CN106340401A - Preparing method of composite electrode material and application thereof - Google Patents
Preparing method of composite electrode material and application thereof Download PDFInfo
- Publication number
- CN106340401A CN106340401A CN201611067395.2A CN201611067395A CN106340401A CN 106340401 A CN106340401 A CN 106340401A CN 201611067395 A CN201611067395 A CN 201611067395A CN 106340401 A CN106340401 A CN 106340401A
- Authority
- CN
- China
- Prior art keywords
- electrode material
- tio
- preparation
- polypyrrole
- pyrrole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a preparing method of a composite electrode material and an application thereof; according to the method, polypyrrole gel is directly covered on the surface of the P25 type TiO2 particle material treated with hydrogenation, wherein the polypyrrole gel adulated with phytic acid is formed through hydrogenation treatment, covering and crosslinking of pyrrole monomeron, phytic acid and ammonium persulfate. Then single-walled carbon nanotube serves as a framework to prepare and obtain the composite electrode material with a 3D reticular structure, the composite electrode material has the advantages of good conductivity, high first discharge capacity and good rate capability and cycle performance. Meanwhile, when the composite electrode material is applied to a super capacitor, conductive agent and binder don't need to be added, which reduces commercial cost, enables more convenient use and is beneficial to commercial popularization of secondary chemical power source.
Description
Technical field
The present invention relates to electrode material field, particularly to a kind of preparation method and applications of combination electrode material.
Background technology
Currently, energy crisis is on the rise, and taps a new source of energy and becomes a great problem of new century, how that these energy are high
Effect quickly storage become a great problem.At present in business-like secondary chemical sources of electric energy (battery, ultracapacitor etc.), lithium from
Ultra high energy density (the 150w h kg that sub- battery is had due to it-1) and higher running voltage (3-4.5v) become current
Study hotspot, but its relatively low power density (＜ 1kw/kg) and shorter cycle life (thousands of times) have impact on it in needs
The application (as pure electric automobile) of high-power output and long circulation life demand side.On the contrary, ultracapacitor has superelevation
Power density (2-5kw kg-1) and overlength cycle life (105Secondary), but its energy density only 5～7wh/kg about,
Well below lithium ion battery and other secondary cells (such as: lead-acid battery and Ni-MH battery).In order to the advantage of both is entered
Row is perfect to be combined, and lithium ion super capacitor arises at the historic moment, and it adopts traditional double layer capacitor material with carbon element as positive pole,
Lithium ion battery negative material (predominantly metal-oxide) is as negative pole.P25 type tio2There is higher theoretical specific capacity
335ma h g-1, but the storage lithium performance of its reality and cyclical stability are all undesirable.Therefore, its electric conductivity and storage how are improved
Lithium performance becomes the key that effectively utilizes commercial materials are studied as energy storage device.
Now there are some researches show: using printing method by carbon coating in the appearance of electrode material although it can be improved first
Specific capacity, but after 20 circle circulations, its hydraulic performance decline obtains it is obvious that the storage lithium performance to electrode material and cyclical stability improve
DeGrain.And introduce Lacking oxygen defect in electrode material surface, can largely improve the electric conductivity of electrode material, increase
Embedding lithium active site, thus lift the chemical property of electrode.Meanwhile, there is document to show, electrode material is being carried out introduce oxygen
In the processing procedure of vacancy defect, the temperature of process and process time have a significant effect to the embedding lithium performance of electrode material.As
To anatase titanium dioxide tio2When carrying out introducing Lacking oxygen defect processing, during using 550 DEG C of Temperature Treatment 1h, anatase titanium dioxide tio2First
Charge/discharge capacity, high rate performance and cycle performance obtain larger raising, but lift the increase with process time again when temperature
Performance declines on the contrary, illustrates that the temperature and time processing affects not being linear relationship on the amount of Lacking oxygen, and the amount pair of Lacking oxygen
Most important in storage lithium performance.
Now although people are made that many research and improve, the head of electrode material to the chemical property of electrode material
Secondary charge/discharge capacity, high rate performance and cycle performance are also provided with significant raising, but, the electricity being prepared by prior art
Pole material is mostly solid granular, and it has poorly conductive, non-cohesive defect, in the application of electrode material, often
Need extra interpolation conductive agent and binding agent, both increased commercialization cost, and made its technique for applying loaded down with trivial details, product with stable quality again
Property poor, be unfavorable for the commercialization of electrode material with and promote.
Content of the invention
It is an object of the invention to overcome that poorly conductive, business are had using the combination electrode material that prior art prepares
Industry high cost, use troublesome defect, there is provided a kind of preparation method and applications of combination electrode material；The inventive method
The polypyrrole gel having phytic acid that mixes being formed by pyrrole monomer, phytic acid and Ammonium persulfate. is directly coated on hydrogenated process
P25 type tio2The surface of granular materialss, then with SWCN as skeleton, form the combination electrode with tridimensional network
Material, this combination electrode material not only has a good conductivity, and first charge-discharge capacity is high, high rate performance and good cycle excellent
Point, meanwhile, this combination electrode material need not be added conductive agent and binding agent again when being applied to ultracapacitor, reduce business
Industry chemical conversion originally, using more convenient, is conducive to the commercialization of secondary chemical sources of electric energy to promote.
In order to realize foregoing invention purpose, the invention provides the preparation method of combination electrode material, comprise the following steps:
1st, hydrogenation treatment: by p25 type tio2Granular materialss carry out hydrogenation treatment and obtain h-tio2Material；
2nd, coat: pyrrole monomer and phytic acid and isopropanol are mixed to form the first solution；By the first solution, Ammonium persulfate. and h-
tio2Material carries out mixing dispersion, carries out polyreaction, cladding at normal temperatures, obtains the h-tio containing polypyrrole gel cladding2
Second solution of granule；
3rd, crosslinked: to add SWCN in the second solution, carry out cross-linking reaction, obtain tio2/ polypyrrole/CNT
Tridimensional network combination electrode material.
A kind of preparation method of combination electrode material, first by p25 type tio2Granule carries out hydrogenation treatment, in tio2On granule
Introduce Lacking oxygen defect, improve p25 type tio2The chemical property of granule；Recycle polyreaction, by h-tio in isopropanol2
Material carries out coating decoration with mixing the polypyrrole gel having phytic acid, strengthens p25 type tio2The electric conductivity of granule simultaneously suppresses its group
Gather and volumetric expansion；It is eventually adding SWCN, make in the hydrogen bonding crosslinking of SWCN and polypyrrole gel
With lower formation tridimensional network, reduce ionic conduction resistance in transition process for the lithium ion, improve combination electrode material
Capacitance and cyclical stability, thus, prepare has a good conductivity, and first charge-discharge capacity is high, high rate performance and following
The good advantage of ring performance；Meanwhile, preparation and course of reaction are carried out in isopropanol, make the polypyrrole gel that polymerization obtains,
This gel polypyrrole contains substantial amounts of moisture, and molecular surface gathers substantial amounts of oh group, thus having good viscosity, and
Crosslinked, solidification can be continued between gel polypyrrole molecule after isopropanol volatilization, reach the technology effect same with binding agent
Really.
A kind of preparation method of above-mentioned combination electrode material, the wherein hydrogenation treatment described in step 1 are in order in tio2?
Introduce Lacking oxygen defect on grain, improve p25 type tio2The chemical property of granule；Preferably, described hydrotreated temperature is
400-650 DEG C, the time of process is 2-4h, and hydrotreated temperature and time has an impact to the amount of the Lacking oxygen introducing, at this
In the range of, the amount of the Lacking oxygen of introducing dramatically increases；Most preferably, described hydrotreated temperature be 550 DEG C, process when
Between be 3h.
A kind of preparation method of above-mentioned combination electrode material, the phytic acid wherein described in step 2 can promote the polymerization of pyrroles,
And mix the chemical property improving polypyrrole in polypyrrole；Preferably, described phytic acid and the volume ratio of pyrrole are 2
～3.5: 1；The polypyrrole polymers chemical property obtaining under this volume ratio is optimal；Most preferably, described phytic acid and monomer
The volume ratio of pyrroles is 2.19: 1.
Preferably, pyrrole described in step 2 and the volume ratio of isopropanol are 1: 20～35；Isopropanol consumption is very few,
To polypyrrole, h-tio2Bad dispersibility, the tio preparing2/ polypyrrole/CNT tridimensional network combination electrode material
Material chemical property is poor；Most preferably, described pyrrole and the volume ratio of isopropanol are 1: 29.76.
A kind of preparation method of above-mentioned combination electrode material, the Ammonium persulfate. energy trigger monomer pyrrole wherein described in step 2
The polymerization coughed up, makes pyrrole be polymerized and obtains polypyrrole；Preferably, described Ammonium persulfate. and the mass ratio of pyrrole are 2～4
∶1；The polypyrrole polymers chemical property obtaining under this mass ratio is optimal, and polymerization reaction time is optimal, h-tio2Granule table
The polypyrrole that bread covers is evenly；Most preferably, described Ammonium persulfate. and the mass ratio of pyrrole are 3.37: 1.
Preferably, h-tio described in step 22Material is 0.5～0.95: 1 with the mass ratio of monomer polypyrrole；In this matter
Amount is than lower h-tio2Evenly, thickness is moderate, and chemical property is more preferable for the polypyrrole of particle surface cladding；Most preferably, described
h-tio2Material is 0.74: 1 with the mass ratio of monomer polypyrrole.
Preferably, the time of the polyreaction described in step 2 is more than 5min；Polymerization reaction time is too short, polyreaction
Not exclusively.
A kind of preparation method of above-mentioned combination electrode material, the SWCN wherein described in step 3 is as skeleton
Section bar material, can bond together to form hydrogen bond with polypyrrole by the hydroxyl on respective surface, thus with polypyrrole be cross-linked to form three-dimensional netted
Structure；Preferably, described SWCN and the mass ratio of monomer polypyrrole are 1: 92～112；Crosslinked under this mass ratio
The tridimensional network electrochemical performance obtaining, Stability Analysis of Structures, caking property is good；Most preferably, described SWCN
Mass ratio with monomer polypyrrole is 1: 102.
Preferably, the time of the cross-linking reaction described in step 3 is more than 5min；Cross-linking reaction time is too short, cross-linking reaction
Not exclusively, tridimensional network is unstable.
In order to realize foregoing invention purpose, further, the invention provides a kind of application of combination electrode material, described
Combination electrode material is obtained by above-mentioned preparation method, and concrete application includes: by the tio obtaining2/ polypyrrole/carbon nanometer
Pipe tridimensional network combination electrode material is applied directly to metal foil surface, obtains electrode slice after drying solidification；Preferably,
Described metal forming is Copper Foil.
A kind of application of combination electrode material, the tio preparing2/ polypyrrole/CNT tridimensional network is combined
Electrode material need not add conductive agent and binding agent again, can be applied directly in metal forming, and after the drying, can adhesive solidification exist
In metal forming, obtaining can be used as the electrode slice of electrode；The direct application of this combination electrode material, reduces commercialization cost, makes
With more convenient, the commercialization of secondary chemical sources of electric energy is conducive to promote.
Preferably, above-mentioned electrode slice can be formed half-cell with lithium piece.
Preferably, can using above-mentioned electrode slice as lithium ion super capacitor negative pole, and using commercial activated carbons as just
Pole is assembled, and forms lithium ion super capacitor.
Compared with prior art, beneficial effects of the present invention:
1st, the gel polypyrrole that the inventive method prepares contains substantial amounts of moisture, and molecular surface gathers substantial amounts of hydroxyl base
Group, has good viscosity, and can make to continue crosslinked, solidification between gel polypyrrole molecule, play after isopropanol volatilization
The technique effect same with binding agent.
2nd, the inventive method is by p25 type tio2Granular hydrogenation temperature and time for Sexual behavior mode so as to get h-
tio2Granule contains more Lacking oxygen, and its chemical property is more preferable.
3rd, the inventive method passes through reasonable selection pyrrole, phytic acid, h-tio2Granule, the consumption of Ammonium persulfate., make
tio2The tridimensional network of/polypyrrole/CNT is more reasonable, and chemical property is more excellent.
4th, the combination electrode material that the present invention prepares may be directly applied to prepare electrode slice, and this electrode slice can be assembled into
Half-cell or lithium ion super capacitor, its commercialization low cost, using more convenient, be conducive to the commercialization of secondary chemical sources of electric energy
Promote.
Brief description:
Fig. 1 is p25 type tio in the inventive method2Xrd comparison diagram before and after hydrogenation treatment.
Fig. 2 is p25 type tio in the inventive method2Before and after hydrogenation treatment, h-tio2With compound electric of the present invention after cladding process
(a is p25 type tio to the sem figure of pole material2Sem figure before hydrogenation treatment, b is p25 type tio2Sem figure after hydrogenation treatment, c is h-
tio2After cladding is processed, sem schemes, and d is that the sem of combination electrode material of the present invention schemes).
(a schemes distribution diagram of element in the combination electrode material that Fig. 3 prepares for the inventive method for sem, and b is ti unit
Element, c is c element, and c is n element).
Fig. 4 is the chemical property comparison diagram of prior art and negative material prepared by the inventive method.
Fig. 5 is assembled into after soft-package battery for the combination electrode material that the inventive method prepares, the electrochemistry of device
(a is cyclic voltammogram to energy test result figure, and b is charge and discharge electrograph, and c is 0.5ag-1Lower 3000 circle circulation figures, d is similar to other
The energy work rate compares figure of system).
Specific embodiment
With reference to test example and specific embodiment, the present invention is described in further detail.But this should not be understood
Scope for the above-mentioned theme of the present invention is only limitted to below example, all belongs to this based on the technology that present invention is realized
The scope of invention.
Embodiment 1
1st, hydrogenation treatment: by p25 type tio2Powder sample is placed in heat treatment 30min in 300 DEG C of argon gas atmosphere in vacuum response stove
To remove the impurity on surface, it is down to room temperature；After processing, material is in ar/h simultaneously2In atmosphere, 300-650 is warmed up to 5 DEG C/min
DEG C (interval 50 DEG C) is incubated 3 hours afterwards, obtains the h-tio of the Lacking oxygen defect with different content2；
2nd, electrode slice preparation: the h-tio under treatment of different temperature2: acetylene black: grind full and uniform be coated at pvdf=8: 1: 1
120 DEG C of dryings of copper foil surface；Then cut into the electrode slice of 16*16mm and be assembled into lithium piece in the glove box full of argon
Half-cell, the chemical property at a temperature of test and comparison different disposal.
| Different disposal temperature DEG C | Specific capacity (after 0.1c 20 circle circulation) mah/g |
| Raw material | 76 |
| 300 | 82 |
| 400 | 125 |
| 450 | 127 |
| 500 | 136 |
| 550 | 159 |
| 600 | 140 |
| 650 | 98 |
From above-described embodiment, using condition of different temperatures to p25 type tio2The hydrogenation treatment of powder, the h- obtaining
tio2Chemical property is different；To p25 type tio2The hydrogenation treatment of powder, when temperature is 300-650 DEG C, can dramatically increase its ratio
Capacity, optimum treatmenting temperature is 550 DEG C.
Embodiment 2
1st, hydrogenation treatment: by p25 type tio2Powder sample is placed in heat treatment 30min in 300 DEG C of argon gas atmosphere in vacuum response stove
To remove the impurity on surface, it is down to room temperature；Then in ar/h2It is warmed up to after 550 DEG C with 5 DEG C/min in atmosphere and is incubated 3 hours, obtain
Must have the h-tio of Lacking oxygen defect2；
2nd, coat: 84 μ l pyrrole monomers and 92 μ l phytic acid are added ultrasonic disperse in 2.50ml isopropanol to obtain the first solution；Will
Aqueous solution containing 0.274g Ammonium persulfate. and 60mgh-tio2And tio2Add in the first solution, carry out ultrasonic disperse, polymerization instead
Answer 5min, respectively obtain the h-tio containing polypyrrole gel cladding2And tio2The gel of granule；
3rd, electrode slice preparation: the h-tio containing polypyrrole gel cladding will be obtained2And tio2The gel Direct Uniform of granule applies
Overlay on copper foil surface, after drying at room temperature solidification, 12h is dried at 120 DEG C of immersion 12h (removal other impurities) in deionized water and obtains
Compound electric pole piece, and it is assembled into half-cell in the glove box full of argon with lithium piece, test chemical property.
Embodiment 3
1st, hydrogenation treatment: by p25 type tio2Powder sample is placed in heat treatment 30min in 300 DEG C of argon gas atmosphere in vacuum response stove
To remove the impurity on surface, after processing, material is in ar/h simultaneously2In atmosphere, insulation 3 after 550 DEG C is warmed up to 5 DEG C/min little
When, obtain the h-tio with Lacking oxygen defect2；
2nd, coat: 84 μ l pyrrole monomers and 184 μ l plant acid solutions (comparing 50% to water quality) are added super in 2.50ml isopropanol
Sound dispersion obtains the first solution；By 0.274g Ammonium persulfate. and 60mgh-tio2Add in the first solution, carry out ultrasonic disperse, gather
Close reaction 20min, obtain the h-tio containing polypyrrole gel cladding2Second solution of granule；
3rd, crosslinked: to add 0.8mg SWCN in the second solution, carry out ultrasonic disperse, cross-linking reaction 5min, obtain
tio2/ polypyrrole/CNT tridimensional network combination electrode material.
4th, electrode slice preparation: by h-tio2/ polypyrrole/CNT tridimensional network is coated in copper foil surface, room temperature
After dry solidification, 12h is dried at 120 DEG C of immersion 12h (removal other impurities) in deionized water and obtains compound electric pole piece, and filling
It is assembled into half-cell with lithium piece in the glove box of full argon, test chemical property.
The electrode material that embodiment 2 is prepared with embodiment 3 and existing method carries out specific capacity contrast, and data is such as
Under:
| Material | Specific capacity (after 1c 20 circle circulation) mah/g |
| raw tio2 | 64 |
| raw tio2-ppy | 94 |
| h-tio2 | 130 |
| h-tio2-ppy | 153 |
| h-tio2-ppy-swcnts | 181 |
From above-described embodiment 2,3, by h-tio2Cladding and crosslinking Treatment, h-tio can be dramatically increased2Specific volume
Amount.
Experimental example:
The tio that step 3 in preparation method described in embodiment 3 is prepared2/ polypyrrole/CNT tridimensional network is multiple
Composite electrode material carries out chemical property detection with the combination electrode material preparing using prior art, and experimental result is painted
Figure, obtains Fig. 4；As shown in Figure 4, the combination electrode material electric conductivity that the inventive method prepares is more preferable, first charge-discharge capacity
Higher, high rate performance and cycle performance more preferable.
The compound electric pole piece that preparation method step 4 described in embodiment 3 is prepared is negative pole, with commercial activated carbons for just
Pole, both positive and negative polarity mass ratio is 5: 1, is assembled into soft-package battery test performance as condition, and assembles with existing conventional cathode piece
The energy work rate of soft-package battery contrasted, experimental result is drawn, and obtains Fig. 5；As shown in Figure 5, prepared using the inventive method
Compound electric pole piece first charge-discharge capacity height, high rate performance and the good cycle obtaining, energy work rate is big, meets secondary chemistry
The requirement to electrode material for the power supply.
Claims (10)
1. a kind of preparation method of combination electrode material is it is characterised in that comprise the following steps:
(1) hydrogenation treatment: by p25 type tio2Granular materialss carry out hydrogenation treatment and obtain h-tio2Material；
(2) coat: pyrrole monomer and phytic acid are mixed to form the first solution with isopropanol；By the first solution, Ammonium persulfate. and h-
tio2Material carries out mixing dispersion, carries out polyreaction, cladding at normal temperatures, obtains the h-tio containing polypyrrole gel cladding2
Second solution of granule；
(3) crosslinked: to add SWCN in the second solution, carry out cross-linking reaction, obtain tio2/ polypyrrole/CNT
Tridimensional network combination electrode material.
2. preparation method according to claim 1 is it is characterised in that hydrotreated temperature described in step 1 is 400-
650 DEG C, the time of process is 2-4h.
3. preparation method according to claim 2 is it is characterised in that hydrotreated temperature described in step 1 is 550
DEG C, the time of process is 3h.
4. preparation method according to claim 1 is it is characterised in that the volume of phytic acid described in step 2 and pyrrole
Than for 2 ~ 3.5:1.
5. preparation method according to claim 1 is it is characterised in that the body of pyrrole described in step 2 and isopropanol
Long-pending ratio is 1:20 ~ 35.
6. preparation method according to claim 1 is it is characterised in that h-tio described in step 22Material and monomer polypyrrole
Mass ratio be 0.5 ~ 0.95:1.
7. preparation method according to claim 1 is it is characterised in that Ammonium persulfate. described in step 2 and pyrrole
Mass ratio is 2 ~ 4:1.
8. preparation method according to claim 1 is it is characterised in that SWCN described in step 3 and the poly- pyrrole of monomer
The mass ratio coughed up is 1:92 ~ 112.
9. the application of the combination electrode material that the preparation method described in a kind of claim 1 prepares is it is characterised in that wrap
Include: combination electrode material is applied directly to metal foil surface, after drying solidification, obtains electrode slice.
10. the application of combination electrode material according to claim 9 is it is characterised in that by described electrode slice and lithium piece group
Fill half-cell or using described electrode slice as negative pole, assemble lithium ion super capacitor using commercial activated carbons as positive pole.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611067395.2A CN106340401B (en) | 2016-11-28 | 2016-11-28 | A kind of preparation method and applications of combination electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611067395.2A CN106340401B (en) | 2016-11-28 | 2016-11-28 | A kind of preparation method and applications of combination electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106340401A true CN106340401A (en) | 2017-01-18 |
| CN106340401B CN106340401B (en) | 2018-05-08 |
Family
ID=57841891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611067395.2A Active CN106340401B (en) | 2016-11-28 | 2016-11-28 | A kind of preparation method and applications of combination electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106340401B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501895A (en) * | 2017-09-19 | 2017-12-22 | 原晋波 | A kind of preparation method of composite nanometer conductive material |
| CN108461301A (en) * | 2018-05-16 | 2018-08-28 | 合肥工业大学 | A kind of MnO2-PPy/H-TiO2Ternary core-shell array hybridizations electrode material and preparation method thereof |
| CN109126891A (en) * | 2018-07-09 | 2019-01-04 | 江汉大学 | A kind of preparation method of the polypyrrole nanocluster of the titania additive of modification |
| CN110112002A (en) * | 2018-02-01 | 2019-08-09 | 南京理工大学 | The mesoporous micron ball of ZnO-CoO@NC, preparation method and applications |
| CN110880589A (en) * | 2019-11-25 | 2020-03-13 | 浙江理工大学 | Carbon nanotube @ titanium dioxide nanocrystal @ carbon composite material and preparation method and application thereof |
| CN111048322A (en) * | 2018-10-14 | 2020-04-21 | 天津大学 | Carbon nanotube-polyaniline-gelatin semi-interpenetrating network flexible electrode and preparation method and application thereof |
| CN112735854A (en) * | 2020-12-23 | 2021-04-30 | 杭州电子科技大学 | Preparation method of double-conducting-network supercapacitor based on MOF electrode |
| CN113479860A (en) * | 2021-07-01 | 2021-10-08 | 中国石油大学(华东) | SbPO4Preparation method of/nitrogen-doped carbon composite material |
| CN113690057A (en) * | 2021-08-24 | 2021-11-23 | 湖南大学 | Phytic acid electrochemical oxidation-polypyrrole/carbon fiber composite material and preparation method and application thereof |
| CN113921796A (en) * | 2021-10-11 | 2022-01-11 | 河南科技大学 | Phytic acid-vanadium pentoxide composite material, preparation method thereof, electrode and battery |
| CN114566628A (en) * | 2022-03-04 | 2022-05-31 | 合肥工业大学 | Preparation method of anode material of phytic acid doped polypyrrole @ vanadate water-based zinc ion battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007119692A (en) * | 2005-10-31 | 2007-05-17 | Achilles Corp | Conductive composite material and conductive thin film using it |
| CN102302955B (en) * | 2011-06-22 | 2013-01-02 | 南京大学 | Floating polypyrrole-TiO2/floating bead photocatalyst, and preparation method and application thereof |
| CN104465123A (en) * | 2014-12-02 | 2015-03-25 | 国家纳米科学中心 | Electrode material of C@MnO2 nanotube super capacitor and preparation method and application of electrode material |
| CN105006376A (en) * | 2015-07-13 | 2015-10-28 | 华北电力大学 | Preparation method of carbon nanotube and nickel oxide composite material |
| CN105390687A (en) * | 2015-11-03 | 2016-03-09 | 盐城工学院 | High-performance three-dimensional carbon nanotube composite negative electrode material, preparation method therefor and application thereof |
-
2016
- 2016-11-28 CN CN201611067395.2A patent/CN106340401B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007119692A (en) * | 2005-10-31 | 2007-05-17 | Achilles Corp | Conductive composite material and conductive thin film using it |
| CN102302955B (en) * | 2011-06-22 | 2013-01-02 | 南京大学 | Floating polypyrrole-TiO2/floating bead photocatalyst, and preparation method and application thereof |
| CN104465123A (en) * | 2014-12-02 | 2015-03-25 | 国家纳米科学中心 | Electrode material of C@MnO2 nanotube super capacitor and preparation method and application of electrode material |
| CN105006376A (en) * | 2015-07-13 | 2015-10-28 | 华北电力大学 | Preparation method of carbon nanotube and nickel oxide composite material |
| CN105390687A (en) * | 2015-11-03 | 2016-03-09 | 盐城工学院 | High-performance three-dimensional carbon nanotube composite negative electrode material, preparation method therefor and application thereof |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501895A (en) * | 2017-09-19 | 2017-12-22 | 原晋波 | A kind of preparation method of composite nanometer conductive material |
| CN110112002A (en) * | 2018-02-01 | 2019-08-09 | 南京理工大学 | The mesoporous micron ball of ZnO-CoO@NC, preparation method and applications |
| CN110112002B (en) * | 2018-02-01 | 2020-12-04 | 南京理工大学 | ZnO-CoO @ NC mesoporous microsphere, preparation method and application thereof |
| CN108461301A (en) * | 2018-05-16 | 2018-08-28 | 合肥工业大学 | A kind of MnO2-PPy/H-TiO2Ternary core-shell array hybridizations electrode material and preparation method thereof |
| CN109126891B (en) * | 2018-07-09 | 2021-08-06 | 江汉大学 | Preparation method of modified titanium dioxide doped polypyrrole nanocluster |
| CN109126891A (en) * | 2018-07-09 | 2019-01-04 | 江汉大学 | A kind of preparation method of the polypyrrole nanocluster of the titania additive of modification |
| CN111048322A (en) * | 2018-10-14 | 2020-04-21 | 天津大学 | Carbon nanotube-polyaniline-gelatin semi-interpenetrating network flexible electrode and preparation method and application thereof |
| CN111048322B (en) * | 2018-10-14 | 2021-07-13 | 天津大学 | Carbon nanotube-polyaniline-gelatin semi-interpenetrating network flexible electrode and preparation method and application thereof |
| CN110880589A (en) * | 2019-11-25 | 2020-03-13 | 浙江理工大学 | Carbon nanotube @ titanium dioxide nanocrystal @ carbon composite material and preparation method and application thereof |
| CN110880589B (en) * | 2019-11-25 | 2021-04-06 | 浙江理工大学 | Carbon nanotube @ titanium dioxide nanocrystal @ carbon composite material and preparation method and application thereof |
| CN112735854A (en) * | 2020-12-23 | 2021-04-30 | 杭州电子科技大学 | Preparation method of double-conducting-network supercapacitor based on MOF electrode |
| CN112735854B (en) * | 2020-12-23 | 2022-03-22 | 杭州电子科技大学 | Preparation method of double-conducting-network supercapacitor based on MOF electrode |
| CN113479860A (en) * | 2021-07-01 | 2021-10-08 | 中国石油大学(华东) | SbPO4Preparation method of/nitrogen-doped carbon composite material |
| CN113479860B (en) * | 2021-07-01 | 2023-08-11 | 中国石油大学(华东) | SbPO (styrene-ethylene-propylene-diene monomer) 4 Preparation method of nitrogen-doped carbon composite material |
| CN113690057A (en) * | 2021-08-24 | 2021-11-23 | 湖南大学 | Phytic acid electrochemical oxidation-polypyrrole/carbon fiber composite material and preparation method and application thereof |
| CN113690057B (en) * | 2021-08-24 | 2022-08-02 | 湖南大学 | Phytic acid electrochemical oxidation-polypyrrole/carbon fiber composite material and preparation method and application thereof |
| CN113921796A (en) * | 2021-10-11 | 2022-01-11 | 河南科技大学 | Phytic acid-vanadium pentoxide composite material, preparation method thereof, electrode and battery |
| CN114566628A (en) * | 2022-03-04 | 2022-05-31 | 合肥工业大学 | Preparation method of anode material of phytic acid doped polypyrrole @ vanadate water-based zinc ion battery |
| CN114566628B (en) * | 2022-03-04 | 2023-02-24 | 合肥工业大学 | Preparation method of phytic acid doped polypyrrole @ vanadate aqueous zinc ion battery positive electrode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106340401B (en) | 2018-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106340401A (en) | Preparing method of composite electrode material and application thereof | |
| Li et al. | A robust network binder via localized linking by small molecules for high-areal-capacity silicon anodes in lithium-ion batteries | |
| CN103680995B (en) | For the mesoporous carbon/RuO of ultracapacitor 2composite material and preparation method | |
| CN107946086A (en) | It is a kind of using graphene as full carbon resistance rod of ultracapacitor flexible self-supporting of binding agent and preparation method thereof | |
| CN106024408B (en) | A kind of ruthenium-oxide-vulcanization carbon/carbon-copper composite material, using and a kind of electrode slice of ultracapacitor | |
| CN101937989A (en) | Three-dimensional nanoporous metal-oxide electrode material of lithium ion battery and preparation method thereof | |
| CN105152170A (en) | Preparation method for cicada slough based porous carbon material used for electrochemical capacitor | |
| CN102516764B (en) | Polyaniline nanowire/ graded porous carbon composite material as well as preparation method and application thereof | |
| CN103839694A (en) | Graphene/metal current collector preparing method | |
| CN108922790A (en) | A kind of manganese dioxide/N doping porous carbon composite preparation method and application of sodium ion insertion | |
| CN107331537A (en) | A kind of preparation method and application of three-dimensional grapheme/graphite-phase nitrogen carbide | |
| CN103839695A (en) | Graphene electrode plate, and preparation method and application thereof | |
| AU2020101283A4 (en) | Method for Manufacturing Straw-Based Activated Carbon Electrode Material for Super Capacitor with Energy Storage Efficiency Enhanced Through Acid Mine Drainage | |
| CN108039283B (en) | A kind of rich N doping multi-stage porous carbon material and the preparation method and application thereof based on in-situ polymerization | |
| CN102130326A (en) | High-capacity functionalized carbon layered electrode and preparation method thereof | |
| Zeng et al. | Hierarchical 3D micro‐nanostructures based on in situ deposited bimetallic metal‐organic structures on carbon fabric for supercapacitor applications | |
| CN108011087A (en) | A kind of manganese dioxide negative material of titanium dioxide modification and preparation method thereof | |
| US20110002085A1 (en) | Electrode for capacitor and electric double layer capacitor having the same | |
| KR101095863B1 (en) | Electrode of super capacitor for high power and manufacturing method thereof | |
| CN101794671B (en) | Super capacitor and manufacture method thereof | |
| CN103086350B (en) | Mesoporous carbon electrode material and preparation method thereof | |
| CN103545115A (en) | Graphene-carbon nano tube composite material, preparation method thereof and super capacitor | |
| CN105513834B (en) | A kind of preparation method and applications of bacteria cellulose graphene paper supported cobaltosic oxide flexible electrode material | |
| CN112038113A (en) | Preparation method of polypyrrole nanotube and graphene material in super capacitor | |
| CN106653388A (en) | Three-dimensional pure graphene hydrogel material with high conductivity and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |