CN109859958A - Negative electrode active material ferric oxide nano point/nitrogen codope graphene preparation method and super capacitor anode - Google Patents
Negative electrode active material ferric oxide nano point/nitrogen codope graphene preparation method and super capacitor anode Download PDFInfo
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Abstract
The invention discloses a kind of negative electrode active material ferric oxide nano point/nitrogen codope graphene preparation methods and super capacitor anode, using little particle ferric oxide nano point as negative electrode active material, it is supported on nitrogen-doped graphene as negative electrode material, effectively improves the specific capacity of supercapacitor.The present invention is using organic molysite as source of iron, the particle of the more traditional inorganic molysite synthesis of the iron oxide particles of synthesis is smaller, when carrying out decentralized processing to graphene using nitrogen-containing solvent, nitrogen-atoms and graphene in solvent combine, become nitrogen-doped graphene, the effect of the collaborative combination of nitrogen and iron can effectively improve the cloud density of material, to improve the capacity of capacitor.The material property finally prepared is good.
Description
Technical field
The present invention relates to supercapacitor field more particularly to a kind of negative electrode active material ferric oxide nano point/nitrogen are double-doped
The preparation method and super capacitor anode of miscellaneous graphene.
Background technique
With the continuous development of science and technology, advanced energy storage device, such as supercapacitor, also face new challenges.
The material of higher performance, more clean and environmental protection becomes new demand.In supercapacitor, compared with positive electrode, for negative
The selection of pole material is very limited, and research is also not thorough enough.
Currently, some metal oxide/hydroxide, iron-based oxide/hydroxide and binary metal oxide are used as
The negative electrode material of supercapacitor has gradually attracted the interest of researcher.These materials have the advantages that there are many (1) iron
Valence state and a variety of redox states；(2) as the negative electrode material in supercapacitor, iron oxides/hydroxides have wide
Operate potential window and good cyclical stability；(3) compared with other metal oxide/hydroxide, iron oxide/hydroxide
Object has hypotoxicity and environment friendly；(4) iron oxides/hydroxides manufacturing cost is low, and iron is mistake most rich on the earth
Metallic element is crossed, therefore cheap.But metal oxide self-conductive is poor, specific surface area is low, is not able to satisfy super
The requirement of capacitor application.
Graphene specific surface area with higher has good electric conductivity, has when being used as electrode material good steady
Qualitative, two-dimentional (2D) structure keeps transfer ion freer.Therefore, graphene and metal oxide are combined as super
The negative electrode material of capacitor is common method.But traditional graphene is since interlamellar spacing is relatively narrow, and conventional metal oxides
Particle again it is excessive, the two binding force is bad, the dissolution of metal oxide is easy to happen in actual application, to influence
The chemical property of material.
Summary of the invention
The technical problem to be solved by the invention is to provide a kind of negative electrode active material ferric oxide nano point/nitrogen codopes
The preparation method and super capacitor anode of graphene, using little particle ferric oxide nano point as negative electrode active material, by it
It is supported on nitrogen-doped graphene as negative electrode material, effectively improves the specific capacity of supercapacitor.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is that: a kind of negative electrode active material iron oxide is received
Rice point/nitrogen codope graphene preparation method, includes the following steps:
(1) graphene for weighing 40~60mg is added in 90~120mL dispersate, after 30~80min of ultrasonic disperse
To mixture A；The dispersate is the mixture of one or both of DMF and nitrine organic solvent；
(2) Fe (C is added in Xiang Suoshu mixture A5H7O2)3Solution obtains mixture B after being ultrasonically treated 20~40min；
(3) the mixture B is transferred in autoclave, autoclave is heated to 170~210 DEG C after sealing, reaction 5~
By autoclave cooled to room temperature after 9 hours, product C therein is taken out；
(4) the product C is successively washed to cleaning solution with deionized water and ethyl alcohol repeatedly and is dried after being in neutrality, done
50~70 DEG C of dry temperature drying time 2~6 hours, finally obtains negative electrode active material ferric oxide nano point/nitrogen codope graphite
Alkene.
Fe (C in the step (2)5H7O2)3Liquor capacity is 8~12mL, and concentration is 1~10mol/L.
Fe (C in the step (2)5H7O2)3Liquor capacity is 10~11mL, and concentration is 6~8mol/L.
A kind of super capacitor anode, including negative electrode active material ferric oxide nano point/nitrogen made from above-mentioned preparation method
Codope graphene and active carbon cloth.
The preparation method of the active carbon cloth the following steps are included:
(1) charcoal cloth is immersed in by 20~40mL H2SO4With 10~30mL HNO3In the mixed acid solution of composition, control
Mixing speed is 50~450r/min, is stirred 1.5 hours；
(2) mixed acid solution described in step (1) is heated to 30~50 DEG C, being kept stirring speed is 50~450r/
Min is slowly added to 3~6g KMnO4, it reacts 1~4 hour, 100~150mL deionized water is added again and stirs 2~4 hours,
Obtain mixture A；
(3) excess hydrogen peroxide solution is added in the mixture A, is kept stirring, until mixture A become it is limpid and
Charcoal cloth is taken out from mixture A after no longer generating bubble, charcoal cloth is washed to cleaning solution repeatedly with distilled water and is in neutrality, is gone forward side by side
Row is dried, and obtains oxidation charcoal cloth；
(4) oxidation charcoal cloth obtained in step (3) is put into autoclave, 50mL H is added2O and 0.5~1.2mL hydration
Hydrazine, and reduction charcoal cloth is obtained after being kept for 10~13 hours at 70~90 DEG C；
(5) will reduction charcoal cloth deionized water and ethanol washing obtained in step (4) for several times until cleaning solution be it is neutral,
Then reduction charcoal is arranged at 50~70 DEG C after drying 6~12 hours up to active carbon cloth.
The mass percent concentration of the hydrogenperoxide steam generator is 35%.
The area of the charcoal cloth is 0.1~100cm2。
The H2SO4Concentration be 5-18M, the HNO3Concentration be 5-15M.
Preferably, H2SO4Concentration be 10-18M, the HNO3Concentration be 10-15M.
The beneficial effects of the present invention are: using organic molysite as source of iron, the more traditional inorganic molysite of the iron oxide of synthesis is closed
At particle it is smaller, graphite layers can be effectively embedding, be not easy, ensure that the steady of capacitor in capacitor operational process
It is fixed；When carrying out decentralized processing to graphene using nitrogen-containing solvent, nitrogen-atoms and graphene in solvent are combined, and become N doping stone
The collaborative combination effect of black alkene, nitrogen and iron can effectively improve the cloud density of material, to improve the capacity of capacitor.Most
The ferric oxide nano point and nitrogen codope graphene (Fe prepared afterwards2O 3NDs@NG) it is functional.
Detailed description of the invention
Fig. 1 is negative electrode active material ferric oxide nano point/nitrogen codope graphene SEM prepared by the embodiment of the present invention 1
Figure；
Fig. 2 is negative electrode active material ferric oxide nano point/nitrogen codope graphene XRD prepared by the embodiment of the present invention 1
Figure；
Fig. 3 is that negative electrode active material ferric oxide nano point/nitrogen codope graphene CV prepared by the embodiment of the present invention 1 is bent
Line；
Fig. 4 is negative electrode active material ferric oxide nano point/nitrogen codope graphene electric discharge prepared by the embodiment of the present invention 1
Curve.
Fig. 5 is negative electrode active material discharge curve prepared by the embodiment of the present invention 1 and comparative example 1.
Fig. 6 is negative electrode active material discharge curve prepared by the embodiment of the present invention 1 and comparative example 3.
Specific embodiment
Invention is further described in detail with reference to the accompanying drawings and detailed description:
Negative electrode active material ferric oxide nano point/nitrogen codope graphene preparation method of the invention, including walk as follows
It is rapid:
(1) graphene for weighing 40~60mg is added in 90~120mL dispersate, after 30~80min of ultrasonic disperse
To mixture A；The dispersate is the mixture of one or both of DMF and nitrine organic solvent；
(2) Fe (C is added in Xiang Suoshu mixture A5H7O2)3Solution obtains mixture B after being ultrasonically treated 20~40min；
(3) the mixture B is transferred in autoclave, autoclave is heated to 170~210 DEG C after sealing, reaction 5~
By autoclave cooled to room temperature after 9 hours, product C therein is taken out；
(4) the product C is successively washed to cleaning solution with deionized water and ethyl alcohol repeatedly and is dried after being in neutrality, done
50~70 DEG C of dry temperature drying time 2~6 hours, finally obtains negative electrode active material ferric oxide nano point/nitrogen codope graphite
Alkene.
Fe (C in the step (2)5H7O2)3Liquor capacity is 8~12mL, and concentration is 1~10mol/L.
Fe (C in the step (2)5H7O2)3Liquor capacity is 10~11mL, and concentration is 6~8mol/L.
A kind of super capacitor anode, including negative electrode active material ferric oxide nano point/nitrogen made from above-mentioned preparation method
Codope graphene and active carbon cloth.
The preparation method of the active carbon cloth the following steps are included:
(1) charcoal cloth is immersed in by 20~40mL H2SO4With 10~30mL HNO3In the mixed acid solution of composition, control
Mixing speed is 50~450r/min, is stirred 1.5 hours；
(2) mixed acid solution described in step (1) is heated to 30~50 DEG C, being kept stirring speed is 50~450r/
Min is slowly added to 3~6g KMnO4, it reacts 1~4 hour, 100~150mL deionized water is added again and stirs 2~4 hours,
Obtain mixture A；
(3) excess hydrogen peroxide solution is added in the mixture A, is kept stirring, until mixture A become it is limpid and
Charcoal cloth is taken out from mixture A after no longer generating bubble, charcoal cloth is washed to cleaning solution repeatedly with distilled water and is in neutrality, is gone forward side by side
Row is dried, and obtains oxidation charcoal cloth；
(4) oxidation charcoal cloth obtained in step (3) is put into autoclave, 50mL H is added2O and 0.5~1.2mL hydration
Hydrazine, and reduction charcoal cloth is obtained after being kept for 10~13 hours at 70~90 DEG C；
(5) will reduction charcoal cloth deionized water and ethanol washing obtained in step (4) for several times until cleaning solution be it is neutral,
Then reduction charcoal is arranged at 50~70 DEG C after drying 6~12 hours up to active carbon cloth.
The mass percent concentration of the hydrogenperoxide steam generator is 35%.
The area of the charcoal cloth is 0.1~100cm2。
The H2SO4Concentration be 5-18M, the HNO3Concentration be 5-15M.
Fe(C5H7O2)3It can be decomposed during using DMF and nitrine organic solvent as the solvent thermal reaction of solvent,
Fe has carried out the N doping of graphene while coordination.
Fe(C5H7O2)3It is used as iron precursor, because it is a kind of metal complex, it can be decomposed at low temperature
And iron ion is provided and is reacted.During solvent thermal reaction, Fe (C5H7O2)3It decomposes, Fe atom disperses in the solution.?
At 170 DEG C, dimethylamine is provided by the hydrolysis of DMF during solvent heat, and dimethylamine occurs de- between the carboxyl and dimethylamine of GO
Water condensation reaction forms peptide bond, causes the N doping of graphene (NG).Meanwhile Fe (C5H7O2)3The Fe atom of decomposition is in solvent
Fe is oxidized in thermal process2O3.Moreover, because the mild decomposition of Organic Iron precursor, reaction nucleation is relatively slow and disperses
The confinement effect of active site can be provided in the defects of NG, it can be by Fe2O3Particle is reduced in size to Fe2O3Nano dot
(ND), lower using reaction temperature needed for Organic Iron presoma for more traditional molysite inorganic precursor, reaction more heats
With the particle size of formation is smaller, is conducive to the transmitting of mass transfer and electronics, and the active material chemical property of preparation is more excellent.
Active carbon cloth of the present invention carries out oxidation process first, increases its Surface oxygen-containing groups, increases its hydrophily, due to
When composition asymmetry or symmetry supercapacitor, electrolyte is aqueous electrolyte, so good hydrophily is device application
Basis.Active carbon cloth restores again process, not only further enhances its electric conductivity, in addition and reduces charcoal cloth surface
Oxygen-containing group will cause fake capacitance when oxygen-containing group is excessive, influence the stability of material.
It is compared with other reducing agents, the reducing power of hydrazine hydrate is stronger, and required amount is less, only needs a little hydrazine hydrate
Reach preferable reduction effect.The molecular formula of hydrazine hydrate is N2H4, from valence state, N is-divalent, is easily oxidised into 0 valence object
Kind, structurally, N-N singly-bound is very unstable, it is easily formed stable three key of nitrogen nitrogen, therefore compare other reducing agents, water
It is very strong for closing the reducing power of hydrazine.
The present invention can make synthesized negative electrode material using the high performance active carbon cloth of preparation as the substrate of negative electrode material
More firm attachment has good electric conductivity and flexible and stability in the application of supercapacitor hereafter.
With Fe2O3NDs NG is cathode, is 4165.7W kg in power density-1When have 14.5Wh kg-1High-energy it is close
Degree after assembling flexible solid-state supercapacitor, has outstanding cyclical stability.
Embodiment 1
A kind of preparation method of super capacitor anode, includes the following steps:
The preparation of charcoal cloth substrate:
It 1) is 4cm by area2Charcoal cloth is immersed in by 20mL H2SO4With 15mL HNO3In the mixed acid solution of composition, control
Mixing speed is 300r/min, is stirred 1.5 hours；H2SO4And HNO3Concentration is 10M；
2) mixed acid solution described in step 1) is heated to 40 DEG C, being kept stirring speed is 300r/min, is slowly added
Enter 5g KMnO4, react 2 hours, 120mL deionized water be added again and stirs 3 hours, obtains mixture A；
3) excess hydrogen peroxide solution is added in the mixture A, is kept stirring, until mixture A become it is limpid and
Charcoal cloth is taken out from mixture A after no longer generating bubble, charcoal cloth is washed to cleaning solution repeatedly with distilled water and is in neutrality, is gone forward side by side
Row is dried, and obtains oxidation charcoal cloth；
4) oxidation charcoal cloth obtained in step 3) is put into autoclave, 50mL H is added2O and 1mL hydrazine hydrate, and 80
Reduction charcoal cloth is obtained after being kept for 10 hours at DEG C；
5) by reduction charcoal cloth deionized water obtained in step 4) and ethanol washing for several times until cleaning solution is neutrality, so
Reduction charcoal is arranged at 60 DEG C after drying 10 hours up to active carbon cloth afterwards.
The preparation of negative electrode active material:
(1) graphene for weighing 50mg is added in 100mL DMF, and mixture A is obtained after ultrasonic disperse 60min；
(2) Fe (C of 10mL 5M is added in Xiang Suoshu mixture A5H7O2)3Solution is mixed after being ultrasonically treated 30min
Object B；
(3) the mixture B is transferred in autoclave, after autoclave is heated to 190 DEG C, reaction 7 hours after sealing
By autoclave cooled to room temperature, product C therein is taken out；
(4) the product C is successively washed to cleaning solution with deionized water and ethyl alcohol repeatedly and is dried after being in neutrality, done
Dry temperature 60 C drying time 4 hours, finally obtains negative electrode active material ferric oxide nano point/nitrogen codope graphene.
Negative electrode active material is supported on charcoal cloth and both obtains super capacitor anode.
Comparative example 1
A kind of preparation method of super capacitor anode, includes the following steps:
The preparation of charcoal cloth substrate: with embodiment 1.
The preparation of negative electrode active material:
(1) graphene for weighing 50mg is added in 100mL DMF, and mixture A is obtained after ultrasonic disperse 60min；
(2) the mixture A is transferred in autoclave, after autoclave is heated to 190 DEG C, reaction 7 hours after sealing
By autoclave cooled to room temperature, product B therein is taken out；
(3) the product B is successively washed to cleaning solution with deionized water and ethyl alcohol repeatedly and is dried after being in neutrality, done
Dry temperature 60 C drying time 4 hours, finally obtains nitrogen-doped graphene material.
Negative electrode active material is supported on charcoal cloth and both obtains super capacitor anode.
Comparative example 2
A kind of preparation method of super capacitor anode, includes the following steps:
The preparation of charcoal cloth substrate: with embodiment 1.
The preparation of negative electrode active material:
(1) graphene for weighing 50mg is added in 100mL ethyl alcohol, and mixture A is obtained after ultrasonic disperse 60min；
(2) Fe (C of 10mL 5M is added in Xiang Suoshu mixture A5H7O2)3Solution is mixed after being ultrasonically treated 30min
Object B；
(3) the mixture B is transferred in autoclave, after autoclave is heated to 190 DEG C, reaction 7 hours after sealing
By autoclave cooled to room temperature, product C therein is taken out；
(4) the product C is successively washed to cleaning solution with deionized water and ethyl alcohol repeatedly and is dried after being in neutrality, done
Dry temperature 60 C drying time 4 hours, finally obtains ferric oxide nano point doped graphene material.
Negative electrode active material is supported on charcoal cloth and both obtains super capacitor anode.
Comparative example 3
A kind of preparation method of super capacitor anode, includes the following steps:
The preparation of charcoal cloth substrate: with embodiment 1.
The preparation of negative electrode active material:
(1) graphene for weighing 50mg is added in 100mL DMF, and mixture A is obtained after ultrasonic disperse 60min；
(2) Fe (NO of 10mL 5M is added in Xiang Suoshu mixture A3)3Solution obtains mixture after being ultrasonically treated 30min
B；
(3) the mixture B is transferred in autoclave, after autoclave is heated to 190 DEG C, reaction 7 hours after sealing
By autoclave cooled to room temperature, product C therein is taken out；
(4) the product C is successively washed to cleaning solution with deionized water and ethyl alcohol repeatedly and is dried after being in neutrality, done
Dry temperature 60 C drying time 4 hours, finally obtains ferric oxide nano point and nitrogen codope grapheme material.
Negative electrode active material is supported on charcoal cloth and both obtains super capacitor anode.
Embodiment 2
A kind of preparation method of super capacitor anode, includes the following steps:
The preparation of charcoal cloth substrate:
It 1) is 10cm by area2Charcoal cloth is immersed in by 20mL H2SO4With 15mL HNO3In the mixed acid solution of composition, control
Mixing speed processed is 200r/min, is stirred 1.5 hours；H2SO4And HNO3Concentration is 8M.
2) mixed acid solution described in step 1) is heated to 40 DEG C, being kept stirring speed is 350r/min, is slowly added
Enter 6g KMnO4, react 2 hours, 120mL deionized water be added again and stirs 3 hours, obtains mixture A；
3) excess hydrogen peroxide solution is added in the mixture A, is kept stirring, until mixture A become it is limpid and
Charcoal cloth is taken out from mixture A after no longer generating bubble, charcoal cloth is washed to cleaning solution repeatedly with distilled water and is in neutrality, is gone forward side by side
Row is dried, and obtains oxidation charcoal cloth；
4) oxidation charcoal cloth obtained in step 3) is put into autoclave, 50mL H is added2O and 1.2mL hydrazine hydrate, and
Reduction charcoal cloth is obtained after being kept for 13 hours at 90 DEG C；
5) by reduction charcoal cloth deionized water obtained in step 4) and ethanol washing for several times until cleaning solution is neutrality, so
Reduction charcoal is arranged at 70 DEG C after drying 12 hours up to active carbon cloth afterwards.
The preparation of negative electrode active material:
(1) graphene for weighing 60mg is added in 100mL nitrine organic solvent, is mixed after ultrasonic disperse 80min
Object A；
(2) Fe (C of 8mL 10M is added in Xiang Suoshu mixture A5H7O2)3Solution is mixed after being ultrasonically treated 40min
Object B；
(3) the mixture B is transferred in autoclave, after autoclave is heated to 210 DEG C, reaction 9 hours after sealing
By autoclave cooled to room temperature, product C therein is taken out；
(4) the product C is successively washed to cleaning solution with deionized water and ethyl alcohol repeatedly and is dried after being in neutrality, done
Dry temperature 70 C drying time 6 hours, finally obtains negative electrode active material ferric oxide nano point/nitrogen codope graphene.
Negative electrode active material is supported on charcoal cloth and both obtains super capacitor anode.
Embodiment 3
A kind of preparation method of super capacitor anode, includes the following steps:
The preparation of charcoal cloth substrate:
It 1) is 1cm by area2Charcoal cloth is immersed in by 20mL H2SO4With 10mL HNO3In the mixed acid solution of composition, control
Mixing speed is 200r/min, is stirred 1.5 hours；H2SO4And HNO3Concentration is 5M；
2) mixed acid solution described in step 1) is heated to 30 DEG C, being kept stirring speed is 200r/min, is slowly added
Enter 3g KMnO4, react 2 hours, 100mL deionized water be added again and stirs 2 hours, obtains mixture A；
3) excess hydrogen peroxide solution is added in the mixture A, is kept stirring, until mixture A become it is limpid and
Charcoal cloth is taken out from mixture A after no longer generating bubble, charcoal cloth is washed to cleaning solution repeatedly with distilled water and is in neutrality, is gone forward side by side
Row is dried, and obtains oxidation charcoal cloth；
4) oxidation charcoal cloth obtained in step 3) is put into autoclave, 50mL H is added2O and 0.5mL hydrazine hydrate, and
Reduction charcoal cloth is obtained after being kept for 10~13 hours at 70~90 DEG C；
5) by reduction charcoal cloth deionized water obtained in step 4) and ethanol washing for several times until cleaning solution is neutrality, so
Reduction charcoal is arranged at 50~70 DEG C after drying 6~12 hours up to active carbon cloth afterwards.
The preparation of negative electrode active material:
(1) graphene for weighing 50mg is added in 100mL DMF, and mixture A is obtained after ultrasonic disperse 60min；
(2) Fe (C of 10mL 5M is added in Xiang Suoshu mixture A5H7O2)3Solution is mixed after being ultrasonically treated 30min
Object B；
(3) the mixture B is transferred in autoclave, after autoclave is heated to 190 DEG C, reaction 7 hours after sealing
By autoclave cooled to room temperature, product C therein is taken out；
(4) the product C is successively washed to cleaning solution with deionized water and ethyl alcohol repeatedly and is dried after being in neutrality, done
Dry temperature 60 C drying time 4 hours, finally obtains negative electrode active material ferric oxide nano point/nitrogen codope graphene.
Negative electrode active material is supported on charcoal cloth and both obtains super capacitor anode.
Embodiment 4
A kind of preparation method of super capacitor anode, includes the following steps:
The preparation of charcoal cloth substrate:
It 1) is 4cm by area2Charcoal cloth is immersed in by 20mL H2SO4With 15mL HNO3In the mixed acid solution of composition, control
Mixing speed is 300r/min, is stirred 1.5 hours；H2SO4And HNO3Concentration is 12M；
2) mixed acid solution described in step 1) is heated to 40 DEG C, being kept stirring speed is 300r/min, is slowly added
Enter 5g KMnO4, react 2 hours, 120mL deionized water be added again and stirs 3 hours, obtains mixture A；
3) excess hydrogen peroxide solution is added in the mixture A, is kept stirring, until mixture A become it is limpid and
Charcoal cloth is taken out from mixture A after no longer generating bubble, charcoal cloth is washed to cleaning solution repeatedly with distilled water and is in neutrality, is gone forward side by side
Row is dried, and obtains oxidation charcoal cloth；
4) oxidation charcoal cloth obtained in step 3) is put into autoclave, 50mL H is added2O and 1mL hydrazine hydrate, and 70
Reduction charcoal cloth is obtained after being kept for 10 hours at DEG C；
5) by reduction charcoal cloth deionized water obtained in step 4) and ethanol washing for several times until cleaning solution is neutrality, so
Reduction charcoal is arranged at 50 DEG C after drying 6 hours up to active carbon cloth afterwards.
The preparation of negative electrode active material:
(1) graphene for weighing 40mg is added in the mixture of 90mL DMF and nitrine organic solvent, ultrasonic disperse
Mixture A is obtained after 30min；
(2) Fe (C of 8mL 1M is added in Xiang Suoshu mixture A5H7O2)3Solution is mixed after being ultrasonically treated 20min
Object B；
(3) the mixture B is transferred in autoclave, after autoclave is heated to 170 DEG C, reaction 5 hours after sealing
By autoclave cooled to room temperature, product C therein is taken out；
(4) the product C is successively washed to cleaning solution with deionized water and ethyl alcohol repeatedly and is dried after being in neutrality, done
Dry temperature 50 C drying time 3 hours, finally obtains negative electrode active material ferric oxide nano point/nitrogen codope graphene.
Negative electrode active material is supported on charcoal cloth and both obtains super capacitor anode.
Comparative example 4
A kind of preparation method of super capacitor anode, includes the following steps:
The preparation of charcoal cloth substrate:
4) oxidation charcoal cloth obtained in step 3) is put into autoclave, 50mL H is added2O, and 10 are kept at 70 DEG C
Reduction charcoal cloth is obtained after hour；
Remaining step is same as Example 4.
The preparation of negative electrode active material:
It is same as Example 4.
Negative electrode active material is supported on charcoal cloth and both obtains super capacitor anode.
Experimental conditions
Scanning electron microscope (SEM) image of product is shown in Fig. 1 in embodiment 1.It will be clear that nitrogen is mixed
Miscellaneous graphene keeps nanometer sheet form after solvent thermal reaction.And Fe2O3Nano particle is evenly dispersed on NG and firmly
It is anchored in NG nanometer sheet.
The XRD spectra of product is as shown in Fig. 2, graphene is recorded in the smaller broad peak at 23.6 ° in embodiment 1
(002) diffraction maximum [22-23].Other peaks in XRD spectra prove that the sample is Fe2O3(JCPDF number 25-1042),
Peak at 11.6 °, 35.8 °, 43.5 ° and 63.6 ° corresponds to (102), (119), the crystal face of (0012) and (4012) Fe2O3.Cause
This, which shows that we are successfully prepared Fe2O3NDs@NG composite material
Fig. 3 is the negative electrode active material of ferric oxide nano point prepared by the embodiment of the present invention 1 and nitrogen codope graphene
CV curve.By NG and Fe2O3The cyclic voltammetric (CV) of NDs@NG compares with constant current charge-discharge (GCD) curve, and NG shows double
Layer capacitance, and it applies Fe2O3The main specific capacitance of NDs is occupied to NG compares Fe2O3ND bigger quality.When by Fe2O3ND
When in conjunction with NG, specific capacitance is improved.Fe is obtained in the three-electrode battery containing 2M KOH electrolyte2O3NDs@NG's
Cyclic voltammetric (CV) and constant current charge-discharge (GCD) curve, as shown.(from 5mV s under different scanning rates-1To 50mV s-1), CV curve is tested under -1 to 0V potential windows.Due to Fe2O3NDs@NG electrode material with NG electric double layer capacitance and
Fe2O3The redox capacitor of NDs, and curve shows Fe2O3The capacitor of NDs@NG electrode material comes from NG and Fe2O3ND
's.
Fig. 4 is that the ferric oxide nano point of the preparation of the embodiment of the present invention 1 and the negative electrode active material of nitrogen codope graphene exist
Different current density (0.5,1,2,3,5,10 and 15A g-1) under constant current charge-discharge curve.Pass through these curves, Wo Menke
To see Fe2O3NDs@NG has symmetrical charging and discharging capabilities, can be seen that Fe from constant current discharge curve2O3NDs@NG electrode
The specific capacitance value of material is respectively 318,290,272,260,245,218 and 195F g-1, respectively 0.5,1,2,3,5,10 He
15Ag-1.With the increase (increasing by 30 times) of current density, specific capacitance will decline, Fe2O3The specific capacitance of NDs@NG electrode material is protected
Holdup is about 70%, shows Fe2O3NDs@NG has good high rate performance.
Table 1 lists the specific capacity of super capacitor anode made from Examples 1 to 4 and comparative example 1~4 and capacity is protected
Holdup.Test condition are as follows: specific capacity: 1A g-1, constant current charge-discharge；Capacity retention ratio: constant current charge and discharge is used after 500 circle CV
Electrical testing specific capacity, the ratio of front and back specific capacity are capacity retention ratio.CV condition: -1 arrives the potential windows of 0V, sweeps fast 10mV s-1。
The specific capacity and capacity retention ratio of 1 different materials of table
The material specific capacity and capacity retention ratio that it can be seen from table prepared by Examples 1 to 4 are all higher, electrochemistry
It can be excellent.
It is compared with embodiment 1, the comparative example 2 of comparative example 1 (Fig. 5) without ferric oxide nano point and not N doping compares
Capacity is lower, and comprehensive performance is poor, it is seen that ferric oxide nano point and N doping are very crucial to the performance for improving material, it is possible to provide
Higher capacitor.
3 performance of comparative example prepared using inorganic source of iron ferric nitrate is also poor, and specific capacity and stability are all lower.This be by
What the property of source of iron determined, Fe (C5H7O2)3The decomposition of Organic Iron precursor is milder, and required temperature is low, generation
Fe2O3The size of particle can be reduced to Fe2O3Nano dot (ND), and for traditional molysite inorganic precursor, decomposition reaction is compared
Acutely, the particle size of formation is larger, and particle can constantly reunite during capacitor cycle, can take off when particle is excessive
Graphene-based bottom out, to influence the stability and chemical property of material.
In addition, the performance of charcoal cloth also influences the performance of material.It is compared with embodiment 4, without using hydrazine hydrate in comparative example 4
The oxide group of processing carbon cloth, charcoal cloth surface is excessive, influences the attachment of negative electrode active material, cause material in cyclic process from
The abjection of charcoal cloth surface, stability decline.
In conclusion the contents of the present invention are not limited in the above embodiments, the knowledgeable people in same area exists
Can propose other embodiments within technological guidance's thought of the invention easily, but this embodiment be included in it is of the invention
Within the scope of.
Claims (8)
1. a kind of negative electrode active material ferric oxide nano point/nitrogen codope graphene preparation method, which is characterized in that including with
Lower step:
(1) graphene for weighing 40~60mg is added in 90~120mL dispersate, is mixed after 30~80min of ultrasonic disperse
Close object A；The dispersate is the mixture of one or both of DMF and nitrine organic solvent；
(2) Fe (C is added in Xiang Suoshu mixture A5H7O2)3Solution obtains mixture B after being ultrasonically treated 20~40min；
(3) the mixture B is transferred in autoclave, autoclave is heated to 170~210 DEG C after sealing, reaction 5~9 is small
When after by autoclave cooled to room temperature, take out product C therein；
(4) the product C is successively washed to cleaning solution with deionized water and ethyl alcohol repeatedly and is dried after being in neutrality, dry temperature
50~70 DEG C of degree, drying time 2~6 hours, finally obtains negative electrode active material ferric oxide nano point/nitrogen codope graphene.
2. negative electrode active material ferric oxide nano point/nitrogen codope graphene preparation method according to claim 1, special
Sign is, the Fe (C in the step (2)5H7O2)3Liquor capacity is 8~12mL, and concentration is 1~10mol/L.
3. negative electrode active material ferric oxide nano point/nitrogen codope graphene preparation method according to claim 3, special
Sign is, the Fe (C in the step (2)5H7O2)3Liquor capacity is 10~11mL, and concentration is 6~8mol/L.
4. a kind of super capacitor anode, which is characterized in that including being born made from any one of the claim 1-3 preparation method
Pole active material ferric oxide nano point/nitrogen codope graphene and active carbon cloth.
5. super capacitor anode according to claim 4, which is characterized in that the preparation method of the active carbon cloth include with
Lower step:
(1) charcoal cloth is immersed in by 20~40mL H2SO4With 10~30mL HNO3In the mixed acid solution of composition, control stirring
Speed is 50~450r/min, is stirred 1~3 hour；
(2) mixed acid solution described in step (1) is heated to 30~50 DEG C, being kept stirring speed is 50~450r/min,
It is slowly added to 3~6g KMnO4, react 1~4 hour, 100~150mL deionized water be added again and stirs 2~4 hours, obtains
Mixture A；
(3) excess hydrogen peroxide solution is added in the mixture A, is kept stirring, until mixture A becomes limpid and no longer
Charcoal cloth is taken out from mixture A after generating bubble, charcoal cloth is washed to cleaning solution repeatedly with distilled water and is in neutrality, and is done
Dry processing obtains oxidation charcoal cloth；
(4) oxidation charcoal cloth obtained in step (3) is put into autoclave, 50mL H is added2O and 0.5~1.2mL hydrazine hydrate, and
Reduction charcoal cloth is obtained after being kept for 10~13 hours at 70~90 DEG C；
(5) by reduction charcoal cloth deionized water obtained in step (4) and ethanol washing for several times until cleaning solution is neutrality, then
Reduction charcoal is arranged at 50~70 DEG C after drying 6~12 hours up to active carbon cloth.
6. super capacitor anode according to claim 5, which is characterized in that the mass percent of the hydrogenperoxide steam generator
Concentration is 35%.
7. super capacitor anode according to claim 5, which is characterized in that the area of the charcoal cloth is 0.1~100cm2。
8. super capacitor anode according to claim 5, which is characterized in that the H2SO4Concentration be 5-18M, it is described
HNO3Concentration be 5-15M.
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| CN111592376A (en) * | 2020-06-08 | 2020-08-28 | 北京化工大学 | Composite aerogel functional material based on ferroferric oxide nanowire/graphene oxide interpenetrating structure and preparation method thereof |
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