CN109216648B - Intercalation electrode constructed by ion pre-embedding two-dimensional layered material and preparation method and application thereof - Google Patents

Intercalation electrode constructed by ion pre-embedding two-dimensional layered material and preparation method and application thereof Download PDF

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CN109216648B
CN109216648B CN201810951829.8A CN201810951829A CN109216648B CN 109216648 B CN109216648 B CN 109216648B CN 201810951829 A CN201810951829 A CN 201810951829A CN 109216648 B CN109216648 B CN 109216648B
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dimensional layered
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CN109216648A (en
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张炳森
李浩杰
鲁铭
韩文娟
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Institute of Metal Research of CAS
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    • H01M10/00—Secondary cells; Manufacture thereof
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    • 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
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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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Abstract

The invention discloses an intercalation electrode constructed by pre-embedding ions into a two-dimensional layered material, and a preparation method and application thereof, and belongs to the technical field of preparation of electrode materials of electrochemical energy storage devices. Firstly, a two-dimensional layered material is used as a working electrode, a solution containing pre-embedded ions is used as an electrolyte, and a high-conductivity material is used as a counter electrode to construct an electrochemical ion pre-embedded reaction system. The electrochemical workstation is used for applying a fluctuating potential (cyclic voltammetry and constant current charging and discharging technologies) to the working electrode in a specific voltage window, so that ions are forced to be periodically inserted and removed in the two-dimensional layered material layer, and the ion insertion and removal is performed to open an ion transport channel in advance. By controlling the final state potential, the pre-embedded ions are anchored between the inner layers of the two-dimensional material, so that the ion supporting effect is realized, a high-speed and stable ion transport channel is constructed, the electrode function of the two-dimensional layered material is further improved, and a high-performance energy storage system is served.

Description

Intercalation electrode constructed by ion pre-embedding two-dimensional layered material and preparation method and application thereof
Technical Field
The invention relates to the technical field of preparation of electrode materials of an energy storage system, in particular to an intercalation electrode constructed by pre-embedding ions into a two-dimensional layered material, and a preparation method and application thereof.
Background
In the design of an electrochemical energy storage and conversion system, the intrinsic physical and chemical properties of an electrode material determine an energy conversion and storage mechanism and electrochemical performance (such as voltage, capacity, rate performance, cycle stability, safety performance, temperature tolerance and the like). Due to the unique organ-shaped microstructure of the two-dimensional layered material, the two-dimensional layered material has a layered space with a nano scale, can effectively prevent electrolyte ions from diffusing and migrating through crystal lattices, promotes the storage and transmission of ions, electrons and charges, and is widely applied to the construction of an insertion layer type energy storage system. E.g. based on lithium ion intercalation/deintercalation of LiCoO2Commercial lithium ion battery system constructed by (anode) and graphite (cathode) based on Na ion intercalation and deintercalationxMO2Sodium ion battery system constructed with (M ═ Fe, Mn, Co, V, Ti) (positive electrode) and hard carbon (negative electrode), and based on Li+At the negative electrode and PF6 -And a double-ion battery system constructed by embedding ions into positive electrodes respectively with a decarburized two-dimensional layered material.
Although the two-dimensional layered material has incomparable intrinsic characteristic advantages compared with other materials in the construction of a high-performance energy storage system, the energy storage system cannot meet the economic requirement of long-term cyclic use due to irreversible damage to the layered structure caused by ion intercalation and deintercalation in the periodic charging and discharging process; in addition, the limited stacking space limits the amount of ionic charge it can accommodate in the electrolyte, resulting in a lower specific electrode capacity for the two-dimensional layered material.
For a long time, the contradiction between the structural stability and the high specific capacity of the two-dimensional layered material and the requirement of a larger space in the layer has limited the further application of the two-dimensional layered material as an electrode material, and how to coordinate the relationship between the two is a technical problem which needs to be solved urgently by the technical personnel in the field.
Disclosure of Invention
Aiming at the problems of low capacity and low cycle performance caused by the limitation of the interlayer spacing and stability of a two-dimensional layered electrode material in the prior art, the invention provides an intercalation electrode constructed by embedding ions into the two-dimensional layered material in advance, a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing intercalation electrode constructed by ion pre-embedding two-dimensional layered material, which adopts electrochemical method to make pre-embedded ion carry out periodic embedding and removing between layers of two-dimensional layered material, thus realizing the purpose of opening ion transport channel in the two-dimensional layered material in advance by ion embedding and removing; meanwhile, the pre-embedded ions are anchored between the inner layers of the two-dimensional layered material to realize the ion supporting effect, so that the intercalation electrode with a high-speed and stable ion transport channel is constructed. The method comprises the following steps:
(1) preparation of a working electrode:
uniformly coating electrode slurry taking a two-dimensional layered material as an active substance on a current collector, and drying in vacuum to obtain a working electrode;
(2) selection of an electrochemical reaction system:
the ion pre-embedding electrochemical reaction system selects a three-electrode system or a two-electrode system; the three-electrode system comprises the working electrode, the counter electrode, the reference electrode and electrolyte prepared in the step (1), wherein the reference electrode is selected according to the type of the pre-embedded ions; the two-electrode system comprises the working electrode prepared in the step (1), a counter electrode and electrolyte, wherein the counter electrode does not react with the pre-embedded ions in the electrochemical process; the electrolyte contains pre-embedded ions;
(3) implementation of electrochemical ion pre-intercalation:
assembling the electrochemical system selected in the step (2) into an electrochemical reaction device, realizing the embedding and the releasing of the pre-embedded ions in the two-dimensional layered material by an electrochemical method, opening an ion transport channel, and simultaneously anchoring the pre-embedded ions between layers of the two-dimensional layered material; and after the reaction is finished, taking out the working electrode, washing the working electrode with deionized water, and drying the working electrode at normal temperature to obtain the intercalation electrode constructed by the ion pre-embedded two-dimensional layered material.
In the step (1), the electrode slurry is prepared by uniformly mixing the two-dimensional layered material, the conductive agent and the binder according to a required proportion, and adding N-methylpyrrolidone (NMP) for stirring to form the electrode slurry with fluidity; or when the electrode slurry can realize the construction of a self-supporting electrode, the two-dimensional layered material is directly used as a working electrode.
In the step (1), the two-dimensional layered material is graphite, MXene or MoS2The conductive agent is acetylene black or Super P, the binder is polyvinylidene fluoride resin PVDF or carboxymethyl cellulose CMC, and the weight mixing ratio of the two-dimensional layered material, the conductive agent and the binder is 8: (1-2): (1-2) addingThe ratio of N-methylpyrrolidone (NMP) to two-dimensional layered material was 200 ml: 1g of a compound; the current collector is made of copper foil, aluminum foil, titanium sheet or carbon paper, the total weight of the two-dimensional layered material, the conductive agent and the binder on the coated current collector is 2-10mg, and the vacuum drying temperature is 60 ℃.
In the step (2), the pre-intercalation ions in the electrolyte are metal cations, non-metal cations or non-metal anions, and specifically may be Na+、Mg2+、Al3+、EMI+、PF6 -And the concentration of the pre-embedded ions is 0.5-3 mol/L; the solvent matched with the pre-embedded ions is selected from a water system or a non-water system (an organic system), for example, the solvent is water, dimethyl sulfoxide or ethers; the water system environment can be tested in the air, the organic system needs to be tested in a glove box, and in the organic system, the numerical values of water and oxygen in the glove box are controlled to be 0.1-0.5 ppm; the concentration of the pre-embedded ions needs to depend on the matching of the pre-embedded ions and the solvent, and a solution with high fluidity is selected as much as possible so as to accelerate the mass transfer process of the ions.
In the step (2), the counter electrode can be made of high-conductivity materials such as carbon paper and titanium sheet, and the reference electrode can be a standard hydrogen electrode (NHE 0V), a saturated calomel electrode (SCE 0.242V), a silver/silver chloride electrode (Ag/AgCl0.199V) or a ferrocene electrode (Fe)+Fe 0.69V), etc., but reaction with pre-intercalating ions should be avoided.
In the step (3), the electrolytic cell used in the electrochemical reaction device is a quartz or polytetrafluoroethylene container with a volume of 10ml to 200 ml.
In the step (3), the electrochemical method is cyclic voltammetry or constant current charging and discharging; the process parameters of the cyclic voltammetry are as follows:
the scanning speed is set to be 0.1-25mV/s, the scanning voltage range is determined according to the voltage window of the pre-intercalation electrochemical reaction system, the pre-intercalation cation: set to the lowest voltage to 0.2-1V above it; pre-intercalating anions: setting the voltage to 0.2-1V below the maximum voltage; the number of the cyclic scanning is 5-100 circles;
the constant current charging and discharging method comprises the following process parameters:
the current density is selected in the range of 0.1-20A/g, cation intercalation: set to the lowest voltage to 0.2-1.0V above it; pre-intercalating anions: setting the voltage to 0.2-1.0V below the maximum voltage; the number of cyclic scans is 5 to 40 cycles; the number of charging and discharging circles is set to be 5-100 circles.
The intercalation electrode constructed by the ion pre-embedded two-dimensional layered material is prepared by adopting the method, the interlayer spacing of the two-dimensional layered material is regulated and controlled by electrochemical ion pre-embedding, and meanwhile, the pre-embedded ions can support the two-dimensional layered material to provide a stable ion channel for the subsequent embedding and extraction of energy storage electrolyte ions in the two-dimensional material, so that the ion transport capacity of the electrode material is improved. The ion pre-embedded two-dimensional layered material is suitable for lithium ion batteries, sodium ion batteries, lithium sulfur battery energy storage systems, dual-ion batteries or high-valence secondary ion batteries.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides an ionic electrochemical pre-embedded two-dimensional layered material for the first time, and the ionic electrochemical pre-embedding is adopted, so that not only can the two-dimensional layered material establish a stable layer space, but also a rapid transport channel is provided for the embedding and the removing of interlayer ions, and meanwhile, the pre-embedded ions can support the two-dimensional layered material to a certain extent, so that the two-dimensional layered material has larger layer spacing, and a more open structure is obtained. Thereby effectively optimizing and improving the structure and the interface of the two-dimensional layered material and constructing a high-performance two-dimensional layered material electrode.
2. The ionic electrochemical pre-intercalation method adopted by the invention can accurately regulate and control the program parameters of the electrochemical pre-intercalation, thereby realizing the pre-intercalation of different anions and cations into various two-dimensional layered compounds, and being a universal ionic pre-intercalation method.
3. The two-dimensional layered electrode material with the pre-embedded ionic electrochemistry prepared by the invention plays an important role in a novel energy storage device, can provide effective technical support for a super capacitor, a lithium secondary battery, a sodium ion battery, a potassium ion battery, a calcium ion battery and a double-ion battery, and provides great guiding significance for realizing the energy storage device with high energy density and high power density.
Drawings
Fig. 1 is a diagram of an electrochemical device for pre-embedding ions into a two-dimensional layered material, wherein the device is a three-electrode system and comprises a working electrode, a counter electrode and a reference electrode, and an electrochemical program for setting specific parameters is controlled by an electrochemical workstation through computer software to perform an ion electrochemical pre-embedding experiment.
FIG. 2 shows Na+、Mg2+And Al3+XRD data result of electrochemical pre-intercalation of MXene, from which it can be seen that Na is electrochemically pre-intercalated by the ions+、Mg2+And Al3+The small angle shift of the (002) peak of MXene is shown, which indicates that Na+、Mg2+And Al3+The embedding of (2) enables MXene to obtain larger interlayer spacing and more stable interlayer space.
FIG. 3 is Na+、Mg2+And Al3+Cyclic voltammogram of the electrochemical pre-intercalation MXene process.
FIG. 4 shows Na+、Mg2+And Al3+As a result of SEM-EDX of MXene pre-embedded by electrochemistry, it can be seen that pre-embedded ions are uniformly distributed in the element distribution diagram of MXenes pre-embedded with ions.
Detailed Description
The invention is described in detail below with reference to the figures and examples.
The invention provides a preparation method for constructing a high-performance intercalation electrode by pre-embedding electrochemical ions into a two-dimensional layered material, which comprises the following steps:
(1) preparing a two-dimensional layered material working electrode:
firstly, uniformly mixing a two-dimensional layered material, a conductive agent and a binder according to a certain proportion, adding N-methyl pyrrolidone (NMP) and stirring to form electrode slurry with fluidity, then uniformly coating the electrode slurry on a current collector, weighing the mass of the coated electrode active substance and drying in vacuum; in addition, a part of two-dimensional materials can realize the construction of a self-supporting electrode and can be directly used as a working electrode for pre-embedding electrochemical ions;
(2) selection of an ion pre-intercalation electrochemical reaction system:
the ion pre-intercalation electrochemical reaction system can be a conventional three-electrode system or a two-electrode system. In a three-electrode system, the electrode prepared in the step (1) is used as a working electrode, an inert and high-conductivity material is used as a counter electrode, and the reference electrode is selected according to the type of pre-embedded ions; if a two-electrode system is selected, the counter electrode is ensured not to react with the pre-embedded ions in the electrochemical pre-embedding process;
(3) selection of electrochemical pre-intercalation ionic electrolyte:
in the electrochemical electrode system selected in step (2), the electrochemically pre-intercalated ions can be metal and non-metal cations and anions, such as Na+、Mg2+、Al3+、EMI+、PF6 -In addition, the solvent matched with the pre-embedded ions can be selected from a water system and a non-water system, the water system environment can carry out experiments in the air, and the organic system needs to carry out experimental operation in a glove box; the concentration of the pre-embedded ions needs to depend on the matching of the pre-embedded ions and a solvent, and a high-fluidity solution is selected as far as possible so as to accelerate the mass transfer process of the ions;
(4) implementation of the ionic electrochemical pre-intercalation:
and (3) carrying out ionic electrochemical pre-intercalation in an electrochemical reaction device consisting of the electrode system selected in the step (2) and the pre-intercalation ionic electrolyte adopted in the step (3). By means of the applied technology of the electrochemical workstation (such as cyclic voltammetry, by setting the scanning speed, the scanning voltage range and the scanning number of turns, and a constant current charging and discharging method, by setting the current density, the voltage range and the charging and discharging number of turns), the control of the mass transfer process of the pre-embedded ions is realized, and the ions are directionally transported into the two-dimensional layered material layer, so that the pre-embedded ions are anchored. Then, taking out the working electrode, washing the electrode with deionized water, and then drying the electrode at normal temperature;
(5) determination of the implementation of ion pre-intercalation:
performing basic characterization and analysis on the two-dimensional layered material electrode subjected to the electrochemical pre-embedding of the ions in the step (4), confirming the content and distribution of the pre-embedded ions through a scanning electron microscope and element distribution measurement (SEM-EDX), simultaneously performing X-ray powder diffraction (XRD) characterization on the electrode, and comparing results of the SEM-EDX and X-ray powder diffraction (XRD) characterization on the electrode to confirm that the electrochemical pre-embedding of the ions into the two-dimensional layered material can be effectively realized;
(6) the performance of the two-dimensional layered material electrode after the ionic electrochemical pre-embedding is as follows:
and (4) carrying out electrochemical performance test on the two-dimensional layered material electrode subjected to the ionic electrochemical pre-embedding in the step (4), and analyzing the structure-effect correlation between the performance and the pre-embedded ions through charge-discharge cycle test, cyclic voltammetry test, multiplying power performance test and alternating current impedance test, so as to provide guidance for the implementation of the ionic pre-embedding.
In the step (1), the two-dimensional layered active material electrode is prepared from the following materials in the preparation process: the two-dimensional layered active material is graphite, MXene, MoS2And the like, wherein the conductive agent is acetylene black or Super P, the binder is polyvinylidene fluoride resin PVDF or carboxymethyl cellulose CMC, and the mixing ratio is 8: (1-2): (1-2), adding N-methyl pyrrolidone (NMP) with the volume to active substance mass ratio of 200ml/g, using copper foil, aluminum foil, titanium sheet, carbon paper and the like as current collectors, wherein the mass of the coated electrode active substance is 2-10mg, and the vacuum drying temperature is 60 ℃;
in the step (2), the selection of the electrodes in the electrode system is as follows: the working electrode is graphite, MXenes, MoS2The materials with two-dimensional layered structure, the counter electrode can be carbon paper, titanium sheet or other high-conductivity materials, and the reference electrode can be standard hydrogen electrode (NHE 0V), saturated calomel electrode (SCE 0.242V), silver/silver chloride electrode (Ag/AgCl0.199V), and ferrocene electrode (Fe)+Fe 0.69V), etc., but reaction with pre-intercalating ions should be avoided.
In the step (3), the concentration of the pre-embedded ions is 0.5-3mol/L, the solvent is water, dimethyl sulfoxide, ethers and the like, and the electrolytic cell can adopt a container made of 10ml-200ml quartz or polytetrafluoroethylene. In organic systems, the water and oxygen values in the glove box should be controlled to be between 0.1 and 0.5 ppm.
In the cyclic voltammetry in the step (4), the scanning speed is set to be 0.1-25mV/s, the scanning voltage range is determined according to the voltage window of the pre-intercalation electrochemical reaction system, and the pre-intercalation cations are as follows: set to the lowest voltage to 0.2-1V above it; pre-intercalating anions: set to the highest voltage to 0.2-1.0V below it. The number of cyclic scans is 5 to 100 cycles; constant current charging and discharging method, current density is selected in the range of 0.1-20A/g, cation is embedded: set to the lowest voltage to 0.2-1.0V above it; pre-intercalating anions: set to the highest voltage to 0.2-1V below it. The number of cyclic scans is 5 to 40 cycles; the number of charge and discharge turns is set to 5 to 100 turns.
Example 1:
a method for constructing a high-performance intercalation electrode by pre-embedding electrochemical ions into a two-dimensional layered material specifically comprises the following steps:
(1) preparation of MXene electrode
Grinding a two-dimensional layered active material MXene, a conductive agent Super-P and a binder polyvinylidene fluoride PVDF according to the mass ratio of 8:1:1 to enable the two-dimensional layered active material MXene, the conductive agent Super-P and the binder polyvinylidene fluoride PVDF to be uniform, adding N-methyl pyrrolidone (NMP) to stir, enabling the volume of the N-methyl pyrrolidone (NMP) to be 200ml/g of the mass of the active material, stirring for more than 24 hours to form a flowable electrode slurry, uniformly brushing the electrode slurry on a current collector of carbon paper by using a brush, drying, weighing the mass of the coated electrode active material by one ten thousandth of the mass of the coated electrode active material, and placing the electrode slurry in a vacuum drying box to perform vacuum drying at 60 ℃ in a balance;
(2) selection of electrochemical electrode system:
the electrochemical electrode system selects a three-electrode system for ionic electrochemical pre-embedding. In a three-electrode system, the MXene active electrode prepared in the step (1) is used as a working electrode, a carbon paper electrode is used as a counter electrode, a KCl electrode of 1mol/L saturated calomel is used as a reference electrode, three electrode materials are fixed by a PTFE platinum sheet electrode clamp, and then the three electrode materials are placed in a 40ml PTFE container electrolytic cell to prepare an experiment;
(3) selection of electrochemical pre-intercalation ionic electrolyte:
in the three-electrode electrochemical electrode system selected in the step (2), the ions for electrochemical pre-intercalation are selected to be sodium ions Na+Therefore, the electrolyte of the system adopts 1mol/L sodium sulfate (Na)2SO4) The solution is an aqueous electrolyte, so that experiments can be carried out in air;
(4) performing ionic electrochemical pre-intercalation:
the electrode system of the three electrodes selected in the step (2) and 1mol/L sodium sulfate (Na) adopted in the step (3)2SO4) Under an electrochemical device consisting of the solution, an MXene electrode is pre-embedded by ion electrochemistry. The following electrochemical program was set by the electrochemical workstation: the cyclic voltammetry regulates and controls the electrochemical pre-embedding of ions by setting the scanning speed, the scanning voltage range and the number of scanning cycles; the scanning speed is set to 10mV/s, the voltage range of scanning is set to-0.8-0.2V, and the number of scanning turns is set to 40 turns. Washing the MXene electrode subjected to the electrochemical pre-embedding by using deionized water, and then drying the MXene electrode at normal temperature;
(5) characterization of the post-ionoelectrochemical pre-intercalation electrode:
characterizing the MXene electrode subjected to the electrochemical pre-embedding of the ions in the step (4), and qualitatively determining the distribution of the pre-embedded ions by combining a scanning electron microscope with element scanning (SEM-EDX), wherein the test elements are Ti, F, Na, O and Al, and meanwhile, carrying out X-ray diffraction (XRD) characterization on the MXene electrode, the test range is 5-85 degrees, and the data are combined to confirm that the electrochemical pre-embedding manner can effectively realize the pre-embedding of the ions into the two-dimensional layered material;
(6) testing the performance of the electrode after the ionic electrochemical pre-embedding:
and (3) carrying out electrochemical performance test on the MXene electrode subjected to the ionic electrochemical pre-embedding in the step (4), carrying out charge-discharge cyclic test, cyclic voltammetry test, multiplying power performance test and alternating current impedance test on the MXene electrode through an electrochemical workstation, and proving through experimental data that the ionic electrochemical pre-embedding two-dimensional layered material can effectively optimize and improve the structure and material interface of the MXene electrode, so that a high-performance two-dimensional layered material electrode is constructed.
With Na+The results of the scanning electron microscope combined with the element scanning (SEM-EDX) and X-ray diffraction XRD characterization of the ionic electrochemical pre-intercalation two-dimensional layered material MXene are shown in the figure 2(a) and figure 4, and through the data, the Na can be seen through the ionic electrochemical pre-intercalation mode+Effectively embedded in MXene material, and Na+The embedding of (b) causes a small angular shift of the (002) peak of MXene, indicating that Na+The embedding of (a) allows MXene to obtain a larger interlayer spacing and a more stable interlayer space, shown as Na in FIG. 3(a)+Cyclic voltammetry pre-embedding experimental curves.
Example 2:
a preparation method for constructing a high-performance intercalation electrode by pre-embedding an ionic electrochemical two-dimensional layered material specifically comprises the following steps:
(1) preparation of MXene electrode
Grinding a two-dimensional layered active material MXene, a conductive agent Super-P and a binder polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1.5:1.5 to ensure that the materials are uniform, wherein the mass of the MXene is 160mg, the mass of the conductive agent Super-P is 30mg, the mass of the binder polyvinylidene fluoride (PVDF) is 30mg, adding N-methyl pyrrolidone (NMP) to stir, the ratio of the volume of the N-methyl pyrrolidone (NMP) to the mass of the active substance is 200ml/g, stirring for more than 26 hours to form electrode slurry with fluidity, uniformly brushing the electrode slurry on a current collector of a Ti sheet by using a brush, weighing the mass of the coated electrode active substance by using a ten-thousandth balance after drying, and placing in a vacuum drying box to carry out vacuum drying at 60 ℃;
(2) selection of electrochemical electrode system:
the electrochemical electrode system selects a three-electrode system for ionic electrochemical pre-embedding. In a three-electrode system, the MXene active electrode prepared in the step (1) is used as a working electrode, a Ti sheet inert electrode is used as a counter electrode, the reference electrode adopts a KCl electrode of 1mol/L saturated calomel, three electrode materials are fixed by adopting a PTFE platinum sheet electrode clamp, and then the three electrode materials are placed in a 30ml PTFE container electrolytic cell to prepare an experiment;
(3) selection of electrochemical pre-intercalation ionic electrolyte:
in the three-electrode electrochemical electrode system selected in the step (2), the ions for electrochemical pre-intercalation are selected to be sodium ions Mg2+Therefore, the electrolyte of the system adopts 1mol/L magnesium sulfate (MgSO)4) The solution is an aqueous electrolyte, so that experiments can be carried out in air;
(4) performing ionic electrochemical pre-intercalation:
the electrode system of the three electrodes selected in the step (2) and the 1mol/L magnesium sulfate MgSO adopted in the step (3)4Under an electrochemical device consisting of the solution, an MXene electrode is pre-embedded by ion electrochemistry. The following electrochemical program was set by the electrochemical workstation: the cyclic voltammetry regulates and controls the electrochemical pre-embedding of ions by setting the scanning speed, the scanning voltage range and the number of scanning cycles; the scanning speed is set to be 15mv/s, the voltage range of scanning is set to be-0.7-0.2V, and the number of scanning turns is set to be 50 turns. Washing the MXene electrode subjected to the electrochemical pre-embedding by using deionized water, and then drying the MXene electrode at normal temperature;
(5) characterization of the post-ionoelectrochemical pre-intercalation electrode:
characterizing the MXene electrode subjected to the electrochemical pre-embedding of the ions in the step (4), characterizing an element energy spectrum of the electrode subjected to the electrochemical pre-embedding of the ions by a scanning electron microscope SEM-EDX, wherein the test elements are Ti, F, Mg, O and Al, and simultaneously performing X-ray diffraction XRD characterization on the MXene electrode, wherein the test range is 5-80 degrees;
(6) electrochemical testing of the electrode after the electrochemical pre-intercalation of ions:
and (3) carrying out electrochemical performance test on the MXene electrode subjected to the ionic electrochemical pre-embedding in the step (4), carrying out charge-discharge cyclic test, cyclic voltammetry test, multiplying power performance test and alternating current impedance test on the MXene electrode through an electrochemical workstation, and proving through experimental data that the ionic electrochemical pre-embedding two-dimensional layered material can effectively optimize and improve the structure and material interface of the MXene electrode, so that a high-performance two-dimensional layered material electrode is constructed.
With Mg2+The results of scanning electron microscopy SEM-EDX and X-ray powder diffraction (XRD) characterization of the ionic electrochemical pre-intercalation two-dimensional layered material MXene are shown in FIG. 2(b) and FIG. 4, and from the data we can see that by this way of ionic electrochemical pre-intercalation, Mg2+Effectively embedded in MXene material, and Mg2+The embedding of (b) causes a small angular shift of the (002) peak of MXene, indicating that Mg2+The embedding of (a) allows MXene to obtain a larger interlayer spacing and a more stable layer space, as shown in FIG. 3(b) as Mg2+Cyclic voltammetry pre-embedding experimental curves.
Example 3:
a preparation method for constructing a high-performance intercalation electrode by pre-embedding an ionic electrochemical two-dimensional layered material specifically comprises the following steps:
(1) preparation of MXene electrode
Grinding a two-dimensional layered active material MXene, a conductive agent Super-P and a binder polyvinylidene fluoride PVDF according to the mass ratio of 8:1:1.5 to enable the materials to be uniform, wherein the mass of the MXene is 80mg, the mass of the conductive agent Super-P is 10mg, the mass of the binder polyvinylidene fluoride PVDF is 15mg, adding N-methyl pyrrolidone (NMP) to stir, the ratio of the volume of the N-methyl pyrrolidone (NMP) to the mass of the active substance is 300ml/g, stirring for more than 28 hours to form electrode slurry with fluidity, uniformly brushing the electrode slurry on a current collector of a Pt sheet by using a brush, weighing the mass of the coated electrode active substance by using a ten-thousandth balance after drying, and then placing in a vacuum drying box to carry out vacuum drying at 60 ℃;
(2) selection of electrochemical electrode system:
the electrochemical electrode system selects a three-electrode system for ionic electrochemical pre-embedding. In a three-electrode system, the MXene active electrode prepared in the step (1) is used as a working electrode, a platinum sheet inert electrode is used as a counter electrode, a KCl electrode of 1mol/L saturated calomel is used as a reference electrode, three electrode materials are fixed by a PTFE platinum sheet electrode clamp, and then the three electrode materials are placed in a container electrolytic cell of 50ml PTFE for preparing an experiment;
(3) selection of electrochemical pre-intercalation ionic electrolyte:
in the three-electrode electrochemical electrode system selected in the step (2), the ions for electrochemical pre-intercalation are selected to be sodium ions Al3+Therefore, the electrolyte of the system adopts 1mol/L aluminum sulfate Al2(SO4)3The solution is an aqueous electrolyte, so that experiments can be carried out in air;
(4) performing ionic electrochemical pre-intercalation:
the electrode system of the three electrodes selected in the step (2) and 1mol/L aluminum sulfate Al adopted in the step (3)2(SO4)3Under an electrochemical device consisting of the solution, an MXene electrode is pre-embedded by ion electrochemistry. The following electrochemical program was set by the electrochemical workstation: the cyclic voltammetry regulates and controls the electrochemical pre-embedding of ions by setting the scanning speed, the scanning voltage range and the number of scanning cycles; the scanning speed is set to 20mV/s, the voltage range of scanning is set to-0.8-0.2V, and the number of scanning turns is set to 60 turns. Washing the MXene electrode subjected to the electrochemical pre-embedding by using deionized water, and then drying the MXene electrode at normal temperature;
(5) characterization of the post-ionoelectrochemical pre-intercalation electrode:
characterizing the MXene electrode subjected to the electrochemical pre-embedding of the ions in the step (4), characterizing an element energy spectrum of the electrode subjected to the electrochemical pre-embedding of the ions by a scanning electron microscope SEM-EDX, wherein the test elements are Ti, F, O and Al, and simultaneously, performing X-ray powder diffraction (XRD) characterization on the MXene electrode, wherein the test range is 5-85 degrees, comparing results of the characterization of the scanning electron microscope SEM-EDX and the characterization of the X-ray powder diffraction (XRD), so that the electrochemical pre-embedding of the ions into the two-dimensional layered material can be effectively realized by an electrochemical pre-embedding mode, and the structure and the surface of the two-dimensional layered material are optimized and improved by the electrochemical pre-embedding of the ions;
(6) electrochemical testing of the electrode after the electrochemical pre-intercalation of ions:
and (3) carrying out electrochemical performance test on the MXene electrode subjected to the ionic electrochemical pre-embedding in the step (4), carrying out charge-discharge cyclic test, cyclic voltammetry test, multiplying power performance test and alternating current impedance test on the MXene electrode through an electrochemical workstation, and proving through experimental data that the ionic electrochemical pre-embedding two-dimensional layered material can effectively optimize and improve the structure and material interface of the MXene electrode, so that a high-performance two-dimensional layered material electrode is constructed.
With Al3+The results of scanning electron microscope SEM-EDX and X-ray diffraction XRD characterization of the ionic electrochemical pre-intercalation two-dimensional layered material MXene are shown in figure 2(c) and figure 4, and through the data, we can see that Al is pre-intercalated by the ionic electrochemical method3+Effectively embedded in MXene material, and Al3+The embedding of (b) causes a small angular shift of the (002) peak of MXene, indicating that Al is present3+The embedding of (a) enables MXene to obtain a larger interlayer spacing and a more stable interlayer space, as shown in FIG. 3(c) as Al3+Cyclic voltammetry pre-embedding experimental curves.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (7)

1. A preparation method of an intercalation electrode constructed by pre-embedding ions into a two-dimensional layered material is characterized by comprising the following steps: the method adopts an electrochemical method to lead pre-embedded ions to be periodically embedded and removed between layers of a two-dimensional layered material, thereby realizing the purpose of punching an ion transport channel in the two-dimensional layered material in advance by ion embedding and removing; meanwhile, pre-embedded ions are anchored between the inner layers of the two-dimensional layered material to realize the ion supporting effect, so that an intercalation electrode with a high-speed and stable ion transport channel is constructed; the method comprises the following steps:
(1) preparation of a working electrode:
uniformly coating electrode slurry taking two-dimensional layered material as active substance on a current collectorVacuum drying to obtain working electrode; the two-dimensional layered material is graphite, MXene or MoS2The conductive agent is acetylene black or Super P, the binder is polyvinylidene fluoride resin PVDF or carboxymethyl cellulose CMC, and the two-dimensional layered material, the conductive agent and the binder are mixed according to the weight ratio of 8: (1-2): (1-2) mixing, wherein the ratio of the added N-methyl pyrrolidone to the two-dimensional layered material is 200 ml: 1g of a compound; the current collector is copper foil, aluminum foil, titanium sheet or carbon paper, the total weight of the two-dimensional layered material, the conductive agent and the binder on the coated current collector is 2-10mg, and the vacuum drying temperature is 60 ℃;
(2) selection of an electrochemical reaction system:
the ion pre-embedding electrochemical reaction system selects a three-electrode system or a two-electrode system; the three-electrode system comprises the working electrode, the counter electrode, the reference electrode and electrolyte prepared in the step (1), wherein the reference electrode is selected according to the type of the pre-embedded ions; the two-electrode system comprises the working electrode prepared in the step (1), a counter electrode and electrolyte, wherein the counter electrode does not react with the pre-embedded ions in the electrochemical process; the electrolyte contains pre-embedded ions;
(3) implementation of electrochemical ion pre-intercalation:
assembling the electrochemical system selected in the step (2) into an electrochemical reaction device, realizing the embedding and the releasing of the pre-embedded ions in the two-dimensional layered material by an electrochemical method, opening an ion transport channel, and simultaneously anchoring the pre-embedded ions between layers of the two-dimensional layered material; taking out the working electrode after the reaction is finished, washing the working electrode with deionized water, and drying the working electrode at normal temperature to obtain an intercalation electrode constructed by the ion pre-embedded two-dimensional layered material; the electrochemical method is a cyclic voltammetry method or a constant current charging and discharging method; the process parameters of the cyclic voltammetry are as follows:
the scanning speed is set to be 0.1-25mV/s, the scanning voltage range is determined according to the voltage window of the pre-intercalation electrochemical reaction system, the pre-intercalation cation: set to the lowest voltage to 0.2-1V above it; pre-intercalating anions: setting the voltage to 0.2-1V below the maximum voltage; the number of the cyclic scanning is 5-100 circles;
the constant current charging and discharging method comprises the following process parameters:
the current density is selected to be in the range of 0.1-20A/g, the pre-intercalation cation: set to the lowest voltage to 0.2-1.0V above it; pre-intercalating anions: setting the voltage to 0.2-1.0V below the maximum voltage; the number of cyclic scans is 5 to 40 cycles; the number of charging and discharging circles is set to be 5-100 circles.
2. The method for preparing an intercalation electrode constructed by pre-embedding ions into a two-dimensional layered material according to claim 1, wherein: in the step (1), the electrode slurry is prepared by uniformly mixing the two-dimensional layered material, the conductive agent and the binder according to a required proportion, and adding N-methylpyrrolidone for stirring.
3. The method for preparing an intercalation electrode constructed by pre-embedding ions into a two-dimensional layered material according to claim 1, wherein: in the step (2), pre-intercalation ions in the electrolyte are metal cations, non-metal cations or non-metal anions, and the concentration of the pre-intercalation ions is 0.5-3 mol/L; the solvent matched with the pre-embedded ions is selected to be a water system or a non-water system; the water system environment can be tested in the air, the non-water system needs to be tested in a glove box, and in the non-water system, the water and oxygen values in the glove box are controlled to be 0.1-0.5 ppm.
4. The method for preparing an intercalation electrode constructed by pre-embedding ions into a two-dimensional layered material according to claim 1, wherein: in the step (2), the counter electrode is made of carbon paper and titanium sheet high-conductivity materials, and the reference electrode is a standard hydrogen electrode, a saturated calomel electrode, a silver/silver chloride electrode and a ferrocene electrode, but the reaction with pre-embedded ions is avoided.
5. The method for preparing an intercalation electrode constructed by pre-embedding ions into a two-dimensional layered material according to claim 1, wherein: in the step (3), the electrolytic cell adopted in the electrochemical reaction device is a quartz or polytetrafluoroethylene container with the volume of 10ml-200 ml.
6. An intercalation electrode constructed using an ion pre-intercalated two-dimensional layered material prepared by the method of any one of claims 1 to 5, wherein: the intercalation electrode regulates and controls the inner layer spacing of the two-dimensional layered material through the pre-embedding of electrochemical ions, and meanwhile, the pre-embedded ions can support the two-dimensional layered material to provide a stable ion channel for the subsequent embedding and releasing of energy storage electrolyte ions in the two-dimensional material, so that the ion transport capacity of the electrode material is improved.
7. The use of an intercalation electrode constructed with an ionic pre-intercalation two-dimensional layered material as claimed in claim 6, wherein: the ion pre-embedded two-dimensional layered material is suitable for lithium ion batteries, sodium ion batteries, lithium sulfur battery energy storage systems or dual-ion batteries.
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