JP2004348973A - Manufacturing method of lithium ion conductive sulfide glass and glass ceramics as well as all solid battery using the glass ceramics - Google Patents
Manufacturing method of lithium ion conductive sulfide glass and glass ceramics as well as all solid battery using the glass ceramics Download PDFInfo
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、リチウムイオン伝導性硫化物ガラス及びガラスセラミックスの製造方法並びに該ガラス又はガラスセラミックスを固体電解質として使用する全固体型電池に関するものである。
【０００２】
【従来の技術】
リチウムイオン伝導性硫化物ガラス及びガラスセラミックスは、全固体型リチウム二次電池の電解質として利用可能であることが公知である。このような硫化物ガラスは、ガラス形成剤であるＳｉＳ２ 、五硫化リン（Ｐ２ Ｓ５ ）及びＢ２ Ｓ３ 等と、ガラス修飾剤である硫化リチウム（Ｌｉ２ Ｓ）を混合し加熱溶融した後、急冷することによって得られる（例えば、特許文献１参照）。
また、本発明者らは、このような硫化物ガラスが硫化物結晶を室温でメカニカルミリングすることにより得られることを開示している（特許文献２参照）。
【０００３】
【発明が解決しようとする課題】
これらの方法では、ガラス修飾剤である硫化リチウムを出発原料の一つとして用いているが、硫化リチウムは反応性が低く、上記ガラス形成剤等と効率良く反応せず、未反応の硫化リチウムが多量に残存するため、目的とする硫化物ガラスを得ることができない。また、多量の未反応の硫化リチウムが残存すると、電解質としての性能が低くなり、全固体型リチウム電池の電解質として使用できなくなるという問題がある。
本発明者らは、より入手が容易で且つ安価な原料を出発物質とするリチウムイオン伝導性硫化物ガラスの製造法について検討を行ってきた。
例えば、本発明者らは、金属リチウム（Ｌｉ）又は硫化リチウム（Ｌｉ２ Ｓ）と単体ケイ素（Ｓｉ）及び単体硫黄（Ｓ）を出発原料として、メカニカルミリングを行うことによりリチウムイオン伝導性硫化物ガラスが得られることを開示した（特許文献２参照）。
しかしながら、この硫化物ガラスは、硫化リチウムとＳｉＳ２ を原料とした場合に比べ、メカニカルミリングの時間が長くなり、得られる硫化物ガラスの電気伝導度も低いという問題点がある。
本発明者らは、より電気伝導度の高い硫化物ガラスの製造を目的に検討を続け、硫化リチウム及び五硫化リンを主成分とした硫化物セラミックスが高いリチウムイオン伝導性を示すことを見出した（特許文献３参照） 。
また、硫化リチウムと五硫化リンをメカニカルミリングすることにより得られる硫化物を、ガラス転移温度以上で焼成処理することにより、室温での電気伝導度が向上することも見出した（非特許文献１参照）。更に、より入手可能な原料として、単体リン（Ｐ）と単体硫黄（Ｓ）をメカニカルミリングによりガラス化したものに、金属リチウムを加え、更にメカニカルミリングすることによって、室温での電気伝導度が１０−５Ｓ／ｃｍオーダーの硫化物ガラスが得られることも見出した（非特許文献２参照）。
【０００４】
【特許文献１】
特開平９−２８３１５６号公報
【特許文献２】
特開平１１−１３４９３７号公報
【特許文献３】
特開２００１−２５０５８０号公報
【非特許文献１】
Ｃｈｅｍｉｓｔｒｙ Ｌｅｔｔｅｒｓ ２００１
【非特許文献２】
辰巳砂ら： 日本化学会２００１年春季大会講演要旨集２Ｅ３４１
【０００５】
【課題を解決するための手段】
本発明者らは、更に、簡便かつ入手が容易な原料を用いた製造方法について検討を行い、金属リチウム又は硫化リチウムと、単体硫黄（Ｓ）と単体リン（Ｐ）を出発原料として用い、メカニカルミリングにより得られた硫化物ガラスが、 硫化リチウムと五硫化リンを原料とし、メカニカルミリングにより製造したリチウムイオン伝導性硫化物ガラスと同等の性能を有することを見出した（特願２００２−００５８５５号）。更に、簡便かつ効率的な製造方法について検討を行い、ガラス修飾剤として水酸化リチウム（ＬｉＯＨ）を用いることにより、固体電解質として有用な硫化物ガラスが得られることを見出し、本発明を完成するに至った。
更に、本発明で得られる硫化物ガラスは、ガラス転移温度以上で一旦焼成処理を行うことにより、室温での電気伝導度が１０−４Ｓ／ｃｍ以上に向上することも見出した。
【０００６】
すなわち、本発明は、
▲１▼ リチウムイオン伝導性硫化物ガラスを製造するにあたり、出発原料として、硫化リチウムと、五硫化リン、単体リン及び単体イオウから選ばれる一種以上を含む原料を用い、該原料に、ガラス修飾剤として、硫化リチウム１００質量部に対して０．９質量部以上の水酸化リチウムを添加し、該原料をメカニカルミリングによりガラス化させることを特徴とする、リチウムイオン伝導性硫化物ガラスの製造方法、
▲２▼ 前記▲１▼に記載の、メカニカルミリングによりガラス化したリチウムイオン伝導性硫化物ガラスをガラス転移温度以上で焼成することを特徴とする、リチウムイオン伝導性硫化物ガラスセラミックスの製造方法、
▲３▼ １５０℃以上で焼成することを特徴とする前記▲２▼に記載のリチウムイオン伝導性硫化物ガラスセラミックスの製造方法、
▲４▼ 前記焼成を真空下又は不活性ガス存在下で行なうことを特徴とする前記▲２▼又は▲３▼に記載のリチウムイオン伝導性硫化物ガラスセラミックスの製造方法、
▲５▼ 前記硫化物ガラスの分解電圧が、少なくとも３Ｖであることを特徴とする前記▲１▼に記載のリチウムイオン伝導性硫化物ガラスの製造方法、
▲６▼ 前記硫化物ガラスセラミックスの分解電圧が、少なくとも３Ｖであることを特徴とする前記▲２▼〜▲４▼のいずれかに記載のリチウムイオン伝導性硫化物ガラスセラミックスの製造方法、
▲７▼ 前記▲１▼又は▲５▼に記載の方法で製造されたリチウムイオン伝導性硫化物ガラスを固体電解質として用いることを特徴とする全固体型電池、
▲８▼ 前記▲２▼〜▲４▼及び▲６▼のいずれかに記載の方法で製造されたリチウムイオン伝導性硫化物ガラスセラミックスを固体電解質として用いることを特徴とする全固体型電池
を提供するものである。
【０００７】
【発明の実施の形態】
本発明においては、出発原料として、硫化リチウム（Ｌｉ２ Ｓ）と、五硫化リン（Ｐ２ Ｓ５ ）、単体リン（Ｐ）及び単体イオウ（Ｓ）から選ばれる一種以上を含む原料を用いる。本発明で用いる硫化リチウム（Ｌｉ２ Ｓ）は、いかなる製造方法により製造されたものでもよく、工業的に生産され、販売されているものであれば、特に限定なく使用することができるが、特開２０００−２４７６０９号公報に記載された製造方法により製造されたものが好ましい。
五硫化リン、単体硫黄及び単体リンは工業的に生産され、販売されているものであれば、特に限定なく使用することができる。更に、単体硫黄は、製油所等で生産される溶融硫黄をそのまま使用することもできる。
【０００８】
出発原料として、硫化リチウム（Ｌｉ２ Ｓ）、単体硫黄（Ｓ）及び単体リン（Ｐ）を用いる場合、硫化リチウム単体硫黄及び単体リンの混合割合は、モル比で硫化リチウム１に対して、単体硫黄０．５〜３．５、単体リン０．２〜１．５が好ましい。また、出発原料として、硫化リチウム（Ｌｉ２ Ｓ）及び五硫化リン（Ｐ２ Ｓ５ ）を用いる場合、モル比で硫化リチウム１に対して、五硫化リン０．０５〜１．０が好ましい。更に、単体ケイ素（Ｓｉ）、金属ゲルマニウム（Ｇｅ）、金属アルミニウム（Ａｌ）、金属鉄（Ｆｅ）、金属亜鉛（Ｚｎ）及び単体ホウ素（Ｂ）も単体硫黄とメカニカルミリングによって、非晶質又は結晶性の硫化物を生成する（辰巳砂ら：日本化学会２００１年春季大会講演要旨集２Ｅ３４１）ため、上記リチウムイオン伝導性硫化物ガラスの出発原料の一部をこれらと置換することができる。
本発明においては、ガラス修飾剤として、水酸化リチウム（ＬｉＯＨ）を用いる。水酸化リチウムの添加量は、硫化リチウム１００質量部に対して０．９質量部以上であることを要し、好ましくは１．２〜２０質量部である。
【０００９】
本発明では、硫化リチウム（Ｌｉ２ Ｓ）と、五硫化リン（Ｐ２ Ｓ５ ）、単体リン（Ｐ）及び単体イオウ（Ｓ）から選ばれる一種以上を含む出発原料をガラス化するために、メカニカルミリングを用いる。メカニカルミリングによれば、室温付近でガラスを合成できるため、出発原料の熱分解が起らず、仕込み組成のガラスを得ることができるという利点がある。また、メカニカルミリングでは、ガラスの合成と同時に、ガラスを微粉末化できるという利点もある。
本発明の方法では、イオン伝導性硫化物ガラスを微粉末化するに際し、改めて粉砕することや、切削する必要がない。かかる微粉末化ガラスは、例えば、直接又はペレット状に加圧成形したものを全固体型電池に組み込み、固体電解質として用いることができる。
本発明の方法によれば、電池用固体電解質としてのイオン伝導性硫化物ガラスの製造工程を簡略化することができ、コストダウンも図れる。更に、メカニカルミリングによれば、微粉末で均一な粒子サイズを有するイオン伝導性硫化物ガラスを生成できる。
このようなガラスセラミックスを、固体電解質として用いれば、正極及び負極との接触界面の増大と密着性を向上できる。
【００１０】
メカニカルミリングによる反応は不活性ガス（窒素ガス、アルゴンガス等）雰囲気下で行う。メカニカルミリングは種々の形式を用いることができるが、遊星型ボールミルを使用するのが特に好ましい。遊星型ボールミルは、ポットが自転回転しながら、台盤が公転回転し、非常に高い衝撃エネルギーを効率良く発生させることができる。
メカニカルミリングの回転速度及び回転時間は特に限定されないが、回転速度が速いほど硫化物ガラスの生成速度は速くなり、回転時間が長いほど硫化物ガラスヘの出発原料の転化率は高くなる。
メカニカルミリングにより得られた硫化物ガラスをガラス転移温度（１５０℃）以上、好ましくは２００〜５００℃で焼成することにより、室温（２５℃）での電気伝導度が向上した、硫化物ガラスセラミックスが得られる。焼成処理を行う硫化物ガラスの形状は特に限定されないが、粉末状のままでもよいし、ペレット状に加圧成形したものでもよい。
焼成処理は不活性ガス（窒素ガス、アルゴンガス等）存在下又は真空下で行うのが好ましい。焼成処理時の昇温速度、降温速度並びに焼成時間は特に限定されない。
このようにして得られた硫化物ガラスセラミックスは、固体電解質として好適なものである。
【００１１】
【実施例】
次に、本発明を実施例により更に詳細に説明するが、本発明はこれらの例によってなんら限定されるものではない。
実施例１
出発原料として、硫化リチウム結晶（Ｌｉ２ Ｓ）及び五硫化リン（Ｐ２ Ｓ５ ）を用い、ガラス修飾剤として、水酸化リチウム（ＬｉＯＨ）を用いた。
アルゴンを雰囲気下のドライボックス中で、硫化リチウム結晶と五硫化リンとをモル比６．９／２（Ｌｉ２ Ｓ／Ｐ２ Ｓ５ ）の割合で秤量し、また、硫化リチウム結晶（Ｌｉ２ Ｓ）１００質量部に対して、水酸化リチウム（ＬｉＯＨ）２．１質量部の割合で秤量し、これらの粉末をアルミナ製のポットに投入し、完全密閉した。このポットを遊星型ボールミル機に取り付け、初期は出発原料を十分混合する目的で数分間、低速回転（回転速度：８５ｒｐｍ）でミリングを行った。その後、徐々に回転数を増大させていき、３７０ｒｐｍで２０時間メカニカルミリングを行った。
得られた粉末ガラスのＸ線回折を行った結果、硫化リチウム（Ｌｉ２ Ｓ）のピークは消失し、ガラス化が進行していることが確認された。
この粉末試料を不活性ガス（窒素）雰囲気下で２０ＭＰａ（２００ｋｇ／ｃｍ２ ）の加圧下でペレット状に成形後、電極としてカーボンペーストを塗布し、交流二端子法により電気伝導度の測定を行ったところ、室温（２５℃）での電気伝導度は８．１×１０−５Ｓ／ｃｍであった。
【００１２】
実施例２
実施例１で得られたペレットを不活性ガス（窒素）の存在下で、２５０℃で焼成処理を行い、硫化物ガラスセラミックスを得た。冷却後、実施例１と同様の方法で電気伝導度を測定したところ、室温（２５℃）での電気伝導度は３．０×１０−４Ｓ／ｃｍであり、焼成により電気伝導度が向上した。
【００１３】
比較例１
硫化リチウム結晶（Ｌｉ２ Ｓ）１００質量部に対して、水酸化リチウム（ＬｉＯＨ）０．５３質量部の割合で秤量し、使用した以外は実施例１と同様にしてガラス粉末を得た。得られた粉末ガラスのＸ線回折を行った結果、未反応硫化リチウム（Ｌｉ２ Ｓ）の大きなピークが検出された。
この粉末ガラスを実施例１と同様にしてペレット状に加圧成形し、電極としてカーボンペーストを塗布し、実施例１と同じ方法で電気伝導度の測定を行ったところ、室温（２５℃）での電気伝導度は１．０×１０−５Ｓ／ｃｍと非常に低い値であった。
【００１４】
比較例２
硫化リチウム結晶（Ｌｉ２ Ｓ）１００質量部に対して、水酸化リチウム（ＬｉＯＨ）０．７４質量部の割合で秤量し、使用した以外は実施例１と同様にしてガラス粉末を得た。得られた粉末ガラスのＸ線回折を行った結果、未反応硫化リチウム（Ｌｉ２ Ｓ）の大きなピークが検出された。
この粉末ガラスを実施例１と同様にしてペレット状に加圧成形し、電極としてカーボンペーストを塗布し、実施例１と同じ方法で電気伝導度の測定を行ったところ、室温（２５℃）での電気伝導度は５．０×１０−６Ｓ／ｃｍと非常に低い値であった。
【００１５】
実施例３
実施例２で得られたペレット状の硫化物ガラスセラミックスを固体電解質に用いて全固体型リチウム二次電池を作製した。
正極として４Ｖを超える電位を示すコバルト酸リチウム、負極にはインジウム金属を使用した。電流密度５０μＡ／ｃｍ２ で、定電流放電測定を行ったところ、充放電が可能であった。また、充放電効率も１００％であり、優れたサイクル特性を示すことが判明した。
【００１６】
【発明の効果】
本発明によれば、入手が容易で且つ安価な原料を出発物質として、簡便な方法で室温での電気伝導度の高いリチウムイオン伝導性硫化物ガラス及びセラミックスを製造することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a lithium ion conductive sulfide glass and a glass ceramic, and an all-solid-state battery using the glass or the glass ceramic as a solid electrolyte.
[0002]
[Prior art]
It is known that lithium ion conductive sulfide glass and glass ceramics can be used as an electrolyte of an all-solid-state lithium secondary battery. Such a sulfide glass is prepared by mixing glass-forming agents such as SiS 2 , phosphorus pentasulfide (P 2 S 5 ) and B 2 S 3 with lithium sulfide (Li 2 S) as a glass modifier and melting by heating. After that, it is obtained by quenching (for example, see Patent Document 1).
The present inventors also disclose that such a sulfide glass can be obtained by mechanically milling a sulfide crystal at room temperature (see Patent Document 2).
[0003]
[Problems to be solved by the invention]
In these methods, lithium sulfide, which is a glass modifier, is used as one of the starting materials. However, lithium sulfide has low reactivity, does not efficiently react with the above-mentioned glass former, etc., and unreacted lithium sulfide is produced. Since a large amount remains, the target sulfide glass cannot be obtained. Further, when a large amount of unreacted lithium sulfide remains, the performance as an electrolyte is lowered, and there is a problem that it cannot be used as an electrolyte of an all-solid-state lithium battery.
The present inventors have been studying a method for producing a lithium ion conductive sulfide glass starting from a more easily available and inexpensive raw material.
For example, the present inventors have performed mechanical milling using metallic lithium (Li) or lithium sulfide (Li 2 S), elemental silicon (Si) and elemental sulfur (S) as starting materials, thereby obtaining lithium ion conductive sulfide. It has been disclosed that glass can be obtained (see Patent Document 2).
However, the sulfide glass has a problem that the mechanical milling time is longer and the electric conductivity of the obtained sulfide glass is lower than when lithium sulfide and SiS 2 are used as raw materials.
The present inventors have continued to study for the purpose of producing a sulfide glass having higher electric conductivity, and have found that a sulfide ceramic mainly containing lithium sulfide and phosphorus pentasulfide exhibits high lithium ion conductivity. (See Patent Document 3).
It has also been found that by subjecting a sulfide obtained by mechanical milling of lithium sulfide and phosphorus pentasulfide to a baking treatment at a temperature equal to or higher than the glass transition temperature, the electrical conductivity at room temperature is improved (see Non-Patent Document 1). ). Further, as a more available raw material, metallic phosphorus is added to vitrified elemental phosphorus (P) and elemental sulfur (S) by mechanical milling, and the resulting mixture is further mechanically milled to have an electric conductivity of 10 at room temperature. It was also found that a sulfide glass on the order of -5 S / cm was obtained (see Non-Patent Document 2).
[0004]
[Patent Document 1]
JP-A-9-283156 [Patent Document 2]
JP-A-11-134937 [Patent Document 3]
JP 2001-250580 A [Non-Patent Document 1]
Chemistry Letters 2001
[Non-patent document 2]
Tatsumi Sanda: Abstracts of the Chemical Society of Japan 2001 Spring Meeting Abstracts 2E341
[0005]
[Means for Solving the Problems]
The present inventors further studied a production method using a raw material which is simple and easily available, and using metallic lithium or lithium sulfide, elemental sulfur (S) and elemental phosphorus (P) as starting materials, It has been found that a sulfide glass obtained by milling has the same performance as a lithium ion conductive sulfide glass produced by mechanical milling using lithium sulfide and phosphorus pentasulfide as raw materials (Japanese Patent Application No. 2002-005855). . Further, a simple and efficient production method was studied, and it was found that a sulfide glass useful as a solid electrolyte can be obtained by using lithium hydroxide (LiOH) as a glass modifier, and the present invention was completed. Reached.
Furthermore, it has also been found that the sulfide glass obtained by the present invention is improved in electrical conductivity at room temperature to 10 −4 S / cm or more by performing a baking treatment once at a glass transition temperature or higher.
[0006]
That is, the present invention
{Circle around (1)} In producing a lithium ion conductive sulfide glass, a raw material containing lithium sulfide and at least one selected from phosphorus pentasulfide, elemental phosphorus and elemental sulfur is used as a starting material, and a glass modifier is used as the starting material. A method for producing lithium ion conductive sulfide glass, characterized by adding 0.9 parts by mass or more of lithium hydroxide to 100 parts by mass of lithium sulfide and vitrifying the raw material by mechanical milling,
(2) The method for producing a lithium ion conductive sulfide glass ceramic according to (1), wherein the lithium ion conductive sulfide glass vitrified by mechanical milling is fired at a glass transition temperature or higher.
(3) The method for producing a lithium ion conductive sulfide glass-ceramic according to (2), wherein the method is carried out at 150 ° C. or more;
(4) The method for producing a lithium ion conductive sulfide glass ceramic according to (2) or (3), wherein the calcination is performed in a vacuum or in the presence of an inert gas.
(5) The method for producing a lithium ion conductive sulfide glass according to (1), wherein the decomposition voltage of the sulfide glass is at least 3 V;
(6) The method for producing a lithium ion conductive sulfide glass ceramic according to any of (2) to (4), wherein the decomposition voltage of the sulfide glass ceramic is at least 3 V;
(7) An all-solid-state battery using the lithium ion conductive sulfide glass produced by the method according to (1) or (5) as a solid electrolyte,
(8) An all-solid-state battery characterized by using a lithium-ion conductive sulfide glass ceramics produced by the method according to any of (2) to (4) and (6) as a solid electrolyte. Is what you do.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
In the present invention, a raw material containing lithium sulfide (Li 2 S) and at least one selected from phosphorus pentasulfide (P 2 S 5 ), simple phosphorus (P) and simple sulfur (S) is used as a starting material. Lithium sulfide (Li 2 S) used in the present invention may be produced by any production method, and may be used without particular limitation as long as it is industrially produced and sold. What was manufactured by the manufacturing method described in Unexamined-Japanese-Patent No. 2000-247609 is preferable.
Phosphorus pentasulfide, elemental sulfur and elemental phosphorus can be used without particular limitation as long as they are industrially produced and sold. Further, as the elemental sulfur, molten sulfur produced in a refinery or the like can be used as it is.
[0008]
When lithium sulfide (Li 2 S), elemental sulfur (S) and elemental phosphorus (P) are used as the starting materials, the mixing ratio of the elemental sulfur and the elemental phosphorus is a molar ratio of 1 to lithium sulfide and 1 to lithium sulfide. Preference is given to 0.5 to 3.5 sulfur and 0.2 to 1.5 simple phosphorus. When lithium sulfide (Li 2 S) and phosphorus pentasulfide (P 2 S 5 ) are used as starting materials, the molar ratio of phosphorus pentasulfide to phosphorus pentasulfide is preferably 0.05 to 1.0. Further, elemental silicon (Si), metallic germanium (Ge), metallic aluminum (Al), metallic iron (Fe), metallic zinc (Zn) and elemental boron (B) are also amorphous or crystalline by elemental sulfur and mechanical milling. (Tatsumi-Suna et al .: Abstracts of the 2nd Annual Meeting of the Chemical Society of Japan, 2001 Spring Conference 2E341), it is possible to replace some of the starting materials of the lithium ion conductive sulfide glass with these.
In the present invention, lithium hydroxide (LiOH) is used as a glass modifier. The addition amount of lithium hydroxide needs to be 0.9 parts by mass or more with respect to 100 parts by mass of lithium sulfide, and is preferably 1.2 to 20 parts by mass.
[0009]
In the present invention, in order to vitrify a starting material containing lithium sulfide (Li 2 S) and at least one selected from phosphorus pentasulfide (P 2 S 5 ), phosphorus (P) and sulfur (S), Use mechanical milling. According to mechanical milling, since glass can be synthesized at around room temperature, there is an advantage that thermal decomposition of a starting material does not occur and a glass having a charged composition can be obtained. In addition, mechanical milling has an advantage that the glass can be finely divided at the same time as the synthesis of the glass.
In the method of the present invention, it is not necessary to pulverize or cut again when pulverizing the ion-conductive sulfide glass. Such a pulverized glass can be used as a solid electrolyte by, for example, directly or pressure-molding a pellet into a solid state battery.
ADVANTAGE OF THE INVENTION According to the method of this invention, the manufacturing process of the ion conductive sulfide glass as a solid electrolyte for batteries can be simplified, and the cost can be reduced. Further, according to the mechanical milling, an ion conductive sulfide glass having a fine powder and a uniform particle size can be produced.
If such a glass ceramic is used as a solid electrolyte, the contact interface between the positive electrode and the negative electrode can be increased and the adhesion can be improved.
[0010]
The reaction by mechanical milling is performed in an inert gas (nitrogen gas, argon gas, etc.) atmosphere. Although various types of mechanical milling can be used, it is particularly preferable to use a planetary ball mill. In a planetary ball mill, the base plate revolves while the pot rotates, and very high impact energy can be efficiently generated.
The rotation speed and rotation time of the mechanical milling are not particularly limited, but the higher the rotation speed, the higher the production speed of the sulfide glass, and the longer the rotation time, the higher the conversion of the starting material to the sulfide glass.
By baking the sulfide glass obtained by mechanical milling at a glass transition temperature (150 ° C.) or higher, preferably 200 to 500 ° C., the sulfide glass ceramics having improved electrical conductivity at room temperature (25 ° C.) is obtained. can get. The shape of the sulfide glass to be subjected to the firing treatment is not particularly limited, but it may be in the form of a powder or may be formed into a pellet by pressure.
The firing treatment is preferably performed in the presence of an inert gas (such as a nitrogen gas or an argon gas) or in a vacuum. The heating rate, the cooling rate, and the firing time during the firing process are not particularly limited.
The sulfide glass ceramics thus obtained is suitable as a solid electrolyte.
[0011]
【Example】
Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Example 1
Lithium sulfide crystals (Li 2 S) and phosphorus pentasulfide (P 2 S 5 ) were used as starting materials, and lithium hydroxide (LiOH) was used as a glass modifier.
In a dry box under argon atmosphere, lithium sulfide crystals and phosphorus pentasulfide were weighed at a molar ratio of 6.9 / 2 (Li 2 S / P 2 S 5 ), and lithium sulfide crystals (Li 2 S) 100 parts by mass of lithium hydroxide (LiOH) was weighed at a ratio of 2.1 parts by mass, and these powders were charged into an alumina pot and completely sealed. This pot was attached to a planetary ball mill, and initially milled at low speed (rotational speed: 85 rpm) for several minutes in order to sufficiently mix the starting materials. Thereafter, the rotational speed was gradually increased, and mechanical milling was performed at 370 rpm for 20 hours.
As a result of X-ray diffraction of the obtained powdered glass, the peak of lithium sulfide (Li 2 S) disappeared, and it was confirmed that vitrification had progressed.
This powder sample was formed into a pellet under an inert gas (nitrogen) atmosphere under a pressure of 20 MPa (200 kg / cm 2 ), and then a carbon paste was applied as an electrode, and the electric conductivity was measured by an AC two-terminal method. As a result, the electrical conductivity at room temperature (25 ° C.) was 8.1 × 10 −5 S / cm.
[0012]
Example 2
The pellets obtained in Example 1 were calcined at 250 ° C. in the presence of an inert gas (nitrogen) to obtain sulfide glass ceramics. After cooling, the electric conductivity was measured in the same manner as in Example 1. The electric conductivity at room temperature (25 ° C.) was 3.0 × 10 −4 S / cm, and the electric conductivity was improved by firing. did.
[0013]
Comparative Example 1
A glass powder was obtained in the same manner as in Example 1 except that 0.53 parts by mass of lithium hydroxide (LiOH) was weighed with respect to 100 parts by mass of lithium sulfide crystal (Li 2 S). As a result of X-ray diffraction of the obtained powder glass, a large peak of unreacted lithium sulfide (Li 2 S) was detected.
The powdered glass was pressed into a pellet in the same manner as in Example 1, a carbon paste was applied as an electrode, and the electrical conductivity was measured by the same method as in Example 1. As a result, at room temperature (25 ° C.) Had a very low electric conductivity of 1.0 × 10 −5 S / cm.
[0014]
Comparative Example 2
A glass powder was obtained in the same manner as in Example 1, except that 0.74 parts by mass of lithium hydroxide (LiOH) was weighed with respect to 100 parts by mass of lithium sulfide crystal (Li 2 S). As a result of X-ray diffraction of the obtained powder glass, a large peak of unreacted lithium sulfide (Li 2 S) was detected.
The powdered glass was pressed into a pellet in the same manner as in Example 1, a carbon paste was applied as an electrode, and the electrical conductivity was measured by the same method as in Example 1. As a result, at room temperature (25 ° C.) Had a very low electric conductivity of 5.0 × 10 −6 S / cm.
[0015]
Example 3
An all-solid-state lithium secondary battery was manufactured using the pelletized sulfide glass ceramics obtained in Example 2 as a solid electrolyte.
Lithium cobalt oxide showing a potential exceeding 4 V was used as a positive electrode, and indium metal was used as a negative electrode. When constant current discharge measurement was performed at a current density of 50 μA / cm 2 , charge and discharge were possible. In addition, the charge and discharge efficiency was 100%, and it was found that the battery exhibited excellent cycle characteristics.
[0016]
【The invention's effect】
According to the present invention, a lithium ion conductive sulfide glass and a ceramic having high electrical conductivity at room temperature can be produced by a simple method using easily available and inexpensive raw materials as starting materials.
Claims (8)
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| JP2003120177A JP4580149B2 (en) | 2003-04-24 | 2003-04-24 | Lithium ion conductive sulfide glass manufacturing method and lithium ion conductive sulfide glass ceramic manufacturing method |
| PCT/JP2004/005914 WO2004095474A1 (en) | 2003-04-24 | 2004-04-23 | Lithium ion-conductive sulfide glass, process for producing glass ceramic, and wholly solid type cell made with the glass ceramic |
| TW093111508A TWI415140B (en) | 2003-04-24 | 2004-04-23 | Lithium-ion conductive sulfide glass and glass-ceramic manufacturing method, and a solid-state battery using the same |
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