CN104465123B - A kind of C@MnO2Nanotube electrode material for super capacitor and its production and use - Google Patents
A kind of C@MnO2Nanotube electrode material for super capacitor and its production and use Download PDFInfo
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- CN104465123B CN104465123B CN201410720452.7A CN201410720452A CN104465123B CN 104465123 B CN104465123 B CN 104465123B CN 201410720452 A CN201410720452 A CN 201410720452A CN 104465123 B CN104465123 B CN 104465123B
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Abstract
The invention provides a kind of three Vcs MnO2Composite nano tube array electrode material for super capacitor and its production and use, the material internal is nanotube-shaped carbon-coating, and outside is MnO2Material；Its preparation method includes：(1) flexible carbon fibre cloth is pre-processed and magnetron sputtering deposition zinc-oxide film；(2) array growth of zinc oxide nano rod；(3) preparing Surface coating has the nanometic zinc oxide rod array carbon cloth of thin layer carbon；(4) carbon cloth obtained using step (3), which is used the electrochemical deposition of three electrode electro-deposition systems progress manganese dioxide as working electrode and carries out rinsing, drying, obtains having three Vc MnO2The super capacitance electrode material of nano-tube structure structure.The material is by the carbon material of good conductivity and specific capacitance are high, electric conductivity is poor MnO2Combine, give full play to the advantage of the two, and hollow nanotube is beneficial to the turnover of electrolyte ion, can increase substantially the high rate performance of capacitor.
Description
Technical field
The invention belongs to energy storage and devices field, more particularly to a kind of three Vcs MnO2Composite nano tube array is super
Capacitance electrode material and its production and use.
Background technology
Flexible wearable electronic product increasingly attracts people more to pay close attention to and interest, but simultaneously to its electric power energy supply portion
Part it is also proposed higher requirement, such as lightweight, flexibility, high power, long-life, high-energy-density etc..The conventional offer energy
The device of storage is mainly lithium battery and ultracapacitor, compared with lithium ion battery, although the energy density of ultracapacitor
It is relatively low, but ultracapacitor can provide higher power density and cycle life, special effect and property can be played
Can, particularly with the electronic device of fast charging and discharging is needed, its advantage is that lithium ion battery is incomparable.
Ultracapacitor can be divided into two classes, a class be mainly using carbon material as the double layer capacitor of electrode material, it is another
Class is for faraday's capacitor, or pseudocapacitors by electrode material of oxide.Double layer capacitor is mainly by various
Carbon material is constituted, such as CNT, graphene, carbon fiber and carbon black etc..The electrode active material of faraday's capacitor is main
It is to aoxidize (RuO by various low transition metals2、NiO、CO3O4、 MnO2Deng) and conducting polymer composition.Faraday's capacitor phase
For double layer capacitor, its energy storage mechnism is that the chemistry of Rapid reversible occurs during discharge and recharge for electrode material instead
Should, therefore can have higher specific capacity, it is also study hotspot in recent years, its shortcoming is that electric conductivity is poor, is attempted to lead to
Crossing various methods improves its electric conductivity.
For the ultracapacitor used in flexible wearable electronic product, device unit area specific capacitance is not required nothing more than
Capacity is high, and requires lighting as far as possible.Carbon cloth is the conductive carbon fibre material worked out by conductive carbon fibre, is a kind of
Excellent lightweight electric double layer super capacitor material, can apply to flexible wearable electronic product, its shortcoming is unit area
Specific capacitance is low, it is difficult to adapt to the demand of high-energy-density device.In order to improve unit area specific capacitance, people are on the basis of carbon cloth
On complex carbon material or faraday's capacitive oxidation thing material, to improve area specific capacitance.Such as Zhou cheng etc. pass through
CVD modes random growth CNT on carbon cloth, is made flexible super capacitor (Zhou cheng, et al.Carbon
nanotube network film directly grown on carbon cloth for high-performance
Solid-state flexible supercapacitors.Nanotechnology.2014, DOI:10.1088/0957-
4484/25/3/035402).Seal big grade uses liquid solution as carbon source and catalyst source in patent CN102354612A, leads to
Cross CVD modes and surface density and draw ratio unusual high carbon pipe are grown on carbon cloth fiber, using the mode of electro-deposition in carbon
MnO has been coated on nanotube2Particle, this carbon pipe easily lodges because draw ratio is too high, is unfavorable for electrolyte into carbon pipe
Array inside and the insertion and abjection of ion, cause high-rate charge-discharge capability and cycle performance poor.
The method of above-mentioned CVD growth carbon pipe is to carry out at high temperature, and equipment requirement is high, complex process, and cost is high, also not
Beneficial to the integrated of energy device and other devices.
ZnO nano-rod array has three-dimensional structure, and the electrode as 3D ultracapacitors prepares template, has given play to latent
Advantage (Yong Zhao, Peng Jiang.MnO2nanosheets grown on the ZnO-nanorod-
Modifiedcarbon fiber paper for supercapacitor electrode materials, Colloids
and SurfacesA：Physicochem.Eng.Aspects, 2014,444,232-239；Yong Zhao, Peng Jiang,
Sishen Xie.Template-mediated synthesis of three-dimensional coral-like
MnO2nanostructure for supercapacitors, Journal of Power Sources, 2013,239,393-
398.), but ZnO nanorod is almost nil for the capacitance contribution of ultracapacitor, and add electrode for capacitors
Quality, is unfavorable for the lighting demand for development of ultracapacitor.
Existing CNT (CNT)@MnO2Hybrid supercapacitor electrode material growth technique is complicated, equipment requirement
High, cost is high, it is difficult to large-scale promotion and application.ZnO@Au@MnO2Although hybrid supercapacitor electrode material excellent performance,
But do not have contributive ZnO nano array to add electrode quality to condenser capacity, and conduction is improved using noble metal
Property, it is impossible to meet the low development trend of ultracapacitor lighting, cost.
There is carbon cloth unit area specific capacitance in the prior art in summary low；ZnO nanorod is for ultracapacitor
Capacitance is not contributed and adds the quality of electrode for capacitors；Coat MnO2The CNT draw ratio of particle is too high and easy
Lodging, be unfavorable for electrolyte into inside array carbon nanotube and ion insertion and abjection, cause high-rate charge-discharge capability with
And cycle performance is poor；Existing CNT hybrid supercapacitor electrode material growth technique is complicated, equipment requirement is high,
Cost is high, it is difficult to large-scale promotion and the problems such as apply.
The content of the invention
The invention provides a kind of novel three Vcs MnO grown based on flexible carbon cloth2The super electricity of composite nano tube array
The preparation method of container electrode material and its device, the material is poor by the carbon material of good conductivity and specific capacitance height, electric conductivity
MnO2Combine, give full play to the advantage of the two, and dexterously utilize the H produced in electrodeposition process+Remove to capacity
ZnO templates without contribution, prepare new lightweight high power capacity electrode material for super capacitor.
For up to this purpose, the present invention uses following technical scheme：
Three Vc MnO of one kind2Composite nano tube array super capacitance electrode material, the material internal is nanotube-shaped carbon
Layer, outside is MnO2Material.
The preparation method of super capacitance electrode material described above, the described method comprises the following steps：
(1) flexible carbon fibre cloth is pre-processed, it is thin then to carry out magnetron sputtering deposition ZnO to pretreated carbon cloth
Film, is used as the growth Seed Layer of ZnO nanorod；
(2) array growth of ZnO nanorod：Carbon cloth after handling in step (1) is placed in container, be separately added into from
Sub- water, the salting liquid of zinc, complexing agent one, complexing agent two and ammoniacal liquor are simultaneously sufficiently stirred for sealing, and then progress heating water bath obtains ZnO and received
Rice rod array, is evenly distributed in carbon cloth fiber peripheral；
(3) carbon cloth that the growth that the 3rd step is obtained has ZnO nano-rod array is rinsed, made after its surface complete wetting
Immerse in saccharide solution, then be dried after carbon cloth taking-up is blown off the saccharide solution of excess surface with inert gas, then
The carbon cloth being completely dried is made annealing treatment under the protection of inert gas so that the sugar around clading ZnO nano rod
Class carbonization, obtaining ZnO nanorod Surface coating has the ZnO@C nano rod arrays of thin layer carbon；
(4) carbon cloth for obtaining being loaded with ZnO@C nano rod arrays using step (3) is sunk as working electrode using three electrodes electricity
The electrochemical deposition that product system carries out manganese dioxide is obtained with C@MnO2The carbon cloth of nano tubular structure, using in deposition process
The H of generation+ZnO nanorod is removed, C@MnO are just can obtain2Nano tubular structure, wherein electrodeposition time need accurate control,
Time, too short ZnO nanorod was removed not exclusively, cannot get hollow nano tube structure；Then it is rinsed again, it is unnecessary to wash off
Electrolyte, and be dried to obtain with three Vc MnO2The super capacitance electrode material of nano-tube structure structure.
Preprocessing process is to carry out ultrasonic wave to flexible carbon fibre cloth with acetone and alcohol respectively to clean in step (1), so
Dried afterwards.
The time of ultrasonic wave cleaning is 1~5min, such as 1min, 1.5min, 2min, 2.5min, 3min,
3.5min, 4min, 4.5min or 5min etc., preferably 2min.
The drying temperature be 105~115 DEG C, such as 105 DEG C, 106 DEG C, 107 DEG C, 108 DEG C, 109 DEG C, 110 DEG C, 111
DEG C, 112 DEG C, 113 DEG C, 114 DEG C or 115 DEG C etc., preferably 110 DEG C.
The drying time is 1~3h, such as 1h, 1.5h, 2h, 2.5h or 3h, preferably 1h.
50~60nm of magnetron sputtering deposition zinc-oxide film on carbon cloth in the step (1) after treatment, for example
50nm, 51nm, 52nm, 53nm, 54nm, 55nm, 56nm, 57nm, 58nm, 59nm or 60nm etc., preferably 50nm.
The carbon cloth after being handled in step (1) is placed in resealable container in the step (2).
The salting liquid of zinc is any one in zinc nitrate, zinc sulfate, zinc chloride, zinc acetate or trbasic zinc phosphate in the step (2)
Kind or at least two combination, the combination is typical but non-limiting examples have：The combination of zinc nitrate and zinc sulfate, zinc chloride and
The combination of the combination of zinc acetate, zinc acetate and trbasic zinc phosphate, the combination of zinc nitrate, zinc sulfate and zinc chloride, zinc sulfate, zinc chloride,
Combination of zinc acetate and trbasic zinc phosphate etc., preferably zinc nitrate.
Step (2) complexing agent one is polyethylenimine solution, phenol solution, malonic acid dimethyl ester solution or ring
Any one in hexanone imide liquor or at least two combination, the combination is typical but non-limiting examples have：Polyvinyl
The combination of imide liquor and phenol solution, the combination of phenol solution and malonic acid dimethyl ester solution, malonic acid dimethyl ester solution and
The combination of cyclohexanoneimine solution, polyethylenimine solution, phenol solution, malonic acid dimethyl ester solution and cyclohexanoneimine are molten
Combination of liquid etc., preferably polyethylenimine solution.
Step (2) complexing agent two is that hexamethylenetetramine solution, ethylenediamine tetrapropionic acid solution, triethylenetetramine are molten
Any one in liquid or diethanolamine solution or at least two combination, the combination is typical but non-limiting examples have：Six times
The combination of tetramine solution and ethylenediamine tetrapropionic acid solution, the combination of ethylenediamine tetrapropionic acid solution and triethylenetetramine solution,
The combination of triethylenetetramine solution and diethanolamine solution, hexamethylenetetramine solution, ethylenediamine tetrapropionic acid solution and three ethylenes
The combination of four amine aqueous solutions, hexamethylenetetramine solution, ethylenediamine tetrapropionic acid solution, triethylenetetramine solution and diethanolamine solution
Combination etc., preferred hexamethylenetetramine solution.
Deionized water in the step (2), the salting liquid of zinc, complexing agent one, the volume ratio of complexing agent two and ammoniacal liquor are 30
~35:2~5:3~5:2~5:1~2, such as 30:2:3:2:1、31:3:4:3:2、32:4:5:4:1、 33:5:3:5:2、34:
3:3:4:2 or 35:4:5:3:1 etc., preferably 32:2:4:2:1.
In the step (2) concentration of the salting liquid of zinc be 0.3~0.7mol/L, such as 0.3mol/L, 0.35mol/L,
0.4mol/L, 0.45mol/L, 0.5mol/L, 0.55mol/L, 0.6mol/L, 0.65mol/L or 0.7mol/L etc., preferably
0.5mol/L。
The concentration of step (2) complexing agent one is 0.05~0.15mol/L, such as 0.05mol/L, 0.06mol/
L、0.07mol/L、0.08mol/L、0.09mol/L、0.1mol/L、0.11mol/L、 0.12mol/L、0.13mol/L、
0.14mol/L or 0.15mol/L etc., preferably 0.1mol/L.
The concentration of step (2) complexing agent two be 0.2~0.3mol/L, such as 0.2mol/L, 0.21mol/L,
0.22mol/L、0.23mol/L、0.24mol/L、0.25mol/L、0.26mol/L、 0.27mol/L、0.28mol/L、
0.29mol/L or 0.3mol/L etc., preferably 0.25mol/L.
In the step (2) concentration of ammoniacal liquor be 70~80%, such as 70%, 71%, 72%, 73%, 74%, 75%,
76%th, 77%, 78%, 79% or 80% etc., preferably 75%.
In the step (2) temperature of heating water bath be 60~70 DEG C, such as 60 DEG C, 61 DEG C, 62 DEG C, 63 DEG C, 64 DEG C,
65 DEG C, 66 DEG C, 67 DEG C, 68 DEG C, 69 DEG C or 70 DEG C etc., preferably 65 DEG C.
In the step (2) time of heating water bath be 8~12h, such as 8h, 8.5h, 9h, 9.5h, 10h, 10.5h,
11h, 11.5h or 12h etc., preferably 10h.
The carbon cloth that nanometic zinc oxide rod array is distributed with is rushed with absolute ethyl alcohol and deionized water successively in the step (3)
Wash.
Saccharide solution in the step (3) is glucose solution, sucrose solution, maltose solution, fructose soln or breast
Any one in sugar juice or at least two combination, the combination is typical but non-limiting examples have：Glucose solution and sugarcane
The combination of the combination of the combination of sugar juice, sucrose solution and maltose solution, maltose solution and fructose soln, fructose soln and
The combination of lactose solution, the combination of glucose solution, sucrose solution and maltose solution, sucrose solution, maltose solution, fructose
The combination of solution and lactose solution, glucose solution, sucrose solution, maltose solution, the combination of fructose soln and lactose solution
Lamp, preferably glucose solution.
In the step (3) concentration of saccharide solution be 0.5~1.5mol/L, such as 0.5mol/L, 0.6mol/L,
0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L or
1.5mol/L etc., preferably 1mol/L.
Carbon cloth soaks 4~7h in saccharide solution in the step (3), such as 4h, 4.5h, 5h, 5.5h, 6h, 6.5h or
7h etc., preferably 5h.
Inert gas is any one in nitrogen, argon gas, helium or neon or at least two group in the step (3)
Close, the combination is typical but non-limiting examples have：The combination of the combination of nitrogen and argon gas, argon gas and helium, helium and neon
Combination, the combination of nitrogen, argon gas and helium, nitrogen, argon gas, the combination of helium and neon etc..
The temperature dried after purging in the step (3) is 75~85 DEG C, such as 75 DEG C, 76 DEG C, 77 DEG C, 78 DEG C, 79
DEG C, 80 DEG C, 81 DEG C, 82 DEG C, 83 DEG C, 84 DEG C or 85 DEG C etc., preferably 80 DEG C.
The time dried in the step (3) is 4~6h, such as 4h, 4.5h, 5h, 5.5h or 6h, preferably 5h.
In the step (3) flow of the inert gas of protective effect be 45~55sccm, such as 45sccm, 46sccm,
47sccm, 48sccm, 49sccm, 50sccm, 51sccm, 52sccm, 53sccm, 54sccm or 55sccm etc., preferably
50sccm。
Annealing is carried out in quartz tube furnace in the step (3).
The temperature of annealing is 500~700 DEG C in the step (3), such as 500 DEG C, 530 DEG C, 550 DEG C, 570 DEG C,
600 DEG C, 630 DEG C, 650 DEG C, 670 DEG C or 700 DEG C etc., preferably 600 DEG C.
The time of annealing is 4~6h in the step (3), such as 4h, 4.5h, 5h, 5.5h or 6h, preferably 5h.
Using saturated calomel electrode as reference electrode in the electrode electro-deposition system of step (4) three, using platinized platinum as to electricity
Pole.
Electrolyte is used as using the mixed solution of manganese salt and metal salt solution in the electrode electro-deposition system of step (4) three.
Manganese salt is manganese nitrate, manganese sulfate, manganese acetate, manganese phosphate or chlorination in the electrode electro-deposition system of step (4) three
Any one in manganese or at least two combination, the combination is typical but non-limiting examples have：The group of manganese nitrate and manganese sulfate
Close, the combination of manganese sulfate and manganese acetate, the combination of manganese phosphate and manganese chloride, the combination of manganese nitrate, manganese sulfate and manganese acetate, sulfuric acid
Manganese, manganese acetate, the combination of manganese phosphate and manganese chloride, manganese nitrate, manganese sulfate, manganese acetate, the combination of manganese phosphate and manganese chloride, preferably
Manganese nitrate.
In the electrode electro-deposition system of step (4) three metal salt solution be sodium nitrate, sodium sulphate, sodium chloride, sodium acetate,
Any one in nickel nitrate, nickel acetate, nickel chloride, potassium nitrate, potassium acetate, potassium chloride or potassium sulfate or at least two combination,
The combination is typical but non-limiting examples have：The combination of the combination of sodium nitrate and sodium sulphate, sodium sulphate and sodium chloride, sodium acetate
With the combination of nickel nitrate, the combination of nickel nitrate, nickel acetate and nickel chloride, the combination of nickel chloride, potassium nitrate and potassium acetate, nitric acid
Potassium, potassium acetate, the combination of potassium chloride and potassium sulfate, sodium nitrate, sodium sulphate, sodium chloride, sodium acetate, nickel nitrate, nickel acetate and chlorine
Change the combination of nickel, nickel acetate, nickel chloride, potassium nitrate, potassium acetate, the combination of potassium chloride and potassium sulfate etc., preferably sodium nitrate.
The concentration of manganese salt is 0.01~0.03mol/L in the electrode electro-deposition system of step (4) three, for example
0.01mol/L、0.013mol/L、0.015mol/L、0.017mol/L、0.02mol/L、0.023mol/L、 0.025mol/L、
0.027mol/L or 0.03mol/L etc., preferably 0.02mol/L.
The concentration of metal salt solution is 0.05~0.15mol/L in the electrode electro-deposition system of step (4) three, for example
0.05mol/L、0.06mol/L、0.07mol/L、0.08mol/L、0.09mol/L、0.1mol/L、 0.11mol/L、
0.12mol/L, 0.13mol/L, 0.14mol/L or 0.15mol/L etc., preferably 0.1mol/L.
The current density of step (4) electrochemical deposition is 1~2mA/cm2, such as 1mA/cm2、 1.1mA/cm2、
1.2mA/cm2、1.3mA/cm2、1.4mA/cm2、1.5mA/cm2、1.6mA/cm2、 1.7mA/cm2、1.8mA/cm2、1.9mA/cm2
Or 2mA/cm2Deng preferably 1.5mA/cm2。
The time of step (4) electrochemical deposition be 35~45min, such as 35min, 36min, 37min, 38min,
39min, 40min, 41min, 42min, 43min, 44min or 45min etc., preferably 40min.
Electrochemical deposition is obtained with C@MnO in the step (4)2The carbon cloth of nano tubular structure is carried out with deionized water
Rinse.
In the step (4) drying temperature be 140~160 DEG C, such as 140 DEG C, 143 DEG C, 145 DEG C, 147 DEG C, 150 DEG C,
153 DEG C, 155 DEG C, 157 DEG C, 159 DEG C or 160 DEG C etc., preferably 150 DEG C.
In the step (4) drying time be 5~15min, such as 5min, 6min, 7min, 8min, 9min, 10min,
11min, 12min, 13min, 14min or 15min etc., preferably 10min.
The three Vc MnO that more than one methods describeds are prepared2Composite nano tube array super capacitance electrode material
Purposes, it is applied in wearable electronic product scope.
Compared with prior art, the present invention at least has the advantages that：
The present invention utilizes ZnO templates, prepares a kind of novel three-dimensional C@MnO grown based on flexible carbon cloth2Composite nano tube
Array electrode material for super capacitor, the material is by the carbon material of good conductivity and specific capacitance are high, electric conductivity is poor MnO2It is multiple
Altogether, the advantage of the two is given full play to, and dexterously utilizes the H produced in electrodeposition process+Remove to capacity without contribution
ZnO templates.
Material prepared by the present invention can as ultracapacitor electrode material, internal nanotube-shaped carbon-coating can be
The MnO of outside high power capacity2Material provides good electron conduction, and hollow nanotube is beneficial to entering for electrolyte ion
Go out, the high rate performance of capacitor can be increased substantially.
The electrode material lightweight, with higher area specific capacitance and power characteristic, cycle performance is superior, utilizes the electrode
The flexible solid-state supercapacitor that material assembling is obtained has good chemical property, is sweeping capacity when speed is 2mV/s
405F/g, 200F/g can be still reached sweeping capacity when speed is 100mV/s.The device has good flexibility simultaneously, in bending
The CV curves of device are basic after 1800 and the CV curves of (00) coincide substantially before not bending, illustrate that the device has excellent electricity
Steady chemical structure.The electrode material cost is low simultaneously, makes simple, can provide energy storage for wearable electronic product,
And the powerful electric discharge demand of electronic device can be met.
Brief description of the drawings
Fig. 1 is the ZnO nano-rod array figure grown on flexible carbon fibre cloth of the present invention；
Fig. 2 is the C@MnO that electro-deposition 40min is obtained2The SEM photograph of nano tube structure different amplification；
Fig. 3 is C@MnO2Nano tube structure TEM photos；
Fig. 4 is to use two panels carbon cloth@C@MnO2The symmetrical solid-state super capacitor free bend figure of electrode material assembling；
Fig. 5 is to light LED figures using two symmetrical solid-state super capacitor series connection；
Fig. 6 is to use two panels carbon cloth@C@MnO2The cyclic voltammogram of the symmetrical solid-state super capacitor of electrode material assembling；
Fig. 7 is the cyclic voltammetry curve compares figure before and after the symmetrical solid-state super capacitor bending 180 degree prepared.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
Embodiment 1：
C@MnO2The preparation of electrode material：
(1) flexible carbon fibre cloth is cleaned 2 minutes with acetone, alcohol ultrasonic wave respectively, then baking 1 is small at 110 DEG C
When；Using magnetron sputtering mode, sputtering sedimentation 50nm ZnO films, are used as zinc oxide nano rod on the carbon cloth of pretreatment
Grow Seed Layer；
(2) nanometic zinc oxide rod array grows：Carbon cloth sample prepared by above-mentioned steps (1) inserts sealable container
It is interior, according to 32:2:4:2:1 volume ratio, be separately added into deionized water, 0.5mol/L zinc nitrate solution, 0.1mol/L it is poly-
The hexamethylenetetramine solution and 75% ammoniacal liquor of ketene imine solution, 0.25mol/L.Sealed after being sufficiently stirred for, Ran Hou
Heating water bath 10 hours at 65 DEG C, obtain the nanometic zinc oxide rod array of 6 microns, are evenly distributed in carbon cloth fiber week
Enclose, as shown in Figure 1.
(3) carbon cloth that the growth that (2) step is obtained has ZnO nanowire array is rushed with absolute ethyl alcohol, deionized water successively
Wash, make its surface complete wetting, 5h is kept in the glucose solution that then carbon cloth is immersed to 1mol/L, carbon cloth is taken out afterwards and is used in combination
Nitrogen blows the glucose solution of excess surface off, and 5h is dried in 80 DEG C of baking oven.Then by the carbon cloth being completely dried,
Under 50sccm argon gas protection, in quartz tube furnace, anneal 5h at 600 DEG C so that the grape around clading ZnO nano rod
Sugared carbonization, can finally obtain ZnO nanorod Surface coating has the ZnO@C nano rod arrays of thin layer carbon.
(4) carbon cloth for being loaded with ZnO@C nano rod arrays obtained with (3) step is directly as working electrode, using three
Electrode electro-deposition system, by reference electrode of saturated calomel electrode, platinized platinum be Mn (NO to electrode, 0.02mol/L3)2With
0.1mol/L NaNO3Mixed solution be electrolyte, in 1.5mA/cm2Current density under carry out MnO2Electrochemical deposition,
Sedimentation time is 40min；Fall unnecessary electrolyte with a large amount of deionized water rinsings afterwards, and 10min is dried at 150 DEG C, obtain
To three Vc MnO of carbon cloth fiber surface growth in situ2Nano-tube structure structure, its electrode structure is as shown in Figures 2 and 3.
The preparation of all-solid-state flexible ultracapacitor：
By lithium chloride and PVA according to mass ratio 2:1 is dissolved in appropriate deionized water, in 85 DEG C of stirring in water bath 1h, consolidate
Body electrolyte.Using two panels carbon cloth/C@MnO2Electrode material (3cm × 2cm), on each plate electrode material, uniform smear is matched somebody with somebody
The PVA/LiCl solid electrolytes put, using ultra-thin filter membrane as barrier film, two panels electrode material is assembled, just obtains soft
Property solid-state super capacitor, as shown in Figure 4.The chemical property of the device is as shown in Figure 6 and Figure 7.
Embodiment 2：
C@MnO2The preparation of electrode material：
(1) ultrasonic wave scavenging period is removed for 1min, is dried at 105 DEG C outside 2h, sputtering sedimentation 55nm ZnO films, other
Process is identical with step (1) in embodiment 1.
(2) remove and press 30:5:5:2:1 volume ratio be separately added into deionized water, 0.3mol/L zinc nitrate solution,
Outside 0.05mol/L phenol solution, 0.2mol/L ethylenediamine tetrapropionic acid solution and 70% ammoniacal liquor, 60 DEG C of washing 12h, its
His process is identical with step (2) in embodiment 1.
(3) remove to immerse carbon cloth in 1.5mol/L sucrose solution and keep 4h, 4h is dried in 85 DEG C of baking oven,
Under 55sccm nitrogen protection, annealed at 500 DEG C outside 6h, other processes are identical with step (3) in embodiment 1.
(4) divided by 0.03mol/L manganese acetate and 0.15mol/L sodium acetate mixed solution be electrolyte, in 2mA/
cm2Current density under carry out MnO2Electrochemical deposition, sedimentation time is 35min, is dried at 160 DEG C outside 5min, other processes
It is identical with step (4) in embodiment 1.
The preparation of all-solid-state flexible ultracapacitor：It is in the same manner as in Example 1.
Embodiment 3：
C@MnO2The preparation of electrode material：
(1) ultrasonic wave scavenging period is removed for 5min, is dried at 115 DEG C outside 3h, sputtering sedimentation 60nm ZnO films, other
Process is identical with step (1) in embodiment 1.
(2) remove and press 35:2:3:5:2 volume ratios be separately added into deionized water, 0.7mol/L liquor zinci chloridi,
0.15mol/L malonic acid dimethyl ester solution, 0.3mol/L triethylenetetramine solution and 80% ammoniacal liquor, 70 DEG C of washing 8h
Outside, other processes are identical with step (2) in embodiment 1.
(3) remove to immerse carbon cloth in 0.5mol/L fructose soln and keep 7h, 6h is dried in 75 DEG C of baking oven,
Under 45sccm nitrogen protection, annealed at 700 DEG C outside 4h, other processes are identical with step (3) in embodiment 1.
(4) divided by 0.01mol/L manganese chloride and 0.05mol/L sodium chloride mixed solution be electrolyte, in 1mA/
cm2Current density under carry out MnO2Electrochemical deposition, sedimentation time is 45min, is dried at 140 DEG C outside 15min, other mistakes
Journey is identical with step (4) in embodiment 1.
The preparation of all-solid-state flexible ultracapacitor：It is in the same manner as in Example 1.
Integrated embodiment 1-3 result can be seen that the present invention utilizes ZnO templates, prepare a kind of based on flexible carbon cloth growth
Novel three-dimensional C@MnO2Composite nano tube array electrode material for super capacitor, the material by the carbon material of good conductivity with than
The MnO that electric capacity is high, electric conductivity is poor2Combine, give full play to the advantage of the two, and dexterously utilize in electrodeposition process
The H of generation+Remove to ZnO template of the capacity without contribution.
The electrode material lightweight, with higher area specific capacitance and power characteristic, cycle performance is superior, is assembled into symmetrical
After capacitor, the cycle performance of its constant current charge-discharge is tested using bipolar electrode, after 5000 times circulate, its capacity remains to protect
Hold the 82% of initial capacity.Obtained flexible solid-state supercapacitor is assembled using the electrode material has good electrochemistry
Can, as shown in Figure 6 and Figure 7.The electrode material cost is low simultaneously, makes simple, can provide the energy for wearable electronic product and deposit
Storage, and the powerful electric discharge demand of electronic device can be met.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (69)
1. a kind of three Vcs MnO2The preparation method of composite nano tube array electrode material for super capacitor, it is characterised in that described
Material internal is nanotube-shaped carbon-coating, and outside is MnO2Material；
It the described method comprises the following steps：
(1) flexible carbon fibre cloth is pre-processed, magnetron sputtering deposition zinc oxide films then is carried out to pretreated carbon cloth
Film；
(2) array growth of zinc oxide nano rod：Carbon cloth after handling in step (1) is placed in container, be separately added into from
Sub- water, the salting liquid of zinc, complexing agent one, complexing agent two and ammoniacal liquor simultaneously stir sealing, then carry out heating water bath and are distributed with
The carbon cloth of nanometic zinc oxide rod array；
(3) immersed after being rinsed to the carbon cloth that nanometic zinc oxide rod array is distributed with saccharide solution, then carbon cloth is taken out into use
It is dried, is then made annealing treatment under the protection of inert gas after inert gas purge, obtaining Surface coating has thin layer
The nanometic zinc oxide rod array carbon cloth of carbon；
(4) carbon cloth obtained using step (3) carries out the electrification of manganese dioxide as working electrode using three electrode electro-deposition systems
Deposition is learned to obtain with C@MnO2The carbon cloth of nano tubular structure, then be rinsed, be dried to obtain with three Vc MnO2Nanotube
The super capacitance electrode material of shape array structure.
2. preparation method according to claim 1, it is characterised in that preprocessing process is to use acetone respectively in step (1)
Ultrasonic wave cleaning is carried out to flexible carbon fibre cloth with alcohol, then dried.
3. preparation method according to claim 2, it is characterised in that the time of the ultrasonic wave cleaning is 1~5min.
4. preparation method according to claim 3, it is characterised in that the time of the ultrasonic wave cleaning is 2min.
5. preparation method according to claim 2, it is characterised in that the drying temperature is 105~115 DEG C.
6. preparation method according to claim 5, it is characterised in that the drying temperature is 110 DEG C.
7. preparation method according to claim 2, it is characterised in that the drying time is 1~3h.
8. preparation method according to claim 7, it is characterised in that the drying time is 1h.
9. preparation method according to claim 1, it is characterised in that magnetic on the carbon cloth in the step (1) after treatment
Control 50~60nm of sputtering sedimentation zinc-oxide film.
10. preparation method according to claim 9, it is characterised in that magnetic on the carbon cloth in the step (1) after treatment
Control sputtering sedimentation 50nm zinc-oxide film.
11. preparation method according to claim 1, it is characterised in that after being handled in the step (2) in step (1)
Carbon cloth be placed in resealable container.
12. preparation method according to claim 1, it is characterised in that the salting liquid of zinc is nitric acid in the step (2)
Any one in zinc, zinc sulfate, zinc chloride, zinc acetate, trbasic zinc phosphate or at least two combination.
13. preparation method according to claim 12, it is characterised in that the salting liquid of zinc is nitric acid in the step (2)
Zinc.
14. preparation method according to claim 1, it is characterised in that step (2) complexing agent one is polyvinyl
Any one in imide liquor, phenol solution, malonic acid dimethyl ester solution or cyclohexanoneimine solution or at least two combination.
15. preparation method according to claim 14, it is characterised in that step (2) complexing agent one is polyethylene
Base imide liquor.
16. preparation method according to claim 1, it is characterised in that step (2) complexing agent two is six methines
Any one in four amine aqueous solutions, ethylenediamine tetrapropionic acid solution, triethylenetetramine solution or diethanolamine solution or at least two
Combination.
17. preparation method according to claim 16, it is characterised in that step (2) complexing agent two is six first
Urotropine solution.
18. preparation method according to claim 1, it is characterised in that deionized water in the step (2), zinc salt it is molten
Liquid, complexing agent one, the volume ratio of complexing agent two and ammoniacal liquor are 30~35:2~5:3~5:2~5:1~2.
19. preparation method according to claim 18, it is characterised in that deionized water in the step (2), zinc salt it is molten
Liquid, complexing agent one, the volume ratio of complexing agent two and ammoniacal liquor are 32:2:4:2:1.
20. preparation method according to claim 1, it is characterised in that the concentration of the salting liquid of zinc is in the step (2)
0.3~0.7mol/L.
21. preparation method according to claim 20, it is characterised in that the concentration of the salting liquid of zinc in the step (2)
For 0.5mol/L.
22. preparation method according to claim 1, it is characterised in that the concentration of step (2) complexing agent one is
0.05~0.15mol/L.
23. preparation method according to claim 22, it is characterised in that the concentration of step (2) complexing agent one is
0.1mol/L。
24. preparation method according to claim 1, it is characterised in that the concentration of step (2) complexing agent two is
0.2~0.3mol/L.
25. preparation method according to claim 24, it is characterised in that the concentration of step (2) complexing agent two is
0.25mol/L。
26. preparation method according to claim 1, it is characterised in that in the step (2) concentration of ammoniacal liquor be 70~
80%.
27. preparation method according to claim 26, it is characterised in that the concentration of ammoniacal liquor is 75% in the step (2).
28. preparation method according to claim 1, it is characterised in that the temperature of heating water bath is 60 in the step (2)
~70 DEG C.
29. preparation method according to claim 28, it is characterised in that the temperature of heating water bath is in the step (2)
65℃。
30. preparation method according to claim 1, it is characterised in that the time of heating water bath is 8 in the step (2)
~12h.
31. preparation method according to claim 30, it is characterised in that the time of heating water bath is in the step (2)
10h。
32. preparation method according to claim 1, it is characterised in that to zinc-oxide nano is distributed with the step (3)
The carbon cloth of rod array uses absolute ethyl alcohol and deionized water rinsing successively.
33. preparation method according to claim 1, it is characterised in that the saccharide solution in the step (3) is glucose
Any one in solution, sucrose solution, maltose solution, fructose soln or lactose solution or at least two combination.
34. preparation method according to claim 33, it is characterised in that the saccharide solution in the step (3) is grape
Sugar juice.
35. preparation method according to claim 1, it is characterised in that the concentration of saccharide solution is in the step (3)
0.5~1.5mol/L.
36. preparation method according to claim 35, it is characterised in that the concentration of saccharide solution is in the step (3)
1mol/L。
37. preparation method according to claim 1, it is characterised in that carbon cloth soaks in saccharide solution in the step (3)
Steep 4~7h.
38. preparation method according to claim 1, it is characterised in that carbon cloth soaks in saccharide solution in the step (3)
Steep 5h.
39. preparation method according to claim 1, it is characterised in that inert gas is nitrogen, argon in the step (3)
Any one in gas, helium or neon or at least two combination.
40. preparation method according to claim 1, it is characterised in that dry temperature is after being purged in the step (3)
75~85 DEG C.
41. preparation method according to claim 40, it is characterised in that the temperature dried after being purged in the step (3)
For 80 DEG C.
42. preparation method according to claim 1, it is characterised in that the time dried in the step (3) is 4~6h.
43. preparation method according to claim 42, it is characterised in that the time dried in the step (3) is 5h.
44. preparation method according to claim 1, it is characterised in that the inert gas of protective effect in the step (3)
Flow be 45~55sccm.
45. preparation method according to claim 44, it is characterised in that the indifferent gas of protective effect in the step (3)
The flow of body is 50sccm.
46. preparation method according to claim 1, it is characterised in that annealing is in quartz tube type in the step (3)
Carried out in stove.
47. preparation method according to claim 1, it is characterised in that the temperature of annealing is in the step (3)
500~700 DEG C.
48. preparation method according to claim 47, it is characterised in that the temperature of annealing is in the step (3)
600℃。
49. preparation method according to claim 1, it is characterised in that the time of annealing is 4 in the step (3)
~6h.
50. preparation method according to claim 1, it is characterised in that the time of annealing is in the step (3)
5h。
51. preparation method according to claim 1, it is characterised in that in the electrode electro-deposition system of step (4) three with
Saturated calomel electrode is as reference electrode, using platinized platinum as to electrode.
52. preparation method according to claim 1, it is characterised in that in the electrode electro-deposition system of step (4) three with
The mixed solution of manganese salt and metal salt solution is sodium nitrate, sodium sulphate, sodium chloride, vinegar as electrolyte, wherein metal salt solution
Any one in sour sodium, nickel nitrate, nickel acetate, nickel chloride, potassium nitrate, potassium acetate, potassium chloride or potassium sulfate or at least two
Combination.
53. preparation method according to claim 52, it is characterised in that in the electrode electro-deposition system of step (4) three
Manganese salt is any one in manganese nitrate, manganese sulfate, manganese acetate, manganese phosphate or manganese chloride or at least two combination.
54. preparation method according to claim 53, it is characterised in that in the electrode electro-deposition system of step (4) three
Manganese salt is manganese nitrate.
55. preparation method according to claim 52, it is characterised in that in the electrode electro-deposition system of step (4) three
Metal salt solution is sodium nitrate.
56. preparation method according to claim 52, it is characterised in that in the electrode electro-deposition system of step (4) three
The concentration of manganese salt is 0.01~0.03mol/L.
57. preparation method according to claim 56, it is characterised in that in the electrode electro-deposition system of step (4) three
The concentration of manganese salt is 0.02mol/L.
58. preparation method according to claim 52, it is characterised in that in the electrode electro-deposition system of step (4) three
The concentration of metal salt solution is 0.05~0.15mol/L.
59. preparation method according to claim 58, it is characterised in that in the electrode electro-deposition system of step (4) three
The concentration of metal salt solution is 0.1mol/L.
60. preparation method according to claim 1, it is characterised in that the current density of step (4) electrochemical deposition
For 1~2mA/cm2。
61. preparation method according to claim 60, it is characterised in that the electric current of step (4) electrochemical deposition is close
Spend for 1.5mA/cm2。
62. preparation method according to claim 1, it is characterised in that the time of step (4) electrochemical deposition is 35
~45min.
63. preparation method according to claim 62, it is characterised in that the time of step (4) electrochemical deposition is
40min。
64. preparation method according to claim 1, it is characterised in that electrochemical deposition is had in the step (4)
C@MnO2The carbon cloth of nano tubular structure is rinsed with deionized water.
65. preparation method according to claim 1, it is characterised in that drying temperature is 140~160 in the step (4)
℃。
66. preparation method according to claim 65, it is characterised in that drying temperature is 150 DEG C in the step (4).
67. preparation method according to claim 1, it is characterised in that in the step (4) drying time be 5~
15min。
68. preparation method according to claim 67, it is characterised in that drying time is 10min in the step (4).
69. a kind of three Vc MnO prepared such as any one of claim 1-68 methods described2Composite nano tube array is super
The purposes of capacitance electrode material, it is applied in wearable electronic product scope.
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| CN104752070B (en) * | 2015-04-01 | 2017-09-26 | 安徽师范大学 | A kind of zinc oxide@manganese dioxide@polypyrrole ternary core-shell heterogeneous structural nanos rod array material, preparation method and applications |
| CN106328952A (en) * | 2015-06-18 | 2017-01-11 | 中国石油化工股份有限公司 | Lithium electrode material, and preparation method and application thereof |
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| CN108010746A (en) * | 2018-01-29 | 2018-05-08 | 南昌航空大学 | A kind of carbon cloth surfaces method of modifying for flexible super capacitor electrode |
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| CN109637839B (en) * | 2018-11-14 | 2021-12-17 | 五邑大学 | Preparation method of carbon nano tube/manganese dioxide composite material electrode |
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| CN113113675B (en) * | 2021-04-16 | 2022-11-01 | 郑州大学 | Quasi-solid state flexible Zn-MnO2Battery and preparation method |
| CN115367737B (en) * | 2022-08-05 | 2024-04-19 | 西北工业大学 | Three-dimensional array carbon nano tube and preparation method thereof |
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