WO2020186665A1 - 一种盐浓度梯度驱动的纳流体发电装置及其制备与应用 - Google Patents

一种盐浓度梯度驱动的纳流体发电装置及其制备与应用 Download PDF

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WO2020186665A1
WO2020186665A1 PCT/CN2019/095690 CN2019095690W WO2020186665A1 WO 2020186665 A1 WO2020186665 A1 WO 2020186665A1 CN 2019095690 W CN2019095690 W CN 2019095690W WO 2020186665 A1 WO2020186665 A1 WO 2020186665A1
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liquid
channel
nano
power generation
electrode
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缪向水
何毓辉
黄卓
张艳
张盼
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Huazhong University of Science and Technology
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    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N3/00—Generators in which thermal or kinetic energy is converted into electrical energy by ionisation of a fluid and removal of the charge therefrom

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  • the present invention belongs to the field of nanofluidic generators. More specifically, it relates to a nanofluid power generation device driven by a salt concentration gradient and its preparation and application.
  • a nanofluid power generation device driven by a seawater-fresh water salt concentration gradient specifically through micro-nano The process prepares channels with nanometer depth, width, and length, and generates electricity by applying salt concentration in the reservoir.
  • Nanochannels refer to tiny channels with at least one-dimensional dimension in the nanometer range, which have many advantages in the field of nanofluid research. Due to the solid-liquid reaction after contact with the fluid, the wall surface of the nanochannel will be charged (taking SiO 2 as an example: negatively charged), and the size of the nanochannel is at the nanometer level. Due to the strong ion selectivity caused by the surface effect, it can be used To collect the chemical potential energy in the concentration difference into electrical energy. Since the preparation of the nanochannel is planar etching, it has the conditions for large-scale preparation, and is compatible with CMOS, and easy to connect external circuits.
  • micro-nano devices such as nano-electromechanical systems, micro-sensors, and wearable flexible Electronic equipment and so on.
  • This kind of emerging nanoscale devices and equipment usually work under extremely low operating voltage and extremely low power consumption, and the matching with them requires nanoscale power generation devices-nanofluid power generation devices.
  • nanofluid power generation devices mainly have the following defects: 1.
  • the power density of 2.6*10 3 W/m 2 can be obtained by using nanopores etched by organic films, but the film in the electrolyte has the problem of expansion and contraction. Affect device stability.
  • the output power density of the CMOS-compatible nano-channel power generation device prepared based on the standard semiconductor manufacturing process is only 7.7W/m 2 .
  • the purpose of the present invention is to provide a nanofluid power generation device driven by a salt concentration gradient and its preparation and application, based on the specific energy conversion principle of converting chemical potential energy of salt concentration differences into electrical energy ,
  • the nanofluid power generation device Through the key nano-channel (especially the specific morphology of the nano-channel, etc.) in the nanofluid power generation device and other structures that cooperate with the nano-channel (such as the first liquid channel and the second liquid channel)
  • the improvement can realize the use of salt concentration gradient to drive power generation, especially the use of seawater-fresh salt concentration to achieve power generation; and the present invention also improves the overall process flow design corresponding to the preparation method, and modifies device parameters (such as nano-channels).
  • the depth, width, and length of the channel, especially the depth and length of the nano-channel can be optimally controlled to achieve high-precision controlled nano-channel structures and high power generation performance.
  • the process means has little damage to device samples and less pollution , High preparation efficiency.
  • a nanofluidic power generation device which is characterized by comprising a nanochannel, and a first liquid channel and a second liquid channel respectively located at two ends of the nanochannel ,
  • the nano channel, the first liquid channel, and the second liquid channel are all located on the substrate, and the first liquid channel and the second liquid channel are connected by the nano channel Pass;
  • the first liquid channel is used to contain the first liquid and is connected to the first electrode;
  • the second liquid channel is used to contain the second liquid and is connected to the second electrode;
  • the nanochannel is used to use the difference in salt concentration between the first liquid and the second liquid to convert chemical potential energy into electrical energy, and to output electrical energy through the cooperation of the first electrode and the second electrode .
  • the depth of the nanochannel is 1-100 nm, the width is 1-400 nm, and the length is 400-1000 nm; preferably, the depth is 1-40 nm.
  • the first liquid channel specifically includes a first micron channel, and at least two liquid reservoirs connected by the first micron channel; the depth of the first micron channel is 1 -100um, width is 1-100um, length is 1-3mm;
  • the second liquid channel specifically includes a second micron channel, and at least two liquid reservoirs connected by the second micron channel; the second micron channel has a depth of 1-100um and a width of 1- 100um, length is 1-3mm.
  • first electrode there is one first electrode, and this first electrode is arranged in a reservoir connected to the first micrometer channel;
  • This second electrode is arranged in a liquid reservoir connected to the second micrometer channel.
  • liquid storage tanks there are 4 liquid storage tanks in total, which are respectively located at the four corners of the upper surface of the substrate.
  • the substrate is a SiO 2 substrate or an Al 2 O 3 substrate.
  • the present invention provides a preparation method for preparing the foregoing nanofluid power generation device, which is characterized in that it comprises the following steps:
  • Nano-channels are processed on the SiO 2 substrate by micro-nanoelectronic technology, which specifically includes electron beam exposure, development, plasma etching, and post-development; and, the processed nano-channels At least 2 mm area to be processed is also left at both ends of the, for preparing the first liquid channel and the second liquid channel;
  • the first liquid channel and the second liquid channel respectively located at the two ends of the nano-channel are prepared by over-etching with a UV lithography machine.
  • the specific operation is: spin coating negative photoresist, and then in the UV lithography machine Align the nano-channel, engrave and expose, then use the corresponding developer for development, plasma etching, and post-development to complete the preparation of the first liquid channel and the second liquid channel at both ends of the nano-channel and Registration
  • (3) PDMS packaging is performed on the SiO 2 substrate of the processed nano channel, the first liquid channel and the second liquid channel, and the PDMS is bonded to the SiO 2 substrate by oxygen plasma treatment.
  • the PDMS plate with small holes arranged in the position corresponding to the liquid storage tank is activated by oxygen plasma treatment, and then the PDMS plate is activated under a microscope. Align and seal on a silicon substrate with nanochannels, a first liquid channel and a second liquid channel. After bonding, the nanofluidic chip preparation is completed; after bonding, the small holes on the PDMS plate and the liquid storage on the silicon substrate The projections of the pool on the surface of the silicon substrate coincide;
  • the thickness of the PDMS plate is 500 ⁇ m, and the diameter of the small holes is 2 mm.
  • the preparation method further includes the steps:
  • the first liquid is seawater
  • the second liquid is fresh water
  • the present invention provides the application method of the above-mentioned nanofluid power generation device, characterized in that the method specifically includes injecting the first liquid channel and the second liquid channel into the first liquid channel and the second liquid channel of the nanofluid power generation device. Liquid and second liquid, the nano channel uses the difference in salt concentration between the first liquid and the second liquid to convert chemical potential energy into electrical energy, which is output through the first electrode and the second electrode in cooperation .
  • the first liquid is seawater
  • the second liquid is fresh water
  • the nanofluid power generation device prepared by the present invention uses standard microelectronics and electron beam exposure processes to prepare nanochannels, and then overlays to prepare nanochannels With the preparation of the first liquid channel and the second liquid channel at both ends and the registration chamber, the power density of the device is increased by two orders of magnitude.
  • the nano channel is preferably connected to the first/second liquid channel with a reservoir and a micro channel.
  • the chemical potential energy can drive the ion movement in the channel, and the surface charge of the nanochannel causes more heterogeneous ion channels to form a net current and the channel
  • the voltage at both ends can then use the net current and voltage to output electrical energy.
  • the nanochannel with the specific preferred shape parameter is especially suitable for the first/second liquid whose concentration ratio is greater than or equal to 1000/1.
  • the present invention can also prevent the collapse of PDMS in the nano-channel by preferably designing the micro-channel with a depth different from that of the nano-channel, and using the micro-channel to communicate with the reservoir.
  • the present invention designs the first micro-channel and the second micro-channel (the first micro-channel and the second micro-channel)
  • the two micrometer channels can be located on both sides of the nanometer channel), and the first micrometer channel and the second micrometer channel are preferably controlled to have a depth of 1-100um, a width of 1-100um, and a length of 1-3mm.
  • the channel occupies a small area, the substrate next to it can support the entire PDMS without collapsing, and the micro-channel has little effect on the ion transport performance of the nano-channel, which is very suitable.
  • EBL Electron Beam Lithography
  • SEM Scanning Electron Microscope
  • the present invention has the following beneficial effects:
  • the energy of the nanofluid power generation device driven by the salt concentration gradient in the present invention can especially be derived from the chemical potential difference between seawater and freshwater, which is a clean and renewable energy source.
  • This nanofluidic device is compatible with CMOS technology, and the external circuit is simple, which is convenient for large-scale integration.
  • Fig. 1 is a structural diagram of the nanofluid power generation device of the present invention.
  • a is a SEM scan image of a micro-channel and a nano-channel processed by a micro-nano process
  • b is an SEM scan image of a part of the nano-channel.
  • Fig. 3 is a current-voltage characteristic diagram for testing the power generation performance of the present invention using a semiconductor tester B1500A.
  • Figure 4 shows the power generation performance test chart of the prepared device, the salt concentration ratio of the reservoir on both sides of the nanochannel and (a) open circuit voltage, (b) short-circuit current, (b) output power density (output power/nanochannel) Cross-section) diagram.
  • the length of the nanochannel in this device is 715nm, the width is 350nm, and the depth is 40nm.
  • the high concentration end is 1Mol/L KCl solution, and the low concentration end is adjusted from 10 -4 Mol/L to 1Mol/L KCl solution.
  • 0 is a silicon wafer
  • 1 is a nano channel
  • 2 is a micro channel
  • 3 is a reservoir
  • 4 is an Ag/AgCl doped electrode
  • 5 is a polydimethylsiloxane Alkane (PDMS) plate.
  • PDMS polydimethylsiloxane Alkane
  • liquid storage tanks are arranged at the left and right ends, and the left and right liquid storage tanks are connected with micrometer channels to communicate, and nanometer channels are arranged between the two micrometer channels. Nano-channels connecting micro-channels.
  • the device is especially a nanofluid power generation device that can be driven by the salt concentration gradient of seawater and freshwater. Sea water is applied to the left reservoir of the device, and fresh water is applied to the right reservoir. Due to the ion selectivity of the nanochannel, more cations generate current through the channel. The voltage and current generated by the device can be detected through the electrodes of the reservoir.
  • the nano-fluid power generation device can be widely used for power supply of various micro-nano devices.
  • the nanofluid power generation device may adopt a processing method including the following steps:
  • the nano-channel 1 of the cashier fluid power generation device is designed and processed.
  • the nano-channel is processed by micro-nano electronic technology on a silicon wafer 0.
  • a SiO 2 channel with a depth of 1-40nm, a width of 1-400nm, and a length of 400-1000nm is prepared (the upper surface of commercially available commercial silicon wafers has SiO 2
  • a pure SiO 2 substrate can also be directly used instead of silicon wafers; SiO 2 substrates represented by silicon wafers are compatible with CMOS technology, which is convenient for subsequent preparation processes).
  • a 2 mm area to be processed is reserved at both ends of the nano-channel for preparing micro-channels and liquid reservoirs;
  • the shape parameters of a single reservoir can be set as follows: a cylinder with a diameter of 2mm and a depth of 1mm;
  • a 500 ⁇ m thick polydimethylsiloxane (PDMS) plate 5 with 4 holes of 2mm diameter was prepared, and then the PDMS was aligned and sealed on the nanochannel chip under the microscope (The hole is aligned and connected to the reservoir) to complete the preparation of the nanofluidic chip. Then inject seawater and fresh water into the two holes located at both ends of the nanochannel respectively, and insert the Ag/AgCl electrode 4 into the other two holes to output electric energy (the two holes inserted into the electrode can also be injected with seawater or fresh water respectively, which is convenient Measure and reduce noise).
  • a 500 ⁇ m thick polydimethylsiloxane (PDMS) board with 4 2mm diameter holes is used to encapsulate the SiO 2 substrate, which can reduce noise during current measurement.
  • the method for testing the power generation performance of the nanofluid power generation device inject different concentrations of KCl solution into two holes at both ends of the nanochannel to form a concentration difference, and simultaneously apply a small voltage on the electrodes of the other two holes and measure the current signal.
  • the current is zero
  • the voltage applied by the electrode is the generating voltage of the power generating device
  • the measured current is the generating current of the power generating device.
  • the current-voltage characteristic test result is shown in Figure 3.
  • the actual power generation is shown in Figure 4, the abscissa represents the salt concentration ratio of the reservoir on both sides of the nanochannel, and the ordinate represents the output power density (output power/cross section of the nanochannel).
  • the location of the reservoir can also be flexibly adjusted, for example, one corner and two One and two at the other corner.
  • the number of electrodes can also be increased. For example, there can be multiple electrodes connected to the same micron channel, and the number of reservoirs can be increased accordingly; the number of reservoirs can also be increased. Separate increase, such as adding a reservoir in the middle of the micro-channel.
  • the present invention is also applicable to other solutions with different salt concentrations, such as other strong acid and strong alkali salt solutions with different concentrations.
  • the silicon substrate corresponding to the SiO 2 substrate
  • the present invention may also use an alumina substrate; the plasma etching used in the present invention may specifically be inductively coupled plasma etching ( Inductively Coupled Plasma Etch, ICPE).

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Abstract

一种盐浓度梯度驱动的纳流体发电装置及其制备与应用，该纳流体发电装置包括纳米沟道（1），以及分别位于该纳米沟道（1）两端、且与该纳米沟道（1）相连通的第一液体沟道（2）与第二液体沟道（2）；其中，第一液体沟道（2）用于容纳第一液体；第二液体沟道（2）用于容纳第二液体；纳米沟道（1）用于利用第一液体与第二液体两者之间的盐浓度差异将化学势能转化为电能，并通过第一电极（4）与第二电极（4）配合输出电能。基于将盐浓度差异的化学势能转化为电能的具体能量转换原理，通过对纳流体发电装置内关键的纳米沟道（1）以及与该纳米沟道（1）配合作用的其他结构进行改进，可实现利用盐浓度梯度驱动发电，尤其可利用海水-淡水盐浓度实现发电。

Description

一种盐浓度梯度驱动的纳流体发电装置及其制备与应用 【技术领域】
本发明属于纳流控发电机领域，更具体地，涉及一种盐浓度梯度驱动的纳流体发电装置及其制备与应用，例如海水-淡水盐浓度梯度驱动的纳流体发电装置，具体通过微纳工艺制备出纳米级深度、宽度、长度的沟道，并通过在储液池施加盐浓度进行发电。
【背景技术】
纳米沟道是指至少有一维尺寸在纳米级的微小沟道，其在纳流体研究领域具有许多优势。由于与流体接触后的固液反应，纳米沟道壁面会带电(以SiO 2为例：带负电)，而纳米沟道的尺寸在纳米级，由于表面效应导致的离子选择性强，因而可以用以收集浓度差中的化学势能转化成电能。由于纳米沟道的制备是平面刻蚀，具备大规模制备的条件，且与CMOS兼容，外部电路并接容易，可广泛应用于微纳设备自供电，如纳米机电系统、微型传感器、可穿戴柔性电子设备等等。这类新兴的纳米尺度器件与设备通常是在极低的工作电压与极低的功耗下工作，与之匹配的就要求纳米尺度的发电装置-纳流体发电装置。
目前纳流体发电装置主要存在着下面的缺陷：1.利用有机薄膜刻蚀的纳米孔可以得到高达2.6*10 3W/m 2的功率密度，但是处在电解质中薄膜有膨胀和收缩的问题，影响器件稳定性。2.基于标准的半导体制造工艺制备的与CMOS兼容的纳米沟道发电装置的输出功率密度仅有7.7W/m 2。
【发明内容】
针对现有技术的以上缺陷或改进需求，本发明的目的在于提供一种盐浓度梯度驱动的纳流体发电装置及其制备与应用，基于将盐浓度差异的化学势能转化为电能的具体能量转换原理，通过对纳流体发电装置内关键的 纳米沟道(尤其是纳米沟道的具体形貌等)以及与该纳米沟道配合作用的其他结构(如第一液体沟道与第二液体沟道)进行改进，可实现利用盐浓度梯度驱动发电，尤其可利用海水-淡水盐浓度实现发电；并且，本发明还通过对制备方法所对应的整体工艺流程设计进行改进，并对器件参数(如纳米沟道的深度、宽度、长度，尤其是纳米沟道的深度、长度)进行优选控制，可实现高精度控制的纳米沟道等结构以及发电的高性能，工艺手段对装置样本的损伤小、污染小、制备效率高。
为实现上述目的，按照本发明的一个方面，提供了一种纳流体发电装置，其特征在于，包括纳米沟道、以及分别位于该纳米沟道两端的第一液体沟道与第二液体沟道，所述纳米沟道、所述第一液体沟道与所述第二液体沟道均位于基底上，所述第一液体沟道与所述第二液体沟道两者通过该纳米沟道相连通；其中，
所述第一液体沟道用于容纳第一液体，并且与第一电极相连；
所述第二液体沟道用于容纳第二液体，并且与第二电极相连；
所述纳米沟道用于利用所述第一液体与所述第二液体两者之间的盐浓度差异将化学势能转化为电能，并通过所述第一电极与所述第二电极配合输出电能。
作为本发明的进一步优选，所述纳米沟道的深度为1-100nm，宽度为1-400nm，长度为400-1000nm；优选的，所述深度为1-40nm。
作为本发明的进一步优选，所述第一液体沟道具体包括第一微米沟道，以及通过该第一微米沟道相连的至少2个储液池；所述第一微米沟道的深度为1-100um，宽度为1-100um，长度为1-3mm；
所述第二液体沟道具体包括第二微米沟道，以及通过该第二微米沟道相连的至少2个储液池；所述第二微米沟道的深度为1-100um，宽度为1-100um，长度为1-3mm。
作为本发明的进一步优选，所述第一电极为1个，这个第一电极设置 在与所述第一微米沟道相连的一个储液池内；
所述第二电极为1个，这个第二电极设置在与所述第二微米沟道相连的一个储液池内。
作为本发明的进一步优选，所述储液池共计4个，分别位于所述基底上表面的四个角。
作为本发明的进一步优选，所述基底为SiO 2基底或者Al 2O 3基底。
按照本发明的另一方面，本发明提供了制备上述纳流体发电装置的制备方法，其特征在于，包括以下步骤：
(1)在SiO 2基底上利用微纳电子工艺加工得到纳米沟道，该微纳电子工艺具体包括电子束曝光、显影、等离子体刻蚀、以及后显影；并且，在加工得到的纳米沟道的两端还分别留有至少2毫米的待加工区域，用于制备第一液体沟道与第二液体沟道；
(2)利用紫外光刻机进行套刻制备分别位于纳米沟道两端的第一液体沟道与第二液体沟道，具体操作为：旋涂负性光刻胶，然后在紫外光刻机中对纳米沟道进行对准，套刻曝光，接着使用对应显影液进行显影，等离子体刻蚀，以及后显影，从而完成纳米沟道两端的第一液体沟道与第二液体沟道的制备以及配准；
(3)对加工好纳米沟道、第一液体沟道与第二液体沟道的SiO 2基底进行PDMS封装，PDMS通过氧等离子体处理与SiO 2基底键合。
作为本发明的进一步优选，所述步骤(3)中，具体是将在与储液池相对应的位置设置有小孔的PDMS板，通过氧等离子体处理激活，然后在显微镜下将该PDMS板对准密封在具有纳米通道、第一液体沟道与第二液体沟道的硅基底上，键合后完成纳流体芯片制备；键合后，PDMS板上的小孔与硅基底上的储液池在硅基底表面所在平面上的投影相重合；
优选的，所述PDMS板的厚度为500μm，小孔的直径为2mm。
作为本发明的进一步优选，所述制备方法还包括步骤：
(4)向纳流体芯片的第一液体沟道和第二液体沟道内分别注入第一液体和第二液体，所述第一液体与所述第二液体两者之间具有盐浓度差异，并将第一电极与第一液体沟道相连，第二电极与第二液体沟道相连；
优选的，所述第一液体为海水，所述第二液体为淡水。
按照本发明的又一方面，本发明提供了上述纳流体发电装置的应用方法，其特征在于，该方法具体是向纳流体发电装置的第一液体沟道和第二液体沟道内分别注入第一液体和第二液体，纳米沟道利用所述第一液体与所述第二液体两者之间具有的盐浓度差异，将化学势能转化为电能，该电能通过第一电极与第二电极配合输出。
作为本发明的进一步优选，所述第一液体为海水，所述第二液体为淡水。
通过本发明所构思的以上技术方案，与现有技术相比，本发明制备的纳流体发电装置，使用标准微电子以及电子束曝光等工艺制备得到纳米沟道，接着再套刻制备纳米沟道两端的第一液体沟道与第二液体沟道的制备以及配准腔室，制得装置的发电功率密度提高了两个量级。由于设计加工出宽度、深度和长度任意一项为纳米级的纳米沟道(尤其是深度为纳米级的纳米沟道；本发明中的纳米沟道其定义，与现有技术一致，只要有一个维度的尺寸在纳米级即可)，该纳米沟道优选与带有储液池、微米沟道的第一/第二液体沟道相连。通过在沟道入口和出口的储液池注入不同浓度的盐溶液，由于化学势能可驱动沟道内离子运动，而由于纳米沟道的表面电荷导致更多的异性离子沟道形成净电流以及沟道两端的电压，进而可以利用净电流以及电压对外输出电能。
本发明通过将纳米沟道的形状参数优选控制为深度1-100nm,宽度1-400nm，长度为400-1000nm(尤其是将深度控制为1-100nm，更优选的控制为1-40nm)，能够取得更佳发电效果。并且，这一特定优选形状参数的纳米沟道，尤其适用于浓度之比大于等于1000/1的第一/第二液体。利用 该沟道本发明尤其可以实现对海水-淡水进行能量转化及特性测试。
并且，本发明还通过优选设计深度不同于纳米沟道的微米沟道，利用微米沟道连通储液池，能够防止PDMS在纳米沟道的塌陷。为了构建稳定的、防塌陷的纳米沟道器件(PDMS软体材料，容易塌陷从而堵住纳米沟道)，本发明设计了第一微米沟道和第二微米沟道(第一微米沟道和第二微米沟道可以分别位于纳米沟道两侧)，并优选将第一微米沟道、第二微米沟道控制为深度为1-100um，宽度为1-100um，长度为1-3mm，微米沟道所占面积小，旁边的基底可以支撑整体PDMS不塌陷，且微米沟道对纳米沟道的离子输运性能影响很小，非常适用。
近年来基于扫描电子显微镜(Scanning Electron Microscope,SEM)的电子束曝光(Electron Beam Lithography,EBL)技术成为纳米加工的有力工具。根据德布罗意的物质波理论，电子是一种波长极短的波。这样，电子束曝光的精度可以达到纳米量级，从而为制作纳米结构提供了很有用的工具。利用EBL的高精密度可以在样本上加工出多种形式的纳米凹槽、沟道等纳米结构。本发明还通过对制备方法所对应的整体工艺流程设计进行改进，与器件参数的改进进一步综合作用，可实现高精度控制的纳米沟道等结构以及发电的高性能，工艺手段对装置样本的损伤小、污染小、制备效率高。
具体说来，本发明具有以下有益效果：
1)本发明中由盐浓度梯度驱动的纳流体发电装置，其能量尤其可以来源于海水-淡水的化学势能差，是清洁、可再生的能源。
2)通过在已优化长度的纳米沟道两端的储液池注入不同浓度的盐溶液，可以实现最高705W/m 2的输出功率密度(当两端为1M/1mM KCl溶液时)，这对微纳器件的供电来说意义重大。
3)本纳流体装置与CMOS工艺兼容，外接电路简单，便于大规模集成。
【附图说明】
图1是本发明的纳流体发电装置的结构图。
图2中，a是微纳工艺加工的微米沟道、纳米沟道的SEM扫描图，b是纳米沟道部分的SEM扫描图。
图3是使用半导体测试仪B1500A测试本发明的发电性能的电流-电压特性图。
图4针对所制备的器件的发电性能测试图，纳米沟道两边储液池的盐浓度比与(a)开路电压、(b)短路电流、(b)输出功率密度(输出功率/纳米沟道横截面)的关系图。该器件中纳米沟道长度为715nm,宽度为350nm,深度为40nm。高浓度端为1Mol/L的KCl溶液，低浓度端依次从10 -4Mol/L调整到1Mol/L的KCl溶液。
图中各附图标记的含义如下：0为硅片，1为纳米沟道，2为微米沟道，3为储液池，4为Ag/AgCl掺比电极，5为聚二甲基硅氧烷(PDMS)板。
【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，以下结合附图及实施例，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仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
实施例1
本发明中纳流体发电装置，左右两端设置储液池，左右两个储液池连有微米沟道连通，所述两个微米沟道之间设置纳米沟道，利用微纳电子工艺加工出连通微米沟道的纳米沟道。
该装置尤其是一种可利用海水-淡水盐浓度梯度驱动的纳流体发电装置。在装置的左边储液池施加海水，右边储液池施加淡水，由于纳米沟道的离子选择性，更多的阳离子通过沟道产生电流。通过储液池的电极可检测装置的发电电压、电流。该纳流体发电装置可广泛应用于各类微纳装置 的供电。
该纳流体发电装置可以采用包括以下步骤的加工方法：
1)纳米沟道的制备：如图1所示，设计加工出纳流体发电装置的纳米沟道1，纳米沟道是在硅片0上由微纳电子工艺(Micro-nano electronic technology)加工完成，包括电子束曝光、显影、ICP刻蚀，后显影，制备出深度为1-40nm,宽度为1-400nm，长度为400-1000nm的SiO 2沟道(市售商业硅片的上表面存在SiO 2层，当然也可以直接采用纯SiO 2基底替代硅片；以硅片为代表的SiO 2基底能够与CMOS工艺兼容，便于后续制备工艺处理)。所述纳米沟道两端留有2毫米待加工区域，用于制备微米沟道以及储液池；
单个储液池的形状参数可以采用如下设置：直径为2mm深度为1mm的圆柱；
2)微米沟道与储液池的制备：利用紫外光刻机(MJB4)进行套刻制备纳米沟道两端的微米沟道2以及储液池3加工，具体操作为：旋涂负性光刻胶，然后用MJB4紫外光刻机中对纳米沟道进行对准，套刻曝光，接着使用专用显影液进行显影，完成纳米沟道两端的微米沟道的制备以及配准；装置四角的储液池的制备；
3)装置的封装与注液：制备了一个带有4个直径为2mm孔的500μm厚的聚二甲基硅氧烷(PDMS)板5，然后在显微镜下将PDMS对准密封在纳米通道芯片上(孔与储液池对准连接)，完成纳流体芯片制备。然后向位于纳米沟道两端的两个孔分别注入海水与淡水，另外两个孔插入Ag/AgCl电极4向外输出电能(插入电极的两个孔中也可以分别对应注入有海水或淡水，便于测量、并减少噪声)。利用带有4个直径为2mm孔的500μm厚的聚二甲基硅氧烷(PDMS)板对SiO 2基底进行封装，可以降低电流测量过程中的噪声。
通过在装置的向位于纳米沟道两端的两个孔施加海水与淡水形成浓度差，更多的阳离子由于沟道的离子选择性通过纳米沟道时，产生净电流与 电压，向另外两个孔插入Ag/AgCl电极向外输出电能。
该纳流体发电装置的发电性能的测试方法：向位于纳米沟道两端的两个孔注入不同浓度的KCl溶液形成浓度差，同时在另外两个孔的电极上施加一个小电压并测量电流信号。当电流为零时，电极施加的电压为发电装置的发电电压，电极施加的电压为零时，测得的电流为发电装置的发电电流。电流-电压特性测试结果如图3所示。实际发电功率如图4所示，横坐标表示纳米沟道两边储液池的盐浓度比，纵坐标是输出功率密度(输出功率/纳米沟道横截面)。
除图1所示的储液池四角设置外(图1所示为在纳米沟道两侧采用微米沟道连通储液池)，储液池的设置位置也可以灵活调整，例如，一个角两个、另一个角两个。除上述实施例中所描述的具体设置外，电极的数量也可以增加，例如与同一微米沟道相连的电极可以是多个，储液池的数量也可以相应增加；储液池的数量也可以单独增加，例如在微米沟道中间再增设储液池等。另外，除了不同溶液的KCl溶液、海水-淡水外，本发明也适用于其他具有盐浓度差异的溶液，如其他具有浓度差异的强酸强碱盐溶液等。另外，除了上述实施例中所采用的硅衬底(对应SiO 2基底)外，本发明还可以采用氧化铝基底；本发明所采用的等离子体刻蚀，具体可以是感应耦合等离子体刻蚀(Inductively CoupledPlasma Etch，ICPE)。
本领域的技术人员容易理解，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、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种纳流体发电装置，其特征在于，包括纳米沟道、以及分别位于该纳米沟道两端的第一液体沟道与第二液体沟道，所述纳米沟道、所述第一液体沟道与所述第二液体沟道均位于基底上，所述第一液体沟道与所述第二液体沟道两者通过该纳米沟道相连通；其中，
    所述第一液体沟道用于容纳第一液体，并且与第一电极相连；
    所述第二液体沟道用于容纳第二液体，并且与第二电极相连；
    所述纳米沟道用于利用所述第一液体与所述第二液体两者之间的盐浓度差异将化学势能转化为电能，并通过所述第一电极与所述第二电极配合输出电能。
  2. 如权利要求1所述纳流体发电装置，其特征在于，所述纳米沟道的深度为1-100nm，宽度为1-400nm，长度为400-1000nm；优选的，所述深度为1-40nm。
  3. 如权利要求1所述纳流体发电装置，其特征在于，所述第一液体沟道具体包括第一微米沟道，以及通过该第一微米沟道相连的至少2个储液池；所述第一微米沟道的深度为1-100um，宽度为1-100um，长度为1-3mm；
    所述第二液体沟道具体包括第二微米沟道，以及通过该第二微米沟道相连的至少2个储液池；所述第二微米沟道深度为1-100um，宽度为1-100um，长度为1-3mm。
  4. 如权利要求3所述纳流体发电装置，其特征在于，所述第一电极为1个，这个第一电极设置在与所述第一微米沟道相连的一个储液池内；
    所述第二电极为1个，这个第二电极设置在与所述第二微米沟道相连的一个储液池内；
    优选的，所述储液池共计4个，分别位于所述基底上表面的四个角。
  5. 如权利要求1所述纳流体发电装置，其特征在于，所述基底为SiO 2 基底或氧化铝基底。
  6. 制备如权利要求1－5任意一项所述纳流体发电装置的制备方法，其特征在于，包括以下步骤：
    (1)在SiO 2基底上利用微纳电子工艺加工得到纳米沟道，该微纳电子工艺具体包括电子束曝光、显影、等离子体刻蚀、以及后显影；并且，在加工得到的纳米沟道的两端还分别留有至少2毫米的待加工区域，用于制备第一液体沟道与第二液体沟道；
    (2)利用紫外光刻机进行套刻制备分别位于纳米沟道两端的第一液体沟道与第二液体沟道，具体操作为：旋涂负性光刻胶，然后在紫外光刻机中对纳米沟道进行对准，套刻曝光，接着使用对应显影液进行显影，等离子体刻蚀，以及后显影，从而完成纳米沟道两端的第一液体沟道与第二液体沟道的制备以及配准；
    (3)对加工好纳米沟道、第一液体沟道与第二液体沟道的SiO 2基底进行PDMS封装，PDMS通过氧等离子体处理与SiO 2基底键合。
  7. 如权利要求6所述制备方法，其特征在于，所述步骤(3)中，具体是将在与储液池相对应的位置设置有小孔的PDMS板，通过氧等离子体处理激活，然后在显微镜下将该PDMS板对准密封在具有纳米通道、第一液体沟道与第二液体沟道的硅基底上，键合后完成纳流体芯片制备；键合后，PDMS板上的小孔与硅基底上的储液池在硅基底表面所在平面上的投影相重合；更优选的，所述PDMS板的厚度为500μm，小孔的直径为2mm。
  8. 如权利要求6所述制备方法，其特征在于，所述制备方法还包括步骤：
    (4)向纳流体芯片的第一液体沟道和第二液体沟道内分别注入第一液体和第二液体，所述第一液体与所述第二液体两者之间具有盐浓度差异，并将第一电极与第一液体沟道相连，第二电极与第二液体沟道相连；
    优选的，所述第一液体为海水，所述第二液体为淡水。
  9. 如权利要求1－5任意一项所述纳流体发电装置的应用方法，其特征在于，该方法具体是向纳流体发电装置的第一液体沟道和第二液体沟道内分别注入第一液体和第二液体，纳米沟道利用所述第一液体与所述第二液体两者之间具有的盐浓度差异，将化学势能转化为电能，该电能通过第一电极与第二电极配合输出。
  10. 如权利要求9所述应用方法，其特征在于，所述第一液体为海水，所述第二液体为淡水。
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