CN105914358B - The preparation method of yolk eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano boxes - Google Patents
The preparation method of yolk eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano boxes Download PDFInfo
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Abstract
Yolk eggshell structure nitrogen-doped carbon coats the preparation method of four oxygen three-iron@tin ash magnetic Nano boxes, belong to nano material production technical field, nano cubic surface parcel layer of silicon dioxide is found in di-iron trioxide, then in the presence of three hydrated stannic acid potassium and urea, form yolk eggshell structure di-iron trioxide@stannic oxide nanometer boxes, finally coat dopamine, introduce carbon source and nitrogen source, calcine under an inert atmosphere, conductive carbon-coating is formed, while di-iron trioxide is converted into ferroso-ferric oxide.The instrument and equipment that the present invention uses is simple, it is low to prepare cost, operating process is easy, course of reaction material requested is less toxic, harmless, and it can effectively control the stoichiometric proportion of multi-component material, acquisition size is homogeneous, is evenly distributed and pattern controls well, can be used for this yolk eggshell structure magnetic nano material of industrial mass production high quality.
Description
Technical field
The invention belongs to nano material production technical field, and in particular to the system of yolk-eggshell structure magnetic nano material
Preparation Method.
Background technology
In transition metal oxide, ferroso-ferric oxide is because of its high theoretical capacity, environment-friendly, cost is cheap and resource is rich
The advantages that rich is 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 bulk effect larger during lithium ion is embedding/de- the defects of, cause its poor multiplying power special
Property and cycle performance, greatly limit its commercial applications.At present, by synthesizing the ferriferrous oxide nano with special construction
Material and design are with preparing ferriferrous oxide composite material to improve its chemical property.
The content 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 are dissolved in deionized water and carry out hydro-thermal reaction, reaction is centrifuged after terminating and washed
Wash, take solid phase to dry, obtain di-iron trioxide nanocube；
2）Di-iron trioxide nanocube is scattered in absolute ethyl alcohol under ultrasound condition, then sequentially add from
Sub- water, concentrated ammonia liquor and tetraethyl orthosilicate, mixed solution is formed, then mixed solution is placed under water bath condition and reacted,
Reaction terminates rear centrifuge washing, takes solid phase to dry, obtains the di-iron trioxide@silica nanometer cubes of nucleocapsid structure；
3）By di-iron trioxide@silica nanometers cube, three hydrated stannic acid potassium and the urea of nucleocapsid structure in ultrasound
Under the conditions of be scattered in deionized water and absolute ethyl alcohol, then carry out hydro-thermal reaction, reaction terminates rear centrifuge washing, takes solid phase to do
It is dry, obtain the di-iron trioxide@stannic oxide nanometer boxes of yolk-eggshell structure；
4）The di-iron trioxide@stannic oxide nanometers box of yolk-eggshell structure is scattered in Tris- under ultrasound condition
In buffer solution, be then blended into Dopamine hydrochloride, form reaction solution, then place reaction liquid under the conditions of stirred in water bath carry out it is anti-
Should, reaction terminates rear centrifuge washing, takes the high-temperature calcination under argon gas atmosphere protection after solid phase drying, obtains yolk-eggshell structure
Nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano boxes.
The present invention is using Dopamine hydrochloride as carbon source and nitrogen source, at room temperature to yolk-eggshell structure di-iron trioxide@dioxies
Change sijna rice box surface and carry out poly-dopamine (PDA) cladding, high-temperature calcination under an argon atmosphere forms yolk-eggshell structure nitrogen
Adulterate carbon coated ferriferrous oxide tin ash magnetic Nano box.The advantages of nitrogen-doped carbon：1）Can on nitrogen-doped carbon shell surface
To form stable solid electrolyte film (SEI), the formation of the film can effectively reduce the loss of initial capacity, improve material
Cycle performance；2）Nitrogen is advantageous 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, first in its Surface coating silica, obtains core-shell structure copolymer using di-iron trioxide nanocube as template
Structure di-iron trioxide@silicon dioxide composite materials, then using three hydrated stannic acid potassium as tin source, egg is obtained by hydro-thermal reaction
Huang-eggshell structure di-iron trioxide@stannic oxide nanometer boxes.Finally, by the use of Dopamine hydrochloride as carbon source and nitrogen source to three oxygen
Change two iron@stannic oxide nanometer boxes to be coated, four oxygen of double-shell structure are formed by high-temperature calcination under an argon atmosphere
Change three-iron@tin dioxide carbon-to-nitrogen magnetic Nano boxes.As a result show, unique nanocube and nucleocapsid structure, be not only
Kernel ferriferrous oxide material lithium ion it is embedding it is de- during caused bulk effect provide effective cushion space, it is also favourable
In the quick transmission of lithium ion；The cooperative effect of two kinds of transition metal oxides of ferroso-ferric oxide and tin ash make its possess compared with
Height ratio capacity and high rate performance, and excellent cyclical stability；And the synergy of tin dioxide carbon shell causes material
During lithiumation/go lithiumation caused bulk effect has obtained effective alleviation so that active material is in high current, long circulating
To effective protection.Therefore, yolk-eggshell structure ferroso-ferric oxide@tin dioxides carbon-to-nitrogen magnetic Nano box is a kind of performance
The lithium ion battery negative material of excellent, great application prospect.
It is an advantage of the invention that：The instrument and equipment of use is simple, and preparation cost is low, and operating process is easy, course of reaction institute
Need material less toxic, harmless, and can effectively control the stoichiometric proportion of multi-component material, acquisition size is homogeneous, is evenly distributed
, can be with and pattern controls good yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide tin ash magnetic Nano box
This yolk-eggshell structure magnetic nano material for industrial mass production high quality.
The magnetic Nano box of manufactured nucleocapsid structure, particle diameter are about 650 nm or so, and silicon dioxide layer disappears and formed
High-visible tin ash hollow shell layer, and it is about 70nm's that the tin dioxide layer forms width with di-iron trioxide kernel
Void area, ferroso-ferric oxide@tin dioxide carbon-to-nitrogen magnetic Nano boxes outer surface carbon-coating, carbon-coating even uniform, thickness is about
For 10nm, this structure has great specific surface area.
In addition, step 1 of the present invention）In, the mass ratio of ferric chloride (FeCl36H2O) and sodium hydroxide is 1: 0.5~2, described
The temperature conditionss of hydro-thermal reaction are 100~180 DEG C.Prepared di-iron trioxide pattern is homogeneous, Stability Analysis of Structures, is prepared to be follow-up
Yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano boxes with good pattern provide
Advantage.
The step 2）In, the mixing quality ratio of di-iron trioxide nanocube, concentrated ammonia liquor and tetraethyl orthosilicate is 1
: 0.15~0.8: 0.3~2；Bath temperature is 30~80 DEG C in reaction.Silica can be uniformly coated on this condition
Nano cubic surface, consistency of thickness and can keep cube structure.
The step 3）In, the di-iron trioxide@silica nanometers cube of nucleocapsid structure, three hydrated stannic acid potassium and
The mixing quality ratio of urea is 1: 0.2~1: 1~2；The temperature conditionss of the hydro-thermal reaction are 150~250 DEG C, reaction time 2-
5h.On this condition, tin dioxide layer is uniformly coated on silica layer surface, with the rising of pH value of solution, silica
Layer is gradually etched, and is left a void between di-iron trioxide and tin dioxide layer, is formed typical yolk-eggshell structure.
The step 4）In, the di-iron trioxide@stannic oxide nanometers 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.Using Tris- buffer solutions as reaction dissolvent,
Dopamine hydrochloride occurs auto polymerization and forms poly-dopamine under this reaction condition, and can be uniformly coated on yolk-eggshell structure
Di-iron trioxide@stannic oxide nanometer box surfaces.
The step 4）In, calcining heat condition is 500~700 DEG C, calcination time 2h.In this calcining heat and calcining
In time range, void area remains intact, and shows good yolk-eggshell structure, and material surface carbon-coating clearly may be used
See, be uniformly coated on the surface of nanometer box.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of the di-iron trioxide nanocube prepared.
Fig. 2 is the cubical transmission electron microscope picture of nucleocapsid structure di-iron trioxide@silica nanometers prepared.
Fig. 3 is the transmission electron microscope picture of the yolk-eggshell structure di-iron trioxide@stannic oxide nanometer boxes prepared.
Fig. 4 is the transmission electron microscope picture of the yolk-eggshell structure di-iron trioxide@tin dioxide PDA nanometer boxes prepared.
Fig. 5 is the yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano boxes prepared
Transmission electron microscope picture.
Fig. 6 is the yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano boxes prepared
Charge-discharge performance figure（Current density is 3 A g-1）.
Fig. 7 is the yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano boxes prepared
The charge-discharge performance figure of different multiplying.
Embodiment
First, preparation technology example：
Embodiment 1：
1st, di-iron trioxide nanocube is prepared：
The sodium hydrate solid of 80mg ferric chloride (FeCl36H2O) and 40mg is dissolved in 90mL deionized waters, in 25 DEG C of conditions
Moved to after being well mixed down in the hydrothermal reaction kettle of 150 mL polytetrafluoroethyllining linings, 100 DEG C of reaction 24h.After question response terminates,
Reactor is taken out by red product deionized water and each centrifuge washing of absolute ethyl alcohol three times, finally dried in vacuum drying chamber
12 h.Products therefrom is di-iron trioxide nanocube.
2nd, nucleocapsid structure di-iron trioxide@silica nanometer cubes are prepared：
By the above-mentioned di-iron trioxide nano cubic ultrasonic disperses of 100mg in 70mL absolute ethyl alcohols, after being uniformly dispersed according to
It is secondary to add 6.5 mL deionized waters, 15 mg ammoniacal liquor and 30 mg tetraethyl orthosilicates (TEOS), react 2 under 30 DEG C of water bath conditions
h.After question response terminates, finally done in vacuum drying chamber by product deionized water and each centrifuge washing of absolute ethyl alcohol three times
Dry 12 h.Products therefrom is nucleocapsid structure di-iron trioxide@silica nanometer cubes.
3rd, yolk-eggshell structure di-iron trioxide@stannic oxide nanometer boxes are prepared：
By the above-mentioned di-iron trioxide@silica nanometer cubes of 100mg, the hydrated stannic acid potassium of 20mg tri- and 100mg urea
Ultrasonic disperse moves to 50 mL polytetrafluoros in the solution containing 12mL deionized waters and 18 mL absolute ethyl alcohols after being uniformly dispersed
In the hydrothermal reaction kettle of ethene liner, 150 DEG C of 5 h of reaction.It is after question response terminates, product deionized water and absolute ethyl alcohol is each
Centrifuge washing three times, finally dries 12 h in vacuum drying chamber.Products therefrom is yolk-eggshell structure di-iron trioxide@
Stannic oxide nanometer box nanocube.
4th, yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano boxes are prepared：
By the above-mentioned di-iron trioxide@stannic oxide nanometers box ultrasonic disperses of 45mg in 50mLTris-buffer (pH ≈
8.5) in solution, 9 mg Dopamine hydrochlorides (3-Hydroxytyramine hydrochloride) are added after being uniformly dispersed, so
Afterwards under 20 DEG C of water bath conditions after the h of stirring reaction 15 by product deionized water and each centrifuge washing of absolute ethyl alcohol three times, finally
12 h are dried in vacuum drying chamber.Dried product is subjected to high-temperature calcination in argon gas atmosphere, temperature programming is to 500 DEG C
2 h, 1 DEG C/min of heating rate are calcined, final products therefrom is yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@
Tin ash magnetic Nano box.
Embodiment 2
1st, di-iron trioxide nanocube is prepared：
The sodium hydrate solid of 80mg ferric chloride (FeCl36H2O) and 80mg is dissolved in 90mL deionized waters, in 25 DEG C of conditions
Moved to after being well mixed down in the hydrothermal reaction kettle of 150 mL polytetrafluoroethyllining linings, 150 DEG C of 36 h of reaction.Question response terminates
Afterwards, reactor is taken out by red product deionized water and each centrifuge washing of absolute ethyl alcohol three times, finally in vacuum drying chamber
Dry 12 h.Products therefrom is di-iron trioxide nanocube.
2nd, nucleocapsid structure di-iron trioxide@silica nanometer cubes are prepared：
By the above-mentioned di-iron trioxide nanocube ultrasonic disperses of 100mg in 70mL absolute ethyl alcohols, after being uniformly dispersed
6.5 mL deionized waters, 18 mg ammoniacal liquor and 50 mg tetraethyl orthosilicates (TEOS) are sequentially added, are reacted under 50 DEG C of water bath conditions
6h.After question response terminates, finally done in vacuum drying chamber by product deionized water and each centrifuge washing of absolute ethyl alcohol three times
Dry 12 h.Products therefrom is nucleocapsid structure di-iron trioxide@silica nanometer cubes.
3rd, yolk-eggshell structure di-iron trioxide@stannic oxide nanometer boxes are prepared：
By the above-mentioned di-iron trioxide@silica nanometer cubes of 100mg, the hydrated stannic acid potassium of 50mg tri- and 120mg urea
Ultrasonic disperse moves to 50 mL poly- four in the solution containing 12 mL deionized waters and 18 mL absolute ethyl alcohols after being uniformly dispersed
In the hydrothermal reaction kettle of PVF liner, 200 DEG C of 3 h of reaction.After question response terminates, by product deionized water and absolute ethyl alcohol
Each centrifuge washing three times, finally dries 12 h in vacuum drying chamber.Products therefrom is the oxidation of yolk-eggshell structure three two
Iron@stannic oxide nanometer boxes.
4th, yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano boxes are prepared：
By the above-mentioned di-iron trioxide@stannic oxide nanometers box ultrasonic disperses of 45mg in 50mLTris-buffer (pH ≈
8.5) in solution, 45 mg Dopamine hydrochlorides (3-Hydroxytyramine hydrochloride) are added after being uniformly dispersed,
Then under 30 DEG C of water bath conditions after stirring reaction 18h by product deionized water and each centrifuge washing of absolute ethyl alcohol three times, most
12 h are dried in vacuum drying chamber afterwards.Dried product is subjected to high-temperature calcination, temperature programming to 600 in argon gas atmosphere
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
Iron@tin ash magnetic Nano boxes.
Embodiment 3
1st, di-iron trioxide nanocube is prepared：
The sodium hydrate solid of 80mg ferric chloride (FeCl36H2O) and 160mg is dissolved in 90mL deionized waters, in 25 DEG C of bars
Moved to after being well mixed under part in the hydrothermal reaction kettle of 150 mL polytetrafluoroethyllining linings, 180 DEG C of reaction 48h.Question response terminates
Afterwards, reactor is taken out by red product deionized water and each centrifuge washing of absolute ethyl alcohol three times, finally in vacuum drying chamber
Dry 12 h.Products therefrom is di-iron trioxide nanocube.
2nd, nucleocapsid structure di-iron trioxide@silica nanometer cubes are prepared：
By the above-mentioned di-iron trioxide nanocube ultrasonic disperses of 100mg in 70mL absolute ethyl alcohols, after being uniformly dispersed
Sequentially add 6.5 mL deionized waters, 80 mg ammoniacal liquor and 200 mg tetraethyl orthosilicates (TEOS), it is anti-under 80 DEG C of water bath conditions
Answer 12 h.After question response terminates, finally in vacuum drying chamber by product deionized water and each centrifuge washing of absolute ethyl alcohol three times
The middle h of drying 12.Products therefrom is nucleocapsid structure di-iron trioxide@silica nanometer cubes.
3rd, yolk-eggshell structure di-iron trioxide@stannic oxide nanometer boxes are prepared：
By the above-mentioned di-iron trioxide@silica nanometer cubes of 100mg, the hydrated stannic acid potassium of 100mg tri- and 200mg urea
Ultrasonic disperse moves to 50 mL polytetrafluoros in the solution containing 12mL deionized waters and 18 mL absolute ethyl alcohols after being uniformly dispersed
In the hydrothermal reaction kettle of ethene liner, 250 DEG C of 2 h of reaction.It is after question response terminates, product deionized water and absolute ethyl alcohol is each
Centrifuge washing three times, finally dries 12 h in vacuum drying chamber.Products therefrom is yolk-eggshell structure di-iron trioxide@
Stannic oxide nanometer box.
4th, yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano boxes are prepared：
By the above-mentioned di-iron trioxide@stannic oxide nanometers box ultrasonic disperses of 45mg in 50mLTris-buffer (pH ≈
8.5) in solution, 90 mg Dopamine hydrochlorides (3-Hydroxytyramine hydrochloride) are added after being uniformly dispersed,
Then under 80 DEG C of water bath conditions after stirring reaction 24h by product deionized water and each centrifuge washing of absolute ethyl alcohol three times, most
12 h are dried in vacuum drying chamber afterwards.Dried product is subjected to high-temperature calcination, temperature programming to 700 in argon gas atmosphere
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
Iron@tin ash magnetic Nano boxes.
2nd, product is verified：
Fig. 1 is the cubical transmission electron microscope picture of ferric oxide nano prepared using the inventive method.From figure：It is prepared
Product for particle diameter be about 500 nm, and surface is smooth.
Fig. 2 is the cubical transmission of nucleocapsid structure di-iron trioxide@silica nanometers prepared using the inventive method
Electron microscope.From figure：The di-iron trioxide 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 using the saturating of the yolk-eggshell structure di-iron trioxide@stannic oxide nanometer boxes of the inventive method preparation
Penetrate electron microscope.From figure：Silicon dioxide layer disappears and forms high-visible tin ash hollow shell layer, and the titanium dioxide
Tin layers form the void area that width is about 70 nm with di-iron trioxide kernel.
Fig. 4 is the yolk-eggshell structure di-iron trioxide@tin dioxide PDA nanometer boxes prepared using the inventive method
Transmission electron microscope picture.From figure：Composite di-iron trioxide@tin dioxides PDA is still cube structure, material table
Face does not have an impact after PDA is coated to internal void area.Good nucleocapsid structure is still kept, can be clearly from figure
Go out tin dioxide PDA shells region, PDA thickness degree is about 10 nm.
Fig. 5 is the yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash prepared using the inventive method
The transmission electron microscope picture of magnetic Nano box.From figure：The particle diameter of prepared purpose product is about 650 nm or so, interstice coverage
Domain remains intact, and shows good nucleocapsid structure, and material surface carbon-coating is high-visible and carbon-coating even uniform, and thickness is about
For 10 nm.
3rd, application effect：
Yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic prepared by the inventive method is received
Rice box is assembled into button cell.
Fig. 6 and Fig. 7 is respectively the yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic prepared
The charge-discharge performance figure of nanometer box, the A g of current density 3-1With high rate performance figure.Fig. 6 is electrode material in 3 A g-1
Constant current density under charge-discharge performance figure, by 600 circle circulation after, nitrogen-doped carbon coated ferriferrous oxide@bis-
The reversible specific capacity of tin oxide magnetic Nano box is 570 mA h g-1, and after the 10th circle coulombic efficiency close to 100%.
Fig. 7 is the charge-discharge performance figure under different multiplying, first by material in 500 mA g-1Under current density, follow
Ring discharge and recharge 300 is enclosed to its capacity and tended towards stability, and now reversible specific capacity is 890 mA h g-1, afterwards respectively in 1 A g-1、2
A g-1With 3 A g-1Current density under each circle of circulation 50, reversible specific capacity is respectively 751,660 and 567 mA h g-1.When following
During ring to 450 circle, 500 mA g are turned again to-1Under current density, specific capacity quickly recovers to 853 mA h g-1, it is about initial
The 95% of capacity, show that there is fabulous high rate performance.
Claims (3)
1. the preparation method of yolk-eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano boxes, it is special
Sign is to comprise the following steps：
1）Ferric chloride (FeCl36H2O) and sodium hydroxide are dissolved in deionized water and carry out hydro-thermal reaction, reaction terminates rear centrifuge washing,
Take solid phase to dry, obtain di-iron trioxide nanocube；
2）Di-iron trioxide nanocube is scattered in absolute ethyl alcohol under ultrasound condition, then sequentially adds deionization
Water, concentrated ammonia liquor and tetraethyl orthosilicate, mixed solution is formed, then mixed solution is placed under water bath condition and reacted, instead
Centrifuge washing after should terminating, takes solid phase to dry, and obtains the di-iron trioxide@silica nanometer cubes of nucleocapsid structure；
3）By di-iron trioxide@silica nanometers cube, three hydrated stannic acid potassium and the urea of nucleocapsid structure in ultrasound condition
Under be scattered in deionized water and absolute ethyl alcohol, then carry out hydro-thermal reaction, reaction terminates rear centrifuge washing, takes solid phase to dry,
Obtain the di-iron trioxide@stannic oxide nanometer boxes of yolk-eggshell structure；
4）The di-iron trioxide@stannic oxide nanometers box of yolk-eggshell structure is scattered in Tris- bufferings under ultrasound condition
In liquid, Dopamine hydrochloride is then blended into, forms reaction solution, then place reaction liquid under the conditions of stirred in water bath and reacted,
Reaction terminates rear centrifuge washing, takes the high-temperature calcination under argon gas atmosphere protection after solid phase drying, and the nitrogen for obtaining yolk-eggshell structure is mixed
Miscellaneous carbon coated ferriferrous oxide@tin ash magnetic Nano box；
The step 1）In, the mass ratio of ferric chloride (FeCl36H2O) and sodium hydroxide is 1: 0.5~2, the temperature of the hydro-thermal reaction
Condition is 100~180 DEG C；
The step 2）In, the mixing quality ratio of di-iron trioxide nanocube, concentrated ammonia liquor and tetraethyl orthosilicate is 1:
0.15~0.8: 0.3~2, bath temperature is 30~80 DEG C in reaction；
The step 3）In, di-iron trioxide@silica nanometers cube, three hydrated stannic acid potassium and the urea of nucleocapsid structure
Mixing quality ratio be 1: 0.2~1: 1~2, the temperature conditionss of the hydro-thermal reaction are 150~250 DEG C, 2~5h of reaction time；
The step 4）In, the di-iron trioxide@stannic oxide nanometers box of yolk-eggshell structure and feeding intake for Dopamine hydrochloride
Mass ratio is 1: 0.2~2.
2. preparation method according to claim 1, it is characterised in that the step 4）In, the bath temperature of the reaction is
20~80 DEG C.
3. preparation method according to claim 1, it is characterised in that the step 4）In, calcining heat condition be 500~
700 DEG C, calcination time 2h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610463788.9A CN105914358B (en) | 2016-06-24 | 2016-06-24 | The preparation method of yolk eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano boxes |
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|---|---|---|---|
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| CN108379581A (en) * | 2018-03-30 | 2018-08-10 | 上海交通大学 | A kind of ferroso-ferric oxide-carbon-gold pharmaceutical carrier and preparation method thereof |
| CN109395762B (en) * | 2018-11-29 | 2021-07-13 | 武汉工程大学 | Tin dioxide/nitrogen-doped graphite/zinc sulfide composite material with core-shell structure and preparation method thereof |
| CN109904421A (en) * | 2019-02-20 | 2019-06-18 | 湖北工程学院 | A kind of lithium ion battery electrode material and preparation method thereof with cube structure |
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| CN110518230A (en) * | 2019-09-24 | 2019-11-29 | 吉林大学 | The preparation method of lithium ion battery negative material |
| 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 |
| CN111477847B (en) * | 2020-04-08 | 2022-07-19 | 扬州大学 | Box-shaped necklace multilevel structure Fe7S8/WS2@ C-CNFs lithium ion battery negative electrode material and preparation method thereof |
| CN112331815B (en) * | 2020-11-04 | 2021-09-10 | 四川大学 | Iron-tin-iron-tin nitrogen compound integrated lithium ion battery cathode and preparation method thereof |
| CN112811473B (en) * | 2021-01-06 | 2022-09-30 | 安徽师范大学 | Nano bracelet iron sesquioxide/graphene quantum dot/tin dioxide core-shell structure composite material, preparation method thereof and battery application |
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