CN108110244A - A kind of hollow nucleocapsid vanadic anhydride anode material for lithium-ion batteries of tremelliform and preparation method thereof - Google Patents
A kind of hollow nucleocapsid vanadic anhydride anode material for lithium-ion batteries of tremelliform and preparation method thereof Download PDFInfo
- Publication number
- CN108110244A CN108110244A CN201711385264.3A CN201711385264A CN108110244A CN 108110244 A CN108110244 A CN 108110244A CN 201711385264 A CN201711385264 A CN 201711385264A CN 108110244 A CN108110244 A CN 108110244A
- Authority
- CN
- China
- Prior art keywords
- tremelliform
- lithium
- hollow
- anode material
- vanadic anhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to lithium ion anode material technical fields, disclose hollow nucleocapsid vanadic anhydride anode material for lithium-ion batteries of a kind of tremelliform and preparation method thereof.The present invention is with ethyl orthosilicate, resorcinol, formaldehyde, ammonium metavanadate etc. for raw material, using simple hydro-thermal method, the hollow nucleocapsid vanadic anhydride anode material for lithium-ion batteries of tremelliform being prepared, the hollow nucleocapsid C V of tremelliform of this special appearance2O5Greatly improve existing V2O5The electric conductivity and stability of positive electrode, so as to significantly improve its chemical property.The pattern of tremelliform increases specific surface area, improves chemical property；The presence of hollow carbon sphere improves the electric conductivity of material；Hollow structure greatly improves the stability of material.
Description
Technical field
The present invention relates to lithium ion anode material technical field, more particularly, to a kind of hollow nucleocapsid of tremelliform
Vanadic anhydride anode material for lithium-ion batteries and preparation method thereof.
Background technology
Lithium ion battery is widely used in various mobile electrons as a kind of electrochemical energy storing device of high-efficiency environment friendly
Product, and have huge application prospect in the emerging fields such as electric vehicle and intelligent grid.But current lithium ion battery is low
Energy and power density make it be restricted in electronic and hybrid vehicle application aspect.
In each component of lithium ion battery, the performance of positive electrode is particularly important, and the quality of performance greatly restricts
The raising of lithium ion battery overall performance.Traditional anode material for lithium-ion batteries, such as LiMn2O4、LiFePO4Deng there are prices
Expensive, the defects of resource is limited, structural instability.Compared with cobalt, manganese, the cheap and rich reserves of vanadium have height ratio capacity
The features such as.With the V in the oxide of vanadium2O5During as anode material for lithium-ion batteries, in theory, 1 V2O5Basic structure
Unit can be embedded in 3 lithium ions, and corresponding specific capacity is 442mAh/g, if 2 lithium ions of deintercalation, corresponding theoretical specific capacity
For 294mAh/g, this, which is mainly due to the layer structure of vanadic anhydride uniqueness and V atoms, has from V5+To V3+A variety of oxygen
Change state.Therefore, V2O5Apparent advantage is shown as positive electrode, is expected to becoming next-generation high performance lithium ion battery just
Pole material.
Although V2O5Theoretical specific capacity be up to more than 442mAh/g, but aoxidized in charge and discharge process since Li+ is embedded in
Vanadium electrode material forms out of phase LixV2O5, in these out of phase barium oxides, the structure of part barium oxide can be sent out
Raw irreversible change, and itself poor structural stability, low electrical conductivity（10-2~10-3S.cm-1）And poor electricity
Chemical kinetics performance（Lithium ion diffusion coefficient is 10-12~10-13S.cm2.S-1）, can all reduce the specific capacity of vanadium oxide electrode
And cyclical stability.
There are many research work to solve vanadium oxide itself to a certain extent by carrying out nanosizing to vanadium oxide at present
The intrinsic defect brought of structure.Vanadium oxide is prepared into a series of composite materials with nanostructured, such as 1-dimention nano knot
The nanometer rods of structure, nano wire, nanotube, nanobelt, the nanometer sheet and three-dimensional of two-dimensional nanostructure or classification nanostructure
Nanosphere, nano flower etc. change the intrinsic appearance structure of vanadium oxide, can increase the memory capacity of lithium ion, shorten ion
Diffusion length, reduce the mechanical stress related with lithium ion deintercalation, and then the high rate performance and specific volume of raising lithium ion battery
Amount, improves chemical property.It is but high reversible there are still the shortcomings that electric conductivity and poor structural stability, causing to be difficult to obtain
Capacity and good cycle performance, in order to obtain and keep V2O5The high reversible capacity of electrode material, good circulation performance and excellent
High rate performance be still a very big challenge.
The content of the invention
Present invention solves the technical problem that in view of the shortcomings of the prior art, improve vanadic anhydride (V2O5) itself poor knot
Structure stability, low electrical conductivity and poor electrochemical kinetics performance, provide a kind of high reversible capacity, good cycle,
The hollow nucleocapsid vanadic anhydride anode material for lithium-ion batteries of tremelliform of efficiency for charge-discharge height and stable structure.
The present invention also provides the preparations of the hollow nucleocapsid vanadic anhydride anode material for lithium-ion batteries of the tremelliform
Method.
The purpose of the present invention is achieved through the following technical solutions：
There is provided a kind of tremelliform hollow nucleocapsid vanadic anhydride method for preparing anode material of lithium-ion battery, including following step
Suddenly：
S1. hollow carbon sphere is dissolved in organic solvent, is uniformly mixing to obtain suspension A；
S2. by ammonium metavanadate and urea, deionized water in mass ratio 10~20:150~225：1 uniformly mixing, is then heated simultaneously
Stirring is completely dissolved up to ammonium metavanadate, obtains pale yellow transparent sol B；
S3. pale yellow transparent sol B is added in suspension A, wherein the mass ratio of hollow carbon sphere and ammonium metavanadate is 0.5~2:
1, and be kept stirring in a water bath, it is then transferred into reaction kettle, hydro-thermal reaction, reaction time 12 is carried out at 180~200 DEG C
~for 24 hours, it is centrifuged after having reacted and obtains black product, calcined after black product is dried, finally obtain the C of yellow product
V2O5Powder body material.
The principle of the present invention is, the fixation of the additive amount of hollow carbon sphere and ammonium metavanadate is proportional, strictly controls its water
The time of thermal response and temperature, so as to which the hollow nucleocapsid C V of tremelliform are made2O5Material, the tremelliform of this special appearance
Hollow nucleocapsid C V2O5Greatly improve existing V2O5The electric conductivity and stability of positive electrode, so as to significantly improve it
Chemical property.The pattern of tremelliform increases specific surface area, improves chemical property；The presence of hollow carbon sphere improves material
The electric conductivity of material；Hollow structure greatly improves the stability of material.
Wherein, the urea in step S2 determines the effect and pattern of cladding as additive.
Further, the present invention also provides the preparation method of the hollow carbon sphere, comprise the following steps：
S11. will 5~10ml absolute ethyl alcohols and 60~80ml deionized waters mix after be put into blender stirring, then successively plus
Enter 1~3ml ethyl orthosilicates, 0.5g resorcinols, 0.5~1ml formaldehyde and 3~5ml ammonium hydroxide, 1~3ml is being added in just after stirring 6h
Silester, and continue to be kept stirring；
S12. stir to pour into afterwards for 24 hours and hydro-thermal reaction is carried out in reaction kettle, temperature is 100~120 DEG C, and the reaction time is nature for 24 hours
Centrifugation is 7 to pH after cooling, is then placed in drying box drying；
S13. dried product is put into tube furnace and calcined, temperature is 700~800 DEG C, time 3h, calcining cooling
Afterwards with hydrofluoric acid etch, it is 7 to be then centrifuged for washing to pH, and hollow carbon sphere is obtained after dry.
The present invention with ethyl orthosilicate, resorcinol, formaldehyde, ammonium metavanadate etc. for raw material, using simple hydro-thermal method,
The hollow carbon sphere of high quality is prepared in low cost.
Further, high-quality hollow carbon sphere in order to obtain of the invention controls to adjust the concentration and infiltrating time of hydrofluoric acid
The silicon in carbon ball can be accurately removed, the addition of hydrofluoric acid described in step S13 is 5~10wt%, and infiltrates 24~48h.
Preferably, organic solvent described in step S1 is ethylene glycol.
Preferably, stirring refers to stir 10min on magnetic stirring apparatus in step S1.
Preferably, heating temperature is 50 DEG C in step S2.
Preferably, bath temperature is 50 DEG C in step S3.
Preferably, calcining heat described in step S3 is 450~550 DEG C, and calcination time is 2~4h.
The present invention also provides a kind of hollow nucleocapsid vanadic anhydride lithiums of tremelliform being prepared using the above method
Ion battery positive electrode, the positive electrode applied to lithium ion battery.
Compared with prior art, the present invention has following advantageous effect：
This tremelliform structure that the present invention synthesizes increases the external contact area of material, not only increases lithium ion battery
Efficiency for charge-discharge can also make lithium ion freely embedded and deintercalation in charge and discharge process, maintain the height of lithium ion battery
Cycle characteristics and stability.Meanwhile the structure of tremelliform is conducive to that the structure of positive electrode in charge and discharge process is kept not broken
It is bad, and then have to the raising of the cycle performance and efficiency for charge-discharge of material and greatly facilitate effect.
The C@V that the present invention synthesizes2O5Positive electrode greatly improves electric conductivity, and its hollow core due to the presence of carbon ball
Shell structure can improve V2O5The stability of material, and the diffusion path of lithium ion can be shortened, the efficiency of transmission of lithium ion is improved, more
Added with beneficial to raising V2O5Chemical property.
The C@V that the present invention synthesizes2O5Positive electrode has good electrochemical stability.Under the multiplying power of 1C, tremelliform is hollow
Nucleocapsid C@V2O5Initial discharge capacity can reach 147mAh/g, and after five different cycling, charge and discharge
The registration of curve is very high.Illustrate the hollow nucleocapsid C V of this tremelliform2O5It is this with good cyclical stability
The hollow nucleocapsid of tremelliform also improves the stable charge/discharge of battery while the efficiency for charge-discharge of battery is improved, and protects
The high capacity characteristics of electrode material are demonstrate,proved；Under the multiplying power of 10C, battery capacity retention ratio after 10 Xun Huans is still up to
99.8%, illustrate the hollow nucleocapsid C V of this tremelliform2O5Material has very strong structural stability, supports quick charge and discharge
Electricity requirement.
The hollow nucleocapsid C V of tremelliform that the present invention synthesizes2O5Positive electrode not only has high reversible capacity, cyclicity
Can good, the advantages such as efficiency for charge-discharge height, also gathered it is at low cost, it is environmentally protective the advantages that.Meanwhile the hollow nucleocapsid of tremelliform
C@V2O5Method for preparing anode material is simple for process, easy to operate.
Description of the drawings
Fig. 1 is C@V2O5Positive electrode XRD diagram.
Fig. 2 is C@V2O5Positive electrode scanning electron microscope (SEM) photograph（5μm）.
Fig. 3 is C@V2O5Positive electrode scanning electron microscope (SEM) photograph（3μm）.
Fig. 4 is the transmission electron microscope picture of hollow carbon balls.
Fig. 5 is C@V2O5Positive electrode transmission electron microscope picture.
Fig. 6 is C@V2O5Five charge-discharge performance figures of positive electrode.
Fig. 7 is C@V2O5High rate performance figure by 10 Xun Huan after of the positive electrode under different multiplying.
Fig. 8 is C@V2O5Coulombic efficiency and cycle performance figure of the positive electrode under the multiplying power of 1C after 400 Xun Huans.
Specific embodiment
It is further illustrated the present invention with reference to specific embodiment.Following embodiment is only illustrative examples, not structure
Into inappropriate limitation of the present invention, the multitude of different ways that the present invention can be limited and covered by the content of the invention is implemented.It is unless special
Do not mentionlet alone bright, the present invention reagent, compound and the equipment that use is the art conventional reagent, compound and equipment.
Embodiment 1
The present embodiment provides a kind of hollow nucleocapsid vanadic anhydride method for preparing anode material of lithium-ion battery of tremelliform, bags
Include following steps：
S1. 100mg hollow carbon spheres are placed in 100ml beakers, the addition of 40ml organic solvents ethylene glycol is taken to fill hollow carbon sphere
Beaker in, be subsequently placed on magnetic stirring apparatus, stir 10min, obtain suspension A；
S2. 25ml urea is measured in another beaker, adds in 10ml deionized waters, and stirring makes urea be added in after being completely dissolved
150mg ammonium metavanadates stir at 50 DEG C, are completely dissolved ammonium metavanadate, obtain pale yellow transparent sol B；
S3. pale yellow transparent sol B is added in suspension A, and is kept stirring in 50 DEG C of water-baths, be then transferred into reaction kettle
In, hydro-thermal reaction is carried out at 180 DEG C, reaction time 12h is centrifuged after having reacted and obtained black product, black product is being dried
It is calcined after dry case drying, specifically in Muffle furnace, calcining heat is 450 DEG C, calcination time 2h, finally obtains yellow production
The C@V of object2O5Powder body material.
Wherein, the preparation method of hollow carbon sphere is as follows described in step S1：
S11. blender stirring is put into after mixing 5ml absolute ethyl alcohols and 60ml deionized waters, then the positive silicon of addition 1ml successively
Acetoacetic ester, 0.5g resorcinols, 0.5ml formaldehyde and 3ml ammonium hydroxide add in 1ml ethyl orthosilicates after stirring 6h, and continue to keep stirring
It mixes；
S12. stir to pour into afterwards for 24 hours and hydro-thermal reaction is carried out in reaction kettle, temperature is 100 DEG C, and the reaction time is natural cooling for 24 hours
After centrifuge to pH be 7, be then placed in drying box drying；
S13. dried product is put into tube furnace and calcined, temperature is 700 DEG C, time 3h, is used after calcining cooling
Hydrofluoric acid etch, the addition of the hydrofluoric acid is 5wt%, and is infiltrated for 24 hours, and it is 7 to be then centrifuged for washing to pH, is obtained after dry
Hollow carbon sphere.
Wherein, the hollow nucleocapsid C V of tremelliform of special appearance are formed in the present embodiment2O5First key point
It is the hollow carbon sphere of step S1 and step S2 configurations and the ratio of ammonium metavanadate, second key point is in the conduct in step S2
Additive urea, the 3rd key point is in the time of hydro-thermal reaction and temperature in step S3.
The concentration of control and regulation hydrofluoric acid and infiltrating time can accurately remove the silicon in carbon ball in step S13, obtain
The hollow carbon sphere of high-quality.
The present embodiment with ethyl orthosilicate, resorcinol, formaldehyde, ammonium metavanadate etc. for raw material, using simple hydro-thermal method,
Preparation method is simple, easy to operate, at low cost, and the hollow nucleocapsid vanadic anhydride lithium ion battery of the tremelliform being prepared is just
Pole material greatly improves existing V2O5The electric conductivity and stability of positive electrode, so as to significantly improve its chemical property.
The pattern of tremelliform increases specific surface area, improves chemical property；The presence of hollow carbon sphere improves the electric conductivity of material；
Hollow structure greatly improves the stability of material.
Embodiment 2
The present embodiment provides a kind of hollow nucleocapsid vanadic anhydride method for preparing anode material of lithium-ion battery of tremelliform, bags
Include following steps：
S1. 150mg hollow carbon spheres are placed in 100ml beakers, the addition of 50ml organic solvents ethylene glycol is taken to fill hollow carbon sphere
Beaker in, be subsequently placed on magnetic stirring apparatus, stir 10min, obtain suspension A；
S2. 30ml urea is measured in another beaker, adds in 10ml deionized waters, and stirring makes urea be added in after being completely dissolved
200mg ammonium metavanadates stir at 50 DEG C, are completely dissolved ammonium metavanadate, obtain pale yellow transparent sol B；
S3. pale yellow transparent sol B is added in suspension A, and is kept stirring in 50 DEG C of water-baths, be then transferred into reaction kettle
In, hydro-thermal reaction is carried out at 200 DEG C, the reaction time for 24 hours, centrifuges after having reacted and obtains black product, black product is being dried
It is calcined after dry case drying, specifically in Muffle furnace, calcining heat is 550 DEG C, calcination time 3h, finally obtains yellow production
The C@V of object2O5Powder body material.
Wherein, the preparation method of hollow carbon sphere is as follows described in step S1：
S11. will 10ml absolute ethyl alcohols and 80ml deionized waters mix after be put into blender stirring, then addition 3ml successively is being just
Silester, 0.5g resorcinols, 1ml formaldehyde and 5ml ammonium hydroxide add in 3ml ethyl orthosilicates after stirring 6h, and continue to keep stirring
It mixes；
S12. stir to pour into afterwards for 24 hours and hydro-thermal reaction is carried out in reaction kettle, temperature is 120 DEG C, and the reaction time is natural cooling for 24 hours
After centrifuge to pH be 7, be then placed in drying box drying；
S13. dried product is put into tube furnace and calcined, temperature is 800 DEG C, time 3h, is used after calcining cooling
Hydrofluoric acid etch, the addition of the hydrofluoric acid is 10wt%, and infiltrates 48h, and it is 7 to be then centrifuged for washing to pH, is obtained after dry
Hollow carbon sphere.
Embodiment 3
The present embodiment provides a kind of hollow nucleocapsid vanadic anhydride method for preparing anode material of lithium-ion battery of tremelliform, bags
Include following steps：
S1. 200mg hollow carbon spheres are placed in 100ml beakers, the addition of 45ml organic solvents ethylene glycol is taken to fill hollow carbon sphere
Beaker in, be subsequently placed on magnetic stirring apparatus, stir 10min, obtain suspension A；
S2. 26ml urea is measured in another beaker, adds in 10ml deionized waters, and stirring makes urea be added in after being completely dissolved
100mg ammonium metavanadates stir at 50 DEG C, are completely dissolved ammonium metavanadate, obtain pale yellow transparent sol B；
S3. pale yellow transparent sol B is added in suspension A, and is kept stirring in 50 DEG C of water-baths, be then transferred into reaction kettle
In, hydro-thermal reaction is carried out at 190 DEG C, reaction time 16h is centrifuged after having reacted and obtained black product, black product is being dried
It is calcined after dry case drying, specifically in Muffle furnace, calcining heat is 480 DEG C, calcination time 4h, finally obtains yellow production
The C@V of object2O5Powder body material.
Wherein, the preparation method of hollow carbon sphere is as follows described in step S1：
S11. blender stirring is put into after mixing 7ml absolute ethyl alcohols and 70ml deionized waters, then the positive silicon of addition 2ml successively
Acetoacetic ester, 0.5g resorcinols, 0.7ml formaldehyde and 4ml ammonium hydroxide add in 2ml ethyl orthosilicates after stirring 6h, and continue to keep stirring
It mixes；
S12. stir to pour into afterwards for 24 hours and hydro-thermal reaction is carried out in reaction kettle, temperature is 110 DEG C, and the reaction time is natural cooling for 24 hours
After centrifuge to pH be 7, be then placed in drying box drying；
S13. dried product is put into tube furnace and calcined, temperature is 750 DEG C, time 3h, is used after calcining cooling
Hydrofluoric acid etch, the addition of the hydrofluoric acid is 8wt%, and infiltrates 30h, and it is 7 to be then centrifuged for washing to pH, is obtained after dry
Hollow carbon sphere.
Embodiment 4
The present embodiment provides a kind of hollow nucleocapsid vanadic anhydride method for preparing anode material of lithium-ion battery of tremelliform, bags
Include following steps：
S1. 100mg hollow carbon spheres are placed in 100ml beakers, the addition of 48ml organic solvents ethylene glycol is taken to fill hollow carbon sphere
Beaker in, be subsequently placed on magnetic stirring apparatus, stir 10min, obtain suspension A；
S2. 28ml urea is measured in another beaker, adds in 10ml deionized waters, and stirring makes urea be added in after being completely dissolved
200mg ammonium metavanadates stir at 50 DEG C, are completely dissolved ammonium metavanadate, obtain pale yellow transparent sol B；
S3. pale yellow transparent sol B is added in suspension A, and is kept stirring in 50 DEG C of water-baths, be then transferred into reaction kettle
In, hydro-thermal reaction is carried out at 195 DEG C, reaction time 20h is centrifuged after having reacted and obtained black product, black product is being dried
It is calcined after dry case drying, specifically in Muffle furnace, calcining heat is 530 DEG C, calcination time 4h, finally obtains yellow production
The C@V of object2O5Powder body material.
Wherein, the preparation method of hollow carbon sphere is as follows described in step S1：
S11. will 8ml absolute ethyl alcohols and 75ml deionized waters mix after be put into blender stirring, then addition 2.5ml successively is being just
Silester, 0.5g resorcinols, 0.9ml formaldehyde and 4.5ml ammonium hydroxide add in 2.5ml ethyl orthosilicates after stirring 6h, and continue
It is kept stirring；
S12. stir to pour into afterwards for 24 hours and hydro-thermal reaction is carried out in reaction kettle, temperature is 115 DEG C, and the reaction time is natural cooling for 24 hours
After centrifuge to pH be 7, be then placed in drying box drying；
S13. dried product is put into tube furnace and calcined, temperature is 790 DEG C, time 3h, is used after calcining cooling
Hydrofluoric acid etch, the addition of the hydrofluoric acid is 8wt%, and infiltrates 36h, and it is 7 to be then centrifuged for washing to pH, is obtained after dry
Hollow carbon sphere.
Performance and characterization
Fig. 1 is C@V2O5Positive electrode XRD diagram, as can be seen from the figure the present invention prepared by C@V2O5Characteristic peak and V2O5Mark
The peak of quasi- card (PDF#41-1426) almost overlaps, and that this explanation is prepared is the V of high-purity2O5.Wherein C is non crystalline structure,
Do not occur diffraction maximum.
It is C@V shown in Fig. 2, Fig. 32O5The scanning electron microscope (SEM) photograph of positive electrode, as can be seen from Fig. C@V2O5Positive electrode is in spy
Different white fungus shape, and grain size is at 3 μm or so.The special appearance of this tremelliform, substantially increases V2O5Surface area, increase
The efficiency for charge-discharge of electrode can be greatly improved in the big response area of material.
Fig. 4 show the transmission electron microscope picture of hollow carbon balls, it can be clearly seen that hollow ball shape structure.Fig. 5 is C@V2O5Anode
The transmission electron microscope picture of material, there are one apparent spheric profile, nano-sheets at the center of sample particle as we can see from the figure
V2O5It is uniformly coated on hollow carbon sphere and forms the tremelliform with special appearance.
It is C@V shown in Fig. 62O5Five charge-discharge performance figures of positive electrode.It can be seen from the figure that under the multiplying power of 1C,
C@V2O5Discharge capacity be as high as 147mAh/g.By five different cycling, it can be seen that the registration of charging and discharging curve is non-
Normal height illustrates C@V prepared by the present invention2O5Material has good cyclical stability in electrochemical reaction process.
Fig. 7 show C@V2O5The high rate performance figure after 10 Xun Huans under different multiplying.As can be seen from the figure
C@V2O5Initial discharge capacity under the multiplying power of 1C is 147.0mAh/g, and capacity retention ratio is 99.72% at this time；In times of 10C
Rate discharge capacity is 102.1 mAh/g, and capacity retention ratio is still up to 99.8%.Show the hollow nucleocapsid knot of this tremelliform
Be conducive to lithium ion free diffusive migration in the material in structure, ensure that lithium ion insertion and the high reversible of deintercalation in guarantor
The high capacity characteristics of battery are demonstrate,proved.
Fig. 8 show C@V2O5Coulombic efficiency and cycle performance figure under the multiplying power of 1C after 400 Xun Huans.From Fig. 7
In it can be seen that C@V2O5Coulombic efficiency initial value is 100%, and after 400 Xun Huans, coulombic efficiency is still up to 98%, and capacity is protected
Holdup is 90.14%.Show the hollow nucleocapsid C V of this tremelliform2O5It is more conducive in lithium ion charge and discharge process in material
Diffusive migration inside material reduces lithium ion waste during insertion and deintercalation, maintains lithium battery high circulation performance
And stability.
Claims (10)
1. a kind of hollow nucleocapsid vanadic anhydride method for preparing anode material of lithium-ion battery of tremelliform, which is characterized in that
Comprise the following steps：
S1. hollow carbon sphere is dissolved in organic solvent, is uniformly mixing to obtain suspension A；
S2. by ammonium metavanadate and urea, deionized water in mass ratio 10~20:150~225：1 uniformly mixing, is then heated simultaneously
Stirring is completely dissolved up to ammonium metavanadate, obtains pale yellow transparent sol B；
S3. pale yellow transparent sol B is added in suspension A, wherein the mass ratio of hollow carbon sphere and ammonium metavanadate is 0.5~2:
1, and be kept stirring in a water bath, it is then transferred into reaction kettle, hydro-thermal reaction, reaction time 12 is carried out at 180~200 DEG C
~for 24 hours, it is centrifuged after having reacted and obtains black product, calcined after black product is dried, finally obtain the C of yellow product
V2O5Powder body material.
2. the hollow nucleocapsid vanadic anhydride anode material for lithium-ion batteries preparation side of tremelliform according to claim 1
Method, which is characterized in that the preparation method of hollow carbon sphere is as follows described in step S1：
S11. will 5~10ml absolute ethyl alcohols and 60~80ml deionized waters mix after be put into blender stirring, then successively plus
Enter 1~3ml ethyl orthosilicates, 0.5g resorcinols, 0.5~1ml formaldehyde and 3~5ml ammonium hydroxide, 1~3ml is being added in just after stirring 6h
Silester, and continue to be kept stirring；
S12. stir to pour into afterwards for 24 hours and hydro-thermal reaction is carried out in reaction kettle, temperature is 100~120 DEG C, and the reaction time is nature for 24 hours
Centrifugation is 7 to pH after cooling, is then placed in drying box drying；
S13. dried product is put into tube furnace and calcined, temperature is 700~800 DEG C, time 3h, calcining cooling
Afterwards with hydrofluoric acid etch, it is 7 to be then centrifuged for washing to pH, and hollow carbon sphere is obtained after dry.
3. the hollow nucleocapsid vanadic anhydride anode material for lithium-ion batteries preparation side of tremelliform according to claim 2
Method, which is characterized in that the addition of hydrofluoric acid described in step S13 is 5~10wt%, and infiltrates 24~48h.
4. the hollow nucleocapsid vanadic anhydride anode material for lithium-ion batteries preparation side of tremelliform according to claim 1
Method, which is characterized in that organic solvent described in step S1 is ethylene glycol.
5. the hollow nucleocapsid vanadic anhydride anode material for lithium-ion batteries preparation side of tremelliform according to claim 1
Method, which is characterized in that stirring refers to stir 10min on magnetic stirring apparatus in step S1.
6. the hollow nucleocapsid vanadic anhydride anode material for lithium-ion batteries preparation side of tremelliform according to claim 1
Method, which is characterized in that heating temperature is 50 DEG C in step S2.
7. the hollow nucleocapsid vanadic anhydride anode material for lithium-ion batteries preparation side of tremelliform according to claim 1
Method, which is characterized in that bath temperature is 50 DEG C in step S3.
8. the hollow nucleocapsid vanadic anhydride anode material for lithium-ion batteries preparation side of tremelliform according to claim 1
Method, which is characterized in that calcining heat described in step S3 is 450~550 DEG C, and calcination time is 2~4h.
9. a kind of hollow nucleocapsid vanadic anhydride anode material for lithium-ion batteries of tremelliform, which is characterized in that will by right
The hollow nucleocapsid vanadic anhydride method for preparing anode material of lithium-ion battery of tremelliform described in 1~8 any one is asked to prepare
It obtains.
10. the application of the hollow nucleocapsid vanadic anhydride anode material for lithium-ion batteries of tremelliform according to claim 9,
It is characterized in that, the positive electrode applied to lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711385264.3A CN108110244A (en) | 2017-12-20 | 2017-12-20 | A kind of hollow nucleocapsid vanadic anhydride anode material for lithium-ion batteries of tremelliform and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711385264.3A CN108110244A (en) | 2017-12-20 | 2017-12-20 | A kind of hollow nucleocapsid vanadic anhydride anode material for lithium-ion batteries of tremelliform and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108110244A true CN108110244A (en) | 2018-06-01 |
Family
ID=62211312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711385264.3A Pending CN108110244A (en) | 2017-12-20 | 2017-12-20 | A kind of hollow nucleocapsid vanadic anhydride anode material for lithium-ion batteries of tremelliform and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108110244A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109817943A (en) * | 2019-02-19 | 2019-05-28 | 珠海光宇电池有限公司 | A kind of carbon coating vanadic anhydride positive electrode and preparation method thereof and the application in lithium battery |
| CN110061209A (en) * | 2019-04-03 | 2019-07-26 | 合肥国轩高科动力能源有限公司 | A kind of MnO2@V2O5Core-shell nano material and preparation method thereof, application |
| CN111527628A (en) * | 2018-07-18 | 2020-08-11 | 株式会社Lg化学 | Electrochemical pretreatment method for vanadium positive electrode for lithium secondary battery and vanadium positive electrode for lithium secondary battery pretreated by said method |
| CN113036311A (en) * | 2021-03-01 | 2021-06-25 | 同济大学 | Porous carbon ball packaged vanadium oxide heterogeneous core-shell ball structure material, preparation method thereof, lithium-sulfur battery diaphragm and lithium-sulfur battery |
| CN114284485A (en) * | 2021-12-31 | 2022-04-05 | 齐鲁工业大学 | V-shaped groove2O3Preparation method of/C hollow nanosphere electrode material |
| CN114284501A (en) * | 2021-12-28 | 2022-04-05 | 厦门大学 | Lithium metal cathode of hollow carbon sphere loaded with silver particles and solid-state battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106409522A (en) * | 2016-10-10 | 2017-02-15 | 华南师范大学 | Manganese dioxide-coated hollow carbon spheres and preparation method and application thereof |
-
2017
- 2017-12-20 CN CN201711385264.3A patent/CN108110244A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106409522A (en) * | 2016-10-10 | 2017-02-15 | 华南师范大学 | Manganese dioxide-coated hollow carbon spheres and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| HAO BIN WU ET AL: "Template-Assisted Formation of Rattle-type V2O5 Hollow Microspheres with Enhanced Lithium Storage Properties", 《ADVANCED FUNCTIONAL MATERIALS》 * |
| LIQIANG MAI ET AL: "Nanoflakes-Assembled Three-Dimensional Hollow-Porous V2O5 as Lithium Storage Cathodes with High-Rate Capacity", 《SMALL》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111527628A (en) * | 2018-07-18 | 2020-08-11 | 株式会社Lg化学 | Electrochemical pretreatment method for vanadium positive electrode for lithium secondary battery and vanadium positive electrode for lithium secondary battery pretreated by said method |
| US11646402B2 (en) | 2018-07-18 | 2023-05-09 | Lg Energy Solution, Ltd. | Method for electrochemical pretreatment of vanadium positive electrode for lithium secondary batteries and vanadium positive electrode for lithium secondary batteries pretreated thereby |
| CN109817943A (en) * | 2019-02-19 | 2019-05-28 | 珠海光宇电池有限公司 | A kind of carbon coating vanadic anhydride positive electrode and preparation method thereof and the application in lithium battery |
| CN110061209A (en) * | 2019-04-03 | 2019-07-26 | 合肥国轩高科动力能源有限公司 | A kind of MnO2@V2O5Core-shell nano material and preparation method thereof, application |
| CN110061209B (en) * | 2019-04-03 | 2022-03-04 | 合肥国轩高科动力能源有限公司 | MnO (MnO)2@V2O5Core-shell nano material and preparation method and application thereof |
| CN113036311A (en) * | 2021-03-01 | 2021-06-25 | 同济大学 | Porous carbon ball packaged vanadium oxide heterogeneous core-shell ball structure material, preparation method thereof, lithium-sulfur battery diaphragm and lithium-sulfur battery |
| CN114284501A (en) * | 2021-12-28 | 2022-04-05 | 厦门大学 | Lithium metal cathode of hollow carbon sphere loaded with silver particles and solid-state battery |
| CN114284501B (en) * | 2021-12-28 | 2023-11-07 | 厦门大学 | Lithium metal negative electrode of hollow carbon sphere loaded with silver particles and solid-state battery |
| CN114284485A (en) * | 2021-12-31 | 2022-04-05 | 齐鲁工业大学 | V-shaped groove2O3Preparation method of/C hollow nanosphere electrode material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108110244A (en) | A kind of hollow nucleocapsid vanadic anhydride anode material for lithium-ion batteries of tremelliform and preparation method thereof | |
| CN105098151B (en) | Molybdenum disulfide-carbon hollow ball hybrid material and preparation method thereof | |
| CN103193263B (en) | Preparation method and application of hollow SnO2@C nanosphere in lithium ion battery | |
| CN105742602B (en) | A kind of sodium-ion battery cathode Sn/MoS2/ C composite and preparation method thereof | |
| CN102583292B (en) | Ferric phosphate having micro-nano structure and preparation method thereof as well as lithium iron phosphate material | |
| CN105938899B (en) | A kind of preparation method and application of fast-ionic conductor coating modification anode material for lithium-ion batteries | |
| CN105470455A (en) | Modified lithium ion battery positive electrode material and preparation method therefor | |
| CN105336924A (en) | Preparation method of carbon coated vanadium sodium phosphate positive electrode material | |
| CN108039486A (en) | The hollow core shell structure vanadic anhydride anode electrode piece of tremelliform and its fastening lithium ionic cell preparation method | |
| CN105236486B (en) | A kind of high performance lithium ion battery anode material vanadium pentoxide hollow microsphere and preparation method | |
| CN104466102B (en) | A kind of porous V2O5/C complex microspheres of positive electrode material of lithium secondary cell and preparation method thereof | |
| CN102299326A (en) | Graphene modified lithium iron phosphate/carbon composite material and its application | |
| CN104176778B (en) | A kind of classifying porous barium oxide microballoon and its preparation method and application | |
| CN107403913A (en) | A kind of nickel cobalt lithium aluminate cathode material of surface modification and preparation method thereof | |
| CN104577094B (en) | A kind of anode material for lithium-ion batteries and preparation method thereof | |
| CN105098181A (en) | Preparation method for nano-flake SnS2 sodium-ion battery negative electrode material with good rate capability | |
| CN104993116B (en) | A kind of self assembly anode material for lithium-ion batteries V2O5Preparation method | |
| CN104852046B (en) | Nanometer piece shaped LMFP material, and manufacturing method and application thereof | |
| CN106711435A (en) | Preparation method of layered lithium-manganese-rich base/GNRs (graphene nanoribbons) anode composite material | |
| CN108172782A (en) | A kind of preparation method and application with shell-core structure carbon package porous oxidation Asia cobalt nano material | |
| Wang et al. | Synthesis and electrochemical properties of LiV3O8 via an improved sol–gel process | |
| CN103413918B (en) | A kind of synthetic method of anode material for lithium ion battery cobalt phosphate lithium | |
| CN103441239A (en) | Synthetic method for nanoscale ternary cathode material | |
| CN103078120A (en) | Ferrous silicate lithium ion battery cathode material with hierarchical structure and preparation method | |
| Wu et al. | Study on Li1+ xV3O8 synthesized by microwave sol–gel route |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180601 |
|
| RJ01 | Rejection of invention patent application after publication |