JP2023509992A - Online Evaluation Method for Separator Roasting of Molten Carbonate Fuel Cells - Google Patents
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- 239000000446 fuel Substances 0.000 title claims abstract description 110
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 105
- 238000011156 evaluation Methods 0.000 title claims abstract description 16
- 239000000853 adhesive Substances 0.000 claims abstract description 9
- 230000001070 adhesive effect Effects 0.000 claims abstract description 9
- 239000004014 plasticizer Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 230000004913 activation Effects 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 7
- 229910001882 dioxygen Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 2
- 238000010248 power generation Methods 0.000 abstract description 7
- 238000010304 firing Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
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Abstract
溶融炭酸塩型燃料電池のセパレータ焙焼のオンライン評価方法であって、溶融炭酸塩型燃料電池のセパレータに含まれる溶媒、粘着剤及び可塑剤の質量を算出するステップ１）と、溶融炭酸塩型燃料電池のセパレータ焙焼の昇温プログラムを設定するステップ２）と、溶融炭酸塩型燃料電池のセパレータの焙焼の昇温プログラムに従って、組み立てられた溶融炭酸塩型燃料電池に対して昇温焙焼を行い、溶融炭酸塩型燃料電池の内部で活性化反応が行われた後、溶融炭酸塩型燃料電池について放電テストを行った結果、溶融炭酸塩型燃料電池の陰極及び陽極でガス溢れやガス漏れの危険がなく、単一電池の平均開回路電圧が予め設定された電圧値よりも大きい場合、溶融炭酸塩型燃料電池のセパレータの焙焼が合格し、これにより、溶融炭酸塩型燃料電池のセパレータ焙焼のオンライン評価が完了するステップ３）を含む。該方法は、溶融炭酸塩型燃料電池の発電性能を効果的に確保できる。
An online evaluation method for separator roasting of a molten carbonate fuel cell, comprising a step 1) of calculating the mass of a solvent, an adhesive and a plasticizer contained in the separator of the molten carbonate fuel cell; The assembled molten carbonate fuel cell is heated and roasted according to the step 2) of setting the temperature raising program for roasting the separator of the fuel cell and the temperature raising program for roasting the separator of the molten carbonate fuel cell. After firing and an activation reaction inside the molten carbonate fuel cell, a discharge test was conducted on the molten carbonate fuel cell. When there is no risk of gas leakage and the average open circuit voltage of the single cell is greater than the preset voltage value, the roasting of the separator of the molten carbonate fuel cell is passed, thereby making the molten carbonate fuel Including step 3) in which the on-line evaluation of battery separator roasting is completed. This method can effectively ensure the power generation performance of the molten carbonate fuel cell.
Description
本発明は、溶融炭酸塩型燃料電池の技術分野に属し、溶融炭酸塩型燃料電池のセパレータ焙焼のオンライン評価方法に関する。 The present invention belongs to the technical field of molten carbonate fuel cells, and relates to an online evaluation method for separator roasting of molten carbonate fuel cells.
溶融炭酸塩型燃料電池（ＭＣＦＣ）は、６５０℃で作動する高温燃料電池であり、貴金属を触媒とする必要がなく、燃料が入手しやすく、騒音が少なく、汚染物がほぼゼロ排出であり、発電効率が高く、熱電併給が図られるなどの利点があり、１００キロワットレベルからメガワットレベルの分散型発電所や固定型発電所に適しており、将来性が期待できる。 The molten carbonate fuel cell (MCFC) is a high temperature fuel cell that operates at 650°C, does not require precious metal catalysts, has easy fuel availability, low noise, and near-zero pollutant emissions; It has advantages such as high power generation efficiency and co-supply of heat and power, and is suitable for distributed power plants and fixed power plants from the 100 kilowatt level to the megawatt level, and is expected to have future potential.
溶融炭酸塩型燃料電池では、重要な部材には、電極、セパレータ、電解質、双極板などがあり、この中でも、セパレータの性能の良否が電池の性能に大きな影響を与える。一般には、セパレータの性能はその気孔率及び平均孔径につながり、成形後のセパレータの細孔分布が主に成形前の膜に含まれる揮発されにくい粘着剤や溶媒の含有量及びこれらの分布の均一さに依存する。含有量が高い場合、成形後の膜の気孔率及び平均孔径が大きく、膜に含浸させた電解質が多くなり、膜の電気抵抗が小さいが、平均孔径が大きいため、陰極や陽極ではガス溢れが発生しやすく、一方、含有量が低い場合、膜の気孔率及び平均孔径が減少し、ガスバリアに有利であるが、膜に含浸させた電解質が少なくなり、イオン伝導に不利である。このため、セパレータについては適切な気孔率及び孔径分布が求められ、一般には、セパレータについて、気孔率は５０～７０％、孔径は１μｍ未満であり、均一に分布していることが期待される。 Important members of a molten carbonate fuel cell include electrodes, separators, electrolytes, bipolar plates, etc. Among them, the performance of the separator has a great influence on the performance of the battery. In general, the performance of a separator is related to its porosity and average pore size. It depends. When the content is high, the porosity and average pore size of the membrane after molding are large, the electrolyte impregnated in the membrane is large, and the electrical resistance of the membrane is small, but the average pore size is large, so gas overflows at the cathode and anode. On the other hand, when the content is low, the porosity and average pore size of the membrane decrease, which is advantageous for gas barrier, but the electrolyte impregnated in the membrane decreases, which is disadvantageous for ion conduction. Therefore, the separator is required to have an appropriate porosity and pore size distribution. In general, the separator is expected to have a porosity of 50 to 70% and a pore size of less than 1 μm, which is uniformly distributed.
溶融炭酸塩型燃料電池のセパレータは、電池の初回起動時に原位置焙焼を行うので、初回の焙焼効果が電池の性能を直接左右する。技術的秘密と技術的封鎖により、中国では、ＭＣＦＣに関する研究はまだ初期段階である。現在、ＭＣＦＣに取り込んでいる機関としては、主に中国科学院大連化学物理研究所、中国華能集団クリーンエネルギー技術研究院有限公司及び一部の大学があり、溶融炭酸塩型燃料電池のセパレータ焙焼効果のオンライン評価に関しては、まだ関連する検討や著作がなく、このため、溶融炭酸塩型燃料電池の発電性能が確保されにくい。 Since the separator of the molten carbonate fuel cell undergoes in-situ roasting at the first start-up of the cell, the effect of the initial roasting directly affects the performance of the cell. Due to technical secrecy and technical blockade, research on MCFC is still in its early stages in China. At present, the institutions that are involved in MCFC are mainly the Dalian Institute of Chemistry and Physics of the Chinese Academy of Sciences, the China Huaneng Group Clean Energy Technology Research Institute Co., Ltd., and some universities. Regarding the online evaluation of the effects, there are no related studies or publications yet, and for this reason, it is difficult to ensure the power generation performance of molten carbonate fuel cells.
本発明の目的は、上記の従来技術の欠点を解決し、溶融炭酸塩型燃料電池の発電性能を効果的に確保できる溶融炭酸塩型燃料電池のセパレータ焙焼のオンライン評価方法を提供することである。 An object of the present invention is to solve the above-mentioned drawbacks of the prior art, and to provide an online evaluation method for separator roasting of a molten carbonate fuel cell that can effectively ensure the power generation performance of the molten carbonate fuel cell. be.
上記の目的を達成させるために、本発明による溶融炭酸塩型燃料電池のセパレータ焙焼のオンライン評価方法は、
溶融炭酸塩型燃料電池を組み立てるに先立って、溶融炭酸塩型燃料電池のセパレータの重量を記録し、溶融炭酸塩型燃料電池のセパレータの組成から、溶融炭酸塩型燃料電池のセパレータに含まれる溶媒、粘着剤及び可塑剤の質量を算出するステップ１）と、
溶融炭酸塩型燃料電池のセパレータの熱重量曲線から、溶融炭酸塩型燃料電池のセパレータの焙焼の昇温プログラムを設定するステップ２）と、
溶融炭酸塩型燃料電池のセパレータの焙焼の昇温プログラムに従って、組み立てられた溶融炭酸塩型燃料電池に対して昇温焙焼を行い、昇温中、溶融炭酸塩型燃料電池の陰極に空気を導入し、溶融炭酸塩型燃料電池の陽極に窒素ガスを導入しながら、陰極の排気口での酸素ガス濃度の変化をオンラインで監視し、酸素ガス濃度が小さくなってから大きくなると、溶融炭酸塩型燃料電池のセパレータ内の溶媒、粘着剤及び可塑剤が完全に燃焼されたことを示し、このとき、溶融炭酸塩型燃料電池のセパレータが多孔質のシート状構造となり、
溶融炭酸塩型燃料電池が４９０～５００℃に安定化すると、陰極への空気導入を停止し、このとき、電解質が徐々に溶融して溶融炭酸塩型燃料電池のセパレータに含浸し、
溶融炭酸塩型燃料電池が６００～６５０℃に安定化すると、溶融炭酸塩型燃料電池が電解質で満たされ、このとき、溶融炭酸塩型燃料電池は発電能力を備えるものとなり、溶融炭酸塩型燃料電池の陽極に水素ガスを導入し、溶融炭酸塩型燃料電池の陰極に空気及び二酸化炭素を導入し、溶融炭酸塩型燃料電池の内部で活性化反応が行われた後、溶融炭酸塩型燃料電池について放電テストを行った結果、溶融炭酸塩型燃料電池の陰極及び陽極でガス溢れやガス漏れの危険がなく、単一電池の平均開回路電圧が予め設定された電圧値よりも大きい場合、溶融炭酸塩型燃料電池のセパレータの焙焼が合格し、それ以外の場合、溶融炭酸塩型燃料電池のセパレータの焙焼が合格しておらず、これにより、溶融炭酸塩型燃料電池のセパレータ焙焼のオンライン評価が完了するステップ３）とを含む。
In order to achieve the above object, an online evaluation method for separator roasting of a molten carbonate fuel cell according to the present invention comprises:
Prior to assembling the molten carbonate fuel cell, the weight of the separator of the molten carbonate fuel cell was recorded, and from the composition of the separator of the molten carbonate fuel cell, the solvent contained in the separator of the molten carbonate fuel cell was determined. , step 1) of calculating the mass of the adhesive and the plasticizer;
Step 2) of setting a temperature rising program for roasting the separator of the molten carbonate fuel cell from the thermogravimetric curve of the separator of the molten carbonate fuel cell;
The assembled molten carbonate fuel cell is subjected to temperature-rising roasting according to the temperature-rising program for roasting the separator of the molten carbonate fuel cell. was introduced, and while nitrogen gas was being introduced into the anode of the molten carbonate fuel cell, changes in the oxygen gas concentration at the exhaust port of the cathode were monitored online. It indicates that the solvent, adhesive and plasticizer in the separator of the salt type fuel cell are completely burned, and at this time, the separator of the molten carbonate type fuel cell becomes a porous sheet-like structure,
When the molten carbonate fuel cell is stabilized at 490 to 500° C., the introduction of air to the cathode is stopped, and the electrolyte gradually melts and impregnates the separator of the molten carbonate fuel cell,
When the molten carbonate fuel cell is stabilized at 600 to 650° C., the molten carbonate fuel cell is filled with electrolyte. Hydrogen gas is introduced into the anode of the cell, air and carbon dioxide are introduced into the cathode of the molten carbonate fuel cell, and after an activation reaction takes place inside the molten carbonate fuel cell, the molten carbonate fuel is After conducting a discharge test on the battery, if there is no risk of gas overflow or gas leakage at the cathode and anode of the molten carbonate fuel cell, and the average open circuit voltage of the single cell is greater than the preset voltage value, The separator roasting of the molten carbonate fuel cell passes, otherwise the separator roasting of the molten carbonate fuel cell does not pass, which leads to the separator roasting of the molten carbonate fuel cell. and step 3) in which the online evaluation of firing is completed.
昇温中、溶融炭酸塩型燃料電池の陰極に１Ｌ／分の空気を導入し、溶融炭酸塩型燃料電池の陽極に０．５Ｌ／分の窒素ガスを導入する。 During the temperature rise, 1 L/min of air is introduced to the cathode of the molten carbonate fuel cell, and 0.5 L/min of nitrogen gas is introduced to the anode of the molten carbonate fuel cell.
溶融炭酸塩型燃料電池が６００～６５０℃に安定化すると、溶融炭酸塩型燃料電池が電解質で満たされ、このとき、溶融炭酸塩型燃料電池は発電能力を備えるものとなり、
溶融炭酸塩型燃料電池の陽極に１Ｌ／分の水素ガスを導入し、溶融炭酸塩型燃料電池の陰極に３Ｌ／分の空気及び１Ｌ／分の二酸化炭素を導入する。
When the molten carbonate fuel cell is stabilized at 600 to 650° C., the molten carbonate fuel cell is filled with electrolyte, and at this time, the molten carbonate fuel cell becomes capable of generating electricity.
1 L/min of hydrogen gas is introduced to the anode of the molten carbonate fuel cell, and 3 L/min of air and 1 L/min of carbon dioxide are introduced to the cathode of the molten carbonate fuel cell.
予め設定された電圧値が１．１Ｖである。 A preset voltage value is 1.1V.
本発明は以下の有益な効果を有する。
本発明による溶融炭酸塩型燃料電池のセパレータ焙焼のオンライン評価方法によれば、具体的に実行される際に、電池の昇温焙焼において、陰極に空気、陽極に窒素ガスが導入されることにより、陽極の酸化が回避され、また、焙焼過程において、陰極の排気口での酸素ガス濃度の変化をオンラインで監視し、酸素ガス濃度が小さくなってから大きくなると、セパレータ内の粘着剤及び可塑剤が完全に燃焼されたことを示し、このとき、セパレータが多孔質のシート状構造となり、また、電池が初期発電能力を備えたものとなったときに、陽極に水素ガス、陰極に空気及び二酸化炭素が導入され、電池内部で短時間の活性化反応が行われた後、電池について放電テストを行うことができ、テストにおいては、電池の陰極及び陽極でガス溢れやガス漏れの危険がなく、単一電池の平均開回路電圧が１．１Ｖよりも大きい場合、電池のセパレータの焙焼が合格し、これにより、溶融炭酸塩型燃料電池のセパレータ焙焼のオンライン評価が実現され、溶融炭酸塩型燃料電池の発電性能が確保され、ＭＣＦＣの発電性能の最適化などにおいて指導的な意義がある。
The invention has the following beneficial effects.
According to the online evaluation method for separator roasting of a molten carbonate fuel cell according to the present invention, air is introduced into the cathode and nitrogen gas is introduced into the anode in the temperature-rising roasting of the battery when specifically executed. As a result, oxidation of the anode is avoided, and during the roasting process, changes in the oxygen gas concentration at the cathode exhaust port are monitored online, and when the oxygen gas concentration decreases and then increases, the adhesive in the separator and the plasticizer are completely burned. At this time, when the separator has a porous sheet-like structure and the battery has the initial power generation capacity, hydrogen gas is supplied to the anode and to the cathode. After air and carbon dioxide are introduced and a short time activation reaction takes place inside the battery, the battery can be subjected to a discharge test, during which there is no risk of gas overflow or gas leakage at the cathode and anode of the battery. and the average open circuit voltage of the single cell is greater than 1.1 V, the separator roasting of the battery is passed, which realizes the online evaluation of the molten carbonate fuel cell separator roasting, The power generation performance of molten carbonate fuel cells is ensured, and it has a guiding significance in optimizing the power generation performance of MCFC.
以下、図面を参照しながら本発明についてさらに詳細に説明する。 The present invention will be described in more detail below with reference to the drawings.
図１に示すように、本発明による溶融炭酸塩型燃料電池のセパレータ焙焼のオンライン評価方法は、
溶融炭酸塩型燃料電池を組み立てるに先立って、溶融炭酸塩型燃料電池のセパレータの重量を記録し、溶融炭酸塩型燃料電池のセパレータの組成から、溶融炭酸塩型燃料電池のセパレータに含まれる溶媒、粘着剤及び可塑剤の質量を算出するステップ１）と、
溶融炭酸塩型燃料電池のセパレータの熱重量曲線から、溶融炭酸塩型燃料電池のセパレータの焙焼の昇温プログラムを設定するステップ２）と、
溶融炭酸塩型燃料電池のセパレータの焙焼の昇温プログラムに従って、組み立てられた溶融炭酸塩型燃料電池に対して昇温焙焼を行い、昇温中、溶融炭酸塩型燃料電池の陰極に空気を導入し、溶融炭酸塩型燃料電池の陽極に窒素ガスを導入しながら、陰極の排気口での酸素ガス濃度の変化をオンラインで監視し、酸素ガス濃度が小さくなってから大きくなると、溶融炭酸塩型燃料電池のセパレータ内の溶媒、粘着剤及び可塑剤が完全に燃焼されたことを示し、このとき、溶融炭酸塩型燃料電池のセパレータが多孔質のシート状構造となり、
溶融炭酸塩型燃料電池が４９０～５００℃に安定化すると、陰極への空気導入を停止し、このとき、電解質が徐々に溶融して溶融炭酸塩型燃料電池のセパレータに含浸し、
溶融炭酸塩型燃料電池が６００～６５０℃に安定化すると、溶融炭酸塩型燃料電池が電解質で満たされ、このとき、溶融炭酸塩型燃料電池は発電能力を備えるものとなり、溶融炭酸塩型燃料電池の陽極に水素ガスを導入し、溶融炭酸塩型燃料電池の陰極に空気及び二酸化炭素を導入し、溶融炭酸塩型燃料電池の内部で活性化反応が行われた後、溶融炭酸塩型燃料電池について放電テストを行った結果、溶融炭酸塩型燃料電池の陰極及び陽極でガス溢れやガス漏れの危険がなく、単一電池の平均開回路電圧が１．１Ｖよりも大きい場合、溶融炭酸塩型燃料電池のセパレータの焙焼が合格し、それ以外の場合、溶融炭酸塩型燃料電池のセパレータの焙焼が合格しておらず、これにより、溶融炭酸塩型燃料電池のセパレータ焙焼のオンライン評価が完了するステップ３）とを含む。
As shown in FIG. 1, the online evaluation method for separator roasting of a molten carbonate fuel cell according to the present invention includes:
Prior to assembling the molten carbonate fuel cell, the weight of the separator of the molten carbonate fuel cell was recorded, and from the composition of the separator of the molten carbonate fuel cell, the solvent contained in the separator of the molten carbonate fuel cell was determined. , step 1) of calculating the mass of the adhesive and the plasticizer;
Step 2) of setting a temperature rising program for roasting the separator of the molten carbonate fuel cell from the thermogravimetric curve of the separator of the molten carbonate fuel cell;
The assembled molten carbonate fuel cell is subjected to temperature-rising roasting according to the temperature-rising program for roasting the separator of the molten carbonate fuel cell. was introduced, and while nitrogen gas was being introduced into the anode of the molten carbonate fuel cell, changes in the oxygen gas concentration at the exhaust port of the cathode were monitored online. It indicates that the solvent, adhesive and plasticizer in the separator of the salt type fuel cell are completely burned, and at this time, the separator of the molten carbonate type fuel cell becomes a porous sheet-like structure,
When the molten carbonate fuel cell is stabilized at 490 to 500° C., the introduction of air to the cathode is stopped, and the electrolyte gradually melts and impregnates the separator of the molten carbonate fuel cell,
When the molten carbonate fuel cell is stabilized at 600 to 650° C., the molten carbonate fuel cell is filled with electrolyte. Hydrogen gas is introduced into the anode of the cell, air and carbon dioxide are introduced into the cathode of the molten carbonate fuel cell, and after an activation reaction takes place inside the molten carbonate fuel cell, the molten carbonate fuel is After conducting a discharge test on the battery, if there is no risk of gas overflow or gas leakage at the cathode and anode of the molten carbonate fuel cell, and the average open circuit voltage of a single cell is greater than 1.1 V, the molten carbonate The roasting of the separator of the molten carbonate fuel cell has passed, otherwise the roasting of the separator of the molten carbonate fuel cell has not passed, which makes the separator roasting of the molten carbonate fuel cell online and step 3) in which the evaluation is completed.
実施例１
本実施例の具体的な操作は以下のとおりである。
１）電極有効面積が０．２ｍ2の溶融炭酸塩型燃料電池のセルを一対用意し、厚さ０．７ｍｍ、重量４２０ｇのセパレータを選択し、セパレータを製造するための組成から推定した結果、メタアルミン酸リチウム粉末の含有量は約７０～８０％であった。
２）セパレータの熱重量曲線から、セパレータ焙焼の昇温プログラムを作成した。
３）昇温プログラムに従って、組み立てられたセルに昇温焙焼を行い、昇温中、陰極に１Ｌ／分の空気を導入し、陽極に０．５Ｌ／分の窒素ガスを導入した。
４）酸素ガス濃度検出装置を用いて、陰極の排気ガスを監視し、酸素ガス濃度が最初の０．２Ｌ／分から０．２Ｌ／分程度になると、セパレータ内の粘着剤及び可塑剤などがほぼ完全に焙焼され、
電池が４９０～５００℃に安定化すると、陰極への空気導入を停止し、
電池が６００～６５０℃に安定化すると、セパレータはほぼ電解質で満たされ、さらに、陽極に１Ｌ／分の水素ガスを導入し、陰極に３Ｌ／分の空気及び１Ｌ／分の二酸化炭素を導入し、電池の内部で短時間の活性化反応が行われた後、電池について放電テストを行うことができ、
ここでは、セパレータ焙焼の品質は、電池の陰極及び陽極でガス溢れやガス漏れの危険の有無に基づいて判定され、セルの開回路電圧が１．１２Ｖに達する場合、今回のセパレータ焙焼が高品質であることを示している。
Example 1
Specific operations of this embodiment are as follows.
1) Prepare a pair of molten carbonate fuel cell cells with an electrode effective area of 0.2 m 2 , select a separator with a thickness of 0.7 mm and a weight of 420 g, and estimate from the composition for manufacturing the separator. The content of lithium metaaluminate powder was about 70-80%.
2) From the thermogravimetric curve of the separator, a temperature rising program for roasting the separator was created.
3) The assembled cell was subjected to temperature-rising roasting according to the temperature-rising program, and during the temperature-rising, 1 L/min of air was introduced into the cathode and 0.5 L/min of nitrogen gas was introduced into the anode.
4) Monitor the cathode exhaust gas using an oxygen gas concentration detector, and when the oxygen gas concentration drops from the initial 0.2 L/min to about 0.2 L/min, the adhesive and plasticizer in the separator will almost perfectly roasted,
When the battery stabilizes at 490-500° C., stop introducing air to the cathode,
When the cell stabilized at 600-650° C., the separator was nearly filled with electrolyte, and 1 L/min of hydrogen gas was introduced to the anode and 3 L/min of air and 1 L/min of carbon dioxide to the cathode. , after a short activation reaction has taken place inside the battery, the battery can be subjected to a discharge test,
Here, the quality of separator roasting is judged based on the presence or absence of risk of gas overflow or gas leakage at the cathode and anode of the battery. It indicates high quality.
Claims (4)
溶融炭酸塩型燃料電池のセパレータの熱重量曲線から、溶融炭酸塩型燃料電池のセパレータの焙焼の昇温プログラムを設定するステップ２）と、
溶融炭酸塩型燃料電池のセパレータの焙焼の昇温プログラムに従って、組み立てられた溶融炭酸塩型燃料電池に対して昇温焙焼を行い、昇温中、溶融炭酸塩型燃料電池の陰極に空気を導入し、溶融炭酸塩型燃料電池の陽極に窒素ガスを導入しながら、陰極の排気口での酸素ガス濃度の変化をオンラインで監視し、酸素ガス濃度が小さくなってから大きくなると、溶融炭酸塩型燃料電池のセパレータ内の溶媒、粘着剤及び可塑剤が完全に燃焼されたことを示し、このとき、溶融炭酸塩型燃料電池のセパレータが多孔質のシート状構造となり、
溶融炭酸塩型燃料電池が４９０～５００℃に安定化すると、陰極への空気導入を停止し、このとき、電解質が徐々に溶融して溶融炭酸塩型燃料電池のセパレータに含浸し、
溶融炭酸塩型燃料電池が６００～６５０℃に安定化すると、溶融炭酸塩型燃料電池が電解質で満たされ、このとき、溶融炭酸塩型燃料電池は発電能力を備えるものとなり、溶融炭酸塩型燃料電池の陽極に水素ガスを導入し、溶融炭酸塩型燃料電池の陰極に空気及び二酸化炭素を導入し、溶融炭酸塩型燃料電池の内部で活性化反応が行われた後、溶融炭酸塩型燃料電池について放電テストを行った結果、溶融炭酸塩型燃料電池の陰極及び陽極でガス溢れやガス漏れの危険がなく、単一電池の平均開回路電圧が予め設定された電圧値よりも大きい場合、溶融炭酸塩型燃料電池のセパレータの焙焼が合格し、それ以外の場合、溶融炭酸塩型燃料電池のセパレータの焙焼が合格しておらず、これにより、溶融炭酸塩型燃料電池のセパレータ焙焼のオンライン評価が完了するステップ３）とを含む、ことを特徴とする溶融炭酸塩型燃料電池のセパレータ焙焼のオンライン評価方法。 Prior to assembling the molten carbonate fuel cell, the weight of the separator of the molten carbonate fuel cell was recorded, and from the composition of the separator of the molten carbonate fuel cell, the solvent contained in the separator of the molten carbonate fuel cell was determined. , step 1) of calculating the mass of the adhesive and the plasticizer;
Step 2) of setting a temperature rising program for roasting the separator of the molten carbonate fuel cell from the thermogravimetric curve of the separator of the molten carbonate fuel cell;
The assembled molten carbonate fuel cell is subjected to temperature-rising roasting according to the temperature-rising program for roasting the separator of the molten carbonate fuel cell. was introduced, and while nitrogen gas was being introduced into the anode of the molten carbonate fuel cell, changes in the oxygen gas concentration at the exhaust port of the cathode were monitored online. It indicates that the solvent, adhesive and plasticizer in the separator of the salt type fuel cell are completely burned, and at this time, the separator of the molten carbonate type fuel cell becomes a porous sheet-like structure,
When the molten carbonate fuel cell is stabilized at 490 to 500° C., the introduction of air to the cathode is stopped, and the electrolyte gradually melts and impregnates the separator of the molten carbonate fuel cell,
When the molten carbonate fuel cell is stabilized at 600 to 650° C., the molten carbonate fuel cell is filled with electrolyte. Hydrogen gas is introduced into the anode of the cell, air and carbon dioxide are introduced into the cathode of the molten carbonate fuel cell, and after an activation reaction takes place inside the molten carbonate fuel cell, the molten carbonate fuel is After conducting a discharge test on the battery, if there is no risk of gas overflow or gas leakage at the cathode and anode of the molten carbonate fuel cell, and the average open circuit voltage of the single cell is greater than the preset voltage value, The separator roasting of the molten carbonate fuel cell passes, otherwise the separator roasting of the molten carbonate fuel cell does not pass, which leads to the separator roasting of the molten carbonate fuel cell. and step 3) in which the online evaluation of baking is completed.
溶融炭酸塩型燃料電池の陽極に１Ｌ／分の水素ガスを導入し、溶融炭酸塩型燃料電池の陰極に３Ｌ／分の空気及び１Ｌ／分の二酸化炭素を導入する、ことを特徴とする請求項１に記載の溶融炭酸塩型燃料電池のセパレータ焙焼のオンライン評価方法。 When the molten carbonate fuel cell is stabilized at 600 to 650° C., the molten carbonate fuel cell is filled with electrolyte, and at this time, the molten carbonate fuel cell becomes capable of generating electricity.
1 L/min of hydrogen gas is introduced into the anode of the molten carbonate fuel cell, and 3 L/min of air and 1 L/min of carbon dioxide are introduced into the cathode of the molten carbonate fuel cell. Item 1. An online evaluation method for separator roasting of a molten carbonate fuel cell according to Item 1.
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