CN107611390A - A kind of metal-doped vanadium phosphate sodium combination electrode material and its preparation method and application - Google Patents

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

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CN107611390A
CN107611390A CN201710777612.5A CN201710777612A CN107611390A CN 107611390 A CN107611390 A CN 107611390A CN 201710777612 A CN201710777612 A CN 201710777612A CN 107611390 A CN107611390 A CN 107611390A
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combination electrode
electrode material
metal
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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Abstract

The present invention relates to a kind of metal-doped vanadium phosphate sodium combination electrode material and its preparation method and application.The metal-doped vanadium phosphate sodium combination electrode material is the Na in micro-nano composite particles shape3V2‑xMx(PO4)3/ C combination electrode materials.The addition of organic matter carbon source can be coated on Na in water-heat process situ in the preparation method3V2‑xMx(PO4)3/ C granular precursors surface, it can be used to prevent Na3V2‑xMx(PO4)3/ C granular precursors are grown up and reunited；It is amorphous carbon that and can thermally decomposes in heat treatment process, and it is Na to form core3V2‑xMx(PO4)3/ C particle, shell are the core shell structures of amorphous carbon.A kind of metal-doped vanadium phosphate sodium combination electrode material of the present invention has the advantages that good electric conductivity, excellent cyclical stability and high rate performance.Belong to electrode material field.

Description

A kind of metal-doped 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 metal-doped vanadium phosphate sodium combination electrode material and its system Preparation Method and application
Background technology
Sodium-ion battery has sodium aboundresources, the cheap and advantage such as widely distributed.The exploitation of sodium-ion battery and The problem of using lithium resource critical shortage can be alleviated to a certain extent, there is certain market competitiveness.Therefore, recent sodium from The research and development of sub- battery electrode material obtains the extensive concern of people, and is increasingly becoming battery material and technical field of energy storage Hot subject.
Na3V2(PO4)3It is a kind of important sodium ion battery electrode material, is polyanionic sodium-ion battery electrode material The Typical Representative of material.Na3V2(PO4)3With larger Three-dimensional Open channel design, it is available for sodium ion to carry out quickly de-/embedding. Na3V2(PO4)3Belong to hexaplanar, space group R-3c.Na3V2(PO4)3As sodium-ion battery positive material in use, filling Typical two phase reaction, changes in crystal structure Na occur in discharge process3V2(PO4)3/NaV2(PO4)3, corresponding V4+/V3+Oxygen Change reduction right, the charge and discharge platform 3.4V of electricity, theoretical specific capacity (it is de-/embedding to correspond to 2 Na+ of per molecule) is 117.6mAhg-1。Na3V2(PO4)3Sodium-ion battery positive material is can be used not only as, negative material can also be used as.Born as sodium-ion battery During the materials'use of pole, based on V3+/V2+Redox couple, charge and discharge platform 1.6V.In current research report, Na3V2(PO4)3 Specific discharge capacity when being used as anode material of lithium-ion battery is less than 150mAhg-1, specific mechanism is not yet clear and definite.
In charge and discharge process, Na3V2(PO4)3Material good crystal structural stability, Volume Changes can be kept small and With good heat endurance, beneficial to raising Na3V2(PO4)3The cyclical stability and job security of electrode material.However, Na3V2(PO4)3Electronic conductance it is poor, its theoretical specific capacity is extremely difficult in charge and discharge process and high rate performance is undesirable.This Na is had a strong impact on3V2(PO4)3The energy density of electrode material, and then unfavorable shadow is caused in terms of extensive stored energy application to it Ring.
The content of the invention
To solve the above problems, the present invention proposes a kind of metal-doped vanadium phosphate sodium combination electrode material and preparation method thereof And application.The metal-doped vanadium phosphate sodium combination electrode material has that electronic conductance is excellent, and specific discharge capacity is high and multiplying power The advantages that function admirable.
The present invention is achieved by the following technical solutions：
A kind of metal-doped vanadium phosphate sodium combination electrode material, the metal-doped vanadium phosphate sodium combination electrode material be in The Na of micro-nano composite particles shape3V2-xMx(PO4)3/ C combination electrode materials；
The Na3V2-xMx(PO4)3/ C composite is core shell structure, core Na3V2-xMx(PO4)3, shell is unformed Carbon-coating；
The amorphous carbon layer thickness is 1-10nm.
Further, the Na3V2-xMx(PO4)3In/C combination electrode materials M be Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, One or more in Cu, Zn and Cd.
Further, the Na3V2-xMx(PO4)3In/C combination electrode materials, x is atomic percent.
Further, the Na3V2-xMx(PO4)3X span is 0 in/C combination electrode materials<x<1.
Further, the Na3V2-xMx(PO4)3X span is 0 in/C combination electrode materials<x≤0.2.
Further, the Na3V2-xMx(PO4)3X span is 0 in/C combination electrode materials<x≤0.1.
Further, the Na3V2-xMx(PO4)3X span is 0 in/C combination electrode materials<x≤0.05.
Further, the Na3V2-xMx(PO4)3X span is 0 in/C combination electrode materials<x≤0.03.
Further, the Na3V2-xMx(PO4)3X span is 0.03≤x in/C combination electrode materials<1.
Further, the Na3V2-xMx(PO4)3X span is 0.05≤x in/C combination electrode materials<1.
Further, the Na3V2-xMx(PO4)3X span is 0.1≤x in/C combination electrode materials<1.
Further, the Na3V2-xMx(PO4)3X span is 0.2≤x in/C combination electrode materials<1.
Further, in Na3V2-xMx (PO4) the 3/C combination electrode materials x value be 0.03,0.05,0.1 or 0.2。
Further, the Na3V2-xMx(PO4)3The lattice structure of/C combination electrode materials is water chestnut square structure, and space group is R-3c。
Further, the Na3V2-xMx(PO4)3In/C combination electrode materials, M is the low price ion that chemical valence is+2, i.e., Low price ion M2+；
The low price ion M2+With V3+Electricity price it is different, belong to aliovalent doping, M2+Be introduced into and will certainly cause to produce in system Raw V4+/V3+Electricity price is mixed, so as to improve the electronic conductivity of combination electrode material, strengthens electrode reaction dynamic process, improves The circulation of material and high rate performance；
The low price ion M2+Compare V3+With bigger ionic radius, appropriate M2+Substitute V3+After can cause unit cell volume Increase, widen Na+Transmission channel, beneficial to the ionic conductivity for improving electrode material, and then improve the cyclical stability of material.
A kind of preparation method of metal-doped vanadium phosphate sodium combination electrode material, the preparation method comprise the following steps：
(1) hydro-thermal auxiliary-carbothermic method prepares precursor solution, including：To seal and include sodium source, vanadium source, M The water heating kettle of the mixed solution in source, phosphorus source and 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；
The water heating kettle is directly placed into the baking oven for having set temperature, is more beneficial for product homoepitaxial；
The carbon source includes organic matter carbon source and inorganic matter carbon source；
The organic matter carbon source can be coated on Na in water-heat process situ3V2-xMx(PO4)3/ C granular precursors surface, On the one hand, for preventing Na3V2-xMx(PO4)3/ C granular precursors are grown up and reunited；On the other hand, in heat treatment process Thermal decomposition is amorphous carbon, and it is Na to form core3V2-xMx(PO4)3/ C particle, shell are the core shell structures of amorphous carbon. This unique nano particle core shell structure can both shorten the transmission path of sodium ion, improve material ions electrical conductivity；It can lead to again In-stiu coating carbon material is crossed to improve electronic conductivity, to improving Na3V2-xMx(PO4)3The chemical property of/C electrode materials has Huge facilitation.
(2) preparation of presoma powder, including：The precursor solution obtained in step (1) is placed in baking oven permanent Temperature drying, 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 metal-doped vanadium phosphate sodium combination electrode material afterwards；
The metal-doped vanadium phosphate sodium combination electrode material is the Na in micro-nano composite particles shape3V2-xMx(PO4)3/C Combination electrode material；
The Na3V2-xMx(PO4)3/ C composite is core shell structure, core Na3V2-xMx(PO4)3, shell is unformed Carbon-coating.
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, Na3V2-xMx(PO4)3/ C presomas it is nanocrystalline nucleation and The effect of growth is better, but soaking time is long not only to reduce preparation efficiency, can also increase prepare composite into This；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, sodium source quality described in step (1) is m1；Vanadium source quality is m2；M sources quality is m3；Institute It is m to state phosphorus source quality4；The carbon source volume is V0。
Further, mixed solution also includes organic reducing agent described in step (1)；The organic reducing agent quality is m5。
Further, the quality of the sodium source is 0<m1≤2g；The quality in the vanadium source is 0<m2≤2g；The matter in the M sources Measure as 0<m3≤2g；The quality of phosphorus source is 0≤m4≤4g；The quality of the organic reducing agent is 0<m5≤ 2g and described The volume of carbon source is 0<V0≤10ml。
Further, sodium source described in step (1) is organic matter or inorganic matter containing Na containing Na or after being thermally decomposed.
Further, vanadium source described in step (1) is V2O5、V2O3, VO, the sulfate of vanadium, the chlorine of the nitrate of vanadium or vanadium Compound.
Further, M sources described in step (1) are to contain or contain Mg after being thermally decomposed2+、Ca2+、Sr2+、Ba2+、Mn2+、 Fe2+、Co2+、Ni2+、Cu2+、Zn2+And Cd2+In one or more kinds of materials.
Further, phosphorus source described in step (1) is NH4H2PO4。
Further, carbon source described in step (1) be citric acid, it is oxalic acid, sucrose, glucose, maleic acid, tartaric acid, anti- Bad hematic acid (vitamin C), resin, polyvinyl alcohol, polyamide, polyvinylpyrrolidone and cetyl trimethylammonium bromide and poly- One or more in ethylene glycol -400 (PEG-400).
Further, the preparation method of mixed solution is as follows described in step (1)：
Under lasting stirring condition, first, the sodium source, the vanadium source, the M sources and phosphorus source are dissolved in deionization In water, 30-50min is persistently stirred, until the sodium source, the vanadium source, the M sources and phosphorus source are dispersed in described go In ionized water；Then, toward the organic reducing agent and the carbon source is added in solution, continue to stir 60-120min, obtain described Mixed solution.
Further, the deionized water volume V is 60-100ml.
A kind of application of metal-doped vanadium phosphate sodium combination electrode material in battery material and technical field of energy storage.
Further, the described material metal doping phosphoric acid vanadium sodium combination electrode material is being used as secondary sodium-ion battery just Pole material or negative material.
The present invention has the advantages that：
(1) a kind of metal-doped vanadium phosphate sodium combination electrode material of the invention in micro-nano composite particles shape and with original position Coat carbon-coating and form core shell structure, there is good electric conductivity, excellent cyclical stability and high rate performance, Ke Yiying For the negative or positive electrode material of secondary sodium-ion battery, and other energy storage fields.
(2) to Na in a kind of metal-doped vanadium phosphate sodium combination electrode material of the invention3V2(PO4)3The V of material3+Position is entered Row low price M2+Modification by ion-doping, low price ion M2+With V3+Electricity price it is different, belong to aliovalent doping, M2+Introducing will certainly lead V is produced in cause system4+/V3+Electricity price is mixed, so as to improve the ion-electron electrical conductivity of material, strengthens electrode reaction power Process.
(3) in a kind of metal-doped vanadium phosphate sodium combination electrode material of the invention, low price ion M2+Compare V3+With bigger Ionic radius, appropriate M2+Substitute V3+After unit cell volume can be caused to increase, widen Na+Transmission channel, beneficial to raising electrode material The ionic conductivity of material, and then improve the cyclical stability of material.
(4) a kind of metal-doped vanadium phosphate sodium combination electrode material of the invention, specially Na3V2-xMx(PO4)3/ C is compound Electrode material, during its positive electrode as secondary sodium-ion battery, its specific volume that discharges first in 2.0-4.3V voltage ranges Amount is up to 117mAhg-1, close to its theoretical specific capacity；As secondary sodium-ion battery negative pole in use, in 0.01-2.5V electricity Its first discharge specific capacity is 551mAhg in the range of pressure-1, reversible capacity 243mAhg-1。
(5) preparation method of a kind of metal-doped vanadium phosphate sodium combination electrode material of the invention, it is to Na3V2(PO4)3 The V of material3+Position carries out low price M2+Ion doping, regulated and controled by rational element ratio, ensure the preparation of material pure phase.
(6) in a kind of preparation method of metal-doped vanadium phosphate sodium combination electrode material of the invention, add in mixed solution Na can be coated in water-heat process situ by entering carbon source3V2-xMx(PO4)3/ C granular precursors surface, on the one hand, for preventing Na3V2-xMx(PO4)3/ C granular precursors are grown up and reunited；On the other hand, thermal decomposition is amorphous in heat treatment process Carbon, it is Na to form core3V2-xMx(PO4)3/ C particle, shell are the core shell structures of amorphous carbon.This unique nanometer Grain core shell structure can both shorten the transmission path of sodium ion, improve material ions electrical conductivity；In-stiu coating carbon material can be passed through again To improve electronic conductivity, to improving Na3V2-xMx(PO4)3The chemical property of/C electrode materials has huge facilitation.
Brief description of the drawings
Fig. 1 is Na prepared by the embodiment of the present invention 13V1.95Ca0.05(PO4)3The XRD of/C-material；
Fig. 2 is Na prepared by the embodiment of the present invention 13V1.95Ca0.05(PO4)3The electron microscope picture of/C-material；
Fig. 3 is Na prepared by the embodiment of the present invention 13V1.95Ca0.05(PO4)3/ C-material is in 2.0-4.3V voltage ranges, electricity Current density is 11.7mA/g typical charging and discharging capacity-voltage curve；
Fig. 4 is Na prepared by the embodiment of the present invention 13V1.95Ca0.05(PO4)3/ C-material in 0.01-2.5V voltage ranges, Current density is 23.4mA/g typical charging and discharging capacity-voltage curve.
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 metal-doped vanadium phosphate sodium combination electrode material that the present embodiment is related to, the preparation method It is as follows：
(1) selection of raw material：It is Na that the present embodiment, which selects the sodium source,2CO3, the vanadium source be V2O5, the M sources be Ca (NO3)2, phosphorus source NH4H2PO4, the carbon source is PEG-4000 (PEG-400) and the organic reducing agent is anti- Bad hematic acid.
(2) raw material measures：The Na2CO3Quality m1For 0.636g, the V2O5Quality m2For 0.709g, the Ca (NO3)2Quality m3For 0.033g, the NH4H2PO4Quality m4For 1.380g, the PEG-4000 (PEG-400) volume V0 For 6ml, the ascorbic acid quality m5It is 70ml for 1.057g and deionized water volume V.
(3) preparation of mixed solution：Under lasting stirring condition, first, by the Na2CO3, the V2O5, the Ca (NO3)2With the NH4H2PO4It is dissolved in the deionized water, persistently stirs 30min, until the Na2CO3, the V2O5, institute State Ca (NO3)2With the NH4H2PO4It is dispersed in the deionized water；Then, toward adding the ascorbic acid in solution With the PEG-4000 (PEG-400), continue to stir 60min, obtain the mixed solution.
(4) hydro-thermal auxiliary-carbothermic method prepares precursor solution：To seal and include sodium source, vanadium source, M sources, phosphorus The mixed solution in source, organic reducing agent and carbon source is placed in capacity for 100ml and in the water heating kettle with polytetrafluoroethyllining lining, so The water heating kettle is placed in baking oven afterwards；The mixed solution reacts under the conditions of 200 DEG C of constant temperature, constant temperature time 40h, before obtaining Drive liquid solution.
(5) acquisition of presoma powder：After the precursor solution is carried out into ultrasonic disperse 60min first, baking oven is placed in Middle constant temperature drying, 125 DEG C of thermostat temperature, constant temperature time 8h, obtains presoma powder；Now, the efficiency and cost of the baking oven It is 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 metal-doped 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 metal-doped phosphorus obtained by a kind of above-mentioned preparation method of metal-doped vanadium phosphate sodium combination electrode material Sour vanadium sodium combination electrode material is Na3V1.95Ca0.05(PO4)3/ C (x=0.05) combination electrode material.
Fig. 1 gives Na3V1.95Ca0.05(PO4)3The XRD diffracting spectrums of/C phase pure materials, space group R-3c.
From Fig. 2 scanning electron microscope diagrams, Na3V1.95Ca0.05 (PO4) 3/C materials are in micro-nano composite particles Shape, particle diameter 20-500nm.
With 70wt%Na3V1.95Ca0.05(PO4)3/ C combination electrode materials, 15wt% acetylene black and 15wt% PVDF Slurry is made, 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, is assembled into button electricity Pond.
Fig. 3 is Na3V1.95Ca0.05(PO4)3/ C-material is in 2.0-4.3V voltage ranges, 0.1C (1C=117.6mAhg-1) typical charging and discharging capacity-voltage curve under current density, as seen from the figure, Na3V1.95Ca0.05(PO4)3/ C positive pole materials Material first discharge specific capacity is 117mAhg-1, close to its theoretical specific capacity.
Fig. 4 is Na3V1.95Ca0.05(PO4)3/ C-material is in 0.01-2.5V voltage ranges, 0.2C (1C=117.6mAh g-1) typical charging and discharging capacity-voltage curve under current density, as seen from the figure, Na3V1.95Ca0.05(PO4)3/ C negative pole materials Material first discharge specific capacity is 551mAhg-1, reversible capacity 243mAhg-1。
Embodiment 2
A kind of preparation method of vanadium phosphate sodium combination electrode material involved by the present embodiment and the preparation method of embodiment 1 It is essentially identical, only unlike：
The M sources are Mg (NO3)2, quality m3For 0.018g.
The V2O5Quality m2For 0.717g.
The metal-doped phosphorus obtained by a kind of above-mentioned preparation method of metal-doped vanadium phosphate sodium combination electrode material Sour vanadium sodium combination electrode material is Na3V1.97Mg0.03(PO4)3/ C (x=0.03) combination electrode material.
With 70wt%Na3V1.97Mg0.03(PO4)3/ C 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.
Embodiment 3
A kind of preparation method of vanadium phosphate sodium combination electrode material involved by the present embodiment and the preparation method of embodiment 1 It is essentially identical, only unlike：
The M sources are Ni (NO3)2, quality m3For 0.116g.
The V2O5Quality m2For 0.691g.
The metal-doped phosphorus obtained by a kind of above-mentioned preparation method of metal-doped vanadium phosphate sodium combination electrode material Sour vanadium sodium combination electrode material is Na3V1.9Ni0.1(PO4)3/ C (x=0.1) combination electrode material.
With 70wt%Na3V1.9Ni0.1(PO4)3/ C 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.
Embodiment 4
A kind of preparation method of vanadium phosphate sodium combination electrode material involved by the present embodiment and the preparation method of embodiment 1 It is essentially identical, only unlike：
The M sources are Mn (NO3)2, quality m3For 0.143g.
The V2O5Quality m2For 0.655g.
The metal-doped phosphorus obtained by a kind of above-mentioned preparation method of metal-doped vanadium phosphate sodium combination electrode material Sour vanadium sodium combination electrode material is Na3V1.8Mn0.2(PO4)3/ C (x=0.2) combination electrode material.
With 70wt%Na3V1.8Mn0.2(PO4)3/ C 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.
Embodiment 5
A kind of preparation method of vanadium phosphate sodium combination electrode material involved by the present embodiment and the preparation method of embodiment 1 It is essentially identical, only unlike：
The M sources are Cu (NO3)2, quality m3For 0.038g.
The V2O5Quality m2For 0.655g.
The metal-doped phosphorus obtained by a kind of above-mentioned preparation method of metal-doped vanadium phosphate sodium combination electrode material Sour vanadium sodium combination electrode material is Na3V1.95Cu 0.05(PO4)3/ C (x=0.05) combination electrode material.
With 70wt%Na3V1.95Cu 0.05(PO4)3/ C combination electrode materials, 15wt% acetylene black, 15wt% PVDF, Slurry is made, 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, is assembled into button electricity Pond.
Embodiment 6
A kind of preparation method of vanadium phosphate sodium combination electrode material involved by the present embodiment and the preparation method of embodiment 1 It is essentially identical, only unlike：
The M sources are Zn (NO3)2, quality m3For 0.059g.
The V2O5Quality m2For 0.655g.
The metal-doped phosphorus obtained by a kind of above-mentioned preparation method of metal-doped vanadium phosphate sodium combination electrode material Sour vanadium sodium combination electrode material is Na3V1.95Zn0.05(PO4)3(x=0.05) combination electrode material.
With 70wt%Na3V1.95Zn 0.05(PO4)3/ C electrode materials, 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.

Claims (10)

  1. A kind of 1. metal-doped vanadium phosphate sodium combination electrode material, it is characterised in that the metal-doped vanadium phosphate sodium compound electric Pole material is the Na in micro-nano composite particles shape3V2-xMx(PO4)3/ C combination electrode materials；
    The Na3V2-xMx(PO4)3/ C composite is core shell structure, core Na3V2-xMx(PO4)3, shell is agraphitic carbon Layer；X is atomic percent；
    The Na3V2-xMx(PO4)3X span is 0 in/C combination electrode materials<x<1.
  2. 2. a kind of metal-doped vanadium phosphate sodium combination electrode material according to claim 1, it is characterised in that described Na3V2-xMx(PO4)3M is one kind or one in Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Cu, Zn and Cd in/C combination electrode materials More than kind.
  3. 3. a kind of preparation method of metal-doped vanadium phosphate sodium combination electrode material, it is characterised in that the preparation method includes Following steps：
    (1) hydro-thermal auxiliary-carbothermic method prepares precursor solution, including：To seal and include sodium source, vanadium source, M sources, phosphorus The water heating kettle of the mixed solution of source and carbon source is placed in baking oven, and the mixed solution is in constant temperature T1, constant temperature time t1Under the conditions of it is anti- Should, obtain precursor solution；
    (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：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 process i.e. Obtain the metal-doped vanadium phosphate sodium combination electrode material；
    The metal-doped vanadium phosphate sodium combination electrode material is the Na in micro-nano composite particles shape3V2-xMx(PO4)3/ C is compound Electrode material；
    The Na3V2-xMx(PO4)3/ C composite is core shell structure, core Na3V2-xMx(PO4)3, shell is agraphitic carbon Layer.
  4. 4. a kind of preparation method of metal-doped vanadium phosphate sodium combination electrode material according to claim 3, its feature exist In step (1) the constant temperature T1For 120~200 DEG C；The constant temperature time t1For 12~48h.
  5. 5. a kind of preparation method of metal-doped vanadium phosphate sodium combination electrode material according to claim 3, its feature exist In step (2) the thermostat temperature T2For 90~150 DEG C；The constant temperature time t2For 6~10h.
  6. 6. a kind of preparation method of metal-doped vanadium phosphate sodium combination electrode material according to claim 3, its feature exist In step (3) the calcining heat T3For 400~800 DEG C；The calcination time t3For 6~10h.
  7. 7. a kind of preparation method of metal-doped vanadium phosphate sodium combination electrode material according to claim 3, its feature exist In sodium source quality described in step (1) is m1；Vanadium source quality is m2；M sources quality is m3；Phosphorus source quality is m4；The carbon source volume is V0；
    The quality of the sodium source is 0<m1≤2g；The quality in the vanadium source is 0<m2≤2g；The quality in the M sources is 0<m3≤2g； The quality of phosphorus source is 0≤m4The volume of≤4g and the carbon source is 0<V0≤10ml。
  8. 8. a kind of preparation method of metal-doped vanadium phosphate sodium combination electrode material according to claim 3, its feature exist In M sources described in step (1) are to contain or contain Mg after being thermally decomposed2+、Ca2+、Sr2+、Ba2+、Mn2+、Fe2+、Co2+、Ni2+、 Cu2+、Zn2+And Cd2+In one or more kinds of materials.
  9. 9. a kind of preparation method of metal-doped vanadium phosphate sodium combination electrode material according to claim 3, its feature exist In, carbon source described in step (1) be citric acid, it is oxalic acid, sucrose, glucose, maleic acid, tartaric acid, ascorbic acid, resin, poly- One kind in vinyl alcohol, polyamide, polyvinylpyrrolidone and cetyl trimethylammonium bromide and PEG-4000 or one More than kind.
  10. 10. a kind of metal-doped vanadium phosphate sodium combination electrode material is in the application of battery material and technical field of energy storage, its feature It is, the metal-doped vanadium phosphate sodium combination electrode material is used as the positive electrode or negative material of secondary sodium-ion battery.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108269988A (en) * 2018-02-01 2018-07-10 桂林理工大学 The preparation method of sodium-ion battery positive material calcium potassium codope vanadium phosphate sodium/carbon
CN108417792A (en) * 2018-02-01 2018-08-17 桂林理工大学 The preparation method of high-performance aluminum potassium codope fluorophosphoric acid vanadium sodium/carbon composite
CN108511704A (en) * 2018-03-06 2018-09-07 上海应用技术大学 A kind of magnesium substitution vanadium phosphate sodium/carbon composite anode material of sodium-ion battery and preparation method thereof
CN108682798A (en) * 2018-04-23 2018-10-19 北大先行科技产业有限公司 A kind of preparation method of cube carbon coating vanadium base anode material
CN108682855A (en) * 2018-05-28 2018-10-19 苏州大学 A kind of method of controllable preparation fluorophosphoric acid vanadium sodium positive electrode
CN109103431A (en) * 2018-08-19 2018-12-28 王子韩 A kind of preparation method of sodium ion battery electrode material vanadium phosphate ferrisodium composite material
CN109755568A (en) * 2019-02-27 2019-05-14 湖北锂诺新能源科技有限公司 The preparation method of potassium and cobalt codope fluorophosphoric acid vanadium lithium anode material
CN112421040A (en) * 2020-11-16 2021-02-26 中国科学院过程工程研究所 Phosphate anode material and preparation method and application thereof
CN114156470A (en) * 2021-11-30 2022-03-08 电子科技大学 Sodium-rich phase zinc vanadium sodium phosphate composite material, preparation and application thereof
CN114256446A (en) * 2020-09-23 2022-03-29 湖南农业大学 Polyanion type positive electrode material and preparation method and application thereof
CN114639829A (en) * 2022-03-01 2022-06-17 太原理工大学 Metal-doped polyanion compound positive electrode material and preparation method thereof
CN114824256A (en) * 2022-06-28 2022-07-29 武汉理工大学三亚科教创新园 Strontium ion doped sodium vanadium phosphate positive electrode material and preparation method thereof
CN115064665A (en) * 2022-04-29 2022-09-16 江苏理工学院 Doped modified carbon-coated sodium titanium phosphate composite material and preparation method and application thereof
CN115966691A (en) * 2022-12-20 2023-04-14 济南大学 Micro co-doped modified sodium vanadium phosphate monocrystal micro-flower and preparation method and application thereof
WO2023071351A1 (en) * 2021-10-26 2023-05-04 广东邦普循环科技有限公司 Method for preparing polyanionic positive electrode material for sodium-ion batteries
CN118016818A (en) * 2024-04-09 2024-05-10 宁波容百新能源科技股份有限公司 Self-supporting electrode, preparation method thereof and sodium ion battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120279850A1 (en) * 2009-11-10 2012-11-08 Centre National De La Recherche Scientifique Metal fluorophosphate synthesis and use as an active material for a battery electrode
CN103000884A (en) * 2011-09-16 2013-03-27 中国科学院物理研究所 Vanadium sodium phosphate composite material as well as preparation method and application thereof
CN104733731A (en) * 2015-03-25 2015-06-24 天津大学 Method for preparing uniform carbon-coated vanadium phosphate sodium material
CN106328911A (en) * 2016-11-30 2017-01-11 合肥工业大学 Material with mixture of ions with sodium vanadium phosphate cathode material coated by carbon and preparing method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120279850A1 (en) * 2009-11-10 2012-11-08 Centre National De La Recherche Scientifique Metal fluorophosphate synthesis and use as an active material for a battery electrode
CN103000884A (en) * 2011-09-16 2013-03-27 中国科学院物理研究所 Vanadium sodium phosphate composite material as well as preparation method and application thereof
CN104733731A (en) * 2015-03-25 2015-06-24 天津大学 Method for preparing uniform carbon-coated vanadium phosphate sodium material
CN106328911A (en) * 2016-11-30 2017-01-11 合肥工业大学 Material with mixture of ions with sodium vanadium phosphate cathode material coated by carbon and preparing method thereof

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108417792A (en) * 2018-02-01 2018-08-17 桂林理工大学 The preparation method of high-performance aluminum potassium codope fluorophosphoric acid vanadium sodium/carbon composite
CN108269988A (en) * 2018-02-01 2018-07-10 桂林理工大学 The preparation method of sodium-ion battery positive material calcium potassium codope vanadium phosphate sodium/carbon
CN108511704A (en) * 2018-03-06 2018-09-07 上海应用技术大学 A kind of magnesium substitution vanadium phosphate sodium/carbon composite anode material of sodium-ion battery and preparation method thereof
CN108682798A (en) * 2018-04-23 2018-10-19 北大先行科技产业有限公司 A kind of preparation method of cube carbon coating vanadium base anode material
CN108682855A (en) * 2018-05-28 2018-10-19 苏州大学 A kind of method of controllable preparation fluorophosphoric acid vanadium sodium positive electrode
CN109103431A (en) * 2018-08-19 2018-12-28 王子韩 A kind of preparation method of sodium ion battery electrode material vanadium phosphate ferrisodium composite material
CN109755568A (en) * 2019-02-27 2019-05-14 湖北锂诺新能源科技有限公司 The preparation method of potassium and cobalt codope fluorophosphoric acid vanadium lithium anode material
CN114256446A (en) * 2020-09-23 2022-03-29 湖南农业大学 Polyanion type positive electrode material and preparation method and application thereof
CN112421040A (en) * 2020-11-16 2021-02-26 中国科学院过程工程研究所 Phosphate anode material and preparation method and application thereof
WO2023071351A1 (en) * 2021-10-26 2023-05-04 广东邦普循环科技有限公司 Method for preparing polyanionic positive electrode material for sodium-ion batteries
CN114156470A (en) * 2021-11-30 2022-03-08 电子科技大学 Sodium-rich phase zinc vanadium sodium phosphate composite material, preparation and application thereof
CN114156470B (en) * 2021-11-30 2023-04-25 电子科技大学 Sodium-rich phase zinc-vanadium-sodium phosphate composite material, preparation and application
CN114639829A (en) * 2022-03-01 2022-06-17 太原理工大学 Metal-doped polyanion compound positive electrode material and preparation method thereof
CN115064665A (en) * 2022-04-29 2022-09-16 江苏理工学院 Doped modified carbon-coated sodium titanium phosphate composite material and preparation method and application thereof
CN114824256A (en) * 2022-06-28 2022-07-29 武汉理工大学三亚科教创新园 Strontium ion doped sodium vanadium phosphate positive electrode material and preparation method thereof
CN115966691A (en) * 2022-12-20 2023-04-14 济南大学 Micro co-doped modified sodium vanadium phosphate monocrystal micro-flower and preparation method and application thereof
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