JPH10247516A - All-solid lithium battery - Google Patents

All-solid lithium battery

Info

Publication number
JPH10247516A
JPH10247516A JP9048667A JP4866797A JPH10247516A JP H10247516 A JPH10247516 A JP H10247516A JP 9048667 A JP9048667 A JP 9048667A JP 4866797 A JP4866797 A JP 4866797A JP H10247516 A JPH10247516 A JP H10247516A
Authority
JP
Japan
Prior art keywords
current collector
solid
metal
lithium battery
battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP9048667A
Other languages
Japanese (ja)
Inventor
Kazuya Iwamoto
和也 岩本
Makoto Fujino
信 藤野
Kazunori Takada
和典 高田
Shigeo Kondo
繁雄 近藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Holdings Corp
Original Assignee
Matsushita Electric Industrial Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Priority to JP9048667A priority Critical patent/JPH10247516A/en
Publication of JPH10247516A publication Critical patent/JPH10247516A/en
Pending legal-status Critical Current

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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

PROBLEM TO BE SOLVED: To provide an all-solid lithium secondary battery having an excellent charge/discharge cycle characteristic by lessening the internal resistance, suppressing its increase in association with the expansion and contraction of the battery at the time of charging and discharging, and enhancing the electricity collecting performance. SOLUTION: To a battery case 2 an electricity collecting body 1 made of metal is fixed at a plurality of points 3 and thereby the contact of the electricity collecting body 1 with the electrode is made movable with respect to the battery case 2 connected with the electricity collecting body and it is possible to generate electric contacting of a battery pellet with the positive and negative electrodes sufficiently even when the battery case 2 and/or sealing plate is deformed or the electrode is expanded or contracted at the time of charging or discharging.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は全固体リチウム電池
に関するものである。[0001] The present invention relates to an all-solid lithium battery.

【０００２】[0002]

【従来の技術】近年、パーソナルコンピュータ，携帯電
話等のポータブル機器の開発に伴い、その電源として電
池の需要は非常に大きなものとなっている。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, with the development of portable devices such as personal computers and mobile phones, demand for batteries as power sources has become extremely large. In particular, since lithium has a small atomic weight and a large ionization energy, lithium batteries have been actively studied in various fields as batteries capable of obtaining a high energy density.

【０００３】一方、これらの用途の電池は、電解質に液
体を使用しているため、電解質の漏液等の問題を皆無と
することができない。こうした問題を解決し信頼性を高
めるため、また素子を小型，薄型化するためにも、液体
電解質を固体電解質に代えて、電池を全固体化する試み
が各方面でなされている。特に、先に述べたリチウム電
池に関しては、そのエネルギー密度の高さのために、電
池に異常が生じた際には電池が発火する等の恐れがあ
る。そのため、電池の安全性を確保するために、不燃性
の固体材料で構成される固体電解質を用いた全固体リチ
ウム電池の開発が望まれている。このような電池に用い
られる固体電解質としては、ハロゲン化リチウム，窒化
リチウム，リチウム酸素酸塩、あるいはこれらの誘導体
等が知られている。また、Ｌｉ2Ｓ−ＳｉＳ2，Ｌｉ2Ｓ
−Ｐ2Ｓ5，Ｌｉ2Ｓ−Ｂ2Ｓ3等のリチウムイオン導電性
硫化物ガラス状固体電解質や、これらのガラスにＬｉＩ
等のハロゲン化リチウム、Ｌｉ3ＰＯ4等のリチウム酸素
酸塩をドープしたリチウムイオン導電性固体電解質は、
１０-4〜１０-3Ｓ／ｃｍの高いイオン導電性を有するこ
とから世界的にその物性を中心とした研究が行われてい
る。[0003] On the other hand, batteries for these applications use a liquid as an electrolyte, so that problems such as electrolyte leakage cannot be eliminated. In order to solve these problems and improve the reliability and to reduce the size and thickness of the element, various attempts have been made in all aspects to replace the liquid electrolyte with a solid electrolyte and make the battery all solid. In particular, with respect to the above-described lithium battery, due to its high energy density, when an abnormality occurs in the battery, the battery may be ignited. Therefore, in order to ensure battery safety, development of an all-solid lithium battery using a solid electrolyte composed of a nonflammable solid material is desired. As a solid electrolyte used for such a battery, lithium halide, lithium nitride, lithium oxyacid salt, a derivative thereof, and the like are known. Li 2 S—SiS 2 , Li 2 S
-P 2 S 5, Li 2 S -B 2 S 3 such as a lithium ion conductive sulfide glassy solid electrolytes and, LiI these glass
Lithium halide, Li 3 PO lithium ion conductive solid electrolyte doped with lithium oxyacid salt such as 4 etc.,
Due to its high ionic conductivity of 10 -4 to 10 -3 S / cm, researches on its physical properties have been conducted worldwide.

【０００４】[0004]

【発明が解決しようとする課題】しかしながら、全固体
リチウム電池を粉末成型法により構成し、従来のコイン
型電池ケースあるいはボタン型電池ケースに挿入し、こ
の周囲をかしめて封口した際には、正極，負極，電解質
層よりなる電池構成群が全て堅い固体からなるため、電
池ケースあるいは封口板にひずみが生じやすく、正極，
負極の電極端子を兼ねるそれぞれの電池ケースあるいは
封口板と電極ペレットとが充分な接触を保つことができ
ず、内部抵抗が増大し充電または放電が困難となる。However, when an all-solid lithium battery is formed by a powder molding method, inserted into a conventional coin-type battery case or button-type battery case, and its periphery is swaged, the positive electrode is closed. , A negative electrode, and an electrolyte layer are all made of a solid solid, so that the battery case or the sealing plate tends to be distorted,
The battery case or sealing plate also serving as the negative electrode terminal cannot keep sufficient contact with the electrode pellet, and the internal resistance increases, making charging or discharging difficult.

【０００５】また、二次電池の場合、初期的に接触を保
つことができ、充放電が可能であった場合でも、充放電
サイクルの進行に伴って、電極の膨脹，収縮が繰り返さ
れることにより、電池ケースあるいは封口板と電極との
間に隙間や電極ペレット中での活物質間の接合の弛みが
生じやすく、内部抵抗が上昇し、充放電容量が低下する
といった課題があった。[0005] In the case of a secondary battery, the contact can be maintained at an initial stage, and even if charging and discharging are possible, the expansion and contraction of the electrode are repeated as the charging and discharging cycle progresses. In addition, there is a problem that the gap between the battery case or the sealing plate and the electrode and the loosening of the bond between the active materials in the electrode pellet are easily generated, the internal resistance increases, and the charge / discharge capacity decreases.

【０００６】従って、この全固体リチウム電池において
は、上述の組み立て時および充放電時における内部抵抗
の低減と高い集電性が要求されている。Therefore, in this all-solid lithium battery, a reduction in internal resistance and a high current collecting property during the above-described assembling and charging and discharging are required.

【０００７】本発明は、以上の課題を解決し、さらに充
放電時における電池の膨脹，収縮に伴う内部抵抗の増加
を低減するとともに集電性を高め、優れた充放電サイク
ル特性を有する全固体リチウム電池を提供することを目
的とする。[0007] The present invention solves the above-mentioned problems and further reduces the increase in internal resistance due to the expansion and contraction of the battery during charging and discharging, enhances current collection, and provides an all-solid having excellent charge-discharge cycle characteristics. It is intended to provide a lithium battery.

【０００８】[0008]

【課題を解決するための手段】この課題を解決するため
に本発明は、電池の組み立て時に電池ケースおよび／ま
たは封口板が歪んだり、また充放電時において電極が膨
脹，収縮した場合でも、電池ペレットの正極および負極
との充分な電気的接触がとれるように構成したものであ
る。SUMMARY OF THE INVENTION In order to solve this problem, the present invention provides a battery which can be used even when the battery case and / or the sealing plate is distorted during the assembly of the battery, or when the electrode expands or contracts during charging and discharging. The pellet is configured such that sufficient electrical contact with the positive electrode and the negative electrode can be obtained.

【０００９】これにより、電池ペレットの正極および負
極と集電体との間に充分な電気的接触が得られる。As a result, sufficient electrical contact between the positive electrode and the negative electrode of the battery pellet and the current collector can be obtained.

【００１０】[0010]

【発明の実施の形態】本発明は各請求項の発明の形態に
よって実施し得る。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention can be embodied by the embodiments of the claims.

【００１１】すなわち、本発明の請求項１に記載の発明
は、電池ケースおよび封口板の少なくとも一方に集電体
を具備し、集電体と電極の接点が電池ケースあるいは封
口板に対して可動的な状態で装填したものであり、電池
ペレットが膨脹，収縮した場合においても接触面がその
厚さ方向の変動に追随するために、正極，負極の電極と
充分な接触を確保することができる。That is, according to the first aspect of the present invention, at least one of the battery case and the sealing plate is provided with a current collector, and the contact between the current collector and the electrode is movable with respect to the battery case or the sealing plate. The contact surface follows the fluctuation in the thickness direction even when the battery pellet expands and contracts, so that sufficient contact with the positive electrode and the negative electrode can be ensured. .

【００１２】また、請求項２に記載の発明は、請求項１
に記載の集電体を金属としたものであり、前記金属の弾
性によって電極が膨脹，収縮した場合においても接触面
がその厚さ方向の変動に追随するために、電池ペレット
の正極および負極との充分な接触を確保することができ
る。The invention described in claim 2 is the first invention.
The current collector according to the above is made of a metal, and even when the electrode expands and contracts due to the elasticity of the metal, the contact surface follows the variation in the thickness direction even when the electrode expands and contracts. Sufficient contact can be secured.

【００１３】請求項３に記載の発明は、請求項２に記載
の金属製の集電体がステンレススチールならびに鉄，チ
タン，銅，ニッケル，アルミニウムもしくはこれらのう
ちの少なくとも一つを主成分とする合金としたものであ
り、前記する金属を用いることにより、集電体は弾性が
得られ、電池ペレットの正極および負極との充分な接触
を確保することができる。According to a third aspect of the present invention, the metal current collector according to the second aspect includes stainless steel and iron, titanium, copper, nickel, aluminum or at least one of these as a main component. The current collector has elasticity by using the above-mentioned metal, and sufficient contact between the positive electrode and the negative electrode of the battery pellet can be secured.

【００１４】請求項４に記載の発明は、請求項２に記載
の金属製の集電体がメッシュ，エキスパンドメタル，発
泡メタル，ワイヤー，パンチングメタル，ファイバーの
群より選ばれる少なくとも一つの形状としたものであ
り、平板状の金属集電体よりも高いバネ弾性が得られ、
電池ペレットの正極および負極との充分な接触を確保す
ることができる。According to a fourth aspect of the present invention, the metal current collector according to the second aspect has at least one shape selected from the group consisting of a mesh, an expanded metal, a foamed metal, a wire, a punched metal, and a fiber. It has higher spring elasticity than a flat metal current collector,
Sufficient contact between the battery pellet and the positive and negative electrodes can be ensured.

【００１５】請求項５に記載の発明は、請求項２に記載
の金属製の集電体の見かけ面積が電池ペレットの正極ま
たは負極の平面部面積の５０〜９９％としたものであ
り、電池の封口時に集電体にかかる圧力により電池ペレ
ットの周辺部に集電体が回り込み、正極と負極が短絡す
ることを防ぐことができる。According to a fifth aspect of the present invention, the apparent area of the metal current collector of the second aspect is 50 to 99% of the plane area of the positive or negative electrode of the battery pellet. It is possible to prevent the current collector from wrapping around the battery pellet due to the pressure applied to the current collector at the time of sealing to prevent a short circuit between the positive electrode and the negative electrode.

【００１６】請求項６に記載の発明は、請求項２に記載
の金属製の集電体が電池ケースおよび封口板の少なくと
も一方に、複数箇所で固定した固定点を有するものであ
り、これにより金属製集電体に固定点を支点としたバネ
弾性が生じ、電池ペレットの正極および負極との充分な
接触を確保することができる。According to a sixth aspect of the present invention, the metal current collector according to the second aspect has a plurality of fixing points fixed to at least one of the battery case and the sealing plate. Spring elasticity with the fixed point as a fulcrum occurs in the metal current collector, and sufficient contact between the positive electrode and the negative electrode of the battery pellet can be secured.

【００１７】請求項７に記載の発明は、請求項１に記載
の集電体が電子伝導性ゴムとしたものであり、特に集電
体に固定点を設けなくとも前記電子伝導性ゴムの弾性に
よって電池ペレットが膨脹，収縮した場合においても接
触面がその厚さ方向の変動に追随するために、電池ペレ
ットの正極および負極との充分な接触を確保することが
できる。According to a seventh aspect of the present invention, the current collector according to the first aspect is an electron conductive rubber, and the elasticity of the electron conductive rubber can be improved without providing a fixed point on the current collector. As a result, even when the battery pellet expands and contracts, the contact surface follows the variation in the thickness direction, so that sufficient contact between the positive electrode and the negative electrode of the battery pellet can be ensured.

【００１８】請求項８に記載の発明は、請求項７に記載
の電子伝導性ゴム製集電体の装填時の態様がシート状ま
たはペースト状としたものであり、特に集電体に固定点
を設けなくとも前記電子伝導性ゴムの弾性によって電池
ペレットの正極および負極との充分な接触を確保するこ
とができる。According to an eighth aspect of the present invention, the electronic conductive rubber current collector according to the seventh aspect is mounted in a sheet-like or paste-like form when it is loaded. Even without providing, a sufficient contact between the positive electrode and the negative electrode of the battery pellet can be secured by the elasticity of the electron conductive rubber.

【００１９】請求項９に記載の発明は、請求項７に記載
の電子伝導性ゴム製集電体の見かけ面積が電池ペレット
の正極または負極の平面部面積の５０〜９９％としたも
のであり、電池の封口時に集電体にかかる圧力により電
池ペレットの周辺部に集電体が回り込み、正極と負極が
短絡することを防ぐことができる。According to a ninth aspect of the present invention, the apparent area of the electron-conductive rubber current collector according to the seventh aspect is 50 to 99% of the plane area of the positive or negative electrode of the battery pellet. In addition, it is possible to prevent the current collector from wrapping around the battery pellet due to the pressure applied to the current collector when the battery is sealed, thereby preventing the positive electrode and the negative electrode from being short-circuited.

【００２０】請求項１０に記載の発明は、正極および負
極の少なくとも一方の中に金属製の集電体を具備させた
ものであり、電極中の金属集電体によって電極内部の電
位分布を均一化し、電池ケースおよび封口板に装着され
た集電体との集電性を高めることができる。According to a tenth aspect of the present invention, a metal current collector is provided in at least one of the positive electrode and the negative electrode, and the potential distribution inside the electrode is made uniform by the metal current collector in the electrode. It is possible to enhance the current collection with the current collector mounted on the battery case and the sealing plate.

【００２１】請求項１１に記載の発明は、請求項１０に
記載の金属製の集電体がメッシュ，エキスパンドメタ
ル，発泡メタル，ワイヤー，パンチングメタル，ファイ
バーの群より選ばれる少なくとも一つの形状としたもの
であり、電極中に電子伝導ネットワークを張り巡らせ、
電極中での電位分布を均一化することができる。According to an eleventh aspect of the present invention, the metal current collector according to the tenth aspect has at least one shape selected from the group consisting of a mesh, an expanded metal, a foamed metal, a wire, a punching metal, and a fiber. The electronic conduction network is stretched through the electrodes,
The potential distribution in the electrode can be made uniform.

【００２２】請求項１２に記載の発明は、請求項１０に
記載の金属製の集電体がステンレススチールならびに
鉄，チタン，銅，ニッケル，アルミニウムもしくはこれ
らのうちの少なくとも一つを主成分とする合金としたも
のであり、これらの金属が有する弾性によって充放電時
における電極の膨脹，収縮を低減させると同時に、金属
の良導電性によって集電効率を高めることができる。According to a twelfth aspect of the present invention, the metal current collector of the tenth aspect is made of stainless steel and iron, titanium, copper, nickel, aluminum or at least one of these as a main component. It is an alloy, and the elasticity of these metals can reduce the expansion and contraction of the electrodes during charge and discharge, and at the same time, the current collection efficiency can be increased by the good conductivity of the metals.

【００２３】請求項１３に記載の発明は、請求項１０に
記載の金属製の集電体の見かけ面積が集電体を中部に有
する正極および／または負極の平面部面積の７０〜９９
％としたものであり、電池ペレットの外部に露出した電
極中の集電体によるエッジ部での短絡を防ぐことができ
る。According to a thirteenth aspect of the present invention, the apparent area of the metal current collector according to the tenth aspect is 70 to 99 of the plane area of the positive electrode and / or the negative electrode having the current collector in the middle.
%, And it is possible to prevent a short circuit at the edge portion due to the current collector in the electrode exposed to the outside of the battery pellet.

【００２４】以下、本発明の実施の形態の１から３につ
いて、図１ないし図４を参照して説明する。Hereinafter, embodiments 1 to 3 of the present invention will be described with reference to FIGS. 1 to 4.

【００２５】（実施の形態１）図１は金属製集電体１を
９つの固定点で固定した電池ケース２を示したものであ
り、図２は図１におけるＡＢ線上での断面を示したもの
である。図１において、金属製集電体１と電極ペレット
の接触点が電池ケース２に対して可動的な状態で装填し
たもの、すなわち、図２に示したように金属製集電体１
を歪んだ形状で設けることにより、電池ペレットが膨
脹，収縮した場合にでも接触面がその厚さ方向に変動に
追随するために、正極，負極の電極と充分な接触を確保
することができる。(Embodiment 1) FIG. 1 shows a battery case 2 in which a metal current collector 1 is fixed at nine fixing points, and FIG. 2 shows a cross section taken along line AB in FIG. Things. In FIG. 1, the metal collector 1 and the electrode pellet are mounted so that the contact point between the metal collector 1 and the electrode pellet is movable with respect to the battery case 2, that is, as shown in FIG.
Is provided in a distorted shape, so that even when the battery pellet expands and contracts, the contact surface follows the fluctuation in the thickness direction, so that sufficient contact with the positive electrode and the negative electrode can be ensured.

【００２６】金属製集電体１としては、例えばステンレ
ススチール，鉄，チタン，銅，ニッケル，アルミニウム
もしくはこれらのうちの少なくとも一つを主成分とする
合金からなるものが使用でき、特に電子伝導性と弾性お
よび耐食性に優れた点ではステンレススチールが好まし
い。As the metal current collector 1, for example, one made of stainless steel, iron, titanium, copper, nickel, aluminum or an alloy containing at least one of these as a main component can be used. Stainless steel is preferred because of its excellent elasticity and corrosion resistance.

【００２７】また、金属製集電体１の形状としては、例
えばメッシュ，エキスパンドメタル，発泡メタル，ワイ
ヤー，パンチングメタル，ファイバー等の形状を用いる
ことができるが、特に高弾性を付与するためには、メッ
シュ，エキスパンドメタルの形状が好ましい。As the shape of the metal current collector 1, for example, mesh, expanded metal, foamed metal, wire, punching metal, fiber and the like can be used. , Mesh and expanded metal are preferred.

【００２８】金属製集電体１の見かけ面積は電池ペレッ
トの電極平面部の面積の４０％以上で効果が認められる
が、特に５０％以上ではその効果が顕著となる。しかし
ながら、電極面積に対して１００％以上になるとエッジ
部における正極，負極の短絡が発生しやすくなるため、
５０〜９９％が好ましい。The effect is recognized when the apparent area of the metal current collector 1 is 40% or more of the area of the electrode flat portion of the battery pellet, and the effect is particularly remarkable when it is 50% or more. However, if the area is 100% or more with respect to the electrode area, a short circuit between the positive electrode and the negative electrode at the edge portion is likely to occur.
50-99% is preferred.

【００２９】さらに、金属製集電体１と電池ケース２と
の固定点３の数は１点以上であれば効果が認められる
が、高い弾性と電池ケース２との電気的接合を得るため
には面積に依らず４点以上が好ましい。また、１３点／
ｃｍ2以上になると固定点３間が著しく近接するため弾
性が低下し、電池ペレットが膨脹，収縮した場合に接触
面がその厚さ方向の変動に追随しにくくなり、正極，負
極の電極と充分な接触が保てなくなる。従って、固定点
３は面積に依らず最低４点、上限は単位面積当たり１３
点／ｃｍ2であることが好ましい。Further, if the number of the fixing points 3 between the metal current collector 1 and the battery case 2 is one or more, the effect is recognized. However, in order to obtain high elasticity and electrical connection with the battery case 2. Is preferably four or more regardless of the area. 13 points /
When it exceeds 2 cm2, the elasticity decreases because the fixed points 3 are extremely close to each other, so that when the battery pellet expands and contracts, the contact surface does not easily follow the variation in the thickness direction. Contact cannot be maintained. Therefore, the fixed point 3 is at least 4 points regardless of the area, and the upper limit is 13 points per unit area.
It is preferably points / cm 2 .

【００３０】（実施の形態２）図３は実施の形態１と異
なり電子伝導性ゴム製集電体４を具備した電池ケース５
を有する実施の形態であり、電子伝導性ゴム製集電体４
と電極ペレットの接触点が電池ケース５に対して可動的
な状態で装填したものであり、前記電子伝導性ゴム製集
電体４の弾性によって、電池ペレットが膨脹，収縮した
場合においても接触面がその厚さ方向の変動に追随する
ために、正極，負極の電極と充部な接触を確保すること
ができる。(Embodiment 2) FIG. 3 is different from Embodiment 1 in that a battery case 5 having an electron conductive rubber current collector 4 is provided.
And a current collector 4 made of an electron conductive rubber.
The contact point between the battery pellet and the electrode pellet is mounted so as to be movable with respect to the battery case 5. Due to the elasticity of the electron-conductive rubber current collector 4, even when the battery pellet expands and contracts, the contact surface is formed. Can follow the variation in the thickness direction, so that a full contact with the positive electrode and the negative electrode can be ensured.

【００３１】電子伝導性ゴム製集電体４はシート状体を
必要な形状，大きさに打ち抜いて電池ケースに装填、あ
るいは前記電子伝導性ゴムのペーストを電池ケースに塗
布，乾燥した後用いてもいずれの場合にも効果が認めら
れるが、均一な膜厚が得られるといった点でシート状体
を用いるのが好ましい。The electron-conductive rubber current collector 4 is used by punching a sheet into a required shape and size and mounting the same in a battery case, or by applying and drying the paste of the electron-conductive rubber to the battery case. In any case, the effect is recognized, but it is preferable to use a sheet-like body in that a uniform film thickness can be obtained.

【００３２】電子伝導性ゴム製集電体４の導電剤はニッ
ケル，鉄，金，銀，白金といった金属粉末やこれらの金
属で被覆した樹脂製マイクロビーズ、あるいはアセチレ
ンブラックやケッチェンブラック，黒鉛といった炭素材
料を用いるとよい。The conductive agent of the electron-conductive rubber current collector 4 is a metal powder such as nickel, iron, gold, silver, or platinum, resin microbeads coated with these metals, or acetylene black, Ketjen black, or graphite. It is preferable to use a carbon material.

【００３３】また、電子伝導性ゴム製集電体４に用いら
れる樹脂としてはアクリル系，シリコン系，スチレン−
ブタジエン共重合体等があるが弾性に富む点でシリコン
系、あるいはスチレン−ブタジエン共重合体が好まし
い。The resin used for the electron conductive rubber current collector 4 may be an acrylic resin, a silicon resin, or a styrene resin.
There are butadiene copolymers and the like, but silicon-based or styrene-butadiene copolymers are preferred because of their high elasticity.

【００３４】なお、以上の説明では電子伝導性ゴム製集
電体４を電池ケース５に装着した構成を例として説明し
たが、電池ケース５の代りに封口板に電子伝導性ゴム製
集電体４を装着しても実施可能であり、同様の効果が得
られることはいうまでもない。In the above description, the configuration in which the electronically conductive rubber current collector 4 is mounted on the battery case 5 has been described as an example. However, instead of the battery case 5, the electronically conductive rubber current collector is provided on the sealing plate. 4 can be implemented, and needless to say, the same effect can be obtained.

【００３５】（実施の形態３）図４は実施の形態３につ
いて示すものであり、正極ペレット６および負極ペレッ
ト７にはそれぞれ金属製集電体８，９を埋設して固体電
池ペレット１０とする。図４において、金属製集電体
８，９は電極との電子的接合をより確実なものとすると
同時に電極中の集電効果を高める作用を有する。(Embodiment 3) FIG. 4 shows Embodiment 3 in which metal current collectors 8, 9 are embedded in a positive electrode pellet 6 and a negative electrode pellet 7, respectively, to form a solid battery pellet 10. . In FIG. 4, the metal current collectors 8 and 9 have the function of increasing the electric current collecting effect in the electrodes while ensuring the electronic connection with the electrodes.

【００３６】金属製集電体８，９は、例えばステンレス
スチール，鉄，チタン，銅，ニッケル，アルミニウムも
しくはこれらのうちの少なくとも一つを主成分とする合
金からなるものが使用でき、特に電子伝導性と弾性およ
び耐食性に優れた点でステンレススチールが好ましい。The metal current collectors 8 and 9 may be made of, for example, stainless steel, iron, titanium, copper, nickel, aluminum or an alloy containing at least one of them as a main component. Stainless steel is preferred because of its excellent properties, elasticity and corrosion resistance.

【００３７】また、金属製集電体８，９の形状として
は、例えばメッシュ，エキスパンドメタル，発泡メタ
ル，ワイヤー，パンチングメタル，ファイバー等の形状
を用いることができる。Further, as the shape of the metal current collectors 8 and 9, for example, mesh, expanded metal, foamed metal, wire, punching metal, fiber and the like can be used.

【００３８】金属製集電体８，９の見かけ面積は固体電
池ペレット１０の電極平面部面積の６０％以上で効果が
認められるが、特に７０％以上ではその効果が顕著とな
る。しかしながら、電極面積に対して１００％以上にな
るとエッジ部における正極，負極の短絡が発生しやすく
なるため、７０〜９９％が好ましい。The apparent area of the metal current collectors 8 and 9 is effective when the area is 60% or more of the plane area of the electrode of the solid battery pellet 10, and the effect is particularly remarkable when the area is 70% or more. However, if the electrode area is 100% or more with respect to the electrode area, a short circuit between the positive electrode and the negative electrode at the edge portion is likely to occur.

【００３９】[0039]

【実施例】次に、本発明の具体的実施例について比較例
と比較しながら説明する。Next, specific examples of the present invention will be described in comparison with comparative examples.

【００４０】（実施例１）Ｌｉ3ＰＯ4−Ｌｉ2Ｓ−Ｓｉ
Ｓ2のガラス状の固体電解質粉末を直径１６．８ｍｍの
ペレットに加圧成形した後、そのペレットの一方に前記
固体電解質粉末に正極活物質としてコバルト酸リチウム
（ＬｉＣｏＯ2）からなる正極合剤を加えて予備成型し
て固体電解質層とした。次いで、固体電解質層を挟んで
対向する他方の面にインジウム粉末と固体電解質粉末か
らなる負極合剤を加えて一体成型を行い、全固体リチウ
ム二次電池ペレットを構成した。Example 1 Li 3 PO 4 —Li 2 S—Si
The glassy solid electrolyte powder of S 2 was pressed into a pellet having a diameter of 16.8 mm, and then, on one of the pellets, a positive electrode mixture comprising lithium cobalt oxide (LiCoO 2 ) as a positive electrode active material was added to the solid electrolyte powder. In addition, it was preformed to obtain a solid electrolyte layer. Next, a negative electrode mixture composed of indium powder and solid electrolyte powder was added to the other surface opposing the solid electrolyte layer, and integrally molded to form an all-solid lithium secondary battery pellet.

【００４１】前記全固体リチウム二次電池ペレットを直
径１４．２ｍｍのステンレス製メッシュ（対電池ケース
の平面部面積比５０％）を図１に示したように９点の固
定点でスポット溶接した正極側電池ケースと加工しない
負極側封口板を用いて封口し、直径２０ｍｍ，厚さ１．
６ｍｍのコイン型全固体リチウム二次電池を得た。A positive electrode obtained by spot-welding the all-solid lithium secondary battery pellets to a stainless steel mesh having a diameter of 14.2 mm (50% of the area ratio of the flat portion of the battery case) at nine fixed points as shown in FIG. The battery is sealed using a side battery case and a non-processed negative electrode side sealing plate, and has a diameter of 20 mm and a thickness of 1.
A 6 mm coin-type all solid lithium secondary battery was obtained.

【００４２】前記実施例１のコイン型全固体リチウム二
次電池の初充電後の内部抵抗は３５０Ωであった。ま
た、本構成によるコイン型全固体リチウム二次電池を１
００個試作した際に内部短絡した電池は皆無であった。
また、前記コイン型全固体リチウム二次電池を５００μ
Ａで充放電した際に充電時のインピーダンスのサイクル
における変化は１００サイクル経過した時点で５％上昇
し、３６８Ωであった。The internal resistance of the coin-type all-solid lithium secondary battery of Example 1 after the initial charge was 350Ω. In addition, the coin-type all-solid lithium secondary battery of this configuration is
There were no batteries that were internally short-circuited when the 00 prototypes were manufactured.
Further, the coin-type all-solid lithium secondary battery is
When charging / discharging with A, the change in the cycle of the impedance at the time of charging increased by 5% after 100 cycles, and was 368Ω.

【００４３】同様に固定点の数を１〜２０点、面積比を
３０〜１０５％とした際のインピーダンスの測定結果を
図５に示した。この図５より面積比５０％以上でインピ
ーダンスの減少が認められた。一方、これらの試験に際
してコイン型全固体リチウム二次電池は各１００個を組
み立て、そのうち面積比が１０５％のものではいずれの
固定点数についても１０個以上のエッジ部での短絡が発
生した。また、これらのコイン型全固体リチウム二次電
池のうちインピーダンスが高かったものについて分解し
てみると１７点以上でスポット溶接した金属製集電体は
電池ペレットと正極の界面が容易に剥離することがわか
り、集電性の低下が生じていた。Similarly, FIG. 5 shows the impedance measurement results when the number of fixed points is 1 to 20 and the area ratio is 30 to 105%. FIG. 5 shows that the impedance was reduced at an area ratio of 50% or more. On the other hand, at the time of these tests, 100 coin-type all solid lithium secondary batteries were assembled, and when the area ratio was 105%, a short circuit occurred at 10 or more edges at any fixed point. In addition, among the coin-type all-solid lithium secondary batteries, those with high impedance were disassembled. The metal current collector spot-welded at 17 points or more showed that the interface between the battery pellet and the positive electrode was easily peeled off. It was found that the current collecting property was reduced.

【００４４】従って、電池ケースの平面部の面積に対す
る金属製集電体の面積は５０〜９９％が最適であり、固
定点は４〜１５点が最適であることがわかった。Accordingly, it was found that the area of the metal current collector with respect to the area of the flat portion of the battery case is optimally 50 to 99%, and the fixed point is optimally 4 to 15 points.

【００４５】（比較例１）実施例１と同様の電池ペレッ
トを金属製集電体を有さない電池ケースおよび封口板を
用いて構成した比較例１のコイン型全固体リチウム二次
電池の初充電後の内部抵抗は１５００Ωであった。ま
た、比較例１のコイン型全固体リチウム二次電池を１０
０個試作した際に内部短絡した電池は皆無であった。比
較例１のコイン型全固体リチウム二次電池を５００μＡ
で充放電した際に充電時のインピーダンスのサイクルに
おける変化は１０サイクル経過した時点で１０％上昇
し、１６５０Ωと極めて変動が大きかった。Comparative Example 1 The coin-type all-solid lithium secondary battery of Comparative Example 1 in which a battery pellet similar to that of Example 1 was formed using a battery case having no metal current collector and a sealing plate was used. The internal resistance after charging was 1500Ω. The coin-type all-solid lithium secondary battery of Comparative Example 1 was
None of the batteries short-circuited internally when zero prototypes were manufactured. 500 μA of the coin-type all-solid lithium secondary battery of Comparative Example 1
When charging / discharging was performed, the change in the cycle of the impedance at the time of charging increased by 10% after 10 cycles, and was extremely large at 1650Ω.

【００４６】（実施例２）実施例１と同様の電池ペレッ
トを直径１４．２ｍｍのステンレス製メッシュ（対封口
板の平面部面積比８１％）を９点の固定点でスポット溶
接した負極側封口板と加工しない正極側電池ケースを用
いて封口し、直径２０ｍｍ，厚さ１．６ｍｍのコイン型
全固体リチウム二次電池を得た。(Example 2) A negative electrode side plug obtained by spot welding the same battery pellet as in Example 1 to nine stainless steel meshes (the area ratio of the flat surface of the sealing plate to 81%) with a diameter of 14.2 mm at nine fixed points. The plate and the positive electrode side battery case which were not processed were sealed to obtain a coin-type all-solid lithium secondary battery having a diameter of 20 mm and a thickness of 1.6 mm.

【００４７】この実施例２のコイン型全固体リチウム二
次電池の初充電後の内部抵抗は３４６Ωであった。ま
た、本構成による実施例２のコイン型全固体リチウム二
次電池を１００個試作した際に内部短絡した電池は皆無
であった。また、前記実施例２のコイン型全固体リチウ
ム二次電池を５００μＡで充放電した際に充電時のイン
ピーダンスのサイクルにおける変化は１００サイクル経
過した時点で１％上昇し、３４９Ωであった。The internal resistance of the coin-type all-solid lithium secondary battery of Example 2 after the initial charge was 346Ω. When 100 coin-type all-solid lithium secondary batteries of Example 2 according to the present configuration were prototyped, none of the batteries had an internal short circuit. Further, when the coin-type all solid lithium secondary battery of Example 2 was charged and discharged at 500 μA, the change in the cycle of the impedance during charging increased by 1% after 100 cycles, and was 349Ω.

【００４８】同様に固定点の数を１〜２０点、面積比を
３０〜１０５％とした際のインピーダンスの測定結果を
図６に示した。この図６より面積比５０％以上でインピ
ーダンスの減少が認められた。一方、これらの試験に際
して電池は各１００個を組み立て、そのうち面積比が１
０５％のものでは、いずれの固定点の数についても１０
個以上のエッジ部での短絡が発生した。従って、封口板
の平面部の面積に対する集電体の面積は５０〜９９％が
最適であることがわかった。Similarly, FIG. 6 shows the measurement results of impedance when the number of fixed points is 1 to 20 and the area ratio is 30 to 105%. FIG. 6 shows that the impedance was reduced at an area ratio of 50% or more. On the other hand, during these tests, 100 batteries were assembled, and the area ratio was 1 unit.
In the case of 05%, the number of any fixed points is 10
Short circuits occurred at more than one edge. Therefore, it was found that the optimal area of the current collector with respect to the area of the flat portion of the sealing plate was 50 to 99%.

【００４９】（実施例３）実施例１と同様の電池ペレッ
トを直径１４．２ｍｍのステンレス製メッシュ（対封口
板の平面部面積比８１％ならびに対電池ケースの平面部
面積比５０％）を９点の固定点でスポット溶接した負極
側封口板と正極側電池ケースを用いて封口し、直径２０
ｍｍ，厚さ１．６ｍｍのコイン型全固体リチウム二次電
池を得た。(Example 3) The same battery pellets as in Example 1 were prepared using a stainless steel mesh having a diameter of 14.2 mm (total area ratio of the sealing plate to 81% and area ratio to the battery case to 50%). Sealing was performed using a negative electrode-side sealing plate and a positive electrode-side battery case spot-welded at the fixed points.
Thus, a coin-type all-solid lithium secondary battery having a thickness of 1.6 mm and a thickness of 1.6 mm was obtained.

【００５０】この実施例３のコイン型全固体リチウム二
次電池の初充電後の内部抵抗は３４０Ωであった。ま
た、本構成による実施例３のコイン型全固体リチウム二
次電池を１００個試作した際に内部短絡した電池は皆無
であった。また、実施例３のコイン型全固体リチウム二
次電池を５００μＡで充放電した際に充電時のインピー
ダンスのサイクルにおける変化は１００サイクル経過し
た時点でもほとんどインピーダンスの増加は生ぜず、３
４１Ωであった。The internal resistance of the coin-type all-solid lithium secondary battery of Example 3 after the initial charge was 340Ω. In addition, when 100 coin-type all-solid lithium secondary batteries of Example 3 according to the present configuration were prototyped, none of the batteries had an internal short circuit. Further, when the coin-type all solid lithium secondary battery of Example 3 was charged and discharged at 500 μA, the change in the cycle of the impedance at the time of charging showed almost no increase in the impedance even after 100 cycles.
It was 41Ω.

【００５１】実施例１と実施例２を併せて考えると、正
極側の面積比と負極側の面積比を種々組み合わせた場合
にも実施例１および実施例２同様の効果が期待できるこ
とは明らかであり、従って、電池ケースおよび封口板に
対するステンレスメッシュ製集電体の面積比は５０〜９
９％、固定点の数は４〜１５点が最適であることがわか
った。When Examples 1 and 2 are considered together, it is clear that the same effects as in Examples 1 and 2 can be expected even when the area ratio on the positive electrode side and the area ratio on the negative electrode side are variously combined. Therefore, the area ratio of the stainless mesh current collector to the battery case and the sealing plate is 50 to 9
9%, and the optimal number of fixed points was found to be 4 to 15 points.

【００５２】以下に実施例３と同様の構成で集電体の材
質，形状のみを変えたものについてインピーダンスの結
果をまとめて表１に示す。ただし、導電性ゴムペースト
は他の集電体と同面積となるように塗布し、乾燥後電池
ペレットを挿入した。また、導電性ゴムシートは同面積
のものを、特にゴムの粘性のみで固定し、装填した。ま
た、ここで用いた導電性ゴムペーストの導電剤はケッチ
ェンブラックであり、導電性ゴムシートの導電剤はニッ
ケル粉末である。Table 1 below summarizes the impedance results for the current collector having the same configuration as that of the third embodiment except for the material and shape of the current collector. However, the conductive rubber paste was applied so as to have the same area as other current collectors, and after drying, battery pellets were inserted. In addition, the conductive rubber sheet having the same area was fixed and loaded only with the viscosity of rubber in particular. The conductive agent of the conductive rubber paste used here is Ketjen black, and the conductive agent of the conductive rubber sheet is nickel powder.

【００５３】[0053]

【表１】 [Table 1]

【００５４】表１の結果から集電体の材質および形状に
依らず実施例３と同様の効果が得られることがわかっ
た。From the results shown in Table 1, it was found that the same effect as in Example 3 was obtained irrespective of the material and shape of the current collector.

【００５５】（実施例４）Ｌｉ3ＰＯ4−Ｌｉ2Ｓ−Ｓｉ
Ｓ2のガラス状の固体電解質粉末を直径１６．８ｍｍの
ペレットに加圧成形した後、そのペレットの一方に前記
固体電解質粉末に正極活物質としてコバルト酸リチウム
（ＬｉＣｏＯ2）からなる正極合剤を加え、さらに直径
１５ｍｍのステンレス製メッシュ（対正極見かけ面積比
８０％）を装填して予備成型し固体電解質層とした。次
いで、固体電解質層を挟んで対向する他方の面にインジ
ウム粉末と固体電解質粉末からなる負極合剤を加えて一
体成型を行い、全固体リチウム二次電池ペレットを構成
した以外は実施例３と同様の構成で直径２０ｍｍ，厚さ
１．６ｍｍのコイン型全固体リチウム二次電池を得た。Example 4 Li 3 PO 4 —Li 2 S—Si
The glassy solid electrolyte powder of S 2 was pressed into a pellet having a diameter of 16.8 mm, and then, on one of the pellets, a positive electrode mixture comprising lithium cobalt oxide (LiCoO 2 ) as a positive electrode active material was added to the solid electrolyte powder. In addition, a stainless steel mesh having a diameter of 15 mm (approximately 80% of the area of the positive electrode) was preliminarily molded and formed into a solid electrolyte layer. Next, the same procedure as in Example 3 was carried out except that a negative electrode mixture composed of indium powder and solid electrolyte powder was added to the other surface opposed to the solid electrolyte layer in between to form an all-solid lithium secondary battery pellet. Thus, a coin-type all solid lithium secondary battery having a diameter of 20 mm and a thickness of 1.6 mm was obtained.

【００５６】この実施例４のコイン型全固体リチウム二
次電池の初充電後の内部抵抗は２５３Ωであった。ま
た、本構成による実施例４のコイン型全固体リチウム二
次電池を１００個試作した際に内部短絡した電池は皆無
であった。また、実施例４のコイン型全固体リチウム二
次電池を５００μＡで充放電した際に充電時のインピー
ダンスのサイクルにおける変化は１００サイクル経過し
た時点ではほとんど変わらず、２５５Ωであった。The internal resistance of the coin-type all-solid lithium secondary battery of Example 4 after the initial charge was 253 Ω. When 100 coin-type all-solid lithium secondary batteries of Example 4 according to this configuration were prototyped, none of the batteries was internally short-circuited. In addition, when the coin-type all-solid lithium secondary battery of Example 4 was charged and discharged at 500 μA, the change in the cycle of the impedance at the time of charging was almost unchanged after 100 cycles, and was 255Ω.

【００５７】以下に正極見かけ面積に対する種々の正極
中集電体面積比を変えた以外は実施例４と同様の電池に
ついての結果を表２に示す。Table 2 below shows the results of a battery similar to that of Example 4 except that the ratio of various current collector area in the positive electrode to the apparent area of the positive electrode was changed.

【００５８】[0058]

【表２】 [Table 2]

【００５９】（比較例２）正極側電池ケースと負極側封
口板に集電体を装填しない以外は実施例４と同様のコイ
ン型全固体リチウム二次電池を構成した。Comparative Example 2 A coin-type all-solid lithium secondary battery was constructed in the same manner as in Example 4 except that no current collector was loaded in the positive electrode side battery case and the negative electrode side sealing plate.

【００６０】前記比較例２のコイン型全固体リチウム二
次電池の初充電後のインピーダンスは９００Ωであっ
た。また、前記比較例２のコイン型全固体リチウム二次
電池を１００個試作した際に内部短絡した電池は皆無で
あった。また、前記比較例２のコイン型全固体リチウム
二次電池を５００μＡで充放電した際に充電時のインピ
ーダンスのサイクルにおける変化は１００サイクル経過
した時点で３３％上昇し、１２００Ωと極めて変動が大
きかった。The impedance after the initial charge of the coin-type all-solid lithium secondary battery of Comparative Example 2 was 900Ω. When 100 coin-type all-solid lithium secondary batteries of Comparative Example 2 were prototyped, none of the batteries had an internal short circuit. In addition, when the coin-type all-solid lithium secondary battery of Comparative Example 2 was charged and discharged at 500 μA, the change in the impedance cycle during charging increased by 33% after 100 cycles, and was extremely large at 1200Ω. .

【００６１】以上の結果から電池ケースまたは封口板に
集電体をスポット溶接した場合よりも正極中に集電体を
装填することによって一層電池のインピーダンスを低減
することができ、サイクル中のインピーダンスの増大も
抑制することができることがわかった。From the above results, it is possible to further reduce the impedance of the battery by loading the current collector in the positive electrode as compared with the case where the current collector is spot-welded to the battery case or the sealing plate, and to reduce the impedance during the cycle. It has been found that the increase can be suppressed.

【００６２】なお、本発明の実施例においては、Ｘ−Ｌ
ｉ2Ｓ−ＳｉＳ2の固体電解質ガラスのＸがリン酸リチウ
ム（Ｌｉ3ＰＯ4）の場合についてのみ説明を行ったが、
Ｘが無い場合、あるいは酸化リチウム（Ｌｉ2Ｏ），硫
酸リチウム（Ｌｉ2ＳＯ4），炭酸リチウム（Ｌｉ2Ｃ
Ｏ3），ホウ酸リチウム（Ｌｉ3ＢＯ3）等、他のリチウ
ム酸素酸塩の場合についても同様の効果が得られること
は明らかであり、本発明はＸがリン酸リチウムの場合に
のみ限定されるものではない。Incidentally, in the embodiment of the present invention, X-L
Although only the case where X of the solid electrolyte glass of i 2 S—SiS 2 is lithium phosphate (Li 3 PO 4 ) has been described,
When there is no X, or lithium oxide (Li 2 O), lithium sulfate (Li 2 SO 4 ), lithium carbonate (Li 2 C
It is clear that similar effects can be obtained in the case of other lithium oxyacid salts such as O 3 ) and lithium borate (Li 3 BO 3 ), and the present invention is limited only to the case where X is lithium phosphate. It is not something to be done.

【００６３】また、本発明の実施例における全固体リチ
ウム二次電池の負極材料にインジウム箔を用いて説明を
行ったが、金属リチウム，アルミニウム，スズ等のリチ
ウムと合金化しやすい金属、あるいはリチウム合金、さ
らに遷移金属酸化物，遷移金属硫化物等を用いても同様
の効果が期待できることは明らかであり、本発明は実施
例にのみ限定されるものではない。In the embodiments of the present invention, an indium foil was used as a negative electrode material for an all-solid lithium secondary battery. However, metals such as metallic lithium, aluminum, and tin, which are easily alloyed with lithium, or lithium alloys It is clear that similar effects can be expected even when transition metal oxides, transition metal sulfides, and the like are used, and the present invention is not limited to only the examples.

【００６４】また、本発明の実施例における全固体リチ
ウム二次電池の正極材料にコバルト酸リチウムを用いて
説明を行ったが、ニッケル酸リチウム，マンガン酸リチ
ウム等、他の遷移金属酸化物や二硫化チタン，二硫化モ
リブデン等の遷移金属硫化物を用いても同様の効果が期
待でき、本発明は実施例にのみ限定されるものではな
い。Further, although lithium cobalt oxide was used as the positive electrode material of the all-solid lithium secondary battery in the examples of the present invention, other transition metal oxides such as lithium nickelate, lithium manganate, etc. The same effect can be expected even if a transition metal sulfide such as titanium sulfide or molybdenum disulfide is used, and the present invention is not limited only to the examples.

【００６５】[0065]

【発明の効果】以上のように本発明によれば、電池ケー
スおよび封口板の少なくとも一方に金属製もしくは導電
性ゴム製の集電体を前記集電体と電極の接点が前記集電
体と接続される電池ケース、あるいは封口板に対して可
動的であるように装填することにより封口時または充放
電に伴う電池ケース、あるいは封口板に膨れを生じた場
合において充分な電子的な接触が確保できるという有利
な効果が得られる。As described above, according to the present invention, a current collector made of metal or conductive rubber is provided on at least one of the battery case and the sealing plate so that the contact between the current collector and the electrode is in contact with the current collector. Sufficient electronic contact is ensured when the battery case to be connected or the sealing plate is movably loaded so that the battery case or the sealing plate swells during sealing or during charging and discharging. The advantageous effect that it can be obtained is obtained.

【００６６】さらに、電極中に集電体を装填することで
電極との電子的接合をより確実なものとすることがで
き、内部抵抗の低い全固体リチウム電池が得られる。Further, by loading the current collector in the electrode, the electronic bonding with the electrode can be made more reliable, and an all-solid lithium battery having a low internal resistance can be obtained.

【図面の簡単な説明】[Brief description of the drawings]

【図１】本発明の実施の形態１における金属製集電体を
設けた電池ケースを示す平面図FIG. 1 is a plan view showing a battery case provided with a metal current collector according to Embodiment 1 of the present invention.

【図２】同図１のＡＢ線による断面図FIG. 2 is a sectional view taken along line AB in FIG. 1;

【図３】本発明の実施の形態２における電子伝導性ゴム
製集電体を設けた電池ケースを示す平面図FIG. 3 is a plan view showing a battery case provided with an electron-conductive rubber current collector according to Embodiment 2 of the present invention.

【図４】本発明の実施の形態３における金属製集電体を
電極中に埋設した固体電池ペレットを示す斜視図FIG. 4 is a perspective view showing a solid battery pellet in which a metal current collector according to Embodiment 3 of the present invention is embedded in an electrode.

【図５】本発明の一実施例におけるインピーダンスと集
電体装着条件の関係を示す説明図FIG. 5 is an explanatory diagram showing a relationship between impedance and current collector mounting conditions in one embodiment of the present invention.

【図６】本発明の他の実施例におけるインピーダンスと
集電体装着条件の関係を示す説明図FIG. 6 is an explanatory diagram showing the relationship between impedance and current collector mounting conditions in another embodiment of the present invention.

【符号の説明】[Explanation of symbols]

１，８，９ 金属製集電体 ２，５ 電池ケース ３ 固定点 ４ 電子伝導性ゴム製集電体 ６ 正極ペレット ７ 負極ペレット １０ 固体電池ペレット 1,8,9 Metal current collector 2,5 Battery case 3 Fixing point 4 Electroconductive rubber current collector 6 Positive electrode pellet 7 Negative electrode pellet 10 Solid battery pellet

───────────────────────────────────────────────────── 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 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shigeo Kondo 1006 Kazuma Kadoma, Osaka Prefecture Inside Matsushita Electric Industrial Co., Ltd.

Claims (13)

【特許請求の範囲】[Claims] 【請求項１】 正極，負極がリチウムイオン導電性固体
電解質を挟んで対峙する全固体リチウム電池において、
前記電池の電池ケースおよび封口板の少なくとも一方に
集電体を具備し、かつ前記集電体と電極の接点が集電体
と接続された電池ケースあるいは封口板に対して可動的
であることを特徴とする全固体リチウム電池。1. An all-solid lithium battery in which a positive electrode and a negative electrode face each other with a lithium ion conductive solid electrolyte interposed therebetween,
A current collector is provided on at least one of the battery case and the sealing plate of the battery, and the contact between the current collector and the electrode is movable with respect to the battery case or the sealing plate connected to the current collector. Features all-solid lithium battery. 【請求項２】 集電体が金属であることを特徴とする請
求項１記載の全固体リチウム電池。2. The all-solid lithium battery according to claim 1, wherein the current collector is a metal. 【請求項３】 集電体がステンレススチールならびに
鉄，チタン，銅，ニッケル，アルミニウムもしくはこれ
らのうちの少なくとも一つを主成分とする合金からなる
ものであることを特徴とする請求項１または２記載の全
固体リチウム電池。3. The current collector according to claim 1, wherein the current collector is made of stainless steel and iron, titanium, copper, nickel, aluminum or an alloy containing at least one of these as a main component. An all-solid lithium battery as described. 【請求項４】 集電体は金属製であって、メッシュ，エ
キスパンドメタル，発泡メタル，ワイヤー，パンチング
メタル，ファイバーの群より選ばれる少なくとも一つの
形状を有することを特徴とする請求項１ないし３のいず
れかに記載する全固体リチウム電池。4. The current collector is made of metal and has at least one shape selected from the group consisting of mesh, expanded metal, foamed metal, wire, punching metal, and fiber. An all-solid lithium battery according to any one of the above. 【請求項５】 集電体は金属製であって、見かけ面積が
電池ペレットの正極または負極の平面部面積の５０〜９
９％であることを特徴とする請求項１ないし４のいずれ
かに記載する全固体リチウム電池。5. The current collector is made of metal and has an apparent area of 50 to 9 times the area of the flat part of the positive or negative electrode of the battery pellet.
The all-solid-state lithium battery according to any one of claims 1 to 4, wherein the content is 9%. 【請求項６】 集電体は金属製であって、電池ケースお
よび封口板の少なくとも一方に、複数箇所で固定される
固定点を有することを特徴とする請求項１ないし５のい
ずれかに記載する全固体リチウム電池。6. The current collector according to claim 1, wherein the current collector is made of metal, and has at least one of a plurality of fixing points on at least one of the battery case and the sealing plate. All-solid-state lithium battery. 【請求項７】 集電体が電子伝導性ゴム製集電体である
ことを特徴とする請求項１記載の全固体リチウム電池。7. The all solid lithium battery according to claim 1, wherein the current collector is a current collector made of an electronic conductive rubber. 【請求項８】 電子伝導性ゴム製集電体の装填時の態様
がシート状またはペースト状であることを特徴とする請
求項１または７記載の全固体リチウム電池。8. The all-solid-state lithium battery according to claim 1, wherein the current collector made of an electronic conductive rubber is loaded in a sheet or paste form. 【請求項９】 電子伝導性ゴム製集電体の見かけ面積が
電池ペレットの正極または負極の平面部面積の５０〜９
９％であることを特徴とする請求項１，７または８のい
ずれかに記載する全固体リチウム電池。9. The apparent area of the current collector made of an electrically conductive rubber is 50 to 9 times the planar area of the positive or negative electrode of the battery pellet.
9. The all-solid-state lithium battery according to claim 1, wherein the content is 9%. 【請求項１０】 正極および負極の少なくとも一方の中
に金属製の集電体を具備させたことを特徴とする請求項
１ないし９のいずれかに記載する全固体リチウム電池。10. The all-solid lithium battery according to claim 1, wherein a metal current collector is provided in at least one of the positive electrode and the negative electrode. 【請求項１１】 正極および負極の少なくとも一方の中
に具備する集電体が金属製であって、メッシュ，エキス
パンドメタル，発泡メタル，ワイヤー，パンチングメタ
ル，ファイバーの群より選ばれる少なくとも一つの形状
を有することを特徴とする請求項１ないし１０のいずれ
かに記載する全固体リチウム電池。11. The current collector provided in at least one of the positive electrode and the negative electrode is made of metal, and has at least one shape selected from the group consisting of mesh, expanded metal, foamed metal, wire, punching metal, and fiber. The all-solid lithium battery according to any one of claims 1 to 10, comprising: 【請求項１２】 正極および負極の少なくとも一方の中
に具備する集電体が金属製であって、ステンレススチー
ルならびに鉄，チタン，銅，ニッケル，アルミニウムも
しくはこれらのうちの少なくとも一つを主成分とする合
金からなるものであることを特徴とする請求項１ないし
１１のいずれかに記載する全固体リチウム電池。12. The current collector provided in at least one of the positive electrode and the negative electrode is made of metal, and contains stainless steel and iron, titanium, copper, nickel, aluminum or at least one of these as a main component. The all-solid-state lithium battery according to any one of claims 1 to 11, wherein the all-solid-state lithium battery is made of an alloy containing: 【請求項１３】 正極および負極の少なくとも一方の中
に具備する集電体が金属製であって、見かけ面積が前記
集電体を具備する正極および／または負極の平面部面積
の７０〜９９％であることを特徴とする請求項１ないし
１２のいずれかに記載する全固体リチウム電池。13. A current collector provided in at least one of the positive electrode and the negative electrode is made of metal, and has an apparent area of 70 to 99% of the plane area of the positive electrode and / or the negative electrode having the current collector. The all-solid-state lithium battery according to any one of claims 1 to 12, wherein
JP9048667A 1997-03-04 1997-03-04 All-solid lithium battery Pending JPH10247516A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP9048667A JPH10247516A (en) 1997-03-04 1997-03-04 All-solid lithium battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP9048667A JPH10247516A (en) 1997-03-04 1997-03-04 All-solid lithium battery

Publications (1)

Publication Number Publication Date
JPH10247516A true JPH10247516A (en) 1998-09-14

Family

ID=12809690

Family Applications (1)

Application Number Title Priority Date Filing Date
JP9048667A Pending JPH10247516A (en) 1997-03-04 1997-03-04 All-solid lithium battery

Country Status (1)

Country Link
JP (1) JPH10247516A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001023603A (en) * 1999-07-13 2001-01-26 Toshiba Battery Co Ltd Flat nonaqueous electrolyte secondary battery
JP2005056827A (en) * 2003-07-23 2005-03-03 Matsushita Electric Ind Co Ltd Coin-shaped all solid battery
US7083877B2 (en) 2002-06-13 2006-08-01 Matsushita Electric Industrial Co., Ltd. All solid state battery with coated substrate
CN1314156C (en) * 2003-07-23 2007-05-02 松下电器产业株式会社 Coin-shaped all solid battery
US7288340B2 (en) 2003-03-20 2007-10-30 Matsushita Electric Industrial Co., Ltd. Integrated battery
JP2008124036A (en) * 2008-01-10 2008-05-29 Sanyo Electric Co Ltd Negative electrode for lithium secondary battery and lithium secondary battery
JP2018098005A (en) * 2016-12-12 2018-06-21 川崎重工業株式会社 Battery
WO2023238926A1 (en) * 2022-06-10 2023-12-14 マクセル株式会社 Electrode stack, method for producing same and electrochemical element

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001023603A (en) * 1999-07-13 2001-01-26 Toshiba Battery Co Ltd Flat nonaqueous electrolyte secondary battery
US7083877B2 (en) 2002-06-13 2006-08-01 Matsushita Electric Industrial Co., Ltd. All solid state battery with coated substrate
US7288340B2 (en) 2003-03-20 2007-10-30 Matsushita Electric Industrial Co., Ltd. Integrated battery
JP2005056827A (en) * 2003-07-23 2005-03-03 Matsushita Electric Ind Co Ltd Coin-shaped all solid battery
CN1314156C (en) * 2003-07-23 2007-05-02 松下电器产业株式会社 Coin-shaped all solid battery
JP4617105B2 (en) * 2003-07-23 2011-01-19 パナソニック株式会社 Coin-type all-solid-state battery
JP2008124036A (en) * 2008-01-10 2008-05-29 Sanyo Electric Co Ltd Negative electrode for lithium secondary battery and lithium secondary battery
JP2018098005A (en) * 2016-12-12 2018-06-21 川崎重工業株式会社 Battery
WO2023238926A1 (en) * 2022-06-10 2023-12-14 マクセル株式会社 Electrode stack, method for producing same and electrochemical element

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