CN108190963A - A kind of hollow CoFe of multistage2O4Material, CoFe2O4The preparation method and application of/C composite - Google Patents
A kind of hollow CoFe of multistage2O4Material, CoFe2O4The preparation method and application of/C composite Download PDFInfo
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
Multistage hollow CoFe is prepared by coordination polymer the present invention provides one kind2O4The method of material and its composite material, its synthesis step are specific as follows：Multistage hollow ferrocenyl coordination polymer is prepared by solvent-thermal method first with cobalt salt and the double formic acid of ferrocene（Co‑Fc‑Hcps）；Using Co Fc Hcps coordination polymers obtained, the method for high-temperature calcination prepares multistage hollow CoFe under air atmosphere2O4Material；By the stirring with Dopamine hydrochloride and the technology of high-temperature calcination obtains CoFe under nitrogen atmosphere2O4@C multistage hollow composite materials.Reaction step of the present invention is easy to operate and environmentally friendly, and equipment requirement is low.With it is existing it is reported compared with, this CoFe with two level nano bar-shape structure2O4The hollow ball composite material of@C has broad application prospects as novel energy-storing electrode material and magnetic applications etc..
Description
Technical field
The present invention relates to a kind of hollow CoFe of multistage2O4And its composite material preparation method and in lithium ion cell electrode
Application on material.
Background technology
Widely available with electronic equipment, people are also higher and higher to the energy storage requirement of battery.Therefore, a large amount of research
Worker is put into the research of electrode material, improves the storage performance of battery with this, and metal oxide and metal hydrogen-oxygen
Compound is due to its high theoretical capacity, it is considered to be significant electrode material.Result of study shows cobalt ferrite and its composite wood
Material as lithium electricity electrode material there is higher specific capacity, Hui et al. to be added to graphene solution using cobalt nitrate and ferric nitrate
In CoFe prepared by hydro-thermal method2O4With the composite material of graphene, specific capacity is in 100 mA g-1When be 910 mAh
g-1（Hui X, Zhu D, Fu Y, et al. CoFe2O4-graphene nanocomposite as a high-
capacity anode material for lithium-ion batteries[J]. Electrochimica Acta,
2012, 83(12):166-174.）.The seminar of Guo synthesizes ferro-cobalt MOF using Prussian blue, is then converted by calcining
Method synthesized cubical cobalt ferrite material, under the long circulating of the current density of 1.0 C, specific capacity be 1043 mAh
g-1（Guo H, Li T, Chen W, et al. General design of hollow porous CoFe2O4
nanocubes from metal-organic frameworks with extraordinary lithium storage
[J]. Nanoscale, 2014, 6(24):15168.）.Ren etc. passes through ferrocene and cobaltocene physical mixed and high-temperature calcination
The obtained cobalt ferrite of method and carbon composite material, in 100 mA g-1Lower specific capacity is 656 mAh g-1（Ren S, Zhao
X, Chen R, et al. A facile synthesis of encapsulated CoFe2O4, into carbon
nanofibres and its application as conversion anodes for lithium ion batteries
[J]. Journal of Power Sources, 2014, 260(7):205-210.）.The seminar of Li utilizes cobaltous sulfate, sulphur
Sour iron and sucrose have prepared classifying porous microballoon cobalt ferrite material by the method for hydro-thermal and calcining, in 2 A g-1Under can reach
To 406 mAh g-1（Shouli, Aihua, Ranran, et al. Hierarchical porous metal ferrite
ball-in-ball hollow spheres: General synthesis, formation mechanism, and high
Performance as anode materials for Li-ion batteries [J] research in nanotechnologys (English edition),
2014, 7(8):1116-1127.）.The method of relevant report synthesis cobalt ferrite mainly has hydro-thermal method, calcination method and MOF conversions
Method, but it is synthesized go out material often do not contain two level nanostructured.
Invention content
This patent is referring initially to Huo J et al.（Huo J, Wang L, Irran E, et al. Synthesis,
characterization and magnetic properties of hollow microspheres with micro-
mesoporous shells assembled from cobalt-based ferrocenyl coordination
polymers[J]. Journal of Colloid & Interface Science, 2012, 367(1):92-100.）It closes
Into going out multistage hollow cobalt-Ferrocenyl coordinated polymer（Co-Fc-Hcps）Then coordination polymer is converted by high-temperature calcination again
For the cobalt ferrite hollow ball containing two level nanostructured, and then wrap up one layer of carbon.Since its spherical shell has unique two level nanometer
Structure, therefore with good storing up electricity performance, therefore it is developed have great significance with research and application value.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of hollow CoFe of multistage2O4The preparation method of material, includes the following steps：
The first step prepares presoma as multistage hollow Co-Fc-Hcps coordination polymers；
Second step obtains calcining under the hollow Co-Fc-Hcps coordination polymers air atmosphere of multistage of first step preparation in multistage
Empty CoFe2O4Material.
Preferably, calcination condition is that 3h is calcined at 350 ~ 550 DEG C in the second step, and heating rate is 3 DEG C/min.
Preferably, the detailed process for presoma being prepared in the first step is：By the double formic acid of 1,1 ＇-ferrocene and cobalt salt
It closes object to be dissolved in respectively in DMF or DMF aqueous solutions, stir evenly, cobalt salt solution is then added to 1, the double formic acid of 1 ＇-ferrocene are molten
In liquid, after stirring evenly, mixed liquor is transferred in reaction kettle, reaction kettle is reacted into 12 ~ 20h at 125 DEG C, after reaction
With DMF or DMF aqueous cleanings to clarifying, Co-Fc-Hcps coordination polymers are made after dry in centrifugation.
Preferably, it is DMF and water according to volume ratio that DMF aqueous solutions in the detailed process of presoma are prepared in the first step
It is 1:1 mixes.
Preferably, the first step prepare cobalt salt compound in the detailed process of presoma be cabaltous nitrate hexahydrate, six water
Close the one of which in cobalt chloride, cobaltous sulfate, cobalt acetate.
Preferably, the first step is prepared 1 in the detailed process of presoma, the double formic acid of 1 ＇-ferrocene and cobalt salt compound
The amount ratio of substance be（0.5~1）: 1.
A kind of hollow CoFe of multistage2O4The preparation method of@C composites, includes the following steps：
Three（Methylol）Dopamine hydrochloride and the CoFe of above-mentioned preparation are added in aminomethane buffer solution2O4, it is lasting to stir
3h cleans solid after centrifugation with distilled water and ethyl alcohol respectively, dry 12h at 65 DEG C, under dried solids nitrogen atmosphere
Calcining obtains multistage hollow CoFe2O4@C composites.
Preferably, the calcination condition is that 3h is calcined at 350 ~ 550 DEG C, and heating rate is 3 DEG C/min.The embodiment of the present invention
In, using being calcined at 450 DEG C, but the calcination temperature in the range of 350 ~ 550 DEG C belongs to the scope of protection of the invention.
Preferably, the Dopamine hydrochloride and CoFe2O4Mass ratio be（0.2~1）: 1.It is further preferred that the salt
Sour dopamine and CoFe2O4Mass ratio be 1:2, a concentration of 0.4g/L of Dopamine hydrochloride, CoFe in mixed liquor before centrifugation2O4's
A concentration of 0.8g/L.
Preferably, described three（Methylol）A concentration of 0.1mol/L of aminomethane buffer solution.
The hollow CoFe of multistage described above2O4Material, CoFe2O4@C composites are as electrode material in lithium-ion electric
Application in pond.
Compared with prior art, beneficial effects of the present invention are：
The hollow CoFe of multistage of the present invention2O4Ball preparation method is to pass through high temperature as presoma using cobalt-Ferrocenyl coordinated polymer
Calcining obtains, and process is simple, and presoma prepares entire reaction process and carried out in DMF, without other additional additives, and forges
Burning method simple process and low cost is honest and clean, is easy to industrialized production；In addition, the preparation method of the present invention can pass through process conditions
Regulation and control obtain different cobalt ferrite three-dimensional composite materials.
Description of the drawings
Fig. 1 is the CoFe with two level nanostructured obtained of the embodiment of the present invention 42O4Hollow material scanning electron microscope (SEM) photograph；
Fig. 2 is the CoFe with two level nano bar-shape structure obtained of the embodiment of the present invention 52O4@C hollow composite materials scanning electricity
Mirror figure；
Fig. 3 is the CoFe with two level nano bar-shape structure obtained of the embodiment of the present invention 52O4@C hollow composite material X ray
Diffraction pattern；
Fig. 4 is the CoFe with two level nano bar-shape structure obtained of the embodiment of the present invention 52O4@C hollow composite materials cycle volt
Antu；
Fig. 5 is the CoFe with two level nano bar-shape structure obtained of the embodiment of the present invention 52O4Different times of@C hollow composite materials
Charge and discharge electrograph under rate.
Specific embodiment
With reference to embodiment, the present invention is described in further detail.
Embodiment 1
The present embodiment prepares CoFe2O4Process include the following steps：
（1）The synthesis of the multistage hollow Co-Fc-Hcps coordination polymers of presoma：Weigh 0.2000g（1.1mmol）1,1 ＇-two cyclopentadienyls
The double formic acid of iron and 0.2124g (1.1mmol) cabaltous nitrate hexahydrate are dissolved in 18mL DMF/H respectively2O (the two volume ratios 1:1) in,
Cobalt nitrate solution is added dropwise into the double formic acid solutions of 1,1 ＇-ferrocene after stirring evenly.Mixed liquor is transferred to after stirring evenly
20h is reacted at 125 DEG C in 50mL reaction kettles, centrifuge and uses DMF/H2O (the two volume ratios 1:1) cleaning is roused to clarifying at 80 DEG C
Co-Fc-Hcps coordination polymers are obtained after air-drying dry 15h；
（2）Obtained Co-Fc-Hcps coordination polymers are calcined into 3h in tube furnace at 350 DEG C（3℃/min）After be made
CoFe2O4Material.
Embodiment 2
The present embodiment prepares CoFe2O4Process include the following steps：
（1）The synthesis of the multistage hollow Co-Fc-Hcps coordination polymers of presoma：Weigh 0.5086g（1.8mmol）1,1 ＇-two cyclopentadienyls
The double formic acid of iron and 0.4326g (1.8mmol) cabaltous nitrate hexahydrate are dissolved in 18mL DMF/H respectively2O (the two volume ratios 1:1) in,
Cobalt nitrate solution is added dropwise into the double formic acid solutions of 1,1 ＇-ferrocene after stirring evenly.Mixed liquor is transferred to after stirring evenly
125 DEG C of reaction 20h, centrifuge and use DMF/H in 50mL reaction kettles2O (the two volume ratios 1:1) cleaning is extremely clarified, air blast at 80 DEG C
Co-Fc-Hcps coordination polymers are obtained after dry 15h；
（2）Obtained Co-Fc-Hcps coordination polymers are calcined into 3h for 450 DEG C in tube furnace（3℃/min）After be made
CoFe2O4Material.
Embodiment 3
The present embodiment prepares CoFe2O4Process include the following steps：
（1）The synthesis of the multistage hollow Co-Fc-Hcps coordination polymers of presoma：Weigh 0.5086g（1.8mmol）1,1 ＇-two cyclopentadienyls
The double formic acid of iron and 0.4326g (1.8mmol) cobalt chloride hexahydrate are dissolved in respectively in 18mL DMF, after stirring evenly that cobalt chloride is molten
Drop is added in the double formic acid solutions of 1,1 ＇-ferrocene.Mixed liquor is transferred to 125 DEG C of reactions in 50mL reaction kettles after stirring evenly
12h centrifuges and is cleaned with DMF to clarification, obtains Co-Fc-Hcps coordination polymers at 80 DEG C after forced air drying 15h；
（2）Obtained Co-Fc-Hcps coordination polymers are calcined into 3h for 550 DEG C in tube furnace（3℃/min）It is made afterwards hollow
CoFe2O4Material.
Embodiment 4
The present embodiment prepares CoFe2O4Process include the following steps：
（1）The synthesis of the multistage hollow Co-Fc-Hcps coordination polymers of presoma：Weigh 0.5086g（1.8mmol）1,1 ＇-two cyclopentadienyls
The double formic acid of iron and 0.4326g (1.8mmol) cobalt chloride hexahydrate are dissolved in respectively in 18mL DMF, after stirring evenly that cobalt chloride is molten
Drop is added in the double formic acid solutions of 1,1 ＇-ferrocene.Mixed liquor is transferred to 125 DEG C of reactions in 50mL reaction kettles after stirring evenly
12h centrifuges and is cleaned with DMF to clarification, obtains Co-Fc-Hcps coordination polymers at 80 DEG C after forced air drying 15h；
（2）Obtained Co-Fc-Hcps coordination polymers are calcined into 3h for 450 DEG C in tube furnace（3℃/min）Being made afterwards has two level
The hollow CoFe of nanostructured2O4Material.
The hollow CoFe of two level nanostructured manufactured in the present embodiment2O4The scanning electron microscope (SEM) photograph of material is as shown in Figure 1, from Fig. 1
In find out the CoFe of preparation2O4Hollow ball is the hollow shell being made of nanometer sheet.
Embodiment 5
The present embodiment prepares CoFe2O4The process of@C composites includes the following steps：
（1）The three of 100mL（Methylol）Aminomethane buffer solution（10mmol）It is middle add in 40mg Dopamine hydrochloride and
The CoFe of 80mg2O4, 3h is persistently stirred, obtained black solid is centrifuged and is cleaned 3 times, 65 DEG C with distilled water and ethyl alcohol respectively again
Lower dry 12h.
（2）The CoFe that will be obtained2O4With the compound of Dopamine hydrochloride in tube furnace 450 DEG C of calcining 3h under nitrogen protection
（3℃/min）The hollow CoFe for having two level nanostructured is made afterwards2O4@C composites.
The hollow CoFe of two level nanostructured manufactured in the present embodiment2O4The scanning electron microscope (SEM) photograph of@C composites such as Fig. 2 institutes
Show, there is no apparent variation occurs in packet carbon for its unique hollow structure as seen from Figure 2.
Hollow CoFe prepared by the present invention2O4Structure with two level nanometer, table when as lithium ion battery electrode material
Excellent electrochemistry capacitance performance, high rate performance and cycle performance are revealed, have had in terms of synthesis multilevel hierarchy and energy storage wide
Wealthy application prospect.
Fig. 3 is the CoFe with two level nanostructured obtained2O4And CoFe2O4The X ray of the hollow three-dimensional composite materials of@C
Diffraction pattern is compared with standard card, and material prepared by the present invention is exactly CoFe2O4And CoFe2O4@C.Fig. 4 is obtained by the present invention
The CoFe with two level nano bar-shape structure2O4@C hollow composite material cyclic voltammograms；Fig. 5 is obtained with two level
The CoFe of nano bar-shape structure2O4Charge and discharge electrograph under@C hollow composite material different multiplyings.From the experimental result table of Fig. 4 and Fig. 5
It is bright, the CoFe with two level nano bar-shape structure prepared by the present invention2O4@C hollow composite materials are preparing lithium ion battery
There is excellent chemical property in terms of electrode material.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (9)
1. a kind of hollow CoFe of multistage2O4The preparation method of material, which is characterized in that include the following steps：
The first step prepares presoma as multistage hollow Co-Fc-Hcps coordination polymers；
Second step obtains calcining under the hollow Co-Fc-Hcps coordination polymers air atmosphere of multistage of first step preparation in multistage
Empty CoFe2O4Material.
2. a kind of hollow CoFe of multistage according to claim 12O4The preparation method of material, which is characterized in that described second
Calcination condition is that 3h is calcined at 350 ~ 550 DEG C in step, and heating rate is 3 DEG C/min.
3. a kind of hollow CoFe of multistage2O4The preparation method of@C composites, which is characterized in that include the following steps：
Three（Methylol）Dopamine hydrochloride and the CoFe of claims 1 or 2 preparation are added in aminomethane buffer solution2O4, hold
Continuous stirring 3h, cleans solid after centrifugation with distilled water and ethyl alcohol respectively, dry 12h, dried solids nitrogen at 65 DEG C
It is calcined under atmosphere, obtains multistage hollow CoFe2O4@C composites.
4. a kind of hollow CoFe of multistage according to claim 32O4The preparation method of@C composites, which is characterized in that institute
It is that 3h is calcined at 350 ~ 550 DEG C to state calcination condition, and heating rate is 3 DEG C/min.
5. a kind of hollow CoFe of multistage according to claim 32O4The preparation method of@C composites, which is characterized in that institute
It is that 3h is calcined at 450 DEG C to state calcination condition, and heating rate is 3 DEG C/min.
6. a kind of hollow CoFe of multistage according to claim 32O4The preparation method of@C composites, which is characterized in that institute
State Dopamine hydrochloride and CoFe2O4Mass ratio be（0.2~1）: 1.
7. a kind of hollow CoFe of multistage according to claim 32O4The preparation method of@C composites, which is characterized in that institute
State Dopamine hydrochloride and CoFe2O4Mass ratio be 1:2, a concentration of 0.4g/L of Dopamine hydrochloride in mixed liquor before centrifugation,
CoFe2O4A concentration of 0.8g/L.
8. a kind of hollow CoFe of multistage according to claim 32O4The preparation method of@C composites, which is characterized in that institute
State three（Methylol）A concentration of 0.1mol/L of aminomethane buffer solution.
9. the hollow CoFe of multistage described in claim 32O4And CoFe2O4@C composites are as electrode material in lithium ion battery
In application.
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Cited By (7)
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| CN109378450A (en) * | 2018-08-29 | 2019-02-22 | 浙江大学 | Layer stephanoporate ZnFe2O4/ C lithium ion battery negative material and preparation method thereof |
| CN109449379A (en) * | 2018-09-12 | 2019-03-08 | 华南师范大学 | A kind of SnFe that nitrogen-doped carbon is compound2O4Lithium ion battery negative material and the preparation method and application thereof |
| CN112151804A (en) * | 2020-09-27 | 2020-12-29 | 广州大学 | Prussian blue analogue-based carbon-coated transition metal oxide and preparation method and application thereof |
| CN112599743A (en) * | 2020-12-15 | 2021-04-02 | 西安交通大学 | Carbon-coated nickel cobaltate multi-dimensional assembled microsphere negative electrode material and preparation method thereof |
| CN113675007A (en) * | 2021-08-13 | 2021-11-19 | 益阳市安兴电子有限公司 | Electrode with good cycle performance, preparation method thereof and super capacitor |
| CN114221024A (en) * | 2022-01-13 | 2022-03-22 | 费县威尚新能源技术中心 | Lithium ion battery |
| CN116618051A (en) * | 2023-06-06 | 2023-08-22 | 中国计量大学 | Oxygen-defect-containing cobalt ferrite nanorod and preparation method and application thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109378450A (en) * | 2018-08-29 | 2019-02-22 | 浙江大学 | Layer stephanoporate ZnFe2O4/ C lithium ion battery negative material and preparation method thereof |
| CN109378450B (en) * | 2018-08-29 | 2021-06-04 | 浙江大学 | Hierarchical porous ZnFe2O4Negative electrode material of/C lithium ion battery and preparation method thereof |
| CN109449379A (en) * | 2018-09-12 | 2019-03-08 | 华南师范大学 | A kind of SnFe that nitrogen-doped carbon is compound2O4Lithium ion battery negative material and the preparation method and application thereof |
| CN109449379B (en) * | 2018-09-12 | 2021-05-11 | 华南师范大学 | Nitrogen-doped carbon composite SnFe2O4Lithium ion battery cathode material and preparation method and application thereof |
| CN112151804A (en) * | 2020-09-27 | 2020-12-29 | 广州大学 | Prussian blue analogue-based carbon-coated transition metal oxide and preparation method and application thereof |
| CN112599743A (en) * | 2020-12-15 | 2021-04-02 | 西安交通大学 | Carbon-coated nickel cobaltate multi-dimensional assembled microsphere negative electrode material and preparation method thereof |
| CN112599743B (en) * | 2020-12-15 | 2022-06-07 | 西安交通大学 | Carbon-coated nickel cobaltate multi-dimensional assembled microsphere negative electrode material and preparation method thereof |
| CN113675007A (en) * | 2021-08-13 | 2021-11-19 | 益阳市安兴电子有限公司 | Electrode with good cycle performance, preparation method thereof and super capacitor |
| CN114221024A (en) * | 2022-01-13 | 2022-03-22 | 费县威尚新能源技术中心 | Lithium ion battery |
| CN114221024B (en) * | 2022-01-13 | 2022-11-18 | 广东顺盈森能源有限公司 | Lithium ion battery |
| CN116618051A (en) * | 2023-06-06 | 2023-08-22 | 中国计量大学 | Oxygen-defect-containing cobalt ferrite nanorod and preparation method and application thereof |
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