JPS63151615A - Production of lithium aluminate fiber - Google Patents
Production of lithium aluminate fiberInfo
- Publication number
- JPS63151615A JPS63151615A JP61299186A JP29918686A JPS63151615A JP S63151615 A JPS63151615 A JP S63151615A JP 61299186 A JP61299186 A JP 61299186A JP 29918686 A JP29918686 A JP 29918686A JP S63151615 A JPS63151615 A JP S63151615A
- Authority
- JP
- Japan
- Prior art keywords
- fibers
- lithium aluminate
- lithium
- holding material
- alumina
- 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.)
- Pending
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 36
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 38
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000000446 fuel Substances 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 4
- 230000004907 flux Effects 0.000 abstract description 3
- 150000001339 alkali metal compounds Chemical class 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- HCQWRNRRURULEY-UHFFFAOYSA-L lithium;potassium;dichloride Chemical compound [Li+].[Cl-].[Cl-].[K+] HCQWRNRRURULEY-UHFFFAOYSA-L 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0289—Means for holding the electrolyte
- H01M8/0295—Matrices for immobilising electrolyte melts
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Inorganic Fibers (AREA)
- Fuel Cell (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は溶融塩燃料電池の電解質保持材として最適なリ
チウムアルミネート繊維の製造方法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing lithium aluminate fibers that are most suitable as an electrolyte holding material for molten salt fuel cells.
炭酸塩の溶融物を電解質として用いる燃料電池の電解質
保持材として電解質に対する安定性の高いリチウムアル
ミネートが注目されている。Lithium aluminate, which has high stability against electrolytes, is attracting attention as an electrolyte holding material for fuel cells that use a molten carbonate as an electrolyte.
このリチウムアルミネートは通常多孔質の焼結体として
使用されるが、電解質の充填量、イオン透過性、電子伝
導性および強度を十分に満足させる多孔体を得るには、
従来の粒状のリチウムアルミネートを焼結させたもので
は不十分である。This lithium aluminate is usually used as a porous sintered body, but in order to obtain a porous body that satisfies the electrolyte filling amount, ion permeability, electronic conductivity, and strength.
Conventional sintered granular lithium aluminate is insufficient.
リチウムアルミネートにはα、β、γ型の３種の結晶形
態が知られているが、このうちα型とγ型は粒状であり
、β型に繊維状のものが知られていた。最近γ型の繊維
状のものの合成が発表されている。この繊維状のリチウ
ムアルミネートを用いれば、繊維の絡み合いにより多孔
質であっても焼結体の強度は飛躍的に増大するはずであ
る。Three types of crystal forms are known for lithium aluminate: α, β, and γ types. Among these, the α type and γ type are granular, and the β type is known to be fibrous. Recently, the synthesis of γ-type fibrous materials has been announced. If this fibrous lithium aluminate is used, the strength of the sintered body should be dramatically increased even if it is porous due to the entanglement of the fibers.
特開昭６０−６５７１９号公報で開示されている製造方
法によれば、酸化アルミニウムあるいはその水和物と水
酸化リチウムから塩化リチウム−塩化カリウム系の融剤
を使用してリチウムアルミネートの繊維状のものを得て
いるが、このリチウムアルミネートは繊維状であっても
繊維長は４μｍ程度であり、繊維としては短かすぎて多
孔体の強度の向上には十分には寄与しないものであった
。According to the manufacturing method disclosed in JP-A-60-65719, fibrous lithium aluminate is produced from aluminum oxide or its hydrate and lithium hydroxide using a lithium chloride-potassium chloride flux. However, even if this lithium aluminate is in the form of fibers, the fiber length is about 4 μm, which is too short to be a fiber and does not contribute enough to improving the strength of the porous body. Ta.
本発明のリチウムアルミネート繊維の製造方法では特別
な融剤を用いず、Ｔ−アルミナ１モルに対し水酸化リチ
ウム５〜１２モルの割合で混合した原料を４００〜ｓｏ
ｏ ”ｃの温度で１５分〜５０時間加熱するだけで、繊
維長が１０〜２０μｍと従来知られているよりはかなり
長いリチウムアルミネート繊維が得られるものである。The method for producing lithium aluminate fibers of the present invention does not use any special fluxing agent, but uses raw materials mixed at a ratio of 5 to 12 moles of lithium hydroxide to 1 mole of T-alumina at a concentration of 400 to so.
Lithium aluminate fibers having a fiber length of 10 to 20 μm, which is considerably longer than conventionally known, can be obtained by simply heating at a temperature of 0 ”c for 15 minutes to 50 hours.
本発明に用いられるアルミナはγ型であり、例えば水酸
化アルミニウムの沈澱を１０００℃以゛下の温度で仮焼
したものが用いられる。The alumina used in the present invention is of the γ type, and for example, aluminum hydroxide precipitate calcined at a temperature of 1000° C. or lower is used.
水酸化リチウムは無水物（ＬｉＯＨ）でも水和物（Ｌｉ
ＯＨ−Ｈ２Ｏ）でもよいが、特に水和物を用いると好結
果が得られる。その使用量はアルミナ１モルに対し水酸
化リチウムを５〜１２モル、好ましくは６〜１０モルと
する。本発明ではこの水酸化リチウムを多量に使用する
点に特徴があり、これによってリチウムアルミネートの
長い繊維が得られるのである。この水酸化リチウムの割
合が５モル未満ではリチウムアルミネート繊維とならず
、また１２モル以上では長さは変わらず、繊維が太（な
り、アスペクト比が低下して電解質保持材として使用し
た際に十分な補強効果が得られなくなる。Lithium hydroxide is anhydrous (LiOH) and hydrated (Li
OH-H2O) may be used, but particularly good results are obtained when a hydrate is used. The amount of lithium hydroxide used is 5 to 12 moles, preferably 6 to 10 moles, per mole of alumina. The present invention is characterized by the use of a large amount of lithium hydroxide, which allows long fibers of lithium aluminate to be obtained. If the proportion of lithium hydroxide is less than 5 moles, lithium aluminate fibers will not be formed, and if the proportion is more than 12 moles, the length will not change, the fibers will become thick (and the aspect ratio will decrease, and when used as an electrolyte holding material) A sufficient reinforcing effect cannot be obtained.
秤量したγ−アルミナと水酸化リチウムを十分混合、混
練後加圧成形する。なお、混練したま＼でも、あるいは
原料混合物に水を加えてペースト状としたものを用いて
もよい。これを電気炉などの適当な加熱装置中で、４０
０〜８００℃、好ましくは５００〜７００℃の温度で１
５分〜５０時間、好ましくは１〜２０時間加熱して繊維
を発達させる。この加熱温度が４００℃未満では繊維と
ならず、８００℃以上ではリチウムアルミネートが塊状
となりいずれも好ましくない。また、加熱時間が１５分
未満では時間が短かすぎて繊維が発達せず、逆に５０時
間以上となると次第に生成した繊維が融着して太（なっ
てしまう。The weighed γ-alumina and lithium hydroxide are thoroughly mixed, kneaded, and then pressure-molded. Note that the mixture may be used either as it is kneaded or as a paste by adding water to the raw material mixture. Heat this in a suitable heating device such as an electric furnace for 40 minutes.
1 at a temperature of 0 to 800°C, preferably 500 to 700°C.
Fibers are developed by heating for 5 minutes to 50 hours, preferably 1 to 20 hours. If the heating temperature is lower than 400°C, the fibers will not form, and if the heating temperature is higher than 800°C, the lithium aluminate will become lumpy, which is not preferable. Furthermore, if the heating time is less than 15 minutes, the time is too short and the fibers will not develop, and if the heating time is more than 50 hours, the fibers formed will gradually fuse and become thick.
こうしてリチウムアルミネートとリチウム化合物の混合
物が得られるが、冷却後水で洗浄することにより長さ１
０〜２０μｍ１直径０．７〜１μｍのリチウムアルミネ
ート繊維を得ることができる。In this way, a mixture of lithium aluminate and lithium compound is obtained, and by washing with water after cooling, the mixture has a length of 1
Lithium aluminate fibers having a diameter of 0 to 20 μm and a diameter of 0.7 to 1 μm can be obtained.
第１表に示す配合を十分混合、混練後圧線成形し、表に
示した温度、時間で電気炉中で焼成しリチウムアルミネ
ート繊維を得た。得られた繊維はすべてβ型であり、そ
の繊維長、繊維径およびアスペクト比の測定値を第１表
に示す。The formulations shown in Table 1 were thoroughly mixed and kneaded, then wire-formed and fired in an electric furnace at the temperature and time shown in the table to obtain lithium aluminate fibers. All of the obtained fibers were of the β type, and the measured values of the fiber length, fiber diameter, and aspect ratio are shown in Table 1.
本発明のγ−アルミナと水酸化リチウムを用いたリチウ
ムアルミネート繊維の製造方法によれば第１表にみられ
るように、従来の製造方法のように融剤としてのアルカ
リ金属化合物を必要とせずに、単に使用する水酸化リチ
ウムの量を多くしただけで繊維長の大きい、アスペクト
比の大きいリチウムアルミネート繊維を得ることができ
た。According to the method for producing lithium aluminate fibers using γ-alumina and lithium hydroxide of the present invention, as shown in Table 1, there is no need for an alkali metal compound as a flux unlike in the conventional production method. In addition, it was possible to obtain lithium aluminate fibers with a large fiber length and a large aspect ratio simply by increasing the amount of lithium hydroxide used.
この繊維は溶融塩燃料電池の電解質保持材として使用し
た場合に、従来知られているリチウムアルミネート繊維
より繊維が長く、しかもアスペクト比も大であるので、
繊維の絡み合いが太き（、従って、多孔質の焼結体とし
ても強度の大きい電解質保持材を得ることができるもの
である。When this fiber is used as an electrolyte holding material in molten salt fuel cells, it has longer fibers and a larger aspect ratio than conventionally known lithium aluminate fibers, so
The entanglement of fibers is thick (therefore, an electrolyte holding material with high strength can be obtained even as a porous sintered body).
手続補正書 昭和６３年１月２６日Procedural amendment January 26, 1986
Claims (1)
の割合で混合した原料を４００〜８００℃の温度で１５
分〜５０時間加熱することを特徴とするリチウムアルミ
ネート繊維の製造方法。Raw materials mixed at a ratio of 5 to 12 moles of lithium hydroxide to 1 mole of γ-alumina are heated at a temperature of 400 to 800°C for 15 minutes.
A method for producing lithium aluminate fibers, the method comprising heating for 50 minutes to 50 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61299186A JPS63151615A (en) | 1986-12-15 | 1986-12-15 | Production of lithium aluminate fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61299186A JPS63151615A (en) | 1986-12-15 | 1986-12-15 | Production of lithium aluminate fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63151615A true JPS63151615A (en) | 1988-06-24 |
Family
ID=17869255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61299186A Pending JPS63151615A (en) | 1986-12-15 | 1986-12-15 | Production of lithium aluminate fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63151615A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02271911A (en) * | 1989-04-12 | 1990-11-06 | Ishikawajima Harima Heavy Ind Co Ltd | Production of porous lithium aluminate fiber |
| US5827495A (en) * | 1995-10-03 | 1998-10-27 | Kabushiki Kaisha Toshiba | Molten carbonate fuel cell and method of manufacturing retaining material for electrolyte body of molten carbonate fuel cell |
| US6340454B1 (en) * | 1998-12-28 | 2002-01-22 | Nippon Chemical Industries Co., Ltd. | α-Lithium aluminate and method of manufacturing the same, and electrolyte support material of molten carbonate fuel cell |
-
1986
- 1986-12-15 JP JP61299186A patent/JPS63151615A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02271911A (en) * | 1989-04-12 | 1990-11-06 | Ishikawajima Harima Heavy Ind Co Ltd | Production of porous lithium aluminate fiber |
| WO1992004496A1 (en) * | 1989-04-12 | 1992-03-19 | Ishikawajima-Harima Heavy Industries Co., Ltd. | Method of producing porous lithium aluminate fiber and coarse particle |
| US5827495A (en) * | 1995-10-03 | 1998-10-27 | Kabushiki Kaisha Toshiba | Molten carbonate fuel cell and method of manufacturing retaining material for electrolyte body of molten carbonate fuel cell |
| US6037076A (en) * | 1995-10-03 | 2000-03-14 | Kabushiki Kaisha Toshiba | Molten carbonate fuel cell and method of manufacturing retaining material for electrolyte body of molten carbonate fuel cell |
| US6340454B1 (en) * | 1998-12-28 | 2002-01-22 | Nippon Chemical Industries Co., Ltd. | α-Lithium aluminate and method of manufacturing the same, and electrolyte support material of molten carbonate fuel cell |
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