JP3343936B2 - Amorphous lithium ion conductive solid electrolyte and its synthesis method - Google Patents
Amorphous lithium ion conductive solid electrolyte and its synthesis methodInfo
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- JP3343936B2 JP3343936B2 JP11869092A JP11869092A JP3343936B2 JP 3343936 B2 JP3343936 B2 JP 3343936B2 JP 11869092 A JP11869092 A JP 11869092A JP 11869092 A JP11869092 A JP 11869092A JP 3343936 B2 JP3343936 B2 JP 3343936B2
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- solid electrolyte
- conductive solid
- ion conductive
- lithium ion
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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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Description
【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 electrochemical devices such as all solid state batteries, capacitors and solid state 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, studies on all solidification of a lithium battery using a lithium ion conductive solid electrolyte have been actively conducted.
【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 SX (X is SiS 2 , GeS 2 ,
There is at least one sulfide-based sulfide glass of P 2 S 5 and B 2 S 3 .
【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 Li 2 S.X sulfide glass, X is Si
It has the highest conductivity value in the Li 2 S.SiS 2 system of S 2 , and 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 ion conductivity, pseudo sulfide obtained by adding lithium iodide (LiI) or lithium phosphate (Li 3 PO 4 ) to these sulfide glasses.
Component-based glasses have been proposed.
【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 proposal of these various solid electrolytes aims at improving the ionic conductivity. Since the conductivity is proportional to the product of the concentration of the mobile ions and the mobility, it is necessary to increase the concentration of the 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 a two- component glass of at least one sulfide of 2 S 3 ), 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 if the composition ratio of Li 2 S is increased, glass formation becomes impossible, resulting in a decrease in conductivity.
【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 to provide a solid electrolyte having higher lithium ion conductivity and a method for synthesizing the same.
【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
> 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 general formula aLi 3 PO 4 .bLi 2
S · cX (a + b + c = 1, X is SiS 2 , GeS 2 ,
The amorphous lithium ion conductive solid electrolyte represented by at least one sulfide of P 2 S 5 and B 2 S 3 ) has composition ratios a, b, and 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
2 , a mixture of GeS 2 , P 2 S 5 , and B 2 S 3 ) is preferably melted and then quenched to synthesize.
【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。[Function] LiS 2 · X (X is SiS 2 , GeS 2 , P 2
By adding Li 3 PO 4 as a third component to the pseudo-two-component glass of at least one of sulfides of S 5 and B 2 S 3 ), the concentration of lithium ions, which are mobile ions, becomes large, and the conductivity becomes high. improves. Furthermore, Li 3 PO
Since PO 4 3-, which is the component 4 , has a glass network forming ability, it can be vitrified even in a composition region containing a large amount of Li 2 S component, which cannot be vitrified 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。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 whose main component is at least one sulfide of 2 S 5 and B 2 S 3 ), the composition ratios a, b and c are a <0.3 and b> 0.3 and c > 0.
Vitrification is possible in a composition region that satisfies No. 2 and an amorphous lithium ion conductive solid electrolyte having 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, in this composition region, the composition ratio a,
It is particularly preferably used because the concentration of mobile ions becomes high in the composition region where b and c satisfy a ≦ 0.1, b ≧ 0.5 and c ≧ 0.3, and the conductivity shows a maximum.
【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 +
b + c = 1), X is Si
When S 2 , SiS 2 is particularly preferably used as X because vitrification can be easily performed.
【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 pseudo-ternary sulfide glass, a two-stage process is generally performed in which a pseudo-binary glass is prepared as a base material, a third component is mixed and melted, and a glass is prepared. Although the method of taking a process is common, 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
To prepare a component system glass for PO 4 3- contribute to glass network formation, it is not necessary to take a process of such a two-step, after mixing the materials at once melted, rapidly cooling Thus, the number of steps in the synthesis can be simplified.
【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 Hereinafter, the present invention will be described in more 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
· SiS 2 in amorphous lithium ion conductive solid electrolyte represented were 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。A Li 2 S.SiS 2 -based sulfide glass was synthesized as a base material, and Li 3 PO 4 was added thereto to form 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 for synthesizing Li 2 S.SiS 2 -based sulfide glass is described. A material powder obtained by mixing lithium sulfide (Li 2 S) and silicon sulfide (SiS 2 ) so as to have a predetermined composition is mixed with glass. The mixture was melted at 950 ° C. for 1.5 hours in an argon gas stream and reacted, then poured into liquid nitrogen and quenched to synthesize Li 2 S.SiS 2 and used 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 thereto with aLi 3 PO 4 .bLi.
2 S · cSiS 2 (a + b + c = 1) is added and mixed so as to have a predetermined composition, and the obtained material powder is placed in a glassy carbon crucible, which is placed in an argon stream at 950 ° C.
And reacted for 1.5 hours, then poured into liquid nitrogen and quenched, and then aLi 3 PO 4 .bLi 2 S.cSiS
2 (a + b + c = 1) A 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, there were a composition region where the product vitrified and a composition region where the product did not vitrify. As shown in FIG. 1, 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 · SiS 2 quasi-two-component system, for example 0.65Li 2 S · 0.
Lithium phosphate was added to 35SiS 2 to add 0.05
Li 3 PO 4. (0.65Li 2 S.0.35Si
It was found that vitrification was possible by setting 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
A particularly high conductivity is exhibited in a composition region of ≧ 0.3, and 2 × 10
−4 to 7 × 10 −4 S / cm. The composition having the maximum conductivity is 0.03Li 3 PO 4 .0.63Li 2 S.
0.34 SiS 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
Addition of lithium phosphate to a composition that was not vitrified in the SiS 2 pseudo two-component system can be vitrified, 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, LiThreePOFour・ LiTwoS
・ GeSTwoAmorphous lithium ion conductive solid represented by
The electrolyte is SiS TwoGeS insteadTwoOther than using
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 was vitrified and a composition region where the product was not vitrified were observed. 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 was possible by setting 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 was exhibited in the composition range of a ≦ 0.1, b ≧ 0.5 and c ≧ 0.3, and 1 ×
10-4 became ~3 × 10 -4 S / cm. The composition having the maximum conductivity is 0.03Li 3 PO 4 .0.63Li 2 S
· 0.34GeS was 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
The composition that was not vitrified in the GeS 2 pseudo-two-component system can be vitrified by adding lithium phosphate, and a solid electrolyte having 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, LiThreePOFour・ LiTwoS
・ PTwoSFiveAmorphous lithium ion conductive solid represented by
The electrolyte is SiS TwoInstead of PTwoSFiveOther than using
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 was vitrified and a composition region where the product was not vitrified were observed. As shown in FIG. 3, 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 · P 2 S 5 quasi-two-component system, for example 0.65Li 2 S · 0.
Lithium phosphate was added to 35P 2 S 5 to add 0.05
Li 3 PO 4・ (0.65Li 2 S ・ 0.35P
It was found that vitrification was 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、交流インピーダンス法により測定した。The above way the ionic conductivity of the composite solid electrolyte 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
A particularly high conductivity is exhibited in a composition region of ≧ 0.3, and 2 × 10
−4 to 4 × 10 −4 S / cm. The composition having the maximum conductivity is 0.03Li 3 PO 4 · 0.65Li 2 S ·
0.32P was 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 that was not vitrified in the P 2 S 5 pseudo two-component system can be vitrified by adding lithium phosphate, and a solid electrolyte having 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, LiThreePOFour・ LiTwoS
・ BTwoSThreeAmorphous lithium ion conductive solid represented by
The electrolyte is SiS TwoB insteadTwoSThreeOther than using
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 was vitrified and a composition region where the product was not vitrified were observed. 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 add 0.05
Li 3 PO 4・ (0.65Li 2 S ・ 0.35B
It was found that vitrification was possible by setting to 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 range of ≧ 0.3 and 1 × 10
−4 to 3 × 10 −4 S / cm. The composition having the maximum conductivity is 0.03Li 3 PO 4 .0.53Li 2 S.
0.44B was 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 that was not vitrified in the B 2 S 3 pseudo two-component system can be vitrified by adding lithium phosphate, and a solid electrolyte having 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 Of the amorphous lithium ion conductive solid electrolyte according to the present invention, Li 3 PO 4 .Li 2 S
· SiS 2 in amorphous lithium ion conductive solid electrolyte represented were 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 ) is placed in a glassy carbon crucible so as to have a predetermined composition. At 950 ° C. in an argon stream.
After melting and reacting for 5 hours, it is poured into liquid nitrogen and rapidly cooled, and 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 vitrified 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 having a 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, LiThreePOFour・ LiTwoS
・ GeSTwoAmorphous lithium ion conductive solid represented by
The electrolyte is SiS TwoGeS insteadTwoOther than using
The compound 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 properties of the vitrified 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 having a 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。Embodiment 7 Among the amorphous lithium ion conductive solid electrolytes according to the present invention, Li 3 PO 4 .Li 2 S
· P 2 S except that the amorphous lithium ion conductive solid electrolyte represented by 5 with P 2 S 5 in place of SiS 2 was synthesized in the same manner as in Example 5.
【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 vitrified 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 base material synthesis step.
【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, LiThreePOFour・ LiTwoS
・ BTwoSThreeAmorphous lithium ion conductive solid represented by
The electrolyte is SiS TwoB insteadTwoSThreeOther than using
The compound 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 properties of the vitrified 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 embodiment 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 relates to a single sulfide as X in Li 3 PO 4 .Li 2 S.X. It is not limited to objects.
【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。The 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 ), the composition ratios a, b, and c of a <0.3, b> 0.3, c> 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, when the composition ratios a, b, and c are a ≦ 0.1, b
By setting ≧ 0.5 and c ≧ 0.3, it is possible to obtain an amorphous lithium ion conductive solid electrolyte exhibiting particularly high ion 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, LiThreePOFourAnd LiTwoS and X (X is
SiSTwo, GeSTwo, PTwoSFive, B TwoSThreeLess of
And quenching after quenching)
High ion transfer without going through the base material synthesis process
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 general formula aLi 3 PO 4.
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 having high ion conductivity can be obtained.
【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.7 識別記号 ＦＩ Ｈ０１Ｍ 6/18 Ｈ０１Ｍ 6/18 Ｚ 10/36 10/36 Ａ (56)参考文献 特開 平４−231346（ＪＰ，Ａ) 特開 平４−202024（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C01D 15/00 C01B 25/30 C01B 17/22 C03C 3/32 C03C 4/14 H01B 1/06 H01M 6/18 H01M 10/36 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI H01M 6/18 H01M 6/18 Z 10/36 10/36 A (56) References JP-A-4-231346 (JP, A) JP-A-4-202024 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C01D 15/00 C01B 25/30 C01B 17/22 C03C 3/32 C03C 4/14 H01B 1 / 06 H01M 6/18 H01M 10/36
Claims (3)
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. The 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 ), wherein the composition ratios a, b, and c satisfy a <0.3, b> 0.3, and c> 0.2. Amorphous lithium ion conductive solid electrolyte.
≧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 ratio a, b, c is a ≦ 0.1 and b
2. The amorphous lithium ion conductive solid electrolyte according to claim 1, wherein ≧ 0.5 and c ≧ 0.3 are satisfied.
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 , Li 2 S and X (X is Si
3. The amorphous lithium according to claim 1, 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 quenched. A method for synthesizing an ion conductive solid electrolyte.
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| US6821675B1 (en) | 1998-06-03 | 2004-11-23 | 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 |
| EP1052711A4 (en) * | 1998-12-02 | 2005-03-30 | Matsushita Electric Ind 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 |
| WO2000033402A1 (en) | 1998-12-02 | 2000-06-08 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary cell and its charging method |
| JP4759256B2 (en) * | 2004-11-29 | 2011-08-31 | 公立大学法人大阪府立大学 | Novel high ion conductive ion glass composition and method for producing the same |
| JP4165536B2 (en) | 2005-06-28 | 2008-10-15 | 住友電気工業株式会社 | Lithium secondary battery negative electrode member and manufacturing method thereof |
| JP4996120B2 (en) * | 2006-03-31 | 2012-08-08 | 出光興産株式会社 | Solid electrolyte, method for producing the same, and all-solid-state secondary battery |
| JP4834442B2 (en) * | 2006-03-31 | 2011-12-14 | 出光興産株式会社 | Solid electrolyte, method for producing the same, and all-solid-state secondary battery |
-
1992
- 1992-05-12 JP JP11869092A patent/JP3343936B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7150943B2 (en) | 2001-02-28 | 2006-12-19 | Sumitomo Electric Industries, Ltd. | Inorganic solid electrolyte and lithium cell component |
| US7517616B2 (en) | 2001-02-28 | 2009-04-14 | Sumitomo Electric Industries, Ltd. | Inorganic solid electrolyte and lithium cell component |
| US7416815B2 (en) | 2004-04-01 | 2008-08-26 | Sumitomo Electric Industries, Ltd. | Negative electrode member for lithium battery and process for producing the same |
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|---|---|
| JPH05310418A (en) | 1993-11-22 |
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