CN106683890A - Carbon/manganese oxide composite material, preparation method thereof and application thereof - Google Patents
Carbon/manganese oxide composite material, preparation method thereof and application thereof Download PDFInfo
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- CN106683890A CN106683890A CN201610937169.9A CN201610937169A CN106683890A CN 106683890 A CN106683890 A CN 106683890A CN 201610937169 A CN201610937169 A CN 201610937169A CN 106683890 A CN106683890 A CN 106683890A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- 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
Abstract
The present invention provides a carbon/manganese oxide composite material and a preparation method thereof. The carbon/manganese oxide composite material can be used as a supercapacitor electrode material. According to the carbon/manganese oxide composite material and the preparation method thereof of the invention, cheap, environmentally friendly, renewable and easily available wood flour is adopted as a raw material to prepare the carbon/manganese oxide composite material, the preparation method of the invention is advantageous in low cost compared with methods according to which excellent but expensive carbon materials such as ordered mesoporous carbon, graphene, carbon nanotubes and fullerenes are adopted; the carbon material in the composite material of the invention is an activated carbon material, and the activated carbon material itself can contribute high capacitance; and manganese oxide is loaded in situ on the surface of the activated carbon material through a high-temperature hydrothermal oxidation reaction, and therefore, the capacitance output capacity of the composite material can be improved.
Description
(1) technical field
The present invention relates to a kind of electrode material for super capacitor and preparation method and application, and in particular to one kind is with wood powder
For inexpensive carbon/manganese oxide composite material prepared by raw material, the composite can be used as electrode material for super capacitor.
(2) background technology
Ultracapacitor is a kind of new electric energy energy storage device between traditional capacitor and battery, with great Rong
Amount, high power density, charging and discharging capabilities are strong, long circulation life, can working at ultra-low temperature, many significant advantages such as pollution-free, its
Automobile (particularly electric automobile, fuel combination automobile and exceptional load vehicle), electric power, railway, communication, national defence, consumer electricity
The presence of the aspects such as sub- product is widely applied.Electrode material is that its performance and production cost are affected in ultracapacitor various assemblies
Key factor.Based on charge-storage mechanism, it is counterfeit that electrode material for super capacitor is generally divided into Electric double-layer capacitor material, faraday
Capacitance material (also referred to as oxidoreduction capacitance material) and compound electrode material.Compound electrode material is generally by electric double layer electricity
Capacity materials organically combine to be formed (Nat.Mater., 2008,7,845-854.) with fake capacitance material.With single Electric double-layer capacitor
Material is compared with fake capacitance material, benefit from Electric double-layer capacitor and fake capacitance dual contribution (Nano Lett., 2011,11,
2905-2911.), compound electrode material generally have higher specific capacitance, energy density or power density (ACS Nano,
2010,4,4403-4411.；ACS Nano,2010,4,5835-5842.).
Carbon/manganese oxide composite material that material with carbon element (offer Electric double-layer capacitor) is compounded to form with manganese oxide (offer fake capacitance)
It is presently the most typical hybrid supercapacitor electrode material (Chem.Soc.Rev., 2011,40,1697-1721.；ACS
Nano,2012,6,656-661.；Small,2016,12,2035–2045.；Adv.Energy Mater.,2016,6,
1501458.).In this composite, material with carbon element is additionally beneficial to surface attachment oxygen in addition to the Electric double-layer capacitor of itself is contributed
Change electric transmission of the manganese to current collector so as to fully contribute itself fake capacitance.Manganese oxide is then in situ raw as substrate using carbon skeleton
Length forms various nanostructureds, reduces self aggregation, improves electrolyte contacts, improves electric capacity and effectively contributes.Although carbon/manganese oxide is multiple
Close electrode material for super capacitor and extremely study concern by outstanding capacitive property, but it is multiple currently used for carbon/manganese oxide is prepared
The material with carbon element of composite electrode material, such as orderly porous carbon, CNT, Graphene, carbon fiber (CN104599854A；
CN104392849A；CN104465130A；CN105140046A；CN105448531A；CN105347334A；
CN105513822A；CN103594254B), in terms of production preparation or have that complicated process of preparation, cost be of a relatively high, raw material
The problems such as scarcity of resources, limit the industrialized production application of this composite.Therefore, cheap renewable money is sought
Source prepares material with carbon element as raw material using relatively green straightforward procedure, and it is used for into the outstanding carbon/manganese oxide of processability
Composite be this hybrid supercapacitor electrode material can reduces cost realize the crucial institute of industrialized production application
.
Timber is the high biomass resource of a kind of renewable environmental protection, abundance, cheap, carbon content, thus by
Electrode of super capacitor material with carbon element (Biomass Bioenerg.2012,46,145. are prepared as cheap raw material；
Electrochim.Acta2013,113,481.；J.Mater.Chem.A 2014,2,11706.；ECS Solid State
Lett.2014,3,M25.).Recently, Northeast Forestry University Li Jian academician seminar reports using cheap timber and is prepared as raw material
Wooden carbon/manganese oxide composite material be used for electrode of super capacitor research work (RSC Adv., 2016,6,64811), show wood
Carbon compound electrode material preparation in application potential.But, the wooden carbon that they are used is non-activated material with carbon element,
And manganese oxide load temperature is low in preparation technology, therefore the wooden material with carbon element for preparing is electric with the ratio of wooden carbon/manganese oxide composite material
Rong Jun is undesirable, and respectively 19F/g and 101F/g (RSC Adv., 2016,6,64811).Up to the present, there are no timber
Active carbon material is prepared first as raw material, then high-performance and low-cost carbon/manganese oxide is prepared by high temperature hydro-thermal method compound super
The report of level capacitor electrode material.
(3) content of the invention
It is an object of the invention to provide outstanding electrode material for super capacitor of a kind of low cost, performance and preparation method thereof
With application, for efficient utilization of the renewable timber resources on electrode material for super capacitor significant reference is provided.Due to
Timber is that a kind of proliferative speed is fast, yield is big, low cost, renewable, environmentally friendly biomass resource, and the present invention is using wood powder as original
Material, Jing carbonizations, alkali activation are obtained activity wood carbon dust, then pass through high-temperature water hot in-place oxidoreduction mode in gained activity wood
Carbon dust surface chemistry deposited oxide manganese, is obtained carbon/manganese oxide composite material finished product.The preparation method using timber low cost, can
The characteristics of regeneration, reduces composite and manufactures cost.Changed using high-temperature water hot in-place oxidoreduction mode deposited oxide manganese
It has been apt to load effect of the manganese oxide in carbon material surface, has been conducive to it to play capacitive property.The electrode material preparation method has uncommon
Prestige becomes the effective way of development low-cost and high-performance carbon/manganese oxide hybrid supercapacitor electrode material.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of carbon/manganese oxide composite material, its preparation method is：
(1) under nitrogen protection, raw material wood powder carries out 1~4h of carbonization treatment in 800~1000 DEG C, and room temperature is cooled to afterwards,
Carbonized product is obtained, by gained carbonized product and 0.5~1.5mol/L dilute hydrochloric acid with feed liquid mass ratio 1：20~70 mixing, stirring
(10~30min), stands (2~4h), filters, and filter cake is washed with deionized to neutrality, then is placed in 80~100 DEG C of vacuum drying
12~24h is dried in case, primary wood carbon dust is obtained；
(2) the primary wood carbon dust for obtaining step (1) is with alkali (sodium hydroxide or potassium hydroxide), water with mass ratio 1：2~
7：2~9 uniform mixing, obtain mixture, and then heating evaporation falls in gained mixture 80%~90% water, obtains paste
Thing；Nitrogen protection under, gained paste carries out 1~4h of activation processing in 800~1000 DEG C, and room temperature is cooled to afterwards, spend from
Sub- water washing is to neutrality, then is placed in 80~100 DEG C of vacuum drying ovens dry 12~24h, and activity wood carbon dust is obtained；
(3) the activity wood carbon dust for obtaining step (2) is with feed liquid mass ratio 1：150~700 ultrasounds (30~40KHz, 10~
30min) it is scattered in deionized water, obtains dispersion liquid, then under room temperature, stirring condition, adds in gained dispersion liquid high
The mixed aqueous solution of potassium manganate and hydrochloric acid, stir (3~10min), be warming up to 120~180 DEG C carry out hydro-thermal reaction 3~
12h, is cooled to afterwards room temperature, filters, and filter cake is washed with deionized to neutrality, then is placed in 60~80 DEG C of vacuum drying ovens dry
Dry 12~24h, obtains final product described carbon/manganese oxide composite material；
The mass ratio of the mixed aqueous solution of the activity wood carbon dust, potassium permanganate and hydrochloric acid is 1：300~1400；The height
In the mixed aqueous solution of potassium manganate and hydrochloric acid, the concentration of potassium permanganate is 6.5~8.5g/L, the concentration of hydrochloric acid is 0.15~
0.25mol/L。
In the present invention, described raw material wood powder is commercially available conventional wood powder, and generally its granularity is 70~200 mesh,
The ash content of coal≤5%, moisture≤5%；Also, it is preferred that described raw material wood powder is poplar (Classification system：Populus)
Powder.
In step (1) of the present invention, described carbonization treatment is generally carried out in temperature programmed control tube furnace, programming rate
For 1~5 DEG C/min.It is preferred that described carbonized product and dilute hydrochloric acid are with liquid material mass ratio 1：40~50 mixing.
In step (2), preferably described primary wood carbon dust and the mass ratio of alkali, water is 1：4~5：5~7.Described activation
Process is generally carried out in temperature programmed control tube furnace, and programming rate is 1~5 DEG C/min.
In step (3), preferably described activity wood carbon dust is with feed liquid mass ratio 1：200~400 ultrasonic disperses are in deionized water
In, the mass ratio of the mixed aqueous solution of preferably described activity wood carbon dust, potassium permanganate and hydrochloric acid is 1：400~700；It is preferred that described
In the mixed aqueous solution of potassium permanganate and hydrochloric acid, the concentration of potassium permanganate is 7~8g/L, the concentration of hydrochloric acid is 0.18~
0.22mol/L.It is preferred that the temperature of the hydro-thermal reaction is 130~150 DEG C, the response time is 5~7h.Recommend the appearance of hydro-thermal reaction
Device is rustless steel hydrothermal reaction kettle.
Heretofore described room temperature is 20~30 DEG C.
Obtained carbon/manganese oxide composite material of the invention has good electrochemical capacitance performance, can be used as super capacitor electrode
Pole material.
Advantages of the present invention is as follows：
(1) material with carbon element is prepared for electrochemical capacitance carbon/oxygen as raw material using the wood powder of cheap, environmentally friendly, renewable, easy acquisition
Change the making of manganese composite, it is outstanding compared to using some performances but expensive material with carbon element is (such as ordered mesopore carbon, graphite
Alkene, CNT, fullerene etc.), the inventive method has obvious cost advantage；
(2) material with carbon element is active carbon material in composite of the present invention, and itself just can contribute higher electric capacity.And aoxidize
Manganese reacts original position and is supported on active carbon material surface by high-temperature water thermal redox, can improve composite electric capacity output energy
Power.
(4) specific embodiment
In order to be better understood from the present invention, it is further detailed below by specific embodiment, but the guarantor of the present invention
Shield scope is not limited to that.
Embodiment 1
(1) carbide wood carbon dust is prepared
By Poplar Powder (manufacturer：Chemical Co., Ltd. of Long Youmu nations, size：100 mesh, the ash content of coal≤5%, moisture
The 80g of content≤5%) is placed in temperature programmed control tube furnace, is risen to temperature from room temperature with the speed of 5 DEG C/min under nitrogen protection
1000 DEG C, and remove within 1 hour with volatile organic matter while carbonized solid residue in this temperature.When temperature is down to room
Brownish black carbide wood carbon dust is obtained after temperature.Then gained carbonized product 21g is uniformly mixed with 1L 1mol/L dilute hydrochloric acid, room
Temperature stands 3h after lower stirring 20min minutes, filters in gained mixture after standing, is directly washed with deionized to neutrality, then
It is placed in 90 DEG C of vacuum drying ovens and is dried 24h, primary wood carbon dust 19g is obtained.
(2) the wooden carbon dust of activation is prepared
Primary wood carbon dust 10g prepared by step (1) and potassium hydroxide 40g, water 50mL (mass ratioes 1：4：5) mix, stir
The content for being heated to water in mixture after mixing uniformly in 100 DEG C of baking ovens is the 18% (mixture obtained by i.e. for being initially added the water yield
In an oven heating evaporation falls 41g water), obtain black paste.Then this black paste is proceeded in tube furnace, nitrogen is protected
Temperature is risen to into 1000 DEG C with the speed of 5 DEG C/min from room temperature under shield, and in this temperature 1 hour fully activating carbon materials
Material.It is cooled to after room temperature and takes out sample, washs neutral to pH after being mixed with distilled water.Vacuum drying of the sample of acquisition at 90 DEG C
After being dried 24 hours in case, you can the wooden carbon dust 2.7g of black activation is obtained.
(3) carbon/manganese oxide composite material is prepared
The activation wood carbon dust of 0.09g steps (2) preparation, 20g deionized waters are weighed respectively with electronic balance adds taper
In bottle, at room temperature in 35KHz ultrasonic disperses 20 minutes.Afterwards, under room temperature, magnetic agitation, in above-mentioned dispersion liquid once
Property adds the mixed aqueous solution of 40g potassium permanganate and hydrochloric acid, and (wherein, potassium permanganate concentration is 7.0g/L, and concentration of hydrochloric acid is
0.18mol/L), stir after 5min under room temperature, mixture is moved in 100mL polytetrafluoroethyllining lining high pressure water heating kettles, seal
Under in 150 DEG C of high temperature ovens react 5 hours.After being cooled to room temperature, with water by gained solid product filtration washing to neutrality.It
Afterwards, solid sample is placed in into the drying 24 hours of 80 DEG C of vacuum drying oven, you can obtain 0.13g brownish black carbon/manganese oxide composite wood
Material.
(4) carbon/manganese oxide complex electrochemical property test
By the carbon/manganese oxide composite powder 0.0160g for preparing and acetylene black 0.0030g, politef 0.0010g
(mass ratio 80：15：5) mix, with fine the milling of a small amount of water (0.1mL) homogeneous slurry is obtained, will be starched using tablet machine
Material is pressed onto on nickel foam current collector and is prepared into electrode.Before carrying out electrochemical properties test, electrode needs true in 1M KOH solutions
Sky degassing 5 hours.Platinum electrode and saturated calomel electrode are used separately as to electrode and reference electrode.By three-electrode system, in room
Under the conditions of temperature, in 1M KOH electrolyte, using electrochemical workstation (CHI 660E, Shanghai Chen Hua equipment companies) to preparing electrode
Carry out constant current charge-discharge test (charging/discharging voltage -0.7~0.3V of scope).
According to formula Cs=I × △ t/ (△ V × m), can be calculated based on charging and discharging curve and prepare sample in different charge and discharges
Corresponding specific capacitance value C under electric electric current densitys.Wherein △ t (s) represents discharge time, and I (A) represents discharge current, △ V (V) table
Show the potential change of discharge process, m (g) represents the quality of active material in electrode.As a result show, in 0.5A/g electric current densities
Under, the specific capacitance (388F/g) of the carbon/manganese oxide complex of preparation far above one-component activate wooden carbon dust (167F/g) and
Manganese oxide (183F/g).
Data above illustrates that carbon/manganese oxide composite material prepared by the inventive method has excellent electrochemical capacitance performance, is
Potential electrode material for super capacitor candidate.
Embodiment 2
(1) carbide wood carbon dust is prepared
By Poplar Powder (manufacturer：Chemical Co., Ltd. of Long Youmu nations, size：100 mesh, the ash content of coal≤5%, moisture
The 80g of content≤5%) is placed in temperature programmed control tube furnace, is risen to temperature from room temperature with the speed of 3 DEG C/min under nitrogen protection
900 DEG C, and remove within 1.5 hours with volatile organic matter while carbonized solid residue in this temperature.When temperature is down to
Brownish black carbide wood carbon dust is obtained after room temperature.Then gained carbonized product 23g is uniformly mixed with 1L 1mol/L dilute hydrochloric acid,
3.5h is stood after stirring 20min minutes under room temperature, filters in gained mixture after standing, be directly washed with deionized into
Property, then be placed in 80 DEG C of vacuum drying ovens and be dried 24h, primary wood carbon dust 21g is obtained.
(2) the wooden carbon dust of activation is prepared
Carbonized product 10g prepared by step (1) and sodium hydroxide 46g, water 50mL (mass ratioes 1：4.6：5) mix, stir
The content for being heated to water in mixture after mixing uniformly in 100 DEG C of baking ovens is the 15% (mixture obtained by i.e. for being initially added the water yield
In an oven heating evaporation falls 42.5g water), obtain black paste.Then this black paste is proceeded in tube furnace, nitrogen
Temperature is risen to into 900 DEG C with the speed of 3 DEG C/min from room temperature under protection, and in this temperature 1.5 hours with abundant activated carbon
Material.It is cooled to after room temperature and takes out sample, washs neutral to pH after being mixed with distilled water.The sample of acquisition is done in 80 DEG C of vacuum
After being dried 24 hours in dry case, you can the wooden carbon dust 2.9g of black activation is obtained.
(3) carbon/manganese oxide composite material is prepared
The activation wood carbon dust of 0.075g steps (2) preparation, 20g deionized waters are weighed respectively with electronic balance adds taper
In bottle, at room temperature in 35KHz ultrasonic disperses 20 minutes.Afterwards, under room temperature, magnetic agitation, in above-mentioned dispersion liquid once
Property adds the mixed aqueous solution of 40g potassium permanganate and hydrochloric acid, and (wherein, potassium permanganate concentration is 7.5g/L, and concentration of hydrochloric acid is
0.2mol/L), stir after 10min under room temperature, mixture is moved in 100mL polytetrafluoroethyllining lining high pressure water heating kettles, seal
Under in 140 DEG C of high temperature ovens react 6 hours.After being cooled to room temperature, with water by gained solid product filtration washing to neutrality.It
Afterwards, solid sample is placed in into the drying 24 hours of 70 DEG C of vacuum drying oven, you can obtain 0.12g brownish black carbon/manganese oxide composite wood
Material.
(4) gained carbon/manganese oxide composite material powder electrochemical property test step is with embodiment 1.As a result show,
Under 0.5A/g electric current densities, the specific capacitance (411F/g) of the carbon/manganese oxide complex of preparation activates wooden carbon far above one-component
Powder (167F/g) and manganese oxide (183F/g).
Embodiment 3
(1) carbide wood carbon dust is prepared
By Poplar Powder (manufacturer：Chemical Co., Ltd. of Long Youmu nations, size：100 mesh, the ash content of coal≤5%, moisture
The 80g of content≤5%) is placed in temperature programmed control tube furnace, is risen to temperature from room temperature with the speed of 2 DEG C/min under nitrogen protection
800 DEG C, and remove within 2 hours with volatile organic matter while carbonized solid residue in this temperature.When temperature is down to room
Brownish black carbide wood carbon dust is obtained after temperature.Then gained carbonized product 25g is uniformly mixed with 1L 1mol/L dilute hydrochloric acid, room
Temperature stands 4h after lower stirring 20min minutes, filters in gained mixture after standing, is directly washed with deionized to neutrality, then
It is placed in 100 DEG C of vacuum drying ovens and is dried 12h, primary wood carbon dust 22.5g is obtained.
(2) the wooden carbon dust of activation is prepared
Carbonized product 10g prepared by step (1) and sodium hydroxide 50g, water 70mL (mass ratioes 1：5：7) mix, stirring
The content for being heated to water in mixture after uniform in 100 DEG C of baking ovens be initially added the water yield 10% (i.e. gained mixture exists
Heating evaporation falls 63g water in baking oven), obtain black paste.Then this black paste is proceeded in tube furnace, nitrogen protection
It is lower that temperature is risen to into 800 DEG C with the speed of 2 DEG C/min from room temperature, and in this temperature 2 hours with abundant activated carbon material.It is cold
But sample is taken out to room temperature, washs neutral to pH after being mixed with distilled water.The sample of acquisition is in 100 DEG C of vacuum drying oven
After being dried 12 hours, you can the wooden carbon dust 3g of black activation is obtained.
(3) carbon/manganese oxide composite material is prepared
The activation wood carbon dust of 0.060g steps (2) preparation, 20g deionized waters are weighed respectively with electronic balance adds taper
In bottle, at room temperature in 35KHz ultrasonic disperses 20 minutes.Afterwards, under room temperature, magnetic agitation, in above-mentioned dispersion liquid once
Property adds the mixed aqueous solution of 40g potassium permanganate and hydrochloric acid, and (wherein, potassium permanganate concentration is 8g/L, and concentration of hydrochloric acid is
0.22mol/L), stir after 8min under room temperature, mixture is moved in 100mL polytetrafluoroethyllining lining high pressure water heating kettles, seal
Under in 130 DEG C of high temperature ovens react 7 hours.After being cooled to room temperature, with water by gained solid product filtration washing to neutrality.It
Afterwards, solid sample is placed in into the drying 24 hours of 60 DEG C of vacuum drying oven, you can obtain 0.11g brownish black carbon/manganese oxide composite wood
Material.
(4) gained carbon/manganese oxide composite material powder electrochemical property test step is with embodiment 1.As a result show,
Under 0.5A/g electric current densities, the specific capacitance (369F/g) of the carbon/manganese oxide complex of preparation activates wooden carbon far above one-component
Powder (167F/g) and manganese oxide (183F/g).
Comparative example
(1) granted patent (B of CN 103594254,2016.02.24 are authorized) discloses a kind of carbon/manganese oxide composite electrodes
The preparation method of material, the method prepares manganese oxide, then first with manganese sulfate and Ammonium persulfate. as reactant by hydro-thermal method
Respectively with phenolic resin and tetraethyl orthosilicate as carbon and silicon dioxide presoma, F127 is constitution controller, through volatilization from
Assembling and carbonization are combined together ordered mesopore carbon and manganese dioxide, and two in material are finally removed with sodium hydrate aqueous solution
Monox nanometer ball, obtains carbon/manganese oxide composite material.
The material preparation process includes at least four complex steps, and the present invention significantly simplify production using three steps
Technique.The method uses phenolic resin as carbon source, is additionally used for pore-creating template using tetraethyl orthosilicate, its cost substantially compared with
Height, the present invention only uses cheap wood powder as carbon source, and its cost of material can at least save more than 50%.Carbon prepared by the method/
Manganese oxide composite material be used as electrode material for super capacitor when, its specific capacitance under 0.5A/g electric current densities, only 260.5F/
G, and the specific capacitance of carbon/manganese oxide composite material prepared by the present invention under same uniform current density is at least up to 369F/g.
(2) Suzhou Institute of Nano-tech. and Nano-bionics, Chinese Academy of Sciences teacher Chen Minghai team reports a kind of carbon and receives
The preparation method (Small, 2016,12,2035-2045) of mitron/manganese dioxide composite electrode material.The method is first by changing
Learn vapor phase method and prepare CNT, then using electrochemical oxidation process surface-modified carbon nanotubes, finally in modified carbon nano-tube
Surface electrochemistry deposition manganese dioxide prepares CNT/manganese dioxide composite material.
The material preparation method prepares material with carbon element using chemical gaseous phase depositing process, and technique and cost requirement are higher, and
The present invention prepares material with carbon element and only needs high-temperature calcination under noble gases, and technological requirement is low.The method is using electrodeposition process in carbon
Material surface loads manganese dioxide, and equipment requirements are high, yield poorly, and the present invention using hydro-thermal method deposition only need high pressure sealing tank and
Thermal source, yield is high, easily amplifies scale.Composite highest specific capacitance prepared by the method can only achieve 300F/g, and
Composite specific capacitance prepared by the inventive method is up to 411F/g.
Claims (10)
1. a kind of carbon/manganese oxide composite material, it is characterised in that described carbon/manganese oxide composite material is prepared as follows
Obtain：
(1) under nitrogen protection, raw material wood powder carries out 1~4h of carbonization treatment in 800~1000 DEG C, and room temperature is cooled to afterwards, obtains
Carbonized product, by gained carbonized product and 0.5~1.5mol/L dilute hydrochloric acid with feed liquid mass ratio 1：20~70 mixing, stirring is quiet
Put, filter, filter cake is washed with deionized to neutrality, then be placed in 80~100 DEG C of vacuum drying ovens dry 12~24h, be obtained
Primary wood carbon dust；
(2) the primary wood carbon dust for obtaining step (1) is with alkali, water with mass ratio 1：2~7：2~9 uniform mixing, are mixed
Thing, then heating evaporation fall gained mixture in 80%~90% water, obtain paste；Under nitrogen protection, gained paste
1~4h of activation processing is carried out in 800~1000 DEG C, room temperature is cooled to afterwards, be washed with deionized to neutrality, then it is placed in 80~
12~24h is dried in 100 DEG C of vacuum drying ovens, activity wood carbon dust is obtained；
(3) the activity wood carbon dust for obtaining step (2) is with feed liquid mass ratio 1：150~700 ultrasonic disperses are obtained in deionized water
To dispersion liquid, then under room temperature, stirring condition, the mixed aqueous solution of potassium permanganate and hydrochloric acid is added in gained dispersion liquid,
Stir, being warming up to 120~180 DEG C carries out 3~12h of hydro-thermal reaction, and room temperature is cooled to afterwards, filter, filter cake deionization
Water washing is to neutrality, then is placed in 60~80 DEG C of vacuum drying ovens dry 12~24h, obtains final product described carbon/manganese oxide composite wood
Material；
The mass ratio of the mixed aqueous solution of the activity wood carbon dust, potassium permanganate and hydrochloric acid is 1：300~1400；The permanganic acid
In the mixed aqueous solution of potassium and hydrochloric acid, the concentration of potassium permanganate is 6.5~8.5g/L, and the concentration of hydrochloric acid is 0.15~0.25mol/
L。
2. carbon/manganese oxide composite material as claimed in claim 1, it is characterised in that in step (1), described raw material wood powder
For Poplar Powder.
3. carbon/manganese oxide composite material as claimed in claim 1, it is characterised in that in step (1), described carbonized product
With dilute hydrochloric acid with liquid material mass ratio 1：40~50 mixing.
4. carbon/manganese oxide composite material as claimed in claim 1, it is characterised in that in step (2), described alkali is hydrogen-oxygen
Change sodium or potassium hydroxide.
5. carbon/manganese oxide composite material as claimed in claim 1, it is characterised in that in step (2), described primary wood carbon
Powder is 1 with the mass ratio of alkali, water：4~5：5~7.
6. carbon/manganese oxide composite material as claimed in claim 1, it is characterised in that in step (3), the activity wood carbon dust
With feed liquid mass ratio 1：200~400 ultrasonic disperses are in deionized water.
7. carbon/manganese oxide composite material as claimed in claim 1, it is characterised in that in step (3), the activity wood carbon dust,
Potassium permanganate is 1 with the mass ratio of the mixed aqueous solution of hydrochloric acid：400~700.
8. carbon/manganese oxide composite material as claimed in claim 1, it is characterised in that in step (3), the potassium permanganate with
In the mixed aqueous solution of hydrochloric acid, the concentration of potassium permanganate is 7~8g/L, and the concentration of hydrochloric acid is 0.18~0.22mol/L.
9. carbon/manganese oxide composite material as claimed in claim 1, it is characterised in that in step (3), the hydro-thermal reaction
Temperature is 130~150 DEG C, and the response time is 5~7h.
10. application of the carbon/manganese oxide composite material as claimed in claim 1 as electrode material for super capacitor.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109650369A (en) * | 2018-12-15 | 2019-04-19 | 华南理工大学 | A kind of wood and the preparation method and application thereof that can be generated electricity |
| CN110492082A (en) * | 2019-08-28 | 2019-11-22 | 中北大学 | A kind of manganese dioxide/carbon nanotube composite material, preparation method and application |
| CN110600278A (en) * | 2019-08-22 | 2019-12-20 | 江苏大学 | Pinecone-shaped MnO2Ball/foam carbon composite material and preparation method thereof |
| CN110706940A (en) * | 2019-10-17 | 2020-01-17 | 福建工程学院 | Three-dimensional porous carbon-manganese oxide core-shell structure material and preparation method and application thereof |
| CN111807419A (en) * | 2020-07-24 | 2020-10-23 | 华侨大学 | Cobalt oxide/plastic derived porous layer carbon composite electrode material and synthesis and application thereof |
| CN111899984A (en) * | 2020-08-04 | 2020-11-06 | 山东理工大学 | In-situ blow molding process for preparing nano manganese oxide/carbon composite material in batches |
| CN113990674A (en) * | 2021-11-11 | 2022-01-28 | 辽宁工程技术大学 | Preparation method and application of composite material with sandwich structure |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008162821A (en) * | 2006-12-27 | 2008-07-17 | Tokyo Institute Of Technology | Carbon composite material and its manufacturing method |
| CN103594254A (en) * | 2013-11-26 | 2014-02-19 | 华东理工大学 | Method for preparing manganese dioxide/mesoporous carbon nanometer graded composite electrode material |
| CN105469999A (en) * | 2015-11-20 | 2016-04-06 | 浙江农林大学 | Method of preparing electrode material for carbon-based supercapacitor by taking bamboo powder as raw material |
| CN105489389A (en) * | 2016-01-21 | 2016-04-13 | 浙江农林大学 | Carbon/nickel-cobalt layered double hydroxide composite material and preparation method and application thereof |
-
2016
- 2016-11-01 CN CN201610937169.9A patent/CN106683890A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008162821A (en) * | 2006-12-27 | 2008-07-17 | Tokyo Institute Of Technology | Carbon composite material and its manufacturing method |
| US20100092865A1 (en) * | 2006-12-27 | 2010-04-15 | Tokyo Institute Of Technology | Carbon composite materials and process for production thereof |
| CN103594254A (en) * | 2013-11-26 | 2014-02-19 | 华东理工大学 | Method for preparing manganese dioxide/mesoporous carbon nanometer graded composite electrode material |
| CN105469999A (en) * | 2015-11-20 | 2016-04-06 | 浙江农林大学 | Method of preparing electrode material for carbon-based supercapacitor by taking bamboo powder as raw material |
| CN105489389A (en) * | 2016-01-21 | 2016-04-13 | 浙江农林大学 | Carbon/nickel-cobalt layered double hydroxide composite material and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| CAICHAO WAN, YUE JIAO AND JIAN LI: "Core–shell composite of wood-derived biochar supported MnO2 nanosheets for supercapacitor applications", 《RSC ADV.》 * |
| SHUAI YU ETC: "Synthesis of wood derived nitrogen-doped porous carbon-polyaniline composites for supercapacitor electrode materials", 《RSC ADV》 * |
| TIANFU HUANG, ZEHAI QIU, DEWU WU, ZHIBIAO HU: "Bamboo-Based Activated Carbon @ MnO2 Nanocomposites for Flexible High-Performance Supercapacitor Electrode Materials", 《INT. J. ELECTROCHEM. SCI.》 * |
| 李增鹏: "MnO2/C复合材料的制备及电化学性能的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑（月刊）》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109650369A (en) * | 2018-12-15 | 2019-04-19 | 华南理工大学 | A kind of wood and the preparation method and application thereof that can be generated electricity |
| CN110600278A (en) * | 2019-08-22 | 2019-12-20 | 江苏大学 | Pinecone-shaped MnO2Ball/foam carbon composite material and preparation method thereof |
| CN110600278B (en) * | 2019-08-22 | 2022-03-22 | 江苏大学 | Pinecone-shaped MnO2Ball/foam carbon composite material and preparation method thereof |
| CN110492082A (en) * | 2019-08-28 | 2019-11-22 | 中北大学 | A kind of manganese dioxide/carbon nanotube composite material, preparation method and application |
| CN110706940A (en) * | 2019-10-17 | 2020-01-17 | 福建工程学院 | Three-dimensional porous carbon-manganese oxide core-shell structure material and preparation method and application thereof |
| CN110706940B (en) * | 2019-10-17 | 2021-09-28 | 福建工程学院 | Three-dimensional porous carbon-manganese oxide core-shell structure material and preparation method and application thereof |
| CN111807419A (en) * | 2020-07-24 | 2020-10-23 | 华侨大学 | Cobalt oxide/plastic derived porous layer carbon composite electrode material and synthesis and application thereof |
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