JP5245373B2 - Non-aqueous electrolyte battery - Google Patents
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Description
本発明は非水電解質電池に関するもので、特に、非水電解質電池に用いる非水電解質に関する。 The present invention relates to a non-aqueous electrolyte battery, and more particularly to a non-aqueous electrolyte used for a non-aqueous electrolyte battery.
近年、高性能化、小型化が進む電子機器用電源、電力貯蔵用電源、移動体用電源等として、リチウム二次電池に代表される非水電解質電池が注目されている。特に、すでに実用化されている電子機器用電源以外の非水電解質電池の用途として、ハイブリッド自動車や電気自動車等の移動体用電源への適用が望まれているが、これら移動体用電源に非水電解質電池を用いるためには、高エネルギー密度であるだけでなく出力特性に優れた電池が強く要求されている。 In recent years, non-aqueous electrolyte batteries typified by lithium secondary batteries have attracted attention as power supplies for electronic equipment, power storage power supplies, power supplies for mobile bodies, and the like that have been improved in performance and size. In particular, as non-electrolyte battery applications other than power supplies for electronic devices that have already been put to practical use, application to mobile power supplies such as hybrid vehicles and electric vehicles is desired. In order to use a water electrolyte battery, a battery having not only high energy density but also excellent output characteristics is strongly demanded.
リチウム二次電池は、一般に、正極集電体と正極活物質を主要構成成分とする正極合剤からなる正極と、負極集電体と負極活物質を主要構成成分とする負極合剤からなる負極と、非水電解質とから構成される。リチウム二次電池を構成する正極活物質としては、リチウム含有遷移金属酸化物が、負極活物質としては、グラファイトに代表される炭素質材料が広く知られている。 Generally, a lithium secondary battery includes a positive electrode composed of a positive electrode mixture mainly composed of a positive electrode current collector and a positive electrode active material, and a negative electrode composed of a negative electrode mixture mainly composed of a negative electrode current collector and a negative electrode active material. And a non-aqueous electrolyte. A lithium-containing transition metal oxide is widely known as a positive electrode active material constituting a lithium secondary battery, and a carbonaceous material typified by graphite is widely known as a negative electrode active material.
また、電解質には、一般的に、常温で液状を呈する非水電解質（非水電解液）が用いられている。該非水電解液は、一般的に常温で液状の有機溶媒に常温で固体状のリチウム塩を溶解させてなるものである。該有機溶媒としては、例えば、エチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート、γ−ブチロラクトン、プロピオラクトン、バレロラクトン、テトラヒドロフラン、ジメトキシエタン、ジエトキシエタン、メトキシエトキシエタン等の有機溶媒が用いられている。また、リチウム塩としてはＬｉＰＦ６やＬｉＢＦ４が広く用いられている。 In general, a non-aqueous electrolyte (non-aqueous electrolyte) that is liquid at room temperature is used as the electrolyte. The non-aqueous electrolyte is generally obtained by dissolving a lithium salt that is solid at room temperature in an organic solvent that is liquid at room temperature. Examples of the organic solvent include organic carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, propiolactone, valerolactone, tetrahydrofuran, dimethoxyethane, diethoxyethane, and methoxyethoxyethane. A solvent is used. LiPF 6 and LiBF 4 are widely used as lithium salts.
特許文献１には、非プロトン性溶媒中に、Ｌｉ＋［（ＦＳＯ２）２Ｎ］−で表されるイオン化合物（以下「ＦＳＩ塩」ともいう）を含むことを特徴とするイオン性伝導材料に関する発明（請求項１）が記載され、ＦＳＩ塩がポリエーテルの中に溶解されて得られた電解質（段落００３２、例２）、ＦＳＩ塩をプロピレンカーボネートに１．０モル濃度、０．５モル濃度及び０．１モル濃度で溶解した電解液（段落００３６〜００３７、例３）あるいは重合体電解質中にＬｉＮ（ＣＦ３ＳＯ２）２とＦＳＩ塩を８／１００のモル比で適用した電池（段落００５１〜００５４、例５）が記載されている。 Patent Document 1 discloses an ionic conductive material containing an ionic compound represented by Li + [(FSO 2 ) 2 N] − (hereinafter also referred to as “FSI salt”) in an aprotic solvent. An electrolyte obtained by dissolving an FSI salt in a polyether (paragraph 0032, Example 2), 1.0 mol concentration of propylene carbonate in propylene carbonate, 0.5 mol A battery in which LiN (CF 3 SO 2 ) 2 and FSI salt are applied at a molar ratio of 8/100 in an electrolytic solution (paragraphs 0036 to 0037, Example 3) or a polymer electrolyte dissolved at a concentration and 0.1 molar concentration ( Paragraphs 0051-0054, Example 5) are described.
しかしながら、特許文献１には、Ｎ（ＳＯ２Ｆ）２アニオン及びその他の含フッ素無機アニオンを共に含有する非水電解質については記載がなく、Ｎ（ＳＯ２Ｆ）２アニオン及びその他の含フッ素無機アニオンを共に含有することで出力特性を向上できることについては記載も示唆もない。 However, Patent Document 1, N (SO 2 F) 2 anion and no description about the non-aqueous electrolyte containing both other fluorine-containing inorganic anion, N (SO 2 F) 2 anions and other fluorine-containing inorganic There is no description or suggestion that the output characteristics can be improved by containing both anions.
なお、ＬｉＮ（ＳＯ２Ｆ）２はＬｉＰＦ６など他のリチウム塩と比較して有機溶媒への溶解性が極めて悪く、例えば後述する比較例にはＬｉＮ（ＳＯ２Ｆ）２のみをリチウム塩として用いた電解液を調整したことを記載したが、このような電解液の調整には、長時間の撹拌や加熱などの非常に繁雑な工程が必要であり、工業上大いに問題があった。 In addition, LiN (SO 2 F) 2 has extremely poor solubility in organic solvents as compared with other lithium salts such as LiPF 6. For example, in a comparative example described later, only LiN (SO 2 F) 2 is used as a lithium salt. Although it was described that the electrolytic solution used was adjusted, the adjustment of such an electrolytic solution required a very complicated process such as long-time stirring and heating, which was very problematic in industry.
特許文献２〜５には、ＬｉＮ（Ｃ２Ｆ５ＳＯ２）２、ＬｉC（ＣＦ３ＳＯ２）２等の有機リチウム塩と、ＬｉＰＦ６、ＬｉＣｌＯ４、ＬｉＢＦ４、ＬｉＡｓＦ６といった無機リチウム塩を共に含有する非水電解質を用いた電池が提案されている。 Patent Documents 2 to 5 include organic lithium salts such as LiN (C 2 F 5 SO 2 ) 2 and LiC (CF 3 SO 2 ) 2 and inorganic lithium salts such as LiPF 6 , LiClO 4 , LiBF 4 , and LiAsF 6. A battery using a non-aqueous electrolyte containing both has been proposed.
しかしながら、特許文献２〜５のいずれにも、Ｎ（ＳＯ２Ｆ）２アニオンを含有する非水電解質についての記載は皆無であり、Ｎ（ＳＯ２Ｆ）２アニオン及びその他の含フッ素無機アニオンを共に含有することで出力特性を向上できることについては記載も示唆もない。
本発明は上記問題点に鑑みてなされたものであり、出力特性に優れた非水電解質電池を提供することを、一の目的とする。 The present invention has been made in view of the above problems, and an object thereof is to provide a nonaqueous electrolyte battery having excellent output characteristics.
上記課題を解決するための本発明の構成は以下の通りである。但し、作用機構については推定を含んでおり、その作用機構の成否は、本発明を制限するものではない。 The configuration of the present invention for solving the above-described problems is as follows. However, the action mechanism includes estimation, and the success or failure of the action mechanism does not limit the present invention.
本発明は、正極と、負極と、有機溶媒及びリチウムカチオンを含有する非水電解質と、を備えた非水電解質電池において、前記非水電解質は、Ｎ（ＳＯ２Ｆ）２アニオン及びその他の含フッ素無機アニオンを含有していることを特徴とする非水電解質電池である。 The present invention provides a non-aqueous electrolyte battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte containing an organic solvent and a lithium cation, wherein the non-aqueous electrolyte includes N (SO 2 F) 2 anion and other contents. A nonaqueous electrolyte battery comprising a fluorine inorganic anion.
ここで、その他の含フッ素無機アニオンとは、Ｎ（ＳＯ２Ｆ）２アニオン以外の含フッ素無機アニオンをいう。その他の含フッ素無機アニオンとしては、限定されるものではないが、具体的には、ＢＦ４、ＰＦ６、ＡｓＦ６、ＳｂＦ６等のアニオンが挙げられる。なかでも、ＰＦ６アニオン及びＢＦ４アニオンの内、少なくとも一種であることが好ましい。なお、これらの含フッ素無機アニオンは、単独で用いてもよく、２種以上混合して用いてもよい。 Here, other fluorine-containing inorganic anions refer to fluorine-containing inorganic anions other than N (SO 2 F) 2 anions. Other fluorine-containing inorganic anions are not limited, but specific examples include anions such as BF 4 , PF 6 , AsF 6 , and SbF 6 . Among them, out of PF 6 anion and BF 4 anion, it is preferably at least one. In addition, these fluorine-containing inorganic anions may be used independently and may be used in mixture of 2 or more types.
このような構成によると、実に驚くべきことに、出力特性に優れた非水電解質電池を提供することができることを見いだし、本発明に至った。 According to such a configuration, it was surprisingly found that a nonaqueous electrolyte battery having excellent output characteristics can be provided, and the present invention has been achieved.
すなわち、電解質がＮ（ＳＯ２Ｆ）２アニオン及びその他の含フッ素無機アニオンを共に含有していることにより、本発明による非水電解質電池は、出力特性に優れた非水電解質電池とすることができる。その作用効果が得られる要因は、必ずしも明らかではないが、初期充電時に負極表面上でＮ（ＳＯ２Ｆ）２アニオンが非水電解質構成成分の中で最も貴な電位から還元分解することにより、負極表面に非常に低抵抗でありながら他の非水電解質構成成分の還元分解を抑制できる保護被膜が形成されるためと本発明者らは推定している。このことは、Ｎ（ＳＯ２Ｆ）２アニオンが電気化学的安定性に劣ることを示唆しているが、ここに、その他の含フッ素無機アニオンが共存することにより、その後の充放電中におけるＮ（ＳＯ２Ｆ）２アニオンの酸化還元分解が抑制され、電気化学特性に優れた非水電解質電池を容易に提供することが可能となるものと推定される。さらに、特に出力特性に優れた非水電解質電池を提供できる作用効果が得られるのは、Ｎ（ＳＯ２Ｆ）２アニオンが良好な保護被膜形成剤として作用することに加え、非水電解質電池に用いられる従来の有機アニオンと比較して分子量が小さく、従来の有機アニオンと無機アニオンの中間に位置する性質を持つことにより、放電開始直後の非水電解質中のリチウムカチオンの移動を妨げにくいためと推定される。 That is, when the electrolyte contains both N (SO 2 F) 2 anion and other fluorine-containing inorganic anions, the non-aqueous electrolyte battery according to the present invention is a non-aqueous electrolyte battery having excellent output characteristics. it can. The reason why the effect is obtained is not necessarily clear, but the N (SO 2 F) 2 anion is reduced and decomposed from the most noble potential among the nonaqueous electrolyte components on the negative electrode surface during initial charging, The present inventors presume that a protective film capable of suppressing the reductive decomposition of other nonaqueous electrolyte components while having a very low resistance is formed on the negative electrode surface. This suggests that the N (SO 2 F) 2 anion is inferior in electrochemical stability, but the presence of other fluorine-containing inorganic anions here causes the N during the subsequent charge / discharge. It is presumed that the oxidation-reduction decomposition of (SO 2 F) 2 anion is suppressed and a nonaqueous electrolyte battery excellent in electrochemical characteristics can be easily provided. Furthermore, the effect of providing a non-aqueous electrolyte battery having particularly excellent output characteristics is obtained because the N (SO 2 F) 2 anion functions as a good protective film forming agent, and in addition to the non-aqueous electrolyte battery. This is because the molecular weight is small compared to the conventional organic anion used, and it is located between the conventional organic anion and the inorganic anion, so that it is difficult to prevent the movement of the lithium cation in the non-aqueous electrolyte immediately after the start of discharge. Presumed.
本発明によれば、出力特性に優れた非水電解質電池を提供することができる。 According to the present invention, a nonaqueous electrolyte battery excellent in output characteristics can be provided.
以下に、本発明の実施の形態を詳細に説明するが、本発明はこれらの記述により限定されるものではない。 Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to these descriptions.
本発明の非水電解質は、少なくともリチウムカチオン、Ｎ（ＳＯ２Ｆ）２アニオン及びその他の含フッ素無機アニオンと、有機溶媒から構成される。本発明の非水電解質を得るための方法については、何ら限定されるものではなく、リチウムカチオンとＮ（ＳＯ２Ｆ）２アニオンからなるリチウム塩及びリチウムカチオンとその他の含フッ素無機アニオンからなるリチウム塩を、有機溶媒に溶解させることにより得ることができる。しかしながら、これに限定されるものではなく、例えば、上記リチウム塩の一方に代えてアンモニウム塩を用いてもよい。 The non-aqueous electrolyte of the present invention is composed of at least a lithium cation, an N (SO 2 F) 2 anion and other fluorine-containing inorganic anions, and an organic solvent. The method for obtaining the non-aqueous electrolyte of the present invention is not limited at all, and a lithium salt composed of a lithium cation and an N (SO 2 F) 2 anion and lithium composed of a lithium cation and other fluorine-containing inorganic anions. The salt can be obtained by dissolving in an organic solvent. However, the present invention is not limited to this. For example, an ammonium salt may be used instead of one of the lithium salts.
本発明の非水電解質は、さらに、他のアニオンとして、ＣｌＯ４、ＣＮ、ＣＯＯ、ＳＯ２ＣＦ２、Ｎ（ＣＦ３ＳＯ２）２、Ｎ（Ｃ２Ｆ５ＳＯ２）２、Ｎ（ＣＦ３ＳＯ２）（Ｃ４Ｆ９ＳＯ２）、Ｃ（ＣＦ３ＳＯ２）３、Ｃ（Ｃ２Ｆ５ＳＯ２）３等のアニオンを含有してもよい。 The nonaqueous electrolyte of the present invention further includes other anions such as ClO 4 , CN, COO, SO 2 CF 2 , N (CF 3 SO 2 ) 2 , N (C 2 F 5 SO 2 ) 2 , N (CF 3 SO 2 ) (C 4 F 9 SO 2 ), C (CF 3 SO 2 ) 3 , C (C 2 F 5 SO 2 ) 3, and the like.
本発明における有機溶媒としては、何ら限定されるものではなく、一般に非水電解質電池用電解液に使用される有機溶媒を使用することができる。具体的には、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ビニレンカーボネート、ビニルエチレンカーボネート、クロロエチレンカーボネート、フルオロエチレンカーボネートなどの環状カーボネート、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート、ジプロピルカーボネート、ジブチルカーボネートなどの鎖状カーボネート、γ−ブチロラクトン、プロピオラクトン、バレロラクトン、テトラヒドロフラン、ジメトキシエタン、ジエトキシエタン、メトキシエトキシエタンなどが挙げられるが、特にこれらに限定されるものではない。これらは単独で用いてもよく、２種以上混合して用いてもよい。 The organic solvent in the present invention is not limited at all, and an organic solvent generally used for an electrolyte solution for a nonaqueous electrolyte battery can be used. Specifically, cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, vinyl ethylene carbonate, chloroethylene carbonate, fluoroethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, dibutyl carbonate, etc. The chain carbonate, γ-butyrolactone, propiolactone, valerolactone, tetrahydrofuran, dimethoxyethane, diethoxyethane, methoxyethoxyethane and the like are not particularly limited thereto. These may be used alone or in combination of two or more.
非水電解質中のＮ（ＳＯ２Ｆ）２アニオンとその他の含フッ素無機アニオンとの混合割合は任意に選択することが可能であるが、本発明の効果を充分に得るためには、アニオン総量に占めるＮ（ＳＯ２Ｆ）２アニオンの混合割合は、８０ｍｏｌ％未満であることが好ましい。Ｎ（ＳＯ２Ｆ）２アニオンの混合割合が８０ｍｏｌ％以上になると、リチウムカチオンとＮ（ＳＯ２Ｆ）２アニオンからなるリチウム塩の非水電解質への溶解度が低いため、対イオンであるリチウムカチオンの非水電解質中の含有量が小さくなり、電池の充放電効率が低下する。逆にＮ（ＳＯ２Ｆ）２アニオンの混合割合が１ｍｏｌ％未満になると、電池の出力特性が低下する。従って、非水電解質中のＮ（ＳＯ２Ｆ）２アニオンの混合割合は、１〜８０ｍｏｌ％の範囲、さらに言うならば、１０〜５０ｍｏｌ％の範囲、なかでも２０〜５０ｍｏｌ％の範囲であることが好ましい。 The mixing ratio of the N (SO 2 F) 2 anion and other fluorine-containing inorganic anions in the non-aqueous electrolyte can be arbitrarily selected, but in order to sufficiently obtain the effects of the present invention, the total amount of anions It is preferable that the mixing ratio of N (SO 2 F) 2 anion to be less than 80 mol%. When the mixing ratio of the N (SO 2 F) 2 anion is 80 mol% or more, the lithium salt composed of the lithium cation and the N (SO 2 F) 2 anion has low solubility in the non-aqueous electrolyte. The content in the non-aqueous electrolyte is reduced, and the charge / discharge efficiency of the battery is reduced. Conversely, when the mixing ratio of N (SO 2 F) 2 anion is less than 1 mol%, the output characteristics of the battery are degraded. Therefore, the mixing ratio of the N (SO 2 F) 2 anion in the non-aqueous electrolyte is in the range of 1 to 80 mol%, more specifically, in the range of 10 to 50 mol%, especially in the range of 20 to 50 mol%. Is preferred.
非水電解質中のリチウムカチオンの含有量は、０．５〜３ｍｏｌ／ｌの範囲であることが好ましい。リチウムカチオンの含有量が０．５ｍｏｌ／ｌ未満になると、電解質抵抗が大きすぎ、電池の充放電効率が低下する。逆にリチウムカチオンの含有量が３ｍｏｌ／ｌを越えると、非水電解質の融点が上昇し、常温で液状を保つのが困難となる。以上の点で、非水電解質中のリチウムカチオンの含有量は、０．５〜３ｍｏｌ／ｌの範囲、さらに言うならば、０．５〜２ｍｏｌ／ｌの範囲であることが好ましい。 The lithium cation content in the non-aqueous electrolyte is preferably in the range of 0.5 to 3 mol / l. When the content of the lithium cation is less than 0.5 mol / l, the electrolyte resistance is too large, and the charge / discharge efficiency of the battery decreases. On the other hand, when the lithium cation content exceeds 3 mol / l, the melting point of the non-aqueous electrolyte rises and it becomes difficult to maintain a liquid state at room temperature. In view of the above, the lithium cation content in the non-aqueous electrolyte is preferably in the range of 0.5 to 3 mol / l, more specifically in the range of 0.5 to 2 mol / l.
本発明に係る非水電解質電池が備える正極に用いることのできる正極活物質としては、何ら限定されるものではなく、種々の酸化物、硫化物等が挙げられる。例えば、二酸化マンガン（ＭｎＯ２）、酸化鉄、酸化銅、酸化ニッケル、リチウムマンガン複合酸化物（例えばＬｉｘＭｎ２Ｏ４又はＬｉｘＭｎＯ２）、リチウムニッケル複合酸化物（例えばＬｉｘＮｉＯ２）、リチウムコバルト複合酸化物（ＬｉｘＣｏＯ２）、リチウムニッケルコバルト複合酸化物（例えばＬｉＮｉ１−ｙＣｏｙＯ２）、リチウムニッケルコバルトマンガン複合酸化物（ＬｉＮｉｘＣｏｙＭｎ１−ｙ−ｚＯ２）、スピネル型リチウムマンガンニッケル複合酸化物（ＬｉｘＭｎ２−ｙＮｉｙＯ４）、オリビン構造を有するリチウムリン酸化物（ＬｉＦｅＰＯ４、ＬｉＣｏＰＯ４、ＬｉＶＰＯ４、ＬｉＶＰＯ４Ｆ、ＬｉＭｎＰＯ４、ＬｉＭｎ７／８Ｆｅ１／８ＰＯ４、ＬｉＮｉＶＯ４、ＬｉＣｏＰＯ４、Ｌｉ３Ｖ２（ＰＯ４）３、Ｆｅ２（ＳＯ４）３、ＬｉＦｅＰ２Ｏ７、Ｌｉ３Ｆｅ２（ＰＯ４）３、Ｌｉ２ＣｏＳｉＯ４、Ｌｉ２ＭｎＳｉＯ４、Ｌｉ２ＦｅＳｉＯ４、ＬｉＴｅＰＯ４等）、硫酸鉄（Ｆｅ２（ＳＯ４）３）、バナジウム酸化物（例えばＶ２Ｏ５）などが挙げられる。また、ポリアニリンやポリピロールなどの導電性ポリマー材料、ジスルフィド系ポリマー材料、イオウ（Ｓ）、フッ化カーボンなどの有機材料及び無機材料も挙げられる。
これらは単独で用いてもよく、２種以上混合して用いてもよい。
The positive electrode active material that can be used for the positive electrode included in the nonaqueous electrolyte battery according to the present invention is not limited at all, and various oxides, sulfides, and the like can be mentioned. For example, manganese dioxide (MnO 2 ), iron oxide, copper oxide, nickel oxide, lithium manganese composite oxide (eg, Li x Mn 2 O 4 or Li x MnO 2 ), lithium nickel composite oxide (eg, Li x NiO 2 ) , Lithium cobalt composite oxide (Li x CoO 2 ), lithium nickel cobalt composite oxide (for example, LiNi 1-y Co y O 2 ), lithium nickel cobalt manganese composite oxide (LiNi x Co y Mn 1-yz O) 2 ), spinel type lithium manganese nickel composite oxide (Li x Mn 2 -y Ni y O 4 ), lithium phosphorus oxide having an olivine structure (LiFePO 4 , LiCoPO 4 , LiVPO 4 , LiVPO 4 F, LiMnPO 4 , LiMn 7/8 Fe 1/8 PO 4 , LiNiVO 4 LiCoPO 4 , Li 3 V 2 (PO 4 ) 3 , Fe 2 (SO 4 ) 3 , LiFeP 2 O 7 , Li 3 Fe 2 (PO 4 ) 3 , Li 2 CoSiO 4 , Li 2 MnSiO 4 , Li 2 FeSiO 4 , LiTePO 4, etc.), iron sulfate (Fe 2 (SO 4 ) 3 ), vanadium oxide (for example, V 2 O 5 ), and the like. In addition, conductive polymer materials such as polyaniline and polypyrrole, disulfide-based polymer materials, organic materials such as sulfur (S) and carbon fluoride, and inorganic materials are also included.
These may be used alone or in combination of two or more.
本発明における非水電解質電池の負極は、主要構成成分である負極活物質として、炭素質材料を用いることができる。黒鉛結晶には良く知られている六方晶系とその他に菱面体晶系に属するものがある。特に、菱面体晶系の黒鉛は、電解液中の溶媒の選択性が広く、例えば、リチウムカチオンと共挿入しやすい有機化合物や、比較的貴な電位で還元分解されやすい有機化合物を、非水電解質の構成材料として用いても、層剥離が抑制され優れた充放電効率を示すことから好ましい。大部分の天然黒鉛及び人造黒鉛は六方晶系であるが、天然黒鉛及び非常に高温で加熱処理された人造黒鉛中に菱面体晶系構造が数％存在していることが知られている。また、粉砕や摩砕することにより六方晶系から菱面体晶系への増加があることが知られている。特に、黒鉛粒子表面に菱面体晶系が多く含まれ、粒子内部は六方晶系が多く含まれるような黒鉛は高容量、耐溶剤性、製造工程などの優位性から最も好ましい。また、炭素質材料として、非黒鉛質炭素材料を用いる場合には、エックス線広角回折法による（００２）面の面間隔が０．３４ｎｍ以上の非黒鉛質炭素材料であることが好ましい。このような非黒鉛質炭素材料を用いると、特に高率充放電特性や出力特性、サイクル充放電特性に優れた非水電解質電池を提供することが可能となる。上記効果が発揮される理由については必ずしも明らかではないが、上記したような非黒鉛質炭素材料は、リチウムカチオンの挿入脱離が起こる反応活性点がランダムに形成されているため、非水電解質を構成する有機溶媒の還元分解や共挿入などの副反応が抑制されるものと推定される。また、化学式Ｌｉ４＋ｘＴｉ５Ｏ１２（０≦ｘ≦３）で表され、スピネル型構造を有するチタン酸リチウムを用いてもよい。ここで、Ｔｉの一部が他の元素で置換されたものを用いてもよく、例えばＴｉの一部がＡｌやＭｇによって特定の比率で置換された構造のチタン酸リチウムを用いると、電位平坦性や高率放電特性の向上を図れるため、好ましい。 In the negative electrode of the nonaqueous electrolyte battery in the present invention, a carbonaceous material can be used as the negative electrode active material which is a main component. Graphite crystals include the well-known hexagonal system and others belonging to the rhombohedral system. In particular, rhombohedral graphite has a wide selectivity for a solvent in an electrolytic solution. For example, an organic compound that easily co-inserts with a lithium cation or an organic compound that easily undergoes reductive decomposition at a relatively noble potential can be obtained using a non-aqueous solution. Even if it uses as a constituent material of electrolyte, delamination is suppressed and it is preferable from showing the outstanding charging / discharging efficiency. Most natural graphite and artificial graphite are hexagonal, but it is known that a few percent of rhombohedral structures exist in natural graphite and artificial graphite heat-treated at a very high temperature. It is also known that there is an increase from hexagonal to rhombohedral by grinding or grinding. In particular, graphite having a large amount of rhombohedral system on the surface of the graphite particle and a large amount of hexagonal system inside the particle is most preferable because of superiority in high capacity, solvent resistance, manufacturing process and the like. Further, when a non-graphitic carbon material is used as the carbonaceous material, it is preferably a non-graphitic carbon material having a (002) plane spacing of 0.34 nm or more according to the X-ray wide angle diffraction method. When such a non-graphitic carbon material is used, it is possible to provide a non-aqueous electrolyte battery that is particularly excellent in high rate charge / discharge characteristics, output characteristics, and cycle charge / discharge characteristics. The reason why the above effect is exerted is not necessarily clear, but the non-graphitic carbon material as described above has reaction active points at which insertion and desorption of lithium cations occur at random. It is presumed that side reactions such as reductive decomposition and co-insertion of the constituent organic solvent are suppressed. Alternatively, lithium titanate represented by the chemical formula Li 4 + x Ti 5 O 12 (0 ≦ x ≦ 3) and having a spinel structure may be used. Here, a material in which a part of Ti is substituted with another element may be used. For example, when lithium titanate having a structure in which a part of Ti is substituted with Al or Mg at a specific ratio, the potential is flattened. This is preferable because it can improve the performance and high rate discharge characteristics.
以下に、本発明を実施例に基づき、さらに詳細に説明するが、本発明はこれらの記載により限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these descriptions.
（本発明電解質１）
エチレンカーボネート（ＥＣ）とジメチルカーボネート（ＤＭＣ）とメチルエチルカーボネート（ＭＥＣ）を体積比１：１：１で混合した１リットルの混合溶媒（以下、混合溶媒Ａという）に、０．８モルのＬｉＰＦ６と０．２モルのＬｉＮ（ＳＯ２Ｆ）２を混合することにより、非水電解質を得た。
(Invention electrolyte 1)
0.8 mol of LiPF was added to 1 liter of a mixed solvent (hereinafter referred to as mixed solvent A) in which ethylene carbonate (EC), dimethyl carbonate (DMC), and methyl ethyl carbonate (MEC) were mixed at a volume ratio of 1: 1: 1. A non-aqueous electrolyte was obtained by mixing 6 and 0.2 mol of LiN (SO 2 F) 2 .
（本発明電解質２）
１リットルの混合溶媒Ａに、０．５モルのＬｉＰＦ６と０．５モルのＬｉＮ（ＳＯ２Ｆ）２を混合することにより、非水電解質を得た。
(Invention electrolyte 2)
A nonaqueous electrolyte was obtained by mixing 0.5 mol of LiPF 6 and 0.5 mol of LiN (SO 2 F) 2 in 1 liter of mixed solvent A.
（比較電解質１）
１リットルの混合溶媒Ａに、１モルのＬｉＰＦ６を混合することにより、非水電解質を得た。
(Comparative electrolyte 1)
By mixing 1 mol of LiPF 6 with 1 liter of mixed solvent A, a non-aqueous electrolyte was obtained.
（比較電解質２）
１リットルの混合溶媒Ａに、１モルのＬｉＮ（ＳＯ２Ｆ）２を混合することにより、非水電解質を得た。
(Comparative electrolyte 2)
1 mol of mixed solvent A was mixed with 1 mol of LiN (SO 2 F) 2 to obtain a nonaqueous electrolyte.
（比較電解質３）
１リットルの混合溶媒Ａに、１モルのＬｉＮ（ＣＦ３ＳＯ２）２を混合することにより、非水電解質を得た。
(Comparative electrolyte 3)
By mixing 1 mol of LiN (CF 3 SO 2 ) 2 with 1 liter of mixed solvent A, a non-aqueous electrolyte was obtained.
（比較電解質４）
１リットルの混合溶媒Ａに、１モルのＬｉＮ（Ｃ２Ｆ５ＳＯ２）２を混合することにより、非水電解質を得た。
(Comparative electrolyte 4)
By mixing 1 mol of LiN (C 2 F 5 SO 2 ) 2 with 1 liter of mixed solvent A, a non-aqueous electrolyte was obtained.
（比較電解質５）
１リットルの混合溶媒Ａに、０．５モルのＬｉＮ（ＣＦ３ＳＯ２）２と０．５モルのＬｉＮ（ＳＯ２Ｆ）２を混合することにより、非水電解質を得た。
(Comparative electrolyte 5)
A non-aqueous electrolyte was obtained by mixing 0.5 mol of LiN (CF 3 SO 2 ) 2 and 0.5 mol of LiN (SO 2 F) 2 in 1 liter of the mixed solvent A.
（比較電解質６）
１リットルの混合溶媒Ａに、０．５モルのＬｉＰＦ６と０．５モルのＬｉＮ（Ｃ２Ｆ５ＳＯ２）２を混合することにより、非水電解質を得た。
(Comparative electrolyte 6)
By mixing 0.5 mol of LiPF 6 and 0.5 mol of LiN (C 2 F 5 SO 2 ) 2 in 1 liter of mixed solvent A, a nonaqueous electrolyte was obtained.
（電解質特性試験）
電解質特性として、円錐−平板型回転式粘度計（東機産業製）を用いて上記した本発明電解質１〜２及び比較電解質１〜６の、２０℃における電解質の粘度を測定した。
(Electrolyte property test)
As electrolyte characteristics, the viscosity of the electrolyte at 20 ° C. of the above-described electrolytes 1 to 2 and comparative electrolytes 1 to 6 of the present invention was measured using a cone-plate type rotary viscometer (manufactured by Toki Sangyo).
（非水電解質電池の作製）
本発明電解質１〜２及び比較電解質１〜６を用いて、非水電解質電池を作製した。実施例に係る非水電解質電池の断面図を図２に示す。実施例に係る非水電解質電池は、正極１、負極２、及びセパレータ３からなる極群４と、非水電解質と、外装材としての金属樹脂複合フィルム５から構成されている。正極１は、正極合剤１１が正極集電体１２上に塗布されてなる。また、負極２は、負極合剤２１が負極集電体２２上に塗布されてなる。非水電解質は極群４に含浸されている。金属樹脂複合フィルム５は、極群４を覆い、その四方を熱溶着により封止されている。
(Preparation of non-aqueous electrolyte battery)
A non-aqueous electrolyte battery was produced using the present invention electrolytes 1-2 and comparative electrolytes 1-6. FIG. 2 shows a cross-sectional view of the non-aqueous electrolyte battery according to the example. The non-aqueous electrolyte battery according to the example is composed of a pole group 4 including a positive electrode 1, a negative electrode 2, and a separator 3, a non-aqueous electrolyte, and a metal resin composite film 5 as an exterior material. The positive electrode 1 is formed by applying a positive electrode mixture 11 on a positive electrode current collector 12. The negative electrode 2 is formed by applying a negative electrode mixture 21 on a negative electrode current collector 22. The nonaqueous electrolyte is impregnated in the pole group 4. The metal resin composite film 5 covers the pole group 4 and is sealed on all four sides by heat welding.
次に、上記構成の非水電解質電池の製造方法を説明する。正極１は次のようにして得た。まず、ＬｉＣｏＯ２と、導電剤であるアセチレンブラックを混合し、さらに結着剤としてポリフッ化ビニリデンのＮ−メチル−２−ピロリドン溶液を混合し、この混合物をアルミ箔からなる正極集電体１２の片面に塗布した後、乾燥し、正極合剤１１の厚さが所定の厚さとなるようにプレスした。以上の工程により正極１を得た。負極２は、次のようにして得た。まず、負極活物質である黒鉛（エックス線広角回折法による（００２）面の面間隔０．３３６ｎｍ）と、結着剤であるポリフッ化ビニリデンのＮ−メチル−２−ピロリドン溶液を混合し、この混合物を銅箔からなる負極集電体２２の片面に塗布した後、乾燥し、負極合剤２１厚みが所定の厚さとなるようにプレスした。以上の工程により負極２を得た。セパレータ３は、ポリエチレン製微孔膜を用いた。極群４は、正極合剤１１と負極合剤２１とを対向させ、その間にセパレータ３を配し、正極１、セパレータ３、負極２の順に積層することにより、構成した。次に、非水電解質中に極群４を浸漬させることにより、極群４に非水電解質を含浸させた。さらに、金属樹脂複合フィルム５で極群４を覆い、その四方を熱溶着により封止した。以上のようにして、本発明電池１〜２及び比較電池１〜６を作製した。 Next, a method for manufacturing the nonaqueous electrolyte battery having the above configuration will be described. The positive electrode 1 was obtained as follows. First, LiCoO 2 and acetylene black, which is a conductive agent, are mixed, and an N-methyl-2-pyrrolidone solution of polyvinylidene fluoride is further mixed as a binder, and this mixture is used as a positive electrode current collector 12 made of an aluminum foil. After coating on one side, it was dried and pressed so that the positive electrode mixture 11 had a predetermined thickness. The positive electrode 1 was obtained by the above process. The negative electrode 2 was obtained as follows. First, graphite (negative electrode active material (002) plane spacing 0.336 nm by X-ray wide angle diffraction method) and N-methyl-2-pyrrolidone solution of polyvinylidene fluoride as a binder were mixed, and this mixture Was applied to one side of a negative electrode current collector 22 made of copper foil, dried, and pressed so that the thickness of the negative electrode mixture 21 was a predetermined thickness. The negative electrode 2 was obtained by the above process. As the separator 3, a polyethylene microporous membrane was used. The pole group 4 was configured by facing the positive electrode mixture 11 and the negative electrode mixture 21, placing the separator 3 therebetween, and laminating the positive electrode 1, the separator 3, and the negative electrode 2 in this order. Next, the electrode group 4 was impregnated with the non-aqueous electrolyte by immersing the electrode group 4 in the non-aqueous electrolyte. Furthermore, the pole group 4 was covered with the metal resin composite film 5, and the four sides were sealed by heat welding. As described above, Invention batteries 1 and 2 and Comparative batteries 1 to 6 were produced.
また、本発明電解質２及び比較電解質１を用いて、負極活物質に難黒鉛化炭素（エックス線広角回折法による（００２）面の面間隔０．３４５ｎｍ）を用いた以外は同様の構成にて非水電解質電池を作製した。これを本発明電池３及び比較電池７とする。 In addition, the non-graphite carbon (non-graphite carbon (002) plane spacing of 0.302 nm by X-ray wide angle diffraction method) was used as the negative electrode active material in the same configuration except that the electrolyte 2 of the present invention and the comparative electrolyte 1 were used. A water electrolyte battery was prepared. This is referred to as the present invention battery 3 and comparative battery 7.
（電池特性試験）
電池特性試験として、本発明電池及び比較電池について、高率放電試験を行った。試験温度は２０℃とした。充電は、電流１０ｍＡ、終止電圧４．２Ｖの定電流充電とした。放電は、電流１０ｍＡ、３０ｍＡ、５０ｍＡにて終止電圧２．７Ｖの定電流放電とした。電流５０ｍＡで放電し、得られた放電容量を、５Ｉｔ高率放電容量とした。また、それぞれの電流で放電したときの放電開始後１０秒目の電池電圧から、最小二乗法で求めた直線（電流−電圧直線）の傾きの絶対値をＳＯＣ１００％ＤＣＲとした。出力特性は、電流−電圧直線の傾きと放電下限電圧の交点から求めることができ、ＳＯＣ１００％ＤＣＲが小さいほど出力特性が優れていることを意味する。なお、本発明電池及び比較電池の設計容量は、全て１０ｍＡｈであり、電流１０ｍＡで放電したときの放電容量はいずれも概ね１０ｍＡｈであった。
(Battery characteristics test)
As a battery characteristic test, a high rate discharge test was performed on the battery of the present invention and the comparative battery. The test temperature was 20 ° C. The charging was a constant current charging with a current of 10 mA and a final voltage of 4.2V. The discharge was a constant current discharge with a final voltage of 2.7 V at a current of 10 mA, 30 mA, and 50 mA. The battery was discharged at a current of 50 mA, and the obtained discharge capacity was defined as a 5 It high-rate discharge capacity. Further, the absolute value of the slope of a straight line (current-voltage straight line) obtained by the least square method from the battery voltage 10 seconds after the start of discharge when discharging at each current was defined as SOC 100% DCR. The output characteristics can be obtained from the intersection of the slope of the current-voltage straight line and the discharge lower limit voltage, and the smaller the SOC 100% DCR, the better the output characteristics. The design capacities of the battery of the present invention and the comparative battery were all 10 mAh, and the discharge capacities when discharged at a current of 10 mA were both approximately 10 mAh.
以上の結果を表１にまとめて示す。なお、５Ｉｔ高率放電容量及びＳＯＣ１００％ＤＣＲは、本発明電池１〜２及び比較電池１〜６については比較電池１の特性を１００％としたときの百分率で、本発明電池３及び比較電池７については比較電池７の特性を１００％としたときの百分率で示す。また、本発明電解質１、２及び比較電解質１、２の粘度及び本発明電池１、２及び比較電池１、２のＳＯＣ１００％ＤＣＲとＬｉＮ（ＳＯ２Ｆ）２濃度との関係を図１に示す。 The above results are summarized in Table 1. The 5 It high rate discharge capacity and the SOC 100% DCR are percentages when the characteristics of the comparative battery 1 are 100% for the inventive batteries 1 to 2 and the comparative batteries 1 to 6, and the inventive batteries 3 and 7 are compared. Is shown as a percentage when the characteristic of the comparative battery 7 is taken as 100%. Further, FIG. 1 shows the relationship between the viscosity of the electrolytes 1 and 2 of the present invention and the comparative electrolytes 1 and 2 and the SOC 100% DCR and the concentration of LiN (SO 2 F) 2 of the batteries 1 and 2 of the present invention and the comparative batteries 1 and 2 . .
一般に、電池特性のいくつかは、非水電解質の粘度との相関が認められ、電解質の粘度を測定することにより予想することができる。図１に示したように、本発明電解質１、２及び比較電解質１、２を比べてみると、これらの電解質の粘度はＬｉＮ（ＳＯ２Ｆ）２濃度に比例して低くなる傾向が認められる。そして、Ｎ（ＳＯ２Ｆ）２アニオンのみを含有する比較電池２は、その他の含フッ素無機アニオンであるＰＦ６アニオンのみを含有する比較電池１と比較して、ＳＯＣ１００％ＤＣＲが小さくなる。 In general, some of the battery characteristics correlate with the viscosity of the non-aqueous electrolyte, and can be predicted by measuring the viscosity of the electrolyte. As shown in FIG. 1, when the present electrolytes 1 and 2 and the comparative electrolytes 1 and 2 are compared, the viscosity of these electrolytes tends to decrease in proportion to the LiN (SO 2 F) 2 concentration. . The comparative battery 2 containing only the N (SO 2 F) 2 anion has a lower SOC 100% DCR than the comparative battery 1 containing only the PF 6 anion which is another fluorine-containing inorganic anion.
これに対し、実に驚くべきことに、Ｎ（ＳＯ２Ｆ）２アニオン及びＰＦ６アニオンを共に含有する非水電解質を用いた本発明電池１及び本発明電池２のＳＯＣ１００％ＤＣＲは、ＰＦ６アニオンのみを含有する比較電池１と比較して大きく低減されていることがわかる。さらに、図１から明らかなように、Ｎ（ＳＯ２Ｆ）２アニオン及びＰＦ６アニオンを共に含有する非水電解質を用いた本発明電池１及び本発明電池２のＳＯＣ１００％ＤＣＲの値は、ＰＦ６アニオンのみを含有する比較電池１のＳＯＣ１００％ＤＣＲの値をプロットした点と、Ｎ（ＳＯ２Ｆ）２アニオンのみを含有する比較電池２のＳＯＣ１００％ＤＣＲの値をプロットした点を結ぶ直線（図中一点鎖線で示す）から逸脱して大きく下回る結果となっている。すなわち、ＳＯＣ１００％ＤＣＲと非水電解質中のＬｉＮ（ＳＯ２Ｆ）２濃度との関係は、電解質の粘度のような比例関係にはなく、Ｎ（ＳＯ２Ｆ）２アニオン及びその他の含フッ素無機アニオンであるＰＦ６アニオンを共に含有することによって、ＳＯＣ１００％ＤＣＲがＮ（ＳＯ２Ｆ）２アニオンのみを含有する場合と同等かそれ以上に小さくなることは、非水電解質の粘度等の物性からは到底予想できるものではない。 On the other hand, surprisingly, the SOC 100% DCR of the present invention battery 1 and the present invention battery 2 using the nonaqueous electrolyte containing both N (SO 2 F) 2 anion and PF 6 anion is PF 6 anion. It can be seen that it is greatly reduced as compared with the comparative battery 1 containing only. Further, as apparent from FIG. 1, the SOC 100% DCR values of the present invention battery 1 and the present invention battery 2 using the nonaqueous electrolyte containing both N (SO 2 F) 2 anion and PF 6 anion are PF A straight line connecting a point where the SOC 100% DCR value of the comparative battery 1 containing only 6 anions is plotted and a point where the SOC 100% DCR value of the comparative battery 2 containing only N (SO 2 F) 2 anions is plotted ( It is a result that deviates from (shown by a one-dot chain line in the figure) and greatly falls. That is, the relationship between the SOC 100% DCR and the LiN (SO 2 F) 2 concentration in the non-aqueous electrolyte is not proportional to the viscosity of the electrolyte, but the N (SO 2 F) 2 anion and other fluorine-containing inorganic substances By including both the PF 6 anion which is an anion, the SOC 100% DCR is equal to or smaller than the case of containing only the N (SO 2 F) 2 anion from the physical properties such as the viscosity of the nonaqueous electrolyte. Is not at all predictable.
なお、本発明電池１〜３及び比較電池１〜７は同等の５Ｉｔ高率放電容量を示しており、本発明電池は、高エネルギー密度を有する非水電解質電池の特性を何ら悪化させるものではない。 In addition, this invention batteries 1-3 and the comparative batteries 1-7 have shown the equivalent 5It high rate discharge capacity, and this invention battery does not worsen the characteristic of the nonaqueous electrolyte battery which has a high energy density at all. .
また、本発明電池２、３及び比較電池１、７間の比較により、負極活物質として用いた炭素材料の種類にかかわらず、本発明の効果が同様に得られることが確認された。 Moreover, it was confirmed by comparison between this invention battery 2 and 3 and the comparison batteries 1 and 7 that the effect of this invention is acquired similarly irrespective of the kind of carbon material used as a negative electrode active material.
なお、本実施例においては、その他の含フッ素無機アニオンとしてＰＦ６アニオンを用いたが、ＢＦ４アニオン等、ＰＦ６アニオン以外の含フッ素無機アニオンを用いても同様の効果が得られる。 In this example, PF 6 anion was used as the other fluorine-containing inorganic anion. However, the same effect can be obtained by using a fluorine-containing inorganic anion other than PF 6 anion, such as BF 4 anion.
以上の結果から、本発明によれば、出力特性に優れた非水電解質電池を提供することができることが明らかとなった。 From the above results, it became clear that according to the present invention, a nonaqueous electrolyte battery having excellent output characteristics can be provided.
１ 正極
１１ 正極合剤
１２ 正極集電体
２ 負極
２１ 負極合剤
２２ 負極集電体
３ セパレータ
４ 極群
５ 金属樹脂複合フィルム
DESCRIPTION OF SYMBOLS 1 Positive electrode 11 Positive electrode mixture 12 Positive electrode collector 2 Negative electrode 21 Negative electrode mixture 22 Negative electrode collector 3 Separator 4 Electrode group 5 Metal resin composite film
Claims (4)
前記有機溶媒は環状カーボネート及び鎖状カーボネートからなるとともに、前記非水電解質は、Ｎ（ＳＯ２Ｆ）２アニオン及びその他の含フッ素無機アニオンを含有し、かつ前記非水電解質中のアニオン総量に占めるＮ（ＳＯ ２ Ｆ） ２ アニオンの混合割合が５０ｍｏｌ％以下であることを特徴とする非水電解質電池。 In a non-aqueous electrolyte battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte containing an organic solvent and a lithium cation,
The organic solvent is composed of a cyclic carbonate and a chain carbonate, and the non-aqueous electrolyte contains N (SO 2 F) 2 anion and other fluorine-containing inorganic anions and occupies the total amount of anions in the non-aqueous electrolyte. A non-aqueous electrolyte battery, wherein the mixing ratio of N (SO 2 F) 2 anion is 50 mol% or less .
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| JP5445103B2 (en) * | 2009-12-18 | 2014-03-19 | ソニー株式会社 | Secondary battery, electrolyte for secondary battery, electric tool, electric vehicle and power storage system |
| EP2511976A4 (en) | 2009-12-07 | 2013-07-17 | Sony Corp | Secondary cell, electrolyte, cell pack, electronic device, electric vehicle |
| EP3792221B1 (en) | 2010-05-28 | 2023-07-12 | Nippon Shokubai Co., Ltd. | Alkali metal salt of fluorosulfonyl imide |
| KR101233325B1 (en) | 2011-04-11 | 2013-02-14 | 로베르트 보쉬 게엠베하 | Electrolyte for rechargeable lithium battery and rechargeable lithium battery inclduing same |
| JP6065367B2 (en) | 2011-06-07 | 2017-01-25 | ソニー株式会社 | Nonaqueous electrolyte battery, battery pack, electronic device, electric vehicle, power storage device, and power system |
| FR2983466B1 (en) | 2011-12-06 | 2014-08-08 | Arkema France | USE OF MIXTURES OF LITHIUM SALTS AS ELECTROLYTES OF LI-ION BATTERIES |
| JP2013145732A (en) * | 2011-12-16 | 2013-07-25 | Nippon Shokubai Co Ltd | Lithium secondary battery |
| JP5893517B2 (en) * | 2012-06-25 | 2016-03-23 | 株式会社日本触媒 | Non-aqueous electrolyte |
| JP6483943B2 (en) * | 2012-06-26 | 2019-03-13 | 株式会社日本触媒 | Lithium secondary battery |
| CN104300176A (en) * | 2013-07-16 | 2015-01-21 | 江苏华盛精化工股份有限公司 | LiPF6/LIFSI/corrosion inhibitors-based lithium-ion battery electrolyte composition |
| JP6315775B2 (en) * | 2014-02-19 | 2018-04-25 | 株式会社日本触媒 | Lithium ion secondary battery |
| JP6661935B2 (en) * | 2015-09-25 | 2020-03-11 | 株式会社豊田自動織機 | Negative electrode for power storage device and power storage device |
| JP6661934B2 (en) * | 2015-09-25 | 2020-03-11 | 株式会社豊田自動織機 | Positive electrode for power storage device and power storage device |
| CN111108642B (en) | 2017-09-22 | 2024-04-02 | 三菱化学株式会社 | Nonaqueous electrolyte, nonaqueous electrolyte secondary battery, and energy device |
| WO2019193756A1 (en) * | 2018-04-06 | 2019-10-10 | 株式会社 東芝 | Nonaqueous electrolyte battery and battery pack |
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