JPH0676830A - Ion conductive polymer electrolyte - Google Patents

Abstract

PURPOSE:To obtain an ion conductive polymer electrolyte, which is safe without flowing at a relatively high temperature and which has a high ion conductivity. CONSTITUTION:A part of hydroxyl groups of polyalkyleneoxide at 1000-50000 of molecular weight having a hydroxyl group at the end of a molecular is substituted with alkoxy group, alkenyloxy group or allylicoxi group. The organic polymer obtained by bridging end modified polyalkyleneoxide, which is obtained by substituting the residual hydroxyl group with allylic group, acryloil group or methacryloil group, includes soluble electrolytic salt compound.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to ion conductive polymer electrolytes.

[0002]

2. Description of the Related Art Conventionally, as an ion conductive polymer electrolyte, for example, polyethylene oxide or a polyethylene oxide portion of a polyfunctional polyether molecular structure and a polypropylene oxide portion are randomly copolymerized. Known are organic polymer electrolytes obtained by doping an organic compound with an electrolyte salt and then crosslinking the same (see, for example, JP-A-62-249361), or thermoplastic homopolymers having no cross-linking with an electrolyte salt. Has been.

However, although the former crosslinked polymer has excellent mechanical properties without flowing even in a relatively high temperature range, it has practically sufficient ionic conductivity because it is constrained by the segmental motion of the molecular chain due to crosslinking. I can't get it. In addition, the latter thermoplastic polymer generally has a higher ionic conductivity than the cross-linked polymer, but has the drawback that it easily flows at high temperatures. Therefore, these conventional ion-conducting polymer electrolytes are often unsatisfactory as electrolytes used for large-scale batteries that operate at relatively high temperatures (60 to 80 ° C.) for power flattening and electric vehicles.

The present invention has been made in view of the above problems of the prior art, and its object is ionic conduction which is safe without flowing even at a relatively high temperature and has high ionic conductivity. To provide a conductive polymer electrolyte.

[0005]

In order to achieve the above object, the gist of the present invention is to provide a molecular weight 1 having a hydroxyl group at the molecular end.
Crosslinking a terminal-modified polyalkylene oxide in which a part of the hydroxyl groups of polyalkylene oxide of 000 to 50,000 is substituted with an alkoxy group, an alkenyloxy group or an aryloxy group and the remaining hydroxyl groups are substituted with an allyl group, an acryloyl group or a methacryloyl group. An ion conductive polymer electrolyte characterized in that a soluble electrolyte salt compound is contained in the organic polymer.

The above-mentioned polyalkylene oxide is obtained by reacting an alkylene oxide with an active hydrogen-containing compound. Examples of the active hydrogen-containing compound include methanol, ethanol, ethylene glycol, propylene glycol and 1,4 butane. Polyhydric alcohols such as diol, glycerin, trimethylolpropane, sorbitol, sucrose, polyglycerin, butylamine, 2-ethylhexylamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, aniline , Amine compounds such as benzylamine, phenylenediamine, bisphenol A,
Examples thereof include phenolic active hydrogen compounds such as hydroquinone and novolac, and compounds having different active hydrogen-containing groups in one molecule such as monoethanolamine and diethanolamine. Among them, polyhydric alcohols are particularly preferable.

The alkylene oxides include ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane. , 1,2-epoxynonane and the like having 4 to 4 carbon atoms
Examples of the α-olefin oxide of 9 and α-olefin oxides having 10 or more carbon atoms, styrene oxides and the like can be mentioned, and ethylene oxide and propylene oxide are preferable.

Some of the end groups of the polyalkylene oxide of the present invention are "alkoxy groups, alkenyloxy groups or aryloxy groups" and the other parts are "allyl groups, acryloyl groups or methacryloyl groups". .
Of the alkoxy group, alkenyloxy group and aryloxy group, an alkoxy group is particularly preferable, and a lower alkoxy group, that is, a methoxy group and an ethoxy group are more preferable. The proportion of these groups is preferably 50 to 98% with respect to the terminal groups. The remaining terminal group is an allyl group, an acryloyl group or a methacryloyl group, of which an acryloyl group or a methacryloyl group is preferable. The ratio of these groups is 2 to 5 with respect to the terminal group.
0% is preferable. This is because if it is less than 2%, the mechanical strength of the obtained ion conductive polymer is low, and if it is more than 50%, high ion conductivity cannot be obtained.

As a method of introducing these groups into the terminal group, for example, a part of the terminal hydroxyl group existing after the polymerization of the above polyalkylene oxide is alkoxylated with an alkyl halide or the like, and the remaining It is possible to employ a method of further substituting the hydroxyl groups of the above by esterification or the like.

The thus-obtained terminal-modified polyalkylene oxide is doped with a soluble electrolyte salt compound exemplified below, and if necessary, a polymerization initiator and / or
Alternatively, a sensitizer can be used to crosslink under irradiation of actinic radiation such as light, heat, and electron beams to obtain the ion conductive polymer electrolyte of the present invention. As the soluble electrolyte salt compound,
For example, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium nitrate, lithium thiocyanate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium tetrafluorofluoride, lithium bistrifluoromethylsulfonylimide, tristrifluoride. Fluoromethylsulfonylmethide lithium, sodium thiocyanate,
Sodium perchlorate, sodium trifluoromethanesulfonate, sodium tetrafluorofluoride, potassium thiocyanate, potassium perchlorate, potassium trifluoromethanesulfonate, potassium tetrafluorofluoride, magnesium thiocyanate, magnesium perchlorate and trifluoromethane At least one or two or more selected from the group consisting of magnesium sulfonate can be used.

Further, when the ion conductive polymer electrolyte of the present invention is obtained, two or more kinds of end-modified polyalkylene oxides can be used together.

[0012]

The ion conductive polymer electrolyte of the present invention is composed of an organic polymer obtained by crosslinking a polyether compound having a specific structure, so that it stabilizes the amorphous phase that contributes to ion conduction, and has high ion conductivity from low temperature to high temperature. Is expressed and does not flow even in a high temperature range.

[0013]

EXAMPLES Examples of the present invention will be described below. Example 1 Glycerin having a molecular weight of 8000 was mixed with ethylene oxide and propylene oxide (weight ratio 4:
1) is reacted in the presence of a catalyst, 0.72 equivalent of sodium methylate is added to the number of terminal hydroxyl groups of the copolymer, methanol is removed at 100 ° C to alcoholate the terminal hydroxyl groups, and then iodinated. 70% of the terminal hydroxyl groups were methoxylated by adding methyl and reacting at 80 ° C. for 6 hours. Next, by reacting 1.2 equivalents of acrylic acid with respect to the number of remaining hydroxyl groups, 50 times the weight (weight) of the acrylic acid, and 0.01 mol% of sulfuric acid at 80 to 90 ° C. for 8 hours, 70% of the groups are methoxylated and 3
A terminal modified polyalkylene oxide having 0% acrylate was obtained. To 3.6 g of the terminal-modified polyalkylene oxide thus obtained, 0.4 g of lithium perchlorate and 0.006 g of a polymerization initiator (1-hydroxycyclohexyl phenyl ketone) were added and uniformly dissolved. And was irradiated with ultraviolet rays at an intensity of 7 mW / cm ² in a nitrogen atmosphere to obtain an ion conductive polymer electrolyte having a thickness of 50 μm.

(Example 2) Glycerin having a molecular weight of 6000 was reacted with a mixture of ethylene oxide and propylene oxide (weight ratio 9: 1) in the presence of a catalyst, and the copolymer was adjusted to 0. After adding 87 equivalents of sodium methylate and removing methanol at 100 ° C. to alcoholate the terminal hydroxyl group, methyl iodide was added,
By reacting at 80 ° C for 6 hours, 85
% Was methoxylated. Next, 1.2 equivalents of acrylic acid with respect to the number of remaining hydroxyl groups, toluene (50 times as much as the acrylic acid) and 0.01 mol% of sulfuric acid are added at 80 to 90 ° C.
85% of the terminal group was methoxylated and 15% of the terminal group was acrylated to obtain a terminal-modified polyalkylene oxide. To 3.6 g of the terminal-modified polyalkylene oxide thus obtained, 0.4 g of lithium perchlorate and 0.006 g of a polymerization initiator (1-hydroxycyclohexyl phenyl ketone) were added and uniformly dissolved. Flow down to 7 mW / cm ² in a nitrogen atmosphere.
An ion conductive polymer electrolyte having a thickness of 50 μm was obtained by irradiating with ultraviolet rays with the intensity of.

(Example 3) Glycerin having a molecular weight of 9000 was reacted with a mixture of ethylene oxide and propylene oxide (weight ratio 9: 1) in the presence of a catalyst to give a copolymer of 0. 92 equivalents of sodium methylate were added, methanol was removed at 100 ° C. to alcoholate the terminal hydroxyl groups, and then methyl iodide was added,
90% of the terminal hydroxyl groups can be obtained by reacting at 80 ° C for 6 hours.
% Was methoxylated. Next, 1.2 equivalents of acrylic acid with respect to the number of remaining hydroxyl groups, toluene (50 times as much as the acrylic acid) and 0.01 mol% of sulfuric acid are added at 80 to 90 ° C.
Was reacted for 8 hours to obtain a terminal-modified polyalkylene oxide in which 90% of the terminal groups were methoxylated and 10% were acrylated. To 3.6 g of the terminal-modified polyalkylene oxide thus obtained, 0.4 g of lithium perchlorate and 0.006 g of a polymerization initiator (1-hydroxycyclohexyl phenyl ketone) were added and uniformly dissolved. Flow down to 7 mW / cm ² in a nitrogen atmosphere.
An ion conductive polymer electrolyte having a thickness of 50 μm was obtained by irradiating with ultraviolet rays with the intensity of.

(Example 4) Glycerin having a molecular weight of 5000 was reacted with ethylene oxide in the presence of a catalyst, 0.85 equivalent of sodium methylate was added to the number of terminal hydroxyl groups of the polymer, and methanol was added at 100 ° C. After removal and alcoholation of the terminal hydroxyl groups, methyl iodide was added and reacted at 80 ° C. for 6 hours to methoxylate 85% of the terminal hydroxyl groups. Then, 1.2 equivalents of acrylic acid with respect to the number of remaining hydroxyl groups, toluene (50 times as much as the acrylic acid) and 0.01 mol% of sulfuric acid are added in an amount of 80 to 9
By reacting at 0 ° C. for 8 hours, 85% of the terminal groups were methoxylated and 15% were acrylated to obtain a terminal-modified polyalkylene oxide. To 3.6 g of the terminal-modified polyalkylene oxide thus obtained, 0.4 g of lithium perchlorate and 0.006 g of a polymerization initiator (1-hydroxycyclohexyl phenyl ketone) were added and uniformly dissolved. 7 mW / in a nitrogen atmosphere
50 μm in thickness by irradiating with ultraviolet light with an intensity of cm ^2.
The ion conductive polymer electrolyte of was obtained.

Example 5 Glycerin having a molecular weight of 7,000 was reacted with a mixture of ethylene oxide and 1,2-epoxybutane (weight ratio 85:15) in the presence of a catalyst,
Sodium methylate in an amount of 0.60 equivalent to the number of terminal hydroxyl groups of the copolymer is added, methanol is removed at 100 ° C. to alcoholate the terminal hydroxyl groups, and then methyl iodide is added, followed by reaction at 80 ° C. for 6 hours. As a result, 60% of the terminal hydroxyl groups were methoxylated. Then, 1.2 equivalents of acrylic acid with respect to the number of remaining hydroxyl groups, and 50 of the acrylic acid.
80% of double amount (weight) of toluene and 0.01 mol% of sulfuric acid
By reacting at ~ 90 ° C for 8 hours,
% Was methoxylated and 40% was acrylated to obtain an end-modified polyalkylene oxide. To 3.6 g of the terminal-modified polyalkylene oxide thus obtained, 0.4 g of lithium perchlorate and 0.006 g of a polymerization initiator (1-
(Hydroxycyclohexyl phenyl ketone) is added and dissolved uniformly, and then it is flowed down on a glass plate, and it is kept at 7 m in a nitrogen atmosphere.
By irradiating ultraviolet rays with an intensity of W / cm ² , thickness 50
A μm ion-conductive polymer electrolyte was obtained.

Example 6 In addition to 1.8 g of the terminal-modified polyalkylene oxide used in Example 1 and 1.8 g of the terminal-modified polyalkylene oxide used in Example 3, 0.4 g and 0.006 g of lithium perchlorate were used. Polymerization initiator (1-hydroxycyclohexyl phenyl ketone) was added and uniformly dissolved, and then the solution was flowed down on a glass plate and placed in a nitrogen atmosphere at 7 mW /
50 μm in thickness by irradiating with ultraviolet light with an intensity of cm ^2.
The ion conductive polymer electrolyte of was obtained.

Example 7 To 3.0 g of the terminal-modified polyalkylene oxide used in Example 1, 0.6 g of propylene carbonate and 0.5 g of lithium perchlorate were added and uniformly dissolved, and then the solution was poured onto a glass plate. Electro-curtain type electron beam irradiation device (output 200kV, absorbed dose 5Mr
Ad) was irradiated with an electron beam in a nitrogen atmosphere to obtain an ion conductive polymer electrolyte having a thickness of 20 μm.

(Comparative Example) An ion conductive polymer electrolyte was obtained in the same manner as in Example 1 except that the polyalkylene oxide used in Example 1 was completely acrylated at the terminal.

(Lithium Ion Conductivity Test) Next, in order to measure the ionic conductivity of the ion conductive polymer electrolytes of Examples 1 to 7 and Comparative Example thus obtained, each polymer electrolyte was coated with a platinum plate. AC impedance between the electrodes was measured and complex impedance analysis was performed. The results are shown in Table 1 below. An impedance analyzer (model: 4192A) manufactured by Yokogawa Hewlett-Packard Company was used as a measuring machine, and the measurement conditions were as follows: applied voltage = 10 mV, measurement working frequency = 5 Hz.
.About.13 MHz.

[0022]

[Table 1]

As is clear from Table 1, the ion conductive polymer electrolyte of the present invention exhibits excellent ionic conductivity, and particularly excellent ionic conductivity at relatively high temperatures.

[0024]

EFFECT OF THE INVENTION The ion conductive polymer electrolyte according to the present invention shows stable and high ion conductivity from low temperature to high temperature. Further, since it is a crosslinked polymer electrolyte, it does not have the fluidity found in conventional thermoplastic polymer electrolytes and can be safely used even at high temperatures.

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[Procedure amendment]

[Submission date] August 4, 1993

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[0013]

EXAMPLES Examples of the present invention will be described below. Example 1 Glycerin was reacted with a mixture of ethylene oxide and propylene oxide (weight ratio 4: 1) in the presence of a catalyst to give a copolymer having a molecular weight of 8000, and its terminal water.
Add 0.72 equivalent of sodium methylate to the acid group, remove methanol at 100 ° C. to alcoholate the terminal hydroxyl group, and then add methyl iodide and react at 80 ° C. for 6 hours to give 70% of the terminal hydroxyl group. % Was methoxylated. Then, 1.2 equivalents of acrylic acid with respect to the remaining hydroxyl groups, toluene (50 times as much as the acrylic acid) and 0.01 mol% of sulfuric acid are reacted at 80 to 90 ° C. for 8 hours.
Esterification was carried out. As described above, a terminal-modified polyalkylene oxide in which 70% of the terminal group was methoxylated and 30% of which was acrylic ester was obtained. To 3.6 g of the terminal-modified polyalkylene oxide thus obtained, 0.4 g of lithium perchlorate and 0.006 g of a polymerization initiator (1-
(Hydroxycyclohexyl phenyl ketone) is added and dissolved uniformly, and then it is flowed down on a glass plate, and it is kept at 7 m in a nitrogen atmosphere.
The thickness is 50 by irradiating ultraviolet rays with the intensity of W / cm2.
A μm ion-conductive polymer electrolyte was obtained.

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(Example 2) A copolymer having a molecular weight of 6000 obtained by reacting glycerin with a mixture of ethylene oxide and propylene oxide (weight ratio 9: 1) in the presence of a catalyst.
To the terminal hydroxyl group, 0.87 equivalent of sodium methylate was added, methanol was removed at 100 ° C. to alcoholate the terminal hydroxyl group, and then methyl iodide was added,
By reacting at 80 ° C for 6 hours, 85
% Was methoxylated. Next, 1.2 equivalents of acrylic acid with respect to the remaining hydroxyl groups, 50 times the weight (weight) of the acrylic acid, and 0.01 mol% of sulfuric acid are added at 80 to 90 ° C.
And reacted for 8 hours for esterification. From the above,
85% of the terminal groups were methoxylated and 15% was acrylic esterified to obtain a terminal-modified polyalkylene oxide. Terminal-modified polyalkylene oxide thus obtained 3.
To 6 g, 0.4 g of lithium perchlorate and 0.006 g of a polymerization initiator (1-hydroxycyclohexyl phenyl ketone) were added and uniformly dissolved, and then the mixture was poured onto a glass plate.
An ion conductive polymer electrolyte having a thickness of 50 μm was obtained by irradiating with ultraviolet rays at an intensity of 7 mW / cm 2 in a nitrogen atmosphere.

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(Example 3) A copolymer having a molecular weight of 9000, which was obtained by reacting glycerin with a mixture of ethylene oxide and propylene oxide (weight ratio 9: 1) in the presence of a catalyst.
To the terminal hydroxyl group, 0.92 equivalent of sodium methylate is added, methanol is removed at 100 ° C. to alcoholate the terminal hydroxyl group, and then methyl iodide is added.
90% of the terminal hydroxyl groups can be obtained by reacting at 80 ° C for 6 hours.
% Was methoxylated. Next, 1.2 equivalents of acrylic acid with respect to the remaining hydroxyl groups, 50 times the weight (weight) of the acrylic acid, and 0.01 mol% of sulfuric acid are added at 80 to 90 ° C.
And reacted for 8 hours for esterification. From the above,
90% of the terminal groups were methoxylated and 10% were acrylic esterified to obtain a terminal-modified polyalkylene oxide. End-modified polyalkylene oxide 3.6 thus obtained
Lithium perchlorate (0.4 g) and 0.006 g of a polymerization initiator (1-hydroxycyclohexyl phenyl ketone) were added to g and uniformly dissolved, and then the mixture was flowed down on a glass plate with a strength of 7 mW / cm2 in a nitrogen atmosphere. By irradiation with ultraviolet rays, an ion conductive polymer electrolyte having a thickness of 50 μm was obtained.

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(Example 4) A polymer having a molecular weight of 5000 obtained by reacting glycerin with ethylene oxide in the presence of a catalyst.
To the terminal hydroxyl group, 0.85 equivalent of sodium methylate was added, methanol was removed at 100 ° C. to alcoholate the terminal hydroxyl group, and then methyl iodide was added.
By reacting at 80 ° C for 6 hours, 85
% Was methoxylated. Next, 1.2 equivalents of acrylic acid with respect to the remaining hydroxyl groups, 50 times the weight (weight) of the acrylic acid, and 0.01 mol% of sulfuric acid are added at 80 to 90 ° C.
And reacted for 8 hours for esterification. From the above,
85% of the terminal groups were methoxylated and 15% was acrylic esterified to obtain a terminal-modified polyalkylene oxide. Terminal-modified polyalkylene oxide thus obtained 3.
To 6 g, 0.4 g of lithium perchlorate and 0.006 g of a polymerization initiator (1-hydroxycyclohexyl phenyl ketone) were added and uniformly dissolved, and then the mixture was poured onto a glass plate.
An ion conductive polymer electrolyte having a thickness of 50 μm was obtained by irradiating with ultraviolet rays at an intensity of 7 mW / cm 2 in a nitrogen atmosphere.

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Example 5 A mixture of glycerin with ethylene oxide and 1,2-epoxybutane (weight ratio 85:
15) was reacted in the presence of a catalyst with a molecular weight of 7,000
To the polymer , add 0.60 equivalent of sodium methylate to the terminal hydroxyl group, remove methanol at 100 ° C to alcoholate the terminal hydroxyl group, and then add methyl iodide and react at 80 ° C for 6 hours. Was used to methoxylate 60% of the terminal hydroxyl groups. Next, with respect to the remaining hydroxyl groups, 1.2 equivalents of acrylic acid, 50 times the weight of the acrylic acid (weight) of toluene and 0.01 mol% of sulfuric acid are added to 80-9.
Esterification was performed by reacting at 0 ° C. for 8 hours . Based on the above
As a result, 60% of the terminal group was methoxylated and 40% of the terminal group was acrylated to obtain a terminal-modified polyalkylene oxide. Terminal-modified polyalkylene oxide thus obtained 3.
To 6 g, 0.4 g of lithium perchlorate and 0.006 g of a polymerization initiator (1-hydroxycyclohexyl phenyl ketone) were added and uniformly dissolved, and then the mixture was poured onto a glass plate.
An ion conductive polymer electrolyte having a thickness of 50 μm was obtained by irradiating with ultraviolet rays at an intensity of 7 mW / cm 2 in a nitrogen atmosphere.

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Claims (3)

[Claims] 1. A molecular weight of 100 having a hydroxyl group at the molecular end.
Crosslinking a terminal modified polyalkylene oxide in which a part of the hydroxyl groups of 0 to 50000 polyalkylene oxide is substituted with an alkoxy group, an alkenyloxy group or an aryloxy group and the remaining hydroxyl groups are substituted with an allyl group, an acryloyl group or a methacryloyl group. An ion conductive polymer electrolyte, characterized in that a soluble electrolyte salt compound is contained in the organic polymer. 2. The ratio of an alkoxy group, an alkenyloxy group or an aryloxy group is 50 to 98%, and the ratio of an allyl group, an acryloyl group or a methacryloyl group is 2 to 50%. The ion-conductive polymer electrolyte described. 3. An organic polymer in which a terminal-modified polyalkylene oxide is cross-linked with a polymerization initiator and / or a sensitizer, if necessary, under irradiation of active radiation such as heat, light or electron beam. The ion conductive polymer electrolyte according to claim 1, wherein