JP2002187892A - Addition compound of ionic metal complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an addition compound of an ionic metal complex excellently usable as an electrolyte for electrochemical devices such as lithium battery, lithium ion battery and electric double layer capacitor, a catalyst, etc. SOLUTION: The compound is an addition compound of a compound expressed by general formula II (M is a transition metal or an element of the group III, IV or V of the periodic table; and Aa+ is a metal ion, hydrogen ion or an onium ion) and an ester compound, an ether compound, a nitrile compound, an alcohol compound, an amide compound or a ketone compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel chemical structure used as an electrolyte for electrochemical devices such as lithium batteries, lithium ion batteries, electric double layer capacitors, polymerization catalysts such as polyolefins, or catalysts for organic synthesis. And an addition compound of an ionic metal complex having the formula:

[0002]

2. Description of the Related Art Conventionally, ionic complexes such as PF ₆ ⁻ , BF ₄ ⁻ , and AsF ₆ ⁻ in which a Lewis acid and F ion are bonded have high solubility and ion dissociation properties. It has been used for applications such as supporting electrolytes for polymerization, polymerization catalysts such as polyolefins, or catalysts for organic synthesis.

[0003] As the range of application is diversified, the most suitable ionic complex for each application is being sought. I have. In such circumstances, the present inventors have found and disclosed a novel ionic metal complex having the chemical structural formula represented by the general formula (1). These complexes have a very weak interaction between anions and cations, so they have high ionic dissociation properties as electrolytes,
As a catalyst, it has very excellent properties of high activity. However, because of this, impurities having adverse effects such as water coordinate to the cations, and the impurities deteriorate the characteristics, and the impurities once coordinated are very difficult to remove by purification such as drying. Have.

[0004]

[Specific means for solving the problem]
As a result of intensive studies in view of the problems of the prior art, the present inventors have found an additional compound obtained by adding an organic compound to an ionic metal complex having a novel chemical structural feature, and have reached the present invention.

That is, the present invention provides a compound having the chemical structural formula represented by the general formula (1), wherein one molecule of the compound is coordinated with one to six organic compounds. A metal complex adduct,

[0006]

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M is a transition metal, group III of the periodic table, IV
Group or group V element, A ^{a +} is a metal ion, hydrogen ion, or onium ion, a is 1 to 3, b is 1 to
3, p is b / a, m is 1-3, n is 0-4, q is
X ¹ is O, S, NR ⁵ , or NR ⁵ R ⁶ , and R ¹ and R ² are each independently H, halogen, C ₁ -C ₁₀ alkyl, or C alkyl halide ₁ -C _10, R ³ is alkylene of C _{1 ~C 10,} C ₁
Aryl halides -C halogenation of ₁₀ alkylene, a C ₄ -C ₂₀ aryl or C ^₄ ~C _20,, R ₄ is halogen, alkyl of C ₁ -C _10, alkyl halide C ₁ -C ₁₀ , C ₄ -C ₂₀ aryl, C ₄ -C ₂₀ aryl halide, or X ² R ⁷ , X ² is O, S, NR ⁵ , or NR ⁵ R ⁶ , R ⁵ , R ⁶ is H Or C ₁ -C ₁₀ alkyl, R ⁷ is C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ halogenated alkyl, C ₄ -C ₂₀ aryl, or C ₄ -C ₂₀ aryl.
A C ₂₀ aryl halide,
An object of the present invention is to provide an ionic metal complex addition compound, wherein the organic compound to be added is an ester compound, an ether compound, a nitrile compound, an alcohol compound, an amide compound, or a ketone compound.

[0008] The alkyl, alkyl halide, aryl and aryl halide used in the present invention include those having other functional groups such as a branch, a hydroxyl group and an ether bond.

Hereinafter, the present invention will be described in more detail.

First, specific examples of the compound represented by the general formula (1) used in the present invention are shown below.

[0011]

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[0012]

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[0013]

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[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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Here, lithium ion is mentioned as A ^{a +} , but as cations other than lithium ion, for example, sodium ion, potassium ion, magnesium ion, calcium ion, barium ion, cesium ion, silver ion, zinc ion, copper ion Ion, cobalt ion, iron ion, nickel ion, manganese ion, titanium ion, lead ion, chromium ion, vanadium ion, ruthenium ion, yttrium ion, lanthanoid ion, actinoid ion, tetrabutylammonium ion, tetraethylammonium ion, tetramethylammonium Ion, triethylmethylammonium ion, triethylammonium ion, pyridinium ion, imidazolium ion, hydrogen ion, tetraethylphospho Ion, tetramethyl phosphonium ion, tetraphenylphosphonium ion, triphenylsulfonium ion, triethylsulfonium ion, etc. is also used.

In consideration of applications such as electrochemical devices, lithium ions, tetraalkylammonium ions and hydrogen ions are preferable. The valence ^{a of the} A ^{a +} cation is preferably from 1 to 3. If it is larger than 3, the crystal lattice energy becomes large, so that there is a problem that it becomes difficult to dissolve in a solvent. Therefore, when solubility is required, 1 is more preferable. Similarly, the valence b of the anion is preferably from 1 to 3, and particularly preferably 1. The constant p representing the ratio of the cation to the anion is the ratio b of the two valences.
/ A inevitably determines.

In the ionic metal complex of the general formula (1) which is a part of the constitution of the present invention, the center M is a transition metal,
It is selected from Group III, Group IV, or Group V elements of the periodic table.
Preferably, Al, B, V, Ti, Si, Zr, Ge,
Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi, P,
It is any of As, Sc, Hf, or Sb, and is more preferably Al, B, or P. Although it is possible to use various elements as the central M, Al,
B, V, Ti, Si, Zr, Ge, Sn, Cu, Y, Z
n, Ga, Nb, Ta, Bi, P, As, Sc, Hf,
Alternatively, in the case of Sb, synthesis is relatively easy, and
In the case of l, B or P, in addition to ease of synthesis, it has excellent properties in all aspects such as low toxicity, stability and cost.

Next, a description will be given of a ligand part which is a feature of the ionic metal complex represented by the general formula (1) which is a part of the constitution of the present invention. Hereinafter, the organic or inorganic portion bonded to M is referred to as a ligand.

X ¹ in the general formula (1) is O, S, NR ⁵ ,
Or NR ⁵ R ⁶ , and through these heteroatoms, M
To join. Here, bonding other than O, S, and N is not impossible but very complicated in synthesis.
As a feature of this compound, since the same ligand has a bond to M through a carboxyl group (—COO—) other than X ¹ , these ligands form a chelate structure with M. Due to the effect of this chelate, the heat resistance of this compound,
Improved chemical stability and hydrolysis resistance. The constant q in the ligand is 0 or 1. Particularly, when it is 0, the chelating ring becomes a five-membered ring, so that the chelating effect is most strongly exerted and the stability is increased. Also,
The negative charge of the central M is dispersed due to the electron-withdrawing effect of the carboxyl group, and the electrical stability of the anion is increased. . Further, other heat resistance, chemical stability and hydrolysis resistance are also improved.

R ¹ and R ² are each independently selected from the group consisting of H, halogen, C ₁ -C ₁₀ alkyl and C ₁ -C ₁₀ halogenated alkyl.
At least one of ¹ and R ² is a fluorinated alkyl, more preferably, at least one of R ¹ and R ² is a trifluoromethyl group. The presence of an electron-withdrawing halogen or alkyl halide in R ¹ and R ² allows the central M
Is dispersed, and the electrical stability of the anion is increased, so that the ion is easily dissociated, and the solubility in a solvent, ionic conductivity, catalytic activity, and the like are increased. Further, other heat resistance, chemical stability and hydrolysis resistance are also improved.
Especially when the halogen is fluorine, the effect is greater,
Further, the effect is the greatest in the case of a trifluoromethyl group.

R^ThreeIs C₁~ C_TenAlkylene, C₁~ C
_TenAlkylene halide, C_Four~ C ₂₀The aryl
Or C_Four~ C₂₀Selected from aryl halides of
But preferably with a central M and a chelating ring
When formed, those forming a 5- to 10-membered ring are preferred. 10
If it is larger than the member ring, the chelating effect will be smaller
Is not preferred. Also, R^ThreeIs hydroxyl or carboxyl
If a group is present in the structure,
It is also possible to make a bond to M.

[0027] R ⁴ is halogen, alkyl of C ₁ -C _4,
Halogenated alkyl C ₁ -C _4, aryl C ₄ -C _20, an aryl halide of C ₄ -C _20, or is made of one selected from X ² R ^7, preferably fluorine being preferred.

X ² is O, S, NR ⁵ , or NR ⁵ R ⁶ and is bonded to M via these heteroatoms. Here, bonding other than O, S, and N is not impossible but very complicated in synthesis.

R ⁵ and R ⁶ are each selected from H or C ₁ -C ₁₀ alkyl. This part does not need an electron-withdrawing group unlike other parts. When an electron-withdrawing group is introduced here, the electron density on N decreases and the central M
Cannot be coordinated.

R ⁷ is C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀
Alkyl halides, aryl C ₄ -C _20, or C ₄ is formed of one selected from an aryl halide of -C _20, preferably fluorinated alkyl C ₁ -C _10. The presence of an electron-withdrawing alkyl halide in R ⁷ disperses the negative charge of the central M, and increases the electrical stability of the anion. Conductivity etc. increase.
Further, other heat resistance, chemical stability and hydrolysis resistance are also improved. In particular, the effect is greater when the alkyl halide is a fluorinated alkyl. The constants m and n related to the number of ligands described so far are determined by the type of M at the center.
To 3, and n is preferably 0 to 4.

In the present invention, the organic compound which forms an addition compound with the ionic metal complex of the general formula (1) is a compound having relatively high coordination, and is an ester compound, an ether compound, a nitrile compound, an alcohol compound, An amide compound, a ketone compound, or the like can be given. Particularly, from the viewpoint of stability, a carbonate ester or an acetate ester is preferable. Specific examples include propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, and ethyl methyl carbonate.

The ionic metal complex addition compound of the present invention comprises
It is dissolved in an organic compound to which the ionic metal complex represented by the general formula (1) is added, and the solution is heated from -20 ° C to 150 ° C
By evaporating or cooling in the temperature range described above to precipitate as crystals. If the temperature is lower than −20 ° C., solidification of the organic substance itself occurs, which is not preferable.
At a temperature of 150 ° C. or higher, the addition compound cannot be stably present.

The ionic metal complex addition compound of the present invention comprises
Since the organic compound is coordinated to the cation, the stability to heat, the stability to hydrolysis, and the stability during storage are both improved compared to the pure ionic metal complex.
Handling is easy.

Further, the ionic metal complex is dissolved in a solvent,
When preparing a solution, there was a problem that the temperature of the solution was raised due to heat of dissolution and solvation, and cooling was required. Since it is in a solvated state, no heat of solvation is generated, and there is also an advantage that the temperature rise is reduced to half or less of the conventional case. Furthermore, the dissolution rate is superior to the conventional one.

Further, in the ionic metal complex addition compound of the present invention, since the organic compound is coordinated to a cation,
Water, which is an impurity remaining in a state coordinated to a cation, is originally expelled, so that there is an advantage that a water having a lower moisture content than that of a single electrolyte can be obtained.

The ionic metal complex addition compound of the present invention comprises
It is superior to conventional ionic metal complexes in purity, ease of handling, and properties for each application.

[0037]

The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples.

Embodiment 1

[0039]

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219 g of the lithium borate derivative having the above structure was dissolved at 20 ° C. in 1000 g of diethyl carbonate. The solvent was removed from this solution at 100 ° C. under reduced pressure of 150 Pa to obtain 278 g of a white solid.

When the obtained solid was confirmed by elemental analysis and NMR analysis, it was confirmed that the obtained solid was an addition compound in which one molecule of lithium borate derivative was added with one molecule of diethyl carbonate.

Example 2 219 g of the same lithium borate derivative as in Example 1 was dissolved in 1000 g of dimethyl carbonate at 20 ° C. The solvent was removed from this solution at 130 ° C. and under a reduced pressure of 150 Pa to obtain 264 g of a white solid.

When the obtained solid was confirmed by elemental analysis and NMR analysis, it was confirmed that the solid was an addition compound in which one molecule of lithium borate derivative was added with one molecule of dimethyl carbonate. The water content of the additional compound was analyzed by the Karl Fischer method and found to be 5 ppm.

Next, ethylene carbonate at 40 ° C. was added to the addition compound to prepare a solution having a concentration of 1 mol / l. At that time, the addition compound dissolved instantaneously. The temperature of the solution increased by 10 ° C. due to the heat of dissolution.

Example 3 The same lithium borate derivative as in Example 1 (219 g) was dissolved in ethyl methyl carbonate (1000 g) at 20 ° C.
The solvent was removed from this solution at 100 ° C. under a reduced pressure of 150 Pa to obtain 271 g of a white solid.

When the obtained solid was confirmed by elemental analysis and NMR analysis, it was confirmed that the obtained solid was an addition compound in which one molecule of ethyl methyl carbonate was added to one molecule of the lithium borate derivative.

Example 4 219 g of the same lithium borate derivative as in Example 1 was dissolved at 20 ° C. in a mixed solvent of 1,000 g of ethyl methyl carbonate and 44 g of ethylene carbonate. The solvent was removed from this solution at 150 ° C. and under a reduced pressure of 150 Pa to obtain 263 g of a white solid.

The obtained solid was subjected to elemental analysis and NMR analysis to confirm the composition. As a result, it was confirmed that the solid was an addition compound obtained by adding one molecule of ethylene carbonate to one molecule of the lithium borate derivative.

Embodiment 5

[0050]

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133 g of the lithium borate derivative having the above structure was dissolved at 20 ° C. in 1000 g of diethyl carbonate. The solvent was removed from this solution at 100 ° C. and under a reduced pressure of 150 Pa to obtain 192 g of a white solid.

When the obtained solid was confirmed by elemental analysis and NMR analysis, it was confirmed that the obtained solid was an addition compound in which one molecule of lithium borate derivative was added with one molecule of diethyl carbonate.

[0053]

Industrial Applicability The ionic metal complex addition compound of the present invention is used for electrochemical devices such as lithium batteries, lithium ion batteries, electric double layer capacitors, and catalysts, and has a higher purity than conventional ionic metal complexes. It is possible to provide an ionic metal complex adduct having high properties, excellent properties, and easy handling.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 4/42 H01M 10/40 A H01M 10/40 H01G 9/00 301D (72) Inventor Mikihiro Takahashi Saitama 2805, Imafukunakadai, Kawagoe City Chemical Research Laboratory, Central Glass Co., Ltd. (72) Inventor Hiromi Sugimoto 2805, Imafukunakadai, Kawagoe City, Saitama Prefecture Chemical Research Laboratory, Central Glass Co., Ltd. 2805, Imafuku-Nakadai, Japan F-term (reference) in Chemical Laboratory, Central Glass Co., Ltd. 4H006 AA01 AB78 AB91 4H048 AA01 AB91 VA50 VA77 VB10 4J015 DA07 5H029 AJ01 AK00 AL00 AM03 AM06 DJ09

Claims (6)

[Claims] 1. An ionic metal complex comprising a compound having the chemical structural formula represented by the general formula (1) and one to six organic compounds coordinated to one molecule of the compound. Addition compound. Embedded image M is a transition metal, a group III, IV, or V element of the periodic table, A ^{a +} is a metal ion, hydrogen ion, or onium ion, a is 1-3, b is 1-3, p Is b /
a and m represent 1 to 3; n represents 0 to 4; and q represents 0 or 1, and X ¹ represents O, S, NR ⁵ , or NR.
⁵ R ⁶ , R ¹ and R ² are each independently H, halogen, C
Alkyl of ₁ -C ₁₀ halogenated alkyl of C _{1 ~C 10,,} R ³ is alkylene of C ₁ -C _10, halogenated alkylene of C ₁ -C _10, aryl of C ₄ -C ₂₀ or C, _Four
Aryl halide to C ₂₀ , R ⁴ is halogen, C ₁ to
Alkyl of C _10, alkyl halide C ₁ ~C _10, C ₄
Aryl -C _20, an aryl halide of C ₄ -C _20,
Or X ² R ⁷ and X ² are O, S, NR ⁵ , or NR
⁵ R ⁶ , R ⁵ , R ⁶ are H or C ₁ -C ₁₀ alkyl,
R ⁷ represents alkyl of C ₁ -C _10, alkyl halide C ₁ -C _10, of C ₄ -C ₂₀ aryl, or C ₄ -C ₂₀ in the aryl halide, respectively. 2. M is Al, B, V, Ti, Si, Z
r, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta,
2. The ionic metal complex addition compound according to claim 1, wherein the compound is any one of Bi, P, As, Sc, Hf, and Sb. 3. The ionic metal complex addition compound according to claim 1, wherein A ^{a +} is one of a Li ion and a quaternary ammonium ion. 4. An ionic metal complex-added compound, wherein the organic compound according to claim 1 is an ester compound, an ether compound, a nitrile compound, an alcohol compound, an amide compound, or a ketone compound. 5. The ionic metal complex addition compound according to claim 4, wherein the ester compound is a carbonate ester or an acetate ester. 6. Carbonate is propylene carbonate.
6. The ionic metal complex addition compound according to claim 5, wherein the ionic metal complex addition compound is selected from the group consisting of ethylene carbonate, diethyl carbonate, dimethyl carbonate, and ethyl methyl carbonate.