CN102912317B - Method for manufacturing shape-controlled nanometer zinc and antimony alloy material - Google Patents
Method for manufacturing shape-controlled nanometer zinc and antimony alloy material Download PDFInfo
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- CN102912317B CN102912317B CN201210375536.2A CN201210375536A CN102912317B CN 102912317 B CN102912317 B CN 102912317B CN 201210375536 A CN201210375536 A CN 201210375536A CN 102912317 B CN102912317 B CN 102912317B
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Abstract
The invention belongs to the technical field of manufacture of cathode materials for lithium ion batteries, and particularly discloses a method for manufacturing a shape-controlled nanometer zinc and antimony alloy material. Chemical vapor deposition is adopted, and the temperature and the pressure of a reaction system are controlled, so that a series of zinc and antimony alloy materials, such as zinc and antimony nano-rods, nano-wires and nano-tubes, with different shapes are deposited on a current collector made of a copper foil, and the zinc and antimony alloy materials can be directly used for assembling lithium ion batteries. The method specifically includes steps of 1, pretreating the copper foil; 2, injecting a sample of solid precursors; and 3, controlling the pressure of the system and feeding gas precursors. The zinc and antimony alloy material manufactured by the method has the advantages of uniform shape, simplicity in synthesis, convenience in battery assembly, good battery circulation performance and the like. The method can also be used for manufacturing other antimony-base alloy materials or tin-base alloy materials and the like, shapes of products are controlled by changing reaction conditions of the system, and the method is further applicable to the fields of lithium ion batteries, thermoelectric conversion and the like.
Description
Technical field
The invention belongs to lithium ion battery negative material preparing technical field, be specifically related to a kind of preparation method of Nano-Zinc antimony alloy material of morphology controllable.
Background technology
Antimony-containing alloy material is the important lithium ion battery negative material of a class, and have good conductivity, theoretical capacity is high, lower-price characteristic.Wherein zinc antimony alloy has suitable crystalline structure, is applicable to the embedding of lithium ion, and the negative pole being used for lithium ion battery has the voltage of higher theoretical capacity and safety.But this material volume change in Lithium-ion embeding with the process of deviating from is comparatively large, easily causes cracked and comes off, thus affecting the cycle performance of battery greatly.Research shows, if material energy nanoscale forms some special pattern, can alleviate the problems referred to above that this volume change is brought, thus improves the cycle performance of battery greatly.In addition, zinc antimony alloy as classics thermo-electric converting material, there is higher thermoelectric figure of merit (being about 1.3).Research shows, if material to be made one dimension shape (as nano wire), is conducive to keeping the specific conductivity of material and reducing its thermal conductivity, thus improves its thermoelectric figure of merit, be finally expected to become the thermo-electric converting material with practical value.Visible, preparation and the characteristic thereof of research Nano-Zinc antimony alloy have great importance.
About the synthesis of zinc antimony alloy controllable appearance causes certain concern in recent years.Zinc antimony alloy nano material can be prepared to the variforms such as nano particle, nano wire, nanotube, nano flake.Such as, the Zhao Xinbing seminar of China and the Sohn Hun-Joon seminar of Korea S use the method for combined with heat treatment high-energy mechanical ball milling to synthesize Zn respectively at 2000 and 2010
4sb
3the negative material of lithium ion battery is applied to the nano particle of ZnSb.The patterns such as nano particle, nano wire, nanotube and nano flake that the Yan Qingyu seminar of Singapore used electrodip process to prepare ZnSb in 2011, and be applied to lithium ion battery negative material, truly achieve the controlledly synthesis of zinc antimony alloy pattern.
At present, the preparation method of the zinc antimony alloy of report has heat treating process, high-energy ball milling method, electrodip process etc., the part but these methods all come with some shortcomings.Such as, the long reaction time that heat treating process needs in conjunction with high-energy ball milling method, make lithium ion battery process complicated, and cycle performance of battery is poor, usually needs by complex carbon material to improve its performance; And electrodip process needs with an organic solvent, and device is more complicated and expensive.
Summary of the invention
The object of this invention is to provide that a kind of simple process, cost are lower, the preparation method of the Nano-Zinc antimony alloy material of morphology controllable.
The preparation method of the Nano-Zinc antimony alloy material of morphology controllable provided by the invention, adopt chemical Vapor deposition process, by controlling the factor such as temperature, pressure of reaction system, successfully the zinc antimony alloy of the multiple different-shapes such as zinc antimony alloy nanometer rod, nano wire and nanotube is deposited directly to current collector material (Copper Foil).
Before the preparation method of the Nano-Zinc antimony alloy material of morphology controllable provided by the invention comprises the pre-treatment of Copper Foil, solid
Drive the control of the sample introduction of thing, system temperature and pressure and passing into of gaseous precursor, its concrete steps are:
(1) pre-treatment of Copper Foil: by Copper Foil dilute hydrochloric acid or dilute sulphuric acid cleaning, clean with alcohol flushing, be then coated with the ethanolic soln of one deck zinc chloride at copper foil surface with spin-coating method, the ethanol solution concentration of wherein said zinc chloride is 8-12mmol/L;
(2) sample introduction of solid precursors: porcelain boat is put in zinc source, is placed in reaction zone central authorities; Porcelain boat is put in antimony source, is placed in front end, reaction zone; Copper Foil is placed in reaction zone downstream position;
(3) control of system pressure and passing into of gaseous precursor: first, clean whole reaction system with rare gas element, then continues logical rare gas element; When system temperature is elevated to 350-450 DEG C, in system, pass into reducing gas, system total pressure is adjusted to 75-600Pa, and wherein in volume 100 sccm, described rare gas element accounts for 40-60%; Described reducing gas accounts for 40-60%; After question response terminates, reducing pressure detaches reaction zone by unreacted for residue gas and gaseous product; Before temperature is down to room temperature, continues logical protection of inert gas reaction product, obtain the zinc antimony alloy material of morphology controllable.
In the present invention, described in step (2), zinc source is selected from any one in zinc chloride, zinc nitrate or zinc sulfate; Described antimony source is selected from any one in antimony chloride, nitric acid antimony or antimony trisulfate, and the mol ratio in described zinc source and antimony source is 1:1.
In the present invention, antimony source described in step (2) is far from reaction zone central authorities 10-12cm; Described Copper Foil is from reaction zone central authorities 13-14cm.
In the present invention, rare gas element described in step (3) be argon gas or nitrogen any one, described reducing gas be hydrogen or methane any one.
In the present invention, in step (3), described reaction system total pressure is 75-100Pa.
In the present invention, in step (3), described reaction system total pressure is 150-300Pa.
In the present invention, in step (3), described reaction system total pressure is 450-600Pa.
In the present invention, the control of temperature: namely the temperature of reaction zone and temperature rise rate mainly rely on high temperature process furnances to regulate and control; The control of product collection district temperature: the warm area position can placed by Copper Foil or use variable-temperaturetube tube furnace are realized.
In the present invention, we improve and have developed chemical vapour deposition technique, introduce air-path control system, pressure control system, temperature controlling system (Fig. 1), regulate the sample introduction of precursor and the collection of product, thus achieve the preparation of nanometer rod, nano wire and nanotube-shaped zinc antimony alloy.
Beneficial effect of the present invention is: this method can provide an easy approach for the preparation of Nano-Zinc antimony alloy and Morphological control, but also can the range of application of this technology be extended in the preparation of other alloy materials, promote the development of type material and device further.
Adopting the zinc antimony alloy prepared in this way, to have pattern homogeneous, and synthesis is simple, and assembled battery is convenient, and the features such as cycle performance of battery is good, can prepare the patterns such as nanometer rod, nano wire and nanotube.The method also can be used for preparing other antimony-containing alloy material or tin-based alloy materials etc., by the change of system reaction conditions, and the pattern of regulation and control product, and then be applied to the field such as lithium ion battery, thermoelectric conversion.
Accompanying drawing explanation
Fig. 1 is the device schematic diagram that chemical Vapor deposition process prepares the zinc antimony alloy nano material of different-shape.
Number in the figure: 1 is air-path control system, 2 is temperature controlling system, and 3 is pressure control system, and 4 is reaction zone, and 5 is antimony source, and 6 is zinc source, and 7 is Copper Foil.
Fig. 2 is the Nano-Zinc antimony alloy of different-shape.Wherein, (a, b) nanometer rod; (c, d) nano wire; (e, f) nanotube.
Fig. 3 is that the Nano-Zinc antimony alloy of different-shape is as performance during lithium ion battery negative material.Wherein, (a) nanotube is at the interval recharge-discharge voltage curve of 0 – 2 V; (b) nanometer rod, nano wire, nanotube cycle performance of battery figure, and the coulombic efficiency figure of nanotube.
Embodiment
The present invention includes the building of reaction system, the sample introduction of pre-reaction material, system pressure Controlling System, system temperature regulator control system four parts:
1. the building of reaction system: whole reaction system comprises following five parts: gas circuit regulator control system, reaction zone, sampling system, pressure control system and temperature regulation system (see accompanying drawing 1).
2. the sample introduction of pre-reaction material: solid or liquid reactions precursor are positioned in porcelain boat, porcelain boat position in the reaction region can regulate and control arbitrarily; Gaseous precursor is controlled by gas circuit regulator control system, can regulate passing into of multipath gas by gas circuit valve control, gas velocity and pass into the time etc.
3. system pressure Controlling System: system pressure can realize the accurate control of low pressure-high pressure.Low pressure is conducive to the cleaning of realization response system and in good time detaching of reactant, and mesolow is conducive to the regulation and control of product morphology.
4. system temperature regulator control system: the temperature at reaction zone and reaction product place can accuracy controlling, thus realizes the regulation and control of product morphology.
Pre-reaction material comprises zinc source: zinc chloride; Antimony source: butter of antimony; Gas: hydrogen, argon gas etc.
The porcelain boat that reaction solid or liquid precursor are housed, under the help of the magnetite of system outside, is pushed to the appropriate location of reaction zone by the magnetite in system; Gas passage comprises the protective gas such as nitrogen, argon gas, the reducing gas such as hydrogen, methane.Each road gas is all furnished with the regulation device such as flow director and valve.
By the adjustment of secondary valve control and vacuum oil pump, realize the accurate control of low pressure (10Pa)-high pressure (10 MPa).
By high temperature process furnances or other heating units, realize room temperature-high temperature (1000
oc) adjustment of accurate control and temperature rise rate.Testing tube furnace used is Thermo Fisher Scientific company of U.S. Lindberg Blue M tube furnace, silica tube internal diameter 2.5cm used.
The preparation of the Nano-Zinc antimony alloy material of embodiment 1 morphology controllable
Selective chlorination zinc and butter of antimony are as zinc source and the antimony source of preparing zinc antimony alloy, and hydrogen is as reducing gas, and argon gas is as protective gas.First, antimony source is placed in the front end of reaction zone, distance reaction zone central authorities 10cm, zinc source is placed in reaction zone central authorities, at distance reaction zone, downstream, reaction zone central authorities 13cm, places the Copper Foil (as Fig. 1) collecting product.
Then, by pressure control system, vacuumize and make system pressure drop to 10 below Pa, repeatedly rinse 3 times with argon gas, the oxygen in removing system.Then, the argon gas passing into 50 sccm in system is continued.Then heat reaction zone with tube furnace, setting temperature of reaction system is 400 DEG C.When system temperature reaches 400 DEG C, in system, pass into the hydrogen of 50 sccm and regulation system pressure to 75Pa, keep 5 minutes.Finally, open valve control and vacuumize, under argon shield condition, system is cooled to room temperature.The zinc antimony alloy material obtained is nanorod structure, and particle diameter is about 500nm, length be 1-2 μm (as Fig. 2 a, b).
If regulation system pressure is to 200Pa, the zinc antimony alloy material obtained is nano thread structure, and particle diameter is 100-800nm, length be 2-5 μm (as Fig. 2 c, d).
If regulate regulation system pressure to 500Pa, the zinc antimony alloy material obtained is nano tube structure, and particle diameter is 50-800nm, length be 2-5 μm (as Fig. 2 e, f).
Test-results shows: when Copper Foil is without pre-treatment, and the zinc antimony alloy that reaction is formed is mainly nano particle or membranaceous pattern; When Copper Foil is after pre-treatment, the controlledly synthesis of zinc antimony alloy pattern can be realized in 75-600 Pa pressure ranges.When system pressure is less than 100 Pa, the zinc antimony alloy of formation is mainly nanometer rod pattern; When system pressure is at 150 – 300 Pa, the zinc antimony alloy of formation is mainly nano wire pattern; When system pressure is at 450 – 600 Pa, the zinc antimony alloy of formation is mainly nanotube pattern; When system pressure is greater than 1000 Pa, the zinc antimony alloy pattern of formation is mixed and disorderly, cannot accuracy controlling.
The assembling of embodiment 2 lithium ion battery and test
The Copper Foil that deposited zinc antimony alloy being cut into the disk of diameter 12mm, without the need to adding the additive such as conductive agent, binding agent, directly moving into the glove box assembling button cell being full of argon gas.The oxygen content of glove box and water-content all should be less than 1ppm.To assemble button cell be half-cell structure, deposited the Copper Foil of zinc antimony alloy as negative pole, using lithium sheet as positive pole, using the NSC 11801/diethyl carbonate of the lithium hexafluoro phosphate of 1mol/L (mass ratio 1:1) solution as electrolytic solution.Electric performance test uses Shenzhen new prestige multi-channel battery test instrument, and use constant current charge-discharge pattern, current density is 100mA/g, and voltage range is 2-0V.
As shown in Figure 3, result shows test result, and the nanotube pattern zinc antimony alloy first circle loading capacity that embodiment 1 obtains is 1160 mAh/g, maintains about 450 mAh/g through 100 charge/discharge capacities.The nano wire pattern zinc antimony alloy first circle loading capacity that embodiment 1 obtains is 720 mAh/g, maintains about 320 mAh/g through 100 charge/discharge capacities.The volume nanometer rod pattern zinc antimony alloy first circle loading capacity that embodiment 1 obtains is 460 mAh/g, maintains 200 mAh through 100 charge/discharge capacities.
Claims (7)
1. the preparation method of the Nano-Zinc antimony alloy material of a morphology controllable, it is characterized in that: adopt chemical Vapor deposition process, by controlling temperature and the pressure of reaction system, the zinc antimony alloy material of zinc antimony nanometer rod, nano wire or nanotube pattern is deposited directly on current collector Copper Foil, for the assembling of lithium ion battery; Concrete steps are:
(1) pre-treatment of Copper Foil: by Copper Foil dilute hydrochloric acid or dilute sulphuric acid cleaning, rinse well with organic solvent, be then coated with the ethanolic soln of one deck zinc chloride with spin-coating method at copper foil surface, the ethanol solution concentration of wherein said zinc chloride is 8-12mmol/L;
(2) sample introduction of solid precursors: porcelain boat is put in zinc source, is placed in reaction zone central authorities; Porcelain boat is put in antimony source, is placed in front end, reaction zone; Copper Foil is placed in reaction zone downstream position;
(3) control of system pressure and passing into of gaseous precursor: first, clean whole reaction system with rare gas element, then continues logical rare gas element; When system temperature is elevated to 350-450 DEG C, in system, pass into reducing gas, system total pressure is adjusted to 75-600Pa, and wherein in volume 100 sccm, described rare gas element accounts for 40-60%, and described reducing gas accounts for 40-60%; After question response terminates, reducing pressure detaches reaction zone by unreacted for residue gas and gaseous product; Before temperature is down to room temperature, continues logical protection of inert gas reaction product, obtain the zinc antimony alloy material of morphology controllable.
2. the preparation method of the Nano-Zinc antimony alloy material of morphology controllable according to claim 1, is characterized in that: described in step (2), zinc source is selected from any one in zinc chloride, zinc nitrate or zinc sulfate; Described antimony source is selected from any one in antimony chloride, nitric acid antimony or antimony trisulfate; The mol ratio in described zinc source and antimony source is 1:1.
3. the preparation method of the Nano-Zinc antimony alloy material of morphology controllable according to claim 1, is characterized in that: antimony source described in step (2) is far from reaction zone central authorities 10-12cm, and described Copper Foil is from reaction zone central authorities 13-14cm.
4. the preparation method of the Nano-Zinc antimony alloy material of morphology controllable according to claim 1, is characterized in that: rare gas element described in step (3) be argon gas or nitrogen any one, described reducing gas be hydrogen or methane any one.
5. the preparation method of the Nano-Zinc antimony alloy material of morphology controllable according to claim 1, is characterized in that: in step (3), and described reaction system total pressure is 75-100Pa.
6. the preparation method of the Nano-Zinc antimony alloy material of morphology controllable according to claim 1, is characterized in that: described in step (3), reaction system total pressure is 150-300Pa.
7. the preparation method of the Nano-Zinc antimony alloy material of morphology controllable according to claim 1, is characterized in that: in step (3), and described reaction system total pressure is 450-600Pa.
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| US9994715B2 (en) | 2016-02-16 | 2018-06-12 | Sila Nanotechnologies Inc. | Formation and modifications of ceramic nanowires and their use in functional materials |
| CN114400331A (en) * | 2022-03-03 | 2022-04-26 | 电子科技大学 | Preparation method of negative current collector capable of improving lithium metal cycle stability |
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