CN105870445A - Method for synthesizing lithium vanadate/carbon/nitrogen-doped graphene serving as lithium ion battery cathode composite material - Google Patents
Method for synthesizing lithium vanadate/carbon/nitrogen-doped graphene serving as lithium ion battery cathode composite material Download PDFInfo
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Abstract
The invention discloses a method for synthesizing lithium vanadate/carbon/nitrogen-doped graphene serving as a lithium ion battery cathode composite material. The method includes steps: scattering graphene oxide into an aqueous solution containing a surfactant while scattering pyrrole into a water and ethanol mixed solution, dropwise adding the pyrrole containing solution into the graphene oxide solution, reacting to obtain polypyrrole graphene oxide, and performing leaching, washing, drying and sintering to obtain nitrogen-doped graphene; mixing the nitrogen-doped graphene, a lithium source, a vanadium source and a carbon source, and performing dispersing, drying and sintering to obtain the lithium vanadate/carbon/nitrogen-doped graphene serving as the lithium ion battery cathode composite material. By coating of lithium vanadate with the carbon material and the nitrogen-doped graphene, electron conduction rate of the lithium vanadate in charging and discharging processes is greatly increased, and accordingly rate performance and cycle performance of the lithium vanadate are improved.
Description
Technical field
The invention belongs to lithium battery material field, specifically a kind of composite cathode material of lithium ion battery lithium vanadate/carbon/mix
The synthetic method of nitrogen Graphene.
Background technology
At present, graphite has higher stability because of it and cost performance is widely used in lithium ion battery cathode material
In, its theoretical capacity is 372mAh/g, belongs to embedding abjection type ion cathode material lithium.But in charge and discharge process, graphite
Intercalation potential is less than 0.1V(vs Li/Li+), cause being likely to occur Li dendrite in cyclic process and pierce through barrier film and cause battery short
Road, thus cause the potential safety hazard of power vehicle.In order to eliminate this kind of phenomenon, researchers find one by effort for many years
The negative material that discharge platform is suitable, capacity is worked as with graphite-phase.Within 2013, Japanese Scientists finds lithium vanadate (Li3VO4) negative pole material
Material, its discharge potential is 0.5 ~ 1V(vs Li/Li+), compared to graphite, there is higher discharge potential thus improve the peace of battery
Full performance, and relative to lithium titanate anode material, there is higher capacity, when matching with other positive electrodes, battery has wider
Discharge voltage so that battery has higher capacity.
Research finds, lithium vanadate (Li3VO4) belong to ion conductor, there is the highest ionic conductivity, but its electronic conduction
The very poor intimate insulator of property so that its chemical property is severely impacted, especially its cycle performance.In order to improve its conduction
Property, researchers start to carry out lithium vanadate granule nanorize and surface modification treatment, and most conventional methods are just introduced into carbon material
Material improves its electric conductivity, and Liang et al. (Journal of Power Sources, 2014,252:244-247) uses colloidal sol
Gel method is to Li3VO4Carry out carbon cladding to process, there is in terms of improving material high rate performance better effects, but in terms of circulation
The decay of material is the most very fast；Li et al. (Adv. Sci. 2015,1500284) uses hydro-thermal method to realize graphene coated in situ
Process, it is possible to be substantially improved the cycle performance of material, but this method is unfavorable for large-scale industrialization promotion.
Summary of the invention
For the defect that the high rate performance of lithium ion battery negative material of prior art and cycle performance are the best, the present invention
The synthetic method of a kind of composite cathode material of lithium ion battery lithium vanadate/carbon/nitrogen-doped graphene is proposed.
The purpose of the present invention can be achieved through the following technical solutions:
The synthetic method of a kind of composite cathode material of lithium ion battery lithium vanadate/carbon/nitrogen-doped graphene, it is characterised in that described
Method comprises the following steps:
(1) surfactant is evenly spread in deionized water, add graphene oxide, ultrasonic disperse, obtain uniform alumina
Graphene solution A, in graphene oxide solution A, graphene oxide concentration is 2 ~ 5mg/ml；
(2) mixed solvent of pyrroles's ultrasonic disperse to deionized water and dehydrated alcohol will form chromium solution B, chromium solution B
Middle pyrrole concentrations is 5 ~ 20mg/ml；Deionized water is 0.5 ~ 1.5:1 with the volume ratio of dehydrated alcohol；
(3) being added drop-wise in graphene oxide solution A by chromium solution B, under room temperature, ultrasonic disperse reaction, obtains pyrroles/oxidation stone
Ink alkene, be then passed through sucking filtration, washing final vacuum be dried, under inert atmosphere protection sinter, obtain nitrogen-doped graphene；
(4) add after nitrogen-doped graphene being mixed with vanadium source, lithium source, carbon source after ball-milling medium carries out ball milling dispersion and obtain lithium vanadate
Presoma, lithium ion and the mol ratio Li:V=3 ~ 3.2:1 of vanadium ion, be dried, sinter, obtain vanadic acid under protective gas atmosphere
Lithium/carbon/nitrogen-doped graphene composite.
Described step (1) surfactant is cetyl trimethylammonium bromide, poly(ethylene oxide) ~ poly(propylene oxide) ~ poly-
In oxirane triblock copolymer P123, poly(ethylene oxide) ~ poly(propylene oxide) ~ poly(ethylene oxide) triblock copolymer F127
One or both, surfactant solution concentration controls at 1 ~ 5mg/ml.
Described step (1) ultrasonic water temperature controls below 60 DEG C, and the ultrasonic disperse time is 0.5 ~ 1h.
Described protective gas is N2、Ar、CO2、H2With N2, one or more in Ar mixed gas, sinter heating rate ＜
5℃/min。
Described step (3) the ultrasonic disperse time is 0.5 ~ 1h, and reaction temperature is 80 ~ 120 DEG C, and the response time is 10 ~ 20h；
Vacuum drying temperature is 50 ~ 80 DEG C, and drying time is 12 ~ 24h；Sintering temperature is 1200 ~ 1800 DEG C, and sintering time is 2 ~ 4h.
Described step (4) lithium source is the one in lithium nitrate, Quilonorm (SKB), Lithium hydroxide monohydrate, lithium carbonate, Lithium acetate dihydrate
Or two kinds；Vanadium source is one or both in ammonium metavanadate, vanadic anhydride, Vanadium sesquioxide；Described carbon source is sucrose, Fructus Vitis viniferae
One or both in sugar, carbon black, citric acid, polyvinyl alcohol, Polyethylene Glycol, ethylenediaminetetraacetic acid.
Described step (4) ball-milling medium is in deionized water, dehydrated alcohol, ethylene glycol, acetone, dimethylformamide
Planting or two kinds, slurry solid content controls 35 ~ 60%.
Described step (4) baking temperature is 80 ~ 120 DEG C, and drying time is 12 ~ 24h；Sintering temperature is 800 ~ 1100 DEG C,
Sintering time is 8 ~ 16h.
Beneficial effects of the present invention: the present invention, at lithium vanadate Surface coating material with carbon element, is coated with one layer of nitrating graphite the most again
Alkene, substantially increases the lithium vanadate electronics conduction velocity at charge and discharge process, thus improves high rate performance and the circulation of lithium vanadate
Performance.
The present invention, while improving lithium vanadate chemical property, uses solid phase method to produce lithium vanadate negative material, no
Only it is easy to control production process, simplification of flowsheet, and is beneficial to produce popularization on a large scale, have a good application prospect.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum that embodiment 1 synthesizes lithium vanadate/carbon/nitrogen-doped graphene composite；
Fig. 2 is the SEM collection of illustrative plates that embodiment 1 synthesizes lithium vanadate/carbon/nitrogen-doped graphene composite；
Fig. 3 is the charging and discharging curve that embodiment 1 synthesizes lithium vanadate/carbon/nitrogen-doped graphene composite assembling button electricity；
Fig. 4 is the curve of double curvature that embodiment 1 synthesizes lithium vanadate/carbon/nitrogen-doped graphene composite assembling button electricity；
Fig. 5 is the cyclic curve that embodiment 1 synthesizes lithium vanadate/carbon/nitrogen-doped graphene composite assembling button electricity.
Detailed description of the invention
Embodiment 1
1, the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer P123 of 0.5g is weighed as surface activity
Agent evenly spreads in 100mL deionized water, and the graphene oxide then weighing 0.4g joins in surfactant solution, super
Uniform graphene oxide suspension A is formed after sound dispersion 1h；
2, weighing pyrroles's ultrasonic disperse of 1g to 200mL deionized water and the mixed solvent of dehydrated alcohol, deionized water is with anhydrous
The volume ratio of ethanol is 1:1, forms chromium solution B；
3, chromium solution B is added drop-wise in graphene oxide solution A, 100 DEG C of reactions after ultrasonic disperse 0.5h under room temperature
Obtain polypyrrole/graphene oxide after 10h, after being then passed through sucking filtration, washing, be vacuum dried 24h at 60 DEG C, at Ar atmosphere protection
Lower 1600 DEG C of sintering 3h obtain nitrogen-doped graphene；
4, the nitrogen-doped graphene of 0.5g, the ammonium metavanadate of 4.68g, the Lithium acetate dihydrate of 12.24g, 1g glucose are weighed as carbon
After the mixing of source, addition 20mL dehydrated alcohol is as ball-milling medium, and slurry solid content is 54%, obtains vanadic acid after carrying out ball milling dispersion
Lithium presoma, after being dried 13h at a temperature of 120 DEG C, at CO2、N2The lower 900 DEG C of sintering 10h of atmosphere protection obtain lithium vanadate/carbon/mix
Nitrogen graphene composite material.
Embodiment 2
1, the cetyl trimethylammonium bromide of 0.3g, 0.1g poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) three are weighed embedding
Section copolymer F127 evenly spreads to, in 100mL deionized water, then weigh the graphene oxide of 0.4g as surfactant
Join in surfactant solution, after ultrasonic disperse 0.5h, form uniform graphene oxide suspension A；
2, pyrroles's ultrasonic disperse of 1g is weighed to 200mL deionized water and the mixed solvent of dehydrated alcohol, deionized water and anhydrous
Ethanol volume ratio is 0.8:1, forms chromium solution B；
3, chromium solution B is added drop-wise in graphene solution A, under room temperature after ultrasonic disperse 0.5h after 120 DEG C of reaction 15h
Obtain polypyrrole/graphene oxide, after being then passed through sucking filtration, washing, be vacuum dried 18h at 50 DEG C, at CO2Under atmosphere protection
1500 DEG C of sintering 4h obtain nitrogen-doped graphene；
4, the nitrogen-doped graphene of 0.5g, the vanadic anhydride of 7.28g, the Lithium acetate dihydrate of 12.24g, 1g glucose conduct are weighed
After carbon source mixing, addition 20mL deionized water is as ball-milling medium, and slurry solid content is 51%, obtains vanadium after carrying out ball milling dispersion
After acid lithium presoma is dried 16h at a temperature of 90 DEG C, under Ar atmosphere protection, 1000 DEG C of sintering 12h obtain lithium vanadate/carbon/nitrating
Graphene composite material.
Embodiment 3
1, the poly(ethylene oxide) ~ poly(propylene oxide) ~ poly(ethylene oxide) triblock copolymer F127 of 0.2g is weighed as surface activity
Agent evenly spreads in 100mL deionized water, and the graphene oxide then weighing 0.4g joins in surfactant solution, super
Uniform graphene oxide suspension A is formed after sound dispersion 1h；
2, pyrroles's ultrasonic disperse of 2g is weighed to 200mL deionized water and the mixed solvent of dehydrated alcohol, deionized water and anhydrous
The volume ratio of ethanol is 1:1, forms chromium solution B；
3, chromium solution B is added drop-wise in graphene solution A, under room temperature, after ultrasonic disperse 50min, reacts 12h at 100 DEG C
After obtain polypyrrole/graphene oxide, be then passed through sucking filtration, washing after 70 DEG C be vacuum dried 15h, at H2With Ar atmosphere protection
Lower 1700 DEG C of sintering 2h obtain nitrogen-doped graphene；
4, weigh the nitrogen-doped graphene of 0.5g, the ammonium metavanadate of 4.68g, the Quilonorm (SKB) of 7.92g, 1g glucose as carbon source mix
After conjunction, addition 20mL ethylene glycol is as ball-milling medium, and slurry solid content is 39%, obtains lithium vanadate forerunner after carrying out ball milling dispersion
After body is dried 22h at a temperature of 80 DEG C, at CO2It is multiple that the lower 800 DEG C of sintering 11h of atmosphere protection obtain lithium vanadate/carbon/nitrogen-doped graphene
Condensation material.
Embodiment 4
1, the poly(ethylene oxide) ~ poly(propylene oxide) ~ poly(ethylene oxide) triblock copolymer P123 of 0.5g is weighed as surface activity
Agent evenly spreads in 100mL deionized water, and the graphene oxide (GO) then weighing 0.4g joins surfactant solution
In, form uniform graphene oxide suspension A after ultrasonic disperse 1h；
2, pyrroles's ultrasonic disperse of 2g is weighed to 200mL deionized water and the mixed solvent of dehydrated alcohol, deionized water and anhydrous
The volume ratio of ethanol is 1:1, forms chromium solution B；
3, chromium solution B is added drop-wise in graphene solution A, under room temperature after ultrasonic disperse 40min after 90 DEG C of reaction 18h
Obtain polypyrrole/graphene oxide, after being then passed through sucking filtration, washing, be vacuum dried 20h at 65 DEG C, at N2Under atmosphere protection 1600
DEG C sintering 3h obtain nitrogen-doped graphene；
4, weigh the nitrogen-doped graphene of 0.5g, the ammonium metavanadate of 4.68g, the lithium nitrate of 8.28g, 1g polyvinyl alcohol as carbon source mix
After conjunction, addition 20mL acetone is as ball-milling medium, and slurry solid content is 48%, obtains lithium vanadate presoma after carrying out ball milling dispersion
After being dried 24h at a temperature of 100 DEG C, at H2With N2The lower 950 DEG C of sintering 16h of atmosphere protection obtain lithium vanadate/carbon/nitrogen-doped graphene
Composite.
Embodiment 5
1, the cetyl trimethylammonium bromide weighing 0.3g evenly spreads in 100mL deionized water as surfactant,
Then the graphene oxide weighing 0.4g joins in surfactant solution, forms uniform graphene oxide after ultrasonic disperse 1h
Suspension A；
2, pyrroles's ultrasonic disperse of 1g is weighed to 200mL deionized water and the mixed solvent of dehydrated alcohol, deionized water and anhydrous
The volume ratio of ethanol is 1:1.2, forms chromium solution B；
3, chromium solution B is added drop-wise in graphene solution A, under room temperature, after ultrasonic disperse 0.5h, reacts 10h at 100 DEG C
After obtain polypyrrole/graphene oxide, be then passed through sucking filtration, washing after 60 DEG C be vacuum dried 24h, at CO2Under atmosphere protection
1600 DEG C of sintering 3h obtain nitrogen-doped graphene；
4, the nitrogen-doped graphene of 0.5g, the Vanadium sesquioxide of 6.0g, the lithium carbonate of 9.32g, 1g Polyethylene Glycol are weighed as carbon source
After mixing, addition 20mL dimethylformamide is as ball-milling medium, and slurry solid content is 47%, obtains vanadium after carrying out ball milling dispersion
Acid lithium presoma is dried after 15h at a temperature of 120 DEG C, and under Ar atmosphere protection, 1000 DEG C of sintering 15h obtain lithium vanadate/carbon/mix
Nitrogen graphene composite material.
Embodiment 6
1, the poly(ethylene oxide) ~ poly(propylene oxide) ~ poly(ethylene oxide) triblock copolymer P123 of 0.1g, 0.4g polycyclic oxygen second are weighed
Alkane ~ poly(propylene oxide) ~ poly(ethylene oxide) triblock copolymer 127 evenly spreads to 100mL deionized water as surfactant
In, the graphene oxide then weighing 0.4g joins in surfactant solution, forms uniform alumina stone after ultrasonic disperse 1h
Ink alkene suspension A；
2, pyrroles's ultrasonic disperse of 2.5g is weighed to 250mL deionized water and the mixed solvent of dehydrated alcohol, deionized water and nothing
The volume ratio of water-ethanol is 1:1, forms chromium solution B；
3, chromium solution B is added drop-wise in graphene solution A, under room temperature after ultrasonic disperse 0.5h after 100 DEG C of reaction 10h
Obtain polypyrrole/graphene oxide, after being then passed through sucking filtration, washing, be vacuum dried 24h at 60 DEG C, at Ar, N2Under atmosphere protection
1500 DEG C of sintering 5h obtain nitrogen-doped graphene；
4, weigh the nitrogen-doped graphene of 0.5g, the ammonium metavanadate of 2.34g, 3.0g Vanadium sesquioxide, the Lithium acetate dihydrate of 12.24g,
After 1g citric acid mixes as carbon source, addition 20mL dehydrated alcohol is as ball-milling medium, and slurry solid content is 55%, carries out ball milling
Lithium vanadate presoma is obtained at a temperature of 120 DEG C after dry 12h, at CO after dispersion2The lower 1100 DEG C of sintering 9h of atmosphere protection obtain
Lithium vanadate/carbon/nitrogen-doped graphene composite.
Embodiment 7
1, the poly(ethylene oxide) ~ poly(propylene oxide) ~ poly(ethylene oxide) triblock copolymer P123 of 0.4g is weighed as surface activity
Agent evenly spreads in 100mL deionized water, and the graphene oxide then weighing 0.4g joins in surfactant solution, super
Uniform graphene oxide suspension A is formed after sound dispersion 1h；
2, pyrroles's ultrasonic disperse of 1g is weighed to 150mL deionized water and the mixed solvent of dehydrated alcohol, deionized water and anhydrous
Ethanol volume ratio is 0.5:1, forms chromium solution B；
3, chromium solution B is added drop-wise in graphene solution A, under room temperature after ultrasonic disperse 0.5h after 100 DEG C of reaction 10h
Obtain polypyrrole/graphene oxide, after being then passed through sucking filtration, washing, be vacuum dried 24h at 60 DEG C, under Ar atmosphere protection 1600
DEG C sintering 3h obtain nitrogen-doped graphene；
4, the nitrogen-doped graphene of 0.5g, the ammonium metavanadate of 4.68g, the Lithium hydroxide monohydrate of 5.2g, 1g glucose are weighed as carbon
After the mixing of source, addition 10mL dehydrated alcohol, 10ml ethylene glycol are as ball-milling medium, and slurry solid content is 38%, carries out ball milling dispersion
After obtain lithium vanadate presoma and be dried after 18h at a temperature of 105 DEG C, under Ar atmosphere protection, 1100 DEG C of sintering 12h obtain vanadic acid
Lithium/carbon/nitrogen-doped graphene composite.
Embodiment 8
1, the poly(ethylene oxide) ~ poly(propylene oxide) ~ poly(ethylene oxide) triblock copolymer F127 of 0.5g is weighed as surface activity
Agent evenly spreads in 100mL deionized water, and the graphene oxide then weighing 0.4g joins in surfactant solution, super
Uniform graphene oxide suspension A is formed after sound dispersion 1h；
2, pyrroles's ultrasonic disperse of 5g is weighed to 250mL deionized water and the mixed solvent of dehydrated alcohol, deionized water and anhydrous
Ethanol volume ratio is 1.5:1, forms chromium solution B；
3, chromium solution B is added drop-wise in graphene solution A, under room temperature after ultrasonic disperse 0.5h after 100 DEG C of reaction 10h
Obtain polypyrrole/graphene oxide, after being then passed through sucking filtration, washing, be vacuum dried 24h at 60 DEG C, at Ar and H2Under atmosphere protection
1600 DEG C of sintering 3h obtain nitrogen-doped graphene；
4, the nitrogen-doped graphene of 0.5g, the ammonium metavanadate of 4.68g, the Lithium hydroxide monohydrate of 5.2g, 1g sucrose are weighed as carbon source
After mixing, addition 20mL dehydrated alcohol is as ball-milling medium, and slurry solid content is 42%, obtains lithium vanadate after carrying out ball milling dispersion
After presoma is dried 20h at a temperature of 110 DEG C, at Ar, CO2The lower 1050 DEG C of sintering 8h of atmosphere protection obtain lithium vanadate/carbon/nitrating
Graphene composite material.
In conjunction with accompanying drawing, with embodiment 1, lithium vanadate/carbon/nitrogen-doped graphene composite thing that the present invention prepares is described
Characterize mutually and chemical property:
Fig. 1 is the XRD figure spectrum that embodiment 1 synthesizes lithium vanadate/carbon/nitrogen-doped graphene composite, finds that diffraction maximum is the strongest, says
The degree of crystallinity of bright material is higher, without obvious impurity peaks.
Fig. 2 is the SEM collection of illustrative plates that embodiment 1 synthesizes lithium vanadate/carbon/nitrogen-doped graphene composite, as can be seen from the figure
Lithium vanadate/carbon/nitrogen-doped graphene composite is dispersed on graphene sheet layer, even particle size, does not occurs reuniting
Phenomenon, the grain diameter of material, substantially at about 500nm, is conducive to improving lithium vanadate electron transfer speed in charge and discharge process
Rate, improves the performance of material electrochemical performance.
Fig. 3 is the charging and discharging curve figure that embodiment 1 synthesizes lithium vanadate/carbon/nitrogen-doped graphene composite, is come by curve
Seeing under 50mA/g electric current density, the reversible specific capacity first through the material of doped graphene cladding is more than 400 mAh/g,
There is the mildest discharge platform in 0.5 ~ 0.8V, higher than the 0.05V of graphite cathode, will be greatly improved the security performance of battery.
Fig. 4 is the curve of double curvature figure that embodiment 1 synthesizes lithium vanadate/carbon/nitrogen-doped graphene composite, it can be seen that material
Show good under 50mA/g, 100mA/g, 200mA/g, 500mA/g, 1000mA/g, 2000mA/g, 5000mA/g electric current density
Good chemical property, returns under 50mA/g electric current density, and material electrochemical performance is still stable, illustrates to be coated with nitrogen-doped graphene pair
Material has good improvement result.
Fig. 5 is the cyclic curve figure that embodiment 1 synthesizes lithium vanadate/carbon/nitrogen-doped graphene composite, as can be seen from Fig.
Under electric current density is 50mA/g multiplying power, significantly improves through the cyclical stability of the material of overdoping, experienced by circulation in 100 weeks
Rear capability retention is still maintained at about 90%, illustrates that the material through nitrogen-doped graphene cladding has good cyclical stability.
Above content is only to present configuration example and explanation, affiliated those skilled in the art couple
Described specific embodiment makes various amendment or supplements or use similar mode to substitute, without departing from invention
Structure or surmount scope defined in the claims, all should belong to protection scope of the present invention.
Claims (8)
1. the synthetic method of composite cathode material of lithium ion battery lithium vanadate/carbon/nitrogen-doped graphene, it is characterised in that institute
The method of stating comprises the following steps:
(1) surfactant is evenly spread in deionized water, add graphene oxide, ultrasonic disperse, obtain uniform alumina
Graphene solution A, in graphene oxide solution A, graphene oxide concentration is 2 ~ 5mg/ml；
(2) mixed solvent of pyrroles's ultrasonic disperse to deionized water and dehydrated alcohol will form chromium solution B, chromium solution B
Middle pyrrole concentrations is 5 ~ 20mg/ml；Deionized water is 0.5 ~ 1.5:1 with the volume ratio of dehydrated alcohol；
(3) being added drop-wise in graphene oxide solution A by chromium solution B, under room temperature, ultrasonic disperse reaction, obtains pyrroles/oxidation stone
Ink alkene, be then passed through sucking filtration, washing final vacuum be dried, under inert atmosphere protection sinter, obtain nitrogen-doped graphene；
(4) add after nitrogen-doped graphene being mixed with vanadium source, lithium source, carbon source after ball-milling medium carries out ball milling dispersion and obtain lithium vanadate
Presoma, lithium ion and the mol ratio Li:V=3 ~ 3.2:1 of vanadium ion, be dried, sinter, obtain vanadic acid under protective gas atmosphere
Lithium/carbon/nitrogen-doped graphene composite.
The synthesis side of composite cathode material of lithium ion battery lithium vanadate/carbon/nitrogen-doped graphene the most according to claim 1
Method, it is characterised in that described step (1) surfactant is cetyl trimethylammonium bromide, poly(ethylene oxide) ~ polycyclic oxygen third
Alkane ~ poly(ethylene oxide) triblock copolymer P123, poly(ethylene oxide) ~ poly(propylene oxide) ~ poly(ethylene oxide) triblock copolymer
One or both in F127, surfactant solution concentration controls at 1 ~ 5mg/ml.
The synthesis side of composite cathode material of lithium ion battery lithium vanadate/carbon/nitrogen-doped graphene the most according to claim 1
Method, it is characterised in that described step (1) ultrasonic water temperature controls below 60 DEG C, the ultrasonic disperse time is 0.5 ~ 1h.
The synthesis side of composite cathode material of lithium ion battery lithium vanadate/carbon/nitrogen-doped graphene the most according to claim 1
Method, it is characterised in that described protective gas is N2、Ar、CO2、H2With N2, one or more in Ar gas, sinter heating rate
5 DEG C/min of ＜.
The synthesis side of composite cathode material of lithium ion battery lithium vanadate/carbon/nitrogen-doped graphene the most according to claim 1
Method, it is characterised in that described step (3) the ultrasonic disperse time is 0.5 ~ 1h, reaction temperature is 80 ~ 120 DEG C, and the response time is 10
~20h；Vacuum drying temperature is 50 ~ 80 DEG C, and drying time is 12 ~ 24h；Sintering temperature is 1200 ~ 1800 DEG C, and sintering time is 2
~4h。
The synthesis side of composite cathode material of lithium ion battery lithium vanadate/carbon/nitrogen-doped graphene the most according to claim 1
Method, it is characterised in that described step (4) lithium source is in lithium nitrate, Quilonorm (SKB), Lithium hydroxide monohydrate, lithium carbonate, Lithium acetate dihydrate
One or both；Vanadium source is one or both in ammonium metavanadate, vanadic anhydride, Vanadium sesquioxide；Described carbon source is sugarcane
One or both in sugar, glucose, carbon black, citric acid, polyvinyl alcohol, Polyethylene Glycol, ethylenediaminetetraacetic acid.
The synthesis side of composite cathode material of lithium ion battery lithium vanadate/carbon/nitrogen-doped graphene the most according to claim 1
Method, it is characterised in that described step (4) ball-milling medium is deionized water, dehydrated alcohol, ethylene glycol, acetone, dimethylformamide
In one or both, slurry solid content controls 35 ~ 60%.
The synthesis side of composite cathode material of lithium ion battery lithium vanadate/carbon/nitrogen-doped graphene the most according to claim 1
Method, it is characterised in that described step (4) baking temperature is 80 ~ 120 DEG C, drying time is 12 ~ 24h；Sintering temperature is 800 ~
1100 DEG C, sintering time is 8 ~ 16h.
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| CN109802113A (en) * | 2019-01-04 | 2019-05-24 | 三峡大学 | A kind of Li3VO4The preparation method of the composite lithium ion battery cathode material of/C/rGO/Sn |
| CN110642293A (en) * | 2019-09-05 | 2020-01-03 | 厦门理工学院 | Oxygen vacancy Li3VO4Lithium ion battery cathode material and preparation method thereof |
| CN114497508A (en) * | 2022-01-29 | 2022-05-13 | 辽宁中宏能源新材料股份有限公司 | Power type artificial graphite composite material and preparation method thereof |
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| CN109802113A (en) * | 2019-01-04 | 2019-05-24 | 三峡大学 | A kind of Li3VO4The preparation method of the composite lithium ion battery cathode material of/C/rGO/Sn |
| CN110642293A (en) * | 2019-09-05 | 2020-01-03 | 厦门理工学院 | Oxygen vacancy Li3VO4Lithium ion battery cathode material and preparation method thereof |
| CN110642293B (en) * | 2019-09-05 | 2022-07-26 | 厦门理工学院 | Oxygen vacancy Li 3 VO 4 Lithium ion battery cathode material and preparation method thereof |
| CN114497508A (en) * | 2022-01-29 | 2022-05-13 | 辽宁中宏能源新材料股份有限公司 | Power type artificial graphite composite material and preparation method thereof |
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