CN110034278B - SnS2Thin film lithium battery cathode, preparation and application thereof - Google Patents

SnS2Thin film lithium battery cathode, preparation and application thereof Download PDF

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CN110034278B
CN110034278B CN201810033576.6A CN201810033576A CN110034278B CN 110034278 B CN110034278 B CN 110034278B CN 201810033576 A CN201810033576 A CN 201810033576A CN 110034278 B CN110034278 B CN 110034278B
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sns
buffer layer
lithium battery
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CN110034278A (en
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张治安
赖延清
王麒羽
汪齐
刘芳洋
洪波
张凯
李劼
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Central South University
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    • 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
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    • 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
    • C23C14/0623—Sulfides, selenides or tellurides
    • 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
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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

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Abstract

The invention belongs to the technical field of thin film materials, and particularly discloses SnS2The negative electrode of the thin-film lithium battery comprises a current collector, a metal buffer layer compounded on the surface of the current collector, and an active material layer compounded on the metal buffer layer; the metal buffer layer is made of metal with a lattice constant of 3.6-4.7 and conductivity; the active material layer is made of SnS with exposed (0,0,1) crystal face2. The invention also discloses the SnS2The preparation method of the negative electrode of the thin film lithium battery comprises the steps of sputtering a metal buffer layer on a current collector in advance, and then using Sn on H2And S, performing reactive sputtering, and forming the active material layer with the structure on the surface of the metal buffer layer in one step. The invention also discloses an application of the cathode. The button cell is assembled by the film and the lithium sheet, and the material is proved to show excellent electrochemical performance, effectively reduce electrode polarization and improve the energy density and the cycling stability of the cell.

Description

SnS2Thin film lithium battery cathode, preparation and application thereof
Technical Field
The invention relates to a SnS2A preparation method of a thin film lithium ion battery electrode belongs to the field of lithium ion batteries.
Background
Energy is a biological material basis for developing national economy and improving the living standard of people, and is also an important factor directly influencing the economic development. Since the 21 st century, the problems of resource shortage, environmental pollution, greenhouse effect and the like brought by the traditional energy utilization mode are increasingly prominent, the improvement of an energy structure and the development of efficient and clean novel energy have become global consensus. Lithium ion batteries are favored because of their superior properties, such as safety, environmental protection, high specific energy, and good electrochemical properties. In order to meet the requirement of energy miniaturization of the traditional microelectronic device and integration of a new composite energy storage system, the lithium ion battery is further developed into an ultrathin and bendable thin-film lithium ion battery with high energy density.
The metal lithium film can be used as the negative electrode of the film lithium ion battery, but the lithium has low melting point, is sensitive to air and is easy to be oxidized, and the lithium negative electrode can generate lithium dendrite growth to form dead lithium or cause short circuit in the battery, and the like, and the defects limit the application of the lithium film negative electrode. The carbon negative electrode material used commercially at present has the defects of low energy density, difficult film formation and the like, and is difficult to meet the requirement of the thin-film lithium ion micro battery on high energy density.
Although the current commercial Si-based negative electrode has extremely high capacity, the addition of noble metal increases the related cost, which also greatly limits the large-scale production of the catalyst, so people look to the metal material catalyst. The main reason Sn-based negative electrode materials are receiving attention is that Sn has a high lithium storage capacity. At present, the volume change of pure Sn materials used by a film electrode in the lithium intercalation process is large, and the volume expansion effect is serious, so in order to overcome the problem of poor cycle performance of a pure Sn film negative electrode, researchers turn to the preparation and research of Sn-M system intermetallic compound or composite films. WeixiangChen (Journal of Power Sources, 2012, 201: 259-2The composite material has higher capacity and good cycling stability. However, this method is not suitable for controlling the thickness of the material to be prepared, and is not effective for preparing thin film electrodes. Gabriel M.Veith (Journal of Power Sources, 2014, 267: 329-) -336) adopts a magnetron sputtering method to prepare the SnSb thin-film electrode,the electrode shows good electrochemical performance, but the method for preparing the thin film electrode by directly sputtering the active substance material is difficult to control the structure and specific functions of the prepared material, and inhibits the exertion of the activity of the material.
In conclusion, there is an urgent need in the art to develop a simple and efficient method for preparing Sn-based thin film electrodes with specific morphology, and thin film electrode preparation with high energy density and excellent cycle performance has been the subject of intense research in the art.
Disclosure of Invention
To solve the technical problems in the prior art, a first object of the present invention is to provide an SnS2The present invention is directed to a thin film lithium battery negative electrode (also referred to as a thin film lithium battery negative electrode, or simply a negative electrode) which is excellent in electrical properties.
The second purpose of the invention is to provide the SnS2A preparation method of a thin film lithium battery cathode aims at providing a preparation method which can well control the crystal structure and the morphology of an active layer.
The third purpose of the invention is to provide the SnS2The thin film lithium battery cathode is applied to a thin film lithium ion battery.
SnS2The negative electrode of the thin-film lithium battery comprises a current collector, a metal buffer layer compounded on the current collector, and an active material layer compounded on the surface of the metal buffer layer;
the metal buffer layer is made of metal with a lattice constant of 3.6-4.7 and conductivity;
the active material layer is made of SnS with exposed (0,0,1) crystal face2。
According to the material, the active material layer has a (0,0,1) crystal face structure, the active material layer is not required to be compositely adhered through an adhesive, the active material layer with the crystal face structure can improve the overall energy density of the battery, and the capacity and the cycle performance of the material can be greatly improved; in addition, be provided with the metal buffer layer between active material layer and the current collector, help promoting the structural stability of material, the volume effect that buffering active material layer brought in charge-discharge process.
Preferably, the active material layer may be partially limited to the metal buffer layer or may be combined on the surface of the metal buffer layer.
Preferably, SnS2The active material layer is compounded on the surface of the metal buffer layer.
Preferably, the current collector is a metal current collector stable at a low potential, and may be, for example, a copper foil, a stainless steel, a nickel foil, an iron foil, a molybdenum foil, a zinc foil, a nickel-titanium alloy, or a noble metal foil.
More preferably, the current collector is a copper foil, a stainless steel, a nickel foil, an iron foil or a molybdenum foil.
The buffer layer of the metal with the lattice parameter can induce SnS with (0,0,1) crystal face2And (4) forming. In addition, the volume effect of the active material during charge and discharge is "buffered" to some extent.
Preferably, the material of the metal buffer layer is at least one of Cu, Ti, Pt and Cr. The preferred metals are more conductive than other non-selected metals and have more outstanding mechanical properties.
Preferably, the thickness of the metal buffer layer is 10-50 nm. Under the metal buffer layer with the optimized thickness, SnS is more favorably induced2Form and buffer volume expansion; if the buffer layer is too thin, the induction effect cannot be achieved; if the buffer layer is too thick, the interfacial resistance may increase, and the energy density and the cycle stability of the thin film electrode may be reduced.
Preferably, the thickness of the active material layer is 200-500 nm. With the active material layer with the optimal thickness, the electrical performance of the negative electrode is better, and if the active material layer is too thin, the volume effect is obvious; if the active material layer is too thick, the material deposition presents larger particles and cannot embody the structural characteristics.
SnS obtained for good control2The structural morphology of the negative electrode of the thin film lithium battery further ensures the electrical property of the prepared negative electrode, and the invention also discloses the SnS2The preparation method of the negative electrode of the thin film lithium battery comprises the following steps:
step (1): sputtering a material of the metal buffer layer on the surface of the current collector by utilizing magnetron sputtering, and forming the metal buffer layer on the surface of the current collector;
step (2): the current collector compounded with the metal buffer layer is used as a substrate, Sn is used as a target material, and H is contained in the current collector2S, performing reactive sputtering in the atmosphere to form an active material layer on the metal buffer layer; 40-80W of reactive sputtering process;
and (3): annealing the material obtained in the step (2) to obtain the SnS2A thin film lithium battery cathode.
The invention provides a preparation method capable of preparing a Sn-based thin film electrode with a specific morphology, which comprises the steps of sputtering a current collector on a metal buffer layer to obtain a pre-sputtered current collector; further reactively sputtering SnS thereon2Then annealing treatment is carried out to obtain SnS exposing (0,0,1) crystal face2A film. By adopting the method, the SnS with the crystal face with the specific shape (exposing (0,0,1) can be prepared2) A Sn-based thin film negative electrode; the method overcomes the technical problem that the cathode structure can not be controlled by the conventional method, is beneficial to preparing the film cathode with high electrode capacity and good cycling stability, and has the advantages of simple process, strong controllability, low cost and the like, thereby having great industrial application prospect.
The method utilizes magnetron sputtering to induce and prepare SnS with exposed (0,0,1) crystal face in one step on the basis of the buffer layer2Material, the method having the following effects: 1. the method is simple, easy to prepare and high in repeatability. 2. The presence of the buffer layer may induce SnS2While buffering to some extent the volume effect of the active material during charging and discharging. The (0,0,1) crystal face is an advantageous interface for lithium ion transmission, and the capacity and the cycle performance of the material can be greatly improved. 4. The binder-free active material layer can improve the energy density of the entire battery.
According to the preparation method, the metal buffer layer is sputtered (magnetron sputtering in step (1)) for the first time, and SnS is sputtered (reactive sputtering in the invention) for the second time2The active material layer is annealed at high temperature to obtain SnS with exposed (0,0,1) crystal face2A film.
In the invention, the current collector is pretreated before magnetron sputtering, and the pretreatment process comprises the following steps: soaking the current collector with dilute acid, washing with deionized water and drying.
Preferably, the dilute acid is one or two of hydrochloric acid and sulfuric acid, and the concentration is 5-15 wt%. High concentrations of acid can corrode the surface of the copper foil, causing surface non-uniformity, affecting the uniformity of the film sputtered thereon, and further affecting its electrochemical performance.
In order to obtain the active material layer with good crystal form and appearance and the advantageous structure, the invention originally forms the metal buffer layer on the current collector in advance; the metal buffer layer obtained by sputtering effectively reduces the contact resistance between the active substance and the pole piece, and simultaneously induces the active substance to grow along a specific crystal direction. The active substance sputtered twice on the buffer layer can grow along a specific crystal direction, presents a special structure, strengthens the discharge process of the material, and improves the energy density and the cycling stability.
Preferably, the material of the metal buffer layer is a metal with a lattice constant of 3.6-4.7 and excellent conductivity; further preferably one or more of Cu, Ti, Pt and Cr.
Preferably, in the step (1), the sputtering power is 10-50W, and the sputtering time is 10-30 mins. The sputtering power and time can directly influence the thickness of the metal buffer layer, and if the buffer layer is too thin, the effect of inducing crystal growth cannot be achieved; if the buffer layer is too thick, too much contact resistance will also result.
Another key of the preparation method of the invention is that the catalyst comprises H2Under the atmosphere of S, the reaction sputtering is directly carried out under the sputtering power, and compared with the previous sputtering of Sn, the reaction is carried out again to form SnS2And the SnS is obtained by directly performing reactive sputtering on the metal buffer layer by adopting the hairstyle2The active material layer with the target crystal face structure can be unexpectedly formed on the surface of the metal buffer layer, so that the cycle performance and the first cycle of the negative electrode can be obviously improvedCoulombic efficiency.
In the present invention, the compound contains H2The atmosphere of S is H2S atmosphere or is H2S-mixed atmosphere of inert gas.
Preferably, H2In a mixed atmosphere of S-inert gas, inert gas/H2The ratio of S is 1:10-10: 1.
The inert gas is other inert gases such as argon. Under the mixed atmosphere, the active material layer with the dominant structure is formed on the surface of the metal buffer layer. When the content of the inert gas is high in the mixed atmosphere, the active material layer is doped with a part of unreacted Sn.
Further preferably, said compound comprises H2The atmosphere of S is H2S or Ar/H2S, wherein Ar/H2The ratio of S is 1:10-10: 1; the SnS prepared by the high Ar gas ratio2The purity was too low, and unreacted Sn was mixed.
In the step (2), the power of the reactive sputtering process needs to be controlled between 40 and 80W. The sputtering power can directly influence the thickness of the active material layer, and if the active material layer is too thin, the volume effect is obvious; if the active material layer is too thick, the material deposition presents larger particles and cannot embody the structural characteristics. In addition, the sputtering power has a direct relation with the reaction rate, and under a certain condition, the sputtering power is too low to generate charged particles of Sn; when the sputtering power is too high, a metal simple substance is generated.
In step (2), the preferred sputtering time is 10-60mins under the preferred reactive sputtering conditions. At this preferred sputtering time, the performance of the resulting negative electrode is better.
Preferably, in step (3), the annealing is performed under a protective atmosphere; the protective atmosphere is preferably nitrogen or argon.
Preferably, in the step (3), the temperature of the annealing treatment is 500-800 ℃. Selection of annealing temperature and SnS under corresponding system2Stability is relevant, and at the optimal temperature, the crystal face structure obtained by reactive sputtering can be kept, which is beneficial to improving the electrical property of the obtained cathode material; if temperature is not highToo high, the Sn and Cu are easy to generate alloying reaction; if the temperature is too low, SnS2It can not be recrystallized, and the crystal structure is incomplete.
Preferably, in the step (3), the temperature is raised to the annealing temperature at a temperature raising rate of 2 to 7 ℃/min.
And the heat preservation time is 30-180mins at the annealing temperature.
Under the annealing process, the active material layer with the dominant crystal form structure can be further prepared, and the electrical property of the obtained negative electrode is further improved.
The invention relates to a preferable preparation method, which comprises the following specific steps:
step a: cutting the copper foil, soaking the cut copper foil in dilute acid, repeatedly washing the cleaned copper foil with deionized water, and drying the washed copper foil.
Step b: fixing the cleaned copper foil on a target platform, and sputtering a buffer layer by utilizing magnetron sputtering under the Ar-filled atmosphere, wherein the thickness is 10-50 nm.
Step c: and c, fixing the copper foil obtained in the step b on a target platform, and performing secondary reactive sputtering on the active material layer by utilizing magnetron sputtering in a specific atmosphere, wherein the target material is an Sn target with the sputtering thickness of 200-500 nm.
Step d: and c, annealing the pole piece obtained in the step c in a protective atmosphere.
Compared with the Sn-based thin film electrode prepared by the traditional method, the thin film lithium ion battery electrode preparation method prepared by the technical scheme of the invention has more outstanding structural characteristics, can effectively inhibit the volume expansion effect, improves the lithium ion transmission efficiency, further can effectively reduce the electrode polarization, and improves the battery discharge performance and the cycle stability.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) the technical scheme of the invention is to directly sputter SnS with a specific structure by reactive sputtering2The volume expansion effect is effectively inhibited, the lithium ion transmission efficiency is improved, the electrode polarization is effectively reduced, and the discharge performance and the cycling stability of the battery are improved.
(2) The buffer layer in the thin film lithium ion battery electrode prepared by the invention can effectively reduce the contact impedance between the current collector and the active substance, and can induce the active substance to grow along a specific crystal direction, so that the buffer layer has good guidance quality and accelerates the crystal generation.
(3) The thin film lithium ion battery electrode prepared by the invention comprises a three-layer structure, the middle buffer layer has a certain bonding effect, the problem that active substances are easy to fall off in the conventional sputtering process is solved, and meanwhile, the stability of the electrode in the circulating process is improved and the battery performance is improved due to the sandwich structure.
(4) The method for preparing the thin film lithium ion battery electrode has high repeatability and simple process, and can be used for large-scale production.
Drawings
FIG. 1 is an SEM photograph of a thin film obtained in example 1;
FIG. 2 is an XRD pattern of the thin film obtained in example 1;
FIG. 3 shows SnS obtained in example 12A constant current charge and discharge performance diagram of the lithium ion battery assembled by the membrane electrode;
Detailed Description
The following examples are intended to illustrate the present invention in further detail, but are not intended to limit the scope of the invention as claimed.
In the following examples and comparative examples, unless otherwise stated, the parameters of the magnetron sputtering and reactive sputtering processes can be selected from conventional parameters, for example, the sputtering pressure is 0.4 to 3Pa, the gas flow rate is 10 to 50sccm, and the distance between the target and the substrate is 8 to 14 cm.
Example 1:
soaking the copper foil in 10 wt% hydrochloric acid for 12h, cleaning, wiping with alcohol, and cutting into 2cm × 2cm pieces. Fixing the copper foil on a target platform, selecting Ti as a target material, carrying out pre-sputtering for 10mins, then removing a baffle, adjusting the power to 20W, and sputtering for 20mins, wherein the thickness of the sputtered Ti layer is 10 nm.
After the primary sputtering is finished, the target material is replaced by the Sn target, and the atmosphere is adjusted to Ar/H2S (1: 4), pre-sputtering for 10mins, then moving away the baffle, adjusting the powerThe whole is 60W, and the sputtering time is 40 mins. SnS obtained by sputtering2The film is placed in a tube furnace, the temperature is raised to 700 ℃ at the speed of 5 ℃/min, the film is roasted for 120mins at high temperature, and SnS can be obtained2A film. SnS2The layer thickness was 450 nm.
SnS prepared by the embodiment2The film electrode and the lithium sheet are assembled into a button cell, and the cycling performance test is carried out on a LAND CT-2001A type charge-discharge tester. The button cell test is carried out at room temperature and 25 ℃, the voltage interval is 0.01-2.0V, and the current density is 2Ag-1. The flow and electrochemical properties are shown in the figure:
FIG. 1 is an SEM image of the thin film electrode. The petal-shaped structures shown in the figure indicate that the method for growing the material is along a specific crystal direction.
Fig. 2 is an XRD pattern of the thin film active material. Through and SnS2The standard card (JCPDS 22-0951) comparison is in agreement, wherein the (001) diffraction peak is particularly obvious, which proves good crystallinity.
FIG. 3 shows that SnS is prepared by the method2Thin film electrodes of 2Ag at room temperature-1During constant-current discharge, the specific capacity of 400 cycles can still be kept at 580mAh/g (capacity retention rate is 78.4%, coulombic efficiency of the first cycle is 99.2%), and good cycle performance is shown.
Example 2
Soaking the copper foil in 10 wt% hydrochloric acid for 12h, cleaning, wiping with alcohol, and cutting into 2cm × 2cm pieces. Fixing the copper foil on a target platform, selecting Cu as a target material, carrying out pre-sputtering for 10mins in an Ar gas atmosphere, then removing a baffle, and adjusting the power to 50W for 10mins of sputtering. The Cu layer thickness was 20 nm.
After the primary sputtering is finished, the target material is replaced by the Sn target, and the atmosphere is adjusted to Ar/H2S (1: 8), the baffle is removed after pre-sputtering for 10mins, the power is adjusted to 60W, and sputtering is carried out for 40 mins. SnS obtained by sputtering2The film is placed in a tube furnace, the temperature is raised to 700 ℃ at the speed of 5 ℃/min, the film is roasted for 120mins at high temperature, and SnS can be obtained2A film. SnS2The layer thickness was 400 nm.
SnS prepared by the embodiment2Film(s)Assembling the lithium-ion battery with a lithium sheet to form a button cell, and taking 2Ag at room temperature-1During constant-current discharge, the specific capacity of 400 cycles can still be kept at 500mAh/g (capacity retention rate is 75.3%, coulombic efficiency of the first cycle is 99.1%), and good cycle performance is shown.
Example 3
Soaking the copper foil in 10 wt% hydrochloric acid for 12h, cleaning, wiping with alcohol, and cutting into 2cm × 2cm pieces. Fixing the copper foil on a target platform, selecting Ti/Cr as a target material, carrying out pre-sputtering for 10mins, then removing a baffle, adjusting the power to 30W, and sputtering for 20 mins. The thickness of the Ti/Cr layer was 50 nm.
After the primary sputtering is finished, the target material is replaced by the Sn target, and the atmosphere is adjusted to Ar/H2S (1: 1), the baffle is removed after pre-sputtering for 10mins, the power is adjusted to 80W, and sputtering is carried out for 30 mins. SnS obtained by sputtering2The film is placed in a tube furnace, the temperature is raised to 800 ℃ at the speed of 5 ℃/min, the film is roasted for 30mins at high temperature, and SnS can be obtained2A film. SnS2The layer thickness was 500 nm.
SnS prepared by the embodiment2The film and the lithium sheet are assembled into a button cell which is prepared by 2Ag at room temperature-1During constant-current discharge, the specific capacity of 400 cycles can still be kept at 524mAh/g (capacity retention rate is 75.9%, and coulombic efficiency of the first cycle is 99.2%); showing good cycling performance.
Example 4
Soaking the copper foil in 10 wt% hydrochloric acid for 12h, cleaning, wiping with alcohol, and cutting into 2cm × 2cm pieces. Fixing the copper foil on a target platform, selecting Cr as a target material, carrying out pre-sputtering for 10mins, then removing a baffle, adjusting the power to 20W, and sputtering for 20 mins. The thickness of the Cr layer was 10 nm.
After the primary sputtering is finished, the target material is replaced by the Sn target, and the atmosphere is adjusted to H2And S, after pre-sputtering for 10mins, removing the baffle, adjusting the power to 40W, and sputtering for 60 mins. SnS obtained by sputtering2The film is placed in a tube furnace, the temperature is raised to 700 ℃ at the speed of 5 ℃/min, the film is roasted for 120mins at high temperature, and SnS can be obtained2A film. SnS2The layer thickness was 200 nm.
Preparation Using this exampleSnS of2The film and the lithium sheet are assembled into a button cell which is prepared by 2Ag at room temperature-1During constant-current discharge, the specific capacity of 400 cycles can still be kept at 550mAh/g (the capacity retention rate is 76.3%, and the coulombic efficiency of the first cycle is 99.1%); showing good cycling performance.
Example 5
Soaking the copper foil in 10 wt% hydrochloric acid for 12h, cleaning, wiping with alcohol, and cutting into 2cm × 2cm pieces. Fixing the copper foil on a target platform, selecting Pt as a target material, carrying out pre-sputtering for 10mins, then removing a baffle, adjusting the power to 10W, and sputtering for 30 mins. The Pt layer was 32nm thick.
After the primary sputtering is finished, the target material is replaced by the Sn target, and the atmosphere is adjusted to Ar/H2S (1: 6), the baffle is removed after pre-sputtering for 10mins, the power is adjusted to 70W, and sputtering is carried out for 20 mins. SnS obtained by sputtering2The film is placed in a tube furnace, the temperature is raised to 600 ℃ at the speed of 5 ℃/min, the film is roasted for 180mins at high temperature, and SnS can be obtained2A film. SnS2The layer thickness was 370 nm.
SnS prepared by the embodiment2The film and the lithium sheet are assembled into a button cell, and the specific capacity of 400 cycles can still be maintained at 548mAh/g (the capacity retention rate is 76.2 percent, and the coulomb efficiency of the first cycle is 99.1 percent) at room temperature when the battery is discharged at a constant current of 0.5C; showing good cycling performance.
Example 6
Soaking stainless steel sheet in 10 wt% hydrochloric acid for 12 hr, cleaning, wiping with alcohol, and cutting into 2cm × 2cm pieces. Fixing the target material on a target platform, selecting Cr as the target material, carrying out pre-sputtering for 10mins, then removing a baffle, adjusting the power to 20W, and sputtering for 20 mins. The thickness of the Cr layer was 15 nm.
After the primary sputtering is finished, the target material is replaced by the Sn target, and the atmosphere is adjusted to H2And S, after pre-sputtering for 10mins, removing the baffle, adjusting the power to 40W, and sputtering for 60 mins. SnS obtained by sputtering2The film is placed in a tube furnace, the temperature is raised to 700 ℃ at the speed of 5 ℃/min, the film is roasted for 120mins at high temperature, and SnS can be obtained2A film. SnS2The layer thickness was 200 nm.
By adopting the present embodimentThe prepared SnS2 film and lithium sheet are assembled into button cell at room temperature with 2Ag-1During constant-current discharge, the specific capacity of 400 cycles can still be kept at 520mAh/g (capacity retention rate is 75.7%, coulombic efficiency of the first cycle is 99.0%), and relatively good cycle performance is shown.
Comparative example 1:
the comparative example discusses that the buffer layer of the present invention was not added, specifically as follows:
soaking the copper foil in 10 wt% hydrochloric acid for 12h, cleaning, wiping with alcohol, and cutting into 2cm × 2cm pieces. Fixing copper foil on a target table, selecting Sn as a target material, and adjusting the atmosphere to Ar/H2S (1: 8), the baffle is removed after pre-sputtering for 10mins, the power is adjusted to 60W, and sputtering is carried out for 40 mins. SnS obtained by sputtering2The film is placed in a tube furnace, the temperature is raised to 700 ℃ at the speed of 5 ℃/min, the film is roasted for 120mins at high temperature, and SnS can be obtained2A film. SnS2The layer thickness was 400 nm.
SnS prepared by the embodiment2The film and the lithium sheet are assembled into a button cell which is prepared by 2Ag at room temperature-1During constant-current discharge, the specific capacity of 400 cycles is kept at 360mAh/g (the capacity retention rate is 48.5%, the coulombic efficiency of the first cycle is 89.2%), and the cycle performance is reduced.
Comparative example 2:
this comparative example discusses the use of Mn as the buffer material layer as follows:
soaking the copper foil in 10 wt% hydrochloric acid for 12h, cleaning, wiping with alcohol, and cutting into 2cm × 2cm pieces. Fixing the copper foil on a target platform, selecting Mn as a target material, adopting Ar gas as an atmosphere, pre-sputtering for 10mins, then removing a baffle, adjusting the power to 20W, and sputtering for 20 mins. The thickness of the Mn layer was 10 nm.
After the primary sputtering is finished, the target material is replaced by the Sn target, and the atmosphere is adjusted to H2And S, after pre-sputtering for 10mins, removing the baffle, adjusting the power to 40W, and sputtering for 60 mins. SnS obtained by sputtering2The film is placed in a tube furnace, the temperature is raised to 700 ℃ at the speed of 5 ℃/min, the film is roasted for 120mins at high temperature, and SnS can be obtained2A film. SnS2The layer thickness was 200 nm.
SnS prepared by the embodiment2The film and the lithium sheet are assembled into a button cell which is prepared by 2Ag at room temperature-1During constant-current discharge, the specific capacity of 400 cycles is kept at 410mAh/g (capacity retention rate is 55.6%, coulombic efficiency in the first cycle is 89.1%), and the cycle performance is reduced.
Comparative example 3:
in this comparative example, the buffer layer is thicker as follows:
soaking the copper foil in 10 wt% hydrochloric acid for 12h, cleaning, wiping with alcohol, and cutting into 2cm × 2cm pieces. Fixing the copper foil on a target platform, selecting Ti as a target material, carrying out pre-sputtering for 10mins, then removing a baffle, adjusting the power to 80W, and carrying out sputtering for 50mins, wherein the thickness of the sputtered Ti layer is 180 nm.
After the primary sputtering is finished, the target material is replaced by the Sn target, and the atmosphere is adjusted to Ar/H2S (1: 4), the baffle is removed after pre-sputtering for 10mins, the power is adjusted to 60W, and sputtering is carried out for 40 mins. SnS obtained by sputtering2The film is placed in a tube furnace, the temperature is raised to 700 ℃ at the speed of 5 ℃/min, the film is roasted for 120mins at high temperature, and SnS can be obtained2A film. SnS2The layer thickness was 450 nm.
SnS prepared by the embodiment2The film and the lithium sheet are assembled into a button cell which is prepared by 2Ag at room temperature-1During constant-current discharge, the specific capacity of 400 cycles is kept at 380mAh/g (capacity retention rate is 50.7%, coulombic efficiency of the first cycle is 87.7%), and the cycle performance is reduced.
Comparative example 4:
the comparative example is discussed and carried out under the condition of higher power of secondary reactive sputtering, and concretely comprises the following steps:
soaking the copper foil in 10 wt% hydrochloric acid for 12h, cleaning, wiping with alcohol, and cutting into 2cm × 2cm pieces. Fixing the copper foil on a target platform, selecting Cu as a target material, carrying out pre-sputtering for 10mins, then removing a baffle, adjusting the power to 50W, and carrying out sputtering for 10mins, wherein the thickness of the sputtered Cu layer is 20 nm.
After the primary sputtering is finished, the target material is replaced by the Sn target, and the atmosphere is adjusted to Ar/H2S (1: 4), pre-sputtering for 10mins, then moving away the baffle plate, andthe power is adjusted to 100W, and the sputtering time is 60 mins. SnS obtained by sputtering2The film is placed in a tube furnace, the temperature is raised to 700 ℃ at the speed of 5 ℃/min, the film is roasted for 120mins at high temperature, and SnS can be obtained2A film. SnS2The layer thickness was 450 nm.
SnS prepared by the embodiment2The film and the lithium sheet are assembled into a button cell which is filled with 1Ag at room temperature-1During constant-current discharge, the specific capacity of 200 cycles is 300mAh/g (the capacity retention rate is 42.5 percent, the coulombic efficiency of the first cycle is 88.1 percent), and the cycle performance is reduced.
Comparative example 5:
the comparative example is discussed and carried out under the lower power of the secondary reactive sputtering, and concretely comprises the following steps:
soaking the copper foil in 10 wt% hydrochloric acid for 12h, cleaning, wiping with alcohol, and cutting into 2cm × 2cm pieces. Fixing the copper foil on a target platform, selecting Cu as a target material, carrying out pre-sputtering for 10mins, then removing a baffle, adjusting the power to 50W, and carrying out sputtering for 10mins, wherein the thickness of the sputtered Cu layer is 20 nm.
After the primary sputtering is finished, the target material is replaced by the Sn target, and the atmosphere is adjusted to Ar/H2S (1: 4), the baffle is removed after pre-sputtering for 10mins, the power is adjusted to 20W, and sputtering is carried out for 30 mins. And (3) placing the film obtained by sputtering in a tube furnace, heating to 700 ℃ at the speed of 5 ℃/min, and roasting at high temperature for 120 mins.
The film prepared in the example and the lithium sheet are assembled into a button cell and 1Ag is added at room temperature-1In constant current discharge, there is no capacity after cycling, which indicates that there is no SnS2And (4) active substance production.
Comparative example 6:
the comparative example discusses that the proportion of the inert atmosphere is large in the reactive sputtering process, and specifically comprises the following steps:
soaking the copper foil in 10 wt% hydrochloric acid for 12h, cleaning, wiping with alcohol, and cutting into 2cm × 2cm pieces. Fixing the copper foil on a target platform, selecting Ti as a target material, adopting Ar gas as atmosphere, pre-sputtering for 10mins, then removing a baffle, adjusting the power to 30W, and sputtering for 20 mins. The Ti layer thickness was 15 nm.
One-time sputteringAfter the end, the target material is replaced by the Sn target, and the atmosphere is adjusted to Ar/H2S (20: 1), the baffle is removed after pre-sputtering for 10mins, the power is adjusted to 80W, and sputtering is carried out for 30 mins. And (3) placing the SnS2 film obtained by sputtering into a tubular furnace, heating to 800 ℃ at the speed of 5 ℃/min, and roasting at high temperature for 30mins to obtain the SnS2 film. SnS2The layer thickness was 500 nm.
SnS prepared by the embodiment2The film and the lithium sheet are assembled into a button cell which is filled with 1Ag at room temperature-1During constant-current discharge, the specific capacity of 200 cycles can still be kept at 160mAh/g, and the capacity attenuation is large, which indicates that the formed active substance contains simple substance Sn and the volume effect is obvious.
Comparative example 7:
this comparative example discusses annealing at higher temperatures as follows:
soaking the copper foil in 10 wt% hydrochloric acid for 12h, cleaning, wiping with alcohol, and cutting into 2cm × 2cm pieces. Fixing the copper foil on a target platform, selecting Ti as a target material, adopting Ar gas as atmosphere, pre-sputtering for 10mins, then removing a baffle, adjusting the power to 30W, and sputtering for 20 mins. The Ti layer thickness was 15 nm.
After the primary sputtering is finished, the target material is replaced by the Sn target, and the atmosphere is adjusted to Ar/H2S (1: 1), the baffle is removed after pre-sputtering for 10mins, the power is adjusted to 80W, and sputtering is carried out for 30 mins. SnS obtained by sputtering2The film is placed in a tube furnace, the temperature is raised to 1000 ℃ at the speed of 7 ℃/min, the film is roasted for 60mins at high temperature, and SnS can be obtained2A film. SnS2The layer thickness was 500 nm.
SnS prepared by the embodiment2The film and the lithium sheet are assembled into a button cell which is prepared by 2Ag at room temperature-1During constant-current discharge, the specific capacity of 400 cycles can still be maintained at 330mAh/g (capacity retention rate is 44.3%, coulomb efficiency of the first cycle is 85.9%), and the capacity attenuation is large.
Comparative example 8:
the comparative example discusses that SnS is obtained without the reactive sputtering one-step forming required by the present invention2By sputtering Sn first, then H2Reaction under S to SnS2The method comprises the following steps:
soaking the copper foil in 10 wt% hydrochloric acid for 12h, cleaning, wiping with alcohol, and cutting into 2cm × 2cm pieces. Fixing the copper foil on a target platform, selecting Cu as a target material, carrying out pre-sputtering for 10mins, then removing a baffle, adjusting the power to 30W, and sputtering for 20 mins. The Cu layer thickness was 15 nm.
After the first sputtering is finished, the target material is changed into an Sn target, the atmosphere is adjusted to Ar, the baffle is removed after the pre-sputtering is carried out for 10mins, the power is adjusted to 80W, and the sputtering is carried out for 30 mins. Placing the Sn film obtained by sputtering in a tube furnace in H2Heating to 700 ℃ at the speed of 7 ℃/min in the S atmosphere, and roasting at high temperature for 180mins to obtain SnS2A film. SnS2The layer thickness was 390 nm.
SnS prepared by the embodiment2The film and the lithium sheet are assembled into a button cell which is prepared by 2Ag at room temperature-1During constant-current discharge, the specific capacity of 400 cycles is kept at 230mAh/g (capacity retention rate is 31.7%, coulombic efficiency at the first cycle is 89.3%), and the capacity attenuation is large.
Comparative example 9:
comparative example discussion direct sputtering of SnS2The method comprises the following steps:
soaking stainless steel sheet in 10 wt% hydrochloric acid for 12 hr, cleaning, wiping with alcohol, and cutting into 2cm × 2cm pieces. Fixing the copper foil on a target platform, selecting Cu as a target material, carrying out pre-sputtering for 10mins, then removing a baffle, adjusting the power to 30W, and sputtering for 20 mins. The Cu layer thickness was 15 nm.
After the primary sputtering is finished, the target material is replaced by SnS2And adjusting the atmosphere to Ar, pre-sputtering for 10mins, removing the baffle, adjusting the power to 100W, and sputtering for 40 mins. Placing the Sn film obtained by sputtering in a tubular furnace, heating to 600 ℃ at the speed of 5 ℃/min in the Ar gas atmosphere, and roasting at high temperature for 30mins to obtain the SnS2A film. SnS2The layer thickness was 400 nm.
SnS prepared by the embodiment2The film and the lithium sheet are assembled into a button cell which is prepared by 2Ag at room temperature-1During constant-current discharge, the specific capacity of 400 cycles is kept at 390mAh/g (capacity retention rate is 55.2%; first cycle coulombs)Efficiency 94.8%), capacity fade is large.
Comparative example 10:
this comparative example discusses, using a porous current collector, as follows:
soaking foamed nickel in 10 wt% hydrochloric acid for 12 hr, washing, wiping with alcohol, and cutting into 2cm × 2cm pieces. Fixing the copper foil on a target platform, selecting Cu as a target material, carrying out pre-sputtering for 10mins, then removing a baffle, adjusting the power to 30W, and sputtering for 20 mins.
After the primary sputtering is finished, the target material is replaced by the Sn target, and the atmosphere is adjusted to Ar/H2S (1: 4), the baffle is removed after pre-sputtering for 10mins, the power is adjusted to 50W, and sputtering is carried out for 60 mins. SnS obtained by sputtering2The film is placed in a tube furnace, the temperature is raised to 700 ℃ at the speed of 5 ℃/min, the film is roasted for 120mins at high temperature, and SnS can be obtained2A film.
SnS prepared by the embodiment2The film and the lithium sheet are assembled into a button cell which is prepared by 2Ag at room temperature-1During constant-current discharge, the specific capacity of 400 cycles is kept at 415mAh/g (capacity retention rate is 60.9%, coulombic efficiency of the first cycle is 95.2%), the capacity attenuation is large, and active substances are unevenly distributed in a foam-shaped porous material, so that the volume effect is obvious.
In summary, the method of the present invention is particularly suitable for planar metal current collectors, and the buffer layer of at least one of Cu, Ti, Pt and Cr is pre-compounded on the surface of the planar metal current collector, and then the buffer layer is matched with the subsequent steps to perform the steps of Sn and H2S one-step reactive sputtering can unexpectedly obtain SnS with exposed (0,0,1) crystal face2An active material layer, the material having excellent electrical properties.

Claims (6)

1. SnS2The negative electrode of the thin film lithium battery is characterized by comprising a current collector, a metal buffer layer compounded on the surface of the current collector, and an active material layer compounded on the metal buffer layer;
the metal buffer layer is made of metal with a lattice constant of 3.6-4.7 and conductivity;
the active material layer is made of exposed (0,0,1)SnS of crystal face2；
The metal buffer layer is made of at least one of Cu, Ti, Pt and Cr;
the current collector is copper foil, stainless steel, nickel foil, iron foil, molybdenum foil, zinc foil, nickel-titanium alloy or noble metal foil;
the thickness of the metal buffer layer is 10-50 nm; the thickness of the active material layer is 200-500 nm.
2. The SnS of claim 12The preparation method of the negative electrode of the thin film lithium battery is characterized by comprising the following steps of:
step (1): sputtering a material of the metal buffer layer on the surface of the current collector by utilizing magnetron sputtering, and forming the metal buffer layer on the surface of the current collector; the buffer layer is made of one or more of Cu, Ti, Pt and Cr, and the thickness of the sputtered buffer layer is 10-50 nm;
step (2): the current collector compounded with the metal buffer layer is used as a substrate, Sn is used as a target material, and H is contained in the current collector2S, performing reactive sputtering in the atmosphere to form an active material layer on the metal buffer layer; 40-80W of reactive sputtering process; said compound comprises H2The atmosphere of S is H2S atmosphere or is H2S-a mixed atmosphere of inert gas;
H2in a mixed atmosphere of S-inert gas, inert gas/H2The ratio of S is 1:10-10: 1; the thickness of the reactive sputtering active material layer is 200-500 nm;
and (3): annealing the material obtained in the step (2) to obtain the SnS2A thin film lithium battery cathode;
the temperature of the annealing treatment is 500-800 ℃.
3. The SnS of claim 22The preparation method of the thin film lithium battery cathode is characterized in that in the step (1), the sputtering power is 10-50W, and the sputtering time is 10-30 mins.
4. The SnS of claim 22Thin film lithium battery negative electrodeThe preparation method of the electrode is characterized in that in the step (2), the time of reactive sputtering is 10-60 mins.
5. The SnS of claim 22The preparation method of the film lithium battery cathode is characterized in that in the step (3), the annealing is carried out in a protective atmosphere, and the annealing heat preservation time is 30-180 mins.
6. The SnS of claim 12Thin film lithium battery cathode or SnS prepared by the preparation method of any one of claims 2 to 52The application of the negative electrode of the thin film lithium battery is characterized in that the negative electrode is used as a film negative electrode, and the film negative electrode, a diaphragm and a film positive electrode are assembled into the thin film lithium battery.
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Publication number Priority date Publication date Assignee Title
CN101157851B (en) * 2007-08-28 2010-05-19 华中师范大学 Preparation method of quantum dot self-assembling nano structural material
CN102054961A (en) * 2010-07-22 2011-05-11 中信国安盟固利动力科技有限公司 Active negative pole piece and preparation method thereof
CN102790212B (en) * 2011-05-18 2014-09-24 国家纳米科学中心 Lithium ion battery cathode active material, preparation method of the lithium ion battery cathode active material, cathode material and cathode
JP5945790B2 (en) * 2012-02-27 2016-07-05 株式会社日本マイクロニクス Method for producing alloy for CZTS solar cell
CN103682368B (en) * 2012-09-20 2016-08-17 中国科学院金属研究所 A kind of flexible lithium ion battery filled soon and the preparation method of electrode thereof
CN102903891B (en) * 2012-10-12 2014-11-19 上海中聚佳华电池科技有限公司 Negative material SnOxS2-x/graphene composite for lithium ion battery and preparation method thereof
CN105428699B (en) * 2014-09-23 2018-04-03 中国科学院大连化学物理研究所 A kind of composite structured lithium-sulfur cell
US20160197352A1 (en) * 2015-01-07 2016-07-07 Ford Global Technologies, Llc. Physiochemical Pretreatment for Battery Current Collector
CN106549082B (en) * 2015-09-21 2019-07-05 云南师范大学 The method that alloys target and sulfide target cosputtering prepare copper-zinc-tin-sulfur film absorbed layer
CN105226258B (en) * 2015-11-06 2017-08-15 杭州电子科技大学 A kind of negative electrode of lithium ion battery composite film material and preparation method thereof
CN105826569A (en) * 2016-05-24 2016-08-03 深圳市国创新能源研究院 Lithium battery current collector and preparing method thereof
CN105977334B (en) * 2016-07-07 2017-06-06 许昌学院 A kind of preparation method of stannic disulfide/trisulfides two tin/stannous sulfide hetero-junction thin-film
CN106450296B (en) * 2016-09-30 2019-04-12 北京科技大学 A kind of SnS of (101) crystal face preferential growth2The preparation method of nanometer sheet negative electrode material
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