CN110034292A - A kind of 3-D ordered multiporous polypyrrole/zinc oxide lithium ion battery negative material and preparation method - Google Patents
A kind of 3-D ordered multiporous polypyrrole/zinc oxide lithium ion battery negative material and preparation method Download PDFInfo
- Publication number
- CN110034292A CN110034292A CN201910358941.5A CN201910358941A CN110034292A CN 110034292 A CN110034292 A CN 110034292A CN 201910358941 A CN201910358941 A CN 201910358941A CN 110034292 A CN110034292 A CN 110034292A
- Authority
- CN
- China
- Prior art keywords
- polypyrrole
- lithium ion
- solution
- ion battery
- zinc oxide
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
- H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention is a kind of 3-D ordered multiporous polypyrrole/zinc oxide lithium ion battery negative material.The composition of the electrode material includes the ZnO nano particle of polypyrrole material and load, and the load quality percentage of ZnO is 20%-60%；Wherein, the carrier polypyrrole material has 3-D ordered multiporous structure, i.e., containing single, orderly aligned, interconnected macropore: pore diameter range is 300~500nm.The present invention makes ZnO nano particle growth in situ on the porous hole wall of PPy using sol-gal process.PPy excellent electric conductivity can provide good conductive path for zinc oxide, and porous duct interconnected can accelerate the transmission of lithium ion and electrolyte inside electrode material, to improve the cycle performance of lithium ion battery.
Description
Technical field:
Technical solution of the present invention is related to the preparation of ion cathode material lithium, specifically plants lithium ion battery oxidation
Zinc/PPy negative electrode material preparation method.
Background technique:
Lithium ion battery is because operating voltage is high, the cyclicity service life is long, has a safety feature, and nuisanceless, memory-less effect etc. is excellent
Point has been widely used in portable electronic device, such as mobile phone, camera, laptop now.In recent years, with mixing
Power vehicle and electric car are continuously increased and develop, and exploitation has a high-energy, high power density and good circulation performance
Lithium ion battery become current social development there is an urgent need to.Present commercial li-ion cell negative electrode material is usually using graphite-like
Material, but due to its low theoretical specific capacity (372mAh g-1), graphite negative electrodes material is limited in high-energy density chemical-electrical
Application in source, therefore develop high performance novel anode material and have become a urgent task.In recent years, oxo transition metal
Theoretical specific capacity and the low production cost of compound (MOx, M:Fe, Co, Ni, Zn etc.) Yin Qigao and the extensive pass for causing people
Note is expected to become next-generation cathode material of lithium ion battery.Wherein, ZnO is because of its high theoretical specific capacity (978mAh g-1),
Low production cost, advantages of environment protection and show one's talent.But it is anti-in electrochemistry as lithium ion battery negative material
Serious Volumetric expansion and agglomeration can should occur in the process, seriously affect the circulation and high rate performance of electrode material.
In order to overcome these problems, being developed the ZnO materials of various nanostructures, (such as nanotube, hollow nano-sphere and monocrystalline are received
Rice stick etc.) to improve active material utilization.Although nano ZnO material can reduce the diffusion length of lithium ion and adapt to lithium
Ion material internal intercalation/deintercalation mechanical strain, but since its high specific surface area and surface can still have thermodynamics
The disadvantages of stability difference and easy aggregation.Therefore, ZnO nano particle and protecting group Material cladding are further increased into electrode material
Performance is very important.Porous carbon materials, graphene and carbon nanotube etc. are because having big specific surface area, excellent electric conductivity
And be widely used as protecting group, but these carbon materials can deposit structure collapses during the reaction, active material falls off, thus
Lead to problems such as stability poor.
Polypyrrole (PPy) is a kind of typical soft conducting polymer, it is conductive it is good, conductivity is adjustable, anticorrosive property
By force, air stability is good, environmental-friendly, non-toxic, good biocompatibility, light specific gravity, preparation method is simple, production cost is low
The advantages that, electric conductivity and the structure that lithium ion battery electrode material can be enhanced when serving as lithium ion battery coating or matrix are steady
It is qualitative.Studies have shown that PPy has good mechanical flexibility and chemical stability in electrochemical process.By ZnO nano particle
With the compound electric conductivity that can significantly improve ZnO as lithium ion battery negative material of PPy phase.However, the lesser specific surface of PPy
Product limits the diffusion of electrolyte in the high degree of dispersion and reaction process of ZnO nano particle.3-D ordered multiporous PPy has hole
The advantages such as diameter is adjustable, specific surface area is high help to improve the dispersibility of ZnO nano particle, and reduce the grain of ZnO particle
Diameter.During the reaction, also the reunion of nano material can be effectively limited, to improve the cycle performance of lithium ion battery.
Summary of the invention:
The purpose of the present invention is provide a kind of 3-D ordered multiporous polypyrrole/oxygen for deficiency present in current techniques
Change zinc lithium ion battery negative material and preparation method.It is deposited by compound improve when single zinc oxide does cathode of ZnO and porous PP y
Poorly conductive, it is easy to fall off the problems such as.The technical solution that the present invention uses is that use silicon dioxide sub-micron sphere array be mould
Plate synthesizes a kind of Porous Polypyrrole material of three-dimensional order.Make ZnO nano particle in the porous of PPy using sol-gal process
Uniform load on wall.PPy excellent electric conductivity can provide good conductive path, porous duct interconnected for zinc oxide
It can accelerate the transmission of lithium ion and electrolyte inside electrode material, to improve the cycle performance of lithium ion battery.
The technical solution adopted by the present invention is that:
A kind of 3-D ordered multiporous polypyrrole/zinc oxide lithium ion battery negative material, it is characterised in that the electrode material
Composition include polypyrrole material and load ZnO nano particle, the load quality percentage of ZnO is 20%-60%；Wherein,
The carrier polypyrrole material have 3-D ordered multiporous structure, i.e., containing it is single, orderly aligned, be interconnected it is big
Hole: pore diameter range is 300~500nm.
The partial size of the ZnO nano particle is 3.0~10.0nm.
3-D ordered multiporous polypyrrole/zinc oxide lithium ion battery negative material preparation method, including it is following
Step:
(1) it prepares silicon dioxide microsphere colloidal sol: silicon dioxide microsphere is distributed in aqueous solution, obtaining mass fraction is
The monodispersed silicon dioxide microsphere colloidal sol of 10%-30%；
(2) monodispersed silicon dioxide microsphere colloidal sol is placed in container, after sealing, stands 10~20 days；Then it breaks a seal,
Supernatant liquor is taken out, continues standing 5~10 days, until solution evaporation finishes, obtains dry silica template；
(3) 3-D ordered multiporous polypyrrole material: in deionized water by pyrroles and sodium acetate dissolution, then it is added upper one
The silica template that step is prepared is eventually adding the FeCl of 0.2-0.4M3Aqueous solution reacts 10~15h in ice-water bath,
After reaction the silica template that deposited polypyrrole will be taken out from solution, remove mould using deionized water cleaning
Plate surface polypyrrole；The compound of polypyrrole and silica is impregnated into 12-24h in HF solution again, through over cleaning, obtains three
Tie up ordered porous polypyrrole material；
Wherein, it is added on 0.1-0.3g pyrroles and 0.1-0.3g sodium acetate and 0.5-2g in every 5-10mL deionized water
The silica template and 10mL FeCl that one step is prepared3Aqueous solution；
(4) 3-D ordered multiporous polypyrrole loading ZnO nano particles are prepared: by 3-D ordered multiporous poly- pyrrole obtained above
Material 0.3-0.5g ultrasonic disperse is coughed up in 15-30mL methanol；0.2-1g zinc acetate is taken to be dissolved in 15-30mL methanol, it will be upper
It states two kinds of solution mixing and persistently stirs 1-2h at 40-70 DEG C and obtain solution A；The potassium hydroxide of 0.15-0.5g is dissolved in
In the methanol of 15mL, and it is warming up to 40-70 DEG C and obtains solution B；Later, solution B is added to by dropwise addition or spray pattern molten
In liquid A and continue stirring 2-4 hours；It is finally that sediment eccentric cleaning is dry, obtain 3-D ordered multiporous polypyrrole loading ZnO
Nano particle；
The sphere diameter of microballoon is 300~500nm in the monodispersed silicon dioxide microsphere colloidal sol.
Monodisperse silica microspheres in the step (1) are to utilizeMethod is made.
ZnO nano particle is obtained by excessive potassium hydroxide solution oxidation zinc acetate in the step (4).
Time for adding in the step (4) is preferably 15-30min.
The mass percentage concentration of HF solution in the step (3) is 5%-20%.
The preparation method of the above-mentioned zinc oxide that can be used for lithium ion battery negative material/PPy composite material, wherein involved
To raw material be commercially available, equipment used and technique are known to those skilled in the art
Substantive distinguishing features of the invention are as follows:
Inventor's previous work prepares 3-D ordered multiporous carbon material supported Zinc oxide nanoparticle, but carbon material is deposited
It is being easy electrochemical corrosion in the reaction, the disadvantages of structure collapses.For the first time by Zinc oxide nanoparticle on material composition of the present invention
Lithium ion battery negative material is prepared in conjunction with 3-D ordered multiporous polypyrrole with good conductivity.The cathode material of oxide-base
Material is generally carrier using carbon material, but carbon material is easy electrochemical corrosion during the reaction, causes loaded oxide
Material falls back makes capacity attenuation.And polypyrrole material not only has preferable electric conductivity, but also stable structure, as oxidation
The carrier of zinc nanoparticles can increase the stability of electrode material.However, the specific surface area of polypyrrole material is smaller, it can not
Anchoring Zinc oxide nanoparticle well, the invention patent are directed to polypyrrole this disadvantage, and invention Porous Polypyrrole material is born
Supported with zinc oxide nano particle.In preparation method, be by the excessive sol-gal process of oxidant KOH, will be lesser nano oxidized
Zinc particulate load is on the macropore hole wall of 3-D ordered multiporous polypyrrole.
The invention has the benefit that
1. the present invention prepares large specific surface area using silica hard mold version, cellular structure prosperity has specific morphology
Conduction high polymer polypyrrole.The aperture of PPy can be controlled by adjusting the size of silicon dioxide microsphere partial size using hard mold version method
Size.
Nano granular of zinc oxide can be made uniformly to divide 2. preparing zinc oxide/PPy composite material by sol-gal process
Cloth on the hole wall of PPy macropore, and nano granular of zinc oxide smaller (when ZnO content is 20wt%, the partial size of ZnO is less than 5nm),
It is of uniform size.ZnO particle reduces, and specific surface area increases, and can provide more reaction active sites.This synthesis technology has system
Preparation Method is simple, at low cost, advantages of environment protection.
The compound conduct lithium ion battery negative material of polypyrrole and nano granular of zinc oxide can be improved into single zinc oxide
The problems such as the swollen effect of volume Peng existing for lithium ion battery negative material and agglomeration, enhance the cyclicity of electrode material
It can be (in 1A g-1Current density under, 200 times circulation after, still keep 899mAh g-1Capacity).
Detailed description of the invention:
Fig. 1 is resulting ZnO/PPy (ZnO content 20wt%) transmission electron microscope photo of embodiment 1.
Fig. 2 is the X-ray diffractogram of the resulting ZnO/PPy (ZnO content 20wt%) of embodiment 1.
Fig. 3 is the transmission electron microscope photo of the resulting ZnO/PPy (ZnO content 60wt%) of embodiment 5.
Fig. 4 is that the resulting PPy of embodiment 5 loads zinc oxide composite as lithium ion battery negative material electric discharge specific volume
Measure curve.
Specific embodiment
Method of the invention is further described below in conjunction with example.These examples have further described and demonstrated this
Embodiment in invention scope.The purpose that the example provided is merely to illustrate, but it is not limited to this, should not constitute to the present invention
Any restriction can carry out various changes to it without departing from the spirit and scope of the present invention.
Silicon dioxide microsphere colloidal sol of the present invention be known substance, preparation may refer to (W,et
al.Controlled growth of monodisperse silica spheres in the micron size
range.Journal of Colloid&Interface Science,1968,26(1):62-69)。
Embodiment 1
The preparation method of 3-D ordered multiporous polypyrrole loading ZnO nano particles, steps are as follows:
(1) 9.0g deionized water, 30.8mL ammonium hydroxide and 160mL dehydrated alcohol are uniformly mixed under magnetic stirring stand-by.
(2) ethanol solution for the ethyl orthosilicate (TEOS) that configuration 200mL contains 10.5g rapidly joins step (1) configuration
Solution in.Magnetic agitation obtains white emulsion after reacting 12 hours at 25 DEG C.
(3) white emulsion obtained in step (2) is obtained into silicon dioxide microsphere by way of centrifugation (sphere diameter is
300nm), silica spheres ultrasonic disperse is prepared into silica spheres colloidal sol, the matter of silicon dioxide microsphere into deionized water
Amount is the 10% of colloidal sol quality.
(4) it in the wide-mouth bottle of the monodispersed silicon dioxide microsphere colloidal sol merging 500mL of the 300mL obtained step (3), uses
Preservative film sealing, stands 20 days.Silicon dioxide microsphere is self-assembled into the silicon dioxide microsphere battle array of three-dimensional order due to gravity
Column.Preservative film is removed, supernatant liquor is taken out, continues to stand 10 days, until solution evaporation finishes, obtains dry silica
Template.
(5) 0.3g pyrroles and 0.3g sodium acetate are added in 10mL water, the silica mould of step (4) preparation is then added
Plate 1g is eventually adding 0.2mol L-1FeCl3Aqueous solution 10mL reacts 12h as oxidant in ice-water bath.After reacting
The silica template that deposited polypyrrole takes out from solution, deionized water cleans to obtain polypyrrole and silica it is compound
Object.
(6) compound of polypyrrole and silica that step (5) obtains is impregnated in the HF solution of 5wt% and is gone for 24 hours
Fall silica template, then cleaned three times with deionized water, finally obtains 3-D ordered multiporous polypyrrole material.
(7) the 3-D ordered multiporous polypyrrole material 0.4g ultrasonic disperse for obtaining step (6) is in 30mL methanol；It takes
0.27g zinc acetate is dissolved in 30mL methanol, above two solution is mixed and is persistently stirred at 60 DEG C 1 hour obtains solution
A.By the potassium hydroxide solution of 0.15g in the methanol of 15mL, and it is warming up to 60 DEG C and obtains solution B.Later, dropwise by solution B
(1-2 drop per second) is added in solution A and continues stirring 2-4 hours.It is finally that sediment eccentric cleaning is dry, obtain ZnO/
PPy (ZnO content 20wt%) material.
Fig. 1 show transmission electron microscope (TEM) figure of ZnO/PPy material made from this example, can from figure
Out, 3-D ordered multiporous structure is presented in polypyrrole, and macropore diameter is uniform, about 300nm.ZnO nano particle presents evenly dispersed
State.Fig. 2 is X-ray diffraction (XRD) map of the ZnO/PPy material prepared in the implementation case.Occur at 20~30 °
The characteristic peak of unformed PPy, remaining is 31.7 °, 34.4 °, 36.2 °, 47.5 °, 56.5 °, 62.8 ° and 67.9 ° in the angle of diffraction
Diffraction maximum corresponds to the characteristic peak (JCPDS card, No.36-1451) of ZnO buergerite, and zinc oxide shows good crystallization
Property.Calculating nano zine oxide diameter by Scherrer formula (D=0.89 λ/Bcos θ) is about 4.8nm.
Embodiment 2
The preparation method of ZnO/PPy, step is with embodiment 1, except that the amount of TEOS is 27.5g in step (2),
The sphere diameter of prepared silicon dioxide microsphere is 400nm.
Embodiment 3
The preparation method of ZnO/PPy, step is with embodiment 1, except that the amount of TEOS is 48.5g in step (2),
The sphere diameter of prepared silicon dioxide microsphere is 500nm.
Embodiment 4
The preparation method of ZnO/PPy, step is with embodiment 1, except that zinc acetate and potassium hydroxide in step (7)
Additional amount be 0.54g and 0.30g, obtain ZnO/PPy (ZnO content 40wt%).
Embodiment 5
The preparation method of ZnO/PPy, step is with embodiment 1, except that zinc acetate and potassium hydroxide in step (7)
Additional amount be 0.81g and 0.45g, obtain ZnO/PPy (ZnO content 60wt%).
Fig. 3 show the TEM figure of ZnO/PPy material made from this example, it can be seen from the figure that ZnO nano particle is equal
It is even dispersion but it is higher compared with one content of embodiment.
Fig. 4 is the circulation figure of the ZnO/PPy material for preparing as lithium ion battery negative material in the implementation case, general
ZnO/PPy composite material and conductive agent Ketjen black, binder Kynoar are mixed in 8:1:1 ratio, grind and N- first is added
Base pyrrolidone solution keeps its evenly dispersed, is coated on copper foil and is placed in drying in baking oven, it is living then will to be loaded with ZnO/PPy
Property substance copper foil be cut into diameter be 14mm round pole piece it is spare.Using CR2032 type button cell shell in the hand for being full of argon gas
Battery assembly is carried out in casing, using obtained pole piece as cathode, lithium piece contains 1M six as diaphragm as anode, polypropylene screen
Dimethyl carbonate/diethyl carbonate/ethylene carbonate mixed solution (three's volume ratio is 1:1:1) of lithium fluophosphate is as electricity
Solve liquid.Carrying out constant current charge-discharge test voltage range after being completed on new prestige cell tester is 0.01-3V, ZnO/PPy
Negative electrode material shows good cyclical stability and high specific discharge capacity, in 1A g-1There is 899mAh after lower circulation 100 times
g-1Capacity show good chemical property.
Embodiment 6
The preparation method of ZnO/PPy, step is with embodiment 1, except that B solution is used spray gun mist in step (7)
Change, is added in the solution A of preparation early period.
Unaccomplished matter of the present invention is well-known technique.
Claims (6)
1. a kind of 3-D ordered multiporous polypyrrole/zinc oxide lithium ion battery negative material, it is characterized in that the group of the electrode material
At the ZnO nano particle including polypyrrole material and load, the load quality percentage of ZnO is 20%-60%；Wherein, described
Carrier polypyrrole material there is 3-D ordered multiporous structure, i.e., containing single, orderly aligned, interconnected macropore: hole
Diameter range is 300~500nm；
The partial size of the ZnO nano particle is 3.0~10.0nm.
2. the preparation method of 3-D ordered multiporous polypyrrole/zinc oxide lithium ion battery negative material as described in claim 1,
It is characterized in that method includes the following steps:
(1) it prepares silicon dioxide microsphere colloidal sol: silicon dioxide microsphere is distributed in aqueous solution, obtaining mass fraction is 10%-
30% monodispersed silicon dioxide microsphere colloidal sol；
(2) monodispersed silicon dioxide microsphere colloidal sol is placed in container, after sealing, stands 10~20 days；Then it breaks a seal, takes out
Supernatant liquor continues standing 5~10 days, until solution evaporation finishes, obtains dry silica template；
(3) 3-D ordered multiporous polypyrrole material: in deionized water by pyrroles and sodium acetate dissolution, previous step is then added
The silica template prepared is eventually adding the FeCl of 0.2-0.4M3Aqueous solution reacts 10~15h, reaction in ice-water bath
After will, the silica template that deposited polypyrrole is taken out from solution, using deionized water cleaning remove template table
Face polypyrrole；The compound of polypyrrole and silica is impregnated into 12-24h in HF solution again, through over cleaning, obtaining three-dimensional has
Sequence Porous Polypyrrole material；
Wherein, 0.1-0.3g pyrroles and 0.1-0.3g sodium acetate and 0.5-2g previous step are added in every 5-10mL deionized water
Suddenly the silica template and 10mL FeCl prepared3Aqueous solution；
(4) 3-D ordered multiporous polypyrrole loading ZnO nano particles are prepared: by 3-D ordered multiporous polypyrrole material obtained above
Expect 0.3-0.5g ultrasonic disperse in 15-30mL methanol；0.2-1g zinc acetate is taken to be dissolved in 15-30mL methanol, by above-mentioned two
Kind solution, which mixes and persistently stirs 1-2h at 40-70 DEG C, obtains solution A；The potassium hydroxide of 0.15-0.5g is dissolved in 15mL
Methanol in, and be warming up to 40-70 DEG C and obtain solution B；Later, solution B is added in solution A by dropwise addition or spray pattern
And continue stirring 2-4 hours；It is finally that sediment eccentric cleaning is dry, obtain 3-D ordered multiporous polypyrrole loading ZnO nanometer
Particle.
3. the preparation method of 3-D ordered multiporous polypyrrole/zinc oxide lithium ion battery negative material as claimed in claim 2,
It is characterized in that the sphere diameter of microballoon is 300~500nm in the monodispersed silicon dioxide microsphere colloidal sol.
4. the preparation method of 3-D ordered multiporous polypyrrole/zinc oxide lithium ion battery negative material as claimed in claim 2,
It is characterized in that the monodisperse silica microspheres in the step (1) are to utilizeMethod is made.
5. the preparation method of 3-D ordered multiporous polypyrrole/zinc oxide lithium ion battery negative material as claimed in claim 2,
It is characterized in that the time for adding in the step (4) is preferably 15-30min.
6. the preparation method of 3-D ordered multiporous polypyrrole/zinc oxide lithium ion battery negative material as claimed in claim 2,
It is characterized in that the mass percentage concentration of the HF solution in the step (3) is 5%-20%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910358941.5A CN110034292B (en) | 2019-04-30 | 2019-04-30 | Three-dimensional ordered porous polypyrrole/zinc oxide lithium ion battery negative electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910358941.5A CN110034292B (en) | 2019-04-30 | 2019-04-30 | Three-dimensional ordered porous polypyrrole/zinc oxide lithium ion battery negative electrode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110034292A true CN110034292A (en) | 2019-07-19 |
| CN110034292B CN110034292B (en) | 2022-05-24 |
Family
ID=67241096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910358941.5A Active CN110034292B (en) | 2019-04-30 | 2019-04-30 | Three-dimensional ordered porous polypyrrole/zinc oxide lithium ion battery negative electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110034292B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111420692A (en) * | 2020-03-23 | 2020-07-17 | 云南电网有限责任公司电力科学研究院 | Composite catalyst and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050208380A1 (en) * | 2004-02-07 | 2005-09-22 | Hong-Kyu Park | Electrode additives coated with electro conductive material and lithium secondary comprising the same |
| CN106941167A (en) * | 2017-04-17 | 2017-07-11 | 中航锂电（洛阳）有限公司 | A kind of porous composite negative pole material of lithium ion battery and preparation method thereof |
| CN107069049A (en) * | 2017-04-10 | 2017-08-18 | 河北工业大学 | A kind of mesoporous polypyrrole nano-rings loaded Pt catalyst and preparation method thereof |
| CN109037552A (en) * | 2018-08-07 | 2018-12-18 | 河北工业大学 | A kind of preparation method of the diaphragm material for sodium-sulphur battery |
-
2019
- 2019-04-30 CN CN201910358941.5A patent/CN110034292B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050208380A1 (en) * | 2004-02-07 | 2005-09-22 | Hong-Kyu Park | Electrode additives coated with electro conductive material and lithium secondary comprising the same |
| CN107069049A (en) * | 2017-04-10 | 2017-08-18 | 河北工业大学 | A kind of mesoporous polypyrrole nano-rings loaded Pt catalyst and preparation method thereof |
| CN106941167A (en) * | 2017-04-17 | 2017-07-11 | 中航锂电（洛阳）有限公司 | A kind of porous composite negative pole material of lithium ion battery and preparation method thereof |
| CN109037552A (en) * | 2018-08-07 | 2018-12-18 | 河北工业大学 | A kind of preparation method of the diaphragm material for sodium-sulphur battery |
Non-Patent Citations (2)
| Title |
|---|
| FUXING YIN等: "ZnO nanoparticles encapsulated in three dimensional ordered macro-/mesoporous carbon as high-performance anode for lithium-ion battery", 《ELECTROCHIMICA ACTA》 * |
| HAIPENG LI等: "Three-dimensionally ordered hierarchically porous polypyrrole loading sulfur as high-performance cathode for lithium/sulfur batteries", 《POLYMER》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111420692A (en) * | 2020-03-23 | 2020-07-17 | 云南电网有限责任公司电力科学研究院 | Composite catalyst and preparation method thereof |
| CN111420692B (en) * | 2020-03-23 | 2023-11-03 | 云南电网有限责任公司电力科学研究院 | Composite catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110034292B (en) | 2022-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11866332B2 (en) | Carbon nanoparticle-porous skeleton composite material, its composite with lithium metal, and their preparation methods and use | |
| Zhang et al. | High performance of electrochemical lithium storage batteries: ZnO-based nanomaterials for lithium-ion and lithium–sulfur batteries | |
| CN106450481B (en) | A kind of lithium ion battery and preparation method thereof | |
| CN106531992B (en) | A kind of composite material containing silicon and the preparation method and application thereof | |
| CN108461723A (en) | A kind of silicon based composite material and preparation method thereof for lithium ion battery | |
| CN105742599B (en) | Si-C composite material and preparation method thereof and negative electrode material and battery | |
| CN109585781A (en) | A kind of lithium ion battery negative electrode and the lithium ion battery using the pole piece | |
| CN104868094B (en) | Porous ruthenium dioxide and manganese dioxide combined electrode and preparation method and application thereof | |
| CN107565112A (en) | A kind of preparation method of graphene coated lithium ion secondary battery anode material | |
| CN109962240A (en) | Method for preparing anode slurry for lithium carbon fluoride battery with carbon nanotube as conductive agent | |
| Lu et al. | A yolk-shell structured CoS2@ NC@ CNC with double carbon shell coating from confined derivatization of ZIF-67 growth in carbon nanocages for superior Li storage | |
| CN109004220A (en) | A kind of boronic acid compounds modification lithium ion battery silicium cathode and preparation method thereof | |
| CN108091856A (en) | A kind of boehmite coated graphite composite negative pole material, preparation method and the usage | |
| Hu et al. | Excellent cyclic and rate performances of SiO/C/Graphite composites as Li-ion battery anode | |
| CN100383037C (en) | Carbon material and nano silicon composite materials and method for preparing same and use thereof | |
| CN108190963A (en) | A kind of hollow CoFe of multistage2O4Material, CoFe2O4The preparation method and application of/C composite | |
| Hai et al. | Facile controlled synthesis of spinel LiMn2O4 porous microspheres as cathode material for lithium ion batteries | |
| CN106654193A (en) | Preparation method of porous CoO@ nitrogen-doped carbon coaxial nanorod | |
| CN110336048A (en) | A kind of low-load amount ruthenium cladding ZIF-67 derivative and preparation method thereof and the application in lithium-air battery | |
| CN109768260A (en) | A kind of two cobalts of phosphatization/carbon composite and its preparation method and application | |
| CN110190265A (en) | A kind of preparation method of antimony-antimony oxide/redox graphene composite material | |
| Xing et al. | CeO2/Ce2S3 modified carbon nanotubes as efficient cathode materials for lithium-sulfur batteries | |
| CN106784845A (en) | A kind of aqueous inorganic glue and preparation method and application | |
| CN108695497A (en) | A kind of preparation method of three-dimensional porous carbon structure anode composite material of lithium sulfur battery | |
| CN110034292A (en) | A kind of 3-D ordered multiporous polypyrrole/zinc oxide lithium ion battery negative material and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |