CN104638228B - 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

Info

Publication number
CN104638228B
CN104638228B CN201510057889.1A CN201510057889A CN104638228B CN 104638228 B CN104638228 B CN 104638228B CN 201510057889 A CN201510057889 A CN 201510057889A CN 104638228 B CN104638228 B CN 104638228B
Authority
CN
China
Prior art keywords
vanadium phosphate
phosphate potassium
solution
carbon coating
coaxial
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201510057889.1A
Other languages
Chinese (zh)
Other versions
CN104638228A (en
Inventor
麦立强
王选朋
孟甲申
牛朝江
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anhui Guoxin New Material Co.,Ltd.
Original Assignee
Wuhan University of Technology WUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan University of Technology WUT filed Critical Wuhan University of Technology WUT
Priority to CN201510057889.1A priority Critical patent/CN104638228B/en
Publication of CN104638228A publication Critical patent/CN104638228A/en
Application granted granted Critical
Publication of CN104638228B publication Critical patent/CN104638228B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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 coating 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, and in particular to coaxial carbon coating pencil vanadium phosphate potassium nanometer Wire material and preparation method thereof, the material can be used as sodium-ion battery positive electrode active materials.
Background technology
With the development and the sharp increase of population of the productivity, consumption of the 21 century to the energy is also increasing, oil, coal The exhaustion of the non-renewable resources such as charcoal and natural gas, an urgent demand are found Renewable resource to fill up energy vacancy, while requiring The sustainability of Renewable resource, seriality, the extensive application in order to which in every field.In existing fossil energy system In system, oil and coal resource are not only non-renewable, and can also produce substantial amounts of CO in using consumption process2、SO2Deng harmful Material, brings the serious environmental problem such as greenhouse effect, acid rain to human society.This just promotes people more to pay attention to setting up new , effective energy supply system, do not break the environment that ring people depend on for existence while economic sustainable growth is ensured.Its In, it is currently to solve this problem most efficient method to tap a new source of energy with renewable and clean energy resource, is must to solve 21 century One of key technology, new energy materialses are then the developments and utilizations for realizing new forms of energy, and support basis and core that it develops. In numerous new energy systems, such as wind energy, solar energy, biomass energy etc., which all possesses discontinuous characteristic, to by its Effectively be connected to the grid system, then the conversion of the energy and storage device are indispensable.
Sodium-ion battery, is a kind of device of new energy storage, compared with lithium ion battery, is meeting basic energy Outside the memory requirement of source, the features such as it has earth resource storage abundant, low cost, this further echoed low-carbon (LC), environmental protection, can Sustainable development strategy.At present, stratiform transition metal oxide, layer structure simple substance, phosphate system etc. mainly are used as which Electrode material.With going deep into for research, phosphate system electrode material not only low cost is gradually found, and there is storage well Sodium performance, is the preferable sodium-ion battery positive electrode material of a class.But phosphate material is led due to the inducing action of phosphate radical Cause its electric conductivity poor so as to have high power capacity to be but difficult to bring into play completely on foot, it is necessary to which we are by the original position of conductive materials Cladding, to improve its electronic conductivity, improves its chemical property.Phosphoric acid vanadium lithium and vanadium phosphate sodium are respectively as lithium ion and sodium The electrode material of ion battery has been widely studied, and vanadium phosphate potassium has close ratio and a structure with both, and due to Potassium ion it is embedded, directly increase the ion diffusion admittance of the material, thus in theory its as sodium-ion battery positive electrical Pole material should have larger potentiality.Mixed by simple stoichiometric proportion, and organic acid auxiliary drying, and later stage in-situ carbon The process of change obtains coaxial carbon coating pencil vanadium phosphate potassium nano-material, and the graphitization carbon-coating on its Jie top layer is improving vanadium phosphate While the electric conductivity of potassium, a relatively stable skeleton is provided for again, suppress its structure in electrochemical process Deterioration.At present, coaxial carbon coating pencil vanadium phosphate potassium nano-material has not been reported.
The content of the invention
It is an object of the invention to provide a kind of its preparation method of coaxial carbon coating pencil vanadium phosphate potassium nano-material, Its preparation process is simple, and energy consumption is relatively low, and yield is higher, and the coaxial carbon coating pencil vanadium phosphate potassium nano-material of gained is used as sodium Ion battery positive electrode has good chemical property.
The present invention solves the technical scheme that adopted of above-mentioned technical problem：The system of coaxial carbon coating vanadium phosphate potassium nano wire Preparation Method, comprises the steps：
1) by NH4VO3Powder dispersion obtains turbid solution in deionized water, adds potassium hydroxide, is stirred to molten under room temperature Liquid is changed into clear；
2) to step 1) H is proportionally added in resulting solution3PO4, stir to solution and be changed into brownish red；
3) again to step 2) add carbon source, strong agitation to be changed into yellow green to solution in resulting solution；
4) by step 3) obtained by solution be transferred in culture dish, be then dried；
5) by step 4) products therefrom, direct baking obtains loose greenish yellow solid；
6) by step 5) products therefrom grinding, then calcine under air conditionses；
7) by step 6) products therefrom moves on to again, obtains coaxial carbon coating pencil vanadium phosphate potassium nanometer Line.
By such scheme, described NH4VO3, KOH and H3PO4Mol 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, during described water-soluble organic acid is oxalic acid, citric acid, malic acid, tartaric acid and ascorbic acid Any one or their mixing.
By such scheme, step 4) described in baking temperature be 60-90 DEG C, drying time be 8-12 hours；Step 5) institute The baking temperature stated is 120-200 DEG C, constant temperature time 18-24 hours；Step 6) described in calcining heat be 200-400 DEG C, forge The burning time is 2-6 hours；Step 7) described in calcining heat be 700-900 DEG C, calcination time be 8-12 hours.
A kind of coaxial carbon coating pencil vanadium phosphate potassium nano wire, it is linear by graphitization thin carbon layer cladding vanadium phosphate potassium nanometer Be 10-40 microns into, length, a diameter of 250-350 nanometers, the wherein thickness of graphitization thin carbon layer are 6-12 nanometers, axle center by Many vanadium phosphate potassium nano wires overlap to be formed.
Described coaxial carbon coating pencil vanadium phosphate potassium nano wire nano material is used as sodium-ion battery positive electrode active materials Application.
The method that binding soln drying-organic acid of the present invention is oriented to assembling and atmosphere calcining, is oriented to by controlling organic acid The content of agent and its ratio in mixed system with complex ion group, allow, be oriented to Nanometer elder generation precursor is assembled into, then by sintering carbonization in-stiu coating, coaxial carbon coating pencil vanadium phosphate potassium is finally given and is received Nanowire material.As a result show, pencil appearance of nano material prepared by the method is homogeneous, and appearance graphitization carbon-coating is evenly coated.Receive Nanowire structure can effectively shorten the diffusion length of sodium ion in electrolyte, there is provided continuous ion-transfer passage.And graphitization Thin carbon layer can greatly improve the electric conductivity of material, and can play cushioning effect, can provide active material embedding in sodium ion The required space of volumetric expansion and contraction during entering and deviating from, from reuniting, electrolyte can to prevent generation between each nano wire Vanadium phosphate potassium nanowire surface is penetrated into by thin carbon layer, the dissolving of active substance can also be reduced.Therefore, the present invention is provided Coaxial carbon coating pencil vanadium phosphate potassium nano-material preparation process is simple is efficient, it is to avoid using the more harsh reality such as hydro-thermal Condition is tested, while its synthesis cost is reduced, the chemical property of sodium-ion battery greatly improved, while improve which following Ring stability and high rate performance, solve phosphate system positive electrode electric conductivity it is too poor, the shortcomings of easily reunite so as to electrochemistry Can bring into play well, have huge development potentiality in sodium-ion battery application.
The invention has the beneficial effects as follows：As sodium-ion battery positive material active substance, good circulation is shown steady Qualitative and higher high rate performance, under the conditions of high current charge-discharge, electrochemically stable performance is excellent；Secondly, present invention process letter Single, the i.e. coaxial carbon coating vanadium phosphate potassium nano-material after simple solution drying and calcination processing, energy consumption are relatively low.It is resulting Coaxial configuration in the quality of graphitized carbon account for the 6.0-8.0% of raw material gross mass, be conducive to market-oriented popularization.As sodium from Sub- cell positive material, under the electric current density of 100mA/g, its specific discharge capacity is 118.6mAh/g, 1000 and 2000mA/ Under the high current density of g, after which circulates 2000 times, capability retention is up to 99.0% and 96.0% respectively.The result shows together Axle carbon coating pencil vanadium phosphate potassium nano-material has excellent cycle performance and more excellent multiplying power property, is sodium ion The potential application material of battery.
Description of the drawings
Fig. 1 is the vanadium phosphate obtained by coaxial carbon coating vanadium phosphate potassium nano wire and embodiment 2 obtained by the embodiment of the present invention 1 The XRD figure of potassium block materials；
Fig. 2 is the vanadium phosphate obtained by coaxial carbon coating vanadium phosphate potassium nano wire and embodiment 2 obtained by the embodiment of the present invention 1 The Raman spectrogram of potassium block materials；
Fig. 3 is the vanadium phosphate obtained by coaxial carbon coating vanadium phosphate potassium nano wire and embodiment 2 obtained by the embodiment of the present invention 1 The TG figures of potassium block materials；
Fig. 4 is the vanadium phosphate obtained by coaxial carbon coating vanadium phosphate potassium nano wire and embodiment 2 obtained by the embodiment of the present invention 1 The FT-IR figures of potassium block materials；
Fig. 5 is the SEM figures of the coaxial carbon coating vanadium phosphate potassium nano wire obtained by the embodiment of the present invention 1；
Fig. 6 is the SEM figures of the vanadium phosphate potassium block obtained by the embodiment of the present invention 2；
Fig. 7 is the distribution diagram of element of the coaxial carbon coating vanadium phosphate potassium nano wire obtained by the embodiment of the present invention 1；
Fig. 8 is the vanadium phosphate potassium block materials distribution diagram of element obtained by the embodiment of the present invention 2；
Fig. 9 is the TEM figures of the coaxial carbon coating vanadium phosphate potassium nano-material obtained by the embodiment of the present invention 1；
Figure 10 is the HRTEM figures of the coaxial carbon coating vanadium phosphate potassium nano-material obtained by the embodiment of the present invention 1；
Figure 11 is the building-up process figure of the coaxial carbon coating vanadium phosphate potassium nano-material of the embodiment of the present invention 1；
Figure 12 is the coaxial carbon coating vanadium phosphate potassium nano wire of the embodiment of the present invention 1 and the vanadium phosphate potassium obtained by embodiment 2 The high rate performance figure of block materials；
Figure 13 is the coaxial carbon coating vanadium phosphate potassium nano wire of the embodiment of the present invention 1 and the vanadium phosphate potassium obtained by embodiment 2 The cyclic voltammetry curve figure of block materials；
Figure 14 is the coaxial carbon coating vanadium phosphate potassium nano wire of the embodiment of the present invention 1 and the vanadium phosphate potassium obtained by embodiment 2 The low range cycle performance figure of block materials；
Figure 15 is the coaxial carbon coating vanadium phosphate potassium nano wire of the embodiment of the present invention 1 and the vanadium phosphate potassium obtained by embodiment 2 The high-multiplying power discharge specific capacity figure of block materials.
Specific embodiment
For a better understanding of the present invention, present disclosure is further elucidated with reference to embodiment, but the present invention Content is not limited solely to the following examples.
Embodiment 1：
The preparation method of coaxial carbon coating pencil vanadium phosphate potassium nano-material, it comprises the steps：
1) by 5.0mmol NH4VO3Powder obtains turbid solution in being dispersed in 20mL deionized waters, add 7.5mmol solids Potassium hydroxide, stirs 10-20 minutes under room temperature, is changed into clear to solution；
2) to step 1) 7.5mmol H are proportionally added in resulting solution3PO4, stir 10-25 minutes to solution and be changed into palm fibre It is red；
3) again to step 2) add in resulting solution 6.0g oxalic acid, strong agitation 6 hours to be changed into yellow green to solution；
4) by step 3) obtained by solution be transferred in culture dish, be then put under 60 DEG C of constant temperature be dried it is 12 little When；
5) by step 4) products therefrom, it is placed directly in 180 DEG C of isoperibol and toasts 24 hours, obtains loose yellowish green Color solid；
6) by step 5) products therefrom grinding, then calcine 4 hours under 300 DEG C of air conditionses；
7) by step 6) products therefrom moves on to again, obtains coaxial carbon coating pencil Vanadium phosphate potassium nano wire.
Embodiment 2：
1) by 5.0mmol NH4VO3Powder obtains turbid solution in being dispersed in 20mL deionized waters, add 7.5mmol solids Potassium hydroxide, stirs 10-20 minutes under room temperature, is changed into clear to solution；
2) to step 1) 7.5mmol H are proportionally added in resulting solution3PO4, stir 10-25 minutes to solution and be changed into palm fibre It is red；
3) again to step 2) 2.0g oxalic acid is added in resulting solution, strong agitation 12 hours at 80 DEG C are changed into deep to solution It is blue；
4) by step 3) obtained by solution be transferred in culture dish, be then put under 60 DEG C of constant temperature be dried it is 12 little When；
5) by step 4) products therefrom, it is placed directly in 180 DEG C of isoperibol and toasts 20 hours, obtains loose yellowish green Color solid；
6) by step 5) products therefrom grinding, then calcine 5 hours under 300 DEG C of air conditionses；
7) by step 6) products therefrom moves on to again, obtains vanadium phosphate potassium block.
With the phosphoric acid that the coaxial carbon coating pencil vanadium phosphate potassium nano wire of 1 invention of this EXPERIMENTAL EXAMPLE and embodiment 2 are obtained As a example by vanadium potassium block, determine through x-ray diffractometer, as shown in figure 1, X-ray diffracting spectrum (XRD) shows, coaxial carbon bag Cover pencil vanadium phosphate potassium nano wire consistent with the peak position of vanadium phosphate potassium block, product has higher crystallinity.As shown in Figure 2, Raman analysis show that coaxial carbon coating pencil vanadium phosphate potassium nano wire and the carbon in vanadium phosphate potassium block are graphited carbon. As shown in figure 3, thermogravimetric analysiss illustrate coaxial carbon coating pencil vanadium phosphate potassium nano wire and the carbon content in vanadium phosphate potassium block point Wei 6.0% and 8.0%.As shown in figure 4, FT-IR test results show coaxial carbon coating pencil vanadium phosphate potassium nano wire and phosphorus Sour vanadium potassium block has identical valence bond structure.As shown in figure 5, field emission scanning electron microscope (FESEM) test shows, sample topography It is homogeneous, nano wire fasciculation favorable dispersibility.Co-axial nano line length be 10-20 microns, a diameter of 250-350 nanometers.Such as Fig. 6 Shown, the pattern of vanadium phosphate potassium block materials is more chaotic, and particle size is larger.Such as Fig. 7, shown in 8, graphitization carbon-coating cladding phosphorus K, V, P, O and C on sour vanadium potassium nano wire and vanadium phosphate potassium block, several Elemental redistributions are very uniform.As shown in figure 9, transmission electricity Mirror (TEM) more clearly from shows the concrete structure of coaxial carbon coating vanadium phosphate potassium nano wire, and which is coated by graphitization carbon-coating Vanadium phosphate potassium nano wire is formed, and wherein coats about 8 nanometers of the thickness of carbon-coating, the nano wire in axle center by monocrystalline constitute it is many It is brilliant.As shown in Figure 10, under high magnification transmission electron microscope (HRTEM) it can be found that obvious lattice fringe, spacing of lattice is about 0.5nm.As shown in Table 1, inductively coupled plasma test result shows, coaxial carbon coating pencil vanadium phosphate potassium nano wire and In vanadium phosphate potassium block, the elemental mole ratios example of K, V and P is sufficiently close to 3：2：3.As shown in figure 11, synthesis mechanism of the invention It is：The method dried using solution, two excessive oxalic acid hydrates are ionized into C2O4 2-, which plays a part of directed agents so that phosphoric acid Vanadium potassium presoma complex ion group is assembled into orderly nanowire alignment, by calcining in pre-burning in later stage air and argon, makes Obtain the brilliant formation nano wire of internal vanadium phosphate potassium complex ion unity, outside C2O4 2-Generation carbonization forms carbon coating layer, finally gives Coaxial carbon coating pencil vanadium phosphate potassium nano-material.
Coaxial carbon coating pencil vanadium phosphate potassium nano-material is used as sodium-ion battery positive electrode active materials, sodium-ion battery Assemble method remaining step it is identical with common preparation method.The assemble method of sodium-ion battery is as follows, using coaxial carbon bag Cover pencil vanadium phosphate potassium nano wire as active material, acetylene black as conductive agent, politef as binding agent, active material Material, acetylene black, the mass ratio of Kynoar are 70:20:10；After they are sufficiently mixed in proportion, a small amount of isopropanol is added, Grinding is uniform, on twin rollers, press about 0.5mm thick electrode slice；The positive plate for pressing was placed in 80 DEG C of oven drying after 24 hours It is standby.With concentration as 1mol/cm3NaClO4Used as electrolyte, it is 1 that its solvent is mass ratio to solution：The ethylene carbonate of 1 mixing And dimethyl carbonate, with metallic sodium piece as negative pole, electrochemical property test is carried out between 1.5-4.0V.
As shown in figure 12, coaxial carbon coating pencil vanadium phosphate potassium nano-material has excellent high rate performance, its Under the electric current density of 100mA/g, initial capacity is 1.8 times of vanadium phosphate potassium block.After the test of continuous multiplying power, its multiplying power Recovery rate is close to 99%.
As shown in figure 13, coaxial carbon coating pencil vanadium phosphate potassium nano wire and vanadium phosphate potassium block materials have close CV Curve, in charge and discharge process only have two pairs of faint redox peaks, these two pair seam be respectively 1.52/3.47,1.73/ 3.64V。
As shown in figure 14, coaxial carbon coating pencil vanadium phosphate potassium nano wire and vanadium phosphate potassium block materials are in permanent direct current charge and discharge When electric, by taking coaxial carbon coating pencil vanadium phosphate potassium nano wire as an example, the constant current charge-discharge test result table carried out under 100mA/g Bright, up to 118.6mAh/g, after 100 circulations, capability retention is up to 99.4% for its first discharge specific capacity.And vanadium phosphate potassium block As a example by body material, the constant current charge-discharge test result carried out under 100mA/g shows, its first discharge specific capacity is 109.1mAh/ G is capability retention after 100 circulations up to 56.2%.By taking coaxial carbon coating pencil vanadium phosphate potassium nano wire as an example, 200mA/g Under the constant current charge-discharge test result that carries out show, 2 times for vanadium phosphate potassium block of its capacity after 600 circulations.With coaxial carbon As a example by cladding pencil vanadium phosphate potassium nano wire, the constant current charge-discharge test result carried out under 500mA/g shows, after 1000 circulations Its capability retention is 93%, and vanadium phosphate potassium block only remains with initial capacity after circulating 300 times under this electric current density 59.6%.
As shown in figure 15, coaxial carbon coating pencil vanadium phosphate potassium nano wire is in higher electric current density 1000,2000mA/g Under, after 2000 circulations, its capability retention is up to 99.0% and 96.0% respectively, and individual pen attenuation rate is respectively 0.0053% and 0.0023%.
2 gained vanadium phosphate potassium block of coaxial carbon coating vanadium phosphate potassium pencil nano wire and embodiment obtained by 1 embodiment 1 of table ICP test results
Embodiment 3：
1) by 10.0mmol NH4VO3Powder obtains turbid solution in being dispersed in 50mL deionized waters, add 15.0mmol solid Body potassium hydroxide, stirs 20-30 minutes under room temperature, is changed into clear to solution；
2) to step 1) 15.0mmol H are proportionally added in resulting solution3PO4, stir 35-55 minutes to solution and be changed into palm fibre It is red；
3) again to step 2) add in resulting solution 4.0g malic acids, strong agitation 12 hours to be changed into yellow green to solution；
4) by step 3) obtained by solution be transferred in culture dish, be then put under 60 DEG C of constant temperature be dried it is 15 little When；
5) by step 4) products therefrom, it is placed directly in 180 DEG C of isoperibol and toasts 24 hours, obtains loose yellowish green Color solid；
6) by step 5) products therefrom grinding, then calcine 6 hours under 300 DEG C of air conditionses；
7) by step 6) products therefrom moves on to again, obtains coaxial carbon coating pencil phosphorus Sour vanadium potassium nano wire.
By taking the coaxial carbon coating pencil vanadium phosphate potassium nano wire obtained by the present embodiment as an example, the constant current carried out under 200mA/g Charge-discharge test result shows that its first discharge specific capacity is reached for capability retention after 100 circulations up to 91.2mAh/g 92.3%.
Embodiment 4：
1) by 5.0mmol NH4VO3Powder obtains turbid solution in being dispersed in 40mL deionized waters, add 7.5mmol solids Potassium hydroxide, stirs 10-20 minutes under room temperature, is changed into clear to solution；
2) to step 1) 7.5mmol H are proportionally added in resulting solution3PO4, stir 15-25 minutes to solution and be changed into palm fibre It is red；
3) again to step 2) add 6.0 ascorbic acid, strong agitation 12 hours to be changed into yellowish green to solution in resulting solution Color；
4) by step 3) obtained by solution be transferred in the glass culture dish of a diameter of 15cm, be then put into 60 DEG C of constant temperature Under the conditions of be dried 10 hours；
5) by step 4) products therefrom, it is placed directly in 180 DEG C of isoperibol and toasts 24 hours, obtains loose yellowish green Color solid；
6) by step 5) products therefrom grinding, then calcine 4 hours under 300 DEG C of air conditionses；
7) by step 6) products therefrom moves on to again, obtains coaxial carbon coating pencil Vanadium phosphate potassium nano wire.
By taking the coaxial carbon coating pencil vanadium phosphate potassium nano wire obtained by the present embodiment as an example, the constant current carried out under 500mA/g Charge-discharge test result shows that up to 72.9mA/g, capability retention reaches its first discharge specific capacity after 1000 circulations 95.0%.
Embodiment 5：
1) by 7.5mmol NH4VO3Powder obtains turbid solution in being dispersed in 40mL deionized waters, add 11.25mmol solid Body potassium hydroxide, stirs 10-25 minutes under room temperature, is changed into clear to solution；
2) to step 1) 11.25mmol H are proportionally added in resulting solution3PO4, stirring 15-35 minutes be changed into solution Brownish red；
3) again to step 2) add in resulting solution 8.0g tartaric acid, strong agitation 10 hours to be changed into yellow green to solution；
4) by step 3) obtained by solution be transferred in culture dish, be then put under 60 DEG C of constant temperature be dried it is 10 little When；
5) by step 4) products therefrom, it is placed directly in 180 DEG C of isoperibol and toasts 24 hours, obtains loose yellowish green Color solid；
6) by step 5) products therefrom grinding, then calcine 2 hours under 300 DEG C of air conditionses；
7) by step 6) products therefrom moves on to again, obtains coaxial carbon coating pencil Vanadium phosphate potassium nano wire.
By taking the coaxial carbon coating pencil vanadium phosphate potassium nano wire obtained by the present embodiment as an example, the constant current carried out under 100mA/g Charge-discharge test result shows that its first discharge specific capacity is reached for capability retention after 100 circulations up to 116.8mAh/g 88.2%.
Embodiment 6：
1) by 5.0mmol NH4VO3Powder obtains turbid solution in being dispersed in 40mL deionized waters, add 7.5mmol solids Potassium hydroxide, stirs 10-25 minutes under room temperature, is changed into clear to solution；
2) to step 1) 7.5mmol H are proportionally added in resulting solution3PO4, stir 15-35 minutes to solution and be changed into palm fibre It is red；
3) again to step 2) 2.0g oxalic acid and 3.0g malic acids is added in resulting solution, strong agitation 10 hours, to solution It is changed into yellow green；
4) by step 3) obtained by solution be transferred in culture dish, be then put under 60 DEG C of constant temperature be dried it is 10 little When；
5) by step 4) products therefrom, it is placed directly in 160 DEG C of isoperibol and toasts 18 hours, obtains loose yellowish green Color solid；
6) by step 5) products therefrom grinding, then calcine 5 hours under 350 DEG C of air conditionses；
7) by step 6) products therefrom moves on to again, obtains coaxial carbon coating pencil Vanadium phosphate potassium nano wire.
By taking the coaxial carbon coating pencil vanadium phosphate potassium nano wire obtained by the present embodiment as an example, the constant current carried out under 100mA/g Charge-discharge test result shows that up to 113.9mAh/g, capability retention reaches its first discharge specific capacity after 100 circulations 96.7%.
Embodiment 7：
1) by 5.0mmol NH4VO3Powder obtains turbid solution in being dispersed in 50mL deionized waters, add 7.5mmol solids Potassium hydroxide, stirs 10-25 minutes under room temperature, is changed into clear to solution；
2) to step 1) 7.5mmol H are proportionally added in resulting solution3PO4, stir 15-35 minutes to solution and be changed into palm fibre It is red；
3) again to step 2) 2.0g oxalic acid, 2.0g malic acids, 2.0g ascorbic acid and 2.0g winestones is added in resulting solution Acid, strong agitation 6 hours, is changed into yellow green to solution；
4) by step 3) obtained by solution be transferred in the glass culture dish of a diameter of 15cm, be then put into 60 DEG C of constant temperature Under the conditions of be dried 10 hours；
5) by step 4) products therefrom, it is placed directly in 180 DEG C of isoperibol and toasts 20 hours, obtains loose yellowish green Color solid；
6) by step 5) products therefrom grinding, then calcine 2 hours under 500 DEG C of air conditionses；
7) by step 6) products therefrom moves on to again, obtains coaxial carbon coating pencil phosphorus Sour vanadium potassium nano wire.
By taking the coaxial carbon coating pencil vanadium phosphate potassium nano wire obtained by the present embodiment as an example, the constant current carried out under 100mA/g Charge-discharge test result shows that up to 115.9mAh/g, capability retention reaches its first discharge specific capacity after 100 circulations 98.4%.

Claims (5)

1. the preparation method of coaxial carbon coating vanadium phosphate potassium nano wire, comprises the steps：
1) by NH4VO3Powder dispersion obtains turbid solution in deionized water, adds potassium hydroxide, stirs to solution and become under room temperature For clear；
2) to step 1) H is proportionally added in resulting solution3PO4, stir to solution and be changed into brownish red；
3) again to step 2) add carbon source, strong agitation to be changed into yellow green to solution in resulting solution；Described carbon source is water-soluble Property organic acid；
4) by step 3) obtained by solution be transferred in culture dish, be then dried；Described baking temperature is 60-90 DEG C, Drying time is 8-12 hours
5) by step 4) products therefrom, direct baking obtains loose greenish yellow solid；Described baking temperature is 120-200 DEG C, constant temperature time 18-24 hours；
6) by step 5) products therefrom grinding, then calcine under air conditionses；Described calcining heat is 200-400 DEG C, is forged The burning time is 2-6 hours；
7) by step 6) products therefrom moves on to again, and described calcining heat is 700-900 DEG C, calcination time For 8-12 hours；Obtain coaxial carbon coating pencil vanadium phosphate potassium nano wire.
2. the preparation method of coaxial carbon coating vanadium phosphate potassium nano wire according to claim 1, it is characterised in that：Described NH4VO3, KOH and H3PO4Mol 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 coating vanadium phosphate potassium nano wire according to claim 1, it is characterised in that：Described Water-soluble organic acid is any one in oxalic acid, citric acid, malic acid, tartaric acid and ascorbic acid or their mixing.
4. the coaxial carbon coating pencil vanadium phosphate potassium nanometer obtained by a kind of preparation method by described in any one of claim 1-3 Line, by graphitization thin carbon layer cladding vanadium phosphate potassium nano wire formed, length be 10-40 microns, a diameter of 250-350 nanometers, its The thickness of middle graphitization thin carbon layer is 6-12 nanometers, and axle center is overlapped by many vanadium phosphate potassium nano wires and formed.
5. the coaxial carbon coating pencil vanadium phosphate potassium nano wire nano material described in claim 4 is lived as sodium-ion battery positive pole The application of property material.
CN201510057889.1A 2015-02-04 2015-02-04 Coaxial carbon-coated bunchy vanadium potassium phosphate nanowire, as well as preparation method and application of nanowire Active CN104638228B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510057889.1A CN104638228B (en) 2015-02-04 2015-02-04 Coaxial carbon-coated bunchy vanadium potassium phosphate nanowire, as well as preparation method and application of nanowire

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510057889.1A CN104638228B (en) 2015-02-04 2015-02-04 Coaxial carbon-coated bunchy vanadium potassium phosphate nanowire, as well as preparation method and application of nanowire

Publications (2)

Publication Number Publication Date
CN104638228A CN104638228A (en) 2015-05-20
CN104638228B true CN104638228B (en) 2017-03-22

Family

ID=53216728

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510057889.1A Active CN104638228B (en) 2015-02-04 2015-02-04 Coaxial carbon-coated bunchy vanadium potassium phosphate nanowire, as well as preparation method and application of nanowire

Country Status (1)

Country Link
CN (1) CN104638228B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105680041B (en) * 2016-01-18 2017-12-29 武汉理工大学 Three-dimensional Na3V2(PO4)3Nanometer line network electrode material and its preparation method and application
CN106684353A (en) * 2016-12-27 2017-05-17 深圳市川马电子股份有限公司 Preparation method for carbon-coated potassium vanadium phosphate and application of carbon-coated potassium vanadium phosphate
CN106887579B (en) * 2017-04-07 2019-09-10 武汉理工大学 Carbon-coated titanium phosphate potassium nano particle and its preparation method and application
CN112201786B (en) * 2020-08-12 2022-03-15 中南大学 Potassium phosphate metal salt organic compound cathode material with vanadium as substrate and preparation method thereof
CN112038605B (en) * 2020-09-04 2021-06-08 洛阳理工学院 Carbon-coated flower-shaped potassium titanium phosphate micro-nano hierarchical structure compound and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102509804A (en) * 2011-11-11 2012-06-20 东莞市迈科科技有限公司 Preparation method for lithium ion battery Li3V2 (Po4)3/C composite material
CN102664263A (en) * 2012-05-24 2012-09-12 陕西科技大学 Preparation method of lithium ion battery cathode material carbon-coated columnar lithium vanadium phosphate
CN103647041A (en) * 2013-12-10 2014-03-19 浙江大学 Carbon-covering ferroferric oxide nanowire as well as preparation method thereof and application in preparation of lithium ion battery

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103545518B (en) * 2013-11-01 2015-12-02 武汉理工大学 Heterogeneous meso-porous nano wire material of phosphoric acid vanadium lithium/carbon and its preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102509804A (en) * 2011-11-11 2012-06-20 东莞市迈科科技有限公司 Preparation method for lithium ion battery Li3V2 (Po4)3/C composite material
CN102664263A (en) * 2012-05-24 2012-09-12 陕西科技大学 Preparation method of lithium ion battery cathode material carbon-coated columnar lithium vanadium phosphate
CN103647041A (en) * 2013-12-10 2014-03-19 浙江大学 Carbon-covering ferroferric oxide nanowire as well as preparation method thereof and application in preparation of lithium ion battery

Also Published As

Publication number Publication date
CN104638228A (en) 2015-05-20

Similar Documents

Publication Publication Date Title
CN104638228B (en) Coaxial carbon-coated bunchy vanadium potassium phosphate nanowire, as well as preparation method and application of nanowire
CN108767260B (en) Carbon-coated FeP hollow nano-electrode material and preparation method and application thereof
CN103779564B (en) High-performance vanadium phosphate sodium symmetric form sodium-ion battery material and its preparation method and application
CN107170967A (en) Pre- intercalated layered barium oxide nano material of bivalent metal ion and its preparation method and application
CN111151279A (en) N, P-doped carbon fiber loaded FeCo/Co2P composite catalyst and preparation method thereof
CN106252616A (en) A kind of nickelous selenide/hollow carbon fiber composite and preparation method thereof
CN110247037B (en) Preparation method and application of sodium vanadium oxygen fluorophosphate/graphene compound
CN108878826B (en) Sodium manganate/graphene composite electrode material and preparation method and application thereof
CN104993159A (en) Dual-function catalyst and preparation thereof and application in metal-air battery
CN102104143A (en) Hydrothermal synthesis method of composite material for high-performance power battery
CN107046126B (en) Preparation method of superfine metal oxide/graphene two-dimensional negative electrode composite material
CN113948681B (en) Biomass-based hard carbon compound composite material and preparation method and application thereof
CN103956483A (en) Preparation method and application of zinc cobaltate/nickel oxide core-shell nanowire array
CN106784651A (en) Connection nano-material and its preparation method and application in carbon-encapsulated iron potassium manganate
CN109148828A (en) One kind includes straw cluster-shaped Co-Fe2O3Electrode of nanocomposite and preparation method thereof
CN107017398A (en) A kind of pyrophosphoric acid vanadium sodium/carbon composite anode material, preparation and its application
CN113948714A (en) In-situ precipitation method self-assembly core-shell structure nanoparticle modified perovskite oxide electrode material and preparation method and application thereof
CN102299327A (en) Preparation method for lithium-aluminum doped carbon cladded lithium iron phosphate anode material
CN111564610B (en) Carbon-coated cuprous phosphide-copper composite particle modified by carbon nanotube and preparation method and application thereof
CN101307461B (en) Method for preparing YSZ-LSM oxygen electrode powder of solid oxidate electrolytic cell
CN106299344A (en) A kind of sodium-ion battery nickel titanate negative material and preparation method thereof
CN102709561A (en) Preparation method of carbon nano-Li2FeSiO4 composite cathode material
CN107946564A (en) Rich sodium manganese base Na4Mn2O5/Na0.7MnO2Composite material and its preparation method and application
CN105206832A (en) Sintering preparation method for zinc anode material
CN110649263A (en) Nickel-ion battery lithium vanadium phosphate positive electrode material, sol-gel preparation method and application

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20220415

Address after: 230022 room 803, building 12, Tianhui zichenge, intersection of Xizang Road and Hangzhou Road, Baohe District, Hefei City, Anhui Province

Patentee after: Anhui Guoxin New Material Co.,Ltd.

Address before: 430070 Hubei Province, Wuhan city Hongshan District Luoshi Road No. 122

Patentee before: WUHAN University OF TECHNOLOGY

TR01 Transfer of patent right