CN113644267B - Multi-element alloy induced flexible sodium metal battery substrate and preparation method thereof - Google Patents

Multi-element alloy induced flexible sodium metal battery substrate and preparation method thereof Download PDF

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CN113644267B
CN113644267B CN202110887764.7A CN202110887764A CN113644267B CN 113644267 B CN113644267 B CN 113644267B CN 202110887764 A CN202110887764 A CN 202110887764A CN 113644267 B CN113644267 B CN 113644267B
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nitrate
alloy
sodium
element alloy
zinc
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CN113644267A (en
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马越
白苗
汤晓宇
刘思员
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Northwestern Polytechnical University
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/4417—Methods specially adapted for coating powder
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M4/625—Carbon or graphite
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    • 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
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a multi-element alloy induced flexible sodium metal battery substrate and a preparation method thereof, wherein zinc alloy is inlaid in a carbon tube and also contains catalytic metal elements or inert metal elements; the catalytic elements in the multi-element alloy can induce the carbon nano tube to form a 3D conductive network skeleton, so that the current density of the electrode can be effectively reduced, and sodium metal deposition can be contained, thereby inhibiting the generation of sodium dendrite and dead sodium and slowing down the volume change of a sodium metal anode in the charge-discharge cycle process; on the other hand, under the action of reaction diffusion, concentration gradient and electric field, the sodium-philic Zn atoms dissolve out the multi-element alloy and migrate into the carbon nano tube, so that the distribution of sodium-philic sites is maximized, and agglomeration, volume expansion and excessive consumption of electrolyte are avoided; the soft package battery matched with the meta alloy substrate has high energy density and good mechanical flexibility; the preparation method of the meta-alloy induced flexible sodium metal battery substrate is simple and easy to implement.

Description

Multi-element alloy induced flexible sodium metal battery substrate and preparation method thereof
Technical Field
The invention belongs to the technical field of electrochemical energy materials, and relates to a multi-element alloy induced flexible sodium metal battery substrate and a preparation method thereof.
Background
Along with the progress and continuous development of industrialization, harmful gases and smoke dust generated in the process of burning traditional fossil fuels not only seriously affect natural environment and social environment, but also form a great threat to the living environment of human beings. Therefore, the development of renewable clean energy is urgent. With the popularization and promotion of the use of lithium batteries, lithium as a key raw material will inevitably become scarce and expensive, and with this, mass production of lithium batteries will also be at a pace. Sodium (Na) has a high theoretical capacity (1165 mA h g) -1 ) The ideal oxidation-reduction potential (-2.714V vs. standard hydrogen electrode) and the abundant crust storage (2.75%) are promising negative electrodes for lithium replacement. For sodium ion batteries, commercial hard carbon has not met the energy density requirements as a negative electrode. While high capacity alloy cathodes such as Sn, sb, bi, etc. provide increased energy density at the cost of rapid powdering of the pole pieces and short life. The Na metal negative electrode directly applied to the Na metal battery shows the greatest potential in energy density. However, uncontrolled sodium dendrite formation will penetrate the separator, causing the cell to short circuit. In addition, na deposition causes infinite expansion of volume, inevitably causes interface fluctuation, internal stress variation and solid electrolyte interface, thereby depleting Na + And (5) storing. Under the action of geometric deformation or mechanical load, the problems aggravate the structural instability and low coulombic efficiency of the metal cathode, and prevent the realization of flexible and energy-intensive metal sodium batteries.
To alleviate the branching in sodium metal batteriesVarious solutions have been proposed for crystal formation, including high modulus artificial SEI construction, electrolyte modification, and deposition substrate modification. In these methods, a metal host with sodium-philic properties and sufficient internal space is included, such as a 3D copper substrate, a porous aluminum current collector, and individual silver nanowires, to condition the homogenized Na + Flux. However, evaluating the performance of these metal substrates based solely on recyclability or capacity is not convincing, as the inactive weight and volume of the 3D substrate would offset the advantage of metal Na in terms of weight/capacity. In addition, light carbonaceous materials have been explored as deposition hosts for sodium. Recently, hu et al developed a carbonized wood composite material with a high specific surface area to stabilize the sodium plating process, and Kim's team developed a carbon thin film decorated with gold nanoparticles, which could uniformly plate Na on the entire composite material. However, these carbon substrates are mostly hard materials and suffer from lower Na storage densities. An optimal "substrate" should balance various properties including adequate deposition space, sodium affinity, high packing density, lightweight design, and mechanical flexibility to provide viable overall performance in practical sodium metal battery systems.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a multi-element alloy induced flexible sodium metal battery substrate and a preparation method thereof, which can effectively inhibit the generation of sodium dendrite and improve the circulation stability;
the invention aims to provide a multi-element alloy induced flexible sodium metal battery substrate which can effectively inhibit the generation of sodium dendrite and improve the circulation stability;
the second purpose of the invention is to provide a multi-element alloy induced flexible sodium metal battery substrate and a preparation method thereof, which are simple and easy to implement and have low cost.
Technical proposal
A multi-element alloy induced flexible sodium metal battery substrate is characterized by comprising zinc alloy and carbon tubes; the zinc alloy is inlaid in the carbon tube, wherein the weight of the zinc alloy is not more than 20% of the total weight of the substrate; the zinc alloy also contains catalytic metal elements.
The zinc alloy also contains inert metal element Al.
The catalytic metal element comprises one or more of Fe, ni, cu, co.
When one or more of Fe, ni and Co are adopted as the catalytic metal element, the molar ratio of Fe, ni, co and Zn is 1:1:1:1.
When Cu and Ni are used as the catalytic metal elements, the molar ratio between Cu and Ni and Zn is 2:1:1.
A method for preparing the multi-element alloy induced flexible sodium metal battery substrate, which is characterized by comprising the following steps:
step 1: zinc nitrate and other nitrate are dissolved in deionized water and stirred to obtain nitrate solution; the other nitrates are as follows: one or more of nickel nitrate, ferric nitrate, cobalt nitrate or aluminum nitrate, wherein the molar ratio of the nitrate is 1;
step 2: dissolving citric acid in the nitrate solution obtained in the step 1, and stirring to obtain sol; the molar ratio of the total amount of the citric acid to the nitrate is 1;
step 3: transferring the sol into an oven for heating to obtain xerogel; the heating temperature is 70-90 ℃ and the heating time is 12-48 h;
step 4: placing the xerogel obtained in the step 3 in a high temperature and inert atmosphere for self-combustion to obtain a multi-element alloy;
step 5, performing chemical vapor deposition on the multi-element alloy: grinding the multi-element alloy powder, spreading the multi-element alloy powder in a magnetic boat, placing the magnetic boat in a tube furnace, introducing inert gas, and when the multi-element alloy powder is heated to 600-800 ℃ at a heating speed of 5-10 ℃/min, introducing an inert gas and acetylene mixed gas for 0.5-1 h, and cooling the multi-element alloy powder along with the furnace to obtain the multi-element alloy carbon-coated tube composite material, namely the multi-element alloy induced flexible sodium metal battery substrate.
In the step 1, when other nitrate is nickel nitrate, copper nitrate is also added to dissolve in deionized water and stirred to obtain nitrate solution; the molar ratio between the copper nitrate and the nickel nitrate to the zinc nitrate is 2:1:1.
The inert gas is argon or hydrogen.
Advantageous effects
The invention provides a multi-element alloy induced flexible sodium metal battery substrate and a preparation method thereof, comprising zinc alloy and a carbon tube, wherein the zinc alloy is inlaid in the carbon tube, and the weight of the zinc alloy is not more than 20% of the total weight of the substrate; the zinc alloy also contains catalytic metal elements and inert metal elements; the catalytic elements in the multi-element alloy can induce the carbon nano tube to form a 3D conductive network skeleton, so that the current density of the electrode can be effectively reduced, and sodium metal deposition can be contained, thereby inhibiting the generation of sodium dendrite and dead sodium and slowing down the volume change of a sodium metal anode in the charge-discharge cycle process; on the other hand, under the action of reaction diffusion, concentration gradient and electric field, the sodium-philic Zn atoms dissolve out the multi-element alloy and migrate into the carbon nano tube, so that the distribution of sodium-philic sites is maximized, and agglomeration, volume expansion and excessive consumption of electrolyte are avoided; the soft package battery matched with the meta alloy substrate has high energy density and good mechanical flexibility; the preparation method of the meta-alloy induced flexible sodium metal battery substrate is simple and easy to implement.
The invention is also characterized in that: wherein zinc is used as an active adsorption site as a sodium philic element; the catalytic metal elements comprise nickel, and or copper, and or iron, and or cobalt for catalyzing the growth of the carbon nano-tubes; the inert metal element comprises aluminum for serving as an alloy skeleton, and is used for slowing down volume expansion.
The invention has the beneficial effects that:
1. according to the flexible sodium metal battery substrate induced by the multi-element alloy, the catalytic elements in the multi-element alloy can induce the carbon nano tubes to form the 3D conductive network skeleton, so that the current density of an electrode can be effectively reduced, sodium metal deposition can be contained, generation of sodium dendrites and dead sodium is inhibited, and the volume change of a sodium metal negative electrode in the charge-discharge cycle process is slowed down; the inert element aluminum plays a role of a framework; on the other hand, under the action of reaction diffusion, concentration gradient and electric field, the sodium-philic Zn atoms dissolve out of the multi-element alloy and migrate into the carbon nano tube, so that the distribution of the sodium-philic sites is maximizedAgglomeration, volume expansion and excessive consumption of electrolyte are avoided; compared with pure sodium metal negative electrode, the multi-element alloy substrate (Cu 2 NiZn@CNT) achieves higher coulombic efficiency (99.4%) and cycling stability (500 h), sodium deposition reaching 10mA h cm -2 The product still has smooth appearance; the alloy substrate (Cu) 2 NiZn@CNT) matched 6A h soft package battery (Cu2NiZn@CNT||NaVPO 4 F) The energy density of (a) is up to 351.6Wh kg -1 And has good mechanical flexibility;
2. the preparation method of the flexible sodium metal battery substrate induced by the meta-alloy is simple and easy to implement, the negative electrode substrate for the sodium metal battery is prepared by a sol-gel method-chemical vapor deposition two-step method, the sol-gel method utilizes metal nitrate, the cost is low, the multi-element nano-alloy is obtained, and each group member in the alloy is dispersed and distributed, so that uniform removal and dispersion of sodium-philic elements are facilitated; time and temperature control during the self-ignition process is critical to the alloy particle size, which determines the aspect ratio of the subsequent carbon nanotubes; the controllable carbon tube prepared by chemical vapor deposition has excellent conductivity, can disperse current density, and the interwoven carbon tube can accommodate metal deposition to obtain a smooth metal negative electrode.
Drawings
FIG. 1 shows Cu obtained in example 1 of the present invention 2 Scanning Electron Microscope (SEM) images of nizn@cnt;
FIG. 2 shows Cu obtained in example 1 of the present invention 2 A Transmission Electron Microscope (TEM) image of the nizn@cnt;
FIG. 3 shows Cu obtained in example 1 of the present invention 2 An X-ray diffraction (XRD) pattern of nizn@cnt;
FIG. 4 shows Cu obtained in example 4 of the present invention 2 Scanning Electron Microscope (SEM) images of nizn@cnt;
FIG. 5 is an SEM image of FeCoNiAlZn@CNT according to example 6 of the present invention;
FIG. 6 shows Cu obtained in example 1 of the present invention 2 Scanning electron microscope (SEM-EDS) images of NiZn@CNT substrates after complexation in sodium batteries;
FIG. 7 shows a process according to example 1 of the present inventionThe obtained Cu 2 NiZn@CNT substrate deposition of 10mA h cm -2 SEM and cross-sectional views of metallic sodium;
FIG. 8 shows Cu obtained in example 1 of the present invention 2 NiZn@CNT, cuNi@CNT electrode obtained in example 5, and sodium foil symmetric cell at 2mA cm -2 ，2mA h cm -2 Voltage-time curve;
FIG. 9 shows Cu obtained in example 1 of the present invention 2 NiZn@CNT electrode at 1mA cm -2 ，10mA h cm -2 Voltage-capacity curve of (2);
FIG. 10 shows a FeCoNiAlZn@CNT electrode deposit of 10mA h cm obtained in example 4 of the present invention -2 SEM images of sodium metal;
FIG. 11 is a graph showing that the FeCoNiAlZn@CNT electrode symmetric cell obtained in example 4 of the present invention is at 2mA cm -2 ，2mA h cm -2 Voltage-time curve;
FIG. 12 shows the coulombic efficiency of FeCoNiAlZn@CNT electrodes obtained in example 4 of the present invention at different current densities;
FIG. 13 shows Cu obtained in example 1 of the present invention 2 The NiZn@CNT electrode is matched with a commercial sodium vanadium fluorophosphate positive electrode material to prepare a capacity retention rate curve chart of the full battery at 0.5C multiplying power, and the inset is a photograph of the soft package battery at different bending.
Detailed Description
The invention will now be further described with reference to examples, figures:
the technical scheme adopted by the invention is that the multi-element alloy induced flexible sodium metal battery substrate comprises zinc alloy and a carbon tube, wherein the zinc alloy is embedded in the carbon tube, and the weight of the zinc alloy is not more than 20% of the total weight of the substrate; the zinc alloy also contains catalytic metal elements and inert metal elements; the metal elements for catalyzing the growth of the carbon tube comprise nickel, copper, iron and cobalt; the inert metal element includes aluminum; zinc, nickel, iron, cobalt and aluminum in a molar ratio of 1;
the embodiment of the invention provides a preparation method of a multi-element alloy induced flexible sodium metal battery substrate, which is realized by the following steps:
firstly, dissolving required nitrate in deionized water and stirring to obtain a nitrate solution, wherein the nitrate comprises copper nitrate, nickel nitrate, zinc nitrate and/or ferric nitrate and/or cobalt nitrate and/or aluminum nitrate;
step 2, dissolving citric acid in the nitrate solution obtained in the step 1, and stirring to obtain sol;
step 3, transferring the sol obtained in the step 2 into an oven for heating, wherein the heating temperature is 70-90 ℃ and the heating time is 12-48 hours, so as to obtain xerogel;
step 4, placing the xerogel obtained in the step 3 in high temperature and inert atmosphere for self-combustion, wherein the heating temperature is 250-350 ℃ and the heating time is 20-40 min, so as to obtain the multi-element alloy;
step 5, performing chemical vapor deposition on the multi-element alloy obtained in the step 4: weighing multi-element alloy powder, grinding and spreading the multi-element alloy powder in a magnetic boat, putting the magnetic boat in a tube furnace, introducing inert gas argon or hydrogen, heating to 600-800 ℃ at a heating speed of 5-10 ℃/min, introducing a mixed gas of inert gas and acetylene for 0.5-1 h, and cooling along with the furnace to obtain the multi-element alloy carbon-coated tube composite material.
Example 1
Step 1, respectively weighing 1mmol of copper nitrate, 1mmol of nickel nitrate and 1mmol of zinc nitrate, and dissolving the copper nitrate, the nickel nitrate and the zinc nitrate into 50mL of deionized water to obtain a nitrate solution;
step 2, weighing 3mmol of citric acid, adding the citric acid into the nitrate solution obtained in the step 1, and stirring to obtain sol;
step 3, transferring the sol obtained in the step 2 into a baking oven at 70 ℃ and heating for 48 hours to obtain xerogel;
step 4, placing the xerogel obtained in the step 3 in a tube furnace filled with nitrogen for self-combustion reaction, wherein the heating temperature is 250 ℃, and the heating time is 30min to obtain Cu 2 A NiZn ternary alloy;
step 5, cu obtained in the step 4 is processed 2 And (3) carrying out chemical vapor deposition on the NiZn ternary alloy: weighing Cu 2 Grinding NiZn powder, spreading in a magnetic boat, introducing argon gas into a tube furnace, heating to 600deg.C at a heating rate of 5deg.C/min, and mixing with acetyleneThe gas (flow rate ratio is 9:1) is cooled along with the furnace for 1h, and the ternary alloy carbon-coated tube composite material (Cu) is obtained 2 NiZn@CNT)。
SEM characterization:
cu of the ternary alloy carbon-coated tube composite material prepared in step 5 in example 1 2 NiZn@CNT was characterized by SEM and TEM as shown in FIG. 1, and may be Cu 2 The NiZn particles uniformly induce the generation of staggered carbon nanotubes, the size of alloy crystal grains is not more than 100nm, and the size is uniform; as seen from the TEM image of FIG. 2, cu 2 The lattice spacing of the NiZn alloy is 0.21nm, corresponding to Cu 2 The (111) crystal face of NiZn; it can also be seen that the lattice spacing of adjacent graphitized carbon tubes is 0.34nm.
XRD pattern:
cu of the ternary alloy carbon-coated tube composite material prepared in step 5 in example 1 2 XRD characterization of NiZn@CNT was performed, as shown in FIG. 3, and XRD test results showed that Cu synthesized in example 1 2 NiZn is pure phase.
Example 2
Step 1, respectively weighing 1mmol of copper nitrate, 1mmol of nickel nitrate and 1mmol of zinc nitrate, and dissolving the copper nitrate, the nickel nitrate and the zinc nitrate into 50mL of deionized water to obtain a nitrate solution;
step 2, weighing 3mmol of citric acid, adding the citric acid into the nitrate solution obtained in the step 1, and stirring to obtain sol;
step 3, transferring the sol obtained in the step 2 into a baking oven at 90 ℃ and heating for 12 hours to obtain xerogel;
step 4, placing the xerogel obtained in the step 3 in a tube furnace filled with nitrogen for self-combustion reaction, wherein the heating temperature is 300 ℃ and the heating time is 25min to obtain Cu 2 A NiZn ternary alloy;
step 5, cu obtained in the step 4 is processed 2 And (3) carrying out chemical vapor deposition on the NiZn ternary alloy: weighing Cu 2 Grinding NiZn powder, spreading in a magnetic boat, placing in a tube furnace, introducing argon, heating to 800 ℃ at a heating speed of 10 ℃/min, introducing a mixed gas of argon and acetylene for 0.5h (a flow speed ratio of 9:1), and cooling along with the furnace to obtain the ternary alloy carbon-coated tube composite material (Cu) 2 NiZn@CNT)。
Example 3
Step 1, respectively weighing 1mmol of copper nitrate, 1mmol of nickel nitrate and 1mmol of zinc nitrate, and dissolving the copper nitrate, the nickel nitrate and the zinc nitrate into 50mL of deionized water to obtain a nitrate solution;
step 2, weighing 3mmol of citric acid, adding the citric acid into the nitrate solution obtained in the step 1, and stirring to obtain sol;
step 3, transferring the sol obtained in the step 2 into an oven at 80 ℃ and heating for 30 hours to obtain xerogel;
step 4, placing the xerogel obtained in the step 3 in a tube furnace filled with nitrogen for self-combustion reaction, wherein the heating temperature is 350 ℃, and the heating time is 20min, so as to obtain Cu 2 A NiZn ternary alloy;
step 5, cu obtained in the step 4 is processed 2 And (3) carrying out chemical vapor deposition on the NiZn ternary alloy: weighing Cu 2 Grinding NiZn powder, spreading in a magnetic boat, placing in a tube furnace, introducing argon, heating to 700 ℃ at a heating speed of 8 ℃/min, introducing a mixed gas (flow speed ratio of 9:1) of argon and acetylene for 1h, and cooling with the furnace to obtain the ternary alloy carbon-coated tube composite material (Cu) 2 NiZn@CNT)。
With the reference to example 4 as a comparative sample,
step 1, respectively weighing 1mmol of copper nitrate, 1mmol of nickel nitrate and 1mmol of zinc nitrate, and dissolving the copper nitrate, the nickel nitrate and the zinc nitrate into 50mL of deionized water to obtain a nitrate solution;
step 2, weighing 3mmol of citric acid, adding the citric acid into the nitrate solution obtained in the step 1, and stirring to obtain sol;
step 3, transferring the sol obtained in the step 2 into an oven at 80 ℃ and heating for 24 hours to obtain xerogel;
step 4, placing the xerogel obtained in the step 3 in a tube furnace filled with nitrogen for self-combustion reaction, wherein the heating temperature is 300 ℃, and the heating time is 15min, so as to obtain Cu 2 A NiZn ternary alloy;
step 5, cu obtained in the step 4 is processed 2 And (3) carrying out chemical vapor deposition on the NiZn ternary alloy: weighing Cu 2 Grinding NiZn powder, spreading in magnetic boat, introducing argon gas into tubular furnace, heating to 700deg.C at heating rate of 8deg.C/min, and introducing mixed gas of argon gas and acetylene for 0.5 hr (flowing)The speed ratio is 9:1), and cooling along with the furnace to obtain the ternary alloy carbon-coated tube composite material (Cu) 2 NiZn@CNT)。
SEM characterization:
cu obtained in step 5 of example 4 2 NiZn@CNT was SEM as shown in FIG. 4, it can be seen that Cu when the heating time in step 4 was insufficient 2 The NiZn particles are small and may have insufficient crystallinity, resulting in a fine growth of the carbon tube when the carbon tube is induced in step 5, which is difficult to be directly applied to the substrate.
With the reference to example 5 as a comparative sample,
step 1, respectively weighing 1mmol of copper nitrate and 1mmol of nickel nitrate, and dissolving the copper nitrate and the nickel nitrate into 50mL of deionized water to obtain a nitrate solution;
step 2, weighing 2mmol of citric acid, adding the citric acid into the nitrate solution obtained in the step 1, and stirring to obtain sol;
step 3, transferring the sol obtained in the step 2 into an oven at 80 ℃ and heating for 36 hours to obtain xerogel;
step 4, placing the xerogel obtained in the step 3 in a tube furnace filled with nitrogen for self-combustion reaction, wherein the heating temperature is 300 ℃, and the heating time is 30min, so as to obtain the CuNi binary alloy;
step 5, carrying out chemical vapor deposition on the CuNi binary alloy obtained in the step 4: and (3) weighing CuNi powder, grinding and spreading the powder in a magnetic boat, putting the magnetic boat in a tube furnace, introducing argon, heating to 700 ℃ at a heating speed of 10 ℃/min, introducing a mixed gas of the argon and acetylene for 0.5h (a flow speed ratio of 9:1), and cooling along with the furnace to obtain the ternary alloy carbon-coated tube composite material (CuNi@CNT). As a substrate without the sodium philic element Zn, a comparison will be made in the subsequent electrochemical characterization, discussing the effect of the substrate on cell performance in the absence of the sodium philic element.
Example 6
Step 1, respectively weighing 1mmol of ferric nitrate, 1mmol of cobalt nitrate, 1mmol of nickel nitrate, 1mmol of aluminum nitrate and 1mmol of zinc nitrate, and dissolving into 80mL of deionized water to obtain a nitrate solution;
step 2, weighing 5mmol of citric acid, adding the citric acid into the nitrate solution obtained in the step 1, and stirring to obtain sol;
step 3, transferring the sol obtained in the step 2 into a baking oven at 90 ℃ and heating for 40 hours to obtain xerogel;
step 4, placing the xerogel obtained in the step 3 in a tube furnace filled with nitrogen for self-combustion reaction, wherein the heating temperature is 300 ℃, and the heating time is 40min, so as to obtain FeCoNiAlZn quinary alloy;
and 5, carrying out chemical vapor deposition on the FeCoNiAlZn quinary alloy obtained in the step 4: the FeCoNiAlZn powder is weighed, ground and tiled in a magnetic boat, placed in a tube furnace, filled with argon, heated to 700 ℃ at a heating speed of 5 ℃/min, filled with a mixed gas of argon and acetylene (the flow speed ratio is 9:1) for 0.5h, and cooled with the furnace to obtain the five-element alloy carbon-coated tube composite material (FeCoNiAlZn@CNT).
SEM characterization:
SEM characterization is carried out on the five-membered alloy carbon-coated tube composite material FeCoNiAlZn@CNT prepared in the step 5 in the example 4, and as shown in fig. 5, the FeCoNiAlZn particles can induce the generation of staggered carbon nanotubes, and the alloy grain size is not more than 100nm and the size is uniform.
Example 7
Step 1, respectively weighing 1mmol of ferric nitrate, 1mmol of cobalt nitrate, 1mmol of nickel nitrate, 1mmol of aluminum nitrate and 1mmol of zinc nitrate, and dissolving into 80mL of deionized water to obtain a nitrate solution;
step 2, weighing 5mmol of citric acid, adding the citric acid into the nitrate solution obtained in the step 1, and stirring to obtain sol;
step 3, transferring the sol obtained in the step 2 into an oven at 80 ℃ and heating for 40 hours to obtain xerogel;
step 4, placing the xerogel obtained in the step 3 in a tube furnace filled with nitrogen for self-combustion reaction, wherein the heating temperature is 300 ℃, and the heating time is 30min, so as to obtain FeCoNiAlZn quinary alloy;
and 5, carrying out chemical vapor deposition on the FeCoNiAlZn quinary alloy obtained in the step 4: the FeCoNiAlZn powder is weighed, ground and tiled in a magnetic boat, placed in a tube furnace, filled with argon, heated to 700 ℃ at a heating speed of 8 ℃/min, filled with a mixed gas of argon and acetylene (flow speed ratio of 9:1) for 1h, and cooled along with the furnace to obtain the five-element alloy carbon-coated tube composite material (FeCoNiAlZn@CNT).
Cell electrochemical performance test:
the multi-element alloy coated carbon nanotubes prepared in examples 1, 5 and 6 of the present invention were mixed with polyvinylidene fluoride (PVDF) at a ratio of 95: mixing and grinding in a weight ratio of 5, preparing slurry by using Dimethylformamide (DMF) as a solvent, coating on a polytetrafluoroethylene plate, peeling after drying, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain the self-supporting substrate Cu of the negative electrode of the sodium metal battery 2 NiZn@CNT, control CuNi@CNT and FeCoNiAlZn@CNT substrates. Cutting into 12mm diameter substrate with a slicer, and using sodium metal foil as counter electrode to obtain NaPF 6 (1M) dissolved in diglyme as an electrolyte. In a glove box filled with high purity argon, water and oxygen concentrations of less than 0.1ppm, 2032 button cells were assembled. After 12h of standing, electrochemical performance testing was performed in constant current mode using the new wiry cell channels.
First at 0.5mA cm -2 After charging to 0.01V, the battery was disassembled and the pole piece was cleaned with diethyl carbonate, and after vacuum drying, elemental energy spectrum testing (SEM-EDS) was performed using an energy spectrometer, and it can be seen from fig. 6 that the elements of C, na, zn were highly coincident, indicating that Zn atoms reacted with sodium and were extracted from the alloy and highly homogeneously migrated into the carbon nanotubes as nucleation sites during alloying. Further sodium deposition to give a capacity of 10mA h cm -2 Na/Cu of (2) 2 The NiZn@CNT pole piece can be seen from SEM of FIG. 7 that the pole piece surface is smooth and flat without dendrites, and the sectional schematic diagram of FIG. 7 shows that the thickness of the sodium pole piece is about 70 μm, and the further reduction of the volume fluctuation improves the long-term stable circulation of the composite negative electrode. Testing of symmetrical cells: first deposit 3mA h cm -2 Sodium metal to Cu obtained in example 1 2 NiZn@CNT working electrode sheet at 2mA cm -2 ，2mA h cm -2 The deposition lift-off symmetric cell test was performed under conditions as shown in the voltage-time curve of fig. 8, cu 2 The NiZn@CNT electrode has stable interface performance beyond 800 hours, the voltage hysteresis is about 42mV, the voltage hysteresis of the comparative CuNi@CNT electrode is up to 64mV, and the short circuit occurs after 300 weeks of circulation, and the Na foil symmetrical battery is short-circuited even after 60 weeks. FIG. 9 is Cu 2 NiZn@CNT electrode at 1mA cm -2 ，10mA h cm -2 The corresponding voltage curve shows that the polarization voltage is stabilized at 18mV at 100 circles, which indicates that the ion and electron transfer kinetics is fast. The same method is used for depositing 10mA h cm -2 The Na/FeCoNiAlZn@CNT sheet of (C) also shows a smooth dendrite-free state (shown in FIG. 10), while the FeCoNiAlZn@CNT symmetrical cell was at 2mA cm -2 ，2mA h cm -2 The deposition stripping curve of (2) remained stable after more than 1800h of cycling with a voltage hysteresis of about 30mV (shown in figure 11). The coulomb efficiency test method of FeCoNiAlZn@CNT sheet was constant current deposition fixed capacity charged to 2.5V at full stripping, shown in FIG. 12, 2mAcm -2 ，2mA h cm -2 And 3mA cm -2 ，3mA h cm -2 The coulombic efficiencies of (2) are 99.2% and 98.8%, respectively, exhibiting excellent reversible efficiencies.
Full cell test: as shown in FIG. 13, cu 2 NiZn@CNT electrode at 0.5mA cm in half cell -2 The current density was pre-cycled 5 times with sodium vanadium fluorophosphate (NaVPO) 4 F) The positive electrode is matched, the retention rate of 200 circles under the 0.5C multiplying power is 93.7%, and the circulation stability is good.
The results show that the multi-element alloy coated carbon nano tube composite material substrate prepared by the technical scheme of the invention is used for sodium metal batteries, and has the advantages of high coulomb efficiency, good cycle stability, effective inhibition of sodium dendrite and the like in the electrical performance.
According to the flexible sodium metal battery substrate induced by the multi-element alloy, the catalytic elements in the multi-element alloy can induce the carbon nano tubes to form the 3D conductive network skeleton, so that the current density of an electrode can be effectively reduced, sodium metal deposition can be contained, generation of sodium dendrites and dead sodium is inhibited, and the volume change of a sodium metal negative electrode in the charge-discharge cycle process is slowed down; the inert element aluminum plays a role of a framework; on the other hand, under the action of reaction diffusion, concentration gradient and electric field, the sodium-philic Zn atoms dissolve out the multi-element alloy and migrate into the carbon nano tube, so that the distribution of sodium-philic sites is maximized, and agglomeration, volume expansion and excessive consumption of electrolyte are avoided; compared with pure sodium metal negative electrode, the multi-element alloy substrate (Cu 2 NiZn@CNT) achieves higher coulombic efficiency (99.4%) and cycling stability (500 h), sodium deposition reaching 10mA h cm -2 The product still has smooth appearance; the alloy substrate (Cu) 2 NiZn@CNT) matched 6A h soft package battery (Cu2NiZn@CNT||NaVPO 4 F) The energy density of (a) is up to 351.6Wh kg -1 And has good mechanical flexibility; the preparation method of the flexible sodium metal battery substrate induced by the element alloy is simple and easy, the negative electrode substrate for the sodium metal battery is prepared by a sol-gel method and a chemical vapor deposition two-step method, the sol-gel method utilizes metal nitrate, the cost is low, the element nano alloy is obtained, and the dispersed distribution of each group member in the alloy is beneficial to the uniform removal and dispersion of sodium-philic elements; time and temperature control during the self-ignition process is critical to the alloy particle size, which determines the aspect ratio of the subsequent carbon nanotubes; the controllable carbon tube prepared by chemical vapor deposition has excellent conductivity, can disperse current density, and the interwoven carbon tube can accommodate metal deposition to obtain a smooth metal negative electrode.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention.

Claims (3)

1. The preparation method of the multi-element alloy induced flexible sodium metal battery substrate is characterized by comprising the following steps:
step 1: zinc nitrate, aluminum nitrate and other nitrate are dissolved in deionized water and stirred to obtain nitrate solution; the other nitrates are as follows: one or more of nickel nitrate, ferric nitrate and cobalt nitrate;
step 2: dissolving citric acid in the nitrate solution obtained in the step 1, and stirring to obtain sol; the mole ratio of the total amount of the citric acid and the nitrate is 1:1, a step of;
step 3: transferring the sol into an oven for heating to obtain xerogel; the heating temperature is 70-90 ℃ and the heating time is 12-48 h;
step 4: placing the xerogel obtained in the step 3 under high temperature and inert atmosphere for self-combustion, wherein the self-combustion heating temperature is 250-350 ℃ and the self-combustion heating time is 20-40 min, so as to obtain a multi-element alloy;
step 5, performing chemical vapor deposition on the multi-element alloy: grinding the multi-element alloy powder, spreading the multi-element alloy powder in a magnetic boat, placing the magnetic boat in a tube furnace, introducing inert gas, and when the multi-element alloy powder is heated to 600-800 ℃ at a heating speed of 5-10 ℃/min, introducing an inert gas and acetylene mixed gas for 0.5-1 h, and cooling the multi-element alloy powder along with the furnace to obtain the multi-element alloy carbon-coated tube composite material, namely the multi-element alloy induced flexible sodium metal battery substrate;
wherein the molar ratio of zinc nitrate to each nitrate in the other nitrates is 1:1, a step of; the molar ratio of zinc nitrate to aluminum nitrate is 1:1, a step of;
the multi-element alloy induced flexible sodium metal battery substrate is characterized by comprising zinc alloy and carbon tubes; the zinc alloy is inlaid in the carbon tube, wherein the weight of the zinc alloy is not more than 20% of the total weight of the substrate; the zinc alloy also contains a catalytic metal element and an inert metal element Al; the catalytic metal element comprises one or more of Fe, ni and Co.
2. The method according to claim 1, characterized in that: in the step 1, when the other nitrate is nickel nitrate,
copper nitrate is also added to be dissolved in deionized water and stirred to obtain nitrate solution; the molar ratio between the copper nitrate and the nickel nitrate to the zinc nitrate is 2:1:1.
3. The method according to claim 1 or 2, characterized in that: the inert gas is argon.
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