CN107055489B - A method of it preparing nano wire and weaves spherical antimony selenide anode material of lithium-ion battery - Google Patents

A method of it preparing nano wire and weaves spherical antimony selenide anode material of lithium-ion battery Download PDF

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CN107055489B
CN107055489B CN201710391694.XA CN201710391694A CN107055489B CN 107055489 B CN107055489 B CN 107055489B CN 201710391694 A CN201710391694 A CN 201710391694A CN 107055489 B CN107055489 B CN 107055489B
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ion battery
lithium
anode material
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CN107055489A (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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Abstract

A method of it preparing nano wire and 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, obtains mixed liquor C；Glycerol is added into mixed liquor C, completely cuts off air and in 80 DEG C~150 DEG C of at a temperature of reaction aging 1h~18h after mixing evenly, is cooled to room temperature after reaction；Finally, washing, dry, obtain nano wire and weave spherical antimony selenide anode material of lithium-ion battery.The present invention prepares nano wire and weaves spherical Sb2Se3Reaction process once complete in the liquid phase, process equipment is simple, reproducible, and the Sb prepared2Se3Electrode material has excellent chemical property.

Description

A method of it preparing nano wire and weaves spherical antimony selenide anode material of lithium-ion battery
Technical field
The present invention relates to a kind of nano wires to weave spherical Sb2Se3Preparation, and in particular to it is a kind of to prepare nano wire woven ball The method of shape antimony selenide anode material of lithium-ion battery.
Background technique
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, it is widely used in solar battery, photocatalysis With the fields such as photoelectric conversion.
Currently, reporting preparation Sb2Se3The main method of nano material has solvent heat, hydro-thermal, solid phase reaction etc.. Rencheng Jin etc. prepares vermiform Sb using solvent heat2Se3Nano material, hydrogen storage capability (228.5mAh with higher 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 are selenium source, and oleyl amine is solvent, and solvent heat combines the Sb prepared with solid phase reaction2Se3Nano wire has Good photothermal conversion 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. is used by solvent of ethyl alcohol 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. uses hydro-thermal method, the nanometer threadiness 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 prepared by Sb for other methods2Se3Nanometer The relevant report of material is fewer.
At present in these preparation methods, solvent heat pass through frequently with the organic matters such as etoh solvent, oleyl amine, ethylenediamine preparing It is easy to happen danger, and high production cost in the process, environmental pollution is also bigger.The product of hydro-thermal method preparation is mostly one-dimensional Structure hinders Sb2Se3The research of electrode material electrochemical behavior.Therefore it is simple, reproducible to develop a kind of equipment, green peace Full preparation three-dimensional S b2Se3The method of electrode material has scientific meaning very much.
Summary of the invention
The purpose of the present invention is to provide a kind of nano wires for preparing to weave spherical antimony selenide anode material of lithium-ion battery Method.
In order to achieve the above objectives, the invention adopts the following technical scheme:
A method of it preparing nano wire and weaves spherical antimony selenide anode material of lithium-ion battery, comprising the following steps:
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 under agitation in solution A, obtains mixed liquor C；
4) glycerol is added into mixed liquor C, after mixing evenly completely cut off air and 80 DEG C~150 DEG C at a temperature of react old Change 1h~18h, is cooled to room temperature after reaction；Finally, washing, dry, obtain nano wire and weave spherical antimony selenide sodium ion Cell negative electrode material.
A further improvement of the present invention lies in that in step 1) ethylene glycol and distilled water volume ratio (1~4): (1~4).
A further improvement of the present invention lies in that polyvinylpyrrolidone average molecular weight is 30000 in step 1), polyethylene The mass ratio of pyrrolidones and potassium antimony tartrate is (0.05~0.3g): (0.0236~1.3516g).
A further improvement of the present invention lies in that the ratio of polyvinylpyrrolidone and glycerol is (0.05~0.3g): (1~ 2mL)。
A further improvement of the present invention lies in that the concentration of step 1) mesotartaric acid antimony potassium is 0.001~0.04mol/L.
A further improvement of the present invention lies in that the mass concentration of hydrazine hydrate is 50%.
A further improvement of the present invention lies in that the ratio of sodium selenite and hydrazine hydrate is 0.0179~1.0372g in step 2): 2~10mL.
A further improvement of the present invention lies in that the molar ratio of sodium selenite and potassium antimony tartrate is 1:1.5.
A further improvement of the present invention lies in that cooled to room temperature；In step 1), step 2), step 3) and step 4) Stirring is all made of magnetic stirring apparatus, and speed of agitator is 500~700r/min, and mixing time is 10~60min；It is anti-in step 4) Should be carried out under oil bath heating.
A further improvement of the present invention lies in that the diameter that nano wire weaves spherical antimony selenide anode material of lithium-ion battery is 500nm~1 μm.
Compared with prior art, the beneficial effects of the present invention are embodied in: whole preparation process of the present invention is primary in the liquid phase It completes, simple process and safe and reliable overcomes solvent heat bring safety and problem of environmental pollution.The present invention is by adjusting second The ratio of glycol and deionized water promotes the growth of nano wire using the distinctive one-dimensional guiding role of ethylene glycol；It adjusts again simultaneously The ratio of polyvinylpyrrolidone and potassium antimony tartrate is mutually glued by polyvinylpyrrolidone chain polymer with solid particle The characteristics of knot, obstruction nanoparticle 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 for the first time 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 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 stablized using oil bath heating, and temperature range is wide and without water pollution, 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.
Detailed description of the invention
Fig. 1 is Sb prepared by embodiment 32Se3X-ray diffraction (XRD) map of electrode material；
Fig. 2 is Sb prepared by embodiment 32Se3Scanning electron microscope (SEM) photo of electrode material；
Fig. 3 is Sb prepared by embodiment 32Se3Partial enlargement scanning electron microscope (SEM) photo of electrode material；
Fig. 4 is Sb prepared by embodiment 32Se3The cycle performance figure of electrode material；Wherein, Cycle number: circulation Number；Capacity: capacity.
Specific embodiment
It elaborates with reference to the accompanying drawings and examples to the present invention.
Embodiment 1
1) by average molecular weight be 30000 polyvinylpyrrolidone and potassium antimony tartrate ethylene glycol and distilled water is added In mixed liquor, stirring (500r/min, 60min) is made it completely dissolved, and 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 additional amount is 0.05g, wine The additional amount of stone acid antimony potassium is 0.0236g；
2) 0.0179g sodium selenite is added in the hydrazine hydrate that 2mL mass concentration is 50%, stirring (500r/min, It 20min) makes it completely dissolved, obtains claret solution B；
3) obtained solution B is added dropwise in solution A under the conditions of stirring (500r/min), obtains mixed liquor C；
4) firstly, three drop (1mL) glycerol are added into mixed liquor C under the conditions of stirring (500r/min), after mixing evenly It is put into oil bath pan, isolation air is in 80 DEG C of at a temperature of reaction aging 18h, cooled to room temperature after reaction；Finally, It is centrifugated product, it is successively multiple with deionized water, dehydrated alcohol and acetone washing, isolated is deposited in vacuum condition Lower freeze-drying obtains the spherical Sb woven by nano wire2Se3Electrode material.
Embodiment 2
1) by average molecular weight be 30000 polyvinylpyrrolidone and potassium antimony tartrate ethylene glycol and distilled water is added In mixed liquor, stirring (500r/min, 30min) is made it completely dissolved, and 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 additional amount is 0.1g, winestone The additional amount of sour antimony potassium is 0.1352g；
2) 0.09g sodium selenite is added in the hydrazine hydrate that 4mL mass concentration is 50%, is stirred (500r/min, 20min) It makes it completely dissolved, obtains claret solution B；
3) obtained solution B is added dropwise in solution A under the conditions of stirring (500r/min), obtains mixed liquor C；
4) firstly, three drops glycerol (1mL) are added into mixed liquor C under the conditions of stirring (700r/min), after mixing evenly It is put into oil bath pan, isolation air is in 100 DEG C of at a temperature of reaction aging 16h, cooled to room temperature after reaction；Most Afterwards, it is centrifugated product, it is successively multiple with deionized water, dehydrated alcohol and acetone washing, isolated is deposited in vacuum Under the conditions of be freeze-dried, obtain by nano wire weave spherical Sb2Se3Electrode material.
Embodiment 3
1) by average molecular weight be 30000 polyvinylpyrrolidone and potassium antimony tartrate ethylene glycol and distilled water is added In mixed liquor, stirring (600r/min, 10min) is made it completely dissolved, and 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 additional amount is 0.15g, wine The additional amount of stone acid antimony potassium is 0.2703g；
2) 0.2075g sodium selenite is added in the hydrazine hydrate that 6mL mass concentration is 50%, stirring (600r/min, It 20min) makes it completely dissolved, obtains claret solution B；
3) obtained solution B is added dropwise in solution A under the conditions of stirring (600r/min), obtains mixed liquor C；
4) firstly, three drops glycerol (1mL) are added into mixed liquor C under the conditions of stirring (700r/min), after mixing evenly It is put into oil bath pan and completely cuts off air in 120 DEG C of at a temperature of reaction aging 12h, after reaction cooled to room temperature；Finally, It is centrifugated product, it is successively multiple with deionized water, dehydrated alcohol and acetone washing, isolated is deposited in vacuum condition Lower freeze-drying obtains the spherical Sb woven by nano wire2Se3Electrode material.
5) sample (Sb is analyzed with Rigaku D/max2000PCX- x ray diffractometer x2Se3Powder), discovery sample with The Sb for the rhombic system that JCPDS number is 15-08612Se3Structure is consistent and occurs without other miscellaneous peaks, referring to Fig. 1；By the sample It is observed with the field emission scanning electron microscope (FESEM) of FEI Co., U.S. S-4800 type, it can be seen that prepared receives Rice noodles weave spherical Sb2Se3Diameter 500nm~1 μm, referring to figs. 2 and 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 as sodium ion When cell negative electrode material, higher electrochemistry capacitance and cyclical stability are shown, referring to fig. 4.
Embodiment 4
1) by average molecular weight be 30000 polyvinylpyrrolidone and potassium antimony tartrate ethylene glycol and distilled water is added In mixed liquor, stirring (700r/min, 10min) is made it completely dissolved, and 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 additional amount is 0.2g, winestone The additional amount of sour antimony potassium is 0.5406g；
2) 0.4151g sodium selenite is added in the hydrazine hydrate that 8mL mass concentration is 50%, stirring (600r/min, It 30min) makes it completely dissolved, obtains claret solution B；
3) obtained solution B is added dropwise in solution A under the conditions of stirring (600r/min), obtains mixed liquor C；
4) it firstly, three drops glycerol (1mL) are added into mixed liquor C under the conditions of stirring 600r/min, puts after mixing evenly Enter to completely cut off in oil bath pan air in 130 DEG C of at a temperature of reaction aging 6h, after reaction cooled to room temperature；Finally, from Heart separation product, it is successively multiple with deionized water, dehydrated alcohol and acetone washing, under vacuum conditions by isolated precipitating Freeze-drying obtains the spherical Sb woven by nano wire2Se3Electrode material.
Embodiment 5
1) by average molecular weight be 30000 polyvinylpyrrolidone and potassium antimony tartrate ethylene glycol and distilled water is added In mixed liquor, stirring (500r/min, 30min) is made it completely dissolved, and 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 additional amount is 0.25g, wine The additional amount of stone acid antimony potassium is 0.9123g；
2) 0.7004g sodium selenite is added in the hydrazine hydrate that 9mL mass concentration is 50%, stirring (700r/min, It 10min) makes it completely dissolved, obtains claret solution B；
3) obtained solution B is added dropwise in solution A under the conditions of stirring (600r/min), obtains mixed liquor C；
4) firstly, three drops glycerol (1mL) are added into mixed liquor C under the conditions of stirring (600r/min), after mixing evenly It is put into oil bath pan and completely cuts off air in 140 DEG C of at a temperature of reaction aging 3h, after reaction cooled to room temperature；Finally, It is centrifugated product, it is successively multiple with deionized water, dehydrated alcohol and acetone washing, isolated is deposited in vacuum condition Lower freeze-drying obtains the spherical Sb woven by nano wire2Se3Electrode material.
Embodiment 6
1) by average molecular weight be 30000 polyvinylpyrrolidone and potassium antimony tartrate ethylene glycol and distilled water is added In mixed liquor, stirring (500r/min, 10min) is made it completely dissolved, and 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 additional amount is 0.30g, wine The additional amount of stone acid antimony potassium is 1.3516g；
2) 1.0376g sodium selenite is added in the hydrazine hydrate that 10mL mass concentration is 50%, stirring (500r/min, It 30min) makes it completely dissolved, obtains claret solution B；
3) obtained solution B is added dropwise in solution A under the conditions of stirring (600r/min), obtains mixed liquor C；
4) firstly, three drops glycerol (1mL) are added into mixed liquor C under the conditions of stirring (700r/min), after mixing evenly It is put into oil bath pan and completely cuts off air in 150 DEG C of at a temperature of reaction aging 1h, after reaction cooled to room temperature；Finally, It is centrifugated product, it is successively multiple with deionized water, dehydrated alcohol and acetone washing, 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, are stirred using magnetic force It mixes device and stirs 10min at 700r/min, obtain solution A；Wherein, the volume ratio 2: 3 of ethylene glycol and distilled water, polyvinyl pyrrole Alkanone average molecular weight 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 glycerol is 0.05g:2mL, and the concentration of potassium antimony tartrate is 0.001mol/L.
2) sodium selenite is added in the hydrazine hydrate that mass concentration is 50%, is stirred at 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 at 700r/min using magnetic stirring apparatus under agitation, is obtained Mixed liquor C；Wherein, the molar ratio of sodium selenite and potassium antimony tartrate is 1:1.5.The volume for controlling mixed liquor C is 70mL.
4) glycerol is added at 700r/min into mixed liquor C using magnetic stirring apparatus, completely cuts off air simultaneously after mixing evenly In 125 DEG C of at a temperature of reaction aging 10h, cooled to room temperature after reaction；Finally, washing, dry, nano wire is obtained 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, are stirred using magnetic force It mixes device and stirs 60min at 500r/min, obtain solution A；Wherein, the volume ratio 4: 3 of ethylene glycol and distilled water, polyvinyl pyrrole Alkanone average molecular weight is 30000, and the mass ratio of polyvinylpyrrolidone and potassium antimony tartrate is 0.3g:1.1488g, polyethylene The mass ratio of pyrrolidones and glycerol is 0.3g:2mL, and the concentration of potassium antimony tartrate is 0.04mol/L.
2) sodium selenite is added in the hydrazine hydrate that mass concentration is 50%, is stirred at 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 at 500r/min using magnetic stirring apparatus under agitation, is obtained Mixed liquor C；Wherein, the molar ratio of sodium selenite and potassium antimony tartrate is 1:1.5, and the volume of control mixed liquor C is 85mL.
4) glycerol is added at 500r/min into mixed liquor C using magnetic stirring apparatus, completely cuts off air simultaneously after mixing evenly In 100 DEG C of at a temperature of reaction aging 16h, cooled to room temperature after reaction；Finally, washing, dry, nano wire is obtained 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, are stirred using magnetic force It mixes device and stirs 30min at 600r/min, obtain solution A；Wherein, the volume ratio 2: 3.5 of ethylene glycol and distilled water, polyethylene pyrrole Pyrrolidone average molecular weight 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 glycerol is 0.2g:2mL, and the concentration of potassium antimony tartrate is 0.01mol/L.
2) sodium selenite is added in the hydrazine hydrate that mass concentration is 50%, is stirred at 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 at 600r/min using magnetic stirring apparatus under agitation, is obtained Mixed liquor C；Wherein, the molar ratio of sodium selenite and potassium antimony tartrate is 1:1.5.The volume for controlling mixed liquor C is 100mL.
4) glycerol is added at 600r/min into mixed liquor C using magnetic stirring apparatus, completely cuts off air simultaneously after mixing evenly In 110 DEG C of at a temperature of reaction aging 13h, cooled to room temperature after reaction；Finally, washing, dry, nano wire is obtained Weave spherical antimony selenide anode material of lithium-ion battery.
In the present invention addition glycerol of glycerol be added to prevent vapor from flowing back, experiment is had an impact.
The innovative ratio by adjusting polyvinylpyrrolidone and potassium antimony tartrate of the invention, rationally controls ethylene glycol The Sb with three-dimensional manometer line braiding chondritic is successfully prepared with the volume ratio of deionized water2Se3Nano material.

Claims (8)

1. a kind of method for preparing nano wire and weaving spherical antimony selenide anode material of lithium-ion battery, which is characterized 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；Wherein, the volume ratio (1~4) of ethylene glycol and distilled water: (1~4)；Polyvinylpyrrolidone average molecular weight is 30000, is gathered The mass ratio of vinylpyrrolidone and potassium antimony tartrate is (0.05~0.3g): (0.0236~1.3516g)；
2) sodium selenite is added in hydrazine hydrate, stirring obtains claret solution B；
3) solution B is added dropwise under agitation in solution A, obtains mixed liquor C；
4) glycerol is added into mixed liquor C, completely cuts off air after mixing evenly and in 80 DEG C~150 DEG C of at a temperature of reaction aging 1h ~18h, is cooled to room temperature after reaction；Finally, washing, dry, obtain nano wire and weave spherical antimony selenide sodium-ion battery Negative electrode material.
2. a kind of side for preparing nano wire and weaving spherical antimony selenide anode material of lithium-ion battery according to claim 1 Method, which is characterized in that the ratio of polyvinylpyrrolidone and glycerol is (0.05~0.3g): (1~2mL).
3. a kind of side for preparing nano wire and weaving spherical antimony selenide anode material of lithium-ion battery according to claim 1 Method, which is characterized in that the concentration of step 1) mesotartaric acid antimony potassium is 0.001~0.04mol/L.
4. a kind of side for preparing nano wire and weaving spherical antimony selenide anode material of lithium-ion battery according to claim 1 Method, which is characterized in that the mass concentration of hydrazine hydrate is 50%.
5. a kind of side for preparing nano wire and weaving spherical antimony selenide anode material of lithium-ion battery according to claim 4 Method, which is characterized in that the ratio of sodium selenite and hydrazine hydrate is 0.0179~1.0372g:2~10mL in step 2).
6. a kind of side for preparing nano wire and weaving spherical antimony selenide anode material of lithium-ion battery according to claim 1 Method, which is characterized in that the molar ratio of sodium selenite and potassium antimony tartrate is 1:1.5.
7. a kind of side for preparing nano wire and weaving spherical antimony selenide anode material of lithium-ion battery according to claim 1 Method, which is characterized in that cooled to room temperature；Stirring is all made of magnetic agitation in step 1), step 2), step 3) and step 4) Device, speed of agitator are 500~700r/min, and mixing time is 10~60min；Reaction in step 4) be under oil bath heating into Capable.
8. a kind of side for preparing nano wire and weaving spherical antimony selenide anode material of lithium-ion battery according to claim 1 Method, which is characterized in that the diameter that nano wire weaves spherical antimony selenide anode material of lithium-ion battery is 500nm~1 μm.
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