CN106952739A - A kind of method that Al colelctor electrodes prepare three-dimensional structure electrode material - Google Patents
A kind of method that Al colelctor electrodes prepare three-dimensional structure electrode material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H—ELECTRICITY
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H—ELECTRICITY
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
A kind of method that Al colelctor electrodes prepare three-dimensional structure electrode material, it is related to a kind of preparation method of electrode material.The invention aims to solve existing Al collector materials to have compact oxidation layer, caused interface resistance is higher, the less problem of specific surface area.Preparation method：First, it is cleaned by ultrasonic and obtains clean Al substrates；2nd, the Al substrates after being imprinted；3rd, anodic oxidation obtains the Al substrates after anodic oxidation；4th, performed etching with plasma etching technology, then the method for using plasma chemical vapor deposition is deposited, and obtains vertical graphene current collector material；5th, sodium thiosulfate, potassium permanganate and deionized water are well mixed and obtain mixed solution；6th, hydro-thermal reaction, obtains reaction product, then is washed and dried, and obtains three-dimensional structure electrode material.Present invention is mainly used for the three-dimensional structure electrode material of preparation.
Description
Technical field
The present invention relates to a kind of preparation method of electrode material.
Background technology
Ultracapacitor is a system for efficiently storing and transmitting energy, and it has power density big, and capacity is big, uses
Long lifespan, the advantages of economic and environment-friendly, is widely used in various power supply supply places；Compared with ordinary capacitor, it has storage
The big advantage of energy.For synthesis, the lower cost of ultracapacitor, good reliability, application is wider, in the energy, number
There is huge application prospect in the fields such as code, electronics, automobile.
Ultracapacitor is made up of bipolar electrode, electrolyte, colelctor electrode, the part of spacer four, wherein, colelctor electrode completes electronics
Assemble function, on influenceing very big in terms of the stability, reliability, capacitance of ultracapacitor.In existing electrode material, heat is steady
It is the topmost problem faced that qualitative, corrosion resistance and active material, which are bonded bad,.Improving collector material can effectively change
Kind performance of the supercapacitor.
In existing collector material, Al materials show very big advantage.With widely used Ni and Fe collection
Electrode material is compared, and Al materials have more preferable electric conductivity, smaller density and lower cost.But Al collector materials are same
When have the disadvantage in that, traditional structure Al colelctor electrode surface oxide layers are comparatively dense, and collector contact area is smaller so that contact resistance
It is larger, have a strong impact on its further applying as collector material.Carried therefore, carrying out surface treatment to Al collector materials
Its high performance has very big necessity, is the effective way for expanding its application.
The content of the invention
The invention aims to solve existing Al collector materials to have a compact oxidation layer, caused interface resistance compared with
Height, the less problem of specific surface area, and a kind of method that Al colelctor electrodes prepare three-dimensional structure electrode material is provided.
A kind of method that Al colelctor electrodes prepare three-dimensional structure electrode material, is specifically realized by the following steps：
First, Al colelctor electrodes are first cleaned by ultrasonic 1min~5min using acetone soln as liquid is cleaned by ultrasonic, then it is molten with propyl alcohol
Liquid is cleaned by ultrasonic 1min~5min as liquid is cleaned by ultrasonic, and obtains clean Al substrates；
2nd, clean Al substrates are imprinted with silicon template, the Al substrates after being imprinted, the surface of the silicon template
Vertical uniform nano-pillar, nano-pillar is highly 150nm~250nm；
3rd, phosphoric acid electrolyte is injected into oxidation unit, then the Al substrates after impressing are placed in oxidation unit as anode
In, using graphite rod as to electrode, regulation voltage is 100V~300V, and anodizing time is 30min~300min, is obtained
Al substrates after anodic oxidation；The phosphoric acid electrolyte is mixed by mass fraction for 85% phosphoric acid, deionized water and ethylene glycol
Form, and mass fraction is 85% in described phosphoric acid electrolyte phosphoric acid and the volume ratio of deionized water are 1:(100~
1000) phosphoric acid and the volume ratio of ethylene glycol that, mass fraction is 85% in described phosphoric acid electrolyte are 1:(100~1000)；
4th, the Al substrates after anodic oxidation are placed in plasma activated chemical vapour deposition vacuum plant, after vacuumizing, with
Hydrogen gas flow is passed through hydrogen for 10sccm~100sccm, and argon is passed through by 10sccm~100sccm of argon gas flow
Pressure is 100Pa~300Pa in gas, regulation plasma activated chemical vapour deposition vacuum plant, then by plasma chemistry gas
Temperature is increased to 300~580 DEG C in phase deposition vacuum device, then pressure in plasma activated chemical vapour deposition vacuum plant is adjusted
To 200Pa~500Pa, and hydrogen gas flow be 10sccm~100sccm, argon gas flow be 10sccm~
100sccm, radio-frequency power are that 100W~200W, pressure are 200Pa~500Pa and temperature is to be carved under the conditions of 300~580 DEG C
Erosion, etch period is 10s~1000s, and etching stops being passed through hydrogen after terminating；Then by 5sccm of methane gas flow~
50sccm is passed through methane, and argon gas flow is adjusted into 50sccm~100sccm, by plasma activated chemical vapour deposition vacuum
Pressure is adjusted to 200Pa~700Pa in device, is then that 5sccm~50sccm, argon gas flow are adjusted in methane gas flow
50sccm~100sccm, radio-frequency power are that 100W~200W, pressure are that 200Pa~700Pa, temperature are 300 DEG C~580 DEG C bars
Deposited under part, sedimentation time is 1000s~5000s, after deposition terminates, close power supply, stopping is passed through methane, in argon gas gas
Room temperature is cooled under atmosphere, that is, obtains vertical graphene-current collector material；
5th, sodium thiosulfate, potassium permanganate and deionized water are well mixed, ultrasonic agitation 0.5h~1h is mixed
Solution；The volume ratio of sodium thiosulfate quality and deionized water is 1g in the mixed solution:(200~500) mL, the mixing
The volume ratio of potassium permanganate quality and deionized water is 1g in solution:(50~150) mL；
6th, the mixed solution that step 5 is obtained is placed in the reactor with polytetrafluoroethyllining lining, then will be vertical
Graphene-current collector material is impregnated in mixed solution, temperature be 100 DEG C~150 DEG C under conditions of hydro-thermal reaction 8h~
24h, obtains reaction product, and reaction product is washed with deionized 3~5 times, washed product is obtained, and is then 90 DEG C in temperature
6h~12h is dried to washed product under conditions of~150 DEG C, obtains depositing the current collector material of manganese dioxide particle, as three
Tie up structure electrode material.
The principle of the invention：By Al colelctor electrodes surface anodization, corona treatment and hydro-thermal reaction technique, improve boundary
Contact resistance between face, increases specific surface area, while realizing the good combination between graphene and manganese dioxide, is conducive to carrying
Rise specific capacity.
Advantage of the present invention：
1st, using the method for anodic oxidation, the Al of the three-dimensional structure of uniqueness is formed on Al colelctor electrodes surface2O3, it is used as one
Template effectively increases specific surface area.
2nd, the method for using plasma chemical vapor deposition, with plasma etching technology, effectively eliminates Al tables
The fine and close oxide-film in face, and by Al on the premise of its three-dimensional structure is retained2O3It is reduced to Al preparation process simple, low cost can
Continuously to be produced.
2nd, there is the graphene-structured of vertical-growth on the Al collector materials surface prepared by the present invention, with traditional Al colelctor electrodes
The oxide-film that surface forms densification is compared, and the graphene of vertical-growth can effectively reduce interface resistance, strengthen electric conductivity.
4th, the method for the present invention is simple, efficiently, is easy to industrialized production, the Al collector material specific surface areas prepared
It is larger, it is more difficult to aoxidize, greatly widen the application of this material.
Three-dimensional structure electrode material prepared by this method has in electrode material for super capacitor field before wide application
Scape.
Brief description of the drawings
Fig. 1 is that three-dimensional structure electrode material prepared by embodiment 1 carries out charging and discharging curve figure, and A is represented in 10mA electricity in figure
Flow down B in charging and discharging curve figure, figure and represent that C represents the discharge and recharge under 2mA electric currents in the charging and discharging curve figure under 5mA electric currents, figure
D represents that E represents the charging and discharging curve figure under 0.5mA electric currents in the charging and discharging curve figure under 1mA electric currents, figure in curve map, figure.
Embodiment
Embodiment one：Present embodiment is a kind of method that Al colelctor electrodes prepare three-dimensional structure electrode material, tool
Body is completed according to the following steps：
First, Al colelctor electrodes are first cleaned by ultrasonic 1min~5min using acetone soln as liquid is cleaned by ultrasonic, then it is molten with propyl alcohol
Liquid is cleaned by ultrasonic 1min~5min as liquid is cleaned by ultrasonic, and obtains clean Al substrates；
2nd, clean Al substrates are imprinted with silicon template, the Al substrates after being imprinted, the surface of the silicon template
Vertical uniform nano-pillar, nano-pillar is highly 150nm~250nm；
3rd, phosphoric acid electrolyte is injected into oxidation unit, then the Al substrates after impressing are placed in oxidation unit as anode
In, using graphite rod as to electrode, regulation voltage is 100V~300V, and anodizing time is 30min~300min, is obtained
Al substrates after anodic oxidation；The phosphoric acid electrolyte is mixed by mass fraction for 85% phosphoric acid, deionized water and ethylene glycol
Form, and mass fraction is 85% in described phosphoric acid electrolyte phosphoric acid and the volume ratio of deionized water are 1:(100~
1000) phosphoric acid and the volume ratio of ethylene glycol that, mass fraction is 85% in described phosphoric acid electrolyte are 1:(100~1000)；
4th, the Al substrates after anodic oxidation are placed in plasma activated chemical vapour deposition vacuum plant, after vacuumizing, with
Hydrogen gas flow is passed through hydrogen for 10sccm~100sccm, and argon is passed through by 10sccm~100sccm of argon gas flow
Pressure is 100Pa~300Pa in gas, regulation plasma activated chemical vapour deposition vacuum plant, then by plasma chemistry gas
Temperature is increased to 300~580 DEG C in phase deposition vacuum device, then pressure in plasma activated chemical vapour deposition vacuum plant is adjusted
To 200Pa~500Pa, and hydrogen gas flow be 10sccm~100sccm, argon gas flow be 10sccm~
100sccm, radio-frequency power are that 100W~200W, pressure are 200Pa~500Pa and temperature is to be carved under the conditions of 300~580 DEG C
Erosion, etch period is 10s~1000s, and etching stops being passed through hydrogen after terminating；Then by 5sccm of methane gas flow~
50sccm is passed through methane, and argon gas flow is adjusted into 50sccm~100sccm, by plasma activated chemical vapour deposition vacuum
Pressure is adjusted to 200Pa~700Pa in device, is then that 5sccm~50sccm, argon gas flow are adjusted in methane gas flow
50sccm~100sccm, radio-frequency power are that 100W~200W, pressure are that 200Pa~700Pa, temperature are 300 DEG C~580 DEG C bars
Deposited under part, sedimentation time is 1000s~5000s, after deposition terminates, close power supply, stopping is passed through methane, in argon gas gas
Room temperature is cooled under atmosphere, that is, obtains vertical graphene-current collector material；
5th, sodium thiosulfate, potassium permanganate and deionized water are well mixed, ultrasonic agitation 0.5h~1h is mixed
Solution；The volume ratio of sodium thiosulfate quality and deionized water is 1g in the mixed solution:(200~500) mL, the mixing
The volume ratio of potassium permanganate quality and deionized water is 1g in solution:(50~150) mL；
6th, the mixed solution that step 5 is obtained is placed in the reactor with polytetrafluoroethyllining lining, then will be vertical
Graphene-current collector material is impregnated in mixed solution, temperature be 100 DEG C~150 DEG C under conditions of hydro-thermal reaction 8h~
24h, obtains reaction product, and reaction product is washed with deionized 3~5 times, washed product is obtained, and is then 90 DEG C in temperature
6h~12h is dried to washed product under conditions of~150 DEG C, obtains depositing the current collector material of manganese dioxide particle, as three
Tie up structure electrode material.
Three-dimensional structure is formed on Al colelctor electrodes surface using anodic oxidation, and vertical graphite is prepared in collection liquid surface original position
Alkene and manganese dioxide particle, form graphene-manganese dioxide composite construction, make three-dimensional structure electrode material charge-conduction path excellent
Different, electric charge transmission resistance is relatively low.
By the method for anodic oxidation, in the collector of aluminium substrate material surface formation three-dimensional structure, increase collector connects
Contacting surface is accumulated；The effect of plasma enhancing is introduced, effective processing has been carried out to the original oxide layer in surface, by the Al of anodic oxidation
Colelctor electrode surface reduction is Al, retains its script three-dimensional structure, and forms the graphene of vertical-growth, reduces surface-active substance
Contact resistance between matter and colelctor electrode；And then high, the cheap metal oxide MnO of composite theory specific capacity2, significantly carry
Rise performance.
Embodiment two：The difference of present embodiment and embodiment is：Al current collections described in step one
Pole is obtained according to the following steps：
1. it is ultrasonic successively, by Al base materials respectively using acetone soln, absolute ethyl alcohol and distilled water as liquid is cleaned by ultrasonic
5min is cleaned, is placed in after cleaning in vacuum drying chamber, is dried in the case where temperature is 60 DEG C, that is, the Al base materials cleaned；
2., by step, 1. the middle Al base materials cleaned are placed in plasma activated chemical vapour deposition vacuum plant, are taken out
Vacuum is postponed, and hydrogen is passed through using hydrogen gas flow as 20sccm, and argon gas, regulation etc. are passed through by 40sccm of argon gas flow
Pressure is 200Pa in ion body chemical vapor phase growing vacuum plant, is that 20sccm, argon gas flow are in hydrogen gas flow
40sccm and pressure heat up for temperature in plasma activated chemical vapour deposition vacuum plant is increased into 550 DEG C under the conditions of 200Pa
Time is 15min, is then that 100W, hydrogen gas flow are that 20sccm, argon gas flow are 40sccm, temperature in radio-frequency power
Degree is 550 DEG C and pressure is to perform etching under the conditions of 200Pa, and etch period is 300s, after etching terminates, and stopping is passed through hydrogen；
Then methane is passed through by 15sccm of methane gas flow, and argon gas flow is adjusted to 85sccm, is adjusted plasmarized
It is 650Pa to learn pressure in vapour deposition vacuum plant, is then that 200W, methane gas flow are 15sccm, argon in radio-frequency power
Gas gas flow is that 85sccm, pressure are 650Pa and temperature is to be deposited under the conditions of 550 DEG C, and sedimentation time is 180s, deposition
After end, radio-frequency power supply and heating power supply are closed, stopping is passed through methane, be under an argon atmosphere to be cooled at 550 DEG C from temperature
Room temperature, that is, obtain the Al colelctor electrodes by plasma etching treatment, as Al colelctor electrodes.
Other are identical with embodiment one.
Embodiment three：One of present embodiment and embodiment one or two difference is：Institute in step one
The Al colelctor electrodes thickness stated is 5 μm~50 μm.Other are identical with embodiment one or two.
Embodiment four：One of present embodiment and embodiment one to three difference is：In step 2
The pressure of impressing is 2 × 104N·cm-2Under the conditions of clean Al substrates are imprinted with silicon template, the Al bases after being imprinted
Bottom.Other are identical with embodiment one to three.
Embodiment five：One of present embodiment and embodiment one to four difference is：Adjusted in step 3
The voltage for saving oxidation unit is 200V.Other are identical with embodiment one to four.
Embodiment six：One of present embodiment and embodiment one to five difference is：Will in step 4
Al substrates after anodic oxidation are placed in plasma activated chemical vapour deposition vacuum plant, after vacuumizing, with hydrogen gas flow
Hydrogen is passed through for 20sccm, argon gas is passed through by 50sccm of argon gas flow, plasma activated chemical vapour deposition vacuum is adjusted
Pressure is 200Pa in device, and temperature in plasma activated chemical vapour deposition vacuum plant then is increased into 560 DEG C, then general etc.
Pressure is adjusted to 200Pa in ion body chemical vapor phase growing vacuum plant, and is 20sccm, argon gas stream in hydrogen gas flow
Amount is that 50sccm, radio-frequency power are that 200W, pressure are 200Pa and temperature is to perform etching under the conditions of 560 DEG C, and etch period is
300s, etching stops being passed through hydrogen after terminating.Other are identical with embodiment one to five.
Embodiment seven：One of present embodiment and embodiment one to six difference is：In step 4 with
Methane gas flow is passed through methane for 10sccm, and argon gas flow is adjusted into 90sccm, and plasma enhanced chemical vapor is sunk
Pressure is adjusted to 500Pa in product vacuum plant, then methane gas flow be 10sccm, argon gas flow be adjusted to 90sccm,
Radio-frequency power is that 200W, pressure are that 500Pa, temperature are to be deposited under the conditions of 560 DEG C, and sedimentation time is 3600s, and deposition terminates
Afterwards, power supply is closed, stopping is passed through methane, room temperature is cooled under an argon atmosphere, that is, obtains vertical graphene-current collector material.
Other are identical with embodiment one to six.
Present invention is not limited only to the content of the respective embodiments described above, the group of one of them or several embodiments
Contract sample can also realize the purpose of invention.
Beneficial effects of the present invention are verified using following instance：
Embodiment one：
A kind of method that Al colelctor electrodes prepare three-dimensional structure electrode material, is specifically realized by the following steps：
First, by Al colelctor electrodes first using acetone soln as be cleaned by ultrasonic liquid be cleaned by ultrasonic 5min, then using propanol solution as
It is cleaned by ultrasonic liquid and is cleaned by ultrasonic 5min, obtains clean Al substrates；
2nd, clean Al substrates are imprinted with silicon template, the Al substrates after being imprinted, the surface of the silicon template
Vertical uniform nano-pillar, nano-pillar average height is 200nm；
3rd, phosphoric acid electrolyte is injected into oxidation unit, then the Al substrates after impressing are placed in oxidation unit as anode
In, using graphite rod as to electrode, regulation voltage is 200V, and anodizing time is 40min, obtains the Al after anodic oxidation
Substrate；The phosphoric acid electrolyte is mixed by 0.5mL mass fractions for 85% phosphoric acid, 200mL deionized waters and 100mL ethylene glycol
Form；
4th, the Al substrates after anodic oxidation are placed in plasma activated chemical vapour deposition vacuum plant, after vacuumizing, with
Hydrogen gas flow is passed through hydrogen for 20sccm, and argon gas is passed through by 50sccm of argon gas flow, adjusts plasma chemistry
The pressure in vacuum plant that is vapor-deposited is 200Pa, is then increased to temperature in plasma activated chemical vapour deposition vacuum plant
560 DEG C, then pressure in plasma activated chemical vapour deposition vacuum plant is adjusted to 200Pa, and be in hydrogen gas flow
20sccm, argon gas flow be 50sccm, radio-frequency power be 200W, pressure is 200Pa and temperature is progress under the conditions of 560 DEG C
Etching, etch period is 300s, and etching stops being passed through hydrogen after terminating；Then it is passed through first using methane gas flow as 10sccm
Alkane, and argon gas flow is adjusted to 90sccm, pressure in plasma activated chemical vapour deposition vacuum plant is adjusted to 500Pa,
Then methane gas flow be 20sccm, argon gas flow be adjusted to 90sccm, radio-frequency power be 200W, pressure be 500Pa,
Temperature is is deposited under the conditions of 560 DEG C, sedimentation time is 3600s, after deposition terminates, and closes power supply, and stopping is passed through methane,
Room temperature is cooled under argon gas atmosphere, that is, obtains vertical graphene-current collector material；
5th, sodium thiosulfate, potassium permanganate and deionized water are well mixed, ultrasonic agitation 0.5h obtains mixed solution；
The volume ratio of sodium thiosulfate quality and deionized water is 1g in the mixed solution:Permanganic acid in 320mL, the mixed solution
The volume ratio of potassium quality and deionized water is 1g:80mL；
6th, the mixed solution that step 5 is obtained is placed in the reactor with polytetrafluoroethyllining lining, then will be vertical
Graphene-current collector material is impregnated in mixed solution, the hydro-thermal reaction 12h under conditions of temperature is 120 DEG C, obtains reaction production
Thing, reaction product is washed with deionized 3 times, washed product is obtained, and then washing is produced under conditions of temperature is 105 DEG C
Thing dries 8h, obtains depositing the current collector material of manganese dioxide particle, as three-dimensional structure electrode material.
Al colelctor electrodes described in step one is obtained according to the following steps：
1. it is ultrasonic successively, by Al base materials respectively using acetone soln, absolute ethyl alcohol and distilled water as liquid is cleaned by ultrasonic
5min is cleaned, is placed in after cleaning in vacuum drying chamber, is dried in the case where temperature is 60 DEG C, that is, the Al base materials cleaned；
2., by step, 1. the middle Al base materials cleaned are placed in plasma activated chemical vapour deposition vacuum plant, are taken out
Vacuum is postponed, and hydrogen is passed through using hydrogen gas flow as 20sccm, and argon gas, regulation etc. are passed through by 40sccm of argon gas flow
Pressure is 200Pa in ion body chemical vapor phase growing vacuum plant, is that 20sccm, argon gas flow are in hydrogen gas flow
40sccm and pressure heat up for temperature in plasma activated chemical vapour deposition vacuum plant is increased into 550 DEG C under the conditions of 200Pa
Time is 15min, is then that 100W, hydrogen gas flow are that 20sccm, argon gas flow are 40sccm, temperature in radio-frequency power
Degree is 550 DEG C and pressure is to perform etching under the conditions of 200Pa, and etch period is 300s, after etching terminates, and stopping is passed through hydrogen；
Then methane is passed through by 15sccm of methane gas flow, and argon gas flow is adjusted to 85sccm, is adjusted plasmarized
It is 650Pa to learn pressure in vapour deposition vacuum plant, is then that 200W, methane gas flow are 15sccm, argon in radio-frequency power
Gas gas flow is that 85sccm, pressure are 650Pa and temperature is to be deposited under the conditions of 550 DEG C, and sedimentation time is 180s, deposition
After end, radio-frequency power supply and heating power supply are closed, stopping is passed through methane, be under an argon atmosphere to be cooled at 550 DEG C from temperature
Room temperature, that is, obtain the Al colelctor electrodes by plasma etching treatment, as Al colelctor electrodes.
Specific surface area test is carried out to three-dimensional structure electrode material prepared by embodiment 1, after tested, prepared by embodiment 1
The specific surface area of three-dimensional structure electrode material can reach 2.8m2/ g, original Al collector materials (i.e. step one 1. described in Al bases
Bottom material) specific surface area be 0.09m2/g。
To embodiment 1 prepare three-dimensional structure electrode material and original Al collector materials (i.e. step one 1. described in Al
Base material) carry out electrochemical AC impedance test, the electrode material of three-dimensional structure prepared by embodiment 1 shows relatively low etc.
Effect series resistance is 5 Ω, and the equivalent series resistance of original Al base materials is 12 Ω.
Charge-discharge test is carried out to three-dimensional structure electrode material prepared by embodiment 1, shown in result figure 1, Fig. 1 is embodiment
The 1 three-dimensional structure electrode material prepared carries out A in charging and discharging curve figure, figure and represents the charging and discharging curve figure under 10mA electric currents, schemes
Middle B represents that C represents that D is represented in the charging and discharging curve figure under 2mA electric currents, figure in the charging and discharging curve figure under 5mA electric currents, figure
E represents the charging and discharging curve figure under 0.5mA electric currents in charging and discharging curve figure under 1mA electric currents, figure, as shown in Figure 1, embodiment 1
The three-dimensional structure electrode material of preparation shows excellent performance, and calculating shows, under 1mA electric currents, three-dimensional prepared by embodiment 1
The specific capacitance value of structure electrode material is 790Fg-1。
Claims (7)
1. a kind of method that Al colelctor electrodes prepare three-dimensional structure electrode material, it is characterised in that it is completed according to the following steps：
First, Al colelctor electrodes are first cleaned by ultrasonic 1min~5min using acetone soln as liquid is cleaned by ultrasonic, then made with propanol solution
It is cleaned by ultrasonic 1min~5min to be cleaned by ultrasonic liquid, obtains clean Al substrates；
2nd, clean Al substrates are imprinted with silicon template, the Al substrates after being imprinted, the surface of the silicon template is vertical
Uniform nano-pillar, nano-pillar is highly 150nm~250nm；
3rd, phosphoric acid electrolyte is injected into oxidation unit, then the Al substrates after impressing are placed in oxidation unit as anode, is adopted
With graphite rod as to electrode, regulation voltage is 100V~300V, and anodizing time is 30min~300min, obtains anode
Al substrates after oxidation；The phosphoric acid electrolyte is mixed by mass fraction for 85% phosphoric acid, deionized water and ethylene glycol,
And the phosphoric acid and the volume ratio of deionized water that mass fraction is 85% in described phosphoric acid electrolyte are 1:(100~1000), institute
The phosphoric acid and the volume ratio of ethylene glycol that mass fraction is 85% in the phosphoric acid electrolyte stated are 1:(100~1000)；
4th, the Al substrates after anodic oxidation are placed in plasma activated chemical vapour deposition vacuum plant, after vacuumizing, with hydrogen
Gas flow is passed through hydrogen for 10sccm~100sccm, and argon gas is passed through by 10sccm~100sccm of argon gas flow, adjusts
It is 100Pa~300Pa to save pressure in plasma activated chemical vapour deposition vacuum plant, then by plasma activated chemical vapour deposition
Temperature is increased to 300~580 DEG C in vacuum plant, then pressure in plasma activated chemical vapour deposition vacuum plant is adjusted to
200Pa~500Pa, and hydrogen gas flow be 10sccm~100sccm, argon gas flow be 10sccm~100sccm,
Radio-frequency power is that 100W~200W, pressure are 200Pa~500Pa and temperature is to perform etching under the conditions of 300~580 DEG C, is etched
Time is 10s~1000s, and etching stops being passed through hydrogen after terminating；Then it is passed through using methane gas flow as 5sccm~50sccm
Methane, and argon gas flow is adjusted to 50sccm~100sccm, by pressure in plasma activated chemical vapour deposition vacuum plant
Be adjusted to 200Pa~700Pa, then methane gas flow be 5sccm~50sccm, argon gas flow be adjusted to 50sccm~
100sccm, radio-frequency power are that 100W~200W, pressure are that 200Pa~700Pa, temperature are progress under the conditions of 300 DEG C~580 DEG C
Deposition, sedimentation time is 1000s~5000s, after deposition terminates, and closes power supply, and stopping is passed through methane, cooled down under an argon atmosphere
To room temperature, that is, obtain vertical graphene-current collector material；
5th, sodium thiosulfate, potassium permanganate and deionized water are well mixed, ultrasonic agitation 0.5h~1h obtains mixed solution；
The volume ratio of sodium thiosulfate quality and deionized water is 1g in the mixed solution:(200~500) mL, the mixed solution
The volume ratio of middle potassium permanganate quality and deionized water is 1g:(50~150) mL；
6th, the mixed solution that step 5 is obtained is placed in the reactor with polytetrafluoroethyllining lining, then by vertical graphite
Alkene-current collector material is impregnated in mixed solution, hydro-thermal reaction 8h~24h under conditions of temperature is 100 DEG C~150 DEG C, is obtained
To reaction product, reaction product is washed with deionized 3~5 times, washed product is obtained, be then 90 DEG C~150 in temperature
6h~12h is dried to washed product under conditions of DEG C, obtains depositing the current collector material of manganese dioxide particle, as three-dimensional structure
Electrode material.
2. the method that a kind of Al colelctor electrodes according to claim 1 prepare three-dimensional structure electrode material, it is characterised in that step
Al colelctor electrodes are obtained according to the following steps described in rapid one：
1., Al base materials are cleaned by ultrasonic successively respectively using acetone soln, absolute ethyl alcohol and distilled water as liquid is cleaned by ultrasonic
It is placed in vacuum drying chamber, is dried in the case where temperature is 60 DEG C, that is, the Al base materials cleaned after 5min, cleaning；
2., by step, 1. the middle Al base materials cleaned are placed in plasma activated chemical vapour deposition vacuum plant, are vacuumized
Postpone, hydrogen is passed through using hydrogen gas flow as 20sccm, argon gas is passed through by 40sccm of argon gas flow, adjust plasma
Pressure is 200Pa in body chemical vapor phase growing vacuum plant, is that 20sccm, argon gas flow are in hydrogen gas flow
40sccm and pressure heat up for temperature in plasma activated chemical vapour deposition vacuum plant is increased into 550 DEG C under the conditions of 200Pa
Time is 15min, is then that 100W, hydrogen gas flow are that 20sccm, argon gas flow are 40sccm, temperature in radio-frequency power
Degree is 550 DEG C and pressure is to perform etching under the conditions of 200Pa, and etch period is 300s, after etching terminates, and stopping is passed through hydrogen；
Then methane is passed through by 15sccm of methane gas flow, and argon gas flow is adjusted to 85sccm, is adjusted plasmarized
It is 650Pa to learn pressure in vapour deposition vacuum plant, is then that 200W, methane gas flow are 15sccm, argon in radio-frequency power
Gas gas flow is that 85sccm, pressure are 650Pa and temperature is to be deposited under the conditions of 550 DEG C, and sedimentation time is 180s, deposition
After end, radio-frequency power supply and heating power supply are closed, stopping is passed through methane, be under an argon atmosphere to be cooled at 550 DEG C from temperature
Room temperature, that is, obtain the Al colelctor electrodes by plasma etching treatment, as Al colelctor electrodes.
3. the method that a kind of Al colelctor electrodes according to claim 1 or 2 prepare three-dimensional structure electrode material, it is characterised in that
Al colelctor electrodes thickness described in step one is 5 μm~50 μm.
4. the method that a kind of Al colelctor electrodes according to claim 1 prepare three-dimensional structure electrode material, it is characterised in that step
Pressure in rapid two in impressing is 2 × 104N·cm-2Under the conditions of clean Al substrates are imprinted with silicon template, imprinted
Al substrates afterwards.
5. the method that a kind of Al colelctor electrodes according to claim 1 prepare three-dimensional structure electrode material, it is characterised in that step
The voltage that oxidation unit is adjusted in rapid three is 200V.
6. the method that a kind of Al colelctor electrodes according to claim 1 prepare three-dimensional structure electrode material, it is characterised in that step
The Al substrates after anodic oxidation are placed in plasma activated chemical vapour deposition vacuum plant in rapid four, after vacuumizing, with hydrogen
Gas flow is passed through hydrogen for 20sccm, and argon gas is passed through by 50sccm of argon gas flow, adjusts plasma enhanced chemical vapor
Pressure is 200Pa in deposition vacuum device, and temperature in plasma activated chemical vapour deposition vacuum plant then is increased into 560
DEG C, then pressure in plasma activated chemical vapour deposition vacuum plant is adjusted to 200Pa, and hydrogen gas flow be 20sccm,
Argon gas flow is that 50sccm, radio-frequency power are that 200W, pressure are 200Pa and temperature is to perform etching under the conditions of 560 DEG C, is carved
The erosion time is 300s, and etching stops being passed through hydrogen after terminating.
7. the method that a kind of Al colelctor electrodes according to claim 1 prepare three-dimensional structure electrode material, it is characterised in that step
Methane is passed through in rapid four by 10sccm of methane gas flow, and argon gas flow is adjusted to 90sccm, will be plasmarized
Learn pressure in vapour deposition vacuum plant and be adjusted to 500Pa, be then that 10sccm, argon gas flow are adjusted in methane gas flow
90sccm, radio-frequency power are that 200W, pressure are that 500Pa, temperature are to be deposited under the conditions of 560 DEG C, and sedimentation time is 3600s,
After deposition terminates, power supply is closed, stopping is passed through methane, room temperature is cooled under an argon atmosphere, that is, obtains vertical graphene-afflux
Body material.
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| CN108550788A (en) * | 2018-04-27 | 2018-09-18 | 北京石墨烯研究院 | Plus plate current-collecting body, battery positive pole piece and lithium ion battery |
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| CN106450154A (en) * | 2016-11-30 | 2017-02-22 | 哈尔滨工业大学 | Preparation method for in-situ growth of graphene on surface of aluminum current collector of lithium ion battery |
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| CN105449225A (en) * | 2015-12-02 | 2016-03-30 | 哈尔滨工业大学 | Preparation method of aluminum collector in three-dimensional porous structure |
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| CN108550788A (en) * | 2018-04-27 | 2018-09-18 | 北京石墨烯研究院 | Plus plate current-collecting body, battery positive pole piece and lithium ion battery |
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