CN111063550A - Preparation method and application of hollow core-shell Fe-Co-based sulfide @ nickel hydroxide nanotube array - Google Patents
Preparation method and application of hollow core-shell Fe-Co-based sulfide @ nickel hydroxide nanotube array Download PDFInfo
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Abstract
The invention belongs to the technical field of composite material synthesis, relates to preparation of a nanotube array, and particularly relates to hollow core-shell FeCo2S4@Ni(OH)2The preparation method of the nanotube array comprises the following steps: mixing iron source, cobalt source and CH4N2O and NH4Dissolving F in deionized water, putting a substrate material into the deionized water, transferring the substrate material into a hydrothermal reaction kettle, and heating the substrate material at 120-160 ℃ for 12-24 hours to obtain a Fe-Co precursor loaded on the surface of the substrate material; then it was placed in a solution containing 0.1mol/L of Na2Heating the S solution in a high-pressure reaction kettle at 120-160 ℃ for 4-8 h; continuing to perform constant voltage electrodeposition with Ni (OH)2Deposition of ultrathin nanosheets on FeCo2S4And (5) obtaining the nanotube array surface. The invention adopts a hydrothermal method and a constant-voltage electrodeposition method, has extremely simple and mature synthesis process, good repeatability, uses cheap and easily-obtained non-toxic raw materials, and is preparedPrepared core-shell FeCo2S4@Ni(OH)2The nanotube array is assembled into a simple Asymmetric Supercapacitor (ASC), the capacity can still keep 98.5% after 10000 cycles, and the method has a predictable good application prospect in the field of asymmetric supercapacitors.
Description
Technical Field
The invention belongs to the technical field of composite material synthesis, relates to preparation of a nanotube array, and particularly relates to a hollow core-shell Fe-Co-based sulfide compositeNickel hydroxide (FeCo)2S4@Ni(OH)2) A preparation method of a nanotube array and application of the nanotube array to an Asymmetric Supercapacitor (ASC).
Background
With the increasing trend of a series of foreseeable energy crisis situations, sustainable and renewable energy concepts enter the public field of vision, and energy storage and conversion become the focus of implementation, and the super capacitor has the advantages of low manufacturing cost, fast charging and discharging and high power density (>10kW·kg-1) And excellent cycle stability (>50000) And the like, and the device becomes a new generation of energy storage device with prospect.
Transition metal sulfides are used as an important and promising pseudo-capacitance multifunctional active material, and are paid attention to the fields of photocatalysis, sensors, supercapacitors, photovoltaic devices and the like due to the excellent optical, electrical and chemical properties of the transition metal sulfides. In particular to ternary mixed transition metal sulfide FeCo prepared by a hydrothermal method2S4The multiple oxidation states of the electrode material have richer active sites for redox reaction, and the electrode material is easy for large-scale production, so that the electrode material becomes a research hotspot of the current electrode material of the super capacitor. Ni (OH)2Due to the unique layered structure, larger interlayer spacing and excellent theoretical specific capacitance (2082F-g)-1) And the coating is easy to prepare, and is suitable for energy storage materials.
Disclosure of Invention
The invention aims to provide a method for preparing hollow core-shell FeCo by combining a hydrothermal method and a constant-voltage electrodeposition method2S4@Ni(OH)2An array of nanotubes.
Hollow core-shell FeCo2S4@Ni(OH)2The preparation method of the nanotube array comprises the following steps:
A. mixing iron source, cobalt source and CH4N2O and NH4Dissolving F in deionized water, putting the substrate material into a hydrothermal reaction kettle, heating at 120-160 ℃ for 12-24 h, preferably at 120 ℃ for 24h, naturally cooling to room temperature, washing for 3 times respectively by using ethanol and deionized water, and drying at 60 ℃ to obtain a Fe-Co precursor loaded on the surface of the substrate material; wherein the iron source is a cobalt source CH4N2O:NH4The molar volume ratio of F to deionized water is 1-4 mmol: 2-8 mmol: 4-16 mmol:40mL, preferably 1mmol:2mmol:4mmol:4mmol:40 mL;
B. placing Fe-Co precursor loaded on the surface of a substrate material in a solution containing 0.1mol/L of Na2Heating the S solution in a high-pressure reaction kettle at 120-160 ℃ for 4-8 h, preferably at 160 ℃ for 8h to prepare FeCo growing on the substrate material2S4A nanotube array;
C. with 0.1M Ni (NO)3)2FeCo as an electrodeposition solution grown on a substrate material2S4The nanotube array is used as a working electrode, the reference electrode is a saturated calomel electrode, the counter electrode is a platinum sheet electrode, the constant voltage deposition potential is-1.0V, and Ni (OH) is added2Deposition of ultrathin nanosheets on FeCo2S4Nanotube array surface, i.e. hollow core-shell FeCo2S4@Ni(OH)2An array of nanotubes.
In a preferred embodiment of the present invention, the iron source in step A is Fe (NO)3)3·9H2O, cobalt source is Co (NO)3)2·6H2O。
In the preferred embodiment of the invention, the substrate material in the step A is carbon paper, the carbon paper is pretreated before use, the carbon paper is cut into squares of 1cm multiplied by 1cm, the squares are sequentially treated by acetone, ethanol and deionized water respectively for 20min, and the squares are dried in an oven at 60 ℃ for later use.
In the preferred embodiment of the present invention, the deposition time in step C is 180s,360s, 720 s.
The invention adopts hollow FeCo2S4Nanotubes and ultrathin Ni (OH)2Nanosheets, and hollow core-shell FeCo is synthesized for the first time by combining a hydrothermal method and a constant-voltage electrodeposition method2S4@Ni(OH)2An array of nanotubes. On the one hand, one-dimensional hollow FeCo2S4The nanotube material is used as a nuclear framework, effectively shortens the transmission path of ion reaction, is beneficial to the infiltration and transfer of electrolytic liquid, and on the other hand, the ultrathin two-dimensional Ni (OH)2The nano sheet is tightly wrapped in the hollow FeCo2S4On the nanotube skeleton, the Faraday active sites of chemical reaction are greatly increased. Such a hollow core-shell FeCo2S4@Ni(OH)2The construction of the nanotube material effectively improves the electrochemical performance of the electrode material, and the core-shell nanotube composite material synthesized for the first time can light the LED under the voltage of 3.2V, thereby providing the possibility for practical application and having great promotion effect on the energy conversion and storage of the new generation.
The product is subjected to morphological structure analysis by instruments such as X-ray diffraction (XRD), Field Emission Scanning Electron Microscope (FESEM), electron transmission microscope (TEM), X-ray photoelectron spectrometer (XPS) and the like, and is tested by an electrochemical workstation to evaluate the electrochemical performance of the product.
Another object of the invention is to provide a hollow core-shell FeCo prepared2S4@Ni(OH)2The simple Asymmetric Super Capacitor (ASC) is assembled by taking a nanotube material as a positive electrode, taking active carbon coated on foamed nickel as a negative electrode and taking potassium hydroxide as an electrolyte solution, and the two ASCs are connected in series. The LED bulb can be lighted by charging with 3.2V voltage.
Advantageous effects
The invention adopts a hydrothermal method and a constant-voltage electrodeposition method to prepare the hollow core-shell FeCo2S4@Ni(OH)2The invention has the advantages of simple and mature synthesis process, good repeatability, cheap and easily-obtained raw materials and no toxicity, and the prepared core-shell FeCo2S4@Ni(OH)2The simple Asymmetric Super Capacitor (ASC) is assembled by the nanotube material, and the capacity can still be maintained at 98.5% after 10000 cycles. The LED bulb can be lightened by charging at the voltage of 3.2V, has excellent electrochemical performance and has good application prospect in the fields of environment, energy and the like.
Drawings
FIG. 1 is a view of a hollow core-shell FeCo prepared2S4@Ni(OH)2XRD diffractogram of nanotube array.
FIG. 2 is a schematic representation of the hollow FeCo prepared2S4Hollow core-shell FeCo2S4@Ni(OH)2Scanning of nanotube arrays wherein (a) FeCo2S4，(b)FeCo2S4@Ni(OH)2(180s)，(c)FeCo2S4@Ni(OH)2(360s)，(d) FeCo2S4@Ni(OH)2(720s) SEM image at 200nm magnification.
Fig. 3(a) TEM image, (b) HRTEM image.
FIG. 4 is a diagram of a hollow core-shell FeCo prepared2S4@Ni(OH)2XPS plot of nanomaterials, wherein (a) the full spectrum; (b) is Fe; (c) is Co; (d) is O; (e) is Ni; (f) is S.
FIG. 5(a) is a view showing the preparation of hollow FeCo2S4Hollow core-shell FeCo2S4@Ni(OH)2(180s,360s and 720s) cyclic voltammogram of the nanomaterial at 2mv/s, and (b) is hollow core-shell FeCo2S4@Ni(OH)2360s constant current charge-discharge diagram, and (c) is a current density and specific capacitance comparison diagram.
FIG. 6(a) is FeCo prepared2S4@Ni(OH)2The schematic diagram of the AC asymmetric super capacitor device is shown in the figure (b), the lighting LED figure is shown in the figure (c), and the cycle experiment figure is shown in the figure (c).
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Unless otherwise defined, terms (including technical and scientific terms) used herein should be construed to have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art, and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Example 1
Hollow core-shell FeCo2S4@Ni(OH)2Preparation of nanotube materialPrepare for
Before the material is synthesized, the following treatments are carried out on the carbon paper: cutting the carbon paper into squares of 1cm multiplied by 1cm, then sequentially carrying out ultrasonic treatment for 20 minutes by using acetone, ethanol and deionized water respectively, and drying the squares in an oven at the temperature of 60 ℃ for later use.
Hollow core-shell FeCo2S4@Ni(OH)2The preparation method of the nanotube array comprises the following steps:
A. 0.2020g of iron nitrate nonahydrate (Fe (NO)3)3·9H2O),0.2911g of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O),0.1201g Urea (CH)4N2O) and 0.0074g of ammonium fluoride (NH)4F) Dissolving in 40ml of deionized water, and stirring for 20 minutes under the action of a magnetic stirrer to form a light pink transparent homogeneous solution;
B. transferring the pretreated carbon paper into a 50ml polytetrafluoroethylene high-pressure reaction kettle along with the homogeneous phase solution, sealing the kettle, reacting for 24 hours at 120 ℃, naturally cooling to room temperature, repeatedly washing for 3 times by absolute pure ethanol and deionized water respectively, and drying in a constant-temperature oven at 60 ℃ for one night to obtain a Fe-Co precursor loaded on the carbon paper;
C. the Fe-Co precursor loaded on the carbon paper contains 0.1M Na2Etching the S solution in a 50ml polytetrafluoroethylene high-pressure reaction kettle at 160 ℃ for 8 hours, cooling to room temperature in a natural environment, repeating the washing operation in the same way, and drying to obtain FeCo which is vertically arranged on the carbon paper and is orderly2S4A hollow nanotube array;
D. outermost "shell" layer Ni (OH)2The ultrathin nanosheet is 50ml of 0.1M emerald Ni (NO) at constant voltage of-1.0V3)2Obtained by electrodeposition in electrolyte solution with electrochemical workstation (CHI 660E, CH Instrument Inc, China), and its working electrode is FeCo-loaded in the above step2S4The carbon paper takes a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode (vs. SCE) to deposit for 180s,360s and 720s respectively to obtain hollow core-shell FeCo with different deposition times2S4@Ni(OH)2An array of nanotubes.
As shown in FIG. 1, it can be seen that FeCo2S4And Ni (OH)2All the characteristic peaks of (A) appear in FeCo2S4@Ni(OH)2And with increasing electrodeposition time, Ni (OH)2The content is gradually increased, the C peak is gradually weakened, and the characteristic peak of the material is more obvious.
FIG. 2 shows that on carbon paper, (a) FeCo2S4，(b)FeCo2S4@Ni(OH)2(180s)，(c) FeCo2S4@Ni(OH)2(360s)，(d)FeCo2S4@Ni(OH)2(720s) SEM image at 200nm magnification.
In FIG. 3, (a) TEM indicates that the composite material has a hollow core-shell structure, and (b) HRTEM indicates that the composite material is made of FeCo2S4And Ni (OH)2And (4) forming.
The XPS chart of FIG. 4 shows the presence of Fe, Ni, Co, S, O elements.
FIG. 5 can observe that at a deposition time of 360s, the hollow core-shell FeCo2S4@Ni(OH)2The nano material can reach the highest current density of 1A and the specific capacity of 2538.2F g-1。
FIGS. 6a-c show two hollow core-shell FeCo2S4@Ni(OH)2(360s)// AC are connected in series to form the super device, and the LED small bulb can be lightened. After 10000 cycles of experiments, 98.3% of capacitance is still remained.
Hollow core-shell FeCo2S4@Ni(OH)2Electrochemical experiments on nanomaterials
(1) FeCo loaded on carbon paper of 1cm x 1cm2S4@Ni(OH)2The nano material is used as a working electrode;
(2) carrying out electrochemical test on the prepared working electrode, a silver/silver chloride electrode and a platinum sheet electrode in 6mol/L KOH electrolyte;
(3) prepared hollow core-shell FeCo2S4@Ni(OH)2Nano material is in 1 A.g-1The specific capacity of the current density of the alloy reaches 2538.2F·g-1。
Example 2
Hollow core-shell FeCo2S4@Ni(OH)2The preparation method of the nanotube array comprises the following steps:
A. 0.4040g of iron nitrate nonahydrate (Fe (NO)3)3·9H2O),0.5821g of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O),0.2402g Urea (CH)4N2O) and 0.1480g of ammonium fluoride (NH)4F) Dissolving in 40ml of deionized water, and stirring for 20 minutes under the action of a magnetic stirrer to form a light pink transparent homogeneous solution;
B. transferring the pretreated carbon paper into a 50ml polytetrafluoroethylene high-pressure reaction kettle along with the homogeneous phase solution, sealing the kettle, reacting for 24 hours at 120 ℃, naturally cooling to room temperature, repeatedly washing for 3 times by absolute pure ethanol and deionized water respectively, and drying in a constant-temperature oven at 60 ℃ for one night to obtain a Fe-Co precursor loaded on the carbon paper;
C. the Fe-Co precursor loaded on the carbon paper contains 0.1M Na2Etching the S solution in a 50ml polytetrafluoroethylene high-pressure reaction kettle at 160 ℃ for 4 hours, cooling to room temperature in a natural environment, repeating the washing operation in the same way, and drying to obtain FeCo which is vertically arranged on the carbon paper and is orderly2S4A hollow nanotube array;
D. outermost "shell" layer Ni (OH)2The ultrathin nanosheet is 50ml of 0.1M emerald Ni (NO) at constant voltage of-1.0V3)2Obtained by electrodeposition in electrolyte solution with electrochemical workstation (CHI 660E, CH Instrument Inc, China), and its working electrode is FeCo-loaded in the above step2S4The carbon paper takes a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode (vs. SCE) to deposit for 180s,360s and 720s respectively to obtain hollow core-shell FeCo with different deposition times2S4@Ni(OH)2An array of nanotubes.
Prepared hollow core-shell FeCo2S4@Ni(OH)2Nano material is in 1 A.g-1The specific capacity of the alloy reaches 1800.4 F.g under the current density-1。
Example 3
Hollow core-shell FeCo2S4@Ni(OH)2The preparation method of the nanotube array comprises the following steps:
A. 1.2120g of iron nitrate nonahydrate (Fe (NO)3)3·9H2O),1.7463g of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O),0.7206g Urea (CH)4N2O) and 0.4440g of ammonium fluoride (NH)4F) Dissolving in 40ml of deionized water, and stirring for 20 minutes under the action of a magnetic stirrer to form a light pink transparent homogeneous solution;
B. transferring the pretreated carbon paper into a 50ml polytetrafluoroethylene high-pressure reaction kettle along with the homogeneous phase solution, sealing the kettle, reacting for 24 hours at 120 ℃, naturally cooling to room temperature, repeatedly washing for 3 times by absolute pure ethanol and deionized water respectively, and drying in a constant-temperature oven at 60 ℃ for one night to obtain a Fe-Co precursor loaded on the carbon paper;
C. the Fe-Co precursor loaded on the carbon paper contains 0.1M Na2Etching the S solution in a 50ml polytetrafluoroethylene high-pressure reaction kettle at 160 ℃ for 8 hours, cooling to room temperature in a natural environment, repeating the washing operation in the same way, and drying to obtain FeCo which is vertically arranged on the carbon paper and is orderly2S4A hollow nanotube array;
D. outermost "shell" layer Ni (OH)2The ultrathin nanosheet is 50ml of 0.1M emerald Ni (NO) at constant voltage of-1.0V3)2Obtained by electrodeposition in electrolyte solution with electrochemical workstation (CHI 660E, CH Instrument Inc, China), and its working electrode is FeCo-loaded in the above step2S4The carbon paper takes a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode (vs. SCE) to deposit for 180s,360s and 720s respectively to obtain hollow core-shell FeCo with different deposition times2S4@Ni(OH)2An array of nanotubes.
Prepared hollow core-shell FeCo2S4@Ni(OH)2Nano material is in 1 A.g-1The specific capacity of the alloy reaches 1763.5 F.g under the current density-1。
Example 4
Hollow core-shell FeCo2S4@Ni(OH)2The preparation method of the nanotube array comprises the following steps:
A. 1.6160g of iron nitrate nonahydrate (Fe (NO)3)3·9H2O),2.3284g of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O),0.9608g Urea (CH)4N2O) and 0.5920g of ammonium fluoride (NH)4F) Dissolving in 40ml of deionized water, and stirring for 20 minutes under the action of a magnetic stirrer to form a light pink transparent homogeneous solution;
B. transferring the pretreated carbon paper into a 50ml polytetrafluoroethylene high-pressure reaction kettle along with the homogeneous phase solution, sealing the kettle, reacting for 24 hours at 120 ℃, naturally cooling to room temperature, repeatedly washing for 3 times by absolute pure ethanol and deionized water respectively, and drying in a constant-temperature oven at 60 ℃ for one night to obtain a Fe-Co precursor loaded on the carbon paper;
C. the Fe-Co precursor loaded on the carbon paper contains 0.1M Na2Etching the S solution in a 50ml polytetrafluoroethylene high-pressure reaction kettle at 120 ℃ for 8 hours, cooling to room temperature in a natural environment, repeating the washing operation in the same way, and drying to obtain FeCo which is vertically arranged on the carbon paper and is orderly2S4A hollow nanotube array;
D. outermost "shell" layer Ni (OH)2The ultrathin nanosheet is 50ml of 0.1M emerald Ni (NO) at constant voltage of-1.0V3)2Obtained by electrodeposition in electrolyte solution with electrochemical workstation (CHI 660E, CH Instrument Inc, China), and its working electrode is FeCo-loaded in the above step2S4The carbon paper takes a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode (vs. SCE) to deposit for 180s,360s and 720s respectively to obtain hollow core-shell FeCo with different deposition times2S4@Ni(OH)2An array of nanotubes.
The specific capacity of the prepared hollow core-shell FeCo2S4@ Ni (OH)2 nano material under the current density of 1 A.g-1 reaches 1912.6 F.g-1。
Example 5
Hollow core-shell FeCo2S4@Ni(OH)2The preparation method of the nanotube array comprises the following steps:
A. 0.2020g of iron nitrate nonahydrate (Fe (NO)3)3·9H2O),0.2911g of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O),0.1201g Urea (CH)4N2O) and 0.0074g of ammonium fluoride (NH)4F) Dissolving in 40ml of deionized water, and stirring for 20 minutes under the action of a magnetic stirrer to form a light pink transparent homogeneous solution;
B. transferring the pretreated carbon paper into a 50ml polytetrafluoroethylene high-pressure reaction kettle along with the homogeneous phase solution, sealing the kettle, reacting for 24 hours at 120 ℃, naturally cooling to room temperature, repeatedly washing for 3 times by absolute pure ethanol and deionized water respectively, and drying in a constant-temperature oven at 60 ℃ for one night to obtain a Fe-Co precursor loaded on the carbon paper;
C. the Fe-Co precursor loaded on the carbon paper contains 0.1M Na2Etching the S solution in a 50ml polytetrafluoroethylene high-pressure reaction kettle at 140 ℃ for 8 hours, cooling to room temperature in a natural environment, repeating the washing operation in the same way, and drying to obtain FeCo which is vertically arranged on the carbon paper and is orderly2S4A hollow nanotube array;
D. outermost "shell" layer Ni (OH)2The ultrathin nanosheet is 50ml of 0.1M emerald Ni (NO) at constant voltage of-1.0V3)2Obtained by electrodeposition in electrolyte solution with electrochemical workstation (CHI 660E, CH Instrument Inc, China), and its working electrode is FeCo-loaded in the above step2S4The carbon paper takes a Pt sheet as a counter electrode and a saturated calomel electrode as a reference electrode (vs. SCE) to deposit for 180s,360s and 720s respectively to obtain hollow core-shell FeCo with different deposition times2S4@Ni(OH)2An array of nanotubes.
The specific capacity of the prepared hollow core-shell FeCo2S4@ Ni (OH)2 nano material under the current density of 1 A.g-1 reaches 1695.4 F.g-1。
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (10)
1. Hollow core-shell FeCo2S4@Ni(OH)2The preparation method of the nanotube array is characterized by comprising the following steps of:
A. mixing iron source, cobalt source and CH4N2O and NH4Dissolving F in deionized water, putting the substrate material into the deionized water, transferring the substrate material into a hydrothermal reaction kettle, heating the substrate material at 120-160 ℃ for 12-24 h, naturally cooling the substrate material to room temperature, washing the substrate material with ethanol and deionized water for 3 times respectively, and drying the substrate material at 60 ℃ to obtain a Fe-Co precursor loaded on the surface of the substrate material; wherein the iron source is a cobalt source CH4N2O:NH4The molar volume ratio of the F to the deionized water is 1-4 mmol: 2-8 mmol: 4-16 mmol:40 mL;
B. placing Fe-Co precursor loaded on the surface of a substrate material in a solution containing 0.1mol/L of Na2Heating the S solution in a high-pressure reaction kettle at 120-160 ℃ for 4-8 h to prepare FeCo growing on the substrate material2S4A nanotube array;
C. with 0.1M Ni (NO)3)2FeCo as an electrodeposition solution grown on a substrate material2S4The nanotube array is used as a working electrode, the reference electrode is a saturated calomel electrode, the counter electrode is a platinum sheet electrode, the constant voltage deposition potential is-1.0V, and Ni (OH) is added2Deposition of ultrathin nanosheets on FeCo2S4And (5) obtaining the nanotube array surface.
2. The hollow core-shell FeCo of claim 12S4@Ni(OH)2The preparation method of the nanotube array is characterized by comprising the following steps: in the step A, the iron source is Fe (NO)3)3·9H2O, cobalt source is Co (NO)3)2·6H2O。
3. According to claim1 said hollow core-shell FeCo2S4@Ni(OH)2The preparation method of the nanotube array is characterized by comprising the following steps: the substrate material in the step A is carbon paper, the carbon paper is pretreated before use, the carbon paper is cut into squares of 1cm multiplied by 1cm, the squares are sequentially subjected to ultrasonic treatment for 20min by acetone, ethanol and deionized water respectively, and the squares are placed into a 60 ℃ drying oven to be dried for later use.
4. The hollow core-shell FeCo of claim 12S4@Ni(OH)2The preparation method of the nanotube array is characterized by comprising the following steps: in the step A, an iron source, a cobalt source and CH4N2O and NH4Dissolving F in deionized water, adding a substrate material, transferring into a hydrothermal reaction kettle, and heating at 120 ℃ for 24 h.
5. The hollow core-shell FeCo of claim 12S4@Ni(OH)2The preparation method of the nanotube array is characterized by comprising the following steps: in the step A, the iron source is a cobalt source CH4N2O:NH4The molar volume ratio of F to deionized water is 1mmol:2mmol:4mmol:4mmol:40 mL.
6. The hollow core-shell FeCo of claim 12S4@Ni(OH)2The preparation method of the nanotube array is characterized by comprising the following steps: in the step B, the Fe-Co precursor loaded on the surface of the substrate material is placed in a solution containing 0.1mol/L of Na2Heating the S solution in a high-pressure reaction kettle at 160 ℃ for 8 h.
7. The hollow core-shell FeCo of claim 12S4@Ni(OH)2The preparation method of the nanotube array is characterized by comprising the following steps: the deposition time in step C is 180s,360s and 720 s.
8. Hollow core-shell FeCo prepared by the method according to any of claims 1 to 72S4@Ni(OH)2An array of nanotubes.
9. Hollow core-shell according to claim 8FeCo2S4@Ni(OH)2A nanotube array characterized by: the hollow core-shell FeCo2S4@Ni(OH)2Nanotube array with one-dimensional hollow FeCo2S4Nanotube as core skeleton, ultrathin two-dimensional Ni (OH)2The nano sheet is tightly wrapped in the hollow FeCo2S4On the nanotube backbone.
10. A hollow core-shell FeCo according to any of claims 8 to 92S4@Ni(OH)2The application of the nanotube array is characterized in that: it is applied to asymmetric supercapacitors.
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| CN113077999A (en) * | 2021-03-26 | 2021-07-06 | 东南大学 | Binder-free CoFe LDH @ Co8FeS8Preparation method of composite electrode material |
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Application publication date: 20200424 |