JPS6031555A - Hybrid ion conductor composed of oxyethylene (meth) acrylate polymer and inogranic lithium salt - Google Patents

Abstract

PURPOSE:To provide a compsn. capable of forming a highly ion-conductive film with good film-formability, by mixing a specified (meth)acrylate (co)polymer with an inorg. lithium salt. CONSTITUTION:A (meth)acrylate (co)polymer having an MW of 10,000-500,000 and the formula [wherein R is H, CH3; R' is a 1-6C alkyl; n is 5-20; x is 100-50% (x+y=100%)] is mixed with at least one inorg. lithium salt selected from LiClO4, LiBF4 and LiPF6 in a molar ratio of 99/1-50/50.

Description

Detailed Description of the Invention The present invention relates to a (meth)acrylate (co)polymer having oligoethylene oxide in the side chain represented by the general formula (1), and LiCl0+ or LIBF4 (or LiP
Fa) and an inorganic lithium salt selected from 99/1
The present invention relates to a conventional hybrid ion conductor formed by mixing at a weight ratio of 50,150 to 50,150.

[Here, R is I] or C8, R' is an alkyl group having 1 to 6 carbon atoms, n is an integer of 5 to 20, X is 100 to 50%,
x + y=l OO%] The polymer-inorganic lithium salt hybrid ion conductor was devised to provide good moldability while maintaining high ionic conductivity, and is particularly suitable for electronic components. Considering its use as a material, being able to make it into a thin film is an important issue. A solid electrolyte in which a predetermined amount of LiClO4 is dispersed in high molecular weight polyethylene oxide [J, E, W
eston et al+ Sol ld 5tate Ion+
cs+ 2 +347 (1981)), but these are because the ibrid solid ionic conductor of the present invention has an oligoethylene oxide with a very low glass transition point in the side chain as a group that interacts with lithium ions. , a formula with a (meth)acrylate main chain to maintain film formability (
Since it is an hybrid of a polymer having the structure No. 11 and an inorganic lithium salt, it is characterized by having both high ionic conductivity and good film-forming ability.

In formula (1), the (meth)acrylate alkyl ester copolymer unit is introduced to change the film formability, and may be reduced by y-0%, and R may be increased to make the film harder. Just use the alkyl in the chain to make y close to 50%.

R=! (, Cl-1, there is almost no difference, but ■=C
H3 gives a slightly harder film.

The inorganic lithium salt obtained in the present invention is LiCl0°, L
iBF, LiPF6, and although there are no major differences, in view of the compatibility with the polymer of formula (1) and the ionic conductivity of the hybrid, LiClO4 and LiPF6 are selected.
F6 is superior to LiBF*.

The hybrid solid ion conductor of the present invention can be formed by casting a film by homogeneously dissolving the polymer of formula (1) and the lithium salt described above in tetrahydrofuran, methanol, acetone, etc., or and y=15
If the polymer and inorganic lithium salt are less than 20%
It can be heated to about 0°C, mixed uniformly, melt-casted, and can be pressed and/or hot-molded to a certain extent. However, when using L i C104, it cannot be heated above 806C due to the risk of explosion. Alternatively, if a mixture of monomers corresponding to formula (1) and an inorganic lithium salt are kneaded in advance and heated in an inert atmosphere, spontaneous polymerization will occur, and the desired hybrid solid ionic conductor can be obtained. It will be done.

The mixing ratio of the polymer of formula (1) and the inorganic lithium salt is 99
A weight ratio of /1 to 50,150 will exhibit the specified performance, but as the proportion of inorganic lithium salt increases, the ionic conductivity will gradually increase. If the amount of inorganic lithium salt is increased beyond this range, the film becomes brittle due to the formation of microcrystals.

Next, the hybrid solid ion conductor of the present invention will be explained with reference to Examples, but first, the synthesis of the polymer of formula (I) and the corresponding monomer of the X unit moiety will be shown in Experimental Examples.

Experimental Example 1 One-terminal methyl ether oligoethylene oxide 202 of molecule i1250 (n□, -5) was converted into anhydrous 'l'l (F
Metal lithium 52 was added to the solution under reflux. After one day of reaction, remove excess metal lithium and
1°2 of methacrylic acid chloride was cooled to TH
A solution diluted with F50- was added dropwise and incubated at ooC for 2 hours.
The reaction was allowed to proceed at room temperature for 5 hours. It was concentrated under reduced pressure to about 1"00, and developed in a basic alumina column with a diameter of 10 m and a length of 30 cm with CICl3 to remove excess methacrylic acid chloride and by-produced LiC1, resulting in one-terminated methyl ether oligoethylene oxide. CI of methacrylate (CI,
A solution was obtained. As a result of fractionating and analyzing a small amount of this solution, the yield was about 229, and de ec f was observed by nuclear magnetic resonance, so the structure of formula (2) was confirmed.

Experimental Examples 2 to 5 Exactly the same as Experimental Example 1, except that the molecular weight was 350. (n〒8)
(Experimental example 2), 550 (n output 13 (Experimental example 3), 750
(n Ki 17) (Experimental Example 4), 900 (n Out 20)
The corresponding methacrylate monomer was obtained using 202 pieces of the one-terminated methyl ether oligoethylene oxide of (Experimental Example 5). The yield is 21 and 202.199 respectively.
．． 199, and gave the same nuclear magnetic resonance spectrum as in Experimental Example 1, except for the difference in the en-roton ratio.

Experimental Examples 6 to 10 Experimental Example 1. -6, except that acrylic acid chloride was used, and the molecular weight was 25o (Experimental Example 6), 35o (Experimental Example 7),
The corresponding acrylate tomo/7-
211.20ii', 19.5f, and 192.1872 were obtained. Compared to Experimental Examples 1 to 5, similar nuclear magnetic resonance spectra were given except for the disappearance of the a proton in formula (2).

Experimental Examples 11-20 Monomer solutions obtained in Experimental Examples 1-10 C1-IC1
3 was distilled off and heated at 60°C for 12 hours under degassing, either as it is or with the monomers listed in Table 1 along with comonomers.
The product was dialyzed into an aqueous solution and dried under reduced pressure to obtain the corresponding copolymer as shown in Table 1.

x% (see formula (1)) in the polymer was determined by nuclear magnetic resonance method.

Table 1, Experimental meal 1) None 10mnoI O, 1rrmol 2 Shin95 100
01゜ Real MflX2+ Butyl methacrylate o a
85 63 3゜10mno1 5mno! 13 Real MID) Methyl methacrylate rt tr
72 □4. 610mmo1 5m+r+o1 14 Experimental fee ■4) Hex7 methacrylate #30
mA 83 77 2315r+vy+ol 5+ym
o1 15 Experiment flXs) None 10m+nO] “ 2°d931000.6 Experiment f
lX6) None 02rrrno14Dd 98 10
0 020m+no 1 1□ Experimental example (71 acrylic acid body ” 20++f 8
8 79 2115 mmo1 5 mmo! +8 "Experiment 91Xsj None 0101-0l20.9
7 100 010rm+ol +9 Experiment 911=r) Acrylic acid sol. 2mno
+ 30++d 85 71 2915mmol 5m
no1 20 Experiment %X10 7'IJl'acid"" 0.2rr
mo120++d 95 55 4510mmol l
omnol Examples 1 to 10 The monomer Cl-ICl3 solutions of Experimental Examples 1 to 10 were distilled off under reduced pressure, changed to THF solvent, mixed with inorganic lithium salt at the ratio shown in Table 3, spread on a Teflon plate, and IIF
was evaporated and polymerized by standing under reduced pressure for 12 hours and at 60°C for 12 hours. The ionic conductivity of the obtained thin film was 100 to 2 with a graphite/membrane/graphite cell configuration.
10) It was determined by measuring the current caused by applying an AC voltage of Iz and plotting the complex impedance. The results are summarized in Table 3.

Third surface film thickness Ionic conductivity example Monomer Inorganic lithium salt THF -(s/
, l) Examples 11 to 20 The polymers of Experimental Examples 11 to 20 were mixed with an inorganic lithium salt in THF or methanol as shown in Table 3, and spread on a Teflon plate to slowly evaporate the solvent. After that, 6
The mixture was dried to dryness under reduced pressure at 0°C, and the ionic conductivity was measured in the same manner as in Examples 1 to 10, and the results are shown in Table 3.

11 Prefectural mackerel 1tt 2. Or LiCIQ 1. Of
Tl(F 5.0 0.11 1.lX1O-512/
/ 12 1.0ta LiPF6 0.01F Methanol 4.0 0.16 6.6X10-'+3 〃
13 2. Of I, +BF, 0.05f THF
5.0 (1218,4X10-'14''+41
．． 01F LiPFa 059 l1j10.11 9
．． 2X10-'15''151.O1' LiCIQ
O: 3f ” IIO, 131, 3X1G-'16
n 16 lot LiBF, I# methanol 10
．． 0 0. +7 9.7XIQ-'17 〃17 zo
r LiPF,,t,oy〃+z 0.17! , 3X
10-518 J/ 182. OY LiCIQ 10
9'IN(F 10.00.16 1.4X10-5
19 +7 19 2. Or LiCl0. 1. Of
li/- +On O, +3 1.3XIO-520
n 201. Of LiPF, 029 TT (F5.0
0. +2 7.6X10-' Examples 21 to 26 A predetermined amount of LiPF was added to the polymers of Experimental Examples 11.13.15.16 to 18, and the mixture was heated to about 200'C under nitrogen and kneaded. It was melt cast onto a board.

After cooling, the ionic conductivity was measured in the same manner as in Experimental Examples 1 to 1o and shown in the fourth light.

21 Experimental Example 11 2. Of O,52201,27,
6X10-622 tt 13ZOf 1.0 260
1.3 1.2xlO-523u 154. Or 1
．． 0 220 0.8 8.4X10-624 Ll
165. Of 1.0 200 11 6.3XIQ”
2s #/173. IM' 1.0 240 +,s
1.3X10-526' 184. Of 1.0 2
60 1.8 9.5X10-' Examples 27 to 32 The hybrids of Examples 21 to 26 were cooled as they were without being cast to form an amorphous solid. This was suitably shaped into strips, heated to 60°C while applying a pressure of about 5K9/c- to form a film, and the ionic conductivity was measured in the same manner as in Examples 1 to 10. It was shown to.

March 1980 Sunset, Mr. Kazuo Wakasugi, Director General of the Patent Office 1 Case description 1988 Patent Application No. 13878.7 2 Title of the invention Comprising oxyethylene (meth)acrylate polymer and inorganic lithium salt / Ibrid-based ion conductor Applicant 4, Date of amendment order November 8, 1982 & Subject of amendment (1) Scope of claims in the specification (2) ``Details of the invention'' in the specification (3) "Experimental Example 1" in the specification (4) "Experimental Example 1-6" in the specification (5) "Experimental Example 1-io4" in the specification (corrected portions are underlined).

(2) On page 4 of the specification, between the second line and the first line from the bottom, [
The polymer used here or the polymer in the hybrid obtained by natural polymerization has a molecular weight in the range of 10,000 to 500,000. ” is inserted.

(3) On page 6 of the specification, delete the next line of structural formula (2) and replace it with “a:20(8)I), b, c:a5, fit(2
1 (), d: 4.2 (2H), e: a6 (18H), f
: a8 (3H)pl)m (in CDC1s), the structure of formula (2) was confirmed. ” is inserted.

(4) Insert the following sentence on page 8 of the specification, below Table 1.

[The molecular weight of these (co)polymers was determined by light scattering method.
15000 (Example 11) and 22000 (1
2), 13000 (13), 10100 (14), 35
000 (15), 78000 (16), 170000 (
17), 495000 (18), 82000 (19),
It was 43,000 (20). (5) On page 9 of the specification, insert the following sentence after the last line.

[Incidentally, a part of the obtained membrane was dissolved in water and dialysis was performed for three days to obtain a solution containing only the polymer, and when molecules 1 were determined by light scattering method, they were 18,000 (Example 1) and 23, respectively.
000(2), 26000(8), 34000(4),
17000 (5), 88000 (6), 71000
(7), 122000 (8), 65000 (9), 44
000 (10'). ” Claims General formula [where kR is H or CHa, R is an alkyl group having 1 to 6 carbon atoms, n is an integer of 5 to 20, X is 100 to 50%, x
+y=loo%, molecular weight is 10,000 to 500,000] and LiCIO4 or LiBF4
Inorganic lithium salt selected from WaneLiPF5,
A hybrid ion conductor formed by mixing at a weight ratio of 99/l to 50,150/l.

Procedural amendment 1987 (A26) Mr. Manabu Shiga, Commissioner of the Japan Patent Office 1, Indication of the case Patent application No. 138787/1987 2, Name of the invention Hybrid system consisting of oxyethylene (meth)acrylate polymer and inorganic lithium Ji1 Ionic conductor 3, relationship with the person making the amendment Patent applicant: 1) Shun Hide 4, agent address: 17 Mori Building 6, 1-26-5 Toranomon, Minato-ku, Tokyo, specification subject to amendment 7, Contents of the amendment (1) “80°C・
・Correct "cannot dispute" to "need to be careful about heating temperature."

(2) In the 6th line of page 5 of the specification, next to ``Becomes brittle.'' ``The ionic conductor of the present invention can be incorporated as a solid electrolyte into electrolytic capacitors, batteries, electrochronic display devices, etc.'' It can also be used as a non-static material.''

Claims (1)

[Claims] General formula [where R is I-1 or Cl-13, R' is carbon number 1]
-6 alkyl group, n is an integer of 5 to 2o, x is 100 to
50%+2+'/=100%] Relforimate, L" 104 i Taij L r BF4 or L
Inorganic lithium salt selected from iPP6, 99/
A hybrid ion conductor formed by mixing in a weight ratio of 1 to 50,150.