JPH0735294B2 - Beta-alumina tube manufacturing method - Google Patents
Beta-alumina tube manufacturing methodInfo
- Publication number
- JPH0735294B2 JPH0735294B2 JP3076833A JP7683391A JPH0735294B2 JP H0735294 B2 JPH0735294 B2 JP H0735294B2 JP 3076833 A JP3076833 A JP 3076833A JP 7683391 A JP7683391 A JP 7683391A JP H0735294 B2 JPH0735294 B2 JP H0735294B2
- Authority
- JP
- Japan
- Prior art keywords
- beta
- alumina
- degreasing
- furnace
- molded body
- 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
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 title claims description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000005238 degreasing Methods 0.000 claims description 31
- 238000010304 firing Methods 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 230000002950 deficient Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Powder Metallurgy (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ナトリウム−硫黄電池
の固体電解質管として使用されるベータアルミナ管を精
度よく、かつ歩留りよく生産することができるベータア
ルミナ管の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a beta-alumina tube capable of producing a beta-alumina tube used as a solid electrolyte tube for a sodium-sulfur battery with high accuracy and yield.
【０００２】[0002]
【従来の技術】例えばナトリウム−硫黄電池において
は、陽極活物質と陰極活物質とを分離する固体電解質管
としてベータアルミナ管が使用されている。そして、該
ベータアルミナ管の製造方法においてはベータアルミナ
成形体を焼成処理する前段階として、前記ベータアルミ
ナ成形体の有機バインダーを除去するための脱脂処理を
施すことが知られている。2. Description of the Related Art For example, in a sodium-sulfur battery, a beta-alumina tube is used as a solid electrolyte tube for separating an anode active material and a cathode active material. Then, in the method for producing the beta-alumina tube, it is known to perform a degreasing treatment for removing the organic binder of the beta-alumina molded body as a pre-treatment step for firing the beta-alumina molded body.
【０００３】ところが、従来の脱脂処理においては所定
形状に成形されたベータアルミナ成形体を強制的に外気
導入しない脱脂炉内で行っているために、炉内の酸素濃
度が低下して有機バインダーの完全燃焼が行われず脱脂
不足となる傾向があり、有機バインダーの残留炭素によ
り後工程である焼成処理時に収縮不足を発生させて、焼
成後に得られるベータアルミナ管が所定寸法よりも大き
な不良品となってしまうという問題点があった。また、
脱脂処理の際の昇温速度を速くすると急激な有機バイン
ダーの分解によって脱脂品にキレを発生させて不良品に
なるという問題点もあった。However, in the conventional degreasing treatment, since the beta-alumina molded body molded into a predetermined shape is carried out in a degreasing furnace in which the outside air is not forcibly introduced into the outside air, the oxygen concentration in the furnace decreases and the organic binder There is a tendency that degreasing is insufficient because complete combustion is not performed, and due to residual carbon in the organic binder, insufficient shrinkage occurs during the firing process that is a post-process, and the beta-alumina tube obtained after firing becomes a defective product that is larger than the specified size. There was a problem that it would end up. Also,
There is also a problem that if the temperature rising rate in the degreasing process is increased, the degreased product is liable to be broken due to the rapid decomposition of the organic binder, resulting in a defective product.
【０００４】[0004]
【発明が解決しようとする課題】本発明は上記のような
従来の問題点を解決して、有機バインダーの完全燃焼が
行われて脱脂不足を生ずることがなく、また、急激な有
機バインダーの分解を防止して脱脂品にキレを発生させ
ることもなく焼成後に所定寸法どおりのベータアルミナ
管を精度よく、かつ歩留りよく生産することができるベ
ータアルミナ管の製造方法を提供することを目的として
完成されたものである。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art so that the organic binder is not completely burned to cause insufficient degreasing, and the organic binder is rapidly decomposed. It was completed for the purpose of providing a method for producing a beta-alumina tube capable of accurately producing a beta-alumina tube having a predetermined dimension after firing without causing cracks in a degreased product and firing it with good yield. It is a thing.
【０００５】[0005]
【課題を解決するための手段】上記の課題を解決するた
めになされた本発明のベータアルミナ管の製造方法は、
一端を開口部とする有底筒状に成形されたベータアルミ
ナ成形体を、前記開口部の開口率が１０％以上に開放さ
れた状態として室温から３００℃まで炉内酸素濃度が１
８％以上の雰囲気中で６０分以上脱脂処理した後焼成処
理を施すことを特徴とするものである。The method for producing a beta-alumina tube of the present invention, which has been made to solve the above problems, comprises:
A beta-alumina molded body having a bottomed tubular shape having one end as an opening is opened to an opening ratio of 10% or more.
The oxygen concentration in the furnace from room temperature to 300 ° C is 1
It is characterized in that it is subjected to a degreasing treatment for 60 minutes or more in an atmosphere of 8% or more and then a firing treatment.
【０００６】本発明においては、先ず最初に加圧成形装
置等を用いて常法により所定形状に成形された一端を開
口部とする有底筒状のベータアルミナ成形体を脱脂処理
用電気炉などの脱脂処理炉内に投入して、室温から３０
０℃までの炉内酸素濃度が１８％以上、室温から３００
℃までの加熱所要時間が６０分以上の条件下で通常の温
度条件に従い脱脂処理を施すのであるが、この際、前記
のベータアルミナ成形体は開口部を閉鎖することなく開
放された状態で脱脂処理を行うことが好ましく、これに
よりベータアルミナ成形体の内外両表面の脱脂が十分に
行われる。In the present invention, first, a bottomed cylindrical beta-alumina molded body having an opening at one end, which is molded into a predetermined shape by a conventional method using a pressure molding apparatus or the like, is subjected to a degreasing treatment electric furnace or the like. Put it in the degreasing treatment furnace at room temperature for 30
Oxygen concentration in the furnace up to 0 ℃ is 18% or more, room temperature to 300
Degreasing treatment is performed according to normal temperature conditions under the condition that the heating time to 60 ° C is 60 minutes or more. At this time, the beta alumina molded body is degreased in an open state without closing the opening. It is preferable to perform the treatment, and thereby the degreasing of the inner and outer surfaces of the beta-alumina molded body is sufficiently performed.
【０００７】このようにベータアルミナ成形体の開口部
が開放された状態で脱脂処理を行うためには、焼台とし
て透孔状の通気路を有するものを使用し、有底筒状のベ
ータアルミナ成形体をその開口部が通気路を通じて脱脂
処理炉内に開放されるよう倒立状態として焼台上へ保持
させこの状態で脱脂処理を行う外、ベータアルミナ成形
体を横置き或いは正立配置等によって開口部を開放した
状態とすることもできるものであるが、有機バインダー
中の揮発成分には空気より重いものもあるため倒立状態
に保持して下方より自然放出させるのが最適である。In order to perform the degreasing treatment with the opening of the beta-alumina compact thus opened, a baking table having a through-hole-like air passage is used, and a bottomed cylindrical beta-alumina is used. The molded body is held on the baking table in an inverted state so that its opening is opened to the inside of the degreasing treatment furnace through the ventilation passage, and the degreasing process is performed in this state.In addition, the beta alumina molded body is placed horizontally or upright. Although it is possible to open the opening, some volatile components in the organic binder are heavier than air, so it is optimal to hold them upside down and spontaneously release from below.
【０００８】また、前記ベータアルミナ成形体の開口部
の開口率は、開口部の全面積に対して１０％以上とする
ことが好ましく、さらに、大量処理を行うときは焼台と
して上面に格子溝状の通気路が形成されたものを使用
し、このような焼台上に多数本のベータアルミナ成形体
をその開口部が前記通気路を通じて炉内に開放されるよ
う倒立させて脱脂処理を行えば、一度に多数のベータア
ルミナ成形体を効率よく脱脂処理することができる。Further, the opening ratio of the openings of the beta-alumina molded body is preferably 10% or more with respect to the total area of the openings. Further, when a large amount of processing is performed, a lattice table is formed on the upper surface as a baking table. Use a sheet-shaped ventilation passage, and place a large number of beta-alumina compacts on such a baking table so that their openings are inverted into the furnace through the ventilation passage to perform degreasing treatment. For example, a large number of beta-alumina compacts can be efficiently degreased at one time.
【０００９】前記の脱脂処理は、室温から３００℃まで
の炉内酸素濃度が１８％以上の条件下で行われるが、こ
こで、酸素濃度とは脱脂炉内における酸素の体積率（vo
l ％）をいい、本発明者の実験によれば１８％未満の場
合には有機バインダーの完全燃焼が妨げられてベータア
ルミナ成形体中に不完全燃焼の有機バインダーが残存
し、脱脂不足を生じて次工程の焼成処理において十分な
収縮ができず所定値よりも大きな寸法の不良品を発生さ
せることとなる。The above-mentioned degreasing treatment is carried out under the condition that the oxygen concentration in the furnace from room temperature to 300 ° C. is 18% or more. Here, the oxygen concentration means the volume ratio of oxygen in the degreasing furnace (vo.
According to the experiments conducted by the present inventor, when the amount is less than 18%, the complete burning of the organic binder is hindered and the incompletely burned organic binder remains in the beta-alumina molded body, resulting in insufficient degreasing. In the firing process of the next step, sufficient shrinkage cannot be achieved, and a defective product having a size larger than a predetermined value is generated.
【００１０】また前記の脱脂処理は、室温から３００℃
までの加熱所要時間が６０分以上の条件下で行われる。
ここで、加熱所要時間とは室温から３００℃まで均一に
昇温するのに要する時間をいい、本発明者の実験によれ
ば６０分よりも短い時間で加熱した場合には昇温が急激
となり有機バインダーの分解反応が均一かつ段階的に行
われず特定の箇所に集中する傾向があり、該部分がキレ
と称される亀裂不良に発展するものと思われる。なお、
前記の酸素濃度と加熱所要時間との相関関係は明らかで
はないが、いずれの条件を欠いても満足な脱脂処理を行
うことはできないものである。The degreasing treatment is carried out at room temperature to 300 ° C.
The heating time is up to 60 minutes.
Here, the heating required time means a time required to uniformly raise the temperature from room temperature to 300 ° C. According to the experiment of the present inventor, the temperature rises rapidly when the heating time is shorter than 60 minutes. The decomposition reaction of the organic binder does not occur uniformly and stepwise and tends to concentrate at a specific portion, and this portion is considered to develop into a crack defect called a crack. In addition,
Although the correlation between the oxygen concentration and the required heating time is not clear, a satisfactory degreasing treatment cannot be performed under any of the conditions.
【００１１】以上のように所定条件下での脱脂処理を終
えた後は、得られたベータアルミナ成形体を焼成炉内へ
投入して通常の焼成条件に従って焼成処理を施す。この
場合、ベータアルミナ成形体は前工程の脱脂処理におい
て有機バインダーの不完全燃焼による残留炭素がないよ
う十分に脱脂がされているので、収縮不足を生ずること
なく焼成が行われることとなり、また、急激な加熱を伴
うことなく脱脂処理が施されているのでキレを発生させ
ることもなく品質基準値に適合するベータアルミナ管が
製造されることとなる。After the degreasing treatment under the predetermined conditions is completed as described above, the obtained beta-alumina molded body is put into a firing furnace and subjected to firing treatment under normal firing conditions. In this case, since the beta-alumina molded body has been sufficiently degreased so that there is no residual carbon due to incomplete combustion of the organic binder in the degreasing treatment in the previous step, firing will be performed without causing insufficient shrinkage, and Since the degreasing treatment is performed without abrupt heating, a beta-alumina tube that meets the quality standard value is manufactured without causing sharpness.
【００１２】[0012]
【実施例】ベータアルミナ原料の乾燥粉末に有機バイン
ダーとしてのポリエチレングリコール５重量％を水とと
もに添加してスラリー状とし、このスラリーをスプレー
ドライヤーを用いて造粒したものを乾式静水圧加圧成形
装置により、成形圧力２．２トン／cm2 で有底筒状の外
径４５mm、内径４０mm、長さ４５０mmのベータアルミナ
成形体を作製した。得られたベータアルミナ成形体を外
気導入型の脱脂電気炉を用いて各々１００本ずつ、表１
に示す脱脂条件により８００℃まで昇温し、８００℃で
１時間保持後、約２７０℃／時間の割合で室温まで降温
して脱脂処理を行った。その後、通常条件に従い１６２
０℃で２０分間保持して焼成処理を行いベータアルミナ
管の焼結体を得た。なお表１中、酸素濃度とは脱脂炉内
における酸素の体積率（vol ％）を、加熱所要時間とは
室温から３００℃まで均一に昇温するのに要する時間を
いう。得られたベータアルミナ管の寸法基準値を越える
不良率は表１に示すとおりであり、比較例に示した従来
方法に対して本発明の優れた効果が確認できた。[Example] To a dry powder of a beta-alumina raw material, 5% by weight of polyethylene glycol as an organic binder was added together with water to form a slurry, and the slurry was granulated using a spray dryer. Thus, a bottomed cylindrical beta-alumina molded body having an outer diameter of 45 mm, an inner diameter of 40 mm and a length of 450 mm was produced at a molding pressure of 2.2 ton / cm 2 . Each of the thus-obtained beta-alumina compacts was placed in an outside air-introducing degreasing electric furnace, and 100 of each of them were prepared in Table 1.
The temperature was raised to 800 ° C. under the degreasing conditions shown in (1), held at 800 ° C. for 1 hour, and then lowered to room temperature at a rate of about 270 ° C./hour for degreasing treatment. Then 162 according to normal conditions
The mixture was held at 0 ° C. for 20 minutes for firing treatment to obtain a sintered body of beta-alumina tube. In Table 1, the oxygen concentration means the volume ratio (vol%) of oxygen in the degreasing furnace, and the heating required time means the time required to uniformly increase the temperature from room temperature to 300 ° C. The defective rate of the obtained beta-alumina tube exceeding the dimensional standard value is as shown in Table 1, and the excellent effect of the present invention could be confirmed over the conventional method shown in the comparative example.
【表１】 [Table 1]
【００１３】[0013]
【発明の効果】以上の説明からも明らかなように本発明
においては、有機バインダーの完全燃焼が行われて脱脂
不足を生ずることがなく、また、急激な有機バインダー
の分解を阻止して脱脂品にキレを発生させることもなく
焼成後に所定寸法どおりの一端を開口部とする有底筒状
のベータアルミナ管を精度よく、かつ歩留りよく生産す
ることができるものであり、更には、従来の脱脂炉や焼
成炉に何等改良等を加えることなくそのまま使用するこ
とができるもので、優れた経済性も有するという利点も
ある。よって、本発明は従来の問題点を一掃したベータ
アルミナ管の製造方法として産業の発展に寄与するとこ
ろは極めて大である。As is clear from the above description, in the present invention, the organic binder is not completely burned to cause insufficient degreasing, and abrupt decomposition of the organic binder is prevented to prevent degreasing. A cylindrical shape with a bottom that opens at one end of the specified dimensions after firing without causing any cracks
The beta-alumina tube of can be produced with high accuracy and yield, and can be used as it is without adding any modification to the conventional degreasing furnace or firing furnace, which is excellent in economic efficiency. There is also an advantage of having the property. Therefore, the present invention greatly contributes to the industrial development as a method for producing a beta-alumina tube that eliminates the conventional problems.
Claims (1)
たベータアルミナ成形体を、前記開口部の開口率が１０
％以上に開放された状態として室温から３００℃まで炉
内酸素濃度が１８％以上の雰囲気中で６０分以上脱脂処
理した後焼成処理を施すことを特徴とするベータアルミ
ナ管の製造方法。1. A beta-alumina molded body having a bottomed cylindrical shape having an opening at one end , wherein the opening ratio of the opening is 10
%, The method for producing a beta-alumina tube is characterized by performing degreasing treatment for 60 minutes or more in an atmosphere in which the oxygen concentration in the furnace is 18% or more from room temperature to 300 ° C. and then performing firing treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3076833A JPH0735294B2 (en) | 1991-03-15 | 1991-03-15 | Beta-alumina tube manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3076833A JPH0735294B2 (en) | 1991-03-15 | 1991-03-15 | Beta-alumina tube manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04285062A JPH04285062A (en) | 1992-10-09 |
| JPH0735294B2 true JPH0735294B2 (en) | 1995-04-19 |
Family
ID=13616680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3076833A Expired - Lifetime JPH0735294B2 (en) | 1991-03-15 | 1991-03-15 | Beta-alumina tube manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0735294B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1583123A1 (en) | 2004-04-01 | 2005-10-05 | Eja Limited | Safety switch assembly |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5717468A (en) * | 1980-06-30 | 1982-01-29 | Toyota Motor Co Ltd | Manufacture of ceramic sintered body |
-
1991
- 1991-03-15 JP JP3076833A patent/JPH0735294B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1583123A1 (en) | 2004-04-01 | 2005-10-05 | Eja Limited | Safety switch assembly |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04285062A (en) | 1992-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2282264C2 (en) | Method for production of niobium oxide | |
| JP6530640B2 (en) | Method of treating positive electrode active material for lithium secondary battery | |
| US3625765A (en) | Production of battery electrode | |
| CN109860753A (en) | A method for roasting positive and negative electrode materials of waste and old lithium ion batteries | |
| RU2335382C2 (en) | Electrode for surface treatment with electric charge, method of its production and storage | |
| JPH0735294B2 (en) | Beta-alumina tube manufacturing method | |
| KR20200045794A (en) | Lead-acid battery with activated carbon powder additive | |
| JPH0694389B2 (en) | Beta-alumina tube manufacturing method | |
| KR101195448B1 (en) | Preparation method of sintered porous plate using spent nuclear fuel, and the sintered porous plate thereby | |
| JPH08273669A (en) | Method for producing positive electrode for non-aqueous electrolyte battery | |
| JP3794123B2 (en) | Method for producing lanthanum manganite ceramic | |
| CN114956816A (en) | High-performance pyrochlore energy storage ceramic material and preparation method and application thereof | |
| JP2610701B2 (en) | Ceramic tube firing method | |
| RU2701542C1 (en) | Method of pelletised fuel production for nuclear reactors fuel elements | |
| KR102855308B1 (en) | artificial graphite negative electrode material and manufacturing method thereof | |
| SU1211244A1 (en) | Method of producing ceramic material for solid electrolyte | |
| RU1804623C (en) | Method of manufacturing solid-electrolyte oxygen sensor | |
| JP2610350B2 (en) | Method for forming beta-alumina tube for sodium-sulfur battery | |
| US1637052A (en) | Process of producing metallic carbon | |
| US20030164570A1 (en) | Method for decarburizing ceramic moulded bodies | |
| JP2003112910A (en) | Method for hydrophilizing carbon molded body | |
| JPH0788830A (en) | Manufacturing method of bottomed ceramics tube and manufacturing die | |
| PL449931A1 (en) | Method of producing activated carbon from Caucasian fir waste wood by chemical activation of the said raw material, activated carbon produced by this method and electrochemical supercapacitor containing it | |
| JP2000028569A (en) | Method for manufacturing oxygen sensor element | |
| JPH03201360A (en) | Manufacture of positive electrode mixture for manganese dry cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 19951003 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090419 Year of fee payment: 14 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100419 Year of fee payment: 15 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100419 Year of fee payment: 15 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110419 Year of fee payment: 16 |
|
| EXPY | Cancellation because of completion of term |