CN111662470B - 一种耐疲劳铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜及其制备方法 - Google Patents
一种耐疲劳铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜及其制备方法 Download PDFInfo
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Abstract
本发明属于多铁性薄膜技术领域,具体涉及一种耐疲劳铁酸钴/聚偏二氟乙烯‑三氟乙烯多层复合薄膜,包括PVDF‑TrFE薄膜,且PVDF‑TrFE薄膜上贴附有至少一层CFO/PVDF‑TrFE复合薄膜;其制备方法为:将PVDF‑TrFE粉末溶解得到溶液A,再向溶液A中加入CFO纳米级粉末得到混合溶液B;然后以FTO导电玻璃为衬底,利用将溶液A在FTO导电玻璃上进行旋转涂膜,制备PVDF‑TrFE薄膜,烘干后,接着将混合溶液B在PVDF‑TrFE薄膜上进行旋转涂膜,制备CFO/PVDF‑TrFE复合薄膜;之后将湿膜置进行退火处理,得到铁酸钴/聚偏二氟乙烯‑三氟乙烯多层复合薄膜,最后在其上镀铂点电极。本发明的铁酸钴/聚偏二氟乙烯‑三氟乙烯多层复合薄膜不仅铁电疲劳特性优良,而且其制备条件温和,工艺过程步骤简单且可控性强。
Description
技术领域
本发明涉及多铁性复合薄膜及其制备方法,具体涉及一种耐疲劳铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜及其制备方法,属于多铁性薄膜技术领域。
背景技术
聚偏二氟乙烯-三氟乙烯(PVDF-TrFE)是一种性能优良的半结晶性有机物和理想的膜材料。PVDF-TrFE具有高弹性和优良的压电铁电性能,在压力和加速度传感器、能量采集、超声传感器、非易失性存储器和波导等领域有广泛的应用前景。特别是近年来随着半导体产业的发展,有机铁电膜的高密度存储更是学术界和工业界的焦点。而铁电疲劳(随着铁电膜开关次数的增加,其剩余极化逐渐减小直至丧失铁电性能)问题成为制约铁电存储器件能否真正走向商业化应用的关键因素,纯铁电有机膜往往疲劳性能不如无机材料。
铁酸钴(CoFe2O4,CFO)为尖晶石晶体结构,具有较大的磁晶各向异性、大的矫顽场、中等饱和磁化强度、高磁致伸缩特性、高电阻率等优点,在永磁体、磁记录、吸波材料和生物医学领域都具有广阔的应用前景。
磁电效应指材料在外磁场中发生电极化响应或外加电场导致的磁化改变现象(后者称为逆磁电效应)。单相磁电材料的室温磁电耦合性能通常都很微弱,因此,近年来层状复合磁电材料一直是国际上研究的热点。因此,针对PVDF-TrFE铁电聚合物耐铁电疲劳特性较差的缺点,有必要设计一种耐疲劳铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜及其制备方法,以克服上述缺点。
发明内容
为了克服上述现有技术存在的不足,本发明的目的是提供一种耐疲劳铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜及其制备方法,不仅铁电疲劳特性优良,而且其工艺设备成本低,工艺过程简单且可控性强。
为实现上述目的,本发明的技术方案为一种耐疲劳铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜,包括CFO/PVDF-TrFE复合薄膜和PVDF-TrFE薄膜,所述PVDF-TrFE薄膜上贴附有至少一层所述CFO/PVDF-TrFE复合薄膜。
本发明还提供一种耐疲劳铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜的制备方法,包括如下步骤:
S1、制备CFO纳米级粉末;
S2、制备铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜;
S2.1、将PVDF-TrFE粉末溶解于碳酸二乙酯溶剂中,充分搅拌,得到溶液A;
S2.2、在持续搅拌的溶液A中加入CFO纳米级粉末,充分搅拌,得到混合溶液B;
S2.3、以FTO导电玻璃为衬底,利用匀胶机将所制备的溶液A在FTO导电玻璃上进行旋转涂膜,制备PVDF-TrFE薄膜;
S2.4、将旋涂好的湿膜置于干燥箱中烘干;
S2.5、利用匀胶机将所制备的混合溶液B在烘干后的PVDF-TrFE薄膜上进行旋转涂膜,制备CFO/PVDF-TrFE复合薄膜;
S2.6、将旋涂好的湿膜置于热处理炉中进行退火处理,得到铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜;
S2.7、制作电极,在步骤S2.6所制得的铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜上镀铂点电极。
进一步地,步骤S2.5和步骤S2.6之间还包括如下步骤:将旋涂好的湿膜置于干燥箱中烘干,再利用匀胶机将所制备的混合溶液B在烘干后的CFO/PVDF-TrFE复合薄膜上进行旋转涂膜,再制备一层CFO/PVDF-TrFE复合薄膜。
进一步地,所述溶液A中PVDF-TrFE的质量分数为5-7%。
进一步地,所述混合溶液B中CFO和PVDF-TrFE的用量配比为0.085-0.1333 g:0.2g。
进一步地,步骤S2.4中,将湿膜置于70-80 ℃的干燥箱中干燥3-5min。
进一步地,退火处理的处理温度为130-140 ℃,处理时间为1.5-2 h。
进一步地,步骤S1中制备CFO纳米级粉末包括如下步骤:
S1.1、将五水硝酸钴和九水硝酸铁按照摩尔比为1.05:1的比例溶解于乙二醇甲醚溶剂中,得到溶液C,溶液C的浓度为0.75 mol/L;将柠檬酸溶解于持续搅拌的溶液C中,柠檬酸与溶液中阳离子的摩尔比为1:1.2,得到铁酸钴前驱体溶胶;
S1.2、将所得的铁酸钴前驱体溶胶持续搅拌2 h得到稳定的铁酸钴溶胶,之后置于80 ℃的干燥箱中干燥5min得到铁酸钴干凝胶;
S1.3、将所得的铁酸钴干凝胶置于热处理炉中,退火温度为800 ℃,保温时间为2h,得到铁酸钴预烧粉末;
S1.4、将所得的铁酸钴预烧粉末置于研钵中研磨30 min,得到CFO纳米级粉末。
进一步地,步骤S1中制备的CFO纳米级粉末的粒径为500-800nm。
进一步地,步骤S2.2中,向溶液A中加入CFO纳米级粉末后,先电动搅拌,再超声分散,重复2-3次,使CFO纳米级粉末分散均匀。
与现有技术相比,本发明具有以下有益效果:
本发明提供的铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜的制备方法将高铁磁性纳米粒子铁酸钴均匀混合于聚偏二氟乙烯-三氟乙烯溶液中复合后旋涂获得结构致密的多层复合薄膜,将铁酸钴的高磁致伸缩系数和PVDF-TrFE的可塑性结合制备出满足磁电材料高磁电效应及形状可控等特点的薄膜,且两相材料各自性能互补的同时获得更优良和可靠的磁电耦合效应,有效地解决了单相铁电聚合物聚偏二氟乙烯-三氟乙烯耐疲劳特性差的缺点,且本发明的制备方法简单,易操作,制备条件温和可控且效率高。
附图说明
图1为PVDF-TrFE薄膜(a)、实施例1制得的CFO(PVDF-TrFE)/PVDF-TrFE/PVDF-TrFE多层复合薄膜(b)及实施例2制得的PVDF-TrFE/CFO(PVDF-TrFE)/CFO(PVDF-TrFE)多层复合薄膜(c)的结构示意图;
图2为 PVDF-TrFE、铁酸钴(CFO)以及实施例1制得的CFO(PVDF-TrFE)/PVDF-TrFE/PVDF-TrFE多层复合薄膜、实施例2制得的PVDF-TrFE/CFO(PVDF-TrFE)/CFO(PVDF-TrFE)多层复合薄膜的XRD图谱;
图3为本发明实施例1制得的CFO(PVDF-TrFE)/PVDF-TrFE/PVDF-TrFE多层复合薄膜的疲劳特性曲线;
图4为本发明实施例1制得的CFO(PVDF-TrFE)/PVDF-TrFE/PVDF-TrFE多层复合薄膜疲劳测试前后的电滞回线;
图5为本发明实施例2制得的PVDF-TrFE/CFO(PVDF-TrFE)/CFO(PVDF-TrFE)多层复合薄膜的疲劳特性曲线;
图6为本发明实施例2制得的PVDF-TrFE/CFO(PVDF-TrFE)/CFO(PVDF-TrFE)多层复合薄膜疲劳测试前后的电滞回线;
图7为本发明制备的CFO纳米级粉末的磁滞回线;
图8为PVDF-TrFE薄膜的疲劳特性。
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
本实施例提供一种铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜,包括CFO/PVDF-TrFE复合薄膜和PVDF-TrFE薄膜,CFO/PVDF-TrFE复合薄膜上贴附有两层PVDF-TrFE薄膜。
上述铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜的制备方法,包括以下步骤:
S1、制备纳米级铁酸钴粉体;
S1.1、将五水硝酸钴和九水硝酸铁按照摩尔比为1.05:1的比例溶解于乙二醇甲醚溶剂中,得到溶液C,溶液C的浓度为0.75 mol/L;将柠檬酸溶解于持续搅拌的溶液C中,柠檬酸与溶液中阳离子的摩尔比为1:1.2,得到铁酸钴前驱体溶胶;
S1.2、将所得的铁酸钴前驱体溶胶持续搅拌2 h得到稳定的铁酸钴溶胶,之后置于80 ℃的干燥箱中干燥5min得到铁酸钴干凝胶;
S1.3、将所得的铁酸钴干凝胶置于热处理炉中,退火温度为800 °C,保温时间为2h,得到铁酸钴预烧粉末;
S1.4、将所得的铁酸钴预烧粉末置于研钵中研磨30 min,得到粒径范围为500nm-800nm的CFO纳米级粉末;
S2、制备铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜;
S2.1、将偏氟乙烯溶解在碳酸二乙酯溶剂中,充分搅拌,获得溶液A,保证溶液质量分数为7 %;
S2.2、在持续搅拌的溶液A中加入CFO纳米级粉末,先电动搅拌1h,再超声分散20min,重复2-3次,得到混合均匀的混合溶液B,保证混合溶液B中CFO和PVDF-TrFE的用量配比为0.1333 g:0.2 g;
S2.3、选择FTO导电玻璃为衬底,利用匀胶机将所制备的混合溶液B在FTO导电玻璃上进行旋转涂膜,通过控制旋涂转速和时间制备CFO/ PVDF-TrFE复合薄膜;旋涂初始转速300r/s持续20s,加速至3000r/s后持续旋涂40s;
S2.4、将旋涂好的湿膜置于80 ℃的干燥箱中干燥5min;
S2.5、利用匀胶机将所制备的溶液A在烘干后的CFO/ PVDF-TrFE复合薄膜上进行旋转涂膜,通过控制旋涂转速和时间制备PVDF-TrFE薄膜;旋涂初始转速300r/s持续20s;加速至3000r/s后持续旋涂40s;
S2.6、重复步骤S2.4和S2.5,在烘干后的PVDF-TrFE薄膜上再制备一层PVDF-TrFE薄膜,获得铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合湿膜;
S2.7、将铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合湿膜置于热处理炉中140 °C退火处理2 h;
S2.8、制作复合多层薄膜的上电极,在步骤S2.7所得的铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜上镀铂点电极,制得CFO(PVDF-TrFE)/PVDF-TrFE/PVDF-TrFE多层复合薄膜。
本实施所制备的CFO(PVDF-TrFE)/PVDF-TrFE/PVDF-TrFE多层复合薄膜的结构如图1中(b)所示,厚度约为1μm。其XRD图谱如图2所示;由图2可见:本实施例的CFO(PVDF-TrFE)/PVDF-TrFE/PVDF-TrFE多层复合薄膜中既出现了铁酸钴晶体的尖晶石单相结构峰又有PVDF-TrFE的b相峰。本实施所制备的CFO(PVDF-TrFE)/PVDF-TrFE/PVDF-TrFE多层复合薄膜的铁电疲劳特性曲线和疲劳前后测试的电滞回线分别如图3和图4所示;由图3可见:本实施例的CFO(PVDF-TrFE)/PVDF-TrFE/PVDF-TrFE多层复合薄膜的疲劳特性为当翻转次数到达105时,开关极化值开始明显变小,仅与纯PVDF-TrFE的106相当(如图8);由图4可见:极化前后剩余极化分别为:4.37 μC/cm2、0.03 μC/cm2,,极化前后矫顽场分别为:563.8 kV/cm、53.4 kV/cm。
实施例2
本实施例提供一种铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜,包括CFO/PVDF-TrFE复合薄膜和PVDF-TrFE薄膜,PVDF-TrFE薄膜上贴附有两层CFO/PVDF-TrFE复合薄膜。
上述铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜的制备方法,包括以下步骤:
S1、制备纳米级铁酸钴粉体:
S1.1:将五水硝酸钴和九水硝酸铁按照摩尔比为1.05:1的比例溶解于乙二醇甲醚溶剂中,得到溶液C,溶液C的浓度为0.5 mol/L;将柠檬酸溶解于持续搅拌的溶液C中,柠檬酸与溶液中阳离子的摩尔比为1:1,得到铁酸钴前驱体溶胶;
S1.2:将所得的铁酸钴前驱体溶胶持续搅拌2~3 h得到稳定的铁酸钴溶胶,之后置于80 ℃的干燥箱中干燥5min得到铁酸钴干凝胶;
S1.3:将所得的铁酸钴干凝胶置于热处理炉中,退火温度为800 °C,保温时间为2~3 h,得到铁酸钴预烧粉末;
S1.4:将所得的铁酸钴预烧粉末置于研钵中研磨20~30 min,得到粒径范围为500nm-800nm的CFO纳米级粉末;
S2、制备铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜:
S2.1、将偏氟乙烯溶解在碳酸二乙酯溶剂中,充分搅拌,获得溶液A,保证溶液质量分数为7 %;
S2.2、在持续搅拌的溶液A中加入CFO纳米级粉末,先电动搅拌1h,再超声分散20min,重复2-3次,得到均匀的混合溶液B,保证混合溶液B中CFO和PVDF-TrFE的用量配比为0.1333 g:0.2 g;
S2.3、选择FTO导电玻璃为衬底,利用匀胶机将所制备的溶液A在FTO导电玻璃上进行旋转涂膜,通过控制旋涂转速和时间制备PVDF-TrFE薄膜;旋涂初始转速300r/s持续20s,加速至3000r/s后持续旋涂40s;
S2.4、将旋涂好的湿膜置于80 ℃的干燥箱中干燥5min;
S2.5、利用匀胶机将所制备的混合溶液B在烘干后的PVDF-TrFE薄膜上进行旋转涂膜,通过控制旋涂转速和时间制备CFO/PVDF-TrFE复合薄膜;旋涂初始转速300r/s持续20s,加速至3000r/s后持续旋涂40s;
S2.6、重复步骤S2.4和S2.5,在烘干后的CFO/PVDF-TrFE复合薄膜上再制备一层CFO/PVDF-TrFE复合薄膜,获得铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合湿膜;
S2.7、将铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合湿膜置于热处理炉中140 ℃退火处理2 h;
S2.8、制作复合多层薄膜的上电极,在步骤S2.7所得的铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜上镀铂点电极,制得PVDF-TrFE/CFO(PVDF-TrFE)/CFO(PVDF-TrFE)多层复合薄膜。本实施例在PVDF-TrFE薄膜上旋涂两层CFO/PVDF-TrFE复合薄膜,保证薄膜表面干净平整且能够保证铂电极镀层的稳定性。
本实施所制备的PVDF-TrFE/CFO(PVDF-TrFE)/ CFO(PVDF-TrFE)多层复合薄膜的结构如图1中(c)所示,厚度约为1.5μm,其XRD图谱如图2所示;由图2可见:本实施例的PVDF-TrFE/CFO(PVDF-TrFE)/ CFO(PVDF-TrFE)多层复合薄膜中既出现了铁酸钴晶体的尖晶石单相结构峰又有PVDF-TrFE的b相峰。本实施所制备的PVDF-TrFE/CFO(PVDF-TrFE)/ CFO(PVDF-TrFE)多层复合薄膜的铁电疲劳特性曲线和疲劳前后测试的电滞回线分别如图5和图6所示;由图5可见:本实施例的PVDF-TrFE/CFO(PVDF-TrFE)/ CFO(PVDF-TrFE)多层复合薄膜的疲劳特性为当翻转次数达到109时,开关极化值开始明显变小,远优于纯PVDF-TrFE105及实施例1的106;电畴钉扎和退钉扎模型(Domain Pinning and Depinning Models)可以用来解释疲劳发生的机制,极化疲劳起源于极化翻转过程中的电子注入,随着高电场下的电子注入,从而导致了界面电极处和内部的电畴相位分离。由于铂电极与薄膜表面存在着一定的界面电荷,这些界面电荷引发针状的电畴成核并翻转;针尖出同样会聚集一下带正电的界面电荷或氧空位,由于这些尖端电荷不能完全被屏蔽,会产生一定的退极化场;引入CFO纳米级颗粒能够充分弥补薄膜内部缺陷,减小薄膜内部漏电流;且掺杂了CFO纳米级颗粒相当于引入更多的自由电荷,可以抵消界面处畴钉扎效应,充分提高聚合物薄膜极化发生的效率,增强导电性;在低频下CFO与PVDF-TrFE基体的偶极子取向极化增强,因此实施例1和实施例2的薄膜疲劳特性优于纯PVDF-TrFE;而实施例2中铂电极直接接触在CFO/PVDFTrFE层,在测试过程中,电子直接注入该层,在界面处形成一定的电势差,而CFO纳米颗粒包含的自由电荷在膜表面缓慢形成电畴后在电场作用下能够翻转,抑制畴钉扎效应,降低材料疲劳,因此实施例2的薄膜疲劳特性远优于实施例1和纯PVDF-TrFE。由图6可见:极化前后剩余极化分别为6.9 μC/cm2、7.8 μC/cm2,极化前后矫顽场分别为:564 kV/cm、574 kV/cm。
实施例3
本实施例提供一种铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜,包括CFO/PVDF-TrFE复合薄膜和PVDF-TrFE薄膜,PVDF-TrFE薄膜上贴附有一层CFO/PVDF-TrFE复合薄膜。
上述铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜的制备方法,包括以下步骤:
S1、制备纳米级铁酸钴粉体:
S1.1:将五水硝酸钴和九水硝酸铁按照摩尔比为1.05:1的比例溶解于乙二醇甲醚溶剂中,得到溶液C,溶液C的浓度为0.5 mol/L;将柠檬酸溶解于持续搅拌的溶液C中,柠檬酸与溶液中阳离子的摩尔比为1:1,得到铁酸钴前驱体溶胶;
S1.2:将所得的铁酸钴前驱体溶胶持续搅拌2~3 h得到稳定的铁酸钴溶胶,之后置于80 ℃的干燥箱中干燥5min得到铁酸钴干凝胶;
S1.3:将所得的铁酸钴干凝胶置于热处理炉中,退火温度为800 °C,保温时间为2~3 h,得到铁酸钴预烧粉末;
S1.4:将所得的铁酸钴预烧粉末置于研钵中研磨20~30 min,得到粒径范围为500nm-800nm的CFO纳米级粉末;当制得颗粒尺寸超过1μm后,薄膜表面旋涂质量变差,膜内漏电流较大,对薄膜性能影响很大;
S2、制备铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜:
S2.1、将偏氟乙烯溶解在碳酸二乙酯溶剂中,充分搅拌,获得溶液A,保证溶液质量分数为7 %;
S2.2、在持续搅拌的溶液A中加入CFO纳米级粉末,先电动搅拌1h,再超声分散20min,重复2-3次,得到均匀的混合溶液B,保证混合溶液B中CFO和PVDF-TrFE的用量配比为0.1333 g:0.2 g;
S2.3、选择FTO导电玻璃为衬底,利用匀胶机将所制备的溶液A在FTO导电玻璃上进行旋转涂膜,通过控制旋涂转速和时间制备PVDF-TrFE薄膜;旋涂初始转速300r/s持续20s,加速至3000r/s后持续旋涂40s;
S2.4、将旋涂好的湿膜置于80 ℃的干燥箱中干燥5min;
S2.5、利用匀胶机将所制备的混合溶液B在烘干后的PVDF-TrFE薄膜上进行旋转涂膜,通过控制旋涂转速和时间制备CFO/PVDF-TrFE复合薄膜;旋涂初始转速300r/s持续20s,加速至3000r/s后持续旋涂40s;
S2.6、将铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合湿膜置于热处理炉中140 ℃退火处理2 h;
S2.7、制作复合多层薄膜的上电极,在步骤S2.7所得的铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜上镀铂点电极,制得PVDF-TrFE/CFO(PVDF-TrFE)多层复合薄膜。
实施例4
本实施例提供一种铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜,包括CFO/PVDF-TrFE复合薄膜和PVDF-TrFE薄膜,PVDF-TrFE薄膜上贴附有两层CFO/PVDF-TrFE复合薄膜。
上述铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜的制备方法,包括以下步骤:
S1、制备纳米级铁酸钴粉体:
S1.1:将五水硝酸钴和九水硝酸铁按照摩尔比为1.05:1的比例溶解于乙二醇甲醚溶剂中,得到溶液C,溶液C的浓度为0.5 mol/L;将柠檬酸溶解于持续搅拌的溶液C中,柠檬酸与溶液中阳离子的摩尔比为1:1,得到铁酸钴前驱体溶胶;
S1.2:将所得的铁酸钴前驱体溶胶持续搅拌2~3 h得到稳定的铁酸钴溶胶,之后置于80 ℃的干燥箱中干燥5min得到铁酸钴干凝胶;
S1.3:将所得的铁酸钴干凝胶置于热处理炉中,退火温度为800 °C,保温时间为2~3 h,得到铁酸钴预烧粉末;
S1.4:将所得的铁酸钴预烧粉末置于研钵中研磨20~30 min,得到粒径范围为500nm-800nm的CFO纳米级粉末;
S2、制备铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜:
S2.1、将偏氟乙烯溶解在碳酸二乙酯溶剂中,充分搅拌,获得溶液A,保证溶液质量分数为5%;
S2.2、在持续搅拌的溶液A中加入CFO纳米级粉末,先电动搅拌1h,再超声分散20min,重复2-3次,得到均匀的混合溶液B,保证混合溶液B中CFO和PVDF-TrFE的用量配比为0.085g:0.2 g;
S2.3、选择FTO导电玻璃为衬底,利用匀胶机将所制备的溶液A在FTO导电玻璃上进行旋转涂膜,通过控制旋涂转速和时间制备PVDF-TrFE薄膜;旋涂初始转速300r/s持续20s,加速至3000r/s后持续旋涂40s;
S2.4、将旋涂好的湿膜置于70 ℃的干燥箱中干燥3min;
S2.5、利用匀胶机将所制备的混合溶液B在烘干后的PVDF-TrFE薄膜上进行旋转涂膜,通过控制旋涂转速和时间制备CFO/PVDF-TrFE复合薄膜;旋涂初始转速300r/s持续20s,加速至3000r/s后持续旋涂40s;
S2.6、重复步骤S2.4和S2.5,在烘干后的CFO/PVDF-TrFE复合薄膜上再制备一层CFO/PVDF-TrFE复合薄膜,获得铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合湿膜;
S2.7、将铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合湿膜置于热处理炉中130 ℃退火处理1.5 h;
S2.8、制作复合多层薄膜的上电极,在步骤S2.7所得的铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜上镀铂点电极,制得PVDF-TrFE/CFO(PVDF-TrFE)/ CFO(PVDF-TrFE)多层复合薄膜。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种耐疲劳铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜,其特征在于:包括CFO/PVDF-TrFE复合薄膜和PVDF-TrFE薄膜,所述PVDF-TrFE薄膜上贴附有两层及两层以上的所述CFO/PVDF-TrFE复合薄膜,且两层及两层以上的所述CFO/PVDF-TrFE复合薄膜位于所述PVDF-TrFE薄膜的同一侧,最外面的一层CFO/PVDF-TrFE复合薄膜上镀有铂点电极。
2.一种耐疲劳铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜的制备方法,其特征在于,包括如下步骤:
S1、制备CFO纳米级粉末;
S2、制备铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜;
S2.1、将PVDF-TrFE粉末溶解于碳酸二乙酯溶剂中,充分搅拌,得到溶液A;
S2.2、在持续搅拌的溶液A中加入CFO纳米级粉末,充分搅拌,得到混合溶液B;
S2.3、以FTO导电玻璃为衬底,利用匀胶机将所制备的溶液A在FTO导电玻璃上进行旋转涂膜,制备PVDF-TrFE薄膜;
S2.4、将旋涂好的湿膜置于70-80℃的干燥箱中干燥3-5min;
S2.5、利用匀胶机将所制备的混合溶液B在烘干后的PVDF-TrFE薄膜上进行旋转涂膜,制备CFO/PVDF-TrFE复合薄膜;
将旋涂好的湿膜置于干燥箱中烘干,再利用匀胶机将所制备的混合溶液B在烘干后的CFO/PVDF-TrFE复合薄膜上进行旋转涂膜,再制备一层CFO/PVDF-TrFE复合薄膜;
S2.6、将旋涂好的湿膜置于热处理炉中进行退火处理,得到铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜;
S2.7、制作电极,在步骤S2.6所制得的铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜上镀铂点电极。
3.如权利要求2所述的一种耐疲劳铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜的制备方法,其特征在于:所述溶液A中PVDF-TrFE的质量分数为5-7%。
4.如权利要求2所述的一种耐疲劳铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜的制备方法,其特征在于:所述混合溶液B中CFO和PVDF-TrFE的用量配比为0.085-0.1333g:0.2g。
5.如权利要求2所述的一种耐疲劳铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜的制备方法,其特征在于:退火处理的处理温度为130-140℃,处理时间为1.5-2h。
6.如权利要求2所述的一种耐疲劳铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜的制备方法,其特征在于:步骤S1中制备CFO纳米级粉末包括如下步骤:
S1.1、将五水硝酸钴和九水硝酸铁按照摩尔比为1.05:1的比例溶解于乙二醇甲醚溶剂中,得到溶液C,溶液C的浓度为0.75mol/L;将柠檬酸溶解于持续搅拌的溶液C中,柠檬酸与溶液中阳离子的摩尔比为1:1.2,得到铁酸钴前驱体溶胶;
S1.2、将所得的铁酸钴前驱体溶胶持续搅拌2h得到稳定的铁酸钴溶胶,之后置于80℃的干燥箱中干燥5min得到铁酸钴干凝胶;
S1.3、将所得的铁酸钴干凝胶置于热处理炉中,退火温度为800℃,保温时间为2h,得到铁酸钴预烧粉末;
S1.4、将所得的铁酸钴预烧粉末置于研钵中研磨30min,得到CFO纳米级粉末。
7.如权利要求2所述的一种耐疲劳铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜的制备方法,其特征在于:步骤S1中制备的CFO纳米级粉末的粒径为500-800nm。
8.如权利要求2所述的一种耐疲劳铁酸钴/聚偏二氟乙烯-三氟乙烯多层复合薄膜的制备方法,其特征在于:步骤S2.2中,向溶液A中加入CFO纳米级粉末后,先电动搅拌,再超声分散,重复2-3次,使CFO纳米级粉末分散均匀。
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