JP7338068B2 - Method for adding electrolyte to molten carbonate type battery - Google Patents
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/14—Fuel cells with fused electrolytes
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Description
本願は溶融炭酸塩型燃料電池の分野に関し、具体的には、溶融炭酸塩型燃料電池の電解質添加方法に関する。 TECHNICAL FIELD The present application relates to the field of molten carbonate fuel cells, and in particular to a method of electrolyte addition for molten carbonate fuel cells.
溶融炭酸塩型燃料電池の発電技術は高温燃料電池の発電技術として、燃料源が広く、モジュール化され、発電効率が高いなどの利点のため、国外では広く使用されている。近年、国内の水素エネルギー分野の技術の持続的な発展に伴い、燃料電池の発電技術も国内の視野に入ってきた。特に燃料電池の重要な材料の製造手段に関しては、溶融炭酸塩型燃料電池の電解質は主に炭酸塩、例えばＬｉ2ＣＯ3とＫ2ＣＯ3又はＬｉＣＯ3とＮａ2ＣＯ3である。電解質を炭酸塩膜としたり、電解質とセパレータとを同時に調製したり、電解質をチャネル内に投入したりすることが国外で使用されている。国外のこのような電解質の調製技術は溶融炭酸塩構造部材に対して設定されるものであり、国内の燃料電池に対しては制限がある。 Molten carbonate fuel cell power generation technology is widely used overseas as a high-temperature fuel cell power generation technology because of its advantages such as wide range of fuel sources, modularization, and high power generation efficiency. In recent years, with the continuous development of technology in the domestic hydrogen energy field, fuel cell power generation technology has also come into domestic view. Especially with regard to the production means of the important materials of fuel cells, the electrolytes of molten carbonate fuel cells are mainly carbonates, eg Li 2 CO 3 and K 2 CO 3 or LiCO 3 and Na 2 CO 3 . A carbonate membrane is used as the electrolyte, the electrolyte and the separator are prepared at the same time, and the electrolyte is introduced into the channel, which are used overseas. Such foreign electrolyte preparation technology is set for molten carbonate structural members, and has limitations for domestic fuel cells.
本願の目的は、従来技術に存在する欠陥を解決するために溶融炭酸塩型燃料電池の電解質添加方法を提供することであり、本願では、電解質を電極に添加することにより、電解質のチャネル内での分布を減少させ、両極板の厚さを効果的に減少させ、しかも、陰極に電解質を添加することで陰極材料のリチウム化を効率化し、燃料電池の性能を向上させることができる。 The object of the present application is to provide a method of electrolyte addition for molten carbonate fuel cells to solve the deficiencies existing in the prior art, in the present application, by adding the electrolyte to the electrode, the By reducing the distribution of , effectively reducing the thickness of the bipolar plates, and adding an electrolyte to the cathode, the lithiation of the cathode material can be made more efficient, and the performance of the fuel cell can be improved.
上記の目的を達成させるために、本願は下記技術的解決手段を採用する。 In order to achieve the above objectives, the present application adopts the following technical solutions.
溶融炭酸塩型燃料電池の電解質添加方法であって、
電解質を水及びエタノールと混合して撹拌し、電解質混合溶液を得るステップ１と、
電極質量を秤量して電極の空隙率を測定し、電極内部の電解質の理論必要質量を算出するステップ２と、
電極を容器に入れて、電解質混合溶液を加えるステップ３と、
容器を乾燥条件下に置いて、水及びエタノールを完全に揮発させるステップ４と、
乾燥後の電極と電極上に付着させた電解質との全質量を秤量して、さらに、電極上に付着させた電解質の質量を算出し、電解質の質量が、電極内部の電解質の理論必要質量の６０％～８０％である電極内部の電解質の実際必要質量を満たさない場合、ステップ３及びステップ４を繰り返し、電解質の質量が電極内部の電解質の実際必要質量を超える場合、電極内部の電解質の実際必要質量の範囲となるまで、余分な電解質を除去するステップ５と、
ステップ５で得られた電極を加熱して昇温し、加熱昇温が終了した後冷却し、溶融炭酸塩型燃料電池の電解質添加を完了するステップ６とを含む。
A method for adding an electrolyte to a molten carbonate fuel cell, comprising:
Step 1 of mixing and stirring an electrolyte with water and ethanol to obtain an electrolyte mixed solution;
Step 2 of weighing the electrode mass to measure the porosity of the electrode and calculating the theoretical required mass of the electrolyte inside the electrode;
step 3 of placing the electrode in a container and adding an electrolyte mixed solution;
step 4, placing the container under dry conditions to completely volatilize water and ethanol;
The total mass of the dried electrode and the electrolyte deposited on the electrode is weighed, and the mass of the electrolyte deposited on the electrode is calculated. The mass of the electrolyte is the theoretical required mass of the electrolyte inside the electrode. If the actual required mass of electrolyte inside the electrode, which is 60% to 80%, is not met, repeat steps 3 and 4; if the mass of electrolyte exceeds the actual required mass of electrolyte inside the electrode, step 5 removing excess electrolyte to the required mass range;
and a step 6 of heating the electrode obtained in step 5 to raise the temperature, cooling after the heating is completed, and completing the electrolyte addition of the molten carbonate fuel cell.
さらに、ステップ１では、電解質はＬｉ2ＣＯ3とＫ2ＣＯ3との混合物を用い、かつＬｉ2ＣＯ3とＫ2ＣＯ3とのモル比が３１：１９である。 Further, in step 1 , the electrolyte uses a mixture of Li2CO3 and K2CO3 , and the molar ratio of Li2CO3 and K2CO3 is 31:19.
さらに、ステップ１では、電解質と水とエタノールとの質量比が、１：（１～２）：（１．５～２）である。 Furthermore, in step 1, the mass ratio of the electrolyte, water, and ethanol is 1:(1-2):(1.5-2).
さらに、ステップ１では、撹拌時間が１．５～２時間である。 Further, in step 1, the stirring time is 1.5-2 hours.
さらに、ステップ２では、電極内部の電解質の理論必要質量の計算式が下式であり、
ｍ電解質＝ρ電解質Ｖ空隙＝ρ電解質（Ｖ電極－ｍ電極／ρニッケル）
ここで、ｍ電解質は電極内部の電解質の理論必要質量を表し、ρ電解質は電解質の密度を表し、Ｖ空隙は電極の空隙の体積を表し、Ｖ電極は電極の体積を表し、ｍ電極は電極の質量を表し、ρニッケルは金属ニッケルの密度を表す。
Furthermore, in step 2, the formula for calculating the theoretical required mass of the electrolyte inside the electrode is the following formula,
m electrolyte = ρ electrolyte V void = ρ electrolyte (V electrode - m electrode /ρ nickel )
Here, m electrolyte represents the theoretical required mass of the electrolyte inside the electrode, ρ electrolyte represents the density of the electrolyte, V void represents the volume of the electrode void, V electrode represents the volume of the electrode, and m electrode represents the volume of the electrode. and ρ nickel represents the density of metallic nickel.
さらに、ステップ４では、乾燥条件は、具体的には、温度３０℃で換気することである。 Furthermore, in step 4, the drying conditions are specifically ventilation at a temperature of 30°C.
さらに、ステップ６では、加熱昇温の工程は、具体的には、まず、窒素ガス雰囲気下、常温から４５０℃に昇温してから、水素ガス雰囲気下、４５０℃から６５０℃に昇温し、最後に、水素ガス雰囲気下、６５０℃で２時間保温する。 Further, in step 6, specifically, the temperature is raised from room temperature to 450° C. in a nitrogen gas atmosphere, and then from 450° C. to 650° C. in a hydrogen gas atmosphere. , Finally, it is kept at 650° C. for 2 hours in a hydrogen gas atmosphere.
さらに、５時間かけて常温から４５０℃に昇温する。 Further, the temperature is raised from room temperature to 450° C. over 5 hours.
さらに、１０時間かけて４５０℃から６５０℃に昇温する。 Further, the temperature is raised from 450° C. to 650° C. over 10 hours.
従来技術に比べて、本願は以下の有益な技術的効果がある。 Compared with the prior art, the present application has the following beneficial technical effects.
本願では、電解質が電極に添加され、電極材料が多孔質構造であり、その内部の７０％以上が空隙であるので、所定質量の電解質を充填することができ、一方、従来の溶融炭酸塩型燃料電池の電解質が一般的にチャネル内に配置され、本願の方法では、加熱昇温によって電解質が電解質の空隙に含浸され、電解質の添加が実現され、このような電解質添加方法は、チャネル内での電解質の分布を減少させ、両極板の厚さを効果的に減少させ、しかも、陰極材料に電解質が添加されるので、加熱昇温においてニッケルが炭酸リチウムと化学反応を起こしてＬｉＮｉＯ2を生成し、これにより、陰極材料のリチウム化を効率化し、燃料電池の性能を向上させることができる。 In the present application, the electrolyte is added to the electrode, the electrode material has a porous structure, and more than 70% of its interior is void, so that it can be filled with a certain mass of electrolyte, while the conventional molten carbonate type The electrolyte of the fuel cell is generally placed in the channel, and in the method of the present application, the electrolyte is impregnated into the voids of the electrolyte by heating to achieve the addition of the electrolyte. The distribution of the electrolyte is reduced, the thickness of the bipolar plate is effectively reduced, and the electrolyte is added to the cathode material, so that nickel and lithium carbonate undergo a chemical reaction during heating to form LiNiO2. This makes it possible to efficiently lithify the cathode material and improve the performance of the fuel cell.
さらに、本願は昇温工程を正確に制御し、室温から４５０℃への昇温は窒素ガスの保護下で行われ、これにより電極の酸化が回避され、４５０℃から６５０℃への昇温は水素ガスの保護下で行われ、電解質が溶融して電極の空隙に含浸し、水素ガス雰囲気下では酸化されたニッケル電極の一部が還元されることができ、６５０℃での保温により、ニッケルが炭酸リチウムと化学反応を起こしてＬｉＮｉＯ2を生成することができ、これにより、陰極材料のリチウム化を効率化する。 Furthermore, the present application precisely controls the heating process, the heating from room temperature to 450°C is performed under the protection of nitrogen gas, which avoids oxidation of the electrodes, and the heating from 450°C to 650°C is Under the protection of hydrogen gas, the electrolyte melts and impregnates the voids of the electrode, and under the hydrogen gas atmosphere, a part of the oxidized nickel electrode can be reduced. can chemically react with lithium carbonate to form LiNiO 2 , thereby facilitating the lithiation of the cathode material.
以下、本願の実施形態についてさらに詳細に説明する。 Hereinafter, embodiments of the present application will be described in further detail.
溶融炭酸塩型燃料電池の電解質添加方法は、以下のステップを含む。
１、電解質（モル比３１：１９のＬｉ2ＣＯ3とＫ2ＣＯ3、）と水とエタノールを１：（１～２）：（１．５～２）の質量比で混合し、１．５～２時間撹拌し、電解質混合溶液を得る。
２、電極質量を秤量して電極の空隙率を測定し、電極内部の電解質の必要量を算出し、計算式が下式であり、
ｍ電解質＝ρ電解質Ｖ空隙＝ρ電解質（Ｖ電極－ｍ電極／ρニッケル）
ここで、ｍ電解質は電極内部の電解質の理論必要質量を表し、ρ電解質は電解質の密度を表し、Ｖ空隙は電極の空隙の体積を表し、Ｖ電極は電極の体積を表し、ｍ電極は電極の質量を表し、ρニッケルは金属ニッケルの密度を表す。
３、電極をトレイに入れて、電解質混合溶液を加える。
４、トレイをオーブンに入れて、水及びエタノールが完全に揮発されるまで、温度３０℃及び通気を保持する。
５、電極と電解質との全質量を秤量して、さらに、電極上に付着させた電解質の質量を算出し、電解質の質量が、電極内部の電解質の理論必要質量の６０％～８０％である電極内部の電解質の実際必要質量を満たさない場合、ステップ３及びステップ４を繰り返し、電解質の質量が電極内部の電解質の実際必要質量を超える場合、電極内部の電解質の実際必要質量の範囲となるまで、余分な電解質を除去する。
６、電極と電解質を加熱炉に入れて、加熱工程として常温～４５０℃（Ｎ2保護）５時間、４５０～６５０℃（Ｈ2保護）１０時間、６５０℃で保温（Ｈ2保護）２時間、炉冷（Ｈ2保護）とし、窒素ガス及び水素ガスの雰囲気により電極の酸化が阻止される。
A molten carbonate fuel cell electrolyte addition method includes the following steps.
1. Mix the electrolyte (Li 2 CO 3 and K 2 CO 3 in a molar ratio of 31:19) with water and ethanol in a mass ratio of 1:(1-2):(1.5-2); Stir for 5 to 2 hours to obtain an electrolyte mixed solution.
2. Weigh the electrode mass to measure the porosity of the electrode, calculate the required amount of electrolyte inside the electrode, the calculation formula is the following formula,
m electrolyte = ρ electrolyte V void = ρ electrolyte (V electrode - m electrode /ρ nickel )
Here, m electrolyte represents the theoretical required mass of the electrolyte inside the electrode, ρ electrolyte represents the density of the electrolyte, V void represents the volume of the electrode void, V electrode represents the volume of the electrode, and m electrode represents the volume of the electrode. and ρ nickel represents the density of metallic nickel.
3. Put the electrode into the tray and add the electrolyte mixed solution.
4. Place the tray in the oven and keep the temperature at 30°C and ventilation until the water and ethanol are completely volatilized.
5. Weigh the total mass of the electrode and the electrolyte, and then calculate the mass of the electrolyte deposited on the electrode, and the mass of the electrolyte is 60% to 80% of the theoretical required mass of the electrolyte inside the electrode. If the actual required mass of the electrolyte inside the electrode is not met, repeat steps 3 and 4, if the mass of the electrolyte exceeds the actual required mass of the electrolyte inside the electrode, until it falls within the range of the actual required mass of the electrolyte inside the electrode. , to remove excess electrolyte.
6. Place the electrodes and electrolyte in a heating furnace, and heat at room temperature to 450°C ( N2 protection) for 5 hours, 450 to 650°C ( H2 protection) for 10 hours, and keep warm at 650°C ( H2 protection) for 2 hours. , furnace cooling (H 2 protection), and an atmosphere of nitrogen and hydrogen gas to prevent oxidation of the electrodes.
本願では、電解質を水及びエタノールと混合して溶液とし、電解質を水及びエタノールに溶解させ、エタノールの添加により溶剤の揮発が効率化され、加熱により電解質が電極に配置され、従来の電解質と電極の混合・調製と異なり、加熱中にガス保護が利用され、これにより、ニッケル電極の酸化が防止され、電極中の有効電解質を確保し、電解質の浪費を回避するために、陰極電解質の添加量は式及び電解質の必要質量範囲に応じて厳格に制御されなければならない。 In the present application, the electrolyte is mixed with water and ethanol to form a solution, the electrolyte is dissolved in water and ethanol, the addition of ethanol makes the volatilization of the solvent more efficient, and the electrolyte is placed on the electrode by heating. Unlike the mixing and preparation of , gas protection is utilized during heating, which prevents oxidation of the nickel electrode, ensures the availability of electrolyte in the electrode, and avoids waste of electrolyte. must be strictly controlled according to the formula and the required mass range of the electrolyte.
以下、実施例を参照しながら本願についてさらに詳細に説明する。 The present application will be described in more detail below with reference to examples.
実施例１
１、電解質Ｌｉ2ＣＯ3、Ｋ2ＣＯ3と水とエタノールを所定の割合（２０：２０：３０、質量比）で混合し、１．５時間撹拌した。
２、電極質量を秤量した結果、３３ｇであり、電極の空隙率を測定した結果、７７％であり、電極内部の電解質の理論必要量を算出した結果、２５．３ｇであった。
３、電解質の添加に必要な電極をトレイに入れて、電解質とエタノールとの混合溶液を加え、質量を１００ｇとした。
４、トレイをオーブンに入れて、エタノールを完全に揮発させるまで、温度を３０℃としながら換気する。
５、電極と電解質との全質量を秤量した結果、電極内部の電解質の必要質量の範囲（７５％理論必要量）を満たす５２ｇであった。
６、電極と電解質を加熱炉に入れて、加熱工程として常温～４５０℃（Ｎ2保護）５時間、４５０～６５０℃（Ｈ2保護）１０時間、６５０℃で保温２時間（Ｈ2保護）、炉冷（Ｈ2保護）とし、窒素ガス及び水素ガスの雰囲気によって電極の酸化が阻止された。
７、冷却後の電極と電解質の重量を秤量した結果、５０．９ｇであり、電解質の添加質量を計算した結果、１７．９ｇであった。
８、電極を電池セルに組み立て、性能をテストし、ここで、電池セルは電解質５０ｇを必要とし、電極には塩１７．９ｇが含まれており、残りの電解質はチャネルに配置された。電池セルの開回路電圧は１．３９０５Ｖであり、電池の電流密度は９３Ａ／ｃｍ2であり、チャネル内に電解質５０ｇを添加するという従来の方法よりも開回路電圧は０．０５Ｖ増加し、電流密度は１０Ａ／ｃｍ2増加した。
Example 1
1. Electrolytes Li 2 CO 3 , K 2 CO 3 , water and ethanol were mixed in a predetermined ratio (20:20:30, mass ratio) and stirred for 1.5 hours.
2. The weight of the electrode was 33 g, the porosity of the electrode was measured and found to be 77%, and the theoretical required amount of electrolyte inside the electrode was calculated and found to be 25.3 g.
3. Put the electrodes necessary for the addition of the electrolyte into the tray, add the mixed solution of the electrolyte and ethanol, and adjust the mass to 100 g.
4. Place the tray in an oven and ventilate at a temperature of 30°C until the ethanol is completely volatilized.
5. As a result of weighing the total mass of the electrode and the electrolyte, it was 52 g, which satisfies the required mass range (75% theoretical required amount) of the electrolyte inside the electrode.
6. Place the electrode and electrolyte in a heating furnace, and heat up to room temperature ~ 450°C ( N2 protection) for 5 hours, 450 ~ 650°C ( H2 protection) for 10 hours, and keep warm at 650°C for 2 hours ( H2 protection). , furnace cooling (H 2 protection), and an atmosphere of nitrogen and hydrogen gas to prevent oxidation of the electrodes.
7. As a result of weighing the weight of the electrode and the electrolyte after cooling, it was 50.9 g, and as a result of calculating the added mass of the electrolyte, it was 17.9 g.
8. The electrode was assembled into a battery cell and tested for performance, where the battery cell required 50 g of electrolyte, the electrode contained 17.9 g of salt, and the rest of the electrolyte was placed in the channel. The open circuit voltage of the battery cell is 1.3905 V, the current density of the battery is 93 A/cm 2 , the open circuit voltage is 0.05 V higher than the conventional method of adding 50 g of electrolyte in the channel, and the current Density increased by 10 A/cm 2 .
実施例２
１、電解質Ｌｉ2ＣＯ3、Ｋ2ＣＯ3と水とエタノールを所定の割合（２０：４０：４０、質量比）で混合し、１．８時間撹拌した。
２、電極質量を秤量した結果、３０ｇであり、電極の空隙率を測定した結果、７７％であり、電極内部の電解質の理論必要量を算出した結果、２４．１ｇであった。
３、電解質の添加に必要な電極をトレイに入れて、電解質とエタノールの混合溶液を加え、質量を１００ｇとした。
４、トレイをオーブンに入れて、エタノールを完全に揮発させるまで、温度を３０℃としながら換気する。
５、電極と電解質の全質量を秤量した結果、電極内部の電解質の必要質量の範囲（電極の電解質理論質量の６０％）を満たす４４．５ｇであった。
６、電極と電解質を加熱炉に入れて、加熱工程として常温～４５０℃（Ｎ2保護）５時間、４５０～６５０℃（Ｈ2保護）１０時間、６５０℃で２時間保温（Ｈ2保護）、炉冷（Ｈ2保護）とし、窒素ガス及び水素ガスの雰囲気によって電極の酸化が阻止された。
７、冷却後の電極と電解質の重量を秤量した結果、４３ｇであり、電解質の添加質量を計算した結果、１３ｇであった。
８、電極を電池セルに組み立て、性能をテストし、ここで、電池セルは、電解質５０ｇを必要とし、電極には塩１３ｇが含まれており、残りの電解質はチャネルに配置された。電池セルの開回路電圧は１．３８８５Ｖであり、電池の電流密度は９４Ａ／ｃｍ2であり、チャネル内に電解質５０ｇを添加するという従来の方法よりも、開回路電圧は０．０４Ｖ増加し、電流密度は９Ａ／ｃｍ2増加した。
Example 2
1. Electrolytes Li 2 CO 3 , K 2 CO 3 , water and ethanol were mixed in a predetermined ratio (20:40:40, mass ratio) and stirred for 1.8 hours.
2. The weight of the electrode was 30 g, the porosity of the electrode was measured and found to be 77%, and the theoretical required amount of electrolyte inside the electrode was calculated and found to be 24.1 g.
3. Put the electrodes necessary for adding the electrolyte into the tray, add the mixed solution of the electrolyte and ethanol, and adjust the mass to 100 g.
4. Place the tray in an oven and ventilate at a temperature of 30°C until the ethanol is completely volatilized.
5. The total mass of the electrode and the electrolyte was weighed and found to be 44.5 g, which satisfies the required mass of the electrolyte inside the electrode (60% of the theoretical electrolyte mass of the electrode).
6. Place the electrode and electrolyte in a heating furnace, and heat at room temperature to 450°C ( N2 protection) for 5 hours, 450 to 650°C ( H2 protection) for 10 hours, and keep warm at 650°C for 2 hours ( H2 protection). , furnace cooling (H 2 protection), and an atmosphere of nitrogen and hydrogen gas to prevent oxidation of the electrodes.
7. As a result of weighing the weight of the electrode and the electrolyte after cooling, it was 43 g, and as a result of calculating the added mass of the electrolyte, it was 13 g.
8. The electrode was assembled into a battery cell and tested for performance, where the battery cell required 50 g of electrolyte, the electrode contained 13 g of salt, and the rest of the electrolyte was placed in the channel. The open circuit voltage of the battery cell is 1.3885 V, the current density of the battery is 94 A/cm 2 , the open circuit voltage is increased by 0.04 V compared to the conventional method of adding 50 g of electrolyte in the channel, Current density increased by 9 A/cm 2 .
実施例３
１、電解質Ｌｉ2ＣＯ3、Ｋ2ＣＯ3と水とエタノールを所定の割合（２０：３０：３５、質量比）で混合し、２時間撹拌した。
２、電極質量を秤量した結果、３５ｇであり、電極の空隙率を測定した結果、７７％であり、電極内部の電解質の理論必要量を算出した結果、２７．１ｇであった。
３、電解質の添加に必要な電極をトレイに入れて、電解質とエタノールの混合溶液を加え、質量を１００ｇとした。
４、トレイをオーブンに入れて、エタノールを完全に揮発させるまで、温度を３０℃としながら換気する。
５、電極と電解質の全質量を秤量した結果、電極内部の電解質の必要質量の範囲（電極の理論電解質必要量の７８％）を満たす５６．１ｇであった。
６、電極と電解質を加熱炉に入れて、加熱工程として常温～４５０℃（Ｎ2保護）５時間、４５０～６５０℃（Ｈ2保護）１０時間、６５０℃で２時間保温（Ｈ2保護）、炉冷（Ｈ2保護）とし、窒素ガス及び水素ガスの雰囲気によって電極の酸化が阻止された。
７、冷却後の電極と電解質の重量を秤量した結果、５５．１ｇであり、電解質の添加質量を計算した結果、２０．１ｇであった。
８、電極を電池セルに組み立て、性能をテストし、ここで、電池セルは電解質５０ｇを必要とし、電極には塩２０．１ｇが含まれており、残りの電解質はチャネルに配置された。電池セルの開回路電圧は１．４０１Ｖであり、電池の電流密度は９６Ａ／ｃｍ2であり、チャネル内に電解質５０ｇを添加するという従来の方法よりも、開回路電圧は０．０６Ｖ増加し、電流密度は１２Ａ／ｃｍ2増加した。
Example 3
1. Electrolytes Li 2 CO 3 , K 2 CO 3 , water and ethanol were mixed in a predetermined ratio (20:30:35, mass ratio) and stirred for 2 hours.
2. The weight of the electrode was 35 g, the porosity of the electrode was measured and found to be 77%, and the theoretical required amount of electrolyte inside the electrode was calculated and found to be 27.1 g.
3. Put the electrodes necessary for adding the electrolyte into the tray, add the mixed solution of the electrolyte and ethanol, and adjust the mass to 100 g.
4. Place the tray in an oven and ventilate at a temperature of 30°C until the ethanol is completely volatilized.
5. The total mass of the electrode and electrolyte was weighed and found to be 56.1 g, which satisfies the required mass of the electrolyte inside the electrode (78% of the theoretical electrolyte required for the electrode).
6. Place the electrode and electrolyte in a heating furnace, and heat at room temperature to 450°C ( N2 protection) for 5 hours, 450 to 650°C ( H2 protection) for 10 hours, and keep warm at 650°C for 2 hours ( H2 protection). , furnace cooling (H 2 protection), and an atmosphere of nitrogen and hydrogen gas to prevent oxidation of the electrodes.
7. As a result of weighing the weight of the electrode and the electrolyte after cooling, it was 55.1 g, and as a result of calculating the added mass of the electrolyte, it was 20.1 g.
8. The electrode was assembled into a battery cell and tested for performance, where the battery cell required 50 g of electrolyte, the electrode contained 20.1 g of salt, and the rest of the electrolyte was placed in the channel. The open circuit voltage of the battery cell is 1.401 V, the current density of the battery is 96 A/cm 2 , the open circuit voltage is increased by 0.06 V compared to the conventional method of adding 50 g of electrolyte in the channel, Current density increased by 12 A/cm 2 .
以上は本願の好適な実施例に過ぎず、本願を限定するためのものではなく、本願の精神及び原則を逸脱することなく行われる全ての修正、等価置換や改良などは、本願の保護範囲に含まれるべきである。 The above are only preferred embodiments of the present application and are not intended to limit the present application. should be included.
Claims (9)
電極質量を秤量して電極の空隙率を測定し、電極内部の電解質の理論必要質量を算出するステップ２と、
電極を容器に入れて、電解質混合溶液を加えるステップ３と、
容器を乾燥条件下に置いて、水及びエタノールを完全に揮発させるステップ４と、
乾燥後の電極と電極上に付着させた電解質との全質量を秤量して、さらに、電極上に付着された電解質の質量を算出し、電解質の質量が、電極内部の電解質の理論必要質量の６０％～８０％である電極内部の電解質の実際必要質量を満たさない場合、ステップ３及びステップ４を繰り返し、電解質の質量が電極内部の電解質の実際必要質量を超える場合、電極内部の電解質の実際必要質量の範囲となるまで、余分な電解質を除去するステップ５と、
ステップ５で得られた電極を加熱して昇温し、加熱昇温が終了した後冷却し、溶融炭酸塩型燃料電池の電解質添加を完了するステップ６とを含む、ことを特徴とする溶融炭酸塩型燃料電池の電解質添加方法。 Step 1 of mixing and stirring an electrolyte with water and ethanol to obtain an electrolyte mixed solution;
Step 2 of weighing the electrode mass to measure the porosity of the electrode and calculating the theoretical required mass of the electrolyte inside the electrode;
step 3 of placing the electrode in a container and adding an electrolyte mixed solution;
step 4, placing the container under dry conditions to completely volatilize water and ethanol;
The total mass of the dried electrode and the electrolyte deposited on the electrode is weighed, and the mass of the electrolyte deposited on the electrode is calculated. The mass of the electrolyte is the theoretical required mass of the electrolyte inside the electrode. If the actual required mass of electrolyte inside the electrode, which is 60% to 80%, is not met, repeat steps 3 and 4; if the mass of electrolyte exceeds the actual required mass of electrolyte inside the electrode, step 5 removing excess electrolyte to the required mass range;
Step 6: heating the electrode obtained in step 5 to raise the temperature; cooling after the heating is completed; Electrolyte addition method for salt type fuel cell.
ｍ電解質＝ρ電解質Ｖ空隙＝ρ電解質（Ｖ電極－ｍ電極／ρニッケル）
ここで、ｍ電解質は電極内部の電解質の理論必要質量を表し、ρ電解質は電解質の密度を表し、Ｖ空隙は電極の空隙の体積を表し、Ｖ電極は電極の体積を表し、ｍ電極は電極の質量を表し、ρニッケルは金属ニッケルの密度を表す、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電解質添加方法。 In step 2, the formula for calculating the theoretical required mass of the electrolyte inside the electrode is the following formula,
m electrolyte = ρ electrolyte V void = ρ electrolyte (V electrode - m electrode /ρ nickel )
Here, m electrolyte represents the theoretical required mass of the electrolyte inside the electrode, ρ electrolyte represents the density of the electrolyte, V void represents the volume of the electrode void, V electrode represents the volume of the electrode, and m electrode represents the volume of the electrode. 2. The method of adding electrolyte to a molten carbonate fuel cell according to claim 1, wherein ρ nickel represents the density of metallic nickel.
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