CN109802112A - A kind of Na4VO(PO4)2The preparation method of/C sodium-ion battery positive material - Google Patents
A kind of Na4VO(PO4)2The preparation method of/C sodium-ion battery positive material Download PDFInfo
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- CN109802112A CN109802112A CN201910008793.4A CN201910008793A CN109802112A CN 109802112 A CN109802112 A CN 109802112A CN 201910008793 A CN201910008793 A CN 201910008793A CN 109802112 A CN109802112 A CN 109802112A
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- sodium
- ion battery
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- positive material
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- 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 provides a kind of intermediate liquid phase method combination spray drying preparation Na4VO(PO4)2/ C porous microsphere sodium-ion battery anode, comprises the concrete steps that and weighs sodium source, vanadium source and carbon source, add deionized water, it stirs to it and is completely dissolved, it transfers them in hydro-thermal liner, adds deionized water, hydro-thermal reaction in convection oven, obtain clear solution, phosphorus source and organic carbon source is added, stirring causes it to be completely dissolved, obtained solution is spray-dried in nitrogen atmosphere, the presoma microballoon pre-burning under argon gas that will be obtained by spraying, then sintering obtains Na at 750 ~ 850 DEG C3V2(PO4)3/ C porous microsphere shows preferable chemical property using it as sodium-ion battery anode.Intermediate liquid phase method is prepared novel Na in conjunction with spray drying for the first time by the present invention4VO(PO4)2/ C sodium-ion battery anode.The process materials are compound uniformly, morphology controllable；Gained sample crystallization is functional, purity is high；Electrochemical property test shows it with apparent charge and discharge platform and preferable cyclical stability.
Description
Technical field
The present invention relates to a kind of NEW TYPE OF COMPOSITE sodium-ion battery anode, in particular to a kind of Na4VO(PO4)2/ C porous microsphere
The preparation method of sodium-ion battery positive material, belongs to field of electrochemical power source.
Background technique
The energy is the material base for supporting entire human civilization.With the high speed development of social economy, people are to the energy
Interdependency constantly improves.Currently, traditional fossil energy such as coal, petroleum, natural gas etc. is used by a large amount of exploitation, atmosphere is dirty
Dye, greenhouse gases discharge the problems such as become increasingly conspicuous, directly affect people's lives.Along with the energy crisis got worse
And environmental pollution, changing existing unreasonable energy resource structure is the matter of utmost importance that human kind sustainable development is faced.Therefore, it finds
Reproducible clean and environmental protection alternative energy source is extremely urgent.The renewable cleaning energy such as the wind energy, water energy, the solar energy that develop and use at present
Source has randomness and intermittence, therefore developing high-performance energy storage device is a new challenge again.
Lithium ion battery is considered as best energy storage system because its energy density is high, has extended cycle life, memory effect is small
System, and it is widely used in the small devices such as mobile phone or notebook.However, deficiency and the relatively high cost revealing of lithium resource
Lithium ion battery is compeled with the potential problems in terms of large-scale application, the cheap excellent lithium ion battery substitute of exploitation in eyebrow for a long time
Eyelash.Sodium-ion battery have and lithium ion battery similar in working principle, and have lower cost, it is considered to be a kind of ideal
Substitute.The key of sodium-ion battery research and development is to develop high-performance storage sodium positive and negative electrode material.As a kind of novel anode material
Material, Na4VO(PO4)2Oxidation/reduction current potential with higher, suitable sodium ion transmission channel, it is shown that before potential application
Scape.However, its existing main problem is that the electron conduction of material is lower, remain to be further improved.Currently, correlative study
Carry out less.Based on background above, this patent combines spraying sintering process using intermediate liquid phase method, is prepared for whole in porous knot
Structure, the Na being made of a large amount of nano particles4VO(PO4)2/ C microballoon.Na in microballoon4VO(PO4)2It is uniformly multiple in micro-scale with C
It closes, material overall conductivity can be obviously improved, and the particle of nano-scale and porous structure are conducive to the expansion of significant increase sodium ion
Dissipate efficiency.Finally, with prepared Na4VO(PO4)2/ C porous microsphere shows good as sodium-ion battery positive material
Chemical property has stronger application value.
Summary of the invention
It is an object of the invention to Na2CO3、V2O5、NH4H2PO4And organic carbon source is raw material, passes through intermediate liquid phase method
The Na of porous structure is prepared in conjunction with spraying sintering process4VO(PO4)2/ C microballoon, as sodium-ion battery positive material.Its principle
It is with Na2CO3、V2O5、C6H12N4For raw material, sodium vanadate interphase liquid is formed by hydro-thermal reaction, then in interphase liquid
Middle introducing NH4H2PO4And organic carbon source, being sufficiently stirred mixes various composition uniformly, is formed by subsequent drying process with atomizing
Microballoon, then sintering makes carbon material in-situ carburization and forms porous Na4VO(PO4)2/ C microballoon.Na in microballoon4VO(PO4)2With C
Uniformly compound, making material integrally has good electric conductivity, and porous structure and nano-scale can be obviously improved sodium ion diffusion
Efficiency.Finally, prepared Na4VO(PO4)2/ C microballoon shows preferable electrochemistry as sodium-ion battery positive material
Energy.
A kind of preparation method of the invention specifically: Na4VO(PO4)2/ C sodium-ion battery positive material, including walk as follows
It is rapid: (1) to weigh Na2CO3、V2O5And C6H12N4It is added in container, adds deionized water, stir to it and be completely dissolved；
(2) step (1) obtained solution is transferred in hydrothermal reaction kettle liner, deionized water is added to one constant volume of liner
Product, 100 ~ 180 DEG C of 12 ~ 48h of hydro-thermal reaction in convection oven；
(3) NH is added after step (2) being obtained clear solution cooled to room temperature4H2PO4And organic carbon source, it stirs complete to its
Fully dissolved；
(4) step (3) is obtained orange solution in nitrogen atmosphere to be spray-dried, controls the import temperature of spray dryer
Degree is 180 ~ 200 DEG C, and outlet temperature is 100 ~ 120 DEG C；
(5) the presoma microballoon for obtaining step (4) by spraying is with 3 ~ 5 DEG C of min-1300 ~ 350 DEG C of 3 ~ 5h of pre-burning under argon gas, so
5 ~ 10h is sintered at 750 ~ 850 DEG C afterwards, obtains Na after natural cooling4VO(PO4)2/ C porous microsphere.
Na in the step (1)2CO3、V2O5、C6H12N4Molar ratio is 3-5:1:2-5.
In further preferred scheme, Na in the step (1)2CO3、V2O5、C6H12N4Molar ratio is 4:1:5.
Hydrothermal temperature is 100 ~ 160 DEG C in the step (2), and the reaction time is 20 ~ 36h.
Machine carbon source described in the step (3) includes C6H12N4、C6H8O7·H2O、C6H12O6In any one.
The NH introduced after hydro-thermal reaction to solution in the step (3)4H2PO4Molar ratio with organic carbon source is 2-3:
2-4。
Spray drying inlet temperature is 200 DEG C in the step (4), and outlet temperature is 120 DEG C.
Sintering is with 3 DEG C of min in the step (5)-1The lower 350 DEG C of pre-burning 5h of argon gas, are then sintered at 800 DEG C
10h。
The present invention uses that intermediate fluid combines spray drying and sintering process is prepared for Na for the first time4VO(PO4)2/ C is porous micro-
Ball is as sodium-ion battery anode.Promote phosphorus source uniformly to mix with carbon source with it using sodium vanadate intermediate fluid phase precursor, passes through
Spray granulation pelletizing.In sintering process, sodium vanadate is first generated by solid phase reaction and further obtains Na4VO(PO4)2, point
Single-step solid phase reaction process is conducive to maintain to stablize micro-sphere structure and generates hole.Carbon source can effectively restore V early period5+, then by edge
Material surface in-situ carburization, finally obtains Na4VO(PO4)2/ C complex microsphere.
A kind of Na involved in the present invention4VO(PO4)2/ C sodium-ion battery positive material and preparation method have following
Outstanding feature:
(1) synthesis technology is simple, in conjunction with intermediate liquid phase and spray drying technology；
(2) Na prepared by4VO(PO4)2Na in/C4VO(PO4)2It is uniformly compound with C, porous microsphere structure, the quality of carbon is presented
Score is in 5%-10% or so；
(3) Na prepared by4VO(PO4)2/ C porous microsphere is having a size of 2 ~ 10 um, by the tiny of about 200 nm of a large amount of average-sizes
Particle composition；
(4) Na prepared by4VO(PO4)2/ C sodium-ion battery has apparent charge and discharge platform and good cyclical stability,
It is had potential application in sodium-ion battery.
Detailed description of the invention
The XRD diagram of sample prepared by Fig. 1 embodiment 1.
The SEM of sample prepared by Fig. 2 embodiment 1 schemes.
(a) of sample prepared by Fig. 3 embodiment 1 charge and discharge curve graph and (b) cycle performance figure for the first time.
(a) of sample prepared by Fig. 4 embodiment 2 charge and discharge curve graph and (b) cycle performance figure for the first time.
(a) of sample prepared by Fig. 5 embodiment 3 charge and discharge curve graph and (b) cycle performance figure for the first time.
Specific embodiment
Embodiment 1
Weigh the Na of 4 mmol2CO3With the V of 1 mmol2O5It is added in beaker, the C of 5 mmol is added6H12N4, add deionization
Water, 30 min of stirring are completely dissolved to it, transfer them in hydro-thermal liner, addition deionized water to the 80% of liner volume,
Hydro-thermal 48h in 100 DEG C of convection oven.It obtains clear solution cooled to room temperature and is transferred to beaker, weigh 4 mmol's
NH4H2PO4And 6 mmol C6H12O6It is dissolved in solution, 30 min of stirring, which are completely dissolved to solution, becomes orange-yellow.By what is obtained
Solution is spray-dried in nitrogen atmosphere, and inlet temperature is 200 DEG C, and outlet temperature is 120 DEG C.The presoma obtained by spraying is micro-
Ball is with 3 DEG C of min-1Then 350 DEG C of pre-burning 5h under argon gas are sintered 10h at 800 DEG C, obtain Na after natural cooling4VO
(PO4)2/ C porous microsphere.Prepared sample is through XRD diagram spectrum analysis as shown in Figure 1, resulting diffraction maximum and Na4VO(PO4)2
(JCPDS, no.53-0241) is corresponding, shows successfully to be prepared for Na4VO(PO4)2.C is amorphous state.Sample is carried out
SEM characterization, as seen from Figure 2, prepared material are spherical, are in porous structure.By the resulting material of embodiment by as follows
Battery is made in method: the ratio that sample obtained and acetylene black and Kynoar are 8:1:1 by weight being mixed, with N- first
It is that slurry is made in solvent that base, which adjoins pyrrolidone, on the copper foil coated in 10 μ m thicks, at 60 DEG C after dry 10h, is cut into diameter
The disk of 14 mm is dried in vacuo 12h at 120 DEG C.It is to electrode with metallic sodium piece, Celgard2400 film is diaphragm, dissolution
There is NaPF6(1 mol L-1) EC+DEC (volume ratio 1:1) solution be electrolyte, argon gas protection glove box in be assembled into
CR2032 type battery.Battery pack stands 8h after installing, then carries out constant current charge-discharge test with CT2001 battery test system, test
Voltage is 2.5 ~ 4 V, current density 1C, if Fig. 3 is prepared Na4VO(PO4)2The filling for the first time of/C sodium-ion battery anode,
Discharge curve and cycle performance figure.As shown, charge and discharge specific capacity distinguishes 58.2 and 43.5 mAh g for the first time-1, have apparent
Charge and discharge platform, charge and discharge capacity is respectively 32.2 and 32.1 mAh g after recycling 40 times-1, it is shown that preferable electrochemistry
Performance.
Embodiment 2
Weigh the Na of 4 mmol2CO3With the V of 1 mmol2O5It is added in beaker, the C of 5 mmol is added6H12N4, add deionization
Water, 30 min of stirring are completely dissolved to it, transfer them in hydro-thermal liner, addition deionized water to the 80% of liner volume,
Hydro-thermal is for 24 hours in 120 DEG C of convection oven.It obtains clear solution cooled to room temperature and is transferred to beaker, weigh 4 mmol's
NH4H2PO4And 5 mmol C6H8O7·H2O is dissolved in solution, and 30 min of stirring, which are completely dissolved to solution, becomes orange-yellow.Will
To solution be spray-dried in nitrogen atmosphere, inlet temperature be 180 DEG C, outlet temperature be 100 DEG C.The forerunner that will be obtained by spraying
Body microballoon is with 5 DEG C of min-1Then 300 DEG C of pre-burning 5h under argon gas are sintered 10h at 750 DEG C, obtain Na after natural cooling4VO
(PO4)2/ C porous microsphere.Battery is made in the resulting material of embodiment as follows: by sample obtained and acetylene black and being gathered
Vinylidene is the ratio mixing of 8:1:1 by weight, adjoins pyrrolidone using N- methyl and slurry is made as solvent, be coated in 10 μm
On the copper foil of thickness, at 60 DEG C after dry 10h, it is cut into the disk of 14 mm of diameter, is dried in vacuo 12h at 120 DEG C.With
Metallic sodium piece is to electrode, and Celgard2400 film is diaphragm, is dissolved with NaPF6(1 mol L-1) EC+DEC (volume ratio 1:
1) solution is electrolyte, is assembled into CR2032 type battery in the glove box of argon gas protection.Battery pack stands 8h after installing, then uses
CT2001 battery test system carries out constant current charge-discharge test, and test voltage is 2.5 ~ 4 V, current density 1C, if Fig. 3 is institute
The Na of preparation4VO(PO4)2The curve of charge and discharge for the first time and cycle performance figure of/C sodium-ion battery anode.As shown, for the first time
Charge and discharge specific capacity distinguishes 58.2 and 45.1 mAh g-1, have apparent charge and discharge platform, charge and discharge are held after circulation 40 times
Amount is respectively 34.2 and 33.9 mAh g-1, it is shown that preferable chemical property.
Embodiment 3
Weigh the Na of 4 mmol2CO3With the V of 1 mmol2O5It is added in beaker, the C of 5 mmol is added6H12N4, add deionization
Water, 30 min of stirring are completely dissolved to it, transfer them in hydro-thermal liner, addition deionized water to the 80% of liner volume,
Hydro-thermal 12h in 160 DEG C of convection oven.It obtains clear solution cooled to room temperature and is transferred to beaker, weigh 4 mmol's
NH4H2PO4And 5 mmol C6H12O6It is dissolved in solution, 30 min of stirring, which are completely dissolved to solution, becomes orange-yellow.By what is obtained
Solution is spray-dried in nitrogen atmosphere, and inlet temperature is 190 DEG C, and outlet temperature is 110 DEG C.The presoma obtained by spraying is micro-
Ball is with 3 DEG C of min-1Then 350 DEG C of pre-burning 5h under argon gas are sintered 10h at 800 DEG C, obtain Na after natural cooling4VO
(PO4)2/ C porous microsphere.Battery is made in the resulting material of embodiment as follows: by sample obtained and acetylene black and being gathered
Vinylidene is the ratio mixing of 8:1:1 by weight, adjoins pyrrolidone using N- methyl and slurry is made as solvent, be coated in 10 μm
On the copper foil of thickness, at 60 DEG C after dry 10h, it is cut into the disk of 14 mm of diameter, is dried in vacuo 12h at 120 DEG C.With
Metallic sodium piece is to electrode, and Celgard2400 film is diaphragm, is dissolved with NaPF6(1 mol L-1) EC+DEC (volume ratio 1:
1) solution is electrolyte, is assembled into CR2032 type battery in the glove box of argon gas protection.Battery pack stands 8h after installing, then uses
CT2001 battery test system carries out constant current charge-discharge test, and test voltage is 2.5 ~ 4V, current density 1C, if Fig. 3 is institute
The Na of preparation4VO(PO4)2The curve of charge and discharge for the first time and cycle performance figure of/C sodium-ion battery anode.As shown, for the first time
Charge and discharge specific capacity distinguishes 59.5 and 44.7 mAh g-1, have apparent charge and discharge platform, charge and discharge are held after circulation 40 times
Amount is respectively 32.5 and 32.2 mAh g-1, it is shown that preferable chemical property.
Claims (8)
1. a kind of Na4VO(PO4)2/ C sodium-ion battery positive material, Na4VO(PO4)2It is in situ uniformly compound with C, it is in porous microsphere
Shape, which is characterized in that the preparation process of the material is as follows:
(1) Na is weighed2CO3、V2O5And C6H12N4It is added in container, adds deionized water, stir to it and be completely dissolved；
(2) step (1) obtained solution is transferred in hydrothermal reaction kettle liner, deionized water is added to one constant volume of liner
Product, 100 ~ 180 DEG C of 12 ~ 48h of hydro-thermal reaction in convection oven；
(3) NH is added after step (2) being obtained clear solution cooled to room temperature4H2PO4And organic carbon source, it stirs complete to its
Fully dissolved；
(4) step (3) is obtained orange solution in nitrogen atmosphere to be spray-dried, controls the import temperature of spray dryer
Degree is 180 ~ 200 DEG C, and outlet temperature is 100 ~ 120 DEG C；
(5) the presoma microballoon for obtaining step (4) by spraying is with 3 ~ 5 DEG C of min-1300 ~ 350 DEG C of 3 ~ 5h of pre-burning under argon gas, so
5 ~ 10h is sintered at 750 ~ 850 DEG C afterwards, obtains Na after natural cooling4VO(PO4)2/ C porous microsphere.
2. Na according to claim 14VO(PO4)2The preparation method of/C sodium-ion battery positive material, which is characterized in that
Na in step (1)2CO3、V2O5、C6H12N4Molar ratio is 3-5:1:2-5.
3. Na according to claim 14VO(PO4)2The preparation method of/C sodium-ion battery positive material, which is characterized in that
Na in step (1)2CO3、V2O5、C6H12N4Molar ratio is 4:1:5.
4. Na according to claim 14VO(PO4)2The preparation method of/C sodium-ion battery positive material, which is characterized in that
Hydrothermal temperature is 100 ~ 160 DEG C in step (2), and the reaction time is 20 ~ 36h.
5. Na according to claim 14VO(PO4)2The preparation method of/C sodium-ion battery positive material, which is characterized in that
Machine carbon source described in step (3) includes C6H12N4、C6H8O7·H2O、C6H12O6In any one.
6. Na according to claim 14VO(PO4)2The preparation method of/C sodium-ion battery positive material, which is characterized in that
The NH introduced after hydro-thermal reaction to solution in step (3)4H2PO4Molar ratio with organic carbon source is 2-3:2-4.
7. Na according to claim 14VO(PO4)2The preparation method of/C sodium-ion battery positive material, which is characterized in that
Spray drying inlet temperature is 200 DEG C in step (4), and outlet temperature is 120 DEG C.
8. Na according to claim 14VO(PO4)2The preparation method of/C sodium-ion battery positive material, which is characterized in that
Sintering is with 3 DEG C of min in step (5)-1The lower 350 DEG C of pre-burning 5h of argon gas, are then sintered 10h at 800 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113764662A (en) * | 2021-07-29 | 2021-12-07 | 武汉理工大学 | Carbon-coated vanadium-titanium-manganese-sodium phosphate micro-spheres and preparation method and application thereof |
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| CN104078676A (en) * | 2014-07-29 | 2014-10-01 | 齐鲁工业大学 | Preparation method of sodium vanadyl phosphate/graphene composite material |
| CN104466099A (en) * | 2014-12-02 | 2015-03-25 | 中南大学 | High-voltage lithium cobaltate based composite cathode material of lithium ion battery and preparation method of high-voltage lithium cobaltate based composite cathode material |
| CN107492635A (en) * | 2017-07-10 | 2017-12-19 | 三峡大学 | A kind of compound sodium-ion battery positive material Na3V2(PO4)3/ C and preparation method thereof |
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| WO2014083313A1 (en) * | 2012-11-28 | 2014-06-05 | Faradion Ltd | Metal-containing compounds |
| CN104078676A (en) * | 2014-07-29 | 2014-10-01 | 齐鲁工业大学 | Preparation method of sodium vanadyl phosphate/graphene composite material |
| CN104466099A (en) * | 2014-12-02 | 2015-03-25 | 中南大学 | High-voltage lithium cobaltate based composite cathode material of lithium ion battery and preparation method of high-voltage lithium cobaltate based composite cathode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113764662A (en) * | 2021-07-29 | 2021-12-07 | 武汉理工大学 | Carbon-coated vanadium-titanium-manganese-sodium phosphate micro-spheres and preparation method and application thereof |
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Application publication date: 20190524 |