CN108257795B - A method for improving supercapacitor capacitance - Google Patents
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Abstract
Description
技术领域technical field
本发明涉及光热转化和能量储存领域，具体涉及一种利用光热效应提高超级电容器电容的方法。The invention relates to the field of photothermal conversion and energy storage, in particular to a method for improving supercapacitor capacitance by utilizing photothermal effect.
背景技术Background technique
太阳能是一种资源丰富、可免费使用、无需运输、而且对环境无任何污染的可再生能源。太阳能转化技术比如光伏、光催化、人工光合作用、光热转换等发展迅速，在这些太阳能转化技术中，光热转化技术具有高转化效率和低成本的优点，因而受到广泛关注。迄今为止，光热转化技术已经被应用于诸多领域，比如太阳能水净化和光热治疗等，而且其应用领域有望进一步得到拓展。Solar energy is a kind of renewable energy that is rich in resources, can be used free of charge, requires no transportation, and does not pollute the environment. Solar energy conversion technologies such as photovoltaics, photocatalysis, artificial photosynthesis, and photothermal conversion have developed rapidly. Among these solar energy conversion technologies, photothermal conversion technology has the advantages of high conversion efficiency and low cost, and thus has received extensive attention. So far, photothermal conversion technology has been used in many fields, such as solar water purification and photothermal therapy, and its application fields are expected to be further expanded.
能量储存器件是当今世界人们生活中不可缺少的元件。超级电容器是一种重要的能量储存器件，具有功率密度高、充放电速率快和循环寿命长等优点。超级电容器一般包括双电层超级电容器、赝电容超级电容器和复合式超级电容器。双电层超级电容器主要基于离子的吸附/解吸附机制，赝电容超级电容器主要基于快速的法拉第反应机制，复合式超级电容器将双电层超级电容器和赝电容超级电容器结合到一个器件里面(一般一个电极为双电层电极一个电极为赝电容电极)。与其他能量储存器件比如电池相似的是，在温度降低的时候，超级电容器的电容、能量密度和功率密度一般都会下降。因而，亟需寻找一种环保无污染的方法来提高超级电容器在低环境温度下的电容，以解决低温环境下超级电容器性能下降的问题，而且还有望发展多功能超级电容器比如可以对温度或光照有响应的超级电容器。Energy storage devices are indispensable components in people's lives in today's world. Supercapacitors are important energy storage devices with the advantages of high power density, fast charge and discharge rates, and long cycle life. Supercapacitors generally include electric double layer supercapacitors, pseudocapacitive supercapacitors and composite supercapacitors. The electric double layer supercapacitor is mainly based on the adsorption/desorption mechanism of ions, the pseudocapacitor supercapacitor is mainly based on the fast Faraday reaction mechanism, and the composite supercapacitor combines the electric double layer supercapacitor and the pseudocapacitor supercapacitor into one device (generally one The electrodes are electric double layer electrodes and one electrode is a pseudocapacitive electrode). Similar to other energy storage devices such as batteries, the capacitance, energy density and power density of supercapacitors generally decrease as the temperature decreases. Therefore, it is urgent to find an environmentally friendly and non-polluting method to improve the capacitance of supercapacitors at low ambient temperature to solve the problem of performance degradation of supercapacitors in low temperature environments. Responsive supercapacitors.
发明内容SUMMARY OF THE INVENTION
本发明提供一种提高超级电容器电容的方法，该方法通过利用光热效应可提高超级电容器的温度，从而提高超级电容器的电容，并随之提高能量密度和功率密度。The present invention provides a method for increasing the capacitance of a supercapacitor. The method can increase the temperature of the supercapacitor by utilizing the photothermal effect, thereby increasing the capacitance of the supercapacitor, thereby increasing the energy density and power density.
为了实现上述目的，本发明采用如下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
本发明提供一种提高超级电容器电容的方法，所述方法包括用光照射超级电容器，使超级电容器的温度升高，以提高超级电容器的电容。The present invention provides a method for increasing the capacitance of a supercapacitor, the method comprising irradiating the supercapacitor with light to increase the temperature of the supercapacitor to increase the capacitance of the supercapacitor.
根据本发明的一个实施方式，所述超级电容器为双电层超级电容器、赝电容超级电容器或复合式超级电容器，所述复合式超级电容器具有双电层电极和赝电容电极。According to an embodiment of the present invention, the supercapacitor is an electric double layer supercapacitor, a pseudocapacitive supercapacitor or a composite supercapacitor, and the composite supercapacitor has an electric double layer electrode and a pseudocapacitive electrode.
根据本发明的一个实施方式，所述超级电容器的电极材料应为光热转化效率大于70％的材料。According to an embodiment of the present invention, the electrode material of the supercapacitor should be a material with a photothermal conversion efficiency greater than 70%.
根据本发明的一个实施方式，所述超级电容器的电极材料选自三维石墨烯、碳纳米管或活性炭中的一种。According to an embodiment of the present invention, the electrode material of the supercapacitor is selected from one of three-dimensional graphene, carbon nanotubes or activated carbon.
根据本发明的一个实施方式，所述超级电容器的电解质选自聚乙烯醇/(酸、碱、盐)电解质、聚丙烯酸钾/硫酸电解质或离子液体电解质中的一种，所述聚乙烯醇/(酸、碱、盐)电解质包括但不限于聚乙烯醇/磷酸(PVA/H3PO4)电解质、聚乙烯醇/硫酸(PVA/H2SO4)电解质、聚乙烯醇/氢氧化钾(PVA/KOH)电解质或聚乙烯醇/氯化钠(PVA/NaCl)电解质中的一种，所述离子液体电解质包括但不限于1-丁基-3-甲基咪唑六氟磷酸盐。According to one embodiment of the present invention, the electrolyte of the supercapacitor is selected from one of polyvinyl alcohol/(acid, alkali, salt) electrolyte, potassium polyacrylate/sulfuric acid electrolyte or ionic liquid electrolyte, and the polyvinyl alcohol/(acid, alkali, salt) electrolyte (Acid, base, salt) electrolytes include but are not limited to polyvinyl alcohol/phosphoric acid (PVA/H 3 PO 4 ) electrolyte, polyvinyl alcohol/sulfuric acid (PVA/H 2 SO 4 ) electrolyte, polyvinyl alcohol/potassium hydroxide ( One of PVA/KOH) electrolyte or polyvinyl alcohol/sodium chloride (PVA/NaCl) electrolyte, the ionic liquid electrolyte includes but is not limited to 1-butyl-3-methylimidazolium hexafluorophosphate.
根据本发明的一个实施方式，所述光照后所达到的超级电容器的温度不超过所用电极材料、电解质或者活性物质的失效温度。According to an embodiment of the present invention, the temperature of the supercapacitor reached after irradiation does not exceed the failure temperature of the electrode material, electrolyte or active material used.
根据本发明的一个实施方式，对超级电容器进行光照的光源包括但不限于太阳光、钠灯光、氙灯光或其它照明光源中的一种，优选为太阳光、钠灯光或氙灯光。According to an embodiment of the present invention, the light source for illuminating the supercapacitor includes but is not limited to one of sunlight, sodium lamp, xenon lamp or other lighting sources, preferably sunlight, sodium lamp or xenon lamp.
根据本发明的一个实施方式，所述对超级电容器进行光照的强度为0.1～100kW/m2。According to an embodiment of the present invention, the intensity of the illumination on the supercapacitor is 0.1-100 kW/m 2 .
根据本发明的一个实施方式，所述超级电容器所处的环境温度为-200℃～100℃。According to an embodiment of the present invention, the ambient temperature where the supercapacitor is located is -200°C to 100°C.
根据本发明的一个实施方式，所述赝电容超级电容器或复合式超级电容器中的赝电容电极所用的活性物质材料选自聚合物活性物质或氧化物活性物质中的一种，优选为聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT：PSS)、聚苯胺(PANI)或二氧化锰(MnO2)。According to an embodiment of the present invention, the active material used in the pseudocapacitive electrode in the pseudocapacitive supercapacitor or the composite supercapacitor is selected from a polymer active material or an oxide active material, preferably poly(3 , 4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT: PSS), polyaniline (PANI) or manganese dioxide (MnO 2 ).
根据本发明的一个实施方式，所述超级电容器的结构为平面状结构、三明治型结构或者圆柱型结构。According to an embodiment of the present invention, the structure of the supercapacitor is a planar structure, a sandwich structure or a cylindrical structure.
根据上述技术方案的描述可知，本发明所述的超级电容器在光照下电容提高的原理为：在光照下，由于光热效应，超级电容器的温度提高，使得法拉第反应速率提高，电解质的介电常数提高，超级电容器内阻下降，从而使得超级电容器的电容提高，从而功率密度和能量密度也随之得到提高。According to the description of the above technical solutions, the principle of increasing the capacitance of the supercapacitor of the present invention under illumination is as follows: under illumination, due to the photothermal effect, the temperature of the supercapacitor increases, which increases the Faradaic reaction rate and the dielectric constant of the electrolyte. , the internal resistance of the supercapacitor decreases, so that the capacitance of the supercapacitor increases, thereby increasing the power density and energy density.
与现有技术相比，本发明的有益效果在于：Compared with the prior art, the beneficial effects of the present invention are:
该方法环保无污染，不需要通过外加电源加热，仅仅通过对超级电容器进行光照，利用光照产生的光热效应，使得超级电容器的温度升高，从而增大超级电容器电容、能量密度和功率密度，适用于储能应用以及太阳能转化的应用。The method is environmentally friendly and pollution-free, does not need to be heated by an external power supply, only illuminates the supercapacitor, and uses the photothermal effect generated by the illumination to increase the temperature of the supercapacitor, thereby increasing the capacitance, energy density and power density of the supercapacitor. For energy storage applications and solar energy conversion applications.
附图说明Description of drawings
图1是本发明实施例1中所用的以三维石墨烯为电极，PVA/H3PO4为电解质的双电层超级电容器结构示意图。1 is a schematic structural diagram of an electric double layer supercapacitor with three-dimensional graphene as an electrode and PVA/H 3 PO 4 as an electrolyte used in Example 1 of the present invention.
图2是本发明实施例1中双电层超级电容器在25℃的环境温度下进行不同太阳光照强度照射时电容的升高情况。FIG. 2 shows the increase in capacitance of the electric double layer supercapacitor in Example 1 of the present invention when irradiated with different sunlight intensities at an ambient temperature of 25°C.
图3是实施例2中所用的以三维石墨烯为电极，PEDOT:PSS为活性物质，PVA/H3PO4为电解质的超级电容器在25℃的环境温度下进行1个太阳光照强度照射时的温度响应曲线。Fig. 3 is used in embodiment 2 with three-dimensional graphene as electrode, PEDOT:PSS as active material, PVA/H 3 PO 4 as electrolyte supercapacitor when irradiating with 1 solar light intensity at an ambient temperature of 25°C temperature response curve.
图4是实施例2中超级电容器在25℃的环境温度下用不同太阳光照强度照射时所达到的平衡温度。FIG. 4 is the equilibrium temperature reached when the supercapacitor in Example 2 is irradiated with different solar light intensities at an ambient temperature of 25°C.
图5a是实施例2中无光照以及随光照强度增大超级电容器电容增大情况；Fig. 5a is no illumination in embodiment 2 and the supercapacitor capacitance increases with the increase of illumination intensity;
图5b是实施例2中无光照以及随光照强度增大能量密度和功率密度增大情况(直流充放电电流密度为3.3mA/cm-3)。Fig. 5b shows the situation of no illumination and the increase of energy density and power density with the increase of illumination intensity in Example 2 (DC charge-discharge current density is 3.3 mA/cm -3 ).
具体实施方式Detailed ways
以下通过特定的具体实施例说明本发明的实施方式，本领域普通技术人员可由本说明书所公开的内容轻易地了解本发明的优点及功效。本发明也可通过其它不同的实施方式加以施行或应用，本说明书中的各项细节也可基于不同观点与应用，在不悖离本发明所公开的构思下赋予不同的修饰与变更。此外，本文所有范围和值都包含及可合并的。落在本文中所述的范围内的任何数值或点，例如任何整数都可以作为最小值或最大值以导出下位范围等。The embodiments of the present invention are described below through specific specific examples, and those skilled in the art can easily understand the advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different embodiments, and various details in this specification can also be given different modifications and changes based on different viewpoints and applications without departing from the concept disclosed in the present invention. Furthermore, all ranges and values herein are inclusive and combinable. Any value or point falling within a range described herein, eg, any integer, can be taken as a minimum or maximum value to derive a lower range, etc.
下述实施例中所述实验方法，如无特殊说明，均为常规方法；所述试剂和材料，如无特殊说明，均可从商业途径获得。The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials can be obtained from commercial sources unless otherwise specified.
实施例1：双电层超级电容器的制备及光照对其性能的影响Example 1: Preparation of Electric Double Layer Supercapacitor and Effect of Lighting on Its Performance
制备双电层超级电容器的方法包括如下步骤：The method for preparing an electric double layer supercapacitor comprises the following steps:
(1)将大片三维石墨烯切割成若干尺寸为10mm×5mm的小片；(1) Cut the large piece of three-dimensional graphene into several small pieces with a size of 10mm×5mm;
(2)将步骤(1)中的两小片三维石墨烯并排放到(聚对苯二甲酸乙二醇酯)PET基底上，用银浆将两小片三维石墨烯分别与导线相连接；(2) the two small pieces of three-dimensional graphene in step (1) are discharged side by side on the (polyethylene terephthalate) PET substrate, and the two small pieces of three-dimensional graphene are connected with wires respectively with silver paste;
(3)将步骤(2)中的三维石墨烯用厚胶带或者硅胶围起来；(3) enclose the three-dimensional graphene in step (2) with thick adhesive tape or silica gel;
(4)将液态PVA/H3PO4电解质倒入步骤(3)中围起来的三维石墨烯内；(4) pouring the liquid PVA/H 3 PO 4 electrolyte into the three-dimensional graphene enclosed in step (3);
(5)将步骤(4)所得部件放入烘箱，60℃下进行烘干；(5) putting the parts obtained in step (4) into an oven, and drying at 60°C;
(6)将步骤(5)烘干后的部件去掉厚胶带或硅胶，并去掉PET基底，即得到双电层超级电容器，其结构如图1所示。(6) Remove the thick adhesive tape or silica gel from the parts dried in step (5), and remove the PET substrate to obtain an electric double-layer supercapacitor, the structure of which is shown in Figure 1 .
在25℃的环境温度下，将制得的双电层超级电容器用模拟太阳光照射，太阳光的光照强度可通过聚光镜片和滤光镜片来调节，如图2所示，为该双电层超级电容器进行不同太阳光照强度照射时电容的升高情况，在1个太阳光(光强：1kW/m2)照射时，超级电容器的温度在4分钟内升到平衡温度约64℃，其电容和能量密度提高约3.7倍，功率密度提高约4倍。At an ambient temperature of 25°C, the prepared electric double layer supercapacitor was irradiated with simulated sunlight, and the illumination intensity of the sunlight could be adjusted by a condenser lens and a filter lens, as shown in Figure 2, for the electric double layer The increase in capacitance of the supercapacitor when irradiated with different sunlight intensities, when irradiated by one sunlight (light intensity: 1kW/m 2 ), the temperature of the supercapacitor rises to the equilibrium temperature of about 64°C within 4 minutes, and its capacitance And the energy density is increased by about 3.7 times, and the power density is increased by about 4 times.
实施例2：赝电容超级电容器的制备及光照对其性能的影响Example 2: Preparation of Pseudocapacitive Supercapacitor and Effect of Lighting on Its Performance
制备赝电容超级电容器方法包括如下步骤：The method for preparing pseudocapacitive supercapacitor includes the following steps:
(1)用质量分数为0.54％的聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)水溶液浸润大片三维石墨烯，然后70℃下进行烘干；(1) Infiltrate a large sheet of three-dimensional graphene with an aqueous solution of poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT:PSS) with a mass fraction of 0.54%, and then dry it at 70°C;
(2)将步骤(1)中烘干后的覆有PEDOT:PSS的大片三维石墨烯切割成若干尺寸为10mm×5mm的小片；(2) the large piece of three-dimensional graphene covered with PEDOT:PSS after drying in step (1) is cut into several small pieces with a size of 10mm×5mm;
(3)将步骤(2)中的两小片三维石墨烯并排放到PET基底上，用银浆将两小片三维石墨烯分别与导线相连接；(3) the two small pieces of three-dimensional graphene in step (2) are discharged side by side on the PET substrate, and the two small pieces of three-dimensional graphene are respectively connected with the wires with silver paste;
(4)将步骤(3)中的三维石墨烯用厚胶带或者硅胶围起来；(4) enclose the three-dimensional graphene in step (3) with thick adhesive tape or silica gel;
(5)将液态PVA/H2SO4电解质倒入步骤(4)中围起来的三维石墨烯内；(5) pouring the liquid PVA/H 2 SO 4 electrolyte into the three-dimensional graphene enclosed in step (4);
(6)将步骤(5)所得部件放入烘箱，60℃下进行烘干；(6) putting the parts obtained in step (5) into an oven, and drying at 60°C;
(7)将步骤(6)烘干后的部件去掉厚胶带或硅胶，并去掉PET基底，即得到赝电容超级电容器。(7) Remove the thick adhesive tape or silica gel from the parts dried in step (6), and remove the PET substrate to obtain a pseudocapacitor supercapacitor.
在25℃的环境温度下，将制得的赝电容超级电容器在模拟太阳光下进行光照，太阳光的光照强度可通过聚光镜片和滤光镜片来调节，图3为该赝电容超级电容器在1个太阳光照强度照射下的温度响应曲线，图4为该赝电容超级电容器在不同太阳光照强度照射时达到的光热平衡温度，图5a是该赝电容超级电容器无光照以及随光照强度增大电容的变化情况，图5b是该赝电容超级电容器无光照以及随光照强度增大能量密度和功率密度的变化情况(其中，直流充放电电流密度为3.3mA/cm-3)，可见，随着光照强度提高，该赝电容超级电容器的温度提高，从而电容、能量密度和功率密度得到提高。At an ambient temperature of 25 °C, the prepared pseudocapacitive supercapacitor was illuminated under simulated sunlight, and the illumination intensity of the sunlight could be adjusted by a condenser lens and a filter lens. Figure 3 shows the pseudocapacitive supercapacitor at 1 Figure 4 shows the photothermal equilibrium temperature of the pseudocapacitive supercapacitor when irradiated with different sunlight intensities, and Figure 5a shows the pseudocapacitive supercapacitor without illumination and the capacitance increases with the illumination intensity. Change situation, Fig. 5b is the change situation of the pseudocapacitive supercapacitor without light and the change of energy density and power density with the increase of light intensity (wherein, the DC charge and discharge current density is 3.3mA/cm -3 ), it can be seen that with the light intensity As the temperature of the pseudocapacitive supercapacitor increases, the capacitance, energy density and power density increase.
实施例3：复合式超级电容器的制备及光照对其性能的影响Example 3: Preparation of composite supercapacitor and the effect of illumination on its performance
制备复合式超级电容器方法包括如下步骤：The method for preparing a composite supercapacitor includes the following steps:
(1)将大片三维石墨烯切割成若干尺寸为10mm×5mm的小片；(1) Cut the large piece of three-dimensional graphene into several small pieces with a size of 10mm×5mm;
(2)用质量分数为0.54％的PEDOT:PSS水溶液浸润大片三维石墨烯，然后70℃下进行烘干；(2) infiltrating large sheets of three-dimensional graphene with a PEDOT:PSS aqueous solution with a mass fraction of 0.54%, and then drying at 70°C;
(3)将步骤(2)中烘干后的覆有PEDOT:PSS的大片三维石墨烯切割成若干尺寸为10mm×5mm的小片；(3) the large sheet of three-dimensional graphene covered with PEDOT:PSS after drying in step (2) is cut into several small pieces with a size of 10mm×5mm;
(4)将步骤(1)中的一小片三维石墨烯和步骤(3)中的一小片三维石墨烯并排放到PET基底上，用银浆将两小片三维石墨烯分别与导线相连接；(4) placing a small piece of three-dimensional graphene in step (1) and a small piece of three-dimensional graphene in step (3) on the PET substrate side by side, and using silver paste to connect the two small pieces of three-dimensional graphene with wires respectively;
(5)将步骤(4)中的三维石墨烯用厚胶带或者硅胶围起来；(5) enclose the three-dimensional graphene in step (4) with thick adhesive tape or silica gel;
(6)将液态PVA/H2SO4电解质倒入步骤(5)中围起来的三维石墨烯内；(6) pouring liquid PVA/H 2 SO 4 electrolyte into the three-dimensional graphene enclosed in step (5);
(7)将步骤(6)所得部件放入烘箱，60℃下进行烘干；(7) putting the parts obtained in step (6) into an oven, and drying at 60°C;
(8)将步骤(7)烘干后的部件去掉厚胶带或硅胶，并去掉PET基底，即得到复合式超级电容器；(8) remove thick adhesive tape or silica gel from the parts after drying in step (7), and remove the PET substrate to obtain a composite supercapacitor;
在25℃的环境温度下，将制得的复合式超级电容器进行太阳光照射，超级电容器的温度提高，从而电容、能量密度和功率密度得到提高。Under the ambient temperature of 25°C, the prepared composite supercapacitor is irradiated with sunlight, the temperature of the supercapacitor is increased, and the capacitance, energy density and power density are improved.
上述实施例仅为例示性说明，而非用于限制本发明。任何本领域普通技术人员均可在不违背本发明的构思及范畴下，对上述实施例进行修饰与改变。因此，本发明的权利保护范围是由本发明所附的权利要求书所定义，只要不影响本发明的效果及实施目的，应涵盖于此公开技术内容中。The above-mentioned embodiments are only illustrative, and are not intended to limit the present invention. Any person of ordinary skill in the art can modify and change the above embodiments without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention is defined by the appended claims of the present invention, and shall be included in the technical content disclosed herein as long as the effect and implementation purpose of the present invention are not affected.
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