JP2869191B2 - Organic electrolyte battery - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an insoluble and infusible substrate having a polyacene-based skeleton structure for a negative electrode and a high-capacity and high-voltage organic electrolyte battery using a metal oxide for a positive electrode.

In recent years, conductive polymers, transition metal oxides, etc. have been used as positive electrodes,
Secondary batteries using lithium metal or lithium alloy for the negative electrode have a high energy density, and thus have been proposed as alternatives to Ni-Cd batteries and lead batteries.

However, when these secondary batteries are repeatedly charged and discharged, the capacity is greatly reduced due to deterioration of the positive electrode or the negative electrode, and there is a problem in practical use. In particular, the deterioration of the negative electrode involves the formation of moss-like lithium crystals called dendrites, and the repetition of charging and discharging eventually causes the dendrites to penetrate the separator, causing a short inside the battery, and in some cases, the battery exploding. 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 a negative electrode and using a lithium-containing metal oxide such as LiCoO _{2 for} a 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 then returned to the positive electrode in discharging. Although the battery is characterized by high voltage and high capacity, its capacity is about 80 to 90 mAh / cc (based on the total volume of electrodes, separators, and current collectors) to obtain high energy density, which is a characteristic of lithium batteries. Has not been reached.

On the other hand, an insoluble and infusible substrate having a polyacene skeleton structure, which is a heat-treated aromatic condensed polymer and has an atomic ratio of hydrogen atoms / carbon atoms of 0.5 to 0.05, generates a larger amount of lithium than a general carbon material. It is possible to dope,
When a battery was assembled using the insoluble and infusible substrate, the capacity remained unsatisfactory.

Therefore, a first object of the present invention is to provide a secondary battery having a high capacity and a high voltage.

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

Still another object of the present invention is to provide a secondary battery which is easy to manufacture.

Further objects of the present invention will become clear from the description below.

In order to achieve the above objects and advantages, the present inventors use a metal oxide for the positive electrode, an insoluble infusible substrate having a polyacene-based skeleton structure for the negative electrode, and adjust the amount of lithium in the battery appropriately. It turned out to be important to control.

More specifically, according to the present invention, the above objects and advantages include an organic electrolyte battery including a positive electrode, a negative electrode, and a solution in which a lithium salt is dissolved in an aprotic organic solvent as an electrolyte. The positive electrode contains a lithium-containing metal oxide; and (2) the negative electrode is a heat-treated aromatic condensed polymer and has a polyacene skeleton structure in which the atomic ratio of hydrogen atoms / carbon atoms is 0.5 to 0.05. Insoluble and infusible substrate (hereinafter PAS)
(3) With respect to the negative electrode PAS, the total amount of lithium contained in the battery is 500 mAh / g or more, and lithium derived from the negative electrode is 10%.
It has been found that this is achieved by an organic electrolyte battery characterized by being at least 0 mAh / g.

The aromatic condensation polymer in the present invention is a condensate of an aromatic hydrocarbon compound and an aldehyde. As the aromatic hydrocarbon compound, for example, so-called phenols such as phenol, cresol and xylenol are suitable. For example, the following formula (A), (Where x and y are each independently 0, 1 or 2
And methylene bisphenols represented by the following formulas, or hydroxy biphenyls and hydroxynaphthalenes. Of these, phenols, particularly phenol, are practically preferred.

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

As the aldehyde, aldehydes such as formaldehyde, acetaldehyde, and furfural can be used, but formaldehyde is preferred. The phenol formaldehyde condensate may be any of a novolak type, a resol type or a mixture thereof.

The insoluble and infusible substrate in the present invention can be obtained by heat-treating the aromatic condensation polymer.
No. 2 (US Pat. No. 4,601,849, EP 67444), and Japanese Patent Publication No. 3-24024 (US Pat. No. 4,615,960, EP 149497)
The insoluble and infusible substrates having a polyacene skeleton structure described in, for example, can be used, and for example, they can also be produced as follows.

The aromatic condensation polymer is heated at 400 ° C. to 800 ° C. in a non-oxidizing atmosphere such as nitrogen or argon (including vacuum).
By gradually heating to an appropriate temperature of ° C., the atomic ratio of hydrogen atoms / carbon atoms (hereinafter referred to as H / C) is 0.50 to 0.05,
Preferably, an insoluble and infusible substrate of 0.35 to 0.10 can be obtained.

Also, Japanese Patent Publication No. 3-24024 (USP 4,615,960, EP149)
497) and the like, an insoluble infusible substrate having a specific surface area of at least 600 m ² / g by a BET method can also be obtained. For example, a solution containing an initial condensate of an aromatic condensation polymer and an inorganic salt such as zinc chloride is prepared, and the solution is heated and cured in a mold. The cured product thus obtained is
After gradually heating in a non-oxidizing atmosphere (including vacuum) to a temperature of 350 ° C. to 800 ° C., preferably to an appropriate temperature of 400 ° C. to 750 ° C., it is sufficiently washed with water or dilute hydrochloric acid. it allows have the H / C, and, for example, 600 meters ² / g
An insoluble and infusible substrate having a specific surface area by the above-described BET method can also be obtained.

The insoluble and infusible substrate used in the present invention is obtained by X-ray diffraction (CuK
According to α), the position of the main peak is expressed as 2θ
There are other peaks below {} and between 41 and 46 ° in addition to the main peak.

That is, it is suggested that the insoluble infusible substrate has a polyacene skeleton structure in which an aromatic polycyclic structure is appropriately developed and has an amorphous structure, and is useful as an active material for a battery because lithium can be stably doped. It is.

When H / C exceeds 0.50, doping and undoping of lithium cannot be performed smoothly because the aromatic polycyclic structure is not sufficiently developed.
The charge / discharge efficiency decreases. When H / C is 0.05 or less,
The capacity of the battery of the present invention is undesirably reduced.

The negative electrode of the present invention is composed of the insoluble and infusible substrate (hereinafter referred to as PAS), and in practice, it is desirable to use PAS in a shape that is easy to mold, such as powder, granule, or short fiber, with a binder. .

As the binder, a fluorine-based binder is preferable, and a fluorine atom / carbon atom atomic ratio (hereinafter, referred to as F / C
Is preferred, and a fluorine-containing binder having an F / C of less than 1.3 and 0.75 or more is particularly preferable.

Examples of the fluorine-based binder include, for example, polyvinylidene fluoride, vinylidene fluoride-3 fluoroethylene copolymer, ethylene-4 fluoroethylene copolymer, propylene-4 fluoroethylene copolymer, and the like. Further, a fluorine-containing polymer in which hydrogen in the main chain is substituted with an alkyl group can also be used. For polyvinylidene fluoride, F /
C is 1, and in the case of vinylidene fluoride-3 ethylene fluoride copolymer, when the molar fraction of vinylidene fluoride is 50% and 80%, the F / C is 1.25 and 1.1, respectively. In the case of the tetrafluoroethylene copolymer, when the propylene mole fraction is 50%, the F / C is 0.75. Among them, polyvinylidene fluoride and vinylidene fluoride have a molar fraction of 50.
% Of vinylidene fluoride-3 ethylene fluoride copolymer is preferred, and polyvinylidene fluoride is practically preferred.

When these binders are used, the lithium doping ability (capacity) of PAS can be fully utilized.

As the positive electrode of the organic electrolyte battery of the present invention, for example, Li
_{xCoO 2, LixNiO 2, LixMnO 2} , LixFeO 2 etc. LixMyOz (metal M capable of forming a plurality of valence, may also be in two or more metals) may be represented by the general formula, electrochemically doped with lithium, An undoped lithium-containing metal oxide is used. In particular, a lithium-containing oxide having a voltage of 4 V or more with respect to lithium metal is preferable. Among them, lithium-containing cobalt oxide and lithium-containing nickel oxide are preferable.

The positive electrode in the present invention is formed by adding the metal oxide, and, if necessary, a conductive material and a binder,
The type, composition, and the like of the conductive material and the binder may be set as appropriate.

The type of the conductive material may be metal powder such as metal nickel. For example, 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 active material, the shape of the electrode, etc., but it is appropriate to add 2 to 40% to the active material.

The type of the binder may be any as long as it is insoluble in the electrolytic solution used in the present invention described later, for example, a rubber-based binder such as SBR, polytetrafluoroethylene, or a fluorine-containing resin such as polyvinylidene fluoride. , Polypropylene, thermoplastic resin such as polyethylene is preferable, the mixing ratio is 20%
It is preferable to set the following.

The shape of the positive electrode and the negative electrode used in the present invention can take various shapes, such as a plate shape, a film shape, a column shape, or a shape formed on a metal foil, depending on a target battery. In particular, a material in which a positive electrode or a negative electrode is formed in a film shape or a plate shape on a metal foil is preferable as a current collector integrated electrode because it can be applied to various batteries.

The battery of the present invention can greatly improve the capacity as compared with the conventional battery by using the above PAS as the negative electrode and appropriately controlling the amount of lithium contained in the battery.

In the present invention, the total amount of lithium in the battery is the total of lithium derived from the positive electrode, lithium derived from the electrolyte, and lithium derived from the negative electrode.

The positive electrode-derived lithium is lithium contained in the positive electrode during battery assembly, and part or all of the lithium is
It is supplied to the negative electrode by an operation (charging or the like) that passes current from an external circuit. The term “lithium derived from an electrolyte” refers to lithium in an electrolyte contained in a separator, a positive electrode, a negative electrode, and the like. Further, the lithium derived from the negative electrode refers to the negative electrode of the present invention.
Lithium supported on PAS (lithium other than lithium derived from the positive electrode and electrolyte).

The method of supporting lithium on the negative electrode PAS is not particularly limited.For example, a method of preliminarily doping lithium into the negative electrode PAS in an electrochemical cell with lithium metal as a counter electrode before assembling the battery, and then assembling the battery, For example, a method in which the negative electrode PAS and lithium metal are made conductive in the battery by a method such as sticking to the negative electrode PAS, and lithium is doped into the PAS in the battery, or the like.

In the present invention, the total amount of lithium in the battery is 500 mAh / g or more with respect to the negative electrode PAS, preferably 600 mAh / g or more,
If it is less than 0 mAh / g, sufficient capacity cannot be obtained.

Further, in the present invention, the lithium derived from the negative electrode is the negative electrode PAS.
100 mAh / g or more, preferably 150 mAh / g or more,
If it is less than 100 mAh / g, a sufficient capacity cannot be obtained even if the total lithium amount is 500 mAh / g or more with respect to the negative electrode PAS.

In the present invention, the lithium derived from the positive electrode and the lithium derived from the electrolyte may satisfy the above conditions, but the lithium derived from the positive electrode is 300 mAh / g or more with respect to the negative electrode PAS, that is, the lithium derived from the positive electrode is 1 g of the negative electrode PAS. It is preferably 300 mAh or more per unit.

When a lithium-containing oxide is used for the positive electrode, it is advantageous that the amount of lithium derived from the negative electrode be 600 mAh / g or less with respect to the negative electrode PAS.

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, for example, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolan, methylene chloride, sulfolane, and the like. A mixture of two or more organic solvents can also be used.

The electrolyte to be mixed or dissolved in a single solvent may be any electrolyte that can generate lithium ions. Such electrolytes include, for example, LiI, LiClO ₄ , L
Examples include iAsF ₆ , LiBF ₄ , LiPF ₆ , or LiHF ₂ .

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

As a current collector for extracting a current outside 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, an electrode is collected. By being molded on a current collector, it can also be used as a current collector integrated electron.

Next, an example of an embodiment of the present invention will be described with reference to the drawings.
FIG. 1 is a diagram illustrating the basic configuration of a battery according to the present invention. FIG.
In the above, (1) is a positive electrode, and (2) is a negative electrode.
(3) and (3 ') are current collectors, which are connected to each electrode and the external terminals (7) and (7') so as not to cause 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 electrolyte is usually liquid, but may be used in a gel or solid state to prevent liquid leakage. (5) is a separator disposed for the purpose of preventing contact between the positive and negative electrodes and holding the electrolyte.

The separator, the electrolyte or the electrode active material, etc.
It is a porous body without electron conductivity having durable interconnected pores, usually glass fiber. A cloth, nonwoven fabric or porous body made of polyethylene or polypropylene is used. The thickness of the separator is preferably thin in order to reduce the internal resistance of the battery, but is determined in consideration of the amount of retained electrolyte, flowability, strength, and the like. The positive and negative electrodes and the separator are fixed in the battery case (6) so that there is no practical problem. The shape, size, and the like of the electrode are appropriately determined depending on the shape and performance of the intended battery.

The shape of the battery of the present invention may be a coin type, a cylindrical type, a square type, a box type, or the like that satisfies the above basic configuration, and the shape is not particularly limited.

As described above, the features and advantages of the organic electrolyte battery of the present invention include the use of PAS for the negative electrode, the use of metal oxide for the positive electrode, and appropriate control of both the amount of lithium in the battery and the amount of lithium derived from the negative electrode PAS. It is a high capacity and high voltage battery.

As described above, the basic feature of the organic electrolyte battery of the present invention is that the total amount of lithium contained in the battery is 500 mAh / g.
As described above, the amount of lithium derived from the negative electrode is controlled to 100 mAh / g or more. Further, preferred embodiments of the present invention are as follows.

(1) As described above, the battery of the present invention controls the amount of lithium contained in the battery appropriately and controls the pore structure of PAS used for the negative electrode as described below. The capacity can be greatly improved as compared with the case of FIG.

The amount of nitrogen gas adsorbed on PAS in the present invention can be measured as follows. That is, 0.035 g of PAS powder having an average particle size of 15 μm pulverized by a disk mill is put into a sample cell of a constant volume apparatus (Autosorb-1 manufactured by Yuasa Ionics), and nitrogen gas is adsorbed at a liquid nitrogen temperature of 77K. From the obtained adsorption isotherm, the adsorption gas layer thickness t (ガ ス)
Plot the amount of adsorbed gas (cc / g). t (Å)
The following equation (1) is used.

In the present invention, the pore structure of PAS used for the negative electrode is obtained from the above nitrogen adsorption isotherm, the nitrogen adsorption thickness
It is preferable to control the amount of adsorbed gas at 10 ° C. to be 100 cc / g or less, particularly 80 cc / g or less.

In the present invention, if the amount of gas adsorbed on the PAS at a nitrogen adsorption thickness of 10 mm exceeds 100 cc / g, sufficient capacity cannot be obtained.

In the present invention, further, the total lithium amount in the battery is:
It is 500 mAh / g or more, and preferably 600 mAh / g or more with respect to the negative electrode PAS, and if it is less than 500 mAh / g, sufficient capacity cannot be obtained.

In the present invention, the amount of lithium derived from the negative electrode is negative electrode PA.
S is 100 mAh / g or more, preferably 150 mAh / g or more, and if it is less than 100 mAh / g, even if the total amount of lithium is negative electrode PA
Even if S is 500 mAh / g or more, sufficient capacity cannot be obtained.

The lithium derived from the positive electrode and the lithium derived from the electrolyte in the present invention may satisfy the above conditions, but it is preferable that the lithium derived from the positive electrode be at least 300 mAh / g with respect to the negative electrode PAS.

(2) Next, a second preferred embodiment of the present invention will be described.

In the present invention, a heat-treated product of an aromatic condensation polymer, which is a powder of an insoluble infusible substrate (hereinafter referred to as PAS) having a polyacene skeleton structure in which the atomic ratio of hydrogen atoms / carbon atoms is 0.5 to 0.05. As described above, it is preferable to use a binder (preferably a granular, powdery, short fiber, etc.) molded with a binder, preferably a fluorine-based binder, as the negative electrode.

Thus, the negative electrode of the present invention comprises the insoluble infusible substrate (PA
S) A powder molded product, which is obtained by molding a PAS powder having a shape that is easy to mold such as a powder or a granule with a binder, and the average particle size of the PAS of the powder is 20 μm or less, and Five
When the 0% diameter is 2aμm, particles having a particle diameter of 1aμm or less are 10% or more by volume to the whole, and particles having a particle diameter of 4aμm or more are 10% or more by volume to the whole. Certain, more preferably, when the 50% diameter is 2aμm, particles having a particle diameter of 1aμm or less are 20% or more by volume relative to the whole, and particles having a particle diameter of 4aμm or more are Those having a volume ratio of 10% or more, particularly preferably, when the 50% diameter is 2a μm, particles having a particle size of 1a μm or less are 20% or more by volume to the whole, and 4a
Particles with a particle size of μm or more account for 20% by volume of the whole
What is described above is advantageous. In the present invention, the granules have a wide particle size distribution, and the average particle size does not exceed 20 μm.
This is advantageous for obtaining a high-capacity battery. Average particle size is 20μ
m, or even if the average particle diameter is 20 μm or less, when the 50% diameter is set to 2 aμm, particles having a particle diameter of 1 aμm or less are less than 10% in volume ratio to the whole, or 4 aμm When the volume ratio of the particles having the above particle diameters is less than 10% with respect to the whole, the capacity of the obtained battery becomes low, which is not preferable.

Here, the average particle diameter is a volume average diameter, and the 50% diameter is a particle diameter corresponding to 50% of an integrated distribution curve (see the following literature).

Ed. Kubo et al., “Powder Theory and Applications,” pp. 450-453 (issued by Maruzen Co., Ltd. on May 12, 1979). PAS of the powder is, for example, heat treatment of a molded article of an aromatic condensation polymer. The resulting insoluble and infusible substrate can be obtained by crushing. The pulverization method is not particularly limited, but a pulverizer having both impact and friction pulverization mechanisms, for example, a pot mill,
It is efficient to use a ball mill such as a vibration mill. In some cases, it can also be obtained by classifying the obtained powder, or by mixing two or more PAS powders having different particle size distributions.

As described above, the binder used for the negative electrode of the present invention is preferably a fluorine-based binder, and more preferably a fluorine-containing binder having an atomic ratio of fluorine atoms / carbon atoms (hereinafter, referred to as F / C) of less than 1.5 and not less than 0.75. A fluorine-based binder is preferable, and a fluorine-based binder having a molecular weight of less than 1.3 and 0.75 or more is particularly preferable.

Examples of the fluorine-based binder include, for example, polyvinylidene fluoride, vinylidene fluoride-3 ethylene fluoride copolymer, ethylene-fluorinated ethylene copolymer, propylene-4-fluorinated ethylene copolymer, and the like. A fluorine-containing polymer in which hydrogen in the main chain is substituted with an alkyl group can also be used.

As described above, the negative electrode of the present invention is obtained by forming the PAS powder with a binder. The porosity of the negative electrode is obtained by impregnating propylene carbonate at 25 ° C., and is 40% or less. Is preferred. When the porosity exceeds 40%, even if the particle size of PAS is controlled as described above, it is difficult to obtain a sufficient capacity in a battery.

The porosity of the negative electrode used in the present invention is 40 as described above.
% Is preferable, but the present inventors have surprisingly found that a high-capacity battery can be obtained even when the porosity of the negative electrode is about 25%. In light of this fact, it is considered that the porosity of the negative electrode may be about 20%.

(3) Hereinafter, a third preferred embodiment of the present invention will be described.

As the negative electrode of the organic electrolyte battery of the present invention, an insoluble infusible substrate having a polyacene skeleton structure in which the negative electrode is a heat-treated aromatic condensation polymer and has an atomic ratio of hydrogen atom / carbon atom of 0.5 to 0.05 ( It is preferable that PAS) be formed on a metal foil using a thermoplastic binder and then heat-treated at a temperature equal to or higher than the melting point of the thermoplastic binder.

As the thermoplastic binder, as described above, a fluorine-containing polymer binder, particularly a fluorine-containing polymer having an atomic ratio of fluorine atom / carbon atom of less than 1.5 to 0.75 or more, particularly polyvinylidene fluoride is preferable.

When these binders are used, the lithium doping ability (capacity) of PAS can be fully utilized.

When the negative electrode of the present invention is obtained by molding the PAS with a binder and then performing heat treatment at a temperature equal to or higher than the melting point of the binder, the method of the heat treatment is not particularly limited. Preferably, it is performed in a high temperature range. If the heat treatment is not performed, for example, the negative electrode PAS formed on a metal foil, when a battery is assembled after preliminarily doping lithium in an electrochemical cell having lithium metal as a counter electrode, the bending strength of the electrode becomes weaker. Peeling is likely to occur, and furthermore, the internal resistance of the assembled battery will increase, making it difficult to obtain a sufficient capacity.

In the present invention, in order to mold an insoluble infusible substrate (PAS) having a polyacene skeleton structure on a metal foil using a thermoplastic binder, preferably a fluorine-containing polymer binder, The conductive substrate, the fluorine-containing polymer, and a solvent or a dispersion medium are sufficiently mixed and molded. The proportion of the fluorine-containing polymer varies depending on the shape and particle size of the insoluble infusible substrate, the strength and shape of the target electrode, and the like, but is preferably 2% by weight based on the insoluble infusible substrate.
To 50%, more preferably 5% to 30%. As the solvent, a solvent such as N, N-dimethylformamide, N-methylpyrrolidone, N, N-dimethylacetamide, which can dissolve the fluorine-containing polymer, is preferable. In the mixture, even if the fluorine-containing polymer is completely dissolved, even if only a part is dissolved, there is no particular problem,
It is preferable that the fluorine-containing polymer is completely dissolved in order to obtain a homogeneous electrode. The viscosity of the mixture can be controlled by the amount of the solvent.For example, the mixture adjusted to a high viscosity is formed into a sheet using a roller or the like, or a mixed slurry adjusted to a low viscosity is applied to a metal foil. , Drying, pressing if necessary for example 10
An ultra-thin electrode of 0 μm or less can be obtained. In particular, when excellent flexibility is required, a coating molding method is desirable.

The electrode shape of the positive electrode and the negative electrode used in the present invention can be various shapes such as a plate shape, a film shape, a cylindrical shape, or formed on a metal foil depending on a target battery. The one molded on a foil is preferable as a current collector integrated electrode because it can be applied to various batteries.

(4) Next, a fourth preferred embodiment of the present invention will be described.

In the organic electrolyte battery according to the present invention, there is further provided: i) an insoluble infusible material having a polyacene skeleton structure in which the negative electrode is a heat-treated aromatic condensation polymer and has an atomic ratio of hydrogen atom / carbon atom of 0.5 to 0.05. Ii) The total amount of lithium contained in the battery is 500 mAh / g or more and the amount of lithium derived from the negative electrode is 100 m with respect to the negative electrode PAS.
Ah / g or more, and iii) lithium derived from the negative electrode, which is previously supported on PAS before assembling the battery, is preferably used.

The lithium derived from the negative electrode in the present invention is lithium supported on the negative electrode PAS of the present invention (lithium other than lithium derived from the positive electrode and lithium derived from the electrolyte).

In the above preferred embodiment of the present invention, the method of supporting lithium on the negative electrode PAS is not particularly limited as long as lithium can be supported on the negative electrode PAS in advance before assembling the battery, but, for example, lithium metal is used as a counter electrode. By applying a constant current or applying a constant voltage in the electrochemical cell, lithium can be previously supported on the negative electrode PAS. When lithium is supported on the negative electrode PAS after the battery is assembled, for example, the negative electrode PAS and the lithium metal are conducted in the battery by a method such as attaching lithium metal to the negative electrode PAS, and lithium is passed through the PAS in the battery.
It is not preferable to take a method such as doping not only because the capacity as a practical battery is lowered but also the internal resistance of the battery is increased.

Also in this case, in the present invention, the total amount of lithium in the battery is 500 mAh / g or more with respect to the negative electrode PAS, preferably 600 mAh / g.
Advantageously, it is at least mAh / g, and if it is less than 500 mAh / g, sufficient capacity cannot be obtained.

Further, in the present invention, the lithium derived from the negative electrode is the negative electrode PAS.
100 mAh / g or more, preferably 150 mAh / g or more,
If it is less than 100 mAh / g, a sufficient capacity cannot be obtained even if the total lithium amount is 500 mAh / g or more with respect to the negative electrode PAS. When a lithium-containing oxide is used for the positive electrode, as described above, it is practical that the amount of lithium derived from the negative electrode is set to 600 mAh / g or less with respect to the negative electrode PAS.

The lithium derived from the positive electrode and the lithium derived from the electrolyte in the present invention may satisfy the above conditions, but it is preferable that the lithium derived from the positive electrode be at least 300 mAh / g with respect to the negative electrode PAS.

Next, an example of still another embodiment of the present invention will be described with reference to the drawings. FIG. 2 is a diagram illustrating the basic configuration of the battery according to the present invention. In FIG. 2, (1) is a positive electrode, and (2) is a negative electrode. (3) and (3 ') are current collectors, and the electrodes are formed on the current collectors. Lead terminals (10), (1
0 ′) is connected to a current collector so as not to cause a voltage drop, and one end thereof is connected to a battery case (6) and a top cover (9).
Connected to. (5) is a separator impregnated with an electrolytic solution, in which the aforementioned compound capable of generating ions that can be doped is dissolved in an aprotic organic solvent. The electrolyte is usually in a liquid state and is impregnated in a separator. However, the electrolyte may be used in a gel or solid state without a separator to prevent liquid leakage. (8)
Is an insulating packing arranged to prevent contact between the positive and negative electrodes (battery case and top cover).

The separator, for the battery solution or the electrode active material,
It is a porous body having durable interconnected pores without electron conductivity, and usually a cloth, nonwoven fabric or porous body made of glass fiber, polyethylene or polypropylene or the like is used. The thickness of the separator is preferably thin in order to reduce the internal resistance of the battery, but is determined in consideration of the amount of retained electrolyte, flowability, strength, and the like. The positive and negative electrodes and the separator are fixed in the battery case (6) so that there is no practical problem. The shape, size, and the like of the electrode are appropriately determined depending on the shape and performance of the intended battery.

The shape of the battery of the present invention is not limited to the cylindrical shape as exemplified above, but includes a coin shape, a square shape, a box shape and the like, and the shape is not particularly limited.

(5) Next, a fifth preferred embodiment of the present invention will be described.

In the present invention, as described above, a positive electrode, a negative electrode, and an aprotic organic solvent solution of a lithium salt are provided as an electrolytic solution. (1) The positive electrode contains a metal oxide, and (2) the negative electrode is an aromatic type. A heat-treated condensed polymer comprising an insoluble infusible substrate (PAS) having a polyacene skeleton structure in which the atomic ratio of hydrogen atoms / carbon atoms is 0.5 to 0.05, (3) the negative electrode PAS The total amount of lithium contained in the battery is 500 mAh / g or more, and the amount of lithium derived from the negative electrode is 10
When manufacturing an organic electrolyte battery having 0 mAh / g or more, it is preferable that lithium derived from the negative electrode is electrochemically supported by applying a potential equal to or lower than the potential of Li metal to the negative electrode.

In the present invention, as described above, the total amount of lithium in the battery is the total of lithium derived from the positive electrode, lithium derived from the electrolyte, and lithium derived from the negative electrode.

The positive electrode-derived lithium is lithium contained in the positive electrode during battery assembly, and part or all of the lithium is
It is supplied to the negative electrode by an operation (charging or the like) that passes current from an external circuit. In addition, the lithium derived from the electrolytic solution is lithium in the electrolytic solution contained in the separator, the positive electrode, the negative electrode, and the like. Further, the lithium derived from the negative electrode refers to the negative electrode of the present invention.
Lithium supported on PAS (lithium other than lithium derived from the positive electrode and electrolyte).

In the present invention, the method of supporting lithium on the negative electrode PAS is, for example, before assembling a battery, in an electrochemical cell having lithium metal as a counter electrode, by passing a constant current, or by applying a constant voltage, or By the combination, lithium can be previously supported on the negative electrode PAS.

In the present invention, when lithium is previously supported on the negative electrode PAS, it is particularly advantageous to apply a potential other than the lithium metal potential to the negative electrode PAS at least once with respect to the lithium metal potential. The voltage to be applied varies depending on the target amount of lithium derived from the negative electrode, the PAS, the type and shape of the electrode, and the type and shape of the electrolytic cell. 10mV to -300mV. It is important to select a potential and a lower voltage so that lithium metal is not deposited. In some cases, lithium is first supported at a potential lower than the lithium metal potential and gradually Method to raise the voltage to the end, finally ending at a positive potential,
Alternatively, it can be initially supported at a positive potential and later supported at a potential equal to or lower than the lithium metal potential.

In the present invention, the total amount of lithium in the battery is 500 mAh / g or more with respect to the negative electrode PAS, preferably 600 mAh / g or more,
If it is less than 0 mAh / g, sufficient capacity cannot be obtained.

Further, in the present invention, the lithium derived from the negative electrode is the negative electrode PAS.
100 mAh / g or more, preferably 150 mAh / g or more,
If it is less than 100 mAh / g, a sufficient capacity cannot be obtained even if the total lithium amount is 500 mAh / g or more with respect to the negative electrode PAS. When a lithium-containing oxide is used for the positive electrode, lithium derived from the negative electrode is 600 mAh /
It is practical to make it less than g.

The lithium derived from the positive electrode and the lithium derived from the electrolyte in the present invention may satisfy the above conditions, but it is preferable that the lithium derived from the positive electrode be at least 300 mAh / g with respect to the negative electrode PAS.

(6) Further, a sixth preferred embodiment of the present invention will be described below.

In the present invention, when lithium derived from the negative electrode described in the above (4) is pre-supported on the PAS before assembling the battery, the lithium derived from the negative electrode is electrochemically formed using a solution of a lithium salt in a cyclic carbonate solvent. It is particularly preferable to carry it.

Here, the lithium salt is, for example, LiClO ₄ , LiAsF ₆ , Li
BF ₄ , LiPF ₆ is an electrolyte capable of producing lithium ions such as, and the cyclic carbonate solvent is a single solvent such as ethylene carbonate and propylene carbonate, or
Two or more mixed solvents can be used. The electrolyte and the 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 mol / mol in order to reduce the internal resistance due to the electrolyte.
It is preferably at least, and more preferably 0.2 to 1.5 mol /. There is no particular limitation as long as lithium can be supported on the negative electrode PAS in advance.For example, by using the above-described electrolyte solution and passing a constant current through an electrochemical cell having lithium metal as a counter electrode, or by applying a constant voltage. By applying the voltage, lithium can be previously supported on the negative electrode PAS.

According to the present invention described above, an organic electrolyte battery that is easy to manufacture and that can be used as a secondary battery having a high capacity and a high voltage is provided.

Further, the organic electrolyte battery of the present invention provides a secondary battery which can be charged and discharged for a long period of time and is excellent in safety.

Further, the first, second, third, fourth and fifth aspects of the present invention are described.
And one or more of the sixth preferred embodiments provide a particularly high capacity secondary battery.

Further, the third and fourth preferred aspects of the present invention are advantageous because they provide a secondary battery having a low internal resistance and a high capacity.

Further, the fifth preferred embodiment of the present invention has an advantage that the high capacity and high voltage secondary battery of the present invention can be manufactured more easily.

Hereinafter, the present invention will be described with reference to examples. However, the following examples are intended to specifically explain aspects of the present invention, and the present invention is not limited to the following examples,
Or are not bound.

The basic structure of the battery according to the present invention shown in FIG. 1 is as follows.

DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Negative electrode 3, 3 'Current collector 4 Electrolyte solution 5 Separator 6 Battery case 7, 7' External terminal Moreover, the basic structure of the battery which concerns on this invention shown in the attached FIG. 2 is as follows.

DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Negative electrode 3 Current collector (positive electrode) 3 'Current collector (negative electrode) 8 Insulating packing 5 Separator 6 Battery case 9 Top cover 10 Terminal (positive electrode) 10' terminal (negative electrode) Example 1 0.5 mm thick phenol -Place the formaldehyde resin molded plate in a silicon electric furnace at 10 ° C /
The temperature was raised at a rate of time and heat-treated to 650 ° C. to synthesize an insoluble and infusible substrate (referred to as PAS). The PAS plate thus obtained is pulverized with a disk mill to obtain an average particle size of 15 μm.
PAS powder was obtained. The H / C ratio was 0.22.

Next, 100 parts by weight of the PAS powder and 100 parts by weight of a solution of 10 parts by weight of polyvinylidene fluoride powder dissolved in 90 parts by weight of N, N-dimethylformamide were sufficiently mixed to obtain a slurry. Thick the slurry using an applicator
It was applied on a 10 μm copper foil (negative electrode current collector), heated, dried and pressed to obtain a 110 μm thick PAS negative electrode.

To 100 parts of commercially available LiCoO ₂ (manufactured by Strem) and 5 parts of graphite, 10 parts by weight of vinylidene fluoride powder was added to N, N
-A slurry was obtained by sufficiently mixing 50 parts by weight of a solution dissolved in 90 parts by weight of dimethylformamide. The slurry was applied on a 20 μm-thick aluminum foil (positive electrode current collector) using an applicator, dried and pressed to obtain a 150 μm-thick positive electrode 1.

The above negative electrode has lithium as a counter electrode, and the electrolyte contains propylene carbonate and diethyl carbonate in a ratio of 1: 1 (weight ratio).
Using a solution in which LiPF ₆ was dissolved to a concentration of 1 mol / mol as the mixed solution, and applying a constant current (an electric current such that 30 mAh / g of lithium is supported on the negative electrode PAS per hour) was set to 150 mAh / negative electrode PAS. g, 200 mAh / g, and 300 mAh / g of lithium were loaded and supported (lithium derived from the negative electrode). The negative electrodes were 1, 2, and 3, respectively.

Using the positive electrode and the negative electrodes 1, 2, and 3 (all 1 × 1 cm ² ), three types of batteries as shown in FIG. 1 were assembled. As the separator, a polypropylene separator having a thickness of 25 μm was used. As the electrolytic solution, a solution obtained by dissolving LiPF ₆ at a concentration of 1 mol / in a 1: 1 (weight ratio) mixed solution of propylene carbonate and diethyl carbonate was used. Table 1 shows the total amount of lithium with respect to the negative electrode PAS in the battery.

Battery voltage at a constant current of 0.25 mA / cm ² in the battery is charged to a 4.3 V, followed by the battery voltage at a constant current of 0.25 mA / cm ² is
Discharged to 2.5V. This cycle of 4.3V-2.5V is repeated, and in the third discharge, the volume capacity (mAh / cc)
Was evaluated. As a volume standard, the total of the electrode volume, the separator volume, and the current collector volume was used. The results are shown in Table 1 below.
Shown in

Example 2 A positive electrode having a thickness of 100 μm and 200 μm was obtained in the same manner as in Example 1. Positive electrode 2 and positive electrode 3, respectively.

A battery was assembled in the same manner as in Example 1 in combination with the negative electrode 2, and the volume capacity was evaluated. The results are shown in Table 2 below.

Comparative Example 1 A positive electrode 4 having a thickness of 260 μm was obtained in the same manner as in Example 1. As the negative electrode, a negative electrode 4 not previously supporting lithium was used. Positive electrodes 1, 3, 4 and negative electrode 4 were combined to form a battery in the same manner as in Example 1, and the volume capacity was evaluated. Table 3 shows the results.

When the amount of lithium derived from the negative electrode was 0, sufficient capacity was not obtained no matter how much the total amount of lithium was increased.

Comparative Example 2 In Example 1, the amount of lithium previously supported was 50 mA.
The negative electrode 5 was obtained as h / g. A battery was assembled in the same manner as in Example 1 in combination with the positive electrode 1, and the volume capacity was evaluated. Table 4 shows the results.

Even if the total amount of lithium in the battery was sufficient, a sufficient amount of lithium could not be obtained if the amount of lithium derived from the negative electrode (lithium doped in advance in this example) was small.

(1) An example of the first preferred embodiment of the present invention will be described below.

Example 3 50 parts by weight of a xylene resin (manufactured by Lignite), 50 parts by weight of novolak (manufactured by Showa Polymer Co., Ltd.), xylene sulfonic acid
0.1 parts by weight was heated at 100 ° C. to obtain a xylene-modified novolak resin. 10 parts by weight of hexamethylenetetramine was mixed with 100 parts by weight of the resin, and the mixture was pulverized and formed into a molded plate by hot pressing.

The xylene-modified novolak resin molded plate is placed in a silicon electric furnace, heated at a rate of 10 ° C./hour under a nitrogen atmosphere, heat-treated to 650 ° C., and insoluble and infusible substrate (referred to as PAS).
Was synthesized. The PAS plate thus obtained was pulverized with a disk mill to obtain a PAS powder having an average particle size of 15 μm. H
The / C ratio was 0.22. The amount of gas adsorbed on the PAS powder at a nitrogen adsorption thickness of 10 mm was 29 cc / g.

Next, 100 parts by weight of the PAS powder and 100 parts by weight of a solution of 10 parts by weight of polyvinylidene fluoride powder dissolved in 90 parts by weight of N, N-dimethylformamide were sufficiently mixed to obtain a slurry. Thick the slurry using an applicator
It was applied on a 10 μm copper foil (negative electrode current collector), dried and pressed to obtain a 110 μm thick PAS negative electrode.

100 parts of commercially available LiCoO ₂ (manufactured by Strem), 5 parts of graphite, 10 parts by weight of polyvinylidene fluoride powder, N, N
-A slurry was obtained by sufficiently mixing 50 parts by weight of a solution dissolved in 90 parts by weight of dimethylformamide. The slurry was applied on an aluminum foil (positive electrode current collector) having a thickness of 20 μm using an applicator, dried and pressed to obtain a positive electrode 5 having a thickness of 165 μm.

The above negative electrode has lithium as a counter electrode, and the electrolyte contains propylene carbonate and diethyl carbonate in a ratio of 1: 1 (weight ratio).
Using a solution in which LiPF ₆ was dissolved to a concentration of 1 mol / mol as the mixed solution, and applying a constant current (an electric current such that 30 mAh / g of lithium is supported on the negative electrode PAS per hour) was set to 150 mAh / negative electrode PAS. g, 200 mAh / g, and 300 mAh / g of lithium were loaded and supported (lithium derived from the negative electrode). The negative electrodes were 6, 7, and 8, respectively. Using the positive electrode and the negative electrodes 6, 7, and 8 (all 1 × 1 cm ² ), three types of batteries as shown in FIG. 1 were assembled. As the separator, a polypropylene separator having a thickness of 25 μm was used. As the electrolyte, propylene carbonate and diethyl carbonate were mixed at a ratio of 1: 1.
(Weight ratio) A solution in which LiPF ₆ was dissolved at a concentration of 1 mol / was used for the mixed solution. Table 5 shows the total amount of lithium with respect to the negative electrode PAS in the battery.

Battery voltage at a constant current of 0.25 mA / cm ² in the battery is charged to a 4.3 V, followed by the battery voltage at a constant current of 0.25 mA / cm ² is
Discharged to 2.5V. This cycle of 4.3V-2.5V is repeated, and in the third discharge, the volume capacity (mAh / cc)
Was evaluated. As a volume standard, the total of the electrode volume, the separator volume, and the current collector volume was used. Table 5 shows the results.

Example 4 A negative electrode was prepared by changing the composition of the PAS raw material in Example 3 to 30 parts by weight of xylene resin, 70 parts by weight of novolak, 10 parts by weight of xylene resin, and 90 parts by weight of novolak.
These negative electrodes PAS were doped with and supported by 300 mAh / g of lithium to form negative electrodes 9 and 10, respectively.

A battery was assembled in the same manner as in Example 3, and the volume capacity was evaluated. Table 6 shows the results.

Comparative Example 3 A negative electrode was prepared by changing the composition of the PAS raw material in Example 3 to 30 parts by weight of xylene resin and 70 parts by weight of novolak. One of these negative electrodes was not loaded with lithium in advance, and the other was doped with and loaded with 50 mAh / g of lithium per negative electrode PAS to form negative electrodes 11 and 12, respectively.

A battery was assembled in the same manner as in Example 3, and the volume capacity was evaluated. Table 7 shows the results.

Comparative Example 4 In Example 3, the composition of the PAS raw material was 100 parts by weight of novolak and 10 parts by weight of hexamethylenetetramine.
And a powder resol ("Regitop" manufactured by Gunei Chemical Industry Co., Ltd.) as a raw material to prepare a negative electrode.
These negative electrodes PAS were doped with 300 mAh / g of lithium and supported to obtain negative electrodes 13 and 14, respectively.

A battery was assembled in the same manner as in Example 3, and the volume capacity was evaluated. Table 8 shows the results.

(2) An example of the second preferred embodiment of the present invention will be described below.

Example 5 A phenolic resin molded plate having a thickness of 0.5 mm was placed in a siliconite electric furnace, heated at a rate of 10 ° C./hour under a nitrogen atmosphere, heat-treated to 650 ° C., and insoluble and infusible substrate (referred to as PAS).
Was synthesized. The H / C ratio was 0.22. P thus obtained
By changing the grinding time of the AS plate with an alumina pot mill, PAS powder having the particle size distribution shown in Table 9 (No. 1, No.
2, No.3, No.4). The particle size distribution was measured using a laser diffraction particle size distribution analyzer after dispersing the obtained powder in water using ultrasonic waves.

Next, 100 parts by weight of the above PAS powder and 100 parts by weight of a solution of 10 parts by weight of polyvinylidene fluoride powder dissolved in 90 parts by weight of N, N-dimethylformamide were sufficiently mixed to obtain a slurry. Thick the slurry using an applicator
It was applied on a 10 μm copper foil (negative electrode current collector), dried and pressed to obtain a 110 μm thick PAS negative electrode. The porosity of the negative electrode is 25
It was determined by impregnating propylene carbonate at ℃. The density of propylene carbonate used was 1.
It was 20 g / cc (measured with a pycnometer). The results are summarized in Table 9. 100 parts of commercially available LiCoO ₂ (manufactured by Strem)
5 parts of graphite, 10 parts of polyvinylidene fluoride powder
A slurry was obtained by sufficiently mixing 50 parts by weight of a solution dissolved in 90 parts by weight of N, N-dimethylformamide by weight. The slurry was applied on a 20 μm-thick aluminum foil (positive electrode current collector) using an applicator, dried, and pressed to a thickness of 16 μm.
Positive electrodes 6 and 7 of 0 μm and 180 μm were obtained.

The above negative electrode has lithium as a counter electrode, and the electrolyte contains propylene carbonate and diethyl carbonate in a ratio of 1: 1 (weight ratio).
A solution in which LiPF ₆ was dissolved at a concentration of 1 mol / mol was used as the mixed solution, and a constant current (an electric current was set such that 30 mAh / g of lithium was supported on the negative electrode PAS per hour) was set to 3 per negative electrode PAS.
00 mAh / g of lithium was doped and carried (lithium derived from the negative electrode).

The above positive electrodes 6 and 7 are used as a negative electrode PAS when the total amount of lithium in the battery is negative.
Negative electrode 15, 16, 17, 18 so as to be about 1100 mAh / g
(In each case 1 × 1 cm ² ), five types of batteries as shown in FIG. 1 were assembled. 25μ thick as separator
m of polypropylene separator was used. As an electrolyte, a 1: 1 (weight ratio) mixture of propylene carbonate and diethyl carbonate was added to a concentration of 1 mol / LiPF ₆
Was used. Table 10 shows the total amount of lithium with respect to the negative electrode PAS in the battery.

Battery voltage at a constant current of 0.25 mA / cm ² in the battery is charged to a 4.3 V, followed by the battery voltage at a constant current of 0.25 mA / cm ² is
Discharged to 2.5V. This cycle of 4.3V-2.5V is repeated, and in the third discharge, the volume capacity (mAh / cc)
Was evaluated. As a volume standard, the total of the electrode volume, the separator volume, and the current collector volume was used. Table also shows the results
See Figure 10.

Example 6 In the same manner as in Example 5, the thickness was 240 μm, 210 μm, and 200 μm.
The positive electrodes 8, 9, and 10 of μm were obtained. In the same manner as in Example 5, the amount of lithium derived from the negative electrode of negative electrode 17 was set to 0 mAh / g (comparative).
A battery was assembled at 150 mAh / g and 200 mAh / g (the present invention) in the same manner as in Example 5 in combination with the above positive electrode, and the volume capacity was evaluated. Table 11 shows the results.

When the amount of lithium derived from the negative electrode was 0, sufficient capacity could not be obtained.

Comparative Example 5 A phenolic resin-formed plate having a thickness of 0.5 mm was placed in a siliconite electric furnace, heated at a rate of 10 ° C./hour under a nitrogen atmosphere, and heat-treated to 650 ° C. to synthesize PAS. H / C ratio is 0.22
Met. Using a jet mill, the PAS plate thus obtained was subjected to PAS powder having the particle size distribution shown in Table 12 (No. 5, No. 5).
6, No. 7). In the same manner as in Example 5, the negative electrode (No. 19,
No. 20 and No. 21) were obtained, and the porosity was determined. Table 12 shows the results.

A positive electrode having a thickness of 150 μm and 130 μm in the same manner as in Example 5.
11 and 12 were obtained. Hereinafter, 300 mAh / g of lithium derived from the negative electrode was supported on the negative electrodes of Nos. 19 to 21 in the same manner as in Example 5, and the same evaluation as in Example 5 was performed. Table 13 shows the results.

Comparative Example 6 Using PAS No. 2 of Example 5, thoroughly mix 100 parts by weight of PAS powder and 110 parts by weight of a solution obtained by dissolving 10 parts by weight of polyvinylidene fluoride powder in 90 parts by weight of N, N-dimethylformamide. Thus, a slurry was obtained. The slurry was applied on a 10 μm-thick copper foil (negative electrode current collector) using an applicator, and dried to obtain a 110 μm-thick PAS negative electrode. The porosity of the negative electrode was determined by impregnating propylene carbonate at 25 ° C. The porosity was 46%.

A positive electrode having a thickness of 130 μm was obtained in the same manner as in Example 1.
Hereinafter, 300 mAh / g of lithium derived from the negative electrode was supported on the negative electrode in the same manner as in Example 5, and the same evaluation as in Example 5 was performed. The volume capacity was 131 mAh / cc.

(3) An example of the third preferred embodiment of the present invention will be described below.

Example 7 A phenol resin molded plate having a thickness of 0.5 mm was placed in a siliconite electric furnace and heated at a rate of 10 ° C./hour under a nitrogen atmosphere.
Heat treatment was performed to 650 ° C. to synthesize an insoluble and infusible substrate (referred to as PAS). The PAS plate thus obtained was pulverized with a bot mill to obtain an average particle size of about 3 μm. The H / C ratio was 0.22.

Next, 100 parts by weight of the PAS powder and 10 parts by weight of a polyvinylidene fluoride powder having a melting point of 172 ° C. were sufficiently mixed with 100 parts by weight of a solution obtained by dissolving 90 parts by weight of N, N-dimethylformamide to obtain a slurry. Was. The slurry was applied on a 10 μm-thick copper foil (negative electrode current collector) using an applicator, dried and pressed, and PAS was applied on both sides to a thickness of 210 μm.
A PAS negative electrode was obtained. The PAS negative electrode under vacuum, 100 ℃, 160 ℃,
Heat treatment was performed at 190 ° C and 220 ° C to obtain negative electrodes 22, 23, 24, and 25.

100 parts of commercially available LiCoO ₂ (manufactured by Strem), 5 parts of graphite, 10 parts by weight of polyvinylidene fluoride powder, N, N
-A slurry was obtained by sufficiently mixing 50 parts by weight of a solution dissolved in 90 parts by weight of dimethylformamide. The slurry was applied on a 20 μm-thick aluminum foil (positive electrode current collector) using an applicator, dried and pressed, and LiCoO ₂
Was applied to obtain a positive electrode having a thickness of 340 μm.

The above negative electrode has lithium as a counter electrode, and the electrolyte contains propylene carbonate and diethyl carbonate in a ratio of 1: 1 (weight ratio).
Using a solution in which LiPF ₆ is dissolved at a concentration of 1 mol / as the mixed solution, and at a constant current (setting a current such that 30 mAh / g of lithium is supported on the negative electrode PAS per hour), 300 mAh / negative electrode PAS is used. g of lithium was loaded and supported (lithium derived from the negative electrode). The negative electrodes were 22, 23, 24, and 25, respectively.

The above positive electrode 1, negative electrode 22, 23, 24, 25 (all 4 × 35 cm
² ), a cylindrical battery as shown in FIG. 2 was assembled. As the separator, a polypropylene separator having a thickness of 25 μm was used. 150μm thickness, 5mm width for positive terminal
As the aluminum terminal and the negative electrode terminal, nickel having the same size as the positive electrode was used, and they were respectively attached to the ends of the electrodes.
As the electrolytic solution, a solution obtained by dissolving LiPF ₆ at a concentration of 1 mol / in a 1: 1 (weight ratio) mixed solution of propylene carbonate and diethyl carbonate was used. Negative electrode PAS in battery
Was 1170 mAh / g in all cases. Here, when the negative electrode 1 treated at 100 ° C. was used, the electrode was peeled off from the metal foil when the electrode was wound, and the battery did not become a battery.

Charge the above battery with a constant current of 0.25 mA / cm ² until the battery voltage reaches 4.3 V, measure the internal resistance, and then
The battery was discharged at a constant current of / cm ² until the battery voltage reached 2.5 V. This cycle of 4.3V-2.5V was repeated, and the third discharge was evaluated by volume capacity (mAh / cc). As a volume standard, the total of the electrode volume, the separator volume, and the current collector volume was used. Table 14 shows the results.

The negative electrodes 24 and 25, which are preferred embodiments of the present invention,
Lower internal resistance and higher volume capacity than 2,23.

Comparative Example 7 A positive electrode 2 having a thickness of 460 μm was obtained in the same manner as in Example 7. The size of the positive electrode and the negative electrode was 4 × 30 cm ² .

Assuming that the lithium derived from the negative electrode is 0 mAh / g, the negative electrodes 22, 23, 2
A battery was assembled in the same manner as in Example 7 in combination with 4 and 25, and the volume capacity was evaluated. The total amount of lithium relative to the negative electrode PAS in the battery was 1090 mAh / g. Table 1 shows the results
See Figure 5.

(4) A preferred embodiment of the fourth aspect of the present invention will be described below.

Example 8 A phenolic resin molded plate having a thickness of 0.5 mm was placed in a siliconite electric furnace, heated at a rate of 10 ° C./hour under a nitrogen atmosphere, and heat-treated to 650 ° C. to synthesize an insoluble infusible substrate (PAS). did. The PAS plate thus obtained was pulverized with a disk mill to obtain a PAS powder having an average particle size of about 15 μm. The H / C ratio was 0.22.

Next, 100 parts by weight of the PAS powder and 100 parts by weight of a solution of 10 parts by weight of polyvinylidene fluoride powder dissolved in 90 parts by weight of N, N-dimethylformamide were sufficiently mixed to obtain a slurry. The slurry was applied on a 10 μm-thick copper foil (negative electrode current collector) using an applicator, dried and pressed to obtain a 210 μm-thick PAS negative electrode coated on both sides with PAS.

To 100 parts of commercially available LiCoO ₂ (manufactured by Strem) and 5 parts of graphite, 10 parts by weight of polyvinylidene fluoride powder was added to N, N
-A slurry was obtained by sufficiently mixing 50 parts by weight of a solution dissolved in 90 parts by weight of dimethylformamide. The slurry was applied on a 20 μm-thick aluminum foil (positive electrode current collector) using an applicator, dried and pressed, and LiCoO ₂
Was applied to obtain a 280 μm thick positive electrode.

The above negative electrode has lithium as a counter electrode, and the electrolyte contains propylene carbonate and diethyl carbonate in a ratio of 1: 1 (weight ratio).
Using a solution in which LiPF ₆ is dissolved at a concentration of 1 mol / as the mixed solution, and at a constant current (setting a current such that 30 mAh / g of lithium is supported on the negative electrode PAS per hour), 300 mAh / negative electrode PAS is used. g of lithium was loaded and supported (lithium derived from the negative electrode).

A cylindrical battery as shown in FIG. 2 was assembled using the above positive electrode and negative electrode (both 4 × 35 cm ² ). As the separator, a polypropylene separator having a thickness of 25 μm was used. An aluminum terminal having a thickness of 150 μm and a width of 5 mm was used as a positive electrode terminal, and nickel having the same size as the positive electrode was used as a negative electrode terminal. As the electrolytic solution, a solution obtained by dissolving LiPF ₆ at a concentration of 1 mol / in a 1: 1 (weight ratio) mixed solution of propylene carbonate and diethyl carbonate was used. The total amount of lithium with respect to the negative electrode PAS in the battery was 1,040 mAh / g.

Charge the above battery with a constant current of 0.25 mA / cm ² until the battery voltage reaches 4.3 V, measure the internal resistance, and then
The battery was discharged at a constant current of / cm ² until the battery voltage reached 2.5 V. This cycle of 4.3V-2.5V was repeated, and the third discharge was evaluated by volume capacity (mAh / cc). As a volume standard, the total of the electrode volume, the separator volume, and the current collector volume was used. Table 16 shows the results.

Comparative Example 8 A positive electrode having a thickness of 380 μm was obtained in the same manner as in Example 8.
The size of the positive electrode and the negative electrode was 4 × 30 cm ² .

A battery was assembled in the same manner as in Example 8 except that lithium derived from the negative electrode was set to 0 mAh / g, and the volume capacity was evaluated. The total amount of lithium with respect to the negative electrode PAS in the battery was 1010 mAh / g. Table 16 shows the results.

Comparative Example 9 In Example 8, 30 mAh / g of lithium metal (about 12
μm) was attached to the negative electrode PAS, and two cylindrical batteries similar to Example 8 were assembled. After leaving at room temperature for 3 days,
When one was disassembled, lithium metal was completely lost. In the same manner as in Example 8, the volume capacity was evaluated. The total lithium content of this battery was 1040 mAh / g. Table 1 shows the results
See Figure 6.

When the amount of lithium derived from the negative electrode is 0, sufficient capacity cannot be obtained, and when lithium derived from the negative electrode is supported in the battery,
The internal resistance of the battery increased, and the battery capacity decreased.

Example 9 In Example 8, lithium metal (about 200 μm) was
The negative electrode PAS was adhered, sandwiched between polypropylene sheets having a thickness of 2 mm, and lithium derived from the negative electrode was carried in the same electrolytic solution as in Example 1. When the lithium metal was peeled off from the PAS negative electrode in about 40 minutes, 300 mAh / g of lithium could be doped. Thereafter, a cylindrical battery similar to that of Example 8 was assembled, and the volume capacity was evaluated in the same manner as in Example 8. The total lithium content of this battery was 1040 mAh / g. Rating Results 16
Shown in

Example 10 In Example 8, the counter electrode lithium metal (about 200 μm)
And the negative electrode PAS were short-circuited, whereby lithium derived from the negative electrode was carried on the negative electrode PAS. It was possible to dope 300 mAh / g of lithium in about 35 minutes. Thereafter, a cylindrical battery similar to that of Example 8 was assembled, and the volume capacity was evaluated in the same manner as in Example 8. The total lithium content of this battery was 1040 mAh / g.
Table 16 shows the results.

(5) An example of the fifth preferred embodiment of the present invention will be described below.

Example 11 A phenolic resin molded plate having a thickness of 0.5 mm was placed in a siliconite electric furnace, heated at a rate of 10 ° C./hour under a nitrogen atmosphere, heat-treated to 650 ° C., and insoluble and infusible substrate (referred to as PAS).
Was synthesized. The PAS plate thus obtained was pulverized with a disk mill to obtain a PAS powder having an average particle size of about 15 μm. The H / C ratio was 0.22.

Next, 100 parts by weight of the above PAS powder and 100 parts by weight of a solution of 10 parts by weight of polyvinylidene fluoride powder dissolved in 90 parts by weight of N, N-dimethylformamide were sufficiently mixed to obtain a slurry. Thick the slurry using an applicator
It was applied on a 10 μm copper foil (negative electrode current collector), dried and pressed to obtain a 210 μm thick PAS negative electrode having both sides coated with PAS.

100 parts of commercially available LiCoO ₂ (manufactured by Strem), 5 parts of graphite, 10 parts by weight of polyvinylidene fluoride powder, N, N
-A slurry was obtained by sufficiently mixing 50 parts by weight of a solution dissolved in 90 parts by weight of dimethylformamide. The slurry was applied on a 20-μm-thick aluminum foil (positive electrode current collector) using an applicator, dried and pressed to obtain a 280-μm-thick positive electrode coated with LiCoO ₂ on both sides.

The above negative electrode has lithium as a counter electrode, and the electrolyte contains propylene carbonate and diethyl carbonate in a ratio of 1: 1 (weight ratio).
An electrolytic cell having a lithium reference electrode was assembled using a solution in which LiPF ₆ was dissolved at a concentration of 1 mol / mol as the mixed solution. PAS negative electrode is + 20mV, 0mV, -20m with respect to lithium reference electrode
V, −50 mV, −100 mV
The time during which 0 mAh / g (lithium derived from the negative electrode) can be supported was measured. Table 17 shows the results.

Using the positive electrode 1 and the negative electrode (both 1 × 1 cm ² ), a battery as shown in FIG. 1 was assembled. As a separator, the thickness
A 25 μm polypropylene separator was used. The total amount of lithium with respect to the negative electrode PAS in the battery was 1,040 mAh / g.

Battery voltage at a constant current of 0.25 mA / cm ² in the battery is charged to a 4.3 V, followed by the battery voltage at a constant current of 0.25 mA / cm ² is
Discharged to 2.5V. This cycle of 4.3-2.5V is repeated, and in the third discharge, the volume capacity (mAh / cc)
Was evaluated. As a volume standard, the total of the electrode volume, the separator volume, and the current collector volume was used. Table 17 shows the results.

Comparative Example 10 In Example 11, lithium metal (about 200 μm) was
The negative electrode PAS was adhered, sandwiched between polypropylene plates having a thickness of 2 mm, and lithium derived from the negative electrode was carried in the same electrolytic solution as in Example 1. When the lithium metal was peeled off from the PAS negative electrode in about 40 minutes, 300 mAh / g of lithium could be doped. It takes more time than when a negative voltage is applied.

Comparative Example 11 In Example 11, the counter electrode lithium metal (about 200 μm)
And the negative electrode PAS were short-circuited, whereby lithium derived from the negative electrode was carried on the negative electrode PAS. It was possible to dope 300 mAh / g of lithium in about 35 minutes. It takes more time than when a negative voltage is applied.

Comparative Example 12 A phenol resin composition plate having a thickness of 0.5 mm was placed in a siliconite electric furnace, heated at a rate of 10 ° C./hour under a nitrogen atmosphere, and heat-treated to 1000 ° C. to obtain a carbonaceous material. The PAS plate thus obtained was pulverized with a disk mill to obtain a carbonaceous material powder having an average particle size of about 13 μm. H / C ratio is 0.02
Met.

The carbonaceous material was used as an electrode in the same manner as in Example 11, and lithium derived from the negative electrode was loaded with lithium in the same manner as in Example 11. In the case of +20 mV, the loading time is 50
Min, 0 mV, the time required for loading is 45 minutes and -20 m
When V, -50 mV, and -100 mV were applied, lithium metal was deposited on the negative electrode carbon material. When left as it was, the lithium metal had disappeared after about 30 hours, but this was not practical as a method for supporting lithium derived from the negative electrode.

In addition, a battery similar to that of Example 11 was assembled using the negative electrode prepared at +20 mV and evaluated. After three cycles, a large amount of lithium metal was deposited on the negative electrode.

(6) An example of the sixth preferred embodiment of the present invention will be described below.

Example 12 A phenolic resin molded plate having a thickness of 0.5 mm was placed in a siliconite electric furnace, heated at a rate of 10 ° C./hour under a nitrogen atmosphere, heat-treated to 650 ° C., and insoluble and infusible substrate (referred to as PAS).
Was synthesized. The PAS plate thus obtained was pulverized with a disk mill to obtain a PAS powder having an average particle size of about 15 μm. The H / C ratio was 0.22.

Next, 100 parts by weight of the above PAS powder and 100 parts by weight of a solution of 10 parts by weight of polyvinylidene fluoride powder dissolved in 90 parts by weight of N, N-dimethylformamide were sufficiently mixed to obtain a slurry. Thick the slurry using an applicator
It was applied on a 10 μm copper foil (negative electrode current collector), dried and pressed to obtain a 210 μm thick PAS negative electrode having both sides coated with PAS.

100 parts of commercially available LiCoO ₂ (manufactured by Strem), 5 parts of graphite, 10 parts by weight of polyvinylidene fluoride powder, N, N
-A slurry was obtained by sufficiently mixing 50 parts by weight of a solution dissolved in 90 parts by weight of dimethylformamide. The slurry was applied on a 20-μm-thick aluminum foil (positive electrode current collector) using an applicator, dried and pressed to obtain a 280-μm-thick positive electrode coated with LiCoO ₂ on both sides.

The negative electrode was lithium as a counter electrode, and a solution of LiPF ₆ dissolved in propylene carbonate at a concentration of 1 mol / in propylene carbonate was used as an electrolytic solution at a constant current (30 mAh per hour for the negative electrode PAS).
/ g of lithium is set to a current that supports lithium)
300 mAh / g of lithium was doped per PAS and supported (lithium derived from the negative electrode).

Using the above positive and negative electrodes (both 1 × 1 cm ² ), FIG.
I assembled batteries like. As a separator, thickness 25
A μm polypropylene separator was used. As an electrolyte, a 1: 1 (weight ratio) mixture of propylene carbonate and diethyl carbonate was added to a concentration of 1 mol / L LiP.
The solution was used which was dissolved F _6. The total amount of lithium with respect to the negative electrode PAS in the battery was 1040 mAh / g.

Battery voltage at a constant current of 0.25 mA / cm ² in the battery is charged to a 4.3 V, followed by the battery voltage at a constant current of 0.25 mA / cm ² is
Discharged to 2.5V. This cycle of 4.3V-2.5V is repeated, and in the third discharge, the volume capacity (mAh / cc)
Was 169 mAh / cc. As a volume standard, the total of the electrode volume, the separator volume, and the current collector volume was used.

Comparative Example 13 Lithium derived from the negative electrode was prepared in the same manner as in Example 1 except that a solution obtained by dissolving LiPF ₆ at a concentration of 1 mol / in a 1: 1 (weight ratio) mixture of propylene carbonate and diethyl carbonate was used. When the battery was assembled and the volume capacity was evaluated, it was 155 mAh / cc.

Example 13 The same method as that of Example 12 was used except that a solution obtained by dissolving LiPF ₆ at a concentration of 1 mol / in a 1: 1 (weight ratio) mixture of propylene carbonate and ethylene carbonate using lithium derived from the negative electrode was used. When the battery was assembled and the volume capacity was evaluated, it was 167 mAh / cc.

 Examples 12 and 13 are about 10% higher in capacity than Comparative Example 13.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hironori Hato 1-6-2 tomobuchi-cho, Miyakojima-ku, Osaka-shi, Osaka-305-72 (72) Inventor Shizukuni Yada 2-6-1 Miyanishi, Harima-cho, Kako-gun, Hyogo 13 Examiner Yoshiki Tanemura (56) References JP-A-3-233861 (JP, A) JP-A-4-34870 (JP, A) JP-A-4-206276 (JP, A) (58) Field (Int.Cl. ⁶ , DB name) H01M 10/40

Claims (12)

(57) [Claims] 1. An organic electrolyte battery comprising a positive electrode, a negative electrode and a solution of a lithium salt in an aprotic organic solvent as an electrolytic solution, wherein (1) the positive electrode contains a lithium-containing metal oxide, and (2) The negative electrode is a heat-treated aromatic condensation polymer, and is an insoluble infusible substrate (PAS) having a polyacene skeleton structure in which the atomic ratio of hydrogen atoms / carbon atoms is 0.5 to 0.05; The total amount of lithium contained in the battery is 50 relative to the insoluble infusible substrate having a polyacene-based
0 mAh / g or more, and lithium derived from the negative electrode is 100 mAh / g
The above is an organic electrolyte battery. 2. A fluorine-containing polymer in which a negative electrode is a molded article comprising an insoluble infusible substrate having a polyacene skeleton structure and a binder, wherein the binder has an atomic ratio of fluorine atom / carbon atom of less than 1.5 and 0.75 or more. The organic electrolyte battery according to claim 1, wherein 3. The organic electrolyte battery according to claim 2, wherein the fluorine-containing polymer is polyvinylidene fluoride. 4. An organic electrolyte battery comprising a positive electrode, a negative electrode and a solution of a lithium salt in an aprotic organic solvent as an electrolytic solution, wherein (1) the positive electrode contains a lithium-containing metal oxide, and (2) The negative electrode is a heat-treated aromatic condensed polymer, and is an insoluble infusible substrate (PAS) having a polyacene skeleton structure in which the atomic ratio of hydrogen atoms / carbon atoms is 0.5 to 0.05, and (3) the negative electrode PAS On the other hand, the total amount of lithium contained in the battery is 500 mAh / g or more, and the amount of lithium derived from the negative electrode is 10
An organic electrolyte battery having a polyacene skeleton structure of 0 mAh / g or more.
S) is obtained from the nitrogen adsorption isotherm.
An organic electrolyte battery, wherein the amount of adsorbed gas in (1) is 100 cc / g or less. 5. A positive electrode, a negative electrode and an aprotic organic solvent solution of a lithium salt as an electrolytic solution, (1) the positive electrode contains a lithium-containing metal oxide, and (2) the negative electrode is an aromatic An insoluble infusible substrate (PAS) having a polyacene skeleton structure in which a hydrogen atom / carbon atom atomic ratio is 0.5 to 0.05, which is a heat-treated product of a condensation polymer; The total amount of lithium contained is 500 mAh / g or more, and lithium derived from the negative electrode is 10
An organic electrolyte battery having a polyacene skeleton structure of 0 mAh / g or more.
S) has an average particle diameter of 20 μm or less and a 50% diameter of 2aμ.
When the particle size is 1 m or less, the particles have a volume ratio of 10% or more, and the particles having a particle size of 4 am or more are 10% or more, and the porosity of the negative electrode is 40% or less. An organic electrolyte battery, characterized in that: 6. A positive electrode, a negative electrode, and a solution of a lithium salt in an aprotic organic solvent as an electrolytic solution. (1) The positive electrode contains a lithium-containing metal oxide; A heat-treated condensed polymer, which is an insoluble and infusible substrate (PAS) having a polyacene skeleton structure in which the atomic ratio of hydrogen atoms / carbon atoms is 0.5 to 0.05; The total amount of lithium contained is 500 mAh / g or more, and lithium derived from the negative electrode is 10
An organic electrolyte battery of 0 mAh / g or more, wherein the negative electrode is formed by molding a receiving infusible substrate (PAS) having a polyacene skeleton structure on a metal foil using a thermoplastic binder. An organic electrolyte battery, which is heat-treated at a temperature equal to or higher than the melting point of a thermoplastic binder. 7. A positive electrode, a negative electrode, and a solution of a lithium salt in an aprotic organic solvent as an electrolytic solution, (1) the positive electrode contains a lithium-containing metal oxide, and (2) the negative electrode is an aromatic A heat-treated condensed polymer, which is an insoluble and infusible substrate (PAS) having a polyacene skeleton structure in which the atomic ratio of hydrogen atoms / carbon atoms is 0.5 to 0.05; The total amount of lithium contained is 500 mAh / g or more, and lithium derived from the negative electrode is 10
An organic electrolyte battery having a capacity of 0 mAh / g or more, wherein lithium derived from the negative electrode is previously supported on PAS before battery assembly. 8. A positive electrode, a negative electrode, and an aprotic organic solvent solution of a lithium salt as an electrolytic solution, (1) the positive electrode contains a lithium-containing metal oxide, and (2) the negative electrode is an aromatic A heat-treated condensed polymer, which is an insoluble and infusible substrate (PAS) having a polyacene skeleton structure in which the atomic ratio of hydrogen atoms / carbon atoms is 0.5 to 0.05; The total amount of lithium contained is 500 mAh / g or more, and lithium derived from the negative electrode is 10
An organic electrolyte battery having a capacity of 0 mAh / g or more, wherein the lithium derived from the negative electrode is electrochemically supported by applying a potential equal to or less than the potential of Li metal. battery. 9. A positive electrode, a negative electrode, and an aprotic organic solvent solution of a lithium salt as an electrolytic solution, (1) the positive electrode contains a lithium-containing metal oxide, and (2) the negative electrode is an aromatic A heat-treated condensed polymer, which is an insoluble and infusible substrate (PAS) having a polyacene skeleton structure in which the atomic ratio of hydrogen atoms / carbon atoms is 0.5 to 0.05; The total amount of lithium contained is 500 mAh / g or more, and lithium derived from the negative electrode is 10
An organic electrolyte battery having a capacity of 0 mAh / g or more, wherein lithium derived from a negative electrode is electrochemically supported using a cyclic carbonate solvent solution of a lithium salt. 10. A molded article comprising an insoluble and infusible substrate (PAS) having a polyacene skeleton structure and a binder, wherein the binder has a fluorine atom / carbon atom ratio of 1.5.
The organic electrolyte battery according to any one of claims 2 to 9, which is a fluorine-containing polymer having a value of less than 0.75 or more. 11. A method according to claim 2, wherein the negative electrode is a molded article comprising an insoluble and infusible substrate (PAS) having a polyacene skeleton structure and a binder, and the fluorine-containing polymer serving as the binder is polyvinylidene fluoride. An organic electrolyte battery according to any of the preceding claims. 12. The organic electrolyte battery according to claim 2, wherein the positive electrode is a lithium-containing metal oxide.