JPH04283225A - Electronically conductive polymer - Google Patents

Abstract

PURPOSE:To obtain an electronically conductive polymer which can give a secondary battery excellent in capacity, repeated charge/discharge performance, self-discharge characteristics, etc., by reacting an oxidizing agent comprising a cupric compound with a specified five-membered ring compound. CONSTITUTION:A compound of formula I (wherein L1 and L2 are each a bivalent bonding group; R1 and R2 are each a bivalent bonding group; R3 is H, alkyl, aryl, a cyclic ester group, an acyclic ester group or the like; R4 is a cyclic ester group, an acyclic ester group, a cyclic ether group or the like; n and n' are each an integer of 1 or greater; R5 and R5' are each H or alkyl; a, b and c are each 0 or 1; X is -NH-, -NR6-, -S-, -O-, -Te or -Se-; and R6 is alkyl or aryl), e.g. one represented by formula II, III or IV, is reacted with an oxidizing agent comprising a cupric compound, e.g. copper borofluoride, to produce an electronically conductive polymer. The obtained polymer can be desirably used as a positive electrode material of a battery, an antistatic material or the like.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention can be applied as an antistatic material for plastic films, and as a conductive material for batteries, capacitors, electrochromic devices, etc. in the electrical and electronic industries.

0002

[Prior Art] Organic polymer materials with electronic conductivity are
In recent years, applications as batteries and various functional devices have been considered. For example, polyaniline (Unexamined Japanese Patent Publication No. 2-63
8), polypyrrole (JP-A No. 62-226568), polyacene (JP-A No. 63-301465), etc. are considered promising. These electronically conductive polymers are produced by electrolytic polymerization or chemical oxidative polymerization. In the electrolytic polymerization method, the amount produced is limited by the size of the electrode. (2) A process of peeling off the polymerization product from the electrode is required, which poses problems in mass production and cost.

[0003] When polyaniline and polypyrrole are used as electrodes for batteries, the capacity is 5.6wh/kg for polyaniline and 8.2wh/kg for polypyrrole.
kg (Chemistry and Industry, Vol. 42, No. 9, p. 1560, 1
989) and was small. In this regard, we are considering electrolytically polymerizing polypyrrole through nitrile-butadiene rubber and washing the nitrile-butadiene rubber afterwards to increase the available active sites in the polypyrrole film and improve its capacity (Aisaka et al., Journal ·of·
The Electrochemical Society, Volume 134,
2479, 1987), and polypyrrole having a polyethylene oxide group at the 3-position was obtained by electrolytic oxidation polymerization (JP-A-2-274723). Both methods showed an improvement in capacity, but because they involved electrolytic oxidation polymerization, they were not practical due to the cost. Also, 3, 6,
Electrolytically polymerized pyrrole containing 9-trioxadecyl group had a capacity 2 to 30 times that of unsubstituted polypyrrole in a system using polyethylene oxide polymer solid electrolyte, but the repeatability (M.G. Minet et al., Synthetic Metals, Vol. 28, p. C211, 1989). Also, 3
Polypyrrole with polyethylene oxide group in position (
JP-A-2-274723) also had poor repeatability. Furthermore, by using the chemical oxidation polymerization method disclosed in JP-A No. 63-215717, polypyrroles with superior capacity than the conventional chemical oxidation polymerization method can be obtained, but it is still difficult to sufficiently improve the capacity. It didn't work out.

0004

SUMMARY OF THE INVENTION An object of the present invention is to provide an electronically conductive polymer which has a higher capacity than conventional polymers and has excellent repeated charging and discharging characteristics, and a method for producing the same.

[0005]

[Means for Solving the Problems] The above problem is achieved by using a cupric compound as the oxidizing agent in an electron conductive polymer obtained by reacting at least a compound represented by the following general formula (1) with an oxidizing agent. This was achieved by using an electronically conductive polymer. General formula (1)

[0006]

[Case 2]

The compound of general formula (1) will be explained in more detail. L1 represents a divalent linking group, preferably -C(O)O- group, -C(O)CH2O-, -C(
O) NR7 - group, -CH2 O- group, -CH2 CH
2 O- group, -C(O)- group, -(O)S(O)- group. R7 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group. Particularly preferred as L1 are -C(O)O- group, -C(O)CH
2 O-, -CH2 O- group, -CH2 CH2 O-
group, -C(O)- group. L2 is synonymous with L1. R1 represents a divalent linking group, preferably an alkylene group or arylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, particularly preferably an alkylene group having 1 to 3 carbon atoms. It is. R2 is R1
is synonymous with R3 is a cyclic ester group, acyclic ester group, cyclic ether group, -(CH2CH2O)n
-R5 group represents a sulfonyl group, and n is an integer of 1 or more. R5 is an alkyl group having 1 to 3 carbon atoms. R3 is preferably a 5- to 7-membered cyclic carbonate group, a 5- to 7-membered lactone group, -C(O)OCH3,
-C(O)OC2 H5, -C(O)OC3 H7
, -C(O)CH3, -C(O)C2H5, -C
(O)C3H7, 3- to 12-membered cyclic ether, -
(O)S(O)CH3, particularly preferably

[0008]

[C3]

[0009] R4 is a hydrogen atom, a cyclic ester group, an acyclic ester group, a cyclic ether group, -(CH2
CH2O)n'-R5' group, sulfonyl group, alkyl group, aryl group, n' is an integer of 1 or more, R
5' is an alkyl group having 1 to 3 carbon atoms. R4 is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a group having the same meaning as the preferred group for R3. Particularly preferred as R4 is a hydrogen atom, carbon number 1
It is a group having the same meaning as the alkyl group, phenyl group, or group particularly preferred in R3. X is -NH-, -N(R
6)-, -S-, -O-, -Te-, -Se-, and R6 represents an alkyl group or an aryl group. X is preferably -NH-, -N(C6H5)-NCH3
-, -N(C2H5)-, -N(C3H7)
-, -S-, -O-, particularly preferably as X -
NH-, -N(CH3), -N(C6H5), -
S-, -O-. a, b, and c are each independently 0 or 1. Specific examples of the compound represented by the general formula (1) of the present invention are shown below, but the invention is not limited thereto.

0010

[C4]

[0011]

[C5]

0012

[C6]

The conductive polymer of the present invention can be obtained by oxidative polymerization using one or more compounds represented by the general formula (I).
) You may use one type or two or more types of monomers other than the compound represented by. Examples of monomers that can be used include heterocyclic compounds containing oxygen, nitrogen, sulfur, selenium, etc. as heteroatoms, and preferably,
These are furan, pyrrole, and thiophene.

When copolymerizing the general formula 1 of the present invention with a heterocyclic compound, the copolymerization can be carried out in any molar ratio, but preferably the compound of general formula 1 is in a molar ratio of 0.1% or more. is preferably contained in an amount of 1% or more. As the chemical oxidative polymerization method of the present invention, any commonly used chemical oxidative polymerization method can be used. For example, the above monomers are dissolved or dispersed in water or any organic solvent (which may contain water), and the catalyst (oxidizing agent) solution is gradually added at 60°C to -20°C (preferably 20°C to 0°C). It can be obtained by dripping. In the chemical oxidative polymerization method of the present invention, an aqueous dispersion of the polymer can be obtained by using an appropriate dispersant or surfactant, which is preferable because it has excellent moldability. When polymerizing the compound of the present invention, a cupric compound is used as an oxidizing agent. Examples of cupric compounds include Cu(BF4)2, Cu(ClO4)2
, Cu(PF6)2, Cu(AsF6)2,
Cu(CH3 C6 H4 SO3)2, Cu(C
Examples include F3 SO3 )2, but the present invention is not limited thereto. The amount of oxidizing agent varies depending on the properties of the compound of the present invention and the catalyst used, but can be used in a molar ratio of catalyst/compound of the present invention ranging from 0.01 to 10. In addition, as a solvent that can be used during polymerization, organic solvents (such as acetonitrile, dimethyl sulfuric acid, N,N-dimethylacetamide, N,N-
Examples include dimethylformamide, dimethylsulfoxide, sulfolane, formamide, dimethoxyethane, propylene carbonate, γ-butyl lactone, dioxane, methanol, ethanol, nitrobenzene, tetrahydrofuran, nitromethane, etc.), water, or a mixture of both. . Further, during chemical oxidative polymerization, a conductive compound may be added and polymerized. Conductive compounds include inorganic acids (e.g. HCl, H2SO
4, HClO4, BF4), organic acids (e.g. sulfonic acids such as toluenesulfonic acid, trifluoromethylsulfonic acid, polystyrene sulfonic acid, carboxylic acids such as formic acid, acetic acid, polyacrylic acid), organic bases (e.g. pyridine, triethanolamine), alkali metal cations (Li+, Na+, K+, etc.), NO+
, NO2 + , cation, onium cation (Et
4 N+, Bu4 N+, Bu3 P+, etc.) and negative ions (BF4 −, AsF6 −, SbF6 −
, SbCl6 − , PF6 − , ClO4 −
, AlF4 − , NiF4 2−, ZrF6 2−,
TiF6 2-, B10Cl102-, HSO4-
, SO4 2-, Cl-, Br-, F-, I-
), sulfonic acid anion (CH3 C6 H
4 SO3 − , C6 H5 SO3 − , CF3
salts containing carboxylic acid anions such as HCOOLi and sodium polyacrylate, chlorides such as FeCl3,
Examples include organic amine salts such as pyridine salts. Preferred specific examples of the polymer compound of the present invention are shown below,
Of course, it is not limited to these. The proportions of each component are expressed as weight percentages.

[0015]

[C7]

[0016]

[Chemical formula 8]

[0017]

[Chemical formula 9]

[0018]

[Chemical formula 10]

[0019]

[Chemical formula 11]

The electron conductive compound obtained in the present invention preferably has an average particle diameter of 1 μm to 250 μm from the viewpoint of self-discharge properties, more preferably 1 to 200 μm,
Particularly preferably, it is 1 to 150 μm.

[0021] Furthermore, when constructing a positive electrode active material for a battery using the electron conductive polymer obtained by the production method of the present invention, the electron conductive polymer can be used after being pulverized. As for the pulverization method, a known pulverization method can be used. For example, grinding with a ball mill, roll mill, rotary grinder, mortar, etc. The specific surface area of this electron conductive polymer is preferably 0.1 m2/g to 1,000 m2/g, and more preferably 0.5 m2/g/1,000 m2/g.
Particularly preferred is 1 m2/g to 1,000 m2/g. Further, the electron conductive polymer of the present invention can contain a conductive material such as carbon or a bonding agent such as Teflon.

The electronically conductive polymer obtained by the production method of the present invention can be laminated with a solid polymer electrolyte and used as a conductive material such as a polymer battery. The electron conductive polymer obtained by the production method of the present invention may form a plurality of layers, or may form a plurality of layers with a known electron conductive polymer. Further, it may further include a layer with a salt of a metal ion of group Ia or group IIa of the periodic table. However, it is preferable that the solid polymer electrolyte and the electronically conductive polymer obtained by the production method of the present invention are in direct contact with each other. Polymer solid electrolytes for obtaining laminated conductive materials with electronic conductive polymers obtained by the production method of the present invention include cationic polymers, anionic polymers, polyacrylonitrile, polyalkylene oxide polymers (
PEO, PPO, silicon compounds containing PEO, phosphazene, etc.), polyvinyl alcohol, etc., in combination with salts. Specific examples of these are disclosed in Japanese Patent Application Laid-open No. 1983
-256573, 61-124001, 62-
No. 20263, No. 62-139266, No. 63-24
No. 1066, No. 63-241026, No. 63-135
No. 477, No. 63-142061, No. 63-1306
No. 13, No. 60-23974, No. 63-136409
No. 63-193954, No. 63-186766, No. 63-205364, Macromolecules 21
It is described on page 648 of Vol. Examples of the salt constituting the solid polymer electrolyte include conductive salts used during polymerization in the chemical oxidative polymerization method described above. Preferably, it is a salt of a metal ion of group Ia or IIa of the periodic table, more preferably a Li salt, for example

002
3] LiBF4, LiClO4, LiCF3SO3
, LiPF6, toluenesulfonic acid lithium salt, and the like. In addition, any organic solvent (e.g. propylene carbonate, ethylene carbonate, γ-butyrolactone, dimethoxyethane, methyltetrahydrofuran, tetrahydrofuran, acetonitrile, 1,3-dioxolane) may be used in the solid polymer electrolyte to facilitate the diffusion of ions of the negative electrode material. , nitromethane, dimethylformamide, dimethyl sulfoxide, etc. may be impregnated alone or in combination.

[0024] When the electron conductive polymer obtained is in the form of a powder or a lump, the laminate conductive material can be produced by pressing a film processed by compression molding onto a solid polymer electrolyte membrane. In addition, when the obtained electron conductive polymer is a dispersion, roller coating, spin coating,
Known coating methods such as Giesser coating, dip coating, spray coating, and extrusion molding, and known drying methods can be used.

[0025] Furthermore, the electronically conductive polymer obtained by the production method of the present invention can also be used as a battery by laminating it with an electrolyte layer containing a salt of a metal ion of Group Ia or Group IIa of the periodic table. The laminated material may be formed by individually creating each component and then laminating them, or by applying or pressing a positive electrode material onto a separator and then laminating the negative electrode. The separator may be made of any organic solvent (e.g. propylene carbonate, ethylene carbonate, γ-butyrolactone, dimethoxyethane, methyltetrahydrofuran, acetonitrile, 1,3-dioxolane, nitromethane, dimethylformamide, Dimethyl sulfoxide, etc.) is preferably impregnated singly or in combination. A lithium salt may be added to the organic solvent. Examples of lithium salts include LiBF4, LiClO4
, LiCF3SO3, LiPF6, lithium toluenesulfonate, and the like. As the separator material, any material such as polyolefin, polyester, vinyl chloride, fluororesin, polyamide, polysulfone, cellulose, polyurethane, glass fiber, etc. can be used. Further, these may be subjected to treatments such as plasma treatment, glow treatment, radiation treatment, plasma polymerization, plasma initiated polymerization, radiation polymerization, and radiation initiated polymerization.

When the electron conductive polymer obtained by the production method of the present invention is used as a battery, oxides such as manganese, molybdenum, vanadium, titanium, chromium, niobium, cobalt, nickel, etc., and sulfides can be used as the positive electrode active material. substances, selenides, activated carbon (described in JP-A-60-167,280),
Carbon fiber (described in JP-A-61-10,882), polyaniline, amino group-substituted aromatic polymer, heterocyclic polymer,
Polyacene, polyyne compounds, etc. can be used in combination. Among them, activated carbon, γ-MnO2 (Japanese Patent Application Laid-open No. 1983-
108,455, 62-108,457), γ
-Mixture of β-MnO2 and Li2MnO3 (U.S. Pat. No. 4,758,484), amorphous V2O5
(JP-A-61-200,667), V6 O13, L
ix Niy Co(1-y) O2 (0.05≦x
≦1.10, 0≦y≦1) (JP-A-1-294372), MoS2 (JP-A-61-64,083), TiS
2 (Japanese Unexamined Patent Publication No. 62-222,578), polyaniline (
JP-A-60-65,031, JP-A No. 60-149,628,
61-281,128, 61-258,831, 62-90,878, 62-93,868, 62-
119,231, 62-181,334, 63-4
6,223), polyacetylene (JP-A-57-121,
168, 57-123,659, 58-40,78
1, 58-40,781, 60-124,370,
60-127,669, 61-285,678),
Polyphenylene is particularly effective. The electrode active material is usually carbon, silver (Japanese Patent Application Laid-Open No. 63-148,554) or polyphenylene derivatives (Japanese Patent Application Laid-open No. 59-20,971).
) or a bonding agent such as Teflon.

Examples of negative electrode active materials include metallic lithium, polyacene, polyacetylene, polyphenylene, and carbon (
In addition to lithium alloys, alloys such as aluminum and magnesium (Japanese Patent Application Laid-open No. 1-204361)
-65,670, 57-98,977), mercury alloy (
JP-A-58-111,265), alloys such as Pt (JP-A-60-79,670), Sn-Ni alloys (JP-A-60-79,670);
-86,759) and wood alloy (JP-A-60-167,
279), alloy with conductive polymer (JP-A-60-26
2,351), Pd-Cd-Bi alloy (JP-A-61-2
9,069), Ga-In alloy (JP-A-61-66,3
68), alloys such as Pb-Mg (JP-A-61-66,3
70), alloys such as Zn (Japanese Patent Application Laid-Open No. 61-68, 864)
, alloys such as Al-Ag (Japanese Patent Application Laid-Open No. 61-74, 258)
, alloys such as Cd-Sn (Japanese Patent Application Laid-Open No. 1986-91,864)
, Al-Ni and other alloys (JP-A-62-119,865
, 62-119,866), alloys such as Al-Mn (
U.S. Pat. No. 4,820,599) and the like are used. Among these, it is effective to use lithium metal, its Al alloy, and carbon.

[0028]

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is of course not limited to these. Example 1 (Compound Example I-1 Synthesis method) 40 g of (2-oxo-1,3-dioxolan-4-yl) methyl acrylate and 45 g of tosylmethyl isocyanide were added to a solution of ethyl ether/dimethyl sulfoxide (volume ratio 2/1). Dissolve in 500 ml of 60% sodium hydride at 15°C under nitrogen atmosphere.
It was added dropwise over 15 minutes to a mixed solution of 2 g and 100 ml of ethyl ether with stirring. Furthermore, the reaction temperature was raised to 40° C. and stirred for 15 minutes. Then ethyl ether 700m
1 was added and the washing was repeated three times with 200 ml of water. After drying the ether layer with magnesium sulfate, the ether was distilled off under reduced pressure and purified by silica gel column chromatography to obtain 17 g of liquid compound I-1. Elemental analysis and
It was confirmed to be I-1 by 1H-NMR. C9 H9
O5 N, C; 51.26%, H; 4.44%, N;
6.51% (calculated value C; 51.18%, H; 4.30%
, N; 6.63%) 1H-NMR solvent CDCl3
4.20~4.70ppm (4H, m), 4.90~
5.10ppm (1H, m), 6.55-6.65pp
m (1H, m), 6.75-6.85 ppm (1H, m
), 7.35-7.45 ppm (1H, m) Example 2 6 g of compound I-1 and 1.8 g of pyrrole were dissolved in 500 ml of acetonitrile and cooled on ice. While vigorously stirring this solution, a solution prepared by dissolving 27 g of a 45% copper borofluoride aqueous solution and 25 ml of acetonitrile was added dropwise over 1 hour while keeping the temperature below 5°C. After stirring was continued for 4 hours while maintaining the temperature at 5° C. or lower, a black precipitate formed was filtered off. This black solid was washed with 100 ml of propylene carbonate and 500 ml of acetonitrile to obtain 4.8 g of product (P-1 polymer). The composition ratio was determined by elemental analysis values. The surface area was measured using the BET method and was 8.5m2/g.
Met. Further, when the particle size was measured using a laser diffraction type particle size distribution analyzer, the particle size was 1 μm to 860 μm, and the average particle size was 110 μm. Further, when pellets were prepared using P-1 polymer and the electrical conductivity was measured by the four-terminal method, it was found to be 1.9 x 10-1 s/cm.

Examples 3 to 14 In the same manner as in Example 2, P-2, 3, 4,
5, 6, 8, 11, 12, 19, 20, 21, 23, 2
4 was synthesized and its specific surface area, average particle size, and electrical conductivity were measured. The results are shown in Table 1.

[0030]

[Table 1]

Example 15 Polymer P-2 was ground using a mortar to obtain polymer P-S. Table 1 shows the specific surface area and electrical conductivity.

Example 16 P-1 polymer 300mg, acetylene black 20m
g and 20 mg of Teflon were mixed and pressure molded to form pellets. The density of the pellet at this time is 1.39g/c
It was m3. This pellet was used as a positive electrode, lithium metal was used as a negative electrode, and propylene carbonate/dimethoxyethane containing 1 mol/l LiBF4 was used as an electrolyte = 1/
1 (volume ratio), the battery shown in Figure 1 was created, and 2.5
Charging and discharging were performed between V and 3.5V. Table 2 shows the discharge capacity at the 10th cycle and the 200th cycle.

[0033]

[Table 2]

Examples 17 to 23 Experiments were conducted in the same manner as in Example 16 except that P-1 was changed. Table 2 shows the compounds used and the results.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 2 using 10 g of pyrrole to obtain a black product C-1. Table 1 shows the average particle size, specific surface area, and electrical conductivity of C-1. Example 16 using C-1
An experiment was conducted in the same manner. The results are shown in Table 2.

Comparative Example 2 Using 10 g of N-position PEO polymer (Compound A), polymerization was carried out in the same manner as in Example-2 to obtain a black product C-2. Table 1 shows the average particle size, specific surface area, and electrical conductivity of C-2. An experiment was conducted in the same manner as in Example 16 using C-2. The results are shown in Table 2. Compound A

[0037]

[Chemical formula 12]

Comparative Example 3 4.0 g of Compound I-1 and 5 g of pyrrole were dissolved in 500 ml of acetonitrile-water (volume ratio 1:1) and kept at 5°C. While stirring this solution vigorously, add 80 g of ferric chloride.
A solution prepared by dissolving this in 200 ml of acetonitrile was gradually added dropwise. The produced black precipitate was washed in the same manner as in Example 1 to obtain 2.9 g of product (C-3). Table 1 shows the specific surface area and electrical conductivity of C-3. An experiment was conducted in the same manner as in Example 16 using C-3. The results are shown in Table 2.

Example 24 The battery prepared in Example 16 was left at 65° C. for 200 days and its capacity was measured, and the self-discharge rate was 13.2%.

Comparative Example 1 Using the battery prepared in Comparative Example 1, the self-discharge rate was measured in the same manner as in Example 24, and the self-discharge rate was 28%. The electron conductive polymer of the present invention has a larger capacity than the unsubstituted polypyrrole shown in Comparative Example 1 in Table 2. Further, as shown in Comparative Example 2 in Table 2, polypyrrole having a polyethylene oxide group at the N position has a relatively high capacity but is inferior to the present invention in terms of repeatability. Furthermore, as shown in Comparative Example 3 in Table 2, when an oxidizing agent other than a cupric compound is used, the capacity is inferior to that oxidized with a cupric compound. Further, as shown in Example 24, the compound of the present invention is also superior to the conventional compound in terms of self-discharge rate. From the above, it is clear that the electron conductive polymer of the present invention is superior to the conventional technology.

[0041]

[Effect of the invention] According to the present invention, the capacity and repeatability characteristics,
An electronically conductive polymer with excellent self-discharge properties can be obtained.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view of a coin-shaped battery used in Examples 16 to 27 and Comparative Examples 1 and 2.

[Explanation of symbols]

1. A positive electrode active material containing the compound of the present invention is shown. 2. A nonwoven fabric impregnated with an electrolyte solution is shown. 3. Indicates the negative electrode active material (lithium). 4. The stainless steel case is shown. 5. Indicates insulating synthetic rubber.

Claims (4)

[Claims] [Claim 1] In a method for producing an electron-conductive polymer obtained by reacting an oxidizing agent with at least one compound represented by the following general formula (1), a cupric compound is used as the oxidizing agent. An electronically conductive polymer characterized by General formula (1) [Chemical formula 1] 2. The electron conductive polymer according to claim 1, wherein the copolymerized repeating unit is a heterocyclic compound. [Claim 3] The average particle diameter of the polymer compound is 1 μm.
The electron conductive polymer according to claim 1 or 2, wherein the electron conductive polymer has a diameter of 200 μm or more. 4. A positive electrode material for a battery, characterized in that the electron conductive polymer according to claim 1, 2 or 3 is used.