CN107055489A - It is a kind of to prepare the method that nano wire weaves spherical antimony selenide anode material of lithium-ion battery - Google Patents

It is a kind of to prepare the method that nano wire weaves spherical antimony selenide anode material of lithium-ion battery Download PDF

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CN107055489A
CN107055489A CN201710391694.XA CN201710391694A CN107055489A CN 107055489 A CN107055489 A CN 107055489A CN 201710391694 A CN201710391694 A CN 201710391694A CN 107055489 A CN107055489 A CN 107055489A
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nano wire
ion battery
lithium
anode material
spherical
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CN107055489B (en
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曹丽云
郭玲
李嘉胤
黄剑锋
吴建鹏
程娅伊
齐慧
弓琴琴
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Shaanxi University of Science and Technology
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/007—Tellurides or selenides of metals
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    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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    • 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
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    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
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    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
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    • C01P2006/40—Electric properties
    • 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
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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
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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    • Y02E60/10—Energy storage using batteries

Abstract

It is a kind of to prepare the method that nano wire weaves spherical antimony selenide anode material of lithium-ion battery, polyvinylpyrrolidone and potassium antimony tartrate are added in the mixed liquor of ethylene glycol and distilled water, stirring obtains solution A；Sodium selenite is added in hydrazine hydrate, stirring obtains claret solution B；Solution B is added dropwise in solution A under agitation, mixed liquor C is obtained；Glycerine is added into mixed liquor C, air and reaction aging 1h~18h at a temperature of 80 DEG C~150 DEG C are completely cut off after stirring, reaction is cooled to room temperature after terminating；Finally, wash, dry, obtain nano wire and weave spherical antimony selenide anode material of lithium-ion battery.The present invention prepares nano wire and weaves spherical Sb2Se3Course of reaction once complete in the liquid phase, process equipment is simple, reproducible, and the Sb prepared2Se3Electrode material has excellent chemical property.

Description

It is a kind of to prepare the method that nano wire weaves spherical antimony selenide anode material of lithium-ion battery
Technical field
Spherical Sb is woven the present invention relates to a kind of nano wire2Se3Preparation, and in particular to one kind prepares nano wire woven ball The method of shape antimony selenide anode material of lithium-ion battery.
Background technology
Sb2Se3It is the simple binary compound with typical layered structure, direct band gap P-type semiconductor, band gap is 1.2eV.With physical properties such as light sensitivity, photoconduction and pyroelectric effects, solar cell, photocatalysis are widely used in With the field such as photoelectric conversion.
At present, preparation Sb is reported2Se3The main method of nano material has solvent heat, hydro-thermal, solid phase reaction etc.. Rencheng Jin etc. prepare vermiform Sb using solvent heat2Se3Nano material, with higher hydrogen storage capability (228.5mAh g-1) and good cycle performance.(Jin R,Chen G,Pei J,et al.Controllable synthesis and electrochemical hydrogen storage properties of Sb2Se3ultralong nanobelts with urchin-like structures.[J].Nanoscale,2011,3(9):3893).Chen G et al. use antimony triphenyl for Antimony source, dibenzyl selenium is selenium source, and oleyl amine is solvent, and solvent heat is combined the Sb prepared with solid phase reaction2Se3Nano wire has Good photothermal deformation performance.(Chen G,Zhou J,Zuo J,et al.Organometallically Anisotropic Growth of Ultra-Long Sb2Se3Nanowires with Highly Enhanced Photothermal Response.[J].Acs Applied Materials&Interfaces,2016).Zhang Y etc. are used by solvent of ethanol Solvent heat prepares spherical Sb2Se3Nano material (Zhang Y, Li G, Zhang B, et al.Synthesis and characterization of hollow Sb2Se3nanospheres[J].Materials Letters,2004,58(17): 2279-2282.).Wenxi Zhao etc. use hydro-thermal method, the nanometer wire Sb of preparation2Se3It is compound with N doping graphene oxide Material shows higher capacity.(Zhao W,Li C M.Mesh-structured N-doped graphene@ Sb2Se3hybrids as an anode for large capacity sodium-ion batteries.[J].Journal of Colloid&Interface Science,2016,488:356-364).But prepare Sb for other method2Se3Nanometer The relevant report of material is fewer.
In these current preparation methods, solvent heat pass through frequently with the organic matter such as etoh solvent, oleyl amine, ethylenediamine preparing During easily cause danger, and production cost is high, and environmental pollution is also than larger.Product prepared by hydro-thermal method is mostly one-dimensional Structure, hinders Sb2Se3The research of electrode material electrochemical behavior.Therefore a kind of equipment is developed simple, reproducible, green peace It is complete to prepare D S b2Se3The method of electrode material has scientific meaning very much.
The content of the invention
Spherical antimony selenide anode material of lithium-ion battery is woven it is an object of the invention to provide a kind of nano wire for preparing Method.
To reach above-mentioned purpose, present invention employs following technical scheme：
It is a kind of to prepare the method that nano wire weaves spherical antimony selenide anode material of lithium-ion battery, comprise the following steps：
1) polyvinylpyrrolidone and potassium antimony tartrate are added in the mixed liquor of ethylene glycol and distilled water, stirring is obtained Solution A；
2) sodium selenite is added in hydrazine hydrate, stirring obtains claret solution B；
3) solution B is added dropwise in solution A under agitation, obtains mixed liquor C；
4) glycerine is added into mixed liquor C, air is completely cut off after stirring and reacts old at a temperature of 80 DEG C~150 DEG C Change 1h~18h, reaction is cooled to room temperature after terminating；Finally, wash, dry, obtain nano wire and weave spherical antimony selenide sodium ion Cell negative electrode material.
Of the invention further improve be, step 1) in ethylene glycol and distilled water volume ratio (1~4): (1~4).
Of the invention further improve be, step 1) in polyvinylpyrrolidone mean molecule quantity be 30000, polyethylene The mass ratio of pyrrolidones and potassium antimony tartrate is (0.05~0.3g)：(0.0236~1.3516g).
Further improve of the invention is that the ratio of polyvinylpyrrolidone and glycerine is (0.05~0.3g)：(1~ 2mL)。
Of the invention further improve be, step 1) concentration of mesotartaric acid antimony potassium is 0.001~0.04mol/L.
Further improve of the invention is that the mass concentration of hydrazine hydrate is 50%.
Of the invention further improve be, step 2) in the ratio of sodium selenite and hydrazine hydrate be 0.0179~1.0372g: 2~10mL.
Further improve of the invention is that the mol ratio of sodium selenite and potassium antimony tartrate is 1:1.5.
Further improve of the invention is, naturally cools to room temperature；Step 1), step 2), step 3) with step 4) in Stirring uses magnetic stirring apparatus, and speed of agitator is 500~700r/min, and mixing time is 10~60min；Step 4) in it is anti- It should be carried out under oil bath heating.
Further improve of the invention is that nano wire weaves a diameter of of spherical antimony selenide anode material of lithium-ion battery 500nm~1 μm.
Compared with prior art, beneficial effects of the present invention are embodied in：Whole preparation process of the present invention is in the liquid phase once Complete, technique is simple and safe and reliable, overcomes safety and problem of environmental pollution that solvent heat is brought.The present invention is by adjusting second The ratio of glycol and deionized water, using the distinctive one-dimensional guide effect of ethylene glycol, promotes the growth of nano wire；Adjust again simultaneously The ratio of polyvinylpyrrolidone and potassium antimony tartrate, mutually glues by polyvinylpyrrolidone chain polymer with solid particle Knot, the characteristics of hindering nano-particle further growth has finally synthesized nano wire and has woven spherical Sb2Se3Nano material.The present invention Prepared nano wire weaves spherical Sb2Se3As anode material of lithium-ion battery, discharge capacity can reach 720mA h first g-1, in 0.1A g-1Under current density, capacity is positively retained at~260mA h g after 50 circulations-1, show preferable electrochemistry Performance, illustrates that the nano wire prepared by the present invention weaves spherical Sb2Se3There is certain grind as anode material of lithium-ion battery Study carefully meaning.
Further, the present invention is stable using oil bath heating, and temperature range is wide and without moisture contamination, and can be in short-term The characteristics of interior nucleation-growth, the Sb of preparation2Se3Electrode material has excellent chemical property, and equipment is simple, repeats Property is good.
Brief description of the drawings
Fig. 1 is the Sb prepared by embodiment 32Se3X-ray diffraction (XRD) collection of illustrative plates of electrode material；
Fig. 2 is the Sb prepared by embodiment 32Se3ESEM (SEM) photo of electrode material；
Fig. 3 is the Sb prepared by embodiment 32Se3Partial enlargement ESEM (SEM) photo of electrode material；
Fig. 4 is the Sb prepared by embodiment 32Se3The cycle performance figure of electrode material；Wherein, Cycle number：Circulation Number of times；Capacity：Capacity.
Embodiment
The present invention is elaborated with reference to the accompanying drawings and examples.
Embodiment 1
1) mean molecule quantity is added into ethylene glycol and distilled water for 30000 polyvinylpyrrolidone and potassium antimony tartrate In mixed liquor, stirring (500r/min, 60min) is completely dissolved it, obtains solution A, wherein, the volume of ethylene glycol and distilled water Than for VEthylene glycol∶VDistilled water=4: 1, antimony tartrate potassium concn is 0.001mol/L, and polyvinylpyrrolidone addition is 0.05g, wine The addition of stone acid antimony potassium is 0.0236g；
2) 0.0179g sodium selenites are added in the hydrazine hydrate that 2mL mass concentrations are 50%, stirring (500r/min, It 20min) is completely dissolved, claret solution B is obtained；
3) obtained solution B is added dropwise in solution A under the conditions of stirring (500r/min), obtains mixed liquor C；
4) three first, are added into mixed liquor C under the conditions of stirring (500r/min) and drips (1mL) glycerine, after stirring It is put into oil bath pan, completely cuts off air reaction aging 18h at a temperature of 80 DEG C, reaction naturally cools to room temperature after terminating；Finally, Product is centrifuged, is washed repeatedly with deionized water, absolute ethyl alcohol and acetone successively, isolated is deposited in vacuum condition Lower freeze-drying, obtains the spherical Sb woven by nano wire2Se3Electrode material.
Embodiment 2
1) mean molecule quantity is added into ethylene glycol and distilled water for 30000 polyvinylpyrrolidone and potassium antimony tartrate In mixed liquor, stirring (500r/min, 30min) is completely dissolved it, obtains solution A, the volume ratio control of ethylene glycol and distilled water System is in VEthylene glycol∶VDistilled water=1: 1, antimony tartrate potassium concn is 0.005mol/L, and polyvinylpyrrolidone addition is 0.1g, winestone The addition of sour antimony potassium is 0.1352g；
2) 0.09g sodium selenites are added 4mL mass concentrations in 50% hydrazine hydrate, to stir (500r/min, 20min) It is completely dissolved, claret solution B is obtained；
3) obtained solution B is added dropwise in solution A under the conditions of stirring (500r/min), obtains mixed liquor C；
4) three first, are added into mixed liquor C under the conditions of stirring (700r/min) and drips glycerine (1mL), after stirring It is put into oil bath pan, completely cuts off air reaction aging 16h at a temperature of 100 DEG C, reaction naturally cools to room temperature after terminating；Most Afterwards, product is centrifuged, is washed repeatedly with deionized water, absolute ethyl alcohol and acetone successively, isolated is deposited in vacuum Under the conditions of be freeze-dried, obtain the spherical Sb woven by nano wire2Se3Electrode material.
Embodiment 3
1) mean molecule quantity is added into ethylene glycol and distilled water for 30000 polyvinylpyrrolidone and potassium antimony tartrate In mixed liquor, stirring (600r/min, 10min) is completely dissolved it, obtains solution A, the volume ratio control of ethylene glycol and distilled water System is in VEthylene glycol∶VDistilled water=1: 3, antimony tartrate potassium concn is 0.010mol/L, and polyvinylpyrrolidone addition is 0.15g, wine The addition of stone acid antimony potassium is 0.2703g；
2) 0.2075g sodium selenites are added in the hydrazine hydrate that 6mL mass concentrations are 50%, stirring (600r/min, It 20min) is completely dissolved, claret solution B is obtained；
3) obtained solution B is added dropwise in solution A under the conditions of stirring (600r/min), obtains mixed liquor C；
4) three first, are added into mixed liquor C under the conditions of stirring (700r/min) and drips glycerine (1mL), after stirring Isolation air reaction aging 12h at a temperature of 120 DEG C in oil bath pan is put into, reaction naturally cools to room temperature after terminating；Finally, Product is centrifuged, is washed repeatedly with deionized water, absolute ethyl alcohol and acetone successively, isolated is deposited in vacuum condition Lower freeze-drying, obtains the spherical Sb woven by nano wire2Se3Electrode material.
5) with Rigaku D/max2000PCX- x ray diffractometer xs analysis sample (Sb2Se3Powder), find sample with The Sb for the rhombic system that JCPDS numberings are 15-08612Se3Structure is consistent and occurs without other miscellaneous peaks, referring to Fig. 1；By the sample Observed with the field emission scanning electron microscope (FESEM) of FEI Co. of U.S. S-4800 types, it can be seen that prepared receives Rice noodles weave spherical Sb2Se3Diameter 500nm~1 μm, referring to Fig. 2 and Fig. 3.
6) with prepared Sb2Se3Nano-powder is assembled into battery as anode material of lithium-ion battery.Use BTS electricity Pond charge-discharge test instrument tests its charge-discharge performance, it can be seen that the Sb of this special construction2Se3Electrode material is used as sodium ion During cell negative electrode material, higher electrochemistry capacitance and cyclical stability is shown, referring to Fig. 4.
Embodiment 4
1) mean molecule quantity is added into ethylene glycol and distilled water for 30000 polyvinylpyrrolidone and potassium antimony tartrate In mixed liquor, stirring (700r/min, 10min) is completely dissolved it, obtains solution A, the volume ratio control of ethylene glycol and distilled water System is in VEthylene glycol∶VDistilled water=1: 1, antimony tartrate potassium concn is 0.02mol/L, and polyvinylpyrrolidone addition is 0.2g, winestone The addition of sour antimony potassium is 0.5406g；
2) 0.4151g sodium selenites are added in the hydrazine hydrate that 8mL mass concentrations are 50%, stirring (600r/min, It 30min) is completely dissolved, claret solution B is obtained；
3) obtained solution B is added dropwise in solution A under the conditions of stirring (600r/min), obtains mixed liquor C；
4) three first, are added into mixed liquor C under the conditions of stirring 600r/min and drips glycerine (1mL), is put after stirring Enter isolation air reaction aging 6h at a temperature of 130 DEG C in oil bath pan, reaction naturally cools to room temperature after terminating；Finally, from Heart separation product, is washed repeatedly, by isolated precipitation under vacuum with deionized water, absolute ethyl alcohol and acetone successively Freeze-drying, obtains the spherical Sb woven by nano wire2Se3Electrode material.
Embodiment 5
1) mean molecule quantity is added into ethylene glycol and distilled water for 30000 polyvinylpyrrolidone and potassium antimony tartrate In mixed liquor, stirring (500r/min, 30min) is completely dissolved it, obtains solution A, the volume ratio control of ethylene glycol and distilled water System is in VEthylene glycol∶VDistilled water=1: 2, antimony tartrate potassium concn is 0.030mol/L, and polyvinylpyrrolidone addition is 0.25g, wine The addition of stone acid antimony potassium is 0.9123g；
2) 0.7004g sodium selenites are added in the hydrazine hydrate that 9mL mass concentrations are 50%, stirring (700r/min, It 10min) is completely dissolved, claret solution B is obtained；
3) obtained solution B is added dropwise in solution A under the conditions of stirring (600r/min), obtains mixed liquor C；
4) three first, are added into mixed liquor C under the conditions of stirring (600r/min) and drips glycerine (1mL), after stirring Isolation air reaction aging 3h at a temperature of 140 DEG C in oil bath pan is put into, reaction naturally cools to room temperature after terminating；Finally, Product is centrifuged, is washed repeatedly with deionized water, absolute ethyl alcohol and acetone successively, isolated is deposited in vacuum condition Lower freeze-drying, obtains the spherical Sb woven by nano wire2Se3Electrode material.
Embodiment 6
1) mean molecule quantity is added into ethylene glycol and distilled water for 30000 polyvinylpyrrolidone and potassium antimony tartrate In mixed liquor, stirring (500r/min, 10min) is completely dissolved it, obtains solution A, the volume ratio control of ethylene glycol and distilled water System is in VEthylene glycol∶VDistilled water=1: 4, antimony tartrate potassium concn is 0.040mol/L, and polyvinylpyrrolidone addition is 0.30g, wine The addition of stone acid antimony potassium is 1.3516g；
2) 1.0376g sodium selenites are added in the hydrazine hydrate that 10mL mass concentrations are 50%, stirring (500r/min, It 30min) is completely dissolved, claret solution B is obtained；
3) obtained solution B is added dropwise in solution A under the conditions of stirring (600r/min), obtains mixed liquor C；
4) three first, are added into mixed liquor C under the conditions of stirring (700r/min) and drips glycerine (1mL), after stirring Isolation air reaction aging 1h at a temperature of 150 DEG C in oil bath pan is put into, reaction naturally cools to room temperature after terminating；Finally, Product is centrifuged, is washed repeatedly with deionized water, absolute ethyl alcohol and acetone successively, isolated is deposited in vacuum condition Lower freeze-drying, obtains the spherical Sb woven by nano wire2Se3Electrode material.
Embodiment 7
1) polyvinylpyrrolidone and potassium antimony tartrate are added in the mixed liquor of ethylene glycol and distilled water, stirred using magnetic force Mix device and stir 10min under 700r/min, obtain solution A；Wherein, the volume ratio 2: 3 of ethylene glycol and distilled water, polyvinyl pyrrole Alkanone mean molecule quantity is 30000, and the mass ratio of polyvinylpyrrolidone and potassium antimony tartrate is 0.05g：0.0236g, poly- second The ratio of alkene pyrrolidone and glycerine is 0.05g：2mL, the concentration of potassium antimony tartrate is 0.001mol/L.
2) sodium selenite is added mass concentration in 50% hydrazine hydrate, to stir under 700r/min using magnetic stirring apparatus 10min is mixed, claret solution B is obtained；Wherein, the ratio of sodium selenite and hydrazine hydrate is 0.0179g:10mL.
3) solution B is added dropwise in solution A under agitation under 700r/min using magnetic stirring apparatus, obtained Mixed liquor C；Wherein, the mol ratio of sodium selenite and potassium antimony tartrate is 1:1.5.The volume for controlling mixed liquor C is 70mL.
4) glycerine is added into mixed liquor C under 700r/min using magnetic stirring apparatus, completely cuts off air simultaneously after stirring The reaction aging 10h at a temperature of 125 DEG C, reaction naturally cools to room temperature after terminating；Finally, wash, dry, obtain nano wire Weave spherical antimony selenide anode material of lithium-ion battery.
Embodiment 8
1) polyvinylpyrrolidone and potassium antimony tartrate are added in the mixed liquor of ethylene glycol and distilled water, stirred using magnetic force Mix device and stir 60min under 500r/min, obtain solution A；Wherein, the volume ratio 4: 3 of ethylene glycol and distilled water, polyvinyl pyrrole Alkanone mean molecule quantity is 30000, and the mass ratio of polyvinylpyrrolidone and potassium antimony tartrate is 0.3g：1.1488g, polyethylene The mass ratio of pyrrolidones and glycerine is 0.3g：2mL, the concentration of potassium antimony tartrate is 0.04mol/L.
2) sodium selenite is added mass concentration in 50% hydrazine hydrate, to stir under 500r/min using magnetic stirring apparatus 60min is mixed, claret solution B is obtained；Wherein, the ratio of sodium selenite and hydrazine hydrate is 1.0372g:10mL
3) solution B is added dropwise in solution A under agitation under 500r/min using magnetic stirring apparatus, obtained Mixed liquor C；Wherein, the mol ratio of sodium selenite and potassium antimony tartrate is 1:1.5, the volume for controlling mixed liquor C is 85mL.
4) glycerine is added into mixed liquor C under 500r/min using magnetic stirring apparatus, completely cuts off air simultaneously after stirring The reaction aging 16h at a temperature of 100 DEG C, reaction naturally cools to room temperature after terminating；Finally, wash, dry, obtain nano wire Weave spherical antimony selenide anode material of lithium-ion battery.
Embodiment 9
1) polyvinylpyrrolidone and potassium antimony tartrate are added in the mixed liquor of ethylene glycol and distilled water, stirred using magnetic force Mix device and stir 30min under 600r/min, obtain solution A；Wherein, the volume ratio 2: 3.5 of ethylene glycol and distilled water, polyethylene pyrrole Pyrrolidone mean molecule quantity is 30000, and the mass ratio of polyvinylpyrrolidone and potassium antimony tartrate is 0.2g：0.3379g, poly- second The mass ratio of alkene pyrrolidone and glycerine is 0.2g：2mL, the concentration of potassium antimony tartrate is 0.01mol/L.
2) sodium selenite is added mass concentration in 50% hydrazine hydrate, to stir under 600r/min using magnetic stirring apparatus 20min is mixed, claret solution B is obtained；Wherein, the ratio of sodium selenite and hydrazine hydrate is 0.4g:6mL
3) solution B is added dropwise in solution A under agitation under 600r/min using magnetic stirring apparatus, obtained Mixed liquor C；Wherein, the mol ratio of sodium selenite and potassium antimony tartrate is 1:1.5.The volume for controlling mixed liquor C is 100mL.
4) glycerine is added into mixed liquor C under 600r/min using magnetic stirring apparatus, completely cuts off air simultaneously after stirring The reaction aging 13h at a temperature of 110 DEG C, reaction naturally cools to room temperature after terminating；Finally, wash, dry, obtain nano wire Weave spherical antimony selenide anode material of lithium-ion battery.
In the present invention addition glycerine of glycerine be added to prevent vapor from flowing back, on experiment produce influence.
The innovative ratio by adjusting polyvinylpyrrolidone and potassium antimony tartrate of the invention, rationally controls ethylene glycol The Sb that chondritic is woven with three-dimensional manometer line is successfully prepared with the volume ratio of deionized water2Se3Nano material.

Claims (10)

1. a kind of prepare the method that nano wire weaves spherical antimony selenide anode material of lithium-ion battery, it is characterised in that including with Lower step：
1) polyvinylpyrrolidone and potassium antimony tartrate are added in the mixed liquor of ethylene glycol and distilled water, stirring obtains solution A；
2) sodium selenite is added in hydrazine hydrate, stirring obtains claret solution B；
3) solution B is added dropwise in solution A under agitation, obtains mixed liquor C；
4) glycerine is added into mixed liquor C, air and the reaction aging 1h at a temperature of 80 DEG C~150 DEG C is completely cut off after stirring ~18h, reaction is cooled to room temperature after terminating；Finally, wash, dry, obtain nano wire and weave spherical antimony selenide sodium-ion battery Negative material.
2. a kind of side for preparing the spherical antimony selenide anode material of lithium-ion battery of nano wire braiding according to claim 1 Method, it is characterised in that step 1) in ethylene glycol and distilled water volume ratio (1~4): (1~4).
3. a kind of side for preparing the spherical antimony selenide anode material of lithium-ion battery of nano wire braiding according to claim 1 Method, it is characterised in that step 1) in polyvinylpyrrolidone mean molecule quantity be 30000, polyvinylpyrrolidone and tartaric acid The mass ratio of antimony potassium is (0.05~0.3g)：(0.0236~1.3516g).
4. a kind of side for preparing the spherical antimony selenide anode material of lithium-ion battery of nano wire braiding according to claim 3 Method, it is characterised in that the ratio of polyvinylpyrrolidone and glycerine is (0.05~0.3g)：(1~2mL).
5. a kind of side for preparing the spherical antimony selenide anode material of lithium-ion battery of nano wire braiding according to claim 1 Method, it is characterised in that step 1) mesotartaric acid antimony potassium concentration be 0.001~0.04mol/L.
6. a kind of side for preparing the spherical antimony selenide anode material of lithium-ion battery of nano wire braiding according to claim 1 Method, it is characterised in that the mass concentration of hydrazine hydrate is 50%.
7. a kind of side for preparing the spherical antimony selenide anode material of lithium-ion battery of nano wire braiding according to claim 6 Method, it is characterised in that step 2) in sodium selenite and hydrazine hydrate ratio be 0.0179~1.0372g:2~10mL.
8. a kind of side for preparing the spherical antimony selenide anode material of lithium-ion battery of nano wire braiding according to claim 1 Method, it is characterised in that the mol ratio of sodium selenite and potassium antimony tartrate is 1:1.5.
9. a kind of side for preparing the spherical antimony selenide anode material of lithium-ion battery of nano wire braiding according to claim 1 Method, it is characterised in that naturally cool to room temperature；Step 1), step 2), step 3) with step 4) in stirring use magnetic agitation Device, speed of agitator is 500~700r/min, and mixing time is 10~60min；Step 4) in reaction be to enter under oil bath heating Capable.
10. a kind of side for preparing the spherical antimony selenide anode material of lithium-ion battery of nano wire braiding according to claim 1 Method, it is characterised in that nano wire weaves a diameter of 500nm~1 μm of spherical antimony selenide anode material of lithium-ion battery.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107959024A (en) * 2017-11-07 2018-04-24 陕西科技大学 A kind of sodium-ion battery anode sheet Sb2Se3Nanocrystalline preparation method
CN109179340A (en) * 2018-09-18 2019-01-11 西安交通大学 Lead base chalcogenide alloy particle with nanostructure and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102583272A (en) * 2012-01-21 2012-07-18 哈尔滨工业大学 Vermicular Sb2Se3 hydrogen storage material and preparation method thereof
CN102583271A (en) * 2012-01-21 2012-07-18 哈尔滨工业大学 Spine-like SbSe3 semiconductor hydrogen storage material and preparation method thereof
CN104692340A (en) * 2014-07-28 2015-06-10 深圳丹邦投资集团有限公司 Selenium precursor for preparing metal selenide nanometer material
US9598283B1 (en) * 2015-09-25 2017-03-21 Sharp Laboratories Of America, Inc. Synthesis method for controlling antimony selenide nanostructure shapes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102583272A (en) * 2012-01-21 2012-07-18 哈尔滨工业大学 Vermicular Sb2Se3 hydrogen storage material and preparation method thereof
CN102583271A (en) * 2012-01-21 2012-07-18 哈尔滨工业大学 Spine-like SbSe3 semiconductor hydrogen storage material and preparation method thereof
CN104692340A (en) * 2014-07-28 2015-06-10 深圳丹邦投资集团有限公司 Selenium precursor for preparing metal selenide nanometer material
US9598283B1 (en) * 2015-09-25 2017-03-21 Sharp Laboratories Of America, Inc. Synthesis method for controlling antimony selenide nanostructure shapes

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107959024A (en) * 2017-11-07 2018-04-24 陕西科技大学 A kind of sodium-ion battery anode sheet Sb2Se3Nanocrystalline preparation method
CN109179340A (en) * 2018-09-18 2019-01-11 西安交通大学 Lead base chalcogenide alloy particle with nanostructure and preparation method thereof
CN109179340B (en) * 2018-09-18 2021-01-05 西安交通大学 Lead-based chalcogenide alloy particles with nano structure and preparation method thereof

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