CN109921006A - A kind of application of oxygen-enriched vanadium nitride - Google Patents
A kind of application of oxygen-enriched vanadium nitride Download PDFInfo
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- CN109921006A CN109921006A CN201910202596.6A CN201910202596A CN109921006A CN 109921006 A CN109921006 A CN 109921006A CN 201910202596 A CN201910202596 A CN 201910202596A CN 109921006 A CN109921006 A CN 109921006A
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- oxygen
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- 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 kind of applications of oxygen-enriched vanadium nitride, are used as water system Zinc ion battery positive electrode, and the molecular formula of the oxygen-enriched vanadium nitride is VNxOy, wherein x:y=1~3:1.The nitrogen low containing electronegativity in the oxygen-enriched vanadium nitride positive electrode of the present invention, therefore and Zn2+Between without apparent interaction force, make Zn2+Deintercalation behavior with quick diffusion rate and high reversible, stable structure, specific capacity are high, have superior cyclical stability and high rate capability.
Description
Technical field
The invention belongs to water system Zinc ion battery field of material technology, and in particular to a kind of application of oxygen-enriched vanadium nitride, it will
It is used as water system Zinc ion battery positive electrode.
Background technique
Although organic system lithium ion battery is widely used because of its energy density height at present, its is at high cost, no
Environmental protection, the disadvantages of security risk is big, seriously limit it in the application of extensive energy storage field.Because aqueous electrolyte has valence
Lattice are cheap, environmentally friendly, safety, ionic conductivity are high, the advantages that being easily-synthesized is concerned water system secondary ion battery
[Science 2015,350,938].Compared to other water system ion batteries, the oxidation with higher of water system Zinc ion battery is also
The nontoxic cheap, zinc load of former potential, electrode material the features such as stability is high in aqueous electrolyte [Nat.Mater.2018,17,
543], unique researching value is made it have.In the water system Zinc ion battery positive electrode currently studied, manganese-base oxide
[Nat.Energy 2016,1,16039], Prussian blue derivative [Adv.Energy Mater.2015,5,1400930] and
Vanadium base oxide [Nat.Energy2016,1,16119] is considered as the most potential positive electrode of several classes.However, so far also
More satisfactory positive electrode is not explored.
Most of positive electrode is oxide at present.In charge and discharge process, Zn2+It is had with these oxides stronger
Interaction causes the structure of positive electrode that transformation has occurred, destroys [Nat.Commun.2017,8,405], or generates and contain Zn2+
Cenotype [Nano Lett.2018,18,2402] limit these materials electrification to seriously hinder the diffusion of zinc ion
Learn giving full play to for performance.Zn2+Stronger interaction is derived from the high electronegativity of oxygen element between oxide, this makes to aoxidize
The Zn of oxonium ion in object to divalent2+Ion has powerful sucking action.Therefore, the battery containing low electronegative element is being developed just
Pole material becomes the new research direction of water system Zinc ion battery.However, there is no the document reports of this respect at present.Present invention hair
The oxygen-enriched vanadium nitride of positive electrode for having showed a kind of new water system Zinc ion battery, to promote Zinc ion battery research and development and improve zinc from
Sub- battery performance is of great significance.
Summary of the invention
In order to solve the problems in the prior art, answering the purpose of the invention is to provide a kind of oxygen-enriched vanadium nitride
With, be used as water system Zinc ion battery positive electrode, stable structure, specific capacity are high, have superior cyclical stability and
High rate capability.
A kind of application of oxygen-enriched vanadium nitride is used as water system Zinc ion battery positive electrode, the oxygen-enriched vanadium nitride
Molecular formula is VNxOy, wherein x:y=1~3:1.
Preferably, the preparation method of the oxygen-enriched vanadium nitride is burnt in inert atmosphere behind vanadium source and nitrogen source mixed grinding
It ties to obtain the final product.
Preferably, the vanadium source is selected from least one of vanadic anhydride and ammonium metavanadate；The nitrogen source is melamine
At least one of amine and urea.
Preferably, the molar ratio of the vanadium source and nitrogen source is 1:1.5~3.
Preferably, the sintering condition are as follows: 2~4 DEG C/min of heating rate, sintering temperature are 700~900 DEG C, when sintering
Between be 2~4h.
Different from other water system zinc ion positive electrodes such as manganese-base oxide, vanadium base oxide etc. in energy storage, only
Redox reaction occurs for metal cation, inventors discovered through research that, oxygen-enriched vanadium nitride is used as water system Zinc ion battery
When positive electrode, for oxygen-enriched vanadium nitride while energy storage, vanadium and nitrogen have been involved in redox reaction, during discharge, just
V in the material of pole3+It is reduced into V2+, and N3-It then loses electronics and is converted into N2-；And during the charging process, in positive electrode
V2+It is oxidized to V3+, and N2-It then obtains electronics and is converted into N3-。
General oxide anode is in charge and discharge process, Zn2+Stronger interaction is had with these oxides, is caused just
The structure of pole material has occurred transformation, destroys, or generates and contain Zn2+Cenotype limit to seriously hinder the diffusion of zinc ion
The giving full play to of these material electrochemical performances.And it is a discovery of the invention that the nitrogen electricity in oxygen-enriched vanadium nitride positive electrode is negative
Property it is relatively weak, with zinc ion formed ionic bond it is also weaker, enable zinc ion in oxygen-enriched vanadium nitride structure quickly
Ground deintercalation, and the structure of positive electrode is not destroyed, to obtain stable cycle performance and excellent high rate performance.
Compared with the prior art, the invention has the following advantages:
1, nitrogen low containing electronegativity in the oxygen-enriched vanadium nitride positive electrode of the present invention, therefore and Zn2+Between without apparent
Interaction force makes Zn2+Deintercalation behavior with quick diffusion rate and high reversible, obtains superior high rate performance.
2, the present invention synthesizes a kind of oxygen-enriched vanadium nitride positive electrode of water system Zinc ion battery by simple sintering method.
Safety of the present invention is good and nontoxic, and synthetic material is at low cost, easy to industrialized production.
Detailed description of the invention
Fig. 1 is VN made from embodiment 1xOyThe XRD spectrum of material；
Fig. 2 is VN made from embodiment 1xOy(a) SEM of material schemes, and (b) TEM schemes；
Fig. 3 is VN made from embodiment 1xOyThe element energy spectrum diagram of material；
Fig. 4 is VN made from embodiment 1xOyVN+V made from material, comparative example 12O3Material and raw material V2O5Electrochemistry
Performance map, wherein (a) 1Ag-1Charge-discharge performance；(b) corresponding coulombic efficiency；(c)VNxOyThe high rate performance of material；
Fig. 5 is VN made from embodiment 1xOyMaterial ex situ XRD spectrum, wherein (a) is recycled for the first time；(b) different numbers follow
Ring；
VN made from Fig. 6 embodiment 1xOyThe Analysis on Mechanism of material, wherein (a) ex situ V 2p XPS map；(b)V L-
Edge and O K-edge NEXAFS map；(c) ex situ N 1s XPS map；(d) N K-edge NEXAFS map；(e,f)
Ex situ scanned picture；(g) the N K-edge NEXAFS map after surface argon gas etching；(h) the infrared figure of ex situ diffusing reflection
Spectrum；(i) solid phase nuclear magnetic resonance spectroscopy；
Fig. 7 is VN made from embodiment 2xOyThe XRD spectrum of material；
Fig. 8 is VN made from embodiment 3xOyThe XRD spectrum of material；
Fig. 9 is VN+V made from comparative example 12O3The XRD spectrum of material.
Specific embodiment
It is intended to further illustrate the present invention with reference to embodiments, is not intended to limit the present invention.
Embodiment 1
Take 10mmol V2O5With 20mmol C3N3(NH2)3, after solid phase mixing is ground to uniformly, it is put into porcelain boat, by porcelain boat
It is placed in atmosphere tube type furnace.Pass to argon gas in tube furnace, be warming up to 800 DEG C with the speed of 2 DEG C/min, and keep the temperature 2h to get
VNxOyMaterial.
Fig. 1 is the XRD spectrum of the embodiment of the present invention 1.As can be seen, diffraction maximum is corresponding with VN well.Fig. 2
It (a) is VN prepared by embodiment 1xOyThe scanning electron microscopic picture of material, it is seen that it is nanometer sheet structure and morphology.Fig. 2 (b) display
Be sample prepared by embodiment 1 transmission electron microscope picture, it will be seen that nanometer sheet is porous, and each nanometer sheet is and by very
Donna rice grain is composed.Fig. 3 is shown sample element power spectrum prepared by embodiment 1, and surface nitrogen and oxygen element rub
You are than being N:O=2:1.
VN prepared by embodiment 1xOyVN+V made from material, comparative example 12O3Material and V2O5Material is allocated as anode, zinc
Metal is as cathode, 2M ZnSO4Solution uses glass fibre membrane as electrolyte, diaphragm.The constant current charge-discharge experiment of battery exists
It is tested at room temperature using the Land CT2001A equipment of Wuhan Lan electricity company.Test voltage range be 0.4~1.4V, reference in
Zn/Zn2+。
The VN of the preparation of embodiment 1 is shown in Fig. 4xOyMaterial and comparative sample VN+V2O3、V2O5The electrification of (original) material
Learn performance.Wherein, Fig. 4 (a) is cyclic voltammetry curve (CV), VNxOyElectrode has preferable invertibity；It (b) is 1Ag-1Fill
Discharge cycle performance, VNxOyShow optimal cycle performance；(c)VNxOyThe high rate performance of material.As it can be seen that relative to VN+
V2O3、V2O5Material, VNxOyMaterial is in 1A g-1It is lower that there is maximum specific discharge capacity (240mAh g-1), superior stable circulation
Property.And VNxOyMaterial also shows excellent high rate performance (Fig. 4 (d), in 20A g-1200mAh g is obtained under current density-1's
Specific discharge capacity).
Fig. 5 (a) shows reversible insertion behavior, and passes through 400 circulation VNxOyThere is no significantly becoming for structure
Change (Fig. 5 (b)).Fig. 6 (a-d) shows that in charge and discharge process, reversible variation (V occurs for the valence state of V and N3+-V2+-V3+；N3--
N2--N3-).Fig. 6 (e, f) shows during discharge, VNxOyShow to generate one layer of perforated membrane, and terminates perforated membrane in charging
It disappears.Appraising at the current rate for analytical proof nitrogen is etched by surface argon gas almost to occur on the surface (Fig. 6 (g)) of material.Pass through electricity
Pole diffusing reflection IR Characterization shows that electrode surface occurs that there is apparent-OH foundation to roll into a ball signal (Fig. 6 (h)) in discharge process, this
It may be in reaction process ,-OH and the material surface of electrolyte react, and cause the variation of nitrogen valence state.Fig. 6 (i) is hydrogen
The solid phase nuclear magnetic resonance of spectrum characterizes, it was demonstrated that in charge and discharge process, H+Reversible insertion has occurred in material internal.Therefore,
- the OH and material surface for further demonstrating electrolyte react.As the H in electrolyte+Inside insert material, remaining-
OH reacts with material surface.
Embodiment 2
Take 10mmol NH4VO3With 20mmol C3N3(NH2)3, after solid phase mixing is ground to uniformly, it is put into porcelain boat, by porcelain
Boat is placed in atmosphere tube type furnace.Argon gas is passed in tube furnace, is warming up to 800 DEG C with the speed of 2 DEG C/min, and keep the temperature 2h.Fig. 7 is
The XRD spectrum of 2 resulting materials of embodiment.
Embodiment 3
Take 10mmol V2O5With 20mmol CH4N2O is put into porcelain boat after solid phase mixing is ground to uniformly, porcelain boat is set
In atmosphere tube type furnace.Argon gas is passed in tube furnace, is warming up to 800 DEG C with the speed of 2 DEG C/min, and keep the temperature 2h.Fig. 8 is to implement
The XRD spectrum of 3 resulting materials of example.
Comparative example 1
Take 10mmol V2O5With 10mmol C3N3(NH2)3, after solid phase mixing is ground to uniformly, it is put into porcelain boat, by porcelain boat
It is placed in atmosphere tube type furnace.Argon gas is passed in tube furnace, is warming up to 800 DEG C with the speed of 2 DEG C/min, and keep the temperature 2h.Fig. 9 is pair
The XRD spectrum of 1 resulting materials of ratio.
Claims (6)
1. a kind of application of oxygen-enriched vanadium nitride, it is characterised in that: it is used as water system Zinc ion battery positive electrode, it is described oxygen-enriched
The molecular formula of vanadium nitride is VNxOy, wherein x:y=1~3:1.
2. a kind of preparation method of oxygen-enriched vanadium nitride described in claim 1, it is characterised in that: by vanadium source and nitrogen source mixed grinding
Afterwards, it is sintered in inert atmosphere to obtain the final product.
3. the preparation method of oxygen-enriched vanadium nitride according to claim 2, it is characterised in that: the vanadium source is selected from five oxidations two
At least one of vanadium and ammonium metavanadate.
4. the preparation method of oxygen-enriched vanadium nitride according to claim 2, it is characterised in that: the nitrogen source be melamine and
At least one of urea.
5. the preparation method of oxygen-enriched vanadium nitride according to claim 2, it is characterised in that: mole in the vanadium source and nitrogen source
Than for 1:1.5~3.
6. the preparation method of oxygen-enriched vanadium nitride according to claim 2, it is characterised in that: the sintering condition are as follows: heating
2~4 DEG C/min of rate, sintering temperature are 700~900 DEG C, and sintering time is 2~4h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111129451A (en) * | 2019-12-12 | 2020-05-08 | 中南大学 | VN fusiform nanorod with core-shell structure and preparation method and application thereof |
| CN115676783A (en) * | 2022-10-13 | 2023-02-03 | 菏泽学院 | Preparation method of water-based zinc ion battery positive electrode material based on vanadium-based MOFs derivative vanadium nitride |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693529A (en) * | 2009-10-12 | 2010-04-14 | 冯良荣 | Method for preparing vanadium nitride |
| US20130309591A1 (en) * | 2012-04-25 | 2013-11-21 | Nanotune Technologies Corp. | Nanoporous energy chips and related devices and methods |
| CN103427080A (en) * | 2013-08-20 | 2013-12-04 | 天津大学 | Sol-gel method for preparing zinc-ion-modified carbon-coated lithium vanadium phosphate used as anode material of lithium ion battery |
| CN103553131A (en) * | 2013-10-29 | 2014-02-05 | 黑龙江大学 | Preparation method of lithium ion battery negative electrode spherical V2O3/C composite material with multilevel structure |
| CN103633309A (en) * | 2013-12-13 | 2014-03-12 | 黑龙江大学 | Preparation method of core-shell structure vanadium trioxide microspheres |
| CN104016314A (en) * | 2014-06-26 | 2014-09-03 | 济南顺源新材料科技有限公司 | Preparation method of vanadium nitride |
| CN105742633A (en) * | 2016-04-08 | 2016-07-06 | 武汉理工大学 | Porous oxygen-rich vanadium nitride nanosheet and preparation method and application therefor |
| CN107221665A (en) * | 2017-06-26 | 2017-09-29 | 南开大学 | A kind of preparation method of Zinc ion battery barium oxide combination electrode material |
| CN108545774A (en) * | 2018-03-30 | 2018-09-18 | 武汉理工大学 | Porous vanadic anhydride micron ball electrode material and its preparation method and application |
-
2019
- 2019-03-18 CN CN201910202596.6A patent/CN109921006B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693529A (en) * | 2009-10-12 | 2010-04-14 | 冯良荣 | Method for preparing vanadium nitride |
| US20130309591A1 (en) * | 2012-04-25 | 2013-11-21 | Nanotune Technologies Corp. | Nanoporous energy chips and related devices and methods |
| CN103427080A (en) * | 2013-08-20 | 2013-12-04 | 天津大学 | Sol-gel method for preparing zinc-ion-modified carbon-coated lithium vanadium phosphate used as anode material of lithium ion battery |
| CN103553131A (en) * | 2013-10-29 | 2014-02-05 | 黑龙江大学 | Preparation method of lithium ion battery negative electrode spherical V2O3/C composite material with multilevel structure |
| CN103633309A (en) * | 2013-12-13 | 2014-03-12 | 黑龙江大学 | Preparation method of core-shell structure vanadium trioxide microspheres |
| CN104016314A (en) * | 2014-06-26 | 2014-09-03 | 济南顺源新材料科技有限公司 | Preparation method of vanadium nitride |
| CN105742633A (en) * | 2016-04-08 | 2016-07-06 | 武汉理工大学 | Porous oxygen-rich vanadium nitride nanosheet and preparation method and application therefor |
| CN107221665A (en) * | 2017-06-26 | 2017-09-29 | 南开大学 | A kind of preparation method of Zinc ion battery barium oxide combination electrode material |
| CN108545774A (en) * | 2018-03-30 | 2018-09-18 | 武汉理工大学 | Porous vanadic anhydride micron ball electrode material and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| FUKUI CHENG ET AL.: "Preparation of nanocrystalline VN by the melamine reduction of V2O5 xerogel and its supercapacitive behavior", 《MATERIALS CHEMISTRY AND PHYSICS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111129451A (en) * | 2019-12-12 | 2020-05-08 | 中南大学 | VN fusiform nanorod with core-shell structure and preparation method and application thereof |
| CN111129451B (en) * | 2019-12-12 | 2021-04-20 | 中南大学 | VN fusiform nanorod with core-shell structure and preparation method and application thereof |
| CN115676783A (en) * | 2022-10-13 | 2023-02-03 | 菏泽学院 | Preparation method of water-based zinc ion battery positive electrode material based on vanadium-based MOFs derivative vanadium nitride |
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