CN105914358A - Preparation method of yolk-eggshell structured nitrogen-doped carbon-coated Fe3O4@SnO2 magnetic nanometer box - Google Patents
Preparation method of yolk-eggshell structured nitrogen-doped carbon-coated Fe3O4@SnO2 magnetic nanometer box Download PDFInfo
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Abstract
The invention discloses a preparation method of a yolk-eggshell structured nitrogen-doped carbon-coated Fe3O4@SnO2 magnetic nanometer box, and belongs to the technical field of production of a nanometer material. The preparation method comprises the following steps of firstly, wrapping the surface of a Fe2O3 nanometer cube with a layer of silicon dioxide; secondly, forming a yolk-eggshell structured Fe2O3@SnO2 nanometer box under the effect of potassium stannate trihydrate and urea; and finally, coating dopamine, introducing a carbon source and a nitrogen source, carrying out calcination in an inertia atmosphere to form a conductive carbon layer, and simultaneously converting Fe2O3 to Fe3O4. The instrument equipment adopted by the invention is simple, the preparation cost is low, the operation process is simple and convenient, the required material during the reaction process is low toxic and is not harmful, the stoichiometric ratio of a multi-constituent material can be effectively controlled, and the high-quality yolk-eggshell structured magnetic nanometer material which is uniform in size, uniform in distribution and favorable in morphology control and can be used for industrial production at a large scale is obtained.
Description
Technical field
The invention belongs to nano material production technical field, be specifically related to the system of yolk-eggshell structure magnetic nano material
Preparation Method.
Background technology
In transition metal oxide, ferroso-ferric oxide because of its high theoretical capacity, environmental friendliness, with low cost and resource is rich
The advantages such as richness are considered as the lithium ion battery negative material of most practical value.But ferroso-ferric oxide is as negative material, its
Intrinsic low conductivity, and the defect such as bulk effect bigger during lithium ion is embedding/de-, cause its poor multiplying power special
Property and cycle performance, greatly limit its commercial applications.At present, be there is the ferriferrous oxide nano of special construction by synthesis
Material and design with prepare ferriferrous oxide composite material to improve its chemical property.
Summary of the invention
It is an object of the invention to propose a kind of yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash
The preparation method of magnetic Nano box.
The present invention comprises the following steps:
1) ferric chloride (FeCl36H2O) and sodium hydroxide being dissolved in deionized water and carry out hydro-thermal reaction, reaction terminates rear centrifuge washing,
Take solid phase to be dried, obtain iron sesquioxide nanocube；
2) under ultrasound condition, iron sesquioxide nanocube is scattered in dehydrated alcohol, then sequentially adds deionization
Water, strong aqua ammonia and tetraethyl orthosilicate, form mixed solution, be then placed in by mixed solution under water bath condition and react, instead
Centrifuge washing after should terminating, takes solid phase and is dried, and obtains the iron sesquioxide@silica nanometer cube of nucleocapsid structure；
3) by iron sesquioxide@silica nanometer cube, three hydrated stannic acid potassium and the carbamide of nucleocapsid structure at ultrasound condition
Under be scattered in deionized water and dehydrated alcohol, then carry out hydro-thermal reaction, reaction terminates rear centrifuge washing, takes solid phase and is dried,
Obtain the iron sesquioxide@stannic oxide nanometer box of yolk-eggshell structure；
4) the iron sesquioxide@stannic oxide nanometer box of yolk-eggshell structure is scattered under ultrasound condition Tris-buffering
In liquid, then it is blended into dopamine hydrochloride, forms reactant liquor, then react under the conditions of placing reaction liquid into stirred in water bath,
Reaction terminates rear centrifuge washing, takes solid phase high-temperature calcination under argon gas atmosphere is protected after drying, and the nitrogen obtaining yolk-eggshell structure is mixed
Miscellaneous carbon coated ferriferrous oxide@tin ash magnetic Nano box.
The present invention is with dopamine hydrochloride as carbon source with nitrogen source, at room temperature to yolk-eggshell structure iron sesquioxide@dioxy
Changing sijna rice box surface and carry out poly-dopamine (PDA) cladding, high-temperature calcination forms yolk-eggshell structure nitrogen under an argon atmosphere
Doping carbon coated ferriferrous oxide@tin ash magnetic Nano box.The advantage of nitrogen-doped carbon: 1) can on nitrogen-doped carbon shell surface
To form stable solid electrolyte film (SEI), the formation of this film can effectively reduce the loss of initial capacity, improve material
Cycle performance；2) nitrogen is conducive to the transfer of electric charge on the surface of carbon, can improve the diffusion of lithium ion, can high power charging-discharging.
The present invention, with iron sesquioxide nanocube as template, first at its Surface coating silicon dioxide, obtains core-shell structure copolymer
Structure iron sesquioxide silicon dioxide composite material, then with three hydrated stannic acid potassium as Xi Yuan, obtains egg by hydro-thermal reaction
Huang-eggshell structure iron sesquioxide@stannic oxide nanometer box.Finally, with dopamine hydrochloride as carbon source and nitrogen source to three oxygen
Change two ferrum@stannic oxide nanometer boxes to be coated with, formed four oxygen of double-shell structure by high-temperature calcination under an argon atmosphere
Change three-iron@tin dioxide carbon-to-nitrogen magnetic Nano box.Result shows, unique nanocube and nucleocapsid structure, is not only
Kernel ferriferrous oxide material lithium ion embedding de-during the bulk effect that produces provide effective cushion space, the most favourable
Quick transmission in lithium ion；The cooperative effect of ferroso-ferric oxide and two kinds of transition metal oxides of tin ash makes it have relatively
Height ratio capacity and high rate performance, and the cyclical stability of excellence；And the synergism of tin dioxide carbon shell makes material
The bulk effect produced during lithiumation/go lithiumation obtained effective alleviation so that active material is in big electric current, long circulating
To effectively protection.Therefore, yolk-eggshell structure ferroso-ferric oxide@tin dioxide carbon-to-nitrogen magnetic Nano box is a kind of performance
The lithium ion battery negative material of application prospect excellent, great.
The invention have the advantage that the instrument and equipment of employing is simple, preparation cost is low, and operating process is easy, course of reaction institute
Need material low toxicity, harmless, and can effectively control the stoichiometric proportion of multi-component material, it is thus achieved that size is homogeneous, is evenly distributed
And the yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano box that morphology control is good, permissible
For the high-quality this yolk-eggshell structure magnetic nano material of industrialized mass.
The magnetic Nano box of the nucleocapsid structure made, particle diameter is about about 650 nm, and silicon dioxide layer disappears and formed
Apparent tin ash hollow shell layer, and this tin dioxide layer and iron sesquioxide kernel form width and be about 70nm's
Void area, ferroso-ferric oxide@tin dioxide carbon-to-nitrogen magnetic Nano box outer surface carbon-coating, carbon-coating even uniform, thickness is about
For 10nm, this structure has great specific surface area.
It addition, in step 1) of the present invention, ferric chloride (FeCl36H2O) is 1: 0.5～2 with the mass ratio of sodium hydroxide, described
The temperature conditions of hydro-thermal reaction is 100～180 DEG C.Prepared iron sesquioxide pattern is homogeneous, and Stability Analysis of Structures, for follow-up preparation
The yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano box with good pattern provides
Advantage.
Described step 2) in, the mixing quality ratio of iron sesquioxide nanocube, strong aqua ammonia and tetraethyl orthosilicate is 1
: 0.15～0.8: 0.3～2；In reaction, bath temperature is 30～80 DEG C.Silicon dioxide can be made with this understanding to be uniformly coated on
Nano cubic surface, consistency of thickness and cube structure can be kept.
In described step 3), the iron sesquioxide@silica nanometer cube of nucleocapsid structure, three hydrated stannic acid potassium and
The mixing quality ratio of carbamide is 1: 0.2～1: 1～2；The temperature conditions of described hydro-thermal reaction is 150～250 DEG C, response time 2-
5h.With this understanding, tin dioxide layer is uniformly coated on silicon dioxide layer surface, along with the rising of pH value of solution, silicon dioxide
Layer is gradually etched, and leaves a void, form typical yolk-eggshell structure between iron sesquioxide and tin dioxide layer.
In described step 4), the iron sesquioxide@stannic oxide nanometer box of yolk-eggshell structure and dopamine hydrochloride
The mass ratio that feeds intake is 1: 0.2～2；The bath temperature of reaction is 20～80 DEG C.Use Tris-buffer as reaction dissolvent,
Under this reaction condition, dopamine hydrochloride generation auto polymerization forms poly-dopamine, and can be uniformly coated on yolk-eggshell structure
Iron sesquioxide@stannic oxide nanometer box surface.
In described step 4), calcining heat condition is 500～700 DEG C, and calcination time is 2h.In this calcining heat and calcining
In time range, void area remains intact, and presents good yolk-eggshell structure, and material surface carbon-coating clearly may be used
See, be uniformly coated on the surface of nanometer box.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of the iron sesquioxide nanocube of preparation.
Fig. 2 is the nucleocapsid structure iron sesquioxide cubical transmission electron microscope picture of@silica nanometer of preparation.
Fig. 3 is the transmission electron microscope picture of the yolk-eggshell structure iron sesquioxide@stannic oxide nanometer box of preparation.
Fig. 4 is the transmission electron microscope picture of the yolk-eggshell structure iron sesquioxide@tin dioxide PDA nanometer box of preparation.
Fig. 5 is the yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano box of preparation
Transmission electron microscope picture.
Fig. 6 is the yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano box of preparation
(electric current density is 3 A g to charge-discharge performance figure-1).
Fig. 7 is the yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano box of preparation
The charge-discharge performance figure of different multiplying.
Detailed description of the invention
One, preparation technology example:
Embodiment 1:
1, iron sesquioxide nanocube is prepared:
The ferric chloride (FeCl36H2O) of 80 mg and the sodium hydrate solid of 40 mg are dissolved in 90mL deionized water, under the conditions of 25 DEG C
Move in 150 mL teflon-lined hydrothermal reaction kettles after mix homogeneously, 100 DEG C of reaction 24h.After question response terminates, take
Go out reactor by each to red product deionized water and dehydrated alcohol centrifuge washing three times, in vacuum drying oven, be finally dried 12
h.Products therefrom is iron sesquioxide nanocube.
2, nucleocapsid structure iron sesquioxide@silica nanometer cube is prepared:
By 100 mg above-mentioned iron sesquioxide nano cubic ultrasonic disperse in 70 mL dehydrated alcohol, after being uniformly dispersed successively
Add 6.5 mL deionized waters, 15 mg ammonia and 30 mg tetraethyl orthosilicates (TEOS), under 30 DEG C of water bath condition, react 2 h.
After question response terminates, by each to product deionized water and dehydrated alcohol centrifuge washing three times, finally it is dried in vacuum drying oven
12 h.Products therefrom is nucleocapsid structure iron sesquioxide@silica nanometer cube.
3, yolk-eggshell structure iron sesquioxide@stannic oxide nanometer box is prepared:
100 mg above-mentioned iron sesquioxide@silica nanometer cube, 20 mg tri-hydrated stannic acid potassium and 100mg carbamide is super
Sound is scattered in the solution containing 12mL deionized water and 18 mL dehydrated alcohol, moves to 50 mL polytetrafluoroethyl-nes after being uniformly dispersed
In the hydrothermal reaction kettle of alkene liner, 150 DEG C of reaction 5 h.After question response terminates, by product deionized water and dehydrated alcohol respectively from
The heart washs three times, is finally dried 12 h in vacuum drying oven.Products therefrom is yolk-eggshell structure iron sesquioxide@bis-
Tin oxide nano box nanocube.
4, yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano box is prepared:
By 45 mg above-mentioned iron sesquioxide@stannic oxide nanometer box ultrasonic disperse in 50 mL Tris-buffer (pH ≈
8.5), in solution, after being uniformly dispersed, 9 mg dopamine hydrochlorides (3-Hydroxytyramine hydrochloride) are added, so
After under 20 DEG C of water bath condition after stirring reaction 15 h by each to product deionized water and dehydrated alcohol centrifuge washing three times, finally
12 h it are dried in vacuum drying oven.Dried product is carried out in argon gas atmosphere high-temperature calcination, temperature programming to 500 DEG C
Calcining 2 h, 1 DEG C/min of heating rate, final products therefrom is yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@
Tin ash magnetic Nano box.
Embodiment 2
1, iron sesquioxide nanocube is prepared:
The ferric chloride (FeCl36H2O) of 80 mg and the sodium hydrate solid of 80 mg are dissolved in 90 mL deionized waters, 25 DEG C of conditions
Move in 150 mL teflon-lined hydrothermal reaction kettles after lower mix homogeneously, 150 DEG C of reaction 36 h.Question response terminates
After, take out reactor by each to red product deionized water and dehydrated alcohol centrifuge washing three times, finally in vacuum drying oven
It is dried 12 h.Products therefrom is iron sesquioxide nanocube.
2, nucleocapsid structure iron sesquioxide@silica nanometer cube is prepared:
By 100 mg above-mentioned iron sesquioxide nanocube ultrasonic disperse in 70 mL dehydrated alcohol, depend on after being uniformly dispersed
Secondary addition 6.5 mL deionized water, 18 mg ammonia and 50 mg tetraethyl orthosilicates (TEOS), react under 50 DEG C of water bath condition
6h.After question response terminates, by each to product deionized water and dehydrated alcohol centrifuge washing three times, finally dry in vacuum drying oven
Dry 12 h.Products therefrom is nucleocapsid structure iron sesquioxide@silica nanometer cube.
3, yolk-eggshell structure iron sesquioxide@stannic oxide nanometer box is prepared:
100 mg above-mentioned iron sesquioxide@silica nanometer cube, 50 mg tri-hydrated stannic acid potassium and 120 mg carbamide are super
Sound is scattered in the solution containing 12 mL deionized waters and 18 mL dehydrated alcohol, moves to 50 mL polytetrafluoros after being uniformly dispersed
In the hydrothermal reaction kettle of ethylene liner, 200 DEG C of reaction 3 h.After question response terminates, by each to product deionized water and dehydrated alcohol
Centrifuge washing three times, is finally dried 12 h in vacuum drying oven.Products therefrom is yolk-eggshell structure iron sesquioxide@
Stannic oxide nanometer box.
4, yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano box is prepared:
By 45 mg above-mentioned iron sesquioxide@stannic oxide nanometer box ultrasonic disperse in 50 mL Tris-buffer (pH ≈
8.5), in solution, after being uniformly dispersed, 45 mg dopamine hydrochlorides (3-Hydroxytyramine hydrochloride) are added,
Then under 30 DEG C of water bath condition after stirring reaction 18h by each to product deionized water and dehydrated alcohol centrifuge washing three times,
After in vacuum drying oven be dried 12 h.Dried product is carried out in argon gas atmosphere high-temperature calcination, temperature programming to 600
DEG C calcining 2 h, 1 DEG C/min of heating rate, final products therefrom be yolk-eggshell structure nitrogen-doped carbon cladding four oxidation three
Ferrum@tin ash magnetic Nano box.
Embodiment 3
1, iron sesquioxide nanocube is prepared:
The ferric chloride (FeCl36H2O) of 80 mg and the sodium hydrate solid of 160 mg are dissolved in 90mL deionized water, 25 DEG C of conditions
Move in 150 mL teflon-lined hydrothermal reaction kettles after lower mix homogeneously, 180 DEG C of reaction 48h.After question response terminates,
Take out reactor by each to red product deionized water and dehydrated alcohol centrifuge washing three times, be finally dried in vacuum drying oven
12 h.Products therefrom is iron sesquioxide nanocube.
2, nucleocapsid structure iron sesquioxide@silica nanometer cube is prepared:
By 100 mg above-mentioned iron sesquioxide nanocube ultrasonic disperse in 70 mL dehydrated alcohol, depend on after being uniformly dispersed
Secondary addition 6.5 mL deionized water, 80 mg ammonia and 200 mg tetraethyl orthosilicates (TEOS), react under 80 DEG C of water bath condition
12 h.After question response terminates, by each to product deionized water and dehydrated alcohol centrifuge washing three times, finally in vacuum drying oven
It is dried 12 h.Products therefrom is nucleocapsid structure iron sesquioxide@silica nanometer cube.
3, yolk-eggshell structure iron sesquioxide@stannic oxide nanometer box is prepared:
By 100 mg above-mentioned iron sesquioxide@silica nanometer cube, 100 mg tri-hydrated stannic acid potassium and 200 mg carbamide
Ultrasonic disperse, in the solution containing 12mL deionized water and 18 mL dehydrated alcohol, moves to 50 mL polytetrafluoros after being uniformly dispersed
In the hydrothermal reaction kettle of ethylene liner, 250 DEG C of reaction 2 h.After question response terminates, by each to product deionized water and dehydrated alcohol
Centrifuge washing three times, is finally dried 12 h in vacuum drying oven.Products therefrom is yolk-eggshell structure iron sesquioxide@
Stannic oxide nanometer box.
4, yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano box is prepared:
By 45 mg above-mentioned iron sesquioxide@stannic oxide nanometer box ultrasonic disperse in 50 mL Tris-buffer (pH ≈
8.5), in solution, after being uniformly dispersed, 90 mg dopamine hydrochlorides (3-Hydroxytyramine hydrochloride) are added,
Then under 80 DEG C of water bath condition after stirring reaction 24h by each to product deionized water and dehydrated alcohol centrifuge washing three times,
After in vacuum drying oven be dried 12 h.Dried product is carried out in argon gas atmosphere high-temperature calcination, temperature programming to 700
DEG C calcining 2 h, 1 DEG C/min of heating rate, final products therefrom be yolk-eggshell structure nitrogen-doped carbon cladding four oxidation three
Ferrum@tin ash magnetic Nano box.
Two, product checking:
Fig. 1 is the cubical transmission electron microscope picture of ferric oxide nano using the inventive method to prepare.From figure: prepared product
Product are that particle diameter is about 500 nm, and smooth surface is smooth.
Fig. 2 is the nucleocapsid structure iron sesquioxide cubical transmission of@silica nanometer using the inventive method to prepare
Electronic Speculum figure.From figure: the iron sesquioxide pattern of coated with silica is homogeneous, still keeps cube structure, and can be clear
Clear finds out that coated with silica layer is completely uniform, and thickness is about 70 nm.
Fig. 3 is use the yolk-eggshell structure iron sesquioxide@stannic oxide nanometer box prepared of the inventive method saturating
Radio mirror figure.From figure: silicon dioxide layer disappears and forms apparent tin ash hollow shell layer, and this titanium dioxide
Tin layers forms, with iron sesquioxide kernel, the void area that width is about 70 nm.
Fig. 4 is the yolk-eggshell structure iron sesquioxide@tin dioxide PDA nanometer box using the inventive method to prepare
Transmission electron microscope picture.From figure: this composite iron sesquioxide@tin dioxide PDA is still cube structure, material list
Face, after PDA is coated with, does not produce impact to internal void area.Still keep good nucleocapsid structure, can be clearly from figure
Going out tin dioxide PDA shell region, PDA layer thickness is about 10 nm.
Fig. 5 is the yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash using the inventive method to prepare
The transmission electron microscope picture of magnetic Nano box.From figure: the particle diameter of prepared purpose product is about about 650 nm, interstice coverage
Territory remains intact, and presents good nucleocapsid structure, and material surface carbon-coating is high-visible and carbon-coating even uniform, and thickness is about
It is 10 nm.
Three, application effect:
Yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano box prepared by the inventive method
Subgroup dresses up button cell.
Fig. 6 and Fig. 7 is respectively the yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic of preparation
The charge-discharge performance figure of nanometer box, electric current density 3 A g-1With high rate performance figure.Fig. 6 is that electrode material is at 3 A g-1
Constant current density under charge-discharge performance figure, through 600 circle circulation after, nitrogen-doped carbon coated ferriferrous oxide@bis-
The reversible specific capacity of stannum oxide magnetic Nano box is 570 mA h g-1, and the 10th circle after coulombic efficiency close to 100%.
Fig. 7 is the charge-discharge performance figure under different multiplying, first by material at 500 mA g-1Under electric current density, follow
Ring discharge and recharge 300 is enclosed and is tended towards stability to its capacity, and now reversible specific capacity is 890 mA h g-1, the most respectively at 1 A g-1、2
A g-1With 3 A g-1Electric current density under each circulation 50 circle, reversible specific capacity is respectively 751,660 and 567 mA h g-1.When following
When ring is to 450 circle, turn again to 500 mA g-1Under electric current density, specific capacity quickly recovers to 853 mA h g-1, it is about initial
The 95% of capacity, shows have fabulous high rate performance.
Claims (9)
1. the preparation method of yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano box, it is special
Levy and be to comprise the following steps:
1) ferric chloride (FeCl36H2O) and sodium hydroxide being dissolved in deionized water and carry out hydro-thermal reaction, reaction terminates rear centrifuge washing,
Take solid phase to be dried, obtain iron sesquioxide nanocube；
2) under ultrasound condition, iron sesquioxide nanocube is scattered in dehydrated alcohol, then sequentially adds deionization
Water, strong aqua ammonia and tetraethyl orthosilicate, form mixed solution, be then placed in by mixed solution under water bath condition and react, instead
Centrifuge washing after should terminating, takes solid phase and is dried, and obtains the iron sesquioxide@silica nanometer cube of nucleocapsid structure；
3) by iron sesquioxide@silica nanometer cube, three hydrated stannic acid potassium and the carbamide of nucleocapsid structure at ultrasound condition
Under be scattered in deionized water and dehydrated alcohol, then carry out hydro-thermal reaction, reaction terminates rear centrifuge washing, takes solid phase and is dried,
Obtain the iron sesquioxide@stannic oxide nanometer box of yolk-eggshell structure；
4) the iron sesquioxide@stannic oxide nanometer box of yolk-eggshell structure is scattered under ultrasound condition Tris-buffering
In liquid, then it is blended into dopamine hydrochloride, forms reactant liquor, then react under the conditions of placing reaction liquid into stirred in water bath,
Reaction terminates rear centrifuge washing, takes solid phase high-temperature calcination under argon gas atmosphere is protected after drying, and the nitrogen obtaining yolk-eggshell structure is mixed
Miscellaneous carbon coated ferriferrous oxide@tin ash magnetic Nano box.
Preparation method the most according to claim 1, it is characterised in that in described step 1), ferric chloride (FeCl36H2O) and hydroxide
The mass ratio of sodium is 1: 0.5～2, and the temperature conditions of described hydro-thermal reaction is 100～180 DEG C.
Preparation method the most according to claim 1, it is characterised in that described step 2) in, iron sesquioxide nano cubic
The mixing quality ratio of body, strong aqua ammonia and tetraethyl orthosilicate is 1: 0.15～0.8: 0.3～2.
Preparation method the most according to claim 1, it is characterised in that described step 2) in, in reaction bath temperature be 30～
80℃。
Preparation method the most according to claim 1, it is characterised in that in described step 3), three oxidations two of nucleocapsid structure
The mixing quality ratio of ferrum@silica nanometer cube, three hydrated stannic acid potassium and carbamide is 1: 0.2～1: 1～2.
Preparation method the most according to claim 1, it is characterised in that in described step 3), the temperature strip of described hydro-thermal reaction
Part is 150～250 DEG C, response time 2-5h.
Preparation method the most according to claim 1, it is characterised in that in described step 4), three oxygen of yolk-eggshell structure
The mass ratio that feeds intake changing two ferrum@stannic oxide nanometer boxes and dopamine hydrochloride is 1: 0.2～2.
Preparation method the most according to claim 1, it is characterised in that in described step 4), the bath temperature of described reaction is
20～80 DEG C.
Preparation method the most according to claim 1, it is characterised in that in described step 4), calcining heat condition be 500～
700 DEG C, calcination time is 2h.
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| CN111072060B (en) * | 2019-12-31 | 2022-04-22 | 青岛科技大学 | Preparation method of nitrogen-containing carbon-coated flaky tin sulfide composite nano box |
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