CN115386855B - Stepwise intermittent lithium plating method based on vertical orientation multiwall carbon nanotube array - Google Patents

Stepwise intermittent lithium plating method based on vertical orientation multiwall carbon nanotube array Download PDF

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CN115386855B
CN115386855B CN202211031157.1A CN202211031157A CN115386855B CN 115386855 B CN115386855 B CN 115386855B CN 202211031157 A CN202211031157 A CN 202211031157A CN 115386855 B CN115386855 B CN 115386855B
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electroplating
lithium
intermittent
carbon nanotube
nanotube array
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CN115386855A (en
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埃泽尔·马丁·阿金诺古
何国宝
陈瑞婷
王新
周国富
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Zhaoqing South China Normal University Optoelectronics Industry Research Institute
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Zhaoqing South China Normal University Optoelectronics Industry Research Institute
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Abstract

The invention belongs to the technical field of lithium metal batteries, and particularly discloses a stepwise intermittent lithium plating method based on a vertically oriented multiwall carbon nanotube array. The method comprises the following steps: s1, preprocessing a substrate; s2, adding the buffer layer and the catalyst layer to the substrate processed in the step S1; s3, growing a vertical orientation multiwall carbon nanotube array on the substrate in the step S2; s4, assembling an electrochemical cell by using the sample with the vertically oriented multiwall carbon nanotube array growing in the step S3 as a working electrode; and S5, performing electrochemical lithium plating on the working electrode by adopting a step-by-step intermittent electroplating method and using the battery assembled in the step S4. The single-step electroplating time, the electroplating current density, the total electroplating time and the single-step intermittent time are adjustable, the uniform deposition of metal coaxial with CNTs can be realized, the strength and the stability of VA-MWCNTs are enhanced, and the single-step electroplating method has great application potential in the fields of electrochemical electroplating, lithium metal batteries and the like.

Description

Stepwise intermittent lithium plating method based on vertical orientation multiwall carbon nanotube array
Technical Field
The invention belongs to the technical field of lithium metal batteries, and particularly discloses a stepwise intermittent lithium plating method based on a vertically oriented multiwall carbon nanotube array.
Background
With the continuous reduction of non-renewable fossil energy reserves, people have become aware of the problem of environmental pollution, and development of new energy and ecological civilization construction, in the new development stage, development of energy storage and conversion of modern energy storage systems is still an important task. For renewable new energy sources such as large yang energy, wind energy and the like, a method for overcoming the intermittence and instability of the energy sources is to convert the energy into electric energy which is convenient to store and utilize so as to relieve the crisis problems such as energy shortage, environmental pollution and the like.
Since Sony in 1991 issued commercial lithium ion batteries using graphite instead of lithium metal as the negative electrode, almost all commercial lithium ion batteries employed different forms of carbon material as the negative electrode material. The lithium ion battery is also widely applied to the fields of portable electronic equipment and the like due to the advantages of high working voltage, excellent cycle performance, large mass specific energy, no memory effect and the like.
Lithium metal has a low density of 0.534g cm -3 High theoretical specific capacity 3860 mAh.g -1 ，Li/Li + Is the lowest (-3.04V vs SHE). The problems of limited lithium dendrite and coulombic efficiency and the like generated in the repeated deposition/stripping process of lithium metal prevent the large-scale application of lithium batteries, but the theoretical capacity of the lithium metal is ten times that of graphite, so in recent years, the adoption of the lithium metal as a cathode of a chargeable and dischargeable lithium battery becomes a key point of scientific research in the field of energy sources. However, the lithium metal negative electrode in the chargeable and dischargeable battery has some problems affecting the battery cycle stability and safety, such as lithium dendrite growth, large volume change, and the like.
VA-MWCNTs are used as electrode materials of lithium-based batteries such as lithium ion batteries, lithium oxygen batteries and lithium sulfur batteries, the porous structure of the VA-MWCNTs provides a large surface area for electrode-electrolyte interface contact, the conductivity and channels among parallel tubes of the VA-MWCNTs enhance electron and ion conduction, and the directional structure of the VA-MWCNTs reduces the agglomeration of active materials on the surface, so that the VA-MWCNTs are also suitable for solving the problems of dendrite growth, volume change and the like on a lithium metal negative electrode. However, in the repeated lithium plating/removal process, the alignment structure of VA-MWCNTs is destroyed, so that the local current density is increased, the voltage is polarized, and the coulomb efficiency is reduced.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a stepwise intermittent lithium plating method based on a vertical orientation multi-wall carbon nano tube array, and the metal lithium preplating on the surface of VA-MWCNTs can well maintain the vertical orientation characteristic morphology of the VA-MWCNTs.
Compared with the existing electrochemical lithium plating method, the invention creatively uses the stepwise intermittent electrochemical plating method, sets the current density and the duration of the single step intermittent step and the single step plating step, carries out electrochemical lithium plating on an electrochemical cell system with a working electrode of a vertically oriented multi-wall carbon nano tube array, and finally obtains the vertically oriented multi-wall carbon nano tube electrode plate which can maintain stable vertical orientation characteristics and has uniform metal lithium covered on the surface of the carbon nano tube.
The primary object of the present invention is to provide a stepwise intermittent lithium plating method based on a vertically oriented multiwall carbon nanotube array.
The invention realizes the aim through the following technical scheme:
a stepwise intermittent lithium plating method based on a vertically oriented multi-walled carbon nanotube array, comprising the steps of:
s1, preprocessing a substrate;
s2, adding the buffer layer and the catalyst layer to the substrate processed in the step S1;
s3, growing a vertical orientation multiwall carbon nanotube array on the substrate in the step S2;
s4, assembling an electrochemical cell by using the sample with the vertically oriented multiwall carbon nanotube array growing in the step S3 as a working electrode;
and S5, performing electrochemical lithium plating on the working electrode by adopting a step-by-step intermittent electroplating method and using the battery assembled in the step S4.
Compared with the existing electroplating technology, the method reduces lithium ions in part of the thin-layer electrolyte between the carbon nano tubes in a single-step electroplating process, and provides new active substances for the thin-layer electrolyte on the wall surface of the carbon nano tubes in an intermittent step. The ion concentration gradient at the interface between the carbon nanotube wall and the thin electrolyte is reduced by intermittent cyclic electroplating for many times. The invention can achieve the effect of controlling the deposition thickness and uniformity of the metallic lithium on the surface of the carbon nano tube by changing the single-step electroplating and the single-step intermittent time, the single-step electroplating current density and the circulation times, and has more possibility and potential in the aspects of reducing the growth of lithium crystal branches and the like. The whole preparation process has low cost and simple flow.
Preferably, the substrate in step S1 is a substrate with water stability, thermal stability and good conductivity, including copper sheet and titanium sheet, and the pretreatment is ultrasonic cleaning with absolute ethanol and deionized water.
Preferably, the buffer layer in the step S2 is a titanium buffer layer with the thickness of 50nm-300nm, the catalyst is one of iron, cobalt and nickel, and the thickness is 5nm-20nm.
Preferably, the buffer layer and the catalyst layer in step S2 are prepared by using an electron beam evaporation or magnetron sputtering method.
Preferably, the length of the vertically oriented multiwall carbon nanotubes in step S3 is 0.5 μm to 4 μm, and the growth method is a thermal chemical vapor deposition method or a plasma enhanced chemical vapor deposition method.
Preferably, the electrochemical cell described in step S4 comprises a three-electrode electrochemical cell comprising a lithium-ion electrolyte, and the counter electrode is a two-electrode electrochemical cell comprising a lithium-ion electrolyte of lithium metal.
Preferably, step S5 sets the current density, duration and cycle number of the single step batch step and the single step electroplating step in the step batch electroplating using an electrochemical workstation multi-current step program.
Preferably, step S5 is described inThe current density of the intermittent step in the step-by-step intermittent electroplating method is 0mA cm -2 The single step intermittent time is 1-300s, the current density of the electroplating step is 2-200mA cm -2 The single-step electroplating time is 1-50s, and the cycle number is 10-200.
The metal lithium film preplated on the surface of the VA-MWCNTs well maintains the vertical orientation characteristic morphology of the VA-MWCNTs, and the stable vertical orientation structure can provide large lithium plating/delithiation surface area, enhance the axial conduction of electrons and ions between tubes, reduce lithium dendrites, relieve the volume expansion of lithium metal, realize the improvement of the structural stability and the cycle performance of the electrode, and play a key role in promoting the reversible electroplating/stripping of lithium.
The invention also provides application of the VA-MWCNTs@Li prepared by the method in preparation of lithium-based battery electrode materials.
Compared with the prior art, the invention has the beneficial effects that:
compared with continuous electroplating, the stepwise intermittent electrochemical lithium plating method is more beneficial to uniform deposition of lithium metal on the surfaces of VA-MWCNTs, and lithium metal agglomeration is effectively reduced. The deposition of lithium metal on the surface of VA-MWCNTs can be optimized by adjusting four conditions of distributed electroplating step number (single-step electroplating time), electroplating current density, total electroplating time and single-step intermittent time in the step intermittent electroplating process, and specific step intermittent electroplating parameters can realize the deposition of the lithium metal in a film form and in a coaxial structure with the VA-MWCNTs. The VA-MWCNTs have good electrochemical lithium plating capability, the strength and stability of the VA-MWCNTs are enhanced by the metal lithium film, the vertical orientation morphology characteristics of the VA-MWCNTs in the electrolyte are maintained, and the cycling stability of the lithium ion battery is improved.
Drawings
FIG. 1 is a schematic illustration of the process flow of the present invention.
FIG. 2 is an SEM topography of VA-MWCNTs produced by PECVD.
Fig. 3 is a SEM topography after cyclic intermittent lithium plating based on a vertically oriented multi-walled carbon nanotube array of examples 1-3, a being example 1, b being example 2, c being example 3.
FIG. 4 is a SEM comparative graph of VA-MWCNTs on electrode sheets after intermittent electroplating at constant current density for the same total electroplating time (30 s) for example 1 and comparative example 1, the interpolated graph is the macroscopically observable size and number of lithium clusters on the electrode sheet surface; a is single-step electroplating time length of 1s, and the cycle is 30 times; b is a single step electroplating duration of 30s, and is cycled 1 time.
Fig. 5 is a graph of electrochemical performance of lithium ion batteries assembled with different electrodes.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The test methods used in the embodiment of the invention are all conventional methods unless specified otherwise; the materials, reagents and the like used, unless otherwise specified, are those commercially available.
Example 1
A method for cyclic intermittent lithium plating based on a vertically oriented multi-walled carbon nanotube array, comprising the steps of:
1) Cleaning and cutting a substrate: firstly, sequentially ultrasonically cleaning a copper sheet by absolute ethyl alcohol and deionized water for 10 minutes, drying and cutting into a round shape with the diameter of 12 mm;
2) Vapor deposition buffer layer and catalyst layer: and respectively loading a crucible of the electron beam evaporation device with a crucible of metallic titanium and metallic cobalt. Sticking the cut copper sheet on a sample stage above a crucible in an electron beam evaporation device, wherein the vacuum degree reaches 8.0 multiplied by 10 -4 And after Pa, transferring the position of the crucible to the crucible filled with metallic titanium, gradually increasing the electron beam current, opening a baffle plate to start evaporating the titanium buffer layer after titanium in the crucible is melted, and transferring the position of the crucible to the crucible filled with metallic cobalt after evaporation is finished, wherein the operation of evaporating the titanium buffer layer is repeated, and the evaporation thickness is 15nm. After the completion, the sample is taken out to obtain the catalyst which is evaporated with a 100nm titanium buffer layer and 15nm cobaltCopper sheet of agent layer;
3) Preparation of VA-MWCNTs by Plasma Enhanced Chemical Vapor Deposition (PECVD): the copper sheet deposited with the 100nmTi buffer layer and the 15nmCo catalyst is put into a PECVD device, and the vacuum degree reaches 8 multiplied by 10 -4 After Pa, introducing 200sccm ammonia gas, heating to 700 ℃ in a stroke sequence, setting the power of a power supply to 20W, after the temperature is stable, turning on a direct current power supply, simultaneously introducing 50sccm acetylene, adjusting the pressure of a plasma enhanced chemical vapor deposition chamber to 1kPa, and the growth time of the carbon nano tubes to 40 minutes, thereby finally obtaining a VA-MWCNTs sample;
4) Assembling a three-electrode battery: in an argon-filled glove box, 18.71g of lithium bis (fluorosulfonyl) imide (LiFSI) was weighed using an electronic balance and dissolved in ethylene glycol dimethyl ether (DME) to a total volume of 100mL. VA-MWCNTs are used as working electrodes, a nested structure of a polytetrafluoroethylene outer shell and a metal conductive inner column is used for fixing a counter electrode to select a platinum sheet, and a reference electrode is a silver wire quasi-reference electrode (Ag PRE);
5) Setting step-by-step intermittent electroplating parameters to carry out lithium plating: multiple current step procedure using electrochemical workstation, set electroplating step current density to 20mA.cm -2 The single-step electroplating time is 1s, and the current density of the intermittent step is 0mA cm -2 The single step interval duration is 60s, and the cycle number is 30. And (5) electroplating operation is carried out after the setting is completed.
Example 2
A method for cyclic intermittent lithium plating based on a vertically oriented multi-walled carbon nanotube array, comprising the steps of:
1) Cleaning and cutting a substrate: firstly, sequentially ultrasonically cleaning a copper sheet by absolute ethyl alcohol and deionized water for 10 minutes, drying and cutting into a round shape with the diameter of 12 mm;
2) Vapor deposition buffer layer and catalyst layer: and respectively loading a crucible of the electron beam evaporation device with a crucible of metallic titanium and metallic cobalt. Sticking the cut copper sheet on a sample stage above a crucible in an electron beam evaporation device, wherein the vacuum degree reaches 8.0 multiplied by 10 -4 After Pa, transferring the position of the crucible to a crucible filled with metallic titanium, gradually increasing the electron beam current, opening a baffle plate to start evaporating a titanium buffer layer after the titanium in the crucible is melted, evaporating the titanium buffer layer to a thickness of 100nm, and after evaporation is finishedAnd (3) transferring the crucible position to a crucible filled with metallic cobalt, and repeating the operation of evaporating the titanium buffer layer, wherein the evaporating thickness is 15nm. Taking out the sample after the completion to obtain a copper sheet evaporated with a 100nm titanium buffer layer and a 15nm cobalt catalyst layer;
3) Preparation of VA-MWCNTs by Plasma Enhanced Chemical Vapor Deposition (PECVD): the copper sheet deposited with the 100nmTi buffer layer and the 15nmCo catalyst is put into a PECVD device, and the vacuum degree reaches 8 multiplied by 10 -4 After Pa, introducing 200sccm ammonia gas, heating to 700 ℃ in a stroke sequence, setting the power of a power supply to 20W, after the temperature is stable, turning on a direct current power supply, simultaneously introducing 50sccm acetylene, adjusting the pressure of a plasma enhanced chemical vapor deposition chamber to 1kPa, and the growth time of the carbon nano tubes to 40 minutes, thereby finally obtaining a VA-MWCNTs sample;
4) Assembling a three-electrode battery: in an argon-filled glove box, 18.71g of lithium bis (fluorosulfonyl) imide (LiFSI) was weighed using an electronic balance and dissolved in ethylene glycol dimethyl ether (DME) to a total volume of 100mL. VA-MWCNTs are used as working electrodes, a nested structure of a polytetrafluoroethylene outer shell and a metal conductive inner column is used for fixing a counter electrode to select a platinum sheet, and a reference electrode is a silver wire quasi-reference electrode (Ag PRE);
5) Setting step-by-step intermittent electroplating parameters to carry out lithium plating: multiple current step procedure using electrochemical workstation, set electroplating step current density to 10mA cm -2 The single-step electroplating time is 1s, and the current density of the intermittent step is 0mA cm -2 The single step interval duration is 60s, and the cycle number is 30. And (5) electroplating operation is carried out after the setting is completed.
Example 3
A method for cyclic intermittent lithium plating based on a vertically oriented multi-walled carbon nanotube array, comprising the steps of:
1) Cleaning and cutting a substrate: firstly, sequentially ultrasonically cleaning a copper sheet by absolute ethyl alcohol and deionized water for 10 minutes, drying and cutting into a round shape with the diameter of 12 mm;
2) Vapor deposition buffer layer and catalyst layer: and respectively loading a crucible of the electron beam evaporation device with a crucible of metallic titanium and metallic cobalt. Sticking the cut copper sheet on a sample stage above a crucible in an electron beam evaporation device, wherein the vacuum degree reaches 8.0 multiplied by 10 -4 After Pa (Pa)And (3) transferring the position of the crucible to the crucible filled with the metallic titanium, gradually increasing the electron beam current, opening a baffle plate to start evaporating the titanium buffer layer after the titanium in the crucible is melted, evaporating the titanium buffer layer to a thickness of 100nm, transferring the position of the crucible to the crucible filled with the metallic cobalt after evaporation is finished, repeating the operation of evaporating the titanium buffer layer, and evaporating the titanium buffer layer to a thickness of 15nm. Taking out the sample after the completion to obtain a copper sheet evaporated with a 100nm titanium buffer layer and a 15nm cobalt catalyst layer;
3) Preparation of VA-MWCNTs by Plasma Enhanced Chemical Vapor Deposition (PECVD): the copper sheet deposited with the 100nmTi buffer layer and the 15nmCo catalyst is put into a PECVD device, and the vacuum degree reaches 8 multiplied by 10 -4 After Pa, introducing 200sccm ammonia gas, heating to 700 ℃ in a stroke sequence, setting the power of a power supply to 20W, after the temperature is stable, turning on a direct current power supply, simultaneously introducing 50sccm acetylene, adjusting the pressure of a plasma enhanced chemical vapor deposition chamber to 1kPa, and the growth time of the carbon nano tubes to 40 minutes, thereby finally obtaining a VA-MWCNTs sample;
4) Assembling a three-electrode battery: in an argon-filled glove box, 18.71g of lithium bis (fluorosulfonyl) imide (LiFSI) was weighed using an electronic balance and dissolved in ethylene glycol dimethyl ether (DME) to a total volume of 100mL. VA-MWCNTs are used as working electrodes, a nested structure of a polytetrafluoroethylene outer shell and a metal conductive inner column is used for fixing a counter electrode to select a platinum sheet, and a reference electrode is a silver wire quasi-reference electrode (Ag PRE);
5) Setting step-by-step intermittent electroplating parameters to carry out lithium plating: multiple current step procedure using electrochemical workstation, set electroplating step current density to 10mA cm -2 The single-step electroplating time is 1s, and the current density of the intermittent step is 0mA cm -2 The single step interval duration is 60s and the number of cycles is 60. And (5) electroplating operation is carried out after the setting is completed.
Comparative example 1
1) Cleaning and cutting a substrate: firstly, sequentially ultrasonically cleaning a copper sheet by absolute ethyl alcohol and deionized water for 10 minutes, drying and cutting into a round shape with the diameter of 12 mm;
2) Vapor deposition buffer layer and catalyst layer: and respectively loading a crucible of the electron beam evaporation device with a crucible of metallic titanium and metallic cobalt. Sticking the cut copper sheet on a sample table above a crucible in an electron beam evaporation device,vacuum degree reaches 8.0 multiplied by 10 -4 And after Pa, transferring the position of the crucible to the crucible filled with metallic titanium, gradually increasing the electron beam current, opening a baffle plate to start evaporating the titanium buffer layer after titanium in the crucible is melted, and transferring the position of the crucible to the crucible filled with metallic cobalt after evaporation is finished, wherein the operation of evaporating the titanium buffer layer is repeated, and the evaporation thickness is 15nm. Taking out the sample after the completion to obtain a copper sheet evaporated with a 100nm titanium buffer layer and a 15nm cobalt catalyst layer;
3) Preparation of VA-MWCNTs by Plasma Enhanced Chemical Vapor Deposition (PECVD): the copper sheet deposited with the 100nmTi buffer layer and the 15nmCo catalyst is put into a PECVD device, and the vacuum degree reaches 8 multiplied by 10 -4 After Pa, introducing 200sccm ammonia gas, heating to 700 ℃ in a stroke sequence, setting the power of a power supply to 20W, after the temperature is stable, turning on a direct current power supply, simultaneously introducing 50sccm acetylene, adjusting the pressure of a plasma enhanced chemical vapor deposition chamber to 1kPa, and the growth time of the carbon nano tubes to 40 minutes, thereby finally obtaining a VA-MWCNTs sample;
4) Assembling a three-electrode battery: in a glove box filled with argon, 18.71g of lithium bis (fluorosulfonyl) imide (LiFSI) was weighed using an electronic balance and dissolved in ethylene glycol dimethyl ether (DME) to a total volume of 100ml. VA-MWCNTs are used as working electrodes, a nested structure of a polytetrafluoroethylene outer shell and a metal conductive inner column is used for fixing a counter electrode to select a platinum sheet, and a reference electrode is a silver wire quasi-reference electrode (Ag PRE);
5) Setting parameters for lithium plating: setting the current density of the electroplating step to 20 mA.cm -2 Electroplating was performed for 30 s.
Performance testing and analysis
As shown in FIG. 3, the carbon nanotubes after step-wise intermittent electroplating in examples 1-3 of the present invention can still maintain a vertical orientation morphology, and meanwhile, the specific step-wise intermittent electroplating parameters can realize that the metal lithium deposited by electroplating is in a film form uniformly covering the wall surface of the VAMWCNTs, and is deposited with the metal lithium of which VA-MWCNTs are coaxial structures, even gradually fills the space between the VA-MWCNTs, which means that lithium ions in the thin-layer electrolyte on the wall surface of the VA-MWCNTs are replenished, and the intermittent electroplating can actually improve the uniformity degree of the metal lithium deposition, enhance the shape retention effect and maintain the independence of each VAMWCNTs.
As shown in FIG. 4, SEM images of VA-MWCNTs on the electrode sheets after constant current density plating for the same total plating time (30 s) in example 1 and comparative example 1. It can be observed that at constant current density (20 mA cm -2 ) Under the electroplating condition, the orientation of the carbon nano tube on the electrode plate is destroyed after the electroplating of the comparative example 1 for 30 seconds (see fig. 4 b), the single-step intermittent time length is 60 seconds and the cycle number is 30 times (see fig. 4 a) along with the reduction of the electroplating time length from 30 seconds to 1 seconds, compared with the continuous electroplating, the uniform deposition of lithium metal on the surface of VAMWCNTs is more facilitated, the agglomeration of lithium metal is effectively reduced, the vertical orientation characteristic of the carbon nano tube on the electrode plate is more completely reserved, and the reduction of the size and the number of lithium clusters on the surface of the electrode plate can be observed macroscopically.
Electrochemical performance analysis
The electrochemical performance was tested and analyzed using Cu-Ti, VA-MWCNTs (no lithium plating operation performed in example 3) and VA-mwcnts@li (example 3) current collectors, respectively, with lithium-tab assembled button cells (Cu-ti|li, VA-mwcnts|li and VA-mwcnts@li|li cells).
The cycling performance of Cu-Ti|Li, VA-MWCNTs|Li and VA-MWCNTs@Li|Li batteries is shown in FIG. 5. Each cycle starts at-2 mA cm -2 The discharge process of current density plated lithium (2 mAh cm) -2 ) Followed by +2mA.cm -2 Is subjected to surface delithiation from the current collector until a battery cut-off voltage of 1V (vs Li/Li + ). It can be seen from fig. 5a that the coulombic efficiency of the first cycle of the cu—ti current collector is quite low (54.7%) and remains stable at 53.7% after 100 cycles. The coulomb efficiency of the VA-MWCNTs current collector is 81% after the first cycle and continuously decreases after the second cycle is increased to 83.5%, the coulomb efficiency of the VA-MWCNTs current collector is similar to that of the Cu-Ti current collector after the 55 th cycle, which indicates that the VA-MWCNTs current collector has similar lithium plating/delithiation behavior to that of a planar current collector, the VA-MWCNTs vertical orientation structure is likely to be damaged, and the coulomb efficiency of the VA-MWCNTs current collector is further reduced after 80 cycles, which is likely to be caused by the local current density increase and voltage polarization on the VA-MWCNTs current collector after the vertical orientation structure is damaged. And VA-MWCNTsThe @ Li current collector has higher initial cycle coulomb efficiency of 83.7%, and the coulomb efficiency of the current collector is improved to a certain extent after 60 times of cycles, and is 60.5% in the 100 th cycle, which proves that the vertical orientation characteristic morphology of the VA-MWCNTs is well maintained by the metal lithium film pre-plated on the surface of the VA-MWCNTs, and the stability of the electrode structure and the improvement of the cycle performance are realized.
The battery assembled by different electrodes is 2mA cm -2 The charge-discharge curves at current density are shown in figures 5 b-d. The Cu-Ti electrode exhibits a large first-time lithium plating/delithiation overpotential (210 mV), the first-time cyclic lithium plating/delithiation overpotential of the VA-MWCNTs electrode is about 151mV, and the first-time cyclic lithium plating/delithiation overpotential of the VA-MWCNTs@Li electrode is about 121mV. The VA-MWCNTs@Li electrode has higher first cycle coulomb efficiency and lower overpotential, and the maintenance of the vertical orientation characteristic morphology provides a fast and stable inter-tube transmission channel for electrons and ions, reduces local current density, is favorable for stable reversible electroplating and stripping actions of lithium metal on a current collector, and inhibits the generation of lithium dendrites and the volume expansion of the lithium metal to a certain extent.
It should be understood that the foregoing description of the specific embodiments is merely illustrative of the invention, and is not intended to limit the invention, and that any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (2)

1. A stepwise intermittent lithium plating method based on a vertically oriented multi-walled carbon nanotube array, comprising the steps of:
s1, preprocessing a substrate;
s2, adding the buffer layer and the catalyst layer to the substrate processed in the step S1;
s3, growing a vertical orientation multiwall carbon nanotube array on the substrate in the step S2;
s4, assembling an electrochemical cell by using the sample with the vertically oriented multiwall carbon nanotube array growing in the step S3 as a working electrode;
s5, performing electrochemical lithium plating on the working electrode by adopting a step-by-step intermittent electroplating method and using the battery assembled in the step S4;
the substrate in the step S1 is a substrate with water stability, heat stability and good conductivity, and comprises a copper sheet and a titanium sheet, wherein the pretreatment is ultrasonic cleaning by absolute ethyl alcohol and deionized water;
the buffer layer in the step S2 is a titanium buffer layer with the thickness of 50nm-300nm, the catalyst is one of iron, cobalt and nickel, and the thickness is 5nm-20nm;
step S2, preparing the buffer layer and the catalyst layer by using an electron beam evaporation or magnetron sputtering method;
the length of the vertical orientation multi-wall carbon nano tube in the step S3 is 0.5-4 mu m, and the growth method is a thermal chemical vapor deposition method or a plasma enhanced chemical vapor deposition method;
the electrochemical cell in the step S4 comprises a three-electrode electrochemical cell containing lithium ion electrolyte, and the counter electrode is a double-electrode electrochemical cell containing lithium ion electrolyte of lithium metal;
step S5, setting the current density of a single-step intermittent step and a single-step electroplating step in the step intermittent electroplating by adopting an electrochemical workstation multi-current step program, and the duration and the cycle times; the current density of the step-by-step intermittent step is 0mA cm -2 The single step intermittent time is 1-300s, the current density of the electroplating step is 2-200mA cm -2 The single-step electroplating time is 1-50s, and the cycle number is 10-200.
2. The use of VA-mwcnts@li prepared by the method of claim 1 in the preparation of lithium-based battery electrode materials.
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