CN109997238A - 压电元件及其制造方法 - Google Patents

压电元件及其制造方法 Download PDF

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Publication number
CN109997238A
CN109997238A CN201780063178.2A CN201780063178A CN109997238A CN 109997238 A CN109997238 A CN 109997238A CN 201780063178 A CN201780063178 A CN 201780063178A CN 109997238 A CN109997238 A CN 109997238A
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CN
China
Prior art keywords
macromolecule
supatex fabric
piezoelectric element
layer
resin sheet
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Pending
Application number
CN201780063178.2A
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English (en)
Inventor
安田健
早川康武
大平晃也
柿本健一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NTN Corp
Nagoya Institute of Technology NUC
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NTN Corp
Nagoya Institute of Technology NUC
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Publication of CN109997238A publication Critical patent/CN109997238A/zh
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    • B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/702—Piezoelectric or electrostrictive devices based on piezoelectric or electrostrictive fibres
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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Textile Engineering (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Laminated Bodies (AREA)
  • Nonwoven Fabrics (AREA)
  • General Electrical Machinery Utilizing Piezoelectricity, Electrostriction Or Magnetostriction (AREA)

Abstract

本发明提供能够在不损害柔软性的情况下显现高发电性能的压电元件及其制造方法。该压电元件包含将保持或配合有压电陶瓷粒子(4)的高分子非织造织物(3)与配合有压电陶瓷粒子的高分子树脂片材(2)以含有至少一层高分子非织造织物的方式层叠而成的层叠体(1)。该层叠体是能够实现由在1层高分子非织造织物的2个主平面侧分别各自层叠了1层高分子树脂片材而成的层叠体产生的发电量以上的发电量的层叠体。

Description

压电元件及其制造方法
技术领域
本发明涉及压电元件及其制造方法，特别涉及适于利用了环境振动的振动发电的压电元件。
背景技术
近年来，采用在身边存在的振动、太阳光、室内光、电波等的能量进行电力转换的环境发电受到关注，向电子设备等的独立型电源的应用在不断发展。环境发电中利用振动的发电称为振动发电，有压电、电磁感应、静电感应等方式。
压电方式使用压电元件作为发电元件，利用材料的压电特性，因此具有如下优点：与电磁感应、静电感应相比，结构单纯。压电元件所需要的特性为高的发电性能、抗冲击性等。
构成压电元件的材料大致分为无机压电材料、有机压电材料。作为无机压电材料，广泛使用了以钛酸锆酸铅(PZT)为代表的具有钙钛矿型晶体结构的陶瓷，作为有机压电材料，可列举出聚偏二氟乙烯(以下称为PVDF)、偏二氟乙烯-三氟乙烯共聚物、聚乳酸等。无机压电材料与有机压电材料相比，发电性能优异，但柔软性、抗冲击性差。
也进行了通过将无机压电材料和有机压电材料复合化从而制作同时具有高发电性能和柔软性、抗冲击性的压电元件的尝试。例如在专利文献1中，提出了将具有树脂和压电粒子的压电体层层叠而成的复合压电元件，是在两个第一压电体层之间配置了压电粒子浓度比该第一压电体层低的第二压电体层的结构。通过降低第二压电体层的压电粒子浓度，从而使复合压电元件的耐弯曲性提高。另外，在专利文献2中公开了一种压电性片材，其包含使用含有有机聚合物的纤维形成的非织造织物(无纺布)或织造织物，并且包含无机填料。
非专利文献1中，提出了如下的压电元件：将由配合了铌酸钠钾固溶体(以下称为NKN)粒子的聚乙烯醇(以下称为PVA)树脂组合物制成的片材层和在由纤维化的PVDF制成的非织造织物中保持有NKN粒子的非织造织物层交替地层叠从而一体化而成的压电元件。该结构具有多孔的非织造织物层，因此认为与专利文献1的结构相比柔软性更高。
现有技术文献
专利文献
专利文献1：日本特开2015-50432号
专利文献2：WO2015/005420
非专利文献
非专利文献1：M.Kato,K.Kakimoto,Materials Letters,156,183-186(2015).
发明内容
发明要解决的课题
但是，在非专利文献1中，压电元件的两面为由配合有NKN粒子的PVA树脂组合物制成的片材层。为了进一步提高发电性能，需要在PVA树脂组合物中高填充NKN粒子，从而提高片材层表面的面电荷密度，使得容易将电荷取出。另外，关于片材层的厚度、非织造织物层的厚度、片材层与非织造织物层的层数，在发电性能将如何变化这一方面尚未研究。对于包含片材层和非织造织物层的层叠体的发电性能，在专利文献2中也尚未研究。
本发明为了应对这样的问题而完成，目的在于提供能够在不损害柔软性的情况下实现高发电性能的压电元件及其制造方法。
用于解决课题的手段
本发明的压电元件是包含层叠体的压电元件，该层叠体是将保持或配合有压电陶瓷粒子的高分子非织造织物(高分子无纺布)与配合有压电陶瓷粒子的高分子树脂片材以含有至少一层上述高分子非织造织物的方式层叠而成的。其特征在于，该层叠体是能够实现由在1层上述高分子非织造织物的2个主平面侧分别各自层叠了1层上述高分子树脂片材而成的层叠体产生的发电量以上的发电量的层叠体。
其特征在于，上述高分子树脂片材是配合有50～80体积％的压电陶瓷粒子的1层的厚度为10～100μm的片材，上述高分子非织造织物是构成该高分子非织造织物的纤维的平均直径为0.05～5μm、保持或配合有30～60体积％的压电陶瓷粒子的1层的厚度为10～300μm的非织造织物。
其特征在于，构成本发明的压电元件的层叠体层叠有多张上述高分子非织造织物、或者交替地层叠有上述高分子非织造织物与上述高分子树脂片材。特别地，其特征在于，上述层叠体的2个主平面侧均为上述高分子树脂片材。
本发明的压电元件的制造方法是包括如下工序的压电元件的制造方法：使保持或配合有压电陶瓷粒子的高分子非织造织物与配合有压电陶瓷粒子的高分子树脂片材以包含至少一层上述高分子非织造织物的方式层叠的工序、和使用压机对上述层叠了的层叠体进行压接从而一体化的工序。另外，其特征在于，保持或配合有上述压电陶瓷粒子的高分子非织造织物是采用对浆料进行电场纺丝的电场纺丝法(静电纺丝法)制造的高分子非织造织物，该浆料通过在使高分子溶解于水或有机溶剂而成的溶液中将上述压电陶瓷粒子分散而得到。
发明效果
本发明的压电元件将高分子树脂片材层和高分子非织造织物层层叠从而使其一体化，因此能够在不损害柔软性的情况下显现出高的压电性。另外，由于在高分子树脂片材中以50～80体积％高填充压电陶瓷粒子，因此能够在压电元件表面诱发电荷，容易地将电荷取出。进而，由于在高分子非织造织物层中以30～60体积％高填充压电陶瓷粒子，因此能够在不损害柔软性的情况下实现高压电性。
本发明的压电元件是能够实现由在1层高分子非织造织物的2个主平面侧分别各自层叠了1层高分子树脂片材而成的层叠体产生的发电量以上的发电量的层叠体，因此能够进一步提高并维持发电性能。
附图说明
图1为示出压电元件的截面图的一例的图。
图2为示出层叠体的极化方法的一例的图。
图3为供试用的压电元件的图。
图4为示出测定通过压电产生的电力的方法的电路图。
图5为示出发电量测定结果的图。
具体实施方式
对于将高分子非织造织物层与高分子树脂片材层层叠从而使其一体化的压电元件的发电量进行研究，结果，发现了如下现象：随着层叠体中的高分子非织造织物的层叠张数增加，发电量增加，进而与增加层叠张数相反地，发电量减少。即，可知在高分子非织造织物层与高分子树脂片材层的层叠张数中，关于发电量，存在最佳值。本发明基于这样的认识。
将本发明的压电元件的截面图的一例示于图1。图1为层叠体的表背2个主平面侧都成为高分子树脂片材的情形，图1(a)为高分子树脂片材与高分子非织造织物交替地层叠的例子，图1(b)为高分子非织造织物多张层叠的例子。应予说明，图1是将厚度放大而示出的层叠体的示意图，将压电陶瓷粒子、非织造织物等概念性地示出。
图1(a)中，配合有压电陶瓷粒子的高分子树脂片材2与压电陶瓷粒子4在非织造织物5内保持或配合的高分子非织造织物3交替地层叠，高分子树脂片材2a和2b形成了层叠体1a的表背。在将高分子树脂片材2的层叠张数设为n，将高分子非织造织物3的层叠张数设为m的情况下，作为层叠体1a中的张数的关系式，为n＝m+1。另外，就最小结构的层叠体而言，n为2张，m为1张，其成为最小结构的层叠体。
图1(b)中，多张上述高分子非织造织物3层叠，高分子树脂片材2a和2b形成了层叠体1b的表背。在这种情况下，就最小层叠体而言，n为2张，m为1张。作为层叠体1b的张数的关系式，n为常数2，m根据高分子非织造织物3的层叠张数，为2、3、4、···的值。
层叠体1并不只限定于图1(a)和(b)中所示的层叠体，只要是以包含至少1层的高分子非织造织物3的方式层叠而成的层叠体即可。例如，能够将多张高分子非织造织物3层叠，将该层叠体与高分子树脂片材2层叠。
对于包含层叠体1的压电元件的发电量进行了研究。作为压电元件，准备了如图1(a)中所示那样将高分子树脂片材2与高分子非织造织物3交替地层叠、高分子树脂片材2a和2b形成层叠体的表背的层叠体1a；和如图1(b)中所示那样多张高分子非织造织物3层叠、高分子树脂片材2a和2b形成层叠体的表背的层叠体1b。
关于高分子树脂片材2，准备了在PVA树脂中配合50体积％的平均粒径1μm的NKN粒子、1张的厚度为40μm的片材。
高分子非织造织物3是使用配合有50体积％的平均粒径1μm的NKN粒子的PVDF浆料采用电场纺丝法制作的1张的厚度为40μm的非织造织物。准备了3个水平的高分子非织造织物3，其纤维的平均直径分别为0.05、0.5、5μm。
就层叠体1a而言，将高分子树脂片材2的层叠张数设为n，将高分子非织造织物3的层叠张数设为m，用n-m结构表示。作为压电元件的发电量测定试样，制成2-1结构、3-2结构、4-3结构、5-4结构、6-5结构和7-6结构这6种层叠体，对于各个层叠体，制作了纤维的平均直径为0.05、0.5、5μm的不同的3个水平的试样。准备的试样合计为18个试样。
就层叠体1b而言，由于形成层叠体的表背的高分子树脂片材2的层叠张数为2张，因此将高分子非织造织物3的层叠张数设为m，用2-m结构表示。作为压电元件的发电量测定试样，制成2-1结构、2-3结构、2-5结构、2-7结构和2-9结构这5种层叠体，对于各个层叠体，制作了纤维的平均直径为0.05、0.5、5μm的不同的3个水平的试样。准备的试样合计为15个试样。
将层叠体1a和层叠体1b分别切割为13mm×28mm的大小，采用压机在压力40MPa、温度65℃的条件下加压3分钟，制成了片状的层叠体。
图2为示出层叠体1a和层叠体1b的极化方法的一例的示意图。在接地的试样台6上放置层叠体1，从层叠体1的上面在垂直方向上以3mm的距离设置针状电极7，利用采用该针状电极7施加直流电场而产生的电晕放电进行极化处理，制作压电元件。处理条件设为室温下，电压为20kV，处理时间为10分钟。
图3为供试用的压电元件的图。将层厚放大而示出。图3(a)为平面图，图3(b)为由图1中所示的层叠体1a得到的压电元件A的A-A截面图，图3(c)为由图1中所示的层叠体1b得到的压电元件B的A-A截面图。在包含进行了极化处理的层叠体1的压电元件A和B的两面涂布银糊剂8，形成上部和下部电极，安装铜箔带9，制成了供试用的压电元件。
图4为示出测定通过压电而产生的电力的方法的电路图。使用图4中所示的电路，在压电元件A和B的纵向(图3中所示的箭头方向)给予170Hz的伸缩振动，测定了每1振动的发电量。压电元件A和B与负载电阻10连接，在负载电阻10中产生的电力采用示波器11测定。
将测定结果示于图5中。图5(a)表示由层叠体1a得到的压电元件A的结果，图5(b)表示由层叠体1b得到的压电元件B的结果。再有，发电量是将最大发电量设为100％、用相对于该最大发电量的百分率表示。压电元件A的最大发电量为纤维的平均直径(纤维径)为0.05和0.5μm时的4-3结构，发电量为529nW。压电元件B的最大发电量为纤维的平均直径(纤维径)为0.05和0.5μm时的2-5结构，发电量为495nW。
另外，压电元件A与压电元件B相比，拉伸试验中的拉伸应力和应变变大。其结果，压电元件A为优选的结构。
如图5中所示那样，在1张高分子非织造织物3的2个主平面侧分别各自层叠了1张(合计2张)高分子树脂片材2的2-1结构的层叠体1a和1b成为层叠体1的最小单元。从该最小单元开始，随着高分子非织造织物3的层叠张数增加，发电量显示增加倾向。但是，该发电量并非单调地增加，在压电元件A的情况下4-3结构成为最大发电量，在压电元件B的情况下2-5结构成为最大发电量，这以后随着高分子非织造织物3的层叠张数增加，发电量显示减小倾向。即，在高分子树脂片材2与高分子非织造织物3的层叠张数中，关于发电量，存在最佳值。
本发明对该最佳值的两侧的一定范围进行限定，制成能够实现由上述最小单元的层叠体1产生的发电量以上的发电量的层叠体。具体地，在压电元件A的情况下，为2-1结构、3-2结构、4-3结构、5-4结构、6-5结构和7-6结构，优选为2-1结构、3-2结构、4-3结构、5-4结构和6-5结构，更优选为3-2结构、4-3结构和5-4结构。另外，在压电元件B的情况下，为2-1结构、2-3结构、2-5结构、2-7结构和2-9结构，优选为2-1结构、2-3结构、2-5结构和2-7结构。
在高分子树脂片材中所配合的压电陶瓷粒子或在高分子非织造织物内所保持或配合的压电陶瓷粒子可以为同一种类的压电陶瓷粒子，也可为不同种类的压电陶瓷粒子。同样地，在高分子树脂片材彼此之间或高分子非织造织物彼此之间，也是压电陶瓷粒子可以为同一种类的压电陶瓷粒子，也可为不同种类的压电陶瓷粒子。优选构成压电元件的层叠体整体使用具有同一组成的压电陶瓷粒子。
压电陶瓷粒子优选为具有钙钛矿型晶体结构的压电陶瓷粒子。例如可列举出包含铌、铅、钛、锌、钡、铋、锆、镧、钾、钠、钙、镁元素中的1种以上的压电陶瓷粒子。这些中，从在人体安全和环境安全方面优异的观点出发，更优选不含铅的NKN粒子或者钛酸钡粒子。NKN粒子是由(Na0.5K0.5)NbO3代表的陶瓷粒子。NKN粒子能够通过碳酸钠、碳酸钾和氧化铌的固体反应制造。
压电陶瓷粒子的平均粒径为0.1μm～10μm，优选为0.5μm～5μm，更优选为1μm～2μm。如果不到0.1μm，则难以在高分子树脂片材或高分子树脂非织造织物中均匀分散，如果超过10μm，则高分子树脂片材或高分子非织造织物的机械强度降低。应予说明，本发明中的平均粒径是采用激光衍射法测定并算出的50％粒径(D50)。
在将压电陶瓷粒子配合于高分子树脂片材中的情况下，优选制成在压电陶瓷粒子中使用高分子粘结剂而使其结合的造粒粉。高分子粘结剂优选为与构成高分子树脂片材的高分子材料不同的材料。作为高分子粘结剂，具体地，可列举出丙烯酸系、纤维素系、PVA系、聚乙烯醇缩醛系、聚氨酯系、醋酸乙烯酯系高分子等。通过使用造粒粉，压电陶瓷粒子可高填充化。对造粒的方法并无特别限定，能够使用喷雾造粒、转动造粒、挤出造粒、压缩造粒等公知的方法。造粒粉的平均粒径为10μm～100μm，优选为30μm～50μm。
就构成高分子树脂片材的高分子材料而言，对其种类并无特别限定，可以是热塑性树脂、热固性树脂、热塑性弹性体、合成橡胶、天然橡胶中的任一种。为了提高压电元件的耐热性，更优选熔点为150℃以上的结晶性树脂或者玻璃化转变温度为150℃以上的非晶性树脂。具体地，可列举出PVA、聚乙烯醇缩丁醛(以下称为PVB)、聚苯乙烯、聚酰亚胺、聚酰胺酰亚胺、聚醚酰亚胺、聚砜、聚苯砜、聚醚砜、聚芳酯、聚苯醚等高分子材料。
在上述高分子材料中配合上述压电陶瓷粒子。就高分子树脂片材而言，优选与上述压电陶瓷粒子一起配合不具有压电性的无机填充剂。在配合无机填充剂的情况下，为了使片材层内的电荷移动变得容易，优选配合导电性填料。作为导电性填料，可列举出石墨、炭黑、碳纳米管、富勒烯、金属粉末、碳纤维、金属纤维等。另外，作为无机填充剂，为了提高片材层的机械强度，可配合补强材料。作为补强材料，可列举出碳纳米管、晶须、碳纤维、玻璃纤维等。
高分子树脂片材优选含有50～80体积％的压电陶瓷粒子，剩余部分设为上述高分子材料，或者剩余部分为高分子材料和不具有压电性的上述无机填充剂，更优选压电陶瓷粒子的配合量为70～80体积％。如果在高分子树脂片材中高填充压电陶瓷粒子，则容易在高分子树脂片材层的表面诱发电荷。另外，在高分子树脂片材中，优选配合至少20体积％的上述高分子材料。如果压电陶瓷粒子不到50体积％，则压电性没有提高，如果超过80体积％，则高分子树脂片材的机械强度降低。应予说明，在配合比例的计算中，压电陶瓷粒子是指制成上述造粒粉之前的粒子。
高分子树脂片材的制造方法只要为可制成薄的片状的方法，就能够使用。本发明中，优选如下的制造方法：在使上述高分子材料溶解的水或有机溶剂中使上述压电陶瓷粒子等填充材料分散，制造浆料，将该浆料在支承体上涂布，制成薄膜，通过干燥等将水或有机溶剂除去。将浆料在支承体上涂布的方法能够使用以刮刀法为代表的带式流延法、旋涂法等公知的方法。
高分子树脂片材1张的厚度为10～100μm，优选为30～50μm。如果高分子树脂片材层的厚度不到10μm，则制成压电元件时的机械强度降低，如果超过100μm，则柔软性降低，对于压电元件给予振动时有时产生裂纹。
高分子非织造织物只要是通过利用热·机械或化学作用使纤维化的高分子材料粘接或缠结而制成的布，就能够使用。构成高分子非织造织物的纤维的平均直径优选为0.05～5μm，更优选0.5～1μm。如果平均直径比5μm大，则非织造织物层的孔隙的体积减小，因此发电性能降低。另外，如果平均直径不到0.05μm，则纤维给予压电陶瓷粒子的应力变小，发电性能降低。应予说明，本发明中的纤维的平均直径是根据采用扫描型电子显微镜得到的图像测定和算出的平均值。
就成为高分子非织造织物的高分子材料而言，对其种类并无特别限定，另外，对有无起因于分子结构的压电性无限制。从耐热性的方面出发，优选熔点为150℃以上的结晶性树脂或者玻璃化转变温度为150℃以上的非晶性树脂，更优选柔软性优异的树脂。具体地，可列举出PVA、PVB、PVDF、四氟乙烯-乙烯共聚物、四氟乙烯-六氟丙烯共聚物、四氟乙烯-全氟烷氧基乙烯共聚物等。
在高分子非织造织物中保持或配合上述压电陶瓷粒子。高分子非织造织物优选与上述压电陶瓷粒子一起保持或配合不具有压电性的无机填充剂。作为无机填充剂，为了使非织造织物层内的电荷移动变得容易，优选保持或配合导电性填料。作为导电性填料，可列举出石墨、炭黑、碳纳米管、富勒烯、金属粉末等。另外，作为无机填充剂，为了提高非织造织物层的机械强度，能够保持或配合补强材料。作为补强材料，可列举出碳纳米管、晶须等。在此，所谓保持，是指在高分子非织造织物的纤维间固定有压电陶瓷粒子，所谓配合，是指在纤维化的高分子材料的内部含有压电陶瓷粒子。
高分子非织造织物优选保持或配合30～60体积％的压电陶瓷粒子，剩余部分设为上述纤维化的高分子材料，或者剩余部分为上述纤维化的高分子材料和不具有压电性的上述无机填充剂，压电陶瓷粒子的保持或配合量更优选为50～60体积％。另外，优选配合至少40体积％的纤维化的高分子材料。如果压电陶瓷粒子不到30体积％，则压电性没有提高，如果超过60体积％，则高分子非织造织物的机械强度降低。
高分子非织造织物的制造方法只要是能够使用平均直径为0.05～5μm的纤维来制成薄的非织造织物的方法，就能够使用。在本发明中，优选使用通过在使高分子材料溶解于水或有机溶剂而成的溶液中将上述压电陶瓷粒子分散而得到的浆料，采用电场纺丝法来制造。电场纺丝法是通过在电场纺丝装置的注射器的针头与集电极之间施加电压、将注射器内的浆料向着集电极射出来，从而制作非织造织物的方法。集电极的形状为转鼓型、圆盘型、板型等，并无特别限定，优选能够制作大面积的非织造织物的转鼓型。通过使得到的非织造织物干燥，能够将水或有机溶剂除去。
1张高分子非织造织物的厚度为10～300μm，优选为120～200μm。如果高分子非织造织物的厚度不到10μm，则制成压电元件时的压电性降低，如果超过300μm，则对压电元件给予振动时有时在高分子非织造织物的内部产生断裂。
就本发明的压电元件而言，通过使上述高分子树脂片材与高分子非织造织物的层叠体一体化，从而得到片状的压电元件。就一体化而言，可列举出使用压机进行压接的方法等。
另外，本发明的压电元件的极化方法优选包括对上述一体化了的压电元件施加直流电场的工序。作为具体的极化方法，可列举出在大气中使用电晕放电的方法、在加热到100～200℃的硅油中施加直流电场的方法等。
本发明的压电元件使高分子树脂片材层与非织造织物层一体化，在高分子树脂片材层中高填充压电陶瓷粒子，从而在压电元件表面容易诱发电荷，能够容易地将电荷取出。另外，通过在非织造织物层中高填充压电陶瓷粒子，从而能够不损害柔软性地显现高的压电性。进而，通过使片材层的厚度、非织造织物层的厚度、片材层与非织造织物层的层数最优化，从而能够提高发电性能。因此，本发明的压电元件能够应用于振动发电、电流传感器、电压传感器的用途，特别适于利用了环境振动的振动发电。
实施例
实施例1～14和比较例1～7
关于用作压电陶瓷的NKN粒子，将Na2CO3(纯度99.9％)、K2CO3(纯度99.9％)、Nb2O5(纯度99.9％)作为原料粉末，将该原料粉末充分地混合，将混合物在1098℃下烧结2小时，之后破碎，从而制作平均粒径1μm的粉末。使该粉末分散于作为高分子粘结剂的聚氨酯溶液中，采用喷雾干燥法制作造粒粉。
在溶解了7质量％的PVA的水溶液中使该造粒粉分散而制备浆料，将该浆料在支承体上带式流延，从而制作高分子树脂片材。在带式流延中，使用了刮刀型涂布机(株式会社井元制作所制造：IMC-70F0-C型)。将得到的片材在室温下干燥，从而将水除去，制成高分子树脂片材。
高分子非织造织物通过对在溶解了PVDF的二甲基亚砜溶液中使上述NKN粒子分散而成的浆料进行电场纺丝而制作。电场纺丝装置使用了井元制作所制：IMC-1639型。使溶解了PVDF的二甲基亚砜溶液的浓度为0.11g/mL，使用相对于PVDF使50体积％的NKN粒子分散而成的浆料，通过在注射器的针头与集电极之间施加18kV的电压，从而使注射器内的浆料向集电极射出，制作非织造织物。通过将得到的非织造织物在室温下干燥，从而将二甲基亚砜除去，制成高分子非织造织物。
将高分子树脂片材、高分子非织造织物分别切割成13mm×28mm的大小，使其交替地层叠后，或者使多张高分子非织造织物层叠后，采用压机在压力40MPa、温度65℃的条件下加压3分钟，从而得到了层叠体。关于层叠体的结构和厚度、在高分子树脂片材和高分子非织造织物中保持或配合的NKN量、高分子树脂片材和高分子非织造织物的厚度、构成高分子非织造织物的纤维的平均直径，示于表1和表2中。
如图3中所示那样，在得到的层叠体的表背两面涂布银糊剂8，形成上部和下部电极，安装铜箔带9，得到了压电元件。使用该压电元件，使用图4中所示的电路，在压电元件的纵向(图3中所示的箭头方向)上给予170Hz的伸缩振动，测定了每1振动的发电量。将结果示于表1和表2中。
[表1]
*注)由于片材层的断裂，不能测定
[表2]
如实施例6中所示那样，结果是，作为层叠体的4-3结构的压电元件成为最大的发电量。另外，高分子树脂片材层中的NKN粒子配合量越多，发电量越为大值，但在比较例3(高分子树脂片材1层的厚度40μm、NKN粒子配合量90体积％)、比较例4(高分子树脂片材1层的厚度5μm、NKN粒子配合量70体积％)中，发生了片材层的断裂，因此不能进行发电量的测定。另外，发电量在高分子非织造织物层的纤维的平均直径为0.05～5μm的范围中显示出良好的值。表2中示出了根据高分子非织造织物层的厚度的发电量。实施例13(1层高分子非织造织物的厚度200μm)为最优异的结果。
产业上的可利用性
本发明能够在利用了环境振动的振动发电的领域中使用。
附图标记说明
1 层叠体
2 高分子树脂片材
3 高分子非织造织物
4 压电陶瓷粒子
5 非织造织物
6 试样台
7 针状电极
8 银糊剂
9 铜箔带
10 负载电阻
11 示波器

Claims (7)

1.压电元件，其包含将保持或配合有压电陶瓷粒子的高分子非织造织物与配合有压电陶瓷粒子的高分子树脂片材以含有至少一层所述高分子非织造织物的方式层叠而成的层叠体，其特征在于，所述层叠体是能够实现由在1层所述高分子非织造织物的2个主平面侧分别各自层叠了1层所述高分子树脂片材而成的层叠体产生的发电量以上的发电量的层叠体。
2.根据权利要求1所述的压电元件，其特征在于，所述高分子非织造织物是构成该高分子非织造织物的纤维的平均直径为0.05～5μm、保持或配合有30～60体积％的压电陶瓷粒子的1层的厚度为10～300μm的非织造织物，所述高分子树脂片材是配合有50～80体积％的压电陶瓷粒子的1层的厚度为10～100μm的片材。
3.根据权利要求1所述的压电元件，其特征在于，所述层叠体层叠有多张所述高分子非织造织物。
4.根据权利要求3所述的压电元件，其特征在于，所述层叠体的2个主平面侧都为所述高分子树脂片材。
5.根据权利要求1所述的压电元件，其特征在于，所述层叠体中，所述高分子非织造织物与所述高分子树脂片材交替地层叠。
6.根据权利要求5所述的压电元件，其特征在于，所述层叠体的2个主平面侧都为所述高分子树脂片材。
7.权利要求1所述的压电元件的制造方法，该压电元件的制造方法包括：
使保持或配合有压电陶瓷粒子的高分子非织造织物与配合有压电陶瓷粒子的高分子树脂片材以包含至少一层所述高分子非织造织物的方式层叠的工序、和
使用压机对所述层叠了的层叠体进行压接从而一体化的工序，
其特征在于，所述保持或配合有压电陶瓷粒子的高分子非织造织物是采用对浆料进行电场纺丝的电场纺丝法制造的高分子非织造织物，所述浆料通过在使高分子溶解于水或有机溶剂而成的溶液中将所述压电陶瓷粒子分散而得到。
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CN111575918B (zh) * 2020-05-26 2022-08-02 哈尔滨理工大学 一种具有双梯度结构的聚醚酰亚胺基复合介质及其制备方法与应用
CN112281222A (zh) * 2020-10-28 2021-01-29 中科传感技术(青岛)研究院 一种静电纺丝法制备压电陶瓷粉的工艺
CN112695462A (zh) * 2020-12-25 2021-04-23 湖北科技学院 一种具有多层梯度结构的复合电介质材料及其制备方法

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