CN108493000B - Flexible nano porous metal/oxide supercapacitor electrode material and preparation method thereof - Google Patents

Flexible nano porous metal/oxide supercapacitor electrode material and preparation method thereof Download PDF

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CN108493000B
CN108493000B CN201810249448.5A CN201810249448A CN108493000B CN 108493000 B CN108493000 B CN 108493000B CN 201810249448 A CN201810249448 A CN 201810249448A CN 108493000 B CN108493000 B CN 108493000B
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electrode material
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alloy material
dealloying
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CN108493000A (en
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姚阿艳
王军强
霍军涛
许巍
李润伟
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Ningbo Institute of Material Technology and Engineering of CAS
University of Chinese Academy of Sciences
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Ningbo Institute of Material Technology and Engineering of CAS
University of Chinese Academy of Sciences
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • 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
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • 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
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • 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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a flexible nano porous metal/oxide supercapacitor electrode material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) preparation AxNiyCozY100‑x‑y‑z‑m‑ nCumMnThe flexible amorphous alloy material is characterized in that A is Al, Fe, Zn or Mg, and M is at least one of Ce, Mn, Au and Pt; 75-90 of x, 0-10 of y, 0-10 of z, 0-10 of m, 0-10 of n, 0 of y and z, 100-x-y-z-m-n is larger than 0 at the same time, and x, y, z, m and n are atomic percentages of corresponding atoms; (2) carrying out heat treatment on the amorphous alloy material under a vacuum condition to obtain a nanocrystalline alloy material; (3) and carrying out dealloying treatment on the nanocrystalline alloy material by adopting an alkaline or acidic solution to obtain the nanocrystalline alloy material. The preparation method is simple to operate, and the prepared electrode material has excellent electrochemical performance.

Description

Flexible nano porous metal/oxide supercapacitor electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of amorphous, electrochemical, nano and functional materials, in particular to a flexible nano porous metal/oxide supercapacitor electrode material and a preparation method thereof.
Background
Supercapacitors have some advantages such as high power density and fast charging and discharging speed, and have become a relatively popular research topic in recent years. Supercapacitors can be divided into two broad categories, depending on the mechanism of energy storage: electric double layer capacitors and pseudocapacitors. The energy storage of the double-layer capacitor is realized by the rapid adsorption-desorption of ions on the surface of an electrode. The energy storage mechanism of the pseudo capacitor is similar to that of the secondary battery, and can occur at the interface of an electrode/electrolyteThe reverse faradaic (redox) reaction stores charge. Transition metal oxides (e.g. NiO, CoO, MnO)2，RuO2) And the compound has high theoretical capacitance, and is widely concerned by researchers as a pseudocapacitor electrode material. Although the traditional methods for preparing the nano-porous pseudocapacitance electrode material are many: electrochemical method, hydrothermal method, template method, etc., however, the electrode materials prepared by these methods have some problems to degrade their electrochemical performance.
The metal oxide has low conductivity and is not favorable for electron transfer. In order to solve this problem, researchers dope a metal in an oxide and form a composite material with carbon nanotubes, graphene, a conductive polymer, etc., thereby improving the electrical conductivity thereof. The preparation of conventional electrodes requires the use of an inactive and insulating binder (e.g., PVDF) and high-pressure (5-10 MPa) post-treatment, and high-pressure treatment of the electrodes does reduce the electrical resistance between the active material and the current collector, but densifies the structure, which is not favorable for ion diffusion. The core-shell structure of the metal/oxide is also helpful for improving the electrical conductivity, however, the core-shell interface of the metal/oxide prepared by the traditional method is difficult to control.
The 3D nano porous structure can be generated by a dealloying method, the metal fragment in the structure can be used as a current collector to avoid the use of a binder, can also be used as a metal core to increase the conductivity, and the oxide shell can grow in situ on the metal core. Therefore, the preparation of the electrode material which has the nano-porous metal/oxide core-shell structure and is doped with metal in the oxide can greatly increase the conductivity and the active sites, thereby improving the capacitance characteristic.
The specific surface area and microstructure of the material are two of the most important factors affecting the electrochemical performance, and are closely related to the preparation method of the material and the used precursor. The small pores can increase the specific surface area, so that the active sites of the material are increased, but the small pores can inhibit the diffusion of ions, the large pores can reduce the specific surface area, and the multistage pores perfectly combine the advantages of the small pores and the large pores. The traditional method for preparing the hierarchical pore has various steps and is not beneficial to practical application.
Disclosure of Invention
The invention provides a preparation method of a flexible nano-porous metal/oxide supercapacitor electrode material, which is characterized in that an amorphous alloy strip is taken as a precursor, and the amorphous alloy strip is subjected to nano-crystallization and then is subjected to one-step dealloying to prepare the flexible nano-porous metal/oxide supercapacitor electrode material.
The invention provides the following technical scheme:
a preparation method of a flexible nano-porous metal/oxide supercapacitor electrode material comprises the following steps:
(1) preparation AxNiyCozY100-x-y-z-m-nCumMnThe flexible amorphous alloy material is characterized in that A is A1, Fe, Zn or Mg, and M is at least one of Ce, Mn, Au and Pt;
75-90 of x, 0-10 of y, 0-10 of z, 0-10 of m, 0-10 of n, 0 of y and z, 100-x-y-z-m-n is larger than 0 at the same time, and x, y, z, m and n are atomic percentages of corresponding atoms;
(2) carrying out heat treatment on the amorphous alloy material under a vacuum condition to obtain a nanocrystalline alloy material;
(3) and carrying out dealloying treatment on the nanocrystalline alloy material by adopting an alkaline or acidic solution to obtain the nanocrystalline alloy material.
The specific surface area and microstructure of the electrode material are two of the most important factors influencing the electrochemical performance of the electrode material, and are closely related to the preparation method of the material and the used precursor.
The elastic strain limit of the amorphous alloy used in the invention is about 2 percent, which is 3-5 times higher than that of the crystal alloy, the elastic modulus of the amorphous alloy is 30 percent lower than that of the crystal, the structure of the amorphous alloy is uniform, the components of the amorphous alloy can be adjusted in a large range, and the amorphous alloy does not have the defects of crystal boundary dislocation and the like in the crystal, the amorphous alloy can be crystallized to form a plurality of nano crystallization phases at different heat treatment temperatures due to the special metastable property of the amorphous alloy, and nano multi-level holes can be formed after dealloying. The method takes the amorphous alloy strip as a precursor, and adopts one-step dealloying after the amorphous alloy strip is subjected to nano crystallization, so that compared with the traditional method for preparing the hierarchical pore, the method has the advantage that the operation steps are greatly simplified.
The flexible amorphous alloy strip is easily obtained by a rapid solidification method of strip casting. The flexible amorphous alloy material used in the invention can be prepared by adopting the prior art.
The composition of the flexible amorphous alloy material as the precursor has important influence on the morphology of the finally prepared electrode material, thereby influencing the electrochemical performance of the electrode material.
In the amorphous alloy precursor, A (Al, Fe, Zn or Mg) is used as a matrix element, Ni and/or Co is used as an active element, and M (Ce, Mn, Au and/or Pt) is used as an auxiliary active element. The amorphous alloy is heat treated and dealloyed to generate (Ni, Co, Cu) O, (Ni, Co) OOH, Y2O3And trace A nanocrystals and A hydroxide precipitates, the lithium ion battery electrode material has a porous structure in which lithium ion battery lithium ions are contained, wherein lithium ion battery lithium ions are contained in the porous structure of the electrode material, and lithium ion battery lithium ions are contained in the porous structure of the electrode material.
Co and Ni exist in the shell in the form of oxides, and the redox reaction of the electrode material corresponds to the mutual transformation of NiO and NiOOH and CoO and CoOOH; the Cu on the surface of the shell layer exists in a metal state, so that the conductivity of the electrode material can be improved; in the amorphous alloy precursor, the addition of Y can improve the amorphous forming capability of the precursor alloy, and Y generated on the surface after dealloying2O3Is the most stable oxide and can improve the stability of the nano porous structure.
Preferably, A isxNiyCozY100-x-y-z-m-nCumMnIn the flexible amorphous alloy material, A is Al, Fe, Zn or Mg, and M is at least one of Ce, Mn, Au and Pt;
75-90 of x, 0-6 of y, 0-6 of z, 1-5 of m, 0-6 of n, 6-12 of y + z, 3-7 of 100-x-y-z-m-n, and the atomic percentages of x, y, z, m and n are corresponding atoms. The alloy has good amorphous forming ability in the element proportion range, and can generate a plurality of nano-crystalline phases after heat treatment, thereby being convenient for better regulating and controlling the microstructure of the electrode material.
For different substrate elements, the specific element proportion needs to be adjusted to obtain a proper amorphous alloy precursor, so that the finally prepared electrode material has excellent electrochemical performance.
Preferably, A isxNiyCozY100-x-y-z-m-nCumMnIn the flexible amorphous alloy material, A is Al, and M is Ce;
75-90 of x, 6 of y, 3-6 of z, 3 of m, 0-3 of n, 6-x-y-z-m-n, and x, y, z, m and n are atomic percentages of corresponding atoms.
Preferably, A isxNiyCozY100-x-y-z-m-nCumMnIn the flexible amorphous alloy material, A is Fe, and M is Ce;
75-90 of x, 3-6 of y, 3-6 of z, 3-3 of m, 0-3 of n, 1-6 of 100-x-y-z-m-n, and the atomic percentages of x, y, z, m and n are corresponding atoms.
Preferably, A isxNiyCozY100-x-y-z-m-nCumMnIn the flexible amorphous alloy material, A is Zn, and M is Ce and/or Mn;
75-90 of x, 3-6 of y, 0 of z, 3 of m, 0-3 of n, 1-3 of 100-x-y-z-m-n, and the atomic percentages of x, y, z, m and n are corresponding atoms.
Preferably, A isxNiyCozY100-x-y-z-m-nCumMnIn the flexible amorphous alloy material, A is Mg, and M is Ce;
x is 75-90, y is 0, z is 1-3, m is 3, n is 0-3, 100-x-y-z-m-n is 1-3, and x, y, z, m and n are atomic percentages of corresponding atoms.
In the step (2), during heat treatment, nanocrystalline phases with different grain diameters are generated in the amorphous alloy material, and during subsequent dealloying treatment, the nanocrystalline phases are dissolved to form pore channel structures with different pore sizes, so that a hierarchical pore structure of the electrode material is formed.
Preferably, in the step (2), the heat treatment temperature is not less than the glass transition starting temperature of the amorphous alloy material.
When the heat treatment temperature is too low, the size of the generated nano crystallization phase is smaller, the aperture of the nano hierarchical pore formed after dealloying is smaller, and the volume change of the electrode material is larger due to atomic diffusion in the dealloying process, so that more cracks are formed on the surface of the electrode material, and the excessive cracks are not beneficial to the transfer of charges in the redox reaction process; when the heat treatment temperature is too high, the size of the generated nano crystallization phase is too large, and the aperture of the nano hierarchical pore formed after dealloying is larger, so that the electrochemical performance of the electrode material is reduced. Therefore, the electrochemical performance of the electrode material is reduced by the heat treatment temperature which is too low or too high.
Further preferably, in the step (2), the heat treatment temperature is 350 to 500 ℃.
Further preferably, in the step (2), the heat treatment temperature is higher than the last crystallization starting temperature of the amorphous alloy material and is lower than 500 ℃.
The heat treatment comprises the following steps: heating to the heat treatment temperature at the heating rate of 150-250 ℃/min, preserving the heat for 5-30 min, preferably 5-10 min, and then rapidly quenching, wherein the quenching time is less than 1min, preferably less than 5 s.
In the step (3), the concentration of alkali in the alkaline solution is 1-6 mol/L; in the acidic solution, the concentration of acid is 1-6 mol/L.
Preferably, the alkali is at least one of NaOH, LiOH and KOH; the acid is H2SO4HCl and HNO3At least one of (1).
Preferably, the dealloying time is 5-60 min; the dealloying temperature is 10-40 ℃.
Preferably, step (3) is followed by:
and (4) performing constant-current circulating charge and discharge for 50-500 times on the flexible nano porous metal/oxide supercapacitor electrode material prepared in the step (3), and performing electrochemical polarization.
Preferably, the current density is 5-10 mA/cm during constant current cyclic charge and discharge2。
Through electrochemical polarization, the electrode material is activated to generate more reactive active sites, which is beneficial to improving the pseudocapacitance characteristic of the electrode material.
The invention also provides the flexible nano-porous metal/oxide supercapacitor electrode material prepared by the preparation method.
The flexible nano-porous metal/oxide supercapacitor electrode material has a uniform hierarchical pore structure: in the heat treatment process, the nanocrystalline nuclei of the substrate elements grow rapidly, macropores (30-100 nm) are formed after dealloying, and some intermetallic compounds (such as Al)3Y) is dissolved to form a mesopore (8-20 nm), and the multi-element intermetallic compound is dissolved to form a small pore (3-4 nm).
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention adopts amorphous alloy as a precursor, generates various nanocrystalline phases after heat treatment, and generates a uniform hierarchical pore structure after dealloying, thereby not only increasing the transport property of ions, but also increasing the active sites of reaction;
(2) the prepared electrode material nano-porous segment forms a metal/oxide core-shell structure in situ, the material with the structure can be directly used as a working electrode of a super capacitor, and the 3D structure can be used as a current collector and has the characteristic of pseudo-capacitance, so that the electrochemical performance of the super capacitor is greatly improved;
(3) the metal state Cu exists in both the core and the shell of the core-shell structure of the metal/oxide, so that the conductivity of the electrode material is increased;
(4) the flexible amorphous alloy is used as a precursor, and the prepared electrode material has flexibility;
(5) the preparation method is simple and is suitable for large-scale production.
Drawings
FIG. 1 is an XRD pattern of the amorphous alloy ribbon obtained in step (2) in examples 1-6;
FIG. 2 is a DSC chart of the amorphous alloy ribbon obtained in step (2) in examples 1 to 6;
FIG. 3 is an XRD pattern of the annealed strip obtained in step (3) in examples 1 to 6;
FIG. 4 is an XRD pattern of the strip obtained in step (4) after dealloying in examples 1 to 6;
FIG. 5 is a CV diagram of the electrode material obtained in step (5) in examples 1 to 6;
FIG. 6 shows the constant current (6 mA/cm) of the electrode material obtained in the step (5) in examples 1 to 62) A charge-discharge curve chart;
FIG. 7 is a graph showing the specific capacitance of the electrode material obtained in step (5) at a specific annealing temperature (257-550 ℃) in examples 1-6;
FIG. 8 shows the specific capacitance of the electrode material obtained in step (5) in accordance with the current density (4-15 mA/cm) in example 12) The inside of the change curve graph is a corresponding constant current charging and discharging curve graph;
FIG. 9 is an SEM photograph of the surface of the electrode material obtained in step (5) in example 1, wherein the scale in (a) is 100 μm and the scale in (b) is 1 μm;
FIG. 10 shows N in the electrode material obtained in step (5) in example 12Adsorption-desorption curve chart;
FIG. 11 is a graph showing the pore size distribution of the electrode material obtained in step (5) in example 1;
FIG. 12 is a TEM photograph of the electrode material obtained in step (5) in example 1, wherein the scale in (a) is 100nm and the scale in (b) is 50 nm;
FIG. 13 is the EDS graph of the electrode material obtained in step (5) in line scan in the green line direction in FIG. 12(b) in example 1;
FIG. 14 is the XPS plot of the surface of the electrode material obtained in step (5) and Co after Ar ion etching in example 1;
FIG. 15 is the XPS plot of the surface of the electrode material obtained in step (5) and Ni after Ar ion etching in example 1;
FIG. 16 is the XPS plot of the surface of the electrode material obtained in step (5) and Cu after Ar ion etching in example 1;
FIG. 17 is an XPS plot of the surface of the electrode material obtained in step (5) and Y after Ar ion etching in example 1;
FIG. 18 is the XPS plot of the surface of the electrode material obtained in step (5) and Al after Ar ion etching in example 1;
FIG. 19 is an SEM photograph of the surface of the electrode material obtained in step (5) in example 2, wherein the scale in (a) is 100 μm and the scale in (b) is 1 μm;
FIG. 20 is an SEM photograph of the surface of the electrode material obtained in step (5) in example 3, wherein the scale in (a) is 100 μm and the scale in (b) is 1 μm;
FIG. 21 is an SEM photograph of the surface of the electrode material obtained in step (5) in example 4, wherein the scale in (a) is 100 μm and the scale in (b) is 1 μm;
FIG. 22 is an SEM photograph of the surface of the electrode material obtained in step (5) in example 5, wherein the scale in (a) is 100 μm and the scale in (b) is 1 μm;
FIG. 23 is an SEM photograph of the surface of the electrode material obtained in step (5) in example 6, wherein the scale in (a) is 100 μm and the scale in (b) is 1 μm;
FIG. 24 is a constant current (8 mA/cm) of the electrode material obtained in the step (5) in example 72) A charge-discharge curve chart;
FIG. 25 is a constant current (8 mA/cm) of the electrode material obtained in the step (5) in example 82) A charge-discharge curve chart;
FIG. 26 is a constant current (8 mA/cm) of the electrode material obtained in the step (5) in example 92) A charge-discharge curve chart;
FIG. 27 is a constant current (8 mA/cm) of the electrode material obtained in the step (5) in example 102) And (4) a charge-discharge curve diagram.
Detailed Description
The invention will be described in further detail below with reference to the drawings and examples, which are intended to facilitate the understanding of the invention without limiting it in any way.
Example 1: a preparation method of a flexible nano-porous metal/oxide supercapacitor electrode material comprises the following steps:
(1) selecting A1, Ni, Co, Y and Cu elements with the purity of more than 99.9 percent according to Al82Ni6Co3Y6Cu3(atomic percentage) and arc melting the alloy elements in the proportion in Ar protective atmosphere.
(2) Remelting the master alloy in a quartz tube, spraying the remelted master alloy on a copper roller with the linear speed of 40m/s, and throwing the remelted master alloy into an amorphous strip, wherein the thickness of the strip is 20-30 mu m, the width of the strip is 1-2 mm, and the length of the strip is more than ten meters.
Winding the amorphous strip into different curvature radiuses, so that the amorphous alloy has good flexibility; the XRD pattern of the strip is shown in figure 1, and only has one diffuse scattering peak, which indicates that the strip is completely amorphous; the DSC curve of the band is shown in FIG. 2, the glass transition temperature T g257 ℃ and the first initial crystallization temperature Tx1275 ℃ and a second initial crystallization temperature Tx2340 deg.C, third initial crystallization temperature T x3367 ℃, a suitable annealing temperature may be selected according to these characteristic temperatures.
(3) The amorphous ribbon is heated at 421 ℃ and the vacuum degree is 5 multiplied by 10-3Annealing under the condition of Pa for 10 min. The XRD pattern of the annealed strip is shown in fig. 3, curve (a), and forms a plurality of nanocrystalline phases.
(4) And (3) putting the annealed strip into a 4mol/L KOH solution, dealloying for 10min at room temperature, and repeatedly cleaning with deionized water and absolute ethyl alcohol to obtain the working electrode. The XRD pattern of the strip after dealloying is shown in the curve (a) in FIG. 4, and the nanocrystalline phase formed by annealing is dissolved to form (Ni, Co, Cu) O, (Ni, Co) OOH, Y2O3And trace amounts of Al nanocrystals and Al (OH)3Precipitation, these oxides/hydroxides play an important role during the use of the supercapacitor.
(5) The method adopts a cyclic voltammetry method and a constant current charge-discharge method through a Zahner Zennium electrochemical workstation, and adopts a three-electrode system: and (4) testing the electrochemical performance of the material in a voltage range of 0-0.55V by taking the electrode prepared in the step (4) as a working electrode, Ag/AgCl as a reference electrode, a Pt sheet as a counter electrode and 4mol/LKOH as an electrolyte. The CV curve of the strip after dealloying was as shown in curve (a) in FIG. 5, with distinct redox peaks indicating that a redox reaction occurred, wherein the redox reaction corresponds to the mutual transformation of NiO and NiOOH and CoO and CoOOH;
the strip after dealloying has a current density of 6mA/cm2When the charge and the discharge are carried out at constant current, the curve is shown as a curve (a) in fig. 6, and obvious steps exist in the curve, which indicates that oxidation-reduction reaction occurs in the charge and discharge process and is consistent with the result of a CV curve;
the specific capacitance was calculated from the constant current charge-discharge curve, and the result is shown in FIG. 7, where the specific capacitance of the material was 2.05F/cm2(932F/cm3). The electrode material is subjected to electrochemical polarization for 200 times of charge-discharge circulation, the electrochemical activity is greatly increased, and the capacitance can reach 3.35F/cm2(1523F/cm3) The electrode material has excellent energy storage function;
adopting 4-15 mA/cm2The constant current of the electrode is tested for charging and discharging, the change curve of the specific capacitance along with the current density is shown in figure 8, and the change of the capacitance is less than 1 percent, which shows that the flexible nano-porous AlNiCoYCu metal/oxide core-shell electrode material prepared by the invention has excellent stability;
the SEM photograph of the surface of the electrode material is shown in fig. 9, and it can be seen from fig. 9(a) that the surface of the material is very smooth and has no obvious cracks, which is related to the enhancement of the moment caused by the growth of the nanocrystalline phase, and is advantageous for the transfer of charges during the redox reaction. From fig. 9(b), it can be seen that isotropic and relatively uniform pores are formed, which is closely related to the nature of the long-range disorder of the amorphous alloy, and the pore size of the nano-porous is relatively large, which is related to the growth of the nano-crystals during the annealing process;
the BET method is adopted to calculate that the electrode material has larger specific surface area: 37.9m2G (N thereof)2The adsorption-desorption curve is shown in fig. 10), which can provide more active sites for the redox reaction;
the pore size distribution curve of the electrode material is shown in fig. 11, and it can be seen that there are 3 pores: the nanocrystalline nuclei of Al grow rapidly during annealing, and macropores (30-100 nm) are formed after dealloying, and some intermetallic compounds (such as Al)3Y) forms mesopores (8-20 nm) after dissolution, and forms micropores (3-4 nm) after dissolution of the multi-element intermetallic compound, and the result is also in TEM photograph is confirmed in FIG. 12;
the chemical composition of the electrode material was determined by performing an EDS line scan along the green line in fig. 12(b), and the results are shown in fig. 13, which indicates that the fragments in the porous structure are composed of a metal core and an oxide shell, and that there is a good chemical bonding interface between them, which facilitates charge transfer during the redox reaction.
The valence state change of the surface element of the electrode material and the surface element etched by Ar ions is researched by adopting an XPS method, and the result is shown in figures 14-18, Co and Ni on the surface exist in the form of oxide, and the active Co/Ni oxide shell layer exists on the ligand of the nano porous structure. Most of the Cu on the surface is still in a metal state, which can improve the electric conductivity of the material. The addition of Y can improve the glass forming ability of the precursor alloy, and Y generated on the surface after dealloying2O3Is the most stable oxide and can improve the stability of the nano porous structure. After 5min of Ar ion etching, metallic elements can be seen, and the existence of metal cores in the margin is determined. Compared with the surface, the peak of the oxide is shifted to a low energy state after Ar ion etching, which shows that the oxide obtains more electrons, and the electron conduction of the material is favorably improved, so that excellent pseudocapacitance characteristics are generated.
Example 2: a preparation method of a flexible nano-porous metal/oxide supercapacitor electrode material comprises the following steps:
steps (1) and (2) were the same as in example 1;
(3) the amorphous ribbon was heated at 257 ℃ under a vacuum of 5X 10-3Annealing under the condition of Pa for 10 min. The XRD pattern of the annealed strip is shown in fig. 3, curve (b), and forms a plurality of nanocrystalline phases.
(4) And (3) putting the annealed strip into a 4mol/L KOH solution, dealloying for 10min at room temperature, and repeatedly cleaning with deionized water and absolute ethyl alcohol to obtain the working electrode. The XRD pattern of the dealloyed strip is shown in the curve (b) in FIG. 4, and the nanocrystalline phase formed by annealing is dissolved to form (Ni, Co, Cu) O, (Ni, Co) OOH, Y2O3And trace amounts of Al nanocrystals and Al (OH)3Precipitation of these oxides/hydroxides in supercapacitorsThe device plays an important role in the using process.
(5) The prepared electrode material was subjected to electrochemical performance test using the method of example 1.
The CV curve of the strip after dealloying, as shown in curve (b) in fig. 5, has a smaller redox peak, indicating that a small amount of redox reaction occurs, wherein the redox reaction corresponds to the mutual transition of NiO and NiOOH and CoO and cooo;
the strip after dealloying has a current density of 6mA/cm2When the charge and the discharge are carried out at constant current, the curve is shown as a curve (b) in fig. 6, and steps exist in the curve, which indicates that oxidation-reduction reaction occurs in the charge and discharge process and is consistent with the result of a CV curve;
the specific capacitance was calculated from the constant current charge-discharge curve, and the result was shown in FIG. 7, where the specific capacitance of the material was 0.58F/cm2(262F/cm3). The electrode material has better energy storage function;
the SEM photograph of the surface of the electrode material is shown in fig. 19, and it can be seen from fig. 19(a) that there are many cracks on the surface of the material, which are related to the volume change of the material caused by the diffusion of atoms during the dealloying process, and the existence of many cracks is not favorable for the transfer of charges during the redox reaction. It can be seen from fig. 19(b) that isotropic and relatively uniform pores are formed, which is closely related to the nature of the long-range disorder of the amorphous alloy, and that the pore size of the nano-porous is small due to the relatively small size of the nano-crystals generated by the low-temperature annealing.
Example 3: a preparation method of a flexible nano-porous metal/oxide supercapacitor electrode material comprises the following steps:
steps (1) and (2) were the same as in example 1;
(3) the amorphous strip was heated at 312 ℃ under a vacuum of 5X 10-3Annealing under the condition of Pa for 10 min. The XRD pattern of the annealed strip is shown in FIG. 3, curve (c), which forms a plurality of nanocrystalline phases.
(4) And (3) putting the annealed strip into a 4mol/L KOH solution, dealloying for 10min at room temperature, and repeatedly cleaning with deionized water and absolute ethyl alcohol to obtain the working electrode. XRD pattern of strip after dealloyingThe spectrum is shown in FIG. 4 as curve (c), in which the nanocrystalline phase formed by annealing is dissolved to form (Ni, Co, Cu) O, (Ni, Co) OOH, Y2O3And trace amounts of Al nanocrystals and Al (OH)3Precipitation, these oxides/hydroxides play an important role during the use of the supercapacitor.
(5) The prepared electrode material was subjected to electrochemical performance test using the method of example 1.
The CV curve of the strip after dealloying, as shown in curve (c) in fig. 5, has a smaller redox peak, indicating that a small amount of redox reaction occurs, wherein the redox reaction corresponds to the mutual transition of NiO and NiOOH and CoO and CoOOH;
the strip after dealloying has a current density of 6mA/cm2When the charge and the discharge are carried out at constant current, the curve is shown as a curve (c) in fig. 6, and steps exist in the curve, which indicates that oxidation-reduction reaction occurs in the charge and discharge process and is consistent with the result of a CV curve;
the specific capacitance was calculated from the constant current charge-discharge curve, and the result was shown in FIG. 7, where the specific capacitance of the material was 0.67F/cm2(305F/cm3) The electrode material has a better energy storage effect;
the SEM photograph of the surface of the electrode material is shown in fig. 20, and it can be seen from fig. 20(a) that there are many cracks on the surface of the material, which are related to the volume change of the material caused by the diffusion of atoms during the dealloying process, and the existence of many cracks is not favorable for the transfer of charges during the redox reaction. It can be seen from fig. 20(b) that isotropic and relatively uniform pores are formed, which is closely related to the nature of the long-range disorder of the amorphous alloy, and that the pore size of the nano-porous is small due to the relatively small size of the nano-crystals generated by the low-temperature annealing.
Example 4: a preparation method of a flexible nano-porous metal/oxide supercapacitor electrode material comprises the following steps:
steps (1) and (2) were the same as in example 1;
(3) the amorphous strip was heated at 367 ℃ under a vacuum of 5X 10-3Annealing under the condition of Pa for 10 min. The XRD pattern of the annealed strip is shown by curve (d) in FIG. 3Various nanocrystalline phases are formed.
(4) And (3) putting the annealed strip into a 4mol/L KOH solution, dealloying for 10min at room temperature, and repeatedly cleaning with deionized water and absolute ethyl alcohol to obtain the working electrode. The XRD pattern of the dealloyed strips is shown in FIG. 4, curve (d), and the nanocrystalline phase formed by annealing is dissolved to form (Ni, Co, Cu) O, (Ni, Co) OOH, Y2O3And trace amounts of Al nanocrystals and Al (OH)3Precipitation, these oxides/hydroxides play an important role during the use of the supercapacitor.
(5) The prepared electrode material was subjected to electrochemical performance test using the method of example 1.
The CV curve of the strip after dealloying was as shown in the curve (d) in FIG. 5, with distinct redox peaks indicating that a redox reaction occurred, wherein the redox reaction corresponds to the mutual transformation of NiO and NiOOH and CoO and CoOOH;
the strip after dealloying has a current density of 6mA/cm2When the charge and the discharge are carried out at constant current, the curve is shown as a curve (d) in fig. 6, and obvious steps exist in the curve, which indicates that the oxidation-reduction reaction occurs in the charge and discharge process and is consistent with the result of a CV curve;
the specific capacitance was calculated from the constant current charge-discharge curve, and the result is shown in FIG. 7, where the specific capacitance of the material was 1.75F/cm2(795F/cm3). The electrode material has better energy storage function;
SEM photograph of the surface of the electrode material is shown in FIG. 21, and it can be seen from FIG. 21(a) that there are few cracks on the surface of the material, which are associated with the increase in the moment of growth of the nanocrystalline phase. It can be seen from fig. 21(b) that isotropic and relatively uniform pores are formed, which is closely related to the nature of the long-range disorder of the amorphous alloy, and that the pore size of the nano-porous is large, which is related to the growth of the nano-crystals during the annealing process.
Example 5: a preparation method of a flexible nano-porous metal/oxide supercapacitor electrode material comprises the following steps:
steps (1) and (2) were the same as in example 1;
(3) the amorphous ribbon was heated at 500 ℃ under vacuum of 5X 10-3Annealing under the condition of Pa for 10 min. The XRD pattern of the annealed strip is shown in FIG. 3, curve (e), which forms a plurality of nanocrystalline phases.
(4) And (3) putting the annealed strip into a 4mol/L KOH solution, dealloying for 10min at room temperature, and repeatedly cleaning with deionized water and absolute ethyl alcohol to obtain the working electrode. The XRD pattern of the dealloyed strips is shown in FIG. 4, curve (e), and the nanocrystalline phase formed by annealing is dissolved to form (Ni, Co, Cu) O, (Ni, Co) OOH, Y2O3And trace amounts of Al nanocrystals and Al (OH)3Precipitation, these oxides/hydroxides play an important role during the use of the supercapacitor.
(5) The prepared electrode material was subjected to electrochemical performance test using the method of example 1.
The CV curve of the strip after dealloying was as shown in curve (e) in FIG. 5, with distinct redox peaks indicating that a redox reaction occurred, wherein the redox reaction corresponds to the mutual transformation of NiO and NiOOH and CoO and CoOOH;
the strip after dealloying has a current density of 6mA/cm2When the charge and the discharge are carried out at constant current, the curve is shown as a curve (e) in fig. 6, and obvious steps exist in the curve, which indicates that the oxidation-reduction reaction occurs in the charge and discharge process and is consistent with the result of a CV curve;
the specific capacitance was calculated from the constant current charge-discharge curve, and the result is shown in FIG. 7, where the specific capacitance of the material was 1.06F/cm2(482F/cm3). The electrode material has better energy storage function;
the SEM photograph of the surface of the electrode material is shown in fig. 22, and it can be seen from fig. 22(a) that there is no significant crack on the surface of the material, which is related to the enhancement of the moment caused by the growth of the nanocrystalline phase, and facilitates the transfer of charge during the redox reaction. It can be seen from fig. 22(b) that isotropic and relatively uniform pores are formed, which is closely related to the nature of the long-range disorder of the amorphous alloy, and the pore size of the nano-porous is large, which is related to the growth of the nano-crystals during the annealing process.
Example 6: a preparation method of a flexible nano-porous metal/oxide supercapacitor electrode material comprises the following steps:
steps (1) and (2) were the same as in example 1;
(3) the amorphous ribbon was heated at 550 ℃ under a vacuum of 5X 10-3Annealing under the condition of Pa for 10 min. The XRD pattern of the annealed strip is shown in FIG. 3, curve (f), which forms a plurality of nanocrystalline phases.
(4) And (3) putting the annealed strip into a 4mol/L KOH solution, dealloying for 10min at room temperature, and repeatedly cleaning with deionized water and absolute ethyl alcohol to obtain the working electrode. The XRD pattern of the dealloyed strips is shown in the curve (f) in FIG. 4, and the nanocrystalline phase formed by annealing is dissolved to form (Ni, Co, Cu) O, (Ni, Co) OOH, Y2O3And trace amounts of Al nanocrystals and Al (OH)3Precipitation, these oxides/hydroxides play an important role during the use of the supercapacitor.
(5) The prepared electrode material was subjected to electrochemical performance test using the method of example 1.
The CV curve of the strip after dealloying was as shown in the curve (f) in FIG. 5, with distinct redox peaks indicating that a redox reaction occurred, wherein the redox reaction corresponds to the mutual transformation of NiO and NiOOH and CoO and CoOOH;
the strip after dealloying has a current density of 6mA/cm2When the charge and the discharge are carried out at constant current, the curve is shown as a curve (f) in fig. 6, and obvious steps exist in the curve, which indicates that the redox reaction occurs in the charge and discharge process and is consistent with the result of a CV curve;
the specific capacitance was calculated from the constant current charge-discharge curve, and the result was shown in FIG. 7, where the specific capacitance of the material was 0.87F/cm2(396F/cm3). The electrode material has better energy storage function;
the SEM photograph of the surface of the electrode material is shown in fig. 23, and it can be seen from fig. 23(a) that there is no significant crack on the surface of the material, which is related to the enhancement of the moment caused by the growth of the nanocrystalline phase, and is advantageous for the transfer of charge during the redox reaction. It can be seen from fig. 23(b) that isotropic and relatively uniform pores are formed, which is closely related to the nature of the long-range disorder of the amorphous alloy, and the pore size of the nano-porous is large, which is related to the growth of the nano-crystal during the annealing process.
Example 7: a preparation method of a flexible nano-porous metal/oxide supercapacitor electrode material comprises the following steps:
(1) selecting Al, Ni, Co, Y, Ce and Cu elements with the purity of more than 99.9 percent according to the Al75Ni6Co6Y7Ce3Cu3(atomic percentage) and arc melting the alloy elements in the proportion in Ar protective atmosphere.
(2) Remelting the master alloy in a quartz tube, spraying the remelted master alloy on a copper roller with the linear speed of 40m/s, and throwing the remelted master alloy into an amorphous strip, wherein the thickness of the strip is 20-30 mu m, the width of the strip is 1-2 mm, and the length of the strip is more than ten meters.
(3) The amorphous ribbon was heated at 450 ℃ under vacuum of 5X 10-3Annealing under the condition of Pa for 10 min.
(4) And (3) putting the annealed strip into a 4mol/L KOH solution, dealloying for 10min at room temperature, and repeatedly cleaning with deionized water and absolute ethyl alcohol to obtain the working electrode.
(5) The prepared electrode material was subjected to electrochemical performance test using the method of example 1.
The strip after dealloying has a current density of 8mA/cm2When the charge and the discharge are carried out at constant current, the curve is shown in figure 24, and obvious steps exist in the curve, which indicates that the redox reaction occurs in the charge and discharge process.
The specific capacitance of the material is calculated to be 0.94F/cm according to the constant-current charge-discharge curve2(427F/cm3) The electrode material has better energy storage effect.
Example 8: a preparation method of a flexible nano-porous metal/oxide supercapacitor electrode material comprises the following steps:
(1) selecting Mg, Co, Y, Ce and Cu elements with purity of more than 99.9 percent according to Mg90Co3Y3Ce1Cu3(atomic percent) mixing, and carrying out electric arc on the alloy elements in the mixture ratio in Ar protective atmosphereAnd (4) smelting.
(2) Remelting the master alloy in a quartz tube, spraying the remelted master alloy on a copper roller with the linear speed of 40m/s, and throwing the remelted master alloy into an amorphous strip, wherein the thickness of the strip is 20-30 mu m, the width of the strip is 1-2 mm, and the length of the strip is more than ten meters.
(3) The amorphous strip was heated at 350 ℃ under vacuum of 5X 10-3Annealing under the condition of Pa for 30 min.
(4) And (3) putting the annealed strip into 2mol/L HCl solution, dealloying for 30min at room temperature, and repeatedly cleaning with deionized water and absolute ethyl alcohol to obtain the working electrode.
(5) The prepared electrode material was subjected to electrochemical performance test using the method of example 1.
The strip after dealloying has a current density of 8mA/cm2When the charge and discharge were carried out with constant current, the curve is shown in fig. 25, and there is no distinct step in the curve, which indicates that only a slight amount of redox reaction was present during the charge and discharge, and the contribution of the capacitance was substantially derived from the electric double layer capacitance, because the content of the active material was small. The specific capacitance of the material is calculated to be 0.35F/cm according to the constant-current charge-discharge curve2(159F/cm3) The electrode material has better energy storage effect.
Example 9: a preparation method of a flexible nano-porous metal/oxide supercapacitor electrode material comprises the following steps:
(1) selecting Fe, Ni, Co, Y and Cu elements with the purity of more than 99.9 percent according to the Fe82Ni6Co3Y6Cu3(atomic percentage) and arc melting the alloy elements in the proportion in Ar protective atmosphere.
(2) Remelting the master alloy in a quartz tube, spraying the remelted master alloy on a copper roller with the linear speed of 40m/s, and throwing the remelted master alloy into an amorphous strip, wherein the thickness of the strip is 20-30 mu m, the width of the strip is 1-2 mm, and the length of the strip is more than ten meters.
(3) The amorphous ribbon was heated at 400 ℃ under a vacuum of 5X 10-3Annealing under the condition of Pa for 10 min.
(4) The annealed strip was placed in a 1mol/L H bath2SO4In the solution, dealloying for 30min, and repeatedly cleaning with deionized water and anhydrous ethanol to obtain the final productA working electrode.
(5) The prepared electrode material was subjected to electrochemical performance test using the method of example 1.
The strip after dealloying has a current density of 8mA/cm2When the charge and the discharge are carried out at constant current, the curve is shown in figure 26, and obvious steps exist in the curve, which indicates that the redox reaction occurs in the charge and discharge process. The specific capacitance of the material is calculated to be 0.85F/cm according to the constant current charging and discharging curve2(386F/cm3) The electrode material has better energy storage effect.
Example 10: a preparation method of a flexible nano-porous metal/oxide supercapacitor electrode material comprises the following steps:
(1) selecting Zn, Ni, Y, Cu, Mn and Ce with purity of more than 99.9 percent according to Zn82Ni6Y3Cu3Mn3Ce3Proportioning (atomic percentage), and smelting the alloy elements in the proportioning in Ar protective atmosphere.
(2) Remelting the master alloy in a quartz tube, spraying the remelted master alloy on a copper roller with the linear speed of 40m/s, and throwing the remelted master alloy into an amorphous strip, wherein the thickness of the strip is 20-30 mu m, the width of the strip is 1-2 mm, and the length of the strip is more than ten meters.
(3) The amorphous ribbon was heated at 450 ℃ under vacuum of 5X 10-3Annealing under the condition of Pa for 10 min.
(4) And (3) putting the annealed strip into a 4mol/L KOH solution, dealloying for 10min at room temperature, and repeatedly cleaning with deionized water and absolute ethyl alcohol to obtain the working electrode.
(5) The prepared electrode material was subjected to electrochemical performance test using the method of example 1.
The strip after dealloying has a current density of 8mA/cm2When the charge and the discharge are carried out at constant current, the curve is shown in FIG. 27, and obvious steps exist in the curve, which indicates that the oxidation-reduction reaction occurs in the charge and discharge process. The specific capacitance of the material is calculated to be 1.2F/cm according to the constant current charging and discharging curve2(545F/cm3) The electrode material has better energy storage effect.
The above-mentioned embodiments are intended to illustrate the technical solutions and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions, equivalents, etc. made within the scope of the principles of the present invention should be included in the scope of the present invention.

Claims (8)

1. A preparation method of a flexible nano-porous metal/oxide supercapacitor electrode material is characterized by comprising the following steps:
(1) preparation AxNiyCozY100-x-y-z-m-nCumMnThe flexible amorphous alloy material is characterized in that A is Al, Fe, Zn or Mg, and M is at least one of Ce, Mn, Au and Pt;
x = 75-90, y = 0-10, z = 0-10, m = 0-10, n = 0-10, y and z are not 0 at the same time, 100-x-y-z-m-n is greater than 0, and x, y, z, m and n are atomic percentages of corresponding atoms;
(2) carrying out heat treatment on the amorphous alloy material under a vacuum condition to obtain a nanocrystalline alloy material; the heat treatment temperature is 350-500 ℃;
the heat treatment comprises the following steps: heating to the heat treatment temperature at the heating rate of 150-250 ℃/min, preserving the heat for 5-30 min, and then rapidly quenching, wherein the quenching time is less than 1 min;
(3) and carrying out dealloying treatment on the nanocrystalline alloy material by adopting an alkaline or acidic solution to obtain the nanocrystalline alloy material.
2. The method according to claim 1, wherein A isxNiyCozY100-x-y-z-m-nCumMnIn the flexible amorphous alloy material, A is Al, Fe, Zn or Mg, and M is at least one of Ce, Mn, Au and Pt;
x =75~90, y =0~6, z =0~6, m =1~5, n =0~6, y + z =6~12, 100-x-y-z-m-n is 3~7, x, y, z, m and n are atomic percent of the corresponding atom.
3. The production method according to claim 1 or 2, wherein in the step (2), the heat treatment temperature is not less than the glass transition starting temperature of the amorphous alloy material.
4. The preparation method according to claim 1, wherein the concentration of the alkali in the alkaline solution is 1-6 mol/L; in the acidic solution, the concentration of acid is 1-6 mol/L.
5. The method of claim 1 or 4, wherein the base is at least one of NaOH, LiOH and KOH; the acid is H2SO4HCl and HNO3At least one of (1).
6. The method according to claim 1 or 4, wherein the time for dealloying is 5 to 60 min; the dealloying temperature is 10-40 ℃.
7. The method of claim 1, wherein step (3) is further followed by:
and (4) performing constant-current circulating charge and discharge for 50-500 times on the flexible nano porous metal/oxide supercapacitor electrode material prepared in the step (3), and performing electrochemical polarization.
8. A flexible nano-porous metal/oxide supercapacitor electrode material is characterized by being prepared by the preparation method of any one of claims 1 to 7.
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