JPH0317348B2 - - Google Patents
Info
- Publication number
- JPH0317348B2 JPH0317348B2 JP59175553A JP17555384A JPH0317348B2 JP H0317348 B2 JPH0317348 B2 JP H0317348B2 JP 59175553 A JP59175553 A JP 59175553A JP 17555384 A JP17555384 A JP 17555384A JP H0317348 B2 JPH0317348 B2 JP H0317348B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium ion
- conductivity
- solid electrolyte
- ion conductive
- linb
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/185—Cells with non-aqueous electrolyte with solid electrolyte with oxides, hydroxides or oxysalts as solid electrolytes
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Conductive Materials (AREA)
- Primary Cells (AREA)
Description
【発明の詳細な説明】
〔発明の分野〕
本発明は、リチウムイオン導電性固体電解質材
料に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to lithium ion conductive solid electrolyte materials.
リチウムを負極活物質として用い、電解質とし
てリチウム導電性の固体電解質を用いた固体電池
は、高工ネルギ密度であり、液漏れがなく、小型
薄幕に出来る等の点で、非常に利点が多い。
Solid-state batteries that use lithium as the negative electrode active material and a lithium-conductive solid electrolyte as the electrolyte have many advantages, such as high energy density, no leakage, and the ability to be made into small and thin sheets. .
このような固体電池への応用を目的としてチリ
ウムイオン導電性固体電解質材料の開発が注目さ
れている。しかし、現在のところ、リチウムイオ
ン導電性固体電解質材料は得られておらず、僅か
に、40mol％Al2O3を添加したLiIのみがリチウム
固体電池に応用され、実用されているにすぎな
い。 The development of thium ion conductive solid electrolyte materials is attracting attention for application to such solid-state batteries. However, at present, no lithium ion conductive solid electrolyte material has been obtained, and only LiI containing 40 mol% Al 2 O 3 has been applied to lithium solid-state batteries and is in practical use.
最近、Li3N、LiAlSiO4等のリチウムイオン導
電性の固体電解質材料が知られているが、まだ固
体電池に必要な特性を充分満足しているとは言い
難い現状である。たとえば、LI3Nは導電率は大
きいが、分解電圧が低いこと、LiAlSiO4は室温
での導電率が10-9Ω-1cm-1以下と小さく、いずれ
も固体電池への適用はなされていない。 Recently, lithium ion conductive solid electrolyte materials such as Li 3 N and LiAlSiO 4 have become known, but it is still difficult to say that they fully satisfy the characteristics required for solid batteries. For example, LI 3 N has high conductivity but low decomposition voltage, and LiAlSiO 4 has low conductivity at room temperature of 10 -9 Ω -1 cm -1 or less, and neither of these has been applied to solid-state batteries. do not have.
このようなわけで、これらの欠点を除去した固
体電解質材料、特に導電率が大きく、化学的に安
定な材料の開発が希求されている。 For this reason, there is a desire to develop solid electrolyte materials that eliminate these drawbacks, particularly materials that have high electrical conductivity and are chemically stable.
本発明は上述の現状に鑑みなされたもので、導
電率が大きく、かつ化学的に安定なリチウムイオ
ン導電性固体電解質材料を提供することを目的と
する。
The present invention was made in view of the above-mentioned current situation, and an object of the present invention is to provide a lithium ion conductive solid electrolyte material that has high electrical conductivity and is chemically stable.
したがつて、本発明によるリチウムイオン導電
性固体電解質材料は、一般式、
LiNb1-xTaxWO6
（但し、０＜ｘ≦１）
で示される組成物よりなることを特徴とするもの
である。 Therefore, the lithium ion conductive solid electrolyte material according to the present invention is characterized by comprising a composition represented by the general formula: LiNb 1-x Ta x WO 6 (where 0<x≦1). be.
本発明によるリチウムイオン導電性固体電解質
材料によれば、トリチル構造を有することによ
り、比較的高いリチウムイオン導電性を示すとと
もに、分解電圧も高く、熱的に安定であり、ま
た、水分に対しても、他のリチウムイオン導電体
に比較して安定であるという利点があり、このた
めこのリチウムイオン導電性固体電解質材料をリ
チウム固体電池の電解質材料に適用することによ
り、固体電池の特性改善が達成しえるという利点
がある。 The lithium ion conductive solid electrolyte material of the present invention has a trityl structure, so it exhibits relatively high lithium ion conductivity, has a high decomposition voltage, is thermally stable, and is resistant to moisture. It also has the advantage of being more stable than other lithium ion conductors, and for this reason, by applying this lithium ion conductive solid electrolyte material to the electrolyte material of lithium solid-state batteries, improvements in the characteristics of solid-state batteries can be achieved. It has the advantage of being strong.
本発明をさらに詳しく説明する。 The present invention will be explained in more detail.
本発明による一般式、
LiNb1-xTaxWO6
（但し、０＜ｘ≦１）
で示される組成物は、リチウムイオン導電率の高
い材料を作ることを目的に、その結晶構造に着目
して製作したものである。 The composition represented by the general formula LiNb 1-x Ta x WO 6 (0<x≦1) according to the present invention was developed by focusing on its crystal structure with the aim of creating a material with high lithium ion conductivity. It was produced by
本発明によるリチウムイオン導電性固体電解質
材料はトリルチル構造を有するものである。すな
わち、このトリルチル構造はルチル構造のＣ軸方
向に３倍伸びた構造をしており、したがつて
（001）方向に隙間があり、この方向にリチウムイ
オンの移動が容易であると考えられることから、
この材料系に着目したのである。 The lithium ion conductive solid electrolyte material according to the present invention has a trirutile structure. In other words, this trirutile structure has a structure that extends three times as much in the C-axis direction as the rutile structure, so there is a gap in the (001) direction, and it is thought that lithium ions can easily move in this direction. from,
We focused on this material system.
前述の一般式において、０＜ｘ≦１にある本発
明によるリチウムイオン導電性固体電解質材料は
トリルチル構造を採り、いずれもリチウムイオン
導電性を示す。 In the above general formula, the lithium ion conductive solid electrolyte material according to the present invention in which 0<x≦1 has a trirutile structure, and all exhibit lithium ion conductivity.
本発明によるリチウムイオン導電性固体電解質
材料の製造方法は、本発明において限定されるも
のではない。たとえば、通常の磁器焼成法あるい
はホツトプレス法により製造することができる。 The method for manufacturing the lithium ion conductive solid electrolyte material according to the present invention is not limited in the present invention. For example, it can be manufactured by a normal porcelain firing method or a hot pressing method.
具体的には、たとえば次のようにして製造する
ことができる。 Specifically, it can be manufactured, for example, as follows.
まず市販特級試薬のLi2CO3、Nb2O55、Ta2O5
およびWO3を原料とし、これらの原料を、
LiNb1-xTaxWO6なる秤量式に基づき、所定量を
秤量し、充分混合した後、アルミナるつぼに移し
て、仮焼成する。仮焼成は、700〜760℃の温度で
24時間、大気中にて行なう。焼成後、生成物を電
気炉より取り出し、粉枠した後、１〜5t／cm2の圧
力で、成形し成形体とする。 First, commercially available special grade reagents Li 2 CO 3 , Nb 2 O 5 5 , Ta 2 O 5
and WO 3 as raw materials, these raw materials,
Based on the weighing formula LiNb 1-x Ta x WO 6 , a predetermined amount is weighed, thoroughly mixed, and then transferred to an alumina crucible and calcined. Temporary firing is at a temperature of 700-760℃
Perform in air for 24 hours. After firing, the product is taken out of the electric furnace, powdered, and then molded into a molded body under a pressure of 1 to 5 t/cm 2 .
この成形体を、さらに760〜780℃の温度で６時
間焼成するか、760〜800℃の温度で、400Kg／cm2
のプレス圧で２時間、ホツトプレス焼成を行う。 This molded body is further baked at a temperature of 760-780℃ for 6 hours, or at a temperature of 760-800℃, 400Kg/cm 2
Hot press firing is carried out for 2 hours at a pressure of .
前述のように製造された焼結体を所要形状に切
り出し、研磨し、リチウム負極活物質とする固体
電池の固体電解質材料とする。 The sintered body produced as described above is cut into a desired shape, polished, and used as a solid electrolyte material for a solid battery, which is used as a lithium negative electrode active material.
本発明によるリチウムイオン導電性固体電解質
材料の導電率は、仮焼成、本焼成あるいはホツト
プレス条件により若干の影響を受けるが、
LiNb1-xTaxWO6なる組成において、ｘ＝0.25の
時、最大の導電率を示す。 The electrical conductivity of the lithium ion conductive solid electrolyte material according to the present invention is slightly affected by the pre-firing, main baking, or hot pressing conditions.
In the composition LiNb 1-x Ta x WO 6 , the maximum conductivity is shown when x=0.25.
以下、本発明の実施例を説明する。 Examples of the present invention will be described below.
以下の実施例における導電率の測定は、焼結体
から、直径12mm、厚み約２mmの円盤状試料に成形
し、その両面にPt−Pd電極を付けて、交流法に
より行い、複数アドミツタンス法により導電率を
求めた。また電子輸率は直流法により電子伝導性
による導電率を求め、全善導電率との比より求め
た。 The conductivity measurements in the following examples were performed by molding a sintered body into a disk-shaped sample with a diameter of 12 mm and a thickness of about 2 mm, attaching Pt-Pd electrodes to both sides, using the AC method, and using the multiple admittance method. The conductivity was determined. In addition, the electron transport number was determined by determining the electrical conductivity by electron conductivity using the direct current method, and by calculating the ratio to the total conductivity.
実施例 １
前述の製造方法にしたがい、LiNbWO6（前記
一般式のx0のばあい）、LiNb0.75Ta0.25WO6（ｘ＝
0.25）、LiNb0.5Ta0.5WO6（ｘ＝0.5）、LiNb0.25
Ta0.7WO6（ｘ＝0.75）、LiTaWO（ｘ＝１）を、次
の条件で製造した。Example 1 According to the above-mentioned manufacturing method, LiNbWO 6 (in the case of x0 in the above general formula), LiNb 0.75 Ta 0.25 WO 6 (x=
0.25), LiNb 0.5 Ta 0.5 WO 6 (x=0.5), LiNb 0.25
Ta 0.7 WO 6 (x=0.75) and LiTaWO (x=1) were produced under the following conditions.
仮焼成を750℃、24時間行つた後、成形し、こ
れを780℃、400Kg／cm2のプレス圧で、２時間ホツ
トプレスを行つた。得られた焼結体材料研磨成形
した後、電極を付けて、交流法により導電率を測
定した。 After pre-firing at 750°C for 24 hours, it was molded and hot pressed at 780°C and a pressing pressure of 400 kg/cm 2 for 2 hours. After the obtained sintered material was polished and molded, electrodes were attached and the electrical conductivity was measured by an alternating current method.
結果を第１図に示す。 The results are shown in Figure 1.
第１図は導電率の温度依存性を示す図であり、
図中、１はLiNbWO6、２はLiNb0.75Ta0.25WO6、
３はLiNb0.5Ta0.5WO6、４はLiNb0.25Ta0.75WO6、
５はLiTaWO6についての結果を示すグラフであ
る。 FIG. 1 is a diagram showing the temperature dependence of conductivity.
In the figure, 1 is LiNbWO 6 , 2 is LiNb 0.75 Ta 0.25 WO 6 ,
3 is LiNb 0.5 Ta 0.5 WO 6 , 4 is LiNb 0.25 Ta 0.75 WO 6 ,
5 is a graph showing the results for LiTaWO 6 .
この第１図における直線の傾きから活性化エネ
ルギが求められる。前述の１の活性化エネルギは
0.50evであり、２，３，４，５の順に大きくな
り、５においては0.59evである。２，
150℃における導電率と組成の関係を第２図に
示す。第２図より明らかなように、組成が
LiNb0.75Ta0.25WO6の付近で導電率が最大にな
る。 Activation energy can be determined from the slope of the straight line in FIG. The activation energy of 1 above is
It is 0.50ev, and increases in the order of 2, 3, 4, and 5, and at 5, it is 0.59ev. 2. Figure 2 shows the relationship between conductivity and composition at 150°C. As is clear from Figure 2, the composition is
The conductivity is maximum near LiNb 0.75 Ta 0.25 WO 6 .
直流法による導電率の測定結果は、150℃にお
いて、LiNbWO6、LiNb0.75Ta0.25WO6それぞれ、
６×10-8Ω-1cm-1、１×10-10Ω-1cm-1、1.5×
10-10Ω-1cm-1であり、電子輸率はそれぞれ、
0.03、0.0001、0.04であつた。このことから、本
発明によるリチウムイオン導電性固体電解質材料
はいずれもLiイオン導電性であることがわかる。 The conductivity measurement results by the DC method are as follows at 150℃: LiNbWO 6 , LiNb 0.75 Ta 0.25 WO 6 ,
6×10 -8 Ω -1 cm -1 , 1×10 -10 Ω -1 cm -1 , 1.5×
10 -10 Ω -1 cm -1 and the electron transport numbers are, respectively.
They were 0.03, 0.0001, and 0.04. This shows that all the lithium ion conductive solid electrolyte materials according to the present invention are Li ion conductive.
〔発明の効果〕
以上説明したように、本発明によるLiNb1-x
TaxWO6なる磁器組成物は、トリルチル構造を有
することにより、比較的高いリチウムイオン導電
性を示す。また、このリチウムイオン導電性固体
電解質材料は分解電圧も高く、熱的および水分に
対しても安定であり、リチウム固体電池の電解質
材料に用いることにより固体電池の特性改善が達
成できる利点がある。[Effect of the invention] As explained above, LiNb 1-x according to the present invention
The ceramic composition Ta x WO 6 exhibits relatively high lithium ion conductivity due to its trirutile structure. Furthermore, this lithium ion conductive solid electrolyte material has a high decomposition voltage and is stable against heat and moisture, and has the advantage of being able to improve the characteristics of solid-state batteries by using it as an electrolyte material for lithium solid-state batteries.
第１図は、本発明の一実施例のリチウムイオン
導電性固体電解質材料の導電率の温度依存性を示
す図であり、第２図は本発明によるリチウムイオ
ン導電性固体電解質材料の150℃における導電率
と組成の関係を示す図である。
FIG. 1 is a diagram showing the temperature dependence of the electrical conductivity of a lithium ion conductive solid electrolyte material according to an embodiment of the present invention, and FIG. FIG. 3 is a diagram showing the relationship between conductivity and composition.
Claims (1)
ウムイオン導電性固体電解質材料。[Scope of Claims] 1. A lithium ion conductive solid electrolyte material comprising a composition represented by the general formula: LiNb 1-x Ta x WO 6 (0<x≦1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59175553A JPS6154161A (en) | 1984-08-23 | 1984-08-23 | Lithium-ion-conducting solid electrolyte material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59175553A JPS6154161A (en) | 1984-08-23 | 1984-08-23 | Lithium-ion-conducting solid electrolyte material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6154161A JPS6154161A (en) | 1986-03-18 |
| JPH0317348B2 true JPH0317348B2 (en) | 1991-03-07 |
Family
ID=15998092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59175553A Granted JPS6154161A (en) | 1984-08-23 | 1984-08-23 | Lithium-ion-conducting solid electrolyte material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6154161A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6853462B2 (en) * | 2016-08-26 | 2021-03-31 | 国立大学法人信州大学 | Strontium adsorbent and its manufacturing method |
| JP7142837B2 (en) * | 2018-01-30 | 2022-09-28 | 国立大学法人信州大学 | Strontium adsorbent and method for producing the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0816455B2 (en) * | 1986-09-02 | 1996-02-21 | 三井造船株式会社 | Method for cooling a gas turbine combustor |
-
1984
- 1984-08-23 JP JP59175553A patent/JPS6154161A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6154161A (en) | 1986-03-18 |
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