JPH0373992B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a battery with good performance. consisting of a transition metal compound and an organometallic compound,
Acetylene polymers obtained by polymerizing acetylene using a so-called Ziegler-Natsuta catalyst are
Because the electrical conductivity is in the semiconductor region,
It is already known that organic semiconductor materials are useful as electrical and electronic devices. However, the acetylene polymer obtained in this way does not melt even when heated, and it easily undergoes oxidative deterioration under heating, so it cannot be molded using the usual molding method used for thermoplastic resins. I can't. Furthermore, no solvent has been found that melts this acetylene polymer. Therefore, the conventional methods for producing practical molded products of acetylene polymers are (a) pressure molding of amorphous powdery acetylene polymers, and (b) polymerization under special polymerization conditions. At the same time, the method was limited to the method of obtaining a film-like acetylene polymer by forming it into a film (Japanese Patent Publication No. 32581/1983). However, with method (a), only molded products with low mechanical strength can be obtained, while with method (b), only molded products with low mechanical strength can be obtained.
Although it has the advantage of having higher mechanical strength than the molded product obtained by the above method, it has the disadvantage that it is difficult to perform post-processing, so only a porous film with a substantially thin film thickness can be obtained. It was hot. The amorphous powdery acetylene polymer molded product obtained by the method (a) above is mixed with BF ₃ , BCl ₃ , HCl, Cl ₂ ,
Chemical treatment with electron-accepting compounds (acceptors) such as SO ₂ , NO ₂ , HCN, O ₂ , and NO increases electrical conductivity by up to three orders of magnitude, while electron-donating compounds such as ammonia and methylamine It is already known that the electrical conductivity decreases by up to four orders of magnitude when treated with (donor) [DJBerets et al., Trans.
Farady Soc., 64 , 823 (1986)]. In addition, I ₂ , Cl ₂ , Br ₂ , ICl, IBr,
By chemically doping electron-accepting compounds such as ASF ₃ , SbF ₅ , PF ₆ etc. or electron-donating compounds such as Na, K, Li, etc., the electrical conductivity of the acetylene polymer can be increased from 10 −8 to 10 ⁻⁸ . It is already known that it can be freely controlled over a wide range of 10 ³ Ω ^-1 cm ^-1 [JCSChem.Commu., 578
(1977), Phys.Rev.Lett., 39 , 1098 (1977), J.
Am.Chem.Soc., 100 , 1013 (1978), J.Chem.
Phys., 69 , 5098 (1978)]. The idea of using this doped film-like acetylene polymer as an anode material for primary batteries has already been proposed (Mole-cular Metals, Metals, NATO
Conference Series, Series VI, 471−489
(1978)). On the other hand, in addition to the above chemical doping method, electrochemical doping methods such as ClO ₄ ^- , PF ₆ ^- , ASF ₄ ^- ,
Anions such as CF ₃ SO ₃ ^- , BF ₄ ^- , etc.
A method for producing p-type and n-type conductive acetylene polymers by doping cations such as R′ ₄ N ⁺ (R′: alkyl group) into acetylene polymers has already been developed [JCSChem.Commu ., 1979 ,
594, C&EN Jan. 26 , 39 (1981), JCSChem.
Comm., 1981 , 317]. A rechargeable battery using electrochemical doping using the crystalline film-like acetylene polymer obtained by method (b) has been reported (Paper Presented at the
International Conference on Low Dimensions
ional Synthctic Metals.Hersinger.Denmark.10
~15, August1980). For example, this battery is made by using two 0.1 mm thick acetylene polymer films obtained by method (b) as positive and negative electrodes, and soaking them in a tetrahydrofuran solution containing lithium iodide to generate a voltage of 9V. When connected to a DC power source, lithium iodide is electrolyzed, and the acetylene polymer film at the anode is doped with iodine, and the acetylene polymer film at the cathode is doped with lithium.
This electrolytic doping corresponds to the charging process. When a load is connected to the two doped electrodes, lithium ions and iodine ions react to generate electricity. In this case, the open circuit voltage (Voc) is
2.8V, the short-circuit current density was 5mA/ ^cm2 , and when a tetrahydrofuran solution of lithium perchlorate was used as the electrolyte, the open circuit voltage was 2.5V, and the short-circuit current density was about 3mA/ ^cm2. . This battery uses an acetylene polymer as its electrode material, which is easy to reduce weight and size, so it is lightweight and has high energy density.
It is attracting attention as a battery that is easy to miniaturize and is inexpensive. However, the acetylene polymers used in these known documents were crystalline porous membrane-like acetylene polymers produced by the method (b) above. This film-like acetylene high polymer is difficult to post-process, and the film thickness of the film-like acetylene high polymer produced by this method is at most 200 μm.
Practically speaking, a film thicker than this is required, and the mechanical strength of this film is not necessarily sufficient.
Furthermore, the performance of batteries using this film as electrodes, such as cycle life, voltage flatness during discharge, and charging/discharging efficiency, was not necessarily satisfactory. Therefore, the use of known batteries using the membrane-like acetylene polymer produced by the method (b) as an electrode material has been extremely limited. On the other hand, JP-A-56-120715
The publication proposes that a high-strength film-like acetylene polymer be obtained by polymerizing acetylene while standing in a catalyst solution in which a polymer is dissolved. However, in the case of acetylene-based high polymer powder as used in the present invention, when polymerization is carried out in a catalyst solution in which the polymer is dissolved, not only the inside but also the surface of the acetylene-based polymer powder is formed. The dissolved polymer precipitates out and becomes very non-uniform. As a result, for example, when used as a battery electrode, when a dopant is doped into a molded product (especially fibrils) of acetylene polymer powder, the polymer not only becomes an obstacle, but also dissolves into the electrolyte. This appears as a decrease in the conductivity of the electrolyte. Furthermore, since it is a polymer that dissolves in the acetylene polymerization solvent, it is not only difficult to say exactly what percentage it will precipitate in the acetylene polymer, but also it is extremely difficult to manufacture because it will elute during the removal of the polymerization catalyst. Therefore, there is a desire among those involved to establish a lightweight, compact, and inexpensive battery that has high energy density, flatness during discharge, and good cycle life, and is made of electrodes that are easy to mold and have high mechanical strength. It was requested. In view of the above points, the present inventors have developed an electrode that is easy to mold, has high energy density, has electrodes with high mechanical strength, has good cycle life and flatness of voltage during discharge, and is lightweight and compact. The present invention was completed as a result of various studies aimed at obtaining a battery that is easy to use and inexpensive. That is, the present invention provides a fibrillar polymer composition in which an acetylene compound is polymerized on the surface of a thermoplastic polymer powder, wherein the ratio of the thermoplastic polymer powder to the entire polymer composition is 1 weight. % to 60% by weight of the molded body in at least one of the positive electrode and the negative electrode. This molded body is obtained by molding a polymer composition obtained by polymerizing an acetylene compound in the presence of a thermoplastic polymer powder. If the battery according to the present invention is a primary battery, ()
Large discharge capacity, () Good voltage flatness during discharge, () Less self-discharge. On the other hand, in the case of secondary batteries, ()
High energy density, () Good voltage flatness during discharge, () Less self-discharge,
(2) It has the advantage of long life after repeated charging and discharging. The acetylene compound used in the present invention has a structure represented by formula (1), and includes homopolymerization and copolymerization thereof, which is herein referred to as polymerization. (Here, R is a hydrogen atom, a halogen, a halogenated hydrocarbon group containing a halogen atom and having 6 or less carbon atoms, an alkyl group having 6 or less carbon atoms, or a halogenated hydrocarbon group having 6 or less carbon atoms.
~10 aryl groups. ) As a representative example,
Examples include acetylene, phenylacetylene, methylacetylene, hexylacetylene, butylacetylene, naphthylacetylene, chloroacetylene, chloromethylacetylene, and bromoacetylene, with acetylene being particularly preferred. Further, there is no particular restriction on the form of the polymerization reactor for producing the acetylene-based high polymer. Moreover, these acetylene-based polymers are produced using a Ziegler type catalyst, a Rutzinger catalyst, or a metathesis catalyst. As the polymerization solvent, an inert solvent that does not dissolve the thermoplastic polymer described below can be used. The thermoplastic polymer powder in the present invention includes:
Those that are substantially insoluble in the polymerization solvent and battery electrolyte are used, preferably those with a softening point or melting point.
A polymer or copolymer having a temperature of 200°C or less is used.
If a polymer with a temperature exceeding 200° C. is used, it becomes necessary to raise the thermoforming temperature of the resulting polymer composition, which is not preferable for certain types of acetylene compounds used. Examples include low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer, poly(tetrafluoroethylene), poly(trifluoroethylene). ), polyolefins such as poly(difluoroethylene), polyamides, polyesters, polycarbonates, etc., or mixtures thereof with conductive materials such as acetylene black, carbon black, graphite, and metal fibers. By polymerizing the acetylene compound in the presence of the powder, a powdery or small-sized polymer composition can be obtained, and a preferred polymerization method includes polymerization under mechanical stirring. The proportion of thermoplastic polymer in the polymer composition is from 1 to
It needs to be 60% by weight, and if it is less than 1% by weight, the effect of improving battery performance will not be sufficiently exhibited, and
If it exceeds 60% by weight, the original characteristics as an electrode material will be lost. Specific examples of methods for producing the polymer composition include a method in which a predetermined amount of thermoplastic polymer powder is added to a catalyst solution and then polymerized by blowing acetylene gas into the catalyst solution; A method for polymerizing by adding a certain amount of thermoplastic polymer powder and then blowing acetylene gas, and a method in which a catalyst solution is prepared in the presence of a predetermined amount of thermoplastic polymer powder, and then polymerizing by blowing acetylene gas. Methods may be mentioned, but the method is not necessarily limited to these methods. Regarding the post-processing method, there are no limitations specific to this manufacturing method, and all known methods can be applied. Furthermore, the polymerization reactor needs to have a configuration that allows sufficient stirring. As a method for manufacturing a molded article from the obtained composition, a known cold working method or a thermoforming method is adopted, and the thermoforming is preferably carried out at a temperature of 200° C. or lower. The electrode forming method is described in Japanese Patent Application Laid-open No. 55-128419.
No. 56-10428, No. 56-63448, No. 56-
No. 133133, Patent Application No. 56-150647, No. 57-88823,
No. 57-88824, No. 57-110842, No. 57-110583
No. 57-110586, No. 57-159532, etc., but the method is not particularly limited to these methods. As the electrode of the battery of the present invention, not only a molded body made of the above composition but also a conductive polymer compound obtained by doping a high polymer of an acetylene compound in the molded body by an appropriate method can be used. can do. Of course, when the molded product of the present invention is used as an electrode for a primary battery, it is necessary to use a composite obtained by doping the molded product with a high polymer of an acetylene compound with a dopant. The doping method may be either chemical doping or electrochemical doping. As dopants for chemical doping,
Various electron-accepting and electron-donating compounds known in the art include (1) halogens such as iodine, bromine and bromine iodide; () arsenic pentafluoride;
Metal halides such as antimony pentafluoride, silicon tetrafluoride, phosphorus pentachloride, phosphorus pentafluoride, aluminum chloride, aluminum bromide and aluminum fluoride, () sulfuric acid, nitric acid, fluorosulfuric acid,
Protic acids such as trifluoromethane sulfuric acid and chlorosulfuric acid, () sulfur trioxide, nitrogen dioxide,
Oxidizing agents such as difluorosulfonyl peroxide, ()AgClO ₄ , ()tetracyanoethylene, tetracyanoquinodimethane, chloranil,
Examples include 2,3-dichloro-5,6-dicyanoparabenzoquinone and 2,3-dibromo-5,6-dicyanoparabenzoquinone. As a dopant for electrochemical doping, ()
Halide anions of group a elements such as PF ₆ ^- , SbF ₆ ^- , AsF ₆ ^- , SbCl ₆ ^-, halide anions of group a elements such as BF ₄ ^- , I ^- (I ₃ ^- ), Br ^- ,
anionic dopants such as halogen anions such as Cl ^- , perchlorate anions such as ClO ₄ ^- and alkali metal ions such as ()Li ⁺ , Na ⁺ , K ⁺ ;
Examples include cations and dopants such as quaternary ammonium ions such as R ₄ N ⁺ (R: a hydrocarbon group having 1 to 20 carbon atoms), but are not necessarily limited to the following. The above-mentioned anion/dopant and cation/dopant
Specific examples of compounds that provide dopants include
LiPF ₆ , LiSbF ₆ , LiAsF ₆ , LiClO ₄ , NaI,
_NaPF6 , _NaSbF6 , _NaAsF6 , _NaClO4 , KI,
KPF ₆ , KSbF ₆ , KAsF ₆ , KClO ₄ , [(n-
Bu) ₄ N] ⁺・(AsF ₆ ) ^- , [(n-Bu) ₄ N] ⁺・(PF ₆ ) ^-
,
[(n-Bu) ₄ N] ⁺ .ClO ₄ , LiAlCl ₄ , and LiBF ₄ can be mentioned, but the material is not necessarily limited to these. These dopants may be used alone or in combination of two or more. As anion dopants other than those mentioned above,
HF ₂ ^-anion , and other cation dopants include pyrylium or pyridinium cations represented by the following formula (): (In the formula, ~10 alkyl group, aryl group having 6 to 15 carbon atoms, m is 0 when X is an oxygen atom, and 1 when X is a nitrogen atom. n is 0 or 1 to 5. ) or a carbonium cation represented by the following formula () or (): and [In the above formula, R ¹ , R ² , R ³ are hydrogen atoms (R ¹ , R ² , R ³
is not a hydrogen atom at the same time), carbon number is 1
-15 alkyl group, allyl group, aryl group having 6 to 15 carbon atoms or ^-OR5 group, provided that R ⁵ is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms ( aryl) group, R ⁴ is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or a C 6 to 15 alkyl group.
15 aryl groups. ] It is. The HF ₂ ^-anion used usually has the following general formula (), () or (): R′ ₄ N·HF ₂ () M·HF ₂ () [However, in the above formula, R', R'' is a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 15 carbon atoms, R is an alkyl group having 1 to 10 carbon atoms,
An aryl group having 6 to 15 carbon atoms, X is an oxygen atom or a nitrogen atom, and n is 0 or a positive integer of 5 or less. M is an alkali metal. ] It can be obtained by dissolving the compound (hydrogen fluoride salt) represented by as a supporting electrolyte in an appropriate organic solvent. Specific examples of compounds represented by the above formulas (), () and () include H ₄ N・HF ₂ ,
^Bun ₄ N・HF ₂ , Na・HF ₂ , K・HF ₂ , Li・HF ₂ and

[Formula] can be given. The pyrylium or pyridium cation represented by the above formula () is the cation represented by the formula () and ClO ₄ ^- , BF ₄ ^- , AlCl ₄ ^- , FeCl ₄ ^- ,
SnCl ₅ ^- , PF ₆ ^- , PCl ₆ ^- , SbF ₆ ^- , AsF ₆ ^- ,
It can be obtained by dissolving it in an appropriate organic solvent using a salt with an anion such as CF ₃ SO ₃ ^- or HF ₂ ^- as a supporting electrolyte. Examples of such salts include

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] etc. can be given. Specific examples of carbonium cations represented by the above formula () or () are (C ₆ H ₅ ) ₃ C ⁺ ,
( _CH3 ) _3C ⁺ ,

【formula】

[Formula] can be given. These carbonium cations can be obtained by dissolving salts of them and anions (carbonium salts) in a suitable organic solvent as a supporting electrolyte. Representative examples of anions used here include BF ₄ ^- , AlCl ₄ ^- , AlBr ₃ Cl ^- , FeCl ₄ ^- ,
SnCl ₃ ^- , PF ₆ ^- , PCl ₆ ^- , SbCl ₆ ^- , SbF ₆ ^- , ClO ₄ ,
^Examples of carbonium salts include (C _{6 H 5 ) 3 C}・
BF ₄ , (CH ₃ ) ₃ C・BF ₄ , HCO・AlCl ₄ , HCO・
Examples include BF ₄ , C ₆ H ₅ CO・SnCl ₃ and the like. The electrolytic solution used in electrochemical doping can be either an aqueous solution or a non-aqueous solution, but is preferably one in which the dopant is dissolved in a non-aqueous organic solvent. The organic solvent referred to herein is preferably one that does not substantially dissolve the thermoplastic resin in the electrode, is aprotic, and has a high dielectric constant. For example, ethers, ketones, nitriles, amides, sulfur compounds, chlorinated hydrocarbons, esters, phosphate ester compounds, phosphite compounds, carbonates, nitro compounds, etc. can be used. Among these, ethers, ketones, nitriles, chlorinated hydrocarbons, and carbonates are preferred. Representative examples of these include tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, monoglyme, acetonitrile, propionitrile, 4-methyl-2-pentanone, butyronitrile, benzonitrile, 1,2-dichloroethane, and γ-butyrolactone. , dimethoxyethane, methylformate, propylene carbonate, ethylene carbonate, dimethylformamide, dimethylsulfoxide, dimethylthioformamide, sulfolane, ethyl phosphate, methyl phosphate, ethyl phosphite, methyl phosphite, etc. However, it is not necessarily limited to these. These organic solvents may be used alone or as a mixed solvent of two or more. The amount of the dopant doped into the acetylene compound high polymer in the composite is 2 to 40 mol%, preferably 2 to 40 mol% per mole of the repeating unit (monomer) of the acetylene compound high polymer. It is 4 to 30 mol%, particularly preferably 5 to 20 mol%. Even if the amount of the doped dopant is less than 2 mol % or more than 40 mol %, a battery with a sufficiently large discharge capacity cannot be obtained. Generally, the electrical conductivity of a high polymer of conductive acetylene compound obtained by doping is
Approximately 10 ^-4 Ω ^-1 cm when used as an electrode for a primary battery
It is preferable that the electrical conductivity is larger than ^-1 . On the other hand, when used as an electrode of a secondary battery, there is no particular restriction on the electrical conductivity. The amount of doping can be freely controlled by measuring the amount of electricity flowing during electrolysis. The doping may be carried out either under constant current, constant voltage or under conditions of varying current and voltage. The current value, voltage value, doping time, etc. during doping vary depending on the bulk density and area of the electrode used, the type of dopant, the type of electrolyte, and the required electrical conductivity of the polymer composition. cannot be specified. The supporting electrolyte and solvent of the electrolyte of the battery of the present invention are the same as those used in the electrochemical doping, and the doping conditions are determined by the method described above or by a conventionally known method (JCS, Chem,
Commu., 1981 , 317). In the battery of the present invention, in addition to the electrolyte described above, a highly ion conductive organic solid electrolyte consisting of polyethylene oxide and NaI, NaSCN, etc., or a mixture of an electrolyte (dopant) with a saturation solubility or higher and an organic solvent may be used. I can do it. Furthermore, the concentration of the electrolyte used in the battery of the present invention cannot be unconditionally defined because it varies depending on the type of positive electrode or negative electrode used, charge/discharge conditions, operating temperature, type of electrolyte, type of organic solvent, etc. It may be either a homogeneously dissolved system or a heterogeneous system, but it is usually in the range of 0.001 to 10 mol/. As a specific example of the secondary battery of the _battery of the present invention, when an acetylene polymer is used as the acetylene polymer in the composite, and if the acetylene polymer is ( _CH ) )/LiClO ₄ (electrolyte)/(CH) _X (negative electrode), (CH) _X (positive electrode)/LiBF ₄
(Electrolyte) / Li (negative electrode), [(CH) ^+0.024 (ClO ₄ ) ^- _{0.0
twenty four} 〕
_X (positive electrode) / (n-Bu ₄ N) ⁺・(ClO ₄ ) ^- (electrolyte) / [(n-Bu ₄ N) ⁺ _0.024 (CH) ^-0.024 ] _X (negative electrode)
,
[(CH) ^+0.06 (PF ₆ ) ^- _0.06 ] _X (positive electrode)/(n-
Bu ₄ N) ⁺・(PF ₆ ) ^- (electrolyte)/[(n-Bu ₄ N) ⁺ _0.06
(CH) ^-0.06 〕 _X (negative electrode), [(CH) ^+0.050 (ClO ₄ ) ^-0.0
50 〕 _X
(Positive electrode) / (n-Bu ₄ N) ⁺・(ClO ₄ ) ^- (Electrolyte) /
[(CH) ^+0.020 (ClO ₄ ) ^-0.020 ] _X (negative electrode), [(n-
Bu ₄ N) ^+0.02 (CH) ^-0.02 ] _X (Positive electrode)/(n-
Bu ₄ N) ⁺・(ClO ₄ ) ^- (electrolyte)/[(n-Bu ₄ N) ⁺ _0.07
(CH) ^-0.07 ] _X (negative electrode), [(CH) ^+0.010 (I ₃ ) ^-0.010
〕 _X
(Positive electrode) / NaI (electrolyte) / [(CH) ^-0.010 (Na) ^+0.0
10 ] (negative electrode). As another specific example, if polyparaphenylene is (C ₆ H _{4 ) X} and poly(2,5-thienylene) is (C ₄ H ₂ S) _X , then ( _{CH ) H4} )
Examples include _X. (CH) _X /LiClO ₄ /(C ₄ H ₂ S). Further, as an example of a primary battery, there can be mentioned one in which a molded body of a polymer composition is used as a positive electrode and a metal having a Pauling's electronegativity not exceeding 1.6 is used as a negative electrode. Examples of the metal used as the negative electrode active material include alkali metals such as lithium and sodium, aluminum, and magnesium. Among these, lithium and aluminum or alloys thereof are preferred. These metals may be used in sheet form as in general lithium batteries, or they may be crimped onto a nickel or stainless steel mesh. In the present invention, if necessary, a porous membrane made of synthetic resin such as glass, polyethylene, or polypropylene, or natural fiber paper may be used as the diaphragm. The battery of the present invention has high energy density, long cycle life, and good voltage flatness during discharge and charge/discharge efficiency. Furthermore, the battery according to the present invention is lightweight, compact, and has a high energy density, so it is suitable for use in portable devices, electric vehicles, gasoline vehicles, and power storage batteries. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 The glass crepe of 1 has a density of 0.93 g/cm ³ ,
Add 1 g of linear low-density polyethylene powder (MI8.2 g/10 min), 200 ml of toluene, 0.8 g (7 mmol) of triisobutylaluminum, and 1.2 g (3.5 mmol) of tetrabutyl titanate, stir at room temperature for 2 hours, and add acetylene gas. I blew it. After polymerization,
Separate the powder part, wash with toluene 6 times and dry.
5 g of powder containing 20% by weight of thermoplastic polymer was obtained. When this composition was observed under an electron microscope, it was found to be fibrillar, and it is presumed that the composition was polymerized on the surface of the thermoplastic polymer. Press this powder to 100
Kg/cm ² , from a molded body made from a polymer composition obtained by hot pressing at a temperature of 100°C, two small pieces with a width of 0.5 cm and a length of 2.0 cm were cut out, and the two pieces were separated into separate pieces. They were mechanically crimped and fixed to a platinum wire to form a positive electrode and a negative electrode, respectively. The concentration of E+4N・BF ₄ is 1.5
Using an acetonitrile solution of mol/cm2 as the electrolyte, charging was carried out for 25 minutes at a constant current (5.0 mA/cm ² ) (amount of electricity equivalent to 6 mol% doping amount for the acetylene polymer), and immediately after charging was completed, A repeated charging/discharging test was conducted in which the battery was discharged at a constant current (5.0 mA/cm ² ) and when the voltage reached 1 V, it was charged again under the same conditions as above, and it was possible to repeat it up to 476 times. As a result of the 10th repeated test, the theoretical energy density for 1 kg of acetylene high polymer in the composite used was 116 W·hr/Kg, and the charge/discharge efficiency was 97%. Furthermore, the ratio of the amount of electricity discharged until the voltage decreased to 1.5V during discharge to the total amount of electricity discharged was 93%. Comparative Example 1 An acetylene high polymer was obtained by polymerizing in the same manner as in Example 1 except that the linear low-density polyethylene was not added. A sample for evaluation was prepared by molding in the same manner as in Example 1. [Battery experiment] was carried out in the same manner as in Example 1 except that the acetylene polymer obtained by the above method was used instead of the molded body used in Example 1.
After repeated charging and discharging tests, charging became impossible after the 169th time. After the test, when we removed the acetylene polymer from the electrode, we found that the membrane had been destroyed. In addition, as a result of the 10th repeated test, the theoretical energy density was 112W・hr/Kg, and the charge/discharge efficiency was
It was 93%. Further, the ratio of the amount of electricity discharged until the voltage decreased to 1.5V during discharge to the total amount of electricity discharged was 84%. Example 2 Instead of the linear low density polyethylene in Example 1, a material with a density of 0.95 g/m containing 5% carbon black was used.
cm ³ , MI 2.0 g/10 min polyethylene was ground into powder, 2 g, and instead of tetrabutyl titanate, 50 g of diethoxymagnesium and 10 g of tetrabutyl titanate were mixed in a vibrating ball mill (1
Approximately 50% of the internal volume is made up of magnetic balls with a diameter of 10 mm. ) Polymerization was carried out in the same manner except that 3 g of the powder pulverized with 3 g of powder was added to obtain 16 g of powder. The proportion of thermoplastic polymer in the resulting composition was about 12% by weight.
From the molded product obtained by molding in the same manner as in Example 1,
Cut out two small pieces with a width of 0.5 cm and a length of 2.0 cm, mechanically press and fix them to a platinum wire, and attach the positive electrode to the platinum wire.
It was used as a negative electrode. The concentration of E+4N・BF ₄ is 1.5 mol/
Using an acetonitrile solution as an electrolyte, charging was carried out at a constant current (3.0 mA/cm ² ) (amount of electricity equivalent to a doping amount of 6 mol%), and after charging was completed,
The battery was immediately discharged under a constant current (3.0 mA/cm ² ), and when the voltage reached 1.0 V, it was charged again under the same conditions as described above. A repeated charging/discharging test was possible up to 493 times. As a result of the 10th repeated charge/discharge test, the theoretical energy density for 1 kg of active material used was
It was 118W・hr/Kg, and the charge/discharge efficiency was 98%. Further, the ratio of the amount of electricity discharged until the voltage decreased to 1.5V during discharge to the total amount of electricity discharged was 93%. Comparative Example 2 Polymerization was carried out in the same manner as in Example 1 except that 20 g of polystyrene having a weight average molecular weight of 200,000 was added and dissolved in place of the linear low density polyethylene in Example 1 to obtain 4 g of powder. Infrared spectroscopy revealed that 5% by weight of polystyrene was present in the powder. When the resulting powder was observed under an electron microscope, it was found that in addition to the fibrillar portions inherent to the acetylene polymer, polystyrene-shaped portions were non-uniformly dispersed. This powder was heated to a pressure of 500Kg/cm ² ,
Example 1 except that a composite of polyacetylene and polystyrene obtained by molding at a temperature of 200°C was used.
When we conducted a [battery experiment] in the same manner as
Charging became impossible after the 258th time. When the electrode was taken out after the test, it was found that the electrode membrane had been destroyed. Furthermore, as a result of the 10th repeated test, the theoretical energy density was 109 W·hr/Kg, and the charge/discharge efficiency was 91%. Further, the ratio of the amount of electricity discharged until the voltage decreased to 1.5V during discharge to the total amount of electricity discharged was 89%. Examples 3 to 5 Comparative Example 3 A battery for evaluation was polymerized and molded in the same manner as in Example 1 except that the amount of linear low-density polyethylene powder was changed as shown in Table 1. was created. Then, a repeated charging/discharging test was conducted, and the results are also shown in Table 1.

【table】

Claims (1)

[Claims] 1 A fibrillar polymer composition in which an acetylene compound is polymerized on the surface of a thermoplastic polymer powder, wherein the proportion of the thermoplastic polymer powder to the total polymer composition is 1% by weight to 60% by weight. % in at least one of the positive and negative electrodes.