CN103531764B - Sodium-ion battery positive material spherical ammonium vanadium oxide and preparation method therefor - Google Patents

Sodium-ion battery positive material spherical ammonium vanadium oxide and preparation method therefor Download PDF

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CN103531764B
CN103531764B CN201310515865.7A CN201310515865A CN103531764B CN 103531764 B CN103531764 B CN 103531764B CN 201310515865 A CN201310515865 A CN 201310515865A CN 103531764 B CN103531764 B CN 103531764B
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sodium
acid
spherical
ion battery
ammonium
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CN103531764A (en
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费海龙
林耘生
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Fuzhou University
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Fuzhou University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • 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 discloses a sodium-ion battery positive material spherical ammonium vanadium oxide and a preparation method therefor. Ammonium metavanadate, organic carboxylic acids, glycol and polyethylene glycol 400 are employed as raw materials, a hydrothermal synthesis method is employed, and spherical ammonium vanadium oxide (NH4)0.38V2O5 is prepared. The process is simple, the repeatability is good, the yield is high, the synthesis conditions are mild, the cost is low, and the prepared electrode material has high specific capacity.

Description

Spherical ammonium barium oxide of a kind of sodium-ion battery positive material and preparation method thereof
Technical field
The invention belongs to cell positive material preparation field, be specifically related to spherical ammonium barium oxide of a kind of sodium-ion battery positive material and preparation method thereof.
Background technology
China's navajoite rich reserves, ammonium barium oxide has cheapness, easily synthesis, energy density is high, in high power capacity sodium-ion battery positive material, has potentiality to be exploited.We find by current research: sodium ion intercalation NH 4v 4o 10, (the NH of formation 4) 0.83na 0.43v 4o 100.26H 2o can change NH 4v 4o 10cell parameter (H.L. Fei, Z.R. Shen, J.G. Wang, H.J. Zhou, D.T. Ding, T.H. Chen, Flower-like (NH 4) 0.83na 0.43v 4o 10nano-structure for stable lithium-ion battery electrodes, j. Power Sources, and can the ammonium sodium vanadium bronze (NH of the new crystalline texture of Induced synthesis 2 (2009) 1164.) 4) 0.26na 0.14v 2o 5[H.L. Fei, Z.R. Shen, J.G. Wang, D.T. Ding, T.H. Chen, Novel bi-cation intercalated vanadium bronze nanostructures for stable and high capacity cathode materials electrochem. Commun. 10 (2008) 1541].The two, as the positive electrode of lithium ion battery, all represents higher specific discharge capacity and good cyclical stability.(NH 4) 0.26na 0.14v 2o 5at 2.0 ~ 3.4 V, initial discharge capacity is 196 mAhg -1, the discharge capacity of the 30th time can reach 200 mAhg -1.(NH 4) 0.83na 0.43v 4o 100.26H 2o also represents good cyclical stability.Sodium ion is to NH 4v 4o 10the improvement of chemical property, owing to change cell parameter, causes the skew at XRD peak.Be converted into (NH thermodynamics more being stablized novel monocline 4) 0.26na 0.14v 2o 5, and sodium ion can be good at carrying out deintercalation.Therefore, ammonium bronze can be used as the positive electrode of sodium-ion battery, and sodium metal or hard carbon are negative pole, during charging, and Na +deviate from from positive pole, embed negative pole.During electric discharge, sodium ion is deviate from from negative pole, inserts ammonium sodium bronze.
But current people only attempt the positive electrode of different ammonium barium oxide as lithium ion battery.Such as NH 4v 4o 10nanobelt (H.Y. Wang, K.L. Huang, C.H. Huang, S.Q. Liu, Y. Ren, X.B. Huang, J. Power Sources 196 (2011) 5645 – 5650; K.F. Zhang, G.Q. Zhang, X. Liu, Z.X. Su, H.L. Li, J. Power Sources 157 (2006) 528 – 532) at 15 mAg -1discharge current density under, initial discharge capacity reaches 225.2 mAhg -1.NH 4v 3o 80.2H 2o thin slice reaches 209.4 mAhg at the 1.8-4V specific discharge capacity after 30 times that circulates -1(H.Y. Wang, K.L. Huang, S.Q. Liu, C.H. Huang, W.J. Wang, Y. Ren, J. Power Sources 196 (2011) 788-792).NH 4v 3o 8nanometer rods represents good cyclical stability and higher specific discharge capacity (H.Y. Wang under high current density, Y.Ren, W.J. Wang, X.B. Huang, K.L. Huang, Y. Wang, S.Q. Liu, J. Power Sources 199 (2012) 315-321).Yet there are no document and patent report using the positive electrode of ammonium barium oxide as sodium-ion battery.
Summary of the invention
The object of the present invention is to provide spherical ammonium barium oxide of a kind of sodium-ion battery positive material and preparation method thereof, present invention process is simple, and reproducible, productive rate is high.Synthesis condition is gentle, and cost is low.Prepared electrode material specific capacity is high.
For achieving the above object, the present invention adopts following technical scheme:
With ammonium metavanadate, organic carboxyl acid, ethylene glycol and PEG400 for raw material, adopt hydrothermal synthesis method, obtained spherical ammonium barium oxide (NH 4) 0.38v 2o 5.Preparation method comprises the following steps:
(1) organic carboxyl acid is dissolved in the mixed solvent of ethylene glycol and PEG400;
(2) under magnetic agitation, ammonium metavanadate is joined in the mixed solution of step (1), continue stirring 5 minutes-2 hours;
(3) move in reactor by step (2) gained solution, sealing, reacts 1-200 h at 120-200 DEG C, and filter, 60 DEG C of drying 12 h, obtain spherical NH 4vO 3;
(4) by NH 4vO 3at 200-300 DEG C of roasting 1-100 hour, obtain spherical (NH 4) 0.38v 2o 5.
Described organic carboxyl acid is formic acid, acetic acid, lactic acid, citric acid, vitamin C, oxalic acid, malic acid, the one in tartaric acid.
In mixed solvent, the volume ratio of ethylene glycol and PEG400 is 3:4-1:1.
The mol ratio 2.73:1 of ammonium metavanadate and organic carboxyl acid.
Spherical (NH 4) 0.38v 2o 5as the active component of the positive electrode of sodium-ion battery; conductive agent is ultrapure carbon; binding agent is Kynoar; the mass ratio of three is 7:2:1; electrolyte is the propylene carbonate ester solution of 1 M sodium perchlorate, and battery case is CR2025 model, and collector is aluminium flake; sodium metal sheet is as negative pole, and battery has been assembled under argon shield.
Remarkable advantage of the present invention is: the present invention adopts the raw material of low cost, and hydrothermal synthesis method is simple, and productive rate is high, and favorable reproducibility is easy to large-scale production.This spherical (NH 4) 0.38v 2o 5as the positive electrode of sodium-ion battery, in discharge process, primary specific discharge capacity is 35 mAhg -1.Secondary specific discharge capacity is 105.3 mAhg -1, charge and discharge cycles 15 times, capacity remains on 89.3 mAhg -1.
Accompanying drawing explanation
Fig. 1 is the spherical NH of the embodiment of the present invention 1 4vO 3(a) and (NH 4) 0.38v 2o 5the scanning electron microscope (SEM) photograph of (b).
Fig. 2 is the spherical NH of the embodiment of the present invention 1 4vO 3(a) and (NH 4) 0.38v 2o 5the XRD figure of (b).
Fig. 3 is the spherical (NH of the embodiment of the present invention 1 4) 0.38v 2o 5cycle performance figure (a) and first time and second time cycle charge-discharge curve chart (b).
Fig. 4 is the spherical (NH of the embodiment of the present invention 2 4) 0.38v 2o 5scanning electron microscope (SEM) photograph.
Fig. 5 is the (NH of the spherical macropore of the embodiment of the present invention 3 4) 0.38v 2o 5scanning electron microscope (SEM) photograph.
Embodiment
With ammonium metavanadate, organic carboxyl acid, ethylene glycol and PEG400 for raw material, adopt hydrothermal synthesis method, obtained spherical ammonium barium oxide (NH 4) 0.38v 2o 5.Crystallographic system: monocline.Cell parameter: a=15.7500, b=3.5800, c=10.2600, α=90.0000, β=109.5000, γ=90.0000.Typical case's pattern is the microballoon in 3 dimension ducts.Preparation method comprises the following steps:
(1) organic carboxyl acid is dissolved in the mixed solvent of ethylene glycol and PEG400;
(2) under magnetic agitation, ammonium metavanadate is joined in the mixed solution of step (1), continue stirring 5 minutes-2 hours;
(3) move in reactor by step (2) gained solution, sealing, reacts 1-200 h at 120-200 DEG C, and filter, 60 DEG C of drying 12 h, obtain spherical NH 4vO 3; NH 4vO 3microballoon yardstick is even, rough surface, sphere have slight crack, and the diameter of microballoon is 1-6 micron;
(4) by NH 4vO 3at 200-300 DEG C of roasting 1-100 hour, obtain spherical (NH 4) 0.38v 2o 5, diameter is 2-6 micron, and piled up by nano particle and form, indivedual microsphere surface has three-dimensional duct.
Described organic carboxyl acid is formic acid, acetic acid, lactic acid, citric acid, vitamin C, oxalic acid, malic acid, the one in tartaric acid.
In mixed solvent, the volume ratio of ethylene glycol and PEG400 is 3:4-1:1.
The mol ratio of ammonium metavanadate and organic carboxyl acid is 2.73:1.
Spherical (NH 4) 0.38v 2o 5as the active component of the positive electrode of sodium-ion battery; conductive agent is ultrapure carbon; binding agent is Kynoar; the mass ratio of three is 7:2:1; electrolyte is the propylene carbonate ester solution of 1 M sodium perchlorate, and battery case is CR2025 model, and collector is aluminium flake; sodium metal sheet is as negative pole, and battery has been assembled under argon shield.
Further describe feature of the present invention below by example, but the present invention is not limited to following example.
Embodiment 1
Spherical ammonium barium oxide (NH 4) 0.38v 2o 5preparation method comprise the following steps:
(1) organic carboxyl acid is dissolved in the mixed solvent of ethylene glycol and PEG400;
(2) under magnetic agitation, ammonium metavanadate is joined in the mixed solution of step (1), continue stirring 2 hours;
(3) move in reactor by step (2) gained solution, sealing, reacts 200 h at 120 DEG C, and filter, 60 DEG C of drying 12 h, obtain spherical NH 4vO 3;
(4) by NH 4vO 3200 DEG C of roastings 100 hours, obtain spherical (NH 4) 0.38v 2o 5.
Described organic carboxyl acid is formic acid, acetic acid, lactic acid, citric acid, vitamin C, oxalic acid, malic acid, the one in tartaric acid.
In mixed solvent, the volume ratio of ethylene glycol and PEG400 is 3:4.
The mol ratio of ammonium metavanadate and organic carboxyl acid is 2.73:1.
Spherical (NH 4) 0.38v 2o 5as the active component of the positive electrode of sodium-ion battery; conductive agent is ultrapure carbon; binding agent is Kynoar; the mass ratio of three is 7:2:1; electrolyte is the propylene carbonate ester solution of 1 M sodium perchlorate, and battery case is CR2025 model, and collector is aluminium flake; sodium metal sheet is as negative pole, and battery has been assembled under argon shield.
Embodiment 2
Spherical ammonium barium oxide (NH 4) 0.38v 2o 5preparation method comprise the following steps:
(1) organic carboxyl acid is dissolved in the mixed solvent of ethylene glycol and PEG400;
(2) under magnetic agitation, ammonium metavanadate is joined in the mixed solution of step (1), continue stirring 1 hour;
(3) move in reactor by step (2) gained solution, sealing, reacts 1 h at 200 DEG C, and filter, 60 DEG C of drying 12 h, obtain spherical NH 4vO 3;
(4) by NH 4vO 3300 DEG C of roastings 1 hour, obtain spherical (NH 4) 0.38v 2o 5.
Described organic carboxyl acid is formic acid, acetic acid, lactic acid, citric acid, vitamin C, oxalic acid, malic acid, the one in tartaric acid.
In mixed solvent, the volume ratio of ethylene glycol and PEG400 is 1:1.
The mol ratio of ammonium metavanadate and organic carboxyl acid is 2.73:1.
Spherical (NH 4) 0.38v 2o 5as the active component of the positive electrode of sodium-ion battery; conductive agent is ultrapure carbon; binding agent is Kynoar; the mass ratio of three is 7:2:1; electrolyte is the propylene carbonate ester solution of 1 M sodium perchlorate, and battery case is CR2025 model, and collector is aluminium flake; sodium metal sheet is as negative pole, and battery has been assembled under argon shield.
Embodiment 3
Spherical ammonium barium oxide (NH 4) 0.38v 2o 5preparation method comprise the following steps:
(1) organic carboxyl acid is dissolved in the mixed solvent of ethylene glycol and PEG400;
(2) under magnetic agitation, ammonium metavanadate is joined in the mixed solution of step (1), continue stirring 5 minutes;
(3) move in reactor by step (2) gained solution, sealing, reacts 100h at 160 DEG C, and filter, 60 DEG C of drying 12 h, obtain spherical NH 4vO 3;
(4) by NH 4vO 3250 DEG C of roastings 50 hours, obtain spherical (NH 4) 0.38v 2o 5.
Described organic carboxyl acid is formic acid, acetic acid, lactic acid, citric acid, vitamin C, oxalic acid, malic acid, the one in tartaric acid.
In mixed solvent, the volume ratio of ethylene glycol and PEG400 is 3:4.
The mol ratio of ammonium metavanadate and organic carboxyl acid is 2.73:1.
Spherical (NH 4) 0.38v 2o 5as the active component of the positive electrode of sodium-ion battery; conductive agent is ultrapure carbon; binding agent is Kynoar; the mass ratio of three is 7:2:1; electrolyte is the propylene carbonate ester solution of 1 M sodium perchlorate, and battery case is CR2025 model, and collector is aluminium flake; sodium metal sheet is as negative pole, and battery has been assembled under argon shield.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.

Claims (4)

1. the spherical ammonium barium oxide of sodium-ion battery positive material, is characterized in that: with ammonium metavanadate, organic carboxyl acid, ethylene glycol and PEG400 for raw material, adopts solvent-thermal process method, obtained spherical ammonium barium oxide (NH 4) 0.38v 2o 5.
2. prepare a method for the spherical ammonium barium oxide of sodium-ion battery positive material as claimed in claim 1, it is characterized in that: comprise the following steps:
(1) organic carboxyl acid is dissolved in the mixed solvent of ethylene glycol and PEG400;
(2) under magnetic agitation, ammonium metavanadate is joined in the mixed solution of step (1), continue stirring 5 minutes-2 hours;
(3) move in reactor by step (2) gained solution, sealing, reacts 1-200 h at 120-200 DEG C, and filter, 60 DEG C of drying 12 h, obtain spherical NH 4vO 3;
(4) by NH 4vO 3at 200-300 DEG C of roasting 1-100 hour, obtain spherical (NH 4) 0.38v 2o 5;
In mixed solvent, the volume ratio of ethylene glycol and PEG400 is 3:4-1:1;
The mol ratio 2.73:1 of ammonium metavanadate and organic carboxyl acid.
3. method according to claim 2, is characterized in that: described organic carboxyl acid is formic acid, acetic acid, lactic acid, citric acid, vitamin C, oxalic acid, malic acid, the one in tartaric acid.
4. an application for the spherical ammonium barium oxide of sodium-ion battery positive material as claimed in claim 1, is characterized in that: spherical (NH 4) 0.38v 2o 5as the active component of the positive electrode of sodium-ion battery; conductive agent is ultrapure carbon; binding agent is Kynoar; the mass ratio of three is 7:2:1; electrolyte is the carbonic allyl ester solution of 1 M sodium perchlorate, and battery case is CR2025 model, and collector is aluminium flake; sodium metal sheet is as negative pole, and battery has been assembled under argon shield.
CN201310515865.7A 2013-10-29 2013-10-29 Sodium-ion battery positive material spherical ammonium vanadium oxide and preparation method therefor Expired - Fee Related CN103531764B (en)

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CN104466178B (en) * 2014-12-05 2016-03-30 武汉理工大学 Classification mesoporous sodium vanadate bending nano wire and its preparation method and application
CN105185998B (en) * 2015-08-11 2017-07-11 陕西科技大学 Chinese ilex derived carbon as anode material of lithium-ion battery preparation method
CN105271158B (en) * 2015-09-16 2017-09-19 湘潭大学 A kind of fusiformis individual layer sheet NaTi2(PO4)3The preparation method of electrode material
CN106865611A (en) * 2017-03-29 2017-06-20 中南大学 A kind of lithium ion battery NaVO3Negative material and preparation method thereof
CN107170984B (en) * 2017-05-24 2020-01-24 江苏大学 Preparation method of ammonium vanadate anode material of lithium ion battery
CN107720822B (en) * 2017-09-15 2019-08-09 陕西科技大学 A kind of preparation method of sea urchin shape anode material for lithium-ion batteries
CN111834628B (en) * 2020-07-28 2021-11-02 湖南工学院 Na-doped NH4V4O10Nano sheet material and preparation method and application thereof
CN115417455A (en) * 2022-10-09 2022-12-02 中国科学技术大学 Vanadium pentoxide intercalation material, preparation method thereof and application thereof in water-based zinc ion battery

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