CN114823153A - Flexible sodium ion capacitor electrode material - Google Patents

Flexible sodium ion capacitor electrode material Download PDF

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CN114823153A
CN114823153A CN202210433953.1A CN202210433953A CN114823153A CN 114823153 A CN114823153 A CN 114823153A CN 202210433953 A CN202210433953 A CN 202210433953A CN 114823153 A CN114823153 A CN 114823153A
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carbon
ion capacitor
electrode material
flexible
bismuth
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CN114823153B (en
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王恭凯
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Huaxing Advanced Science And Technology Application Research Tianjin Co ltd
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Huaxing Advanced Science And Technology Application Research Tianjin Co ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04Hybrid capacitors
    • H01G11/06Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • H01G11/36Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

Abstract

The invention provides a flexible sodium ion capacitor electrode material, which is a carbon-based two-dimensional film electrode material loaded with bismuth nanoparticles obtained by instantaneously heating a carbon-based two-dimensional film loaded with metal bismuth salt. According to the method, the nano-scale metal bismuth is successfully loaded on the carbon-based two-dimensional film by means of vacuum filtration and instantaneous heating, the volume change of bismuth in the alloying process can be effectively relieved by the size distribution of the nano-scale metal bismuth, the problem of violent volume change of the metal bismuth in the alloying process is solved, the structural pulverization of a flexible electrode is effectively avoided, and the flexible sodium ion capacitor is ensured to obtain excellent cycling stability. Meanwhile, the carbon-based material is used as an instantaneous heating substrate, so that the structure stability is excellent, and the damage to the carbon-based substrate can be avoided due to the second-level heating time.

Description

Flexible sodium ion capacitor electrode material
Technical Field
The invention belongs to the field of secondary battery electrode materials. The invention particularly relates to a flexible sodium ion capacitor electrode material.
Background
Currently, highly integrated wearable electronic devices are widely used in people's lives, and portable, flexible portable electronic devices are changing people's life style. Meanwhile, the flexible wearable electronic product needs energy storage equipment with high volume ratio performance to drive so as to achieve the purposes of long endurance and meeting complex working conditions (such as mechanical deformation). Compared with other existing energy storage systems, the lithium ion battery is an energy storage device with optimal performance in the application of the current mobile device, and has the advantages of highest energy density per unit mass/volume, long service life and wide working temperature range. Research into flexible lithium ion batteries has attracted extensive attention in both academia and industry. However, despite the desirable volume-specific performance of lithium-based flexible energy storage devices, lower crustal reserves result in an increasing cost of lithium resources. The price of lithium anode materials (such as high nickel materials, lithium iron phosphate and the like) applied to lithium-based energy storage equipment is rising year by year, and the development of the lithium-based energy storage equipment is limited by high cost.
In contrast, sodium is naturally abundant and is an alkali metal with lithium, both having similar physicochemical properties. The low cost and high safety of the sodium-based energy storage device enable the sodium-based energy storage device to be expected to replace lithium to be used as a mainstream electrochemical energy storage system in the future to realize large-scale application, so that the development of the flexible sodium-based energy storage device with high volume ratio performance has extremely high market value and long-term strategic significance.
In the flexible sodium-based energy storage device, the flexible sodium-ion capacitor integrates the advantages of a super capacitor and a secondary battery, and two anode and cathode materials with different basic working principles are mainly adopted. Wherein, the non-Faraday charge-discharge process is carried out on the capacitance carbon electrode, and the oxidation-reduction reaction of surface and near surface restraint is carried out on the negative electrode. The preparation of the flexible electrode material is the core of the flexible sodium ion capacitor. The flexible electrode material with high volume ratio performance can provide higher energy density for the flexible sodium ion capacitor, and meanwhile, good cycle stability is kept.
Compared with Li + ,Na + The larger ionic radius can cause the slow electrochemical reaction kinetics, low reversible capacity, poor rate capability and poor cycle stability of the sodium-based energy storage device in the charging and discharging processes. The metal bismuth can store a large amount of Na under low potential due to larger interlayer spacing and higher sodium storage theoretical capacity + Therefore, the method becomes a research hotspot of sodium-based energy storage equipment. However, as the alloy type negative electrode material, the drastic volume change of the metal bismuth in the alloying process is a hindrance to further alloyingThe main limitation of step application.
In addition, in order to maintain stable energy output of the flexible sodium ion capacitor under repeated mechanical deformation conditions, the flexible electrode material also needs to have excellent mechanical properties. Therefore, an electrode material suitable for a flexible sodium-based energy storage device, which has both high volume ratio performance and excellent mechanical properties, is an important direction for current research of researchers.
Disclosure of Invention
The invention aims to provide a flexible sodium ion capacitor electrode material, which aims to develop a flexible electrode material with excellent mechanical stability, high volume ratio performance and rapid electrochemical reaction kinetics for a flexible sodium ion capacitor and solve the problem that metal bismuth is easy to pulverize due to violent volume change in an alloying process when the metal bismuth is used as a negative electrode material.
The purpose of the invention is realized as follows:
the embodiment of the application discloses a flexible sodium ion capacitor electrode material, which is prepared by loading bismuth nanoparticles with nanometer-level particle sizes on a carbon-based two-dimensional film and adopting the following process:
1) adding the carbon-based material into a surfactant solution and dispersing to obtain a carbon-phase dispersion liquid;
2) metal bismuth salt and/or Bi according to a certain mass ratio 2 O 3 Adding the bismuth salt into the carbon phase dispersion liquid and dispersing to obtain metal bismuth salt and/or Bi 2 O 3 A carbon phase dispersion;
3) the metal bismuth salt and/or Bi 2 O 3 The carbon phase dispersion liquid is filtered and dried to obtain the loaded metal bismuth salt and/or Bi 2 O 3 Carbon-based two-dimensional thin films;
4) for the obtained supported metal bismuth salt and/or Bi 2 O 3 The carbon-based two-dimensional film is subjected to instantaneous heating treatment to obtain the bismuth nanoparticle-loaded carbon-based two-dimensional film electrode material which can be used as a negative electrode material of the flexible sodium-ion capacitor.
In a preferred embodiment, the instantaneous heating conditions of step 2) are: heating at the temperature rising rate of 200-. In a more preferred embodiment, the heating is maintained for a period of 15. + -.3 seconds.
In a preferred embodiment, the transient heating means includes, but is not limited to, microwave irradiation, joule heating, carbon thermal shock, and the like.
In the embodiment of the present application, the instantaneous heating operation in the order of seconds not only causes the metal bismuth salt and/or Bi 2 O 3 The bismuth is reduced into bismuth nano-particles with small and uniform particle size, the agglomeration problem is avoided, meanwhile, the damage of a carbon-based two-dimensional film structure is avoided, and the instantaneous heating time has important influence on the performance of the electrode material.
In one embodiment, in step 1) of the examples of the present application, the mass ratio of the carbon-based material to the surfactant in the solution is 1: 2-3, and the dispersing process is to continue the ultrasonic treatment for 1-2 hours after magnetically stirring for 2-4 hours. Further, surfactants include, but are not limited to, any one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, cetyltrimethyl ammonium bromide, triton, and the like.
In one embodiment, carbon-based materials in the present invention include, but are not limited to, carbon nanotubes, graphene, carbon nanofibers, and the like having sp 2 A carbon material having a carbon hybrid structure.
In one embodiment, in step 2) of the examples herein, the metal bismuth salt and/or Bi 2 O 3 The mass ratio of the carbon-based material to the carbon-based material is 2-3: 1; the dispersing process is to grind the metal bismuth salt and/or Bi 2 O 3 Adding into carbon phase dispersion, magnetically stirring for 4-6 hr, and performing ultrasonic treatment for 30-60 min.
In one embodiment, the metallic bismuth salts of the present invention include, but are not limited to, Bi (NO) 3 ) 3 ·5H 2 O、BiCl 3 Bismuth citrate, which may also be other inorganic trivalent bismuth compounds.
The purpose of the ultrasound in the above step 1) and step 2) is to obtain a carbon phase dispersion liquid and a metal bismuth salt/carbon phase dispersion liquid, respectively, which have good dispersion properties.
In one embodiment of the present application, in the suction filtration operation, a two-dimensional film having a thickness of 40 to 80 μm can be obtained from a carbon phase dispersion obtained from 50 to 100 mg of the carbon-based material, and the film thickness can be customized as desired.
In one embodiment of the present application, deionized water is added during the suction filtration operation to remove the residual surfactant.
In a more preferred embodiment, the bismuth nanoparticle-loaded carbon-based two-dimensional thin-film electrode material is prepared according to the following process:
(1) preparing a sodium dodecyl sulfate solution: sodium dodecyl sulfate was dissolved in 500 mL deionized water and the concentration was maintained at 1.4-1.8 mg mL −1 Stirring for 20-40 min by using a magnetic stirrer;
(2) preparing a carbon phase dispersion liquid: adding a carbon-based material (including but not limited to carbon nano tubes, graphene, carbon nano fibers and the like) to the sodium dodecyl sulfate solution in the step (1) in a mass ratio of 1: 2, stirring for 2-4 h by using a magnetic stirrer, and then ultrasonically treating the mixed solution for 1-2 h to obtain a carbon phase dispersion liquid;
(3) preparing a metal bismuth salt/carbon phase dispersion liquid: with metallic bismuth salts (including but not limited to Bi (NO) 3 ) 3 ·5H 2 O、BiCl 3 Bismuth citrate, etc.): carbon-based material = 3: weighing the ground bismuth salt according to the mass ratio of 1, adding the bismuth salt into the carbon phase dispersion liquid obtained in the step (2), stirring for 4-6 h by using a magnetic stirrer, and then carrying out ultrasonic treatment on the mixed solution for 30-60 min to obtain metal bismuth salt/carbon phase dispersion liquid;
(4) preparing a bismuth salt loaded carbon-based two-dimensional film material by vacuum filtration: placing the dispersion liquid obtained in the step (3) in a vacuum filtration device for filtration, adding 500 mL deionized water, and drying in a vacuum oven for 6-8 h after the two-dimensional film filtration is finished;
(5) and (4) carrying out instantaneous heating treatment on the two-dimensional film obtained in the step (4) for 10-30 s to finally obtain the bismuth nanoparticle-loaded two-dimensional film negative electrode material. The instantaneous heating conditions are a heating rate of 200-.
In addition, the embodiment of the application also designs a positive electrode material matched with the negative electrode material of the flexible sodium-ion capacitor, which is characterized in that activated carbon and a carbon-based material are compounded according to a proper proportion, and then an activated carbon/carbon-based flexible electrode is prepared through vacuum filtration, and the electrode can be directly used as the positive electrode of the flexible sodium-ion capacitor. The preparation method comprises the following specific steps:
(1) preparing a sodium dodecyl sulfate solution: sodium dodecyl sulfate was dissolved in 500 mL deionized water and the concentration was maintained at 1.4-1.8 mg mL −1 Stirring for 20-40 min by using a magnetic stirrer;
(2) preparing a carbon phase dispersion liquid: adding a carbon-based material into the sodium dodecyl sulfate solution obtained in the step (1) according to the mass ratio of the carbon-based material to the sodium dodecyl sulfate = 1: 2, stirring for 2-4 h by using a magnetic stirrer, and then carrying out ultrasonic treatment on the mixed solution for 1-2 h to obtain a carbon phase dispersion liquid;
(3) preparing an activated carbon/carbon phase dispersion liquid: adding activated carbon into the carbon phase dispersion liquid obtained in the step (2) according to the mass ratio of activated carbon to carbon-based material = 2: 1, stirring for 4-6 h by using a magnetic stirrer, and then carrying out ultrasonic treatment on the mixed solution for 30-60 min to obtain the activated carbon/carbon phase dispersion liquid;
(4) preparing an active carbon/carbon-based two-dimensional film anode material by vacuum filtration: and (4) placing the dispersion liquid obtained in the step (3) into a vacuum filtration device for filtration, adding 800 mL of deionized water during the filtration, and drying the two-dimensional film in a vacuum oven for 6-8 h after the filtration of the two-dimensional film is finished to obtain the active carbon/carbon-based two-dimensional film anode material.
In a further embodiment, the assembly process of the flexible sodium ion capacitor by using the positive/negative flexible electrode material is as follows:
1) connecting a nickel lug and an aluminum lug with a nano bismuth/carbon-based negative electrode and an active carbon/carbon-based positive electrode which are matched in capacity through conductive copper paste respectively;
2) immersing the P (VDF-HFP) film into the electrolyte for 3-6 h, wherein the electrolyte-immersed P (VDF-HFP) film is taken as a quasi-solid electrolyte;
3) and (3) assembling the flexible sodium ion capacitor by utilizing a vacuum plastic package.
The embodiment of the application has beneficial technical effects of multiple aspects:
firstly, the carbon-based material with high conductivity and mechanical property is used as a flexible substrate, any conductive agent and binder are not required to be added, namely the flexible substrate can be used as a positive electrode/negative electrode of a flexible sodium ion capacitor without further treatment, and the flexible substrate has excellent conductivity and mechanical property, so that the process flow is further simplified, and dredging of active sites in the electrode is facilitated. The carbon-based material (such as carbon nano tube, graphene, carbon nano fiber and the like) with excellent mechanical properties can ensure that the flexible electrode realizes complex mechanical deformation, so that the flexible sodium ion capacitor obtains excellent comprehensive sodium storage performance.
Secondly, in the preparation process of the cathode material, nanometer-level metal bismuth is successfully loaded on the carbon-based two-dimensional film by means of vacuum filtration and instantaneous heating, the instantaneous heating in-situ reduction process has excellent heating efficiency, high temperature generated by instantaneous heating ensures excellent conversion efficiency of bismuth salt and excellent nanometer-level size distribution, bismuth nanoparticles with the minimum average particle size of 18 nm uniformly coat the carbon-based substrate, the nanometer-level size distribution can effectively relieve volume change of bismuth in the alloying process, structural pulverization of a flexible electrode is effectively avoided, and excellent cycle stability of the flexible sodium-ion capacitor is ensured. Solves the problem of violent volume change of the metal bismuth in the alloying process. Meanwhile, the carbon-based material is used as an instantaneous heating substrate, so that the structure stability is excellent, and the damage to the carbon-based substrate can be avoided due to the second-level heating time.
Finally, the nano bismuth/carbon nanotube negative electrode prepared by the invention is at 5A g −1 Still has 356 mAh g at high current density −1 Specific discharge capacity of (2). The positive pole of the active carbon/carbon nano tube is 1.6A g −1 At a current density of 25 mAh g −1 Specific discharge capacity of (2).
The nano bismuth/carbon-based cathode and the activated carbon/carbon-based anode prepared by the method have excellent mechanical properties while obtaining excellent electrochemical properties, so that the assembled flexible sodium ion capacitor can meet complex use conditions, and a new development idea is developed for flexible energy storage devices. The positive and negative electrode materials prepared by the inventionThe constant current charge-discharge curve of the flexible sodium ion capacitor prepared from the material still has no abnormal distortion under different bending angles, and the constant current charge-discharge curve is 0.22 mA cm −2 After 1200 cycles at the current density of (1), the capacity retention rate is close to 91%. For the simple and convenient compounding of the anode, the activated carbon and the carbon-based material have excellent compatibility.
In addition, the method adopting instant heating also shortens the time and the economic cost, is simple, convenient and efficient, and is easy to realize large-scale commercial application.
Drawings
Fig. 1 is an X-ray diffraction (XRD) pattern of the negative electrode material prepared in example 1.
In fig. 2, (a), (b), and (c) are Scanning Electron Microscope (SEM) images of the anode materials prepared in examples 1, 2, and 3, respectively.
In fig. 3, (a), (b) and (c) are statistical graphs of particle size distributions of the anode materials prepared in examples 1, 2 and 3, respectively.
Fig. 4 is a Scanning Electron Microscope (SEM) image of the cathode material prepared in example 1.
Fig. 5 is a graph of rate performance data for the cathode material prepared in example 1.
Fig. 6 is a graph of rate performance data for the anode materials prepared in examples 1, 2, and 3.
Fig. 7 is a graph of cycle performance data for the anode material prepared in example 1.
Fig. 8 is a graph of constant current charge and discharge curve data for the flexible sodium ion capacitor prepared in example 1.
Fig. 9 is a graph of cycle performance data for the flexible sodium ion capacitor prepared in example 1.
Detailed Description
The invention prepares the carbon nano tube loaded with the metal bismuth salt by vacuum filtration, and then reduces the bismuth salt into bismuth nano particles in situ by instantaneous heating treatment, thus obtaining the flexible sodium-ion capacitor anode material. And preparing the active carbon/carbon nanotube two-dimensional film by vacuum filtration to obtain the flexible sodium-ion capacitor cathode material. And then the prepared positive/negative electrode materials are further utilized to assemble to obtain the flexible sodium ion capacitor.
For a better understanding of the present invention, reference will now be made in detail to the present invention, which is to be considered in conjunction with the following examples, which are set forth to illustrate, but are not to be construed to limit the present invention. The experimental raw materials used in the following examples are commercially available or can be prepared by conventional methods known to those skilled in the art; the laboratory instruments used are commercially available.
Example 1
Preparation of nano bismuth/carbon nano tube two-dimensional film cathode
The method comprises the following steps: sodium dodecyl sulfate was dissolved in 500 mL deionized water to maintain the concentration of the solution at 1.4 mg mL −1 And stirring for 30 min by using a magnetic stirrer.
Step two: adding carbon nanotubes into the sodium dodecyl sulfate solution in the first step according to the mass ratio of carbon nanotubes to sodium dodecyl sulfate = 1: 2, stirring for 2 hours by using a magnetic stirrer, and then performing ultrasonic treatment on the mixed solution for 1 hour to obtain a carbon nanotube dispersion liquid; the carbon nanotube parameter used in this step is single-walled carbon nanotube with length of 10-30 μm.
Step three: with Bi (NO) 3 ) 3 ·5H 2 Weighing milled Bi (NO) at a mass ratio of O to carbon nanotubes = 3: 1 3 ) 3 ·5H 2 O, adding the mixture into the carbon nano tube dispersion liquid obtained in the second step, stirring for 4 hours by using a magnetic stirrer, and then carrying out ultrasonic treatment on the mixed solution for 40 min to obtain Bi (NO) 3 ) 3 ·5H 2 O/carbon nanotube dispersion.
Step four: and (4) placing the dispersion obtained in the third step into a vacuum filtration device for filtration, adding 600 mL of deionized water during the filtration, and drying the two-dimensional film in a vacuum oven for 6 hours after the filtration of the two-dimensional film is finished.
Step five: and (3) carrying out instantaneous heating treatment (the heating rate is 600 ℃/s, the temperature is 1100 ℃) on the two-dimensional film obtained in the fourth step for 15 s, and then obtaining the bismuth nanoparticle-loaded two-dimensional film cathode material.
Preparation of active carbon/carbon nano tube two-dimensional film anode
The method comprises the following steps: sodium lauryl sulfate was dissolved in a quantity of deionized water to maintain the concentration of the solution at 1.4 mg mL −1 And stirring for 30 min by using a magnetic stirrer.
Step two: and (2) adding the carbon nano tubes into the sodium dodecyl sulfate solution in the first step according to the mass ratio of the carbon nano tubes to the sodium dodecyl sulfate = 1: 2, stirring for 2 hours by using a magnetic stirrer, and then carrying out ultrasonic treatment on the mixed solution for 1 hour to obtain a carbon nano tube dispersion liquid.
Step three: and (3) adding activated carbon into the carbon nanotube dispersion liquid obtained in the second step according to the mass ratio of activated carbon to carbon nanotube = 2: 1, stirring for 4 hours by using a magnetic stirrer, and then carrying out ultrasonic treatment on the mixed solution for 40 min to obtain the activated carbon/carbon nanotube dispersion liquid.
Step four: and (3) placing the dispersion obtained in the third step into a vacuum filtration device for filtration, adding 600 mL of deionized water during the filtration, and drying the two-dimensional film in a vacuum oven for 6 hours after the filtration of the two-dimensional film is finished, so as to obtain the active carbon/carbon nanotube two-dimensional film cathode material.
Thirdly, assembling the flexible sodium ion capacitor:
the method comprises the following steps: connecting a nickel lug and an aluminum lug with a nano bismuth/carbon nanotube negative electrode and an activated carbon/carbon nanotube positive electrode which are matched in capacity through conductive copper paste respectively;
step two: immersing the P (VDF-HFP) film into the electrolyte for 5 hours, wherein the P (VDF-HFP) film which is fully soaked with the electrolyte is used as a quasi-solid electrolyte;
step three: and (3) assembling the flexible sodium ion capacitor by utilizing a vacuum plastic package.
Example 2
Example 2 differs from example 1 only in that the instantaneous heat treatment time was 20 s.
Example 3
Example 3 differs from example 1 only in that the instantaneous heat treatment time was 25 s.
The performance of the electrode materials and the capacitor prepared in the examples 1, 2 and 3 is examined and tested. The electrochemical performance of the electrode material was tested as follows: (1) electrochemical performance measurements were performed on each example using a button CR2025 type cell systemTest (by using the Xinwei battery test system, the voltage range is selected to be 0.1-3.5V, and the current density is 0.1-5A g −1 ) (ii) a (2) And (3) assembling a flexible sodium ion capacitor in a glove box by using a vacuum plastic package bag, and testing the conditions in the same step (1).
1. X-ray diffraction analysis
The negative electrode material prepared in example 1 was subjected to X-ray diffraction analysis, and the results are shown in fig. 1. Fig. 1 is an X-ray diffraction pattern of the nano bismuth/carbon nanotube cathode after the instantaneous heating treatment, and the result shows that after the instantaneous heating, the characteristic diffraction peaks of the in-situ reduced bismuth nanoparticles can correspond to standard PDF cards JCPDS nos. 44-1246 one by one, which indicates that pure-phase bismuth nanoparticles are formed on the carbon-based two-dimensional film.
2. Analysis by scanning Electron microscope
SEM examination was performed on the anode materials prepared in examples 1 to 3, and the results are shown in FIG. 2. Fig. 2 is a scanning electron microscope picture of the nano bismuth/carbon nanotube cathode with different instantaneous heating times (15 s, 20 s and 25 s), it can be observed from the figure that the different instantaneous heating times correspond to very different particle size distributions of bismuth nanoparticles, the bismuth nanoparticles have excellent morphology distribution after instantaneous heating for 15 s (fig. 2 (a)), and as can be seen from the statistical graph of the particle size distribution in fig. 3 (a), the average particle size after instantaneous heating for 15 s is 18 nm, the bismuth nanoparticles are tightly wrapped on the surface of the carbon nanotube, and the particle size distribution is very uniform. As can be seen from fig. 2 (b), the particle size of the bismuth nanoparticles after being heated for 20 s instantly significantly exceeds the diameter of the carbon nanotubes, the uniformity of the bismuth nanoparticles is reduced compared to 15 s, and the particle size distribution statistical chart of fig. 3 (b) shows that the average particle size after being heated for 20 s instantly is 53 nm. As can be seen from fig. 2 (c), the bismuth nanoparticles after being instantaneously heated for 25 s cannot be coated on the surface of the single carbon nanotube, and the particle size distribution statistical diagram of fig. 3 (c) shows that the average particle size after being instantaneously heated for 25 s is 240 nm. (ii) a
The SEM examination of the positive electrode material prepared in example 1 was performed, and the result is shown in fig. 4. Fig. 4 is a scanning electron microscope picture of the active carbon/carbon nanotube anode, and it can be seen from the figure that after the active carbon and the carbon nanotube are compounded, the micron-sized active carbon particles are tightly coated by the carbon nanotube, so that the efficient electron transmission of the anode can be ensured.
3. Rate capability detection
FIG. 5 is the rate capability data of the activated carbon/carbon nanotube anode, and it can be seen that the activated carbon/carbon nanotube anode has excellent rate capability, which is 1.6A g −1 At a current density of 25 mAh g −1 Specific discharge capacity of (2).
FIG. 6 is the rate performance data of nano bismuth/carbon nanotube cathodes at different instant heating times (15 s, 20 s and 25 s) with flexible electrodes at 5A g for 15 s of instant heating time −1 The discharge specific capacity can reach 356 mAh g under high current density −1 The nano-scale bismuth particles can provide rich alloying active sites for the charge-discharge process, ensure the rapid electrochemical reaction kinetics and present excellent rate performance. This corresponds to the characterization of the scanning electron microscope in fig. 2. And at instant heating time of 20 s, 25 s, at 5A g −1 The specific discharge capacity of the lithium ion secondary battery is 344 mAh g respectively at the current density of −1 、307 mAh g −1 The rate capability is lower than that of instantaneous heating for 15 s, which corresponds to the characterization result of the scanning electron microscope in fig. 2, because the more excellent particle size distribution after the instantaneous heating for 15 s provides richer active sites for the alloying process, the excellent nano-state distribution provides fast electrochemical reaction kinetics, the excellent ionic and electronic conductivity is ensured, and the excellent rate capability is further realized.
4. Cycle number test
FIG. 7 is a graph of cycle performance data for nano bismuth/carbon nanotube anodes at 5A g −1 Under the current density of the nano bismuth/carbon nano tube negative electrode, after the flexible electrode is cycled for 1000 times, the performance is stable, and the capacity retention rate is close to 100%, which shows that the nano bismuth particles prepared by the invention can effectively relieve the volume change of the nano bismuth particles, avoid the structural pulverization of the electrode, and ensure the excellent cycling stability of the nano bismuth/carbon nano tube negative electrode.
5. Charging and discharging of capacitor at different bending angles
Fig. 8 is a constant current charging and discharging curve diagram of the flexible sodium ion capacitor assembled by the nano bismuth/carbon nanotube negative electrode and the activated carbon/carbon nanotube positive electrode (example 1) at bending angles of 0 °, 90 ° and 180 °, and it can be seen from the diagram that the flexible sodium ion capacitor can still stably work at different bending angles of 0-180 °, and the charging and discharging curve has no abnormal distortion, indicating that the flexible sodium ion capacitor has excellent electrochemical stability and exhibits excellent practical application potential.
6. Cycling performance of capacitor
FIG. 9 is a graph of the cycling performance of a flexible sodium ion capacitor assembled from a nano-bismuth/carbon nanotube negative electrode and an activated carbon/carbon nanotube positive electrode (example 1) at 0.22 mA cm −2 Under the current density of (3), after the flexible sodium ion capacitor is stably cycled for 1200 circles, the capacity retention rate is close to 91%.
Comparative example 1
Comparative example 1 is different from example 1 in that the instantaneous heat treatment was not performed.
Comparative example 2
Comparative example 2 is different from example 1 in that the instantaneous heat treatment operation was changed to high-temperature calcination (1100 ℃, 1.5 hours).
The rate performance of the negative electrode materials prepared in comparative examples 1 and 2 is detected (the detection refers to the above detection "3, rate performance detection"), and the result shows that: in comparative example 1, since the instantaneous heat treatment was not performed, the metallic bismuth salt could not provide a capacity as an active material at 0.2A g −1 Has a current density of only 35 mAh g −1 The capacity of (a) is mainly contributed by the carbon nanotubes; in comparative example 2, at 5A g −1 The specific discharge capacity is only 205 mAh g at the current density of (2) −1
Scanning electron microscope analysis is carried out on the bismuth nanoparticles of the cathode material prepared in the comparative example 2, and the result is as follows: because the high-temperature calcination does not have an instantaneous temperature rise-rapid quenching mechanism, the heating process is very slow, and the bismuth is in a molten state for a long time, so that the obtained bismuth does not have a uniform distribution form, and even is partially separated from the carbon substrate.
For electrode materials prepared in comparative examples 1 and 2The cycle number test was performed with the results: in comparative example 1, at 0.8A g −1 The capacity retention rate is 74% after only 500 cycles under the current density of (3); comparative example 2 at 5A g −1 The capacity retention ratio was 85% when the current density of (1) was changed only 600 cycles.
The above-mentioned embodiments only express some preferred embodiments of the present invention, and the description is specific and detailed, but not understood to limit the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. In addition, other embodiments within the scope of the claimed invention include heating rate, holding temperature, other inorganic trivalent bismuth compounds, other compounds with sp 2 The carbon material of the carbon hybrid structure and all embodiments relating to the mass ratio of the metal bismuth salt to the carbon-based material can achieve a level substantially equivalent to that of the anode materials prepared in the above-described examples 1 to 3, and thus are not exemplified.

Claims (7)

1. A flexible sodium ion capacitor electrode material is characterized by being prepared according to the following process:
1) adding the carbon-based material into a surfactant solution and dispersing to obtain a carbon-phase dispersion liquid;
2) metal bismuth salt and/or Bi according to a certain mass ratio 2 O 3 Adding the bismuth salt into the carbon phase dispersion liquid and dispersing to obtain metal bismuth salt and/or Bi 2 O 3 A carbon phase dispersion;
3) the metal bismuth salt and/or Bi 2 O 3 The carbon phase dispersion liquid is filtered and dried to obtain the loaded metal bismuth salt and/or Bi 2 O 3 Carbon-based two-dimensional thin films of (1);
4) for the obtained supported metal bismuth salt and/or Bi 2 O 3 The carbon-based two-dimensional film is subjected to instantaneous heating treatment to obtain the bismuth nanoparticle-loaded carbon-based two-dimensional film electrode material which can be used as a negative electrode material of the flexible sodium-ion capacitor.
2. The flexible sodium ion capacitor electrode material of claim 1, wherein the instantaneous heating conditions are: heating at the temperature rising rate of 200-.
3. The flexible sodium ion capacitor electrode material of claim 1, wherein the transient heating means includes, but is not limited to, microwave irradiation, joule heating, carbon thermal shock.
4. The flexible sodium-ion capacitor electrode material of claim 1, wherein the metallic bismuth salt includes but is not limited to Bi (NO) 3 ) 3 ·5H 2 O、BiCl 3 And bismuth citrate.
5. The flexible sodium ion capacitor electrode material of claim 1, wherein the carbon-based material is sp-bearing 2 A carbon material having a carbon hybrid structure.
6. The flexible sodium-ion capacitor electrode material of claim 5, wherein the carbon-based material includes, but is not limited to, carbon nanotubes, graphene, carbon nanofibers.
7. The flexible sodium-ion capacitor electrode material as claimed in any one of claims 1 to 6, wherein in step 2), the metal bismuth salt and/or Bi 2 O 3 The mass ratio of the carbon-based material to the carbon-based material is 2-3: 1; the dispersing process is to grind the metal bismuth salt and/or Bi 2 O 3 Adding into carbon phase dispersion, magnetically stirring for 4-6 hr, and performing ultrasonic treatment for 30-60 min.
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