CN108257794A - A kind of preparation method and application of cobalt sulfide nickel/graphene plural gel - Google Patents
A kind of preparation method and application of cobalt sulfide nickel/graphene plural gel Download PDFInfo
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- CN108257794A CN108257794A CN201711481447.5A CN201711481447A CN108257794A CN 108257794 A CN108257794 A CN 108257794A CN 201711481447 A CN201711481447 A CN 201711481447A CN 108257794 A CN108257794 A CN 108257794A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 68
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 235000019441 ethanol Nutrition 0.000 claims abstract description 20
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 17
- 239000010439 graphite Substances 0.000 claims abstract description 17
- 239000003990 capacitor Substances 0.000 claims abstract description 13
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002604 ultrasonography Methods 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 61
- 239000000499 gel Substances 0.000 claims description 59
- 229910052759 nickel Inorganic materials 0.000 claims description 26
- 239000007795 chemical reaction product Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000017 hydrogel Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 150000001868 cobalt Chemical class 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 150000002815 nickel Chemical class 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000007772 electrode material Substances 0.000 description 44
- 229910003266 NiCo Inorganic materials 0.000 description 19
- 239000006260 foam Substances 0.000 description 18
- 239000002002 slurry Substances 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 239000002131 composite material Substances 0.000 description 10
- 230000005611 electricity Effects 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000006230 acetylene black Substances 0.000 description 6
- 239000010405 anode material Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000000840 electrochemical analysis Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000007710 freezing Methods 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 4
- 239000002120 nanofilm Substances 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- -1 carbon nano tube compound Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention discloses a kind of preparation method of cobalt sulfide nickel/graphene plural gel, prepares raw material and includes：Graphene oxide (GO), cobalt salt, nickel salt, thioacetamide and 95wt% ethyl alcohol etc., preparation process includes：Graphene oxide and ethyl alcohol are mixed into merga pass ultrasound and are prepared graphite oxide enolate solution, then by one step hydro thermal method in graphene oxide on piece growth in situ cobalt sulfide nickel microballoon, so as to obtain cobalt sulfide nickel/graphene plural gel.A kind of preparation method of cobalt sulfide nickel/graphene plural gel of the present invention, of low cost, preparation process is simple, and the cobalt sulfide nickel/graphene plural gel being prepared has excellent chemical property, can be applied to the positive electrode of asymmetric super-capacitor.
Description
Technical field
The present invention relates to transient metal sulfide-carbon material technical fields, and in particular to be a kind of cobalt sulfide nickel/graphite
The preparation method and application of alkene plural gel.
Background technology
Compared to secondary cell, ultracapacitor as energy storage device of new generation, have power density is high, have extended cycle life,
Charging is quick to wait outstanding advantages, has in fields such as portable electronic product, the pure electric automobiles of higher-wattage output requirement important
Application.But the specific capacity of ultracapacitor and energy density etc. are relatively low at present, the electrode material of ultracapacitor is to influence
The key of its specific capacity and energy density.
Graphene has an excellent performance, such as higher electric conductivity, excellent mechanical property, high specific surface area, light
Low and good chemical stability of density etc..These special natures make it be applied to energy conversion and the carrier neck of memory device
Domain, it is considered to be one of big most potential new material of future ten.However, graphene sheet layer is easy to stack, make the excellent of graphene
The opposite sex can be not fully utilized.
Cobalt sulfide nickel is a kind of typical bimetallic sulfide, has nontoxic, environmental-friendly, easily prepared, self-conductive
Property preferably and theoretical capacity value it is high the advantages that.Compared with monometallic nickel sulfide or cobalt sulfide, cobalt sulfide nickel has higher lead
Electrical property and theoretical capacity are widely paid close attention in fields such as electro-catalysis, ultracapacitor and lithium ion battery electrode materials
And application.But pure nanometer vulcanization cobalt granule nickel is easy to reunite, its active site is made not exposed fully, serious shadow
Ring the cyclical stability and specific capacity of energy stores.
Research shows that by adding in nanometer cobalt sulfide nickel between graphene sheet layer, the heap of graphene can be effectively inhibited
It is folded, while also can inhibit a nanometer reunion for cobalt sulfide nickel.Therefore, cobalt sulfide nickel is carried out with the graphene haveing excellent performance effectively multiple
Conjunction is of great significance.
" one kind is used for electrode material for super capacitor sulphur to publication No. CN107010676A (application number 201710316636.0)
Change the simple and convenient process for preparing of cobalt nickel nano film ", using two step solvent-thermal process, cobalt nickel presoma is first synthesized, then with thio second
Amide prepares cobalt sulfide nickel nano film for sulphur source, and the cobalt sulfide nickel nano film being prepared has repeatability height, building-up process
Simply, it is easy to control, the advantages of yield is big.Publication No. CN105244482A (application number 201510577445.0) " cobalt sulfide nickel/stone
Black alkene/carbon nano tube compound material and its preparation method and application " prepares sulphur using thiocarbamide as sulphur source hydrothermal synthesis is subsequently heat-treated
Change cobalt nickel/graphene/carbon nano-tube trielement composite material, the cobalt sulfide nickel/Graphene/carbon nanotube composite material being prepared
With the three-dimensional net structure being coupled to each other, preferable electric conductivity and higher specific surface area make with high electrochemical activity
It is evenly distributed on graphene/carbon nanofiber aeroge with the cobalt sulfide nickel nano film of high theoretical capacity, makes cobalt sulfide nickel
The active site of nanometer sheet is fully exposed, and is the ideal electrode material of the new energy devices such as ultracapacitor, lithium ion battery
Material.
Invention content
It is of low cost the purpose of the present invention is to provide a kind of preparation method of cobalt sulfide nickel/graphene plural gel, system
Standby process is simple, and the cobalt sulfide nickel/graphene plural gel being prepared has excellent chemical property.
The preparation-obtained cobalt sulfide nickel/graphene plural gel of the present invention can be applied to asymmetric super-capacitor just
Pole material.
In order to achieve the above objectives, solution of the invention is：
A kind of preparation method of cobalt sulfide nickel/graphene plural gel, includes the following steps：
(1) first by rate of charge, by Ni (NO3)2·6H2O、Co(NO3)2·6H2O and thioacetamide be dissolved in a concentration of 1~
In the graphite oxide enolate solution of 5mg/mL, 1~3h of ultrasound, obtains mixed solution after stirring evenly；
(2) and then by step (1) mixed solution obtained is transferred in autoclave, and autoclave is put in locking
Heating reaction is carried out in constant temperature blast drying oven；
(3) after the completion of heating reaction, autoclave is cooled to room temperature, takes out hydrogel reaction product；
(4) and then by step (3) the hydrogel reaction product obtained is placed in magnetic agitation in deionized water and purifies, respectively
With deionized water and 95wt% ethyl alcohol, slightly washing is multiple, is finally freeze-dried the hydrogel reaction product of washes clean, i.e.,
Cobalt sulfide nickel/graphene the plural gel is obtained, is denoted as NiCo2S4/ rGO plural gels.
In step (1), the Ni (NO3)2·6H2O、Co(NO3)2·6H2The molar ratio of O and thioacetamide is 1:2:4,
The dosage of the graphite oxide enolate solution is 35mL, with the cobalt sulfide nickel (NiCo of synthesis2S4) in nickel quality and graphene
Mass ratio meter, the rate of charge control is 1.68~0.33:In the range of 1.
In step (1), the rate of charge is 0.42:1.
In step (2), the temperature of the heating reaction is 150 DEG C, and the time of the heating reaction is for 24 hours.
In step (4), the time of the purification process is 12h, and the detailed process of the freeze-drying is, first that washing is dry
Net hydrogel reaction product is placed at -15 DEG C of refrigerator after frost, then is placed in freeze drier at -50 DEG C and is dried for 24 hours.
A kind of cobalt sulfide nickel/graphene plural gel is used as the system of the positive electrode of asymmetric super-capacitor in the present invention
Standby process includes the following steps：
It first will be by above-mentioned steps and requirement NiCo well prepared in advance2S4/ rGO plural gels, conductive agent acetylene black and bonding
Agent 60wt% polytetrafluoroethylene (PTFE) concentrates are according to 8：1：1 mass ratio mixing, then adds in suitable ethanol solution, stirs
Ultrasound 1h, obtains finely dispersed diluted NiCo after uniformly2S4/ rGO composite material powder suspension slurries；It then will with glass bar
The slurry being stirred uniformly slowly is coated in and pre-processes in clean nickel foam, to be coated to be uniformly placed on vacuum drying chamber
In, dry 1h at 110 DEG C, dry record quality of weighing, so repeatedly uniformly coating, it is dry for several times to nickel foam weightening 2~
3mg/cm2；Vacuum drying chamber is finally placed in, is dried overnight at 60 DEG C, makes electrode active material NiCo2S4Curing to get to
NiCo2S4/ rGO combination electrode materials, last electricity consumption transmission roller press is to NiCo2S4/ rGO combination electrode materials carry out tabletting so that
Electrode active material NiCo2S4Tightly securely it is incorporated in the nickel foam of porous structure.
This hair is characterized using scanning electron microscope (SEM), transmission electron microscope (TEM) and electrochemical test system
The pattern and structure of bright preparation-obtained cobalt sulfide nickel/graphene plural gel and the electricity as super capacitor anode material
Chemical property, result are as follows：
(1) SEM test results show：Prepared NiCo in the present invention2S4In/rGO plural gels, NiCo2S4Presentation is received
Meter level microspheroidal, diameter of nano particles are distributed between graphene two-dimensional slice, effectively press down about between 100~200nm
The stacking of graphene sheet layer is made.These NiCo2S4Nano microsphere particles are uniformly coated by big grain size rGO pieces, form one
Effective three-dimensional channel.Such unique three-dimensional structure necessarily improves NiCo2S4The electron transfer rate of nano-particle, and shape
The active path spread into electrolyte ion, increases the active site of faraday's redox reaction, can be obviously improved
The chemical property of electrode material for super capacitor.Referring to Fig. 1.
(2) TEM test results show：A large amount of NiCo2S4Nano microsphere particles are uniformly coated by rGO pieces.RGO pieces are in fold
Structure, similar corrugated, more fully shows NiCo2S4The presence of rGO in/rGO plural gels.Heterogeneous Composite object structure it is uniform
Consistency shows NiCo2S4Nano-particle and rGO are well effectively combined, and improve the specific surface area of active site and material,
Be conducive to active material and more fully contact electrolyte, increase operation rate, so as to improve chemical property.Referring to Fig. 2.
(3) electrochemical property test：It is carried out in the system of 2mol/L KOH aqueous solutions, supplemented by platinized platinum (3cm × 3cm)
Help electrode, Hg/HgO is reference electrode, NiCo2S4/ rGO or NiCo2S4For working electrode.
It is specific that test result is as follows：Fig. 3 shows NiCo2S4/ rGO electrodes and NiCo2S4The cyclic voltammetry curve of electrode is all gathered around
There are a pair of apparent redox peaks, the cyclic voltammetry curve of two kinds of electrodes there are apparent redox peaks, shows the electricity
Chemical process is reversible faraday's reaction, shows typical faraday's capacitance characteristic.For NiCo2S4Electrode, Ke Yiqing
Clear sees in 0.26V and 0.44V (Ni2+/Ni3+And Co2+/Co3+/Co4+) at have a pair of apparent redox peaks, explanation
NiCo2S4Reversible faraday's redox reaction has occurred in active material here.NiCo2S4The cycle of/rGO combination electrodes
Volt ampere area is much larger than pure NiCo2S4Electrode, and peak current is also very prominent, is also much higher than pure NiCo2S4.Explanation
It has more prominent remarkable super capacitor chemical property.Being obviously improved for its chemical property, is attributed to the fact that three-dimensional graphite
The assistance of alkene skeleton bigger serface and high electronic conductivity characteristic, not only electrode material chemical reaction provide abundant work
Property site, and effectively facilitated ion diffusion and electron transfer；In addition, benefit from the electric double layer electricity of three-dimensional grapheme contribution
Hold；Also on the one hand it is NiCo2S4It is prominent faraday's material, there is the abundant redox reaction appraised at the current rate.
Fig. 4 is NiCo under graphene oxide (GO) concentration different in the present invention2S4/ rGO electrodes are in 1A g-1Electric discharge it is bent
Line.(graphite oxide enol is added in when the GO concentration of addition is respectively 1mg/mL, 2mg/mL, 3mg/mL, 4mg/mL, 5mg/mL
The volume of solution is 35mL), the specific capacity of combination electrode material is respectively 415.0C g-1、525.5C g-1、649.0C g-1、
714.0C g-1、525.0C g-1.Specific capacity is presented one and is first incremented by the process successively decreased afterwards.To find out its cause, add in suitable quality
RGO can preferably improve the electric conductivity of combination electrode material, effectively facilitate the transfer of electrode material body phase internal charge.Pass through
NiCo2S4Ratio allotment with rGO can influence rGO and NiCo2S4The dispersion and reunion of nano-particle, obtain chemical property
To steadily improving.But after rGO contents are more than certain value, combination electrode material will appear the phenomenon that many unfavorable, especially multiple
The reunion of composite electrode active material causes ill effect to material structure and performance so that the specific capacity of combination electrode material
Anti- drop is not risen.
Fig. 5 is NiCo2S4Charge and discharge (GCD) curve of/rGO combination electrodes under each current density, be intuitively with
Current density is from 1A g-1Increase to 20A g-1, the GCD curves of combination electrode still keep preferable symmetry, embody
NiCo2S4/ rGO plural gel electrodes good invertibity and possess excellent times in test job in charge and discharge process
Rate performance and fast charging and discharging ability.
Fig. 6 is NiCo2S4The cycle life figure of/rGO combination electrodes, in the incipient stage of test, the capacity of combination electrode goes out
A process constantly risen is showed.When reaching 400 cycle charge-discharges, NiCo2S4The specific capacity of/rGO combination electrode materials
Reach maximum value.This is derived from the progress of reaction, more and more electrode active material NiCo2S4Come into full contact with electrolyte from
Son, electrochemical reaction improved efficiency.When loop test continues, the slow of fluctuation is just presented in the specific capacity of combination electrode material
Slow decay trend.After 5000 cycle charge-discharges, capacity is intended to a stationary value, the capacity of combination electrode material according to
So maintaining maximum value obtains 90.21%, and in other words capacitance loss rate only has 9.79%.This fully shows the NiCo2S4/ rGO is compound
Electrode material has excellent long circulation life.Outstanding advantage in terms of specific capacity, high rate performance and cyclical stability makes
NiCo2S4/ rGO combination electrode materials show huge commercial application value in ultracapacitor energy storage field.
After adopting the above technical scheme, a kind of preparation method of cobalt sulfide nickel/graphene plural gel of the present invention, passes through letter
Single technique, is prepared a kind of novel cobalt sulfide nickel/graphene plural gel, which has following advantage：
(1) cobalt sulfide nickel/graphene plural gel has unique three-dimensional net structure and high-specific surface area, can be sulphur
Change cobalt nickel and more growth sites are provided, restrained effectively a nanometer reunion for cobalt sulfide nickel, make the active site of cobalt sulfide nickel
Fully exposed；
(2) graphene film and its excellent electric conductivity of the three-dimensional conductive skeleton constructed are conducive to the transmission of electronics, improve
The electric conductivity of plural gel entirety；
(3) cobalt sulfide nickel nanoparticle has higher theoretical capacity in itself, can improve the specific capacity of plural gel entirety,
Therefore, it is cobalt sulfide nickel nanoparticle and graphene film progress is compound, it can realize good synergistic effect, it is excellent to prepare performance
Different combination electrode material.
Description of the drawings
Fig. 1 is NiCo in the present invention2S4The SEM figure of/rGO plural gels under different amplification；
Fig. 2 is NiCo in the present invention2S4The TEM figures of/rGO plural gels；
Fig. 3 is that sweep speed is 5mV s in the present invention-1When NiCo2S4And NiCo2S4The cyclic voltammetric (CV) of/rGO electrodes
Curve；
Fig. 4 is NiCo under difference GO concentration in the present invention2S4/ rGO electrodes are in 1A g-1Discharge curve；
Fig. 5 is NiCo in the present invention2S4Charge and discharge (GCD) curve of/rGO electrodes under different current densities；
Fig. 6 is NiCo2S4The cycle life figure of/rGO combination electrode materials.
Specific embodiment
In order to further explain the technical solution of the present invention, the present invention is explained in detail below by specific embodiment
It states.
Embodiment one
1st, the preparation of cobalt sulfide nickel/graphene plural gel
(1) it first adds graphene oxide into 95wt% ethyl alcohol, ultrasonic disperse, obtains the 1mg/mL oxidations of stable dispersion
Graphite enolate solution；
(2) and then according to 1.68:1 rate of charge is (with the NiCo of synthesis2S4The quality of middle nickel and the mass ratio of graphene
Meter), by 0.2908g (1mmol) Ni (NO3)2·6H2O、0.5821g(2mmol)Co(NO3)2·6H2O and 0.3005g (4mmol)
Thioacetamide is dissolved in the graphite oxide enolate solution of 35mL, 1mg/mL, and ultrasound 3h, obtains mixed solution after stirring evenly；
(3) and then by obtained mixed solution it is transferred in 50mL autoclaves, locks, autoclave is placed in perseverance
In warm air dry oven, 150 DEG C of heating reactions are for 24 hours；
(4) after the completion of thermal response to be added, autoclave is cooled to room temperature, takes out the columnar water of black obtained by the reaction
Gel reaction product；
(5) and then obtained hydrogel reaction product is placed in magnetic agitation in 500mL deionized waters and purifies 12h, point
Not Yong deionized water and 95wt% ethyl alcohol slightly washing is multiple；
(6) finally the hydrogel reaction product of washes clean is placed at -15 DEG C of refrigerator after freezing, then is placed in freeze-drying
It is dried at -50 DEG C for 24 hours to get to cobalt sulfide nickel/graphene plural gel in machine, is denoted as NiCo2S4/ rGO plural gels.
2nd, cobalt sulfide nickel/graphene plural gel is used as the preparation of super capacitor anode material
First by NiCo well prepared in advance2S4/ rGO plural gels, conductive agent acetylene black and binding agent 60wt% polytetrafluoroethyl-nes
Alkene concentrate is according to 8：1：1 mass ratio mixing, then adds in suitable ethanol solution, surpasses after being stirred evenly with glass bar
Sound 1h obtains finely dispersed diluted NiCo2S4/ rGO composite material powder suspension slurries；Then it will be stirred with glass bar
Slurry is uniformly slowly coated in and pre-processes in clean nickel foam, to be coated to be uniformly placed in vacuum drying chamber, at 110 DEG C
Dry 1h, drying, which is weighed, records quality, so uniformly coats repeatedly, is dry for several times to 2~3mg of nickel foam weightening；Finally it is placed in
Vacuum drying chamber is dried overnight at 60 DEG C, makes electrode active material NiCo2S4Curing is to get to NiCo2S4/ rGO combination electrodes
Material, last electricity consumption transmission roller press is to NiCo2S4/ rGO combination electrode materials carry out tabletting so that electrode active material NiCo2S4
Tightly securely it is incorporated in the nickel foam of porous structure.
3、NiCo2S4The electro-chemical test of/rGO combination electrode materials
It is 1A g in current density-1Constant-current discharge mechanism under, specific capacity be 415.0C g-1。
Embodiment two
1st, the preparation of cobalt sulfide nickel/graphene plural gel
(1) it first adds graphene oxide into 95wt% ethyl alcohol, ultrasonic disperse, obtains the 2mg/mL oxidations of stable dispersion
Graphite enolate solution；
(2) and then according to 0.84:1 rate of charge is (with the NiCo of synthesis2S4The quality of middle nickel and the mass ratio of graphene
Meter), by 0.2908g (1mmol) Ni (NO3)2·6H2O、0.5821g(2mmol)Co(NO3)2·6H2O and 0.3005g (4mmol)
Thioacetamide is dissolved in the graphite oxide enolate solution of 35mL, 2mg/mL, and ultrasound 3h, obtains mixed solution after stirring evenly；
(3) and then by obtained mixed solution it is transferred in 50mL autoclaves, locks, autoclave is placed in perseverance
In warm air dry oven, 150 DEG C of heating reactions are for 24 hours；
(4) after the completion of thermal response to be added, autoclave is cooled to room temperature, takes out the columnar water of black obtained by the reaction
Gel reaction product；
(5) and then obtained hydrogel reaction product is placed in magnetic agitation in 500mL deionized waters and purifies 12h, point
Not Yong deionized water and 95wt% ethyl alcohol slightly washing is multiple；
(6) finally the hydrogel reaction product of washes clean is placed at -15 DEG C of refrigerator after freezing, then is placed in freeze-drying
It is dried at -50 DEG C for 24 hours to get to cobalt sulfide nickel/graphene plural gel in machine, is denoted as NiCo2S4/ rGO plural gels.
2nd, cobalt sulfide nickel/graphene plural gel is used as the preparation of super capacitor anode material
First by NiCo well prepared in advance2S4/ rGO plural gels, conductive agent acetylene black and binding agent 60wt% polytetrafluoroethyl-nes
Alkene concentrate is according to 8：1：1 mass ratio mixing, then adds in suitable ethanol solution, surpasses after being stirred evenly with glass bar
Sound 1h obtains finely dispersed diluted NiCo2S4/ rGO composite material powder suspension slurries；Then it will be stirred with glass bar
Slurry is uniformly slowly coated in and pre-processes in clean nickel foam, to be coated to be uniformly placed in vacuum drying chamber, at 110 DEG C
Dry 1h, drying, which is weighed, records quality, so uniformly coats repeatedly, is dry for several times to 2~3mg of nickel foam weightening；Finally it is placed in
Vacuum drying chamber is dried overnight at 60 DEG C, makes electrode active material NiCo2S4Curing is to get to NiCo2S4/ rGO combination electrodes
Material, last electricity consumption transmission roller press is to NiCo2S4/ rGO combination electrode materials carry out tabletting so that electrode active material NiCo2S4
Tightly securely it is incorporated in the nickel foam of porous structure.
3、NiCo2S4The electro-chemical test of/rGO combination electrode materials
It is 1A g in current density-1Constant-current discharge mechanism under, specific capacity be 525.5C g-1。
Embodiment three
1st, the preparation of cobalt sulfide nickel/graphene plural gel
(1) it first adds graphene oxide into 95wt% ethyl alcohol, ultrasonic disperse, obtains the 3mg/mL oxidations of stable dispersion
Graphite enolate solution；
(2) and then according to 0.56:1 rate of charge is (with the NiCo of synthesis2S4The quality of middle nickel and the mass ratio of graphene
Meter), by 0.2908g (1mmol) Ni (NO3)2·6H2O、0.5821g(2mmol)Co(NO3)2·6H2O and 0.3005g (4mmol)
Thioacetamide is dissolved in the graphite oxide enolate solution of 35mL, 3mg/mL, and ultrasound 3h, obtains mixed solution after stirring evenly；
(3) and then by obtained mixed solution it is transferred in 50mL autoclaves, locks, autoclave is placed in perseverance
In warm air dry oven, 150 DEG C of heating reactions are for 24 hours；
(4) after the completion of thermal response to be added, autoclave is cooled to room temperature, takes out the columnar water of black obtained by the reaction
Gel reaction product；
(5) and then obtained hydrogel reaction product is placed in magnetic agitation in 500mL deionized waters and purifies 12h, point
Not Yong deionized water and 95wt% ethyl alcohol slightly washing is multiple；
(6) finally the hydrogel reaction product of washes clean is placed at -15 DEG C of refrigerator after freezing, then is placed in freeze-drying
It is dried at -50 DEG C for 24 hours to get to cobalt sulfide nickel/graphene plural gel in machine, is denoted as NiCo2S4/ rGO plural gels.
2nd, cobalt sulfide nickel/graphene plural gel is used as the preparation of super capacitor anode material：
First by NiCo well prepared in advance2S4/ rGO plural gels, conductive agent acetylene black and binding agent 60wt% polytetrafluoroethyl-nes
Alkene concentrate is according to 8：1：1 mass ratio mixing, then adds in suitable ethanol solution, surpasses after being stirred evenly with glass bar
Sound 1h obtains finely dispersed diluted NiCo2S4/ rGO composite material powder suspension slurries；Then it will be stirred with glass bar
Slurry is uniformly slowly coated in and pre-processes in clean nickel foam, to be coated to be uniformly placed in vacuum drying chamber, at 110 DEG C
Dry 1h, drying, which is weighed, records quality, so uniformly coats repeatedly, is dry for several times to 2~3mg of nickel foam weightening；Finally it is placed in
Vacuum drying chamber is dried overnight at 60 DEG C, makes electrode active material NiCo2S4Curing is to get to NiCo2S4/ rGO combination electrodes
Material, last electricity consumption transmission roller press is to NiCo2S4/ rGO combination electrode materials carry out tabletting so that electrode active material NiCo2S4
Tightly securely it is incorporated in the nickel foam of porous structure.
3、NiCo2S4The electro-chemical test of/rGO combination electrode materials
It is 1A g in current density-1Constant-current discharge mechanism under, specific capacity be 649.0C g-1。
Example IV
1st, the preparation of cobalt sulfide nickel/graphene plural gel
(1) it first adds graphene oxide into 95wt% ethyl alcohol, ultrasonic disperse, obtains the 4mg/mL oxidations of stable dispersion
Graphite enolate solution；
(2) and then according to 0.42:1 rate of charge is (with the NiCo of synthesis2S4The quality of middle nickel and the mass ratio of graphene
Meter), by 0.2908g (1mmol) Ni (NO3)2·6H2O、0.5821g(2mmol)Co(NO3)2·6H2O and 0.3005g (4mmol)
Thioacetamide is dissolved in the graphite oxide enolate solution of 35mL, 4mg/mL, and ultrasound 3h, obtains mixed solution after stirring evenly；
(3) and then by obtained mixed solution it is transferred in 50mL autoclaves, locks, autoclave is placed in perseverance
In warm air dry oven, 150 DEG C of heating reactions are for 24 hours；
(4) after the completion of thermal response to be added, autoclave is cooled to room temperature, takes out the columnar water of black obtained by the reaction
Gel reaction product；
(5) and then obtained hydrogel reaction product is placed in magnetic agitation in 500mL deionized waters and purifies 12h, point
Not Yong deionized water and 95wt% ethyl alcohol slightly washing is multiple；
(6) finally the hydrogel reaction product of washes clean is placed at -15 DEG C of refrigerator after freezing, then is placed in freeze-drying
It is dried at -50 DEG C for 24 hours to get to cobalt sulfide nickel/graphene plural gel in machine, is denoted as NiCo2S4/ rGO plural gels.
2nd, cobalt sulfide nickel/graphene plural gel is used as the preparation of super capacitor anode material：
First by NiCo well prepared in advance2S4/ rGO plural gels, conductive agent acetylene black and binding agent 60wt% polytetrafluoroethyl-nes
Alkene concentrate is according to 8：1：1 mass ratio mixing, then adds in suitable ethanol solution, surpasses after being stirred evenly with glass bar
Sound 1h obtains finely dispersed diluted NiCo2S4/ rGO composite material powder suspension slurries；Then it will be stirred with glass bar
Slurry is uniformly slowly coated in and pre-processes in clean nickel foam, to be coated to be uniformly placed in vacuum drying chamber, at 110 DEG C
Dry 1h, drying, which is weighed, records quality, so uniformly coats repeatedly, is dry for several times to 2~3mg of nickel foam weightening；Finally it is placed in
Vacuum drying chamber is dried overnight at 60 DEG C, makes electrode active material NiCo2S4Curing is to get to NiCo2S4/ rGO combination electrodes
Material, last electricity consumption transmission roller press is to NiCo2S4/ rGO combination electrode materials carry out tabletting so that electrode active material NiCo2S4
Tightly securely it is incorporated in the nickel foam of porous structure.
3、NiCo2S4The electro-chemical test of/rGO combination electrode materials
It is 1A g in current density-1Constant-current discharge mechanism under, specific capacity be 714.0C g-1。
Embodiment five
1st, the preparation of cobalt sulfide nickel/graphene plural gel
(1) it first adds graphene oxide into 95wt% ethyl alcohol, ultrasonic disperse, obtains the 5mg/mL oxidations of stable dispersion
Graphite enolate solution；
(2) and then according to 0.33:1 rate of charge is (with the NiCo of synthesis2S4The quality of middle nickel and the mass ratio of graphene
Meter), by 0.2908g (1mmol) Ni (NO3)2·6H2O、0.5821g(2mmol)Co(NO3)2·6H2O and 0.3005g (4mmol)
Thioacetamide is dissolved in the graphite oxide enolate solution of 35mL, 5mg/mL, and ultrasound 3h, obtains mixed solution after stirring evenly；
(3) and then by obtained mixed solution it is transferred in 50mL autoclaves, locks, autoclave is placed in perseverance
In warm air dry oven, 150 DEG C of heating reactions are for 24 hours；
(4) after the completion of thermal response to be added, autoclave is cooled to room temperature, takes out the columnar water of black obtained by the reaction
Gel reaction product；
(5) and then obtained hydrogel reaction product is placed in magnetic agitation in 500mL deionized waters and purifies 12h, point
Not Yong deionized water and 95wt% ethyl alcohol slightly washing is multiple；
(6) finally the hydrogel reaction product of washes clean is placed at -15 DEG C of refrigerator after freezing, then is placed in freeze-drying
It is dried at -50 DEG C for 24 hours to get to cobalt sulfide nickel/graphene plural gel in machine, is denoted as NiCo2S4/ rGO plural gels.
2nd, cobalt sulfide nickel/graphene plural gel is used as the preparation of super capacitor anode material
First by NiCo well prepared in advance2S4/ rGO plural gels, conductive agent acetylene black and binding agent 60wt% polytetrafluoroethyl-nes
Alkene concentrate is according to 8：1：1 mass ratio mixing, then adds in suitable ethanol solution, surpasses after being stirred evenly with glass bar
Sound 1h obtains finely dispersed diluted NiCo2S4/ rGO composite material powder suspension slurries；Then it will be stirred with glass bar
Slurry is uniformly slowly coated in and pre-processes in clean nickel foam, to be coated to be uniformly placed in vacuum drying chamber, at 110 DEG C
Dry 1h, drying, which is weighed, records quality, so uniformly coats repeatedly, is dry for several times to 2~3mg of nickel foam weightening；Finally it is placed in
Vacuum drying chamber is dried overnight at 60 DEG C, makes electrode active material NiCo2S4Curing is to get to NiCo2S4/ rGO combination electrodes
Material, last electricity consumption transmission roller press is to NiCo2S4/ rGO combination electrode materials carry out tabletting so that electrode active material NiCo2S4
Tightly securely it is incorporated in the nickel foam of porous structure.
3、NiCo2S4The electro-chemical test of/rGO combination electrode materials
It is 1A g in current density-1Constant-current discharge mechanism under, specific capacity be 525.0C g-1。
The product form and style of above-described embodiment and schema and the non-limiting present invention, any technical field it is common
The appropriate variation or modification that technical staff does it all should be regarded as not departing from the patent category of the present invention.
Claims (6)
1. a kind of preparation method of cobalt sulfide nickel/graphene plural gel, it is characterised in that：Include the following steps：
(1) first by rate of charge, by Ni (NO3)2·6H2O、Co(NO3)2·6H2O and thioacetamide are dissolved in a concentration of 1~5mg/
In the graphite oxide enolate solution of mL, 1~3h of ultrasound, obtains mixed solution after stirring evenly；
(2) and then by step (1) mixed solution obtained is transferred in autoclave, and autoclave is placed in perseverance by locking
Heating reaction is carried out in warm air dry oven；
(3) after the completion of heating reaction, autoclave is cooled to room temperature, takes out hydrogel reaction product；
(4) and then by step (3) the hydrogel reaction product obtained is placed in magnetic agitation in deionized water and purifies, and spends respectively
Slightly washing is multiple for ionized water and 95wt% ethyl alcohol, finally by the hydrogel reaction product of washes clean be freeze-dried to get to
Cobalt sulfide nickel/graphene the plural gel.
2. a kind of preparation method of cobalt sulfide nickel/graphene plural gel according to claim 1, it is characterised in that：Step
Suddenly in (1), the Ni (NO3)2·6H2O、Co(NO3)2·6H2The molar ratio of O and thioacetamide is 1:2:4, the oxidation stone
The dosage of black enolate solution is 35mL, in terms of the quality of nickel in the cobalt sulfide nickel of synthesis and the mass ratio of graphene, the throwing
Material is than control 1.68~0.33:In the range of 1.
3. a kind of preparation method of cobalt sulfide nickel/graphene plural gel according to claim 2, it is characterised in that：Step
Suddenly in (1), the rate of charge is 0.42:1.
4. a kind of preparation method of cobalt sulfide nickel/graphene plural gel according to claim 1, it is characterised in that：Step
Suddenly in (2), the temperature of the heating reaction is 150 DEG C, and the time of the heating reaction is for 24 hours.
5. a kind of preparation method of cobalt sulfide nickel/graphene plural gel according to claim 1, it is characterised in that：Step
Suddenly in (4), the time of the purification process is 12h, and the detailed process of the freeze-drying is, first by the hydrogel of washes clean
Reaction product is placed at -15 DEG C of refrigerator after frost, then is placed in freeze drier at -50 DEG C and is dried for 24 hours.
6. a kind of preparation method of cobalt sulfide nickel/graphene plural gel according to claim 1, it is characterised in that：Institute
The cobalt sulfide nickel being prepared/application of the graphene plural gel as the positive electrode of asymmetric super-capacitor.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108993536A (en) * | 2018-07-25 | 2018-12-14 | 河南大学 | A kind of palladium grown in conductive substrates-nickel cobalt sulphur composite nano tube array elctro-catalyst and preparation method thereof, application |
| CN109003827A (en) * | 2018-07-27 | 2018-12-14 | 福州大学 | A kind of preparation method and application of spongy graphene/nickel cobalt sulfide composite material |
| CN109243843A (en) * | 2018-10-08 | 2019-01-18 | 西安交通大学 | A kind of ultra-fine sulfide/graphene Two-dimensional Composites and its preparation method and application |
| CN110136989A (en) * | 2019-06-10 | 2019-08-16 | 东北大学秦皇岛分校 | A kind of positive, preparation method and supercapacitor obtained |
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| CN110627134A (en) * | 2019-09-26 | 2019-12-31 | 广东工业大学 | Preparation method of cobalt-nickel sulfide electrode material and battery |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104299797A (en) * | 2014-11-06 | 2015-01-21 | 中南大学 | Water-system asymmetric super-capacitor based on NiCo2S4 and NiCo2S4 composite material |
| CN105161317A (en) * | 2015-06-03 | 2015-12-16 | 南京理工大学 | Method for quickly preparing cobalt sulfide/graphene hydrogel nano composite material |
| CN106328947A (en) * | 2016-10-12 | 2017-01-11 | 北京化工大学 | Graphene aerogel loaded two-phase transition metal sulfide as well as preparation method and application thereof |
-
2017
- 2017-12-29 CN CN201711481447.5A patent/CN108257794A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104299797A (en) * | 2014-11-06 | 2015-01-21 | 中南大学 | Water-system asymmetric super-capacitor based on NiCo2S4 and NiCo2S4 composite material |
| CN105161317A (en) * | 2015-06-03 | 2015-12-16 | 南京理工大学 | Method for quickly preparing cobalt sulfide/graphene hydrogel nano composite material |
| CN106328947A (en) * | 2016-10-12 | 2017-01-11 | 北京化工大学 | Graphene aerogel loaded two-phase transition metal sulfide as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZHONGCHUN LI ET AL.: "NiCo2S4nanoparticles anchored on reduced graphene oxide sheets:In-situ synthesis and enhanced capacitive performance", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
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| CN108993536B (en) * | 2018-07-25 | 2021-01-29 | 河南大学 | Palladium-nickel-cobalt-sulfur composite nanotube array electrocatalyst growing on conductive substrate and preparation method and application thereof |
| CN109003827A (en) * | 2018-07-27 | 2018-12-14 | 福州大学 | A kind of preparation method and application of spongy graphene/nickel cobalt sulfide composite material |
| CN109243843A (en) * | 2018-10-08 | 2019-01-18 | 西安交通大学 | A kind of ultra-fine sulfide/graphene Two-dimensional Composites and its preparation method and application |
| CN110136989A (en) * | 2019-06-10 | 2019-08-16 | 东北大学秦皇岛分校 | A kind of positive, preparation method and supercapacitor obtained |
| CN110155993A (en) * | 2019-06-27 | 2019-08-23 | 中素新科技有限公司 | Hydrophobic graphene aerogel and its preparation method and application |
| CN110155993B (en) * | 2019-06-27 | 2021-01-26 | 中素新科技有限公司 | Hydrophobic graphene aerogel and preparation method and application thereof |
| CN110627134A (en) * | 2019-09-26 | 2019-12-31 | 广东工业大学 | Preparation method of cobalt-nickel sulfide electrode material and battery |
| CN111508722A (en) * | 2020-04-26 | 2020-08-07 | 梁汉日 | Polypyrrole coated MnO2-NiCo2S4Super capacitor electrode material and preparation method thereof |
| CN113104904A (en) * | 2021-04-07 | 2021-07-13 | 合肥师范学院 | Preparation method and application of heterojunction bridging graphene sulfide aerogel |
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