JPH05310418A - Amorphous lithium ion conductive solid electrolyte and its synthesis - Google Patents

Amorphous lithium ion conductive solid electrolyte and its synthesis

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Publication number
JPH05310418A
JPH05310418A JP4118690A JP11869092A JPH05310418A JP H05310418 A JPH05310418 A JP H05310418A JP 4118690 A JP4118690 A JP 4118690A JP 11869092 A JP11869092 A JP 11869092A JP H05310418 A JPH05310418 A JP H05310418A
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Japan
Prior art keywords
solid electrolyte
ion conductive
lithium ion
conductive solid
sis
Prior art date
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Application number
JP4118690A
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Japanese (ja)
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JP3343936B2 (en
Inventor
Noboru Aotani
登 青谷
Shigeo Kondo
繁雄 近藤
Kazunori Takada
和典 高田
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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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
    • 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

Abstract

PURPOSE:To provide a solid electrolyte having high lithium ion conductivity by enhancing the concentration of movable ions and simultaneously vitrifying the solid electrolyte for increasing the ion conductivity of the solid electrolyte. CONSTITUTION:In amorphous lithium ion conductive solid electrolyte represented by the general formula aLi3PO4.bLi S2.cX (a+b+c=1; X is at least one sulfide selected from SiS2, GeS2, P2S5 and B2S3), the solid electrolyte having a composition range of a<0.3, b>0.3 and c>0.2 is employed.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、全固体電池、コンデン
サ、固体エレクトロクロミック表示素子等の固体電気化
学素子の電解質として利用されるリチウムイオン伝導性
固体電解質に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium ion conductive solid electrolyte used as an electrolyte for solid-state electrochemical devices such as all-solid-state batteries, capacitors, and solid electrochromic display devices.

【０００２】[0002]

【従来の技術】近年、リチウムイオン伝導性固体電解質
を用いたリチウム電池の全固体化に関する研究が盛んに
行われている。2. Description of the Related Art In recent years, much research has been conducted on the solidification of lithium batteries using a lithium ion conductive solid electrolyte.

【０００３】この様なリチウムイオン伝導性固体電解質
の一つとしてＬｉ2 Ｓ・Ｘ（ＸはＳｉＳ2 ，ＧｅＳ2 ，
Ｐ2 Ｓ5 ，Ｂ2 Ｓ3 のうち少なくとも一種の硫化物）系
硫化物ガラスが存在する。As one of such lithium ion conductive solid electrolytes, Li 2 S.X (X is SiS 2 , GeS 2 ,
At least one sulfide-based sulfide glass of P 2 S 5 and B 2 S 3 is present.

【０００４】Ｌｉ2 Ｓ・Ｘ系硫化物ガラスは、ＸがＳｉ
Ｓ2 のＬｉ2 Ｓ・ＳｉＳ2 系において最も高い伝導率の
値を有し、その値は、５×１０-4Ｓ／ｃｍ程度である。In the Li 2 S.X-based sulfide glass, X is Si
Has a value of highest conductivity in Li 2 S · SiS 2 system S 2, the value is about 5 × 10 -4 S / cm.

【０００５】また、さらに高いイオン伝導性を得るため
に、これら硫化物ガラスにヨウ化リチウム（ＬｉＩ）あ
るいはリン酸リチウム（Ｌｉ3 ＰＯ4 ）を添加した擬３
成分系ガラスの提案が行われている。Further, in order to obtain higher ionic conductivity, a pseudo-3 obtained by adding lithium iodide (LiI) or lithium phosphate (Li 3 PO 4 ) to these sulfide glasses.
Proposals for component glass have been made.

【０００６】[0006]

【発明が解決しようとする課題】これら各種の固体電解
質の提案は、そのイオン伝導性を向上させることを目的
としている。伝導率は可動イオンの濃度と移動度の積に
比例するため、固体電解質の伝導率を向上させるために
は可動イオンの濃度を上げることが必要となる。例えば
ＬｉＳ2 ・Ｘ（ＸはＳｉＳ2 ，ＧｅＳ2 ，Ｐ2 Ｓ5 ，Ｂ
2 Ｓ3 のうち少なくとも一種の硫化物）２成分系ガラス
ではＬｉ2 Ｓ成分を増やすことにより伝導率が向上す
る。The proposals of these various solid electrolytes are aimed at improving their ionic conductivity. Since the conductivity is proportional to the product of the concentration of mobile ions and the mobility, it is necessary to increase the concentration of mobile ions in order to improve the conductivity of the solid electrolyte. For example, LiS 2 · X (X is SiS 2 , GeS 2 , P 2 S 5 , B
In at least one sulfide of 2 S 3 ) binary glass, the conductivity is improved by increasing the Li 2 S component.

【０００７】しかしながら、これらの系でのガラス化領
域は限られており、Ｌｉ2 Ｓの組成比を大きくするとガ
ラス形成が不可能となり逆に伝導率が低下する結果とな
る。However, the vitrification region in these systems is limited, and when the composition ratio of Li 2 S is increased, glass formation becomes impossible and conversely the conductivity is lowered.

【０００８】本発明は、以上の課題を解決し、より高い
リチウムイオン伝導性を有する固体電解質とその合成法
を提供することを目的とする。An object of the present invention is to solve the above problems and provide a solid electrolyte having higher lithium ion conductivity and a method for synthesizing the solid electrolyte.

【０００９】[0009]

【課題を解決するための手段】本発明の非晶質リチウム
イオン伝導性固体電解質は、一般式ａＬｉ3 ＰＯ4 ・ｂ
Ｌｉ2 Ｓ・ｃＸ（ａ＋ｂ＋ｃ＝１、ＸはＳｉＳ2 ，Ｇｅ
Ｓ2 ，Ｐ2 Ｓ5 ，Ｂ2Ｓ3 のうち少なくとも一種の硫化
物）で表され、組成比ａ、ｂ、ｃ、がａ＜０．３かつｂ
＞０．３かつｃ＞０．２をみたすことを特徴とする。The amorphous lithium ion conductive solid electrolyte of the present invention has the general formula aLi 3 PO 4 .b.
Li 2 S · cX (a + b + c = 1, X is SiS 2 , Ge
Is represented by S 2, at least one sulfide of P 2 S 5, B 2 S 3), the composition ratio a, b, c, but a <0.3 and b
It is characterized by satisfying> 0.3 and c> 0.2.

【００１０】尚、前記一般式ａＬｉ3 ＰＯ4 ・ｂＬｉ2
Ｓ・ｃＸ（ａ＋ｂ＋ｃ＝１、ＸはＳｉＳ2 ，ＧｅＳ2 ，
Ｐ2 Ｓ5 ，Ｂ2 Ｓ3 のうち少なくとも一種の硫化物）で
表される非晶質リチウムイオン伝導性固体電解質は、組
成比ａ、ｂ、ｃ、がａ≦０．１かつｂ≧０．５かつｃ≧
０．３をみたす領域を用いることが好ましい。The above general formula aLi 3 PO 4 .bLi 2
S · cX (a + b + c = 1, X is SiS 2 , GeS 2 ,
An amorphous lithium ion conductive solid electrolyte represented by at least one sulfide of P 2 S 5 and B 2 S 3 has a composition ratio a, b, c of a ≦ 0.1 and b ≧ 0. .5 and c ≧
It is preferable to use a region satisfying 0.3.

【００１１】また、前記非晶質リチウムイオン伝導性固
体電解質は、Ｌｉ3 ＰＯ4 とＬｉ2ＳとＸ（ＸはＳｉＳ
2 ，ＧｅＳ2 ，Ｐ2 Ｓ5 ，Ｂ2 Ｓ3 のうち少なくとも一
種の硫化物）の混合物を溶融し、その後急冷することに
より合成するのが好ましい。The amorphous lithium ion conductive solid electrolyte is composed of Li 3 PO 4 , Li 2 S and X (X is SiS).
It is preferable that a mixture of 2 , GeS 2 , P 2 S 5 , and B 2 S 3 of at least one sulfide) is melted and then rapidly cooled to synthesize it.

【００１２】[0012]

【作用】ＬｉＳ2 ・Ｘ（ＸはＳｉＳ2 ，ＧｅＳ2 ，Ｐ2
Ｓ5 ，Ｂ2 Ｓ3 のうち少なくとも一種の硫化物）擬２成
分系ガラスに第３成分としてＬｉ3 ＰＯ4 を加えること
で、可動イオンであるリチウムイオンの濃度が大きなも
のとなり、伝導率が向上する。またさらに、Ｌｉ3 ＰＯ
4 の成分であるＰＯ4 3-はガラスネットワーク形成能を
有することから、２成分系ではガラス化が不可能であっ
たＬｉ2 Ｓ成分が多い組成領域でもガラス化が可能とな
る。Operation: LiS 2 · X (X is SiS 2 , GeS 2 , P 2
By adding Li 3 PO 4 as a third component to at least one sulfide (quasi-binary glass of S 5 and B 2 S 3 ) as a third component, the concentration of lithium ions, which are mobile ions, becomes large, and the conductivity increases. improves. Furthermore, Li 3 PO
Since PO 4 3−, which is the fourth component, has the ability to form a glass network, vitrification is possible even in a composition region containing a large amount of Li 2 S component, which was not possible in the two-component system.

【００１３】一般式ａＬｉ3 ＰＯ4 ・ｂＬｉ2 Ｓ・ｃＸ
（ａ＋ｂ＋ｃ＝１、ＸはＳｉＳ2 ，ＧｅＳ2 ，Ｐ
2 Ｓ5 ，Ｂ2 Ｓ3 のうち少なくとも一種の硫化物）を主
成分とするリチウムイオン伝導性固体電解質では、組成
比ａ、ｂ、ｃがａ＜０．３かつｂ＞０．３かつｃ＞０．
２をみたす組成領域でガラス化が可能となり、高いイオ
ン伝導性を示す非晶質リチウムイオン伝導性固体電解質
を得ることができる。The general formula aLi 3 PO 4 .bLi 2 S.cX
(A + b + c = 1, X is SiS 2 , GeS 2 , P
In a lithium ion conductive solid electrolyte containing at least one sulfide of 2 S 5 and B 2 S 3 as a main component, the composition ratios a, b and c are a <0.3 and b> 0.3 and c. > 0.
Vitrification is possible in the composition region satisfying 2, and an amorphous lithium ion conductive solid electrolyte exhibiting high ion conductivity can be obtained.

【００１４】さらにこの組成領域の中でも、組成比ａ、
ｂ、ｃがａ≦０．１かつｂ≧０．５かつｃ≧０．３をみ
たす組成領域で可動イオンの濃度が高いものとなり、伝
導率が極大を示すことから、特に好ましく用いられる。Further, within this composition region, the composition ratio a,
In the composition region where b and c satisfy a ≦ 0.1 and b ≧ 0.5 and c ≧ 0.3, the concentration of mobile ions becomes high and the conductivity shows a maximum, so that it is particularly preferably used.

【００１５】ａＬｉ3 ＰＯ4 ・ｂＬｉ2 Ｓ・ｃＸ（ａ＋
ｂ＋ｃ＝１）を主成分とする化合物において、ＸがＳｉ
Ｓ2 であるときガラス化が容易にできることから、Ｘと
してＳｉＳ2 が特に好ましく用いられる。ALi 3 PO 4 .bLi 2 S.cX (a +
In a compound containing b + c = 1) as the main component, X is Si
SiS 2 is particularly preferably used as X, because vitrification can be easily carried out when it is S 2 .

【００１６】また、擬３成分系硫化物ガラスを作製する
には、一般に擬２成分系ガラスを母材として作製し、こ
れに第３成分を混合、溶融し、ガラスを作製するといっ
た２段階のプロセスをとる方法が一般的であるが、Ｌｉ
3 ＰＯ4 ・Ｌｉ2 Ｓ・Ｘ（ＸはＳｉＳ2 ，ＧｅＳ2 ，Ｐ
2 Ｓ5 ，Ｂ2 Ｓ3 のうち少なくとも一種の硫化物）擬３
成分系ガラスを作製するには、ＰＯ4 3-がガラスネット
ワーク形成に寄与するために、このような２段階のプロ
セスをとる必要はなく、材料を一度に混合し、溶融した
後、急冷することで合成の際の工数を簡略化することが
できる。In order to produce a quasi-three-component system sulfide glass, generally, a quasi-two-component system glass is prepared as a base material, and a third component is mixed and melted in this to produce a glass. The process is generally used, but Li
3 PO 4 · Li 2 S · X (X is SiS 2 , GeS 2 , P
At least one sulfide of 2 S 5 and B 2 S 3 ) Pseudo 3
In order to produce the component type glass, PO 4 3− contributes to the formation of the glass network, and thus it is not necessary to perform such a two-step process. The materials are mixed at once, melted, and then rapidly cooled. Can simplify the man-hours for the synthesis.

【００１７】[0017]

【実施例】以下、本発明を具体的実施例により詳細に説
明するが、本発明は、これら実施例に限定されるもので
はない。EXAMPLES The present invention will now be described in detail with reference to specific examples, but the present invention is not limited to these examples.

【００１８】（実施例１）本発明による非晶質リチウム
イオン伝導性固体電解質の内、Ｌｉ3 ＰＯ4 ・Ｌｉ2 Ｓ
・ＳｉＳ2 で表される非晶質リチウムイオン伝導性固体
電解質を以下の方法で合成した。Example 1 Among the amorphous lithium ion conductive solid electrolytes according to the present invention, Li 3 PO 4 .Li 2 S
An amorphous lithium ion conductive solid electrolyte represented by SiS 2 was synthesized by the following method.

【００１９】母材としてＬｉ2 Ｓ・ＳｉＳ2 系硫化物ガ
ラスを合成し、これにＬｉ3 ＰＯ4を添加して、ａＬｉ
3 ＰＯ4 ・ｂＬｉ2 Ｓ・ｃＳｉＳ2 （ａ＋ｂ＋ｃ＋＝
１）を合成した。Li 2 S.SiS 2 type sulfide glass was synthesized as a base material, and Li 3 PO 4 was added to this to obtain aLi.
3 PO 4 · bLi 2 S · cSiS 2 (a + b + c + =
1) was synthesized.

【００２０】先ず、Ｌｉ2 Ｓ・ＳｉＳ2 系硫化物ガラス
の合成法を示すと、硫化リチウム（Ｌｉ2 Ｓ）と硫化珪
素（ＳｉＳ2 ）を所定の組成となるように混合した材料
粉末をガラス状カーボン坩堝にいれ、これを、アルゴン
気流中９５０°Ｃで１．５時間溶融し反応させた後、液
体窒素中に投入して急冷し、Ｌｉ2 Ｓ・ＳｉＳ2 を合成
し母材とした。First, a method of synthesizing a Li 2 S.SiS 2 type sulfide glass will be described. Lithium sulfide (Li 2 S) and silicon sulfide (SiS 2 ) are mixed so as to have a predetermined composition, and a material powder is mixed with glass. In a rectangular carbon crucible, which was melted and reacted at 950 ° C. for 1.5 hours in an argon stream, then put into liquid nitrogen and rapidly cooled to synthesize Li 2 S.SiS 2 as a base material. ..

【００２１】次に、これらの母材を粉砕し、これにリン
酸リチウム（Ｌｉ3 ＰＯ4 ）をａＬｉ3 ＰＯ4 ・ｂＬｉ
2 Ｓ・ｃＳｉＳ2 （ａ＋ｂ＋ｃ＝１）の所定の組成とな
るように加えて混合し、得られた材料粉末をガラス状カ
ーボン坩堝にいれ、これを、アルゴン気流中９５０°Ｃ
で１．５時間溶融し反応させた後、液体窒素中に投入し
て急冷し、ａＬｉ3 ＰＯ4 ・ｂＬｉ2 Ｓ・ｃＳｉＳ
2 （ａ＋ｂ＋ｃ＝１）リチウムイオン伝導性固体電解質
を合成した。Next, these base materials were pulverized, and lithium phosphate (Li 3 PO 4 ) was added to this, aLi 3 PO 4 .bLi.
2 S · cSiS 2 (a + b + c = 1) was added and mixed so as to have a predetermined composition, and the obtained material powder was put into a glassy carbon crucible and placed in an argon stream at 950 ° C.
In After melted 1.5 hours, then quenched by poured into liquid nitrogen, aLi 3 PO 4 · bLi 2 S · cSiS
2 (a + b + c = 1) lithium ion conductive solid electrolyte was synthesized.

【００２２】合成の結果、生成物がガラス化する組成領
域とガラス化しない組成領域がみられた。ガラス化範囲
は図１に示すように、ａ＜０．３、ｂ＞０．３、ｃ＞
０．２の範囲であり、Ｌｉ2 Ｓ・ＳｉＳ2 擬２成分系で
はガラス化しない組成、例えば０．６５Ｌｉ2 Ｓ・０．
３５ＳｉＳ2 に対し、リン酸リチウムを加えて０．０５
Ｌｉ3 ＰＯ4 ・（０．６５Ｌｉ2 Ｓ・０．３５Ｓｉ
Ｓ2 ）とすることによりガラス化が可能であることがわ
かった。As a result of the synthesis, a composition region in which the product vitrified and a composition region in which the product did not vitrify were observed. The vitrification range is a <0.3, b> 0.3, c> as shown in FIG.
In the range of 0.2, the composition does not vitrify the Li 2 S · SiS 2 quasi-two-component system, for example 0.65Li 2 S · 0.
Lithium phosphate was added to 35SiS 2 to obtain 0.05
Li 3 PO 4 · (0.65Li 2 S · 0.35Si
It was found that vitrification is possible by using S 2 ).

【００２３】以上のようにして合成した固体電解質のイ
オン伝導率を、交流インピーダンス法により測定した。The ionic conductivity of the solid electrolyte synthesized as described above was measured by the AC impedance method.

【００２４】測定の結果、ａ≦０．１、ｂ≧０．５、ｃ
≧０．３の組成領域で特に高い伝導率を示し、２×１０
-4〜７×１０-4Ｓ／ｃｍであった。伝導率が最大となる
組成は、０．０３Ｌｉ3 ＰＯ4 ・０．６３Ｌｉ2 Ｓ・
０．３４ＳｉＳ2 であった。As a result of the measurement, a ≦ 0.1, b ≧ 0.5, c
Particularly high conductivity is exhibited in the composition region of ≧ 0.3, 2 × 10
It was −4 to 7 × 10 −4 S / cm. The composition that maximizes the conductivity is 0.03Li 3 PO 4 0.63Li 2 S
It was 0.34SiS 2 .

【００２５】以上のように、本発明によると、Ｌｉ2 Ｓ
・ＳｉＳ2 擬２成分系ではガラス化しなかった組成もリ
ン酸リチウムを加えることによりガラス化が可能とな
り、また、よりイオン伝導率の大きな固体電解質とする
ことができる。As described above, according to the present invention, Li 2 S
The composition which was not vitrified in the SiS 2 pseudo binary system can be vitrified by adding lithium phosphate, and a solid electrolyte having a higher ionic conductivity can be obtained.

【００２６】（実施例２）本発明による非晶質リチウム
イオン伝導性固体電解質の内、Ｌｉ3 ＰＯ4 ・Ｌｉ2 Ｓ
・ＧｅＳ2 で表される非晶質リチウムイオン伝導性固体
電解質を、ＳｉＳ 2 にかえてＧｅＳ2 を用いた以外は実
施例１と同様の方法で合成した。(Example 2) Amorphous lithium according to the present invention
Among the ion conductive solid electrolytes, Li3POFour・ Li2S
・ GeS2Amorphous lithium ion conductive solid represented by
Electrolyte, SiS 2GeS instead2Except using
It was synthesized in the same manner as in Example 1.

【００２７】合成の結果、生成物がガラス化する組成領
域とガラス化しない組成領域が見られた。ガラス化範囲
は図２で示すように、ａ＜０．３、ｂ＞０．３、ｃ＞
０．２の範囲であり、Ｌｉ2 Ｓ・ＧｅＳ2 擬２成分系で
はガラス化しない組成、例えば０．６５Ｌｉ2 Ｓ・０．
３５ＧｅＳ2 に対し、リン酸リチウムを加えて０．０５
Ｌｉ3 ＰＯ4 ・（０．６５Ｌｉ2 Ｓ・０．３５Ｇｅ
Ｓ2 ）とすることによりガラス化が可能であることがわ
かった。As a result of the synthesis, a composition region where the product vitrified and a composition region where the product did not vitrify were found. As shown in FIG. 2, the vitrification range is a <0.3, b> 0.3, c>
In the range of 0.2, the composition does not vitrify the Li 2 S · GeS 2 quasi-two-component system, for example 0.65Li 2 S · 0.
Lithium phosphate was added to 35 GeS 2 to obtain 0.05
Li 3 PO 4 · (0.65Li 2 S · 0.35Ge
It was found that vitrification is possible by using S 2 ).

【００２８】以上のようにして合成した固体電解質のイ
オン伝導率を、交流インピーダンス法により測定した。The ionic conductivity of the solid electrolyte synthesized as described above was measured by the AC impedance method.

【００２９】測定の結果、ａ≦０．１かつｂ≧０．５か
つｃ≧０．３の組成領域で特に高い伝導率を示し、１×
１０-4〜３×１０-4Ｓ／ｃｍとなった。伝導率が最大と
なる組成は、０．０３Ｌｉ3 ＰＯ4 ・０．６３Ｌｉ2 Ｓ
・０．３４ＧｅＳ2 であった。As a result of the measurement, a particularly high conductivity is shown in the composition region of a ≦ 0.1 and b ≧ 0.5 and c ≧ 0.3, 1 ×
It was 10 −4 to 3 × 10 −4 S / cm. The composition that maximizes the conductivity is 0.03Li 3 PO 4 0.63Li 2 S
-It was 0.34 GeS 2 .

【００３０】以上のように、本発明によると、Ｌｉ2 Ｓ
・ＧｅＳ2 擬２成分系ではガラス化しなかった組成もリ
ン酸リチウムを加えることによりガラス化が可能とな
り、また、よりイオン伝導率の大きな固体電解質とする
ことができる。As described above, according to the present invention, Li 2 S
-A composition that was not vitrified in the GeS 2 pseudo binary system can be vitrified by adding lithium phosphate, and a solid electrolyte having a higher ionic conductivity can be obtained.

【００３１】（実施例３）本発明による非晶質リチウム
イオン伝導性固体電解質の内、Ｌｉ3 ＰＯ4 ・Ｌｉ2 Ｓ
・Ｐ2 Ｓ5 で表される非晶質リチウムイオン伝導性固体
電解質を、ＳｉＳ 2 にかえてＰ2 Ｓ5 を用いた以外は実
施例１と同様の方法で合成した。Example 3 Amorphous lithium according to the present invention
Among the ion conductive solid electrolytes, Li3POFour・ Li2S
・ P2SFiveAmorphous lithium ion conductive solid represented by
Electrolyte, SiS 2Instead of P2SFiveExcept using
It was synthesized in the same manner as in Example 1.

【００３２】合成の結果、生成物がガラス化する組成領
域とガラス化しない組成領域が見られた。ガラス化範囲
は図３で示すように、ａ＜０．３、ｂ＞０．３、ｃ＞
０．２の範囲であり、Ｌｉ2 Ｓ・Ｐ2 Ｓ5 擬２成分系で
はガラス化しない組成、例えば０．６５Ｌｉ2 Ｓ・０．
３５Ｐ2 Ｓ5 に対し、リン酸リチウムを加えて０．０５
Ｌｉ3 ＰＯ4 ・（０．６５Ｌｉ2 Ｓ・０．３５Ｐ
2 Ｓ5 ）とすることによりガラス化が可能であることが
わかった。As a result of the synthesis, a composition region where the product vitrified and a composition region where the product did not vitrify were found. The vitrification range is a <0.3, b> 0.3, c> as shown in FIG.
It is in the range of 0.2 and does not vitrify in the Li 2 S · P 2 S 5 pseudo binary system, for example, 0.65 Li 2 S · 0.
Lithium phosphate was added to 35P 2 S 5 to obtain 0.05
Li 3 PO 4 · (0.65Li 2 S · 0.35P
It was found that vitrification is possible by using 2 S 5 ).

【００３３】以上のようにして合成した固体電解質のイ
オン伝導率を調べるため、交流インピーダンス法により
測定した。In order to investigate the ionic conductivity of the solid electrolyte synthesized as described above, it was measured by the AC impedance method.

【００３４】測定の結果、ａ≦０．１、ｂ≧０．５、ｃ
≧０．３の組成領域で特に高い伝導率を示し、２×１０
-4〜４×１０-4Ｓ／ｃｍとなった。伝導率が最大となる
組成は、０．０３Ｌｉ3 ＰＯ4 ・０．６５Ｌｉ2 Ｓ・
０．３２Ｐ2 Ｓ5 であった。As a result of the measurement, a ≦ 0.1, b ≧ 0.5, c
Particularly high conductivity is exhibited in the composition region of ≧ 0.3, 2 × 10
-4 to 4 x 10 -4 S / cm. The composition conductivity is maximized, 0.03Li 3 PO 4 · 0.65Li 2 S ·
It was 0.32P 2 S 5 .

【００３５】以上のように、本発明によると、Ｌｉ2 Ｓ
・Ｐ2 Ｓ5 擬２成分系ではガラス化しなかった組成もリ
ン酸リチウムを加えることによりガラス化が可能とな
り、また、よりイオン伝導率の大きな固体電解質とする
ことができる。As described above, according to the present invention, Li 2 S
The composition which was not vitrified in the P 2 S 5 pseudo binary system can be vitrified by adding lithium phosphate, and a solid electrolyte having a higher ionic conductivity can be obtained.

【００３６】（実施例４）本発明による非晶質リチウム
イオン伝導性固体電解質の内、Ｌｉ3 ＰＯ4 ・Ｌｉ2 Ｓ
・Ｂ2 Ｓ3 で表される非晶質リチウムイオン伝導性固体
電解質を、ＳｉＳ 2 にかえてＢ2 Ｓ3 を用いた以外は実
施例１と同様の方法で合成した。Example 4 Amorphous lithium according to the present invention
Among the ion conductive solid electrolytes, Li3POFour・ Li2S
・ B2S3Amorphous lithium ion conductive solid represented by
Electrolyte, SiS 2Instead of B2S3Except using
It was synthesized in the same manner as in Example 1.

【００３７】合成の結果、生成物がガラス化する組成領
域とガラス化しない組成領域が見られた。ガラス化範囲
は図４で示すように、ａ＜０．３、ｂ＞０．３、ｃ＞
０．２の範囲であり、Ｌｉ2 Ｓ・Ｂ2 Ｓ3 擬２成分系で
はガラス化しない組成、例えば０．６５Ｌｉ2 Ｓ・０．
３５Ｂ2 Ｓ3 に対し、リン酸リチウムを加えて０．０５
Ｌｉ3 ＰＯ4 ・（０．６５Ｌｉ2 Ｓ・０．３５Ｂ
2 Ｓ3 ）とすることによりガラス化が可能であることが
わかった。As a result of the synthesis, a composition region where the product vitrified and a composition region where the product did not vitrify were found. As shown in FIG. 4, the vitrification range is a <0.3, b> 0.3, c>
In the range of 0.2, the composition does not vitrify the Li 2 S · B 2 S 3 pseudo binary system, for example 0.65Li 2 S · 0.
Lithium phosphate was added to 35B 2 S 3 to obtain 0.05.
Li 3 PO 4 · (0.65Li 2 S · 0.35B
It was found that vitrification is possible by using 2 S 3 ).

【００３８】以上のようにして合成した固体電解質のイ
オン伝導率を、交流インピーダンス法により測定した。The ionic conductivity of the solid electrolyte synthesized as described above was measured by the AC impedance method.

【００３９】測定の結果、ａ≦０．１、ｂ≧０．５、ｃ
≧０．３の組成領域で特に高い伝導率を示し、１×１０
-4〜３×１０-4Ｓ／ｃｍとなった。伝導率が最大となる
組成は、０．０３Ｌｉ3 ＰＯ4 ・０．５３Ｌｉ2 Ｓ・
０．４４Ｂ2 Ｓ3 であった。As a result of the measurement, a ≦ 0.1, b ≧ 0.5, c
Particularly high conductivity is exhibited in the composition region of ≧ 0.3 and 1 × 10
-4 to 3 × 10 -4 S / cm. The composition that maximizes the conductivity is 0.03Li 3 PO 4 .0.53Li 2 S.
It was 0.44 B 2 S 3 .

【００４０】以上のように、本発明によると、Ｌｉ2 Ｓ
・Ｂ2 Ｓ3 擬２成分系ではガラス化しなかった組成もリ
ン酸リチウムを加えることによりガラス化が可能とな
り、また、よりイオン伝導率の大きな固体電解質とする
ことができる。As described above, according to the present invention, Li 2 S
The composition which was not vitrified in the B 2 S 3 pseudo binary system can be vitrified by adding lithium phosphate, and a solid electrolyte having a higher ionic conductivity can be obtained.

【００４１】（実施例５）本発明による非晶質リチウム
イオン伝導性固体電解質の内、Ｌｉ3 ＰＯ4 ・Ｌｉ2 Ｓ
・ＳｉＳ2 で表される非晶質リチウムイオン伝導性固体
電解質を以下の方法で合成した。Example 5 Among the amorphous lithium ion conductive solid electrolytes according to the present invention, Li 3 PO 4 .Li 2 S
An amorphous lithium ion conductive solid electrolyte represented by SiS 2 was synthesized by the following method.

【００４２】所定の組成となるように、リン酸リチウム
（Ｌｉ3 ＰＯ4 ）と硫化リチウム（Ｌｉ2 Ｓ）と硫化珪
素（ＳｉＳ2 ）を混合した材料粉末をガラス状カーボン
坩堝にいれ、これを、アルゴン気流中９５０°Ｃで１．
５時間溶融し反応させた後、液体窒素中に投入して急冷
し、ａＬｉ3 ＰＯ4 ・ｂＬｉ2 Ｓ・ｃＳｉＳ2 （ａ＋ｂ
＋ｃ＝１）リチウムイオン伝導性固体電解質を合成し
た。A material powder obtained by mixing lithium phosphate (Li 3 PO 4 ), lithium sulfide (Li 2 S) and silicon sulfide (SiS 2 ) so as to have a predetermined composition is put in a glassy carbon crucible, and the powder is put into the crucible. At 950 ° C in an argon stream.
After melting and reacting for 5 hours, the mixture was poured into liquid nitrogen and rapidly cooled to obtain aLi 3 PO 4 .bLi 2 S.cSiS 2 (a + b
+ C = 1) A lithium ion conductive solid electrolyte was synthesized.

【００４３】合成の結果、ガラス化領域や伝導率の特性
は、実施例１で示した場合とほぼ同様となった。As a result of the synthesis, the characteristics of the vitrification region and the conductivity were almost the same as those shown in Example 1.

【００４４】以上のように、本発明によると、母材の合
成工程を経ることなしに、高いイオン伝導率を示すリチ
ウムイオン伝導性固体電解質を得ることができる。As described above, according to the present invention, a lithium ion conductive solid electrolyte exhibiting high ionic conductivity can be obtained without going through a step of synthesizing a base material.

【００４５】（実施例６）本発明による非晶質リチウム
イオン伝導性固体電解質の内、Ｌｉ3 ＰＯ4 ・Ｌｉ2 Ｓ
・ＧｅＳ2 で表される非晶質リチウムイオン伝導性固体
電解質を、ＳｉＳ 2 にかえてＧｅＳ2 を用いた以外は実
施例５と同様の方法で合成した。Example 6 Amorphous lithium according to the present invention
Among the ion conductive solid electrolytes, Li3POFour・ Li2S
・ GeS2Amorphous lithium ion conductive solid represented by
Electrolyte, SiS 2GeS instead2Except using
It was synthesized in the same manner as in Example 5.

【００４６】合成の結果、ガラス化領域や伝導率の特性
は、実施例２で示した場合とほぼ同様となった。As a result of the synthesis, the characteristics of the vitrification region and the conductivity were almost the same as those shown in Example 2.

【００４７】以上のように、本発明によると、母材の合
成工程を経ることなしに、高いイオン伝導率を示すリチ
ウムイオン伝導性固体電解質を得ることができる。As described above, according to the present invention, a lithium ion conductive solid electrolyte exhibiting high ionic conductivity can be obtained without going through a step of synthesizing a base material.

【００４８】（実施例７）本発明による非晶質リチウム
イオン伝導性固体電解質の内、Ｌｉ3 ＰＯ4 ・Ｌｉ2 Ｓ
・Ｐ2 Ｓ5 で表される非晶質リチウムイオン伝導性固体
電解質をＳｉＳ2にかえてＰ2 Ｓ5 を用いた以外は実施
例５と同様の方法で合成した。Example 7 Among the amorphous lithium ion conductive solid electrolytes according to the present invention, Li 3 PO 4 .Li 2 S
It was synthesized in the same manner as in Example 5, except that the amorphous lithium ion conductive solid electrolyte represented by P 2 S 5 was replaced with SiS 2 and P 2 S 5 was used.

【００４９】合成の結果、ガラス化領域や伝導率の特性
は、実施例３で示した場合とほぼ同様となった。As a result of the synthesis, the characteristics of the vitrification region and the conductivity were almost the same as those shown in Example 3.

【００５０】以上のように、本発明によると、母材の合
成工程を経ることなしに、高いイオン伝導率を示すリチ
ウムイオン伝導性固体電解質を得ることができる。As described above, according to the present invention, a lithium ion conductive solid electrolyte exhibiting high ionic conductivity can be obtained without going through a step of synthesizing a base material.

【００５１】（実施例８）本発明による非晶質リチウム
イオン伝導性固体電解質の内、Ｌｉ3 ＰＯ4 ・Ｌｉ2 Ｓ
・Ｂ2 Ｓ3 で表される非晶質リチウムイオン伝導性固体
電解質を、ＳｉＳ 2 にかえてＢ2 Ｓ3 を用いた以外は実
施例５と同様の方法で合成した。Example 8 Amorphous lithium according to the present invention
Among the ion conductive solid electrolytes, Li3POFour・ Li2S
・ B2S3Amorphous lithium ion conductive solid represented by
Electrolyte, SiS 2Instead of B2S3Except using
It was synthesized in the same manner as in Example 5.

【００５２】合成の結果、ガラス化領域や伝導率の特性
は、実施例４で示した場合とほぼ同様となった。As a result of the synthesis, the characteristics of the vitrification region and the conductivity were almost the same as those shown in Example 4.

【００５３】以上のように、本発明によると、母材の合
成工程を経ることなしに、高いイオン伝導率を示すリチ
ウムイオン伝導性固体電解質を得ることができる。As described above, according to the present invention, a lithium ion conductive solid electrolyte exhibiting high ionic conductivity can be obtained without going through a step of synthesizing a base material.

【００５４】尚、本発明の実施例においては、一般式Ｌ
ｉ3 ＰＯ4 ・Ｌｉ2 Ｓ・Ｘで表される固体電解質とし
て、ＸがＳｉＳ2 ，ＧｅＳ2 ，Ｐ2 Ｓ5 ，Ｂ2 Ｓ3 であ
るものについて説明を行ったが、ＸとしてＳｉＳ2 とＧ
ｅＳ2 の混合物など、ＳｉＳ2，ＧｅＳ2 ，Ｐ2 Ｓ5 ，
Ｂ2 Ｓ3 から選ばれる複数の硫化物の混合物を用いても
同様の結果が得られることはいうまでもなく、本発明は
Ｌｉ3 ＰＯ4 ・Ｌｉ2 Ｓ・ＸにおけるＸとして単一の硫
化物に限定されるものではない。In the examples of the present invention, the general formula L
As solid electrolyte represented by i 3 PO 4 · Li 2 S · X, but X has been described what is SiS 2, GeS 2, P 2 S 5, B 2 S 3, and SiS 2 as X G
such as a mixture of eS 2 , SiS 2 , GeS 2 , P 2 S 5 ,
It goes without saying that the same result can be obtained by using a mixture of a plurality of sulfides selected from B 2 S 3 and the present invention provides a single sulfide as X in Li 3 PO 4 .Li 2 S.X. It is not limited to the thing.

【００５５】[0055]

【発明の効果】一般式ａＬｉ3 ＰＯ4 ・ｂＬｉ2 Ｓ・ｃ
Ｘ（ａ＋ｂ＋ｃ＝１、ＸはＳｉＳ2 ，ＧｅＳ2 ，Ｐ2 Ｓ
5 ，Ｂ2 Ｓ3 のうち少なくとも一種の硫化物）で表され
るリチウムイオン伝導性固体電解質において、その組成
比ａ、ｂ、ｃをａ＜０．３、ｂ＞０．３、ｃ＞０．２と
することで、高いイオン伝導性を示す非晶質リチウムイ
オン伝導性固体電解質を得ることができる。EFFECT OF THE INVENTION General formula aLi 3 PO 4 .bLi 2 S.c
X (a + b + c = 1, X is SiS 2 , GeS 2 , P 2 S
5 , at least one sulfide of B 2 S 3 ) and a lithium ion conductive solid electrolyte represented by a composition ratio a, b, c of a <0.3, b> 0.3, c> 0. By setting the ratio to 0.2, an amorphous lithium ion conductive solid electrolyte exhibiting high ion conductivity can be obtained.

【００５６】また、組成比ａ、ｂ、ｃをａ≦０．１、ｂ
≧０．５、ｃ≧０．３とすることで、特に高いイオン伝
導性を示す非晶質リチウムイオン伝導性固体電解質を得
ることができる。Further, the composition ratios a, b and c are a ≦ 0.1 and b.
By setting ≧ 0.5 and c ≧ 0.3, it is possible to obtain an amorphous lithium ion conductive solid electrolyte exhibiting particularly high ionic conductivity.

【００５７】また、Ｌｉ3 ＰＯ4 とＬｉ2 ＳとＸ（Ｘは
ＳｉＳ2 ，ＧｅＳ2 ，Ｐ2 Ｓ5 ，Ｂ 2 Ｓ3 のうち少なく
とも一種の硫化物）の混合物を溶融し、その後急冷する
ことで、母材の合成工程を経ることなしに高いイオン伝
導性を示す前記非晶質リチウムイオン伝導性固体電解質
を得ることができる。In addition, Li3POFourAnd Li2S and X (X is
SiS2, GeS2, P2SFive, B 2S3Less of
And a kind of sulfide) are melted and then quenched.
This enables high ion transmission without going through the synthesis process of the base material.
The amorphous lithium ion conductive solid electrolyte exhibiting conductivity
Can be obtained.

【００５８】また、特に、前記一般式ａＬｉ3 ＰＯ4 ・
ｂＬｉ2 Ｓ・ｃＸ（ａ＋ｂ＋ｃ＝１）で表される化合物
において、ＸとしてＳｉＳ2 を用いることで、高いイオ
ン伝導性を示す非晶質リチウムイオン伝導性固体電解質
を得ることができる。Further, in particular, the above general formula aLi 3 PO 4 .multidot.
By using SiS 2 as X in the compound represented by bLi 2 S · cX (a + b + c = 1), an amorphous lithium ion conductive solid electrolyte exhibiting high ion conductivity can be obtained.

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

【図１】ａＬｉ3 ＰＯ4 ・ｂＬｉ2 Ｓ・ｃＳｉＳ2 擬３
成分系のガラス化領域を示す三成分組成図FIG. 1 aLi 3 PO 4 .bLi 2 S.cSiS 2 pseudo-3
Three-component composition diagram showing the vitrification region of the component system

【図２】ａＬｉ3 ＰＯ4 ・ｂＬｉ2 Ｓ・ｃＧｅＳ2 擬３
成分系のガラス化領域を示す三成分組成図FIG. 2 aLi 3 PO 4 .bLi 2 S.cGeS 2 pseudo-3
Three-component composition diagram showing the vitrification region of the component system

【図３】ａＬｉ3 ＰＯ4 ・ｂＬｉ2 Ｓ・ｃＰ2 Ｓ5 擬３
成分系のガラス化領域を示す三成分組成図FIG. 3 aLi 3 PO 4 .bLi 2 S.cP 2 S 5 pseudo-3
Three-component composition diagram showing the vitrification region of the component system

【図４】ａＬｉ3 ＰＯ4 ・ｂＬｉ2 Ｓ・ｃＢ2 Ｓ3 擬３
成分系のガラス化領域を示す三成分組成図FIG. 4 aLi 3 PO 4 .bLi 2 S.cB 2 S 3 pseudo-3
Three-component composition diagram showing the vitrification region of the component system

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｍ 10/36 Ａ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location H01M 10/36 A

Claims (3)

【特許請求の範囲】[Claims] 【請求項１】 一般式ａＬｉ3 ＰＯ4 ・ｂＬｉ2 Ｓ・ｃ
Ｘ（ａ＋ｂ＋ｃ＝１、ＸはＳｉＳ2 ，ＧｅＳ2 ，Ｐ2 Ｓ
5 ，Ｂ2 Ｓ3 のうち少なくとも一種の硫化物）で表さ
れ、組成比ａ、ｂ、ｃ、がａ＜０．３かつｂ＞０．３か
つｃ＞０．２をみたすことを特徴とする非晶質リチウム
イオン伝導性固体電解質。1. A general formula aLi 3 PO 4 .bLi 2 S.c.
X (a + b + c = 1, X is SiS 2 , GeS 2 , P 2 S
5 , B 2 S 3 of at least one sulfide), and the composition ratios a, b, and c satisfy a <0.3 and b> 0.3 and c> 0.2. Amorphous lithium ion conductive solid electrolyte. 【請求項２】 組成比ａ、ｂ、ｃ、がａ≦０．１かつｂ
≧０．５かつｃ≧０．３をみたすことを特徴とする請求
項１記載の非晶質リチウムイオン伝導性固体電解質。2. The composition ratios a, b, and c are a ≦ 0.1 and b.
The amorphous lithium ion conductive solid electrolyte according to claim 1, wherein ≧ 0.5 and c ≧ 0.3 are satisfied. 【請求項３】 Ｌｉ3 ＰＯ4 とＬｉ2 ＳとＸ（ＸはＳｉ
Ｓ2 ，ＧｅＳ2 ，Ｐ2Ｓ5 ，Ｂ2 Ｓ3 のうち少なくとも
一種の硫化物）の混合物を溶融し、その後急冷すること
を特徴とする請求項１または請求項２記載の非晶質リチ
ウムイオン伝導性固体電解質の合成法。3. Li 3 PO 4 and Li 2 S and X (X is Si
Amorphous lithium according to claim 1 or 2, wherein a mixture of at least one sulfide of S 2 , GeS 2 , P 2 S 5 , and B 2 S 3 is melted and then rapidly cooled. Synthesis of ion conductive solid electrolyte.
JP11869092A 1992-05-12 1992-05-12 Amorphous lithium ion conductive solid electrolyte and its synthesis method Expired - Lifetime JP3343936B2 (en)

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WO1995034515A1 (en) * 1994-06-13 1995-12-21 Mitsui Petrochemical Industries, Ltd. Lithium ion-conductive glass film and thin carbon dioxide gas sensor using the same film
EP0704920A1 (en) * 1994-09-21 1996-04-03 Matsushita Electric Industrial Co., Ltd. Solid-state lithium secondary battery
WO2000033400A1 (en) * 1998-12-02 2000-06-08 Matsushita Electric Industrial Co., Ltd. Non-aqueous electrolyte secondary cell
US6277524B1 (en) 1997-12-09 2001-08-21 Toyota Jidosha Kabushiki Kaisha Lithium-ion-conductive solid electrolyte and solid-electrolyte lithium battery
US6506520B1 (en) 1998-12-02 2003-01-14 Matsushita Electric Industrial Co., Ltd. Non-aqueous electrolyte secondary battery
US6605386B1 (en) 1998-12-02 2003-08-12 Matsushita Electric Industrial Co., Ltd. Non-aqueous electrolyte secondary battery comprising composite particles
US6653019B1 (en) 1998-06-03 2003-11-25 Matsushita Electric Industrial Co., Ltd. Non-aqueous electrolyte secondary cell
US6821675B1 (en) 1998-06-03 2004-11-23 Matsushita Electric Industrial Co., Ltd. Non-Aqueous electrolyte secondary battery comprising composite particles
US6824920B1 (en) 1997-06-03 2004-11-30 Matsushita Electric Industrial Co., Ltd. Non-aqueous electrolyte secondary battery comprising composite particles
JP2006156083A (en) * 2004-11-29 2006-06-15 Osaka Prefecture New high ionic conductivity ionic glass composition and manufacturing method of the same
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JP2007273214A (en) * 2006-03-31 2007-10-18 Idemitsu Kosan Co Ltd Solid electrolyte, its manufacturing method and all solid secondary battery
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US5755940A (en) * 1994-06-13 1998-05-26 Mitsui Petrochemical Industries, Ltd. Lithium ionic conducting glass thin film and carbon dioxide sensor comprising the glass thin film
WO1995034515A1 (en) * 1994-06-13 1995-12-21 Mitsui Petrochemical Industries, Ltd. Lithium ion-conductive glass film and thin carbon dioxide gas sensor using the same film
EP0704920A1 (en) * 1994-09-21 1996-04-03 Matsushita Electric Industrial Co., Ltd. Solid-state lithium secondary battery
US5677081A (en) * 1994-09-21 1997-10-14 Matsushita Electric Industrial Co., Ltd. Solid-state lithium secondary battery
US6824920B1 (en) 1997-06-03 2004-11-30 Matsushita Electric Industrial Co., Ltd. Non-aqueous electrolyte secondary battery comprising composite particles
US6277524B1 (en) 1997-12-09 2001-08-21 Toyota Jidosha Kabushiki Kaisha Lithium-ion-conductive solid electrolyte and solid-electrolyte lithium battery
US6653019B1 (en) 1998-06-03 2003-11-25 Matsushita Electric Industrial Co., Ltd. Non-aqueous electrolyte secondary cell
US6821675B1 (en) 1998-06-03 2004-11-23 Matsushita Electric Industrial Co., Ltd. Non-Aqueous electrolyte secondary battery comprising composite particles
WO2000033400A1 (en) * 1998-12-02 2000-06-08 Matsushita Electric Industrial Co., Ltd. Non-aqueous electrolyte secondary cell
US6605386B1 (en) 1998-12-02 2003-08-12 Matsushita Electric Industrial Co., Ltd. Non-aqueous electrolyte secondary battery comprising composite particles
US6506520B1 (en) 1998-12-02 2003-01-14 Matsushita Electric Industrial Co., Ltd. Non-aqueous electrolyte secondary battery
JP2006156083A (en) * 2004-11-29 2006-06-15 Osaka Prefecture New high ionic conductivity ionic glass composition and manufacturing method of the same
EP1739769A1 (en) * 2005-06-28 2007-01-03 Sumitomo Electric Industries, Ltd. Lithium secondary battery anode member and method for manufacturing the same
US8709106B2 (en) 2005-06-28 2014-04-29 Sumitomo Electric Industries, Ltd. Lithium secondary battery anode member and method for manufacturing the same
JP2007273214A (en) * 2006-03-31 2007-10-18 Idemitsu Kosan Co Ltd Solid electrolyte, its manufacturing method and all solid secondary battery
JP2007273217A (en) * 2006-03-31 2007-10-18 Idemitsu Kosan Co Ltd Solid electrolyte, manufacturing method therefor and all-solid secondary battery

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