CN109473649B - Composite negative electrode material of sodium-ion battery and preparation method thereof - Google Patents
Composite negative electrode material of sodium-ion battery and preparation method thereof Download PDFInfo
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Abstract
A composite cathode material of a sodium ion battery and a preparation method thereof belong to the field of cathode materials of sodium ion batteries. The invention aims to solve the technical problem of developing a novel sodium-ion battery cathode material. The preparation method comprises the steps of preparing a graphene foam material, growing carbon nanotubes on the prepared graphene foam material, preparing a carbon nanotube-graphene foam composite material, carrying out surface treatment on the prepared carbon nanotube-graphene foam composite material, preparing vanadium dioxide nanosheet reaction liquid, completely placing the prepared carbon nanotube-graphene foam composite material in the prepared vanadium dioxide nanosheet reaction liquid, controlling the reaction temperature to be 175-185 ℃ and the reaction time to be 3-3.5 hours, taking out a product after the reaction, washing the product with deionized water and alcohol for a plurality of times, drying and annealing the product for 2-2.5 hours. The invention is used for the negative electrode material of the sodium-ion battery, and improves the conductivity of the active substance and the energy density of the battery.
Description
Technical Field
The invention belongs to the field of negative electrode materials of sodium ion batteries; in particular to a composite cathode material of a sodium-ion battery and a preparation method thereof.
Background
At present, the main way for human beings to obtain energy is through the combustion of fossil fuel, however, the massive combustion of fossil fuel not only leads to resource exhaustion, but also brings about serious problems of environmental pollution, climate warming and the like. Therefore, the development of renewable, environmentally friendly energy storage and conversion technologies has become a global research goal. The lithium ion battery attracts the attention of the majority of researchers with the advantages of high reversible specific capacity, long cycle life, environmental protection and the like, and is widely applied to portable electronic equipment. However, the lithium resources on earth are scarce, and it is difficult to maintain the increasing energy demand of human beings. Therefore, a novel energy storage and conversion system which is rich in development resources, low in cost, green and safe and can replace a lithium ion battery is urgent.
Sodium element of the same main group has electrochemical properties similar to lithium, and sodium element is widely distributed in the earth crust, so the research heat of sodium ion batteries has been increasing year by year in recent years. As is well known, similar to lithium ion batteries, the main factor restricting the electrochemical performance of sodium ion batteries is electrode materials, and therefore, the search for suitable sodium storage materials is important in research. Sodium ions have larger ionic radius, and a wider ion channel is needed in the charge and discharge process, so that a host material of lithium ions cannot be directly used as an electrode material of a sodium ion battery. Most materials have slow electrochemical reaction kinetics when used as sodium ion battery electrodes, so that not all lithium ion battery electrode materials are suitable for being used as sodium ion electrodes.
Disclosure of Invention
The invention aims to provide a composite cathode material of a sodium-ion battery and a preparation method thereof.
The invention is realized by the following technical scheme:
a preparation method of a composite anode material of a sodium-ion battery comprises the following steps:
step a, preparing a graphene foam material for later use;
b, growing carbon nanotubes on the graphene foam material prepared in the step a, and preparing a carbon nanotube-graphene foam composite material for later use;
c, performing surface treatment on the carbon nano tube-graphene foam composite material prepared in the step b, and treating for later use;
d, preparing vanadium dioxide nanosheet reaction liquid for later use;
and e, completely placing the carbon nano tube-graphene foam composite material prepared in the step c into the vanadium dioxide nanosheet reaction solution prepared in the step d, controlling the reaction temperature to be 175-185 ℃ and the reaction time to be 3-3.5 h, taking out a product after reaction, washing the product with deionized water and alcohol for 3-5 times, and placing the product in a vacuum oven at 120-130 ℃ to dry for 6-7 h. And finally, annealing the product in air at 400-420 ℃ for 2-2.5 hours to obtain the sodium-ion battery composite negative electrode material.
The preparation method of the composite cathode material of the sodium-ion battery comprises the following steps:
a1, cleaning a nickel foam substrate, soaking the nickel foam substrate in 5% diluted hydrochloric acid for 4-6 hours, washing the nickel foam substrate with deionized water for 3-5 times, and drying the nickel foam substrate at 60 ℃ for later use;
step a2, placing the nickel foam substrate processed in the step a1 in a horizontal quartz tube furnace, introducing mixed gas of argon and hydrogen into the horizontal quartz tube furnace, heating to 1000 ℃, keeping for 5min, taking the mixed gas of argon and hydrogen as carrier gas, introducing the mixed gas into a reaction cavity through liquid ethanol, keeping for 5min at 1000 ℃, then recovering to be the mixed gas introduced with argon and hydrogen, and rapidly cooling to room temperature to obtain a sample for later use;
step a3, soaking the sample obtained in the step a2 in 1mol/l FeCl3And 5wt% of dilute hydrochloric acid, and taking out after 48 hours to obtain the graphene foam material.
According to the preparation method of the composite cathode material of the sodium-ion battery, the size of the nickel foam substrate in the step a1 is 2cm multiplied by 2 cm-8 cm multiplied by 8cm, and the thickness of the nickel foam substrate is 0.9-1.1 mm.
The invention relates to a preparation method of a composite cathode material of a sodium-ion battery, wherein the flow rate of argon in the mixed gas of argon and hydrogen in the step a2 is 280sccm, the flow rate of hydrogen is 20sccm, the flow rate of argon in the mixed gas of argon and hydrogen carrier gas is 160sccm, and the flow rate of hydrogen is 40 sccm.
The preparation method of the sodium-ion battery composite negative electrode material comprises the following steps:
step b1, preparing nickel cobalt catalyst, adding 1mmolNi (NO)3)2·6H2O and 2mmol Co (NO)3)2·6H2Adding O into 40ml of deionized water in sequence, adding 12mmol of urea after carrying out ultrasonic treatment for 15 minutes, and carrying out ultrasonic treatment for 15 minutes to obtain the nickel-cobalt catalyst;
b2, placing the carbon nano tube growing on the graphene foam material prepared in the step a in the nickel-cobalt catalyst obtained in the step b1, carrying out hydrothermal reaction for 2 hours at 120 ℃, and naturally cooling to room temperature to obtain a nickel-cobalt composite graphene foam material;
and b3, placing the nickel-cobalt composite graphene foam material prepared in the step b2 in a horizontal quartz tube furnace, introducing argon into the horizontal quartz tube furnace, heating to 750 ℃, introducing a mixed gas of argon, hydrogen and ethylene, keeping for 10min, and then returning to the state that the introduced argon is rapidly cooled to room temperature to obtain the carbon nano tube-graphene foam composite material.
According to the preparation method of the sodium-ion battery composite negative electrode material, the flow rate of argon in the step b3 is 100sccm, the flow rate of argon in the mixed gas of argon, hydrogen and ethylene is 100sccm, the flow rate of hydrogen is 40sccm, and the flow rate of ethylene is 20 sccm.
According to the preparation method of the sodium-ion battery composite negative electrode material, the surface of the carbon nano tube-graphene foam composite material in the step c is treated by placing the carbon nano tube-graphene foam composite material prepared in the step b in concentrated sulfuric acid and boiling the mixture for 2 hours at 120 ℃.
The invention relates to a preparation method of a sodium ion battery composite negative electrode material, and the surface of the materialThe mass density of the treated carbon nano tube-graphene foam composite material is 0.65-0.66 mg/cm2。
The preparation method of the composite cathode material of the sodium-ion battery comprises the following steps:
step d1, weigh 1.2gV2O5Dissolving the powder and 1.8g of oxalic acid powder in 40ml of deionized water, and performing hot water bath at 75 ℃ until the powder is completely dissolved to obtain a mixed solution for later use;
and d2, measuring 5ml of the mixed solution obtained in the step 1, transferring the mixed solution to a 30ml reaction kettle, adding 1ml of 30wt% hydrogen peroxide and 20ml of absolute ethyl alcohol, and continuously stirring for 20min to obtain the vanadium dioxide nanosheet reaction solution.
The capacity of the composite negative electrode material of the sodium-ion battery is less than or equal to 650mAhg-1。
Compared with the traditional powder electrode material, the composite anode material for the sodium-ion battery generally pursues smaller particle size, namely a nano material. Compared with a bulk material, the nano material has larger active surface area and is more beneficial to the embedding and the separation of sodium ions, however, the particle agglomeration phenomenon is easily generated in the charge and discharge process due to the undersized nano size, and the advantages of the nano material are weakened. The invention combines the nano material with the array electrode, successfully utilizes a one-step solvent thermal method to carry out VO2The nano-sheets are uniformly embedded on the surface of a conductive substrate GF (graphene Foam)/CNTs (carbon nanotubes), so that the advantage of the high-activity surface of the nano-material is exerted, the conductivity of an active substance is improved, and the energy density of the battery is improved.
The sodium ion battery composite negative electrode material has the following beneficial effects:
(1) GF is a porous, lightweight, electrically conductive substrate material, and CNTs grown on GF is a one-dimensional material providing high porosity, high flexibility, and high aspect ratio. The GF/CNTs nano composite film with the three-dimensional structure has the advantages of super large specific surface area, super high conductivity, high porosity and good wettability, thus being a very good ion and electron transmission framework structure;
(2) the three-dimensional CNTs/GF film has super-strong conductivity as a flexible substrate, is an excellent current collector, has super-light weight, and greatly improves the specific capacity of the sodium-ion battery;
(3) two-dimensional ultrathin VO2The nano-sheets are directly embedded on the surface of the GF/CNTs film, and a conductive substance and an adhesive are not required to be added, so that the energy density of the traditional powder electrode material is further improved;
(4) compared with a bulk material, the nano material has larger active surface area and is more beneficial to the embedding and the separation of sodium ions, however, the particle phenomenon is easily generated in the charge and discharge process due to the undersized nano size, and the advantages of the nano material are weakened. According to the sodium-ion battery composite negative electrode material, the nano material is combined with the array electrode, and the VO2 nanosheet is successfully and uniformly embedded on the surface of the conductive substrate GF/CNTs, so that the agglomeration of the nano material is overcome, the advantages of the nano material are exerted, and meanwhile, the conductivity of an active substance is improved;
(5) VO of layered structure2Is favorable for the intercalation and deintercalation of sodium ions and is an ultrathin VO2The topography shortens the ion/electron diffusion distance and provides a larger surface for sodium ion storage, enhancing sodium ion diffusion and charge transfer.
(6)VO2The flexible characteristic of the/CNTs/GF composite material can effectively relieve the volume change in the charge and discharge process to a certain extent, thereby improving the cycle stability of the battery.
The composite cathode material for the sodium-ion battery overcomes the defect of low active surface of the traditional cathode material for the sodium-ion battery, increases the specific capacity, removes the addition of conductive substances and binders, improves the energy density of the battery, and is a promising cathode material for the sodium-ion battery.
Drawings
FIG. 1 is an X-ray diffraction pattern of a composite anode material for a sodium-ion battery prepared by a method according to an embodiment;
FIG. 2 is a 150 times scanning electron microscope image of a composite cathode material of a sodium ion battery prepared by a method according to an embodiment;
FIG. 3 is a scanning electron microscope image of 1 ten thousand times of the composite cathode material of the sodium-ion battery prepared by the method of the embodiment;
FIG. 4 is a scanning electron microscope image of 10 ten thousand times of a composite cathode material of a sodium ion battery prepared by a method according to an embodiment;
FIG. 5 is a transmission electron microscope image of 10 ten thousand times of a composite cathode material of a sodium ion battery prepared by a method according to an embodiment;
FIG. 6 is a transmission electron microscope image of 200 ten thousand times of a composite anode material of a sodium ion battery prepared by a method according to an embodiment;
FIG. 7 is a high-resolution TEM image of a composite cathode material of a Na-ion battery prepared by a method according to an embodiment;
FIG. 8 is a selected area electron diffraction pattern of a composite anode material for a sodium ion battery prepared by a method according to an embodiment;
FIG. 9 is a graph of the cycle performance of a composite anode material for a sodium ion battery prepared according to a method of an embodiment;
fig. 10 is a rate performance curve of a composite anode material of a sodium ion battery prepared by a method of an embodiment.
Detailed Description
The first embodiment is as follows:
a preparation method of a composite anode material of a sodium-ion battery comprises the following steps:
step a, preparing a graphene foam material for later use;
b, growing carbon nanotubes on the graphene foam material prepared in the step a, and preparing a carbon nanotube-graphene foam composite material for later use;
c, performing surface treatment on the carbon nano tube-graphene foam composite material prepared in the step b, and treating for later use;
d, preparing vanadium dioxide nanosheet reaction liquid for later use;
and e, completely placing the carbon nano tube-graphene foam composite material prepared in the step c into the vanadium dioxide nanosheet reaction solution prepared in the step d, controlling the reaction temperature to be 180 ℃, reacting for 3 hours, taking out a product after reaction, washing the product with deionized water and alcohol for 4 times, and placing the product in a vacuum oven at 120 ℃ for drying for 6 hours. And finally, annealing the product in air at 400 ℃ for 2 hours to obtain the sodium-ion battery composite negative electrode material.
In the preparation method of the sodium-ion battery composite negative electrode material according to the embodiment, the preparation method of the graphene foam material in the step a includes the following steps:
step a1, cleaning the nickel foam substrate, soaking the nickel foam substrate for 5 hours by using 5% diluted hydrochloric acid, washing the nickel foam substrate for 4 times by using deionized water, and drying the nickel foam substrate at 60 ℃ for later use;
step a2, placing the nickel foam substrate processed in the step a1 in a horizontal quartz tube furnace, introducing mixed gas of argon and hydrogen into the horizontal quartz tube furnace, heating to 1000 ℃, keeping for 5min, taking the mixed gas of argon and hydrogen as carrier gas, introducing the mixed gas into a reaction cavity through liquid ethanol, keeping for 5min at 1000 ℃, then recovering to be the mixed gas introduced with argon and hydrogen, and rapidly cooling to room temperature to obtain a sample for later use;
step a3, soaking the sample obtained in the step a2 in 1mol/l FeCl3And 5wt% of dilute hydrochloric acid, and taking out after 48 hours to obtain the graphene foam material.
In the method for preparing the composite negative electrode material of the sodium-ion battery according to the embodiment, the size of the nickel foam substrate in the step a1 is 8cm × 8cm, and the thickness of the nickel foam substrate is 1 mm.
In the preparation method of the sodium-ion battery composite negative electrode material, in the step a2, the flow rate of argon in the mixed gas of argon and hydrogen is 280sccm, the flow rate of hydrogen is 20sccm, then the mixed gas of argon and hydrogen is taken as carrier gas and is brought into the reaction cavity through liquid ethanol, the flow rate of argon in the mixed gas of argon and hydrogen carrier gas is 160sccm, the flow rate of hydrogen is 40sccm, the mixture is kept at 1000 ℃ for 5min, and then the mixture is recovered to be the mixed gas into which argon and hydrogen are introduced, and the temperature is rapidly reduced to room temperature to obtain a sample.
In the preparation method of the sodium-ion battery composite negative electrode material according to the embodiment, the preparation method of the carbon nanotube-graphene foam composite material in the step b includes the following steps:
step b1, preparing nickel cobalt catalyst, adding 1mmolNi (NO)3)2·6H2O and 2mmol Co (NO)3)2·6H2Adding O into 40ml of deionized water in sequence, adding 12mmol of urea after carrying out ultrasonic treatment for 15 minutes, and carrying out ultrasonic treatment for 15 minutes to obtain the nickel-cobalt catalyst;
b2, placing the carbon nano tube growing on the graphene foam material prepared in the step a in the nickel-cobalt catalyst obtained in the step b1, carrying out hydrothermal reaction for 2 hours at 120 ℃, and naturally cooling to room temperature to obtain a nickel-cobalt composite graphene foam material;
and b3, placing the nickel-cobalt composite graphene foam material prepared in the step b2 in a horizontal quartz tube furnace, introducing argon into the horizontal quartz tube furnace, heating to 750 ℃, introducing a mixed gas of argon, hydrogen and ethylene, keeping for 10min, and then returning to the state that the introduced argon is rapidly cooled to room temperature to obtain the carbon nano tube-graphene foam composite material.
In the method for preparing a composite negative electrode material for a sodium-ion battery according to this embodiment, the flow rate of argon in step b3 is 100sccm, the flow rate of argon in a mixed gas of argon, hydrogen and ethylene is 100sccm, the flow rate of hydrogen is 40sccm, and the flow rate of ethylene is 20 sccm.
In the preparation method of the sodium-ion battery composite negative electrode material according to the embodiment, the surface treatment of the carbon nanotube-graphene foam composite material in the step c is to place the carbon nanotube-graphene foam composite material prepared in the step b in concentrated sulfuric acid and boil the carbon nanotube-graphene foam composite material at 120 ℃ for 2 hours.
The preparation method and surface of the composite anode material for the sodium-ion batteryThe mass density of the treated carbon nano tube-graphene foam composite material is 0.65mg/cm2。
In the preparation method of the composite anode material for the sodium-ion battery according to the embodiment, the preparation method of the vanadium dioxide nanosheet reaction solution in the step d includes the following steps:
step d1, weigh 1.2gV2O5Dissolving the powder and 1.8g of oxalic acid powder in 40ml of deionized water, and performing hot water bath at 75 ℃ until the powder is completely dissolved to obtain a mixed solution for later use;
and d2, measuring 5ml of the mixed solution obtained in the step 1, transferring the mixed solution to a 30ml reaction kettle, adding 1ml of 30wt% hydrogen peroxide and 20ml of absolute ethyl alcohol, and continuously stirring for 20min to obtain the vanadium dioxide nanosheet reaction solution.
The second embodiment is as follows:
according to the sodium-ion battery composite negative electrode material prepared by the preparation method of the sodium-ion battery composite negative electrode material, according to the specific embodiment, the capacity of the sodium-ion battery composite negative electrode material is less than or equal to 650mAhg-1。
An X-ray diffraction test of the sodium-ion battery composite negative electrode material prepared by the preparation method of the sodium-ion battery composite negative electrode material according to the embodiment is shown in fig. 1, and as can be seen from an X-ray diffraction spectrum, a strong diffraction peak is present at about 26 degrees, the strong diffraction peak is a diffraction peak of graphene (JCPDS-No.75-1621), corresponds to a (002) crystal face of 2H-phase graphene, and all the rest diffraction peaks can be matched with a monoclinic phase VO2(B) (JCPDS-No.31-1438) in a PDF card without other miscellaneous peaks, and the result shows that a pure-phase VO2 nanosheet is successfully prepared.
The sodium ion battery composite negative electrode material prepared by the preparation method of the sodium ion battery composite negative electrode material according to the embodiment is subjected to scanning electron microscope tests, and scanning electron microscope pictures with different magnifications are shown in fig. 2, 3 and 4, so that it can be seen from the pictures that the carbon nanotubes are uniformly distributed on the graphene foam, and the VO is VO2The nano-sheets are vertically embedded on the surface of the carbon nano-tube to form a structure with high porosity and large specific surface area. Such a knotThe unique structural design of the composite cathode material of the sodium ion battery can realize the storage of high-rate sodium ions and can obtain good electrochemical performance.
The sodium-ion battery composite negative electrode material prepared by the preparation method of the sodium-ion battery composite negative electrode material according to the embodiment is subjected to transmission electron microscope tests, transmission electron microscope pictures with different magnifications are shown in fig. 5-8, and the structure of the VO2/CNTs/GF composite nanosheet array is further verified, and fig. 5 is VO2/CNTs/GF composite nanosheet array2And (3) a TEM image of the CNTs composite nanosheet, wherein the VO2 nanosheet is uniformly wrapped on the surface of the carbon nanotube. FIG. 6 is an enlarged view of the red dashed box in FIG. 5, and it can be seen from FIG. 6 that the diameter of the carbon nanotube is about 20nm and the VO2 nanosheets are tightly connected to CNTs. FIG. 7 is a photograph of a high-power transmission electron microscope, from which it can be clearly seen that the interplanar spacing is about
Corresponds to the (200) crystal plane of VO 2. VO2 nanosheets of single crystal structure can be corroborated by fig. 8.
The electrochemical performance test of the sodium-ion battery composite negative electrode material prepared by the preparation method of the sodium-ion battery composite negative electrode material according to the embodiment is performed, as shown in fig. 9 and 10. FIG. 9 is a cycle stability test, as can be seen in FIG. 9, at 0.2Ag-1The sodium-ion battery composite negative electrode material adopts CNTs/GF substrate to improve VO (vanadium oxide) and has good cycle stability, the capacity is hardly attenuated after the current density is cycled for 250 circles, the coulombic efficiency is about 100 percent, and the good cycle stability is shown2Conductivity of the nanosheet, increased VO2The specific capacity of the nano-sheet is beneficial to improving the cycling stability of the composite cathode material of the sodium-ion battery. FIG. 10 is a graph of stability of electrode materials at different current densities, the electrode materials being 0.1Ag respectively-1，0.2Ag-1，0.5Ag-1，1Ag-1，2Ag-1，3Ag-1，5Ag-1，10Ag-1At current density ofCirculating, its capacity can be stabilized at 650mAhg-1，600mAhg-1，560mAhg-1，490mAhg-1，440mAhg-1，375mAhg-1，300mAhg-1，200mAhg-1Left and right, and when the cycle returns to the low current density of 2Ag-1When tested, the capacity of the material is also increased to 410mAhg-1. The specific structural design of the composite cathode material of the sodium ion battery realizes the storage of the high-rate sodium ions.
The third concrete implementation mode:
a preparation method of a composite anode material of a sodium-ion battery comprises the following steps:
step a, preparing a graphene foam material for later use;
b, growing carbon nanotubes on the graphene foam material prepared in the step a, and preparing a carbon nanotube-graphene foam composite material for later use;
c, performing surface treatment on the carbon nano tube-graphene foam composite material prepared in the step b, and treating for later use;
d, preparing vanadium dioxide nanosheet reaction liquid for later use;
and e, completely placing the carbon nano tube-graphene foam composite material prepared in the step c into the vanadium dioxide nanosheet reaction solution prepared in the step d, controlling the reaction temperature to be 175-185 ℃ and the reaction time to be 3-3.5 h, taking out a product after reaction, washing the product with deionized water and alcohol for 3-5 times, and placing the product in a vacuum oven at 120-130 ℃ to dry for 6-7 h. And finally, annealing the product in air at 400-420 ℃ for 2-2.5 hours to obtain the sodium-ion battery composite negative electrode material.
The composite negative electrode material for the sodium-ion battery has the advantages that: GF is a porous, lightweight, electrically conductive substrate material, and CNTs grown on GF is a one-dimensional material providing high porosity, high flexibility, and high aspect ratio. The GF/CNTs nano composite film with the three-dimensional structure has the advantages of super large specific surface area, super high conductivity, high porosity and good wettability, thus being an excellent ion and electron transmission framework structure.
The composite negative electrode material for the sodium-ion battery has the advantages that: the three-dimensional CNTs/GF film has super-strong conductivity as a flexible substrate, is an excellent current collector, has super-light weight, and greatly improves the specific capacity of the sodium-ion battery.
The composite negative electrode material for the sodium-ion battery has the advantages that: two-dimensional ultrathin VO2The nano-sheet is directly embedded on the surface of the GF/CNTs film, and a conductive substance and an adhesive are not required to be added, so that the energy density of the traditional powder electrode material is further improved.
The composite negative electrode material for the sodium-ion battery has the advantages that: compared with a bulk material, the nano material has larger active surface area and is more beneficial to the embedding and the separation of sodium ions, however, the particle phenomenon is easily generated in the charge and discharge process due to the undersized nano size, and the advantages of the nano material are weakened. According to the sodium-ion battery composite negative electrode material, the nano material is combined with the array electrode, and the VO2 nanosheets are successfully and uniformly embedded on the surface of the conductive substrate GF/CNTs, so that the agglomeration of the nano material is overcome, the advantages of the nano material are brought into play, and meanwhile, the conductivity of the active substance is improved.
The composite negative electrode material for the sodium-ion battery has the advantages that: VO of layered structure2Is favorable for the intercalation and deintercalation of sodium ions and is an ultrathin VO2The topography shortens the ion/electron diffusion distance and provides a larger surface for sodium ion storage, enhancing sodium ion diffusion and charge transfer.
The composite negative electrode material for the sodium-ion battery has the advantages that: VO (vacuum vapor volume)2The flexible characteristic of the/CNTs/GF composite material can effectively relieve the volume change in the charge and discharge process to a certain extent, thereby improving the cycle stability of the battery.
The fourth concrete implementation mode:
according to the third specific embodiment, the preparation method of the graphene foam material in step a comprises the following steps:
a1, cleaning a nickel foam substrate, soaking the nickel foam substrate in 5% diluted hydrochloric acid for 4-6 hours, washing the nickel foam substrate with deionized water for 3-5 times, and drying the nickel foam substrate at 60 ℃ for later use;
step a2, placing the nickel foam substrate processed in the step a1 in a horizontal quartz tube furnace, introducing mixed gas of argon and hydrogen into the horizontal quartz tube furnace, heating to 1000 ℃, keeping for 5min, taking the mixed gas of argon and hydrogen as carrier gas, introducing the mixed gas into a reaction cavity through liquid ethanol, keeping for 5min at 1000 ℃, then recovering to be the mixed gas introduced with argon and hydrogen, and rapidly cooling to room temperature to obtain a sample for later use;
step a3, soaking the sample obtained in the step a2 in 1mol/l FeCl3And 5wt% of dilute hydrochloric acid, and taking out after 48 hours to obtain the graphene foam material.
The fifth concrete implementation mode:
according to the third specific embodiment of the preparation method of the composite anode material for the sodium-ion battery, the size of the nickel foam substrate in the step a1 is 2cm × 2 cm-8 cm × 8cm, and the thickness of the nickel foam substrate is 0.9-1.1 mm.
The sixth specific implementation mode:
according to the third specific embodiment, in the step a2, the flow rate of argon in the mixed gas of argon and hydrogen is 280sccm, the flow rate of hydrogen is 20sccm, then the mixed gas of argon and hydrogen is taken as a carrier gas and is brought into the reaction cavity through liquid ethanol, the flow rate of argon in the mixed gas of argon and hydrogen is 160sccm, the flow rate of hydrogen is 40sccm, the mixture is kept at 1000 ℃ for 5min, and then the mixture is recovered to be the mixed gas into which argon and hydrogen are introduced, and the temperature is rapidly reduced to room temperature, so as to obtain a sample.
The seventh embodiment:
according to a third specific embodiment, the method for preparing the composite anode material for the sodium-ion battery in step b, which is implemented by using the carbon nanotube-graphene foam composite material, comprises the following steps:
step b1, preparing nickel cobalt catalyst, adding 1mmolNi (NO)3)2·6H2O and 2mmol Co (NO)3)2·6H2Adding O into 40ml of deionized water in sequence, adding 12mmol of urea after carrying out ultrasonic treatment for 15 minutes, and carrying out ultrasonic treatment for 15 minutes to obtain the nickel-cobalt catalyst;
b2, placing the carbon nano tube growing on the graphene foam material prepared in the step a in the nickel-cobalt catalyst obtained in the step b1, carrying out hydrothermal reaction for 2 hours at 120 ℃, and naturally cooling to room temperature to obtain a nickel-cobalt composite graphene foam material;
and b3, placing the nickel-cobalt composite graphene foam material prepared in the step b2 in a horizontal quartz tube furnace, introducing argon into the horizontal quartz tube furnace, heating to 750 ℃, introducing a mixed gas of argon, hydrogen and ethylene, keeping for 10min, and then returning to the state that the introduced argon is rapidly cooled to room temperature to obtain the carbon nano tube-graphene foam composite material.
The specific implementation mode is eight:
according to the third embodiment of the present invention, in the step b3, the flow rate of argon is 100sccm, the flow rate of argon in the mixed gas of argon, hydrogen and ethylene is 100sccm, the flow rate of hydrogen is 40sccm, and the flow rate of ethylene is 20 sccm.
The specific implementation method nine:
according to the third specific embodiment, in the step c, the surface of the carbon nanotube-graphene foam composite material is treated by placing the carbon nanotube-graphene foam composite material prepared in the step b in concentrated sulfuric acid, and boiling the mixture at 120 ℃ for 2 hours.
The detailed implementation mode is ten:
according to the third specific embodiment, in the preparation method of the sodium-ion battery composite negative electrode material, the mass density of the carbon nanotube-graphene foam composite material subjected to surface treatment is 0.65-0.66 mg/cm2。
The concrete implementation mode eleven:
according to the third specific embodiment, the preparation method of the composite anode material for the sodium-ion battery comprises the following steps:
step d1, weigh 1.2gV2O5Dissolving the powder and 1.8g of oxalic acid powder in 40ml of deionized water, and performing hot water bath at 75 ℃ until the powder is completely dissolved to obtain a mixed solution for later use;
and d2, measuring 5ml of the mixed solution obtained in the step 1, transferring the mixed solution to a 30ml reaction kettle, adding 1ml of 30wt% hydrogen peroxide and 20ml of absolute ethyl alcohol, and continuously stirring for 20min to obtain the vanadium dioxide nanosheet reaction solution.
The specific implementation mode twelve:
according to the sodium-ion battery composite negative electrode material prepared by the preparation method of the sodium-ion battery composite negative electrode material according to the third to eleventh specific embodiments, the capacity of the sodium-ion battery composite negative electrode material is less than or equal to 650mAhg-1。
Claims (1)
1. A preparation method of a composite cathode material of a sodium-ion battery is characterized by comprising the following steps: the method comprises the following steps:
step a, preparing a graphene foam material for later use;
a1, cleaning a nickel foam substrate, soaking the nickel foam substrate in 5% diluted hydrochloric acid for 4-6 hours, washing the nickel foam substrate with deionized water for 3-5 times, and drying the nickel foam substrate at 60 ℃ for later use;
the size of the nickel foam substrate in the step a1 is 2cm multiplied by 2 cm-8 cm multiplied by 8cm, and the thickness of the nickel foam substrate is 0.9-1.1 mm;
step a2, placing the nickel foam substrate treated in the step a1 into a horizontal quartz tube furnace, and feeding the nickel foam substrate into the horizontal quartz tube furnace
Introducing mixed gas of argon and hydrogen, heating to 1000 ℃, keeping for 5min, taking the mixed gas of argon and hydrogen as carrier gas, carrying the mixed gas into a reaction cavity through liquid ethanol, keeping for 5min at 1000 ℃, and then recovering the mixed gas of argon and hydrogen to rapidly cool to room temperature to obtain a sample for later use;
the flow rate of argon in the mixed gas of argon and hydrogen in the step a2 is 280sccm, the flow rate of hydrogen is 20sccm, the flow rate of argon in the mixed gas of argon and hydrogen carrier gas is 160sccm, and the flow rate of hydrogen is 40 sccm;
step a3, soaking the sample obtained in the step a2 in 1mol/L FeCl3And 5wt% of dilute hydrochloric acid, and taking out after 48 hours to obtain a graphene foam material;
b, growing carbon nanotubes on the graphene foam material prepared in the step a, and preparing a carbon nanotube-graphene foam composite material for later use;
the preparation method of the carbon nanotube-graphene foam composite material in the step b comprises the following steps:
step b1, preparing a nickel cobalt catalyst, and adding 1mmol of Ni (NO)3)2·6H2O and 2mmol Co (NO)3)2·6H2Adding O into 40ml of deionized water in sequence, adding 12mmol of urea after carrying out ultrasonic treatment for 15 minutes, and carrying out ultrasonic treatment for 15 minutes to obtain the nickel-cobalt catalyst;
step b2, placing the carbon nanotubes grown on the graphene foam material prepared in the step a on the nickel obtained in the step b1
Carrying out hydrothermal reaction on a cobalt catalyst at 120 ℃ for 2h, and naturally cooling to room temperature to obtain a nickel-cobalt composite graphene foam material;
b3, placing the nickel-cobalt composite graphene foam material prepared in the step b2 in a horizontal quartz tube furnace, introducing argon into the horizontal quartz tube furnace, heating to 750 ℃, introducing a mixed gas of argon, hydrogen and ethylene, keeping for 10min, and then returning to the state that the introduced argon is rapidly cooled to room temperature to obtain a carbon nano tube-graphene foam composite material;
the flow rate of argon in the step b3 is 100sccm, the flow rate of argon in the mixed gas of argon, hydrogen and ethylene is 100sccm, the flow rate of hydrogen is 40sccm, and the flow rate of ethylene is 20 sccm;
c, performing surface treatment on the carbon nano tube-graphene foam composite material prepared in the step b, and treating for later use;
the surface treatment of the carbon nanotube-graphene foam composite material in the step c comprises the following steps: b, placing the carbon nano tube-graphene foam composite material prepared in the step b in concentrated sulfuric acid, and boiling for 2 hours at 120 ℃;
the mass density of the carbon nano tube-graphene foam composite material after surface treatment is 0.65-0.66 mg/cm2；
D, preparing vanadium dioxide nanosheet reaction liquid for later use;
the preparation method of the vanadium dioxide nanosheet reaction solution in the step d comprises the following steps:
step d1, weigh 1.2gV2O5Dissolving the powder and 1.8g of oxalic acid powder in 40mL of deionized water, and performing hot water bath at 75 ℃ until the powder is completely dissolved to obtain a mixed solution for later use;
step d2, measuring 5mL of the mixed solution obtained in the step d1, transferring the mixed solution to a 30mL reaction kettle, adding 1mL of 30wt% hydrogen peroxide and 20mL of absolute ethyl alcohol, and continuously stirring for 20min to obtain a vanadium dioxide nanosheet reaction solution;
step e, completely placing the carbon nano tube-graphene foam composite material prepared in the step c into the vanadium dioxide nanosheet reaction solution prepared in the step d, controlling the reaction temperature to be 180 ℃ and the reaction time to be 3h, taking out a product after the reaction, washing the product with deionized water and alcohol for 4 times, placing the product in a vacuum oven at 120 ℃ for drying for 6h, and finally annealing the product in air at 400 ℃ for 2h to obtain the sodium-ion battery composite negative electrode material;
the composite negative electrode material of the sodium-ion battery is 0.1 A.g-1Can be circulated at a current density of 650mAh g and the capacity of the capacitor can be stabilized at 650mAh g-1。
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| CN111509226B (en) * | 2020-04-24 | 2021-09-10 | 北京石墨烯研究院有限公司 | Graphene foam compound, preparation method thereof, and composite electrode and lithium-sulfur battery comprising graphene foam compound |
| CN111924873A (en) * | 2020-07-31 | 2020-11-13 | 广东凯金新能源科技股份有限公司 | Novel sodium-ion battery negative electrode material and preparation method thereof |
| CN112357959B (en) * | 2020-10-19 | 2022-07-29 | 成都先进金属材料产业技术研究院股份有限公司 | Preparation method of nano vanadium dioxide/reticular graphite-based composite electrode material |
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