JP2703696B2 - 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 material 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. Above all, Ni-Cd batteries are currently the mainstream as power supplies for small devices, but the performance improvement is approaching the limit for needs such as higher capacity. In addition, discussions on global environmental issues have been active in recent years, and public opinion on the harmfulness of Cd, which is an active material, is increasing. Therefore, there is great expectation for the development of a secondary battery having higher performance than a Ni-Cd battery and having high reliability and safety. The present applicant has previously proposed a secondary battery using, as an electrode active material, a material obtained by doping an insoluble and infusible substrate containing a polyacene-based skeleton structure, which is a kind of organic semiconductor, with an electron donating substance or an electron accepting substance. (JP-A-60-170163).
This battery is a promising secondary battery because it has high performance, has the potential of being thin and light, has high oxidation stability of the electrode active material, and is easy to mold. Further, the present applicant has used a composite of the polyacene-based organic semiconductor and the metal oxide as an active material, and doped and supported lithium on a molded article containing the polyacene-based organic semiconductor on the negative electrode.
A secondary battery that can be charged and discharged for a long time at a high voltage has been proposed (Japanese Patent Application No. 3-204679). 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, there remains an unsatisfactory capacity, particularly the capacity per unit volume.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have made intensive studies in view of the above problems, and as a result, have controlled the average particle size of lithium cobalt oxide in the positive electrode and the pore volume of the positive electrode to specific ranges. The present invention has been completed by finding that when combined with a negative electrode in which lithium is supported on a molded article containing a polyacene-based organic semiconductor, the capacity per unit volume of this battery is significantly increased. An object of the present invention is to provide a secondary battery having a large capacity and capable of being charged and discharged for a long time at a high voltage. Another object of the present invention is to provide a secondary battery which is excellent in quick charging characteristics and safety, is easy to manufacture, and is economical.

[0004]

That is, the present invention relates to an organic electrolyte battery comprising a positive electrode, a negative electrode, and an electrolytic solution containing a solution in which a lithium salt is dissolved in an aprotic organic solvent. (A) a heat-treated product of an aromatic condensed polymer comprising carbon, hydrogen and oxygen, which contains a polyacene-based skeletal structure having a hydrogen atom / carbon atom number ratio of 0.05 to 0.5, and An insoluble infusible substrate having a specific surface area of 600 m ² / g or more by a BET method;
(B) a composite with lithium cobalt oxide particles having an average particle diameter of 1 μm or less, and (2) a pore volume having a pore diameter of 0.1 μm or less accounts for 70% or more of the total pore volume. Wherein the negative electrode is (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.
(3) Lithium is supported on a molded article containing an insoluble infusible substrate having a polyacene-based skeleton structure, and (b) a thermosetting resin, in an atomic percentage of 3% or more with respect to carbon atoms of the insoluble infusible substrate. It is characterized in that it is.

In the present invention, the insoluble and infusible substrate (hereinafter referred to as PA
S) is disclosed in Japanese Patent Application Laid-Open No.
No. 0-152554 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. As the aromatic hydrocarbon compound, for example, so-called phenols such as phenol, cresol, and xylenol are suitable, but not limited thereto. For example:

Embedded image (Where x and y are each independently 0, 1 or 2)
Methylene bisphenols, or hydroxybiphenyls and hydroxynaphthalenes. Of these, phenols, particularly phenol, are practically preferred.

As the aromatic condensation polymer in the present invention, a part of the above-mentioned aromatic hydrocarbon compound having a phenolic hydroxyl group is converted into an aromatic hydrocarbon compound having no phenolic hydroxyl group, for example, xylene, toluene, aniline or the like. A substituted modified aromatic polymer, for example, a modified aromatic polymer which is a condensate of phenol, xylene and formaldehyde can be used, and a modified aromatic polymer substituted with melamine or urea 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, or 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 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 into the above-mentioned 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 at 350 to 800 ° C. in a non-acidic atmosphere, 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 the heat treatment of the aromatic condensation polymer is performed is, for example, a nitrogen, argon, helium, neon, carbon dioxide atmosphere, or a 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 salt contained in the heat-treated body can be removed, and then dried to obtain PAS having a large specific surface area.

The PAS used in the present invention has a hydrogen atom / carbon atom number ratio (hereinafter referred to as H / C) of 0.05 to 0.5, preferably 0.1 to 0.35. It has a system skeleton structure. X-ray analysis (CuKα)
According to the above, the position of the main peak is represented by 2θ.
There is another peak between 41 and 46 degrees apart from this main peak between 5 and 23.5 degrees. In other words, it is understood that the PAS is a polyacene-based benzene having a polycyclic structure 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 BET specific surface area of the PAS used in the positive electrode of the present invention is at least 600 m ² / g. 600
If it is less than 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 positive electrode of the present invention, since the PAS has a high specific surface area of 600 m ² / g or more as described above, the PAS has sufficient performance as an active material regardless of its particle size, that is, PA
The capacity of S can be sufficiently extracted. However, if the particle size of the PAS is too large, it is difficult to disperse lithium cobalt oxide (hereinafter, LiCoO ₂ ), which is likely to undergo secondary aggregation, in the PAS matrix, that is, between the PAS particles. Preferably it is.

In the positive electrode of the battery of the present invention, LiCo
The average particle size of O ₂ is 1
It is necessary to be less than μm. This is because PAS having a large surface area can sufficiently draw out its capacity irrespective of the particle size, whereas, in the case of LiCoO ₂ , if the particle size is too large, it is difficult to sufficiently draw out its capacity. That's why. That is, when LiCoO ₂ having a particle size larger than 1 μm is used, its capacity is not sufficient even if the condition of pore distribution in the positive electrode described later is satisfied.

[0012] Lithium cobalt oxide can be easily produced by a known appropriate method. For example, lithium carbonate (Li ₂ C
O ₃ ) and cobalt carbonate (CoCO ₃ ) are obtained by heating at 900 ° C., but the lithium cobalt oxide in the present invention is not particularly limited in the production method. Lithium cobalt oxide is generally represented as Li _x CoO ₂ , but the value of x is in the range of 0 ≦ x ≦ 1 due to its synthesis method and charge / discharge in a battery system. In the lithium cobalt oxide (hereinafter abbreviated as LiCoO ₂ ) in the present invention, the value of x is not particularly limited.

In the electrode of the present invention, PAS / LiCo
Although the ratio of O ₂ varies depending on the use of the electrode containing these, it is 90/10 to 10/90 (weight ratio), particularly 70/30 to
It is preferably 20/80. In particular, if the amount of LiCoO ₂ is too large, the rapid chargeability, which is a feature of the composite, tends to be lost. The battery electrode of the present invention using a composite of PAS and LiCoO ₂ as an active material can be manufactured, for example, as follows. That is, after pulverizing and mixing PAS and LiCoO ₂ , a conductive agent and a binder are added as necessary, and then molded. At this time, the PAS and LiCoO ₂ may be in any form as long as they are easily mixed with powder, short fiber, etc., but are practically powder. The conductive agent, the binder, and the like used are not particularly limited, and those generally used for battery electrodes are preferable. PAS and LiCoO ₂ can be mixed after pulverizing individually to a predetermined particle size in advance, or
AS and LiCoO ₂ may be pulverized and mixed at the same time.

Although there is no particular limitation on the pulverizing method, it is preferable to use a fine pulverizer such as a ball mill such as a pot mill or a vibration mill. When an electrode is made by mixing fine PAS and LiCoO ₂ having a small particle size by mixing, it is necessary to control the pore ratio to be described later by using LiCoO _2.
Is difficult due to secondary agglomeration (apparent increase in particle size). Therefore, in order to disperse LiCoO ₂ homogeneously in the matrix made by PAS, PAS and L
A method of simultaneously pulverizing and mixing iCoO ₂ and the like is desirable. 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 battery electrode of the present invention thus obtained comprises:
It is necessary that the pore volume having a pore diameter of 0.1 μm or less accounts for 70% or more, preferably 75% or more of the total pore volume. 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 with 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 per electrode unit weight.
It means the total volume of pores having a pore diameter of not less than μm and not more than 100 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 100 μm or less. In the present invention, since fine LiCoO ₂ particles of 1 μm or less are uniformly distributed between the PAS particles, the ratio of pores of 0.1 μm or less is large. Especially L of about 0.1 μm or less
It is desirable that iCoO ₂ be uniformly dispersed between PAS particles of about 0.2 to 0.6 μm. The shape of the electrode of the present invention is not particularly limited, and can take various shapes such as a plate shape, a film shape, and a cylindrical shape.

Next, the negative electrode of the electrode of the present invention is obtained by doping lithium on a molded body containing an insoluble and infusible substrate having a polyacene-based skeleton structure and a thermosetting resin. The insoluble and infusible substrate having a polyacene skeleton structure used in the negative electrode is hereinafter referred to as PAS '.
As the PAS ', the same PAS as in the positive electrode having a polyacene-based skeleton structure having an H / C ratio of 0.05 to 0.5, preferably 0.1 to 0.35 can be used. Even in the negative electrode, the H / C ratio of PAS 'was 0.05
When it is less than 3, when carrying lithium or taking lithium in and out (during charge and discharge), the structure of the base is likely to change, and the cycle characteristics deteriorate. On the other hand, H
When the / 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 a large self-discharge. Further in the negative electrode, not suitable in the positive electrode, the BET specific surface area of 600 meters ² / g
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 PAS 'for molding include those capable of suppressing loosening of the electrode, for example, phenol resin, melamine resin, and furan resin. The ratio of the thermosetting resin in the molded article is determined by the shape of the PAS ', the specific surface area of the PAS', the amount of the binder, the amount of lithium to be supported, and the like. ~ 70%, more preferably 5 ~ 50%. 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 a method of mixing P such as powder, short fiber, etc.
AS 'and the initial condensate of the thermosetting resin are kneaded by adding a solvent such as methanol, toluene or water, if necessary, and then kneaded.
This is a method of performing pressure molding at the same time as curing under heating at ~ 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 kneaded and molded as necessary. 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. Further, it can also be supported by bringing an appropriate amount of lithium foil into direct contact with the molded body.

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 3% or more, preferably 10% or more 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 combined positive electrode, and the like. The potential of the PAS' molded body supporting lithium is 1.0 to 1.0 with respect to Li / Li ⁺ .
It is desirable to carry lithium so as to be 0V.
When the amount of lithium is small, the capacity of the battery of the present invention is reduced. When the amount is large, excess lithium is deposited on the surface of the PAS 'molded body.

An aprotic organic solvent is used as a solvent constituting the electrolytic solution used in the present invention. Examples of the aprotic organic solvent include ethylene carbonate, propylene carbonate, γ-butyrolactone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolan, methylene chloride, and sulfolane. 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 that can generate lithium ions. Such electrolytes include, for example, LiI, LiClO ₄ , LiAsF
₆ , LiBF ₄ or LiHF ₂ . The above electrolyte and solvent are mixed in a sufficiently dehydrated state to make an electrolyte, but the concentration of the electrolyte in the electrolyte is:
In order to reduce the internal resistance due to the electrolyte, it is preferably at least 0.1 mol / l or more, and more preferably 0.2 to 1.5 mol / l.

The organic electrolyte battery of the present invention comprises the above-described positive electrode,
A negative electrode and an electrolytic solution are provided. Generally, a positive electrode and a negative electrode are arranged via a separator. Hereinafter, the present invention will be described specifically with reference to examples.

[0023]

EXAMPLES Example 1 Preparation of I (for positive and negative electrodes) polyacene-based materials: Water-soluble resol type phenolic resin (about 60% concentration) / zinc chloride / water in a weight ratio of 10/25/5. The mixed slurry was poured into a mold of 10 cm × 10 cm × 1 cm, covered with a glass plate, and cured by heating at 100 ° C. for 1 hour while suppressing evaporation of water. 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 was washed with diluted hydrochloric acid to remove zinc chloride, washed with water, and then dried to obtain a plate-like PAS. The specific surface area of this PAS measured by the BET method was an extremely large value of 2000 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, and 2θ
, A broad main peak was present at around 20 to 22 °, and a small peak was found at around 41 to 46 °.

The PAS thus obtained was pulverized by a ball mill made of nylon while changing the pulverization time to 10 minutes, 24 hours and 48 hours, each having an average particle size of 5.2 μm.
PAS powders of (PAS powder A), 0.7 μm (PAS powder B) and 0.4 μm (PAS powder C) were obtained. The average particle size of the PAS powder was determined by electron microscopy ("powder", edited by Keiichiro Kubo et al., 1979, 2nd revised edition, Maruzen Co., Ltd.).

II (for negative electrode) Production of polyacene-based material: Novolak-type phenol resin is placed in a siliconite electric furnace, and heated to 750 ° C. in a nitrogen atmosphere at a rate of 10 ° C./hour.
And heat-treated. H / of the obtained PAS '
The C ratio was 0.12. This PAS 'was pulverized with a ball mill made of nylon while changing the pulverization time to 10 minutes and 24 hours, and the average particle diameter was 3.4 μm (PAS').
PA of powder D) and 0.79 μm (PAS ′ powder E)
S ′ powder was obtained. The specific surface areas by the respective BET methods were 230 m ² / g and 240 m ² / g. Note that P
The average particle size of the AS 'powder was determined by a centrifugal sedimentation method.

[0026] LiCoO ₂ in producing: - commercial LiCoO ₂ the grinding time 10 minutes using an alumina ball mill for 48 hours, then milled for 72 hours, an average particle diameter of each 6.5 [mu] m (LiCoO ₂ powder A),
0.6 μm (LiCoO ₂ powder B), 0.4 μm (Li
LiCoO ₂ powder of CoO ₂ powder C) was obtained. The average particle size was measured by electron microscopy as in PAS '. In each case, LiCoO ₂ particles were secondary aggregated,
It was measured by the size of the primary particles.

(1) Production of positive electrode PAS powder A and LiCoO ₂ powder A were mixed with PAS / LiC
24 hours ( Example 1a ) and 48 hours ( Example 1b ) in an alumina ball mill at oO ₂ = 40/60 (weight ratio)
Crushed. When the obtained composite of PAS and LiCoO ₂ was observed with an electron microscope, the average particle size of PAS was 0.5 μm and 0.4 μm, respectively. Also LiC
Because the oO ₂ particles were homogeneously mixed with the PAS particles,
Although accurate measurement of the particle diameter was difficult, the average particle diameter was about 0.5 μm in each case.

To 100 parts by weight of the obtained composite, 25 parts by weight of carbon black as a conductive agent and 8 parts by weight of polytetrafluoroethylene as a binder were added, mixed and kneaded in a mortar, and then sheeted with a roller. Molding was performed to obtain an electrode sheet having a thickness of 750 μm. The pore distribution of this electrode sheet was measured with a mercury porosimeter (Poresizer, manufactured by Shimadzu Corporation), and was measured to be 0.006 μm to 0.1 μm.
Pore volume having the following pore diameter) / (0.006 μm
The ratio of the pore volume (pore diameter having a pore diameter of 100 μm or less) was 78% and 81%, respectively. This electrode sheet was punched into a 15 mmφ
o. 1a and No. 1 1b.

(2) Production of Negative Electrode To 100 parts by weight of PAS 'powder E, 10 parts by weight of polytetrafluoroethylene as a binder was added, mixed and kneaded in a mortar, formed into a sheet by a roller, and formed into a sheet having 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, and this was molded. It was set to 1.

The obtained negative electrode molded product No. 1 as a working electrode, lithium metal as a counter electrode and a reference electrode, 1M LiC
An electrochemical cell was assembled by using an propylene carbonate solution of 10 _{4 as} an electrolyte. By applying a voltage of 0.2 V to lithium for 12 hours, lithium was supported on the molded negative electrode. 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 1a and No. 1 1b, negative electrode no. A battery as shown in FIG. 1 was assembled by using 1 and a 1M LiPF ₆ propylene carbonate / diethyl carbonate solution as an electrolytic solution, and a glass nonwoven fabric as a separator. After charging the battery for the first time at a constant voltage of 4.1 V for 2 hours, 2 m
A discharged to 2.0V. Thereafter, this charge / discharge was repeated up to 100 times and compared with the initial capacity. Table 1 shows the results.

Example 2 (1) Production of Positive Electrode PAS powder C and LiCoO ₂ powder C were mixed with PAS / LiC
The mixture was placed in a nylon ball mill at oO ₂ = 40/60 (weight ratio) and mixed for 1 hour. PAS and LiCo obtained
Observation of the O ₂ composite with an electron microscope showed that there was no significant change in the particle size of PAS and LiCoO ₂ . Using this composite, a positive electrode was manufactured in the same manner as in Example 1, and this was used as a positive electrode No. And 2. The proportion of pores of 0.1 μm or less was 82%.

(2) Assembling of 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, charging and discharging were performed 100 times in the same manner as in Example 1. 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 D was used, and impregnated with a phenol resin and cured in the same manner as in Example 1. Thus, 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) Assembling of the battery Except that 2 was used as the negative electrode
A battery was assembled in the same manner as in Example 1b . Using this battery, charging and discharging were performed 100 times in the same manner as in Example 2. Table 1 shows the results.

Example 4 The positive electrode No. 1 produced in Example 2 Anode was prepared in 2 and Example 3 No. A battery was assembled in the same manner as in Example 1 except that Battery No. 2 was used. Using this battery, charging and discharging were performed 100 times in the same manner as in Example 1 . Table 1 shows the results.

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 impregnated with a phenol resin and cured in the same manner as in Example 1. Thus, a molded negative electrode was produced. 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) Assembling of the battery Except that 3 was used as the negative electrode
A battery was assembled in the same manner as in Example 1b . Using this battery, charging and discharging were performed 100 times in the same manner as in Example 1. Table 1 shows the results.

The positive electrode prepared in Example 6 Example 2 No. Anode was prepared in 2 and Example 5 No. A battery was assembled in the same manner as in Example 1 except that Battery No. 3 was used. Using this battery, charging and discharging were performed 100 times in the same manner as in Example 1 . Table 1 shows the results.

Comparative Example 1 (1) Production of Positive Electrode PAS powder A and LiCoO ₂ powder A were mixed with PAS / LiC
The mixture was mixed in a mortar at oO ₂ = 40/60 (weight ratio). When the obtained composite of PAS and LiCoO ₂ was observed with an electron microscope, there was no significant change in the particle size of PAS and LiCoO ₂ . Using this composite, the following Example 1
A positive electrode was manufactured in the same manner as in It was set to 3. The proportion of pores having a diameter of 0.1 μm or less was 53% .

(2) Assembling of the battery Except that 3 was used as the positive electrode
A battery was assembled in the same manner as in Example 1 . Using this battery, charging and discharging were performed 100 times in the same manner as in Example 1 . Table 1 shows the results.

Comparative Example 2 PAS powder C and LiCoO ₂ powder A were mixed with PAS / LiC
The mixture was placed in a mortar at oO ₂ = 40/60 (weight ratio) and mixed. When the obtained composite of PAS and LiCoO ₂ was observed with an electron microscope, there was no significant change in the particle size of PAS and LiCoO ₂ . Using this composite, less real
A positive electrode was manufactured in the same manner as in Example 1, and this was used as a positive electrode No. 4
And

(2) Assembling of the battery Except that 4 was used as the positive electrode
A battery was assembled in the same manner as in Example 1 . Using this battery, charging and discharging were performed 100 times in the same manner as in Example 1 . Table 1 shows the results.

[0044]

[Table 1]

[0045]

According to the present invention, it is possible to provide a secondary battery having a large capacity, a high voltage and capable of charging and discharging for a long time. Further, the secondary battery of the present invention is excellent in safety, and 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]

 DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Negative electrode 3 Current collector 3 'Current collector 4 Electrolyte 5 Separator 6 Battery case 7 External terminal 7' External terminal

 ──────────────────────────────────────────────────の Continued on the front page Examiner Junko Yoshimizu (56) References JP-A-5-159807 (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 in which a lithium salt is dissolved in an aprotic organic solvent, wherein the positive electrode comprises: (1) (a) carbon, hydrogen and oxygen A heat-treated product of an aromatic condensed polymer comprising a polyacene-based skeleton structure having an atomic ratio of hydrogen atoms / carbon atoms of 0.05 to 0.5, and having a specific surface area value of 600 m ² by a BET method.
/ G or more, and (b) the average particle size is 1
(2) a pore volume having a pore diameter of 0.1 μm or less accounts for 70% or more of the total pore volume; (A) a heat-treated aromatic condensed polymer composed of carbon, hydrogen and oxygen, which has a polyacene skeleton structure in which the atomic ratio of hydrogen atoms / carbon atoms is 0.05 to 0.5; A molded product containing an infusible substrate and (b) a thermosetting resin, wherein lithium is supported on the insoluble infusible substrate at an atomic percentage of 3% or more based on carbon atoms. Organic electrolyte battery. 2. The organic electrolyte battery according to claim 1, wherein in the positive electrode, the insoluble and infusible substrate comprises particles having an average particle size of 1 μm or less. 3. The negative electrode according to claim 1, wherein the insoluble infusible substrate is BET.
The organic electrolyte battery 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.