阅读说明：本技术 镍插层二氧化锰基柔性对称准固态超级电容器材料及其制备方法和应用 (Nickel intercalation manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material and preparation method and application thereof ) 是由 杨正龙 徐梦瑶 钟瑞 于 2019-09-27 设计创作，主要内容包括：本发明涉及一种镍插层二氧化锰基柔性对称准固态超级电容器材料及其制备方法和应用,该材料通过水热反应在碳布基底上合成Ni-Mn-O纳米阵列制得；将两个超级电容器材料浸泡在PVA-Na<Sub>2</Sub>SO<Sub>4</Sub>溶液,取出用隔膜隔开并封装起来,得到镍插层二氧化锰基柔性对称准固态超级电容器。与现有技术相比,本发明原料易得、价格低廉,是一种绿色环保的电极材料,掺杂镍后电压窗口明显提高,碳布可弯曲、可折叠,固态电解质不像液态电解质易泄漏,可用于携可穿戴产品；此外采用水热合成法,工艺流程简单,所需设备、药品少,生产周期短,对环境零污染；与市面上普遍使用的传统电池和电容器相比,本发明具有更高的能量密度、功率密度和循环使用寿命。(The invention relates to a nickel intercalation manganese dioxide base flexible symmetrical quasi-solid super capacitor material and a preparation method and application thereof, wherein the material is prepared by synthesizing a Ni-Mn-O nano array on a carbon cloth substrate through hydrothermal reaction; soaking two supercapacitor materials in PVA-Na 2 SO 4 And taking out the solution, separating and packaging the solution by using a diaphragm to obtain the nickel intercalation manganese dioxide-based flexible symmetrical quasi-solid supercapacitor. Compared with the prior artCompared with the prior art, the nickel-doped carbon cloth has the advantages that the raw materials are easy to obtain and low in cost, the nickel-doped carbon cloth is a green and environment-friendly electrode material, the voltage window is obviously improved after nickel is doped, the carbon cloth can be bent and folded, the solid electrolyte is not easy to leak like a liquid electrolyte, and the nickel-doped carbon cloth can be used for portable wearable products; in addition, the hydrothermal synthesis method is adopted, the process flow is simple, the required equipment and medicines are few, the production period is short, and the environmental pollution is zero; compared with the traditional battery and capacitor commonly used in the market, the invention has higher energy density, power density and cycle life.)

1. A preparation method of a nickel intercalation manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material is characterized in that a Ni-Mn-O nano array is synthesized on a carbon cloth substrate through a hydrothermal reaction to prepare a carbon cloth electrode, namely the nickel intercalation manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material.

2. The method for preparing the nickel intercalated manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material according to claim 1, characterized in that the method comprises the following steps:

(1) mixing KMnO₄Mixing concentrated hydrochloric acid, deionized water and a nickel source to form a uniform solution;

(2) adding the solution into a reaction kettle, and then immersing the carbon cloth substrate in the solution;

(3) carrying out hydrothermal reaction;

(4) and after the reaction, naturally cooling to room temperature, taking out the carbon cloth substrate, washing and drying to obtain the carbon cloth electrode, namely the nickel intercalation manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material.

3. The method for preparing nickel intercalated manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material according to claim 2, wherein the KMnO in step (1)₄The usage amount ratio of the concentrated hydrochloric acid, the deionized water and the nickel source is as follows: 0.5 to 1.5mmol, 0.1 to 1mL, 15 to 50mL, 0.01 to 0.4 mmol.

4. The method for preparing the nickel intercalated manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material according to claim 2, wherein the nickel source in the step (1) is NiCl₂·6H₂O。

5. The preparation method of the nickel intercalated manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material according to claim 1 or 2, wherein the carbon cloth substrate is conductive carbon cloth treated by hydrochloric acid, and the treatment method comprises the following steps: cutting the carbon cloth to a required size, respectively putting the carbon cloth into acetone, ethanol and deionized water for ultrasonic treatment, then putting the cleaned and dried carbon cloth into concentrated hydrochloric acid for ultrasonic treatment, and drying to obtain the carbon cloth substrate.

6. The method for preparing the nickel intercalated manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material according to claim 2, wherein in the step (3), the hydrothermal reaction conditions are as follows: reacting for 1-8h at 70-125 ℃.

7. The preparation method of the nickel intercalated manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material according to claim 2, characterized in that in the step (4), washing is performed for multiple times by adopting ionized water washing, and drying is performed at 45-65 ℃.

8. The nickel intercalation manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material prepared by the preparation method according to any one of claims 1 to 7.

9. The use of the nickel-intercalated manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material according to claim 8, wherein two of the nickel-intercalated manganese dioxide-based flexible symmetrical quasi-solid supercapacitor materials are immersed in a PVA-Na2SO4 solution, taken out and separated by a separator and packaged to obtain the nickel-intercalated manganese dioxide-based flexible symmetrical quasi-solid supercapacitor.

10. The use of nickel intercalated manganese dioxide based flexible symmetric quasi-solid supercapacitor material according to claim 9, wherein two nickel intercalated manganese dioxide based flexible symmetric quasi-solid supercapacitor materials are in PVA-Na₂SO₄The soaking time of the solution is 1-10 min, and the diaphragm is a non-woven fabric diaphragm.

Technical Field

The invention relates to the field of super capacitors, in particular to a nickel intercalation manganese dioxide-based flexible symmetrical quasi-solid super capacitor material and a preparation method and application thereof.

Background

With the rapid development of scientific technology and market economy, fossil fuels are gradually replaced by new clean energy sources due to the defects of non-regeneration and serious pollution. For energy storage devices and energy conversion devices, development of advanced, low-cost and environment-friendly materials has important strategic significance. In the aspect of electrochemical energy storage materials, the super capacitor is used as a novel material between a traditional rechargeable battery and a traditional capacitor, has the advantages of high energy density, long cycle life, low cost and the like, is also composed of positive and negative electrodes, an electrolyte, a diaphragm and an encapsulation material, active materials used by the electrodes are pseudo-capacitance materials (such as metal oxides and conductive polymers) and double-layer capacitance materials (such as carbon-based materials), and compared with the traditional capacitor, the capacity of the super capacitor is improved by 3-4 orders of magnitude, and the super capacitor has good use value and a wide use range. The flexible super capacitor takes a flexible material as a substrate, can be compressed, bent and stretched, and is suitable for portable wearable equipment, and the electrolyte leakage is avoided due to the use of the solid electrolyte, so that the development of the flexible quasi-solid super capacitor becomes the research direction of people.

Manganese dioxide has rich reserves, low cost, high theoretical specific capacitance and relatively wide voltage window, is a metal oxide electrode material with great development potential, but the problems of low conductivity, poor conductivity and the like still need to be solved. The growth amount and growth morphology of metal are controlled by changing reaction conditions such as reaction time, reaction temperature, reactant consumption and the like, nano-array design is carried out, and the metal oxide is grown by utilizing simple hydrothermal reaction to find out the optimal reaction conditions, so that the metal oxide electrode material with the best performance can be obtained. The metal nickel with better conductivity and manganese dioxide are subjected to hydrothermal reaction synthesis together, so that the conductivity of the electrode material can be obviously improved, the voltage window is enlarged, the current density is improved, the method is also an effective optimization means, and the development prospect is better.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a nickel intercalation manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material, a preparation method and application thereof.

The purpose of the invention can be realized by the following technical scheme:

the invention provides a preparation method of a nickel intercalation manganese dioxide base flexible symmetrical quasi-solid super capacitor material, which synthesizes a Ni-Mn-O nano array on a carbon cloth substrate through hydrothermal reaction to prepare a carbon cloth electrode, namely the nickel intercalation manganese dioxide base flexible symmetrical quasi-solid super capacitor material.

Preferably, the method comprises the steps of:

(1) mixing KMnO₄Mixing concentrated hydrochloric acid, deionized water and a nickel source to form a uniform solution;

(2) adding the solution into a reaction kettle, and then immersing the carbon cloth substrate in the solution;

(3) carrying out hydrothermal reaction;

(4) and after the reaction, naturally cooling to room temperature, taking out the carbon cloth substrate, washing and drying to obtain the carbon cloth electrode, namely the nickel intercalation manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material.

Preferably, the KMnO described in step (1)₄The usage amount ratio of the concentrated hydrochloric acid, the deionized water and the nickel source is as follows: 0.5 to 1.5mmol, 0.1 to 1mL, 15 to 50mL, 0.01 to 0.4 mmol.

Preferably, the nickel source in step (1) is NiCl₂·6H₂O。

Preferably, the carbon cloth substrate is conductive carbon cloth treated by hydrochloric acid, and the treatment method comprises the following steps: cutting the carbon cloth to a required size, respectively putting the carbon cloth into acetone, ethanol and deionized water for ultrasonic treatment, then putting the cleaned and dried carbon cloth into concentrated hydrochloric acid for ultrasonic treatment, and drying to obtain the carbon cloth substrate.

Preferably, in the step (3), the hydrothermal reaction conditions are as follows: reacting for 1-8h at 70-125 ℃.

Preferably, in the step (4), washing is performed for multiple times by adopting ionized water washing, and drying is performed at 45-65 ℃.

The invention also provides a nickel intercalation manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material prepared by the preparation method.

The invention also provides an application of the nickel intercalation manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material, and the two nickel intercalation manganese dioxide-based flexible symmetrical quasi-solid supercapacitor materials are soaked in PVA-Na2SO4 solution, taken out and separated by a diaphragm and packaged to obtain the nickel intercalation manganese dioxide-based flexible symmetrical quasi-solid supercapacitor.

Preferably, the two nickel intercalated manganese dioxide-based flexible symmetrical quasi-solid supercapacitor materials are prepared from PVA-Na₂SO₄The soaking time of the solution is 1-10 min, and the diaphragm is a non-woven fabric diaphragm.

Preferably, the PVA-Na is₂SO₄The preparation method of the solution comprises the following steps:

adding PVA into deionized water, stirring at normal temperature, heating and stirring, cooling, and adding Na dropwise while stirring₂SO₄The solution is continuously stirred after the dropwise addition is finished, and finally the stirring is stopped and the solution is cooled to the room temperature to obtain the PVA-Na₂SO₄And (3) solution.

Preferably:

the usage amount ratio of PVA to deionized water is 4.0-8.0 g: 40-80 mL;

stirring at normal temperature for 0.5 h;

the heating and stirring are carried out for 0.5 to 2.5 hours at a constant temperature of between 90 and 95 ℃;

the temperature reduction means that the temperature is reduced to 35-55 ℃;

Na₂SO₄the solution is prepared by dissolving Na₂SO₄Dissolving in deionized water to obtain Na₂SO₄The usage amount of the deionized water is 0.5-2.5 g: 10-30 mL;

and continuously stirring for 0.1-1.0 h after the dropwise addition is finished.

According to the invention, the nickel-manganese eutectic nanosheet grows on the flexible substrate through a simple hydrothermal reaction, the electrochemical performance of the electrode material is improved through the intercalation and the nano array structure of the metal nickel, and the electrode material is assembled into a symmetrical flexible supercapacitor, so that the electrochemical performance of the supercapacitor is further expanded.

Preferably, in the present invention, KMnO₄Purple black solid small particles at normal temperature, the melting point is 238 ℃, and the density is about 1.01g/cm³And has strong oxidizing property when meeting acid.

Preferably, the concentrated HCl of the present invention is a colorless liquid having a density of about 1.2g/cm³It is volatile and has pungent odor.

Preferably, NiCl is used in the present invention₂·6H₂O is a pale green solid powder at room temperature and has a density of about 1.92g/cm³And is easily soluble in water and ethanol.

Preferably, the PVA is white flocculent solid at normal temperature, the viscosity is 5.6, the PVA is dissolved in water at 90-95 ℃, and the pH value is 6.8.

Preferably, the invention Na₂SO₄White powder at room temperature, no odor and toxicity, and density of about 2.68g/cm³It is easily dissolved in water and the water solution is neutral.

Compared with the prior art, the invention has the following beneficial effects:

(1) the nickel intercalation manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material takes metal oxide manganese dioxide as an active substance, carbon cloth as a flexible substrate and a solid substance as an electrolyte. The manganese dioxide is easy to obtain raw materials and low in price, is a green and environment-friendly electrode material, the voltage window is obviously improved after nickel is doped in the electrode material, the carbon cloth can be bent and folded, the solid electrolyte is not easy to leak like a liquid electrolyte, and the electrode material is suitable for large-scale application in a portable and wearable product.

(2) The nickel intercalation manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material is prepared by adopting a simple hydrothermal synthesis method, and has the advantages of simple process flow, less required equipment and medicines, short production period and zero environmental pollution.

(3) Compared with the traditional battery and the traditional capacitor which are commonly used in the market, the nickel intercalation manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material has higher energy density and power density and longer cycle service life.

Drawings

FIG. 1 is SEM image of flexible symmetrical quasi-solid supercapacitor material with nickel intercalated manganese dioxide base, wherein (a) magnification is 10000 times, and (b) magnification is 40000 times.

FIG. 2 is a TEM image of a nickel intercalation manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material, (a) medium-low magnification; (b) selecting an electron diffraction pattern; (c) and (d) high magnification.

FIG. 3 is an XPS spectrum of a non-intercalated manganese dioxide based flexible and nickel intercalated manganese dioxide based flexible symmetric quasi-solid supercapacitor material, (a) full spectrum; (b) MnO₂XPS spectra of medium Mn 2 p.

FIG. 4 is a constant current charge-discharge (GCD) curve for a nickel intercalated manganese dioxide based electrode material (Ni-Mn-O nanoarray), (a) comparison between different nickel contents; (b) comparing different hydrothermal times; (c) comparison of different hydrothermal temperatures.

FIG. 5 is a Cyclic Voltammetry (CV) curve of a nickel intercalated manganese dioxide based electrode material (Ni-Mn-O nanoarray), (a) comparison between different nickel contents; (b) comparing different hydrothermal times; (c) comparison of different hydrothermal temperatures.

FIG. 6 is a performance test of a nickel intercalated manganese dioxide-based flexible symmetrical quasi-solid supercapacitor, (a) cyclic voltammetry curve; (b) a charge-discharge curve; (c) comparing CV curves before and after 1000 cycles; (d) comparison of CV curves before and after 10 times of bending

Detailed Description

Synthesizing a Ni-Mn-O nano array on a carbon cloth substrate through a hydrothermal reaction to prepare a carbon cloth electrode, namely the nickel intercalation manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material; two carbon cloth electrodes are soaked in PVA-Na₂SO₄Taking out the solution, separating and packaging the solution by using a diaphragm to prepare the flexible symmetrical quasi-solid of the nickel intercalation manganese dioxide baseA state supercapacitor.

More specifically, the method comprises the following steps:

(1) 0.5-1.5 mmol of KMnO₄0.1-1 mL of concentrated hydrochloric acid, 15-50 mL of deionized water and 0.01-0.4mmol of NiCl₂·6H₂And O, stirring for 10min on an electromagnetic stirrer to dissolve to form a uniform solution.

(2) And taking 10-50 mL of the solution out of the solution, adding the solution into a 20-60 mL high-pressure reaction kettle, weighing the carbon cloth, and then putting the carbon cloth into the high-pressure reaction kettle to immerse the carbon cloth in the solution.

(3) And (3) sealing the high-pressure reaction kettle, and reacting for 1-8 hours at 70-125 ℃.

(4) And naturally cooling the reacted carbon cloth to room temperature, taking out the carbon cloth, washing the carbon cloth with deionized water for several times, putting the carbon cloth into a blast drying oven, drying the carbon cloth at 45-65 ℃, and weighing the dried carbon cloth to obtain a carbon cloth electrode, namely the nickel intercalated manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material.

(5) Then weighing 4.0-8.0 g of PVA, putting the PVA into a beaker filled with 40-80 mL of deionized water, stirring for half an hour at normal temperature, stirring for 0.5-2.5 hours at constant temperature in an oil bath kettle at 90-95 ℃, then cooling to 35-55 ℃, slowly stirring, and dropwise adding Na₂SO₄Solution (0.5-2.5 g Na)₂SO₄Dissolving in 10-30 mL of deionized water), continuously stirring for 0.1-1.0 h after the dropwise addition is finished, stopping stirring, and cooling to room temperature.

(6) Soaking the prepared carbon cloth electrode in PVA-Na₂SO₄And (4) taking out the solution for 1-10 min, separating by using a non-woven fabric diaphragm, and packaging to obtain the quasi-solid symmetrical supercapacitor.

The carbon cloth is preferably conductive carbon cloth treated by hydrochloric acid, and the more preferable size is 1 × 1cm, and the specific treatment scheme is as follows: and respectively putting the purchased carbon cloth into acetone, ethanol and deionized water for ultrasonic treatment for 15min, then putting the cleaned and dried carbon cloth into concentrated hydrochloric acid for continuous ultrasonic treatment for 8min, and drying the carbon cloth for direct use.

The invention is described in detail below with reference to the figures and specific embodiments.

A preparation method of a nickel intercalation manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material comprises the following steps:

(1) 1mmol of KMnO₄0.5mL of concentrated hydrochloric acid, 35mL of deionized water, 0.05mmol of NiCl₂·6H₂And O, stirring for 10min on an electromagnetic stirrer to dissolve to form a uniform solution.

(2) 28mL of the solution was taken out and charged into a 40mL autoclave, and then the carbon cloth was weighed and placed in the autoclave so as to be immersed in the solution.

(3) The high-pressure reaction kettle is sealed and reacts for 2 hours at 85 ℃.

(4) And naturally cooling the reacted carbon cloth to room temperature, taking out the carbon cloth, washing the carbon cloth with deionized water for several times, drying the carbon cloth in a blast drying oven at 60 ℃, and weighing the dried carbon cloth to obtain the carbon cloth electrode.

(5) Weighing 6.0g of PVA, putting the PVA into a beaker filled with 60mL of deionized water, stirring for half an hour at normal temperature, stirring for 1.5 hours at constant temperature in an oil bath kettle at 85 ℃, then cooling to 45 ℃, slowly stirring, and dropwise adding Na₂SO₄Solution (1.5g Na)₂SO₄Dissolved in 20mL deionized water), and stirring for 0.5h after the dropwise addition is finished, stopping stirring, and cooling to room temperature.

(6) Soaking the prepared carbon cloth electrode plate in PVA-Na₂SO₄And (4) taking out the solution for 5min, separating and packaging the solution by using a non-woven fabric diaphragm, and finally obtaining the nickel intercalation manganese dioxide-based flexible quasi-solid symmetrical supercapacitor material.