CN109768259A - A kind of graded structure germanium dioxide of Fe2O3 doping - Google Patents
A kind of graded structure germanium dioxide of Fe2O3 doping Download PDFInfo
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- CN109768259A CN109768259A CN201910062463.3A CN201910062463A CN109768259A CN 109768259 A CN109768259 A CN 109768259A CN 201910062463 A CN201910062463 A CN 201910062463A CN 109768259 A CN109768259 A CN 109768259A
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- germanium dioxide
- fe2o3 doping
- graded structure
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- structure germanium
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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 by GeO the invention discloses a kind of graded structure germanium dioxide of Fe2O3 doping2And FeCl3·6H2O is put in proportion into the mixed solution of ethanol amine and ethyl alcohol composition, after adjusting pH with 2- methyl piperazine, through simple solvent thermal response, dries, the graded structure germanium dioxide of the Fe2O3 doping is made in annealing.Resulting materials have good electrochemical stability and higher specific capacity, can be used for preparing lithium ion battery.
Description
Technical field
The invention belongs to lithium ion battery material technical fields, and in particular to a kind of graded structure titanium dioxide of Fe2O3 doping
Germanium.
Background technique
Germanium sill because of theoretical capacity with higher, and than the silicon of same main group have higher electric conductivity and by extensive
Concern.But since there are biggish volume expansions during embedding de- lithium for the substance, so that active material be easily caused to exist
Generated on pole piece it is serious fall off, and decline cyclical stability sharply, this is but also such material above receives very in application
Big limitation.Germanium dioxide is as a kind of conversion hysteria germanium base negative electrode material, because having very high theoretical capacity to be closed extensively by everybody
Note, however due to conversion reaction that itself and lithium ion occur be considered as it is irreversible, it is significant that this allows for capacity attenuation speed
Accelerate.The present invention can be such that the chemical property of germanium dioxide is significantly promoted by Fe2O3 doping, and not yet have to use at present and mix
Miscellaneous means are applied to lithium ion battery with excellent storage lithium the method that synthesizes graded structure germanium dioxide
Performance, therefore the germanium dioxide for preparing Fe2O3 doping has important research significance.
Summary of the invention
To improve above-mentioned phenomenon, the present invention provides a kind of graded structure germanium dioxide of Fe2O3 doping for the first time, passes through letter
Single ground solvent-thermal method realizes in situ doping of the transition metal iron in germanium dioxide matrix, and using molysite as structure directing agent
So that germanium dioxide is self-assembled into graded structure after dissolution, and there is good electrochemical stability and higher specific volume
Amount, suitable for preparing lithium ion battery.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of graded structure germanium dioxide of Fe2O3 doping, preparation method include the following steps:
1) by GeO2And FeCl3·6H210:1 puts into mixed solution (ethanol amine and the second that ethanol amine and ethyl alcohol form to O in molar ratio
The volume ratio of alcohol is 1:2) in, 2- methyl piperazine is added then to adjust pH value of solution > 7；
2) mixture obtained by step 1) is placed in polytetrafluoroethyl-ne alkene reaction liner, in reacting 24 hours in 180 DEG C of baking ovens, then
It is cooled to room temperature；
3) it after products therefrom is washed with deionized for several times, is dried 12 hours in 70 DEG C of baking ovens, obtains Fe-GeO2Yellow powder
End；
4) gained yellow powder is annealed 1 hour in ar gas environment, under the conditions of 550-650 DEG C, obtains point of the Fe2O3 doping
Hierarchical organization germanium dioxide.
The graded structure germanium dioxide of gained Fe2O3 doping can be used for preparing lithium ion battery.
Remarkable advantage of the invention is:
First passage Fe2O3 doping of the present invention improves the property of germanium sill, and wherein molysite serves not only as structure directing agent, so that
Germanium dioxide main body becomes graduation nanometer sheet and is self-assembled into a micron floral structure, to improve material electrochemical stability, and can
The volume expansion of classification buffering germanium dioxide, and iron atom can be used as dopant simultaneously after calcining, mix GeO2Lattice
Inside increases more embedding lithium sites, to improve the specific capacity of material so that distortion of lattice, causes lattice defect.And
The use of 2- methyl piperazine can also introduce many active sites while increasing electric conductivity, to increase embedding lithium site, further
Improve the specific capacity of material.
Electrochemical research the result shows that, using graded structure Fe2O3 doping germanium dioxide of the present invention prepare lithium ion battery
Under the current density of 0.5A/g, by the charge and discharge cycles of 300 circles, capacity still can achieve 1114.1 mAh/g.
Detailed description of the invention
Fig. 1 is doping and undoped germanium dioxide XRD spectra.
Fig. 2 is the scanning electron microscope (SEM) photograph of the germanium dioxide micro-flowers of Fe2O3 doping.
Fig. 3 is the chemical property figure of the germanium dioxide micro-flowers of Fe2O3 doping.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
Embodiment
1) by 1 mmol GeO2With 0.1 mmol FeCl3·6H2O puts into 5-10 ml ethanol amine and 10-20 ml ethanol group
At mixed solution (the two volume ratio be 1:2) in, 2- methyl piperazine is added then to adjust pH value of solution > 7；
2) mixture obtained by step 1) is placed in polytetrafluoroethyl-ne alkene reaction liner, in reacting 24 hours in 180 DEG C of baking ovens, then
It is cooled to room temperature；
3) it after products therefrom is washed with deionized for several times, is dried 12 hours in 70 DEG C of baking ovens, obtains Fe-GeO2Yellow powder
End；
4) gained yellow powder is annealed 1 hour in ar gas environment, under the conditions of 550-650 DEG C, obtains point of the Fe2O3 doping
Hierarchical organization germanium dioxide.
Doping is shown in Fig. 1 with undoped germanium dioxide XRD spectra.As seen from Figure 1, two lines belong to the two of pure phase
Germanium oxide, no other miscellaneous peaks exist, and from the picture of amplification can be seen that doping after germanium dioxide peak it is obviously inclined toward low-angle
It moves, it was demonstrated that the successful synthesis of Fe2O3 doping germanium dioxide.
The scanning electron microscope (SEM) photograph of the germanium dioxide micro-flowers of Fe2O3 doping is shown in Fig. 2.From Figure 2 it can be seen that it is by nanometer sheet self assembly
Made of micro-flowers, size is about 2 μm.
Lithium battery assembling:
It will be uniform after graded structure germanium dioxide, Kynoar, acetylene black the 7:2:1 mixed grinding in mass ratio of Fe2O3 doping
Ground, which is coated on copper mesh, does cathode, reference electrode and be lithium metal to electrode, and electrolyte is by 1M LiPF6EC+DMC+EMC
(v/v of EC/DMC/EMC=1/1/1) solution.All assemblings carry out in glove box.
Electrochemical property test result is shown in Fig. 3.As seen from Figure 3, the charge and discharge cycles enclosed by 300, gained lithium battery
Capacity still can achieve 1114.1 mAh/g, and still with the Fabrication of High Specific Capacitance of 511 mAh/g under the current density of 10 Ah/g
Amount, shows excellent high rate performance.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (4)
1. a kind of graded structure germanium dioxide of Fe2O3 doping, it is characterised in that: preparation method includes the following steps:
1) by GeO2And FeCl3·6H2O put into ethanol amine and ethyl alcohol composition mixed solution in, then be added 2- methyl piperazine with
Adjust pH value of solution > 7；
2) mixture obtained by step 1) is placed in polytetrafluoroethyl-ne alkene reaction liner, in reacting 24 hours in 180 DEG C of baking ovens, then
It is cooled to room temperature；
3) it is dried 12 hours after products therefrom is washed with deionized in 70 DEG C, obtains Fe-GeO2Yellow powder；
4) gained yellow powder is annealed 1 hour in ar gas environment, under the conditions of 550-650 DEG C, obtains point of the Fe2O3 doping
Hierarchical organization germanium dioxide.
2. the graded structure germanium dioxide of Fe2O3 doping according to claim 1, it is characterised in that: GeO used2With
FeCl3·6H2The molar ratio of O is 10:1.
3. the graded structure germanium dioxide of Fe2O3 doping according to claim 1, it is characterised in that: the ethanol amine and second
In the mixed solution of alcohol composition, the volume ratio of ethanol amine and ethyl alcohol is 1:2.
4. a kind of graded structure germanium dioxide of Fe2O3 doping as described in claim 1 is preparing the application in lithium ion battery.
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| CN201910062463.3A CN109768259B (en) | 2019-01-23 | 2019-01-23 | Iron-doped germanium dioxide with hierarchical structure |
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| CN201910062463.3A CN109768259B (en) | 2019-01-23 | 2019-01-23 | Iron-doped germanium dioxide with hierarchical structure |
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| CN109768259A true CN109768259A (en) | 2019-05-17 |
| CN109768259B CN109768259B (en) | 2021-04-27 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790304A (en) * | 2019-11-13 | 2020-02-14 | 福州大学 | Preparation of germanium dioxide/nitrogen-doped carbon composite material with sea urchin-shaped structure and application of composite material in lithium ion battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120080648A1 (en) * | 2010-10-01 | 2012-04-05 | Ali Abouimrane | Anode materials for lithium ion batteries |
| CN103964492A (en) * | 2014-05-16 | 2014-08-06 | 安徽师范大学 | GeOx material, preparation method thereof and application of GeOx material in lithium ion battery |
| US20150171426A1 (en) * | 2011-12-02 | 2015-06-18 | Brookhaven Science Associates, Llc | POROUS AMORPHOUS GeOx AND ITS APPLICATION AS AN ANODE MATERIAL IN LI-ION BATTERIES |
| CN106950274A (en) * | 2017-04-06 | 2017-07-14 | 吉林大学 | A kind of dimethylbenzene gas sensor for the NiO graded structures nanometer bouquet sensitive material that adulterated based on Sn and preparation method thereof |
-
2019
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120080648A1 (en) * | 2010-10-01 | 2012-04-05 | Ali Abouimrane | Anode materials for lithium ion batteries |
| US20150171426A1 (en) * | 2011-12-02 | 2015-06-18 | Brookhaven Science Associates, Llc | POROUS AMORPHOUS GeOx AND ITS APPLICATION AS AN ANODE MATERIAL IN LI-ION BATTERIES |
| CN103964492A (en) * | 2014-05-16 | 2014-08-06 | 安徽师范大学 | GeOx material, preparation method thereof and application of GeOx material in lithium ion battery |
| CN106950274A (en) * | 2017-04-06 | 2017-07-14 | 吉林大学 | A kind of dimethylbenzene gas sensor for the NiO graded structures nanometer bouquet sensitive material that adulterated based on Sn and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790304A (en) * | 2019-11-13 | 2020-02-14 | 福州大学 | Preparation of germanium dioxide/nitrogen-doped carbon composite material with sea urchin-shaped structure and application of composite material in lithium ion battery |
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