A kind of super capacitor composite electrode and preparation method thereof
Technical field
The present invention relates to a kind of electrode for capacitors, particularly a kind of super capacitor composite electrode and preparation method thereof.
Background technology
There is charging rate slowly in the capacitor of general production and sales in the market, and current density is little, the problems such as average life span is short.Graphite composite material is a potential ideal material, because Graphene has outstanding electric property, and uncommon mechanical strength, high chemical stability, and graphite cost is low, can gather in a large number, that based on Graphene, prepares ultracapacitor also has a lot.
Three-dimensional grapheme material, structurally be different from the Graphene of two dimension, two-dimensional graphene is easily reunited, difficult dispersion, be difficult to the material obtaining high-specific surface area, it has three-dimensional hollow porous network structure, net wall is Graphene, for the graphite of layer structure and the graphitic carbon foam of porous, the advantage such as there is extremely-low density surface area, high heat conduction, high temperature resistant, corrosion-resistant, ductility, pliability are good, single-layer and transparent and quality is higher.
Chemical vapour deposition technique utilizes the atomic structure of growth substrate " kind " to go out Graphene, with metal single crystal or metallic film for substrate, expose also pyrolysis carbon compound in its surface and can generate graphene-structured, the Graphene that this method obtains is single layer structure, and performance is also more satisfactory.At present, the experiment preparing Graphene in this way selects metal Ru as host substrate.But because ruthenium belongs to rare precious metals, resource-constrained, and price is high.
Our laboratory also adopts this method to prepare grapheme material, but we choosing be that metallic nickel is as host substrate.Recently, some groups report sulfide of cobalt and the sulfide composite material of cobalt have been employed as Low-cost electric chemical material, because they can produce very high desirable solid-state reaction.The electric conductivity of metallic nickel is also fine.But experiment shows, the nickel/Graphene of cycle performance is a very unstable electrode material, nickel/Co
3s
4electrode is also a unstable electrode material, and nickel/its stability of three-dimensional grapheme/cobalt sulfide is high, and the life-span that can be recycled is long, and same copper/three-dimensional grapheme/cobalt sulfide also has same excellent performance.
Summary of the invention
The object of this invention is to provide super capacitor composite electrode of a kind of high current charge-discharge and preparation method thereof, not only charging rate is fast for it, only needs 10min just to charge complete, and in large current charge situation, its performance is still constant, and average life span is elongated, can recycle more than 8000 time.
A kind of super capacitor composite electrode, comprises basalis nickel screen or copper mesh, outer Co
3s
4nanosphere film and the intermediate layer individual layer three-dimensional grapheme between basalis and skin.
Described Co
3s
4nanosphere film is hollow cobalt sulfide nanosphere continuous, of uniform size.
Described Co
3s
4the diameter of nanosphere is 3 ~ 50nm, preferred 10-20nm.
Described nickel screen or the aperture of copper mesh are 0.01-0.6mm, the preferred 0.01-0.1mm in aperture.
Prepare a method for super capacitor composite electrode, using nickel screen or copper mesh as basalis, utilize chemical vapour deposition technique to grow three-dimensional grapheme layer on the base layer, then on three-dimensional grapheme layer, grow Co by hydro thermal method
3s
4nanosphere thin layer, its concrete preparation process is as follows:
1) at protection gas and hydrogen, under 800 ~ 1300 DEG C of conditions, pass into carbon-source gas again after removing substrate surface oxide skin(coating), close carbon source after 2-10 minute, sample is cooled to room temperature rapidly, protection gas and hydrogen is closed;
2) thioacetyl amine aqueous solution is slowly joined Co (CH
3cOO)
24H
2react in O solution, ultrasonic, then the sample of the first step is put into reactant liquor, be heated to 80 ~ 180 DEG C of reactions, wherein Co (CH
3cOO)
24H
2o and thioacetamide mol ratio 1:1-20;
3) pass into protection gas, be heated to 200 ~ 500 DEG C of reactions after the sample clean be obtained by reacting by second step, drying, obtain basalis/three-dimensional grapheme/Co
3s
4nanosphere film (i.e. Ni(Cu)/G/CS).
The removal time described in step 1 is 5-20 minute, described carbon-source gas be selected from methane, methyl alcohol, ethanol or ethane one or more; Described protection gas is selected from argon gas or neon; Described carbon-source gas be methane or ethane time carbon-source gas flow velocity be 1-10s.c.c.m., preferred 3-7s.c.c.m.; Described carbon-source gas be methyl alcohol or ethanol time, with 1-10s.c.c.m., the protection gas bell of preferred 3-7s.c.c.m.; The flow velocity of described hydrogen is 100-300s.c.c.m., preferred 150-250s.c.c.m.; Described shielding gas flow speed is 300-600s.c.c.m.; Described cooldown rate is 200-300 DEG C/min.
Co (CH described in step 2
3cOO)
24H
2o and the preferred 1:5-15 of thioacetamide mol ratio, described ultrasonic time is 5-25 minute; The described heating reaction time is 1-6 hour, preferred 2-4 hour; The preferred 100-140 DEG C of described heating-up temperature.
Baking temperature described in step 3 is 30-40 DEG C, and described drying condition is under vacuum, and described drying time is 3-4h; Described heating-up temperature preferably 300 DEG C, the described reaction time is 0.5-3 hour, preferably 1 hour.
Compared with prior art, its remarkable advantage is in the present invention:
This individual layer three-dimensional grapheme is transparent and quality is higher, and forms sandwich structure basalis/three-dimensional grapheme/Co
3s
4nanosphere film is a highly stable superior structural, and its electrode capacitance value is far above general capacitor.
1) Co of hollow
3s
4come the surface of three-dimensional grapheme, and nanosphere size is when 20-30nm, nanosphere specific area is large, makes Co nanosphere uniformly continous
3s
4and contact area between electrolyte is large, thus cause the large increase of more effective transferring charge and capacitance;
2) unique sandwich structure basalis/three-dimensional grapheme/Co
3s
4nanosphere membrane structure is a highly stable superior structural, and its electrode capacitance value is far above general capacitor, and the discharge and recharge number of times of battery that this material is made is up to 8000 times;
3) the middle three-dimensional grapheme layer of basalis/three-dimensional graphene framework, especially individual layer three-dimensional grapheme layer, has excellent conductivity, pliability, ductility and mechanical strength, electronics can be made can more effectively to transmit during rushing discharge and recharge fast;
4) Co
3s
4nanosphere and single-layer graphene at high temperature react, and make ohmic contact between nanosphere and single-layer graphene;
5) preparation method is easy, convenient and swift low cost, the sandwich structure obtained basalis/three-dimensional grapheme/Co
3s
4nanosphere film is a highly stable superior structural, and its electrode capacitance value is far above general capacitor.
Accompanying drawing explanation
Fig. 1 is the structural representation of super capacitor composite electrode of the present invention.
Fig. 2 is configuration of surface and the structural characterization photo (A-C is the SEM figure under different multiples, and D is TEM figure, and E is Raman spectrogram) of the individual layer three-dimensional grapheme of the embodiment of the present invention 1.
Fig. 3 is that (A-C is the SEM figure of Ni/G/CS under different multiples, and D-E is Co under high multiple for the Ni/G/CS configuration of surface of the embodiment of the present invention 6 and structural characterization photo
3s
4layer SEM figure, F are the SEM figure of Ni/G/CS side, and G is Co
3s
4the long TEM figure on three-dimensional grapheme of layer, H is hollow Co
3s
4the TEM figure of nanosphere, J-I are that high-resolution TEM schemes, and K is the XRD figure of Ni/G/CS).
Fig. 4 is the embodiment of the present invention 6 electric capacity vs discharge and recharge number of times performance test curve chart.
Embodiment
Below in conjunction with accompanying drawing, describe embodiments of the present invention in detail.
Embodiment 1
Nickel screen (aperture 0.01mm) is placed in horizontal pipe furnace, under passing into argon gas (flow velocity 500s.c.c.m) and hydrogen (200s.c.c.m.), 1000 DEG C of conditions, heat 10 minutes, after removing oxide layer, then pass into methane gas (5s.c.c.m.), after 5 minutes, close methane gas, keep the flow velocity of argon gas and hydrogen constant, sample is quickly cooled to room temperature with the speed of 200 DEG C/min, close argon gas and hydrogen, obtained individual layer three-dimensional grapheme.
Carry out electron-microscope scanning to individual layer three-dimensional grapheme, as shown in fig. 2 a-d, known, long Graphene on nickel screen has three-dimensional structure, and surface smoothing, thinner thickness.Fig. 2 E is known, and three-dimensional grapheme is single layer structure.
Embodiment 2
Nickel screen (aperture 0.1mm) is placed in horizontal pipe furnace, under passing into neon (flow velocity 300s.c.c.m) and hydrogen (100s.c.c.m.), 800 DEG C of conditions, heat 10 minutes, after removing oxide layer, then pass into ethane gas (1s.c.c.m.), after 10 minutes, close ethane gas, keep the flow velocity of neon and hydrogen constant, sample is quickly cooled to room temperature with the speed of 200 DEG C/min, close neon and hydrogen.
Embodiment 3
Nickel screen (aperture 0.6mm) is placed in horizontal pipe furnace, under passing into argon gas (flow velocity 400s.c.c.m) and hydrogen (150s.c.c.m.), 1300 DEG C of conditions, heat 5 minutes, after removing oxide layer, then use argon gas (6s.c.c.m.) to carry out bubbling in the tank of methyl alcohol, pass into methanol gas after 2 minutes, close methanol gas, keep the flow velocity of argon gas and hydrogen constant, sample is quickly cooled to room temperature with the speed of 300 DEG C/min, close argon gas and hydrogen.
Embodiment 4
Copper mesh (aperture 0.01mm) is placed in horizontal pipe furnace, under passing into argon gas (flow velocity 600s.c.c.m) and hydrogen (250s.c.c.m.), 900 DEG C of conditions, heat 20 minutes, after removing oxide layer, then pass into methane gas (10s.c.c.m.), after 5 minutes, close methane gas, keep the flow velocity of argon gas and hydrogen constant, sample is quickly cooled to room temperature with the speed of 250 DEG C/min, close argon gas and hydrogen.
Embodiment 5
Nickel screen (aperture 0.6mm) is placed in horizontal pipe furnace, under passing into argon gas (flow velocity 400s.c.c.m) and hydrogen (300s.c.c.m.), 1200 DEG C of conditions, heat 15 minutes, after removing oxide layer, then use argon gas (5s.c.c.m.) to carry out bubbling in the tank of ethanol, pass into alcohol gas after 8 minutes, close alcohol gas, keep the flow velocity of argon gas and hydrogen constant, sample is quickly cooled to room temperature with the speed of 200 DEG C/min, close argon gas and hydrogen.
Embodiment 6
Step (1) is with embodiment 1.
(2) by thioacetamide 8mmol and Co (CH
3cOO)
24H
2o0.8mmol is dissolved in the deionized water of 30ml respectively, and thioacetamide is slowly added Co (CH under the condition of magnetic agitation
3cOO)
24H
2react in O solution, 20 minutes are mixed again under ultrasound condition, the sample of the first step and reactant liquor are transferred in polytetrafluoroethylene line style stainless steel autoclave, heat 3 hours under 120 DEG C of reaction conditions, be cooled to room temperature, after products obtained therefrom deionized water and absolute ethyl alcohol rinse vacuum, at 30 DEG C dry 4 hours.Finally, passing under argon gas and 300 DEG C of conditions, the basalis/three-dimensional grapheme/Co obtaining sandwich structure for 1 hour is heated
3s
4nanosphere film nano combination electrode, as shown in Figure 1, intermediate layer 2 is individual layer three-dimensional grapheme to its structural representation, and basalis 1 is nickel screen, and outer 3 is Co
3s
4nanosphere film.
Being ESEM and XRD as shown in Figure 3 to embodiment 6, as can be seen from Fig. 3 B-C, Ni/G/CS rough surface, is because the three-dimensional structure of Graphene causes.From Fig. 3 D-E, Co
3s
4layer is made up of continuous print nanosphere, and the diameter of nanosphere is at 10-20nm.Be 3-tier architecture from Fig. 3 F, Ni/G/CS, thickness is that about 100nm, Fig. 3 H is known, Co
3s
4nanosphere is hollow-core construction, and diameter is at 10-20nm, Co
3s
4nanosphere is arranged in single-layer graphene surface.From Fig. 3 I, hollow Co
3s
4nano microsphere shows high-crystallinity, spacing of lattice 0.17,0.18,0.23 and 0.28nm place corresponding (440), (511), (400) and (311) crystal plane structure.
Carry out electrochemical test to embodiment 6, under its different current density, capacitance size is as table 1.Under different current density and cycle-index, capacitance variations curve chart as indicated at 4, and as can be seen from Figure 4, under different current density is impacted, particularly under excess current densities, discharge and recharge does not affect the cycle life of electric capacity, shows excellent capacitive property.
The test result of capacitance size under the different current densities of table 1 embodiment 6
Embodiment 7
Step (1) is with embodiment 1;
(2) by thioacetamide 15mmol and Co (CH
3cOO)
24H
2o3mmol is dissolved in the deionized water of 60ml respectively, and thioacetamide is slowly added Co (CH under the condition of magnetic agitation
3cOO)
24H
2react in O solution, 5 minutes are mixed again under ultrasound condition, the sample of the first step and reactant liquor are transferred in polytetrafluoroethylene line style stainless steel autoclave, heat 1 hour under 140 DEG C of reaction conditions, be cooled to room temperature, after products obtained therefrom deionized water and absolute ethyl alcohol rinse vacuum, at 40 DEG C dry 3 hours.Finally, passing under argon gas 3s.c.c.m. and 200 DEG C condition, heating the basalis/three-dimensional grapheme/Co obtaining sandwich structure for 3 hours
3s
4nanosphere film nano compound, Co
3s
4nanosphere diameter is 10-20nm, at 100mAcm
-2lower discharge and recharge, its electric capacity is 0.24F/cm
2.
Embodiment 8
Step (1) is with embodiment 1;
(2) by thioacetamide 12mmol and Co (CH
3cOO)
24H
2o0.8mmol is dissolved in the deionized water of 40ml respectively, and thioacetamide is slowly added Co (CH under the condition of magnetic agitation
3cOO)
24H
2react in O solution, 25 minutes are mixed again under ultrasound condition, the sample of the first step and reactant liquor are transferred in polytetrafluoroethylene line style stainless steel autoclave, heat 4 hours under 100 DEG C of reaction conditions, be cooled to room temperature, after products obtained therefrom deionized water and absolute ethyl alcohol rinse vacuum, at 35 DEG C dry 4 hours.Finally, passing under argon gas 7s.c.c.m. and 500 DEG C condition, heating the basalis/three-dimensional grapheme/Co obtaining sandwich structure for 0.5 hour
3s
4nanosphere film nano compound, Co
3s
4nanosphere diameter is 20-30nm, at 100mAcm
-2lower discharge and recharge, its electric capacity is 0.20F/cm
2.
Embodiment 9
Step (1) is with embodiment 1;
(2) by thioacetamide 8mmol and Co (CH
3cOO)
24H
2o8mmol is dissolved in the deionized water of 50ml respectively, and thioacetamide is slowly added Co (CH under the condition of magnetic agitation
3cOO)
24H
2react in O solution, 15 minutes are mixed again under ultrasound condition, the sample of the first step and reactant liquor are transferred in polytetrafluoroethylene line style stainless steel autoclave, heat 6 hours under 80 DEG C of reaction conditions, be cooled to room temperature, after products obtained therefrom deionized water and absolute ethyl alcohol rinse vacuum, at 30 DEG C dry 4 hours.Finally, passing under argon gas 5s.c.c.m. and 400 DEG C condition, heating the basalis/three-dimensional grapheme/Co obtaining sandwich structure for 2 hours
3s
4nanosphere film nano compound.
Embodiment 10
Step (1) is with embodiment 5;
(2) by thioacetamide 16mmol and Co (CH
3cOO)
24H
2o0.8mmol is dissolved in the deionized water of 60ml respectively, and thioacetamide is slowly added Co (CH under the condition of magnetic agitation
3cOO)
24H
2react in O solution, 20 minutes are mixed again under ultrasound condition, the sample of the first step and reactant liquor are transferred in polytetrafluoroethylene line style stainless steel autoclave, heat 2 hours under 180 DEG C of reaction conditions, be cooled to room temperature, after products obtained therefrom deionized water and absolute ethyl alcohol rinse vacuum, at 30 DEG C dry 4 hours.Finally, passing under argon gas 3s.c.c.m. and 300 DEG C condition, heating the basalis/three-dimensional grapheme/Co obtaining sandwich structure for 1 hour
3s
4nanosphere film nano compound, Co
3s
4nanosphere diameter is 10-20nm, at 100mAcm
-2lower discharge and recharge, its electric capacity is 0.25F/cm
2.