CN109935826A - A kind of tin oxide nano piece to be rich in oxygen defect is the magnesium cell of anode - Google Patents
A kind of tin oxide nano piece to be rich in oxygen defect is the magnesium cell of anode Download PDFInfo
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- CN109935826A CN109935826A CN201910060563.2A CN201910060563A CN109935826A CN 109935826 A CN109935826 A CN 109935826A CN 201910060563 A CN201910060563 A CN 201910060563A CN 109935826 A CN109935826 A CN 109935826A
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- oxygen defect
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- 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
It is positive magnesium cell that the invention discloses a kind of with the tin oxide nano piece rich in oxygen defect.The magnesium cell includes: negative electrode casing, elastic slice, gasket, cathode, diaphragm, anode, molybdenum sheet, anode cover, electrolyte；The cathode is the tin oxide nano piece rich in oxygen defect；The cathode is magnesium foil.First passage atom method of substitution of the present invention, by SnS2Nanometer sheet is converted to the porous black SnO rich in oxygen defect2‑xNanometer sheet, and confirm oxygen defect to SnO2‑xNanometer sheet, which stores up magnesium ability, has humidification.Electrochemical results show that it is the effective way for designing rechargeable magnesium battery electrode material that oxygen defect is introduced in transition metal oxide electrode material.
Description
Technical field
This application involves electrochemical energy storage almost fields, in particular to a kind of oxidation sijna to be rich in oxygen defect
Rice piece is the magnesium cell of anode.
Background technique
Rechargeable battery is widely used in mobile power source, electric vehicle, power grid storage etc..
Currently, ever-increasing energy storage demand is mainly met by battery and lithium ion battery.However, in the world
In the interior transition for discharging the energy from fossil fuel to low temperature chamber gas, a variety of different energy storage technologies will be needed.Battery will be not
Central role is played in the global energy deposit come, is especially that the development and application of non-lithium battery will solve lithium-ion technology still
An open question.In this field, the battery of multivalent ion is due to its superior theoretical volumetric energy density, extensive
It is very attractive in stored energy application.It is matched however, the development of multivalence battery is still suffered from specific operation voltage window
Electrolyte, realize the key scientific challenges of reversible metal dissolution/deposition and the suitable electrode material of design etc..
In multivalent ion battery, magnesium cell is big because of the nature rich content of its magnesium metal, theoretical volumetric energy density
(3833mAh cm-3) and when circulation it is big without dendritic growth and be concerned.
However, divalent magnesium ion has very strong polarizability, strong electrostatic phase interaction occurs between the lattice of electrode material
With this can lead to slow Mg2+It spreads and inhibits it reversibly embedding and abjection, therefore the electrode material in many lithium ion batteries
It cannot be used in magnesium cell.
Summary of the invention
For technological gap in the prior art, it is necessary to for the new synthesis of the developing material of reversible insertion divalent magnesium ion
Strategy.
Crystal defect, such as Lacking oxygen play a crucial role in the property of transition metal oxide.Lacking oxygen can
As shallow donor, carrier concentration is improved, to improve the conductivity of transition metal oxide.But seldom have been reported that discussion
Influence of the Lacking oxygen to magnesium cell.
The invention provides a kind of magnesium cell with the tin oxide nano piece rich in oxygen defect for anode.It is described
Magnesium cell include: negative electrode casing, elastic slice, gasket, cathode, diaphragm, anode, molybdenum sheet, anode cover, electrolyte；The cathode is
Tin oxide nano piece rich in oxygen defect；The cathode is magnesium foil.
Specifically, the diaphragm is glass fibre membrane.
Specifically, the electrolyte is phenyl-magnesium-chloride/aluminium chloride tetrahydrofuran solution.
Specifically, the metal of the protection anode shell is molybdenum, tungsten, tantalum.
Specifically, the tin oxide nano piece rich in oxygen defect obtains by the following method:
(1) sulphur powder is added in oleyl amine, under an inert atmosphere, is heated to 90~120 DEG C and is kept for two hours, removes
Moisture and oxygen, then Temperature fall to room temperature；
(2) by SnCl4It injects in above-mentioned solution, is slowly warming up to 150~250 DEG C, and kept for 2~5 hours；
(3) after natural cooling, centrifugation, chloroform and dehydrated alcohol washing several times, after 50~80 DEG C of vacuum drying, are obtained
SnS2Nanometer sheet；
(4) by resulting SnS2Nanometer sheet is dispersed in water, and is stirred 2~5 days at room temperature, centrifugation, after ethanol washing, vacuum
Drying is to get the tin oxide nano piece for being rich in oxygen defect.
In the above method, the dosage of reactant are as follows: every 20~40mL oleyl amine, corresponding 20~30mmol of sulphur powder dosage are corresponding
SnCl414~22mmol of dosage.
Specifically, the described anode obtains by the following method: will be enriched in the tin oxide nano piece of oxygen defect, acetylene black and
Gather inclined tetrafluoroethene to grind uniformly by the mass ratio of 8:1:1, N-Methyl pyrrolidone is added, homogenate is made, be coated on carbon paper, and
It is dried in vacuo 10~20 hours in 50~80 DEG C, the disk being then cut into, i.e. magnesium cell cathode.The N-Methyl pyrrolidone
Additional amount be every 1.0g SnS use 4~5mL N-Methyl pyrrolidone.
Specifically, the cathode obtains by the following method: will be polishing to a thickness of the magnesium foil of 0.05mm with SiC sand paper
Then light is cut into sequin as magnesium cell cathode.Further,
The magnesium foil is with a thickness of 0.05mm.
The utility model has the advantages that first passage atom method of substitution of the present invention, by SnS2Nanometer sheet is converted to rich in the porous of oxygen defect
Black SnO2-xNanometer sheet, and confirm oxygen defect to SnO2-xNanometer sheet, which stores up magnesium ability, has humidification.Electro-chemical test knot
Fruit shows that it is the effective way for designing rechargeable magnesium battery electrode material that oxygen defect is introduced in transition metal oxide electrode material
Diameter.
Detailed description of the invention
Fig. 1 is SnO2-xThe SEM of nanometer sheet schemes.
Fig. 2 is magnesium cell installation diagram.
Fig. 3 is the electrical performance testing figure of battery of the present invention.
Fig. 4 is 300mA g-1Loop test figure when current density.
Specific embodiment
In order to make those skilled in the art more fully understand application scheme, below in conjunction in the embodiment of the present application
Attached drawing, the technical scheme in the embodiment of the application is clearly and completely described, it is clear that described embodiment is only
The embodiment of the application a part, instead of all the embodiments.
Embodiment 1
Prepare porous SnO2-xNanometer sheet:
(1) sulphur powder of 800mg is added in the oleyl amine of 30mL, under an inert atmosphere, is heated to 100 DEG C and keeps two small
When, to remove moisture and oxygen, then Temperature fall to room temperature；
(2 by a certain amount of SnCl4It injects in above-mentioned solution, is slowly warming up to 200 DEG C, and kept for 3 hours；
(3) after natural cooling, centrifugation, several times, 60 DEG C of vacuum drying obtain SnS for chloroform and dehydrated alcohol washing2It receives
Rice piece.
(4) by a certain amount of resulting SnS2Nanometer sheet is dispersed in 20mL water, is stirred 2 days at room temperature, centrifugation, ethanol washing
Afterwards, vacuum drying is to get SnO2-x。
Fig. 1 shows the SnO2-xThe scanning electron microscope diagram (SEM) of nanometer sheet, it can be seen that should from Fig. 1 a and b
SnO2-xPattern is nanometer sheet.
Embodiment 2
The preparation of battery:
(1) it will be enriched in the SnO of oxygen defect2-xNanometer sheet nanometer sheet, conductive carbon black gather inclined tetrafluoroethene with mass ratio 8:1:1
~6:3:1 grinding uniformly, is then transferred into vial, suitable N-Methyl pyrrolidone is added, stir into homogenate；
(2) slurry by above-mentioned preparation is evenly coated on carbon paper, is dried in a vacuum drying oven, is then cut into diameter and is
1.4 centimetres of disk, i.e., it is positive, it is then transferred into glove box；
(3) in glove box, magnesium sheet is polishing to light with golden mesh sand paper, wipes clean rear naturally dry with anhydrous acetonitrile,
It is cut into the disk that diameter is 1.2 centimetres, i.e. cathode；
(4) battery assembles: anode cover upward, thickness 0.05mm, 2.0 centimetres of diameter of molybdenum sheet is put into, for protecting electricity
Then anode is put by casing upward, be put into diaphragm and instill appropriate electrolyte later, then successively by magnesium sheet cathode, gasket and bullet
Piece is put into, and finally buckles negative electrode casing, and (Fig. 2) is packaged to it with battery sealing machine；
(5) battery standing 12~24 hours, setup test.
Embodiment 3
Electrochemical property test:
Magnesium cell is in anhydrous and oxygen-free full of assembling in argon gas glove box, and electrochemical property test is in blue electrical testing
It is completed in system (LAND).
Blue electrical measurement test system is opened, experiment parameter, starting test are set.
SnO rich in oxygen defect2-xNanometer sheet is used for magnesium cell anode, shows good chemical property.Fig. 3 a and b
It is SnO respectively2-xWhen nanometer sheet is as magnesium electricity anode, charging and discharging curve and multiplying power test under different current densities can be seen
Out, which has preferable high rate performance in 0.05~2.1V voltage range.Fig. 4 is SnO2-xCathode is in 300mA g-1Electric current
Long circulating test when density, it can be seen that its maximum specific discharge capacity is up to 106mAh g-1, specific capacity after circulation 300 is enclosed
Still up to 91mAh g-1。
The present invention has synthesized the SnO rich in oxygen defect by atom method of substitution2-xNanometer sheet, and it is used for magnesium ion electricity
Pond anode, this chemical property that electrode is promoted by introducing defect into material have the development of magnesium cell important
Meaning.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application.
Claims (10)
1. the magnesium cell that a kind of tin oxide nano piece to be rich in oxygen defect is anode, which is characterized in that the magnesium cell packet
It includes: negative electrode casing, elastic slice, gasket, cathode, diaphragm, anode, molybdenum sheet, anode cover, electrolyte；The cathode is rich in oxygen defect
Tin oxide nano piece；The cathode is magnesium foil.
2. the magnesium cell that the tin oxide nano piece according to claim 1 to be rich in oxygen defect is anode, which is characterized in that
The diaphragm is glass fibre membrane.
3. the magnesium cell that the tin oxide nano piece according to claim 1 to be rich in oxygen defect is anode, which is characterized in that
The electrolyte is phenyl-magnesium-chloride/aluminium chloride tetrahydrofuran solution.
4. the magnesium cell that the tin oxide nano piece according to claim 1 to be rich in oxygen defect is anode, which is characterized in that
The metal of the anode cover is molybdenum, tungsten, tantalum.
5. the magnesium cell that the tin oxide nano piece according to claim 1 to be rich in oxygen defect is anode, which is characterized in that
The tin oxide nano piece rich in oxygen defect obtains by the following method:
(1) sulphur powder is added in oleyl amine, under an inert atmosphere, is heated to 90~120 DEG C and is kept for two hours, to remove moisture
And oxygen, then Temperature fall to room temperature；
(2) by SnCl4It injects in above-mentioned solution, is slowly warming up to 150~250 DEG C, and kept for 2~5 hours；
(3) after natural cooling, centrifugation, chloroform and dehydrated alcohol washing several times, after 50~80 DEG C of vacuum drying, obtain SnS2
Nanometer sheet；
(4) by resulting SnS2Nanometer sheet is dispersed in water, and is stirred 2~5 days at room temperature, centrifugation, after ethanol washing, vacuum drying,
Up to the tin oxide nano piece for being rich in oxygen defect.
6. the magnesium cell that the tin oxide nano piece according to claim 5 to be rich in oxygen defect is anode, which is characterized in that
The dosage of reactant are as follows: every 20~40mL oleyl amine, corresponding 20~30mmol of sulphur powder dosage, corresponding SnCl414~22mmol of dosage.
7. the magnesium cell that the tin oxide nano piece according to claim 1 to be rich in oxygen defect is anode, which is characterized in that
The described anode obtains by the following method: will be enriched in the tin oxide nano piece of oxygen defect, acetylene black and gather inclined tetrafluoroethene by
The mass ratio grinding of 8:1:1 uniformly, is added N-Methyl pyrrolidone and homogenate is made, be coated on carbon paper, and in 50~80 DEG C of vacuum
It is 10~20 hours dry, the disk being then cut into, i.e. magnesium cell cathode.
8. the magnesium cell that the tin oxide nano piece according to claim 7 to be rich in oxygen defect is anode, which is characterized in that
The additional amount of the N-Methyl pyrrolidone is that every 1.0g SnS uses 4~5mL N-Methyl pyrrolidone.
9. the magnesium cell that the tin oxide nano piece according to claim 1 to be rich in oxygen defect is anode, which is characterized in that
The cathode obtains by the following method: will be polishing to light with SiC sand paper with a thickness of the magnesium foil of 0.05mm, is then cut into small
Disk is as magnesium cell cathode.
10. the tin oxide nano piece according to claim 9 to be rich in oxygen defect is the magnesium cell of anode, feature exists
In the magnesium foil is with a thickness of 0.05mm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910060563.2A CN109935826A (en) | 2019-01-22 | 2019-01-22 | A kind of tin oxide nano piece to be rich in oxygen defect is the magnesium cell of anode |
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| CN201910060563.2A CN109935826A (en) | 2019-01-22 | 2019-01-22 | A kind of tin oxide nano piece to be rich in oxygen defect is the magnesium cell of anode |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110396701A (en) * | 2019-08-19 | 2019-11-01 | 青岛科技大学 | A kind of efficient electro-catalysis reduction carbon dioxide prepares catalyst of formic acid and preparation method thereof |
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| CN103534853A (en) * | 2011-03-08 | 2014-01-22 | 派立昂技术公司 | Rechargeable magnesium ion cell components and assembly |
| CN103872375A (en) * | 2014-03-07 | 2014-06-18 | 上海交通大学 | Application method of disulfide in rechargeable magnesium battery |
| WO2015160944A1 (en) * | 2014-04-15 | 2015-10-22 | North Carolina Agricultural And Technical State University | Paper-based magnesium battery and the use thereof |
| CN105514425A (en) * | 2015-12-11 | 2016-04-20 | 南开大学 | High-performance indoor-temperature sodium ion battery and preparation method thereof |
| CN108630911A (en) * | 2018-03-02 | 2018-10-09 | 杭州电子科技大学 | A kind of SnO of oxygen-containing vacancy defect2Graphene nanocomposite material and application in room temperature sodium-ion battery cathode |
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2019
- 2019-01-22 CN CN201910060563.2A patent/CN109935826A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103534853A (en) * | 2011-03-08 | 2014-01-22 | 派立昂技术公司 | Rechargeable magnesium ion cell components and assembly |
| CN103872375A (en) * | 2014-03-07 | 2014-06-18 | 上海交通大学 | Application method of disulfide in rechargeable magnesium battery |
| WO2015160944A1 (en) * | 2014-04-15 | 2015-10-22 | North Carolina Agricultural And Technical State University | Paper-based magnesium battery and the use thereof |
| CN105514425A (en) * | 2015-12-11 | 2016-04-20 | 南开大学 | High-performance indoor-temperature sodium ion battery and preparation method thereof |
| CN108630911A (en) * | 2018-03-02 | 2018-10-09 | 杭州电子科技大学 | A kind of SnO of oxygen-containing vacancy defect2Graphene nanocomposite material and application in room temperature sodium-ion battery cathode |
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| YANRONG WANG ET AL.: "Atomic Substitution Enabled Synthesis of Vacancy-Rich Two-Dimensional Black TiO2–x Nanoflakes for High-Performance Rechargeable Magnesium Batteries", 《ACS NANO》 * |
| 李艳阳等: "镁二次电池正极材料研究进展", 《材料导报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110396701A (en) * | 2019-08-19 | 2019-11-01 | 青岛科技大学 | A kind of efficient electro-catalysis reduction carbon dioxide prepares catalyst of formic acid and preparation method thereof |
| CN110396701B (en) * | 2019-08-19 | 2021-10-22 | 青岛科技大学 | Electrode for preparing formic acid by efficiently electro-catalytically reducing carbon dioxide |
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Application publication date: 20190625 |
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