JP2627033B2 - Manufacturing method of 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 method of manufacturing a secondary battery, and more particularly, to a method of manufacturing 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, a small, lightweight and high-performance battery has been demanded as a power source. At present, so-called primary batteries such as dry batteries and secondary batteries such as Ni-Cd batteries and lead batteries are used as power supplies for the above devices. However, recently, a secondary battery that can be repeatedly charged for a primary battery that has a short life and needs to be replaced has been frequently used. Among them, Ni-Cd batteries are currently the mainstream as power supplies for small devices, but their performance improvement is approaching the limit for needs such as high capacity. In addition, global environmental issues have been debated in recent years, and public opinion on the harmfulness of Cd, an active material, has been 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.

[0003] The present applicant has previously disclosed a secondary in which an insoluble and infusible substrate containing a polyacene skeleton structure, which is a kind of organic semiconductor, doped with an electron donating substance or an electron accepting substance is used 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 has a high voltage characteristic, which is a characteristic of a lithium-based battery, but is a highly safe battery free of dendrite (Li dendritic crystals). However, the capacity of the battery 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 Accordingly, an object of the present invention is to provide a method for manufacturing 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 at a high voltage for a long period of time, is excellent in safety, is easy to manufacture, and is economical. .

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above-mentioned problems, and as a result, have found that a positive electrode in which the average particle diameter and the pore volume of vanadium pentoxide are controlled to specific ranges is polyacene-based. When combined with a negative electrode in which lithium is supported on a molded body containing a systemic organic semiconductor, if the positive electrode is manufactured by specifying the order and combination of pulverizing and mixing the substances constituting the positive electrode, the rapid chargeability of this battery Was found to improve.

That is, the present invention provides (1) (a) a heat-treated product of an aromatic condensed polymer comprising carbon, hydrogen and oxygen, wherein the atomic ratio of hydrogen atoms / carbon atoms is 0.05 to 0.5. And has a specific surface area of 600 m ² / g by the BET method.
An active material that is a composite of the insoluble infusible substrate described above and (b) vanadium pentoxide particles having an average particle size of 1 μm or less; and (c) a conductive material, and at least 0.1 μm
A cathode having a pore volume having a pore diameter of at least 70% of the total pore volume (measured by a mercury intrusion method), (2) (a) an aromatic composed of carbon, hydrogen and oxygen A heat-treated product of a polycondensation polymer, comprising: an insoluble infusible substrate having a polyacene skeleton structure in which the atomic ratio of hydrogen atoms / carbon atoms is 0.05 to 0.5; and (b) a thermosetting resin. A negative electrode in which lithium is supported on a molded body containing at least 3% by atomic percentage of carbon atoms of an insoluble and infusible substrate; and (3) an electrolysis including a solution in which a lithium salt is dissolved in an aprotic organic solvent. A method for producing an organic electrolyte battery provided with a liquid, wherein, when producing said positive electrode, (b) and a part of (c) are simultaneously pulverized and mixed, and then mixed with (a) and (c). Provide a method of mixing or grinding and mixing the remainder and then molding It is intended.

In the present invention, the insoluble and infusible substrate having a polyacene-based skeleton structure (hereinafter referred to as P
AS).
These are described in JP-A-60-152554 and JP-A-60-170163. Here, the aromatic condensation polymer is a condensate of an aromatic hydrocarbon compound having a phenolic hydroxyl group with an aldehyde. Suitable aromatic hydrocarbon compounds include, but are not limited to, so-called phenols such as phenol, cresol, and xylenol.

For example, the following formula (Formula 1):

[0012]

Embedded image (Where x and y are each independently 0, 1, or 2)
Methylene bisphenols, or hydroxy-biphenyls and hydroxynaphthalenes. Of these, phenols, particularly phenol, are suitable for practical use.

As the aromatic condensation polymer in the present invention, one part of the above-mentioned aromatic hydrocarbon compound having a phenolic hydroxyl group may be replaced with an aromatic hydrocarbon compound having no phenolic hydroxyl group, for example, xylene or toluene. , A modified aromatic polymer substituted with aniline, etc., 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 can also be used. 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 any of a novolak type, a resol type and a composite thereof. A spherical phenolic resin (sphere diameter of about 100 μm or less) commercially available as Bellpearl R (trade name, manufactured by Kanebo Co., Ltd.) can also be used.

The PAS in the present invention is a heat-treated 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 into the aromatic condensation polymer. As a mixing method, an 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 fusible one such as novolak, it may be mixed under heating. The mixing ratio of the aromatic condensed polymer and the above-mentioned inorganic substance varies depending on the type and shape of the polymer to be mixed and the inorganic substance.
0/1 to 1/7 are preferred.

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

The cured product thus obtained is then heated in a non-acidic atmosphere at 350 to 800 ° C., preferably at 350 to 70 ° C.
It is heated to a temperature of 0 ° C, particularly preferably 400-600 ° C. The non-oxidizing atmosphere in which such 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. Such a non-oxidizing atmosphere may be stationary or flowing.

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

Such a PAS used for a positive electrode in the present invention
Has a polyacene skeleton structure in which the atomic ratio of hydrogen atoms / carbon atoms (hereinafter referred to as H / C ratio) is 0.05 to 0.5, preferably 0.1 to 0.35. According to X-ray diffraction (CuKα), the position of the main peak is represented by 2θ and is 20.5 to 23.5.
°, and besides this main peak, 41-46
There are other peaks between degrees.

That is, it is understood that the PAS is one in which the polycyclic structure of polyacene-based benzene is uniformly and appropriately 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.

The 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 regardless of its particle size, that is, the capacity of the PAS to be used, 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 according to the present invention comprises:
The above-described composite of PAS and vanadium pentoxide is used as an active material. Vanadium pentoxide is generally represented by a formula of V ₂ O ₅ , but actually has a width as represented by a formula of V ₂ O _x (4.5 ≦ x <5.5). . Vanadium pentoxide is a lithium ion intercalation,
Alternatively, it is a kind of metal oxide which can be deintercalated, and becomes a compound represented by LiV ₂ O ₅ or Li ₂ V ₂ O ₅ by intercalation of lithium ions. 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, in order to obtain a high-voltage secondary battery, crystalline vanadium pentoxide is particularly preferable.

In the positive electrode of the battery according to the present invention, it is necessary that the average particle diameter of the above-mentioned vanadium pentoxide is 1 μm or less finally, that is, when the positive electrode is obtained. 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. That is, when vanadium pentoxide having a particle size larger than 1 μm is used, the capacity is not sufficient even if the pore distribution conditions in the positive electrode described later are satisfied.

The positive electrode of the battery according to the present invention is a composite of PAS having a high specific surface area and vanadium pentoxide,
Taking advantage of the characteristics of vanadium pentoxide, which can produce 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 PAS. It is a proposal. Therefore, the PAS / vanadium pentoxide ratio is important,
90/10 to 30/70 (weight ratio), especially 70/30 to
It is preferably 30/70. In particular, when the amount of vanadium pentoxide is excessively increased, only the characteristics of vanadium pentoxide are emphasized, and the advantage of the composite with PAS is lost.

The conductive material used in the present invention is preferably a carbon-based conductive material such as carbon black such as graphite, acetylene black and Ketjen black. Particularly, carbon blacks are preferred. The conductive material preferably has as small a particle size as possible. The amount of conductive material in the positive electrode may vary depending on the use of the positive electrode,
It is preferable that the content be from 40% by weight to 40% by weight. If the amount of the conductive material is too large, the amount of the active material becomes relatively small, so that the capacity of the battery becomes low.

In the positive electrode according to the present invention, after a part of the above (b) and (c) is simultaneously pulverized and mixed (first step), this is mixed with the remaining part of (a) and (c) or pulverized and mixed. (Second
Step) and then molding. The amount of (c) that is initially ground and mixed with (b) is preferably at least 5% by weight, more preferably 25% by weight, based on the amount of (b).
It is. The amount of the conductive material added later is preferably 2% by weight based on the total weight of PAS and vanadium pentoxide.
The content is more preferably at least 5% by weight, particularly preferably at least 15% by weight. The conductive material pulverized and mixed together with (b) and the remaining conductive material added later may be the same type of conductive material or different. In the present invention,
First, vanadium pentoxide is crushed and mixed with a conductive material by simultaneously crushing and mixing a part of (b) and (c), and the conductive material is present in a sufficient vicinity of vanadium pentoxide having low electric conductivity. It is thought to be. As a result, the conductive material particles can collect the current of vanadium pentoxide. The form of vanadium pentoxide used at this time is
Any form that can be easily mixed, such as a lump, a granule, and a powder, may be used. In order to sufficiently obtain the effects of the present invention, it is preferable to grind a material having a relatively large particle size together with the conductive material particles. Next, the composite of the conductive material and vanadium pentoxide, PAS and the remaining conductive material are mixed or pulverized. At this time, the PAS and the conductive material particles may only be mixed, and may be subjected to some degree of grinding. The PAS used here is preferably a pre-ground powder of 1 μm or less. In this way, it is presumed that the conductive material added later is dispersed throughout the powder composite in a continuous manner, and current collection of PAS and vanadium pentoxide, that is, current collection of the entire active material, is assumed. For example
When (a) and (b) are simultaneously pulverized and mixed, and then (c) is mixed to form a positive electrode, a large capacity battery can be obtained because vanadium pentoxide is homogeneously dispersed in PAS. However, the quick charging characteristics are not satisfactory.

The pulverization and mixing method of (b) and (c) is not particularly limited, but it is preferable to use a fine pulverizer such as a ball mill such as a pot mill or a vibration mill. The pulverization time should be determined depending on the pulverization method, the amount of pulverization, and the type of the substance to be pulverized, but is preferably one hour or more. When a method with a low pulverization force is used, the pulverization is preferably performed for a longer time.

The mixing or pulverization in the second step can be performed by a gentle pulverizing or mixing means such as a mortar or a nylon ball mill. The mixing time depends on the type and amount of the substance used. Excessive mixing or pulverization mixing that destroys the relationship between vanadium pentoxide and the conductive material formed earlier, or mixing that is too slow to collect current from the entire active material, reduces the capacity of the battery, It is not preferable because it leads to a decrease in the rapid charging characteristics.

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 preferred.

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 with respect to the total pore volume.
%, Preferably 75% or more. Examples of the method for measuring the pore volume include a mercury intrusion method and a capillary condensation method. In the present invention, a mercury intrusion method having a wide measurement width (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. Further, the pore volume having a pore diameter of 0.1 μm or less refers to 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 according to the present invention, 1
Since fine vanadium pentoxide particles of not more than μm are uniformly distributed between the PAS particles, the ratio of pores of not more than 0.1 μm 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 according to the present invention is obtained by doping lithium on a molded body containing an insoluble and infusible substrate having a polyacene skeleton structure and a thermosetting resin, and supporting the molded body. The insoluble and infusible substrate having a polyacene 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%.
PAS having a polyacene-based skeletal structure of 1 to 0.35 and the same PAS as in the positive electrode can be used. Even in the negative electrode, when the H / C ratio of PAS ′ is less than 0.05,
When carrying lithium or taking lithium in and out (during charging and discharging), the structure of the base is likely to change, and the cycle characteristics deteriorate. On the other hand, if the H / C ratio exceeds 0.5, lithium cannot be stably supported,
A battery manufactured using such a negative electrode in which lithium is supported on PAS 'has a 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's less than. The PAS 'having such a low specific surface area can be used as the PAS in the positive electrode described above.
In the production process, the aromatic condensation polymer is cured without adding an inorganic substance such as zinc chloride, and then in a non-oxidizing atmosphere (including a vacuum state) at 400 to 1000 ° C.
, Preferably at a temperature of 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 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
In the Stokes diameter obtained by centrifugal sedimentation or the like (diameter of spherical particles of the same density sedimenting in the same medium at the same speed as the sample particles), it was defined as the particle diameter at which the integrated sieving percentage was 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 to be supported, and the like. Preferably, the proportion in the negative electrode is 1 to 70% by weight, more preferably 5 to 50%. It is. If the amount of the thermosetting resin is too small, the effect of suppressing the loosening of the negative electrode is small. If the amount is too large, the amount of PAS 'naturally becomes small, so that sufficient lithium cannot be supported, and the battery capacity decreases. I will.

A molded article containing PAS 'and a thermosetting resin is:
It can be roughly divided 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. Further, the second method is to use the PAS '
Is mixed with a binder generally used for battery electrodes, for example, polytetrafluoroethylene, polyethylene, polypropylene, etc., or mixed or kneaded as necessary, and then molded. After impregnating the resin initial condensate,
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 according to the present invention is reduced. When the amount is large, excessive 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 mixture of two or more.

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 an 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 according to the present invention includes the above-described positive electrode, negative electrode, and electrolytic solution. Generally, 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 In the examples, the following substances were used. Polyacene-based substance I (for positive electrode and negative electrode) A slurry obtained by mixing a water-soluble resol type phenol resin (about 60% concentration) / zinc chloride / water in a weight ratio of 10/25/5, Pour into a 10 cm × 10 cm × 1 cm mold, cover with a glass plate, and
The composition was cured by heating at 0 ° C. for 1 hour. The cured product was placed in a siliconite electric furnace, heated at a rate of 40 ° C./hour and heated to 500 ° C. in a nitrogen stream to perform a heat treatment. Next, the heat-treated product is washed with dilute hydrochloric acid to remove zinc chloride, washed with water, and then dried to obtain a plate-shaped P.
AS was obtained. The specific surface area of this PAS by the BET method is 2
It was an extremely large value of 000 m ² / g. Elemental analysis revealed that the ratio of the number of hydrogen atoms to the number of carbon atoms was 0.23. The shape of the peak from X-ray diffraction is a pattern based on the polyacene-based skeletal structure.
A broad main peak was present around 0 to 22 °, and a small peak was found around 41 to 46 °.

The PAS thus obtained was divided into blocks of about 1 to 5 cm square (PAS-A). Further, the mixture was pulverized with a nylon ball mill for 24 hours to obtain a PAS powder having an average particle diameter of 0.7 μm. This is PAS powder B
Called. The average particle diameter of the PAS powder was determined by electron microscopy ("Powder", edited by Teruichiro Kubo et al., 1979, 2nd revised edition, Maruzen Co., Ltd.). Polyacene-based material II (for negative electrode) Novolac-type phenol resin is placed in a siliconite electric furnace, and heated at a rate of 750 ° C./hour under a nitrogen atmosphere at a rate of 10 ° C./hour.
C. and heat-treated.

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

This PAS ′ was pulverized by a ball mill made of nylon while changing the pulverization time to 10 minutes and 24 hours, each having an average particle size of 3.4 μm (PAS ′ powder C).
And a PAS ′ powder of 0.79 μm (PAS ′ powder D). The specific surface area by each BET method is 230
m ² / g and 240 m ² / g. In addition, PA
The average particle size of the S 'powder was determined by a centrifugal sedimentation method. V ₂ O ₅ Commercially available crystalline V ₂ O ₅ was pulverized for 10 minutes using an alumina ball mill to have an average particle size of 5.3 μm.
Of V ₂ O ₅ powder was obtained. The average particle size was measured by electron microscopy as in PAS. Example 1 (1) Production of Positive Electrode V ₂ O ₅ having an average particle diameter of 5.3 μm and carbon black (average particle diameter of 0.02 μm, manufactured by Cabot Corp.)
Trademark: Black Pearl, a hereinafter referred to as BP) and, V ₂ O
_The mixture was placed in an alumina ball mill at ₅ / BP = 40/5 (weight ratio) and pulverized and mixed for 48 hours. V ₂ O ₅ and B obtained
When the composite of P was observed with an electron microscope, the V ₂ O ₅ particles and the BP particles were very small and homogeneously mixed, and it was difficult to accurately measure the diameter of each single particle. No single particles of 0.1 μm or more were found.

PAS powder (PAS powder B) having a composite of V ₂ O ₅ and BP of 45 parts by weight and an average particle size of 0.7 μm
60 parts by weight and the same BP 20 used above
The parts by weight were placed in a nylon ball mill and mixed for 1 hour. When the obtained composite was observed with an electron microscope,
The V ₂ O ₅ particles, BP particles and PAS particles were well mixed with each other, and it was difficult to accurately specify the particle size distribution of each particle.

To 100 parts by weight of this composite, 8 parts by weight of polytetrafluoroethylene as a binder was added, mixed and kneaded with a mortar, and then formed into a sheet with a roller.
An electrode sheet having a thickness of 750 μm was obtained. The pore distribution of this electrode sheet was measured with a mercury porosimeter (Poresizer, manufactured by Shimadzu Corporation),
m / pore volume having pore diameter of not more than m) / (0.006μ)
The ratio (pore volume having a pore diameter of m or more and 100 μm or less) was found to be 84%. 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 was added as a binder, mixed and kneaded with a mortar, and then formed into a sheet with a roller to obtain a thickness of 400 μm.
m, thereby obtaining a negative electrode preform. Next, the preform was immersed in a methanol solution (about 25% concentration) of a resol type phenol resin precondensate to impregnate the phenol resin into the preform. The impregnation amount of the phenol resin 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 size of 15 mmφ. It was set to 1.

The obtained negative electrode molded product 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
Lithium was carried on the molded negative electrode by applying the voltage for a time. The amount of lithium carried, determined by integrating the current values flowing through the circuit, was 32 atomic%. This was designated as negative electrode No. Let it be 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. Table 1 shows the results. Example 2 (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 impregnated with a phenol resin and cured in the same manner as in Example 1, A negative electrode molded body was manufactured.
The impregnation amount of the phenol resin 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 lithium carried was 28 atomic%. This was designated as negative electrode No. Let it be 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.
The capacity after charging at a constant voltage for 0 minutes was measured to evaluate the quick charging characteristics. Table 1 shows the results. Example 3 (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 impregnated with a phenol resin and cured in the same manner as in Example 1 to obtain a negative electrode. A molded body was manufactured. The impregnation amount of the phenol resin is 3
It was 6% by weight. Next, the obtained molded body (N
o. 3) was loaded with lithium in the same manner as in Example 1. The amount of lithium carried was 78 atomic%. This was designated as negative electrode No. 3 is assumed. (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.
The capacity after charging at a constant voltage for 0 minutes was measured to evaluate the quick charging characteristics. Table 1 shows the results. Example 4 (1) Production of Positive Electrode In Example 1, the ratio at the time of pulverizing and mixing V ₂ O ₅ and BP was set to V ₂ O ₅ / BP = 40/10 (weight ratio). Composite of V ₂ O ₅ and BP, PAS
An electrode was manufactured in the same manner as in Example 1 except that the amount of BP when mixing BP and BP was changed to 15 parts by weight. And 2. The pore ratio of 0.1 μm or less is 8
6%. (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.
The capacity after charging at a constant voltage for 0 minutes was measured to evaluate the quick charging characteristics. Table 1 shows the results. Example 5 The positive electrode no. 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. Table 1 shows the results. Example 6 The positive electrode no. No. 2 and the negative electrode Nos. 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. Table 1 shows the results. Comparative Example 1 (1) Production of Positive Electrode V ₂ O ₅ and BP having an average particle size of 5.3 μm were converted to V ₂ O ₅ /
The mixture was placed in an alumina ball mill with BP = 40/25 (weight ratio) and pulverized for 48 hours. Observation of the obtained composite of V ₂ O ₅ and BP with an electron microscope revealed that V ₂ O ₅ particles and B
It was very small and homogeneously mixed with the P particles, and it was difficult to accurately measure the diameter of each single particle, but no single particle of 0.1 μm or more was found.

65 parts by weight of the above composite of V ₂ O ₅ and BP and 60 parts by weight of PAS powder (PAS powder B) having an average particle size of 0.7 μm were put in a nylon ball mill and mixed for 1 hour.

From the obtained composite, an electrode was manufactured in the same manner as in Example 1, and this was used as a positive electrode No. It was set to 3.
The ratio of pores having a diameter of 0.1 μm or less was 80%. (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.
The capacity after charging at a constant voltage for 0 minutes was measured to evaluate the quick charging characteristics. Table 1 shows the results. Comparative Example 2 (1) Production of positive electrode Lumpy PAS (PAS-A) and V having an average particle size of 5.3 μm
And _{2 O 5, PAS / V 2} O 5 = 60/40 ( weight ratio)
Was put into an alumina ball mill and pulverized and mixed for 48 hours. To 100 parts by weight of the obtained composite of PAS and V ₂ O ₅ , 25 parts by weight of BP used in Example 1 was added, and the mixture was placed in a nylon ball mill and mixed for 1 hour.
Observation of the obtained composite with an electron microscope revealed that PAS
Was 0.4 μm. On the other hand, V ₂ O ₅ particles are very small and homogeneously mixed with PAS particles and BP particles, and are particularly entangled indistinguishable from BP particles, so that accurate measurement of the particle diameter is difficult. However, no single particles of V ₂ O ₅ or BP having a size of 0.1 μm or more were found.

From the obtained composite, an electrode was manufactured in the same manner as in Example 1, and this was And 4.
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 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.
The capacity after charging at a constant voltage for 0 minutes was measured to evaluate the quick charging characteristics. Table 1 shows the results.

[0061]

[Table 1]

[0062]

According to the present invention, it is possible to provide a method for manufacturing a secondary battery having a large capacity and an excellent quick charge characteristic. The secondary battery manufactured according to the present invention is further excellent in safety that can be charged and discharged for a long time,
Moreover, it is easy and economical to manufacture.

[Brief description of the 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 denotes a separator, 6 denotes a battery case, and 7, 7 ′ denote external terminals.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Akihiro Anekawa 1-6-10-503, Tomobuchi-cho, Miyakojima-ku, Osaka-shi, Osaka-shi (56) References JP-A-3-53450 (JP, A) JP-A-5-159805 (JP, A)

Claims (3)

(57) [Claims] (1) A heat-treated product of (a) an aromatic condensation polymer comprising carbon, hydrogen and oxygen, wherein the polyacene has a hydrogen atom / carbon atom ratio of 0.05 to 0.5. An active material having a system skeletal structure and a composite of an insoluble and infusible substrate having a specific surface area of at least 600 m ² / g by a BET method and (b) vanadium pentoxide particles having an average particle size of 1 μm or less. And (c) at least a conductive material,
And a positive electrode in which a pore volume having a pore diameter of 0.1 μm or less accounts for 70% or more of the total pore volume (measured by a mercury intrusion method); (2) (a) carbon, hydrogen and oxygen A heat-treated product of an aromatic condensed polymer comprising a polyacene skeleton having a hydrogen atom / carbon atom ratio of 0.05 to 0.5, and (b) thermosetting A negative electrode in which lithium is supported on an insoluble infusible substrate in an amount of 3% or more based on carbon atoms of an insoluble and infusible substrate on a molded body containing a conductive resin, and (3) a lithium salt is dissolved in an aprotic organic solvent. A method for producing an organic electrolyte battery provided with an electrolytic solution containing a solution, wherein in producing the positive electrode, (b) and a part of (c) are simultaneously pulverized and mixed, and then mixed with (a) and (a). The remaining part of (c) is mixed or pulverized and then molded. Method. 2. The method according to claim 1, wherein in the positive electrode, the insoluble and infusible substrate comprises particles having an average particle diameter of 1 μm or less. 3. The negative electrode according to claim 1, wherein the insoluble infusible substrate is BET.
The method according to claim 1, comprising particles having a specific surface area of less than 600 m ² / g and an average particle size of 0.1 to 5 μm.