JPH0128465B2 - - Google Patents
Info
- Publication number
- JPH0128465B2 JPH0128465B2 JP55001331A JP133180A JPH0128465B2 JP H0128465 B2 JPH0128465 B2 JP H0128465B2 JP 55001331 A JP55001331 A JP 55001331A JP 133180 A JP133180 A JP 133180A JP H0128465 B2 JPH0128465 B2 JP H0128465B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- film
- ionic conductivity
- lithium battery
- powder
- 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
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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physical Vapour Deposition (AREA)
- Primary Cells (AREA)
- Secondary Cells (AREA)
Description
【発明の詳細な説明】
〔発明の利用分野〕
本発明は、固体電解質を有するリチウム電池に
関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a lithium battery having a solid electrolyte.
近年、超イオン伝導性物質、とくにアルカリイ
オン伝導体を用いたリチウム電池への関心が高ま
りつつある。これは、電子機器の小型化、薄型化
に伴い、電池の薄型化への要望が強まつてきたた
めである。
In recent years, interest in lithium batteries using superionically conductive materials, particularly alkaline ion conductors, has been increasing. This is because as electronic devices become smaller and thinner, there is an increasing demand for thinner batteries.
そのため、イオン伝導度の高い安定な固体電解
質の出現が強く望まれている。また、固体電解質
を薄膜化し、抵抗を下げることも望まれている。
しかし、従来のセラミツク技術では、膜厚10μｍ
以下の薄膜を作成することは困難である。また、
従来の製膜技術であるCVD法、スパツタリング
法を用いても、イオン伝導度の大きい薄膜は得ら
れていなかつた。この原因は、(1)上記固体電解質
の合成温度が高いこと、(2)薄膜形成中にアルカリ
金属酸化物が蒸発などによつて失われるため、組
成制御が困難である、ことなどである。さらに、
通常の低温における膜形成では得られた膜の結晶
性が悪いため、イオン伝導性の良好な薄膜は得ら
れていなかつた。 Therefore, the emergence of stable solid electrolytes with high ionic conductivity is strongly desired. It is also desired to reduce the resistance by making the solid electrolyte thinner.
However, with conventional ceramic technology, the film thickness is 10 μm.
It is difficult to create thin films that: Also,
Even using conventional film-forming techniques such as CVD and sputtering, thin films with high ionic conductivity have not been obtained. The reasons for this are (1) the synthesis temperature of the solid electrolyte is high, and (2) it is difficult to control the composition because the alkali metal oxide is lost through evaporation or the like during thin film formation. moreover,
When forming a film at a normal low temperature, the resulting film has poor crystallinity, so a thin film with good ion conductivity has not been obtained.
本発明の目的は、優れたイオン伝導性を示す固
体電解質を有するリチウム電池を提供することに
ある。
An object of the present invention is to provide a lithium battery having a solid electrolyte exhibiting excellent ionic conductivity.
本発明のリチウム電池は、アルカリイオンの超
イオン伝導体、例えばβ−Al2O3、β−Ga2O3、
Na3Zr2Si2PO12、Li14Zn（GeO4）4などと、
LiAlO2、LiGaO2、Li2CO3、NaAlO2、
NaGaO2、Na2CO3などのアルカリ金属化合物と
の混合物をターゲツトとして、スパツタリング法
により、超イオン伝導性薄膜を形成して固体電解
質とすることを特徴とする。この場合、両者の混
合粉末を用いることが好ましい。粉末を用いる理
由は、
(1) 薄膜中のアルカリ濃度を自由に制御できるこ
と、
(2) NaMO2（Ｍ＝Al、Ga）などが潮解性である
ため、混合焼結体ターゲツトを作ることが困難
であることなどである。
The lithium battery of the present invention is made of a superionic conductor of alkali ions, such as β-Al 2 O 3 , β-Ga 2 O 3 ,
Na 3 Zr 2 Si 2 PO 12 , Li 14 Zn(GeO 4 ) 4 , etc.
LiAlO 2 , LiGaO 2 , Li 2 CO 3 , NaAlO 2 ,
It is characterized by forming a superionically conductive thin film using a sputtering method using a mixture with an alkali metal compound such as NaGaO 2 or Na 2 CO 3 as a solid electrolyte. In this case, it is preferable to use a mixed powder of both. The reasons for using powder are: (1) the alkali concentration in the thin film can be freely controlled; and (2) NaMO 2 (M = Al, Ga) is deliquescent, making it difficult to create a mixed sintered target. etc.
両者の混合粉末を用いる代わりに、超イオン伝
導性化合物の原料粉末を焼成し、この焼成物をタ
ーゲツトとし、アルカリ金属化合物をペレツトと
したものをターゲツト上に配置し、スパツタアツ
プ方式とし薄膜形成を行う如き周知の方法も当然
用い得る。 Instead of using a mixed powder of both, a raw material powder of a superionic conductive compound is fired, this fired product is used as a target, and a pellet of an alkali metal compound is placed on the target to form a thin film using a sputtering method. Of course, well-known methods such as these can also be used.
電池の正極、負極材料としては、リチウム電池
として周知のものを用いることができる。例え
ば、負極材料としては、Li又はLi合金などが用い
られる。正極材料としては、Liイオンを受容、放
出するものであればなにも用いてもよいが、
TiS2などが好ましい。 As the positive electrode and negative electrode materials of the battery, materials well known as lithium batteries can be used. For example, Li or a Li alloy is used as the negative electrode material. As the positive electrode material, any material that accepts and releases Li ions may be used, but
TiS 2 and the like are preferred.
以下、本発明を実施例によつて詳細に説明す
る。
Hereinafter, the present invention will be explained in detail with reference to Examples.
実施例 １
Ga2O3およびNa2CO3原料粉末を４：１のモル
比で秤量混合し、1100℃、10時間反応させてNa
−β″−Ga2O3を作成する。また、モル比を調整
し、同様な方法にて、NaGaO2粉末を作成する。
これら粉末をNa2O・4Ga2O3：NaGaO2＝１：２
（mol）となるように混合し、この粉末をターゲ
ツトとし、スパツタアツプ方式とし薄膜形成を行
なつた。また、本実施例は、プレーナーマグネト
ロン高速スパツタリング法を採用した。上記ター
ゲツトを用い、基板温度：300℃、真空度：２×
10-2mmHg、放電ガス：（Ar／O2＝60／40）膜形
成速度：0.4μｍ／ｈのスパツタリング条件で膜を
作成した。SiO2、アルミナ基板上に膜厚約2μｍ
の膜を作成し、イオン伝導度を測定した結果300
℃にて２×10-5mho・cm-1であつた。なお、β″−
Ga2O3の粉末のみからなるターゲツトを用いたと
きは、上記同一条件で作成した膜のイオン伝導度
が、４×10-7mho・cm-1であつた。これは、スパ
ツタ中にアルカリ金属が蒸発により失われたこと
によるもので、ターゲツト組成を所望通りに制御
することが非常に重要であることがわかる。Example 1 Ga 2 O 3 and Na 2 CO 3 raw material powders were weighed and mixed at a molar ratio of 4:1, and reacted at 1100°C for 10 hours to produce Na.
−β″−Ga 2 O 3 is created. Also, the molar ratio is adjusted and NaGaO 2 powder is created in the same manner.
These powders were mixed into Na 2 O・4Ga 2 O 3 :NaGaO 2 =1:2.
(mol), and using this powder as a target, a thin film was formed using a sputter up method. Further, in this example, a planar magnetron high speed sputtering method was adopted. Using the above target, substrate temperature: 300℃, degree of vacuum: 2×
A film was formed under sputtering conditions of 10 −2 mmHg, discharge gas: (Ar/O 2 =60/40), and film formation rate: 0.4 μm/h. SiO 2 , film thickness approximately 2 μm on alumina substrate
The results of creating a membrane and measuring its ionic conductivity were 300
It was 2×10 -5 mho·cm -1 at ℃. In addition, β″−
When a target consisting only of Ga 2 O 3 powder was used, the ionic conductivity of the film prepared under the same conditions as above was 4×10 −7 mho·cm −1 . This is due to the alkali metal being lost by evaporation during sputtering, and it can be seen that it is very important to control the target composition as desired.
実施例 ２
MgAl2O4あるいはアルミナを基板とし、実施
例１と同様のスパツタリング条件にて、1.5μｍ厚
みのNa−βGa2O3薄膜を作成した。第１図は、こ
の薄膜の基板面に平行方向に測定したイオン伝導
度の温度変化を示したもの（アレニウスプロツ
ト）である。図から、優れた特性の薄膜であるこ
とがわかる。Example 2 Using MgAl 2 O 4 or alumina as a substrate, a 1.5 μm thick Na-βGa 2 O 3 thin film was produced under the same sputtering conditions as in Example 1. FIG. 1 shows the temperature change (Arrhenius plot) of the ionic conductivity of this thin film measured in a direction parallel to the substrate surface. The figure shows that the film has excellent properties.
Na−βAl2O3の場合も、ターゲツト組成を
Na2O・11Al2O3：NaAlO2＝１：２（mol）とす
ることで、β−Ga2O3とほぼ同様のイオン伝導度
を示す薄膜が得られた。 In the case of Na−βAl 2 O 3 , the target composition is
By setting Na 2 O.11Al 2 O 3 :NaAlO 2 =1:2 (mol), a thin film exhibiting almost the same ionic conductivity as β-Ga 2 O 3 was obtained.
実施例 ３
Na2CO3、ZrO2、NH4H2PO4、SiO2原料粉末
をNa3Zr2Si2PO12組成となるように秤量混合し、
固相反応によりNa3Zr2Si2PO12粉末を作成した。
さらに、この粉末にNaCO3をNa3Zr2Si2PO12：
NaCO3＝１：３（mol）となるよう混合しターゲ
ツトとした。Example 3 Na 2 CO 3 , ZrO 2 , NH 4 H 2 PO 4 , and SiO 2 raw material powders were weighed and mixed to have a composition of Na 3 Zr 2 Si 2 PO 12 ,
Na 3 Zr 2 Si 2 PO 12 powder was prepared by solid phase reaction.
Additionally, add NaCO3 to this powder with Na3Zr2Si2PO12 :
NaCO 3 was mixed at a ratio of 1:3 (mol) and used as a target.
実施例１と同様なスパツタリング条件で5μｍ
厚みの薄膜を作成し、その後800℃にて熱処理し
た。この様にして得られた薄膜のイオン伝導度
は、200℃において、２×10-3mho・cm-1であつ
た。 5μm under the same sputtering conditions as Example 1
A thin film with a certain thickness was created and then heat treated at 800°C. The ionic conductivity of the thin film thus obtained was 2×10 -3 mho·cm -1 at 200°C.
前記各種の固体電解質を、基板上の正極材料
（TiS2）の上に前述のようなスパツタリング法に
より形成し、その上に負極材料、負極集電体を積
層し、全固体リチウム電池とした。このリチウム
電池は、固体電解質が薄膜であるため、電池全体
としても薄型で、かつ内部抵抗も小さいため、優
れたリチウム電池であつた。 The various solid electrolytes described above were formed on a positive electrode material (TiS 2 ) on a substrate by the sputtering method as described above, and a negative electrode material and a negative electrode current collector were laminated thereon to form an all-solid-state lithium battery. This lithium battery was an excellent lithium battery because the solid electrolyte was a thin film, the battery as a whole was thin, and the internal resistance was low.
以上説明したごとく本発明のリチウム電池は、
その固体電解質が5μｍ以下の薄膜においても、
イオン伝導度の著しく高い薄膜であり、バルク材
料に比べ薄膜は厚みが３桁程小さいため、イオン
伝導は３桁大きくなる。それ故、リチウム電池と
して従来にない薄い電池を得ることができた。
As explained above, the lithium battery of the present invention is
Even if the solid electrolyte is a thin film of 5 μm or less,
It is a thin film with extremely high ionic conductivity, and since the thickness of the thin film is three orders of magnitude smaller than that of the bulk material, the ionic conductivity is three orders of magnitude greater. Therefore, it was possible to obtain a thinner lithium battery than ever before.
第１図は、本発明の方法により製造した超イオ
ン伝導性薄膜におけるイオン伝導のアレニウスプ
ロツトを示す線図である。
FIG. 1 is a diagram showing an Arrhenius plot of ion conduction in a superionically conductive thin film produced by the method of the present invention.
Claims (1)
とアルカリ金属化合物とをターゲツトとして、ス
パツタリング法により形成された超イオン伝導性
薄膜を固体電解質として有することを特徴とする
リチウム電池。1. A lithium battery comprising, as a solid electrolyte, a superionically conductive thin film formed by sputtering using a superionically conductive compound of alkali metal ions and an alkali metal compound as targets.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP133180A JPS5699979A (en) | 1980-01-11 | 1980-01-11 | Manufacture of super ionic conductive thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP133180A JPS5699979A (en) | 1980-01-11 | 1980-01-11 | Manufacture of super ionic conductive thin film |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58105856A Division JPS5931569A (en) | 1983-06-15 | 1983-06-15 | Whole solid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5699979A JPS5699979A (en) | 1981-08-11 |
| JPH0128465B2 true JPH0128465B2 (en) | 1989-06-02 |
Family
ID=11498509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP133180A Granted JPS5699979A (en) | 1980-01-11 | 1980-01-11 | Manufacture of super ionic conductive thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5699979A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5931569A (en) * | 1983-06-15 | 1984-02-20 | Hitachi Ltd | Whole solid battery |
| JPS5937604A (en) * | 1983-06-15 | 1984-03-01 | 株式会社日立製作所 | How to create superionically conductive thin films |
| JPS63206462A (en) * | 1987-02-24 | 1988-08-25 | Kawatetsu Kogyo Kk | Production of thin conductive or superconductive film |
| KR100294467B1 (en) * | 1994-06-07 | 2001-10-24 | 남창우 | Process for producing solid electrolyte for sodium-sulfur battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5085585A (en) * | 1973-12-03 | 1975-07-10 |
-
1980
- 1980-01-11 JP JP133180A patent/JPS5699979A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5699979A (en) | 1981-08-11 |
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