CN103779564B - High-performance vanadium phosphate sodium symmetric form sodium-ion battery material and its preparation method and application - Google Patents
High-performance vanadium phosphate sodium symmetric form sodium-ion battery material and its preparation method and application Download PDFInfo
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- CN103779564B CN103779564B CN201410037623.6A CN201410037623A CN103779564B CN 103779564 B CN103779564 B CN 103779564B CN 201410037623 A CN201410037623 A CN 201410037623A CN 103779564 B CN103779564 B CN 103779564B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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
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- 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 vanadium phosphate sodium symmetric form sodium ion battery electrode material, it is respectively particle, tubulose and sheet for pattern, and described vanadium phosphate sodium nano particle size is 60-90nm, described vanadium phosphate sodium nanotube, diameter, at 20-30nm, is intertwined in curling tubulose; Described vanadium phosphate sodium nanometer sheet, thickness is at 150-200nm, long and wide all at 5-6 μm.Vanadium phosphate sodium symmetric form sodium ion battery electrode material can be used as the application of the active material of sodium-ion battery.During the positive electrode of this electrode as sodium-ion battery, show excellent multiplying power, higher specific capacity and good cyclical stability.When vanadium phosphate sodium nano particle is used as the both positive and negative polarity of battery, full battery equally also has good circulation and high rate performance, and present invention process is simple, and economical and practical.
Description
Technical field
The invention belongs to nano material and technical field of electrochemistry, be specifically related to a kind of high-performance different-shape vanadium phosphate sodium symmetric form sodium-ion battery material and preparation method thereof, it can be used as sodium-ion battery positive material and negative material.
Background technology
Growing along with to energy demand, seeking new energy storage system has become a current challenge to overcome traditional fuel energy storage.Due to the low price of chargeable lithium cell, long circulation life, high-energy-density and good reversible feature, it has become the focus of many research.Certainly, the with low cost and energy-storage system efficiently of the large-scale demand for development implementing regenerative resource.But, quantize to produce along with lithium ion battery enters, to the wilderness demand of lithium metal, its price surely can be caused significantly to go up in the near future.
Sodium metal, in the periodic table of elements, is positioned at the below of lithium metal.To a certain extent, they have similar physical property and chemical property.Therefore, in rechargeable battery, sodium metal likely becomes the substitute of the most potentiality of lithium metal.And the content of sodium metal is very considerable (richness in the earth's crust occupies the 4th) at occurring in nature.Moreover, cheapness is also one of its advantage.The advantage that everything sodium metal possesses, imparts the possibility based on the research of sodium ion rechargeable battery, and that is, due to the similitude of sodium metal and lithium metal, the development that can realize with it at lithium metal, also should in like manner can be embodied on sodium metal.According to this viewpoint, obviously, sodium-ion battery opens the new direction of a development energy-storage system.
Vanadium phosphate sodium is the one very potential electrode material of tool, because it is typical sodium superionic conductors type combination.It is high that it has charge and discharge platform, the plurality of advantages such as theoretical capacity height and Stability Analysis of Structures.
Summary of the invention
The object of the present invention is to provide a kind of technique simple, meet the requirement of Green Chemistry, the vanadium phosphate sodium sodium-ion battery material with the different-shape of good electric chemical property and preparation method thereof.
The present invention solves the problems of the technologies described above adopted technical scheme: vanadium phosphate sodium symmetric form sodium ion battery electrode material, it is the outer vanadium phosphate sodium nano particle with even carbon-coating, vanadium phosphate sodium nano particle size is 60-90nm, adopts following method to obtain, comprises the following steps:
1) first measure 10ml deionized water and be placed in 100ml beaker, the ammonium metavanadate taking 2mmol is put into beaker and is stirred 20-30 minute, mixes to mixed solution;
2) measure in the mixed solution of phosphoric acid instillation step 1) of 3mmol, completely after instillation, continue stirring 30 minutes;
3) sodium carbonate taking 1.5mmol slowly adds step 2) in brown mixed solution in, continue stirring 20 minutes;
4) in step 3) gained solution, add acetylene black, its addition accounts for 10% of added ammonium metavanadate, phosphoric acid and sodium carbonate gross mass, stirs 4-6 hour at normal temperatures, obtains mixed solution;
5) mixed solution of step 4) gained is put into the oven for drying 24 hours of 70 DEG C;
6) sinter in step 5) gained dried powder taking-up placement vacuum tube furnace in argon atmosphere, wherein first sinter 4 hours with 300-400 DEG C, then sinter 8 hours with 700-900 DEG C; After tube furnace slowly cools, namely obtain the outer vanadium phosphate sodium nano particle with even carbon-coating.
Vanadium phosphate sodium symmetric form sodium ion battery electrode material, it is vanadium phosphate sodium nanotube, and diameter, at 20-30nm, is intertwined in curling tubulose; Adopt following method to obtain, comprise the following steps:
1) first measure 10ml deionized water and be placed in 100ml beaker, the ammonium metavanadate taking 2mmol is put into beaker and is stirred 20-30 minute, mixes to mixed solution;
2) measure in the mixed solution of phosphoric acid instillation step 1) of 3mmol, completely after instillation, continue stirring 30 minutes;
3) sodium carbonate taking 1.5mmol slowly adds step 2) in brown mixed solution in, continue stirring 20 minutes;
4) in step 3) gained solution, add carbon nano-tube, its addition accounts for 10% of added ammonium metavanadate, phosphoric acid and sodium carbonate gross mass, stirs 4-6 hour at normal temperatures, obtains mixed solution;
5) mixed solution of step 4) gained is put into the oven for drying 24 hours of 70 DEG C;
6) sinter in step 5) gained dried powder taking-up placement vacuum tube furnace in argon atmosphere, wherein first sinter 4 hours with 300-400 DEG C, then sinter 8 hours with 700-900 DEG C; After tube furnace slowly cools, namely obtain vanadium phosphate sodium nanotube.
Vanadium phosphate sodium symmetric form sodium ion battery electrode material, it is vanadium phosphate sodium nanometer sheet, and thickness is at 150-200nm, long and wide all at 5-6 μm; All adopt following method to obtain, comprise the following steps:
1) first measure 10ml deionized water and be placed in 100ml beaker, the ammonium metavanadate taking 2mmol is put into beaker and is stirred 20-30 minute, mixes to mixed solution;
2) measure in the mixed solution of phosphoric acid instillation step 1) of 3mmol, completely after instillation, continue stirring 30 minutes;
3) sodium carbonate taking 1.5mmol slowly adds step 2) in brown mixed solution in, continue stirring 20 minutes;
4) in step 3) gained solution, add graphite, its addition accounts for 10% of added ammonium metavanadate, phosphoric acid and sodium carbonate gross mass, stirs 4-6 hour at normal temperatures, obtains mixed solution;
5) mixed solution of step 4) gained is put into the oven for drying 24 hours of 70 DEG C;
6) sinter in step 5) gained dried powder taking-up placement vacuum tube furnace in argon atmosphere, wherein first sinter 4 hours with 300-400 DEG C, then sinter 8 hours with 700-900 DEG C; After tube furnace slowly cools, namely obtain the vanadium phosphate sodium of the different-shape that need prepare.
Described vanadium phosphate sodium symmetric form sodium ion battery electrode material is as the application of the active material of sodium-ion battery.
By such scheme, the just very vanadium phosphate sodium symmetric form sodium ion battery electrode material of described sodium-ion battery, sodium sheet is used as negative pole and assembles.
By such scheme, the both positive and negative polarity of described sodium-ion battery adopts vanadium phosphate sodium symmetric form sodium ion battery electrode material.
The invention has the beneficial effects as follows: homogeneous and there is excellent conductive performance based on the nano particle of preparation, nanotube and nanometer sheet pattern, during the positive electrode of this electrode as sodium-ion battery, show excellent multiplying power, higher specific capacity and good cyclical stability.When vanadium phosphate sodium nano particle is used as the both positive and negative polarity of battery, full battery equally also has good circulation and high rate performance, present invention process is simple, and it is economical and practical, material requested is all prepare voluntarily substantially, got final product the vanadium phosphate sodium of the different-shape of synthesis of high purity by sintering process, meet the requirement of Green Chemistry, be beneficial to the marketization and promote.
Accompanying drawing explanation
Fig. 1 is the XRD figure of embodiment 1;
Fig. 2 is the SEM figure of embodiment 1;
Fig. 3 is the TEM figure of embodiment 1;
Fig. 4 is the chemical property figure of embodiment 1;
Fig. 5 is the chemical property figure of the full battery of embodiment 1;
Fig. 6 is the structural design drawing of embodiment 1.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1:
Sintering process prepares different-shape vanadium phosphate sodium sodium-ion battery positive and negative pole material, comprises the steps:
1) ammonium metavanadate (NH used
4vO
3), phosphoric acid (H
3pO
4), sodium carbonate (Na
2cO
3) mol ratio be: 2:3:1.5.
2) first measure 10ml deionized water and be placed in 100ml beaker, the ammonium metavanadate taking 2mmol is put into beaker and is stirred 20-30 minute, mixes to mixed solution;
3) phosphoric acid then measuring 3mmol slowly instills step 2) in the mixed solution that stirs, mixed solution becomes brown by white, completely after instillation, continues stirring 30 minutes;
4) sodium carbonate next taking 1.5mmol slowly adds in the brown mixed solution in step 3), continues stirring 20 minutes;
5) finally in order to prepare the vanadium phosphate sodium of different-shape, add different carbon sources respectively: acetylene black, carbon nano-tube and graphite, the amount added accounts for 10% of other materials (ammonium metavanadate, phosphoric acid and sodium carbonate, lower same) gross mass.Above-mentioned solution is stirred 4-6 hour at normal temperatures;
6) mixed solution in step 5) is put into the oven for drying 24 hours of 70 DEG C;
7) then sinter in powder complete for drying in step 6) taking-up placement vacuum tube furnace in argon atmosphere, wherein first sinter 4 hours with 300 DEG C, then sinter 8 hours with 800 DEG C.After tube furnace slowly cools, namely obtain the vanadium phosphate sodium of the different-shape that need prepare.
During assembling sodium ion half-cell, the vanadium phosphate sodium electrode material of different-shape prepared in step 7) is used as anode, and sodium sheet is assembled as negative pole.In order to carry out the test of full battery performance, when assembling the full battery of sodium ion, the both positive and negative polarity that the vanadium phosphate sodium electrode material of different-shape prepared in step 7) is used separately as battery is assembled.
As shown in Figure 1, XRD proves to have synthesized the Nanoparticulate of pure phase, the nanotube-shaped vanadium phosphate sodium with nano-sheet, there is no miscellaneous existence.
As shown in Figure 2, the vanadium phosphate sodium nano particle of size uniformity, nanotube and nanometer sheet is observed out in ESEM (SEM) clearly.
As shown in Figure 3, high resolution TEM (HRTEM) observes the microstructure of vanadium phosphate sodium nano particle, nanotube and nanometer sheet further.Vanadium phosphate sodium nano particle size is about 60-90nm; Vanadium phosphate sodium nanotube, diameter, about 20 to 30nm, is intertwined in curling tubulose; Vanadium phosphate sodium nanometer sheet, thickness is at 150-200nm, long and wide all at 5-6 μm.
As shown in Figure 4, vanadium phosphate sodium nano particle, nanotube and nanometer sheet prepared by the present invention, carry out charge-discharge test after carry out the assembling of battery in glove box.Cyclic voltammetry shows, vanadium phosphate sodium nano particle has higher capacity and cyclical stability, and its conductivity increases significantly.Under the current density of 5C, after circulation 200 circle, vanadium phosphate sodium has higher capability retention, and close to 100%, and capacity is at 90mAh/g, and vanadium phosphate sodium nanotube and nanometer sheet capacity are only at 60mAh/g and 30mAh/g.
As shown in Figure 5, vanadium phosphate sodium nano particle is used as positive and negative pole material assembling and helps battery, can find out that its high rate performance is very excellent, when do under current density (10C), its capacity reaches 50mAh/g, and after 200 circles that circulate under the condition of 1C, the capability retention of vanadium phosphate sodium nano particle is 80%.
As shown in Figure 6, Design Mechanism of the present invention, utilize the carbon of different-shape as the base material of vanadium phosphate sodium, then good in the sintering process structure maintaining carbon substrate self, obtain the vanadium phosphate sodium particle be distributed in different-shape carbon substrate, carbon substrate provides different electronic and ionic conductive channels, can study the carbon substrate of different-shape to the Electrochemical Performances of vanadium phosphate sodium.
Embodiment 2:
Sintering process prepares different-shape vanadium phosphate sodium sodium-ion battery positive and negative pole material, comprises the steps:
1) ammonium metavanadate (NH used
4vO
3), phosphoric acid (H
3pO
4), sodium carbonate (Na
2cO
3) mol ratio be: 2:3:1.5.
2) first measure 10ml deionized water and be placed in 100ml beaker, the ammonium metavanadate taking 2mmol is put into beaker and is stirred 20-30 minute, mixes to mixed solution;
3) phosphoric acid then measuring 3mmol slowly instills step 2) in the mixed solution that stirs, mixed solution becomes brown by white, completely after instillation, continues stirring 30 minutes;
4) sodium carbonate next taking 1.5mmol slowly adds in the brown mixed solution in step 3), continues stirring 20 minutes;
5) last in order to prepare the vanadium phosphate sodium of different-shape, add different carbon sources respectively: acetylene black, carbon nano-tube and graphite, the amount added accounts for 10% of other material gross masses.Above-mentioned solution is stirred 4-6 hour at normal temperatures;
6) mixed solution in step 5) is put into the oven for drying 24 hours of 70 DEG C;
7) then sinter in powder complete for drying in step 6) taking-up placement vacuum tube furnace in argon atmosphere, wherein first sinter 4 hours with 300 DEG C, then sinter 8 hours with 700 DEG C.After tube furnace slowly cools, namely obtain the vanadium phosphate sodium of the different-shape that need prepare.
During assembling sodium ion half-cell, the vanadium phosphate sodium electrode material of different-shape prepared in step 7) is used as anode, and sodium sheet is assembled as negative pole.In order to carry out the test of full battery performance, when assembling the full battery of sodium ion, the both positive and negative polarity that the vanadium phosphate sodium electrode material of different-shape prepared in step 7) is used separately as battery is assembled.
Vanadium phosphate sodium symmetric form sodium ion battery electrode material prepared by the present invention, carries out charge-discharge test after carry out the assembling of battery in glove box.Show in cyclic voltammetry, under the discharge and recharge of high current density (1C), vanadium phosphate sodium nano particle battery still has high capacity 110mAh/g and good capability retention, and 500 circles that circulate under high current density.Simultaneously vanadium phosphate sodium nano particle has excellent high rate performance, and to compare chemical property more excellent with vanadium phosphate sodium nanotube and vanadium phosphate sodium nanometer sheet.As in high rate performance test, vanadium phosphate sodium nanotube still has the capacity of 60mAh/g under high current density 5C, and vanadium phosphate sodium nanometer sheet only has the capacity of 30mAh/g.
Embodiment 3:
Sintering process prepares different-shape vanadium phosphate sodium sodium-ion battery positive and negative pole material, comprises the steps:
1) ammonium metavanadate (NH used
4vO
3), phosphoric acid (H
3pO
4), sodium carbonate (Na
2cO
3) mol ratio be: 2:3:1.5.
2) first measure 10ml deionized water and be placed in 100ml beaker, the ammonium metavanadate taking 2mmol is put into beaker and is stirred 20-30 minute, mixes to mixed solution;
3) phosphoric acid then measuring 3mmol slowly instills step 2) in the mixed solution that stirs, mixed solution becomes brown by white, completely after instillation, continues stirring 30 minutes;
4) sodium carbonate next taking 1.5mmol slowly adds in the brown mixed solution in step 3), continues stirring 20 minutes;
5) last in order to prepare the vanadium phosphate sodium of different-shape, add different carbon sources respectively: acetylene black, carbon nano-tube and graphite, the amount added accounts for 10% of other material gross masses.Above-mentioned solution is stirred 4-6 hour at normal temperatures;
6) mixed solution in step 5) is put into the oven for drying 24 hours of 70 DEG C;
7) then sinter in powder complete for drying in step 6) taking-up placement vacuum tube furnace in argon atmosphere, wherein first sinter 4 hours with 300 DEG C, then sinter 8 hours with 900 DEG C.After tube furnace slowly cools, namely obtain the vanadium phosphate sodium of the different-shape that need prepare.
During assembling sodium ion half-cell, the vanadium phosphate sodium electrode material of different-shape prepared in step 7) is used as anode, and sodium sheet is assembled as negative pole.In order to carry out the test of full battery performance, when assembling the full battery of sodium ion, the both positive and negative polarity that the vanadium phosphate sodium electrode material of different-shape prepared in step 7) is used separately as battery is assembled.
Vanadium phosphate sodium symmetric form sodium ion battery electrode material prepared by the present invention, carries out charge-discharge test after carry out the assembling of battery in glove box.Show in cyclic voltammetry, under the discharge and recharge of high current density (5C), vanadium phosphate sodium nano particle still has high capacity 90mAh/g, and the capacity of vanadium phosphate sodium nanotube is 60mAh/g, and the capacity of vanadium phosphate sodium nanometer sheet is 30mAh/g.And vanadium phosphate sodium nano particle has best capability retention, and 500 circles that circulate under high current density.As in high rate performance test, vanadium phosphate sodium nano particle still has the capacity of 90mAh/g under high current density 5C, and vanadium phosphate sodium nanometer sheet only has the capacity of 30mAh/g.
Embodiment 4:
Sintering process prepares different-shape vanadium phosphate sodium sodium-ion battery positive and negative pole material, comprises the steps:
1) ammonium metavanadate (NH used
4vO
3), phosphoric acid (H
3pO
4), sodium carbonate (Na
2cO
3) mol ratio be: 2:3:1.5.
2) first measure 10ml deionized water and be placed in 100ml beaker, the ammonium metavanadate taking 2mmol is put into beaker and is stirred 20-30 minute, mixes to mixed solution;
3) phosphoric acid then measuring 3mmol slowly instills step 2) in the mixed solution that stirs, mixed solution becomes brown by white, completely after instillation, continues stirring 30 minutes;
4) sodium carbonate next taking 1.5mmol slowly adds in the brown mixed solution in step 3), continues stirring 20 minutes;
5) last in order to prepare the vanadium phosphate sodium of different-shape, add different carbon sources respectively: acetylene black, carbon nano-tube and graphite, the amount added accounts for 10% of other material gross masses.Above-mentioned solution is stirred 4-6 hour at normal temperatures;
6) mixed solution in step 5) is put into the oven for drying 24 hours of 70 DEG C;
7) then sinter in powder complete for drying in step 6) taking-up placement vacuum tube furnace in argon atmosphere, wherein first sinter 4 hours with 400 DEG C, then sinter 8 hours with 900 DEG C.After tube furnace slowly cools, namely obtain the vanadium phosphate sodium of the different-shape that need prepare.
During assembling sodium ion half-cell, the vanadium phosphate sodium electrode material of different-shape prepared in step 7) is used as anode, and sodium sheet is assembled as negative pole.In order to carry out the test of full battery performance, when assembling the full battery of sodium ion, the both positive and negative polarity that the vanadium phosphate sodium electrode material of different-shape prepared in step 7) is used separately as battery is assembled.
Vanadium phosphate sodium symmetric form sodium ion battery electrode material prepared by the present invention, carries out charge-discharge test after carry out the assembling of battery in glove box.Show in cyclic voltammetry, under the discharge and recharge of high current density (5C), vanadium phosphate sodium nano particle still has high capacity 90mAh/g, and the capacity of vanadium phosphate sodium nanotube is 60mAh/g, and the capacity of vanadium phosphate sodium nanometer sheet is 30mAh/g.And vanadium phosphate sodium nano particle has best capability retention, and 500 circles that circulate under high current density.As in high rate performance test, vanadium phosphate sodium nanotube still has the capacity of 60mAh/g under high current density 5C, and vanadium phosphate sodium nanometer sheet only has the capacity of 30mAh/g.
Embodiment 5:
Sintering process prepares different-shape vanadium phosphate sodium sodium-ion battery positive and negative pole material, comprises the steps:
1) ammonium metavanadate (NH used
4vO
3), phosphoric acid (H
3pO
4), sodium carbonate (Na
2cO
3) mol ratio be: 2:3:1.5.
2) first measure 10ml deionized water and be placed in 100ml beaker, the ammonium metavanadate taking 2mmol is put into beaker and is stirred 20-30 minute, mixes to mixed solution;
3) phosphoric acid then measuring 3mmol slowly instills step 2) in the mixed solution that stirs, mixed solution becomes brown by white, completely after instillation, continues stirring 30 minutes;
4) sodium carbonate next taking 1.5mmol slowly adds in the brown mixed solution in step 3), continues stirring 20 minutes;
5) last in order to prepare the vanadium phosphate sodium of different-shape, add different carbon sources respectively: acetylene black, carbon nano-tube and graphite, the amount added accounts for 10% of other material gross masses.Above-mentioned solution is stirred 4-6 hour at normal temperatures;
6) mixed solution in step 5) is put into the oven for drying 24 hours of 70 DEG C;
7) then sinter in powder complete for drying in step 6) taking-up placement vacuum tube furnace in argon atmosphere, wherein first sinter 4 hours with 400 DEG C, then sinter 8 hours with 700 DEG C.After tube furnace slowly cools, namely obtain the vanadium phosphate sodium of the different-shape that need prepare.
During assembling sodium ion half-cell, the vanadium phosphate sodium electrode material of different-shape prepared in step 7) is used as anode, and sodium sheet is assembled as negative pole.In order to carry out the test of full battery performance, when assembling the full battery of sodium ion, the both positive and negative polarity that the vanadium phosphate sodium electrode material of different-shape prepared in step 7) is used separately as battery is assembled.
Vanadium phosphate sodium symmetric form sodium ion battery electrode material prepared by the present invention, carries out charge-discharge test after carry out the assembling of battery in glove box.Show in cyclic voltammetry, under the discharge and recharge of high current density (5C), vanadium phosphate sodium nano particle still has high capacity 90mAh/g, and the capacity of vanadium phosphate sodium nanotube is 60mAh/g, and the capacity of vanadium phosphate sodium nanometer sheet is 30mAh/g.And vanadium phosphate sodium nano particle has best capability retention, and 500 circles that circulate under high current density.
Embodiment 6:
Sintering process prepares different-shape vanadium phosphate sodium sodium-ion battery positive and negative pole material, comprises the steps:
1) ammonium metavanadate (NH used
4vO
3), phosphoric acid (H
3pO
4), sodium carbonate (Na
2cO
3) mol ratio be: 2:3:1.5.
2) first measure 10ml deionized water and be placed in 100ml beaker, the ammonium metavanadate taking 2mmol is put into beaker and is stirred 20-30 minute, mixes to mixed solution;
3) phosphoric acid then measuring 3mmol slowly instills step 2) in the mixed solution that stirs, mixed solution becomes brown by white, completely after instillation, continues stirring 30 minutes;
4) sodium carbonate next taking 1.5mmol slowly adds in the brown mixed solution in step 3), continues stirring 20 minutes;
5) last in order to prepare the vanadium phosphate sodium of different-shape, add different carbon sources respectively: acetylene black, carbon nano-tube and graphite, the amount added accounts for 10% of other material gross masses.Above-mentioned solution is stirred 4-6 hour at normal temperatures;
6) mixed solution in step 5) is put into the oven for drying 24 hours of 70 DEG C;
7) then sinter in powder complete for drying in step 6) taking-up placement vacuum tube furnace in argon atmosphere, wherein first sinter 4 hours with 400 DEG C, then sinter 8 hours with 800 DEG C.After tube furnace slowly cools, namely obtain the vanadium phosphate sodium of the different-shape that need prepare.
During assembling sodium ion half-cell, the vanadium phosphate sodium electrode material of different-shape prepared in step 7) is used as anode, and sodium sheet is assembled as negative pole.In order to carry out the test of full battery performance, when assembling the full battery of sodium ion, the both positive and negative polarity that the vanadium phosphate sodium electrode material of different-shape prepared in step 7) is used separately as battery is assembled.
Vanadium phosphate sodium symmetric form sodium ion battery electrode material prepared by the present invention, carries out charge-discharge test after carry out the assembling of battery in glove box.Show in cyclic voltammetry, under the discharge and recharge of high current density (5C), vanadium phosphate sodium nano particle still has high capacity 90mAh/g, and the capacity of vanadium phosphate sodium nanotube is 60mAh/g, and the capacity of vanadium phosphate sodium nanometer sheet is 30mAh/g.And vanadium phosphate sodium nano particle has best capability retention, and 500 circles that circulate under high current density.
Claims (9)
1. vanadium phosphate sodium symmetric form sodium ion battery electrode material, it is the outer vanadium phosphate sodium nano particle with even carbon-coating, and vanadium phosphate sodium nano particle size is 60-90nm, adopts following method to obtain, comprises the following steps:
1) first measure 10ml deionized water and be placed in 100ml beaker, the ammonium metavanadate taking 2mmol is put into beaker and is stirred 20-30 minute, mixes to mixed solution;
2) measure the phosphoric acid instillation step 1 of 3mmol) mixed solution in, completely after instillation, continue stirring 30 minutes;
3) sodium carbonate taking 1.5mmol slowly adds step 2) in mixed solution in, continue stirring 20 minutes;
4) to step 3) add acetylene black in gained solution, its addition accounts for 10% of added ammonium metavanadate, phosphoric acid and sodium carbonate gross mass, stirs 4-6 hour at normal temperatures, obtains mixed solution;
5) by step 4) mixed solution of gained puts into the oven for drying 24 hours of 70 DEG C;
6) by step 5) gained dried powder takes out to place in vacuum tube furnace and sinters in argon atmosphere, wherein first with 300-400 DEG C of sintering 4 hours, then with 700-900 DEG C of sintering 8 hours; After tube furnace slowly cools, namely obtain the outer vanadium phosphate sodium nano particle with even carbon-coating.
2. the preparation method of vanadium phosphate sodium symmetric form sodium ion battery electrode material according to claim 1, comprises the following steps:
1) first measure 10ml deionized water and be placed in 100ml beaker, the ammonium metavanadate taking 2mmol is put into beaker and is stirred 20-30 minute, mixes to mixed solution;
2) measure the phosphoric acid instillation step 1 of 3mmol) mixed solution in, completely after instillation, continue stirring 30 minutes;
3) sodium carbonate taking 1.5mmol slowly adds step 2) in mixed solution in, continue stirring 20 minutes;
4) to step 3) add acetylene black in gained solution, its addition accounts for 10% of added ammonium metavanadate, phosphoric acid and sodium carbonate gross mass, stirs 4-6 hour at normal temperatures, obtains mixed solution;
5) by step 4) mixed solution of gained puts into the oven for drying 24 hours of 70 DEG C;
6) by step 5) gained dried powder takes out to place in vacuum tube furnace and sinters in argon atmosphere, wherein first with 300-400 DEG C of sintering 4 hours, then with 700-900 DEG C of sintering 8 hours; After tube furnace slowly cools, namely obtain the outer vanadium phosphate sodium nano particle with even carbon-coating.
3. vanadium phosphate sodium symmetric form sodium ion battery electrode material, it is vanadium phosphate sodium-carbon nano tube compound material, and carbon nanotube diameter, at 20-30nm, is intertwined in curling tubulose; Adopt following method to obtain, comprise the following steps:
1) first measure 10ml deionized water and be placed in 100ml beaker, the ammonium metavanadate taking 2mmol is put into beaker and is stirred 20-30 minute, mixes to mixed solution;
2) measure the phosphoric acid instillation step 1 of 3mmol) mixed solution in, completely after instillation, continue stirring 30 minutes;
3) sodium carbonate taking 1.5mmol slowly adds step 2) in mixed solution in, continue stirring 20 minutes;
4) to step 3) add carbon nano-tube in gained solution, its addition accounts for 10% of added ammonium metavanadate, phosphoric acid and sodium carbonate gross mass, stirs 4-6 hour at normal temperatures, obtains mixed solution;
5) by step 4) mixed solution of gained puts into the oven for drying 24 hours of 70 DEG C;
6) by step 5) gained dried powder takes out to place in vacuum tube furnace and sinters in argon atmosphere, wherein first with 300-400 DEG C of sintering 4 hours, then with 700-900 DEG C of sintering 8 hours; After tube furnace slowly cools, namely obtain vanadium phosphate sodium-carbon nano tube compound material.
4. the preparation method of vanadium phosphate sodium symmetric form sodium ion battery electrode material according to claim 3, comprises the following steps:
1) first measure 10ml deionized water and be placed in 100ml beaker, the ammonium metavanadate taking 2mmol is put into beaker and is stirred 20-30 minute, mixes to mixed solution;
2) measure the phosphoric acid instillation step 1 of 3mmol) mixed solution in, completely after instillation, continue stirring 30 minutes;
3) sodium carbonate taking 1.5mmol slowly adds step 2) in mixed solution in, continue stirring 20 minutes;
4) to step 3) add carbon nano-tube in gained solution, its addition accounts for 10% of added ammonium metavanadate, phosphoric acid and sodium carbonate gross mass, stirs 4-6 hour at normal temperatures, obtains mixed solution;
5) by step 4) mixed solution of gained puts into the oven for drying 24 hours of 70 DEG C;
6) by step 5) gained dried powder takes out to place in vacuum tube furnace and sinters in argon atmosphere, wherein first with 300-400 DEG C of sintering 4 hours, then with 700-900 DEG C of sintering 8 hours; After tube furnace slowly cools, namely obtain vanadium phosphate sodium-carbon nano tube compound material.
5. vanadium phosphate sodium symmetric form sodium ion battery electrode material, it is vanadium phosphate sodium-graphite nano plate composite material, and graphite nano plate thickness is at 150-200nm, long and wide all at 5-6 μm; Adopt following method to obtain, comprise the following steps:
1) first measure 10ml deionized water and be placed in 100ml beaker, the ammonium metavanadate taking 2mmol is put into beaker and is stirred 20-30 minute, mixes to mixed solution;
2) measure the phosphoric acid instillation step 1 of 3mmol) mixed solution in, completely after instillation, continue stirring 30 minutes;
3) sodium carbonate taking 1.5mmol slowly adds step 2) in mixed solution in, continue stirring 20 minutes;
4) to step 3) add graphite in gained solution, its addition accounts for 10% of added ammonium metavanadate, phosphoric acid and sodium carbonate gross mass, stirs 4-6 hour at normal temperatures, obtains mixed solution;
5) by step 4) mixed solution of gained puts into the oven for drying 24 hours of 70 DEG C;
6) by step 5) gained dried powder takes out to place in vacuum tube furnace and sinters in argon atmosphere, wherein first with 300-400 DEG C of sintering 4 hours, then with 700-900 DEG C of sintering 8 hours; After tube furnace slowly cools, namely obtain vanadium phosphate sodium-graphite nano plate composite material.
6. the preparation method of vanadium phosphate sodium symmetric form sodium ion battery electrode material according to claim 5, comprises the following steps:
1) first measure 10ml deionized water and be placed in 100ml beaker, the ammonium metavanadate taking 2mmol is put into beaker and is stirred 20-30 minute, mixes to mixed solution;
2) measure the phosphoric acid instillation step 1 of 3mmol) mixed solution in, completely after instillation, continue stirring 30 minutes;
3) sodium carbonate taking 1.5mmol slowly adds step 2) in mixed solution in, continue stirring 20 minutes;
4) to step 3) add graphite in gained solution, its addition accounts for 10% of added ammonium metavanadate, phosphoric acid and sodium carbonate gross mass, stirs 4-6 hour at normal temperatures, obtains mixed solution;
5) by step 4) mixed solution of gained puts into the oven for drying 24 hours of 70 DEG C;
6) by step 5) gained dried powder takes out to place in vacuum tube furnace and sinters in argon atmosphere, wherein first with 300-400 DEG C of sintering 4 hours, then with 700-900 DEG C of sintering 8 hours; After tube furnace slowly cools, namely obtain vanadium phosphate sodium-graphite nano plate composite material.
7. claim 1 or the vanadium phosphate sodium symmetric form sodium ion battery electrode material described in 3 or 5 are as the application of the active material of sodium-ion battery.
8. application according to claim 7, it is characterized in that the positive pole of described sodium-ion battery adopts vanadium phosphate sodium symmetric form sodium ion battery electrode material, sodium sheet is used as negative pole and assembles.
9. application according to claim 7, is characterized in that the both positive and negative polarity of described sodium-ion battery adopts vanadium phosphate sodium symmetric form sodium ion battery electrode material.
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| CN107845796B (en) * | 2017-10-27 | 2020-10-23 | 东北大学秦皇岛分校 | Carbon-doped sodium vanadium phosphate cathode material and preparation method and application thereof |
| CN113054184B (en) * | 2019-12-27 | 2023-03-10 | 深圳新宙邦科技股份有限公司 | Symmetric sodium-ion battery and preparation method thereof |
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| CN114824256A (en) * | 2022-06-28 | 2022-07-29 | 武汉理工大学三亚科教创新园 | Strontium ion doped sodium vanadium phosphate positive electrode material and preparation method thereof |
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