CN108987673B - Lithium negative electrode containing conductive protection film and preparation method and application thereof - Google Patents

Lithium negative electrode containing conductive protection film and preparation method and application thereof Download PDF

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CN108987673B
CN108987673B CN201810813974.XA CN201810813974A CN108987673B CN 108987673 B CN108987673 B CN 108987673B CN 201810813974 A CN201810813974 A CN 201810813974A CN 108987673 B CN108987673 B CN 108987673B
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lithium
negative electrode
conductive
tray
vacuum
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CN108987673A (en
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唐琼
李合琴
潘媛媛
林志伟
张静
陈勇
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Hefei University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0423—Physical vapour deposition
    • H01M4/0426—Sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method and application of a lithium cathode containing a conductive protection film. A vacuum sputtered Cu film was attached to the surface of the lithium sheet. The preparation method comprises the following steps: in an argon glove box, firstly, a lithium sheet is pasted on a tray to be sputtered by using a conductive double-sided adhesive tape, the lithium sheet and the tray are placed into a sealing box together, then, the tray in the sealing box is transferred into a magnetron sputtering coating instrument, and vacuum direct-current sputtering Cu is carried out, wherein the sputtering time is 360 seconds. The conductive Cu film prepared by the invention has a layered and conductive composite morphology, can avoid direct contact between a lithium sheet and an electrolyte, can disperse current, reduce current density, inhibit growth of lithium dendrite, and promote electrochemical reaction kinetics. The lithium-sulfur battery has good cycle stability and capacity maintenance rate when being applied to the lithium-sulfur battery. The preparation process is simple and controllable, and has practical application value.

Description

Lithium negative electrode containing conductive protection film and preparation method and application thereof
Technical Field
The invention relates to a lithium cathode containing a conductive protection film, and a preparation method and application thereof, and belongs to the field of nano materials and electrochemical energy storage.
Background
With the rapid development of portable electronic devices and electric vehicles, commercial lithium ion batteries cannot meet the current requirements for high specific energy and long-cycle energy storage devices due to their low theoretical energy density and specific capacity, and therefore, new generation lithium metal batteries such as lithium oxygen and lithium sulfur batteries have focused on the public. Unlike the 'de-intercalation' mechanism of a rocking chair type lithium ion battery, the lithium metal battery takes metal lithium as a negative electrode and generates capacity through the oxidation-reduction reaction between the positive electrode and the negative electrode. Lithium, being light in weight, has the highest theoretical energy density of 11680Wh/kg and the lowest standard electrode potential of-3.04V (relative to the standard hydrogen potential), and is considered to be the best anode material. However, practical application of lithium negative electrodes faces some problems to be solved. Firstly, dendritic crystals are easily formed on the surface of lithium and are separated from a negative electrode substrate to form 'dead lithium', so that the cycle life of the battery is shortened; more seriously, the dendrites that do not detach continue to grow, pierce the separator, short-circuiting the battery, and causing serious safety hazards. In addition, the electrolyte reacts with lithium due to its low potential to form a solid electrolyte interface film (SEI) on the surface, but such a film is unstable and consumes the electrolyte and lithium continuously, resulting in a decrease in cycle efficiency. In addition, during the charging and discharging processes, the lithium sheet is continuously deposited/dissolved, unlimited volume change can be generated, and the physical structure of the negative electrode is easy to damage.
There have been many proposals to improve the above-mentioned problems of the lithium negative electrode. Such as the incorporation of LiNO in the electrolyte3(Electrochem.Commun.51(2015):59–63.)、AlCl3(Nano Energy 36(2017): 411-417.), they can react with lithium rapidly to generate a dense SEI film to prevent lithium from further reacting with the electrolyte, however, the SEI film generated in situ is very complex and difficult to control. The use of ex situ methods to produce a SEI film has also been shown to improve lithium anodes, such as atomic layer deposition of Al2O3(J.Mater.chem.A. 24(2017): 12297-. There have been other studies to modify the deposition dissolution behavior of lithium by designing the current collector such as to suppress dendrite formation using a 3D copper current collector as a lithium negative electrode backbone (nat. commun.6(2015):8058), synthesizing interconnected amorphous carbon hollow sphere modified conventional copper current collectors (nat. nanotechnol.8(2014): 618-. However modified current collectorsThe strategy of (2) is that lithium is firstly deposited on a current collector through electrochemistry and then transferred to a secondary battery for assembly, which undoubtedly increases the difficulty and complexity of operation, and the operation repeatability and performance stability can not be ensured, thus being not beneficial to actual large-scale production. Therefore, the development of a scheme with high material conductivity, controllable preparation process and simple process to improve the lithium negative electrode has very important significance for promoting the practical application of the lithium metal battery.
Disclosure of Invention
The invention aims to: the method can prevent lithium from being directly corroded by electrolyte, inhibit the growth of lithium dendrite, and prolong the cycle life of the lithium metal battery when being applied to the lithium metal battery.
In order to achieve the above purpose, the invention provides the following technical scheme:
a lithium cathode containing a conductive protection film takes copper as a target material, and a vacuum Cu plating film is attached to the surface of a lithium sheet by using a magnetron sputtering technology and has an island-shaped and layered composite appearance.
A preparation method of a lithium negative electrode containing a conductive protection film comprises the following specific steps:
(1) in an argon glove box, firstly, adhering a lithium sheet on a tray to be sputtered by using a conductive double-sided adhesive tape, putting the tray and the lithium sheet into a sealing box together, and then transferring the tray in the sealing box into a magnetron sputtering coating instrument; wherein, the volume fraction of the water content in the argon glove box is less than 0.1ppm, and the volume fraction of the oxygen content is less than 0.1 ppm;
(2) and carrying out vacuum direct-current magnetron sputtering copper plating on the surface of the lithium sheet.
Preferably, the specific process of step (2) is: when the vacuum degree in the vacuum coating chamber reaches 1.0 multiplied by 10-4When Pa, introducing Ar gas as sputtering gas with the pressure of 0.5-1.0Pa and the power of 30-50W, pre-sputtering for 8-15min, and then carrying out vacuum copper plating.
Preferably, the flow rate of Ar gas in step (2) is 30 to 40 sccm.
Preferably, the vacuum copper plating time in the step (2) is 240-360 s.
Preferably, the purity of Cu in the step (2) is more than or equal to 99.99 percent.
The application of the lithium cathode containing the conductive protection film can be used as the cathode of a lithium-sulfur battery to be applied to the field of electrochemical energy storage.
The invention has the beneficial effects that:
the preparation method provided by the invention has the advantages of simple process and short time consumption, the sputtered Cu film has two composite forms of a layer and an island, and the surface of the lithium sheet is completely covered, so that the direct contact between the lithium sheet and the electrolyte can be prevented, and the corrosion of the lithium sheet and the electrolyte can be avoided. Meanwhile, a large number of dispersed pores exist in the Cu film, which is equivalent to forming a porous conductive Cu framework on the surface of the lithium sheet, so that lithium ion transmission is ensured, current is dispersed, and the current density is reduced, thereby inhibiting the growth of lithium dendrite. In addition, the highly conductive Cu film can promote electrochemical reaction kinetics, reducing polarization. In addition, the Cu film prepared by the method has a good film-substrate bonding effect with the surface of the lithium sheet, and can enhance the mechanical strength of the lithium sheet, so that the lithium sheet is not easy to damage in the charging and discharging process.
At 2mA/cm2Under the current density of (1), the voltage of the symmetrical battery adopting the Cu-plated lithium cathode is stable and gradually reduced along with the change of time through a continuous 140-hour lithium deposition/dissolution cycle test, and the hysteresis voltage is less than 80 mV. The fluctuation of the voltage curve of the symmetrical battery adopting the original lithium cathode is fluctuated, and the hysteresis voltage after circulation is about 111mV, which shows that the lithium cathode prepared by the invention can obviously reduce polarization. In addition, the first specific discharge capacity of the lithium-sulfur battery adopting the original lithium cathode is 1279mAh/g under the current density of 0.5C, and the capacity is reduced to 490mAh/g after 200 charge-discharge cycles. And the coulombic efficiency average value exceeds 100 percent, and the coulombic efficiency is defined as the ratio of the discharge capacity to the charge capacity, and the result reflects that lithium dendrites are dissolved in the discharge process and then become 'dead lithium' and can not be reversibly converted into metal lithium in the subsequent charge process, so the charge capacity is smaller than the discharge capacity. The first discharge specific volume of the lithium-sulfur battery adopting the copper-plated lithium cathode is 1148mAh/g, the capacity is 603mAh/g after 200 times of charge-discharge cycles, the capacity is 526mAh/g after 300 times of cycles, and the coulombic efficiency is up to 99.6%. Showing good cycling stability and capacity retention.
Drawings
FIG. 1 is a scanning electron microscope image of the front surface morphology of a lithium negative electrode containing a conductive protective film;
FIG. 2 is a scanning electron microscope image of the cross-sectional morphology of a lithium negative electrode containing a conductive protective film;
FIG. 3 is a graph comparing the cycling curves of a lithium sulfur battery in example 1 with a pristine lithium negative electrode in comparative example 1, with a lithium negative electrode containing a conductive protective film;
FIG. 4 is a graph of the voltage-time cycling of a symmetric cell in example 2 for a lithium anode with a conductive protective film that exhibits stable cycling and less voltage polarization;
FIG. 5 is a graph of the voltage-time cycling of a symmetrical cell of an original lithium negative electrode in comparative example 2, the lithium negative electrode containing a conductive protective film exhibiting fluctuating cycling stability and large voltage polarization;
FIG. 6 is a scanning electron micrograph of a lithium negative electrode comprising a conductive protective film after cycling in example 2 showing no lithium dendrites;
fig. 7 is a scanning electron micrograph of the pristine lithium negative electrode after cycling in comparative example 2, the surface being full of dendrites.
Fig. 8 (a) is a schematic diagram of an original lithium negative electrode lithium deposition in which charges are accumulated at the tips of dendrites, and fig. 8 (b) is a schematic diagram of a lithium negative electrode lithium deposition including a conductive protective film in which no dendrites are formed and charges are uniformly distributed.
Detailed Description
The experimental procedures used in the following examples are conventional unless otherwise specified.
Reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
In the following examples, a novice test system is adopted for testing the battery performance, Celgard 2400 is used as a diaphragm, a 1, 3-Dioxolane (DOL)/ethylene glycol dimethyl ether (DME) mixed solution (volume ratio is 1:1) with the concentration of 1M lithium bistrifluoromethanesulfonimide (LiTFSI) is selected as an electrolyte, the electrolyte simultaneously contains 1% by mass of anhydrous lithium nitrate as an additive, and the 2032 coin battery is assembled in the following examples in a glove box filled with argon.
Example 1
(1) Mixing nano calcium carbonate and glucose according to a mass ratio of 1:1, adding deionized water, carrying out magnetic stirring at 80 ℃ until the mixture becomes colloidal, drying in an oven, and introducing flowing Ar gas into a tubular furnace, and heating for 2 hours at 950 ℃. And washing the calcium carbonate template by using dilute hydrochloric acid, washing by using deionized water until the solution is neutral, and putting the solution into an oven to dry to obtain the porous carbon.
(2) Mixing and grinding sulfur and porous carbon according to the mass ratio of 6:4, introducing flowing Ar gas into a tubular furnace, heating for 6 hours at 155 ℃, and then heating for 2 hours at 300 ℃. And uniformly mixing the obtained residues, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 7:2:1, dissolving the mixture in an NMP solution to prepare slurry, and uniformly coating the slurry on an aluminum current collector to prepare the anode.
(3) In an argon glove box, the glove box conditions were: the water and oxygen contents are both less than 0.1ppm by volume fraction. Firstly, the lithium sheet is pasted on a tray to be sputtered by using a conductive double-sided adhesive tape, the lithium sheet and the tray are placed in a sealing box together, and then the tray is transferred into a magnetron sputtering coating instrument.
(4) Performing direct-current magnetron sputtering copper plating on the surface of a lithium sheet: when the vacuum degree in the vacuum coating chamber reaches 1.0 multiplied by 10-4When Pa, Ar gas (the flow rate is 35sccm) is introduced as sputtering gas, the gas pressure is 1.0Pa, the power is 30W, after pre-sputtering for 10min, vacuum copper plating is carried out for 300 seconds, and the prepared lithium sheet is used as a negative electrode.
(5) And assembling the lithium-sulfur battery according to the sequence of the anode, the electrolyte, the diaphragm, the electrolyte and the cathode, and performing performance test, wherein the test voltage is 1.7-2.8V.
The surface appearance of the lithium sheet after being plated with Cu is shown in figure 1, the section appearance is shown in figure 2, and a layer of Cu thin film covered on the surface of the lithium sheet is well combined with a lithium substrate and has nano pores so as to ensure the transmission of lithium ions.
Comparative example 1
An original lithium sheet is used as a negative electrode, a positive electrode, electrolyte and a diaphragm are the same as those in example 1, a lithium-sulfur battery is assembled, and a performance test is performed, wherein the test voltage is the same as that in example 1.
FIG. 3 is a comparison of the cycling curves of lithium sulfur batteries showing that the cycling performance of lithium cathodes fabricated using the invention is significantly better than that of the original lithium cathodes.
Example 2
(1) In an argon glove box, the glove box conditions were: the water and oxygen contents are both less than 0.1ppm by volume fraction. Firstly, the lithium sheet is pasted on a tray to be sputtered by using a conductive double-sided adhesive tape, the lithium sheet and the tray are placed in a sealing box together, and then the tray is transferred into a magnetron sputtering coating instrument.
(2) Performing direct-current magnetron sputtering copper plating on the surface of a lithium sheet: when the vacuum degree in the vacuum coating chamber reaches 1.0 multiplied by 0-4When Pa, Ar gas (flow rate: 35sccm) was introduced as a sputtering gas, the pressure was 1.0Pa, the power was 30W, and after 10 minutes of pre-sputtering, vacuum copper plating was performed for 300 seconds. The prepared lithium sheet is used as a negative electrode.
(3) An original lithium sheet is taken as a positive electrode, a symmetrical battery is assembled according to the sequence of the positive electrode, electrolyte, a diaphragm, the electrolyte and a negative electrode, performance test is carried out, and the test current density is 2mA/cm2。
(4) After 140 hours of cycling, the negative electrode was disassembled from the cell in a glove box and rinsed with DOL, followed by scanning electron microscopy characterization.
Comparative example 2
(1) The original lithium plate is used as a negative electrode, the positive electrode, the electrolyte and the diaphragm are the same as those in the embodiment 2, a symmetrical battery is assembled, the performance test is carried out, and the test current density is the same as that in the embodiment 2.
(2) And (3) performing scanning electron microscope characterization on the original lithium sheet cathode after circulation in the same process as the example 2.
As can be seen from fig. 4 and 5, the lithium negative electrode prepared by the present invention has stable voltage form and hysteresis voltage after cycling of less than 80mV in the cycling test of the symmetric battery, while the unprotected lithium negative electrode has unstable voltage form fluctuation and hysteresis voltage of 111mV in the cycling test of the symmetric battery. It is demonstrated that the present invention can reduce battery polarization by protecting the lithium negative electrode.
FIG. 6 is a scanning electron microscope morphology photograph taken after the lithium negative electrode prepared by the present invention is cycled, it can be seen that the surface of the lithium sheet is not corroded by the electrolyte, and no generation of lithium dendrite is observed, which is not significantly different from the morphology of the lithium sheet before cycling. And fig. 7 is a scanning electron microscope morphology photograph taken after the original lithium negative electrode was cycled, showing that there was extensive dendrite formation. Fig. 8 (a) is a schematic diagram of original lithium negative lithium deposition, and uneven lithium dissolution/deposition is highly likely to form lithium dendrites, while charges are mainly accumulated at the top of the dendrites due to the tip effect, resulting in the continued growth of the dendrites. Fig. 8 (b) is a schematic diagram of lithium deposition of the lithium negative electrode after Cu film plating, and the charge is approximately uniformly distributed on the surface, thereby inhibiting the formation of lithium dendrite. Accordingly, the present invention provides a scheme that can significantly improve a lithium negative electrode.

Claims (3)

1. A lithium negative electrode comprising a conductive protective film, characterized in that: the method comprises the following steps of (1) attaching a vacuum plated Cu film to the surface of a lithium sheet by using copper as a target material and using a magnetron sputtering technology, wherein the vacuum plated Cu film has an island-shaped and layered composite morphology, and a large number of dispersed pores exist in the Cu film;
the preparation method of the lithium negative electrode containing the conductive protection film comprises the following specific steps:
(1) in an argon glove box, firstly, adhering a lithium sheet on a tray to be sputtered by using a conductive double-sided adhesive tape, putting the tray and the lithium sheet into a sealing box together, and then transferring the tray in the sealing box into a magnetron sputtering coating instrument; wherein, the volume fraction of the water content in the argon glove box is less than 0.1ppm, and the volume fraction of the oxygen content is less than 0.1 ppm;
(2) when the vacuum degree in the vacuum coating chamber reaches 1.0 multiplied by 10-4When Pa, introducing Ar gas as sputtering gas, wherein the flow rate of the Ar gas is 30-40sccm, the gas pressure is 0.5-1.0Pa, the power is 30-50W, carrying out vacuum copper plating after pre-sputtering for 8-15min, and the vacuum copper plating time is 240-360 s.
2. The lithium negative electrode comprising a conductive protective film according to claim 1, wherein: the purity of Cu in the step (2) is more than or equal to 99.99 percent.
3. Use of a lithium negative electrode comprising a conductive protective film according to claim 1, wherein: can be used as the cathode of the lithium-sulfur battery in the field of electrochemical energy storage.
CN201810813974.XA 2018-07-23 2018-07-23 Lithium negative electrode containing conductive protection film and preparation method and application thereof Active CN108987673B (en)

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CN110048116A (en) * 2019-04-25 2019-07-23 电子科技大学 A kind of lithium band/foil and preparation method thereof having good stability in air
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