JP2007103130A - Thin film solid secondary battery and method of manufacturing thin film solid secondary battery - Google Patents

Thin film solid secondary battery and method of manufacturing thin film solid secondary battery Download PDF

Info

Publication number
JP2007103130A
JP2007103130A JP2005290257A JP2005290257A JP2007103130A JP 2007103130 A JP2007103130 A JP 2007103130A JP 2005290257 A JP2005290257 A JP 2005290257A JP 2005290257 A JP2005290257 A JP 2005290257A JP 2007103130 A JP2007103130 A JP 2007103130A
Authority
JP
Japan
Prior art keywords
active material
material layer
electrode active
negative electrode
positive electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2005290257A
Other languages
Japanese (ja)
Inventor
Mamoru Baba
Hiromi Nakazawa
Kimihiro Sano
弘実 中澤
公宏 佐野
守 馬場
Original Assignee
Geomatec Co Ltd
Iwate Univ
ジオマテック株式会社
国立大学法人岩手大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Geomatec Co Ltd, Iwate Univ, ジオマテック株式会社, 国立大学法人岩手大学 filed Critical Geomatec Co Ltd
Priority to JP2005290257A priority Critical patent/JP2007103130A/en
Publication of JP2007103130A publication Critical patent/JP2007103130A/en
Application status is Pending legal-status Critical

Links

Images

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/54Manufacturing of lithium-ion, lead-acid or alkaline secondary batteries

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thin film solid secondary battery having high charge/discharge capacity and high cycle characteristics. <P>SOLUTION: In the thin film solid secondary battery formed by laminating a positive current collecting layer 20, a positive active material layer 30, a solid electrolyte layer 40, a negative active material layer 50, and a negative current collecting layer 20 on a substrate 10, the thickness of the positive active material layer 30 and that of the negative active material layer 5 are decided so that when the ratio of the reverse number of a maximum charge/discharge capacity per volume to the negative active material layer 50 of the positive active material layer 330 is represented by R, the film thickness ratio to the negative active material layer 50 of the positive active material layer 30 satisfies the condition of 0.2≤R≤X≤10R. As the maximum charge/discharge capacity pre volume of the positive active material layer 30 and the negative active material layer 50, a value obtained by actual measurement is used. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a thin film solid secondary battery and a method for manufacturing a thin film solid secondary battery, and more particularly to a thin film solid secondary battery having a large charge / discharge capacity and excellent cycle characteristics and a method for manufacturing the thin film solid secondary battery. .

Currently, lithium ion secondary batteries are widely used mainly in electronic devices such as portable devices. This is because a lithium ion secondary battery has a higher voltage, a larger charge / discharge capacity, and no adverse effects such as a memory effect, compared to a nickel cadmium battery or the like.
Further, electronic devices and the like are being further reduced in size and weight, and lithium ion secondary batteries are also being developed to be reduced in size and weight as batteries mounted on the electronic devices and the like. For example, development of thin and small lithium ion secondary batteries that can be mounted on IC cards, small medical devices, and the like is underway. It is expected that further reduction in thickness and size will be required in the future.

A conventional lithium ion secondary battery uses metal pieces or metal foils for the positive electrode and the negative electrode, which are immersed in an electrolytic solution and covered with a container. For this reason, there was a limit to thinning and miniaturization. Actually, the limit is about 1 mm in thickness and about 1 cm 3 in volume.
However, recently, in order to enable further reduction in thickness and size, a polymer battery using a gel electrolyte instead of an electrolytic solution (for example, see Patent Document 1) or a thin film solid secondary battery using a solid electrolyte (for example, Patent Documents 2 to 4) have been developed.

The polymer battery described in Patent Document 1 has a positive electrode current collector inside an exterior body, a composite positive electrode containing a polymer solid electrolyte inside, an electrolyte layer made of an ion conductive polymer compound, and a polymer solid electrolyte inside. A composite negative electrode and a negative electrode current collector are sequentially arranged.
Although such a polymer battery can be made thinner and smaller than a normal lithium ion secondary battery using an electrolytic solution, it requires a gel electrolyte, a bonding agent, a sealing member, etc. Is about 0.1 mm, and is not suitable for further thinning and downsizing.

On the other hand, as described in Patent Documents 2 to 4, the thin film solid secondary battery is formed by sequentially stacking a current collector thin film, a negative electrode active material thin film, a solid electrolyte thin film, a positive electrode active material thin film, and a current collector thin film on a substrate. It is configured by stacking the above layers on the substrate in the reverse order.
With such a configuration, the thin-film solid secondary battery can be made as thin as about 1 μm except for the substrate. Further, if the thickness of the substrate is reduced or a thin solid electrolyte film is used instead of the substrate, the overall thickness can be reduced and the size can be reduced.

  Patent Document 2 discloses a thin film solid state secondary battery in which lithium phosphate is used for the solid electrolyte layer, vanadium oxide or niobium oxide is used for the positive electrode layer and the negative electrode layer. And in the thin film solid secondary battery of patent document 2, lithium is inject | poured into the negative electrode side. Thus, when lithium is injected into the negative electrode side, for example, after the negative electrode layer is formed, it is necessary to take it out into the atmosphere and then inject lithium using a lithium injection device. At the same time, it takes time for the injection work, so that there is a problem that extra time and cost are required.

Further, the negative electrode layer such as vanadium oxide into which lithium is injected is easily oxidized and is also susceptible to moisture. For this reason, when lithium is injected, film quality such as oxidation and moisture absorption is often deteriorated, and there is a problem that a thin-film solid secondary battery having good battery characteristics cannot be formed stably.
In addition, since vanadium oxide is toxic, there is a problem that it is troublesome to handle during the manufacturing process and when using the battery.

  Patent Document 3 discloses a thin-film solid secondary battery in which lithium phosphate containing nitrogen is used for the solid electrolyte layer, a metal oxide containing lithium is used for the positive electrode layer, and vanadium oxide is used for the negative electrode layer. Unlike the thin film solid state secondary battery of Patent Document 2, the thin film solid state secondary battery of Patent Document 3 contains lithium from the beginning, so that lithium injection work is not required, and the time and cost required for this work are not required. And a thin film solid secondary battery having relatively good battery characteristics can be stably produced.

  However, when vanadium oxide is used for the negative electrode layer, the voltage decrease at the time of discharge is faster than that of a normal solution type secondary battery, and the capacity to maintain a voltage of about 1 V or more necessary for normal device driving is sufficient. There was a problem of few. Further, as described above, vanadium oxide has a problem that handling is troublesome because it is weak against moisture and is toxic.

  As described above, vanadium oxide used for the negative electrode material has problems in handling and battery characteristics. However, when lithium phosphate, which is stable and has relatively high ionic conductivity, is used for the solid electrolyte layer, other negative electrode materials react with each other at the interface between the lithium phosphate and the electrode material to form another product. Therefore, there arises a problem that the battery characteristics are deteriorated. For this reason, when lithium phosphate is used for the solid electrolyte layer, vanadium oxide has been used for the negative electrode material.

On the other hand, in Patent Document 4, other lithium ion conductor (a composite oxide composed of Li, Ta, Nb, N, and O having high ion conductivity) is used for the solid electrolyte layer instead of lithium phosphate, and lithium is used for the positive electrode layer. A thin film solid secondary battery in which a metal oxide (LiCoO 2 or LiMn 2 O 4 or the like) containing a material other than vanadium oxide (Si or Li 4 Ti 5 O 12 or the like) is used for the negative electrode layer is disclosed.

Japanese Patent Laid-Open No. 10-74496 (page 3-6, FIG. 1-2) JP-A-10-284130 (page 3-4, FIG. 1-4) Japanese Patent Laid-Open No. 2002-42863 (page 9-16, FIG. 1-16) Japanese Patent Laying-Open No. 2004-179158 (page 3-11, FIG. 1)

  In the thin-film solid secondary batteries disclosed in Patent Documents 2 and 3, those that require lithium injection have a problem in that the manufacturing time and manufacturing cost are excessive, and stable battery characteristics are difficult to obtain. In addition, in the type in which lithium is initially included in the electrode material, there is a problem that the voltage decrease during discharge is fast. Further, when vanadium oxide is used for the negative electrode, there is a problem that handling is troublesome because it is weak against moisture and is toxic. On the other hand, the thin film solid secondary battery of Patent Document 4 has no problem of lithium injection work or use of vanadium oxide.

  However, in the thin-film solid secondary batteries of Patent Documents 2 to 4, since the optimum film thickness ratio between the positive electrode and the negative electrode is not taken into account, the charge / discharge capacity cannot be sufficiently extracted, and the capacity is reduced when the thickness is further reduced. There is a problem of shortage. Furthermore, in the thin film solid secondary battery of Patent Document 4, since a negative electrode material other than vanadium oxide is used, the capacity is significantly reduced by repeated charge and discharge, the cycle characteristics are poor, and it is suitable for repeated use. There was a problem.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a thin-film solid secondary battery having a large charge / discharge capacity and excellent cycle characteristics.

According to the present invention, the problem is that a positive electrode current collector layer, a positive electrode active material layer, a solid electrolyte layer, a negative electrode active material layer, and a negative electrode current collector layer are laminated on a substrate in this order or in the reverse order. A thin film solid secondary battery, wherein the positive electrode active material layer has a film thickness ratio X to the negative electrode active material layer, and a reciprocal of a maximum charge / discharge capacity per unit volume of the negative electrode active material layer. The ratio R of the reciprocal of the maximum charge / discharge capacity per unit volume is solved by satisfying the conditional expression of 0.2R ≦ X ≦ 10R.
As described above, in the present invention, by optimizing the film thickness ratio between the positive electrode active material layer and the negative electrode active material layer, the charge / discharge capacity per unit volume close to the maximum can be obtained, and the thinning is efficiently promoted. be able to. In addition, it is possible to obtain excellent cycle characteristics with little decrease in capacity even after repeated charge and discharge. Moreover, since favorable battery characteristics can be obtained by controlling the film thickness ratio, it is possible to easily design a battery that is thin without degrading the battery characteristics.

In the present invention, the solid electrolyte layer is made of either lithium phosphate (Li 3 PO 4 ) or lithium phosphate added with nitrogen (LIPON).
In the present invention, the positive electrode active material layer is a lithium-manganese oxide, lithium-cobalt, which is a metal oxide containing at least one transition metal and lithium of manganese, cobalt, nickel, and titanium. It is characterized by comprising any one of oxide, lithium-nickel oxide, and lithium-manganese-cobalt oxide.
Thus, in the present invention, when a material containing lithium is used for the positive electrode active material layer, it is not necessary to inject lithium later, and a thin film solid secondary battery with good battery characteristics can be obtained with less manufacturing time and processes. Can be created stably.

Furthermore, the negative electrode active material layer is made of silicon-manganese alloy (Si-Mn), silicon-cobalt alloy (Si-Co), silicon-nickel alloy (Si-Ni), lithium-titanium oxide, niobium pentoxide ( Nb 2 O 5 ), titanium oxide (TiO 2 ), indium oxide (In 2 O 3 ), zinc oxide (ZnO), tin oxide (SnO 2 ), nickel oxide (NiO), indium oxide added with tin (ITO) ), Zinc oxide with aluminum added (AZO), zinc oxide with gallium added (GZO), tin oxide with antimony added (ATO), tin oxide with fluorine added (FTO), lithium added It is characterized by comprising any of nickel oxide (NiO-Li).
Thus, in the present invention, since vanadium oxide is not used for the negative electrode active material layer, it is not affected by moisture, and toxicity is not a problem, and handling is easy.

In the present invention, it is preferable that the surface exposed to the atmosphere is covered with a moisture prevention film. If comprised in this way, since a lithium ion movable part can be sealed with a moisture prevention film | membrane, deterioration of battery performance can be suppressed and battery performance can be hold | maintained for a long period of time.
In the present invention, it is preferable that the positive electrode current collector layer, the positive electrode active material layer, the solid electrolyte layer, the negative electrode active material layer, and the negative electrode current collector layer are formed by a sputtering method. According to the sputtering method, there is little deviation in the atomic composition from the vapor deposition material, and a uniform film can be formed.

In addition, the above problem is that a positive electrode current collector layer, a positive electrode active material layer, a solid electrolyte layer, a negative electrode active material layer, and a negative electrode current collector layer are laminated on a substrate in a predetermined thickness in this order or in the reverse order. A thin film solid state secondary battery manufacturing method comprising: a preparatory step for obtaining a maximum charge / discharge capacity per unit volume of each of the positive electrode active material layer and the negative electrode active material layer by a predetermined method; The ratio R of the reciprocal of the maximum charge / discharge capacity per unit volume of the positive electrode active material layer to the reciprocal of the maximum charge / discharge capacity per unit volume of the negative electrode active material layer calculated based on the measured value, and the positive electrode active material A design step of determining the film thicknesses of the positive electrode active material layer and the negative electrode active material layer so that the film thickness ratio X of the layer to the negative electrode active material layer satisfies a conditional expression of 0.2R ≦ X ≦ 10R; The positive electrode active material layer and the negative electrode active material And a deposition step of depositing a predetermined film thickness determined in each of the design process, is solved by performing.
As described above, if the maximum charge / discharge capacity per unit volume is accurately determined by a predetermined method, for example, actual measurement, and the optimum film thickness ratio is determined based on the determined value, the positive electrode active material layer and the negative electrode active material layer Since the film thickness ratio is determined based on the most accurate maximum charge / discharge capacity per unit volume, the battery characteristics can be improved, and the performance of the actual product can be brought closer to the target value at the time of design. .

According to the thin-film solid secondary battery and the method for producing a thin-film solid secondary battery of the present invention, the following effects can be obtained.
(1) In the present invention, by optimizing the film thickness ratio of the positive electrode active material layer and the negative electrode active material layer, it is possible to obtain a charge / discharge capacity per unit volume that is close to the maximum, and promote efficient thinning. be able to. At that time, it is possible to ensure excellent cycle characteristics with little decrease in capacity even when charging and discharging are repeated.
(2) The battery characteristics can be improved by optimizing the film thickness ratio based on the measured values of the maximum charge / discharge capacity per unit volume of the positive electrode active material layer and the negative electrode active material layer, and the performance of the actual product Can be made as close as possible to the target value at the time of design.
(3) Since a material containing lithium is used for the positive electrode active material layer, it is not necessary to inject lithium later, and a thin film solid secondary battery having good battery characteristics can be stably produced with less manufacturing time and process. .
(4) Since vanadium oxide is not used in the negative electrode active material layer, it is not affected by moisture, and toxicity is not a problem, and handling is easy.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. The members, arrangements, configurations, and the like described below do not limit the present invention and can be variously modified within the scope of the gist of the present invention.
1 is a cross-sectional view of a thin film solid state secondary battery according to an embodiment of the present invention, FIG. 2 is a cross-sectional view of an electrode substrate (positive electrode active material substrate) manufactured in Example 1, and FIG. 4 is a cross-sectional view of the produced electrode substrate (negative electrode active material substrate), FIG. 4 is a cross-sectional view of the thin-film solid secondary battery of Example 1, and FIG. 5 is a graph of charge / discharge characteristics of the thin-film solid secondary battery of Example 1. . 6 is a graph of charge / discharge characteristics of the thin-film solid secondary battery of Example 2, and FIG. 7 is a cross-sectional view of the thin-film solid secondary battery of Example 5.

(First embodiment)
As shown in FIG. 1, the thin-film solid secondary battery 1 of the present embodiment includes a positive electrode side current collector layer 20, a positive electrode active material layer 30, a solid electrolyte layer 40, a negative electrode active material layer 50, on a substrate 10. The current collector layer 20 on the negative electrode side and the moisture prevention film 60 are sequentially laminated. Note that the stacking order on the substrate 10 is the order in which the positive electrode active material layer 30 and the negative electrode active material layer 50 are replaced, that is, the negative electrode current collector layer 20, the negative electrode active material layer 50, the solid electrolyte layer 40, The order may be the positive electrode active material layer 30, the positive electrode current collector layer 20, and the moisture prevention film 60.

  The substrate 10 is formed using a substance such as glass, semiconductor silicon, ceramic, stainless steel, or resin. For example, polyimide, PET, or the like can be used as the resin substrate. In addition, the substrate 10 can be formed into a thin film that can be bent.

The current collector layer 20 may be a metal thin film that has good adhesion to each of the positive electrode active material layer 30, the negative electrode active material layer 50, and the solid electrolyte layer 40, and has low electrical resistance. In order for the current collector layer 20 to function satisfactorily as an extraction electrode, the sheet resistance is desirably 1 kΩ / □ or less. When the film thickness of the current collector layer 20 is set to about 0.1 μm or more, the current collector layer 20 needs to be formed of a substance having a resistivity of about 1 × 10 −2 Ω · cm or less. As such a substance, for example, vanadium, aluminum, copper, nickel, gold or the like can be used. With these materials, the current collector layer 20 can be formed to a thickness of about 0.1 μm, which is as thin as possible and has a low electrical resistance.

As the positive electrode active material layer 30, a metal oxide thin film containing lithium and any one or more of manganese, cobalt, and nickel, which are transition metals capable of detaching and inserting lithium ions, can be used. For example, lithium-manganese oxide (LiMn 2 O 4 , Li 2 Mn 2 O 4, etc.), lithium-cobalt oxide (LiCoO 2 , LiCo 2 O 4, etc.), lithium-nickel oxide (LiNiO 2 , LiNi 2 O, etc.) 4 ), lithium-manganese-cobalt oxide (LiMnCoO 4 , Li 2 MnCoO 4, etc.) and the like can be used.
As described above, when a material containing lithium is used for the positive electrode active material layer, it is not necessary to inject lithium later, and a thin-film solid secondary battery having good battery characteristics can be stably manufactured with less manufacturing time and process. it can.

  The film thickness of the positive electrode active material layer 30 is desirably as thin as possible, but is preferably about 0.01 to 1 μm that can ensure charge / discharge capacity. At this time, the film thickness of the positive electrode active material layer 30 is set to the maximum per unit volume of the negative electrode active material layer 50 in consideration of the maximum charge / discharge capacity per unit volume of the positive electrode active material layer 30 as described later. It is determined according to the charge / discharge capacity and the film thickness of the negative electrode active material layer 50.

For the solid electrolyte layer 40, lithium phosphate (Li 3 PO 4 ) having good lithium ion conductivity, a substance obtained by adding nitrogen thereto (LiPON), or the like can be used. The film thickness of the solid electrolyte layer 40 is preferably about 0.1 to 1 [mu] m, which is as thin as possible and reduces the occurrence of pinholes.

Negative electrode active material layer 50 is silicon - manganese alloy (Si-Mn), silicon - cobalt alloy (Si-Co), silicon - nickel alloy (Si-Ni), lithium - titanium oxide (LiTi 2 O 4, Li 4 Ti 5 O 12 etc.), niobium pentoxide (Nb 2 O 5 ), titanium oxide (TiO 2 ), indium oxide (In 2 O 3 ), zinc oxide (ZnO), tin oxide (SnO 2 ), nickel oxide (NiO) ), Indium oxide added with tin (ITO), zinc oxide added with aluminum (AZO), zinc oxide added with gallium (GZO), tin oxide added with antimony (ATO), fluorine added In addition, tin oxide (FTO), nickel oxide to which lithium is added (NiO-Li), or the like can be used.
Thus, when vanadium oxide is not used for the negative electrode active material layer, it is not affected by moisture, and toxicity is not a problem, and handling is easy.

  The film thickness ratio between the positive electrode active material layer 30 and the negative electrode active material layer 50 is a film thickness ratio X of the positive electrode active material layer 30 to the negative electrode active material layer 50 (X = positive electrode film thickness: negative electrode film thickness = positive electrode film thickness / negative electrode film thickness). ) R (R = 1 / maximum charge / discharge capacity per unit volume of positive electrode: 1 / maximum charge / discharge capacity per unit volume of negative electrode = negative electrode ratio) It is preferable that X = R, where “maximum charge / discharge capacity per unit volume / maximum charge / discharge capacity per unit volume of positive electrode”. That is, the film thickness ratio such that X = R is the optimum film thickness ratio.

The reason why the film thickness ratio where X = R is the optimum film thickness ratio is that when the positive electrode layer and the negative electrode layer are formed at such a film thickness ratio, the amount of lithium ions that can be inserted and removed from the positive electrode layer and the negative electrode layer Are almost equal, Li ions can be inserted and removed from the positive electrode and negative electrode without excess and deficiency, and unnecessary Li ions are eliminated, and the capacity per unit volume when viewed from the whole thin film solid secondary battery is maximized. is there. That is, if the entire film thickness is the same, the capacity is maximized when the optimum film thickness ratio is obtained, and the battery can be thinned while ensuring the maximum capacity.
However, even when the film thickness ratio X is set to a value slightly deviated from the optimum film thickness ratio, it is preferable that the capacity is not reduced so much and the cycle characteristics and the like are not problematic. Such a range of the film thickness ratio is a range in which the relationship between X and R satisfies the conditional expression of 0.2R ≦ X ≦ 10R. Therefore, it is preferable to determine the film thickness ratio X so as to be a value within this range.

  In the present invention, the maximum charge / discharge capacity per unit volume of the positive electrode active material layer 30 and the negative electrode active material layer 50 is obtained by forming an electrochemical cell by forming a single film of the positive electrode active material or the negative electrode active material on the substrate. It is obtained by actual measurement by performing charge / discharge measurement. For example, an electrode substrate in which Li metal is used as a negative electrode and a positive electrode thin film or a negative electrode thin film is formed on a current collector thin film is produced, an electrochemical cell is produced using an electrolyte solution using this electrode substrate as a positive electrode, and charge / discharge measurement is performed. An actual measurement value can be obtained by performing.

Further, it is preferable that the surface of the thin film solid secondary battery 1 exposed to the atmosphere is covered with a moisture preventing film 60 having a moisture preventing effect. In this way, battery performance can be kept longer. As the moisture prevention film 60, silicon oxide (SiO 2 ), silicon nitride (SiN x ), or the like can be used. The thickness of the moisture prevention film 60 is preferably about 0.2 μm which is as thin as possible and has a high moisture prevention effect.

  As a method for forming each of the above thin films, a vacuum film forming method such as a sputtering method, an electron beam evaporation method, or a heating evaporation method, a coating method, or the like can be used. It is preferable to use a vacuum film-forming method that can form a thin film more thinly and uniformly. More preferably, it is preferable to use a sputtering method in which there is little deviation in the atomic composition from the vapor deposition material and uniform film formation is possible.

When the thin-film solid secondary battery 1 is charged, lithium is separated from the positive electrode active material layer 30 as ions, and is inserted in the negative electrode active material layer 50 through the solid electrolyte layer 40. At this time, electrons are emitted from the positive electrode active material layer 30 to the outside.
Further, at the time of discharging, lithium is separated from the negative electrode active material layer 50 as ions, and is inserted into the positive electrode active material layer 30 through the solid electrolyte layer 40. At this time, electrons are emitted from the negative electrode active material layer 50 to the outside.
In addition, as a means for obtaining the maximum charge / discharge capacity per unit volume of the positive electrode active material layer and the negative electrode active material layer, a calculation method or the like is used when a value with the same accuracy as the actual measurement can be calculated. May be. Further, the actual measurement method is not limited to the charge / discharge measurement as described above, and other methods may be used.

Example 1
In Example 1 according to the above-described embodiment, as described above, the positive electrode and the negative electrode are each formed as a single film using the positive electrode active material and the negative electrode core material, and the actual electrochemical cell is manufactured using the electrolyte solution. Charging / discharging measurement was performed about these. And the conditions of the film thickness ratio of a positive electrode layer and a negative electrode layer were determined based on the measured value obtained as a result. And the thin film solid secondary battery 1 was produced within the range of the conditions of the obtained film thickness ratio, and the battery performance of the produced thin film solid secondary battery 1 was measured and evaluated. The details will be described below.

(1) Charge / Discharge Measurement First, the maximum charge / discharge capacity per unit volume of each active material used for the positive electrode active material layer 30 and the negative electrode active material layer 50 was determined by actual measurement. Specifically, the positive electrode active material substrate 31 and the negative electrode active material substrate 51 shown below were prepared, and charge / discharge measurement was performed.
As shown in FIG. 2, the positive electrode active material substrate 31 was formed by forming a current collector layer 20 and a positive electrode active material layer 30 in this order on the substrate 10 by a sputtering method. At the time of this film formation, a stainless steel mask having an outer shape of 50 mm × 50 mm and a thickness of 0.3 mm with an opening of about 32 mm × 32 mm provided at the center so that the electrode can be drawn from the current collector layer 20 (the width of each side is 9 mm) was used to form the uppermost positive electrode active material layer 30.

As the substrate 10, soda lime glass having a length of 50 mm, a width of 50 mm, and a thickness of 1 mm was used.
The current collector layer 20 was formed by a DC magnetron sputtering method using a vanadium metal target. The film was formed with a DC power of 1 KW and no heating. Thereby, a 0.1 μm-thick vanadium thin film was formed as the current collector layer 20.
The positive electrode active material layer 30 was formed by RF magnetron sputtering using a sintered manganate (Li 2 Mn 2 O 4 ) sintered target and introducing oxygen. The film was formed with an RF power of 1 KW and no heating. Thus, a lithium manganate thin film having a thickness of 0.2 μm was formed.

As shown in FIG. 3, the negative electrode active material substrate 51 was formed by forming a current collector layer 20 and a negative electrode active material layer 50 in this order on the substrate 10 by a sputtering method. As in the case of the positive electrode active material substrate 31, an outer diameter of about 32 mm × 32 mm provided with an opening of about 32 mm × 32 mm at the center and a thickness of 0.3 mm so that the electrode can be drawn from the current collector layer 20. The uppermost negative electrode active material layer 50 was formed using a stainless mask (the width of each side was 9 mm).
The substrate 10 and the current collector layer 20 were the same as the positive electrode active material substrate 31. The negative electrode active material layer 50 was formed by RF magnetron sputtering using a sintered compact target of lithium titanate (Li 4 Ti 5 O 12 ) and introducing oxygen. The film was formed with an RF power of 1 KW and no heating. Thereby, a lithium titanate thin film having a thickness of 0.2 μm was formed.

An electrochemical cell using the positive electrode active material substrate 31 or the negative electrode active material substrate 51 obtained as described above as a positive electrode, lithium metal as a negative electrode, and 1.0 M-LiPF 6 / EC-DEC as an electrolytic solution is manufactured. did. And the charging / discharging characteristic of this electrochemical cell was measured.
The measurement conditions were a measurement current of 0.1 mA, and charge and discharge stop voltages of 4.5 V and 3.0 V in the case of a lithium manganate positive electrode active material (positive electrode active material layer 30), respectively. In the case of the negative electrode active material (negative electrode active material layer 50), it was set to 3.0 V and 1.5 V, respectively.

As a result, the charge / discharge capacity of each active material was 0.2 mAh in the lithium manganate positive electrode active material (positive electrode active material layer 30). Moreover, in the lithium titanate negative electrode active material (negative electrode active material layer 50), it was 0.1 mAh. Next, this measured value was converted into a capacity per unit volume. Since any active material has a film thickness of 0.2 μm and an effective area of 32 mm × 32 mm, the volume (0.2 × 10 −4 cm × 3.2 cm × 3.2 cm = 2.05 × 10 −4 cm). 3 ) When the measured value is divided by, the maximum charge / discharge capacity per unit volume is 976 mAh / cm 3 in the case of the lithium manganate positive electrode active material (positive electrode active material layer 30), and in the case of the lithium titanate negative electrode active material (negative electrode) The active material layer 50) was 488 mAh / cm 3 .
As described above, the maximum charge / discharge capacity per unit volume of each active material was determined by actual measurement.

(2) Determination of conditions for film thickness ratio X Subsequently, based on the actual measurement values obtained as described above, the ratio of the reciprocal of the maximum charge / discharge capacity per unit volume of the positive electrode active material layer to the negative electrode active material layer R was determined. Based on this ratio R, an optimum film thickness ratio X (= R) that can most efficiently and efficiently insert and desorb Li ions was determined. Further, the range of the film thickness ratio X in which a thin film solid secondary battery having no problem in cycle characteristics and battery capacity was obtained from the conditional expression of 0.2R ≦ X ≦ 10R.
Specifically, when the lithium manganate positive electrode active material and the lithium titanate negative electrode active material are the positive electrode active material layer 30 and the negative electrode active material layer 50, respectively, the optimum film thickness ratio X of the positive electrode layer to the negative electrode layer is The ratio of the reciprocal of the maximum capacity per unit volume, that is, X (= R) = 1/976 ÷ 1/488 = 1 ÷ 2 (= 0.5). Further, by substituting R = 0.5 into the conditional expression of 0.2R ≦ X ≦ 10R, the condition of the film thickness ratio X for preventing the problem in cycle characteristics and battery capacity is 0.1 ≦ X ≦ 5.

(3) Production of Thin Film Solid Secondary Battery 1 Subsequently, the thin film solid secondary in which the positive electrode active material layer 30 and the negative electrode active material layer 50 are formed with a film thickness satisfying the conditional expression of the film thickness ratio X. Battery 1 is produced. In this example, as shown in FIG. 4, the current collector layer 20, the positive electrode active material layer 30, the solid electrolyte layer 40, the negative electrode active material layer 50, and the current collector layer 20 are formed on the substrate 10 in this order by sputtering. A film was formed. In this example, in order to confirm the effectiveness of the conditional expression, seven types of thin-film solid secondary batteries 1 in which the film thickness of the negative electrode active material layer 50 was changed so as to include the range of the conditional expression were manufactured.

  In this example, as shown in FIG. 4, each layer of the thin-film solid secondary battery 1 was laminated so that the upper thin film had a pyramid shape sequentially smaller than the lower thin film. For this purpose, a stainless steel mask having an opening at the center was selected so that the size of the opening was reduced in order toward the upper layer, and each layer was formed. That is, the collector layer 20 is formed by disposing the layer with the largest opening first, and then the masks are replaced in the order in which the openings gradually become smaller. Form a film. The uppermost current collector layer 20 that determines the effective area of the thin-film solid-state secondary battery 1 has a 50 mm × 50 mm outer diameter 0.3 mm-thick stainless steel mask (each of which is provided with an opening of about 32 mm × 32 mm in the center (each The film was formed using a side width of 9 mm). As a result, the effective area was 32 mm × 32 mm.

  The substrate 10, the current collector layer 20, and the positive electrode active material layer 30 used in the thin film solid secondary battery 1 are the same as the positive electrode active material substrate 31. That is, soda lime glass having a length of 50 mm, a width of 50 mm, and a thickness of 1 mm was used as the substrate 10. Further, a 0.1 μm-thick vanadium thin film was formed as the current collector layer 20, and a 0.2 μm-thick lithium manganate thin film was formed as the positive electrode active material layer 30 in the same manner as the positive electrode active material substrate 31.

As the solid electrolyte layer 40, a lithium phosphate thin film to which nitrogen having a thickness of 0.1 μm was added was used. This thin film was formed by RF magnetron sputtering using a sintered target of lithium phosphate (Li 3 PO 4 ) and introducing nitrogen gas. The film was formed with an RF power of 1 KW and no heating.
Further, a thin film of lithium-titanium oxide formed in the same manner as the negative electrode active material substrate 51 was used for the negative electrode active material layer 50. In this example, the film thickness of the negative electrode active material layer 50 was determined based on the measurement result of the charge / discharge capacity. That is, in this example, since the film thickness of the positive electrode active material layer 30 is 0.2 μm, the film thickness of the negative electrode active material layer 50 for achieving the optimum film thickness ratio X = 0.5 is 0.00. 4 μm. Then, 7 including 0.02 μm, 0.04 μm, 0.2 μm, 0.4 μm, 0.8 μm, 2.0 μm, and 4.0 μm so as to include the optimum film thickness and the range of 0.1 ≦ X ≦ 5. The film thickness of the kind was determined and seven kinds of thin film solid secondary batteries 1 were produced.

(4) Measurement and evaluation of battery performance In order to evaluate the battery performance of seven types of thin film solid secondary batteries 1 having different thicknesses of the negative electrode active material layer 50 obtained as described above, charge / discharge measurement was performed. Charge / discharge characteristics were measured using a container. The measurement conditions were such that the current during charging and discharging was 0.1 mA, and the voltage at the end of charging and discharging was 3.5 V and 0.3 V, respectively. As a result, it was confirmed that any of the seven types of thin film solid secondary batteries 1 exhibited repeated charge / discharge operations.

FIG. 5 shows a graph of charge / discharge characteristics at the 10th cycle of the thin-film solid secondary battery 1 in which the film thickness of the negative electrode active material layer 50 is 0.4 μm (optimum film thickness ratio). As shown in this figure, the discharge start voltage and the charge start voltage at the 10th cycle when the charge / discharge operation was stable were 3.4 V and 0.5 V, respectively. Moreover, the charge capacity and the discharge capacity were almost equal, 0.17 mAh.
When these results are converted into the capacity per unit volume, the unit positive electrode volume conversion (capacity per unit volume of the positive electrode layer) is 829 mAh / cm 3 , and the unit negative electrode volume conversion (capacity per unit volume of the negative electrode layer) is 415 mAh /. cm 3 . This numerical value is obtained by measuring the positive electrode active material obtained from the actual measurement value of the electrochemical cell prepared using the electrolyte solution by forming each electrode of the positive electrode and the negative electrode as a single film in order to determine the condition of the film thickness ratio. It was about 85% of the maximum charge / discharge capacity per unit volume of the negative electrode active material. The reason why the capacity is smaller than that of the electrochemical cell is considered to be that the electrolyte is solid. The capacity per unit volume of the positive electrode and the negative electrode is 276 mAh / cm 3 .

Moreover, although charging / discharging measurement was performed to 100 cycles, it has confirmed that it showed the substantially constant charging / discharging curve and charging / discharging capacity | capacitance stably.
Table 1 shows the discharge capacity at the 10th and 100th cycles, the discharge capacity per unit volume of the positive electrode and the negative electrode, and the capacity retention rate.
As shown in this table, for the thin film solid secondary battery 1 in which the negative electrode active material layer 50 has a film thickness other than 0.4 μm (optimum film thickness ratio), the film thickness of the negative electrode active material layer 50 is 0.02 μm. Except for those of 4.0 μm and 4.0 μm, the same charge / discharge operation as that of the optimum film thickness ratio was shown, and it was confirmed that the charge / discharge curve and charge / discharge capacity were stable and stable until the 100th cycle. . However, the charge / discharge capacity decreased from the optimum film thickness ratio, and the capacity per unit volume of the positive electrode and the negative electrode also decreased.
The negative electrode active material layer having a thickness of 0.02 μm and 4.0 μm exhibited the same charge / discharge operation as that of the above-mentioned optimum film thickness ratio until the 10th cycle. The charge / discharge capacity decreased, and at the 100th cycle, the capacity decreased to about half of the capacity at the 10th cycle.

From the results of Table 1, the thin film solid secondary battery 1 having the optimum film thickness ratio (negative electrode film thickness 0.4 μm) in the present invention has the best characteristics. It can be seen that the decrease in capacity is suppressed to a small extent. When the film thickness of the negative electrode active material layer 50 is 0.04 μm and 2.0 μm, the capacity is slightly smaller than these, but charging and discharging are stably repeated up to the 100th cycle, and there is no decrease in capacity due to progress of the cycle.
Negative electrode active material layer 50 satisfying the conditional expression of 0.2R ≦ X ≦ 10R (X: film thickness ratio, R: ratio of reciprocal of maximum charge / discharge capacity per unit volume of positive electrode active material and negative electrode active material) of the present invention. As described above, since the value of R = 0.5 is obtained from the actually measured value as described above, when the thickness of the positive electrode active material layer 30 is 0.2 μm as in this example, 0.04 μm ≦ the thickness of the negative electrode active material layer 50 ≦ 2.0 μm. The thin-film solid secondary battery 1 having a film thickness (0.02 μm and 4.0 μm) in which the negative electrode active material layer 50 does not satisfy this conditional expression has a small capacity according to Table 1 and a large decrease in capacity due to cycle progress. .

That is, the upper limit value and the lower limit value of the film thickness in the thin-film solid secondary battery 1 in which the upper limit value and the lower limit value of the film thickness determined from the conditional expression of the present invention are obtained in Table 1 are good. Since they are almost equal, it can be said that the effectiveness of the conditional expression of the present invention has been confirmed.
As described above, in this example, by optimizing the film thickness ratio between the positive electrode active material layer and the negative electrode active material layer, it is possible to obtain a charge / discharge capacity per unit volume that is close to the maximum, and the thickness is reduced efficiently. Can proceed. At that time, it is possible to ensure excellent cycle characteristics with little decrease in capacity even when charging and discharging are repeated. In addition, by optimizing the film thickness ratio based on the measured maximum charge / discharge capacity per unit volume of the positive electrode active material layer and the negative electrode active material layer, the performance of the actual product is brought close to the target value at the time of design. be able to.

(Example 2)
Example 2 is different from Example 1 only in that a silicon-manganese alloy (Si-Mn) is used as the negative electrode active material. Hereinafter, only differences from the first embodiment will be described, and description of similar parts will be omitted.

  The negative electrode active material layer 50 of this example was produced by an RF magnetron sputtering method using a target of a Si—Mn alloy (Mn 25 wt%). The film was formed with an RF power of 1 KW and no heating. Thus, a Si—Mn alloy thin film having a thickness of 0.2 μm was formed. At the time of this film formation, as in Example 1, using a stainless steel mask (width of each side is 9 mm) having an outer shape of 50 mm × 50 mm with a hole of about 32 mm × 32 mm and a thickness of 0.3 mm, The negative electrode active material layer substrate 51 was formed so that the cross section had the configuration shown in FIG.

As in Example 1, 1.0M-LiPF 6 / EC-DEC was electrolyzed using the negative electrode active material layer substrate 51 using the Si—Mn alloy obtained as described above as a positive electrode and lithium metal as a negative electrode. The electrochemical cell used as a liquid was produced, and charge / discharge characteristics were measured. The measurement conditions were a measurement current of 0.1 mA and a charge and discharge stop voltage of 2.0 V and 0.5 V, respectively.
As a result, a value of 0.4 mAh was obtained as the charge / discharge capacity of the Si—Mn alloy negative electrode active material. When this capacity is converted into a capacity per unit volume, the film thickness is 0.2 μm and the effective area is 32 mm × 32 mm, so this volume (0.2 × 10 −4 cm × 3.2 cm × 3.2 cm = 2). .05 × 10 −4 cm 3 ), and in the case of the Si—Mn alloy negative electrode active material, 1951 mAh / cm 3 is the maximum charge / discharge capacity per unit volume.
The maximum charge / discharge capacity per unit volume of the lithium manganate positive electrode active material used as the positive electrode active material layer 30 is 976 mAh / cm 3 as in Example 1.

  As described above, since the maximum charge / discharge capacity per unit volume of each active material was obtained by actual measurement in the same manner as in Example 1, the positive electrode active material layer 30 in this example per unit volume relative to the negative electrode active material layer 50 was obtained. The ratio R of the reciprocal of the maximum charge / discharge capacity is obtained. In this example, R = 1/976 ÷ 1/1951 = 2 ÷ 1 (= 2.0). That is, when the thin-film solid secondary battery 1 is manufactured using lithium manganate, Si—Mn alloy as the positive electrode and the negative electrode active material as in this example, the positive electrode and the negative electrode that can most efficiently insert and desorb Li ions. The film thickness ratio X is X = 2.0. Further, by substituting R = 2.0 into the conditional expression of 0.2R ≦ X ≦ 10R, the condition of the film thickness ratio X in order to prevent problems in cycle characteristics and battery capacity is 0.4 ≦ X ≦ 20.

Subsequently, in the same manner as in Example 1, the thin film solid secondary battery 1 was manufactured with a film thickness satisfying the conditional expression of the film thickness ratio X, and the above-described conditional expression was confirmed in order to confirm the effectiveness. Seven types of thin-film solid secondary batteries 1 in which the thickness of the negative electrode active material layer 50 made of an Si—Mn alloy was changed so as to include a range satisfying the conditional expression were produced.
The negative electrode active material layer 50 was formed using an Si—Mn alloy target and changing the film thickness by RF magnetron sputtering. The film was formed with an RF power of 1 KW and no heating. In this example, the film thickness of the negative electrode active material layer 50 was determined based on the measurement result of the charge / discharge capacity. In the case of this example, since the film thickness of the positive electrode active material layer 30 is 0.2 μm, the film thickness of the negative electrode active material layer 50 for achieving the optimum film thickness ratio (X = 2.0) is 0.00. 1 μm. A total of seven types of film thicknesses of 0.005 μm, 0.01 μm, 0.05 μm, 0.1 μm, 0.2 μm, 0.5 μm, and 1.0 μm are included so as to include this optimum film thickness and the range of the above conditional expression. Were determined.

FIG. 6 shows a graph of charge / discharge characteristics at the 10th cycle of the thin-film solid secondary battery 1 in which the film thickness of the negative electrode active material layer 50 is 0.1 μm (optimum film thickness ratio). As shown in this figure, the discharge start voltage and the charge start voltage at the 10th cycle in which the charge / discharge operation was stable were 4.0 V and 2.0 V, respectively. Moreover, the charge capacity and the discharge capacity were almost equal, 0.12 mAh.
When these results are converted into the capacity per unit volume, the unit positive electrode volume conversion (capacity per unit volume of the positive electrode layer) is 585 mAh / cm 3 and the unit negative electrode volume conversion (capacity per unit volume of the negative electrode layer) is 1170 mAh /. cm 3 . This numerical value is obtained by measuring the positive electrode active material obtained from the actual measurement value of the electrochemical cell prepared using the electrolyte solution by forming each electrode of the positive electrode and the negative electrode as a single film in order to determine the condition of the film thickness ratio. It was about 60% of the maximum charge / discharge capacity per unit volume of the negative electrode active material. The reason why it is smaller than 85% in the case of Example 1 is considered to be due to the fact that the irreversible capacity at which lithium ions cannot be separated from the Si—Mn alloy is large, in addition to the fact that the electrolyte is solid.
The capacity per unit volume of the positive electrode and the negative electrode is 390 mAh / cm 3 , which is larger than the value in Example 1. This is considered to be due to the large capacity per unit volume of the Si—Mn alloy single layer.

In this example, charge / discharge measurement was performed up to 100 cycles, but it was confirmed that the charge / discharge curve and charge / discharge capacity were stable and substantially constant.
The lower part of Table 1 shows the discharge capacity at the 10th cycle and the 100th cycle, the discharge capacity per unit volume of the positive electrode and the negative electrode, and the capacity retention rate in the same manner as in Example 1.
As shown in this table, for the thin-film solid secondary battery 1 in which the negative electrode active material layer 50 has a film thickness other than 0.1 μm (optimum film thickness ratio), the film thickness of the negative electrode active material layer 50 is 0.005 μm. Except for those of 1.0 μm and 1.0 μm, the charge / discharge operation was the same as that of the above-mentioned optimum film thickness ratio, and it was confirmed that the charge / discharge curve and charge / discharge capacity were stable and stable until the 100th cycle. . However, the charge / discharge capacity decreased from the optimum film thickness ratio, and the capacity per unit volume of the positive electrode and the negative electrode also decreased.
In addition, the negative electrode active material layer having a thickness of 0.005 μm and 1.0 μm exhibited the same charge / discharge operation as that of the above-mentioned optimum film thickness ratio until the 10th cycle. The charge / discharge capacity decreased, and at the 100th cycle, the capacity decreased to about half of the capacity at the 10th cycle.

  From the results in Table 1, the thin film solid secondary battery 1 having the best film thickness ratio (negative electrode film thickness is 0.1 μm) in the present invention has the best characteristics. It can be seen that the decrease in capacity is kept small. When the film thickness of the negative electrode active material layer 50 is 0.01 μm and 0.5 μm, the capacity is slightly smaller than these, but charging and discharging are stably repeated up to the 100th cycle, and there is no decrease in capacity due to progress of the cycle. . Since the range of the film thickness of the negative electrode active material layer 50 satisfying the conditional expression (0.2R ≦ X ≦ 10R) of the present invention is determined as R = 2.0 from the measured value as described above, the positive electrode When the film thickness of the active material layer 30 is 0.2 μm, 0.01 μm ≦ the film thickness of the negative electrode active material layer 50 ≦ 0.5 μm. The thin-film solid secondary battery 1 having a thickness (0.005 μm and 1.0 μm) in which the negative electrode active material layer 50 does not satisfy this conditional expression has a small capacity according to Table 1 and a large decrease in capacity due to cycle progress. .

  That is, also in Example 2, as in Example 1, the upper limit value and the lower limit value of the film thickness determined from the conditional expression of the present invention are the results of the thin film solid 2 in which the result that the characteristics are good in Table 1 was obtained. Since the upper limit value and the lower limit value of the film thickness of the secondary battery 1 are almost the same, it can be said that the effectiveness of the conditional expression of the present invention has been confirmed.

(Example 3)
Example 3 differs from Example 3 only in that a different material from Examples 1 and 2 was used as the positive electrode active material. Hereinafter, only differences from the above-described embodiments will be described, and description of similar parts will be omitted.

In this example, four types of lithium-cobalt oxide (LiCoO 2 ), lithium-nickel oxide (LiNiO 2 ), and lithium-manganese-cobalt oxide (LiMnCoO 4 , Li 2 MnCoO 4 ) are used as the positive electrode active material. It was. That is, the positive electrode active material substrate 31 is prepared using each of these four types, an electrochemical cell using lithium metal as the negative electrode is prepared in the same manner as in each of the above-described Examples 1, and charge / discharge measurement is performed. The charge / discharge capacity was measured.
Then, the maximum charge / discharge capacity per unit volume is obtained from the obtained actual measurement value, and compared with the maximum charge / discharge capacity of the lithium titanate negative electrode active material substrate 51 measured in Example 1, the lithium titanate thin film is negative electrode active. The optimum film thickness ratio of each of the four types of positive electrode active materials was determined. Further, based on the conditional expression 0.2R ≦ X ≦ 10R of the present invention, the film thickness ratio X is 0.1R, 0.2R, 0.5R, R, 2R, 10R, 20R for each of the four types of positive electrode active materials. 4 × 7 = 28 types of thin-film solid secondary batteries 1 were manufactured by changing the film thickness of the positive electrode active material layer 30 so that there were 7 types of the following.

And the charge / discharge characteristic was measured about each of these. The measurement conditions were as in Example 1, in which the current during charging and discharging was 0.1 mA, and the voltage at which charging and discharging were terminated was 3.5 V and 0.3 V, respectively.
As a result, it can be confirmed that any thin film solid secondary battery 1 repeatedly shows charge / discharge operation, and as in Example 2, the charge / discharge characteristics and cycle characteristics are the best in the case of the configuration with the optimum film thickness ratio. It was confirmed that there was. It was also confirmed that the film thickness ratio was relatively good even when the film thickness ratio was close to the optimum film thickness ratio. Further, when the film thickness ratio between the positive electrode active material layer 30 and the negative electrode active material layer 50 is X, the sample capacity in the range of 0.2R ≦ X ≦ 10R with respect to the optimal film thickness ratio R is the capacity due to cycle progress. However, in the samples having the film thickness ratios of 0.1R and 20R outside the range, it was confirmed that the capacity decrease due to the cycle progress was large.

Example 4
Example 4 differs from Example 4 only in that a different material from the above examples was used as the negative electrode active material. Hereinafter, only differences from the above-described embodiments will be described, and description of similar parts will be omitted.

In this example, as the negative electrode active material, silicon-manganese alloy (Si-Mn), silicon-cobalt alloy (Si-Co), silicon-nickel alloy (Si-Ni), niobium pentoxide (Nb 2 O 5 ), oxidation Titanium (TiO 2 ), indium oxide (In 2 O 3 ), zinc oxide (ZnO), tin oxide (SnO 2 ), nickel oxide (NiO), indium oxide with tin added (ITO), aluminum added Zinc oxide (AZO), zinc oxide to which gallium is added (GZO), tin oxide to which antimony is added (ATO), tin oxide to which fluorine is added (FTO), nickel oxide to which lithium is added (NiO-Li) 15 types) were used. That is, the negative electrode active material substrate 51 was prepared using each of these 15 types, and an electrochemical cell using lithium metal as the negative electrode was prepared in the same manner as in each of the above Examples 1, and charge / discharge measurement was performed. The charge / discharge capacity was measured.

  Then, the maximum charge / discharge capacity per unit volume is obtained from the obtained actual measurement value, and compared with the maximum charge / discharge capacity of the lithium manganate negative electrode active material substrate 31 measured in Example 1, the lithium manganate thin film is positive electrode active. The optimum film thickness ratio of each of the 15 types of positive electrode active materials was determined. In addition, the film thickness ratio X is 0.1R, 0.2R, 0.5R, R, 2R for each of the 15 positive electrode active materials so as to include the range of conditional expression 0.2R ≦ X ≦ 10R of the present invention. The film thickness of the positive electrode active material layer 30 was changed so that there were seven types of 10R and 20R, and 15 × 7 = 105 types of thin film solid secondary batteries 1 were produced.

And the charge / discharge characteristic was measured about each of these. The measurement conditions were as in Example 1, in which the current during charging and discharging was 0.1 mA, and the voltage at which charging and discharging were terminated was 3.5 V and 0.3 V, respectively.
As a result, it can be confirmed that any thin film solid secondary battery 1 repeatedly shows charge / discharge operation, and as in Example 2, the charge / discharge characteristics and cycle characteristics are the best in the case of the configuration with the optimum film thickness ratio. It was confirmed that there was. It was also confirmed that the film thickness ratio was relatively good even when the film thickness ratio was close to the optimum film thickness ratio. In addition, when the film thickness ratio between the positive electrode active material layer 30 and the negative electrode active material layer 50 is X, the sample having a range of 0.2RX ≦ 10R with respect to the optimum film thickness ratio R decreases the capacity due to cycle progress. However, in the samples having the film thickness ratios of 0.1R and 20R outside the range, it was confirmed that the capacity was greatly decreased by the progress of the cycle.

(Example 5)
In this example, the surface exposed to the atmosphere of the thin-film solid secondary battery 1 having the optimum film thickness ratio of Examples 1 and 2, that is, the exposed surface of the current collector layer 20 on the negative electrode side, as shown in FIG. A thin film silicon secondary battery 2 was fabricated by forming a silicon nitride thin film as the moisture preventing film 60 by sputtering.
The moisture preventing film 60 was formed by introducing a nitrogen gas by an RF magnetron sputtering method using a Si semiconductor target. The film was formed with an RF power of 1 KW and no heating. Thereby, a silicon nitride thin film having a thickness of 0.2 μm was formed.

When the charge / discharge characteristics of the thin-film solid secondary battery 2 covered with the moisture prevention film 60 obtained as described above were measured immediately after creation, the moisture prevention film 60 of Examples 1 and 2 was not covered. A charge / discharge voltage and charge / discharge capacity equivalent to those of the thin-film solid secondary battery 1 were obtained.
Then, about one month later, the charge / discharge characteristics of the thin film solid secondary battery 1 of Examples 1 and 2 were measured again. Since the thin-film solid secondary batteries 1 of Examples 1 and 2 were not covered with the moisture prevention film 60, the discharge capacity was reduced by about 5%. On the other hand, in the thin-film solid secondary battery 2 of this example covered with the moisture prevention film 60, no decrease in charge / discharge capacity was observed even in the measurement after one month.
Thus, by covering the surface with the moisture preventing film 60, it was confirmed that the thin-film solid secondary battery 2 has durability against moisture in the air, and the battery characteristics are hardly deteriorated.

It is sectional drawing of the thin film solid secondary battery which concerns on this embodiment. 1 is a cross-sectional view of an electrode substrate (positive electrode active material substrate) of Example 1. FIG. 3 is a cross-sectional view of an electrode substrate (negative electrode active material substrate) of Example 1. FIG. 1 is a cross-sectional view of a thin film solid secondary battery of Example 1. FIG. 2 is a graph of charge / discharge characteristics of the thin-film solid secondary battery of Example 1. 4 is a graph of charge / discharge characteristics of the thin-film solid secondary battery of Example 2. 6 is a cross-sectional view of a thin film solid secondary battery of Example 5. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 2 ... Thin film solid secondary battery 10 ... Board | substrate 20 ... Current collector layer 30 ... Positive electrode active material layer 31 ... Positive electrode active material substrate 40 ... Solid electrolyte layer 50 ... Negative electrode active material layer 51 ... Negative electrode active material substrate 60 ... Water | moisture content Prevention film

Claims (7)

  1. A thin-film solid secondary battery in which a positive electrode current collector layer, a positive electrode active material layer, a solid electrolyte layer, a negative electrode active material layer, and a negative electrode current collector layer are laminated in this order or in the reverse order on a substrate,
    The thickness ratio X of the positive electrode active material layer to the negative electrode active material layer and the maximum charge / discharge capacity per unit volume of the positive electrode active material layer with respect to the reciprocal of the maximum charge / discharge capacity per unit volume of the negative electrode active material layer A thin film solid-state secondary battery, wherein a reciprocal ratio R satisfies a conditional expression of 0.2R ≦ X ≦ 10R.
  2. 2. The thin-film solid secondary battery according to claim 1, wherein the solid electrolyte layer is made of either lithium phosphate (Li 3 PO 4 ) or lithium phosphate (LIPON) to which nitrogen is added.
  3.   The positive electrode active material layer is a metal oxide containing at least one transition metal and lithium of manganese, cobalt, nickel, and titanium, lithium-manganese oxide, lithium-cobalt oxide, lithium-nickel. 2. The thin film solid secondary battery according to claim 1, wherein the thin film solid secondary battery is made of any one of an oxide and a lithium-manganese-cobalt oxide.
  4. The negative active material layer, a silicon - manganese alloy (Si-Mn), silicon - cobalt alloy (Si-Co), silicon - nickel alloy (Si-Ni), lithium - titanium oxide, niobium pentoxide (Nb 2 O 5 ), titanium oxide (TiO 2 ), indium oxide (In 2 O 3 ), zinc oxide (ZnO), tin oxide (SnO 2 ), nickel oxide (NiO), indium oxide (ITO) with tin added, aluminum Zinc oxide (AZO) to which gallium is added, zinc oxide (GZO) to which gallium is added, tin oxide (ATO) to which antimony is added, tin oxide (FTO) to which fluorine is added, nickel oxide to which lithium is added The thin film solid secondary battery according to claim 1, wherein the thin film solid secondary battery is made of any one of (NiO—Li).
  5.   The thin film solid secondary battery according to claim 1, wherein a surface exposed to the atmosphere is covered with a moisture prevention film.
  6.   2. The thin film solid secondary battery according to claim 1, wherein the positive electrode current collector layer, the positive electrode active material layer, the solid electrolyte layer, the negative electrode active material layer, and the negative electrode current collector layer are formed by a sputtering method. .
  7. A thin-film solid secondary battery in which a positive electrode current collector layer, a positive electrode active material layer, a solid electrolyte layer, a negative electrode active material layer, and a negative electrode current collector layer are laminated in a predetermined thickness in this order or in the reverse order on a substrate. A manufacturing method of
    A preparation step for determining a maximum charge / discharge capacity per unit volume of each of the positive electrode active material layer and the negative electrode active material layer by a predetermined method;
    The ratio R of the reciprocal of the maximum charge / discharge capacity per unit volume of the positive electrode active material layer to the reciprocal of the maximum charge / discharge capacity per unit volume of the negative electrode active material layer calculated based on the value obtained in the preparation step; The film thickness ratio X of the positive electrode active material layer to the negative electrode active material layer satisfies the conditional expression 0.2R ≦ X ≦ 10R, and the film thicknesses of the positive electrode active material layer and the negative electrode active material layer are respectively The design process to be determined;
    A method for producing a thin film solid secondary battery, comprising: performing a film forming step of forming the positive electrode active material layer and the negative electrode active material layer in a predetermined film thickness determined in the design step.
JP2005290257A 2005-10-03 2005-10-03 Thin film solid secondary battery and method of manufacturing thin film solid secondary battery Pending JP2007103130A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2005290257A JP2007103130A (en) 2005-10-03 2005-10-03 Thin film solid secondary battery and method of manufacturing thin film solid secondary battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2005290257A JP2007103130A (en) 2005-10-03 2005-10-03 Thin film solid secondary battery and method of manufacturing thin film solid secondary battery

Publications (1)

Publication Number Publication Date
JP2007103130A true JP2007103130A (en) 2007-04-19

Family

ID=38029878

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2005290257A Pending JP2007103130A (en) 2005-10-03 2005-10-03 Thin film solid secondary battery and method of manufacturing thin film solid secondary battery

Country Status (1)

Country Link
JP (1) JP2007103130A (en)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008029888A1 (en) * 2006-09-07 2008-03-13 Toyota Jidosha Kabushiki Kaisha Negative electrode active material, negative electrode and lithium secondary battery
JP2009046340A (en) * 2007-08-17 2009-03-05 Ulvac Material Kk Method for producing lithium phosphate sintered compact, and sputtering target
JP2009181931A (en) * 2008-02-01 2009-08-13 Murata Mfg Co Ltd Battery
JP2010027414A (en) * 2008-07-22 2010-02-04 Murata Mfg Co Ltd Manufacturing method for battery
WO2010090125A1 (en) * 2009-02-03 2010-08-12 ソニー株式会社 Solid state thin film lithium ion secondary battery and manufacturing method therefor
WO2010090124A1 (en) * 2009-02-03 2010-08-12 ソニー株式会社 Solid state thin film lithium ion secondary battery and manufacturing method therefor
WO2010090126A1 (en) * 2009-02-03 2010-08-12 ソニー株式会社 Solid state thin film lithium ion secondary battery and manufacturing method therefor
JP2010242199A (en) * 2009-04-09 2010-10-28 Ulvac Japan Ltd Method for removing thin film adhering to vacuum part
JP2010251077A (en) * 2009-04-14 2010-11-04 Ulvac Japan Ltd Thin-film lithium ion secondary battery, protective film for thin-film lithium ion secondary battery and thin-film lithium ion secondary battery forming method
KR101084207B1 (en) * 2009-10-01 2011-11-17 삼성에스디아이 주식회사 Negative electrode for lithium battery, method for manufacturing the same and lithium battery comprising the same
JP2012059497A (en) * 2010-09-08 2012-03-22 Sony Corp Solid electrolyte battery
JP2012520552A (en) * 2009-03-16 2012-09-06 コミサリア ア レネルジー アトミック エ オ ゼネルジー アルテルナティブCommissariat A L’Energie Atomique Et Aux Energies Alternatives Lithium micro battery and manufacturing method thereof
JP2013060618A (en) * 2011-09-12 2013-04-04 Ulvac Japan Ltd Mask for forming solid electrolyte membrane and method for producing lithium secondary battery
KR20160133832A (en) * 2015-05-13 2016-11-23 주식회사 엘지화학 Method for manufacturing electrode for lithium-sulphur battery, and electrode for lithium-sulphur battery using the same
CN107615557A (en) * 2015-05-15 2018-01-19 应用材料公司 Manufacture hull cell in lithium depositing operation in use covering appts, the equipment for lithium depositing operation, manufacture hull cell electrode method and hull cell

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0574494A (en) * 1991-09-13 1993-03-26 Asahi Chem Ind Co Ltd Nonaqueous secondary battery
JPH06275321A (en) * 1993-03-18 1994-09-30 Toshiba Corp Lithium secondary battery
JP2000123873A (en) * 1998-10-16 2000-04-28 Sony Corp Solid electrolyte battery
JP2000268880A (en) * 1999-03-19 2000-09-29 Toyota Central Res & Dev Lab Inc Lithium secondary battery
JP2002151154A (en) * 2000-11-07 2002-05-24 Toyota Central Res & Dev Lab Inc Lithium secondary battery
JP2002203606A (en) * 2000-12-28 2002-07-19 Sony Corp Nonaqueous electrolyte solution battery
JP2002231312A (en) * 2001-01-29 2002-08-16 Japan Storage Battery Co Ltd Nonaqueous electrolyte secondary battery
JP2002352850A (en) * 2001-05-24 2002-12-06 Matsushita Electric Ind Co Ltd Chip cell and its manufacturing method
JP2004087229A (en) * 2002-08-26 2004-03-18 Sanyo Electric Co Ltd Lithium secondary battery
JP2004319449A (en) * 2003-04-02 2004-11-11 Matsushita Electric Ind Co Ltd Energy device and its manufacturing method
JP2004335133A (en) * 2003-04-30 2004-11-25 Matsushita Electric Ind Co Ltd Solid state battery
JP2004362809A (en) * 2003-06-02 2004-12-24 Nissan Motor Co Ltd Negative electrode for nonaqueous battery, nonaqueous battery using it, and method of manufacturing negative active material
JP2005150039A (en) * 2003-11-19 2005-06-09 Sanyo Electric Co Ltd Lithium secondary battery

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0574494A (en) * 1991-09-13 1993-03-26 Asahi Chem Ind Co Ltd Nonaqueous secondary battery
JPH06275321A (en) * 1993-03-18 1994-09-30 Toshiba Corp Lithium secondary battery
JP2000123873A (en) * 1998-10-16 2000-04-28 Sony Corp Solid electrolyte battery
JP2000268880A (en) * 1999-03-19 2000-09-29 Toyota Central Res & Dev Lab Inc Lithium secondary battery
JP2002151154A (en) * 2000-11-07 2002-05-24 Toyota Central Res & Dev Lab Inc Lithium secondary battery
JP2002203606A (en) * 2000-12-28 2002-07-19 Sony Corp Nonaqueous electrolyte solution battery
JP2002231312A (en) * 2001-01-29 2002-08-16 Japan Storage Battery Co Ltd Nonaqueous electrolyte secondary battery
JP2002352850A (en) * 2001-05-24 2002-12-06 Matsushita Electric Ind Co Ltd Chip cell and its manufacturing method
JP2004087229A (en) * 2002-08-26 2004-03-18 Sanyo Electric Co Ltd Lithium secondary battery
JP2004319449A (en) * 2003-04-02 2004-11-11 Matsushita Electric Ind Co Ltd Energy device and its manufacturing method
JP2004335133A (en) * 2003-04-30 2004-11-25 Matsushita Electric Ind Co Ltd Solid state battery
JP2004362809A (en) * 2003-06-02 2004-12-24 Nissan Motor Co Ltd Negative electrode for nonaqueous battery, nonaqueous battery using it, and method of manufacturing negative active material
JP2005150039A (en) * 2003-11-19 2005-06-09 Sanyo Electric Co Ltd Lithium secondary battery

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8507133B2 (en) 2006-09-07 2013-08-13 Toyota Jidosha Kabushiki Kaisha Anode active material, anode, and lithium secondary battery
WO2008029888A1 (en) * 2006-09-07 2008-03-13 Toyota Jidosha Kabushiki Kaisha Negative electrode active material, negative electrode and lithium secondary battery
JP2009046340A (en) * 2007-08-17 2009-03-05 Ulvac Material Kk Method for producing lithium phosphate sintered compact, and sputtering target
JP2009181931A (en) * 2008-02-01 2009-08-13 Murata Mfg Co Ltd Battery
JP2010027414A (en) * 2008-07-22 2010-02-04 Murata Mfg Co Ltd Manufacturing method for battery
JP2010205718A (en) * 2009-02-03 2010-09-16 Sony Corp Thin-film solid lithium-ion secondary battery and its manufacturing method
WO2010090126A1 (en) * 2009-02-03 2010-08-12 ソニー株式会社 Solid state thin film lithium ion secondary battery and manufacturing method therefor
JP2010182447A (en) * 2009-02-03 2010-08-19 Sony Corp Solid-state thin film lithium ion secondary battery, and method of manufacturing the same
JP2010182448A (en) * 2009-02-03 2010-08-19 Sony Corp Solid-state thin film lithium ion secondary battery and method of manufacturing the same
WO2010090124A1 (en) * 2009-02-03 2010-08-12 ソニー株式会社 Solid state thin film lithium ion secondary battery and manufacturing method therefor
US9673481B2 (en) 2009-02-03 2017-06-06 Sony Corporation Thin film solid state lithium ion secondary battery and method of manufacturing the same
CN102301520A (en) * 2009-02-03 2011-12-28 索尼公司 Thin film solid state lithium ion secondary battery and manufacturing method thereof
WO2010090125A1 (en) * 2009-02-03 2010-08-12 ソニー株式会社 Solid state thin film lithium ion secondary battery and manufacturing method therefor
US20110281167A1 (en) * 2009-02-03 2011-11-17 Sony Corporation Thin film solid state lithium ion secondary battery and method of manufacturing the same
CN102301518A (en) * 2009-02-03 2011-12-28 索尼公司 Thin film solid state lithium ion secondary battery and manufacturing method thereof
JP2012520552A (en) * 2009-03-16 2012-09-06 コミサリア ア レネルジー アトミック エ オ ゼネルジー アルテルナティブCommissariat A L’Energie Atomique Et Aux Energies Alternatives Lithium micro battery and manufacturing method thereof
JP2010242199A (en) * 2009-04-09 2010-10-28 Ulvac Japan Ltd Method for removing thin film adhering to vacuum part
JP2010251077A (en) * 2009-04-14 2010-11-04 Ulvac Japan Ltd Thin-film lithium ion secondary battery, protective film for thin-film lithium ion secondary battery and thin-film lithium ion secondary battery forming method
KR101084207B1 (en) * 2009-10-01 2011-11-17 삼성에스디아이 주식회사 Negative electrode for lithium battery, method for manufacturing the same and lithium battery comprising the same
JP2012059497A (en) * 2010-09-08 2012-03-22 Sony Corp Solid electrolyte battery
JP2013060618A (en) * 2011-09-12 2013-04-04 Ulvac Japan Ltd Mask for forming solid electrolyte membrane and method for producing lithium secondary battery
KR20160133832A (en) * 2015-05-13 2016-11-23 주식회사 엘지화학 Method for manufacturing electrode for lithium-sulphur battery, and electrode for lithium-sulphur battery using the same
KR101989498B1 (en) * 2015-05-13 2019-06-14 주식회사 엘지화학 Method for manufacturing electrode for lithium-sulphur battery, and electrode for lithium-sulphur battery using the same
CN107615557A (en) * 2015-05-15 2018-01-19 应用材料公司 Manufacture hull cell in lithium depositing operation in use covering appts, the equipment for lithium depositing operation, manufacture hull cell electrode method and hull cell
JP2018521219A (en) * 2015-05-15 2018-08-02 アプライド マテリアルズ インコーポレイテッドApplied Materials,Incorporated Masking device used in a lithium deposition process in the manufacture of a thin film battery, an apparatus configured for the lithium deposition process, a method for manufacturing an electrode of a thin film battery, and a thin film battery

Similar Documents

Publication Publication Date Title
Yin et al. Micrometer-scale amorphous Si thin-film electrodes fabricated by electron-beam deposition for Li-ion batteries
KR100826814B1 (en) Solid electrolyte cell
TWI466367B (en) A lithium ion secondary battery, an electrode for the secondary battery, an electrode for an electrolytic copper foil
EP2728652B1 (en) Secondary battery of improved lithium ion mobility and cell capacity
JP4777593B2 (en) Method for producing lithium ion secondary battery
JP4415241B2 (en) Negative electrode for secondary battery, secondary battery using the same, and method for producing negative electrode
US6143444A (en) Method of preparing an electrode for lithium based secondary cell
EP1391959B1 (en) Non-aqueous electrolyte secondary battery
JP2006066341A (en) Nonaqueous electrolyte secondary cell
JP5043338B2 (en) Lithium secondary battery
Tamura et al. Advanced structures in electrodeposited tin base negative electrodes for lithium secondary batteries
CN100421284C (en) Lithium secondary battery-use electrode and lithium secondary battery
JP4319250B2 (en) Current collector device and manufacturing method thereof
JP4225727B2 (en) Negative electrode for lithium secondary battery and lithium secondary battery
JP2006134770A (en) Cathode and battery
US10263277B2 (en) Flexible thin film solid state lithium ion batteries
US7901468B2 (en) Rechargeable battery and method for fabricating the same
JP5217076B2 (en) Lithium ion battery
JP4152086B2 (en) Electrode for lithium secondary battery and lithium secondary battery
Ramadass et al. Performance study of commercial LiCoO2 and spinel-based Li-ion cells
JP4321584B2 (en) Negative electrode for secondary battery and secondary battery
US6280873B1 (en) Wound battery and method for making it
KR101500545B1 (en) Negative electrode and secondary cell
KR100728441B1 (en) Cathode for battery and battery using thereof
WO1994019836A1 (en) Electrodes for rechargeable lithium batteries

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20080926

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20110614

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20110628

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20110825

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20120417

A02 Decision of refusal

Free format text: JAPANESE INTERMEDIATE CODE: A02

Effective date: 20120814