CN108550874A - A kind of cerium oxide-barium cerate base solid-oxide fuel battery electrolyte and preparation method - Google Patents
A kind of cerium oxide-barium cerate base solid-oxide fuel battery electrolyte and preparation method Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 53
- 239000000446 fuel Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 title abstract description 8
- RKMSYLGAZSHVGJ-UHFFFAOYSA-N barium(2+) cerium(3+) oxygen(2-) Chemical compound [O-2].[Ba+2].[Ce+3] RKMSYLGAZSHVGJ-UHFFFAOYSA-N 0.000 title abstract description 3
- 239000002131 composite material Substances 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000008187 granular material Substances 0.000 claims abstract description 7
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 5
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 5
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 238000000748 compression moulding Methods 0.000 claims abstract description 3
- 238000005469 granulation Methods 0.000 claims abstract description 3
- 230000003179 granulation Effects 0.000 claims abstract description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 101150058765 BACE1 gene Proteins 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 238000010304 firing Methods 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 229910052684 Cerium Inorganic materials 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 229910052788 barium Inorganic materials 0.000 description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 5
- 229910000420 cerium oxide Inorganic materials 0.000 description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 3
- 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 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 2
- 229940075613 gadolinium oxide Drugs 0.000 description 2
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910002430 Ce0.8Gd0.2O2-δ Inorganic materials 0.000 description 1
- 229910002436 Ce0.8Gd0.2O2−δ Inorganic materials 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- -1 oxygen ion Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Classifications
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- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
-
- 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
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- 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
技术领域technical field
本发明涉及固体氧化物燃料电池的电解质领域,具体涉及一种氧化铈-铈酸钡基固体氧化物燃料电池电解质及制备方法。The invention relates to the field of electrolytes for solid oxide fuel cells, in particular to a cerium oxide-barium cerate-based solid oxide fuel cell electrolyte and a preparation method.
背景技术Background technique
固体氧化物燃料电池(SOFCs)因能量转化率高、无污染以及燃料多样性等优点而成为燃料电池领域的研究热点。电解质是SOFCs的关键与核心材料。目前,YSZ(氧化钇掺杂氧化锆)是发展最为成熟的SOFCs电解质材料。不过,YSZ通常在1000℃以上才具有较高的离子电导率,过高的工作温度给SOFCs带来了一系列问题,比如:电极活性降低、对连接体材料要求高、电池密封不好等。因此,降低SOFCs的工作温度,是扩大电池组件材料选择范围和提高电池长期运行稳定性的重要发展方向。但是,随着工作温度的降低,YSZ电解质的电导率迅速下降,导致电池性能急剧降低。开发新型的中温固体氧化物燃料电池电解质是当前的重点研究方向。Solid oxide fuel cells (SOFCs) have become a research hotspot in the field of fuel cells due to their high energy conversion efficiency, no pollution, and fuel diversity. Electrolyte is the key and core material of SOFCs. At present, YSZ (yttrium oxide doped zirconia) is the most mature electrolyte material for SOFCs. However, YSZ usually has a high ionic conductivity above 1000 ° C. Too high operating temperature has brought a series of problems to SOFCs, such as: reduced electrode activity, high requirements for connector materials, and poor battery sealing. Therefore, reducing the operating temperature of SOFCs is an important development direction to expand the selection of battery component materials and improve the long-term operation stability of batteries. However, as the operating temperature decreases, the conductivity of the YSZ electrolyte decreases rapidly, leading to a sharp decrease in battery performance. The development of new intermediate temperature solid oxide fuel cell electrolytes is the current key research direction.
中国专利文件 CN101000966公开了“一种复合掺杂氧化铈电解质及其制备方法”,该复合掺杂氧化铈电解质是符合Ce1-xGdx-yYyO2-0.5x化学计量比的氧化铈、氧化钆和氧化钇的复合氧化物,在600℃空气条件下的电导率为0.038 S·cm-1。中国专利文件CN102544559A公开了“ 一种用于固体氧化物燃料电池的氧化铈基电解质及其制备方法”,通过向氧化铈中添加氧化镧、氧化钒降低了烧成温度,该电解质在600℃空气条件下的电导率为0.0178S·cm-1。但是,氧化铈基电解质中的Ce4+在低氧分压或还原气氛下极易被部分还原成Ce3+,产生电子电导,导致SOFCs的开路电压下降,进而导致电池性能降低。Chinese patent document CN101000966 discloses "a composite doped cerium oxide electrolyte and its preparation method " . The composite oxide of gadolinium oxide and yttrium oxide has an electrical conductivity of 0.038 S·cm -1 at 600°C in air. Chinese patent document CN102544559A discloses "a cerium oxide-based electrolyte for solid oxide fuel cells and its preparation method". The firing temperature is reduced by adding lanthanum oxide and vanadium oxide to cerium oxide. The conductivity under the condition is 0.0178S·cm -1 . However, Ce 4+ in ceria-based electrolytes is easily partially reduced to Ce 3+ under low oxygen partial pressure or reducing atmosphere, resulting in electronic conductance, resulting in a decrease in the open-circuit voltage of SOFCs, which in turn leads to a decrease in battery performance.
中国专利文件 CN103086716A公开了“ 基于稀土氧化物掺杂铈酸钡的复合质子导体材料及其制备方法”,该电解质为氧化钆或氧化钇掺杂的铈酸钡,在550℃空气条件下的电导率高于10-2 S·cm-1。但是,铈酸钡电解质在含有CO2、H2O的条件下不稳定,易发生化学反应生成碳酸钡、氢氧化钡等,进而导致电导率下降。Chinese patent document CN103086716A discloses "composite proton conductor material based on rare earth oxide doped barium cerate and its preparation method". The electrolyte is barium cerate doped with gadolinium oxide or yttrium oxide. The rate is higher than 10 -2 S·cm -1 . However, the barium cerate electrolyte is unstable in the presence of CO 2 and H 2 O, and is prone to chemical reactions to form barium carbonate, barium hydroxide, etc., resulting in a decrease in conductivity.
Wenping Sun等(A novel electronic current-blocked stable mixed ionicconductor for solid oxide fuel cells, Journal of Power Sources, 2011, 196(1):62-68)介绍了一种稀土元素掺杂CeO2/BaCeO3复合电解质,实现了氧化铈基电解质和铈酸钡基电解质的性能优势互补,解决了氧化铈基电解质易被部分还原和铈酸钡基电解质化学不稳定的问题。但是,该复合电解质的烧成温度较高(>1350℃),两种电解质之间容易发生界面反应或元素扩散,导致电导率较低。Wenping Sun et al. (A novel electronic current-blocked stable mixed ionicconductor for solid oxide fuel cells, Journal of Power Sources, 2011, 196(1):62-68) introduced a rare earth element doped CeO 2 /BaCeO 3 composite electrolyte , realizing the complementary performance advantages of the cerium oxide-based electrolyte and the barium cerate-based electrolyte, and solving the problems that the cerium oxide-based electrolyte is easily partially reduced and the barium cerate-based electrolyte is chemically unstable. However, the firing temperature of the composite electrolyte is high (>1350°C), and interfacial reaction or element diffusion is prone to occur between the two electrolytes, resulting in low conductivity.
发明内容Contents of the invention
本发明针对现有技术存在的上述不足,提出一种Bi掺杂型Ce0.8Bi x Re(0.2-x)O2-δ-BaCe0.8Bi x Re(0.2-x)O3-δ (0≤x≤0.2,Re=La、Nd、Eu、Gd、Dy、Er、Yb等)复合电解质及制备方法。所制备的电解质具有烧成温度低、电导率高等优点。所提出的制备方法具有工艺简单、便于产业化的优点。Aiming at the above-mentioned deficiencies in the prior art, the present invention proposes a Bi-doped Ce 0.8 Bi x Re (0.2- x ) O 2-δ -BaCe 0.8 Bi x Re (0.2- x ) O 3-δ (0≤ x≤0.2, Re=La, Nd, Eu, Gd, Dy, Er, Yb, etc.) composite electrolyte and its preparation method. The prepared electrolyte has the advantages of low firing temperature and high electrical conductivity. The proposed preparation method has the advantages of simple process and convenient industrialization.
本发明是通过以下技术方案实现的,包括以下步骤。The present invention is realized through the following technical solutions, including the following steps.
1、Ce0.8Bi x Re(0.2-x)O2-δ-BaCe0.8Bi x Re(0.2-x)O3-δ复合粉体的制备方法如下所述。1. The preparation method of Ce 0.8 Bi x Re (0.2- x ) O 2-δ -BaCe 0.8 Bi x Re (0.2- x ) O 3-δ composite powder is as follows.
1.1 按Ce0.8Bi x Re(0.2-x)O2-δ-BaCe0.8Bi x Re(0.2-x) O3-δ化学计量比称取BaCO3、CeO2、Bi2O3、Re2O3 (Re=La、Nd、Eu、Gd、Dy、Er、Yb等),放入聚氨酯球磨罐中,加入无水乙醇,以氧化锆球为介质球磨8~12小时,原料、氧化锆球、无水乙醇的质量比为1: (2.5~3.5): (0.8~0.9),得到浆料。1.1 Weigh BaCO 3 , CeO 2 , Bi 2 O 3 , Re 2 O according to the stoichiometric ratio of Ce 0.8 Bi x Re ( 0.2- x ) O 2 -δ -BaCe 0.8 Bi x Re ( 0.2- x ) O 3- δ 3 (Re=La, Nd, Eu, Gd, Dy, Er, Yb, etc.), put it into a polyurethane ball mill tank, add absolute ethanol, and use zirconia balls as the medium for ball milling for 8 to 12 hours. Raw materials, zirconia balls, The mass ratio of absolute ethanol is 1: (2.5-3.5): (0.8-0.9), and the slurry is obtained.
1.2 烘干,造粒,在5~15MPa压力下压制成型,得到坯体。1.2 Drying, granulation, and compression molding under a pressure of 5-15 MPa to obtain a green body.
1.3 将坯体放入加热炉,升温至900~1050℃,保温10~15小时,然后随炉冷却。1.3 Put the green body into the heating furnace, raise the temperature to 900-1050°C, keep it warm for 10-15 hours, and then cool it with the furnace.
1.4 将煅烧后的块料破碎,得到Ce0.8BixRe(0.2-x)O2-δ-Ba Ce0.8BixRe(0.2-x)O3-δ复合粉体。1.4 Break the calcined block to obtain Ce 0.8 Bi x Re (0.2-x) O 2-δ -Ba Ce 0.8 Bi x Re (0.2-x) O 3-δ composite powder.
2、Ce0.8BixRe(0.2-x)O2-δ-Ba Ce0.8BixRe(0.2-x)O3-δ复合电解质的制备方法如下所述。2. The preparation method of Ce 0.8 Bi x Re (0.2-x) O 2-δ -Ba Ce 0.8 Bi x Re (0.2-x) O 3-δ composite electrolyte is as follows.
2.1 向Ce0.8BixRe(0.2-x)O2-δ-Ba Ce0.8BixRe(0.2-x)O3-δ复合粉体中加入1 wt.% 粘结剂,混合均匀,造粒,在30~60MPa压力下压制成厚度为0.3~1.5 mm的片状电解质坯体。2.1 Add 1 wt.% binder to the Ce 0.8 Bi x Re (0.2-x) O 2-δ -Ba Ce 0.8 Bi x Re (0.2-x) O 3-δ composite powder, mix well, and granulate , Pressed under a pressure of 30-60 MPa to form a sheet-shaped electrolyte green body with a thickness of 0.3-1.5 mm.
2.2 将电解质坯体放入加热炉,升温至1100~1250℃,保温2~6小时,得到固体氧化物燃料电池电解质。2.2 Put the electrolyte green body into the heating furnace, raise the temperature to 1100-1250°C, and keep it warm for 2-6 hours to obtain the solid oxide fuel cell electrolyte.
本发明中所述的原料纯度大于99.9%;所述的无水乙醇为分析纯级。The purity of the raw materials described in the present invention is greater than 99.9%; the described absolute ethanol is of analytical grade.
本发明所述的步骤1.1中Ce0.8Bi x Re(0.2-x)O2-δ和BaCe0.8Bi x Re(0.2-x) O3-δ的质量比为(95~50):(5~50)。The mass ratio of Ce 0.8 Bi x Re (0.2- x ) O 2-δ to BaCe 0.8 Bi x Re (0.2- x ) O 3-δ in step 1.1 of the present invention is (95~50): (5~ 50).
根据本发明优选的,步骤1.1中Ce0.8Bi x Re(0.2-x)O2-δ-BaCe0.8Bi x Re(0.2-x) O3-δ中0.05≤x≤0.12。Preferably according to the present invention, in step 1.1, in Ce 0.8 Bi x Re (0.2- x ) O 2-δ -BaCe 0.8 Bi x Re (0.2- x ) O 3-δ , 0.05≤x≤0.12.
本发明所述的步骤1.2中烘干温度为80~100℃,烘干时间为12~15小时。造粒粉的过筛目数为40目。In step 1.2 of the present invention, the drying temperature is 80-100° C., and the drying time is 12-15 hours. The sieve mesh of the granulated powder is 40 mesh.
根据本发明优选的,步骤1.3中的升温制度为:以3~6℃/min升温至950~1000℃,保温11~13小时。Preferably according to the present invention, the heating regime in step 1.3 is: heating at 3-6°C/min to 950-1000°C, and keeping the temperature for 11-13 hours.
本发明步骤2.1所述的粘结剂为浓度为5wt.% PVA(聚乙烯醇)水溶液或PVB(聚乙烯醇缩丁醛)乙醇溶液中的一种。The binder described in step 2.1 of the present invention is one of 5wt.% PVA (polyvinyl alcohol) aqueous solution or PVB (polyvinyl butyral) ethanol solution.
根据本发明优选的,步骤2.1中破碎粉体的过筛目数为40目。Preferably according to the present invention, the sieve mesh number of the crushed powder in step 2.1 is 40 mesh.
根据本发明优选的,步骤2.1中片状电解质片的厚度为0.6~1.2mm。Preferably according to the present invention, the thickness of the sheet-shaped electrolyte sheet in step 2.1 is 0.6-1.2 mm.
根据本发明优选的,步骤1.3中的升温制度为:以2~4℃/min升温至1150~1200℃,保温3~5小时。Preferably according to the present invention, the heating regime in step 1.3 is: heating up to 1150-1200°C at 2-4°C/min, and keeping the temperature for 3-5 hours.
有益效果Beneficial effect
1、烧成温度低:Bi2O3的熔点低,Bi掺杂使得CeO2/BaCeO3复合电解质的烧成温度降低100℃以上。1. Low firing temperature: Bi 2 O 3 has a low melting point, and Bi doping reduces the firing temperature of the CeO 2 /BaCeO 3 composite electrolyte by more than 100°C.
2、氧离子电导率高:与未掺杂Bi的单元素掺杂CeO2/BaCeO3复合电解质相比,离子电导率高3倍以上。2. High oxygen ion conductivity: Compared with single-element doped CeO 2 /BaCeO 3 composite electrolyte without Bi doping, the ion conductivity is more than 3 times higher.
3、通过一步反应即可制备出复合掺杂CeO2/BaCeO3粉体,不需要后续的混合工艺,工艺流程简单,便于产业化。3. Composite-doped CeO 2 /BaCeO 3 powder can be prepared through one-step reaction without subsequent mixing process, the process flow is simple, and it is convenient for industrialization.
具体实施方式Detailed ways
下面结合实施例对本发明的技术方案做进一步说明,但本发明所保护范围不限于此。The technical solutions of the present invention will be further described below in conjunction with the examples, but the protection scope of the present invention is not limited thereto.
实施例1Example 1
按90wt.% Ce0.8Bi0.1La0.1O2-δ-10 wt.% BaCe0.8Bi0.1La0.1O3-δ化学计量比称取BaCO3、CeO2、Bi2O3、La2O3,放入聚氨酯球磨罐中,加入无水乙醇,以氧化锆球为介质球磨10小时,原料、氧化锆球、无水乙醇的质量比为1: 3: 0.8,得到浆料。在90℃干燥12小时,过40目筛造粒,在10MPa压力下压制成型,得到坯体。将坯体放入加热炉,以3℃/min升温至1000℃,保温12小时,然后随炉冷却。将煅烧后的块料破碎,得到90wt.% Ce0.8Bi0.1La0.1O2-δ-10 wt.%BaCe0.8Bi0.1La0.1O3-δ复合粉体。向复合粉体中加入1 wt.% PVA水溶液,混合均匀,过40目筛造粒,在50MPa压力下压制成厚度为1.0 mm的片状电解质坯体。将电解质坯体放入加热炉,以3℃/min升温至1150℃,保温4小时,得到固体氧化物燃料电池电解质。Weigh BaCO 3 , CeO 2 , Bi 2 O 3 , La 2 O 3 according to 90wt.% Ce 0.8 Bi 0.1 La 0.1 O 2-δ -10 wt . % BaCe 0.8 Bi 0.1 La 0.1 O 3 - δ stoichiometric ratio, Put it into a polyurethane ball mill jar, add absolute ethanol, and use zirconia balls as the medium for ball milling for 10 hours. The mass ratio of raw materials, zirconia balls, and absolute ethanol is 1: 3: 0.8 to obtain a slurry. Dry at 90° C. for 12 hours, pass through a 40-mesh sieve to granulate, and press under a pressure of 10 MPa to obtain a green body. Put the green body into the heating furnace, raise the temperature to 1000°C at 3°C/min, keep it warm for 12 hours, and then cool down with the furnace. The calcined block was crushed to obtain 90wt.% Ce 0.8 Bi 0.1 La 0.1 O 2-δ -10 wt.% BaCe 0.8 Bi 0.1 La 0.1 O 3-δ composite powder. Add 1 wt.% PVA aqueous solution to the composite powder, mix well, pass through a 40-mesh sieve to granulate, and press under a pressure of 50 MPa to form a sheet-shaped electrolyte body with a thickness of 1.0 mm. Put the electrolyte body into a heating furnace, raise the temperature to 1150°C at 3°C/min, and keep it warm for 4 hours to obtain a solid oxide fuel cell electrolyte.
采用电化学工作站(上海辰华、CHI660E)测试,90wt.% Ce0.8Bi0.1La0.1O2-δ-10 wt.%BaCe0.8Bi0.1La0.1O3-δ复合电解质在600℃空气条件下的离子电导率为0.031 S cm-1。Using electrochemical workstation (Shanghai Chenhua, CHI660E) test, 90wt.% Ce 0.8 Bi 0.1 La 0.1 O 2-δ -10 wt.% BaCe 0.8 Bi 0.1 La 0.1 O 3-δ composite electrolyte under 600 ℃ air condition The ionic conductivity is 0.031 S cm -1 .
实施例2Example 2
按70wt.% Ce0.8Bi0.1Gd0.1O2-δ-30 wt.% BaCe0.8Bi0.1Gd0.1O3-δ化学计量比称取BaCO3、CeO2、Bi2O3、Gd2O3,放入聚氨酯球磨罐中,加入无水乙醇,以氧化锆球为介质球磨10小时,原料、氧化锆球、无水乙醇的质量比为1: 3.1: 0.9,得到浆料。在80℃干燥15小时,过40目筛造粒,在8MPa压力下压制成型,得到坯体。将坯体放入加热炉,以5℃/min升温至980℃,保温13小时,然后随炉冷却。将煅烧后的块料破碎,得到70wt.% Ce0.8Bi0.1Gd0.1O2-δ-30 wt.%BaCe0.8Bi0.1Gd0.1O3-δ复合粉体。向复合粉体中加入1 wt.% PVB乙醇溶液,混合均匀,过40目筛造粒,在40MPa压力下压制成厚度为0.9 mm的片状电解质坯体。将电解质坯体放入加热炉,以4℃/min升温至1200℃,保温5小时,得到固体氧化物燃料电池电解质。Weigh BaCO 3 , CeO 2 , Bi 2 O 3 , Gd 2 O 3 according to 70wt.% Ce 0.8 Bi 0.1 Gd 0.1 O 2-δ -30 wt .% BaCe 0.8 Bi 0.1 Gd 0.1 O 3-δ stoichiometric ratio, Put it into a polyurethane ball mill jar, add absolute ethanol, and use zirconia balls as the medium for ball milling for 10 hours. The mass ratio of raw materials, zirconia balls, and absolute ethanol is 1: 3.1: 0.9 to obtain a slurry. Dry at 80°C for 15 hours, pass through a 40-mesh sieve to granulate, and press to form under a pressure of 8 MPa to obtain a green body. Put the green body into the heating furnace, raise the temperature to 980°C at 5°C/min, keep it warm for 13 hours, and then cool down with the furnace. The calcined block was crushed to obtain 70wt.% Ce 0.8 Bi 0.1 Gd 0.1 O 2-δ -30 wt.% BaCe 0.8 Bi 0.1 Gd 0.1 O 3-δ composite powder. Add 1 wt.% PVB ethanol solution to the composite powder, mix well, pass through a 40-mesh sieve to granulate, and press under a pressure of 40MPa to form a sheet-shaped electrolyte body with a thickness of 0.9 mm. Put the electrolyte body into a heating furnace, raise the temperature to 1200°C at 4°C/min, and keep it warm for 5 hours to obtain a solid oxide fuel cell electrolyte.
采用电化学工作站(上海辰华、CHI660E)测试,70wt.% Ce0.8Bi0.1Gd0.1O2-δ-30 wt.%BaCe0.8Bi0.1Gd0.1O3-δ复合电解质在600℃、空气条件下的离子电导率为0.028 S cm-1。Using an electrochemical workstation (Shanghai Chenhua, CHI660E) test, 70wt.% Ce 0.8 Bi 0.1 Gd 0.1 O 2-δ -30 wt.% BaCe 0.8 Bi 0.1 Gd 0.1 O 3-δ composite electrolyte at 600 ℃, air conditions The ionic conductivity is 0.028 S cm -1 .
对比例1Comparative example 1
如实施例1所述,不同的是:未掺杂Bi元素。即:复合电解质的成分为90wt.%Ce0.8La0.2O2-δ-10 wt.% BaCe0.8La0.2O3-δ。该电解质的烧成温度为1300℃。在600℃、空气条件下的离子电导率为0.0078 S cm-1。As described in Example 1, the difference is: no Bi element is doped. That is: the composition of the composite electrolyte is 90wt.%Ce 0.8 La 0.2 O 2-δ -10 wt.% BaCe 0.8 La 0.2 O 3-δ . The firing temperature of this electrolyte is 1300°C. The ion conductivity at 600°C under air conditions is 0.0078 S cm -1 .
对比例2Comparative example 2
如实施例1所述,不同的是:未掺杂Bi元素。即:复合电解质的成分为70wt.%Ce0.8Gd0.2O2-δ-30 wt.% BaCe0.8Gd0.2O3-δ。该电解质的烧成温度为1350℃。在600℃、空气条件下的离子电导率为0.0071 S cm-1。As described in Example 1, the difference is: no Bi element is doped. That is: the composition of the composite electrolyte is 70wt.%Ce 0.8 Gd 0.2 O 2-δ -30 wt.% BaCe 0.8 Gd 0.2 O 3-δ . The firing temperature of this electrolyte is 1350°C. The ionic conductivity at 600°C under air conditions is 0.0071 S cm -1 .
本发明实施例1-2与对比例1-2相比,烧成温度显著降低,电导率提高3倍以上。说明Bi元素掺杂有利于降低CeO2/BaCeO3复合电解质的烧成温度和提高其离子电导率。Compared with Comparative Example 1-2, the firing temperature of Example 1-2 of the present invention is significantly lowered, and the electrical conductivity is increased by more than 3 times. It shows that Bi element doping is beneficial to reduce the firing temperature of CeO 2 /BaCeO 3 composite electrolyte and improve its ionic conductivity.
需要说明的是,以上列举的仅是本发明的若干个具体实施例,显然本发明不仅仅限于以上实施例,还可以有其他变形。本领域的技术人员从本发明公开内容直接导出或间接引申的所有变形,均应认为是本发明的保护范围。It should be noted that the above examples are only a few specific embodiments of the present invention, and obviously the present invention is not limited to the above embodiments, and other modifications are also possible. All deformations directly derived or indirectly derived from the disclosure content of the present invention by those skilled in the art should be considered as the protection scope of the present invention.
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