JPS63318074A - Electrolyte feeding method for molten carbonate fuel cell - Google Patents
Electrolyte feeding method for molten carbonate fuel cellInfo
- Publication number
- JPS63318074A JPS63318074A JP62153741A JP15374187A JPS63318074A JP S63318074 A JPS63318074 A JP S63318074A JP 62153741 A JP62153741 A JP 62153741A JP 15374187 A JP15374187 A JP 15374187A JP S63318074 A JPS63318074 A JP S63318074A
- Authority
- JP
- Japan
- Prior art keywords
- carbonate
- lithium carbonate
- cell
- temperature
- electrolyte
- 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.)
- Granted
Links
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 28
- 239000003792 electrolyte Substances 0.000 title claims abstract description 25
- 239000000446 fuel Substances 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 22
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 20
- 238000002844 melting Methods 0.000 claims abstract description 19
- 230000008018 melting Effects 0.000 claims abstract description 19
- 238000007789 sealing Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- -1 O3 are used Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000112 cooling gas Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001052 transient effect Effects 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
-
- 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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04276—Arrangements for managing the electrolyte stream, e.g. heat exchange
- H01M8/04283—Supply means of electrolyte to or in matrix-fuel cells
-
- 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
- H01M8/14—Fuel cells with fused electrolytes
- H01M8/141—Fuel cells with fused electrolytes the anode and the cathode being gas-permeable electrodes or electrode layers
- H01M8/142—Fuel cells with fused electrolytes the anode and the cathode being gas-permeable electrodes or electrode layers with matrix-supported or semi-solid matrix-reinforced electrolyte
-
- 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
- H01M8/14—Fuel cells with fused electrolytes
- H01M2008/147—Fuel cells with molten carbonates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0048—Molten electrolytes used at high temperature
- H01M2300/0051—Carbonates
-
- 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
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)
- Fuel Cell (AREA)
Abstract
Description
【発明の詳細な説明】
イフ 産業上の利用分野
本発明は溶融炭酸塩燃料”酸油における炭酸塩電解質の
補給方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for replenishing carbonate electrolyte in molten carbonate fuel "acid oil".
（ロ）従来の技術
溶融炭酸塩型燃料電池の電解質に、ＬｉｚＣＯζＫｚＣ
Ｏ３などの炭酸塩が用いらｎるが、電池作動中溶融状態
の炭酸塩が蒸発や漏出により失はれて電池特性の劣下全
もたらすと共に、電解質板周辺部と接するセル枠のシー
ル面が、溶融炭酸塩に侵されて前記漏出を一層促進する
ことになる。(b) LizCOζKzC is used as the electrolyte of the conventional molten carbonate fuel cell.
Carbonates such as O3 are used, but during battery operation, molten carbonates are lost due to evaporation or leakage, resulting in a total deterioration of battery characteristics and the sealing surface of the cell frame in contact with the periphery of the electrolyte plate. , which will be attacked by molten carbonate and further promote the leakage.
したがって電池寿命の延長と特性低下の防止を図るため
に、炭識塩ｔ−電解質仮に補給することが必要となる。Therefore, in order to extend the life of the battery and prevent deterioration of its characteristics, it is necessary to temporarily replenish the carbonaceous salt t-electrolyte.
通常セル枠のシール面に設けた溜溝に補給用の電解質ｔ
−溜めておく方法が採用されるが、電池作動中この補給
用炭酸塩も溶融状態にあるため溜溝が腐蝕して補給が確
実に行はｎ難いという問題があった。Normally, the electrolyte t for replenishment is placed in the reservoir groove provided on the sealing surface of the cell frame.
- A method of storing the carbonate is adopted, but since the carbonate for replenishment is also in a molten state during battery operation, the reservoir groove corrodes and it is difficult to replenish the replenishment reliably.
（ハ）発明が解決しようとする問題点
この発明は電池作動中溶融炭酸塩による溜溝の腐蝕？防
止すると同時に電解質の補給金円滑・確実に行う方ｌＥ
、全提供するものである。(c) Problems to be solved by the invention Does this invention solve the problem of corrosion of the reservoir groove by molten carbonate during battery operation? How to prevent this and at the same time ensure smooth and reliable electrolyte replenishment lE
, all we offer.
に）問題点全解決するだめの手段
この発明はＬｉ／に系混合炭酸塩を含有する電解質板の
周辺部全上下セル枠のシール面で封止し、前記上セル枠
のシール面に形設した凹溝に、融点が電池作動温度より
高い炭酸リチウム全保持し、補給時電池温度を一時的に
前記融点以上に昇温することによ勺前記炭酸すチクム全
溶融して前記混合炭酸塩に混入せしめるものである。B) Means to solve all the problems This invention involves sealing the entire periphery of an electrolyte plate containing a Li/based mixed carbonate with the sealing surfaces of the upper and lower cell frames, and forming a seal on the sealing surface of the upper cell frame. All of the lithium carbonate, whose melting point is higher than the battery operating temperature, is held in the groove, and by temporarily raising the battery temperature above the melting point during replenishment, the lithium carbonate is completely melted and turned into the mixed carbonate. It is something that causes it to be mixed in.
（ホ）作 用
この発明では凹溝に保持さ扛た炭酸リチウムは、電池作
動中溶融しないで固相状態ｆ：Ｍ持するので、青金腐蝕
するおそｎなく、補給が必要なとき電池温度を一時的に
昇温すれば炭酸リチウムが溶融して電解質の補給が行は
在る。(E) Function In this invention, the lithium carbonate held in the groove does not melt during battery operation and maintains a solid state f:M, so there is no risk of corrosion of the blue metal, and the temperature of the battery when replenishment is required. If the temperature is temporarily raised, the lithium carbonate will melt and the electrolyte will be replenished.
（へ）実施例
第１図は本発明による溶融炭酸塩型燃料電池の断面図で
、簡単化のため単セルとして示した。(f) Example FIG. 1 is a sectional view of a molten carbonate fuel cell according to the present invention, which is shown as a single cell for simplicity.
電解質板［１１は、リチウムアルミネートヲ保持材とし
−（Ｌｉ／に系の混合炭酸塩全含浸し、燃料極（２）と
酸化剤極（３）との開に介在している。６極（２Ｊ （
３］は集電板（４）ヲ介してステンレス製上下セル枠（
５）（６）によシ押しつＣすらｎると共に電解質板（１
）の周辺部は上下セル枠（５）（６）のシール面により
封止さｔている。The electrolyte plate [11 is made of lithium aluminate as a holding material and is completely impregnated with mixed carbonate of Li/ system, and is interposed between the fuel electrode (2) and the oxidizer electrode (3). 6 electrodes. (2J (
3] is a stainless steel upper and lower cell frame (
5) After pressing (6), press the electrolyte plate (1)
) are sealed by the sealing surfaces of the upper and lower cell frames (5) and (6).
この上セル枠（５）のシール面に形設した凹溝（力には
、電池作動温度（約６５０℃）で固相状態全維持する補
給用炭酸ｙ＋ウム（８）〔融点７２３℃〕 が粉末状も
しくに固形状で充填もしくは収納さ牡ている。The recessed groove formed in the sealing surface of the upper cell frame (5) contains replenishing y+ium carbonate (8) [melting point 723°C] that maintains its solid state at the battery operating temperature (approximately 650°C). It is packed or stored in powder or solid form.
周知のように炭酸塩はその融点までは固体で娶るが、融
点以上になると溶融して無色・透明のかなり粘度の低い
液体となる。ＳＮ２図はＬｌ−に系炭酸塩の固・液相状
態図全示し、Ｌｉ２ＣＯ３／に２Ｃｏ ｓ＝６２／３８
ｍｏ ／ ９６のものが共融組成の中で最も融点が低く
（４９１℃〕、Ｌｉ ｚｃＯｓのｍｏ／％が４ｚ以下及
び６２以上となるといづｎも溶融温度が上昇する。又図
より明らかなようＫＫｚＣＯ３のみ及びＬ１２ＣＯ５の
みの場合の融点に夫々９００℃及び７２３℃でめる。As is well known, carbonates are solids up to their melting point, but when the temperature rises above their melting point, they melt into a colorless, transparent liquid with a fairly low viscosity. The SN2 diagram shows the entire solid-liquid phase diagram of carbonate in Ll- system, Li2CO3/2Co s=62/38
The one with mo/96 has the lowest melting point (491°C) among the eutectic compositions, and when the mo/% of LizcOs becomes 4z or less and 62 or more, the melting temperature increases.Also, as is clear from the figure. The melting points for KKzCO3 only and L12CO5 only are reached at 900°C and 723°C, respectively.
本発明では補給用炭酸塩とし工炭酸すチワム単独で用い
た。補給用炭酸リチウム（８）は電池作動温度（約６５
０℃〕では溶融せず固体のま＼であり、電解質板（１）
への補給が必要となった時点で一時的に電池温度を７２
３℃以上に昇温して、溶融させることで補給が行はれる
。補給終了時点で作動温度１／（降温するが、この昇温
−降温ぼあくまで過渡的なもの（たかだか２〜３時間ン
であり、電池特性に与える影響は殆どない。この電池の
温度の一時的昇温に、冷却ガス流１ｔｔ−低減して冷却
能全低下させればよい。In the present invention, engineered carbonate was used alone as a supplementary carbonate. Replenishment lithium carbonate (8) is at battery operating temperature (approximately 65
0℃], it does not melt and remains solid, and the electrolyte plate (1)
Temporarily lower the battery temperature to 72℃ when it becomes necessary to replenish the battery.
Replenishment is performed by raising the temperature to 3°C or higher and melting it. At the end of replenishment, the operating temperature decreases by 1/(temperature decreases, but this temperature increase-temperature decrease is strictly transient (2 to 3 hours at most, and has almost no effect on battery characteristics. To increase the temperature, the cooling gas flow may be reduced by 1 tt to completely reduce the cooling capacity.
尚炭酸リチウムのみが補給さｎるので、電解質板（１）
全体の電解質組成が多少Ｌｌリツｙ−側に移行するが、
その補給量が全電解質量比しわづかであって電池作動温
度が６５０℃に復元しても溶融状態？維持する。もし補
給」ｌによる組成変化が無視し得ない場合電解質板（１
）ｉＣ予め含浸式ｎた炭酸塩は通常ノＬ ｉ ２ ＣＯ
ｓ ／Ｋ ２ Ｃ○５＝６２／３８ｍ０１９６よすＬｌ
の少い例えばＬｉ２ＣＯ３／ＫｚＣＯｓ＝５０１５０ｍ
ｏ／９６の組成のものを用いｎばよい。Since only lithium carbonate is being replenished, the electrolyte plate (1)
Although the overall electrolyte composition shifts somewhat to the Ll-ly-side,
Even if the amount of replenishment is small compared to the total electrolyte mass and the battery operating temperature is restored to 650°C, is it in a molten state? maintain. If the composition change due to replenishment cannot be ignored, the electrolyte plate (1
) iC pre-impregnated carbonate is usually used as i2CO
s /K 2 C○5=62/38m0196YosLl
For example, Li2CO3/KzCOs=50150m
It is sufficient to use one having a composition of o/96.
（トノ発明の効果
本発明によｎば凹溝に保持さｔした補給用炭酸塩が、融
点の高い炭酸リチウム単独であるから、電池作動温度で
は固相を保って溶融しないため凹ｐｔｔ腐蝕するおそｎ
なく、補給の必要なとき電池温度全一時的に昇温するこ
とで、炭酸リチウム全溶融して電解質板中の混合炭酸塩
に混入さ扛るので、補給が支障なく確央に行ｉ”ｔｎる
。(Effects of the Invention According to the present invention, since the replenishing carbonate held in the groove is lithium carbonate alone, which has a high melting point, it maintains a solid phase and does not melt at the battery operating temperature, causing corrosion of the depression. Oson
By temporarily raising the battery temperature when replenishment is required, lithium carbonate is completely melted and mixed into the mixed carbonate in the electrolyte plate, so replenishment can be carried out without any problems. Ru.
第１図は本発明による溶融炭酸塩燃料電池の断面図、第
２図はＬｉ−に系混合炭酸塩の固・液相状態を示す特性
図である。
（１）：電解質板、（２）：燃料極、（３）：酸化剤極
、（５）（６）：上下セル枠、（７）：凹溝、（８）：
補給用炭酸リチウムFIG. 1 is a sectional view of a molten carbonate fuel cell according to the present invention, and FIG. 2 is a characteristic diagram showing the solid and liquid phase states of a Li-based mixed carbonate. (1): Electrolyte plate, (2): Fuel electrode, (3): Oxidizer electrode, (5) (6): Upper and lower cell frames, (7): Concave groove, (8):
Replenishment lithium carbonate
Claims (2)
部を上下各セル枠のシール面で封止し、前記上セル枠の
シール面に形設した凹溝に、融点が電池作動温度より高
い炭酸リチウムを保持してなり、電解質の補給時電池温
度を一時的に前記融点以上に昇温することにより前記炭
酸リチウムを溶融して前記混合炭酸塩に混入せしめるこ
とを特徴とする溶融炭酸塩燃料電池の電解質補給方法。(1) The periphery of the electrolyte plate containing Li/K mixed carbonate is sealed with the sealing surfaces of the upper and lower cell frames, and the melting point is set in the groove formed in the sealing surface of the upper cell frame. Melting characterized by holding lithium carbonate at a temperature higher than the temperature, and melting the lithium carbonate and mixing it into the mixed carbonate by temporarily raising the battery temperature to the melting point or higher when replenishing the electrolyte. Electrolyte replenishment method for carbonate fuel cells.
行はれることを特徴とする特許請求の範囲第１項記載の
溶融炭酸塩燃料電池の電解質補給方法。(2) The electrolyte replenishment method for a molten carbonate fuel cell according to claim 1, wherein the temperature increase of the cell is carried out by lowering the cooling capacity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62153741A JPH0665047B2 (en) | 1987-06-19 | 1987-06-19 | Molten carbonate fuel cell electrolyte replenishment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62153741A JPH0665047B2 (en) | 1987-06-19 | 1987-06-19 | Molten carbonate fuel cell electrolyte replenishment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63318074A true JPS63318074A (en) | 1988-12-26 |
| JPH0665047B2 JPH0665047B2 (en) | 1994-08-22 |
Family
ID=15569094
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62153741A Expired - Fee Related JPH0665047B2 (en) | 1987-06-19 | 1987-06-19 | Molten carbonate fuel cell electrolyte replenishment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0665047B2 (en) |
-
1987
- 1987-06-19 JP JP62153741A patent/JPH0665047B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0665047B2 (en) | 1994-08-22 |
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| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |