CN114380595A - 一种低烧结温度的氧离子导电陶瓷材料及其制备方法 - Google Patents
一种低烧结温度的氧离子导电陶瓷材料及其制备方法 Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 claims abstract description 32
- -1 oxygen ion Chemical class 0.000 claims abstract description 20
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Abstract
本发明属于陶瓷燃料电池领域,尤其涉及一种低烧结温度的氧离子导电陶瓷材料及其制备方法。本发明的目的是针对现有技术中氧离子导体氧化铈基电解质的烧结性能差、烧结助剂影响电解质的电导率等问题,提供了一种低烧结温度的陶瓷燃料电池氧离子导电陶瓷电解质及其制备方法。所述电解质材料表达式为(Ce0.90Gd0.10O1.95)1‑x+(Fe2O3)x,其中,x为烧结助剂Fe2O3的添加量,0<x≤0.015。通过使用低廉的Fe2O3作为GDC的烧结助剂,不仅能使GDC的烧结温度降低200‑300℃,也能使GDC的电导率提高10‑15%。本发明制备工艺简单,易于工业化生产,适用于陶瓷燃料电池及其相关高性能电化学器件。
Description
技术领域
本发明属于陶瓷技术领域,具体涉及一种低烧结温度的陶瓷燃料电池氧离子导电陶瓷电解质及其制备方法。
背景技术
陶瓷燃料电池(SOFC)是能直接高效的将化学能转化为电能的重要电化学装置,其可广泛用于固定发电和交通运输中。传统常用的SOFC电解质材料主要是氧化钇稳定的氧化锆(YSZ),然而YSZ需要在800-1000℃的高温运行,由此导致了组成材料的高成本、物理和化学降解等一系列问题。因此,急需使电池的运行温度降低到800℃以下,从而可以使用廉价的材料并可扩大其潜在的应用范围。掺杂CeO2由于具有高的氧离子电导率并与电极有良好的兼容性,因而被认为是最有前景的中温SOFC(IT-SOFCs)陶瓷电解质材料之一。掺杂各种不同浓度掺杂物(如Gd3+,Sm3+,Y3+,Ca2+等)CeO2基材料的离子电导率已被广泛研究,其中Gd3+是被认为CeO2基(GDC)固体电解质中最好的掺杂物之一。
然而,氧化铈基材料的主要问题之一是烧结性比较差。为降低烧结温度,可以使用各种物理化学方法合成超细氧化铈基粉末,如:溶胶-凝胶法、共沉淀法、化学燃烧蒸发法和高强机械球磨法等。另一方面,使用如CuO、Al2O3、MnO2、ZnO和CoO等烧结助剂也能促进致密,但是这些添加剂对氧化铈陶瓷的电导率是相对有害的。
为了解决现有技术中氧化铈基电解质的烧结性能差、烧结助剂影响电解质的电导率等问题,本发明公开了一种低烧结温度的氧离子导电陶瓷材料及其制备方法,通过使用低廉的Fe2O3作为烧结助剂,不仅能够有效降低GDC的烧结温度,甚至也能够提高GDC的电导率。
发明内容
本发明的目的是针对现有技术中氧化铈基电解质的烧结性能差、烧结助剂影响电解质的电导率等问题,提供了一种低烧结温度的氧离子导电陶瓷材料及其制备方法,通过使用低廉的Fe2O3作为GDC(钆掺杂的氧化铈,Ce0.90Gd0.10O1.95)的烧结助剂,不仅能使GDC的烧结温度降低200-300℃,也能使GDC的电导率提高10-15%。
为实现上述目的,本发明采用的技术方案是:
一种低烧结温度的氧离子导电陶瓷材料,所述电解质材料表达式为(Ce0.90Gd0.10O1.95)1-x+(Fe2O3)x,其中,x为Fe2O3的添加量,0<x≤0.015。
本发明的另一目的是提供所述的一种氧离子导电陶瓷电解质的制备方法,包括如下步骤:
(a)本发明的方法是首先制备GDC粉末,然后再将烧结助剂Fe2O3粉末添加入GDC粉末中;
(b)按照GDC的化学计量比,分别称取一定量的Gd2O3和CeO2粉体原料;
(c)将上述粉体与去离子水和球充分混合,并放在行星式球磨机上球磨,球磨后将料倒入烧杯并放入烘箱中烘干;
(d)将烘干后的样品倒入研钵中充分碾碎、过筛;
(e)将过筛后的粉料装于坩埚内,并放入马弗炉中进行煅烧,合成GDC粉末;
(f)将预烧后的GDC粉末与适量Fe2O3粉末混合后进行二次球磨、干燥、研磨、过筛,得到GDC与Fe2O3混合物;
(g)将得到的粉料破碎、加入质量分数5%的聚乙烯醇(PVA)造粒,并在150MPa的压力下经干压成圆片(直径约为13mm,厚度约为1mm),分别在不同温度烧结,GDC试样需在1600℃空气中保温5小时,得到所需的电解质圆片。
优选的,步骤(c)中料∶球∶水质量比1∶2∶3,球磨机转速为300r/min,球磨时间为8h。
优选的,步骤(d)中过筛目数为80目。
优选的,步骤(e)中煅烧温度1200℃,煅烧时间为2h。
优选的,步骤(f)中二次球磨的料∶球∶水质量比1∶2∶3,球磨机转速为250r/min,球磨时间为8-16h,并且过筛目数为80-100目。
优选的,步骤(g)中(Ce0.90Gd0.10O1.95)1-x+(Fe2O3)x圆片的烧结温度为1250-1500℃,烧结时间为2h。
与现有技术相比,本发明的有益效果是:
(1)本发明通过简单的固相反应法,通过使用低廉的Fe2O3作为GDC的烧结助剂,获得一种适用于陶瓷燃料电池的电解质材料,本发明制备方法操作简单。
(2)本发明使用的烧结助剂,不仅能使GDC的烧结温度降低200-300℃,也能使GDC的电导率提高10-15%。
(3)本发明制备的陶瓷燃料电池电解质材料具有良好的烧结性能和电导率,解决现有陶瓷燃料电池GDC电解质的烧结性能及其在中温区域(600-800℃)的使用问题。
附图说明
图1是本发明实施例1中制备烧结的(Ce0.90Gd0.10O1.95)0.985+(Fe2O3)0.015电解质的XRD图;
图2是本发明实施例1中制备烧结的(Ce0.90Gd0.10O1.95)0.985+(Fe2O3)0.015与GDC电解质在不同烧结温度下的相对密度;
图3是本发明实施例1中制备烧结的(Ce0.90Gd0.10O1.95)0.985+(Fe2O3)0.015电解质在最佳烧结温度(1350℃/2h)的SEM图;
图4是本发明实施例1中制备烧结的(Ce0.90Gd0.10O1.95)0.985+(Fe2O3)0.015与GDC电解质在不同测试温度下的离子电导率;
图5是本发明实施例2中制备烧结的(Ce0.90Gd0.10O1.95)0.995+(Fe2O3)0.005电解质的XRD图;
图6是本发明实施例2中制备烧结的(Ce0.90Gd0.10O1.95)0.995+(Fe2O3)0.005与GDC电解质在不同烧结温度下的相对密度;
图7是本发明实施例2中制备烧结的(Ce0.90Gd0.10O1.95)0.995+(Fe2O3)0.005电解质在最佳烧结温度(1400℃/2h)的SEM图;
图8是本发明实施例2中制备烧结的(Ce0.90Gd0.10O1.95)0.995+(Fe2O3)0.005与GDC电解质在不同测试温度下的离子电导率。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明;应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明;除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1
本实施例提供一种低烧结温度的氧离子导电陶瓷材料,表达式为(Ce0.90Gd0.10O1.95)0.985+(Fe2O3)0.015。即,烧结助剂Fe2O3的添加量为1.5mol%。
本实施例中(Ce0.90Gd0.10O1.95)0.985+(Fe2O3)0.015陶瓷燃料电池氧离子导电陶瓷电解质的制备方法,包括如下步骤:
(a)按照GDC的化学计量比,分别称量3.57 Gd2O3和30.5g CeO2粉体原料;
(b)将上述粉体与去离子水和球充分混合,料∶球∶水质量比1∶2∶3,并放在行星式球磨机上球磨,球磨机转速为300r/min,球磨时间为8h,球磨后将料倒入烧杯并放入烘箱中烘干;
(c)将烘干后的样品倒入研钵中充分碾碎、过80目筛;
(d)将过筛后的粉料装于坩埚内,并放入马弗炉中进行煅烧,煅烧温度1200℃,煅烧时间为2h,合成GDC粉末;
(e)将预烧后的GDC粉末与0.48g Fe2O3粉末混合后进行二次球磨、干燥、研磨、过筛,其中,料∶球∶水质量比1∶2∶3,球磨机转速为250r/min,球磨时间为12h,并且过筛目数为100目,得到GDC与Fe2O3混合物;
(f)将得到的粉料破碎、加入质量分数5%的PVA造粒,并在150MPa的压力下经干压成圆片(直径约为13mm,厚度约为1mm),分别在不同温度烧结(烧结温度为1250-1500℃,烧结时间为2h),GDC试样需在1600℃空气中保温5小时,得到所需的电解质圆片。
对本实施例制备的(Ce0.90Gd0.10O1.95)0.985+(Fe2O3)0.015电解质进行XRD表征,结果如图1所示,由图1中结果可知,(Ce0.90Gd0.10O1.95)0.985+(Fe2O3)0.015电解质为纯相的萤石结构,表明该添加量的Fe2O3已经完全溶解到CeO2中去了。
对本实施例制备的(Ce0.90Gd0.10O1.95)0.985+(Fe2O3)0.015电解质进行烧结性能测试,结果如图2所示,由图2中结果可知,GDC需要在1600℃温度下烧结5小时才可以达到致密,而(Ce0.90Gd0.10O1.95)0.985+(Fe2O3)0.015在1350℃温度下烧结2小时即可达到致密,表明1.5mol%的Fe2O3添加使GDC的烧结温度降低了250℃
对本实施例制备的在最佳烧结温度(1350℃/2h)获得的(Ce0.90Gd0.10O1.95)0.985+(Fe2O3)0.015电解质进行SEM表征,结果如图3所示,由图3中结果可知,在该条件下烧结的电解质非常致密。
对本实施例制备的(Ce0.90Gd0.10O1.95)0.985+(Fe2O3)0.015电解质进行电导率测试,结果如图4所示,由图4中结果可知,800℃时,(Ce0.90Gd0.10O1.95)0.985+(Fe2O3)0.015的电导率比GDC的电导率高了近15%。
以上结果表明,添加1.5mol%的Fe2O3烧结助剂,不仅使GDC的烧结温度降低了250℃,也使GDC的电导率提高了近15%。
实施例2
本实施例提供一种低烧结温度的氧离子导电陶瓷材料,表达式为(Ce0.90Gd0.10O1.95)0.995+(Fe2O3)0.005。即,烧结助剂Fe2O3的添加量为0.5mol%。
本实施例中(Ce0.90Gd0.10O1.95)0.995+(Fe2O3)0.005陶瓷燃料电池氧离子导电陶瓷电解质的制备方法,包括如下步骤:
(a)按照GDC的化学计量比,分别称量3.6g Gd2O3和30.8g CeO2粉体原料;
(b)将上述粉体与去离子水和球充分混合,料∶球∶水质量比1∶2∶3,并放在行星式球磨机上球磨,球磨机转速为300r/min,球磨时间为8h,球磨后将料倒入烧杯并放入烘箱中烘干;
(c)将烘干后的样品倒入研钵中充分碾碎、过80目筛;
(d)将过筛后的粉料装于坩埚内,并放入马弗炉中进行煅烧,煅烧温度1200℃,煅烧时间为2h,合成GDC粉末;
(e)将预烧后的GDC粉末与0.16g Fe2O3粉末混合后进行二次球磨、干燥、研磨、过筛,其中,料∶球∶水质量比1∶2∶3,球磨机转速为250r/min,球磨时间为8h,并且过筛目数为80目,得到GDC与Fe2O3混合物;
(f)将得到的粉料破碎、加入质量分数5%的PVA造粒,并在150MPa的压力下经干压成圆片(直径约为13mm,厚度约为1mm),分别在不同温度烧结(烧结温度为1250-1500℃,烧结时间为2h),GDC试样需在1600℃空气中保温5小时,得到所需的电解质圆片。
对本实施例制备的(Ce0.90Gd0.10O1.95)0.995+(Fe2O3)0.005电解质进行X射线衍射(XRD)表征,结果如图5所示,由图5中结果可知,(Ce0.90Gd0.10O1.95)0.995+(Fe2O3)0.005电解质为纯相的萤石结构,表明该添加量的Fe2O3已经完全溶解到CeO2中去了。
对本实施例制备的(Ce0.90Gd0.10O1.95)0.995+(Fe2O3)0.005电解质进行烧结性能测试,结果如图6所示,由图6中结果可知,GDC需要在1600℃温度下烧结5小时才可以达到致密,而(Ce0.90Gd0.10O1.95)0.995+(Fe2O3)0.005在1400℃温度下烧结2小时即可达到致密,表明0.5mol%的Fe2O3添加使GDC的烧结温度降低了200℃
对本实施例制备的在最佳烧结温度(1400℃/2h)获得的(Ce0.90Gd0.10O1.95)0.995+(Fe2O3)0.005电解质进行扫描电镜(SEM)表征,结果如图7所示,由图7中结果可知,在该条件下烧结的电解质非常致密。
对本实施例制备的(Ce0.90Gd0.10O1.95)0.995+(Fe2O3)0.005电解质进行电导率测试,结果如图8所示,由图8中结果可知,800℃时,(Ce0.90Gd0.10O1.95)0.995+(Fe2O3)0.005的电导率比GDC的电导率高了近11%。
以上结果表明,添加0.5mol%的Fe2O3烧结助剂,不仅使GDC的烧结温度降低了200℃,也使GDC的电导率提高了近11%。
以上所述的实施例对本发明的技术方案和有益效果进行了详细说明,应理解的是以上所述仅为本发明的具体实施例,并不用于限制本发明,凡在本发明的原则范围内所做的任何修改和改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种低烧结温度的氧离子导电陶瓷材料,其特征在于,所述陶瓷电解质材料为萤石矿结构,表达式为(Ce0.90Gd0.10O1.95)1-x+(Fe2O3)x,其中,x为烧结助剂Fe2O3的添加量,0<x≤0.015。
2.权利要求1所述的一种低烧结温度的氧离子导电陶瓷电解质的制备方法,其特征在于,包括如下步骤:
(a)本发明的方法是首先制备GDC粉末,然后再将烧结助剂Fe2O3粉末添加入GDC粉末中;
(b)按照GDC的化学计量比,分别称取一定量的Gd2O3和CeO2粉体原料;
(c)将上述粉体与去离子水和球充分混合,并放在行星式球磨机上球磨,球磨后将料倒入烧杯并放入烘箱中烘干;
(d)将烘干后的样品倒入研钵中充分碾碎、过筛;
(e)将过筛后的粉料装于坩埚内,并放入马弗炉中进行煅烧,合成GDC粉末;
(f)将预烧后的GDC粉末与适量Fe2O3粉末混合后进行二次球磨、干燥、研磨、过筛,得到GDC与Fe2O3混合物;
(g)将得到的粉料破碎、加入质量分数5%的聚乙烯醇(PVA)造粒,并在150MPa的压力下经干压成圆片(直径约为13mm,厚度约为1mm),分别在不同温度烧结,GDC试样需在1600℃空气中保温5小时,得到所需的电解质圆片。
3.根据权利要求2所述的一种低烧结温度的氧离子导电陶瓷电解质的制备方法,其特征在于,步骤(c)中料∶球∶水质量比1∶2∶3,球磨机转速为300r/min,球磨时间为8h。
4.根据权利要求2所述的一种低烧结温度的氧离子导电陶瓷电解质的制备方法,其特征在于,步骤(d)中过筛目数为80目。
5.根据权利要求2所述的一种低烧结温度的氧离子导电陶瓷电解质的制备方法,其特征在于,步骤(e)中煅烧温度1200℃,煅烧时间为2h。
6.根据权利要求2所述的一种低烧结温度的氧离子导电陶瓷电解质的制备方法,其特征在于,步骤(f)中二次球磨的料∶球∶水质量比1∶2∶3,球磨机转速为250r/min,球磨时间为8-16h,并且过筛目数为80-100目。
7.根据权利要求2所述的一种低烧结温度的氧离子导电陶瓷电解质的制备方法,其特征在于,步骤(g)中(Ce0.8Sm0.2O1.9)1-x+(Fe2O3)x圆片的烧结温度为1250-1500℃,烧结时间为2h。
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