WO2016110126A1 - 一种含无机纳米颗粒的超级电容器有机电解液 - Google Patents

一种含无机纳米颗粒的超级电容器有机电解液 Download PDF

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WO2016110126A1
WO2016110126A1 PCT/CN2015/089622 CN2015089622W WO2016110126A1 WO 2016110126 A1 WO2016110126 A1 WO 2016110126A1 CN 2015089622 W CN2015089622 W CN 2015089622W WO 2016110126 A1 WO2016110126 A1 WO 2016110126A1
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compound particles
inorganic compound
nano
electrolyte
nano inorganic
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阮殿波
杨斌
傅冠生
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宁波南车新能源科技有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/64—Liquid electrolytes characterised by additives
    • 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 relates to the technical field of supercapacitors, in particular to a supercapacitor organic electrolyte containing inorganic nanoparticles.
  • Electrochemical capacitors also known as super capacitors, extreme capacitors, etc.
  • super capacitors are new energy storage devices between secondary batteries and conventional electrostatic capacitors. They have higher energy density than conventional electrostatic capacitors and have higher energy density than secondary batteries. Larger power density, with high power density, long cycle life, wide operating temperature range, good cycle stability, maintenance-free, environmentally friendly, etc., has been in many fields, such as rail transit, wind power, hybrid power The backup power supply for vehicles and electronic devices has shown broad application prospects.
  • Current supercapacitor organic system electrolytes are mainly composed of organic solvents and organic salts.
  • the solvent includes, for example, acetonitrile, propylene carbonate and the like
  • the organic salt includes ammonium tetraethylammonium tetrafluoroborate, ammonium triethylmethyltetrafluoroborate or the like.
  • the operating voltage is generally 0 to 2.7V, and the maximum operating temperature is 65 °C. This is because the voltage above 2.7V will cause the electrochemical reaction of the electrolyte, affecting the normal operation and service life of the supercapacitor.
  • the temperature above 65 °C will lead to an increase in the leakage current of the capacitor, the attenuation of the capacity, and the vaporization of the solvent of the electrolyte, resulting in bulging of the capacitor unit, posing a safety hazard.
  • the organic electrolyte is flammable, especially the most widely used acetonitrile solvent electrolyte.
  • the flash point of acetonitrile is only 6 °C. This has led to limitations in the application of supercapacitors in many fields. For example, when a large supercapacitor is used as an energy storage device for energy storage and feedback in the field of rail transit, continuous high current charging and discharging may cause the temperature of the supercapacitor to rise, posing a safety hazard. Other military and other fields require energy storage devices to operate at high temperatures, which limits the further expansion of supercapacitor applications.
  • An object of the present invention is to solve the above problems and to provide a supercapacitor organic electrolyte containing inorganic nanoparticles.
  • a supercapacitor organic electrolyte containing inorganic nanoparticles consisting of the following components: an organic solvent, an electrolyte salt, and nano inorganic compound particles.
  • the nano inorganic compound particles are nano magnesium oxide, nano aluminum oxide or nano silicon oxide.
  • the nano inorganic compound particles account for 0.01% to 5% by mass of the electrolyte.
  • the electrolyte salt is tetraethylammonium tetrafluoroborate, ammonium tetramethyltetrafluoroborate, ammonium triethylmethyltetrafluoroborate, ammonium N,N-diethylpyrrolidine tetrafluoroborate, N- Methyl-N-ethylpyrrolidine ammonium tetrafluoroborate, N,N-dimethylpyrrolidine tetrafluoroboron Ammonium acid or ammonium 5-azaspiro[4,4]decane tetrafluoroborate.
  • the organic solvent is acetonitrile, propylene carbonate, ethylene carbonate, dimethyl carbonate, r-butyrolactone, butylene carbonate or diethyl carbonate.
  • the nano inorganic compound particles have a particle diameter of 20 to 100 nm.
  • the modification is carried out before the nano inorganic compound particles are added to the electrolyte.
  • the modification of the nano inorganic compound particles comprises the steps of: adding a mixture of formaldehyde and diethyl ether in a volume ratio of 1:2 in a heating vessel, and a ratio of a liquid to a mixture of the nano inorganic compound particles and formaldehyde and diethyl ether is 1 g: 5mL, heated to 45 ° C on a magnetic stirrer, adding nano-inorganic compound particles to the solution under constant stirring, stirring for 30 min, adding 3 times the mass of nano-inorganic compound particles of triethanolamine, stirring for 45 min, adding the mass of nano-inorganic compound particles 5 times hexamethoxymethyl melamine, adding silicone oil to the container, the silicone oil is added in an amount of 30% of hexamethoxymethyl melamine, and the temperature is raised to 75 ° C, and then 20% by weight of the nano inorganic compound particles is added to the stearamide.
  • the reaction is cooled to 50 ° C, then add graphene, glass beads and sodium dibutyl naphthalene sulfonate, graphene, glass beads and sodium dibutyl naphthalene sulfonate are added in the amount of nano-inorganic compound particles.
  • 3 times wherein the mass ratio of graphene, glass microbeads to sodium dibutylnaphthalene sulfonate is 1:2:1, the temperature is raised to 120 ° C, and stirring is maintained for 50 min, plus Sodium hydroxide of the same quality as the nano inorganic compound particles and kept for 15 minutes, cooled, dried and then calcined in a muffle furnace at a temperature of 750 ° C for 2 h.
  • the present invention in order to improve the dispersibility of the nano inorganic compound particles in the electrolyte and improve the safety performance of the electrolyte, the present invention is modified before the nano inorganic compound particles are added to the electrolyte, and the graphene is a carbon.
  • the particles are highly uniformly dispersed in the electrolyte; sodium dibutylnaphthalene sulfonate can cause the surface of the nano inorganic compound particles to have a charge, and form a diffusion electric double layer around the particles to generate an electromotive force and increase the absolute value of the surface potential of the particles.
  • stearic acid amide is added to reduce the interfacial tension between the particles and the electrolyte, causing the contact angle to be small, the wettability to be enhanced, and the repellency of the solvated film to be enhanced.
  • the modification of the nano inorganic compound particles comprises the following steps:
  • the secondary modified nano inorganic compound particles and the perchloric acid having a mass concentration of 50-60% are uniformly mixed according to the ratio of material to liquid of 1g: 20-30mL, heated to 90-150 ° C for 24 hours, cooled, filtered, washed with water.
  • the nano inorganic compound particles are obtained by vacuum drying.
  • the step (1) mixes the nano inorganic compound particles with a dimethylformamide solution and an acid solution having a mass concentration of 30-50%, and is supplemented by stirring to expand the contact surface of the nano inorganic compound particles with the liquid.
  • the nano-inorganic compound particles are uniformly dispersed, and the specific solvent combination system of the dimethylformamide solution and the acid solution having a mass concentration of 30-50% can make the nano-inorganic compound particles more uniformly dispersed in the system and effectively avoid the nano-inorganic compound. Particle agglomeration.
  • Step (1) firstly dispersing the nano inorganic compound particles uniformly, thereby facilitating the shearing of the step (2), and hydrolyzing the nano inorganic compound particles uniformly dispersed in the step (1) with the specific chemical shear liquid of the present invention, which is effective
  • the nano inorganic compound particles are cut to obtain uniform nano inorganic compound particles having a relatively uniform length (about 100-150 nm in length), and such nano inorganic compound particles can be more excellent in a smaller amount when used for an electrode material.
  • Conductive and thermal conductivity are used for an electrode material.
  • Step (3) The homogenized nano inorganic compound particles obtained in the step (2) are hydrothermally reacted in perchloric acid, and the perchloric acid molecules can intercalate and swell the nano inorganic compound particles to separate the nano inorganic compound particles from each other and Surface high reactivity is exposed to achieve selective functionalization. Similar to the surfactant, it has amphiphilicity and assists in the dispersion of the nano inorganic compound particles, thereby greatly improving the uniform dispersion performance of the nano inorganic compound particles in the electrolyte.
  • the acid solution is a mixture of concentrated nitric acid having a mass concentration of 70% and concentrated sulfuric acid having a mass concentration of 98% in a volume ratio of 1-2:1.
  • the chemical shearing solution is a mixture of a sodium molybdate solution having a concentration of 0.5 to 0.8 mol/L and a silicomolybdic acid solution having a concentration of 0.3 to 0.5 mol/L in a volume ratio of 1:1.
  • the invention has the beneficial effects of improving the high temperature resistance and the withstand voltage performance of the prepared supercapacitor and prolonging the service life thereof, thereby enhancing the safety performance of the super capacitor.
  • the materials used in the examples of the present invention are all raw materials commonly used in the art, and the methods used in the examples are all conventional methods in the art.
  • Magnesium oxide particles having a mass ratio of 1% and a particle diameter of 30 to 50 nm were added to 1 mol/L of a 5-azaspiro[4,4]nonane tetrafluoroborate/acetonitrile system organic electrolytic solution, and the mixture was uniformly stirred.
  • the specific capacity of the supercapacitor prepared by this electrolyte was 98% of the organic electrolyte without inorganic nanoparticles, and the internal resistance was 1.2 times. After 80 ° C, 2.85 V high temperature float charge test for 2 months, the capacity retention rate was 89%, and the internal resistance increased by 65%.
  • the nano inorganic compound particles are modified before being added to the electrolyte, and the following steps are included: adding a mixture of formaldehyde and diethyl ether in a volume ratio of 1:2 in a heating vessel, and the ratio of the liquid to liquid of the mixture of nano-silica and formaldehyde and diethyl ether is 1g: 5mL, heated to 45 ° C on a magnetic stirrer, adding nano-silica to the solution under constant stirring, stirring for 30 min, adding 3 times the mass of nano-silica triethanolamine, stirring for 45 min, adding 5 mass of nano-silica Double hexamethoxymethyl melamine, adding silicone oil to the container, the silicone oil is added in an amount of 30% of hexamethoxymethyl melamine, and the temperature is raised to 75 ° C, and then 20% by weight of nanosilica is added to the stearylamine.
  • a silica particle having a particle diameter of 0.1% and having a particle diameter of 20 to 30 nm was added and stirred uniformly.
  • the specific capacity of the supercapacitor prepared by this electrolyte was 95% of the organic electrolyte without inorganic nanoparticles, and the internal resistance was 1.2 times. After 80 ° C, 2.85 V high temperature float charge test for 2 months, the capacity retention rate was 86%, and the internal resistance increased by 61%.
  • Modification of nano-alumina includes the following steps:
  • Nano alumina (2) Mixing the primary modified nano-alumina with the chemical shear solution according to the ratio of material to liquid of 1g: 15-30mL, heating to 230-260 ° C, hydrothermal reaction for 4-6 h, cooling, washing with water to obtain secondary modification.
  • Nano alumina (2) Mixing the primary modified nano-alumina with the chemical shear solution according to the ratio of material to liquid of 1g: 15-30mL, heating to 230-260 ° C, hydrothermal reaction for 4-6 h, cooling, washing with water to obtain secondary modification.
  • the secondary modified nano-alumina and the perchloric acid with a mass concentration of 50-60% are uniformly mixed according to the ratio of material to liquid of 1g: 20-30mL, heated to 90-150 ° C for 24 hours, cooled, filtered, washed with water, After drying in vacuum, the modified nano-alumina is obtained; wherein the acid solution is a mixture of concentrated nitric acid having a mass concentration of 70% and a concentrated sulfuric acid having a mass concentration of 98% in a volume ratio of 1:1; the chemical shearing solution is a concentration A mixture of 0.5 mol/L sodium molybdate solution and a concentration of 0.3 mol/L silicomolybdic acid solution in a volume ratio of 1:1.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
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  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

一种含无机纳米颗粒的超级电容器有机电解液，由以下各组分组成：有机溶剂、电解质盐和纳米无机化合物颗粒。该电解液提高了制备的超级电容器的耐高温性能、并延长了其使用寿命，从而增强了超级电容器的安全性能。

Description

一种含无机纳米颗粒的超级电容器有机电解液 技术领域
本发明涉及超级电容器技术领域，具体涉及一种含无机纳米颗粒的超级电容器有机电解液。
背景技术
电化学电容器又称超级电容器(super capacitors)，极端电容器等，是介于二次电池与传统静电电容器之间的新型能量储存器件，比传统静电电容器有更高的能量密度，比二次电池有更大的功率密度，其具有功率密度高、循环寿命长、工作温度范围宽、循环稳定性好，免维护，环境友好等优点，已经在很多领域，如轨道交通、风力发电、油电混合动力车、电子器件的后备电源等展现出广阔的应用前景。
当前超级电容器有机体系电解液主要由有机溶剂和有机盐组成。溶剂包括如乙腈、碳酸丙烯酯等，有机盐包括四乙基四氟硼酸铵、三乙基甲基四氟硼酸铵等。工作电压一般在0～2.7V，最高工作温度为65℃。这是由于电压高于2.7V会导致电解液的电化学反应，影响超级电容器的正常工作和使用寿命。而温度高于65℃则会导致电容器漏电流的增大，容量的衰减，加上电解液的溶剂的气化，导致电容器单体的鼓胀，造成安全隐患。
有机电解液易燃，尤其是应用最为广泛的乙腈溶剂电解液，乙腈闪点仅为6℃。这点导致了超级电容器在很多领域中的应用受到限制。例如大型超级电容器用于轨道交通领域作为能量储存和回馈的储能器件时，连续大电流充放电会导致超级电容器温度升高，造成安全隐患。另外一些军事等领域要求储能器件在高温下工作，这都限制了超级电容器应用的进一步扩大。
发明内容
本发明的目的是为了解决上述问题，提供一种含无机纳米颗粒的超级电容器有机电解液。
为了达到上述发明目的，本发明采用以下技术方案：
一种含无机纳米颗粒的超级电容器有机电解液，所述电解液由以下各组分组成：有机溶剂、电解质盐和纳米无机化合物颗粒。
作为优选，纳米无机化合物颗粒为纳米氧化镁、纳米氧化铝或纳米氧化硅。
作为优选，所述纳米无机化合物颗粒在电解液中所占的质量百分数为0.01-5％。
作为优选，所述电解质盐为四乙基四氟硼酸铵、四甲基四氟硼酸铵、三乙基甲基四氟硼酸铵、N,N-二乙基吡咯烷四氟硼酸铵、N-甲基-N-乙基吡咯烷四氟硼酸铵、N,N-二甲基吡咯烷四氟硼 酸铵或5-氮杂螺环[4,4]壬烷四氟硼酸铵。
作为优选，所述的有机溶剂为乙腈、碳酸丙烯酯、碳酸乙烯酯、碳酸二甲酯、r-丁内酯、碳酸丁烯酯或碳酸二乙酯。
作为优选，所述纳米无机化合物颗粒的粒径为20-100nm。
作为优选，在纳米无机化合物颗粒加入电解液前进行改性。
作为优选，纳米无机化合物颗粒进行改性包括以下步骤：在加热容器中加入体积比为1:2的甲醛与乙醚混合液，纳米无机化合物颗粒与甲醛、乙醚的混合液的料液比为1g:5mL，在磁力搅拌器上加热至45℃，在不断搅拌下向溶液加入纳米无机化合物颗粒，搅拌30min后加入纳米无机化合物颗粒质量3倍的三乙醇胺，继续搅拌45min后加入纳米无机化合物颗粒质量的5倍的六甲氧基甲基三聚氰胺，向容器中加入硅油，硅油的加入量为六甲氧基甲基三聚氰胺的30％，升温至75℃，然后加入纳米无机化合物颗粒质量的20％的硬脂酰胺，反应2h，降温至50℃，再加入石墨烯、玻璃微珠与二丁基萘磺酸钠，石墨烯、玻璃微珠与二丁基萘磺酸钠的加入量为纳米无机化合物颗粒质量的3倍，其中，石墨烯、玻璃微珠与二丁基萘磺酸钠的质量比为1:2:1，升温至120℃，并保持搅拌50min，加入与纳米无机化合物颗粒质量相同的氢氧化钠并保温15min，冷却、干燥后在马弗炉中焙烧，温度750℃，时间2h，取出后冷却至65℃时放入正丁醇中静置10min后过滤，用无水乙醇洗涤沉淀物10次，在真空干燥箱内进行多温度段干燥，研磨得到改性的纳米无机化合物颗粒；其中，多温度段干燥的温度段分别为60℃、100℃、155℃，时间均为45min。
在本技术方案中，为了提高纳米无机化合物颗粒在电解液中的分散性并提高电解液的安全性能，本发明在将纳米无机化合物颗粒加入电解液前进行改性，石墨烯是一种由碳原子构成的单层片状结构的新材料，具有强度高，比表面积大，高化学反应活性，高填充性的特点；玻璃微珠粒度合适，流动性好，分散度高，可以使纳米无机化合物颗粒在电解液中高度均匀分散；二丁基萘磺酸钠可以使纳米无机化合物颗粒表面带有电荷，并在颗粒周围形成扩散双电层，产生电动势，增大颗粒表面电位的绝对值。同时加入了硬脂酰胺，用于降低颗粒与电解液的界面张力，引起接触角变小，润湿性增强，提高溶剂化膜的排斥作用。
作为优选，纳米无机化合物颗粒进行改性包括以下步骤：
(1)将纳米无机化合物颗粒、质量浓度30-50％的二甲基甲酰胺溶液及酸溶液按照1g：25-30mL：10-12mL的料液比混合，控制温度65-85℃下搅拌混合30-50min，过滤，分别用水和无水乙醇洗涤，130-150℃下真空干燥30-60min得初级改性纳米无机化合物颗粒；
(2)将初级改性纳米无机化合物颗粒与化学剪切液按照1g：15-30mL的料液比混合，加热至 230-260℃，水热反应4-6h，冷却，水洗，得次级改性纳米无机化合物颗粒；
(3)次级改性纳米无机化合物颗粒与质量浓度50-60％的高氯酸按照1g：20-30mL的料液比混合均匀，加热至90-150℃保持24小时，冷却，过滤，水洗，真空干燥后得改性纳米无机化合物颗粒。
在本技术方案中，步骤(1)将纳米无机化合物颗粒与质量浓度30-50％的二甲基甲酰胺溶液及酸溶液混合，同时辅以搅拌，以扩大纳米无机化合物颗粒与液体的接触面，使得纳米无机化合物颗粒分散均匀，质量浓度30-50％的二甲基甲酰胺溶液及酸溶液的特定溶剂组合体系，能够使得纳米无机化合物颗粒能在体系中分散更均匀，有效避免纳米无机化合物颗粒团聚。
步骤(1)先将纳米无机化合物颗粒分散均匀，这样利于步骤(2)的剪切，将步骤(1)分散均匀的纳米无机化合物颗粒与本发明特定的化学剪切液水热反应，能有效切断纳米无机化合物颗粒，获得长度较均一(长度大约在100-150nm)左右的均一化纳米无机化合物颗粒，这样的纳米无机化合物颗粒在用于电极材料时，可以用更少的量发挥更优异的导电导热效果。步骤(3)将步骤(2)得到的均一化纳米无机化合物颗粒在高氯酸中水热反应，高氯酸分子能够插层、溶胀纳米无机化合物颗粒，使纳米无机化合物颗粒彼此分开并将其表面高反应活性暴露出来，从而实现选择性功能化。与表面活性剂类似，具有两亲性，协助纳米无机化合物颗粒分散，从而大大提高纳米无机化合物颗粒在电解液中的均匀分散性能。
作为优选，所述酸溶液为质量浓度70％的浓硝酸与质量浓度98％的浓硫酸按照1-2:1的体积比的混合物。
作为优选，所述化学剪切液为浓度0.5-0.8moL/L的钼酸钠溶液与浓度0.3-0.5moL/L的硅钼酸溶液按照1:1的体积比的混合物。
本发明与现有技术相比，有益效果是：提高了制备的超级电容器耐高温性能和耐电压性能，以及延长了其使用寿命，从而增强了超级电容器的安全性能。
具体实施方式
下面通过具体实施例对本发明的技术方案作进一步描述说明。
如果无特殊说明，本发明的实施例中所采用的原料均为本领域常用的原料，实施例中所采用的方法，均为本领域的常规方法。
实施例1：
向1mol/L的四乙基四氟硼酸铵/乙腈体系有机电解液中加入质量比0.1％的粒径为20-30nm的 氧化硅颗粒，搅拌均匀。以此电解液制作的超级电容器的比容量为不加无机纳米颗粒的有机电解液的95％，内阻为1.2倍。经过80℃，2.85V高温浮充测试2个月，容量保持率为86％，内阻增大61％。
实施例2：
向1mol/L的三乙基甲基四氟硼酸铵/乙腈体系有机电解液中加入质量比0.05％的粒径为50-100nm的氧化铝颗粒，搅拌均匀。以此电解液制作的超级电容器的比容量为不加无机纳米颗粒的有机电解液的97％，内阻为1.15倍。经过80℃，2.85V高温浮充测试2个月，容量保持率为84％，内阻增大70％。
实施例3：
向1mol/L的5-氮杂螺环[4,4]壬烷四氟硼酸铵/乙腈体系有机电解液中加入质量比1％的粒径为30-50nm的氧化镁颗粒，搅拌均匀。以此电解液制作的超级电容器的比容量为不加无机纳米颗粒的有机电解液的98％，内阻为1.2倍。经过80℃，2.85V高温浮充测试2个月，容量保持率为89％，内阻增大65％。
实施例4：
向1mol/L的5-氮杂螺环[4,4]壬烷四氟硼酸铵/乙腈体系有机电解液中加入质量比1％的粒径为30-50nm的氧化铝颗粒，搅拌均匀。以此电解液制作的超级电容器的比容量为不加无机纳米颗粒的有机电解液的98％，内阻为1.1倍。经过80℃，2.85V高温浮充测试2个月，容量保持率为88％，内阻增大68％。
实施例5
在纳米无机化合物颗粒加入电解液前进行改性，包括以下步骤：在加热容器中加入体积比为1:2的甲醛与乙醚混合液，纳米氧化硅与甲醛、乙醚的混合液的料液比为1g:5mL，在磁力搅拌器上加热至45℃，在不断搅拌下向溶液加入纳米氧化硅，搅拌30min后加入纳米氧化硅质量3倍的三乙醇胺，继续搅拌45min后加入纳米氧化硅质量的5倍的六甲氧基甲基三聚氰胺，向容器中加入硅油，硅油的加入量为六甲氧基甲基三聚氰胺的30％，升温至75℃，然后加入纳米氧化硅质量的20％的硬脂酰胺，反应2h，降温至50℃，再加入石墨烯、玻璃微珠与二丁基萘磺酸钠，石墨烯、玻璃微珠与二丁基萘磺酸钠的加入量为纳米氧化硅质量的3倍，其中，石墨烯、玻璃微珠与二丁基萘磺酸钠的质量比为1:2:1，升温至120℃，并保持搅拌50min，加入与纳米氧化硅质量相同的氢氧化钠并保温15min，冷却、干燥后在马弗炉中焙烧，温度750℃，时间2h，取出后冷却至65℃时放入正丁醇中静置10min后过滤，用无水乙醇洗涤沉淀物10次，在真空干燥箱内进行多温度段干燥，研磨得到改性的纳米氧化硅；其中，多温度 段干燥的温度段分别为60℃、100℃、155℃，时间均为45min。
向1mol/L的四乙基四氟硼酸铵/乙腈体系有机电解液中加入质量比0.1％的粒径为20-30nm的氧化硅颗粒，搅拌均匀。以此电解液制作的超级电容器的比容量为不加无机纳米颗粒的有机电解液的95％，内阻为1.2倍。经过80℃，2.85V高温浮充测试2个月，容量保持率为86％，内阻增大61％。
实施例6
纳米氧化铝进行改性包括以下步骤：
(1)将纳米氧化铝、质量浓度30-50％的二甲基甲酰胺溶液及酸溶液按照1g：25-30mL：10-12mL的料液比混合，控制温度65-85℃下搅拌混合30-50min，过滤，分别用水和无水乙醇洗涤，130-150℃下真空干燥30-60min得初级改性纳米氧化铝；
(2)将初级改性纳米氧化铝与化学剪切液按照1g：15-30mL的料液比混合，加热至230-260℃，水热反应4-6h，冷却，水洗，得次级改性纳米氧化铝；
(3)次级改性纳米氧化铝与质量浓度50-60％的高氯酸按照1g：20-30mL的料液比混合均匀，加热至90-150℃保持24小时，冷却，过滤，水洗，真空干燥后得改性纳米氧化铝；其中，所述酸溶液为质量浓度70％的浓硝酸与质量浓度98％的浓硫酸按照1:1的体积比的混合物；所述化学剪切液为浓度0.5moL/L的钼酸钠溶液与浓度0.3moL/L的硅钼酸溶液按照1:1的体积比的混合物。
向1mol/L的5-氮杂螺环[4,4]壬烷四氟硼酸铵/乙腈体系有机电解液中加入质量比1％的粒径为30-50nm的氧化铝颗粒，搅拌均匀。以此电解液制作的超级电容器的比容量为不加无机纳米颗粒的有机电解液的98％，内阻为1.1倍。经过80℃，2.85V高温浮充测试2个月，容量保持率为88％，内阻增大68％。

Claims (11)

  1. 一种含无机纳米颗粒的超级电容器有机电解液，其特征在于，所述电解液由以下各组分组成：有机溶剂、电解质盐和纳米无机化合物颗粒。
  2. 根据权利要求1所述的一种含无机纳米颗粒的超级电容器有机电解液，其特征在于，纳米无机化合物颗粒为纳米氧化镁、纳米氧化铝或纳米氧化硅。
  3. 根据权利要求1所述的一种含无机纳米颗粒的超级电容器有机电解液，其特征在于，所述纳米无机化合物颗粒在电解液中所占的质量百分数为0.01-5％。
  4. 根据权利要求1所述的一种含无机纳米颗粒的超级电容器有机电解液，其特征在于，所述电解质盐为四乙基四氟硼酸铵、四甲基四氟硼酸铵、三乙基甲基四氟硼酸铵、N,N-二甲基吡咯烷四氟硼酸铵、N,N-二乙基吡咯烷四氟硼酸铵、N-甲基-N-乙基吡咯烷四氟硼酸铵、N,N-二甲基吡咯烷四氟硼酸铵或5-氮杂螺环[4,4]壬烷四氟硼酸铵。
  5. 根据权利要求1所述的一种含无机纳米颗粒的超级电容器有机电解液，其特征在于，所述的有机溶剂为乙腈、碳酸丙烯酯、碳酸乙烯酯、碳酸二甲酯、r-丁内酯、碳酸丁烯酯或碳酸二乙酯。
  6. 根据权利要求1所述的一种含无机纳米颗粒的超级电容器有机电解液，其特征在于，所述纳米无机化合物颗粒的粒径为20-100nm。
  7. 根据权利要求1所述的一种含无机纳米颗粒的超级电容器有机电解液，其特征在于，在纳米无机化合物颗粒加入电解液前进行改性。
  8. 根据权利要求7所述的一种含无机纳米颗粒的超级电容器有机电解液，其特征在于，纳米无机化合物颗粒进行改性包括以下步骤：在加热容器中加入体积比为1:2的甲醛与乙醚混合液，纳米无机化合物颗粒与甲醛、乙醚的混合液的料液比为1g:5mL，在磁力搅拌器上加热至45℃，在不断搅拌下向溶液加入纳米无机化合物颗粒，搅拌30min后加入纳米无机化合物颗粒质量3倍的三乙醇胺，继续搅拌45min后加入纳米无机化合物颗粒质量的5倍的六甲氧基甲基三聚氰胺，向容器中加入硅油，硅油的加入量为六甲氧基甲基三聚氰胺的30％，升温至75℃，然后加入纳米无机化合物颗粒质量的20％的硬脂酰胺，反应2h，降温至50℃，再加入石墨烯、玻璃微珠与二丁基萘磺酸钠，石墨烯、玻璃微珠与二丁基萘磺酸钠的加入量为纳米无机化合物颗粒质量的3倍，其中，石墨烯、玻璃微珠与二丁基萘磺酸钠的质量比为1:2:1，升温至120℃，并保持搅拌50min，加入与纳米无机化合物颗粒质量相同的氢氧化钠并保温15min，冷却、干燥后在马弗炉中焙烧，温度750℃，时间2h，取出后冷却至65℃时放入正丁醇中静置10min后过滤，用无水乙醇洗涤沉淀物10次，在真空干燥箱内进行多温度段干燥，研磨得到改性的纳米无机化合物颗粒；其中，多温度段干燥的温度段分别为60℃、 100℃、155℃，时间均为45min。
  9. 根据权利要求7所述的一种含无机纳米颗粒的超级电容器有机电解液，其特征在于，纳米无机化合物颗粒进行改性包括以下步骤：
    (1)将纳米无机化合物颗粒、质量浓度30-50％的二甲基甲酰胺溶液及酸溶液按照1g：25-30mL：10-12mL的料液比混合，控制温度65-85℃下搅拌混合30-50min，过滤，分别用水和无水乙醇洗涤，130-150℃下真空干燥30-60min得初级改性纳米无机化合物颗粒；
    (2)将初级改性纳米无机化合物颗粒与化学剪切液按照1g：15-30mL的料液比混合，加热至230-260℃，水热反应4-6h，冷却，水洗，得次级改性纳米无机化合物颗粒；
    (3)次级改性纳米无机化合物颗粒与质量浓度50-60％的高氯酸按照1g：20-30mL的料液比混合均匀，加热至90-150℃保持24小时，冷却，过滤，水洗，真空干燥后得改性纳米无机化合物颗粒。
  10. 根据权利要求9所述的一种含无机纳米颗粒的超级电容器有机电解液，其特征在于：所述酸溶液为质量浓度70％的浓硝酸与质量浓度98％的浓硫酸按照1-2:1的体积比的混合物。
  11. 根据权利要求9所述的一种含无机纳米颗粒的超级电容器有机电解液，其特征在于：所述化学剪切液为浓度0.5-0.8moL/L的钼酸钠溶液与浓度0.3-0.5moL/L的硅钼酸溶液按照1:1的体积比的混合物。
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