CN107425190A - A kind of vanadium phosphate sodium combination electrode material and its preparation method and application - Google Patents

A kind of vanadium phosphate sodium combination electrode material and its preparation method and application Download PDF

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CN107425190A
CN107425190A CN201710777618.2A CN201710777618A CN107425190A CN 107425190 A CN107425190 A CN 107425190A CN 201710777618 A CN201710777618 A CN 201710777618A CN 107425190 A CN107425190 A CN 107425190A
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combination electrode
electrode material
source
phosphate sodium
vanadium phosphate
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赵海雷
赵丽娜
杜志鸿
李兆麟
张子佳
张旸
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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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
    • H01M4/362—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
    • 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
    • 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
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to a kind of vanadium phosphate sodium combination electrode material and its preparation method and application.The vanadium phosphate sodium combination electrode material is the Na of core shell structure3TixV2‑x(PO4)3/ C combination electrode materials.The preparation method selects organic reducing agent and carbon source, and carbon source thermal decomposition is amorphous carbon in heat treatment process, and it is Na to form core3TixV2‑x(PO4)3Particle, shell are the core shell structures of amorphous carbon；This unique nano particle core shell structure can not only shorten the transmission path of sodium ion, and improve material ions electrical conductivity but also can improve electronic conductivity by in-stiu coating carbon material, to improving Na3TixV2‑x(PO4)3The chemical property of/C combination electrode materials has huge facilitation.The combination electrode material of the present invention is widely used in energy storage material and secondary sodium-ion battery technical field.Belong to electrode material field.

Description

A kind of vanadium phosphate sodium combination electrode material and its preparation method and application
Technical field
The invention belongs to electrode material field, and in particular to a kind of vanadium phosphate sodium combination electrode material and preparation method thereof and Using.
Background technology
With the successful commercialization of lithium ion battery, the demand of lithium greatly increases, and the reserves of lithium are limited, and is distributed not , this is stored up for the long-life of cheap, the safe intelligent grid of demand for development and the extensive energy storage of regenerative resource To be a serious bottleneck problem for energy battery.Therefore, it is new to need the excellent energy-storage battery of development comprehensive effectiveness of future generation badly System.Compared with lithium ion battery, sodium-ion battery has sodium aboundresources, the cheap and advantage such as widely distributed.Therefore, As a kind of potential substitute of lithium ion battery, sodium-ion battery has obtained the extensive concern of people in the recent period.
Electrode material is the key of sodium-ion battery technology.Because sodium ion has heavier atom matter compared with lithium ion Amount, bigger ionic radius and lower standard electrode potential, this make it that Na+ is de-/embedding more slow in electrode material, entered And influence circulation and the high rate performance of battery.Therefore, in order to develop the sodium-ion battery of excellent performance, exploitation has high-energy close The electrode material of degree is most important.
As a kind of important sodium ion battery electrode material, Na3V2(PO4)3It is Na3M2(PO4)3(M=Al3+, Sc3+, Ti3+And Fe3+) a member important in compounds of group, belong to NASICON type polyanionic compounds, and polyanionic sodium from The Typical Representative of sub- battery electrode material.Na3V2(PO4)3With larger three-dimensional channel structure, it is available for sodium ion to carry out quick It is de-/embedding.Na3V2(PO4)3Belong to hexaplanar, space group R-3c, cell parameter is Na3V2(PO4)3Each structure cell includes 6 Na3V2(PO4)3Chemical combination formula weight, its crystal structure are by each VO6Octahedron passes through altogether With oxygen atom and 3 PO4Tetrahedron is connected to form, wherein Na+There are two to occupy site：Na1 and Na2.Wherein, Na1 positions Na+ Occupation rate be 1, and Na2 positions Na+ occupation rate is 2/3, and 2 Na+ of Na2 positions are de- first in charge and discharge process Go out or embedded, changes in crystal structure Na3V2(PO4)3/NaV2(PO4)3, corresponding V4+/V3+Oxidation-reduction pair, charge and discharge level Platform is 3.4V.In charge and discharge process, Na3V2(PO4)3Material can keep good crystal structural stability, Volume Changes small and have There is good heat endurance, beneficial to promotion Na3V2(PO4)3The cyclical stability and job security of electrode material.
As sodium-ion battery positive material, Na3V2(PO4)3Theoretical specific capacity (correspond to 2 Na of per molecule+It is de-/embedding) It is 117.6mAhg-1, slightly below transition metal oxide sodium-ion battery positive material.Also, Na3V2(PO4)3Electronics electricity Difference is led, its theoretical specific capacity is extremely difficult in charge and discharge process, and causes its high rate performance undesirable.These have a strong impact on Na3V2(PO4)3The energy density of electrode material, and then it is adversely affected in terms of extensive stored energy application.Therefore, How Na is improved3V2(PO4)3The electronic conductivity of material, improve its specific discharge capacity, high rate during charging-discharging is sodium ion The technical problem of the urgent need to resolve of battery popularization and application.
The content of the invention
To solve the above problems, the present invention proposes a kind of vanadium phosphate sodium combination electrode material and its preparation method and application. The vanadium phosphate sodium combination electrode material has the characteristics that height ratio capacity high rate capability.
The present invention is achieved by the following technical solutions：
A kind of vanadium phosphate sodium combination electrode material, the vanadium phosphate sodium combination electrode material are the Na of core shell structure3TixV2-x (PO4)3/ C combination electrode materials；
The core shell structure core is Na3TixV2-x(PO4)3, shell is amorphous carbon layer, and x is atomic percent.
Further, the Na3TixV2-x(PO4)3X span is 0≤x in/C combination electrode materials<1.
Further, the Na3TixV2-x(PO4)3X span is 0 in/C combination electrode materials<x<1.
Further, the Na3TixV2-x(PO4)3X span is 0≤x≤0.15 in/C combination electrode materials.
Further, the Na3TixV2-x(PO4)3X span is 0≤x≤0.10 in/C combination electrode materials.
Further, the Na3TixV2-x(PO4)3X span is 0≤x≤0.05 in/C combination electrode materials.
Further, the Na3TixV2-x(PO4)3X span is 0.05≤x in/C combination electrode materials<1.
Further, the Na3TixV2-x(PO4)3X span is 0.10≤x in/C combination electrode materials<1.
Further, the Na3TixV2-x(PO4)3X span is 0.15≤x in/C combination electrode materials<1.
Further, the Na3TixV2-x(PO4)3X value is 0.05,0.10 or 0.15 in/C combination electrode materials.
Further, the Na3TixV2-x(PO4)3/ C combination electrode materials are in Nanoparticulate.
Further, the Na3TixV2-x(PO4)3/ C combination electrode materials are water chestnut square structure, space group R-3c.
Further, the thickness of the amorphous carbon layer is 2-10nm.
Further, the Na3TixV2-x(PO4)3In/C combination electrode materials, titanium is high valence ion Ti4+；
The high valence ion Ti4+With electro-chemical activity, along with Na in charge and discharge process+De-/embedding generation Ti3+/Ti4+ Oxidation/reduction reaction, make Na3V2(PO4)3(0<x<When 1) the intrinsic V of combination electrode material3+/V4+Electrochemical reaction increase, and then Improve its specific discharge capacity；
The high valence ion Ti4+Compare V3+With lighter molecular weight so that Na3TixV2-x(PO4)3(0<x<When 1) molecule Amount is compared with Na3V2(PO4)3Molecular weight it is low, as de-/embedding Na+When number is identical, Na3TixV2-x(PO4)3(0<x<When 1) combination electrode material Material has higher theoretical specific capacity；
The high valence ion Ti4+Compare V3+With smaller ionic radius, appropriate Ti4+Substitute V3+After can cause structure cell body Product is shunk, and improves Na3TixV2-x(PO4)3/C(0<x<When 1) structural stability of combination electrode material, and then be advantageous to improve electricity The cyclical stability of pole material；
The high valence ion Ti4+With V3+Electricity price it is different, high valence ion Ti4+Belong to aliovalent doping, Ti in system4+Draw Enter to cause to produce V in system2+/V3+Electricity price is mixed, so as to improve the electronic conductivity of material, strengthens electrode reaction and moves Mechanical process, improve circulation and the high rate performance of material.
A kind of preparation method of vanadium phosphate sodium combination electrode material, the preparation method comprise the following steps：
(1) hydro-thermal auxiliary-carbothermic method prepares precursor solution, including：It will seal and include vanadium source, phosphorus source, sodium The water heating kettle of the mixed solution in source, organic reducing agent and carbon source is placed in baking oven, and the mixed solution is in constant temperature T1, constant temperature time t1Under the conditions of react, obtain precursor solution；
The water heating kettle is directly placed into the baking oven for having set temperature, is more beneficial for product homoepitaxial；
The organic reducing agent and the carbon source are coated on Na in water-heat process situ3TixV2-x(PO4)3Presoma Grain surface, on the one hand, can both prevent Na3TixV2-x(PO4)3Granular precursor is grown up, and can effectively be suppressed particle again and sintered During reunion；On the other hand, thermal decomposition is amorphous carbon in heat treatment process, and it is Na to form core3TixV2-x (PO4)3Particle, shell are the core shell structures of amorphous carbon；This unique nano particle core shell structure can both shorten sodium ion Transmission path, raising material ions electrical conductivity can improve electronic conductivity by in-stiu coating carbon material again, to improving Na3TixV2-x(PO4)3The chemical property of/C combination electrode materials has huge facilitation；
The organic reducing agent is used to reduce high price vanadium source；
(2) preparation of presoma powder, including：The precursor solution obtained in step (1) is placed in into constant temperature in baking oven to dry It is dry, thermostat temperature T2, constant temperature time t2, obtain presoma powder；
(3) presoma powder described in high-temperature calcination, including：Tube furnace is placed in after the presoma powder is fully ground In, high-temperature calcination, calcining heat T are carried out to the presoma powder under inert gas atmosphere3, calcination time t3, high-temperature process Obtain the vanadium phosphate sodium combination electrode material afterwards；
The vanadium phosphate sodium combination electrode material is the Na of core shell structure3TixV2-x(PO4)3/ C combination electrode materials；It is described Core shell structure core is Na3TixV2-x(PO4)3, shell is amorphous carbon layer, and x is atomic percent.
Further, before precursor solution is placed in baking oven described in step (2), by the precursor solution with ultrasound point Dissipate, mechanical agitation or magnetic agitation mode are disperseed to the precursor solution；The jitter time is 60-120min.
Further, the water heating kettle capacity is 50-200ml.
Further, the water heating kettle carries liner；The inner lining material is polytetrafluoroethylene (PTFE), polyparaphenylene phenol or tetrafluoro Ethene-perfluorinated alkoxy vinyl ether copolymer；The liner need to have high temperature resistant, acid and alkali-resistance property.
Further, step (1) the constant temperature T1For 120~200 DEG C；The constant temperature time t1For 12~48h.
Further, because in step (1), reaction temperature is higher, Na3TixV2-x(PO4)3(0≤x<1) presoma nanometer Crystalline substance nucleation and the effect of growth are better, but constant temperature time is long not only to reduce preparation efficiency, can also increase prepare it is compound The cost of material；Therefore, step (1) the constant temperature T1For 200 DEG C；The constant temperature time t1For 40h.
Further, step (2) the thermostat temperature T2For 90~150 DEG C；The constant temperature time t2For 6~10h.
Further, step (2) the thermostat temperature T2For 125 DEG C；The constant temperature time t2For 8h；Now, the baking oven Efficiency and cost it is minimum.
Further, step (3) the calcining heat T3For 400~800 DEG C；The calcination time t3For 6~10h.
Further, because the relatively low heat treatment temperature of step (3) is beneficial to reduce particle size and saving prepares composite wood The cost of material；Soaking time is more short more beneficial to improving efficiency with cost-effective, but soaking time is too short can be unfavorable for phase pure material Preparation；Therefore, step (3) the calcining heat T3For 650 DEG C；The calcination time t3For 6h.
Further, the mixed solution also includes titanium source.
Further, vanadium source quality is m1, phosphorus source quality is m2, the sodium source quality is m3, the titanium source matter Measure as m4, the organic reducing agent quality is m5, the volume of the carbon source is V0。
Further, the quality in the vanadium source is 0<m1≤2g；The quality of phosphorus source is 0<m2≤2g；The sodium source Quality is 0<m3≤2g；The quality of the titanium source is 0≤m4≤4g；The quality of the organic reducing agent is 0<m5≤ 2g and institute The volume for stating carbon source is 0<V0≤10ml。
Further, the vanadium source is V2O5。
Further, phosphorus source NH4H2PO4。
Further, the sodium source is Na2CO3。
Further, the titanium source is butyl titanate (C16H36O4Ti)。
Further, the organic reducing agent is ascorbic acid.
Further, the carbon source is PEG-4000 (PEG-400) and ascorbic acid.
Further, the vanadium source is V2O5, phosphorus source NH4H2PO4, the sodium source be Na2CO3, it is described it is organic also Former agent is ascorbic acid, the titanium source is butyl titanate C16H36O4Ti, the carbon source be PEG-4000 (PEG-400) and Ascorbic acid.
Further, the V2O5Quality be 0<m1≤2g；The NH4H2PO4Quality be 0<m2≤2g；It is described Na2CO3Quality be 0<m3≤2g；The quality of the butyl titanate is 0≤m4≤4g；The quality of the ascorbic acid is 0<m5 The volume of≤2g and the PEG-4000 is 0<V0≤10ml。
Further, pre-dispersed processing need to be first carried out during the butyl titanate use, the butyl titanate is uniform It is dispersed in alcohol；The pre-dispersed processing mode is as follows：
First, the ratio for measuring the butyl titanate and the alcohol is butyl titanate：Alcohol=5-10mmol： 100-200ml；Then, the butyl titanate is dispersed in the alcohol, obtains finely dispersed butyl titanate Alcoholic solution.
Further, the preparation method of mixed solution is as follows described in step (1)：
Under lasting stirring condition, first, the vanadium source, phosphorus source, the sodium source are dissolved in deionized water, then The titanium source is added, persistently stirs 30-50min, until the vanadium source, phosphorus source, the sodium source and the titanium source are uniformly divided Dissipate in the deionized water；Finally, toward the organic reducing agent and the carbon source is added in solution, continue to stir 60- 120min, obtain the mixed solution.
Further, the deionized water volume V is 60-100ml.
A kind of vanadium phosphate sodium combination electrode material is used as energy storage material or prepares secondary sodium-ion battery.
Further, a kind of vanadium phosphate sodium combination electrode material is applied to storage as the secondary sodium-ion battery of electrode In energy equipment.
The present invention has the advantages that：
(1) a kind of Na of the invention3TixV2-x(PO4)3In/C combination electrode materials, high valence ion Ti4+Lived with electrochemistry Property, along with Na in charge and discharge process+De-/embedding generation Ti3+/Ti4+Oxidation/reduction reaction, make Na3V2(PO4)3(0<x<When 1) it is multiple The intrinsic V of composite electrode material3+/V4+Electrochemical reaction increase, and then improve its specific discharge capacity；
(2) a kind of Na of the invention3TixV2-x(PO4)3In/C combination electrode materials, high valence ion Ti4+Compare V3+With lighter Molecular weight so that Na3TixV2-x(PO4)3(0<x<When 1) molecular weight compared with Na3V2(PO4)3Molecular weight it is low, as de-/embedding Na+ When number is identical, Na3TixV2-x(PO4)3(0<x<When 1) combination electrode material has higher theoretical specific capacity；
(3) a kind of Na of the invention3TixV2-x(PO4)3In/C combination electrode materials, high valence ion Ti4+Compare V3+With smaller Ionic radius, appropriate Ti4+Substitute V3+After unit cell volume can be caused to shrink, improve Na3V2(PO4)3(0<x<When 1) compound electric The structural stability of pole material, and then be advantageous to improve the cyclical stability of electrode material；
(4) a kind of Na of the invention3TixV2-x(PO4)3In/C combination electrode materials, high valence ion Ti4+With V3+Electricity price not Together, high valence ion Ti4+Belong to aliovalent doping, Ti in system4+Be introduced into and will certainly cause to produce V in system2+/V3+Mix electricity price, So as to improve the electronic conductivity of material, strengthen electrode reaction dynamic process, improve circulation and the high rate performance of material.
(5) a kind of Na of the invention3TixV2-x(PO4)3/ C combination electrode materials are core shell structure, this unique nanometer Particle core shell structure can not only shorten the transmission path of sodium ion, and improve material ions electrical conductivity but also can be by in-stiu coating carbon material To improve electronic conductivity, to improving Na3TixV2-x(PO4)3/C(0≤x<1) chemical property of combination electrode material has huge Facilitation.
(6) titanium doped modified Na of the invention3TixV2-x(PO4)3/C(0<x<1) combination electrode material is as secondary Also there is new electricity in use, in addition to intrinsic 3.4V voltage platforms in 2.3V and 3.9V or so in sodium-ion battery positive material Chemically react platform, shows as being more than its theoretical capacity 117.6mAhg-1Specific discharge capacity.
(7) a kind of Na of the invention3TixV2-x(PO4)3In the preparation method of/C combination electrode materials, aided in using hydro-thermal Method, from ascorbic acid as reducing agent and carbon source, PEG-4000 (PEG-400) is used as carbon source, in water-heat process Middle generation high polymer in-stiu coating is in Na3TixV2-x(PO4)3(0≤x<1) granular precursor surface, on the one hand, can both prevent Na3TixV2-x(PO4)3(0≤x<1) granular precursor is grown up, and can effectively suppress reunion of the particle in sintering process again； On the other hand, thermal decomposition is amorphous carbon in sintering process, and it is Na to form core3TixV2-x(PO4)3(0≤x<1) particle, Shell is the core shell structure of amorphous carbon.
Brief description of the drawings
Fig. 1 is the XRD diffracting spectrums of vanadium phosphate sodium combination electrode material prepared by 1-4 of the embodiment of the present invention.
Fig. 2 a are the electron microscope picture of vanadium phosphate sodium combination electrode material prepared by the embodiment of the present invention 1.
Fig. 2 b are the electron microscope picture of vanadium phosphate sodium combination electrode material prepared by the embodiment of the present invention 2.
Fig. 2 c are the electron microscope picture of vanadium phosphate sodium combination electrode material prepared by the embodiment of the present invention 3.
Fig. 2 d are the electron microscope picture of vanadium phosphate sodium combination electrode material prepared by the embodiment of the present invention 4.
Fig. 3 a are the Flied emission transmission electron microscope of vanadium phosphate sodium combination electrode material prepared by the embodiment of the present invention 3 Figure.
Fig. 3 b are the partial enlarged drawing of the part that dotted line is drawn in Fig. 3 a.
Fig. 4 is the first charge-discharge curve map of vanadium phosphate sodium combination electrode material prepared by 1-4 of the embodiment of the present invention；
Fig. 5 is the high rate performance figure of vanadium phosphate sodium combination electrode material prepared by 1-4 of the embodiment of the present invention.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples The present invention is explained in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, and It is not used in the restriction present invention.
On the contrary, the present invention covers any replacement done in the spirit and scope of the present invention being defined by the claims, repaiied Change, equivalent method and scheme.Further, in order that the public has a better understanding to the present invention, below to the thin of the present invention It is detailed to describe some specific detail sections in section description.Part without these details for a person skilled in the art Description can also understand the present invention completely.
Embodiment 1
A kind of preparation method for vanadium phosphate sodium combination electrode material that the present embodiment is related to, the preparation method are as follows：
(1) selection of raw material：It is V that the present embodiment, which selects the vanadium source,2O5, phosphorus source NH4H2PO4, the sodium source be Na2CO3, the organic reducing agent be ascorbic acid, the titanium source be butyl titanate C16H36O4Ti, the carbon source are poly- second two Alcohol -400 (PEG-400) and ascorbic acid；
(2) raw material measures：The V2O5Quality m1For 0.728g；The NH4H2PO4Quality m2For 1.380g；Institute State Na2CO3Quality m3For 0.636g；The quality m of the butyl titanate4For 0g；The quality m of the ascorbic acid5For 1.507g；The volume V of the PEG-4000 (PEG-400)0It is 70ml for 6ml and deionized water volume V.
(3) preparation of mixed solution：Under lasting stirring condition, first, by the vanadium source, phosphorus source, the sodium source It is dissolved in deionized water, persistently stirs 30min；Finally, toward the organic reducing agent and carbon source is added in solution, continue to stir 60min, obtain the mixed solution.
(4) hydro-thermal auxiliary-carbothermic method prepares precursor solution：It will seal and include vanadium source, phosphorus source, sodium source, have The water heating kettle of machine reducing agent and the mixed solution of carbon source is placed in baking oven, and the mixed solution is in 200 DEG C of constant temperature, constant temperature time Reacted under the conditions of 40h, obtain precursor solution；
(5) acquisition of presoma powder：The precursor solution obtained in step (4) is subjected to ultrasonic disperse 60min first Afterwards, constant temperature drying in baking oven is placed in, 125 DEG C of thermostat temperature, constant temperature time 8h, obtains presoma powder；Now, the baking oven Efficiency and cost are minimum.
(6) presoma powder described in high-temperature calcination, including：Tube furnace is placed in after the presoma powder is fully ground In, high-temperature calcination, 650 DEG C, calcination time 6h of calcining heat, high temperature are carried out to the presoma powder under inert gas atmosphere The vanadium phosphate sodium combination electrode material is obtained after calcining.
The relatively low heat treatment temperature of the step (6) be beneficial to reduce particle size and saving prepare combination electrode material into This；Soaking time is more short more is beneficial to improve efficiency with cost-effective, but the too short preparation that can be unfavorable for phase pure material of soaking time.
The vanadium phosphate sodium combination electrode material obtained by a kind of above-mentioned preparation method of vanadium phosphate sodium combination electrode material Expect for Na3V2(PO4)3Combination electrode material.
Fig. 1 has Na3V2(PO4)3The XRD diffracting spectrums of combination electrode material, Fig. 2 a are Na3V2(PO4)3Combination electrode material Electron microscope picture.As seen from the figure, Na3V2(PO4)3Combination electrode material space group is R-3C.
With 70wt%Na3V2(PO4)3/ C combination electrode materials, 15wt% acetylene black, 15wt% PVDF, are made slurry Material, is coated uniformly on aluminium foil, circular electrode pole piece is stamped into after vacuum drying, using metallic sodium as to electrode, 1mol/L NaClO4/ DMC+EC (volume ratios 1:1)+5%FEC is electrolyte, and Whatman DF/D are barrier film, are assembled into button cell. Detect Na3V2(PO4)3The first charge-discharge situation of/C combination electrode materials, as a result as shown in Figure 4.
Embodiment 2
A kind of preparation method for vanadium phosphate sodium combination electrode material that the present embodiment is related to, the preparation method are as follows：
(1) selection of raw material：It is V that the present embodiment, which selects the vanadium source,2O5, phosphorus source NH4H2PO4, the sodium source be Na2CO3, the organic reducing agent be ascorbic acid, the titanium source be butyl titanate C16H36O4Ti, the carbon source are poly- second two Alcohol -400 (PEG-400) and ascorbic acid；
(2) raw material measures：The V2O5Quality m1For 0.709g；The NH4H2PO4Quality m2For 1.380g；Institute State Na2CO3Quality m3For 0.636g；The quality m of the butyl titanate4For 0.0680g；The quality m of the ascorbic acid5For 1.507g；The volume V of the PEG-4000 (PEG-400)0For 6ml and and deionized water volume V be 70ml.
(3) C is prepared16H36O4Ti alcoholic solutions：First, 0.680g (2nmol) butyl titanates and 40ml institutes are measured State alcohol (5nmol：100ml)；Then, the butyl titanate is dispersed in the alcohol, obtained finely dispersed Butyl titanate alcoholic solution；4ml (butyl titanate quality m therein are measured from the butyl titanate alcoholic solution4For 0.0680g) it is used to prepare mixed solution.
(4) preparation of mixed solution：Under lasting stirring condition, first, by the vanadium source, phosphorus source, the sodium source It is dissolved in deionized water, is then rapidly added butyl titanate alcoholic solution described in 4ml, persistently stirs 30min；Finally, toward molten The organic reducing agent and carbon source are added in liquid, continues to stir 60min, obtains the mixed solution.
(5) hydro-thermal auxiliary-carbothermic method prepares precursor solution：It will seal and include vanadium source, phosphorus source, sodium source, have The water heating kettle of machine reducing agent and the mixed solution of carbon source is placed in baking oven, and the mixed solution is in 200 DEG C of constant temperature, constant temperature time Reacted under the conditions of 40h, obtain precursor solution；The water heating kettle capacity is 100ml and carries polytetrafluoroethyllining lining.
(6) acquisition of presoma powder：The precursor solution obtained in step (5) is subjected to ultrasonic disperse 60min first Afterwards, constant temperature drying in baking oven is placed in, 125 DEG C of thermostat temperature, constant temperature time 8h, obtains presoma powder；Now, the baking oven Efficiency and cost are minimum.
(7) presoma powder described in high-temperature calcination, including：Tube furnace is placed in after the presoma powder is fully ground In, high-temperature calcination, 650 DEG C, calcination time 6h of calcining heat, high temperature are carried out to the presoma powder under inert gas atmosphere The vanadium phosphate sodium combination electrode material is obtained after calcining；
The vanadium phosphate sodium combination electrode material is the Na of core shell structure3TixV2-x(PO4)3/ C combination electrode materials；It is described Core shell structure core is Na3TixV2-x(PO4)3, shell is amorphous carbon layer, and x is atomic percent.
The relatively low heat treatment temperature of the step (7) be beneficial to reduce particle size and saving prepare combination electrode material into This；Soaking time is more short more is beneficial to improve efficiency with cost-effective, but the too short preparation that can be unfavorable for phase pure material of soaking time.
The vanadium phosphate sodium combination electrode material obtained by a kind of above-mentioned preparation method of vanadium phosphate sodium combination electrode material Expect for Na3Ti0.05V1.95(PO4)3/ C combination electrode materials.
Fig. 1 has Na3Ti0.05V1.95(PO4)3The XRD diffracting spectrums of/C combination electrode materials.Fig. 2 b are Na3Ti0.05V1.95 (PO4)3The electron microscope picture of/C combination electrode materials, as seen from the figure, Na3Ti0.05V1.95(PO4)3/ C combination electrode material grains Footpath is 20-500nm.
With 70wt%Na3Ti0.05V1.95(PO4)3/ C combination electrode materials, 15wt% acetylene black, 15wt% PVDF, system Into slurry, it is coated uniformly on aluminium foil, circular electrode pole piece is stamped into after vacuum drying, using metallic sodium as to electrode, 1mol/L NaClO4/ DMC+EC (volume ratios 1:1)+5%FEC is electrolyte, and Whatman DF/D are barrier film, are assembled into button cell. Detect Na3Ti0.05V1.95(PO4)3The first charge-discharge situation of/C combination electrode materials, as a result as shown in Figure 4.
Embodiment 3
A kind of preparation method of vanadium phosphate sodium combination electrode material involved by the present embodiment is substantially the same manner as Example 2, Unlike only：
8ml (butyl titanate quality m therein are measured from the butyl titanate alcoholic solution4For 0.136g) it is used for Prepare mixed solution.
The V2O5Quality m1For 0.691g.
By a kind of Na of the present embodiment3TixV2-x(PO4)3The Na that the preparation method of/C combination electrode materials obtains3TixV2-x (PO4)3/ C combination electrode materials are Na3Ti0.10V1.90(PO4)3/ C combination electrode materials.
Fig. 1 has Na3Ti0.10V1.90(PO4)3The XRD diffracting spectrums of/C combination electrode materials.Fig. 2 c are Na3Ti0.10V1.90 (PO4)3The electron microscope picture of/C combination electrode materials.Fig. 3 a are Na3Ti0.10V1.90(PO4)3The field hair of/C combination electrode materials Penetrate transmission electron microscope figure.Fig. 3 b are the partial enlarged drawing of the part that dotted line is drawn in Fig. 3 a.As seen from the figure, it is made Na3Ti0.10V1.90(PO4)3/ C combination electrode materials are core shell structure, core Na3Ti0.10V1.90(PO4)3, shell is amorphous Carbon-coating, the carbon layers having thicknesses are 1-5nm, average thickness 3nm.
With 70wt%Na3Ti0.10V1.90(PO4)3Combination electrode material, 15wt% acetylene black, 15wt% PVDF, are made Slurry, it is coated uniformly on aluminium foil, circular electrode pole piece is stamped into after vacuum drying, using metallic sodium as to electrode, 1mol/L NaClO4/ DMC+EC (volume ratios 1:1)+5%FEC is electrolyte, and Whatman DF/D are barrier film, are assembled into button cell. Detect Na3Ti0.10V1.90(PO4)3The first charge-discharge situation of combination electrode material, as a result as shown in Figure 4.
Fig. 4 is 0.1C (1C=117.6mAhg-1) first charge-discharge capacitance-voltage curves figure under current density, as schemed institute Show, Na3Ti0.10V1.90(PO4)3/ C combination electrode materials first discharge specific capacity is 124.6mAhg-1, exceeded its theoretical ratio Capacity.
Embodiment 4
A kind of preparation method of vanadium phosphate sodium combination electrode material involved by the present embodiment is substantially the same manner as Example 2, Unlike only：
12ml (butyl titanate quality m therein are measured from the butyl titanate alcoholic solution4For 0.204g) use In preparing mixed solution.
The V2O5Quality m1For 0.673g.
The vanadium phosphate sodium obtained by a kind of preparation method of vanadium phosphate sodium combination electrode material of the present embodiment is compound Electrode material is Na3Ti0.15V1.85(PO4)3/ C combination electrode materials.
Fig. 1 has Na3Ti0.15V1.85(PO4)3The XRD diffracting spectrums of/C combination electrode materials.Fig. 2 d are Na3Ti0.15V1.85 (PO4)3The electron microscope picture of/C combination electrode materials
With 70wt%Na3Ti0.15V1.85(PO4)3/ C combination electrode materials, 15wt% acetylene black, 15wt% PVDF, system Into slurry, it is coated uniformly on aluminium foil, circular electrode pole piece is stamped into after vacuum drying, using metallic sodium as to electrode, 1mol/L NaClO4/ DMC+EC (volume ratios 1:1)+5%FEC is electrolyte, and Whatman DF/D are barrier film, are assembled into button cell. Detect Na3Ti0.15V1.85(PO4)3The first charge-discharge situation of/C combination electrode materials, as a result as shown in Figure 4.
Fig. 5 is Na3Ti0.15V1.85(PO4)3The high rate performance of/C combination electrode materials, as seen from the figure, high price Ti4+Ion is mixed It is miscellaneous to be remarkably improved Na3V2(PO4)3The high rate performance of combination electrode material.When current density increases to 100C, its ratio that discharges Capacity still can reach ＞ 100mAhg-1。

Claims (10)

1. a kind of vanadium phosphate sodium combination electrode material, it is characterised in that the vanadium phosphate sodium combination electrode material is core shell structure Na3TixV2-x(PO4)3/ C combination electrode materials；
The core shell structure core is Na3TixV2-x(PO4)3, shell is amorphous carbon layer, and x is atomic percent.
A kind of 2. vanadium phosphate sodium combination electrode material according to claim 1, it is characterised in that the Na3TixV2-x (PO4)3X span is 0 in/C combination electrode materials<x<1.
3. a kind of preparation method of vanadium phosphate sodium combination electrode material, it is characterised in that the preparation method comprises the following steps：
(1) hydro-thermal auxiliary-carbothermic method prepares precursor solution, including：It will seal and include vanadium source, phosphorus source, sodium source, have The water heating kettle of machine reducing agent and the mixed solution of carbon source is placed in baking oven, and the mixed solution is in constant temperature T1, constant temperature time t1Condition Lower reaction, obtains precursor solution；
(2) preparation of presoma powder, including：The precursor solution obtained in step (1) is placed in constant temperature drying in baking oven, it is permanent Temperature T2, constant temperature time t2, obtain presoma powder；
(3) presoma powder described in high-temperature calcination, including：It is placed in after the presoma powder is fully ground in tube furnace, High-temperature calcination, calcining heat T are carried out to the presoma powder under inert gas atmosphere3, calcination time t3, after high-temperature calcination i.e. Obtain the vanadium phosphate sodium combination electrode material；
The vanadium phosphate sodium combination electrode material is the Na of core shell structure3TixV2-x(PO4)3/ C combination electrode materials；The nucleocapsid Structural core is Na3TixV2-x(PO4)3, shell is amorphous carbon layer, and x is atomic percent.
A kind of 4. preparation method of vanadium phosphate sodium combination electrode material according to claim 3, it is characterised in that step (1) the constant temperature T1For 120~200 DEG C；The constant temperature time t1For 12~48h.
A kind of 5. preparation method of vanadium phosphate sodium combination electrode material according to claim 3, it is characterised in that step (2) the thermostat temperature T2For 90~150 DEG C；The constant temperature time t2For 6~10h.
A kind of 6. preparation method of vanadium phosphate sodium combination electrode material according to claim 3, it is characterised in that step (3) the calcining heat T3For 400~800 DEG C；The calcination time t3For 6~10h.
7. the preparation method of a kind of vanadium phosphate sodium combination electrode material according to claim 3, it is characterised in that described mixed Closing solution also includes titanium source.
A kind of 8. preparation method of vanadium phosphate sodium combination electrode material according to claim 7, it is characterised in that the vanadium Source quality is m1, phosphorus source quality is m2, the sodium source quality is m3, the titanium source is m4, the organic reducing agent quality is m5, the volume of the carbon source is V0；
The quality in the vanadium source is 0<m1≤2g；The quality of phosphorus source is 0<m2≤2g；The quality of the sodium source is 0<m3≤ 2g；The quality of the titanium source is 0≤m4≤4g；The quality of the organic reducing agent is 0<m5≤ 2g and the carbon source volume For 0<V0≤10ml。
A kind of 9. preparation method of vanadium phosphate sodium combination electrode material according to claim 7, it is characterised in that the vanadium Source is V2O5, phosphorus source NH4H2PO4, the sodium source be Na2CO3, the organic reducing agent be ascorbic acid, the titanium source For butyl titanate C16H36O4Ti, the carbon source are PEG-4000 and ascorbic acid.
10. a kind of vanadium phosphate sodium combination electrode material according to any one of claim 1 or 2 is used as energy storage material or preparation Secondary sodium-ion battery.
CN201710777618.2A 2017-09-01 2017-09-01 A kind of vanadium phosphate sodium combination electrode material and its preparation method and application Pending CN107425190A (en)

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CN113929069A (en) * 2021-10-08 2022-01-14 中国科学院过程工程研究所 Manganese-rich phosphate cathode material and preparation method and application thereof
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