CN113644267A - 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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CN113644267A
CN113644267A CN202110887764.7A CN202110887764A CN113644267A CN 113644267 A CN113644267 A CN 113644267A CN 202110887764 A CN202110887764 A CN 202110887764A CN 113644267 A CN113644267 A CN 113644267A
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alloy
nitrate
sodium
sodium metal
substrate
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CN113644267B (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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    • 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
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    • H01M10/00—Secondary cells; Manufacture thereof
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    • H—ELECTRICITY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H—ELECTRICITY
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    • 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 multielement alloy induced flexible sodium metal battery substrate and a preparation method thereof, wherein a zinc alloy is embedded in a carbon tube, and the zinc alloy also contains a catalytic metal element or an inert metal element; the catalytic elements in the multi-component alloy can induce the carbon nano tubes to form a 3D conductive network framework, so that the current density of the electrode can be effectively reduced, and sodium metal deposition can be accommodated, so that the generation of sodium dendrites and 'dead sodium' is inhibited, and the volume change of a sodium metal cathode in the charge-discharge cycle process is slowed down; 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 the sodium-philic sites is maximized, and agglomeration, volume expansion and excessive consumption of electrolyte are avoided; the soft package battery matched with the element alloy substrate has high energy density and good mechanical flexibility; the preparation method of the element 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
With the progress and continuous development of industrialization, harmful gas and smoke generated in the burning process of the traditional fossil fuel not only seriously affect the natural environment and social environment, but also pose a great threat to the living environment of human beings. Therefore, it is urgent to develop renewable clean energy. As the use of lithium batteries is popularized and popularized, lithium as a key raw material inevitably becomes scarce and expensive, and the mass production of lithium batteries will take great steps. Sodium (Na) has higher theoretical capacity (1165mA h g-1) Ideal redox potential (-2.714V vs. standard hydrogen electrode) and abundant earth crust storage (2.75%) are promising negative electrodes to replace lithium. For sodium ion batteries, the energy density requirements have not been met by commercial hard carbon as the negative electrode. The increase in energy density provided by high capacity alloy type cathodes such as Sn, Sb, Bi, etc. comes at the expense of rapid pulverization of the pole pieces and short life. Therefore, the application of the Na metal negative electrode directly to the Na metal battery shows the greatest potential in energy density. However, uncontrolled sodium dendrite formation will penetrate the separator, causing a short circuit in the cell. In addition, Na deposition causes volume infinite expansion, inevitably leading to interface fluctuation, internal stress variation, and solid electrolyte interface, thereby depleting Na+And (7) 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 mitigate dendrite formation in sodium metal batteries, various solutions have been proposed, including high modulus artificial SEI construction, electrolyte modification, and deposition substrate modificationAnd (4) sex. In these methods, metal hosts with sodium-philic properties and sufficient internal space are included, such as 3D copper substrates, porous aluminum current collectors, and freestanding silver nanowires to condition homogenized Na+Flux. However, it is not convincing to evaluate the performance of these metal substrates based on recyclability or capacity alone, as the inactive weight and volume of the 3D substrate would offset the weight/capacity advantages of metallic Na. In addition, light carbonaceous materials have also 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 group developed a carbon film decorated with gold nanoparticles that can be uniformly plated with Na throughout the composite material. However, these carbon substrates are mostly hard materials and suffer from a low Na storage density. An optimal "substrate" should balance various properties including sufficient deposition space, sodium affinity, high packing density, lightweight design, and mechanical flexibility to provide feasible overall performance in a practical sodium metal battery system.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides the multi-element alloy induced flexible sodium metal battery substrate and the preparation method thereof, which can effectively inhibit the generation of sodium dendrites and improve the cycle stability;
one of the purposes of the invention is to provide a multi-component alloy induced flexible sodium metal battery substrate which can effectively inhibit the generation of sodium dendrites and improve the cycle stability;
the second purpose of the invention is to provide a multi-component alloy induced flexible sodium metal battery substrate and a preparation method thereof, which are simple and feasible and have low price.
Technical scheme
A multi-component alloy induced flexible sodium metal battery substrate is characterized by comprising zinc alloy and a carbon tube; the zinc alloy is embedded in the carbon tube, wherein the weight of the zinc alloy accounts for not more than 20 percent of the total weight of the substrate; the zinc alloy also contains catalytic metal elements.
The zinc alloy also contains an inert metal element Al.
The catalytic metal element comprises one or more of Fe, Ni, Cu and Co.
When one or more of Fe, Ni and Co is 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 is characterized by comprising the following steps:
step 1: dissolving zinc nitrate and other nitrates in deionized water and stirring to obtain a nitrate solution; the other nitrates are: one or more of nickel nitrate, ferric nitrate, cobalt nitrate or aluminum nitrate, wherein the molar ratio of each 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 and the nitrate is 1;
and step 3: transferring the sol into a drying oven to be heated to obtain dry gel; the heating temperature is 70-90 ℃, and the heating time is 12-48 h;
and 4, step 4: placing the xerogel obtained in the step 3 in a high-temperature inert atmosphere for self-combustion to obtain a multi-element alloy;
and 5, performing chemical vapor deposition on the multi-element alloy: grinding the multi-component alloy into powder, spreading the powder in a magnetic boat, placing the magnetic boat in a tube furnace, introducing inert gas, heating the magnetic boat to 600-800 ℃ at a heating speed of 5-10 ℃/min, introducing a mixed gas of the inert gas and acetylene for 0.5-1 h, and cooling the magnetic boat along with the furnace to obtain the multi-component alloy carbon-coated tube composite material, namely the multi-component alloy induced flexible sodium metal battery substrate.
In the step 1, when other nitrates are nickel nitrate, adding copper nitrate, dissolving in deionized water and stirring to obtain a nitrate solution; the molar ratio of the copper nitrate to 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, wherein the multi-element alloy induced flexible sodium metal battery substrate comprises a zinc alloy and a carbon tube, wherein the zinc alloy is embedded in the carbon tube, and the weight of the zinc alloy accounts for 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-component alloy can induce the carbon nano tubes to form a 3D conductive network framework, so that the current density of the electrode can be effectively reduced, and sodium metal deposition can be accommodated, so that the generation of sodium dendrites and 'dead sodium' is inhibited, and the volume change of a sodium metal cathode in the charge-discharge cycle process is slowed down; 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 the sodium-philic sites is maximized, and agglomeration, volume expansion and excessive consumption of electrolyte are avoided; the soft package battery matched with the element alloy substrate has high energy density and good mechanical flexibility; the preparation method of the element 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 a sodium affinity element to be used as an active adsorption site; the catalytic metal elements comprise nickel, and/or copper, and/or iron, and/or cobalt for catalyzing the growth of the carbon nano tube; the inert metal element includes aluminum for use as an alloy skeleton, which slows down the volume expansion.
The invention has the beneficial effects that:
1. according to the multi-component alloy induced flexible sodium metal battery substrate, catalytic elements in the multi-component alloy can induce the carbon nano tubes to form a 3D conductive network framework, so that the current density of an electrode can be effectively reduced, and sodium metal deposition can be accommodated, so that sodium dendrite and 'dead sodium' are inhibited, and the volume change of a sodium metal negative electrode in the charge-discharge cycle process is slowed down; the inert element aluminum acts as 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 the sodium-philic sites is maximized, and agglomeration, volume expansion and excessive consumption of electrolyte are avoided; multi-element alloy compared with pure metal sodium metal cathodeSubstrate (Cu)2NiZn @ CNT) achieves higher coulombic efficiency (99.4%) and circulation stability (500h), and sodium deposition reaches 10mA h cm-2Still have a smooth topography; using this elemental alloy substrate (Cu)2NiZn @ CNT) matched 6A h pouch cell (Cu2NiZn @ CNT | | NaVPO)4F) The energy density of (A) is up to 351.6Wh kg-1And has good mechanical flexibility;
2. the preparation method of the element alloy induced flexible sodium metal battery substrate 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 price is low, the multielement nano alloy is obtained, and all members in the alloy are in dispersed distribution, so that the uniform separation and dispersion of sodium-philic elements are facilitated; the time and temperature control in the self-combustion process are crucial to the size of alloy particles, and the alloy particles determine the length-diameter ratio of the subsequent carbon nano tubes; the controllable carbon tube prepared by chemical vapor deposition has excellent conductivity, current density can be dispersed, and the interlaced carbon tube can accommodate metal deposition to obtain a smooth metal cathode.
Drawings
FIG. 1 shows Cu obtained in example 1 of the present invention2Scanning Electron Microscope (SEM) image of NiZn @ CNT;
FIG. 2 shows Cu obtained in example 1 of the present invention2Transmission Electron Microscopy (TEM) image of NiZn @ CNT;
FIG. 3 shows Cu obtained in example 1 of the present invention2An X-ray diffraction (XRD) pattern of NiZn @ CNT;
FIG. 4 shows Cu obtained in example 4 of the present invention2Scanning Electron Microscope (SEM) image of NiZn @ CNT;
FIG. 5 is an SEM image of FeCoNiAlZn @ CNT prepared in example 6 of the present invention;
FIG. 6 shows Cu obtained in example 1 of the present invention2Scanning electron microscopy energy spectrum analysis (SEM-EDS) picture of NiZn @ CNT substrate after complexing in sodium battery;
FIG. 7 shows Cu obtained in example 1 of the present invention2NiZn @ CNT substrate deposition 10mA h cm-2SEM and cross-sectional views of sodium metal;
FIG. 8 shows Cu obtained in example 1 of the present invention2NiZn @ CNT, CuNi @ CNT electrode from example 5, and sodium foil symmetric cell at 2mA cm-2，2mA h cm-2A voltage-time curve;
FIG. 9 shows Cu obtained in example 1 of the present invention2NiZn @ CNT electrode at 1mA cm-2，10mA h cm-2Voltage-capacity curve of (d);
FIG. 10 shows FeCoNiAlZn @ CNT electrode deposition of 10mA h cm prepared in example 4 of the present invention-2SEM image of sodium metal;
FIG. 11 shows that the FeCoNiAlZn @ CNT electrode symmetric battery obtained in example 4 of the present invention is at 2mA cm-2，2mA h cm-2A voltage-time curve;
FIG. 12 is a graph showing the coulombic efficiencies 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 invention2The NiZn @ CNT electrode is matched with a commercial sodium vanadium fluorophosphate cathode material, a capacity retention rate curve graph of the full battery under the multiplying power of 0.5C is prepared, and the inset is a photo of a soft package battery under different bending conditions.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
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 accounts for no 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, and/or copper, and/or iron, and/or cobalt; the inert metal element includes aluminum; the molar ratio of zinc, nickel, iron, cobalt and aluminum is 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:
step 1, 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 a drying oven to be heated, 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 a high-temperature inert atmosphere for self-combustion, wherein the heating temperature is 250-350 ℃, and the heating time is 20-40 min, so as to obtain a multi-element alloy;
and 5, carrying out chemical vapor deposition on the multi-element alloy obtained in the step 4: weighing multi-element alloy powder, grinding and spreading in a magnetic boat, placing 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 tube-coated 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 1mmol of nickel nitrate and the 1mmol of 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 to a 70 ℃ oven to be heated for 48 hours to obtain xerogel;
and 4, placing the xerogel obtained in the step 3 into a tubular furnace filled with nitrogen for self-combustion reaction, wherein the heating temperature is 250 ℃, and the heating time is 30min to obtain Cu2A NiZn ternary alloy;
step 5, the Cu obtained in the step 42Carrying out chemical vapor deposition on the NiZn ternary alloy: weighing Cu2Grinding NiZn powder, spreading in a magnetic boat, placing in a tube furnace, introducing argon, heating to 600 deg.C at a heating rate of 5 deg.C/min, introducing mixed gas of argon and acetylene (flow rate ratio of 9:1) for 1h, and cooling with the furnace to obtain ternary alloy carbon-coated tube composite material (Cu)2NiZn@CNT)。
And (4) SEM characterization:
the ternary alloy carbon tube-coated composite material Cu prepared in the step 5 in the example 12NiZn @ CNT was characterized by SEM and TEM and can be Cu as shown in FIG. 12The 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, Cu2The lattice spacing of the NiZn alloy is 0.21nm, corresponding to Cu2The (111) crystal face of NiZn; it can also be seen that the lattice spacing of the adjacent graphitized carbon tubes is 0.34 nm.
An XRD spectrum:
the ternary alloy carbon tube-coated composite material Cu prepared in the step 5 in the example 12The NiZn @ CNT is subjected to XRD characterization, and as shown in figure 3, XRD test results show that the Cu synthesized in example 12NiZn 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 1mmol of nickel nitrate and the 1mmol of 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 drying oven at 90 ℃ and heating for 12 hours to obtain xerogel;
and 4, placing the xerogel obtained in the step 3 into a tubular furnace filled with nitrogen for self-combustion reaction, wherein the heating temperature is 300 ℃, the heating time is 25min, and Cu is obtained2A NiZn ternary alloy;
step 5, the Cu obtained in the step 42Carrying out chemical vapor deposition on the NiZn ternary alloy: weighing Cu2Grinding NiZn powder, spreading in a magnetic boat, placing in a tube furnace, introducing argon, heating to 800 deg.C at a heating rate of 10 deg.C/min, introducing mixed gas of argon and acetylene for 0.5h (flow rate ratio of 9:1), and furnace cooling to obtain ternary alloy carbon-coated tube composite material (Cu)2NiZn@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 1mmol of nickel nitrate and the 1mmol of 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 to an oven with the temperature of 80 ℃ for heating for 30 hours to obtain xerogel;
and 4, putting the xerogel obtained in the step 3 into a nitrogen-filled tubular furnace for self-combustion reaction, wherein the heating temperature is 350 ℃, and the heating time is 20min to obtain Cu2A NiZn ternary alloy;
step 5, the Cu obtained in the step 42Carrying out chemical vapor deposition on the NiZn ternary alloy: weighing Cu2Grinding NiZn powder, spreading in a magnetic boat, placing in a tube furnace, introducing argon, heating to 700 deg.C at a heating rate of 8 deg.C/min, introducing mixed gas of argon and acetylene (flow rate ratio of 9:1) for 1h, and cooling with the furnace to obtain ternary alloy carbon-coated tube composite material (Cu)2NiZn@CNT)。
By taking example 4 as a control sample,
step 1, respectively weighing 1mmol of copper nitrate, 1mmol of nickel nitrate and 1mmol of zinc nitrate, and dissolving the copper nitrate, the 1mmol of nickel nitrate and the 1mmol of 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;
and 4, placing the xerogel obtained in the step 3 into a tubular furnace filled with nitrogen for self-combustion reaction, wherein the heating temperature is 300 ℃, and the heating time is 15min, so as to obtain Cu2A NiZn ternary alloy;
step 5, the Cu obtained in the step 42Carrying out chemical vapor deposition on the NiZn ternary alloy: weighing Cu2Grinding NiZn powder, spreading in a magnetic boat, placing in a tube furnace, introducing argon, heating to 700 deg.C at a heating rate of 8 deg.C/min, introducing mixed gas of argon and acetylene for 0.5h (flow rate ratio of 9:1), and furnace cooling to obtain ternary alloy carbon-coated tube composite material (Cu)2NiZn@CNT)。
And (4) SEM characterization:
cu prepared in step 5 of example 42SEM with NiZn @ CNT, as shown in FIG. 4, it can be seen that when the heating time in step 4 is insufficient, Cu2The NiZn particles are small and may have insufficient crystallinity, resulting in fine carbon tube growth upon carbon tube induction in step 5, which is difficult to directly apply to the substrate.
By taking example 5 as a control 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 to an oven with the temperature of 80 ℃ for heating for 36 hours to obtain xerogel;
step 4, putting the xerogel obtained in the step 3 into a tubular furnace filled with nitrogen for self-combustion reaction, wherein the heating temperature is 300 ℃, and the heating time is 30min, so as to obtain a CuNi binary alloy;
and 5, carrying out chemical vapor deposition on the CuNi binary alloy obtained in the step 4: weighing CuNi powder, grinding, spreading in a magnetic boat, placing in a tube furnace, introducing argon, heating to 700 ℃ at a heating speed of 10 ℃/min, introducing a mixed gas of argon and acetylene for 0.5h (flow rate 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, comparison will be made in subsequent electrochemical characterization to investigate the effect of the substrate on battery 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 drying oven at 90 ℃ and heating for 40h to obtain xerogel;
step 4, putting the xerogel obtained in the step 3 into 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 five-element alloy obtained in the step 4: weighing FeCoNiAlZn powder, grinding, spreading in a magnetic boat, placing in a tube furnace, introducing argon, heating to 700 ℃ at a heating speed of 5 ℃/min, introducing a mixed gas of argon and acetylene (flow rate ratio is 9:1) for 0.5h, and cooling with the furnace to obtain the five-element alloy carbon-coated tube composite material (FeCoNiAlZn @ CNT).
And (4) SEM characterization:
SEM representation is carried out on the five-element alloy carbon tube-coated composite material FeCoNiAlZn @ CNT prepared in the step 5 in the embodiment 4, as shown in figure 5, the generation of staggered carbon nanotubes can be induced by FeCoNiAlZn particles, the size of alloy crystal grains is not more than 100nm, and the alloy crystal grains are uniform in size.
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 40h to obtain xerogel;
step 4, putting the xerogel obtained in the step 3 into 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 five-element alloy obtained in the step 4: weighing FeCoNiAlZn powder, grinding, 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 of argon and acetylene (flow rate ratio is 9:1) for 1h, and cooling along with the furnace to obtain the five-element alloy carbon-coated tube composite material (FeCoNiAlZn @ CNT).
And (3) testing the electrochemical performance of the battery:
the carbon nanotubes coated with the multi-component alloy prepared in examples 1, 5 and 6 of the present invention and polyvinylidene fluoride (PVDF) were mixed in a ratio of 95: 5 weight ratio, mixing and grinding, preparing slurry by using dimethyl formamide (DMF) as a solvent, coating the slurry on a polytetrafluoroethylene plate, drying, peeling, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain the self-supporting substrate Cu of the cathode of the sodium metal battery2NiZn @ CNT, control CuNi @ CNT, and FeCoNiAlZn @ CNT substrates. Cutting into 12mm diameter substrate with slicer, using sodium metal foil as counter electrode, NaPF6(1M) dissolved in diglyme as an electrolyte. The 2032 button cell was assembled in a glove box filled with high purity argon, water and oxygen both less than 0.1 ppm. After being placed for 12h, the electrochemical performance test is carried out by adopting a Xinwei battery channel under a constant current mode.
First at 0.5mA cm-2After charging to 0.01V, the battery is disassembled, the electrode plate is washed by diethyl carbonate, and after vacuum drying, an energy spectrometer is used for element energy spectrum testing (SEM-EDS), and the element height coincidence of C, Na and Zn can be seen from figure 6, which shows that Zn atoms react with sodium and are separated from the alloy to be highly and uniformly transferred to the carbon nano tube as a nucleation site in the alloying process. Further sodium deposition was carried out to obtain a volume of 10mA h cm-2Na/Cu of2The NiZn @ CNT pole piece can be seen from the SEM of figure 7 that the surface of the pole piece is smooth and flat without dendrites, and the cross-sectional schematic diagram of figure 7 shows that the thickness of the sodium pole piece is about 70 mu m, and the further reduction of the volume fluctuation improves the long-term stable cycle of the composite negative pole. Testing of symmetric cells: firstly depositing 3mA h cm-2Sodium Metal to Cu obtained in example 12NiZn @ CNT working pole piece at 2mA cm-2，2mA h cm-2Deposition stripping symmetric cell testing was performed under conditions, as shown by the voltage-time curve of FIG. 8, Cu2The NiZn @ CNT electrode has stable interface performance and voltage hysteresis of about 42mV when the NiZn @ CNT electrode exceeds 800h, while the comparative CuNi @ CNT electrode has voltage hysteresis of up to 64mV, and the short circuit occurs after 300 cycles, and the short circuit occurs after 60 cycles in a Na foil symmetrical battery. FIG. 9 is Cu2NiZn @ CNT electrode at 1mA cm-2，10mA h cm-2Corresponding voltage curve ofThe polarization voltage is stabilized at 18mV at 100 circles, which shows that the ion and electron transfer dynamics are fast. In the same way, deposit 10mA h cm-2The Na/FeCoNiAlZn @ CNT electrode sheet also shows a smooth and dendrite-free state (shown in FIG. 10), while the FeCoNiAlZn @ CNT symmetrical cell is at 2mA cm-2，2mA h cm-2The deposition lift-off curve of (1) was stable after cycling over 1800 hours with a voltage hysteresis of about 30mV (shown in figure 11). The coulombic efficiency test method of the FeCoNiAlZn @ CNT pole piece is that constant current is deposited to fix the capacity, the capacity is charged to 2.5V after complete stripping, and the volume is 2mAcm shown in figure 12-2，2mA h cm-2And 3mA cm-2，3mA h cm-2The coulomb efficiencies of (a) were 99.2% and 98.8%, respectively, exhibiting excellent reversible efficiencies.
And (3) full battery test: as shown in FIG. 13, Cu2NiZn @ CNT electrode at 0.5mA cm in half cell-2Current density pre-cycle 5 cycles with sodium vanadium fluorophosphate (NaVPO)4F) The anode is matched, the retention rate of 200 circles at 0.5C multiplying power is 93.7%, and the cycle stability is good.
The results show that the multielement alloy coated carbon nanotube composite material substrate prepared by the technical scheme of the invention is used for sodium metal batteries, and has the advantages of high coulombic efficiency, good cycle stability, effective inhibition of sodium dendrite and the like in electrical properties.
According to the multi-component alloy induced flexible sodium metal battery substrate, catalytic elements in the multi-component alloy can induce the carbon nano tubes to form a 3D conductive network framework, so that the current density of an electrode can be effectively reduced, and sodium metal deposition can be accommodated, so that sodium dendrite and 'dead sodium' are inhibited, and the volume change of a sodium metal negative electrode in the charge-discharge cycle process is slowed down; the inert element aluminum acts as 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 the sodium-philic sites is maximized, and agglomeration, volume expansion and excessive consumption of electrolyte are avoided; multi-element alloy substrate (Cu) compared to pure sodium metal negative electrode2NiZn @ CNT) achieves higher coulombic efficiency (99.4%) and circulation stability (500h), and sodium deposition reaches 10mA h cm-2Still have a smooth topography; using this elemental alloy substrate (Cu)2NiZn @ CNT) matched 6A h pouch cell (Cu2NiZn @ CNT | | NaVPO)4F) The energy density of (A) is up to 351.6Wh kg-1And has good mechanical flexibility; the preparation method of the element alloy induced flexible sodium metal battery substrate 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 price is low, the multielement nano alloy is obtained, and all members in the alloy are in dispersed distribution, so that the uniform separation and dispersion of sodium-philic elements are facilitated; the time and temperature control in the self-combustion process are crucial to the size of alloy particles, and the alloy particles determine the length-diameter ratio of the subsequent carbon nano tubes; the controllable carbon tube prepared by chemical vapor deposition has excellent conductivity, current density can be dispersed, and the interlaced carbon tube can accommodate metal deposition to obtain a smooth metal cathode.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention.

Claims (8)

1. A multi-component alloy induced flexible sodium metal battery substrate is characterized by comprising zinc alloy and a carbon tube; the zinc alloy is embedded in the carbon tube, wherein the weight of the zinc alloy accounts for not more than 20 percent of the total weight of the substrate; the zinc alloy also contains catalytic metal elements.
2. The multi-alloy induced flexible sodium metal battery substrate of claim 1, wherein: the zinc alloy also contains an inert metal element Al.
3. The multi-alloy induced flexible sodium metal battery substrate of claim 1, wherein: the catalytic metal element comprises one or more of Fe, Ni, Cu and Co.
4. The multi-alloy induced flexible sodium metal battery substrate of claim 1 or 3, wherein: when one or more of Fe, Ni and Co is adopted as the catalytic metal element, the molar ratio of Fe, Ni, Co and Zn is 1:1:1: 1.
5. The multi-alloy induced flexible sodium metal battery substrate of claim 1 or 3, wherein: when Cu and Ni are used as the catalytic metal elements, the molar ratio between Cu and Ni and Zn is 2:1: 1.
6. A method for preparing the multi-component alloy-induced flexible sodium metal battery substrate as defined in any one of claims 1 to 5, characterized by the steps of:
step 1: dissolving zinc nitrate and other nitrates in deionized water and stirring to obtain a nitrate solution; the other nitrates are: one or more of nickel nitrate, ferric nitrate, cobalt nitrate or aluminum nitrate, wherein the molar ratio of each 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 and the nitrate is 1;
and step 3: transferring the sol into a drying oven to be heated to obtain dry gel; the heating temperature is 70-90 ℃, and the heating time is 12-48 h;
and 4, step 4: placing the xerogel obtained in the step 3 in a high-temperature inert atmosphere for self-combustion to obtain a multi-element alloy;
and 5, performing chemical vapor deposition on the multi-element alloy: grinding the multi-component alloy into powder, spreading the powder in a magnetic boat, placing the magnetic boat in a tube furnace, introducing inert gas, heating the magnetic boat to 600-800 ℃ at a heating speed of 5-10 ℃/min, introducing a mixed gas of the inert gas and acetylene for 0.5-1 h, and cooling the magnetic boat along with the furnace to obtain the multi-component alloy carbon-coated tube composite material, namely the multi-component alloy induced flexible sodium metal battery substrate.
7. The method of claim 6, wherein: in the step 1, when other nitrates are nickel nitrate, adding copper nitrate, dissolving in deionized water and stirring to obtain a nitrate solution; the molar ratio of the copper nitrate to the nickel nitrate to the zinc nitrate is 2:1: 1.
8. The method according to claim 6 or 7, characterized in that: the inert gas is argon or hydrogen.
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