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CN109346723A - Preparation method of lithium-ion battery based on molybdenum foil-supported molybdenum disulfide nanosheet array structure - Google Patents

Preparation method of lithium-ion battery based on molybdenum foil-supported molybdenum disulfide nanosheet array structure Download PDF

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CN109346723A
CN109346723A CN201811204440.3A CN201811204440A CN109346723A CN 109346723 A CN109346723 A CN 109346723A CN 201811204440 A CN201811204440 A CN 201811204440A CN 109346723 A CN109346723 A CN 109346723A
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lithium
molybdenum foil
ion battery
electrolyte
battery
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彭志坚
郭飞
郭一飞
符秀丽
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China University of Geosciences Beijing
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China University of Geosciences Beijing
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Condensed Matter Physics & Semiconductors (AREA)
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Abstract

本发明涉及一种基于钼箔负载的MoS2纳米片阵列结构的锂离子电池的制备方法，属于新能源材料及其器件制备技术领域。本发明以MoO3和S粉为蒸发源，通过简单的一步化学气相沉积法，直接在钼箔上生长出MoS2纳米片阵列结构，并将其直接用作锂离子电池的阳极材料；配合金属锂箔阴极、隔膜、电解液等直接组装成了锂离子电池。采用本技术制备的锂离子电池阳极材料，MoS2纳米片阵列结构产量大、纯度高、结晶性好、形貌规整；MoS2纳米片阵列结构紧密地结合在钼箔上；且合成生长条件严格可控、设备和工艺简单、成本低。采用本技术制备锂离子电池，过程简单、环境友好、无污染、无需后处理；且这种新型锂离子电池比容量高，充放电循环稳定性稳定。

The invention relates to a preparation method of a lithium ion battery based on a MoS2 nanosheet array structure supported by molybdenum foil, and belongs to the technical field of new energy materials and device preparation. In the invention, MoO3 and S powder are used as evaporation sources, and MoS2 nanosheet array structure is directly grown on molybdenum foil by a simple one-step chemical vapor deposition method, and it is directly used as anode material of lithium ion battery; Lithium foil cathode, separator, electrolyte, etc. are directly assembled to form a lithium ion battery. The anode material of lithium ion battery prepared by this technology has the advantages of large yield, high purity, good crystallinity and regular morphology of MoS 2 nanosheet array structure; the MoS 2 nanosheet array structure is closely combined on the molybdenum foil; and the synthesis and growth conditions are strict Controllable, simple equipment and process, and low cost. The lithium-ion battery prepared by this technology has the advantages of simple process, environment-friendly, no pollution and no post-treatment; and the new lithium-ion battery has high specific capacity and stable charge-discharge cycle stability.

Description

The system of the lithium ion battery of molybdenum disulfide nano sheet array structure based on molybdenum foil load Preparation Method
Technical field
The present invention relates to a kind of preparations of the lithium ion battery of molybdenum disulfide nano sheet array structure based on molybdenum foil load Method belongs to new energy materials and its device preparation technical field.
Background technique
Lithium ion battery has many advantages, such as density is big, specific power is high, is widely used, it is considered to be next For mixed motivity type automobile or the ideal functionality device of electric vehicle, anode material therein is the commercialized key of lithium ion battery One of material.Currently, commercialized anode material is mainly graphite material, but its theoretical specific capacity only has 372mAh/ g.Further, since its problems such as there are safety and cycle lives, constrain it in extensive energy storage and electric car field Extensive use.Therefore, seek the anode material that a kind of specific capacity is high, good cycle and high rate performance are excellent, for mentioning High-lithium ion battery performance has great importance.
Molybdenum disulfide (MoS2) it is used as a kind of typical class graphene transient metal sulfide, because of its unique excellent electricity The performances such as, calorifics, mechanics receive significant attention in fields such as new energy, electronic device and photoelectric conversions.MoS2Theoretical hold Measure higher, about 670mAh/g；And it has many advantages, such as relatively low volume change, rich reserves and at low cost.But make For lithium ion battery anode material, MoS2Poor electric conductivity inhibit charge its lithium ion energy storage position and external circuit it Between transfer ability, and then influence the performance of its specific capacity and high rate performance.Recent studies indicate that relative to block material Material, MoS2Nano structural material is conducive to improve the high rate performance and stable circulation performance of lithium ion battery, because of nanostructure There is material big specific surface area and high mechanical strength can effectively shorten when as lithium ion battery anode material The diffusion path of lithium ion promotes its insertion and abjection；Surface area that can be bigger with exposed material, thus provide more lithiums from The channel of son insertion and abjection；The cyclical stability that lithium ion battery can be improved is effectively prevented from volume in charge and discharge process Expansion and structure destroy (H.Hwang, et al.MoS2nanoplates consisting of disordered graphene-like layers for high rate lithium battery anode materials.Nano Letters,2011,11:4826-4830)。
However, the electrode material as lithium ion battery, traditional method be all by electrode material and polymer bonding agent, The mixing such as conductive black, is then uniformly coated in conductive current collector.This Fabrication Technology of Electrode will increase the series connection of electrode Resistance, the diffusion for inhibiting electrolyte and coming into full contact with for electrolyte and active material is interfered, thus reduces the multiplying power of lithium battery Performance and cycle performance.In order to overcome these disadvantages, there is document to propose and directly grow into active material nano array structure As the method for electrode on collector matrix, this unique self-supporting electrode can promote the electric conductivity of electrode entirety, thus Promote charge-discharge performance (S.Chen, et the al.Self-supported Li of battery4Ti5O12nanosheet arrays for lithium ion batteries with excellent rate capability and ultralong cycle life.Energy Environmental Science,2014,7:1924-1930)；In addition, nano structural material is directly grown On a current collector, the mechanical strength that electrode can be improved is effectively prevented from reunion and shape of the active material in charge and discharge process Cash as, and then promoted lithium ion battery cyclical stability；Also, the excellent collector matrix of electric conductivity is directly as electricity Pole, assembly operation is easier, cheap.In short, in conjunction with MoS2Class graphene stratiform architectural characteristic, develop a kind of high Effect, easy method directly grow MoS on collector matrix2Nano-chip arrays structural material, and be used as in lithium ion The anode of battery will have Important Project value.
Therefore, the invention proposes a kind of MoS based on molybdenum foil load2The system of the lithium ion battery of nano-chip arrays structure Preparation Method.The present invention is using molybdenum trioxide and sulphur powder as evaporation source, by simple step chemical vapour deposition technique, directly in molybdenum foil On grow high-purity, high density, high crystalline MoS2Nano-chip arrays structure, and it is directly used as lithium ion battery Anode material；Complexed metal lithium foil cathode, diaphragm, electrolyte, direct-assembling is at lithium ion in the glove box of argon gas filling Battery.The lithium ion battery anode material prepared using the method, MoS2The yield of nano-chip arrays structure is big, purity is high, ties Crystalline substance is good, regular appearance；MoS2It is incorporated on molybdenum foil to nano-chip arrays close structure；And synthesis growth conditions it is stringent controllable, It is equipment and simple process, low in cost.Lithium ion battery is prepared using the method, preparation process is simple, it is environmental-friendly, without dirt Dye is not necessarily to post-processing；And this new type lithium ion battery proposed by the present invention, specific capacity is big, battery first time specific discharge capacity Up to 1041mAh/g, also there is good cyclical stability and high rate performance, be a kind of lithium-ion electric with excellent properties Pond.
Summary of the invention
It is an object of the invention to propose a kind of MoS based on molybdenum foil load2The lithium ion battery of nano-chip arrays structure Preparation method.This technology passes through essence using molybdenum trioxide and sulphur powder as evaporation source using simple step chemical vapour deposition technique The synthesis technologic parameter of true control directly grows vertical, ultra-thin MoS on molybdenum foil2Nano-chip arrays structure (nanometer Wall)；Then, by this anode material for being directly used as lithium ion battery with height-oriented, ordering growth nano structural material Expect (self-supporting anode is constituted together with molybdenum foil), metallic lithium foil is assembled with electrolyte, diaphragm and battery case and made as cathode At high performance lithium ion battery.The MoS prepared using the method2Nano-chip arrays structure anode material, MoS2Nano-chip arrays The yield of structure is big, density is high, with high purity, good crystallinity, regular appearance；MoS2It is incorporated in molybdenum to nano-chip arrays close structure On foil；And synthesis growth conditions is stringent controllable, equipment and simple process, low in cost.Lithium ion battery is prepared using the method, Preparation process is simple, it is environmental-friendly, pollution-free, without post-processing, it is economic and environment-friendly；And this new type lithium ion proposed by the present invention Battery, specific capacity is big, and battery first time specific discharge capacity also has good cyclical stability and multiplying power up to 1041mAh/g Performance is a kind of lithium ion battery with excellent properties.
MoS proposed by the present invention based on molybdenum foil load2The preparation method of the lithium ion battery of nano-chip arrays structure, It is characterized in that, the battery uses and grows vertical, ultra-thin MoS on molybdenum foil2Nano-chip arrays structure is as self-supporting sun Pole directly assembles with metallic lithium foil cathode, diaphragm, electrolyte, battery case；The self-supporting anode is with molybdenum trioxide With sulphur powder be evaporation source, by simple step chemical vapour deposition technique, the high-purity directly grown on molybdenum foil, high density, High crystalline, vertical, ultra-thin MoS2Nano-chip arrays structure.
MoS proposed by the present invention based on molybdenum foil load2The preparation method of the lithium ion battery of nano-chip arrays structure, packet Include following steps and content:
(1) in vacuum tube furnace, pretreated molybdenum foil is tipped upside down on equipped with the pure MoO of analysis3The aluminium oxide ceramics of powder On crucible, and the central heating region of tube furnace is placed it in, then will be placed equipped with the alumina ceramic crucible for analyzing pure S powder Distance is equipped with MoO above air-flow3At the crucible 14-20cm of powder.
(2) before heating, 0.02Pa first is evacuated to whole system hereinafter, being then passed through height into system with vacuum pump Pure argon is as carrier gas and protects gas, remaining oxygen in removal system.When heating, added with the heating rate of 10-20 DEG C/min Heat arrives 600-700 DEG C, then keeps the temperature 0.5-1.5 hours；In entire heating process, it is continually fed into 100-150 standard cube li The high-purity argon gas of rice (sccm) per minute, until the MoS that cooled to room temperature loads to get molybdenum foil2Nano-chip arrays structure Sample.
(3) in vacuum glove box, by the MoS of obtained molybdenum foil load2Nano-chip arrays structure sample be used as lithium from The anode of sub- battery analyzes pure metal lithium foil as cathode, and assembled with electrolyte, diaphragm and battery case etc..In group Before dress, 10 first are evacuated to entire vacuum glove box-3Pa lays equal stress on hereinafter, being then passed through high-purity argon gas thereto as protection gas It is multiple multiple, to the air in removal system.In an assembling process, the MoS first loaded obtained molybdenum foil2Nanometer sheet battle array Array structure sample is directly placed into battery case, electrolyte is then added, then be sequentially placed into diaphragm and metallic lithium foil, is covered outer Battery is finally sealed by shell.
(4) outer packing is carried out to battery.
In the above preparation method, in the step (1) molybdenum foil pretreating process are as follows: by molybdenum foil successively in 0.5- Dilute hydrochloric acid, acetone and the EtOH Sonicate of 2.5mol/L cleans 10 minutes, then dries spare.Wherein, hydrochloric acid, acetone and ethyl alcohol are equal For ommercially available AR.
In the above preparation method, molybdenum foil is commercially available common conductive metals in the step (1), with a thickness of 0.05- 0.15mm, size and shape are consistent with commercial li-ion battery case.
In the above preparation method, evaporation source MoO in the step (1)3Powder and S powder are ommercially available AR, are used Amount is respectively 100-140mg and 500-600mg.
In the above preparation method, in the step (1) sample and raw material setting are as follows: in vacuum tube furnace, Pretreated molybdenum foil is tipped upside down on equipped with the pure MoO of analysis3On the alumina ceramic crucible of powder, and place it in tube furnace Heating region is entreated, then distance above air-flow will be placed on equipped with the alumina ceramic crucible for analyzing pure S powder and MoO is housed3Powder At crucible 14-20cm.
In the above preparation method, carrier gas and protection gas are high-purity argon gas in the step (2), and purity exists 99.99vol.% or more, flow are 100-150 sccm (sccm).
In the above preparation method, heating process in the step (2) are as follows: heated with the heating rate of 10-20 DEG C/min To 600-700 DEG C, 0.5-1.5 hours then are kept the temperature, finally naturally cools to room temperature.
In the above preparation method, in the step (3), the MoS of obtained molybdenum foil load2Nano-chip arrays structure sample Product directly as lithium ion battery anode, without carrying out any post-processing.
In the above preparation method, in the step (3), the metallic lithium foil as cathode is ommercially available AR.
In the above preparation method, in the step (3), electrolyte is made of electrolyte and organic solvent.Wherein, it is electrolysed Matter is lithium hexafluoro phosphate (LiPF6), lithium perchlorate (LiClO4), LiBF4 (LiBF4) one kind；Organic solvent is carbonic acid Vinyl acetate (EC), the mixed solution of EC and dimethyl carbonate (DMC), the mixed solution of EC and diethyl carbonate (DEC), EC, DMC With one kind of the mixed solution of methyl ethyl ester (EMC).
In the above preparation method, in the step (3), the diaphragm in lithium battery is polyethylene porous membrane, polypropylene is more One kind of pore membrane, polyvinylidene fluoride porous film, cellulose laminated film.
In the above preparation method, according to solid and gel electrolyte in the step (3), then electrolyte is played simultaneously With the effect of diaphragm, solid electrolyte material can be LiPON compound (LiPON), Li at this time0.5La0.5TiO3Or polymer One kind of electrolyte.
In the above preparation method, in the step (3), battery case is high insulating rigid material.
In the above preparation method, in the step (3), the argon gas as protection gas is high-purity gas, and purity exists 99.99vol.% or more.
In the above preparation method, in the step (3), before assembling, 10 first are evacuated to entire vacuum glove box- 3Then Pa is hereinafter, being passed through high-purity argon gas as protection gas thereto and being repeated as many times, to the air in removal system.
In the above preparation method, in the step (3), lithium ion battery sealing after must do so without leakage, it is air tight, Leakproof.
In the above preparation method, in the step (4), prepared lithium ion battery is button, pillar, case in appearance One kind of formula or All-solid film batteries.
One of the advantages of the present invention is: the MoS prepared using this technology2In nano-chip arrays structure anode material, MoS2 The yield of nano-chip arrays structure is big, density is high, with high purity, good crystallinity, regular appearance；MoS2Nano-chip arrays close structure Ground is incorporated on molybdenum foil；And synthesis growth conditions is strictly controllable, equipment and simple process, product yield is high, production process cleaning Environmental protection, it is low in cost.
The two of advantages of the present invention are: lithium ion battery is prepared using this technology, preparation process is simple, it is environmental-friendly, It is pollution-free, without post-processing, it is economic and environment-friendly；And this new type lithium ion battery proposed by the present invention, specific capacity is big, battery first Secondary specific discharge capacity also has good cyclical stability and high rate performance up to 1041mAh/g, is a kind of with excellent properties Lithium ion battery.
Detailed description of the invention
Fig. 1 is the MoS of the load of molybdenum foil obtained by the embodiment of the present invention 12The x-ray diffraction pattern of nano-chip arrays structure
Fig. 2 is the MoS of the load of molybdenum foil obtained by the embodiment of the present invention 12The stereoscan photograph of nano-chip arrays structure
Fig. 3 is the MoS based on molybdenum foil load obtained by the embodiment of the present invention 12The lithium-ion electric of nano-chip arrays structure The structural schematic diagram in pond
Fig. 4 is the MoS based on molybdenum foil load obtained by the embodiment of the present invention 12The lithium-ion electric of nano-chip arrays structure The charging and discharging curve in pond
Specific embodiment
Below with reference to embodiment, technical scheme is described further.
The present invention proposes a kind of MoS based on molybdenum foil load2The preparation method of the lithium ion battery of nano-chip arrays structure, It is characterized in that, the battery is used grows vertical, ultra-thin MoS on molybdenum foil2Nano-chip arrays structure is as self-supporting Anode directly assembles with metallic lithium foil cathode, diaphragm, electrolyte, battery case；The self-supporting anode is with three oxidations Molybdenum and sulphur powder are evaporation source, the high-purity directly grown on molybdenum foil, highly dense by simple step chemical vapour deposition technique Degree, high crystalline, vertical, ultra-thin MoS2Nano-chip arrays structure；Include the following steps and content:
(1) in vacuum tube furnace, 10 points will be successively cleaned by ultrasonic with the dilute hydrochloric acid, acetone and ethyl alcohol of 0.5-2.5mol/L The drying molybdenum foil of the pretreated 0.05-0.15mm thickness of clock, which is tipped upside down on, analyzes pure MoO equipped with 100-140mg3The aluminium oxide of powder is made pottery On porcelain crucible, and the central heating region of tube furnace is placed it in, the aluminium oxide of pure S powder then will be analyzed equipped with 500-600mg Ceramic crucible is placed on distance above air-flow and MoO is housed3At the crucible 14-20cm of powder.
(2) before heating, 0.02Pa first is evacuated to whole system hereinafter, being then passed through into system pure with vacuum pump High-purity argon gas of the degree in 99.99vol.% or more as carrier gas and protects gas, remaining oxygen in removal system.When heating, with The heating rate of 10-20 DEG C/min is heated to 600-700 DEG C, then keeps the temperature 0.5-1.5 hours；In entire heating process, hold The continuous high-purity argon gas for being passed through 100-150 sccm (sccm), until cooled to room temperature is negative to get molybdenum foil The MoS of load2Nano-chip arrays structure sample, it is spare.
(3) preparation of lithium-ion battery module.Electrolyte in lithium ion battery is made of electrolyte and organic solvent, Middle electrolyte is lithium hexafluoro phosphate (LiPF6), lithium perchlorate (LiClO4), LiBF4 (LiBF4) one kind；Organic solvent For ethylene carbonate (EC), the mixed solution of EC and dimethyl carbonate (DMC), the mixed solution of EC and diethyl carbonate (DEC), One kind of the mixed solution of EC, DMC and methyl ethyl ester (EMC).Diaphragm in lithium ion battery be polyethylene porous membrane, One kind of polypropylene porous film, polyvinylidene fluoride porous film, cellulose laminated film.According to solid and gel electrolyte, then Play the effect of electrolyte and diaphragm simultaneously, at this time solid electrolyte material can for LiPON compound (LiPON), Li0.5La0.5TiO3Or one kind of polymer dielectric.The shell of lithium ion battery is high insulating rigid material.
(4) battery assembly.In vacuum glove box, by the MoS of obtained molybdenum foil load2Nano-chip arrays structure sample Anode as lithium ion battery analyzes pure metal lithium foil as cathode, and carry out group with electrolyte, diaphragm and battery case etc. Dress.Before assembling, 10 first are evacuated to entire vacuum glove box-3Then Pa hereinafter, be passed through high-purity argon gas as guarantor thereto It protects gas and is repeated as many times, to the air in removal system.In an assembling process, the MoS first loaded obtained molybdenum foil2 Nano-chip arrays structure sample is directly placed into battery case, electrolyte is then added, then be sequentially placed into diaphragm and metallic lithium foil, Shell is covered, is finally sealed battery.Lithium ion battery after sealing must do so without leakage, air tight, leakproof.
(5) outer packing is carried out to battery.Final prepared lithium ion battery is button in appearance, pillar, box or complete Solid-state thin-film battery.
The MoS of obtained molybdenum foil load2Nano-chip arrays structure sample is black thin film sample in appearance.X-ray is spread out Penetrate analysis shows, this material be high-purity, the good MoS of crystallinity2Phase (see Fig. 1).Under a scanning electron microscope, in molybdenum Foil surface is it is observed that ultra-thin MoS highdensity, vertical-growth, in a crisscross manner2Nano-chip arrays structure (nm wall), receives Rice piece thickness about 10nm (see Fig. 2).
Cyclic charging and discharging test shows that obtained this lithium ion battery specific capacity is big, battery first time electric discharge specific volume It measures up to 1041mAh/g, and also there is good cyclical stability and high rate performance.
In short, the MoS based on molybdenum foil load can be prepared with this technology2The high performance lithium of nano-chip arrays structure from Sub- battery.
Embodiment 1: in vacuum tube furnace, pure MoO will be analyzed equipped with 120mg3The alumina ceramic crucible of powder is placed on Tube furnace center heating region, then the molybdenum foil (thickness 0.08mm) of Φ 19mm size is buckled on this crucible.Then it will be equipped with The alumina ceramic crucible that 550mg analyzes pure S powder is placed on air-flow upstream distance equipped with MoO3At the crucible 16cm of powder.It is heating Before, being first just evacuated to 0.02Pa to whole system with vacuum pump, (purity exists hereinafter, being then passed through high-purity argon gas into system 99.99vol.% or more), and be so repeated 3 times.Then tube furnace is raised to 650 DEG C with the rate of 15 DEG C/min, and keeps the temperature 60 Minute.In entire heating process, it is continually fed into the high-purity argon gas of 100 sccms (sccm), until nature It is cooled to room temperature the MoS to get molybdenum foil load2Nano-chip arrays structure sample.
The MoS that resulting molybdenum foil is loaded2Nano-chip arrays structure sample directly as lithium ion battery anode, 0.8 The metallic lithium foil of × 0.6cm size is as cathode, 1mol/L LiPF6(solvent volume is than EC and DEC for 1:1) is as electrolysis Liquid, polyethylene porous membrane are that diaphragm, button cell shell etc. are placed into vacuum glove box structural schematic diagram group as shown in Figure 3 Dress up button cell.
Before assembling, 10 first are evacuated to entire vacuum glove box-3Then Pa hereinafter, be passed through high-purity argon gas work thereto It for protection gas and is repeated as many times, to the air in removal system.In an assembling process, obtained molybdenum foil is loaded first MoS2Nano-chip arrays structure sample is directly placed into battery case, electrolyte is then added, then be sequentially placed into diaphragm and metal Lithium foil, covers shell.Battery is sealed.Finally carry out outer packing.
X-ray diffraction analysis shows, the MoS of synthesized this molybdenum foil load2Nano-chip arrays structural material is high-purity Degree, the good six sides MoS of crystallinity2Phase (see Fig. 1).Under a scanning electron microscope, on molybdenum foil surface it is observed that high density Vertical-growth, ultra-thin MoS2Nano-chip arrays structure (nm wall), nanometer sheet thickness about 10nm (see Fig. 2).
The MoS that prepared button is loaded based on molybdenum foil2The lithium ion battery of nano-chip arrays structure, in 0.01-3V electricity Cyclic charging and discharging test is carried out under pressure, 0.1A/g current density, charge-discharge performance is good (see Fig. 4), and specific capacity is big, battery first Secondary specific discharge capacity also has good cyclical stability and high rate performance up to 1041mAh/g, is a kind of high performance lithium Ion battery.

Claims (3)

1.基于钼箔负载的MoS2纳米片阵列结构的锂离子电池的制备方法，其特征在于，所述电池采用在钼箔上生长出垂直、超薄的MoS2纳米片阵列结构作为自支撑阳极，直接与金属锂箔阴极、隔膜、电解液、电池外壳组装而成；所述自支撑阳极是以三氧化钼和硫粉为蒸发源，通过简单的一步化学气相沉积法，直接在钼箔上生长的高纯度、高密度、高结晶性、垂直、超薄的MoS2纳米片阵列结构；包括以下步骤：1. A method for preparing a lithium-ion battery based on a MoS nanosheet array structure supported by molybdenum foil, wherein the battery uses a vertical, ultra - thin MoS nanosheet array structure grown on molybdenum foil as a self-supporting anode , directly assembled with metal lithium foil cathode, diaphragm, electrolyte, and battery shell; the self-supporting anode uses molybdenum trioxide and sulfur powder as evaporation sources, and is directly deposited on the molybdenum foil by a simple one-step chemical vapor deposition method. Growth of high-purity, high-density, high - crystalline, vertical, ultrathin MoS2 nanosheet array structures; including the following steps: (1)在真空管式炉中，将预处理过的0.05-0.15mm厚的钼箔倒扣在装有100-140mg分析纯MoO3粉的氧化铝陶瓷坩埚上，并将其放在管式炉的中央加热区域，然后将装有500-600mg分析纯S粉的氧化铝陶瓷坩埚放置在气流上方距离装有MoO3粉的坩埚14-20cm处；(1) In a vacuum tube furnace, put the pretreated 0.05-0.15mm thick molybdenum foil upside down on the alumina ceramic crucible containing 100-140mg analytical pure MoO3 powder, and place it in the tube furnace Then place the alumina ceramic crucible containing 500-600mg of analytically pure S powder above the airflow at a distance of 14-20cm from the crucible containing MoO powder; (2)在加热前，先用真空泵对整个系统抽真空至0.02Pa以下，然后向系统中通入纯度99.99vol.％以上的高纯氩气作为载气和保护气，排除系统中残余的氧气；加热时，以10-20℃/min的升温速率加热到600-700℃，然后保温0.5-1.5小时；在整个加热过程中，持续通入100-150标准立方厘米每分钟(sccm)的高纯氩气，直到自然冷却至室温，即得钼箔负载的MoS2纳米片阵列结构样品；(2) Before heating, first use a vacuum pump to evacuate the entire system to below 0.02Pa, and then inject high-purity argon with a purity of more than 99.99vol.% into the system as carrier gas and protective gas to remove residual oxygen in the system ; During heating, heat to 600-700°C at a heating rate of 10-20°C/min, and then keep the temperature for 0.5-1.5 hours; during the whole heating process, continue to feed 100-150 standard cubic centimeters per minute (sccm) high Pure argon gas until naturally cooled to room temperature to obtain MoS2 nanosheet array structure samples supported by molybdenum foil ; (3)在真空手套箱中，将所制得的钼箔负载的MoS2纳米片阵列结构样品用作锂离子电池的阳极，分析纯金属锂箔作为阴极，并与电解液、隔膜和电池外壳等进行组装；在组装前，先对整个真空手套箱抽真空至10-3Pa以下，然后向其中通入高纯氩气作为保护气并重复多次，用以排除系统中的空气；在组装过程中，首先将所制得的钼箔负载的MoS2纳米片阵列结构样品直接放入电池外壳中，然后加入电解液，再依次放入隔膜和金属锂箔，盖上外壳，最后将电池进行密封；( 3 ) In a vacuum glove box, the prepared MoS2 nanosheet array structure sample supported by molybdenum foil was used as the anode of the lithium ion battery, and the analytically pure metal lithium foil was used as the cathode, and was combined with the electrolyte, separator and battery shell. Wait for assembly; before assembly, first vacuum the entire vacuum glove box to below 10 -3 Pa, and then pass high-purity argon into it as a protective gas and repeat it for several times to remove the air in the system; after assembly In the process, the prepared MoS2 nanosheet array structure sample supported by molybdenum foil was firstly put into the battery casing, then the electrolyte was added, and then the separator and metal lithium foil were placed in sequence, and the casing was covered, and finally the battery was carried out. seal; (4)对电池进行外包装。(4) Outer packaging the battery. 2.按照权利要求1所述的制备方法，其特征在于，所述步骤(1)中MoO3粉和S粉均为市售分析纯试剂，钼箔为市售普通导电金属，厚度为0.05-0.15mm；钼箔的预处理工艺为：将钼箔依次在0.5-2.5mol/L的稀盐酸、丙酮和乙醇超声清洗10分钟，然后晾干备用；样品与原料的安置方式为：在真空管式炉中，将预处理过的钼箔倒扣在装有分析纯MoO3粉的氧化铝陶瓷坩埚上，并将其放在管式炉的中央加热区域，然后将装有分析纯S粉的氧化铝陶瓷坩埚放置在气流上方距离装有MoO3粉的坩埚14-20cm处；所述步骤(2)和(3)中高纯氩气纯度在99.99vol.％以上；所述步骤(2)中加热过程为：以10-20℃/min的升温速率加热到600-700℃，然后保温0.5-1.5小时，最后自然冷却到室温，且在整个加热过程中，持续通入100-150标准立方厘米每分钟(sccm)的高纯氩气。2. preparation method according to claim 1, is characterized in that, in described step (1), MoO powder and S powder are commercially available analytical reagents, and molybdenum foil is commercially available common conductive metal, and thickness is 0.05- 0.15mm; the pretreatment process of the molybdenum foil is as follows: the molybdenum foil is ultrasonically cleaned in 0.5-2.5mol/L dilute hydrochloric acid, acetone and ethanol for 10 minutes, and then dried for use; the arrangement of samples and raw materials is as follows: in a vacuum tube type In the furnace, the pretreated molybdenum foil was inverted on the alumina ceramic crucible filled with analytically pure MoO3 powder, and placed in the central heating area of the tube furnace, and then the oxidized The aluminum ceramic crucible is placed above the air flow at a distance of 14-20 cm from the crucible containing MoO powder; in the steps (2) and ( 3 ), the purity of the high-purity argon gas is above 99.99 vol.%; in the step (2), heating The process is: heating to 600-700°C at a heating rate of 10-20°C/min, then maintaining the temperature for 0.5-1.5 hours, and finally cooling to room temperature naturally, and during the whole heating process, continuously feed 100-150 standard cubic centimeters per minutes (sccm) of high-purity argon. 3.按照权利要求1所述的制备方法，其特征在于，所述步骤(3)中电解液由电解质和有机溶剂组成，其中电解质为六氟磷酸锂、高氯酸锂、四氟硼酸锂之一种；有机溶剂为碳酸乙烯酯(EC)，EC和碳酸二甲酯(DMC)的混合溶液，EC和碳酸二乙酯(DEC)的混合溶液，EC、DMC和碳酸甲基乙基酯(EMC)的混合溶液之一种；隔膜为聚乙烯多孔膜、聚丙烯多孔膜、聚偏氟乙烯多孔膜、纤维素复合薄膜之一种；若采用固体和凝胶电解质，则同时发挥电解液和隔膜的作用，此时固体电解质材料可为锂磷氧氮化合物(LiPON)、Li0.5La0.5TiO3或聚合物电解质之一种；电池外壳为高绝缘硬质材料；所制备的锂离子电池外观上为扣式、柱式、箱式或全固态薄膜电池之一种。3. according to the preparation method of claim 1, it is characterized in that, in described step (3), electrolyte is made up of electrolyte and organic solvent, and wherein electrolyte is a kind of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate; The organic solvent is ethylene carbonate (EC), the mixed solution of EC and dimethyl carbonate (DMC), the mixed solution of EC and diethyl carbonate (DEC), the mixed solution of EC, DMC and methyl ethyl carbonate (EMC) A kind of mixed solution; the diaphragm is one of polyethylene porous film, polypropylene porous film, polyvinylidene fluoride porous film, and cellulose composite film; if solid and gel electrolytes are used, it will play the role of electrolyte and diaphragm at the same time At this time, the solid electrolyte material can be one of lithium phosphorus oxynitride (LiPON), Li 0.5 La 0.5 TiO 3 or polymer electrolyte; the battery shell is a high-insulation hard material; the prepared lithium ion battery has a button-like appearance. One of the type, column type, box type or all-solid-state thin film battery.
CN201811204440.3A 2018-10-16 2018-10-16 Preparation method of lithium-ion battery based on molybdenum foil-supported molybdenum disulfide nanosheet array structure Withdrawn CN109346723A (en)

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CN111514916A (en) * 2020-05-12 2020-08-11 刘志国 Method for preparing nitrogen-doped molybdenum-based chalcogenide catalytic material for hydrogen evolution by water electrolysis
CN113484341A (en) * 2021-07-01 2021-10-08 南京工业大学 Method for preparing TEM sample based on hybrid lead-based perovskite nanosheets
CN115020118A (en) * 2022-07-20 2022-09-06 兰州大学 A kind of preparation method of composite electrode material, super capacitor and battery
CN115020118B (en) * 2022-07-20 2024-04-09 兰州大学 Preparation method of composite electrode material, supercapacitor and battery

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