WO2021142579A1 - 基于石墨烯气凝胶的能量收集与自清洁系统及其制备方法 - Google Patents

基于石墨烯气凝胶的能量收集与自清洁系统及其制备方法 Download PDF

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WO2021142579A1
WO2021142579A1 PCT/CN2020/071793 CN2020071793W WO2021142579A1 WO 2021142579 A1 WO2021142579 A1 WO 2021142579A1 CN 2020071793 W CN2020071793 W CN 2020071793W WO 2021142579 A1 WO2021142579 A1 WO 2021142579A1
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graphene aerogel
energy harvesting
self
graphene
cleaning system
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PCT/CN2020/071793
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French (fr)
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丁建宁
周小双
李绿洲
程广贵
袁宁一
胡兴好
董旭
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江苏大学
常州大学
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Priority to PCT/CN2020/071793 priority Critical patent/WO2021142579A1/zh
Publication of WO2021142579A1 publication Critical patent/WO2021142579A1/zh
Priority to US17/558,729 priority patent/US20220115963A1/en

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    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N1/00—Electrostatic generators or motors using a solid moving electrostatic charge carrier
    • H02N1/06—Influence generators
    • H02N1/08—Influence generators with conductive charge carrier, i.e. capacitor machines
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/04—Coating on selected surface areas, e.g. using masks
    • C23C14/046—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N11/00—Generators or motors not provided for elsewhere; Alleged perpetua mobilia obtained by electric or magnetic means
    • H02N11/002—Generators
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

Definitions

  • the invention relates to an energy collection and cleaning system, in particular to a graphene aerogel-based ocean energy collection and self-cleaning system and a preparation method thereof.
  • Graphene aerogel is a light, highly elastic, and highly absorbent material. It has ultra-fast and ultra-high adsorption capacity for organic solvents, and is the material with the strongest oil absorption capacity that has been reported. At the same time, it may become an ideal energy storage and thermal insulation material, catalyst carrier and high-efficiency composite material, which has broad prospects.
  • the first main purpose of the present invention is to propose an energy harvesting and self-cleaning system based on graphene aerogel to realize energy collection and cleaning of the system, and to apply the prepared graphene aerogel to energy harvesting and cleaning System; and then proposed a new energy harvesting mechanism: when applied to the ocean and forming a system, the graphene aerogel in the electrolyte is mechanically compressed due to the adsorption of positive and negative ions in the material of the graphene aerogel. The difference in the layers causes the asynchronous migration of positive and negative ions in this process, so that a voltage difference and current will be generated with the counter electrode during the compression recovery process, thereby achieving the purpose of energy harvesting.
  • a layer of metal collector is sputtered on both sides of the freeze-dried graphene aerogel by magnetron sputtering; the graphene with collector is prepared
  • the aerogel is fixed on the side and bottom surface of the substrate in series and/or parallel, and then put into the electrolyte to obtain the target system.
  • the precious metal used for the sputtered metal collector is silver or platinum, and the common metal is aluminum or copper; the thickness of the sputtering is 500nm-50um; furthermore The sputtering thickness is preferably 500nm-5um; the more preferred sputtering thickness is 1um.
  • the electrolyte used is organic or inorganic electrolyte, and the preferred electrolyte is sodium chloride solution with a concentration of 0.1mol/L-5mol/L .
  • the graphene aerogel-based energy harvesting and self-cleaning system proposed in the present invention can also be applied to systems other than the ocean.
  • the characteristics of graphene aerogel can be used to perform mechanical energy. Collect, at the same time, it can also absorb impurities such as oil stains in the electrolyte, and play a cleaning role.
  • the second main purpose of the present invention is to propose a method for preparing a graphene aerogel-based energy harvesting and self-cleaning system, mainly the preparation of the graphene aerogel used therein, by controlling the properties of the materials used, Ensure that the system collects energy and cleans effectively.
  • the preparation method of the graphene aerogel-based energy harvesting and self-cleaning system wherein the preparation of the graphene aerogel is carried out through the following steps:
  • Graphene oxide can be prepared by Hummer's.
  • the size of the flake graphite used in the preparation of graphene oxide is 30 to 50 mesh. It is dispersed in self-made ultrapure water using ultrasonic technology to form an aqueous solution.
  • the ultrasonic power is 800W, and the ultrasonic time is 5min; the self-made ultrapure water is prepared by the MilliQ ultrapure water system.
  • the concentration of the graphene oxide aqueous solution in step (1) is 5mg/ml-15mg/ml; further preferred the concentration of the graphene oxide aqueous solution 5mg/ml-10mg/ml; more preferably, the concentration of the graphene oxide aqueous solution is 5mg/ml; if the concentration of the prepared graphene oxide aqueous solution is too high to exceed 15mg/ml, or the concentration is too low to be less than 5mg/ml , Then the prepared aerogels are easier to collapse, and the elasticity is not as good as 5mg/ml.
  • the nanocomposite material in step (2) is carbon nanotube, MXene or one of conductive polymer PEDOT:PSS, PPy or PAN kind or more.
  • the volume mixing ratio of the graphene oxide and the nanocomposite material is 1:1-1:30; a further preferred volume mixing ratio of the graphene oxide and the nanocomposite material is 1:1-1:20; more preferably, The volume mixing ratio of graphene oxide and nanocomposite is 1:1-1:10; most preferably, the volume mixing ratio of graphene oxide and nanocomposite is 1:5; when the volume of graphene oxide and nanocomposite When the mixing ratio is high, the elasticity of the final aerogel will be relatively good; when the volume mixing of graphene oxide and nanocomposites is relatively low, the conductivity of the final aerogel will be relatively high; it can be based on the actual use scenario Make the corresponding selection within the set ratio of 1:30.
  • the reducing agent in step (2) is one or any two of ethylenediamine, hydroiodic acid, ammonia, or hydrazine hydrate And the above mixed solution; the further preferred reducing agent is ethylenediamine; since the final performance of aerogels prepared by different reducing agents will be different, the affinity of the prepared aerogels will have a certain influence, therefore, there is a selective choice Among the above reducing agents, the aerogel prepared by using ethylenediamine as the reducing agent has better hydrophilicity. Therefore, when used in water systems, ethylenediamine is selected as the reducing agent.
  • the heat preservation temperature in the high-pressure reactor in step (2) is 90-180 degrees, and the heat preservation time is 60 minutes-120 minutes; further preferred The heat preservation temperature in the high-pressure reactor is 90 degrees, and the heat preservation time is 60 minutes;
  • the low-temperature freezing temperature is -20-100°C, and the holding time is 1min-300min; further preferred low temperature
  • the freezing temperature is -20°C, and the holding time is 120min.
  • the freeze-drying temperature in the step (4) is -70°C, and the freeze-drying time is 24-72h; further preferred The freeze-drying time is 48h.
  • the control of heating temperature, holding temperature and holding time in the above operation is mainly to control the progress of reflection, and then to obtain the final optimized stable structure;
  • the control of low temperature freezing temperature and freezing time is mainly to control the speed of ice crystal growth to control the lamella
  • the size of the voids during the stacking process is optimized to obtain the most stable aerogel structure; the joint control of temperature and time is required to achieve the above-mentioned purpose.
  • the third main purpose of the present invention is to propose a graphene aerogel prepared according to the above-mentioned graphene aerogel preparation method.
  • the fourth main purpose of the present invention is to provide a preparation method for preparing graphene aerogel, in which the stacking morphology of the pores can be adjusted by controlling the process parameters.
  • the present invention has the following beneficial effects:
  • the present invention controls the growth of ice crystals by controlling the doped materials and the freezing speed and freezing time in the freezing process to adjust the size of the graphene aerogel pores.
  • the adjusted size can effectively control the energy harvesting of the graphene aerogel The characteristic of ion transmission, so as to realize the regulation and control of the performance for different application scenarios.
  • the present invention pioneered the introduction of a new energy harvesting mechanism: during the mechanical compression of the graphene aerogel in the electrolyte, due to the difference between the positive and negative ion adsorption layers of the graphene aerogel itself, The positive and negative ions produce asynchrony of migration during this process, so in the process of compression and recovery, a voltage difference and current will be generated with the counter electrode to realize energy collection.
  • the present invention provides a new idea of mechanical energy harvesting.
  • graphene aerogel is introduced into the field of mechanical energy harvesting.
  • the proposed system can not only collect mechanical energy but also absorb impurities such as oil in the ocean. , Play a role in cleaning the ocean.
  • the energy harvesting system formed by a single aerogel can generate an open circuit voltage of ⁇ 220mV in a sodium chloride solution or an organic electrolyte, and generate a power density of 2W/kg.
  • Figure 1 is a schematic diagram of the working principle of a graphene aerogel-based energy harvesting and self-cleaning system
  • Figure 2 is an enlarged schematic diagram of simulated graphene aerogel pores
  • Figure 3 is a schematic diagram of a parallel connection mode of graphene aerogel-based energy harvesting and self-cleaning systems
  • Figure 4 is a scanning electron microscope cross-sectional view of the graphene aerogel used in the system
  • Figure 5 is a performance diagram of a single graphene aerogel used in the system in sodium chloride electrolyte
  • Figure 6 shows the electricity generation performance of a single graphene aerogel used in the system in organic TEABF4/PC electrolyte
  • Ultrapure water Milli Q ultrapure water system preparation
  • Foam board Kunshan Guangjia New Material Co., Ltd.
  • FIG 1 and Figure 2 are schematic diagrams of the working principle of the graphene aerogel-based energy harvesting and self-cleaning system proposed by the present invention. Specifically, due to the difference in the adsorption layer of positive and negative ions in the graphene aerogel itself, The positive and negative ions are not synchronized in the process of migration, so in the process of compression and recovery, a voltage difference and current will be generated with the counter electrode to achieve the purpose of energy harvesting.
  • the preparation method of graphene aerogel provided by the present invention includes the following operation steps:
  • the taken-out sample was frozen at -20°C and freeze-dried after 120 minutes.
  • the temperature of the freeze-drying was -70°C and the freeze-drying time was 48 hours to obtain the target product.
  • Using the prepared graphene aerogel to prepare a marine energy harvesting and self-cleaning system includes the following steps:
  • FIG. 5 and Figure 6 it is a graph of the energy harvesting performance of a single graphene aerogel applied to the energy harvesting and self-cleaning system.
  • the aerogel can reach an open pressure of 220mV and load power in water and organic systems. Up to 2W/Kg.
  • the preparation method of graphene aerogel provided by the present invention includes the following operation steps:
  • the taken-out sample was frozen at -20°C and freeze-dried after 120 minutes.
  • the temperature of the freeze-drying was -70°C and the freeze-drying time was 48 hours to obtain the target product.
  • Using the prepared graphene aerogel to prepare a marine energy harvesting and self-cleaning system includes the following steps:
  • the preparation method of graphene aerogel provided by the present invention includes the following operation steps:
  • the taken-out sample was frozen at -20°C and freeze-dried after 120 minutes.
  • the temperature of the freeze-drying was -70°C and the freeze-drying time was 48 hours to obtain the target product.
  • Using the prepared graphene aerogel to prepare a marine energy harvesting and self-cleaning system includes the following steps:
  • the preparation method of graphene aerogel provided by the present invention includes the following operation steps:
  • the taken-out sample was frozen at -20°C and freeze-dried after 120 minutes.
  • the temperature of the freeze-drying was -70°C and the freeze-drying time was 48 hours to obtain the target product.
  • Using the prepared graphene aerogel to prepare a marine energy harvesting and self-cleaning system includes the following steps:
  • the preparation method of graphene aerogel provided by the present invention includes the following operation steps:
  • the taken-out sample is frozen at -40°C and freeze-dried after 120 minutes of freezing.
  • the freeze-drying temperature is -70°C and the freeze-drying time is 72 hours to obtain the target product.
  • Using the prepared graphene aerogel to prepare a marine energy harvesting and self-cleaning system includes the following steps:
  • the preparation method of graphene aerogel provided by the present invention includes the following operation steps:
  • the taken-out sample is frozen at -40°C and freeze-dried after 120 minutes of freezing.
  • the freeze-drying temperature is -70°C and the freeze-drying time is 72 hours to obtain the target product.
  • Using the prepared graphene aerogel to prepare a marine energy harvesting and self-cleaning system includes the following steps:
  • the graphene aerogel-based energy collection and self-cleaning system proposed by the present invention is not limited to the collection and cleaning of ocean energy, but also on the basis of mechanical motion, including lake waves, rivers, hydropower stations, or moving electrolytes. Existing scenes can be formed and applied to the system to achieve energy collection and cleaning.

Abstract

提供一种基于石墨烯气凝胶的能量收集与自清洁系统及其制备方法。该系统是将冷冻干燥的石墨烯气凝胶（3）两侧通过磁控溅射的方法溅射一层金属集电极（2）；将带有集电极的石墨烯气凝胶，按照串联和/或并联的方式固定在基板的侧面和底面，然后放入电解液（4）中得到的。其中氧化石墨烯气凝胶的制备方法包括：制备氧化石墨烯水溶液；将氧化石墨烯水溶液与纳米复合材料的溶液混匀，加入还原剂，得到混合液；将混合液在高压反应釜中加热保温；取出进行低温冷冻和冷冻干燥，得到石墨烯气凝胶。将气凝胶引入到机械能量收集领域，同时还能够吸附海洋中的油污等杂质，起到海洋清洁的作用。单个气凝胶形成的能量收集系统在氯化钠溶液中或者有机电解液中可以产生～220mV的开路电压，产生2W/kg的功率密度。

Description

基于石墨烯气凝胶的能量收集与自清洁系统及其制备方法 技术领域
本发明涉及一种能量收集和清洁系统，尤其涉及基于石墨烯气凝胶的海洋能量收集与自清洁系统及其制备方法。
背景技术
石墨烯气凝胶作为一种轻柔、高弹性、高吸附性的材料，它对有机溶剂有超快、超高的吸附力，是已被报道的吸油力最强的材料。同时还可能成为理想的储能保温材料、催化剂载体及高效复合材料，有广阔前景。
同时机械能作为大自然界中丰富存在的一种能量，一直广受关注，对于发展环境友好和可持续的机械能收集技术也越来越迫切。同时海洋机械能作为一种有效的机械能量也越来越成为研究的焦点。随着压电材料，摩擦起电技术的发展，越来越多的器件利用压电或摩擦起电来收集环境中存在的机械能。但是对于石墨烯气凝胶的应用还未涉及到能量收集领域。
有鉴于上述现有的环境能量收集存在的技术缺陷，本发明人基于从事此类产品设计制造多年丰富的实务经验及专业知识，并配合学理的运用，积极加以研究创新，以期创设一种基于石墨烯气凝胶的海洋能量收集与自清洁系统及其制备方法，使其更具有实用性。经过不断的研究、设计，并经反复试作样品及改进后，终于创设出确具实用价值的本发明。
发明内容
本发明的第一个主要目的在于，提出一种基于石墨烯气凝胶的能量收集与自清洁系统，实现能量的收集以及系统的清洁作用，将制备的石墨烯气凝胶应用于能量收集清洁系统；进而提出一种新的能量收集机理：应用到海洋中、形成系统时，电解液中的石墨烯气凝胶在机械压缩过程中，由于石墨烯气凝胶本身材料中对正负离子的吸附层的差异，造成正负离子在这个过程中产生迁移的不同步，因而在压缩恢复的过程中会与对电极产生电压差和电流，进而达到能量收集的目的。
本发明的上述技术目的是通过以下技术方案得以实现的：
基于石墨烯气凝胶的能量收集与自清洁系统，将冷冻干燥的石墨烯气凝胶两侧通过磁控溅射的方法溅射一层金属集电极；将制备的带有集电极的石墨烯气凝胶，按照串联和/并联的方式固定在基板的侧面和底面，然后放入电解液中得到目标系统。
作为优选的基于石墨烯气凝胶的能量收集与自清洁系统，溅射的金属集电极使用的贵金属为银或铂，普通金属为铝或铜；溅射的厚度为500nm-50um；更进一步的溅射厚度优选为500nm-5um；更优选的溅射厚度为1um。
作为优选的基于石墨烯气凝胶的能量收集与自清洁系统，其中所使用的电解液为有机或者无机电解液，优选的电解液是氯化钠溶液，浓度为0.1mol/L-5mol/L。
本发明提出的基于石墨烯气凝胶的能量收集与自清洁系统，还可以应用于除海洋之外的系统中，在存在机械运动的基础上，就可以利用石墨烯气凝胶的特性进行机械能收集，同时还能够吸附电解液中的油污等杂质，起到清洁的作用。
本发明的第二个主要目的在于，提出一种基于石墨烯气凝胶的能量收集与自清洁系统的制备方法，主要是其中使用的石墨烯气凝胶的制备，通过控制使用材料的性能，保证系统收集能量和清洁作用的有效发挥。
本发明的上述技术目的是通过以下技术方案得以实现的：
基于石墨烯气凝胶的能量收集与自清洁系统的制备方法，其中制备石墨烯气凝胶通过如下操作步骤：
(1)称取氧化石墨烯，其中氧化石墨烯可以采用Hummer’s制备，制备氧化石墨烯使用的鳞片石墨的大小为30目-50目，利用超声技术分散在自制超纯水中配置成水溶液，采用的超声功率为800W，超声时间为5min；自制超纯水为采用Milli Q超纯水系统制备获得。
(2)称取氧化石墨烯水溶液与纳米复合材料的溶液超声混合均匀后，加入还原剂，得到混合液；
(3)将(2)中的混合液在高压反应釜中加热并保温，得到混合液；
(4)取出(3)制备的混合液进行低温冷冻并进行冷冻干燥，得到石墨烯气凝胶；
作为优选的基于石墨烯气凝胶的能量收集与自清洁系统的制备方法，步骤(1)中的氧化石墨烯的水溶液浓度为5mg/ml-15mg/ml；进一步优选的氧化石墨烯的水溶液浓度为5mg/ml-10mg/ml；更优选的，氧化石墨烯的水溶液浓度为5mg/ml；若制备的氧化石 墨烯的水溶液浓度过高超过15mg/ml，或者浓度过低而低于5mg/ml，那么制备的气凝胶均较容易坍塌，并且弹性不如5mg/ml的好。
作为优选的基于石墨烯气凝胶的能量收集与自清洁系统的制备方法，步骤(2)中的纳米复合材料为碳纳米管，MXene或导电性聚合物PEDOT:PSS、PPy或PAN中的一种或多种。
所述氧化石墨烯和纳米复合材料的体积混合比为1：1-1：30；更进一步优选的氧化石墨烯和纳米复合材料的体积混合比为1：1-1：20；更优选的，氧化石墨烯和纳米复合材料的体积混合比为1：1-1：10；最优选的，氧化石墨烯和纳米复合材料的体积混合比为1：5；当氧化石墨烯和纳米复合材料的体积混合比较高时，最终制备的气凝胶弹性相对会好；当氧化石墨烯和纳米复合材料的体积混合比较低时，最终制备的气凝胶导电性会相对较高；可以根据实际的使用场景在设定的1：30比例范围内做相应的选择。
作为优选的基于石墨烯气凝胶的能量收集与自清洁系统的制备方法，步骤(2)中的还原剂为乙二胺、氢碘酸、氨水或水合肼其中的一种或者其中任意两种及以上的混合溶液；进一步优选的还原剂为乙二胺；由于不同还原剂制备的气凝胶最终性能会有差异，制备的气凝胶的亲疏性有一定的影响，因此，有选择的选用上述的还原剂，其中采用乙二胺作为还原剂制备的气凝胶亲水性较好，因此应用在水系中时，选用乙二胺作为还原剂。
作为优选的基于石墨烯气凝胶的能量收集与自清洁系统的制备方法，在步骤(2)中的高压反应釜中保温温度为90-180度，保温时间为60分钟-120分钟；进一步优选的高压反应釜中保温温度为90度，保温时间为60分钟；
作为优选的基于石墨烯气凝胶的能量收集与自清洁系统的制备方法，在所述步骤(4)中低温冷冻温度为-20--100℃，保温时间为1min-300min；进一步优选的低温冷冻温度为-20℃，保温时间为120min。
作为优选的基于石墨烯气凝胶的能量收集与自清洁系统的制备方法，在所述步骤(4)中冷冻干燥的温度为-70℃，所述冷冻干燥的时间为24-72h；进一步优选的冷冻干燥时间为48h。
上述操作中加热温度、保温温度和保温时间的控制，主要是控制反映的进度，进而得到最终优化的稳定结构；低温冷冻温度和冷冻时间的控制，主要是通过控制冰晶生长的速度来调控片层堆叠过程中空隙的大小，而优化得到最稳定的气凝胶结构；需要温度 和时间的共同控制才能够实现上述的目的。
本发明的第三个主要目的在于，提出了根据上述石墨烯气凝胶制备方法制备的石墨烯气凝胶。
本发明的第四个主要目的在于，提出了制备石墨烯气凝胶的制备方法，通过控制工艺参数可以调整其中孔道的堆叠形态。
综上所述，本发明具有以下有益效果：
1.本发明通过控制掺杂的材料以及控制冷冻过程中的冷冻速度和冷冻时间，来控制冰晶生长从而调节石墨烯气凝胶孔道尺寸，调控的尺寸可以有效的控制石墨烯气凝胶能量收割的离子传输特性，从而实现针对不同应用场景性能的调控。
2.本发明开创性的引入了一种新的能量收集机理：处于电解液中的石墨烯气凝胶在机械压缩过程中，由于石墨烯气凝胶本身材料对正负离子吸附层的差异，造成正负离子在这个过程中产生迁移的不同步性，因而在压缩恢复的过程中会与对电极产生电压差和电流，进而实现能量的收集。
3.本发明提供了一种机械能量收集的新思路，第一次将石墨烯气凝胶引入到机械能量收集领域，同时提出的系统，不仅可以收集机械能同时还能够吸附海洋中的油污等杂质，起到海洋清洁的作用。单个气凝胶形成的能量收集系统在氯化钠溶液中或者有机电解液中可以产生～220mV的开路电压，产生2W/kg的功率密度。
附图说明
图1为基于石墨烯气凝胶的能量收集与自清洁系统工作原理示意图；
图2为模拟的石墨烯气凝胶孔道放大示意图；
图3为基于石墨烯气凝胶的能量收集与自清洁系统并联方式示意图；
图4为系统用的石墨烯气凝胶的扫描电镜截面图；
图5为系统用的单个石墨烯气凝胶在氯化钠电解液中的性能图；
图6为系统用的单个石墨烯气凝胶在有机TEABF4/PC电解液中的产电性能；
图中标记含义：1.泡沫板，2.金属集电极，3.石墨烯气凝胶，4.电解质溶液，5.金属对电极。
具体实施方式
为更进一步阐述本发明为达成预定发明目的所采取的技术手段及功效，对依据本发 明提出的基于石墨烯气凝胶的能量收集与自清洁系统及其制备方法、特征及其功效，详细说明如后。
以下实施例所用原料来源如下：
石墨：麦克林试剂有限公司
超纯水：Milli Q超纯水系统制备
MXene：11科技有限公司
乙二胺：国药试剂有限公司
碳纳米管：深圳纳米港公司
泡沫板：昆山广嘉新材料有限公司
实施例1
如图1和图2是本发明提出的基于石墨烯气凝胶的能量收集与自清洁系统工作原理示意图，具体的，由于石墨烯气凝胶本身材料中对正负离子的吸附层的差异，造成正负离子在这个过程中产生迁移的不同步，因而在压缩恢复的过程中会与对电极产生电压差和电流，进而达到能量收集的目的。
本发明提出的石墨烯气凝胶的制备方法包括如下操作步骤：
(1)称取用Hummer’s制备的氧化石墨烯，制备氧化石墨烯所用的天然石墨的尺寸为30目，然后利用功率为800W超声分散机，将氧化石墨烯片分散在超纯水中配置成5mg/mL的水溶液。
(2)称取氧化石墨烯水溶液与浓度为1mg/ml的MXene水溶液以1：1的体积比超声混合均匀后，加入20ul的乙二胺还原剂后，
(3)放入20mL的高压反应釜中，在90℃的温度下保温120min后，
(4)取出来的样品在-20℃下进行低温冷冻，冷冻120min后进行冷冻干燥,冷冻干燥的温度为-70℃，冷冻干燥的时间为48小时，得到目标产物。
利用制备的石墨烯气凝胶制备海洋能量收集与自清洁系统，包括如下操作步骤：
(1)将冷冻干燥的气凝胶两侧通过磁控溅射的方法溅射一层金属银集电极2，厚度为1um。
(2)将带有集电极的石墨烯气凝胶3，按照并联的方式固定在商业泡沫板1的侧面和底面，然后放入不同浓度的氯化钠电解液中来获得一个能量收集和环境清理系统如图 3所示。
对于系统中使用的石墨烯气凝胶3，通过扫描电镜来观察微观结构，如图4所示，可以清晰看到由石墨烯片层堆砌而成的孔道，孔道大小为100-200微米，保证了微流体的传输通道。
如图5和图6所示，是应用于能量收集与自清洁系统内单个石墨烯气凝胶的能量收集性能图，该气凝胶在水系和有机体系内可以达到220mV的开压，负载功率可达2W/Kg。
实施例2
本发明提出的石墨烯气凝胶的制备方法包括如下操作步骤：
(1)称取用Hummer’s制备的氧化石墨烯，制备氧化石墨烯所用的天然石墨的尺寸为50目，然后利用功率为800W超声分散机，将氧化石墨烯片分散在超纯水中配置成15mg/mL的水溶液。
(2)称取氧化石墨烯水溶液与浓度为1mg/ml的MXene水溶液以1：5的比例超声混合均匀后，加入20ul的乙二胺还原剂后，
(3)放入20mL的高压反应釜中，在90℃的温度下保温120min后，
(4)取出来的样品在-20℃下进行低温冷冻，冷冻120min后进行冷冻干燥,冷冻干燥的温度为-70℃，冷冻干燥的时间为48小时，得到目标产物。
利用制备的石墨烯气凝胶制备海洋能量收集与自清洁系统，包括如下操作步骤：
(1)将冷冻干燥的石墨烯气凝胶3两侧通过磁控溅射的方法溅射一层金属铂集电极2，厚度为1um。
(2)将带有集电极的石墨烯气凝胶，如图1所示按照并联的方式固定在商业泡沫板1的侧面和底面，然后放入不同浓度的氯化钠电解液中来获得一个能量收集和环境清理系统。
实施例3
本发明提出的石墨烯气凝胶的制备方法包括如下操作步骤：
(1)称取用Hummer’s制备的氧化石墨烯，制备氧化石墨烯所用的天然石墨的尺寸为50目，然后利用功率为800W超声分散机，将氧化石墨烯片分散在超纯水中配置成15mg/mL的水溶液。
(2)称取氧化石墨烯水溶液与浓度为1mg/ml的PEDOT-PSS聚合物水溶液以1：5的比例超声混合均匀后，加入20ul的乙二胺还原剂后，
(3)放入20mL的高压反应釜中，在90℃的温度下保温120min后，
(4)取出来的样品在-20℃下进行低温冷冻，冷冻120min后进行冷冻干燥,冷冻干燥的温度为-70℃，冷冻干燥的时间为48小时，得到目标产物。
利用制备的石墨烯气凝胶制备海洋能量收集与自清洁系统，包括如下操作步骤：
(1)将冷冻干燥的石墨烯气凝胶两侧通过磁控溅射的方法溅射一层金属银集电极，厚度为1um。
(2)将带有集电极的石墨烯气凝胶，按照串联的方式固定在商业泡沫板的侧面和底面(未在图中示出)，然后放入不同浓度的海水电解液中来获得一个能量收集和环境清理系统。
实施例4
本发明提出的石墨烯气凝胶的制备方法包括如下操作步骤：
(1)称取用Hummer’s制备的氧化石墨烯，制备氧化石墨烯所用的天然石墨的尺寸为30目，然后利用功率为800W超声分散机，将氧化石墨烯片分散在超纯水中配置成5mg/mL的水溶液。
(2)称取氧化石墨烯水溶液与浓度为1mg/ml的碳纳米管水溶液以1：1，1:2,1:5，1:10等的比例超声混合均匀后，加入20ul-80ul的乙二胺还原剂后，
(3)放入20mL的高压反应釜中，在90℃的温度下保温120min后，
(4)取出来的样品在-20℃下进行低温冷冻，冷冻120min后进行冷冻干燥,冷冻干燥的温度为-70℃，冷冻干燥的时间为48小时，得到目标产物。
利用制备的石墨烯气凝胶制备海洋能量收集与自清洁系统，包括如下操作步骤：
(1)将冷冻干燥的石墨烯气凝胶两侧通过磁控溅射的方法溅射一层金属银集电极，厚度为1um。
(2)将带有集电极的石墨烯气凝胶，按照串联方式固定在商业泡沫板的侧面和底面，然后放入不同浓度的氯化钠电解液中来获得一个能量收集和环境清理系统。
实施例5
本发明提出的石墨烯气凝胶的制备方法包括如下操作步骤：
(1)称取用Hummer’s制备的氧化石墨烯，制备氧化石墨烯所用的天然石墨的尺寸为30目，然后利用功率为800W超声分散机，将氧化石墨烯片分散在超纯水中配置成5mg/mL的水溶液。
(2)称取氧化石墨烯水溶液与浓度为1mg/ml的碳纳米管水溶液以1：1，1:2,1:5，1:10等的比例超声混合均匀后，加入20ul-80ul的乙二胺还原剂后，
(3)放入20mL的高压反应釜中，在120℃的温度下保温120min后，
(4)取出来的样品在-40℃下进行低温冷冻，冷冻120min后进行冷冻干燥,冷冻干燥的温度为-70℃，冷冻干燥的时间为72小时，得到目标产物。
利用制备的石墨烯气凝胶制备海洋能量收集与自清洁系统，包括如下操作步骤：
(1)将冷冻干燥的气凝胶两侧通过磁控溅射的方法溅射一层金属铜集电极2，厚度为1um。
(2)将带有集电极的石墨烯气凝胶3，如图1所示按照并联的方式固定在商业泡沫板1的侧面和底面，然后放入不同浓度的氯化钠电解液中来获得一个能量收集和环境清理系统。
实施例6
本发明提出的石墨烯气凝胶的制备方法包括如下操作步骤：
(1)称取用Hummer’s制备的氧化石墨烯，制备氧化石墨烯所用的天然石墨的尺寸为30目，然后利用功率为800W超声分散机，将氧化石墨烯片分散在超纯水中配置成5mg/mL的水溶液。
(2)称取氧化石墨烯水溶液与浓度为1mg/ml的碳纳米管水溶液以1：1，1:2,1:5，1:10等的比例超声混合均匀后，加入20ul-80ul的乙二胺还原剂后，
(3)放入20mL的高压反应釜中，在120℃的温度下保温120min后，
(4)取出来的样品在-40℃下进行低温冷冻，冷冻120min后进行冷冻干燥,冷冻干燥的温度为-70℃，冷冻干燥的时间为72小时，得到目标产物。
利用制备的石墨烯气凝胶制备海洋能量收集与自清洁系统，包括如下操作步骤：
(1)将冷冻干燥的石墨烯气凝胶两侧通过磁控溅射的方法溅射一层金属银集电极，厚度为1um。
(2)将带有集电极的石墨烯气凝胶，按照串联方式固定在商业泡沫板的侧面和底 面，然后放入TEABF4/PC有机电解液中来获得一个能量收集和环境清理系统。
本发明提出的基于石墨烯气凝胶的能量收集与自清洁系统不仅仅局限于对海洋能量的收集和清洁，存在机械运动的基础上，包括湖波、河流、水电站或者是有运动的电解液存在的场景均可以形成并应用该系统，实现能量的收集与清洁。
本具体实施例仅仅是对本发明的解释，其并不是对本发明的限制，本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改，但只要在本发明的权利要求范围内都受到专利法的保护。

Claims (10)

  1. 一种基于石墨烯气凝胶的能量收集与自清洁系统，其特征在于：将冷冻干燥的石墨烯气凝胶两侧通过磁控溅射的方法溅射一层金属集电极；将制备的带有集电极的石墨烯气凝胶，按照串联和/并联的方式固定在基板的侧面和底面，然后放入电解液中得到目标系统。
  2. 根据权利要求1所述基于石墨烯气凝胶的能量收集与自清洁系统，其特征在于：所述的金属集电极使用的金属为银、铂、铝或铜。
  3. 根据权利要求1或2所述基于石墨烯气凝胶的能量收集与自清洁系统，其特征在于：所述金属集电极溅射的厚度为500nm-50um。
  4. 根据权利要求1-3任一项所述的基于石墨烯气凝胶的能量收集与自清洁系统的制备方法，其特征在于：制备所述石墨烯气凝胶通过如下操作步骤：
    (1)称取氧化石墨烯，利用超声技术分散在自制超纯水中配置成氧化石墨烯水溶液；
    (2)称取氧化石墨烯水溶液与纳米复合材料的溶液超声混合均匀后，加入还原剂，得到混合液；
    (3)将(2)制备的混合液在高压反应釜中加热并保温；
    (4)将(3)加热保温的混合液取出进行低温冷冻并进行冷冻干燥，得到石墨烯气凝胶。
  5. 根据权利要求4所述的基于石墨烯气凝胶的能量收集与自清洁系统的制备方法，其特征在于：所述步骤(1)中的所述的氧化石墨烯的水溶液浓度为5mg/ml-15mg/ml。
  6. 根据权利要求5所述的基于石墨烯气凝胶的能量收集与自清洁系统的制备方法，其特征在于：所述步骤(2)中的纳米复合材料为碳纳米管、MXene或导电性聚合物PEDOT中的一种或多种；所述氧化石墨烯和纳米复合材料的体积混合比为1：1-1：30。
  7. 根据权利要求4或5所述的基于石墨烯气凝胶的能量收集与自清洁系统的制备方法，其特征在于：所述步骤(2)中的还原剂为乙二胺、氢碘酸、氨水或水合肼其中的一种或者其中任意两种及以上的混合溶液。
  8. 根据权利要求7所述的基于石墨烯气凝胶的能量收集与自清洁系统的制备方法，其特征在于：在所述步骤(2)中的高压反应釜中保温温度为90-180℃，保温时间为60分钟-120分钟。
  9. 根据权利要求8所述的基于石墨烯气凝胶的能量收集与自清洁系统的制备方法，其特征在于：在所述步骤(4)中低温冷冻温度为-20—100℃，保温时间为1min-300min。
  10. 根据权利要求8或9所述的基于石墨烯气凝胶的能量收集与自清洁系统的制备方法，其特征在于：在所述步骤(4)中冷冻干燥的温度为-70℃，所述冷冻干燥的时间为24-72h。
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