CN110034278A - A kind of SnS2Film lithium cell cathode and its preparation and application - Google Patents
A kind of SnS2Film lithium cell cathode and its preparation and application Download PDFInfo
- Publication number
- CN110034278A CN110034278A CN201810033576.6A CN201810033576A CN110034278A CN 110034278 A CN110034278 A CN 110034278A CN 201810033576 A CN201810033576 A CN 201810033576A CN 110034278 A CN110034278 A CN 110034278A
- Authority
- CN
- China
- Prior art keywords
- sns
- sputtering
- film
- buffer layer
- lithium cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C23C14/0623—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
Abstract
The invention belongs to thin-film material technical fields, specifically disclose a kind of SnS2Film lithium cell cathode, including collector are compounded in the metal buffer layer of collection liquid surface, and the active material layer being compounded on metal buffer layer;The material of the metal buffer layer is lattice constant metal conductive between 3.6-4.7;The material of the active material layer is the SnS of exposure (0,0,1) crystal face2.The invention also discloses the SnS2The preparation method of film lithium cell cathode, splash-proofing sputtering metal buffer layer on a current collector in advance, then again with Sn in H2Reactive sputtering under S obtains the active material layer of the structure in metal buffer layer surface one-step shaping.The invention also discloses the applications of the cathode.The film and lithium piece are assembled into button cell, it was demonstrated that the material shows excellent chemical property, and electrode polarization can be effectively reduced, and improves the energy density and cyclical stability of battery.
Description
Technical field
The present invention relates to a kind of SnS2The preparation method of film lithium ion battery electrode, belongs to field of lithium ion battery.
Background technique
The energy is that material base is wanted in developing national economy and the life uplifted the people's living standard, and directly affects economic hair
One key factor of exhibition.Since the 21th century, shortage of resources, environmental pollution brought by traditional energy utilization patterns,
The problems such as greenhouse effects, becomes increasingly conspicuous, and improves energy resource structure, develops efficient, clean new energy and has become global common recognition.Lithium
Ion battery receives the blueness of people due to superior performances such as its is safe and environment-friendly, high-energy-density and good chemical properties
It looks at.For energy miniaturization and the emerging integrated requirement of composite energy storage system, the lithium-ion electric for meeting traditional microelectronic device
Pond is further development of film lithium ion battery ultra-thin, flexible, with high-energy density.
Lithium metal film can be used as the cathode of film lithium ion battery, but the fusing point of lithium is low, to air-sensitive, easily by
Oxidation, and cathode of lithium will appear Li dendrite and grow up, form " dead lithium " or cause internal short-circuit of battery etc., these defects limit
The application of lithium film cathode.At present it is low and be not easy filming etc. and lack then to there is energy density in the carbon negative electrode material that commercially uses
Point, it is also difficult to meet the requirement of film lithium ion micro cell high-energy density.
Although the Si base cathode of commercialization at present has a high capacity, the addition of noble metal improve it is related at
This, this also significantly limits the large-scale production of such catalyst, therefore sight has been transferred to metal material catalysis by people
In agent.The main reason for Sn base negative electrode material is concerned is that Sn has very high lithium storage content.Currently, membrane electrode is used
Volume change of the pure Sn material in process of intercalation it is very big, Volumetric expansion is serious, therefore in order to overcome pure Sn film negative
The problem of pole poor circulation, researcher have turned to the preparation and research of Sn-M system intermetallic compound or complex thin film.
WeixiangChen (Journal ofPower Sources, 2012,201:259-266) is compounded with using graphene hydro-thermal
SnS2, composite material capacity with higher and good cyclical stability.But such preparation method is not suitable for control system
Standby material thickness, can not effectively prepare membrane electrode.Gabriel M.Veith (Journal of Power Sources,
2014,267:329-336) SnSb membrane electrode is prepared for using the method for magnetron sputtering, this electrode presents better
Chemical property, but this kind of directly sputtering active material prepares method material prepared more difficult to control of membrane electrode
Structure and specific function, it is suppressed that the performance of material activity.
In conclusion this field is badly in need of developing a kind of preparation for being simple and efficient and can preparing specific morphology Sn base film electrode
Method has the hot research topic of membrane electrode preparation always this field of high-energy density and excellent cycle performance.
Summary of the invention
To solve technical problem of the existing technology, an object of the present disclosure is, provides a kind of SnS2Thin film lithium electricity
A kind of pond cathode (present invention is also referred to as film lithium cell cathode, or referred to as cathode), it is desirable to provide film that electric property is excellent
Cathode.
Second purpose of the invention is, provides the SnS2The preparation method of film lithium cell cathode, it is desirable to provide
A kind of preparation method that can well control active layer crystalline structure and pattern.
Third purpose of the present invention is, provides the SnS2Film lithium cell cathode answering in film lithium ion battery
With.
A kind of SnS2Film lithium cell cathode, including collector, compound metal buffer layer on a current collector and compound
In the active material layer of metal buffer layer surface;
The material of the metal buffer layer is lattice constant metal conductive between 3.6-4.7;
The material of the active material layer is the SnS of exposure (0,0,1) crystal face2。
Material of the present invention, active material layer have (0,0,1) crystal plane structure, and active material layer is without passing through bonding
The energy density of battery entirety can be improved in the compound adhesion of agent, the active material layer of the crystal plane structure, and material can be greatly improved
Capacity and cycle performance;In addition, being provided with metal buffer layer between active material layer and collector, help to promote material
Structural stability, buffers active material layer bring bulk effect in charge and discharge process.
Preferably, the active material layer can part lower limit to metal buffer layer or be compounded in metal buffer layer table
Face.
Preferably, SnS2Film lithium cell cathode, active material layer are compounded in metal buffer layer surface.
Preferably, the collector is stable metal collector under low potential, for example, can for copper foil, stainless steel,
Nickel foil, iron foil, molybdenum foil, zinc foil, Nitinol, noble metal paillon.
Further preferably, the collector is copper foil, stainless steel, nickel foil, iron foil or molybdenum foil.
The buffer layer of the metal of lattice parameter of the present invention can induce the SnS with (0,0,1) crystal face2It is formed.
In addition, " buffering " active material bring bulk effect in charge and discharge process to a certain extent.
Preferably, the material of the metal buffer layer is Cu, Ti, Pt, at least one of Cr.These preferred gold
Belong to electric conductivity be better than other it is non-select metal, and its mechanical performance is also more prominent.
Preferably, the metal buffer layer with a thickness of 10-50nm.Under the metal buffer layer of the preferred thickness,
More conducively induce SnS2Form and buffer volume expansion;If buffer layer is excessively thin, inducing action can not be played;If buffer layer is blocked up,
It will lead to interface impedance increase, reduce the energy density and cyclical stability of the membrane electrode.
Preferably, the active material layer with a thickness of 200-500nm.In the active material layer of the preferred thickness
Under, the electric property of cathode is more excellent, and if active material layer is excessively thin, bulk effect is obvious;If active material layer is blocked up, material deposition
Biggish graininess is presented, design feature can not be embodied.
For the SnS well controlled2The structure and morphology of film lithium cell cathode is further ensured that cathode obtained
Electric property, the invention also discloses the SnS described in one kind2The preparation method of film lithium cell cathode, comprising the following steps:
Step (1): it using magnetron sputtering in the material of collection liquid surface splash-proofing sputtering metal buffer layer, is formed in collection liquid surface
Metal buffer layer;
Step (2): it using the collector for being compounded with metal buffer layer as substrate, uses Sn as target, is including H2The gas of S
Reactive sputtering in atmosphere forms active material layer on metal buffer layer;The 40-80W of reactive sputtering process;
Step (3): the material that step (2) obtains is made annealing treatment, and obtains the SnS2Film lithium cell cathode.
The present invention provides the preparation methods that one kind can prepare specific morphology Sn base film electrode, and this method is by afflux
Body splash-proofing sputtering metal buffer layer, obtains the collector of pre-sputtering;Further reactive sputtering SnS on it2, then carry out at annealing
Reason, is exposed the SnS of (0,0,1) crystal face2Film.Using the method for the present invention, specific morphology (exposure (0,0,1) can be prepared
The SnS of crystal face2) Sn base film cathode;And the technical issues of being unable to control negative pole structure the method overcome conventional method, it uses
The method of the present invention helps that electrode capacity height, the film cathode of good cycling stability, in addition, the method for the present invention also has is made
The advantages that simple process, controllable type are strong, low in cost has great prospects for commercial application.
This method is prepared for exposure (0,0,1) crystal face on the basis of buffer layer, using one one-step inducing of magnetron sputtering
SnS2Material, this method have the effect that 1. this method are simple, easily prepare, and repeatability is high.2. the presence of buffer layer can be with
Induce SnS2Formation, while buffers active substance bring bulk effect in charge and discharge process to a certain extent.3. (0,
0,1) crystal face is the advantage interface of lithium ion transport, and the capacity and cycle performance of material can be greatly improved.4. free bonding agent
The energy density of battery entirety can be improved in active material layer.
Preparation method of the present invention passes sequentially through primary sputtering (magnetron sputtering described in step (1)) metal buffer layer, secondary
Reactive sputtering (present invention is also referred to as reactive sputtering) SnS2Active material layer after the high temperature anneal, is exposed (0,0,1) crystalline substance
The SnS in face2Film.
In the present invention, collector preprocessing process preprocessed, described in advance before magnetron sputtering are as follows: use collector
Diluted acid impregnates, through deionized water washing, drying after.
Preferably, diluted acid is hydrochloric acid, one or both of sulfuric acid, concentration 5-15wt%.High concentrated acid can corrode
Copper foil surface causes surface uneven, influences the uniformity for sputtering at film above, and then influence its chemical property.
In order to obtain the active material layer with good crystalline form, pattern, with dominance structure of the present invention, the present invention
Originally form the metal buffer layer on a current collector in advance;It sputters obtained metal buffer layer and effectively reduces active matter
Contact resistance between matter and pole piece, while being grown induction of active material along particular crystal orientation.The secondary sputtering on the buffer layer
Active material can be grown along particular crystal orientation, show special construction, enhance the discharge process of the material, it is close to improve energy
Degree and cyclical stability.
Preferably, the material of the metal buffer layer is that lattice constant has superior electrical conductivity between 3.6-4.7
Metal;One or more of further preferably Cu, Ti, Pt, Cr.
Preferably, in step (1), sputtering power 10-50W, sputtering time 10-30mins.Sputtering power and when
Between will have a direct impact on metal buffer thickness degree, if buffer layer is excessively thin, induced crystal growth can not be played the role of;If buffer layer mistake
It is excessive to also result in contact impedance for thickness.
Preparation method of the present invention it is another it is critical that comprising including H2Under the atmosphere of S, under the sputtering power
Direct reactive sputtering compared to preparatory sputtering Sn, then reacts into SnS2Deng technology, using this hair style directly in metal buffer layer
Upper reactive sputtering obtains SnS2, can the work of the purpose crystal plane structure unexpectedly be formed in the metal buffer layer surface
Property material layer, can be obviously improved the cycle performance and first circle coulombic efficiency of cathode.
In the present invention, that described includes H2The atmosphere of S is H2S atmosphere, or be H2The mixed atmosphere of S- inert gas.
Preferably, H2In the mixed atmosphere of S- inert gas, inert gas/H2The ratio of S is 1: 10-10: 1.
The inert gas is, for example, other inert gases such as argon gas.Under the mixed atmosphere, facilitate slow in metal
Rush the active material layer that layer surface forms the dominance structure.In mixed atmosphere, when the content of inert gas is higher, active material
Layer can the unreacted Sn of doped portion.
Further preferably, that described includes H2The atmosphere of S is H2S or Ar/H2S, wherein Ar/H2The ratio of S is 1: 10-10:
1;The excessively high SnS that will lead to preparation of Ar gas ratio2Purity is too low, is contaminated with unreacted Sn.
In step (2), the power of reactive sputtering process needs to control between 40-80W.Sputtering power will have a direct impact on work
Property material layer thickness, if active material layer is excessively thin, bulk effect is obvious;If active material layer is blocked up, material deposition presents larger
Graininess, design feature can not be embodied.In addition, sputtering power and reaction rate have direct relation, and under certain condition, sputtering
Power is too low, can not generate the charged particle of Sn;Sputtering power is excessively high, has metal simple-substance generation.
In step (2), under the conditions of the preferred reactive sputtering, preferred sputtering time is 10-60mins.It is preferred at this
Sputtering time under, the performance of obtained cathode is more excellent.
Preferably, the annealing carries out under protective atmosphere in step (3);Protective atmosphere is preferably nitrogen
Or argon gas.
Preferably, the temperature of annealing is 500-800 DEG C in step (3).The selection of annealing temperature and corresponding system
Under SnS2Stability is related, and at the preferred temperature, the crystal plane structure that reactive sputtering can be kept to obtain helps to be promoted
The electric property of the material of the cathode arrived;If temperature is excessively high, alloying reaction easily occurs between Sn and Cu;If temperature is too low,
SnS2It can not recrystallize, crystal structure is imperfect.
Preferably, in step (3), the heating rate for being 2-7 DEG C/min with heating rate is warming up to the annealing temperature
Degree.
Under the annealing temperature, soaking time 30-180mins.
Under annealing process of the present invention, the active material with the advantage crystalline structure can further be made
Layer, facilitates the electric property for further promoting obtained cathode.
A kind of preferred preparation method of the present invention, the specific steps are as follows:
Step a: copper foil is impregnated after cutting with diluted acid, and the copper foil after cleaning is dried after being washed repeatedly with deionized water.
Step b: the copper foil after cleaning is fixed on target platform, sputters one layer of buffering in the case where filling Ar atmosphere using magnetron sputtering
Layer, with a thickness of 10-50nm.
Step c: the copper foil obtained using step b is fixed on target platform, as substrate using magnetron sputtering in particular atmosphere
Lower secondary response sputters active material layer, and target selects Sn target, sputters with a thickness of 200-500nm.
Step d: pole piece obtained by step c is made annealing treatment under protective atmosphere.
The film lithium ion battery electrode preparation method of technical solution of the present invention preparation is with respect to Sn base prepared by conventional method
Membrane electrode has architectural characteristic more outstanding, can effectively inhibit Volumetric expansion, improves lithium ion transport efficiency, into
And electrode polarization can be effectively reduced, improve cell discharge performance and cyclical stability.
Compared with the prior art, technical solution of the present invention bring the utility model has the advantages that
(1) technical solution of the present invention directly sputters the SnS of specific structure with reactive sputtering2, effectively inhibit volume
Bulking effect improves lithium ion transport efficiency, is effectively reduced electrode polarization, improves cell discharge performance and cyclical stability.
(2) buffer layer in film lithium ion battery electrode prepared by the present invention can effectively reduce collector and activity
Contact impedance between substance, while can be grown with induced activity substance along particular crystal orientation, there is good guiding performance, accelerate brilliant
Body generates.
(3) film lithium ion battery electrode prepared by the present invention includes three-decker, and intermediate buffer layer, which plays, to be glued
Effect is connect, active material is caducous during solving the problems, such as conventional sputter, while the presence of this sandwich structure improves
Stability of the electrode in cyclic process improves battery performance.
(4) the method degree of repeatability for preparing film lithium ion battery electrode of the invention is high, and simple process can give birth on a large scale
It produces.
Detailed description of the invention
Fig. 1 is the SEM figure that embodiment 1 obtains film;
Fig. 2 is the XRD diagram for the film that embodiment 1 obtains;
Fig. 3 is the SnS that embodiment 1 obtains2The constant current charge-discharge performance map of the lithium ion battery of membrane electrode assembling;
Specific embodiment
Following embodiment is intended to be described in further details the content of present invention, rather than protects to the claims in the present invention
The limitation of range.
Following embodiment and comparative example, unless specified or limited otherwise, the parameter of magnetron sputtering and reactive sputtering process can be selected
Conventional parameter, for example, sputtering pressure is, for example, 0.4~3Pa, gas flow rate is, for example, 10-50sccm, target at a distance from substrate
For example, 8-14cm.
Embodiment 1:
Copper foil is immersed in 12h in the hydrochloric acid of 10wt%, is cut into the small pieces of 2cm × 2cm after cleaning with wipes of alcohol dry doubling.
Copper foil is fixed on target platform, target selects Ti, and atmosphere is Ar gas, removes baffle after pre-sputtering 10mins, is by power adjustment
20W sputters 20mins, sputters Ti layers at this time with a thickness of 10nm.
After primary sputtering, replacement target is Sn target, and atmosphere is adjusted to Ar/H2S (1: 4), pre-sputtering 10mins
After remove baffle, by power adjustment be 60W, sputter 40mins.The SnS that sputtering is obtained2Film is placed in tube furnace, with 5 DEG C/
The rate of min is warming up to progress high-temperature roasting 120mins at 700 DEG C, and SnS can be obtained2Film.SnS2Layer is with a thickness of 450nm.
Using SnS manufactured in the present embodiment2Membrane electrode and lithium piece are assembled into button cell, in LAND CT-2001A type
Cycle performance test is carried out on charge-discharge test instrument.Button cell test is carried out at 25 DEG C of room temperature condition, voltage range
For 0.01-2.0V, current density 2Ag-1.Its process and chemical property are as shown in the figure:
Fig. 1 is that the SEM of the membrane electrode schemes.It is edge by the method that the petal-like structures showed in figure know the Material growth
What particular crystal orientation occurred.
Fig. 2 is the XRD diagram of the film active material.By with SnS2Standard card (JCPDS 22-0951) comparison is consistent
It closes, wherein (001) diffraction maximum is particularly evident, it was demonstrated that its good crystallinity.
Fig. 3 shows to prepare SnS using this method2Membrane electrode, at room temperature with 2Ag-1When constant-current discharge, 400 circle of circulation
Specific capacity may remain in 580mAh/g (capacity retention ratio 78.4%;First circle coulombic efficiency 99.2%), show good follow
Ring performance.
Embodiment 2
Copper foil is immersed in 12h in the hydrochloric acid of 10wt%, is cut into the small pieces of 2cm × 2cm after cleaning with wipes of alcohol dry doubling.
Copper foil is fixed on target platform, target selects Cu, and atmosphere is Ar gas, removes baffle after pre-sputtering 10mins, is by power adjustment
50W sputters 10mins.Cu layers with a thickness of 20nm.
After primary sputtering, replacement target is Sn target, and atmosphere is adjusted to Ar/H2S (1: 8), pre-sputtering 10mins
After remove baffle, by power adjustment be 60W, sputter 40mins.The SnS that sputtering is obtained2Film is placed in tube furnace, with 5 DEG C/
The rate of min is warming up to progress high-temperature roasting 120mins at 700 DEG C, and SnS can be obtained2Film.SnS2Layer is with a thickness of 400nm.
Using SnS manufactured in the present embodiment2Film and lithium piece are assembled into button cell, at room temperature, with 2Ag-1Constant current is put
When electric, 400 circle specific capacity of circulation may remain in 500mAh/g (capacity retention ratio 75.3%;First circle coulombic efficiency 99.1%),
Show good cycle performance.
Embodiment 3
Copper foil is immersed in 12h in the hydrochloric acid of 10wt%, is cut into the small pieces of 2cm × 2cm after cleaning with wipes of alcohol dry doubling.
Copper foil is fixed on target platform, target selects Ti/Cr, and atmosphere is Ar gas, baffle is removed after pre-sputtering 10mins, by power adjustment
For 30W, 20mins is sputtered.Ti/Cr layers with a thickness of 50nm.
After primary sputtering, replacement target is Sn target, and atmosphere is adjusted to Ar/H2S (1: 1), pre-sputtering 10mins
After remove baffle, by power adjustment be 80W, sputter 30mins.The SnS that sputtering is obtained2Film is placed in tube furnace, with 5 DEG C/
The rate of min is warming up to progress high-temperature roasting 30mins at 800 DEG C, and SnS can be obtained2Film.SnS2Layer is with a thickness of 500nm.
Using SnS manufactured in the present embodiment2Film and lithium piece are assembled into button cell, at room temperature, with 2Ag-1Constant current is put
When electric, 400 circle specific capacity of circulation may remain in 524mAh/g (capacity retention ratio 75.9%;First circle coulombic efficiency 99.2%);
Show good cycle performance.
Embodiment 4
Copper foil is immersed in 12h in the hydrochloric acid of 10wt%, is cut into the small pieces of 2cm × 2cm after cleaning with wipes of alcohol dry doubling.
Copper foil is fixed on target platform, target selects Cr, and atmosphere is Ar gas, removes baffle after pre-sputtering 10mins, is by power adjustment
20W sputters 20mins.Cr layers with a thickness of 10nm.
After primary sputtering, replacement target is Sn target, and atmosphere is adjusted to H2Gear is removed after S, pre-sputtering 10mins
Power adjustment is 40W, sputters 60mins by plate.The SnS that sputtering is obtained2Film is placed in tube furnace, with the speed of 5 DEG C/min
Rate is warming up to progress high-temperature roasting 120mins at 700 DEG C, and SnS can be obtained2Film.SnS2Layer is with a thickness of 200nm.
Using SnS manufactured in the present embodiment2Film and lithium piece are assembled into button cell, at room temperature, with 2Ag-1Constant current is put
When electric, 400 circle specific capacity of circulation may remain in 550mAh/g (capacity retention ratio 76.3%;First circle coulombic efficiency 99.1%);
Show good cycle performance.
Embodiment 5
Copper foil is immersed in 12h in the hydrochloric acid of 10wt%, is cut into the small pieces of 2cm × 2cm after cleaning with wipes of alcohol dry doubling.
Copper foil is fixed on target platform, target selects Pt, and atmosphere is Ar gas, removes baffle after pre-sputtering 10mins, is by power adjustment
10W sputters 30mins.Pt layers with a thickness of 32nm.
After primary sputtering, replacement target is Sn target, and atmosphere is adjusted to Ar/H2S (1: 6), pre-sputtering 10mins
After remove baffle, by power adjustment be 70W, sputter 20mins.The SnS that sputtering is obtained2Film is placed in tube furnace, with 5 DEG C/
The rate of min is warming up to progress high-temperature roasting 180mins at 600 DEG C, and SnS can be obtained2Film.SnS2Layer is with a thickness of 370nm.
Using SnS manufactured in the present embodiment2Film and lithium piece are assembled into button cell, at room temperature, are put with 0.5C constant current
When electric, 400 circle specific capacity of circulation may remain in 548mAh/g (capacity retention ratio 76.2%;First circle coulombic efficiency 99.1%);
Show good cycle performance.
Embodiment 6
Stainless steel substrates are immersed in 12h in the hydrochloric acid of 10wt%, are cut into 2cm × 2cm's with wipes of alcohol dry doubling after cleaning
Small pieces.It is fixed on target platform, target selects Cr, and atmosphere is Ar gas, baffle is removed after pre-sputtering 10mins, by power adjustment
For 20W, 20mins is sputtered.Cr layers with a thickness of 15nm.
After primary sputtering, replacement target is Sn target, and atmosphere is adjusted to H2Gear is removed after S, pre-sputtering 10mins
Power adjustment is 40W, sputters 60mins by plate.The SnS that sputtering is obtained2Film is placed in tube furnace, with the speed of 5 DEG C/min
Rate is warming up to progress high-temperature roasting 120mins at 700 DEG C, and SnS can be obtained2Film.SnS2Layer is with a thickness of 200nm.
Button cell is assembled into using SnS2 film manufactured in the present embodiment and lithium piece, at room temperature, with 2Ag-1Constant current is put
When electric, 400 circle specific capacity of circulation may remain in 520mAh/g (capacity retention ratio 75.7%;First circle coulombic efficiency 99.0%),
Show better cycle performance.
Comparative example 1:
This comparative example is inquired into, and buffer layer of the invention is not added with, specific as follows:
Copper foil is immersed in 12h in the hydrochloric acid of 10wt%, is cut into the small pieces of 2cm × 2cm after cleaning with wipes of alcohol dry doubling.
Copper foil is fixed on target platform, target selects Sn, and atmosphere is adjusted to Ar/H2Gear is removed after S (1: 8), pre-sputtering 10mins
Power adjustment is 60W, sputters 40mins by plate.The SnS that sputtering is obtained2Film is placed in tube furnace, with the speed of 5 DEG C/min
Rate is warming up to progress high-temperature roasting 120mins at 700 DEG C, and SnS can be obtained2Film.SnS2Layer is with a thickness of 400nm.
Using SnS manufactured in the present embodiment2Film and lithium piece are assembled into button cell, at room temperature, with 2Ag-1Constant current is put
When electric, 400 circle specific capacity of circulation is maintained at 360mAh/g (capacity retention ratio 48.5%;First circle coulombic efficiency 89.2%), circulation
Performance is declined.
Comparative example 2:
This comparative example is inquired into, specific as follows using Mn as cushioned material layer:
Copper foil is immersed in 12h in the hydrochloric acid of 10wt%, is cut into the small pieces of 2cm × 2cm after cleaning with wipes of alcohol dry doubling.
Copper foil is fixed on target platform, target selects Mn, and atmosphere is Ar gas, removes baffle after pre-sputtering 10mins, is by power adjustment
20W sputters 20mins.Mn layers with a thickness of 10nm.
After primary sputtering, replacement target is Sn target, and atmosphere is adjusted to H2Gear is removed after S, pre-sputtering 10mins
Power adjustment is 40W, sputters 60mins by plate.The SnS that sputtering is obtained2Film is placed in tube furnace, with the speed of 5 DEG C/min
Rate is warming up to progress high-temperature roasting 120mins at 700 DEG C, and SnS can be obtained2Film.SnS2Layer is with a thickness of 200nm.
Using SnS manufactured in the present embodiment2Film and lithium piece are assembled into button cell, at room temperature, with 2Ag-1Constant current is put
When electric, 400 circle specific capacity of circulation is maintained at 410mAh/g (capacity retention ratio 55.6%;First circle coulombic efficiency 89.1%), circulation
Performance is declined.
Comparative example 3:
This comparative example is inquired into, and the thickness of buffer layer is thicker, specific as follows:
Copper foil is immersed in 12h in the hydrochloric acid of 10wt%, is cut into the small pieces of 2cm × 2cm after cleaning with wipes of alcohol dry doubling.
Copper foil is fixed on target platform, target selects Ti, and atmosphere is Ar gas, removes baffle after pre-sputtering 10mins, is by power adjustment
80W sputters 50mins, sputters Ti layers at this time with a thickness of 180nm.
After primary sputtering, replacement target is Sn target, and atmosphere is adjusted to Ar/H2S (1: 4), pre-sputtering 10mins
After remove baffle, by power adjustment be 60W, sputter 40mins.The SnS that sputtering is obtained2Film is placed in tube furnace, with 5 DEG C/
The rate of min is warming up to progress high-temperature roasting 120mins at 700 DEG C, and SnS can be obtained2Film.SnS2Layer is with a thickness of 450nm.
Using SnS manufactured in the present embodiment2Film and lithium piece are assembled into button cell, at room temperature, with 2Ag-1Constant current is put
When electric, 400 circle specific capacity of circulation is maintained at 380mAh/g (capacity retention ratio 50.7%;First circle coulombic efficiency 87.7%), circulation
Performance is declined.
Comparative example 4:
This comparative example is inquired into, and is carried out under the power of higher secondary response sputtering, specific as follows:
Copper foil is immersed in 12h in the hydrochloric acid of 10wt%, is cut into the small pieces of 2cm × 2cm after cleaning with wipes of alcohol dry doubling.
Copper foil is fixed on target platform, target selects Cu, and atmosphere is Ar gas, removes baffle after pre-sputtering 10mins, is by power adjustment
50W sputters 10mins, sputters Cu layers at this time with a thickness of 20nm.
After primary sputtering, replacement target is Sn target, and atmosphere is adjusted to Ar/H2S (1: 4), pre-sputtering 10mins
After remove baffle, by power adjustment be 100W, sputter 60mins.The SnS that sputtering is obtained2Film is placed in tube furnace, with 5
DEG C/rate of min is warming up to progress high-temperature roasting 120mins at 700 DEG C, SnS can be obtained2Film.SnS2Layer with a thickness of
450nm。
Using SnS manufactured in the present embodiment2Film and lithium piece are assembled into button cell, at room temperature, with 1Ag-1Constant current is put
When electric, 200 circle specific capacity of circulation is in 300mAh/g (capacity retention ratio 42.5%;First circle coulombic efficiency 88.1%), cycle performance
Declined.
Comparative example 5:
This comparative example is inquired into, and is carried out under the power of lower secondary response sputtering, specific as follows:
Copper foil is immersed in 12h in the hydrochloric acid of 10wt%, is cut into the small pieces of 2cm × 2cm after cleaning with wipes of alcohol dry doubling.
Copper foil is fixed on target platform, target selects Cu, and atmosphere is Ar gas, removes baffle after pre-sputtering 10mins, is by power adjustment
50W sputters 10mins, sputters Cu layers at this time with a thickness of 20nm.
After primary sputtering, replacement target is Sn target, and atmosphere is adjusted to Ar/H2S (1: 4), pre-sputtering 10mins
After remove baffle, by power adjustment be 20W, sputter 30mins.Sputtering is obtained film to be placed in tube furnace, with 5 DEG C/min's
Rate is warming up to progress high-temperature roasting 120mins at 700 DEG C.
Button cell is assembled into using film manufactured in the present embodiment and lithium piece, at room temperature, with 1Ag-1When constant-current discharge,
There is no capacity after circulation, illustrates that there is no SnS2Active material production.
Comparative example 6:
This comparative example is inquired into, and in reactive sputtering process, the large percentage of inert atmosphere is specific as follows:
Copper foil is immersed in 12h in the hydrochloric acid of 10wt%, is cut into the small pieces of 2cm × 2cm after cleaning with wipes of alcohol dry doubling.
Copper foil is fixed on target platform, target selects Ti, and atmosphere is Ar gas, removes baffle after pre-sputtering 10mins, is by power adjustment
30W sputters 20mins.Ti layers with a thickness of 15nm.
After primary sputtering, replacement target is Sn target, and atmosphere is adjusted to Ar/H2S (20: 1), pre-sputtering 10mins
After remove baffle, by power adjustment be 80W, sputter 30mins.The obtained SnS2 film of sputtering is placed in tube furnace, with 5 DEG C/
The rate of min is warming up to progress high-temperature roasting 30mins at 800 DEG C, and SnS2 film can be obtained.SnS2Layer is with a thickness of 500nm.
Using SnS manufactured in the present embodiment2Film and lithium piece are assembled into button cell, at room temperature, with 1Ag-1Constant current is put
When electric, 200 circle specific capacity of circulation may remain in 160mAh/g, and capacity attenuation is larger, illustrates there is list in the active material to be formed
Matter Sn, bulk effect are obvious.
Comparative example 7:
This comparative example is inquired into, and is annealed at a higher temperature, specific as follows:
Copper foil is immersed in 12h in the hydrochloric acid of 10wt%, is cut into the small pieces of 2cm × 2cm after cleaning with wipes of alcohol dry doubling.
Copper foil is fixed on target platform, target selects Ti, and atmosphere is Ar gas, removes baffle after pre-sputtering 10mins, is by power adjustment
30W sputters 20mins.Ti layers with a thickness of 15nm.
After primary sputtering, replacement target is Sn target, and atmosphere is adjusted to Ar/H2S (1: 1), pre-sputtering 10mins
After remove baffle, by power adjustment be 80W, sputter 30mins.The SnS that sputtering is obtained2Film is placed in tube furnace, with 7 DEG C/
The rate of min is warming up to progress high-temperature roasting 60mins at 1000 DEG C, and SnS can be obtained2Film.SnS2Layer is with a thickness of 500nm.
Using SnS manufactured in the present embodiment2Film and lithium piece are assembled into button cell, at room temperature, with 2Ag-1Constant current is put
When electric, 400 circle specific capacity of circulation may remain in 330mAh/g (capacity retention ratio 44.3%;First circle coulombic efficiency 85.9%),
Capacity attenuation is larger.
Comparative example 8:
This comparative example is inquired into, and does not obtain SnS using reactive sputtering one-step shaping of the presently claimed invention2, by first sputtering
Sn, then H again2Reaction is at SnS under S2, it is specific as follows:
Copper foil is immersed in 12h in the hydrochloric acid of 10wt%, is cut into the small pieces of 2cm × 2cm after cleaning with wipes of alcohol dry doubling.
Copper foil is fixed on target platform, target selects Cu, and atmosphere is Ar gas, removes baffle after pre-sputtering 10mins, is by power adjustment
30W sputters 20mins.Cu layers with a thickness of 15nm.
After primary sputtering, replacement target is Sn target, and atmosphere is adjusted to Ar, and gear is removed after pre-sputtering 10mins
Power adjustment is 80W, sputters 30mins by plate.The Sn film that sputtering obtains is placed in tube furnace, in H2With 7 under the atmosphere of S
DEG C/rate of min is warming up to progress high-temperature roasting 180mins at 700 DEG C, SnS can be obtained2Film.SnS2Layer with a thickness of
390nm。
Using SnS manufactured in the present embodiment2Film and lithium piece are assembled into button cell, at room temperature, with 2Ag-1Constant current is put
When electric, 400 circle specific capacity of circulation is maintained at 230mAh/g (capacity retention ratio 31.7%;First circle coulombic efficiency 89.3%), capacity
Decay larger.
Comparative example 9:
This comparative example is inquired into, directly sputtering SnS2, it is specific as follows:
Stainless steel substrates are immersed in 12h in the hydrochloric acid of 10wt%, are cut into 2cm × 2cm's with wipes of alcohol dry doubling after cleaning
Small pieces.Copper foil is fixed on target platform, target selects Cu, and atmosphere is Ar gas, baffle is removed after pre-sputtering 10mins, by power tune
Whole is 30W, sputters 20mins.Cu layers with a thickness of 15nm.
After primary sputtering, replacement target is SnS2Target, and atmosphere is adjusted to Ar, gear is removed after pre-sputtering 10mins
Power adjustment is 100W, sputters 40mins by plate.The Sn film that sputtering obtains is placed in tube furnace, under the atmosphere of Ar gas
It is warming up to progress high-temperature roasting 30mins at 600 DEG C with the rate of 5 DEG C/min, SnS can be obtained2Film.SnS2Layer with a thickness of
400nm。
Using SnS manufactured in the present embodiment2Film and lithium piece are assembled into button cell, at room temperature, with 2Ag-1Constant current is put
When electric, 400 circle specific capacity of circulation is maintained at 390mAh/g (capacity retention ratio 55.2%;First circle coulombic efficiency 94.8%), capacity
Decay larger.
Comparative example 10:
This comparative example is inquired into, specific as follows using porous current collector:
Nickel foam is immersed in 12h in the hydrochloric acid of 10wt%, is cut into the small of 2cm × 2cm with wipes of alcohol dry doubling after cleaning
Piece.Copper foil is fixed on target platform, target selects Cu, and atmosphere is Ar gas, baffle is removed after pre-sputtering 10mins, by power adjustment
For 30W, 20mins is sputtered.
After primary sputtering, replacement target is Sn target, and atmosphere is adjusted to Ar/H2S (1: 4), pre-sputtering 10mins
After remove baffle, by power adjustment be 50W, sputter 60mins.The SnS that sputtering is obtained2Film is placed in tube furnace, with 5 DEG C/
The rate of min is warming up to progress high-temperature roasting 120mins at 700 DEG C, and SnS can be obtained2Film.
Using SnS manufactured in the present embodiment2Film and lithium piece are assembled into button cell, at room temperature, with 2Ag-1Constant current is put
When electric, 400 circle specific capacity of circulation is maintained at 415mAh/g (capacity retention ratio 60.9%;First circle coulombic efficiency 95.2%), capacity
Decay larger, wherein active material is unevenly distributed in foam-like porous material, causes bulk effect obvious.
To sum up to analyze, the method for the present invention is especially suitable for planar metal collector, and in advance in its surface recombination Cu, Ti,
The buffer layer of at least one of Pt, Cr, then cooperate subsequent step in Sn and H2The sputtering of S single step reaction, unexpected can be had
There is the SnS of exposure (0,0,1) crystal face2Active material layer, the material have excellent electric property.
Claims (10)
1. a kind of SnS2Film lithium cell cathode, which is characterized in that including collector, be compounded in the metal buffer of collection liquid surface
Layer, and the active material layer being compounded on metal buffer layer;
The material of the metal buffer layer is lattice constant metal conductive between 3.6-4.7;
The material of the active material layer is the SnS of exposure (0,0,1) crystal face2。
2. SnS as described in claim 12Film lithium cell cathode, which is characterized in that the material of the metal buffer layer is
At least one of Cu, Ti, Pt, Cr.
3. SnS as described in claim 12Film lithium cell cathode, which is characterized in that the collector is metal collector,
Preferably copper foil, stainless steel, nickel foil, iron foil, molybdenum foil, zinc foil, Nitinol or noble metal paillon.
4. SnS as claimed in any one of claims 1 to 32Film lithium cell cathode, which is characterized in that the metal buffer layer
With a thickness of 10-50nm;The active material layer with a thickness of 200-500nm.
5. a kind of described in any item SnS of Claims 1 to 42The preparation method of film lithium cell cathode, which is characterized in that including
Following steps:
Step (1): using magnetron sputtering in the material of collection liquid surface splash-proofing sputtering metal buffer layer, metal is formed in collection liquid surface
Buffer layer;
Step (2): it using the collector for being compounded with metal buffer layer as substrate, uses Sn as target, is including H2In the atmosphere of S
Reactive sputtering forms active material layer on metal buffer layer;The 40-80W of reactive sputtering process;
Step (3): the material that step (2) obtains is made annealing treatment, and obtains the SnS2Film lithium cell cathode.
6. SnS as claimed in claim 52The preparation method of film lithium cell cathode, which is characterized in that described in step (1)
The material of buffer layer is Cu, Ti, Pt, one or more of Cr, sputtering power 10-50W, sputtering time 10-30mins;
The thickness of the buffer layer of sputtering is preferably 10-50nm.
7. SnS as claimed in claim 52The preparation method of film lithium cell cathode, which is characterized in that described in step (2)
Include H2The atmosphere of S is H2S atmosphere, or be H2The mixed atmosphere of S- inert gas;
H2In the mixed atmosphere of S- inert gas, inert gas/H2The ratio of S is preferably 1: 10-10: 1.
8. SnS as claimed in claim 72The preparation method of film lithium cell cathode, which is characterized in that in step (2), reaction
The time of sputtering is 10-60mins;The active material layer of reactive sputtering with a thickness of 200-500nm.
9. SnS as claimed in claim 52The preparation method of film lithium cell cathode, which is characterized in that described in step (3)
Annealing carried out under protective atmosphere, the temperature of annealing is 500-800 DEG C, soaking time 30-180mins.
10. a kind of described in any item SnS of Claims 1 to 42Any one of film lithium cell cathode or claim 5~9 institute
SnS made from the preparation method stated2The application of film lithium cell cathode, which is characterized in that be used as film cathode and diaphragm, film just
Pole is assembled into film lithium cell.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810033576.6A CN110034278B (en) | 2018-01-12 | 2018-01-12 | SnS2Thin film lithium battery cathode, preparation and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810033576.6A CN110034278B (en) | 2018-01-12 | 2018-01-12 | SnS2Thin film lithium battery cathode, preparation and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110034278A true CN110034278A (en) | 2019-07-19 |
CN110034278B CN110034278B (en) | 2022-04-05 |
Family
ID=67234520
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810033576.6A Active CN110034278B (en) | 2018-01-12 | 2018-01-12 | SnS2Thin film lithium battery cathode, preparation and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110034278B (en) |
Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101157851A (en) * | 2007-08-28 | 2008-04-09 | 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 |
CN102790212A (en) * | 2011-05-18 | 2012-11-21 | 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 |
CN102903891A (en) * | 2012-10-12 | 2013-01-30 | 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 |
CN103682368A (en) * | 2012-09-20 | 2014-03-26 | 中国科学院金属研究所 | Rapidly charged flexible lithium ion battery and preparation method of electrodes of rapidly charged flexible lithium ion battery |
CN104245573A (en) * | 2012-02-27 | 2014-12-24 | 日本麦可罗尼克斯股份有限公司 | Method for fabricating alloy for czts solar cell |
CN105226258A (en) * | 2015-11-06 | 2016-01-06 | 杭州电子科技大学 | A kind of lithium ion battery negative composite film material and preparation method thereof |
CN105428699A (en) * | 2014-09-23 | 2016-03-23 | 中国科学院大连化学物理研究所 | Lithium-sulfur battery with composite structure |
CN105762327A (en) * | 2015-01-07 | 2016-07-13 | 福特全球技术公司 | Physiochemical pretreatment for battery current collector |
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 |
CN105977334A (en) * | 2016-07-07 | 2016-09-28 | 许昌学院 | Method for preparing stannic sulfide/ antimony trisulfide/stannous sulfide heterojunction film |
CN106450296A (en) * | 2016-09-30 | 2017-02-22 | 北京科技大学 | Preparation method of SnS2 nanosheet negative electrode material preferably growing along (101) crystal face |
CN106549082A (en) * | 2015-09-21 | 2017-03-29 | 云南师范大学 | The method that alloys target prepares copper-zinc-tin-sulfur film absorbed layer with sulfide target cosputtering |
CN107452939A (en) * | 2017-01-04 | 2017-12-08 | 中国地质大学(北京) | A kind of high power capacity flexible lithium ion battery negative material and preparation method thereof |
-
2018
- 2018-01-12 CN CN201810033576.6A patent/CN110034278B/en active Active
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101157851A (en) * | 2007-08-28 | 2008-04-09 | 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 |
CN102790212A (en) * | 2011-05-18 | 2012-11-21 | 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 |
CN104245573A (en) * | 2012-02-27 | 2014-12-24 | 日本麦可罗尼克斯股份有限公司 | Method for fabricating alloy for czts solar cell |
CN103682368A (en) * | 2012-09-20 | 2014-03-26 | 中国科学院金属研究所 | Rapidly charged flexible lithium ion battery and preparation method of electrodes of rapidly charged flexible lithium ion battery |
CN102903891A (en) * | 2012-10-12 | 2013-01-30 | 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 |
CN105428699A (en) * | 2014-09-23 | 2016-03-23 | 中国科学院大连化学物理研究所 | Lithium-sulfur battery with composite structure |
CN105762327A (en) * | 2015-01-07 | 2016-07-13 | 福特全球技术公司 | Physiochemical pretreatment for battery current collector |
CN106549082A (en) * | 2015-09-21 | 2017-03-29 | 云南师范大学 | The method that alloys target prepares copper-zinc-tin-sulfur film absorbed layer with sulfide target cosputtering |
CN105226258A (en) * | 2015-11-06 | 2016-01-06 | 杭州电子科技大学 | A kind of lithium ion battery negative 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 |
CN105977334A (en) * | 2016-07-07 | 2016-09-28 | 许昌学院 | Method for preparing stannic sulfide/ antimony trisulfide/stannous sulfide heterojunction film |
CN106450296A (en) * | 2016-09-30 | 2017-02-22 | 北京科技大学 | Preparation method of SnS2 nanosheet negative electrode material preferably growing along (101) crystal face |
CN107452939A (en) * | 2017-01-04 | 2017-12-08 | 中国地质大学(北京) | A kind of high power capacity flexible lithium ion battery negative material and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN110034278B (en) | 2022-04-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111224115B (en) | Zinc-based battery negative electrode and preparation and application thereof | |
CN108695488A (en) | Zinc oxide-lithium metal composite negative pole and preparation method, lithium metal secondary battery | |
CN101222047B (en) | Cathode material of thin film lithium ion battery and method for producing the same | |
CN105226258A (en) | A kind of lithium ion battery negative composite film material and preparation method thereof | |
CN107785586A (en) | Three-dimensional porous copper/graphene composite current collector for secondary metals cathode of lithium battery | |
CN101414674A (en) | Cathode material for lithium ion battery tin/carbon nanometer multilayer film, and preparation method and application thereof | |
CN112909229A (en) | Silver coating method of three-dimensional lithium-philic metal foam framework and preparation method of application of silver coating method in lithium metal negative electrode | |
CN101339989A (en) | Aluminum-tin alloy film for lithium ionic cell negative electrode and method for preparing the same | |
CN103606683B (en) | Germanium nano material of a kind of Coiling-type and preparation method thereof | |
CN209747642U (en) | lithium-copper composite electrode and secondary battery | |
CN100353594C (en) | Metal oxide electrode material for producing adulterant utilizing electro-deposition-heat treatment technology | |
CN111769251A (en) | Method for protecting metal electrode | |
CN103400980A (en) | Iron sesquioxide/nickel oxide core-shell nanorod array film as well as preparation method and application thereof | |
CN112018394A (en) | Lithium-copper composite electrode and preparation method and application thereof | |
CN112421115B (en) | Lithium metal-based battery with copper selenide in-situ coated foam copper as lithium metal carrier and preparation method thereof | |
CN110034273B (en) | Sn-based sulfide and/or nitride modified tin oxide thin-film lithium battery cathode and preparation and application thereof | |
CN105552320B (en) | A kind of Ni-based Sn/SnO/SnO of foam2Three-dimensional porous negative electrode material of stratiform and preparation method thereof | |
CN108987673B (en) | Lithium negative electrode containing conductive protection film and preparation method and application thereof | |
CN110034278A (en) | A kind of SnS2Film lithium cell cathode and its preparation and application | |
CN113046795B (en) | Three-dimensional flexible zinc cathode with three-dimensional titanium structure and long service life, and preparation method and application thereof | |
CN111162283A (en) | Preparation method and application of nano porous foamed nickel current collector | |
CN110029317A (en) | A kind of preparation method of CZTSSe film and its application in lithium ion battery | |
CN110034271A (en) | A kind of CZTS film lithium cell cathode and its preparation and application | |
CN114335559B (en) | Lithium metal battery current collector and preparation method and application thereof | |
WO2023070872A1 (en) | Negative-electrode-free zinc ion hybrid capacitor and preparation method therefor |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |