阅读说明：本技术 一种新型非对称纤维状柔性超级电容器的制备方法 (Preparation method of novel asymmetric fibrous flexible supercapacitor ) 是由 董立峰 张乾 杨丰键 章朝哲 于建华 隋静 董红周 于 2020-11-16 设计创作，主要内容包括：一种新型非对称纤维状柔性超级电容器的制备方法,其特征在于该方法利用原位生长的碳纳米管层为外电极,并利用一步法去除硬模板二氧化硅和灌装电解质溶液,主要包括以下步骤：首先,以高锰酸钾作为锰源,利用水热法在导电丝上沉积生长二氧化锰；其次,利用水热法在二氧化锰外包覆二氧化硅,利用浸渍法将金属催化剂附着于其表面,并利用化学气相沉积法制备碳纳米管层,然后将其与聚乙烯醇/氢氧化钾电解质溶液一同转移至反应釜中,在一定温度下保温一定时间,即得到了一种新型非对称纤维状柔性超级电容器。本发明的优点是原位生长的碳纳米管层外电极,使其相互间接触良好。在灌装电解质溶液的同时,刻蚀去除二氧化硅层,简化了工艺流程。(A preparation method of a novel asymmetric fibrous flexible supercapacitor is characterized in that the method utilizes a carbon nanotube layer grown in situ as an external electrode, and utilizes a one-step method to remove hard template silicon dioxide and fill electrolyte solution, and mainly comprises the following steps: firstly, taking potassium permanganate as a manganese source, and depositing and growing manganese dioxide on a conductive wire by using a hydrothermal method; secondly, coating silicon dioxide outside manganese dioxide by using a hydrothermal method, attaching a metal catalyst to the surface of the manganese dioxide by using an impregnation method, preparing a carbon nanotube layer by using a chemical vapor deposition method, transferring the carbon nanotube layer and a polyvinyl alcohol/potassium hydroxide electrolyte solution into a reaction kettle together, and preserving heat for a certain time at a certain temperature to obtain the novel asymmetric fibrous flexible supercapacitor. The invention has the advantage that the carbon nano tube layer with in-situ growth has good mutual contact with the outer electrode. When the electrolyte solution is filled, the silicon dioxide layer is removed by etching, so that the process flow is simplified.)

1. A novel preparation method of an asymmetric fibrous flexible supercapacitor comprises a manganese dioxide nano tube inner electrode taking a conductive wire as a substrate, a carbon nano tube layer outer electrode and a polyvinyl alcohol/potassium hydroxide solid electrolyte solution between the two electrodes, and is characterized in that the preparation process of the supercapacitor adopts a method for growing the carbon nano tube layer in situ, so that the carbon nano tube layer is well contacted with each other, the utilization rate of the electrodes is effectively improved, and a hydrothermal method is utilized, so that the etching removal of a hard template silicon dioxide layer and the filling of the polyvinyl alcohol/potassium hydroxide electrolyte solution are completed simultaneously, the process is simplified, and the preparation method of the novel asymmetric fibrous flexible supercapacitor comprises the following steps:

(1) sequentially soaking and cleaning the conductive wire by using acetone and dilute hydrochloric acid solution, and then washing the conductive wire to be neutral by using deionized water; transferring the treated conductive wire and a potassium permanganate solution with a certain concentration into a reaction kettle, and placing the reaction kettle into a drying oven with the reaction temperature raised for heat preservation for a certain time;

(2) placing the product in a mixed solution of ammonia water, tetraethyl orthosilicate, ethanol and deionized water, keeping the reaction at a reaction temperature for a certain reaction time, taking out and washing the product to be neutral, then soaking the product in a cobalt-based soluble salt solution with a certain concentration for a certain time, taking out and drying the product;

(3) placing the product in a tubular furnace, introducing acetylene into the tubular furnace to atmospheric pressure under a certain reaction temperature condition by taking argon-hydrogen mixed gas as carrier gas and acetylene as carbon source gas, keeping the reaction temperature for a certain time, naturally cooling the reaction product after the reaction is finished, and taking out the product;

(4) and transferring the product and a polyvinyl alcohol/potassium hydroxide solution with a certain concentration into a reaction kettle, preserving the heat at a certain temperature for a certain time, taking out, and drying at room temperature to obtain the novel asymmetric fibrous flexible supercapacitor.

2. The method for preparing the novel asymmetric fibrous flexible supercapacitor according to claim 1, wherein the conductive wires in the step (1) can be carbon fibers, copper wires, nickel wires, stainless steel wires; the concentration of the potassium permanganate solution is 0.003-0.006 mol/L, the reaction temperature is 80-150 ℃, and the reaction time is 8-24 h.

3. The method for preparing the novel asymmetric fibrous flexible supercapacitor according to claim 1, wherein the reaction temperature in the step (2) is 50 ℃ to 80 ℃. The reaction time is 8-12 h, the cobalt-based soluble salt is cobalt chloride, cobalt sulfate or cobalt nitrate, and the soaking time is 15-20 min.

4. The preparation method of the fibrous coaxial asymmetric flexible supercapacitor according to claim 1, wherein the reaction temperature of the tubular furnace in the step (3) is 600-900 ℃, and the reaction time is 5-10 min.

5. The preparation method of the fibrous coaxial asymmetric flexible supercapacitor according to claim 1, wherein the reaction temperature in the step (4) is 70-90 ℃ and the reaction time is 4-12 h.

Technical Field

The invention belongs to the technical field of new energy storage, and relates to a preparation method of a novel asymmetric fibrous flexible supercapacitor.

Technical Field

With the increasing demand of people for fossil energy, environmental pollution is also becoming more serious and affects the normal life and production of human beings, and at the moment, the development and research of novel energy utilization and storage modes are promoted by people. The super capacitor is a novel high-efficiency energy storage device between a traditional capacitor and a rechargeable battery, and has the characteristics of quick charge and discharge of the capacitor and the energy storage characteristic of the battery. With the development of miniaturization of electronic devices, flexible supercapacitors have received more and more extensive attention, wherein fibrous flexible supercapacitors are considered to be an electrochemical energy storage device with great potential by virtue of their small size, excellent mechanical stability and high electrochemical performance. According to the difference of the relative positions of two electrodes of the capacitor, the fibrous flexible super capacitor can be generally divided into a fibrous super capacitor with a parallel structure, a fibrous super capacitor with a winding structure, a fibrous super capacitor with a coaxial structure and the like. The coaxial structure can also ensure that the two electrodes can not be peeled off when the supercapacitor is bent or kinked, thereby prolonging the service life of the device. On the other hand, due to the coaxial structure characteristics of the inner electrode and the outer electrode of the capacitor, the device is difficult to manufacture and complex in process. The current common methods are dipping-pulling method and two-dimensional sheet-shaped outer electrode coating method. In the dip-draw method, a substrate is first immersed in a solution containing an active material or a colloidal electrolyte solution, held for a certain period of time, and then taken out and dried to attach the electrode active material or the electrolyte solution to the surface of the one-dimensional substrate. This method has disadvantages in that the uniformity of the distance between the two electrodes and the good contact of the electrode active material with the electrolyte solution cannot be ensured, resulting in the degradation of the device performance. In the two-dimensional sheet-shaped outer electrode coating method, the outer electrode soaked by the electrolyte solution is coated on the inner electrode by the action of external force, and the method has the defects of high interface resistance and complex process in the device. In order to solve the problems, the patent provides a method for realizing the removal of a hard template silicon dioxide layer and the filling of an electrolyte solution by in-situ growth of active substances of inner and outer electrodes and a one-step method.

The conductive wire is used as a current collector of an inner electrode of a fibrous flexible super capacitor, and the excellent conductivity and mechanical property of the conductive wire are beneficial to the application of the conductive wire in the super capacitor. The good conductivity of the conductive wire effectively solves the defect of poor conductivity of pseudocapacitance materials such as manganese dioxide; the excellent mechanical property of the conductive wire can ensure that the super capacitor has longer service life.

The invention relates to a preparation method of a novel asymmetric fibrous flexible supercapacitor, which comprises the steps of firstly depositing and growing a manganese dioxide pseudocapacitance material on the surface of a conductive wire by using a hydrothermal method, then coating a hard template silicon dioxide layer, uniformly dispersing a cobalt-based catalyst on the surface of the hard template silicon dioxide layer, preparing a carbon nanotube layer by using a chemical vapor deposition method, then etching and removing the hard template silicon dioxide layer by using polyvinyl alcohol/potassium hydroxide under the hydrothermal condition, and simultaneously completing electrolyte solution filling, thus obtaining the novel asymmetric fibrous flexible supercapacitor. The method overcomes the defects of the existing production process, and has the advantages of simple process, wide application range, important research value and application prospect.

Disclosure of Invention

The invention relates to a preparation method of a novel asymmetric fibrous flexible supercapacitor, wherein in the preparation process, an outer electrode of the supercapacitor is prepared by adopting a carbon nanotube layer in-situ growth mode, then a hard template silicon dioxide layer is removed by utilizing polyvinyl alcohol/potassium hydroxide etching, and the filling of an electrolyte solution is completed, so that the novel asymmetric fibrous flexible supercapacitor is obtained, and the preparation process mainly comprises the following steps:

(1) sequentially soaking and cleaning the conductive wire by using acetone and dilute hydrochloric acid solution, and then washing the conductive wire to be neutral by using deionized water; transferring the treated conductive wire and a potassium permanganate solution with a certain concentration into a reaction kettle, and placing the reaction kettle into a drying oven with the reaction temperature raised for heat preservation for a certain time;

(2) placing the product in a mixed solution of ammonia water, tetraethyl orthosilicate, ethanol and deionized water, keeping the reaction at a reaction temperature for a certain reaction time, taking out and washing the product to be neutral, then soaking the product in a cobalt-based soluble salt solution with a certain concentration for a certain time, taking out and drying the product;

(3) placing the product in a tubular furnace, introducing acetylene into the tubular furnace to atmospheric pressure under a certain reaction temperature condition by taking argon-hydrogen mixed gas as carrier gas and acetylene as carbon source gas, keeping the reaction temperature for a certain time, naturally cooling the reaction product after the reaction is finished, and taking out the product;

(4) and transferring the product and a polyvinyl alcohol/potassium hydroxide solution with a certain concentration into a reaction kettle, preserving the heat at a certain temperature for a certain time, taking out, and drying at room temperature to obtain the novel asymmetric fibrous flexible supercapacitor.

2. The method for preparing the novel asymmetric fibrous flexible supercapacitor according to claim 1, wherein the conductive wires in the step (1) can be carbon fibers, copper wires, nickel wires, stainless steel wires; the concentration of the potassium permanganate solution is 0.003-0.006 mol/L, the reaction temperature is 80-150 ℃, and the reaction time is 8-24 h.

3. The method for preparing the novel asymmetric fibrous flexible supercapacitor according to claim 1, wherein the reaction temperature in the step (2) is 50 ℃ to 80 ℃. The reaction time is 8-12 h, the cobalt-based soluble salt is cobalt chloride, cobalt sulfate or cobalt nitrate, and the soaking time is 15-20 min.

4. The preparation method of the fibrous coaxial asymmetric flexible supercapacitor according to claim 1, wherein the reaction temperature of the tubular furnace in the step (3) is 700-900 ℃ and the reaction time is 5-10 min.

5. The preparation method of the fibrous coaxial asymmetric flexible supercapacitor according to claim 1, wherein the reaction temperature in the step (4) is 70-90 ℃ and the reaction time is 4-12 h.

Drawings

Fig. 1 is a schematic structural diagram of a novel asymmetric fibrous coaxial asymmetric flexible supercapacitor:

1-polyvinyl alcohol; a 2-carbon nanotube layer; 3-polyvinyl alcohol-potassium hydroxide; 4-manganese dioxide; 5-conductive filaments.

Fig. 2 is a scanning electron micrograph of a copper wire @ manganese dioxide inner electrode.

FIG. 3 is a scanning electron micrograph of the copper wire @ manganese dioxide @ silicon dioxide @ carbon nanotube layer structure.

FIG. 4 is a CV curve of the novel asymmetric fibrous coaxial asymmetric flexible supercapacitor under different sweep speeds.

Fig. 5 is a constant current charge and discharge curve of the novel asymmetric fibrous coaxial asymmetric flexible supercapacitor.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

The technical solution of the invention is described in more detail with the following specific examples, but the examples are not to be construed as limiting the invention.

Detailed description of the preferred embodiment 1

(1) And (3) respectively soaking the copper wire in acetone and dilute hydrochloric acid solution for 10min and 30s, washing the copper wire to be neutral by using deionized water after each soaking, and drying the copper wire.

(2) Weighing 0.0316g potassium permanganate and dissolving in 50mL deionized water, stirring at room temperature for 10min, transferring the potassium permanganate and the copper wire to a reaction kettle, keeping the temperature at 150 ℃ for 8h, cooling, and washing and drying the product with deionized water.

(3) Measuring 10mL of ammonia water, adding the ammonia water into 30mL of deionized water, adding 20mL of ethanol after stirring for 20min, continuing stirring for 20min, then adding 9mL of tetraethyl orthosilicate, carrying out ultrasonic oscillation on the mixed solution for 10s, transferring the mixed solution and the product obtained in the step (2) into a reaction kettle, carrying out heat preservation at 60 ℃ for 12h, washing the product to be neutral, soaking the product in a saturated cobalt nitrate solution for 20min, and then drying the product at 60 ℃.

(4) And placing the product in the middle of a tubular furnace, heating to 700 ℃ in argon-hydrogen mixed atmosphere, preserving heat for 10min, introducing acetylene gas to atmospheric pressure, keeping the atmospheric pressure for 5min, vacuumizing the reaction tube, and naturally cooling to room temperature to obtain the carbon nanotube layer.

(5) 4g of polyvinyl alcohol and 5.941g of potassium hydroxide are respectively weighed, added into 45mL of deionized water and stirred at the temperature of 85 ℃ until the solution is clear, and the solution is the polyvinyl alcohol/potassium hydroxide electrolyte solution.

(6) And (3) transferring the product obtained in the step (4) and a polyvinyl alcohol/potassium hydroxide electrolyte solution into a reaction kettle together, keeping the temperature for 4 hours at 85 ℃, and naturally airing the product to finally obtain the novel asymmetric fibrous flexible supercapacitor.

Specific example 2

(1) And (3) respectively soaking the copper wire in acetone and dilute hydrochloric acid solution for 10min and 30s, washing the copper wire to be neutral by using deionized water after each soaking, and drying the copper wire.

(2) Weighing 0.0316g potassium permanganate and dissolving in 50mL deionized water, stirring at room temperature for 10min, transferring the potassium permanganate and the copper wire to a reaction kettle, keeping the temperature at 150 ℃ for 8h, cooling, and washing and drying the product with deionized water.

(3) Measuring 10mL of ammonia water, adding the ammonia water into 30mL of deionized water, adding 20mL of ethanol after stirring for 20min, continuing stirring for 20min, then adding 9mL of tetraethyl orthosilicate, carrying out ultrasonic oscillation on the mixed solution for 10s, transferring the mixed solution and the product obtained in the step (2) into a reaction kettle, carrying out heat preservation at 60 ℃ for 12h, washing the product to be neutral, soaking the product in a saturated cobalt nitrate solution for 20min, and then drying the product at 60 ℃.

(4) And placing the product in the middle of a tubular furnace, heating to 650 ℃ in argon-hydrogen mixed atmosphere, preserving heat for 10min, introducing acetylene gas to atmospheric pressure, keeping the atmospheric pressure for 5min, vacuumizing the reaction tube, and naturally cooling to room temperature to obtain the carbon nanotube layer.

(5) 4g of polyvinyl alcohol and 5.941g of potassium hydroxide are respectively weighed, added into 45mL of deionized water and stirred at the temperature of 85 ℃ until the solution is clear, and the solution is the polyvinyl alcohol/potassium hydroxide electrolyte solution.

(6) And (3) transferring the product obtained in the step (4) and a polyvinyl alcohol/potassium hydroxide electrolyte solution into a reaction kettle together, keeping the reaction kettle at the temperature of 80 ℃ for 4 hours, and naturally airing the product to finally obtain the novel asymmetric fibrous flexible supercapacitor.

Specific example 3

(1) And (3) respectively soaking the copper wire in acetone and dilute hydrochloric acid solution for 10min and 30s, washing the copper wire to be neutral by using deionized water after each soaking, and drying the copper wire.

(2) Weighing 0.0316g potassium permanganate and dissolving in 50mL deionized water, stirring at room temperature for 10min, transferring the potassium permanganate and the copper wire to a reaction kettle, keeping the temperature at 150 ℃ for 8h, cooling, and washing and drying the product with deionized water.

(3) Measuring 10mL of ammonia water, adding the ammonia water into 30mL of deionized water, adding 20mL of ethanol after stirring for 20min, continuing stirring for 20min, then adding 9mL of tetraethyl orthosilicate, carrying out ultrasonic oscillation on the mixed solution for 10s, transferring the mixed solution and the product obtained in the step (2) into a reaction kettle, carrying out heat preservation at 60 ℃ for 12h, washing the product to be neutral, soaking the product in a saturated cobalt nitrate solution for 20min, and then drying the product at 60 ℃.

(4) And placing the product in the middle of a tubular furnace, heating to 650 ℃ in argon-hydrogen mixed atmosphere, preserving heat for 10min, introducing acetylene gas to atmospheric pressure, keeping the atmospheric pressure for 5min, vacuumizing the reaction tube, and naturally cooling to room temperature to obtain the carbon nanotube layer.

(5) 4g of polyvinyl alcohol and 5.941g of potassium hydroxide are respectively weighed, added into 45mL of deionized water and stirred at the temperature of 85 ℃ until the solution is clear, and the solution is the polyvinyl alcohol/potassium hydroxide electrolyte solution.

(6) And (3) transferring the product obtained in the step (4) and a polyvinyl alcohol/potassium hydroxide electrolyte solution into a reaction kettle together, keeping the reaction kettle at the temperature of 90 ℃ for 4 hours, and naturally airing the product to finally obtain the novel asymmetric fibrous flexible supercapacitor.

The foregoing has described the basic principles, principal features, and advantages of the present experiment. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.