JP3403894B2 - Organic electrolyte battery - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an organic electrolyte battery having a high capacity and a high voltage, which uses an insoluble and infusible substrate having a polyacene skeleton structure for a negative electrode.

[0002]

2. Description of the Related Art In recent years, secondary batteries using a conductive polymer, a transition metal oxide or the like as a positive electrode and a lithium metal or a lithium alloy as a negative electrode have high energy density.
It has been proposed as an alternative to Ni-Cd batteries and lead batteries.

[0003]

However, when these secondary batteries are repeatedly charged and discharged, the capacity is greatly reduced due to the deterioration of the positive electrode or the negative electrode, and a problem remains in practical use. In particular, the deterioration of the negative electrode is accompanied by the generation of moss-like lithium crystals called dendrites, and the dendrites eventually penetrate the separator due to repeated charging and discharging, causing a short circuit inside the battery, and in some cases, the battery bursts, etc. There was also a problem in terms of safety.

Recently, in order to solve the above problems, a battery using a carbon material such as graphite for the negative electrode and a lithium-containing metal oxide such as LiCoO _{2 for} the positive electrode has been proposed. This battery is a so-called rocking chair type battery in which lithium is supplied from the lithium-containing metal oxide of the positive electrode to the negative electrode by charging after the battery is assembled, and the negative electrode lithium is returned to the positive electrode by discharging. However, although this battery is characterized by having a high voltage and a high capacity, since the lithium stored in the negative electrode is limited to C ₆ Li, there is a limit to increase the capacity.

On the other hand, it is a heat-treated product of an aromatic condensation polymer and has an atomic ratio of hydrogen atoms / carbon atoms of 0.50 to 0.0.
The insoluble and infusible substrate having a polyacene-based skeleton structure of No. 5 is capable of being doped with a large amount of lithium as compared with a general carbon material, and thus is useful as a negative electrode material for a lithium battery which replaces the above carbon material. It is thought that
When a battery was actually assembled using this insoluble and infusible substrate as a negative electrode, the capacity was unsatisfactory. That is, for example, in Japanese Unexamined Patent Publication No. 8-64202, an insoluble immiscible material having a polyacene skeleton structure having a heat treatment product of an aromatic condensation polymer and having a hydrogen atom / carbon atom atomic ratio of 0.50 to 0.05 is disclosed. A negative electrode material that is a fusible substrate and has an adsorbed gas amount of 100 cc / g or less at a nitrogen adsorption thickness of 10 Å obtained from the nitrogen adsorption isotherm of the insoluble infusible substrate has been proposed, but a sufficient capacity is still solved. The reality is that it has not reached.

The present inventors have completed the present invention as a result of intensive studies in view of the above-mentioned circumstances, and the present invention is a secondary battery having a high capacity and a high voltage, which can be obtained for a long period of time. It is intended to provide an organic electrolyte battery that can be charged and discharged.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have made an insoluble infusible substrate having a polyacene skeleton structure in which the ratio of true specific gravities measured with two or more different solvents falls within a specific range as a negative electrode. It has been found that a secondary battery having a high capacity and a high voltage can be obtained by using it for the purpose of the present invention, and arrived at the present invention.
That is, the present invention is an organic electrolyte battery comprising a positive electrode, a negative electrode, and an aprotic organic solvent solution of a lithium salt as an electrolytic solution, wherein the negative electrode is a heat-treated product of an aromatic condensation polymer and contains hydrogen atoms / carbon atoms. Atomic ratio of 0.50
It is an insoluble and infusible substrate having a polyacene skeleton structure of 0.05, and a true specific gravity (ρ1) measured by impregnating the insoluble and infusible substrate with propylene carbonate and a true specific gravity measured by impregnation with dimethyl carbonate. Specific gravity (ρ
The ratio of 2) satisfies 0.9 ≦ (ρ2) / (ρ1) ≦ 1.1.

The true specific gravity (ρ1) measured by impregnating the insoluble and infusible substrate with propylene carbonate and the true specific gravity (ρ3) measured by impregnating ethyl alcohol.
Ratio of 0.95 ≦ (ρ3) / (ρ1) ≦ 1.15 is preferable, and further, the positive electrode preferably contains a metal oxide. Where propylene carbonate
Is a cyclic molecule with a molecular weight of 102.3,
Carbonate is a linear molecule with a molecular weight of 90.1.
Nol is a linear molecule with a molecular weight of 46.1. (Ρ2)
/ (Ρ1) is the propylene catalyst in the insoluble and infusible substrate.
True specific gravity and dimethyl carbonate measured by carbonate impregnation.
Shows the ratio of true specific gravity measured by carbonate impregnation.
You That the ratio is around 1 means that the insoluble and infusible group is
When the body is impregnated with molecules of different molecular weight and morphology, the same amount of
It has a technical meaning of showing true specific gravity. (Ρ3) / (ρ1)
Is an insoluble and infusible substrate in which propylene carbonate
True Density and Ethyl Alcohol Content Measured by Impregnation of
The ratio of true specific gravity measured by immersion is shown. The ratio is 1
The technical meaning of before and after is also the same as described above.

Examples of the aromatic condensation polymer in the present invention include a condensation product of an aromatic hydrocarbon compound having a phenolic hydroxyl group and 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

[Chemical 1] (Wherein x and y are each independently 0, 1 or 2), or may be hydroxy biphenyls or hydroxynaphthalenes. Of these, phenols, particularly phenol, are suitable for practical use. In particular, as the aromatic condensation polymer in the present invention, a modified aromatic compound obtained by substituting a part of the aromatic hydrocarbon compound having a phenolic hydroxyl group with an aromatic hydrocarbon compound having no phenolic hydroxyl group, for example, xylene. Group-based condensation polymers such as condensation products of phenol, xylene and formaldehyde are preferably used. Also,
A modified aromatic condensation polymer substituted with melamine or urea or a furan resin can also be used. As the aldehyde, aldehydes such as formaldehyde, acetaldehyde and furfural can be used, and formaldehyde is preferable among them. As the phenol-formaldehyde condensate, any of novolac type or resol type or a mixture thereof can be used.

The insoluble and infusible substrate in the present invention can be prepared by subjecting the above aromatic condensation polymer to a non-oxidizing atmosphere (including vacuum) as described in, for example, Japanese Patent Publication No. 1-44212. By gradually heating to an appropriate temperature of 400 to 800 ° C, an insoluble having a polyacene skeleton structure in which the atomic ratio of hydrogen atoms / carbon atoms (hereinafter referred to as H / C) is 0.50 to 0.05 The step of obtaining an infusible substrate (first step), and the insoluble infusible substrate in a non-oxidizing atmosphere containing an aromatic polymer decomposing gas or in a non-oxidizing atmosphere containing an aromatic gas, 800 °
It can be obtained by the step (second step) of heating to an appropriate temperature of C.

Specifically, the second step can be carried out as follows. That is, the insoluble and infusible substrate obtained in the first step has an appropriate shape (as it is if the insoluble and infusible substrate is already in a shape suitable for electrodes or electrode molding), if necessary, in practical use. Pulverize and classify into a shape that is easy to form into an electrode such as powder, granules, or short fiber. In the case of powder, the size thereof varies depending on the intended electrode shape, but is preferably 30 μm or less, more preferably 20 μm or less.
μm or less. The insoluble infusible substrate thus obtained is heated in a non-oxidizing atmosphere containing an aromatic polymer decomposing gas or in a non-oxidizing atmosphere containing an aromatic gas. The aromatic-based polymer decomposition gas is, for example, a phenol-based resin, a furan resin, a petroleum-based pitch, a coal-based pitch, or the like, which is 300 to 500 °
It is a gas generated by thermal decomposition in C, and generally contains various aromatic compounds. Examples of the aromatic gas include benzene, naphthalene, anthracene, xylene, toluene, phenol and the like, but are not particularly limited thereto.

Practically, the above gas is supplied to the heating furnace in a state of being mixed with a non-oxidizing gas such as nitrogen or argon. As the supply method, a heating furnace charged with the insoluble and infusible substrate is heated to 400 to 800 ° C. in a non-oxidizing atmosphere.
After heating, the aromatic polymer decomposition gas or aromatic gas is blown in a state of being mixed with a non-oxidizing gas such as nitrogen or argon, or the aromatic condensation polymer and the insoluble infusible substrate are heated in advance. A method of charging in a furnace and heating in a non-oxidizing atmosphere, reducing the flow rate of the non-oxidizing gas from the decomposition gas generation temperature to the target maximum heating temperature, and allowing the decomposition gas to stay in the heating furnace can be mentioned. What is important here is that the insoluble and infusible substrate is heated at a temperature higher than the gas generation temperature in a non-oxidizing atmosphere containing an aromatic polymer decomposition gas or in a non-oxidizing atmosphere containing an aromatic gas. It is to be. Therefore, when using a continuous heating furnace such as a rotary kiln or a conveyor furnace, it is possible to simultaneously perform the first step and the second step.

The insoluble and infusible substrate thus obtained is H /
C is 0.50 to 0.05, preferably 0.35 to 0.1
According to X-ray diffraction (CuKα), the position of the main peak is 2 ° or less and is 24 ° or less, and other than the main peak, it is broad between 41 and 46 °. There is a peak. That is, the insoluble and infusible substrate is suggested to have a polyacene skeleton structure in which an aromatic polycyclic structure is appropriately developed, and to have an amorphous structure, and lithium can be stably doped, so that the active material for a battery is Is useful as However, when the above H / C exceeds 0.50, the aromatic polycyclic structure is not sufficiently developed, so that lithium doping and dedoping cannot be smoothly performed, and the battery is assembled. The charging / discharging efficiency at that time decreases. On the other hand, if H / C is less than 0.05, the battery capacity will decrease,
Neither is preferable.

The insoluble and infusible substrate in the present invention has a true specific gravity (ρ determined by impregnation with propylene carbonate).
1) and the true specific gravity (ρ2) measured by impregnation with dimethyl carbonate is 0.9 ≦ (ρ2) / (ρ1) ≦ 1.
1, and more preferably 0.95 ≦ (ρ2) /
(Ρ1) ≦ 1.05. That is, (ρ2)
In either case where / (ρ1) exceeds 1.1 or is less than 0.9, the capacity of the battery decreases, which is not suitable. Further, the ratio of the true specific gravity (ρ1) measured by impregnating the insoluble and infusible substrate with propylene carbonate and the true specific gravity (ρ3) measured by impregnating ethyl alcohol is 0.95 ≦ (ρ3) / (ρ1). ≤
Particularly preferably, it is 1.15.

The negative electrode in the present invention comprises the above-mentioned insoluble infusible substrate, and in practice, an insoluble infusible substrate having a shape such as powder, granules, short fibers, etc., which can be easily molded, is molded with a binder. Is preferably used. Further, the electrode in the present invention can be formed by adding the above-mentioned insoluble and infusible substrate and, if necessary, a conductive material and a binder, and the kind and composition of these conductive material and binder are not particularly limited. . That is, the conductive material may be metal powder such as metallic nickel, but carbon-based materials such as activated carbon, carbon black, acetylene black and graphite are particularly preferable. The mixing ratio varies depending on the electric conductivity of the insoluble infusible substrate and the shape of the electrode, but it is appropriate to add 2 to 40% to the insoluble infusible substrate. As the binder, for example, a rubber-based binder such as SBR, a fluorine-containing resin such as polytetrafluoroethylene or polyvinylidene fluoride, or a thermoplastic resin such as polypropylene or polyethylene is preferable, and its mixing ratio is 20% or less. Preferably.

As the positive electrode of the organic electrolyte battery of the present invention,
Polymer materials such as polyacene-based organic semiconductors and polyaniline can be used, but when a secondary battery having a higher capacity is required, it is preferable to use a metal oxide, and more preferably Li _X CoO 2, for example. _2, Li _X N
Li _X M such as iO _2, Li _X MnO ₂ , and Li _X FeO _2.
A lithium-containing metal oxide capable of being electrochemically doped or dedoped with lithium, which may be represented by the general formula of _y O _Z (M may be a metal, or two or more kinds of metals), or cobalt,
A transition metal oxide such as manganese or nickel is used. Among them, a lithium-containing oxide having a voltage of 4 V or more with respect to lithium metal is preferable, and a lithium-containing cobalt oxide and a lithium-containing nickel oxide are particularly preferably used.

The positive electrode in the present invention is formed by adding the above-mentioned active material and, if necessary, a conductive material and a binder, and the kind and composition of the conductive material and the binder can be appropriately set. That is, the conductive material may be a metal powder such as metallic nickel, activated carbon, carbon black,
Carbon-based materials such as acetylene black and graphite are particularly preferable. The mixing ratio varies depending on the electrical conductivity of the active material, the shape of the electrodes, etc., but it is appropriate to add 2 to 40% to the active material. Further, the binder may be one that is insoluble in the electrolytic solution in the present invention to be described later, and examples thereof include rubber-based binders such as SBR, fluorine-containing resins such as polytetrafluoroethylene and polyvinylidene fluoride, polypropylene, polyethylene and the like. Thermoplastic resin of,
The mixing ratio is preferably 20% or less.

The electrode shapes of the positive electrode and the negative electrode used in the present invention are as follows.
Depending on the intended battery, various shapes such as a plate shape, a film shape, a column shape, or molding on a metal foil can be adopted. Particularly, the one formed on a metal foil is preferable because it can be applied to various batteries as a collector-integrated electrode.

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, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolane, methylene chloride, sulfolane and the like can be mentioned, and a mixture of two or more of these aprotic organic solvents can also be used. .

The electrolyte mixed or dissolved in a single solvent may be any electrolyte capable of producing lithium ions. As such an electrolyte, for example, L
iI, LiClO ₄ , LiAsF ₆ , LiBF ₄ , Li
PF ₆ , LiHF _2, etc. may be mentioned.

The above-mentioned electrolyte and solvent are mixed in a sufficiently dehydrated state to form an electrolytic solution. The concentration of the electrolyte in the electrolytic solution is at least 0 in order to reduce the internal resistance of the electrolytic solution. 0.1 mol / l or more is preferable, and 0.2 to 1.5 mol / l is particularly preferable.

As the current collector for taking out the current to the outside of the battery, for example, carbon, platinum, nickel, stainless steel,
Aluminum, copper, or the like can be used. When a foil-shaped or net-shaped current collector is used, it can be used as a current collector-integrated electrode by molding the electrode on the current collector.

FIG. 1 is an explanatory view of the basic constitution of the organic electrolyte battery according to the present invention. In this figure, (1) is a positive electrode and (2) is a negative electrode. (3) and (3 ') are current collectors, which are connected to the electrodes and the external terminals (7) and (7') without causing a voltage drop. (4) is an electrolytic solution in which the above-mentioned compound capable of generating ions that can be doped is dissolved in an aprotic organic solvent. The electrolytic solution (4) is usually liquid, but it may be used in the form of gel or solid in order to prevent liquid leakage. (5) is a separator arranged for the purpose of preventing contact between the positive and negative electrodes (1) and (2) and holding the electrolytic solution.

The above-mentioned separator (5) is a porous material having continuous ventilation holes that are durable to an electrolytic solution or an electrode active material and has no electron conductivity, and is usually a cloth made of glass fiber, polyethylene, polypropylene or the like. A non-woven fabric or a porous body is used. The thickness of the separator (5) is preferably thin in order to reduce the internal resistance of the battery, but is appropriately determined in consideration of the amount of electrolyte retained, flowability, strength and the like. The positive and negative electrodes (1), (2) and the separator (5) are fixed in the battery case (6) so as not to cause practical problems.

The shape and size of the electrode are appropriately determined depending on the shape and performance of the intended battery. As the shape of the battery of the present invention, a coin type, which satisfies the above basic configuration,
Examples thereof include a cylinder type, a square type, and a box type, but are not particularly limited.

[0026]

INDUSTRIAL APPLICABILITY As described above, the organic electrolyte battery of the present invention has an insoluble and infusible structure having a polyacene skeleton structure in which the ratio of true specific gravities measured with two or more different solvents is within a specific range. By using the substrate as the negative electrode, high capacity and high voltage can be realized.

[0027]

EXAMPLES The present invention will be specifically described below with reference to examples.

[Measurement Method of True Specific Gravity] (1) Accurately measure the weight of a pycnometer having an internal volume of about 10 cc that has been sufficiently dried in advance. Then, a sample (70 ° C., dried under reduced pressure for about 2 hours) is placed flat on the bottom of the sample, and its weight is accurately measured. To this, the solvent previously kept under reduced pressure for 20 minutes or longer is gently added until about 7 minutes of the pycnometer. Then, the pycnometer was lightly shaken to confirm that the generation of large bubbles had disappeared, and then ultrasonic waves were applied for 10 minutes. Further, it is filled with a solvent, capped, and immersed in a constant temperature water bath (adjusted at 25 ° C) for 15 minutes or longer, and the liquid level of the solvent is adjusted to the rating line. Next, this is taken out, the outside is wiped well, the weight is accurately measured, the weight is again put in the constant temperature water tank, and the same operation is repeated to obtain an average value of four times. Next, the same pycnometer is filled with a solvent, and the same pycnometer is immersed in a constant temperature water bath in the same manner as described above, the evaluation lines are matched, the weight is measured, and this operation is repeated to obtain an average value of four times. Immediately before use, boil the distilled water and remove the dissolved gas in a pycnometer, dip it in a constant temperature water bath as described above, match the rating lines, measure the weight, and repeat this operation 4 times. Take the average value of.

(2) The true specific gravity of the sample is calculated by the following formula.
However, it is summarized in two digits after the decimal point. [Where d₁: True specific gravity, w₁: Pycnometer weight
(G), w₂: Weight when the sample is put in the pycnometer
Sa (g), w₃: Pycnometer only solvent up to rating line
Weight when put (g), w_Four: Sample on pycnometer
, And the weight (g) when the solvent is added up to the rating line,
w_Five: When I put only distilled water into the pycnometer up to the rating line
Mushroom weight (g), d: Specific gravity of water (0.9970 25 °
C)]

(3) The solvent used is propylene carbonate (manufactured by Toyama Yakuhin), dimethyl carbonate (manufactured by Toyama Yakuhin), ethyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.), and the true specific gravity measured using propylene carbonate is (ρ
1), the true specific gravity measured using dimethyl carbonate was (ρ2), and the true specific gravity measured using ethyl alcohol was (ρ3).

[Production Example 1 of PAS] 50 parts by weight of xylene resin (manufactured by Lignite Co., Ltd.), 50 parts by weight of novolac (manufactured by Showa High Polymer Co., Ltd.), and 0.1 part by weight of xylene sulfonic acid were used.
It heated at 00 degreeC and the xylene modified novolak resin was obtained. Hexamethylenetetramine (10 parts by weight) was mixed with 100 parts by weight of this resin, and the mixture was crushed and molded into a molded plate by hot pressing. This xylene-modified novolac resin molded plate was placed in a square electric furnace (50 cm × 40 cm × 100 cm), and heated up to 400 ° C. at 100 ° C./hour and then at 10 ° C./hour in a nitrogen atmosphere. , 650 ° C
Heat treatment was performed until the insoluble and infusible substrate (referred to as PAS) was synthesized. The PAS plate thus obtained was crushed with a jet mill to obtain a PAS powder (PAS powder having an average particle size of 7 μm).
0) was obtained. The H / C of PAS0 was 0.22. Next, 100 g of this PAS0 and 400 g of the above xylene-modified novolac resin molded body were simultaneously charged in a square electric furnace, and the temperature up to 400 ° C. was 100 ° C./hour, and then 50 ° C.
The temperature was raised at a rate of ° C / hour and heat treatment was performed up to 650 ° C. Nitrogen flow rate from 400 ° C to 650 ° C is 1L / mi
n, 10 L / min, 50 L / min, PAS
1, PAS2 and PAS3 were obtained. Table 1 shows the H / C and true density ratios of the respective powders.

[Production Example 2 of PAS] PAS0 of Production Example 1
Was put into a crucible and charged into a cylindrical silicon knit furnace. At the same time, when the temperature of PAS0 of the silicon knit furnace becomes 650 ° C, xylene resin (manufactured by Lignite Co., Ltd.) is put in a crucible at a position of 350 ° C, and 100 ° C / hour up to 400 ° C under a nitrogen stream, Thereafter, the temperature was raised at a rate of 50 ° C./hour, and heat treatment was performed up to 650 ° C. to obtain PAS4. In this case, when the temperature of PAS reaches 650 ° C., the xylene resin (manufactured by Lignite Co., Ltd.) is heated to 350 ° C., decomposed gas is generated, mixed with nitrogen gas, and conveyed to the charging position of PAS. Table 1 shows the H / C and true density ratios of PAS4.

Examples 1 to 4 As Examples 1 to 4, 90 parts by weight of PAS1, PAS2, PAS3 and PAS4, 10 parts by weight of acetylene black and 10 parts by weight of polyvinylidene fluoride powder were added to N-methylpyrrolidone. A slurry was obtained by thoroughly mixing 110 parts by weight of a solution dissolved in 100 parts by weight. These slurries were applied on a copper foil (negative electrode current collector) with a thickness of 10 μm using an applicator, dried and pressed to a thickness of 110 μm.
m PAS negative electrode was obtained.

Poly (4) is added to 100 parts by weight of LiCoO _2.
5 parts by weight of fluorinated ethylene and 10 parts by weight of acetylene black were mixed well, and a roller was used to obtain a positive electrode sheet having a thickness of 300 μm.

The above-mentioned positive and negative electrodes (1 × 1 cm ² ) were used to assemble the battery shown in FIG. 1 and described above. The positive and negative electrode current collectors are made of stainless steel wire, and the separators have a thickness of 2
A 5 μm polypropylene separator was used. A solution prepared by dissolving LiPF ₆ at a concentration of 1 mol / l in a mixed solvent of ethylene carbonate / diethyl carbonate = 1: 1 was used as the electrolytic solution.

The following studies were conducted on each of the above batteries. That is, at 25 ° C, 0.25 mA /
cm ² constant current charge, charged to 4.2V, followed by 0.25 mA / cm ² constant current discharge,
It discharged until the open circuit voltage became 2.0V. The cycle of 4.2 V to 2.0 V was repeated for this battery, and the capacity was evaluated in the third discharge. The results are shown in Table 1.

[Comparative Example] 90 parts by weight of the above PAS0,
A slurry was obtained by sufficiently mixing 110 parts by weight of a solution prepared by dissolving 10 parts by weight of acetylene black and 10 parts by weight of polyvinylidene fluoride powder in 100 parts by weight of N-methylpyrrolidone. The slurry was applied onto a copper foil (negative electrode current collector) having a thickness of 10 μm using an applicator, dried and pressed to obtain a PAS negative electrode having a thickness of 110 μm.

Poly (4) is added to 100 parts by weight of LiCoO _2.
5 parts by weight of fluorinated ethylene and 10 parts by weight of acetylene black were mixed well, and a roller was used to obtain a positive electrode sheet having a thickness of 300 μm.

Using the positive and negative electrodes (1 × 1 cm ² ) described above, the battery shown in FIG. 1 was assembled in the same manner as in Examples 1 to 4. A stainless wire mesh was used as the positive and negative electrode current collectors, and a polypropylene separator having a thickness of 25 μm was used as the separator. A solution prepared by dissolving LiPF ₆ at a concentration of 1 mol / l in a mixed solvent of ethylene carbonate / diethyl carbonate = 1: 1 was used as the electrolytic solution.

This battery was evaluated in the same manner as in Examples 1 to 4 above. The results are shown in Table 1.

[0041]

[Table 1]

From this result, it can be seen that the embodiment having the value of (ρ2) / (ρ1) of 1.1 or less has a high capacity,
In comparison, it can be clearly seen that the capacity of the comparative example in which the value of (ρ2) / (ρ1) exceeds 1.1 is low. Further, the values of (ρ3) / (ρ1) of the examples are all 1.15 or less, while (ρ3) / of the comparative example.
The value of (ρ1) exceeded 1.15.

[Brief description of drawings]

FIG. 1 is a diagram illustrating the basic configuration of an organic electrolyte battery according to the present invention.

[Explanation of symbols]

1 positive electrode 2 Negative electrode 3, 3'current collector 4 Electrolyte 5 separator 6 battery case 7, 7'external terminals

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shizukuni Yata 2-6-13 Miyanishi, Harima-cho, Kako-gun, Hyogo (56) References JP-A-6-20679 (JP, A) JP-A-7-122300 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) H01M 4/58-4/60 H01M 4/02-4/04 H01M 10/40

Claims (3)

(57) [Claims] 1. An organic electrolyte battery comprising a positive electrode, a negative electrode and an aprotic organic solvent solution of a lithium salt as an electrolytic solution, wherein the negative electrode is a heat-treated product of an aromatic condensation polymer and contains hydrogen atoms / carbon atoms. An insoluble infusible substrate having a polyacene skeleton structure with an atomic ratio of 0.50 to 0.05, and a true specific gravity (ρ1) and dimethyl carbonate measured by impregnating the insoluble infusible substrate with propylene carbonate. The ratio of the true specific gravity (ρ2) measured by the impregnation of is 0.9 ≦
An organic electrolyte battery characterized by satisfying (ρ2) / (ρ1) ≦ 1.1. 2. The ratio of the true specific gravity (ρ1) measured by impregnating an insoluble and infusible substrate with propylene carbonate and the true specific gravity (ρ3) measured by impregnating ethyl alcohol is:
The organic electrolyte battery according to claim 1, wherein 0.95 ≦ (ρ3) / (ρ1) ≦ 1.15 is satisfied. 3. The organic electrolyte battery according to claim 1, wherein the positive electrode contains a metal oxide.