JPH0335777B2 - - Google Patents
Info
- Publication number
- JPH0335777B2 JPH0335777B2 JP59014435A JP1443584A JPH0335777B2 JP H0335777 B2 JPH0335777 B2 JP H0335777B2 JP 59014435 A JP59014435 A JP 59014435A JP 1443584 A JP1443584 A JP 1443584A JP H0335777 B2 JPH0335777 B2 JP H0335777B2
- Authority
- JP
- Japan
- Prior art keywords
- carbonate
- reaction
- electrolyte
- present
- holding material
- 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
- 239000000463 material Substances 0.000 claims description 22
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 21
- 239000003792 electrolyte Substances 0.000 claims description 12
- 239000000446 fuel Substances 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000001721 carbon Chemical class 0.000 claims 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000003247 decreasing effect Effects 0.000 description 9
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 LaBO 3 Chemical compound 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 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
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)
Description
【発明の詳細な説明】
［発明の技術分野］
本発明は、炭酸塩の優れた保持機能を長期に亘
つて維持できる溶融炭酸塩燃料電池の電解質保持
材に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to an electrolyte retention material for a molten carbonate fuel cell that can maintain an excellent carbonate retention function over a long period of time.
［発明の技術的背景とその問題点］
従来、高能率のエネルギ変換装置として燃料電
池が広く知られている。燃料電池は、使用する電
解質によつて、リン酸塩型、溶融炭酸塩型、固体
電解質型に分類される。なかでも、溶融炭酸塩燃
料電池は、動作温度が高いため、電極反応が起こ
り易く、高価な貴金属触媒を必要としないこと、
また発電熱効率が高いことなどの大きな特徴を有
している。[Technical background of the invention and its problems] Fuel cells have been widely known as a highly efficient energy conversion device. Fuel cells are classified into phosphate type, molten carbonate type, and solid electrolyte type depending on the electrolyte used. Among these, molten carbonate fuel cells have high operating temperatures that allow electrode reactions to occur easily and do not require expensive precious metal catalysts.
It also has great features such as high heat generation efficiency.
このような溶融炭酸塩燃料電池は、通常、対抗
配置された一対の多孔質電極板、すなわち酸化剤
極および燃料極と、これら電極間に介在させたア
ルカリ炭酸塩を電解質とする電解質層とからなる
単位電池を通常、インタコネクタを介して複数積
層して構成されている。そして運転時において
は、上記アルカリ炭素塩を500〜750℃の高温下で
溶融状態にし、この炭酸塩と、各電極板にそれぞ
れ拡散された酸化剤ガスおよび燃料ガスとを反応
させて、電気化学的プロセスによつて直流出力を
得るようにしている。 Such molten carbonate fuel cells typically consist of a pair of opposed porous electrode plates, namely an oxidizer electrode and a fuel electrode, and an electrolyte layer containing an alkali carbonate as an electrolyte interposed between these electrodes. Usually, a plurality of unit batteries are stacked together via interconnectors. During operation, the alkali carbonate is molten at a high temperature of 500 to 750°C, and this carbonate is reacted with the oxidant gas and fuel gas diffused in each electrode plate, resulting in an electrochemical reaction. DC output is obtained through a process of
ところで、このような溶融炭酸塩燃料電池の電
解質層は、溶融状態の炭酸塩を用いるので、炭酸
塩と、これを保持する保持剤とで形成されてい
る。保持剤としては、従来、例えば粉末状のジル
コニア、チタン酸カリウム、アルミナ、アルミン
酸リチウム等が用いられていた。 Incidentally, since the electrolyte layer of such a molten carbonate fuel cell uses carbonate in a molten state, it is formed of carbonate and a holding agent that holds it. Conventionally, powdered zirconia, potassium titanate, alumina, lithium aluminate, etc. have been used as the retaining agent.
しかしながら、ジルコニアやチタン酸カリウム
は、強力な溶解力を有する炭酸塩に対して十分な
化学的安定性を有するものではないため、長時間
の運転による電解質保持能力の低下は否めなかつ
た。 However, since zirconia and potassium titanate do not have sufficient chemical stability against carbonates, which have a strong dissolving power, it is unavoidable that the electrolyte retention ability deteriorates due to long-term operation.
また、アルミナやアルミン酸リチウムは、溶融
炭酸塩との反応により粒成長を起こすので、炭酸
塩の密度の経時的低下をもたらし、電池特性の低
下を招く。 Furthermore, since alumina and lithium aluminate cause grain growth due to reaction with molten carbonate, the density of carbonate decreases over time, leading to deterioration of battery characteristics.
これらの保持材にあつて、アルミン酸リチウム
は、炭酸塩に対する化学的安定性が最も高い。こ
のような理由から現在のところ炭酸塩の保持材と
して、専らアルミン酸リチウムが使用されてい
る。 Among these holding materials, lithium aluminate has the highest chemical stability against carbonates. For these reasons, lithium aluminate is currently exclusively used as a carbonate retention material.
しかし、アルミン酸リチウムは前述の如く粒成
長を起こす性質を有しているので、アルミン酸リ
チウムに替わる保持材の出現が望まれているるの
が実情である。 However, since lithium aluminate has the property of causing grain growth as described above, the reality is that there is a desire for a retaining material to replace lithium aluminate.
［発明の目的］
本発明は、かかる点に鑑みてなされたものであ
り、その目的とするところは、炭酸塩を長期に亘
つて安定に保持することのできる溶融炭酸燃料電
池の炭酸塩保持材を提供することにある。[Object of the Invention] The present invention has been made in view of the above points, and its purpose is to provide a carbonate retaining material for a molten carbonate fuel cell that can stably retain carbonate over a long period of time. Our goal is to provide the following.
［発明の概要］
本発明に係る電解質保持材は希土類元素と硼素
とを含む複合酸化物からなることを特徴としてい
る。上記複合酸化物としては、たとえばLaBO3、
CeBO3またはSmBO3が用いられる。[Summary of the Invention] The electrolyte holding material according to the present invention is characterized by being made of a composite oxide containing a rare earth element and boron. Examples of the above composite oxide include LaBO 3 ,
CeBO3 or SmBO3 is used.
［発明の効果］
本発明者等は、保持材の研究の過程で希土類元
素と硼素とを含む複合酸化物、特にLaBO3、
CeBO3、SmBO3が炭酸塩に対し、極めて安定で
あることを見出した。その理由は明らかではない
が、本発明に係る保持材で溶融炭酸塩を保持し、
CO2ガス雰囲気下、650℃、100時間の反応試験で
は、以下のような結果を得ることができた。[Effects of the Invention] In the course of research on holding materials, the present inventors developed a complex oxide containing rare earth elements and boron, particularly LaBO 3 ,
We found that CeBO 3 and SmBO 3 are extremely stable against carbonates. Although the reason is not clear, the holding material according to the present invention holds molten carbonate,
In a reaction test conducted at 650°C for 100 hours in a CO 2 gas atmosphere, the following results were obtained.
すなわち、従来用いられたジルコニア、チタン
酸カリウムは、反応前後でその容量が15％以上減
少したのに対し、本発明に係る保持材のそれは５
％以内の減少に止まつた。 That is, while the capacity of conventionally used zirconia and potassium titanate decreased by 15% or more before and after the reaction, the capacity of the retaining material according to the present invention decreased by 5%.
The decrease remained within 1%.
また、ジルコニア、チタン酸カリウムは、反応
前後でその粒径変化量が８％以上であつたのに対
し、本発明に係る保持材のそれは４％以内に収ま
つていることが確認された。 Furthermore, it was confirmed that while the particle size change of zirconia and potassium titanate was 8% or more before and after the reaction, the change of the particle size of the holding material according to the present invention was within 4%.
このように、本発明によれば、炭酸塩を長期に
わたつて安定に保持することのできる溶融炭酸塩
燃料電池の電解質保持材を提供できる。 As described above, according to the present invention, it is possible to provide an electrolyte holding material for a molten carbonate fuel cell that can stably hold carbonate over a long period of time.
［発明の実施例］ 以下、本発明の実施例につき詳述する。[Embodiments of the invention] Examples of the present invention will be described in detail below.
実施例 １
LaBO3からなる保持部材粉末２ｇと、炭酸リ
チウム粉末28ｇと、炭酸カリウム粉末3.2ｇとを
混合し、ホツトプレスによつて直径12mm厚さ５mm
の板状試験片を成形した。得られた試験片をAu
容器中に収納し、CO2雰囲気下、650℃で100時間
放置した。上記反応試験の前後における試験片の
組成変化および保持材粉末の粒径変化をそれぞれ
Ｘ線回折およびSEM観察により調査した。Example 1 2 g of holding member powder made of LaBO 3 , 28 g of lithium carbonate powder, and 3.2 g of potassium carbonate powder were mixed and heated to a diameter of 12 mm and a thickness of 5 mm.
A plate-shaped test piece was molded. The obtained specimen was Au
It was stored in a container and left at 650° C. for 100 hours under a CO 2 atmosphere. Changes in the composition of the test piece and changes in the particle size of the holding material powder before and after the reaction test were investigated by X-ray diffraction and SEM observation, respectively.
Ｘ線回折で、反応前後におけるそれぞれの炭酸
リチウムのピーク値の積分強度値と、LaBO3の
ピーク値の積分強度値との相対強度比を求めたと
ころ、反応前後での相対強度比が５％の減少に止
まつていることが確認された。 When the relative intensity ratio between the integrated intensity value of each lithium carbonate peak value before and after the reaction and the integrated intensity value of the peak value of LaBO 3 was determined by X-ray diffraction, the relative intensity ratio before and after the reaction was 5%. It was confirmed that the decrease has stopped.
また、SEM観察では、保持材粉末の粒径変化
が反応前後で４％以内に収まつていることが確認
された。 Furthermore, SEM observation confirmed that the change in particle size of the holding material powder was within 4% before and after the reaction.
これに対し、比較例としてジルコニア、チタン
酸カリウムを保持材粉末に用い、上記実施例１と
同様の試験を行なつた。 On the other hand, as a comparative example, the same test as in Example 1 was conducted using zirconia and potassium titanate as the holding material powder.
この結果、Ｘ線回折での相対強度比は、反応前
後でジルコニアが15％減少、チタン酸カリウムが
20％減少という結果であつた。また、粒径変化に
ついては、反応前後でジルコニアが８％減少、チ
タン酸カリウムが10％減少という結果であつた。 As a result, the relative intensity ratio in X-ray diffraction showed that zirconia decreased by 15% before and after the reaction, and potassium titanate decreased by 15%.
The result was a 20% decrease. Regarding particle size changes, zirconia decreased by 8% and potassium titanate decreased by 10% before and after the reaction.
以上の結果から明らかな如く、LaBO3を保持
材とした場合には、ジルコニアやチタン酸カリウ
ムに比べ優れた炭酸塩の保持能力を有する。した
がつて前述した効果を得ることができる。 As is clear from the above results, when LaBO 3 is used as a retention material, it has a superior carbonate retention ability compared to zirconia and potassium titanate. Therefore, the above-mentioned effects can be obtained.
実施例 ２
保持粉末としてCeBO3を用い、前記実施例１
と同様の試験を行なつたところ、反応前後での相
対強度比が５％減少に止まり、粒径変化が４％以
内の変化に止まつた。Example 2 CeBO 3 was used as the retention powder, and Example 1 was used as the retention powder.
When a similar test was conducted, the relative strength ratio before and after the reaction decreased by only 5%, and the change in particle size remained within 4%.
実施例 ３
保持材粉末としてSmBO3を用い、前記実施例
１と同様の試験を行なつたところ、反応前後での
相対強度比が５％減少に止まり、粒径変化が４％
の減少に止まつた。Example 3 When the same test as in Example 1 was conducted using SmBO 3 as the retaining material powder, the relative strength ratio before and after the reaction decreased by only 5%, and the particle size change was 4%.
stopped decreasing.
以上の如く、保持材にCeBO3、SmBO3を用い
ても、本発明の効果を奏することができる。 As described above, the effects of the present invention can be achieved even when CeBO 3 or SmBO 3 is used as the holding material.
なお、本発明に係る保持材は、電解質板におけ
る含有量が20〜70重量％であれば、より良好なる
電解質保持機能を発揮する。 Note that the holding material according to the present invention exhibits a better electrolyte holding function when the content in the electrolyte plate is 20 to 70% by weight.
また、本発明に係る保持材と、アルミン酸リチ
ウムとの混合体を、例えば骨材と補助保持材の如
く組合わせて用いるようにしても、本発明の効果
を発揮することができる。 Furthermore, the effects of the present invention can be exhibited even if the mixture of the retaining material according to the present invention and lithium aluminate is used in combination, for example, as aggregate and auxiliary retaining material.
Claims (1)
る溶融炭酸塩燃料電池の電解質保持材。 ２ 前記複合酸化物は、LaBO3、CeBO3または
SmBO3からなるものであることを特徴とする特
許請求の範囲第１項記載の溶融炭素塩燃料電池の
電解質保持材。[Scope of Claims] 1. An electrolyte holding material for a molten carbonate fuel cell made of a composite oxide containing a rare earth element and boron. 2 The composite oxide is LaBO 3 , CeBO 3 or
The electrolyte holding material for a molten carbon salt fuel cell according to claim 1, characterized in that it is made of SmBO3 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59014435A JPS60160571A (en) | 1984-01-31 | 1984-01-31 | Electrolyte support material of molten carbonate fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59014435A JPS60160571A (en) | 1984-01-31 | 1984-01-31 | Electrolyte support material of molten carbonate fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60160571A JPS60160571A (en) | 1985-08-22 |
| JPH0335777B2 true JPH0335777B2 (en) | 1991-05-29 |
Family
ID=11860934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59014435A Granted JPS60160571A (en) | 1984-01-31 | 1984-01-31 | Electrolyte support material of molten carbonate fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60160571A (en) |
-
1984
- 1984-01-31 JP JP59014435A patent/JPS60160571A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60160571A (en) | 1985-08-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |