CN101527202B - Oxidized grapheme/polyaniline super capacitor composite electrode material and preparation method - Google Patents
Oxidized grapheme/polyaniline super capacitor composite electrode material and preparation method Download PDFInfo
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Abstract
The invention discloses an oxidized grapheme/polyaniline super capacitor composite electrode material and the preparation method and the application thereof. The preparation method comprise the following steps: firstly, adding oxidized graphite to water for ultrasonic dispersion so as to form an oxidized grapheme solution with uniformly dispersed single pieces; at room temperature, dropping aniline to the obtained oxidized grapheme solution for continuous ultrasonic dispersion to from a mixed solution; at a low temperature condition, adding hydrogen peroxide, ferric trichloride and a hydrochloric acid solution dropwise to the mixed solution, and stirring the solution for polymerization; and after the reaction is finished, centrifugating, washing and roasting the obtained mixed solution in vacuum to obtain the oxidized grapheme/polyaniline super capacitor composite electrode material which is used as the electrode material of an electricity storage system of a super capacitor and a battery. The oxidized grapheme/polyaniline super capacitor composite electrode material with good electrochemistry performance is obtained by the method, and the specific capacity of the oxidized grapheme and the polyaniline is greatly improved. In addition, the addition of the oxidized grapheme improves the charge and discharge service life of the polyaniline.
Description
Technical field
The invention belongs to organic and inorganic composite material, particularly a kind of graphene oxide/polyaniline super capacitor composite electrode material and preparation method thereof.
Background technology
Ultracapacitor has huge using value and market potential at aspects such as automobile, electric power, railway, communication, national defence, consumption electronic products, by countries in the world institute extensive concern.But there is bottleneck in the production of the core of ultracapacitor one high performance electrode material always.Current most of electrochemical capacitance product is based on the material with carbon element of the cheapness of electric double layer capacitance accumulate mechanism, desires to improve its power density simultaneously on this basis and the energy density difficulty is very big; The preparation cost that carbon nano-tube material is expensive is very limited its practical application.Electrically conductive polyaniline based on the fake capacitance store charge of redox reaction; Has high energy density; But its ion doping/go doping can cause that expansion appears in the volume of its film makes the film cracking, finally causes the electrical property of electrode material to descend; Charge and discharge circulation life is short, poor stability, influences its utilance etc.For this reason; Material with carbon element and polyaniline be combined into to excavate had one of approach of high-performance electrode new material; Such as electrically conductive polyaniline/CNT (Mi, H.et al., Microwave-Assisted Synthesis and Electrochemical Capacitance of Polyaniline/Multi-Wall Carbon Nanotubes Composite.Electrochem.Commun.2007; 9,2859-2862; Deng Meigen etc.; Chinese invention patent CN 1887965A), polyaniline/active carbon (Wang Qin etc.; Ultracapacitor is with the research of polyaniline/active carbon combination electrode. novel charcoal material .2008, and 23,275-280) wait the electrochemical properties of composite material that raising has to a great extent all been arranged.Though the specific area of active carbon is bigger, because its conductivity is bad, performance of composites improves not obvious; The higher also big limitations of the preparation cost of CNT its application performance.
Graphene is the two-dimentional graphite nano plate that exists with an atomic thickness, has a lot of unique physical and chemical performances, like the specific area of super large, and excellent conductivity, thermal conductivity and mechanicalness etc., and therefore caused extensive concern rapidly.It is the thinnest a kind of in the known materials, but the material that hardness is maximum, toughness is maximum.Its oxide is that graphene oxide also has unique physical and chemical performance; " graphene oxide " paper of U.S. scientist preparation is that a kind of intensity is high, pliability is strong and novel type of paper material (Dmitriy A.Dikin et al.Preparation and characterization of graphene oxide paper.Nature 2007 of lightweight; 448; 457-460); This new material both can be as the electrolyte of fuel cell or the electrode of hydrogen storage material, ultracapacitor and battery, ultrathin chemical filter, also can mix the new material of production with polymer etc.In composite material, introduce Graphene class material (like first macromolecule/graphene complex; Sasha Stankovich et al.Graphene-based composite materials.Nature 2006; 442,282-286), utilize its special two-dimensional nanostructure, ultra-high surface area, good conductivity, superpower advantages such as mechanical property; Can prepare some new functional composite materials, open up the application of novel carbon-based material.
Summary of the invention
The object of the present invention is to provide a kind of graphene oxide/polyaniline composite electrode material that is used for energy storage device such as ultracapacitor and preparation method thereof, this method can improve the polyaniline specific volume and prolong it and discharge and recharge the life-span.
The technical solution that realizes the object of the invention is: a kind of graphene oxide/polyaniline super capacitor composite electrode material is got by the following steps preparation:
(1) graphite oxide is added to ultrasonic dispersion in the water, forms with the homodisperse graphene oxide solution of monolithic layer;
(2) under the room temperature, in gained graphene oxide solution, drip aniline, continue ultrasonic dispersion and form mixed liquor;
(3) under cryogenic conditions, in mixed liquor, dropwise add hydrogen peroxide, ferric trichloride and hydrochloric acid solution successively, stir polymerization;
(4) reaction finishes, and the mixed liquor that obtains is centrifugal, washing, vacuum drying obtain graphene oxide/polyaniline composite electrode material.
A kind of preparation method of graphene oxide/polyaniline super capacitor composite electrode material, step is following:
(1) graphite oxide is added to ultrasonic dispersion in the water, forms with the homodisperse graphene oxide solution of monolithic layer;
(2) under the room temperature, in gained graphene oxide solution, drip aniline, continue ultrasonic dispersion and form mixed liquor;
(3) under cryogenic conditions, in mixed liquor, dropwise add hydrogen peroxide, ferric trichloride and hydrochloric acid solution successively, make aniline equate behind the constant volume with the concentration of hydrogen peroxide, stir polymerization;
(4) reaction finishes, and the mixed liquor that obtains is centrifugal, washing, vacuum drying obtain graphene oxide/polyaniline composite electrode material.
The present invention compared with prior art, its remarkable advantage: (1) makes full use of the electric double layer capacitance that improves compound with the super large specific area of the graphene oxide of monolithic layer form stable existence; (2) utilize oxy radical such as graphene oxide surface carboxyl to form binding site; Chemical doping effect through hydroxy-acid group; And two a large amount of hydrogen bond action and pi-pi accumulation effects between component, make graphene oxide and polyaniline skeleton organically combine, form graphene oxide/polyaniline nano-composite material; Synergy between component makes the super capacitor performance of combination electrode material improve greatly, especially aspect specific capacity and charge and discharge circulation life; (3) utilize the excellent mechanical property of graphene oxide to improve the charge and discharge circulation life of combination electrode material; (4) one in-situ doped polymerizations of step have realized the even dispersion of single-layer oxidized graphite alkene and polyaniline material, and while graphene oxide in polymerization process has also served as the template role of nanofiber assembly; Preparation method's operating process of (5) one in-situ doped polymerizations of step is easy, compares with other material with carbon element/polyaniline composite material, and its production cost is lower than CNT or carbon fibre composite, than the superior performance of absorbent charcoal composite material; (6) use the compound of the present invention's preparation,, can application promise in clinical practice and economic benefit be arranged at ultracapacitor and other energy electrode material fields in conjunction with the characteristic of graphene oxide and polyaniline and nano material.
Below in conjunction with accompanying drawing the present invention is described in further detail.
Description of drawings
Fig. 1 is the graphite oxide and the aniline mass ratio (GO: ANI) be the TEM (a) and IR (b) figure of graphene oxide/polyaniline composite electrode material of 1: 100 of instance 1 preparation of the present invention.
Fig. 2 is graphite oxide and the aniline mass ratio (GO: be that graphene oxide/polyaniline composite electrode material of 1: 100 charges and discharge electrograph under the different electric current density ANI) of instance of the present invention 1 preparation.
Fig. 3 is the different graphite oxides of instance 1～5 preparation of the present invention and the cyclic voltammogram of combination electrode material when 10mV/S of aniline mass ratio.
Embodiment
Graphene oxide/polyaniline super capacitor composite electrode material of the present invention and preparation method thereof, step system is following:
(1) graphite oxide is added to ultrasonic dispersion in the water, forms with the homodisperse graphene oxide solution of monolithic layer; Ultrasonic time is ultrasonic 20～120min.
(2) under the room temperature, in gained graphene oxide solution, drip aniline, continue ultrasonic dispersion and form mixed liquor; Ultrasonic time is ultrasonic 10～60min.
(3) under cryogenic conditions, in mixed liquor, dropwise add hydrogen peroxide, ferric trichloride and hydrochloric acid solution successively, stir polymerization; Reaction temperature is 0～20 ℃, stirs polymerization time 4～24h.
(4) reaction finishes, and the mixed liquor that obtains is centrifugal, washing, vacuum drying obtain graphene oxide/polyaniline composite electrode material.
Wherein, the ratio of water and the consumption of graphite oxide 1: 1～100: 1, graphite oxide is 1: 10～1: 300 with the ratio of the quality of aniline, the ratio of the mole of aniline, hydrogen peroxide, ferric trichloride is 300～1000: 300～1000: 1; Wherein, the consumption of the ferric trichloride of water, aniline, 30% hydrogen peroxide, 37% hydrochloric acid, 0.1mol/L is in milliliter; The consumption of graphite oxide is in milligram.All between 0.05～0.5mol/L, the concentration of hydrochloric acid is between 0.5～1.5mol/L for the concentration of aniline and hydrogen peroxide.
The purposes of graphene oxide/polyaniline super capacitor composite electrode material of the present invention is with the electrode material of graphene oxide/polyaniline composite material as the power storage system of ultracapacitor, battery.
The present invention is being that oxidant, ferric trichloride are that catalyst, hydrochloric acid are to add graphene oxide in the aniline polymerization process of main dopant acid with the hydrogen peroxide; By graphene oxide surface oxygen base group; Doping effect through hydroxy-acid group; Hydrogen bond action between two components and pi-pi accumulation effect make graphene oxide and polyaniline skeleton organically combine, and form graphene oxide/polyaniline nano-composite material; Synergy between component makes the super capacitor performance of combination electrode material improve greatly, especially aspect the specific capacity and cycle life that improve polyaniline.
Embodiment 1: the preparation of graphite oxide.10g phosphorus pentoxide and 10g potassium peroxydisulfate joined take out after stirring 30min in 80 ℃, the 30mL concentrated sulfuric acid, normal temperature down behind the reaction 6h with product filter, washing is to neutral and dry to constant weight at normal temperatures.Above-mentioned product is joined in the concentrated sulfuric acid of 0 ℃ of 460mL; Stir and the slow potassium permanganate that adds, hierarchy of control temperature is no more than 15 ℃ simultaneously, is warming up to 35 ± 3 ℃ after stirring; After continuing to stir certain hour; In system, slowly add the 1L deionized water, the control temperature is no more than 100 ℃, continues to stir 15min.Adding 2.8L deionized water and 50mL mass concentration are 30% hydrogen peroxide solution.After stirring 5min gained brown suspension suction filtration, dialysis there is not sulfate ion to filtrating.With product at 60 ℃ of following vacuum dryings.
(1) graphite oxide with 18.6mg is added in the 192.26mL water ultrasonic 20～120min., form with the homodisperse graphene oxide solution of monolithic layer; (2) under the room temperature, in gained graphene oxide solution, drip 1.86mL aniline, ultrasonic 10～60min disperses to form the mixed liquor of 0.1mol/L aniline; (3) under 4 ℃; In mixed liquor, dropwise add 30% hydrogen peroxide of 2.06mL, the 0.1mol/L ferric trichloride of 0.4mL and 37% hydrochloric acid solution of 3.42mL respectively; The concentration of hydrogen peroxide is 0.1mol/L, and the concentration of hydrochloric acid is 1.5mol/L, stirs polymerization 24h; (4) reaction finishes, and behind the mixed liquor that obtains is centrifugal, water, the ethanol cyclic washing, obtains graphite oxide and aniline mass ratio (GO: ANI) be graphene oxide/polyaniline composite electrode material of 1: 100 through 40 ℃ of vacuumizes.
The pattern of composite material and structure use ESEM (SEM) and infrared spectrometer to characterize respectively, and the result is shown in Fig. 1 (a and b).TEM explanation gained compound is a nanofibrous structures.The infrared comparing result of graphite oxide (GO), polyaniline (PANI), graphene oxide/polyaniline composite electrode material proves; Red shift all takes place in the characteristic peak of oxy radicals such as the carbonyl of GO and hydroxyl in graphene oxide/polyaniline composite material; Show that graphene oxide and polyaniline skeleton organically combine through active forces such as doping and hydrogen bond actions, have formed graphene oxide/polyaniline composite material.
Gained electrode material, conductive agent (acetylene black) and binding agent (PTFE) mixed in proportion to be pressed onto process electrode on the collector; Carry out the cyclic voltammetric test of different constant current charge-discharges and 10mV/s sweep speed, the result is shown in 1: 100 curve among Fig. 2 and Fig. 3.Unipolar specific capacitance (the C of ultracapacitor; F/g) can be according to discharging and recharging formula C=(I Δ t)/(m Δ E) or C=I)/(mv) calculating; Wherein I is a discharging current, and Δ t is discharge time, and m is the quality of active material on the single electrode; Δ E joins the pressure drop interval that internal resistance (ESR) causes in the equivalence for the voltage drop of discharging does not include, v is the voltage scan rate of cyclic voltammetric.The specific capacity of the graphene oxide/polyaniline composite electrode material of preparation is 530F/g, and the polyaniline specific capacity is 216F/g.
Embodiment 2: the preparation of graphite oxide is with embodiment 1.
(1) graphite oxide with 15.5mg is added to ultrasonic 20～120min in the 196.79mL water, forms with the homodisperse graphene oxide solution of monolithic layer; (2) under the room temperature, in gained graphene oxide solution, drip 0.93mL aniline, ultrasonic 10～60min disperses to form the mixed liquor of 0.05mol/L aniline; (3) under 0 ℃; In mixed liquor, dropwise add 30% hydrogen peroxide of 1.72mL, the 0.1mol/L ferric trichloride of 0.33mL and 37% hydrochloric acid solution of 0.23mL respectively; The concentration of hydrogen peroxide is 0.083mol/L, and the concentration of hydrochloric acid is 0.1mol/L, stirs polymerization 24h; (4) reaction finishes, and behind the mixed liquor that obtains is centrifugal, water, the ethanol cyclic washing, obtains graphite oxide and aniline mass ratio (GO: ANI) be graphene oxide/polyaniline composite electrode material of 1: 60 through 40 ℃ of vacuumizes.
Cyclic voltammetric test result under the 10mV/s of graphene oxide/polyaniline composite electrode material of preparation is shown in 1: 60 curve among Fig. 3.The specific capacity of combination electrode material is 650F/g.
Embodiment 3: the preparation of graphite oxide is with embodiment 1.
(1) graphite oxide with 186.2mg is added to ultrasonic 20～120min in the 190.61mL water, forms with the homodisperse graphene oxide solution of monolithic layer; (2) under the room temperature, in gained graphene oxide solution, drip 3.73mL aniline, ultrasonic 10～60min disperses to form the mixed liquor of 0.2mol/L aniline; (3) under 10 ℃; In mixed liquor, dropwise add 30% hydrogen peroxide of 4.12mL, the 0.1mol/L ferric trichloride of 0.4mL and 37% hydrochloric acid solution of 1.14mL respectively; The concentration of hydrogen peroxide is 0.2mol/L, and the concentration of hydrochloric acid is 0.5mol/L, stirs polymerization 12h; (4) reaction finishes, and behind the mixed liquor that obtains is centrifugal, water, the ethanol cyclic washing, obtains graphite oxide and aniline mass ratio (GO: ANI) be graphene oxide/polyaniline composite electrode material of 1: 20 through 40 ℃ of vacuumizes.
Cyclic voltammetric test result under the 10mV/s of graphene oxide/polyaniline composite electrode material of preparation is shown in 1: 20 curve among Fig. 3.The specific capacity of combination electrode material is 461F/g.
Embodiment 4: the preparation of graphite oxide is with embodiment 1.
(1) graphite oxide with 372.5mg is added in the 188.54mL water ultrasonic 20～120min., form with the homodisperse graphene oxide solution of monolithic layer; (2) under the room temperature, in gained graphene oxide solution, drip 3.73mL aniline, ultrasonic 10～60min disperses to form the mixed liquor of 0.2mol/L aniline; (3) under 20 ℃; In mixed liquor, dropwise add 30% hydrogen peroxide of 4.12mL, the 0.1mol/L ferric trichloride of 1.33mL and 37% hydrochloric acid solution of 2.28mL respectively; The concentration of hydrogen peroxide is 0.2mol/L, and the concentration of hydrochloric acid is 1.0mol/L, stirs polymerization 4h; (4) reaction finishes, and behind the mixed liquor that obtains is centrifugal, water, the ethanol cyclic washing, obtains graphite oxide and aniline mass ratio (GO: ANI) be graphene oxide/polyaniline composite electrode material of 1: 10 through 40 ℃ of vacuumizes.
Cyclic voltammetric test result under the 10mV/s of graphene oxide/polyaniline composite electrode material of preparation is shown in 1: 10 curve among Fig. 3.The specific capacity of combination electrode material is 350F/g.
Embodiment 5: the preparation of graphite oxide is with embodiment 1.
(1) graphite oxide with 31mg is added in the 176.11mL water ultrasonic 20～120min., form with the homodisperse graphene oxide solution of monolithic layer; (2) under the room temperature, in gained graphene oxide solution, drip 9.31mL aniline, ultrasonic 10～60min disperses to form the mixed liquor of 0.5mol/L aniline; (3) under 15 ℃; In mixed liquor, dropwise add 30% hydrogen peroxide of 10.3mL, the 0.1mol/L ferric trichloride of 2.0mL and 37% hydrochloric acid solution of 2.28mL respectively; The concentration of hydrogen peroxide is 0.5mol/L, and the concentration of hydrochloric acid is 1.0mol/L, stirs polymerization 24h; (4) reaction finishes, and behind the mixed liquor that obtains is centrifugal, water, the ethanol cyclic washing, obtains graphite oxide and aniline mass ratio (GO: ANI) be graphene oxide/polyaniline composite electrode material of 1: 300 through 40 ℃ of vacuumizes.
Cyclic voltammetric test result under the 10mV/s of graphene oxide/polyaniline composite electrode material of preparation is shown in 1: 10 curve among Fig. 3.The specific capacity of combination electrode material is 430F/g.
Claims (7)
1. graphene oxide/polyaniline super capacitor composite electrode material is characterized in that by the following steps preparation and gets:
(1) graphite oxide is added to ultrasonic dispersion in the water, forms with the homodisperse graphene oxide solution of monolithic layer;
(2) under the room temperature, in gained graphene oxide solution, drip aniline, continue ultrasonic dispersion and form mixed liquor;
(3) under cryogenic conditions, in mixed liquor, dropwise add hydrogen peroxide, ferric trichloride and hydrochloric acid solution successively, stir polymerization, wherein reaction temperature is 0～20 ℃;
(4) reaction finishes, and the mixed liquor that obtains is centrifugal, washing, vacuum drying obtain graphene oxide/polyaniline composite electrode material.
2. graphene oxide/polyaniline super capacitor composite electrode material according to claim 1; It is characterized in that: the ratio of water and the consumption of graphite oxide 1: 1～100: 1; Graphite oxide is 1: 10～1: 300 with the ratio of the quality of aniline, and the ratio of the mole of aniline, hydrogen peroxide, ferric trichloride is 300～1000: 300～1000: 1; Wherein, the consumption of the ferric trichloride of water, aniline, 30% hydrogen peroxide, 37% hydrochloric acid, 0.1mol/L is in milliliter; The consumption of graphite oxide is in milligram.
3. graphene oxide/polyaniline super capacitor composite electrode material according to claim 1 is characterized in that: all between 0.05～0.5mol/L, the concentration of hydrochloric acid is between 0.5～1.5mol/L for the concentration of aniline and hydrogen peroxide.
4. graphene oxide/polyaniline super capacitor composite electrode material according to claim 1 is characterized in that: ultrasonic time is ultrasonic 20～120min in (1) step.
5. graphene oxide/polyaniline super capacitor composite electrode material according to claim 1 is characterized in that: ultrasonic time is ultrasonic 10～60min in (2) step.
6. graphene oxide/polyaniline super capacitor composite electrode material according to claim 1 is characterized in that: the stirring polymerization time 4～24h in (3) step.
7. the preparation method of a graphene oxide/polyaniline super capacitor composite electrode material is characterized in that step is following:
(1) graphite oxide is added to ultrasonic dispersion in the water, forms with the homodisperse graphene oxide solution of monolithic layer;
(2) under the room temperature, in gained graphene oxide solution, drip aniline, continue ultrasonic dispersion and form mixed liquor;
(3) under cryogenic conditions, in mixed liquor, dropwise add hydrogen peroxide, ferric trichloride and hydrochloric acid solution successively, make aniline equate behind the constant volume with the concentration of hydrogen peroxide, stir polymerization, wherein reaction temperature is 0～20 ℃;
(4) reaction finishes, and the mixed liquor that obtains is centrifugal, washing, vacuum drying obtain graphene oxide/polyaniline composite electrode material.
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| CN115172065B (en) * | 2022-06-16 | 2023-04-25 | 宁德师范学院 | Three-dimensional capacitance electrode material with polyaniline/titanium dioxide grafted on graphene surface |
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| CN101302341A (en) * | 2007-05-09 | 2008-11-12 | 郑州泰达电子材料科技有限公司 | Conductive composite material, composite electrode, and super large capacitor and lithium battery using the composite electrode |
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