JPH08148180A - Total solid lithium secondary battery - Google Patents
Total solid lithium secondary batteryInfo
- Publication number
- JPH08148180A JPH08148180A JP7240323A JP24032395A JPH08148180A JP H08148180 A JPH08148180 A JP H08148180A JP 7240323 A JP7240323 A JP 7240323A JP 24032395 A JP24032395 A JP 24032395A JP H08148180 A JPH08148180 A JP H08148180A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- negative electrode
- active material
- battery
- solid electrolyte
- 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.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、リチウムイオン導
電性固体電解質を用いた全固体リチウム二次電池に関す
るものである。TECHNICAL FIELD The present invention relates to an all solid lithium secondary battery using a lithium ion conductive solid electrolyte.
【０００２】[0002]
【従来の技術】近年、カメラ一体型ＶＴＲ・携帯電話等
のポータブル機器の小型化・軽量化が進むなかで、その
電源としての電池に対して、高エネルギー密度化が望ま
れている。特に、リチウム電池は、リチウムが小さな原
子量を持ちかつイオン化エネルギーが大きな物質である
ことから、高エネルギー密度を得ることができる電池と
して各方面で盛んに研究が行われている。2. Description of the Related Art In recent years, as portable devices such as a camera-integrated VTR and a mobile phone have become smaller and lighter, higher energy density has been demanded for a battery as a power source thereof. In particular, since lithium is a substance having a small atomic weight and a large ionization energy, a lithium battery has been actively researched in various fields as a battery capable of obtaining a high energy density.
【０００３】その一方、これらの用途に用いられるリチ
ウム二次電池には、電解液として有機電解液が使用され
ている。このため、負極にアルミニウムやインジウムと
いった金属を用いた場合にはリチウムとの合金化によっ
て脆化し、活物質が微細化し、電極の結着性が悪くな
る。そして、電極から活物質の脱落が生じ、見かけの表
面積の低下を引き起こしたり、電解液との反応により金
属負極が不動態化し、インピーダンスが増大したりす
る。その結果、インピーダンスの低い部分に電流集中が
起こり、デンドライトが発生し、このデンドライトが正
負極間に存在するセパレータを貫通し、これによって電
池が内部短絡するといった問題が生じやすい。一方、ヨ
ウ化リチウムなどのハロゲン化物からなる固体電解質を
用いた固体電池においては、金属負極表面にハロゲン化
物が生成することにより、高インピーダンス部が生じ
る。このためインピーダンスの低い部分に電流集中が起
こり、デンドライトが発生するといった問題が生じた
り、また、高インピーダンス部が生成することにより、
この部分で電気化学反応速度が低下し、見かけ上、反応
表面積が減少する結果、充放電サイクル特性の劣化を招
くといった問題が生じやすい。このようなデンドライト
発生の問題を解決し電池の信頼性を高めるために、層間
にリチウムを吸蔵・放出することが可能な炭素材料を用
いたり、電解液中にデンドライト抑制剤を添加するなど
の方法が提案されている。On the other hand, an organic electrolytic solution is used as an electrolytic solution in a lithium secondary battery used for these purposes. Therefore, when a metal such as aluminum or indium is used for the negative electrode, it becomes brittle due to alloying with lithium, the active material becomes finer, and the binding property of the electrode deteriorates. Then, the active material falls off from the electrode, causing an apparent decrease in surface area, or the reaction with the electrolytic solution causes the metal negative electrode to be passivated and the impedance to increase. As a result, current concentration occurs in the portion with low impedance, dendrites are generated, and the dendrites penetrate the separator existing between the positive and negative electrodes, which easily causes a problem such as internal short circuit of the battery. On the other hand, in a solid battery using a solid electrolyte made of a halide such as lithium iodide, a high impedance portion is generated due to the formation of the halide on the surface of the metal negative electrode. For this reason, current concentration occurs in the low impedance part, which causes problems such as dendrites, and the high impedance part creates
At this portion, the electrochemical reaction rate decreases, and apparently the reaction surface area decreases. As a result, problems such as deterioration of charge / discharge cycle characteristics tend to occur. In order to solve such a problem of dendrite generation and improve the reliability of the battery, a method of using a carbon material capable of inserting and extracting lithium between layers, adding a dendrite suppressor to the electrolytic solution, etc. Is proposed.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、こうし
た方法をとった場合でも、大電流で充電を行った場合に
おいては、完全にデンドライトの発生を抑制することが
できなかった。また、有機電解液を用いたリチウム電池
では、そのエネルギー密度の高さのために、リチウムデ
ンドライトの発生により正負極間の短絡が生じた際に
は、電池が発火する恐れがあった。本発明は、このよう
な課題を解決するものであり、有機電解液や、ハロゲン
化物からなる固体電解質を用いた場合に発生していた負
極でのデンドライトの発生や活物質の脱落を防止するこ
とができる全固体リチウム二次電池を提供することを目
的とするものである。However, even when such a method is adopted, it is not possible to completely suppress the generation of dendrites when charging is performed with a large current. Further, in the lithium battery using the organic electrolytic solution, due to its high energy density, when the short circuit between the positive and negative electrodes occurs due to the generation of lithium dendrite, the battery may ignite. The present invention is to solve such a problem, and to prevent the generation of dendrites or the dropout of the active material in the negative electrode that has occurred when an organic electrolyte solution or a solid electrolyte composed of a halide is used. It is an object of the present invention to provide an all-solid-state lithium secondary battery capable of achieving the above.
【０００５】[0005]
【課題を解決するための手段】本発明は、正極活物質と
して遷移金属酸化物および遷移金属硫化物よりなる群か
ら選択される化合物を含む正極、Ｌｉ2Ｓを含むガラス
からなるリチウムイオン導電性の固体電解質、およびリ
チウムと合金化する金属を含む負極を具備し、前記正極
の活物質および負極金属の少なくとも一方がリチウムを
含む全固体リチウム二次電池を提供する。さらに詳しく
は、本発明の全固体リチウム二次電池は、負極の金属活
物質は、少なくとも充電状態においてリチウムを含み、
正極の活物質は少なくとも放電状態においてリチウムを
含む。According to the present invention, a positive electrode containing a compound selected from the group consisting of transition metal oxides and transition metal sulfides as a positive electrode active material, and a lithium ion conductive film made of glass containing Li 2 S. An all-solid-state lithium secondary battery is provided, which comprises a solid electrolyte of 1 above, and a negative electrode containing a metal alloying with lithium, and at least one of the positive electrode active material and the negative electrode metal contains lithium. More specifically, in the all-solid-state lithium secondary battery of the present invention, the metal active material of the negative electrode contains lithium at least in a charged state,
The positive electrode active material contains lithium at least in a discharged state.
【０００６】本発明の好ましい態様において、負極の金
属活物質は、Ｉｎ、Ｐｂ、Ｚｎ、Ｓｎ、Ｓｂ、Ｂｉ、Ｃ
ｄ、Ｇａ、およびＴｉよりなる群から選ばれる単一の金
属、または二種以上の金属からなる合金である。本発明
はまた、Ｉｎ、Ｐｂ、Ｚｎ、Ｓｎ、Ｓｂ、Ｂｉ、Ｃｄ、
Ｇａ、およびＴｉよりなる群から選ばれる少なくとも一
種を主成分とする合金を負極に用いることもできる。本
発明の好ましい他の態様において、負極の金属活物質
は、ＡｌまたはＡｌを主成分とする合金である。前記負
極の金属活物質は、少なくとも充電状態においてはリチ
ウムと合金化している。In a preferred embodiment of the present invention, the metal active material of the negative electrode is In, Pb, Zn, Sn, Sb, Bi, C.
It is a single metal selected from the group consisting of d, Ga, and Ti, or an alloy composed of two or more metals. The present invention also includes In, Pb, Zn, Sn, Sb, Bi, Cd,
An alloy containing at least one selected from the group consisting of Ga and Ti as the main component can also be used for the negative electrode. In another preferred embodiment of the present invention, the metal active material of the negative electrode is Al or an alloy containing Al as a main component. The metal active material of the negative electrode is alloyed with lithium at least in a charged state.
【０００７】本発明の好ましい態様において、正極の活
物質はＬｉxＣｏＯ2、ＬｉxＭｎＯ2、ＬｉxＭｎ2Ｏ4、
ＬｉxＮｉＯ2、ＬｉxＴｉＳ2、ＬｉxＭｏＳ2、およびＬ
ｉxＭｏ6Ｓ8よりなる群から選択される化合物（ただ
し、ｘ≧０）である。本発明の好ましい態様において、
前記固体電解質は、さらにＳｉＳ2、Ａｌ2Ｓ3、Ｐ
2Ｓ5、およびＢ2Ｓ3よりなる群から選択される少なくと
も一種を含む。本発明のさらに好ましい態様において、
前記固体電解質は、さらにＬｉ2Ｏ、Ｌｉ3ＰＯ4、Ｌｉ2
ＳＯ4、およびＬｉ2ＣＯ3よりなる群から選択される少
なくとも一種を含んでいる。In a preferred embodiment of the present invention, the positive electrode active material is Li x CoO 2 , Li x MnO 2 , Li x Mn 2 O 4 ,
Li x NiO 2 , Li x TiS 2 , Li x MoS 2 , and L
It is a compound (provided that x ≧ 0) selected from the group consisting of i x Mo 6 S 8 . In a preferred embodiment of the present invention,
The solid electrolyte further includes SiS 2 , Al 2 S 3 , P
At least one selected from the group consisting of 2 S 5 and B 2 S 3 . In a further preferred embodiment of the present invention,
The solid electrolyte further includes Li 2 O, Li 3 PO 4 , Li 2
It contains at least one selected from the group consisting of SO 4 and Li 2 CO 3 .
【０００８】本発明の全固体リチウム二次電池は、好ま
しい態様において、電解質層にＬｉ2Ｓ−Ｘ、またはＬ
ｉ2Ｓ−Ｘ−Ｙからなるガラス固体電解質を用いてい
る。ここで、ＸはＳｉＳ2、Ａｌ2Ｓ3、Ｐ2Ｓ5、および
Ｂ2Ｓ3よりなる群から選択される少なくとも一種を表
し、ＹはＬｉ2Ｏ、Ｌｉ3ＰＯ4、Ｌｉ2ＳＯ4、およびＬ
ｉ2ＣＯ3よりなる群から選択される少なくとも一種を表
す。これらのガラス固体電解質は、ハロゲン化物を含ま
ないため、負極金属活物質表面にハロゲン化物との反応
による高インピーダンス層は生成しない。また、固体電
解質が負極表面に接しているので、負極活物質がリチウ
ムとの合金化によって微細化しても、電極からの脱落を
防止することができ、さらに反応表面積の増大といった
好ましい作用を示す。その結果、電流分布が均一とな
り、リチウムデンドライトが発生せず、このデンドライ
トによる電池の内部短絡を防止することができ、極めて
信頼性の高いリチウム二次電池を得ることができる。In a preferred embodiment of the all-solid-state lithium secondary battery of the present invention, Li 2 S-X or L is used as the electrolyte layer.
A glass solid electrolyte composed of i 2 S-X-Y is used. Here, X represents at least one selected from the group consisting of SiS 2 , Al 2 S 3 , P 2 S 5 , and B 2 S 3 , and Y is Li 2 O, Li 3 PO 4 , Li 2 SO 4 , And L
It represents at least one selected from the group consisting of i 2 CO 3 . Since these glass solid electrolytes do not contain a halide, a high impedance layer is not formed on the surface of the negative electrode metal active material by the reaction with a halide. Further, since the solid electrolyte is in contact with the surface of the negative electrode, even if the negative electrode active material is made finer by alloying with lithium, it is possible to prevent the negative electrode active material from coming off from the electrode, and further it is preferable to increase the reaction surface area. As a result, the current distribution becomes uniform, lithium dendrites do not occur, it is possible to prevent an internal short circuit of the battery due to the dendrites, and it is possible to obtain an extremely reliable lithium secondary battery.
【０００９】ここにおいて、固体電解質の組成をａＬｉ
2Ｓ−（１−ａ）ＸまたはｂＹ−（１−ｂ）［ａＬｉ2Ｓ
−（１−ａ）Ｘ］で表したとき、０．３＜ａ、ｂ＜０．
３であることが好ましい。電極活物質に粉末を用いる場
合は、固体電解質粉末と混合して電極を構成するのが好
ましい。正極活物質粉末と固体電解質粉末との混合比は
重量比で、活物質：電解質＝３：７〜９．５：０．５が
好ましい。また、負極においては、合金粉末の重量百分
率２５％以上が好ましい。硫化物のみからなる固体電解
質は、分解電圧が３〜３．５Ｖ（ｖｓ．Ｌｉ+／Ｌｉ）
程度と低い。このため同電解質は、正極活物質に約４Ｖ
（ｖｓ．Ｌｉ+／Ｌｉ）の高い起電力を発生する遷移金
属酸化物を用いる電池に適用すると、酸化されて分解す
る。従って、遷移金属酸化物を正極活物質に用いる電池
の電解質には、本発明によるＬｉ2Ｓ−Ｘ−Ｙからなる
固体電解質が適している。Here, the composition of the solid electrolyte is aLi
2 S- (1-a) X or bY- (1-b) [aLi 2 S
-(1-a) X], 0.3 <a, b <0.
It is preferably 3. When a powder is used as the electrode active material, it is preferable to mix it with the solid electrolyte powder to form the electrode. The mixing ratio of the positive electrode active material powder and the solid electrolyte powder is a weight ratio, and the active material: electrolyte = 3: 7 to 9.5: 0.5 is preferable. Further, in the negative electrode, the weight percentage of the alloy powder is preferably 25% or more. A solid electrolyte composed of only sulfide has a decomposition voltage of 3 to 3.5 V (vs. Li + / Li).
The degree is low. Therefore, the same electrolyte was added to the positive electrode active material at about 4V.
When applied to a battery using a transition metal oxide that generates a high electromotive force of (vs. Li + / Li), it is oxidized and decomposed. Therefore, the solid electrolyte composed of Li 2 S—X—Y according to the present invention is suitable for the electrolyte of the battery using the transition metal oxide as the positive electrode active material.
【００１０】[0010]
【発明の実施の形態】以下、本発明の実施例を説明す
る。以下の実施例における操作は全て不活性ガスを満た
したドライボックス中にて行った。また、以下の実施例
において、固体電解質は次のようにして製造した。すな
わち、所定量の原材料を十分に混合した後、グラッシー
カーボン製るつぼに充填し、アルゴンガス気流中におい
て１０００℃で２時間反応させた後、得られた融液を双
ローラーを用いて超急冷して固体電解質ガラスを得た。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. All the operations in the following examples were carried out in a dry box filled with an inert gas. Further, in the following examples, the solid electrolyte was manufactured as follows. That is, after thoroughly mixing a predetermined amount of raw materials, a glassy carbon crucible was filled and allowed to react at 1000 ° C. for 2 hours in an argon gas stream, and then the resulting melt was rapidly quenched using twin rollers. A solid electrolyte glass was obtained.
【００１１】［実施例１］負極活物質としてインジウム
（Ｉｎ）箔を用い、リチウムイオン導電性固体電解質と
して０．０１Ｌｉ3ＰＯ4−０．６３Ｌｉ2Ｓ−０．３６
ＳｉＳ2 ガラスを用い、正極活物質にコバルト酸リチウ
ム（ＬｉＣｏＯ2）を用いて、リチウム電池を構成し
た。以下にその詳細を示す。まず、０．０１Ｌｉ3ＰＯ4
−０．６３Ｌｉ2Ｓ−０．３６ＳｉＳ2で表されるリチウ
ムイオン導電性ガラス状固体電解質を乳鉢で１００メッ
シュ以下に粉砕し、直径１０ｍｍ、厚さ１．０ｍｍのデ
ィスク状に加圧成形した。Example 1 Indium (In) foil was used as the negative electrode active material, and 0.01 Li 3 PO 4 -0.63 Li 2 S-0.36 was used as the lithium ion conductive solid electrolyte.
A lithium battery was constructed by using SiS 2 glass and using lithium cobalt oxide (LiCoO 2 ) as a positive electrode active material. The details are shown below. First, 0.01Li 3 PO 4
A lithium ion conductive glassy solid electrolyte represented by -0.63Li 2 S-0.36SiS 2 was crushed to 100 mesh or less in a mortar and pressure-molded into a disk shape having a diameter of 10 mm and a thickness of 1.0 mm.
【００１２】また、コバルト酸リチウム（ＬｉＣｏ
Ｏ2）と前記リチウムイオン導電性ガラス状固体電解質
粉末を重量比で２：３の割合で混合し、この混合物を加
圧成形して厚さ０．５ｍｍ、直径１０ｍｍの円盤状正極
とした。負極は厚さ０．１ｍｍのインジウム箔を直径１
０ｍｍの円盤に切り抜いて用いた。そして、前記固体電
解質の成形体を前記正極および負極で挟んで圧接し、全
固体リチウム二次電池とした。Also, lithium cobalt oxide (LiCo
O 2 ) and the lithium ion conductive glassy solid electrolyte powder were mixed in a weight ratio of 2: 3, and the mixture was pressure-molded to obtain a disk-shaped positive electrode having a thickness of 0.5 mm and a diameter of 10 mm. The negative electrode is 0.1 mm thick indium foil with a diameter of 1
It was cut out into a 0 mm disk for use. Then, the molded body of the solid electrolyte was sandwiched between the positive electrode and the negative electrode and pressure-welded to obtain an all-solid lithium secondary battery.
【００１３】このリチウム二次電池を電流密度１００μ
Ａ／ｃｍ2で充放電サイクル試験を行った。その結果、
１０００サイクル経過しても充放電容量は初期から低下
することなく、また充放電効率も１００％で推移し安定
に動作することがわかった。また、このリチウム電池を
充電状態で解体し、負極と固体電解質の界面の状態を顕
微鏡で観察したところ、リチウムデンドライトの発生は
認められなかった。さらに、充電状態にあるこの電池を
８０℃の恒温槽に入れ、インピーダンスの経時変化を測
定した結果、２０００時間経過してもインピーダンスの
変化は認められなかった。以上のように、本発明による
とリチウムデンドライトの生成がなく安全性が高いリチ
ウム二次電池を得ることができることがわかった。This lithium secondary battery has a current density of 100 μm.
A charge / discharge cycle test was performed at A / cm 2 . as a result,
It was found that the charge / discharge capacity did not decrease from the beginning even after 1000 cycles, and the charge / discharge efficiency remained at 100% to operate stably. Further, when this lithium battery was disassembled in a charged state and the state of the interface between the negative electrode and the solid electrolyte was observed with a microscope, generation of lithium dendrite was not observed. Further, the battery in a charged state was placed in a constant temperature bath at 80 ° C. and the change in impedance with time was measured. As a result, no change in impedance was observed even after 2000 hours. As described above, according to the present invention, it was found that a lithium secondary battery having high safety without generation of lithium dendrite can be obtained.
【００１４】［実施例２〜３０］以下に、正極、固体電
解質、負極の材料を変え種々の組み合わせによって実施
例１と同様にして電池を構成した。これらの組み合わせ
を表１、３および５に、また実施例１と同条件での評価
結果を表２、４および表６にそれぞれ示す。[Examples 2 to 30] A battery was constructed in the same manner as in Example 1 except that the materials of the positive electrode, the solid electrolyte and the negative electrode were changed and various combinations were made. These combinations are shown in Tables 1, 3 and 5, and the evaluation results under the same conditions as in Example 1 are shown in Tables 2, 4 and 6, respectively.
【００１５】[0015]
【表１】 [Table 1]
【００１６】[0016]
【表２】 [Table 2]
【００１７】[0017]
【表３】 [Table 3]
【００１８】[0018]
【表４】 [Table 4]
【００１９】[0019]
【表５】 [Table 5]
【００２０】[0020]
【表６】 [Table 6]
【００２１】［比較例１］比較のために負極に直径１０
ｍｍ、厚さ０．１ｍｍの円盤状インジウム箔を用い、正
極にコバルト酸リチウム（ＬｉＣｏＯ2）の粉末を加圧
成形し厚さ０．５ｍｍ、直径１０ｍｍの円盤としたもの
を用い、これらをポリエチレン製のセパレータを介して
それぞれを対向させ、電池ケースに収納した。そして１
Ｍ−ＬｉＣｌＯ4 のプロピレンカーボネート溶液を電池
ケースに注入して有機電解液リチウム二次電池を構成し
た。Comparative Example 1 For comparison, the negative electrode had a diameter of 10
mm, 0.1 mm thick disc-shaped indium foil, using lithium cobalt oxide (LiCoO 2 ) powder pressure-molded on the positive electrode to form a disc with a thickness of 0.5 mm and a diameter of 10 mm. They were faced to each other via a separator made of, and housed in a battery case. And 1
A propylene carbonate solution of M-LiClO 4 was injected into the battery case to form an organic electrolyte lithium secondary battery.
【００２２】この電池を電流密度１００μＡ／ｃｍ2で
充放電サイクル試験を行った。その結果、初期および２
回目の放電容量が著しく異なり、２回目の放電容量は初
期の約８０％を示した。その後約５０サイクルを経過す
ると、充放電容量の低下が認められ、２３０サイクルで
充放電不能となった。この電池を解体し、観察した結
果、負極のリチウムと合金化したインジウムが微細化
し、部分的に脱落しているのがわかった。また、脱落に
到っていない部分においてリチウムのデンドライトが発
生しており、デンドライトがセパレータを貫通している
のが確認された。また、同様の構成の電池を充電状態で
８０℃の恒温槽に入れ、インピーダンスの経時変化を測
定したところ、金属負極表面の不動態化によると考えら
れるインピーダンスの増加が初期段階より観測された。This battery was subjected to a charge / discharge cycle test at a current density of 100 μA / cm 2 . As a result, initial and 2
The discharge capacities of the second time were remarkably different, and the discharge capacities of the second time were about 80% of the initial values. After about 50 cycles, a decrease in charge / discharge capacity was observed, and charge / discharge was impossible after 230 cycles. As a result of disassembling and observing this battery, it was found that indium alloyed with lithium in the negative electrode was finely divided and partly dropped. In addition, it was confirmed that dendrites of lithium were generated in the portions that had not fallen off and that the dendrites penetrated the separator. In addition, when a battery having the same configuration was put in a thermostat at 80 ° C. in a charged state and the change in impedance with time was measured, an increase in impedance, which was considered to be due to passivation of the surface of the metal negative electrode, was observed from the initial stage.
【００２３】［比較例２］比較のために固体電解質を
０．４５ＬｉＩ−０．３５Ｌｉ2Ｓ−０．２ＳｉＳ2ガラ
スとした以外は実施例１３と同様の電池を構成した。こ
のリチウム電池について電流密度１００μＡ／ｃｍ2で
充放電サイクル試験を行ったところ、サイクル数を重ね
るごとに放電容量が漸次減少する現象が認められ、３０
０サイクルを経過したところで充電途中で電圧が上昇し
なくなった。このリチウム電池を解体し、負極と固体電
解質の界面の状態を顕微鏡で観察したところ、デンドラ
イトの生成が観察された。デンドライトにより短絡した
ために充電が不能になったと考えられる。さらに、充電
状態にある電池を８０℃の恒温槽に入れ、インピーダン
スの経時変化を測定した結果、１５時間後からインピー
ダンスの増大が観測された。Comparative Example 2 For comparison, a battery similar to that of Example 13 was constructed except that 0.45LiI-0.35Li 2 S-0.2SiS 2 glass was used as the solid electrolyte. When a charge / discharge cycle test was conducted on this lithium battery at a current density of 100 μA / cm 2 , a phenomenon was observed in which the discharge capacity gradually decreased as the number of cycles increased.
The voltage did not rise during charging when 0 cycles had elapsed. When this lithium battery was disassembled and the state of the interface between the negative electrode and the solid electrolyte was observed with a microscope, generation of dendrites was observed. It is thought that charging was disabled because of a short circuit due to a dendrite. Furthermore, the battery in the charged state was placed in a constant temperature bath at 80 ° C., and the change in impedance with time was measured. As a result, an increase in impedance was observed after 15 hours.
【００２４】［比較例３］比較のために固体電解質を
０．６Ｌｉ2Ｓ−０．４Ｂ2Ｓ3ガラスとした以外は実施
例１３と同様の電池を構成した。このリチウム電池につ
いて電流密度１００μＡ／ｃｍ2で充放電サイクル試験
を行ったところ、サイクル数を重ねるごとに放電容量が
漸次低下した。また、この電池を充放電サイクル試験を
しながら、充電後の休止時間中にインピーダンス測定を
行った結果、サイクル数の進行とともにインピーダンス
の増加が認められたことから、固体電解質の分解が起こ
っているものと考えられる。[Comparative Example 3] For comparison, a battery similar to that of Example 13 was constructed except that the solid electrolyte was changed to 0.6Li 2 S-0.4B 2 S 3 glass. A charge / discharge cycle test was conducted on this lithium battery at a current density of 100 μA / cm 2 , and the discharge capacity gradually decreased as the number of cycles increased. In addition, while performing a charge-discharge cycle test on this battery, impedance measurement was performed during a rest period after charging, and as a result, an increase in impedance was observed as the number of cycles progressed, and thus solid electrolyte decomposition occurred. It is considered to be a thing.
【００２５】［比較例４］比較のために固体電解質を
０．６Ｌｉ2Ｓ−０．４Ｐ2Ｓ5ガラスに、正極活物質を
ＬｉＮｉＯ2 に、負極金属をＰｂとした以外は実施例１
と同様にして電池を構成した。このリチウム電池につい
て電流密度１００μＡ／ｃｍ2で充放電サイクル試験を
行ったところ、サイクル数を重ねるごとに放電容量が十
数％の減少が認められた。また、この電池を充放電サイ
クル試験をしながら、充電後の休止時間中にインピーダ
ンス測定を行った結果、サイクル数の進行とともにイン
ピーダンスの増加が認められたことから、固体電解質の
分解が起こっているものと考えられる。Comparative Example 4 For comparison, Example 1 was used except that the solid electrolyte was 0.6Li 2 S-0.4P 2 S 5 glass, the positive electrode active material was LiNiO 2 , and the negative electrode metal was Pb.
A battery was constructed in the same manner as in. When this lithium battery was subjected to a charge / discharge cycle test at a current density of 100 μA / cm 2 , the discharge capacity was found to decrease by more than 10% as the number of cycles was increased. In addition, while performing a charge-discharge cycle test on this battery, impedance measurement was performed during a rest period after charging, and as a result, an increase in impedance was observed as the number of cycles progressed, and thus solid electrolyte decomposition occurred. It is considered to be a thing.
【００２６】［実施例３１］負極にインジウム（Ｉｎ）
粉末を、リチウムイオン導電性固体電解質として０．０
１Ｌｉ3 ＰＯ4 −０．６３Ｌｉ2Ｓ−０．３６ＳｉＳ2ガ
ラスを、正極にコバルト酸リチウム（ＬｉＣｏＯ2） を
用いて、リチウム電池を構成した。以下にその詳細を示
す。まず、０．０１Ｌｉ3 ＰＯ4 −０．６３Ｌｉ2Ｓ−
０．３６ＳｉＳ2で表されるリチウムイオン導電性ガラ
ス状固体電解質を乳鉢で１００メッシュ以下に粉砕し、
直径１０ｍｍ、厚さ０．５ｍｍの円盤に加圧成形した。
また、コバルト酸リチウム（ＬｉＣｏＯ2） と上記リチ
ウムイオン導電性ガラス状固体電解質粉末を重量比で
２：３の割合で混合し、この混合物を加圧成形して厚さ
０．５ｍｍ、直径１０ｍｍの円盤状正極とした。負極は
インジウム粉末と上記リチウムイオン導電性ガラス状固
体電解質粉末を重量比で２：１の割合で混合したものを
加圧成形し、厚さ０．１ｍｍ、直径１０ｍｍの円盤とし
たものを用いた。そして、前記固体電解質の成形体を前
記正極および負極で挟んで圧接し、全固体リチウム二次
電池を構成した。[Example 31] Indium (In) was used for the negative electrode.
The powder was used as a lithium ion conductive solid electrolyte with 0.0
The 1Li 3 PO 4 -0.63Li 2 S- 0.36SiS 2 glass, using a lithium cobaltate (LiCoO 2) in the positive electrode, to constitute a lithium battery. The details are shown below. First, 0.01Li 3 PO 4 -0.63Li 2 S-
Lithium ion conductive glassy solid electrolyte represented by 0.36SiS 2 is pulverized in a mortar to 100 mesh or less,
It was pressure molded into a disk having a diameter of 10 mm and a thickness of 0.5 mm.
Further, lithium cobalt oxide (LiCoO 2 ) and the above lithium ion conductive glassy solid electrolyte powder were mixed in a weight ratio of 2: 3, and this mixture was pressure-molded to have a thickness of 0.5 mm and a diameter of 10 mm. A disk-shaped positive electrode was used. As the negative electrode, a mixture of indium powder and the above lithium ion conductive glassy solid electrolyte powder in a weight ratio of 2: 1 was pressure-molded and used as a disk having a thickness of 0.1 mm and a diameter of 10 mm. . Then, the molded body of the solid electrolyte was sandwiched between the positive electrode and the negative electrode and pressed into contact with each other to form an all-solid lithium secondary battery.
【００２７】このリチウム二次電池を電流密度１００μ
Ａ／ｃｍ2で充放電サイクル試験を行った結果、８００
サイクル経過しても充放電容量は初期から低下すること
なく、また充放電効率も１００％で推移し安定に動作す
ることがわかった。また、電池を充電状態で解体し、負
極と電解質の界面を顕微鏡観察を行ったが、デンドライ
トの生成は認められなかった。さらに、この構成の電池
を８０℃の恒温槽に入れ、インピーダンスの経時変化を
測定した結果、１０００時間経過してもインピーダンス
の変化は認められなかった。This lithium secondary battery was tested with a current density of 100 μm.
The result of the charge / discharge cycle test at A / cm 2 is 800
It was found that the charge / discharge capacity did not decrease from the beginning even after the cycle passed, and the charge / discharge efficiency remained at 100% and the operation was stable. Further, the battery was disassembled in a charged state, and the interface between the negative electrode and the electrolyte was observed under a microscope, but no dendrite formation was observed. Further, the battery having this structure was placed in a constant temperature bath at 80 ° C., and the change in impedance with time was measured. As a result, no change in impedance was observed even after 1000 hours had elapsed.
【００２８】［実施例３２］負極にインジウム−鉛合金
（０．６Ｉｎ−０．４Ｐｂ）箔を用いた以外は、実施例
１３と同様の方法で全固体リチウム二次電池を構成し
た。インジウム−鉛合金は、インジウム箔と鉛箔を原子
比で３：２の割合のものを圧接し、アルゴン雰囲気中に
おいて２００℃で４８時間固相反応させることにより得
た。このリチウム電池の充放電サイクル試験を電流密度
１００μＡ／ｃｍ2で行ったところ、８００サイクルに
到達しても初期の放電容量を維持し、さらに充放電効率
は１００％となり、充放電曲線にも変化は起こらなかっ
た。また、このリチウム電池を充電状態で解体し、負極
と固体電解質の界面の状態を顕微鏡で観察したところ、
デンドライトの生成は認められなかった。[Example 32] An all-solid-state lithium secondary battery was constructed in the same manner as in Example 13 except that an indium-lead alloy (0.6In-0.4Pb) foil was used for the negative electrode. The indium-lead alloy was obtained by press-contacting an indium foil and a lead foil with an atomic ratio of 3: 2 and performing a solid phase reaction at 200 ° C. for 48 hours in an argon atmosphere. When the charge / discharge cycle test of this lithium battery was performed at a current density of 100 μA / cm 2 , the initial discharge capacity was maintained even after reaching 800 cycles, and the charge / discharge efficiency was 100%, and the charge / discharge curve also changed. Did not happen. Further, when this lithium battery was disassembled in a charged state and the state of the interface between the negative electrode and the solid electrolyte was observed with a microscope,
No dendrite formation was observed.
【００２９】なお、上記実施例においては、負極に特定
の金属を用いたが、他のインジウム、鉛、錫、亜鉛、カ
ドミウム、アンチモン、ビスマス、ガリウム、チタンの
いずれか、またはこれらのうちの二種以上からなる合金
を用いても同様の効果が得られる。正極材料、負極材料
および固体電解質の組み合わせあるいは組成比を本発明
の材料の範囲内で変えても本質的な効果に差違はなく同
様な効果が得られる。Although a specific metal was used for the negative electrode in the above-mentioned examples, any other indium, lead, tin, zinc, cadmium, antimony, bismuth, gallium, titanium, or two of these may be used. The same effect can be obtained by using an alloy composed of at least one kind. Even if the combination or composition ratio of the positive electrode material, the negative electrode material and the solid electrolyte is changed within the range of the material of the present invention, there is no difference in the essential effect and the same effect can be obtained.
【００３０】［実施例３３］負極活物質としてインジウ
ム−リチウム合金（０．５Ｉｎ−０．５Ｌｉ）箔を用
い、リチウムイオン導電性固体電解質として０．０１Ｌ
ｉ3ＰＯ4−０．６３Ｌｉ2Ｓ−０．３６ＳｉＳ2ガラスを
用い、正極活物質にコバルト酸リチウム（ＬｉＣｏ
Ｏ2）を用いて、リチウム電池を構成した。以下にその
詳細を示す。まず、０．０１Ｌｉ3ＰＯ4−０．６３Ｌｉ
2Ｓ−０．３６ＳｉＳ2で表されるリチウムイオン導電性
ガラス状固体電解質を乳鉢で１００メッシュ以下に粉砕
し、直径１０ｍｍ、厚さ１．０ｍｍのディスク状に加圧
成形した。また、コバルト酸リチウム（ＬｉＣｏＯ2）
と前記リチウムイオン導電性ガラス状固体電解質粉末を
重量比で２：３の割合で混合したものを加圧成形し、厚
さ０．５ｍｍ、直径１０ｍｍの円盤状正極とした。負極
は厚さ０．１ｍｍのインジウム−リチウム合金（０．５
Ｉｎ−０．５Ｌｉ）箔を直径１０ｍｍの円盤に切り抜い
て用いた。このインジウム−リチウム合金箔は、インジ
ウム箔とリチウム箔とを原子比で１：１の割合となる量
を圧接し、厚さ０．１ｍｍまで圧延することにより得
た。そして、前記固体電解質の成形体を前記正極および
負極で挟んで圧接し、全固体リチウム二次電池とした。[Example 33] Indium-lithium alloy (0.5In-0.5Li) foil was used as the negative electrode active material, and 0.01 L was used as the lithium ion conductive solid electrolyte.
i 3 PO 4 -0.63Li 2 using S-0.36SiS 2 glass, lithium cobaltate positive electrode active material (LiCo
A lithium battery was constructed using O 2 ). The details are shown below. First, 0.01Li 3 PO 4 -0.63Li
A lithium ion conductive glassy solid electrolyte represented by 2 S-0.36SiS 2 was crushed to 100 mesh or less in a mortar and pressure-molded into a disk shape having a diameter of 10 mm and a thickness of 1.0 mm. In addition, lithium cobalt oxide (LiCoO 2 )
And a mixture of the lithium ion conductive glassy solid electrolyte powder in a weight ratio of 2: 3 were pressure-molded to obtain a disk-shaped positive electrode having a thickness of 0.5 mm and a diameter of 10 mm. The negative electrode is a 0.1 mm thick indium-lithium alloy (0.5
The In-0.5Li) foil was used by cutting it into a disk having a diameter of 10 mm. This indium-lithium alloy foil was obtained by press-contacting an indium foil and a lithium foil in an atomic ratio of 1: 1 and rolling to a thickness of 0.1 mm. Then, the molded body of the solid electrolyte was sandwiched between the positive electrode and the negative electrode and pressure-welded to obtain an all-solid lithium secondary battery.
【００３１】このリチウム二次電池を電流密度１００μ
Ａ／ｃｍ2で充放電サイクル試験を行った。その結果、
１０００サイクル経過しても充放電容量は初期から低下
することなく、また充放電効率もほぼ１００％で推移し
安定に動作することがわかった。また、このリチウム電
池を充電状態で解体し、負極と固体電解質の界面の状態
を顕微鏡で観察したところ、デンドライトの発生は認め
られなかった。さらに、充電状態にあるこの電池を８０
℃の恒温槽に入れインピーダンスの経時変化を測定した
結果、２０００時間経過してもインピーダンスの変化は
認められなかった。以上のように、本発明によると、リ
チウムデンドライトの生成がなく、安全性が高いリチウ
ム二次電池を得ることができることがわかった。This lithium secondary battery was tested with a current density of 100 μm.
A charge / discharge cycle test was performed at A / cm 2 . as a result,
It was found that the charge / discharge capacity did not decrease from the beginning even after 1000 cycles, and the charge / discharge efficiency remained at almost 100% and the operation was stable. Further, when this lithium battery was disassembled in a charged state and the state of the interface between the negative electrode and the solid electrolyte was observed with a microscope, generation of dendrite was not observed. In addition, charge this battery 80
As a result of measuring the change with time of impedance in a constant temperature bath of ° C, no change in impedance was observed even after 2000 hours. As described above, according to the present invention, it was found that a lithium secondary battery having high safety without generation of lithium dendrite can be obtained.
【００３２】［実施例３４〜６２］以下に、正極、固体
電解質、負極の材料を変え種々の組み合わせによって実
施例３３と同様にして電池を構成した。これらの組み合
わせを表７、９および１１に、また評価結果を表８、１
０および表１２に示す。[Examples 34 to 62] In the following, batteries were constructed in the same manner as in Example 33, except that the materials of the positive electrode, the solid electrolyte and the negative electrode were changed. These combinations are shown in Tables 7, 9 and 11, and the evaluation results are shown in Tables 8 and 1.
0 and Table 12.
【００３３】[0033]
【表７】 [Table 7]
【００３４】[0034]
【表８】 [Table 8]
【００３５】[0035]
【表９】 [Table 9]
【００３６】[0036]
【表１０】 [Table 10]
【００３７】[0037]
【表１１】 [Table 11]
【００３８】[0038]
【表１２】 [Table 12]
【００３９】［比較例５］比較のために負極に１０ｍ
ｍ、厚さ０．１ｍｍのインジウム−リチウム合金（０．
５Ｉｎ−０．５Ｌｉ）箔を用い、正極にコバルト酸リチ
ウム（ＬｉＣｏＯ2）の粉末を加圧成形し厚さ０．５ｍ
ｍ、直径１０ｍｍの円盤状ディスクとしたものを用い、
これらをポリエチレン製のセパレータを介してそれぞれ
を対向させ、電池ケースに収納した。そして１Ｍ−Ｌｉ
ＣｌＯ4のプロピレンカーボネート溶液を電池ケースに
注入して有機電解液を用いたリチウム二次電池を構成し
た。[Comparative Example 5] For comparison, the negative electrode had a length of 10 m.
m, 0.1 mm thick indium-lithium alloy (0.
5In-0.5Li) foil was used, and lithium cobalt oxide (LiCoO 2 ) powder was pressure-molded on the positive electrode to form a 0.5 m thick film.
m, using a disc-shaped disc with a diameter of 10 mm,
These were made to oppose each other through the polyethylene separator and housed in the battery case. And 1M-Li
A propylene carbonate solution of ClO 4 was injected into a battery case to form a lithium secondary battery using an organic electrolytic solution.
【００４０】この電池を電流密度１００μＡ／ｃｍ2で
充放電サイクル試験を行った。その結果、初期および２
回目の放電容量が著しく異なり、２回目の放電容量は初
期の約８０％を示した。その後、約８０サイクルを経過
すると、充放電容量の低下が認められ、２５０サイクル
で充放電不能となった。この電池を解体し、観察した結
果、負極のインジウム−リチウム合金箔が微細化し、部
分的に脱落しているのがわかった。また、脱落に到って
いない部分においてリチウムのデンドライトが発生して
おり、セパレータを貫通しているのが確認された。ま
た、同様の構成の電池を充電状態で８０℃の恒温槽に入
れ、インピーダンスの経時変化を測定したところ、金属
負極表面の不動態化によると考えられるインピーダンス
の増加が初期段階より観測された。The battery was subjected to a charge / discharge cycle test at a current density of 100 μA / cm 2 . As a result, initial and 2
The discharge capacities of the second time were remarkably different, and the discharge capacities of the second time were about 80% of the initial values. Then, after about 80 cycles, a decrease in charge / discharge capacity was observed, and charge / discharge became impossible after 250 cycles. As a result of disassembling and observing this battery, it was found that the indium-lithium alloy foil of the negative electrode was miniaturized and partially dropped off. In addition, it was confirmed that dendrite of lithium was generated in a portion that had not fallen off and penetrated the separator. Further, when a battery having the same configuration was charged in a thermostat at 80 ° C. in a charged state and the change in impedance with time was measured, an increase in impedance, which was considered to be due to passivation of the surface of the metal negative electrode, was observed from the initial stage.
【００４１】［比較例６］比較のために固体電解質を
０．４５ＬｉＩ−０．３５Ｌｉ2Ｓ−０．２ＳｉＳ2ガラ
スとした以外は実施例４５と同様の電池を構成した。こ
のリチウム電池について電流密度１００μＡ／ｃｍ2で
充放電サイクル試験を行ったところ、サイクル数を重ね
るごとに放電容量が漸次減少する現象が認められ、３０
０サイクルを経過したところで充電途中で電圧が上昇し
なくなった。このリチウム電池を解体し、負極と固体電
解質の界面の状態を顕微鏡で観察したところ、デンドラ
イトの生成が観察された。電池の充電が不能になったの
は、短絡したためと考えられる。さらに、充電状態にあ
る電池を８０℃の恒温槽に入れインピーダンスの経時変
化を測定した結果、２０時間後からインピーダンスの増
大が観測された。[Comparative Example 6] For comparison, a battery was prepared in the same manner as in Example 45 except that the solid electrolyte was 0.45LiI-0.35Li 2 S-0.2SiS 2 glass. When a charge / discharge cycle test was conducted on this lithium battery at a current density of 100 μA / cm 2 , a phenomenon was observed in which the discharge capacity gradually decreased as the number of cycles increased.
The voltage did not rise during charging when 0 cycles had elapsed. When this lithium battery was disassembled and the state of the interface between the negative electrode and the solid electrolyte was observed with a microscope, generation of dendrites was observed. The reason why the battery could not be charged is probably due to a short circuit. Furthermore, as a result of placing the battery in a charged state in a thermostat at 80 ° C. and measuring the change in impedance over time, an increase in impedance was observed after 20 hours.
【００４２】［比較例７］比較のために固体電解質を
０．６Ｌｉ2Ｓ−０．４Ｂ2Ｓ3ガラスとした以外は実施
例４５と同様の電池を構成した。このリチウム電池につ
いて電流密度１００μＡ／ｃｍ2で充放電サイクル試験
を行ったところ、サイクル数を重ねるごとに放電容量が
漸次低下した。また、この電池を充放電サイクル試験を
しながら充電後の休止時間中にインピーダンス測定を行
った結果、サイクル数の進行とともにインピーダンスの
増加が認められたことから、固体電解質の分解が起こっ
ているものと考えられる。[Comparative Example 7] A battery was prepared in the same manner as in Example 45 except that the solid electrolyte was changed to 0.6Li 2 S-0.4B 2 S 3 glass for comparison. A charge / discharge cycle test was conducted on this lithium battery at a current density of 100 μA / cm 2 , and the discharge capacity gradually decreased as the number of cycles increased. In addition, as a result of impedance measurement during the rest period after charging while charging / discharging cycle test of this battery, an increase in impedance was observed as the number of cycles progressed, so that decomposition of the solid electrolyte occurred. it is conceivable that.
【００４３】［比較例８］比較のために固体電解質を
０．６Ｌｉ2Ｓ−０．４Ｐ2Ｓ5ガラスに、正極活物質を
ＬｉＮｉＯ2に、負極金属をＰｂ−Ｌｉ合金（０．６Ｐ
ｂ−０．４Ｌｉ）とした以外は実施例３３と同様にして
電池を構成した。このリチウム電池について電流密度１
００μＡ／ｃｍ2で充放電サイクル試験を行ったとこ
ろ、サイクル数を重ねるごとに放電容量が十数％の減少
が認められた。また、この電池を充放電サイクル試験を
しながら充電後の休止時間中にインピーダンス測定を行
った結果、サイクル数の進行とともにインピーダンスの
増加が認められたことから、固体電解質の分解が起こっ
ているものと考えられる。[Comparative Example 8] For comparison, the solid electrolyte was 0.6Li 2 S-0.4P 2 S 5 glass, the positive electrode active material was LiNiO 2 , and the negative electrode metal was Pb-Li alloy (0.6P).
A battery was constructed in the same manner as in Example 33 except that b-0.4Li) was used. Current density 1 for this lithium battery
When the charge / discharge cycle test was performed at 00 μA / cm 2 , the discharge capacity was decreased by 10% or more as the number of cycles was increased. In addition, as a result of impedance measurement during the rest period after charging while charging / discharging cycle test of this battery, an increase in impedance was observed as the number of cycles progressed, so that decomposition of the solid electrolyte occurred. it is conceivable that.
【００４４】［実施例６３］負極にインジウム−リチウ
ム合金（０．５Ｉｎ−０．５Ｌｉ）粉末を、リチウムイ
オン導電性固体電解質として０．０１Ｌｉ3ＰＯ4−０．
６３Ｌｉ2Ｓ−０．３６ＳｉＳ2ガラスを、正極にコバル
ト酸リチウム（ＬｉＣｏＯ2）を用いて、リチウム二次
電池を構成した。以下にその詳細を示す。まず、０．０
１Ｌｉ3ＰＯ4−０．６３Ｌｉ2Ｓ−０．３６ＳｉＳ2で表
されるリチウムイオン導電性ガラス状固体電解質を乳鉢
で１００メッシュ以下に粉砕し、直径１０ｍｍ、厚さ
０．５ｍｍの円盤に加圧成形した。また、コバルト酸リ
チウム（ＬｉＣｏＯ2）と上記リチウムイオン導電性ガ
ラス状固体電解質粉末を重量比で２：３の割合で混合し
たものを加圧成形し、厚さ０．５ｍｍ、直径１０ｍｍの
円盤状正極とした。負極はインジウム−リチウム合金
（０．５Ｉｎ−０．５Ｌｉ）粉末と上記リチウムイオン
導電性ガラス状固体電解質粉末を重量比で２：１の割合
で混合し、その混合物を加圧成形し、厚さ０．１ｍｍ、
直径１０ｍｍの円盤としたものを用いた。そして、前記
固体電解質の成形体を前記正極および負極で挟んで圧接
し、全固体リチウム二次電池を構成した。[0044] [Example 63] anode of indium - lithium alloy (0.5In-0.5Li) powder, 0.01Li 3 PO 4 -0 as a lithium-ion conductive solid electrolyte.
A lithium secondary battery was constructed by using 63Li 2 S-0.36SiS 2 glass and lithium cobalt oxide (LiCoO 2 ) for the positive electrode. The details are shown below. First, 0.0
1 Li 3 PO 4 -0.63Li 2 S-0.36SiS 2 Lithium ion conductive glassy solid electrolyte is crushed to 100 mesh or less in a mortar and pressed into a disk with a diameter of 10 mm and a thickness of 0.5 mm. Molded. Further, a mixture of lithium cobalt oxide (LiCoO 2 ) and the above lithium ion conductive glassy solid electrolyte powder in a weight ratio of 2: 3 was pressure-molded to form a disk shape having a thickness of 0.5 mm and a diameter of 10 mm. It was used as the positive electrode. The negative electrode was prepared by mixing the indium-lithium alloy (0.5In-0.5Li) powder and the lithium ion conductive glassy solid electrolyte powder in a weight ratio of 2: 1 and press-molding the mixture to obtain a thickness. 0.1 mm,
A disc having a diameter of 10 mm was used. Then, the molded body of the solid electrolyte was sandwiched between the positive electrode and the negative electrode and pressed into contact with each other to form an all-solid lithium secondary battery.
【００４５】このリチウム二次電池を電流密度１００μ
Ａ／ｃｍ2で充放電サイクル試験を行った結果、９００
サイクル経過しても充放電容量は初期から低下すること
なく、また充放電効率も１００％で推移し安定に動作す
ることがわかった。また、電池を充電状態で解体し、負
極と電解質の界面を顕微鏡観察を行ったが、デンドライ
トの生成は認められなかった。さらに、この構成の電池
を８０℃の恒温槽に入れ、インピーダンスの経時変化を
測定した結果、１０００時間経過してもインピーダンス
の変化は認められなかった。This lithium secondary battery was tested with a current density of 100 μm.
As a result of charge / discharge cycle test at A / cm 2 , 900
It was found that the charge / discharge capacity did not decrease from the beginning even after the cycle passed, and the charge / discharge efficiency remained at 100% and the operation was stable. Further, the battery was disassembled in a charged state, and the interface between the negative electrode and the electrolyte was observed under a microscope, but no dendrite formation was observed. Further, the battery having this structure was placed in a constant temperature bath at 80 ° C., and the change in impedance with time was measured. As a result, no change in impedance was observed even after 1000 hours had elapsed.
【００４６】［実施例６４］負極にインジウム−鉛−リ
チウム合金（０．５Ｉｎ−０．２Ｐｂ−０．３Ｌｉ）箔
を用いた以外は、実施例４５と同様の方法で全固体リチ
ウム二次電池を構成した。インジウム−鉛−リチウム合
金箔は、インジウム箔と鉛箔およびリチウム箔を原子比
で５：２：３となる割合の量を圧接し、アルゴン雰囲気
中において１５０℃で４８時間固相反応させることによ
り得た。[Example 64] An all-solid-state lithium secondary battery was manufactured in the same manner as in Example 45 except that an indium-lead-lithium alloy (0.5In-0.2Pb-0.3Li) foil was used for the negative electrode. Configured. The indium-lead-lithium alloy foil is obtained by pressing indium foil, lead foil, and lithium foil in an amount of 5: 2: 3 in atomic ratio, and subjecting them to solid phase reaction at 150 ° C. for 48 hours in an argon atmosphere. Obtained.
【００４７】このリチウム電池の充放電サイクル試験を
電流密度１００μＡ／ｃｍ2で行ったところ、８００サ
イクルに到達しても初期の放電容量を維持し、さらに充
放電効率は１００％となり、充放電曲線にも変化は起こ
らなかった。また、このリチウム電池を充電状態で解体
し、負極と固体電解質の界面の状態を顕微鏡で観察した
ところ、デンドライトの生成は認められなかった。When a charge / discharge cycle test of this lithium battery was conducted at a current density of 100 μA / cm 2 , the initial discharge capacity was maintained even after reaching 800 cycles, and the charge / discharge efficiency was 100%. No change occurred. In addition, when this lithium battery was disassembled in a charged state and the state of the interface between the negative electrode and the solid electrolyte was observed with a microscope, dendrite formation was not observed.
【００４８】［実施例６５］負極にガリウム−アルミニ
ウム−リチウム合金（０．５Ｇａ−０．３Ａｌ−０．２
Ｌｉ）粉末を用いた以外は、実施例４５と同様の全固体
リチウム二次電池を構成した。ガリウム−アルミニウム
−リチウム合金は、アルミニウム粉末とガリウム粉末お
よびリチウム粉末の原子比で３：５：２の割合の混合物
を乳鉢で粉末状になるまで充分混合した後、アルゴン雰
囲気中において１５０℃で２４時間反応させることによ
り得た。この合金粉末と０．０２Ｌｉ3ＰＯ4−０．６３
Ｌｉ2Ｓ−０．３５ＳｉＳ2で表されるリチウムイオン導
電性ガラス粉末を重量比で２：１の割合で混合し、厚さ
０．１ｍｍ、直径１０ｍｍの円盤に加圧成形し、負極と
して用いた。[Example 65] A gallium-aluminum-lithium alloy (0.5Ga-0.3Al-0.2) was used for the negative electrode.
An all-solid lithium secondary battery was constructed in the same manner as in Example 45 except that Li) powder was used. The gallium-aluminum-lithium alloy was prepared by thoroughly mixing a mixture of aluminum powder, gallium powder and lithium powder in an atomic ratio of 3: 5: 2 until powdery in a mortar, and then adding 24 at 150 ° C. in an argon atmosphere. Obtained by reacting for a time. This alloy powder and 0.02Li 3 PO 4 -0.63
A lithium ion conductive glass powder represented by Li 2 S-0.35SiS 2 is mixed at a weight ratio of 2: 1 and pressure-molded into a disk having a thickness of 0.1 mm and a diameter of 10 mm to be used as a negative electrode. I was there.
【００４９】このリチウム電池を電流密度１００μＡ／
ｃｍ2で充放電サイクル試験を行ったところ、９００サ
イクルに到達しても初期の放電容量を維持し、さらに充
放電効率は１００％となり、充放電曲線にも変化は起こ
らなかった。また、このリチウム電池を充電状態で解体
し、負極と固体電解質の界面の状態を顕微鏡で観察した
ところ、デンドライトの生成は認められなかった。This lithium battery was tested with a current density of 100 μA /
When the charge / discharge cycle test was conducted at cm 2 , the initial discharge capacity was maintained even after reaching 900 cycles, the charge / discharge efficiency was 100%, and the charge / discharge curve did not change. In addition, when this lithium battery was disassembled in a charged state and the state of the interface between the negative electrode and the solid electrolyte was observed with a microscope, dendrite formation was not observed.
【００５０】なお、上記実施例３３〜６５においては、
負極のリチウム合金として特定の合金を用いて説明した
が、他のインジウム−リチウム、鉛−リチウム、錫−リ
チウム、亜鉛−リチウム、カドミウム−リチウム、アン
チモン−リチウム、ビスマス−リチウム、ガリウム−リ
チウム、チタン−リチウムのいずれか、もしくはこれら
を主体とする合金を用いても同様の効果が得られる。本
発明は合金種について上記に限定されるものではない。Incidentally, in the above Examples 33 to 65,
Although a specific alloy has been described as the lithium alloy for the negative electrode, other indium-lithium, lead-lithium, tin-lithium, zinc-lithium, cadmium-lithium, antimony-lithium, bismuth-lithium, gallium-lithium, titanium. The same effect can be obtained by using any one of lithium or an alloy mainly containing them. The present invention is not limited to the above alloy types.
【００５１】［実施例６６］負極活物質としてアルミニ
ウム（Ａｌ）箔を用い、リチウムイオン導電性固体電解
質として０．０１Ｌｉ3ＰＯ4−０．６３Ｌｉ2Ｓ−０．
３６ＳｉＳ2ガラスを用い、正極活物質にコバルト酸リ
チウム（ＬｉＣｏＯ2）を用いて、リチウム電池を構成
した。以下にその詳細を示す。まず、０．０１Ｌｉ3Ｐ
Ｏ4−０．６３Ｌｉ2Ｓ−０．３６ＳｉＳ2で表されるリ
チウムイオン導電性ガラス状固体電解質を乳鉢で１００
メッシュ以下に粉砕し、直径１０ｍｍ、厚さ１．０ｍｍ
のディスク状に加圧成形した。また、コバルト酸リチウ
ム（ＬｉＣｏＯ2）と前記リチウムイオン導電性ガラス
状固体電解質粉末を重量比で２：３の割合で混合し、こ
の混合物を加圧成形し厚さ０．５ｍｍ、直径１０ｍｍの
円盤状正極とした。負極は厚さ０．１ｍｍのアルミニウ
ム箔を直径１０ｍｍの円盤に切り抜いて用いた。そし
て、前記固体電解質の成形体を前記正極および負極で挟
んで圧接し、全固体リチウム二次電池とした。Example 66 Aluminum (Al) foil was used as the negative electrode active material, and 0.01 Li 3 PO 4 -0.63 Li 2 S-0.
A lithium battery was constructed by using 36SiS 2 glass and using lithium cobalt oxide (LiCoO 2 ) as a positive electrode active material. The details are shown below. First, 0.01Li 3 P
A lithium ion conductive glassy solid electrolyte represented by O 4 -0.63Li 2 S-0.36SiS 2 was used in a mortar for 100 times.
Grinded into mesh or less, diameter 10 mm, thickness 1.0 mm
Was pressed into a disk shape. Further, lithium cobalt oxide (LiCoO 2 ) and the lithium ion conductive glassy solid electrolyte powder were mixed in a weight ratio of 2: 3, and this mixture was pressure-molded to form a disk having a thickness of 0.5 mm and a diameter of 10 mm. Shaped positive electrode. For the negative electrode, an aluminum foil having a thickness of 0.1 mm was cut out into a disk having a diameter of 10 mm and used. Then, the molded body of the solid electrolyte was sandwiched between the positive electrode and the negative electrode and pressure-welded to obtain an all-solid lithium secondary battery.
【００５２】このリチウム二次電池を電流密度１００μ
Ａ／ｃｍ2で充放電サイクル試験を行った。その結果、
１０００サイクル経過しても充放電容量は初期から低下
することなく、また充放電効率もほぼ１００％で推移し
安定に動作することがわかった。また、このリチウム電
池を充電状態で解体し、負極と固体電解質の界面の状態
を顕微鏡で観察したところ、デンドライトの発生は認め
られなかった。さらに、充電状態にあるこの電池を８０
℃の恒温槽に入れインピーダンスの経時変化を測定した
結果、１８００時間経過してもインピーダンスの変化は
認められなかった。以上のように、本発明によるとリチ
ウムデンドライトの生成がなく安全性が高いリチウム二
次電池を得ることができることがわかった。This lithium secondary battery was tested at a current density of 100 μm.
A charge / discharge cycle test was performed at A / cm 2 . as a result,
It was found that the charge / discharge capacity did not decrease from the beginning even after 1000 cycles, and the charge / discharge efficiency remained at almost 100% and the operation was stable. Further, when this lithium battery was disassembled in a charged state and the state of the interface between the negative electrode and the solid electrolyte was observed with a microscope, generation of dendrite was not observed. In addition, charge this battery 80
As a result of measuring the change with time of impedance in a constant temperature bath at ℃, no change in impedance was observed even after 1800 hours. As described above, according to the present invention, it was found that a lithium secondary battery having high safety without generation of lithium dendrite can be obtained.
【００５３】［実施例６７〜８７］以下に、正極、固体
電解質、負極の材料を変え種々の組み合わせによって実
施例６６と同様にして電池を構成した。これらの組み合
わせを表１３、１５および１７に、また評価結果を表１
４、１６および表１７にそれぞれ示す。[Examples 67 to 87] In the following, batteries were constructed in the same manner as in Example 66 by changing the materials of the positive electrode, the solid electrolyte and the negative electrode, and various combinations. These combinations are shown in Tables 13, 15 and 17, and the evaluation results are shown in Table 1.
4, 16 and Table 17, respectively.
【００５４】[0054]
【表１３】 [Table 13]
【００５５】[0055]
【表１４】 [Table 14]
【００５６】[0056]
【表１５】 [Table 15]
【００５７】[0057]
【表１６】 [Table 16]
【００５８】[0058]
【表１７】 [Table 17]
【００５９】[0059]
【表１８】 [Table 18]
【００６０】［比較例９］比較のために負極に直径１０
ｍｍ、厚さ０．１ｍｍの円盤状アルミニウム−リチウム
合金（０．６Ａｌ−０．４Ｌｉ）箔を用い、正極にコバ
ルト酸リチウム（ＬｉＣｏＯ2）の粉末を加圧成形し厚
さ０．５ｍｍ、直径１０ｍｍの円盤としたものを用い、
これらをポリエチレン製のセパレータを介してそれぞれ
を対向させ、電池ケースに収納した。そして、１Ｍ−Ｌ
ｉＣｌＯ4のプロピレンカーボネート溶液を電池ケース
に注入して有機電解液を用いたリチウム二次電池を構成
した。Comparative Example 9 For comparison, the negative electrode had a diameter of 10
mm-thickness 0.1 mm thick disc-shaped aluminum-lithium alloy (0.6Al-0.4Li) foil is used, and lithium cobalt oxide (LiCoO 2 ) powder is pressure-molded on the positive electrode to have a thickness of 0.5 mm and a diameter. Using a 10 mm disc,
These were made to oppose each other through the polyethylene separator and housed in the battery case. And 1M-L
A propylene carbonate solution of iClO 4 was injected into a battery case to form a lithium secondary battery using an organic electrolytic solution.
【００６１】この電池を電流密度１００μＡ／ｃｍ2で
充放電サイクル試験を行った。その結果、初期および２
回目の放電容量が著しく異なり、２回目の放電容量は１
回目の約８０％を示した。その後約８０サイクルを経過
すると、充放電容量の低下が認められ、２５０サイクル
で充放電不能となった。この電池を解体し、観察した結
果、負極のインジウム−リチウム合金箔が微細化し、部
分的に脱落しているのがわかった。また、脱落に到って
いない部分においてリチウムのデンドライトが発生して
おり、セパレータを貫通しているのが確認された。ま
た、同様の構成の電池を充電状態で８０℃の恒温槽に入
れ、インピーダンスの経時変化を測定したところ、金属
負極表面の不動態化によると考えられるインピーダンス
の増加が初期段階より観測された。The battery was subjected to a charge / discharge cycle test at a current density of 100 μA / cm 2 . As a result, initial and 2
The discharge capacity of the second time is significantly different, and the discharge capacity of the second time is 1
It showed about 80% of the first time. After about 80 cycles, a decrease in charge / discharge capacity was observed, and charge / discharge became impossible after 250 cycles. As a result of disassembling and observing this battery, it was found that the indium-lithium alloy foil of the negative electrode was miniaturized and partially dropped off. In addition, it was confirmed that dendrite of lithium was generated in a portion that had not fallen off and penetrated the separator. Further, when a battery having the same configuration was charged in a thermostat at 80 ° C. in a charged state and the change in impedance with time was measured, an increase in impedance, which was considered to be due to passivation of the surface of the metal negative electrode, was observed from the initial stage.
【００６２】［比較例１０］比較のために固体電解質を
０．４５ＬｉＩ−０．３５Ｌｉ2Ｓ−０．２ＳｉＳ2ガラ
スとした以外は実施例７９と同様の電池を構成した。[Comparative Example 10] For comparison, a battery was constructed in the same manner as in Example 79 except that 0.45LiI-0.35Li 2 S-0.2SiS 2 glass was used as the solid electrolyte.
【００６３】このリチウム電池について電流密度１００
μＡ／ｃｍ2で充放電サイクル試験を行ったところ、サ
イクル数を重ねるごとに放電容量が漸次減少する現象が
認められ、３００サイクルを経過したところで充電途中
で電圧が上昇しなくなった。このリチウム電池を解体
し、負極と固体電解質の界面の状態を顕微鏡で観察した
ところ、デンドライトの生成が観察された。短絡したた
めに充電が不能になったと考えられる。さらに、充電状
態にある電池を８０℃の恒温槽に入れインピーダンスの
経時変化を測定した結果、３０時間後からインピーダン
スの増大が観測された。Regarding this lithium battery, the current density was 100.
When a charge / discharge cycle test was conducted at μA / cm 2 , a phenomenon in which the discharge capacity gradually decreased as the number of cycles was repeated was observed, and after 300 cycles, the voltage did not rise during charging. When this lithium battery was disassembled and the state of the interface between the negative electrode and the solid electrolyte was observed with a microscope, generation of dendrites was observed. It is considered that charging was disabled due to a short circuit. Furthermore, as a result of placing the battery in a charged state in a thermostat at 80 ° C. and measuring the time-dependent change in impedance, an increase in impedance was observed after 30 hours.
【００６４】［比較例１１］比較のために固体電解質を
０．６Ｌｉ2Ｓ−０．４Ｂ2Ｓ3ガラスとした以外は実施
例７９と同様の電池を構成した。[Comparative Example 11] For comparison, a battery was constructed in the same manner as in Example 79 except that the solid electrolyte was changed to 0.6Li 2 S-0.4B 2 S 3 glass.
【００６５】このリチウム電池について電流密度１００
μＡ／ｃｍ2で充放電サイクル試験を行ったところ、サ
イクル数を重ねるごとに放電容量が漸次低下した。ま
た、この電池を充放電サイクル試験をしながら充電後の
休止時間中にインピーダンス測定を行った結果、サイク
ル数の進行とともにインピーダンスの増加が認められた
ことから、固体電解質の分解が起こっているものと考え
られる。This lithium battery has a current density of 100.
When a charge / discharge cycle test was performed at μA / cm 2 , the discharge capacity gradually decreased as the number of cycles was increased. In addition, as a result of impedance measurement during the rest period after charging while charging / discharging cycle test of this battery, an increase in impedance was observed as the number of cycles progressed, so that decomposition of the solid electrolyte occurred. it is conceivable that.
【００６６】［比較例１２］比較のために固体電解質を
０．６Ｌｉ2Ｓ−０．４Ｐ2Ｓ5ガラスに、正極活物質を
ＬｉＮｉＯ2に、負極金属をアルミニウム−鉛−リチウ
ム合金（０．５Ａｌ−０．２Ｐｂ−０．３Ｌｉ）とした
以外は実施例６６と同様にして電池を構成した。COMPARATIVE EXAMPLE 12 For comparison, the solid electrolyte was 0.6Li 2 S-0.4P 2 S 5 glass, the positive electrode active material was LiNiO 2 , and the negative electrode metal was aluminum-lead-lithium alloy (0. A battery was formed in the same manner as in Example 66, except that 5Al-0.2Pb-0.3Li) was used.
【００６７】このリチウム電池について電流密度１００
μＡ／ｃｍ2で充放電サイクル試験を行ったところ、サ
イクル数を重ねるごとに放電容量が十数％の減少が認め
られた。また、この電池を充放電サイクル試験をしなが
ら充電後の休止時間中にインピーダンス測定を行った結
果、サイクル数の進行とともにインピーダンスの増加が
認められたことから、固体電解質の分解が起こっている
ものと考えられる。This lithium battery has a current density of 100.
When the charge / discharge cycle test was conducted at μA / cm 2 , the discharge capacity decreased by 10% or more as the number of cycles was increased. In addition, as a result of impedance measurement during the rest period after charging while charging / discharging cycle test of this battery, an increase in impedance was observed as the number of cycles progressed, so that decomposition of the solid electrolyte occurred. it is conceivable that.
【００６８】［実施例８８］負極にアルミニウム−リチ
ウム（０．５Ａｌ−０．５Ｌｉ）合金粉末を、リチウム
イオン導電性固体電解質として０．０１Ｌｉ3ＰＯ4−
０．６３Ｌｉ2Ｓ−０．３６ＳｉＳ2ガラスを、正極にコ
バルト酸リチウム（ＬｉＣｏＯ2）を用いて、リチウム
電池を構成した。以下にその詳細を示す。まず、０．０
１Ｌｉ3ＰＯ4−０．６３Ｌｉ2Ｓ−０．３６ＳｉＳ2で表
されるリチウムイオン導電性ガラス状固体電解質を乳鉢
で１００メッシュ以下に粉砕し、直径１０ｍｍ、厚さ
０．５ｍｍの円盤に加圧成形した。また、コバルト酸リ
チウム（ＬｉＣｏＯ2）と上記リチウムイオン導電性ガ
ラス状固体電解質粉末を重量比で２：３の割合で混合
し、この混合物を加圧成形して厚さ０．５ｍｍ、直径１
０ｍｍの円盤状正極とした。負極はインジウム−リチウ
ム合金（０．５Ａｌ−０．５Ｌｉ）粉末と上記リチウム
イオン導電性ガラス状固体電解質粉末を重量比で２：１
の割合で混合し、この混合物を加圧成形し、厚さ０．１
ｍｍ、直径１０ｍｍの円盤としたものを用いた。そし
て、前記固体電解質の成形体を前記正極および負極で挟
んで圧接し、全固体リチウム二次電池を構成した。[0068] [Example 88] aluminum anode - 0.01Li 3 PO 4 and lithium (0.5Al-0.5Li) alloy powder, a lithium ion conductive solid electrolyte -
A lithium battery was constructed using 0.63Li 2 S-0.36SiS 2 glass and lithium cobalt oxide (LiCoO 2 ) for the positive electrode. The details are shown below. First, 0.0
1 Li 3 PO 4 -0.63Li 2 S-0.36SiS 2 Lithium ion conductive glassy solid electrolyte is crushed to 100 mesh or less in a mortar and pressed into a disk with a diameter of 10 mm and a thickness of 0.5 mm. Molded. Further, lithium cobalt oxide (LiCoO 2 ) and the lithium ion conductive glassy solid electrolyte powder were mixed in a weight ratio of 2: 3, and this mixture was pressure-molded to have a thickness of 0.5 mm and a diameter of 1 mm.
The disk-shaped positive electrode was 0 mm. The negative electrode is composed of indium-lithium alloy (0.5Al-0.5Li) powder and the lithium ion conductive glassy solid electrolyte powder in a weight ratio of 2: 1.
And the mixture is pressure-molded to a thickness of 0.1.
A disc having a diameter of 10 mm and a diameter of 10 mm was used. Then, the molded body of the solid electrolyte was sandwiched between the positive electrode and the negative electrode and pressed into contact with each other to form an all-solid lithium secondary battery.
【００６９】このリチウム二次電池を電流密度１００μ
Ａ／ｃｍ2で充放電サイクル試験を行った結果、８００
サイクル経過しても充放電容量は初期から低下すること
なく、また充放電効率も１００％で推移し安定に動作す
ることがわかった。また、電池を充電状態で解体し、負
極と電解質の界面を顕微鏡観察を行ったが、デンドライ
トの生成は認められなかった。さらに、この構成の電池
を８０℃の恒温槽に入れ、インピーダンスの経時変化を
測定した結果、１０００時間経過してもインピーダンス
の変化は認められなかった。This lithium secondary battery was tested with a current density of 100 μm.
The result of the charge / discharge cycle test at A / cm 2 is 800
It was found that the charge / discharge capacity did not decrease from the beginning even after the cycle passed, and the charge / discharge efficiency remained at 100% and the operation was stable. Further, the battery was disassembled in a charged state, and the interface between the negative electrode and the electrolyte was observed under a microscope, but no dendrite formation was observed. Further, the battery having this structure was placed in a constant temperature bath at 80 ° C., and the change in impedance with time was measured. As a result, no change in impedance was observed even after 1000 hours had elapsed.
【００７０】［実施例８９］負極にアルミニウム−イン
ジウム−リチウム合金（０．４Ａｌ−０．４Ｉｎ−０．
２Ｌｉ）箔を用いた以外は、実施例７９と同様の方法で
全固体リチウム二次電池を構成した。アルミニウム−イ
ンジウム−リチウム合金箔は、アルミニウム箔とインジ
ウム箔およびリチウム箔を原子比で４：４：２の割合と
なる量を圧接し、アルゴン雰囲気において１５０℃で４
８時間固相反応させることにより得た。[Example 89] An aluminum-indium-lithium alloy (0.4Al-0.4In-0.
2Li) An all-solid-state lithium secondary battery was constructed in the same manner as in Example 79 except that the foil was used. The aluminum-indium-lithium alloy foil is obtained by pressing aluminum foil, indium foil and lithium foil in an atomic ratio of 4: 4: 2 at a ratio of 4 at 150 ° C. in an argon atmosphere.
It was obtained by solid phase reaction for 8 hours.
【００７１】このリチウム電池の充放電サイクル試験を
電流密度１００μＡ／ｃｍ2で行ったところ、９００サ
イクルに到達しても初期の放電容量を維持し、さらに充
放電効率は１００％となり、充放電曲線にも変化は起こ
らなかった。また、このリチウム電池を充電状態で解体
し、負極と固体電解質の界面の状態を顕微鏡で観察した
ところ、デンドライトの生成は認められなかった。When the charge / discharge cycle test of this lithium battery was conducted at a current density of 100 μA / cm 2 , the initial discharge capacity was maintained even after 900 cycles were reached, and the charge / discharge efficiency was 100%. No change occurred. In addition, when this lithium battery was disassembled in a charged state and the state of the interface between the negative electrode and the solid electrolyte was observed with a microscope, dendrite formation was not observed.
【００７２】［実施例９０］負極にアルミニウム−ガリ
ウム−リチウム合金（０．４Ａｌ−０．３Ｇａ−０．３
Ｌｉ）粉末を用いた以外は、実施例７９と同様の全固体
リチウム二次電池を構成した。アルミニウム−ガリウム
−リチウム合金は、アルミニウム粉末とガリウム粉末、
およびリチウム箔を原子比で４：３：３の割合で混ぜ、
これを乳鉢で粉末状になるまで充分混合した後、アルゴ
ン雰囲気において１５０℃で２４時間反応させることに
より得た。この合金粉末と０．０２Ｌｉ3ＰＯ4−０．６
３Ｌｉ2Ｓ−０．３５ＳｉＳ2で表されるリチウムイオン
導電性ガラス粉末を重量比で２：１の割合で混合し、こ
の混合物を厚さ０．１ｍｍ、直径１０ｍｍの円盤に加圧
成形し、負極として用いた。Example 90 An aluminum-gallium-lithium alloy (0.4Al-0.3Ga-0.3) was used as the negative electrode.
An all-solid lithium secondary battery was constructed in the same manner as in Example 79 except that Li) powder was used. Aluminum-gallium-lithium alloy, aluminum powder and gallium powder,
And lithium foil at an atomic ratio of 4: 3: 3,
It was obtained by thoroughly mixing it in a mortar until it became powdery and then reacting it at 150 ° C. for 24 hours in an argon atmosphere. The alloy powder and 0.02Li 3 PO 4 -0.6
Lithium ion conductive glass powder represented by 3Li 2 S-0.35SiS 2 was mixed at a weight ratio of 2: 1, and this mixture was pressure-molded into a disk having a thickness of 0.1 mm and a diameter of 10 mm, Used as a negative electrode.
【００７３】このリチウム電池を用いて、電流密度１０
０μＡ／ｃｍ2で充放電サイクル試験を行ったところ、
８００サイクルに到達しても初期の放電容量を維持し、
さらに充放電効率は１００％となり、充放電曲線にも変
化は起こらなかった。また、このリチウム電池を充電状
態で解体し、負極と固体電解質の界面の状態を顕微鏡で
観察したところ、デンドライトの生成は認められなかっ
た。Using this lithium battery, a current density of 10
When the charge / discharge cycle test was performed at 0 μA / cm 2 ,
Maintains the initial discharge capacity even after reaching 800 cycles,
Further, the charging / discharging efficiency was 100%, and the charging / discharging curve did not change. In addition, when this lithium battery was disassembled in a charged state and the state of the interface between the negative electrode and the solid electrolyte was observed with a microscope, dendrite formation was not observed.
【００７４】なお、上記の実施例６６〜９０において
は、アルミニウム−リチウムを主体とする合金としてア
ルミニウム−インジウム−リチウム合金、アルミニウム
−ガリウム−リチウム合金を用いて説明したが、他の合
金を用いても同様の効果が得られる。本発明は合金種に
ついて上記に限定されるものではない。In the above Examples 66 to 90, aluminum-indium-lithium alloy and aluminum-gallium-lithium alloy were used as the alloy mainly containing aluminum-lithium, but other alloys were used. Also has the same effect. The present invention is not limited to the above alloy types.
【００７５】また、上記実施例においては、正極と負極
および固体電解質の組成や組み合わせを特定のものに限
定して説明したが、本発明はそれらに限定されるもので
はない。Further, in the above embodiments, the composition and combination of the positive electrode, the negative electrode and the solid electrolyte are limited to specific ones, but the present invention is not limited to them.
【００７６】[0076]
【発明の効果】以上のように本発明によれば、デンドラ
イトの発生による短絡がなく、充放電サイクル特性に優
れた安全性の高い全固体リチウム二次電池が得られる。As described above, according to the present invention, it is possible to obtain an all-solid-state lithium secondary battery which is free from short circuit due to generation of dendrite and has excellent charge / discharge cycle characteristics and high safety.
フロントページの続き (72)発明者 近藤 繁雄 大阪府門真市大字門真1006番地 松下電器 産業株式会社内Front page continued (72) Inventor Shigeo Kondo 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.
Claims (9)
遷移金属硫化物よりなる群から選択される化合物を含む
正極、Ｌｉ2Ｓを含むリチウムイオン導電性のガラス固
体電解質、およびリチウムと合金化する金属を活物質と
して含む負極を具備し、前記正極の活物質および負極金
属活物質の少なくとも一方がリチウムを含むことを特徴
とする全固体リチウム二次電池。1. A positive electrode containing a compound selected from the group consisting of transition metal oxides and transition metal sulfides as a positive electrode active material, a lithium ion conductive glass solid electrolyte containing Li 2 S, and an alloy with lithium. An all-solid-state lithium secondary battery comprising a negative electrode containing a metal as an active material, wherein at least one of the positive electrode active material and the negative electrode metal active material contains lithium.
ｎ、Ｓｎ、Ｓｂ、Ｂｉ、Ｃｄ、Ｇａ、およびＴｉよりな
る群から選ばれる金属、または前記金属の少なくとも一
種を含む合金である請求項１記載の全固体リチウム二次
電池2. The metal active material of the negative electrode is In, Pb, Z
The all-solid-state lithium secondary battery according to claim 1, which is a metal selected from the group consisting of n, Sn, Sb, Bi, Cd, Ga, and Ti, or an alloy containing at least one of the metals.
主成分とする合金である請求項１記載の全固体リチウム
二次電池。3. The all-solid-state lithium secondary battery according to claim 1, wherein the metal active material of the negative electrode is Al or an alloy containing Al as a main component.
している請求項２または３記載の全固体リチウム二次電
池。4. The all-solid-state lithium secondary battery according to claim 2, wherein the metal active material of the negative electrode is alloyed with lithium.
ＭｎＯ2、ＬｉxＭｎ2Ｏ4、ＬｉxＮｉＯ2、ＬｉxＴｉ
Ｓ2、ＬｉxＭｏＳ2、およびＬｉxＭｏ6Ｓ8よりなる群か
ら選択される化合物（ただし、ｘ≧０）である請求項１
記載の全固体リチウム二次電池。5. The active material of the positive electrode is Li x CoO 2 , Li x
MnO 2 , Li x Mn 2 O 4 , Li x NiO 2 , Li x Ti
A compound (where x ≧ 0) selected from the group consisting of S 2 , Li x MoS 2 , and Li x Mo 6 S 8.
The all-solid-state lithium secondary battery described.
3、Ｐ2Ｓ5、およびＢ2Ｓ3よりなる群から選択される少
なくとも一種を含む請求項１〜５のいずれかに記載の全
固体リチウム二次電池。6. The solid electrolyte further comprises SiS 2 , Al 2 S
The all-solid-state lithium secondary battery according to any one of claims 1 to 5, containing at least one selected from the group consisting of 3 , P 2 S 5 , and B 2 S 3 .
だし、ＸはＳｉＳ2、Ａｌ2Ｓ3、Ｐ2Ｓ5、およびＢ2Ｓ3
よりなる群から選択される少なくとも一種であり、０．
３＜ａ）で表される請求項６記載の全固体リチウム二次
電池。7. The solid electrolyte has the formula aLi 2 S—X, where X is SiS 2 , Al 2 S 3 , P 2 S 5 , and B 2 S 3.
At least one selected from the group consisting of:
The all-solid-state lithium secondary battery according to claim 6, represented by 3 <a).
Ｏ4、Ｌｉ2ＳＯ4、およびＬｉ2ＣＯ3よりなる群から選
択される少なくとも一種を含む請求項６記載の全固体リ
チウム二次電池。8. The solid electrolyte further comprises Li 2 O and Li 3 P.
The all-solid-state lithium secondary battery according to claim 6, containing at least one selected from the group consisting of O 4 , Li 2 SO 4 , and Li 2 CO 3 .
［ａＬｉ2Ｓ−（１−ａ）Ｘ］（ただし、ＸはＳｉＳ2、
Ａｌ2Ｓ3、Ｐ2Ｓ5、およびＢ2Ｓ3よりなる群から選択さ
れる少なくとも一種であり、ＹはＬｉ2Ｏ、Ｌｉ3Ｐ
Ｏ4、Ｌｉ2ＳＯ4、およびＬｉ2ＣＯ3よりなる群から選
択される少なくとも一種であり、０．３＜ａ、ｂ＜０．
３）で表される請求項８記載の全固体リチウム二次電
池。9. The solid electrolyte has the formula bY- (1-b).
[ALi 2 S- (1-a) X] (where X is SiS 2 ,
At least one selected from the group consisting of Al 2 S 3 , P 2 S 5 , and B 2 S 3 , and Y is Li 2 O, Li 3 P
At least one selected from the group consisting of O 4 , Li 2 SO 4 , and Li 2 CO 3 , and 0.3 <a, b <0.
The all-solid-state lithium secondary battery according to claim 8, which is represented by 3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24032395A JP3332133B2 (en) | 1994-09-21 | 1995-09-19 | All-solid lithium secondary battery |
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22657894 | 1994-09-21 | ||
| JP6-226580 | 1994-09-21 | ||
| JP6-226578 | 1994-09-21 | ||
| JP6-226579 | 1994-09-21 | ||
| JP22657994 | 1994-09-21 | ||
| JP22658094 | 1994-09-21 | ||
| JP24032395A JP3332133B2 (en) | 1994-09-21 | 1995-09-19 | All-solid lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08148180A true JPH08148180A (en) | 1996-06-07 |
| JP3332133B2 JP3332133B2 (en) | 2002-10-07 |
Family
ID=27477221
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|---|---|---|---|
| JP24032395A Expired - Fee Related JP3332133B2 (en) | 1994-09-21 | 1995-09-19 | All-solid lithium secondary battery |
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| Country | Link |
|---|---|
| JP (1) | JP3332133B2 (en) |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000173587A (en) * | 1998-12-02 | 2000-06-23 | Matsushita Electric Ind Co Ltd | Non-aqueous electrolyte secondary battery |
| JP2000173588A (en) * | 1998-12-02 | 2000-06-23 | Matsushita Electric Ind Co Ltd | Non-aqueous electrolyte secondary battery |
| JP2006179243A (en) * | 2004-12-21 | 2006-07-06 | Sanyo Electric Co Ltd | Lithium secondary battery |
| WO2008123394A1 (en) * | 2007-03-23 | 2008-10-16 | Toyota Jidosha Kabushiki Kaisha | Mixed material layer, method for production of the mixed material layer, solid battery, and method for production of the solid battery |
| US7517616B2 (en) | 2001-02-28 | 2009-04-14 | Sumitomo Electric Industries, Ltd. | Inorganic solid electrolyte and lithium cell component |
| WO2009048146A1 (en) * | 2007-10-10 | 2009-04-16 | Kobelco Research Institute, Inc. | Negative electrode active material for rechargeable battery, rechargeble battery using the negative electrode active material, and air rechargeable battery |
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1995
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