CN107658454A - The selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet and preparation method - Google Patents
The selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet and preparation method Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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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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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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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- Y02E60/10—Energy storage using batteries
Abstract
The selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet and preparation method, the negative material are made up of following methods：（1）Vanadium source is added in solvent, heating stirring, until dissolving, obtains solution A；（2）Selenium source is added in solution A, stirring, until dissolving, and reducing agent is added, stir, obtain solution B；（3）Graphene is added in solution B, ultrasound, obtains liquid C；（4）Heating, hydro-thermal reaction, obtains presoma, washs, and centrifuges, and dries,.Two selenizing vanadium are pure phase in two selenizing vanadium/graphene nanometer sheet of the invention, and two selenizing vanadium particles are wrapped up by upper and lower two layer graphene and are in sandwich structure；Sodium-ion battery is assembled into it, specific capacity is high, good cycling stability；The inventive method is simple to operate, and cost is low, and controllability is strong, reproducible, is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of anode material of lithium-ion battery and preparation method, and in particular to a kind of sodium-ion battery negative pole
The selenizing vanadium of material two/graphene nanometer sheet and preparation method.
Background technology
In recent years, with the fast developments such as electronic equipment, electric tool, small power electric electrical automobile, research high energy efficiency, resource
Abundant and environment-friendly energy storage material is the necessary condition that human society realizes sustainable development.It is in large scale to meet
The market demand, it is far from being enough to only rely on the performance measure battery material such as energy density, charge-discharge magnification.Battery is manufactured into
Sheet and energy consumption, if polluted to environment and the recovery utilization rate of resource is also by as the important finger of evaluation battery material
Mark.At present, lithium ion battery is development prospect high-energy battery system the brightest and the clearest, but as the industries such as number, traffic are to lithium
Ion battery relies on aggravation, and limited lithium resource will face shortage problem.The research and development of sodium-ion battery are to a certain degree
On can relax the problem of battery development triggered by lithium resource shortage is limited.If function admirable, safety are developed on this basis
Stable material, sodium-ion battery will possess the market competition advantage bigger than lithium battery.According to current progress, sodium from
Sub- battery has 3 outstanding advantages compared with lithium ion battery：（1）Raw material resources are enriched, and cost is cheap, widely distributed；（2）Sodium from
The half-cell potential of sub- battery 0.3~0.4 V high compared with lithium ion potential, can utilize the lower electrolyte solvent of decomposition potential and
Electrolytic salt, the range of choice of electrolyte are wider；（3）Sode cell has a metastable chemical property, and use is safer.Cause
This, in energy storage field, sodium-ion battery is expected to the substitute as lithium ion battery.
But being relatively large in diameter due to sodium ion, the deintercalation of a large amount of sodium ions can cause the enormousness of material to change, and
So that material structure destroys so that capacity sharp-decay.Carbon coating is one of effective way for slowing down material volume change.
In recent years, two-dimensional layer transient metal sulfide has attracted the sight of increasing researchers.This kind of material
With layer structure：Metal atomic layer is between upper and lower two layers of S atom, and metal and S atom are by covalent key connection, and S layers
It is connected between S layers by faint Van der Waals force.The research of early stage is thought, this to be advantageous to layer structure as graphite-like
Na+Quick embedded abjection, thus sodium ion battery electrode material can be used as.Pass through the research to its chemical property, hair
Such existing material possesses higher specific discharge capacity and circulation specific capacity.VSe2Research is also enjoyed as one kind in such material
The concern of persons.With MoSe2、WSe2And SnSe2Compared Deng material, VSe2It is lighter, higher theoretical specific capacity has been provided simultaneously with,
Its degree of metallization is higher simultaneously, is advantageous to the transmission of electronics, therefore, its chemical property is more excellent.But as one
Kind negative material, VSe2Also there are some defects.During electrochemical property test, a large amount of deintercalations of sodium ion can cause VSe2
Volume Changes so that VSe2Structure is destroyed, and causes VSe2Material specific capacity reduces, and cyclical stability weakens.
The A of CN 104051733 disclose a kind of two selenizing vanadium/C-base composte material, preparation method and lithium ion battery and born
Electrode, still, because graphene is not thorough enough to the cladding of two selenizing vanadium, during material carries out long-range charge and discharge, Wu Fafei
The often effective Volume Changes for suppressing material, reduce the cycle performance of material.
The content of the invention
The technical problems to be solved by the invention are to overcome drawbacks described above existing for prior art, there is provided a kind of purity is high,
High with the sodium-ion battery specific capacity of its preparation, good cycling stability is easy to operate, and cost is low, is suitable for industrialized production
The selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet and preparation method.
The technical solution adopted for the present invention to solve the technical problems is as follows：A kind of selenizing of anode material of lithium-ion battery two
Vanadium/graphene nanometer sheet, is made up of following methods：
（1）Vanadium source is added in solvent, heats and continues to stir, until dissolving, obtains solution A；
（2）Selenium source is added into step（1）In resulting solution A, lasting stirring, until dissolving, and reducing agent is added, stirring is until molten
Liquid is well mixed, and obtains solution B；
（3）Graphene is added into step（2）In resulting solution B, then ultrasound is uniform to graphene dispersion, obtains liquid C；
（4）To step（3）Gained liquid C is heated, and is carried out hydro-thermal reaction, is obtained presoma, is washed, and is centrifuged, and is dried, and obtains sodium ion electricity
The selenizing vanadium of pond negative material two/graphene nanometer sheet.
Preferably, step（1）In, the concentration of v element in a solvent is 5~100mmol/L in the vanadium source.If vanadium is dense
Spend high or too low be all difficult to form Stability Analysis of Structures, two pure selenizing vanadium.
Preferably, step（1）In, the temperature of the heating is 40~60 DEG C.
Preferably, step（1）In, the speed of the stirring is 80~900 turns/min（More preferably 300~600 turns/min）.
Preferably, step（1）In, the vanadium source is one in sodium metavanadate, potassium metavanadate, ammonium metavanadate or sodium vanadate etc.
Kind is several.
Preferably, step（1）In, the solvent is that the volume ratio of water and ethanol is 1:0.5~2.0 mixed solution.Second
The boiling point of alcohol is less than water, and the mixed ratio is more beneficial for during hydro-thermal is carried out, preparing excellent performance, structure is steady
It is fixed, the good two selenizing vanadium/graphene nanometer sheet of pattern.
Preferably, step（2）In, selenium element and the mol ratio of v element in vanadium source are 2~3 in the selenium source:1.Raw material
The difference of concentration can influence to ultimately form the purity and pattern of material, prepared two selenizing vanadium/graphene under the ratio
Nanometer sheet best performance.
Preferably, step（2）In, the mol ratio of the reducing agent and selenium element in selenium source is 5~55:1（More preferably 20~
30:1）.Reducing agent can be reduced the selenium in raw material and vanadium, ultimately form two selenizing vanadium/graphene nanometer sheet.
Preferably, step（2）In, the speed of the stirring is 80~900 turns/min（More preferably 300~600 turns/min）.
Preferably, step（2）In, the selenium source is the one or more in selenium dioxide, sodium selenate or sodium selenite etc..
Preferably, step（2）In, the reducing agent is the one or more in formic acid, sodium borohydride or hydrazine hydrate etc..
Preferably, step（3）In, the mass ratio in the graphene and vanadium source is 0.08~3.50:1（More preferably 0.09~
2.00:1, still more preferably 0.1~0.5:1）.If graphene dosage is very few, graphene is difficult to fully wrapped around two selenizings vanadium
Particle, if graphene dosage is excessive, the overall chemical property of material can be reduced.Preparation system of the present invention in two selenizing vanadium
In improve the amount of graphene so that the graphene in two selenizing vanadium/graphene nano sheet material of sandwich structure can be complete
Two selenizing vanadium materials of full parcel, farthest inhibit Volume Changes of the material during long-range charge and discharge, improve material
Cyclical stability；The raising of graphene content also can further improve the electric conductivity of material simultaneously.
Preferably, step（3）In, the ultrasonic power is 100~600W（More preferably 300~500W）, when ultrasonic
Between be 1~6h（More preferably 3~5h）.
Preferably, step（4）In, the temperature of the hydro-thermal reaction is 140~240 DEG C（More preferably 160~220 DEG C）, water
The time of thermal response is 8~48h（More preferably 10~40h）.Water-heat process is had under suitable temperature and time, is just more had
Grown beneficial to the forming core of material, prepare the material of two selenizing vanadium/graphene of sandwich structure.The sandwich structure is formed
The reason for be that agglomeration can occur in water-heat process for graphene, and two selenizing vanadium forming core between two layer graphenes grows,
Final two selenizings vanadium particle is clipped in the middle by two layer graphenes, forms the structure of similar sandwich.
Preferably, step（4）In, the washing refers to use deionized water and ethanol cross washing, number >=3 of washing
It is secondary.
Preferably, step（4）In, the rotating speed of the centrifugation is 3000~9000 turns/min（More preferably 7000~8800 turns/
min）.
Preferably, step（4）In, the temperature of the drying is 45~90 DEG C, and the dry time is 8~18h.
The method that the present invention uses solvent heat, wherein reducing agent respectively can reduce the vanadium in vanadium source and selenium source and selenium, and
Two selenizing vanadium are ultimately formed, and graphene solvent can reunite in water-heat process, two selenizing vanadium are in graphite in the process
Forming core between alkene layer, grow up, ultimately form two selenizing vanadium/graphene nano sheet material of sandwich structure.Because graphene is complete
Two selenizing vanadium particles of full parcel, can effectively suppressing two selenizing vanadium particles, volume caused by during a large amount of sodium ion deintercalations becomes
Change, while the carbon network structure that graphene is formed, electric transmission can be accelerated, the passage that carbon network is formed can also be electrolyte
Flowing provide passage, finally improve its chemical property.
Beneficial effects of the present invention are as follows：
（1）In the selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet of sandwich structure of the present invention, two selenizing vanadium
Grain is wrapped up by upper and lower two layer graphene and is in sandwich structure, wherein, two selenizing vanadium are 700~1100nm of length of side square
Grain, two selenizing vanadium are pure phase；
（2）The selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet of the present invention is assembled into sodium-ion battery, 0~
In 3V voltage ranges, under 100mA/g current densities, the gram volume that discharges first may be up to 1261.2mAh/g, and coulombic efficiency is stable；
Reversible specific capacity can reach 305 mAh/g first, be 260.7 mAh/g after 78 circulations, and its capability retention is 85.5%,
Illustrating the battery of two selenizing vanadium of the invention/graphene nanometer sheet assembling has very high specific capacity and fabulous stable circulation
Property, there is significant economic value；
（3）The inventive method is simple to operate, and cost is low, and controllability is strong, reproducible, and applicability is wide, is suitable for industrialized production.
Brief description of the drawings
Fig. 1 is the XRD of the selenizing vanadium of 1 gained anode material of lithium-ion battery of the embodiment of the present invention two/graphene nanometer sheet；
Scheme for the SEM of the selenizing vanadium of 1 gained anode material of lithium-ion battery of the embodiment of the present invention two/graphene nanometer sheet Fig. 2~4
（Wherein, Fig. 2 multiplication factors are 20000 times, and Fig. 3 multiplication factors are 40000 times, and Fig. 4 multiplication factors are 80000 times）；
Fig. 5 is that the selenizing vanadium of 1 gained anode material of lithium-ion battery of the embodiment of the present invention two/graphene nanometer sheet is applied to sodium ion
The charge-discharge magnification performance chart of battery；
Fig. 6 is that the selenizing vanadium of 1 gained anode material of lithium-ion battery of the embodiment of the present invention two/graphene nanometer sheet is applied to sodium ion
The charge-discharge performance figure of battery.
Embodiment
With reference to embodiment and accompanying drawing, the invention will be further described.
The density of formic acid used in the embodiment of the present invention is 1.22g/mL, and the density of used hydrazine hydrate is 1.03g/
mL；Chemical reagent used in the embodiment of the present invention, unless otherwise specified, obtained by routine business approach.
Embodiment 1
（1）By 3mmol sodium metavanadates（365.8mg）Add the mixed solution of 60mL water and ethanol（The volume ratio of water and ethanol is
1:0.5）In, 50 DEG C are heated to, and under 400 turns/min, lasting stirring, until dissolving, obtains solution A；
（2）6mmol selenium dioxide is added into step（1）In resulting solution A, under 450 turns/min, lasting stirring, until dissolving,
And add 6mL formic acid（160mmol）, under 500 turns/min, stirring is well mixed up to solution, obtains solution B；
（3）100mg graphenes are added into step（2）In resulting solution B, then under 300W, ultrasonic 4h is equal to graphene dispersion
It is even, obtain liquid C；
（4）To step（3）Gained liquid C is heated, and at 200 DEG C, is carried out hydro-thermal reaction 24h, is obtained presoma, with deionized water and
Ethanol cross washing 3 times, is centrifuged under 8000 turns/min, at 80 DEG C, is dried 14h, is obtained anode material of lithium-ion battery two
Selenizing vanadium/graphene nanometer sheet.
As shown in figure 1, the selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet XRD obtained by the embodiment of the present invention
On peak value and standard items peak value it is basically identical, it may be determined that what the embodiment of the present invention obtained is two selenizing vanadium pure phases.
As shown in figs. 2 to 4, the selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet obtained by the embodiment of the present invention
In, two selenizing vanadium particles are wrapped up by upper and lower two coatings graphene film, and heave, and overall is in sandwich structure, wherein, two selenizings
Vanadium particle is length of side 700nm square particle.
Battery assembles：The selenizing vanadium of anode material of lithium-ion battery two/graphene obtained by 0.24g the present embodiment is weighed respectively to receive
Rice piece adds 0.03g acetylene blacks as negative material（SP）Make conductive agent and 0.03g PVDF（HSV-900）Make binding agent, fill
2mL NMP dispersion mixings are added after dividing grinding, sizes mixing and cathode pole piece uniformly is made after slurry on the copper foil of 16 μ m-thicks, in anaerobism
Using metallic sodium piece as positive pole in glove box, using Whatman GF/D glass fibres as barrier film, 1mol/L NaClO4/EC:PC（Body
Product ratio 1:1）For electrolyte, CR2025 button cell is assembled into.In the case where voltage range is 0~3V, to the sodium ion electricity of assembling
The constant current charge-discharge performance in pond is tested.
As shown in figure 5, under 100mA/g current density, discharge capacity can first for the negative pole of the sodium-ion battery of assembling
Reach 1261.2mAh/g；Under 5000mA/g current density, its specific discharge capacity still can reach 73.5mAh/g, coulombic efficiency
It is stable.
As shown in fig. 6, under 100mA/g current density, the reversible specific capacity first of the sodium-ion battery of assembling is reachable
It is 260.7 mAh/g after 70 circulations to 305 mAh/g, its capability retention is 85.5%.
From the foregoing, it will be observed that the selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet institute group obtained by the embodiment of the present invention
The sodium-ion battery of dress has higher specific capacity and good cyclical stability.
Embodiment 2
（1）By 5mmol sodium metavanadates（609.7mg）Add the mixed solution of 50mL water and ethanol（The volume ratio of water and ethanol is
1:2）In, 55 DEG C are heated to, and under 450 turns/min, lasting stirring, until dissolving, obtains solution A；
（2）10mmol selenium dioxide is added into step（1）In resulting solution A, under 400 turns/min, lasting stirring, until molten
Solution, and add 10mL formic acid（265mmol）, under 480 turns/min, stirring is well mixed up to solution, obtains solution B；
（3）61mg graphenes are added into step（2）In resulting solution B, then under 350W, ultrasonic 3h is equal to graphene dispersion
It is even, obtain liquid C；
（4）To step（3）Gained liquid C is heated, and at 210 DEG C, is carried out hydro-thermal reaction 26h, is obtained presoma, with deionized water and
Ethanol cross washing 3 times, is centrifuged under 8200 turns/min, at 68 DEG C, is dried 10h, is obtained anode material of lithium-ion battery two
Selenizing vanadium/graphene nanometer sheet.
After testing, two selenizing vanadium pure phases are contained in anode material of lithium-ion battery obtained by the embodiment of the present invention.
After testing, in the selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet obtained by the embodiment of the present invention, two selenium
Change vanadium particle to be wrapped up by upper and lower two coatings graphene film, and heave, overall is in sandwich structure, wherein, two selenizing vanadium particles
For length of side 900nm square particle.
Battery assembles：With embodiment 1.In the case where voltage range is 0~3V, the constant current charge and discharge to the sodium-ion battery of assembling
Electrical property is tested.
After testing, under 100mA/g current density, discharge capacity can reach the negative pole of the sodium-ion battery of assembling first
1000.5mAh/g；Under 5000mA/g current density, its specific discharge capacity still can reach 52.1mAh/g.
After testing, under 100mA/g current density, the reversible specific capacity first of the sodium-ion battery of assembling can reach
270.5mAh/g, is 219.3mAh/g after 70 circulations, and its capability retention is 81.1%.
From the foregoing, it will be observed that the selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet institute group obtained by the embodiment of the present invention
The sodium-ion battery of dress has higher specific capacity and good cyclical stability.
Embodiment 3
（1）By 0.5mmol sodium metavanadates（61mg）Add the mixed solution of 55mL water and ethanol（The volume ratio of water and ethanol is 1:
1）In, 58 DEG C are heated to, and under 500 turns/min, lasting stirring, until dissolving, obtains solution A；
（2）1.5mmol selenium dioxide is added into step（1）In resulting solution A, under 480 turns/min, lasting stirring, until molten
Solution, and add 1mL formic acid（26.5mmol）, under 520 turns/min, stirring is well mixed up to solution, obtains solution B；
（3）120mg graphenes are added into step（2）In resulting solution B, then under 330W, ultrasonic 3h is equal to graphene dispersion
It is even, obtain liquid C；
（4）To step（3）Gained liquid C is heated, and at 200 DEG C, is carried out hydro-thermal reaction 30h, is obtained presoma, with deionized water and
Ethanol cross washing 3 times, is centrifuged under 8300 turns/min, at 60 DEG C, is dried 13h, is obtained anode material of lithium-ion battery two
Selenizing vanadium/graphene nanometer sheet.
After testing, two selenizing vanadium pure phases are contained in anode material of lithium-ion battery obtained by the embodiment of the present invention.
After testing, in the selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet obtained by the embodiment of the present invention, two selenium
Change vanadium particle to be wrapped up by upper and lower two coatings graphene film, and heave, overall is in sandwich structure, wherein, two selenizing vanadium particles
For length of side 850nm square particle.
Battery assembles：With embodiment 1.In the case where voltage range is 0~3V, the constant current charge and discharge to the sodium-ion battery of assembling
Electrical property is tested.
After testing, under 100mA/g current density, discharge capacity can reach the negative pole of the sodium-ion battery of assembling first
950.5mAh/g；Under 5000mA/g current density, its specific discharge capacity still can reach 46.1mAh/g.
After testing, under 100mA/g current density, the reversible specific capacity first of the sodium-ion battery of assembling can reach
230.5mAh/g, is 179.8 mAh/g after 70 circulations, and its capability retention is 78%.
From the foregoing, it will be observed that the selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet institute group obtained by the embodiment of the present invention
The sodium-ion battery of dress has higher specific capacity and good cyclical stability.
Embodiment 4
（1）By 3mmol potassium metavanadates（413.8mg）Add the mixed solution of 50mL water and ethanol（The volume ratio of water and ethanol is
1:0.7）In, 46 DEG C are heated to, and under 400 turns/min, lasting stirring, until dissolving, obtains solution A；
（2）6mmol sodium selenates are added into step（1）In resulting solution A, under 490 turns/min, lasting stirring, until dissolving, and
30mmol sodium borohydrides are added, under 520 turns/min, stirring is well mixed up to solution, obtains solution B；
（3）110mg graphenes are added into step（2）In resulting solution B, then under 330W, ultrasonic 5h is equal to graphene dispersion
It is even, obtain liquid C；
（4）To step（3）Gained liquid C is heated, and at 200 DEG C, is carried out hydro-thermal reaction 20h, is obtained presoma, with deionized water and
Ethanol cross washing 3 times, is centrifuged under 8800 turns/min, at 85 DEG C, is dried 10h, is obtained anode material of lithium-ion battery two
Selenizing vanadium/graphene nanometer sheet.
After testing, two selenizing vanadium pure phases are contained in anode material of lithium-ion battery obtained by the embodiment of the present invention.
After testing, in the selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet obtained by the embodiment of the present invention, two selenium
Change vanadium particle to be wrapped up by upper and lower two coatings graphene film, and heave, overall is in sandwich structure, wherein, two selenizing vanadium particles
For length of side 950nm square particle.
Battery assembles：With embodiment 1.In the case where voltage range is 0~3V, the constant current charge and discharge to the sodium-ion battery of assembling
Electrical property is tested.
After testing, under 100mA/g current density, discharge capacity can reach the negative pole of the sodium-ion battery of assembling first
918.5mAh/g；Under 5000mA/g current density, its specific discharge capacity still can reach 42.8mAh/g.
After testing, under 100mA/g current density, the reversible specific capacity first of the sodium-ion battery of assembling can reach
217.5mAh/g, is 168.8 mAh/g after 70 circulations, and its capability retention is 77.6%.
From the foregoing, it will be observed that the selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet institute group obtained by the embodiment of the present invention
The sodium-ion battery of dress has higher specific capacity and good cyclical stability.
Embodiment 5
（1）By 4mmol potassium metavanadates（551.7mg）Add the mixed solution of 55mL water and ethanol（The volume ratio of water and ethanol is
1:1.2）In, 50 DEG C are heated to, and under 400 turns/min, lasting stirring, until dissolving, obtains solution A；
（2）8mmol sodium selenates are added into step（1）In resulting solution A, under 465 turns/min, lasting stirring, until dissolving, and
Add 9mL hydrazine hydrates（185.2mmol）, under 490 turns/min, stirring is well mixed up to solution, obtains solution B；
（3）90mg graphenes are added into step（2）In resulting solution B, then under 420W, ultrasonic 3h is equal to graphene dispersion
It is even, obtain liquid C；
（4）To step（3）Gained liquid C is heated, and at 160 DEG C, is carried out hydro-thermal reaction 40h, is obtained presoma, with deionized water and
Ethanol cross washing 3 times, is centrifuged under 7800 turns/min, at 75 DEG C, is dried 15h, is obtained anode material of lithium-ion battery two
Selenizing vanadium/graphene nanometer sheet.
After testing, two selenizing vanadium pure phases are contained in anode material of lithium-ion battery obtained by the embodiment of the present invention.
After testing, in the selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet obtained by the embodiment of the present invention, two selenium
Change vanadium particle to be wrapped up by upper and lower two coatings graphene film, and heave, overall is in sandwich structure, wherein, two selenizing vanadium particles
For length of side 1000nm square particle.
Battery assembles：With embodiment 1.In the case where voltage range is 0~3V, the constant current charge and discharge to the sodium-ion battery of assembling
Electrical property is tested.
After testing, under 100mA/g current density, discharge capacity can reach the negative pole of the sodium-ion battery of assembling first
885.5mAh/g；Under 5000mA/g current density, its specific discharge capacity still can reach 40.1mAh/g.
After testing, under 100mA/g current density, the reversible specific capacity first of the sodium-ion battery of assembling can reach
200.5mAh/g, is 144.4 mAh/g after 70 circulations, and its capability retention is 72%.
From the foregoing, it will be observed that the selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet institute group obtained by the embodiment of the present invention
The sodium-ion battery of dress has higher specific capacity and good cyclical stability.
Embodiment 6
（1）By 4.5mmol potassium metavanadates（620.7mg）Add the mixed solution of 50mL water and ethanol（The volume ratio of water and ethanol
For 1:0.9）In, 50 DEG C are heated to, and under 400 turns/min, lasting stirring, until dissolving, obtains solution A；
（2）9mmol sodium selenates are added into step（1）In resulting solution A, under 450 turns/min, lasting stirring, until dissolving, and
Add 10mL formic acid（265mmol）, under 450 turns/min, stirring is well mixed up to solution, obtains solution B；
（3）90mg graphenes are added into step（2）In resulting solution B, then under 300W, ultrasonic 5h is equal to graphene dispersion
It is even, obtain liquid C；
（4）To step（3）Gained liquid C is heated, and at 220 DEG C, is carried out hydro-thermal reaction 10h, is obtained presoma, with deionized water and
Ethanol cross washing 4 times, is centrifuged under 8300 turns/min, at 85 DEG C, is dried 8h, is obtained the selenium of anode material of lithium-ion battery two
Change vanadium/graphene nanometer sheet.
After testing, two selenizing vanadium pure phases are contained in anode material of lithium-ion battery obtained by the embodiment of the present invention.
After testing, in the selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet obtained by the embodiment of the present invention, two selenium
Change vanadium particle to be wrapped up by upper and lower two coatings graphene film, and heave, overall is in sandwich structure, wherein, two selenizing vanadium particles
For length of side 1100nm square particle.
Battery assembles：With embodiment 1.In the case where voltage range is 0~3V, the constant current charge and discharge to the sodium-ion battery of assembling
Electrical property is tested.
After testing, under 100mA/g current density, discharge capacity can reach the negative pole of the sodium-ion battery of assembling first
920.5mAh/g；Under 5000mA/g current density, its specific discharge capacity still can reach 50.1mAh/g.
After testing, under 100mA/g current density, the reversible specific capacity first of the sodium-ion battery of assembling can reach
230.5mAh/g, is 182.4mAh/g after 70 circulations, and its capability retention is 79.1%.
From the foregoing, it will be observed that the selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet institute group obtained by the embodiment of the present invention
The sodium-ion battery of dress has higher specific capacity and good cyclical stability.
Comparative example 1
（1）3mmol sodium metavanadates are added to the mixed solution of 60mL water and ethanol（The volume ratio of water and ethanol is 1:0.5）In,
50 DEG C are heated to, and under 400 turns/min, lasting stirring, until dissolving, obtains solution A；
（2）6mmol selenium dioxide is added into step（1）In resulting solution A, under 450 turns/min, lasting stirring, until dissolving,
And 6mL formic acid is added, under 500 turns/min, stirring is well mixed up to solution, obtains solution B；
（3）To step（2）Resulting solution B is heated, and at 200 DEG C, is carried out hydro-thermal reaction 24h, is obtained presoma, with deionized water and
Ethanol cross washing 3 times, is centrifuged under 8000 turns/min, at 80 DEG C, is dried 14h, is obtained anode material of lithium-ion battery two
Selenizing vanadium.
After testing, two selenizing vanadium pure phases are contained in anode material of lithium-ion battery obtained by this comparative example.
After testing, the selenizing vanadium of anode material of lithium-ion battery two obtained by this comparative example is the length of side about 1500nm square.
Battery assembles：With embodiment 1.In the case where voltage range is 0~3V, the constant current charge and discharge to the sodium-ion battery of assembling
Electrical property is tested.
After testing, under 100mA/g current density, discharge capacity is the negative pole of the sodium-ion battery of assembling first
820.5mAh/g；Under 5000mA/g current density, its specific discharge capacity is still 20.1mAh/g.
After testing, under 100mA/g current density, the reversible specific capacity first of the sodium-ion battery of assembling is 150.5
MAh/g, is 97.4mAh/g after 70 circulations, and its capability retention is 64.7%.
From the foregoing, it will be observed that the selenizing vanadium of 1~6 gained anode material of lithium-ion battery of the embodiment of the present invention two/graphene nanometer sheet
The sodium-ion battery that the sodium-ion battery of assembling assembles relative to the selenizing vanadium of anode material of lithium-ion battery two obtained by this comparative example,
Chemical property is more excellent, while capability retention is also higher, it is seen that the gained sodium-ion battery of the embodiment of the present invention 1~6 is born
The sodium-ion battery of the selenizing vanadium of pole material two/graphene nanometer sheet assembling is more stable in long-range charge and discharge process.This be by
The Volume Changes caused by graphene inhibits material during a large amount of sodium ion deintercalations, improve the high rate performance of material with
And cycle performance.The network of graphene structure is advantageous to the transmission of electronics simultaneously, and provides passage for the circulation of electrolyte,
Improve the chemical property of material.
Claims (8)
1. a kind of selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet, it is characterised in that be made up of following methods：
（1）Vanadium source is added in solvent, heats and continues to stir, until dissolving, obtains solution A；
（2）Selenium source is added into step（1）In resulting solution A, lasting stirring, until dissolving, and reducing agent is added, stirring is until molten
Liquid is well mixed, and obtains solution B；
（3）Graphene is added into step（2）In resulting solution B, then ultrasound is uniform to graphene dispersion, obtains liquid C；
（4）To step（3）Gained liquid C is heated, and is carried out hydro-thermal reaction, is obtained presoma, is washed, and is centrifuged, and is dried, and obtains sodium ion electricity
The selenizing vanadium of pond negative material two/graphene nanometer sheet.
2. the selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet according to claim 1, it is characterised in that：Step
Suddenly（1）In, the concentration of v element in a solvent is 5~100mmol/L in the vanadium source.
3. the selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet according to claim 1 or claim 2, it is characterised in that：
Step（1）In, the temperature of the heating is 40~60 DEG C；The speed of the stirring is 80~900 turns/min.
4. according to one of claims 1 to 3 selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet, its feature
It is：Step（1）In, the vanadium source is the one or more in sodium metavanadate, potassium metavanadate, ammonium metavanadate or sodium vanadate；Institute
It is 1 to state the volume ratio that solvent is water and ethanol:0.5~2.0 mixed solution.
5. according to one of Claims 1 to 4 selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet, its feature
It is：Step（2）In, selenium element and the mol ratio of v element in vanadium source are 2~3 in the selenium source:1；The reducing agent and selenium
The mol ratio of selenium element is 5~55 in source:1；The speed of the stirring is 80~900 turns/min；The selenium source be selenium dioxide,
One or more in sodium selenate or sodium selenite；The reducing agent is one kind or several in formic acid, sodium borohydride or hydrazine hydrate
Kind.
6. according to one of Claims 1 to 5 selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet, its feature
It is：Step（3）In, the mass ratio in the graphene and vanadium source is 0.08~3.50:1；The ultrasonic power be 100~
600W, ultrasonic time are 1~6h.
7. according to one of claim 1~6 selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet, its feature
It is：Step（4）In, the temperature of the hydro-thermal reaction is 140~240 DEG C, and the time of hydro-thermal reaction is 8~48h.
8. according to one of claim 1~7 selenizing vanadium of anode material of lithium-ion battery two/graphene nanometer sheet, its feature
It is：Step（4）In, the washing refers to use deionized water and ethanol cross washing, number >=3 time of washing；The centrifugation
Rotating speed be 3000~9000 turns/min；The temperature of the drying is 45~90 DEG C, and the dry time is 8~18h.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108648921A (en) * | 2018-04-19 | 2018-10-12 | 信阳师范学院 | A kind of preparation method of-two selenizing vanadium nano particle composite electrode material for super capacitor of graphene |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104051733A (en) * | 2014-06-12 | 2014-09-17 | 江苏大学 | Vanadium selenide/carbon-based composite material, preparation method of material, and negative electrode of lithium ion battery |
| CN105226277A (en) * | 2015-09-10 | 2016-01-06 | 中国科学院上海硅酸盐研究所 | A kind of high-performance transition metal dichalcogenide nanometer sheet radial direction assembling micro-sphere material and preparation method thereof |
| CN105609745A (en) * | 2016-03-27 | 2016-05-25 | 华南理工大学 | Nickel selenide/graphene sodium ion battery composite negative material as well as preparation method and application thereof |
-
2017
- 2017-09-22 CN CN201710865828.7A patent/CN107658454A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104051733A (en) * | 2014-06-12 | 2014-09-17 | 江苏大学 | Vanadium selenide/carbon-based composite material, preparation method of material, and negative electrode of lithium ion battery |
| CN105226277A (en) * | 2015-09-10 | 2016-01-06 | 中国科学院上海硅酸盐研究所 | A kind of high-performance transition metal dichalcogenide nanometer sheet radial direction assembling micro-sphere material and preparation method thereof |
| CN105609745A (en) * | 2016-03-27 | 2016-05-25 | 华南理工大学 | Nickel selenide/graphene sodium ion battery composite negative material as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| YANGPING WANG 等: "VSe2/graphene nanocomposites as anode materials for lithium-ion batteies", 《MATERIALS LETERS》 * |
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