CN106611845A - Molybdenum-doped vanadium sodium phosphate/carbon three-dimensional porous nano material and preparation method and application thereof - Google Patents

Molybdenum-doped vanadium sodium phosphate/carbon three-dimensional porous nano material and preparation method and application thereof Download PDF

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CN106611845A
CN106611845A CN201710003338.6A CN201710003338A CN106611845A CN 106611845 A CN106611845 A CN 106611845A CN 201710003338 A CN201710003338 A CN 201710003338A CN 106611845 A CN106611845 A CN 106611845A
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molybdenum
sodium
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carbon
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方臻
王笑笑
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Anhui Normal University
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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
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • H01M10/00—Secondary cells; Manufacture thereof
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention discloses a molybdenum-doped vanadium sodium phosphate/carbon three-dimensional porous nano material and a preparation method and an application thereof. The molybdenum-doped vanadium sodium phosphate three-dimensional porous nano material is of a three-dimensional porous structure, the grain size is 200-500nm and the size of cavities is 80-200nm, wherein in the vanadium sodium phosphate/carbon three-dimensional porous nano material, relative to 3mmol of sodium elements, a total molar weight of molybdenum elements and vanadium elements is 2mmol; a molar weight of phosphate radicals is 3mmol; and the molar weight of the molybdenum elements is 0.01-0.2mmol. The vanadium sodium phosphate/carbon three-dimensional porous nano material prepared with the method has excellent electrochemical performance, so that the vanadium sodium phosphate/carbon three-dimensional porous nano material can be applied to in a secondary sodium-ion battery; and meanwhile, the preparation method is simple in process and convenient to operate.

Description

The vanadium phosphate sodium of molybdenum doping/carbon three-dimensional porous nano material and preparation method thereof and Using
Technical field
The present invention relates to vanadium phosphate sodium nano material, in particular it relates to the vanadium phosphate sodium/carbon three-dimensional porous nano of molybdenum doping Material and preparation method thereof and application.
Background technology
With the development of society, the demand of the energy is more and more serious.In nature, some regenerative resources are expected to solve This global problem, such as wind energy, water energy, solar energy and tide energy etc..But these energy are subject to intermittent natural The restriction of condition, therefore the high energy accumulating device of cost performance is just extremely important.Lithium ion battery is a kind of very typical energy Amount storage device, through development for many years, it has in new energy electric motor vehicle of future generation and extensive energy storage system application Very big advantage.However, in large-scale application, cost and reserves will replace energy density to become a critically important impact Factor.Sodium-ion battery relative to lithium ion battery advantageously.First, the reserves of sodium element rank on earth the 6th, lithium Reserves then come the 32nd.Secondly, the price of sodium carbonate be 0.07-0.37 sterlings/kilogram, relative to lithium carbonate 4.11-4.49 sterlings/kilogram cheap a lot.Importantly, sodium and lithium have identical physics and chemical property.Therefore, exist The theory set up on lithium ion battery can be applied equally on sodium-ion battery.Na3V2(PO4)3Positive electrode have with LiFePO4Similar discharge platform, more excellent multiplying power sexual function, more economical raw material, as sodium-ion battery electrode material Material application has big advantage, and be widely used prospect.
But, Na3V2(PO4)3Material has and LiFePO4Similar property, in charge and discharge process, the conduction of ion Property is poor, and first coulombic efficiency is low, and these can all cause the rapid decay of battery capacity.Therefore, to Na3V2(PO4)3Material enters The regulation and control of row structure and composition, obtain the Na with higher performance3V2(PO4)3Material is that the technology that this area is badly in need of solving is asked Topic.
The content of the invention
It is an object of the invention to provide the vanadium phosphate sodium of a kind of molybdenum doping/carbon three-dimensional porous nano material and preparation method thereof And application, there is excellent chemical property by vanadium phosphate sodium obtained in the method/carbon three-dimensional porous nano material so that Obtaining it can be applied in secondary sodium-ion battery, while the preparation method operation is simple, be easy to operation.
To achieve these goals, the invention provides a kind of vanadium phosphate sodium of molybdenum doping/carbon three-dimensional porous nano material, The vanadium phosphate sodium three-dimensional porous nano material of the molybdenum doping is three-dimensional porous structure, and crystallite dimension is 200-500nm, the chi in cavity It is very little for 80-200nm；Wherein, in vanadium phosphate sodium/carbon three-dimensional porous nano material, relative to the sodium element of 3mmol, molybdenum element It is 3mmol with the integral molar quantity of v element, the mole of phosphate radical is 3mmol, and the mole of molybdenum element is 0.01-0.2mmol.
Present invention also offers a kind of preparation side of the vanadium phosphate sodium of molybdenum doping described above/carbon three-dimensional porous nano material Method, including：
1) sodium source, vanadium source, phosphoric acid root are added to the water and are stirred, be subsequently added into molybdenum source, organic carbon source and stir, then System is carried out into hydro-thermal reaction, reaction cools down to obtain blue gel after terminating；
2) blue gel is dried to obtain linen presoma；
3) by presoma grind into powder, then powder is carried out into calcination processing in the presence of gaseous mixture and is mixed with obtaining molybdenum Miscellaneous vanadium phosphate sodium/carbon three-dimensional porous nano material；
Wherein, on the basis of the sodium element of 3mmol in sodium source, the integral molar quantity of v element and molybdenum element in vanadium source, molybdenum source For 2mmol, the mole of phosphate radical is 3mmol in phosphoric acid root, and the mole of molybdenum element is 0.01-0.2mmol in molybdenum source, institute The mole for stating organic carbon source is 0.08-010mmol；Gaseous mixture is made up of noble gases and reducibility gas.
Invention further provides a kind of vanadium phosphate sodium of molybdenum doping described above/carbon three-dimensional porous nano material exists Application in secondary sodium-ion battery.
In above-mentioned technical proposal, sodium source, vanadium source, phosphoric acid root, molybdenum source, organic carbon source are passed through water by the present invention first The blue gel intermediate product of heat-collosol and gel legal system, then obtains afterwards linen solid (presoma), then by white Powder after grinding is finally calcined and reduced by solid in grind into powder under protective atmosphere, finally gives Mo-Na3V2 (PO4)3The three-dimensional porous shape nano materials of/C, learn that the nano material has excellent chemical property through electro-chemical test, It is fully able to be used as the electrode material of sodium-ion battery.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of description, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is to detect the scanning electron microscope (SEM) photograph in example 1 under 10,000 times of the amplification of A1；
Fig. 2 is to detect the scanning electron microscope (SEM) photograph in example 1 under 70,000 times of the amplification of A1；
Fig. 3 is transmission electron microscope pictures of the A1 under low power in detection example 1；
Fig. 4 is transmission electron microscope pictures of the A1 under high power in detection example 1；
Fig. 5 is the X-ray diffraction spectra figure for detecting A1 in example 2；
Fig. 6 is Na in document3V2(PO4)3X-ray diffraction spectra figure；
Fig. 7 is the Raman spectrogram for detecting A1 in example 2.
Fig. 8 is the EDX spectrograms for detecting Mo in A1 in example 2；
Fig. 9 is to detect that A1 is in 0.1C discharge curves in example 2；
Figure 10 is A1 500 discharge cycles curve charts under 5C in detection example 2；
Figure 11 is A1 1000 discharge cycles curve charts under 10C in detection example 1；
Figure 12 is the curve of double curvature figure for detecting A1 in example 1.
Figure 13 is the cyclic voltammetry curve figure for detecting A1 in example 1.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that described herein concrete Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of vanadium phosphate sodium of molybdenum doping/carbon three-dimensional porous nano material, the vanadium phosphate of the molybdenum doping Sodium three-dimensional porous nano material is three-dimensional porous structure, and crystallite dimension is 200-500nm, and the size in cavity is 80-200nm；Its In, in vanadium phosphate sodium/carbon three-dimensional porous nano material, relative to the total moles of the sodium element of 3mmol, molybdenum element and v element Measure as 2mmol, the mole of phosphate radical is 3mmol, and the mole of molybdenum element is 0.01-0.2mmol.
Present invention also offers a kind of preparation side of the vanadium phosphate sodium of molybdenum doping described above/carbon three-dimensional porous nano material Method, including：
1) sodium source, vanadium source, phosphoric acid root are added to the water and are stirred, be subsequently added into molybdenum source, organic carbon source and stir, then System is carried out into hydro-thermal reaction, reaction cools down to obtain blue gel after terminating；
2) blue gel is dried to obtain linen presoma；
3) by presoma grind into powder, then powder is carried out into calcination processing in the presence of gaseous mixture and is mixed with obtaining molybdenum Miscellaneous vanadium phosphate sodium/carbon three-dimensional porous nano material；
Wherein, on the basis of the sodium element of 3mmol in sodium source, the integral molar quantity of v element and molybdenum element in vanadium source, molybdenum source For 2mmol, the mole of phosphate radical is 3mmol in phosphoric acid root, and the mole of molybdenum element is 0.01-0.2mmol in molybdenum source, institute The mole for stating organic carbon source is 0.08-010mmol；Gaseous mixture is made up of noble gases and reducibility gas.
In the step 1 of the present invention) in, the actual conditions of hydro-thermal reaction can be selected in wide scope, but in order that Obtained vanadium phosphate sodium/carbon three-dimensional porous nano material has more excellent electrochemical properties, it is preferable that in step 1) in, water Thermal response at least meets following condition：Reaction temperature is 160-200 DEG C, and the response time is 12-24h.
In the step 1 of the present invention) in, sodium source, vanadium source, phosphoric acid root, molybdenum source, the respective species of organic carbon source can be Select in wide scope, but in order that obtained vanadium phosphate sodium/carbon three-dimensional porous nano material has more excellent electrochemistry Property, it is preferable that sodium source is selected from Na2CO3、NaHCO3, at least one of sodium citrate and sodium acetate；Vanadium source be NH4VO3 And/or V2O5；Phosphoric acid root is selected from NH4H2PO4、(NH4)2HPO4With phosphoric acid at least one；Molybdenum source be acetyl acetone and/ Or molybdenum dioxide；Organic carbon source is selected from least one of ethylene glycol, glycerol, Propylene Glycol and butanediol.
In the step 1 of the present invention) in, the consumption of water can be selected in wide scope, but in order that obtained phosphoric acid Vanadium sodium/carbon three-dimensional porous nano material has more excellent electrochemical properties, it is preferable that the sodium element with 3mmol in sodium source is Benchmark, the consumption of water is 30-60mL.
In the step 2 of the present invention) in, dry actual conditions can be selected in wide scope, but in order that be obtained Vanadium phosphate sodium/carbon three-dimensional porous nano material there are more excellent electrochemical properties, it is preferable that in step 2) in, be dried full Be enough to lower condition：Baking temperature is 80-120 DEG C, and drying time is 8-12h.
In the step 2 of the present invention) in, the actual conditions and process of calcination processing can be selected in wide scope, but In order that obtained vanadium phosphate sodium/carbon three-dimensional porous nano material has more excellent electrochemical properties, it is preferable that in step 3) In, calcination processing is carried out in the way of calcine by steps：First presoma is calcined into 2-6h at 340-360 DEG C, then in 650-950 5-10h is calcined at DEG C；It is highly preferred that the calcination processing is concretely comprised the following steps：First by the presoma from 15-35 DEG C with 4-6 DEG C/ramp of min at 340-360 DEG C and 2-6h is incubated, then with the ramp of 1.5-2.5 DEG C/min to 650- 950 DEG C and 5-10h is incubated, is finally cooled to 15-35 DEG C with the speed of 9-11 DEG C/min.
In the step 3 of the present invention) in, the concrete species of noble gases and reducibility gas can be selected in wide scope Select, but in order that obtained vanadium phosphate sodium/carbon three-dimensional porous nano material has more excellent electrochemical properties, it is preferable that In step 3) in, noble gases are selected from least one of nitrogen, argon and helium；Reducibility gas are hydrogen and/or an oxygen Change carbon.
In the step 3 of the present invention) in, the content of reducibility gas can be selected in wide scope, but in order that system Vanadium phosphate sodium/carbon three-dimensional porous nano the material for obtaining has more excellent electrochemical properties, it is preferable that with the cumulative volume of gaseous mixture On the basis of, the content of reducibility gas is 5 volumes %.
Invention further provides a kind of vanadium phosphate sodium of molybdenum doping described above/carbon three-dimensional porous nano material exists Application in secondary sodium-ion battery.
Hereinafter will be described the present invention by embodiment.
Embodiment 1
1) at 25 DEG C, 1.5mmol Na are taken respectively2CO3、1.85mmol NH4VO3、3mmol NH4H2PO4、0.15mmol Acetyl acetone is added in 40mL deionized waters, under stirring state, in adding the ethylene glycol of 5mL, continues to stir after 30min, Mixed solution is proceeded in 60mL ptfe autoclaves, in an oven 180 DEG C of reaction 24h, after being cooled to 25 DEG C, obtain indigo plant Color gel.
2) blue gel obtained above is placed in an oven, 120 DEG C of baking 10h obtain linen presoma；
3) by above-mentioned linen presoma grind into powder, shielding gas (contains 5%H in tube furnace2H2/ Ar mixes Gas) under conditions of calcining (first from 25 DEG C of ramps with 5 DEG C/min to 350 DEG C and 2h is incubated, then with 2 DEG C/min's Ramp is to 850 DEG C and is incubated 6h, is finally cooled to 25 DEG C with the speed of 10 DEG C/min), obtain Mo-Na3V2(PO4)3/ C tri- Dimension cellular nano material A1.
Embodiment 2
Method according to embodiment 1 carries out that Mo-Na is obtained3V2(PO4)3Three-dimensional porous shape nano materials A2 of/C, institute is different Be, step 1) in acetyl acetone amount be 0.01mmol, NH4VO3Consumption be 1.99mmol.
Embodiment 3
Method according to embodiment 1 carries out that Mo-Na is obtained3V2(PO4)3Three-dimensional porous shape nano materials A3 of/C, institute is different Be, step 1) in acetyl acetone amount be 0.05mmol, NH4VO3Consumption be 1.95mmol.
Embodiment 4
Method according to embodiment 1 carries out that Mo-Na is obtained3V2(PO4)3Three-dimensional porous shape nano materials A4 of/C, institute is different Be, step 1) in acetyl acetone amount be 0.1mmol, NH4VO3Consumption be 1.9mmol.
Embodiment 5
Method according to embodiment 1 carries out that Mo-Na is obtained3V2(PO4)3Three-dimensional porous shape nano materials A5 of/C, institute is different Be, step 1) in acetyl acetone amount be 0.20mmol, NH4VO3Consumption be 1.8mmol.
Embodiment 6
Method according to embodiment 1 carries out that Mo-Na is obtained3V2(PO4)3Three-dimensional porous shape nano materials A6 of/C, institute is different Be, step 1) in hydrothermal temperature be 160 DEG C.
Embodiment 7
Method according to embodiment 1 carries out that Mo-Na is obtained3V2(PO4)3Three-dimensional porous shape nano materials A7 of/C, institute is different Be, step 1) in hydrothermal temperature be 170 DEG C.
Embodiment 8
Method according to embodiment 1 carries out that Mo-Na is obtained3V2(PO4)3Three-dimensional porous shape nano materials A8 of/C, institute is different Be, step 1) in hydrothermal temperature be 190 DEG C.
Embodiment 9
Method according to embodiment 1 carries out that Mo-Na is obtained3V2(PO4)3Three-dimensional porous shape nano materials A9 of/C, institute is different Be, step 1) in hydrothermal temperature be 200 DEG C.
Embodiment 10
Method according to embodiment 1 carries out that Mo-Na is obtained3V2(PO4)3Three-dimensional porous shape nano materials A10 of/C, institute is different Be, step 3) in calcining temperature be 650 DEG C.
Embodiment 11
Method according to embodiment 1 carries out that Mo-Na is obtained3V2(PO4)3Three-dimensional porous shape nano materials A11 of/C, institute is different Be, step 4) in calcining temperature be 750 DEG C.
Embodiment 12
Method according to embodiment 1 carries out that Mo-Na is obtained3V2(PO4)3Three-dimensional porous shape nano materials A12 of/C, institute is different Be, step 3) in calcining temperature be 950 DEG C.
Embodiment 13
Method according to embodiment 1 carries out that Mo-Na is obtained3V2(PO4)3Three-dimensional porous shape nano materials A13 of/C, institute is different , by Na2CO3It is changed to NaHCO3, by NH4VO3It is changed to V2O5, by NH4H2PO4It is changed to (NH4)2HPO4, acetyl acetone is changed For molybdenum dioxide, ethylene glycol is changed to into glycerol.
Embodiment 14
Method according to embodiment 1 carries out that Mo-Na is obtained3V2(PO4)3Three-dimensional porous shape nano materials A14 of/C, institute is different , by Na2CO3Sodium citrate is changed to, by NH4VO3It is changed to V2O5, by NH4H2PO4Phosphoric acid is changed to, acetyl acetone is changed to into two Molybdenum oxide, by ethylene glycol Propylene Glycol is changed to.
Embodiment 15
Method according to embodiment 1 carries out that Mo-Na is obtained3V2(PO4)3Three-dimensional porous shape nano materials A15 of/C, institute is different , by Na2CO3Sodium acetate is changed to, by NH4VO3It is changed to V2O5, by NH4H2PO4Phosphoric acid is changed to, acetyl acetone is changed to into dioxy Change molybdenum, ethylene glycol is changed to into butanediol.
Comparative example 1
Method according to embodiment 1 carries out that Mo-Na is obtained3V2(PO4)3Three-dimensional porous shape nano materials B1 of/C, institute is different Be, step 1) in be added without acetyl acetone.
Detection example 1
1) Electronic Speculum detection is scanned to A1 by Hitachi S-4800, as a result sees Fig. 1 and Fig. 2, can by Fig. 1 and Fig. 2 Know, A1 is three-dimensional porous structure.
2) transmission electron microscope detection is carried out to A1 by FEI TECNAI-G2, as a result sees Fig. 3, from the figure 3, it may be seen that A1 have it is bright Aobvious loose structure.
3) high-resolution-ration transmission electric-lens detection is carried out to A1 by JEOL-2010, as a result sees Fig. 4, as shown in Figure 4, A1 surfaces With obvious carbon-coating.
A2-A15 is detected according to above-mentioned identical method, result and the A1 of detection are consistent substantially.
Detection example 2
1) X-ray diffraction spectra detection is carried out to A1 by D8Advance X-ray power diffactometer, is tied Fruit sees Fig. 5, by Fig. 5 and document (Hybrid aqueous battery based on Na3V2 (PO4) 3/C cathode and zinc anode for potential large-scale energy storage.Journal of Power Sources 308 (2016) 52e57) in Fig. 6 control understand, A1 is the Na of NASICON structures3V2(PO4)3。
2) Raman spectrum detection is carried out to A1 by Jobin Yvon HR800, as a result sees Fig. 7, as shown in Figure 7, 1359cm-1There are D bands at place, in 1587cm-1There are G bands at place, it was demonstrated that have the presence of C.
3) elementary analysiss detection is carried out to A1 by Hitachi S-4800, as a result sees Fig. 8, it is first containing Mo as shown in Figure 8 Element.
4) by Mikrouna, Super (1220/750/900) glove box (H2O<0.1ppm, O2<1ppm) A1 materials are made It is electrode assembling into 2032 type button cells, it is tested on New ware cell tester, A1 is in electric current density Charge-discharge test during 0.1C, through multiple cycle charge discharge electro-detection when 5C, 10C, is as a result shown in Fig. 9, Figure 10, Figure 11, by Fig. 9, figure 10th, Figure 11, illustrates that the material has good cyclical stability.
5) by Mikrouna, Super (1220/750/900) glove box (H2O<0.1ppm, O2<1ppm) A1 materials are made It is electrode assembling into 2032 type button cells, it is tested on New ware cell tester, A1 carries out electric multiplying power and follows Ring detects that as a result see Figure 12, as shown in Figure 12, under conditions of 20C, capacity remains to reach 85.7mAh.g A1-1, illustrate the material Material has good high rate performance.
6) volt-ampere is circulated to A1 by CHI660E electrochemical workstations to survey, as a result sees Figure 13, as shown in Figure 13, followed Ring volt-ampere curve is consistent with charging and discharging curve result.
Detect that concrete testing result is shown in Table 1 to A2-A12, B1 according to above-mentioned identical method.
Table 1
Material XRD analysis EDS is analyzed Raman analysis Head puts 0.1C 5C/500 time 10C/1000 time
A1 Na3V2(PO4)3 Containing Mo Containing carbon 117.2mAh/g 101.2mAh/g 98.2mAh/g
B1 Na3V2(PO4)3 Without Mo Containing carbon 110.3mAh/g 68.3mAh/g 52.4mAh/g
A2 Na3V2(PO4)3 Containing Mo Containing carbon 116.8mAh/g 92.6mAh/g 82.5mAh/g
A3 Na3V2(PO4)3 Containing Mo Containing carbon 115.7mAh/g 93.7mAh/g 85.2mAh/g
A4 Na3V2(PO4)3 Containing Mo Containing carbon 116.4mAh/g 95.9mAh/g 87.7mAh/g
A5 Na3V2(PO4)3 Containing Mo Containing carbon 115.9mAh/g 91.8mAh/g 81.8mAh/g
A6 Na3V2(PO4)3 Containing Mo Containing carbon 112.1mAh/g 90.2mAh/g 80.4mAh/g
A7 Na3V2(PO4)3 Containing Mo Containing carbon 111.8mAh/g 87.3mAh/g 79.8mAh/g
A8 Na3V2(PO4)3 Containing Mo Containing carbon 108.4mAh/g 88.5mAh/g 80.1mAh/g
A9 Na3V2(PO4)3 Containing Mo Containing carbon 109.9mAh/g 92.7mAh/g 81.7mAh/g
A10 Na3V2(PO4)3 Containing Mo Containing carbon 108.6mAh/g 65.5mAh/g 47.6mAh/g
A11 Na3V2(PO4)3 Containing Mo Containing carbon 110.7mAh/g 78.9mAh/g 62.1mAh/g
A12 Na3V2(PO4)3 Containing Mo Containing carbon 112.1mAh/g 89.2mAh/g 73.5mAh/g
The result of A1-A12, B1 detection as shown in table 1, learns that nano material A1 has outstanding through electro-chemical test Chemical property：First discharge capacity is 117.2mAh/g (theoretical capacity is 117.5mAh/g), after 5C circulates 500 times, capacity For 101.2mAh/g, after 10C circulates 1000 times, capacity is 98.2mAh/g, and cyclical stability is good；And the nano material exists Under conditions of 20C, capacity remains to reach more than 85.7mAh/g, and its high rate performance is also good；Can make as the electrode of sode cell With.Meanwhile, the performance of A1-A12 is substantially better than B1.In addition, also detected to A13-A15, its chemical property and A1 bases Originally it is consistent, it is also possible to use as the electrode of sode cell.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment Detail, the present invention range of the technology design in, various simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The compound mode of energy is no longer separately illustrated.
Additionally, combination in any can also be carried out between a variety of embodiments of the present invention, as long as it is without prejudice to this The thought of invention, it should equally be considered as content disclosed in this invention.

Claims (10)

1. a kind of vanadium phosphate sodium of molybdenum doping/carbon three-dimensional porous nano material, it is characterised in that the vanadium phosphate sodium of the molybdenum doping Three-dimensional porous nano material is three-dimensional porous structure, and crystallite dimension is 200-500nm, and the size in cavity is 80-200nm；Wherein, In the vanadium phosphate sodium/carbon three-dimensional porous nano material, relative to the sodium element of 3mmol, molybdenum element always rubs with v element Your amount is 2mmol, and the mole of phosphate radical is 3mmol, and the mole of molybdenum element is 0.01-0.2mmol.
2. the preparation method of the vanadium phosphate sodium of a kind of molybdenum doping as claimed in claim 1/carbon three-dimensional porous nano material, it is special Levy and be, including：
1) sodium source, vanadium source, phosphoric acid root are added to the water and are stirred, be subsequently added into molybdenum source, organic carbon source and stir, then by body System carries out hydro-thermal reaction, and reaction cools down to obtain blue gel after terminating；
2) blue gel is dried to obtain linen presoma；
3) by the presoma grind into powder, then the powder is carried out into calcination processing to obtain in the presence of gaseous mixture The vanadium phosphate sodium of the molybdenum doping/carbon three-dimensional porous nano material；
Wherein, on the basis of the sodium element of 3mmol in the sodium source, v element and molybdenum element always rubs in the vanadium source, molybdenum source Your amount is 2mmol, and the mole of phosphate radical is 3mmol in the phosphoric acid root, and the mole of molybdenum element is in the molybdenum source 0.01-0.2mmol, the mole of the organic carbon source is 0.08-010mmol；The gaseous mixture is by noble gases and reproducibility Gas is constituted.
3. preparation method according to claim 2, wherein, in step 1) in, the hydro-thermal reaction at least meets following bar Part：Reaction temperature is 160-200 DEG C, and the response time is 12-24h.
4. preparation method according to claim 2, wherein, the sodium source is selected from Na2CO3、NaHCO3, sodium citrate and second At least one of sour sodium；Described vanadium source is NH4VO3、V2O5At least one；The phosphoric acid root is selected from NH4H2PO4、 (NH4)2HPO4With phosphoric acid at least one；Described molybdenum source is acetyl acetone and/or molybdenum dioxide；The organic carbon source choosing From at least one of ethylene glycol, glycerol, Propylene Glycol and butanediol.
5. preparation method according to claim 2, wherein, on the basis of the sodium element of 3mmol in the sodium source, the water Consumption be 30-60mL.
6. the preparation method according to any one in claim 2-5, wherein, in step 2) in, it is described it is dry meet with Lower condition：Baking temperature is 80-120 DEG C, and drying time is 8-12h.
7. preparation method according to claim 6, wherein, in step 3) in, the calcination processing is with the side of calcine by steps Formula is carried out：First the presoma is calcined into 2-6h at 340-360 DEG C, then calcine 5-10h at 650-950 DEG C；
Preferably, the calcination processing is concretely comprised the following steps：First by the presoma from the 15-35 DEG C of speed with 4-6 DEG C/min 2-6h is warming up at 340-360 DEG C and is incubated, then so that the ramp of 1.5-2.5 DEG C/min is to 650-950 DEG C and is incubated 5- 10h, is finally cooled to 15-35 DEG C with the speed of 9-11 DEG C/min.
8. preparation method according to claim 7, wherein, in step 3) in, the noble gases selected from nitrogen, argon and At least one of helium；The reducibility gas are hydrogen and/or carbon monoxide.
9. preparation method according to claim 7, wherein, on the basis of the cumulative volume of the gaseous mixture, the reproducibility The content of gas is 5 volumes %.
10. a kind of vanadium phosphate sodium/carbon three-dimensional porous nano material of molybdenum doping as claimed in claim 1 is in secondary sodium ion electricity Application in pond.
CN201710003338.6A 2017-01-04 2017-01-04 Molybdenum-doped vanadium sodium phosphate/carbon three-dimensional porous nano material and preparation method and application thereof Pending CN106611845A (en)

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CN107871865A (en) * 2017-11-02 2018-04-03 华中科技大学 A kind of preparation method of the sodium-ion battery positive material of doping vario-property vanadium phosphate sodium
CN109616651A (en) * 2018-12-11 2019-04-12 南京工业大学 Heteroatom-doped graphene-based vanadium sodium phosphate composite nano material for sodium ion anode material
CN109921001A (en) * 2019-03-25 2019-06-21 四川大学 A kind of vanadium phosphate sodium/carbon composite anode material and its Microwave-assisted synthesis and application
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CN105932277A (en) * 2016-03-01 2016-09-07 马鞍山宇驰新能源材料有限公司 Preparation method of three-dimensional porous vanadium phosphate sodium / carbon anode material
CN106025275A (en) * 2016-08-11 2016-10-12 安徽工业大学 Vanadium phosphate sodium composite nano porous cathode material and method for preparing material by using freeze drying method

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CN103000884A (en) * 2011-09-16 2013-03-27 中国科学院物理研究所 Vanadium sodium phosphate composite material as well as preparation method and application thereof
CN105932277A (en) * 2016-03-01 2016-09-07 马鞍山宇驰新能源材料有限公司 Preparation method of three-dimensional porous vanadium phosphate sodium / carbon anode material
CN106025275A (en) * 2016-08-11 2016-10-12 安徽工业大学 Vanadium phosphate sodium composite nano porous cathode material and method for preparing material by using freeze drying method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107871865A (en) * 2017-11-02 2018-04-03 华中科技大学 A kind of preparation method of the sodium-ion battery positive material of doping vario-property vanadium phosphate sodium
US11444278B2 (en) 2017-11-24 2022-09-13 Lg Energy Solution, Ltd. Cathode material for lithium secondary battery, and preparation method therefor
CN109616651A (en) * 2018-12-11 2019-04-12 南京工业大学 Heteroatom-doped graphene-based vanadium sodium phosphate composite nano material for sodium ion anode material
CN109616651B (en) * 2018-12-11 2022-03-11 南京工业大学 Heteroatom-doped graphene-based vanadium sodium phosphate composite nano material for sodium ion anode material
CN109921001A (en) * 2019-03-25 2019-06-21 四川大学 A kind of vanadium phosphate sodium/carbon composite anode material and its Microwave-assisted synthesis and application
CN109921001B (en) * 2019-03-25 2021-07-20 四川大学 Sodium vanadium phosphate/carbon composite cathode material and microwave-assisted synthesis and application thereof

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Application publication date: 20170503