JP6341360B2 - Nonaqueous electrolyte secondary battery - Google Patents

Description

  The present invention relates to a non-aqueous electrolyte secondary battery comprising a positive electrode material, a non-aqueous electrolyte, and a negative electrode material. More specifically, the positive electrode material contains a tripyrazinylene compound and a carbon compound, and is specified as a non-aqueous electrolyte. The present invention relates to a non-aqueous electrolyte secondary battery that is excellent in charge / discharge characteristics under a high-temperature environment and that is excellent in safety and reliability.

  Conventionally, a non-aqueous electrolyte secondary battery represented by a lithium ion battery has been used in the form of a solution or a paste from the viewpoint of ionic conductivity. However, since there is a risk of equipment damage due to liquid leakage, various safety measures are necessary, which is a barrier to the development of large batteries.

  On the other hand, solid electrolytes such as inorganic crystalline substances, inorganic glasses, and organic polymer substances have been proposed. However, although the inorganic electrolyte has high ionic conductivity, it is difficult to increase the size of the battery because the electrolyte is crystalline or amorphous and it is difficult to reduce the volume change due to the positive and negative electrode active materials during charge and discharge. On the other hand, organic polymer materials are generally expected to progress in view of excellent flexibility, bending workability, and moldability, and increasing the degree of freedom in designing the applied devices.

  If the organic polymer solid electrolyte can be combined with positive and negative electrode materials conventionally used in lithium ion batteries, it becomes possible to develop a large battery having higher safety. However, good characteristics have not been reported so far for batteries using the above positive and negative electrode materials and polymer solid electrolyte.

  For example, as an existing report on a combination of a lithium ion conductive polymer (polymer solid electrolyte) and a positive electrode transition metal oxide, Patent Document 1 uses an inorganic material for the purpose of suppressing deterioration of an organic electrolyte located near the positive electrode. There is a report that the surface of the positive electrode is protected and the cycle life is thereby improved. However, when 50 cycles have elapsed, the discharge capacity has decreased to 60% of the initial capacity, and there has been a problem with respect to the cycle life.

  On the other hand, a secondary battery using an organic compound as a positive electrode active material has recently been proposed in order to solve the problem of slow movement of lithium ions in the transition metal oxide of the positive electrode in the lithium ion secondary battery. Research and development of secondary batteries using organic radical compounds among these organic compounds are being actively conducted.

  For example, Patent Document 2 proposes an electrode containing a compound having a diazine N, N′-dioxide structure as an electrode active material, and Patent Document 3 discloses a diazine N, N′-dioxide structure as a side chain. An electrode active material containing an oligomer or polymer compound is proposed.

  In Patent Document 3, an organic compound containing a pyrazine structure bonded to a cycloalkane in a constitutional unit is capable of a multi-electron reaction, and is excellent in oxidation-reduction reaction stability, and has a large molecular weight with a small molecular weight. The knowledge that can be charged.

  However, when the electrolytic solution described in Patent Document 4 is not used, a solid electrolyte such as a polymer solid electrolyte is interposed between the positive electrode and the negative electrode. In such a case, the contact property at the interface between the solid electrolyte and the electrode is very important, and there is a problem in the contact between the electrode and the solid electrolyte interface.

JP 2003-338321 A JP 2003-115297 A JP 2012-79479 A JP 2007-157696 A

  In view of the circumstances as described above, the object of the present invention is to provide basic performance as a battery, high capacity and excellent charge / discharge characteristics even when a positive electrode active material of a specific organic compound is used, and safety and reliability. It is to provide an excellent nonaqueous electrolyte secondary battery.

  As a result of intensive studies to solve the above problems, the inventors of the present invention contain a tripyrazinylene compound and a carbon compound in the positive electrode, and appropriately select a specific polyether copolymer and electrolyte salt compound as the electrolyte composition. It has been found that a non-aqueous electrolyte secondary battery having basic performance as a battery, having a high energy density, excellent charge / discharge characteristics, and excellent safety and reliability can be obtained by sandwiching with a negative electrode. The present invention has been completed.

[式中、Ｒは炭素数１〜１２のアルキル基、または−ＣＨ_２Ｏ（ＣＲ^１Ｒ^２Ｒ^３）である。Ｒ^１、Ｒ^２、Ｒ^３は水素原子または−ＣＨ_２Ｏ（ＣＨ_２ＣＨ_２Ｏ）_ｎＲ^４であり、ｎおよびＲ^４はＲ^１、Ｒ^２、Ｒ^３の間で異なっていてもよい。Ｒ^４は炭素数１〜１２のアルキル基であり、ｎは０〜１２の整数である。]
で示される単量体から誘導される繰り返し単位５〜９５モル％、および
式（２）：

で示される単量体から誘導される繰り返し単位９５〜５モル％、および
式（３）：

[式中、Ｒ^５はエチレン性不飽和基である。] で示される単量体から誘導される繰り返し単位０〜１０モル％から構成されるポリエーテル共重合体またはその架橋物ならびに電解質塩化合物が含まれる電解質組成物、（ｉｉ）式（４）：

（ただし、式中、Ｒ^６〜Ｒ^１１は、水素原子、置換もしくは無置換のアルキル基、アリール基、アラルキル基、シクロアルキル基、アルコキシル基、アルケニル基、アリールオキシ基、アリールアミノ基、アルキルアミノ基、チオアリール基、チオアルキル基、複素環基、ホルミル基、シリル基、ボリル基、スタンニル基、シアノ基、ニトロ基、ニトロソ基、カルボキシル基、アルコキシカルボニル基、およびハロゲン原子の少なくともいずれか１種を示す。Ｒ^６〜Ｒ^１１は同一の場合を含み、互いに連結して飽和もしくは不飽和の環を形成する場合を含む。）
で表わされるトリピラジニレン系化合物を正極活物質として含む正極、そして負極を備えることを特徴とする非水電解質二次電池である。
項２
前記正極が正極活物質と導電助剤と結着剤との混合物を有し、かつ、その正極活物質として式（４）で表されるトリピラジニレン系化合物を、その導電助剤として炭素化合物をそれぞれ使用することを特徴とする項１に記載の非水電解質二次電池である。
項３
前記負極が負極活物質と導電助剤と結着剤との混合物を有し、かつ、その負極活物質が、リチウム、カーボン、シリコン系化合物、スズ系化合物、アルミニウム系化合物、チタン系化合物のうちの１種、あるいは２種以上の混合物からなることを特徴とする項１または２に記載の非水電解質二次電池である。
項４
前記電解質組成物が、非プロトン性有機溶媒を含有することを特徴とする項１〜３のいずかに記載の非水電解質二次電池である。
項５
前記非プロトン性有機溶媒が、エーテル類およびエステル類からなる群より選択される少なくとも１種であることを特徴とする項４に記載の非水電解質二次電池である。
項６
式（１）：

[式中、Ｒは炭素数１〜１２のアルキル基、または−ＣＨ_２Ｏ（ＣＲ^１Ｒ^２Ｒ^３）である。Ｒ^１、Ｒ^２、Ｒ^３は水素原子または−ＣＨ_２Ｏ（ＣＨ_２ＣＨ_２Ｏ）_ｎＲ^４であり、ｎおよびＲ^４はＲ^１、Ｒ^２、Ｒ^３の間で異なっていてもよい。Ｒ^４は炭素数１〜１２のアルキル基であり、ｎは０〜１２の整数である。]
で示される単量体から誘導される繰り返し単位５〜９５モル％、および
式（２）：

で示される単量体から誘導される繰り返し単位９５〜５モル％、および
式（３）：

[式中、Ｒ^５はエチレン性不飽和基である。] で示される単量体から誘導される繰り返し単位０〜１０モル％から構成されるポリエーテル共重合体またはその架橋物を、前記正極および／または負極の表面上に存在させるか、あるいは、前記正極および／または負極の内部に一構成成分として存在させることを特徴とする項１〜５に記載の非水電解質二次電池である。 The present invention has been completed based on the above findings.
at least,
(I) Formula (1):

[Wherein, R represents an alkyl group having 1 to 12 carbon atoms, or —CH ₂ O (CR ¹ R ² R ³ ). R ¹ , R ² and R ³ are hydrogen atoms or —CH ₂ O (CH ₂ CH ₂ O) _n R ⁴ , and n and R ⁴ may be different among R ¹ , R ² and R ^3. . R ⁴ is an alkyl group having 1 to 12 carbon atoms, and n is an integer of 0 to 12. ]
5 to 95 mol% of repeating units derived from the monomer represented by formula (2):

And 95 to 5 mol% of repeating units derived from the monomer represented by formula (3):

[Wherein R ⁵ represents an ethylenically unsaturated group. An electrolyte composition comprising a polyether copolymer composed of 0 to 10 mol% of a repeating unit derived from a monomer represented by the following formula or a cross-linked product thereof and an electrolyte salt compound, (ii) Formula (4):

(In the formula, R ^{6 to} R ¹¹ are each a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkoxyl group, an alkenyl group, an aryloxy group, an arylamino group, an alkylamino group) A group, thioaryl group, thioalkyl group, heterocyclic group, formyl group, silyl group, boryl group, stannyl group, cyano group, nitro group, nitroso group, carboxyl group, alkoxycarbonyl group, and halogen atom. R ^{6 to} R ¹¹ include the same case and include a case where they are connected to each other to form a saturated or unsaturated ring.)
A non-aqueous electrolyte secondary battery comprising a positive electrode containing a tripyrazinylene compound represented by the above formula as a positive electrode active material, and a negative electrode.
Item 2
The positive electrode has a mixture of a positive electrode active material, a conductive additive, and a binder, and a tripyrazinylene compound represented by the formula (4) is used as the positive electrode active material, and a carbon compound is used as the conductive auxiliary agent. The nonaqueous electrolyte secondary battery according to Item 1, wherein the nonaqueous electrolyte secondary battery is used.
Item 3
The negative electrode has a mixture of a negative electrode active material, a conductive additive, and a binder, and the negative electrode active material is selected from lithium, carbon, a silicon compound, a tin compound, an aluminum compound, and a titanium compound. Item 3. The nonaqueous electrolyte secondary battery according to Item 1 or 2, comprising one or a mixture of two or more.
Item 4
Item 4. The nonaqueous electrolyte secondary battery according to any one of Items 1 to 3, wherein the electrolyte composition contains an aprotic organic solvent.
Item 5
Item 5. The nonaqueous electrolyte secondary battery according to Item 4, wherein the aprotic organic solvent is at least one selected from the group consisting of ethers and esters.
Item 6
Formula (1):

[Wherein, R represents an alkyl group having 1 to 12 carbon atoms, or —CH ₂ O (CR ¹ R ² R ³ ). R ¹ , R ² and R ³ are hydrogen atoms or —CH ₂ O (CH ₂ CH ₂ O) _n R ⁴ , and n and R ⁴ may be different among R ¹ , R ² and R ^3. . R ⁴ is an alkyl group having 1 to 12 carbon atoms, and n is an integer of 0 to 12. ]
5 to 95 mol% of repeating units derived from the monomer represented by formula (2):

And 95 to 5 mol% of repeating units derived from the monomer represented by formula (3):

[Wherein R ⁵ represents an ethylenically unsaturated group. A polyether copolymer composed of 0 to 10 mol% of a repeating unit derived from the monomer represented by Item 6. The nonaqueous electrolyte secondary battery according to Item 1, wherein the nonaqueous electrolyte secondary battery is present as a constituent component inside the positive electrode and / or the negative electrode.

  According to the present invention, the positive electrode contains an electrode active material composed of a tripyrazinylene compound and a carbon compound, contains a specific polyether copolymer and an electrolyte salt compound as an electrolyte composition, and is sandwiched between the negative electrode and a battery. It is possible to provide a non-aqueous electrolyte secondary battery that has the above basic performance, high capacity, excellent charge / discharge characteristics, and excellent safety and reliability.

  Hereinafter, the configuration of the present invention will be described in detail.

The compound of the formula (1) can be easily synthesized by obtaining it from a commercial product or by a general ether synthesis method from epihalohydrin and alcohol. Examples of commercially available compounds include propylene oxide, butylene oxide, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, tert-butyl glycidyl ether, benzyl glycidyl ether, 1,2-epoxydodecane, 1,2 -Epoxyoctane, 1,2-epoxyheptane, 2-ethylhexyl glycidyl ether, 1,2-epoxydecane, 1,2-epoxyhexane, glycidyl phenyl ether, 1,2-epoxypentane, glycidyl isopropyl ether, etc. can be used. . Among these commercially available products, propylene oxide, butylene oxide, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, and glycidyl isopropyl ether are preferable, and propylene oxide, butylene oxide, methyl glycidyl ether, and ethyl glycidyl ether are particularly preferable.
In the monomer represented by the formula (1) obtained by synthesis, R is preferably —CH ₂ O (CR ¹ R ² R ³ ), and at least one of R ¹ , R ² , and R ³ is —CH ₂ O. it is preferably _{(CH 2 CH 2 O) n} R 4. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. n is preferably 0 to 6, and more preferably 0 to 4.

  The compound of the formula (2) is a basic chemical product, and a commercially available product can be easily obtained.

In the compound of formula (3), R ⁵ is a substituent containing an ethylenically unsaturated group. Examples of the monomer component containing an ethylenically unsaturated group include allyl glycidyl ether, 4-vinylcyclohexyl glycidyl ether, α-terpinyl glycidyl ether, cyclohexenyl methyl glycidyl ether, p-vinylbenzyl glycidyl ether, allyl phenyl glycidyl ether, vinyl Glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-1-pentene, 4,5-epoxy-2-pentene, 1,2-epoxy-5,9-cyclododecandiene, 3,4 -Epoxy-1-vinylcyclohexene, 1,2-epoxy-5-cyclooctene, glycidyl acrylate, glycidyl methacrylate, glycidyl sorbate, glycidyl cinnamate, glycidyl crotonic acid, glycidyl-4-hexenoate are used. Preferred are allyl glycidyl ether, glycidyl acrylate, and glycidyl methacrylate.

[式中、Ｒは炭素数１〜１２のアルキル基、または−ＣＨ_２Ｏ（ＣＲ^１Ｒ^２Ｒ^３）である。Ｒ^１、Ｒ^２、Ｒ^３は水素原子または−ＣＨ_２Ｏ（ＣＨ_２ＣＨ_２Ｏ）_ｎＲ^４であり、ｎおよびＲ⁴はＲ^１、Ｒ^２、Ｒ^３の間で異なっていてもよい。Ｒ^４は炭素数１〜１２のアルキル基であり、ｎは０〜１２の整数である。]
および
（Ｂ）：式（２）の単量体から誘導された繰り返し単位、

および必要なら、
（Ｃ）：式（３）の単量体から誘導された繰り返し単位、

[式中、Ｒ^５はエチレン性不飽和基を含む置換基である。]
から構成される。 The polyether copolymer (i) of the present invention comprises (A): a repeating unit derived from the monomer of formula (1)

[Wherein, R represents an alkyl group having 1 to 12 carbon atoms, or —CH ₂ O (CR ¹ R ² R ³ ). R ¹ , R ² and R ³ are hydrogen atoms or —CH ₂ O (CH ₂ CH ₂ O) _n R ⁴ , and n and R ⁴ may be different among R ¹ , R ² and R ^3. . R ⁴ is an alkyl group having 1 to 12 carbon atoms, and n is an integer of 0 to 12. ]
And (B): a repeating unit derived from the monomer of formula (2),

And if necessary
(C): a repeating unit derived from the monomer of formula (3),

[Wherein R ⁵ is a substituent containing an ethylenically unsaturated group. ]
Consists of

  Here, the repeating units (A) and (C) may each be derived from two or more monomers.

The polyether copolymer of the present invention can be synthesized as follows. As a ring-opening polymerization catalyst, a catalyst system mainly composed of organoaluminum, a catalyst system mainly composed of organic zinc, a coordination anion initiator such as an organotin-phosphate ester condensate catalyst system, or potassium containing K ⁺ as a counter ion By using an anionic initiator such as alkoxide, diphenylmethyl potassium, potassium hydroxide and the like, each of the monomers is reacted in the presence or absence of a solvent at a reaction temperature of 10 to 120 ° C. with stirring to obtain a polyether copolymer. can get. From the viewpoint of the degree of polymerization or the properties of the resulting copolymer, a coordination anion initiator is preferable, and an organotin-phosphate ester condensate catalyst system is particularly preferable because it is easy to handle.

  In the polyether copolymer of the present invention, the molar ratio of the repeating units (A), (B), and (C) is (A) 5 to 95 mol%, (B) 95 to 5 mol%, and ( C) 0 to 10 mol% is suitable, preferably (A) 10 to 95 mol%, (B) 90 to 5 mol%, and (C) 0 to 10 mol%, more preferably (A) 10 to 10 mol%. 80 mol%, (B) 90-20 mol%, and (C) 0-10 mol%. If the repeating unit (B) exceeds 95 mol%, the glass transition temperature rises and the oxyethylene chain crystallizes, resulting in a marked deterioration in the ionic conductivity of the solid electrolyte. In general, it is known that the ionic conductivity is improved by reducing the crystallinity of polyethylene oxide, but the polyether copolymer of the present invention is remarkably superior in this respect.

The molecular weight of the polyether copolymer of the present invention is within the range of the weight average molecular weight of 10 ⁴ to 10 ⁷ , preferably 5 × 10 ^{4 to} 5 × 10 in order to obtain good processability, mechanical strength and flexibility. ⁶ range, more preferably suitable are those of ¹⁰ 5 to 5 × 10 ⁶ range. A copolymer having a weight average molecular weight of less than 10 ⁴ needs to have a high crosslinking density in order to enhance shape stability, so that only a plastic form can be obtained, there is almost no elongation, and ionic conductivity is low. . A copolymer having a weight average molecular weight of more than 10 ⁷ has remarkably poor processability and is difficult to handle.

  The polyether copolymer of the present invention may be a copolymer type of either a block copolymer or a random copolymer. Random copolymers are preferred because they have a greater effect of reducing the crystallinity of polyethylene oxide.

  In order to suppress a short circuit between the electrodes, it is preferable to interpose a crosslinked polymer solid electrolyte between the electrodes. Cross-linked solid polymer electrolytes include, for example, a method of attaching a pre-cross-linked solid polymer electrolyte membrane between electrodes, a polymer solid electrolyte containing a radical polymerization initiator on the surface of the negative electrode, It can be introduced by the method of applying.

  The crosslinked polymer solid electrolyte of the present invention comprises an electrolyte salt compound in the composition containing a polyether copolymer and a radical polymerization initiator to constitute an electrolyte, and in the presence or absence of an aprotic organic solvent. The crosslinked product is crosslinked by applying heat or irradiating active energy rays such as ultraviolet rays.

  In the case of crosslinking by heat, a radical polymerization initiator selected from organic peroxides, azo compounds and the like is used. As organic peroxides, ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxy esters, etc., which are usually used for crosslinking are used. As azo compounds, azonitriles are used. A compound, an azoamide compound, an azoamidine compound, or the like that is usually used for crosslinking is used. The amount of radical polymerization initiator added varies depending on the type, but is usually in the range of 0.1 to 10% by weight based on 100% by weight of the polyether copolymer.

  As the radical polymerization initiator in the case of crosslinking by irradiation with active energy rays, alkylphenone-based, benzophenone-based, acylphosphine oxide-based, titanocenes, triazines, bisimidazoles, oxime esters, and the like are used. The addition amount of these radical polymerization initiators varies depending on the type, but is usually in the range of 0.01 to 5.0% by weight with 100% by weight of the polyether copolymer.

In the present invention, a crosslinking aid may be used when the polymer solid electrolyte is crosslinked. Crosslinking aid is usually polyfunctional compound - a _{(e.g., CH 2 = CH-, CH 2} = CHCH 2, CF 2 = CF- at least two containing compound).

  The electrolyte salt compound that can be used in the present invention is preferably compatible with a mixture of a polyether copolymer or a crosslinked product thereof and, if necessary, an aprotic organic solvent. Here, “compatible” means a state in which the electrolyte salt does not precipitate due to crystallization or the like.

The electrolyte salt compound of the present invention may contain an electrolyte salt compound other than LiCF ₃ SO ₃ , LiN (FSO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) _2. Examples thereof include LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , LiSCN, LiBr, LiI, and Li ₂ SO ₄ .

  In the present invention, the amount of the electrolyte salt compound used is preferably 0.0001 to 5, more preferably 0.001 to 5 in terms of the number of moles of the electrolyte salt compound / the total number of moles of ether oxygen atoms in the polyether copolymer. A range of 0.5 is good.

  In the present invention, an aprotic organic solvent or an ionic liquid may be added as a plasticizer, for example. When an aprotic organic solvent or ionic liquid is mixed into the polymer solid electrolyte composition, the crystallization of the polymer is suppressed, the glass transition temperature is lowered, and a large number of amorphous phases are formed even at low temperatures, so that the ionic conductivity is good. Become. An aprotic organic solvent or an ionic liquid is suitable for obtaining a high-performance battery having a low internal resistance when combined with a solid polymer electrolyte composition that can be used in the present invention. The polymer solid electrolyte of the present invention may be gelled by combining with an aprotic organic solvent or an ionic liquid. Here, the gel is a polymer swollen by a solvent.

  As the aprotic organic solvent, aprotic ethers and esters are preferable. Specifically, propylene carbonate, γ-butyrolactone, butylene carbonate, vinyl carbonate, ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl monoglyme, methyl diglyme, methyl triglyme, methyl tetraglyme, ethyl monoglyme , Ethyl diglyme, ethyl triglyme, ethyl methyl monoglyme, butyl diglyme, 3-methyl-2-oxazolidone, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4,4-methyl-1,3-dioxolane , Methyl formate, methyl acetate, methyl propionate, etc., among them, propylene carbonate, γ-butyrolactone, butylene carbonate, vinyl carbonate, ethylene Carbonate, methyl triglyme, methyl tetraglyme, ethyl triglyme, ethyl methyl monoglyme preferred. A mixture of two or more of these may be used.

  As the ionic liquid, pyridine-based, aliphatic amine-based, and alicyclic amine-based quaternary ammonium organic cation are known. Examples of the quaternary ammonium organic cation include imidazolium ions such as dialkylimidazolium and trialkylimidazolium, tetraalkylammonium ions, alkylpyridinium ions, pyrazolium ions, pyrrolidinium ions, and piperidinium ions. In particular, an imidazolium cation is preferable.

  Examples of the tetraalkylammonium ion include, but are not limited to, trimethylethylammonium ion, trimethylethylammonium ion, trimethylpropylammonium ion, trimethylhexylammonium ion, and tetrapentylammonium ion.

  Examples of the alkyl pyridinium ion include N-methyl pyridinium ion, N-ethyl pyridinium ion, N-propyl pyridinium ion, N-butyl pyridinium ion, 1-ethyl-2methyl pyridinium ion, 1-butyl-4-methyl. Examples thereof include, but are not limited to, pyridinium ions and 1-butyl-2,4 dimethylpyridinium ions.

  As the imidazolium cation, as the dialkylimidazolium ion, 1,3-dimethylimidazolium ion, 1-ethyl-3-methylimidazolium ion, 1-methyl-3-ethylimidazolium ion, 1-methyl-3- Examples thereof include butyl imidazolium ion, 1-butyl-3-methyl imidazolium ion, and the like. Trialkyl imidazolium ions include 1,2,3-trimethylimidazolium ion and 1,2-dimethyl-3-ethyl imidazolium ion. Ions, 1,2-dimethyl-3-propylimidazolium ions, 1-butyl-2,3-dimethylimidazolium ions, and the like, but are not limited thereto.

  In addition, the ionic liquid which has these cations may be used independently, or may mix and use 2 or more types.

  There is no particular limitation on the method of mixing the electrolyte salt compound and the necessary aprotic organic solvent or ionic liquid into the polyether copolymer, but the electrolyte salt compound and the solution containing the necessary aprotic organic solvent or ionic liquid may be mixed. Method of impregnating and impregnating ether copolymer for a long time, Method of mechanically mixing electrolyte salt compound and necessary aprotic organic solvent or ionic liquid into polyether copolymer, polyether copolymer and electrolyte salt There are a method in which a compound is dissolved and mixed in an aprotic organic solvent or an ionic liquid, or a method in which a polyether copolymer is once dissolved in another solvent and then mixed with an aprotic organic solvent or an ionic liquid. Other polar solvents such as tetrahydrofuran, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide, dioxane, methyl ethyl ketone, methyl isobutyl ketone, etc. used alone or in combination are used as other solvents in the case of producing using other solvents. It is done. The other solvent can be removed before, during or after crosslinking when the polyether copolymer is crosslinked.

The positive electrode is, for example, a metal electrode substrate as an electrode material substrate, a positive electrode active material, a conductive auxiliary agent, and an electrolyte that exchanges good ions with the metal electrode substrate, and the conductive auxiliary agent and the positive electrode active material are transferred to the metal substrate. It is comprised from the binder for fixing to. In this case, for example, aluminum is used for the metal electrode substrate, but the metal electrode substrate is not limited thereto, and may be nickel, stainless steel, gold, platinum, titanium, or the like.
In order to reduce the interfacial resistance between the positive electrode active material and the electrolyte, the polyether copolymer of the present invention or a cross-linked product thereof is present on the surface of the positive electrode, or is present as a constituent component inside the positive electrode. May be.

A tripyrazinylene compound containing a pyrazine structure bonded to a cycloalkane as a positive electrode active material in a structural unit can be specifically represented by the general formula (4).

Here, R ^{6 to} R ¹¹ are hydrogen atom, substituted or unsubstituted alkyl group, aryl group, aralkyl group, cycloalkyl group, alkoxyl group, alkenyl group, aryloxy group, arylamino group, alkylamino group, thioaryl. Group, a thioalkyl group, a heterocyclic group, a formyl group, a silyl group, a boryl group, a stannyl group, a cyano group, a nitro group, a nitroso group, a carboxyl group, an alkoxycarbonyl group, and a halogen atom. R ^{6 to} R ¹¹ include the same case and include a case where they are linked to each other to form a saturated or unsaturated ring. Preferably, the alkyl group, aryl group, aralkyl group, cycloalkyl group, alkoxyl group, alkenyl group, cyano group, nitro group, and R ^{6 to} R ¹¹ are structures that form an unsaturated ring linked to each other.

  When the molecular weight of the general formula (4) increases, the amount of charge that can be accumulated per unit mass of the active material decreases, so the molecular weight is within the range of 230 to 1,200, preferably within the range of 230 to 1,000. Is suitable.

  The general formula (4) generates a polyanion by an electrochemical reduction reaction. Since one molecule of the tripyrazinylene compound reacts with six electrons to generate a polyanion, the capacity density can be drastically increased as compared with the case of a one-electron reaction.

Further, in the present invention, a carbon compound is contained as a conductive auxiliary agent for holding the positive electrode together with a tripyrazinylene compound which is a positive electrode active material after the drying (firing) step at the time of manufacturing the positive electrode. The conductive additive, acetylene black, ketjen black, carbon fibers, and conductive carbon such as graphite, conductive polymers, metal powders, and the like, conductive carbon is particularly preferred. The weight ratio between the tripyrazinylene compound and the carbon compound is preferably in the range of 5:95 to 95: 5.

The negative electrode material is, for example, a metal electrode substrate as an electrode material substrate, a negative electrode active material on the metal electrode substrate, and exchange of good ions with the electrolyte, and the conductive auxiliary agent and the negative electrode active material are fixed to the metal substrate. It is comprised from the binder for. In this case, for example, copper is used for the metal electrode substrate, but the metal electrode substrate is not limited to this, and may be nickel, stainless steel, gold, platinum, titanium, or the like.
In order to reduce the interfacial resistance between the negative electrode active material and the electrolyte, the polyether copolymer of the present invention or a cross-linked product thereof is present on the surface of the negative electrode, or is present as a component within the negative electrode. May be.

  The negative electrode active material used in the present invention is a carbon material (natural graphite, artificial graphite, amorphous carbon, etc.) having a structure (porous structure) capable of occluding and releasing alkali metal ions such as lithium ions, or lithium. It is a powder made of a metal such as lithium, an aluminum compound, a tin compound, or a silicon compound that can occlude and release alkali metal ions such as ions. The particle diameter is preferably from 10 nm to 100 μm, more preferably from 20 nm to 20 μm. Moreover, you may use as a mixed active material of a metal and a carbon material.

  As the binder, for example, one or more compounds selected from a fluorine-based binder, acrylic rubber, modified acrylic rubber, styrene-butadiene rubber, acrylic polymer, and vinyl polymer can be used. In addition, it is preferable to use an acrylic polymer because oxidation resistance, sufficient adhesion with a small amount, and flexibility in the electrode plate can be obtained. These binders are preferably added in an amount of 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on the electrode excluding the metal electrode substrate.

  Moreover, a thickener can also be mentioned as what is contained in an electrode. Examples of the thickener include carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose and the like, or alkali metal salts thereof, polyethylene oxide and the like. These thickeners are preferably added in an amount of 0 to 10% by weight with respect to the electrodes excluding the metal electrode substrate.

  Formation of the positive electrode active material and the negative electrode active material on the metal electrode substrate is performed by a doctor blade method, a silk screen method, or the like.

For example, in the doctor blade method, a positive electrode active material or a negative electrode active material dispersed in water or an organic solvent such as N-methylpyrrolidone is applied to a metal electrode substrate, and then applied to a blade having a predetermined slit width. Uniform to an appropriate thickness. The electrode is dried at 40 ° C. or higher, preferably 50 to 150 ° C., more preferably 80 to 120 ° C., in order to remove excess solvent after application of the active material. An electrode material is manufactured by press-molding the dried electrode with a pressing device. For example, it is preferable to use a pressure bonded pressure of 0 to 5 ton / cm ² , particularly 0 to ² ton / cm ² .

  Thereafter, a polymer solid electrolyte is applied to the surface of the electrode material using, for example, a doctor blade method. The polymer solid electrolyte is mixed with a solvent such as acetonitrile according to its viscosity, applied after adjusting to an appropriate viscosity, allowed to stand as necessary, and impregnated with a polymer solid electrolyte solution in the porous portion, This may be heated and dried. The thickness of the coating layer (polymer solid electrolyte) after drying the solvent is preferably 400 μm or less, and more preferably 200 μm or less.

  A nonaqueous electrolyte secondary battery is assembled by superimposing the positive electrode and the negative electrode coated with the polymer solid electrolyte composition. At this time, when the thickness or mechanical strength of the applied polymer solid electrolyte is insufficient, it is preferable to interpose a crosslinked polymer solid electrolyte between the electrode materials. The crosslinked polymer solid electrolyte can be introduced by a technique in which a separately prepared crosslinked polymer solid electrolyte membrane is interposed between electrodes, or a technique in which a polymer solid electrolyte composition disposed on the active material surface is crosslinked.

  When evaluating the characteristics of only the positive electrode material, the reversibility of the electrode material can be evaluated by using a lithium sheet for the counter electrode. In the case of evaluating the combination of the positive electrode material and the negative electrode material, a combination of the positive electrode material and the carbon-based negative electrode material is used without using the lithium sheet.

EXAMPLES Specific modes for carrying out the present invention will be described below with reference to examples. However, the present invention is not limited to the following examples without departing from the gist thereof.
In this example, the following experiment was conducted to compare reversible capacity and cycle performance in a nonaqueous electrolyte secondary battery including a positive electrode, a nonaqueous electrolyte, and a negative electrode.

[Synthesis Example 1 (Production of Polyether Copolymer Catalyst)]
A 3-necked flask equipped with a stirrer, thermometer and distillation apparatus is charged with 10 g of tributyltin chloride and 35 g of tributyl phosphate, and heated at 250 ° C. for 20 minutes with stirring under a nitrogen stream to distill off the distillate and leave a residue. A solid condensate was obtained. It used as a polymerization catalyst in the following polymerization examples.

The monomer equivalent composition of the polyether copolymer was determined by ¹ H NMR spectrum.
For measuring the molecular weight of the polyether copolymer, gel permeation chromatography (GPC) measurement was performed, and the weight average molecular weight was calculated in terms of standard polystyrene. GPC measurement was performed at 60 ° C. using RID-6A manufactured by Shimadzu Corporation, Showdex KD-807, KD-806, KD-806M and KD-803 columns manufactured by Showa Denko KK, and DMF as a solvent. .

１５０ｇ、及び溶媒としてｎ−ヘキサン１，０００ｇを仕込み、化合物（ａ）の重合率をガスクロマトグラフィーで追跡しながら、エチレンオキシド１５０ｇを逐次添加した。このときの重合温度は２０℃とし、１０時間反応を行った。重合反応はメタノールを１ｍＬ加え反応を停止した。デカンテーションによりポリマーを取り出した後、常圧下４０℃で２４時間、更に減圧下４５℃で１０時間乾燥してポリマー２８０ｇを得た。得られたポリエーテル共重合体の重量平均分子量およびモノマー換算組成分析結果を表１に示す。 [Polymerization Example 1]
The inside of a glass four-necked flask having an internal volume of 3 L was purged with nitrogen, and 1 g of the condensate shown in the synthesis example of the catalyst as a polymerization catalyst and a glycidyl ether compound (a) adjusted to a water content of 10 ppm or less:

150 g of ethylene oxide and 1,000 g of n-hexane were charged, and 150 g of ethylene oxide was sequentially added while monitoring the polymerization rate of the compound (a) by gas chromatography. The polymerization temperature at this time was 20 ° C., and the reaction was carried out for 10 hours. The polymerization reaction was stopped by adding 1 mL of methanol. After taking out the polymer by decantation, it was dried at 40 ° C. under normal pressure for 24 hours and further under reduced pressure at 45 ° C. for 10 hours to obtain 280 g of polymer. Table 1 shows the weight average molecular weight and monomer conversion composition analysis results of the obtained polyether copolymer.

[Polymerization Example 2]
The inside of a glass four-necked flask having an internal volume of 3 L is purged with nitrogen, and 1 g of the condensate shown in the synthesis example of the catalyst as a polymerization catalyst and 150 g of glycidyl ether compound (a) adjusted to a water content of 10 ppm or less, allyl glycidyl ether 30 g and 1,000 g of n-hexane were charged as a solvent, and 150 g of ethylene oxide was successively added while monitoring the polymerization rate of the compound (a) by gas chromatography. The polymerization temperature at this time was 20 ° C., and the reaction was carried out for 10 hours. The polymerization reaction was stopped by adding 1 mL of methanol. After taking out the polymer by decantation, it was dried at 40 ° C. under normal pressure for 24 hours and further at 45 ° C. under reduced pressure for 10 hours to obtain 290 g of polymer. Table 1 shows the weight average molecular weight and monomer conversion composition analysis results of the obtained polyether copolymer.

[Crosslinking example 1]
1.0 g of the polyether copolymer obtained in Polymerization Example 2, 0.002 g of photoinitiator benzophenone, N, N ′ crosslinking aid
LiN (CF ₃ SO ₂ ) so that 0.05 g of m-phenylene bismaleimide and a molar ratio (number of moles of electrolyte salt compound) / (total number of moles of ether oxygen atoms in the copolymer) are 0.05. ₂ dissolved in 10 ml of acetonitrile was applied onto a polyethylene terephthalate film using a 500 μm gap bar coater, heated to 80 ° C. and dried as it was, and then the electrolyte surface was covered with a laminate film. A crosslinked polymer solid electrolyte membrane was prepared by irradiation with a mercury lamp (30 mW / cm ² ) for 30 seconds.

[Synthesis Example 2 (Production of tripyrazinylene compound (b) having an unsaturated ring)]
A tripyrazinylene compound (b) was synthesized according to the following synthesis scheme.

  200 mg (0.6 mmol) of hexaketocyclohexane octahydrate and 486 mg (4.5 mmol) of 1,2-phenylenediamine were dissolved in 40 mL of acetic acid and reacted under reflux for 24 hours. The insoluble matter was separated by filtration, and 50 mL of water and 50 mL of chloroform were added to the filtrate to separate the layers. The organic layer was concentrated, and the residue was purified by silica gel column chromatography (eluent chloroform) to obtain 140 mg of a tripyrazinylene compound (b) as a pale yellow solid.

[Synthesis Example 3 (Production of tripyrazinylene-based compound (c) having a cyano group)]
A tripyrazinylene compound (c) was synthesized according to the following synthesis scheme.

  200 mg (0.6 mmol) of hexaketocyclohexane octahydrate and 504 mg (4.5 mmol) of 1,2-diamino-1,2-dicyanoethane were dissolved in 40 mL of acetic acid and reacted under reflux for 24 hours. The insoluble matter was separated by filtration, and 50 mL of water and 50 mL of chloroform were added to the filtrate to separate the layers. The organic layer was concentrated and the residue was purified by silica gel column chromatography (eluent chloroform) to obtain 120 mg of a tripyrazinylene compound (c) having a cyano group as a pale yellow solid.

Example 1 Production of Battery Consisting of Positive Electrode Material / Polymer Solid Electrolyte / Metal Lithium Tripyrazinylene compound (b) having an unsaturated ring was used as the positive electrode active material. For 0.4 g of this positive electrode active material, 1.6 g of acetylene black as a conductive additive, 0.04 g of styrene-butadiene rubber (SBR) as a binder, and carboxymethylcellulose sodium salt (CMC) as a thickener. Add 0.06g, knead in a mortar with water as a solvent, apply to aluminum collector using a 100μm gap bar coater, dry at 80 ° C under vacuum for 12 hours or more, roll press and positive electrode A sheet was used.
Further, 1.0 g of the polyether copolymer obtained in Polymerization Example 1 and a molar ratio (number of moles of electrolyte salt compound) / (total number of moles of ether oxygen atoms in the copolymer) are 0.10. A solution obtained by dissolving LiBF ₄ in 10 ml of acetonitrile was applied onto the above positive electrode sheet using a 500 μm gap bar coater, heated to 80 ° C. as it was, and well impregnated with the polymer solid electrolyte composition in the positive electrode sheet, And it dried and produced the positive electrode / electrolyte sheet | seat in which the polymer solid electrolyte composition was integrated on the positive electrode sheet | seat.
In a glove box substituted with argon gas, the cross-linked polymer solid electrolyte film obtained in the cross-linking example 1 was bonded onto the positive electrode / electrolyte sheet, and metal lithium was bonded as a counter electrode to prepare a test 2032 type coin battery. Assembled. The electrochemical characteristics are constant using a charge / discharge device manufactured by Hokuto Denko Co., Ltd. under the test conditions (C / 20) in which predetermined charge and discharge can be performed in 4 hours, with 4.2V as the upper limit and 1.2V as the lower limit. The positive electrode was evaluated by current application. The test temperature was 60 ° C. environment. The test results are shown in Table 2.

[Example 2] Production of Battery Consisting of Positive Electrode Material / Polymer Solid Electrolyte / Metal Lithium Acetylene as a conductive auxiliary agent with respect to 1.0 g of the tripyrazinylene compound (b) having an unsaturated ring of the positive electrode active material. A positive electrode / electrolyte sheet was produced in the same manner as in Example 1 except that 1.0 g of black was used. To this, metallic lithium was bonded as a counter electrode to prepare a coin battery, and the electrochemical characteristics of the positive electrode were evaluated. The test results are shown in Table 2.

[Example 3] Production of battery composed of positive electrode material / polymer solid electrolyte / lithium metal Except for using tripyrazinylene compound (c) having a cyano group instead of tripyrazinylene compound (b) of the positive electrode active material, A positive electrode / electrolyte sheet was produced in the same manner as in Example 1. To this, metallic lithium was bonded as a counter electrode to prepare a coin battery, and the electrochemical characteristics of the positive electrode were evaluated. The test results are shown in Table 2.

[Comparative Example 1] Production of Battery Consisting of Positive Electrode Material / Polymer Solid Electrolyte / Metal Lithium LiCoO ₂ which is a typical positive electrode active material of a lithium secondary battery was used as the positive electrode active material. To 1.82 g of this positive electrode active material, 0.12 g of acetylene black as a conductive additive, 0.02 g of SBR as a binder, 0.04 g of CMC as a thickener are added, and water is used as a solvent in a mortar. After kneading, it was coated on an aluminum current collector using a 100 μm gap bar coater, dried at 80 ° C. in a vacuum state for 12 hours or more, and then roll pressed to obtain a positive electrode sheet.
Further, 1.0 g of the polyether copolymer obtained in Polymerization Example 1 and a molar ratio (number of moles of electrolyte salt compound) / (total number of moles of ether oxygen atoms in the copolymer) are 0.10. A solution obtained by dissolving LiBF ₄ in 10 ml of acetonitrile was applied onto the above positive electrode sheet using a 500 μm gap bar coater, heated to 80 ° C. as it was, and well impregnated with the polymer solid electrolyte composition in the positive electrode sheet, And it dried and produced the positive electrode / electrolyte sheet | seat in which the polymer solid electrolyte was integrated on the positive electrode sheet | seat.
In a glove box substituted with argon gas, the cross-linked polymer solid electrolyte film obtained in the cross-linking example 1 was bonded onto the positive electrode / electrolyte sheet, and metal lithium was bonded as a counter electrode to prepare a test 2032 type coin battery. Assembled. Electrochemical characteristics are constant with 4.2V upper limit and 2.5V lower limit under test conditions (C / 20) that can perform predetermined charging and discharging in 4 hours using a charge / discharge device manufactured by Hokuto Denko Co., Ltd. The positive electrode was evaluated by current application. The test temperature was 60 ° C. environment. The test results are shown in Table 2.

Comparative Example 2 Preparation of Battery Consisting of Positive Electrode Material / Polymer Solid Electrolyte / Metal Lithium Wako Pure Chemical Industries, Ltd. Polyethylene oxide (molecular weight 1,000) instead of the polyether copolymer obtained in Polymerization Example 1 , 000) was used to produce a positive electrode / electrolyte sheet in the same manner as in Example 1. To this, metallic lithium was bonded as a counter electrode to prepare a coin battery, and the electrochemical characteristics of the positive electrode were evaluated. The test results are shown in Table 2.

When the secondary batteries of Examples 1 to 3 were repeatedly charged and discharged in the range of 4.2 to 1.2 V, the initial capacity of 85% or more could be secured even after 100 cycles. That is, it was found that a secondary battery having excellent stability with little decrease in capacity can be obtained even when charging and discharging are repeated. In the first charge / discharge, the discharge average voltage is about 2.0 V, the energy density per weight of the active material is 600 Wh / kg or more, and exceeds LiCoO ₂ which is a typical positive electrode active material of a lithium secondary battery. all right. That is, a secondary battery having a high energy density and excellent charge / discharge characteristics could be obtained.

  A secondary battery with high energy density, excellent charge / discharge characteristics, and excellent safety and reliability will be realized.

Claims (6)

at least,
(I) Formula (1):

[ Wherein , R is —CH ₂ O (CR ¹ R ² R ³ ). R ¹ , R ² and R ³ are hydrogen atoms or —CH ₂ O (CH ₂ CH ₂ O) _n R ⁴ , and n and R ⁴ may be different among R ¹ , R ² and R ^3. . R ⁴ is an alkyl group having 1 to 12 carbon atoms, and n is an integer of 0 to 12. ] 5 to 95 mol% of repeating units derived from the monomer represented by formula (2):

And 95 to 5 mol% of repeating units derived from the monomer represented by formula (3):

[Wherein R ⁵ represents an ethylenically unsaturated group. An electrolyte composition comprising a polyether copolymer composed of 0 to 10 mol% of a repeating unit derived from a monomer represented by the following formula:
(Ii) Formula (4):

(In the formula, R ^{6 to} R ¹¹ are each a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkoxyl group, an alkenyl group, an aryloxy group, an arylamino group, an alkylamino group) A group, thioaryl group, thioalkyl group, heterocyclic group, formyl group, silyl group, boryl group, stannyl group, cyano group, nitro group, nitroso group, carboxyl group, alkoxycarbonyl group, and halogen atom. R ^{6 to} R ¹¹ include the same case and include a case where they are connected to each other to form a saturated or unsaturated ring.)
A non-aqueous electrolyte secondary battery comprising: a positive electrode containing a tripyrazinylene compound represented by the formula: The non-aqueous electrolyte secondary battery according to claim 1, wherein the positive electrode has a mixture of a positive electrode active material, a conductive auxiliary agent, and a binder, and a carbon material is used as the conductive auxiliary agent .   The negative electrode has a mixture of a negative electrode active material, a conductive additive, and a binder, and the negative electrode active material is selected from lithium, carbon, a silicon compound, a tin compound, an aluminum compound, and a titanium compound. The nonaqueous electrolyte secondary battery according to claim 1, wherein the nonaqueous electrolyte secondary battery is composed of one kind or a mixture of two or more kinds.   The non-aqueous electrolyte secondary battery according to claim 1, wherein the electrolyte composition contains an aprotic organic solvent.   The non-aqueous electrolyte secondary battery according to claim 4, wherein the aprotic organic solvent is at least one selected from the group consisting of ethers and esters. Formula (1):

[ Wherein , R is —CH ₂ O (CR ¹ R ² R ³ ). R ¹ , R ² and R ³ are hydrogen atoms or —CH ₂ O (CH ₂ CH ₂ O) _n R ⁴ , and n and R ⁴ may be different among R ¹ , R ² and R ^3. . R ⁴ is an alkyl group having 1 to 12 carbon atoms, and n is an integer of 0 to 12. And 5 to 95 mol% of repeating units derived from the monomer represented by formula (2):

And 95 to 5 mol% of repeating units derived from the monomer represented by formula (3):

[Wherein R ⁵ represents an ethylenically unsaturated group. A polyether copolymer composed of 0 to 10 mol% of a repeating unit derived from the monomer represented by the formula (1) or a cross-linked product thereof is present on the surface of the positive electrode and / or the negative electrode, or The nonaqueous electrolyte secondary battery according to claim 1, wherein the nonaqueous electrolyte secondary battery is present as a constituent component inside the positive electrode and / or the negative electrode.