JPS61232563A - Nonaqueous solvent secondary battery - Google Patents

Abstract

PURPOSE:To improve cycle life by using an active material mainly comprising polythiophene or polythiophene derivative, aluminum, and lithium in a negative electrode. CONSTITUTION:8mg of Al-Li alloy having an atomic percentage of 55:45 and 2mg of polythiophene powder obtained by washing with tetrahydrofuran and drying under a reduced pressure is mixed with a mortar in an atmosphere of argon. The mixture is molded in a pellet having a 10mm diameter and wrapped with nickel net 3, and a nickel wire 3 is drawn out from the nickel net 3 to form a negative active material. About 50g of lithium foil pressed on a nickel net 4 is used as a counter electrode. About 20ml of solution obtained by dissolving 1mol/l of LiBF4 in the mixture solvent of 2Me-THF and TMS having a volume ratio of 1:1 is used as electrolyte 5. They are accommodated into a glass cell with cover to form a secondary battery. The cycle life of this battery is lengthened.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a high-performance non-aqueous solvent secondary battery that has high energy density, good charge/discharge reversibility, and extremely low self-discharge rate. Regarding.

[Problems to be solved by the conventional technology and invention 1 Currently used secondary batteries include lead-N batteries, Ni/Cd batteries, etc.
There is W Pond etc. These secondary batteries have a single cell battery voltage of about 2.0 V at maximum, and are generally aqueous batteries. Recently, as a secondary battery capable of achieving a high battery voltage, research has been actively conducted on the development of a secondary battery using l-i as a negative electrode.

When 1-i is used as an electrode, the high G between water and li)
Due to the reactivity, it is necessary to use a non-aqueous electrolyte.

However, when carrying out a secondary battery reaction using li as a negative electrode active material, dendrites are generated when li+ is reduced during charging, resulting in problems such as a decrease in charge/discharge efficiency and a short circuit between the positive and negative electrodes. Therefore, many technological developments have been reported to prevent dendrites and improve the charge/discharge efficiency and cycle life of negative electrodes. M Abraham et al. “Lithium Batches”,
J.P. Gapano Collection, published by Academic Press,
London (1983), M.

Abraham et al.
thium 13 atteries”.

J, P, Gabano, ediicr, Ac
academic press.

ヰ#≠Short London (1983)), a method of preventing Ll dendrites by adding additives to the electrolytic solution system, or alloying the electrode itself with helical metal [JP-A-59-108281], etc. is proposed.

However, in these conventional techniques, the reversibility of charging and discharging li is still insufficient, and the cycle life is not necessarily satisfactory.

In addition, if only an alloy of An and l-i is used for the negative electrode, not only will there be a problem of brittleness of the negative electrode itself during use, but also when charging and discharging at high electric density (1 mA/ci! or more), Ll will be used as the negative electrode. As in the case where dendrites were used, dendrites were unavoidable. In particular, when the l-i content in the AFL-Li alloy is increased in order to increase the utilization rate of Ll and increase the energy density, the occurrence of the above-mentioned problems such as dendrites is noticeable, and it is difficult to use as a secondary battery. The performance, especially the repeated charging and discharging, was not good enough for practical use.

The reason for this is that even if an alloy of l-i and Ai is used, the rate at which l-i diffuses through the alloy of l-i and Al during charging is insufficient at high current density (more than 5 mA/CI!). First, the alloy ratio Lifit has increased considerably in some areas (for example, in some areas, Ll is 100% and is considered to be almost a single metal), and Li
This is thought to be because it exhibits the same @ dance as when the metal itself is used as the negative electrode.

[Means for Solving the Problems] As a result of intensive studies to solve the drawbacks of the conventional method, the present inventors found that by using an active material having a specific composition as a negative electrode, reversibility of charging and discharging can be improved. The present inventors have discovered that a high-performance non-aqueous solvent secondary battery can be obtained that has good performance, long cycle life, high energy density, and extremely low self-discharge rate, and has completed the present invention.

That is, the present invention relates to a non-aqueous solvent-based secondary battery characterized in that an active material mainly composed of polythiophene or a polythiophene derivative, Al, and lj is used as a negative electrode.

[Function] In the present invention, the effect of using an active material mainly composed of polythiophene or a polythiophene derivative, An and l-i in the negative electrode is remarkable, and although the details of the mechanism of action are not clear, When polythiophene or polythiophene derivatives are used, polythiophene or polythiophene derivatives are uniformly dispersed, which has the effect of increasing the specific surface area of the entire electrode and slowing down the diffusion rate of l-i. l! ! It is thought that dendrites cannot be formed because the conductor itself reacts reversibly with li+ and plays a part in the electrician through a so-called doping phenomenon. Moreover, the polythiophene or polythiophene derivative itself also has binding agent properties, and the addition of the polythiophene or polythiophene derivative is thought to have the effect of maintaining the dimensional stability of the negative electrode.

[Means for Solving the Problems] The polythiophene used as one of the components of the negative electrode active material of the present invention has a conjugated structure similar to that of cis-type polyacetylene and contains a sulfur atom. Since it has an electronic structure, it is expected to be a conductive material, and various synthesis examples have been reported.

For example, in Journal of Polymer Science, Part A-1, Volume 5, Page 1527 (1967),
There is a report by M. Armor et al., in which a yellow-brown polymer is obtained by polymerizing thiophene using trifluoroacetic acid as a catalyst, but this polymer has 4 repeating units.
It is described that it is a low polymer that has a molecular weight of about 1 mole and is soluble in solvents such as benzene and chloroform. Also, in Journal of Chemical Society (c), Vol. 1971, p. 234, there is a report by R.F. Curtius et al., which states that when thiophene is polymerized in polyphosphoric acid, several types of low polymers are formed. It is stated that the main product obtained is a non-conjugated compound consisting of 2,4-di-2-chenyltetrahydrothiophene.

On the other hand, Sansui et al. reported in the Journal of Polymer Science Polymer Letters Edition Vol. It is described that when an active organomagnesium compound is produced by reacting with metallic magnesium in an ether solvent such as dibutyl ether, and a nickel complex catalyst is added to this, polymerization easily occurs to obtain polythiophene.

Furthermore, in Chemistry Letters, p. 1079 (1981), Sansui et al. state that the polymer obtained by this method is of poor quality, and that when this polymer is doped with iodine or sulfuric anhydride, its electrolyte is lower than that of the non-added polymer. It is stated that the conductivity of the semiconductor is 7 to 9 orders of magnitude higher than that of polymers, and has a conductivity of about 10 to 1 G'S/α.

As mentioned above, the polythiophene obtained by this method is of poor quality, and the yield of the hot chloroform-insoluble part is low.
Further, JP-A-56-47421 describes that the average molecular weight is 1730 (average degree of polymerization of about 19) based on the results of elemental analysis, and the degree of polymerization is not very high.

In addition, as a method for synthesizing crystalline polythiophene, as described in Japanese Patent Application No. 58-95857, under an inert atmosphere,
reacting 2,5-dihalogenothiophene or a derivative thereof with metallic magnesium in an aliphatic ether solvent to form a substantially active organic monomagnesium compound;
After removing the aliphatic ether solvent, there is a method of depleting the organic monomagnesium compound in an aromatic ether solvent in the presence of a nickel complex catalyst under an inert atmosphere, and the 2, It is known that polythiophene bonded at the 5-position is not only obtained in extremely high yield and in the form of four molecular claws, but also crystalline. Furthermore, Macromolecular Chemistry, Rabid Communication Vol. 4, pp. 639-643 (198
N0B to low molecular weight compounds such as thiophene monomers or 2,2'-bichenyl, as described in
There is also known a method of doping a nido-0sonium salt such as F4 or N08b Fe in an organic solvent and cationically polymerizing the above-mentioned low-molecular-weight compound a. Furthermore, the method of Kaneto et al., which involves electrochemical polymerization, is also known, as described in Applied Physics Vol. 52, No. 11 (1983). This electrochemical polymerization method uses, for example, monovalent metal cations, Li + , Na + and salts consisting of tetrabutylammonium, hexafluorophosphate or hexafluoroarsenide anions in a benzonitrile or acetonitrile solvent as supporting electrolyte. A low resistance Nesaglass (indium-tin oxide film) is used as the anode, a platinum plate is used as the cathode, and the supporting electrolyte is a solution containing, for example, 500 mojl/rrt3 of thiophene as the electrolyte. In this method, a voltage of +20 V is applied to the negative side of the platinum plate to cause a polymerization current to flow, thereby obtaining a polythiophene film doped with blue anions on the platinum glass plate. Neutral polythiophene can be easily obtained by dedoping the above polymer.

The polythiophene used in the present invention may be produced by any of the above methods, but is not necessarily limited to those produced by these methods. Also,
Polythiophene derivatives can also be produced in the same manner as above. Examples of polythiophene derivatives include poly-3-methylthiophene, poly-3,4-dimethylthiophene, and poly-3-ethylthiophene.

Polythiophene and polythiophene derivatives may be used in combination.

As a method for producing an active material mainly composed of the three components polythiophene or polythiophene derivative, AI, and 1-i used as the negative electrode in the present invention, for example, (1) polythiophene or polythiophene derivative,
A method of mixing An and Li alloy powder and then press-forming the mixture.

That is, a prepolymerized powder or granular polythiophene or polythiophene derivative and a Li-hexagonal alloy (Li content of 6 to 73 wt%) are mechanically mixed and molded to form a pellet or film active material. make. Note that this active material may be molded in a form that includes a current collecting substrate, that is, N i , F (! 1 stainless steel, a helical plate, etc.).

(2) After electrochemically or chemically neutralizing the polythiophene or polythiophene derivative obtained by electrochemical polymerization, the polythiophene or polythiophene derivative is electrochemically applied to A3+ and L using a cathode.
A method of reducing 1+ to precipitate AI and Ll in polythiophene or polythiophene derivatives.

That is, a film-like polythiophene or polythiophene derivative obtained by electrochemically polymerizing thiophene or a thiophene derivative in advance is brought into a neutral state, and then immersed in an electrolytic solution containing Al salt and Li salt. This is a method in which AI and li are precipitated in polythiophene or polythiophene derivatives while alloying AI and L:, and the ratio of AU and li in the alloy is determined by the electrolysis of Al salt and li salt. It is greatly influenced by the molecular weight ratio in the liquid.

As an electrolytic solution for electrolytically depositing Al, for example, Masayuki Yoshio, Tsuyoshi Yamayo-1 stone 11fflhiko, Electrochemistry, (44) No. 7
462-467 (described in 197B>. As a solvent for this electrolytic solution, in addition to tetrahydrofuran (TI-IF) described in the above-mentioned Bunyu, 2-methyl-, which can be used as a battery solvent, is used. Tetrahydrofuran (2
Me-THF), dioquinrane, 4-methyl-dioxolane <4Me-dioquinrane), dimethoxyethane (DME), tetramethylene sulfone <TMS), and mixtures thereof may also be used.

Furthermore, in order to increase the amount of Li chains in the alloy, L
There is a method of reducing li+ at a low electric density of 5 TrLA/cIi or less using an electrolytic solution system containing only i salt.

(3) Mixing powdered or granular polythiophene or polythiophene derivative and powdered AIL and press-molding,
A method in which, after forming an electrode, Li is electrochemically reduced to precipitate Ll in a mixture of polythiophene or a polythiophene derivative and AfL.

In this method, prepolymerized powdered or granular polythiophene or polythiophene derivative and powdered An are mixed, molded into an electrode shape, and then immersed in an electrolytic solution containing Li salt.
1+ is electrolytically reduced to create a mixed electrode. Electrolysis in this case
A mixed electrode in which li is evenly dispersed can be obtained with a low electric density of M flow seedling density of 57FLA/7FL2 or less.

(4) AfL in polythiophene or polythiophene derivative after polymerization? [So that the amount is appropriate, A! Thiophene or a thiophene derivative is chemically polymerized in a polymerization solution containing L powder, and the resulting mixture of polythiophene or polythiophene derivative and Δ is used as an electrode to electrochemically polymerize thiophene or a thiophene derivative.
A method of reducing -i to precipitate l-i in a polythiophene or polythiophene derivative and A [compound. This method involves, for example, dissolving thiophene or a thiophene derivative derivative in an ether solvent according to the Shiraki method (Japanese Patent Application Laid-Open No. 56-47421), and then reacting metallic magnesium with a monomer to produce an active organomagnesium compound. m of An powder was added, and while stirring the whole well,
When a NiN catalyst is added, a polythiophene or polythiophene derivative containing AILrfJ is obtained. When this polymer is used as an electrode and 1-i+ is electrolytically reduced with an electrolytic solution containing l-i salt in the same manner as in method (3), a three-component material electrode of polythiophene or polythiophene derivative, Al, and l-i is obtained. It will be done.

In methods (2), (3), and (4) above, (
Similar to 1), the electrode may include a current collecting substrate and the like.

The mixing ratio of the negative electrode active material during charging is expressed as an atomic St degree ratio as follows.

That is, assuming that the atomic weight of AI is 27, the atomic weight of li is 7, and in the case of polythiophene and polythiophene derivatives, the intermolecular distance per repeating unit is considered as the atomic weight here, and the atomic weight of polythiophene is 82, polythiophene or polythiophene derivative 1 .3 to 34 atomic weight%, preferably 4.4 to 9.6 atomic weight%, A1 is 11 to 7
7 atomic weight %, preferably 30 to 14 atomic a%, L
L is preferably in the range of 18 to 77 atoms, preferably 19 to 59 atoms. Note that, as a matter of course, these values exclude the weight of the current collecting substrate and the like in the electrode.

Next, the active materials of the counter electrode, that is, the positive electrode when these active materials are used for the negative electrode will be described.

There are no particular regulations regarding the positive electrode active material, but
When l-i salt is used as an electrolyte, it is a substance that is stable and undergoes a reversible reaction, and it is important that it is a substance that can be charged and discharged as a secondary battery. It must exhibit high energy density and high power density, have good cycle characteristics, and be able to maintain a low self-discharge rate.

Specific examples of compounds that reversibly form compounds with l-i+ cations in non-aqueous solvent systems include Ti 82 and V205.

Vs 013. Examples include MO82, NbSe s , graphite 7 tsunide, and examples of compounds that reversibly form compounds or charge transfer complexes with anions in the electrolyte include polymers with conjugated double bonds, such as polyacetylene and polypyrrole. and polypyrrole derivatives, polythiophene and polythiophene derivatives, polyaniline and polyaniline derivatives, polyparaphenylene and polyparaphenylene derivatives, but are not necessarily limited to these.

The electrolytic solution for the non-aqueous solvent secondary battery of the present invention is one in which an electrolyte is dissolved in a non-aqueous organic solvent.

The organic solvent mentioned here is preferably one that is aprotic and has a high dielectric constant. For example, ethers, ketones,
Amides, sulfur compounds, phosphate ester compounds, chlorinated hydrocarbons, esters, carbonates, nitro compounds, sulfolanes, etc. can be used, but among these, ethers, ketones, phosphate esters, etc. Preferred are compounds, chlorinated hydrocarbons, carbonates, and sulfolanes. Representative examples of these include tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, monoglyme, 4-methyl-2-pentanone, 1
, 2-dichloroethane, γ-buty-O-lactone, valerolactone, dimethoxyethane, methylformate, propylene carbonate, ethylene carbonate, dimethylformamide, dimethyl sulfoxide, dimethylthioformamide, ethyl phosphate, methyl phosphate, chlorobenzene, sulfolane, 3 -Methylsulfolane and the like can be mentioned.

Among these organic solvents, ethers or a mixed system of ethers and other organic solvents are preferred as stable organic solvents that can reversibly redox l-i with the negative electrode active material of the present invention.

As the electrolyte, for example, 1-iBF+.

Li AJLC1+, Li AJ8r3G love.

Li l"e C14, Li Sn C10, Li P
Fe.

Li PCjte Li Sb C 吏e, Li S
bFe.

Examples include Li, As, and Fe.

[Effects of the Invention 1] As described above, a nonaqueous solvent-based secondary battery using an active material mainly composed of the three components of polythiophene or polythiophene derivative, A and l of the present invention as a negative electrode has the following effects: Various combinations can be considered depending on the type of positive electrode active material, electrolyte, etc., but in any case, the oxidation and reduction system of Li in the negative electrode active material is reversible, has extremely low self-discharge, and has high energy density. In particular, the secondary battery of the present invention can prevent the formation of dendrites on the l-i electrode side during charging when the Li electrode is used as a negative electrode to form a secondary battery, which has been a problem in the past. Cycle life can be significantly improved.

[Example 1] Hereinafter, the present invention will be explained in more detail by giving Examples and Comparative Examples.

Example 1 Al with an atomic concentration ratio of Ax:L+ of 55:45
-Li alloy 8q and the method of Sansui et al. (JP-A-56-4742
After washing the polythiophene produced according to No. 1) with THF, it was thoroughly mixed with powdered polythiophene 2q dried under reduced pressure in a mortar under an argon atmosphere. Next, the mixture was formed into a disk shape with a diameter of 1G and φ using a mold press machine, and then wrapped in a bag with 50 mesh nickel wire mesh, a nickel wire was pulled out from a part of the nickel wire mesh, and this was used as the negative electrode active material. did.

It is complete.

As a counter electrode, about 50 g of lithium foil was press-molded on a nickel wire gauze, and was sufficiently thick so as not to be consumed during the experiment.

As the electrolyte, 1iBF4 was used with 2Me-THF and TM.
Approximately 20 m of a solution of LiBF4 having a concentration of 1 mol/l dissolved in a mixed solvent of S at a volume ratio of 1:1 was used.

The battery experimental cell shown in FIG. 1 was used as a glass cell with a sealed lid in which a platinum wire was sealed with glass to serve as a conducting wire. All battery experiments were conducted in a globe vox replaced with argon gas so that the atmosphere inside the experimental cell was an argon gas atmosphere. The distance between the negative electrode and the counter electrode was maintained at 1.01.

In the experiment, first, the current density was set to 5 mA/d, and the negative electrode Li
A current was applied in the direction that oxidized to li+. Opposite l-
When the electric current with i rose rapidly and reached 2.0V, the current was stopped and the amount of electricity that had flowed up to that point was recorded, and it was 14.5G (coulombs). This amount of electricity is
This corresponds to 15% of the amount assuming that all the Li (approximately 1.411 g) used in the negative electrode becomes L1+. Then, in the direction opposite to the negative electrode, at the same flow density of 5 mA/ctd, the amount of electricity was 2. O
A current was allowed to flow until it reached the amount of electricity that flowed until it reached v, that is, 14.5G.

The above operation is one cycle, and the negative electrode l-i
When the current flows in the direction where becomes L1+, the voltage is 2.0
If you want to continue until V and then flow in the opposite direction, do 2. in the first half of the cycle. It was repeated to flow the same amount of electricity as the amount of electricity that reached Ov.

At the 50th cycle, it flowed in the direction of releasing l-i+.
``The amount of electricity is 14.50, and the amount of electricity extracted per 1 io² of the weight of the negative electrode is 14.5G, which corresponds to 1.450,0OOG per 1 kg, or 15.0 far days.

Further, even after 100 cycles of charging and discharging, no l-i dendrite was found on the negative electrode side.

Comparative Example 1 Ai instead of the three-component active material used in the negative electrode of Example 1
:The atomic S* ratio of Ll is 55: 45(7) A i
An experiment was conducted in exactly the same manner as in Example 1, except that only -1-i alloy 8j19 was molded using a mold press machine and used as the negative electrode.

The amount of electricity that flowed until reaching 2.0 .mu. at the beginning of the first cycle was 15.4 C, which reached 80% of the reaction amount of l-i in the alloy. Next, when current is passed in the opposite direction, li dendrites have already appeared, and in the second cycle 2,
The amount of electricity that flowed until it reached 0■ was 12.5G, and gradually decreased with each cycle. And 100
The amount of electricity that could be extracted by the time the battery reached 2.0 cm in the first cycle was 3.2 C, which was only 21% of the amount in the first cycle.

Dendrites were strongly visible on the negative electrode after 50 cycles, and this is considered to be the cause of the decrease in the amount of electricity. In addition, lithium pieces with peeled dendrites were floating on the surface of the electrolyte.

Example 2 Electrolytic legal polymerization conditions: Electrolytic polymerization solution; 1 mol/N-LiBF++ 0.05 mol/
Electrolytic polymerization of crossthiophene in propylene carbonate solution: 10 mA/ai constant current method Counter electrode: While stirring the solution with a Li plate, a film-like polythiophene was prepared, and then the 8F'4 dopant doped during polymerization was prepared. 2 for the counter electrode 1-i. It was held at a constant voltage of Ov for 24 hours and then subjected to and-pumping to obtain a neutral polythiophene. This polythiophene film was peeled off from both sides of the platinum substrate separately, washed several times with acetonitrile, and dried under reduced pressure repeatedly. When the 41 of the polythiophene was measured, one sheet had 2.5Rg, and the other sheet had 2.5Rg. is 2.2#
It was I9.

Next, the polythiophene film with [t of 2.51Rg] was wrapped with Ni net, and a 1 mol/l
ΔIC of i and 3.0.5 mol/1 TH of LiAuH+
Using solution F as an electrolytic solution, AfL was deposited into the polythiophene film at a constant weight of 0.57 rLA/cj.

This polythiophene film on which An was precipitated was heated in THF.
After washing with water and drying under reduced pressure, the weight was 7.4 cm, and when observed with a microscope, A1 metal was almost uniformly precipitated in the pores of the polythiophene.

Further, this film was further added to 0.5 mol/1 Li
PFe /2M11! - 1-i at a constant current of 0.5 mA/ai by electrolytic method using F vs. 1k-Li metal in HF solution
When the weight was measured after reducing, the weight was 8.9
II1g. The atomic concentration of this active material is 7 atomic weight % for polythiophene, 43 atomic weight % for Al, and 50 atomic weight % for 1.

The active material consisting of the three components of polythiophene, An and Li prepared by the above method was sandwiched between Ni meshes and used as a negative electrode, and the positive electrode was used as a positive electrode. T I S 2 of the weight of OIIg,
Binder Teflon 2JI9 and conductive agent Carbon Black 2
q was mixed and molded by placing it on a nickel mesh.

As the electrolyte, LiPFe was used as 2Me-T)-IF
A solution having a concentration of 1.0 mol/l of 1ipFe dissolved in a solvent containing 1ipFe and DME mixed at a volume ratio of 2:1 was used.

The current density of the battery during the battery experiment was a constant current of 577 LA/m, and the cell voltage was 0.5.
When the current was passed until the voltage reached 18.
It was 70. Thereafter, the battery was charged with the same amount of electricity at the same current density, and then discharged until the cell voltage reached O and SV.The above operations were then repeated to examine the cycle characteristics of this battery.

As a result, it was found that the ratio of discharged electricity i to charged electricity at the 100th cycle was 99%, indicating that this battery worked almost completely reversibly.

The energy density of this battery calculated from the 100th discharge electricity amount is 6351/l/per negative electrode active material.
-hr/I was drunk.

After charging this battery for the 5th cycle, it was left in the circuit for 24 hours, and then discharged until it reached 1.0■, and the self-discharge rate (SD) was calculated using the formula: 5D = 0. It was 8%.

Example 3 2.0 mm of polythiophene powder obtained by polymerization in the same manner as in Example 1, A1 powder purified according to a conventional method, 6.
After mixing 01115 well in a mortar, mold it into a pellet and use it as an electrode, and use a Li plate as a counter electrode.
A glass separator with a thickness of 2 am is sandwiched between the counter electrode and l-i+ is reduced into the above electrode in 1M LiBF4/THE with a constant current of 1.0 mA/d to reduce l-i to 1.5μ. An amount of electricity equivalent to that of

This electrode was washed with TI-IF and then dried under reduced pressure to prepare a negative electrode active material. Expressing this negative electrode active material in terms of atomic concentration, polythiophene is 5 atomic weight %, Al is 48 atomic weight %,
The composition has a l−i ratio of 47 atomic percent.

Then, add fresh 1 mol Li BF4 /-rHF again
Ti 82 immersed in an electrolytic solution and used as a counter electrode exactly the same as in Example 2.
A discharge was started at a current density of 5'rrLA/cd using the cell shown in FIG. 2 with a glass separator having a thickness of 1jI#I sandwiched between the system electrode and the counter electrode.

When the end of discharge was set to O, SV, the amount of discharged electricity was 19.
It was 1C.

Thereafter, the battery was charged for an amount equivalent to the amount of electricity discharged for the first time, and then discharged until the cell voltage reached 0°5V.The above operation was then repeated to examine the cycle characteristics of this battery.

As a result, the ratio of the amount of discharged electricity to the charged electrical layer at the 100th cycle was 99% or more.

The energy density of the battery calculated from the amount of electricity discharged for the 100th time was 556 W-hr/Kg per negative electrode active material. In addition, when the self-discharge rate was examined by the same method as in Example 2, it was found to be 1.0% (31).

Comparative Example 2 Instead of the negative electrode active material used in Example 3, 1.5
i-foil was used as the negative electrode active material, and the same Ti 82-based electrode as in Example 3 was used as the positive electrode.

Otherwise, the cycle characteristics of the battery were examined in exactly the same manner as in Example 3.

The first discharge electricity is 19. IC, and the amount of electricity was approximately equal to the amount of electricity in Example 3.

After that, when the charging and discharging electricity of Example 3 was charged and discharged, the charging and discharging efficiency started to decrease from the 5th cycle.
Discharge became impossible at the 0th cycle. When this battery was disassembled, it was found that 1-i dendrites were heavily formed in the separator, which was presumed to have reduced the battery performance.

[Brief explanation of the drawing]

FIG. 1 is a schematic cross-sectional view of a glass cell for testing a battery with a sealed lid, which is an example of the present invention, and FIG. 2 is a battery for measuring the characteristics of a non-aqueous solvent-based secondary battery, which is a specific example of the present invention. It is a cross-sectional schematic diagram of a cell. 1...Platinum wire 2...Nickel wire 3.
...Nickel mesh (working electrode) 4...Nickel mesh (counter electrode) 5...Electrolyte 6...
Glass airtight lid 7...Glass IJ battery cell 8...Negative electrode lead wire 9...Negative electrode current collector 10...Negative electrode 1
1... Porous glass separator 12... Positive electrode 13... Positive electrode current collector 14... Positive electrode lead wire 15... Teflon container Fig. 1 Fig. 2

Claims (1)

[Claims] A non-aqueous solvent secondary battery characterized in that an active material mainly composed of three components: polythiophene or a polythiophene derivative, aluminum, and lithium is used as a negative electrode.