CN109461908B - High-performance thin-film electrode material and preparation method and application thereof - Google Patents

High-performance thin-film electrode material and preparation method and application thereof Download PDF

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CN109461908B
CN109461908B CN201811174582.XA CN201811174582A CN109461908B CN 109461908 B CN109461908 B CN 109461908B CN 201811174582 A CN201811174582 A CN 201811174582A CN 109461908 B CN109461908 B CN 109461908B
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film
electrode material
active layer
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CN109461908A (en
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胡仁宗
兰雪侠
张厚泼
王辉
曾美琴
朱敏
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South China University of Technology SCUT
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/627—Expanders for lead-acid accumulators
    • 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 relates to high-performance Mo/SnO2The preparation method and the application of the/Mo sandwich structure film electrode material comprise the following steps: a. depositing a Mo film on the brass substrate by adopting a magnetron sputtering method; b. SnO is sputtered and deposited on the surface of the Mo film2An active layer; c. Mo/SnO obtained in step b2The film is used as a substrate, and the Mo film is continuously sputtered and deposited. The method has the advantages of simple preparation process, designability, controllability, high flexibility and the like. Mo/SnO of the present invention2the/Mo film electrode material is applied to the lithium ion battery cathode material, and the SnO can be greatly improved by controlling the film thickness of the sandwich structure2The conversion reaction reversibility and stability of the electrode can be realized, and simultaneously SnO can be effectively buffered2The volume expansion of the electrode shows the characteristics of high first coulombic efficiency, high reversible capacity, high cycle stability and high rate performance.

Description

High-performance thin-film electrode material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion battery manufacturing, relates to a lithium ion battery material, and particularly relates to high-performance Mo/SnO2an/Mo film electrode material, a preparation method and application thereof.
Background
The lithium ion battery is an important device for converting, storing and utilizing new energy, has the advantages of large specific capacity, high working voltage, long cycle life, small environmental pollution and the like, and is widely applied to the fields of portable electronic equipment, aerospace, military, medical treatment and the like. However, the biggest problem of the current commercial carbon negative electrode material is that the theoretical specific capacity is low, and even if various modification methods such as doping treatment, surface coating and the like are adopted, the requirements of the commercial carbon negative electrode material on high-energy-density energy storage systems such as power batteries, thin-film micro batteries and the like are difficult to meet. Therefore, the development of novel non-carbon-based negative electrode materials with higher energy density is the key point of the development of lithium ion batteries, and SnO2The cathode is widely researched and paid attention to due to the advantages of high theoretical specific capacity (1494mAh/g), low cost, moderate lithium intercalation potential and the like.
Using SnO2When the base material is used as a negative electrode, the problems that the cycle stability is poor due to structural collapse caused by stress effect in the electrode cycle process and the irreversible capacity is generated at the initial stage of the cycle due to poor reversibility of conversion reaction are mainly faced. At present, the problem of improving the cycle performance is relatively easy to solve, and researchers make a great deal of progress through modification methods such as doping, compounding, pore forming and the like, wherein the most common method is to use SnO2The phases are dispersed in the graphite matrix, and the volume expansion is reduced by the buffer effect of the matrix phase, however, although the method can effectively improve the cycle stability, the problem of low coulombic efficiency for the first time is brought, and furthermore, the problem of poor reversibility of the conversion reaction cannot be solved.
Chinese patent publication No. CN105226258APlease disclose a lithium ion battery cathode composite film material and a preparation method thereof. The negative film is ZnO/SnO2The composite film takes a current collector copper foil or a copper foil deposited with a metal copper film as a substrate, the substrate is soaked by weak acid to remove surface oxides, and then the substrate is placed into a vacuum cavity of vacuum coating equipment for ZnO transition layer film deposition and SnO2Depositing active layer film to obtain final ZnO/SnO2And (3) compounding the film. The obtained film is used as a lithium ion battery cathode material to assemble a lithium ion battery, and electrochemical tests show that ZnO/SnO2Composite film ratio SnO2The film can form good interface contact with the current collector, and the active film without the transition layer ZnO is more SnO2The lithium ion battery is easy to fall off from a current collector in the charging and discharging processes to lose efficacy; using ZnO/SnO2The lithium ion battery with the composite film as the cathode has high first discharge specific capacity, good stability and high rate capability.
Chinese patent application publication No. CN104157788A discloses a perovskite thin film photovoltaic and a preparation method thereof. The perovskite thin film photovoltaic adopts SnO which can be prepared at low temperature2As an electron transport layer to replace the conventional TiO requiring high temperature sintering2An electron transport layer. SnO prepared based on low temperature2The perovskite film photovoltaic of the electron transport layer achieves high photoelectric conversion efficiency of 14.60 percent, and is greatly superior to TiO based on traditional high-temperature sintering2Perovskite solar of electron transport layer. SnO2The film has stable chemical properties and simple preparation process, greatly simplifies the preparation process of the perovskite, effectively reduces the manufacturing cost, and can well improve the stability of the photovoltaic performance of the perovskite film.
The above studies have only solved the problem of stability, but have not solved the problem of poor reversibility of the conversion reaction. The reversible regulation and control of the conversion reaction depend on the size of Sn particles generated by the dealloying reaction, and the modification technical means adopted at present cannot give consideration to SnO2The key reason of the problems of the cycle stability and the reversibility of the conversion reaction of the film cathode material is that the added matrix has no regulation and control effect on the size of Sn particles, and the reason is thatThis results in a large irreversible capacity. It has been confirmed that the addition of a transition metal M (Fe, Co, Mn, etc.) is effective as a means for suppressing coarsening of Sn particles and thereby improving the reversibility of conversion reaction. However, no more specific research reports on this aspect are found.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide high-performance Mo/SnO2The film can solve SnO of lithium ion battery at the same time2The problems of poor long-term circulation stability of the film cathode and reversibility and stability attenuation of the conversion reaction are solved. Another object of the present invention is to provide the above high performance Mo/SnO2Application of the/Mo film electrode material. The invention adopts Mo film and SnO with good conductivity and ductility2The active layer forms a sandwich structure, which not only can well support active substances and improve the structural integrity, thereby improving the circulation stability, but also utilizes Mo to diffuse into SnO2Plays a pinning role on Sn particles, inhibits the coarsening of the Sn particles, and improves the reversibility and the stability of the conversion reaction. Such a novel structure and method for regulating SnO2And other metal oxide systems have important significance in obtaining high first coulombic efficiency, high reversible capacity, high cycling stability and high rate performance.
The purpose of the invention is realized by the following technical scheme: high-performance Mo/SnO2The Mo film electrode material consists of Mo film and SnO2The active layer forms a sandwich structure, and the upper and lower Mo films wrap SnO2And an active layer.
In a preferred embodiment of the invention, SnO2The thickness of the active layer is about 300-400nm, the thickness of the bottom Mo layer is about 70-120nm, and the thickness of the top Mo layer is about 70-120 nm.
In a preferred embodiment of the invention, the high performance Mo/SnO2the/Mo film electrode material is prepared by a vacuum magnetron sputtering deposition coating mode.
The invention also protects a high-performance Mo/SnO2The preparation method of the/Mo film electrode material comprisesThe method comprises the following steps:
a. using yellow copper foil as a substrate, and depositing a Mo film on the substrate by a vacuum magnetron sputtering deposition coating method;
b. SnO is sputtered and deposited on the surface of the Mo film2An active layer;
c. taking the sample obtained in the step b as a matrix, and continuously sputtering and depositing a Mo film to obtain Mo/SnO2a/Mo sandwich structure film.
In a preferred embodiment of the invention, the sputtering power in the vacuum magnetron sputtering deposition coating process in the steps a to c is 80 to 120W, and the sputtering time is 1 to 10 min; more preferably, the sputtering time is 2-10 min.
In a preferred embodiment of the present invention, the sputtering process is performed under a high purity inert gas pressure of 0.5 to 2.0Pa, the gas flow rate is controlled to 16 to 20sccm, and SnO is2The Mo target and the Mo target are both arranged on a radio frequency power supply target head; more preferably, the high-purity inert gas is argon, and the pressure is 1.0-2.0 Pa.
In a preferred embodiment of the present invention, the high purity argon gas is an argon gas having a purity of 99.99% or more.
In a preferred embodiment of the present invention, the brass foil substrate is cleaned prior to use to reduce the adverse effects of surface oil and oxides on film-to-substrate bonding.
In a preferred embodiment of the present invention, the cleaning is performed by sequentially cleaning the substrate with distilled water, diluted hydrochloric acid, distilled water, absolute ethyl alcohol and acetone in ultrasonic wave, and drying the substrate with a vacuum oven.
The invention also protects the Mo/SnO2The application of the/Mo film electrode material in the lithium ion battery cathode material.
The invention is compared with the existing SnO of other lithium ion batteries2Compared with the base film electrode material, the base film electrode material has the following advantages and beneficial effects:
(1) the invention adopts Mo inactive phase as SnO2The added phase of the negative electrode is deposited by vacuum magnetron sputteringThe Mo/SnO with a certain nano-thickness level is prepared by optimizing2the/Mo sandwich structure film electrode material. SnO is wrapped by upper and lower Mo films2Active layer, Mo layer and SnO2The bonding between the layers is good. Mo/SnO of the present invention2the/Mo film electrode material is applied to the lithium ion battery cathode material, and the SnO can be greatly improved by controlling the film thickness of the sandwich structure2The conversion reaction reversibility and stability of the electrode can be realized, and simultaneously SnO can be effectively buffered2The volume expansion of the electrode shows the characteristics of high first coulombic efficiency, high reversible capacity, high cycle stability and high rate performance, and simultaneously solves the problem of SnO of the lithium ion battery2The problems of poor long-term circulation stability of the film cathode and reversibility and stability attenuation of the conversion reaction are solved.
(2) The Mo/SnO provided by the invention2The preparation method of the/Mo film electrode material has the advantages of simple process, high flexibility and high repeatability.
(3) Mo/SnO of the present invention2the/Mo film electrode material can be used as a lithium ion battery cathode material, and the addition of the Mo layer can effectively support the active substance not to be peeled off due to volume change, so that the stability of electrode cycle is improved. SnO is isolated by the Mo layer2The direct contact between the active layer and the electrolyte is favorable to raising the stability of SEI film and improving the electron transfer and Li+Diffusion capability, thereby promoting electrochemical reaction kinetics. Second, diffusion to SnO2Mo in the layer has a pinning effect relative to Sn particles, and the aggregation and growth of the Sn particles are inhibited, so that the reversibility and reversibility stability of a conversion reaction are improved. Compared with other SnO2The base film cathode material solves the problems of poor cycle stability, and poor reversibility and stability of conversion reaction.
Drawings
The following is further described with reference to the accompanying drawings.
FIG. 1 is a Mo/SnO alloy prepared in example 1 of the invention2XRD pattern of/Mo film cathode material;
FIG. 2 is Mo/SnO prepared in example 12SEM image of/Mo film cathode material;
FIG. 3 isMo/SnO prepared in example 12A charge-discharge curve diagram of the/Mo film negative electrode material;
FIG. 4 is Mo/SnO prepared in example 12A cycle performance curve diagram of a lithium ion battery made of a negative electrode material of a/Mo film;
FIG. 5 is Mo/SnO prepared in example 22A multiplying power performance curve diagram of a lithium ion battery made of a/Mo film negative electrode material;
FIG. 6 is Mo/SnO prepared in example 32FIB-SEM (focused ion beam-scanning electron microscope) images of the cross section of the/Mo film negative electrode material;
FIG. 7 is Mo/SnO prepared in example 32A cycle performance curve diagram of a lithium ion battery made of a negative electrode material of a/Mo film;
FIG. 8 is Mo/SnO prepared in example 42A cyclic voltammetry characteristic curve diagram of a/Mo film negative electrode material lithium ion battery;
FIG. 9 is Mo/SnO prepared in example 52A cross-sectional SEM image of the/Mo film cathode material;
FIG. 10 is Mo/SnO prepared in example 62A cycle performance curve diagram of a lithium ion battery made of a negative electrode material of a/Mo film;
FIG. 11 is a Mo/SnO alloy prepared in examples 1 and 62Mo film negative electrode material and pure SnO prepared by comparative example2And (3) comparing the cycle performance curves of the thin film negative electrode material.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
Mo/SnO for negative electrode of lithium ion battery of this example2The preparation method of the/Mo film negative electrode material comprises the following steps:
the sputtering is carried out by adopting an ultrahigh vacuum multi-target magnetron sputtering instrument (JGP-560, Shenyang scientific instruments research center, Ltd.) with the sputtering power of 120W. Firstly, Mo with the purity of 99.99 percent and SnO2The target materials are respectively arranged on the target heads of the radio frequency power supplies; cleaning the brass foil substrate in ultrasonic wave by using distilled water, dilute hydrochloric acid, distilled water, absolute ethyl alcohol and acetone in sequenceAfter the surface oil stains and oxides of the matrix are washed, the matrix is placed in a vacuum drying box to be dried, the copper foil matrix is taken out and installed on a sample base of a sputtering chamber, and the distance between a target material and a substrate is kept to be about 10 cm.
Respectively using a mechanical pump and a molecular pump to pump air until the vacuum degree in the sputtering chamber reaches 6 multiplied by 10-4And after Pa, filling working gas Ar with the purity of 99.99% and the pressure of 2.0Pa into the sample at the flow rate of 20sccm, firstly turning on a radio frequency power supply corresponding to the Mo target, pre-sputtering for 5 minutes, then rotating the sample to a position right above the target, and starting sputtering for 3 minutes. Closing the radio frequency power supply corresponding to the Mo target after the sputtering is finished, and opening SnO2The radio frequency power supply corresponding to the target starts to sputter and deposit SnO2Film sputtering for 3min, and finally SnO2The surface was continued to be coated with a Mo layer with the same process parameters. FIG. 1 shows Mo/SnO prepared in this example2XRD pattern of the/Mo film negative electrode material.
Mo/SnO prepared in this example2The SEM image of the/Mo film negative electrode material is shown in figure 2, as shown in the figure, the surface of the film has obvious granular feeling, and the film layer is continuous and compact, which is beneficial to SnO treatment of the Mo layer in the electrode circulation process2The supporting and protecting functions of the active layer.
Mo/SnO obtained in this example2A/Mo film negative electrode material is used as a working electrode for performance test, and a button cell is assembled by using metallic lithium (with the purity of 99.99%) as a counter electrode and 1mol/L of Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (volume ratio of 2:1) solution as an electrolyte in an argon atmosphere glove box for test. The test condition is that the charge-discharge current density is 200uA/cm2The cut-off voltage of charge and discharge is 0.01V-3.0V (vs. Li/Li)+). The charging and discharging curve chart obtained by the test is shown in figure 3, and as shown in the figure, the Mo/SnO prepared by the embodiment2The first reversible capacity of the negative electrode of the/Mo film is 0.137mAh/cm2The first coulombic efficiency was as high as 86.5%, and the charging curves of cycles 1, 2 and 20 almost overlapped, indicating that the reversible capacity was well maintained during the previous 20 cycles.
FIG. 4 is Mo/SnO prepared2Of a/Mo film negative electrodeThe cycle-capacity performance curve shows that the specific capacity hardly decays within 150 cycles, and the first discharge specific capacity is 0.153mAh/cm2The 2 nd discharge specific capacity is 0.137mAh/cm2After 150 cycles, the capacity value is 0.138mAh/cm2. The generation of irreversible capacity is completely avoided after the first cycle, the capacity retention rate is up to 100% in the 2 nd to 150 th cycles, and simultaneously the problem of SnO2Poor self-circulation stability, reversibility of conversion reaction and stability attenuation.
Example 2
Mo/SnO of this example2The preparation steps of the/Mo film negative electrode material are basically the same as those described in example 1, except that the sputtering power used for sputtering the upper and lower Mo films is 100W. Mo/SnO prepared in this example2the/Mo film negative electrode material is assembled into a button cell in an argon atmosphere glove box by taking metal lithium as a counter electrode for testing. The test conditions were: the charging and discharging current density is respectively 200uA/cm2、500uA/cm2、1mA/cm2、2mA/cm2And 5mA/cm2And the cut-off voltage of charging and discharging is 0.01V-3.0V. The graph of the rate performance obtained by the test is shown in FIG. 5, and as shown in the figure, when the current density is 200 μ A/cm2When the charge capacity is 0.141mAh/cm2When the current density is 1mA/cm2When the charge capacity is 0.124mAh/cm2When the current density continues to increase to 5mA/cm2Then, it still has 0.094mAh/cm2The specific charge capacity of (a). When the current density is recovered to 200mA/cm2When the charging capacity is increased, the charging specific capacity can be completely recovered to the initial level and reaches 0.146mAh/cm2. In addition, the cycle remains steady at each current density. Thus, the Mo/SnO prepared in this example2the/Mo film negative electrode material has excellent rate performance.
Example 3
Mo/SnO of this example2The preparation steps of the/Mo film negative electrode material are basically the same as those described in example 1, except that SnO2The sputtering power of the active layer is 80W, and the upper and lower Mo addition layersThe sputtering power is 80W, and the sputtering time is 5 min. Mo/SnO obtained in this example2The FIB-SEM image of the cross section of the negative electrode material of the/Mo film is shown in FIG. 6, and as shown in the figure, the total thickness of the sandwich structure film is about 535nm, wherein SnO2The thickness of the active layer is about 350nm, the thickness of the bottom Mo layer is about 110nm, and the thickness of the top Mo layer is about 75 nm. While SnO can be found2The combination of the layer and the Mo layer is better, and the Mo layer is favorable for SnO in electrochemical cycle process2The support and protection of the active particles, thereby improving long-term cycling stability.
Mo/SnO obtained in this example2The electrochemical test method of the/Mo film anode material is the same as that described in example 1. The charge-discharge cycle test performed according to the method gave a cycle-capacity performance curve as shown in FIG. 7, in which the Mo/SnO prepared in this example was shown2the/Mo film negative electrode material keeps stable in the previous 25 cycles, and the capacity retention rate reaches 94.1% from the 2 nd cycle to the 20 th cycle, which shows that the sandwich structure greatly improves SnO2The conversion reaction of the film is reversible.
Example 4
Mo/SnO of this example2The preparation steps of the/Mo film negative electrode material are basically the same as those described in example 1, except that SnO2The sputtering time of the active layer is 10min, in SnO2The sputtering time of the Mo addition layer on the surface was 2 min. Mo/SnO prepared in this example2And the/Mo film negative electrode material is assembled into a button cell in an argon atmosphere glove box by taking metal lithium as a counter electrode to carry out CV test. And (3) testing conditions are as follows: the scanning speed is 0.2mV/s, and the voltage range is 0.01V-3.0V. FIG. 8 is Mo/SnO prepared in this example2As shown in the graph of the cyclic voltammetry characteristic of the/Mo film negative electrode material, oxidation peaks at about 1.3V and about 1.8V respectively represent SnO generated by Sn and SnO continuing to Li2O reaction to form SnO2The reverse reaction process of the conversion reaction is almost overlapped in the peak type in the first 5 times of circulation, which shows that the electrochemical reaction of the electrode material and lithium is stable, and the reversibility of the conversion reaction is good.
Example 5
Mo/SnO of this example2The preparation steps of the/Mo film negative electrode material are basically the same as those described in example 1, except that SnO2The sputtering time of the active layer is 10min, the sputtering power is 110W, and the sputtering time of the Mo layer is 2 min. Mo/SnO prepared in this example2The SEM image of the cross section of the/Mo film cathode material is shown in FIG. 9, as shown in the figure, the upper Mo layer and the lower Mo layer are tightly wrapped with SnO2Active layer, avoiding SnO2The electrolyte is directly contacted with the electrolyte, so that an SEI film is formed on the surface of the Mo layer, the stability of the SEI film is improved, and charge transfer and Li are improved+Transport capacity, thereby promoting electrochemical reaction kinetics.
Example 6
Mo/SnO of this example2The preparation steps of the/Mo film negative electrode material are basically the same as those described in example 1, except that SnO2The sputtering time of the active layer is 2min, the sputtering time of the upper Mo layer and the lower Mo layer is 2min, and the working pressure of Ar gas is 1.0 Pa. Mo/SnO prepared in this example2the/Mo film negative electrode material is assembled into a button cell in an argon atmosphere glove box by taking metal lithium as a counter electrode for testing. The test conditions were: the charge-discharge current density is 200uA/cm2And the cut-off voltage of charging and discharging is 0.01V-3.0V. The measured cycle-capacity performance graph is shown in FIG. 10, in which the Mo/SnO prepared in this example is shown2The first coulombic efficiency of the/Mo film negative electrode material is up to 89%, and the first discharge specific capacity is 0.1129mAh/cm2The 100 th cycle discharge specific capacity is 0.1121, the capacity retention rate almost reaches 100%, and the lithium ion battery has the excellent performances of high first efficiency, high reversible capacity and high cycle performance.
Comparative examples
Pure SnO of this example2Preparation steps of thin film negative electrode material and SnO in embodiment 12The preparation process of the active layer is consistent, and the pure SnO obtained in the example2The electrochemical test method for the thin film anode material was the same as described in example 1. According to the method, charge-discharge cycle test is carried out, and the obtained cycle performance data and the Mo/SnO obtained in examples 1 and 62Cycling performance data of/Mo film negative electrode materialFor comparison, the comparison results are shown in fig. 11. From the figure, it can be seen that pure SnO2The film is subject to stress effects during long-term cycling causing the active material to peel off, thus showing a capacity drop after 100 cycles, and more importantly, a low first effect (76.1%) due to the poor reversibility and stability of the conversion reaction and an irreversible capacity generation in the initial 20 cycles. While Mo/SnO prepared in example 62The first coulombic efficiency of the/Mo film negative electrode material is up to 89%, the circulation capacity retention rate of the first 20 times is nearly 100%, and the key problem of poor reversibility and stability of the conversion reaction is effectively solved. Meanwhile, Mo/SnO prepared in example 12The negative electrode material of the/Mo film not only avoids the generation of irreversible capacity in the initial stage of circulation, but also solves the problem of capacity reduction caused by the structural damage of the electrode after 100 times of circulation.
Thus, the invention overcomes the defect that SnO is treated in the prior art2The base film is difficult to give full play to theoretical capacity when applied to the lithium ion battery cathode material, and excellent performances of high first efficiency, high reversible capacity and high cycle stability are obtained.
The above embodiments are only some preferred embodiments of the present invention, but the embodiments of the present invention are not intended to limit the implementation and the scope of the invention, and all equivalent changes, modifications, substitutions, combinations, simplifications made according to the content and principle of the claims of the present invention should be included in the scope of the present invention.

Claims (8)

1. High-performance Mo/SnO2the/Mo film electrode material is characterized by comprising a Mo film and SnO2The active layer forms a sandwich structure, and the upper and lower Mo films wrap SnO2An active layer;
SnO2the thickness of the active layer is 300-400nm, the thickness of the Mo film at the bottom is 70-120nm, and the thickness of the Mo film at the top is 70-120 nm;
the coating is prepared by a vacuum magnetron sputtering deposition coating mode.
2. High-performance Mo/SnO2The preparation method of the/Mo film electrode is characterized by comprising the following steps:
a. using yellow copper foil as a substrate, and depositing a Mo film on the substrate by a vacuum magnetron sputtering deposition coating method, wherein the thickness of the Mo film is 70-120 nm;
b. SnO is sputtered and deposited on the surface of the Mo film by a vacuum magnetron sputtering deposition coating method2Active layer, SnO2The thickness of the active layer is 300-400 nm;
c. taking the sample obtained in the step b as a matrix, continuously sputtering and depositing a Mo film by a vacuum magnetron sputtering deposition coating method, wherein the thickness of the Mo film is 70-120nm, and thus obtaining Mo/SnO2a/Mo sandwich structure film.
3. The preparation method according to claim 2, wherein the sputtering power in the vacuum magnetron sputtering deposition coating process in the steps a to c is 80 to 120W, and the sputtering time is 1 to 10 min.
4. The preparation method according to claim 2, wherein the sputtering is performed under a high purity inert gas pressure of 0.5 to 2.0Pa, a gas flow rate is controlled to be 16 to 20sccm, and SnO is performed2And the Mo target material are both arranged on a radio frequency power supply target head.
5. The method according to claim 4, wherein the high purity inert gas is argon having a purity of 99.99% or more, and the pressure is 1.0 to 2.0 Pa.
6. The method according to any one of claims 2 to 5, wherein the brass foil base material is cleaned before use to reduce the adverse effects of the surface oil and oxides on film-to-film bonding.
7. The method according to claim 6, wherein the cleaning is performed by sequentially cleaning the substrate with distilled water, diluted hydrochloric acid, distilled water, absolute ethyl alcohol and acetone in ultrasonic waves, and drying the substrate with a vacuum oven.
8. Mo/SnO according to claim 12A/Mo film electrode material or Mo/SnO prepared by the preparation method of any one of claims 2-62the/Mo film electrode material is applied to the negative electrode material of the lithium ion battery.
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