CN108773859A - A kind of vulcanization nano material and its preparation method and application - Google Patents

A kind of vulcanization nano material and its preparation method and application Download PDF

Info

Publication number
CN108773859A
CN108773859A CN201810823020.7A CN201810823020A CN108773859A CN 108773859 A CN108773859 A CN 108773859A CN 201810823020 A CN201810823020 A CN 201810823020A CN 108773859 A CN108773859 A CN 108773859A
Authority
CN
China
Prior art keywords
nano
hollow
ball
vulcanization
electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201810823020.7A
Other languages
Chinese (zh)
Other versions
CN108773859B (en
Inventor
张莉
韩欣茹
陈群
张宏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anhui Normal University
Original Assignee
Anhui Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Anhui Normal University filed Critical Anhui Normal University
Priority to CN201810823020.7A priority Critical patent/CN108773859B/en
Publication of CN108773859A publication Critical patent/CN108773859A/en
Application granted granted Critical
Publication of CN108773859B publication Critical patent/CN108773859B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • C01G53/006Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • C01G53/11Sulfides
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/80Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/04Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/30Particle morphology extending in three dimensions
    • C01P2004/32Spheres
    • C01P2004/34Spheres hollow
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/40Electric properties
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

Abstract

The present invention relates to electrode nano materials, specifically disclose a kind of preparation method of vulcanization nano material, the preparation method comprises the following steps:(1) hexa, divalent nickel source are dissolved in the water, reaction is heated under lasting mixing condition, nano material presoma is made;(2) nano material presoma is calcined;(3) product after calcining is scattered in the absolute ethyl alcohol containing thioacetamide, then heating reaction.Vulcanization nano material has been made by using hydrothermal method, in conjunction with calcining, sulfuration process in this method, which can be used as capacitor electrode material, has excellent specific capacitance.Moreover, the preparation method is simple, and controllably, it includes technique not need complicated equipment and gas, at low cost, has higher application value.

Description

A kind of vulcanization nano material and its preparation method and application
Technical field
The present invention relates to electrode nano materials, and in particular, to a kind of vulcanization nano material and its preparation method and application.
Background technology
Also increase rapidly with the consumption of the energy, and due to the shadow using environmental pollution and global climate of fossil energy Getting worse is rung, so exploring the energy storage system of efficient, green and sustainable development becomes urgent demand.In face of these Challenge, encourages researcher to pursue the energy storage device and technology of high performance.Ultracapacitor and other energy storage equipment phases Than (such as Li+Battery, Ni-MH battery), there are height ratio capacity, high circulation and the characteristics such as environmentally friendly, therefore as most having before One of the energy stores on way and converting apparatus.
According to energy storage mechanism, ultracapacitor can be divided into double electric layers supercapacitor (EDLCs) and pseudocapacitors.Fake capacitance Device can form a series of quick and reversible redox reactions in electrode surface energy storage, provide higher compared to EDLC Specific capacitance.Electrode material is to influence one of most important factor of performance of the supercapacitor.And in all kinds of super capacitor electrodes In the material of pole, the material of hollow structure is since its surface area is big, and Surface Permeability is good, and the diffusion path of ion and electronics is short and makes It obtains internal resistance reduction and power capability improves and causes great concern.
Currently, the method for having developed the hollow structure of many electrode materials for ultracapacitor, such as from group Dress technique, template, Ostwald ripening technique and solvent heat hydro-thermal method.For the electrode material applied to ultracapacitor In terms of expecting type, transient metal sulfide material is paid attention to by people in recent years.Since when applied to ultracapacitor, ternary Transient metal sulfide and binary transition metal sulfide have excellent ratio compared with traditional correspondence transition metal oxide The characteristics such as capacitance, stability, high rate performance.
Therefore, the transient metal sulfide material with hollow-core construction how is obtained, to obtain the specific capacitance for having excellent Electrode material, be the hot spot studied at present.
Invention content
The object of the present invention is to provide a kind of vulcanization nano materials and its preparation method and application, and this method is by using water Vulcanization nano material has been made in conjunction with calcining, sulfuration process in hot method, which can be used as electrode for capacitors material Material has excellent specific capacitance.Moreover, the preparation method is simple, and controllably, it includes work not need complicated equipment and gas Skill, it is at low cost, there is higher application value.
To achieve the goals above, the present invention provides a kind of preparation method of vulcanization nano material, the preparation methods Include the following steps:(1) hexa, divalent nickel source are dissolved in the water, reaction, system is heated under lasting mixing condition Obtain nano material presoma;(2) nano material presoma is calcined;(3) product after calcining is scattered in containing thio In the absolute ethyl alcohol of acetamide, then heating reaction.
The present invention also provides a kind of vulcanization nano materials being prepared according to previously described preparation method.
Moreover, the present invention also provides a kind of according to previously described vulcanization nano material in as electrode material Using.
Through the above technical solutions, sodium sulfide has been made by using hydrothermal method, in conjunction with calcining, sulfuration process in the present invention Rice material, the vulcanization nano material can be used as capacitor electrode material, have excellent specific capacitance.Moreover, the preparation side Method is simple, and controllably, it includes technique not need complicated equipment and gas, at low cost, has higher application value.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the microcosmic display figure of carbon ball in preparation example 1:(a), (b) is respectively the low power scanning electron microscope (SEM) photograph and height of carbon ball Times transmission electron microscope picture;
Fig. 2 is NiCo2(OH)6The detection figure of/C products:(a), (b) is respectively the NiCo of 1 gained of embodiment2(OH)6/ C is produced The low power scanning electron microscope (SEM) photograph and high power transmission electron microscope picture of object;
Fig. 3 is NiCo2O4The detection figure of hollow ball:(a), (b) is respectively the NiCo of 1 gained of embodiment2O4Low power scanning Electron microscope and high power transmission electron microscope picture;(c), (d) is respectively the NiCo of 1 gained of embodiment2O4EDX figure and X-ray powder diffraction Figure;
Fig. 4 is the detection figure of Ni-Co-S hollow balls:(a), the low power that (b) is respectively the Ni-Co-S of 1 gained of embodiment is swept Retouch electron microscope and high power transmission electron microscope picture;(c), (d) is respectively the EDX figures and x-ray powder of the Ni-Co-S of 1 gained of embodiment Diffraction pattern;(e), (f) is respectively the CV figures and constant current charge-discharge figure of the Ni-Co-S of 1 gained of embodiment;(g), (h) is respectively The high rate performance figure and EIS figures of the Ni-Co-S of 1 gained of embodiment;
Fig. 5 is Ni (OH)2The detection figure of/C:(a), (b) is respectively the Ni (OH) of 2 gained of embodiment2The low power of/C products is swept Retouch electron microscope and high power transmission electron microscope picture;
Fig. 6 is the detection figure of NiO hollow balls:(a), (b) is respectively the low power scanning electron microscope (SEM) photograph of the NiO of 2 gained of embodiment With high power transmission electron microscope picture;(c), (d) is respectively the EDX figures and X-ray powder diffraction figure of the NiO of 2 gained of embodiment;
Fig. 7 is the detection figure of Ni-S hollow balls:(a) it is the low power scanning electron microscope (SEM) photograph of the Ni-S of 2 gained of embodiment;(b), (c) be respectively the gained of embodiment 2 Ni-S EDX figures and X-ray powder diffraction figure;(d), (e) is the Ni-S of 2 gained of embodiment CV figure and constant current charge-discharge figure;(f) it is the EIS figures of the Ni-S of 2 gained of embodiment;
Fig. 8 is the NiCo of 3 gained of embodiment2(OH)6The low power scanning electron microscope (SEM) photograph of product;
Fig. 9 is NiCo in embodiment 32O4Detection figure:(a) it is the NiCo of 3 gained of embodiment2O4Low power scanning electron microscope Figure;(b) it is the NiCo of 3 gained of embodiment2O4X-ray powder diffraction figure;
Figure 10 is the detection figure of Ni-Co-S nano materials in embodiment 3:(a) it is the low of the Ni-Co-S of 3 gained of embodiment Times scanning electron microscope (SEM) photograph;(b) it is the X-ray powder diffraction figure of the Ni-Co-S of 3 gained of embodiment;(c), (d) is 3 gained of embodiment Ni-Co-S CV figure and constant current charge-discharge figure;(e) it is the EIS figures of the Ni-Co-S of 3 gained of embodiment.
Figure 11 is NiCo2O4Hollow ball as electrode material be applied to three electrode bodies when performance map:(a), (b) difference For the NiCo of 1 gained of comparative example2O4The CV figures and constant current charge-discharge figure of hollow ball;(c) it is the NiCo of 1 gained of comparative example2O4In The EIS of empty ball schemes;
Figure 12 is Co in comparative example 23O4The detection figure of hollow ball:(a) it is the Co of 2 gained of comparative example3O4Low power scanning electricity Mirror figure;(b) it is the Co of 2 gained of comparative example3O4X-ray powder diffraction figure;
Figure 13 is the detection figure of Co-S hollow balls:(a) it is the low power scanning electron microscope (SEM) photograph of the Co-S of 2 gained of comparative example;(b) it is The X-ray powder diffraction figure of the Co-S of 2 gained of comparative example;(c), (d) is respectively the CV figures and perseverance electricity of the Co-S of 2 gained of comparative example Flow charge and discharge electrograph;(e) it is the EIS figures of the Co-S of 2 gained of comparative example.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of preparation methods of vulcanization nano material, and the preparation method comprises the following steps:(1) will Hexa, divalent nickel source are dissolved in the water, and reaction is heated under lasting mixing condition, and nano material presoma is made; (2) nano material presoma is calcined;(3) product after calcining is scattered in the absolute ethyl alcohol containing thioacetamide In, then heating reaction.
Through the above technical solutions, sodium sulfide has been made by using hydrothermal method, in conjunction with calcining, sulfuration process in the present invention Rice material, the vulcanization nano material can be used as capacitor electrode material, have excellent specific capacitance.Moreover, the preparation side Method is simple, and controllably, it includes technique not need complicated equipment and gas, at low cost, has higher application value.
In the above-mentioned technical solutions, it for the concentration of bivalent nickel ion in water, can be adjusted in wider range, in order to Obtain that there is excellent specific capacitance and the vulcanization nano material of morphology controllable, it is preferable that bivalent nickel ion is a concentration of in solution 0.002-0.010mol/L。
Meanwhile for the molar ratio of bivalent nickel ion and hexa, can be adjusted in wider range, it can obtain To the vulcanization nano material with excellent specific capacitance and morphology controllable.In order to improve the yield of target substance, it is preferable that divalent The molar ratio of nickel ion and hexa is 1:0.5-3.
In addition, in step (3), absolute ethyl alcohol, the additive amount of product and thioacetamide after calcining can be wider It is adjusted in range, in order to obtain the vulcanization nano material with excellent specific capacitance and morphology controllable, it is preferable that step (3) in, relative to the absolute ethyl alcohol of 20mL, the additive amount of the product after calcining is 0.05-0.2mmol, and thioacetamide adds Dosage is 0.15-0.3mmol.
In addition, in order to improve the specific capacitance of material, in a kind of preferred embodiment of the present invention, the water in step (1) In also be added with divalent cobalt source.
Moreover, in order to keep the pattern of material more controllable, and the specific surface area of material is improved, to obtain specific capacitance Superior vulcanization nano material, in a kind of more preferred embodiment of the present invention, it is preferable that in the water in step (1) Also add citrate.In the case, the vulcanization nano material of nanometer sheet accumulation can be obtained.
In addition, in order to improve the specific surface area of material, the permeability of material is improved, further improves the ratio electricity of material Hold, it is preferable that carbon ball is also added in the water in step (1), in this way, nano material is deposited in the surface of carbon ball so that material Pattern it is more controllable, and in subsequent calcine technology, carbon ball can be removed, and obtain hollow vulcanization nano material, more Further increase the specific capacitance of material.
Certainly, one kind in the water in step (1) in selection addition divalent cobalt source, carbon ball and citrate, also can be two-by-two Addition, can improve the specific capacitance of material to a certain extent, in a kind of more preferred embodiment of the present invention, step (1) simultaneously added with divalent cobalt source, carbon ball and citrate in the water in.
Amount for the divalent cobalt source, carbon ball and the citrate that are added in the water in above-mentioned steps (1), can be in wider range It is inside selected, it is preferable that morphology controllable in order to obtain, the vulcanization nano material that specific capacitance is had excellent performance, it is preferable that nickelous Source, divalent cobalt source, the molar ratio of hexa and citrate are 1:0-2:0.5-3:0-0.3.
Morphology controllable in order to obtain, the vulcanization nano material that specific capacitance is had excellent performance, it is highly preferred that divalent nickel source, divalent The molar ratio of cobalt source, hexa and citrate is 1:1-2:0.75-2.5:0.125-0.25.
In addition, in the above-mentioned technical solutions, for the dosage of carbon ball, can be selected in wider range, it is preferable that phase For the divalent nickel source of 1mmol, the dosage of carbon ball is 0-50mg.
For the condition of heating reaction in step (1), can be adjusted in wider range, in order to obtain morphology controllable, The excellent vulcanization nano material of specific capacitance, it is preferable that the condition of heating reaction includes in step (1):Temperature is 80-95 DEG C, when Between be 4-8h.
Meanwhile the condition for being calcined in step (2), it can be adjusted in wider range, in order to obtain morphology controllable And the vulcanization nano material that specific capacitance is excellent, it is preferable that the condition of calcining includes in step (2):Temperature is 300 DEG C~500 DEG C, Time is 1-4h.
It for the product dispersing mode after calcining in step (3), can be selected in wider range, such as stirring, shake It swings, ultrasound etc., as long as mixed system is made to keep the state of nonstatic, the present invention can be achieved.Shape, uniform in size in order to obtain Vulcanization nano material, it is preferable that the mode disperseed in step (3) is ultrasonic disperse.
Shape, vulcanization nano material of uniform size in order to obtain, it is highly preferred that the time of ultrasonic disperse is 5-60min, Supersonic frequency is 30-50kHZ.
For the condition of heating reaction in step (3), can be adjusted in wider range, in order to obtain morphology controllable, The vulcanization nano material that specific capacitance is had excellent performance, in a kind of preferred embodiment of the present invention, heating reaction in step (3) Condition includes:Temperature is 120 DEG C~190 DEG C, time 10-14h.
In the above-mentioned technical solutions, carbon ball is Nano carbon balls, and carbon ball can not only play branch during the reaction as template Support frame frame acts on, and can be removed by calcining, and keeps reaction process more simple, controllable.Wherein, nano carbon microsphere can pass through A variety of preparation methods obtain, such as are recorded in Carbon, and 2005,43:1944-1953, by Y.Z.Jin, C.Gao, W.K.Hsu, Y.Zhu, D.R.M.Walton, the Large-scale synthiesis and characterization of delivered Chemical vapor deposition disclosed in carbon spheres prepared by direct pyrolysis of hydrocarbons Area method;It is recorded in Adv.Mater., 2002,19:1390-1393, J.Jang, B.Lim, the Selective delivered fabrication of carbon nanocapsules and mesocellular foams by surface-modified Template disclosed in colloidal silica templating;It is recorded in Solid State Commun., 2004,131: In 749-752, by G.Zou, D.Yu, J.Lu, D.Wang, Y.Qian, the A self-generated template that are delivered Carbon source cracking process disclosed in route to hollow carbon nanospheres in a short time;It is recorded in Angew.Chem.2004,116,607-611, the Colloidal carbon spheres delivered by X.M.Sun, Y.D.Li Hydro-thermal method disclosed in and their core/shell structures with noble-metal nanoparticles, Carbon ball obtained by the above method has similar property, state, is applicable as the carbon ball template of the present invention.
In a kind of preferred embodiment of the present invention because hydro-thermal method has a high purity product, shape and size controllably and The features such as cheap operating cost, it is preferable that nano carbon microsphere is synthesized using hydro-thermal method.
In order to further obtain the controllable high-purity carbon ball of shape and size, and reduce manufacturing cost, it is preferable that described Hydro-thermal method is carried out by following steps:Cetyl trimethylammonium bromide and glucose are dissolved into water, then in 160-180 DEG C reaction 10-14h, obtain brown product;Wherein, relative to the water of 20mL, the dosage of cetyl trimethylammonium bromide is 0.04- The dosage of 0.08g, glucose are 1.5-2.5g.
The controllable carbon ball of shape and size is can be obtained according to above-mentioned hydrothermal method, in order to be further reduced impurity, with When subsequently preparing Ni-Co-S/Ni-S/Co-S hollow nano-spheres, it is more advantageous to obtain that specific surface area is high, density is low, infiltration is made It makes good use of, the electrode material of electrochemical performance, it is preferable that the hydro-thermal method further includes by the brown product deionized water And/or after absolute ethyl alcohol washs 2-6 times, is dried in 50-70 DEG C of baking oven and obtain nano carbon microsphere powder.
It in the above technical solution, for divalent nickel source, may be present compared with more options, as long as it can have in aqueous solution It is the requirement for meeting the present invention that effect, which ionizes out bivalent nickel ion,.In order to improve reaction efficiency and reduce manufacturing cost, it is preferable that two Valence nickel source is NiSO4、Ni(NO3)2、NiCl2、NiBr2And NiAc2In it is one or more.
It in the above technical solution, for divalent cobalt source, may be present compared with more options, as long as it can have in aqueous solution It is the requirement for meeting the present invention that effect, which ionizes out divalent cobalt ion,.In order to improve reaction efficiency and reduce manufacturing cost, it is preferable that two Valence cobalt source is CoSO4、Co(NO3)2、CoCl2、CoBr2And CoAc2In it is one or more.
For citrate, in order to improve preparation efficiency, and manufacturing cost is reduced, it is preferable that citrate is citric acid Sodium and/or potassium citrate.
In the above-mentioned technical solutions, can be deionized water for the selection of water, ultra-pure water can also be single flash Water, distilled water etc., as long as routine experiment water, may conform to the requirement of the present invention, details are not described herein.
In addition for the addition manner of each component, there are many selection, dissolving latter substance adds another again, also may be used It is added simultaneously with many kinds of substance, continues mixed dissolution, these modes change, and do not interfere with the substantial effect of the present invention.
In addition, for the mode of lasting mixing, those skilled in the art can select in wider range, such as can be with It is stirring rod stirring, can also be magnetic agitation, can also be ultrasonic mixing, concussion etc., as long as makes liquid continuous in non-quiet The present invention can be achieved in only state.In embodiment later, carried out in a manner of magnetic agitation.
In addition, for the present invention mode of heating, can be selected in wider range, can select water-bath, oil bath, Insulating box, incubator, baking oven, reaction kettle etc., as long as reaction system is made to reach the temperature requirement that the present invention is required above, you can Realize the present invention, the mode in following Example, and unique embodiment of non-present invention, details are not described herein.
The present invention also provides a kind of vulcanization nano materials being prepared according to previously described preparation method.
Preferably, vulcanization nano material of the invention is the Ni-Co-S hollow balls of hollow ball-type.
Through the above technical solutions, sodium sulfide has been made by using hydrothermal method, in conjunction with calcining, sulfuration process in the present invention Rice material, the vulcanization nano material can be used as capacitor electrode material, have excellent specific capacitance.Moreover, the preparation side Method is simple, and controllably, it includes technique not need complicated equipment and gas, at low cost, has higher application value.
Moreover, the present invention also provides a kind of according to previously described vulcanization nano material in as electrode material Using.
The electrode material of vulcanization nano material prepared by the above method as ultracapacitor, for example, it is with process: The vulcanization nano material obtained is fabricated to application of electrode in three electrodes, wherein vulcanization nano material is as activity work electricity Pole, Pt are used as to electrode, and Hg/HgO electrodes are as reference electrode, and the potassium hydroxide solution of 3mol/L is as electrolyte.This hair The bright ultracapacitor that is applied to has excellent charge and discharge coulomb effect and larger specific capacitance.
The present invention will be described in detail by way of examples below.In the following embodiments, ultracapacitor is characterized Chemical property is by being documented in Applied Surface Science, and 2018,434:Cyclic voltammetry in 861-870 (CV), RSC Advances, 2016,6 (55) are documented in:It constant current charge-discharge method (GCD) in 50209-50216 and is documented in RSc Advances,2016,6(64):The means of testing such as the impedance spectrum (EIS) in 58916-58924.
Preparation example 1
It weighs 0.05g cetyl trimethylammonium bromides (CTAB) to be dissolved in 20mL deionized waters, add under magnetic stirring Enter 2g glucose, until completely dissolved, stops stirring, above-mentioned solution is poured into the reaction kettle of 25mL, be put into baking oven, heat up To 170 DEG C, 12h is reacted, is cooled to room temperature, centrifuges to obtain sediment, respectively washed for several times, in vacuum with deionized water and absolute ethyl alcohol 60 DEG C of dryings obtain carbon ball to constant weight in drying box.
The microcosmic display figure of carbon ball is shown in Fig. 1, as seen from Figure 1, wherein the low power scanning electron microscope (SEM) photograph of carbon ball is shown in Fig. 1 (a);Carbon The high power transmission electron microscope picture of ball is shown in Fig. 1 (b);Carbon ball template is the solid of size uniform it can be seen from Fig. 1 (a) and Fig. 1 (b) Ball, diameter are about 800nm, and independently of each other.
Preparation example 2
0.04g cetyl trimethylammonium bromides and 1.5g glucose are dissolved into 20mL water, then reacted at 160 DEG C 14h obtains brown product;Then it after brown product deionized water and absolute ethyl alcohol being washed 3 times, is dried in 50 DEG C of baking ovens To nano carbon microsphere powder.
Preparation example 3
0.08g cetyl trimethylammonium bromides and 2.5g glucose are dissolved into 20mL water, then reacted at 180 DEG C 10h obtains brown product;Then it after brown product deionized water and absolute ethyl alcohol being washed 6 times, is dried in 70 DEG C of baking ovens To nano carbon microsphere powder.
After testing, the character of nano carbon microsphere obtained is similar in preparation example 1 in preparation example 2 and preparation example 3.
Embodiment 1
By the carbon ball 20mg in preparation example 1 be added to containing 40mL deionized waters, six water nickel nitrates of 0.08mmol, In the solution of 0.16mmol cobalt nitrate hexahydrates, ultrasonic 10min, under stiring be added 0.2mmol hexas (HMTA) and 0.02mmol sodium citrates (TSC) continue to stir 60min acquisition homogeneous solutions;Previous solu is transferred to 50mL round-bottomed flasks In, by 90 DEG C of oil bath hydro-thermal, 4h is reacted, prepares nano material presoma NiCo2(OH)6/C;
Removing template will be removed in 500 DEG C of calcinings in Muffle furnace after the washing drying of nano material presoma, obtained hollow NiCo2O4
By above-mentioned hollow NiCo2O40.075mmol be added to the thioacetamide (TAA) containing 0.3mmol and 20mL without In the solution of water-ethanol, ultrasonic 5min obtains homogeneous solution;The solution is transferred in the reaction kettle of teflon coatings, by molten 170 DEG C of agent heat, reacts 12h in baking oven;It will be dried after the black powder washing centrifugation of acquisition, obtain Ni-Co-S hollow balls.
NiCo2(OH)6The detection figure of/C products is shown in Fig. 2, wherein Fig. 2 (a) is low power scanning electron microscope (SEM) photograph;NiCo2(OH)6/C The high power transmission electron microscope picture of product is shown in Fig. 2 (b);The NiCo it can be seen from Fig. 2 (a) and Fig. 2 (b)2O4The presoma of hollow ball is The medicine ball of laminated structure and size uniform, diameter are about 900nm.
NiCo2O4The detection figure of hollow ball is shown in Fig. 3, wherein NiCo2O4The low power scanning electron microscope (SEM) photograph of hollow ball is shown in Fig. 3 (a); NiCo2O4The high power transmission electron microscope picture of hollow ball is shown in Fig. 3 (b);NiCo2O4The EDX figures of hollow ball are shown in Fig. 3 (c);NiCo2O4It is hollow The X-ray powder diffraction figure of ball is shown in Fig. 3 (d);The NiCo it can be seen from Fig. 3 (a) and Fig. 3 (b)2O4Hollow ball be laminated structure and The hollow ball of size uniform, about 900nm;The ratio of display elements Ni, Co, O are close to 1 in Fig. 3 (c):2:4, with NiCo2O4 Substance coincide;Fig. 3 (d) is NiCo2O4The X-ray powder diffraction figure of hollow ball, with NiCo2O4(JCPDS No.20-0781) phase Meet.
The detection figure of Ni-Co-S hollow balls is shown in Fig. 4, wherein the low power scanning electron microscope (SEM) photograph of Ni-Co-S hollow balls is shown in Fig. 4 (a);The high power transmission electron microscope picture of Ni-Co-S hollow balls is shown in Fig. 4 (b);The EDX figures of Ni-Co-S hollow balls are shown in Fig. 4 (c);Ni-Co- The X-ray powder diffraction figure of S hollow balls is shown in Fig. 4 (d);The CV figures of Ni-Co-S hollow balls are shown in Fig. 4 (e);Ni-Co-S hollow balls Constant current charge-discharge figure is shown in Fig. 4 (f);The high rate performance figure of Ni-Co-S hollow balls is shown in Fig. 4 (g);The EIS of Ni-Co-S hollow balls schemes See Fig. 4 (h);Ni-Co-S hollow balls are the sky of surface rice-shaped structure and size uniform it can be seen from Fig. 4 (a) and Fig. 4 (b) Bulbus cordis, about 900nm;The ratio of display elements Ni, Co, S are close to 1 in Fig. 4 (c):3:5, with NiCo2S4/Co9S8Mixed phase It coincide;Fig. 4 (d) is the X-ray powder diffraction figure of Ni-Co-S hollow balls, with NiCo2S4(JCPDS No.20-0782)、Co9S8 (JCPDS No.19-0364) is consistent;It can be obtained by Fig. 4 (e), Fig. 4 (f) and Fig. 4 (h), Ni-Co-S hollow balls are as electricity When pole material is applied to three electrodes, at current density 1A/g, the specific capacitance of institute's invention material reaches 2210F/g;By Fig. 4 (g) With excellent high rate performance when can obtain Ni-Co-S hollow balls as electrode material applied to three electrodes;Fig. 4 (h) is shown To be Ni-Co-S hollow balls be applied to as electrode material three electrode when impedance spectra, from curve it is observed that in height There is a small semicircle, a diameter of charge transfer resistance (being denoted as Rct) of this semicircle in frequency domain;In low frequency range, then occur one The larger straight line of slope, the part due of straight line be the diffusion impedance (being denoted as W) of electrolyte, and wherein high frequency region and real axis is cut Away from expression solution resistance (being denoted as Rs);By analysis, it is located at the radius very little of high frequency region, illustrates the hollow ball electrode materials of Ni-Co-S The resistance of material is small;Compare inclination positioned at the curve of low frequency range, shows that this electrode material is a kind of ideal electrode of super capacitor Material.
When electrode material is applied to ultracapacitor, the resistance of impedance detection is one of the factor for influencing chemical property. Generally by the rectilinear(-al) of the semicircle of high frequency region and low frequency range, our institute's invention vulcanizing materials have smaller impedance diagram in high frequency region Radius is semicircle, shows there is lower charge transfer resistance, low charge transfer resistance is attributable to the high conductance of vulcanizing material Rate, and high conductivity promotes fast transfer of the charge in charge and discharge process, has preferable multiplying power so as to cause this material Performance;In addition, our institute's invention vulcanizing materials have the straight line of larger slope in low frequency range, it was demonstrated that it is with highest capacitive character Energy.
Embodiment 2
Carbon ball 20mg in preparation example 1 is added to the solution containing 40mL deionized waters, 0.4mmol six water nickel nitrates In beaker, 0.3mmol HMTA and 0.1mmol TSC are added in ultrasonic 30min under stiring, continue to stir 30min acquisitions uniformly Solution;Above-mentioned solution is transferred in 50mL round-bottomed flasks, by 90 DEG C of oil bath hydro-thermal, black powder Ni is made in 5h reactions (OH)2/C;Removing template will be removed in 300 DEG C of calcinings in Muffle furnace after the black powder washing drying of acquisition, before obtaining hollow NiO Drive body;
The hollow NiO presomas 0.16mmol of acquisition is added to TAA the and 20mL absolute ethyl alcohols containing 0.16mmol In solution, ultrasonic 10min obtains homogeneous solution;It transfers the solution into the reaction kettle of teflon coatings, passes through solvent heat 170 DEG C, 11h reacts in baking oven, obtains black powder;It will be dried after black powder washing centrifugation again, obtain Ni-S hollow balls.
Ni(OH)2The detection of/C is shown in Fig. 5 wherein, Ni (OH)2The low power scanning electron microscope (SEM) photograph of/C is shown in Fig. 5 (a);Ni(OH)2/ C is produced The high power transmission electron microscope picture of object is shown in Fig. 5 (b);The presoma of NiO hollow balls is sheet knot it can be seen from Fig. 5 (a) and Fig. 5 (b) The medicine ball of structure and size uniform, about 900nm.
The detection figure of NiO hollow balls is shown in Fig. 6, wherein the low power scanning electron microscope (SEM) photograph of NiO hollow balls is shown in Fig. 6 (a);NiO is hollow The high power transmission electron microscope picture of ball is shown in Fig. 6 (b);The EDX figures of NiO hollow balls are shown in Fig. 6 (c);The X-ray powder diffraction of NiO hollow balls Figure is shown in Fig. 6 (d);NiO hollow balls are the hollow ball of laminated structure and size uniform it can be seen from Fig. 6 (a) and Fig. 6 (b), greatly About 900nm;The ratio of display elements Ni, O is close to 1 in Fig. 6 (c):1, it coincide with NiO substances;Fig. 6 (d) is NiO hollow balls X-ray powder diffraction figure is consistent with NiO (JCPDS No.44-1159).
The detection figure of Ni-S hollow balls is shown in Fig. 7, wherein the low power scanning electron microscope (SEM) photograph of Ni-S hollow balls is shown in Fig. 7 (a);Ni-S The EDX figures of hollow ball are shown in Fig. 7 (b);The X-ray powder diffraction figure of Ni-S hollow balls is shown in Fig. 7 (c);The CV figures of Ni-S hollow balls are shown in Fig. 7 (d);The constant current charge-discharge figure of Ni-S hollow balls is shown in Fig. 7 (e);The EIS figures of Ni-S hollow balls are shown in Fig. 7 (f);By Fig. 7 (a) As can be seen that Ni-S hollow balls are rice-shaped structure and the more uniform hollow ball of size, about 900nm;Display in Fig. 7 (b) The ratio of element Ni, S are close to 1:1, it matches with NiS;Fig. 7 (c) is the X-ray powder diffraction figure of Ni-S hollow balls, with NiS (JCPDS No.02-1280), NiO (JCPDS No.44-1159) are consistent;It can be obtained by Fig. 7 (d), Fig. 7 (e) and Fig. 7 (f) Go out, when Ni-S hollow balls are applied to three electrodes as electrode material, at current density 1A/g, the specific capacitance of institute's invention material reaches To 1592F/g.Impedance spectra when Ni-S hollow balls are applied to three electrodes as electrode material is shown in Fig. 7 (f), from curve In it is observed that the semicircle radius occurred in high-frequency region is relatively large, illustrate that the resistance of Ni-S hollow ball electrode materials is more real Example 1 is applied compared to slightly larger;But the straight incline degree in low frequency range is smaller compared to Ni-Co-S, compared to Co-S, NiCo2O4Material It is larger, it is better than Co-S, NiCo when showing this material as electrode material for super capacitor2O4Electrode material.
Embodiment 3
Ni-Co-S sulfide nano-materials are prepared according to the method in embodiment 1, unlike, do not add carbon ball.
Corresponding NiCo2(OH)6The low power scanning electron microscope (SEM) photograph of product is shown in Fig. 8;As seen from Figure 8, NiCo2O4Forerunner Body is laminated structure but random structure.NiCo2O4Detection figure see Fig. 9, wherein NiCo2O4Low power scanning electron microscope (SEM) photograph See Fig. 9 (a);NiCo2O4X-ray powder diffraction figure see Fig. 9 (b);The NiCo it can be seen from Fig. 9 (a)2O4For laminated structure but There is no uniform shape;Fig. 9 (b) is NiCo2O4X-ray powder diffraction figure, with NiCo2O4(JCPDS No.20-0781) phase Meet.
The detection figure of corresponding Ni-Co-S nano materials is shown in Figure 10, wherein the low power scanning electricity of Ni-Co-S nano materials Mirror figure is shown in Figure 10 (a);The X-ray powder diffraction figure of Ni-Co-S is shown in Figure 10 (b);The CV figures of Ni-Co-S are shown in Figure 10 (c);Ni-Co- The constant current charge-discharge figure of S is shown in Figure 10 (d);The EIS figures of Ni-Co-S are shown in Figure 10 (e);The Ni-Co-S it can be seen from Figure 10 (a) For graininess shape structure;Figure 10 (b) is the X-ray powder diffraction figure of Ni-Co-S, with NiCo2S4(JCPDS No.20-0782)、 Co9S8(JCPDS No.19-0364) is consistent;It can be obtained by Figure 10 (c), Figure 10 (d), not using carbon ball as the Ni- of template When Co-S nano materials are applied to three electrodes as electrode material, at current density 1A/g, the specific capacitance of institute's invention material is only Reach 1472F/g;The Ni-Co-S nano materials not using carbon ball as template are shown as electrode material application in Figure 10 (e) Impedance spectra when three electrodes is observed that the semicircle radius occurred in high-frequency region is big from curve, illustrates this electrode The resistance of material is slightly larger;But the Ni-Co-S materials in embodiment 1 are only second in the straight incline degree of low frequency range, show this material It is only second to Ni-Co-S electrode materials in embodiment 1 when material is as electrode material for super capacitor.
Embodiment 4
Ni-Co-S hollow ball nano materials are prepared according to the method for embodiment 1, unlike, hollow NiCo2O4With it is thio The heating temperature of acetamide reaction vulcanization is changed to 120 DEG C, obtains corresponding Ni-Co-S hollow balls nano material.
Corresponding Ni-Co-S nano materials are hollow ball, and surface is rice-shaped structure;Its X-ray powder diffraction figure, with NiCo2S4(JCPDS No.20-0782)、Co9S8(JCPDS No.19-0364) is consistent.
Embodiment 5
Ni-Co-S hollow ball nano materials are prepared according to the method for embodiment 1, unlike, hollow NiCo2O4With it is thio The heating temperature of acetamide reaction vulcanization is changed to 160 DEG C, obtains corresponding Ni-Co-S hollow balls nano material.
Corresponding Ni-Co-S nano materials are hollow ball, and surface is rice-shaped structure;Its X-ray powder diffraction figure, with NiCo2S4(JCPDS No.20-0782)、Co9S8(JCPDS No.19-0364) is consistent.
Embodiment 6
Ni-Co-S hollow ball nano materials are prepared according to the method for embodiment 1, unlike, hollow NiCo2O4With it is thio The heating temperature of acetamide reaction vulcanization is changed to 180 DEG C, obtains corresponding Ni-Co-S hollow balls nano material.
Corresponding Ni-Co-S nano materials are hollow ball and size is more uniform, and surface is rice-shaped structure;Its X-ray powder Last diffraction pattern, with NiCo2S4(JCPDS No.20-0782)、Co9S8(JCPDS No.19-0364) is consistent.
Embodiment 7
Ni-Co-S hollow ball nano materials are prepared according to the method for embodiment 1, unlike, hollow NiCo2O4With it is thio The heating temperature of acetamide reaction vulcanization is changed to 190 DEG C, obtains corresponding Ni-Co-S hollow balls nano material.
Corresponding Ni-Co-S nano materials are hollow ball and size is more uniform, and surface is rice-shaped structure;Its X-ray powder Last diffraction pattern, with NiCo2S4(JCPDS No.20-0782)、Co9S8(JCPDS No.19-0364) is consistent.
The performance of Ni-Co-S nano materials synthesized under different curing temperatures is compared:Different curing temperature institutes Sample is applied as electrode material in three-electrode system, in current density under 5A/g, 120 DEG C, 160 DEG C, 170 DEG C, The specific capacitance of 180 DEG C, 190 DEG C curing temperatures is respectively 1345F/g, 1720F/g, 1940F/g, 1760F/g, 1030F/g, show and It is clear to, when curing temperature is 170 DEG C, when prepared sulfide is as electrode material, there is best specific capacitance.
Embodiment 8
Vulcanization nano material is prepared according to the method for embodiment 1, unlike, do not add sodium citrate.Obtained vulcanization Nano material is compared with the vulcanization nano material in embodiment 1, on pattern, the surface of hollow vulcanization nano material in embodiment 8 By larger nano particle accumulate rather than embodiment 1 in rice-shaped accumulate.Experiment proves that the sulphur in embodiment 8 When change nano material is applied to three electrodes as electrode material, at current density 1A/g, the specific capacitance of institute's invention material reaches 980F/g。
Embodiment 9
The preparation method for vulcanizing nano material, includes the following steps:
(1) hexa, nickel nitrate are dissolved in the water, in 95 DEG C under lasting mixing condition, heating reaction 4h, Nano material presoma is made;A concentration of 0.010mol/L of bivalent nickel ion, bivalent nickel ion and hexa rub You are than being 1:0.5;
(2) nano material presoma is carried out at 500 DEG C of calcining 1h;
(3) the product ultrasonic disperse 5min after calcining is scattered in the absolute ethyl alcohol containing thioacetamide, relative to The additive amount of the absolute ethyl alcohol of 20mL, the product after calcining is 0.2mmol, and the additive amount of thioacetamide is 0.3mmol;Then In 190 DEG C, heating reaction 10h.
Experiment proves that when the vulcanization nano material in embodiment 9 is applied to three electrodes as electrode material, it is close in electric current It spends under 1A/g, the specific capacitance of institute's invention material reaches 1300F/g.
Embodiment 10
The preparation method for vulcanizing nano material, includes the following steps:
(1) hexa, nickel nitrate are dissolved in the water, in 80 DEG C under lasting mixing condition, heating reaction 8h, Nano material presoma is made;A concentration of 0.002mol/L of bivalent nickel ion, bivalent nickel ion and hexa rub You are than being 1:3;
(2) nano material presoma is carried out at 300 DEG C of DEG C of calcining 4h;
(3) the product ultrasonic disperse 60min after calcining is scattered in the absolute ethyl alcohol containing thioacetamide, relative to The additive amount of the absolute ethyl alcohol of 20mL, the product after calcining is 0.05mmol, and the additive amount of thioacetamide is 0.15mmol;So Afterwards in 120 DEG C DEG C, heating reaction 14h.
Experiment proves that when the vulcanization nano material in embodiment 10 is applied to three electrodes as electrode material, in electric current Under density 1A/g, the specific capacitance of institute's invention material reaches 890F/g.
Comparative example 1
According to embodiment 1 method prepare nano material, unlike, without by calcining after product be scattered in containing In the absolute ethyl alcohol of thioacetamide, then the step of heating reaction, therefore, obtains NiCo2O4Nano material.
NiCo2O4The detection figure of hollow ball is shown in Fig. 3 in embodiment 1.
NiCo2O4Performance when being applied to three electrode bodies as electrode material of hollow ball is shown in Figure 11, wherein NiCo2O4In The CV figures of empty ball are shown in Figure 11 (a), NiCo2O4The constant current charge-discharge figure of hollow ball is shown in Figure 11 (b), NiCo2O4The EIS of hollow ball Figure is shown in Figure 11 (c), can be obtained by Figure 11 (a), Figure 11 (b), NiCo2O4Hollow ball is applied to three electrode bodies as electrode material There is preferable specific capacitance performance when being, at current density 1A/g, the specific capacitance of institute's invention material reaches 660F/g, is less than Ni- The specific capacitance value of Co-S hollow balls;NiCo is shown in Figure 11 (c)2O4Hollow ball as electrode material be applied to three electrodes when Impedance spectra is observed that the semicircle radius occurred in high-frequency region is relatively small from curve, illustrates NiCo2O4Hollow ball The resistance of electrode material is smaller;But the straight slope in low frequency range is small, shows that this electrode material performance will be inferior to Ni-Co-S skies Bulbus cordis material.
Comparative example 2
By the carbon ball 20mg obtained in preparation example 2 be added to containing 40mL deionized waters, 0.4mmol cobalt nitrate hexahydrates it is molten In the beaker of liquid, 0.5mmol HMTA and 0.05mmol TSC are added in ultrasonic 10min under stiring, continue to stir 40min acquisitions Homogeneous solution;Above-mentioned solution is transferred in 50mL round-bottomed flasks, by 90 DEG C of oil bath hydro-thermal, 6h reactions prepare black powder Co(OH)2/C;By the black powder Co (OH) of acquisition2Removing template is removed in calcining in Muffle furnace after/C washings are dry, obtains hollow Co3O4Presoma;
By the hollow Co of above-mentioned acquisition3O4Presoma 0.065mmol is added to the TAA containing 0.261mmol and 20mL is anhydrous In the solution of ethyl alcohol, ultrasonic 20min obtains homogeneous solution;The solution is transferred in the reaction kettle of teflon coatings, by molten 170 DEG C of agent heat, 13h reacts to obtain sulfide black powder in baking oven.
It will be dried after the sulfide black powder washing centrifugation of acquisition, obtain Co-S hollow balls.
Co3O4The detection figure of hollow ball is shown in Figure 12, wherein Co3O4The low power scanning electron microscope (SEM) photograph of hollow ball is shown in Figure 12 (a); Co3O4The X-ray powder diffraction figure of hollow ball is shown in Figure 12 (b);The Co it can be seen from Figure 12 (a)3O4For laminated structure and size Uniform hollow ball, about 900nm;Fig. 9 (b) is Co3O4The X-ray powder diffraction figure of hollow ball, with Co3O4(JCPDS No.43-1003) it is consistent.
The detection figure of Co-S hollow balls is shown in Figure 13, wherein the low power scanning electron microscope (SEM) photograph of Co-S hollow balls is shown in Figure 13 (a);Co- The X-ray powder diffraction figure of S hollow balls is shown in Figure 13 (b);The CV figures of Co-S hollow balls are shown in Figure 13 (c);The perseverance electricity of Co-S hollow balls Stream charge and discharge electrograph is shown in Figure 13 (d);The EIS figures of Co-S hollow balls are shown in Figure 13 (e).
Co-S hollow balls are rice-shaped structure and the more uniform hollow ball of size it can be seen from Figure 13 (a), and diameter is about For 900nm;Figure 13 (b) is the X-ray powder diffraction figure of Co-S hollow balls, with Co4S3(JCPDS No.02-1458)、Co9S8 (JCPDS No.02-1459) is consistent;It can be obtained by Figure 13 (c), Figure 13 (d), Co-S hollow balls are as electrode material application When three electrodes, at current density 1A/g, the specific capacitance of institute's invention material reaches 578F/g;Co-S is shown in Figure 13 (e) Hollow ball is applied to impedance spectra when three electrodes as electrode material, it is observed that occurring in high-frequency region from curve Semicircle radius size is only second to the Ni-Co-S hollow ball materials not using carbon ball as template, illustrates the resistance phase of this electrode material To smaller;But only compare NiCo in the straight incline degree of low frequency range2O4Material is big, shows this material as super capacitor electrode It is relatively poor when the material of pole, but it is better than NiCo2O4Electrode material.
To sum up, when vulcanization nano material of the invention is used as applied to three electrodes, at current density 1A/g, than electricity Hold and is up to 2210F/g, it is minimum also to reach 900F/g or so and larger in the straight incline degree of low frequency range, it is excellent super Capacitor electrode material.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (10)

1. a kind of preparation method of vulcanization nano material, which is characterized in that the preparation method comprises the following steps:
(1) hexa, divalent nickel source are dissolved in the water, reaction is heated under lasting mixing condition, nanometer material is made Material precursor;
(2) nano material presoma is calcined;
(3) product after calcining is scattered in the absolute ethyl alcohol containing thioacetamide, then heating reaction.
2. preparation method according to claim 1, wherein a concentration of 0.002- of bivalent nickel ion in solution 0.010mol/L;And/or the molar ratio of bivalent nickel ion and hexa is 1:0.5-3;
And/or in step (3), relative to the absolute ethyl alcohol of 20mL, the additive amount of the product after calcining is 0.05-0.2mmol, The additive amount of thioacetamide is 0.15-0.3mmol.
3. preparation method according to claim 1 or 2, wherein be also added with divalent cobalt source, carbon in the water in step (1) It is one or more in ball and citrate;
Preferably, the molar ratio of divalent nickel source, divalent cobalt source, hexa and citrate is 1:0-2:0.5-3:0- 0.3;
It is further preferred that divalent nickel source, divalent cobalt source, the molar ratio of hexa and citrate are 1:1-2: 0.75-2.5:0.125-0.25;
Still further preferably, relative to the divalent nickel source of 1mmol, the dosage of carbon ball is 0-50mg.
4. preparation method according to claim 1 or 2, wherein the condition of heating reaction includes in step (1):Temperature is 80-95 DEG C, time 4-8h;
And/or the condition calcined in step (2) includes:Temperature is 300 DEG C~500 DEG C, time 1-4h.
5. preparation method according to claim 1 or 2, wherein the mode disperseed in step (3) is ultrasonic disperse;It is preferred that The time on ground, ultrasonic disperse is 5-60min;
And/or the condition of heating reaction includes in step (3):Temperature is 120 DEG C~190 DEG C, time 10-14h.
6. preparation method according to claim 2, wherein the carbon ball passes through chemical vapour deposition technique, template, carbon source Cracking process or hydro-thermal method are made;
Preferably, the carbon ball is made by hydro-thermal method;
It is further preferred that the hydro-thermal method is carried out by following steps:Cetyl trimethylammonium bromide and glucose is molten In solution to water, 10-14h is then reacted at 160-180 DEG C, obtains brown product;Wherein, relative to the water of 20mL, cetyl three The dosage of methyl bromide ammonium is 0.04-0.08g, and the dosage of glucose is 1.5-2.5g;
It is further preferred that the hydro-thermal method further includes washing the brown product with deionized water and/or absolute ethyl alcohol After 2-6 times, is dried in 50-70 DEG C of baking oven and obtain nano carbon microsphere powder.
7. preparation method according to claim 1 or 2, wherein divalent nickel source is NiSO4、Ni(NO3)2、NiCl2、NiBr2 And NiAc2In it is one or more.
8. preparation method according to claim 1 or 2, wherein divalent cobalt source is CoSO4、Co(NO3)2、CoCl2、CoBr2 And CoAc2In it is one or more;
And/or citrate is sodium citrate and/or potassium citrate.
9. the vulcanization nano material being prepared according to claim 1-8 any one of them preparation methods;
Preferably, the vulcanization nano material has hollow ball shape structure.
10. vulcanization nano material according to claim 9 is as the application in electrode material.
CN201810823020.7A 2018-07-25 2018-07-25 Vulcanized nano material and preparation method and application thereof Active CN108773859B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810823020.7A CN108773859B (en) 2018-07-25 2018-07-25 Vulcanized nano material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810823020.7A CN108773859B (en) 2018-07-25 2018-07-25 Vulcanized nano material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN108773859A true CN108773859A (en) 2018-11-09
CN108773859B CN108773859B (en) 2021-05-14

Family

ID=64031427

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810823020.7A Active CN108773859B (en) 2018-07-25 2018-07-25 Vulcanized nano material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN108773859B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109817899A (en) * 2018-12-05 2019-05-28 盐城工学院 A kind of preparation method and application of miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material
CN110797206A (en) * 2019-10-31 2020-02-14 上海应用技术大学 Co-Mn-S composite material and preparation method and application thereof
CN110942924A (en) * 2019-12-05 2020-03-31 桂林电子科技大学 Yeast cell-based Ni-Co-S-loaded porous carbon material and preparation method and application thereof
CN111054393A (en) * 2019-12-13 2020-04-24 江南大学 Co1-xS/BiVO4Nano-fiber composite photocatalyst and preparation method thereof
CN112010361A (en) * 2020-08-02 2020-12-01 北京理工大学 Preparation method for synthesizing heteroatom-doped nickel sulfide with various shapes by using metal organic framework

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103943826A (en) * 2014-04-21 2014-07-23 西安交通大学 Preparation method of metal oxide/sulfide and ordered mesoporous carbon composite energy-storage material
CN104129818A (en) * 2014-07-09 2014-11-05 奇瑞汽车股份有限公司 Nickel-cobalt oxide material and preparation method thereof
CN106587179A (en) * 2017-01-04 2017-04-26 安阳师范学院 Preparation method for hollow ellipsoidal nickel-manganese binary sulfide
CN107086304A (en) * 2017-03-30 2017-08-22 复旦大学 The preparation method of lithium-air battery transient metal sulfide air cathode material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103943826A (en) * 2014-04-21 2014-07-23 西安交通大学 Preparation method of metal oxide/sulfide and ordered mesoporous carbon composite energy-storage material
CN104129818A (en) * 2014-07-09 2014-11-05 奇瑞汽车股份有限公司 Nickel-cobalt oxide material and preparation method thereof
CN106587179A (en) * 2017-01-04 2017-04-26 安阳师范学院 Preparation method for hollow ellipsoidal nickel-manganese binary sulfide
CN107086304A (en) * 2017-03-30 2017-08-22 复旦大学 The preparation method of lithium-air battery transient metal sulfide air cathode material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109817899A (en) * 2018-12-05 2019-05-28 盐城工学院 A kind of preparation method and application of miscellaneous element doping carbon nanotube encapsulation metal sulfide composite negative pole material
CN110797206A (en) * 2019-10-31 2020-02-14 上海应用技术大学 Co-Mn-S composite material and preparation method and application thereof
CN110942924A (en) * 2019-12-05 2020-03-31 桂林电子科技大学 Yeast cell-based Ni-Co-S-loaded porous carbon material and preparation method and application thereof
CN111054393A (en) * 2019-12-13 2020-04-24 江南大学 Co1-xS/BiVO4Nano-fiber composite photocatalyst and preparation method thereof
CN111054393B (en) * 2019-12-13 2021-05-28 江南大学 Co1-xS/BiVO4Nano-fiber composite photocatalyst and preparation method thereof
CN112010361A (en) * 2020-08-02 2020-12-01 北京理工大学 Preparation method for synthesizing heteroatom-doped nickel sulfide with various shapes by using metal organic framework

Also Published As

Publication number Publication date
CN108773859B (en) 2021-05-14

Similar Documents

Publication Publication Date Title
CN108773859A (en) A kind of vulcanization nano material and its preparation method and application
CN106972155A (en) A kind of bimetallic oxide and preparation method and application based on MOFs
CN103594246A (en) Preparation method for electrode material of porous NiCo2O4 nanowire array supercapacitor
CN108390014A (en) The preparation method of foamed nickel supported different-shape cobalt black nano material
CN106910639B (en) A kind of NiTe for electrode material for super capacitor2Preparation method
CN102509628A (en) Nanometre Ni(OH)2 and Co(OH)2 composite material for super-capacitor and preparation method of nanometre Ni(OH)2 and Co(OH)2 composite material
CN106277078A (en) A kind of hollow sub-microsphere with multilamellar nickel sulfide shell and its preparation method and application
CN107195470A (en) Nanotube-shaped composite of nickel cobalt iron ternary metal oxide and preparation method thereof
CN106971855A (en) A kind of nickel ferrite based magnetic loaded nanoparticle electrode material and preparation method and purposes
CN105609325B (en) A kind of LaNiO with hollow structure3Sub-meter grade microballoon electrode material preparation method
CN106876150A (en) A kind of porous C oAl bimetallic oxides two dimension hierarchical structure electrode material and preparation method thereof
CN105931857A (en) Preparation method of LaCoO3 sub-micron sphere electrode material with porous structure
CN106409528B (en) A kind of ZnFe2O4Nano particle/Carbon fibe hybrid supercapacitor electrode material and preparation method thereof
CN106006763A (en) Method for preparing nickel cobaltate nanocrystalline assembly
CN108962617A (en) A kind of preparation method and applications of self assembly cobaltosic oxide classification microballoon
CN107316749B (en) Co3O4@CoWO4The preparation method and applications of nano-wire array Core-shell structure material
CN109616331A (en) A kind of hud typed nickel hydroxide nano piece/manganese cobalt/cobalt oxide combination electrode material and preparation method thereof
CN106186086A (en) A kind of preparation method and applications of mesoporous cobalt oxide nano material
CN106853997A (en) A kind of positive electrode and preparation method thereof and positive pole coating material and lithium ion battery
CN109671574B (en) MnCo2O4Nano-spherical particles, preparation method thereof and application thereof in super capacitor
CN106340403A (en) Preparation method and purpose of zinc cobaltate nano wire or nanometer band electrode material
CN109545573B (en) Preparation method of metal 1T-phase rhenium sulfide hollow nanosphere supercapacitor electrode material
CN106450236B (en) A kind of preparation method of lithium ion battery negative material
CN109052487B (en) MnCo2O4.5Hollow nanosphere and preparation method and application thereof
CN106876151B (en) A kind of MnSe/Ni electrode material and preparation method thereof for supercapacitor

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant