JP5678394B2 - Batteries containing polytrimethylene oxide and polytrimethylene oxide as electrolyte - Google Patents

Description

  The present invention relates to a novel polytrimethylene oxide and a battery containing the polytrimethylene oxide as an electrolyte.

  In recent years, devices that operate on batteries, such as mobile phones, personal computers, and even electric vehicles, are often used. Along with this, various studies have been made on increasing the capacity, increasing the output or safety of the battery, and possibly reducing the size.

  In particular, a battery using a non-aqueous electrolyte containing an inorganic compound such as lithium ion has attracted attention. These liquid electrolytes are excellent in ion migration and have high load charge / discharge characteristics, but the possibility of causing liquid leakage cannot be denied, and there is a problem in safety. Therefore, it has been proposed to hold these electrolyte solutions with a polymer material and use them as so-called gels. However, even in the case of generally gelled electrolytes, at high temperatures, the liquids are still separated and liquid leakage is completely prevented. It cannot be avoided, and there is a tendency for performance to decrease at low temperatures.

  Therefore, it has also been proposed to use a so-called solid polymer electrolyte that does not substantially use a liquid electrolyte. Advantages of the polymer solid electrolyte are not limited to the risk of liquid leakage as in the case of using a liquid or gelled electrolyte, and the polymer solid electrolyte is easy to process and has a desired shape, and Since there is no problem of liquid leakage, the battery container can be simplified, and there are advantages such as lighter and smaller products. However, conventional solid electrolytes generally have low ionic conductivity, which is not sufficient for practical use, and many proposals have been made on techniques for increasing ionic conductivity. For example, a technique of using a polymer of a monomer having a cyano group and a polyfunctional monomer as a solid electrolyte via a linking group (Patent Document 1), or a crosslinked structure obtained by reacting an isocyanate group with cellulose having a cyano group A polymer solid electrolyte (Patent Document 2) having a cation is known.

  Furthermore, one of the inventors also paid attention to polyoxetane, and used a polymer of an oxetane derivative having one cyano group in the side chain, and a solid electrolyte having excellent conductivity especially for divalent metal salts. It has been proposed (Patent Document 3).

  The solid electrolyte of Patent Document 1 is characterized by being excellent in high-load charge / discharge characteristics and cycle characteristics, and capable of providing a high-capacity and safe lithium secondary battery, and having high ionic conductivity. In addition, the solid electrolyte disclosed in Patent Document 2 is characterized in that it can be handled even if it contains a large amount of solvent, and has high ionic conductivity.

  Further, the solid electrolyte of Patent Document 3 proposed by one of the present inventors is a polymer having one cyano group in the side chain of the polymer of the oxetane derivative, the main chain having a polytrimethylene oxide structure, This polymer having a trimethylene oxide structure has the same effect as a polymer having an ethylene oxide structure, which is generally used as a solid electrolyte. However, since the number of carbons existing between oxygen atoms in the main chain is large, a divalent ion is used. In contrast, it has a feature that almost the same performance as ethylene oxide in monovalent ions can be obtained. That is, the same degree of conductivity as that of the ethylene oxide solid electrolyte using lithium ions can be obtained for divalent ions such as magnesium ions.

However, the conventional solid electrolyte is superior to the liquid electrolyte in terms of safety, reliability, and design simplicity as shown as a review in Non-Patent Document 1, but a solid electrolyte is generally used. Ion conductivity is low compared with liquid electrolyte. In fact, when lithium ions or the like are used as an ion carrier, the conductivity of the solid electrolyte is generally about 10 ⁻⁶ s · cm ^{−1 around} 30 ° C. to 70 ° C., and one of the inventors previously proposed. Even in a polymer solid electrolyte, it is about 10 ⁻⁴ to 10 ⁻⁵ s · cm ⁻¹ , which is inferior by about 1 to 2 digits compared to the case of a solution electrolyte.

JP 2000-294284 A JP2002-25336 JP 2008-277218 A

J. of Power Sources, 195 (2010), 4569

  For the purpose of obtaining a polymer solid electrolyte with higher conductivity, the present inventors have attempted improvement based on polytrimethylene oxide having a cyano group in the side chain previously proposed by one of the present inventors. As a result, the present inventors have succeeded in developing a solid electrolyte having high conductivity comparable to that of a liquid electrolyte and have proposed the present invention.

  The invention according to claim 1 of the present invention is a polytrimethylene oxide represented by the following general formula (1).

（但し、Ｒ^１は炭素数１〜６のアルキル基、Ｒ^２は炭素数１〜６のアルキレン基、炭素数４〜６のシクロアルキレン基又はアリーレン基、Ｒ^３は炭素数２〜６のアルキレン基又は、−（Ｒ^４Ｏ）_ｍ−Ｃ_２Ｈ_４−基を表す。なお、Ｒ^４炭素数２〜３の炭化水素基、ｍは１〜３の整数。またｎは整数を表す。）
請求項２に係る発明は、Ｒ^２及びＲ^３がそれぞれ独立してメチレン基又はジメチレン基である請求項１記載のポリトリメチレンオキシドである。

(However, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group or arylene group having 4 to 6 carbon atoms, and R ³ is an alkylene group having 2 to 6 carbon atoms. Or a — (R ⁴ O) _m —C ₂ H ₄ — group, wherein R ^{4 is} a hydrocarbon group having 2 to 3 carbon atoms, m is an integer of 1 to 3, and n is an integer.)
The invention according to claim 2 is the polytrimethylene oxide according to claim 1, wherein R ² and R ³ are each independently a methylene group or a dimethylene group.

The invention according to claim 3 is the polytrimethylene oxide according to claim 1 or 2, wherein R ¹ is an ethyl group.

  The invention according to claim 4 is a solid electrolyte made of the polytrimethylene oxide according to any one of claims 1 to 3.

  The invention according to claim 5 is a solid electrolyte made of polytrimethylene oxide according to claim 4 containing an ion carrier.

  The invention according to claim 6 is a solid electrolyte made of polytrimethylene oxide according to claim 4 or 5 containing a reinforcing material.

  The invention according to claim 7 is a battery including a solid electrolyte made of polytrimethylene oxide according to any one of claims 4 to 6 as an electrolyte.

  The present invention is a novel polymer composed of polytrimethylene oxide having three cyano groups in the side chain per monomer, and is a solid electrolyte substantially free of a solvent. The polymer of the present invention is particularly useful as an electrolyte of a battery such as a lithium battery. When used as a solid electrolyte of a battery, the characteristics of a known solid electrolyte, that is, safety due to no liquid leakage, and liquid leakage associated therewith. Since no measures are required, in addition to light weight and miniaturization by simplification of the container, it has a conductive performance equivalent to that of a liquid electrolyte.

Is a comparison diagram of conductivity between a conventional polyalkylene oxide-based solid electrolyte and the polytrimethylene oxide of the present application (converted from FIG. 14 of Non-Patent Document 1) Is N- [2- (2-cyanoethoxy) -1,1-bis [(2-cyanoethoxy) methyl] ethyl] -3-ethyl-3-oxetamide amide polymer [Poly ( FIG. 4 is an FT-IR spectrum diagram of [abbreviated as COA)]. FIG. 2 is a ¹ HNMR spectrum diagram of Poly (COA). FIG. 4 is an FT-IR spectrum diagram of tris (cyanoethoxymethyl) aminomethane (abbreviated as TCEMAM), which is one of reference examples of monomer synthesis for obtaining the polymer of the present invention. FIG. 2 is a ¹ HNMR spectrum diagram of TCEMAM. FIG. 3 is a ¹³ CNMR spectrum diagram of TCEMAM. Is one of the reference examples of synthesis for obtaining the polymer of the present invention. FIG. 3 is an FT-IR spectrum diagram of 3-ethyl-3-carboxyl oxetane (abbreviated as ECO). FIG. 3 is a ¹ HNMR spectrum diagram of ECO. FIG. 3 is a ¹³ C NMR spectrum of ECO. FIG. 4 is an FT-IR spectrum diagram of COA, which is an example of a monomer for synthesizing the polymer of the present invention. FIG. 3 is a ¹ HNMR spectrum diagram of COA. FIG. 3 is a ¹³ C NMR spectrum diagram of COA. These are the X-ray-diffraction measurement figures of the polymer of this invention.

  The greatest feature of the present invention resides in a novel polytrimethylene oxide represented by the following general formula (1).

ここで、Ｒ^１は、メチル、エチル、プロピル、ブチル、ヘキシル等炭素数１〜６のアルキル基であり、好ましくは、エチル基である。炭素数が６を超えて長くなると重合し難くなるので、好ましくない。また、炭素数１の場合は、主鎖の酸素原子による影響により、重合体の伝導性が少し劣る傾向がある。

Here, R ¹ is an alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl, and preferably an ethyl group. Since it will become difficult to superpose | polymerize when carbon number becomes long exceeding six, it is not preferable. When the number of carbon atoms is 1, the conductivity of the polymer tends to be slightly inferior due to the influence of oxygen atoms in the main chain.

R ² is an alkylene group having 1 to 6 carbon atoms such as methylene, ethylene, propylene or hexamethylene, a cycloalkylene group having 4 to 6 carbon atoms such as cyclohexene, or an arylene group such as phenylene. Of these, a methylene group is preferred. Cycloalkylene, arylene, and the like contribute to improvement in conductivity, but there is a tendency for the synthesis problem and the degree of polymerization to increase when polymerized.

R ³ is an alkylene group having 2 to 6 carbon atoms such as ethylene, propylene, hexamethylene or the like, or — (R ⁴ O) _m — group, and R ⁴ is a hydrocarbon group having 2 to 3 carbon atoms, that is, an ethylene group. Alternatively, it is an ethylene group having a methyl group as a side chain. These are due to the ease of synthesis and the like. Moreover, m is an integer of 1-3. When m increases, polymerization of the present compound becomes difficult. n is an integer, generally up to several picks.

  The feature of the present invention is that the trimethylene oxide group forms a main chain and has a side chain at the central carbon of the monomer unit and that there are three cyano groups in the side chain. . One of the inventors of the present invention has already proposed a solid electrolyte made of an oxetane polymer having one cyano group in the side chain, but in the present invention, prediction is made by having three cyano groups in the side chain. Beyond that, the conductivity of the polymer is improved.

That is, FIG. 1 shows the conductivity (logσs · cm ⁻¹ ) between about 0 ° C. and 80 ° C. containing lithium ions for the improved polyethylene oxide solid electrolyte shown in FIG. 14 of Non-Patent Document 1. Yes, when the example of the present invention is overlapped in this table, it looks like an inverted triangle line filled in black. In addition, the line (-) which shows the conductivity in the case of CYAMEO of FIG. 1 also shows the conductivity by the polymer of patent document 3 for reference. In the figure, PEOMA is methyl ethyl methacrylate, PAEOA is poly (acryl-oligo (ethylene oxide) acrylate), PEDA-PEG is poly (ethylene glycol (PEG) diallylate) copolymer, PDEIG is poly (ethylene glycol) Dimethacrylate), PME is poly (ethylene glycol) methacrylate, PEGMA is poly (ethylene glycol) methyl ether, methacrylate, TEGDA is tri (ethylene glycol) diacrylate, which are almost the same as polyethylene oxide Or higher. However, the present invention is clearly high between about 20 ° C. and 80 ° C. and exhibits a conductivity of the order of 10 ⁻³ S · cm ⁻¹ .

  The polymer of the present invention is characterized by having trimethylene oxide monomer units as the main chain, and the central carbon is substituted on the one hand with an alkyl group, and on the other hand through a tertiary carbon by an amide bond. Three alkyleneoxy groups, cycloalkylene groups, or aryleneoxy groups are bonded, and a cyano group is bonded to each terminal via each alkylene group.

  The reason why the polymer of the present invention exhibits high conductivity is not necessarily clear, but the main chain is a repeating unit of three carbons and oxygen, and there are three via at least one ether bond for each repeating unit. It is considered that the structure has a cyano group.

  Since the polymer of the present invention has a relatively long side chain, the degree of polymerization is not so large, it is at most 10 to several positions, generally soft and viscous and ductile, and in particular, the side chain based on a cyano group is long. As a result, the degree of polymerization of the monomer does not increase.

  Rather, the polymer of the present invention has viscosity and ductility, but is also characterized by facilitating the mixing of inorganic salts which are ion carriers and the contact with the electrode active material or current collector.

When the polymer of the present invention is used as a battery electrolyte, the monovalent or divalent metal salts used in conventional lithium batteries can be used without any limitation as the inorganic salts used as ion carriers. For example, LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , Li ₂ SiF ₆ , LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, Li (CF ₃ CF ₂ SO ₂ ) ₂ N, LiB (C ₂ Examples include, but are not limited to, lithium oxalyl compounds such as O ₂ ) ₂ and LiPF ₃ (CF ₃ CF ₂ ) ₃ , Mg (ClO ₄ ) ₂ , and Mg (CF ₃ SO ₃ ) _2. . Particularly preferred inorganic salts are lithium salts and magnesium salts, especially LiPF ₆ and LiBF ₄ .

  The inorganic salt is generally mixed in a solid electrolyte by about 10 to 100% by weight (not including a reinforcing material described later). Preferably, it is 50 to 80% by weight. If it is less than 10%, the conductivity and the high-load charge / discharge performance are inferior. Moreover, it is difficult to mix a large amount of inorganic salts exceeding 100%, and the whole becomes hard and brittle, resulting in poor moldability.

  The polymer of the present invention can be used as a solid electrolyte by itself for a battery or the like, but as already mentioned, it is a soft polymer, and other polymer substances are mixed as a reinforcing material to maintain moldability and shape. You can increase your power.

  Other polymer substances used in this case include vinylidene fluoride-hexafluoropropylene copolymer (abbreviated as PVDF-HFP), polyacrylonitrile, acrylic acid ester, or methacrylic acid ester polymer, acrylic acid, Alternatively, a polymer having a polar group such as a polymer of methacrylic acid, polyvinyl acetate, polyvinyl alcohol, or polyethylene oxide can be used, but PVDF-HFP is particularly preferable because of its durability.

  These reinforcing materials can generally be mixed up to about 200% by weight with respect to the polymer of the present invention. If the mixing ratio of the reinforcing material is small, the strength at the time of formation is inferior, and if it is mixed in a large amount exceeding 200%, the strength is improved, but the conductivity is lowered. Therefore, in general, the mixing ratio may be appropriately determined according to the purpose, using about 50 to 100% as a guide.

  Next, when used as a battery, the structure is not particularly limited, and the same structure as a general battery, in particular, a primary battery or a secondary battery using a known solid electrolyte is adopted.

  That is, a positive electrode, a negative electrode, and a short-circuit preventing diaphragm are disposed between the positive electrode and the negative electrode as necessary, and a solid electrolyte is present between the two electrodes.

The positive electrode is a material that can occlude and release ion carriers. As the positive electrode, as a positive electrode active material, for example, in the case of a lithium battery, LixMO ₂ , LiyM ₂ O ₄ (where M is a transition metal, X is a number from 0 to 1, y is a number from 0 to 2), etc. Specifically _{LiCoO 2, LiMnO 2, LiMn 2} O 4, LizMO 2 (M is, Ni, Mn, Co, Al or Mg, Z represents a number of 0.9 to 1.2).

Examples of the positive electrode active material not containing lithium include S, MnO ₂ , FeO ₂ , FeS ₂ , V ₂ O ₅ , V ₆ O ₁₃ , TiO ₂ , TiS ₂ , MoS ₂ , NbSe, or polyaniline, polythiophene, polyacetylene. Polypyrrole or the like can also be a positive electrode active material.

  Among these, a lithium-containing compound is preferable because a high voltage and a high energy density can be obtained.

  The particle diameter of the positive electrode active material is generally 0.1 μm to 100 μm, preferably 1 μm to 10 μm.

  The positive electrode is generally applied to the positive electrode current collector by adding a conductive additive or a binder to the positive electrode active material to form a paste. In the present invention, since the polymer itself of the present invention has adhesiveness, the conductive auxiliary agent and the binder can be omitted, which is further advantageous.

  The positive electrode current collector is Al, Ni or stainless steel foil or nonwoven fabric.

  The negative electrode is an inorganic salt constituting metal serving as an ion carrier as a negative electrode active material, for example, a material that can occlude or release lithium ions, such as metallic lithium, or amorphous carbon, graphite, pyrolytic carbon, coke, glassy carbon, carbon Carbon, such as fiber, activated carbon, carbon black, or a fired body of phenol resin or furan resin can also be used. Furthermore, metal ions that serve as ion carriers, for example, alloys of lithium and other metals can also serve as the negative electrode active material. For example, alloys such as Ti, Sn, Pb, Al, In, Si, Zn, Sb, Bi, Ga, Ge, As, Ag, Hf, Zr, and Y can be used. Among these, Ti, Si, Sn and the like are preferable alloy materials.

  The negative electrode active material has a particle size of 0.1 μm to 100 μm, preferably 1 μm to 10 μm.

  As with the positive electrode, a conductive additive and a binder are added to the negative electrode, and if necessary, dispersed in a solvent to form a base and applied to the negative electrode current collector. As with the positive electrode, the viscosity and stretching of the polymer itself of the present invention are used. You can also

  The current collector for the negative electrode is, for example, a foil, a nonwoven fabric, or the like such as Cu, Ni, or stainless steel.

  Moreover, the separator used as needed is an insulating film having high ion permeability and excellent mechanical strength. For example, a woven cloth, a porous film such as polyethylene, polypropylene, or the like is used.

  The polymer of the present invention is a novel polymer, and its production method is not particularly limited. From the synthesis of the monomer, one scheme can be shown as follows.

ここで、（Ａ）、（Ｃ）及び（Ｄ）は、市販品であり、例えば、（Ａ）は、シグマアルドリッチ社、（Ｃ）及び（Ｄ）は、和光純薬工業株式会社から購入して新規出願用している。また、Ｒ^１,Ｒ^２,Ｒ^３及びｎは前記一般式（１）と同じである。

［本発明のポリマーの製造］

Here, (A), (C) and (D) are commercially available products. For example, (A) is purchased from Sigma-Aldrich, and (C) and (D) are purchased from Wako Pure Chemical Industries, Ltd. For new applications. R ¹ , R ² , R ³ and n are the same as in the general formula (1).

[Production of polymer of the present invention]

以下に本発明の代表的な実施例を示す。
なお、実施例中に示す文献は、次の参考文献である。
参考文献
［1］ Partha Basu, Victor N. Nemykin, and Raghvendra S. Sengar,
Inorg.Chem. ,42,7489-7501（2003）
［2］ 学校法人神奈川大学、東亜合成株式会社、自己重付加反応性化合物、重合物及びその製造方法、特開2007-210946、2007-08-23
［3］ 学校法人神奈川大学、宇部興産株式会社、ポリアミノ酸誘導体及びその製造方法、特開2010-65159、2010-3-25
［4］ A.Bowers, T.G.Halsall, E.R.H.Jones, A.J.Lemin, J. Chem. Soc, 2548, （1953）
［5］ Ye Lin, Feng Zeng-Guo, Zhao Yu-Mei, Wu Feng, Chen Shi, Wang
Guo-Qing, Polymer Chemistry, 44, 3650-3665 （2006）

The following are typical examples of the present invention.
In addition, the literature shown in an Example is the following reference.
Reference [1] Partha Basu, Victor N. Nemykin, and Raghvendra S. Sengar,
Inorg. Chem., 42, 7489-7501 (2003)
[2] Kanagawa University, Toa Gosei Co., Ltd., self-polyaddition reactive compound, polymer and method for producing the same, JP2007-210946, 2007-08-23
[3] Kanagawa University, Ube Industries, Ltd., polyamino acid derivative and method for producing the same, JP 2010-65159, 2010-3-25
[4] A. Bowers, TGHalsall, ERH Jones, AJ Lemin, J. Chem. Soc, 2548, (1953)
[5] Ye Lin, Feng Zeng-Guo, Zhao Yu-Mei, Wu Feng, Chen Shi, Wang
Guo-Qing, Polymer Chemistry, 44, 3650-3665 (2006)

First, as a reference example, a method for synthesizing and fixing a monomer is shown.
(Reference Example 1)
Synthesis of tris (cyanoethoxymethyl) aminomethane (TCEMAM)

The synthesis was performed with reference to the literature [1]. 10 g (82.5 mmol) of tris (hydroxymethyl) aminomethane, 10 mL of dioxane, and 2.5 mL of 20 wt% potassium hydroxide aqueous solution were added to the eggplant flask, and then 17.6 mL (268 mmol) of acrylonitrile was added and stirred at room temperature for 24 hours. After stirring, the solvent was removed under reduced pressure using a rotary evaporator. After removing the solvent, the residue was dissolved in 100 mL of dichloromethane, and 50 mL of ion-exchanged water was added and washed 4 times. Anhydrous magnesium sulfate was added to the washed organic layer for dehydration treatment, and the resulting organic layer was removed of the solvent under reduced pressure using a rotary evaporator to obtain a yellow liquid. The yield was 10.15 g and the yield was 43.9%. The synthesis route in this reaction is shown below.

以下の方法で同定を行った。
１）ＴＣＥＭＡＭのＦＴ−ＩＲスペクトル

図４の（ａ）にアクリロニトリル、（ｂ）にトリス（ヒドロキシメチル）アミノメタン、（ｃ）にＴＣＥＭＡＭのＦＴ−ＩＲスペクトルを示す。（ａ）と（ｃ）を比較すると、ビニル基に帰属されるピーク（６５０〜７００ｃｍ^−１及び９５０〜１０００ｃｍ^−１）が減少し、エーテル構造に帰属されるピーク（５５０〜６５０ｃｍ^−１及び１０５０〜１１５０ｃｍ^−１）が観測された。このことからＴＣＥＭＡＭが合成できたと考えられる。また、（ａ）,（ｂ）,（ｃ）における観測されたスペクトルの帰属を以下に示す。
（ａ）のスペクトル
６５０〜７００ｃｍ^−１（ＣＨ_２＝ＣＨ_２）
９５０〜１０００ｃｍ^−１（ＣＨ_２＝ＣＨ_２）
２１００〜２２００ｃｍ^−１（−ＣＮ）
（ｂ）のスペクトル
３３００〜３４００ｃｍ^−１（−ＯＨ）
（ｃ）のスペクトル
２１００〜２２００ｃｍ^−１（−ＣＮ）
５５０〜６５０ｃｍ^−１及び１０５０〜１１５０ｃｍ^−１（Ｃ−Ｏ−Ｃ、エーテル構造由来）

２）ＴＣＥＭＡＭの^１Ｈ ＮＭＲスペクトル
図５の（ａ）にアクリロニトリル,（ｂ）にトリス（ヒドロキシメチル）アミノメタン,（ｃ）にＴＣＥＭＡＭの^１Ｈ ＮＭＲスペクトルを示す。（ａ）と（ｃ）を比較すると、（ｃ）では、（ａ）でみられたビニル基に帰属されるピークが消失し、新たに（１）と（３）に帰属されるピーク（２．５４ｐｐｍ,３．６１ｐｐｍ）が観測された。このことからＴＣＥＭＡＭが合成できたと考えられる。また、（ａ）,（ｂ）,（ｃ）における観測されたスペクトルの帰属を以下に示す。

Identification was performed by the following method.
1) FT-IR spectrum of TCEMAM

4A shows acrylonitrile, FIG. 4B shows tris (hydroxymethyl) aminomethane, and FIG. 4C shows the FT-IR spectrum of TCEMAM. When (a) and (c) are compared, the peaks attributed to the vinyl group (650 to 700 cm ⁻¹ and 950 to 1000 cm ⁻¹ ) decrease, and the peaks attributed to the ether structure (550 to 650 cm ⁻¹ and 1050). ˜1150 cm ⁻¹ ) was observed. From this, it is considered that TCEMAM could be synthesized. In addition, assignment of observed spectra in (a), (b), and (c) is shown below.
Spectrum (a) 650 to 700 cm ⁻¹ (CH ₂ ═CH ₂ )
950 to 1000 cm ⁻¹ (CH ₂ ═CH ₂ )
2100-2200cm ^-1 (-CN)
Spectrum of (b) 3300-3400 cm ⁻¹ (—OH)
Spectrum (c) 2100-2200 cm ⁻¹ (—CN)
550 to 650 cm ⁻¹ and 1050 to 1150 cm ⁻¹ (C—O—C, derived from ether structure)

2) ¹ H NMR spectrum of TCEMAM FIG. 5A shows acrylonitrile, FIG. 5B shows tris (hydroxymethyl) aminomethane, and FIG. 5C shows ¹ H NMR spectrum of TCEMAM. When (a) and (c) are compared, in (c), the peak attributed to the vinyl group observed in (a) disappears and the peak attributed to (1) and (3) newly (2 .54 ppm, 3.61 ppm) was observed. From this, it is considered that TCEMAM could be synthesized. In addition, assignment of observed spectra in (a), (b), and (c) is shown below.

３） ＴＣＥＭＡＭの^１３Ｃ ＮＭＲスペクトル
図６の（ａ）にアクリロニトリル,（ｂ）にトリス（ヒドロキシメチル）アミノメタン,（ｃ）にＴＣＥＭＡＭの^１３Ｃ ＮＭＲスペクトルを示す。（ａ）と（ｃ）を比較すると、（ｃ）では、（ａ）でみられたビニル基に帰属されるピークが消失し、新たに（１）に帰属されるピーク（１８．８６
ｐｐｍ）が観測された。このことからＴＣＥＭＡＭが合成できたと考えられる。また、（ａ）,（ｂ）,（ｃ）における観測されたスペクトルの帰属を以下に示す。

3) ¹³ C NMR spectrum of TCEMAM FIG. 6A shows acrylonitrile, FIG. 6B shows tris (hydroxymethyl) aminomethane, and FIG. 6C shows ¹³ C NMR spectrum of TCEMAM. When (a) and (c) are compared, in (c), the peak attributed to the vinyl group observed in (a) disappears and a new peak attributed to (1) (18.86)
ppm) was observed. From this, it is considered that TCEMAM could be synthesized. In addition, assignment of observed spectra in (a), (b), and (c) is shown below.

（参考例２）
３−エチル−３−カルボキシルオキセタン（ＥＣＯ）の合成

文献［２−４］を参考に合成を行った。５００ｍＬナスフラスコにＪｏｎｅｓ試薬４６ｍＬ（１．５ｅｑ）、アセトン３００ｍＬを加え、０℃にて撹拌した。これに、３−エチル−３−ヒドロキシルメチルオキセタン（ＥＨＯ）を５．５６ｇ（２４ｍｍｏｌ）とアセトン１００ｍＬの混合物を５ｈかけて滴下し、続いて室温にて１ｈ撹拌を行った。反応終了後、０℃にてイソプロピルアルコールを５ｍＬ加え反応を停止させた。得られた混合物を減圧ろ過し、その後セライトにて自然ろ過を行った。次に、得られたろ液をロータリーエバポレーターを用いて減圧下でアセトン、イソプロピルアルコールの除去を行った。残留した液体にＮａＯＨ水溶液を加えｐＨ１１とした後、ジクロロメタンを用いて洗浄を3回行った。水層にＨ_２ＳＯ_４を加えｐＨ１とした後、ジクロロメタンによる抽出を行い、有機層を無水硫酸マグネシウムで脱水処理を行った。その後、溶媒を減圧下で除去した後、減圧蒸留により生成し、無色透明液体を得た。収量は、３．１３７ｇ、収率は５０．４％であった。なお、この反応における合成経路を下記に示す。

(Reference Example 2)
Synthesis of 3-ethyl-3-carboxyl oxetane (ECO)

The synthesis was performed with reference to the literature [2-4]. Jones reagent 46mL (1.5eq) and acetone 300mL were added to a 500mL eggplant flask, and it stirred at 0 degreeC. To this, a mixture of 5.56 g (24 mmol) of 3-ethyl-3-hydroxylmethyloxetane (EHO) and 100 mL of acetone was added dropwise over 5 h, followed by stirring at room temperature for 1 h. After completion of the reaction, 5 mL of isopropyl alcohol was added at 0 ° C. to stop the reaction. The obtained mixture was filtered under reduced pressure, and then naturally filtered through Celite. Next, acetone and isopropyl alcohol were removed from the obtained filtrate under reduced pressure using a rotary evaporator. A NaOH aqueous solution was added to the remaining liquid to adjust the pH to 11, followed by washing with dichloromethane three times. H ₂ SO ₄ was added to the aqueous layer to adjust the pH to 1, followed by extraction with dichloromethane, and the organic layer was dehydrated with anhydrous magnesium sulfate. Then, after removing the solvent under reduced pressure, it was produced by distillation under reduced pressure to obtain a colorless transparent liquid. The yield was 3.137 g, and the yield was 50.4%. The synthesis route in this reaction is shown below.

以下の方法で同定を行った。

１）ＥＣＯのＦＴ−ＩＲスペクトル

図７の（ａ）に３−エチル−３−ヒドロキシメチルオキセタン（ＥＨＯ）、（ｂ）にＥＣＯのＦＴ−ＩＲスペクトルを示す。（ａ）、（ｂ）を比較すると、カルボキシル基に帰属されるピーク（１６５０〜１７５０ｃｍ^−１及び２５００〜３３００ｃｍ^−１）が観測された。このことからＴＣＥＭＡＭが合成できたと考えられる。また、（ａ）、（ｂ）における観測されたスペクトルの帰属を以下に示す。

（ａ）のスペクトル
９００〜１０００ｃｍ^−１（ｒｉｎｇ’ｓ Ｃ−Ｏ−Ｃ）
１０００〜１１００ｃｍ^−１（ＯＨ）
２８００〜３０００ｃｍ^−１（ＣＨ_２）
３１００〜３６００ｃｍ^−１（ＯＨ）

（ｂ）のスペクトル
９００〜１０００ｃｍ^−１（ｒｉｎｇ’ｓ Ｃ−Ｏ−Ｃ）
１２００〜１３００ｃｍ^−１（−ＣＯＯＨ）
１６５０〜１７５０ｃｍ^−１（−ＣＯＯＨ）
２８００〜３０００ｃｍ^−１（ＣＨ_２）
２５００〜３５００ｃｍ^−１（−ＣＯＯＨ）

２） ＥＣＯの^１Ｈ ＮＭＲスペクトル

図８に（ａ）ＥＨＯと（ｂ）ＥＣＯの^１Ｈ ＮＭＲスペクトルを示す。（ａ）と（ｂ）を比較すると、（ｂ）では、（ａ）でみられたヒドロキシル基に帰属されるピークが消失し、新たにカルボキシル基に帰属されるピーク（１０．６ｐｐm）が観測された。このことから、ＥＣＯが合成できたと考えられる。
また、（ａ）,（ｂ）における観測されたスペクトルの帰属を以下に示す。

Identification was performed by the following method.

1) FT-IR spectrum of ECO

FIG. 7 (a) shows 3-ethyl-3-hydroxymethyloxetane (EHO), and FIG. 7 (b) shows the FT-IR spectrum of ECO. When (a) and (b) were compared, peaks (1650 to 1750 cm ⁻¹ and 2500 to 3300 cm ⁻¹ ) attributed to carboxyl groups were observed. From this, it is considered that TCEMAM could be synthesized. In addition, assignment of the observed spectra in (a) and (b) is shown below.

Spectrum of (a) 900 to 1000 cm ⁻¹ (ring's C—O—C)
1000-1100 cm ⁻¹ (OH)
2800 to 3000 cm ⁻¹ (CH ₂ )
3100-3600 cm ⁻¹ (OH)

Spectrum of (b) 900 to 1000 cm ⁻¹ (ring's C—O—C)
1200-1300 cm ⁻¹ (—COOH)
1650-1750 cm < ^-1 > (-COOH)
2800 to 3000 cm ⁻¹ (CH ₂ )
2500-3500 cm ⁻¹ (—COOH)

2) ¹ H NMR spectrum of ECO

FIG. 8 shows ¹ H NMR spectra of (a) EHO and (b) ECO. When (a) and (b) are compared, in (b), the peak attributed to the hydroxyl group observed in (a) disappears, and a new peak attributed to the carboxyl group (10.6 ppm) is observed. It was done. From this, it is considered that ECO was synthesized.
In addition, assignment of the observed spectra in (a) and (b) is shown below.

３） ＥＣＯの^１３Ｃ ＮＭＲスペクトル
図９に（ａ）ＥＨＯ,（ｂ）ＥＣＯの^１３Ｃ ＮＭＲスペクトルを示す。（ａ）と（ｂ）を比較すると、（ｂ）では、（ａ）でみられた（４）に帰属されるピークが消失し、新たにカルボン酸に帰属されるピーク（１７９．２６ｐｐｍ）が観測された。このことから、ＥＣＯは合成できたと考えられる。また、（ａ）,（ｂ）における観測されたスペクトルの帰属を以下に示す。

3) the ECO of ¹³ C NMR spectra Figure 9 (a) EHO, shows the ¹³ C NMR spectrum of (b) ECO. When (a) and (b) are compared, in (b), the peak attributed to (4) seen in (a) disappears and a new peak attributed to carboxylic acid (179.26 ppm) is observed. Observed. From this, it is considered that ECO could be synthesized. In addition, assignment of the observed spectra in (a) and (b) is shown below.

（参考例３）
Ｎ−［２−（２−シアノエトキシ−１−ビス［（２−シアノエトキシ）メチル］エチル］−３−エチル−３−オキセタンアミド（ＣＯＡ）の合成

文献［２，３］を参考に合成を行った。１００ｍＬナスフラスコに１−エチル−３−（３−ジメチルアミノプロピル）カルボジイミドヒドロクロライド（ＥＤＣ塩酸塩）３．８３ｇ（２０ｍｍｏｌ）、ジクロロメタン２０ｍＬを加え窒素雰囲気下、０℃で１ｈ撹拌した。この後、ＥＣＯ２．６ｇ、ＴＣＥＭＡＭ５．６ｇ、トリエチルアミン２．２３ｍＬ、ジクロロメタン２５ｍＬを加え、室温、窒素雰囲気下で２４ｈ撹拌を行った。反応終了後、反応液を１Ｍ
ＨＣｌで２回、重曹水で２回、さらに水で２回洗浄を行った後、有機層を無水硫酸マグネシウムで脱水処理を行った。溶媒を減圧下にて除去し黄色液体を得た。収量は３．３３ｇ、収率は４２．６％であった。なお、この反応における合成経路を下記に示す。

(Reference Example 3)
Synthesis of N- [2- (2-cyanoethoxy-1-bis [(2-cyanoethoxy) methyl] ethyl] -3-ethyl-3-oxetamide (COA)

The synthesis was carried out with reference to the literature [2, 3]. To a 100 mL eggplant flask were added 3.83 g (20 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC hydrochloride) and 20 mL of dichloromethane, and the mixture was stirred at 0 ° C. for 1 h under a nitrogen atmosphere. Thereafter, 2.6 g of ECO, 5.6 g of TCEMAM, 2.23 mL of triethylamine, and 25 mL of dichloromethane were added, and the mixture was stirred for 24 hours at room temperature in a nitrogen atmosphere. After completion of the reaction, the reaction solution is 1M.
After washing twice with HCl, twice with aqueous sodium bicarbonate, and twice with water, the organic layer was dehydrated with anhydrous magnesium sulfate. The solvent was removed under reduced pressure to give a yellow liquid. The yield was 3.33 g, and the yield was 42.6%. The synthesis route in this reaction is shown below.

以下の方法で同定を行った。

３-１-３ ＣＯＡの同定

１） ＣＯＡのＦＴ−ＩＲスペクトル

図１０の（ａ）にＥＣＯ,（ｂ）にＴＣＥＭＡＭ,（ｃ）にＣＯＡのＦＴ−ＩＲスペクトルを示す。（ｂ）と（ｃ）を比較すると、（ｃ）では新たにオキセタン環に帰属されるピーク（９００〜１０００ｃｍ^−１）とアミド基に帰属されるピーク（１４５０〜１６５０ｃｍ^−１）が観測された。このことからＣＯＡが合成できたと考えられる。また、（ａ）,（ｂ）,（ｃ）における観測されたスペクトルの帰属を以下に示す。

（ａ）のスペクトル
９００〜１０００ｃｍ^−１（ｒｉｎｇ’ｓ Ｃ−Ｏ−ｃ）
１２００〜１３００ｃｍ^−１（−ＣＯＯＨ）
１６５０〜１７５０ｃｍ^−１（−ＣＯＯＨ）
２８００〜３０００ｃｍ^−１（ＣＨ_２）
２５００〜３５００ｃｍ^−１（−ＣＯＯＨ）

（ｂ）のスペクトル
５５０〜６５０ｃｍ^−１（ＣＨ_２−Ｏ−ＣＨ_２）
８００〜９００ｃｍ^−１（ＮＨ_２）
１０５０〜１１５０ｃｍ^−１（ＣＨ_２−Ｏ−ＣＨ_２）
１３５０〜１５００ｃｍ^−１（ＣＨ_２）
１６００〜１７００ｃｍ^−１（ＮＨ_２）
２２００〜２２５０ｃｍ^−１（ＣＮ）
２７００〜３０００ｃｍ^−１（ＣＨ_２）
３３００〜３６００ｃｍ^−１（ＮＨ_２）

（ｃ）のスペクトル
９００〜１０００ｃｍ^−１（ｒｉｎｇ’ｓ Ｃ−Ｏ−Ｃ）
１４５０〜１６５０ｃｍ^−１（ＣＯＮＨＲ）
１６５０〜１７５０ｃｍ^−１（ＣＯＮＨＲ）
２２００〜２２５０ｃｍ^−１（ＣＮ）
２７００〜３０００ｃｍ^−１（ＣＨ_２）
３３００〜３６００ｃｍ^−１（ＣＯＮＨＲ）

２） ＣＯＡの^１Ｈ ＮＭＲスペクトル

図１１の（ａ）にＥＣＯ,（ｂ）にＴＣＥＭＡＭ,（ｃ）にＣＯＡの^１Ｈ ＮＭＲスペクトルを示す。（ｂ）の（２）のピークが磁場環境の変化により、（ｃ）では、低磁場側にシフトしている。また、（ａ）のカルボン酸に帰属されるピーク（１０．６ｐｐｍ）が（ｃ）では存在しない。このようなことから、ＣＯＡは合成できたと考えられる。また、（ａ）,（ｂ）,（ｃ）における観測されたスペクトルの帰属を以下に示す。

Identification was performed by the following method.

3-1-3 Identification of COA

1) FT-IR spectrum of COA

FIG. 10A shows ECO, FIG. 10B shows TCEMAM, and FIG. 10C shows the FT-IR spectrum of COA. (B) and a comparison of (c), were observed peaks attributed to the newly oxetane ring in (c) peak attributed to a (900~1000cm ^-1) and amide groups (1450~1650cm ^-1) . From this, it is considered that COA could be synthesized. In addition, assignment of observed spectra in (a), (b), and (c) is shown below.

Spectrum of (a) 900 to 1000 cm ⁻¹ (ring's C—Oc)
1200-1300 cm ⁻¹ (—COOH)
1650-1750 cm < ^-1 > (-COOH)
2800 to 3000 cm ⁻¹ (CH ₂ )
2500-3500 cm ⁻¹ (—COOH)

Spectrum of (b) 550 to 650 cm ⁻¹ (CH ₂ —O—CH ₂ )
800 to 900 cm ⁻¹ (NH ₂ )
1050-1150 cm ⁻¹ (CH ₂ —O—CH ₂ )
1350-1500 cm ⁻¹ (CH ₂ )
1600-1700 cm ⁻¹ (NH ₂ )
2200-2250cm ^-1 (CN)
2700 to 3000 cm ⁻¹ (CH ₂ )
3300-3600 cm ⁻¹ (NH ₂ )

Spectrum of (c) 900 to 1000 cm ⁻¹ (ring's C—O—C)
1450-1650 cm ⁻¹ (CONHR)
1650-1750 cm ⁻¹ (CONHR)
2200-2250cm ^-1 (CN)
2700 to 3000 cm ⁻¹ (CH ₂ )
3300-3600cm ^-1 (CONHR)

2) ¹ H NMR spectrum of COA

FIG. 11 (a) shows ECO, (b) shows TCEMAM, and (c) shows the ¹ H NMR spectrum of COA. The peak of (2) in (b) is shifted to the low magnetic field side in (c) due to the change in the magnetic field environment. Moreover, the peak (10.6 ppm) attributed to the carboxylic acid of (a) does not exist in (c). For this reason, it is considered that COA could be synthesized. In addition, assignment of observed spectra in (a), (b), and (c) is shown below.

３） ＣＯＡの^１３Ｃ ＮＭＲスペクトル

図１２の（ａ）にＥＣＯ、（ｂ）にＴＣＥＭＡＭ、（ｃ）にＣＯＡの^１３Ｃ ＮＭＲスペクトルを示す。（ａ）と（ｃ）を比較すると、（ｃ）では、（ａ）のカルボニル炭素に帰属されるピーク（１７９．２２ｐｐｍ）が消失し、新たにアミド結合の炭素に帰属されるピーク（１７４．０４ｐｐｍ）が観測された。このようなことからＣＯＡが合成できたと考えられる。また、（ａ）,（ｂ）,（ｃ）における観測されたスペクトルの帰属を以下に示す。

（実施例１）
Ｎ-[2-(2-シアノエトキシ)-1,1-ビス[(2-シアノエトキシ)メチル]エチル]-3-エチル-3-オキセタンアミド(ＣＯＡ)の重合

文献[5]を参考に合成を行った。50 mLナスフラスコにジクロロメタン2 mLと、モノマー と 開始剤BF₃・Et₂Oをモル比が8.2 : 1 、5.9 : 1になるように加え、窒素雰囲気下で72 h撹拌した。得られた溶液を100 mLのエタノールを用いて再沈殿し、上澄みを取り除いた。得られた沈殿物を室温で24 h以上溶媒の除去を行いpoly(ＣＯＡ)を回収した。表１に反応条件を示す。なお、この重合反応における反応機構を下記に示す。

3) ¹³ C NMR spectrum of COA

FIG. 12 (a) shows ECO, FIG. 12 (b) shows TCEMAM, and FIG. 12 (c) shows the ¹³ C NMR spectrum of COA. When (a) and (c) are compared, in (c), the peak (179.22 ppm) attributed to the carbonyl carbon in (a) disappears, and a new peak (174. 04 ppm) was observed. From this, it is considered that COA could be synthesized. In addition, assignment of observed spectra in (a), (b), and (c) is shown below.

Example 1
Polymerization of N- [2- (2-cyanoethoxy) -1,1-bis [(2-cyanoethoxy) methyl] ethyl] -3-ethyl-3-oxetanamide (COA)

The synthesis was performed with reference to the literature [5]. To a 50 mL eggplant flask, 2 mL of dichloromethane, a monomer and an initiator BF ₃ · Et ₂ O were added so that the molar ratios were 8.2: 1 and 5.9: 1, and the mixture was stirred for 72 hours under a nitrogen atmosphere. The obtained solution was reprecipitated using 100 mL of ethanol, and the supernatant was removed. The resulting precipitate was subjected to removal of the solvent at room temperature for 24 hours or more to recover poly (COA). Table 1 shows the reaction conditions. The reaction mechanism in this polymerization reaction is shown below.

  The polymer was a yellow solid with viscosity and elongation. The glass transition point was -12.2 ° C.

以下の方法で同定を行った。
１) poly(ＣＯＡ)のFT-IRスペクトル


図３−１−４−１の(a)にＣＯＡ, (b)にpoly(ＣＯＡ)のＦＴ−ＩＲスペクトルを示す。(a), (b)を比較すると、(b)では環状エーテルに帰属されるピーク(900〜1000 cm^-1)が減少していた。このことからpoly(ＣＯＡ)は合成できたと考えられる。また、(a), (b)における観測されたスペクトルの帰属を以下に示す。

(a)のスペクトル
900〜1000 cm^-1(ring’s C-O-C)
1450〜1650 cm^-1(CONHR)
1650〜1750 cm^-1(CONHR)
2200〜2250 cm^-1(CN)
2700〜3000 cm^-1(CH₂)
3300〜3600 cm^-1(CONHR)

(b)のスペクトル
1450〜1650 cm^-1(CONHR)
1650〜1750 cm^-1(CONHR)
2200〜2250 cm^-1(CN)
2700〜3000 cm^-1(CH₂)
3300〜3600 cm^-1(CONHR)

2) poly(ＣＯＡ)の¹H NMRスペクトル

図３の(a)にＣＯＡ,(b)にpoly(ＣＯＡ)の¹H NMRスペクトルを示す。(a)と(b)を比較すると、(b)では、(a)でみられた環状エーテルに帰属されるピーク(4.42 ppm,4.83 ppm)が消失した。このようなことからpoly(ＣＯＡ)は合成できたと考えられる。また、(a), (b)における観測されたスペクトルの帰属を以下に示す。

Identification was performed by the following method.
1) FT-IR spectrum of poly (COA)


3-1-4-1 (a) shows the FT-IR spectrum of COA, and (b) shows the FT-IR spectrum of poly (COA). When comparing (a) and (b), the peak (900 to 1000 cm ⁻¹ ) attributed to the cyclic ether decreased in (b). From this, it is considered that poly (COA) could be synthesized. The observed spectral assignments in (a) and (b) are shown below.

Spectrum of (a)
900-1000 cm ^-1 (ring's COC)
1450-1650 cm ^-1 (CONHR)
1650-1750 cm ^-1 (CONHR)
2200-2250 cm ^-1 (CN)
2700 ~ 3000 cm ^-1 (CH ₂ )
3300-3600 cm ^-1 (CONHR)

Spectrum of (b)
1450-1650 cm ^-1 (CONHR)
1650-1750 cm ^-1 (CONHR)
2200-2250 cm ^-1 (CN)
2700 ~ 3000 cm ^-1 (CH ₂ )
3300-3600 cm ^-1 (CONHR)

2) ¹ H NMR spectrum of poly (COA)

3A shows the ¹ H NMR spectrum of COA, and FIG. 3B shows the ¹ H NMR spectrum of poly (COA). When (a) and (b) were compared, in (b), the peaks (4.42 ppm, 4.83 ppm) attributed to the cyclic ether observed in (a) disappeared. Therefore, it is considered that poly (COA) has been synthesized. The observed spectral assignments in (a) and (b) are shown below.

  Conductivity measurement

The electrolyte membrane was prepared by changing the ratio of the polymer and the lithium salt. RunN0.1,2 and a comparative example are shown below.
<No.1>
0.0303 g of poly (COA) synthesized under the conditions shown in Table 1 above and 0.0304 of PVDF-HFP in the sample tube
g, 0.0124 g of LiBF ₄ was added. To this, 2 ml of acetone was added and stirred to obtain a homogeneous solution. This solution was cast on a Teflon (registered trademark) plate and then placed in a vacuum dryer for 12 hours or longer to remove the solvent, thereby preparing an electrolyte membrane.

<No.2>
0.0285 g poly (COA) synthesized under the conditions shown in Table 1 above, 0.0290 g PVDF-HFP, and 0.0238 g LiBF ₄ were added to the sample tube. To this, 2 ml of acetone was added and stirred to obtain a homogeneous solution. This solution was cast on a Teflon (registered trademark) plate and then placed in a vacuum dryer for 12 hours or longer to remove the solvent, thereby preparing an electrolyte membrane.
<Comparative Example 1>
0.0408 g of PVDF-HFP used in Reference Example 4 and 0.0168 g of LiBF ₄ were added to the sample tube. To this, 2 ml of acetone was added and stirred to obtain a homogeneous solution. This solution was cast on a Teflon (registered trademark) plate and then placed in a vacuum dryer for 12 hours or longer to remove the solvent, thereby preparing an electrolyte membrane.

<Comparative Example 2>
0.0409 g of PVDF-HFP and 0.0322 g of LiBF ₄ used in Reference Example 4 were added to the sample tube. To this, 2 ml of acetone was added and stirred to obtain a homogeneous solution. This solution was cast on a Teflon (registered trademark) plate and then placed in a vacuum dryer for 12 hours or longer to remove the solvent, thereby preparing an electrolyte membrane.
The composition of each component of the prepared polymer solid electrolyte membrane is shown in Table 2 on the basis of the mass of COA. For example, the electrolyte of No. 1 indicates that 1 g of PVDF-HFP and 0.4 g of LiBF ₄ are contained with respect to 1 g of COA.

イオン伝導度の測定は、以下の手順により行った。
調製したフィルムのイオン伝導度を20〜70℃の温度範囲で測定した。調製したフィルムを直径10mmの円形に切り抜き、このフィルムを2枚のステンレス板で挟み、ステンレス板間のインピーダンスを測定した。測定は印加電圧50
mVにて、100kHz〜10Hzまで行った。なお、使用機器はＨＩＯＫＩ3532-80ＬＣＲHitester[日置電機(株)]である。その測定結果を表3に示した。

なお、導電率(σ)は、次の式(1)により求めた。

σ = L / (R × S)・・・(1)
但し、式中、σは導電率( S / ｃｍ)、Ｒは抵抗(Ω)、Ｓは高分子固体電解質膜の測定時の断面積(ｃｍ²)、Ｌは電極間距離(ｃｍ)を示す。

The ion conductivity was measured by the following procedure.
The ionic conductivity of the prepared film was measured in a temperature range of 20 to 70 ° C. The prepared film was cut out into a circle having a diameter of 10 mm, the film was sandwiched between two stainless plates, and the impedance between the stainless plates was measured. Measurement is applied voltage 50
It was performed from 100 kHz to 10 Hz at mV. The equipment used is HIOKI3532-80LCR Hitester [Hioki Electric Co., Ltd.]. The measurement results are shown in Table 3.

The conductivity (σ) was obtained by the following equation (1).

σ = L / (R × S) (1)
However, in the formula, σ is the conductivity (S / cm), R is the resistance (Ω), S is the cross-sectional area (cm ² ) when measuring the polymer solid electrolyte membrane, and L is the distance between the electrodes (cm). .

表の数字は、×10^-3 Scm^-1 である。

表3から、No.1のイオン伝導度は、比較例1と比較すると二桁向上した。また、表3から、No.2のイオン伝導度は、比較例2と比較すると二桁向上した。この結果から、poly(COA)は伝導性を向上させることが分かる。

図13のa)はNo.1、b)はNo.2、c)は比較例1、d)は比較例2でそれぞれ得られた高分子固体電解質のＸ線回折測定の結果である。

図13から、No.1〜2あるいは比較例1〜2で調製された高分子固体電解質膜は、非晶質であり、添加したリチウム塩もポリマーにより疑似溶媒和され、イオンに解離していることが分かる。

なお測定装置は、以下を用いた。
（１）NMR フーリエ変換核磁気共鳴装置 GSX-500[日本電子(株)]
測定は合成物をクロロホルム-d、もしくはジメチルスルホキシド-d₆に溶解し、NMR測定用サンプルチューブに充填して行った。

（２）FTIR フーリエ変換赤外分光光度計IR Prestige-21[島津製作所(株)]
測定はKBｒ錠剤法あるいは、フィルム法により測定した。

（３）DSC 示差走査熱量測定装置[ブルカー・エイ・エックス・エス(株) DSC3100S]
測定は調製した膜を所定のシール容器に秤量し、サンプルシーラーにより密封後、同様なシール容器にα-アルミナを詰めた標準試料と共に測定装置にセットし、測定を行った。測定条件は、昇温速度・降温速度を共に10℃ min^-1とし、-100 〜 100℃の温度範囲で2サイクル測定を行った。


（４）伝導度 ＣＨＥＭＩＣＡＬ
ＩＭＰＥＤＡＮＣＥＭＥＴＥＲ[日置電機(株) 3532-80]
交流インピーダンス法により、調製した各電解質膜のイオン伝導度を測定した。測定試料は調製した膜を直径1.5 cmもしくは1.0 cmの円形にそれぞれ切り抜き、スクリューセルを用いて恒温水槽[東京理科器機(株) EYELA
NCB-3100]中で温度制御を行いながら20〜70℃の温度範囲で測定を行った。

（５）Ｘ線回折測定は、粉末X線回折装置（(株)島津製作所 ＸＲＤ−D１）を用いて室温下において測定を行った。測定に用いたＸ線は、Ｃｕｋα線を用いて行った。

The numbers in the table are × 10 ⁻³ Scm ⁻¹ .

From Table 3, the ionic conductivity of No. 1 was improved by two orders of magnitude compared with Comparative Example 1. Also, from Table 3, the ionic conductivity of No. 2 was improved by two orders of magnitude as compared with Comparative Example 2. From this result, it can be seen that poly (COA) improves conductivity.

In FIG. 13, a) is the result of X-ray diffraction measurement of the solid polymer electrolyte obtained in No. 1, b) is No. 2, c) is Comparative Example 1, and d) is Comparative Example 2.

From FIG. 13, the polymer solid electrolyte membranes prepared in Nos. 1 and 2 or Comparative Examples 1 and 2 are amorphous, and the added lithium salt is also pseudo-solvated by the polymer and dissociated into ions. I understand that.

The following measuring apparatus was used.
(1) NMR Fourier transform nuclear magnetic resonance system GSX-500 [JEOL Ltd.]
The measurement was performed by dissolving the synthesized product in chloroform-d or dimethyl sulfoxide-d ₆ and filling the sample tube for NMR measurement.

(2) FTIR Fourier transform infrared spectrophotometer IR Prestige-21 [Shimadzu Corporation]
The measurement was performed by the KBr tablet method or the film method.

(3) DSC differential scanning calorimeter [Bruker AXS Co., Ltd. DSC3100S]
For the measurement, the prepared membrane was weighed into a predetermined sealed container, sealed with a sample sealer, and then set in a measuring apparatus together with a standard sample packed with α-alumina in a similar sealed container. The measurement conditions were a temperature increase rate and a temperature decrease rate of 10 ° C. min ^−1, and two-cycle measurement was performed in a temperature range of −100 to 100 ° C.


(4) Conductivity CHEMICAL
IMPENCANCEMETER [Hioki Electric Co., Ltd. 3532-80]
The ionic conductivity of each prepared electrolyte membrane was measured by the AC impedance method. Samples were prepared by cutting out the prepared membranes into circles with a diameter of 1.5 cm or 1.0 cm, respectively, and using a screw cell, a constant temperature water bath [Tokyo Science Equipment Co., Ltd.
NCB-3100] was measured in the temperature range of 20 to 70 ° C. with temperature control.

(5) X-ray diffraction measurement was performed at room temperature using a powder X-ray diffractometer (Shimadzu Corporation XRD-D1). X-rays used for the measurement were performed using Cukα rays.

The polymer of the present invention is used as a solid electrolyte in batteries and capacitors. Further, it can be used as a lithium battery or the like for an electronic device such as a mobile phone or a personal computer, an automobile battery, or the like.

Claims (7)

Polytrimethylene oxide represented by the following general formula (1).

(However, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group or arylene group having 4 to 6 carbon atoms, and R ³ is an alkylene group having 2 to 6 carbon atoms. Represents a group or — (R ⁴ O) _m —C ₂ H ₄ — group, wherein R ⁴ represents a hydrocarbon group having 2 to 3 carbon atoms, m represents an integer of 1 to 3, and n represents an integer. Represents.) The polytrimethylene oxide according to claim 1, wherein R ² and R ³ are each independently a methylene group or a dimethylene group. The polytrimethylene oxide according to claim 1 or 2, wherein R ¹ is an ethyl group.   A solid electrolyte comprising the polytrimethylene oxide according to any one of claims 1 to 3.   The solid electrolyte which consists of polytrimethylene oxide of Claim 4 containing an ion carrier.   The solid electrolyte which consists of polytrimethylene oxide of Claim 4 or 5 containing a reinforcing material. A battery comprising a solid electrolyte made of the polytrimethylene oxide according to any one of claims 4 to 6 as an electrolyte.

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