WO2021184947A1 - Lignin-based flexible fibrous electrode, preparation method therefor and application thereof - Google Patents

Lignin-based flexible fibrous electrode, preparation method therefor and application thereof Download PDF

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WO2021184947A1
WO2021184947A1 PCT/CN2021/072460 CN2021072460W WO2021184947A1 WO 2021184947 A1 WO2021184947 A1 WO 2021184947A1 CN 2021072460 W CN2021072460 W CN 2021072460W WO 2021184947 A1 WO2021184947 A1 WO 2021184947A1
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lignin
preparation
fibrous electrode
electrode
graphene oxide
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PCT/CN2021/072460
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French (fr)
Chinese (zh)
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陈嘉川
李凤凤
贾倩倩
杨桂花
张志礼
吉兴香
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齐鲁工业大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention belongs to the field of biomass functional materials, and specifically relates to a lignin-based flexible fibrous electrode and a preparation method and application thereof.
  • Lignin is the second largest biomass resource on the earth after cellulose. It is cheap, easily available, and renewable. Moreover, as the only natural polymer rich in aromatic ring structures in nature, lignin itself and its derivatives contain abundant electroactive groups such as methoxy groups and phenolic hydroxyl groups, which have the potential to be used as electrode materials. Therefore, the development of economical and efficient lignin-based electrode materials can not only expand the high-value applications of lignin, but also provide new ideas for the design and preparation of high-performance biomass-based electrode materials. The development of electrodes is of great significance. However, the inventor found that the electrical insulation of lignin itself makes it difficult to directly use.
  • the purpose of the present invention is to provide a lignin-based flexible fibrous electrode and a preparation method and application thereof.
  • One aspect of the present invention provides a method for preparing a lignin-based flexible fibrous electrode, which includes the following steps:
  • the temperature of the low-temperature hydrothermal reaction is 60-80°C.
  • the second aspect of the present invention provides a lignin-based flexible fibrous electrode prepared by the above preparation method.
  • the third aspect of the present invention provides the application of the lignin-based flexible fibrous electrode in the preparation of flexible supercapacitors, and further, the application in the preparation of portable, wearable, and foldable electronic devices.
  • the fourth aspect of the present invention provides a flexible supercapacitor, which is prepared from the lignin-based flexible fibrous electrode.
  • an electronic device is provided, and the power source is the flexible super capacitor.
  • Green, cheap, and renewable lignin is used as raw material to prepare flexible electrodes, which can effectively replace expensive electrode materials such as metal oxides and conductive polymers, and is of great significance to the development of low-cost, renewable new flexible electrodes ;
  • Graphene oxide is low in cost and easy to disperse, and the price of vitamin C reducing agent is also low.
  • the reduced graphene oxide obtained by reduction can meet the experimental needs; graphene is difficult to disperse, and the cost is high, so graphene oxide and reducing agent are used as raw materials .
  • the lignin-based fiber electrode is prepared by a gentle and efficient low-temperature hydrothermal method, which overcomes the damage to the lignin structure caused by the high-temperature carbonization process in the prior art, protects the inherent active groups of lignin to the greatest extent, and improves the electrode material Performance.
  • the reaction mechanism is: in the hydrothermal system, the benzene ring structure of lignin and the benzene ring structure on the graphene oxide nanosheets are stably combined through ⁇ - ⁇ conjugation and dispersed on the surface of the graphene oxide sheet; at the same time, the graphene oxide It is gradually reduced by the reducing agent vitamin C and self-assembled layer by layer to form a fiber skeleton, thus forming a lignin-based fibrous electrode.
  • flexible lignin-based fiber electrodes are prepared by physical cross-linking, which avoids the use of toxic and harmful chemical cross-linking agents and reduces the resulting environment problem.
  • Figure 1 is a picture of a lignin-based flexible fibrous electrode prepared in Example 1;
  • Figure 2 is a picture of a lignin-based flexible fibrous electrode prepared in Example 2;
  • Figure 3 is the cyclic voltammetry curve of the lignin-based flexible fibrous electrode prepared in Examples 1-3.
  • One aspect of the present invention provides a method for preparing a lignin-based flexible fibrous electrode, which includes the following steps:
  • the temperature of the low-temperature hydrothermal reaction is 60-80°C.
  • the alkali lignin is extracted from biomass alkali pulping black liquor.
  • the biomass here can be fiber raw materials such as coniferous woods and hardwoods, such as rhizomes and leaves, or non-wood fiber raw materials, such as grass.
  • the purity of the alkali lignin is 90-95%.
  • the water content in the alkali lignin is 5 to 7%.
  • the particle size of the alkali lignin is 90-95 mesh.
  • the molecular weight of the alkali lignin is 2500-4000.
  • the purity, water content, particle size and molecular weight of lignin significantly affect the preparation and performance of flexible fibrous electrode materials.
  • the purity of lignin is too low and the moisture content is too large, which is not conducive to the combination of lignin and graphene oxide, and is not conducive to wood.
  • the graphene oxide is prepared by the Hummers method.
  • the mass ratio of alkali lignin to graphene oxide in the mixed dispersion liquid is (0.5-2):1.
  • the reducing agent is vitamin C.
  • the purity of the vitamin C is 95% to 98%.
  • the mass ratio of the graphene oxide to vitamin C is 1:(0.5-2).
  • the method of mixing alkali lignin, graphene oxide, and reducing agent in a solvent is ultrasonic dispersion, and the power of the ultrasonic dispersion is 400-600W.
  • the ultrasonic dispersion time is 15-25 minutes.
  • reaction time of the low-temperature hydrothermal method is 2-10h.
  • the second aspect of the present invention provides a lignin-based flexible fibrous electrode prepared by the above preparation method.
  • the third aspect of the present invention provides the application of the lignin-based flexible fibrous electrode in the preparation of flexible supercapacitors, and further, the application in the preparation of portable, wearable, and foldable electronic devices.
  • the fourth aspect of the present invention provides a flexible supercapacitor, which is prepared from the lignin-based flexible fibrous electrode.
  • the tensile strength can reach 64MPa.
  • the tensile strength can reach 57MPa.
  • the tensile strength can reach 41MPa.
  • the lignin-based flexible fibrous electrode prepared in Examples 1-3 was subjected to a cyclic voltammetry test within the voltage range of 0-1V, and the cyclic voltammetry curve is shown in FIG. 3.
  • the cyclic voltammetry curve of the obtained lignin-based flexible fibrous electrode material presents a rectangular shape, indicating that the electrode material has excellent electrochemical energy storage properties.
  • the area of the closed curve can reflect the specific capacitance, that is, the energy storage capacity. It can be seen from FIG. 3 that, relatively speaking, the electrode material of Example 3 has a larger specific capacitance and better performance.

Abstract

A lignin-based flexible fibrous electrode, a preparation method therefor and an application thereof. The preparation method comprises the following steps: uniformly dispersing an alkali lignin, graphene oxide, and a reducing agent into a solvent to form a mixed dispersion liquid; and performing a low-temperature hydrothermal method reaction on the mixed dispersion liquid to obtain a lignin-based flexible fibrous electrode by preparation, wherein the temperature of the low-temperature hydrothermal method reaction is 60-80ºC. Green, cheap and renewable lignin is used as a raw material to prepare the flexible electrode, expensive electrode materials such as a metal oxide and a conductive macromolecule can be effectively replaced, and the method has important significance in the development of a low-cost and renewable novel flexible electrode.

Description

一种木质素基柔性纤维状电极及其制备方法与应用A lignin-based flexible fibrous electrode and its preparation method and application
本申请要求于2020年03月18日提交中国专利局、申请号为202010191293.1、发明名称为“一种木质素基柔性纤维状电极及其制备方法与应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application filed with the Chinese Patent Office on March 18, 2020, the application number is 202010191293.1, and the invention title is "a lignin-based flexible fibrous electrode and its preparation method and application". All of them The content is incorporated in this application by reference.
技术领域Technical field
本发明属于生物质功能材料领域，具体涉及一种木质素基柔性纤维状电极及其制备方法与应用。The invention belongs to the field of biomass functional materials, and specifically relates to a lignin-based flexible fibrous electrode and a preparation method and application thereof.
背景技术Background technique
公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。Disclosure of the background information is only intended to increase the understanding of the overall background of the present invention, and is not necessarily regarded as an acknowledgement or any form of suggestion that the information constitutes the prior art known to those of ordinary skill in the art.
随着新一代便携式、可穿戴、可折叠电子设备的相继出现，为之提供能量的柔性超级电容器的开发成为当前学术界和产业界的研究热点。柔性电极材料是决定超级电容器性能的最重要因素，可控设计、高性能、低成本及可再生的柔性电极材料一直是科研工作者孜孜以求的目标。With the emergence of a new generation of portable, wearable, and foldable electronic devices, the development of flexible supercapacitors that provide energy for them has become a current research hotspot in academia and industry. Flexible electrode materials are the most important factor that determines the performance of supercapacitors. Controllable design, high performance, low cost and renewable flexible electrode materials have always been the goal of scientific researchers.
木质素是地球上仅次于纤维素的第二大生物质资源，廉价、易得、可再生。而且，木质素作为自然界中唯一富含芳香环结构的天然高分子，其本身及其衍生物含有丰富的电活性基团如甲氧基、酚羟基等，具有作为电极材料的潜质。因此，经济、高效木质素基电极材料的开发，既可以拓展木质素的高值化应用，又为高性能生物质基电极材料的设计与制备提供新思路，对低成本、可再生的新型柔性电极的开发具有重要意义。然而，发明人发现，木质素本身的电绝缘性使其很难被直接利用。Lignin is the second largest biomass resource on the earth after cellulose. It is cheap, easily available, and renewable. Moreover, as the only natural polymer rich in aromatic ring structures in nature, lignin itself and its derivatives contain abundant electroactive groups such as methoxy groups and phenolic hydroxyl groups, which have the potential to be used as electrode materials. Therefore, the development of economical and efficient lignin-based electrode materials can not only expand the high-value applications of lignin, but also provide new ideas for the design and preparation of high-performance biomass-based electrode materials. The development of electrodes is of great significance. However, the inventor found that the electrical insulation of lignin itself makes it difficult to directly use.
发明内容Summary of the invention
为了解决现有技术中存在的技术问题，本发明的目的是提供一种木质素基柔性纤维状电极及其制备方法与应用。In order to solve the technical problems existing in the prior art, the purpose of the present invention is to provide a lignin-based flexible fibrous electrode and a preparation method and application thereof.
为了解决以上技术问题，本发明的一个或多个实施例提供的技术方案 如下：In order to solve the above technical problems, the technical solutions provided by one or more embodiments of the present invention are as follows:
本发明的一方面提供一种木质素基柔性纤维状电极的制备方法，包括如下步骤：One aspect of the present invention provides a method for preparing a lignin-based flexible fibrous electrode, which includes the following steps:
将碱木质素、氧化石墨烯和还原剂均匀分散于溶剂中，形成混合分散液；Disperse alkali lignin, graphene oxide and reducing agent uniformly in the solvent to form a mixed dispersion;
将所述混合分散液进行低温水热法反应，制备得到木质素柔性纤维电极；Subjecting the mixed dispersion to a low-temperature hydrothermal reaction to prepare a lignin flexible fiber electrode;
所述低温水热法反应的温度为60-80℃。The temperature of the low-temperature hydrothermal reaction is 60-80°C.
本发明的第二个方面，提供上述制备方法制备得到的木质素基柔性纤维状电极。The second aspect of the present invention provides a lignin-based flexible fibrous electrode prepared by the above preparation method.
本发明的第三个方面，提供上述木质素基柔性纤维状电极在制备柔性超级电容器中的应用，进一步的，在制备便携式、可穿戴、可折叠电子设备中的应用。The third aspect of the present invention provides the application of the lignin-based flexible fibrous electrode in the preparation of flexible supercapacitors, and further, the application in the preparation of portable, wearable, and foldable electronic devices.
本发明的第四个方面，提供一种柔性超级电容器，由所述木质素基柔性纤维状电极制备。The fourth aspect of the present invention provides a flexible supercapacitor, which is prepared from the lignin-based flexible fibrous electrode.
本发明的第五个方面，提供一种电子设备，电源为所述柔性超级电容器。In a fifth aspect of the present invention, an electronic device is provided, and the power source is the flexible super capacitor.
与现有技术相比，本发明的以上一个或多个实施例的有益效果为：Compared with the prior art, the beneficial effects of the above one or more embodiments of the present invention are:
(1)采用绿色、廉价、可再生的木质素作为原料制备柔性电极，可以有效替代金属氧化物、导电高分子等昂贵的电极材料，对低成本、可再生的新型柔性电极的开发具有重要意义；(1) Green, cheap, and renewable lignin is used as raw material to prepare flexible electrodes, which can effectively replace expensive electrode materials such as metal oxides and conductive polymers, and is of great significance to the development of low-cost, renewable new flexible electrodes ；
氧化石墨烯成本低、易分散，维C还原剂价格也低，其还原得到的还原氧化石墨烯可以满足实验需求；石墨烯很难分散，而且成本高，所以采用氧化石墨烯和还原剂作为原料。Graphene oxide is low in cost and easy to disperse, and the price of vitamin C reducing agent is also low. The reduced graphene oxide obtained by reduction can meet the experimental needs; graphene is difficult to disperse, and the cost is high, so graphene oxide and reducing agent are used as raw materials .
(2)采用温和、高效的低温水热法制备木质素基纤维电极，克服了现有技术中高温碳化过程对木质素结构的破坏，最大限度的保护木质素固有的活性基团，提高电极材料的性能。反应机理为：水热体系中，木质素的苯环结构与氧化石墨烯纳米片上的苯环结构通过π-π共轭作用稳定结合，分散于氧化石墨烯片表面；与此同时，氧化石墨烯被还原剂维生素C逐步还原，发生层层自组装，形成了纤维骨架，由此形成了木质素基纤维 状电极。(2) The lignin-based fiber electrode is prepared by a gentle and efficient low-temperature hydrothermal method, which overcomes the damage to the lignin structure caused by the high-temperature carbonization process in the prior art, protects the inherent active groups of lignin to the greatest extent, and improves the electrode material Performance. The reaction mechanism is: in the hydrothermal system, the benzene ring structure of lignin and the benzene ring structure on the graphene oxide nanosheets are stably combined through π-π conjugation and dispersed on the surface of the graphene oxide sheet; at the same time, the graphene oxide It is gradually reduced by the reducing agent vitamin C and self-assembled layer by layer to form a fiber skeleton, thus forming a lignin-based fibrous electrode.
(3)利用木质素与石墨烯片层间稳定的界面结合力，通过物理交联方式制备柔性的木质素基纤维电极，避免了有毒有害化学交联剂的使用，并减少由此引发的环境问题。(3) Using the stable interfacial bonding force between lignin and graphene sheets, flexible lignin-based fiber electrodes are prepared by physical cross-linking, which avoids the use of toxic and harmful chemical cross-linking agents and reduces the resulting environment problem.
附图说明Description of the drawings
构成本发明的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。The drawings of the specification forming a part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments and descriptions of the present invention are used to explain the present invention, and do not constitute an improper limitation of the present invention.
图1为实施例1制得的木质素基柔性纤维状电极图片；Figure 1 is a picture of a lignin-based flexible fibrous electrode prepared in Example 1;
图2为实施例2制得的木质素基柔性纤维状电极图片；Figure 2 is a picture of a lignin-based flexible fibrous electrode prepared in Example 2;
图3为实施例1-3制得的木质素基柔性纤维状电极的循环伏安曲线。Figure 3 is the cyclic voltammetry curve of the lignin-based flexible fibrous electrode prepared in Examples 1-3.
具体实施方式Detailed ways
应该指出，以下详细说明都是示例性的，旨在对本发明提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。It should be pointed out that the following detailed descriptions are all exemplary and are intended to provide further description of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention belongs.
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本发明的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。It should be noted that the terms used here are only for describing specific embodiments, and are not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should also be understood that when the terms "comprising" and/or "including" are used in this specification, they indicate There are features, steps, operations, devices, components, and/or combinations thereof.
本发明的一方面提供一种木质素基柔性纤维状电极的制备方法，包括如下步骤：One aspect of the present invention provides a method for preparing a lignin-based flexible fibrous electrode, which includes the following steps:
将碱木质素、氧化石墨烯和还原剂均匀分散于溶剂中，形成混合分散液；Disperse alkali lignin, graphene oxide and reducing agent uniformly in the solvent to form a mixed dispersion;
将所述混合分散液进行低温水热法反应，制备得到木质素柔性纤维电极；Subjecting the mixed dispersion to a low-temperature hydrothermal reaction to prepare a lignin flexible fiber electrode;
所述低温水热法反应的温度为60～80℃。The temperature of the low-temperature hydrothermal reaction is 60-80°C.
在一些实施例中，所述碱木质素从生物质碱法制浆黑液中提取而来。此处的生物质可以为针叶木、阔叶木中的根茎叶等纤维原料，或者是非木纤维原料，如，草。In some embodiments, the alkali lignin is extracted from biomass alkali pulping black liquor. The biomass here can be fiber raw materials such as coniferous woods and hardwoods, such as rhizomes and leaves, or non-wood fiber raw materials, such as grass.
进一步的，所述碱木质素的纯度为90～95％。Further, the purity of the alkali lignin is 90-95%.
更进一步的，所述碱木质素中的含水量为5～7％。Furthermore, the water content in the alkali lignin is 5 to 7%.
进一步的，所述碱木质素的粒径为90～95目。Further, the particle size of the alkali lignin is 90-95 mesh.
进一步的，所述碱木质素的分子量为2500～4000。Further, the molecular weight of the alkali lignin is 2500-4000.
木质素的纯度、含水量、粒径、分子量，显著影响柔性纤维状电极材料的制备及性能，如木质素纯度过低、水分含量过大，不利于木质素与氧化石墨烯结合，不利于木质素基柔性纤维电极材料的制备；此外，木质素粒径和分子量影响木质素在水溶液中的分散度，分散度越高，反应越充分，性能更优。The purity, water content, particle size and molecular weight of lignin significantly affect the preparation and performance of flexible fibrous electrode materials. For example, the purity of lignin is too low and the moisture content is too large, which is not conducive to the combination of lignin and graphene oxide, and is not conducive to wood. Preparation of element-based flexible fiber electrode materials; in addition, the particle size and molecular weight of lignin affect the dispersion of lignin in aqueous solution. The higher the dispersion, the more sufficient the reaction and the better performance.
在一些实施例中，所述氧化石墨烯通过Hummers方法制备。In some embodiments, the graphene oxide is prepared by the Hummers method.
以下实施例中氧化石墨烯的具体制备步骤如下：取浓硫酸20mL、石墨粉(1.0g)、硝酸钠(0.7g)分别加入烧杯中，在冰水浴中搅拌一段时间后，将高锰酸钾(3.2g)缓慢加入到烧杯中，将反应体系在30℃下反应25分钟，然后缓慢加入50mL去离子水，使温度维持在90℃反应15分钟，继续加入160mL水后，加入5mL双氧水，溶液颜色从黑褐色变为亮黄色。将产物过滤后用0.15mol/L HCl水溶液(150mL)清洗后，加入200mL去离子水抽滤去除残留的杂质和酸。抽滤完成后加入500mL去离子水稀释，透析去掉残留的金属离子，在超声(功率450W)中处理后20分钟，随后离心得到氧化石墨烯溶液，测定其浓度，备用。The specific preparation steps of graphene oxide in the following examples are as follows: Take 20 mL of concentrated sulfuric acid, graphite powder (1.0 g), and sodium nitrate (0.7 g) into a beaker, stir for a period of time in an ice water bath, and add potassium permanganate. (3.2g) slowly added to the beaker, react the reaction system at 30℃ for 25 minutes, then slowly add 50mL deionized water, keep the temperature at 90℃ for 15 minutes, continue to add 160mL water, add 5mL hydrogen peroxide, solution The color changes from dark brown to bright yellow. After filtering the product, it was washed with 0.15 mol/L HCl aqueous solution (150 mL), and then 200 mL of deionized water was added for suction filtration to remove residual impurities and acid. After the suction filtration is completed, add 500 mL of deionized water to dilute, dialyze to remove the remaining metal ions, treat in ultrasound (power 450W) for 20 minutes, and then centrifuge to obtain a graphene oxide solution, and determine its concentration for use.
进一步的，所述混合分散液中碱木质素与氧化石墨烯的质量比为(0.5～2):1。Further, the mass ratio of alkali lignin to graphene oxide in the mixed dispersion liquid is (0.5-2):1.
在一些实施例中，所述还原剂为维生素C。In some embodiments, the reducing agent is vitamin C.
进一步的，所述维生素C的纯度为95％～98％。Further, the purity of the vitamin C is 95% to 98%.
进一步的，所述氧化石墨烯与维生素C的质量比为1:(0.5～2)。Further, the mass ratio of the graphene oxide to vitamin C is 1:(0.5-2).
在一些实施例中，将碱木质素、氧化石墨烯和还原剂在溶剂中混匀的方法为超声分散，所述超声分散的功率为400～600W。In some embodiments, the method of mixing alkali lignin, graphene oxide, and reducing agent in a solvent is ultrasonic dispersion, and the power of the ultrasonic dispersion is 400-600W.
进一步的，所述超声分散的时间为15～25min。Further, the ultrasonic dispersion time is 15-25 minutes.
在一些实施例中，所述低温水热法反应的时间为2～10h。In some embodiments, the reaction time of the low-temperature hydrothermal method is 2-10h.
本发明的第二个方面，提供上述制备方法制备得到的木质素基柔性纤维状电极。The second aspect of the present invention provides a lignin-based flexible fibrous electrode prepared by the above preparation method.
本发明的第三个方面，提供上述木质素基柔性纤维状电极在制备柔性超级电容器中的应用，进一步的，在制备便携式、可穿戴、可折叠电子设备中的应用。The third aspect of the present invention provides the application of the lignin-based flexible fibrous electrode in the preparation of flexible supercapacitors, and further, the application in the preparation of portable, wearable, and foldable electronic devices.
本发明的第四个方面，提供一种柔性超级电容器，由所述木质素基柔性纤维状电极制备。The fourth aspect of the present invention provides a flexible supercapacitor, which is prepared from the lignin-based flexible fibrous electrode.
实施例1Example 1
取5mg针叶木碱法木质素(纯度为90％、含水量在5％、粒径90目、分子量为2500)分散到5mL氧化石墨烯溶液(浓度为2mg/mL)中，加入10mg维生素C(纯度为98％)，超声处理的时间为15分钟，超声功率为600W，得到混合分散液。随后利用精密注射泵将混合分散液注入内径为1mm外径为2mm的聚四氟乙烯管，将两端用止血钳密封，在烘箱中处理6h，温度为80℃，反应结束后将其置于25℃恒温条件下冷却，并用电导率为20μS/cm去离子水冲洗，得到木质素基柔性纤维状电极，其图片如图1所示。Take 5mg of conifer lignin (purity of 90%, water content of 5%, particle size of 90 mesh, molecular weight of 2500) dispersed into 5mL graphene oxide solution (concentration of 2mg/mL), add 10mg vitamin C ( The purity is 98%), the ultrasonic treatment time is 15 minutes, the ultrasonic power is 600W, and the mixed dispersion liquid is obtained. Then use a precision syringe pump to inject the mixed dispersion into a polytetrafluoroethylene tube with an inner diameter of 1mm and an outer diameter of 2mm. The two ends are sealed with a hemostatic forceps, and treated in an oven for 6 hours at a temperature of 80°C. After the reaction, place it in Cool down at a constant temperature of 25°C, and rinse with deionized water with a conductivity of 20 μS/cm to obtain a lignin-based flexible fibrous electrode. The picture is shown in Figure 1.
所得纤维状电极在应变为8.26％时，拉伸强度可达64MPa。When the strain of the obtained fibrous electrode is 8.26%, the tensile strength can reach 64MPa.
实施例2Example 2
取5mg阔叶木碱法木质素(纯度为95％、含水量在6％、粒径95目、分子量为3000)分散到5mL氧化石墨烯溶液(浓度为2mg/mL)中，加入20mg维生素C(纯度为96％)，超声处理的时间为20分钟，超声功率为500W，得到混合分散液。随后利用精密注射泵将混合分散液注入内径为1mm、外径为2mm的聚四氟乙烯管，将两端用止血钳密封，在烘箱中处理4h，温度为70℃，反应结束后将其置于25℃恒温条件下冷却，并用电导率为15μS/cm去离子水冲洗，得到木质素基柔性纤维状电极，其图片如图2所示。Take 5mg hardwood alkali lignin (purity 95%, water content 6%, particle size 95 mesh, molecular weight 3000) dispersed into 5mL graphene oxide solution (concentration 2mg/mL), add 20mg vitamin C ( The purity is 96%), the ultrasonic treatment time is 20 minutes, the ultrasonic power is 500 W, and the mixed dispersion liquid is obtained. Then use a precision syringe pump to inject the mixed dispersion into a polytetrafluoroethylene tube with an inner diameter of 1 mm and an outer diameter of 2 mm. The two ends are sealed with a hemostatic forceps. The mixture is treated in an oven for 4 hours at a temperature of 70°C. After the reaction, it is placed It was cooled at a constant temperature of 25° C., and washed with deionized water with a conductivity of 15 μS/cm to obtain a lignin-based flexible fibrous electrode. The picture is shown in Figure 2.
所得纤维状电极在应变为7.75％时，拉伸强度可达57MPa。When the strain of the obtained fibrous electrode is 7.75%, the tensile strength can reach 57MPa.
实施例3Example 3
取5mg麦草碱法木质素(纯度为95％、含水量在7％、粒径100目、分子量为4000)分散到2mL氧化石墨烯溶液(浓度为5mg/mL)中，加入10mg维生素C(纯度为98％)，超声处理的时间为25分钟，超声功率为400W，得到混合分散液。随后利用精密注射泵将混合分散液注入内 径为3mm、外径为5mm的聚四氟乙烯管，将两端用止血钳密封，在烘箱中处理10h，温度为60℃，反应结束后将其置于25℃恒温条件下冷却，并用电导率为10μS/cm去离子水冲洗，得到木质素基柔性纤维状电极。Take 5mg of wheat straw soda lignin (purity of 95%, water content of 7%, particle size of 100 mesh, molecular weight of 4000) dispersed into 2mL graphene oxide solution (concentration of 5mg/mL), add 10mg vitamin C (purity 98%), the ultrasonic treatment time is 25 minutes, the ultrasonic power is 400W, and the mixed dispersion liquid is obtained. Then use a precision syringe pump to inject the mixed dispersion into a polytetrafluoroethylene tube with an inner diameter of 3 mm and an outer diameter of 5 mm. The two ends are sealed with a hemostatic forceps. The mixture is treated in an oven for 10 hours at a temperature of 60°C. After the reaction, it is placed Cooling at a constant temperature of 25° C., and washing with deionized water with a conductivity of 10 μS/cm, to obtain a lignin-based flexible fibrous electrode.
所得纤维状电极在应变为9.19％时，拉伸强度可达41MPa。When the strain of the obtained fibrous electrode is 9.19%, the tensile strength can reach 41MPa.
在电压为0-1V的范围内对实施例1-3中制备的木质素基柔性纤维状电极进行循环伏安试验，其循环伏安曲线如图3所示。The lignin-based flexible fibrous electrode prepared in Examples 1-3 was subjected to a cyclic voltammetry test within the voltage range of 0-1V, and the cyclic voltammetry curve is shown in FIG. 3.
由图3可知，所得木质素基柔性纤维状电极材料的循环伏安曲线呈现类矩形形状，说明该电极材料具有优异的电化学储能性质。图中，封闭曲线面积可体现比电容大小即储能容量，由图3可知，相对而言，实施例3电极材料的比电容大，性能更优。It can be seen from Fig. 3 that the cyclic voltammetry curve of the obtained lignin-based flexible fibrous electrode material presents a rectangular shape, indicating that the electrode material has excellent electrochemical energy storage properties. In the figure, the area of the closed curve can reflect the specific capacitance, that is, the energy storage capacity. It can be seen from FIG. 3 that, relatively speaking, the electrode material of Example 3 has a larger specific capacitance and better performance.
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above are only preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (17)

  1. 一种木质素基柔性纤维状电极的制备方法，其特征在于：包括如下步骤：A method for preparing a lignin-based flexible fibrous electrode, which is characterized in that it comprises the following steps:
    将碱木质素、氧化石墨烯和还原剂均匀分散于溶剂中，形成混合分散液；Disperse alkali lignin, graphene oxide and reducing agent uniformly in the solvent to form a mixed dispersion;
    将所述混合分散液进行低温水热法反应，得到木质素柔性纤维状电极；Subjecting the mixed dispersion to a low-temperature hydrothermal reaction to obtain a lignin flexible fibrous electrode;
    所述低温水热法反应的温度为60～80℃；The temperature of the low-temperature hydrothermal reaction is 60-80°C;
    所述还原剂为维生素C。The reducing agent is vitamin C.
  2. 根据权利要求1所述的制备方法，其特征在于：所述碱木质素从生物质碱法制浆黑液中提取而来。The preparation method according to claim 1, wherein the alkali lignin is extracted from biomass alkali pulping black liquor.
  3. 根据权利要求2所述的制备方法，其特征在于：所述碱木质素的纯度为90～95％。The preparation method according to claim 2, wherein the purity of the alkali lignin is 90-95%.
  4. 根据权利要求2或3所述的制备方法，其特征在于：所述碱木质素中的含水量为5～7％。The preparation method according to claim 2 or 3, wherein the water content in the alkali lignin is 5 to 7%.
  5. 根据权利要求2所述的制备方法，其特征在于：所述碱木质素的粒径为90～95目。The preparation method according to claim 2, wherein the particle size of the alkali lignin is 90-95 mesh.
  6. 根据权利要求2所述的制备方法，其特征在于：所述碱木质素的分子量为2500～4000。The preparation method according to claim 2, wherein the molecular weight of the alkali lignin is 2500-4000.
  7. 根据权利要求1所述的制备方法，其特征在于：所述氧化石墨烯通过Hummers方法制备。The preparation method according to claim 1, wherein the graphene oxide is prepared by the Hummers method.
  8. 根据权利要求1或7所述的制备方法，其特征在于：所述混合分散液中碱木质素与氧化石墨烯的质量比为(0.5～2):1。The preparation method according to claim 1 or 7, characterized in that the mass ratio of alkali lignin to graphene oxide in the mixed dispersion is (0.5-2):1.
  9. 根据权利要求1所述的制备方法，其特征在于：所述维生素C的纯度为95％～98％。The preparation method according to claim 1, wherein the purity of the vitamin C is 95% to 98%.
  10. 根据权利要求1或9所述的制备方法，其特征在于：所述氧化石墨烯与维生素C的质量比为1:(0.5～2)。The preparation method according to claim 1 or 9, wherein the mass ratio of the graphene oxide to vitamin C is 1:(0.5-2).
  11. 根据权利要求1所述的制备方法，其特征在于：将碱木质素、氧化石墨烯和还原剂均匀分散于溶剂中的方法为超声分散，所述超声分散的功率为400～600W；所述超声分散的时间为15～25min。The preparation method according to claim 1, wherein the method for uniformly dispersing alkali lignin, graphene oxide and reducing agent in a solvent is ultrasonic dispersion, and the power of the ultrasonic dispersion is 400-600W; The dispersion time is 15-25min.
  12. 根据权利要求1所述的制备方法，其特征在于：所述低温水热法反应的时间为2～10h。The preparation method according to claim 1, wherein the reaction time of the low-temperature hydrothermal method is 2-10h.
  13. 权利要求1～12任一所述制备方法制备得到的木质素基柔性纤维状电极。The lignin-based flexible fibrous electrode prepared by the preparation method of any one of claims 1-12.
  14. 权利要求13所述木质素基柔性纤维状电极在制备柔性超级电容器中的应用。The application of the lignin-based flexible fibrous electrode of claim 13 in the preparation of a flexible supercapacitor.
  15. 权利要求13所述木质素基柔性纤维状电极在制备便携式、可穿戴、可折叠电子设备中的应用。The application of the lignin-based flexible fibrous electrode of claim 13 in the preparation of portable, wearable, and foldable electronic devices.
  16. 一种柔性超级电容器，其特征在于：所述柔性超级电容器由权利要求13所述木质素基柔性纤维状电极制备。A flexible supercapacitor, characterized in that: the flexible supercapacitor is prepared from the lignin-based flexible fibrous electrode according to claim 13.
  17. 一种电子设备，其特征在于：所述电子设备的电源为权利要求16所述柔性超级电容器。An electronic device, characterized in that: the power source of the electronic device is the flexible supercapacitor according to claim 16.
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