CA2451181C - Lithium ion secondary battery and a method for manufacturing the same - Google Patents

Lithium ion secondary battery and a method for manufacturing the same Download PDF

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CA2451181C
CA2451181C CA2451181A CA2451181A CA2451181C CA 2451181 C CA2451181 C CA 2451181C CA 2451181 A CA2451181 A CA 2451181A CA 2451181 A CA2451181 A CA 2451181A CA 2451181 C CA2451181 C CA 2451181C
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lithium ion
solid electrolyte
thin film
negative electrode
ion conductive
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CA2451181A1 (en
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Yasushi Inda
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Ohara Inc
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Ohara Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0436—Small-sized flat cells or batteries for portable equipment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making
    • Y10T29/49115—Electric battery cell making including coating or impregnating

Abstract

A lithium ion secondary battery includes a positive electrode, a negative electrode and a thin film solid electrolyte including lithium ion conductive inorganic substance. The thin film solid electrolyte has thickness of 20 µm or below and is formed directly on an electrode material or materials for the positive electrode and/or the negative electrode. The thin film solid electrolyte has lithium ion conductivity of 10-5Scm-1 or over and contains lithium ion conductive inorganic substance powder in an amount of 40 weight % or over in a polymer medium. The average particle diameter of the inorganic substance powder is 0.5 µm or below. According to a method for manufacturing the lithium ion secondary battery, the thin film solid electrolyte is formed by coating the lithium ion conductive inorganic substance directly on the electrode material or materials for the positive electrode and/or the negative electrode.

Description

Title of the Invention Lithium ion secondary battery and a method for manufacturing the same Background of the Invention This invention relates to a lithium ion secondary battery employing a thin film solid electrolyte and a method for manufacturing the same.

In the past, a non-aqueous electrolytic solution was generally used as an electrolytic solution for a lithium ion secondary battery. A lithium ion secondary battery employing a polymer electrolyte made of polymer as disclosed by Japanese Patent Application Laid-open Publication No.
2000-067917 has recently attracted more attention of the industry than such electrolytic solution employing liquid.

The lithium ion secondary battery employing a polymer electrolyte holds a liquid electrolytic solution in the polymer electrolyte and, therefore, has the advantage that there is little possibility of leakage of the liquid, that there is little possibility of corrosion, that short-circuiting between electrodes caused by precipitation of lithium in the form of dendrite can be prevented and that assembly of the battery is easy because the structure of the battery is very simple.

Since lithium ion conductivity of such polymer electrolyte is lower than an electrolyte containing only an electrolytic solution, there has occurred a practice to reduce thickness of the polymer electrolyte. There, however, has arisen a problem in such polymer electrolyte whose thickness is reduced that, since its mechanical strength is reduced, the polymer electrolyte tends to be broken or give rise to a hole during production of the battery resulting in short-circuiting between the positive electrode and the negative electrode.
The gel polymer electrolyte is reported to have thickness in the order of 30 At m to 801um.

For improving the mechanical strength, there is a proposal in Japanese Patent Application Laid-open Publication No. 2001-015164 for a compound electrolyte containing lithium ion conductive glass-ceramic powder. This proposal however has not realized a thin Elm electrolyte having thickness of 20,u m or below.

There are also many proposals, e.g., in Japanese Patent Application Laid-open Publication No. Hei 07-326373, for a solid electrolyte battery which does not employ an electrolytic solution at all. Since a lithium ion secondary battery employing a solid electrolyte does not require an organic electrolytic solution as in the prior art batteries, there is no risk of leakage of solution and combustion and, therefore, a highly safe battery can be provided. In the prior art battery employing an organic electrolytic solution, the positive electrode and the negative electrode contact each other by means of the organic electrolytic solution through the solid electrolyte and, therefore, resistance in moving of ions in the interface does not cause a serious problem.
If, however, all of the positive electrode, negative electrode and electrolyte composing the battery are made of solid, contact in the interface between the positive electrode and the electrolyte and contact in the interface between the negative electrode and the electrolyte become contacts between solids which include point contacts in some parts of the interfaces and thereby produce a large interface resistance as compared with the prior art batteries employing the electrolytic solution. Hence, the solid electrolyte battery has a large impedance in the interfaces which tends to cause polarization and thereby restrict moving of lithium ion in the interfaces with the result that it is difficult to realize a battery having a large capacity and a large output by such solid electrolyte battery.

It is, therefore, an object of the present invention to provide a lithium ion secondary battery which has solved the above problems and has a thin electrolyte and thereby has small resistance notwithstanding that a solid electrolyte is employed and, therefore, has a high battery capacity and a high output and an excellent charging-discharging characteristic and thereby ensures a stabilized use over a long period of time.

Summary of the Invention As a result of detailed studies and experiments, the inventor of the present invention has found, which has led to the present invention, that an inorganic substance having a certain crystal has a high lithium ion conductivity and its lithium ion transport number is 1 and that, by employing this substance as a solid electrolyte in the form of a thin film in a lithium ion secondary battery, a battery of a high performance can be realized.

In a broad aspect, the present invention relates to a lithium ion secondary battery comprising a positive electrode, a negative electrode and a solid electrolyte, said solid electrolyte being made in the form of a thin film comprising a lithium ion conductive inorganic substance, selected from a group consisting of a lithium ion conductive crystal and a lithium ion conductive glass-ceramic, said thin film solid electrolyte having a thickness of 201.1m or below.
In another broad aspect, the present invention relates to a method for manufacturing a lithium ion secondary battery having a thin film solid electrolyte comprising a lithium ion 3a conductive inorganic substance, selected from a group consisting of a lithium ion conductive crystal and a lithium ion conductive glass-ceramic. said thin film solid electrolyte having a thickness of 20 [tm or below, comprising a step of forming the thin film solid electrolyte by coating the lithium ion conductive inorganic substance having an average particle diameter of 0.15 - 1.0 m and comprising one or more selected from the group consisting of a crystal of õALTiõSi,.133,0,2 where 0< x<1, 0y1 and glass-ceramic containing Li, ,,,,,ALTi2_,Si\Põ).012 where 0x I. Oy 1 as a predominant crystal phase directly on an electrode material or materials for a positive or negative electrode.

In another broad aspect, the present invention relates to a method for manufacturing a lithium ion secondary battery having a thin film solid electrolyte comprising a lithium ion conductive inorganic substance, selected from a group consisting of a lithium ion conductive crystal and a lithium ion conductive glass-ceramic, said thin film solid electrolyte having a thickness of 20 m or below comprising a step of forming the thin film solid electrolyte by coating the lithium ion conductive inorganic substance having an average particle diameter of 0.15 - 1.0 la m and comprising one or more selected from the group consisting of a crystal of Li, ,,,,./11,TiõSi,1330,2 where 0x 1. 0 1 and glass-ceramic containing Li, .,,ALTi2_,Si,,P3_,.012 where 0x 1. (ky.1 as a predominant crystal phase directly on an electrode material or materials for a positive and negative electrode. In the thin film solid electrolyte used in the lithium ion secondary battery of the invention, the thinner the thin film solid electrolyte, the shorter is moving distance of lithium ion and, therefore, the higher is the output of the battery. In the lithium ion secondary battery, therefore, the thin film solid electrolyte should preferably have thickness of 20,u m or below and, more preferably, 101um or below and, most preferably, 5,u m or below.

Mobility of lithium ion during charging and discharging in the lithium ion secondary battery of the present invention depends upon lithium ion conductivity and lithium ion transport number of the solid electrolyte.
Accordingly, in the lithium ion secondary battery of the invention, the thin film solid electrolyte should preferably have lithium ion conductivity of 10-5Scmi or over.

Brief Description of the Drawings In the accompanying drawings, FIG. 1 is a schematic sectional view showing an internal structure of the lithium ion secondary battery of the present invention;

FIG. 2 is a graph showing change in the discharging capacity accompanying the charging-discharging cycles of the lithium ion secondary battery s of Example 1 and Comparative Example 1; and FIG. 3 is a graph showing change in the discharging capacity accompanying the charging-discharging cycles of the lithium ion secondary batteries of Example 4 and Comparative Example 4 Description of Preferred Embodiment of the Invention In a preferred embodiment of the invention, the thin film solid electrolyte should preferably comprise the inorganic substance in an amount of 40 weight % or over. The inorganic substance should preferably be an ion conductive crystal, glass or glass-ceramic. The inorganic substance should preferably be powder of the inorganic substance. The inorganic substance powder in the thin film solid electrolyte should preferably have an average partide diameter of 1.0 ,um or below, more preferably 0.5,um or below and, most preferably, 0.3 dam or below.

In the lithium ion secondary battery of the invention, the thin film solid electrolyte may comprise a lithium ion conductive inorganic substance powder in a polymer medium. The thin film solid electrolyte should preferably comprise a lithium inorganic salt and lithium ion conductive glass-ceramic powder.

In the lithium ion secondary battery of the invention, the thin film solid electrolyte may be formed by direct coating on an electrode material or materials for the positive electrode and/or the negative electrode.

The method for manufacturing a lithium ion secondary battery having a thin film solid electrolyte comprising a lithium ion conductive inorganic substance according to the invention comprises a step of forming the thin film solid electrolyte by coating the lithium ion conductive inorganic substance directly on an electrode material or materials for the positive and/or negative electrode.

As described above, the thinner the solid electrolyte, the less is resistance and the shorter is moving distance of ion and, therefore, the higher is the output of the battery. However, in a case where the solid electrolyte is produced independently and separately from the other components of the battery, there is limitation in making the solid electrolyte thin for reasons of strength and handling as well as the manufacturing process. According to the method for manufacturing a lithium ion secondary battery of the invention, the solid electrolyte is formed directly on an electrode material or materials for the positive electrode and/or the negative electrode and, therefore, there is no problem caused by handling an independent solid electrolyte and hence the solid electrolyte can be made even thinner.

The thin film solid electrolyte may be formed by preparing slurry comprising lithium ion conductive crystal, glass or glass-ceramic as the inorganic substance, and coating the slurry directly on the electrode material or materials for the positive and/or negative electrode.

For coating the slurry directly on the electrode material or materials for the positive electrode and/or the negative electrode, dipping, spin coating or tape casting may be employed or printing technique such as ink jetting or screen printing may be employed. As the slurry, lithium ion conductive powder of an inorganic substance may be dispersed with a binder in a medium. Preferable inorganic substances are a crystal, glass and glass-ceramic. The thin film solid electrolyte should preferably comprise an inorganic substance in an amount of 40 weight % or over.

The lithium ion conductive powder used in the present invention should preferably have a high lithium ion conductivity and, more preferably, a chemically stable glass-ceramic. A specific example of the powder of the chemically stable glass-ceramic is powder of glass-ceramic which is produced by heat-treating a Li20-A1203-Ti02-Si02-P205 mother glass for crystallization and contains Lii+x+yALTi2-.SiyP37012 (0 5 x 5 1, 0 5y 5 I) as a predominant crystal phase.

For binding particles of crystal, glass or glass-ceramic powder to one another and also binding these particles to the electrodes which constitute substrates, an organic polymer material may be employed as the binder.
Specifically, a polymer material such as polyethylene oxide, polyethylene, polypropyrene, polyolefin, fluorine resin such as polytetrafluoroethylene, polychlorotrifluoroethylene and polyvinylydene fluoride, polyamides, polyesters and polyacrylates, or a polymer material comprising such polymer as a constituent element may be used. A binder having lithium ion conductivity or a polymer imparted with lithium ion conductivity by adding lithium salt or the like material is more preferably because such binder improves ion conductivity of the compound electrolyte. As the medium, an organic medium in which the above described polymer material is dissolved or dispersed may be used.

In the lithium ion secondary battery of the invention, the thin film solid electrolyte may also be formed by coating a lithium ion conductive inorganic substance directly on an electrode material. For the direct coating known methods for making a thin film such as sputtering, laser abrasion and plasma spraying may be used. In this case, a lithium ion conductive crystal or glass or a compound material induding such lithium ion conductive crystal or glass may be used as a target for forming a thin film directly on an electrode material.

As a target material, the above described chemically stable and highly lithium ion conductive glass-ceramic may preferably be employed. In making a thin film, this glass-ceramic sometimes becomes amorphous but, in this case, there will be no problem if the above described predominant crystal phase is caused to precipitate by crystallizing the amorphous glass by heat-treating. Similarly, the mother glass from which this glass-ceramic is obtained may be employed as the target. In this case also, the above described predominant crystal phase can be produced by the crystallizing process after the film has been formed. A target made of a compound material can be obtained by mixing an inorganic binder to powder of a lithium ion conductive crystal, glass or glass-ceramic and sintering the mixture. The glass-ceramic powder should preferably have lithium ion conductivity and, more preferably, should contain Liii-x+yAlxTi2..SiyP31,012 as a predominant crystal phase. This glass-ceramic powder should preferably have an average particle diameter of 5,um or below and, more preferably, 3,a m or below. The inorganic binder used should preferably be a crystal or glass which is an inorganic oxide having a low melting point. The amount of this inorganic binder should preferably be 20 weight % or below.

In the lithium ion secondary battery using the thin film solid electrolyte of the invention, the positive electrode may be made by forming a material containing a transition metal oxide as a positive electrode active material on an aluminum foil used as a positive electrode collector. As the positive electrode active material, a transition metal compound capable of absorbing and storing and discharging lithium may be used. For example, an oxide or oxides containing at least one transition metal selected from manganese, cobalt, iron, nickel, vanadium, niobium, molybdenum, titanium etc. may be used. In a case where a material which does not contain lithium is used as a negative electrode active material, a transition metal oxide containing lithium may preferably be used.
In the lithium ion secondary battery using the thin film solid electrolyte of the invention, the lithium ion conductive inorganic substance may preferably be used not only for the thin film solid electrolyte but also in the positive electrode as an ion conductive additive. As the lithium ion conductive inorganic substance used for the positive electrode, glass-ceramic powder containing Lii+.1-yAlai2..SiyP3.y012 as a predominant crystal phase as is used in the thin film solid electrolyte may preferably be used. This glass-ceramic powder should preferably have an average particle diameter of 5,um or below and, more preferably, 3,um or below.

In the lithium ion secondary battery using the thin film solid electrolyte of the invention, an electric conductive additive and/or a binder may preferably be used in the positive electrode. As the electric conductive additive, acetylene black may preferably be used and, as the binder, polyvinylidene fluoride PVdF may be preferably be used.

In the lithium ion secondary battery of the invention, the negative electrode may be made by forming a material containing a negative electrode active material on a copper foil used as a negative electrode collector. As the negative electrode active material, a metal or alloy capable of absorbing and storing and discharging lithium such as metal lithium, lithium-aluminum alloy and lithium-indium alloy, transition metal oxides such as titanium and vanadium, and carbon materials such as graphite, active carbon and mesophase pitch carbon fiber may be used.

In the lithium ion secondary battery of the invention, the lithium ion conductive inorganic substance may preferably be used not only for the thin film solid electrolyte but also in the negative electrode as an ion conductive additive. As the lithium ion conductive inorganic substance used for the negative electrode, glass-ceramic powder containing Lii+.+5TALTi2-.SiyP3-y012 as a predominant crystal phase as is used in the thin film solid electrolyte may preferably be used. The negative electrode may be produced by mixing a negative electrode active material with an ion conductive additive and a binder in acetone solvent and coating the mixture on the negative electrode collector. As the negative electrode active material, commercially available graphite powder may be used.

In the following description, the thin film solid electrolyte and the lithium ion secondary battery using it will be described with reference to specific examples and advantages of the lithium ion secondary battery having the thin film solid electrolyte of the invention will be described with reference to comparative examples. It should be noted that the present invention is not limited by the following examples but various modifications can be made within the scope and spirit of the invention.

Examples Example 1 Preparation of the positive electrode As the positive electrode active material, commercially available lithium cobalt oxide (LiCo02) was used. This positive electrode active material, acetylene black used as an electric conductive additive, glass-ceramic powder containing Lii-fx+yAL,Ti2-.SiyP3,012 as a predominant crystal phase used as an ion conductive additive and polyvinylidene fluoride PVdF used as a binder were mixed together in acetone solvent and this mixture was coated on a positive electrode collector made of an aluminum sheet having thickness of 10 gm to thickness of about 501um and was dried under temperature of 100 C
to prepare a positive electrode in the form of a sheet. As the glass-ceramic powder, glass-ceramic powder having an average particle diameter of 1.0,um (average in volume) and a maximum particle diameter of 8 Atm was used.
The particle diameter was measured using a laser diffraction/dispersion particle distribution measuring device.

Preparation of the negative electrode As the negative electrode active material, commercially available graphite powder was used. This negative electrode active material, glass-ceramic powder used as an ion-conductive additive which was the same material used for the positive electrode, i.e., containing Lii+x+yAlxTi2..SiyP3.y01.2 as a predominant crystal phase and having an average particle diameter of 1.0,u.m and a maximum particle diameter of 8,u m, and polyvinylidene fluoride PVdF used as a binder were mixed together in acetone solvent and this mixture was coated on a negative electrode collector made of a copper sheet having thickness of 10 gm up to thickness of about 50 g m and was used under temperature of 100 C to prepare a negative electrode in the form or a sheet.

Preparation of the thin film solid electrolyte and production of the battery Glass-ceramic powder containing Lii+x+,ALTi2-.SiyP3-y012 as a predominant crystal phase and having an average particle diameter of 0.15g m and a maximum particle diameter of 0.3,um and polyethyleneoxide added with LiBF4 as a lithium salt were mixed uniformly in acetone solvent. This mixture was coated respectively on the active material side of the positive electrode and the active material side of the negative electrode and then acetone used as the solvent was dried and thereby removed whereby a thin Mm solid electrolyte layer was formed directly on the electrode materials for the positive and negative electrodes. The positive and negative electrodes were passed through a roll press with the coated sides of these electrodes being in contact with each other and was cut into a sheet having a size of 40 X 50mm. Thus, a lithium ion secondary battery shown in FIG. 1 having a thin film solid electrolyte 3 formed between a positive electrode 2 and a negative electrode 4 was produced. The total thickness of this battery was 110 gm and the thickness of the thin film solid electrolyte in the battery was 3gm.

Lead wires were connected to a positive electrode collector 1 and a negative electrode collector 5 and the charging discharging cycle test was conducted at 25 C with charging finish voltage of 4.2V and discharging finish voltage of 3.5V. The cycle characteristic of the discharging capacity up to 20 cycles is shown in FIG. 2. Initial discharging capacity of Example 1 was 36.2raAh and discharging capacity after 20 cycles was 34.1mAh, thus maintaining more than 96% of the initial discharging capacity.

Comparative Example 1 The same battery as the battery of Example 1 was produced except that glass-ceramic powder was not used but polyethyleneoxide added with LiBF4 only was used for the thin film solid electrolyte. The charging-discharging cycle test was conducted under the same conditions as in Example 1. The cycle characteristic of the discharging capacity up to 20 cycles is shown in FIG. 2.
Example 2 Commercially available lithium cobalt oxide (LiCo02) was used as the positive electrode active material. This positive electrode active material and the same electric conductive additive, ion conductive additive and binder as used in Example 1 were mixed in acetone solvent. This mixture was coated on a positive electrode collector made of an aluminum sheet having thickness of 10,um to thickness of about 50/2m to form a positive electrode layer. Immediately thereafter, the same mixture of glass-ceramic powder and polyethyleneoxide added with a lithium salt as used in preparation of the thin film solid electrolyte in Example 1 was coated thinly on the positive electrode layer to form an electrolyte layer. Then, the same mixture as used in preparation of the negative electrode in Example 1 was coated on the electrolyte layer to thickness of about 50 ,u m. A copper sheet which constituted the negative electrode collector was attached to the coated side of the negative electrode and, after drying under 100 C, the assembly was passed through a roll press and was cut into a sheet having a size of 40 x 50mm. Thus, a lithium ion secondary battery shown in FIG. 1 having a thin film solid electrolyte 3 formed between a positive electrode 2 and a negative electrode 4 was produced. The total thickness of this battery was 100,um and the thickness of the thin film solid electrolyte in the battery was about ,um. Since no drying process was inserted in the coating of the positive electrode, the electrolyte and the negative electrode, the positive electrode layer and the solid electrolyte layer existed in a mixed state in some portions of the interface between them and the solid electrolyte layer and the negative electrode existed in a mixed state in some portions of the interface between them.

Lead wires were connected to a positive electrode collector 1 and a =
negative electrode collector 5 and the charging-discharging cyde test was conducted at 25 C and a constant current of 0.1mA/cm2 and with charging finish voltage of 4.2V and discharging finish voltage of 3.5V. The charging-discharging cycle test was also conducted at constant current of lmAh/cm2.

Comparative Example 2 The same battery as the battery of Example 2 was produced except that glass-ceramic powder was not used for the thin film solid electrolyte. The charging-discharging cycle test was conducted under the same condition as in Example 2. Comparison between Example 2 and Comparative Example 2 of the initial discharging capacity of charging and discharging densities of 0.1mA/cm2 and 1mA/cm2 and the discharging capacity after 20 cycles are = shown in Table 1.

Table 1 Example 2 Comparative Example 2 0.1mAcm2 1mAcm2 0.1mAcm2 imAcm2 Initial discharging capacity (mAh) 39.2 38.8 35.0 32.2 Discharging capacity after 20 cycles (mAh) 36.3 35.1 31.2 26.5 As will be understood from Table 1, in the battery of Example 2, deterioration of the discharging capacity with lapse of the cycle and deterioration of the discharging capacity due to rapid charging and discharging were both mitigated compared with Comparative Example 2.
Example 3 The same glass-ceramic powder containing Lii+.4-yALTi2-.SiyP37012 as a predominant crystal phase and having an average particle diameter of 1.0/2 m as used in preparation of the positive electrode in Example 1 was pressed and formed to a disk by using lithium phosphate L13PO4 as the inorganic binder and thereafter the disk was sintered to provide a target material. A
sputtering target having a diameter of 100mm and thickness of lmm was obtained by grinding and polishing the outer periphery and both surfaces of the target material.

A thin film was formed on a lithium-aluminum alloy foil having a diameter of 20mm and thickness of 20 ,u m by using an RF magnetron sputtering device. The solid electrolyte obtained had thickness of 0.1,um.
Then, a LiCo02 positive electrode film was formed on thin film solid electrolyte. The positive electrode film obtained had thickness of 2,um. An aluminum film was formed as a positive electrode collector on this positive electrode film to thickness of 0.1,um. Since the solid electrolyte and the positive electrode film became amorphous, heat treatment at 550 C was applied and a thin film battery having thickness of about 221um was obtained.
A disk having a diameter of 18mm was stamped out from this battery and put in a coin battery having a diameter of 20mm to assemble a coin type battery.

The charging discharging cycle test was conducted at -20 C, 25 C and 80 C and a constant current of 1mAh/cm2 and with charging finish voltage of 3.5V and discharging finish voltage of 2.5V. Also, the assembled coin type battery was mounted on a circuit substrate by reflow soldering at 250 C and a similar cycle test was conducted at 25 C.
Comparative Example 3 An electrolyte was prepared by impregnating non-woven cloth with a conventional electrolytic solution and a battery was produced using this electrolyte. The same negative electrode made of lithium-aluminum alloy as in Example 1 was used and a positive electrode was prepared by forming a film of LiCo02 on an aluminum foil having thickness of 10 ,u m by a sputtering device in the same manner as in Example 1. The positive electrode and the negative electrode were attached to each other through a separator made of non-woven cloth having thickness of 26,u m and the separator was impregnated with propylene carbonate added with L1N(C2F5S02)2 as a lithium salt whereby a thin film battery having thickness of about 58,u m was produced. In all other respects, the same process as in Example 3 was followed to produce a coin type battery. The charging-discharging test was conducted under the same conditions as in Example 3.

Comparison between Example 3 and Comparative Example 3 of initial discharging capacity discharging capacity after 300 cycles, initial discharging capacity and discharging capacity after 300 cycles after reflow soldering at different temperatures are shown in Table 2.

Table 2 Example 3 Comparative Example 3 Initial capacity Capacity after Initial capacity Capacity after (mAh) 300 cydes(mAh) (mAh) 300 cydes(mAh) ¨20 C 0.12 0.11 0.05 0.02 25 C 0.22 0.20 0.22 0.16 80 C 0.24 0.19 0.22 0.12 25 C (reflow 0.21 0.18 bursting soldering) From Table 2, it will be understood that the battery of Example 3 had excellent cyde characteristic at the respective temperature and, even at ¨
25 C, maintained about 50% of the capacity at the room temperature. The battery of Comparative Example 3 was burst by reflow soldering whereas the battery of Example 3 caused little change in the capacity by reflow soldering.

Example 4 Preparation of the positive electrode A positive electrode layer and a think film electrolyte layer were formed on a positive electrode collector made of aluminum in the same manner as in Example 1 except that LiMn204 was used as the positive electrode active material.

Preparation of the negative electrode As the negative electrode active material, Li4Ti5012 was used. This negative electrode active material, glass-ceramic powder used as an ion conductive additive and polyvinylidene fluoride PVdF used as a binder were mixed together in acetone solvent and this mixture was coated on a negative electrode collector made of a copper sheet having thickness of 10 kt m to thickness of about 50 /..t m to prepare a negative electrode layer on the negative electrode collector. Immediately thereafter, the same mixture of glass-ceramic powder and polyethyleneoxide added with a lithium salt as used for preparation of the thin film solid electrolyte in Example 1 was coated thinly on the negative electrode layer to form a thin film electrolyte layer.

Production of the battery The positive electrode and the negative electrode were attached to each other on their electrolyte side and were passed through a roll press at 100 C
and dried. The positive electrode layer had thickness of 601um, the thin film solid electrolyte layer had thickness of 3,u.m, the negative electrode layer had thickness of 100 ,u m and the total thickness was about 180 ,u m. The assembly was cut into a sheet having a size of 40 x 50mm and lead wires were connected to the positive electrode collector and the negative electrode collector. Charging-discharging cycle test was conducted at 25 C at a constant current of 0.1mA/cm2 and with charging finish voltage of 3.0V and discharging finish voltage of 2.2V.

Comparative Example 4 The same battery as the battery of Example 4 was produced except that glass-ceramic powder was not used for the electrolyte layers of the positive and negative electrodes. The charging-discharging cycle test was conducted under the same conditions as in Example 4. The cycle characteristic of the discharging capacity up to 20 cydes is shown in FIG. 3. The initial discharging capacity of Example 4 was slightly lower than that of Comparative Example 4 but Example 4 exhibited little deterioration in the cycle characteristic and maintained 98% of the initial capacity after 20 cycles.

Example 5 The same battery as that of Example 4 was produced and the charging-discharging cycle test was conducted at 25 C and at constant current of 0.1mAtk/cm2 and rapid charging-discharging of 1 and 3mA/cm2 with charging finish voltage of 3.0V and discharging finish voltage of 2.2V.

Comparative Example 5 Glass-ceramic powder and polyethyleneoxide added with LiBF4 as a lithium salt was uniformly mixed in acetone solvent and this mixture was coated on a cast sheet to thickness of 501um, dried and passed through a roll press to produce a solid electrolyte in the form of a sheet having thickness of 301um. In the same manner as in Example 4, a positive electrode layer was formed on a positive electrode collector made of aluminum and a negative electrode layer was formed on a negative electrode collector made of a copper sheet. The positive electrode layer and the negative electrode layer were attached to both surfaces of the solid electrolyte (separator) in the form of a sheet and the assembly was passed through a roll press to produce a battery in the form of a sheet having thickness of 210,um. The battery was cut into a sheet having a size of 40 x 50mm and lead wires were connected to the positive electrode collector and the negative electrode collector. The charging ¨discharging cyde test was conducted under the same conditions as in Example 4. The initial discharging capacity and the discharging capacity after 20 cycles of Example 5 and Comparative Example 5 are shown in Table 3.
Table 3 Example 5 Comparative Example 5 Initial capacity Capacity after Initial capacity Capacity after (mAh) 20 cydes(mAh) (mAh) 20 cydes(mAh) Charging/
discharging density 0.1mA/cm2 32.0 31.3 30.8 29.0 lmAkm2 32.0 31.1 25.3 23.1 3mA/cm2 31.5 30.3 20.4 16.5 There was not much difference between the batteries of Example 5 and Comparative Example 5 at the charging-discharging rate of 0.1mA/cm2 but, as the charging-discharging density was raised to perform rapid charging-discharging, reduction in the capacity was clearly observed in Comparative Example 5. This reduction was caused by increase in resistance to moving of ion in the interface between the positive electrode and the solid electrolyte and the interface between the solid electrolyte and the negative electrode. In Example 5 in which the solid electrolyte was formed directly on the electrode, a battery capable of functioning adequately at a large output was obtained.

As described above, the lithium ion secondary battery having the thin film solid electrolyte of the present invention has a high output and excellent charging-discharging cycle characteristic. Further, since the battery of the invention does not contain an organic electrolytic solution a lithium ion secondary battery which is safer and more durable than the prior art batteries can be realized.

Further, in comparison with the prior art secondary battery having a solid electrolyte which has large electrochemical resistance in the interface between the positive electrode and the electrolyte or the interface between the electrolyte and the negative electrode, the lithium ion secondary battery having the thin film solid electrolyte of the present invention has realized excellent contact in the interface between the positive or negative electrode and the electrolyte by forming the solid electrolyte directly on the electrode whereby a battery having a high capacity and a large output can be provided.

In the prior art lithium ion secondary battery, there was a problem that, if the electrolyte is extremely thin, short-circuiting due to internal short-circuiting takes place when external stress is applied to the battery or the battery is bent. In the lithium ion secondary battery having the thin film solid electrolyte of the invention, a relatively large quantity of inorganic substance such as glass-ceramic powder is present in the solid electrolyte and, therefore, internal short-circuiting due to external stress does not take place.
Besides, in a case where the thin film solid electrolyte is formed by sputtering, the entire solid electrolyte can be made of glass-ceramic and, in this case, possibility of short-circuiting can be totally eliminated.

Claims (3)

1. A method for manufacturing a lithium ion secondary battery having a thin film solid electrolyte comprising a lithium ion conductive inorganic substance, selected from a group consisting of a lithium ion conductive crystal and a lithium ion conductive glass-ceramic, said thin film solid electrolyte having a thickness of 20 µm or below, comprising a step of forming the thin film solid electrolyte by coating the lithium ion conductive inorganic substance having an average particle diameter of 0.15 - 1.0 µ m and comprising one or more selected from the group consisting of a crystal of Li1+x+y Al x Ti2-x Si y P3-y O12 0 <= .y <= 1 as a predominant crystal phase directly on an electrode material or materials for a positive or negative electrode.
2. A method for manufacturing a lithium ion secondary battery having a thin film where 0 <= x <= 1, 0 <= .y <= 1 and glass-ceramic containing Li1+x+y Al x Ti2-x Si y P3-y O12 where 0 <= x <= 1, solid electrolyte comprising a lithium ion conductive inorganic substance, selected from a group consisting of a lithium ion conductive crystal and a lithium ion conductive glass-ceramic, said thin film solid electrolyte having a thickness of 20 µm or below comprising a step of forming the thin film solid electrolyte by coating the lithium ion conductive inorganic substance having an average particle diameter of 0.15 - 1.0 µ m and comprising 0 <= .y <= 1 as a predominant crystal phase directly on an electrode material or materials for a positive and negative electrode.
3. A method for manufacturing a lithium ion secondary battery as defined in claim one or more selected from the group consisting of a crystal of Li1+x+y Al x Ti2-x Si y P3-y O12 1 or 2 comprising a step of preparing slurry comprising the lithium ion conductive inorganic substance and a step of forming the thin film solid electrolyte by coating the slurry directly on the electrode material or materials for the positive or negative electrode.

where 0 <= .x <= 1, 0 <= .y <= 1 and glass-ceramic containing Li1+x+y Al x Ti2-x Si y P3-y O12 where 0 <= .x <= 1,
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