CN110957145A - Flexible all-solid-state asymmetric fibrous energy storage device and manufacturing method thereof - Google Patents
Flexible all-solid-state asymmetric fibrous energy storage device and manufacturing method thereof Download PDFInfo
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- 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
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Abstract
The invention discloses a flexible all-solid-state asymmetric fibrous energy storage device and a manufacturing method thereof. The flexible all-solid-state asymmetric fibrous energy storage device comprises a flexible all-solid-state asymmetric fibrous energy storage device and a flexible all-solid-state asymmetric fibrous energy storage device, wherein the flexible all-solid-state asymmetric fibrous energy storage device comprises a fibrous anode, a fibrous cathode and an electrolyte which are matched with each other; the positive electrode comprises flexible conductive fibers and a three-dimensional transition bimetallic compound nanowire array formed on the surfaces of the flexible conductive fibers, wherein the transition bimetallic compound nanowire is erected on the surfaces of the conductive fibers. The fibrous supercapacitor provided by the embodiment of the invention has the advantages of high volume energy density, high volume-to-capacity ratio, good electrochemical performance and good mechanical flexibility.
Description
Technical Field
The invention relates to a super capacitor, in particular to a flexible all-solid-state asymmetric fibrous energy storage device and a manufacturing method thereof, and belongs to the technical field of materials.
Background
The flexible electrochemical energy storage device has received wide attention because of its wide application prospect in the next generation portable and flexible wearable electronic products such as flexible displays, distributed sensors and wearable electronic devices. Among several types of flexible power sources, such as flexible batteries and flexible supercapacitors, flexible solid-state Asymmetric Supercapacitors (ASCs) are considered as one of the most advanced flexible energy storage devices due to their fast charge/discharge, long cycle life, high safety and energy density comparable to that of conventional batteries. With the rapid promotion and development of wearable electronic technology industry, a matching power supply with higher electrochemical performance, flexibility and textile characteristics is urgently needed; the flexible Fibrous Supercapacitor (FSC) is one of the more ideal flexible wearable power supply devices for wearable electronic devices due to its small size, light weight, high mechanical flexibility and strong knittability. However, the energy density of the current fibrous supercapacitor is low, which severely limits the practical application and development prospect of the flexible fibrous supercapacitor, and the prior art mainly adopts a metal oxide material with higher specific capacity to improve the volumetric specific energy density of the device. However, the conductivity of the metal oxide material is relatively low, which limits the improvement of the performance of the supercapacitor. How to prepare the fibrous supercapacitor with both high energy density and high power density characteristics is a main technical problem in the research field.
Disclosure of Invention
The invention mainly aims at the problem that the volumetric specific energy density of the conventional fibrous supercapacitor is low, and provides a flexible all-solid-state asymmetric fibrous energy storage device and a manufacturing method thereof so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a flexible all-solid-state asymmetric fibrous energy storage device, which comprises a fibrous anode, a fibrous cathode and an electrolyte, wherein the fibrous anode, the fibrous cathode and the electrolyte are matched with each other; the positive electrode comprises flexible conductive fibers and a three-dimensional transition bimetallic compound nanowire array formed on the surfaces of the flexible conductive fibers, wherein the transition bimetallic compound nanowire is erected on the surfaces of the flexible conductive fibers.
Further, the negative electrode comprises flexible conductive fibers and vanadium nitride nanosheets erected on the surfaces of the flexible conductive fibers.
Preferably, the thickness of the vanadium nitride nanosheet is 10-500nm, and the length is 50nm-5 μm.
Further, at least one of the positive electrode and the negative electrode is wrapped by electrolyte, and the positive electrode and the negative electrode are mutually wound.
Preferably, the surface of the positive electrode and the surface of the negative electrode are both wrapped with electrolyte.
Further, the length of the transition bimetallic compound nanowire is 100nm-80 μm, and the diameter of the transition bimetallic compound nanowire is 10nm-80 nm.
Preferably, the transition bimetallic compound nanowire is made of transition bimetallic sulfide or transition bimetallic phosphide.
Preferably, the transition bimetallic sulfide comprises NiCo2S4The transition bimetal phosphide comprises CoNiP.
Further, the flexible conductive fibers comprise carbon nanotube fibers.
Further, the diameter of the flexible conductive fiber is 5-80 μm.
Further, the electrolyte is selected from gel electrolytes.
Preferably, the gel electrolyte includes a neutral gel electrolyte and an alkaline gel electrolyte.
More preferably, the neutral gel electrolyte includes polyvinyl alcohol and lithium chloride, but is not limited thereto.
More preferably, the alkaline gel electrolyte includes polyvinyl alcohol and potassium hydroxide, but is not limited thereto.
Further, the flexible all-solid-state asymmetric fibrous energy storage device comprises a capacitor.
Further, the volume ratio capacity of the flexible all-solid-state asymmetric fibrous energy storage device is 2332F cm-3The volume energy density is 30.64mWh cm-3。
Further, after 5000 bending cycles, the capacity of the flexible all-solid-state asymmetric fibrous energy storage device is 91.94% of the original capacity.
Further, the flexible all-solid-state asymmetric fibrous energy storage device comprises a fibrous supercapacitor.
The embodiment of the invention also provides a manufacturing method of the flexible all-solid-state asymmetric fibrous energy storage device, which comprises the steps of manufacturing the anode, the cathode and the electrolyte and the step of assembling and combining the anode, the cathode and the electrolyte, wherein the step of manufacturing the anode comprises the following steps of:
providing a catalyst comprising a soluble first transition metal salt, a soluble second transition metal salt, and CO (NH)2)2And NH4F, mixing the solution; wherein, CO (NH)2)2And NH4F is mainly used for providing alkaline conditions;
immersing the pretreated flexible conductive fibers into the mixed solution, transferring the immersed flexible conductive fibers into a sealed reaction kettle, and reacting for 2-8h at the temperature of 100-150 ℃ to obtain bimetallic precursor fibers;
immersing the bimetallic precursor fiber into a soluble sulfide solution, and reacting for 2-8h at the temperature of 100-150 ℃ to obtain a positive electrode, or immersing the bimetallic precursor fiber in a solution filled with NaH2PO2The tubular furnace is calcined for 1 to 5 hours under the condition of 240 ℃ and 450 ℃ of inert gas to obtain the transition bimetal phosphide anode; the positive electrode comprises flexible conductive fibers and a three-dimensional transition bimetallic compound nanowire array formed on the surfaces of the flexible conductive fibers, wherein the transition bimetallic compound nanowire is erected on the surfaces of the flexible conductive fibers.
Furthermore, the length of the transition bimetallic sulfide nanowire and the transition bimetallic phosphide nanowire is 100nm-80 μm, and the diameter of the transition bimetallic sulfide nanowire and the transition bimetallic phosphide nanowire is 10nm-80 nm.
Further, the first transition metal salt includes, but is not limited to, nickel nitrate, and the second transition metal salt includes, but is not limited to, cobalt nitrate.
Further, the mass ratio of the first transition metal salt to the second transition metal salt contained in the mixed solution is 2-4: 1; co (NH) contained in the mixed solution2)2And NH4The mass ratio of F is 2-5: 1.
Further, the step of manufacturing the negative electrode includes: immersing the pretreated flexible conductive fibers into an organic vanadium compound solution, transferring the flexible conductive fibers into a sealed reaction kettle together, and reacting at the temperature of 150-210 ℃ for 1-3h to obtain vanadium precursor fibers;
and (3) placing the vanadium precursor fiber in an ammonia gas atmosphere, and reacting for 2-5h at the temperature of 500-800 ℃ to obtain the negative electrode, wherein the negative electrode comprises a flexible conductive fiber and a vanadium nitride nanosheet erected on the surface of the flexible conductive fiber.
Preferably, the thickness of the vanadium nitride nanosheet is 10-500nm, and the length is 50nm-5 μm.
Preferably, the organic vanadium compound includes triisopropoxytriantivaquoxide, but is not limited thereto.
Further, the preparation method of the pretreated flexible conductive fiber comprises the following steps: and pretreating the flexible conductive fiber by oxygen plasma with the power of 100-200W for 5-10 min.
Preferably, the flexible conductive fibers comprise carbon nanotube fibers.
Preferably, the diameter of the flexible conductive fiber is 5-80 μm.
Further, the step of assembling and combining the positive electrode, the negative electrode, and the electrolyte includes:
and respectively soaking the anode and the cathode in the gel electrolyte for 10-30min, taking out, drying at 50-100 ℃ for 1-5h, and then mutually winding the anode and the cathode with the electrolyte wrapped on the surfaces.
Preferably, the electrolyte is selected from gel electrolytes.
More preferably, the gel electrolyte includes a neutral gel electrolyte and an alkaline gel electrolyte.
More preferably, the neutral gel electrolyte includes polyvinyl alcohol and lithium chloride, but is not limited thereto.
Preferably, the mass ratio of the polyvinyl alcohol to the lithium chloride is 1-2: 1.
more preferably, the alkaline gel electrolyte includes polyvinyl alcohol and potassium hydroxide, but is not limited thereto.
Preferably, the mass ratio of the polyvinyl alcohol to the lithium chloride is 1-2: 1.
compared with the prior art, the embodiment of the invention adopts the transition bimetallic compound with good conductivity and high specific capacity as the positive active material, combines the carbon nanotube fiber with high conductivity and high mechanical flexibility to prepare the flexible fibrous positive electrode, adopts the vanadium nitride as the negative active material to prepare the fibrous negative electrode, further manufactures and forms the asymmetrical fibrous super capacitor, and widens the voltage window of the super capacitor to 1.6V; the fibrous supercapacitor provided by the embodiment of the invention has the advantages of high volume energy density, high volume-to-capacity ratio, good electrochemical performance and good mechanical flexibility.
Drawings
FIG. 1 is a schematic representation of a NiCo sample in an exemplary embodiment of the invention2S4The manufacturing flow diagram of the @ CNT// VN @ CNT flexible all-solid-state asymmetric fiber supercapacitor;
FIG. 2a is an SEM image of a nickel cobalt precursor fiber of example 1 of the present invention;
FIG. 2b is a partial SEM image of the nickel cobalt precursor fiber of FIG. 2 a;
FIG. 2c shows NiCo in example 1 of the present invention2S4@ CNT fibrous composite electrode NiCo on carbon nanotube fiber surface2S4SEM images of nanowire arrays;
FIG. 2c1 is a partial enlarged view of FIG. 2 c;
FIG. 2d shows NiCo in example 1 of the present invention2S4Low power TEM images of nanowires;
FIG. 2e shows NiCo in FIG. 2d2S4Local high-power TEM images of nanowires;
FIG. 2f shows NiCo in example 1 of the present invention2S4HAADF (high angle annular dark field image) map of nanowires;
FIG. 2g, FIG. 2h, and FIG. 2i are NiCo in example 1 of the present invention2S4EDS elements (Co, Ni and S in sequence) distribution images of the nanowires;
FIG. 3a is 0.4A cm in example 1 of the present invention-3Lower NiCo2S4@ CNT fiber electrode and NiCo2O4@ CNT fiber GCD contrast curve;
FIG. 3b shows NiCo in example 1 of the present invention2S4@ CV curve of CNT fiber electrode;
FIG. 3c shows NiCo in example 1 of the present invention2S4A constant current charge-discharge curve diagram of the @ CNT fibrous composite electrode;
FIG. 3d shows NiCo in example 1 of the present invention at different current densities2S4@ CNT fiber electrode and NiCo2O4@ CNT fiber volume capacitance contrast plot;
FIG. 4a shows a NiCo sample in example 1 of the present invention2S4A CV curve of electrochemical performance of the flexible all-solid-state asymmetric fiber supercapacitor of @ CNT// VN @ CNT;
FIG. 4b shows a NiCo sample in example 1 of the present invention2S4The constant current charge-discharge curve of electrochemical performance of the @ CNT// VN @ CNT flexible all-solid-state asymmetric fiber supercapacitor;
FIG. 4c shows a NiCo sample of example 1 of the present invention2S4A capacity graph of electrochemical performance of the @ CNT// VN @ CNT flexible all-solid-state asymmetric fiber supercapacitor;
FIG. 4d shows a NiCo sample of example 1 of the present invention2S4Graph comparing energy density and power density reported by @ CNT// VN @ CNT flexible all-solid-state asymmetric fiber super capacitor with other documents;
FIG. 4e shows a NiCo sample in example 1 of the present invention2S4The constant current charge-discharge curve of the @ CNT// VN @ CNT flexible all-solid-state asymmetric fiber super capacitor under different bending conditions of 0-180 degrees;
FIG. 4f shows a NiCo sample in example 1 of the present invention2S4@ CNT// VN @ CNT flexible all-solid-state asymmetric fiber supercapacitor cycle stability test under 90 ° bending condition.
Fig. 5a, 5b and 5c are scanning electron microscope images of VN nanowires in embodiment 1 of the invention;
FIG. 5d is a CV curve for the VN @ CNT fiber negative electrode in example 1 of the invention;
FIG. 5e is the constant current charge-discharge curve of the VN @ CNT fiber negative electrode in example 1 of the present invention;
FIG. 5f is a graph of the volumetric capacitance of the VN @ CNT fiber negative electrode at different current densities in example 1 of the invention;
FIGS. 6a and 6b show NiCo in comparative example 12O4Scanning electron microscopy of nanowires:
FIG. 7 is a NiCo reference example 12O4@ CV curve of CNT fiber-like composite electrode;
FIG. 8 is a NiCo sample of comparative example 12O4@ CNT fibrous composite electrode constant current discharge curve;
FIG. 9 is NiCo of comparative example 12O4@ CNT fibrous composite electrode bulk capacitance at different current densities;
FIG. 10 is a NiCo sample of comparative example 12O4A CV curve of electrochemical performance of the @ CNT/VN @ CNT flexible all-solid-state asymmetric fiber supercapacitor;
FIG. 11 is a NiCo sample of comparative example 12O4The constant current charging and discharging curve of the @ CNT/VN @ CNT flexible all-solid-state asymmetric fiber super capacitor under different voltage windows;
FIG. 12 is NiCo of comparative example 12O4The constant current charging and discharging curve of the @ CNT/VN @ CNT flexible all-solid-state asymmetric fiber super capacitor under different current densities;
FIG. 13 is NiCo of comparative example 12O4The flexible all-solid-state asymmetric fiber supercapacitor has the following capacity and energy curves at different current densities.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
How to effectively improve the energy density on the premise of keeping the high power density is an urgent problem to be solved in the research of the fibrous super capacitor. From the energy formula analysis of the supercapacitor, E-1/2 CV2The strategy for effectively improving the energy density of the super capacitor mainly comprises the steps of constructing an asymmetric super capacitor to expand a voltage window and developing a fibrous electrode with larger specific surface area and higher specific capacity.
NiCo, a typical pseudocapacitive electrode active material2S4The bimetallic sulfide has been much more attentive and studied than its corresponding metal oxide, and has very excellent conductivity (10)5-106S m-1) Excellent intrinsic activity and high stability, and is an ideal electrode active material for developing a high-energy density super capacitor. In addition, the energy density of the super capacitor can be improved by matching two active materials which work under different voltage windowsAnd the construction of the positive and negative fiber electrodes is adopted to manufacture the asymmetric super capacitor, so that the working voltage window of the energy storage device is widened, and the energy density of the device is improved.
The embodiment of the invention obtains the high-energy storage device based on the sulfur-cobalt-nickel/vanadium nitride system, and the electrical conductivity of the sulfur-cobalt-nickel and the vanadium nitride is relatively high, which is beneficial to improving the overall capacity of the energy storage device; secondly, the sulfur-cobalt-nickel and the vanadium nitride are respectively used as the anode active material and the cathode active material, so that the working voltage window of the energy storage device is effectively widened, and the energy density of the device is favorably improved.
In the embodiment of the invention, sulfur-cobalt-nickel/carbon nanotube fibers (NiCo) are respectively prepared by a two-step hydrothermal method2S4@ CNT) flexible composite electrode (namely the first working electrode) and vanadium nitride/carbon nanotube fiber (VN @ CNT) flexible composite electrode (namely the second working electrode) and carrying out electrochemical performance characterization on the flexible composite electrode; then, with NiCo2S4The flexible composite electrode @ CNT is used as a positive electrode, the flexible composite electrode VN/carbon nanotube fiber (VN @ CNT) is used as a negative electrode, polyvinyl alcohol/lithium chloride (PVA/LiCl) is used as a gel electrolyte, and the positive electrode and the negative electrode are mutually wound to form NiCo with a winding structure2S4a/VN flexible all-solid-state asymmetric fiber super capacitor (hereinafter, the super capacitor can be simply referred to).
Example 1
Referring to FIG. 1, in some more specific embodiments, NiCo2S4The manufacturing method of the @ CNT// VN @ CNT flexible all-solid-state asymmetric fiber supercapacitor can comprise the following steps of:
1) firstly, pretreating the carbon nano tube fiber by adopting oxygen plasma for 5min under the power condition of 200W, and then quickly fixing the carbon nano tube fiber on a polytetrafluoroethylene bracket; as shown in FIG. 1, NiCo2S4The preparation of the @ CNT fiber electrode can be synthesized by a two-step hydrothermal process.
2) Growing 3D vertical NiCo on the surface of carbon nanotube fibers (CNTs)2S4Nanowire array for preparing NiCo2S4@ CNT fibrous composite electrode:
2.1) preparing NiCo-precursor fiber; first, 162.47mg of Ni (NO)3)2·6H2O and 348mg Co (NO)3)2·6H2Dissolving O in 35mL Deionized (DI) water, and fully and uniformly stirring to form a first mixed solution; then, 180mgCo (NH)2)2And 44.4mg NH4F, adding the mixture into the first mixed solution to form a second mixed solution, stirring for 10min, transferring the second mixed solution into a reaction kettle, immersing the pretreated carbon nanotube fibers into the second mixed solution, sealing and placing the second mixed solution in an oven, and treating the second mixed solution at 120 ℃ for 5 hours; after the reaction is finished, after the reaction kettle is naturally cooled to the room temperature, washing the obtained light purple nickel cobalt precursor fiber with ethanol and DI water for several times respectively, and drying for 12 hours, wherein shape SEM images of the nickel cobalt precursor fiber are shown in figures 2a and 2 b;
2.2) vulcanizing treatment; soaking the dried NiCo-precursor fiber into 35mL of 0.13M sodium sulfide aqueous solution, treating for 4h at 120 ℃, cooling, taking out, washing with ethanol and DI water for several times, and drying to obtain NiCo2S4Preparation of a @ CNT fibrous composite electrode, NiCo2S4@ CNT fibrous composite electrode NiCo on carbon nanotube fiber surface2S4SEM images of nanowire arrays as shown in FIGS. 2c and 2c1, NiCo2S4The low-power and high-power TEM images of the nanowires are shown in fig. 2d and fig. 2e, respectively, and the inset in fig. 2d is a TEM image of the nickel cobalt-precursor; FIG. 2f is NiCo2S4HAADF (high angle annular dark field image) of nanowires, FIGS. 2g, 2h, 2i show NiCo, respectively2S4EDS element (Co, Ni, S) distribution image of nanowires;
3) VN @ CNT fibrous composite electrode is prepared by adopting a two-step method;
3.1) firstly, adding 300 mu L of triisopropoxyl vanadium oxide into 40mL of isopropanol by using a liquid transfer gun to form a third mixed solution, uniformly stirring, and transferring to an autoclave; then, immersing the pretreated carbon nanotube fibers in a third mixed solution; sealing the high-pressure autoclave, placing the high-pressure autoclave in an oven, treating the high-pressure autoclave for 10 hours at the temperature of 200 ℃ to obtain VN-precursor fibers, washing the VN-precursor fibers by using alcohol, and drying the VN-precursor fibers; finally, treating the dried VN-precursor fiber for 2h under the condition of an ammonia atmosphere and 600 ℃ to obtain a VN @ CNT fibrous composite electrode, wherein scanning electron micrographs of the VN nanowire are shown in FIGS. 5a, 5b and 5 c; the CV curve of the VN @ CNT fiber negative electrode is shown in figure 5d, the constant current charge-discharge curve of the VN @ CNT fiber negative electrode is shown in figure 5e, and the volume capacitance of the VN @ CNT fiber negative electrode under different current densities is shown in figure 5 f;
4) preparing a gel electrolyte; the preparation method of the neutral LiCl/PVA gel electrolyte comprises the following steps: mixing 8.4g LiCl and 10g PVA powder in 80mL deionized water, and stirring for 2h at 80 ℃ to obtain a neutral LiCl/PVA gel electrolyte; the preparation method of the alkaline KOH/PVA gel electrolyte comprises the following steps: firstly, adding 10g of PVA powder into 80ml of deionized water, and stirring for 2h at 80 ℃ to obtain a PVA solution; then, 11.2g of KOH was dissolved in 20ml of deionized water, and then added dropwise to the PVA solution, and after stirring sufficiently and uniformly, the alkaline KOH/PVA gel electrolyte was obtained.
5) After the preparation of the gel electrolyte is completed, a gel electrolyte is selected and NiCo is prepared2S4Soaking @ CNT composite electrode and VN @ CNT fibrous composite electrode in gel electrolyte for 20min, and then coating NiCo with gel electrolyte2S4The @ CNT composite electrode and the VN @ CNT fibrous composite electrode are subjected to drying treatment at 80 ℃ for 2h to evaporate excessive moisture in the gel electrolyte;
6)NiCo2S4assembling the flexible all-solid-state supercapacitor of @ CNT// VN @ CNT; NiCo with gel electrolyte coated on surface2S4And (3) winding the @ CNT composite electrode and the VN @ CNT fibrous composite electrode to form a winding structure, namely, finishing the manufacture of the supercapacitor.
The super capacitor obtained by the embodiment of the invention can stably work under a voltage window of 0-1.6V, and the volume specific capacitance of the super capacitor is 2332F cm-3The energy density is 30.64mWh cm-3. In addition, the super capacitor has good flexibility and can keep stable performance under various bending angles. After 5000 bending cycles, itThe capacity can still keep 91.94% of the original capacity.
Example 2
In this embodiment, a method for manufacturing a CoNiP @ CNT// VN @ CNT flexible all-solid-state asymmetric fiber supercapacitor and a NiCo capacitor in embodiment 12S4The manufacturing methods of the @ CNT// VN @ CNT flexible all-solid-state asymmetric fiber super capacitor are basically the same, and the difference is that the preparation method of the CoNiP @ CNT positive electrode in the embodiment is different.
The preparation process of the CoNiP @ CNT positive electrode in the embodiment comprises the following steps:
growing a 3D vertical CoNiP nanowire array on the surface of a carbon nanotube fiber (CNT) to obtain a CoNiP @ CNT fibrous composite electrode:
1) preparing NiCo-precursor fiber; first, 162.47mg of Ni (NO)3)2·6H2O and 348mg Co (NO)3)2·6H2Dissolving O in 35mL Deionized (DI) water, and fully and uniformly stirring to form a first mixed solution; then, 180mg of Co (NH)2)2And 44.4mg NH4F, adding the mixture into the first mixed solution to form a second mixed solution, stirring for 10min, transferring the second mixed solution into a reaction kettle, immersing the pretreated carbon nanotube fibers into the second mixed solution, sealing and placing the second mixed solution in an oven, and treating the second mixed solution at 120 ℃ for 5 hours; after the reaction is finished, after the reaction kettle is naturally cooled to room temperature, washing the obtained light purple nickel-cobalt precursor fiber with ethanol and DI water for several times respectively, and drying for 12 hours;
2) NiCo-precursor fiber is filled with NaH2PO2The tubular furnace is calcined for 1-5h under the inert gas condition of 240-450 ℃ to obtain the CoNiP @ CNT fibrous composite electrode.
The inventor also performed performance tests on CoNiP @ CNT positive electrodes and supercapacitors obtained in the present example, and the test results are the same as those of NiCo in example 12S4The performance of the @ CNT fiber electrode and the performance of the supercapacitor are basically consistent.
Comparative example 1
The fibrous supercapacitor made in the comparative example was substantially identical to the fibrous supercapacitor made in example 1, except thatAlso, in the comparative example, 3D vertical NiCo was grown on the surface of carbon nanotube fiber (CNT) using the method as in example 12O4Nanowire array for preparing NiCo2O4A @ CNT fibrous composite electrode as a positive electrode, the NiCo2O4Scanning electron micrographs of nanowires are shown in fig. 6a, 6 b: NiCo2O4The CV curve of the @ CNT fiber composite electrode is shown in FIG. 7, and NiCo2O4The constant current discharge curve of the @ CNT fiber composite electrode is shown in FIG. 8, and NiCo2O4The volumetric capacitance of the @ CNT fibrous composite electrode at different current densities is shown in FIG. 9;
NiCo2O4the CV curve of electrochemical performance of the flexible all-solid-state asymmetric fiber supercapacitor with @ CNT/VN @ CNT is shown in FIG. 10, and NiCo2O4The constant current charge-discharge curve of the @ CNT/VN @ CNT flexible all-solid-state asymmetric fiber super capacitor under different voltage windows is shown in FIG. 11; NiCo2O4The constant current charge-discharge curve of the @ CNT/VN @ CNT flexible all-solid-state asymmetric fiber supercapacitor under different current densities is shown in FIG. 12; NiCo2O4The capacity and energy curves of the @ CNT/VN @ CNT flexible all-solid-state asymmetric fiber supercapacitor at different current densities are shown in FIG. 13.
FIG. 3a is 0.4A cm in example 1 of the present invention-3Lower NiCo2S4@ CNT fiber electrode and NiCo2O4@ CNT fiber GCD contrast curve; FIG. 3b is a CV curve of a NiCo2S4@ CNT fiber electrode of example 1 in accordance with the present invention; FIG. 3c shows NiCo in example 1 of the present invention2S4A constant current charge-discharge curve diagram of the @ CNT fibrous composite electrode; FIG. 3d shows NiCo in example 1 of the present invention at different current densities2S4@ CNT fiber electrode and NiCo2O4@ CNT fiber volume capacitance contrast plot.
In the embodiment of the invention, a transition bimetallic compound with good conductivity and high specific capacity is used as a positive active material, a carbon nanotube fiber with high conductivity and high mechanical flexibility is combined, a flexible fibrous positive electrode is prepared and formed by a simple method, vanadium nitride is used as a negative active material to prepare a fibrous negative electrode, an asymmetric fibrous super capacitor is further prepared and formed, and the voltage window of the super capacitor is widened to 1.6V; the fibrous supercapacitor provided by the embodiment of the invention has high volume energy density, better electrochemical performance and mechanical flexibility.
The embodiment of the invention provides the high-performance fibrous electrode which is simple in manufacturing method and low in cost, and the flexible fibrous super capacitor is constructed by using the high-performance fibrous electrode, so that more possibilities are provided for developing a flexible wearable energy storage device with higher performance.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A flexible all-solid-state asymmetric fibrous energy storage device comprises a fibrous anode, a fibrous cathode and an electrolyte which are matched with each other; the method is characterized in that: the positive electrode comprises flexible conductive fibers and a three-dimensional transition bimetallic compound nanowire array formed on the surfaces of the flexible conductive fibers, wherein the transition bimetallic compound nanowire is erected on the surfaces of the flexible conductive fibers.
2. The flexible all-solid-state asymmetric fibrous energy storage device of claim 1, wherein: the negative electrode comprises flexible conductive fibers and vanadium nitride nanosheets erected on the surfaces of the flexible conductive fibers; preferably, the thickness of the vanadium nitride nanosheet is 10-500nm, and the length is 50nm-5 μm.
3. The flexible all-solid-state asymmetric fibrous energy storage device of claim 1, wherein: the surface of at least one of the positive electrode and the negative electrode is wrapped with electrolyte, and the positive electrode and the negative electrode are mutually wound; preferably, the surface of the positive electrode and the surface of the negative electrode are both wrapped with electrolyte.
4. A flexible all-solid-state asymmetric fibrous energy storage device according to claim 1 or 3, wherein: the length of the transition bimetallic compound nanowire is 100nm-80 mu m, and the diameter of the transition bimetallic compound nanowire is 10nm-80 nm; preferably, the transition bimetallic compound nanowire is made of transition bimetallic sulfide or transition bimetallic phosphide, and preferably, the transition bimetallic sulfide comprises NiCo2S4The transition bimetal phosphide comprises CoNiP; and/or, the flexible conductive fibers comprise carbon nanotube fibers; preferably, the diameter of the flexible conductive fiber is 5-80 μm; and/or, the electrolyte is selected from a gel electrolyte; preferably, the gel electrolyte comprises a neutral gel electrolyte and an alkaline gel electrolyte; more preferably, the neutral gel electrolyte comprises polyvinyl alcohol and lithium chloride; more preferably, the alkaline gel electrolyte includes polyvinyl alcohol and potassium hydroxide.
5. The flexible all-solid-state asymmetric fibrous energy storage device of claim 1, wherein: the flexible all-solid-state asymmetric fibrous energy storage device comprises a capacitor.
6. A method for manufacturing a flexible all-solid-state asymmetric fibrous energy storage device comprises the steps of manufacturing a positive electrode, a negative electrode and an electrolyte and combining the positive electrode, the negative electrode and the electrolyte, and is characterized in that the step of manufacturing the positive electrode comprises the following steps:
providing a catalyst comprising a soluble first transition metal salt, a soluble second transition metal salt, and CO (NH)2)2And NH4F, mixing the solution;
immersing the pretreated flexible conductive fibers into the mixed solution, transferring the immersed flexible conductive fibers into a sealed reaction kettle, and reacting for 2-8h at the temperature of 100-150 ℃ to obtain bimetallic precursor fibers;
immersing the bimetal precursor fiber into a soluble sulfide solution, and reacting for 2-8h at the temperature of 100-150 ℃ to obtain the transition bimetal sulfideA pole; or, the bimetallic precursor fiber is filled with NaH2PO2The tubular furnace is calcined for 1 to 5 hours under the condition of 240 ℃ and 450 ℃ of inert gas to obtain the transition bimetal phosphide anode; the transition bimetal sulfide anode comprises flexible conductive fibers and a transition bimetal sulfide nanowire array formed on the surfaces of the flexible conductive fibers, the transition bimetal phosphide anode comprises flexible conductive fibers and a transition bimetal phosphide nanowire array formed on the surfaces of the flexible conductive fibers, and the transition bimetal sulfide nanowire array or the transition bimetal phosphide nanowire array is erected on the surfaces of the flexible conductive fibers.
7. The method of manufacturing according to claim 6, wherein: the length of the transition bimetallic sulfide nanowire and the transition bimetallic phosphide nanowire is 100nm-80 mu m, and the diameter of the transition bimetallic sulfide nanowire and the transition bimetallic phosphide nanowire is 10nm-80 nm; and/or, the first transition metal salt comprises nickel nitrate and the second transition metal salt comprises cobalt nitrate; and/or the molar ratio of the first transition metal salt to the second transition metal salt contained in the mixed solution is 2-4:1, CO (NH) contained in the mixed solution2)2And NH4The molar ratio of F is 2-5: 1.
8. The method according to claim 6, wherein the step of manufacturing the negative electrode includes:
immersing the pretreated flexible conductive fibers into an organic vanadium compound solution, transferring the flexible conductive fibers into a sealed reaction kettle together, and reacting at the temperature of 150-210 ℃ for 1-3h to obtain vanadium precursor fibers;
placing the vanadium precursor fiber in an ammonia gas atmosphere, and reacting at the temperature of 500-800 ℃ for 2-5h to obtain a negative electrode, wherein the negative electrode comprises a flexible conductive fiber and a vanadium nitride nanosheet erected on the surface of the flexible conductive fiber;
preferably, the thickness of the vanadium nitride nanosheet is 10-500nm, and the length is 50nm-5 μm;
preferably, the concentration of the organic vanadium compound solution ranges from 0.01 mol/ml to 0.1 mol/ml;
preferably, the organo vanadium compound comprises triisopropoxytriantivaquo.
9. The method of manufacturing according to claim 8, wherein the method of preparing the pre-treated flexible conductive fiber comprises: pretreating the flexible conductive fiber for 5-10min by oxygen plasma with the power of 100-200W; preferably, the flexible conductive fiber comprises carbon nanotube fiber, and preferably, the diameter of the flexible conductive fiber is 5-80 μm.
10. The method of claim 8, wherein the step of combining the positive electrode, the negative electrode, and the electrolyte assembly comprises:
respectively soaking the anode and the cathode in the gel electrolyte for 10-30min, taking out, drying at 50-100 ℃ for 1-5h, and then mutually winding the anode and the cathode with the electrolyte wrapped on the surfaces;
preferably, the electrolyte is selected from the group consisting of gel electrolytes; more preferably, the gel electrolyte includes a neutral gel electrolyte and an alkaline gel electrolyte; more preferably, the neutral gel electrolyte comprises polyvinyl alcohol and lithium chloride; preferably, the mass ratio of the polyvinyl alcohol to the lithium chloride is 1-2: 1; more preferably, the alkaline gel electrolyte comprises polyvinyl alcohol and potassium hydroxide; preferably, the mass ratio of the polyvinyl alcohol to the lithium chloride is 1-2: 1.
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