CN109192549B - Stabilized lithium powder-carbon nanotube-ultra-long nanowire composite electrode and preparation method thereof, and super capacitor - Google Patents
Stabilized lithium powder-carbon nanotube-ultra-long nanowire composite electrode and preparation method thereof, and super capacitor Download PDFInfo
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
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- 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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- 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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- 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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- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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Abstract
The invention provides a stabilized lithium powder-carbon nanotube-ultra-long nanowire composite electrode, a preparation method thereof and a super capacitor. The invention utilizes the stabilized lithium powder coated with lithium fluoride on the surface to carry out pre-lithiation treatment on the carbon nano tube-hydroxyapatite ultra-long nano wire pole piece to obtain the stabilized lithium powder-carbon nano tube-ultra-long nano wire composite electrode, the lithium fluoride coated on the surface of the lithium powder can effectively prevent excessive lithium from forming lithium dendrite, and the lithium powder coated with the lithium fluoride on the surface can stably exist in the air, so that the pre-lithiation treatment is more convenient. The composite electrode provided by the invention has excellent electrochemical performance, and a super capacitor assembled by using the composite electrode provided by the invention has high energy density and good cycle performance.
Description
Technical Field
The invention relates to the technical field of super capacitors, in particular to a stabilized lithium powder-carbon nanotube-ultra-long nanowire composite electrode, a preparation method thereof and a super capacitor.
Background
With the rapid development of industry and the rapid increase of population, the global energy consumption is increasing at an incredible speed, and the energy shortage and environmental pollution become two major challenges facing the current human development. New low cost, sustainable and environmentally friendly energy conversion and storage devices must therefore be vigorously developed to meet the development needs of today's society and to alleviate the increasingly prominent environmental problems. Among the various energy storage systems, the most prominent are electrochemical energy storage systems, including lithium ion batteries, supercapacitors and fuel cells. In recent years, with the rapid development of new technologies in the fields of information technology, electronic products, vehicle energy and the like, lithium ion supercapacitors attract great interest of researchers by virtue of the characteristics of large specific capacity, high charging and discharging speed, long cycle life and the like.
The electrochemical performance of the super capacitor can be improved by carrying out pre-lithiation treatment on the negative electrode material of the lithium ion super capacitor, and in the existing pre-lithiation treatment method, the method of coating metal lithium powder on the surface of a negative electrode sheet is the most convenient and effective pre-lithiation mode. However, the addition amount of lithium powder during the prelithiation treatment is too small to achieve the effect, excessive metal lithium powder is easy to form lithium dendrite to destroy the separator, a thick SEI film is formed on the surface of the negative electrode, the resistance is increased, the electrochemical performance of the supercapacitor is reduced, and the lithium powder is easy to oxidize in the air and has poor stability.
Disclosure of Invention
In view of the above, the present invention provides a stabilized lithium powder-carbon nanotube-ultra-long nanowire composite electrode, a method for preparing the same, and a super capacitor, wherein the composite electrode provided by the present invention uses stabilized lithium powder with fluorinated surface for pre-lithiation, so as to solve the problem that lithium powder is easily oxidized, and lithium dendrite is not easily formed.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of a stabilized lithium powder-carbon nanotube-ultra-long nanowire composite electrode comprises the following steps:
(1) mixing a dispersing agent, a carbon nano tube and water, and then sequentially carrying out ultrasonic treatment and sand milling treatment to obtain a carbon nano tube dispersion liquid;
(2) mixing the hydroxyapatite ultralong nanowire with an alcohol solvent, and pulping to obtain a hydroxyapatite ultralong nanowire suspension;
(3) mixing the carbon nano tube dispersion liquid and the hydroxyapatite ultralong nanowire suspension, coating the obtained mixed slurry on a substrate, and stripping the substrate to obtain a carbon nano tube-hydroxyapatite ultralong nanowire wet pole piece; drying the wet pole piece to obtain a carbon nano tube-hydroxyapatite ultra-long nanowire pole piece;
(4) carrying out heat treatment on the perfluorinated resin and the metal lithium powder under the condition of spaced placement to obtain stabilized lithium powder;
(5) carrying out pre-lithiation treatment on the carbon nano tube-hydroxyapatite ultra-long nanowire pole piece by using the stabilized lithium powder to obtain a stabilized lithium powder-carbon nano tube-ultra-long nanowire composite electrode;
the steps (1), (2) and (4) are not limited by time sequence;
the steps (3) and (4) are not limited in chronological order.
Preferably, the prelithiation treatment in step (5) includes the steps of: and dispersing the stabilized lithium powder in an organic solvent, coating the obtained stabilized lithium powder dispersion liquid on the surface of the carbon nano tube-hydroxyapatite ultra-long nanowire pole piece, and then carrying out hot press molding.
Preferably, the hot-press forming temperature is 150-180 ℃, the pressure is 10-12 MPa, and the time is 5-10 min.
Preferably, the mass ratio of the carbon nanotubes to the hydroxyapatite ultralong nanowires in the mixed slurry obtained in the step (3) is 3: 7-7: 3.
Preferably, the mass ratio of the perfluoro resin to the lithium metal powder in the step (4) is 2-5: 1.
Preferably, the heat treatment in the step (4) includes a high-temperature heat treatment and a low-temperature heat treatment which are sequentially performed;
the temperature of the high-temperature heat treatment is 330-350 ℃, and the time is 1-2 h;
the temperature of the low-temperature heat treatment is 150-180 ℃, and the time is 10-12 hours.
The invention provides a stabilized lithium powder-carbon nano tube-ultra-long nano wire composite electrode prepared by the preparation method in the scheme, which comprises a carbon nano tube-ultra-long nano wire pole piece and stabilized lithium powder loaded on the pole piece, wherein the loading capacity of the stabilized lithium powder on the surface of the composite electrode is 0.01-0.1 g/m2。
The invention provides a super capacitor which comprises a positive electrode, a diaphragm, a negative electrode and electrolyte, wherein the negative electrode is the stabilized lithium powder-carbon nano tube-ultra-long nano wire composite electrode.
Preferably, the positive electrode is an activated carbon-hydroxyapatite ultra-long nanowire composite electrode;
the preparation method of the active carbon-hydroxyapatite ultra-long nanowire composite electrode comprises the following steps:
mixing activated carbon and water, and then performing dispersion treatment to obtain an activated carbon dispersion liquid;
mixing the hydroxyapatite ultralong nanowire with an alcohol solvent, and pulping to obtain a hydroxyapatite ultralong nanowire suspension;
mixing the active carbon dispersion liquid and the hydroxyapatite ultralong nanowire suspension, coating the mixed slurry on a substrate, and stripping the substrate to obtain an active carbon-hydroxyapatite ultralong nanowire wet pole piece; and drying the wet pole piece to obtain the active carbon-hydroxyapatite ultra-long nanowire composite electrode.
Preferably, the diaphragm is a polypropylene microporous membrane; the electrolyte is LiPF6And (3) an electrolyte.
The invention provides a preparation method of a stabilized lithium powder-carbon nanotube-ultra-long nanowire composite electrode. According to the invention, the pole piece is subjected to pre-lithiation treatment by using the stabilized lithium powder, and the lithium fluoride coated on the surface of the lithium powder can effectively prevent excessive lithium from forming lithium dendrites, so that the problem of the addition amount of the lithium powder in the pre-lithiation process is solved, and the lithium powder coated with the lithium fluoride on the surface can stably exist in the air, so that the pre-lithiation treatment is more convenient.
The invention provides a stabilized lithium powder-carbon nano tube-ultra-long nanowire composite electrode prepared by the preparation method in the scheme, which comprises a carbon nano tube-ultra-long nanowire pole piece and stabilized lithium powder loaded on the pole piece, wherein the loading capacity of the stabilized lithium powder on the surface of the composite electrode is 0.01-0.1 g/m2. In the invention, the pole piece is composed of the hydroxyapatite super-long nanowire and the carbon nanotube, the hydroxyapatite super-long nanowire has good flexibility, high temperature resistance, corrosion resistance and biological safety, the carbon nanotube has a good porous structure, the stabilized lithium powder can be well blended into the pole piece, and the composite electrode prepared from the carbon nanotube and the hydroxyapatite super-long nanowire has good electrolyte wettability, thereby improving the electrochemical performance of the electrode. The embodiment result shows that the super capacitor assembled by taking the composite electrode as the negative electrode has high energy density and good cycle performance, and the capacitance retention rate after 3500 cycles can reach about 90%.
Drawings
FIG. 1 is a graph of power density versus energy density for a # 1 ultracapacitor and a # 2 ultracapacitor in an embodiment of the present invention;
FIG. 2 is a graph showing the cycle performance test of # 1 supercapacitor and # 2 supercapacitor according to the embodiment of the present invention.
Detailed Description
The invention provides a preparation method of a stabilized lithium powder-carbon nanotube-ultra-long nanowire composite electrode, which comprises the following steps:
(1) mixing a dispersing agent, a carbon nano tube and water, and then sequentially carrying out ultrasonic treatment and sand milling treatment to obtain a carbon nano tube dispersion liquid;
(2) mixing the hydroxyapatite ultralong nanowire with an alcohol solvent, and pulping to obtain a hydroxyapatite ultralong nanowire suspension;
(3) mixing the carbon nano tube dispersion liquid and the hydroxyapatite ultralong nanowire suspension, coating the mixed slurry on a substrate, and stripping the substrate to obtain a carbon nano tube-hydroxyapatite ultralong nanowire wet pole piece; drying the wet pole piece to obtain a carbon nano tube-hydroxyapatite ultra-long nanowire pole piece;
(4) carrying out heat treatment on the perfluorinated resin and the metal lithium powder under the condition of spaced placement to obtain stabilized lithium powder;
(5) carrying out pre-lithiation treatment on the carbon nano tube-hydroxyapatite ultra-long nanowire pole piece by using the stabilized lithium powder to obtain a stabilized lithium powder-carbon nano tube-ultra-long nanowire composite electrode;
the steps (1), (2) and (4) are not limited by time sequence;
the steps (3) and (4) are not limited in chronological order.
The dispersing agent, the carbon nano tube and water are mixed and then sequentially subjected to ultrasonic treatment and sand milling treatment to obtain the carbon nano tube dispersion liquid. In the invention, the dispersant is preferably one or more of Sodium Dodecyl Sulfate (SDS), polyvinyl pyrrolidone (PVP) and sodium dodecyl sulfate (SDBS); the mass ratio of the dispersing agent to the carbon nano tubes is preferably 0.05-0.2: 1, and more preferably 0.05-0.1: 1; the mass concentration of the carbon nanotube dispersion liquid is preferably 3 to 8%, and more preferably 4 to 6%.
In the invention, the power of ultrasonic treatment is preferably 50-150 KHz, more preferably (80-130) KHz, and the time of ultrasonic treatment is preferably 20-40 min, more preferably 25-35 min; the rotation speed of the sanding treatment is preferably 1000-2000 r/min, and more preferably 1200-1500 r/min; the sanding treatment time is preferably 15-60 min, and more preferably 20-50 min. The present invention preferably uses a sand mill for the sanding process.
The invention mixes the hydroxyapatite ultralong nanowire and an alcohol solvent and then carries out pulping to obtain the hydroxyapatite ultralong nanowire suspension. In the invention, the diameter of the hydroxyapatite ultralong nanowire is preferably 5-100 nm, and more preferably 30-50 nm; the length of the hydroxyapatite overlong nanowire is preferably 30-1200 um, and more preferably 300-500 um. The source of the hydroxyapatite ultralong nanowire is not specially required, and the hydroxyapatite ultralong nanowire with the source known by the technicians in the field can be used, such as a commercially available hydroxyapatite ultralong nanowire.
In the present invention, the alcohol solvent is preferably ethanol; the mass concentration of the hydroxyapatite ultralong nanowire suspension is preferably 3-8%, and more preferably 4-6%; the preferable time of beating is 5-10 min. The invention has no special requirements on the specific pulping method, and can obtain uniform suspension.
After the carbon nano tube dispersion liquid and the hydroxyapatite ultralong nanowire suspension are obtained, the carbon nano tube dispersion liquid and the hydroxyapatite ultralong nanowire suspension are mixed to obtain mixed slurry. In the invention, the volume ratio of the carbon nanotube dispersion liquid to the hydroxyapatite ultralong nanowire suspension liquid is preferably 1: 1-5, and more preferably 1: 2-4; the invention preferably uses a micro-flow mixer to mix the carbon nano tube dispersion liquid and the hydroxyapatite ultra-long nano wire suspension liquid; in the invention, the mass ratio of the carbon nanotubes to the hydroxyapatite ultralong nanowires in the mixed slurry is preferably 3: 7-7: 3, and more preferably 4: 6-6: 4.
After the mixed slurry is obtained, the mixed slurry is coated on a substrate, and the substrate is peeled off to obtain the carbon nano tube-hydroxyapatite ultra-long nanowire wet pole piece. In the present invention, the coating is preferably spray coating, more preferably spray coating using a high-pressure airless sprayer; the substrate is preferably a foil; the invention does not require a particular thickness for the coating, and in particular embodiments of the invention, the coating thickness is preferably determined based on the target thickness of the composite electrode. The method of peeling off the substrate in the present invention is not particularly required, and a peeling method well known to those skilled in the art may be used.
After stripping, the carbon nanotube-hydroxyapatite ultralong nanowire wet pole piece is dried to obtain the carbon nanotube-hydroxyapatite ultralong nanowire pole piece. In the invention, the drying temperature is preferably 30-80 ℃, more preferably 50-70 ℃, the drying time has no special requirement, and the wet pole piece can be completely dried.
And (3) carrying out heat treatment on the perfluorinated resin and the metal lithium powder under the condition of spaced placement to obtain the stabilized lithium powder. In the invention, the mass ratio of the perfluorinated resin to the lithium metal powder is preferably 2-5: 1, and more preferably 3-4: 1; the perfluoro resin and the lithium metal powder are placed in a separated manner, so that the problem that the subsequent lithium metal powder and the resin are not easy to separate is solved; in the embodiment of the invention, the perfluorinated resin and the lithium powder are not contacted with each other by spacing, and the perfluorinated resin can be also spaced by using an asbestos plate.
In the present invention, the heat treatment preferably includes a high-temperature heat treatment and a low-temperature heat treatment which are sequentially performed; the temperature of the high-temperature heat treatment is preferably 330-350 ℃, and more preferably 340 ℃; the time of the high-temperature treatment is preferably 1-2 h, and more preferably 1.5 h; the temperature of the low-temperature heat treatment is preferably 150-180 ℃, more preferably 160-170 ℃, and the time of the low-temperature heat treatment is preferably 10-12 hours, more preferably 11 hours. In the high-temperature heat treatment process, the perfluoro resin is heated to generate fluorine gas, and in the low-temperature heat treatment process, the fluorine gas reacts with the lithium powder to generate lithium fluoride on the surface of the lithium powder.
According to the invention, the lithium powder is subjected to stabilization treatment (surface fluorination treatment) so that lithium fluoride is wrapped on the surface of the lithium powder, and the lithium fluoride wrapped on the surface of the lithium powder can effectively prevent excessive lithium from forming lithium dendrites, thereby solving the problem of the addition amount of the lithium powder in the pre-lithiation process; and the lithium powder coated with lithium fluoride on the surface can exist in the air very stably, so that the pre-lithiation operation is more convenient.
After the stabilized lithium powder is obtained, the stabilized lithium powder is used for carrying out pre-lithiation treatment on the carbon nano tube-hydroxyapatite ultra-long nano wire pole piece, and the stabilized lithium powder-carbon nano tube-ultra-long nano wire composite electrode is obtained. In the present invention, the prelithiation treatment preferably comprises the steps of: and dispersing the stabilized lithium powder in an organic solvent, coating the obtained stabilized lithium powder dispersion liquid on the surface of the carbon nano tube-hydroxyapatite ultra-long nanowire pole piece, and then carrying out hot press molding.
The invention disperses the stabilized lithium powder in the organic solvent to obtain the stabilized lithium powder dispersion liquid. In the present invention, the organic solvent is preferably a non-polar solvent or a weakly polar solvent, more preferably benzene and/or toluene; the mass of the stabilized lithium powder and the volume ratio of the organic solvent are preferably 0.5-1 g: 100 to 200mL, more preferably 0.5 to 0.75 g: 100-150 ml. The present invention has no particular requirement on the specific method of dispersion, and the stabilized lithium powder can be uniformly dispersed in the organic solvent using a dispersion method well known to those skilled in the art.
After the stabilized lithium powder dispersion liquid is obtained, the stabilized lithium powder dispersion liquid is coated on the surface of the carbon nano tube-hydroxyapatite ultra-long nanowire pole piece. The present invention does not require a particular method for the coating, and a coating method well known to those skilled in the art may be used. The thickness of the coating is not particularly required in the present invention, and it is preferable to determine the coating thickness according to the target loading amount of the lithium powder and the concentration of the stabilized lithium powder dispersion.
In the invention, the hot-press forming temperature is preferably 150-180 ℃, more preferably 160-170 ℃, the time is preferably 5-10 min, more preferably 6-8 min, and the pressure is preferably 10-12 MPa, more preferably 11 MPa. The present invention preferably uses a press vulcanizer for hot press molding.
The invention provides a stabilized lithium powder-carbon nanotube-ultra-long nanowire composite electrode prepared by the preparation method in the scheme, which comprises a carbon nanotube-ultra-long nanowire pole piece and stabilized lithium powder loaded on the pole piece. In the invention, the preferable load capacity of the stabilized lithium powder on the surface of the composite electrode is 0.01-0.1 g/cm2More preferably 0.05 to 0.08g/cm2. In the invention, the pole piece is composed of the hydroxyapatite ultralong nanowire and the carbon nanotube, the hydroxyapatite ultralong nanowire has good flexibility, high temperature resistance, corrosion resistance and good biological safety, the carbon nanotube has a good porous structure, and the stabilized lithium powder can be well blended into the pole piece, thereby improving the quality of the lithium batteryElectrochemical performance of the electrode.
The invention provides a super capacitor which comprises a positive electrode, a diaphragm, a negative electrode and electrolyte. In the present invention, the negative electrode is the stabilized lithium powder-carbon nanotube-ultra-long nanowire composite electrode described in the above scheme, and details are not repeated here.
In the invention, the positive electrode is preferably an activated carbon-hydroxyapatite ultra-long nanowire composite electrode, and the preparation method of the activated carbon-hydroxyapatite ultra-long nanowire composite electrode preferably comprises the following steps:
mixing activated carbon and water, and dispersing to obtain an activated carbon dispersion liquid;
mixing the hydroxyapatite ultralong nanowire with an alcohol solvent, and pulping to obtain a hydroxyapatite ultralong nanowire suspension;
mixing the active carbon dispersion liquid and the hydroxyapatite ultralong nanowire suspension, coating the mixed slurry on a substrate, and stripping the substrate to obtain an active carbon-hydroxyapatite ultralong nanowire wet pole piece; and drying the wet pole piece to obtain the active carbon-hydroxyapatite ultra-long nanowire composite electrode.
The invention mixes activated carbon and water and then disperses the mixture to obtain the activated carbon dispersion liquid. In the invention, the dispersing and dispersing preferably comprises ultrasonic dispersing and shear dispersing which are sequentially carried out, the ultrasonic dispersing time is preferably 20-40 min, and the shear dispersing time is preferably 15-60 min; the present invention has no special requirement on the specific method of the shear dispersion, and the shear dispersion method known to those skilled in the art can be used, such as stirring; the invention has no special requirements on the power of ultrasonic dispersion and the shearing dispersion strength, and can uniformly disperse the activated carbon. In the present invention, the mass concentration of the activated carbon in the activated carbon dispersion liquid is preferably 3 to 8%, and more preferably 4 to 6%.
In the present invention, the preparation method of the hydroxyapatite ultra-long nanowire suspension, the types of the alcohol solvents, and the concentration of the suspension are consistent with the above scheme, and are not described herein again.
In the invention, the active carbon dispersion liquid and the hydroxyapatite ultralong nanowire suspension are mixed to obtain mixed slurry. In the invention, the volume ratio of the activated carbon dispersion liquid to the hydroxyapatite ultralong nanowire suspension is preferably 1-3: 1, and more preferably 2: 1.
After the mixed slurry is obtained, the mixed slurry is coated on a substrate, and the substrate is peeled off to obtain an active carbon-hydroxyapatite ultralong nanowire wet pole piece; and drying the wet pole piece to obtain the active carbon-hydroxyapatite ultra-long nanowire composite electrode. In the invention, the processes of coating, substrate stripping and drying of the wet electrode plate are the same as the process for preparing the carbon nanotube-hydroxyapatite ultralong nanowire in the scheme, and are not described again.
In the invention, the diaphragm of the supercapacitor is preferably a polypropylene microporous membrane, and the electrolyte is preferably LiPF6And (3) an electrolyte.
In the present invention, the supercapacitor preferably further comprises a positive electrode can and a negative electrode can, and the present invention does not require the positive electrode can and the negative electrode can, and can be used as is well known to those skilled in the art.
The method for assembling the super capacitor has no special requirement, and the super capacitor can be assembled by using a method well known by the technical personnel in the field.
The present invention provides a stabilized lithium powder-carbon nanotube-ultra-long nanowire composite electrode, a method for preparing the same, and a supercapacitor, which are described in detail below with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Placing 0.5g of carbon nanotube, 0.05g of SDS and water in a beaker, and performing ultrasonic dispersion for 30min and sanding for 30min by a sand mill to obtain the carbon nanotube aqueous dispersion liquid.
(2) Pulping the hydroxyapatite ultralong nanowire in alcohol for 5min by using a beater to obtain a hydroxyapatite ultralong nanowire suspension.
(3) Uniformly mixing the prepared carbon nanotube dispersion liquid and the hydroxyapatite ultralong nanowire suspension liquid by using an airflow collider, spraying the mixed slurry (the mass ratio of the carbon nanotubes to the hydroxyapatite ultralong nanowires in the mixed slurry is 3:7) on a foil substrate by using a high-pressure airless sprayer, stripping the foil, and drying in a drying box at 60 ℃ to obtain the carbon nanotube-hydroxyapatite ultralong nanowire pole piece.
(4) And 3g of perfluoro resin is placed in a quartz cup, 1g of metal lithium powder is added, the metal lithium powder and the perfluoro resin are placed at a distance, the quartz cup is placed in a tube furnace and heated to 350 ℃ for heat preservation for 2h, and then the temperature is reduced to 150 ℃ for heat preservation for 12h, so that the stabilized lithium powder is obtained.
(5) Dissolving stabilized lithium powder in benzene for dispersion, uniformly coating the stabilized lithium powder dispersion liquid on a prepared carbon nano tube-hydroxyapatite super-long nanowire pole piece, carrying out hot pressing for 10min at the temperature of 150 ℃ and the pressure of 10Mpa by a flat vulcanizing machine, and cutting into pole pieces with the diameter of 14mm to obtain the stabilized lithium powder-carbon nano tube-super-long nanowire composite electrode, wherein the loading capacity of the stabilized lithium powder is 0.05g/cm2。
Example 2
(1) Placing 1g of carbon nanotube, 0.06g of SDS and water in a beaker, and performing ultrasonic dispersion for 30min and sanding for 30min by a sand mill to obtain the carbon nanotube aqueous dispersion liquid.
(2) Pulping the hydroxyapatite ultralong nanowire in alcohol for 5min by using a beater to obtain a hydroxyapatite ultralong nanowire suspension.
(3) Uniformly mixing the prepared carbon nanotube dispersion liquid and the hydroxyapatite ultralong nanowire suspension liquid by using an airflow collider, spraying the mixed slurry (the mass ratio of the carbon nanotubes to the hydroxyapatite ultralong nanowires in the mixed slurry is 4:6) on a foil substrate by using a high-pressure airless sprayer, stripping the foil, and drying in a drying box at 60 ℃ to obtain the carbon nanotube-hydroxyapatite ultralong nanowire pole piece.
(4) And (2) placing 5g of perfluoro resin in a quartz cup, adding 1g of metal lithium powder, placing the metal lithium powder and the perfluoro resin at a certain distance, placing the quartz cup in a tubular furnace, heating to 330 ℃, preserving heat for 1h, cooling to 180 ℃, and preserving heat for 10h to form the stabilized lithium powder.
(5) Dissolving stabilized lithium powder in benzene for dispersionUniformly coating the lithium powder dispersion liquid on a prepared carbon nano tube-hydroxyapatite super-long nano wire pole piece, hot-pressing the carbon nano tube-hydroxyapatite super-long nano wire pole piece for 5min at the temperature of 180 ℃ and under the pressure of 12MPa by a flat vulcanizing machine, and cutting the carbon nano tube-hydroxyapatite super-long nano wire pole piece into pole pieces with the diameter of 14mm to obtain the stabilized lithium powder-carbon nano tube-super-long nano wire composite electrode, wherein the loading capacity of the stabilized lithium powder is 0.1g/cm2。
Example 3
0.5g of activated carbon is weighed and placed in a beaker, and is subjected to ultrasonic dispersion for 30min and shearing dispersion for 30min to obtain the aqueous activated carbon dispersion.
And pulping the hydroxyapatite ultralong nanowire in alcohol for 10min by using a pulping machine to obtain a hydroxyapatite ultralong nanowire suspension.
And uniformly mixing the prepared active carbon dispersion liquid and the hydroxyapatite ultra-long nanowire suspension liquid by using an air flow collider, spraying the mixed slurry on a foil substrate by using a high-pressure airless sprayer, peeling the foil, drying in a drying box at 60 ℃, and cutting into a pole piece with the diameter of 14mm to obtain the active carbon-hydroxyapatite ultra-long nanowire composite electrode.
The stabilized lithium powder-carbon nanotube-ultra-long nanowire composite electrode prepared in example 1 was used as a negative electrode, the activated carbon-hydroxyapatite ultra-long nanowire composite electrode was used as a positive electrode, and LiPF was used6And adding the electrolyte into the vacuum glove box, and assembling the lithium ion super capacitor by the negative electrode shell, the negative electrode plate, the diaphragm, the positive electrode plate and the positive electrode shell in sequence, wherein the lithium ion super capacitor is marked as a # 1 super capacitor.
And (3) using the carbon nanotube-hydroxyapatite ultra-long nanowire pole piece in the step (3) in the embodiment 1 as a negative pole, and assembling the super capacitor according to the same method, wherein the super capacitor is marked as a # 2 super capacitor.
The power density and the energy density of the 1# super capacitor and the 2# super capacitor are tested under the following conditions: the current density of constant current charging and discharging is 100 mA/g-7000 mA/g, and the voltage window of charging and discharging is 2-4V. The results are shown in fig. 1, where fig. 1 is a plot of power density versus energy density for a supercapacitor. As can be seen from fig. 1, the energy density reduction amplitude is significantly reduced with the increase of the power density in the 1# supercapacitor and the 2# capacitor.
The cycle performance of the 1# super capacitor and the 2# super capacitor is tested under the test conditions that the charge and discharge current density is 400mA/g, the charge and discharge voltage window is 2-4V, the test result is shown in figure 2, and figure 2 is a cycle performance test chart of the super capacitor. According to fig. 2, after 3500 cycles, the capacity retention rate of the 1# super capacitor can reach about 90%, and the capacity retention rate of the 2# capacitor is below 70%.
According to the results, the stabilized lithium powder-carbon nanotube-ultra-long nanowire composite electrode provided by the invention has more excellent electrochemical performance, and a super capacitor assembled by taking the composite electrode as a negative electrode has high energy density and good cycle performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of a stabilized lithium powder-carbon nanotube-ultra-long nanowire composite electrode comprises the following steps:
(1) mixing a dispersing agent, a carbon nano tube and water, and then sequentially carrying out ultrasonic treatment and sand milling treatment to obtain a carbon nano tube dispersion liquid;
(2) mixing the hydroxyapatite ultralong nanowire with an alcohol solvent, and pulping to obtain a hydroxyapatite ultralong nanowire suspension;
(3) mixing the carbon nano tube dispersion liquid and the hydroxyapatite ultralong nanowire suspension, coating the obtained mixed slurry on a substrate, and stripping the substrate to obtain a carbon nano tube-hydroxyapatite ultralong nanowire wet pole piece; drying the wet pole piece to obtain a carbon nano tube-hydroxyapatite ultra-long nanowire pole piece;
(4) carrying out heat treatment on the perfluorinated resin and the metal lithium powder under the condition of spaced placement to obtain stabilized lithium powder; the heat treatment comprises high-temperature heat treatment and low-temperature heat treatment which are sequentially carried out; the temperature of the high-temperature heat treatment is 330-350 ℃, and the time is 1-2 h; the temperature of the low-temperature heat treatment is 150-180 ℃, and the time is 10-12 hours;
(5) carrying out pre-lithiation treatment on the carbon nano tube-hydroxyapatite ultra-long nanowire pole piece by using the stabilized lithium powder to obtain a stabilized lithium powder-carbon nano tube-ultra-long nanowire composite electrode;
the steps (1), (2) and (4) are not limited by time sequence;
the steps (3) and (4) are not limited in chronological order.
2. The production method according to claim 1, characterized in that the prelithiation treatment in the step (5) includes the steps of: and dispersing the stabilized lithium powder in an organic solvent, coating the obtained stabilized lithium powder dispersion liquid on the surface of the carbon nano tube-hydroxyapatite ultra-long nanowire pole piece, and then carrying out hot press molding.
3. The preparation method according to claim 2, wherein the hot press forming temperature is 150-180 ℃, the pressure is 10-12 MPa, and the time is 5-10 min.
4. The preparation method according to claim 1, wherein the mass ratio of the carbon nanotubes to the hydroxyapatite ultralong nanowires in the mixed slurry in the step (3) is 3:7 to 7: 3.
5. The preparation method according to claim 1, wherein the mass ratio of the perfluoro resin to the lithium metal powder in the step (4) is 2-5: 1.
6. The stabilized lithium powder-carbon nanotube-ultra-long nanowire composite electrode prepared by the preparation method of any one of claims 1 to 5, which comprises a carbon nanotube-ultra-long nanowire pole piece and the stabilized lithium powder loaded on the pole piece, wherein the loading amount of the stabilized lithium powder on the surface of the composite electrode is 0.01 to 0.1g/m2。
7. A super capacitor, comprising a positive electrode, a diaphragm, a negative electrode and an electrolyte, wherein the negative electrode is the stabilized lithium powder-carbon nanotube-ultra-long nanowire composite electrode of claim 6.
8. The supercapacitor according to claim 7, wherein the positive electrode is an activated carbon-hydroxyapatite ultra-long nanowire composite electrode;
the preparation method of the active carbon-hydroxyapatite ultra-long nanowire composite electrode comprises the following steps:
mixing activated carbon and water, and then performing dispersion treatment to obtain an activated carbon dispersion liquid;
mixing the hydroxyapatite ultralong nanowire with an alcohol solvent, and pulping to obtain a hydroxyapatite ultralong nanowire suspension;
mixing the active carbon dispersion liquid and the hydroxyapatite ultralong nanowire suspension, coating the mixed slurry on a substrate, and stripping the substrate to obtain an active carbon-hydroxyapatite ultralong nanowire wet pole piece; and drying the wet pole piece to obtain the active carbon-hydroxyapatite ultra-long nanowire composite electrode.
9. The supercapacitor according to claim 7 or 8, wherein the separator is a polypropylene microporous membrane; the electrolyte is LiPF6And (3) an electrolyte.
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| WO2012057031A1 (en) * | 2010-10-27 | 2012-05-03 | 協立化学産業株式会社 | Conductive undercoating agent composition |
| WO2014119663A1 (en) * | 2013-02-01 | 2014-08-07 | 株式会社日本触媒 | Electrode precursor, electrode, and battery |
| CN106654215A (en) * | 2016-12-30 | 2017-05-10 | 温州大学 | Small biological molecule and graphene composite material functional film and preparation method thereof |
| CN107565081A (en) * | 2017-07-11 | 2018-01-09 | 中国科学院上海硅酸盐研究所 | A kind of hydroxyapatite overlong nanowire based high-temp-resistant battery diaphragm and its application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012057031A1 (en) * | 2010-10-27 | 2012-05-03 | 協立化学産業株式会社 | Conductive undercoating agent composition |
| WO2014119663A1 (en) * | 2013-02-01 | 2014-08-07 | 株式会社日本触媒 | Electrode precursor, electrode, and battery |
| CN106654215A (en) * | 2016-12-30 | 2017-05-10 | 温州大学 | Small biological molecule and graphene composite material functional film and preparation method thereof |
| CN107565081A (en) * | 2017-07-11 | 2018-01-09 | 中国科学院上海硅酸盐研究所 | A kind of hydroxyapatite overlong nanowire based high-temp-resistant battery diaphragm and its application |
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