CN106920698B - A kind of ultracapacitor NixCo3-xS4/NiCo2O4Composite material and preparation method - Google Patents
A kind of ultracapacitor NixCo3-xS4/NiCo2O4Composite material and preparation method Download PDFInfo
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Abstract
The present invention relates to a kind of ultracapacitor NixCo3‑xS4/NiCo2O4Composite material and preparation method, composite material NixCo3‑xS4/NiCo2O4Composite material.It prepares：By NiSO4·6H2O、CoSO4·6H2O and K2S2O8It is uniformly mixed, then by above-mentioned with NixCo3‑xS4The nickel foam of nano-chip arrays is vertically put into mixed solution and is added ammonia spirit, keeps 3 20min, calcining to get.The Ni that the present invention designs and synthesizesxCo3‑xS4@NiCo2O4Composite material shows excellent chemical property, has critically important application prospect.
Description
Technical field
The invention belongs to super capacitor material and its preparation field, more particularly to a kind of ultracapacitor NixCo3-xS4/
NiCo2O4Composite material and preparation method.
Background technology
With the getting worse of the fast development of global economy, the continuous consumption of fossil energy, environmental pollution, research is a kind of
Efficiently, inexpensive, environmental-friendly, high performance energy conversion and stocking system have become more and more important.Ultracapacitor
Due to having many advantages, such as high power density, fast charging and discharging rate and long cycle life and under being considered most promising
Generation energy is converted and storage facilities.However, being compared with battery with fuel cell, the low energy density of ultracapacitor is seriously made
About its following large-area applications.Developing one kind that novel, high performance electrode material is raising super capacitor energy density has
Efficacious prescriptions method.Transient metal sulfide is due to being considered excellent with specific capacitance more higher than carbon material and conducting polymer
Electrode material.In numerous transient metal sulfides, NiCo2S4Since there is superior electricity than single metal sulfide
Conductance and multiple oxidation state can be provided for faraday's reversible reaction is considered as new class high performance electrode material.Therefore, structure
It builds and is based on NiCo2S4The combination electrode material of material is of great significance to improving ultracapacitor chemical property.The present invention is set
The Ni for counting and synthesizingxCo3-xS4@NiCo2O4Composite material shows excellent chemical property, before having critically important application
Scape.
Invention content
Technical problem to be solved by the invention is to provide a kind of ultracapacitor NixCo3-xS4/NiCo2O4Composite material
And preparation method thereof, the ultracapacitor Ni prepared by the present inventionxCo3-xS4/NiCo2O4Composite material shows excellent electrification
Performance is learned, there is actual application prospect.
A kind of ultracapacitor Ni of the present inventionxCo3-xS4/NiCo2O4Composite material, it is characterised in that：The composite wood
Material is
NixCo3-xS4/NiCo2O4Composite material, wherein x=0-1.
A kind of ultracapacitor Ni of the present inventionxCo3-xS4/NiCo2O4The preparation method of composite material, including：
(1) Nickelous nitrate hexahydrate Ni (NO3)2·6H2O, cabaltous nitrate hexahydrate Co (NO3)2·6H2O and hexamethylenetetramine
HMT is dissolved in solvent, and is sufficiently stirred, and mixed solution is obtained；
(2) above-mentioned mixed solution is poured into reaction kettle and is put into nickel foam, reaction kettle is put into air dry oven,
React 3-12h under 90-120 DEG C of hydrothermal condition, cool down reaction kettle after reaction to room temperature, washing, and dry, obtain with
NixCo3-xS4The nickel foam of presoma；
(3) by above-mentioned with NixCo3-xS4The nickel foam of presoma is put into reaction kettle and is added sodium sulfide solution,
React 2-12 hours under 100-150 DEG C of hydrothermal condition, cool down reaction kettle after reaction to room temperature, wash, it is dry, obtain with
NixCo3-xS4The nickel foam of nano-chip arrays；
(4) by NiSO4·6H2O、CoSO4·6H2O and K2S2O8Solution be uniformly mixed, then by it is above-mentioned with
NixCo3-xS4The nickel foam of nano-chip arrays is vertically put into mixed solution and is added ammonium hydroxide, keeps 3-20min, calcining to get.
Ni (NO in the step (1)3)2·6H2O、Co(NO3)2·6H2O, the ratio of HMT is 1-10mmol:1-
10mmol： 0.1-10g.
Solvent is the mixed solution of water and ethyl alcohol in the step (1).
Reaction kettle is polytetrafluoroethylene (PTFE) hydrothermal reaction kettle in the step (2), (3).
Nickelous nitrate hexahydrate Ni (NO in step (1)3)2·6H2The molal weight ratio of vulcanized sodium is in O and step (3)
1-10mmol：0.1-2g.
The quality of vulcanized sodium is 0.1-2g in the step (3).
Washing is to be washed respectively with deionized water and alcohol solvent in the step (2), (3).
NiSO in the step (4)4·6H2O, CoSO4·6H2O and K2S2O8Molar ratio be 1:2:0.4.
The volume ratio of mixed solution and ammonium hydroxide is 180 in the step (4)：5-100.
Ammonia volume is 5-100mL in the step (4).
It is preferred that ammonia vol is 5-50ml.
Calcining is to be calcined in tube furnace in the step (4), and calcination temperature is 350-550 DEG C, and the time is 1-10 hours.
Advantageous effect
The ratio of the present invention research Ni and Co are to NixCo3-xS4The Electrochemical Performances of electrode material, and with electrochemistry
Ni that can be most excellentxCo3-xS4Electrode material builds combination electrode material, whole due to having synergistic effect that can improve therebetween
The chemical property of a electrode can meet the growth requirement of the following practical application.
Description of the drawings
Fig. 1 is the Ni that in the present invention prepared by embodiment 1xCo3-xS4@NiCo2O4(x=1.8) scanning electron microscope of composite material
Scheme (a, b)；Fig. 2 is the Ni that in the present invention prepared by embodiment 1xCo3-xS4@NiCo2O4(x=1.8) composite material and NixCo3-xS4
(x=1.8) cyclic voltammetric (a) of material, charge and discharge (b), area specific capacitance (c) and cyclical stability (d) figure.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
1)NixCo3-xS4The preparation of nano-chip arrays
(a) raw material 1.8mmol Nickelous nitrate hexahydrates (Ni (NO are weighed3)2·6H2O), 1.2mmol cabaltous nitrate hexahydrates (Co
(NO3)2·6H2O it) is dissolved into water (30ml) and ethyl alcohol (20ml) mixed solution, and fills with 0.8g hexamethylenetetramines (HMT)
Divide stirring.
(b) above-mentioned mixed solution is poured into polytetrafluoroethylene (PTFE) hydrothermal reaction kettle and is put into one piece of foam being cleaned
Reaction kettle is put into air dry oven by nickel, is reacted under 95 DEG C of hydrothermal conditions 8 hours, cools down reaction kettle after reaction to room
Temperature, and take out with NixCo3-xS4The nickel foam of presoma, is washed with deionized water and alcohol solvent respectively, and dry.
(c) by above-mentioned preparation with NixCo3-xS4The nickel foam of presoma is put into polytetrafluoroethylene (PTFE) hydrothermal reaction kettle simultaneously
0.5g sodium sulfide solutions are added, reaction kettle is put into air dry oven, is reacted 8 hours under 120 DEG C of hydrothermal conditions, react
Terminate postcooling reaction kettle to room temperature, and takes out with NixCo3-xS4The nickel foam of nano-chip arrays, respectively use deionized water and
Alcohol solvent washs, and dry.
2)NixCo3-xS4/NiCo2O4The preparation of composite material：By the 1M NiSO of 50mL4·6H2The 2M of O, 50mL
CoSO4·6H2The 0.25M K of O and 80mL2S2O8It is uniformly mixed, then by above-mentioned with NixCo3-xS4The foam of nano-chip arrays
Nickel is vertically put into mixed solution, and ammonia spirit (20mL) is added, and is taken out after being kept for 8 minutes.Finally the sample of taking-up is put
Enter calcining in the tube furnace of argon gas protection (calcination temperature is 300 DEG C, and the time is 2 hours), obtains NixCo3-xS4/NiCo2O4It is multiple
Condensation material.
NiCo2O4Nanometer sheet uniform fold is in NixCo3-xS4Material surface forms high porosity.Above-mentioned composite material
Area specific capacitance be up to 4.44F/cm2。
Embodiment 2
1)NixCo3-xS4The preparation of nano-chip arrays
(a) raw material 1.2mmol Nickelous nitrate hexahydrates (Ni (NO are weighed3)2·6H2O), 1.8mmol cabaltous nitrate hexahydrates (Co
(NO3)2·6H2O it) is dissolved into water (30ml) and ethyl alcohol (20ml) mixed solution, and fills with 0.8g hexamethylenetetramines (HMT)
Divide stirring.
(b) above-mentioned mixed solution is poured into polytetrafluoroethylene (PTFE) hydrothermal reaction kettle and is put into one piece of foam being cleaned
Reaction kettle is put into air dry oven by nickel, is reacted under 95 DEG C of hydrothermal conditions 8 hours, cools down reaction kettle after reaction to room
Temperature, and take out with NixCo3-xS4The nickel foam of presoma, is washed with deionized water and alcohol solvent respectively, and dry.
(c) by above-mentioned preparation with NixCo3-xS4The nickel foam of presoma is put into polytetrafluoroethylene (PTFE) hydrothermal reaction kettle simultaneously
1g sodium sulfide solutions are added, reaction kettle is put into air dry oven, is reacted 8 hours under 120 DEG C of hydrothermal conditions, reaction knot
Beam postcooling reaction kettle takes out to room temperature with NixCo3-xS4The nickel foam of nano-chip arrays uses deionized water and second respectively
Alcoholic solvent washs, and dry.
2)NixCo3-xS4/NiCo2O4The preparation of composite material：By the 1M NiSO of 50mL4·6H2The 2M of O, 50mL
CoSO4·6H2The 0.25M K of O and 80mL2S2O8It is uniformly mixed, then by above-mentioned with NixCo3-xS4The foam of nano-chip arrays
Nickel is vertically put into mixed solution, and ammonia spirit (50mL) is added, and is taken out after being kept for 8 minutes.Finally the sample of taking-up is put
Enter calcining in the tube furnace of argon gas protection (calcination temperature is 300 DEG C, and the time is 2 hours), obtains NixCo3-xS4/NiCo2O4It is multiple
Condensation material.
Claims (7)
1. a kind of ultracapacitor NixCo3-xS4/NiCo2O4The preparation method of composite material, including：
(1) Nickelous nitrate hexahydrate Ni (NO3)2·6H2O, cabaltous nitrate hexahydrate Co (NO3)2·6H2O and hexamethylenetetramine HMT are molten
It in solvent, and is sufficiently stirred, obtains mixed solution；
(2) above-mentioned mixed solution is poured into reaction kettle and is put into nickel foam, reaction kettle is put into air dry oven, in 90-
React 3-12h under 120 DEG C of hydrothermal conditions, cool down reaction kettle after reaction to room temperature, washing, and dry, obtain with
NixCo3-xS4The nickel foam of presoma；
(3) by above-mentioned with NixCo3-xS4The nickel foam of presoma is put into reaction kettle and is added sodium sulfide solution, in 100-
React 2-12 hours under 150 DEG C of hydrothermal conditions, cool down reaction kettle after reaction to room temperature, wash, it is dry, obtain with
NixCo3-xS4The nickel foam of nano-chip arrays；
(4) by NiSO4·6H2O、CoSO4·6H2O and K2S2O8It is uniformly mixed, then by above-mentioned with NixCo3-xS4Nanometer sheet battle array
The nickel foam of row is vertically put into mixed solution and is added ammonium hydroxide, keeps 3-20min, calcining to get；Wherein x=1.8.
2. a kind of ultracapacitor Ni according to claim 1xCo3-xS4/NiCo2O4The preparation method of composite material, it is special
Sign is：Ni (NO in the step (1)3)2·6H2O、Co(NO3)2·6H2O, the ratio of HMT is 1-10mmol:1-10mmol：
0.1-10g。
3. a kind of ultracapacitor Ni according to claim 1xCo3-xS4/NiCo2O4The preparation method of composite material, it is special
Sign is：Solvent is the mixed solution of water and ethyl alcohol in the step (1).
4. a kind of ultracapacitor Ni according to claim 1xCo3-xS4/NiCo2O4The preparation method of composite material, it is special
Sign is：The quality of vulcanized sodium is 0.1-2g in the step (3).
5. a kind of ultracapacitor Ni according to claim 1xCo3-xS4/NiCo2O4The preparation method of composite material, it is special
Sign is：NiSO in the step (4)4·6H2O, CoSO4·6H2O and K2S2O8Molar ratio be 1:2:0.4.
6. a kind of ultracapacitor Ni according to claim 1xCo3-xS4/NiCo2O4The preparation method of composite material, it is special
Sign is：Ammonia volume is 5-100mL in the step (4).
7. a kind of ultracapacitor Ni according to claim 1xCo3-xS4/NiCo2O4The preparation method of composite material, it is special
Sign is：Calcining is to be calcined in tube furnace in the step (4), and calcination temperature is 350-550 DEG C, and the time is 1-10 hours.
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| CN108258238B (en) * | 2018-01-16 | 2020-06-19 | 吉林大学 | Sodium ion battery cathode material NiCo with nano-sheet structure2S4And method for preparing the same |
| CN108597893B (en) * | 2018-05-28 | 2020-08-28 | 江苏大学 | Preparation method of supercapacitor composite electrode material based on foamed nickel |
| CN109119258A (en) * | 2018-08-27 | 2019-01-01 | 江南大学 | A kind of preparation method of electrode material |
| CN110330058A (en) * | 2019-06-20 | 2019-10-15 | 东华大学 | A kind of supercapacitor NixCoySzElectrode material and its preparation and application |
| CN112863887B (en) * | 2020-12-28 | 2022-02-08 | 沈阳工业大学 | Preparation method of high-performance cabbage-shaped heterostructure electrode material |
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