CN110660970A - Flexible self-supporting MXene/zinc composite electrode and preparation method and application thereof - Google Patents

Flexible self-supporting MXene/zinc composite electrode and preparation method and application thereof Download PDF

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CN110660970A
CN110660970A CN201910954273.2A CN201910954273A CN110660970A CN 110660970 A CN110660970 A CN 110660970A CN 201910954273 A CN201910954273 A CN 201910954273A CN 110660970 A CN110660970 A CN 110660970A
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zinc
mxene
film
fluoride
flexible self
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冯金奎
田园
安永灵
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Shandong University
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Abstract

The invention relates to a flexible self-supporting three-dimensional layered MXene/zinc composite electrode and a preparation method and application thereof. Composite material consisting of three-dimensional layered MXene film and metal zinc, wherein the three-dimensional layered MXene film is formed by Ti3C2、Nb4C3、Ti2C、Ta4C3、TiNbC、(V0.5Cr0.5)3C2、V2C、Nb2C、Ti3CN、Ti3C2、Ti2C、Ta4C3、TiNbC、(V0.5Cr0.5)3C2、V2C、Nb2C、Nb4C3Or Ti3CN, and zinc is loaded on the three-dimensional layered MXene film. The zinc-doped lithium ion battery has larger specific surface area, can load more zinc, can be used as a zinc metal negative electrode or a current collector of a lithium metal negative electrode, can well inhibit the growth of zinc dendrites or lithium dendrites, and can be used as a negative electrode material of secondary charge and discharge batteries such as lithium ion batteries, sodium ion batteries or potassium ion batteries, or an electrode material of a super capacitor.

Description

Flexible self-supporting MXene/zinc composite electrode and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrode material preparation, and particularly relates to a flexible self-supporting MXene/zinc composite electrode and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
With the increasing demand of electric vehicles, large-scale energy storage, light electric vehicles and the like, and the decreasing of global non-renewable resources, the development of secondary energy storage chargeable and dischargeable batteries with high performance and large capacity is urgent based on the urgent demand of current green, efficient and practical energy storage materials.
The zinc (Zn) is environment-friendly, rich in earth reserves, low in price, good in ductility and highly stable in air and aqueous solution systems, and most importantly, the zinc cathode has very high theoretical specific capacity (875mAh/g) and lower reduction potential (-3.04V relative to the potential of a standard hydrogen electrode), so that the zinc ion battery has great potential, is widely researched at present and is an energy storage system with the highest market application value. However, in the charging process of the zinc metal battery, metal zinc dendrites are easily formed on the surface of the negative electrode in the repeated deposition and precipitation processes of zinc ions during the reduction process, and the sharp metal zinc dendrites are likely to lose efficacy and even cause safety problems such as explosion and the like; in addition, the formation of zinc dendrites also reduces the capacity of zinc metal batteries, and the problem of zinc dendrites severely limits their practical application.
Similarly, the lithium metal has extremely high theoretical specific capacity (3879mAh/g) and a lower voltage window in the lithium metal battery, and can meet the requirement of a high-energy-density battery system. But also can generate serious lithium dendrites in the circulation process, the sharp lithium dendrites can pierce through the diaphragm to generate safety problems, the growth of the lithium dendrites can lead to the continuous growth of an SEI film and the continuous consumption of electrolyte, and the service life of the battery is greatly shortened along with capacity attenuation, so that the practical application of the lithium metal battery is greatly limited.
Therefore, the suppression of the growth of metal dendrites is imminent. At present, strategies for effectively inhibiting the growth of metal dendrites and improving the cycling stability and safety performance of a metal negative electrode are gradually increased, such as increasing the specific surface area of the metal negative electrode, pre-depositing nucleation sites on a current collector and the like. The novel two-dimensional MXene material discovered by Yury et al at present has the advantages of good mechanical flexibility, high specific surface, stable chemistry, high conductivity, unique photoelectric property and the like, the colloidal solution of the two-dimensional MXene can be assembled into a self-supporting, hydrophilic, flexible and conductive film without additives, the film has the characteristic similar to graphene, but the film is better than the graphene in many performances, so that the MXene attracts researchers in various material and chemical fields, has great potential for inhibiting the growth of a metal cathode, and related reports are few at present.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a flexible self-supporting MXene/zinc composite electrode and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows:
in a first aspect, the flexible self-supporting MXene/zinc composite electrode is a composite material consisting of a three-dimensional layered MXene film and metallic zinc, wherein the MXene film is loaded with zinc.
In some embodiments, the three-dimensional layered MXene film is formed from Ti3C2、Nb4C3、Ti2C、Ta4C3、TiNbC、(V0.5Cr0.5)3C2、V2C、Nb2C、Ti3CN、Ti3C2、Ti2C、Ta4C3、TiNbC、(V0.5Cr0.5)3C2、V2C、Nb2C、Nb4C3Or Ti3One or a mixture of more than two of CN.
In some embodiments, the thickness of the composite electrode is 6-9 μm.
The composite film has a three-dimensional layered structure, has a larger specific surface area, can load more zinc, improves the conductivity, can be directly used as a negative electrode of a zinc battery, has a better buffering effect, and improves the effect of inhibiting the growth of zinc dendrites. As the current collector of the negative electrode of the lithium battery, the effect of inhibiting the growth of lithium dendrites is improved. The composite membrane has better mechanical flexibility.
In some embodiments, the mass ratio of zinc in the composite electrode is 8-12% or 30-60%.
The loading capacity is controlled by controlling the electrodeposition time, and when the zinc-based metal cathode is used, more zinc is loaded, namely about 30-60 wt%; when the lithium ion battery is used as a lithium metal negative electrode current collector, the load is correspondingly reduced, and the control amount is only 8-12%.
In a second aspect, the preparation method of the composite film comprises the following specific steps:
preparation of MXene film: adding MAX phase raw materials into a mixed solution of acid and fluoride, and sequentially performing etching and stripping methods to obtain an MXene film;
and electrodepositing the MXene film with metal zinc to obtain the composite film.
The preparation method of the composite membrane comprises the following specific steps:
preparation of MXene film: adding MAX phase raw materials into a mixed solution of acid and fluoride, centrifuging the obtained mixture of the washed solid-phase substances by a stripping method to obtain MXene colloidal solution, filtering the colloidal solution, and drying to obtain an MXene membrane;
the MXene film and the counter electrode form an electrode system, the zinc salt is used as electrolyte, and the metal zinc is electrodeposited to obtain the composite film.
The MXene film is prepared by a simple vacuum filtration method, and can be directly self-assembled into a flexible self-supporting film without adding any conductive additive or binder. The bonding strength is higher, the durability of the composite membrane is improved, and the battery is pollution-free.
In some embodiments, the MAX phase raw material is Ti3AlC2、Nb4AlC3、Ti3SiC2、Ta4SiC3、Nb4SiC3、Ti2AlC、Ta4AlC3、TiNbAlC、(V0.5Cr0.5)3AlC2、Mo3AlC2、V2AlC、Nb2AlC、Ti3AlCN、Ti2SiC、TiNbSiC、(V0.5Cr0.5)3SiC2、V2SiC、Nb2SiC or Ti3One or a mixture of two or more of SiCN.
In some embodiments, the acid is one or a mixture of two or more of hydrochloric acid, acetic acid, gluconic acid, citric acid, oxalic acid, carbonic acid, sulfuric acid, and the like. In some embodiments, the fluoride comprises a mixture of one or more of zinc fluoride, sodium fluoride, potassium fluoride, zinc fluoride, aluminum fluoride, calcium fluoride. In some embodiments, the mass ratio of MAX phase starting material to acid fluoride is 1: 8-12: 8-12; preferably 1: 10: 10.
in some embodiments, the centrifugation speed is 3000-. In some embodiments, the filter membrane for colloidal solution filtration is 4-6cm in diameter.
In some embodiments, the stripping is performed by ultrasonic stripping or mechanical stripping with an appropriate amount of deionized water.
According to the invention, the substance after the etching reaction is layered by a stripping method to obtain the colloidal solution containing the single-layer MXene sheet, which is beneficial to obtaining the three-dimensional layered structure.
In some embodiments, the zinc salt is any one of zinc sulfate, zinc chloride, zinc acetate, zinc carbonate, and zinc nitrate, preferably zinc sulfate. In some embodiments, the concentration of zinc salt is 1.5 to 2.5 moles per liter. In some embodiments, the solvent of the zinc salt is one or a mixture of two or more of deionized water, absolute ethyl alcohol, butanol, ethylene glycol, n-hexane and dimethyl sulfoxide; preferably deionized water.
In some embodiments, the current of electrodeposition is 0.5 to 2 milliamps per square centimeter.
In a third aspect, the flexible self-supporting MXene/zinc composite electrode is applied to a zinc metal negative electrode of a zinc battery.
The flexible self-supporting MXene/zinc composite electrode is used as a lithium metal negative electrode current collector, a negative electrode material of a lithium/sodium/potassium ion battery or a super capacitor.
When the flexible three-dimensional layered MXene/zinc composite material is used as a zinc metal cathode, the flexible three-dimensional layered MXene/zinc composite material has a flexible layered structure and good conductivity, and the MXene layer can play a good buffering role and inhibit the growth of zinc dendrites. When the lithium metal negative electrode current collector is used, metal zinc can react with lithium at low temperature according to the alloying reaction of lithium-zinc alloy, zinc has a very good lithium affinity effect, the lithium metal negative electrode current collector has the advantages of providing more nucleation sites, effectively reducing nucleation potential barrier, finally reducing the actual current density of lithium in the deposition and dissolution process, being beneficial to reducing the deposition and dissolution overpotential, improving the deposition uniformity, improving the internal lithium ion transmission rate, being capable of changing the lithium deposition direction and relieving the battery safety problem caused by the fact that lithium dendrite pierces a diaphragm.
The invention has the beneficial effects that:
(1) the electrodeposition method is simple and convenient to operate and can be used for large-scale production. The three-dimensional layered structure of the flexible self-supporting three-dimensional layered MXene membrane can provide more nucleation sites and can load more metal zinc, the layered structure can provide an effective and better buffer layer, and the MXene membrane has high conductivity, good hydrophilicity and better mechanical flexibility. In addition, the MXene membrane can be prepared into an integrated three-dimensional flexible electrode through simple suction filtration without any conductive agent or additive, so that the preparation cost of the electrode is greatly saved.
(2) The invention adopts the electrodeposition method to load the metal zinc on the MXene, and the prepared flexible electrode can be directly used as a zinc metal cathode and has better effect of inhibiting the growth of metal zinc dendrites.
(3) The material prepared by the invention has excellent universality and wide application. The composite material is used as a current collector of a lithium metal negative electrode, the lithium affinity of zinc can be used as a nucleation site, the nucleation barrier is effectively reduced, the actual current density in the lithium deposition and dissolution process is reduced, the reduction of the deposition and dissolution overpotential is facilitated, the deposition uniformity is improved, the internal lithium ion transmission rate is improved, the lithium deposition direction can be changed, the battery safety problem caused by the fact that lithium dendrite pierces a diaphragm is relieved, and the composite material has an excellent effect of inhibiting the growth of the lithium dendrite.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is a micro-topography of the electrodeposition of metallic zinc onto a three-dimensional layered MXene film prepared in example 1;
FIG. 2 is an X-ray diffraction pattern of an MXene film and an MXene/zinc composite prepared in example 1;
fig. 3 is a diagram of the electrochemical performance of the MXene/zinc composite material prepared in example 1 as a zinc metal negative electrode.
Fig. 4 is a graph of electrochemical performance of the MXene/zinc composite material prepared in example 1 as a current collector of a lithium metal negative electrode.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise. The invention will be further illustrated by the following examples
Example 1
MAX phase selection of the most common Ti3AlC2Stirring the powder in a mixed solution of 10ml of hydrochloric acid and 0.8g of zinc fluoride, adding water, centrifuging, washing to remove redundant acid and fluoride, peeling multiple layers of MXene, ultrasonically peeling and centrifuging to obtain a few-layer/multiple-layer MXene colloidal solution, selecting 50ml of the colloidal solution, filtering, and drying in a vacuum oven at 50 ℃ to obtain a flexible self-supporting three-dimensional layered MXene film;
preparing 2 mol/L zinc sulfate aqueous solution, selecting ultrapure water as a solvent, and stirring for half an hour at room temperature until the solution is clear and transparent to obtain electrodeposition solution containing divalent zinc salt;
then, 20ml of electroplating solution is placed in an electrolytic bath, constant current deposition is carried out for a proper time at a current density of 1 milliampere per square centimeter, an MXene film is used as a working electrode, unreacted liquid is removed by washing with ultrapure water, and drying is carried out in an oven to obtain a flexible self-supporting three-dimensional layered MXene/zinc composite electrode;
and assembling the battery. When used as a zinc metal negative electrode, the cell can be assembled in an air atmosphere at room temperature. When used as a lithium metal negative current collector, metallic lithium is pre-deposited on a flexible self-supporting three-dimensional layered MXene/zinc current collector and electrodeposited at a current density of 0.5 milliamps per square centimeter, resulting in an alternative lithium metal negative electrode.
In the application of the composite film prepared in the embodiment 1 as a current collector in a lithium metal negative electrode, the cut-off voltage of the deposited metal lithium is set to be 0.5V, compared with the existing lithium deposition potential, the deposition dissolution overpotential is reduced, and the deposition is more uniform.
As can be seen from FIG. 1, the side view of the composite film of the present invention shows a multilayer structure, the thickness of the composite film is about 7 μm, and the XRD pattern is shown in FIG. 2. As can be seen from fig. 3, when the zinc metal negative electrode is used as the zinc metal negative electrode, the cycle number is 150, the good coulombic efficiency is still maintained, and the capacity reduction of the zinc metal battery caused by zinc dendrites does not occur; as can be seen from fig. 4, when the lithium metal negative electrode current collector is used, the good coulombic efficiency is still maintained when the cycle number is 200, and the capacity reduction phenomenon of the zinc metal battery caused by lithium dendrites does not occur.
Example 2
MAX phase selection is V2AlC powder, MAX phase is V2Etching AlC powder by using hydrochloric acid and lithium fluoride at 50 ℃ to remove an aluminum atomic layer, then stripping to obtain MXene colloidal solution, and carrying out suction filtration to obtain MXene film; then, an aqueous solution of zinc chloride at 2 mol/l was prepared as an electrodeposition solution, and electrodeposition was performed in an electrolytic cell.
Example 3
MAX phase is Ti3AlC2Powder, MXene preparation method example 1, the main salt of the electrodeposition solution is zinc chloride, the solvent is absolute ethyl alcohol, the concentration is 2 mol per liter, electrodeposition and drying are carried out under the electrodeposition conditions the same as example 1, and the three-dimensional layered MXene/Zn composite film can effectively inhibit the growth of metal dendrites when used as a zinc metal negative electrode and a lithium metal negative electrode current collector.
Example 4
Nb is selected for MAX phase2The preparation method of AlC powder, MXene, example 1, zinc acetate was used as the main salt of the electrodeposition solution, absolute ethyl alcohol was used as the solvent, the concentration was 2 mol/l, and electrodeposition and baking were performed under the same electrodeposition conditions as in example 1. The three-dimensional layered MXene/Zn composite film can effectively inhibit the growth of metal dendrites when being used as a zinc metal negative electrode and a lithium metal negative electrode current collector.
Example 5
MAX phase selects Mo3AlC2Powder, MXene preparation method example 1, zinc sulfate was used as the main salt of the electrodeposition solution and deionized water was used as the solvent, preferably at a concentration of 2 mol/l, and the electrodeposition and drying were carried out under the same electrodeposition conditions as in example 1, and used as the current collectors of zinc metal negative electrode and lithium metal negative electrode to suppress the growth of metal dendrites.
The three-dimensional layered MXene membrane is electrodeposited with metal zinc, and the obtained three-dimensional layered MXene/Zn composite flexible material not only can be used for inhibiting the growth of metal zinc dendrites or lithium dendrites, but also can be used as a lithium ion battery cathode material, a sodium ion battery cathode material, a potassium ion battery cathode material or an electrode material of a super capacitor because the metal zinc has higher theoretical specific capacity when being used as the cathode material of a chargeable and dischargeable battery.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A flexible self-supporting MXene/zinc composite electrode is characterized in that: the composite material consists of three-dimensional layered MXene film and metal zinc, and the MXene film is loaded with zinc.
2. The flexible self-supporting MXene/zinc composite electrode of claim 1, wherein: the thickness of the composite electrode is 6-9 μm;
or, three-dimensional layered MXene film made of Ti3C2、Nb4C3、Ti2C、Ta4C3、TiNbC、(V0.5Cr0.5)3C2、V2C、Nb2C、Ti3CN、Ti3C2、Ti2C、Ta4C3、TiNbC、(V0.5Cr0.5)3C2、V2C、Nb2C、Nb4C3Or Ti3One or a mixture of more than two of CN.
3. The flexible self-supporting MXene/zinc composite electrode of claim 1, wherein: the mass ratio of zinc in the composite electrode is 8-12% or 30-60%.
4. The method for preparing the flexible self-supporting MXene/zinc composite electrode of any one of claims 1-3, wherein: the method comprises the following steps:
preparation of MXene film: adding MAX phase raw materials into a mixed solution of acid and fluoride, and sequentially performing etching and stripping methods to obtain an MXene film;
and electrodepositing the MXene film with metal zinc to obtain the composite film.
5. The method for preparing the flexible self-supporting MXene/zinc composite electrode according to claim 4, wherein: the method comprises the following specific steps:
preparation of MXene film: adding MAX phase raw materials into a mixed solution of acid and fluoride, centrifuging the obtained mixture of the washed solid-phase substances by a stripping method to obtain MXene colloidal solution, filtering the colloidal solution, and drying to obtain an MXene membrane;
the MXene film and the counter electrode form an electrode system, zinc salt is used as electrolyte, and metal zinc is electrodeposited to obtain a composite film;
preferably, the fluoride comprises one or a mixture of more than two of zinc fluoride, sodium fluoride, potassium fluoride, zinc fluoride, aluminum fluoride and calcium fluoride;
preferably, the mass ratio of the MAX phase raw material to the acid to the fluoride is 1: 8-12: 8-12; more preferably 1: 10: 10;
preferably, the centrifugal speed is 3000-;
preferably, the diameter of the filter membrane for filtering the colloidal solution is 4-6 cm;
preferably, the stripping method is ultrasonic stripping or mechanical stripping by adding a proper amount of deionized water;
preferably, the zinc salt is any one of zinc sulfate, zinc chloride, zinc acetate, zinc carbonate, zinc nitrate and the like; further preferably zinc sulfate;
preferably, the concentration of zinc salt is 1.5 to 2.5 moles per liter;
preferably, the MAX phase raw material is Ti3AlC2、Nb4AlC3、Ti3SiC2、Ta4SiC3、Nb4SiC3、Ti2AlC、Ta4AlC3、TiNbAlC、(V0.5Cr0.5)3AlC2、Mo3AlC2、V2AlC、Nb2AlC、Ti3AlCN、Ti2SiC、TiNbSiC、(V0.5Cr0.5)3SiC2、V2SiC、Nb2SiC or Ti3One or a mixture of two or more of SiCN.
6. The method for preparing the flexible self-supporting MXene/zinc composite electrode according to claim 5, wherein: the acid is one or more of hydrochloric acid, acetic acid, gluconic acid, citric acid, oxalic acid, carbonic acid, and sulfuric acid.
7. The method for preparing the flexible self-supporting MXene/zinc composite electrode according to claim 5, wherein: the solvent of the zinc salt is one or a mixture of more than two of deionized water, absolute ethyl alcohol, butanol, ethylene glycol, n-hexane and dimethyl sulfoxide; preferably deionized water.
8. The method for preparing the flexible self-supporting MXene/zinc composite electrode according to claim 5, wherein: the current of the electrodeposition is 0.5-2 milliamperes per square centimeter.
9. The flexible self-supporting MXene/zinc composite electrode of any one of claims 1-3 used as zinc metal negative electrode for inhibiting zinc dendrite growth well.
10. Use of the flexible self-supporting MXene/zinc composite electrode of any one of claims 1 to 3 as a negative electrode current collector for lithium metal or as a negative electrode material for lithium, sodium, potassium ion batteries, or as an electrode material for supercapacitors.
CN201910954273.2A 2019-10-09 2019-10-09 Flexible self-supporting MXene/zinc composite electrode and preparation method and application thereof Pending CN110660970A (en)

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