CN108963237A - A kind of preparation method of anode material of lithium-ion battery - Google Patents
A kind of preparation method of anode material of lithium-ion battery Download PDFInfo
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- CN108963237A CN108963237A CN201810889045.7A CN201810889045A CN108963237A CN 108963237 A CN108963237 A CN 108963237A CN 201810889045 A CN201810889045 A CN 201810889045A CN 108963237 A CN108963237 A CN 108963237A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y02E60/10—Energy storage using batteries
Abstract
The present invention is a kind of preparation method of anode material of lithium-ion battery.This method is using antimony trichloride, selenium powder, triethylene glycol as raw material, rodlike antimony selenide is prepared by polyol process, again using antimony selenide, carbon nanotube as main material, is etched and be spray-dried by vapor, obtain antimony selenide nanometer rods and the equally distributed microballoon of carbon nanotube.The chondritic of the material can effectively solve the problems, such as that antimony selenide is widely varied as the volume generated when positive electrode in sodium-ion battery, and more defect is formed on antimony selenide/carbon nano tube compound material surface by water etching, the transmission speed of electronics and ion is improved, to improve the chemical property and cyclical stability of lithium-sulfur cell on the whole.
Description
Technical field
The present invention relates to the technical fields of anode material of lithium-ion battery, in particular to a kind of to be used for sodium-ion battery cathode
Antimony selenide/carbon nano tube compound material preparation method.
Background technique
The energy is one of the important elements for driving human civilization progress.With the development of modern industrialization and emerging technology,
The just accelerated consumption of the traditional energies such as fossil, coal, oil and gas.And bring global energy crisis not only gives people therewith
Basic living bring and seriously affect.In addition, traditional energy excessively uses bring environmental problem that can not similarly be neglected
Depending on.To cope with the above variety of problems, the clean energy resourcies such as wind energy, solar energy, tide energy, biological energy source and geothermal energy are just gradually developed
With use.The total amount of these renewable and clean energy resources is big but energy density is small, and there is also randomnesss in the time and space for energy supply
With discontinuity.Therefore, these clean energy resourcies are easy to use to meet people in life, it is various to can satisfy actual demand
Energy storage device be widely deployed and use.
Currently, lithium ion battery is widely used in mancarried electronic aid, with power vehicle and electronic portable device
Large-scale development and application, the cost that limited lithium resource would potentially result in lithium ion battery on the earth increases, finally by quickly
It is depleted.Therefore, chemical property sodium ion secondary battery similar with lithium ion battery property becomes and the most suitably replaces
Dai Zhe.Although sodium ion is than lithium ion weight, other than power vehicle needs to consider the energy content of battery and bulk density, other are small-sized
Energy storage device (such as battery of mobile phone, Notebook Battery) mobility is smaller, this has sodium-ion battery very in practical application
A possibility that big.Be all the Ith main group of the periodic table of elements sodium element and elemental lithium property there are many similarity, so construction
Sodium-ion battery there are many aspect it is similar to lithium ion battery." the rocking chair type electricity of its basic functional principle and lithium ion battery
Pond " principle is identical, using the positive and negative anodes that reversible can be embedded in the simple substance or compound of abjection sodium ion as battery system.Sodium
Element resource is abundant, is easily obtained and sodium is relative to lithium higher half-cell prtential, so the electricity of low decomposition voltage can be used
Liquid is solved, therefore security performance is expected to better than lithium ion battery.Therefore, it to realize battery industry sustainable development, develops to environment
Free of contamination novel energy storage cell is trend of the times, and sodium-ion battery is exactly a member in this kind of novel high-energy green battery.
Although sodium-ion battery have the advantages that it is above, since sodium ion radius is larger, when the interlamellar spacing of cathode is less than
When the diameter of sodium ion, it will lead to sodium ion and be difficult to be embedded in cathode to which sodium ion embedded quantity is considerably less, so as to cause sodium ion
The specific capacity of battery is extremely low.Moreover, sodium can be compounded to form compound when can be embedded in negative electrode material, but when forming the compound
The volume expansion of material is very serious, even results in that electrode is broken, dusting, so that chemical property declines rapidly, therefore, circulation
Stability is difficult to solve.Generally speaking, the sodium-ion battery of lithium ion battery can be replaced to cause the concern of global scientist,
But sodium-ion battery needs further to be researched and solved there is also a large amount of problems.
Antimony sill becomes promising anode material of lithium-ion battery due to the deintercalation capacity with very high sodium ion.
Wherein, antimony selenide is the direct band gap P-type semiconductor with layer structure, is answered extensively as typical V-VI compounds of group
For fields such as hydrogen storage, photocatalysis and electrochemical energy storages.Also, the antimony selenide of 1mol can be embedded in the sodium ion of 12mol, and
The reaction occurred is reversible, and may finally obtain up to 678mAh g-1Theoretical specific capacity.However antimony selenide is as sodium
When ion battery cathode material, biggish volume expansion, contraction can be generated during reversible reaction occurs, with circulation time
Several increases may result in cracking and the crushing of electrode, therefore cause its cyclical stability poor, this disadvantage limits significantly
It is widely applied.Therefore the reactivity for needing to improve battery by control product morphology, by reducing scantling
Or with other materials it is compound reduce charge and discharge process in volume change, to improve its cycle performance.CN 107140609A is public
It has opened a kind of micro-wave oven hydro-thermal and has prepared the sodium-ion battery cathode method for antimony selenide electrode material of getting one's things ready.The selenium of material preparation
Change antimony nanometer bundle size is larger, and length is up to 6-7 μm, and the top of nanometer bundle is that antimony selenide nano wire is reunited, this is right
Volume expansion and contraction when it is as anode material of lithium-ion battery in charge and discharge process be it is totally unfavorable, be easy to cause electricity
The cracking of pole and crushing, this is detrimental to the cyclical stability of lithium-sulfur cell.Therefore, it is negative to develop novel antimony selenide sodium-ion battery
Pole material becomes focus concerned by people.
Summary of the invention
The technical problems to be solved by the patent is to provide a kind of sodium-ion battery for deficiency existing for current techniques center
The preparation method of negative electrode material.This method is prepared rodlike using antimony trichloride, selenium powder, triethylene glycol as raw material by polyol process
Antimony selenide, then using antimony selenide, carbon nanotube as main material, etched and be spray-dried by vapor, obtain antimony selenide nanometer
Stick and the equally distributed microballoon of carbon nanotube.The chondritic of the material can effectively solve antimony selenide as in sodium-ion battery just
Problem is widely varied in the volume generated when the material of pole, and by water etching in antimony selenide/carbon nano tube compound material surface shape
At more defect, the transmission speed of electronics and ion is improved, to improve the chemical property of lithium-sulfur cell on the whole and follow
Ring stability.
Technical scheme is as follows:
A kind of preparation method of anode material of lithium-ion battery, includes the following steps:
Step 1: configuration antimony trichloride solution；Wherein, solvent is triethylene glycol, in every 20~50mL triethylene glycol be added 0.5~
The antimony trichloride of 2g；
Step 2: compound concentration is 0.2~2mmol/mL selenium liquid；Wherein, solvent is ethanol amine and hydrazine hydrate, volume ratio second
Hydramine and hydrazine hydrate=1~5:1；
Step 3: antimony selenide dispersion liquid is prepared:
The selenium liquid prepared in step 2, polyethylene pyrrole network alkanone and triethylene glycol are added in closed container, vacuumized
After be passed through argon gas, then heat to 200~250 DEG C, then the antimony trichloride solution obtained by injection step one in syringe, protect
It holds and is stirred at 200~250 DEG C, reacts 20~50min；After being cooled to room temperature, centrifugation, obtain antimony selenide, be added into from
Sub- water ultrasonic disperse obtains antimony selenide water phase suspension；
Wherein, the selenium liquid prepared in every 7~20mL step 2 adds 0.2~2g polyethylene pyrrole network alkanone, 10~50mL, tri- second
The antimony trichloride solution of two pure and mild 20~200mL；10~20mL deionized water is added in every 1g antimony selenide；
Step 4: powder is prepared by spraying: antimony selenide water phase suspension being diluted to 10~100 times of original volume, ultrasound
0.5~1.5h；Carbon nanotube powder is added, 0.5~1.5h of ultrasound is continued；Then antimony selenide/carbon nanotube powders are obtained by spraying
End；
Wherein, antimony selenide and the mass ratio of carbon nanotube are 1:0.2~1.5, spray-drying apparatus parameter are as follows: intake
100%, 3~10mLmin of charging rate-1, 150~200 DEG C of inlet air temperature；
Step 5: vapor etching:
Antimony selenide/carbon nanotube powder is placed in tube furnace, airtight tube type furnace under argon atmosphere；Then heated Tube
Furnace is warming up to 200~400 DEG C；3~10min of mixed gas is then passed to, turns off tube furnace, it is to be cooled to after room temperature, obtain selenium
Change antimony/carbon nano tube compound material, the i.e. preparation method of anode material of lithium-ion battery；Wherein, the group of mixed gas becomes water
Steam and argon gas, the volume of vapor are the 10~30% of mixed gas volume.
Heating rate in the step five is 5~10 DEG C of min-1。
Above-mentioned antimony selenide/carbon nano tube compound material preparation method for sodium-ion battery cathode, wherein involved
To raw material be commercially available, equipment used and technique are known to those skilled in the art.
Compared with prior art, the method for the present invention has substantive distinguishing features outstanding as follows:
1, the interlamellar spacing of antimony selenide is larger, and the antimony selenide of 1mol can be embedded in the sodium ion of 12mol, and be occurred anti-
It should be reversible, so as to obtain higher specific capacity.
2, antimony selenide/carbon nano tube compound material preparation process is simple, and technique is intuitive, at low cost.
3, antimony selenide/carbon nano tube compound material is prepared by spray drying process, carbon nanotube formation one is three-dimensional netted
Structure, and rodlike antimony selenide uniformly interts wherein, and this structure greatly shortens reaction process intermediate ion and electronics
Transmission path, and due to carbon nanotube have stronger flexibility, the body of electrode in charge and discharge process can be effectively relieved
Product variation, to improve the chemical property of lithium-sulfur cell.
4, it is etched by vapor, antimony selenide/carbon nano tube compound material surface generates more atom defect, this is advantageous
The transmission of electronics and ion in reaction process, and the hole that its surface etch goes out then is conducive to alleviate electrode in charge and discharge process
The volume change of generation keeps the integrality of electrode, improves its cycle performance.
Compared with prior art, marked improvement possessed by the method for the present invention is as follows:
1, compared with 107256967 A of prior art CN, the present invention will have nanostructure and equally distributed antimony selenide
Stick is combined with each other with the carbon nanotube with outstanding electric conductivity and flexility by spray drying, can effectively be buffered
Volume change when it is as anode material of lithium-ion battery, and it is rodlike inside spherical antimony selenide/carbon nano tube compound material
Antimony selenide, which intersects, to be generated a large amount of holes and can also buffer the volume change generated in charge and discharge process, thus makes the property of battery
It can improve.And spherical antimony selenide prepared in 107256967 A of prior art CN is easily reunited, therefore it is as sodium ion
Significantly volume change is easy to produce when cell negative electrode material causes pole piece cracking and active material to fall off, and leads to cyclicity
It can be bad.And the antimony selenide ball surface prepared in 107256967 A of prior art CN is smooth, and the present invention is carved due to vapor
Losing surface has a large amount of defects, and therefore, 107256967 A of prior art CN defect compared with the present invention is less, is unfavorable for reacting
The transmission of electronics and ion in the process causes active material utilization low, can be shown by the charging and discharging capacity of electrochemistry.
Prepared antimony selenide/carbon nano tube compound material is as second of specific discharge capacity of sodium-ion battery cathode in the present invention
657mAh g-1, the significantly larger than 495mAh g of 107256967 A of prior art CN, second of discharge capacity-1。
2, compared with 107140608 A of prior art CN, the reaction time of the invention is short, and experimental period is short, dry without freezing
It is dry, a dry and step is reached by one step of spray drying and carbon nanotube is uniformly compound, hydrazine hydrate is joined in confined reaction instrument
With react, it is few to air pollution.And 107140608 A of prior art CN experiment is long reaction time, and hydrazine hydrate needs and selenium powder
It is ultrasonic under air to be configured to solution, has larger pollution to environment.It is received in the present invention by antimony selenide/carbon that spray drying obtains
The size that mitron composite material is formed by ball is smaller, is evenly distributed between 3-3.5 μm, and prior art CN 107140608
Prepared antimony selenide negative electrode material is reunited serious in A, and diameter is distributed in 20-30 μm, therefore obtained material in the present invention
It is bigger with the contact area of electrolyte when as sodium-ion battery cathode, be conducive to the utilization rate for improving active material.And this
The defect that three-dimensional netted carbon nanotube and the vapor etching obtained in invention by spray drying generates further provides for ion
Transmission channel, and the relatively multiple hole that the flexility of carbon nanotube and vapor etch further alleviates antimony selenide conduct
The volume expansion problem that battery cathode generates, and be that single-phase antimony selenide nanometer rods are reunited in 107140608 A of prior art CN
The irregular chondritic that diameter is 20-30 μm is formed, can be produced in charge and discharge process as anode material of lithium-ion battery
Raw great volume change, and its cushion space is minimum, and pole piece is be easy to cause to crack, and cycle performance is caused to be not added.And this
Carbon nanotube is added in invention can further shorten the transmission path of electronics and ion, improve the utilization rate of active material, and
It is then no in 107140608 A of technology CN, therefore causes electrochemical results poor, second of charge and discharge in the present invention
Curve shows second of discharge capacity up to 657mAh g-1, coulombic efficiency is up to 99.7%, and has 107140608 A's of technology CN
Electrochemical results obtained capacity when discharging for second is 608mAh g-1Left and right, far below the electric discharge specific volume in the present invention
Amount.
In short, antimony selenide/carbon nano tube compound material that the present invention prepares, solves existing antimony selenide material as sodium
The problem of ion battery capacity is low, Cycle Difference, carbon nanotube and antimony selenide compound make carbon nanotube form three by being spray-dried
Reticular structure is tieed up, and interts rodlike antimony selenide uniformly therebetween, and rodlike antimony selenide is interlaced while in chondritic
Inside generates a large amount of holes, to overcome antimony selenide as the volume expansion of cell negative electrode material and lacking for poor circulation
Point.And it is etched by vapor, spherical antimony selenide/carbon nano tube compound material surface generates more surface defect, this has
Conducive to the transmission during ion and electron reaction, to improve the utilization rate of active material, therefore antimony selenide/carbon nanotube is multiple
Condensation material is excellent as the sodium-ion battery high rate performance and cycle performance of cathode, is a kind of battery of great market prospects.
Detailed description of the invention
Fig. 1 is antimony selenide/carbon nano tube compound material X-ray diffractogram prepared by embodiment 2.
Fig. 2 is antimony selenide/carbon nano tube compound material scanning electron microscope diagram prepared by embodiment 2.
Fig. 3 be embodiment 2 prepared by antimony selenide/carbon nano tube compound material as sodium-ion battery cathode when in electric current
Density is second of charging and discharging curve under 0.1C.
Specific embodiment
Embodiment 1
The first step is equipped with solution:
The antimony trichloride for weighing 1g is added in 20mL triethylene glycol, and is put it on magnetic stirring apparatus and stirred, and trichlorine is made
Change antimony to be completely dissolved and be placed on spare on one side.
Second step prepares selenium liquid:
Ethanol amine and hydrazine hydrate are mixed according to the ratio of 4:1, and selenium powder is added thereto, being made into concentration is
The selenium liquid of 1mmol/mL is placed on spare on one side.
Third step prepares antimony selenide dispersion liquid:
A three-necked flask is taken, selenium liquid, 1g polyethylene pyrrole network alkanone and the 20mL prepared in 7mL step 2 is added thereto
Triethylene glycol blocks the bottleneck on the left side with the bottle stopper with syringe needle, and intermediate bottleneck is connected with condenser pipe, the insertion of the right bottleneck
Thermometer, confirmation instrument is closed, starts to vacuumize, argon gas is passed through after laboratory apparatus inner vacuum, and 3 times repeatedly.It will be equipped with
The syringe for the mixed liquor being equipped in 20mL step 1 is inserted into there-necked flask, opens agitating and heating device and starts agitating and heating, is warming up to
210 DEG C, the liquid in syringe is all injected, temperature is controlled at 210 DEG C, reacts 20min.It is cooled to room temperature to there-necked flask
Afterwards, centrifugation obtains 1.05g Sb2Se3, 15mL deionized water ultrasound is added and uniformly obtains Sb2Se3Water phase suspension.
4th step, prepares powder by spraying:
Antimony selenide water phase suspension is diluted to 350mL and is put into ultrasound 0.5h in ultrasonic machine.Take 0.5g carbon nanotube powders
End is added in antimony selenide dispersion liquid and continues to be put into ultrasonic in ultrasonic machine, time 0.5h.Then antimony selenide/carbon is obtained by spraying
Nanotube powder, spray-drying apparatus parameter are as follows: intake 100%, charging rate 5mL/min, 180 DEG C of inlet air temperature.
5th step, vapor etching:
Antimony selenide/carbon nanotube powder is placed in tube furnace, tube furnace both ends are sealed.Prepare a conical flask simultaneously
With band, there are three the rubber stoppers of snorkel to be sealed against, and three snorkels pass through rubber tube and water bottle, argon bottle and tubular type respectively
Furnace is connected.The rubber tube being connected with water bottle is fastened first, argon gas is passed through into conical flask, enters argon gas by conical flask
Air is caught up with to the greatest extent after continuing 1h, diamond heating switch is opened, with 10 DEG C of min by tube furnace-1Heating rate be warming up to 200
℃.20mL deionized water is passed through into conical flask simultaneously, and opening water-bath makes the water in conical flask be heated to 85 DEG C.Then will
Argon gas is passed through tube furnace after being passed through the deionized water that temperature is 85 DEG C again, makes to contain vapor in the argon gas being passed through in tube furnace,
The content of vapor is passed through the flow control of argon gas in 2L/min by being passed through the flow control of argon gas, at this time vapor in argon gas
Content be 25%, be passed through 5min, be then turned off tube furnace, to be cooled to after room temperature, obtained sample, that is, vapor etching
Antimony selenide/carbon nano tube compound material afterwards.
6th step, the preparation of battery cathode sheet and the assembling of battery:
The ratio for being 8: 1: 1 according to mass ratio by antimony selenide/carbon nano tube compound material obtained and conductive agent and binder
Example is placed in mortar, and ground and mixed uniformly scratches on copper foil at slurry, by slurry, and drying for 24 hours, is existed using tablet press machine at 55 DEG C
5MPa pressure pushes flakiness, obtains negative electrode tab.It is anode by cathode, metal Li piece of gained antimony selenide/carbon nanotube, is added
Electrolyte carries out battery assembly in glove box, obtains button CR2025 half-cell.
Chemical property analysis (BTS-5V5mA, new prestige) is carried out to prepared sample.
For rodlike antimony selenide distribution of lengths prepared by embodiment 1 at 1~1.5 μm, width is 50~100nm, spraying made
Standby antimony selenide/carbon nano tube compound material nanosphere diameter is evenly distributed between 3.5~4.1 μm.And since water steams
Gas etching, surface are generated compared with multi-pore structure.Electrochemical results show that second of discharge capacity is 628mAh g-1。
Embodiment 2
Antimony selenide water phase suspension is diluted to 500mL for the 4th step with embodiment 1, difference by other, and the 5th step will
Tube furnace is warming up to 300 DEG C.
Fig. 1 is antimony selenide/carbon nano tube compound material X-ray diffractogram prepared by embodiment 2.It can from figure
Out, there is one than wider peak in 26 ° of place, this peak is the carbon peak of carbon nanotube.And remaining peak with antimony selenide
Peak is corresponding, to demonstrate the successful synthesis of antimony selenide/carbon nanotube composite material.
Fig. 2 is antimony selenide/carbon nano tube compound material scanning electron microscope diagram prepared by embodiment 2.It can be seen that
For rodlike antimony selenide distribution of lengths at 1~1.5 μm, width is 50~100nm, and spraying obtained antimony selenide/carbon nanotube is in equal
The near-spherical structure that the diameter of even distribution is 3~3.5 μm, rodlike antimony selenide is by carbon nanotube uniform winding.And chondritic
There are a large amount of hole configurationss on surface.
Fig. 3 be embodiment 2 prepared by antimony selenide/carbon nano tube compound material as sodium-ion battery cathode when in electric current
Density is second of charging and discharging curve under 0.1C.The sodium-ion battery that antimony selenide/carbon nanotube does cathode discharges appearance for the second time
Amount is 657mAh g-1, coulombic efficiency is up to 99.7%.
Embodiment 3
Antimony selenide water phase suspension is diluted to 650mL, the 5th step pipe for the 4th step with embodiment 1, difference by other
Formula furnace is warming up to 400 DEG C.
For rodlike antimony selenide distribution of lengths prepared by embodiment 3 at 1~1.5 μm, width is 50~100nm, spraying made
Standby antimony selenide/carbon nano tube compound material, since the Concentration of precursor solution prepared before being spray-dried is lower, spraying prepared selenium
Change antimony/carbon nano tube compound material nanostructure size is smaller, and diameter is evenly distributed between 2~2.8 μm, and since water steams
Gas etching temperature is higher, and surface hole defect significantly increases.Electrochemical results show that second of discharge capacity is 649mAh g-1。
Embodiment 4
Other are with embodiment 1, and difference is that 1.5g antimony selenide is added in 20mL triethylene glycol by the first step, and second step is matched
The concentration for the selenium liquid set is 1.5mmol/mL.
Rodlike antimony selenide distribution of lengths prepared by embodiment 4 is at 1.2~1.6 μm, and width distribution is in 80~120nm, spray
Antimony selenide/carbon nano tube compound material diameter obtained by mist is distributed in 3.1~3.5 μm, and surface has more vapor etching to generate
Hole.Electrochemical results show that second of discharge capacity is 622mAh g-1。
Embodiment 5
Other are with embodiment 1, and difference is that 2g antimony selenide is added in 20mL triethylene glycol by the first step, second step configuration
Selenium liquid concentration be 2mmol/mL.
Rodlike antimony selenide distribution of lengths prepared by embodiment 5 is at 1.5~1.9 μm, and width distribution is in 90~135nm, spray
Antimony selenide/carbon nano tube compound material diameter obtained by mist is distributed in 3.2~3.6 μm, and surface has more vapor etching to generate
Hole.Electrochemical results show that second of discharge capacity is 628mAh g-1。
Embodiment 6
Reaction temperature is upgraded to 230 DEG C for third step with embodiment 1, difference by other, and the reaction time extends to
35min。
Rodlike antimony selenide distribution of lengths prepared by embodiment 6 is at 1.8~1.9 μm, and width distribution is in 70~105nm, spray
Antimony selenide/carbon nano tube compound material diameter obtained by mist is distributed in 3.1~3.3 μm, and surface has more vapor etching to generate
Hole.Electrochemical results show that second of discharge capacity is 638mAh g-1。
Embodiment 7
Reaction temperature is upgraded to 250 DEG C for third step with embodiment 1, difference by other, and the reaction time extends to
50min。
Rodlike antimony selenide distribution of lengths prepared by embodiment 7 is at 1.85~2 μm, and width distribution is in 90~110nm, by spraying
Gained antimony selenide/carbon nano tube compound material diameter is distributed in 3.2~3.5 μm, the hole that surface has more vapor etching to generate
Hole.Electrochemical results show that second of discharge capacity is 630mAh g-1。
In order to what is generated when solving the problems, such as that antimony selenide is applied to sodium-ion battery cathode, carved in the present invention by water vapour
Technical treatment antimony selenide/carbon nano tube compound material is lost, antimony selenide/carbon nano tube compound material surface is made to generate a large amount of atom
Defect, this is conducive to the transmission of charge and discharge process intermediate ion and electronics, to improve efficiency for charge-discharge.And its surface generates hole
Hole is conducive to alleviate the bulk effect in charge and discharge process, keeps the integrality of structure.In addition, by doing by spraying in the present invention
Dry method prepares negative electrode material of the antimony selenide/carbon nano tube compound material as sodium-ion battery.Since carbon nano-tube material has
Some excellent features, and antimony selenide is compound can improve problems existing for antimony selenide, such as further increases it and lead
Electrically, the transmission path for shortening electronics and ion, to improve its chemical property.And carbon nanotube is with higher flexible
Property, by interlaced formation three-dimensional net structure, the volume change of antimony selenide in charge and discharge process is effectively buffered, to come
Improve the cycle performance of battery.
Unaccomplished matter of the present invention is well-known technique.
Claims (2)
1. a kind of preparation method of anode material of lithium-ion battery, it is characterized in that including the following steps:
Step 1: configuration antimony trichloride solution；Wherein, solvent is triethylene glycol, is added 0.5~2g's in every 20~50mL triethylene glycol
Antimony trichloride；
Step 2: compound concentration is 0.2~2mmol/mL selenium liquid；Wherein, solvent is ethanol amine and hydrazine hydrate, volume ratio ethanol amine
With hydrazine hydrate=1~5:1；
Step 3: antimony selenide dispersion liquid is prepared:
The selenium liquid prepared in step 2, polyethylene pyrrole network alkanone and triethylene glycol are added in closed container, led to after vacuumizing
Enter argon gas, then heats to 200~250 DEG C, then the antimony trichloride solution obtained by injection step one in syringe, keep
It stirred at 200~250 DEG C, react 20~50min；After being cooled to room temperature, centrifugation obtains antimony selenide, is added into deionization
Water ultrasonic disperse obtains antimony selenide water phase suspension；
Wherein, the selenium liquid prepared in every 7~20mL step 2 adds 0.2~2g polyethylene pyrrole network alkanone, 10~50mL triethylene glycol
With the antimony trichloride solution of 20~200mL；10~20mL deionized water is added in every 1g antimony selenide；
Step 4: powder is prepared by spraying: antimony selenide water phase suspension is diluted to 10~100 times of original volume, ultrasound 0.5~
1.5h；Carbon nanotube powder is added, 0.5~1.5h of ultrasound is continued；Then antimony selenide/carbon nanotube powder is obtained by spraying；
Wherein, antimony selenide and the mass ratio of carbon nanotube are 1:0.2~1.5, spray-drying apparatus parameter are as follows: intake 100%,
3~10mLmin of charging rate-1, 150~200 DEG C of inlet air temperature；
Step 5: vapor etching:
Antimony selenide/carbon nanotube powder is placed in tube furnace, airtight tube type furnace under argon atmosphere；Then heated Tube-furnace,
It is warming up to 200~400 DEG C；3~10min of mixed gas is then passed to, turns off tube furnace, it is to be cooled to after room temperature, obtain selenizing
Antimony/carbon nano tube compound material, the i.e. preparation method of anode material of lithium-ion battery；Wherein, the group of mixed gas is steamed as water
Gas and argon gas, the volume of vapor are the 10~30% of mixed gas volume.
2. the preparation method of anode material of lithium-ion battery as described in claim 1, it is characterized in that in the step five
Heating rate is 5~10 DEG C of min-1。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111063873A (en) * | 2019-12-11 | 2020-04-24 | 肇庆市华师大光电产业研究院 | Preparation method of cobalt sulfide-cobalt oxide composite sodium ion battery cathode material |
| CN111293292A (en) * | 2020-02-19 | 2020-06-16 | 肇庆市华师大光电产业研究院 | Preparation method of lithium-sulfur battery positive electrode material |
| CN112490413A (en) * | 2019-09-11 | 2021-03-12 | 肇庆市华师大光电产业研究院 | Preparation method of carbon nano tube sulfur positive electrode material and application of carbon nano tube sulfur positive electrode material in sodium-sulfur battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106145096A (en) * | 2015-05-13 | 2016-11-23 | 储晞 | Three-dimensional grapheme production method, device, combination electrode material and preparation and application |
| CN106898752A (en) * | 2017-03-31 | 2017-06-27 | 中南大学 | A kind of porous spherical vanadium phosphate sodium/carbon pipe composite positive pole and preparation method thereof |
| CN107934923A (en) * | 2017-11-07 | 2018-04-20 | 陕西科技大学 | A kind of nanometer sheet self assembly flower ball-shaped Sb2Se3The preparation method of anode material of lithium-ion battery |
| 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 |
| CN108123112A (en) * | 2016-11-30 | 2018-06-05 | 比亚迪股份有限公司 | A kind of N doping porous graphene aggregation and its preparation method and application |
-
2018
- 2018-08-07 CN CN201810889045.7A patent/CN108963237B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106145096A (en) * | 2015-05-13 | 2016-11-23 | 储晞 | Three-dimensional grapheme production method, device, combination electrode material and preparation and application |
| CN108123112A (en) * | 2016-11-30 | 2018-06-05 | 比亚迪股份有限公司 | A kind of N doping porous graphene aggregation and its preparation method and application |
| CN106898752A (en) * | 2017-03-31 | 2017-06-27 | 中南大学 | A kind of porous spherical vanadium phosphate sodium/carbon pipe composite positive pole and preparation method thereof |
| CN107934923A (en) * | 2017-11-07 | 2018-04-20 | 陕西科技大学 | A kind of nanometer sheet self assembly flower ball-shaped Sb2Se3The preparation method of anode material of lithium-ion battery |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| XIA WANG等: "Antimony Selenide Nanorods Decorated on Reduced Graphene Oxide with Excellent Electrochemical Properties for Li-Ion Batteries", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112490413A (en) * | 2019-09-11 | 2021-03-12 | 肇庆市华师大光电产业研究院 | Preparation method of carbon nano tube sulfur positive electrode material and application of carbon nano tube sulfur positive electrode material in sodium-sulfur battery |
| CN111063873A (en) * | 2019-12-11 | 2020-04-24 | 肇庆市华师大光电产业研究院 | Preparation method of cobalt sulfide-cobalt oxide composite sodium ion battery cathode material |
| CN111063873B (en) * | 2019-12-11 | 2022-06-03 | 肇庆市华师大光电产业研究院 | Preparation method of cobalt sulfide-cobalt oxide composite sodium ion battery cathode material |
| CN111293292A (en) * | 2020-02-19 | 2020-06-16 | 肇庆市华师大光电产业研究院 | Preparation method of lithium-sulfur battery positive electrode material |
| CN111293292B (en) * | 2020-02-19 | 2022-08-09 | 肇庆市华师大光电产业研究院 | Preparation method of lithium-sulfur battery positive electrode material |
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