JPH0324164A - Solid polyelectrolyte - Google Patents

Abstract

PURPOSE:To prepare a solid polyelectrolyte having an excellent chemical or electrochemical stability and a high ionic conductivity by incorporating a specific salt and, if necessary, an org. liq. capable of dissolving the salt into a crosslinked polyether derived from a polyethylene oxide and/or a polypropylene oxide. CONSTITUTION:A solid polyelectrolyte is prepd. by incorporating at least one salt selected from the group consisting of an alkali metal salt, an alkaline earth metal salt, and an org. ammonium salt and, if necessary, an org. liq. capable of dissolving the salt into a crosslinked polyether. The crosslinked polyether is obtd. by reacting a polyether which has a reactive double bond and which is prepd. by substituting a group of formula I (wherein R1 is H, CH3, or formula III) or formula II (wherein R2 is CH3 or formula III) for the hydrogen atom of at least one hydroxyl group of a polyether having at least one hydroxyl group and a polyethylene oxide, polypropylene oxide, or ethylene oxide-propylene oxide backbone structure. The reaction is conducted by heating or by irradiating with ultraviolet rays or electron beams.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to solid polymer electrolytes used in primary batteries, secondary batteries, electromagnetic batteries, capacitors, and other vaporizers. I) ゛.

Conventional technology ε between points A/potash gold solution, ρ potash metal recommendation salt and high concentration K.
What happens when the dissolved Bolie de A' becomes a game A?
An example of using liquid borate as a solid electrolyte material by converting it into a gel by crosslinking has attracted wide interest in its use as a solid electrolyte due to its relatively high ionic conductivity. As for JP-A-63-13
No. 5477, No. 65-76275, No. 62-
249361 and the like.

JP-A-63-135477 proposes the use of a crosslinked acroyl-modified poly(ethylene oxide) as a solid electrolyte material.

This cross-linked product has good productivity because it is cross-linked with light, and because it contains esthetic bonds in the structure of the cross-linked product, its mechanical strength can be reduced by chemically or electrochemically decomposing or cutting the esthetic bonds. Decrease becomes a problem. In JP-A-65-76275, it has been proposed that boriethe μ is cross-linked by the reaction of boriethe μ with diacrylate to preserve the ester p bond. Therefore, it also causes a decrease in mechanical strength. JP-A No. 62-249361 proposes crosslinking polyether by reacting polyether with diyne V-anate to form urethane bonds. Although urethane bonds are thermally stable compared to NTE bonds, when used as an electrolyte in batteries, they cause decomposition and breakage due to electrochemical reactions, causing a decrease in mechanical strength. Furthermore, since the crosslinking methods based on the formation of ester bonds and V-tan bonds are both two-liquid mixing methods, the productivity is extremely low.

Purpose of the Invention The present invention has been made in view of the above-mentioned problems.
The purpose of the present invention is to provide a solid polymer electrolyte with high ionic conductivity.The purpose of the present invention is to provide a solid polymer electrolyte having at least one hydroxyl group and a polyethylene oxide structure. , or a polyether having a bolideropylene oxide V-do structure, or a copolymer structure of ethylV-oxide and deropylene-V-oxide, the hydrogen of one or more of the hydroxyl groups can be replaced by the following general formula [! ],
or (1) -OH2 - 0 - OH, ...... (1
, 11 The crosslinked polyether obtained by reacting Te contains an organic liquid capable of dissolving one or more salts selected from alkali metal salts, alkaline earth metal salts, and organic ammonium salts and a vI salt. This is a polymer solid electrolyte characterized by the following.

Cobolymer W of ethylene oxide and propylene oxide
The II structure may be a block copolymer structure or a random copolymer structure. In particular, the HUNDAM copolymer structure is advantageous because it exhibits high ionic conductivity at low temperatures. Although the ratio of ethylene oxide units to dep-pylene oxide V-do units is not particularly limited, when the ratio of ethylene oxide units is 70% or more at a 7 μ ratio, a solid electrolyte exhibiting high ionic conductivity can be obtained.

Polyate μ having a reactive double bond is obtained by reacting a polyate having at least one hydroxyl group with a halide of a group having a reactive double bond under basic conditions. As the halogen of the halide, 01, Br, and I are generally used. The group having the reactive double bond is:
These are the ant μ group, the cinnamic μ group, the black group, and the metal group. This reaction method is well known as the Williamson combination method.

Alkali gold m salt contained in the boriethe ρ crosslinked product, a
As a potash earth metal base or an organic ammonium salt, L
i 010 4 , L i B F 4 , L
i A S F 6, LiOF3SO3, LiPF6,
LiI LiBr LiSCNN&X, NaBr,
NaSON, KSON, MgOl2, Mg (0104)
2. (OH3)4MBF4, (CH3)4NBr(0
2H5)4NOl04, (02H5)4N Eng, (0
3H7)4NBr(n-04H?)4NOl04,Cn
-04H9)4'' (n-05H11)4N work is preferred, but is not particularly limited.

Organic liquids that can dissolve salts are Tetowo1≦Dorofufun, 2-methyρTetofEdoro7fun, 1,5-di Chukei Soran, 4,4-Dimegu A/-1, s-spikizan, γ - Petitlovkton, Engineering Carpone F1 Grebilenka ~ Bowinter - F, Petitlenka = - Bonate, :)
'1%' Hofun, 5-Me4-A/Sfi' Hofun, t6
rt. -F〃工-F I's isc) Ichiguchi/1
/5-deμ, 1,2ν methoxyethane, 1,25-methoxymethane V-ethane, medi-8 diglyme, medi'/ll
I. Regrime, Mechi μ Detofughuim, Engineering 4-/lI
Gufim, Echipt) Gufim, Nato A method of anticentering the reactive double bond's 5-te μ is a heating method. ．． UV light and/or visible light
Either a method of irradiating with an electron beam or a method of irradiating with an electron beam may be used. Combination of heating methods, Fuji Rokuμ reaction initiator L
Then, Bezokuzoi ρ Ichito μ Oga・Vdo, Azobisisogu f
Lot! If 1N Go is added, the reaction becomes #sJj and super-coscoL is created. In addition, in the case of a method of irradiating ultraviolet rays and/or visible light, a photoinitiator,! :L, benzoin, benzophenone% acetopue/ysα-pheniμ
If you add a bit of non-adhesive to it, it will easily cause a reaction.

EXAMPLES Below, the details of the present invention will be explained from "C. Dormitory Example C".

Case 1o 10 Double pouch area A/. C-tep-modified polyethylene oxide
0) C, 25! Gubiren carbonate prepared by Sakube, 1 part by weight of lithium perchlorate, and 0.1 part by weight of Bezoi PbeΔ・oxide were uniformly mixed and dissolved in an IC. This mixture was cast on a glass plate at 90 7"Q in a gas stream.
After reacting for 1 hour, a film of 200 m was obtained. The ionic conductivity of this membrane was measured using the complex impedance method and was found to be 7 at 25°C. It was O X 1 O-'S-1.

Mechanical strength is tensile strength of 1. Q #e*-
2 was shown. This film was energized at −80° C. in an ▲r air flow at a current density of EF1 0 sAem T for 1000 hours. The strength of the membrane after energization was 10.2'', and there were no problems for dormitory use.

Example Z 10 Juhobe's aliμ-technized polyethylene oxide (
Allyl ether/Il conversion rate 911, average molecular fi 3000
), 25 double quadrants of Bribirenca 1 bone 1, 1 double quadrants of Lidium A, 0. OIM parts of Penzof 1-non were uniformly dissolved in a mixed stand. Place this mixture on a gas plate and irradiate it for 4 minutes from a distance of 15C with ultraviolet light at 1 hour in an argon stream ps 1QOp! n
obtained the film. As a result of measuring this ion conduction using the complex in-vehicle method, the results were 6. O x 1
It was 0-'3 cm-'. Mechanical strength is tensile strength to. It showed 3k9C+*. Using this g-t, Example 1. The same energization was performed. The strength of the film after energization was 9.5 & 9 cm-', and there was no practical problem. It! Examples & 10 cinnamyl etherified boryates A/(V Nnamip etherification rate 98%, average molecule JIJ3oO)
Ic, 2 5! j 1 part propylene carbonate, 1
! The lowest portion of lithium perchlorate, 0.01 part by weight of Bezoff I, was uniformly mixed and dissolved. This mixture is on the gaffus plate, and in the airflow, IK'W
Irradiated with ultraviolet rays from a distance of 15 cm for 4 minutes,
A film of 00 μm was obtained. The ionic conductivity of this catch is
As a result of measurement t2 using the complex impedance method, 7.
The temperature was -1°C at 0x10-'Sc. Mechanical strength is tensile strength! ``'e 1 t3 k9C solution-2 was shown.Using this film, the same energization as in Example 1o was carried out.

The strength of pus after electricity is applied is 10. 0 kg equipment - 2 indication,
There were no practical problems.

Example 4 o Cinna ξ etherified boryate/I/(E
/ Nnami Aete p conversion rate 98%, average amount 3300)
Ic, 251 parts of delobylene carbonate and 1 part by weight of lithium perchlorate were uniformly mixed and dissolved. This mixture was cast on a glass plate, and in an argon stream, an acceleration voltage of 500 KeV, an electron beam current of 10 m▲, and an electron beam dose of ? i. Perform electron beam irradiation with OMGr, 100*m
I got a film of. The ionic conductivity of this membrane was measured using the complex impedance method and was found to be 5.5% at 25°C. OX10'
It was SC111-'. The mechanical strength showed a tensile strength of 10.4 to CII-2. Using this membrane, Example 1. The same energization was performed. The strength of the membrane after energization is 9
．． 8#c1m-2, and there were no practical problems.

Effects of the Invention As described above, the present invention can provide a polymer solid electrolyte with excellent chemical or electrochemical stability, excellent productivity, and high ionic conductivity. The value is extremely great.

Claims (1)

[Claims] 1) A polyether having at least one hydroxyl group and having a polyethylene oxide structure, a polypropylene oxide structure, or a copolymer structure of ethylene oxide and propylene oxide has hydrogen of one or more hydroxyl groups as shown below. General formula [I] or [II] -CH_2-CH=CHR_1...[I](
R_1 is -H, or -CH_3, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼)▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[II] , tables, etc.▼) A polyether crosslinked product obtained by reacting a polyether having a reactive double bond substituted with an alkali metal salt,
A solid polymer electrolyte comprising one or more salts selected from alkaline earth metal salts and organic ammonium salts and an organic liquid capable of dissolving the salts. 2) The solid polymer electrolyte according to claim 1, wherein the copolymer structure of ethylene oxide and propylene oxide is a random copolymer structure. 3) The solid polymer electrolyte according to claim 1, wherein the polyether having reactive double bonds is crosslinked by irradiation with ultraviolet rays and/or visible light. 4) The solid polymer electrolyte according to claim 1, wherein the polyether having reactive double bonds is crosslinked by irradiation with an electron beam.