JP2015026588A5

JP2015026588A5 -

Info

Publication number: JP2015026588A5
Application number: JP2013157184A
Authority: JP
Filing date: 2013-07-29
Publication date: 2015-12-03
Anticipated expiration: 2033-07-29

Description

上記の課題は以下の手段により解決された。
〔１〕正極、負極、および非水電解液を有する非水二次電池であって、非水電解液はアミノ基を有するホスファゼン化合物であるリン含有化合物（Ａ）を含有し、正極は正極活物質の少なくとも一部が活物質成分とは異なる金属誘導体で被覆された活物質複合体を含有する非水二次電池。
〔２〕前記活物質複合体において、前記正極活物質と前記金属誘導体の質量比が、前記正極活物質１００部に対し、前記金属誘導体１〜７部である〔１〕に記載の非水二次電池。
〔３〕正極活物質がＮｉ、Ｍｎ、およびＣｏから選ばれる元素を含有してなる〔１〕または〔２〕に記載の非水二次電池。
〔４〕金属誘導体がＺｒ、Ｍｇ、Ｔｉ、Ｈｆ、Ｖ、Ｚｎ、Ｓｉ、Ｂ、Ｍｇ、またはＡｌを有する〔１〕〜〔３〕のいずれか１項に記載の非水二次電池。
〔５〕金属誘導体が金属酸化物またはそのリチウム塩である〔１〕〜〔４〕のいずれか１項に記載の非水二次電池。
〔６〕リン含有化合物（Ａ）が下記式（Ａ１）で表される化合物または下記式（Ａ２）で表される構造を有する化合物である〔１〕〜〔５〕のいずれか１項に記載の非水二次電池。

Ｒａ^１１〜Ｒａ^１３は独立に、アルキル基、アラルキル基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、ハロゲン原子、アミノ基、または−（ＣＨ_２）_ｎＣ（＝Ｏ）−（Ｏ）_ｍＲｂ^４（ｎは０または１、ｍは０または１、Ｒｂ^４はアルキル基、アルケニル基、アリール基、アラルキル基である。）である。ＸはＮ（Ｒａ^１４）を表す。Ｒａ^１４は水素原子または１価の置換基を表す。
Ｒａ^２１はそれぞれ独立に１価の置換基を表す。近接のＲ^２１は置換基同士が環を形成していても良い。ｎは２以上の整数を表す。式（Ａ２）の構造は、その結合端同士が結合して環を形成しても良い。
〔７〕式（Ａ２）で表される構造を有する化合物が下記式（Ａ２−１）または（Ａ２−２）で表される化合物である〔６〕に記載の非水二次電池。

Ｒａ^３１〜Ｒａ^３６、Ｒａ^４１〜Ｒａ^４８はそれぞれ独立にＲａ^２１と同義である。
〔８〕リン含有化合物を電解液全量（電解質を含む）中、０．５質量％以上２０質量％以下で含有させる〔１〕〜〔７〕のいずれか１項に記載の非水二次電池。
The above problem has been solved by the following means.
[1] A non-aqueous secondary battery having a positive electrode, a negative electrode, and a non-aqueous electrolyte, the non-aqueous electrolyte containing a phosphorus-containing compound (A) that is a phosphazene compound having an amino group, and the positive electrode A non-aqueous secondary battery comprising an active material composite in which at least a part of a material is coated with a metal derivative different from an active material component.
[2] In the active material composite, the mass ratio of the positive electrode active material and the metal derivative is 1 to 7 parts of the metal derivative with respect to 100 parts of the positive electrode active material. Next battery.
[3] The non-aqueous secondary battery according to the positive electrode active material comprising an element selected Ni, Mn, and Co, [1] or [2].
[4 ] The nonaqueous secondary battery according to any one of [1] to [ 3 ], wherein the metal derivative includes Zr, Mg, Ti, Hf, V, Zn, Si, B, Mg, or Al.
[ 5 ] The nonaqueous secondary battery according to any one of [1] to [ 4 ], wherein the metal derivative is a metal oxide or a lithium salt thereof.
[ 6 ] The compound according to any one of [1] to [ 5 ], wherein the phosphorus-containing compound (A) is a compound represented by the following formula (A1) or a compound having a structure represented by the following formula (A2): Non-aqueous secondary battery.

R a ^{11 to} Ra ¹³ are independently an alkyl group, an aralkyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, a halogen atom, an amino group, or — (CH ₂ ) _n C (═O) — (O) _m. Rb ⁴ (n is 0 or 1, m is 0 or 1, and Rb ⁴ is an alkyl group, an alkenyl group, an aryl group, or an aralkyl group). X represents N (Ra ¹⁴ ). Ra ¹⁴ represents a hydrogen atom or a monovalent substituent .
R a ²¹ each independently represents a monovalent substituent. In the adjacent R ^21, the substituents may form a ring. n represents an integer of 2 or more. In the structure of the formula (A2), the bond ends may be bonded to form a ring .
[ 7 ] The nonaqueous secondary battery according to [ 6 ], wherein the compound having a structure represented by the formula (A2) is a compound represented by the following formula (A2-1) or (A2-2).

^{^{^{R a 31 ~Ra 36, Ra 41}}} ~Ra 48 has the same meaning as ^{Ra 21} independently.
[8 ] The nonaqueous secondary battery according to any one of [1] to [ 7 ], wherein the phosphorus-containing compound is contained in the total amount of the electrolyte solution (including the electrolyte) in an amount of 0.5% by mass to 20% by mass. .

リン含有化合物（Ａ）
リン含有化合物（Ａ）としては、特に制限はないが、Ｐ−Ｏ結合、Ｐ＝Ｏ結合、Ｐ−Ｎ結合、Ｐ＝Ｎから選ばれる少なくとも１種を有している化合物が好ましい。
リン含有化合物（Ａ）としては下記式（Ａ１）で表される化合物または（Ａ２）で表される構造を含む化合物が好ましい。本発明においては、リン含有化合物（Ａ）としてアミノ基を有するホスファゼン化合物が用いられる。

（Ａ１）において
Ｒａ^１１〜Ｒａ^１３は、それぞれ独立に、アルキル基、アラルキル基、アルコキシ基、アリールオキシ基、アラルキルオキシ基、ハロゲン原子、アミノ基、または−（ＣＨ_２）_ｎＣ（＝Ｏ）−（Ｏ）_ｍＲｂ^４（ｎ＝０または１、ｍ＝０または１、Ｒｂ^４はアルキル基、アルケニル基、アリール基、またはアラルキル基である。）である。
Ｘは酸素原子、硫黄原子、Ｎ（Ｒａ^１４）を表す。Ｒａ^１４は水素原子または１価の置換基を表す。
Ｒａ^１１〜Ｒａ^１３におけるアルキル基としては炭素数１〜４が好ましく、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基などが挙げられる。
アラルキル基としては、炭素数７〜２０のアラルキル基であることが好ましく、炭素数７〜１１のアラルキル基であることがより好ましい。具体的に、−Ａｌｋ−Ａｒにおいて、Ａｌｋが炭素数１〜６のアルキレン基が好ましく、Ａｒが炭素数６〜１４のアリール基が好ましい。
アルコキシ基としては炭素数１〜８が好ましく、メトキシ基、エトキシ基、ブトキシ基などの無置換アルコキシ基、２、２、２−トリフロロエトキシ基、１，１，１，３，３，３−ヘキサフロロイソプロポキシ基、パーフロロブチルエチル基などのフッ素置換されたアルコキシ基が挙げられ、メトキシ基、２、２、２−トリフロロエトキシ基、１，１，１，３，３，３−ヘキサフロロイソプロポキシ基が好ましい。
アラルキルオキシ基としては、炭素数７〜２０のアラルキルオキシ基であることが好ましく、炭素数７〜１１のアラルキルオキシ基であることがより好ましい。具体的に、−Ｏ−Ａｌｋ−Ａｒにおいて、Ａｌｋが炭素数１〜６のアルキレン基が好ましく、Ａｒが炭素数６〜１４のアリール基が好ましい。
アリールオキシ基としてはフェノキシ基、フッ素置換されたフェノキシ基が好ましい。
ハロゲン原子としては塩素原子、フッ素原子が好ましく、フッ素原子がより好ましい。
アミノ基としてはジアルキルアミノ基が好ましく、ジメチルアミノ基、ジエチルアミノ基、ジブチルアミノ基など総炭素数２〜８のジアルキルアミノ基が好ましい。
−（ＣＨ_２）_ｎＣ（＝Ｏ）−（Ｏ）_ｍＲｂ^４におけるＲｂ^４としてはメチル基、エチル基が好ましい。
Ｒａ^１４における１価の置換基として好ましくはアルキル基（炭素数１〜６が好ましい）、−Ｓ（＝Ｏ）_２Ｒａ^１５（Ｒａ^１５はアルキル基（炭素数１〜６が好ましい）、アリール基（炭素数６〜１４が好ましい）、アラルキル基（炭素数７〜１５が好ましい）、アルケニル基（炭素数１〜６が好ましい））、−Ｐ（＝Ｏ）（Ｒａ^１６）_２（Ｒａ^１６はアルコキシ基（炭素数１〜６が好ましい）、アリールオキシ基（炭素数６〜１４が好ましい）、アルキル基（炭素数１〜６が好ましい）、アリール基（炭素数６〜１４が好ましい）、ハロゲン原子）を挙げることができる。
Phosphorus-containing compound (A)
Although there is no restriction | limiting in particular as a phosphorus containing compound (A), The compound which has at least 1 sort (s) chosen from PO bond, P = O bond, PN bond, and P = N is preferable.
The phosphorus-containing compound (A) is preferably a compound represented by the following formula (A1) or a compound containing a structure represented by (A2). In the present invention, a phosphazene compound having an amino group is used as the phosphorus-containing compound (A).

In (A1), Ra ^{11 to} Ra ¹³ are each independently an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a halogen atom, an amino group, or — (CH ₂ ) _n C (═O). - a _{^{(O) m Rb 4 (n}} = 0 or 1, m = 0 or 1, Rb ⁴ represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group.).
X represents an oxygen atom, a sulfur atom, or N (Ra ¹⁴ ). Ra ¹⁴ represents a hydrogen atom or a monovalent substituent.
The alkyl group in Ra ^{11 to} Ra ¹³ preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.
The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 11 carbon atoms. Specifically, in -Alk-Ar, Alk is preferably an alkylene group having 1 to 6 carbon atoms, and Ar is preferably an aryl group having 6 to 14 carbon atoms.
The alkoxy group preferably has 1 to 8 carbon atoms, and is an unsubstituted alkoxy group such as a methoxy group, an ethoxy group, or a butoxy group, 2,2,2-trifluoroethoxy group, 1,1,1,3,3,3- Examples include fluorine-substituted alkoxy groups such as hexafluoroisopropoxy group and perfluorobutylethyl group, methoxy group, 2,2,2-trifluoroethoxy group, 1,1,1,3,3,3-hexa A fluoroisopropoxy group is preferred.
The aralkyloxy group is preferably an aralkyloxy group having 7 to 20 carbon atoms, and more preferably an aralkyloxy group having 7 to 11 carbon atoms. Specifically, in -O-Alk-Ar, Alk is preferably an alkylene group having 1 to 6 carbon atoms, and Ar is preferably an aryl group having 6 to 14 carbon atoms.
The aryloxy group is preferably a phenoxy group or a fluorine-substituted phenoxy group.
As a halogen atom, a chlorine atom and a fluorine atom are preferable, and a fluorine atom is more preferable.
The amino group is preferably a dialkylamino group, and a dialkylamino group having 2 to 8 carbon atoms in total, such as a dimethylamino group, a diethylamino group, or a dibutylamino group.
_{_{- (CH 2) n C (}} = O) - (O) m Rb methyl group as Rb ⁴ of ⁴ and an ethyl group are preferable.
The monovalent substituent in Ra ¹⁴ is preferably an alkyl group (preferably having 1 to 6 carbon atoms), -S (= O) ₂ Ra ¹⁵ (Ra ¹⁵ is an alkyl group (preferably having 1 to 6 carbon atoms), or an aryl group. (Preferably 6 to 14 carbon atoms), aralkyl group (preferably 7 to 15 carbon atoms), alkenyl group (preferably 1 to 6 carbon atoms), -P (= O) (Ra ¹⁶ ) ₂ (Ra ¹⁶ is Alkoxy group (preferably having 1 to 6 carbon atoms), aryloxy group (preferably having 6 to 14 carbon atoms), alkyl group (preferably having 1 to 6 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), halogen Atom).

試験Ｎｏ．：ｃで始まるものが比較例、１０１〜１１５、１１９および１２０が参考例
ｃｏｍｐ：例示化合物番号
ｃｏｎｃ：化合物の濃度（質量％）
ＬＣＯ：被覆されていないＬｉＣｏＯ_２
ＬＭＯ：被覆されていないＬｉＭｎ_２Ｏ_４
ＮＭＣ：被覆されていないＬｉＮｉ_１／３Ｍｎ_１／３Ｃｏ_１／３Ｏ_２

Test No. : Comparative examples 101 to 115, 119 and 120 are reference examples comp: Exemplified compound number conc: Concentration of compound (% by mass)
LCO: uncoated LiCoO ₂
LMO: Uncoated LiMn ₂ O ₄
NMC: uncoated LiNi _1/3 Mn _1/3 Co _1/3 O ₂

試験Ｎｏ．：ｃで始まるものが比較例、２０１〜２０９、２１２および２１３が参考例
ｃｏｍｐ：例示化合物番号
ｃｏｎｃ：化合物の濃度（質量％）

Test No. : Starting with c is a comparative example, 201-209 , 212 and 213 are reference examples comp: Exemplified compound number conc: Concentration of compound (% by mass)

Claims

A non-aqueous secondary battery having a positive electrode, a negative electrode, and a non-aqueous electrolyte, wherein the non-aqueous electrolyte contains a phosphorus-containing compound (A) that is a phosphazene compound having an amino group, and the positive electrode is a positive electrode active material A non-aqueous secondary battery comprising an active material composite in which at least a part of is coated with a metal derivative different from the active material component.

2. The non-aqueous secondary battery according to claim 1, wherein in the active material composite, a mass ratio of the positive electrode active material and the metal derivative is 1 to 7 parts of the metal derivative with respect to 100 parts of the positive electrode active material.

The nonaqueous secondary battery according to claim 1 or 2, wherein the positive electrode active material contains an element selected from Ni, Mn, and Co.

Non-aqueous secondary battery according to any one of claims 1 to 3, wherein the metal derivative has Zr, Mg, Ti, Hf, V, Zn, Si, B, Mg or Al,.

The nonaqueous secondary battery according to any one of claims 1 to 4 , wherein the metal derivative is a metal oxide or a lithium salt thereof.

The non-aqueous two according to any one of claims 1 to 5 , wherein the phosphorus-containing compound (A) is a compound represented by the following formula (A1) or a compound having a structure represented by the following formula (A2). Next battery.

R a ^{11 to} Ra ¹³ are independently an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a halogen atom, an amino group, or — (CH ₂ ) _n C (═O) — (O) _m. Rb ⁴ (n is 0 or 1, m is 0 or 1, and Rb ⁴ is an alkyl group, an alkenyl group, an aryl group, or an aralkyl group). X represents N (Ra ¹⁴ ). Ra ¹⁴ represents a hydrogen atom or a monovalent substituent .
R a ²¹ each independently represents a monovalent substituent. In the adjacent R ^21, the substituents may form a ring. n represents an integer of 2 or more. In the structure of the formula (A2), the bond ends may be bonded to form a ring .

The nonaqueous secondary battery according to claim 6 , wherein the compound having a structure represented by the formula (A2) is a compound represented by the following formula (A2-1) or (A2-2).

^{^{^{R a 31 ~Ra 36, Ra 41}}} ~Ra 48 has the same meaning as the ^{Ra 21} independently.

The nonaqueous secondary battery according to any one of claims 1 to 7 , wherein the phosphorus-containing compound is contained in an amount of 0.5% by mass or more and 20% by mass or less in the total amount of the electrolyte solution (including the electrolyte).