JP3475530B2 - Non-aqueous electrolyte secondary battery - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a non-aqueous electrolyte secondary battery.

[0002]

2. Description of the Related Art Recent advances in electronic technology have made electronic devices smaller and lighter one after another. Along with this, there is an increasing demand for batteries as portable power sources that are smaller and lighter and have high energy density.

Conventionally, an aqueous solution type battery such as a lead battery or a nickel-cadmium battery has been mainly used as a secondary battery for general use. However, although these aqueous solution type batteries can satisfy cycle characteristics to some extent, they cannot be said to be satisfactory characteristics in terms of battery weight and energy density.

On the other hand, in recent years, research and development of lithium secondary batteries using lithium or a lithium alloy as a negative electrode have been actively conducted. This battery has a high energy density,
It has low self-discharge and has excellent characteristics such as light weight. However, as the charge / discharge cycle progresses,
There is a drawback that lithium in the negative electrode grows in the form of dendrite and reaches the positive electrode, causing an internal short circuit, which is a major obstacle to practical use.

Therefore, in order to solve such a drawback, a lithium ion secondary battery has been proposed in which a carbon material capable of doping and dedoping lithium is used for a negative electrode. This battery utilizes the doping / dedoping of lithium between carbon layers for the negative electrode reaction, and deposition of lithium metal is not observed even if the charging / discharging cycle proceeds, and good charging / discharging cycle characteristics are exhibited.

By the way, a typical shape of the lithium ion secondary battery is a cylindrical shape or a coin shape.

In a cylindrical battery, a positive electrode in which a positive electrode mixture composed of a positive electrode active material, a conductive agent and a binder is held as a thin layer on a strip-shaped positive electrode current collector, a negative electrode active material and a binder. An electrode winding body is used in which the negative electrode mixture is laminated as a thin layer on a strip-shaped negative electrode current collector with a separator interposed therebetween and is wound many times. A cylindrical lithium ion secondary battery is constructed by accommodating this electrode winding body together with an electrolytic solution in a cylindrical battery can, and caulking and sealing the battery lid.

In the coin type battery, a positive electrode and a negative electrode obtained by compressing and molding the positive electrode mixture and the negative electrode mixture into pellets are used. Each of the positive electrode and the negative electrode is housed in a positive electrode can and a negative electrode can, laminated via a separator, impregnated with an electrolytic solution, and then the positive electrode can and the negative electrode can are caulked and sealed.

Of these, the cylindrical battery has a large contact area with the electrolytic solution because the positive electrode and the negative electrode are thin. Therefore, the battery reaction easily progresses uniformly in the electrode, rapid charging is possible, and the cycle life is long.

On the other hand, in the case of a coin-type battery, when the size of the coin-type battery becomes particularly large, the battery reaction in the positive electrode and the negative electrode may be delayed as the distance from the surface facing the separator increases. Such a difference in battery reaction rate in the electrodes causes an apparent overvoltage state, resulting in deterioration of the active material and deterioration of battery characteristics such as cycle characteristics and heavy load characteristics.

In order to suppress such variations in battery reaction, it has been attempted to use a negative electrode and a positive electrode having a small thickness and stack them in multiple layers via a current collector. However, with such a configuration, the ratio of the current collector portion increases, the electrode filling property becomes small, and there arises a disadvantage that a sufficient battery capacity cannot be obtained.

Therefore, it is possible to use the foamed nickel used for the positive electrode in a nickel-cadmium battery or a nickel-hydrogen battery as a device that can make the battery reaction uniform while suppressing the ratio of the current collector portion small. -2
It is proposed in Japanese Patent No. 0680.

That is, in this publication, the negative electrode is constituted by supporting a carbon material, which is a negative electrode active material, on nickel foam. In the negative electrode in which the carbon material is supported on such a metal foam, the resistance of the battery reaction in the electrode is reduced and the overvoltage in the electrode thickness direction is suppressed by the metal foam. In addition, this metal foam has a smaller occupied volume than the plate-shaped current collector, and a sufficient amount of the active material can be secured.

[0014]

However, since the metal foam is a hard material, it has poor moldability and cannot form the electrode surface sufficiently smooth. Therefore, for example, burrs formed on the surface of the metal foam are likely to penetrate the separator to induce an internal short circuit, which causes a problem in battery reliability.

Therefore, the present invention has been proposed in view of such a conventional situation, and it is used as an electrode structure which is excellent in moldability and can make the battery reaction of the thick electrode uniform. The purpose is to provide a battery.

[0016]

The non-aqueous electrolyte secondary battery of the present invention which achieves the above-mentioned object is a negative electrode comprising an electrode structure which is a foam containing a carbon material powder and a polymer binder, and a lithium. It is characterized in that a compound is used as a positive electrode active material, and a positive electrode containing a binder or a conductive agent and a non-aqueous electrolyte are provided.

The non-aqueous electrolyte secondary battery of the present invention comprises a negative electrode which is an electrode structure in which a foam material layer containing carbon material powder and a polymer binder is held on a current collector, and a lithium compound. The positive electrode active material comprises a positive electrode containing a binder or a conductive agent, and a non-aqueous electrolyte.

Further, the non-aqueous electrolyte secondary battery of the present invention contains a negative electrode composed of an electrode structure which is a foam containing carbon material powder and a polymer binder, a conductive agent, a polymer binder and metal powder. It is characterized in that it is composed of an electrode structure which is a foam, and is provided with a positive electrode using a lithium compound as a positive electrode active material and a non-aqueous electrolyte.

The electrode structure used in the battery of the present invention is a foam containing carbon material powder and a polymer binder. This electrode structure is in the form of a sponge having a large number of fine pores, and an electrode material mixture containing an active material, a binder and, if necessary, a conductive agent is compressed and filled. Give the electrode.

The electrode in which such an electrode structure is compressed and filled with the electrode mixture is in a state in which the active material is present in the three-dimensional matrix having conductivity, and therefore, the resistance of the battery reaction is thereby increased. Decrease. Therefore, even if the thickness is increased, the battery reaction progresses uniformly, the overvoltage rise caused by the nonuniform battery reaction and the deterioration of the active material caused thereby are suppressed, and the charge and discharge cycle is relatively heavy. Good cycle characteristics are exhibited even under conditions.

Moreover, since this electrode structure contains a polymer binder, it is soft and has excellent moldability, and the surface can be easily smoothed by performing a press treatment. Therefore, burrs and the like do not break through the separator, which is advantageous in ensuring the reliability of the battery.

The carbon material powder contained in the electrode structure is not particularly limited. However, when applied to a negative electrode using a carbon material as a negative electrode active material such as a lithium-ion secondary battery, the carbon material in this electrode structure can also be involved in the battery capacity, so that both conductivity and lithium ion It is advantageous to select in consideration of the doping / dedoping ability of

As such a carbon material, a graphite material,
There are graphitizable carbon materials and non-graphitizable carbon materials.

As a graphite material, the true density is 2.1 g / c
It is preferably m ³ or more, and more preferably 2.18 g / cm ³ or more.

The graphite material having the above true density preferably has a (002) plane spacing obtained by X-ray diffractometry of 0.340.
less than 0.3 nm, more preferably 0.335 nm or more, 0.
It is necessary that the thickness is 337 nm or less and the C-axis crystallite thickness of the (002) plane is 14.0 nm or more.

Further, the G value in the Raman spectrum is also important in order to achieve the true density in the above range. The G value is represented by the ratio of the area intensity of the signal originating in the graphite structure to the area intensity of the signal originating in the amorphous structure in the Raman spectrum, and serves as an index of microscopic structural defects. It is preferable that the G value of the carbon material is 2.5 or more. Carbon materials with a G value of less than 2.5 are
It may not have a true density of 2.1 g / cm ³ or more.

As a typical graphite material exhibiting the above-mentioned crystal structure parameters, natural graphite can be mentioned. Also,
Artificial graphite obtained by carbonizing an organic material and further treating it at high temperature also exhibits the above-mentioned crystal structure parameters.

Coal and pitch are typical examples of the organic material which is a starting material for producing the artificial graphite.

As pitch, distillation (vacuum distillation, atmospheric distillation, steam distillation), thermal polycondensation, extraction, chemical polycondensation from coal tar, ethylene bottom oil, tars obtained by high temperature thermal decomposition of crude oil, asphalt, etc. There are those obtained by operations such as condensation, and other pitches produced during carbonization of wood.

Further, as a starting material for forming the pitch, there are polyvinyl chloride resin, polyvinyl acetate, polyvinyl butyrate, 3,5-dimethylphenol resin and the like.

During the carbonization, these coals and pitches exist in a liquid state at a maximum temperature of about 400 ° C., and by maintaining the temperature at that temperature, aromatic rings are condensed and polycyclic to be in a laminated orientation, after which 500 At temperatures above about 0 ° C., a solid carbon precursor, that is, semi-coke is formed. Such a process is called a liquid-phase carbonization process, and is a typical formation process of graphitizable carbon.

In addition, condensed polycyclic hydrocarbon compounds such as naphthalene, phenanthrene, anthracene, triphenylene, pyrene, perylene, pentaphene and pentacene, other derivatives (for example, carboxylic acids, carboxylic acid anhydrides, carboxylic acid imides, etc.) thereof, Or mixture, acenaphthylene, indole, isoindole, quinoline,
Fused heterocyclic compounds such as isoquinoline, quinoxaline, phthalazine, carbazole, acridine, phenazine, and phenanthridine, and derivatives thereof can also be used as a raw material.

In order to produce desired artificial graphite using the above organic materials as starting materials, for example, after carbonizing the above organic materials at 300 to 700 ° C. in a stream of an inert gas such as nitrogen,
In an inert gas stream, the temperature rising rate is 1 to 100 ° C. per minute, the reached temperature is 900 to 1500 ° C., the holding time at the reached temperature is 0 to 30.
Calcination is carried out under conditions of time (the one which has undergone this process is a graphitizable carbon material). And further 2000
Artificial graphite can be obtained by heat treatment at a temperature of not lower than ℃, preferably 2500 ℃. Of course, the carbonization and calcination operations may be omitted in some cases.

On the other hand, as the non-graphitizable carbon material, (0
02) The surface spacing is 0.37 nm or more, and the true density is 1.70 g.
Materials having a physical property parameter of less than / cm ³ and having no exothermic peak at 700 ° C. or higher in differential thermal analysis (DTA) in air are suitable.

Typical examples of the above non-graphitizable carbon material are:
There are furfuryl alcohol or furfural homopolymers, copolymers, or furan resins obtained by copolymerization with other resins, which are calcined and carbonized.

Further, as an organic material as a starting material, a conjugated resin such as phenol resin, acrylic resin, vinyl halide resin, polyimide resin, polyamideimide resin, polyamide resin, polyacetylene, poly (p-phenylene), or cellulose is used. And its derivative, and any organic polymer compound can be used.

Further, a functional group containing oxygen is introduced into petroleum pitch having a specific H / C atomic ratio (so-called oxidative crosslinking).
As with the furan resin, the carbonization process (4
It becomes the final non-graphitizable carbon material in the solid state without melting at 00 ° C or higher).

The petroleum pitch is tars obtained by high temperature pyrolysis of coal tar, ethylene bottom oil, crude oil, etc.,
It is obtained from asphalt and the like by operations such as distillation (vacuum distillation, atmospheric distillation, steam distillation), thermal polycondensation, extraction, chemical polycondensation and the like. At this time, the H / C atomic ratio of the petroleum pitch is important, and the H / C atomic ratio of 0.
It must be 6 to 0.8.

The specific means for introducing a functional group containing oxygen into these petroleum pitches is not limited, but, for example, nitric acid,
Wet method using an aqueous solution of mixed acid, sulfuric acid, hypochlorous acid, etc., or dry method using oxidizing gas (air, oxygen), and further reaction with solid reagents such as sulfur, ammonia nitrate, ammonium persulfate, ferric chloride, etc. Used.

The oxygen content is not particularly limited, but as described in JP-A-3-252053, it is preferably 3% or more, more preferably 5% or more.
This oxygen content affects the crystal structure of the finally produced carbon material, and when the oxygen content is in this range, the (002) plane spacing is 0.37 nm or more, and in DTA in an air stream. It has a physical property parameter that it does not have an exothermic peak of 700 ° C. or higher, and has a large negative electrode capacity.

Further, the compounds containing phosphorus, oxygen and carbon as the main components described in JP-A-3-137010 can be used because they have substantially the same physical parameters as those of the non-graphitizable carbon material.

Furthermore, any other organic material can be used as long as it becomes non-graphitizable carbon through a solid phase carbonization process such as oxygen crosslinking treatment, and the treatment method for oxygen crosslinking is not limited.

In order to obtain a carbon material using the above-mentioned raw material organic material, for example, after carbonizing at 300 to 700 ° C., the temperature rising rate is 1 to 100 ° C. per minute, and the ultimate temperature is 900 to 1300 ° C.
The firing may be performed under the condition that the temperature is maintained for about 0 to 30 hours. Of course, in some cases, the carbonization operation may be omitted.

The carbon material as described above is crushed and classified to be used for the electrode structure, and this crushing may be performed before or after carbonization, calcination, high temperature heat treatment or during the temperature rising process. Absent.

On the other hand, when the electrode structure is applied to a positive electrode using a lithium compound as the positive electrode active material, the carbon material powder is selected with emphasis on the conductivity because the lithium compound generally has low conductivity. It is desirable to do. For example, graphite, carbon black or the like which is usually used as a conductive agent is suitable.

As the polymer binder to be contained in the electrode structure, urethane, polyethylene or the like that can be foam-molded is used, and one of the constituent elements of these resins is used in order to improve the solvent resistance to the non-aqueous solvent. A modified material having a part substituted with a fluorine atom or the like is suitable. Furthermore, a mixed material in which an existing fluorine-based resin material is mixed with these resins to enhance solvent resistance without substitution with fluorine atoms or the like can also be used. In addition, other non-foaming resins may be arbitrarily selected and mixed according to required characteristics.

Further, metal powder may be added to the electrode structure as an auxiliary material to further enhance the conductivity. As the metal powder, one that causes an alloying reaction with an alkali metal such as lithium or one that does not cause an alloying reaction can be appropriately selected. However, it is necessary to select, as the metal powder to be added, one that does not dissolve depending on the electrode potential of the positive electrode.

Examples of the metal powder that causes an alloying reaction with lithium metal or the like include Al, Bi, Cd, Pb, Sn, Si and Z.
n is mentioned. In addition, those which are already alloys or intermetallic compounds, such as LiB and β-LiAl-
Cu, Cd-Sn, Bi-Cd, Pb-Cd, Cd-S
n, Bi-Cd-Pb, Pb-Cd-Sn can also be used. Among them, in the case of an electrode structure applied to a 4V class battery, it is desirable to add Al as a metal powder because dissolution does not occur even with such a high electrode potential.

On the other hand, examples of the metal powder that does not cause an alloying reaction with lithium metal include CuNiTi and various stainless steels.

The electrode structure is manufactured by dispersing the above-mentioned carbon material powder, polymer binder and, if necessary, metal powder in a solvent to form a slurry, and foam-molding into a desired electrode shape. Optimum conditions such as the shape and size of the carbon material powder and metal powder to be mixed, the type of polymer binder, the composition ratio of these materials, etc. should be ensured according to the combination of materials such as conductivity, moldability, mechanical strength, etc. It is appropriately adjusted from the viewpoint. For example, if the content of the polymer binder is too high, it becomes difficult to secure conductivity, but it is desirable to set the content to 8% by weight or more to obtain moldability.

The foaming means may be either a physical method using gas or a chemical reaction method using a foaming agent.

In the physical method, when the above slurry is cast-molded, a foam is formed by rapidly heating and drying while blowing bubbles. As the gas for forming bubbles, carbon dioxide gas, nitrogen gas, ammonia, argon gas, oxygen gas, or the like that does not react with the slurry composition can be appropriately selected.

In the chemical method, bubbles are generated in the slurry by the decomposition of the foaming agent to form a foam. As the foaming agent, inorganic compounds such as baking soda and ammonia carbonate, and organic compounds such as azo compounds, nitroso compounds, sulfonyl hydrazides and azodicarbonamides are suitable. These generate carbon dioxide gas, nitrogen gas, ammonia, etc. by heat decomposition to form a bubble structure.

The porosity of the electrode structure formed by foaming is 80%.
The above is preferable, and 90% or more is further preferable. When the porosity is small, the filling amount of the active material mixture becomes small, and the battery capacity is impaired.

The electrode structure as described above may be held on the current collector to ensure the mechanical strength.

As the current collector, a foil, punching metal, expanded metal, mesh-like material or the like is suitable because it occupies a small volume and does not affect the active material filling rate so much. Further, the preferable material of this current collector differs depending on whether it is used for the positive electrode or the negative electrode, and Al is suitable for the positive electrode and Cu, Ni, Ti is suitable for the negative electrode.

In the electrode structure having the above structure, the negative electrode mixture and the positive electrode mixture are compressed and filled as described above to provide the negative electrode and the positive electrode, respectively. For example, in a lithium ion secondary battery, the following negative electrode mixture and positive electrode mixture are used.

The negative electrode mixture is a mixture of a carbon material capable of doping and dedoping lithium as a negative electrode active material and a binder together with an organic solvent. Examples of the carbon material serving as the negative electrode active material include a graphite material excellent in lithium doping / dedoping ability, a graphitizable carbon material, and a non-graphitizable carbon material, which have been exemplified as the carbon material to be contained in the electrode structure. Appropriate. Further, polyvinylidene fluoride or the like is used as the binder because of its excellent solvent resistance, and dimethylformamide or the like is used as the organic solvent.

The positive electrode mixture is obtained by kneading a lithium compound having a high redox potential as a positive electrode active material and a binder together with an organic solvent. This lithium compound contains Li _x
A lithium-transition metal composite oxide represented by MO ₂ (where M is at least one of Co, Ni, and Mn), that is, LiCoO ₂ , LiNiO ₂ , and LiNi _y Co.
_{1-y O 2, Li 0.5} MnO 2, LiMnO 2 or the like is used as a mixture of one kind alone or in combination. As the binder and the organic solvent, those used in the negative electrode mixture can be used.

[0060]

[Function] The foam containing the raw material powder and the polymer binder has a sponge shape having a large number of fine pores, and the active material, the binder and, if necessary, the conductive agent are mixed. The electrode mixture is compressed and filled to give an electrode.

The electrode obtained by compressing and filling the electrode mixture as the foamed electrode structure with the electrode mixture is in a state where the active material is present in the three-dimensional matrix having conductivity. Resistance decreases. Therefore, even if the thickness is increased, the battery reaction progresses uniformly, the overvoltage rise caused by the nonuniform battery reaction and the deterioration of the active material caused thereby are suppressed, and the charge and discharge cycle is relatively heavy. Good cycle characteristics are exhibited even under conditions.

Moreover, since this electrode structure contains a polymer binder, it is soft and has excellent moldability, and the surface can be easily smoothed by performing a press treatment or the like. Therefore, burrs and the like do not break through the separator, which is advantageous in ensuring the reliability of the battery.

[0063]

EXAMPLES The present invention will be described below with reference to specific examples, but it goes without saying that the present invention is not limited to these examples.

[0064]Example 1 The coin-type battery produced in this example is shown in FIG. This phone
The pond consists of pellet-shaped positive electrode 2 and negative electrode 1, respectively.
It is housed in the positive electrode can 5 and the negative electrode can 4 and is inserted through the separator 3.
It is constructed by stacking and crimping the positive electrode can and the negative electrode can.
It will be. In this embodiment, a carp having such a configuration is used.
In order to fabricate a battery cell, first set the negative electrode as follows.
Was prepared.

A graphite material powder (trade name: KS-75, manufactured by Lonza Co., Ltd.), which serves as the negative electrode active material, was added to one of the powders as a binder.
A negative electrode mix was prepared by adding polyvinylidene fluoride in an amount of 0% by weight and an appropriate amount of dimethylformamide, and mixing them.

Then, the negative electrode mix was filled under pressure with the negative electrode mix, heated and dried, and then pressed to obtain a strip-shaped molded body. The negative electrode structure is formed by mixing natural graphite powder and polyethylene and foaming the mixture, and has a thickness of 1 mm and a porosity of 95%. Then, the obtained strip-shaped molded body was formed into a diameter of 15.5 mm and a thickness of 0.4
The negative electrode 1 was produced by punching out into a 5 mm pellet. The graphite weight of the negative electrode 1 was 91 mg.

Next, the positive electrode 2 was manufactured as follows.

0.5 mol of lithium carbonate and 1 cobalt carbonate
By mixing the moles and firing in air at a temperature of 900 ° C. for 5 hours, LiCoO ₂ as a positive electrode active material was obtained. This L
3% by weight of polyvinylidene fluoride, 6% by weight of a graphite material (Lonza Co., trade name KS-15) and dimethylformamide as conductive materials were added to iCoO ₂ powder, and mixed to mix the positive electrode. Was prepared.

This positive electrode mix was pressure-filled into a positive electrode structure, heated and dried, and then pressed to obtain a strip-shaped molded body. The positive electrode structure is formed by foaming carbon black and polyethylene and has a thickness of 1
mm, porosity 97%. Then, the obtained strip-shaped molded body was punched into a pellet shape having a diameter of 15.3 mm and a thickness of 0.5 mm to prepare the positive electrode 2. The LiCoO ₂ weight of this positive electrode 2 is 219 mg.

The negative electrode 1 produced as described above,
The positive electrode 2 was housed in each of the negative electrode can 4 and the positive electrode can 5 and was laminated via a polypropylene membrane having a thickness of 25 μm to be the separator 3. Then, 1 mL of LiPF ₆ was added to an equal volume mixed solvent of ethylene carbonate and diethyl carbonate.
A coin-shaped battery having a diameter of 20 mm and a height of 16 mm as shown in FIG. 1 was produced by impregnating an electrolytic solution dissolved at a concentration of ol / l and caulking and sealing the negative electrode can 4 and the positive electrode can 5.

Example 2 The positive electrode mix was dried as it was without using the positive electrode structure, and then the diameter was 15.3 mm and the thickness was 0.5.
It was produced by pressure molding into a pellet of mm. A coin-type battery was produced in the same manner as in Example 1 except that this positive electrode was used. The LiC of this positive electrode
The oO ₂ weight is 219 mg.

Example 3 The negative electrode mix was dried as it was without using the negative electrode structure, and then the diameter was 15.5 mm and the thickness was 0.4.
It was produced by pressure molding into a pellet of 5 mm. A coin-type battery was produced in the same manner as in Example 1 except that this negative electrode was used. The graphite weight of this negative electrode was 91 mg.

Example 4 As a negative electrode structure, a 10 μm thick Cu metal foil was used, in which a material layer formed by mixing and foaming natural graphite fine powder and polyethylene was held, and a positive electrode was used. As the structure, an Al metal foil having a thickness of 20 μm was used in which a material layer formed by mixing carbon black and polyethylene and foam-molding was held. Then, a coin-type battery was produced in the same manner as in Example 1 except that the negative electrode mix and the positive electrode mix were charged under pressure into the respective material layers of the negative electrode electrode structure and the positive electrode electrode structure. The material layer of the negative electrode structure has a thickness of 1 mm and a porosity of 90%.
The material layer of the positive electrode electrode structure has a thickness of 1 mm and a porosity of 92%.

Example 5 As an electrode structure for a positive electrode, 70% by weight of carbon black, 30% by weight of Al powder as an auxiliary material, and polyethylene were mixed,
A coin-type battery was produced in the same manner as in Example 1 except that the one formed by foam molding was used. The positive electrode structure has a thickness of 1 mm and a porosity of 97%.

Comparative Example 1 The positive electrode mix was dried as it was without using the positive electrode structure, and then the diameter was 15.3 mm and the thickness was 0.5.
mm pellets were produced by pressure molding, and the negative electrode mix was dried as it was without using the negative electrode structure, and then the diameter was 15.5 mm and the thickness was 0.45.
A coin-type battery was manufactured in the same manner as in Example 1 except that the coin-shaped battery was manufactured by press-molding into pellets of mm. The LiCoO ₂ weight of the positive electrode is 219 mg, and the graphite weight of the negative electrode is 91 mg.

Comparative Example 2 The positive electrode mix was dried as it was without using the positive electrode structure, and then the diameter was 15.3 mm and the thickness was 0.5.
A coin-type battery was produced in the same manner as in Example 1 except that it was produced by pressure molding into a pellet having a size of mm, and nickel foam was used as the structure for the negative electrode.

The weight of LiCoO _{2 of} the positive electrode is 21.
It is 9 mg. Further, the nickel foam is manufactured by Sumitomo Electric, and has a thickness of 1.2 mm and a porosity of 98%.

The batteries prepared in Examples 1 to 5 and Comparative Example 1 as described above were subjected to a charge / discharge test, and the initial charge capacity, discharge capacity and Coulombic efficiency were measured. In addition, in the charge / discharge test, charging was performed at a constant current of 1 m
A / cm ² and maximum voltage of 4.2V for 3 hours,
Discharge is constant current 1mA / cm ² , cut-off voltage 2.5V
It went under the condition. Table 1 shows the initial charge capacity, discharge capacity and Coulomb efficiency, and FIG. 2 shows the relationship between the number of cycles and Coulomb efficiency.

[0079]

[Table 1]

As shown in Table 1, the batteries of Examples 1 to 5 using the electrode structure for the negative electrode and / or the positive electrode have a higher charge capacity than the batteries of Comparative Example 1 not using the electrode structure. The discharge capacity and coulombic efficiency are both high values.

Further, referring to FIG. 2, the battery of Comparative Example 1
The Coulombic efficiency greatly decreases with the progress of the number of cycles, whereas the batteries of Examples 1 to 5 almost maintain the initial Coulombic efficiency even after repeating the charge / discharge cycle 100 times.

From this, it was found that using the electrode structure formed by foaming the carbon material powder and the polymer binder for the negative electrode and / or the positive electrode is very effective in improving the battery performance. .

Next, for the batteries of Example 2 and Comparative Example 2,
Each of 100 pieces was charged for the first time and then left for one month. Then, after standing, the open circuit voltage of each battery was measured and the defect rate was investigated. In addition, here, when the open circuit voltage after being left is lower than the initial value by 1 V or more, it was determined to be defective. Table 2 shows the number of defective batteries and the defective rate.

[0084]

[Table 2]

As shown in Table 2, the battery of Comparative Example 2 using the nickel foam as the electrode structure was the same as that of Example 2 in which the carbon material powder and the polymer binder were mixed and foam-molded. The defect rate is higher than that of batteries.

In the battery of Comparative Example 2, the defect rate became such a large value that the nickel foam was harder and had more burrs than the foam made of the carbon material powder and the polymer binder. This is because the burr penetrates the separator and causes an internal short circuit because it exists.

From this, it was found that a hard material such as nickel foam is not preferable as the electrode structure, and a foam made of a carbon material powder having a high flexibility and a polymer binder is suitable. .

[0088]

As is apparent from the above description, the electrode structure used in the present invention is a foam containing a carbon material powder and a polymer binder. Even if the electrode obtained by filling is thick, the cell reaction proceeds uniformly due to the conductivity of the foam. Therefore, in the battery using such an electrode structure, the increase in overvoltage caused by the nonuniform battery reaction and the deterioration of the active material caused thereby are suppressed, and the battery is good even under a relatively heavy load / discharge cycle condition. Excellent cycle characteristics can be obtained.

Moreover, this electrode structure is soft and has excellent moldability, and can be formed into a desired electrode shape with good surface properties. Therefore, burrs and the like do not break through the separator, which is advantageous in ensuring the reliability of the battery.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing a coin-type battery to which an electrode structure is applied.

FIG. 2 is a characteristic diagram showing the relationship between the number of cycles and Coulombic efficiency.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI H01M 10/40 H01M 10/40 Z (58) Fields investigated (Int.Cl. ⁷ , DB name) H01M 4/00-4 / 04 H01M 4/36-4/62 H01M 4/66 H01M 4/80 H01M 10/40

Claims (11)

(57) [Claims] 1. A negative electrode comprising an electrode structure which is a foam containing a carbon material powder and a polymer binder, and lithium.
Compound as positive electrode active material, containing binder or conductive agent
Non-aqueous electrolyte characterized by comprising a positive electrode and a non-aqueous electrolyte
Degradable secondary battery. 2. A foam containing a conductive agent and a polymer binder.
Features a positive electrode consisting of a foamed electrode structure
The non-aqueous electrolyte secondary battery according to claim 1 . 3. The binder is polyvinylidene fluoride.
The non-aqueous electrolyte secondary battery according to claim 1, wherein
pond. 4. The non-aqueous electrolyte secondary according to claim 1, wherein the content of the polymer binder is 8% by weight or more.
battery. 5. The non-aqueous electrolyte secondary battery according to claim 1, wherein the carbon material powder is graphite . 6. The non-aqueous electrolyte secondary battery according to claim 1, wherein the carbon material powder is a graphitizable carbon material . 7. The non-aqueous electrolyte secondary battery according to claim 1, wherein the carbon material powder is a non- graphitizable carbon material . 8. A negative electrode, which is an electrode structure in which a foam material layer containing a carbon material powder and a polymer binder is held on a current collector, and a lithium compound as a positive electrode active material, and a binder or a conductive material. A non-aqueous electrolyte secondary battery comprising a positive electrode containing an agent and a non-aqueous electrolyte. 9. The non-aqueous electrolyte secondary battery according to claim 8 , wherein the current collector is in the form of foil, punched metal, expanded metal or mesh . 10. A carbon material powder and a polymer binder are included.
A negative electrode composed of an electrode structure that is a foam having, and a conductive agent
Is a foam containing a polymer binder and metal powder
It consists of a polar structure and uses a lithium compound as the positive electrode active material.
Non-aqueous electrolyte characterized by comprising a positive electrode and a non-aqueous electrolyte
Degradable secondary battery . 11. The metal powder is Al, Bi, Cd, Pb, S.
n, Si, Zn, LiB, β-LiAl-Cu, Cd-
Sn, Bi-Cd, Pb-Cd, Cd-Sn, Bi-C
11. Any one of d-Pb, Pb-Cd-Sn, Cu, Ni, Ti, and stainless steel.
Non-aqueous electrolyte secondary battery listed.