電解液のサイクリックボルタンメトリー
測定を行った。DESCRIPTION OF THE PREFERRED EMBODIMENTS The non-aqueous electrolyte battery according to the present invention will be described below. FIG. 1 shows an evaluation cell for cyclic voltammetry used for evaluating the corrosion of Al. a is a working electrode, and an Al foil of 1 cm 2 is used. b and c are a counter electrode and a reference electrode, respectively, both of which are obtained by pressing lithium on a nickel plate. d is a non-aqueous electrolyte, and uses a non-aqueous electrolyte in which a lithium salt is dissolved in a non-aqueous solvent, or a polymer gel electrolyte which is a composite material of a non-aqueous solvent, a lithium salt and a polymer. Evaluation condition is 30
C. atmosphere, at a potential sweep rate of 0.1 mV / s. (Example 1) 1 mol of LiTFSI was used as a non-aqueous electrolyte.
Sulfolane dissolved at a concentration of 1 / l was used. Cyclic voltammetry measurement of this electrolyte was performed using the cell of FIG.
【００１１】（比較例１）非水電解液として、ＬｉＴＦ
ＳＩを１ｍｏｌ／ｌの濃度で溶解したγ−ブチロラクト
ンを用い、図１のセルを用いてこの電解液のサイクリッ
クボルタンメトリー測定を行った。Comparative Example 1 LiTF was used as a non-aqueous electrolyte.
Using γ-butyrolactone in which SI was dissolved at a concentration of 1 mol / l, cyclic voltammetry measurement of this electrolytic solution was performed using the cell of FIG.
【００１２】図２に実施例１および比較例１のサイクリ
ックボルタンメトリー測定の結果を示す。比較例１で見
られる３．７Ｖ以上での酸化電流が実施例１では観測さ
れず、実施例１でＡｌの溶出が抑制されていることが確
認された。しかしながら、実施例１における電解液はイ
オン伝導度が低いため、スルホランと他の溶媒との混合
溶媒を用いる必要がある。混合に用いる溶媒にはエチレ
ンカーボネートやプロピレンカーボネート等の環状炭酸
エステル、γ−ブチロラクトン等の環状カルボン酸エス
テル、テトラヒドロフランや１，３−ジオキソラン等の
環状エーテル、１，２−ジメトキシエタン等の鎖状エー
テル、ジメチルカーボネートやエチルメチルカーボネー
ト等の鎖状炭酸エステル、プロピオン酸メチル等の鎖状
カルボン酸エステルなどが挙げられるが、これに限定さ
れるものではなく、また、２種類以上を混合することも
可能である。FIG. 2 shows the results of cyclic voltammetry measurements of Example 1 and Comparative Example 1. The oxidation current at 3.7 V or more observed in Comparative Example 1 was not observed in Example 1, and it was confirmed that the elution of Al was suppressed in Example 1. However, since the electrolyte in Example 1 has low ionic conductivity, it is necessary to use a mixed solvent of sulfolane and another solvent. Examples of the solvent used for mixing include cyclic carbonates such as ethylene carbonate and propylene carbonate, cyclic carboxylic esters such as γ-butyrolactone, cyclic ethers such as tetrahydrofuran and 1,3-dioxolan, and chain ethers such as 1,2-dimethoxyethane. Chain carbonates such as dimethyl carbonate and ethyl methyl carbonate, and chain carboxylate such as methyl propionate, but are not limited thereto, and two or more kinds can be mixed. It is.
【００１３】（実施例２）γ−ブチロラクトンとスルホ
ランを重量比１：４で混合した後、ＬｉＴＦＳＩを１ｍ
ｏｌ／ｌの濃度で溶解して電解液を調製した。図１のセ
ルを用いてこの電解液のサイクリックボルタンメトリー
測定を行った。(Example 2) After mixing γ-butyrolactone and sulfolane at a weight ratio of 1: 4, 1 m
The solution was dissolved at a concentration of ol / l to prepare an electrolytic solution. Cyclic voltammetry measurement of this electrolyte was performed using the cell of FIG.
【００１４】（実施例３）γ−ブチロラクトンとスルホ
ランを重量比２：３で混合した後、ＬｉＴＦＳＩを１ｍ
ｏｌ／ｌの濃度で溶解して電解液を調製した。図１のセ
ルを用いてこの電解液のサイクリックボルタンメトリー
測定を行った。Example 3 After mixing γ-butyrolactone and sulfolane at a weight ratio of 2: 3, 1 m of LiTFSI was added.
The solution was dissolved at a concentration of ol / l to prepare an electrolytic solution. Cyclic voltammetry measurement of this electrolyte was performed using the cell of FIG.
【００１５】（比較例２）非水電解液として、ＬｉＢＦ
4 を１ｍｏｌ／ｌの濃度で溶解したγ−ブチロラクトン
を用い、図１のセルを用いてこの電解液のサイクリック
ボルタンメトリー測定を行った。Comparative Example 2 LiBF was used as the non-aqueous electrolyte.
Using γ-butyrolactone in which 4 was dissolved at a concentration of 1 mol / l, cyclic voltammetry of this electrolytic solution was performed using the cell of FIG.
【００１６】図３に実施例１、２、３および比較例２の
サイクリックボルタンメトリー測定の結果を示す。γ−
ブチロラクトンの含有量が増加するにつれ、３．８Ｖ以
上での酸化電流値の増加が確認された。しかしながら、
酸化ピーク電流値は図２の比較例１よりも約１／１００
と小さく、Ａｌの溶出が抑制されていることが確認され
た。FIG. 3 shows the results of cyclic voltammetry measurements of Examples 1, 2, and 3 and Comparative Example 2. γ-
As the butyrolactone content increased, an increase in the oxidation current value at 3.8 V or higher was confirmed. However,
The oxidation peak current value is about 1/100 that of Comparative Example 1 in FIG.
It was confirmed that the elution of Al was suppressed.
【００１７】（実施例４および５）ジメチルカーボネー
トとスルホランをそれぞれ重量比で１：４および２：３
で混合した後、ＬｉＴＦＳＩを１ｍｏｌ／ｌの濃度で溶
解して電解液を調製した。表１に実施例１、２、３、４
および５の電解液を用いて２０℃におけるイオン伝導度
を測定した結果を示す。γ−ブチロラクトンあるいはジ
メチルカーボネートを加えることによりイオン伝導度の
向上が確認された。Examples 4 and 5 Dimethyl carbonate and sulfolane were used in a weight ratio of 1: 4 and 2: 3, respectively.
Then, LiTFSI was dissolved at a concentration of 1 mol / l to prepare an electrolytic solution. Table 1 shows Examples 1, 2, 3, and 4
5 shows the results of measuring the ionic conductivity at 20 ° C. using the electrolyte solutions of Examples 5 and 5. It was confirmed that the addition of γ-butyrolactone or dimethyl carbonate improved the ionic conductivity.
【００１８】[0018]
【表１】 [Table 1]
【００１９】また、高分子と実施例１〜５のような電解
液との複合体である高分子ゲル電解質においても同様な
Ａｌの溶出が抑制されていることが確認された。以下、
高分子ゲル電解質を用いた電池について説明する。図４
は評価に用いた電池であり、１はＡｌ集電体、２は正極
活物質、３は高分子ゲル電解質、４は負極活物質、５は
負極集電体、６は外装を示す。It was also confirmed that similar elution of Al was suppressed in the polymer gel electrolyte which was a composite of the polymer and the electrolytic solution as in Examples 1 to 5. Less than,
A battery using a polymer gel electrolyte will be described. FIG.
Denotes a battery used for evaluation, 1 denotes an Al current collector, 2 denotes a positive electrode active material, 3 denotes a polymer gel electrolyte, 4 denotes a negative electrode active material, 5 denotes a negative electrode current collector, and 6 denotes an exterior.
【００２０】（実施例６）高分子ゲル電解質として、ポ
リエーテル、ＬｉＴＦＳＩ、γ−ブチロラクトンおよび
スルホランからなる複合材料を用い、図４で示される電
池を用いて充放電サイクル試験を行った。γ−ブチロラ
クトンとスルホランの混合比は重量比で２：３とした。
正極活物質としてはＬｉＣｏＯ2 、負極活物質にはカー
ボンを用いた。充放電は１ｍＡの電流値で２．７〜４．
２Ｖの範囲で行った。Example 6 A charge / discharge cycle test was performed using a battery shown in FIG. 4 using a composite material composed of polyether, LiTFSI, γ-butyrolactone and sulfolane as a polymer gel electrolyte. The mixing ratio of γ-butyrolactone and sulfolane was 2: 3 by weight.
LiCoO 2 was used as the positive electrode active material, and carbon was used as the negative electrode active material. Charging / discharging is performed at a current value of 1 mA from 2.7 to 4.
The test was performed in the range of 2V.
【００２１】（比較例３）高分子ゲル電解質として、ポ
リエーテル、ＬｉＴＦＳＩ、γ−ブチロラクトンからな
る複合材料を用い、図４で示される電池を用いて充放電
サイクル試験を行った。正極活物質としてはＬｉＣｏＯ
2 、負極活物質にはカーボンを用いた。充放電は１ｍＡ
の電流値で２．７〜４．２Ｖの範囲で行った。Comparative Example 3 A charge / discharge cycle test was carried out using a battery shown in FIG. 4 by using a composite material composed of polyether, LiTFSI, and γ-butyrolactone as a polymer gel electrolyte. LiCoO as the positive electrode active material
2. Carbon was used as the negative electrode active material. Charge and discharge is 1mA
At a current value of 2.7 to 4.2 V.
【００２２】実施例６および比較例３における充放電サ
イクル試験の結果を図５に示す。比較例３では１サイク
ル目から放電容量が低く、電池の解体後Ａｌの腐食が確
認されたのに対し、実施例６では初期サイクルより高い
放電容量が得られ、サイクルを繰り返すことによる容量
劣化も小さい結果となった。また、電池の解体後Ａｌの
腐食は確認されなかった。FIG. 5 shows the results of the charge / discharge cycle test in Example 6 and Comparative Example 3. In Comparative Example 3, the discharge capacity was low from the first cycle, and corrosion of Al was confirmed after dismantling of the battery. On the other hand, in Example 6, a higher discharge capacity was obtained than in the initial cycle, and capacity deterioration due to repeated cycles was also observed. The result was small. Further, no corrosion of Al was confirmed after dismantling of the battery.
【００２３】[0023]
【発明の効果】以上説明したように、化１、化２あるい
は化３で示されるフッ素有機物アニオンからなる支持電
解質を用いた非水電解液あるいは高分子ゲル電解質にお
いて、スルホラン又はスルトンに類似する構造を有する
溶媒を含有することにより、リチウム電池の集電体に用
いられるＡｌの腐食が抑制される。したがって、ＬｉＰ
Ｆ6 やＬｉＢＦ4 に比較して熱的および化学的に安定で
ある含フッ素有機物アニオンからなるリチウム塩を用い
ることにより、安全性および信頼性に優れた二次電池を
提供できる。As described above, the structure similar to sulfolane or sultone in a non-aqueous electrolyte or a polymer gel electrolyte using a supporting electrolyte comprising a fluorine organic anion represented by Chemical Formula 1, Chemical Formula 2, or Chemical Formula 3 By containing a solvent having the following formula, corrosion of Al used for the current collector of the lithium battery is suppressed. Therefore, LiP
By using a lithium salt composed of a fluorine-containing organic anion that is more thermally and chemically stable than F 6 and LiBF 4 , a secondary battery excellent in safety and reliability can be provided.
【図１】サイクリックボルタンメトリー測定用セルの斜
視図である。FIG. 1 is a perspective view of a cell for cyclic voltammetry measurement.
【図２】各種電解液を用いた場合におけるＡｌ極のサイ
クリックボルタモグラムの比較図である。FIG. 2 is a comparison diagram of a cyclic voltammogram of an Al electrode when various electrolytic solutions are used.
【図３】各種電解液を用いた場合におけるＡｌ極のサイ
クリックボルタモグラムの比較図である。FIG. 3 is a comparison diagram of a cyclic voltammogram of an Al electrode when various electrolytic solutions are used.
【図４】評価に用いた電池の断面図である。FIG. 4 is a cross-sectional view of a battery used for evaluation.
【図５】充放電サイクル試験におけるサイクル数と放電
容量との関係図である。FIG. 5 is a relationship diagram between the number of cycles and a discharge capacity in a charge / discharge cycle test.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０１Ｍ 6/16 Ｈ０１Ｍ 6/16 Ａ Ｆターム(参考） 4C023 AA01 5H017 AA03 AS02 CC03 EE05 5H024 AA01 CC04 DD15 EE01 FF23 GG00 HH01 5H029 AJ12 AJ13 AK03 AL06 AM00 AM16 DJ07 DJ09 EJ01 EJ11 HJ01 HJ02 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) H01M 6/16 H01M 6/16 A F term (Reference) 4C023 AA01 5H017 AA03 AS02 CC03 EE05 5H024 AA01 CC04 DD15 EE01 FF23 GG00 HH01 5H029 AJ12 AJ13 AK03 AL06 AM00 AM16 DJ07 DJ09 EJ01 EJ11 HJ01 HJ02
Claims (3)
を正極の集電体とする電池において、電解液あるいは高
分子ゲル電解質が、化１、化２あるいは化３で示される
化合物のうち少なくとも一つを含み、且つスルホラン又
はスルトンに類似する構造を有する溶媒を主溶媒とする
ことを特徴とする非水電解質電池。 【化１】 【化２】 【化３】 （式中Ｒｆ１〜６は−Ｆ、−Ｃk Ｆ2k+1、−ＯＣm Ｈ2m
Ｃn Ｆ2n+1であり、ｋ＝１〜５、ｍ＝１あるいは２、ｎ
＝１〜５である。）1. A battery using aluminum or an aluminum alloy as a positive electrode current collector, wherein the electrolytic solution or the polymer gel electrolyte contains at least one of the compounds represented by Chemical Formula 1, Chemical Formula 2, or Chemical Formula 3, and A non-aqueous electrolyte battery comprising, as a main solvent, a solvent having a structure similar to sulfolane or sultone. Embedded image Embedded image Embedded image (Wherein Rf1~6 is -F, -C k F 2k + 1 , -OC m H 2m
C n F 2n + 1 , k = 1 to 5, m = 1 or 2, n
= 1-5. )
構造を有する溶媒の全溶媒中における含有量が、重量部
で６０％以上であることを特徴とする請求項１記載の非
水電解質電池。2. The nonaqueous electrolyte battery according to claim 1, wherein the content of the solvent having a structure similar to sulfolane or sultone in all solvents is 60% or more by weight.
構造を有する溶媒が、化４および／または化５で示され
る化合物であることを特徴とする請求項１記載の非水電
解質電池。 【化４】 【化５】 （式中Ｒ１〜１４は、−Ｈまたは−ＣＨ3 である。）3. The non-aqueous electrolyte battery according to claim 1, wherein the solvent having a structure similar to sulfolane or sultone is a compound represented by Chemical Formula 4 and / or Chemical Formula 5. Embedded image Embedded image (Wherein R1~14 is -H or -CH 3.)
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|---|---|---|---|
| JP24272998A JP4281030B2 (en) | 1998-08-28 | 1998-08-28 | Non-aqueous electrolyte battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24272998A JP4281030B2 (en) | 1998-08-28 | 1998-08-28 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000077098A true JP2000077098A (en) | 2000-03-14 |
| JP4281030B2 JP4281030B2 (en) | 2009-06-17 |
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ID=17093388
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|---|---|---|---|
| JP24272998A Expired - Fee Related JP4281030B2 (en) | 1998-08-28 | 1998-08-28 | Non-aqueous electrolyte battery |
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