CN114864919A - Preparation 3D prints Nb 2 CT x Method for preparing/rGO composite sodium metal cathode - Google Patents
Preparation 3D prints Nb 2 CT x Method for preparing/rGO composite sodium metal cathode Download PDFInfo
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Abstract
The invention is suitable for the technical field of new energy batteries, and provides a method for preparing 3D printing Nb 2 CT x A method for preparing a/rGO composite sodium metal anode comprises the following steps: preparing GO dispersion liquid by using Hummer method, mixing the liquid with Nb 2 CT x Solution and ZnSO 4 ·7H 2 Mixing the O solutionStirring and centrifuging to obtain Nb 2 CT x a/GO composite ink; transferring the porous structure into a syringe barrel, printing a three-dimensional ordered porous structure by adopting a 3D printing technology, and freeze-drying; nb after treatment 2 CT x Annealing the/GO composite three-dimensional ordered porous structure to obtain the 3D printed Nb 2 CT x a/rGO composite aerogel; putting the mixture into a button cell, and performing discharge treatment; disassembling the button cell to obtain the 3D printing Nb 2 CT x The invention combines a 3D printing technology, and has the advantages of saving raw materials and reducing cost.
Description
Technical Field
The invention relates to the technical field of new energy batteries, in particular to a method for preparing 3D printing Nb 2 CT x A method for compounding a sodium metal negative electrode with/rGO.
Background
At present, rechargeable batteries are widely applied, such as mobile phones, notebook computers, electric or hybrid electric vehicles, and are ubiquitous in every life. Particularly in the field of electric vehicles, in order to eliminate the future dependence on conventional fossil fuels, it is urgently required to develop a battery having high energy density and high cycle stability. Since the 90 s of the 20 th century, lithium battery technology has been widely used due to its high energy density and cycling stability. However, the increasing demand for lithium resources places more and more pressure on the supply chain related to lithium resources, and lithium ions are generally stored in politically and economically unstable areas, and extraction is expensive, complicated, time-consuming, and heavily polluted, so that a material suitable for replacing lithium is urgently found. Sodium metal batteries have attracted more and more attention and research in recent years because of abundant sodium resources, low cost, and similar electrochemical properties to lithium, and because sodium metal has a higher theoretical specific capacity (1166mAh/g) and a lower electrochemical potential (-2.71V vs reversible hydrogen electrode). However, the research on sodium metal batteries is in the beginning and there are many problems to be solved, such as safety problems caused by the growth of sodium dendrites, low coulombic efficiency and unsatisfactory cycle stability. Therefore, the application of sodium metal batteries still requires more scientific research and technical improvement.
Past studies have shown that a three-dimensional porous framework with a high specific surface area can reduce local current density, promote uniform nucleation of sodium, and inhibit the growth of sodium dendrites. Moreover, the porous structure can be used as a space for accommodating sodium metal, and the volume change in the sodium metal deposition process is relieved. In addition, the 3D printing technology can independently design and manufacture a hierarchical ordered porous structure as an ion transmission path to accelerate the sodium ion transmission rate. The surface of the two-dimensional material MXenes (transition metal carbide/nitride) has rich functional groups, so that the nucleation barrier of sodium metal can be reduced, and the uniform deposition of sodium metal is promoted. The pi-pi bonds between the graphene oxide nanosheets can enhance the interaction between the nanosheets, so that the nanosheets have appropriate rheological properties to meet the requirements of ink required for 3D printing. And the graphene has good conductivity, so that the use of a conductive agent can be avoided. However, the current 3D printed structure still faces some serious problems, such as the change of three-dimensional structure morphology caused by the poor mechanical strength of the three-dimensional grid structure during the sodium metal repeated deposition/peeling process. Therefore, how to solve the problems of sodium dendrite growth, volume expansion, improvement of mechanical strength of a 3D printing electrode and the like in the sodium metal negative electrode deposition process through an advanced material preparation method and an electrode structure with reasonable design is a key point for promoting the application of the 3D printing graphene-based sodium metal negative electrode. As can be seen from the above, the existing method is difficult to be widely applied.
Therefore, in view of the above situation, there is an urgent need to provide a method for preparing 3D printing Nb 2 CT x A method for compounding a sodium metal negative electrode with/rGO overcomes the defects in the current practical application.
Disclosure of Invention
The invention aims to provide a method for preparing 3D printing Nb 2 CT x A method for compounding a sodium metal negative electrode with/rGO solves the problems in the technical background.
The invention is realized in such a way that the 3D printing Nb is prepared 2 CT x A method of forming a/rGO composite sodium metal anode, the method comprising the steps of:
step 1: preparing GO dispersion liquid by adopting improved Hummer method, and mixing the liquid and Nb 2 CT x Solution and ZnSO 4 ·7H 2 Mixing, stirring and centrifuging the O solution at low temperature, and grinding black gel at the bottom of a centrifuge tube to obtain Nb 2 CT x a/GO composite ink;
step 2: nb obtained in step 1 2 CT x the/GO composite ink is transferred into a syringe barrel at a certain pressure, a direct-writing 3D printing technology is adopted, a three-dimensional ordered porous structure is printed layer by layer through a needle point, and a freeze dryer is used for Nb 2 CT x Freezing and drying the/GO composite three-dimensional ordered porous structure;
and step 3: the Nb after the freeze-drying treatment in the step 2 is added 2 CT x Moving the/GO composite three-dimensional ordered porous structure into a tube furnace for high-temperature annealing to obtain the 3D printed Nb 2 CT x a/rGO composite aerogel;
and 4, step 4: printing the 3D prepared in the step 3 into Nb 2 CT x Loading the/rGO composite aerogel into a CR2032 type button cell, wherein a counter electrode is a sodium sheet, and performing constant-current discharge treatment under the condition of a certain area current density;
and 5: disassembling the button cell subjected to the discharging treatment in the step 4, and then printing the 3D into Nb 2 CT x Taking out the/rGO composite aerogel to obtain the 3D printed Nb 2 CT x the/rGO composite sodium metal cathode.
As a further scheme of the invention: in step 1, the Nb 2 CT x The mass fraction of the solution is 20 percent;
the ZnSO 4 ·7H 2 The mass fraction of the O solution is 0.1-0.8%, and ZnSO 4 ·7H 2 O solution as induced Nb 2 CT x A binder that gels rapidly.
As a further scheme of the invention: in step 1, during the low temperature centrifugation treatment, the temperature of the sample is maintained at 0-10 ℃, the rotation speed of the centrifuge is 15000-20000rpm, and the centrifugation time is 10-30 minutes.
As a further scheme of the invention: in the step 2, the pressure is 0.15-0.25MPa, and the moving speed of the needle point is 5-10 mm/s.
As a further scheme of the invention: in step 2, the Nb 2 CT x the/GO composite three-dimensional ordered porous structure is a porous array structure with the thickness of (0.8-1.2) cm multiplied by (2-10) mm.
As a further scheme of the invention: in step 2, Nb is freeze-dried using a freeze dryer 2 CT x The temperature condition of freeze drying the/GO composite three-dimensional ordered porous structure is-30-40 ℃, and the time is 24-48 hours.
As a further scheme of the invention: in step 3, Nb is added 2 CT x The annealing conditions for moving the/GO composite three-dimensional ordered porous structure into the tubular furnace are as follows: introducing Ar/H at a gas flow rate of 30-40sccm 2 (95/5%) mixing gas, heating and cooling rate is 1-2 deg.C/min, heat preservation temperature is 450 deg.C, and time is 1-3 hr.
As a further scheme of the invention: in step 4, 3D printed Nb 2 CT x Placing the/rGO composite aerogel in a CR2032 type button battery and then standing for 2 min;
the upper limit of the voltage range is 0.5V and the area current density is 1mA/cm 2 Constant current discharge was performed for 2 hours under the conditions.
Compared with the prior art, the invention has the beneficial effects that:
(1) the autonomous design of the shape and the structure of the electrode material can be realized through the 3D printing technology, the loss of raw materials is reduced, the sodium ion transmission can be accelerated through the ordered porous array structure, and the electrode reaction kinetics rate is improved. The microporous structure of the three-dimensional grid structure can be used as a space for storing sodium metal, so that the problem of volume expansion in the sodium deposition process is solved;
(2) at Nb 2 CT x Introduction of Zn into solution 2+ Ions, capable of destroying Nb 2 CT x Electrostatic repulsion force between the nano sheets to form stable three-dimensional Nb 2 CT x A hydrogel. Using metal ions as attachment sites, Nb 2 CT x The nano sheets are connected with each other, so that Nb is effectively inhibited 2 CT x Re-production of nanosheetsStacking;
(3) adding Nb in printing ink 2 CT x Solution, 3D printed Nb produced 2 CT x The rich functional groups in the/rGO composite sodium metal negative electrode can promote uniform nucleation and deposition of sodium metal.
Drawings
FIG. 1 is a flow chart of the preparation of an embodiment of the present invention.
FIG. 2 shows a 3D printed Nb prepared in an embodiment of the invention 2 CT x Scanning electron microscope images of/rGO composite aerogel under different magnifications.
FIG. 3 shows a 3D printed Nb prepared in an embodiment of the invention 2 CT x XRD pattern of/rGO composite aerogel sodium metal cathode.
FIG. 4 shows an Nb for 3D printing in an embodiment of the invention 2 CT x Stress-strain curve during testing of/rGO composite aerogels.
FIG. 5 shows Nb for 3D printing in embodiment 4 of the present invention 2 CT x the/rGO composite aerogel sodium metal cathode is at 10mA/cm 2 ，1mAh/cm 2 Cycle performance plot under conditions.
FIG. 6 shows Nb for 3D printing in embodiment 4 of the present invention 2 CT x the/rGO composite aerogel sodium metal cathode is at 3mA/cm 2 ，1mAh/cm 2 Coulombic efficiency plots under conditions.
FIG. 7 shows an example of 3D printing Nb 2 CT x the/rGO is used as a negative electrode, and the rGO/Na is printed by 3D 3 V 2 (PO 4 ) 3 The circulation curve graph and the inset (the inset shows that the assembled full battery successfully lights up the LED lamp) of the full battery composed of the @ C composite micro-grid aerogel used as the anode under the current density of 100 mA/g.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Specific implementations of the present invention are described in detail below with reference to specific embodiments.
Example 1
Referring to FIGS. 1-7, a method for preparing 3D printed Nb 2 CT x A method of/rGO composite sodium metal negative electrode, the method comprising the steps of:
step 1: preparation of GO dispersions by the modified Hummer method, for the above liquids and Nb 2 CT x Mixing, stirring and centrifuging the solution at low temperature, and grinding black gel at the bottom of a centrifuge tube to obtain Nb 2 CT x a/GO composite ink;
step 2: nb obtained in step 1 2 CT x the/GO composite ink is transferred into a syringe barrel at a certain pressure, a direct-writing 3D printing technology is adopted, a three-dimensional ordered porous structure is printed layer by layer through a needle point, and a freeze dryer is used for Nb 2 CT x Freezing and drying the/GO composite three-dimensional ordered porous structure;
and step 3: the Nb after the freeze-drying treatment in the step 2 is added 2 CT x Moving the/GO composite three-dimensional ordered porous structure into a tube furnace for high-temperature annealing to obtain the 3D printed Nb 2 CT x a/rGO composite aerogel;
and 4, step 4: printing the 3D prepared in the step 3 into Nb 2 CT x loading/rGO composite aerogel into a CR2032 type button cell, taking a sodium sheet as a counter electrode, taking Celgard 2400 as a diaphragm, and taking NaPF as 80 muL 1M solute 6 And an electrolyte with a solvent of diglyme, deposited to an area capacity of 2mAh/cm 2 Performing constant current discharge treatment;
and 5: disassembling the button cell subjected to the discharging treatment in the step 4, and then printing the 3D into Nb 2 CT x Taking out the/rGO composite aerogel to obtain the 3D printed Nb 2 CT x /rGO composite sodium metal cathode, p Nb 2 CT x And carrying out electrochemical test and mechanical strength tensile test on the/rGO composite aerogel sodium metal cathode.
Mixing GO hydrogel with Na 3 V 2 (PO 4 ) 3 Mixing the @ C powder with the mass ratio of 1:1 to obtain GO/Na 3 V 2 (PO 4 ) 3 @ C composite ink, GO/Na printed by 3D printing technology 3 V 2 (PO 4 ) 3 @ C microgrid electrode at Ar/H 2 (95/5%) keeping the temperature at 600 ℃ for 2 hours under the control conditions that the atmosphere is 40sccm, the gas flow rate is 40sccm, and the heating and cooling rates are 1 ℃/min, and finally obtaining the 3D printed rGO/Na 3 V 2 (PO 4 ) 3 @ C cathode, 3D printed Nb prepared as described above 2 CT x rGO/Na printed by matching of/rGO sodium metal cathode with 3D 3 V 2 (PO 4 ) 3 The @ C positive electrode was assembled with a CR2032 coin full cell using the same electrolyte and separator as described above, and its application is shown in the inset in fig. 7.
FIG. 2 shows a 3D printed Nb prepared in this example 2 CT x Scanning electron microscope pictures of the/rGO composite aerogel under different magnifications can be seen from the pictures, namely the GO dispersion liquid and the Nb 2 CT x After the solution is stirred, centrifuged and ground, Nb is prepared by using 3D printing technology 2 CT x the/GO is in a micro-grid structure and is subjected to freeze drying and high-temperature heat treatment to obtain Nb 2 CT x a/rGO composite aerogel; 3D printing Nb as shown in a of FIG. 2 2 CT x the/rGO composite aerogel consists of ribs about 400 microns wide and holes 500 microns in size; 3D printing Nb as shown in b of FIG. 2 2 CT x The surface of the/rGO composite aerogel has a plurality of microporous structures; as shown in c in FIG. 2, Nb 2 CT x Uniformly attached to the rGO surface.
FIG. 3 is a 3D printing Nb 2 CT x XRD (X-ray diffraction) pattern of/rGO composite aerogel sodium metal cathode as shown in figure, Zn is added 2+ Then, Nb is destroyed 2 CT x Electrostatic repulsion between the nanosheets, joining them together to form a stable three-dimensional Nb 2 CT x Hydrogel, Nb 2 CT x The distance between the nano-sheet layers is reduced, and the XRD peak position shifts to a large-angle direction.
FIG. 4 is Nb 2 CT x Stress-strain curve of/rGO composite aerogels, Nb 2 CT x /rGO-0: indicates that no Zn is contained 2+ ；Nb 2 CT x /rGO-1: containing Zn 2+ (ii) a At Nb 2 CT x Introduction of Zn into solution 2+ Destruction of Nb 2 CT x Electrostatic repulsion between the nano sheets to form stable three-dimensional Nb 2 CT x Hydrogel, effective suppression of Nb 2 CT x The re-accumulation of the nano-sheets is beneficial to improving the Nb in the material 2 CT x The degree of correlation between the nanosheets and between the graphene nanosheets is obviously improved 2 CT x Mechanical properties of/rGO aerogels.
FIG. 5 is a 3D printing Nb 2 CT x the/rGO composite aerogel sodium metal cathode is at 10mA/cm 2 Area current density of 1mAh/cm 2 Long cycle test pattern under area specific capacity condition, as shown in the figure, 3D prints Nb 2 CT x Half cell assembled by/rGO composite aerogel sodium metal cathode at 10mA/cm 2 Can be stably cycled for more than 150 hours under high current density.
FIG. 6 is a 3D printing Nb 2 CT x the/rGO composite aerogel sodium metal cathode is at 3mA/cm 2 Area current density of 1mAh/cm 2 Coulombic efficiency graph under area specific capacity condition, as shown in figure 3D printed Nb 2 CT x The average coulombic efficiency for the first 1000 cycles of the half-cell assembled with the/rGO composite aerogel sodium metal negative electrode was 99.25%.
FIG. 7 is a 3D printing Nb 2 CT x rGO/rGO composite aerogel sodium metal cathode matched with 3D printed rGO/Na 3 V 2 (PO 4 ) 3 @ C is a cycle curve of a full battery composed of a positive electrode at a current density of 100mA/g, and an inset is 3D printed Nb 2 CT x rGO/rGO composite aerogel sodium metal cathode matched with 3D printed rGO/Na 3 V 2 (PO 4 ) 3 The demonstration picture of the LED lamp is lighted up by the CR2032 type button full cell of the @ C positive electrode.
Example 2
Referring to FIGS. 1-7, a method for preparing 3D printed Nb 2 CT x A method of forming a/rGO composite sodium metal anode, the method comprising the steps of:
step 1: by using a modified Hummer methodPreparation of GO Dispersion with Nb 2 CT x Solution and ZnSO with mass fraction of 0.1% 4 ·7H 2 Mixing, stirring and centrifuging the O solution at low temperature, and grinding black gel at the bottom of a centrifuge tube to obtain Nb 2 CT x a/GO composite ink; in this process, at Nb 2 CT x Introduction of Zn into solution 2+ Destructive of Nb 2 CT x Electrostatic repulsion between the nano sheets to form stable three-dimensional Nb 2 CT x Hydrogel, effective suppression of Nb 2 CT x And (4) re-stacking the nanosheets. Simultaneously is beneficial to improving Nb in the material 2 CT x Correlation degree between nanosheets and between graphene nanosheets, and further 3D printing of Nb 2 CT x The strength of the/rGO composite aerogel electrode is improved;
step 2: nb obtained in step 1 2 CT x the/GO composite ink is transferred into a syringe barrel at a certain pressure, a direct-writing 3D printing technology is adopted, a three-dimensional ordered porous structure is printed layer by layer through a needle point, and a freeze dryer is used for Nb 2 CT x Freezing and drying the/GO composite three-dimensional ordered porous structure;
and step 3: the Nb after the freeze-drying treatment in the step 2 is added 2 CT x Moving the/GO composite three-dimensional ordered porous structure into a tube furnace for high-temperature annealing to obtain the 3D printed Nb 2 CT x a/rGO composite aerogel;
and 4, step 4: printing the 3D prepared in the step 3 into Nb 2 CT x loading/rGO composite aerogel into a CR2032 type button cell, taking a sodium sheet as a counter electrode, taking Celgard 2400 as a diaphragm, and taking NaPF as 80 muL 1M solute 6 And an electrolyte with a solvent of diglyme, deposited to an area capacity of 2mAh/cm 2 Performing constant current discharge treatment;
and 5: disassembling the button cell subjected to the discharging treatment in the step 4, and then printing the 3D into Nb 2 CT x Taking out the/rGO composite aerogel to obtain the 3D printed Nb 2 CT x a/rGO composite sodium metal cathode, and finally ZnSO with the mass fraction of 0.1 percent is added 4 ·7H 2 The samples of O were subjected to electrochemical testing as well as mechanical strength tensile testing.
Mixing GO hydrogel with Na 3 V 2 (PO 4 ) 3 Mixing the @ C powder with the mass ratio of 1:1 to obtain GO/Na 3 V 2 (PO 4 ) 3 @ C composite ink, GO/Na printed by 3D printing technology 3 V 2 (PO 4 ) 3 @ C microgrid electrode at Ar/H 2 (95/5%) keeping the temperature at 600 ℃ for 2 hours under the control conditions that the atmosphere is 40sccm, the gas flow rate is 40sccm, and the heating and cooling rates are 1 ℃/min, and finally obtaining the 3D printed rGO/Na 3 V 2 (PO 4 ) 3 @ C cathode, 3D printed Nb prepared as described above 2 CT x rGO/Na printed by matching of/rGO sodium metal cathode with 3D 3 V 2 (PO 4 ) 3 The @ C positive electrode was assembled with a CR2032 coin full cell using the same electrolyte and separator as described above, and its application is shown in the inset in fig. 7.
Example 3
Referring to FIGS. 1-7, a method for preparing 3D printed Nb 2 CT x A method of/rGO composite sodium metal negative electrode, the method comprising the steps of:
step 1: preparing GO dispersion liquid by adopting improved Hummer method, and mixing the liquid and Nb 2 CT x Solution and ZnSO with mass fraction of 0.3% 4 ·7H 2 Mixing, stirring and centrifuging the O solution at low temperature, and grinding black gel at the bottom of a centrifuge tube to obtain Nb 2 CT x a/GO composite ink; in this process, at Nb 2 CT x Introduction of Zn into solution 2+ Destruction of Nb 2 CT x Electrostatic repulsion between the nano sheets to form stable three-dimensional Nb 2 CT x Hydrogel, effective suppression of Nb 2 CT x And (4) re-stacking the nanosheets. Simultaneously is beneficial to improving Nb in the material 2 CT x Correlation degree between nanosheets and between graphene nanosheets, and further 3D printing of Nb 2 CT x The strength of the/rGO composite aerogel electrode is improved;
step 2: obtained in step 1Nb of 2 CT x the/GO composite ink is transferred into a syringe barrel at a certain pressure, a direct-writing 3D printing technology is adopted, a three-dimensional ordered porous structure is printed layer by layer through a needle point, and a freeze dryer is used for Nb 2 CT x Freezing and drying the/GO composite three-dimensional ordered porous structure;
and step 3: the Nb after the freeze-drying treatment in the step 2 is added 2 CT x Moving the/GO composite three-dimensional ordered porous structure into a tube furnace for high-temperature annealing to obtain the 3D printed Nb 2 CT x a/rGO composite aerogel;
and 4, step 4: printing the 3D prepared in the step 3 into Nb 2 CT x loading/rGO composite aerogel into a CR2032 type button cell, taking a sodium sheet as a counter electrode, taking Celgard 2400 as a diaphragm, and taking NaPF as 80 muL 1M solute 6 And an electrolyte with a solvent of diglyme, deposited to an area capacity of 2mAh/cm 2 Performing constant current discharge treatment;
and 5: disassembling the button cell subjected to discharge treatment in the step 4, and then printing the 3D printed Nb 2 CT x Taking out the/rGO composite aerogel to obtain the 3D printed Nb 2 CT x a/rGO composite sodium metal cathode, and finally ZnSO with the mass fraction of 0.3 percent is added 4 ·7H 2 The samples of O were subjected to electrochemical testing as well as mechanical strength tensile testing.
Mixing GO hydrogel with Na 3 V 2 (PO 4 ) 3 Mixing the @ C powder with the mass ratio of 1:1 to obtain GO/Na 3 V 2 (PO 4 ) 3 @ C composite ink, GO/Na printed by 3D printing technology 3 V 2 (PO 4 ) 3 @ C microgrid electrode at Ar/H 2 (95/5%) keeping the temperature at 600 ℃ for 2 hours under the control conditions that the atmosphere is 40sccm, the gas flow rate is 40sccm, and the heating and cooling rates are 1 ℃/min, and finally obtaining the 3D printed rGO/Na 3 V 2 (PO 4 ) 3 @ C cathode, 3D printed Nb prepared as described above 2 CT x rGO/Na printed by matching of/rGO sodium metal cathode with 3D 3 V 2 (PO 4 ) 3 @ C cathode, using the same electrolyte and separator as described above, assembled into a CR2032 typeA button full cell, the application of which is shown in the insert of figure 7.
Example 4
Referring to FIGS. 1-7, a method for preparing 3D printed Nb 2 CT x A method of/rGO composite sodium metal negative electrode, the method comprising the steps of:
step 1: preparing GO dispersion liquid by adopting improved Hummer method, and mixing the liquid and Nb 2 CT x Solution and ZnSO with mass fraction of 0.6% 4 ·7H 2 Mixing, stirring and centrifuging the O solution at low temperature, and grinding black gel at the bottom of a centrifuge tube to obtain Nb 2 CT x a/GO composite ink; in this process, at Nb 2 CT x Introduction of Zn into solution 2+ Destruction of Nb 2 CT x Electrostatic repulsion between the nano sheets to form stable three-dimensional Nb 2 CT x Hydrogel, effective suppression of Nb 2 CT x And (4) re-stacking the nanosheets. Simultaneously is beneficial to improving Nb in the material 2 CT x Correlation degree between nanosheets and between graphene nanosheets, and further 3D printing of Nb 2 CT x The strength of the/rGO composite aerogel electrode is improved;
step 2: nb obtained in step 1 2 CT x the/GO composite ink is transferred into a syringe barrel at a certain pressure, a direct-writing 3D printing technology is adopted, a three-dimensional ordered porous structure is printed layer by layer through a needle point, and a freeze dryer is used for Nb 2 CT x Freezing and drying the/GO composite three-dimensional ordered porous structure;
and step 3: the Nb after the freeze-drying treatment in the step 2 is added 2 CT x Moving the/GO composite three-dimensional ordered porous structure into a tube furnace for high-temperature annealing to obtain the 3D printed Nb 2 CT x a/rGO composite aerogel;
and 4, step 4: printing the 3D prepared in the step 3 into Nb 2 CT x loading/rGO composite aerogel into a CR2032 type button cell, taking a sodium sheet as a counter electrode, taking Celgard 2400 as a diaphragm, and taking NaPF as 80 muL 1M solute 6 And an electrolyte with a solvent of diglyme, deposited to an area capacity of 2mAh/cm 2 Performing constant current discharge treatment;
and 5: disassembling the button cell subjected to the discharging treatment in the step 4, and then printing the 3D into Nb 2 CT x Taking out the/rGO composite aerogel to obtain the 3D printed Nb 2 CT x a/rGO composite sodium metal cathode, and finally ZnSO with the mass fraction of 0.6 percent is added 4 ·7H 2 The sample of O was subjected to electrochemical testing and mechanical strength tensile testing, and found: adding ZnSO with the mass fraction of 0.6 percent 4 ·7H 2 Sample of O the assembled cell was at 3mA/cm 2 ，1mAh/cm 2 The average coulombic efficiency of the first 1000 cycles under the condition of the cycle test can reach 99.25 percent and is 10mA/cm 2 Can be stably cycled for more than 150 hours under high current density.
Mixing GO hydrogel with Na 3 V 2 (PO 4 ) 3 Mixing the @ C powder with the mass ratio of 1:1 to obtain GO/Na 3 V 2 (PO 4 ) 3 @ C composite ink, GO/Na printed by 3D printing technology 3 V 2 (PO 4 ) 3 @ C microgrid electrode at Ar/H 2 (95/5%) keeping the temperature at 600 ℃ for 2 hours under the control conditions that the atmosphere is 40sccm, the gas flow rate is 40sccm, and the heating and cooling rates are 1 ℃/min, and finally obtaining the 3D printed rGO/Na 3 V 2 (PO 4 ) 3 @ C cathode, 3D printed Nb prepared as described above 2 CT x rGO/Na printed by matching of/rGO sodium metal cathode with 3D 3 V 2 (PO 4 ) 3 The @ C positive electrode was assembled with a CR2032 coin full cell using the same electrolyte and separator as described above, and its application is shown in the inset in fig. 7.
Example 5
Referring to FIGS. 1-7, a method for preparing 3D printed NB 2 CT x A method of/rGO composite sodium metal negative electrode, the method comprising the steps of:
step 1: preparing GO dispersion liquid by adopting improved Hummer method, and mixing the liquid and Nb 2 CT x Solution and ZnSO with mass fraction of 0.8% 4 ·7H 2 Mixing, stirring and low-temperature centrifuging the O solution, and taking a centrifuge tubeGrinding the black gel at the bottom to obtain Nb 2 CT x a/GO composite ink; in this process, at Nb 2 CT x Introduction of Zn into solution 2+ Destruction of Nb 2 CT x Electrostatic repulsion between the nano sheets to form stable three-dimensional Nb 2 CT x Hydrogel, effective suppression of Nb 2 CT x And (4) re-stacking the nanosheets. Simultaneously is beneficial to improving Nb in the material 2 CT x Correlation degree between nanosheets and between graphene nanosheets, and further 3D printing of Nb 2 CT x The strength of the/rGO composite aerogel electrode is improved;
step 2: nb obtained in step 1 2 CT x the/GO composite ink is transferred into a syringe barrel at a certain pressure, a direct-writing 3D printing technology is adopted, a three-dimensional ordered porous structure is printed layer by layer through a needle point, and a freeze dryer is used for Nb 2 CT x Freezing and drying the/GO composite three-dimensional ordered porous structure;
and step 3: the Nb after the freeze-drying treatment in the step 2 is added 2 CT x Moving the/GO composite three-dimensional ordered porous structure into a tube furnace for high-temperature annealing to obtain the 3D printed Nb 2 CT x a/rGO composite aerogel;
and 4, step 4: printing the 3D prepared in the step 3 into Nb 2 CT x loading/rGO composite aerogel into a CR2032 type button cell, taking a sodium sheet as a counter electrode, taking Celgard 2400 as a diaphragm, and taking NaPF as 80 muL 1M solute 6 And an electrolyte with a solvent of diglyme, deposited to an area capacity of 2mAh/cm 2 Performing constant current discharge treatment;
and 5: disassembling the button cell subjected to the discharging treatment in the step 4, and then printing the 3D into Nb 2 CT x Taking out the/rGO composite aerogel to obtain the 3D printed Nb 2 CT x a/rGO composite sodium metal cathode is added with ZnSO with the mass fraction of 0.8 percent 4 ·7H 2 The samples of O were subjected to electrochemical testing as well as mechanical strength tensile testing.
Mixing GO hydrogel with Na 3 V 2 (PO 4 ) 3 Mixing at a mass ratio of 1:1 to obtain @ C powderTo GO/Na 3 V 2 (PO 4 ) 3 @ C composite ink, GO/Na printed by 3D printing technology 3 V 2 (PO 4 ) 3 @ C microgrid electrode at Ar/H 2 (95/5%) keeping the temperature at 600 ℃ for 2 hours under the control conditions that the atmosphere is 40sccm, the gas flow rate is 40sccm, and the heating and cooling rates are 1 ℃/min, and finally obtaining the 3D printed rGO/Na 3 V 2 (PO 4 ) 3 @ C cathode, 3D printed Nb prepared as described above 2 CT x rGO/Na printed by matching of/rGO sodium metal cathode with 3D 3 V 2 (PO 4 ) 3 The @ C positive electrode was assembled with a CR2032 coin full cell using the same electrolyte and separator as described above, and its application is shown in the inset in fig. 7.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. Preparation 3D prints Nb 2 CT x The method for preparing the/rGO composite sodium metal negative electrode is characterized by comprising the following steps:
step 1: preparing GO dispersion liquid by adopting improved Hummer method, and mixing the liquid and Nb 2 CT x Solution and ZnSO 4 ·7H 2 Mixing, stirring and centrifuging the O solution at low temperature, and grinding black gel at the bottom of a centrifuge tube to obtain Nb 2 CT x a/GO composite ink;
step 2: nb obtained in step 1 2 CT x Transferring the/GO composite ink into a syringe barrel at a certain pressure, printing a three-dimensional ordered porous structure layer by layer through a needle point by adopting a direct-writing 3D printing technology, and performing Nb freeze drying by using a freeze dryer 2 CT x Freezing and drying the/GO composite three-dimensional ordered porous structure;
and step 3: the Nb after the freeze-drying treatment in the step 2 is added 2 CT x Moving the/GO composite three-dimensional ordered porous structure into a tube furnace for high-temperature annealing to obtain the 3D printed Nb 2 CT x a/rGO composite aerogel;
and 4, step 4: printing the 3D prepared in the step 3 into Nb 2 CT x the/rGO composite aerogel is filled into a CR2032 type button cell, a counter electrode is a sodium sheet, and constant current discharge treatment is carried out under the condition of certain area current density;
and 5: disassembling the button cell subjected to the discharging treatment in the step 4, and then printing the 3D into Nb 2 CT x Taking out the/rGO composite aerogel to obtain the 3D printed Nb 2 CT x the/rGO composite sodium metal cathode.
2. Preparing a 3D printed Nb according to claim 1 2 CT x The method for compounding the sodium metal negative electrode with/rGO is characterized in that in the step 1, Nb is adopted 2 CT x The mass fraction of the solution is 20 percent;
the ZnSO 4 ·7H 2 The mass fraction of the O solution is 0.1-0.8%, and ZnSO 4 ·7H 2 O solution as induced Nb 2 CT x A binder that gels rapidly.
3. Preparing a 3D printed Nb according to claim 1 2 CT x The method for preparing the/rGO composite sodium metal cathode is characterized in that in the step 1, in the low-temperature centrifugation treatment process, the temperature of a sample is kept at 0-10 ℃, the rotation speed of a centrifuge is 15000-.
4. Preparing a 3D printed Nb according to claim 1 2 CT x The method for preparing the/rGO composite sodium metal cathode is characterized in that in the step 2, the pressure is 0.15-0.25MPa, and the moving speed of the needle tip is 5-10 mm/s.
5. Preparing a 3D printed Nb according to claim 1 2 CT x Method for preparing/rGO composite sodium metal cathode, characterized in that in step 2, Nb is adopted 2 CT x the/GO composite three-dimensional ordered porous array junction with the porous structure of (0.8-1.2) cm x (2-10) mmAnd (5) forming.
6. Preparing a 3D printed Nb according to claim 1 2 CT x The method for preparing the/rGO composite sodium metal cathode is characterized in that in the step 2, a freeze dryer is used for drying Nb 2 CT x The temperature condition of freeze drying the/GO composite three-dimensional ordered porous structure is-30-40 ℃ and the time is 24-48 hours.
7. Preparing a 3D printed Nb according to claim 1 2 CT x The method for compounding the sodium metal negative electrode with/rGO is characterized in that in the step 3, Nb is added 2 CT x The annealing condition of moving the/GO composite three-dimensional ordered porous structure into the tube furnace is as follows: introducing Ar/H at a gas flow rate of 30-40sccm 2 (95/5%) mixing gas, heating and cooling rate is 1-2 deg.C/min, heat preservation temperature is 450 deg.C, and heat preservation time is 1-3 hr.
8. Preparing a 3D printed Nb according to claim 1 2 CT x The method for preparing/rGO composite sodium metal cathode is characterized in that in step 4, 3D printing Nb is performed 2 CT x Placing the/rGO composite aerogel in a CR2032 type button battery and then standing for 2 min;
the upper limit of the voltage range is 0.5V and the area current density is 1mA/cm 2 Constant current discharge was performed for 2 hours under the conditions.
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