CN107032785B - 一种窄带隙高极性的无铅铁电陶瓷及其制备方法 - Google Patents
一种窄带隙高极性的无铅铁电陶瓷及其制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000000498 ball milling Methods 0.000 claims abstract description 33
- 239000002270 dispersing agent Substances 0.000 claims abstract description 15
- 238000000462 isostatic pressing Methods 0.000 claims abstract description 9
- 238000009768 microwave sintering Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000007040 multi-step synthesis reaction Methods 0.000 claims abstract description 3
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- 238000001035 drying Methods 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 27
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 24
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 230000002194 synthesizing effect Effects 0.000 claims description 14
- 229910010252 TiO3 Inorganic materials 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
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Abstract
本发明公开了一种可调窄带隙高极性无铅铁电陶瓷，组成通式为：(1‑x)Ba0.9Ca0.1TiO3‑xBaBiO3+0.06Bi2WO6；其中x表示摩尔分数，0.01≤x≤0.3。这种陶瓷用多步合成方法，结合球磨混合添加分散剂以及等静压与微波烧结制备方法制备而成，该系列产品具有可调窄带隙Eg=1.2‑2.2eV，高的稳定性，优良的铁电性能P max=21‑35μC/cm2，绿色环保。
Description
技术领域
本发明涉及光电应用的无铅铁电陶瓷材料，具体是一种ABO3型钙钛矿结构的具有窄带隙高极性的无铅铁电陶瓷及其制备方法。
背景技术
光伏发电技术可以将能量来源巨大的太阳辐射光能直接转换为清洁的电能，是新能源中最具开发规模和商业化发展前景的发电方式。光伏发电是利用半导体界面p-n结的光生伏特效应，将光能直接转变为电能的一种技术。光伏效应依赖于两个基本过程来实现：光生载流子的产生与内建电场的作用下光生电子和空穴分离和收集，形成向特定方向流动的净电流。其中最核心的问题之一是通过光伏材料吸收太阳光子分离电子-空穴产生光伏效应，但是传统p-n 结分离电子-空穴的光伏器件的能量转换效率受到限制。为了避免上述缺陷、获得更高的能量转换效率，需要开发无结场结构光伏器件。
铁电材料是指在居里温度以下具有铁电自发极化的功能材料，铁电极化所形成的极化电场可有效地分离光激发下产生的电子—空穴对，可产生明显的光伏效应。然而铁电材料是宽带隙的绝缘体，无法有效地吸收太阳光中的可见光，光电转换效率低。为了提高铁电材料的光电转换效率，必须同时具有窄带隙、高极性。但是，传统的钙钛矿结构氧化物铁电材料很难同时具有铁电性与半导特性。因此开发高极性铁电半导体材料是目前的研究热点。
发明内容
本发明的目的是正对现有技术的不足，而提供一种窄带隙高极性的无铅铁电陶瓷及其制备方法。这种陶瓷材料可有效吸收太阳光能量，同时保持合理内建电场，获得光生电子和空穴分离、收集，具有高的稳定性、优良的铁电性能P max=21-35μC/cm2，绿色环保,内建电场可有效分离电子与空穴，具有优良的光电转换效率。
实现本发明目的的技术方案是：
一种窄带隙高极性的无铅铁电陶瓷，组成通式为：
(1-x) Ba0.9Ca0.1TiO3-xBaBiO3+0.06Bi2WO6；其中x表示摩尔分数，0.01≤x≤0.3。
上述窄带隙高极性的无铅铁电陶瓷的制备方法，该方法为多步合成，球磨混合添加分散剂以及等静压与微波烧结结合，具体包括如下步骤：
(1) 第一步以分析纯BaCO3、CaCO3、TiO2为原料按照化学计量式Ba0.9Ca0.1TO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于1200℃保温6小时预合成主晶相Ba0.9Ca0.1TiO3；
(2) 第二步以分析纯BaCO3、Bi2O3为原料按照化学计量式BaBiO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于760℃保温3小时预合成主晶相BaBiO3；
(3) 第三步以分析纯WO3、Bi2O3为原料按照化学计量式Bi2WO6配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于600℃保温2小时预合成主晶相Bi2WO6；
(4) 第四步以合成好的Ba0.9Ca0.1TiO3、BaBiO3、Bi2WO6为原料按照化学计量式(1-x) Ba0.9Ca0.1TiO3-xBaBiO3+0.06Bi2WO6，其中x表示摩尔分数(0.01≤x≤0.3)配料；以无水乙醇为介质，加入甲基戊醇分散剂球磨，干燥，再在高铝坩埚中于980℃保温3小时预合成固溶体；
(5) 预合成的固溶体以无水乙醇为介质，加入甲基戊醇分散剂球磨12小时，干燥，加入5%的PVA造粒，150Mpa等静压成型；
(6) 在950-1000℃微波烧结0.3小时，粉碎，粉碎后的粉末测量吸收光谱；
(7) 烧结的样品加工成两面光滑，直径12.0mm，厚度0.5mm的薄片，两面镀银电极即成，测量铁电性能。
这种方法通过Bi2WO6的辅助烧结与提供A位Bi离子协同作用，结合BaBiO3组成中B位Bi的变价，在B位出现相同元素的不同价态Bi3+/ Bi5+，诱导出现特殊的同素异价B位离子有序态，产生电子跳跃导电机制，由于这种电子跳跃是局域束缚状态，产生类似极化子的导电与极化双重作用，结合多步合成主晶相，微波短时烧结，形成多层次成分/结构梯度层结构，一方面降低带隙，同时保持铁电高极性。
这种方法所得陶瓷材料可有效吸收太阳光能量，同时保持合理内建电场，获得光生电子和空穴分离、收集，具有高的稳定性、优良的铁电性能P max=21-35μC/cm2，绿色环保。
具体实施方式：
下面结合具体实施例对本发明内容作进一步的阐述，但不是对本发明的限定。
实施例1：
制备成分为：(1-x) Ba0.9Ca0.1TiO3-xBaBiO3+0.06Bi2WO6 的陶瓷材料，其中x=0.015。
制备方法包括如下步骤：
(1)第一步以分析纯BaCO3、CaCO3、TiO2为原料，按照化学计量式Ba0.9Ca0.1TO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于1200℃保温6小时预合成主晶相Ba0.9Ca0.1TiO3；
(2)第二步以分析纯BaCO3、Bi2O3为原料按照化学计量式BaBiO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于760℃保温3小时预合成主晶相BaBiO3；
(3)第三步以分析纯WO3、Bi2O3为原料按照化学计量式Bi2WO6配料；以无水乙醇为介质球磨12h，干燥，再在高铝坩埚中于600℃保温2小时预合成主晶相Bi2WO6；
(4)第四步以合成好的Ba0.9Ca0.1TiO3、BaBiO3、Bi2WO6为原料，按照化学计量式(1-x) Ba0.9Ca0.1TiO3-xBaBiO3+0.06Bi2WO6；其中x表示摩尔分数(x=0.015)配料；以无水乙醇为介质，加入甲基戊醇分散剂球磨，干燥，再在高铝坩埚中于980℃保温3小时预合成固溶体；
(5)预合成的固溶体以无水乙醇为介质，加入甲基戊醇分散剂球磨12h，干燥，加入5%的PVA造粒，150Mpa等静压成型；
(6)在990℃微波烧结0.3小时，粉碎，粉碎后的粉末测量吸收光谱；
（7）烧结的样品加工成两面光滑，直径12.0mm，厚度0.5mm的薄片，两面镀银电极即成，镀银电极可测量铁电性能。
性能测量结果如表1所示。
实施例2：
制备成分为：(1-x) Ba0.9Ca0.1TiO3-xBaBiO3+0.06Bi2WO6的陶瓷材料，其中x=0.025。
制备方法包括如下步骤：
（1）第一步以分析纯BaCO3、CaCO3、TiO2为原料按照化学计量式Ba0.9Ca0.1TO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于1200℃保温6小时预合成主晶相Ba0.9Ca0.1TiO3；
（2）第二步以分析纯BaCO3、Bi2O3为原料按照化学计量式BaBiO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于760℃保温3小时预合成主晶相BaBiO3；
（3）第三步以分析纯WO3、Bi2O3为原料按照化学计量式Bi2WO6配料；以无水乙醇为介质球磨12h，干燥，再在高铝坩埚中于600℃保温2小时预合成主晶相Bi2WO6；
（4）第四步以合成好的Ba0.9Ca0.1TiO3、BaBiO3、Bi2WO6为原料按照化学计量式(1-x)Ba0.9Ca0.1TiO3-xBaBiO3+0.06Bi2WO6；其中x表示摩尔分数(x=0.25)配料；以无水乙醇为介质，加入甲基戊醇分散剂球磨，干燥，再在高铝坩埚中于980℃保温3小时预合成固溶体；
（5）预合成的固溶体以无水乙醇为介质，加入甲基戊醇分散剂球磨12h，干燥，加入5%的PVA造粒，150Mpa等静压成型；
（6）在950℃微波烧结0.3小时，粉碎，粉碎后的粉末可测量吸收光谱；
（7）烧结的样品加工成两面光滑，直径12.0mm，厚度0.5mm的薄片，两面镀银电极即成，镀银电极可测量铁电性能。
性能测量结果如表1所示。
实施例3：
制备成分为：(1-x) Ba0.9Ca0.1TiO3-xBaBiO3+0.06Bi2WO6的陶瓷材料，其中x=0.15。
制备方法包括如下步骤：
（1）第一步以分析纯BaCO3、CaCO3、TiO2为原料按照化学计量式Ba0.9Ca0.1TO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于1200℃保温6小时预合成主晶相Ba0.9Ca0.1TiO3；
（2）第二步以分析纯BaCO3、Bi2O3为原料按照化学计量式BaBiO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于760℃保温3小时预合成主晶相BaBiO3；
（3）第三步以分析纯WO3、Bi2O3为原料按照化学计量式Bi2WO6配料；以无水乙醇为介质球磨12h，干燥，再在高铝坩埚中于600℃保温2小时预合成主晶相Bi2WO6；
（4）第四步以合成好的Ba0.9Ca0.1TiO3、BaBiO3、Bi2WO6为原料按照化学计量式(1-x)Ba0.9Ca0.1TiO3-xBaBiO3+0.06Bi2WO6；其中x表示摩尔分数(x=0.15)配料；以无水乙醇为介质，加入甲基戊醇分散剂球磨，干燥，再在高铝坩埚中于980℃保温3小时预合成固溶体；
（5）预合成的固溶体以无水乙醇为介质，加入甲基戊醇分散剂球磨12h，干燥，加入5%的PVA造粒，150Mpa等静压成型；
（6）在970℃微波烧结0.3小时，粉碎，粉碎后的粉末可测量吸收光谱；
（7）烧结的样品加工成两面光滑，直径12.0mm，厚度0.5mm的薄片，两面镀银电极即成，镀银电极可测量铁电性能。
性能测量结果如表1所示。
实施例4：
制备成分为：(1-x) Ba0.9Ca0.1TiO3-xBaBiO3+0.06Bi2WO6的陶瓷材料，其中x=0.2。
制备方法包括如下步骤：
（1）第一步以分析纯BaCO3、CaCO3、TiO2为原料按照化学计量式Ba0.9Ca0.1TO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于1200℃保温6小时预合成主晶相Ba0.9Ca0.1TiO3；
（2）第二步以分析纯BaCO3、Bi2O3为原料按照化学计量式BaBiO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于760℃保温3小时预合成主晶相BaBiO3；
（3）第三步以分析纯WO3、Bi2O3为原料按照化学计量式Bi2WO6配料；以无水乙醇为介质球磨12h，干燥，再在高铝坩埚中于600℃保温2小时预合成主晶相Bi2WO6；
（4）第四步以合成好的Ba0.9Ca0.1TiO3、BaBiO3、Bi2WO6为原料按照化学计量式(1-x)Ba0.9Ca0.1TiO3-xBaBiO3+0.06Bi2WO6；其中x表示摩尔分数(x=0.015)配料；以无水乙醇为介质，加入甲基戊醇分散剂球磨，干燥，再在高铝坩埚中于980℃保温3小时预合成固溶体；
（5）预合成的固溶体以无水乙醇为介质，加入甲基戊醇分散剂球磨12h，干燥，加入5%的PVA造粒，150Mpa等静压成型；
（6）在990℃微波烧结0.3小时，粉碎，粉碎后的粉末可测量吸收光谱；
（7）烧结的样品加工成两面光滑，直径12.0mm，厚度0.5mm的薄片，两面镀银电极即成，镀银电极可测量铁电性能。
性能测量结果如表1所示。
表1 ：(1-x) Ba0.9Ca0.1TiO3-xBaBiO3+0.06Bi2WO6陶瓷的带隙Eg与铁电最大极性P max (为了对比，表中列出了Ba0.9Ca0.1TiO3陶瓷的带隙Eg与铁电最大极性P max)
| 成分<i>x</i> | 带 隙<i>E</i>g(eV) | 最大极性<i>P</i><sub>max</sub>(μC/cm<sup>2</sup>) | 最大极性电场<i>E</i>(kV/cm) | 实施例 |
| Ba<sub>0.9</sub>Ca<sub>0.1</sub>TO<sub>3</sub> | 3.1 | 28 | 25 | 对比 |
| 0.015 | 2.1 | 35 | 20 | 1 |
| 0.25 | 1.2 | 23 | 18 | 2 |
| 0.15 | 1.5 | 26 | 21 | 3 |
| 0.2 | 1.8 | 29 | 23 | 4 |
通过以上给出的实施例，可以进一步的清楚的了解本发明的内容，但他们不是对本发明的限定。
Claims (2)
1.一种窄带隙高极性的无铅铁电陶瓷，其特征在于，组成通式为：
(1-x) Ba0.9Ca0.1TiO3-xBaBiO3+0.06Bi2WO6；其中x表示摩尔分数，0.01≤x≤0.3。
2.如权利要求1所述的窄带隙高极性的无铅铁电陶瓷的制备方法，其特征是多步合成，球磨混合添加分散剂以及等静压与微波烧结结合，具体包括如下步骤：
（1）第一步以分析纯BaCO3、CaCO3、TiO2为原料按照化学计量式Ba0.9Ca0.1TO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于1200℃保温6小时预合成主晶相Ba0.9Ca0.1TiO3；
（2）第二步以分析纯BaCO3、Bi2O3为原料按照化学计量式BaBiO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于760℃保温3小时预合成主晶相BaBiO3；
（3）第三步以分析纯WO3、Bi2O3为原料按照化学计量式Bi2WO6配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于600℃保温2小时预合成主晶相Bi2WO6；
（4）第四步以合成好的Ba0.9Ca0.1TiO3、BaBiO3、Bi2WO6为原料按照化学计量式(1-x)Ba0.9Ca0.1TiO3-xBaBiO3+0.06Bi2WO6，其中x表示摩尔分数(0.01≤x≤0.3)配料；以无水乙醇为介质，加入甲基戊醇分散剂球磨，干燥，再在高铝坩埚中于980℃保温3小时预合成固溶体；
（5）预合成的固溶体以无水乙醇为介质，加入甲基戊醇分散剂球磨12小时，干燥，加入5%的PVA造粒，150Mpa等静压成型；
（6）在950-1000℃微波烧结0.3小时，粉碎；
（7）烧结的样品加工成两面光滑，直径12.0mm，厚度0.5mm的薄片，两面镀银电极即成。
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| CN104557024A (zh) * | 2014-12-18 | 2015-04-29 | 天津大学 | 高居里温度无铅钛酸钡基ptcr陶瓷材料及制备和应用 |
| CN105884350A (zh) * | 2016-04-08 | 2016-08-24 | 江苏大学 | 一种锆钛酸钡钙无铅压电陶瓷材料及其制备方法 |
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| CN103086712A (zh) * | 2012-12-14 | 2013-05-08 | 广西新未来信息产业股份有限公司 | 一种Bi2WO6改性的钛酸钡基无铅正温度系数电阻材料及其制备方法 |
| CN103787652A (zh) * | 2013-12-17 | 2014-05-14 | 江苏省陶瓷研究所有限公司 | 一种新型复相的ntc热敏电阻材料及其制备方法 |
| CN104557024A (zh) * | 2014-12-18 | 2015-04-29 | 天津大学 | 高居里温度无铅钛酸钡基ptcr陶瓷材料及制备和应用 |
| CN105884350A (zh) * | 2016-04-08 | 2016-08-24 | 江苏大学 | 一种锆钛酸钡钙无铅压电陶瓷材料及其制备方法 |
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