CN106410152B - A kind of one-dimensional antimony trisulfide-carbon composite, preparation method and application - Google Patents
A kind of one-dimensional antimony trisulfide-carbon composite, preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of one-dimensional antimony trisulfide-carbon nanocoils composite material and preparation method, the one-dimensional Sb that the present invention is prepared2S3/ C nano line composite material, structure is uniform, antimony trisulfide particle rule is unified and is evenly distributed on inside carbon nanocoils and surface, preparation method have the advantages that raw material is simple and easy to get, cheap, synthetic method is simple, environmental-friendly；When the material is used as lithium ion battery negative material, good cycling stability, specific capacity height, the volume expansion that can effectively inhibit alloying in cyclic process, when being used for lithium ion battery negative material, in 100mA g‑1, 150 circle circulation after have up to 551mAh g‑1Capacity.
Description
Technical field
The present invention relates to energy storage material, new energy and electrochemical field, especially a kind of one-dimensional antimony trisulfide-carbon composite wood
Material, preparation method and application.
Background technique
The energy and environment are two stern challenges that the mankind stride into that 21 century must face, tap a new source of energy with it is renewable
Clean energy resource is most one of the technology of decisive influence in current world economy.Especially along with petroleum, coal, natural gas
The environmental problem for gradually decreasing and getting worse of equal non-renewable energy resources, efficient, environmentally friendly, energy-saving novel energy resource material technology
Research and application more seem important.Lithium ion battery has the characteristics that other secondary cells are incomparable, emerging portable
Formula electronic product is such as: laptop computer, video camera and mobile phone etc. are widely used, related lithium ion battery
Research also becomes hot spot concerned by people.
Nano metal sulfide material cures antimony has the characteristic of high capacity, theoretical due to there is two step lithium insertion process
Particular capacity is very high, is 946mAh g–1.But the antimony trisulfide composite material that the prior art is used as lithium cell cathode material is to pass through
Hydro-thermal prepares rodlike, pencil antimony trisulfide, and no and carbon compound, cyclical stability is poor, and capacity is low.In addition antimony trisulfide is received with carbon
Mitron is compound to have production difficulty, expensive problem.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, one-dimensional antimony trisulfide carbon nanocoils are mixed the present invention provides a kind of
Composite material and preparation method and application, its object is to be designed by unique structure, using electrostatic spinning technique,
SbCl3Reduction method and vacuum high-temperature vulcanize the mode combined, and active nano material cures antimony insertion carbon nanocoils are prepared into
To lithium ion battery antimony trisulfide negative electrode material of the invention, the composite material of prior art antimony trisulfide is thus solved as lithium ion
The problems such as cyclical stability present in cell negative electrode material is poor, specific capacity is low, compound difficult with carbon nanotube.
To achieve the above object, according to one aspect of the present invention, it is compound that a kind of one-dimensional antimony trisulfide-carbon nanocoils are provided
The chemical formula group of material, the composite material becomes Sb2S3/ C, wherein antimony trisulfide particle distribution inside carbon nanocoils and surface,
The mass percent of its antimony trisulfide is 33~41%, surplus C.
Preferably, the size of the carbon nanocoils is 150~300nm.
Preferably, the size of the antimony trisulfide particle is 15~30nm.
Preferably, when the composite material is used for lithium ion battery material, in 100mA g-1, 150 circle circulation after have
510~551mA h g-1Capacity.
Other side according to the invention provides a kind of preparation method of one-dimensional antimony trisulfide-carbon composite, including
Following steps:
(1) by antimony chloride, polyacrylonitrile, N,N-dimethylformamide according to mass ratio be 0.07~0.11:0.07~
0.11:1 is uniformly mixed, and antimonic salt spinning liquid as precursor is prepared；
(2) the spinning liquid as precursor spinning under high pressure for obtaining step (1), obtains presoma one-dimensional nano line；Wherein
Spinning voltage is 18~22KV, and it is 0.2~1.0mm/min that rate is injected in spinning；
(3) one-dimensional nano line for obtaining step (2) is calcined in hydrogen/argon atmospher high temperature, obtains one-dimensional mixing antimony after cooling
Carbon nanocoils；The calcination temperature is 550~750 DEG C, and calcination time is 6~10h；
(4) the one-dimensional of step (3) acquisition is mixed into antimony carbon nanocoils in a vacuum, vulcanization reaction 6 occurs at 300~350 DEG C
~10h obtains one-dimensional antimony trisulfide-carbon composite.
Preferably, spinning voltage described in step (2) is 20KV, and it is 0.6mm/min that rate is injected in spinning.
Preferably, the volume ratio of hydrogen and argon gas is 10:90 in step (3) hydrogen/argon atmospher.
Preferably, step (4) vulcanization reaction is to be carried out by the way that excessive sulphur powder is added.
Preferably, high-temperature calcination heating rate described in step (4) is 5~10 DEG C/min.
Other side according to the invention provides the one-dimensional antimony trisulfide carbon nanocoils composite material mixed described in one kind
Using negative electrode material applied to lithium ion battery.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect.
(1) one-dimensional antimony trisulfide-carbon nanocoils composite material for being prepared of the present invention, wherein Sb2S3The size of particle is 20
~30nm or so, the size of carbon nanocoils are 150~300nm.When applied to ion cathode material lithium, stability is good, specific capacity
Volume expansion that is high, can effectively inhibiting alloying in cyclic process.When for lithium ion battery negative material, in 100mA g-1, 150 circle circulation after have up to 521mAh g-1Capacity.
(2) one-dimensional antimony trisulfide-carbon nanocoils composite material provided by the invention during the preparation process there is synthesis material to close
Simple at method, environmental-friendly, unique structure, and the material property synthesized is good, stablizes, pattern is uniform, high with specific capacity,
The advantages of stable structure, small toxicity, mature production technology.
(3) one-dimensional antimony trisulfide-carbon nanocoils composite material prepared by the present invention, Sb2S3Nano particle and one-dimensional carbon fiber
Composite material and pure Sb2S3Material is compared, by by Sb2S3It is prepared into equally distributed nano particle, rule is unified and uniform
It is distributed in carbon nanocoils inside and surface, insertion and abjection of the lithium/sodium ion in charge and discharge process is effectively alleviated and causes
Volume change, so that cycle performance and service life be made to be greatly improved, meanwhile, carbon fiber also provides for composite material
Good electric conductivity and mechanical performance.
Detailed description of the invention
Fig. 1 is one-dimensional antimony trisulfide-carbon nanocoils composite material preparation technology flow chart of the invention；
Fig. 2 is one-dimensional antimony trisulfide-carbon nanocoils composite material SEM figure that the embodiment of the present invention 1 is prepared；
Fig. 3 is one-dimensional antimony trisulfide-carbon nanocoils composite material TEM figure that the embodiment of the present invention 1 is prepared；
Fig. 4 is one-dimensional antimony trisulfide-carbon nanocoils composite material X-ray diffractogram that the embodiment of the present invention 1 is prepared；
Fig. 5 is one-dimensional antimony trisulfide-carbon nanocoils composite material cycle performance figure that the embodiment of the present invention 1 is prepared.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
A kind of one-dimensional antimony trisulfide-carbon nanocoils composite material provided by the invention, chemical composition Sb2S3/ C, wherein
Sb2S3Nanoparticle is evenly distributed on inside carbon nanocoils and surface, Sb2S3Mass percent be 33~41%, surplus is
C, the size of the carbon nanocoils are 150~300nm, and the size of the antimony trisulfide particle is 15~30nm.
One-dimensional Sb of the invention2S3When/C nano line composite material is applied to lithium ion battery negative material, cyclical stability
Good, specific capacity is high, can effectively inhibit the volume expansion of alloying in cyclic process.When for lithium ion battery material,
100mA g-1, 150 circle circulation after have 510~551mAh g-1Capacity.
The preparation method of one-dimensional antimony trisulfide-carbon nanocoils composite material proposed by the present invention, comprising the following steps:
(1) by antimony chloride, polyacrylonitrile, N,N-dimethylformamide according to mass ratio be 0.07~0.11:0.07~
0.11:1 is uniformly mixed, and antimonic salt spinning liquid as precursor is prepared；
(2) the spinning liquid as precursor spinning under high pressure for obtaining step (1), obtains presoma one-dimensional nano line；Wherein
Spinning voltage is 18~22KV, and preferably 20KV, it is 0.2~1.0mm/min, preferably 0.6mm/min that rate is injected in spinning；
(3) one-dimensional nano line for obtaining step (2) is calcined in hydrogen/argon atmospher high temperature, the hydrogen/argon-mixed volume
Ratio is 10:90, obtains one-dimensional mixing antimony carbon nanocoils after cooling；The calcination temperature be 550~750 DEG C, calcination time be 6~
10h；
(4) by step (3) obtain it is one-dimensional mix antimony carbon nanocoils in a vacuum, it is high temperature vulcanized with excessive sulphur powder, then with two
Nitric sulfid washes away remaining sulphur powder, obtains one-dimensional antimony trisulfide-carbon nanocoils composite material, wherein heating rate be 5~10 DEG C/
Min, vulcanization reaction temperature are 300~350 DEG C, the vulcanization reaction time 20~for 24 hours.
The present invention is by by SbCl3It is reduced into antimony simple substance, then it is vulcanized by vacuum sealing tube high temperature sulphur powder as vulcanization
Antimony, the preparation method is simple and feasible, synthetic product purity is high.
The present invention uses electrostatic spinning technique, uses SbCl for the first time3Reduction method and vacuum sealing tube is high temperature vulcanized combines
Active material antimony trisulfide insertion carbon nanocoils are prepared one-dimensional antimony trisulfide-carbon nanocoils composite material, are applied to lithium by mode
Ion battery antimony trisulfide negative electrode material shows superior performance, 100mA gUnder -1Circulation for the first time can be reached after 150 circle of circulation to hold
The 86% of amount, and the antimony trisulfide lithium ion battery negative material that the method for prior art hydrothermal synthesis is prepared is in 100mA gUnder -1Its capacity is reduced to the 79% of circulation volume for the first time after 100 circle of circulation.
Step (1) selects SbCl3It is that many experiments are explored as a result, once attempting Sb (NO in test as antimony source3)3、Sb
(CH3COO)3Equal antimonic salts find that its Sb particle in high-temperature calcination reduction process overflows carbon nanocoils, or even reunion is together, cannot
Be prepared as described in the present invention it is one-dimensional mix antimony trisulfide carbon nanocoils composite material, this is because it was restored in high-temperature calcination
It decomposes in journey and generates a large amount of NO2、CO2Caused by equal gases.And SbCl3It does not have decomposition and leads to the problem of gas, because
This, selects SbCl3The antimony source that antimony trisulfide carbon nanocoils composite material synthesis process is mixed as the present invention, in reduction process, sulphur
That changes that antimony can be stable is embedded in inside and outside carbon nanocoils, to be made uniform, be embedded in the vulcanization on inside carbon nanocoils and surface
Antimony nanoparticle.
The following are embodiments:
Embodiment 1:
A kind of one-dimensional antimony trisulfide-carbon nanocoils composite material preparation method as shown in Figure 1, comprising the following steps:
(1) preparation of spinning precursor solution: weighing antimony chloride, PAN and DMF in mass ratio for 0.09:0.09:1, stirring
For 24 hours, it is uniformly mixed it, obtains spinning precursor solution.
(2) preparation of nanowire precursor: by spinning precursor solution made from above-mentioned steps (1) in electrospinning device
Voltage 20KV, middle spinning injects rate 0.6mm/min.
(3) above-mentioned (2) resulting nanowire precursor the preparation of one-dimensional Sb/C nanowire composite: is placed in tube furnace
In be passed through hydrogen/argon-mixed calcining (10:90, Vol), 650 DEG C of calcination temperature, calcination time 6h, heating rate is 5 DEG C/min.
(4) one-dimensional antimony trisulfide-carbon nanocoils composite material preparation: the nano wire for the stable structure that step (3) are obtained
With 30mg sulphur powder in 350 degree of vulcanization 22h of high temperature in vacuum sealing tube, then remaining sulphur powder is washed away with carbon disulfide and obtains Fig. 2, figure
One-dimensional antimony trisulfide-carbon nanocoils composite material shown in 3.Fig. 2 is that one-dimensional antimony trisulfide-carbon that the present embodiment preparation process obtains is received
The SEM of rice noodles composite material schemes, it can be seen that the width dimensions of the negative electrode material are 200nm or so；Fig. 3 is the present embodiment system
One-dimensional antimony trisulfide-carbon nanocoils composite material TEM figure that standby technique obtains, it can be seen that Sb2S3Particle is uniform to be distributed in
Inside carbon nanocoils and surface, Sb2S3The size of particle is 20~30nm, through analyzing Sb2S3The mass fraction of particle is 39%.
Through detecting, one-dimensional antimony trisulfide-carbon nanocoils composite material diffracting spectrum (XRD) that the present embodiment is prepared is such as
Shown in Fig. 4, it was demonstrated that its object phase composition is Sb2S3/ C compound；Fig. 5 is one-dimensional antimony trisulfide-carbon nanometer that the present embodiment is prepared
The cycle performance figure of the preparation of line composite material, it can be seen that after circulation 150 times, coulombic efficiency is still 99%；The material is used
When making the negative electrode material of lithium ion battery, in 100mA g-1, 150 circle circulation after have up to 551mAh g-1Capacity.
Embodiment 2:
A kind of one-dimensional antimony trisulfide-carbon nanocoils composite material preparation method as shown in Figure 1, comprising the following steps:
(1) preparation of spinning precursor solution: weighing antimony chloride, PAN and DMF in mass ratio for 0.07:0.11:1, stirring
For 24 hours, it is uniformly mixed it, obtains spinning precursor solution.
(2) preparation of nanowire precursor: by spinning precursor solution made from above-mentioned steps (1) in electrospinning device
Voltage 18KV, middle spinning injects rate 0.2mm/min.
(3) above-mentioned (2) resulting nanowire precursor the preparation of one-dimensional Sb/C nanowire composite: is placed in tube furnace
In be passed through hydrogen/argon-mixed calcining (10:90, Vol), 750 DEG C of calcination temperature, calcination time 10h, heating rate is 10 DEG C/
Min obtains one-dimensional Sb/C nanowire composite.
(4) one-dimensional antimony trisulfide-carbon nanocoils composite material preparation: the nano wire for the stable structure that step (3) are obtained
For 24 hours, then with carbon disulfide remaining sulphur powder is washed away in 300 degree of high temperature vulcanizations with 33mg sulphur powder in vacuum sealing tube.Through detecting, this
The one-dimensional Sb that embodiment is prepared2S3The width dimensions of/C nano line are 150~200nm or so, Sb2S3The size of particle is
20~30nm, through analyzing Sb2S3The mass fraction of particle is 33%.
One-dimensional antimony trisulfide-carbon nanocoils composite material that the present embodiment is prepared is for ion cathode material lithium and tests
Its circulation volume, in 100mA g-1, 150 circle circulation after have up to 510mAh g-1Capacity.
Embodiment 3:
A kind of one-dimensional antimony trisulfide-carbon nanocoils composite material preparation method as shown in Figure 1, comprising the following steps:
(1) preparation of spinning precursor solution: weighing antimony chloride, PAN and DMF in mass ratio for 0.11:0.07:1, stirring
For 24 hours, it is uniformly mixed it, obtains spinning precursor solution.
(2) preparation of nanowire precursor: by spinning precursor solution made from above-mentioned steps (1) in electrospinning device
Voltage 22KV, middle spinning injects rate 1.0mm/min.
(3) preparation of one-dimensional Sb/C nano wire compound lithium ion, sodium ion negative electrode material: above-mentioned steps (2) are resulting
Nanowire precursor, which is placed in tube furnace, is passed through hydrogen/argon-mixed calcining (10:90, Vol), and 550 DEG C of calcination temperature, calcination time
6h, heating rate are 5 DEG C/min, obtain one-dimensional Sb/C nanowire composite.
(4) one-dimensional antimony trisulfide-carbon nanocoils composite material preparation: the nano wire for the stable structure that step (3) are obtained
Remaining sulphur powder is washed away in 350 degree of vulcanization 20h of high temperature, then with carbon disulfide with 27mg sulphur powder in vacuum sealing tube.It is detected, is made
Standby obtained one-dimensional Sb2S3The width dimensions of/C nano line are 200~300nm or so, Sb2S3The size of particle is 20~30nm,
Through analyzing Sb2S3The mass fraction of particle is 33%.
Through detecting, one-dimensional antimony trisulfide-carbon nanocoils composite material that the present embodiment is prepared is used for lithium ion battery material
When expecting negative electrode material, in 100mA g-1, 150 circle circulation after have up to 541mAh g-1Capacity.
Embodiment 4:
A kind of one-dimensional antimony trisulfide-carbon nanocoils composite material preparation method as shown in Figure 1, comprising the following steps:
(1) the step of the present embodiment (1) is identical as (1) the step of embodiment 1.
(2) preparation of nanowire precursor: by spinning precursor solution made from above-mentioned steps (1) in electrospinning device
Voltage 22KV, middle spinning injects rate 0.2mm/min.
(3) nano wire of above-mentioned (3) resulting stable structure the preparation of one-dimensional Sb/C nanowire composite: is placed in pipe
Be passed through in formula furnace hydrogen/argon-mixed (10:90, Vol) calcining, 650 DEG C of calcination temperature, calcination time 6h, heating rate be 5 DEG C/
Min obtains Fig. 2, one-dimensional Sb/C nanowire composite shown in Fig. 3.
(4) one-dimensional antimony trisulfide-carbon nanocoils composite material preparation: the nano wire for the stable structure that step (3) are obtained
Remaining sulphur powder is washed away in 300 DEG C of vulcanization 20h, then with carbon disulfide with 33mg sulphur powder in vacuum sealing tube.It is detected, is prepared into
One-dimensional antimony trisulfide-carbon nanocoils composite material the size arrived is 200nm or so, Sb2S3The size of particle is on the left side 15~20nm
The right side, through analyzing Sb2S3The mass fraction of particle is 38%.
Through detecting, one-dimensional antimony trisulfide-carbon nanocoils composite material that the present embodiment is prepared is used for lithium ion battery material
When expecting negative electrode material, in 100mA g-1, 150 circle circulation after have up to 538mAh g-1Capacity.
By the above various embodiments as it can be seen that one-dimensional antimony trisulfide-carbon nanocoils composite material prepared by the present invention is used as lithium ion
When cell negative electrode material, have many advantages, such as high comprehensive performance, unique structure, good cycle.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (6)
1. a kind of preparation method of one-dimensional antimony trisulfide-carbon composite, which comprises the following steps:
It (1) is 0.07~0.11:0.07~0.11:1 according to mass ratio by antimony chloride, polyacrylonitrile, N,N-dimethylformamide
It is uniformly mixed, antimonic salt spinning liquid as precursor is prepared；
(2) the spinning liquid as precursor spinning under high pressure for obtaining step (1), obtains presoma one-dimensional nano line；Wherein spinning
Voltage is 18~22KV, and it is 0.2~1.0mm/min that rate is injected in spinning；
(3) one-dimensional nano line for obtaining step (2) is calcined in hydrogen/argon atmospher high temperature, is obtained one-dimensional antimony carbon of mixing after cooling and is received
Rice noodles；The calcination temperature of the high-temperature calcination is 550~750 DEG C, and calcination time is 6~10h；
(4) by step (3) obtain it is one-dimensional mix antimony carbon nanocoils in a vacuum, at 300~350 DEG C occur vulcanization reaction 20~
24h。
2. the preparation method of composite material as described in claim 1, which is characterized in that spinning voltage described in step (2) is
20KV, it is 0.6mm/min that rate is injected in spinning.
3. the preparation method of composite material as described in claim 1, which is characterized in that hydrogen in step (3) hydrogen/argon atmospher
The volume ratio of gas and argon gas is 10:90.
4. the preparation method of composite material as described in claim 1, which is characterized in that step (4) described vulcanization reaction is logical
The excessive sulphur powder of addition is crossed to carry out.
5. the preparation method of composite material as described in claim 1, which is characterized in that high-temperature calcination liter described in step (4)
Warm rate is 5~10 DEG C/min.
6. a kind of preparation method of one-dimensional antimony trisulfide-carbon composite as claimed in any one of claims 1 to 5, wherein is prepared
Composite material application, which is characterized in that the negative electrode material applied to lithium ion battery.
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| CN106992293A (en) * | 2017-05-22 | 2017-07-28 | 浙江大学 | The preparation method of the composite of metal sulfide and carbon and its application in sodium-ion battery |
| CN107331842A (en) * | 2017-06-30 | 2017-11-07 | 华南理工大学 | It is a kind of with the antimony trisulfide base negative material of high reversible capacity and its preparation and application |
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