JPH0247409B2 - - Google Patents
Info
- Publication number
- JPH0247409B2 JPH0247409B2 JP58064871A JP6487183A JPH0247409B2 JP H0247409 B2 JPH0247409 B2 JP H0247409B2 JP 58064871 A JP58064871 A JP 58064871A JP 6487183 A JP6487183 A JP 6487183A JP H0247409 B2 JPH0247409 B2 JP H0247409B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- disulfide
- sulfur
- molar ratio
- stoichiometric
- 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
- 239000010936 titanium Substances 0.000 claims description 37
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 claims description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- RXKSUMQTYBHJHU-UHFFFAOYSA-N [S-2].[S-2].S.[Ti+4] Chemical compound [S-2].[S-2].S.[Ti+4] RXKSUMQTYBHJHU-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- -1 titanium halide Chemical class 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
本発明は高圧力下における二硫化チタンの高圧
合成方法に関するものである。
二硫化チタンは結合様式が二次元的な層状構造
を持つ無機化合物であり、ホスト層間相互はフア
ンデアワールス力によつて比較的弱く結び付けら
れているが、この弱い結合を破つて異種の分子、
原子、イオンをゲストとして取り込むことがで
き、また逆に抜き出すことも可能である。
これらの反応は可逆的であり、ホストの構造変
化も小さいので、繰り返し何回も反応を行わせる
ことができ、この点に注目して二次電池への応用
が考えられている。
特にリチウムを負極とし、二硫化チタンを正極
として組み合わせたTi／TiS2電池は高電位、高
電力密度等の優れた性質を有している。
しかしこの場合リチウムイオンの、二硫化チタ
ン層間での拡散が電池正極材料としての性能に大
きく影響を与えるため、二硫化チタンの定比性が
問題となる。つまり二硫化チタンはTi1+xS2（ｘ≧
０）で示される不定比組成をとりやすく、過剰の
チタンがホスト層間に位置するので、リチウムイ
オンを拡散が妨げられたり、リチウムイオンの這
入る量が少なくなるなど、電池としての能力を低
下させる原因となる。
このため出来るだけ定比の二硫化チタンを合成
する必要があるが、従来の方法としては、第１に
チタンハロゲン化物と硫化水素とを400〜800℃、
約１時間で反応させる方法、第２に反応管中に金
属チタンとイオウとを入れ、ヨウ素またはシユウ
素を輸送材として少量加え真空に引いた後密封
し、反応温度500〜800℃で数日間かけて反応させ
る方法、第３に反応管中に金属チタンとイオウと
を入れ、真空に引いた後密封し、500〜800℃で１
昼夜以上加熱保持して合成する方法が知られてい
る。
しかし第１の方法は反応後ハロゲンが生成した
二硫化チタンの層間に残留し、不定比二硫化チタ
ンの過剰チタンの場合と同じく、電池としての性
能を低下させる原因となるので好ましくない。
また第２の方法は第１の方法と同じくハロゲン
が残留するほか、合成に要する時間が非常に長
く、さらに第３の方法では高温にするとチタン過
剰不定比二硫化チタンを生成し、逆に低温では低
温側で安定な三硫化チタンが同時に生成するとい
う欠点がある。
このような第３の方法の改良として、試料を入
れて真空に引き密封した反応管の一方を500〜600
℃に保ち、もう一方をこれより50〜300℃低くし
て、不定比二硫化チタンと三硫化チタンとの生成
を妨げ、高温側に定比の二硫化チタン、低温側に
イオウを析出させる方法があるが、この方法では
低温部、高温部のそれぞれを独立に温度制御する
必要があり、かつ約１日の反応時間が必要であ
る。
これらの方法に対し本発明は、イオウの蒸気圧
を上げることにより比較的高温においても定比の
二硫化チタンが得られることに着目し、従来のよ
うに真空に引く方法とは逆に、チタン原料とイオ
ウ原料との混合物を0.1GPa（ギガパスカル）（約
1000気圧）以上の圧力で加圧することにより、
600〜1800℃の反応温度において、数十分〜数時
間の短時間で定比の二硫化チタンを合成すること
が可能となり、しかも原料にハロゲン等の異種イ
オウを含むことがないので生成した定比二硫化チ
タンが汚染されることもなく、また反応容器に温
度勾配をつける必要がないという特長をもつた方
法である。
本発明では0.1GPa以上の高圧で原料を加圧し
ながら反応させることが重要であり、これ以下の
圧力では定比二硫化チタンの生成に充分なイオウ
蒸気圧が得られず不定比二硫化チタンが生成す
る。
使用する原料としては、主として金属チタンと
イオウとをTi／Ｓ＝１／２〜0.7／２のモル比で
混合したものを使用するのが適当であるが、その
ほかに金属チタンと三硫化チタンとをTi／TiS3
＝１／２〜0.7／２のモル比で配合したもの、不
定比二硫化チタンとイオウとをTi1+xS2／Ｓ＝
１／2x〜0.7／2xのモル比で配合したもの、不定
比二硫化チタンと三硫化チタンとをTi1+xS2／
TiS3＝１／2x〜0.7／2xのモル比で配合したもの
を原料としても良い。
これらの場合、原料中のチタン成分とイオウ成
分とのモル比がTi／Ｓ＝１／２以下になるよう
にすることが重要であり、これを超えると不定比
二硫化チタンが生成する。またTi／Ｓ＝0.7／２
未満では三硫化チタンが生成しやすくなる。
反応温度は定比二硫化チタンの生成速度に大き
く影響し、高温にするほど反応時間が速くなるが
600〜1800℃が適当である。温度が1800℃を超え
ると不定比二硫化チタンの生成を妨げることがむ
づかしくなり、また温度が600℃未満では三硫化
チタンが二硫化チタンになるまでに長時間を要
し、本方法の意味を失うこととなる。また600〜
1800℃において二硫化チタンが生成した後も反応
を続けると二硫化チタンの結晶成長が進み粒径の
大きい定比二硫化チタンを得ることができる。
つぎに本発明の実施例を記載する。
実施例 １
金属チタン粉末とイオウとをTi／Ｓ＝１／２，
0.9／２のモル比で混合し高圧発生装置にて3GPa
で加圧し、800〜1200℃で、15分〜４時間加熱し
て合成した。生成物の同定を粉末Ｘ線回折により
行つた結果を表−１に示す。温度800℃、1000℃
では三硫化チタンのピークが消失するのに４時間
の反応時間が必要であるのに対し、1200℃では15
分で消失した。
実施例 ２
金属チタン粉末とイオウとをTi／Ｓ＝１／２
のモル比で混合し、高圧発生装置にて圧力3GPa、
反応温度1000℃で合成した場合の反応時間による
三硫化チタンと二硫化チタンとの生成比の推移お
よび二硫化チタンの定比性の変化を追跡した結果
を表−２に示す。
生成比の推移は粉末Ｘ線回折により両者の
（001）面からの回折ピークの高さ比TiS3／TiS2
で示し、定比性については粉末Ｘ線回折によりＣ
軸格子定数を求めることによつて調べた。これは
不定比二硫化チタンでは過剰チタンが層間に位置
することにより層間隔が広がるため、不定比性が
増すに従つて層面に垂直なＣ軸格子定数が定比の
5.695から徐々に大きくなることに基づくもので
ある。
実施例 ３
金属チタン粉末とイオウとをTi／Ｓ＝１／２
のモル比で混合し、高圧発生装置にて3GPaで加
圧、1000℃に昇温し、６時間保持して合成した。
生成物の粉末Ｘ線回折と熱重量分析とによる同定
の結果、Ｃ軸格子定数5.696を持つTi1.00S2であつ
た。
実施例 ４
金属チタン粉末とイオウとをTi／Ｓ＝0.9／２
のモル比で混合し、高圧発生装置にて3GPaで加
圧、1200℃に昇温し、30分間保持して合成した。
生成物の粉末Ｘ線回折と熱重量分析とによる同定
の結果、Ｃ軸格子定数5.697を持つTi1.01S2であつ
た。
実施例 ５
金属チタン粉末と三硫化チタンとをTi／TiS3
＝１／２のモル比で混合し、高圧発生装置にて
3GPaで加圧、1000℃に昇温し、４時間保持して
合成した。生成物の粉末Ｘ線回折と熱重量分析と
による同定の結果、Ｃ軸格子定数5.697を持つ
Ti1.01S2であつた。
The present invention relates to a method for high-pressure synthesis of titanium disulfide under high pressure. Titanium disulfide is an inorganic compound with a two-dimensional layered structure, and the host layers are relatively weakly bound by the Van der Waals force.
Atoms and ions can be taken in as guests, and conversely, they can also be extracted. These reactions are reversible and structural changes in the host are small, so the reactions can be repeated many times, and with this in mind, applications to secondary batteries are being considered. In particular, Ti/TiS 2 batteries, which combine lithium as a negative electrode and titanium disulfide as a positive electrode, have excellent properties such as high potential and high power density. However, in this case, the stoichiometry of titanium disulfide becomes a problem because the diffusion of lithium ions between the titanium disulfide layers greatly affects the performance as a battery positive electrode material. In other words, titanium disulfide is Ti 1+x S 2 (x≧
0), and excessive titanium is located between the host layers, which impedes the diffusion of lithium ions and reduces the amount of lithium ions that enter, which reduces the performance of the battery. becomes. For this reason, it is necessary to synthesize titanium disulfide in a stoichiometric ratio as much as possible, but as a conventional method, first, titanium halide and hydrogen sulfide are heated at 400 to 800°C.
The second method is to put titanium metal and sulfur into a reaction tube, add a small amount of iodine or sulfur as a transport material, evacuate it, seal it, and keep it at a reaction temperature of 500 to 800°C for several days. The third method is to put titanium metal and sulfur into a reaction tube, evacuate it, seal it, and heat it at 500 to 800℃ for 1 hour.
A method of synthesizing by heating and holding for more than day and night is known. However, the first method is not preferable because halogen remains between the layers of the produced titanium disulfide after the reaction, and as in the case of excess titanium in non-stoichiometric titanium disulfide, this causes a decrease in the performance of the battery. In addition, in the second method, halogen remains as in the first method, and the time required for synthesis is extremely long.Furthermore, in the third method, when the temperature is raised, excessive titanium and non-stoichiometric titanium disulfide are produced; However, the drawback is that titanium trisulfide, which is stable at low temperatures, is simultaneously produced. As an improvement to the third method, one side of the reaction tube containing the sample, evacuated, and sealed was heated to 500 to 600
℃, and lower the other temperature by 50 to 300℃ to prevent the formation of non-stoichiometric titanium disulfide and titanium trisulfide, and precipitate stoichiometric titanium disulfide on the high temperature side and sulfur on the low temperature side. However, this method requires independent temperature control of the low-temperature section and high-temperature section, and requires about one day of reaction time. In contrast to these methods, the present invention focuses on the fact that titanium disulfide can be obtained at a constant ratio even at relatively high temperatures by increasing the vapor pressure of sulfur. The mixture of raw material and sulfur raw material is heated to 0.1GPa (gigapascal) (approx.
By pressurizing at a pressure of 1000 atmospheres or more,
At a reaction temperature of 600 to 1800°C, it is possible to synthesize stoichiometric titanium disulfide in a short period of several minutes to several hours, and since the raw materials do not contain foreign sulfur such as halogens, the produced sulfur can be easily synthesized. This method has the advantage that titanium disulfide is not contaminated and there is no need to create a temperature gradient in the reaction vessel. In the present invention, it is important to react while pressurizing the raw materials at a high pressure of 0.1 GPa or higher; if the pressure is lower than this, sufficient sulfur vapor pressure cannot be obtained to produce stoichiometric titanium disulfide, and non-stoichiometric titanium disulfide is produced. generate. As raw materials to be used, it is appropriate to mainly use a mixture of metallic titanium and sulfur at a molar ratio of Ti/S = 1/2 to 0.7/2, but in addition, metallic titanium and titanium trisulfide may be used. Ti/TiS 3
= non-stoichiometric titanium disulfide and sulfur mixed at a molar ratio of 1/2 to 0.7/2, Ti 1+x S 2 /S =
Ti 1+ x S 2 / non-stoichiometric titanium disulfide and titanium trisulfide blended at a molar ratio of 1/2x to 0.7/2x .
TiS 3 mixed at a molar ratio of 1/2x to 0.7/2x may be used as the raw material. In these cases, it is important to keep the molar ratio of the titanium component to the sulfur component in the raw material to Ti/S=1/2 or less; if this is exceeded, non-stoichiometric titanium disulfide will be produced. Also, Ti/S=0.7/2
If it is less than that, titanium trisulfide is likely to be produced. The reaction temperature greatly affects the rate of stoichiometric titanium disulfide production, and the higher the temperature, the faster the reaction time.
A temperature of 600 to 1800°C is suitable. When the temperature exceeds 1800°C, it becomes difficult to prevent the formation of non-stoichiometric titanium disulfide, and when the temperature is below 600°C, it takes a long time for titanium trisulfide to become titanium disulfide, making this method difficult. It will lose its meaning. 600~
If the reaction continues even after titanium disulfide is produced at 1800°C, the crystal growth of titanium disulfide will progress and stoichiometric titanium disulfide with a large particle size can be obtained. Next, examples of the present invention will be described. Example 1 Metallic titanium powder and sulfur were mixed at Ti/S=1/2,
Mix at a molar ratio of 0.9/2 and generate 3 GPa using a high pressure generator.
The mixture was synthesized by heating at 800 to 1200°C for 15 minutes to 4 hours. Table 1 shows the results of product identification by powder X-ray diffraction. Temperature 800℃, 1000℃
At 1200℃, a reaction time of 4 hours is required for the peak of titanium trisulfide to disappear;
Disappeared in minutes. Example 2 Metallic titanium powder and sulfur at Ti/S=1/2
Mix at a molar ratio of
Table 2 shows the results of tracking changes in the production ratio of titanium trisulfide and titanium disulfide and changes in the stoichiometry of titanium disulfide depending on the reaction time when synthesized at a reaction temperature of 1000°C. The transition in the production ratio is determined by the height ratio of the diffraction peaks from the (001) plane of both TiS 3 /TiS 2 by powder X-ray diffraction.
The stoichiometry is determined by powder X-ray diffraction.
This was investigated by determining the axial lattice constant. This is because in non-stoichiometric titanium disulfide, the layer spacing increases due to excess titanium being located between the layers, so as the non-stoichiometric property increases, the C-axis lattice constant perpendicular to the layer plane becomes less stoichiometric.
This is based on the fact that it gradually increases from 5.695. Example 3 Metallic titanium powder and sulfur at Ti/S=1/2
The mixture was mixed at a molar ratio of 1,000,000, and then pressurized at 3GPa using a high-pressure generator, heated to 1000°C, and held for 6 hours to synthesize.
Identification of the product by powder X-ray diffraction and thermogravimetric analysis revealed that it was Ti 1.00 S 2 with a C-axis lattice constant of 5.696. Example 4 Metallic titanium powder and sulfur at Ti/S=0.9/2
The mixture was mixed at a molar ratio of , and was then pressurized at 3 GPa using a high pressure generator, heated to 1200°C, and held for 30 minutes to synthesize.
Identification of the product by powder X-ray diffraction and thermogravimetric analysis revealed that it was Ti 1.01 S 2 with a C-axis lattice constant of 5.697. Example 5 Metallic titanium powder and titanium trisulfide were combined into Ti/TiS 3
= Mix at a molar ratio of 1/2 and use a high pressure generator
The mixture was synthesized by applying pressure to 3 GPa, raising the temperature to 1000°C, and holding it for 4 hours. Identification of the product by powder X-ray diffraction and thermogravimetric analysis revealed that it has a C-axis lattice constant of 5.697.
It was Ti 1.01 S 2 .
【表】【table】
【表】【table】
【表】 原料組成 Ti／Ｓ＝１／２（モル比） 圧 力 3GPa 温 度 1000℃【table】 Raw material composition Ti/S=1/2 (molar ratio) Pressure 3GPa Temperature 1000℃
Claims (1)
0.7／２のモル比で配合したもの、金属チタンと
三硫化チタンとをTi／TiS3＝１／２〜0.7／２の
モル比で配合したもの、チタン過剰不定比二硫化
チタン（Ti1+xS2）とイオウとをTi1+xS2／Ｓ＝
１／２〜0.7／2xのモル比で配合したもの、三硫
化チタンとチタン過剰不定比二硫化チタン
（Ti1+xS2）とをTi1+xS2／TiS3＝１／2x〜0.7／2x
のモル比で配合したもののいずれか１組あるいは
複数の組を組合せたものを原料とし、この原料を
0.1GPa（約1000気圧）以上の高圧力を用いて加圧
しながら反応温度600〜1800℃で合成することを
特徴とする二硫化チタンの高圧合成方法。1 Metallic titanium and sulfur at Ti/S=1/2~
A mixture of titanium metal and titanium trisulfide at a molar ratio of 0.7/2, a mixture of titanium metal and titanium trisulfide at a molar ratio of Ti/TiS 3 = 1/2 to 0.7/2, and an excess of titanium, non-stoichiometric titanium disulfide (Ti 1+ x S 2 ) and sulfur as Ti 1+x S 2 /S=
Titanium trisulfide and titanium-excess non-stoichiometric titanium disulfide (Ti 1+x S 2 ) are blended at a molar ratio of 1/2 to 0.7/2x, with Ti 1+x S 2 /TiS 3 = 1/2x to 0.7/2x
The raw material is any one set or a combination of multiple sets blended at a molar ratio of
A method for high-pressure synthesis of titanium disulfide, which is characterized by synthesizing at a reaction temperature of 600 to 1800°C while applying high pressure of 0.1 GPa (approximately 1000 atm) or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58064871A JPS59190221A (en) | 1983-04-13 | 1983-04-13 | Process for high-pressure synthesis of titanium disulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58064871A JPS59190221A (en) | 1983-04-13 | 1983-04-13 | Process for high-pressure synthesis of titanium disulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59190221A JPS59190221A (en) | 1984-10-29 |
| JPH0247409B2 true JPH0247409B2 (en) | 1990-10-19 |
Family
ID=13270630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58064871A Granted JPS59190221A (en) | 1983-04-13 | 1983-04-13 | Process for high-pressure synthesis of titanium disulfide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59190221A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5809574A (en) * | 1996-08-15 | 1998-09-22 | Cabot Safety Intermediate Corporation | Hearing protection device |
-
1983
- 1983-04-13 JP JP58064871A patent/JPS59190221A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59190221A (en) | 1984-10-29 |
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