RU2807442C1 - SOLID OXIDE ELECTROLYTE MATERIAL WITH PROTON CONDUCTIVITY BASED ON BARIUM-LANTHANUM INDATE BaLa2In2O7 DOPED WITH STRONTIUM AND CALCIUM - Google Patents
SOLID OXIDE ELECTROLYTE MATERIAL WITH PROTON CONDUCTIVITY BASED ON BARIUM-LANTHANUM INDATE BaLa2In2O7 DOPED WITH STRONTIUM AND CALCIUM Download PDFInfo
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- RU2807442C1 RU2807442C1 RU2023108814A RU2023108814A RU2807442C1 RU 2807442 C1 RU2807442 C1 RU 2807442C1 RU 2023108814 A RU2023108814 A RU 2023108814A RU 2023108814 A RU2023108814 A RU 2023108814A RU 2807442 C1 RU2807442 C1 RU 2807442C1
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- lanthanum
- indate
- barium
- proton conductivity
- solid oxide
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- 239000011575 calcium Substances 0.000 title claims abstract description 19
- IQONKZQQCCPWMS-UHFFFAOYSA-N barium lanthanum Chemical compound [Ba].[La] IQONKZQQCCPWMS-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000007787 solid Substances 0.000 title claims abstract description 10
- 239000002001 electrolyte material Substances 0.000 title claims abstract description 8
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 6
- 229910052712 strontium Inorganic materials 0.000 title claims abstract description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 title claims abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 244000191761 Sida cordifolia Species 0.000 claims description 18
- 239000000463 material Substances 0.000 abstract description 27
- 239000000446 fuel Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- -1 calcium cations Chemical class 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001566 impedance spectroscopy Methods 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012078 proton-conducting electrolyte Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
Abstract
Description
Изобретение относится к производству материалов для электрохимических устройств, а именно, к твердооксидным электролитным материалам с протонной проводимостью на основе индата бария-лантана (BaLa2In2O7), которые могут быть использованы в качестве материала электролита в протонпроводящих твердооксидных топливных элементах, используемых для получения электроэнергии. The invention relates to the production of materials for electrochemical devices, namely, to solid oxide electrolyte materials with proton conductivity based on barium-lanthanum indate (BaLa 2 In 2 O 7 ), which can be used as an electrolyte material in proton-conducting solid oxide fuel cells used for receiving electricity.
Большинство известных материалов, характеризующихся протонной проводимостью в сочетании с низкой химической устойчивостью, обладают структурой перовскита или производной от нее. К таким материалам относится, например, материал протонпроводящего электролита на основе BaCeO3 (Ryu K.H., Haile S.M. Chemical stability and proton conductivity of doped BaCeO3-BaZrO3 solid solutions // Solid State Ionics. - 1999. V. 125, P. 355-367. https://doi.org/ 10.1016/S0167-2738(99)00196-4) [1]. Данный материал обладает низкой химической устойчивостью к углекислому газу, что снижает его эффективность при работе в топливных элементах. Most known materials characterized by proton conductivity combined with low chemical stability have a perovskite structure or a derivative of it. Such materials include, for example, a proton-conducting electrolyte material based on BaCeO 3 (Ryu KH, Haile SM Chemical stability and proton conductivity of doped BaCeO 3 -BaZrO 3 solid solutions // Solid State Ionics. - 1999. V. 125, P. 355 - 367. https://doi.org/ 10.1016/S0167-2738(99)00196-4) [1]. This material has low chemical resistance to carbon dioxide, which reduces its efficiency when used in fuel cells.
В качестве новых перспективных протонных проводников можно рассматривать химические соединения со структурой, отличной от структуры перовскита. В качестве таковых известен индат бария-лантана, характеризующийся блочно-слоевой структурой Раддлесдена-Поппера. Этот материал представляет собой протонный проводник при температуре ниже 450°C и влажности атмосферы pH2O = 2⋅10-2 атм, однако значения протонной проводимости для него сравнительно невысоки и при 450°C составляют 1.7⋅10-6 Ом-1∙см-1.Chemical compounds with a structure different from the perovskite structure can be considered as new promising proton conductors. As such, barium-lanthanum indate is known, characterized by a Ruddlesden-Popper block-layer structure. This material is a proton conductor at temperatures below 450°C and atmospheric humidity p H 2 O = 2⋅10 -2 atm, however, the values of proton conductivity for it are relatively low and at 450°C are 1.7⋅10 -6 Ohm -1 ∙ cm -1 .
Задача настоящего изобретения состоит в повышении протонной проводимости материала на основе индата бария-лантана, который может быть использован в качестве электролита в твердооксидном топливном элементе.The object of the present invention is to increase the proton conductivity of a barium lanthanum indate material, which can be used as an electrolyte in a solid oxide fuel cell.
Для этого предложен твердооксидный электролитный материал с протонной проводимостью, представляющий собой индат бария-лантана, допированный стронцием и кальцием, имеющий состав: BaLa1.9Sr0.1In1.95Ca0.05O6.925.For this purpose, a solid oxide electrolyte material with proton conductivity has been proposed, which is barium-lanthanum indate doped with strontium and calcium, having the composition: BaLa 1.9 Sr 0.1 In 1.95 Ca 0.05 O 6.925 .
При введении катионов стронция и кальция в подрешетку лантана образуются вакансии кислорода, вследствие чего возрастают значения кислородно-ионной и протонной проводимости.When strontium and calcium cations are introduced into the lanthanum sublattice, oxygen vacancies are formed, as a result of which the values of oxygen-ion and proton conductivity increase.
Полученный индат бария-лантана, допированный стронцием и кальцием характеризуется высокими значениями протонной проводимости с доминированием протонного транспорта при T < 450°C и pH2O = 2⋅10-2 атм, что является необходимыми условиями для применения материала в качестве электролита протонпроводящего топливного элемента.The resulting barium-lanthanum indate, doped with strontium and calcium, is characterized by high values of proton conductivity with the dominance of proton transport at T < 450°C and p H 2 O = 2⋅10 -2 atm, which are necessary conditions for the use of the material as a proton-conducting fuel electrolyte element.
Новый технический результат, достигаемый заявленным изобретением, заключается в создании материала на основе индата бария-лантана, характеризующегося высокими значениями протонной проводимости при T < 450°C и pH2O = 2⋅10-2 атм.The new technical result achieved by the claimed invention is the creation of a material based on barium-lanthanum indate, characterized by high values of proton conductivity at T < 450°C and p H 2 O = 2⋅10 -2 atm.
Изобретение иллюстрируется рисунками. На фиг. 1 показана дифрактограмма образца материала BaLa1.9Sr0.1In1.95Ca0.05O6.925. На фиг. 2 и 3 представлены температурные зависимости электропроводности образца материала BaLa1.9Sr0.1In1.95Ca0.05O6.925 в сравнении с материалом BaLa2In2O7 в сухой (pH2O = 3.5⋅10-5 атм) и влажной (pH2O = 2⋅10-2 атм) атмосферах соответственно. На фиг. 4 представлены температурные зависимости протонной проводимости образца материала BaLa1.9Sr0.1In1.95Ca0.05O6.925 в сравнении с материалом BaLa2In2O7.The invention is illustrated by drawings. In fig. Figure 1 shows a diffraction pattern of a sample of the material BaLa 1.9 Sr 0.1 In 1.95 Ca 0.05 O 6.925 . In fig. Figures 2 and 3 show the temperature dependences of the electrical conductivity of a sample of the material BaLa 1.9 Sr 0.1 In 1.95 Ca 0.05 O 6.925 in comparison with the material BaLa 2 In 2 O 7 in dry ( p H 2 O = 3.5⋅10 -5 atm) and wet ( p H 2 O = 2⋅10 -2 atm) atmospheres, respectively. In fig. Figure 4 shows the temperature dependences of the proton conductivity of a sample of the material BaLa 1.9 Sr 0.1 In 1.95 Ca 0.05 O 6.925 in comparison with the material BaLa 2 In 2 O 7 .
Материал BaLa1.9Sr0.1In1.95Ca0.05O6.925 получен методом твердофазного синтеза, известным из (Caldes M., Michel C., Rouillon T., Hervieu M., Raveau B. Novel indates Ln2BaIn2O7, n = 2 members of the Ruddlesden- Popper family (Ln = La, Nd) // Journal of Materials Chemistry. - V. 12. - P. 473-476. https://doi.org/10.1039/B108987K) [2]. Проведен рентгенофазовый анализ образца материала BaLa1.9Sr0.1In1.95Ca0.05O6.925 (Фиг. 1) на дифрактометре Bruker Advance D8 в СuКα-излучении при напряжении на трубке 40 кВ и токе 40 мА. Съемка производилась в интервале 2θ = 20°-80° с шагом 0.05°θ и экспозицией 1 секунда на точку. Анализ показал, что материал BaLa1.9Sr0.1In1.95Ca0.05O6.925 является однофазными и характеризуется тетрагональной симметрией.The material BaLa 1.9 Sr 0.1 In 1.95 Ca 0.05 O 6.925 was obtained by solid-phase synthesis, known from (Caldes M., Michel C., Rouillon T., Hervieu M., Raveau B. Novel indates Ln 2 BaIn 2 O 7 , n = 2 members of the Ruddlesden-Popper family (Ln = La, Nd) // Journal of Materials Chemistry. - V. 12. - P. 473-476. https://doi.org/10.1039/B108987K) [2]. An X-ray phase analysis of a sample of the material BaLa 1.9 Sr 0.1 In 1.95 Ca 0.05 O 6.925 (Fig. 1) was carried out on a Bruker Advance D8 diffractometer in CuKα radiation at a tube voltage of 40 kV and a current of 40 mA. The shooting was carried out in the interval 2θ = 20°-80° with a step of 0.05°θ and an exposure of 1 second per point. The analysis showed that the material BaLa 1.9 Sr 0.1 In 1.95 Ca 0.05 O 6.925 is single-phase and characterized by tetragonal symmetry.
Методом импедансной спектроскопии на приборе Impendancemeter Elins Z-1000P определяли электропроводность полученного материала BaLa1.9Sr0.1In1.95Ca0.05O6.925, (в температурном диапазоне от 300°C до 900°С, в частотном интервале 1 Гц÷1 МГц и в атмосферах воздуха (pO2 = 0.21 атм) и аргона (pO2 = 10-5 атм). Результаты измерения показаны на фиг. 2 и 3 в сухой (pH2O = 3.5⋅10−5 атм) и влажной (pH2O = 2⋅10-2 атм) атмосферах соответственно. Данные демонстрируют высокие значения электропроводности в исследуемом температурном интервале, которые для материала BaLa1.9Sr0.1In1.95Ca0.05O6.925 выше, чем для материала BaLa2In2O7.Using the impedance spectroscopy method on an Impendancemeter Elins Z-1000P device, the electrical conductivity of the resulting material BaLa 1.9 Sr 0.1 In 1.95 Ca 0.05 O 6.925 was determined (in the temperature range from 300°C to 900°C, in the frequency range 1 Hz ÷ 1 MHz and in air atmospheres (pO 2 = 0.21 atm) and argon (pO 2 = 10 -5 atm).The measurement results are shown in Fig. 2 and 3 in dry ( p H 2 O = 3.5⋅10 -5 atm) and wet ( p H 2 O = 2⋅10 -2 atm) atmospheres, respectively.The data demonstrate high values of electrical conductivity in the temperature range under study, which for the material BaLa 1.9 Sr 0.1 In 1.95 Ca 0.05 O 6.925 are higher than for the material BaLa 2 In 2 O 7 .
Значения протонной проводимости были получены, как разность значений электропроводности в атмосферах влажного и сухого аргона при одинаковой температуре. Температурные зависимости протонной проводимости материалов BaLa1.9Sr0.1In1.95Ca0.05O6.925 и BaLa2In2O7 представлены на фиг. 4, из которой видно, что при 450°C величина протонной проводимости материала BaLa1.9Sr0.1In1.95Ca0.05O6.925 составляет 1.3∙10−5 Ом−1∙см−1, а материала BaLa2In2O7 - 1.7∙10−6 Ом−1∙см−1.The proton conductivity values were obtained as the difference between the electrical conductivity values in atmospheres of wet and dry argon at the same temperature. The temperature dependences of the proton conductivity of the materials BaLa 1.9 Sr 0.1 In 1.95 Ca 0.05 O 6.925 and BaLa 2 In 2 O 7 are presented in Fig. 4, from which it can be seen that at 450°C the proton conductivity of the material BaLa 1.9 Sr 0.1 In 1.95 Ca 0.05 O 6.925 is 1.3∙10 −5 Ohm −1 ∙cm −1 , and the material BaLa 2 In 2 O 7 is 1.7∙ 10 −6 Ohm −1 ∙cm −1 .
Таким образом, получен новый протонпроводящий материал на основе индата бария-лантана, и который потенциально может быть применен в качестве материала электролита протонпроводящего твердооксидного элемента.Thus, a new proton-conducting material based on barium-lanthanum indate has been obtained, which can potentially be used as an electrolyte material for a proton-conducting solid oxide cell.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1145722A (en) * | 1997-07-29 | 1999-02-16 | Tokyo Gas Co Ltd | Manufacturing method of air pole for solid electrolytic fuel cell and solid electrolytic fuel cell having air pole manufactured by this method |
| RU2681947C1 (en) * | 2017-12-08 | 2019-03-14 | Федеральное государственное бюджетное учреждение науки Институт высокотемпературной электрохимии Уральского отделения Российской Академии наук | Solid oxide proton conducting material |
| KR20210080956A (en) * | 2019-12-23 | 2021-07-01 | 인천대학교 산학협력단 | Perovskite oxide for anode functional layer of Solid Oxide Fuel Cell, Composition of anode functional layer comprising the same, and Solid Oxide Fuel Cell comprising the same |
| RU2781270C1 (en) * | 2022-02-01 | 2022-10-11 | Федеральное государственное бюджетное учреждение науки Институт высокотемпературной электрохимии Уральского отделения Российской академии наук (ИВТЭ УрО РАН) | Solid oxide electrolyte material with proton conductivity |
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1145722A (en) * | 1997-07-29 | 1999-02-16 | Tokyo Gas Co Ltd | Manufacturing method of air pole for solid electrolytic fuel cell and solid electrolytic fuel cell having air pole manufactured by this method |
| RU2681947C1 (en) * | 2017-12-08 | 2019-03-14 | Федеральное государственное бюджетное учреждение науки Институт высокотемпературной электрохимии Уральского отделения Российской Академии наук | Solid oxide proton conducting material |
| KR20210080956A (en) * | 2019-12-23 | 2021-07-01 | 인천대학교 산학협력단 | Perovskite oxide for anode functional layer of Solid Oxide Fuel Cell, Composition of anode functional layer comprising the same, and Solid Oxide Fuel Cell comprising the same |
| RU2781270C1 (en) * | 2022-02-01 | 2022-10-11 | Федеральное государственное бюджетное учреждение науки Институт высокотемпературной электрохимии Уральского отделения Российской академии наук (ИВТЭ УрО РАН) | Solid oxide electrolyte material with proton conductivity |
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