CN109585836A - A kind of antimony based micro-nano heterojunction material and its preparation method and application - Google Patents
A kind of antimony based micro-nano heterojunction material and its preparation method and application Download PDFInfo
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Abstract
The present invention is a kind of antimony based micro-nano heterojunction material and its preparation method and application, its main feature is that, preparation method is used only under the method for calcination in air or fixed atmosphere and makes annealing treatment method, by one-step oxidation process oxidation processes will be carried out to antimony trisulfide or antimony selenide material, one layer of antimony oxide of appearance uniform fold, the antimony based micro-nano heterojunction material that package antimony trisulfide or antimony selenide are formed in antimony oxide layer is prepared.That is the antimony oxide of N-shaped, core are the antimony trisulfide or antimony selenide of p-type, and the two contacts with each other composition heterojunction structure, and as the negative electrode material of the secondary cells such as sodium-ion battery or lithium ion battery, significantly improves battery performance.
Description
Technical field
It is a kind of antimony based micro-nano heterojunction material and preparation method thereof the present invention relates to energy storage field of material technology
And application.
Background technique
The energy storage with conversion from become restrict world today's energy industry develop biggest obstacle, at present compared with
Be secondary cell for effective energy storage means, lithium ion battery technology is very mature, sodium-ion battery as lithium from
Effective replacer of sub- battery also has huge development potentiality.In the research of secondary cell, the selection of cell negative electrode material
There is very important status.Antimony-based compounds are because its higher theoretical capacity and lower material cost have become at present
Research hot topic, including antimony trisulfide, antimony selenide, antimony oxide etc. in negative electrode material.But research finds that antimony-based compounds are filling
There is very serious volume expansion problem in discharge process, keeps the broken powdered of electrode material serious, so as to cause the circulation of battery
Stability and capacity substantially reduce, and seriously constrain its extensive use in terms of energy storage.
Research finds the material of two kinds of different band gaps carrying out combined processing, constructs heterojunction structure, in hetero-junctions
The induction field that portion generates in charge and discharge process can greatly promote the transmission speed of charge and ion, at the same the two is compound can
It is effective to alleviate volume expansion problem, so as to improve the low problem with cyclical stability difference of its capacity.It finds after further study
Antimony-based compounds and the compound of antimony oxide will construct the heterojunction structure for being conducive to material electrochemical performance, and construct at present different
The method of matter junction structure is commonly two one-step hydrothermals or solvent-thermal method, and it is various that there is steps, and process is complicated, and Variable Control is difficult,
The disadvantages of energy consumption is big.
Therefore become very necessary using a kind of simple method synthesis antimony based micro-nano heterojunction material, also exactly big rule
Urgently needed for mould energy-storage system.
Summary of the invention
The object of the present invention is to overcome the deficiencies of the prior art and provide a kind of antimony based micro-nano of excellent electrochemical performance
Heterojunction material；And provide scientific and reasonable, simple to be applicable in, easy to operate, safety and environmental protection, the period is short, is suitble to large-scale industrial raw
The antimony based micro-nano heterojunction material preparation method of production；And antimony based micro-nano heterojunction material is provided as secondary battery negative pole
Using
Realize one of the object of the invention the technical solution adopted is that: a kind of preparation method of antimony based micro-nano heterojunction material,
It is characterized in that, oxidation processes is carried out to antimony trisulfide or antimony selenide material, one layer of antimony oxide of appearance uniform fold is prepared, are aoxidized
The antimony based micro-nano heterojunction material that cladding antimony trisulfide or antimony selenide are formed in antimony layer.
Further, the oxidation processes use one-step oxidation process, in the antimony trisulfide of p-type or the table of antimony selenide micro Nano material
Face forms the antimony oxide of N-shaped, the one-step oxidation process that specific oxidation processes use are as follows:
1) using calcination method in air:
1. antimony trisulfide material is placed on heated at constant temperature platform, 350-500 DEG C of temperature, calcination time 2-15 min is aoxidized
Antimony trisulfide heterojunction material is coated in antimony layer；
2. antimony selenide material is placed on heated at constant temperature platform, 400-550 DEG C of temperature, calcination time 2-15min obtains antimony oxide
Antimony selenide heterojunction material is coated in layer；
2) using annealing method under fixed atmosphere:
3. antimony trisulfide material is placed in vacuum heater, atmosphere selects 40% oxygen, 60% nitrogen, flow velocity 30-60
300-450 DEG C of temperature, annealing time 3-8min, it is heterogeneous to obtain cladding antimony trisulfide in antimony oxide layer by sccm, atmosphere pressures 100Pa
Tie material；
4. antimony selenide material is placed in vacuum heater, atmosphere selects 40% oxygen, 60% nitrogen, flow velocity 30-60
350-500 DEG C of temperature, annealing time 3-8min, it is heterogeneous to obtain cladding antimony selenide in antimony oxide layer by sccm, atmosphere pressures 100Pa
Tie material.
Further, the antimony based micro-nano heterojunction material being prepared is three-dimensional spherical shape, cube, can be two
The nanobelt of dimension, nanometer sheet, or one-dimensional nanowire structure, scale is in 200nm to 2 μ ms.
Realize the object of the invention two the technical solution adopted is that: a kind of preparation method of antimony based micro-nano heterojunction material
The antimony based micro-nano heterojunction material directly obtained.
Realize the object of the invention three the technical solution adopted is that: the antimony based micro-nano heterojunction material being prepared
In the application of sodium-ion battery or lithium ion battery negative material.
A kind of having the beneficial effect that for antimony based micro-nano heterojunction material of the invention and its preparation method and application is obtained
Antimony based micro-nano heterojunction material structure, outer layer is the antimony oxide layer uniformly coated, and kernel is antimony trisulfide or antimony selenide, oxygen
Change antimony is n-type semiconductor, and antimony trisulfide or antimony selenide are p-type semiconductor, and the two forms hetero-junctions by contact, in charge and discharge process
In can all form induction field, promote the transmission of ion and electronics, so as to improve the chemical property of material, antimony based micro-nano is different
The preparation method of matter knot material is aoxidized using calcination in air or the method annealed under fixed atmosphere, simplifies synthesis step
Suddenly, synthesis cost is reduced, methodological science is reasonable, and simple to be applicable in, easy to operate, safety and environmental protection, the period is short, is suitble to scale chemical industry
Industry production；It is high using the sodium-ion battery or specific capacity of negative electrode material of lithium ion battery of antimony based micro-nano heterojunction material preparation,
Good cycle, high rate performance are good.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is that a kind of preparation method of antimony based micro-nano heterojunction material of the present invention obtains coating antimony trisulfide in antimony oxide layer
The XRD diagram of heterojunction material；
Fig. 2 is a kind of charging and discharging curve figure of the antimony based micro-nano heterojunction material of the present invention at 100mA/g；
Specific embodiment
Below in conjunction with drawings and examples, the present invention will be described in detail, and described embodiment is only of the invention one
Section Example, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not doing
Every other embodiment obtained under the premise of creative work out, shall fall within the protection scope of the present invention.
Preparation method is illustrated with reference to the accompanying drawings and examples, it is to be understood that, embodiment is only intended to illustrate
The present invention, and and be not in any way limit the scope of the present invention.
A kind of preparation method of antimony based micro-nano heterojunction material of the invention, particular content are as follows: to antimony trisulfide or selenizing
Antimony material carries out oxidation processes, and one layer of antimony oxide of appearance uniform fold, cladding antimony trisulfide or selenizing in antimony oxide layer is prepared
The antimony based micro-nano heterojunction material that antimony is formed.
Further, the oxidation processes use one-step oxidation process, in the antimony trisulfide of p-type or the table of antimony selenide micro Nano material
Face forms the antimony oxide of N-shaped, the one-step oxidation process that specific oxidation processes use are as follows:
1) using calcination method in air:
1. antimony trisulfide material is placed on heated at constant temperature platform, 350-500 DEG C of temperature, calcination time 2-15 min is aoxidized
Antimony trisulfide heterojunction material is coated in antimony layer；
2. antimony selenide material is placed on heated at constant temperature platform, 400-550 DEG C of temperature, calcination time 2-15min obtains antimony oxide
Antimony selenide heterojunction material is coated in layer；
2) using annealing method under fixed atmosphere:
3. antimony trisulfide material is placed in vacuum heater, atmosphere selects 40% oxygen, 60% nitrogen, flow velocity 30-60
300-450 DEG C of temperature, annealing time 3-8min, it is heterogeneous to obtain cladding antimony trisulfide in antimony oxide layer by sccm, atmosphere pressures 100Pa
Tie material；
4. antimony selenide material is placed in vacuum heater, atmosphere selects 40% oxygen, 60% nitrogen, flow velocity 30-60
350-500 DEG C of temperature, annealing time 3-8min, it is heterogeneous to obtain cladding antimony selenide in antimony oxide layer by sccm, atmosphere pressures 100Pa
Tie material.
Further, the antimony based micro-nano heterojunction material being prepared is three-dimensional spherical shape, cube, can be two
The nanobelt of dimension, nanometer sheet, or one-dimensional nanowire structure, scale is in 200nm to 2 μ ms.
A kind of antimony based micro-nano heterojunction material that the preparation method of antimony based micro-nano heterojunction material directly obtains.
The antimony based micro-nano heterojunction material being prepared is in sodium-ion battery or lithium ion battery negative material
Using.
Embodiment 1: a kind of preparation method of antimony based micro-nano heterojunction material, particular content are as follows: to antimony trisulfide material into
One layer of antimony oxide of appearance uniform fold, the antimony base micro-nano that cladding antimony trisulfide is formed in antimony oxide layer is prepared in row oxidation processes
Rice heterojunction material.
Further, the oxidation processes use one-step oxidation process, form n on the surface of the antimony trisulfide micro Nano material of p-type
The antimony oxide of type, the one-step oxidation process that specific oxidation processes use are as follows: calcination method in air；
Using calcination method in air: antimony trisulfide material being placed on heated at constant temperature platform, 350 DEG C of temperature, calcination time 2min is obtained
Antimony trisulfide heterojunction material is coated in antimony oxide layer.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 2 is substantially the same manner as Example 1, difference
It is, using calcination method in air: antimony trisulfide material being placed on heated at constant temperature platform, 425 DEG C of temperature, calcination time 8min is obtained
Antimony trisulfide heterojunction material is coated in antimony oxide layer.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 3 is substantially the same manner as Example 1, difference
It is, using calcination method in air: antimony trisulfide material being placed on heated at constant temperature platform, 500 DEG C of temperature, calcination time 15min is obtained
Antimony trisulfide heterojunction material is coated in antimony oxide layer.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 4 is substantially the same manner as Example 1, difference
It is, using calcination method in air: antimony trisulfide material being placed on heated at constant temperature platform, 350 DEG C of temperature, calcination time 15min is obtained
Antimony trisulfide heterojunction material is coated in antimony oxide layer.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 5 is substantially the same manner as Example 1, difference
It is, using calcination method in air: antimony trisulfide material being placed on heated at constant temperature platform, 500 DEG C of temperature, calcination time 2min is obtained
Antimony trisulfide heterojunction material is coated in antimony oxide layer.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 6 is substantially the same manner as Example 1, difference
It is, using calcination method in air: antimony trisulfide material being placed on heated at constant temperature platform, 350 DEG C of temperature, calcination time 8min is obtained
Antimony trisulfide heterojunction material is coated in antimony oxide layer.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 7 is substantially the same manner as Example 1, difference
It is, using calcination method in air: antimony trisulfide material being placed on heated at constant temperature platform, 500 DEG C of temperature, calcination time 8min is obtained
Antimony trisulfide heterojunction material is coated in antimony oxide layer.
Embodiment 8: a kind of preparation method of antimony based micro-nano heterojunction material, particular content are as follows: to antimony selenide material into
One layer of antimony oxide of appearance uniform fold, the antimony base micro-nano that cladding antimony selenide is formed in antimony oxide layer is prepared in row oxidation processes
Rice heterojunction material.
Further, the oxidation processes use one-step oxidation process, form n on the surface of the antimony selenide micro Nano material of p-type
The antimony oxide of type, the one-step oxidation process that specific oxidation processes use are as follows: calcination method in air；
Using calcination method in air: antimony selenide material being placed on heated at constant temperature platform, 400 DEG C of temperature, calcination time 2min is obtained
Antimony selenide heterojunction material is coated in antimony oxide layer.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 9 is substantially the same manner as Example 8, difference
It is, using calcination method in air: antimony selenide material being placed on heated at constant temperature platform, 475 DEG C of temperature, calcination time 8min is obtained
Antimony selenide heterojunction material is coated in antimony oxide layer.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 10 is substantially the same manner as Example 8, difference
Place is, using calcination method in air: antimony selenide material is placed on heated at constant temperature platform, 550 DEG C of temperature, calcination time 15min,
It obtains coating antimony selenide heterojunction material in antimony oxide layer.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 11 is substantially the same manner as Example 8, difference
Place is, using calcination method in air: antimony selenide material is placed on heated at constant temperature platform, 400 DEG C of temperature, calcination time 15min,
It obtains coating antimony selenide heterojunction material in antimony oxide layer.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 12 is substantially the same manner as Example 8, difference
Place is, using calcination method in air: antimony selenide material is placed on heated at constant temperature platform, 550 DEG C of temperature, calcination time 2min,
It obtains coating antimony selenide heterojunction material in antimony oxide layer.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 13 is substantially the same manner as Example 8, difference
Place is, using calcination method in air: antimony selenide material is placed on heated at constant temperature platform, 400 DEG C of temperature, calcination time 8min,
It obtains coating antimony selenide heterojunction material in antimony oxide layer.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 14 is substantially the same manner as Example 8, difference
Place is, using calcination method in air: antimony selenide material is placed on heated at constant temperature platform, 550 DEG C of temperature, calcination time 8min,
It obtains coating antimony selenide heterojunction material in antimony oxide layer.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 15, particular content are as follows: to antimony trisulfide material
Oxidation processes are carried out, one layer of antimony oxide of appearance uniform fold is prepared, the antimony base that cladding antimony trisulfide is formed in antimony oxide layer is micro-
Nano heterojunction material.
Further, the oxidation processes use one-step oxidation process, form n on the surface of the antimony trisulfide micro Nano material of p-type
The antimony oxide of type, the one-step oxidation process that specific oxidation processes use are as follows: annealing method under fixed atmosphere:
Using annealing method under fixed atmosphere: antimony trisulfide material is placed in vacuum heater, atmosphere selects 40% oxygen,
60% nitrogen, flow velocity 30sccm, atmosphere pressures 100Pa, obtain coating sulphur in antimony oxide layer by 300 DEG C of temperature, annealing time 3min
Change antimony heterojunction material.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 16 is substantially the same manner as Example 15, difference
Place is, using annealing method under fixed atmosphere: antimony trisulfide material is placed in vacuum heater, atmosphere selects 40% oxygen,
60% nitrogen, flow velocity 30sccm, atmosphere pressures 100Pa, obtain coating sulphur in antimony oxide layer by 450 DEG C of temperature, annealing time 8min
Change antimony heterojunction material.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 17 is substantially the same manner as Example 15, difference
Place is, using annealing method under fixed atmosphere: antimony trisulfide material is placed in vacuum heater, atmosphere selects 40% oxygen,
60% nitrogen, flow velocity 45sccm, atmosphere pressures 100Pa, obtain coating sulphur in antimony oxide layer by 375 DEG C of temperature, annealing time 5min
Change antimony heterojunction material.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 18 is substantially the same manner as Example 15, difference
Place is, using annealing method under fixed atmosphere: antimony trisulfide material is placed in vacuum heater, atmosphere selects 40% oxygen,
60% nitrogen, flow velocity 60 sccm, atmosphere pressures 100Pa, obtains coating sulphur in antimony oxide layer by 450 DEG C of temperature, annealing time 8min
Change antimony heterojunction material.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 19 is substantially the same manner as Example 15, difference
Place is, using annealing method under fixed atmosphere: antimony trisulfide material is placed in vacuum heater, atmosphere selects 40% oxygen,
60% nitrogen, flow velocity 45 sccm, atmosphere pressures 100Pa, obtains coating sulphur in antimony oxide layer by 375 DEG C of temperature, annealing time 6min
Change antimony heterojunction material.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 20 is substantially the same manner as Example 15, difference
Place is, using annealing method under fixed atmosphere: antimony trisulfide material is placed in vacuum heater, atmosphere selects 40% oxygen,
60% nitrogen, flow velocity 60 sccm, atmosphere pressures 100Pa, obtains coating sulphur in antimony oxide layer by 300 DEG C of temperature, annealing time 3min
Change antimony heterojunction material.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 21 is substantially the same manner as Example 15, difference
Place is, using annealing method under fixed atmosphere: antimony trisulfide material is placed in vacuum heater, atmosphere selects 40% oxygen,
60% nitrogen, flow velocity 45 sccm, atmosphere pressures 100Pa, obtains coating sulphur in antimony oxide layer by 350 DEG C of temperature, annealing time 4min
Change antimony heterojunction material.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 22, particular content are as follows: to antimony selenide material
Oxidation processes are carried out, one layer of antimony oxide of appearance uniform fold is prepared, the antimony base that cladding antimony selenide is formed in antimony oxide layer is micro-
Nano heterojunction material.
Further, the oxidation processes use one-step oxidation process, form n on the surface of the antimony selenide micro Nano material of p-type
The antimony oxide of type, the one-step oxidation process that specific oxidation processes use are as follows: annealing method under fixed atmosphere:
Using annealing method under fixed atmosphere: antimony selenide material is placed in vacuum heater, atmosphere selects 40% oxygen,
60% nitrogen, flow velocity 30sccm, atmosphere pressures 100Pa, obtain coating selenium in antimony oxide layer by 350 DEG C of temperature, annealing time 3min
Change antimony heterojunction material.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 23 is substantially the same manner as Example 22, difference
Place is, using annealing method under fixed atmosphere: antimony selenide material is placed in vacuum heater, atmosphere selects 40% oxygen,
60% nitrogen, flow velocity 30sccm, atmosphere pressures 100Pa, obtain coating selenium in antimony oxide layer by 500 DEG C of temperature, annealing time 8min
Change antimony heterojunction material.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 24 is substantially the same manner as Example 22, difference
Place is, using annealing method under fixed atmosphere: antimony selenide material is placed in vacuum heater, atmosphere selects 40% oxygen,
60% nitrogen, flow velocity 45sccm, atmosphere pressures 100Pa, obtain coating selenium in antimony oxide layer by 425 DEG C of temperature, annealing time 5min
Change antimony heterojunction material.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 25 is substantially the same manner as Example 22, difference
Place is, using annealing method under fixed atmosphere: antimony selenide material is placed in vacuum heater, atmosphere selects 40% oxygen,
60% nitrogen, flow velocity 60 sccm, atmosphere pressures 100Pa, obtains coating selenium in antimony oxide layer by 450 DEG C of temperature, annealing time 8min
Change antimony heterojunction material.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 26 is substantially the same manner as Example 22, difference
Place is, using annealing method under fixed atmosphere: antimony selenide material is placed in vacuum heater, atmosphere selects 40% oxygen,
60% nitrogen, flow velocity 45 sccm, atmosphere pressures 100Pa, obtains coating selenium in antimony oxide layer by 375 DEG C of temperature, annealing time 6min
Change antimony heterojunction material.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 27 is substantially the same manner as Example 22, difference
Place is, using annealing method under fixed atmosphere: antimony selenide material is placed in vacuum heater, atmosphere selects 40% oxygen,
60% nitrogen, flow velocity 60sccm, atmosphere pressures 100Pa, obtain coating selenium in antimony oxide layer by 350 DEG C of temperature, annealing time 3min
Change antimony heterojunction material.
A kind of preparation method of antimony based micro-nano heterojunction material of embodiment 28 is substantially the same manner as Example 22, difference
Place is, using annealing method under fixed atmosphere: antimony selenide material is placed in vacuum heater, atmosphere selects 40% oxygen,
60% nitrogen, flow velocity 45sccm, atmosphere pressures 100Pa, obtain coating selenium in antimony oxide layer by 500 DEG C of temperature, annealing time 4min
Change antimony heterojunction material.
Embodiment 29: cladding antimony trisulfide heterojunction material is electric as sodium ion in prepared antimony oxide layer through the invention
The active component of pond negative electrode material, conductive agent are acetylene black, and binder is Kynoar, mass ratio 6:3:1；Electrolyte is
1 mole of trifluoromethayl sulfonic acid sodium (CF3NaO3S diethylene glycol diethyl ether (G2) solution)；Battery case model 2032, collector
For copper sheet, diaphragm is glass fibre；Sodium sheet metal is used to electrode, the assembled battery under the protection of argon gas (0.01 PPM) atmosphere.
Using antimony trisulfide and antimony oxide composite material as the negative electrode material of sodium-ion battery, charge and discharge platform is 2.5 V, in current density
When for 0.1 A/g, first discharge specific capacity reaches 1165.5 mAh/g, and second of charge and discharge reversible specific capacity can reach 670.3
MAh/g, after charge and discharge 5 times, specific capacity remains at 683 mAh/g.
Embodiment 30: cladding antimony selenide heterojunction material is electric as sodium ion in prepared antimony oxide layer through the invention
The active component of pond negative electrode material, conductive agent are acetylene black, and binder is Kynoar, mass ratio 6:3:1；Electrolyte is
1 mole of trifluoromethayl sulfonic acid sodium (CF3NaO3S diethylene glycol diethyl ether (G2) solution)；Battery case model 2032, collector
For copper sheet, diaphragm is glass fibre；Sodium sheet metal is used to electrode, the assembled battery under the protection of argon gas (0.01 PPM) atmosphere.
Using antimony selenide and antimony oxide composite material as the negative electrode material of sodium-ion battery, charge and discharge platform is 2.5 V, in current density
When for 0.1 A/g, first discharge specific capacity reaches 878.4 mAh/g, and second of charge and discharge reversible specific capacity can reach 507.8
MAh/g, after charge and discharge 5 times, specific capacity remains at 509.1 mAh/g.
Embodiment 31: antimony trisulfide heterojunction material is coated in prepared antimony oxide layer through the invention as lithium-ion electric
The active component of pond negative electrode material, conductive agent superP, binder are Kynoar, mass ratio 6:3:1；Electrolyte is
1 mole of lithium perchlorate (LiClO3) diethylene glycol diethyl ether (G2) solution；Battery case model 2032, collector are copper sheet,
Diaphragm is glass fibre；Lithium metal piece is used to electrode, the assembled battery under the protection of argon gas (0.01 PPM) atmosphere.By antimony trisulfide
Negative electrode material with antimony oxide composite material as lithium ion battery, charge and discharge platform are 2.5 V, are 0.1 A/ in current density
When g, first discharge specific capacity reaches 814.9 mAh/g, and second of charge and discharge reversible specific capacity can reach 572.0 mAh/g, fill
After electric discharge 5 times, specific capacity remains at 570.4 mAh/g.
For the antimony sill for using no heterojunction structure, either from effective specific capacity or cyclical stability
On have compared with promotion, this also can more illustrate that heterojunction structure can effectively improve the chemical property of material.
The foregoing description of the disclosed embodiments can be realized those skilled in the art or using the present invention.To reality
The a variety of modifications for applying example will be apparent for a person skilled in the art, and General Principle defined in the present invention can be with
Without departing from the spirit or scope of the present invention, it realizes in other embodiments.Therefore, the present invention will not be limited
The embodiment shown in the present invention, and it is to fit to the widest model consistent with principles of this disclosure and features of novelty
It encloses.
Claims (5)
1. a kind of preparation method of antimony based micro-nano heterojunction material, which is characterized in that carried out to antimony trisulfide or antimony selenide material
One layer of antimony oxide of appearance uniform fold, the antimony that cladding antimony trisulfide or antimony selenide are formed in antimony oxide layer is prepared in oxidation processes
Based micro-nano heterojunction material.
2. a kind of preparation method of antimony based micro-nano heterojunction material according to claim 1, which is characterized in that be prepared into
The antimony based micro-nano heterojunction material arrived is three-dimensional spherical shape, cube, can be two-dimensional nanobelt, nanometer sheet,
It can be one-dimensional nanowire structure, scale is in 200nm to 2 μ ms.
3. a kind of preparation method of antimony based micro-nano heterojunction material according to claim 1, which is characterized in that the oxygen
Change processing and use one-step oxidation process, forms the antimony oxide of N-shaped, tool in the antimony trisulfide of p-type or the surface of antimony selenide micro Nano material
The one-step oxidation process that body oxidation processes use are as follows:
1) using calcination method in air:
1. antimony trisulfide material is placed on heated at constant temperature platform, 350-500 DEG C of temperature, calcination time 2-15 min is aoxidized
Antimony trisulfide heterojunction material is coated in antimony layer；
2. antimony selenide material is placed on heated at constant temperature platform, 400-550 DEG C of temperature, calcination time 2-15min obtains antimony oxide
Antimony selenide heterojunction material is coated in layer；
2) using annealing method under fixed atmosphere:
3. antimony trisulfide material is placed in vacuum heater, atmosphere selects 40% oxygen, 60% nitrogen, flow velocity 30-60
300-450 DEG C of temperature, annealing time 3-8min, it is heterogeneous to obtain cladding antimony trisulfide in antimony oxide layer by sccm, atmosphere pressures 100Pa
Tie material；
4. antimony selenide material is placed in vacuum heater, atmosphere selects 40% oxygen, 60% nitrogen, flow velocity 30-60
350-500 DEG C of temperature, annealing time 3-8min, it is heterogeneous to obtain cladding antimony selenide in antimony oxide layer by sccm, atmosphere pressures 100Pa
Tie material.
4. the antimony base micro-nano that a kind of preparation method of antimony based micro-nano heterojunction material according to claim 1 directly obtains
Rice heterojunction material.
5. a kind of preparation method of antimony based micro-nano heterojunction material according to claim 1, which is characterized in that be prepared into
Application of the antimony based micro-nano heterojunction material arrived in sodium-ion battery or lithium ion battery negative material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112002893A (en) * | 2020-08-26 | 2020-11-27 | 中南大学 | Research of taking antimony-based composite metal sulfide as potassium ion battery negative electrode material |
| CN113675283A (en) * | 2021-08-24 | 2021-11-19 | 昆明理工大学 | Antimony-based photocathode Sb2S3/Sb2O3Heterojunction structure and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86104335A (en) * | 1986-06-20 | 1987-12-16 | 云南工学院 | From low-grade antimony sulfide ore, directly extract the method for stibium trioxide |
| CN102627324A (en) * | 2011-12-09 | 2012-08-08 | 兰州理工大学 | Preparation method of nanometer antimony oxide |
| US20140329355A1 (en) * | 2008-05-09 | 2014-11-06 | International Business Machines Corporation | Techniques for Enhancing Performance of Photovoltaic Devices |
| CN106299316A (en) * | 2016-10-19 | 2017-01-04 | 清华大学深圳研究生院 | A kind of lithium ion battery and negative material thereof and preparation method |
-
2018
- 2018-12-13 CN CN201811528673.9A patent/CN109585836B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86104335A (en) * | 1986-06-20 | 1987-12-16 | 云南工学院 | From low-grade antimony sulfide ore, directly extract the method for stibium trioxide |
| US20140329355A1 (en) * | 2008-05-09 | 2014-11-06 | International Business Machines Corporation | Techniques for Enhancing Performance of Photovoltaic Devices |
| CN102627324A (en) * | 2011-12-09 | 2012-08-08 | 兰州理工大学 | Preparation method of nanometer antimony oxide |
| CN106299316A (en) * | 2016-10-19 | 2017-01-04 | 清华大学深圳研究生院 | A kind of lithium ion battery and negative material thereof and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| GANGQIANG ZHU ET AL.: "Preparation of Sb2S3 film on functional organic self-assembled monolayers by chemical bath deposition", 《J MATER SCI》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112002893A (en) * | 2020-08-26 | 2020-11-27 | 中南大学 | Research of taking antimony-based composite metal sulfide as potassium ion battery negative electrode material |
| CN113675283A (en) * | 2021-08-24 | 2021-11-19 | 昆明理工大学 | Antimony-based photocathode Sb2S3/Sb2O3Heterojunction structure and preparation method thereof |
| CN113675283B (en) * | 2021-08-24 | 2024-05-24 | 昆明理工大学 | Antimony-based photocathode Sb2S3/Sb2O3Heterojunction structure and preparation method thereof |
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