CN104638228A - Coaxial carbon-coated bunchy vanadium potassium phosphate nanowire, as well as preparation method and application of nanowire - Google Patents

Coaxial carbon-coated bunchy vanadium potassium phosphate nanowire, as well as preparation method and application of nanowire Download PDF

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CN104638228A
CN104638228A CN201510057889.1A CN201510057889A CN104638228A CN 104638228 A CN104638228 A CN 104638228A CN 201510057889 A CN201510057889 A CN 201510057889A CN 104638228 A CN104638228 A CN 104638228A
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vanadium phosphate
phosphate potassium
solution
nano wire
coaxial
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CN104638228B (en
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麦立强
王选朋
孟甲申
牛朝江
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Anhui Guoxin New Material Co.,Ltd.
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Wuhan University of Technology WUT
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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 invention relates to a coaxial carbon-coated bunchy vanadium potassium phosphate nanowire and a method for preparing the nanowire. The material can be used as a sodium-ion battery cathode active material and formed by coating the vanadium potassium phosphate nanowire with a thin graphitizing carbon layer, wherein the length is in the range from 10 to 40 micrometers and the diameter is in the range from 250 to 350 nanometers; the thickness of the thin graphitizing carbon layer is in the range from 6 to 12 nanometers and the axis is formed by lapping multiple vanadium potassium phosphate nanowires. The coaxial carbon-coated bunchy vanadium potassium phosphate nanowire has the beneficial effects that the vanadium potassium phosphate nanowire is excellent in cycling stability and relatively high in rate performance when being used as the sodium-ion battery cathode active material, and excellent in electrochemical stability under large-current charge and discharge conditions; secondly, the coaxial carbon-coated bunchy vanadium potassium phosphate nanowire is simple in preparation method, prepared by a simple solution drying and calcination treatment method and low in energy consumption.

Description

Coaxial carbon coated pencil vanadium phosphate potassium nano wire and its preparation method and application
Technical field
The invention belongs to nano material and technical field of electrochemistry, be specifically related to coaxial carbon coated pencil vanadium phosphate potassium nano-material and preparation method thereof, this material can be used as sodium-ion battery positive electrode active materials.
Background technology
Along with the development of productivity and the sharp increase of population, 21 century is also increasing to the consumption of the energy, the exhaustion of the non-renewable resources such as oil, coal and natural gas, an urgent demand is found renewable resource and is filled up energy vacancy, require the sustainability of renewable resource, continuity, so that its extensive use in every field simultaneously.In existing fossil energy system, oil and coal resource not only non-renewable, and use consumption process in also can produce a large amount of CO 2, SO 2etc. harmful substance, to the environmental problem that human society brings greenhouse effect, acid rain etc. serious.This just impels people more to pay attention to setting up novel, effective energy supply system, the environment that not broken ring people depend on for existence while ensureing economic sustainable growth.Wherein, to tap a new source of energy and renewable and clean energy resource currently addresses this problem most effective method, be one of key technology that must solve 21 century, new energy materials is then the development and utilization realizing new forms of energy, and supports basis and the core of its development.In numerous new energy systems, as wind energy, solar energy, biomass energy etc., it all possesses discontinuous characteristic, and to the system that it is effectively connected to the grid, so the conversion of the energy and storage device are indispensable.
Sodium-ion battery, be a kind of device of novel energy storage, compared with lithium ion battery, meeting outside basic energy storage requirement, it has earth resource and stores the features such as abundant, cost is low, and this has echoed low-carbon (LC), environmental protection, the strategy of sustainable development further.At present, mainly contain stratiform transition metal oxide, layer structure simple substance, phosphate system etc. and be used as its electrode material.Along with going deep into of research, not only cost is low to find phosphate system electrode material gradually, and has well storage sodium performance, is the good sodium-ion battery positive electrode material of a class.But phosphate material causes its conductivity poor due to the induction of phosphate radical, make it have high power capacity to be but difficult to bring into play completely on foot, just need us by the in-stiu coating of conductive materials, to improve its electronic conductivity, improve its chemical property.Phosphoric acid vanadium lithium and vanadium phosphate sodium are widely studied respectively as the electrode material of lithium ion and sodium-ion battery, and vanadium phosphate potassium and both there is close ratio and structure, and due to the embedding of potassium ion, directly increase the ion diffuse passage of this material, therefore it should have larger potentiality as sodium-ion battery positive electrode material in theory.Mixed by simple stoichiometric proportion, and organic acid drying aid, and the process of later stage in-situ carburization obtains coaxial carbon coated pencil vanadium phosphate potassium nano-material, the graphitization carbon-coating on its Jie top layer is while the conductivity improving vanadium phosphate potassium, again for which providing a comparatively stable skeleton, suppress its structure deterioration in electrochemical process.At present, coaxial carbon coated pencil vanadium phosphate potassium nano-material have not been reported.
Summary of the invention
The object of the present invention is to provide its preparation method of a kind of coaxial carbon coated pencil vanadium phosphate potassium nano-material, its preparation process is simple, energy consumption is lower, productive rate is higher, and the coaxial carbon coated pencil vanadium phosphate potassium nano-material of gained has good chemical property as sodium-ion battery positive material.
The present invention solves the problems of the technologies described above adopted technical scheme: the preparation method of coaxial carbon coated vanadium phosphate potassium nano wire, comprises the steps:
1) by NH 4vO 3powder dispersion obtains turbid solution in deionized water, adds potassium hydroxide, and stirred at ambient temperature becomes clear to solution;
2) to step 1) add H in proportion in gained solution 3pO 4, be stirred to solution and become brownish red;
3) again to step 2) add carbon source in gained solution, strong agitation becomes yellow green to solution;
4) by step 3) solution of gained transfers in culture dish, then carries out drying;
5) by step 4) products therefrom, direct baking, obtains the greenish yellow solid loosened;
6) by step 5) products therefrom grinding, then calcine under air conditions;
7) by step 6) products therefrom calcines under moving on to argon gas condition again, obtains coaxial carbon coated pencil vanadium phosphate potassium nano wire.
By such scheme, described NH 4vO 3, KOH and H 3pO 4mol ratio be 2:3:3; Step 1) described in solution in K +ion concentration is 3/8-3/16mol/L.
By such scheme, step 3) described in carbon source be water-soluble organic acid.
By such scheme, described water-soluble organic acid is the mixing of any one or they in oxalic acid, citric acid, malic acid, tartaric acid and ascorbic acid.
By such scheme, step 4) described in baking temperature be 60-90 DEG C, drying time is 8-12 hour; Step 5) described in baking temperature be 120-200 DEG C, constant temperature time 18-24 hour; Step 6) described in calcining heat be 200-400 DEG C, calcination time is 2-6 hour; Step 7) described in calcining heat be 700-900 DEG C, calcination time is 8-12 hour.
A kind of coaxial carbon coated pencil vanadium phosphate potassium nano wire, formed by graphitization thin carbon layer coated vanadium phosphate potassium nano wire, length is 10-40 micron, and diameter is 250-350 nanometer, wherein the thickness of graphitization thin carbon layer is 6-12 nanometer, and axle center is overlapped by many vanadium phosphate potassium nano wires and formed.
Described coaxial carbon coated pencil vanadium phosphate potassium nano wire nano material is as the application of sodium-ion battery positive electrode active materials.
The method of binding soln oven dry-organic acid guiding of the present invention assembling and atmosphere calcining, by controlling content and its ratio of rolling into a ball with complex ion in mixed system of organic acid directed agents, allow and carry out electrostatic coordination balance between the two, guiding is assembled into the first precursor of nanometer, then by sintering carbonization in-stiu coating, coaxial carbon coated pencil vanadium phosphate potassium nano-material is finally obtained.Result shows, and pencil appearance of nano material prepared by the method is homogeneous, and appearance graphitization carbon-coating is evenly coated.Nano thread structure effectively can shorten the diffusion length of sodium ion in electrolyte, provides continuous print ion-transfer passage.And graphitization thin carbon layer significantly can improve the conductivity of material, and can cushioning effect be played, active material can be provided to embed at sodium ion and deviate from volumetric expansion and the space needed for contraction in process, prevent from occurring from reuniting between each nano wire, electrolyte penetrates into vanadium phosphate potassium nanowire surface by thin carbon layer, can also reduce the dissolving of active material.Therefore, preparation technology is simply efficient for coaxial carbon provided by the invention coated pencil vanadium phosphate potassium nano-material, avoid the experiment condition using hydro-thermal etc. comparatively harsh, while its synthesis cost of reduction, significantly improve the chemical property of sodium-ion battery, improve its cyclical stability and high rate performance simultaneously, solve the shortcomings such as phosphate system positive electrode conductivity is too poor, easy reunion, its chemical property is well brought into play, has huge development potentiality in sodium-ion battery application.
The invention has the beneficial effects as follows: as sodium-ion battery positive material active material, show good cyclical stability and higher high rate performance, under high current charge-discharge condition, electrochemical stability performance is excellent; Secondly, present invention process is simple, and by being coaxial carbon coated vanadium phosphate potassium nano-material after simple solution oven dry and calcination processing, energy consumption is lower.The quality of the graphitized carbon in the coaxial configuration obtained accounts for the 6.0-8.0% of raw material gross mass, is conducive to the marketization and promotes.As sodium-ion battery positive material, under the current density of 100mA/g, its specific discharge capacity is 118.6mAh/g, 1000 and 2000mA/g high current density under, its circulation 2000 times after, capability retention is respectively up to 99.0% and 96.0%.This result shows that coaxial carbon coated pencil vanadium phosphate potassium nano-material has excellent cycle performance and comparatively excellent multiplying power property, is the potential application material of sodium-ion battery.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the coaxial carbon coated vanadium phosphate potassium nano wire of the embodiment of the present invention 1 gained and the vanadium phosphate potassium block materials of embodiment 2 gained;
Fig. 2 is the Raman spectrogram of the coaxial carbon coated vanadium phosphate potassium nano wire of the embodiment of the present invention 1 gained and the vanadium phosphate potassium block materials of embodiment 2 gained;
Fig. 3 is the TG figure of the coaxial carbon coated vanadium phosphate potassium nano wire of the embodiment of the present invention 1 gained and the vanadium phosphate potassium block materials of embodiment 2 gained;
Fig. 4 is the FT-IR figure of the coaxial carbon coated vanadium phosphate potassium nano wire of the embodiment of the present invention 1 gained and the vanadium phosphate potassium block materials of embodiment 2 gained;
Fig. 5 is the SEM figure of the coaxial carbon coated vanadium phosphate potassium nano wire of the embodiment of the present invention 1 gained;
Fig. 6 is the SEM figure of the vanadium phosphate potassium block of the embodiment of the present invention 2 gained;
Fig. 7 is the distribution diagram of element of the coaxial carbon coated vanadium phosphate potassium nano wire of the embodiment of the present invention 1 gained;
Fig. 8 is the vanadium phosphate potassium block materials distribution diagram of element of the embodiment of the present invention 2 gained;
Fig. 9 is the TEM figure of the coaxial carbon coated vanadium phosphate potassium nano-material of the embodiment of the present invention 1 gained;
Figure 10 is the HRTEM figure of the coaxial carbon coated vanadium phosphate potassium nano-material of the embodiment of the present invention 1 gained;
Figure 11 is the building-up process figure of the coaxial carbon coated vanadium phosphate potassium nano-material of the embodiment of the present invention 1;
Figure 12 is the high rate performance figure of the coaxial carbon coated vanadium phosphate potassium nano wire of the embodiment of the present invention 1 and the vanadium phosphate potassium block materials of embodiment 2 gained;
Figure 13 is the cyclic voltammetry curve figure of the coaxial carbon coated vanadium phosphate potassium nano wire of the embodiment of the present invention 1 and the vanadium phosphate potassium block materials of embodiment 2 gained;
Figure 14 is the low range cycle performance figure of the coaxial carbon coated vanadium phosphate potassium nano wire of the embodiment of the present invention 1 and the vanadium phosphate potassium block materials of embodiment 2 gained;
Figure 15 is the high rate cyclic performance map of the coaxial carbon coated vanadium phosphate potassium nano wire of the embodiment of the present invention 1 and the vanadium phosphate potassium block materials of embodiment 2 gained.
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:
The preparation method of coaxial carbon coated pencil vanadium phosphate potassium nano-material, it comprises the steps:
1) by 5.0mmol NH 4vO 3powder dispersion obtains turbid solution in 20mL deionized water, adds 7.5mmol solid potassium hydroxide, and stirred at ambient temperature 10-20 minute, becomes clear to solution;
2) to step 1) add 7.5mmol H in proportion in gained solution 3pO 4, stir and become brownish red to solution in 10-25 minute;
3) again to step 2) add 6.0g oxalic acid in gained solution, strong agitation 6 hours, becomes yellow green to solution;
4) by step 3) solution of gained transfers in culture dish, to be then put under the constant temperature of 60 DEG C dry 12 hours;
5) by step 4) products therefrom, be directly put in the isoperibol of 180 DEG C and toast 24 hours, obtain the greenish yellow solid loosened;
6) by step 5) products therefrom grinding, then calcine 4 hours under 300 DEG C of air conditionses;
7) by step 6) products therefrom to move on under 800 DEG C of argon gas conditions calcining 10 hours again, obtains coaxial carbon coated pencil vanadium phosphate potassium nano wire.
Embodiment 2:
1) by 5.0mmol NH 4vO 3powder dispersion obtains turbid solution in 20mL deionized water, adds 7.5mmol solid potassium hydroxide, and stirred at ambient temperature 10-20 minute, becomes clear to solution;
2) to step 1) add 7.5mmol H in proportion in gained solution 3pO 4, stir and become brownish red to solution in 10-25 minute;
3) again to step 2) add 2.0g oxalic acid in gained solution, at 80 DEG C, strong agitation 12 hours, becomes navy blue to solution;
4) by step 3) solution of gained transfers in culture dish, to be then put under the constant temperature of 60 DEG C dry 12 hours;
5) by step 4) products therefrom, be directly put in the isoperibol of 180 DEG C and toast 20 hours, obtain the greenish yellow solid loosened;
6) by step 5) products therefrom grinding, then calcine 5 hours under 300 DEG C of air conditionses;
7) by step 6) products therefrom to move on under 800 DEG C of argon gas conditions calcining 12 hours again, obtains vanadium phosphate potassium block.
For the vanadium phosphate potassium block that coaxial carbon coated pencil vanadium phosphate potassium nano wire and the embodiment 2 of this EXPERIMENTAL EXAMPLE 1 invention obtain, determine through x-ray diffractometer, as shown in Figure 1, X-ray diffracting spectrum (XRD) shows, coaxial carbon coated pencil vanadium phosphate potassium nano wire is consistent with the peak position of vanadium phosphate potassium block, and product has higher crystallinity.As shown in Figure 2, the carbon that Raman analysis demonstrates in coaxial carbon coated pencil vanadium phosphate potassium nano wire and vanadium phosphate potassium block is graphited carbon.As shown in Figure 3, thermogravimetric analysis illustrates that the carbon content in coaxial carbon coated pencil vanadium phosphate potassium nano wire and vanadium phosphate potassium block is respectively 6.0% and 8.0%.As shown in Figure 4, FT-IR test result shows coaxial carbon coated pencil vanadium phosphate potassium nano wire and vanadium phosphate potassium block has identical valence bond structure.As shown in Figure 5, field emission scanning electron microscope (FESEM) test shows, sample topography is homogeneous, nano wire fasciculation favorable dispersibility.Co-axial nano line length is 10-20 micron, and diameter is 250-350 nanometer.As shown in Figure 6, the pattern of vanadium phosphate potassium block materials is comparatively chaotic, and particle size is larger.As Fig. 7, shown in 8, K, V, P, O and C on graphitization carbon-coating coated vanadium phosphate potassium nano wire and vanadium phosphate potassium block, several Elemental redistribution is all very even.As shown in Figure 9, transmission electron microscope (TEM) more clearly demonstrates the concrete structure of coaxial carbon coated vanadium phosphate potassium nano wire, it is formed by graphitization carbon-coating coated vanadium phosphate potassium nano wire, wherein the thickness of coated carbon-coating is about 8 nanometers, the polycrystalline that the nano wire in axle center is made up of monocrystalline.As shown in Figure 10, can find obvious lattice fringe under high magnification transmission electron microscope (HRTEM), spacing of lattice is about 0.5nm.As shown in Table 1, inductively coupled plasma test result shows, in coaxial carbon coated pencil vanadium phosphate potassium nano wire and vanadium phosphate potassium block, the elemental mole ratios example of K, V and P is very close to 3:2:3.As shown in figure 11, synthesis mechanism of the present invention is: adopt the method that solution is dried, two excessive oxalic acid hydrates are ionized into C 2o 4 2-, it plays the effect of directed agents, makes vanadium phosphate potassium presoma complex ion group be assembled into orderly nanowire alignment, by calcining in pre-burning and argon gas in later stage air, makes inner vanadium phosphate potassium complex ion unity crystalline substance form nano wire, outside C 2o 4 2-there is carbonization and form carbon coating layer, finally obtain coaxial carbon coated pencil vanadium phosphate potassium nano-material.
Coaxial carbon coated pencil vanadium phosphate potassium nano-material is as sodium-ion battery positive electrode active materials, and all the other steps of the assemble method of sodium-ion battery are identical with common preparation method.The assemble method of sodium-ion battery is as follows, adopts coaxial carbon coated pencil vanadium phosphate potassium nano wire as active material, and acetylene black is as conductive agent, and polytetrafluoroethylene is as binding agent, and the mass ratio of active material, acetylene black, Kynoar is 70:20:10; After they fully being mixed in proportion, add a small amount of isopropyl alcohol, grinding evenly, twin rollers is pressed the electrode slice that about 0.5mm is thick; It is for subsequent use after 24 hours that the positive plate pressed is placed in the oven drying of 80 DEG C.Take concentration as 1mol/cm 3naClO 4solution is as electrolyte, and the ethylene carbonate of its solvent to be mass ratio be 1:1 mixing and dimethyl carbonate, with sodium metal sheet for negative pole, carry out electrochemical property test between 1.5-4.0V.
As shown in figure 12, coaxial carbon coated pencil vanadium phosphate potassium nano-material has excellent high rate performance, and it is under the current density of 100mA/g, and initial capacity is 1.8 times of vanadium phosphate potassium block.After the test of continuous print multiplying power, its multiplying power recovery rate is close to 99%.
As shown in figure 13, coaxial carbon coated pencil vanadium phosphate potassium nano wire and vanadium phosphate potassium block materials have close CV curve, and in charge and discharge process, only have two to faint redox peak, this two opposite joint is respectively 1.52/3.47,1.73/3.64V.
As shown in figure 14, coaxial carbon coated pencil vanadium phosphate potassium nano wire and vanadium phosphate potassium block materials are when permanent direct current charge-discharge, for coaxial carbon coated pencil vanadium phosphate potassium nano wire, the constant current charge-discharge test result of carrying out under 100mA/g shows, its first discharge specific capacity can reach 118.6mAh/g, and after 100 circulations, capability retention reaches 99.4%.And vanadium phosphate potassium block materials is example, the constant current charge-discharge test result of carrying out under 100mA/g shows, its first discharge specific capacity is 109.1mAh/g, for capability retention reaches 56.2% after 100 circulations.For coaxial carbon coated pencil vanadium phosphate potassium nano wire, the constant current charge-discharge test result of carrying out under 200mA/g shows, after 600 circulations, its capacity is 2 times of vanadium phosphate potassium block.For coaxial carbon coated pencil vanadium phosphate potassium nano wire, the constant current charge-discharge test result of carrying out under 500mA/g shows, after 1000 circulations, its capability retention is 93%, and vanadium phosphate potassium block circulates after 300 times and only remains with 59.6% of initial capacity under this current density.
As shown in figure 15, coaxial carbon coated pencil vanadium phosphate potassium nano wire is under higher current density 1000,2000mA/g, after 2000 circulations, its capability retention is respectively up to 99.0% and 96.0%, and individual pen attenuation rate is respectively 0.0053% and 0.0023%.
The ICP test result of the coaxial carbon of table 1 embodiment 1 gained coated vanadium phosphate potassium pencil nano wire and embodiment 2 gained vanadium phosphate potassium block
Embodiment 3:
1) by 10.0mmol NH 4vO 3powder dispersion obtains turbid solution in 50mL deionized water, adds 15.0mmol solid potassium hydroxide, and stirred at ambient temperature 20-30 minute, becomes clear to solution;
2) to step 1) add 15.0mmol H in proportion in gained solution 3pO 4, stir and become brownish red to solution in 35-55 minute;
3) again to step 2) add 4.0g malic acid in gained solution, strong agitation 12 hours, becomes yellow green to solution;
4) by step 3) solution of gained transfers in culture dish, to be then put under the constant temperature of 60 DEG C dry 15 hours;
5) by step 4) products therefrom, be directly put in the isoperibol of 180 DEG C and toast 24 hours, obtain the greenish yellow solid loosened;
6) by step 5) products therefrom grinding, then calcine 6 hours under 300 DEG C of air conditionses;
7) by step 6) products therefrom to move on under 900 DEG C of argon gas conditions calcining 8 hours again, obtains coaxial carbon coated pencil vanadium phosphate potassium nano wire.
For the coaxial carbon coated pencil vanadium phosphate potassium nano wire of the present embodiment gained, the constant current charge-discharge test result of carrying out under 200mA/g shows, its first discharge specific capacity can reach 91.2mAh/g, for capability retention reaches 92.3% after 100 circulations.
Embodiment 4:
1) by 5.0mmol NH 4vO 3powder dispersion obtains turbid solution in 40mL deionized water, adds 7.5mmol solid potassium hydroxide, and stirred at ambient temperature 10-20 minute, becomes clear to solution;
2) to step 1) add 7.5mmol H in proportion in gained solution 3pO 4, stir and become brownish red to solution in 15-25 minute;
3) again to step 2) add 6.0 ascorbic acid in gained solution, strong agitation 12 hours, becomes yellow green to solution;
4) by step 3) to transfer to diameter be in the glass culture dish of 15cm for the solution of gained, to be then put under the constant temperature of 60 DEG C dry 10 hours;
5) by step 4) products therefrom, be directly put in the isoperibol of 180 DEG C and toast 24 hours, obtain the greenish yellow solid loosened;
6) by step 5) products therefrom grinding, then calcine 4 hours under 300 DEG C of air conditionses;
7) by step 6) products therefrom to move on under 700 DEG C of argon gas conditions calcining 10 hours again, obtains coaxial carbon coated pencil vanadium phosphate potassium nano wire.
For the coaxial carbon coated pencil vanadium phosphate potassium nano wire of the present embodiment gained, the constant current charge-discharge test result of carrying out under 500mA/g shows, its first discharge specific capacity can reach 72.9mA/g, and after 1000 circulations, capability retention reaches 95.0%.
Embodiment 5:
1) by 7.5mmol NH 4vO 3powder dispersion obtains turbid solution in 40mL deionized water, adds 11.25mmol solid potassium hydroxide, and stirred at ambient temperature 10-25 minute, becomes clear to solution;
2) to step 1) add 11.25mmol H in proportion in gained solution 3pO 4, stir and become brownish red to solution in 15-35 minute;
3) again to step 2) add 8.0g tartaric acid in gained solution, strong agitation 10 hours, becomes yellow green to solution;
4) by step 3) solution of gained transfers in culture dish, to be then put under the constant temperature of 60 DEG C dry 10 hours;
5) by step 4) products therefrom, be directly put in the isoperibol of 180 DEG C and toast 24 hours, obtain the greenish yellow solid loosened;
6) by step 5) products therefrom grinding, then calcine 2 hours under 300 DEG C of air conditionses;
7) by step 6) products therefrom to move on under 800 DEG C of argon gas conditions calcining 10 hours again, obtains coaxial carbon coated pencil vanadium phosphate potassium nano wire.
For the coaxial carbon coated pencil vanadium phosphate potassium nano wire of the present embodiment gained, the constant current charge-discharge test result of carrying out under 100mA/g shows, its first discharge specific capacity can reach 116.8mAh/g, for capability retention reaches 88.2% after 100 circulations.
Embodiment 6:
1) by 5.0mmol NH 4vO 3powder dispersion obtains turbid solution in 40mL deionized water, adds 7.5mmol solid potassium hydroxide, and stirred at ambient temperature 10-25 minute, becomes clear to solution;
2) to step 1) add 7.5mmol H in proportion in gained solution 3pO 4, stir and become brownish red to solution in 15-35 minute;
3) again to step 2) add 2.0g oxalic acid and 3.0g malic acid in gained solution, strong agitation 10 hours, becomes yellow green to solution;
4) by step 3) solution of gained transfers in culture dish, to be then put under the constant temperature of 60 DEG C dry 10 hours;
5) by step 4) products therefrom, be directly put in the isoperibol of 160 DEG C and toast 18 hours, obtain the greenish yellow solid loosened;
6) by step 5) products therefrom grinding, then calcine 5 hours under 350 DEG C of air conditionses;
7) by step 6) products therefrom to move on under 800 DEG C of argon gas conditions calcining 12 hours again, obtains coaxial carbon coated pencil vanadium phosphate potassium nano wire.
For the coaxial carbon coated pencil vanadium phosphate potassium nano wire of the present embodiment gained, the constant current charge-discharge test result of carrying out under 100mA/g shows, its first discharge specific capacity can reach 113.9mAh/g, and after 100 circulations, capability retention reaches 96.7%.
Embodiment 7:
1) by 5.0mmol NH 4vO 3powder dispersion obtains turbid solution in 50mL deionized water, adds 7.5mmol solid potassium hydroxide, and stirred at ambient temperature 10-25 minute, becomes clear to solution;
2) to step 1) add 7.5mmol H in proportion in gained solution 3pO 4, stir and become brownish red to solution in 15-35 minute;
3) again to step 2) add 2.0g oxalic acid, 2.0g malic acid, 2.0g ascorbic acid and 2.0g tartaric acid in gained solution, strong agitation 6 hours, becomes yellow green to solution;
4) by step 3) to transfer to diameter be in the glass culture dish of 15cm for the solution of gained, to be then put under the constant temperature of 60 DEG C dry 10 hours;
5) by step 4) products therefrom, be directly put in the isoperibol of 180 DEG C and toast 20 hours, obtain the greenish yellow solid loosened;
6) by step 5) products therefrom grinding, then calcine 2 hours under 500 DEG C of air conditionses;
7) by step 6) products therefrom to move on under 800 DEG C of argon gas conditions calcining 9 hours again, obtains coaxial carbon coated pencil vanadium phosphate potassium nano wire.
For the coaxial carbon coated pencil vanadium phosphate potassium nano wire of the present embodiment gained, the constant current charge-discharge test result of carrying out under 100mA/g shows, its first discharge specific capacity can reach 115.9mAh/g, and after 100 circulations, capability retention reaches 98.4%.

Claims (7)

1. the preparation method of coaxial carbon coated vanadium phosphate potassium nano wire, comprises the steps:
1) by NH 4vO 3powder dispersion obtains turbid solution in deionized water, adds potassium hydroxide, and stirred at ambient temperature becomes clear to solution;
2) to step 1) add H in proportion in gained solution 3pO 4, be stirred to solution and become brownish red;
3) again to step 2) add carbon source in gained solution, strong agitation becomes yellow green to solution;
4) by step 3) solution of gained transfers in culture dish, then carries out drying;
5) by step 4) products therefrom, direct baking, obtains the greenish yellow solid loosened;
6) by step 5) products therefrom grinding, then calcine under air conditions;
7) by step 6) products therefrom calcines under moving on to argon gas condition again, obtains coaxial carbon coated pencil vanadium phosphate potassium nano wire.
2. the preparation method of coaxial carbon according to claim 1 coated pencil vanadium phosphate potassium nano wire, is characterized in that: described NH 4vO 3, KOH and H 3pO 4mol ratio be 2:3:3; Step 1) described in solution in K +ion concentration is 3/8-3/16mol/L.
3. the preparation method of coaxial carbon according to claim 1 coated pencil vanadium phosphate potassium nano wire, is characterized in that: step 3) described in carbon source be water-soluble organic acid.
4. the preparation method of coaxial carbon according to claim 3 coated pencil vanadium phosphate potassium nano wire, is characterized in that: described water-soluble organic acid is the mixing of any one or they in oxalic acid, citric acid, malic acid, tartaric acid and ascorbic acid.
5. the preparation method of coaxial carbon according to claim 1 coated pencil vanadium phosphate potassium nano wire, is characterized in that: step 4) described in baking temperature be 60-90 DEG C, drying time is 8-12 hour; Step 5) described in baking temperature be 120-200 DEG C, constant temperature time 18-24 hour; Step 6) described in calcining heat be 200-400 DEG C, calcination time is 2-6 hour; Step 7) described in calcining heat be 700-900 DEG C, calcination time is 8-12 hour.
6. one kind by the coaxial carbon of any preparation method of claim 1-5 gained coated pencil vanadium phosphate potassium nano wire, formed by graphitization thin carbon layer coated vanadium phosphate potassium nano wire, length is 10-40 micron, diameter is 250-350 nanometer, wherein the thickness of graphitization thin carbon layer is 6-12 nanometer, and axle center is overlapped by many vanadium phosphate potassium nano wires and formed.
7. coaxial carbon according to claim 6 coated pencil vanadium phosphate potassium nano wire nano material is as the application of sodium-ion battery positive electrode active materials.
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