JP6150424B2 - Ion conductive solid electrolyte and ion secondary battery using the same - Google Patents

Description

  The present invention relates to an ion conductive solid electrolyte and an ion secondary battery (for example, a lithium ion battery or a sodium ion battery) using the same.

Non-aqueous electrolyte secondary batteries such as lithium secondary batteries are widely used as power sources for so-called portable electronic devices such as mobile phones and notebook computers, to in-vehicle power sources for automobiles and large power sources for stationary applications. It is being put into practical use. In recent years, sodium ion secondary batteries that have been supplied in abundant amounts and can be made of inexpensive materials have been proposed as secondary batteries that can replace lithium ion secondary batteries.
However, with the recent high performance of electronic devices and the application to in-vehicle power supplies for driving and large power supplies for stationary applications, the demand for applied secondary batteries is increasing, and the performance of battery characteristics such as lithium In a secondary battery, it is required to achieve high capacity, high temperature storage characteristics, cycle characteristics, and the like, and at the same time, ensure safety at a high level.

Until now, as electrolytes used in electric devices such as lithium secondary batteries and electric double layer capacitors, organic electrolytes in which a supporting electrolyte is dissolved in an organic solvent have been mainly used. However, organic electrolytes are combustible. Therefore, there are problems in terms of ignitability and liquid leakage.
Therefore, for lithium secondary batteries, attempts to improve the safety of electrical devices by preventing electrolyte leakage or making the electrolyte nonflammable by solidifying or gelling the electrolyte or making it nonflammable. Has been made.

  Conventional solid or gel electrolytes (hereinafter sometimes simply referred to as solid electrolytes) have been studied for both organic and inorganic electrolytes.

  Examples of organic electrolytes include gel electrolytes, polymer electrolytes, ion gel electrolytes, plastic crystal (flexible crystal) electrolytes, and liquid crystal electrolytes.

  The gel electrolyte is obtained by solidifying an organic solvent in which a lithium salt is dissolved in a gelling agent or a host polymer. Gel electrolytes have the same ionic conductivity, lithium ion transport number and usable potential window as current liquid electrolytes, and have become the mainstream technology for solidifying electrolytes. However, since the gel electrolyte, which is widely used in current lithium ion batteries, is obtained by coagulating an organic solvent with a gelling agent, the problems caused by the organic solvent are essentially solved. It is difficult and the mechanical strength is not sufficient.

  Examples of the polymer electrolyte include a polymer in which a lithium salt is mixed with a polymer having ion conductivity such as polyethylene oxide and polypropylene oxide. The polymer electrolyte is superior in mechanical strength to the gel electrolyte, and a self-supporting film made of a polymer acts as an electrolyte, so that the occurrence of liquid leakage can be essentially solved. However, the polymer electrolyte has a low ionic conductivity, and the deterioration of properties under low temperature conditions in which the polymer chain segmental movement is suppressed becomes a problem.

  An ionic gel electrolyte is a gel of an ionic liquid, and a plastic crystal (flexible crystal) electrolyte / liquid crystal electrolyte is a mixture of a lithium salt with a substance in a flexible crystal phase or a liquid crystal phase that falls between the liquid and the crystal. . Although these electrolytes have been confirmed to have relatively high ionic conductivity, rapid changes in ionic conductivity due to phase transitions due to temperature changes such as melting under high temperature conditions and solidification at low temperatures become a problem.

  Examples of inorganic electrolytes include ceramic electrolytes and glass electrolytes.

  Examples of the ceramic electrolyte include an ionic conductor using NASICON type or perovskite type ceramics. Since ceramic electrolytes are nonflammable, they are one of the most safe materials among conventional solid electrolyte materials. However, it is difficult to improve the adhesion with the electrode, and the ionic conductivity may depend on the orientation of the ceramic crystal forming the ceramic electrolyte.

Examples of the glass electrolyte include an ionic conductor using an amorphous material such as Li ₂ S or P ₂ S ₅ . The reported glass electrolyte exhibits high ionic conductivity and a usable potential as large as 10 V or more. However, it is difficult to improve the adhesion with the electrode, and Li ₂ S and P ₂ S ₅ employed as a constituent material have a problem of generating hydrogen sulfide when in contact with water.

JP 2010-225525 A JP 2008-288098 A JP 2008-130529 A JP 2008-37823 A

  There is a demand for a solid electrolyte that exhibits high ion conductivity and ensures high safety.

The present invention has been completed in view of the above circumstances, and by exhibiting ion conduction by a mechanism different from the conventional one, high ion conductivity that could not be achieved by the conventional method and high safety were ensured. A novel solid electrolyte is provided. In order to solve the above problems, the present inventors have conducted intensive studies. As a result, in order to develop high ionic conductivity as a solid electrolyte, by using a small molecule, the interaction between the cation and the anion is moderately increased. The present inventors have obtained the knowledge that the technique for securing the ion conduction path while maintaining it is effective, and have completed the present invention. This molecular solid ionic conductor has the advantages of both an organic electrolyte material and an inorganic electrolyte material. The magnitude of the interaction between the cation and the anion can be controlled by adjusting the steric and / or electronic factors of the cation and the anion. Acquired knowledge that it is effective to contain a low molecular weight electron donating organic compound containing 1 to 3 electron donating atoms selected from the group of atoms, or to make the anion structure cyclic. The present invention has been completed.
Although the detailed mechanism is not detailed and is not particularly limited, in the case of a conventional organic solid electrolyte, for example, a Li electrolyte system using polyethylene oxide (PEO), the Li cation is 4 in the PEO matrix. While ion conduction is performed while maintaining multidentate coordination such as coordination, in the system of the present invention, Li cations maintain interaction with anions, while low molecular weight electron donating organic compounds Since the compound contains only 1 to 3 electron-donating atoms, it is presumed that high ionic conductivity is manifested in the solid crystal because it conducts ions only with a weak coordination interaction of 3 or less.

で表されるアニオンである、（ａ）に記載のイオン伝導性固体電解質。
（ｆ）ＬｉＢＦ_４、ＬｉＰＦ_６、ＬｉＣＦ_３ＳＯ_３、ＬｉＮ（ＳＯ_２ＣＦ_３）_２、ＬｉＮ（ＳＯ_２ＣＦ_２ＣＦ_３）_２、ＬｉＮ（ＳＯ_２Ｆ）_２、Ｌｉ（ＳＯ_３ＣＦ_３）_ｎ（Ｎ（ＳＯ_２ＣＦ_３）_２）_ｍ （ここで、ｎ＋ｍ＝１である）、ＬｉＳＣＮ、

からなる群より選択される１以上のリチウム塩を更に含有する、（ａ）乃至（ｅ）のいずれか一つに記載のイオン伝導性固体電解質。
（ｇ）リチウムを吸蔵・放出することが可能な負極、及びリチウムを吸蔵・放出することが可能な正極と、（ａ）乃至（ｆ）のいずれか一つに記載のイオン電解性固体電解質とを備えている、リチウムイオン電池。
（ｈ）ＮａＢＦ_４、ＮａＰＦ_６、ＮａＣＦ_３ＳＯ_３、ＮａＮ（ＳＯ_２ＣＦ_３）_２、ＮａＮ（ＳＯ_２ＣＦ_２ＣＦ_３）_２、ＮａＮ（ＳＯ_２Ｆ）_２、Ｎａ（ＳＯ_３ＣＦ_３）_ｎ（Ｎ（ＳＯ_２ＣＦ_３）_２）_ｍ （ここで、ｎ＋ｍ＝１である）、ＮａＳＣＮ、からなる群より選択される１以上のナトリウム塩をさらに含有する、（ａ）乃至（ｅ）のいずれか一つに記載のイオン伝導性固体電解質。
（ｉ）ナトリウムを吸蔵・放出することが可能な負極、及びナトリウムを吸蔵・放出することが可能な正極と、（ａ）乃至（ｅ）又は（ｈ）のいずれか一つに記載のイオン電解性固体電解質とを備えている、ナトリウムイオン電池。 That is, the gist of the present invention is as follows.
(A) At least (A) an electron donating organic compound containing 1 to 3 atoms selected from the group of nitrogen, oxygen, phosphorus and sulfur atoms, or (B) selected from the group of nitrogen, phosphorus and sulfur atoms An ion conductive solid electrolyte containing any one of anions having a cyclic structure containing at least one atom.
(B) The electron donating organic compound containing 1 to 3 atoms selected from the group of (A) nitrogen, oxygen, phosphorus and sulfur atoms is an amine, nitrile, ether or thioether compound. The ion-conducting solid electrolyte described.
(C) 1 to 3 atoms selected from the group of nitrogen, oxygen, phosphorus and sulfur atoms are coordinated with a cation to exhibit monodentate, bidentate or tridentate coordination, (a) or (b ) The ion conductive solid electrolyte according to the above.
(D) (B) the anion having a cyclic structure containing at least one atom selected from the group of nitrogen, phosphorus and sulfur atoms is at least 1 with the atom selected from the group of nitrogen, phosphorus and sulfur atoms as a ring atom; The ion-conductive solid electrolyte according to (a), which is an anion containing one ion.
(E) An anion having a cyclic structure containing at least one atom selected from the group of (B) nitrogen, phosphorus and sulfur atoms has the following structural formula:

The ion conductive solid electrolyte according to (a), which is an anion represented by:
(F) LiBF ₄ , LiPF ₆ , LiCF ₃ SO ₃ , LiN (SO ₂ CF ₃ ) ₂ , LiN (SO ₂ CF ₂ CF ₃ ) ₂ , LiN (SO ₂ F) ₂ , Li (SO ₃ CF ₃ ) _n (N (SO ₂ CF ₃ ) ₂ ) _m (where n + m = 1), LiSCN,

The ion conductive solid electrolyte according to any one of (a) to (e), further containing one or more lithium salts selected from the group consisting of:
(G) a negative electrode capable of inserting and extracting lithium, a positive electrode capable of inserting and extracting lithium, and the ion-electrolyzed solid electrolyte according to any one of (a) to (f) A lithium ion battery.
(H) NaBF ₄ , NaPF ₆ , NaCF ₃ SO ₃ , NaN (SO ₂ CF ₃ ) ₂ , NaN (SO ₂ CF ₂ CF ₃ ) ₂ , NaN (SO ₂ F) ₂ , Na (SO ₃ CF ₃ ) _n Any one of (a) to (e), further comprising one or more sodium salts selected from the group consisting of (N (SO ₂ CF ₃ ) ₂ ) _m (where n + m = 1), NaSCN The ion conductive solid electrolyte according to any one of the above.
(I) a negative electrode capable of inserting and extracting sodium; a positive electrode capable of inserting and extracting sodium; and ion electrolysis according to any one of (a) to (e) or (h) Sodium ion battery comprising a conductive solid electrolyte.

  According to the present invention, the obtained ion conductive solid electrolyte is in a crystal or gel form, and high safety can be realized when it is used as an electrolyte for a battery. In addition, the ion conductive solid electrolyte of the present invention exhibits high ion conductivity even at room temperature or low temperature due to the formation of the above-described ion conductive path such as lithium. In addition, it is known that the segmental motion of the polymer chain, which is a driving force for ionic conduction, is suppressed in a previously reported organic polymer electrolyte under low temperature conditions, and thus its characteristics are remarkably deteriorated under low temperature conditions.

  Furthermore, since the ion conductive solid electrolyte of the present invention is made of an organic material, it is flexible while being solid. Therefore, compared to inorganic ceramic electrolytes, the degree of freedom of the shape of the battery is increased, and it is easy to handle and is excellent in handling.

The ion conductivity measurement result of the electrolytes 1 and 2 is shown. The ion conductivity measurement result of electrolytes 3-6 is shown. The ion conductivity measurement result of electrolytes 7-10 is shown. The measurement result of the ionic conductivity of the electrolyte 11 is shown. The ion conductivity measurement result of the electrolytes 14 and 19-21 is shown. The ion conductivity measurement result of electrolytes 24-26 is shown. The measurement result of the ionic conductivity of the electrolyte 27 is shown. The measurement result of the ionic conductivity of the electrolyte 28 is shown. The ion conductivity measurement result of the electrolytes 29 and 30 is shown. The ion conductivity measurement result of electrolyte 31-33 is shown. The measurement result of the ionic conductivity of the electrolyte 34 is shown. The ion conductivity measurement result of the electrolytes 35 and 36 is shown.

<Ion conductive solid electrolyte>
The ion conductive solid electrolyte of the present invention is an ionic compound composed of a cation and an anion and contains at least 1 to 3 atoms selected from the group of (A) nitrogen, oxygen, phosphorus and sulfur atoms. Any one of an electron-donating organic compound or (B) an anion having a cyclic structure containing at least one atom selected from the group consisting of nitrogen, phosphorus and sulfur atoms.

[(A) Electron-donating organic compound containing 1 to 3 atoms selected from the group consisting of nitrogen, oxygen, phosphorus and sulfur atoms (hereinafter sometimes simply referred to as electron-donating organic compound)]
The electron donating organic compound used in the present invention is selected from compounds containing 1 to 3 atoms selected from the group consisting of nitrogen, oxygen, phosphorus and sulfur atoms, and a compound containing a plurality of these atoms. Are also preferably used. Especially, the compound containing 1-3 atoms chosen from the group of nitrogen, oxygen, and a sulfur atom is preferable. The electron donating organic compound used in the present invention has a monodentate, bidentate or tridentate coordination property by coordinating 1 to 3 atoms selected from the group of nitrogen, oxygen, phosphorus and sulfur atoms with a cation. Show.

等が挙げられる。これら電子供与性有機化合物は、フッ素、塩素、臭素等のハロゲン原子や、ニトリル等の電子吸引性置換基を有していてもよい。
一方、ニトリルとしては、上記のニトリル含有化合物以外に、アセトニトリル、プロピオニトリル、ブチロニトリル、イソブチロニトリル、バレロニトリル、イソバレロニトリル、ラウロニトリル、ヘキサンニトリル、シクロペンタンカルボニトリル、シクロヘキサンカルボニトリル、アクリロニトリル、メタクリロニトリル、クロトノニトリル、２−ペンテンニトリル、２−ヘキセンニトリル、マロノニトリル、スクシノニトリル、グルタロニトリル、アジポニトリル、ピメロニトリル、スベロニトリル、アゼラニトリル、セバコニトリル、ウンデカンジニトリル、ドデカンジニトリル、メチルマロノニトリル、エチルマロノニトリル、ｉ−プロピルマロノニトリル、ｔ−ブチルマロノニトリル、メチルスクシノニトリル、２，２−ジメチルスクシノニトリル、２，３−ジメチルスクシノニトリル、トリメチルスクシノニトリル、テトラメチルスクシノニトリル、３，３’−（エチレンジオキシ）ジプロピオニトリル、３，３’−（エチレンジチオ）ジプロピオニトリル、１，２，３−トリス（２−シアノエトキシ）プロパン、トリス（２−シアノエチル）アミン等が挙げられる。これらニトリルは、フッ素、塩素、臭素等のハロゲン原子を有していてもよい。 Examples of the electron-donating organic compound containing a nitrogen atom include amines, amides, and nitriles. Specifically, as amine and amide,

Etc. These electron donating organic compounds may have a halogen atom such as fluorine, chlorine or bromine, or an electron withdrawing substituent such as nitrile.
On the other hand, as the nitrile, in addition to the above nitrile-containing compounds, acetonitrile, propionitrile, butyronitrile, isobutyronitrile, valeronitrile, isovaleronitrile, lauronitrile, hexanenitrile, cyclopentanecarbonitrile, cyclohexanecarbonitrile, acrylonitrile , Methacrylonitrile, crotononitrile, 2-pentenenitrile, 2-hexenenitrile, malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, azeronitrile, sebacononitrile, undecandinitrile, dodecandinitrile, methylmalononitrile , Ethylmalononitrile, i-propylmalononitrile, t-butylmalononitrile, methylsuccinonitrile, 2,2-dimethyl Succinonitrile, 2,3-dimethylsuccinonitrile, trimethylsuccinonitrile, tetramethylsuccinonitrile, 3,3 ′-(ethylenedioxy) dipropionitrile, 3,3 ′-(ethylenedithio) dipropionitrile 1,2,3-tris (2-cyanoethoxy) propane, tris (2-cyanoethyl) amine and the like. These nitriles may have a halogen atom such as fluorine, chlorine or bromine.

等が挙げられる。これら電子供与性有機化合物は、フッ素、塩素、臭素等のハロゲン原子や、ニトリル等の電子吸引性置換基を有していてもよい。 Examples of the electron-donating organic compound containing an oxygen atom include esters, ethers, ketones, alcohols, aldehydes, carbonates, and the like.

Etc. These electron donating organic compounds may have a halogen atom such as fluorine, chlorine or bromine, or an electron withdrawing substituent such as nitrile.

等が挙げられる。これら電子供与性有機化合物は、フッ素、塩素、臭素等のハロゲン原子や、ニトリル等の電子吸引性置換基を有していてもよい。 Examples of the electron-donating organic compound containing a phosphorus atom include phosphine, phosphine oxide, phosphinimine, and the like.

Etc. These electron donating organic compounds may have a halogen atom such as fluorine, chlorine or bromine, or an electron withdrawing substituent such as nitrile.

等が挙げられる。これら電子供与性有機化合物は、フッ素、塩素、臭素等のハロゲン原子や、ニトリル等の電子吸引性置換基を有していてもよい。 On the other hand, examples of the electron donating organic compound containing a sulfur atom include sulfide, thioether, thiol, thiocarbonate, thioester, sulfoxide, sulfone, sulfamide, and the like.

Etc. These electron donating organic compounds may have a halogen atom such as fluorine, chlorine or bromine, or an electron withdrawing substituent such as nitrile.

Among these electron-donating organic compounds, amine, nitrile, ether or thioether compounds are preferable because of their excellent ionic conductivity, and among them, amine, ether or thioether compounds may be more preferable, but are not particularly limited. .
Among the above-mentioned electron-donating organic compounds, those containing two or more atoms selected from the group of nitrogen, oxygen, phosphorus and sulfur atoms and having a chelation coordination with lithium ions or sodium ions are preferably used. There is a case where it is not limited. In the present invention, a compound having a low electron donating property may be preferably used as the electron donating organic compound. In that case, for example, a halogen atom such as fluorine, chlorine or bromine, or an electron such as nitrile is used. An electron donating organic compound having an attractive substituent is preferably used. As the substituent, a fluorine atom, a chlorine atom and a nitrile group are preferable, a fluorine atom and a nitrile group are more preferable, and a fluorine atom is still more preferable.

  In the present invention, the electron-donating organic compound may preferably include an alkylene group that forms a chelate ring. In this case, for example, the alkylene group that forms the chelate ring is preferably a branched alkylene group. . By this method, the crystallinity of the ion conductive solid electrolyte can be controlled to improve the ion conductivity.

で表される環状構造を有するアニオンである。 [(B) An anion having a cyclic structure containing at least one atom selected from the group consisting of nitrogen, phosphorus and sulfur atoms (hereinafter sometimes referred to simply as an anion having a cyclic structure)]
The anion having a cyclic structure used in the present invention is an anion containing at least one atom selected from the group of nitrogen, phosphorus and sulfur atoms, and an atom selected from the group of nitrogen, phosphorus and sulfur atoms in the cyclic skeleton. It is preferable to contain at least one. The anion having a cyclic structure may have a halogen atom such as fluorine, chlorine or bromine, or an electron-withdrawing substituent such as nitrile. Preferably, the anion having a cyclic structure has the following structural formula:

It is an anion which has the cyclic structure represented by these.

[Lithium salt and sodium salt]
The ion conductive solid electrolyte of the present invention contains a lithium salt or a sodium salt.

を有する）（適宜「ＬｉＣＰＦＳＡ」と称する）、及びＬｉＮ（ＳＯ_２ＣＦ_２）_２（下記構造式：

を有する）
からなる群より選択される１以上のリチウム塩が好ましいリチウム塩として例示できる。
また、リチウム塩として、ＬｉＡｓＦ_６、ＬｉＣ（ＳＯ_２ＣＦ_３）_３、ＬｉＮ（ＳＯ_２ＣＦ_３）（ＳＯ_２Ｃ_４Ｆ_９）、ＬｉＳｂＦ_６、ＬｉＣｌＯ_４、ＬｉＡｌＣｌ_４、ＬｉＮ（ＣＮ）_２、ＬｉＢ（Ｃ_２Ｏ_４）_２、ＬｉＯＣＮ、ＬｉＢ（Ｃ_６Ｈ_５）_４、Ｌｉ（Ｂ（Ｃ_６Ｆ_５）_４）、リチウム テトラキス［３，５−ビス（トリフルオロメチル)フェニル]ボレート、リチウム テトラキス（１−イミダゾリル）ボレートなども例示できる。
これらの中では、ＬｉＢＦ_４、ＬｉＰＦ_６、ＬｉＣＦ_３ＳＯ_３、ＬｉＮ（ＳＯ_２ＣＦ_３）_２、ＬｉＮ（ＳＯ_２ＣＦ_２ＣＦ_３）_２、ＬｉＮ（ＳＯ_２Ｆ）_２、Ｌｉ（ＳＯ_３ＣＦ_３）_ｎ（Ｎ（ＳＯ_２ＣＦ_３）_２）_ｍ （ここで、ｎ＋ｍ＝１である）、ＬｉＳＣＮ、ＬｉＮＣＳ、ＬｉＮ（ＳＯ_２ＣＦ_２）_２ＣＦ_２、ＬｉＮ（ＳＯ_２ＣＦ_２）_２、ＬｉＣ（ＳＯ_２ＣＦ_３）_３、ＬｉＮ（ＳＯ_２ＣＦ_３）（ＳＯ_２Ｃ_４Ｆ_９）、ＬｉＢ（Ｃ_２Ｏ_４）_２、ＬｉＯＣＮ、ＬｉＢ（Ｃ_６Ｈ_５）_４、Ｌｉ（Ｂ（Ｃ_６Ｆ_５）_４）、リチウム テトラキス［３，５−ビス（トリフルオロメチル）フェニル］ボレート、リチウム テトラキス（１−イミダゾリル）ボレートが好ましく、その中でも、ＬｉＣＦ_３ＳＯ_３、ＬｉＮ（ＳＯ_２ＣＦ_３）_２、ＬｉＮ（ＳＯ_２ＣＦ_２ＣＦ_３）_２、Ｌｉ（ＳＯ_３ＣＦ_３）_ｎ（Ｎ（ＳＯ_２ＣＦ_３）_２）_ｍ （ここで、ｎ＋ｍ＝１である）、ＬｉＳＣＮ、ＬｉＮＣＳ、ＬｉＮ（ＳＯ_２ＣＦ_２）_２ＣＦ_２、ＬｉＮ（ＳＯ_２ＣＦ_２）_２、ＬｉＣ（ＳＯ_２ＣＦ_３）_３、ＬｉＮ（ＳＯ_２ＣＦ_３）（ＳＯ_２Ｃ_４Ｆ_９）、ＬｉＢ（Ｃ_２Ｏ_４）_２、ＬｉＯＣＮ、ＬｉＢ（Ｃ_６Ｈ_５）_４、Ｌｉ（Ｂ（Ｃ_６Ｆ_５）_４）、リチウム テトラキス［３，５−ビス（トリフルオロメチル）フェニル］ボレート、リチウム テトラキス（１−イミダゾリル）ボレートがイオン伝導特性の観点から特に好ましいが限定はされない。
ナトリウム塩の具体例としては、公知のものであれば特に限定しないが、例えば、ＮａＢＦ_４、ＮａＰＦ_６、ＮａＣＦ_３ＳＯ_３（適宜「ＮａＯＴｆ」と称する）、ＮａＮ（ＳＯ_２ＣＦ_３）_２（適宜「ＮａＴＦＳＩ」と称する）、ＮａＮ（ＳＯ_２ＣＦ_２ＣＦ_３）_２、ＮａＮ（ＳＯ_２Ｆ）_２、Ｎａ（ＳＯ_３ＣＦ_３）_ｎ（Ｎ（ＳＯ_２ＣＦ_３）_２）_ｍ （ここで、ｎ＋ｍ＝１である）、ＮａＳＣＮ、ＮａＮＣＳ、ＮａＮ（ＳＯ_２ＣＦ_２）_２ＣＦ_２（適宜「ＮａＣＰＦＳＡ」と称する）、ＮａＮ（ＳＯ_２ＣＦ_２）_２からなる群より選択される１以上のナトリウム塩が好ましいナトリウム塩として例示できる。
また、ナトリウム塩として、ＮａＡｓＦ_６、ＮａＣ（ＳＯ_２ＣＦ_３）_３、ＮａＮ（ＳＯ_２ＣＦ_３）（ＳＯ_２Ｃ_４Ｆ_９）、ＮａＳｂＦ_６、ＮａＣｌＯ_４、ＮａＡｌＣｌ_４、ＮａＮ（ＣＮ）_２、ＮａＢ（Ｃ_２Ｏ_４）_２、ＮａＯＣＮ、ＮａＢ（Ｃ_６Ｈ_５）_４、Ｎａ（Ｂ（Ｃ_６Ｆ_５）_４）、ナトリウム テトラキス［３，５−ビス（トリフルオロメチル）フェニル］ボレート、ナトリウム テトラキス（１−イミダゾリル）ボレートなども例示できる。
これらの中では、ＮａＢＦ_４、ＮａＰＦ_６、ＮａＣＦ_３ＳＯ_３、ＮａＮ（ＳＯ_２ＣＦ_３）_２、ＮａＮ（ＳＯ_２ＣＦ_２ＣＦ_３）_２、ＮａＮ（ＳＯ_２Ｆ）_２、Ｎａ（ＳＯ_３ＣＦ_３）_ｎ（Ｎ（ＳＯ_２ＣＦ_３）_２）_ｍ （ここで、ｎ＋ｍ＝１である）、ＮａＳＣＮ、ＮａＮＣＳ、ＮａＮ（ＳＯ_２ＣＦ_２）_２ＣＦ_２、ＮａＮ（ＳＯ_２ＣＦ_２）_２、ＮａＣ（ＳＯ_２ＣＦ_３）_３、ＮａＮ（ＳＯ_２ＣＦ_３）（ＳＯ_２Ｃ_４Ｆ_９）、ＮａＢ（Ｃ_２Ｏ_４）_２、ＮａＯＣＮ、ＮａＢ（Ｃ_６Ｈ_５）_４、Ｎａ（Ｂ（Ｃ_６Ｆ_５）_４）、ナトリウム テトラキス［３，５−ビス（トリフルオロメチル）フェニル］ボレート、ナトリウム テトラキス（１−イミダゾリル）ボレートが好ましく、その中でも、ＮａＣＦ_３ＳＯ_３、ＮａＮ（ＳＯ_２ＣＦ_３）_２、ＮａＮ（ＳＯ_２ＣＦ_２ＣＦ_３）_２、Ｎａ（ＳＯ_３ＣＦ_３）_ｎ（Ｎ（ＳＯ_２ＣＦ_３）_２）_ｍ （ここで、ｎ＋ｍ＝１である）、ＮａＳＣＮ、ＮａＮＣＳ、ＮａＮ（ＳＯ_２ＣＦ_２）_２ＣＦ_２、ＮａＮ（ＳＯ_２ＣＦ_２）_２、ＮａＣ（ＳＯ_２ＣＦ_３）_３、ＮａＮ（ＳＯ_２ＣＦ_３）（ＳＯ_２Ｃ_４Ｆ_９）、ＮａＢ（Ｃ_２Ｏ_４）_２、ＮａＯＣＮ、ＮａＢ（Ｃ_６Ｈ_５）_４、Ｎａ（Ｂ（Ｃ_６Ｆ_５）_４）、ナトリウム テトラキス［３，５−ビス（トリフルオロメチル）フェニル］ボレート、ナトリウム テトラキス（１−イミダゾリル）ボレートがイオン伝導特性の観点から特に好ましいが限定はされない。 The lithium salt is not particularly limited as long as it is a known one. For example, LiBF ₄ , LiPF ₆ , LiCF ₃ SO ₃ (referred to as “LiOTf” as appropriate), LiN (SO ₂ CF ₃ ) ₂ (referred to as “LiTFSI” as appropriate). LiN (SO ₂ CF ₂ CF ₃ ) ₂ , LiN (SO ₂ F) ₂ , Li (SO ₃ CF ₃ ) _n (N (SO ₂ CF ₃ ) ₂ ) _m (where n + m = 1) ), LiSCN, LiNCS, LiN (SO ₂ CF ₂ ) ₂ CF ₂ (the following structural formula:

(Referred to as “LiCPFSA” where appropriate), and LiN (SO ₂ CF ₂ ) ₂ (the following structural formula:

Have)
One or more lithium salts selected from the group consisting of can be exemplified as preferred lithium salts.
Furthermore, as the lithium _{salt, LiAsF 6, LiC (SO 2} CF 3) 3, LiN (SO 2 CF 3) (SO 2 C 4 F 9), LiSbF 6, LiClO 4, LiAlCl 4, LiN (CN) 2, LiB (C ₂ O ₄ ) ₂ , LiOCN, LiB (C ₆ H ₅ ) ₄ , Li (B (C ₆ F ₅ ) ₄ ), lithium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, lithium tetrakis Examples thereof include (1-imidazolyl) borate.
Among these, LiBF ₄ , LiPF ₆ , LiCF ₃ SO ₃ , LiN (SO ₂ CF ₃ ) ₂ , LiN (SO ₂ CF ₂ CF ₃ ) ₂ , LiN (SO ₂ F) ₂ , Li (SO ₃ CF ₃ ) _N (N (SO ₂ CF ₃ ) ₂ ) _m (where n + m = 1), LiSCN, LiNCS, LiN (SO ₂ CF ₂ ) ₂ CF ₂ , LiN (SO ₂ CF ₂ ) _2, LiC ( _{SO 2 CF 3) 3, LiN} (SO 2 CF 3) (SO 2 C 4 F 9), LiB (C 2 O 4) 2, LiOCN, LiB (C 6 H 5) 4, Li (B (C 6 F _{5) 4),} lithium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, lithium tetrakis (1-imidazolyl) borate, more preferably a hydrogen atom, LiCF ₃ S _{3, LiN (SO 2 CF 3} ) 2, LiN (SO 2 CF 2 CF 3) 2, Li (SO 3 CF 3) n (N (SO 2 CF 3) 2) m ( where is n + m = 1 ), LiSCN, LiNCS, LiN (SO ₂ CF ₂ ) ₂ CF ₂ , LiN (SO ₂ CF ₂ ) _2, LiC (SO ₂ CF ₃ ) ₃ , LiN (SO ₂ CF ₃ ) (SO ₂ C ₄ F ₉ ) LiB (C ₂ O ₄ ) ₂ , LiOCN, LiB (C ₆ H ₅ ) ₄ , Li (B (C ₆ F ₅ ) ₄ ), lithium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, Lithium tetrakis (1-imidazolyl) borate is particularly preferred from the viewpoint of ionic conductivity, but is not limited.
Specific examples of the sodium salt are not particularly limited as long as they are known, but for example, NaBF ₄ , NaPF ₆ , NaCF ₃ SO ₃ (referred to as “NaOTf” as appropriate), NaN (SO ₂ CF ₃ ) ₂ (as appropriate) (Referred to as “NaTFSI”), NaN (SO ₂ CF ₂ CF ₃ ) ₂ , NaN (SO ₂ F) ₂ , Na (SO ₃ CF ₃ ) _n (N (SO ₂ CF ₃ ) ₂ ) _m (where n + m = 1), one or more sodium salts selected from the group consisting of NaSCN, NaNCS, NaN (SO ₂ CF ₂ ) ₂ CF ₂ (referred to as “NaCPFSA” where appropriate), NaN (SO ₂ CF ₂ ) ₂ It can be illustrated as a preferred sodium salt.
Further, as sodium salts, NaAsF ₆ , NaC (SO ₂ CF ₃ ) ₃ , NaN (SO ₂ CF ₃ ) (SO ₂ C ₄ F ₉ ), NaSbF ₆ , NaClO ₄ , NaAlCl ₄ , NaN (CN) ₂ , NaB (C ₂ O ₄ ) ₂ , NaOCN, NaB (C ₆ H ₅ ) ₄ , Na (B (C ₆ F ₅ ) ₄ ), sodium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, sodium tetrakis Examples thereof include (1-imidazolyl) borate.
Among _{these, NaBF 4, NaPF 6, NaCF} 3 SO 3, NaN (SO 2 CF 3) 2, NaN (SO 2 CF 2 CF 3) 2, NaN (SO 2 F) 2, Na (SO 3 CF 3 ) _N (N (SO ₂ CF ₃ ) ₂ ) _m (where n + m = 1), NaSCN, NaNCS, NaN (SO ₂ CF ₂ ) ₂ CF ₂ , NaN (SO ₂ CF ₂ ) _2, NaC ( SO ₂ CF ₃ ) ₃ , NaN (SO ₂ CF ₃ ) (SO ₂ C ₄ F ₉ ), NaB (C ₂ O ₄ ) ₂ , NaOCN, NaB (C ₆ H ₅ ) ₄ , Na (B (C ₆ F) ₅ ) ₄ ), sodium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and sodium tetrakis (1-imidazolyl) borate are preferable, and among them, NaCF ₃ SO ₃ , NaN (SO ₂ CF ₃ ) ₂ , NaN (SO ₂ CF ₂ CF ₃ ) ₂ , Na (SO ₃ CF ₃ ) _n (N (SO ₂ CF ₃ ) ₂ ) _m (where n + m = 1) A), NaSCN, NaNCS, NaN (SO ₂ CF ₂ ) ₂ CF ₂ , NaN (SO ₂ CF ₂ ) _2, NaC (SO ₂ CF ₃ ) ₃ , NaN (SO ₂ CF ₃ ) (SO ₂ C ₄ F ₉ ), NaB (C ₂ O ₄ ) ₂ , NaOCN, NaB (C ₆ H ₅ ) ₄ , Na (B (C ₆ F ₅ ) ₄ ), sodium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate Sodium tetrakis (1-imidazolyl) borate is particularly preferred from the viewpoint of ionic conductivity, but is not limited.

  (A) The mixing ratio of the electron-donating organic compound and the lithium salt or sodium salt is not particularly limited, but the lithium salt or sodium salt is selected from (A) 1 atom selected from the group of nitrogen, oxygen, phosphorus, and sulfur atoms. The lower limit is usually 0.1 equivalents or more, preferably 0.2 equivalents or more, more preferably 0.25 equivalents or more, more preferably 0, based on the molar amount of ~ 3 electron donating organic compounds. On the other hand, the upper limit is usually 1000 equivalents or less, preferably 100 equivalents or less, more preferably 10 equivalents or less, still more preferably 5 equivalents or less, and particularly preferably 2 equivalents or less.

  (B) The mixing ratio of the anion having a cyclic structure and the lithium salt or sodium salt is not particularly limited, but the lithium salt or sodium salt is selected from (B) at least one atom selected from the group of nitrogen, phosphorus and sulfur atoms. The lower limit is usually 0.001 equivalent or more, preferably 0.01 equivalent or more, more preferably 0.1 equivalent or more, particularly preferably 0.5 equivalent, based on the molar amount of the anion having a cyclic structure to be contained. On the other hand, the upper limit is usually 10 equivalents or less, preferably 5 equivalents or less, more preferably 1 equivalent or less.

The mixing / dispersing method with the lithium salt or sodium salt is not particularly limited. For example, when the (A) electron donating organic compound is liquid, the lithium salt or sodium salt is mixed as it is, or the electron donating organic compound is heated to mix the lithium salt or sodium salt, (A) There is a method in which an electron-donating organic compound and a lithium salt are mixed in a state in which they are dissolved without being decomposed and then the solvent is removed.
(A) When the electron-donating organic compound is a solid, after mixing with a lithium salt or sodium salt, a mechanochemical mixing method such as a ball mill may be used. Moreover, the method of coexisting lithium salt and sodium salt in the synthesis | combining process of (A) electron donating organic compound can also be employ | adopted.
These methods are also preferably used in (B) mixing / dispersing an anion having a cyclic structure and a lithium salt or sodium salt.

  Here, some ion conductive solid electrolytes crystallize after mixing (A) an electron-donating organic compound or (B) an anion having a cyclic structure with a lithium salt or sodium salt. In that case, there are those in which the progress of crystallization is slow, and there are those in which crystallization takes several hours to several days. In that case, after disposing in a gel state at a site used as an ion conductive solid electrolyte, crystallization can be advanced at that site.

  The ion conductive solid electrolyte of the present invention is preferably solid or gelled at normal temperature (25 ° C.). A solid is particularly desirable.

  The ion conductive solid electrolyte of the present invention can be used by mixing with other known electrolytes. For example, other solid or gel electrolytes (gel electrolytes that are organic electrolytes, polymer electrolytes, ion gel electrolytes, plastic crystal (flexible crystal) electrolytes, liquid crystal electrolytes, etc .; ceramic electrolytes that are inorganic electrolytes, glass electrolytes, etc.) It can also be used as a mixture. It can also be used with a liquid electrolyte.

<Ion secondary battery>
The ion conductive solid electrolyte of the present invention can be used as an electrolyte for an ion secondary battery such as a lithium ion battery or a sodium ion battery. That is, another embodiment of the present invention includes a negative electrode capable of inserting and extracting lithium and sodium, a positive electrode capable of inserting and extracting lithium and sodium, and the ion electrolytic solid electrolyte described above A lithium ion battery or a sodium ion battery. These ion secondary batteries have a positive electrode, a negative electrode, an electrolyte, and other battery members selected as necessary.

Hereinafter, the details of the ion secondary battery will be described using a lithium ion battery as an example.
In the lithium ion battery, a known battery structure such as a coin-type battery, a button-type battery, a cylindrical battery, a square battery, and a laminated battery can be used. In any case, the positive electrode and the negative electrode are superimposed or wound through a solid electrolyte to form an electrode body, and the positive electrode current collector and the negative electrode current collector used as necessary After connecting between the positive electrode terminal and the negative electrode terminal connected to each other using a current collecting lead or the like, it is inserted into a battery case and sealed to complete a lithium ion battery. An electrolyte is interposed between the opposing surfaces of the positive electrode and the negative electrode. An example of the interposition method is to apply an electrolyte layer on the surface of the electrode by dissolving the electrolyte in some solvent and then drying. There is a method of forming. A layer of an electrolyte material with high adhesion can be formed by forming a layer made of an electrolyte on both the positive electrode and the negative electrode and bonding them together. Alternatively, an electrolyte solution can be applied on a member having a flat surface to form an electrolyte layer, and then the electrolyte layer can be peeled and interposed between the positive electrode and the negative electrode. As described above, since some of the electrolytes transition to a crystalline state through a gel state immediately after preparation, such an electrolyte can be interposed between the positive electrode and the negative electrode in a gel state.

  For the positive electrode, a conductive material and a binder are mixed with a positive electrode active material capable of inserting and extracting lithium ions, and an appropriate solvent is added as necessary to form a paste-like positive electrode mixture, such as a metal such as aluminum. It can be formed by coating and drying on the surface of the current collector made of foil, and then increasing the active material density by pressing.

  The positive electrode active material is not particularly limited as long as it can electrochemically occlude and release lithium ions. For example, a material containing lithium and at least one transition metal is preferable. Specific examples include lithium transition metal composite oxides and lithium-containing transition metal phosphate compounds.

V, Ti, Cr, Mn, Fe, Co, Ni, Cu and the like are preferable as the transition metal of the lithium transition metal composite oxide. Specific examples include lithium-cobalt composite oxides such as LiCoO ₂ , LiMnO ₂ , LiMn. Examples thereof include lithium / manganese composite oxides such as ₂ O ₄ and Li ₂ MnO ₄ , lithium / nickel composite oxides such as LiNiO ₂ , and the like. Further, some of the transition metal atoms that are the main components of these lithium transition metal composite oxides are Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, and Si. Specific examples include lithium / cobalt / nickel composite oxides, lithium / cobalt / manganese composite oxides, lithium / nickel / manganese composite oxides, lithium / nickel / Cobalt / manganese composite oxides are listed.

Specific examples of the substituted ones include, for example, Li _{1 + a} Ni _0.5 Mn _0.5 O ₂ , Li _{1 + a} Ni _0.8 Co _0.2 O ₂ , Li _{1 + a} Ni _0.85 Co _0.10 Al _{0. 05} O ₂ , Li _{1 + a} Ni _0.33 Co _0.33 Mn _0.33 O ₂ , Li _{1 + a} Ni _0.45 Co _0.45 Mn _0.1 O ₂ , Li _{1 + a} Mn _1.8 Al _0.2 O ₄ , Li _{1 + a} Mn _1.5 Ni _0.5 O ₄ , xLi ₂ MnO _3. (1-x) Li _{1 + a} MO ₂ (M = transition metal) and the like (a = 0 <a ≦ 3.0).

The lithium-containing transition metal phosphate compound is LixMPO ₄ (M = a kind of element selected from the group consisting of Group 4 to Group 11 transition metals in the periodic table, x is 0 <x <1.2). The transition metal (M) is at least one selected from the group consisting of V, Ti, Cr, Mg, Zn, Ca, Cd, Sr, Ba, Co, Ni, Fe, Mn, and Cu. It is preferable that it is at least one element selected from the group consisting of Co, Ni, Fe, and Mn. For _{example, LiFePO 4, Li 3 Fe 2} (PO 4) 3, LiFeP 2 O 7 , etc. of phosphorus Santetsurui, cobalt phosphate such as LiCoPO _4, manganese phosphate such as LiMnPO _4, phosphoric acids such as LiNiPO ₄ Nickel, a part of transition metal atoms that are the main components of these lithium transition metal phosphate compounds are Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Examples include those substituted with other metals such as Nb and Si. Among these, lithium-manganese complex oxides such as LiMnO ₂ , LiMn ₂ O ₄ and Li ₂ MnO ₄ , and iron phosphates such as LiFePO ₄ , Li ₃ Fe ₂ (PO ₄ ) ₃ and LiFeP ₂ O ₇ However, it is preferably used because metal elution is not likely to occur at high temperature and in a charged state and is inexpensive.

  The said positive electrode active material may be used independently and may use 2 or more types together.

The conductive material is for ensuring the electrical conductivity of the positive electrode, and a mixture of one or two or more carbon material powders such as carbon black, acetylene black, and graphite can be used.
The binder is not particularly limited as long as it plays a role of securing the active material particles and the conductive material particles. Specific examples include polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, polyimide, aromatic polyamide, and cellulose. Resin polymers such as nitrocellulose; rubbery polymers such as SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), fluorine rubber, isoprene rubber, butadiene rubber, ethylene-propylene rubber; styrene-butadiene- Styrene block copolymer or hydrogenated product thereof, EPDM (ethylene / propylene / diene terpolymer), styrene / ethylene / butadiene / ethylene copolymer, styrene / isoprene / styrene block copolymer or hydrogenated product thereof Thermoplastic elastomeric polymers such as: Syndiotactic-1,2-polybutadiene, polyvinyl acetate, ethylene / vinyl acetate copolymers, propylene / α-olefin copolymers, etc .; polyvinylidene fluoride Fluorine polymers such as (PVdF), polytetrafluoroethylene, fluorinated polyvinylidene fluoride, polytetrafluoroethylene / ethylene copolymer; polymer compositions having alkali metal ion ionic conductivity, and the like. In addition, these substances may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
The solvent for dispersing the active material, the conductive material, and the binder is not particularly limited, and either an aqueous solvent or an organic solvent may be used. Examples of the aqueous medium include water, a mixed medium of alcohol and water, and the like. Examples of the organic medium include aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene; heterocyclic compounds such as quinoline and pyridine; ketones such as acetone, methyl ethyl ketone, and cyclohexanone. Esters such as methyl acetate and methyl acrylate; amines such as diethylenetriamine and N, N-dimethylaminopropylamine; ethers such as diethyl ether, propylene oxide and tetrahydrofuran (THF); N-methylpyrrolidone (NMP) Amides such as dimethylformamide and dimethylacetamide; and aprotic polar solvents such as hexamethylphosphalamide and dimethylsulfoxide.

  Regarding the negative electrode, the negative electrode active material is not particularly limited as long as it can electrochemically occlude and release lithium ions. Specific examples thereof include carbonaceous materials, alloy-based materials, lithium-containing metal composite oxide materials, and the like. These may be used individually by 1 type, and may be used together combining 2 or more types arbitrarily. Among these, it is particularly preferable to use a carbon material. Since the specific surface area can be made relatively large and the lithium occlusion and release speed is fast, the charge / discharge characteristics at a large current and the output / regeneration density are good. In particular, considering the balance between output and regenerative density, it is preferable to use a carbon material having a relatively large voltage change with charge / discharge. Among them, it is preferable to use those made of natural graphite or artificial graphite having high crystallinity. By using such a highly crystalline carbon material, the lithium ion delivery efficiency of the negative electrode can be improved.

  Thus, when a carbon material is used as the negative electrode active material, a negative electrode mixture obtained by mixing a conductive material and a binder as described for the positive electrode is applied to the current collector as necessary. It is preferable to use what is formed.

  A separator can be employed as necessary. The separator plays a role of electrically insulating the positive electrode and the negative electrode and holding the electrolyte. For example, a porous synthetic resin film, particularly a polyolefin polymer (polyethylene, polypropylene) porous film may be used. The separator is preferably larger than the positive electrode and the negative electrode in order to ensure insulation between the positive electrode and the negative electrode.

  The case is not particularly limited and can be made of a known material and form.

  The gasket secures electrical insulation between the case and both the positive and negative terminal portions and airtightness in the case. For example, it can be composed of a polymer such as polypropylene that is chemically and electrically stable to the electrolyte.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

(Examples 1 and 2)
[Preparation of electrolyte]
Electrolyte 1: 1,2-dimethoxybenzene LiN (SO ₂ CF ₃ ) ₂ (hereinafter referred to as LiTFSI) (1.02 g, 3.54 mmol) was weighed into a Schlenk reaction tube substituted with nitrogen, and 1,2- Dimethoxybenzene (0.977 g, 7.07 mmol) was added and stirred at room temperature for 30 minutes. This was heated to 100 ° C. in an oven and melted, and then allowed to stand at room temperature, whereby Li {N (SO ₂ CF ₃ ) ₂ } {C ₆ H ₄ (OCH ₃ ) ₂ } ₂ was obtained as colorless and transparent crystals. Obtained as a crystalline solid.

Electrolyte 2: 1,2-difluoro-4,5-dimethoxybenzene LiTFSI (0.299 g, 1.05 mmol) was weighed into a nitrogen-substituted Schlenk reaction tube and 1,2-difluoro-4,5-dimethoxybenzene (0 365 g, 2.10 mmol) was added. This was heated with a 120 ° C. dryer to obtain a clear viscous solution. By allowing this to stand at room temperature, a crystal of Li {N (SO ₂ CF ₃ ) ₂ } {C ₆ H ₂ F ₂ (OCH ₃ ) ₂ } ₂ was obtained.

[Ion conductivity measurement]
The sample obtained here was press-molded into a disk shape, and the ionic conductivity was measured by an alternating current impedance method in a sealed cell, and it was confirmed that the ionic conductivity was exhibited in a solid state. The results are shown in FIG.

(Examples 3 to 6)
[Preparation of electrolyte]
Electrolyte 3: (H ₃ C) ₂ NCH ₂ CH ₂ N (CH ₃ ) ₂
In accordance with a previously reported method, LiTFSI (1.85 g, 6.44 mmol) was taken into a Schlenk reaction tube purged with nitrogen, 5 ml of dehydrated toluene was added, and N, N, N ′, N′-tetramethylethylenediamine (0.96 ml, 6 .44 mmol) was added and heated to 80 ° C. to dissolve. The solution was allowed to stand at room temperature overnight to precipitate crystals, and then the solvent was removed by decantation. The resulting colorless and transparent crystals were washed with hexane three times and dried overnight under reduced pressure to obtain the desired product (2.50 g, 96%).

Electrolyte 4: (H ₃ C) ₂ N (CH ₂ ) ₂ NCH ₃ (CH ₂ ) ₂ N (CH ₃ ) ₂
According to a previously reported method, LiTFSI (1.5712 g, 5.473 mmol) was taken into a Schlenk reaction tube purged with nitrogen, 5 ml of dehydrated toluene was added, and N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (1. 14 ml, 5.473 mmol) was added and heated to 80 ° C. to dissolve. The solution was allowed to stand at room temperature overnight to precipitate crystals, and then the solvent was removed by decantation. The resulting colorless and transparent crystals were washed with hexane three times and dried overnight under reduced pressure to obtain the desired product (2.197 g, 87%).

Electrolyte 5: (H ₃ C) ₂ NCH (CH ₃ ) CH ₂ N (CH ₃ ) ₂
LiTFSI (0.938 g, 3.27 mmol) was taken into a Schlenk reaction tube purged with nitrogen, 3 ml of dehydrated toluene was added, and then N, N, N ′, N′-tetramethyl-1,2-diaminopropane (0.532 ml) was added. ) Was added and heated to 80 ° C. to dissolve. The solution was allowed to stand at room temperature overnight to precipitate crystals, and then the solvent was removed by decantation. The resulting colorless and transparent crystals were washed with hexane three times and dried under reduced pressure overnight to obtain the desired product (1.153 g, 78.1%).

Electrolyte 6: (H ₃ C) ₂ N (CH ₂ ) ₃ N (CH ₃ ) ₂
LiTFSI (1.5019 g, 5.232 mmol) is added to a nitrogen-substituted Schlenk reaction tube, 8 ml of dehydrated toluene is added, and N, N, N ′, N′-tetramethyl-1,3-diaminopropane (0.532 mL, 3.308 mmol) was added and dissolved by heating to 80 ° C. The solution was allowed to stand overnight at room temperature to precipitate crystals, and then the solvent was removed by decantation. After washing with hexane three times, the product was dried overnight under reduced pressure to obtain the desired product (1.815 g, 83%).

[Ion conductivity measurement]
The sample obtained here was press-molded into a disk shape, and the ionic conductivity was measured by an alternating current impedance method in a sealed cell, and it was confirmed that the ionic conductivity was exhibited in a solid state. The results are shown in FIG.

(Examples 7 to 11)
[Preparation of electrolyte]
Electrolytes 7 to 11: Trithian In a glove box under an argon atmosphere, a desired amount of 1,3,5-trithiane, LiTFSI, acetonitrile, and zirconia balls were placed in order in a zirconia ball mill container and sealed. The rotation speed of the container was 700 revolutions per minute, and the operation was performed for 5 minutes and stopped for 5 minutes, and the sample was synthesized. Reagents were mixed at a mixing ratio. The ratio of Trithian and LiTFSI was 2: 1 (electrolyte 7), 1: 1 (electrolyte 8), 1: 2 (electrolyte 9), and 1: 3 (electrolyte 10). Acetonitrile was added in an equimolar amount with LiTFSI. The sample was dried overnight at room temperature under reduced pressure after ball milling. A sample in which a double molar amount of LiBETI (LiN (SO ₂ CF ₂ CF ₃ ) ₂ was allowed to act on trithiane was also obtained in the same manner (electrolyte 11).

[Ion conductivity measurement]
The sample obtained here was press-molded into a disk shape, and the ionic conductivity was measured by an alternating current impedance method in a sealed cell, and it was confirmed that the ionic conductivity was exhibited in a solid state. The results are shown in FIGS.

(Examples 12 to 23)
[Preparation of electrolyte]
Electrolyte 12: [N (CH ₃ ) ₄ ] [N (SO ₂ CF ₂ ) ₂ CF ₂ ] (N ₁₁₁₁ CPFSI)
Tetramethylammonium bromide (0.491 g, 3.19 mmol) was dissolved in 2 ml of ion exchange water, and then LiCPFSI (Li [N (SO ₂ CF ₂ ) ₂ CF ₂ ] dissolved in 6 ml of ion exchange water. ) (0.951 g, 3.18 mmol) was added dropwise. The mixed solution is stirred for 3 hours at room temperature, and then filtered using a membrane filter (0.45 μm). The solid remaining on the filter is collected in a Schlenk tube and dried in a vacuum at about 100 ° C. for 48 hours. Was synthesized (yield: 72%).
N ₁₁₁₁ CPFSI: ¹ H NMR (400 MHz, rt, DMSO-d ₆ ): 3.08 (s, 12H, N (CH ₃ ) ₄ ). ¹³ C NMR (68 MHz, rt, DMSO-d ₆ ): 54.5 ( t, J _CN = 3.9 Hz, N (CH ₃ ) ₄ ), 109.3 (tt, ¹ J _CF = 272.9 Hz, ² J _CF = 25.4 Hz, -CF ₂ -CF ₂ -CF _2- ), 112.4 (tt, ¹ J _CF = 296.6 Hz, ² J _CF = 25.1 Hz, -CF ₂ -CF ₂ -CF _2- ). ¹⁹ F NMR (376 MHz, rt, DMSO-d ₆ ): -120.4 (br), -105.4 ( br). Anal. Calcd for C ₇ H ₁₂ F ₆ N ₂ O ₄ S ₂ : C, 22.95; H, 3.30; N, 7.65. Found: C, 23.12; H, 3.20; N, 7.46.

Electrolyte 13: [N (CH ₃ ) ₃ (CH ₂ CH ₃ )] [N (SO ₂ CF ₂ ) ₂ CF ₂ ] (N ₁₁₁₂ CPFSI)
The synthesis was performed in the same procedure as the electrolyte 12 except that ethyltrimethylammonium iodide was used as a raw material (yield: 72%).
N ₁₁₁₂ CPFSI: ¹ H NMR (400 MHz, rt, DMSO-d ₆ ): 1.23 (t, 3H, J _HH = 7.3 Hz, N (CH ₃ ) ₃ (CH ₂ CH ₃ )), 3.00 (s, 9H , N (CH ₃ ) ₃ (CH ₂ CH ₃ )), 3.31 (q, 2H, J _HH = 7.3 Hz, N (CH ₃ ) ₃ (CH ₂ CH ₃ )). ¹³ C NMR (67.8 MHz, rt, DMSO-d ₆ ): 7.9 (s, N (CH ₃ ) ₃ (CH ₂ CH ₃ )), 51.7 (t, J _CN = 4.2 Hz, N (CH ₃ ) ₃ (CH ₂ CH ₃ )), 61.0 ( t, J _CN = 2.8 Hz, N (CH ₃ ) ₃ (CH ₂ CH ₃ )), 109.4 (tt, ¹ J _CF = 272.9 Hz, ² J _CF = 25.1 Hz, -CF ₂ -CF ₂ -CF _2- ), 112.5 (tt, ¹ J _CF = 297.7 Hz, ² J _CF = 25.1 Hz, -CF ₂ -CF ₂ -CF _2- ). ¹⁹ F NMR (376 MHz, rt, DMSO-d ₆ ): -120.4 ( br), -105.4 (br). Anal. Calcd for C ₈ H ₁₄ F ₆ N ₂ O ₄ S ₂ : C, 25.26; H, 3.71; N, 7.37. Found: C, 25.27; H, 3.87; N, 7.56.

Electrolyte 14: [N (CH ₃ ) (CH ₂ CH ₃ ) ₃ ] [N (SO ₂ CF ₂ ) ₂ CF ₂ ] (N ₁₂₂₂ CPFSI)
The synthesis was performed in the same procedure as the electrolyte 12 except that triethylmethylammonium chloride was used as a raw material (yield: 79%).
N ₁₂₂₂ CPFSI: ¹ H NMR (400 MHz, rt, DMSO-d ₆ ): 1.19 (t, 9H, J _HH = 7.3 Hz, N (CH ₃ ) (CH ₂ CH ₃ ) ₃ ), 2.86 (s, 3H _{, N (CH 3) (CH} 2 CH 3) 3), 3.24 (q, 6H, J HH = 7.3 Hz, N (CH 3) (CH 2 CH 3) 3). 13 C NMR (67.8 MHz, rt, DMSO-d ₆ ): 7.2 (s, N (CH ₃ ) (CH ₂ CH ₃ ) ₃ ), 45.9 (t, J _CN = 4.2 Hz, N (CH ₃ ) (CH ₂ CH ₃ ) ₃ ), 55.1 ( t, J _CN = 2.8 Hz, N (CH ₃ ) (CH ₂ CH ₃ ) ₃ ), 109.5 (tt, ¹ J _CF = 272.7 Hz, ² J _CF = 25.1 Hz, -CF ₂ -CF ₂ -CF _2- ), 112.5 (tt, ¹ J _CF = 298.0 Hz, ² J _CF = 25.1 Hz, -CF ₂ -CF ₂ -CF _2- ) ¹⁹ F NMR (376 MHz, rt, DMSO-d ₆ ): -120.4 (br ), -105.4 (br). Anal. Calcd for C ₁₀ H ₁₈ F ₆ N ₂ O ₄ S ₂ : C, 29.41; H, 4.44; N, 6.86. Found: C, 29.40; H, 4.36; N, 6.74 .

Electrolyte 15: [N (CH ₂ CH ₃ ) ₄ ] [N (SO ₂ CF ₂ ) ₂ CF ₂ ] (N ₂₂₂₂ CPFSI)
The synthesis was performed in the same procedure as the electrolyte 12 except that tetraethylammonium bromide was used as a raw material (quant.).
N ₂₂₂₂ TFSI: ¹ H NMR (400 MHz, rt, DMSO-d ₆ ): 1.17 (t, 12H, J _HH = 6.8 Hz, N (CH ₂ CH ₃ ) ₄ ), 3.21 (q, 8H, J _HH = _{. 6.8 Hz, N (CH 2} CH 3) 4) 13 C NMR (68 MHz, rt, DMSO-d 6): 6.9 (s, N (CH 2 CH 3) 4), 51.5 (t, J CN = 3.1 Hz, N (CH ₂ CH ₃ ) ₄ ), 109.3 (tt, ¹ J _CF = 272.9 Hz, ² J _CF = 25.4 Hz, -CF ₂ -CF ₂ -CF _2- ), 112.4 (tt, ¹ J _CF = 296.6 Hz, ² J _CF = 25.1 Hz, -CF ₂ -CF ₂ -CF _2- ). ¹⁹ F NMR (376MHz, rt, DMSO-d ₆ ): -120.4 (br), -105.5 (br). Anal. Calcd for C ₁₁ H ₂₀ F ₆ N ₂ O ₄ S ₂ : C, 31.28; H, 4.77; N, 6.63. Found: C, 31.30; H, 4.74; N, 6.70.

Electrolyte 16: [N (CH ₃ ) ₂ (CH ₂ CH ₃ ) ₂ ] [N (SO ₂ CF ₂ ) ₂ CF ₂ ] (N ₁₁₂₂ CPFSI)
N, N-diethylmethylamine (1.59 ml, 13.4 mol) and iodomethane (1.0 ml, 16.1 mmol) were mixed in 4.7 ml of acetonitrile and stirred at room temperature for 24 hours. Thereafter, the solvent was distilled off under reduced pressure, the product was washed with hexane (5 ml × 6), dried in vacuo at about 100 ° C. for 48 hours, and N-methyl-N, N-dimethylethylammonium iodide (N ₁₁₂₂ I ) Was synthesized (white solid, yield: 62%). The synthesized N-ethyl-N, N-dimethylethylammonium iodide (0.8614 g, 3.76 mmol) was dissolved in 2 ml of ion-exchanged water, and LiCPFSI (1. 1264 g, 3.76 mmol) was added dropwise. The mixed solution was cooled in an ice bath for 30 minutes, and the precipitated solid was collected by filtration through a membrane filter (0.45 μm). The solid remaining on the filter was washed with ion-exchanged water (10 ml × 6), then transferred to a Schlenk tube and dried in vacuum at about 100 ° C. for 48 hours to synthesize a sample (white solid, yield: 65%). .
N ₁₁₂₂ CPFSI: ¹ H NMR (400 MHz, rt, DMSO-d ₆ ): 1.22 (t, 6H, J _HH = 6.8 Hz), 2.94 (s, 6H), 3.29 (q, 4H, J _HH = 6.8 Hz ¹³ C NMR (67.8 MHz, rt, DMSO-d ₆ ): 7.6 (s, CH ₃ -CH ₂ -N), 48.9 (t, J _CN = 4.2 Hz, CH ₃ -N), 58.0 (t, J _CN = 3.1 Hz, CH ₃ -CH ₂ -N), 109.4 (tt, ¹ J _CF = 272.9 Hz, ² J _CF = 25.1 Hz, -CF ₂ -CF ₂ -CF _2- ), 112.5 (tt, ¹ J _CF = 297.7 Hz, ² J _CF = 25.1 Hz, -CF2-CF2-CF2-). ¹⁹ F (376 MHz, rt, DMSO-d ₆ ): -120.5 (br), -105.5 (br) .Anal. Calcd for C ₉ H ₁₆ F ₆ N ₂ O ₄ S ₂ : C, 27.41; H, 4.09; N, 7.10. Found: C, 27.34; H, 4.02; N, 7.16.

Electrolyte 17: [N (CH ₃ ) ₂ (CH ₂ CH ₂ CH ₂ CH ₂ )] [N (SO ₂ CF ₂ ) ₂ CF ₂ ] (P ₁₁ CPSFI)
1-methylpyrrolidinium (1.91 ml, 18 mmol) and iodomethane (1.34 ml, 22 mmol) were mixed in 5 ml of acetonitrile and stirred at room temperature for 24 hours. Thereafter, the solvent was distilled off under reduced pressure, and the product was washed with hexane (10 ml × 4) and dried in vacuum at about 100 ° C. for 48 hours to synthesize N, N-dimethylpyrrolidinium iodide (yield: 89%). The synthesis was performed in the same procedure as the electrolyte 12 except that the synthesized N, N-dimethylpyrrolidinium iodide was used as a raw material (yield: 65%).
P ₁₁ CPFSI: ¹ H NMR (400 MHz, rt, DMSO-d ₆ ): 2.10 (m, 4H, N (-CH ₂ CH ₂ CH ₂ CH _2- ) (CH ₃ ) ₂ ), 3.08 (s, 6H _{, N (-CH 2 CH 2 CH} 2 CH 2 -) (CH 3) 2), 3.44 (m, 4H, N (-CH 2 CH 2 CH 2 CH 2 -). (CH 3) 2) 13 C NMR (68 MHz, rt, DMSO-d ₆ ): 21.4 (s, N (-CH ₂ CH ₂ CH ₂ CH _2- ) (CH ₃ ) ₂ ), 51.1 (t, J _CN = 3.9 Hz, N (-CH ₂ CH ₂ CH ₂ CH _2- ) (CH ₃ ) ₂ ), 64.9 (t, J _CN = 3.1 Hz, N (-CH ₂ CH ₂ CH ₂ CH _2- ) (CH ₃ ) ₂ ), 109.3 (tt, ¹ J _CF = 272.6 Hz, ² J _CF = 25.7 Hz, -CF ₂ -CF ₂ -CF _2- ), 112.5 (tt, ¹ J _CF = 298.0 Hz, ² J _CF = 25.1 Hz, -CF ₂ -CF ₂ -CF _2- ). ¹⁹ F NMR (376MHz, rt, DMSO-d ₆ ): -120.4 (br), -105.3 (br). Anal. Calcd for C ₉ H ₁₄ F ₆ N ₂ O ₄ S ₂ : C , 27.55; H, 3.60; N, 7.14. Found: C, 27.56; H, 3.46; N, 7.11.

Electrolyte 18: [N (CH ₃ ) (CH ₂ CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₂ )] [N (SO ₂ CF ₂ ) ₂ CF ₂ ] (P ₁₂ CPFSI)
N-ethyl-N-methylpyrrolidinium iodide was synthesized in the same procedure as N, N-dimethylpyrrolidinium iodide using iodoethane as a raw material. Thereafter, synthesis was performed in the same procedure as the electrolyte 12 except that the synthesized N-ethyl-N-methylpyrrolidinium iodide was used as a raw material (yield: 72%).
P ₁₂ CPFSI: ¹ H NMR (400 MHz, rt, DMSO-d ₆ ): 1.24-1.27 (m, 3H, N (-CH ₂ CH ₂ CH ₂ CH _2- ) (CH ₂ CH ₃ ) (CH ₃ ) ), 2.05 (m, 4H, N (-CH ₂ CH ₂ CH ₂ CH _2- ) (CH ₂ CH ₃ ) (CH ₃ )), 2.94 (s, 3H, N (-CH ₂ CH ₂ CH ₂ CH ₂ -) (CH ₂ CH ₃ ) (CH ₃ )), 3.32-3.42 (m, 6H, N (-CH ₂ CH ₂ CH ₂ CH _2- ) (CH ₂ CH ₃ ) (CH ₃ )). ¹³ C NMR (68 MHz, rt, DMSO-d ₆ ): 8.7 (s, N (-CH ₂ CH ₂ CH ₂ CH _2- ) (CH ₂ CH ₃ ) (CH ₃ )), 21.1 (s, N (-CH ₂ CH ₂ CH ₂ CH _2- ) (CH ₂ CH ₃ ) (CH ₃ )), 47.0 (t, J _CN = 3.9 Hz, N (-CH ₂ CH ₂ CH ₂ CH _2- ) (CH ₂ CH ₃ ) ( CH ₃ )), 58.5 (t, J _CN = 3.1 Hz, N (-CH ₂ CH ₂ CH ₂ CH _2- ) (CH ₂ CH ₃ ) (CH ₃ )), 62.0 (t, J _CN = 3.3 Hz, N (-CH ₂ CH ₂ CH ₂ CH _2- ) (CH ₂ CH ₃ ) (CH ₃ )), 109.3 (tt, ¹ J _CF = 272.6 Hz, ² J _CF = 25.7 Hz, -CF ₂ -CF _2- CF _2- ), 112.4 (tt, ¹ J _CF = 297.6 Hz, ² J _CF = 25.7 Hz, -CF ₂ -CF ₂ -CF _2- ). ¹⁹ F NMR (376MHz, rt, DMSO-d ₆ ):- 120.5 (br), -105.5 (br). Anal. Calcd for C ₁₀ H ₁₆ F ₆ N ₂ O ₄ S ₂ : C, 29.56; H, 3.97; N, 6.89. Found: C, 29.52; H, 3.82; N, 6.81.

Electrolytes 19 to 21: [N (CH ₃ ) (CH ₂ CH ₃ ) ₃ ] [N (SO ₂ CF ₂ ) ₂ CF ₂ ] + nLiTFSI (n = 0.01, 0.5, 0.1) (N ₁₂₂₂ CPFSI) [N (CH ₃ ) (CH ₂ CH ₃ ) ₃ ] [N (SO ₂ CF ₂ ) ₂ CF ₂ ] (N ₁₂₂₂ CPFSI) is [N (CH ₃ ) (CH ₂ CH ₃ ) ₃ ] Cl ( N ₁₂₂₂ Cl) and LiCPFSI were synthesized by an ion exchange method. In addition, 0.01 times mole of LiTFSI (0.0056 g, 0.0195 mmol) with respect to N ₁₂₂₂ CPFSI (0.7972 g, 1.98 mmol) was mixed using acetonitrile (5 ml) as a solvent, and then the solvent. Was distilled off under reduced pressure and dried in vacuum at about 100 ° C. for 72 hours or longer to obtain a sample (electrolyte 19). It was confirmed by ¹ H NMR and DSC that acetonitrile was not contained in the prepared sample. Further, in a similar _{manner, N 1222 CPFSI (0.8848g, 2.17mmol} ) doped samples the 0.05, 0.1 fold molar LiTFSI prepared against (each, an electrolyte 20 and 21).

アセトニトリル（９ml）中でテトラメチルエチレンジアミン（ＴＭＥＤＡ，２．４ml，１６mmol）とクロロメチルメチルスルフィド（３．２ml，３２mmol）を混合し、２４時間還流した。溶媒を減圧留去した後ヘキサン（２０ml×３）とアセトン（２０ml×３）で洗浄し、減圧下６０℃で４８時間以上乾燥した（収率：８７%）。生成物（０．５０１２g，１．６２mmol）とＬｉＣＰＦＳＩ（０．９７４７g，３．２４mmol）をイオン交換水中で混合し、析出した白色固体をメンブレンフィルターで濾別後シュレンク反応管に移した。減圧下７５℃で４８時間以上乾燥を行い、上図にあるジカチオン性アンモニウムＣＰＦＳＩ塩を生成物として得た（収率：９７%）（電解質２２）。 Electrolytes 22 and 23: Addition of a dication ammonium salt having a sulfide group and a lithium salt

Tetramethylethylenediamine (TMEDA, 2.4 ml, 16 mmol) and chloromethyl methyl sulfide (3.2 ml, 32 mmol) were mixed in acetonitrile (9 ml) and refluxed for 24 hours. The solvent was distilled off under reduced pressure, washed with hexane (20 ml × 3) and acetone (20 ml × 3), and dried at 60 ° C. under reduced pressure for 48 hours or more (yield: 87%). The product (0.5012 g, 1.62 mmol) and LiCPFSI (0.9747 g, 3.24 mmol) were mixed in ion-exchanged water, and the precipitated white solid was filtered off with a membrane filter and transferred to a Schlenk reaction tube. Drying was performed at 75 ° C. for 48 hours or more under reduced pressure to obtain the dicationic ammonium CPFSI salt in the above figure as a product (yield: 97%) (electrolyte 22).

  Further, the above-mentioned dicationic ammonium CPFSI salt (0.8794 g, 1.07 mmol) and LiTFSI (0.0305 g, 0.106 mmol) were taken in a Schlenk reaction tube, and acetonitrile (10 ml) was added and mixed to obtain a uniform solution. Thereafter, the solvent was distilled off under reduced pressure and dried at 90 ° C. for 48 hours or longer to prepare a sample (electrolyte 23).

The synthesis of the sample was confirmed by NMR. The NMR data is shown below.
¹ H NMR (400 MHz, rt, DMSO-d ₆ ): 2.48 (s, 6H), 3.27 (s, 12H), 4.02 (s, 4H), 4.77 (s, 4H). ¹³ C NMR (67.8 MHz, rt, DMSO-d ₆ ): 18.1 (s), 49.2 (s), 54.2 (s), 71.1 (s), 109.4 (tt, ¹ J _CF = 272.9 Hz, ² J _CF = 25.1 Hz, -CF _2- CF ₂ -CF _2- ), 112.5 (tt, ¹ J _CF = 297.7 Hz, ² J _CF = 25.1 Hz, -CF ₂ -CF ₂ -CF _2- ). ¹⁹ F (376 MHz, rt, DMSO-d ₆ ): -120.4 (br), -105.4 (br).

[Ion conductivity measurement]
The sample obtained here was press-molded into a disk shape, and the ionic conductivity was measured by an alternating current impedance method in a sealed cell, and it was confirmed that the ionic conductivity was exhibited in a solid state. The results are shown in FIG.

(Examples 24-26)
[Preparation of electrolyte]
Electrolytes 24 to 26: LiN (SO ₂ CF ₃ ) ₂ + nCH ₃ CN (n = 0.33, 0.5, 0.67)
A desired amount of acetonitrile was added to LiN (SO ₂ CF ₃ ) ₂ (hereinafter referred to as LiTFSI) under a nitrogen atmosphere, and the mixture was stirred at room temperature for 1 hour to obtain a target sample as a white powder. . The ratio of LiTFSI to acetonitrile was 1: 0.33 (electrolyte 24), 1: 0.5 (electrolyte 25), and 1: 0.67 (electrolyte 26).

[Ion conductivity measurement]
The sample obtained here was press-molded into a disk shape, and the ionic conductivity was measured by an alternating current impedance method in a sealed cell, and it was confirmed that the ionic conductivity was exhibited in a solid state. The results are shown in FIG.

(Example 27)
[Preparation of electrolyte]
Electrolyte 27: Li [N (SO ₂ CF ₃ ) ₂ ] (CH ₃ CN)
Samples were synthesized with reference to the method described in Acta Cryst. 2011, E67, m534. After making LiTFSI about 1.5 g in a Schlenk reaction tube under an inert gas atmosphere, a 5-fold molar amount of acetonitrile was added and stirred at room temperature for about 1 hour to obtain a colorless and transparent solution. Toluene was added until this solution separated into two phases, and the mixture was allowed to stand at room temperature, whereby Li [N (SO ₂ CF ₃ ) ₂ ] (CH ₃ CN) (Li (TFSI) (CH ₃ CN)) was colorless. Obtained as a transparent single crystal.

[Ion conductivity measurement]
The sample obtained here was press-molded into a disk shape, and the ionic conductivity was measured by an alternating current impedance method in a sealed cell, and it was confirmed that the ionic conductivity was exhibited in a solid state. The results are shown in FIG.

(Example 28)
[Preparation of electrolyte]
Electrolyte 28: Li (CF ₃ SO ₃ ) (CH ₃ CN)
An excess amount of acetonitrile was added to Li (CF ₃ SO ₃ ) (hereinafter referred to as LiOTf) and dissolved, and then toluene was added and left at room temperature to give colorless plate crystals. The mother liquor was removed and the crystals were washed with pentane. Li (CF ₃ SO ₃ ) (CH ₃ CN) was obtained by drying the crystals under a nitrogen stream.

[Ion conductivity measurement]
The sample obtained here was press-molded into a disk shape, and the ionic conductivity was measured by an alternating current impedance method in a sealed cell, and it was confirmed that the ionic conductivity was exhibited in a solid state. The results are shown in FIG.

(Examples 29 and 30)
[Preparation of electrolyte]
Electrolyte _{29~30: Li (X) {(} H 3 C) 2 NCH 2 CH 2 N (CH 3) 2} (X = N (SO 2 CF 2) 2 CF 2 (CPFSA) and _CF 3 _SO 3 (OTf ))
Toluene was added to Li [N (SO ₂ CF ₂ ) ₂ CF ₂ ] (hereinafter referred to as LiCPFSA) to obtain a suspension, and then an equimolar amount of (H ₃ C) ₂ NCH ₂ CH ₂ N ( CH ₃ ) ₂ (tetramethylethylenediamine, hereinafter referred to as TMEDA) was added. After heating at 40 ° C. to completely dissolve LiCPFSA, the reaction solution was cooled to room temperature and allowed to stand to obtain colorless crystals. The mother liquor was removed, washed with pentane, and then dried under reduced pressure to obtain the target product Li (CPFSA) (TMEDA) (electrolyte 29).
Li (OTf) (TMEDA) was obtained by using Li (CF ₃ SO ₃ ) (hereinafter referred to as LiOTf) instead of LiCPFSA in the same manner (electrolyte 30).

[Ion conductivity measurement]
The sample obtained here was press-molded into a disk shape, and the ionic conductivity was measured by an alternating current impedance method in a sealed cell, and it was confirmed that the ionic conductivity was exhibited in a solid state. The results are shown in FIG.

(Examples 31-33)
[Preparation of electrolyte]
Electrolytes 31-33: [N (CH ₃ ) (CH ₂ CH ₃ ) ₃ ] [N (SO ₂ CF ₂ ) ₂ CF ₂ ] (N ₁₂₂₂ CPFSA) + 0.1LiX (X═N (SO ₂ CF ₂ ) ₂ CF ₂ (CPFSA), N (SO ₂ CF ₃ ) ₂ (TFSI) and CF ₃ SO ₃ (OTf))
The plastic crystal ion pair [N (CH ₃ ) (CH ₂ CH ₃ ) ₃ ] [N (SO ₂ CF ₂ ) ₂ CF ₂ ] (N ₁₂₂₂ CPFSA) has a molar ratio of LiX (where X Are N (SO ₂ CF ₂ ) ₂ CF ₂ (CPFSA) (electrolyte 31), N (SO ₂ CF ₃ ) ₂ (TFSI) (electrolyte 32), and CF ₃ SO ₃ (OTf) (electrolyte 33). ) Was added and dissolved using acetonitrile, and then the solvent was distilled off under heating conditions. The resulting white powder was heated and melted to dope lithium salt into the plastic crystal ion pair.

[Ion conductivity measurement]
The sample obtained here was press-molded into a disk shape, and the ionic conductivity was measured by an alternating current impedance method in a sealed cell, and it was confirmed that the ionic conductivity was exhibited in a solid state. The results are shown in FIG.

(Example 34)
[Preparation of electrolyte]
Electrolyte 34: Li [N (SO ₂ CF ₃ ) ₂ ] _0.67 [CF ₃ SO ₃ ] _0.33 (Li (TFSI) _0.67 (OTf) _0.33 ) + 0.33CH ₃ CN
LiN (SO ₂ CF ₃ ) ₂ (hereinafter referred to as LiTFSI) and Li (CF ₃ SO ₃ ) (hereinafter referred to as LiOTf) were placed in a flask, and acetonitrile was added and dissolved. Acetonitrile was distilled off under heating conditions to obtain a white powder. The obtained powder was heated and melted to mix two kinds of salts, and then cooled to room temperature. Thereafter, 0.5 times molar amount of acetonitrile was again added to LiTFSI, and the mixture was stirred to obtain a target sample.

[Ionic conductivity measurement] The sample obtained here was press-molded into a disk shape, and the ionic conductivity was measured by an alternating current impedance method in a sealed cell, and it was confirmed that the ionic conductivity was exhibited in a solid state. The results are shown in FIG.

(Examples 35 and 36)
[Preparation of electrolyte]
Electrolyte 35 and _{36: NaX + 0.5CH 3 CN (} X = N (SO 2 CF 3) 2 and SCN)
NaX was placed in a flask, 0.5 times the molar amount of acetonitrile was added, and the mixture was stirred at room temperature for 1 hour to obtain the intended sample. Here, X is N (SO ₂ CF ₃ ) ₂ (electrolyte 35) or SCN (electrolyte 36).

[Ion conductivity measurement]
The sample obtained here was press-molded into a disk shape, and the ionic conductivity was measured by an alternating current impedance method in a sealed cell, and it was confirmed that the ionic conductivity was exhibited in a solid state. The results are shown in FIG.
(Example 37)
[Lithium ion battery]
Using an R2032 coin-type cell, 0.1 times molar amount of LiCPFSA was added to electrolyte 31 (N ₁₂₂₂ CPFSA described above) press-molded into a thin plate shape on a LiCoO ₂ positive electrode sheet (made by Hosen Co., Ltd.). (Thickness: about 300 μm) was placed, and a lithium foil was placed thereon to form a lithium battery. When a charge / discharge test at 0.02 C was performed at 60 ° C., the initial battery capacity was 30 mAh g ⁻¹ .

According to the ion conductive solid electrolyte of the present invention, it is possible to provide a solid electrolyte exhibiting high ion conductivity and ensuring high safety. Therefore, when used as a battery electrolyte, high safety can be realized.
Specific examples include notebook computers, pen input computers, mobile computers, electronic book players, mobile phones, mobile faxes, mobile copy, mobile printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, minidiscs, etc. , Walkie Talkie, Electronic Notebook, Calculator, Memory Card, Portable Tape Recorder, Radio, Backup Power Supply, Motor, Automobile, Motorcycle, Motorbike, Bicycle, Lighting Equipment, Toy, Game Equipment, Clock, Electric Tool, Strobe, Camera, Load Examples include leveling power sources and natural energy storage power sources.

Claims (8)

At least (A) an electron-donating organic compound containing 1 to 3 atoms selected from the group of nitrogen, oxygen, phosphorus and sulfur atoms, or (B) at least an atom selected from the group of nitrogen, phosphorus and sulfur atoms Any one of anions having a cyclic structure containing one ,
LiPF ₆ , LiCF ₃ SO ₃ , LiN (SO ₂ CF ₃ ) ₂ , LiN (SO ₂ CF ₂ CF ₃ ) ₂ , LiN (SO ₂ F) ₂ , Li (SO ₃ CF ₃ ) _n (N (SO ₂ CF ₃ ) ₂ ) _m (where n + m = 1), LiSCN,

At least one lithium salt selected from the group consisting of NaBF ₄ , NaPF ₆ , NaCF ₃ SO ₃ , NaN (SO ₂ CF ₃ ) ₂ , NaN (SO ₂ CF ₂ CF ₃ ) ₂ , NaN (SO ₂ F ) ₂ , Na (SO ₃ CF ₃ ) _n (N (SO ₂ CF ₃ ) ₂ ) _m (where n + m = 1) and at least one sodium salt selected from the group consisting of NaSCN An ion-conducting solid electrolyte comprising a crystal comprising one of the two . (A) an electron-donating organic compound containing 1 to 3 atoms selected from the group of nitrogen, oxygen, phosphorus and sulfur atoms, or (B) at least one atom selected from the group of nitrogen, phosphorus and sulfur atoms Any one of an anion having a cyclic structure to contain,
LiPF ₆ , LiCF ₃ SO ₃ , LiN (SO ₂ CF ₃ ) ₂ , LiN (SO ₂ CF ₂ CF ₃ ) ₂ , LiN (SO ₂ F) ₂ , Li (SO ₃ CF ₃ ) _n (N (SO ₂ CF ₃ ) ₂ ) _m (Where n + m = 1), LiSCN,

One or more lithium salts selected from the group consisting of: NaBF ₄ , NaPF ₆ , NaCF ₃ SO ₃ NaN (SO ₂ CF ₃ ) ₂ NaN (SO ₂ CF ₂ CF ₃ ) ₂ NaN (SO ₂ F) ₂ , Na (SO ₃ CF ₃ ) _n (N (SO ₂ CF ₃ ) ₂ ) _m The ion-conductive solid electrolyte according to claim 1, comprising a crystal formed from at least one of one or more sodium salts selected from the group consisting of (where n + m = 1) and NaSCN. (A) the nitrogen, oxygen, an electron-donating organic compound containing one to three are atoms selected from the group consisting of phosphorus and sulfur atoms, an amine, a nitrile, an ether or thioether compound, according to claim 1 or 2 Ion conductive solid electrolyte. The electron donating organic compound containing 1 to 3 atoms selected from the group of (A) nitrogen, oxygen, phosphorus and sulfur atoms is 1 to 3 selected from the group of nitrogen, oxygen, phosphorus and sulfur atoms. The ion conductive solid electrolyte according to any one of claims 1 to 3 , which exhibits monodentate, bidentate, or tridentate coordination by coordination of atoms with a cation. (B) The anion having a cyclic structure containing at least one atom selected from the group of nitrogen, phosphorus and sulfur atoms contains at least one atom selected from the group of nitrogen, phosphorus and sulfur atoms as a ring atom. it is an anion, ion conductive solid electrolyte according to claim 1 or 2. The (B) anion having a cyclic structure containing at least one atom selected from the group consisting of nitrogen, phosphorus and sulfur atoms has the following structural formula:

In an anion represented claim 1, 2 or 5 ion conductive solid electrolyte according to. The ion-electrolytic solid electrolyte according to any one of claims 1 to 6 , comprising a negative electrode capable of inserting and extracting lithium , a positive electrode capable of inserting and extracting lithium , and the lithium salt. And a lithium ion battery. The ion electrolytic solid electrolyte according to any one of claims 1 to 6 , comprising a negative electrode capable of inserting and extracting sodium , a positive electrode capable of inserting and extracting sodium , and the sodium salt. A sodium ion battery.

Images