CN106783222B - Ruthenium coordination polypyrrole nanosphere cluster and its preparation method and application - Google Patents
Ruthenium coordination polypyrrole nanosphere cluster and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of ruthenium coordination polypyrrole nanosphere clusters and its preparation method and application, the ruthenium coordination polypyrrole nanosphere cluster is made of ruthenium coordination polypyrrole nanosphere, nanosphere is tightly packed to form nanosphere cluster, and nanosphere cluster mutually assembles to form micropore between nanosphere cluster.Ruthenium coordination polypyrrole nanosphere cluster is prepared using monomer coordination electropolymerization.It first using direct complexation reaction synthetic method, is interacted using the unpaired electron of nitrogen-atoms on the unoccupied orbital of ruthenium ion and pyrrole monomer strand, ruthenium, which is made, by direct complexation reaction is coordinated pyrrole monomer.Then using cyclic voltammetric electric polymerization reaction synthetic method, ruthenium is coordinated pyrrole monomer under the effect of π pi accumulations power, and ruthenium, which is made, by electric polymerization reaction is coordinated polypyrrole.Relative to the prior art, the material has larger specific surface area, preferable electric conductivity and structural stability, and superior capacitive property and electrochemical stability are shown in electrochemical applications.
Description
Technical field
The present invention relates to a kind of ruthenium coordination polypyrrole nanosphere cluster and preparation method thereof and ultracapacitor electrifications
Stored energy application is learned, belongs to macromolecule novel energy Material Field.
Background technology
In conducting polymer, polypyrrole is as classical conducting polymer, since it is with good air stability,
Higher electric conductivity, environment nontoxicity and reversible oxidation-reduction quality, has in microelectronics, electrochemistry, biotechnology etc.
Tempting application prospect, therefore especially paid attention to.
Electrode material of the electric polypyrrole as ultracapacitor, energy storage are also by Faraday pseudo-capacitance principle reality
Existing, its electrochemical reaction had both been happened at the surface of electrode material, also occurred in the two dimension of the body phase of electrode material or quasi- two dimension
Space so as to which electric polypyrrole be enable to store the charge of high-energy density, generates higher Faraday pseudo-capacitance.And poly- pyrrole
It coughs up that synthesis is convenient, antioxygenic property is good, and compared with other conducting polymers, has higher conductivity, easy film forming, the softness etc. excellent
Point.But electric polypyrrole, as capacitor electrode material, capacitance internal resistance is larger, high power discharge poor performance, long-term cycle
Stability is poor, these problems all greatly limit application of the polypyrrole in ultracapacitor energy storage field.
Invention content
Goal of the invention：In order to solve the above technical problem, the present invention provides a kind of rutheniums to be coordinated polypyrrole nanosphere cluster
Material and its preparation method and application has both higher electrochemistry high rate performance and cyclical stability.
Technical solution：To achieve these goals, the invention discloses a kind of rutheniums to be coordinated polypyrrole nanosphere cluster,
It is mainly made of ruthenium coordination polypyrrole nanosphere, and nanosphere is tightly packed to form nanosphere cluster, and nanosphere cluster is mutually interpolymerized
Collection forms micropore between nanosphere cluster.
Preferably, the ruthenium coordination polypyrrole nanosphere cluster is by ruthenium coordination polypyrrole nanosphere, nanosphere
Micropore forms between the nanosphere cluster and nanosphere cluster of tightly packed formation mutually assemble the nanosphere cluster of formation, described
Ruthenium coordination polypyrrole nanosphere diameter range be 150-200nm；Ruthenium coordination polypyrrole nanosphere is tightly packed to form ruthenium coordination
Polypyrrole nanosphere cluster, nanosphere cluster diameter range are 550-600nm；Ruthenium coordination polypyrrole nanosphere cluster is mutually assembled
It forms ruthenium and is coordinated micropore between polypyrrole nanosphere cluster, micropore diameter range 400-450nm.
The present invention also provides the preparation method of the ruthenium coordination polypyrrole nanosphere cluster, mainly including following
Step：
First using direct complexation reaction synthetic method, using the acetonitrile/water solution of pyrrole monomer and ruthenium trichloride as reaction electricity
Electrolyte solution, the unoccupied orbital of ruthenium ion are made ruthenium by complexation reaction with the unpaired electron of nitrogen-atoms on pyrrole ring strand and match
Position pyrrole monomer.Then using cyclic voltammetric electric polymerization reaction synthetic method, with ruthenium be coordinated the acetonitrile of pyrrole monomer and lithium perchlorate/
Aqueous solution is reaction electrolyte solution, and active carbon paper is working electrode, carries out continuous cyclic voltammetry scan, and ruthenium coordination pyrroles is single
Body is made ruthenium by cyclic voltammetric electric polymerization reaction under the effect of pi-pi accumulation active force and is coordinated polypyrrole nanosphere cluster.
The direct complexation reaction method is：Using the acetonitrile/water solution of pyrrole monomer and ruthenium trichloride as reaction solution,
Acetonitrile/water volume ratio is 1:1-1:3, the molar concentration of pyrrole monomer is 0.1-0.2mol/L, and the molar concentration of ruthenium trichloride is
0.0001-0.0003mol/L, complexation reaction time are 2-16h, and reaction temperature is 25 DEG C.
The cyclic voltammetric electric polymerization reaction method is：The acetonitrile/water that pyrrole monomer and lithium perchlorate are coordinated with ruthenium is molten
Liquid is electrolyte solution, and acetonitrile/water volume ratio is 1:1-1:3, the molar concentration of ruthenium coordination pyrrole monomer is 0.1-0.2mol/L,
The molar concentration of lithium perchlorate is 0.1-0.2mol/L, and using three-electrode electro Chemical reaction system, active carbon paper is working electrode,
Platinized platinum is auxiliary electrode, and saturated calomel electrode is reference electrode, cyclic voltammetry scan setting working electrode take-off potential
For 0.5V, termination current potential is 0.9V, sweep speed 0.1V/s, and the cycle number of turns is 30 circles.
The active carbon paper is prepared using hydro-thermal method：Using graphite carbon paper as presoma, graphite carbon paper first is with ethyl alcohol/the third
Immersion treatment 8h in ketone mixed solution, ethanol/acetone volume ratio are 1:1；Then graphite carbon paper obtained is positioned over hydro-thermal reaction
In kettle, using the mixed solution of 3mol/L aqueous sulfuric acids and 30% aqueous hydrogen peroxide solution as hydro-thermal reaction solution, sulfuric acid is water-soluble
The volume ratio of liquid and aqueous hydrogen peroxide solution is 2：1, hydrothermal temperature is 180 DEG C, the hydro-thermal reaction time 2h；Graphite obtained
Carbon paper is fully washed with distilled water to neutrality, obtains active carbon paper.
Finally, the present invention provides the rutheniums to be coordinated polypyrrole nanosphere cluster as electrode of super capacitor material
Material carries out electrochemical energy storage application.The ruthenium coordination polypyrrole nanosphere cluster is deposited on activation carbon paper directly as work
Make electrode, using polyvinyl alcohol-sulfogel as working electrolyte, ruthenium coordination polypyrrole nanosphere cluster-activity carbon paper electrode and
Polyvinyl alcohol-sulfogel electrolyte is assembled into the all-solid-state supercapacitor of symmetric form, carries out chemical energy storage application.
The orphan of the invention for rationally applying nitrogen-atoms on the strong coordination ability and pyrroles's chain of transition metal ruthenium ion is to electricity
Son, interaction form coordinate bond；Simultaneously as molecule bonding electrons cloud Density Distribution changes in complexation process, match
Polarization occurs for position key, and induction generates polaron or bipolaron, so as to effectively improve the electric conductivity of polypyrrole material.
On the other hand, from the point of view of crystal field theory, under ligand field action energy level splitting, d electricity occur for the d tracks of ruthenium ion
Son rearranges on the d tracks of division, changes the energy of d electronics so that and the gross energy of coordination complex system reduces, from
And improve the stability of polypyrrole.And by coordination, the molecular structure of polypyrrole also becomes four from planar structure
Face body structure, structural stability higher.Therefore, the ruthenium coordination polypyrrole energy storage material of present invention design synthesis, has larger
Electroactive material effective ratio area, higher electric conductivity and structural stability, effectively increase Platinum material and exist
The high rate performance and cyclical stability of charge and discharge under high current density.
Ruthenium coordination polypyrrole nanosphere cluster of the present invention has the following advantages.
(1) ruthenium coordination polypyrrole nanosphere cluster is prepared by being first coordinated the method for electrochemical polymerization again, is had
Not in traditional electrochemistry and chemical oxidation preparation approach, and environmental protection easy to operate.
(2) loose nanosphere cluster pattern is presented in the ruthenium coordination polypyrrole being prepared, and improves the reunion of polypyrrole
Phenomenon.Micropore between nanosphere cluster, on the one hand effectively increases specific surface area, on the other hand optimizes determining for reactive ion
To migration path, the diffusion rate of ion is improved, electrochemical energy storage performance can be improved applied to electrode material for super capacitor.
(3) it is right rationally to apply the orphan of nitrogen-atoms on the strong coordination ability and pyrroles's chain of transition metal ruthenium ion by the present invention
Electronics, interaction form coordinate bond；Simultaneously because in complexation process, molecule bonding electrons cloud Density Distribution changes,
Polarization occurs for coordinate bond, and induction generates polaron or bipolaron, can effectively improve the electric conductivity of polypyrrole material, should
It can improve electrochemistry high rate performance for electrode material for super capacitor.
(4) on the other hand, from the point of view of crystal field theory, under ligand field action energy occurs for the d tracks of ruthenium ion
Grade division, d electronics rearranges on the d tracks of division, changes the energy of d electronics so that coordination complex system it is total
Energy reduces, and improves the stability of polypyrrole, can improve electrochemical cycle stability applied to electrode material for super capacitor
Property.
(5) by coordination, the molecular structure of polypyrrole becomes tetrahedral structure from planar structure, in quick charge and discharge
Polypyrrole volume change is small in electric process, and macrostructure stability higher can improve applied to electrode material for super capacitor
Electrochemical cycle stability.
Technique effect：Relative to the prior art, the ruthenium coordination polypyrrole nanosphere cluster energy storage material of present invention design synthesis
Material has higher electric conductivity, electroactive material effective ratio area and structural stability, effectively increases Platinum
The high rate performance and cyclical stability of material charge and discharge under high current density.
Description of the drawings
Fig. 1：A is the molecular formula of ruthenium coordination polypyrrole；B is the molecular structure of ruthenium coordination polypyrrole.
Fig. 2：Ruthenium is coordinated the preparation technology flow chart of polypyrrole nanosphere cluster.
Fig. 3：A and B is the scanning electron microscope diagram piece of PPy-Ru (12) material；C and D is the scanning electricity of polypyrrole material
Sub- microscope photograph；E and F is the scanning electron microscope diagram piece of PPy-Ru (4) material.
Fig. 4：A is the elemental analysis spectrogram of PPy-Ru (12) material；B is the elemental analysis spectrogram of polypyrrole material.
Fig. 5：The ruthenium coordination polypyrrole material and the Raman test spectrogram of polypyrrole material that the difference coordination time obtains；In figure
A, b, c and d represent the Raman spectrogram of PPy, PPy-Ru (4), PPy-Ru (8) and PPy-Ru (12) material respectively.
Fig. 6：A and B is the picture that PPy-Ru (12) and polypyrrole material react in hydrogenperoxide steam generator respectively.
Fig. 7：Ruthenium is coordinated the electrochemical alternate impedance spectrum figure of polypyrrole and Platinum material.A and b are represented respectively in figure
PPy-Ru (12) and PPy electrode materials.
Fig. 8：A is that the ruthenium obtained the different coordination times is coordinated polypyrrole and Platinum material is molten in 1.0mol/L sulfuric acid
Cyclic voltammetry curve graph when sweep speed is 100mV/s in liquid；A, b, c, d and e represent PPy, PPy-Ru respectively in figure
(4), PPy-Ru (8), PPy-Ru (12) and PPy-Ru (16) electrode material；B and C is PPy and PPy-Ru (12) electrode material respectively
Expect the cyclic voltammetry curve figure of different scanning rates；A, b, c, d, e and f marked in figure represent respectively different scanning rates 5,
10th, cyclic voltammetry curve during 20,50,100 and 200mV/s.D is the quality specific capacitance of PPy and PPy-Ru (12) material
With sweep speed trend chart.
Fig. 9：The ruthenium that the difference coordination time is prepared is coordinated polypyrrole and Platinum material is in current density
1Ag-1Charging and discharging curve；A, b, c and d represent PPy, PPy-Ru (4), PPy-Ru (8) and PPy-Ru (12) electrode respectively in figure
Material.
Figure 10：A and B is quality specific capacitance the becoming with current density change of PPy-Ru (12) and PPy electrode materials respectively
Gesture figure.
Figure 11：It is 20.0Ag that A and B, which is PPy-Ru (12) and PPy electrode materials respectively in current density,-12000 cycle fill
Discharge curve；C is the quality specific capacitance of PPy-Ru (12) and PPy electrode materials with cycle-index trend chart.
Figure 12：The ruthenium symmetric form ultracapacitor that is assembled into of coordination polypyrrole nanosphere cluster and lightening LED lamp
Picture.
Figure 13：A is cyclic voltammetry curve figure of the ruthenium coordination polypyrrole ultracapacitor in different scanning rates；It is marked in figure
A, b, c and the d shown represents cyclic voltammetry curve during 10,20,50 and 100mV/s of different scanning rates respectively.B is that ruthenium is matched
The quality specific capacitance of position polypyrrole ultracapacitor is with sweep speed trend chart.
Figure 14：A be ruthenium coordination polypyrrole ultracapacitor current density be 1.0Ag-1Charging and discharging curve；B is that ruthenium is matched
The energy density of position polypyrrole ultracapacitor is with power density trend chart.
Figure 15：A be ruthenium coordination polypyrrole ultracapacitor current density be 2.0Ag-1The charge and discharge of different cycle-indexes
Curve；B is the quality specific capacitance of ruthenium coordination polypyrrole ultracapacitor with the trend chart of cycle-index.
Figure 16：The space structure schematic diagram of ruthenium coordination polypyrrole nanosphere cluster of the present invention.
Specific embodiment
The technical solution of the present invention is further described below in conjunction with the accompanying drawings.
Embodiment 1
The molecular formula and structure diagram of ruthenium coordination polypyrrole material of the present invention, refer to Figure of description 1.It utilizes
The unpaired electron interaction of nitrogen-atoms, coordination obtain monomer complex pyrroles's ruthenium on the unoccupied orbital of ruthenium ion and pyrroles's chain；
Then electrochemical polymerization obtains coordination polymer again.Ruthenium coordination polypyrrole molecular structure is in tetrahedral structure.Ruthenium coordination of the present invention
The space structure schematic diagram of polypyrrole nanosphere cluster, refers to attached drawing 16, it is seen that it is mainly coordinated polypyrrole nanometer by ruthenium
Ball 1 is formed, and nanosphere is tightly packed to form nanosphere cluster 2, and nanosphere cluster mutually assembles to form micropore between nanosphere cluster
3。
Embodiment 2
The preparation technology flow chart of ruthenium coordination polypyrrole nanosphere cluster of the present invention, refers to Figure of description
2.The specific preparation process of ruthenium coordination polypyrrole material is as follows：
(1) using the acetonitrile/water solution of pyrrole monomer and ruthenium trichloride as reaction solution, the unoccupied orbital and pyrrole of ruthenium ion are utilized
The unpaired electron interaction of nitrogen-atoms on chain is coughed up, direct complexation reaction at normal temperatures obtains matching for pyrrole monomer and ruthenium ion
Close object ruthenium coordination pyrrole monomer.
(2) in electrochemistry three-electrode system, using active carbon paper as electrode base materials and as working electrode, platinized platinum is
Auxiliary electrode, saturated calomel electrode are reference electrode, and the acetonitrile/water solution of pyrrole monomer and lithium perchlorate is coordinated as reaction using ruthenium
Ruthenium coordination is obtained by the reaction in electrolyte solution, the electrochemical polymerization reaction method regulated and controled using cyclic voltammetry in carbon paper substrate
Polypyrrole nanosphere cluster.
The activity carbon paper is prepared using hydro-thermal method：Using graphite carbon paper as presoma, graphite carbon paper ethanol/acetone first
Immersion treatment 8h in mixed solution, ethanol/acetone volume ratio are 1:1；Then graphite carbon paper obtained is positioned over hydrothermal reaction kettle
In, using the mixed solution of 3mol/L aqueous sulfuric acids and 30% aqueous hydrogen peroxide solution as hydro-thermal reaction solution, aqueous sulfuric acid
Volume ratio with aqueous hydrogen peroxide solution is 2：1, hydrothermal temperature is 180 DEG C, the hydro-thermal reaction time 2h；Graphitic carbon obtained
Paper is fully washed with distilled water to neutrality, obtains active carbon paper.
Embodiment 3
The specific preparation method of ruthenium coordination polypyrrole nanosphere cluster electrode material of the present invention is as follows：
(1) the standing coordination method described in：Using the acetonitrile/water solution of pyrrole monomer and ruthenium trichloride as reaction solution, second
Nitrile/water volume ratio is 1:3, the molar concentration of pyrrole monomer is 0.1mol/L, and the molar concentration of ruthenium trichloride is 0.0003mol/
L, complexation reaction time are 12h, and reaction temperature is 25 DEG C.
(2) the cyclic voltammetric electropolymerization method described in is：The acetonitrile/water solution of pyrrole monomer and lithium perchlorate is coordinated with ruthenium
For electrolyte solution, acetonitrile/water volume ratio is 1:3, the molar concentration of ruthenium coordination pyrrole monomer is 0.1mol/L, lithium perchlorate
Molar concentration is 0.1mol/L, and using three-electrode electro Chemical reaction system, active carbon paper is working electrode, and platinized platinum is auxiliary electricity
Pole, saturated calomel electrode are reference electrode, and the cyclic voltammetry scan sets working electrode take-off potential as 0.5V, terminate electricity
Position is 0.9V, sweep speed 0.1V/s, and the cycle number of turns is 30 circles, and obtained electrode material is cleaned repeatedly with deionized water, and
60 DEG C of drying of vacuum drying chamber are placed in, sample is denoted as PPy-Ru (12).
Embodiment 4
All methods and 3 all same of embodiment, the method the difference lies in complexation reaction in step (1) are as follows：
Using the acetonitrile/water solution of pyrrole monomer and ruthenium trichloride as reaction solution, acetonitrile/water volume ratio is 1:3, Bi Kadan
The molar concentration of body is 0.1mol/L, and the molar concentration of ruthenium trichloride is 0.0003mol/L, and reaction temperature is 25 DEG C, during reaction
Between become 4,8 and 16h respectively, the ruthenium that is prepared after corresponding electrochemical polymerization coordination polypyrrole nanosphere cluster is remembered respectively
Make PPy-Ru (4), PPy-Ru (8) and PPy-Ru (16).
Embodiment 5 (comparative example)
All methods and 3 all same of embodiment, the preparation method the difference lies in step (1) and step (2) are as follows：
Using the acetonitrile/water solution of pyrrole monomer and lithium perchlorate as electrolyte solution, acetonitrile/water volume ratio is 1:3, pyrroles
The molar concentration of monomer is 0.1mol/L, and the molar concentration of lithium perchlorate is 0.1mol/L, and reaction temperature is 25 DEG C.Electrolyte is molten
Liquid directly using cyclic voltammetric electropolymerization method, the cyclic voltammetry scan set take-off potential on the working electrode (s as
0.5V, termination current potential are 0.9V, sweep speed 0.1V/s, and the cycle number of turns is enclosed for 30, obtained electrode material deionized water
It cleans repeatedly, is placed in 60 DEG C of drying of vacuum drying chamber, obtains polypyrrole material, be denoted as PPy.
Embodiment 6
Ruthenium coordination polypyrrole nanosphere cluster of the present invention carries out pattern Characterization for Microstructure, and it is attached to refer to specification
Fig. 3.Attached drawing A and B are the scanning electron microscope diagram pieces of PPy-Ru (12) material；It tests as a comparison, attached drawing 3C and D are PPy
The scanning electron microscope diagram piece of material (with the material identical described in embodiment 5)；Attached drawing 3E and F be PPy-Ru (4) material (with
Material identical described in embodiment 4) scanning electron microscope diagram piece.Scheme A and B and show PPy-Ru (12) material nano pelletizing cluster
Structure feature, the diameter range of nanosphere is 150-200nm or so, and nanosphere is tightly packed to form nanosphere cluster, nanometer
Pelletizing cluster mutually assembles that form the diameter of micropore be about 400-450nm.Figure C and D shows that polypyrrole material is poly- by many
Irregularly tight agglomeration to together, is uneven pyrroles's nano particle, not of uniform size.Scheme E and F to show, PPy-Ru (4) material
Structure feature with loose nano particle, the diameter of nano particle is about 500nm.The result shows that coordination and coordination
Time has a major impact the microscopic appearance of polypyrrole, when be coordinated the time be 12h when complexation reaction reach abundant, obtain at this time
The smaller nanosphere cluster of loose and grain size is presented in ruthenium coordination polypyrrole material.
Embodiment 7
Ruthenium coordination polypyrrole nanosphere cluster of the present invention carries out EDX element characterizations, refers to Figure of description
4.Attached drawing 4A is the EDX elemental analysis spectrograms of PPy-Ru (12) material.Test as a comparison, attached drawing 4B be polypyrrole material (with
Material identical described in embodiment 5) EDS elemental analysis spectrograms；Figure B is shown, at 0.268KeV, 0.377KeV and 0.517KeV
Characteristic peak correspond to C, N and O element respectively, their corresponding atomic ratios are 62.12%, 17.28% and 20.60%, are illustrated poly-
Electrochemical polymerization is covered on carbon paper pyrroles.Figure A show, in addition to figure B in three characteristic peaks, have also appeared four newly
Characteristic peak is at 1.745KeV, 2.313KeV and 2.802KeV at the corresponding Ru elements in three peaks and 2.632KeV respectively
Corresponding Cl elements；Their atomic ratio is 0.10% and 2.34% respectively, illustrates that coordination polymer may have been formed.
Embodiment 8
Ruthenium coordination polypyrrole nanosphere cluster of the present invention carries out Raman spectrum test, refers to Figure of description
5.Test as a comparison, in attached drawing 5 a, b, c and d represent respectively PPy, PPy-Ru (4), PPy-Ru (8) and PPy-Ru (12) (with
Material identical described in embodiment 4 and 5) material Raman spectrogram.From spectrogram a it will be clear that the Raman light of polypyrrole
Spectrum signature peak, positioned at 931cm-1,1060cm-1,1094cm-1The wave crest at place is as caused by the annular strain vibration of c h bond；It is located at
1248cm-1The wave crest at place is caused by the in-plane bending vibration of c h bond；Positioned at 1359cm-1、1497cm-1And 1579cm-1
Three at peak be as caused by the stretching vibration of C-N, C-C and C=C key respectively, can be seen that this black material from above analysis
Expect for polypyrrole.Spectrogram b, c and d show that these characteristic peaks still remain, but the position at peak gradually deviates, Er Qiexiang
The peak intensity answered has apparent enhancing.Specific peak change is as shown in the table.
As seen from table, the C-H annular strains of polypyrrole vibrate and C-C stretching vibrations are respectively from 1094cm-1And 1497cm-1Place
Gradually it has been displaced to the 1081cm of PPy-Ru (12)-1And 1481cm-1Place.C-N the and C=C stretching vibrations of PPy respectively from
1359cm-1And 1579cm-1Place has gradually been displaced to the 1375cm of PPy-Ru (12)-1And 1594cm-1Place.These variations are mainly
The tensile stress or compression in film are changed due to coordination, then affects atom bonding lengths so that the force constant of film
It is decreased or increased, the vibration frequency of atom accordingly changes, and is finally embodied in Raman peaks and is deviated to low frequency or high frequency direction.
Embodiment 9
Ruthenium coordination polypyrrole nanosphere cluster of the present invention carries out catalytic performance test, refers to Figure of description
6A.It tests as a comparison, attached drawing 6B is the result of polypyrrole material catalytic performance test.Ruthenium is coordinated polypyrrole nanosphere cluster material
Material acts not only as the electrode material of ultracapacitor, while is also a kind of good catalyst, has done simple reality thus
It tests, ruthenium coordination polypyrrole PPy-Ru (12) and polypyrrole PPy materials is respectively placed in the small burning for filling 30% hydrogenperoxide steam generator
In cup, from figure A it is observed that minute bubbles occurs at once in ruthenium coordination polypyrrole material surface, and reacts more and more violent, say
Bright ruthenium coordination polypyrrole material can be with fast decoupled hydrogen peroxide；But polypyrrole (figure B) surface does not occur bubble, material
Surface that any variation does not occur, illustrates the ability that polypyrrole material does not have peroxynitrite decomposition hydrogen, is indicated above coordinate bond always
N-Ru may have been formed.
Embodiment 10
Ruthenium coordination polypyrrole nanosphere cluster of the present invention carries out electrochemical alternate impedance spectrum test, refers to
Bright book attached drawing 7.Electro-chemical test system is as follows：Polypyrrole electrode material is coordinated as working electrode using ruthenium, platinized platinum
For auxiliary electrode, saturated calomel electrode is reference electrode, and 1.0M aqueous sulfuric acids are working electrolyte, open-circuit voltage 0.2V
(Vs.SCE), disturbance current potential is 5mV, frequency sweeping ranges 100KHz-10mHz, and three electrodes are established by electrochemical workstation
Electrochemical property test system.It tests as a comparison, attached drawing 7b is the electrochemical alternate impedance spectrum figure of polypyrrole.By to electrode
The electrochemical alternate impedance spectrum of material is fitted analysis, and equivalent circuit diagram element fitting result is as follows.
It can be seen from the figure that the AC impedance spectroscopy of two kinds of electrode materials is mainly by the semi arch of high band and low-frequency range
Rectilinear(-al).Equivalent circuit diagram element includes solution resistance Ro, charge transfer resistance Rct, diffusion resistance RwAnd often phase angle is first
Part CPE.It is understood according to experimental fit result and result of calculation：It is molten compared to polypyrrole material in electrochemical reaction process
Liquid resistance Ro(0.813 Ω) and charge transfer resistance Rct(0.790 Ω), ruthenium coordination polypyrrole electrode material have relatively low solution
Resistance (0.579 Ω) and charge transfer resistance (0.512 Ω) illustrate that ruthenium coordination polypyrrole electrode material is passed with better electronics
Movement Capabilities and higher electric charge transfer rate.Ruthenium is coordinated the W of polypyrrole materialRFor 0.536 Ω, less than Platinum material
(0.848 Ω) illustrates that diffusion of the ruthenium coordination polypyrrole material in sulfuric acid electrolyte is relatively easy to.Normal phase angle is mainly used to
The even property of current distribution is uneven caused by prescribed electrode surface roughness and porosity, has reacted the power of dispersion effect.Ruthenium is coordinated
The n values of polypyrrole and polypyrrole material are respectively 0.864 and 0.737, illustrate that ruthenium coordination polypyrrole material has preferably electrification
Learn capacitance behavior.Electrochemical impedance spectroscopy analysis result shows compared to polypyrrole material, ruthenium coordination polypyrrole nanosphere cluster material
Material has better charge transport and Ionic diffusion advantage, effectively increases electrochemistry storing up electricity performance.
Embodiment 11
Ruthenium coordination polypyrrole nanosphere cluster electrode material of the present invention carries out electrochemistry cyclic voltammetric performance test,
Refer to Figure of description 8.Attached drawing 8A is the ruthenium coordination polypyrrole and polypyrrole material obtained the different coordination times in 1.0mol/L
Cyclic voltammetry curve graph when sweep speed is 100mV/s in sulfuric acid solution, in figure a, b, c, d and e represent respectively PPy,
PPy-Ru (4), PPy-Ru (8), PPy-Ru (12) and PPy-Ru (16) (with the material identical described in embodiment 4 and 5)；Attached drawing 8B
It is the cyclic voltammetry curve figure of PPy-Ru (12) and PPy electrode material different scanning rates respectively with C, a, b, c, d, e and f in figure
5,10,20,50,100 and 200mV/s of different scanning rates is represented respectively；Attached drawing 8D is the quality of PPy-Ru (12) and PPy materials
Specific capacitance is with sweep speed trend chart.Similar square is all presented in the cyclic voltammetry curve that can be seen that five kinds of materials from figure A
Shape, while observe that there are two distant redox peaks, show preferable Faraday pseudo-capacitance behavior.In addition, not
The current-responsive of ruthenium coordination polypyrrole electrode material being prepared with the coordination time is all significantly higher than pure Platinum, from
Experimental result can obtain in figure, and when voltage is 0.2V, the current density of PPy-Ru (12) and PPy are respectively 32.3Ag-1With
7.6Ag-1, show the preferable electric conductivity of PPy-Ru (12) electrode material.The cyclic voltammetry curve of PPy-Ru (12) electrode has
Higher than the closed area area of other electrode materials, this shows that PPy-Ru (12) has fast ionic transmission and exchange capacity, because
This shows higher current density and specific capacitance.In addition, we have also observed that the current-responsive of PPy-Ru (16) electrode and
PPy-Ru (12) electrode it is identical, this illustrates that the complexation reaction of pyrrole monomer and ruthenium ion has saturability, is reached when the coordination time
By 12 hours, coordination was abundant, and PPy-Ru (12) electrode shows best electrochemical capacitor performance.Figure B and C shows
The current density of PPy-Ru (12) and PPy electrodes is all improved with the increase of sweep speed, according to cyclic voltammetry curve, we
The specific capacitance under different scanning rates can be calculated respectively.It can see from figure D, the PPy-Ru under same scan rate
(12) electrode shows the specific capacitance of high PPy；And as sweep speed is from 5 to 200mV s-1, the specific capacitance of PPy-Ru (12) from
458F g-1Drop to 227F g-1, capacity retention 49.6%；The quality specific capacitance of PPy electrodes is from 245F g-1To 103F
g-1, conservation rate only have 42.0%, PPy-Ru (12) electrode have relatively low capacitance loss.The experimental results showed that ruthenium polycomplexation pyrrole
Electrode material is coughed up with higher electric conductivity and high rate performance.This is mainly due in pyrrole monomer and ruthenium ion complexation process
In, bonding electrons cloud density changes, and makes chemical bond that polarization occur, and induction generates polaron or bipolaron so as to produce
Raw electric conductivity, the coordination polymer of high conductivity promote the transmittability of electronics, thus PPy-Ru (12) material show compared with
Good electric conductivity, electrochemical capacitor and high rate performance.
Embodiment 12
Ruthenium coordination polypyrrole nanosphere cluster electrode material of the present invention carries out electrochemistry constant current charge-discharge performance
Test, sets potential range as -0.2-0.6V, refers to Figure of description 9.Attached drawing 9 is the ruthenium being prepared the different coordination times
It is 1.0Ag that polypyrrole and Platinum material, which are coordinated, in current density-1Charging and discharging curve；A, b, c and d are represented respectively in figure
PPy, PPy-Ru (4), PPy-Ru (8) and PPy-Ru (12) electrode material.It is special all to show similar isosceles triangle for curve in figure
Sign, thus illustrates, material has good reversible feature；It is clear that the constant current discharge of PPy-Ru (12) electrode material
Time is longer than other materials, illustrates it with higher specific capacitance.PPy, PPy-Ru (4), PPy-Ru can be calculated from figure
(8) and the quality specific capacitance of PPy-Ru (12) electrode material is respectively 249F g-1,325F g-1,469F g-1With 618F g-1.It is real
It is consistent with cyclic voltammetry result to test result, illustrates that coordination polymer PPy-Ru (12) has better electron transport ability.
In addition, the pressure drop of PPy, PPy-Ru (4), PPy-Ru (8) and PPy-Ru (12) electrode be respectively 11.5mV, 11.0mV, 4.6mV and
Their impedance, respectively 5.8m Ω g can be calculated according to pressure drop by 4.4mV-1,5.7mΩg-1,2.3mΩg-1And 2.2m
Ωg-1, as a result equally illustrate that PPy-Ru (12) material has higher electric conductivity, so as to improve the transmittability of electronics.
Embodiment 13
Ruthenium coordination polypyrrole nanosphere cluster electrode material of the present invention carries out electrochemistry constant current charge-discharge performance
Test, sets potential range as -0.2-0.6V, current density range 1.0-20.0Ag-1, refer to Figure of description 10.Attached drawing
10A is the quality specific capacitance of PPy-Ru (12) electrode material with the tendency chart of current density change；It tests as a comparison, attached drawing
10B is the quality specific capacitance of PPy electrode materials (consistent with the material described in embodiment 5) with the tendency chart of current density change.
As can be seen from Fig., it is 1.0-20.0Ag in current density-1, constant current charge-discharge curve all keeps linear symmetric feature, explanation
Electrode material has good electrochemical reversibility during constant current charge-discharge.As can be seen from Figure 10A, as electric current is close
The variation of degree, the quality specific capacitance of PPy-Ru (12) electrode is from 618Fg-1Drop to 301F g-1, capacity retention 48.7%.
Figure 10 B can be obtained, and the quality specific capacitances of PPy electrodes is from 249Fg-1Drop to 102F g-1, capacity retention 40.9%.Knot
Fruit again shows that the coordination of pyrrole monomer and ruthenium ion effectively reduces the electric charge transfer internal resistance of electrode material, therefore is promoted
The electrochemical capacitor performance and high rate performance of material.
Embodiment 14
Ruthenium coordination polypyrrole nanosphere cluster electrode material of the present invention carries out electrochemistry cycle charge discharge electrical property and surveys
Examination.Potential range is set as -0.2-0.6V, constant current density 20.0Ag-1, it is attached to refer to specification cycle charge-discharge 2000 times
Figure 11.It is 20Ag that attached drawing 11A, which is PPy-Ru (12) electrode materials in current density,-12000 cycle charge-discharge curve graphs；As
Contrast experiment, it is 20.0Ag that attached drawing 11B, which is PPy electrode materials (consistent with the material described in embodiment 5) in current density,-1's
2000 cycle charge-discharge curve graphs；Attached drawing 11C is that the quality specific capacitance of PPy-Ru (12) and PPy electrode materials becomes with cycle-index
Change tendency chart.PPy-Ru (12) and PPy electrode materials are can be seen that in high current density 20.0A g from figure A and B-1Under have passed through
After 2000 cycle charge-discharges, curve still keeps symmetric characteristics, illustrates its preferable electrochemical capacitor performance.It can be with from figure C
Find out, the quality specific capacitance of PPy-Ru (12) electrode material is by 301F g-1Drop to 275F g-1, the conservation rate of specific capacitance is
91.4%；Corresponding, the quality specific capacitance of PPy electrode materials is by 102F g-1Drop to 81F g-1, the conservation rate of specific capacitance
It is 79.4%；The experimental results showed that PPy-Ru (12) electrode material has superior electrochemical cycle stability.Due to poly- pyrrole
Coughing up construction debris caused by material main chain in charge and discharge process is repeatedly expanded/shunk causes the electrochemistry of polypyrrole to recycle
Stability is poor.But pyrrole monomer and ruthenium ion, in complexation process, the energy level of ruthenium ion d tracks is fissioned, electronics hair
Raw to reset the energy for changing electronics, so as to reduce the gross energy of coordination polymerization objects system, PPy-Ru (12) is more stable；It is another
Aspect, compared to the PPy of planar structure, the PPy-Ru (12) of tetrahedral structure helps to limit polypyrrole material in charge and discharge
Irreversible volume change in journey, so as to be effectively improved the electrochemical cycle stability performance of polypyrrole material.
Embodiment 15
Ruthenium of the present invention coordination polypyrrole nanosphere cluster electrode material be applied to electrode material for super capacitor into
The application of row electrochemical energy storage.Described ruthenium coordination polypyrrole nanosphere Cluster deposition in activation carbon paper as working electrode, with
Polyvinyl alcohol-sulfogel is working electrolyte, and the ruthenium coordination Platinum of two area equations is coagulated with polyvinyl alcohol-sulfuric acid
Glue electrolyte is assembled into the all-solid-state supercapacitor of symmetric form, and carries out electrochemical energy storage application, refers to Figure of description 12.
It is that ruthenium coordination polypyrrole material uses transparent PET (Polyethylene terephthalate) film as model shown in Figure 12
Outer packing, the size of ultracapacitor model is 1cm × 5cm.The ultracapacitor list of ruthenium coordination polypyrrole electrode material assembling
It is a to light red diodes.
Embodiment 16
The ultracapacitor that ruthenium coordination polypyrrole nanosphere cluster electrode material of the present invention is assembled into carries out electrification
Cyclic voltammetric performance test is learned, refers to Figure of description 13.Attached drawing 13A is that ruthenium is coordinated polypyrrole ultracapacitor in different scanning
The cyclic voltammetry curve figure of rate；A, b, c and d marked in figure represent 10,20,50 and 100mV/ of different scanning rates respectively
Cyclic voltammetry curve during s.Attached drawing 13B is that the quality specific capacitance of ruthenium coordination polypyrrole ultracapacitor becomes with sweep speed
Change tendency chart.It can be seen from the figure that it is the cyclic voltammetry curve of ultracapacitor in the range of -1.0V-1.0V in potential range
In class rectangle, good electrochemical capacitor performance is showed.Simultaneously as sweep speed is from 10mVs-1To 100mVs-1, super capacitor
The quality specific capacitance of device is from 108F g-1Drop to 71F g-1, quality is 65.7% than capacity retention；Illustrate ruthenium polycomplexation pyrrole
Cough up nanosphere cluster still has good electrochemistry storing up electricity performance in gel electrolyte, it is shown that the excellent electricity of material
Conductance and electron transport ability.
Embodiment 17
The ultracapacitor that ruthenium coordination polypyrrole nanosphere cluster electrode material of the present invention is assembled into carries out electrification
Constant current charge-discharge performance test is learned, refers to Figure of description 14.Attached drawing 14A is that ruthenium is coordinated polypyrrole ultracapacitor in electric current
Density is 1.0A g-1Charging and discharging curve；Attached drawing 14B is the energy density of ruthenium coordination polypyrrole ultracapacitor with power density
Trend chart.It can see by Figure 14 A, the charging and discharging curve of ruthenium coordination polypyrrole ultracapacitor presents ideal straight
Line symmetric form trigonometric curve；As current density is from 0.5Ag-1To 2Ag-1, ultracapacitor quality specific capacitance is from 169F g-1Under
It is reduced to 122F g-1, capacity retention 72.2%；If Figure 14 B are shown according to active material Mass Calculation, power density from
500W Kg-1To 2000W Kg-1Variation range in, the mass energy density variation range of ultracapacitor is 93.9Wh Kg-1
To 67.8Wh Kg-1；Illustrate that ruthenium coordination polypyrrole nanosphere cluster has higher high rate performance and mass energy density,
It is a kind of ideal electrode material for super capacitor.
Embodiment 18
The ultracapacitor that ruthenium coordination polypyrrole nanosphere cluster electrode material of the present invention is assembled into carries out electrification
Learn cycle charge discharge electric performance test.Potential range is set as -1.0-1.0V, constant current density 2.0Ag-1, cycle charge-discharge 500
It is secondary, refer to Figure of description 15.Attached drawing 15A be ruthenium coordination polypyrrole ultracapacitor current density be 2.0Ag-1Difference cycle
The charging and discharging curve of number；Attached drawing 15B is the quality specific capacitance of ruthenium coordination polypyrrole ultracapacitor with the variation of cycle-index
Tendency chart.It can be obtained by figure, with increasing for cycle-index, ruthenium is coordinated the charging and discharging curve shape of polypyrrole ultracapacitor
Almost keep symmetrical triangle constant；But with the extension of time, the constant current discharge time shortening of ultracapacitor, explanation
With the extension of time, ultracapacitor quality specific capacitance reduces.Attached drawing 15 (B) shows by 500 constant current charge-discharges
It examines, the quality specific capacitance of ruthenium coordination polypyrrole ultracapacitor is from 122F g-1Drop to 101F g-1, capacity retention is
82.8%.Experimental result illustrates that prepared ruthenium coordination pyrroles's nanosphere cluster ultracapacitor has higher high current density
Cyclical stability has a good application prospect in energy storage device application.
Claims (8)
1. a kind of ruthenium is coordinated polypyrrole nanosphere cluster, it is characterised in that：The ruthenium coordination polypyrrole nanosphere cluster
Material is made of ruthenium coordination polypyrrole nanosphere (1), and ruthenium coordination polypyrrole nanosphere (1) is tightly packed to form ruthenium coordination polypyrrole
Nanosphere cluster (2), ruthenium coordination polypyrrole nanosphere cluster (2) mutually aggregation formed ruthenium coordination polypyrrole nanosphere cluster between it is micro-
Hole (3)；
The preparation method of ruthenium coordination polypyrrole nanosphere cluster is：Direct complexation reaction synthetic method is used first, with
The acetonitrile/water solution of pyrrole monomer and ruthenium trichloride is reaction electrolyte solution, the unoccupied orbital of ruthenium ion and pyrrole ring strand
The unpaired electron of upper nitrogen-atoms is made ruthenium by direct complexation reaction and is coordinated pyrrole monomer；Then cyclic voltammetric electropolymerization is used
Reaction synthesis method, the acetonitrile/water solution that pyrrole monomer and lithium perchlorate are coordinated using ruthenium are as electrolyte solution, active carbon paper is reacted
Working electrode, carries out continuous cyclic voltammetry scan, and ruthenium is coordinated pyrrole monomer under the effect of pi-pi accumulation power by cyclic voltammetric electricity
Ruthenium coordination polypyrrole nanosphere cluster is made in polymerisation.
2. ruthenium according to claim 1 is coordinated polypyrrole nanosphere cluster, it is characterised in that：The ruthenium polycomplexation
Pyrroles's nanosphere (1) diameter range is 80-150nm；Described ruthenium coordination polypyrrole nanosphere cluster (2) diameter range is 500-
600nm；Micropore (3) diameter range is 400-500nm.
3. the preparation method of the ruthenium coordination polypyrrole nanosphere cluster described in claims 1 or 2, it is characterised in that：First
Using direct complexation reaction synthetic method, using the acetonitrile/water solution of pyrrole monomer and ruthenium trichloride as reaction electrolyte solution, ruthenium from
The unpaired electron of the unoccupied orbital of son and nitrogen-atoms on pyrrole ring strand is made ruthenium by direct complexation reaction and is coordinated pyrroles's list
Body；Then using cyclic voltammetric electric polymerization reaction synthetic method, using ruthenium be coordinated the acetonitrile/water solution of pyrrole monomer and lithium perchlorate as
Electrolyte solution is reacted, active carbon paper is working electrode, carries out continuous cyclic voltammetry scan, and ruthenium is coordinated pyrrole monomer in π-π
Accumulation force effect is lower to be made ruthenium coordination polypyrrole nanosphere cluster by cyclic voltammetric electric polymerization reaction.
4. preparation method according to claim 3, it is characterised in that：The direct complexation reaction method is：With pyrroles
The acetonitrile/water solution of monomer and ruthenium trichloride is reaction solution, and acetonitrile/water volume ratio is 1:1-1:3, pyrrole monomer it is mole dense
It spends for 0.1-0.2mol/L, the molar concentration of ruthenium trichloride is 0.0001-0.0003mol/L, and the direct complexation reaction time is 2-
16h, reaction temperature are 25 DEG C.
5. preparation method according to claim 3, it is characterised in that：The cyclic voltammetric electric polymerization reaction method is：
Using the acetonitrile/water solution of ruthenium coordination pyrrole monomer and lithium perchlorate as electrolyte solution, acetonitrile/water volume ratio is 1:1-1:3, ruthenium
The molar concentration for being coordinated pyrrole monomer is 0.1-0.2mol/L, and the molar concentration of lithium perchlorate is 0.1-0.2mol/L, using three
Electrode electro Chemical reaction system, active carbon paper are working electrode, and platinized platinum is auxiliary electrode, and saturated calomel electrode is reference electrode,
The cyclic voltammetry scan sets working electrode take-off potential as 0.5V, termination current potential be 0.9V, sweep speed 0.1V/s,
The number of turns is recycled as 30 circles.
6. preparation method according to claim 3, it is characterised in that：The active carbon paper is prepared using hydro-thermal method：With
Graphite carbon paper be presoma, graphite carbon paper immersion treatment 8h in ethanol/acetone mixed solution first, ethanol/acetone volume ratio
It is 1:1；Then graphite carbon paper obtained is positioned in hydrothermal reaction kettle, with 3mol/L aqueous sulfuric acids and 30% aquae hydrogenii dioxidi
The mixed solution of solution is hydro-thermal reaction solution, and the volume ratio of aqueous sulfuric acid and aqueous hydrogen peroxide solution is 2：1, hydro-thermal reaction
Temperature is 180 DEG C, the hydro-thermal reaction time 2h；Graphite carbon paper obtained is fully washed with distilled water to neutrality, obtains active carbon paper.
7. electricity of the ruthenium coordination polypyrrole nanosphere cluster as electrode material for super capacitor described in claims 1 or 2
Chemical energy storage application.
8. application according to claim 7, it is characterised in that：The ruthenium is coordinated polypyrrole nanosphere Cluster deposition in work
Property carbon paper surface and as working electrode, using polyvinyl alcohol-sulfogel as working electrolyte, ruthenium coordination polypyrrole nanosphere group
Cluster-activity carbon paper electrode is assembled into the all-solid-state supercapacitor of symmetric form, and carry out with polyvinyl alcohol-sulfogel electrolyte
Electrochemical energy storage application.
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| CN103401008A (en) * | 2013-07-31 | 2013-11-20 | 华南理工大学 | Method and device for storing bioelectrical energy by virtue of capacitive anode |
| CN103903869A (en) * | 2014-03-27 | 2014-07-02 | 华中科技大学 | Paper super capacitor and preparing method thereof |
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| CN103401008A (en) * | 2013-07-31 | 2013-11-20 | 华南理工大学 | Method and device for storing bioelectrical energy by virtue of capacitive anode |
| CN103903869A (en) * | 2014-03-27 | 2014-07-02 | 华中科技大学 | Paper super capacitor and preparing method thereof |
Non-Patent Citations (2)
| Title |
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| Preparation and characterization of ruthenium-doped polypyrrole composites for supercapacitor;Ben-Lin He;《Materials Science and Engineering A 》;20040615;第347卷(第1-2期);experimental部分，results and discussion部分，图 * |
| 新型钌系聚吡咯络合物的合成、结构和表征;丁洪生;《石油化工高等学校学报》;19980630;第11卷(第2期);第15页左栏第16行-第16页右栏最后一行，图2 * |
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