JPH08167425A - Manufacture of total solid lithium battery - Google Patents
Manufacture of total solid lithium batteryInfo
- Publication number
- JPH08167425A JPH08167425A JP6308695A JP30869594A JPH08167425A JP H08167425 A JPH08167425 A JP H08167425A JP 6308695 A JP6308695 A JP 6308695A JP 30869594 A JP30869594 A JP 30869594A JP H08167425 A JPH08167425 A JP H08167425A
- Authority
- JP
- Japan
- Prior art keywords
- solid
- argon gas
- lithium battery
- sulfide
- lithium
- 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
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
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- Secondary Cells (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電解質としてリチウム
イオン導電性固体電解質を用いた全固体リチウム電池の
製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an all-solid lithium battery using a lithium ion conductive solid electrolyte as an electrolyte.
【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普及にともない、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、
リチウム二次電池は、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実用化さ
れつつある。2. Description of the Related Art In recent years, with the widespread use of portable devices such as personal computers and mobile phones, the demand for batteries as a power source thereof has become very large. In particular,
BACKGROUND ART A lithium secondary battery is being put to practical use as a battery that can obtain a high energy density because lithium has a small atomic weight and a large ionization energy.
【０００３】しかしながら、リチウム電池は電解質とし
て有機溶媒を用いることから、電池が短絡するなど不測
の事態が生じた際には発火等の危険性を皆無とすること
ができない。リチウム電池の安全性を高めるための方法
の一つは、電解質として不燃性の材料である固体電解質
を用い、電池を不燃性材料のみより構成する方法であ
り、現在全固体リチウム電池の研究開発が各方面で行わ
れている。However, since an organic solvent is used as an electrolyte in a lithium battery, there is no risk of ignition when an unexpected situation such as short circuit of the battery occurs. One of the methods for improving the safety of lithium batteries is to use a solid electrolyte, which is a non-combustible material, as the electrolyte, and to configure the battery with only non-combustible materials. It is carried out in all directions.
【０００４】[0004]
【発明が解決しようとする課題】全固体リチウム電池の
負極活物質としては、金属リチウム、リチウム−アルミ
ニウム合金などが用いられるが、これらの材料のリチウ
ムは酸素あるいは窒素と接触することにより（化１）な
らびに（化２）に示した反応で、各々酸化リチウムなら
びに窒化リチウムを生成する。Metallic lithium, lithium-aluminum alloys, and the like are used as the negative electrode active material of all-solid-state lithium batteries, and lithium of these materials is contacted with oxygen or nitrogen (Chemical Formula 1). ) And (Chemical Formula 2), lithium oxide and lithium nitride are produced, respectively.
【０００５】[0005]
【化１】 Embedded image
【０００６】[0006]
【化２】 Embedded image
【０００７】また、全固体リチウム電池電解質として用
いられるリチウムイオン導電性固体電解質の中で、硫化
物系非晶質固体電解質は１０-3／ｃｍ前後の高いイオン
導電率を示しており、全固体リチウム電池用の電解質と
して好適なものの一つである。しかし、これら硫化物系
非晶質固体電解質は、酸素と接触することにより反応す
る。例えば、硫化リチウムと硫化ケイ素を含む物質より
なる固体電解質は、（化３）に示したように酸素との接
触により固体電解質中の硫黄と気相の酸素との交換反応
が生じ、その結果、固体電解質のイオン導電率が低下す
る。Among the lithium ion conductive solid electrolytes used as the all-solid-state lithium battery electrolyte, the sulfide-based amorphous solid electrolyte exhibits a high ionic conductivity of about 10 −3 / cm, It is one of the suitable electrolytes for lithium batteries. However, these sulfide-based amorphous solid electrolytes react by contacting with oxygen. For example, in a solid electrolyte composed of a substance containing lithium sulfide and silicon sulfide, an exchange reaction between sulfur in the solid electrolyte and oxygen in the gas phase occurs as a result of contact with oxygen as shown in (Chemical Formula 3). The ionic conductivity of the solid electrolyte is reduced.
【０００８】[0008]
【化３】 Embedded image
【０００９】したがって、全固体リチウム電池の組み立
てには、アルゴンガスやヘリウムガスなどの不活性ガス
を用いる必要がある。しかし、これらのガスの価格が高
いものであるため、全固体リチウム電池の製造に用いた
場合には製造コストが高いものになるという課題を有し
ていた。Therefore, it is necessary to use an inert gas such as argon gas or helium gas for assembling the all-solid-state lithium battery. However, since the prices of these gases are high, there is a problem that the manufacturing cost becomes high when used for manufacturing the all-solid-state lithium battery.
【００１０】本発明はこれらの課題を解決するものであ
り、製造コストの低い全固体リチウム電池の製造法を提
供することを目的とするものである。The present invention solves these problems, and an object of the present invention is to provide a method for manufacturing an all-solid-state lithium battery with low manufacturing cost.
【００１１】[0011]
【課題を解決するための手段】これらの課題を解決する
ために本発明の全固体リチウム電池の製造法は、固体電
解質層が硫化物を主体とするリチウムイオン導電性固体
電解質であり、前記固体電解質を一対の電極がはさみ接
して構成される全固体リチウム電池の組み立てを、再生
アルゴンガス雰囲気下で行う。In order to solve these problems, the method for manufacturing an all-solid-state lithium battery of the present invention is a solid electrolyte layer is a lithium ion conductive solid electrolyte mainly sulfide, the solid An all-solid-state lithium battery constructed by sandwiching an electrolyte between a pair of electrodes is assembled in a regenerated argon gas atmosphere.
【００１２】また、再生アルゴンガスは、脱水工程を経
たものを用いる。さらに、再生アルゴンガスは、脱酸素
工程を経たものを用いる。As the regenerated argon gas, one which has undergone a dehydration process is used. Furthermore, the regenerated argon gas used is one that has undergone a deoxidation step.
【００１３】また、硫化物を主体とするリチウムイオン
導電性固体電解質として、硫化リチウムと硫化ケイ素を
含む物質よりなる固体電解質を用いる。A solid electrolyte composed of a substance containing lithium sulfide and silicon sulfide is used as the lithium ion conductive solid electrolyte mainly containing sulfide.
【００１４】さらに、硫化物を主体とするリチウムイオ
ン導電性固体電解質として、リチウム酸化物あるいはリ
チウム酸素酸塩より選ばれる少なくとも一種の化合物を
含み、硫化リチウムと硫化ケイ素を含むリチウムイオン
導電性固体電解質を用いる。Further, as the lithium ion conductive solid electrolyte mainly composed of sulfide, a lithium ion conductive solid electrolyte containing lithium sulfide and silicon sulfide, containing at least one compound selected from lithium oxide or lithium oxyacid salt. To use.
【００１５】[0015]
【作用】再生アルゴンガスは、純アルゴンガスに比べて
不純物の濃度は高いものであるが、硫化物系固体電解質
あるいは金属リチウムに対して不活性であるため、電解
質として硫化物系固体電解質を用い、負極活物質として
金属リチウムあるいはリチウム合金を用いた場合でも、
再生したアルゴンガスを用いることで、製造コストを押
さえ、かつ固体電解質や負極活物質との反応による電池
性能の低下のない全固体リチウム電池を製造することが
できる。[Function] Although the recycled argon gas has a higher impurity concentration than pure argon gas, it is inactive with respect to the sulfide-based solid electrolyte or metallic lithium, so the sulfide-based solid electrolyte is used as the electrolyte. , Even when metallic lithium or lithium alloy is used as the negative electrode active material,
By using the regenerated argon gas, it is possible to suppress the manufacturing cost and manufacture an all-solid-state lithium battery without deterioration in battery performance due to reaction with the solid electrolyte or the negative electrode active material.
【００１６】また、再生アルゴンガスとしてアルゴンガ
スの脱水工程を経て再生されたものを用いると、水分と
の反応性の高い全固体リチウム電池の固体電解質および
負極活物質の反応を抑制することができる。When the regenerated argon gas regenerated through the dehydration step of argon gas is used, it is possible to suppress the reaction between the solid electrolyte and the negative electrode active material of the all-solid-state lithium battery having high reactivity with water. .
【００１７】さらに、再生アルゴンガスとしてアルゴン
ガスの脱酸素工程を経て再生されたものを用いると、全
固体リチウム電池の固体電解質が酸素と反応してイオン
導電性が低下するのを抑制することができる。Further, when the regenerated argon gas that is regenerated through the deoxygenation step of argon gas is used, it is possible to prevent the solid electrolyte of the all-solid-state lithium battery from reacting with oxygen to lower the ionic conductivity. it can.
【００１８】また、簡便な再生装置により再生した再生
アルゴンガス中の水分や酸素などの不純物の濃度は、純
アルゴンガスに比べ高い値を示すため、再生アルゴンガ
ス下で製造される全固体リチウム電池としては、これら
不純物の影響を受けにくい、より安定な材料より構成さ
れるものが望ましい。Since the concentration of impurities such as water and oxygen in the regenerated argon gas regenerated by a simple regenerating device is higher than that of pure argon gas, the all-solid-state lithium battery manufactured under the regenerated argon gas. As the material, it is desirable to use a material that is less susceptible to these impurities and is made of a more stable material.
【００１９】硫化物を主体とする固体電解質としては、
Ｌｉ2Ｓ−ＳｉＳ2，Ｌｉ2Ｓ−Ｐ2Ｓ 5，Ｌｉ2Ｓ−Ｂ2Ｓ3
などがあるが、その中でも特に硫化リチウムと硫化ケイ
素を含む物質よりなる固体電解質が再生アルゴンガス中
の不純物の影響を受けにくい。このため、再生アルゴン
ガス下で製造される全固体リチウム電池としては、硫化
物を主体とする固体電解質として、硫化リチウムと硫化
ケイ素を含む物質よりなる固体電解質を用いることが好
ましい。As the solid electrolyte mainly composed of sulfide,
Li2S-SiS2, Li2SP2S Five, Li2S-B2S3
Among them, especially lithium sulfide and silicon sulfide
Solid electrolyte consisting of a substance containing element in regenerated argon gas
Less susceptible to impurities. For this reason, regenerated argon
As an all-solid-state lithium battery manufactured under gas,
Lithium sulfide and sulfide
It is preferable to use a solid electrolyte made of a substance containing silicon.
Good.
【００２０】さらには、リチウム酸化物あるいはリチウ
ム酸素酸塩より選ばれる少なくとも一種の化合物を含
み、硫化リチウムと硫化ケイ素を含む物質よりなるリチ
ウムイオン導電性固体電解質は、硫化物ガラスの構造の
硫黄の一部が酸素により置換された構造であり、安定な
ガラス骨格を形成する。そのため、再生アルゴンガス中
に水分あるいは酸素などの不純物が存在した場合でも安
定性が良いことから、再生アルゴンガス下で製造される
全固体リチウム電池としては、硫化物を主体とする固体
電解質として、リチウム酸化物あるいはリチウム酸素酸
塩より選ばれる少なくとも一種の化合物を含み、硫化リ
チウムと硫化ケイ素を含む物質よりなる固体電解質を用
いることが好ましい。Further, a lithium ion conductive solid electrolyte containing a substance containing at least one compound selected from lithium oxide or lithium oxyacid salt and containing lithium sulfide and silicon sulfide is a sulfur-containing structure of sulfide glass. It has a structure in which a part is replaced by oxygen, and forms a stable glass skeleton. Therefore, since stability is good even when impurities such as water or oxygen are present in the regenerated argon gas, as an all-solid-state lithium battery produced under regenerated argon gas, as a solid electrolyte mainly composed of sulfide, It is preferable to use a solid electrolyte containing a substance containing at least one compound selected from lithium oxide and lithium oxyacid salt and containing lithium sulfide and silicon sulfide.
【００２１】[0021]
【実施例】以下、本発明について実施例を用いて詳細に
説明する。EXAMPLES The present invention will be described in detail below with reference to examples.
【００２２】（実施例１）本実施例では、アルゴンガス
の脱水工程として冷凍乾燥機による脱水、脱酸素工程と
して加熱した金属銅にアルゴンガスを通ずる脱酸素装置
による脱酸素の各工程を備えたアルゴンガス再生装置を
備えた電池組み立て装置を用い、全固体リチウム電池の
組み立てを行ったものについて説明する。(Embodiment 1) In this embodiment, each step of dehydration of argon gas was carried out by freeze-drying, and the step of deoxygenation was carried out by deoxygenation by an oxygen scavenger for passing argon gas through heated copper metal. What assembled the all-solid-state lithium battery using the battery assembly device provided with the argon gas regeneration device is demonstrated.
【００２３】図１に本発明による全固体リチウム電池組
み立て装置の模式図を示す。図中１は再生アルゴンガス
により満たされているアルゴンガスボックスであり、こ
の中に全固体リチウム電池組み立てライン２が設置され
ている。ここで使用されるアルゴンガスは、ガス流出口
３より冷凍乾燥器４に送られ脱水された後、脱酸素装置
５で酸素が取り除かれ、加圧ポンプ６により加圧され、
ガス流入口７よりアルゴンガスボックス１中に再び送ら
れる。このときアルゴンガスボックス１中の内圧低下時
には補充用アルゴンガス容器８より純アルゴンガスが送
られ補充される。FIG. 1 shows a schematic view of an all-solid-state lithium battery assembling apparatus according to the present invention. In the figure, 1 is an argon gas box filled with regenerated argon gas, and an all-solid-state lithium battery assembly line 2 is installed in this box. The argon gas used here is sent from the gas outlet 3 to the freeze dryer 4 for dehydration, then oxygen is removed by the deoxidizer 5 and pressurized by the pressure pump 6,
It is fed again into the argon gas box 1 from the gas inlet 7. At this time, when the internal pressure in the argon gas box 1 decreases, pure argon gas is sent from the replenishing argon gas container 8 to be replenished.
【００２４】上記の電池組み立て装置を用いて、硫化物
を主体とする固体電解質として０．６Ｌｉ2Ｓ−０．４
ＳｉＳ2で表されるリチウムイオン導電性非晶質固体電
解質、正極活物質としてＴｉＳ2で表される二硫化チタ
ン、負極活物質として金属リチウムを用い、下記のよう
に全固体リチウム電池を構成した。Using the above battery assembling apparatus, 0.6 Li 2 S-0.4 as a solid electrolyte mainly composed of sulfide was prepared.
A lithium ion conductive amorphous solid electrolyte represented by SiS 2 , titanium disulfide represented by TiS 2 as a positive electrode active material, and metallic lithium as a negative electrode active material were used to construct an all-solid-state lithium battery as follows. .
【００２５】まず、硫化物系リチウムイオン導電性固体
電解質０．６Ｌｉ2Ｓ−０．４ＳｉＳ2は、以下のように
合成した。First, the sulfide-based lithium ion conductive solid electrolyte 0.6Li 2 S-0.4SiS 2 was synthesized as follows.
【００２６】硫化リチウム（Ｌｉ2Ｓ）と硫化ケイ素
（ＳｉＳ2）をモル比で３：２に混合し、その混合物を
ガラス状カーボンの坩堝中に入れた。その坩堝を縦型炉
中に入れアルゴンガス気流中で９５０℃まで加熱し、混
合物を溶融状態とした。２時間加熱の後、融液を双ロー
ラーにより急冷し、０．６Ｌｉ2Ｓ−０．４ＳｉＳ2で表
されるリチウムイオン導電性非晶質固体電解質を得た。Lithium sulfide (Li 2 S) and silicon sulfide (SiS 2 ) were mixed at a molar ratio of 3: 2, and the mixture was placed in a glassy carbon crucible. The crucible was placed in a vertical furnace and heated to 950 ° C. in an argon gas stream to melt the mixture. After heating for 2 hours, the melt was rapidly cooled by a twin roller to obtain a lithium ion conductive amorphous solid electrolyte represented by 0.6Li 2 S-0.4SiS 2 .
【００２７】正極活物質であるＴｉＳ2は、市販の特級
試薬を用い、固体電解質と重量比で１：１の割合で混合
し、正極とした。For TiS 2 as the positive electrode active material, a commercially available special grade reagent was used and mixed with the solid electrolyte in a weight ratio of 1: 1 to obtain a positive electrode.
【００２８】負極としては、市販の金属リチウム箔（厚
み０．１ｍｍ）を用いた。これらの固体電解質、正極、
負極を図１の電池組み立てライン２に持ち込み、全固体
リチウム電池の構成を行った。As the negative electrode, a commercially available metallic lithium foil (thickness 0.1 mm) was used. These solid electrolytes, positive electrodes,
The negative electrode was brought into the battery assembly line 2 in FIG. 1 to construct an all-solid-state lithium battery.
【００２９】図２に構成した全固体リチウム電池の断面
図を示す。上記で得た正極９と１０ｍｍφの大きさに打
ち抜いた金属リチウム箔の負極１０を、固体電解質
（０．６Ｌｉ2Ｓ−０．４ＳｉＳ2）層１１を介して１０
ｍｍφの円筒状に一体に加圧成形した。その後、正極リ
ード１２、負極リード１３をカーボンペースト１４によ
り接着し、全体を封止樹脂１５により封止し、全固体リ
チウム電池を得た。FIG. 2 shows a sectional view of the all-solid-state lithium battery constructed. The positive electrode 9 obtained above and the negative electrode 10 of a metal lithium foil punched out in a size of 10 mmφ were placed 10 with a solid electrolyte (0.6Li 2 S-0.4SiS 2 ) layer 11 interposed therebetween.
It was integrally pressure-molded into a cylindrical shape of mmφ. Then, the positive electrode lead 12 and the negative electrode lead 13 were adhered with a carbon paste 14, and the whole was sealed with a sealing resin 15 to obtain an all-solid lithium battery.
【００３０】比較のために、図１に示した電池組み立て
装置の冷凍乾燥器４と脱酸素装置５を作動させず、補充
用アルゴンガス容器７から補充される純アルゴンガスの
みによりアルゴンボックス１内の雰囲気を制御し、この
組み立て装置内で上記と同様の方法で全固体リチウム電
池の組み立てを行った。なお電池組み立て中のアルゴン
ガスの露点は−３０℃以下、酸素含有量は０．１％以下
となるようにアルゴンガス再生装置の作動ならびに補充
用アルゴンガス容器からの補充を行った。For comparison, the freeze-dryer 4 and the deoxidizer 5 of the battery assembling apparatus shown in FIG. 1 are not operated and only the pure argon gas replenished from the replenishing argon gas container 7 is used in the argon box 1. The atmosphere was controlled, and the all-solid-state lithium battery was assembled in the assembly apparatus in the same manner as described above. During the battery assembly, the argon gas regenerator was operated and replenished from the replenishing argon gas container so that the dew point of the argon gas was −30 ° C. or lower and the oxygen content was 0.1% or lower.
【００３１】このようにして得た全固体リチウム電池の
性能を、内部インピーダンスと放電容量を測定し調べ
た。電池の内部インピーダンスは交流インピーダンス法
により測定し、放電容量は５０μＡの定電流で１．８Ｖ
まで放電し測定した。（表１）にその結果を示す。The performance of the thus obtained all-solid-state lithium battery was examined by measuring the internal impedance and the discharge capacity. The internal impedance of the battery is measured by the AC impedance method, and the discharge capacity is 1.8 V at a constant current of 50 μA.
It was discharged up to and measured. The results are shown in (Table 1).
【００３２】[0032]
【表１】 [Table 1]
【００３３】この結果より、再生アルゴンガス雰囲気下
で構成した全固体リチウム電池も、純アルゴンガス雰囲
気下で構成した全固体リチウム電池もほとんど同等の特
性を示すことがわかった。また、電池構成中の補充用ア
ルゴンガス容器からの純アルゴンガスの消費量は、再生
アルゴンガスを用いたアルゴンガスボックスでは１時間
当たり１．２ｄｍ3であったのに対し、純アルゴンガス
のみを用いたアルゴンガスボックスでは１０６ｄｍ3で
あった。From these results, it was found that the all-solid-state lithium battery constructed in the regenerated argon gas atmosphere and the all-solid-state lithium battery constructed in the pure argon gas atmosphere showed almost the same characteristics. Further, the consumption of pure argon gas from the replenishing argon gas container in the battery configuration was 1.2 dm 3 per hour in the argon gas box using the regenerated argon gas, whereas the pure argon gas was consumed only. The argon gas box used was 106 dm 3 .
【００３４】以上のように、本発明によると高価な純ア
ルゴンガスの消費量を減らし、低コストで全固体リチウ
ム電池を構成できることがわかった。As described above, according to the present invention, it was found that the consumption of expensive pure argon gas can be reduced and an all-solid-state lithium battery can be constructed at low cost.
【００３５】（実施例２）本実施例においては、全固体
リチウム電池の電解質として実施例１で用いた０．６Ｌ
ｉ2Ｓ−０．４ＳｉＳ2に代えて、リチウム酸化物あるい
はリチウム酸素酸塩より選ばれる少なくとも一種の化合
物を含み、硫化リチウムと硫化ケイ素を含む物質よりな
るリチウムイオン導電性固体電解質の一つである０．０
２Ｌｉ3ＰＯ4−０．５９Ｌｉ2Ｓ−０．３９ＳｉＳ2で表
されるリチウムイオン導電性非晶質固体電解質を用いた
以外は実施例１と同様の方法で、再生アルゴンガスを用
いる電池組み立て装置内で全固体リチウム電池の組み立
てを行った。また、比較のために再生アルゴンガスを使
用せずに、純アルゴンガスのみの雰囲気下で全固体リチ
ウム電池を構成した。Example 2 In this example, 0.6 L used in Example 1 as an electrolyte for an all-solid-state lithium battery was used.
One of the lithium ion conductive solid electrolytes made of a substance containing lithium sulfide and silicon sulfide, containing at least one compound selected from lithium oxide or lithium oxyacid salt in place of i 2 S-0.4SiS 2. Yes 0.0
2Li 3 PO 4 -0.59Li 2 S-0.39SiS 2 A battery assembly apparatus using regenerated argon gas in the same manner as in Example 1 except that the lithium ion conductive amorphous solid electrolyte represented by the formula was used. An all-solid lithium battery was assembled inside. For comparison, an all-solid-state lithium battery was constructed in an atmosphere of pure argon gas only, without using regenerated argon gas.
【００３６】このようにして得た全固体リチウム電池の
性能を、実施例１と同様の方法で内部インピーダンスと
放電容量を測定し調べた。（表２）に本発明の電池なら
びに比較の電池のインピーダンスと放電容量を示す。The performance of the thus obtained all-solid-state lithium battery was examined by measuring the internal impedance and the discharge capacity in the same manner as in Example 1. Table 2 shows the impedance and discharge capacity of the battery of the present invention and the comparative battery.
【００３７】[0037]
【表２】 [Table 2]
【００３８】この結果より、再生アルゴンガス雰囲気下
で構成した全固体リチウム電池も、純アルゴンガス雰囲
気下で構成した全固体リチウム電池もほとんど同等の特
性を示すことがわかった。また、電池構成中のアルゴン
ガス補充装置からの純アルゴンガスの消費量は、実施例
１の場合と同じであった。From these results, it was found that the all-solid-state lithium battery constructed in the regenerated argon gas atmosphere and the all-solid-state lithium battery constructed in the pure argon gas atmosphere showed almost the same characteristics. Further, the amount of pure argon gas consumed from the argon gas replenishing device in the battery configuration was the same as in the case of Example 1.
【００３９】また、実施例１では再生アルゴンガス雰囲
気下で構成した全固体リチウム電池と純アルゴンガス下
で構成した全固体リチウム電池のインピーダンスは前者
が２４Ω大きいものであったが、実施例２の電池での差
は２Ωだけであった。これは、実施例２では全固体リチ
ウム電池の電解質として、不純物に対して安定性のある
リチウム酸化物あるいはリチウム酸素酸塩より選ばれる
少なくとも一種の化合物を含み、硫化リチウムと硫化ケ
イ素を含む物質よりなるリチウムイオン導電性固体電解
質の一つである０．０２Ｌｉ3ＰＯ4−０．５９Ｌｉ2Ｓ
−０．３９ＳｉＳ2で表されるリチウムイオン導電性非
晶質固体電解質を用いたためである。In Example 1, the impedance of the all-solid-state lithium battery constructed under the regenerated argon gas atmosphere and the impedance of the all-solid-state lithium battery constructed under the pure argon gas were 24Ω higher than those of the former Example 2. The difference in the batteries was only 2Ω. This is because, in Example 2, as an electrolyte of an all-solid-state lithium battery, a substance containing at least one compound selected from lithium oxide or lithium oxyacid salt, which is stable against impurities, and containing lithium sulfide and silicon sulfide is used. made, one of a lithium ion conductive solid electrolyte 0.02Li 3 PO 4 -0.59Li 2 S
This is because using a lithium ion conductive amorphous solid electrolyte represented by -0.39SiS 2.
【００４０】以上のように、本発明によると高価な純ア
ルゴンガスの消費量を減らして低コストで全固体リチウ
ム電池を構成できることがわかった。As described above, according to the present invention, it was found that the consumption of expensive pure argon gas can be reduced and an all-solid-state lithium battery can be constructed at low cost.
【００４１】（実施例３）本実施例においては、全固体
リチウム電池の電解質として実施例１で用いた０．６Ｌ
ｉ2Ｓ−０．４ＳｉＳ2に代えて、リチウム酸化物あるい
はリチウム酸素酸塩より選ばれる少なくとも一種の化合
物を含み、硫化リチウムと硫化ケイ素を含む物質よりな
るリチウムイオン導電性固体電解質の一つである０．０
４Ｌｉ4ＳｉＯ4−０．５８Ｌｉ2Ｓ−０．３８ＳｉＳ2で
表されるリチウムイオン導電性非晶質固体電解質を用い
た以外は実施例１と同様の方法で、再生アルゴンガスを
用いる電池組み立て装置内で全固体リチウム電池の組み
立てを行った。また、比較のために再生アルゴンガスを
使用せずに、純アルゴンガスのみの雰囲気下で全固体リ
チウム電池を構成した。Example 3 In this example, 0.6 L used in Example 1 as an electrolyte for an all-solid-state lithium battery was used.
One of the lithium ion conductive solid electrolytes made of a substance containing lithium sulfide and silicon sulfide, containing at least one compound selected from lithium oxide or lithium oxyacid salt in place of i 2 S-0.4SiS 2. Yes 0.0
4Li 4 SiO 4 -0.58Li 2 S-0.38SiS 2 A battery assembly apparatus using regenerated argon gas in the same manner as in Example 1 except that the lithium ion conductive amorphous solid electrolyte represented by An all-solid lithium battery was assembled inside. For comparison, an all-solid-state lithium battery was constructed in an atmosphere of pure argon gas only, without using regenerated argon gas.
【００４２】このようにして得た全固体リチウム電池の
性能を、実施例１と同様の方法で内部インピーダンスと
放電容量を測定し調べた。The performance of the thus obtained all-solid-state lithium battery was examined by measuring the internal impedance and the discharge capacity in the same manner as in Example 1.
【００４３】この結果、再生アルゴンガス雰囲気下で構
成した全固体リチウム電池も、純アルゴンガス雰囲気下
で構成した全固体リチウム電池もほとんど同等の特性を
示すことがわかった。また、電池構成中のアルゴンガス
補充装置からの純アルゴンガスの消費量は、実施例１の
場合と同じであった。As a result, it was found that the all-solid-state lithium battery constructed in the regenerated argon gas atmosphere and the all-solid-state lithium battery constructed in the pure argon gas atmosphere showed almost the same characteristics. Further, the amount of pure argon gas consumed from the argon gas replenishing device in the battery configuration was the same as in the case of Example 1.
【００４４】以上のように、本発明によると高価なアル
ゴンガスの消費量を減らして低コストで全固体リチウム
電池を構成できることがわかった。As described above, according to the present invention, it was found that the consumption of expensive argon gas can be reduced and an all-solid-state lithium battery can be constructed at low cost.
【００４５】（実施例４）本実施例においては、全固体
リチウム電池の電解質として実施例１で用いた０．６Ｌ
ｉ2Ｓ−０．４ＳｉＳ2に代えて、リチウム酸化物あるい
はリチウム酸素酸塩より選ばれる少なくとも一種の化合
物を含み、硫化リチウムと硫化ケイ素を含む物質よりな
るリチウムイオン導電性固体電解質の一つである０．０
２Ｌｉ2Ｏ−０．５９Ｌｉ2Ｓ−０．３９ＳｉＳ2で表さ
れるリチウムイオン導電性非晶質固体電解質を用いた以
外は実施例１と同様の方法で、再生アルゴンガスを用い
る電池組み立て装置内で全固体リチウム電池の組み立て
を行った。また、比較のために再生アルゴンガスを使用
せずに、純アルゴンガスのみの雰囲気下で全固体リチウ
ム電池を構成した。Example 4 In this example, 0.6 L used in Example 1 as an electrolyte of an all-solid-state lithium battery was used.
It is one of lithium ion conductive solid electrolytes containing a substance containing lithium sulfide and silicon sulfide, containing at least one compound selected from lithium oxide or lithium oxyacid salt in place of i 2 S-0.4SiS 2. Yes 0.0
2Li 2 O-0.59Li 2 S-0.39SiS 2 In the battery assembly apparatus using regenerated argon gas in the same manner as in Example 1 except that the lithium ion conductive amorphous solid electrolyte represented by Then, an all-solid-state lithium battery was assembled. For comparison, an all-solid-state lithium battery was constructed in an atmosphere of pure argon gas only, without using regenerated argon gas.
【００４６】このようにして得た全固体リチウム電池の
性能を、実施例１と同様の方法で内部インピーダンスと
放電容量を測定し調べた。The performance of the thus obtained all-solid-state lithium battery was examined by measuring the internal impedance and the discharge capacity in the same manner as in Example 1.
【００４７】この結果、再生アルゴンガス雰囲気下で構
成した全固体リチウム電池も、純アルゴンガス雰囲気下
で構成した全固体リチウム電池もほとんど同等の特性を
示すことがわかった。また、電池構成中のアルゴンガス
補充用装置からの純アルゴンガスの消費量は、実施例１
の場合と同じであった。As a result, it was found that the all-solid-state lithium battery constructed in the regenerated argon gas atmosphere and the all-solid-state lithium battery constructed in the pure argon gas atmosphere showed almost the same characteristics. In addition, the consumption of pure argon gas from the argon gas replenishing device in the battery configuration is as shown in Example 1.
Was the same as
【００４８】以上のように、本発明によると高価な純ア
ルゴンガスの消費量を減らして低コストで全固体リチウ
ム電池を構成できることがわかった。As described above, according to the present invention, it was found that the consumption of expensive pure argon gas can be reduced and an all-solid-state lithium battery can be constructed at low cost.
【００４９】（実施例５）本実施例においては、正極活
物質としてＬｉＣｏＯ2で表されるコバルト酸リチウム
を用いた以外は実施例１と同様の方法で、再生アルゴン
ガスを用いる電池組み立て装置内で全固体リチウム電池
の組み立てを行った。また、比較のために再生アルゴン
ガスを使用せずに、純アルゴンガスのみの雰囲気下で全
固体リチウム電池を構成した。(Embodiment 5) In this embodiment, in the same manner as in Embodiment 1 except that lithium cobalt oxide represented by LiCoO 2 was used as the positive electrode active material, in a battery assembly apparatus using regenerated argon gas. Then, an all-solid-state lithium battery was assembled. For comparison, an all-solid-state lithium battery was constructed in an atmosphere of pure argon gas only, without using regenerated argon gas.
【００５０】ただし、正極活物質であるＬｉＣｏＯ
2は、酸化コバルト（Ｃｏ3Ｏ4）と炭酸リチウム（Ｌｉ2
ＣＯ3）を混合し、大気中で９００℃で焼成することに
より合成した。このコバルト酸リチウムと固体電解質と
導電材としてアセチレンブラックを重量比で４８：４
８：４の割合で混合したものを正極として用いた。However, the positive electrode active material LiCoO 2
2 is cobalt oxide (Co 3 O 4 ) and lithium carbonate (Li 2
CO 3 ) was mixed and calcined at 900 ° C. in the atmosphere to synthesize. The lithium cobalt oxide, the solid electrolyte, and acetylene black as a conductive material are used in a weight ratio of 48: 4.
A mixture of 8: 4 was used as the positive electrode.
【００５１】このようにして得た全固体リチウム電池の
性能を、実施例１と同様の方法で内部インピーダンスを
測定し調べた。さらに、４．３Ｖ〜２．５Ｖの電圧範囲
で充放電試験を行い放電容量を測定した。The performance of the thus obtained all-solid-state lithium battery was examined by measuring the internal impedance in the same manner as in Example 1. Further, a charge / discharge test was performed in a voltage range of 4.3 V to 2.5 V to measure the discharge capacity.
【００５２】この結果、再生アルゴンガス雰囲気下で構
成した全固体リチウム電池も、純アルゴンガス雰囲気下
で構成した全固体リチウム電池もほとんど同等の特性を
示すことがわかった。また、電池構成中のアルゴンガス
補充装置からの純アルゴンガスの消費量は実施例１の場
合と同じであった。As a result, it was found that the all-solid-state lithium battery constructed in the regenerated argon gas atmosphere and the all-solid-state lithium battery constructed in the pure argon gas atmosphere showed almost the same characteristics. Further, the amount of pure argon gas consumed from the argon gas replenishing device in the battery structure was the same as in the case of Example 1.
【００５３】以上のように、本発明によると高価なアル
ゴンガスの消費量を減らして低コストで全固体リチウム
電池を構成できることがわかった。As described above, according to the present invention, it was found that the consumption of expensive argon gas can be reduced and an all-solid-state lithium battery can be constructed at low cost.
【００５４】[0054]
【発明の効果】以上説明したように、本発明によれば、
電池の性能を低下させることなく、低コストで全固体リ
チウム電池の組み立てを行うことができた。As described above, according to the present invention,
It was possible to assemble an all-solid-state lithium battery at low cost without degrading the battery performance.
【図１】本発明の一実施例における全固体リチウム電池
組み立て装置の模式図。FIG. 1 is a schematic diagram of an all-solid-state lithium battery assembling apparatus according to an embodiment of the present invention.
【図２】本発明の一実施例における全固体リチウム電池
の断面図。FIG. 2 is a sectional view of an all-solid-state lithium battery according to an embodiment of the present invention.
１ アルゴンガスボックス ２ 電池組み立てライン ３ ガス流出口 ４ 冷凍乾燥器 ５ 脱酸素装置 ６ 加圧ポンプ ７ ガス流入口 ８ 補充用アルゴンガス容器 ９ 正極 １０ 負極 １１ 固体電解質層 １２ 正極リード １３ 負極リード １４ カーボンペースト １５ 封止樹脂 1 Argon Gas Box 2 Battery Assembly Line 3 Gas Outlet 4 Freeze Dryer 5 Deoxidizer 6 Pressure Pump 7 Gas Inlet 8 Replenishing Argon Gas Container 9 Positive Electrode 10 Negative Electrode 11 Solid Electrolyte Layer 12 Positive Electrode Lead 13 Negative Lead 14 Carbon Paste 15 Sealing resin
───────────────────────────────────────────────────── 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 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shigeo Kondo 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.
Claims (5)
ムイオン導電性固体電解質であり、前記固体電解質層を
一対の電極がはさみ接して構成される全固体リチウム電
池の組み立てを、再生アルゴンガス雰囲気下で行うこと
を特徴とする全固体リチウム電池の製造法。1. An all-solid-state lithium battery assembly in which the solid electrolyte layer is a lithium ion conductive solid electrolyte mainly composed of sulfide, and a pair of electrodes are sandwiched in contact with the solid electrolyte layer to assemble a regenerated argon gas. A method for manufacturing an all-solid-state lithium battery, which is characterized in that it is performed in an atmosphere.
工程を経て再生され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の製造法。2. The method for producing an all-solid-state lithium battery according to claim 1, wherein the regenerated argon gas is regenerated through a dehydration step of argon gas.
素工程を経て再生されることを特徴とする請求項１また
は請求項２記載の全固体リチウム電池の製造法。3. The method for producing an all-solid-state lithium battery according to claim 1 or 2, wherein the regenerated argon gas is regenerated through a deoxidation step of argon gas.
固体電解質が、硫化リチウムと硫化ケイ素を含む物質よ
りなる固体電解質であることを特徴とする請求項１〜請
求項３のいずれかに記載の全固体リチウム電池の製造
法。4. The lithium ion conductive solid electrolyte mainly composed of sulfide is a solid electrolyte composed of a substance containing lithium sulfide and silicon sulfide. Method for manufacturing all-solid-state lithium battery.
固体電解質が、リチウム酸化物あるいはリチウム酸素酸
塩より選ばれる少なくとも一種の化合物を含み、硫化リ
チウムと硫化ケイ素を含む物質よりなるリチウムイオン
導電性固体電解質であることを特徴とする請求項４記載
の全固体リチウム電池の製造法。5. A lithium ion conductive solid electrolyte containing sulfide as a main component contains at least one compound selected from a lithium oxide and a lithium oxyacid salt, and is made of a substance containing lithium sulfide and silicon sulfide. 5. The method for producing an all-solid-state lithium battery according to claim 4, wherein the all-solid lithium battery is a solid electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6308695A JPH08167425A (en) | 1994-12-13 | 1994-12-13 | Manufacture of total solid lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6308695A JPH08167425A (en) | 1994-12-13 | 1994-12-13 | Manufacture of total solid lithium battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08167425A true JPH08167425A (en) | 1996-06-25 |
Family
ID=17984175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6308695A Pending JPH08167425A (en) | 1994-12-13 | 1994-12-13 | Manufacture of total solid lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08167425A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002097564A (en) * | 2000-07-19 | 2002-04-02 | Sumitomo Electric Ind Ltd | Member with thin film of alkali metal and manufacturing method therefor |
| WO2009101501A1 (en) | 2008-02-12 | 2009-08-20 | Toyota Jidosha Kabushiki Kaisha | All-solid lithium secondary battery |
| JP2011165504A (en) * | 2010-02-10 | 2011-08-25 | Toshiba Corp | Jig for drying, drying device, and drying method |
| JP2015115294A (en) * | 2013-12-13 | 2015-06-22 | 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． | All-solid-state secondary battery and method for manufacturing all-solid-state secondary battery |
| US9819019B2 (en) | 2013-12-13 | 2017-11-14 | Samsung Electronics Co., Ltd. | All solid secondary battery and method of preparing all solid secondary battery |
| WO2019035418A1 (en) * | 2017-08-14 | 2019-02-21 | 三井金属鉱業株式会社 | Positive electrode active material for all-solid-state lithium secondary batteries |
| WO2019054191A1 (en) * | 2017-09-14 | 2019-03-21 | 富士フイルム株式会社 | Solid electrolyte composition, method for producing same, storage method and kit, solid electrolyte-containing sheet, storage method and kit therefor, and all-solid secondary battery |
| JP2019102321A (en) * | 2017-12-05 | 2019-06-24 | トヨタ自動車株式会社 | Sulfide solid electrolyte secondary battery |
| JP2021140947A (en) * | 2020-03-05 | 2021-09-16 | トヨタ自動車株式会社 | Battery manufacturing facility and manufacturing space formation method of electrode stack |
-
1994
- 1994-12-13 JP JP6308695A patent/JPH08167425A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002097564A (en) * | 2000-07-19 | 2002-04-02 | Sumitomo Electric Ind Ltd | Member with thin film of alkali metal and manufacturing method therefor |
| WO2009101501A1 (en) | 2008-02-12 | 2009-08-20 | Toyota Jidosha Kabushiki Kaisha | All-solid lithium secondary battery |
| US9017839B2 (en) | 2008-02-12 | 2015-04-28 | Toyota Jidosha Kabushiki Kaisha | All-solid lithium secondary battery |
| JP2011165504A (en) * | 2010-02-10 | 2011-08-25 | Toshiba Corp | Jig for drying, drying device, and drying method |
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