JPS59112584A - Battery - Google Patents

Abstract

PURPOSE:To obtain a battery which has a high energy density, a good cycle life, good charge and discharge efficiency and a good flatness in voltage during discharge and can easily be reduced in weight and size by providing a metallic film layer on the current-collector-side surface of an electrode. CONSTITUTION:In a battery in which either macromolecular compound having conjugated double bond in the principal chain or a conductive macromolecular compound obtained by doping the above macromolecular compound with a dopant is used as an active material for at least one of the electrodes, a metallic film layer is provided on the current-collector-side surface of the above electrode. Vacuum vapordeposition, ion sputtering, ion plating or similar method is used in forming the metallic film layer on one surface of the conjugate macromolecular compound. Al or the like is used as the metal and the thickness of the metallic layer usually is adjusted to 10-1,000Angstrom . If the thickness of the metallic layer is less than 10Angstrom , sufficient improvement of the battery performance will not be achieved. Besides, no greater improvement of the battery performance will be observed even if the thickness exceeds 1,000Angstrom .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides that 1 ft of a polymer compound having a conjugated double bond in its main chain and having a metal film layer on the surface on the current collector side is used as an active material of an electrode by adding a dopant to the polymer compound. This invention relates to a battery with good performance using a conductive polymer compound obtained by doping.

It consists of a transition metal compound and an organometallic compound.

It is already known that the acetylene polymer obtained by polymerizing acetylene using a so-called Ziegler-Natsuta catalyst is an organic semiconductor material useful as electrical and electronic devices because its insulating conductivity is in the semiconductor region. It is being However, the acetylene polymer obtained in this way does not melt even when heated and easily undergoes oxidative deterioration under excessive heating, so it cannot be molded using the usual molding methods used for thermoplastic resins. Can not. Unfortunately, no solvent has been found that dissolves this acetylene polymer. Therefore, conventional methods for producing practical molded products of acetylene high polymers include (c) a method of pressure molding powdered acetylene high polymers;
Or @ form it into a membrane at the same time as polymerization under special polymerization conditions,
The method was limited to a method for obtaining a membranous acetylene polymer having a fibrous microcrystalline (5-fibril) structure and high mechanical strength (Japanese Patent Publication No. 32581/1981).

However, with method (a), only molded products with low mechanical strength can be obtained, while with method (b), molded products with low mechanical strength can be obtained compared to molded products that cannot be obtained with method (a). Although it has the advantage of high strength, the bulk density of the resulting acetylene polymer molded product is at most 0.609/CC,
(Embodiment II-], 20!y/cc) There was a drawback that only a porous film could be obtained.

BF3. BC7,, l-1cl, C12,
When chemically treated with electron-accepting compounds (acceptors) such as S('J, No. 2.11CN, 02, and NO, the electrical conductivity increases by up to three orders of magnitude, and conversely, 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 a reactive compound (donor).
ns, F”arady Soc,.

(i4, 823 (1968)).

In addition, I2. CIJ2. Br2. ICCIBr,
It is already known that electron-accepting compounds such as PF6, etc., or electron-donating compounds such as Na, Ig, and Ll can be freely controlled chemically to AsF, Sb, etc. [J, C, Sb] , Chem, Commu
, , 578 (1977) +Phys, Rev.
Lett, 39.1098 (1977), J. Am.

5oc-, 100, 1013 (1975), J.
Chem, Phys, 69.

5098 (1978)], the idea of using this doped film-like acetylene polymer as a filler material for the anode of a primary battery has already been proposed (Molec.
ularMetals, NATOConferenc
c 5eries, 5eries VI.

471-489 (1978)),,) On the other hand, in addition to the chemical doping method described above, c7 can be electrochemically doped.
o4-1PF6, AsF6-, AsF, -1C
Anions such as 503-%BF4- and RλN''
CJ has already developed a method for producing P-type and n-type conductive acetylene polymers by doping cations such as -(R': alkyl group) into acetylene polymers.
,C,S,Cbem,Commu, ,1
97 History 594. C & ENJan, 26, 39
(1981), J.C.S., Chem., Comm.
u, .

1981, 317). A rechargeable battery using electrochemical doping using a film-like acetylene polymer that cannot be obtained by the method (b) has been reported (P
aper Presented at the Int.
ernationnal 0Jnferenccon
Low l）Imensional 5ynth
etic Metals, Hersinger.

1) cnmark, 10-15, August
1980), this battery is obtained by the method ((b)). For example, two acetylene polymer films with a thickness of 0.1 M are used as positive and negative electrodes, respectively, and a tetrahydrofurano solution containing lithium iodide is used. Soak Nikoi''I and 9v
When connected to a DC power source, lithium iodide is electrolyzed,
The acetylene polymer film of the anode is doped with iodine, and the acetylene polymer film of 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 2.8 V, the short circuit current density is 5 mA/cnt, and when a tetrahydrofurano solution of lithium perchlorate is used as the electrolyte,
The open circuit voltage is 25■.

The short circuit current density was approximately 3 mA/cJ.

This battery uses an acetylene polymer as its electrode material, which is easy to reduce weight and size, so it is attracting attention as an inexpensive battery that has high energy density and is easy to reduce weight and size. There is. It is also not known that poly(paraphenylene), in addition to acetylene polymers, is also useful as an electrode material. However, the cycle life, voltage flatness during discharge, charging/discharging efficiency, etc. of batteries using these known molecular compounds having conjugated double bonds in the main chain as active materials for electrodes have been limited. Performance was not always satisfactory.

In view of the above points, the present inventors have found that the present invention has a low energy density, good cycle life, good charging/discharging efficiency, and voltage flatness during discharging, and is easy to reduce weight and size. The present invention was completed as a result of 8;1 tests on the glaze in order to obtain an inexpensive battery.

That is, the present invention provides a battery in which a polymer compound having a conjugated double bond in the main chain or a conductive polymer compound obtained by doping the polymer compound with a dopanode is used as an active material of at least one electrode. The present invention relates to a battery characterized in that a metal film layer is provided on the surface of the electrode on the current collector side.

The battery obtained by the method of the present invention uses a conventional polymer compound having a conjugated double bond in its main chain or a conductive polymer compound obtained by doping the polymer compound with a dopant as the active material of the electrode. Compared to batteries, negative batteries have the following advantages: (1) higher discharge capacity, (11) better voltage flatness during discharge, and less self-discharge. On the other hand, in the case of a secondary '5 pond, (1)
The present invention has the following advantages: high energy density, (11) good voltage flatness during discharge, low self-discharge, and long life after repeated charging and discharging. A secondary battery is more suitable as a battery that maximizes its characteristics.

Specific examples of the polymer compound having a conjugated double bond in the main chain used in the present invention include acetylene polymer (polyacetylene), polyphenylacetyleno, polyparaphenylene, polymetaphenylene, HoIJ (2, 5-f enylene)% poly(3-methyl-2,5-chenylene I/)),
Polypyrrole, polyimide.

Examples include thermally decomposed products of polyacrylonitrile and poly-α-cyanoacryl, but they are not necessarily limited to stiffness, and any polymer compound having a conjugated double bond in the main chain may be used.

Among the above polymer compounds, preferred are:
Acetyleno high polymer, polyparaphenylene, poly(25
- Chenille 7), polypyrrole, and preferred examples include acetylene high polymers, particularly preferably highly crystalline acetylene high polymers.

The method for producing the acetyleno polymer preferably used in the present invention is not particularly limited, and any method may be used. Kaisho 55-129404, Kaisho 55-128419, Kaisho 557142012,
No. 56-10428, No. 56-133133, Tr.
ans, Farady Soc, .

64, 823 (1968), J.PoIym=
r Sci, , A-1, E, 3419 (196
9), Makromol, iChem, , Rapj<l
Corrrn, , l+621 (1980), J.
Chem, Phys, 69 (1), 106
(1978).

5ynthetic Metals, 4 + 81 (
1981).

The polymer compound having a conjugated double bond in the main chain used in the present invention can be in the form of a film, powder, short fibers, etc., but other than film forms can be prepared by the person concerned. It is desirable to mold the molded article by a method known in the art to obtain a molded article having the necessary mechanical strength. It is also possible to mix other suitable conductive materials such as graphite, carbon blank, acetylene black, metal powder, carbon fiber, etc. with the polymer compound having a conjugated double bond in the main chain. There is no problem in using metal ropes etc. as a protection.

As the electrode of the battery of the present invention, not only a polymer compound having a conjugated double bond in its main chain but also a conductive polymer compound obtained by doping the polymer compound with a dopanode can be used as the electrode. .

Either chemical doping or electrochemical doping may be used as the method for dopant incorporation into a polymer compound having a conjugated double bond in its main chain (hereinafter referred to as a conjugated polymer compound). .

The dopanodides to be chemically doped include 0+ various conventionally known electron-accepting compounds and electron-donating compounds, namely (1) halogens such as iodine, bromine, and bromine iodide, arsenic fluoride, Metal halides such as fluorine/fluoride, silicon tetrafluoride, phosphorus pentachloride, phosphorus pentafluoride, aluminum chloride, aluminum bromide and aluminum fluoride, ΦD sulfuric acid, nitric acid, fluorosulfuric acid, trifluoromethanosulfuric acid and chloro Protonoacids such as sulfuric acid, σ■ sulfur trioxide, nitrogen dioxide, @ml forming agents such as difluorosulfonyl peroxide, M
AgCA O4゜(Vl) Tetrananoethylene, Tetracyanoquinodimethane, Floranil, 2.3--/
Chlorou 5.6- dicyanobara benzoquino/, 23-
Dibromo-56-dicyanobarabenzoquinone and the like can be mentioned.

On the other hand, as a dopanode for electrochemical doping, (i) PF6-1SbF6-1AsF6-1SbC4
Halide aniono of Va group elements such as -, BF4
- a halide aniono of an element of group 111a such as
I-(I,-).

l3r-%C1-NOYO 1'rogenoaniono, CIO,
Anionic dopants such as perchlorate anions such as - (Isunemo is also effective as a dopanodide to give P-type electrophilic conjugated polymer compounds) and (ii) Li+, K+, Na
Cation dopants such as alkali metal ions such as +, quaternary ammonium ions such as 14N+ (R: hydrocarbon group having 1 to 20 carbon atoms), etc. (St'L also provides n-type conductive conjugated polymer compounds) (effective as a dopant), but it is not necessarily limited to stiff hemorrhoids.

Specific examples of compounds providing the anionic dopant and cationic dopant mentioned above include LiPg, 1i +
S b 几, LiAsF6. LiC10,, NaI, N
aPF6, N a S b Fa, NaAsF, , N
aCd04, Igu■, IguPF6. I<S bF6
, I(asF6, KCI)OI, ((n-13u)
, + :]”・(AsFa)−,C(n-Bu)4]
"・(PF,)1C(n-Bu)4Nl"
- Examples include CIJO4, LtA7C&, and LiBF+, but are not necessarily limited to these. One type of Kowara dopanode may be used, or a mixture of two or more types may be used.

The anion/dopant other than the above is an HF27 anion, and the cation dopant other than the above is a pyrylium or pyridinium cation represented by the following formula (D: where X is an oxygen atom or nitrogen atom, R is a hydrogen atom, k is an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 15 carbon atoms, Ru is a halogen atom or an alkyl group having 1 to 10 carbon atoms, and 6 carbon atoms ~15 aryl group, m is O when X is an oxygen atom, and 1 when X is a nitrogen atom.■] is 0 or 1 to 5
It is. ) lfr is a carbonium cation represented by the following formula 〇 or (IID: and i<' -C″-1 [In the above formula, R1,
%R3 is not a hydrogen atom at the same time), carbon number 1
-15 alkyl group, allyl group, aryl group having 6 to 15 carbon atoms -OR
5g, provided that LR' represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, and R4
is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, and 6 carbon atoms.
~15 aryl groups. ] It is.

■<2N・11F2 0■M・I
IF2(Vl (R''')n [However, in the above formula, R' and R'' are hydrogen atoms or carbon atoms 5
1-15 alkyl group, carbon ii6-15)7 II
-/l/(aryl) group %R''' is alkyl having 1 to 10 carbon atoms, alkyl having 6 to 15 carbon atoms,
group, X is an acid atom or a nitrogen atom, and n is 0 or an integer of 5 or less. M is an alkali metal] It can be obtained by dissolving a compound (hydrogen fluoride salt) represented by the following as a supporting substance in an appropriate organic solvent. Table A Tsusane 7 with the above formula (IV), M and ■
) Specific example of compound '+914 L''C Id I
7NJII'',,,Bu.jlN-111.'.

Na11) TF2, K-I-Ii;',, , Li
- 1(1i'2 and 4) The pyrite or pyridinium-thione represented by the above formula (I''l) is the cation represented by the formula (1) and CI
O4-, BF4-, MCI, ,, FeC14-,
SnC4-, I) I, Na-, l) CA,-.

SbF6-%AsF-, CF3803-, HF,,-
It can be obtained by dissolving a salt of Anime-7 in a suitable organic solvent using as a supporting electrolyte. Specific examples of such salts include the following.

Specific examples of carbonium cations represented by the above formula (I) or ΦD include (C6H5)3C+, (CI
]3)3(”.

Carbonium cations from kneading can be obtained by dissolving anionic salts (carbonium salts) in suitable organic solvents as supporting electrolytes! T-lane. Typical examples of anions used here are:

BIi4-1MC4-%MBr3CIJ, FeC4
, SUC&-1PJ-'6-.

PC&-%5bcz6-5SbF6-1C7 (14-%
Specific examples of carbonium salts include (Ca t-1,,)3
c -B F (C113)3C・13■I", %HC
O-A7C4%1(Co-BF4.C6H,,CO
” 5n04 etc. can be given.

The amount of dopanod doped into the conjugated polymer compound is 2 to 40 per mole of repeating unit of the conjugated polymer compound.
The mole fraction is preferably 4 to 30 moles, particularly preferably 5 to 20 moles. When doping, it is not possible to obtain a battery with a sufficiently large discharge level even if the dopanodide level is less than 2 molar or more than 40 molar.

The electrical conductivity of the conjugated polymer compound before doping is 10-5Ω-1・cln-' or less, and the electrical conductivity of the conductive conjugated polymer compound that cannot be obtained by doping with the dopant-4 is about 1O-1. )~104Ω-1・crn-
' When used in the range of about 10-10 to about 10-4
Ω−” Cln−’ even 1 * s about 10−
It may be thicker than 4Ω-1·Crn-'.

The amount of dope can be freely controlled by controlling the amount of electricity that flows during electrolysis. The doping may be carried out in an in-situ manner under constant current, constant voltage, or under conditions of varying current and voltage. The current value, voltage value, doping time, etc. during doping depend on the type of conjugated polymer compound used, the bulk density per area,
It cannot be unconditionally defined because it varies depending on the type of dopant, the type of electrolyte, and the required electrical conductivity.

Examples of organic solvents for the electrolyte during electrochemical doping include ethers, ketones, and nitrile.

Aminos 7, amides, sulfur compounds, chlorinated hydrocarbons,
Ester products, carbonates, nitro compounds, phosphate ester compounds, sulfolano thread compounds, etc. can be used, but among the stiff ones, ethers, ketones, nitriles, chlorinated hydrocarbons, carbonate) M, Sulfolano compounds are preferred. Typical examples of stiffness include tetrahydrofuran% 2-methyltetrahydrofurano, 1
．． 4-dioxa7, anisole, monocryme, acetonitrile, propionitrile, 4-methyl-2-penta/
7. Butyronitrile, l,2-dichloroethane, γ-butyrolact/, dimethoxyethane, methylformate, propylenocarbonate.

Examples include ethylenocarbonate, dimethylformamino acid trimethyl, triethyl phosphate, etc., but are not necessarily limited to stiffness.

It is also possible to use Isune's methods such as the Klinobu method and the Ionbletinobu method. The metal used in the present invention is not particularly limited, but is usually M.

Au%PL, Ag%Ni%In, '1. "i etc. are not used. 1k.

Conductive metal oxides such as J, n203, and SnO□ can also be used. The thickness of the metal film layer varies depending on the type of conjugated polymer compound used, battery configuration, etc., so it cannot be defined unconditionally, but it is usually 10A to 1.000A.
It is. If the thickness of the gold layer is less than IOA, the improvement in battery performance will not be sufficient, and even if the thickness exceeds 1.00OA', no further improvement in battery performance will be observed.

To prepare a conductive conjugated polymer compound tK9 having a metal film layer on the surface on the current collector side, dopant 6 is added to the conjugated polymer compound in advance.
A metal film layer may be provided on one side of the doped conductive conjugated polymer compound by the above method.
Alternatively, a metal film layer may be provided on one side of the conjugated polymer compound and then the dopant may be doped.

In the present invention, when a conjugated polymer compound having a metal film layer on the surface on the current collector side or a conductive conjugated polymer compound obtained by doping the polymer compound with a dopanode is used as a positive electrode and/or a straddling negative electrode, The support chamber for the battery electrolyte is the same as that used in the vapor chemical doping described in +3iJ, and the Dobi/G method is similar to the one described above and the conventionally known method (J, C,S,
, Chem, Commu, , 1981, 317
).

The concentration of electrolytic qfuj used in the battery of the present invention depends on the types of positive and negative electrodes used, charging/discharging conditions, operating temperature,
It cannot be unconditionally defined as it varies depending on the type of electrolyte and type of organic solvent, etc., but it is usually 0.001.
~10 mol/l.

In the present invention, a conjugated polymer compound having a metal film layer on the current collector side or a conductive conjugated polymer compound obtained by doping the conjugated polymer compound with a dopane is used for a battery (1).
) It can be used as a positive electrode or (11) negative electrode, or as an active substance for both positive and negative electrodes.

Preferred cells are of the type (1) or 19, but particularly preferred are cells of the type (10).

As a specific example in the case of a secondary battery, for example, acetylene polymer 'k (C1-()x, (C1-1)
x (positive electrode) / LiC10, (supporting electrolyte) / Li (
negative electrode), (CI-D engineering (positive electrode) / LiC1Q4 (supporting electrolyte) / (CI-I) x (negative electrode).

C(C1l)-” 00” (C1l O4);, ++
241x (positive electrode) / (n-Bu4N)+-(Cl
O4)-(supporting electrolyte)/C(n-Bu, N).

24ru'(・cc+1)-0,1124]x (negative 4k), [(CI-I)+006(PFa)o,o
6) x (jlE pole)/(Et4N)-(PF'0)-
(Supporting electrolyte) / C(Li)00G(CII)-
1+06]x (negative electrode), [(CH)”050 (C104
)oo5゜゜゛(positive electrode)/(■荊4゛・((J?04)
-(Supporting electrolyte) /[C1-1)-0020(CIO
4')) m'3X (negative electrode), ((n-Bu4N) oz (C1-0-0,02)8 (positive +?) / (
n Bu4N)”・(CIJO<) (Supporting electrolyte)
/[(Bu4N)Kichi. 7(CII)-”07)X (negative electrode), [(C)1),,o+o(1,+)o,o+o]
x (positive electrode) / LiI (supporting electrolyte) / C (CI-1
)−0010σJi)mu,. ] (negative electrode), etc.

In the case of HoIJ paraphenylene, (CaI(4)x) is substituted for the above (CI)
In the case of (CH)x<7”? instead (C411□S)
In the case of polypyrrole, x is (C4H3N)x and used in the same type of secondary battery as above.

Furthermore, in the present invention, different conjugated polymer compounds can be used for the positive and negative electrodes, and a specific example thereof is (C
I) X/L 1cAO+ /(C6114)X, (C
I-I)x/LiC11O4/ (C4”'2 S)-
(C6I'14) x/ Licz O+ / (C
o l14) x, etc.

As an example of a primary battery, the electrical conductivity is io'Ω-1・α
Examples include those in which the above-mentioned conductive conjugated polymer compound is used as the positive electrode active material fl2, and a metal whose Pauling's electronegative 4 does not exceed 16 is used as the negative electrode active material. Metals used as negative electrode active materials include lithium,
Examples include alkali metals such as sodium, aluminum, magnesium, and the like. Among the stiff materials, lithium and aluminum are preferable. The stiff metal may be used in the form of a sheet like that of a general lithium battery, or the sheet may be crimped onto a nickel or stainless steel mesh.

In the present invention, if necessary, a porous membrane of synthetic resin such as polyethylene or polypropylene or natural fiber paper may be used as the diaphragm.

i fr sSome of the conjugated polymer compounds used in the present invention undergo a gradual oxidation reaction with oxygen, reducing the performance of the battery. It is necessary that there be. Additionally, the cells of the present invention may be thin cells, even paper-thin cells, multiple layers may be stacked on top of each other and coupled together in series or parallel, or a single long cell may be assembled by itself. It may be rolled or spiraled.

A battery using as an electrode a conjugated polymer compound having a metal film layer on the surface on the current collector side or a conductive conjugated polymer compound obtained by doping the conjugated polymer compound with a dopant, It has high energy density, high charge/discharge efficiency, long cycle life, low self-discharge rate, and good voltage flatness during discharge. Further, the battery of the present invention has
lightweight.

Because it is small and has high energy density, it is ideal for portable devices, electric vehicles, gasoline vehicles, and power storage batteries.

EXAMPLES The present invention will be explained in more detail below with reference to Examples and Comparative Examples.

Example 1 [Production of film-like acetylene polymer] 1.7-titanium tetrabutoxide was added to a glass reaction vessel with a capacity of 500 rnl under a nitrogen atmosphere.
30m7! of anisole, then 2.7
A catalyst solution was prepared by adding ml of triethylaluminum with stirring.

This reaction vessel was cooled with liquid nitrogen, and the nitrogen gas in the system was exhausted using a vacuum pump. Next, this reaction vessel was
It was cooled to 0.degree. C. and purified acetylene scum was blown in at a pressure of 1 atmosphere while the catalyst solution remained stationary.

Immediately, polymerization occurred on the surface of the catalyst solution, producing a film-like acetylene high polymer. 49 minutes after the introduction of acetylene, the acetylene gas in the reaction vessel system was exhausted to stop the polymerization.

After removing the catalyst solution with a syringe under nitrogen atmosphere, -78
It was washed 5 times with purified Trugeno 100d while keeping the temperature at °C. The one box-shaped acetyrefaction polymer that swelled by +171 in the Toll treatment was a uniform film-like swollen product in which fibrils were tightly intertwined. Next, this expanded 4" material was vacuum-dried to a reddish-purple color with a metallic luster, a thickness of 85 μm, and a mineral content of 98 μm.
A film-like acetylene high polymer of 1 was obtained. Moreover, the bulk density of this film-like acetylene high polymer is 0.45 g/CC, and its 'IL air conduction J1 degree (DC four terminal method) is 3.2X10'Ω-1・tyn- at 20°C. 'Met.

[Battery experiment]

1) From the film-like acetylene polymer having a film thickness of 85 μm and a bulk density of 0.45 g/cc obtained by the method described in II, two sheets with a width of 0.5 cnl and a length of 2.0 cm were prepared. A small piece was cut out, and gold was deposited on one side to a thickness of about 50× by vacuum deposition. This vapor-deposited surface was mechanically pressed onto a platinum plate (current collector) to form a positive electrode and a negative electrode, respectively. The distance between the positive and negative electrodes was set to 3 mm. Et4~・B cloudy concentration 1,0
Using a sulfolane solution of mol/l as the electrolyte, charging was carried out for 70 minutes under a constant current (0.5 mA/ca) (amount of electricity equivalent to a doping amount of 78 mol). Immediately after charging, the battery was charged under a constant current ( 0.5mA/crA), discharge is performed until the voltage reaches 1.5mA/crA). When the battery reached OV, a repeated charging/discharging test was conducted in which charging was performed again under the same conditions as described above, and it was possible to repeat the battery up to 406 times.

The energy density (theoretical energy density) for I kg of active material was 204 W·hr/h, and the charge/discharge efficiency was 95. The voltage is 1.5V when discharging.
The ratio of the electrical loss caused by discharging at 1 to the total amount of discharged electricity is 96 cm.

When the battery is discharged for 48 hours in a fully charged state, its self-discharge rate is 5%. ,.

Comparative Example 1 [Battery Experiment] The battery 'i' obtained in Example 1 also had a bulk density of 0.45/CC,
, film thickness is 85 μm, electrical conductivity is 3.2 x 10-9
0-"cnl', except that gold was not deposited on the film-like acetylene polymer, the battery was repeatedly charged and discharged in exactly the same manner as in the experiment fjl. As a result, charging was completed at the 198th repetition. After the test, when the film-like acetylene polymer was taken out, it was discovered that the film had been destroyed, and elemental analysis of a portion of it was performed, and infrared spectroscopy revealed that the theoretical energy density of this battery was 180 W- The light/discharge efficiency was 82 cm at 9 h/hr.The voltage during discharge was 1.5
The ratio of the amount of electricity to the total amount of electricity discharged when the voltage decreased to 1 was 89.

Unfortunately, when I left it charged for 48 hours, the self-discharge rate was 0%.

Example 2 [Battery experiment] From the NFC acetylene polymer obtained in Example 1.

Two small pieces with a width of 0.5 cm and a length of 2.0 crn were cut out, and approximately 500 A of aluminum was vacuum-deposited on one side of the pieces. This was mechanically pressed onto a platinum plate (current collector) in the same manner as in Example 1 to form a positive electrode and a negative electrode, respectively.

(I3LL,N)+(PF6)-'&iM is 05 mol/
1 of 3-methylsulfolane and 1 of dimethoxyethane:
Using a solution of a mixed solvent of 1 (mi amount ratio) as the electrolyte, charging was performed for 70 minutes under a constant current (0.5 mA / ar!) (amount of electricity equivalent to a doping amount of 78 moles), and after charging was completed. , immediately start a constant current (0.5mA/
A repeated test of charging and discharging was conducted in which the battery was discharged at a voltage of 1 cm2 and then charged again under the same conditions as above when the voltage reached 1.5 cm, and it was possible to perform up to 388 times.

The theoretical energy density of this battery is 204 w-hr/K
The charging/discharging efficiency was 93 g, but the voltage dropped to 1.5 g during discharge, and the ratio of the amount of air to the total amount of discharged electricity was 92 g. there were.

Furthermore, the self-discharge rate was 6 when left in a charged state for 48 hours.

Comparative Example 2 [Battery Experiment] A battery was charged and charged in exactly the same manner as in Example 2, except that aluminum was not vapor-deposited on the acetylene polymer.
When repeated discharge experiments were conducted, charging became impossible at the 35th repetition. After the experiment, when the film-like acetylene polymer was taken out, it was found that the film had not yet been destroyed, and part of it was analyzed by elemental analysis and infrared spectroscopy, and it was found that it had suffered significant deterioration. -1: The electrolyte was colored brown.

The theoretical energy density of this battery was 101 W·hr/7, and the charge/discharge efficiency was 46. Furthermore, the ratio of the amount of electricity discharged until the voltage decreased to x,5 V during discharge to the total amount of electricity discharged was 59 times. 1
However, when I left it in a charged state for 48 hours, its self-discharge rate was 48%.

Example 3 2 m6 (5.9 mmol) of toluene 200-% tetrabutoxytitanium and 2 ml (14.6 mmol) of triethylaluminum were charged into 11 glass autoclaves equipped with a blade-type mechanical stirrer under a nitrogen atmosphere, and acetylene was added. Partial pressure 09Kg/C1, polymerization temperature -2
Polymerization was carried out at 0° C. with stirring for 2 hours. Simultaneously with the introduction of acetylene gas, short fibrous acetylene polymers of reddish-purple color and approximately 1 mm in length began to form.

After the polymerization was completed, the produced short fibrous acetylene polymer was placed on a glass filter and thoroughly washed with about 11 toluene solvent to remove the catalyst. After catalyst removal, the short fibrous acetylene polymer contained 52 parts by weight of toluene. This toluene-containing short fibrous acetylene polymer was press-molded at room temperature under a pressure of 1 tom/cni to obtain a sheet-like molded product. A 2m square molded product was cut out from the obtained molded product, and one side was coated with Example 1.
Gold was deposited to a thickness of about 50 OA using the same method. This was mechanically pressed onto a platinum plate (current collector) to form a positive electrode, while lithium metal was used as a negative electrode, and the same lithium metal was used as a reference electrode.IJIBI! The concentration of λ is 1.0 mol/
l of propylene carbonate solution as the electrolyte,
Charging was carried out for 90 minutes under a constant current (], f) 111A10ri) (amount of electricity equivalent to 6 moles of doping), and immediately after charging was completed, the battery was charged under a constant current (1,0 mA/c).
A repeated charging/discharging test was conducted in which the battery was discharged at 2.5 V and then charged again under the same conditions as above, and it was possible to repeat up to 381 times.

As a result of the first repeated charge/discharge test, after using
The energy density for the acetylene 1/one high polymer I Ky was 492 Whr/Kp, and the charge/discharge efficiency was 95 factors. Further, the ratio of the amount of electricity discharged at the time when the voltage decreased to 2■ during discharge to the total amount of electricity discharged was 94 times.

Comparative Example 3 In Example 3, a battery charging/discharging repetition experiment was conducted in exactly the same manner as in Example 3, except that gold was not vapor-deposited on the acetylene polymer molded product, and the number of repetitions was 233rd. Natsu woman is unable to charge the battery. When the acetylene polymer molded article was taken out after the test, it was found to have been destroyed, and when a portion of it was analyzed by elemental analysis and infrared spectroscopy, it was found to have suffered oxidative deterioration.

The first charging/discharging cycle! As a result of the llll-return test, the A-lugie density for I kg of the acetylene high polymer used was 398 w - + 1 r 7 kg, the light discharge efficiency was 76, and the voltage decreased to 2 ■ when discharging. The ratio of the amount of electricity already discharged to the total amount of electricity discharged was 81.

Example 4 Bull, Chem, Soc, Japan, 51
．． 1 ton/cat of poly(paraphenylene) prepared by the method described in 2091 (1978).
0.5cm x 2. After molding to the width of OCn+, approximately 50OA of gold was applied to one side of the molded product in the same manner as in Example 1.
[Battery experiments] were carried out in the same manner as in Example 1, except that the positive and negative electrodes were vapor-deposited to a thickness of 312 cycles of charging and discharging.

this? The energy density of Ji Pond is 311W・hr/
K9, and the charge/discharge efficiency was 83chi. Mak,
After charging and leaving it for 48 hours at 1 k, the self-discharge rate was 9%.

Example 5 J, Polym, Sci, Polym, Iz
ts, Ed, 188 (1980) was molded into a width of 0.5ctn x 2.0z at a pressure of 1 ton/crti, and then Example 1 was prepared. [Battery experiment] was carried out in exactly the same manner as in Example 1, except that gold was evaporated to a thickness of about 50 OA on one side of the molded product using the same method as in Example 1, and gold was used as the positive and negative electrodes.As a result, repeated charging and discharging were performed. The 303rd test was 0. The theoretical energy density of this battery is 195 W.
The charge/discharge efficiency was 93 at -hr 7Kg.

When I left a fully charged 11 for 48 hours, the self-discharge rate was 10%.

Patent applicant: Showa Denko Co., Ltd. Hitachi, Ltd. Agent: Patent Attorney Sei Kikuchi

Claims (1)

[Claims] A polymer compound having a conjugated double bond in the main chain or the i.
1': A conductive polymer compound obtained by doping a dopanol compound with a dopant is applied to at least one electrode.
//A battery used as J quality, characterized in that a metal film layer is provided on the current collector side surface of the electrode.