JP7447830B2 - Deactivating agent for non-aqueous secondary batteries and method for deactivating non-aqueous secondary batteries - Google Patents
Deactivating agent for non-aqueous secondary batteries and method for deactivating non-aqueous secondary batteries Download PDFInfo
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- JP7447830B2 JP7447830B2 JP2021004000A JP2021004000A JP7447830B2 JP 7447830 B2 JP7447830 B2 JP 7447830B2 JP 2021004000 A JP2021004000 A JP 2021004000A JP 2021004000 A JP2021004000 A JP 2021004000A JP 7447830 B2 JP7447830 B2 JP 7447830B2
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- agent
- aqueous secondary
- secondary battery
- redox
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- 229910052802 copper Inorganic materials 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 25
- 230000000415 inactivating effect Effects 0.000 claims description 21
- 239000003125 aqueous solvent Substances 0.000 claims description 20
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Images
Description
本開示は、非水系二次電池の不活性化剤及び非水系二次電池の不活性化方法に関する。 The present disclosure relates to a deactivating agent for a non-aqueous secondary battery and a method for deactivating a non-aqueous secondary battery.
従来、非水系二次電池をリサイクル又は廃棄する際に、回収電池を不活性化させる不活性化処理が行われている。こうした処理として、例えば、回収電池を充放電装置につないで０Ｖまで放電させる処理が可能であるが、その場合、放電に時間がかかることがあった。また、回収電池が電流遮断機構（ＣＩＤ）作動後の電池である場合には、放電させること自体ができなかった。そこで、回収電池の内部にリチウムの酸化還元電位に対して３．０～４．５Ｖの範囲に酸化還元電位を示すレドックスシャトル剤（例えばフェロセン）を添加することが提案されている（特許文献１参照）。これにより、充放電装置を用いることなく、安全かつ迅速に非水系二次電池の電池電圧を０Ｖまで下げることができる。 Conventionally, when recycling or disposing of non-aqueous secondary batteries, inactivation treatment is performed to inactivate the recovered batteries. As such a process, for example, it is possible to connect the recovered battery to a charging/discharging device and discharge it to 0V, but in that case, the discharge sometimes takes a long time. Furthermore, when the recovered battery was a battery whose current interrupting device (CID) had been activated, it was not possible to discharge the battery itself. Therefore, it has been proposed to add a redox shuttle agent (for example, ferrocene) that exhibits a redox potential in the range of 3.0 to 4.5 V with respect to the redox potential of lithium into the interior of the recovered battery (Patent Document 1 reference). Thereby, the battery voltage of the non-aqueous secondary battery can be safely and quickly lowered to 0V without using a charging/discharging device.
ところで、特許文献１のレドックスシャトル剤を用いて非水系二次電池を不活性化した場合、不活性化後の負極電位が高いことがあった。負極電位が高いと、負極集電体の銅などが溶出して正極で析出し、不活性化後に非水系二次電池をリサイクル又は廃棄する際、析出物の正極からの除去又は回収が困難であるといった問題がある。このため、負極電位を低く保つことのできる不活性化剤及び不活性化方法が望まれていた。 By the way, when a non-aqueous secondary battery is inactivated using the redox shuttle agent of Patent Document 1, the negative electrode potential after inactivation is sometimes high. If the negative electrode potential is high, copper from the negative electrode current collector will be eluted and deposited on the positive electrode, making it difficult to remove or recover the deposits from the positive electrode when recycling or disposing of the non-aqueous secondary battery after inactivation. There are some problems. For this reason, a deactivating agent and a deactivating method that can keep the negative electrode potential low have been desired.
本開示はこのような課題を解決するためになされたものであり、負極電位を低く保つことのできる非水系二次電池の不活性化剤及び非水系二次電池の不活性化方法を提供することを主目的とする。 The present disclosure has been made to solve such problems, and provides a deactivating agent for a non-aqueous secondary battery and a method for deactivating a non-aqueous secondary battery that can maintain a low negative electrode potential. The main purpose is to
上述した目的を達成するために鋭意研究したところ、本発明者らは、酸化還元電位がＬｉ基準電位で負極活物質よりも高く正極活物質よりも低くかつ３．０Ｖ未満であるレドックスシャトル剤と非水系溶媒とを含む不活性化剤を非水系二次電池の内部に添加すると、非水系二次電池を不活性化させる際に負極電位が低く保たれることを見出し、本開示の発明を完成するに至った。 As a result of intensive research to achieve the above-mentioned objective, the present inventors have developed a redox shuttle agent whose redox potential is higher than the negative electrode active material and lower than the positive electrode active material and less than 3.0 V at Li reference potential. The present inventors have discovered that when a deactivating agent containing a non-aqueous solvent is added to the inside of a non-aqueous secondary battery, the negative electrode potential is kept low when the non-aqueous secondary battery is inactivated, and the invention of the present disclosure has been achieved. It was completed.
即ち、本開示の非水系二次電池の不活性化剤は、
非水系二次電池を不活性化する不活性化剤であって、
酸化還元電位がＬｉ基準電位で前記非水系二次電池の負極活物質よりも高く前記非水系二次電池の正極活物質よりも低くかつ３．０Ｖ未満であるレドックスシャトル剤と、非水系溶媒と、を含む、
ものである。
That is, the deactivating agent for the non-aqueous secondary battery of the present disclosure is
A deactivating agent that deactivates a non-aqueous secondary battery,
a redox shuttle agent whose redox potential is higher than the negative electrode active material of the non-aqueous secondary battery and lower than the positive electrode active material of the non-aqueous secondary battery and less than 3.0 V at a Li reference potential; and a non-aqueous solvent. ,including,
It is something.
また、本開示の非水系二次電池の不活性化方法は、
前記非水系二次電池の内部に、上述の非水系二次電池の不活性化剤を添加する添加工程、を含む、
ものである。
Further, the method for inactivating a non-aqueous secondary battery of the present disclosure includes:
an addition step of adding the above-described non-aqueous secondary battery deactivator into the non-aqueous secondary battery;
It is something.
この非水系二次電池の不活性化剤及び非水系二次電池の不活性化方法では、非水系二次電池を不活性化する際に、負極電位を低く保つことができる。このような効果が得られる理由は、例えば、以下のように推察される。充電状態の非水系二次電池に、酸化還元電位がＬｉ基準電位で正極電位より低く負極電位より高いレドックスシャトル剤を添加すると、正極及び負極とレドックスシャトル剤との電位差を駆動力として、電池の放電が進行する。放電は、正極電位及び負極電位がレドックスシャトル剤の酸化還元電位に等しくなるまで進行する。このため、酸化還元電位がＬｉ基準電位で３．０Ｖ未満のレドックスシャトル剤を用いることで、不活性化の際の負極電位を低く（例えばＬｉ基準電位で３．０Ｖ未満）に保つことができる。 With this non-aqueous secondary battery inactivating agent and non-aqueous secondary battery inactivating method, the negative electrode potential can be kept low when inactivating a non-aqueous secondary battery. The reason why such an effect is obtained is presumed to be as follows, for example. When a redox shuttle agent whose oxidation-reduction potential is lower than the positive electrode potential and higher than the negative electrode potential at the Li reference potential is added to a nonaqueous secondary battery in a charged state, the potential difference between the positive electrode, the negative electrode, and the redox shuttle agent is used as a driving force, and the battery The discharge progresses. Discharge proceeds until the positive and negative electrode potentials are equal to the redox potential of the redox shuttle agent. Therefore, by using a redox shuttle agent whose redox potential is less than 3.0 V at Li reference potential, the negative electrode potential during inactivation can be kept low (for example, less than 3.0 V at Li reference potential). .
本開示の非水系二次電池の不活性化剤は、非水系二次電池を不活性化する不活性化剤であって、酸化還元電位がＬｉ基準電位で負極活物質よりも高く正極活物質よりも低くかつ３．０Ｖ未満であるレドックスシャトル剤と、非水系溶媒と、を含むものである。本明細書において、レドックスシャトル剤とは、正極と負極との間で電荷を繰り返し輸送することができる、酸化及び還元可能な化合物を指す。 The deactivating agent for a non-aqueous secondary battery of the present disclosure is a deactivating agent that deactivates a non-aqueous secondary battery, and the redox potential is higher than that of the negative electrode active material at a Li reference potential. and a non-aqueous solvent. As used herein, a redox shuttle agent refers to an oxidizable and reducible compound that can repeatedly transport charge between a positive electrode and a negative electrode.
［非水系二次電池］
まず、不活性化の対象となる非水系二次電池について説明する。非水系二次電池は、正極活物質を有する正極と、負極活物質を有する負極と、正極と負極との間に介在しキャリアイオンを伝導する非水系のイオン伝導媒体と、を備えている。キャリアイオンとしては、例えば、第１族元素イオンや第２族元素イオンが挙げられる。第１族元素イオンとしては、例えば、リチウムイオンやナトリウムイオン、カリウムイオンが挙げられる。第２族元素イオンとしては、例えば、マグネシウムイオン、カルシウムイオンが挙げられる。以下では、説明の便宜のため、非水系二次電池がリチウムイオン二次電池である場合について主に説明する。
[Non-aqueous secondary battery]
First, a non-aqueous secondary battery to be deactivated will be explained. A non-aqueous secondary battery includes a positive electrode having a positive electrode active material, a negative electrode having a negative electrode active material, and a non-aqueous ion conductive medium interposed between the positive electrode and the negative electrode to conduct carrier ions. Examples of carrier ions include Group 1 element ions and Group 2 element ions. Examples of Group 1 element ions include lithium ions, sodium ions, and potassium ions. Examples of Group 2 element ions include magnesium ions and calcium ions. Below, for convenience of explanation, the case where the non-aqueous secondary battery is a lithium ion secondary battery will be mainly described.
正極は、例えば正極活物質と導電材と結着材とを混合し、適当な溶剤を加えてペースト状の正極合材としたものを、集電体の表面に塗布乾燥し、必要に応じて電極密度を高めるべく圧縮して形成してもよい。正極活物質は、Ｌｉ基準の酸化還元電位が不活性化剤に含まれるレドックスシャトル剤よりも高いものであればよいが、酸化還元電位がＬｉ基準電位で３．０Ｖ超過のものとしてもよく、３．５Ｖ以上のものが好ましく、３．８Ｖ以上のものがより好ましく、４．０Ｖ以上のものがさらに好ましい。正極活物質としては、遷移金属元素を含む硫化物や、リチウムと遷移金属元素とを含む酸化物などを用いることができる。具体的には、ＴｉＳ2、ＴｉＳ3、ＭｏＳ3、ＦｅＳ2などの遷移金属硫化物、Ｌｉ(1-x)ＭｎＯ2（０＜ｘ＜１など、以下同じ）、Ｌｉ(1-x)Ｍｎ2Ｏ4などのリチウムマンガン複合酸化物、Ｌｉ(1-x)ＣｏＯ2などのリチウムコバルト複合酸化物、Ｌｉ(1-x)ＮｉＯ2などのリチウムニッケル複合酸化物、Ｌｉ(1-x)ＮｉaＭｎbＯ2（ａ＋ｂ＝１）やＬｉ(1-x)ＮｉaＭｎbＯ4（ａ＋ｂ＝２）などのリチウムニッケルマンガン複合酸化物、Ｌｉ(1-x)ＮｉaＣｏbＭｎcＯ2（ａ＋ｂ＋ｃ＝１）などのリチウムニッケルコバルトマンガン複合酸化物、ＬｉＶ2Ｏ3などのリチウムバナジウム複合酸化物、Ｖ2Ｏ5などの遷移金属酸化物などを用いることができる。また、Ｌｉ(1-x)ＭｎＰＯ4などのオリビン型リチウムリン酸マンガン系化合物、Ｌｉ(1-x)ＣｏＰＯ4などのオリビン型リチウムリン酸コバルト系化合物、Ｌｉ(1-x)ＮｉＰＯ4などのオリビン型リチウムリン酸ニッケル系化合物などを用いることができる。また、Ｌｉ(1-x)ＭｎＶＯ4などの逆スピネル型リチウムバナジン酸マンガン系化合物、Ｌｉ(1-x)ＣｏＰＯ4などの逆スピネル型リチウムバナジン酸コバルト系化合物、Ｌｉ(1-x)ＮｉＰＯ4などの逆スピネル型リチウムバナジン酸ニッケル系化合物などを用いることができる。正極活物質は、ニッケル、マンガン、コバルトのうちの１以上を含む酸化物であることが好ましく、例えば、ＬｉＣｏＯ2、ＬｉＮｉＯ2、ＬｉＭｎＯ2、ＬｉＮｉ1/3Ｃｏ1/3Ｍｎ1/3Ｏ2などが好ましい。 For the positive electrode, for example, a positive electrode active material, a conductive material, and a binder are mixed, an appropriate solvent is added to make a paste-like positive electrode mixture, and the mixture is applied and dried on the surface of a current collector, and then mixed as necessary. It may be formed by compressing it in order to increase the electrode density. The positive electrode active material may have a Li-based redox potential higher than the redox shuttle agent contained in the deactivating agent, but may have a redox potential exceeding 3.0 V based on the Li-based potential. The voltage is preferably 3.5V or higher, more preferably 3.8V or higher, and even more preferably 4.0V or higher. As the positive electrode active material, a sulfide containing a transition metal element, an oxide containing lithium and a transition metal element, or the like can be used. Specifically, transition metal sulfides such as TiS 2 , TiS 3 , MoS 3 , and FeS 2 , Li (1-x) MnO 2 (0<x<1, etc., the same applies hereinafter), Li (1-x) Mn Lithium manganese composite oxides such as 2 O 4 , lithium cobalt composite oxides such as Li (1-x) CoO 2 , lithium nickel composite oxides such as Li (1-x) NiO 2 , Li (1-x) Ni Lithium nickel manganese composite oxides such as a Mn b O 2 (a+b=1) and Li (1-x) Ni a Mn b O 4 (a+b=2), Li (1-x) Ni a Co b Mn c O Lithium nickel cobalt manganese composite oxides such as 2 (a+b+c=1), lithium vanadium composite oxides such as LiV 2 O 3 , transition metal oxides such as V 2 O 5 and the like can be used. In addition, olivine-type lithium manganese phosphate compounds such as Li (1-x) MnPO 4 , olivine-type lithium cobalt phosphate compounds such as Li (1-x) CoPO 4 , Li (1-x) NiPO 4 , etc. Olivine-type lithium nickel phosphate compounds and the like can be used. In addition, inverted spinel-type lithium manganese vanadate-based compounds such as Li (1-x) MnVO 4 , inverted spinel-type lithium cobalt vanadate-based compounds such as Li (1-x) CoPO 4 , Li (1-x) NiPO 4 An inverted spinel type lithium nickel vanadate-based compound such as lithium nickel vanadate can be used. The positive electrode active material is preferably an oxide containing one or more of nickel, manganese, and cobalt, such as LiCoO 2 , LiNiO 2 , LiMnO 2 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 etc. are preferable.
正極の導電材としては、例えば、天然黒鉛（鱗状黒鉛、鱗片状黒鉛）や人造黒鉛などの黒鉛、アセチレンブラック、カーボンブラック、ケッチェンブラック、カーボンウィスカ、ニードルコークス、炭素繊維、金属（銅、ニッケル、アルミニウム、銀、金など）などを用いることができる。結着材としては、例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリフッ化ビニリデン（ＰＶｄＦ）、フッ素ゴム等の含フッ素樹脂、或いはポリプロピレン、ポリエチレン等の熱可塑性樹脂、エチレンプロピレンジエンゴム（ＥＰＤＭ）、スルホン化ＥＰＤＭゴム、天然ブチルゴム（ＮＢＲ）等を用いることができる。また、水系バインダーであるセルロース系やスチレンブタジエンゴム（ＳＢＲ）の水分散体等を用いることもできる。溶剤としては、例えば、Ｎ－メチルピロリドン、ジメチルホルムアミド、ジメチルアセトアミド、メチルエチルケトン、シクロヘキサノン、酢酸メチル、アクリル酸メチル、ジエチレントリアミン、Ｎ，Ｎ－ジメチルアミノプロピルアミン、エチレンオキシド、テトラヒドロフランなどの有機溶剤を用いることができる。また、水に分散剤、増粘剤等を加え、ＳＢＲなどのラテックスで活物質をスラリー化してもよい。増粘剤としては、例えば、カルボキシメチルセルロース、メチルセルロースなどの多糖類を単独で、あるいは２種以上の混合物として用いることができる。塗布方法としては、例えば、アプリケータロールなどのローラコーティング、スクリーンコーティング、ドクターブレイド方式、スピンコーティング、バーコータなどが挙げられ、これらのいずれかを用いて任意の厚さ・形状とすることができる。集電体としては、アルミニウム、チタン、ステンレス鋼、ニッケル、鉄、焼成炭素、導電性高分子、導電性ガラスなどのほか、接着性、導電性及び耐酸化性向上の目的で、アルミニウムや銅などの表面をカーボン、ニッケル、チタンや銀などで処理したものを用いることができる。これらについては、表面を酸化処理することも可能である。集電体の形状については、箔状、フィルム状、シート状、ネット状、パンチ又はエキスパンドされたもの、ラス体、多孔質体、発泡体、繊維群の形成体などが挙げられる。集電体の厚さは、例えば１～５００μｍのものが用いられる。 Examples of conductive materials for the positive electrode include graphite such as natural graphite (scaly graphite, flaky graphite) and artificial graphite, acetylene black, carbon black, Ketjen black, carbon whisker, needle coke, carbon fiber, metals (copper, nickel), etc. , aluminum, silver, gold, etc.). Examples of the binder include fluorine-containing resins such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), and fluororubber, thermoplastic resins such as polypropylene and polyethylene, ethylene propylene diene rubber (EPDM), and sulfone. Chemically modified EPDM rubber, natural butyl rubber (NBR), etc. can be used. Furthermore, an aqueous binder such as a cellulose binder or an aqueous dispersion of styrene-butadiene rubber (SBR) can also be used. As the solvent, for example, organic solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, methylethylketone, cyclohexanone, methyl acetate, methyl acrylate, diethylenetriamine, N,N-dimethylaminopropylamine, ethylene oxide, and tetrahydrofuran can be used. can. Alternatively, the active material may be slurried with latex such as SBR by adding a dispersant, a thickener, etc. to water. As the thickener, for example, polysaccharides such as carboxymethyl cellulose and methyl cellulose can be used alone or as a mixture of two or more. Application methods include, for example, roller coating using an applicator roll, screen coating, doctor blade method, spin coating, bar coater, etc. Any of these methods can be used to obtain an arbitrary thickness and shape. Current collectors include aluminum, titanium, stainless steel, nickel, iron, sintered carbon, conductive polymers, conductive glass, etc., as well as aluminum, copper, etc. for the purpose of improving adhesiveness, conductivity, and oxidation resistance. It is possible to use materials whose surfaces have been treated with carbon, nickel, titanium, silver, etc. It is also possible to oxidize the surface of these materials. Examples of the shape of the current collector include foil, film, sheet, net, punched or expanded material, lath material, porous material, foam material, and fiber group formed material. The thickness of the current collector used is, for example, 1 to 500 μm.
負極は、例えば、負極活物質と導電材と結着材とを混合し、適当な溶剤を加えてペースト状の負極合材としたものを、集電体の表面に塗布乾燥し、必要に応じて電極密度を高めるべく圧縮して形成してもよいし、負極活物質と集電体とを密着させて形成したものとしてもよい。負極活物質は、Ｌｉ基準の酸化還元電位が不活性化剤に含まれるレドックスシャトル剤よりも低いものであればよいが、酸化還元電位がＬｉ基準電位で１．５Ｖ未満のものが好ましく、１．０Ｖ以下のものがより好ましく、０．５Ｖ以下のものがさらに好ましい。負極活物質としては、リチウム、リチウム合金、スズ化合物などの無機化合物、リチウムイオンを吸蔵・放出可能な炭素質材料、複数の元素を含む複合酸化物、導電性ポリマーなどが挙げられる。炭素質材料は、例えば、コークス類、ガラス状炭素類、グラファイト類、難黒鉛化性炭素類、熱分解炭素類、炭素繊維などが挙げられる。複合酸化物としては、例えば、Ｌｉ4Ｔｉ5Ｏ12などのリチウムチタン複合酸化物やＬｉＶ2Ｏ3などのリチウムバナジウム複合酸化物が挙げられる。負極活物質としては、このうち、グラファイト類などの炭素質材料が好ましい。また、負極に用いられる導電材、結着材、溶剤などは、それぞれ正極で例示したものを用いることができる。負極の集電体には、銅、ニッケル、ステンレス鋼、チタン、アルミニウム、焼成炭素、導電性高分子、導電性ガラス、Ａｌ－Ｃｄ合金などのほか、接着性、導電性及び耐還元性向上の目的で、例えば銅などの表面をカーボン、ニッケル、チタンや銀などで処理したものも用いることができる。これらについては、表面を酸化処理することも可能である。集電体の形状は、正極と同様のものを用いることができる。負極の集電体は、これらのうち、銅を含むものであることが好ましい。銅は、酸化還元電位がＬｉ基準電位で約３．０～３．５Ｖであるため（J. Electrochem. Soc. 144 (1997) 3476-3483、J. Mater. Chem. 21 (2011) 9891-9911等参照）、不活性化の際、負極電位を３．０Ｖ未満に保てば銅の溶出が抑制されると考えられ、本開示の不活性化剤及び不活性化方法を適用する意義が特に高いからである。負極からの銅の溶出が抑制されると、正極での銅の析出も抑制されるため、不活性化後に非水系二次電池をリサイクル又は廃棄する際に、析出物を正極から除去又は回収する必要がなく、効率よくリサイクル又は廃棄できるため好ましい。 For the negative electrode, for example, a negative electrode active material, a conductive material, and a binder are mixed, an appropriate solvent is added to make a paste-like negative electrode mixture, which is applied and dried on the surface of a current collector, and then applied as needed. The negative electrode active material and the current collector may be formed by being compressed to increase the electrode density, or the negative electrode active material and the current collector may be formed in close contact with each other. The negative electrode active material may have a Li-based redox potential lower than the redox shuttle agent contained in the deactivating agent, but it is preferable that the redox potential is less than 1.5 V with the Li-based potential. It is more preferably .0V or less, and even more preferably 0.5V or less. Examples of negative electrode active materials include inorganic compounds such as lithium, lithium alloys, and tin compounds, carbonaceous materials capable of intercalating and deintercalating lithium ions, composite oxides containing multiple elements, and conductive polymers. Examples of carbonaceous materials include cokes, glassy carbons, graphites, non-graphitizable carbons, pyrolytic carbons, and carbon fibers. Examples of the composite oxide include lithium titanium composite oxides such as Li 4 Ti 5 O 12 and lithium vanadium composite oxides such as LiV 2 O 3 . Among these, carbonaceous materials such as graphites are preferred as the negative electrode active material. Further, as the conductive material, binding material, solvent, etc. used in the negative electrode, those exemplified for the positive electrode can be used. The current collector of the negative electrode is made of copper, nickel, stainless steel, titanium, aluminum, fired carbon, conductive polymer, conductive glass, Al-Cd alloy, etc., as well as materials with improved adhesiveness, conductivity, and reduction resistance. For this purpose, for example, copper or the like whose surface is treated with carbon, nickel, titanium, silver, etc. can also be used. It is also possible to oxidize the surface of these materials. The shape of the current collector can be similar to that of the positive electrode. Among these, the current collector of the negative electrode preferably contains copper. Copper has an oxidation-reduction potential of about 3.0 to 3.5 V based on Li reference potential (J. Electrochem. Soc. 144 (1997) 3476-3483, J. Mater. Chem. 21 (2011) 9891-9911 It is thought that elution of copper is suppressed by keeping the negative electrode potential below 3.0 V during inactivation, and the significance of applying the inactivating agent and inactivating method of the present disclosure is particularly significant. This is because it is expensive. When copper elution from the negative electrode is suppressed, copper precipitation at the positive electrode is also suppressed, so when recycling or disposing of a non-aqueous secondary battery after inactivation, the precipitates must be removed or collected from the positive electrode. This is preferable because it is unnecessary and can be recycled or disposed of efficiently.
イオン伝導媒体としては、支持塩を含む非水系電解液や非水系ゲル電解液などを用いることができる。非水系電解液の溶媒としては、例えば、カーボネート化合物、エステル化合物、エーテル化合物、ニトリル化合物、アミド化合物、フラン化合物、スルホラン化合物及びジオキソラン化合物などが挙げられ、これらを単独又は混合して用いることができる。具体的には、カーボネート化合物としてエチレンカーボネート（ＥＣ）やプロピレンカーボネート、ビニレンカーボネート、ブチレンカーボネート、クロロエチレンカーボネートなどの環状カーボネート化合物や、ジメチルカーボネート（ＤＭＣ）、エチルメチルカーボネート（ＥＭＣ）、ジエチルカーボネート（ＤＥＣ）、エチル－ｎ－ブチルカーボネート、メチル－ｔ－ブチルカーボネート、ジ－ｉ－プロピルカーボネート、ｔ－ブチル－ｉ－プロピルカーボネートなどの鎖状カーボネート化合物などが挙げられる。また、エステル化合物としてγ－ブチルラクトン、γ－バレロラクトンなどの環状エステル化合物、ギ酸メチル、酢酸メチル、酢酸エチル、酪酸メチルなどの鎖状エステル化合物などが挙げられる。また、エーテル化合物としてジメトキシエタン、エトキシメトキシエタン、ジエトキシエタンなどが挙げられ、ニトリル化合物としてアセトニトリル、ベンゾニトリルなどが挙げられ、アミド化合物としてジメチルアセトアミド（ＤＭＡ）、ジメチルホルムアミドなどが挙げられ、フラン化合物としてテトラヒドロフラン、メチルテトラヒドロフランなどが挙げられ、スルホラン化合物としてスルホラン、テトラメチルスルホランなどが挙げられ、オキソラン化合物として１，３－ジオキソラン、メチルジオキソランなどが挙げられる。これらは単独又は混合して用いることができる。このうち、非水系電解液の溶媒としては、例えば、ＤＭＣ－ＥＣや、ＤＥＣ－ＥＣ、ＤＭＣ－ＥＭＣ－ＥＣなど、環状カーボネート化合物と鎖状カーボネート化合物との混合液が好ましい。支持塩としては、例えば、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＡｓＦ6、ＬｉＣｌＯ4 などの無機塩や、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＣ（ＣＦ3ＳＯ2）3、などの有機塩が挙げられ、これらを単独又は組み合わせて用いることができる。支持塩は、電解液中の濃度が０．１ｍｏｌ／Ｌ以上５ｍｏｌ／Ｌ以下であることが好ましく、０．５ｍｏｌ／Ｌ以上２ｍｏｌ／Ｌ以下であることがより好ましい。また、イオン伝導媒体としては、液状のイオン伝導媒体の代わりに、イオン伝導性ポリマー、無機固体電解質あるいは有機ポリマー電解質と無機固体電解質の混合材料、若しくは有機バインダーによって結着された無機固体粉末などを利用することができる。 As the ion conductive medium, a nonaqueous electrolyte containing a supporting salt, a nonaqueous gel electrolyte, or the like can be used. Examples of the solvent for the nonaqueous electrolyte include carbonate compounds, ester compounds, ether compounds, nitrile compounds, amide compounds, furan compounds, sulfolane compounds, and dioxolane compounds, and these can be used alone or in combination. . Specifically, carbonate compounds include cyclic carbonate compounds such as ethylene carbonate (EC), propylene carbonate, vinylene carbonate, butylene carbonate, and chloroethylene carbonate, as well as dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), and diethyl carbonate (DEC). ), ethyl-n-butyl carbonate, methyl-t-butyl carbonate, di-i-propyl carbonate, and t-butyl-i-propyl carbonate. Examples of ester compounds include cyclic ester compounds such as γ-butyllactone and γ-valerolactone, and chain ester compounds such as methyl formate, methyl acetate, ethyl acetate, and methyl butyrate. In addition, ether compounds include dimethoxyethane, ethoxymethoxyethane, diethoxyethane, etc., nitrile compounds include acetonitrile, benzonitrile, etc., amide compounds include dimethylacetamide (DMA), dimethylformamide, etc., and furan compounds include dimethylacetamide (DMA), dimethylformamide, etc. Examples of the sulfolane compound include sulfolane, tetramethylsulfolane, etc., and oxolane compounds include 1,3-dioxolane, methyldioxolane, etc. These can be used alone or in combination. Among these, as the solvent for the nonaqueous electrolyte, a mixed solution of a cyclic carbonate compound and a chain carbonate compound, such as DMC-EC, DEC-EC, and DMC-EMC-EC, is preferable. Examples of supporting salts include inorganic salts such as LiPF 6 , LiBF 4 , LiAsF 6 , and LiClO 4 , and organic salts such as LiCF 3 SO 3 , LiN(CF 3 SO 2 ) 2 , and LiC(CF 3 SO 2 ) 3 . Salts are mentioned, and these can be used alone or in combination. The concentration of the supporting salt in the electrolytic solution is preferably 0.1 mol/L or more and 5 mol/L or less, more preferably 0.5 mol/L or more and 2 mol/L or less. In addition, as the ion conductive medium, instead of a liquid ion conductive medium, an ion conductive polymer, an inorganic solid electrolyte, a mixed material of an organic polymer electrolyte and an inorganic solid electrolyte, or an inorganic solid powder bound by an organic binder may be used. can be used.
この非水系二次電池は、正極と負極との間にセパレータを備えていてもよい。セパレータは、非水系二次電池の使用範囲に耐えうる組成であれば特に限定されないが、例えば、ポリプロピレン製不織布などの高分子不織布、ポリエチレンなどのオレフィン系樹脂の薄い微多孔膜が挙げられる。これらは単独で用いてもよいし、複数を混合して用いてもよい。 This non-aqueous secondary battery may include a separator between the positive electrode and the negative electrode. The separator is not particularly limited as long as it has a composition that can withstand the usage range of non-aqueous secondary batteries, but examples thereof include polymeric nonwoven fabrics such as polypropylene nonwoven fabrics, and thin microporous membranes made of olefin resins such as polyethylene. These may be used alone or in combination.
この非水系二次電池の形状は、特に限定されないが、例えばコイン型、ボタン型、シート型、積層型、円筒型、偏平型、角型などが挙げられる。また、電気自動車等に用いる大型のものとしてもよい。非水系二次電池の一例を図１に示す。図１は、コイン型の非水系二次電池２０の構成の概略を表す断面図である。図１に示すように、非水系二次電池２０は、カップ形状の電池ケース２１と、正極活物質を有しこの電池ケース２１の下部に設けられた正極２２と、負極活物質を有し正極２２に対してセパレータ２４を介して対向する位置に設けられた負極２３と、絶縁材により形成されたガスケット２５と、電池ケース２１の開口部に配設されガスケット２５を介して電池ケース２１を密封する封口板２６と、を備えている。この非水系二次電池２０は、正極２２と負極２３との間の空間にリチウム塩を溶解したイオン伝導媒体２７を備えている。
The shape of this nonaqueous secondary battery is not particularly limited, and examples thereof include a coin shape, a button shape, a sheet shape, a stacked type, a cylindrical shape, a flat shape, a square shape, and the like. It may also be a large one used in electric vehicles and the like. An example of a non-aqueous secondary battery is shown in FIG. FIG. 1 is a cross-sectional view schematically showing the configuration of a coin-shaped non-aqueous
［不活性化剤］
次に、不活性化剤について説明する。不活性化剤は、レドックスシャトル剤と、非水系溶媒と、を含む。
[Deactivating agent]
Next, the deactivating agent will be explained. The deactivating agent includes a redox shuttle agent and a non-aqueous solvent.
不活性化剤に含まれる非水系溶媒は、特に限定されるものではないが、例えば非水系二次電池のイオン伝導媒体に用いられる非水系電解液の溶媒としてもよい。こうした非水系溶媒としては、例えば、カーボネート化合物、エステル化合物、エーテル化合物、ニトリル化合物、アミド化合物、フラン化合物、スルホラン化合物及びジオキソラン化合物などが挙げられ、これらを単独又は混合して用いることができる。具体的には、カーボネート化合物としてエチレンカーボネートやプロピレンカーボネート、ビニレンカーボネート、ブチレンカーボネート、クロロエチレンカーボネートなどの環状カーボネート化合物や、ジメチルカーボネート、エチルメチルカーボネート、ジエチルカーボネート、エチル－ｎ－ブチルカーボネート、メチル－ｔ－ブチルカーボネート、ジ－ｉ－プロピルカーボネート、ｔ－ブチル－ｉ－プロピルカーボネートなどの鎖状カーボネート化合物などが挙げられる。また、エステル化合物としてγ－ブチルラクトン、γ－バレロラクトンなどの環状エステル化合物、ギ酸メチル、酢酸メチル、酢酸エチル、酪酸メチルなどの鎖状エステル化合物などが挙げられる。また、エーテル化合物としてジメトキシエタン、エトキシメトキシエタン、ジエトキシエタンなどが挙げられ、ニトリル化合物としてアセトニトリル、ベンゾニトリルなどが挙げられ、アミド化合物としてジメチルアセトアミド、ジメチルホルムアミドなどが挙げられ、フラン化合物としてテトラヒドロフラン、メチルテトラヒドロフランなどが挙げられ、スルホラン化合物としてスルホラン、テトラメチルスルホランなどが挙げられ、オキソラン化合物として１，３－ジオキソラン、メチルジオキソランなどが挙げられる。この非水系溶媒は、不活性化の対象となる非水系二次電池のイオン伝導媒体に含まれる溶媒と同じでもよいし、異なってもよい。不活性化剤に含まれる非水系溶媒は、例えば、レドックスシャトル剤が後述のビオロゲン類の場合には、ＥＣやＤＭＣ、ＥＭＣなどのカーボネート化合物を含むものが好ましく、レドックスシャトル剤が後述のキノン類の場合にはＤＭＡなどのアミド化合物を含むものが好ましい。こうしたレドックスシャトル剤と非水系溶媒との組合せでは、レドックスシャトル剤の酸化体及び還元体が非水系溶媒との相互作用によって安定化され、レドックスシャトル剤がより安定した酸化還元を示すと考えられる。 The non-aqueous solvent contained in the deactivator is not particularly limited, but may be, for example, a solvent for a non-aqueous electrolyte used in an ion-conducting medium of a non-aqueous secondary battery. Examples of such non-aqueous solvents include carbonate compounds, ester compounds, ether compounds, nitrile compounds, amide compounds, furan compounds, sulfolane compounds, and dioxolane compounds, which can be used alone or in combination. Specifically, carbonate compounds include cyclic carbonate compounds such as ethylene carbonate, propylene carbonate, vinylene carbonate, butylene carbonate, and chloroethylene carbonate, as well as dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, ethyl-n-butyl carbonate, and methyl-t. Examples include chain carbonate compounds such as -butyl carbonate, di-i-propyl carbonate, and t-butyl-i-propyl carbonate. Examples of ester compounds include cyclic ester compounds such as γ-butyllactone and γ-valerolactone, and chain ester compounds such as methyl formate, methyl acetate, ethyl acetate, and methyl butyrate. Further, ether compounds include dimethoxyethane, ethoxymethoxyethane, diethoxyethane, etc., nitrile compounds include acetonitrile, benzonitrile, etc., amide compounds include dimethylacetamide, dimethylformamide, etc., and furan compounds include tetrahydrofuran, Examples of the sulfolane compound include sulfolane and tetramethylsulfolane, and examples of the oxolane compound include 1,3-dioxolane and methyldioxolane. This non-aqueous solvent may be the same as or different from the solvent contained in the ion conductive medium of the non-aqueous secondary battery to be inactivated. The non-aqueous solvent contained in the inactivating agent preferably contains a carbonate compound such as EC, DMC, or EMC when the redox shuttle agent is a viologen as described below, and a nonaqueous solvent containing a carbonate compound such as EC, DMC, or EMC is preferable when the redox shuttle agent is a quinone as described below. In this case, those containing an amide compound such as DMA are preferred. In such a combination of a redox shuttle agent and a non-aqueous solvent, the oxidized form and reduced form of the redox shuttle agent are stabilized by interaction with the non-aqueous solvent, and it is thought that the redox shuttle agent exhibits more stable redox.
不活性化剤に含まれるレドックスシャトル剤は、酸化還元電位がＬｉ基準電位で、不活性化の対象となる非水系二次電池の負極活物質よりも高く、不活性化の対象となる非水系二次電池の正極活物質よりも低く、かつ３．０Ｖ未満のものである。 The redox shuttle agent contained in the deactivating agent has an oxidation-reduction potential higher than the negative electrode active material of the non-aqueous secondary battery, which is the target of deactivation, at the Li reference potential. It is lower than the positive electrode active material of the secondary battery and less than 3.0V.
レドックスシャトル剤の酸化還元電位は、サイクリックボルタンメトリーで求めることができる。具体的には、レドックスシャトル剤の酸化還元電位は、サイクリックボルタンメトリーで求めた酸化側のピーク電位をＥpa［Ｖ］、還元側のピーク電位をＥpc［Ｖ］としたときに、Ｅ0＝（Ｅpa＋Ｅpc）／２で求められる値Ｅ0［Ｖ］とする。電位窓内に２つ以上の酸化還元電位がある場合には、全ての酸化還元電位が３．０Ｖ未満（好ましくは後述する好適範囲内）であることが好ましい。サイクリックボルタンメトリーは、非水系溶媒と支持電解質とレドックスシャトル剤と含む測定溶液に対して行うことが好ましい。測定溶液の非水系溶媒としては、不活性化剤の非水系溶媒として例示したものとしてもよく、目的とする不活性化剤の非水系溶媒と同種のものとしてもよい。測定溶液の支持電解質としては、例えば、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＡｓＦ6、ＬｉＣｌＯ4 などの無機塩や、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＣ（ＣＦ3ＳＯ2）3、などの有機塩が挙げられ、これらを単独又は組み合わせて用いることができる。測定溶液の支持電解質は、不活性化の対象となる非水系二次電池の支持塩と同種のものとしてもよい。測定溶液中の支持電解質の濃度は、０．１ｍｏｌ／Ｌ以上５ｍｏｌ／Ｌ以下としてもよく、０．５ｍｏｌ／Ｌ以上２ｍｏｌ／Ｌ以下としてもよく、不活性化の対象となる非水系二次電池のイオン伝導媒体中の支持塩の濃度と同じとしてもよい。測定溶液中のレドックスシャトル剤の濃度は、１ｍｍｏｌ／Ｌ以上溶解度以下としてもよく、３０ｍｍｏｌ／Ｌ以上溶解度以下としてもよく、５０ｍｍｏｌ／Ｌ以上１００ｍｍｏｌ／Ｌ以下としてもよい。測定溶液中のレドックスシャトル剤の濃度は、目的とする不活性化剤のレドックスシャトル剤の濃度と同じとしてもよい。 The redox potential of the redox shuttle agent can be determined by cyclic voltammetry. Specifically, the redox potential of the redox shuttle agent is E 0 when the peak potential on the oxidation side determined by cyclic voltammetry is E pa [V] and the peak potential on the reduction side is E pc [V ] . The value E 0 [V] is determined by = (E pa +E pc )/2. When there are two or more redox potentials within the potential window, it is preferable that all the redox potentials are less than 3.0 V (preferably within the preferred range described below). Cyclic voltammetry is preferably performed on a measurement solution containing a nonaqueous solvent, a supporting electrolyte, and a redox shuttle agent. The non-aqueous solvent of the measurement solution may be one exemplified as the non-aqueous solvent of the deactivating agent, or the same type as the non-aqueous solvent of the target deactivating agent. Examples of the supporting electrolyte of the measurement solution include inorganic salts such as LiPF 6 , LiBF 4 , LiAsF 6 , and LiClO 4 , LiCF 3 SO 3 , LiN(CF 3 SO 2 ) 2 , LiC(CF 3 SO 2 ) 3 , These organic salts can be used alone or in combination. The supporting electrolyte of the measurement solution may be of the same type as the supporting salt of the non-aqueous secondary battery to be inactivated. The concentration of the supporting electrolyte in the measurement solution may be 0.1 mol/L or more and 5 mol/L or less, or 0.5 mol/L or more and 2 mol/L or less. may be the same as the concentration of supporting salt in the ionically conductive medium. The concentration of the redox shuttle agent in the measurement solution may be 1 mmol/L or more and less than solubility, 30 mmol/L or more and less than solubility, or 50 mmol/L or more and 100 mmol/L or less. The concentration of the redox shuttle agent in the measurement solution may be the same as the concentration of the redox shuttle agent of the target inactivating agent.
レドックスシャトル剤は、酸化還元電位がＬｉ基準電位で３．０Ｖ未満のものであればよいが、０．５Ｖ以上３．０Ｖ未満のものが好ましく、１．０Ｖ以上３．０Ｖ未満のものがより好ましく、１．５Ｖ以上２．９Ｖ以下のものがさらに好ましい。酸化還元電位がＬｉ基準電位で３．０Ｖ未満のレドックスシャトル剤としては、例えば、ビオロゲン類やキノン類が挙げられる。なお、本明細書において、ビオロゲン類とは、ビオロゲン及びビオロゲン誘導体を指し、キノン類とは、キノン及びキノン誘導体を指す。 The redox shuttle agent may have an oxidation-reduction potential of less than 3.0V based on the Li reference potential, but it is preferably 0.5V or more and less than 3.0V, more preferably 1.0V or more and less than 3.0V. Preferably, 1.5V or more and 2.9V or less is more preferable. Examples of the redox shuttle agent having an oxidation-reduction potential of less than 3.0 V based on Li reference potential include viologens and quinones. In addition, in this specification, viologens refer to viologen and viologen derivatives, and quinones refer to quinones and quinone derivatives.
ビオロゲン類は、４，４’－ビピリジン骨格の二つのピリジン環窒素原子に各々炭化水素基が結合した構造を有する化合物であり、例えば式（ｖ１）の構造を有する。式（ｖ１）において、Ｒ及びＲ’は、同じであっても異なってもよい炭化水素基である。炭化水素基としては、鎖状（直鎖でもよいし分岐鎖を有していてもよい）の炭化水素基や環状の炭化水素基が好ましい。鎖状の炭化水素基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デカニル基、ウンデカニル基、ドデカニル基などのアルキル基；ビニル基、プロペニル基、ブテニル基、ペンテニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基などのアルケニル基などが挙げられる。また、環状の炭化水素基としては、シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基などのシクロアルキル基；フェニル基、ナフチル基などのアリール基などが挙げられる。また、これらの炭化水素基は、カルボキシル基、アルコキシ基、ニトロ基、アミノ基、ハロゲン（Ｆ、Ｃｌ、Ｂｒ等）などの置換基を有していてもよい。炭化水素基は、これらのうち、直鎖のアルキル基が好ましく、置換基を有さないものが好ましい。炭化水素基は、各々、炭素数２０以下が好ましく、１０以下がより好ましく、６以下がさらに好ましい。ビオロゲン類は、４，４’－ビピリジン骨格の炭素のうちの１以上に、炭化水素基や、カルボキシル基、アルコキシ基、ニトロ基、アミノ基、ハロゲンなどの置換基が導入された構造を有するものとしてもよい。炭化水素基としては、上述したＲやＲ’の炭化水素基として例示したものなどが挙げられる。ビオロゲン類は、置換基を複数有する場合、置換基同士が結合して環を形成していてもよい。ビオロゲン類は、炭素数３０以下が好ましく、２０以下がより好ましく、１４以下がさらに好ましい。 Viologens are compounds having a structure in which hydrocarbon groups are bonded to two pyridine ring nitrogen atoms of a 4,4'-bipyridine skeleton, and have, for example, the structure of formula (v1). In formula (v1), R and R' are hydrocarbon groups which may be the same or different. As the hydrocarbon group, a chain (which may be straight chain or may have a branched chain) hydrocarbon group or a cyclic hydrocarbon group is preferable. Examples of chain hydrocarbon groups include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decanyl group, undecanyl group, and dodecanyl group; vinyl and alkenyl groups such as a propenyl group, a butenyl group, a pentenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, and a dodecenyl group. Further, examples of the cyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group; and aryl groups such as phenyl group and naphthyl group. Further, these hydrocarbon groups may have a substituent such as a carboxyl group, an alkoxy group, a nitro group, an amino group, or a halogen (F, Cl, Br, etc.). Among these, the hydrocarbon group is preferably a straight-chain alkyl group, and preferably has no substituent. Each hydrocarbon group preferably has 20 or less carbon atoms, more preferably 10 or less carbon atoms, and even more preferably 6 or less carbon atoms. Viologens have a structure in which a substituent such as a hydrocarbon group, carboxyl group, alkoxy group, nitro group, amino group, or halogen is introduced into one or more of the carbon atoms in the 4,4'-bipyridine skeleton. You can also use it as Examples of the hydrocarbon group include those exemplified as the hydrocarbon group for R and R' described above. When the viologens have a plurality of substituents, the substituents may bond to each other to form a ring. The viologens preferably have 30 or less carbon atoms, more preferably 20 or less carbon atoms, and even more preferably 14 or less carbon atoms.
ビオロゲン類としては、具体的には、式（ｖ１）の構造として、メチルビオロゲン（式（ｖ２））、エチルビオロゲン（式（ｖ３））、プロピルビオロゲン（式（ｖ４））、ブチルビオロゲン（式（ｖ５））、ペンチルビオロゲン（式（ｖ６））、ヘキシルビオロゲン（式（ｖ７））、ヘプチルビオロゲン（式（ｖ８））、オクチルビオロゲン（式（ｖ９））などを有するものが挙げられる。また、ビオロゲン類としては、式（ｖ１）の構造として、１，１’－ジメチル－３，３’－［メチレンビス（オキシ）］－４，４’－ビピリジニウム（式（ｖ１０））、フェニルビオロゲン（式（ｖ１１））、１－（４－アミノフェニル）－１’－メチル－４，４’－ビピリジニウム（式（ｖ１２））などを有するものが挙げられる。 Specifically, the viologens have the structure of formula (v1), methyl viologen (formula (v2)), ethyl viologen (formula (v3)), propyl viologen (formula (v4)), butyl viologen (formula (v4)), and butyl viologen (formula (v4)). v5)), pentyl viologen (formula (v6)), hexyl viologen (formula (v7)), heptyl viologen (formula (v8)), and octyl viologen (formula (v9)). In addition, as viologens, the structure of formula (v1) is 1,1'-dimethyl-3,3'-[methylenebis(oxy)]-4,4'-bipyridinium (formula (v10)), phenyl viologen ( Formula (v11)), 1-(4-aminophenyl)-1'-methyl-4,4'-bipyridinium (formula (v12)), and the like.
ビオロゲン類は、式（ｖ１）のカチオンの対アニオンとして、ヘキサフルオロホスフェートアニオン（ＰＦ6 -）、テトラフルオロボレートアニオン（ＢＦ4 -）、ペンタフルオロアルシンアニオン（ＡｓＦ6 -）、パークロレートアニオン（ＣｌＯ4 -）、Ｂｒ-、Ｃｌ-、Ｆ-などの無機アニオンや、トリフルオロメタンスルホン酸アニオン（ＣＦ3ＳＯ3 -）、ビス（トリフルオロメタンスルホニル）イミドアニオン（Ｎ（ＣＦ3ＳＯ2）2 -、ＴＦＳＩ）、トリス（トリフルオロメチルスルホニル）メチドアニオン（Ｃ（ＣＦ3ＳＯ2）3 -）、などの有機アニオンを有していてもよい。対アニオンは、不活性化の対象となる非水系二次電池の支持塩のアニオンと同種のものとしてもよい。 Viologens include hexafluorophosphate anion (PF 6 -), tetrafluoroborate anion (BF 4 - ), pentafluoroarsine anion ( AsF 6 - ), perchlorate anion (ClO) as a counter anion to the cation of formula (v1). 4 - ), Br - , Cl - , F - and other inorganic anions, trifluoromethanesulfonate anion (CF 3 SO 3 - ), bis(trifluoromethanesulfonyl)imide anion (N(CF 3 SO 2 ) 2 - , TFSI), tris(trifluoromethylsulfonyl)methide anion (C(CF 3 SO 2 ) 3 − ), and the like. The counter anion may be of the same type as the anion of the supporting salt of the non-aqueous secondary battery to be inactivated.
キノン類は、芳香族炭化水素骨格の２つの炭素上のＣ－Ｈ基を各々Ｃ＝Ｏ基に置き換えた構造を有する化合物である。キノン類は、４～７員環の芳香族炭化水素骨格を有するものとしてもよく、６員環の芳香族炭化水素骨格を有するもの（ベンゾキノン構造を有するもの）が好ましい。キノン類は、例えば、式（ｑ１）のｐ－ベンゾキノン構造や、式（ｑ２）のｏ－ベンゾキノン構造を有するものとしてもよく、式（ｑ１）のｐ－ベンゾキノン構造を有するものが好ましい。キノン類は、芳香族炭化水素骨格の炭素のうちＣ＝Ｏ基を構成しない炭素の１以上に、炭化水素基や、カルボキシル基、アルコキシ基、ニトロ基、アミノ基、ハロゲン（Ｆ、Ｃｌ、Ｂｒ等）などの置換基が導入された構造を有していてもよい。炭化水素基としては、ビオロゲン類のＲやＲ’の炭化水素基として例示したものなどが挙げられる。キノン類は、置換基を複数有する場合、置換基同士が結合して環を形成していてもよい。置換基同士が結合して環を形成したキノン類としては、例えば、ナフトキノン（１，４－ナフトキノンや１，２－ナフトキノン等）、アントラキノン（９，１０－アントラキノン等）、それらの誘導体などが挙げられる。キノン類は、炭素数２０以下が好ましく、１４以下がより好ましく、１０以下がさらに好ましい Quinones are compounds having a structure in which the CH groups on two carbon atoms of an aromatic hydrocarbon skeleton are each replaced with a C═O group. The quinones may have a 4- to 7-membered aromatic hydrocarbon skeleton, and preferably have a 6-membered aromatic hydrocarbon skeleton (having a benzoquinone structure). The quinones may have, for example, a p-benzoquinone structure of formula (q1) or an o-benzoquinone structure of formula (q2), and those having a p-benzoquinone structure of formula (q1) are preferred. Quinones have a hydrocarbon group, a carboxyl group, an alkoxy group, a nitro group, an amino group, a halogen (F, Cl, Br, etc.) may have a structure in which a substituent is introduced. Examples of the hydrocarbon group include those exemplified as the hydrocarbon group of R and R' of viologens. When quinones have a plurality of substituents, the substituents may be bonded to each other to form a ring. Examples of quinones in which substituents are bonded to each other to form a ring include naphthoquinone (1,4-naphthoquinone, 1,2-naphthoquinone, etc.), anthraquinone (9,10-anthraquinone, etc.), and derivatives thereof. It will be done. The quinones preferably have 20 or less carbon atoms, more preferably 14 or less carbon atoms, and even more preferably 10 or less carbon atoms.
キノン類としては、具体的には、ｐ－ベンゾキノン（式（ｑ３））や、メチル－ｐ－ベンゾキノン（式（ｑ４））、２，５－ジメチル－１，４－ベンゾキノン（式（ｑ５））、メトキシベンゾキノン（式（ｑ６））、２，５－ジヒドロキシ－１，４－ベンゾキノン（式（ｑ７））、１，４－ナフトキノン（式（ｑ８））、２－メチル－１，４－ナフトキノン（式（ｑ９））、２，３－ジクロロ－１，４－ナフトキノン（式（ｑ１０））、２－ヒドロキシ－１，４－ナフトキノン（式（ｑ１１））、アントラキノン（式（ｑ１２））、２－メチルアントラキノン（式（ｑ１３））、２－ｔｅｒｔ－ブチルアントラキノン（式（ｑ１４））、１－クロロアントラキノン（式（ｑ１５））、１，４－ジヒドロキシアントラキノン（式（ｑ１６））、１－ニトロアントラキノン（式（ｑ１７））などが挙げられる。 Specific examples of quinones include p-benzoquinone (formula (q3)), methyl-p-benzoquinone (formula (q4)), and 2,5-dimethyl-1,4-benzoquinone (formula (q5)). , methoxybenzoquinone (formula (q6)), 2,5-dihydroxy-1,4-benzoquinone (formula (q7)), 1,4-naphthoquinone (formula (q8)), 2-methyl-1,4-naphthoquinone ( Formula (q9)), 2,3-dichloro-1,4-naphthoquinone (formula (q10)), 2-hydroxy-1,4-naphthoquinone (formula (q11)), anthraquinone (formula (q12)), 2- Methylanthraquinone (formula (q13)), 2-tert-butylanthraquinone (formula (q14)), 1-chloroanthraquinone (formula (q15)), 1,4-dihydroxyanthraquinone (formula (q16)), 1-nitroanthraquinone (Formula (q17)) and the like.
レドックスシャトル剤は、不活性化剤に含まれる非水溶媒に対する２０℃での溶解度が１ｍｍｏｌ／Ｌ以上であることが好ましく、３０ｍｍｏｌ／Ｌ以上であることがより好ましく、５０ｍｍｏｌ／Ｌ以上であることがさらに好ましい。レドックスシャトル剤の溶解度が高いほど不活性化剤のレドックスシャトル剤濃度を高めることが可能であり、不活性化剤のレドックスシャトル剤濃度が高いほど電気自動車（ＥＶ）用など高エネルギー密度の電池を短時間で放電させることができるからである。上述したビオロゲン類やキノン類は、非水系溶媒への溶解度が比較的高いため、これらをレドックスシャトル剤とすれば、不活性化剤に含まれるレドックスシャトル剤の濃度を高めることができ、好ましい。レドックスシャトル剤は、不活性化剤に含まれる非水溶媒に対する２０℃での溶解度が１０００ｍｍｏｌ／Ｌ以下としてもよく、１００ｍｍｏｌ／Ｌ以下としてもよい。 The solubility of the redox shuttle agent in the nonaqueous solvent contained in the deactivating agent at 20°C is preferably 1 mmol/L or more, more preferably 30 mmol/L or more, and 50 mmol/L or more. is even more preferable. The higher the solubility of the redox shuttle agent, the higher the concentration of the redox shuttle agent in the deactivating agent.The higher the concentration of the redox shuttle agent in the deactivating agent, the higher the concentration of the redox shuttle agent in the deactivating agent. This is because discharge can be performed in a short time. The above-mentioned viologens and quinones have relatively high solubility in non-aqueous solvents, so using them as a redox shuttle agent is preferable because the concentration of the redox shuttle agent contained in the inactivating agent can be increased. The redox shuttle agent may have a solubility at 20° C. of 1000 mmol/L or less in the nonaqueous solvent contained in the deactivating agent, or may have a solubility of 100 mmol/L or less.
不活性化剤に含まれるレドックスシャトル剤の濃度は、１ｍｍｏｌ／Ｌ以上が好ましく、３０ｍｍｏｌ／Ｌ以上がより好ましく、５０ｍｍｏｌ／Ｌ以上がさらに好ましい。レドックスシャトル剤の濃度が高いほど、電気自動車（ＥＶ）用など高エネルギー密度の電池を短時間で放電させることができるからである。不活性化剤に含まれるレドックスシャトル剤の濃度は、溶解度以下としてもよく、１００ｍｍｏｌ／Ｌ以下としてもよい。 The concentration of the redox shuttle agent contained in the inactivating agent is preferably 1 mmol/L or more, more preferably 30 mmol/L or more, and even more preferably 50 mmol/L or more. This is because the higher the concentration of the redox shuttle agent, the faster a battery with high energy density, such as for an electric vehicle (EV), can be discharged. The concentration of the redox shuttle agent contained in the inactivating agent may be less than the solubility, or may be less than 100 mmol/L.
不活性化剤は、レドックスシャトル剤以外には溶質（例えば支持塩）を含まないことが好ましく、レドックスシャトル剤以外の溶質を含むとしても、０．１ｍｍｏｌ／Ｌ未満や０．０１ｍｍｏｌ／Ｌ未満であることが好ましい。不活性化剤において、レドックスシャトル剤以外の溶質が少ないほど、粘度が低い傾向にあるため、不活性化がより迅速に進行するからである。こうした観点から、不活性化剤は、支持塩を含まないことが好ましいが、支持塩を含んでいてもよい。支持塩としては、例えば、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＡｓＦ6、ＬｉＣｌＯ4などの無機塩、及びＬｉＣＦ3ＳＯ3、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＣ（ＣＦ3ＳＯ2）3などの有機塩などが挙げられる。支持塩は、不活性化の対象となる非水系二次電池のイオン伝導媒体に含まれる支持塩と同じでもよいし、異なってもよい。 The inactivating agent preferably does not contain any solutes (e.g. supporting salts) other than the redox shuttle agent, and even if it contains solutes other than the redox shuttle agent, the amount is less than 0.1 mmol/L or less than 0.01 mmol/L. It is preferable that there be. This is because the less solutes other than the redox shuttle agent are contained in the inactivating agent, the lower the viscosity tends to be, and the more quickly inactivation proceeds. From this point of view, the deactivating agent preferably does not contain a supporting salt, but may contain a supporting salt. Examples of supporting salts include inorganic salts such as LiPF 6 , LiBF 4 , LiAsF 6 , and LiClO 4 , and organic salts such as LiCF 3 SO 3 , LiN(CF 3 SO 2 ) 2 , and LiC(CF 3 SO 2 ) 3 . Examples include. The supporting salt may be the same as or different from the supporting salt contained in the ion conductive medium of the non-aqueous secondary battery to be inactivated.
［不活性化方法］
続いて、上述した不活性化剤を用いて上述した非水系二次電池を不活性化する方法について説明する。この不活性化方法は、非水系二次電池の内部に不活性化剤を添加する添加工程を含む。
[Inactivation method]
Next, a method of inactivating the above-mentioned non-aqueous secondary battery using the above-mentioned inactivating agent will be explained. This deactivation method includes an addition step of adding a deactivating agent inside the non-aqueous secondary battery.
添加工程では、非水系二次電池の内部に不活性化剤を添加する。具体的には、非水系二次電池の正極及び負極と不活性化剤とが接触するように、不活性化剤を添加する。不活性化剤の添加方法は、特に限定されないが、電池容器を一旦開封して不活性化剤を注入した後再び封止してもよいし、電池容器の外部から注射器によって注入しその後封止してもよい。添加工程は、アルゴン雰囲気などの不活性雰囲気下で行うことが好ましい。 In the addition step, a deactivating agent is added inside the non-aqueous secondary battery. Specifically, the deactivating agent is added so that the deactivating agent comes into contact with the positive electrode and negative electrode of the non-aqueous secondary battery. The method of adding the deactivating agent is not particularly limited, but the battery container may be opened once, the deactivating agent is injected, and then sealed again, or it may be injected with a syringe from the outside of the battery container and then sealed. You may. The addition step is preferably performed under an inert atmosphere such as an argon atmosphere.
不活性化剤の添加量は、例えば、０．１ｍＬ以上１０ｍＬ未満としてもよく、０．５ｍＬ以上５．０ｍＬ以下としてもよい。不活性化剤の添加量は、例えば、不活性化の対象となる非水系二次電池に含まれるイオン伝導媒体の体積［ｍＬ］に対して、０．１％以上５００％以下としてもよく、１０％以上３００％以下としてもよい。不活性化剤の添加によって非水系二次電池に添加されるレドックスシャトル剤の量（以下レドックスシャトル剤の添加量とも称する）は、例えば、不活性化の対象となる非水系二次電池の満充電時の電池容量［Ａｈ］あたり、０．０００１ｍｏｌ／Ａｈ以上０．１ｍｏｌ／Ａｈ以下としてもよく、０．００１ｍｏｌ／Ａｈ以上０．０１ｍｏｌ／Ａｈ以下としてもよい。 The amount of the deactivating agent added may be, for example, 0.1 mL or more and less than 10 mL, or 0.5 mL or more and 5.0 mL or less. The amount of the deactivating agent added may be, for example, 0.1% or more and 500% or less with respect to the volume [mL] of the ion conductive medium contained in the non-aqueous secondary battery to be deactivated. It is good also as 10% or more and 300% or less. The amount of the redox shuttle agent added to the non-aqueous secondary battery by adding the deactivating agent (hereinafter also referred to as the amount of redox shuttle agent added) is, for example, the amount of the redox shuttle agent added to the non-aqueous secondary battery to be deactivated. It may be set to 0.0001 mol/Ah or more and 0.1 mol/Ah or less, or 0.001 mol/Ah or more and 0.01 mol/Ah or less per battery capacity [Ah] during charging.
この添加工程は、銅を含む負極集電体を有する非水系二次電池に対して行うことが好ましい。銅は、上述した通り酸化還元電位がＬｉ基準電位で約３．０～３．５Ｖであるため、不活性化の際、負極電位を３．０Ｖ未満に保てば銅の溶出が抑制されると考えられ、本開示の不活性化剤を添加する意義が特に高いからである。 This addition step is preferably performed on a non-aqueous secondary battery having a negative electrode current collector containing copper. As mentioned above, copper has an oxidation-reduction potential of about 3.0 to 3.5 V based on the Li reference potential, so elution of copper can be suppressed by keeping the negative electrode potential below 3.0 V during inactivation. This is because adding the inactivating agent of the present disclosure has particularly high significance.
添加工程後の非水系二次電池は、例えば、静置して保持してもよいし、加振しながら保持してもよい。保持時間は、不活性化が完了するまでの時間として経験的に定められる時間とすればよいが、例えば、６時間以上５００時間以下としてもよく、３０時間以上３００時間以下としてもよく、５０時間以上２００時間以下としてもよい。 After the addition step, the non-aqueous secondary battery may be held stationary or may be held while being shaken, for example. The retention time may be determined empirically as the time until inactivation is completed; for example, it may be 6 hours or more and 500 hours or less, 30 hours or more and 300 hours or less, or 50 hours. It may be more than 200 hours or less.
この不活性化方法で非水系二次電池が不活性化するメカニズムは、以下のように推察される。図２は、非水系二次電池が不活性化するメカニズムを示す説明図である。正極電位より低く負極電位より高い酸化還元電位を示すレドックスシャトル剤（図中のＲＳ）を電池に添加すると、正極あるいは負極とレドックスシャトル剤の電位差を駆動力として、負極からレドックスシャトル剤およびレドックスシャトル剤から正極への電子移動が進行し、電池が放電する。具体的には、レドックスシャトル剤の還元体（図中のＲＳ(red)）が正極に電子を与えて酸化体（図中のＲＳ(ox)）となり、レドックスシャトル剤の酸化体が負極から電子を受け取って還元体となる、という動作が繰り返し進行し、電池が放電する。正極電位あるいは負極電位がレドックスシャトル剤の酸化還元電位に等しくなると、その電極の放電はそれ以上進行しなくなる。従って、正極電位と負極電位は、最終的にはレドックスシャトル剤の電位に等しくなり、不活性化が完了する。なお、「不活性化が完了」とは、少なくとも非水系二次電池のＳＯＣ（Ｓｔａｔｅ ｏｆ ｃｈａｒｇｅ）が０％になるまで放電されていることをいうものとしてもよい。ＳＯＣが０％になるまで放電されていれば、負極電位が低すぎない（例えばＬｉ基準電位で１．５Ｖ超過３．０Ｖ未満）ため、イオン伝導媒体（電解液等）の分解によるガス発生が生じにくく、電極自体の安全性も高い。したがって、不活性化後のリサイクルや廃棄を安全に行うことができる。不活性化後の電池電圧は低いほどスパークが起こりにくいため好ましく、例えば、３．０Ｖ以下としてもよく、１．２Ｖ以下や、１．０Ｖ以下、０．５Ｖ以下などとすることがより好ましい。 The mechanism by which a non-aqueous secondary battery is inactivated by this inactivation method is presumed to be as follows. FIG. 2 is an explanatory diagram showing the mechanism by which a non-aqueous secondary battery is inactivated. When a redox shuttle agent (RS in the figure) that exhibits an oxidation-reduction potential lower than the positive electrode potential and higher than the negative electrode potential is added to the battery, the redox shuttle agent and the redox shuttle are released from the negative electrode using the potential difference between the positive electrode or negative electrode and the redox shuttle agent as a driving force. Electron transfer from the agent to the positive electrode progresses, and the battery is discharged. Specifically, the reduced form of the redox shuttle agent (RS (red) in the figure) donates electrons to the positive electrode to become the oxidized form (RS (ox) in the figure), and the oxidized form of the redox shuttle agent transfers electrons from the negative electrode. The process of receiving and becoming a reductant progresses repeatedly, and the battery is discharged. When the positive electrode potential or the negative electrode potential becomes equal to the redox potential of the redox shuttle agent, the discharge at that electrode will no longer proceed. Therefore, the positive electrode potential and the negative electrode potential eventually become equal to the potential of the redox shuttle agent, and inactivation is completed. Note that "inactivation is completed" may mean that the nonaqueous secondary battery is discharged until at least the SOC (state of charge) of the nonaqueous secondary battery becomes 0%. If the SOC is discharged until it reaches 0%, the negative electrode potential is not too low (for example, Li reference potential is more than 1.5 V and less than 3.0 V), so gas generation due to decomposition of the ion conductive medium (electrolyte, etc.) will not occur. It is unlikely that this occurs, and the electrode itself is highly safe. Therefore, recycling and disposal after inactivation can be performed safely. The lower the battery voltage after inactivation is, the less likely sparks will occur, so it is preferable, and for example, it may be set to 3.0V or less, more preferably 1.2V or less, 1.0V or less, 0.5V or less.
以上説明した不活性化剤及び不活性化方法では、非水系二次電池を不活性化する際に、負極電位を低く保つことができる。このような効果が得られる理由は、例えば、以下のように推察される。充電状態の非水系二次電池に、酸化還元電位がＬｉ基準電位で正極電位より低く負極電位より高いレドックスシャトル剤を添加すると、正極及び負極とレドックスシャトル剤との電位差を駆動力として、電池の放電が進行する。放電は、正極電位及び負極電位がレドックスシャトル剤の酸化還元電位に等しくなるまで進行する。このため、酸化還元電位がＬｉ基準電位で３．０Ｖ未満のレドックスシャトル剤を用いることで、不活性化の際の負極電位を低く（例えばＬｉ基準電位で３．０Ｖ未満）に保つことができる。また、銅を負極集電体として備えた非水系二次電池にこの不活性化剤及び不活性化方法を適用すると、負極集電体からの銅の溶出を抑制できる。負極集電体からの銅の溶出が抑制されると、正極での銅の析出も抑制されるため、不活性化後に非水系二次電池をリサイクル又は廃棄する際に、析出物を正極から除去又は回収する必要がなく、効率よくリサイクル又は廃棄できる。 With the deactivating agent and the deactivating method described above, the negative electrode potential can be kept low when deactivating a nonaqueous secondary battery. The reason why such an effect is obtained is presumed to be as follows, for example. When a redox shuttle agent whose oxidation-reduction potential is lower than the positive electrode potential and higher than the negative electrode potential at the Li reference potential is added to a nonaqueous secondary battery in a charged state, the potential difference between the positive electrode, the negative electrode, and the redox shuttle agent is used as a driving force, and the battery The discharge progresses. Discharge proceeds until the positive and negative electrode potentials are equal to the redox potential of the redox shuttle agent. Therefore, by using a redox shuttle agent whose redox potential is less than 3.0 V at Li reference potential, the negative electrode potential during inactivation can be kept low (for example, less than 3.0 V at Li reference potential). . Moreover, when this deactivating agent and deactivation method are applied to a non-aqueous secondary battery equipped with copper as a negative electrode current collector, the elution of copper from the negative electrode current collector can be suppressed. When the elution of copper from the negative electrode current collector is suppressed, copper precipitation on the positive electrode is also suppressed, so when recycling or disposing of a non-aqueous secondary battery after inactivation, the precipitates can be removed from the positive electrode. Or, there is no need to collect it, and it can be efficiently recycled or disposed of.
なお、本開示は、上述した実施形態に何ら限定されることはなく、本開示の技術的範囲に属する限り種々の態様で実施し得ることはいうまでもない。 It goes without saying that the present disclosure is not limited to the embodiments described above, and can be implemented in various forms as long as they fall within the technical scope of the present disclosure.
［実施例１］
実施例１では、レドックスシャトル剤として、メチルビオロゲンヘキサフルオロホスフェート（式（ｖ２）の構造を有し対アニオンはＰＦ6
-、以下ではメチルビオロゲンとも称する）を用いた場合について検討した。
[Example 1]
In Example 1, the case where methyl viologen hexafluorophosphate (having the structure of formula (v2) and the counter anion is PF 6 - , hereinafter also referred to as methyl viologen) was investigated as a redox shuttle agent.
（１）レドックスシャトル剤の酸化還元電位
エチレンカーボネート（ＥＣ）とジメチルカーボネート（ＤＭＣ）とエチルメチルカーボネート（ＥＭＣ）を３：４：３の体積比で混合した混合溶媒に、支持電解質としてヘキサフルオロリン酸リチウム（ＬｉＰＦ6）と、レドックスシャトル剤であるメチルビオロゲンヘキサフルオロホスフェートとを溶解させ、支持電解質を１ｍｏｌ／Ｌ、レドックスシャトル剤を５０ｍｍｏｌ／Ｌの濃度で含む測定溶液を調製した。この測定溶液を用い、Ｈ型セルを用いたサイクリックボルタンメトリーにより、レドックスシャトル剤の酸化還元電位を評価した。作用極としてグラッシーカーボン、対極として金属リチウム、参照電極としてニッケル線に金属リチウムを圧着したものを用いた。測定温度は２０℃、電位範囲はリチウム基準電位で１．５～３．５Ｖ、電位掃引速度は５０ｍＶ／ｓｅｃ．とした。
(1) Redox potential of redox shuttle agent Hexafluoroline was added as a supporting electrolyte to a mixed solvent of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) in a volume ratio of 3:4:3. Lithium oxide (LiPF 6 ) and methyl viologen hexafluorophosphate, which is a redox shuttle agent, were dissolved to prepare a measurement solution containing a supporting electrolyte at a concentration of 1 mol/L and a redox shuttle agent at a concentration of 50 mmol/L. Using this measurement solution, the redox potential of the redox shuttle agent was evaluated by cyclic voltammetry using an H-type cell. Glassy carbon was used as the working electrode, metallic lithium was used as the counter electrode, and metallic lithium was crimped onto a nickel wire as the reference electrode. The measurement temperature was 20°C, the potential range was 1.5 to 3.5V as a lithium reference potential, and the potential sweep rate was 50mV/sec. And so.
（２）非水系二次電池の不活性化
（非水系二次電池の準備）
ＬｉＮｉ1/3Ｃｏ1/3Ｍｎ1/3Ｏ2とアセチレンブラックとポリフッ化ビニリデンとを９３：４：３の重量比で含む正極合材をアルミニウム集電箔に塗工し、正極を作製した。また、黒鉛とカルボキシメチルセルロースとスチレンブタジエンゴムとを９８：１：１の重量比で含む正極合材を銅集電箔に塗工し、負極を作製した。ＥＣとＤＭＣとＥＭＣとを３：４：３の体積比で含む混合溶媒にＬｉＰＦ6を溶解させ、ＬｉＰＦ6を１ｍｏｌ／Ｌの濃度で含む電解液を調製した。セパレータとしては、ポリエチレン単層微多孔膜から構成されるものを用いた。正極と負極を、電解液を浸み込ませたセパレータを介して対向させ、ラミネートフィルム内に封入して、リチウムイオン二次電池を作製した。そして、３．０～４．１Ｖの電圧範囲で充放電を２サイクル実施した後、４．１Ｖまで充電し、満充電状態とした。
(2) Inactivation of non-aqueous secondary batteries (preparation of non-aqueous secondary batteries)
A positive electrode mixture containing LiNi 1/3 Co 1/3 Mn 1/3 O 2 , acetylene black, and polyvinylidene fluoride in a weight ratio of 93:4:3 was applied to an aluminum current collector foil to produce a positive electrode. . Further, a positive electrode mixture containing graphite, carboxymethyl cellulose, and styrene-butadiene rubber in a weight ratio of 98:1:1 was applied to a copper current collector foil to prepare a negative electrode. LiPF 6 was dissolved in a mixed solvent containing EC, DMC, and EMC at a volume ratio of 3:4:3 to prepare an electrolytic solution containing LiPF 6 at a concentration of 1 mol/L. The separator used was one composed of a polyethylene single-layer microporous membrane. A positive electrode and a negative electrode were made to face each other with a separator impregnated with an electrolyte solution interposed therebetween, and the electrodes were sealed in a laminate film to produce a lithium ion secondary battery. After carrying out two cycles of charging and discharging in a voltage range of 3.0 to 4.1V, the battery was charged to 4.1V to bring it into a fully charged state.
（不活性化）
非水系溶媒として、ＥＣとＤＭＣとＥＭＣとを３：４：３の体積比で含む混合溶媒を用いた。また、レドックスシャトル剤として、メチルビオロゲンヘキサフルオロホスフェートを用いた。非水系溶媒にレドックスシャトル剤を溶解させて、レドックスシャトル剤を５０ｍｍｏｌ／Ｌの濃度で含む不活性化剤を調製した。満充電状態の電池を、アルゴン雰囲気下で開封し、不活性化剤を１．２６８ｍＬ（非水系二次電池の電解液の体積［ｍＬ］に対して不活性化剤が２８０％、非水系二次電池の満充電時の電池容量［Ａｈ］あたりレドックスシャトル剤が０．００４ｍｏｌ／Ａｈ）注入し、電池を再度封じて、温度２０ ℃で電圧変化を測定し、リチウムイオン二次電池の不活性化挙動を評価した。
(inactivation)
A mixed solvent containing EC, DMC, and EMC in a volume ratio of 3:4:3 was used as the nonaqueous solvent. Furthermore, methyl viologen hexafluorophosphate was used as a redox shuttle agent. A deactivating agent containing the redox shuttle agent at a concentration of 50 mmol/L was prepared by dissolving the redox shuttle agent in a non-aqueous solvent. A fully charged battery was opened in an argon atmosphere, and 1.268 mL of the deactivating agent was added (the deactivating agent was 280% of the volume [mL] of the electrolyte of the non-aqueous secondary battery). The redox shuttle agent was injected (0.004 mol/Ah per battery capacity [Ah] when the battery was fully charged), the battery was sealed again, and the voltage change was measured at a temperature of 20 °C. The oxidation behavior was evaluated.
（不活性化後の負極及び正極の電位測定）
不活性化後のリチウムイオン二次電池をアルゴン雰囲気下で解体し、負極及び正極を取り出した。リチウムイオン二次電池の電解液と同様に調製した電解液を入れたビーカー内に負極と金属リチウムとを静置し、負極と金属リチウムとの間の電圧をテスターで測定し、それをＬｉ基準の負極電位とした。また、リチウムイオン二次電池の電解液と同様に調製した電解液を入れたビーカー内に正極と金属リチウムとを静置し、正極と金属リチウムとの間の電圧をテスターで測定し、それをＬｉ基準の正極電位とした。
(Potential measurement of negative and positive electrodes after inactivation)
The lithium ion secondary battery after inactivation was disassembled under an argon atmosphere, and the negative electrode and positive electrode were taken out. The negative electrode and metallic lithium are placed in a beaker containing an electrolytic solution prepared in the same manner as the electrolytic solution of a lithium ion secondary battery, and the voltage between the negative electrode and metallic lithium is measured with a tester, and the voltage is determined based on the Li standard. The negative electrode potential was set to . In addition, the positive electrode and metallic lithium were placed in a beaker containing an electrolytic solution prepared in the same manner as the electrolytic solution for lithium-ion secondary batteries, and the voltage between the positive electrode and metallic lithium was measured with a tester. The positive electrode potential was based on Li.
［実施例２］
実施例２では、レドックスシャトル剤としてｐ－ベンゾキノン（式（ｑ３））を用いた場合について検討した。
[Example 2]
In Example 2, a case was investigated in which p-benzoquinone (formula (q3)) was used as a redox shuttle agent.
（１）レドックスシャトル剤の酸化還元電位
Ｎ，Ｎ－ジメチルアセトアミド（ＤＭＡ）に、支持電解質としてリチウムビス（トリフルオロメタンスルホニル）イミド（ＬｉＴＦＳＩ）と、レドックスシャトル剤であるｐ－ベンゾキノンとを溶解させ、支持電解質を０．１ｍｏｌ／Ｌ、レドックスシャトル剤を５０ｍｍｏｌ／Ｌの濃度で含む測定溶液を調製した。この測定溶液を用い、電位範囲をリチウム基準電位で２．１～４．０Ｖとした以外は、実施例１と同様にサイクリックボルタンメトリーを行い、レドックスシャトル剤の酸化還元電位を評価した。
(1) Redox potential of redox shuttle agent Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as a supporting electrolyte and p-benzoquinone as a redox shuttle agent are dissolved in N,N-dimethylacetamide (DMA), A measurement solution containing a supporting electrolyte at a concentration of 0.1 mol/L and a redox shuttle agent at a concentration of 50 mmol/L was prepared. Using this measurement solution, cyclic voltammetry was performed in the same manner as in Example 1, except that the potential range was 2.1 to 4.0 V based on the lithium reference potential, and the redox potential of the redox shuttle agent was evaluated.
（２）非水系二次電池の不活性化
非水系溶媒として、ＤＭＡを用いた。また、レドックスシャトル剤としてｐ－ベンゾキノンを用いた。非水系溶媒にレドックスシャトル剤を溶解させて、レドックスシャトル剤を５０ｍｍｏｌ／Ｌの濃度で含む不活性化剤を調製した。この不活性化剤を用いた以外は、実施例１と同様にリチウムイオン二次電池の不活性化挙動を評価した。
(2) Inactivation of non-aqueous secondary battery DMA was used as the non-aqueous solvent. Furthermore, p-benzoquinone was used as a redox shuttle agent. A deactivating agent containing the redox shuttle agent at a concentration of 50 mmol/L was prepared by dissolving the redox shuttle agent in a non-aqueous solvent. The deactivation behavior of a lithium ion secondary battery was evaluated in the same manner as in Example 1 except that this deactivating agent was used.
［比較例１］
比較例１では、レドックスシャトル剤としてフェロセンを用いた場合について検討した。
[Comparative example 1]
In Comparative Example 1, a case where ferrocene was used as a redox shuttle agent was investigated.
（１）レドックスシャトル剤の酸化還元電位
ＥＣとＤＭＣとＥＭＣとを３：４：３の体積比で含む混合溶媒に、支持電解質としてＬｉＰＦ6と、レドックスシャトル剤としてフェロセンとを溶解させ、支持電解質を１ｍｏｌ／Ｌ、レドックスシャトル剤を５０ｍｍｏｌ／Ｌの濃度で含む測定溶液を調製した。この測定溶液を用い、電位範囲をリチウム基準電位で２．５～４．３Ｖとした以外は、実施例１と同様にサイクリックボルタンメトリーを行い、レドックスシャトル剤の酸化還元電位を評価した。
(1) Redox potential of redox shuttle agent LiPF 6 as a supporting electrolyte and ferrocene as a redox shuttle agent are dissolved in a mixed solvent containing EC, DMC, and EMC at a volume ratio of 3:4:3. A measurement solution was prepared containing a concentration of 1 mol/L and a redox shuttle agent of 50 mmol/L. Using this measurement solution, cyclic voltammetry was performed in the same manner as in Example 1, except that the potential range was 2.5 to 4.3 V based on lithium reference potential, and the redox potential of the redox shuttle agent was evaluated.
（２）非水系二次電池の不活性化
レドックスシャトル剤としてメチルビオロゲンではなくフェロセンを含む不活性化剤を用いた以外は、実施例１と同様にリチウムイオン二次電池の不活性化挙動を評価し、不活性化後の負極電位及び正極電位を測定した。
(2) Inactivation of nonaqueous secondary batteries The inactivation behavior of lithium ion secondary batteries was evaluated in the same manner as in Example 1, except that a deactivation agent containing ferrocene was used as the redox shuttle agent instead of methyl viologen. The negative electrode potential and positive electrode potential after inactivation were measured.
［参考例１］
ビオロゲン類の種々の化合物（カチオン）に関し、密度汎関数法により酸化還元電位を計算した。酸化体のギブズ自由エネルギー（ΔＧOX）と還元体のギブズ自由エネルギー（ΔＧRED）をそれぞれ計算し、一電子還元を想定して下記数式（１）から対象の酸化還元電位Ｅabsを絶対電位として算出した。
Ｅabs＝（ΔＧOX－ΔＧRED）／Ｆ ・・・数式（１）
数式（１）中、Ｆはファラデー定数９６４８５Ｃ／ｍｏｌである。
[Reference example 1]
Redox potentials of various viologen compounds (cations) were calculated using density functional theory. Calculate the Gibbs free energy of the oxidant (ΔG OX ) and the Gibbs free energy of the reductant (ΔG RED ), and assuming one-electron reduction, use the following formula (1) to calculate the target redox potential E abs as an absolute potential. Calculated.
E abs = (ΔG OX - ΔG RED )/F ... Formula (1)
In formula (1), F is a Faraday constant of 96485 C/mol.
得られた絶対電位から下記数式（２）を用いてリチウム電極基準の酸化還元電位ＥRedOxを計算した。
ＥRedOx［Ｖ ｖｓ．Ｌｉ+／Ｌｉ］＝Ｅabs－１．４ ・・・数式（２）
The oxidation-reduction potential E RedOx based on the lithium electrode was calculated from the obtained absolute potential using the following mathematical formula (2).
E RedOx [V vs. Li + /Li] = E abs -1.4 ... Formula (2)
自由エネルギーは密度汎関数法を用いて計算した。Ｇａｕｓｓｉａｎ０９ Ｒｅｖｉｓｉｏｎ Ｅパッケージで汎関数及び基底関数にＢ３ＬＹＰ及び６－３１１＋＋ＧＧ（ｄ，ｐ）を用い、連続分極モデルにより溶媒の誘電率を２９．１１として溶媒和効果を取り入れた。 Free energy was calculated using density functional theory. Using the Gaussian09 Revision E package, B3LYP and 6-311++GG(d,p) were used as the functional and basis functions, and the dielectric constant of the solvent was set to 29.11 using a continuous polarization model to incorporate the solvation effect.
［参考例２］
キノン類の種々の化合物に関し、参考例１と同様の方法で酸化還元電位を計算した。
[Reference example 2]
Redox potentials of various quinone compounds were calculated in the same manner as in Reference Example 1.
［参考例３］
ＤＭＡに支持電解質としてＬｉＴＦＳＩと、レドックスシャトル剤として１，４－ナフトキノン（式（ｑ８））とを溶解させ、支持電解質を０．１ｍｏｌ／Ｌ、レドックスシャトル剤を５０ｍｍｏｌ／Ｌの濃度で含む測定溶液を調製した。この測定溶液を用いた以外は、実施例１と同様にサイクリックボルタンメトリーを行い、レドックスシャトル剤の酸化還元電位を評価した。なお、電位範囲はリチウム基準電位で１．５～３．５Ｖとした。
[Reference example 3]
A measurement solution in which LiTFSI as a supporting electrolyte and 1,4-naphthoquinone (formula (q8)) as a redox shuttle agent are dissolved in DMA, and the supporting electrolyte is contained at a concentration of 0.1 mol/L and the redox shuttle agent at a concentration of 50 mmol/L. was prepared. Cyclic voltammetry was performed in the same manner as in Example 1, except that this measurement solution was used, and the redox potential of the redox shuttle agent was evaluated. Note that the potential range was 1.5 to 3.5 V based on lithium reference potential.
［参考例４］
ＤＭＡに支持電解質としてＬｉＴＦＳＩと、レドックスシャトル剤としてアントラキノン（式（ｑ１２））とを溶解させ、支持電解質を０．１ｍｏｌ／Ｌの濃度で含み、レドックスシャトル剤を溶解度（５０ｍｍｏｌ／Ｌ未満）だけ含む測定溶液を調製した。この測定溶液を用い、電位範囲をリチウム基準電位で１．５～３．０Ｖとした以外は、実施例１と同様にサイクリックボルタンメトリーを行い、レドックスシャトル剤の酸化還元電位を評価した。
[Reference example 4]
LiTFSI as a supporting electrolyte and anthraquinone (formula (q12)) as a redox shuttle agent are dissolved in DMA, the supporting electrolyte is contained at a concentration of 0.1 mol/L, and the redox shuttle agent is contained by the solubility (less than 50 mmol/L). A measurement solution was prepared. Using this measurement solution, cyclic voltammetry was performed in the same manner as in Example 1, except that the potential range was 1.5 to 3.0 V based on lithium reference potential, and the redox potential of the redox shuttle agent was evaluated.
［実験結果］
図３～５に、実施例１（メチルビオロゲン）、実施例２（ｐ－ベンゾキノン）、比較例１（フェロセン）のサイクリックボルタンメトリー測定結果を示した。メチルビオロゲンの場合は二対の酸化還元ピークが、ｐ－ベンゾキノンとフェロセンの場合は一対の酸化還元ピークが見られた。酸化方向のピーク電位Ｅpa、還元方向のピーク電位Ｅpcの値から、以下の数式で標準酸化還元電位Ｅ0を算出した。
Ｅ0＝（Ｅpa＋Ｅpc）／２ ・・・数式（３）
[Experimental result]
3 to 5 show the cyclic voltammetry measurement results of Example 1 (methyl viologen), Example 2 (p-benzoquinone), and Comparative Example 1 (ferrocene). Two pairs of redox peaks were observed in the case of methyl viologen, and a pair of redox peaks were observed in the case of p-benzoquinone and ferrocene. The standard oxidation-reduction potential E 0 was calculated from the values of the peak potential E pa in the oxidation direction and the peak potential E pc in the reduction direction using the following formula.
E 0 = (E pa + E pc )/2 ... Formula (3)
表１に、サイクリックボルタンメトリー測定結果から得られた各レドックスシャトル剤の酸化方向のピーク電位Ｅpa、還元方向のピーク電位Ｅpcおよび標準酸化還元電位Ｅ0を示した。メチルビオロゲン、ｐ－ベンゾキノンの標準酸化還元電位は、銅の酸化還元電位 (リチウム基準電位で３．０～３．５Ｖ) より低いのに対し、フェロセンの標準酸化還元電位はリチウム基準電位で３．０Ｖより高かった。上述したように、レドックスシャトル剤による放電時、正負極電位は最終的にはレドックスシャトル剤の酸化還元電位に等しくなると考えられることから、レドックスシャトル剤としてメチルビオロゲン又はｐ－ベンゾキノンを用いて不活性化した場合、負極電位を低く（例えば３．０Ｖ未満）保つことができ、負極電位が銅の酸化還元電位より高くなることはなく、銅の溶出等を抑制できると推察された。一方、レドックスシャトル剤としてフェロセンを用いると、負極電位はフェロセンの酸化還元電位（リチウム基準電位で３．２５Ｖ）まで高くなると考えられることから、負極集電箔の銅の溶出が懸念された。 Table 1 shows the peak potential E pa in the oxidation direction, the peak potential E pc in the reduction direction, and the standard redox potential E 0 of each redox shuttle agent obtained from the cyclic voltammetry measurement results. The standard redox potential of methyl viologen and p-benzoquinone is lower than that of copper (3.0 to 3.5 V with lithium reference potential), while the standard redox potential of ferrocene is 3.0 V with lithium reference potential. It was higher than 0V. As mentioned above, during discharge using a redox shuttle agent, the positive and negative electrode potentials are considered to eventually become equal to the redox potential of the redox shuttle agent, so methyl viologen or p-benzoquinone is used as the redox shuttle agent to inactivate It was inferred that when this happens, the negative electrode potential can be kept low (for example, less than 3.0 V), the negative electrode potential will not become higher than the oxidation-reduction potential of copper, and copper elution etc. can be suppressed. On the other hand, when ferrocene is used as a redox shuttle agent, the negative electrode potential is thought to increase to the oxidation-reduction potential of ferrocene (3.25 V based on lithium reference potential), so there was a concern that copper from the negative electrode current collector foil might be eluted.
図６，７に、実施例１（メチルビオロゲン）、実施例２（ｐ－ベンゾキノン）の不活性化剤を添加した後の電池の放電挙動を示した。いずれも、不活性化剤の添加直後から、電池の放電が進行した。メチルビオロゲンを用いた実施例１では、不活性化剤の添加から３０時間後にはＳＯＣ（Ｓｔａｔｅ ｏｆ ｃｈａｒｇｅ）が０％（電池電圧３．０Ｖ）になり、さらに５０時間後には電池電圧が１Ｖ以下になった。ｐ－ベンゾキノンを用いた実施例２では、不活性化剤の添加から６時間後にはＳＯＣが０％（電池電圧３．０Ｖ）になり、３０時間後には電池電圧が１Ｖ以下になった。以上より、メチルビオロゲンを用いた不活性化剤及びｐ－ベンゾキノンを用いた不活性化剤は、いずれも、電池の不活性化剤として機能することがわかった。 6 and 7 show the discharge behavior of the battery after adding the deactivating agents of Example 1 (methyl viologen) and Example 2 (p-benzoquinone). In all cases, the discharge of the battery proceeded immediately after the addition of the deactivating agent. In Example 1 using methyl viologen, the SOC (state of charge) becomes 0% (battery voltage 3.0 V) 30 hours after the addition of the deactivating agent, and the battery voltage drops to 1 V or less after another 50 hours. Became. In Example 2 using p-benzoquinone, the SOC became 0% (battery voltage 3.0 V) 6 hours after the addition of the deactivating agent, and the battery voltage became 1 V or less 30 hours later. From the above, it was found that both the deactivating agent using methyl viologen and the deactivating agent using p-benzoquinone function as deactivating agents for batteries.
実施例１の不活性化後の電池について、負極電位を確認したところ、Ｌｉ基準電位で約２．５Ｖであり、理論通り負極電位が３．０Ｖ未満となることが確認された。なお、不活性化後の正極電位は約３．５Ｖであった。 When the negative electrode potential of the inactivated battery of Example 1 was checked, it was found to be about 2.5 V based on Li reference potential, and it was confirmed that the negative electrode potential was less than 3.0 V as theoretically expected. Note that the positive electrode potential after inactivation was about 3.5V.
実施例１，２において、レドックスシャトル剤の添加量は、ＳＯＣ１００％からＳＯＣ０％まで放電するときの電荷量の約１／５に相当する量であった。そして、実施例１，２では、ＳＯＣ０％まで放電可能であったことから、少なくとも５サイクルはレドックスシャトル反応が進行したものと推察された。 In Examples 1 and 2, the amount of the redox shuttle agent added was equivalent to about 1/5 of the amount of charge when discharging from 100% SOC to 0% SOC. In Examples 1 and 2, since it was possible to discharge down to SOC 0%, it was inferred that the redox shuttle reaction proceeded for at least 5 cycles.
図８に、比較例１（フェロセン）の不活性化剤を添加した後の電池の放電挙動を示した。比較例１でも、不活性化剤の添加直後から電池の放電が進行し、不活性化剤の添加から５時間後にはＳＯＣが０％になり、１５時間後には電池電圧は０Ｖになった。以上より、フェロセンを用いた不活性化剤は、電池の不活性化剤として機能することがわかった。一方で、比較例１の不活性化後の電池について負極電位を確認したところ、Ｌｉ基準電位で３．２４Ｖであり、理論通り負極電位がＬｉ基準電位で３．０Ｖ以上となることが確認された。つまり、フェロセンを用いた不活性化剤を用いた場合には、負極集電箔の銅の溶出が懸念されることがわかった。 FIG. 8 shows the discharge behavior of the battery after adding the deactivating agent of Comparative Example 1 (ferrocene). In Comparative Example 1 as well, the discharge of the battery proceeded immediately after the addition of the deactivating agent, and the SOC reached 0% 5 hours after the addition of the deactivating agent, and the battery voltage reached 0 V 15 hours after the addition of the deactivating agent. From the above, it was found that the deactivating agent using ferrocene functions as a battery deactivating agent. On the other hand, when the negative electrode potential of the battery after inactivation of Comparative Example 1 was confirmed, it was 3.24 V at the Li reference potential, and it was confirmed that the negative electrode potential was 3.0 V or more at the Li reference potential as in theory. Ta. In other words, it has been found that when a deactivating agent containing ferrocene is used, there is a concern that copper from the negative electrode current collector foil may be eluted.
表２に、参考例１（ビオロゲン類）のＬｉ基準電位での酸化還元電位の計算結果を示した。なお、表２では、２段階目（低電位側）の酸化還元電位のみを示した。メチルビオロゲンの酸化還元電位の計算結果は、実施例１の実験結果（図３及び表１参照）に概ね一致した。参考例１の計算結果から、酸化還元電位がアルキル基の構造によらず同程度の値を示すと推察された。表３に、J. Mater. Chem. A, 7 (2019) 23337-23360に開示されたビオロゲン類の酸化還元電位を示した。表３の酸化還元電位は、いずれもＬｉ基準電位に換算すると３．０Ｖ未満であった。以上より、ビオロゲン類であれば、置換基の構造によらず、酸化還元電位が３．０Ｖ未満であると推察された。 Table 2 shows the calculation results of the redox potential of Reference Example 1 (viologens) at the Li reference potential. Note that Table 2 shows only the second stage (lower potential side) redox potential. The calculation results of the redox potential of methyl viologen generally agreed with the experimental results of Example 1 (see FIG. 3 and Table 1). From the calculation results of Reference Example 1, it was inferred that the oxidation-reduction potential showed a similar value regardless of the structure of the alkyl group. Table 3 shows the redox potential of the viologens disclosed in J. Mater. Chem. A, 7 (2019) 23337-23360. All of the oxidation-reduction potentials in Table 3 were less than 3.0 V when converted to Li reference potential. From the above, it was inferred that in the case of viologens, the redox potential is less than 3.0 V, regardless of the structure of the substituent.
表４に、参考例２（キノン類）のＬｉ基準電位での酸化還元電位の計算結果を示した。ｐ－ベンゾキノンの酸化還元電位の計算結果は、実施例２の実験結果（図４及び表１参照）に比べて０．１Ｖ程度低い値となった。そこで、参考例３（１，４－ナフトキノン）および参考例４（アントラキノン）のサイクリックボルタンメトリー測定を実施した。図９に参考例３、図１０に参考例４のサイクリックボルタンメトリー測定結果を示した。また、表５に、参考例３及び参考例４のサイクリックボルタンメトリー測定結果から得られた各レドックスシャトル剤の酸化方向のピーク電位Ｅpa、還元方向のピーク電位Ｅpcおよび標準酸化還元電位Ｅ0を示した。参考例３及び参考例４はいずれも計算結果の方が０．１～０．２Ｖ程度低かったものの、Ｌｉ基準電位で３．０Ｖ未満で酸化還元を示した。従って、表４に示すキノン類はいずれもＬｉ基準電位で３．０Ｖ未満の酸化還元電位を示すものと推察された。以上より、いずれのビオロゲン類及びキノン類を不活性化剤のレドックスシャトル剤として使用した場合も、負極の電位を低く（例えば３．０Ｖ未満）保つことができ、例えば銅の溶出等を抑制できると推察された。 Table 4 shows the calculation results of the oxidation-reduction potential of Reference Example 2 (quinones) at the Li reference potential. The calculated redox potential of p-benzoquinone was about 0.1 V lower than the experimental results of Example 2 (see FIG. 4 and Table 1). Therefore, cyclic voltammetry measurements were performed on Reference Example 3 (1,4-naphthoquinone) and Reference Example 4 (anthraquinone). FIG. 9 shows the cyclic voltammetry measurement results of Reference Example 3, and FIG. 10 shows the results of cyclic voltammetry measurement of Reference Example 4. Table 5 also shows the peak potential E pa in the oxidation direction, the peak potential E pc in the reduction direction, and the standard redox potential E 0 of each redox shuttle agent obtained from the cyclic voltammetry measurement results of Reference Examples 3 and 4. showed that. Both Reference Example 3 and Reference Example 4 showed oxidation-reduction at less than 3.0 V at the Li reference potential, although the calculated results were lower by about 0.1 to 0.2 V. Therefore, it was inferred that all of the quinones shown in Table 4 exhibited an oxidation-reduction potential of less than 3.0 V based on the Li reference potential. From the above, when any of the viologens and quinones is used as a redox shuttle agent as an inactivating agent, the potential of the negative electrode can be kept low (for example, less than 3.0 V), and for example, the elution of copper can be suppressed. It was inferred that.
本発明は、電池産業の分野に利用可能である。 The present invention can be used in the field of battery industry.
２０ 非水系二次電池、２１ 電池ケース、２２ 正極、２３ 負極、２４ セパレータ、２５ ガスケット、２６ 封口板、２７ イオン伝導媒体。 20 non-aqueous secondary battery, 21 battery case, 22 positive electrode, 23 negative electrode, 24 separator, 25 gasket, 26 sealing plate, 27 ion conductive medium.
Claims (4)
酸化還元電位がＬｉ基準電位で前記非水系二次電池の負極活物質よりも高く前記非水系二次電池の正極活物質よりも低くかつ３．０Ｖ未満であるレドックスシャトル剤と、非水系溶媒と、を含み、前記レドックスシャトル剤はビオロゲン類であり前記非水系溶媒はカーボネート化合物を含むものであるか、前記レドックスシャトル剤はキノン類であり前記非水系溶媒はアミド化合物を含むものである、
非水系二次電池の不活性化剤。 A deactivating agent that deactivates a non-aqueous secondary battery,
a redox shuttle agent whose redox potential is higher than the negative electrode active material of the non-aqueous secondary battery and lower than the positive electrode active material of the non-aqueous secondary battery and less than 3.0 V at a Li reference potential; and a non-aqueous solvent. , the redox shuttle agent is a viologen and the non-aqueous solvent contains a carbonate compound, or the redox shuttle agent is a quinone and the non-aqueous solvent contains an amide compound,
Deactivator for non-aqueous secondary batteries.
非水系二次電池の不活性化方法。 An addition step of adding the inactivating agent for a non-aqueous secondary battery according to claim 1 or 2 into the non-aqueous secondary battery.
Method for inactivating non-aqueous secondary batteries.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012028150A (en) | 2010-07-22 | 2012-02-09 | Toyota Motor Corp | Lithium ion secondary battery |
| JP2013232326A (en) | 2012-04-27 | 2013-11-14 | Asahi Kasei Corp | Nonaqueous secondary battery |
| JP2013232328A (en) | 2012-04-27 | 2013-11-14 | Asahi Kasei Corp | Redox shuttle reagent for nonaqueous secondary battery, nonaqueous electrolyte, and nonaqueous secondary battery |
| JP2017526108A (en) | 2014-06-27 | 2017-09-07 | ツェントゥルム フューア ゾンネンエネルギー−ウント ヴァッサーシュトッフ−フォルシュング バーデン−ヴァルテムベルク ゲマインニュッツィヒ シュティフトゥング | Controlled discharge of energy storage using redox shuttle additives. |
| WO2020204830A1 (en) | 2019-04-01 | 2020-10-08 | National University Of Singapore | A redox flow battery |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012028150A (en) | 2010-07-22 | 2012-02-09 | Toyota Motor Corp | Lithium ion secondary battery |
| JP2013232326A (en) | 2012-04-27 | 2013-11-14 | Asahi Kasei Corp | Nonaqueous secondary battery |
| JP2013232328A (en) | 2012-04-27 | 2013-11-14 | Asahi Kasei Corp | Redox shuttle reagent for nonaqueous secondary battery, nonaqueous electrolyte, and nonaqueous secondary battery |
| JP2017526108A (en) | 2014-06-27 | 2017-09-07 | ツェントゥルム フューア ゾンネンエネルギー−ウント ヴァッサーシュトッフ−フォルシュング バーデン−ヴァルテムベルク ゲマインニュッツィヒ シュティフトゥング | Controlled discharge of energy storage using redox shuttle additives. |
| WO2020204830A1 (en) | 2019-04-01 | 2020-10-08 | National University Of Singapore | A redox flow battery |
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