CN104637699B - A kind of method that ultracapacitor is prepared based on three-dimensional porous graphene composite material - Google Patents
A kind of method that ultracapacitor is prepared based on three-dimensional porous graphene composite material Download PDFInfo
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Abstract
The present invention relates to a kind of method that ultracapacitor is prepared based on three-dimensional porous graphene composite material, including：Ptfe emulsion by three-dimensional porous graphene composite material and acetylene black, mass fraction 15% according to weight part ratio is（76~84）：（12~18）：（5~8）Ratio ground and mixed into electrode slurry, and be dispersed in a small amount of absolute ethyl alcohol and form liquid/paste and be coated on foam nickel surface and laminate, obtain electrode slice；Polypropylene porous film is used for barrier film and immersion in the electrolyte aqueous solution is put into, the barrier film soaked is placed in the middle of two electrode slices, the ultracapacitor of two electrodes is made in encapsulation.The present invention is based on described three-dimensional porous graphene composite material, and when encapsulated current density is 0.1A/g, specific capacity can reach between 236~160F/g.
Description
Technical field
Surpass the invention belongs to new material technology field, more particularly to a kind of prepared based on three-dimensional porous graphene composite material
The method of level capacitor.
Technical background
Ultracapacitor (supercapacitor) is the novel energy-storing device between secondary cell and traditional capacitor
Part, has the advantages that high power density, fast charging and discharging, high security, long circulation life, environmental protection, both with battery
Energy storage characteristic, the power characteristic with capacitor a, it is considered to be revolution in energy storage field, in hybrid power
The various fields such as automobile, communication, national defence, consumption electronic product show huge application value.It is main inside ultracapacitor
Be made up of electrode, electrolyte and barrier film, wherein electrode decides the main performance index of ultracapacitor, electrode by collector and
It is incorporated into the electrode material composition on its surface.Ultracapacitor is divided into two classes by energy storage mechnism：(1) double layer capacitor, its energy
The storage of amount is main to be formed electric double layer and is completed by ion is separated in electrolyte and electrode surface, and electrode material is mainly porous carbon
Material（Including activated carbon, charcoal-aero gel, carbon fiber and CNT etc.）；(2) Faraday pseudo-capacitance device, the storage master of its energy
If being completed by the quick faraday's reaction of electrode material, with the capacity density bigger than double layer capacitor, electrode material
Material mainly has transition metal oxide（RuO2、MnO2Deng）And conducting polymer（Polyaniline, polypyrrole, polythiophene and its derivative
Deng）.Either double layer capacitor or Faraday pseudo-capacitance device, seek bigger capacity density, and key factor is to find
Good electrode material.
Graphene（graphene）It is mesh with the two-dimensional and periodic honeycomb lattice structure by carbon hexatomic ring arrangement form
Most thin but most hard nano material on former world, with excellent conduction, heat conductivility, electrochemically stable, electrical conductivity it is high and
Charge-discharge is fast, is preferable electrode material.But, there is strong Van der Waals force in graphene film interlayer, make it easy to reunite,
This necessarily causes the specific surface area and electric conductivity of grapheme material to be greatly lowered, and makes the specific capacitance of graphene super capacitor fast
Speed is reduced, and seriously constrains extensive use of the graphene in ultracapacitor.
Hydrotalcite (Layered double hydroxides) has stratiform by what divalence and trivalent metal ion were constituted
The inorganic compound of crystal structure, constituting formula is：[M(II)1-xM(III)x(OH)2]x+(An− x/n).mH2O, wherein, M (II)
It is respectively divalence and trivalent metal ion with M (III), A is the interlayer anion that valence mumber is-n, and x is M (III) molal quantity, and m is
It is hydrated water number.The layer structure of hydrotalcite be by metallic hydrogen oxygen octahedra by common edge be connected with each other form, positively charged, layer with
Layer is superimposed to top, and interlayer is with hydrogen bond association, and interlayer has tradable anion as ion balance, makes total in electricity
Property.Hydrotalcite flaggy metal ion can modulation, interlayer anion has intercalation assembleability, and assembling can be regulated and controled as needed, thus
Hydrotalcite material species is various, is used widely in terms of catalysis, absorption, medicine.
Graphitization is to make carbon atom the having from Turbostratic to crystal structure of graphite of thermodynamic instability using thermal activation
Sequence is converted, and in graphitizing process, to use high-temperature heat treatment（More than 2000 DEG C）Energy is provided to atomic rearrangement and structure transformation
Amount, therefore condition is harsh, cost is high.
A kind of " preparation method of three-dimensional porous graphene composite material " of Fujian Normal University's invention（Application invention on the same day
Patent）, this method introduces electroactive transition metal oxide while graphene is prepared, is allowed to play the work of space obstacle
With the reunion of reduction graphene film interlayer increases specific surface area（The sample is obtained with specific surface area and pore analysis instrument measurement
Brunauer-Emmett-Teller specific surface areas be up to 1828m2/ g, single-point pore volume (P/P0=0.99) be 1.08~
1.35cm3Between/g）, the electric double-layer capacitance of graphene is improved, meanwhile, the introducing of electroactive transition metal oxide answers this
Condensation material can provide the Faraday pseudo-capacitance bigger than its electric double layer capacitance.In this way, the shortcoming that graphene is easily reunited both had been overcome,
The cooperative effect that graphene and transition metal oxide have complementary advantages is generated again.
The content of the invention：
It is an object of the invention to overcome the shortcomings of electrode material there is provided one kind based on three-dimensional porous graphene composite material
The method for preparing ultracapacitor
Three-dimensional porous graphene composite material of the present invention, is obtained using following technical scheme：
（1）Chlorate or nitrate aqueous solution A, the chlorination of trivalent metal cation of divalent metal are prepared respectively
Salt or nitrate aqueous solution B；
（2）Take organic anion to be well-dispersed in solvent D, obtain solution C；
（3）Under the conditions of ceaselessly strong agitation solution C, while water solution A and aqueous solution B are added dropwise in solution C；
（4）The NaOH solution for being 30% with mass ratio after being added dropwise to complete regulation pH value is 6.0~12.0 acquisition samples；By sample
Product are aged 10~18 hours under the conditions of being placed in 50~90 DEG C；
（5）The sample of ageing is washed with deionized to whole filtrate pH=7~8, filtering, by obtained filter cake 50~
Vacuum drying 3~8 hours, obtain organic anion intercalated houghite in 100 DEG C of temperature ranges；
（6）Organic anion intercalated houghite is placed in tube furnace, calcined under the protection of inert gas, is heated up
To between 600~1600 DEG C, then calcining at constant temperature 1~6 hour, then cooling down obtains crude product to room temperature；
（7）Crude product is washed with deionized to go after the removal of impurity, vacuum drying, which is obtained, at 80 DEG C has three-dimensional porous knot
The graphene composite material of structure.
In water solution A of the present invention, divalent metal refers to Zn2+、Ni2+、Co2+、Mn2+Or Cu2 +In one
Kind；
In aqueous solution B of the present invention, trivalent metal cation refers to Co3+、Cr3+、Fe3+、V3+Or Sc3 +In one
Kind；
Solvent D of the present invention, refers to one kind in distilled water, acetone, ethyl acetate, ethanol, toluene or chloroform；
Organic anion of the present invention refers to succinic ion, and adipic acid radical ion, decanedioic acid radical ion is stearic
In acid ion, benzoate anion ion, dodecyl sulphate radical ion, DBSA ion or abietate ion
One kind；
By step（3）Afterwards, in solution C of the present invention, divalent metal, trivalent metal cation, have
Mol ratio between machine anion is 0.8~4.3:1:0.5~5.2；
Inert gas of the present invention refers to one kind in nitrogen, argon gas or helium.
A kind of method that ultracapacitor is prepared based on three-dimensional porous graphene composite material of the present invention, use with
Lower technical scheme is realized.
（1）By the three-dimensional porous graphene composite material prepared and acetylene black, ptfe emulsion (mass fraction
15%) it is according to weight part ratio（76~84）：（12~18）：（5~8）Ratio ground and mixed be uniformly made into electrode slurry, ultrasound
2~3h makes electrode slurry be dispersed in a small amount of absolute ethyl alcohol to form liquid/paste, be then spread evenly across foam nickel surface,
After being dried in vacuo at 100 DEG C, thin slice of the thickness as 0.1 mm is pressed into using 15 MPa pressure on hand oil-pressure machine, electricity is obtained
Pole piece；
（2）Use polypropylene porous film for barrier film and be put into the electrolyte 30wt% KOH aqueous solution（6mol∕L）Middle immersion 8
~15 minutes, then the barrier film soaked is placed in the middle of two electrode slices, button cell shell is used（CR2032）Encapsulation, is made two
The ultracapacitor of electrode.
Based on above-mentioned three-dimensional porous graphene composite material, through button cell shell（CR2032）Encapsulation, is made two electrodes and surpasses
After level capacitor, LAND battery test systems（CT2001A, LAND）Constant current charge-discharge test is carried out to electrode capacitor（Electric current
0.1 ~ 0.5A/g of density, voltage range is 0 ~ 1.2 V）：When it is 0.1A/g to test current density, specific capacity can reach 236~
Between 160F/g.
Brief description of the drawings
Fig. 1 is in different current densities based on the ultracapacitor obtained by three-dimensional porous graphene composite material of the invention
Under specific capacity.
Embodiment:
The present invention is more specifically described in detail with nonlimiting examples below, it will help to the present invention and its
The understanding of advantage, and it is not as a limitation of the invention, for the technological parameter not indicated especially, it can refer to routine techniques and enter
OK.
Embodiment 1
The preparation of three-dimensional porous graphene composite material
（1）0.3MZn (Cl) is prepared respectively2Aqueous solution 1L, 0.1M Co (Cl)3Aqueous solution 1L be solution A and B；
（2）Take 0.03mol sodium succinate to be scattered in advance in 100ml distilled water, then add and contain under vigorous stirring
There is the 0.25mol NaOH aqueous solution fully to react, add appropriate distilled water and be configured to mixed serum C；
（3）Under the conditions of ceaselessly strong agitation mixed serum C, while water solution A and aqueous solution B are added dropwise into mixing
In slurries C；
（4）The NaOH solution for being 30% with mass ratio after being added dropwise to complete regulation pH value is 9.0 acquisition samples；Sample is placed in
It is aged 12 hours under the conditions of 80 DEG C；
（5）The sample of ageing is washed with deionized to whole filtrate pH=7, filtering, by obtained filter cake in 80 DEG C of temperature
It is dried in vacuo 5 hours in the range of degree, obtains succinic intercalated houghite；
（6）Succinic intercalated houghite is placed in tube furnace, is calcined under the protection of argon gas, is warming up to 1000
DEG C, then calcining at constant temperature 3 hours, then cooling down obtain crude product to room temperature；
（7）Crude product is washed with deionized to go after the removal of impurity, vacuum drying, which is obtained, at 80 DEG C has three-dimensional porous knot
The graphene composite material of structure；The Brunauer-Emmett- of the sample is obtained with specific surface area and pore analysis instrument measurement
Teller specific surface areas are up to 1540m2/ g, single-point pore volume (P/P0=0.99) is 1.28cm3/g；
The method that a kind of three-dimensional porous graphene composite material of the present invention prepares ultracapacitor, using following skill
Art scheme is realized.
Ultracapacitor is prepared based on novel porous graphene composite material
（1）By the graphene composite material prepared and acetylene black, ptfe emulsion (mass fraction 15%) according to
Mass ratio is 80：15：5 ratio ground and mixed is uniformly made into electrode slurry, and ultrasonic 3h makes electrode slurry be dispersed on a small quantity
Liquid/paste is formed in absolute ethyl alcohol, is then spread evenly across after being dried in vacuo at foam nickel surface, 100 DEG C, in hand oil-pressure
Thin slice of the thickness as 0.1 mm is pressed into using 15 MPa pressure on machine, electrode slice is obtained；
（2）Use polypropylene porous film for barrier film and be put into the electrolyte 30wt% KOH aqueous solution（6mol∕L）Middle immersion
10 minutes, then the barrier film soaked is placed in the middle of two electrode slices, button cell shell is used（CR2032）Encapsulation, is made two electricity
Electrode capacitor.
（3）Using LAND battery test systems（CT2001A, LAND）Constant current charge-discharge is carried out to above-mentioned two electrode capacitor
Test（0.1 ~ 0.5A/g of current density, voltage range is 0 ~ 1.2 V）：When it is 0.1A/g to test current density, specific capacity is
180F/g.As shown in Figure 1.
Embodiment 2
The preparation of three-dimensional porous graphene composite material
（1）0.8M Cu (NO are prepared respectively3)2Aqueous solution 1L, 0.48M Fe (NO3)3Aqueous solution 1L for solution A and
B；
（2）1.7mol neopelex is taken to be well-dispersed in 100ml distilled water, this is solution C；
（3）Under the conditions of ceaselessly strong agitation solution C, while water solution A and aqueous solution B are added dropwise in solution C；
（4）The NaOH solution for being 30% with mass ratio after being added dropwise to complete regulation pH value is 8.0 acquisition samples；Sample is placed in
It is aged 16 hours under the conditions of 70 DEG C；
（5）The sample of ageing is washed with deionized to whole filtrate pH=7, filtering, by obtained filter cake in 60 DEG C of temperature
It is dried in vacuo 8 hours in the range of degree, obtains DBSA root intercalated houghite；
（6）DBSA root intercalated houghite is placed in tube furnace, calcined under the protection of nitrogen, is risen
Temperature is to 800 DEG C, then calcining at constant temperature 6 hours, and then cooling down obtains crude product to room temperature；
（7）Crude product is washed with deionized to go after the removal of impurity, vacuum drying, which is obtained, at 80 DEG C has three-dimensional porous knot
The graphene composite material of structure；The Brunauer-Emmett- of the sample is obtained with specific surface area and pore analysis instrument measurement
Teller specific surface areas are up to 1670m2/ g, single-point pore volume (P/P0=0.99) is 1.31cm3/g；
Ultracapacitor is prepared based on three-dimensional porous graphene composite material
（1）By the graphene composite material prepared and acetylene black, ptfe emulsion (mass fraction 15%) according to
Mass ratio is 76：18：5 ratio ground and mixed is uniformly made into electrode slurry, and it is few that ultrasonic 2.5h is dispersed in electrode slurry
Liquid/paste is formed in amount absolute ethyl alcohol, is then spread evenly across after being dried in vacuo at foam nickel surface, 100 DEG C, in manual oil
Thin slice of the thickness as 0.1 mm is pressed into using 15 MPa pressure on press, electrode slice is obtained.
（2）Use polypropylene porous film for barrier film and be put into the electrolyte 30wt% KOH aqueous solution（6mol∕L）Middle immersion 8
Minute, then the barrier film soaked is placed in the middle of two electrode slices, button cell shell is used（CR2032）Encapsulation, is made two electrodes
Ultracapacitor.
（3）Using LAND battery test systems（CT2001A, LAND）Constant current is carried out to above-mentioned two electrode super capacitor to fill
Discharge test（0.1 ~ 0.5A/g of current density, voltage range is 0 ~ 1.2 V）：When it is 0.1A/g to test current density, specific volume
Measure as 220F/g, as shown in Figure 1.
Embodiment 3
The preparation of three-dimensional porous graphene composite material
（1）0.3M Ni (Cl) are prepared respectively2Aqueous solution 1L, 0.12M V (Cl)3Aqueous solution 1L be solution A and B；
（2）0.01mol superfine pure rosin is taken to be well-dispersed in 100ml absolute ethyl alcohols, this is solution C；
（3）Under the conditions of ceaselessly strong agitation solution C, while water solution A and aqueous solution B are added dropwise in solution C；
（4）The NaOH solution for being 30% with mass ratio after being added dropwise to complete regulation pH value is 11.0 acquisition samples；Sample is placed in
It is aged 10 hours under the conditions of 90 DEG C；
（5）The sample of ageing is washed with deionized to whole filtrate pH=8, filtering, by obtained filter cake in 100 DEG C of temperature
It is dried in vacuo 3 hours in the range of degree, obtains abietate intercalated houghite；
（6）Abietate intercalated houghite is placed in tube furnace, is calcined under the protection of helium, is warming up to 1500
DEG C, then calcining at constant temperature 1 hour, then cooling down obtain crude product to room temperature；
（7）Crude product is washed with deionized to go after the removal of impurity, vacuum drying, which is obtained, at 80 DEG C has three-dimensional porous knot
The graphene composite material of structure；The Brunauer-Emmett- of the sample is obtained with specific surface area and pore analysis instrument measurement
Teller specific surface areas are up to 1810m2/ g, single-point pore volume (P/P0=0.99) is 1.15cm3/g。
Ultracapacitor is prepared based on three-dimensional porous graphene composite material
（1）By the graphene composite material prepared and acetylene black, ptfe emulsion (mass fraction 15%) according to
Mass ratio is 84：12：8 ratio ground and mixed is uniformly made into electrode slurry, and ultrasonic 2h makes electrode slurry be dispersed on a small quantity
Liquid/paste is formed in absolute ethyl alcohol, is then spread evenly across after being dried in vacuo at foam nickel surface, 100 DEG C, in hand oil-pressure
Thin slice of the thickness as 0.1 mm is pressed into using 15 MPa pressure on machine, electrode slice is obtained.
（2）Use polypropylene porous film for barrier film and be put into the electrolyte 30wt% KOH aqueous solution（6mol∕L）Middle immersion
15 minutes, then the barrier film soaked is placed in the middle of two electrode slices, button cell shell is used（CR2032）Encapsulation, is made two electricity
Electrode capacitor.
（3）Using LAND battery test systems（CT2001A, LAND）Constant current charge-discharge is carried out to above-mentioned two electrode capacitor
Test（0.1 ~ 0.5A/g of current density, voltage range is 0 ~ 1.2 V）：When it is 0.1A/g to test current density, specific capacity is
236F/g, as shown in Figure 1.
Claims (8)
1. a kind of method that ultracapacitor is prepared based on three-dimensional porous graphene composite material, it is characterised in that
（1）By three-dimensional porous graphene composite material and acetylene black, mass fraction 15% ptfe emulsion according to parts by weight
Than for（76~84）：（12~18）：（5~8）Ratio ground and mixed be uniformly made into electrode slurry, 2~3h of ultrasound makes electrode slurry
Material, which is dispersed in a small amount of absolute ethyl alcohol, forms liquid/paste, is then spread evenly across foam nickel surface, is made after vacuum drying
Flakiness, obtains electrode slice；
（2）Polypropylene porous film is used for barrier film and immersion in the electrolyte aqueous solution is put into, then the barrier film soaked is placed in
In the middle of two electrode slices, encapsulated with CR2032 button cells shell, the ultracapacitor of two electrodes is made；
The preparation method of described three-dimensional porous graphene composite material is：
（1）Respectively prepare divalent metal chlorate or nitrate aqueous solution A, the chlorate of trivalent metal cation or
Nitrate aqueous solution B；
（2）Take organic anion to be well-dispersed in solvent D, obtain solution C；
（3）Under the conditions of ceaselessly strong agitation solution C, while water solution A and aqueous solution B are added dropwise in solution C；
（4）The NaOH solution for being 30% with mass ratio after being added dropwise to complete regulation pH value is 6.0~12.0 acquisition samples；Sample is put
It is aged 10~18 hours under the conditions of 50~90 DEG C；
（5）The sample of ageing is washed with deionized to whole filtrate pH=7~8, filtering, by obtained filter cake 50~100
Vacuum drying 3~8 hours, obtain organic anion intercalated houghite in DEG C temperature range；
（6）Organic anion intercalated houghite is placed in tube furnace, is calcined, is warming up under the protection of inert gas
Between 600~1600 DEG C, then calcining at constant temperature 1~6 hour, then cooling down obtains crude product to room temperature；
（7）Crude product is washed with deionized to go after the removal of impurity, vacuum drying is obtained with three-dimensional porous structure at 80 DEG C
Graphene composite material；
Described organic anion refers to succinic ion, adipic acid radical ion, decanedioic acid radical ion, stearate radical ion,
One kind in benzoate anion ion, dodecyl sulphate radical ion, DBSA ion, abietate ion.
2. a kind of method that ultracapacitor is prepared based on three-dimensional porous graphene composite material according to claim 1,
Characterized in that, in described water solution A, divalent metal refers to Zn2+、Ni2+、Co2+、Mn2+Or Cu2 +In one kind.
3. a kind of method that ultracapacitor is prepared based on three-dimensional porous graphene composite material according to claim 1,
It is characterized in that in described aqueous solution B, trivalent metal cation refers to Co3+、Cr3+、Fe3+、V3+Or Sc3 +In one kind.
4. a kind of method that ultracapacitor is prepared based on three-dimensional porous graphene composite material according to claim 1,
It is characterized in that described solvent D, refers to one kind in distilled water, acetone, ethyl acetate, ethanol, toluene or chloroform.
5. a kind of method that ultracapacitor is prepared based on three-dimensional porous graphene composite material according to claim 1,
It is characterized in that by step（3）Afterwards, in described solution C, divalent metal, trivalent metal cation, You Jiyin
Mol ratio between ion is 0.8~4.3:1:0.5~5.2.
6. a kind of method that ultracapacitor is prepared based on three-dimensional porous graphene composite material according to claim 1,
It is characterized in that described inert gas refers to one kind in nitrogen, argon gas or helium.
7. a kind of method that ultracapacitor is prepared based on three-dimensional porous graphene composite material according to claim 1,
It is characterized in that the vacuum drying that described liquid/paste is spread evenly across foam nickel surface is carried out at 100 DEG C；It is described
Thin slice, be that thin slice of the thickness as 0.1 mm be pressed into using 15 MPa pressure on hand oil-pressure machine.
8. a kind of method step that ultracapacitor is prepared based on three-dimensional porous graphene composite material according to claim 1
Suddenly, it is characterised in that described electrolyte is the 30wt% 6mol ∕ L KOH aqueous solution；Described immersion, the time is 8~15 points
Clock.
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| CN104934231A (en) * | 2015-06-19 | 2015-09-23 | 中国第一汽车股份有限公司 | Super capacitor electrode material |
| CN105304350A (en) * | 2015-11-17 | 2016-02-03 | 南通绿业中试技术研究院有限公司 | Abuse capacitor with wide temperature range and manufacturing method of abuse capacitor |
| CN105513813B (en) * | 2015-12-09 | 2018-08-10 | 中南大学 | One kind mixing the carbon mixed button ultracapacitor of cerium polyaniline/activity |
| CN105513825B (en) * | 2015-12-09 | 2018-08-10 | 中南大学 | A kind of symmetry button type electrode material for super capacitor and symmetry button type ultracapacitor |
| CN106898495A (en) * | 2017-03-28 | 2017-06-27 | 江苏大学 | A kind of assay method of high temperature energy-storage device and its high temperature rated voltage |
| CN111755259B (en) * | 2020-06-28 | 2021-09-03 | 同济大学 | Structure supercapacitor based on graphene/polymer/cement composite material and preparation method thereof |
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