JP2556408B2 - Organic electrolyte battery - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a secondary battery, and more particularly to a secondary battery using an insoluble and infusible substance having semiconductor properties for a positive electrode and a negative electrode.

[0002]

2. Description of the Related Art In recent years, portable and cordless home appliances and electronic devices have been rapidly advancing. Along with this, compact and lightweight batteries with high performance have been demanded as power sources. Currently, so-called primary batteries such as dry batteries and secondary batteries such as Ni-Cd batteries and lead batteries are used as power sources for the above devices. However, recently, a secondary battery which has a short life and needs to be replaced and which can be repeatedly charged has been widely used. Among them, Ni-Cd batteries are currently the mainstream as a power source for small devices, but the performance improvement is approaching the limit due to the need for higher capacity. In addition, discussions on global environmental issues have been active in the last few years, and public opinion about the harmfulness of Cd, which is an active material, is increasing. Therefore, there is great expectation for the development of secondary batteries that have higher performance than Ni-Cd batteries, and that are more reliable and safer.

The applicant of the present invention has previously used, as an electrode active material, a material obtained by doping an insoluble and infusible substrate containing a polyacene skeleton structure, which is a kind of organic semiconductor, with an electron donating substance or an electron accepting substance as an electrode active material. A battery has been proposed (JP-A-60-170163). This battery is high performance and thin,
It is a promising secondary battery because it has the potential for weight reduction, has high oxidation stability of the electrode active material, and is easy to mold.

Further, the applicant of the present invention has used a composite of a polyacene-based organic semiconductor and a metal oxide as an active material, and a lithium-doped molded article containing the polyacene-based organic semiconductor on a negative electrode, which is supported at a high voltage. We have proposed a secondary battery that can be charged and discharged for a long time (Japanese Patent Application No. 3-204769).
This secondary battery is a highly safe battery that does not generate dendrite (a dendrite of Li) while having the characteristic of high voltage, which is a characteristic of lithium-based batteries. However, the battery capacity was still insufficient.

Further, the applicant of the present invention discloses that a polyacene-based organic semiconductor and vanadium pentoxide having an average particle size of 1 μm or less are used as active materials, and a ratio of pores of 0.1 μm or less is 70%.
A secondary battery having a positive electrode occupying the above and a negative electrode using a polyacene-based organic semiconductor has also been proposed (Heisei 3
Patent application filed on December 2, 2012). Although this battery is characterized by a large capacity per unit volume, its rapid chargeability is not yet satisfactory.

[0006]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a secondary battery having a large capacity and excellent quick charging characteristics.

Another object of the present invention is to provide a secondary battery which can be charged and discharged for a long period of time, is excellent in safety, is easy to manufacture, and is economical.

[0008]

Means for Solving the Problems As a result of intensive studies in view of the above problems, the present inventors have controlled the average particle size of vanadium pentoxide in the positive electrode and the pore volume of the positive electrode within a specific range. When the positive electrode is formed into a composite body obtained by simultaneously pulverizing the active material and the conductive material, and is combined with the negative electrode in which lithium is supported on the body containing the polyacene-based organic semiconductor, the battery has a rapid charging characteristic. The inventors have found that it is improved and have reached the present invention.

That is, the present invention provides an organic electrolyte battery comprising a positive electrode, a negative electrode, and an electrolytic solution containing a solution of a lithium salt dissolved in an aprotic organic solvent, wherein the positive electrode is
(1) (a) A heat-treated product of an aromatic condensed polymer composed of carbon, hydrogen and oxygen, which has a polyacene skeleton structure having a hydrogen atom / carbon atom number ratio of 0.05 to 0.5,
And an active material which is a composite of (b) vanadium pentoxide particles having an average particle size of 1 μm or less and (b) an insoluble infusible substrate having a specific surface area of 600 m ² / g or more as measured by the BET method, and
(c) At least a conductive material is included, and (2) the pore volume having a pore diameter of 0.1 μm or less is 70% of the total pore volume.
Occupies the above (measured by mercury porosimetry), and (3) (a)
, (B) and (c) are simultaneously pulverized and mixed, and the negative electrode is a heat-treated product of (a) an aromatic condensation polymer composed of carbon, hydrogen and oxygen. hand,
The carbon of the insoluble infusible substrate containing lithium is added to a molded product containing an insoluble infusible substrate having a polyacene skeleton structure having a hydrogen atom / carbon atom atomic ratio of 0.05 to 0.5 and (b) a thermosetting resin. It is characterized in that it is supported by 3% or more in terms of atomic percentage with respect to atoms.

In the present invention, the insoluble and infusible substrate having a polyacene-based skeleton structure (hereinafter referred to as P
AS).
No. 60-152554, JP-A No. 60-170163, and the like. Here, the aromatic condensation polymer is a condensation product of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde. As the aromatic hydrocarbon compound, so-called phenols such as phenol, cresol and xylenol are preferable, but not limited to these.

For example, the following formula (Formula 1):

[0012]

Embedded image (Where x and y are independently 0, 1 or 2)
Can be methylene bisphenols, or hydroxy-biphenyls and hydroxynaphthalenes. Of these, phenols are practically preferable, and phenol is particularly preferable.

As the aromatic condensation polymer in the present invention, a part of the above-mentioned aromatic hydrocarbon compound having a phenolic hydroxyl group is an aromatic hydrocarbon compound having no phenolic hydroxyl group, for example, xylene and toluene. It is also possible to use a modified aromatic polymer substituted with aniline or the like, for example, a modified aromatic polymer which is a condensate of phenol, xylene and formaldehyde, and a modified aromatic polymer substituted with melamine or urea. Polymers can also be used. Furan resins are also suitable.

As the aldehyde, formaldehyde, acetaldehyde, furfural and the like can be used, and formaldehyde is preferred. The phenol / aldehyde condensate may be a novolac type, a resole type, or a composite thereof. It is also possible to use a spherical phenolic resin (sphere diameter of about 100 μm or less) commercially available as Bellpearl R (trademark: manufactured by Kanebo Co., Ltd.). The PAS in the present invention is a heat-treated product of the aromatic compound as described above, and can be produced, for example, as follows.

An inorganic substance such as zinc chloride, sodium phosphate, sodium hydroxide, potassium hydroxide or potassium sulfide is mixed with the aromatic condensation polymer. As a mixing method, the aromatic condensation polymer may be dissolved in a solvent such as methanol, acetone, or water, and then the above-mentioned inorganic substance may be added and sufficiently mixed. Further, if the aromatic condensation polymer is a meltable one such as novolac, it may be mixed under heating. The mixing ratio of the aromatic condensation polymer and the above-mentioned inorganic substance varies depending on the type and shape of the polymer and the inorganic substance to be mixed, but the weight ratio is 1
0/1 to 1/7 is preferable.

Next, the above mixture is cured into a film, plate, fiber, cloth, granule or a mixture thereof.

The cured product thus obtained is then in a non-acidic atmosphere at 350 to 800 ° C., preferably 350 to 70.
It is heated to a temperature of 0 ° C, particularly preferably 400-600 ° C. The non-oxidizing atmosphere in which the heat treatment of the aromatic condensation polymer is performed is, for example, nitrogen, argon, helium, neon, carbon dioxide atmosphere, or vacuum,
Nitrogen is preferably used. The non-oxidizing atmosphere may be stationary or flowing.

By thoroughly washing the obtained heat-treated body with water, dilute hydrochloric acid or the like, the inorganic salt contained in the heat-treated body can be removed, and then, when this is dried, PAS having a large specific surface area can be obtained. it can.

Such a PAS used in the positive electrode in the present invention has a hydrogen atom / carbon atom atomic ratio (hereinafter referred to as H / C).
The ratio) is 0.05 to 0.5, preferably 0.1 to 0.35. X-ray diffraction (CuKα)
According to, the position of the main peak is 20.5
It exists between ~ 23.5 °, and besides this main peak
There are other peaks between 41 and 46 degrees.

That is, it is understood that the PAS is a polyacene-based benzene polycyclic structure uniformly and moderately developed between polyacene-based molecules. When the H / C ratio exceeds 0.5, the charge efficiency of charging and discharging of a secondary battery using a composite of PAS and vanadium pentoxide as a positive electrode is deteriorated. On the other hand, if this value is less than 0.05, the capacity of the battery will decrease.

B of PAS used for the positive electrode in the present invention
The specific surface area value by the ET method is 600 m ² / g or more.
If it is less than 600 m ² / g, in a battery using this as a positive electrode, it is difficult to smoothly dope ions having a relatively large ionic radius, such as ClO ₄ ⁻ and BF ₄ ⁻ , so that the charging voltage is increased. Therefore, the energy efficiency is lowered and the electrolyte is deteriorated.

In the present invention, since the PAS of the positive electrode has a high specific surface area of 600 m ² / g or more as described above, sufficient performance as an active material, that is, the capacity of the PAS to be used has no relation to the particle size. Can be pulled out enough. However, if the particle size of the PAS is too large, in the PAS matrix, that is, between the PAS particles,
Since it becomes difficult to disperse vanadium pentoxide, which is liable to secondary aggregation, the particle size is preferably 1 μm or less.

The positive electrode in the secondary battery of the present invention uses the above-mentioned composite of PAS and vanadium pentoxide as an active material. Vanadium pentoxide is generally represented by the formula of V ₂ O ₅ , but actually has a width as represented by the formula of V ₂ O _x (4.5 ≦ x <5.5). . Vanadium pentoxide is a kind of metal oxide capable of intercalating or deintercalating lithium ions.
It becomes a compound represented by iV ₂ O ₅ and Li ₂ V ₂ O ₅ .
Vanadium pentoxide in the present invention also includes such a composite oxide obtained by intercalation of lithium ions. Further, vanadium pentoxide may be in a crystalline state, in an amorphous state by heat treatment or the like, or in a mixture of both. However, crystalline vanadium pentoxide is particularly preferable for obtaining a high-voltage secondary battery.

In the positive electrode of the battery of the present invention, the average particle size of vanadium pentoxide must be 1 μm or less finally, that is, when it becomes a positive electrode. This is because the above-mentioned PAS having a large surface area can sufficiently draw out its available capacity irrespective of the particle size, whereas in the case of vanadium pentoxide, if the particle size is too large, the available capacity can be sufficiently drawn out. Because it becomes difficult. Further, vanadium pentoxide has a low electric conductivity, and therefore a large particle size is disadvantageous for rapid charging. That is, when vanadium pentoxide having a particle size of more than 1 μm is used, even if the pore distribution condition in the positive electrode, which will be described later, is satisfied, the capacity is not sufficient and the rapid chargeability is poor.

The positive electrode of the battery of the present invention is a composite of PAS and vanadium pentoxide having a high specific surface area.
Proposed in consideration of utilizing the characteristic of vanadium pentoxide that it can produce a high capacity at a specific voltage, for example, 2.5 V (relative to Li / Li ⁺ ) while taking advantage of the stability and rapid charging characteristics that are the characteristics of It was done. Therefore,
The ratio of PAS / vanadium pentoxide is important, 90 /
10-30 / 70 (weight ratio), especially 70 / 30-30 /
It is preferably 70. Especially when vanadium pentoxide increases too much, only the characteristics of vanadium pentoxide are emphasized,
The advantages of combining with PAS are lost.

Next, examples of the conductive material used in the present invention include carbon black such as acetylene black and Ketjen black, and those having a particle diameter as small as possible are preferable. The amount of the conductive material in the electrode may vary depending on the use of the electrode, but 2% to 40% by weight of the active material
It is preferred that If the amount of the conductive material is too large, the amount of the active material is relatively small, so that the capacity of the battery is low.

The battery electrode of the present invention has the above-mentioned (a) PA.
It is obtained by molding a composite in which S, (b) vanadium pentoxide and (c) a conductive material are simultaneously pulverized and mixed. It is important to grind and mix the three members at the same time, and the effects of the present invention cannot be obtained only by grinding and mixing the two members, PAS and vanadium pentoxide. For example, when (a) and (b) are crushed and mixed at the same time and then (c) is simply mixed to form an electrode, vanadium pentoxide is homogeneously dispersed in PAS, so that a battery having a large capacity can be obtained. However, it is not satisfactory in terms of rapid charging characteristics.

The three forms of crushing are massive, granular,
Any form that allows easy mixing, such as plate, powder, and short fiber, may be used. When using powder of PAS and vanadium pentoxide, if the particle size before pulverization is too small, the effect of simultaneous pulverization is small, and thus the advantages of the present invention are difficult to obtain.

The pulverizing and mixing method is not particularly limited, but it is preferable to use a fine pulverizer represented by a ball mill such as a pot mill or a vibration mill.

The crushing time should be determined according to the crushing method, the crushing amount, and the kind of the substance to be crushed, but it is preferably 1 hour or longer, and when the method having a weak crushing power is used, the crushing time may be longer. preferable.

The positive electrode according to the present invention can be obtained by molding a composite to which a binder and the like are added, if necessary, in addition to the above three components. The binder and the like are not specified in the present invention, and those generally used for battery electrodes are suitable.

The molding method is not particularly limited, and a conventional molding method used for powders, for example, a pressure molding method can be used.

The positive electrode thus obtained has a pore volume having a pore diameter of 0.1 μm or less of 70 with respect to the total pore volume.
%, Preferably 75% or more. The method of measuring the pore volume mainly includes the mercury porosimetry method and the capillary condensation method. In the present invention, the mercury porosimetry method having a wide measurement range (pore distribution of 0.006 μm to 100 μm) was used. Therefore, the total pore volume in the present invention is 0.006 μm or more per unit weight of the electrode.
It means the sum of the volumes of pores having a pore diameter of not more than μm. The pore volume having a pore diameter of 0.1 μm or less means the total volume of pores having a pore volume of 0.006 μm or more and 0.1 μm or less.

In the positive electrode of the battery of the present invention, since fine vanadium pentoxide particles of 1 μm or less are uniformly distributed among the PAS particles, the proportion of pores of 0.1 μm or less is large. In particular, it is preferable that vanadium pentoxide of about 0.1 μm or less is uniformly dispersed between PAS particles of about 0.2 to 0.6 μm.

The shape of the positive electrode is not particularly limited, and may take various shapes such as a plate, a film, and a cylinder.

Next, the negative electrode of the battery of the present invention is obtained by doping and supporting lithium on a molded body containing an insoluble and infusible substrate having a polyacene skeleton structure and a thermosetting resin. The insoluble and infusible substrate having a polyacene-based skeleton structure used in the negative electrode is hereinafter referred to as PAS '.
PAS 'has an H / C ratio of 0.05 to 0.5, preferably 0.1 to 0.
With 35 polyacene skeleton structures, the same PAS as in the positive electrode can be used. Also in the negative electrode, when the H / C ratio of PAS 'is less than 0.05, the structure of the base body is apt to change when lithium is carried or when lithium is taken in and out (during charge and discharge), and the cycle characteristics are deteriorated. . On the other hand, when the H / C ratio exceeds 0.5, lithium cannot be stably supported, and a battery manufactured using such a negative electrode in which lithium is supported on PAS 'has large self-discharge.

The negative electrode further had a specific surface area of 600 m ² / g, which was not suitable for the positive electrode.
It is also possible to use PAS 'which is less than. Such a low specific surface area PAS 'is the PAS in the positive electrode described above.
In the production process of, the aromatic condensation polymer is cured without adding an inorganic substance such as zinc chloride, and then 400 to 1000 ° C. in a non-oxidizing atmosphere (including a vacuum state).
Can be produced by heat-treating at a temperature of, preferably 600 to 800 ° C. to obtain a heat-treated product having an H / C ratio of the above value.

In the negative electrode, the average particle size of PAS 'is preferably 0.1 to 5 μm. In particular, when PAS 'having a specific surface area value by BET method of less than 600 m ² / g and an average particle diameter of 0.1 to 5 μm is used for the negative electrode, the effect of the present invention becomes remarkable. Here, the average particle size of PAS 'is
The Stokes diameter obtained by the centrifugal sedimentation method or the like (the diameter of spherical particles of the same density that sediment in the same medium at the same velocity as the sample particles) was defined as the particle diameter at which the cumulative sieving percentage is 50%.

Examples of the thermosetting resin used in the negative electrode together with the PAS 'for molding include those capable of suppressing loosening of the electrode, for example, phenol resin, melamine resin, furan resin and the like. The ratio of thermosetting resin in the molded product is P
It is determined by the shape of AS ', the specific surface area of PAS', the amount of binder, the amount of lithium supported, etc., but the proportion in the negative electrode is preferably 1 to 70% by weight, more preferably 5 to 50%. Is. If the amount of the thermosetting resin is too small, the effect of suppressing the loosening of the negative electrode is small, and if the amount is too large, the amount of PAS ′ is naturally small, and sufficient lithium cannot be supported, resulting in a decrease in battery capacity. I will end up.

A molded article containing PAS 'and a thermosetting resin is
It can be roughly classified into two methods. First
Is to knead PAS 'in the form of powder, short fiber or the like which is easy to mix with an initial condensate of a thermosetting resin, if necessary, by adding a solvent such as methanol, toluene or water, and kneading the mixture.
This is a method of performing pressure molding simultaneously with curing under heating at 0 to 200 ° C. The second method is the PAS 'in the above embodiment.
Is mixed with a binder generally used for battery electrodes, such as polytetrafluoroethylene, polyethylene, or polypropylene, or if necessary, kneaded and molded, and then this molded body is thermosettable. After impregnating the initial condensate of the resin,
This is a method of drying and curing by heating or the like.

The loading of lithium on the thus obtained molded body may be appropriately selected from known doping methods such as an electrolytic method, a gas phase method, a liquid phase method, and an ion implantation method. For example, when lithium is supported by an electrolytic method, the PAS ′ molded body is immersed in an electrolytic solution containing lithium ions as a working electrode, and a current is applied to the counter electrode in the same electrolytic solution, or a voltage is applied. Is applied.

The above-mentioned molded product can also be supported by directly contacting an appropriate amount of lithium foil.

When the gas phase method is used, the PAS 'compact is exposed to, for example, lithium vapor. When the liquid phase method is used, for example, a complex containing lithium ions is brought into contact with PAS '. Examples of the complex used in this reaction include, but are not limited to, an alkali metal naphthalene complex and an alkoxide.

The amount of lithium supported on the PAS 'by the above method is at least 3%, preferably at least 10%, in atomic percentage (percentage of the number of lithium atoms to one carbon atom of PAS'). The amount of lithium varies depending on the specific surface area of the PAS ', the capacity of the positive electrode to be combined, and the like. The potential of the PAS' molded article supporting lithium is Li / Li
^It is desirable to carry lithium so as to be 1.0 to ⁰ V with respect to ⁺ . When the amount of lithium is small, the capacity of the battery of the present invention decreases, and when it is large, excess lithium is deposited on the surface of the PAS 'molded body.

As a solvent constituting the electrolytic solution used in the present invention, an aprotic organic solvent is used. Examples of the aprotic organic solvent include ethylene carbonate, propylene carbonate, γ-butyrolactone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolan, methylene chloride, sulfolane and the like. These aprotic organic solvents can be used alone or as a mixed solution of two or more kinds.

The electrolyte mixed or dissolved in a single solvent may be any electrolyte capable of generating lithium ions. Such electrolytes include, for example, LiI,
LiClO ₄ , LiAsF ₆ , LiBF ₄ or LiH
It is F ₂ .

The above-mentioned electrolyte and solvent are mixed in a sufficiently dehydrated state to form an electrolyte. The concentration of the electrolyte in the electrolyte is at least 0.1% in order to reduce the internal resistance due to the electrolyte. It is preferably at least 1 mol / l, more preferably 0.2 to 1.5 mol / l.

The organic electrolyte battery of the present invention comprises the above positive electrode,
It is provided with a negative electrode and an electrolytic solution, and in general, the positive electrode and the negative electrode are arranged via a separator.

In the present invention, when a composite of PAS and vanadium pentoxide is used for the positive electrode, it is considered that the high capacity and average potential of the vanadium pentoxide itself are exploited by the combination with the negative electrode using PAS '. .

Hereinafter, the present invention will be described in more detail with reference to examples.

[0051]

EXAMPLES The following polyacene materials were used in the examples. I (for positive electrode and negative electrode) Water-soluble resole type phenol resin (about 60% concentration) / zinc chloride / water at a ratio of 10/25/5 by weight, a slurry 10 cm x 10 cm Pour into a mold of × 1 cm and cover it with a glass plate to prevent evaporation of water.
It was cured by heating at 0 ° C. for 1 hour. This cured product was placed in a silicon knit electric furnace and heated in a nitrogen stream at a rate of 40 ° C./hour to 500 ° C. for heat treatment. Next, this heat-treated product is washed with dilute hydrochloric acid to remove zinc chloride, then washed with water, and then dried to obtain a plate-shaped P
I got AS. The specific surface area of this PAS by the BET method is 2
It was an extremely large value of 000 m ² / g. In addition, elemental analysis revealed that the atomic ratio of hydrogen atoms / carbon atoms was 0.23. The shape of the peak from X-ray diffraction is a pattern based on the polyacene-based skeleton structure and is 2 at 2θ.
A broad main peak was present in the vicinity of 0 to 22 °, and a small peak was confirmed in the vicinity of 41 to 46 °.

The PAS thus obtained was divided into lumps of about 1 to 5 cm square, and this was used as lump PAS (PAS-A) in the following examples. Also, PA with an average particle size of 0.7 μm was crushed for 24 hours with a nylon ball mill.
S powder was obtained. This is referred to as PAS powder B. In addition, PA
The average particle diameter of the S powder was determined by electron microscopy ("Powder", edited by Teruichiro Kubo et al., 1979, revised 2nd edition, Maruzen Co., Ltd.). II (for negative electrode) novolac type phenol resin was placed in a silicon knit electric furnace and heated at 750 at a temperature rising rate of 10 ° C./hour under a nitrogen atmosphere.
It heats up to (degreeC) and heat-processes.

The H / C ratio of the obtained PAS 'was 0.12.

This PAS 'was crushed with a nylon ball mill for 10 minutes and 24 hours while changing the crushing time to obtain an average particle size of 3.4 μm (PAS' powder C).
And a PAS ′ powder of 0.79 μm (PAS ′ powder D). Specific surface area by BET method is 230m ² each
/ G and 240 m ² / g. The average particle size of PAS 'powder was determined by the centrifugal sedimentation method. Example 1 (1) Production of Positive Electrode 60 parts by weight of bulk PAS (PAS-A), V ₂ O ₅ 4
0 parts by weight and carbon black as a conductive material (trade name: Black Pearl, manufactured by Cabot Corporation, average particle size 0.02μ
m) 25 parts by weight were put into an alumina ball mill and pulverized and mixed for 24 hours. When the resulting composite powder was observed with an electron microscope, the average particle size of PAS was 0.5 μm. However, V ₂ O ₅ particles are very small, and PAS
Are homogeneously mixed with particles and a conductive material particles, V ₂ O
Accurate measurement of the ₅ particle diameter was difficult, but none of the V ₂ O ₅ particles above 0.1 μm was found.

With respect to 100 parts by weight of the obtained composite powder,
5 parts by weight of polytetrafluoroethylene was added as a binder, mixed and kneaded in a mortar, and then formed into a sheet with a roller to obtain an electrode sheet having a thickness of 750 μm. The pore distribution of this electrode sheet was measured by a mercury porosimeter (Poresizer, manufactured by Shimadzu Corp.), and was (0.006 μm or more:
Pore volume having a pore diameter of 1 μm or less) / (0.00
The ratio of the volume of pores having a pore diameter of 6 μm or more and 100 μm or less) was 81%. This electrode sheet was punched into a 15 mmφ, It was set to 1. (2) Production of negative electrode To 100 parts by weight of PAS 'powder D, 10 parts by weight of polytetrafluoroethylene as a binder was added and mixed in a mortar,
After kneading, the sheet is formed with a roller to a thickness of 400
It was formed into a film having a thickness of μm to obtain a preform of the negative electrode. Next, this preform was immersed in a methanol solution (about 25% concentration) of a resol type phenol resin initial condensate to impregnate the preform with the phenol resin. The amount of the phenol resin impregnated was 8.7% by weight based on the preform.
This impregnated film was cured at 200 ° C. for 2 hours under a nitrogen atmosphere. The obtained negative electrode molded body was punched out to a diameter of 15 mm and this was molded body No. It was set to 1.

The obtained negative electrode molded body No. Electrochemical cell was assembled by using 1 as a working electrode, lithium metal as a counter electrode and a reference electrode, and a 1 mol / liter solution of LiClO ₄ dissolved in sufficiently dehydrated propylene carbonate as an electrolyte. A voltage of 0.2 V is applied to lithium for 12
By applying for a time, the negative electrode molded body was made to carry lithium. The amount of lithium carried was 32 atom%, which was determined by integrating the values of the currents flowing in the circuit. This is the negative electrode No. Set to 1. (3) Battery assembly 1, negative electrode No. 1 and a 1M LiClO ₄ propylene carbonate solution as an electrolytic solution, and a glass nonwoven fabric as a separator were assembled as shown in FIG. The battery was charged at a constant voltage of 3.6 V for 6 hours, then discharged at 2 mA to 2.0 V, and the initial capacity was measured. Subsequently, constant-voltage charging was performed at 3.6 V for 30 minutes, followed by discharging in the same manner as described above to measure the capacity, and the ratio of this value to the initial capacity was evaluated as a rapid charging characteristic. The results are shown in Table 1. Example 2 (1) Production of Positive Electrode 60 parts by weight of lump PAS, 40 parts by weight of V ₂ O ₅ and 25 parts by weight of carbon black (trade name: Black Pearl, average particle size 0.02 μm, manufactured by Cabot Corporation) as a conductive material were made of alumina. The mixture was put into a ball mill made for pulverization and mixed for 48 hours. When the resulting composite powder was observed with an electron microscope, the average particle size of PAS was 0.3 μm. But,
The V ₂ O ₅ particles were very small and were intimately mixed with the PAS particles and the conductive material particles, making accurate measurement of the V ₂ O ₅ particle diameter difficult, but for the V ₂ O ₅ particles 0 Nothing exceeding 1 μm was found.

When an electrode sheet was prepared from the obtained composite powder in the same manner as in Example 1, the proportion of pores of 0.1 μm or less was 86%. This electrode sheet was punched into a 15 mmφ, And 2. (2) Assembling the battery A battery was assembled in the same manner as in Example 1 except that 2 was used as the positive electrode. Using this battery, the initial capacity was measured in the same manner as in Example 1, and 3
The capacity after charging at a constant voltage for 0 minutes was measured to evaluate the quick charging characteristics. The results are shown in Table 1. Example 3 (1) Production of Negative Electrode A preform was produced in the same manner as in Example 1 except that PAS ′ powder C was used, and a preform was impregnated and cured in the same manner as in Example 1, A negative electrode molded body was manufactured.
The amount of the phenol resin impregnated was 8.1% by weight based on the preform. Next, lithium was carried on the obtained molded body (this was designated as No. 2) in the same manner as in Example 1. The amount of supported lithium was 28 atomic%. This is the negative electrode No. Set to 2. (2) Battery assembly A battery was assembled in the same manner as in Example 1 except that 2 was used as the negative electrode. Using this battery, the initial capacity was measured in the same manner as in Example 1, and 3
The capacity after charging at a constant voltage for 0 minutes was measured to evaluate the quick charging characteristics. The results are shown in Table 1. Example 4 Positive electrode No. manufactured in Example 2 No. 2 and the negative electrode Nos. A battery was assembled in the same manner as in Example 1 except that Battery No. 2 was used. Using this battery, the initial capacity was measured in the same manner as in Example 1, and the capacity after constant-voltage charging for 30 minutes was measured to evaluate the rapid charging characteristics. The results are shown in Table 1. Example 5 (1) Production of Negative Electrode A preform was produced in the same manner as in Example 1 except that PAS powder B was used, and a preform was impregnated and cured in the same manner as in Example 1 to obtain a negative electrode. A molded body was manufactured. The amount of phenol resin impregnated was 3 for the preform.
It was 6% by weight. Next, the obtained molded body (this is
o. 3) was loaded with lithium in the same manner as in Example 1. The amount of supported lithium was 78 atomic%. This is the negative electrode No. Set to 3. (2) Battery assembly A battery was assembled in the same manner as in Example 1 except that No. 3 was used as the negative electrode. Using this battery, the initial capacity was measured in the same manner as in Example 1, and 3
The capacity after charging at a constant voltage for 0 minutes was measured to evaluate the quick charging characteristics. The results are shown in Table 1. Example 6 Positive electrode No. manufactured in Example 2 2 and the negative electrode No. manufactured in Example 5. A battery was assembled in the same manner as in Example 1 except that Battery No. 3 was used. Using this battery, the initial capacity was measured in the same manner as in Example 1, and the capacity after constant-voltage charging for 30 minutes was measured to evaluate the rapid charging characteristics. The results are shown in Table 1. Example 7 (1) Production of positive electrode Acetylene black as a conductive material (made by Denki Kagaku Kogyo Co., Ltd., trademark: Denka Black, average particle size 0.03 μm)
A composite powder was obtained in the same manner as in Example 2 except that 30 parts by weight was used. The average particle size of PAS was 0.3 μm. However, V ₂ O ₅ particles are very small, and PAS
The particles and the conductive material particles are homogeneously mixed,
Nothing exceeding μm was found.

When an electrode sheet was prepared from the obtained composite powder in the same manner as in Example 1, the proportion of pores of 0.1 μm or less was 75%. This electrode sheet was punched into a 15 mmφ, It was set to 3. (2) Assembling the battery A battery was assembled in the same manner as in Example 1 except that No. 3 was used as a positive electrode. Using this battery, the initial capacity was measured in the same manner as in Example 1, and 3
The capacity after charging at a constant voltage for 0 minutes was measured to evaluate the quick charging characteristics. The results are shown in Table 1. Comparative Example 1 (1) Production of Positive Electrode The same PAS and V ₂ O ₅ used in Example 1 were mixed with P
AS / V ₂ O ₅ = 60/40 (weight ratio) was put into an alumina ball mill and pulverized for 24 hours. The obtained PAS
When the composite of V ₂ O ₅ and V ₂ O ₅ was observed with an electron microscope, the average particle size of PAS was 0.5 μm. But,
The V ₂ O ₅ particles were very small and were intimately mixed with the PAS particles, none above 0.1 μm was found.

To 100 parts by weight of the obtained composite, 25 parts by weight of carbon black (trade name: Black Pearl, manufactured by Cabot Corporation) as a conductive agent and 5 parts by weight of polytetrafluoroethylene as a binder were added, After mixing in a mortar,
A positive electrode was manufactured in the same manner as in Example 1, and the positive electrode No.
It was set to 4. The proportion of pores having a diameter of 0.1 μm or less was 86%. (2) Assembling the battery A battery was assembled in the same manner as in Example 1 except that 4 was used as the positive electrode. Using this battery, the initial capacity was measured in the same manner as in Example 1, and 3
The capacity after charging at a constant voltage for 0 minutes was measured to evaluate the quick charging characteristics. The results are shown in Table 1. Comparative Example 2 (1) Production of Positive Electrode The same PAS and V ₂ O ₅ used in Example 1 were mixed with P
AS / V ₂ O ₅ = 60/40 (weight ratio) was put into an alumina ball mill and pulverized for 48 hours. The obtained PAS
When the composite of V ₂ O ₅ and V ₂ O ₅ was observed with an electron microscope, the average particle size of PAS was 0.4 μm. But,
The V ₂ O ₅ particles were very small and were intimately mixed with the PAS particles, none above 0.1 μm was found.

Using the obtained composite, a positive electrode was manufactured in the same manner as in Example 1 below. It was set to 5.
The proportion of pores having a diameter of 0.1 μm or less was 84%. (2) Assembling the battery A battery was assembled in the same manner as Comparative Example 1 except that 5 was used as the positive electrode. Using this battery, the initial capacity was measured in the same manner as in Example 1, and 3
The capacity after charging at a constant voltage for 0 minutes was measured to evaluate the quick charging characteristics. The results are shown in Table 1.

[0061]

[Table 1]

[0062]

According to the present invention, it is possible to provide a secondary battery having a large capacity and excellent rapid charging characteristics.
Further, the secondary battery of the present invention can be charged and discharged for a long period of time, is excellent in safety, is easy to manufacture, and is economical.

[Brief description of drawings]

FIG. 1 shows a basic configuration of a battery according to the present invention.

[Explanation of symbols]

1 is a positive electrode, 2 is a negative electrode, 3 is a current collector, 4 is an electrolytic solution,
Reference numeral 5 is a separator, 6 is a battery case, and 7 and 7'are external terminals.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Akihiro Anekawa 1-6-10-503, Tomobuchi-cho, Miyakojima-ku, Osaka-shi, Osaka (72) Inventor Shizukuni Yada 2-6-13 Miyanishi, Harima-cho, Kako-gun, Hyogo (56) References JP-A-2-230668 (JP, A) JP-A-3-233860 (JP, A) JP-A-5-28985 (JP, A) JP-A-5-29023 (JP, A)

Claims (3)

(57) [Claims] 1. An organic electrolyte battery comprising a positive electrode, a negative electrode, and an electrolytic solution containing a solution of a lithium salt dissolved in an aprotic organic solvent, wherein the positive electrode comprises (1) (a) carbon, hydrogen and oxygen. Which is a heat-treated product of an aromatic condensed polymer having a polyacene skeleton structure in which the number ratio of hydrogen atoms / carbon atoms is 0.05 to 0.5,
And an active material which is a composite of (b) vanadium pentoxide particles having an average particle size of 1 μm or less and (b) an insoluble infusible substrate having a specific surface area of 600 m ² / g or more as measured by the BET method, and
(c) contains at least a conductive material, (2) the pore volume having a pore diameter of 0.1 μm or less accounts for 70% or more of the total pore volume (measured by mercury porosimetry), and (3) A composite powder compact obtained by simultaneously pulverizing and mixing (a), (b) and (c), wherein the negative electrode comprises (a) an aromatic condensed polymer composed of carbon, hydrogen and oxygen.
Which has a hydrogen atom / carbon atom atomic ratio of
In a molded body containing an insoluble and infusible substrate having a polyacene-based skeleton structure of 0.05 to 0.5 and (b) a thermosetting resin, lithium was added at an atomic percentage of 3 with respect to carbon atoms of the insoluble and infusible substrate.
% Or more of the supported organic electrolyte battery. 2. The organic electrolyte battery according to claim 1, wherein the insoluble and infusible substrate in the positive electrode comprises particles having an average particle size of 1 μm or less. 3. In the negative electrode, the insoluble and infusible substrate is BET.
3. The organic electrolyte battery according to claim 1, which has a specific surface area of less than 600 m ² / g according to the method and is composed of particles having an average particle diameter of 0.1 to 5 μm.