JPH09102320A - Solid electrolyte battery and its manufacture - Google Patents
Solid electrolyte battery and its manufactureInfo
- Publication number
- JPH09102320A JPH09102320A JP7282609A JP28260995A JPH09102320A JP H09102320 A JPH09102320 A JP H09102320A JP 7282609 A JP7282609 A JP 7282609A JP 28260995 A JP28260995 A JP 28260995A JP H09102320 A JPH09102320 A JP H09102320A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- solid electrolyte
- electrolyte battery
- electrode material
- battery
- Prior art date
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Classifications
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- 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
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、正極と負極との
間に高分子固体電解質を備えた固体電解質電池及びこの
ような固体電解質電池の製造方法に係り、正極と高分子
固体電解質高分子固体電解質との界面抵抗が少なく、放
電特性に優れると共に、二次電池として使用する場合
に、大電流での充放電が行なえ、充放電サイクル特性に
も優れた固体電解質電池及びこの固体電解質電池の製造
方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid electrolyte battery having a polymer solid electrolyte between a positive electrode and a negative electrode, and a method for manufacturing such a solid electrolyte battery. Manufacture of a solid electrolyte battery and an excellent solid-state electrolyte battery that has low interface resistance with an electrolyte and is excellent in discharge characteristics, and can be charged and discharged at a large current when used as a secondary battery, and is also excellent in charge-discharge cycle characteristics. It is about the method.
【０００２】[0002]
【従来の技術】従来より、電池における電解質として
は、一般に水系或いは非水系の電解液が使用されていた
が、近年、このような液体の電解質に代えて、高分子で
構成された高分子固体電解質を用いた固体電解質電池が
注目されるようになった。すなわち、このような固体電
解質電池は電解質が液体でないため、漏液の心配がな
く、腐食性も小さく、また電解液の注液等を必要とせ
ず、電池構造が簡単で、その組立ても容易になる等の利
点があった。2. Description of the Related Art Conventionally, an aqueous or non-aqueous electrolyte has been generally used as an electrolyte in a battery. In recent years, instead of such a liquid electrolyte, a polymer solid composed of a polymer has been used. Attention has been focused on solid electrolyte batteries using electrolytes. That is, in such a solid electrolyte battery, since the electrolyte is not a liquid, there is no fear of liquid leakage, the corrosiveness is small, and there is no need to inject the electrolytic solution, the battery structure is simple, and its assembly is easy. There were advantages such as becoming.
【０００３】ここで、このような固体電解質電池を製造
するにあたり、従来においては、正極上に高分子固体電
解質用のモノマー材料を塗布し、これに紫外線や電子線
を照射して、このモノマー材料を重合させて高分子固体
電解質を形成することが行なわれていた。Here, in manufacturing such a solid electrolyte battery, conventionally, a monomer material for a polymer solid electrolyte is coated on a positive electrode, and this monomer material is irradiated with ultraviolet rays or electron beams. Was polymerized to form a polymer solid electrolyte.
【０００４】しかし、このように正極上に高分子固体電
解質用のモノマー材料を塗布して紫外線や電子線を照射
させた場合、上記正極と高分子固体電解質との界面部分
における正極材料が上記のモノマー材料と反応し、また
電子線によるエネルギー等によって不活性化し、これに
より高分子固体電解質との界面部分における正極材料が
劣化する。そして、正極と高分子固体電解質との界面抵
抗が増大し、得られた電池における放電容量が低下し、
また二次電池として使用した場合に、大電流での充放電
が困難になり、また充放電サイクル特性が低下する等の
問題があった。However, when the monomer material for polymer solid electrolyte is coated on the positive electrode and irradiated with ultraviolet rays or electron beams, the positive electrode material at the interface between the positive electrode and the polymer solid electrolyte is as described above. It reacts with the monomer material and is inactivated by the energy of the electron beam or the like, which deteriorates the positive electrode material at the interface with the solid polymer electrolyte. Then, the interface resistance between the positive electrode and the solid polymer electrolyte increases, and the discharge capacity of the obtained battery decreases.
Further, when used as a secondary battery, there are problems that charging / discharging with a large current becomes difficult, and charging / discharging cycle characteristics deteriorate.
【０００５】[0005]
【発明が解決しようとする課題】この発明は、正極と負
極との間に高分子固体電解質が設けられた固体電解質電
池における上記のような問題を解決することを課題とす
るものであり、正極上に高分子固体電解質を形成する際
に、高分子固体電解質との界面において正極材料が劣化
するのを抑制し、正極と高分子固体電解質との界面抵抗
を低くすることができ、放電特性に優れると共に、二次
電池として使用する場合に、大電流での充放電が行な
え、充放電サイクル特性にも優れた固体電解質電池が得
られるようにすることを課題とするものである。SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems in a solid electrolyte battery in which a polymer solid electrolyte is provided between a positive electrode and a negative electrode. When forming a solid polymer electrolyte on the very top, it is possible to suppress deterioration of the positive electrode material at the interface with the solid polymer electrolyte, and it is possible to reduce the interfacial resistance between the positive electrode and the solid polymer electrolyte, and to improve discharge characteristics. An object of the present invention is to obtain a solid electrolyte battery which is excellent and can be charged and discharged with a large current when used as a secondary battery, and has excellent charge and discharge cycle characteristics.
【０００６】[0006]
【課題を解決するための手段】この発明における固体電
解質電池においては、上記のような課題を解決するた
め、正極と負極との間に高分子固体電解質を備える固体
電解質電池において、正極と高分子固体電解質の界面部
分において、上記正極における正極材料と結晶性の異な
る正極材料の層を形成するようにしたのである。In the solid electrolyte battery of the present invention, in order to solve the above problems, in a solid electrolyte battery having a polymer solid electrolyte between a positive electrode and a negative electrode, the positive electrode and the polymer At the interface portion of the solid electrolyte, a layer of a positive electrode material having a crystallinity different from that of the positive electrode material of the positive electrode is formed.
【０００７】また、この発明における固体電解質電池の
製造方法においては、上記のような課題を解決するた
め、正極と負極との間に高分子固体電解質を備える固体
電解質電池を製造するにあたり、正極上に高分子固体電
解質を形成する前に、高分子固体電解質との界面部分に
物理的手法により正極における正極材料と結晶性の異な
る正極材料の層を形成するようにしたのである。Further, in order to solve the above-mentioned problems, in the method for manufacturing a solid electrolyte battery according to the present invention, in manufacturing a solid electrolyte battery including a polymer solid electrolyte between a positive electrode and a negative electrode, Before forming the solid polymer electrolyte, a layer of a positive electrode material having a different crystallinity from the positive electrode material in the positive electrode was formed by a physical method at the interface with the solid polymer electrolyte.
【０００８】この発明のように、正極と高分子固体電解
質との界面部分において、正極における正極材料と結晶
性の異なる正極材料の層を設けると、前記のように正極
上に高分子固体電解質用のモノマー材料を塗布し、これ
に紫外線や電子線を照射して、このモノマー材料を重合
させて高分子固体電解質を形成する際に、上記の結晶性
の異なる正極材料の層により、正極を構成する正極材料
が上記のモノマー材料と反応したり、電子線等のエネル
ギーにより不活性化して劣化するのが抑制され、これに
より正極と高分子固体電解質との界面抵抗の増大が抑制
され、放電特性が向上すると共に、二次電池として使用
する場合においても、大電流での充放電が可能となると
共に、充放電サイクル特性も向上すると考えられる。When a layer of a positive electrode material having a crystallinity different from that of the positive electrode material in the positive electrode is provided at the interface between the positive electrode and the solid polymer electrolyte as in the present invention, the solid polymer electrolyte for the positive electrode is formed on the positive electrode as described above. Of the positive electrode material having different crystallinity when forming a solid polymer electrolyte by polymerizing this monomer material by irradiating it with ultraviolet rays or an electron beam. It is suppressed that the positive electrode material that reacts with the above-mentioned monomer material or is inactivated by the energy of the electron beam or the like and deteriorates, thereby suppressing the increase in the interfacial resistance between the positive electrode and the solid polymer electrolyte, and the discharge characteristics. It is considered that, when used as a secondary battery, charging and discharging can be performed with a large current, and charging and discharging cycle characteristics are also improved.
【０００９】ここで、上記のように正極における正極材
料と結晶性の異なる正極材料の層を形成する物理的方法
としては、スパッタ法，ＣＶＤ法，真空蒸着法等を使用
することができ、この結晶性の異なる正極材料の層につ
いては、モノマー材料との反応や、電子線等のエネルギ
ーによる劣化が少ない非晶質の正極材料の層を形成する
ことが好ましい。Here, as a physical method for forming a layer of a positive electrode material having a crystallinity different from that of the positive electrode material in the positive electrode as described above, a sputtering method, a CVD method, a vacuum deposition method or the like can be used. As for the layers of the positive electrode material having different crystallinity, it is preferable to form an amorphous positive electrode material layer which is less likely to be deteriorated due to the reaction with the monomer material or the energy such as electron beam.
【００１０】また、上記のように正極と高分子固体電解
質との界面部分に形成する結晶性の異なる正極材料の層
の厚みについては、その厚みが薄すぎると、この結晶性
の異なる正極材料の層によって正極を構成する正極材料
の劣化を十分に抑制することができなくなる一方、その
厚みが厚すぎると、正極を構成する正極材料におけるイ
オンの吸蔵・放出が抑制されるため、結晶性の異なる正
極材料の層を形成する場合、その厚みを０．１〜１μｍ
の範囲にすることが好ましい。Regarding the thickness of the layer of the positive electrode material having different crystallinity formed at the interface between the positive electrode and the solid polymer electrolyte as described above, when the thickness is too thin, the positive electrode material having different crystallinity is formed. While it becomes impossible to sufficiently suppress the deterioration of the positive electrode material that constitutes the positive electrode by the layer, if the thickness is too thick, the absorption and desorption of ions in the positive electrode material that constitutes the positive electrode is suppressed, so that the crystallinity is different. When forming the layer of the positive electrode material, the thickness thereof is 0.1 to 1 μm.
It is preferable to be within the range.
【００１１】また、上記の正極を構成する正極材料と、
高分子固体電解質との界面に形成する結晶性の異なる正
極材料の層を構成する正極材料とは同じ材料であって
も、異なった材料であっても良いが、正極としての特性
が似たものを使用することが好ましく、特に、上記のよ
うなモノマー材料との反応や、電子線等のエネルギーに
よる劣化を抑制する点からは、上記の正極を構成する正
極材料及び結晶性の異なる正極材料がリチウムの吸蔵・
放出が可能な遷移金属酸化物で構成されている場合に有
効である。Further, a positive electrode material constituting the above positive electrode,
The positive electrode material forming the layer of the positive electrode material having different crystallinity formed at the interface with the solid polymer electrolyte may be the same material or different material, but the characteristics of the positive electrode are similar. In particular, from the viewpoint of suppressing the reaction with the monomer material as described above and deterioration due to energy such as an electron beam, the positive electrode material and the positive electrode material having different crystallinity constituting the above positive electrode are Storage of lithium
It is effective when it is composed of a transition metal oxide that can be released.
【００１２】ここで、このようなリチウムの吸蔵・放出
が可能な遷移金属酸化物を、正極を構成する正極材料
や、結晶性の異なる正極材料の層に使用する場合、例え
ば、正極を構成する正極材料に、結晶性のＬｉＣｏＯ
2 ，ＬｉＭｎＯ2 ，ＬｉＮｉＯ2，ＬｉＦｅＯ2 ，Ｌｉ
ＴｉＯ2 ，ＬｉＣｒＯ2 のいずれかを使用した場合に
は、結晶性の異なる正極材料の層に、非晶質のＬｉＣｏ
Ｏ2 ，ＬｉＭｎＯ2 ，ＬｉＮｉＯ2 ，ＬｉＦｅＯ2 ，Ｌ
ｉＴｉＯ2 ，ＬｉＣｒＯ2 のいずれかを選択して使用す
ることができる。Here, when such a transition metal oxide capable of inserting and extracting lithium is used for a positive electrode material constituting a positive electrode or a layer of a positive electrode material having different crystallinity, for example, it constitutes a positive electrode. For the positive electrode material, crystalline LiCoO 2
2, LiMnO 2, LiNiO 2, LiFeO 2, Li
When either TiO 2 or LiCrO 2 is used, amorphous LiCo is formed on the layer of the positive electrode material having different crystallinity.
O 2, LiMnO 2, LiNiO 2 , LiFeO 2, L
Either iTiO 2 or LiCrO 2 can be selected and used.
【００１３】また、上記のように正極材料にリチウムの
吸蔵・放出が可能な遷移金属酸化物を使用してリチウム
イオンを高分子固体電解質を通して移動させる場合、負
極材料としては、金属リチウム或いはリチウムの吸蔵・
放出が可能な合金、金属酸化物、炭素材料等が使用され
る。ここで、上記の合金としては、例えば、Ｌｉ−Ａｌ
合金，Ｌｉ−Ｉｎ合金，Ｌｉ−Ｓｎ合金，Ｌｉ−Ｐｂ合
金，Ｌｉ−Ｂｉ合金，Ｌｉ−Ｇａ合金，Ｌｉ−Ｓｒ合
金，Ｌｉ−Ｓｉ合金，Ｌｉ−Ｚｎ合金，Ｌｉ−Ｃｄ合
金，Ｌｉ−Ｃａ合金，Ｌｉ−Ｂａ合金等のリチウム合金
を、また上記の金属酸化物としては、例えば、Ｆｅ2 Ｏ
3 ，ＴｉＯ2 ，Ｎｂ2 Ｏ3 ，ＷＯ3 等の金属酸化物を、
また上記の炭素材料としては、例えば、天然黒鉛，人造
黒鉛，無定形炭素等を使用することができる。When a lithium metal is used as the positive electrode material to move lithium ions through the polymer solid electrolyte by using a transition metal oxide capable of inserting and extracting lithium, the negative electrode material may be metallic lithium or lithium. Occlusion
Releaseable alloys, metal oxides, carbon materials, etc. are used. Here, as the above-mentioned alloy, for example, Li-Al
Alloy, Li-In alloy, Li-Sn alloy, Li-Pb alloy, Li-Bi alloy, Li-Ga alloy, Li-Sr alloy, Li-Si alloy, Li-Zn alloy, Li-Cd alloy, Li-Ca Alloys, lithium alloys such as Li-Ba alloys, and the above metal oxides include, for example, Fe 2 O.
Metal oxides such as 3 , TiO 2 , Nb 2 O 3 and WO 3 ,
Further, as the above-mentioned carbon material, for example, natural graphite, artificial graphite, amorphous carbon or the like can be used.
【００１４】また、上記のようにリチウムイオンを移動
させる場合において、この高分子固体電解質に加える溶
質としては、例えば、トリフルオロメタンスルホン酸リ
チウムＬｉＣＦ3 ＳＯ3 ，ヘキサフルオロリン酸リチウ
ムＬｉＰＦ6 ，テトラフルオロホウ酸リチウムＬｉＢＦ
4 ，過塩素酸リチウムＬｉＣｌＯ4 ，トリフルオロメタ
ンスルホン酸イミドリチウムＬｉＮ（ＣＦ3 ＳＯ2 ）2
等を使用することができる。When the lithium ions are moved as described above, the solute to be added to the polymer solid electrolyte is, for example, lithium trifluoromethanesulfonate LiCF 3 SO 3 , lithium hexafluorophosphate LiPF 6 , tetrafluoromethane. Lithium borate LiBF
4 , lithium perchlorate LiClO 4 , trifluoromethanesulfonic acid imide lithium LiN (CF 3 SO 2 ) 2
Etc. can be used.
【００１５】また、高分子固体電解質に上記のような溶
質を加えるにあたっては、上記の溶質を溶解する溶媒を
加え、上記の高分子固体電解質をゲル状にして使用する
こともでき、このような溶媒としては、例えば、プロピ
レンカーボネート，エチレンカーボネート，γ−ブチロ
ラクトン，ブチレンカーボネート，１，２−ジメトキシ
エタン，ジメチルカーボネート，ジエチルカーボネート
等を使用することができる。In addition, when adding the above-mentioned solute to the polymer solid electrolyte, it is also possible to add a solvent for dissolving the above-mentioned solute to make the above-mentioned polymer solid electrolyte into a gel and use it. As the solvent, for example, propylene carbonate, ethylene carbonate, γ-butyrolactone, butylene carbonate, 1,2-dimethoxyethane, dimethyl carbonate, diethyl carbonate or the like can be used.
【００１６】[0016]
【実施例】以下、この発明に係る固体電解質電池及びそ
の製造方法について実施例を挙げて具体的に説明すると
共に、比較例を挙げ、この実施例に係る固体電解質電池
が放電特性や充放電サイクル特性の点において優れてい
ることを明らかにする。なお、この発明における固体電
解質電池は下記の実施例に示したものに限定されるもの
ではなく、その要旨を変更しない範囲において適宜変更
して実施できるものである。EXAMPLES Hereinafter, the solid electrolyte battery and the method for producing the same according to the present invention will be specifically described with reference to Examples, and comparative examples will be given. The solid electrolyte batteries according to this Example show discharge characteristics and charge / discharge cycles. It reveals that it is superior in terms of characteristics. The solid electrolyte battery according to the present invention is not limited to the ones shown in the following examples, and can be implemented by appropriately changing it without departing from the scope of the invention.
【００１７】［実施例１］この実施例においては、正
極，負極及び高分子固体電解質を下記のようにして作製
し、図１に示すような扁平型の固体電解質二次電池を得
るようにした。[Example 1] In this example, a positive electrode, a negative electrode and a polymer solid electrolyte were prepared as follows to obtain a flat type solid electrolyte secondary battery as shown in FIG. .
【００１８】（正極の作製）正極材料としては７００〜
９００℃の温度で熱処理したリチウム含有二酸化コバル
トＬｉＣｏＯ2 を用い、このリチウム含有二酸化コバル
トと、導電剤であるカーボン粉末と、結着剤であるフッ
素樹脂粉末とを８５：１０：５の重量比で混合し、この
混合物をドクターブレード法により正極集電体５上に塗
布した後、これを１００〜１５０℃で真空熱処理し、厚
さが約７０μｍ、直径が１０ｍｍの円板状になった正極
１を得た。なお、正極集電体５にはフェライト系ステン
レス鋼を使用した。(Production of Positive Electrode) The positive electrode material is 700 to
Using lithium-containing cobalt dioxide LiCoO 2 heat-treated at a temperature of 900 ° C., this lithium-containing cobalt dioxide, carbon powder as a conductive agent, and fluororesin powder as a binder were mixed at a weight ratio of 85: 10: 5. After mixing and applying this mixture on the positive electrode current collector 5 by the doctor blade method, this was subjected to vacuum heat treatment at 100 to 150 ° C. to form a disk-shaped positive electrode 1 having a thickness of about 70 μm and a diameter of 10 mm. Got In addition, ferritic stainless steel was used for the positive electrode current collector 5.
【００１９】次に、このようにして作製した正極１上に
対して、下記の表１に示すスパッタ条件でスパッタリン
グを行ない、上記の正極材料と結晶性が異なる非晶質の
リチウム含有二酸化コバルトＬｉＣｏＯ2 により厚みが
約０．７５μｍになった非晶質層１ａを上記の正極１上
に形成した。Next, the positive electrode 1 thus produced was subjected to sputtering under the sputtering conditions shown in Table 1 below, and amorphous lithium-containing cobalt dioxide LiCoO 2 having crystallinity different from that of the above positive electrode material. the amorphous layer 1a of thickness by 2 became about 0.75μm was formed on the positive electrode 1 above.
【００２０】[0020]
【表１】 [Table 1]
【００２１】（負極の作製）負極材料としては黒鉛粉末
を用い、この黒鉛粉末と結着剤であるフッ素樹脂とを９
５：５の重量比で混合し、この混合物をドクターブレー
ド法により負極集電体６上に塗布した後、これを１００
〜１５０℃で真空熱処理して、厚みが約５０μｍ，直径
が１０ｍｍの円板状になった負極２を得た。なお、負極
集電体６にはフェライト系ステンレス鋼を使用した。(Production of Negative Electrode) Graphite powder was used as a negative electrode material, and the graphite powder and a fluororesin as a binder were mixed with each other.
The mixture was mixed in a weight ratio of 5: 5, and the mixture was applied onto the negative electrode current collector 6 by the doctor blade method, and then this was mixed with 100
Vacuum heat treatment was performed at ˜150 ° C. to obtain a disk-shaped negative electrode 2 having a thickness of about 50 μm and a diameter of 10 mm. In addition, ferritic stainless steel was used for the negative electrode current collector 6.
【００２２】（高分子固体電解質の作製）高分子固体電
解質におけるモノマー材料に、下記の化１に示す分子量
が約１０００のアクリレート系モノマーを用い、このモ
ノマー材料に対し、エチレンカーボネートとジメチルカ
ーボネートとが４：６の割合になった混合溶媒に過塩素
酸リチウムＬｉＣｌＯ4 を１ｍｏｌ／ｌ溶解させた電解
液を重量比１：３の割合で混合させて高分子固体電解質
用の溶液を調製し、この高分子固体電解質用の溶液を上
記のようにして作製した正極１上における非晶質層１ａ
の上に２５〜１００μｍの厚みになるように塗布し、そ
の後、この高分子固体電解質形成用溶液にエレクトロカ
ーテン式電子線照射装置から出力２００ｋＶ、照射線量
２〜５Ｍｒａｄで電子線を照射して上記のモノマー材料
を重合させ、上記の非晶質層１ａ上にゲル状になった高
分子固体電解質３を作製した。(Preparation of Solid Polymer Electrolyte) An acrylate-based monomer having a molecular weight of about 1000 shown in the following chemical formula 1 is used as a monomer material in the solid polymer electrolyte, and ethylene carbonate and dimethyl carbonate are added to the monomer material. An electrolyte solution in which 1 mol / l of lithium perchlorate LiClO 4 was dissolved in a mixed solvent having a ratio of 4: 6 was mixed at a weight ratio of 1: 3 to prepare a solution for a polymer solid electrolyte. Amorphous layer 1a on the positive electrode 1 prepared by the above-mentioned solution for solid polymer electrolyte
To a thickness of 25 to 100 μm, and then the solution for forming a polymer solid electrolyte is irradiated with an electron beam at an output of 200 kV and an irradiation dose of 2 to 5 Mrad from the electrocurtain type electron beam irradiation device. The monomer material of 1 was polymerized to prepare a gelled polymer solid electrolyte 3 on the amorphous layer 1a.
【００２３】[0023]
【化１】 Embedded image
【００２４】（電池の作製）そして、この実施例１の固
体電解質電池においては、図１に示すように、上記のよ
うにして作製した高分子固体電解質３の上に上記の負極
１を重ね、正極１における非晶質層１ａと負極２との間
に高分子固体電解質３を挾むようにして正極缶４ａと負
極缶４ｂとが形成する電池ケース４内に収容させ、正極
集電体５を介して正極１を正極缶４ａに接続させる一
方、負極集電体６を介して負極２を負極缶４ｂに接続さ
せ、この正極缶４ａと負極缶４ｂとを絶縁性パッキン７
により電気的に絶縁し、この電池内部で生じた化学エネ
ルギーを正極缶４ａと負極缶４ｂの両端子から電気エネ
ルギーとして外部へ取り出すようにした。(Preparation of Battery) In the solid electrolyte battery of Example 1, as shown in FIG. 1, the negative electrode 1 was placed on the solid polymer electrolyte 3 prepared as described above. The solid polymer electrolyte 3 is sandwiched between the amorphous layer 1a and the negative electrode 2 in the positive electrode 1 and housed in the battery case 4 formed by the positive electrode can 4a and the negative electrode can 4b. While the positive electrode 1 is connected to the positive electrode can 4a, the negative electrode 2 is connected to the negative electrode can 4b through the negative electrode current collector 6, and the positive electrode can 4a and the negative electrode can 4b are insulated by the insulating packing 7
The electric energy is electrically insulated by means of and the chemical energy generated inside the battery is taken out as electric energy from both terminals of the positive electrode can 4a and the negative electrode can 4b.
【００２５】［比較例１］この比較例においては、上記
実施例１の固体電解質電池において正極１上に非晶質層
１ａを設ける工程をなくし、それ以外については、上記
実施例１の場合とと同様にして、図２に示す固体電解質
電池を作製した。[Comparative Example 1] In this comparative example, the step of providing the amorphous layer 1a on the positive electrode 1 in the solid electrolyte battery of the above-mentioned Example 1 was omitted, and other than that, the case of the above-mentioned Example 1 was omitted. The solid electrolyte battery shown in FIG. 2 was produced in the same manner as in.
【００２６】次に、上記のようにして作製した実施例１
及び比較例１の各固体電解質電池について、それぞれ温
度２５℃の雰囲気下において、充電電流密度５００μＡ
／ｃｍ2 で４．２０Ｖまで充電した後、放電電流密度５
００μＡ／ｃｍ2 で２．５０Ｖまで放電し、このような
充放電のサイクルを繰り返して行ない、サイクル数の増
加に伴う放電容量の変化を測定して、これらの固体電解
質電池における充放電サイクル特性を調べ、その結果を
図３に示した。Next, Example 1 manufactured as described above was used.
And each solid electrolyte battery of Comparative Example 1 under a temperature of 25 ° C., a charging current density of 500 μA
Discharge current density of 5 after charging to 4.20 V at 1 / cm 2
The solid-state battery was discharged to 2.50 V at 00 μA / cm 2 and the charging / discharging cycle was repeated, and the change in the discharging capacity with the increase in the number of cycles was measured to determine the charging / discharging cycle characteristics of these solid electrolyte batteries. The investigation was conducted and the results are shown in FIG.
【００２７】この結果、正極１と高分子固体電解質３と
の間に正極１における正極材料と結晶性の異なる非晶質
層１ａを形成した実施例１の固体電解質電池は、非晶質
層１ａを形成しなかった比較例１の固体電解質電池に比
べて、サイクル数の増加に伴う放電容量の減少が著しく
少なくなっており、充放電サイクル特性が非常に向上し
ていた。As a result, the solid electrolyte battery of Example 1 in which the amorphous layer 1a having a crystallinity different from that of the positive electrode material in the positive electrode 1 was formed between the positive electrode 1 and the solid polymer electrolyte 3 was the amorphous layer 1a. Compared to the solid electrolyte battery of Comparative Example 1 in which the battery was not formed, the decrease in discharge capacity with the increase in the number of cycles was significantly reduced, and the charge / discharge cycle characteristics were significantly improved.
【００２８】また、実施例１と比較例１の固体電解質電
池について、上記のように温度２５℃の雰囲気下で、充
電電流密度５００μＡ／ｃｍ2 で４．２０Ｖまで充電さ
せた後、放電電流密度５００μＡ／ｃｍ2 で２．５０Ｖ
まで放電させるようにして、これらの各固体電解質電池
における充放電特性を調べた。ここで、充放電特性を調
べるにあたっては、縦軸に電池電圧、横軸に充放電容量
をとり、充放電容量による電池電圧の変動を調べ、その
結果を図４に示した。なお、同図においては、実施例１
の固体電解質電池における結果を実線で、比較例１の固
体電解質電池における結果を破線で示すと共に、放電時
における結果を太線で、充電時における結果を細線で示
した。Further, the solid electrolyte batteries of Example 1 and Comparative Example 1 were charged at a charging current density of 500 μA / cm 2 to 4.20 V in the atmosphere at a temperature of 25 ° C. as described above, and then discharged at a discharge current density. 2.50 V at 500 μA / cm 2
The charging / discharging characteristics of each of these solid electrolyte batteries were examined by discharging the solid electrolyte batteries. Here, in examining the charge / discharge characteristics, the vertical axis represents the battery voltage, and the horizontal axis represents the charge / discharge capacity. The variation of the battery voltage due to the charge / discharge capacity was investigated, and the results are shown in FIG. In addition, in FIG.
The results for the solid electrolyte battery of No. 2 are shown by a solid line, the results for the solid electrolyte battery of Comparative Example 1 are shown by a broken line, the results at the time of discharging are shown by a thick line, and the results at the time of charging are shown by a thin line.
【００２９】この結果、上記のように非晶質層１ａを設
けた実施例１の固体電解質電池は、非晶質層１ａを設け
ていない比較例１の固体電解質電池に比べて、放電時に
おける電池電圧の変動が少なく、比較例１の電池に比べ
て放電特性が優れていた。As a result, the solid electrolyte battery of Example 1 provided with the amorphous layer 1a as described above has a higher discharge time than the solid electrolyte battery of Comparative Example 1 not provided with the amorphous layer 1a. The fluctuation of the battery voltage was small, and the discharge characteristics were superior to those of the battery of Comparative Example 1.
【００３０】次に、上記実施例１における固体電解質電
池において、上記のように正極１を作製した後、この正
極１上に非晶質ＬｉＣｏＯ2 からなる非晶質層１ａを形
成するにあたり、この非晶質層１ａの厚みを変化させた
複数の固体電解質電池を作製した。Next, in the solid electrolyte battery of Example 1, the positive electrode 1 was prepared as described above, and then the amorphous layer 1a made of amorphous LiCoO 2 was formed on the positive electrode 1. A plurality of solid electrolyte batteries having different thicknesses of the amorphous layer 1a were produced.
【００３１】そして、このように非晶質層１ａの厚みが
異なった各固体電解質電池に対し、上記の充放電条件と
同じ条件で充放電を５０サイクル行ない、その時点での
各固体電解質電池における容量保存率を測定し、上記の
非晶質層１ａの厚みと容量保存率との関係を調べ、その
結果を図５に示した。Then, for each solid electrolyte battery having the amorphous layer 1a having a different thickness as described above, 50 cycles of charge and discharge are performed under the same conditions as the above charge and discharge conditions, and in each solid electrolyte battery at that time. The capacity storage rate was measured, and the relationship between the thickness of the amorphous layer 1a and the capacity storage rate was examined, and the results are shown in FIG.
【００３２】この結果、上記の非晶質層１ａの厚みが
０．１〜１．０μｍの範囲では容量保存率が９０％以上
で、容量保存率の低下が少なかったのに対して、非晶質
層１ａの厚みが０．１μｍより薄い場合や、１μｍより
厚い場合には、容量保存率が低下していた。As a result, when the thickness of the amorphous layer 1a is in the range of 0.1 to 1.0 μm, the capacity retention rate is 90% or more, and the decrease in the capacity retention rate was small, whereas the amorphous layer 1a was amorphous. When the thickness of the textured layer 1a was thinner than 0.1 μm or thicker than 1 μm, the capacity retention rate was low.
【００３３】［実施例２］この実施例においては、上記
実施例１の固体電解質電池における正極１の部分だけを
変更し、それ以外については上記実施例１と同様にして
固体電解質電池を作製した。Example 2 In this example, a solid electrolyte battery was manufactured in the same manner as in Example 1 except that only the positive electrode 1 portion in the solid electrolyte battery of Example 1 was changed. .
【００３４】ここで、この実施例２においては、正極１
を作製するにあたり、原料として炭酸リチウムＬｉＣＯ
3 と二酸化マンガンＭｎＯ2 を用い、これらを大気中で
７００〜１０００℃の温度で２０時間熱処理して得たリ
チウム含有二酸化マンガンＬｉＭｎＯ2 を正極材料とし
て使用し、このリチウム含有二酸化マンガンと、導電剤
であるカーボン粉末と、結着剤であるフッ素樹脂粉末と
を８５：１０：５の重量比で混合し、この混合物をドク
ターブレード法により正極集電体５上に塗布した後、こ
れを１００〜１５０℃で真空熱処理し、厚さが約７０μ
ｍ、直径が１０ｍｍの円板状になった正極１を作製し
た。Here, in this Example 2, the positive electrode 1
LiCO 3 as a raw material for producing
Lithium-containing manganese dioxide LiMnO 2 obtained by heat-treating 3 and manganese dioxide MnO 2 in the air at a temperature of 700 to 1000 ° C. for 20 hours was used as a positive electrode material. Of the carbon powder and the fluororesin powder of the binder are mixed in a weight ratio of 85: 10: 5, and the mixture is applied on the positive electrode current collector 5 by the doctor blade method, and then 100- Vacuum heat treatment at 150 ℃, thickness about 70μ
A disk-shaped positive electrode 1 having a diameter of m and a diameter of 10 mm was produced.
【００３５】その後は、この正極１上に上記実施例１の
場合と同様にして、非晶質のリチウム含有二酸化コバル
トＬｉＣｏＯ2 からなる厚みが約０．７５μｍになった
非晶質層１ａを形成した。Thereafter, the amorphous layer 1a made of amorphous lithium-containing cobalt dioxide LiCoO 2 and having a thickness of about 0.75 μm is formed on the positive electrode 1 in the same manner as in the first embodiment. did.
【００３６】［比較例２］この比較例においては、上記
実施例２の固体電解質電池において正極１上に非晶質層
１ａを設ける工程をなくし、それ以外については、上記
実施例２と同様にして固体電解質電池を作製した。[Comparative Example 2] In this comparative example, the step of providing the amorphous layer 1a on the positive electrode 1 in the solid electrolyte battery of the above-described Example 2 was omitted, and otherwise the same as in Example 2 above. Then, a solid electrolyte battery was produced.
【００３７】次に、上記のようにして作製した実施例２
及び比較例２の各固体電解質電池に対して、上記実施例
１及び比較例１の場合と同様にして充放電を行ない、充
放電のサイクル数の増加に伴う放電容量の変化を測定
し、これらの固体電解質電池における充放電サイクル特
性を調べ、その結果を図６に示した。Next, Example 2 produced as described above
And each solid electrolyte battery of Comparative Example 2 was charged and discharged in the same manner as in Example 1 and Comparative Example 1 above, and the change in discharge capacity with the increase in the number of charge and discharge cycles was measured. The charge / discharge cycle characteristics of the solid electrolyte battery of No. 3 were investigated, and the results are shown in FIG.
【００３８】この結果、正極１と高分子固体電解質３と
の間に正極１における正極材料と結晶性の異なる非晶質
層１ａを形成した実施例２の固体電解質電池は、非晶質
層１ａを形成しなかった比較例２の固体電解質電池に比
べて、サイクル数の増加に伴う放電容量の減少が著しく
少なくなっており、充放電サイクル特性が非常に向上し
ていた。As a result, the solid electrolyte battery of Example 2 in which the amorphous layer 1a having a crystallinity different from that of the positive electrode material in the positive electrode 1 was formed between the positive electrode 1 and the solid polymer electrolyte 3 was the amorphous layer 1a. Compared with the solid electrolyte battery of Comparative Example 2 in which the battery was not formed, the decrease in discharge capacity with the increase in the number of cycles was significantly reduced, and the charge / discharge cycle characteristics were greatly improved.
【００３９】［実施例３］この実施例においても、上記
実施例１の固体電解質電池における正極１の部分だけを
変更し、それ以外については、上記実施例１と同様にし
て固体電解質電池を作製した。[Example 3] Also in this example, a solid electrolyte battery was prepared in the same manner as in Example 1 except that only the positive electrode 1 portion in the solid electrolyte battery of Example 1 was changed. did.
【００４０】ここで、この実施例３においては、正極１
を作製するにあたり、原料として水酸化リチウムＬｉＯ
Ｈと水酸化ニッケルＮｉ（ＯＨ）2 を用い、これらを酸
素雰囲気中で７００〜８００℃の温度で２０時間熱処理
して得たリチウム含有二酸化ニッケルＬｉＮｉＯ2 を正
極材料として使用し、このリチウム含有二酸化ニッケル
と、導電剤であるカーボン粉末と、結着剤であるフッ素
樹脂粉末とを８５：１０：５の重量比で混合し、この混
合物をドクターブレード法により正極集電体５上に塗布
した後、これを１００〜１５０℃で真空熱処理し、厚さ
が約７０μｍ、直径が１０ｍｍの円板状になった正極１
を作製した。Here, in the third embodiment, the positive electrode 1
Lithium hydroxide LiO as a raw material for producing
Lithium-containing nickel dioxide LiNiO 2 obtained by heat-treating H and nickel hydroxide Ni (OH) 2 at a temperature of 700 to 800 ° C. for 20 hours in an oxygen atmosphere was used as a positive electrode material. After nickel, carbon powder as a conductive agent, and fluororesin powder as a binder were mixed in a weight ratio of 85: 10: 5, and this mixture was applied on the positive electrode current collector 5 by the doctor blade method. This was subjected to vacuum heat treatment at 100 to 150 ° C. to form a disk-shaped positive electrode 1 having a thickness of about 70 μm and a diameter of 10 mm.
Was prepared.
【００４１】そして、この実施例においては、この正極
１上にスパッタリングによって非晶質層１ａを形成する
にあたり、スパッタリングのターゲットに上記実施例２
において使用したリチウム含有二酸化マンガンＬｉＭｎ
Ｏ2 を用い、それ以外については、上記実施例１の場合
と同じスパッタ条件でスパッタリングを行ない、上記の
正極１上に、非晶質のリチウム含有二酸化マンガンＬｉ
ＭｎＯ2 で構成され厚みが約０．７５μｍになった非晶
質層１ａを形成した。In this embodiment, when the amorphous layer 1a is formed on the positive electrode 1 by sputtering, the sputtering target is used in Embodiment 2 described above.
Lithium-containing manganese dioxide LiMn used in
O 2 was used, and other than that, sputtering was performed under the same sputtering conditions as in the case of Example 1 above. Amorphous lithium-containing manganese dioxide Li was formed on the positive electrode 1 described above.
An amorphous layer 1a made of MnO 2 and having a thickness of about 0.75 μm was formed.
【００４２】［比較例３］この比較例においては、上記
実施例３の固体電解質電池において正極１上に非晶質層
１ａを設ける工程をなくし、それ以外については、上記
実施例３と同様にして固体電解質電池を作製した。[Comparative Example 3] In this Comparative Example, the step of providing the amorphous layer 1a on the positive electrode 1 in the solid electrolyte battery of the above Example 3 was omitted, and otherwise the same as in Example 3 above. Then, a solid electrolyte battery was produced.
【００４３】次に、上記のようにして作製した実施例３
及び比較例３の各固体電解質電池に対して、上記実施例
１及び比較例１の場合と同様にして、これらの各固体電
解質電池における充放電特性を調べ、その結果を図７に
示した。なお、同図においては、実施例３の固体電解質
電池における結果を実線で、比較例３の固体電解質電池
における結果を破線で示すと共に、放電時における結果
を太線で、充電時における結果を細線で示した。Next, Example 3 produced as described above
For each of the solid electrolyte batteries of Comparative Example 3 and Comparative Example 3, the charge and discharge characteristics of each of the solid electrolyte batteries were examined in the same manner as in Example 1 and Comparative Example 1, and the results are shown in FIG. In the figure, the results of the solid electrolyte battery of Example 3 are shown by solid lines, the results of the solid electrolyte battery of Comparative Example 3 are shown by broken lines, the results of discharging are shown by thick lines, and the results of charging are shown by thin lines. Indicated.
【００４４】この結果、上記のように非晶質層１ａを設
けた実施例３の固体電解質電池は、非晶質層１ａを設け
ていない比較例３の固体電解質電池に比べて、放電時に
おける電池電圧の変動が少なく、比較例３の電池に比べ
て放電特性が優れていた。As a result, the solid electrolyte battery of Example 3 in which the amorphous layer 1a was provided as described above was discharged during discharging as compared with the solid electrolyte battery of Comparative Example 3 in which the amorphous layer 1a was not provided. The fluctuation of the battery voltage was small, and the discharge characteristics were superior to those of the battery of Comparative Example 3.
【００４５】[0045]
【発明の効果】以上詳述したように、この発明において
は、正極と高分子固体電解質との界面部分において、正
極における正極材料と結晶性の異なる正極材料の層を設
けるようにしたため、前記のようにこの結晶性の異なる
正極材料の層によって正極を構成する正極材料の劣化が
抑制され、これによりこの固体電解質電池の放電特性が
向上すると共に、二次電池として使用した場合には、大
電流での充放電が可能となり、その充放電サイクル特性
も著しく向上した。As described above in detail, in the present invention, a layer of a positive electrode material having a crystallinity different from that of the positive electrode material in the positive electrode is provided at the interface between the positive electrode and the solid polymer electrolyte. As described above, the deterioration of the positive electrode material that constitutes the positive electrode is suppressed by the layer of the positive electrode material having different crystallinity, thereby improving the discharge characteristics of the solid electrolyte battery and, when used as a secondary battery, a large current Charging and discharging have been made possible, and the charging and discharging cycle characteristics have been significantly improved.
【図１】この発明における実施例１〜３の各固体電解質
電池の構造を示した断面説明図である。FIG. 1 is an explanatory cross-sectional view showing the structure of each solid electrolyte battery of Examples 1 to 3 in the present invention.
【図２】比較例１〜３の各固体電解質電池の構造を示し
た断面説明図である。FIG. 2 is a cross-sectional explanatory view showing the structure of each solid electrolyte battery of Comparative Examples 1 to 3.
【図３】実施例１及び比較例１の各固体電解質電池にお
ける充放電サイクル特性を示した図である。FIG. 3 is a diagram showing charge / discharge cycle characteristics in each solid electrolyte battery of Example 1 and Comparative Example 1.
【図４】実施例１及び比較例１の各固体電解質電池にお
ける充放電特性を示した図である。FIG. 4 is a diagram showing charge / discharge characteristics in each solid electrolyte battery of Example 1 and Comparative Example 1.
【図５】実施例１の固体電解質電池において、正極上に
形成する非晶質層の厚みを変化させた場合における容量
保存率の変化を示した図である。FIG. 5 is a diagram showing changes in the capacity retention rate when the thickness of the amorphous layer formed on the positive electrode is changed in the solid electrolyte battery of Example 1.
【図６】実施例２及び比較例２の各固体電解質電池にお
ける充放電サイクル特性を示した図である。FIG. 6 is a diagram showing charge / discharge cycle characteristics in each solid electrolyte battery of Example 2 and Comparative Example 2.
【図７】実施例３及び比較例３の各固体電解質電池にお
ける充放電特性を示した図である。FIG. 7 is a diagram showing charge / discharge characteristics in each solid electrolyte battery of Example 3 and Comparative Example 3.
１ 正極 １ａ 結晶性の異なる正極材料の層（非晶質層） ２ 負極 ３ 高分子固体電解質 1 Positive Electrode 1a Positive Electrode Material Layer with Different Crystallinity (Amorphous Layer) 2 Negative Electrode 3 Polymer Solid Electrolyte
───────────────────────────────────────────────────── フロントページの続き (72)発明者 西尾 晃治 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Koji Nishio 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd.
Claims (4)
備える固体電解質電池において、正極と高分子固体電解
質の界面部分において、上記正極における正極材料と結
晶性の異なる正極材料の層が形成されてなることを特徴
とする固体電解質電池。1. In a solid electrolyte battery comprising a solid polymer electrolyte between a positive electrode and a negative electrode, a layer of a positive electrode material having a crystallinity different from that of the positive electrode material in the positive electrode is formed at an interface portion between the positive electrode and the solid polymer electrolyte. A solid electrolyte battery characterized by comprising:
いて、正極と高分子固体電解質との界面部分における結
晶性の異なる正極材料の層の厚みが０．１〜１μｍであ
ることを特徴とする固体電解質電池。2. The solid electrolyte battery according to claim 1, wherein the thickness of the layer of the positive electrode material having different crystallinity at the interface between the positive electrode and the solid polymer electrolyte is 0.1 to 1 μm. Solid electrolyte battery.
いて、上記正極を構成する正極材料及び上記結晶性の異
なる正極材料がリチウムの吸蔵・放出が可能なリチウム
含有遷移金属酸化物で構成されていることを特徴とする
固体電解質電池。3. The solid electrolyte battery according to claim 1, wherein the positive electrode material forming the positive electrode and the positive electrode material having different crystallinity are made of a lithium-containing transition metal oxide capable of inserting and extracting lithium. A solid electrolyte battery characterized in that
備える固体電解質電池を製造するにあたり、正極上に高
分子固体電解質を形成する前に、高分子固体電解質との
界面部分に物理的手法により正極における正極材料と結
晶性の異なる正極材料の層を形成することを特徴とする
固体電解質電池の製造方法。4. When manufacturing a solid electrolyte battery comprising a solid polymer electrolyte between a positive electrode and a negative electrode, before forming the solid polymer electrolyte on the positive electrode, a physical interface is formed at the interface with the solid polymer electrolyte. A method for producing a solid electrolyte battery, which comprises forming a layer of a positive electrode material having a crystallinity different from that of the positive electrode material in the positive electrode by a method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28260995A JP3384661B2 (en) | 1995-10-03 | 1995-10-03 | Solid electrolyte battery and method for manufacturing solid electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28260995A JP3384661B2 (en) | 1995-10-03 | 1995-10-03 | Solid electrolyte battery and method for manufacturing solid electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09102320A true JPH09102320A (en) | 1997-04-15 |
| JP3384661B2 JP3384661B2 (en) | 2003-03-10 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28260995A Expired - Fee Related JP3384661B2 (en) | 1995-10-03 | 1995-10-03 | Solid electrolyte battery and method for manufacturing solid electrolyte battery |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001015162A (en) * | 1999-06-29 | 2001-01-19 | Sony Corp | Solid electrolyte battery |
| US6444369B1 (en) | 1998-01-08 | 2002-09-03 | Sanyo Electric Co., Ltd. | Gelled polymer electrolyte lithium secondary cell |
| JP2009070591A (en) * | 2007-09-11 | 2009-04-02 | Sumitomo Electric Ind Ltd | Cathode, all-solid battery and manufacturing method of all-solid battery |
| JPWO2009063747A1 (en) * | 2007-11-13 | 2011-03-31 | 住友電気工業株式会社 | Lithium battery and manufacturing method thereof |
| JP2014060020A (en) * | 2012-09-18 | 2014-04-03 | Toshiba Corp | Nonaqueous electrolyte battery |
| JP2016225281A (en) * | 2015-05-26 | 2016-12-28 | パナソニックＩｐマネジメント株式会社 | All-solid lithium ion secondary battery and method of manufacturing the same |
-
1995
- 1995-10-03 JP JP28260995A patent/JP3384661B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6444369B1 (en) | 1998-01-08 | 2002-09-03 | Sanyo Electric Co., Ltd. | Gelled polymer electrolyte lithium secondary cell |
| JP2001015162A (en) * | 1999-06-29 | 2001-01-19 | Sony Corp | Solid electrolyte battery |
| JP2009070591A (en) * | 2007-09-11 | 2009-04-02 | Sumitomo Electric Ind Ltd | Cathode, all-solid battery and manufacturing method of all-solid battery |
| JPWO2009063747A1 (en) * | 2007-11-13 | 2011-03-31 | 住友電気工業株式会社 | Lithium battery and manufacturing method thereof |
| JP5316809B2 (en) * | 2007-11-13 | 2013-10-16 | 住友電気工業株式会社 | Lithium battery and manufacturing method thereof |
| JP2014060020A (en) * | 2012-09-18 | 2014-04-03 | Toshiba Corp | Nonaqueous electrolyte battery |
| JP2016225281A (en) * | 2015-05-26 | 2016-12-28 | パナソニックＩｐマネジメント株式会社 | All-solid lithium ion secondary battery and method of manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3384661B2 (en) | 2003-03-10 |
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