CN107615639A - 元件和发电机 - Google Patents
元件和发电机 Download PDFInfo
- Publication number
- CN107615639A CN107615639A CN201680014552.5A CN201680014552A CN107615639A CN 107615639 A CN107615639 A CN 107615639A CN 201680014552 A CN201680014552 A CN 201680014552A CN 107615639 A CN107615639 A CN 107615639A
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- organic polymer
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Abstract
提供一种元件,其包括:第一电极、中间层和第二电极;第一电极、中间层和第二电极以此顺序布置,中间层包括有机聚合物材料,其中有机聚合物材料的分子结构包括由下式(1)表示的结构,其中R1为羰基、醚基、硫醚基或有机聚硅氧烷,且R1可与R2形成环状结构(酰亚胺基团);且R2至R6为可相同或不同的有机基团,其中所述有机基团各自可具有2价或更高的化学价并且可形成另外的结构。
Description
技术领域
本公开涉及元件和发电机。
背景技术
常规上,已经有这样的尝试:有效地利用通过结构体(例如道路、桥梁和建筑物)的振动、运动物体(例如小汽车和火车车厢)的振动和由于人类活动引起的振动所产生的能量。对于有效地利用由振动产生的能量的方法,存在其中将振动能转化为电能的方法。这样的方法的实例包括利用压电元件的系统和利用静电感应的系统。
利用压电元件的系统主要使用基于陶瓷的压电元件,并且利用当由于振动向压电元件施加形变时在压电元件的表面处感生电荷的现象。
利用静电感应的系统通常使用半永久地保留电荷的驻极体电介质(例如参见PTL1至PTL 3)。在前述文献中使用的驻极体电介质为能够使电介质带电以半永久地产生静电场的材料。借助通过由于振动改变驻极体电介质和远离驻极体电介质布置的电极之间的相对位置的静电感应而使电极感生电荷。结果,产生电。
由于利用压电元件的系统主要使用基于陶瓷的压电元件,因此存在所述元件不具有挠性并且元件容易断裂的问题。
在利用静电感应的系统中,当制造使用的驻极体衍生物时,需要在电介质上进行充电处理。充电处理的实例包括电晕放电和等离子体放电处理。然而,这些处理具有需要大量电能的问题。而且,元件的挠性不足。另外,通常布置机械容量变化系统,且因此难以实现挠性元件。
引文列表
专利文献
PTL 1:日本专利No.5563746
PTL 2:日本未审专利申请公布No.2012-164727
PTL 3:日本未审专利申请公布2012-164917
发明内容
技术问题
本发明旨在提供具有优异的挠性和优异的耐久性并且不需要充电处理的元件。
问题的解决方案
作为前述问题的解决手段,本发明的元件包括第一电极、中间层和第二电极(以此顺序布置)。中间层包括有机聚合物材料,其中有机聚合物材料的分子结构包括由下式(1)表示的结构。
[化学式1]
在上式(1)中,R1为羰基、醚基、硫醚基或有机聚硅氧烷,且R1与R2可形成环状结构(酰亚胺基团);且R2-R6为可相同或不同的有机基团,所述有机基团各自可具有2价或更高的化学价且可形成另外的结构。
发明的有益效果
本发明可提供具有优异的挠性和优异的耐久性且不需要充电处理的元件。
附图说明
[图1-1]图1-1为说明本发明的元件的实施方式的示意性横截面视图。
[图1-2]图1-2为说明本发明的其中在一个电极和中间层之间布置间隔的元件的实施方式的示意性横截面视图。
[图1-3]图1-3为说明本发明的其中在一个电极和中间层之间布置间隔且在另一个电极和中间层之间布置间隔的元件的实施方式的示意性横截面视图。
[图2-1]图2-1为说明其中在图1-2中说明的元件中的电极的每一个和各自的覆盖材料之间布置电线的实例的示意性横截面视图。
[图2-2]图2-2为说明其中使用间隔物在图2-1中说明的元件的第一电极和中间层之间布置间隔的实例的示意性横截面视图。
[图3]图3为说明本发明发电机的实施方式的示意性横截面视图。
[图4]图4为说明本发明发电机的另一个实施方式的示意性横截面视图。
具体实施方式
(元件)
本发明的元件包括第一电极、中间层和第二电极(以此顺序布置)。本发明的元件视需要可还包括其它部件。
<第一电极和第二电极>
第一电极和第二电极各自的材料、形状、尺寸和结构取决于预期意图适当地选择而没有任何限制。
第一电极的材料、形状、尺寸和结构与第二电极的材料、形状、尺寸和结构可相同或不同,但是第一电极的材料、形状、尺寸和结构优选地与第二电极的材料、形状、尺寸和结构相同。
第一电极和第二电极的材料的实例包括金属、碳类导电材料和导电橡胶组合物。
金属的实例包括金、银、铜、铝、不锈钢、钽、镍和磷青铜。
碳类导电材料的实例包括石墨、碳纤维和碳纳米管。
导电橡胶组合物的实例包括含有导电填料和橡胶的组合物。
导电填料的实例包括碳材料(例如克特晏黑(Ketjenblack)、乙炔黑、石墨、碳纤维、碳纳米纤维和碳纳米管)、金属填料(例如金、银、铂、铜、铁、镍和铝)、导电聚合物材料(例如聚噻吩、聚乙炔、聚苯胺、聚吡咯、聚对亚苯(poly(p-phenylene))和聚(对亚苯基)亚乙烯基衍生物的任一种的衍生物,或用掺杂剂例如阴离子和阳离子掺杂的衍生物)和离子液体。这些可单独或以组合使用。
橡胶的实例包括有机硅橡胶、改性的有机硅橡胶、含氟有机硅橡胶、丙烯酸类橡胶、氯丁二烯橡胶、聚硫橡胶、聚氨酯橡胶、异丁基橡胶、丁二烯橡胶、苯乙烯丁二烯橡胶、丁基橡胶、乙烯橡胶和天然橡胶(胶乳)。
第一电极的形态和第二电极的形态的实例包括片(sheet)、膜、膜、机织织物、无纺织物、网状物、海绵状物和沉积膜。第一电极的形态和第二电极的形态可取决于元件的形状适当地选择而没有任何限制。
第一电极的尺寸和第二电极的尺寸没有特别限制,并且取决于元件的形状适当地选择。
第一电极的平均厚度和第二电极的平均厚度取决于元件的结构可适当地选择。考虑到所得元件的导电性和挠性,第一电极的平均厚度和第二电极的平均厚度优选在0.01μm-1mm范围内、更优选在0.1μm-500μm范围内。当第一电极的平均厚度和第二电极的平均厚度为0.01μm或更大时,可获得适当的机械强度,且因此所得元件的导电性改善。当第一电极的平均厚度和第二电极的平均厚度为1mm或更小时,所得元件是可形变的,且因此可获得优异的发电性能。
<中间层>
中间层包括有机聚合物材料,其中有机聚合物材料的分子结构包括由下式(1)表示的结构。在本发明中,可在有机聚合物材料的主链或侧链中包括前述结构。而且,可包括所述结构作为用于将有机聚合物材料的分子彼此键合的交联剂。
[化学式2]
在上式(1)中,R1为羰基、醚基、硫醚基或有机聚硅氧烷,且R1和R2可形成环状结构(酰亚胺基团);且R2至R6为可相同或不同的有机基团,其中所述有机基团各自可具有2价或更高的化学价且可形成另外的结构。
其中在材料的主链中包括由式(1)表示的结构的有机聚合物材料的实例包括热塑性树脂(例如聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯和聚氨酯)、热固性树脂(例如环氧树脂、酚醛树脂和三聚氰胺树脂)、工程塑料(例如芳香族聚酰胺、芳香族聚酰亚胺和聚碳酸酯)和高级工程塑料(例如聚亚苯基硫醚、聚醚酰亚胺、聚醚醚酮和聚醚砜)。
其中在材料的侧链中包括由式(1)表示的结构的有机聚合物材料的实例包括热塑性树脂(例如聚苯乙烯和丙烯腈丁二烯苯乙烯树脂)和热固性弹性体(例如苯乙烯丁二烯橡胶和苯基有机硅橡胶)。
而且,包括由式(1)表示的结构的交联剂的实例包括酸酐(例如邻苯二甲酸酐和马来酸酐)和异氰脲酸衍生物[例如二乙烯基苯、异氰脲酸三烯丙基酯、异氰脲酸三缩水甘油基酯、异氰脲酸三(3-三甲氧基甲硅烷基丙基)酯、异氰脲酸三(2-羟乙基)酯、异氰脲酸三(2-羧乙基)酯、异氰脲酸烯丙基二缩水甘油基酯、异氰脲酸二烯丙基缩水甘油基酯和异氰脲酸甲基二烯丙基酯]。由于中间层包括前述材料,所得元件可实现大的发电量。
而且,当在由式(1)表示的结构中包含吸电子取代基时,可实现元件的更大发电量。吸电子取代基的实例包括硝基、氰基、卤素、苯基、羧基、酰基、醛基(aldehyde)、磺酸基(sulfonic acid)、亚砜基团、乙烯基、烯丙基、炔基和异氰脲酸酯基(异氰脲酸基,isocyanurate)。
中间层可包含赋予多种功能的多种填料。
填料的实例包括金属氧化物(例如氧化钛、氧化锌、氧化铁和二氧化硅)、金属复合氧化物(例如钛酸钡和钛锆酸铅)、金属碳酸盐(例如碳酸钙)、碳材料(例如炭黑、石墨、碳纤维、碳纳米管、富勒烯[包括衍生物]和石墨烯)、有机化合物(例如苯乙烯树脂、丙烯酸类树脂、三聚氰胺树脂、丙烯腈树脂、有机硅树脂和PTFE)、矿物(例如云母、粘土和合成水滑石)和单质金属(例如金、银、铜和铝)。
中间层可为单层或多层。
中间层的平均厚度取决于预期意图适当地选择而没有任何限制。中间层的平均厚度优选在1μm-10mm范围内、更优选在20μm-200μm范围内。当中间层的平均厚度在前述范围内时,可形成均匀膜作为所述中间层,并且中间层不抑制所得元件的形变。当所述平均厚度为1μm或更大时,可获得适当的机械强度,且因此所得元件的发电性能改善。当所述平均厚度为10mm或更小时,中间层具有优异的挠性,且因此所得元件的发电性能改善。
对于中间层的电性质,中间层优选为绝缘的。对于绝缘性,中间层优选具有108Ωcm或更大、更优选地1010Ωcm或更大的体积电阻率。通过将中间层的体积电阻率调节到前述优选的数值范围,可实现优异的发电性能。
<<表面改性处理>>
中间层可经历表面改性处理。表面改性处理的实例包括等离子体处理、电晕放电处理、UV-射线照射处理、臭氧处理和射线(X-射线、α-射线、β-射线、γ-射线、电子束、中子或重离子)照射处理。在它们中,考虑到加工效率,等离子体处理、电晕放电处理和电子束照射处理是优选的。然而,所述表面改性处理不限于前述处理,只要所进行的表面改性处理为施加一定水平的辐射能,以便对待处理的材料进行改性的处理。
--等离子体处理--
在等离子体处理的情形中,等离子体发生装置为例如大气压等离子体装置以及平行板等离子体装置、电容耦合等离子体装置或电感耦合等离子体装置。考虑到处理的中间层的耐久性,等离子体处理优选为低压等离子体处理。
等离子体处理的反应压力取决于预期意图适当地选择而没有任何限制。反应压力优选在0.05Pa-100Pa范围内、更优选在1Pa-20Pa范围内。当反应压力在前述范围内时,可增大通过中间层的发电量,且可维持耐久性,因为未施加过量的能量。
等离子体处理的反应气氛取决于预期意图适当地选择而没有任何限制。例如,气体例如惰性气体、稀有气体和氧气作为反应气氛是有效的。考虑到效果的连续性,所述反应气氛优选为氩气。而且,优选的是,将反应气氛的氧分压调节到5,000ppm或更小。当反应气氛的氧分压为5,000ppm或更小时,可抑制臭氧的产生,并且可避免臭氧处理装置的使用。
等离子体处理中的电辐射剂量(辐射电量)由(输出功率×照射的持续时间)定义。电辐射剂量优选在5Wh-200Wh范围内、更优选在10Wh-50Wh范围内。当电辐射剂量在前述的优选范围内时,可增大通过中间层的发电量,且可维持耐久性,因为未施加过量的能量。
--电晕放电处理--
电晕放电处理中施加的能量(累积能量)优选在6J/cm2-300J/cm2范围内、更优选在12J/cm2-60J/cm2范围内。当施加的能量在前述的优选范围内时,可增大通过中间层的发电量,且可维持耐久性,因为未施加过量的能量。而且,电晕放电处理中施加的电压优选在50V-150V范围内、更优选为100V。电晕放电处理的反应气氛优选为空气。
--电子束照射处理--
电子束照射处理的辐射剂量优选为1kGy或更大、更优选在300kGy-10MGy范围内。当所述辐射剂量在前述的优选范围内时,可增大通过中间层的发电量,且可维持耐久性,因为未施加过量的能量。
电子束照射处理的反应气氛取决于预期意图适当地选择而没有任何限制。反应气氛优选为通过用惰性气体例如氩气、氖气、氦气和氮气进行填充将其氧分压调节到5,000ppm或更小的气氛。当反应气氛的氧分压为5,000ppm或更小时,可抑制臭氧的产生,并且可避免臭氧处理装置的使用。
--UV-射线照射处理--
UV-射线照射处理中使用的UV射线优选具有200nm或更长但是365nm或更短、更优选地具有240nm或更长但是320nm或更短的波长。
UV-射线照射处理的累积辐射优选在5J/cm2-500J/cm2范围内、更优选在50J/cm2-400J/cm2范围内。当所述累积辐射在前述的优选范围内时,可增大通过中间层的发电量,且可维持耐久性,因为未施加过量的能量。
UV-射线照射处理的反应气氛取决于预期意图适当地选择而没有任何限制。反应气氛优选为通过用惰性气体例如氩气、氖气、氦气和氮气进行填充将其氧分压调节到5,000ppm或更小的气氛。当反应气氛的氧分压为5,000ppm或更小时,可抑制臭氧的产生,且可避免臭氧处理装置的使用。
在相关技术中,提出了通过经由等离子体处理、电晕放电处理、UV-射线照射处理或电子束照射处理激发或氧化材料从而形成活性基团来增强层间粘附力。然而,这些技术只限于层间的施加,且不适用于最外表面,因为光滑性(lubricity)降低。而且,前述处理中任一个的反应在富氧状态下进行以有效地引入反应活性基团(羟基)。因此,前述的相关技术和本发明中进行的表面改性处理在根本上是不同的。
所述表面改性处理为在低氧含量的反应环境中在低压下进行的处理(例如等离子体处理)。因此,表面改性处理例如由于“具有高键能的Si-O键的增加”加快表面的再交联和键合而改善耐久性。
<元件的结构>
本发明的元件包括第一电极、中间层和第二电极,第一电极、中间层和第二电极以此顺序布置,中间层包括有机聚合物材料,其中有机聚合物材料的分子结构包括由下式(1)表示的结构。
[化学式3]
在式(1)中,R1为羰基、醚基、硫醚基或有机聚硅氧烷,且R1和R2可形成环状结构(酰亚胺基团);且R2-R6为可相同或不同的有机基团,其中所述有机基团各自可具有2价或更高的化学价且可形成另外的结构。
本发明的元件通过外力例如振动而形变,从而发电。本发明的元件的发电机制尚不清楚,但是设想如下。当施加负荷时,通过和摩擦带电相似的机制使邻近电极的中间层带电或在中间层内部产生电荷。作为前述带电的结果,在元件内导致表面电位差。如果连接电线,则为了使表面电位差变成零而使电荷运动,且因此电流流动(产生)。
当向元件施加负荷例如外力或振动时,本发明的元件变形而发电。本发明的元件的发电机制尚不清楚,但是设想如下。当施加负荷时,通过和摩擦带电相似的机制使邻近电极的中间层带电或在中间层内部产生电荷。作为前述带电的结果,在元件内导致表面电位差。为了使表面电位差变成零而使电荷运动,从而发电。
元件优选地包括布置在中间层和第一电极之间、或在中间层和第二电极之间、或两者的间隔。当布置所述间隔时,可增加所得元件的发电量。用于布置间隔的方法取决于预期意图适当地选择而没有任何限制。所述方法的实例包括包括在中间层和第一电极之间、或在中间层和第二电极之间、或两者处布置间隔的方法。
示出了说明本发明的元件的一个实例的示意图。图1(图1-1、1-2和1-3)为说明本发明的元件的实施方式的一些实例的示意性横截面视图。各实例的元件具有相同的基本结构,其中第一电极1、中间层3和第二电极2以此顺序布置。
图1-1说明其中第一电极1、中间层3和第二电极2以此顺序布置的元件。
图1-2说明其中在电极1和中间层3之间布置间隔4的元件。
注意,可在电极2和中间层3之间布置间隔4来代替在电极1和中间层3之间布置间隔4。
图1-3说明其中在电极1和中间层3之间以及在电极2和中间层3之间布置间隔的元件。
而且,图2(图2-1和2-2)为说明用于评估本发明的元件的发电量的元件的一个实例的示意性横截面视图。图2-1说明其中第一电极1、中间层3和第二电极2以此顺序布置、在第一电极1和中间层3之间布置间隔、且在第一电极1和覆盖材料6之间布置用于引出电流的电线5的元件。图2-2说明图2-1的其中进一步布置用于保持间隔4的间隔物7的元件。
(发电机)
本发明的发电机至少包括本发明的元件,并且视需要可还包括其它部件。
<其它部件>
前述的其它部件的实例包括覆盖材料、电线和电路。
-覆盖材料-
覆盖材料12取决于预期意图适当地选择而没有任何限制。
覆盖材料的材料的实例包括聚合物材料和橡胶。聚合物材料的实例包括聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯、聚氯乙烯、聚酰亚胺树脂、含氟树脂和丙烯酸类树脂。橡胶的实例包括有机硅橡胶、改性的有机硅橡胶、丙烯酸类橡胶、氯丁二烯橡胶、聚硫橡胶、聚氨酯橡胶、异丁基橡胶、含氟有机硅橡胶、乙烯橡胶和天然橡胶(胶乳)。
覆盖材料的形态(foam)、形状、尺寸和厚度取决于发电机适当地选择而没有任何限制。
(电线)
电线13取决于预期意图适当地选择而没有任何限制。
电线的材料的实例包括金属和合金。金属的实例包括金,银,铜,铝和镍。
电线的形态、形状和厚度取决于发电机适当地选择而没有任何限制。
<<电路>>
电路取决于预期意图适当地选择而没有任何限制,只要电路为将元件中产生的电流从其中取出的电路。
<电装置的结构>
参考图3和4解释装备有本发明的元件的发电机的实例。
图3中说明的发电机20包括元件10、覆盖材料6、电线5和电路21。
而且,图4为说明本发明的发电机20的结构的另一个实例的横截面视图。在图4中说明的发电机20的元件10中,布置间隔6。由于元件10具有间隔6,元件10具有容易变形的结构。因此,甚至在弱振动的情况下,元件10的电容也改变,从而增加发电量。
<用途>
例如,发电机适宜用于多种传感器,例如超声传感器、压力传感器、触觉传感器、变形传感器、加速度传感器、冲击传感器、振动传感器、压敏传感器、电场传感器和声压传感器。特别地,发电机适宜用于可穿戴的传感器,因为不需要高压。而且,发电机适宜用作头挂听筒、扬声器、麦克风、水听器、显示器、风扇、泵、可调焦距透镜、超声换能器、压电变压器、隔音器、隔音材料、制动器或键盘中的具有优异的加工性的压电膜。而且,发电机可用于音频系统、信息处理装置、测量装置、医疗装置、车辆、建筑、用于运动器械例如滑雪板和球拍的缓冲材料和其它领域。
此外,发电机适宜用于如下应用。
-使用天然能例如波力(wave power)、水力和风力的发电。
-当嵌入在鞋靴、衣物、地板或装饰品(accessories)时通过人的行走的发电。
-当发电机嵌入在汽车轮胎中时使用由行进导致的振动的发电。
而且,预期所述发电机作为通过在挠性基底上形成发电机而制作的板式发电机、通过施加电压而充电的二次电池或新颖的致动装置(例如人造肌肉)应用。
实施例
下面对本发明的实施例进行解释,但是以下实施例不应解释为以任何方式限制本发明的范围。在以下描述中,“份”指代“质量份”,且“%”指代“质量%”,除非另外声明。
(实施例1)
元件的制造>
<<中间层>>
将聚对苯二甲酸乙二醇酯(下文称为PET)膜(LUMIRROR(注册商标)T60,由TORAYINDUSTRIES,INC.制造,厚度:100μm)切割成50mm×70mm尺寸的块(piece)。之后,在以下条件下对切割的块进行作为表面改性处理的等离子体放电处理,从而获得中间层。
-等离子体放电处理的条件-
装置:PR-500(由Yamato Scientific Co.,Ltd.制造)
输出功率:100W
处理时间:4分钟
反应气氛:氩气(99.999%)
反应压力:10Pa
<<电极>>
对于在该实施例中使用的电极,使用由镀有铜和镍的PET纤维形成的导电性无纺织物(SUI-80-M30,由SEIREN Co.,Ltd.制造,平均厚度:35μm)。将已经进行表面改性处理的中间层夹在两个电极中间,并且将引线(C3/RV-90/0.75SQ,由Taiyo CabletecCorporation制造)连接到各电极。然后,当用由聚氯乙烯形成的层压膜(SLF-K02G,由Europort Co.,Ltd.制造,厚度:80μm)对整体进行密封时,将切割成5mm宽度的导电性布胶带(E05R1020,由SEIWA ELECTRIC MFG CO.,LTD.制造,厚度:120μm)作为间隔物布置,从而获得其中在电极和中间层之间形成间隔的元件。
(实施例2-7)
以和实施例1中相同的方式各自获得元件,条件是将PET膜用以下树脂膜替代。
实施例2:聚酰亚胺(UPILEX(注册商标)125S,由UBE INDUSTRIES,LTD.制造,厚度:130μm)
实施例3:聚醚酰亚胺(ULTEM(注册商标)1000,由SABIC制造,厚度:70μm)
实施例4:聚醚砜(VERADEL(注册商标)A-300A,由Solvay Japan,Ltd.制造,厚度:100μm)
实施例5:聚亚苯基硫醚(TORELINA(注册商标)E1380,由TORAY INDUSTRIES,INC.制造,厚度:95μm)
实施例6:聚醚醚酮(APTIV(注册商标)2000,由Victrex PLC制造,厚度:100μm)
实施例7:聚萘二甲酸乙二醇酯(TEONEX(注册商标)Q51,由Teijin DuPont FilmsJapan Limited制造,厚度:75μm)
(实施例8)
<元件的制造>
<<中间层>>
向100份充当基础材料的二甲基有机硅橡胶(TSE3033,由Momentive PerformanceMaterials Inc.制造)中混合6份50%的二乙烯基苯(D0958,由Tokyo Chemical IndustryCo.,Ltd.制造)的甲苯溶液。通过刮涂将所得混合物施加到PET膜上,随后在热风炉中在120摄氏度下烘烤30分钟,从而获得具有90μm厚度的薄膜。
随后,在以下条件下向获得的薄膜上施加电子束,从而获得中间层。
-电子束照射处理的条件-
装置:线照射低能电子束光源(由Hamamatsu Photonics K.K制造)
辐射剂量:1MGy
反应气氛:氮气(包括具有5,000ppm或更小的分压的氧气)
<<电极>>
对于电极,使用铝/PET复合膜(AL-PET(注册商标)9-100,由PANAC CO.,LTD.制造,铝:9μm/PET:100μm)。
将已经进行表面改性处理的中间层以各电极的铝表面面向中间层的方式夹在两个电极中间,并且将引线(C3/RV-90/0.75SQ,由Taiyo Cabletec Corporation制造)连接到各电极。然后,当用由聚氯乙烯形成的层压膜(SLF-K02G,由Europort Co.,Ltd.制造,厚度:80μm)将整体密封时,布置PET膜间隔物(LUMIRROR(注册商标)H10,由TORAY INDUSTRIES,INC.制造,厚度:480μm),从而获得其中在电极和中间层之间形成间隔的元件。
(实施例9和10)
以和实施例8中相同的方式各自获得元件,条件是基础材料用以下有机硅橡胶替代。
实施例9:二甲基有机硅橡胶(DY35-2083,由DOW CORNING TORAY CO.,LTD.制造)
实施例10:二甲基有机硅橡胶(KE-1300,由Shin-Etsu Chemical Co.,Ltd.制造)
(实施例11)
以和实施例8中相同的方式获得元件,条件是将6份50%的二乙烯基苯的甲苯溶液用10份50%的异氰脲酸甲基二烯丙基酯(MEDAIC,由Shikoku Chemicals Corporation制造)的甲苯溶液替代。
(实施例12和13)
以和实施例11中相同的方式各自获得元件,条件是基础材料用以下有机硅橡胶替代。
实施例12:二甲基有机硅橡胶(DY35-2083,由DOW CORNING TORAY CO.,LTD.制造)
实施例13:二甲基有机硅橡胶(KE-1300,由Shin-Etsu Chemical Co.,Ltd.制造)
(实施例14)
通过刮涂将100份苯基有机硅橡胶(XE14-C3450,由Momentive PerformanceMaterials Inc.制造)施加到PET膜上,随后在热风炉中在120摄氏度下烘烤30分钟,从而获得具有80μm厚度的薄膜。随后,在和实施例8的条件相同的条件下向获得的薄膜施加电子束,从而获得中间层。将已经进行表面改性处理的中间层以各电极的铝表面面向中间层的方式夹在两个电极AL-PET(注册商标)中间,并且将引线(C3/RV-90/0.75SQ,由TaiyoCabletec Corporation制造)连接到各电极。然后,用由聚氯乙烯形成的层压膜(SLF-K02G,由Europort Co.,Ltd.制造,厚度:80μm)将整体密封,从而获得其中在电极和中间层之间未形成间隔的元件。
(实施例15)
其中在中间层和电极之间布置间隔的元件以和实施例14中相同的方式获得,条件是当用所述层压膜将整体密封时,将切割成5mm宽度的导电性布胶带(E05R1020,由SEIWAELECTRIC MFG CO.,LTD.制造,厚度:120μm)作为间隔物布置。
(实施例16)
其中在中间层和电极之间布置间隔的元件以和实施例14中相同的方式获得,条件是当用所述层压膜将整体密封时,将PET膜(LUMIRROR(注册商标)H10,由TORAYINDUSTRIES,INC.制造,厚度:480μm)作为间隔物布置。
(实施例17)
75μm厚度的薄膜以和实施例15相同的方式获得,条件是用二甲基有机硅橡胶(TSE3033,由Momentive Performance Materials Inc.制造)代替苯基有机硅橡胶,且向100份二甲基有机硅橡胶加入10份1%可溶的富勒烯衍生物([60]PCBM,产品编号:M2088,由Tokyo Chemical Industry Co.,Ltd.制造)的甲苯溶液。在形成薄膜之后,其中在中间层和电极之间布置间隔的元件以和实施例15相同的方式获得。
(实施例18)
具有75μm厚度的薄膜以和实施例15中相同的方式获得,条件是用二甲基有机硅橡胶(TSE3033,由Momentive Performance Materials Inc.制造)代替苯基有机硅橡胶,且向100份二甲基有机硅橡胶加入10份1%的氢化富勒烯(nanom spectra A100,由FrontierCarbon Corporation制造)的二甲苯溶液。在形成薄膜之后,其中在中间层和电极之间布置间隔的元件以和实施例15相同的方式获得。
(实施例19)
<元件的制造>
使用实施例8中制造的元件。
<评价>
将实施例8的元件以彼此面向的电极具有相互不同的极性的方式连接到函数发生器(function generator,FG-274,由TEXIO TECHNOLOGY CORPORATION制造)。在以下条件下向元件施加电压,并且判断从距离所述元件1m的位置的声音的可听度。将其中元件的声音在所有频率的情况下均可听见的情形判断为合格水平。结果列于表2中。
<施加条件>
-CMOS输出:±5V
-输出波形:方波(占空比:50%)
-频率:400Hz、2kHz和12kHz
(对比例1)
元件以和实施例1中相同的方式获得,条件是用低密度聚乙烯膜(NOVATEC(注册商标)LD LF280H,由Japan Polyethylene Corporation制造,厚度:80μm)代替充当中间层的PET膜。
(对比例2)
元件以和对比例1中相同的方式获得,条件是用聚丙烯膜代替中间层。
(对比例3-5)
以和实施例14中相同的方式各自获得对比例3-5的元件,条件是用以下橡胶代替苯基有机硅橡胶。
对比例3:二甲基有机硅橡胶(TSE3033,由Momentive Performance MaterialsInc.制造)
对比例4:二甲基有机硅橡胶(DY35-2083,由DOW CORNING TORAY CO.,LTD.制造)
对比例5:二甲基有机硅橡胶(KE-1300,由Shin-Etsu Chemical Co.,Ltd.制造)
(对比例6)
<元件的制造>
元件以和实施例19中相同的方式获得,条件是未进行表面改性处理。
<评价>
以和实施例19中相同的方式评价获得的元件。结果列于表2中。
<评价>
<<发电量的测量>>
将示波器(WaveAce1001,由Teledyne LeCroy Japan Corporation制造)连接到从获得的元件伸出的电线。让铁球(重量:200g)从10cm高掉落在所述元件上,且测量在电极之间产生的峰值电压。进行所述测量5次以测定平均值。使用对比例1的平均值作为标准通过等级对发电性能进行评价。结果列于表1中。
-评价标准-
A:相比于对比例1的测量值,所述值为10倍或更大。
B:相比于对比例1的测量值,所述值为5倍或更大但是小于10倍。
C:相比于对比例1的测量值,所述值为3倍或更大但是小于5倍。
D:相比于对比例1的测量值,所述值小于3倍。
[表1-1-1]
[表1-1-2]
[表1-2-1]
[表1-2-2]
在表1-1-1到1-2-2中,产品名称的细节于下。
<中间层>
<<基础材料>>
LUMIRROR T60:聚对苯二甲酸乙二醇酯,由TORAY INDUSTRIES,INC.制造
UPILEX 125S:聚酰亚胺,由UBE INDUSTRIES,LTD.制造
ULTEM1000:聚醚酰亚胺,由SABIC制造
VERADEL A-300A:聚醚砜,由Solvay Japan,Ltd.制造
TORELINA E 1380:聚亚苯基硫醚,由TORAY INDUSTRIES,INC.制造
APTIV 2000:聚醚醚酮,由Victrex PLC制造
TEONEX Q51:聚萘二甲酸乙二醇酯,由Teijin DuPont Films Japan Limited制造
TSE 3033:二甲基有机硅橡胶,由Momentive Performance Materials Inc.制造
DY35-2083:二甲基有机硅橡胶,由DOW CORNING TORAY CO.,LTD.制造
KE-1300:二甲基有机硅橡胶,由Shin-Etsu Chemical Co.,Ltd.制造
XE14-C3450:苯基有机硅橡胶,由Momentive Performance Materials Inc.制造
<<添加剂>>
D0958:二乙烯基苯,由Tokyo Chemical Industry Co.,Ltd.制造
MEDAIC:异氰脲酸甲基二烯丙基酯,由Shikoku Chemicals Corporation制造
M2088:可溶的富勒烯,由Tokyo Chemical Industry Co.,Ltd.制造
NS-A100:氢化富勒烯,由Frontier Carbon Corporation制造
<电极>
SUI-80-M30:导电性布,由SEIREN Co.,Ltd.制造
AL-PET 9-100:铝/PET复合膜,由PANAC CO.,LTD.制造
<间隔物>
E05R1020:导电性布胶带,由SEIWA ELECTRIC MFG CO.,LTD.制造
LUMIRROR H10:PET膜,由TORAY INDUSTRIES,INC.制造
[表2]
由实施例1-7以及对比例1和2发现,在其主链的骨架中包括由下式(1)表示的结构或的吸电子官能团的材料具有较大的发电量。
[化学式4]
在上式(1)中,R1为羰基、醚基、硫醚基或有机聚硅氧烷,且R1与R2可形成环状结构(酰亚胺基团);且R2至R6为可相同或不同的有机基团,其中所述有机基团各自可具有2价或更高的化学价且可形成另外的结构。
由实施例14和对比例3-5发现,在不加入添加剂的情况下获得大的发电量,因为苯基有机硅包含吸电子的苯基。
由实施例8-10和对比例3-5发现,在不包含吸电子官能团的二甲基有机硅橡胶的情况下通过经由乙烯基的共交联引入苯基改善发电量。
由实施例11-13和对比例3-5发现,在不包含吸电子官能团的二甲基有机硅橡胶的情况下通过经由烯丙基的共交联引入异氰脲酸酯基改善了发电量。
由实施例14-16发现,通过借助变更间隔物的厚度来改变间隔的高度改善发电量。
由实施例17和18以及对比例3发现,还通过向所述基础材料加入具有和式(1)相似结构的富勒烯改善发电量。
而且,根据实施例19和对比例6,通过向元件施加电压确认元件的独立于频率的作用(行为)。结果,发现进行过表面改性处理时,本发明的元件表现出“逆压电效应”。
例如,本发明的实施方式于下。
<1>元件,其包括:
第一电极;
中间层;和
第二电极,
第一电极、中间层和第二电极以此顺序布置,
中间层包括有机聚合物材料,其中有机聚合物材料的分子结构包括由下式(1)表示的结构:
[化学式5]
其中R1为羰基、醚基、硫醚基或有机聚硅氧烷,且R1能与R2形成环状结构(酰亚胺基团);且R2至R6为可相同或不同的有机基团,其中所述有机基团各自能具有2价或更高的化学价并且能形成另外的结构。
<2>根据<1>的元件,其中由式(1)表示的结构包括吸电子取代基。
<3>根据<1>或<2>的元件,其中有机聚合物材料的主链包括硅氧烷键。
<4>根据<1>至<3>任一项的元件,其中有机聚合物材料的主链包括由式(1)表示的结构。
<5>根据<1>至<3>任一项的元件,其中有机聚合物材料的侧链包括由式(1)表示的结构。
<6>根据<1>至<3>任一项的元件,其中用于将有机聚合物材料的分子彼此键合的交联剂包括由式(1)表示的结构。
<7>根据<6>的元件,其中有机聚合物材料包括其中通过由式(1)表示的结构和包含两个或更多个烯丙基或乙烯基的化合物将有机聚合物材料的分子彼此交联的结构。
<8>根据<7>的元件,其中包含两个或更多个烯丙基或乙烯基的化合物包括异氰脲酸衍生物。
<9>根据<1>至<8>任一项的元件,其中在中间层和第一电极之间、或在中间层和第二电极之间、或两者处布置间隔。
<10>发电机,其包括:
根据<1>至<9>任一项的元件。
[参考标记列表]
1:第一电极
2:第二电极
3:中间层
4:间隔
5:电线
6:覆盖材料
7:间隔物
10:元件
20:发电机
21:电路
Claims (10)
1.元件,其包括:
第一电极;
中间层;和
第二电极,
第一电极、中间层和第二电极以此顺序布置,
中间层包括有机聚合物材料,其中有机聚合物材料的分子结构包括由下式(1)表示的结构:
[化学式1]
其中R1为羰基、醚基、硫醚基或有机聚硅氧烷,且R1能与R2形成环状结构(酰亚胺基团);且R2至R6为可相同或不同的有机基团,其中所述有机基团各自能具有2价或更高的化学价并且能形成另外的结构。
2.根据权利要求1的元件,其中由式(1)表示的结构包括吸电子取代基。
3.根据权利要求1或2的元件,其中所述有机聚合物材料的主链包括硅氧烷键。
4.根据权利要求1-3任一项的元件,其中所述有机聚合物材料的主链包括由式(1)表示的结构。
5.根据权利要求1-3任一项的元件,其中所述有机聚合物材料的侧链包括由式(1)表示的结构。
6.根据权利要求1-3任一项的元件,其中用于将所述有机聚合物材料的分子彼此键合的交联剂包括由式(1)表示的结构。
7.根据权利要求6的元件,其中所述有机聚合物材料包括其中通过由式(1)表示的结构和包含两个或更多个烯丙基或乙烯基的化合物将有机聚合物材料的分子彼此交联的结构。
8.根据权利要求7的元件,其中所述包含两个或更多个烯丙基或乙烯基的化合物包括异氰脲酸衍生物。
9.根据权利要求1-8任一项的元件,其中在中间层和第一电极之间、或在中间层和第二电极之间、或两者处布置间隔。
10.发电机,其包括:
根据权利要求1-9任一项的元件。
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US10476405B2 (en) | 2019-11-12 |
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