CN113488343A - MOFs porous carbon-based multi-component flexible electrode, preparation method and application - Google Patents
MOFs porous carbon-based multi-component flexible electrode, preparation method and application 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 belongs to the technical field of electrode material preparation, and discloses a multi-component flexible electrode based on MOFs porous carbon, a preparation method and application thereof, wherein MOFs is synthesized on the surface of a flexible conductive carbon material by a solvothermal method; carrying out double doping on MOFs based on the flexible conductive carbon material; the MOFs porous carbon-based multi-component flexible electrode with an adsorption-intercalation-conversion synergistic mechanism is constructed on the basis of double-doped MOFs. The electrode fully utilizes the synergistic effect among materials, overcomes the limitation of a single anode material, and weakens the electrochemical dynamics retardation of sodium ions; the double-doped MOFs derivative flexible electrode is prepared on the surface of the flexible carbon material conductive substrate, so that the flexible anode material substrate which has the advantages of large specific surface area, high network conductivity and carrier mobility, good structural stability and the like is obtained; and the deep mechanism of SICs energy density, power density, multiplying power characteristic and cycle stability is improved.
Description
Technical Field
The invention belongs to the technical field of electrode material preparation, and particularly relates to a multi-component flexible electrode based on MOFs porous carbon, a preparation method and application thereof.
Background
At present, sodium ion hybrid Supercapacitors (SICs) have important application potential in current electric vehicles and smart grid energy technologies due to their lower cost and richer resources than lithium ion hybrid supercapacitors, and have attracted scientific attention. The working principle of the device is that a pseudocapacitance reaction that sodium ions are embedded in/removed from the anode of an active substance and an electric double layer process that anions in organic electrolyte are reversibly adsorbed/desorbed on the surface of the cathode store charges, so that an energy storage mechanism for improving power density, rate characteristics and cycle stability is provided. In 2012, Kuratani et al reported for the first time that hard carbon pre-intercalated with sodium was used as the anode, Activated Carbon (AC) as the cathode, and 1.0M NaPF 6 as SICs of the electrolyte solution. In 2017, the preparation structure of the periseismic topic group is TiO2The SICs anode of @ CNT @ C finds that the introduction of the multi-walled carbon nanotube can enhance the electron migration and ion transport efficiency of the anode and improve the rate characteristic of a device. The majority of the relevant research has been around to improve the kinetics of the electrochemical reaction of SICs anodes, mainly because the pseudocapacitive reaction process of the anodes is much slower than the cathodic double layer process, but this results in high power density of the hybrid supercapacitors at the expense of impairing their energy density.
The anode materials of SICs are differentIon storage mechanisms are largely divided into four types: alloy type (Sn, Sb, Ge, etc.); transformation type (MoS)2、WS2CoP, etc.); insert layer Type (TiO)2、Na2Ti3O7、Nb2O5、V2 O5Etc.) and adsorption type (carbon based). Each of these materials has advantages and disadvantages: the alloy type and conversion type anode materials have high specific capacity but poor cycle stability; the intercalation type and the adsorption type anodes have low specific capacity, but have the advantages of small volume expansion, good cycle stability and the like. However, how to combine the advantages of various types of NSFC anode materials, and simultaneously exert the high-efficiency and stable sodium ion deintercalation capability of adsorption, type and intercalation type anode materials, and the excellent specific capacity of the conversion type anode material, so as to design an anode with high power density, high energy density and long cycle stability is still a challenge in the current SICs research.
The MOFs are metal-organic framework compounds assembled by transition metal ions and organic connecting groups in a highly modular manner, and have the advantages of stable electrochemical activity, large specific surface area, high porosity and the like. By Zn2+Sulfurization with Thioacetamide (TAA), and Zn2+And Sb3+Metal cation exchange reaction of the reaction product to synthesize ZnS-Sb at high temperature2 S3The structure of the @ C double-shell polyhedron has the advantages that the carbon layer plays an important role in buffering and protecting active substances of the sodium ion energy storage device, the transmission efficiency of electrons is improved, and the ion transportation and the circulation stability of the device are optimized. The chemical composition of the precursor is adjusted, one or two transition metal ions are doped, the morphology of the MOFs can be adjusted, the components of the MOFs can be controlled, and the MOFs can be subjected to subsequent treatment to realize the construction of a functional module. So far, most of the doping of the MOFs is modified by the whole element doping, and the MOFs is composed of an organic substance and a metal compound coated inside the organic substance, and for this point, an element selective double-element doping process combining self-doping and external doping can be used for the MOFs. Firstly, organic matters are added as nitrogen sources in the synthesis process of MOFs, the MOFs is subjected to specific-process pyrolysis carbonization in an inert atmosphere, and nitrogen is simultaneously doped into a carbon material to form the material with high conductivityNitrogen is self-doped with a hard carbon material. Meanwhile, the metal compound is reduced by carbon to form metal nano particles, and the nano structure which is formed by embedding the metal nano particles into the nitrogen-doped hard carbon and takes the hard carbon material as a main body is formed. On the basis, metal nanoparticles in the electrode are doped with elements such as phosphorus, sulfur and selenium to form metal phosphide, sulfide and selenide, so that the conductivity, ion transmission and rapid induction of pseudocapacitance reaction of the hard carbon-based electrode derived from the MOFs are further improved, and the wettability of the electrode to an electrolyte is enhanced. The MOFs processed by the double doping process becomes a metal compound nanoparticle embedding nitrogen-doped hard carbon anode material which takes a conversion reaction as a main part, the metal compound can effectively improve the energy density of an electrode, and the embedded structure can improve the conductivity of the metal compound and buffer the volume expansion of the metal compound in the reaction process. Rogach et al developed a simultaneous process of carbonization, selenization, and selenium vapor deposition to directly convert the original MOFs into selenium/selenide/carbon composite nanoparticle anode materials with selenium content up to 76 wt%, improving the capacity and rate characteristics of sodium-electricity energy storage. At present, the research of the MOFs derivatives in the field of SICs is less, most of prepared SICs anodes are powder materials derived from MOFs, and the flexibility based on the MOFs derivatives has great significance in the field of SICs.
In recent years, flexible devices such as flexible displays, wearable health devices, flexible solar panels, etc. have attracted wide attention in various fields, and it is important to develop bendable flexible hybrid supercapacitors capable of continuously providing and storing energy and matching with the flexible devices. Among them, designing and preparing flexible electrodes are the first step of developing flexible SICs, and the most important step. In addition, the metal collector-free, binder-free flexible electrode has a higher energy density than conventional energy storage electrodes. For example, a silicon electrode prepared by coating a slurry on a copper collector can obtain more than 2000mAhg considering only the active material self weight-1However, if the weight of the entire copper current collector is taken into account, the capacity of the entire anode will be less than 100mAh g-1. Topic group of Sujinyu in 2019Preparing a multilayer structure flexible anode compounded by vertically grown graphene and CoSe 2 on carbon fiber cloth by means of combining plasma enhanced chemical vapor deposition and a wet chemical method, wherein when SICs are formed by the electrode and Activated Carbon (AC), 0.5Ag is used-1The current density of the battery is charged and discharged in a potential range of 0.5-3.3V, the stability of 1800 cycles is kept, and 116Wh kg is obtained-1High energy density. Therefore, the MOFs derivatives are prepared on the surface of a conductive substrate made of flexible carbon materials such as carbon fiber cloth, electrostatic spinning carbon fibers and two-dimensional carbon paper, and a flexible SICs anode with high energy density and high network conductivity, high carrier mobility, high porosity, good structural stability and the like can be formed. However, the flexible electrode based on the above MOFs derivatives can provide limited power density, and further establishing a surface pseudocapacitance reaction with rapid ion insertion/extraction on the nano hard carbon surface of the embedded conversion type metal compound is an important way to obtain the SICs flexible anode with combined energy density, power density and cycling stability.
Orthorhombic V2O5Due to the inherent structural advantages, the material becomes an insertion layer type energy storage material with rapid pseudocapacitance reaction and long cycle life, and has great potential in the research of sodium electric anodes. Theoretical calculation shows that V2O5Has an inherent lithium ion intercalation rapid pseudocapacitance mechanism although the radius of sodium ions
Greater than the radius of lithium ion
But V2O5The (001) side of has
The large interplanar spacing of the crystal plates can also provide an effective channel for the insertion or extraction of sodium ions. In 2012, V of a layered structure compounded on the surface of a carbon nanotube by a hydrothermal method earlier in the Luyunfeng topic group2O5Obtaining V of the porous interconnection network type2O5The anode has excellent sodium de-intercalation and electron transfer channels, and provides possibility for manufacturing high-performance flexible SICs by using organic electrolyte. Due to the poor conductivity of most of the conversion metal compounds, intrinsic defects such as volume expansion and the like are generated in the process of sodium ion deintercalation, which causes the problems of poor capacity retention capability and rate characteristics, low coulombic efficiency in the first cycle, unstable solid electrolyte interface film and the like. And, the nano-sized type intercalation type V2O5The high reactivity due to the high specific surface area of the material tends to accumulate during the electrochemical reaction, resulting in parasitic chemical reactions that are generally irreversible, thereby affecting the life and performance of the electrode.
Through the above analysis, the problems and defects of the prior art are as follows:
(1) the research of the existing MOFs derivatives in the field of SICs is less, most of prepared SICs anodes are powder materials derived based on MOFs, and the flexibility based on the MOFs derivatives has great research significance in the field of SICs.
(2) The power density that can be provided by the existing flexible electrodes based on the MOFs derivatives is limited.
(3) Most of the existing conversion type metal compounds have poor conductivity, and can generate inherent defects such as volume expansion and the like in the process of sodium ion extraction, so that the capacity retention capacity and rate characteristic of the conversion type metal compounds are poor. And, the nano-sized type intercalation type V2O5The high reactivity due to the high specific surface area of the material tends to accumulate during the electrochemical reaction, resulting in a parasitic chemical reaction that is generally irreversible, affecting the life and performance of the electrode.
The difficulty in solving the above problems and defects is: however, how to combine the advantages of various types of anode materials, and simultaneously exert the high-efficiency and stable sodium ion deintercalation capability of adsorption, type and intercalation type anode materials, and the excellent specific capacity of the conversion type anode material, so as to design an anode with high power density, high energy density and long cycle stability is still a challenge of the current research on SICs.
The significance of solving the problems and the defects is as follows: the method overcomes the defect of short performance of a single active material, combines different materials, fully exerts the advantages of various active materials, maintains the energy density of a device constructed by the electrode, improves the power density and the cycle stability of the device, and provides a new idea for manufacturing an information electrochemical energy storage device.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a multi-component flexible electrode based on MOFs porous carbon, a preparation method and application.
The invention is realized in such a way that a preparation method of a multi-component flexible electrode based on MOFs porous carbon comprises the following steps:
step one, synthesizing MOFs on the surface of a flexible conductive carbon material by using a solvothermal method; increase specific surface area and conductivity of carbon material
Step two, carrying out double doping on MOFs of the flexible conductive carbon-based material; and activating the MOFs to form an alloy type active substance coated by the MOFs nano carbon sheet, and providing a certain energy density for the electrode.
And step three, constructing a multi-component flexible electrode based on MOFs porous carbon with an adsorption-intercalation-conversion synergistic mechanism. Electrode material forming multi-component synergistic effect
Further, in the step one, the synthesizing of the MOFs on the surface of the flexible conductive carbon material by using the solvothermal method comprises: under a certain temperature condition, placing a flexible carbon material conductive substrate such as carbon fiber cloth, an electrostatic spinning carbon material or two-dimensional carbon paper with the surface being treated by plasma into a precursor solution, soaking for a certain period of time, taking out, and placing a sample into a vacuum drying oven for drying to obtain the MOFs based on the flexible carbon material conductive substrate.
Further, in the second step, the double doping of the MOFs of the flexible conductive carbon-based material includes:
(1) synchronously carbonizing MOFs (metal-organic frameworks) based on a flexible conductive carbon material and self-doping nitrogen elements: placing a proper amount of the MOFs flexible electrode in a quartz boat, and performing Ar protection at 1-5 DEG Cmin-1The temperature is raised to 450-900 ℃ in the temperature raising rate range, and the temperature is raised for a certain time at constant temperature, so as to form MOFs derived hard carbon with metal nano particles embedded in the nitrogen-doped hard carbon;
(2) the external doping of the elements adopts a chemical vapor deposition method: placing the derived hard carbon in a chemical vapor deposition furnace tube, heating to 300-500 ℃, under the protection of Ar, contacting substances containing phosphorus, sulfur, selenium or the like with the MOFs derived hard carbon along with argon gas flow, and heating at constant temperature for a certain time, thereby completing the external doping of metal particles embedded in the derivatives by active elements, and forming the MOFs derivatives of metal compound nanoparticles embedded in the nitrogen-doped hard carbon material.
Further, in the third step, the MOFs porous carbon-based multi-component flexible electrode for constructing the adsorption-intercalation-conversion synergistic mechanism comprises: v is deposited on the surface of the MDFS by using a hydrothermal synthesis method or a magnetron sputtering method2O5The film is placed in a reaction kettle with glucose solution for heating to complete the hydrothermal reaction; naturally cooling and drying to realize V2O5High temperature annealing and V2O5Coating of soft carbon thin layer on MDFS surface, and completing cooperative mechanism of MOFs porous carbon-based multi-component flexible electrode SC/V2O5Construction of MDFS.
The invention also aims to provide the MOFs porous carbon-based multi-component flexible electrode prepared by the preparation method of the MOFs porous carbon-based multi-component flexible electrode.
Another object of the present invention is to provide a sodium ion hybrid supercapacitor comprising said MOFs porous carbon based multi-component flexible electrode.
The invention also aims to provide an electric automobile provided with the sodium ion hybrid supercapacitor.
The invention also aims to provide a smart grid energy system provided with the sodium ion hybrid supercapacitor.
Another object of the present invention is to provide an unmanned aerial vehicle equipped with the sodium ion hybrid supercapacitor.
The invention also aims to provide an intelligent terminal provided with the sodium ion hybrid supercapacitor.
By combining all the technical schemes, the invention has the advantages and positive effects that:
(1) according to the preparation method of the MOFs porous carbon-based multi-component flexible electrode, provided by the invention, the electrode fully utilizes the synergistic effect of the materials, the limitation of a single anode material is overcome, and the electrochemical dynamics retardation in the sodium ion deintercalation process is weakened.
(2) According to the invention, the conversion type metal compound is embedded in the hard carbon derived from the double-doped MOFs, so that higher energy density is provided for the electrode, meanwhile, the insertion layer type anode material compounded on the surface provides higher power density for the electrode, and the improvement of the conductivity and stability of the electrode is realized by sequentially depositing soft carbon on the surface of the electrode, so that the electrode design is scientific.
(3) According to the invention, the structure-activity relationship of electrode structure-component-performance is established by changing the morphological structure and element composition of MOFs derivatives and intercalation type anode materials, and the SICs energy density, power density, multiplying power characteristic and cycling stability are improved.
(4) According to the invention, the double-doped MOFs derivative flexible electrode is prepared on the surface of the flexible carbon material conductive substrate, so that the flexible anode material substrate with the advantages of large specific surface area, high network conductivity and carrier mobility, good structural stability and the like is obtained. The influence of nitrogen element doping on the conductivity of MOFs-derived hard carbon materials is disclosed, and the novel structure can be applied to the batteries of SICs, sodium ion batteries, lithium ion batteries, potassium ion batteries and the like by embedding a compound consisting of phosphorus, sulfur, selenium and metal and a carbon material, so that the application value in the field of energy storage is realized.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments of the present application will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings can be obtained from the drawings without creative efforts.
Fig. 1 is a flow chart of a preparation method of a multi-component flexible electrode based on MOFs porous carbon according to an embodiment of the present invention.
Fig. 2 is a flow chart of an implementation of a method for preparing a multi-component flexible electrode based on MOFs porous carbon according to an embodiment of the present invention.
FIG. 3 shows an embodiment of the present invention, which is used for constructing an SC/V based on MOFs derivatives on a surface of a flexible carbon material conductive substrate2O5The process design flow chart of the multi-component flexible electrode based on the MOFs porous carbon of the MDFS is shown.
Fig. 4 is a schematic diagram of fabricating a MOFs-derived porous carbon flexible electrode (NPC) according to an embodiment of the present invention.
In the figure: (a) - (c) preparing metal organic frameworks with different shapes on the surface of the flexible carbon fiber through precursor regulation and control; (d) embedding the metal particles after high-temperature carbonization into MOFs derivatives of hard carbon materials; (e) the MOFs derivative porous carbon flexible electrode (NPC) is manufactured by an etching and de-doping process; (f) bi2 S3Compounding the NPC; (g) NiFe2 O4Compounding the NPC; (h) alpha-MnO2And (4) compounding the NPC.
FIG. 5 shows porous hard carbon (NPC/CF) and composite alpha-MnO provided by an embodiment of the present invention2Porous hard carbon (alpha-MnO)2a/NPC/CF) diagram;
in the figure, (a) cyclic voltammetry test (scan rate 20mV s)-1) And (b) testing the charge and discharge performance (the current value is 5mA-5 mA); at 1.0M NaSO4Cyclic voltammetry test (c) in solution (scan rate 20mV s)-1) And (d) testing the charge and discharge performance (current value is 5mA-5 mA).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Aiming at the problems in the prior art, the invention provides a multi-component flexible electrode based on MOFs porous carbon, a preparation method and application thereof, and the technical scheme of the invention is described in detail below by combining with the attached drawings.
As shown in fig. 1-fig. 2, a method for preparing a multi-component flexible electrode based on MOFs porous carbon according to an embodiment of the present invention includes the following steps:
s101, synthesizing MOFs on the surface of the flexible conductive carbon material by using a solvothermal method;
s102, carrying out double doping on MOFs (metal-organic frameworks) based on the flexible conductive carbon material;
s103, constructing a multi-component flexible electrode based on MOFs porous carbon with an adsorption-intercalation-conversion synergistic mechanism.
In step S101, the synthesizing of MOFs on the surface of the flexible conductive carbon material by using the solvothermal method provided by the embodiment of the present invention includes: under a certain temperature condition, placing a flexible carbon material conductive substrate such as carbon fiber cloth, an electrostatic spinning carbon material or two-dimensional carbon paper with the surface being treated by plasma into a precursor solution, soaking for a certain period of time, taking out, and placing a sample into a vacuum drying oven for drying to obtain the MOFs based on the flexible carbon material conductive substrate.
In step S102, the double doping of MOFs of the flexible conductive carbon-based material according to the embodiment of the present invention includes:
(1) synchronously carbonizing MOFs (metal-organic frameworks) based on a flexible conductive carbon material and self-doping nitrogen elements: placing a proper amount of the MOFs flexible electrode in a quartz boat, and placing the quartz boat under the protection of Ar at the temperature of 1-5 ℃ for min-1The temperature is raised to 450-900 ℃ in the temperature raising rate range, and the temperature is raised for a certain time at constant temperature, so as to form MOFs derived hard carbon with metal nano particles embedded in the nitrogen-doped hard carbon;
(2) the external doping of the elements adopts a chemical vapor deposition method: placing the derived hard carbon in a chemical vapor deposition furnace tube, heating to 300-500 ℃, under the protection of Ar, contacting substances containing phosphorus, sulfur, selenium or the like with the MOFs derived hard carbon along with argon gas flow, and heating at constant temperature for a certain time, thereby completing the external doping of metal particles embedded in the derivatives by active elements, and forming the MOFs derivatives of metal compound nanoparticles embedded in the nitrogen-doped hard carbon material.
As shown in fig. 3, in step S103, the embodiment of the present invention providesThe multi-component flexible electrode based on MOFs porous carbon for constructing an adsorption-intercalation-conversion synergistic mechanism comprises: v is deposited on the surface of the MDFS by using a hydrothermal synthesis method or a magnetron sputtering method2O5The film is placed in a reaction kettle with glucose solution for heating to complete the hydrothermal reaction; naturally cooling and drying to realize V2O5High temperature annealing and V2O5Coating of soft carbon thin layer on MDFS surface, and completing cooperative mechanism of MOFs porous carbon-based multi-component flexible electrode SC/V2O5Construction of MDFS.
The technical solution of the present invention is further described below with reference to examples.
The analysis of the components and the structure of the multi-component flexible electrode based on the MOFs porous carbon provided by the embodiment of the invention is as follows: carrying out the physical phase analysis of crystallinity, components and the like on the series of electrodes by adopting X-ray diffraction (XRD); the morphology, size, structure, element distribution, and other characteristics of the series of electrodes were observed by a Scanning Electron Microscope (SEM) and a high-resolution transmission electron microscope (HRTEM). The electrode surface electronic structure and bonding type will be determined by X-ray photoelectron spectroscopy (XPS). And judging the change condition of the characteristic peak of the organic group before and after MOFs carbonization and doping by using the infrared spectrogram of the sample.
The invention discloses the position, relative strength, peak width and shape change of the carbon material peak in the prepared sample through Raman spectroscopy (Raman spectroscopy), and the graphitization degree of the sample is researched. And determining the Raman spectra of the D band and the G band typical of the carbon material in the prepared series of electrodes. The peak position, peak intensity and peak width of the D band relative to the G band depend on the nature and disorder type of impurities and functional groups, and R is measured and calculated to be I D/I G to judge the graphitization degree of hard carbon and soft carbon and the relation with the electrode sodium ion deintercalation performance. The smaller the R value, the higher the graphitization degree, and the smaller the crystallite size; conversely, the larger the R value, the higher the degree of disorder of the hard carbon and the soft carbon.
The invention passes through N2Analyzing information such as specific surface area, pore size distribution, pore volume, pore channel type and the like of the electrodes in series by an adsorption/desorption curve, and combining the electrochemical performance of SICs with the phase of constant current intermittent titrationAnd (5) data is obtained, and the relation between the rapid transport and diffusion of sodium ions in the SICs and the structural characteristics of electrode pores is obtained.
The research on the diffusion coefficient of sodium ions in SICs by adopting a constant current intermittent titration technology provided by the embodiment of the invention is as follows: generally, the electron transport process in SICs is much faster than the ion diffusion and migration process, and the diffusion and migration speed of sodium ions in a liquid phase is much higher than that of sodium ions in a solid phase. Therefore, the diffusion process of sodium ions in the solid active material particles tends to become a key step in the rate control of the SICs charge-discharge process. And (3) applying constant current to the SICs under a specific environment by using a constant current intermittent titration technology, cutting off the current after the constant current is applied for a period of time, and observing the change of the system potential of the applied current section along with the time and the voltage reaching the balance after relaxation. Relaxation information of overpotential in the electrode process is obtained by analyzing the change of the potential along with time, SICs reaction kinetic information is further calculated, and the kinetic characteristics of sodium ion diffusion between the anode and the cathode are determined.
The diffusion coefficient of sodium ions in the prepared series of electrodes was estimated according to fick's second law:
DNa＝4(Vm/nAF)2[I0(dE/dx)/(dE/dt1/2)]2/π (1)
in the formula, DNaIs the diffusion coefficient of sodium ions in the electrode, Vm is the volume of the active material, A is the real electrode area immersed in the electrolyte, F is the Faraday constant, n is the number of electrons participating in the reaction, I0For titration current values, dE/dx is the slope on the coulometric titration curve and dE/dt 1/2 is the slope of the square root of the polarization voltage versus time curve. By combining coulometric titration, the difference of the diffusion coefficients of the electrode in different sodium intercalation amounts can be obtained, so that the relationship among the electrode structure, components and reaction kinetics is deeply researched. At the same time, the pull-out diffusion coefficient D was measured by applying a reverse current (applying a negative current, i.e., discharging) to the electrode in the same equilibrium state+And embedded diffusion coefficient D-When all parameters are consistent, D can be accurately compared+And D-The difference of (1):
D+/D-＝[(dE/dt1/2)-]2/[(dE/dt1/2)+]2 (2)
the difference of the sodium ion intercalation and deintercalation diffusion coefficients of the series electrodes is measured in a short time, and the reason of imbalance of electrochemical dynamics of the anode and the cathode of the SICs in the charging and discharging processes is determined.
The test of the electrochemical performance of the multi-component flexible electrode based on the MOFs porous carbon and the test of the corresponding SICs device are as follows: and judging the capacity contribution, the conductivity, the rate characteristic, the coulombic efficiency, the power density and the energy density of the multi-component flexible electrode based on the MOFs porous carbon by carrying out a constant current charge-discharge curve on the sample. The reversible degree and the polarization degree of the reaction of the active substance on the surface of the electrode are judged by researching the diffusion control and capacitance control ratio characteristics of the electrode by cyclic voltammetry on a sample. According to analysis and fitting of an impedance spectrum, the solution resistance and the charge transfer capacity of the electrode in a high-frequency region and the capacitance behavior of the electrode in a low-frequency region are quantified, the dynamic rate control step of the material and the interface is determined, relevant dynamic data are obtained, and a method for comprehensively evaluating the electrochemical performance of the electrode is established. A multi-component flexible electrode with optimized structural performance and based on MOFs porous carbon is used as an anode, activated carbon is used as a cathode, 1.0M NaPF 6 is added to serve as an electrolyte solution, a SICs device is manufactured through a packaging process of a hybrid supercapacitor device, and electrochemical test and analysis of a system are carried out on the SICs device.
The multi-component flexible electrode based on MOFs porous carbon and constructed by a synergistic mechanism of nano material 'structure engineering' and 'pore engineering' provided by the embodiment of the invention is an important way for further improving the energy storage performance of sodium ions. The MOFs is prepared on the surface of the flexible carbon material conductive substrate by a solvothermal method, the process is simple, the equipment is reliable, and the morphological structure and the element composition of the MOFs derivatives can be further regulated and controlled according to requirements. The method shows that the MOFs-derived hard carbon with nano metal particles embedded in the graphite shell prepared on the surface of the carbon material can be obtained by a high-temperature pyrolysis MOFs method.
The MOFs derivative flexible electrode with the nitrogen-doped hard carbon embedded in the metal compound is prepared by a double doping method on the basis of high-temperature carbonization of the MOFs, the method is clear in steps, relevant research reports are provided for the self-doping and the external doping of the MOFs, and the manufacturing process is sufficiently feasible. The invention skillfully masters the controllable doping technology of elements such as nitrogen, phosphorus, sulfur, selenium and the like of different materials, and prepares the flexible electrode by phosphorizing the metal compound on the surface of the flexible carbon fiber through an external doping process, and finds that the electrochemical activity of the phosphorized nano material is obviously enhanced, thereby demonstrating that the project has sufficient feasibility for carrying out the double doping process on the MOFs based on the flexible carbon material.
The invention prepares V controllably by a hydrothermal method or a magnetron sputtering method2O5Mature process of film, controllable preparation of V on MOFs derivative flexible electrode surface2O5Thin films are feasible. Research shows that the hydrothermal reaction can realize the uniform deposition of the V with the nano structure on the surface of the carbon material2O5Nanosheet, and V is regulated and controlled by changing parameters such as components, reaction time, temperature and the like of a precursor in a hydrothermal method2O5Morphology and thickness of the film. The method can prepare crystalline and amorphous V by magnetron sputtering2O5The film is formed by controlling parameters such as sputtering time, oxygen partial pressure, sputtering power and the like, and V is regulated and controlled2O5The structure-performance structure-activity relationship of the MOFs porous carbon-based multi-component flexible electrode is helpful for deeply researching the structure-activity relationship of the MOFs porous carbon-based multi-component flexible electrode. And finally, a layer of soft carbon is deposited on the surface of the active nano material by a hydrothermal method, so that the method is simple in step, good in stability and beneficial to improvement of electrode performance. Research shows that a layer of soft carbon film is uniformly deposited on the surface of the anode of the sodium ion battery by a method of hydrothermal glucose and then high-temperature annealing to form Nb2 O5@MoS2The @ SC composite electrode is coated with soft carbon, so that the rate characteristic, the conductivity and the stability of the electrode are effectively improved.
The technical effects of the present invention will be described in detail below with reference to the accompanying drawings.
The invention relates to a synthesis and application research based on a nano porous adsorption type soft carbon materialFirstly, a layer of nano porous adsorption type soft carbon film is manufactured on the surface and inside of the ordered macroporous conductive network by a hydrothermal glucose post-annealing carbonization method, and alpha-MnO is uniformly deposited on the surface of the porous soft carbon film2And the influence of the introduction of the soft carbon material on the performance of the electrode is researched.
As shown in fig. 4-5, the applicant has made preliminary experiments according to the concept of the project application, and has deposited MOFs with different morphological structures on flexible carbon fibers by regulating the composition of organic matters and metal ions in the precursor solution; carrying out high-temperature carbonization on MOFs to obtain MOFs derivatives of metal particles embedded in hard carbon materials; removing metal particles embedded in the derivatives through a de-doping process on the basis of the MOFs derivatives to prepare porous hard carbon (NPC) with a certain pore structure; adding Bi2 S3、NiFe2O4、α-MnO2The materials are deposited separately on porous hard carbon. Respectively for MOFs-derived porous carbon and for depositing alpha-MnO2MOFs-derived porous carbon compliant electrodes (α -MnO)2/NPC/CC) to fully confirm the research scheme of improving the performance of SICs by the MOFs porous carbon-based multi-component flexible electrode based on the MOFs derivative synergistic mechanism. However, the doping treatment of MOFs changes the electrode conductivity and energy density, and the intercalation type anode material V2O5The introduction of the soft carbon material and the coating of the soft carbon material are related to the improvement of the sodium ion deintercalation performance of the electrode.
The above description is only for the purpose of illustrating the present invention and the appended claims are not to be construed as limiting the scope of the invention, which is intended to cover all modifications, equivalents and improvements that are within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a multi-component flexible electrode based on MOFs porous carbon is characterized by comprising the following steps:
synthesizing MOFs on the surface of the flexible conductive carbon material by using a solvothermal method;
carrying out double doping on MOFs of the flexible conductive carbon-based material;
and (3) constructing a multi-component flexible electrode based on MOFs porous carbon with a synergistic mechanism of adsorption, intercalation and conversion.
2. The method for preparing the multi-component flexible electrode based on MOFs porous carbon according to claim 1, wherein the step of synthesizing the MOFs on the surface of the flexible conductive carbon material by using the solvothermal method comprises the following steps: under a certain temperature condition, placing a flexible carbon material conductive substrate such as carbon fiber cloth, an electrostatic spinning carbon material or two-dimensional carbon paper with the surface being treated by plasma into a precursor solution, soaking for a certain period of time, taking out, and placing a sample into a vacuum drying oven for drying to obtain the MOFs based on the flexible carbon material conductive substrate.
3. The method according to claim 1, wherein said double doping of the MOFs in a flexible conductive carbon based material comprises:
(1) synchronously carbonizing MOFs (metal-organic frameworks) based on a flexible conductive carbon material and self-doping nitrogen elements: placing a proper amount of the MOFs flexible electrode in a quartz boat, and placing the quartz boat under the protection of Ar at the temperature of 1-5 ℃ for min-1The temperature is raised to 450-900 ℃ in the temperature raising rate range, and the temperature is heated for a certain time at constant temperature to form MOFs derived hard carbon with metal nano particles embedded into the nitrogen-doped hard carbon;
(2) the external doping of the elements adopts a chemical vapor deposition method: placing the derived hard carbon in a chemical vapor deposition furnace tube, heating to 300-500 ℃, under the protection of Ar, contacting substances containing phosphorus, sulfur, selenium or the like with the MOFs derived hard carbon along with argon gas flow, and heating at constant temperature for a certain time, thereby completing the external doping of metal particles embedded in the derivatives by active elements, and forming the MOFs derivatives of metal compound nanoparticles embedded in nitrogen-doped hard carbon materials.
4. The method for preparing a multi-component flexible electrode based on MOFs porous carbon according to claim 1, wherein said structuring is performedThe MOFs porous carbon-based multi-component flexible electrode with the attached-intercalated-converted synergistic mechanism comprises: v is deposited on the surface of the double-doped MOFs derivative MDFS by using a hydrothermal synthesis or magnetron sputtering method2 O5、TiO2、Na2Ti3O7Or Nb2O5The film is placed in a reaction kettle with glucose solution for heating to complete the hydrothermal reaction; naturally cooling and drying to realize V2O5High temperature annealing and V2O5Coating of soft carbon thin layer on MDFS surface, and completing cooperative mechanism of MOFs porous carbon-based multi-component flexible electrode SC/V2O5Construction of MDFS.
5. The MOFs porous carbon-based multi-component flexible electrode prepared by the preparation method of the MOFs porous carbon-based multi-component flexible electrode disclosed by any one of claims 1 to 4.
6. A sodium-ion hybrid supercapacitor comprising the MOFs porous carbon based multi-component flexible electrode of claim 5.
7. An electric vehicle equipped with the sodium ion hybrid supercapacitor of claim 6.
8. A smart grid energy system incorporating the sodium ion hybrid supercapacitor of claim 6.
9. An unmanned aerial vehicle equipped with the sodium ion hybrid supercapacitor of claim 6.
10. An intelligent terminal equipped with the sodium ion hybrid supercapacitor of claim 6.
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