JP4498688B2 - Method for producing lithium ion conductive sulfide glass and glass ceramics - Google Patents
Method for producing lithium ion conductive sulfide glass and glass ceramics Download PDFInfo
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- JP4498688B2 JP4498688B2 JP2003120176A JP2003120176A JP4498688B2 JP 4498688 B2 JP4498688 B2 JP 4498688B2 JP 2003120176 A JP2003120176 A JP 2003120176A JP 2003120176 A JP2003120176 A JP 2003120176A JP 4498688 B2 JP4498688 B2 JP 4498688B2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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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硫酸リチウム（Ｌｉ2 ＳＯ4 ）及びチオ硫酸リチウム（Ｌｉ2 Ｓ2 Ｏ3 ）から選ばれる一種以上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７〜２０質量部の硫酸リチウム及び２．７〜１５質量部のチオ硫酸リチウムを添加し、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、
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、硫酸リチウム（Ｌｉ2 ＳＯ4 ）及びチオ硫酸リチウム（Ｌｉ2 Ｓ2 Ｏ3 ）から選ばれる一種以上を用いる。硫酸リチウムの添加量は、硫化リチウム１００質量部に対して６．５質量部以上であることを要し、好ましくは７〜２０質量部である。また、チオ硫酸リチウムの添加量は、硫化リチウム１００質量部に対して２．２質量部以上であることを要し、好ましくは２．７〜１５質量部である。硫酸リチウム（Ｌｉ2 ＳＯ4 ）とチオ硫酸リチウム（Ｌｉ2 Ｓ2 Ｏ3 ）とを併用する場合、その使用割合は質量比でＬｉ2 ＳＯ4 ：Ｌｉ2 Ｓ2 Ｏ3 ＝１：０．１３５〜２が好ましく、Ｌｉ2 ＳＯ4 ：Ｌｉ2 Ｓ2 Ｏ3 ＝１：０．１５〜１．８がより好ましい。
【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、硫酸リチウム（Ｌｉ2 ＳＯ4 ）及びチオ硫酸リチウム（Ｌｉ2 Ｓ2 Ｏ3 ）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、硫酸リチウム（Ｌｉ2 ＳＯ4 ）１１．４質量部及びチオ硫酸リチウム（Ｌｉ2 Ｓ2 Ｏ3 ）３．６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１．７×１０-4Ｓ／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７．２×１０-4Ｓ／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、硫酸リチウム（Ｌｉ2 ＳＯ4 ）６．３質量部及びチオ硫酸リチウム（Ｌｉ2 Ｓ2 Ｏ3 ）１．９３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、硫酸リチウム（Ｌｉ2 ＳＯ4 ）５．６質量部及びチオ硫酸リチウム（Ｌｉ2 Ｓ2 Ｏ3 ）２．０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]
BACKGROUND OF THE INVENTION
The present invention relates to the production how the lithium ion conductive sulfide glass and glass ceramic.
[0002]
[Prior art]
It is known that lithium ion conductive sulfide glass and glass ceramics can be used as an electrolyte for an all-solid-state lithium secondary battery. Such a sulfide glass is prepared by mixing glass forming agents SiS 2 , phosphorus pentasulfide (P 2 S 5 ), B 2 S 3 and the like with a glass modifier lithium sulfide (Li 2 S) and heating and melting them. Then, it is obtained by quenching (see, for example, Patent Document 1).
The present inventors have also disclosed 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 react efficiently with the above glass forming agent, and unreacted lithium sulfide is generated. Since a large amount remains, the target sulfide glass cannot be obtained. Further, if a large amount of unreacted lithium sulfide remains, there is a problem that the performance as an electrolyte is lowered, and it cannot be used as an electrolyte for an all-solid-state lithium battery.
The inventors of the present invention have studied a method for producing a lithium ion conductive sulfide glass starting from an easily available and inexpensive raw material.
For example, the present inventors perform lithium ion conductive sulfide by performing mechanical milling using metallic lithium (Li) or lithium sulfide (Li 2 S), simple silicon (Si), and simple sulfur (S) as starting materials. It disclosed that glass was obtained (refer patent document 2).
However, this sulfide glass has a problem that the mechanical milling time becomes longer and the electrical conductivity of the obtained sulfide glass is low as compared with the case where 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 found that sulfide ceramics mainly composed of lithium sulfide and phosphorus pentasulfide exhibit high lithium ion conductivity. (See Patent Document 3).
It has also been found that the electrical conductivity at room temperature is improved by firing a sulfide obtained by mechanical milling of lithium sulfide and phosphorus pentasulfide at a glass transition temperature or higher (see Non-Patent Document 1). ). Furthermore, as a more available raw material, metallic lithium is added to a material obtained by vitrification of simple phosphorus (P) and simple sulfur (S) by mechanical milling, and further, electrical conductivity at room temperature is 10 by further mechanical milling. It was also found that sulfide glass of -5 S / cm order can be obtained (see Non-Patent Document 2).
[0004]
[Patent Document 1]
JP-A-9-283156 [Patent Document 2]
Japanese Patent Laid-Open No. 11-134937 [Patent Document 3]
JP 2001-250580 A [Non-Patent Document 1]
Chemistry Letters 2001
[Non-Patent Document 2]
Kasuna et al: Chemical Society of Japan 2001 Spring Conference Abstracts 2E341
[0005]
[Means for Solving the Problems]
The present inventors further examined a production method using a simple and easily available raw material, and used metallic lithium or lithium sulfide, simple sulfur (S) and simple phosphorus (P) as starting materials, and mechanical It has been found that the sulfide glass obtained by milling has the same performance as lithium ion conductive sulfide glass produced by mechanical milling using lithium sulfide and phosphorus pentasulfide as raw materials (Japanese Patent Application No. 2002-005855). . Furthermore, a simple and efficient production method is studied, and a solid electrolyte is obtained by using one or more kinds selected from lithium sulfate (Li 2 SO 4 ) and lithium thiosulfate (Li 2 S 2 O 3 ) as a glass modifier. As a result, the inventors have found that a useful sulfide glass can be obtained, and have completed the present invention.
Furthermore, it has also been found that the sulfide glass obtained in 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
(1) In manufacturing lithium ion conductive sulfide glass, a raw material containing at least one selected from lithium sulfide and phosphorus pentasulfide, elemental phosphorus and elemental sulfur is used as a starting material. Lithium sulfate is characterized in that 7 to 20 parts by mass of lithium sulfate and 2.7 to 15 parts by mass of lithium thiosulfate are added to 100 parts by mass of lithium sulfide, and the raw material is vitrified by mechanical milling. Production method of ion-conductive sulfide glass,
(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) , characterized by firing at 150 ° C. or higher,
(4) The method for producing a lithium ion conductive sulfide glass ceramic according to (2) or (3) , wherein the firing is performed in a vacuum or in the presence of an inert gas ,
Is to provide.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, a raw material containing at least one selected from lithium sulfide (Li 2 S), phosphorus pentasulfide (P 2 S 5 ), simple phosphorus (P) and simple sulfur (S) is used as a starting material. The lithium sulfide (Li 2 S) used in the present invention may be produced by any production method and can be used without particular limitation as long as it is industrially produced and sold. What was manufactured by the manufacturing method described in Kai 2000-247609 is preferable.
As long as phosphorus pentasulfide, elemental sulfur, and elemental phosphorus are industrially produced and sold, they can be used without particular limitation. Further, as the elemental sulfur, molten sulfur produced at a refinery or the like can be used as it is.
[0008]
When using lithium sulfide (Li 2 S), elemental sulfur (S) and elemental phosphorus (P) as starting materials, the mixing ratio of lithium sulfide elemental sulfur and elemental phosphorus is in terms of molar ratio to elemental lithium sulfide 1 Sulfur 0.5-3.5 and simple phosphorus 0.2-1.5 are preferred. Further, as a starting material, when using the lithium sulfide (Li 2 S) and phosphorus pentasulfide (P 2 S 5), with respect to the lithium sulfide at a molar ratio of 1, preferably phosphorus pentasulfide 0.05 to 1.0. Furthermore, simple silicon (Si), metallic germanium (Ge), metallic aluminum (Al), metallic iron (Fe), metallic zinc (Zn) and simple boron (B) are also amorphous or crystalline by simple sulfur and mechanical milling. In order to produce a water-soluble sulfide (Sasara et al .: Abstracts of Annual Meeting 2001 Spring Meeting of the Chemical Society of Japan 2E341), a part of the starting material of the lithium ion conductive sulfide glass can be replaced with these.
In the present invention, at least one selected from lithium sulfate (Li 2 SO 4 ) and lithium thiosulfate (Li 2 S 2 O 3 ) is used as the glass modifier. The addition amount of lithium sulfate needs to be 6.5 parts by mass or more, preferably 7 to 20 parts by mass with respect to 100 parts by mass of lithium sulfide. Moreover, the addition amount of lithium thiosulfate needs to be 2.2 mass parts or more with respect to 100 mass parts of lithium sulfide, Preferably it is 2.7-15 mass parts. When lithium sulfate (Li 2 SO 4 ) and lithium thiosulfate (Li 2 S 2 O 3 ) are used in combination, the use ratio is Li 2 SO 4 : Li 2 S 2 O 3 = 1: 0.135 in terms of mass ratio. ˜2 is preferable, and Li 2 SO 4 : Li 2 S 2 O 3 = 1: 0.15 to 1.8 is more preferable.
[0009]
In the present invention, in order to vitrify a starting material containing at least one selected from lithium sulfide (Li 2 S), phosphorus pentasulfide (P 2 S 5 ), elemental phosphorus (P) and elemental sulfur (S), Use mechanical milling. According to mechanical milling, since glass can be synthesized near room temperature, there is an advantage that glass having a charged composition can be obtained without thermal decomposition of the starting material. Mechanical milling also has the advantage that glass can be made into fine powder simultaneously with the synthesis of glass.
In the method of the present invention, there is no need to pulverize or cut the ion-conductive sulfide glass again when it is pulverized. Such finely powdered glass can be used, for example, as a solid electrolyte by incorporating it directly or in a pellet form into an all-solid battery.
According to the method of the present invention, the production process of the ion conductive sulfide glass as the solid electrolyte for a battery can be simplified, and the cost can be reduced. Furthermore, according to mechanical milling, ion-conductive sulfide glass having a uniform particle size with fine powder can be generated.
If such a glass ceramic is used as a solid electrolyte, an increase in contact interface with the positive electrode and the negative electrode and 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. The planetary ball mill can efficiently generate very high impact energy by rotating the platform while the pot rotates.
The rotation speed and rotation time of mechanical milling are not particularly limited, but the higher the rotation speed, the faster the generation rate of sulfide glass, and the longer the rotation time, the higher the conversion rate of the starting material to sulfide glass.
A sulfide glass ceramic having improved electrical conductivity at room temperature (25 ° C.) by firing the sulfide glass obtained by mechanical milling at a glass transition temperature (150 ° C.) or higher, preferably 200 to 500 ° C. can get. The shape of the sulfide glass to be baked is not particularly limited, but may be a powder or may be pressure-molded into a pellet.
The firing treatment is preferably performed in the presence of an inert gas (nitrogen gas, argon gas, etc.) or under vacuum. There are no particular limitations on the rate of temperature rise, the rate of temperature drop, and the firing time during the firing treatment.
The sulfide glass ceramic thus obtained is suitable as a solid electrolyte.
[0011]
【Example】
EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited at all by these examples.
Example 1
Lithium sulfide crystals (Li 2 S) and phosphorus pentasulfide (P 2 S 5 ) are used as starting materials, and lithium sulfate (Li 2 SO 4 ) and lithium thiosulfate (Li 2 S 2 O 3 ) are used as glass modifiers. Was used.
In a dry box under an atmosphere of argon, 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 sulfate (Li 2 SO 4 ) 11.4 parts by mass and lithium thiosulfate (Li 2 S 2 O 3 ) 3.6 parts by mass, and these powders were alumina. It was put into a pot made of metal and completely sealed. This pot was attached to a planetary ball mill and initially milled at a low speed (rotation 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 powder glass, the peak of lithium sulfide (Li 2 S) disappeared, and it was confirmed that vitrification was progressing.
This powder sample was formed into a pellet under pressure of 20 MPa (200 kg / cm 2 ) under an inert gas (nitrogen) atmosphere, and then carbon paste was applied as an electrode, and the electrical conductivity was measured by the AC two-terminal method. As a result, the electric conductivity at room temperature (25 ° C.) was 1.7 × 10 −4 S / cm.
[0012]
Example 2
The pellets obtained in Example 1 were fired at 250 ° C. in the presence of an inert gas (nitrogen) to obtain sulfide glass ceramics. After cooling, the electrical conductivity was measured in the same manner as in Example 1. As a result, the electrical conductivity at room temperature (25 ° C.) was 7.2 × 10 −4 S / cm, and the electrical conductivity was improved by firing. did.
[0013]
Comparative Example 1
Weighed at a ratio of 6.3 parts by mass of lithium sulfate (Li 2 SO 4 ) and 1.93 parts by mass of lithium thiosulfate (Li 2 S 2 O 3 ) with respect to 100 parts by mass of the lithium sulfide crystal (Li 2 S). A glass powder was obtained in the same manner as in Example 1 except that it was used. As a result of X-ray diffraction of the obtained powder glass, a large peak of unreacted lithium sulfide (Li 2 S) was detected.
This powder glass was pressure-molded into a pellet shape in the same manner as in Example 1, and a carbon paste was applied as an electrode. The electrical conductivity was measured in the same manner as in Example 1. At room temperature (25 ° C.) The electrical conductivity of was as low as 1.0 × 10 −5 S / cm.
[0014]
Comparative Example 2
Weighing at a ratio of 5.6 parts by mass of lithium sulfate (Li 2 SO 4 ) and 2.0 parts by mass of lithium thiosulfate (Li 2 S 2 O 3 ) with respect to 100 parts by mass of the lithium sulfide crystal (Li 2 S). A glass powder was obtained in the same manner as in Example 1 except that it was used. As a result of X-ray diffraction of the obtained powder glass, a large peak of unreacted lithium sulfide (Li 2 S) was detected.
This powder glass was pressure-molded into a pellet shape in the same manner as in Example 1, and a carbon paste was applied as an electrode. The electrical conductivity was measured in the same manner as in Example 1. At room temperature (25 ° C.) The electrical conductivity of was as low as 5.0 × 10 −6 S / cm.
[0015]
Example 3
An all-solid-state lithium secondary battery was fabricated using the pelletized sulfide glass ceramic obtained in Example 2 as a solid electrolyte.
Lithium cobaltate showing a potential exceeding 4 V was used as the positive electrode, and indium metal was used for the negative electrode. When constant current discharge measurement was performed at a current density of 50 μA / cm 2 , charging / discharging was possible. The charge / discharge efficiency was also 100%, and it was found that excellent cycle characteristics were exhibited.
[0016]
【The invention's effect】
According to the present invention, lithium ion conductive sulfide glass and ceramics having high electrical conductivity at room temperature can be produced by a simple method using an easily available and inexpensive raw material as a starting material.
Claims (4)
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| JP2003120176A JP4498688B2 (en) | 2003-04-24 | 2003-04-24 | Method for producing lithium ion conductive sulfide glass and glass ceramics |
| 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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| JP5414143B2 (en) * | 2006-06-21 | 2014-02-12 | 出光興産株式会社 | Method for producing sulfide solid electrolyte |
| JP5848801B2 (en) * | 2006-10-19 | 2016-01-27 | 出光興産株式会社 | Lithium ion conductive solid electrolyte sheet and method for producing the same |
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| JP6320983B2 (en) | 2015-12-01 | 2018-05-09 | 出光興産株式会社 | Method for producing sulfide glass ceramics |
| KR102651625B1 (en) * | 2016-06-22 | 2024-03-27 | 주식회사 솔리비스 | Lithium secondary battery solid electrolytes and method of preparing the same |
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