A kind of composite electrochemical energy storage Carbon Materials and its preparation method and application
Technical field
The invention belongs to electrochemical energy storage carbon composite technical fields, and in particular to zip mode synthesizes two dimension C/Fe3O4It is multiple
Close electrochemical energy storage Carbon Materials and its preparation method and application.
Background technique
As a kind of novel electrochemical energy storage materials, supercapacitor is with power density is big, the charging time is short, circulation
The advantages that service life is long.Electrode material is the major part for influencing supercapacitor chemical property, and wherein the application of carbon material is gone through
History longest, commercialized degree highest, however since it is limited come the specific capacitance obtained in the form of storing energy by electric double layer,
Constrain carbon material further applying in supercapacitor field.Another common electrode material is transiting metal oxidation
Object, the faraday's reaction of Rapid reversible occurs by the two-dimentional or quasi- two-dimensional surface on electrode and electrolyte liquor surface or body phase to store up in it
Energy is deposited, the energy that can be stored is 1-100 times of carbon material, however the generally existing electric conductivity of transition metal oxide
Difference, the disadvantages of physicochemical properties are unstable, therefore be also difficult to complete large-scale practical application.Both the above electrode material is all
Possess itself unique advantage and deficiency, in order to obtain better electrochemical effects, for the shortcoming of every kind of material itself
A large amount of research has been done, however since the defect of every kind of material itself is difficult to perfectly be solved, so the material finally obtained
Preferable electrochemical effects are not shown.
In order to solve problem above, research finds transition metal oxide and carbon material can organically be combined group
At composite material, and it is finally obtained good effect.In this composite material, the effect of carbon material is mainly shown as: being made
For support frame, movement of the metal oxide particle in electrochemical process can be effectively limited;The hole of active carbon prosperity
Structure and huge specific surface area can then optimize the delivering path of electrolyte, reduce effective series resistance, and increase metal
The contact area of oxide particle and electrolyte;The efficiency of transmission of electronics can be improved in good electric conductivity.And oxo transition metal
Compound middle can then distribute the energy storage effect for waving itself, become the main source of storage energy.This composite material can be abundant
It plays the advantage of the two itself and learns from other's strong points to offset one's weaknesses, finally obtain excellent electrochemical effects.However this composite material is closing
At there are still certain problems in application process.It is that the size of transition metal oxide particle cannot be controlled effectively first
System, transition metal oxide are unevenly distributed carbon base body, cause effective active site negligible amounts, cannot give full play to
The chemical property of transition metal oxide;Followed by binding force is weaker between transition metal oxide and carbon base body, causes
Mobile even reunion occurs during electrochemical manipulation, causes the unstable of chemical property;It is finally to solve above two
A problem, it will lead to that synthesis step is cumbersome, condition is harsh, higher cost, it is difficult to form industrialization.
Therefore, reasonable structure design, the synthetic method of simple green and cheap cost are for carbon material and transition
Metal oxide composite has great importance.
Summary of the invention
The technical issues of solution: the present invention provides a kind of composite electrochemical energy storage Carbon Materials and its preparation method and application,
This method has the characteristics that step simple, green non-pollution, low in cost, and Fe in the composite material synthesized3O4Partial size compared with
It is small, be equably embedded in layer of charcoal, excellent chemical property is shown as electrode material for super capacitor.
Technical solution: a kind of preparation method of composite electrochemical energy storage Carbon Materials, including following synthesis step: 1- is prepared
3wt.% nano-cellulose aqueous solution, stirs 3-4h at room temperature, and excessive molysite water is then added under conditions of being stirred continuously
Solution, until gel not soluble in water is precipitated;The spawn in above-mentioned steps is taken out, is washed with deionized, vacuum is dry
It is dry;Under nitrogen protection, the heating rate for controlling tube furnace is 5 DEG C/min, right under conditions of carbonization temperature is 600 DEG C -800 DEG C
Spawn after drying carbonizes 1h, after cooling to room temperature, wash to carbide with deionized water and ethyl alcohol respectively
Composite electrochemical energy storage material.
Preferably, above-mentioned nano-cellulose concentration of aqueous solution is respectively 1wt.%, 2wt.% or 3wt.%.
Preferably, above-mentioned molysite is FeCl3。
Preferably, the additional amount of above-mentioned molysite aqueous solution is during being added dropwise without more gel analysis not soluble in water
Until out.
Preferably, the temperature of above-mentioned vacuum oven is 80 DEG C.
Preferably, above-mentioned carbonization temperature is respectively 600 DEG C, 700 DEG C or 800 DEG C.
Preferably, composite electrochemical energy storage material made from the above method
Application of the above-mentioned composite electrochemical energy storage Carbon Materials in preparation supercapacitor.
Two-dimentional C/Fe obtained by the present invention3O4Composite material, the application in supercapacitor pass through electro-chemical test
To evaluate, the specific steps are as follows:
Sample powder is mixed with conductive agent (acetylene black) and binder (PTFE) with the mass ratio of 8:1:1, and
And by the way that suitable ethanol wet is added, it is sufficiently stirred and mud is made, and it is uniformly smeared to 50 DEG C of drying on the working electrode (s
5h is tested in three electrode test systems, and electrolyte is 6M KOH, and electro-chemical test project includes constant current charge-discharge, follows
Ring volt-ampere curve, ac impedance measurement and cycle life test.
Key of the invention is that a large amount of oxygen-containing functional group can occur with metal ion in nano-cellulose molecular structure
Chelation.Excessive Fe3+As source metal introduce, by the chelation with nano-cellulose make the macromolecular of its chain with
The mode to zip connects, and ultimately forms two-dimensional lamellar structure.Due to the beam of chelation in carbonization process
It ties up the size that can effectively control metallic particles and is uniformly distributed, and transition metal oxide particle is embedded in securely
In layer of charcoal, and the two-dimensional Char Residues Structure obtained can then effectively promote electrolyte in transmission wherein.
The utility model has the advantages that Fe3+Introducing nano-cellulose threadiness macromolecular has been assembled into two-dimensional slice structure, be conducive to subtract
Transport resistance of the small electrolyte in electrode material;Chelation between the two will be by will can effectively control Fe3O4Size
And distribution, more active sites can be provided to store energy;This synthesis process in situ can be enhanced two kinds of materials it
Between binding ability, therefore the cycle life of electrode material is effectively ensured.
Detailed description of the invention
Fig. 1 is the two-dimentional C/Fe that embodiment 2 obtains3O4The scanning electron microscope and transmission electron microscope picture of composite material;
Fig. 2 is the scanning electron microscope (SEM) photograph for the simple nano-cellulose Carbon Materials that comparative example obtains;
Fig. 3 is the cyclic voltammetry curve comparison of material prepared by embodiment 2 and comparison example;
Fig. 4 is cyclic voltammetry curve of the embodiment 2 under different scanning rates;
Fig. 5 is constant current charge-discharge curve of the embodiment 2 under different current densities;
The comparison of Fig. 1 and Fig. 2 can illustrate that nano-cellulose is successfully assembled into two-dimentional C/ by the inventive method
Fe3O4Composite material;Fig. 3-Fig. 5 can illustrate that the composite material presents good chemical property.
Specific embodiment
Preferably to illustrate the present invention to reach the technical means and efficacy that predetermined goal of the invention is taken, below by tool
Body embodiment and attached drawing are illustrated.
Embodiment 1
At room temperature, 0.2g nano-cellulose powder is added in the distilled water of 10mL, and stirring 3h dissolution obtains clarifying molten
Liquid then prepares the FeCl that mass concentration is 2%3Solution is added drop-wise in the nano-cellulose solution being stirred continuously, meeting with needle tubing
There is gel not soluble in water to be precipitated, continue to be added dropwise, until being precipitated without apparent spawn, it is small persistently to stir two
When, gel is obtained by filtration, is washed with deionized, 80 DEG C of drying 12h of vacuum oven.Sample after drying is placed in tube furnace
In, under nitrogen protection, control heating rate is that 5 DEG C/min is cooled to room temperature in 600 DEG C of charing 1h, uses deionized water respectively
And ethanol washing, 80 DEG C of drying obtain two-dimentional C/Fe3O4Composite material.Nano oxidized iron particle is equal in obtained composite material
It is even to be embedded in two-dimensional layer of charcoal, the specific capacitance of 400F/g can be obtained when current density is 1A/g, and in electric current
Density still can obtain the specific capacitance of 200F/g when being 10A/g, 67% specific capacitance can be kept after 2000 circle of circulation.
Embodiment 2
At room temperature, 0.2g nano-cellulose powder is added in the distilled water of 10mL, and stirring 3h dissolution obtains clarifying molten
Liquid then prepares the FeCl that mass concentration is 2%3Solution is added drop-wise in the nano-cellulose solution being stirred continuously, meeting with needle tubing
There is gel not soluble in water to be precipitated, continue to be added dropwise, until being precipitated without apparent spawn, it is small persistently to stir two
When, gel is obtained by filtration, is washed with deionized, 80 DEG C of drying 12h of vacuum oven.Sample after drying is placed in tube furnace
In, under nitrogen protection, 700 DEG C is risen to the heating rate of 5 DEG C/min, and keep 1h, be cooled to room temperature, use deionization respectively
Water and ethanol washing, 80 DEG C of drying obtain two-dimentional C/Fe3O4Composite material.Nano oxidized iron particle in obtained composite material
It is uniformly embedded in two-dimensional layer of charcoal, the specific capacitance of 550F/g can be obtained when current density is 1A/g, and in electricity
Current density still can obtain the specific capacitance of 292F/g when being 10A/g, 86% specific capacitance can be kept after 2000 circle of circulation.
Embodiment 3
At room temperature, 0.2g nano-cellulose powder is added in the distilled water of 10mL, and stirring 3h dissolution obtains clarifying molten
Liquid then prepares the FeCl that mass concentration is 2%3Solution is added drop-wise in the nano-cellulose solution being stirred continuously, meeting with needle tubing
There is gel not soluble in water to be precipitated, continue to be added dropwise, until being precipitated without apparent spawn, it is small persistently to stir two
When, gel is obtained by filtration, is washed with deionized, 80 DEG C of drying 12h of vacuum oven.Sample after drying is placed in tube furnace
In, under nitrogen protection, 800 DEG C is risen to the heating rate of 5 DEG C/min, and keep 1h, be cooled to room temperature, use deionization respectively
Water and ethanol washing, 80 DEG C of drying obtain two-dimentional C/Fe3O4Composite material.Nano oxidized iron particle in obtained composite material
It is uniformly embedded in two-dimensional layer of charcoal, but there are apparent gap, the two between ferriferrous oxide particles and Carbon Materials
In conjunction with not close, the specific capacitance of 311F/g, specific capacitance when current density is 10A/g can not be obtained when current density is 1A/g
For 103F/g, circulation 2000 can keep 50% specific capacitance after enclosing.
Embodiment 4
At room temperature, 0.1g nano-cellulose powder is added in the distilled water of 10mL, and stirring 3h dissolution obtains clarifying molten
Liquid then prepares the FeCl that mass concentration is 2%3Solution is added drop-wise in the nano-cellulose solution being stirred continuously, meeting with needle tubing
There is gel not soluble in water to be precipitated, continue to be added dropwise, until being precipitated without apparent spawn, it is small persistently to stir two
When, gel is obtained by filtration, is washed with deionized, 80 DEG C of drying 12h of vacuum oven.Sample after drying is placed in tube furnace
In, under nitrogen protection, control heating rate is that 5 DEG C/min is cooled to room temperature in 700 DEG C of charing 1h, uses deionized water respectively
And ethanol washing, 80 DEG C of drying obtain two-dimentional C/Fe3O4Composite material.Obtained composite material and not formed two-dimensional layer of charcoal
Structure, Carbon Materials are size and non-uniform bulk, and ferriferrous oxide particles are distributed in charcoal material surface, and size is larger, in electricity
Current density can obtain the specific capacitance of 198F/g when being 1A/g, specific capacitance is 86F/g when current density is 10A/g, circulation 2000
43% specific capacitance can be kept after circle.
Embodiment 5
At room temperature, 0.3g nano-cellulose powder is added in the distilled water of 10mL, and stirring 3h dissolution obtains clarifying molten
Liquid then prepares the FeCl that mass concentration is 2%3Solution is added drop-wise in the nano-cellulose solution being stirred continuously, meeting with needle tubing
There is gel not soluble in water to be precipitated, continue to be added dropwise, until being precipitated without apparent spawn, it is small persistently to stir two
When, gel is obtained by filtration, is washed with deionized, 80 DEG C of drying 12h of vacuum oven.Sample after drying is placed in tube furnace
In, under nitrogen protection, control heating rate is that 5 DEG C/min is cooled to room temperature in 700 DEG C of charing 1h, uses deionized water respectively
And ethanol washing, 80 DEG C of drying obtain two-dimentional C/Fe3O4Composite material.Obtained composite material and not formed two-dimensional layer of charcoal
Structure, part ferriferrous oxide particles are embedded in Carbon Materials, most of to be distributed in charcoal material surface, ferriferrous oxide particles
Size is uneven, is differed by tens nanometers to several microns, and the specific capacitance of 264F/g, electricity can be obtained when current density is 1A/g
Specific capacitance is 124F/g when current density is 10A/g, and 48% specific capacitance can be kept after 2000 circle of circulation.
Comparative example
0.2g nano-cellulose is placed in tube furnace, under nitrogen protection, rises to 700 DEG C with the heating rate of 5 DEG C/min,
And 1h is kept, it is cooled to room temperature, uses deionized water and ethanol washing respectively, 80 DEG C of drying obtain simple Carbon Materials.It is obtained
Carbon Materials are the non-uniform carbon block of size, and the specific capacitance of 145F/g can be obtained when current density is 1A/g, and current density is
Specific capacitance is 76F/g when 10A/g, and 67% specific capacitance can be kept after 2000 circle of circulation.
Technical solution of the present invention is described in detail in above-described embodiment, it should be understood that more than
Described is only presently preferred embodiments of the present invention, is not intended to restrict the invention, any person skilled in the art, is not taking off
From within the scope of technical solution of the present invention, when the technology contents using the disclosure above make few modifications or are modified to equivalent variations
Equivalent embodiment, still, it is all done in spirit of the invention it is any modify or improve, should be included in this hair
Within the scope of bright.