CN104037318A - Flexible thermoelectric power generation microcell structure - Google Patents

Flexible thermoelectric power generation microcell structure Download PDF

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CN104037318A
CN104037318A CN201410223834.9A CN201410223834A CN104037318A CN 104037318 A CN104037318 A CN 104037318A CN 201410223834 A CN201410223834 A CN 201410223834A CN 104037318 A CN104037318 A CN 104037318A
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type thermoelectric
thermoelectric
circular cavity
power generation
arms
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梅德庆
刘海燕
姚喆赫
陈子辰
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

本发明公开了一种柔性温差发电微单元结构。在基底上开有多排和多偶数列的蜂窝型圆形腔,除了边缘两列圆形腔外,其它圆形腔底部开有一个微孔,向开有微孔的圆形腔内底部滴涂银基纳米粒子油墨,填充微孔并覆盖住圆形腔底部。每排圆形腔中均相间填充有P型热电臂和N型热电臂,每对P型热电臂和N型热电臂的顶端分别用上层铜导线相连,每排开有微孔的N型热电臂和P型热电臂为一组,开有微孔的圆形腔外底面分别用下层铜导线相连构成柔性温差发电微单元结构。本发明具有高度柔性,稳定性高,当温差发电单元受冲击时,包裹热电臂的基底可避免延展性差的碲化铋热电材料发生断裂、失效。它能针对体内植入式医疗微装置的供能,具有推广应用价值。

The invention discloses a micro-unit structure for flexible thermoelectric power generation. There are multiple rows and even columns of honeycomb-shaped circular cavities on the base. Except for the two rows of circular cavities on the edge, there is a micropore at the bottom of the other circular cavities, which drips into the bottom of the circular cavity with micropores. Silver-based nanoparticle ink is applied to fill the pores and cover the bottom of the circular cavity. Each row of circular cavities is filled with P-type thermoelectric arms and N-type thermoelectric arms alternately, and the tops of each pair of P-type thermoelectric arms and N-type thermoelectric arms are connected with upper-layer copper wires, and each row has micro-holed N-type thermoelectric arms. The arm and the P-type thermoelectric arm form a group, and the outer bottom surface of the circular cavity with micro-holes is respectively connected with the lower layer of copper wires to form a flexible thermoelectric power generation micro-unit structure. The invention has high flexibility and high stability, and when the thermoelectric power generation unit is impacted, the substrate wrapping the thermoelectric arm can prevent the bismuth telluride thermoelectric material with poor ductility from breaking and failing. It can supply energy for implanted medical micro-device in the body, and has the value of popularization and application.

Description

柔性温差发电微单元结构Micro-unit structure of flexible thermoelectric power generation

技术领域 technical field

本发明涉及一种温差发电装置,尤其涉及一种柔性温差发电微单元结构。 The invention relates to a thermoelectric power generation device, in particular to a flexible thermoelectric microunit structure.

背景技术 Background technique

体内植入式医疗装置应用越来越广泛,例如心脏起搏器、除颤器、药物泵等,能够代替或提高器官的功能或者治疗某种疾病。为植入式医疗装置提供持久稳定的供能是当今世界一个研究热点和难题。目前几种应用于植入式医疗装置的电源主要有:锂电池、生物燃料电池、核电池、无线能量传输等。微小型锂电池往往寿命短,病人还需长期更换电池,带来许多痛苦;核电池工作寿命可以超过十年,但一般体积较大,而且对人体具有毒性和辐射;生物燃料电池利用酶或者微生物作为催化剂,将葡萄糖等生物燃料的化学能转换成电能,但是供电寿命一般只有几天;无线能量传输则通过电磁波、电磁耦合、超声波、光波等无线传输方式对体内植入式电源进行充电或直接供电,采用该方法往往需要病人长期配戴外部附加机构,给病人的日常生活和活动带来不便。 Implantable medical devices in the body are used more and more widely, such as pacemakers, defibrillators, drug pumps, etc., which can replace or improve the function of organs or treat certain diseases. Providing durable and stable energy supply for implantable medical devices is a research hotspot and difficult problem in the world today. At present, there are several power sources used in implantable medical devices: lithium batteries, biofuel cells, nuclear batteries, wireless energy transmission, etc. Micro lithium batteries often have a short lifespan, and patients need to replace batteries for a long time, causing a lot of pain; nuclear batteries can work for more than ten years, but they are generally large in size and have toxicity and radiation to the human body; biofuel cells use enzymes or microorganisms As a catalyst, it converts the chemical energy of biofuels such as glucose into electrical energy, but the power supply life is generally only a few days; wireless energy transmission uses electromagnetic waves, electromagnetic coupling, ultrasonic waves, light waves and other wireless transmission methods to charge the implanted power supply in the body or directly Power supply, adopting this method often requires the patient to wear an external additional mechanism for a long time, which brings inconvenience to the patient's daily life and activities.

温差发电利用热电半导体的塞贝克效应,可将热能转化为电能。由于温差发电器件具有无移动部件、无污染、结构简单、易于小型化等优点,同时,由于正常人体的体温恒定且体内与体表间具有较小的温差,而温差发电对温差的下限没有要求,因此,可以直接利用人体存在的温差进行发电。 Thermoelectric power generation uses the Seebeck effect of thermoelectric semiconductors to convert thermal energy into electrical energy. Since the thermoelectric power generation device has the advantages of no moving parts, no pollution, simple structure, and easy miniaturization, etc., at the same time, because the body temperature of the normal human body is constant and there is a small temperature difference between the body and the body surface, the thermoelectric power generation has no requirement for the lower limit of the temperature difference , Therefore, the temperature difference existing in the human body can be used directly to generate electricity.

现有的微型柔性温差发电构件通常是在基底上直接布置热电臂或者在块体的微型热电材料间采用柔性连接,因为人体内环境有许多曲面而且人体活动具有灵活性,热电臂经常会受到挤压拉伸等冲击,这类温差发电器稳定性不够,这样就需要温差发电构件具有更好的柔性;采用碲化铋及其合金可以提高温差发电装置的发电功率,但是,碲化铋(BiTe)材料力学性能较差,材料较脆,受压力或冲击时,直接加工在柔性基底上的碲化铋及其合金材料容易断裂,使温差发电单元失效。因此,开发一种能够减小冲击,稳定可靠、柔性较好的温差发电微单元结构是十分必要的。 Existing miniature flexible thermoelectric power generation components usually arrange thermoelectric arms directly on the substrate or use flexible connections between bulk miniature thermoelectric materials, because the internal environment of the human body has many curved surfaces and the human body is flexible, and the thermoelectric arms are often squeezed. Stability of this kind of thermoelectric generator is not enough, so it is necessary to have better flexibility of thermoelectric power generation components; the use of bismuth telluride and its alloys can improve the power generation of thermoelectric power generation devices, but bismuth telluride (BiTe ) The mechanical properties of the material are poor, and the material is relatively brittle. When subjected to pressure or impact, the bismuth telluride and its alloy materials directly processed on the flexible substrate are easy to break, which makes the thermoelectric power generation unit invalid. Therefore, it is very necessary to develop a thermoelectric power generation micro-unit structure that can reduce the impact, is stable, reliable and flexible.

发明内容 Contents of the invention

本发明的目的在于提供一种柔性温差发电微单元结构,具有稳定可靠、热电转换效率高、适用曲面、可加工成多种形式的温差发电器等特点。 The purpose of the present invention is to provide a flexible micro-unit structure for thermoelectric power generation, which has the characteristics of stability and reliability, high thermoelectric conversion efficiency, applicable to curved surfaces, and can be processed into various forms of thermoelectric generators.

本发明采用的技术方案是: The technical scheme adopted in the present invention is:

在基底上开有多排和多偶数列的蜂窝型圆形腔,除了边缘两列圆形腔之外,其它圆形腔底部开有一个微孔,开有微孔的圆形腔内底部滴涂银基纳米粒子油墨填充所述的微孔,并覆盖住圆形腔底部;每排圆形腔中均相间填充有P型热电臂和N型热电臂,每对P型热电臂和N型热电臂的顶端分别用上层铜导线相连,上层铜导线铺设在上层柔性电路板下面,每排开有微孔的N型热电臂和P型热电臂为一组,开有微孔的圆形腔外底面分别用下层铜导线相连,然后,以相同连接方式依次构成柔性温差发电微单元结构。 There are multiple rows and even columns of honeycomb circular cavities on the base. Except for the two rows of circular cavities on the edge, there is a micropore at the bottom of the other circular cavities. The bottom of the circular cavity with micropores drops Silver-based nano-particle ink fills the micropores and covers the bottom of the circular cavity; each row of circular cavity is filled with P-type thermoelectric arms and N-type thermoelectric arms alternately, and each pair of P-type thermoelectric arms and N-type thermoelectric arms The tops of the tops are respectively connected with the upper layer copper wires, and the upper layer copper wires are laid under the upper layer flexible circuit board. Each row of N-type thermoelectric arms and P-type thermoelectric arms with micro-holes is a group, and the outer bottom surface of the circular cavity with micro-holes They are respectively connected with the copper wires of the lower layer, and then the flexible thermoelectric power generation micro-unit structure is sequentially formed in the same connection manner.

所述P型热电臂和N型热电臂的材料均为掺杂的碲化铋。 The materials of the P-type thermoelectric arm and the N-type thermoelectric arm are both doped bismuth telluride.

所述基底和上层柔性电路板的材料均为聚酰亚胺。 Both the base and the upper flexible circuit board are made of polyimide.

本发明具有的有益效果是: The beneficial effects that the present invention has are:

本发明采用聚酰亚胺蜂窝型基底包裹热电臂并且下层铜导线成弯曲结构使得温差发电单元具有高度柔性,可在多个方向变形。当温差发电单元发生结构变形时,圆形聚酰亚胺空腔包裹热电臂可避免延展性差的碲化铋热电材料发生断裂,避免温差发电单元的失效。该发明主要针对体内植入式医疗微装置的供能,具有推广应用价值。 The invention adopts the polyimide honeycomb base to wrap the thermoelectric arm, and the copper wire in the lower layer has a curved structure, so that the thermoelectric power generation unit has high flexibility and can be deformed in multiple directions. When the thermoelectric unit undergoes structural deformation, the circular polyimide cavity wrapping the thermoelectric arm can prevent the bismuth telluride thermoelectric material with poor ductility from breaking and avoid the failure of the thermoelectric unit. The invention is mainly aimed at the energy supply of implanted medical micro-device in the body, and has the value of popularization and application.

附图说明 Description of drawings

图1是本发明结构正面等轴测视图。 Figure 1 is a frontal isometric view of the structure of the present invention.

图2是本发明结构背面等轴测视图。 Figure 2 is an isometric view of the back of the structure of the present invention.

图3是本发明结构背面正视图。 Fig. 3 is a rear front view of the structure of the present invention.

图4是图3的D-D剖视图。 Fig. 4 is a D-D sectional view of Fig. 3 .

图5是P型与N型热电臂分布示意图。 Fig. 5 is a schematic diagram of distribution of P-type and N-type thermoelectric arms.

图6是上层柔性电路板示意图。 Fig. 6 is a schematic diagram of the upper flexible circuit board.

图7是下层柔性电路板背面正视图。 Fig. 7 is a front view of the back of the lower flexible circuit board.

图8是图7的H-H剖视图。 Fig. 8 is a sectional view taken along line H-H of Fig. 7 .

图9是蜂窝型聚酰亚胺基底的模具图。 Figure 9 is a mold drawing of a honeycomb polyimide substrate.

图10是溅射下层铜导线所需的掩模板图。 Figure 10 is a diagram of the mask template required for sputtering the underlying copper wires.

图11是往圆形空腔中喷墨打印热电材料示意图。 Fig. 11 is a schematic diagram of inkjet printing thermoelectric materials into a circular cavity.

图中:1、基底,2、银基纳米粒子油墨,3、P型热电臂,4、N型热电臂,5、上层柔性电路板,6、上层铜导线,7、下层铜导线,8、聚酰亚胺基底模具的上模,9、聚酰亚胺基底模具的下膜,10、掩模板,11、针头。 In the figure: 1. Substrate, 2. Silver-based nanoparticle ink, 3. P-type thermoelectric arm, 4. N-type thermoelectric arm, 5. Upper layer flexible circuit board, 6. Upper layer copper wire, 7. Lower layer copper wire, 8. The upper mold of the polyimide base mold, 9, the lower film of the polyimide base mold, 10, the mask plate, 11, the needle head.

具体实施方式 Detailed ways

下面结合附图和实施例对本发明作进一步的说明。 The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

如图9所示,本发明在聚酰亚胺基底模具的下膜9内浇注聚酰亚胺,用聚酰亚胺基底模具的上模8挤压,固化成蜂窝型圆形腔的基底1。如图2、图3、图4、图5、图6、图7、图8所示,本发明在基底1上开有多排和多偶数列的蜂窝型圆形腔(图中开有四排四列圆形腔,只需如图2中间两列进行阵列即可增加列数),除了边缘两列圆形腔之外,其它圆形腔底部开有一个微孔,如图11所示,在开孔的圆形腔中开有微孔的圆形腔内底部滴涂银基纳米粒子油墨2填充所述的微孔并覆盖住圆形腔底部。如图5每排圆形腔中均相间填充有P型热电臂3和N型热电臂4,每对P型热电臂3和N型热电臂4的顶端分别用上层铜导线6相连,上层铜导线铺设在上层柔性电路板5下面(如图6所示),每排开有微孔的P型热电臂3和N型热电臂4为一组,开有微孔的圆形腔外底面分别用下层铜导线7相连,然后,以相同连接方式依次构成柔性温差发电微单元结构。 As shown in Figure 9, the present invention casts polyimide in the lower film 9 of the polyimide base mold, extrudes with the upper mold 8 of the polyimide base mold, and solidifies into the base 1 of the honeycomb circular cavity . As shown in Fig. 2, Fig. 3, Fig. 4, Fig. 5, Fig. 6, Fig. 7 and Fig. 8, the present invention has multiple rows and multiple even-numbered rows of honeycomb circular cavities on the substrate 1 (there are four Arrange four rows of circular cavities, only need to array the two rows in the middle as shown in Figure 2 to increase the number of columns), except for the two rows of circular cavities on the edge, there is a micro-hole at the bottom of the other circular cavities, as shown in Figure 11 , in the circular chamber with micropores in the bottom of the circular chamber with micropores, drop-coat silver-based nanoparticle ink 2 to fill the micropores and cover the bottom of the circular chamber. As shown in Figure 5, each row of circular cavities is evenly filled with P-type thermoelectric arms 3 and N-type thermoelectric arms 4, and the tops of each pair of P-type thermoelectric arms 3 and N-type thermoelectric arms 4 are connected with upper-layer copper wires 6 respectively. The wires are laid under the upper flexible circuit board 5 (as shown in Figure 6). Each row of P-type thermoelectric arms 3 and N-type thermoelectric arms 4 with micro-holes is a group, and the outer bottom surface of the circular cavity with micro-holes is respectively The lower-layer copper wires 7 are used to connect, and then the flexible thermoelectric power generation micro-unit structure is sequentially formed in the same connection manner.

所述P型热电臂3和N型热电臂4的材料均为掺杂的碲化铋。 The materials of the P-type thermoelectric arm 3 and the N-type thermoelectric arm 4 are both doped bismuth telluride.

所述基底1和上层柔性电路板5的材料均为聚酰亚胺。 Both the base 1 and the upper flexible circuit board 5 are made of polyimide.

滴涂银基纳米粒子油墨2填充所述的微孔并覆盖住圆形腔底部,如图5在每个圆型腔中相间用滴涂法填充P型热电臂3和N型热电臂4,每排每对P型热电臂3和N型热电臂4的顶端用溅射的上层铜导线6相连,每对带微孔的P型热电臂3和N型热电臂4的背面,用如图10所示的掩模板溅射的下层铜导线7连接,银基纳米粒子油墨2与下层铜导线7导通,使被包裹的N型热电臂4的底端与相邻的P型热电臂3的底端导通,以相同连接方式依次构成柔性温差发电微单元结构,上层柔性电路板5的伸出端跟外电路连接,该单元结构贴合在人体上即可利用人体温差发电。 Drop-coating silver-based nanoparticle ink 2 fills the micropores and covers the bottom of the circular cavity, as shown in Figure 5. Filling the P-type thermoelectric arm 3 and the N-type thermoelectric arm 4 with the drop-coating method in each circular cavity, each row The tops of every pair of P-type thermoelectric arms 3 and N-type thermoelectric arms 4 are connected with sputtered upper-layer copper wires 6, and the back sides of each pair of P-type thermoelectric arms 3 and N-type thermoelectric arms 4 with micro-holes are used as shown in Figure 10. The lower-layer copper wire 7 sputtered by the mask plate shown is connected, and the silver-based nanoparticle ink 2 is connected to the lower-layer copper wire 7, so that the bottom end of the wrapped N-type thermoelectric arm 4 is connected to the bottom of the adjacent P-type thermoelectric arm 3 The ends are turned on, and the flexible thermoelectric power generation micro-unit structure is sequentially formed in the same connection mode. The protruding end of the upper flexible circuit board 5 is connected to the external circuit.

所述的热电臂的材料为掺杂的碲化铋及其合金,P型热电臂3和N型热电臂4交替排列,蜂窝型聚酰亚胺基底可以使装置充分柔性化。 The material of the thermoelectric arms is doped bismuth telluride and its alloys, the P-type thermoelectric arms 3 and the N-type thermoelectric arms 4 are alternately arranged, and the honeycomb polyimide substrate can make the device fully flexible.

柔性温差发电微单元结构,可以折弯成所需形状,再通过封装复合薄膜等导热绝缘的柔性材料,形成能量密度高的温差发电装置。 The micro-unit structure of flexible thermoelectric power generation can be bent into the desired shape, and then a thermoelectric power generation device with high energy density can be formed by packaging composite films and other thermally conductive and insulating flexible materials.

填充微孔和热电材料工艺是如图11所示的滴涂法:点胶机的针头11先将银基纳米粒子油墨滴入微孔中并覆盖圆形腔底部,再在每排圆形腔中相间滴入P型热电材料粉末与粘结剂和N型热电材料粉末与粘结剂,在室温下固化成型。上层柔性电路板的加工工艺:在上层柔性电路板基底上用丝网印刷方法铺上层铜导线6,下层铜导线可用如图10所示的掩膜板溅射得到:在基底背面涂正性光刻胶,用铜掩模板10曝光显影,用铜靶材溅射导线图案,去胶完成铜导线。每排P型热电臂和N型热电臂交替排列,相互平行组成热电偶。柔性温差发电装置的材料和结构都具有高度柔性,可以贴合曲面。 The process of filling micropores and thermoelectric materials is a drop coating method as shown in Figure 11: the needle 11 of the dispenser first drops the silver-based nanoparticle ink into the micropores and covers the bottom of the circular cavity, and then sprays the silver-based nanoparticle ink on the bottom of each row of circular cavities. The P-type thermoelectric material powder and binder and the N-type thermoelectric material powder and binder are dropped into the middle phase, and solidified and formed at room temperature. The processing technology of the upper flexible circuit board: Lay the upper layer of copper wire 6 on the base of the upper layer of flexible circuit board by screen printing method, and the lower layer of copper wire can be obtained by sputtering with a mask plate as shown in Figure 10: apply positive light on the back of the substrate The resist is exposed and developed with a copper mask 10, the copper target is used to sputter the wire pattern, and the glue is removed to complete the copper wire. Each row of P-type thermoelectric arms and N-type thermoelectric arms are arranged alternately, forming thermocouples parallel to each other. The material and structure of the flexible thermoelectric power generation device are highly flexible and can fit curved surfaces.

本发明的工作原理是: The working principle of the present invention is:

由塞贝克效应,P型及N型热电臂的温度差会在两端产生电压差,由于单个热电偶产生的电压很低,因此,可采用“热路并联,电路串联”的方式,将P型和N型热电臂组成的热电偶设计并布置形成单排多对或多排阵列型的热电模块从而提高输出电压值。 Due to the Seebeck effect, the temperature difference between the P-type and N-type thermoelectric arms will generate a voltage difference at both ends. Since the voltage generated by a single thermocouple is very low, the method of "parallel connection of thermal circuits and series connection of circuits" can be used to connect P The thermocouples composed of type and N-type thermoelectric arms are designed and arranged to form single-row multi-pair or multi-row array thermoelectric modules to increase the output voltage value.

实现在柔性聚酰亚胺基底圆形腔中填充热电臂,聚酰亚胺物理、化学性能稳定,与玻璃或硅基底比较,能使结构柔性且轻便、增加了鲁棒性,其灵活性可以适应不同曲面。 Realize the filling of thermoelectric arms in the circular cavity of the flexible polyimide substrate. The physical and chemical properties of polyimide are stable. Compared with glass or silicon substrates, it can make the structure flexible and light, and increase the robustness. Its flexibility can Adapt to different surfaces.

室温下碲化铋材料的热电优值较高,采用碲化铋及其合金可以提高温差发电装置的发电功率。但是,由于碲化铋(BiTe)材料力学性能较差,容易断裂。使得直接加工在柔性基底上的碲化铋材料容易断裂引起温差发电单元失效。所以,将碲化铋材料包裹在聚酰亚胺圆形腔里面,基底本身具有的柔性减少碲化铋材料上施加的压力和冲击,从而避免热电材料断裂引起温差发电单元失效。 The thermoelectric figure of merit of bismuth telluride material at room temperature is relatively high, and the use of bismuth telluride and its alloys can increase the power generation of thermoelectric power generation devices. However, due to poor mechanical properties of bismuth telluride (BiTe) material, it is easy to fracture. The bismuth telluride material directly processed on the flexible substrate is easy to break and cause the failure of the thermoelectric power generation unit. Therefore, the bismuth telluride material is wrapped in the polyimide circular cavity, and the flexibility of the substrate itself reduces the pressure and impact on the bismuth telluride material, thereby avoiding the failure of the thermoelectric power generation unit caused by the fracture of the thermoelectric material.

上述具体实施方式用来解释说明本发明,而不是对本发明进行限制,在本发明的精神和权利要求的保护范围内,对本发明作出的任何修改和改变,都落入本发明的保护范围。 The above specific embodiments are used to explain the present invention, rather than to limit the present invention. Within the spirit of the present invention and the protection scope of the claims, any modification and change made to the present invention will fall into the protection scope of the present invention.

Claims (3)

1. a flexible thermo-electric generation micro unit structure, it is characterized in that: the honeycomb type circular cavity that has many rows and many even columns in substrate (1), except edge two row circular cavities, other circular cavity bottom has a micropore, interior the dripping of circular cavity that has micropore is coated with the described micropore of money base nano particle ink (2) filling, and covers bottom circular cavity; Equal alternate P type thermoelectric arm (3) and N-type thermoelectric arms (4) of being filled with in every row's circular cavity, the top of every pair of P type thermoelectric arm (3) and N-type thermoelectric arm (4) is connected with upper strata copper conductor respectively, upper copper wire is laid on upper strata flexible PCB (5) below, the P type thermoelectric arm (3) and the N-type thermoelectric arm (4) that often arrange micropore are one group, the circular cavity outer bottom that has micropore is connected with lower floor's copper conductor respectively, then, form successively flexible thermo-electric generation micro unit structure with identical connected mode.
2. the flexible thermo-electric generation micro unit of one according to claim 1 structure, is characterized in that: the material of described P type thermoelectric arm (3) and N-type thermoelectric arm (4) is the bismuth telluride of doping.
3. the flexible thermo-electric generation micro unit of one according to claim 1 structure, is characterized in that: the material of described substrate (1) and upper strata flexible PCB (5) is polyimides.
CN201410223834.9A 2014-05-23 2014-05-23 Flexible thermoelectric power generation microcell structure Pending CN104037318A (en)

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