CN105118956B - A kind of preparation method of three-dimensional porous material by different level - Google Patents
A kind of preparation method of three-dimensional porous material by different level Download PDFInfo
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- CN105118956B CN105118956B CN201510474813.9A CN201510474813A CN105118956B CN 105118956 B CN105118956 B CN 105118956B CN 201510474813 A CN201510474813 A CN 201510474813A CN 105118956 B CN105118956 B CN 105118956B
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- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/045—Electrochemical coating; Electrochemical impregnation
- H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- 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
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
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- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- 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
Abstract
A kind of preparation method of three-dimensional porous material by different level, it is related to a kind of preparation method of porous structure material.It is largely expanded the invention aims to solve existing high-capacity electrode material volume in charge and discharge process, destroys the pattern of original electrode material, causes the problem of cell performance decay.Method：First, micron order three-dimensional collector pre-treatment；2nd, colloidal solution is configured；3rd, colloid template is grown on micron order three-dimensional collector；4th, ionic liquid electrodeposition；5th, the colloid template on the micron order three-dimensional collector containing three-dimensional hierarchy skeleton is removed using annealing method or solvent method, obtains three-dimensional porous material by different level.Three-dimensional porous material by different level prepared by the present invention, first coulombic efficiency be up to more than 65%, after 100 times circulate, specific discharge capacity residue 989mAh/g~990mAh/g.The present invention can obtain a kind of preparation method of three-dimensional porous material by different level.
Description
Technical field
The present invention relates to a kind of preparation method of porous structure material.
Background technology：
The exhausted threat of future source of energy and startling, the new energy of exploitation Novel clean green of the pollution of current environment
Source is very urgent.The various energy-storage batteries such as fuel cell, solar cell, lithium ion battery start greatly to be paid close attention to.Battery
Electrode material performance be determine electrochmical power source performance key factor, the electrode material of traditional industry is generally dusty material,
Need to be bonded in conductive current collector using binding agent during its composite electrode, there is complex process and volume energy density is low
The problems such as.
By taking traditional lithium ion battery as an example, the carbon material with graphite as representative is existing lithium ion battery commercialization negative pole material
The main flow selection of material, however graphite cathode to there is theoretical capacity relatively low, the problems such as charge-discharge velocity is slow, it is difficult to meet produce reality
In to high power density, the active demand of high-energy-density negative material, the new electricity such as including germanium, silicon, transiting metal oxidation
The appearance of pole, to the new hope that the development of following electrode material brings, there is provided more rich selection, but it is new on these
Type electrode material research still suffer from some so with such problem urgently to be resolved hurrily, still also have a segment distance from practical application.
The huge volumetric expansion problem that the high-capacity electrode material such as germanium, silicon is all suffered from charge and discharge process needs solution
Certainly, no matter by which kind of mode, the embedding and removing reaction during circulating battery can all cause the volume of negative material swollen
It is swollen, so as to destroy the original pattern of negative material, and cause cell performance decay.
The content of the invention
It is largely expanded the invention aims to solve existing high-capacity electrode material volume in charge and discharge process, is broken
The pattern of original electrode material is broken, causes the problem of cell performance decay, and a kind of three-dimensional porous material by different level is provided
Preparation method.
A kind of preparation method of three-dimensional porous material by different level, completes according to the following steps：
First, micron order three-dimensional collector pre-treatment：
1. it is 10min~20min in the HCl of 1mol/L that micron order three-dimensional collector, is immersed in into concentration, is further taken out, and is obtained
Micron order three-dimensional collector after to HCl immersions；The micron order three-dimensional collection liquid surface rinsed after HCl soaks using absolute ethyl alcohol
2 times~4 times, then be dipped into it is ultrasonically treated in absolute ethyl alcohol further take out and dry twice, obtain dry micron order three-dimensional afflux
Body；
Step one 1. described in each ultrasonically treated time be 30min~40min, power be 50W~200W；
Step one 1. described in micron order three-dimensional collector be nickel screen or copper mesh；
2., by step one 1. in obtain dry micron order three-dimensional collector be immersed in aniline and 1-METHYLPYRROLIDONE
Mixed solution in 1h~2h, then by micron order three-dimensional collector take out, then in the drying box that temperature is 50 DEG C~70 DEG C dry
It is dry, then be cut out, a width of 1cm~1.5cm is obtained, the micron order three-dimensional collector after the treatment of a length of 4cm~5cm；
Step one 2. described in aniline and 1-METHYLPYRROLIDONE mixed solution in the mass fraction of aniline be
0.025%~0.050%；
2nd, colloidal solution is configured：
Colloid micro ball is distributed in deionized water, dispersant is added, colloidal solution is obtained；
Colloid micro ball described in step 2 is polystyrene microsphere, SiO2Microballoon, TiO2Microballoon or AgI microballoons；
Colloid micro ball and the mass ratio of deionized water described in step 2 are (0.1~0.5):100；
Dispersant and the mass ratio of deionized water described in step 2 are (0.025~0.050):100；
3rd, colloid template is grown on micron order three-dimensional collector：
The colloidal solution that will be obtained in step 2 ultrasonically treated 20min~30min in the case where ultrasonic power is 50W~200W,
Obtain it is ultrasonically treated after colloidal solution；Colloidal solution after again will be ultrasonically treated is heated to 50 DEG C~60 DEG C, then by a width of 1cm
~1.5cm, the micron order three-dimensional collector after the treatment of a length of 4cm~5cm is immersed at the ultrasound that temperature is 50 DEG C~60 DEG C
48h~72h in colloidal solution after reason, then colloidal solution is volatilized naturally at room temperature, obtaining growing has the micro- of colloid template
Meter level three-dimensional current collector plate；
4th, ionic liquid electrodeposition：
The micron order three-dimensional current collector plate that the growth that will be obtained in step 3 has colloid template cuts, and obtains radius for 50mm
Growth have colloid template micron order three-dimensional collector；Ionic liquid electrodeposition liquid is put into electrolytic cell, is made with platinum filament
It is comparison electrode, using filamentary silver as reference electrode, the growth with radius as 50mm has the micron order three-dimensional collector of colloid template
As working electrode, working electrode is immersed in ionic liquid electrodeposition liquid, it is three-dimensional in micron order using potentiostatic electrodeposition method
Deposited metal in colloid template hole on collector, obtains the micron order three-dimensional afflux containing three-dimensional hierarchy skeleton
Body；
Ionic liquid electrodeposition liquid described in step 4 is prepared as follows：By dissolving metal salts to 1- second
In the double trifluoromethanesulfonimide salt of base -3- methylimidazoles, ionic liquid electrodeposition liquid is obtained；Described ionic liquid electrodeposition
The concentration of slaine is 0.1mol/L~1mol/L in liquid；Described slaine is GeCl4Or SiCl4；
Use potentiostatic electrodeposition method described in step 4 is sunk in the colloid template hole on micron order three-dimensional collector
The voltage of product metal is 1.6V~2.4V, and current density is -5 × 10-3A/m2~-3 × 10-2A/m2；Sedimentation time be 5min~
60min, the temperature of electro-deposition is room temperature；
5th, the glue on the micron order three-dimensional collector of three-dimensional hierarchy skeleton will be contained using annealing method or solvent method
Body template is removed, and obtains three-dimensional porous material by different level；
The concrete operations of the annealing method described in step 5 are：Will be containing three-dimensional by different level with the heating rate of 3 DEG C/min
The micron order three-dimensional collector of structural framework rises to 200 DEG C~220 DEG C from room temperature, is incubated 60min~70min, then with 3 DEG C/min
Heating rate rise to 600 DEG C~620 DEG C from 200 DEG C~220 DEG C, 120min~130min is incubated, then with the drop of 5 DEG C/min
Warm speed is down to 200 DEG C~220 DEG C from 600 DEG C~620 DEG C, then is naturally cooling to room temperature, and annealing terminates；
The concrete operations of the solvent method described in step 5 are：Using isopropanol to containing three-dimensional hierarchy skeleton
Micron order three-dimensional collector is rinsed 3 times~5 times, then is immersed in 5min~120min in tetrahydrofuran, is immersed again after taking-up
5min~120min in isopropanol, dries after taking-up, that is, complete solvent method；The mass fraction of described isopropanol is
99.9%；The mass fraction of described tetrahydrofuran is 99.9%.
Compared with prior art, the invention has the advantages that：
First, the present invention uses out-of-flatness, and rough micron order three-dimensional current collector plate (nickel screen or copper mesh) as substrate,
Existing common colloid template preparation method is difficult to meet this requirement；The present invention has been obtained with semiconductor alloy germanium or silicon as skeleton
Three-dimensional porous structure material by different level, be used directly in battery electrode material；
2nd, the present invention uses micron order three-dimensional current collector plate (nickel screen or copper mesh), there is provided electric conductivity is good, hole
The big active ingredient carriers of rate；When active material is the metals such as germanium, the theoretical specific capacity of battery can be greatly improved；Micron order three
Dimension current collector plate (nickel screen or copper mesh) itself is porous, and active material configuration is three-dimensional porous structure, in macroscopic three dimensional loose structure
On increased microcosmic three-dimensional porous structure, the contact area of active material and ionic liquid electrodeposition liquid can be effectively increased,
During embedding and removing, effective buffers active mass volume expansion improves battery performance；
3rd, the present invention is in preparation process, and preparation process is simple, preparation condition are gentle, cheap；In this approach, no
Only can construct most common metals be skeleton nano-porous structure, and commonsense method be able to can not be deposited germanium,
The transient period metal such as silicon, in ionic liquid electrodeposition mode, is deposited in colloid template hole, obtains three-dimensional layering by different level
Secondary porous structure material；
4th, three-dimensional porous material by different level prepared by the present invention, relative to common material excellent performance, coulombic efficiency first
Up to more than 65%, after 100 times circulate, specific discharge capacity residue 989mAh/g~990mAh/g, with the second circle electric discharge ratio
Capacity 1563mAh/g~1564mAh/g is compared, and remaining 63%~64%；Under high magnification, circulated with 3A/g current densities, put
Electric specific capacity is up to 485%~486%；Compared with direct ion liquid electric deposit Germanium obtains material on nickel screen, prepared by the present invention
Three-dimensional porous material by different level apparently higher than this Common deposition germanium material, coulombic efficiency is less than 40% to this material first, passes through
After 100 circulations, specific discharge capacity is remaining to be less than 200mAh/g, is circulated under high magnification 3A/g current densities, specific discharge capacity
Residue is less than 400mAh/g.
The present invention can obtain a kind of preparation method of three-dimensional porous material by different level.
Brief description of the drawings
Fig. 1 is that the growth that the step 3 of embodiment one is obtained has colloid template in the micron order three-dimensional current collector plate of colloid template
Amplify 2500 times of SEM figures；
Fig. 2 is that the growth that the step 3 of embodiment one is obtained has colloid template in the micron order three-dimensional current collector plate of colloid template
Amplify 500 times of SEM figures；
Fig. 3 is that the growth that the step 3 of embodiment two is obtained has colloid template in the micron order three-dimensional current collector plate of colloid template
Amplify 4000 times of SEM figures；
Fig. 4 is that the growth that the step 3 of embodiment two is obtained has colloid template in the micron order three-dimensional current collector plate of colloid template
Amplify 1300 times of SEM figures；
Fig. 5 is the SEM figures that the three-dimensional porous material by different level that the step 5 of embodiment one is obtained amplifies 7000 times；
Fig. 6 is the SEM figures that the three-dimensional porous material by different level that the step 5 of embodiment two is obtained amplifies 10000 times；
Fig. 7 is three-dimensional charge and discharge of the porous material in the case where current density is 0.1A/g by different level that the step 5 of embodiment one is obtained
Electric cycle performance figure；
Fig. 8 is the high rate performance figure of the three-dimensional porous material by different level that the step 5 of embodiment one is obtained；1 is implementation in Fig. 8
High rate performance curve of the three-dimensional porous material by different level that the step 5 of example one is obtained in the case where the density of charging current is 0.1A/g, 2 are
High rate performance curve of the three-dimensional porous material by different level that the step 5 of embodiment one is obtained in the case where the density of charging current is 0.3A/g,
3 is that high rate performance of the three-dimensional porous material by different level that obtains of the step 5 of embodiment one in the case where the density of charging current is 0.5A/g is bent
Line, 4 is high rate performance of the three-dimensional porous material by different level that obtains of the step 5 of embodiment one in the case where the density of charging current is 1A/g
Curve, 5 is that the three-dimensional porous material by different level that the step 5 of embodiment one is obtained is forthright again in the case where the density of charging current is 3A/g
Can curve；
Fig. 9 is the high rate performance figure of the three-dimensional porous material by different level that the step 5 of embodiment one is obtained；1 is implementation in Fig. 9
High rate performance curve of the three-dimensional porous material by different level that the step 5 of example one is obtained in the case where discharge current density is 0.1A/g, 2 are
High rate performance curve of the three-dimensional porous material by different level that the step 5 of embodiment one is obtained in the case where discharge current density is 0.3A/g,
3 is that high rate performance of the three-dimensional porous material by different level that obtains of the step 5 of embodiment one in the case where discharge current density is 0.5A/g is bent
Line, 4 is high rate performance of the three-dimensional porous material by different level that obtains of the step 5 of embodiment one in the case where discharge current density is 1A/g
Curve, 5 is that the three-dimensional porous material by different level that the step 5 of embodiment one is obtained is forthright again in the case where discharge current density is 3A/g
Can curve.
Specific embodiment
Specific embodiment one：Present embodiment is that a kind of preparation method of three-dimensional porous material by different level is by following step
Rapid completion：
First, micron order three-dimensional collector pre-treatment：
1. it is 10min~20min in the HCl of 1mol/L that micron order three-dimensional collector, is immersed in into concentration, is further taken out, and is obtained
Micron order three-dimensional collector after to HCl immersions；The micron order three-dimensional collection liquid surface rinsed after HCl soaks using absolute ethyl alcohol
2 times~4 times, then be dipped into it is ultrasonically treated in absolute ethyl alcohol further take out and dry twice, obtain dry micron order three-dimensional afflux
Body；
Step one 1. described in each ultrasonically treated time be 30min~40min, power be 50W~200W；
Step one 1. described in micron order three-dimensional collector be nickel screen or copper mesh；
2., by step one 1. in obtain dry micron order three-dimensional collector be immersed in aniline and 1-METHYLPYRROLIDONE
Mixed solution in 1h~2h, then by micron order three-dimensional collector take out, then in the drying box that temperature is 50 DEG C~70 DEG C dry
It is dry, then be cut out, a width of 1cm~1.5cm is obtained, the micron order three-dimensional collector after the treatment of a length of 4cm~5cm；
Step one 2. described in aniline and 1-METHYLPYRROLIDONE mixed solution in the mass fraction of aniline be
0.025%~0.050%；
2nd, colloidal solution is configured：
Colloid micro ball is distributed in deionized water, dispersant is added, colloidal solution is obtained；
Colloid micro ball described in step 2 is polystyrene microsphere, SiO2Microballoon, TiO2Microballoon or AgI microballoons；
Colloid micro ball and the mass ratio of deionized water described in step 2 are (0.1~0.5):100；
Dispersant and the mass ratio of deionized water described in step 2 are (0.025~0.050):100；
3rd, colloid template is grown on micron order three-dimensional collector：
The colloidal solution that will be obtained in step 2 ultrasonically treated 20min~30min in the case where ultrasonic power is 50W~200W,
Obtain it is ultrasonically treated after colloidal solution；Colloidal solution after again will be ultrasonically treated is heated to 50 DEG C~60 DEG C, then by a width of 1cm
~1.5cm, the micron order three-dimensional collector after the treatment of a length of 4cm~5cm is immersed at the ultrasound that temperature is 50 DEG C~60 DEG C
48h~72h in colloidal solution after reason, then colloidal solution is volatilized naturally at room temperature, obtaining growing has the micro- of colloid template
Meter level three-dimensional current collector plate；
4th, ionic liquid electrodeposition：
The micron order three-dimensional current collector plate that the growth that will be obtained in step 3 has colloid template cuts, and obtains radius for 50mm
Growth have colloid template micron order three-dimensional collector；Ionic liquid electrodeposition liquid is put into electrolytic cell, is made with platinum filament
It is comparison electrode, using filamentary silver as reference electrode, the growth with radius as 50mm has the micron order three-dimensional collector of colloid template
As working electrode, working electrode is immersed in ionic liquid electrodeposition liquid, it is three-dimensional in micron order using potentiostatic electrodeposition method
Deposited metal in colloid template hole on collector, obtains the micron order three-dimensional afflux containing three-dimensional hierarchy skeleton
Body；
Ionic liquid electrodeposition liquid described in step 4 is prepared as follows：By dissolving metal salts to 1- second
In the double trifluoromethanesulfonimide salt of base -3- methylimidazoles, ionic liquid electrodeposition liquid is obtained；Described ionic liquid electrodeposition
The concentration of slaine is 0.1mol/L~1mol/L in liquid；Described slaine is GeCl4Or SiCl4；
Use potentiostatic electrodeposition method described in step 4 is sunk in the colloid template hole on micron order three-dimensional collector
The voltage of product metal is 1.6V~2.4V, and current density is -5 × 10-3A/m2~-3 × 10-2A/m2；Sedimentation time be 5min~
60min, the temperature of electro-deposition is room temperature；
5th, the glue on the micron order three-dimensional collector of three-dimensional hierarchy skeleton will be contained using annealing method or solvent method
Body template is removed, and obtains three-dimensional porous material by different level；
The concrete operations of the annealing method described in step 5 are：Will be containing three-dimensional by different level with the heating rate of 3 DEG C/min
The micron order three-dimensional collector of structural framework rises to 200 DEG C~220 DEG C from room temperature, is incubated 60min~70min, then with 3 DEG C/min
Heating rate rise to 600 DEG C~620 DEG C from 200 DEG C~220 DEG C, 120min~130min is incubated, then with the drop of 5 DEG C/min
Warm speed is down to 200 DEG C~220 DEG C from 600 DEG C~620 DEG C, then is naturally cooling to room temperature, and annealing terminates；
The concrete operations of the solvent method described in step 5 are：Using isopropanol to containing three-dimensional hierarchy skeleton
Micron order three-dimensional collector is rinsed 3 times~5 times, then is immersed in 5min~120min in tetrahydrofuran, is immersed again after taking-up
5min~120min in isopropanol, dries after taking-up, that is, complete solvent method；The mass fraction of described isopropanol is
99.9%；The mass fraction of described tetrahydrofuran is 99.9%.
Compared with prior art, present embodiment has the advantage that：
First, present embodiment uses out-of-flatness, and three-dimensional current collector plate (the nickel screen or copper mesh) conduct of rough micron order
Substrate, existing common colloid template preparation method is difficult to meet this requirement；Present embodiment has been obtained with semiconductor alloy germanium
Or silicon is the three-dimensional porous structure material by different level of skeleton, is used directly in battery electrode material；
2nd, present embodiment uses micron order three-dimensional current collector plate (nickel screen or copper mesh), there is provided electric conductivity is good,
The big active ingredient carriers of porosity；When active material is the metals such as germanium, the theoretical specific capacity of battery can be greatly improved；Micron
The three-dimensional current collector plate (nickel screen or copper mesh) of level itself is porous, and active material configuration is three-dimensional porous structure, porous in macroscopic three dimensional
Microcosmic three-dimensional porous structure is increased in structure, the contact surface of active material and ionic liquid electrodeposition liquid can be effectively increased
Product, during embedding and removing, effective buffers active mass volume expansion improves battery performance；
3rd, present embodiment is in preparation process, and preparation process is simple, preparation condition are gentle, cheap；With this side
Method, can not merely construct most common metals and be the nano-porous structure of skeleton, and can not deposit commonsense method
The transient period metal such as germanium, silicon, in ionic liquid electrodeposition mode, be deposited in colloid template hole, obtain by different level three
Tie up porous structure material by different level；
4th, three-dimensional porous material by different level prepared by present embodiment, relative to common material excellent performance, coulomb first
Efficiency high up to more than 65%, after 100 times circulate, with the second circle put by specific discharge capacity residue 989mAh/g~990mAh/g
Electric specific capacity 1563mAh/g~1564mAh/g is compared, and remaining 63%~64%；Under high magnification, to be followed under 3A/g current densities
Ring, specific discharge capacity is up to 485%~486%；Compared with direct ion liquid electric deposit Germanium obtains material on nickel screen, this implementation
, apparently higher than this Common deposition germanium material, coulombic efficiency is less than three-dimensional porous material by different level prepared by mode this material first
40%, after 100 times circulate, specific discharge capacity is remaining to be less than 200mAh/g, is circulated under high magnification 3A/g current densities, puts
Electric specific capacity is remaining to be less than 400mAh/g.
Present embodiment can obtain a kind of preparation method of three-dimensional porous material by different level.
Specific embodiment two：Present embodiment is with the difference of specific embodiment one：Step nickel 1. described in one
The thickness of net is 1.5mm, and PPI is 110, and aperture is 0.3mm, and surface density is 300g/m2~340g/m2.Other steps and specific reality
Apply mode one identical.
Specific embodiment three：One of present embodiment and specific embodiment one or two difference is：Step one 1. in
The thickness of described copper mesh is 1.6mm, and PPI is 90, and aperture is 0.28mm, and surface density is 430g/cm2~470g/cm2.Other steps
Suddenly it is identical with specific embodiment one or two.
Specific embodiment four：One of present embodiment and specific embodiment one to three difference is：Step one 2. in
The mass fraction of aniline is 0.025% in described aniline and the mixed solution of 1-METHYLPYRROLIDONE.Other steps with it is specific
Implementation method one to three is identical.
Specific embodiment five：One of present embodiment and specific embodiment one to four difference is：Institute in step 2
The particle diameter of the colloid micro ball stated is 100nm~1000nm.Other steps are identical with specific embodiment one to four.
Specific embodiment six：One of present embodiment and specific embodiment one to five difference is：Institute in step 2
The dispersant stated is polysorbate, neopelex, octadecane alcohol radical APEO or di-2-ethylhexylphosphine oxide naphthalene sulfonic acids
Sodium.Other steps are identical with specific embodiment one to five.
Specific embodiment seven：One of present embodiment and specific embodiment one to six difference is：Will in step 3
The colloidal solution obtained in step 2 ultrasonic power be 200W under ultrasonically treated 30min, obtain it is ultrasonically treated after colloid it is molten
Liquid；Colloidal solution after again will be ultrasonically treated is heated to 55 DEG C, then by a width of 1.5cm, the micron order three after the treatment of a length of 4m
It is 60h in colloidal solution after 55 DEG C ultrasonically treated that dimension collector is immersed in temperature, then colloidal solution is natural at room temperature
Volatilization, obtains growing the micron order for having colloid template three-dimensional current collector plate.Other steps are identical with specific embodiment one to six.
Specific embodiment eight：One of present embodiment and specific embodiment one to seven difference is：Institute in step 4
The ionic liquid electrodeposition liquid stated is prepared as follows：By dissolving metal salts to the double trifluoros of 1- ethyl-3-methylimidazoles
In sulfonyl methane inferior amine salt, ionic liquid electrodeposition liquid is obtained；The concentration of slaine is in described ionic liquid electrodeposition liquid
0.5mol/L；Described slaine is GeCl4Or SiCl4.Other steps are identical with specific embodiment one to seven.
Specific embodiment nine：One of present embodiment and specific embodiment one to eight difference is：Institute in step 4
It is 2V that states uses the voltage of deposited metal in colloid template hole of the potentiostatic electrodeposition method on micron order three-dimensional collector, electricity
Current density is -4 × 10-2A/m2；Sedimentation time is 20min, and the temperature of electro-deposition is room temperature.Other steps and specific embodiment
One to eight is identical.
Specific embodiment ten：One of present embodiment and specific embodiment one to nine difference is：Institute in step 5
The concrete operations of the annealing method stated are：The micron order three of three-dimensional hierarchy skeleton will be contained with the heating rate of 3 DEG C/min
Dimension collector rises to 200 DEG C from room temperature, is incubated 60min, then 600 DEG C, insulation are risen to from 200 DEG C with the heating rate of 3 DEG C/min
120min, is then down to 200 DEG C from 600 DEG C with the rate of temperature fall of 5 DEG C/min, then is naturally cooling to room temperature, and annealing terminates.Other
Step is identical with specific embodiment one to nine.
Beneficial effects of the present invention are verified using following examples：
Embodiment one：A kind of preparation method of three-dimensional porous material by different level, completes according to the following steps：
First, micron order three-dimensional collector pre-treatment：
1. it is 20min in the HCl of 1mol/L that micron order three-dimensional collector, is immersed in into concentration, is further taken out, and obtains HCl leachings
Micron order three-dimensional collector after bubble；Micron order three-dimensional collection liquid surface after being soaked using absolute ethyl alcohol flushing HCl 3 times, then
Be dipped into it is ultrasonically treated in absolute ethyl alcohol further take out and dry twice, obtain dry micron order three-dimensional collector；
Step one 1. described in each ultrasonically treated time be 30min, power is 200W；
Step one 1. described in micron order three-dimensional collector be nickel screen；The thickness of described nickel screen is 1.5mm, and PPI is
110, aperture is 0.3mm, and surface density is 320g/m2；
2., by step one 1. in obtain dry micron order three-dimensional collector be immersed in aniline and 1-METHYLPYRROLIDONE
Mixed solution in 1h~2h, then by micron order three-dimensional collector take out, then in the drying box that temperature is 50 DEG C~70 DEG C dry
It is dry, then be cut out, a width of 1.5cm is obtained, the micron order three-dimensional collector after the treatment of a length of 4cm；
Step one 2. described in aniline and 1-METHYLPYRROLIDONE mixed solution in the mass fraction of aniline be
0.025%；
2nd, colloidal solution is configured：
Colloid micro ball is distributed in deionized water, dispersant is added, colloidal solution is obtained；
Colloid micro ball described in step 2 is polystyrene microsphere；The particle diameter of described polystyrene microsphere is 529nm；
Colloid micro ball and the mass ratio of deionized water described in step 2 are 0.2:100；
Dispersant and the mass ratio of deionized water described in step 2 are 0.025:100；
Dispersant described in step 2 is polysorbate；
3rd, colloid template is grown on micron order three-dimensional collector：
The colloidal solution that will be obtained in step 2 ultrasonically treated 20min in the case where ultrasonic power is 200W, obtains ultrasonically treated
Colloidal solution afterwards；Colloidal solution after again will be ultrasonically treated is heated to 60 DEG C, then by a width of 1.5cm, after the treatment of a length of 4cm
Micron order three-dimensional collector to be immersed in temperature be 72h in colloidal solution after 60 DEG C ultrasonically treated, then colloidal solution is existed
Volatilize naturally at room temperature, obtain growing the micron order for having colloid template three-dimensional current collector plate；
4th, ionic liquid electrodeposition：
The micron order three-dimensional current collector plate that the growth that will be obtained in step 3 has colloid template cuts, and obtains radius for 50mm
Growth have colloid template micron order three-dimensional collector；Ionic liquid electrodeposition liquid is put into electrolytic cell, is made with platinum filament
It is comparison electrode, using filamentary silver as reference electrode, the growth with radius as 50mm has the micron order three-dimensional collector of colloid template
As working electrode, working electrode is immersed in ionic liquid electrodeposition liquid, it is three-dimensional in micron order using potentiostatic electrodeposition method
Deposited metal in colloid template hole on collector, obtains the micron order three-dimensional afflux containing three-dimensional hierarchy skeleton
Body；
Ionic liquid electrodeposition liquid described in step 4 is prepared as follows：By dissolving metal salts to 1- second
In the double trifluoromethanesulfonimide salt of base -3- methylimidazoles, ionic liquid electrodeposition liquid is obtained；Described ionic liquid electrodeposition
The concentration of slaine is 0.1mol/L in liquid；Described slaine is GeCl4；
Use potentiostatic electrodeposition method described in step 4 is sunk in the colloid template hole on micron order three-dimensional collector
The voltage of product metal is 2V, and current density is -4 × 10-2A/m2；Sedimentation time is 20min, and the temperature of electro-deposition is room temperature；
5th, the colloid template on the micron order three-dimensional collector containing three-dimensional hierarchy skeleton is gone using solvent method
Remove, obtain three-dimensional porous material by different level；
The concrete operations of the solvent method described in step 5 are：Using isopropanol to containing three-dimensional hierarchy skeleton
Micron order three-dimensional collector is rinsed 4 times, then is immersed in 30min in tetrahydrofuran, is immersed in isopropanol again after taking-up
30min, dries after taking-up, that is, complete solvent method；The mass fraction of described isopropanol is 99.9%；Described tetrahydrofuran
Mass fraction is 99.9%.
Fig. 1 is that the growth that the step 3 of embodiment one is obtained has colloid template in the micron order three-dimensional current collector plate of colloid template
Amplify 2500 times of SEM figures；
Fig. 2 is that the growth that the step 3 of embodiment one is obtained has colloid template in the micron order three-dimensional current collector plate of colloid template
Amplify 500 times of SEM figures；
Fig. 5 is the SEM figures that the three-dimensional porous material by different level that the step 5 of embodiment one is obtained amplifies 7000 times；
From fig. 1, it can be seen that by after step 3, growing the colloid mould that regular orderly particle diameter is 529nm on nickel screen skeleton
Hardened structure；Fig. 2 is same region low range SEM figure, as can be seen from Figure 2, it is known that large area region is all in micron order three-dimensional current collector plate
With colloid template；
As can be seen from Figure 5, by after step 5, colloid micro ball is removed, the three-dimensional loose structure by different level of large area is obtained.
Fig. 7 is three-dimensional charge and discharge of the porous material in the case where current density is 0.1A/g by different level that the step 5 of embodiment one is obtained
Electric cycle performance figure；
As can be seen from Figure 7, coulombic efficiency is 68.98%, second to the three-dimensional porous material by different level that prepared by embodiment one first
Circle charging and discharging capacity is respectively 1444.5mAh/g and 1563.2mAh/g, after 100 times circulate, charging and discharging capacity difference
It is 985.5mAh/g and 989.7mAh/g.
Fig. 8 is the high rate performance figure of the three-dimensional porous material by different level that the step 5 of embodiment one is obtained；1 is implementation in Fig. 8
High rate performance curve of the three-dimensional porous material by different level that the step 5 of example one is obtained in the case where the density of charging current is 0.1A/g, 2 are
High rate performance curve of the three-dimensional porous material by different level that the step 5 of embodiment one is obtained in the case where the density of charging current is 0.3A/g,
3 is that high rate performance of the three-dimensional porous material by different level that obtains of the step 5 of embodiment one in the case where the density of charging current is 0.5A/g is bent
Line, 4 is high rate performance of the three-dimensional porous material by different level that obtains of the step 5 of embodiment one in the case where the density of charging current is 1A/g
Curve, 5 is that the three-dimensional porous material by different level that the step 5 of embodiment one is obtained is forthright again in the case where the density of charging current is 3A/g
Can curve；
Fig. 9 is the high rate performance figure of the three-dimensional porous material by different level that the step 5 of embodiment one is obtained；1 is implementation in Fig. 9
High rate performance curve of the three-dimensional porous material by different level that the step 5 of example one is obtained in the case where discharge current density is 0.1A/g, 2 are
High rate performance curve of the three-dimensional porous material by different level that the step 5 of embodiment one is obtained in the case where discharge current density is 0.3A/g,
3 is that high rate performance of the three-dimensional porous material by different level that obtains of the step 5 of embodiment one in the case where discharge current density is 0.5A/g is bent
Line, 4 is high rate performance of the three-dimensional porous material by different level that obtains of the step 5 of embodiment one in the case where discharge current density is 1A/g
Curve, 5 is that the three-dimensional porous material by different level that the step 5 of embodiment one is obtained is forthright again in the case where discharge current density is 3A/g
Can curve.
Knowable to Fig. 8 and Fig. 9, the high rate performance of the three-dimensional porous material by different level that the step 5 of embodiment one is obtained is preferable,
Under the current density of 3A/g, charging and discharging capacity is respectively 481.8mAh/g and 485.4mAh/g, when the electricity for recovering 0.1A/g
During current density, charging and discharging capacity returns to 858.7mAh/g and 956.7mAh/g respectively, close to the discharge and recharge specific volume of the initial segment
Amount.
Embodiment two：A kind of preparation method of three-dimensional porous material by different level, completes according to the following steps：
First, micron order three-dimensional collector pre-treatment：
1. it is 20min in the HCl of 1mol/L that micron order three-dimensional collector, is immersed in into concentration, is further taken out, and obtains HCl leachings
Micron order three-dimensional collector after bubble；Micron order three-dimensional collection liquid surface after being soaked using absolute ethyl alcohol flushing HCl 3 times, then
Be dipped into it is ultrasonically treated in absolute ethyl alcohol further take out and dry twice, obtain dry micron order three-dimensional collector；
Step one 1. described in each ultrasonically treated time be 30min, power is 200W；
Step one 1. described in micron order three-dimensional collector be nickel screen；The thickness of described nickel screen is 1.5mm, and PPI is
110, aperture is 0.3mm, and surface density is 320g/m2；
2., by step one 1. in obtain dry micron order three-dimensional collector be immersed in aniline and 1-METHYLPYRROLIDONE
Mixed solution in 2h, then micron order three-dimensional collector is taken out, then dried in the drying box that temperature is 50 DEG C, then cut
Cut out, obtain a width of 1.5cm, the micron order three-dimensional collector after the treatment of a length of 4cm；
Step one 2. described in aniline and 1-METHYLPYRROLIDONE mixed solution in the mass fraction of aniline be
0.025%；
2nd, colloidal solution is configured：
Colloid micro ball is distributed in deionized water, dispersant is added, colloidal solution is obtained；
Colloid micro ball described in step 2 is polystyrene microsphere；The particle diameter of described polystyrene microsphere is 703nm；
Colloid micro ball and the mass ratio of deionized water described in step 2 are 0.2:100；
Dispersant and the mass ratio of deionized water described in step 2 are 0.025:100；
Dispersant described in step 2 is polysorbate；
3rd, colloid template is grown on micron order three-dimensional collector：
The colloidal solution that will be obtained in step 2 ultrasonically treated 20min in the case where ultrasonic power is 200W, obtains ultrasonically treated
Colloidal solution afterwards；Colloidal solution after again will be ultrasonically treated is heated to 60 DEG C, then by a width of 1.5cm, after the treatment of a length of 4cm
Micron order three-dimensional collector to be immersed in temperature be 72h in colloidal solution after 60 DEG C ultrasonically treated, then colloidal solution is existed
Volatilize naturally at room temperature, obtain growing the micron order for having colloid template three-dimensional current collector plate；
4th, ionic liquid electrodeposition：
The micron order three-dimensional current collector plate that the growth that will be obtained in step 3 has colloid template cuts, and obtains radius for 50mm
Growth have colloid template micron order three-dimensional collector；Ionic liquid electrodeposition liquid is put into electrolytic cell, is made with platinum filament
It is comparison electrode, using filamentary silver as reference electrode, the growth with radius as 50mm has the micron order three-dimensional collector of colloid template
As working electrode, working electrode is immersed in ionic liquid electrodeposition liquid, it is three-dimensional in micron order using potentiostatic electrodeposition method
Deposited metal in colloid template hole on collector, obtains the micron order three-dimensional afflux containing three-dimensional hierarchy skeleton
Body；
Ionic liquid electrodeposition liquid described in step 4 is prepared as follows：By dissolving metal salts to 1- second
In the double trifluoromethanesulfonimide salt of base -3- methylimidazoles, ionic liquid electrodeposition liquid is obtained；Described ionic liquid electrodeposition
The concentration of slaine is 0.1mol/L in liquid；Described slaine is GeCl4；
Use potentiostatic electrodeposition method described in step 4 is sunk in the colloid template hole on micron order three-dimensional collector
The voltage of product metal is 2V, and current density is -4 × 10-2A/m2；Sedimentation time is 20min, and the temperature of electro-deposition is room temperature；
5th, the colloid template on the micron order three-dimensional collector containing three-dimensional hierarchy skeleton is gone using annealing method
Remove, obtain three-dimensional porous material by different level；
The concrete operations of the annealing method described in step 5 are：Will be containing three-dimensional by different level with the heating rate of 3 DEG C/min
The micron order three-dimensional collector of structural framework rises to 200 DEG C from room temperature, is incubated 60min, then with the heating rate of 3 DEG C/min from
200 DEG C rise to 600 DEG C, are incubated 120min, and 200 DEG C, then Temperature fall are then down to from 600 DEG C with the rate of temperature fall of 5 DEG C/min
To room temperature, annealing terminates.
Fig. 3 is that the growth that the step 3 of embodiment two is obtained has colloid template in the micron order three-dimensional current collector plate of colloid template
Amplify 4000 times of SEM figures；
Fig. 4 is that the growth that the step 3 of embodiment two is obtained has colloid template in the micron order three-dimensional current collector plate of colloid template
Amplify 1300 times of SEM figures；
Fig. 6 is the SEM figures that the three-dimensional porous material by different level that the step 5 of embodiment two is obtained amplifies 10000 times；
Knowable to Fig. 3 and Fig. 4, by after step 3, growing the glue that regular orderly particle diameter is 703nm on nickel screen skeleton
Body formwork structure；Fig. 2 is same region low range SEM figures, it is known that large area region all carries glue in micron order three-dimensional current collector plate
Body template；
As can be seen from Figure 6, by after step 5, colloid micro ball is removed, the three-dimensional loose structure by different level of large area is obtained.
The three-dimensional porous material by different level that the step 5 of embodiment two is obtained, coulomb is electric in 0.1A/g more than 55% first
Cyclical stability is good under current density, and after 100 times circulate, charging and discharging capacity is still in more than 900mAh/g；It is forthright again
Can be good, under 3A/g current densities, more than charging and discharging capacity 400mAh/g, when 0.1A/g current densities are recovered, charge and discharge
Electric specific capacity returns to more than 850mAh/g, close to the charging and discharging capacity of the initial segment.
Claims (10)
1. a kind of a kind of preparation method of three-dimensional porous material by different level, it is characterised in that preparation of three-dimensional porous material by different level
Method is completed according to the following steps：
First, micron order three-dimensional collector pre-treatment：
1. it is 10min~20min in the HCl of 1mol/L that micron order three-dimensional collector, is immersed in into concentration, is further taken out, and obtains HCl
Micron order three-dimensional collector after immersion；The micron order three-dimensional collection liquid surface 2 times rinsed after HCl soaks using absolute ethyl alcohol~
4 times, then be dipped into it is ultrasonically treated in absolute ethyl alcohol further take out and dry twice, obtain dry micron order three-dimensional collector；
Step one 1. described in each ultrasonically treated time be 30min~40min, power be 50W~200W；
Step one 1. described in micron order three-dimensional collector be nickel screen or copper mesh；
2., by step one 1. in the dry micron order three-dimensional collector that obtains be immersed in the mixed of aniline and 1-METHYLPYRROLIDONE
1h~2h in solution is closed, then micron order three-dimensional collector is taken out, then dried in the drying box that temperature is 50 DEG C~70 DEG C, then
It is cut out, obtains a width of 1cm~1.5cm, the micron order three-dimensional collector after the treatment of a length of 4cm~5cm；
Step one 2. described in aniline and 1-METHYLPYRROLIDONE mixed solution in aniline mass fraction for 0.025%~
0.050%；
2nd, colloidal solution is configured：
Colloid micro ball is distributed in deionized water, dispersant is added, colloidal solution is obtained；
Colloid micro ball described in step 2 is polystyrene microsphere, SiO2Microballoon, TiO2Microballoon or AgI microballoons；
Colloid micro ball and the mass ratio of deionized water described in step 2 are (0.1~0.5):100；
Dispersant and the mass ratio of deionized water described in step 2 are (0.025~0.050):100；
3rd, colloid template is grown on micron order three-dimensional collector：
The colloidal solution that will be obtained in step 2 ultrasonically treated 20min~30min in the case where ultrasonic power is 50W~200W, obtains
Colloidal solution after ultrasonically treated；Colloidal solution after again will be ultrasonically treated is heated to 50 DEG C~60 DEG C, then by a width of 1cm~
1.5cm, it is 50 DEG C~60 DEG C ultrasonically treated that the micron order three-dimensional collector after the treatment of a length of 4cm~5cm is immersed in temperature
48h~72h in colloidal solution afterwards, then colloidal solution is volatilized naturally at room temperature, obtain growing the micron for having colloid template
The three-dimensional current collector plate of level；
4th, ionic liquid electrodeposition：
The micron order three-dimensional current collector plate that the growth that will be obtained in step 3 has colloid template cuts, and obtains the life that radius is 50mm
Length has the micron order three-dimensional collector of colloid template；Ionic liquid electrodeposition liquid is put into electrolytic cell, using platinum filament as right
Than electrode, using filamentary silver as reference electrode, the growth using radius as 50mm have colloid template micron order three-dimensional collector as
Working electrode, working electrode is immersed in ionic liquid electrodeposition liquid, using potentiostatic electrodeposition method in micron order three-dimensional afflux
Deposited metal in colloid template hole on body, obtains the micron order three-dimensional collector containing three-dimensional hierarchy skeleton；
Ionic liquid electrodeposition liquid described in step 4 is prepared as follows：By dissolving metal salts to 1- ethyls -3-
In the double trifluoromethanesulfonimide salt of methylimidazole, ionic liquid electrodeposition liquid is obtained；In described ionic liquid electrodeposition liquid
The concentration of slaine is 0.1mol/L~1mol/L；Described slaine is GeCl4Or SiCl4；
Use potentiostatic electrodeposition method described in step 4 deposits gold in the colloid template hole on micron order three-dimensional collector
The voltage of category is 1.6V~2.4V, and current density is -5 × 10-3A/m2~-3 × 10-2A/m2；Sedimentation time be 5min~
60min, the temperature of electro-deposition is room temperature；
5th, the colloid mould on the micron order three-dimensional collector of three-dimensional hierarchy skeleton will be contained using annealing method or solvent method
Plate is removed, and obtains three-dimensional porous material by different level；
The concrete operations of the annealing method described in step 5 are：Three-dimensional hierarchy will be contained with the heating rate of 3 DEG C/min
The micron order three-dimensional collector of skeleton rises to 200 DEG C~220 DEG C from room temperature, is incubated 60min~70min, then with the liter of 3 DEG C/min
Warm speed rises to 600 DEG C~620 DEG C from 200 DEG C~220 DEG C, is incubated 120min~130min, then with the cooling speed of 5 DEG C/min
Rate is down to 200 DEG C~220 DEG C from 600 DEG C~620 DEG C, then is naturally cooling to room temperature, and annealing terminates；
The concrete operations of the solvent method described in step 5 are：Using isopropanol to the micron containing three-dimensional hierarchy skeleton
The three-dimensional collector of level is rinsed 3 times~5 times, then is immersed in 5min~120min in tetrahydrofuran, is immersed in again after taking-up different
5min~120min in propyl alcohol, dries after taking-up, that is, complete solvent method；The mass fraction of described isopropanol is 99.9%；Institute
The mass fraction of the tetrahydrofuran stated is 99.9%.
2. the preparation method of a kind of three-dimensional porous material by different level according to claim 1, it is characterised in that step one is 1.
Described in nickel screen thickness be 1.5mm, PPI is 110, and aperture is 0.3mm, and surface density is 300g/m2~340g/m2。
3. the preparation method of a kind of three-dimensional porous material by different level according to claim 1, it is characterised in that step one is 1.
Described in copper mesh thickness be 1.6mm, PPI is 90, and aperture is 0.28mm, and surface density is 430g/m2~470g/m2。
4. the preparation method of a kind of three-dimensional porous material by different level according to claim 1, it is characterised in that step one is 2.
Described in aniline and 1-METHYLPYRROLIDONE mixed solution in aniline mass fraction be 0.025%.
5. the preparation method of a kind of three-dimensional porous material by different level according to claim 1, it is characterised in that in step 2
The particle diameter of described colloid micro ball is 100nm~1000nm.
6. the preparation method of a kind of three-dimensional porous material by different level according to claim 1, it is characterised in that in step 2
Described dispersant is polysorbate, neopelex, octadecane alcohol radical APEO or di-2-ethylhexylphosphine oxide naphthalene sulphur
Sour sodium.
7. the preparation method of a kind of three-dimensional porous material by different level according to claim 1, it is characterised in that in step 3
The colloidal solution that will be obtained in step 2 ultrasonic power be 200W under ultrasonically treated 30min, obtain it is ultrasonically treated after colloid
Solution；Colloidal solution after again will be ultrasonically treated is heated to 55 DEG C, then by a width of 1.5cm, the micron order after the treatment of a length of 4cm
It is 60h in colloidal solution after 55 DEG C ultrasonically treated that three-dimensional collector is immersed in temperature, then by colloidal solution at room temperature from
So volatilization, obtains growing the micron order for having colloid template three-dimensional current collector plate.
8. the preparation method of a kind of three-dimensional porous material by different level according to claim 1, it is characterised in that in step 4
Described ionic liquid electrodeposition liquid is prepared as follows：By dissolving metal salts to 1- ethyl-3-methylimidazoles double three
In fluoromethane sulfimide salt, ionic liquid electrodeposition liquid is obtained；The concentration of slaine in described ionic liquid electrodeposition liquid
It is 0.5mol/L；Described slaine is GeCl4Or SiCl4。
9. the preparation method of a kind of three-dimensional porous material by different level according to claim 1, it is characterised in that in step 4
The described voltage for using deposited metal in colloid template hole of the potentiostatic electrodeposition method on micron order three-dimensional collector is 2V,
Current density is -4 × 10-2A/m2；Sedimentation time is 20min, and the temperature of electro-deposition is room temperature.
10. the preparation method of a kind of three-dimensional porous material by different level according to claim 1, it is characterised in that in step 5
The concrete operations of described annealing method are：The micron order of three-dimensional hierarchy skeleton will be contained with the heating rate of 3 DEG C/min
Three-dimensional collector rises to 200 DEG C from room temperature, is incubated 60min, then 600 DEG C are risen to from 200 DEG C with the heating rate of 3 DEG C/min, protects
Warm 120min, is then down to 200 DEG C from 600 DEG C with the rate of temperature fall of 5 DEG C/min, then is naturally cooling to room temperature, and annealing terminates.
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