CN114864919B - Nb printing for preparing 3D 2 CT x Method for preparing rGO composite sodium metal anode - Google Patents
Nb printing for preparing 3D 2 CT x Method for preparing rGO composite sodium metal anode Download PDFInfo
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Abstract
The invention is applicable to the technical field of new energy batteries, and provides a method for preparing 3D printing Nb 2 CT x The method of the rGO composite sodium metal anode comprises the following steps: preparing GO dispersion liquid by Hummer method, mixing the above liquid with Nb 2 CT x Solution and ZnSO 4 ·7H 2 Mixing, stirring and centrifuging the O solution to obtain Nb 2 CT x GO composite ink; transferring the porous material into a syringe barrel, printing out a three-dimensional ordered porous structure by adopting a 3D printing technology, and freeze-drying; to be processed Nb 2 CT x Annealing the composite three-dimensional ordered porous structure of the GO to obtain the 3D printing Nb 2 CT x rGO composite aerogel; putting the powder into a button cell, and performing discharge treatment; disassembling the button cell to obtain the 3D printed Nb 2 CT x The rGO composite sodium metal anode combines with a 3D printing technology, and has the advantages of raw material saving and cost reduction.
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 anode by rGO.
Background
Currently, rechargeable batteries are widely used, such as mobile phones, notebook computers, electric or hybrid cars, and are ubiquitous in everyone's life. Particularly in the field of electric automobiles, in order to eliminate the future dependence on traditional fossil fuels, development of a battery with high energy density and high cycle stability is urgently required. 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 increasing pressure on the lithium resource-related supply chain, and lithium ions are generally stored in politically and economically unstable areas, and extraction is expensive, complex, time-consuming, and severely contaminated, 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 their abundant resources, low cost, and electrochemical properties similar to lithium, and their higher theoretical specific capacity (1166 mAh/g) and lower electrochemical potential (-2.71V vs reversible hydrogen electrode). However, the study of sodium metal batteries is in the beginning stage, and there are many problems to be solved, such as safety problems caused by the growth of sodium dendrites, low coulombic efficiency, unsatisfactory cycle stability, and the like. Therefore, the use of sodium metal batteries still requires more scientific research and technological improvement.
Past studies have shown that a three-dimensional porous framework with a high specific surface area can reduce local current density, promote uniform sodium nucleation and inhibit sodium dendrite growth. Moreover, the porous structure can be used as a space for containing sodium metal, so that the volume change in the sodium metal deposition process is relieved. In addition, the 3D printing technology can be independently designed and manufactured into a hierarchical ordered porous structure, and the hierarchical ordered porous structure is used as an ion transmission path to accelerate the sodium ion transmission rate. The surface of the two-dimensional material MXnes (transition metal carbide/nitride) has rich functional groups, which can reduce the nucleation barrier of sodium metal and further promote the uniform deposition of sodium metal. The pi-pi bond between graphene oxide nano-sheets can enhance the interaction between nano-sheets, so that the graphene oxide nano-sheets have proper rheological property to meet the requirement of ink required by 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 also faces some serious problems, such as the change of the morphology of the three-dimensional structure caused by the poor mechanical strength of the three-dimensional grid structure during the repeated deposition/stripping process of sodium metal. Therefore, how to solve the problems of sodium dendrite growth, volume expansion, improvement of the mechanical strength of a 3D printing electrode and the like in the deposition process of the sodium metal negative electrode through an advanced material preparation method and a reasonably designed electrode structure is an important point for promoting the application of the current 3D printing graphene-based sodium metal negative electrode. From the above, it is difficult to widely apply the conventional technology.
Accordingly, in view of the above circumstances, there is an urgent need to provide a method for preparing 3D printed Nb 2 CT x Method for preparing rGO composite sodium metal anodeTo overcome 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 The method of the rGO composite sodium metal anode solves the problems in the technical background.
The invention is realized in such a way that a 3D printing Nb is prepared 2 CT x A method of a rGO composite sodium metal anode, the method comprising the steps of:
step 1: preparing GO dispersion by improved Hummer method, and mixing the above liquid with Nb 2 CT x Solution and ZnSO 4 ·7H 2 Mixing and stirring the O solution, centrifuging at low temperature, and grinding black gel at the bottom of the centrifuge tube to obtain Nb 2 CT x GO composite ink;
step 2: the Nb obtained in the step 1 is taken 2 CT x the/GO composite ink is transferred into a syringe barrel at a certain pressure, a direct writing type 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 Freeze-drying the GO composite three-dimensional ordered porous structure;
step 3: the Nb after the freeze drying treatment in the step 2 2 CT x Transferring the composite three-dimensional ordered porous structure into a tube furnace for high-temperature annealing to obtain 3D printed Nb 2 CT x rGO composite aerogel;
step 4: printing Nb in 3D prepared in the step 3 2 CT x Putting the rGO composite aerogel into a CR2032 button cell, wherein a counter electrode is a sodium sheet, and performing constant current discharge treatment under the condition of certain area current density;
step 5: disassembling the button cell after the discharging treatment in the step 4, and printing Nb in 3D 2 CT x Taking out the rGO composite aerogel to obtain 3D printed Nb 2 CT x rGO composite sodium metal negative electrode.
As a further scheme of the invention: in step 1, the Nb 2 CT x The mass fraction of the solution is 20%;
the ZnSO is 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 fast gelling binder.
As a further scheme of the invention: in the step 1, during the low-temperature centrifugation treatment, the temperature of the sample is kept 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 tip is 5-10mm/s.
As a further scheme of the invention: in step 2, the Nb 2 CT x The composite three-dimensional ordered porous structure of the GO is a porous array structure with the length of (0.8-1.2) cm multiplied by (2-10) mm.
As a further scheme of the invention: in step 2, a freeze dryer is used to cool the Nb 2 CT x The temperature condition of freeze drying the composite three-dimensional ordered porous structure of the GO is-30-40 ℃ and the time is 24-48 hours.
As a further scheme of the invention: in step 3, nb is added to 2 CT x The annealing conditions of the GO composite three-dimensional ordered porous structure moving into the tube furnace are as follows: ar/H is introduced at a gas flow rate of 30-40sccm 2 (95/5%) of mixed gas, the heating and cooling rate is 1-2 ℃/min, the heat preservation temperature is 450 ℃ and the time is 1-3 hours.
As a further scheme of the invention: in step 4, nb is printed in 3D 2 CT x Placing the rGO composite aerogel into a CR2032 button battery and then standing for 2min;
at an upper limit of the voltage range of 0.5V and an area current density of 1mA/cm 2 Constant current discharge was carried out for 2 hours under the condition.
Compared with the prior art, the invention has the beneficial effects that:
(1) The electrode material shape and structure can be designed independently through a 3D printing technology, the raw material loss is reduced, the ordered porous array structure can accelerate sodium ion transmission, and the electrode reaction kinetic rate is improved. The micropore structure of the three-dimensional grid structure can be used as a space for storing sodium metal, so that the volume expansion problem in the sodium deposition process is relieved;
(2) In Nb 2 CT x Zn is introduced into the solution 2+ Ions capable of destroying Nb 2 CT x Electrostatic repulsive force between nano sheets to form stable three-dimensional Nb 2 CT x A hydrogel. Nb using metal ion as a connecting site 2 CT x The nano sheets are connected with each other, thereby effectively inhibiting Nb 2 CT x Re-stacking of nanoplates;
(3) Adding Nb to printing ink 2 CT x Solution, 3D printed Nb made 2 CT x The rGO composite sodium metal anode has rich functional groups inside, and 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 is a 3D printed Nb prepared in an embodiment of the present invention 2 CT x Scanning electron microscope pictures of the rGO composite aerogel under different magnifications.
FIG. 3 is a 3D printed Nb prepared in an embodiment of the present invention 2 CT x XRD pattern of rGO composite aerogel sodium metal negative electrode.
FIG. 4 is a 3D printed Nb in an embodiment of the present invention 2 CT x Stress-strain graph during the rGO composite aerogel test.
FIG. 5 is a 3D printed Nb in example 4 of the present invention 2 CT x rGO composite aerogel sodium metal anode at 10mA/cm 2 ，1mAh/cm 2 Cycling performance graph under conditions.
FIG. 6 is a 3D printed Nb in example 4 of the present invention 2 CT x rGO composite aerogel sodium metal anode at 3mA/cm 2 ，1mAh/cm 2 Coulombic efficiency plot under conditions.
FIG. 7 is a 3D printed Nb in an embodiment of the present invention 2 CT x 3D printing rGO/Na as negative electrode 3 V 2 (PO 4 ) 3 Full battery with @ C composite micro-grid aerogel as positive electrode and 100mA/g currentCycling plots at density with illustrations (illustrations are illustrations of assembled full cell successful ignition LED lamp).
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Specific implementations of the invention are described in detail below in connection with specific embodiments.
Example 1
Referring to FIGS. 1-7, a method for preparing 3D printed Nb 2 CT x A method of a rGO composite sodium metal anode, the method comprising the steps of:
step 1: GO dispersion was prepared by modified Hummer method for the above liquid and Nb 2 CT x Mixing and stirring the solution, centrifuging at low temperature, and grinding black gel at the bottom of the centrifuge tube to obtain Nb 2 CT x GO composite ink;
step 2: the Nb obtained in the step 1 is taken 2 CT x the/GO composite ink is transferred into a syringe barrel at a certain pressure, a direct writing type 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 Freeze-drying the GO composite three-dimensional ordered porous structure;
step 3: the Nb after the freeze drying treatment in the step 2 2 CT x Transferring the composite three-dimensional ordered porous structure into a tube furnace for high-temperature annealing to obtain 3D printed Nb 2 CT x rGO composite aerogel;
step 4: printing Nb in 3D prepared in the step 3 2 CT x the/rGO composite aerogel is put into a CR2032 button cell, a counter electrode is a sodium sheet, celgard 2400 is used as a diaphragm, and 80 mu L1M solute is used as NaPF 6 And an electrolyte solution of diglyme as solvent, deposited to an area capacity of 2mAh/cm 2 Constant current discharge treatment is carried out;
step 5: for a pair ofDisassembling the button cell after discharging treatment in the step 4, and printing Nb in 3D 2 CT x Taking out the rGO composite aerogel to obtain 3D printed Nb 2 CT x rGO composite sodium metal negative electrode for Nb 2 CT x And carrying out electrochemical test and mechanical strength tensile test on the rGO composite aerogel sodium metal anode.
GO hydrogel and Na 3 V 2 (PO 4 ) 3 Mixing the @ C powder in a mass ratio of 1:1 to obtain GO/Na 3 V 2 (PO 4 ) 3 @C composite ink and 3D printed GO/Na obtained by using 3D printing technology 3 V 2 (PO 4 ) 3 At Ar/H @ C micro-grid electrode 2 (95/5%) atmosphere, gas flow rate of 40sccm, heating and cooling rate of 1 deg.C/min, and maintaining at 600deg.C for 2 hr to obtain 3D printed rGO/Na 3 V 2 (PO 4 ) 3 @C positive electrode, 3D-printed Nb prepared as described above 2 CT x rGO/Na printed by 3D matching with rGO sodium metal negative electrode 3 V 2 (PO 4 ) 3 The CR2032 type button full cell was assembled using the same electrolyte and separator as described above, and the application thereof is shown in the inset of fig. 7, for example.
FIG. 2 is a 3D printed Nb prepared in this example 2 CT x Scanning electron microscope pictures of/rGO composite aerogel under different magnifications, and from the pictures, it can be known that GO dispersion liquid and Nb 2 CT x After stirring, centrifuging and grinding the solution, preparing Nb by using a 3D printing technology 2 CT x Performing freeze drying and high temperature heat treatment on the GO micro-grid structure to obtain Nb 2 CT x rGO composite aerogel; as shown by a in fig. 2, nb is 3D printed 2 CT x the/rGO composite aerogel consisted of ribs about 400 microns wide and pores 500 microns in size; as shown in b in fig. 2, nb is 3D printed 2 CT x The surface of the rGO composite aerogel has a plurality of micropore structures; as shown in c of fig. 2, nb 2 CT x Uniformly adhere to the rGO surface.
FIG. 3 is a 3D printed Nb 2 CT x XRD pattern of rGO composite aerogel sodium metal anode,as shown in the figure, zn is added 2+ After that, break down Nb 2 CT x Electrostatic repulsive force between nano sheets is connected together to form stable three-dimensional Nb 2 CT x Hydrogel, nb 2 CT x The spacing between the nano-sheets is reduced, and the XRD peak position is shifted to a large angle direction.
FIG. 4 is Nb 2 CT x Stress-strain curve of/rGO composite aerogel, nb 2 CT x rGO-0: indicating no Zn content 2+ ；Nb 2 CT x rGO-1: zn-containing alloy 2+ The method comprises the steps of carrying out a first treatment on the surface of the In Nb 2 CT x Zn is introduced into the solution 2+ Destruction of Nb 2 CT x Electrostatic repulsive force between nano sheets to form stable three-dimensional Nb 2 CT x Hydrogels effectively inhibit Nb 2 CT x The re-stacking of the nano-sheets is beneficial to improving Nb in the material 2 CT x The association degree between the nano sheets and between the graphene nano sheets is obviously improved 2 CT x Mechanical properties of rGO aerogel.
FIG. 5 is a 3D printed Nb 2 CT x rGO composite aerogel sodium metal anode at 10mA/cm 2 And an area current density of 1mAh/cm 2 Long-cycle test chart under specific area capacity condition, as shown in figure, nb is 3D printed 2 CT x Half cell assembled by rGO composite aerogel sodium metal negative electrode at 10mA/cm 2 Can be cycled steadily over 150 hours at high current densities.
FIG. 6 is a 3D printed Nb 2 CT x rGO composite aerogel sodium metal anode at 3mA/cm 2 And an area current density of 1mAh/cm 2 Coulombic efficiency plot under specific area capacity conditions, as shown in 3D printed Nb 2 CT x The average coulombic efficiency of the first 1000 cycles of the assembled half cell of the/rGO composite aerogel sodium metal anode was 99.25%.
FIG. 7 is a 3D printed Nb 2 CT x rGO composite aerogel sodium metal negative electrode matched with 3D printing rGO/Na 3 V 2 (PO 4 ) 3 The @ C is used as a circulation curve of the full battery formed by the positive electrode at the current density of 100mA/g, and is insertedFIG. 3D prints Nb 2 CT x rGO composite aerogel sodium metal negative electrode matched with 3D printing rGO/Na 3 V 2 (PO 4 ) 3 CR2032 button full cell at @ C positive pole lights up LED lamp demonstration photographs.
Example 2
Referring to FIGS. 1-7, a method for preparing 3D printed Nb 2 CT x A method of a rGO composite sodium metal anode, the method comprising the steps of:
step 1: preparing GO dispersion by improved Hummer method, and mixing the above liquid with Nb 2 CT x Solution and ZnSO with mass fraction of 0.1% 4 ·7H 2 Mixing and stirring the O solution, centrifuging at low temperature, and grinding black gel at the bottom of the centrifuge tube to obtain Nb 2 CT x GO composite ink; in this process, at Nb 2 CT x Zn is introduced into the solution 2+ Destruction of Nb 2 CT x Electrostatic repulsive force between nano sheets to form stable three-dimensional Nb 2 CT x Hydrogels effectively inhibit Nb 2 CT x And (3) re-stacking the nano-sheets. At the same time facilitate the improvement of Nb in the material 2 CT x Correlation degree between nano sheets and between graphene nano sheets, and further 3D printing Nb 2 CT x The strength of the rGO composite aerogel electrode is improved;
step 2: the Nb obtained in the step 1 is taken 2 CT x the/GO composite ink is transferred into a syringe barrel at a certain pressure, a direct writing type 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 Freeze-drying the GO composite three-dimensional ordered porous structure;
step 3: the Nb after the freeze drying treatment in the step 2 2 CT x Transferring the composite three-dimensional ordered porous structure into a tube furnace for high-temperature annealing to obtain 3D printed Nb 2 CT x rGO composite aerogel;
step 4: printing Nb in 3D prepared in the step 3 2 CT x the/rGO composite aerogel is put into a CR2032 type button cell, the counter electrode is a sodium sheet,celgard 2400 was used as a membrane with 80. Mu.L 1M solute as NaPF 6 And an electrolyte solution of diglyme as solvent, deposited to an area capacity of 2mAh/cm 2 Constant current discharge treatment is carried out;
step 5: disassembling the button cell after the discharging treatment in the step 4, and printing Nb in 3D 2 CT x Taking out the rGO composite aerogel to obtain 3D printed Nb 2 CT x rGO composite sodium metal negative electrode, and finally, 0.1% ZnSO is added into the negative electrode 4 ·7H 2 Samples of O were subjected to electrochemical testing and mechanical strength tensile testing.
GO hydrogel and Na 3 V 2 (PO 4 ) 3 Mixing the @ C powder in a mass ratio of 1:1 to obtain GO/Na 3 V 2 (PO 4 ) 3 @C composite ink and 3D printed GO/Na obtained by using 3D printing technology 3 V 2 (PO 4 ) 3 At Ar/H @ C micro-grid electrode 2 (95/5%) atmosphere, gas flow rate of 40sccm, heating and cooling rate of 1 deg.C/min, and maintaining at 600deg.C for 2 hr to obtain 3D printed rGO/Na 3 V 2 (PO 4 ) 3 @C positive electrode, 3D-printed Nb prepared as described above 2 CT x rGO/Na printed by 3D matching with rGO sodium metal negative electrode 3 V 2 (PO 4 ) 3 The CR2032 type button full cell was assembled using the same electrolyte and separator as described above, and the application thereof is shown in the inset of fig. 7, for example.
Example 3
Referring to FIGS. 1-7, a method for preparing 3D printed Nb 2 CT x A method of a rGO composite sodium metal anode, the method comprising the steps of:
step 1: preparing GO dispersion by improved Hummer method, and mixing the above liquid with Nb 2 CT x Solution and ZnSO with mass fraction of 0.3% 4 ·7H 2 Mixing and stirring the O solution, centrifuging at low temperature, and grinding black gel at the bottom of the centrifuge tube to obtain Nb 2 CT x GO composite ink; in this process, at Nb 2 CT x Introduction of Z into solutionn 2+ Destruction of Nb 2 CT x Electrostatic repulsive force between nano sheets to form stable three-dimensional Nb 2 CT x Hydrogels effectively inhibit Nb 2 CT x And (3) re-stacking the nano-sheets. At the same time facilitate the improvement of Nb in the material 2 CT x Correlation degree between nano sheets and between graphene nano sheets, and further 3D printing Nb 2 CT x The strength of the rGO composite aerogel electrode is improved;
step 2: the Nb obtained in the step 1 is taken 2 CT x the/GO composite ink is transferred into a syringe barrel at a certain pressure, a direct writing type 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 Freeze-drying the GO composite three-dimensional ordered porous structure;
step 3: the Nb after the freeze drying treatment in the step 2 2 CT x Transferring the composite three-dimensional ordered porous structure into a tube furnace for high-temperature annealing to obtain 3D printed Nb 2 CT x rGO composite aerogel;
step 4: printing Nb in 3D prepared in the step 3 2 CT x the/rGO composite aerogel is put into a CR2032 button cell, a counter electrode is a sodium sheet, celgard 2400 is used as a diaphragm, and 80 mu L1M solute is used as NaPF 6 And an electrolyte solution of diglyme as solvent, deposited to an area capacity of 2mAh/cm 2 Constant current discharge treatment is carried out;
step 5: disassembling the button cell after the discharging treatment in the step 4, and printing Nb in 3D 2 CT x Taking out the rGO composite aerogel to obtain 3D printed Nb 2 CT x rGO composite sodium metal negative electrode, and finally adding ZnSO with mass fraction of 0.3% 4 ·7H 2 Samples of O were subjected to electrochemical testing and mechanical strength tensile testing.
GO hydrogel and Na 3 V 2 (PO 4 ) 3 Mixing the @ C powder in a mass ratio of 1:1 to obtain GO/Na 3 V 2 (PO 4 ) 3 @C composite ink and 3D printed GO/Na obtained by using 3D printing technology 3 V 2 (PO 4 ) 3 At Ar/H @ C micro-grid electrode 2 (95/5%) atmosphere, gas flow rate of 40sccm, heating and cooling rate of 1 deg.C/min, and maintaining at 600deg.C for 2 hr to obtain 3D printed rGO/Na 3 V 2 (PO 4 ) 3 @C positive electrode, 3D-printed Nb prepared as described above 2 CT x rGO/Na printed by 3D matching with rGO sodium metal negative electrode 3 V 2 (PO 4 ) 3 The CR2032 type button full cell was assembled using the same electrolyte and separator as described above, and the application thereof is shown in the inset of fig. 7, for example.
Example 4
Referring to FIGS. 1-7, a method for preparing 3D printed Nb 2 CT x A method of a rGO composite sodium metal anode, the method comprising the steps of:
step 1: preparing GO dispersion by improved Hummer method, and mixing the above liquid with Nb 2 CT x Solution and ZnSO with mass fraction of 0.6% 4 ·7H 2 Mixing and stirring the O solution, centrifuging at low temperature, and grinding black gel at the bottom of the centrifuge tube to obtain Nb 2 CT x GO composite ink; in this process, at Nb 2 CT x Zn is introduced into the solution 2+ Destruction of Nb 2 CT x Electrostatic repulsive force between nano sheets to form stable three-dimensional Nb 2 CT x Hydrogels effectively inhibit Nb 2 CT x And (3) re-stacking the nano-sheets. At the same time facilitate the improvement of Nb in the material 2 CT x Correlation degree between nano sheets and between graphene nano sheets, and further 3D printing Nb 2 CT x The strength of the rGO composite aerogel electrode is improved;
step 2: the Nb obtained in the step 1 is taken 2 CT x the/GO composite ink is transferred into a syringe barrel at a certain pressure, a direct writing type 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 Freeze-drying the GO composite three-dimensional ordered porous structure;
step 3: freeze-drying in step 2Processed Nb 2 CT x Transferring the composite three-dimensional ordered porous structure into a tube furnace for high-temperature annealing to obtain 3D printed Nb 2 CT x rGO composite aerogel;
step 4: printing Nb in 3D prepared in the step 3 2 CT x the/rGO composite aerogel is put into a CR2032 button cell, a counter electrode is a sodium sheet, celgard 2400 is used as a diaphragm, and 80 mu L1M solute is used as NaPF 6 And an electrolyte solution of diglyme as solvent, deposited to an area capacity of 2mAh/cm 2 Constant current discharge treatment is carried out;
step 5: disassembling the button cell after the discharging treatment in the step 4, and printing Nb in 3D 2 CT x Taking out the rGO composite aerogel to obtain 3D printed Nb 2 CT x rGO composite sodium metal negative electrode, and finally, 0.6% ZnSO is added in the negative electrode 4 ·7H 2 Samples of O were tested electrochemically and mechanically as tensile testing, and found: adding ZnSO with mass fraction of 0.6% 4 ·7H 2 O sample assembled cell at 3mA/cm 2 ，1mAh/cm 2 The average coulomb efficiency of the first 1000 cycles under the cyclic test condition can reach 99.25 percent, and the average coulomb efficiency is 10mA/cm 2 Can be cycled steadily over 150 hours at high current densities.
GO hydrogel and Na 3 V 2 (PO 4 ) 3 Mixing the @ C powder in a mass ratio of 1:1 to obtain GO/Na 3 V 2 (PO 4 ) 3 @C composite ink and 3D printed GO/Na obtained by using 3D printing technology 3 V 2 (PO 4 ) 3 At Ar/H @ C micro-grid electrode 2 (95/5%) atmosphere, gas flow rate of 40sccm, heating and cooling rate of 1 deg.C/min, and maintaining at 600deg.C for 2 hr to obtain 3D printed rGO/Na 3 V 2 (PO 4 ) 3 @C positive electrode, 3D-printed Nb prepared as described above 2 CT x rGO/Na printed by 3D matching with rGO sodium metal negative electrode 3 V 2 (PO 4 ) 3 Positive electrode @ C, CR2032 button full cell was assembled using the same electrolyte and separator as described above, and its application was as shown in the inset of FIG. 7Shown.
Example 5
Referring to fig. 1-7, a method for preparing a 3D printed NB 2 CT x A method of a rGO composite sodium metal anode, the method comprising the steps of:
step 1: preparing GO dispersion by improved Hummer method, and mixing the above liquid with Nb 2 CT x Solution and ZnSO with mass fraction of 0.8% 4 ·7H 2 Mixing and stirring the O solution, centrifuging at low temperature, and grinding black gel at the bottom of the centrifuge tube to obtain Nb 2 CT x GO composite ink; in this process, at Nb 2 CT x Zn is introduced into the solution 2+ Destruction of Nb 2 CT x Electrostatic repulsive force between nano sheets to form stable three-dimensional Nb 2 CT x Hydrogels effectively inhibit Nb 2 CT x And (3) re-stacking the nano-sheets. At the same time facilitate the improvement of Nb in the material 2 CT x Correlation degree between nano sheets and between graphene nano sheets, and further 3D printing Nb 2 CT x The strength of the rGO composite aerogel electrode is improved;
step 2: the Nb obtained in the step 1 is taken 2 CT x the/GO composite ink is transferred into a syringe barrel at a certain pressure, a direct writing type 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 Freeze-drying the GO composite three-dimensional ordered porous structure;
step 3: the Nb after the freeze drying treatment in the step 2 2 CT x Transferring the composite three-dimensional ordered porous structure into a tube furnace for high-temperature annealing to obtain 3D printed Nb 2 CT x rGO composite aerogel;
step 4: printing Nb in 3D prepared in the step 3 2 CT x the/rGO composite aerogel is put into a CR2032 button cell, a counter electrode is a sodium sheet, celgard 2400 is used as a diaphragm, and 80 mu L1M solute is used as NaPF 6 And an electrolyte solution of diglyme as solvent, deposited to an area capacity of 2mAh/cm 2 Constant current discharge treatment is carried out;
step 5: disassembling the button cell after the discharging treatment in the step 4, and printing Nb in 3D 2 CT x Taking out the rGO composite aerogel to obtain 3D printed Nb 2 CT x rGO composite sodium metal negative electrode, wherein ZnSO with mass percent of 0.8% is added into the negative electrode 4 ·7H 2 Samples of O were subjected to electrochemical testing and mechanical strength tensile testing.
GO hydrogel and Na 3 V 2 (PO 4 ) 3 Mixing the @ C powder in a mass ratio of 1:1 to obtain GO/Na 3 V 2 (PO 4 ) 3 @C composite ink and 3D printed GO/Na obtained by using 3D printing technology 3 V 2 (PO 4 ) 3 At Ar/H @ C micro-grid electrode 2 (95/5%) atmosphere, gas flow rate of 40sccm, heating and cooling rate of 1 deg.C/min, and maintaining at 600deg.C for 2 hr to obtain 3D printed rGO/Na 3 V 2 (PO 4 ) 3 @C positive electrode, 3D-printed Nb prepared as described above 2 CT x rGO/Na printed by 3D matching with rGO sodium metal negative electrode 3 V 2 (PO 4 ) 3 The CR2032 type button full cell was assembled using the same electrolyte and separator as described above, and the application thereof is shown in the inset of fig. 7, for example.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (5)
1. Nb printing for preparing 3D 2 CT x The method of the rGO composite sodium metal anode is characterized by comprising the following steps:
step 1: preparing GO dispersion by improved Hummer method, and mixing the above liquid with Nb 2 CT x Solution and ZnSO 4 ·7H 2 Mixing and stirring the O solution, centrifuging at low temperature, and grinding black gel at the bottom of the centrifuge tube to obtain Nb 2 CT x GO composite ink;
step 2: the Nb obtained in the step 1 is taken 2 CT x the/GO composite ink is transferred into a syringe barrel at a certain pressure, a direct writing type 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 Freeze-drying the GO composite three-dimensional ordered porous structure;
step 3: the Nb after the freeze drying treatment in the step 2 2 CT x Transferring the composite three-dimensional ordered porous structure into a tube furnace for high-temperature annealing to obtain 3D printed Nb 2 CT x rGO composite aerogel;
step 4: printing Nb in 3D prepared in the step 3 2 CT x Putting the rGO composite aerogel into a CR2032 button cell, wherein a counter electrode is a sodium sheet, and performing constant current discharge treatment under the condition of certain area current density;
step 5: disassembling the button cell after the discharging treatment in the step 4, and printing Nb in 3D 2 CT x Taking out the rGO composite aerogel to obtain 3D printed Nb 2 CT x rGO composite sodium metal negative electrode;
in step 1, the Nb 2 CT x The mass fraction of the solution is 20%;
the ZnSO is 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 rapidly gelling binder that increases mechanical strength and stability;
in step 2, the Nb 2 CT x The composite three-dimensional ordered porous structure of the GO is a porous array structure with the length of (0.8-1.2) cm multiplied by (2-10) mm;
in step 3, nb is added to 2 CT x The annealing condition of the GO composite three-dimensional ordered porous structure moving into the tube furnace is as follows: introducing 95/5% Ar/H at a gas flow rate of 30-40sccm 2 The temperature of the mixed gas is 1-2 ℃/min, the temperature of the mixed gas is 450 ℃, and the temperature of the mixed gas is 1-3 hours.
2. The method of preparing 3D printed Nb according to claim 1 2 CT x /rGThe method for O-compounding the sodium metal anode is characterized in that in the step 1, the temperature of a sample is kept at 0-10 ℃ in the low-temperature centrifugal treatment process, the rotating speed of a centrifugal machine is 15000-20000rpm, and the centrifugal time is 10-30 minutes.
3. The method of preparing 3D printed Nb according to claim 1 2 CT x The method of the rGO composite sodium metal anode is characterized in that in the step 2, the pressure is 0.15-0.25MPa, and the moving speed of the needle point is 5-10mm/s.
4. The method of preparing 3D printed Nb according to claim 1 2 CT x A method for preparing a composite sodium metal anode of rGO, characterized in that in step 2, a freeze dryer is used for Nb 2 CT x The temperature condition of freeze drying of the composite three-dimensional ordered porous structure of/GO is-30 to-40 ℃ and the time is 24-48 hours.
5. The method of preparing 3D printed Nb according to claim 1 2 CT x Method of/rGO composite sodium metal negative electrode, characterized in that in step 4, nb is printed in 3D 2 CT x Placing the rGO composite aerogel into a CR2032 button battery and then standing for 2min;
at an upper limit of the voltage range of 0.5V and an area current density of 1mA/cm 2 Constant current discharge was carried out for 2 hours under the condition.
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