CN111217354B - Self-supporting sodium ion battery cathode material based on 3D printing and preparation method thereof - Google Patents
Self-supporting sodium ion battery cathode material based on 3D printing and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a self-supporting sodium-ion battery cathode material based on 3D printing and a preparation method thereof. The method comprises the following steps: a. uniformly mixing base resin, chlorella and other raw materials; b. melting, granulating and extruding to obtain a wire; c. printing a three-dimensional electrode slice structure on the carbon fiber prepreg cloth by an FDM 3D printing technology; d. and adsorbing a vanadium source by using an electrode plate printed on carbon fiber prepreg cloth, drying and selenizing to obtain the self-supporting V/Se-chlorella derived carbon sodium ion battery cathode. According to the invention, a 3D printing technology is adopted, chlorella-containing wires are used as printing materials, a three-dimensional electrode plate structure with adjustable size and designable shape is prepared, and then a vanadium source is introduced onto the electrode plate to obtain a self-supporting electrode plate structure with excellent performance; secondly, the complex process that the common powdery active material needs to be added with a conductive agent and a binder to form slurry and then coated on a current collector in the battery assembly process is avoided.
Description
Technical Field
The invention belongs to the technical field of preparation of sodium ion battery electrode materials, and particularly relates to a self-supporting sodium ion battery cathode material based on 3D printing and a preparation method thereof.
Background
The commercially utilized lithium ion battery has the advantages of large specific capacity, long cycle life, wide working temperature range, safety, no pollution and the like, and is widely applied to respective energy storage equipment, but the storage demand of future energy cannot be met due to uneven distribution and limited lithium resources in the earth crust. The specific capacity of the sodium-ion battery is lower than that of lithium, but the rich storage capacity (2.36 wt% of Na vs 0.0017 wt% of Li) of the sodium-ion battery and an energy storage mechanism similar to that of the lithium-ion battery enable the sodium-ion battery to become a large-scale energy storage battery technology with great development potential after the lithium battery. However, the conventional electrode preparation process generally requires the application of an electrode active material onto a current collector using a conductive agent, a binder, or the like, and is cumbersome and liable to cause the active material to be induced to be detached from the current collector in the case of electrode bending.
The 3D printing technique is an additive manufacturing technique that can be used to manufacture solid objects of any shape or size. The principle of the method is that preset model parameters needing to be printed are led into a 3D printing device, then prepared thermoplastic resin wires are fed, the wires are heated and melted by a heating device, materials in a viscous flow state are extruded out under certain pressure, printing is carried out according to a 3D printing model stored in an SD card, after the first layer is printed, a printing platform descends to continuously print the next layer according to a printing path, and final printing is completed by overlapping layer by layer. The model manufactured by FDM 3D printing can be designed into various shapes according to requirements, the surface gloss of the obtained material is textured, and the obtained material can be directly taken down after printing is finished without any post-processing operation. Therefore, the electrode plate structure is prepared by using the efficient and accurate FDM technology, a conductive agent and a binder in the traditional electrode are not needed, and the electrode plate structure has great application advantages.
In addition, the chlorella is a unicellular algae with high protein, high polysaccharide, low fat and rich vitamins and minerals, contains functional groups such as amino, carboxyl, hydroxyl and the like, and has strong adsorption performance. The vanadium-based material has the advantages of rich reserves, active chemical properties, no toxicity and the like, and has higher specific capacity when being used as an electrode material, so that the chlorella is utilized to introduce a vanadium source onto an electrode device, and the electrochemical performance of the electrode slice can be improved. Moreover, the existence of the N, P, C-enriched chlorella is also beneficial to improving the conductivity of the material, the osmotic diffusion of electrolyte and the electronic conductivity of an electrode material.
Therefore, the biomass chlorella which is strong in adsorption capacity and rich in N, P, C is added into the FDM 3D printing wire, a three-dimensional electrode plate structure is printed on carbon fiber prepreg cloth, and the self-supporting vanadium and selenium-doped chlorella-derived carbon sodium ion battery cathode material is obtained after vanadium source adsorption, selenization and carbonization. The preparation process is convenient and simple, the traditional dispersing agent, conductive agent and binder are not needed, the printed electrode plate can be directly used as an electrode plate, and the preparation method is green and environment-friendly. When the electrode plate is used as a negative electrode of a sodium ion battery, the electrode plate shows excellent electrochemical performance.
Disclosure of Invention
The invention aims to solve the defect that the active material is fixed on a copper sheet by adopting a dispersing agent, a conductive agent and a binder in the traditional electrode, so that the active material is easily induced to be separated from a current collector under the bending condition of the electrode, and provides a self-supporting sodium-ion battery cathode material and a preparation method thereof by utilizing FDM 3D printing technology.
The preparation method is characterized in that the electrode plate structure is prepared by drying, mixing, melting and granulating raw materials such as matrix resin, chlorella and the like, extruding wires, printing and the like, and then selenizing and carbonizing the raw materials to obtain the self-supporting cathode electrode plate of the V/Se-chlorella derived carbon sodium ion battery.
The purpose of the invention is realized by the following technical scheme:
a self-supporting sodium-ion battery negative electrode material based on 3D printing is characterized by being prepared from the following components in percentage by weight:
35-58 parts of matrix resin
41-60 parts of chlorella
0.1-5% of white oil
A preparation method of a self-supporting sodium-ion battery negative electrode material based on 3D printing comprises the following steps:
A. mixing the matrix resin, the pellets and the white oil according to the formula ratio, and then melting, extruding and granulating through a double-screw extruder;
B. the obtained granules are drawn into a 3D printing wire rod through a single-screw wire rod extruder;
C. printing a 3D printing wire into an electrode plate structure on a bottom plate paved with carbon fiber prepreg cloth by an FDM technology;
D. c, enabling the electrode plate structure obtained in the step C to be 1: 2-5, placing the mixture in a beaker containing a vanadium source solution, and slowly stirring for 24 hours to obtain a vanadium modified chlorella electrode plate structure;
E. and D, calcining the electrode plate structure of the vanadium modified chlorella obtained in the step D and selenium powder at high temperature, and naturally cooling to room temperature to obtain the self-supporting sodium-ion battery negative electrode material. The matrix resin is at least one selected from polylactic acid (PLA), polybutylene adipate terephthalate (PBAT), acrylonitrile-butadiene-styrene (ABS) and Thermoplastic Polyurethane (TPU).
At least one of the Chlorella is selected from Chlorella vulgaris with high protein content, Chlorella vulgaris or Chlorella ellipsoidea.
The vanadium source is at least one selected from vanadyl acetylacetonate (VO (acac) 2 ) Sodium metavanadate (NaVO) 3 ) Ammonium metavanadate (NH) 4 VO 3 ）。
The concentration of the vanadium source solution is 20-60 mg/L.
The technological parameters of the double-screw extruder are that the temperature of each section is 120-240 ℃, the temperature of a die head is 170-220 ℃, and the rotating speed of a screw is 10-180 rpm.
The single-screw wire rod extruder has the technical parameters that the processing temperature is 60-250 ℃, the screw rotating speed is 10-180 rpm, and the water temperature of the first water-cooling section is 25-65 ℃; the water temperature of the second section is 5-25 ℃.
The carbon fiber prepreg is at least one selected from carbon fiber epoxy resin prepreg and carbon fiber bismaleimide resin prepreg.
The calcination is carried out at 5% H 2 Placing active substances on the electrode plate structure and selenium powder with the mass ratio of 1:2 in a tubular furnace under the Ar atmosphere of/95%, setting the gas flow rate to be 50-100 mL/min, the heating rate to be 1-5 ℃ per min, and calcining for 2-4 h at the temperature of 400-800 ℃.
The self-supporting sodium ion battery cathode material based on 3D printing is used for a sodium ion battery cathode, and the loading capacity of active substances in the battery cathode material is 1-6 mg/cm 2 。
Compared with the prior art, the invention has the following specific advantages:
1. the self-supporting electrode plate device prepared by using the 3D printing technology has the characteristics of simple preparation process, controllable structural appearance and low cost, does not need a conductive agent or a binder, overcomes the defect that the traditional electrode induces an active material to be separated from a current collector under the bending condition, and has the prospect of large-scale application.
2. The biomass chlorella is a small-volume unicellular autotroph, is rich in functional groups such as hydroxyl groups and the like, has strong adsorption performance, can be added into an electrode device and can be used as an adsorbent to introduce a vanadium source with high specific capacity into an electrode slice so as to improve the sodium storage performance.
3. The material is used as a negative electrode material of a sodium-ion battery, and shows excellent electrochemical performance. The specific capacity can reach 194 mA h g after 700 charge-discharge cycles under the current density of 500 mA/g -1 The specific capacity of the lithium ion battery can be still stabilized at 106 mAh g after 2000 times of charge-discharge circulation under the high current density of 2A/g -1 Coulomb efficiency ofNearly 100%, show that the 3D printing self-supporting material can be applied to the field of battery materials, and industrial application of preparing batteries in laboratories is realized.
Drawings
Fig. 1 is an SEM image of the 3D printed self-supporting sodium ion battery negative electrode material obtained in example 1.
Fig. 2 is a SEM-EDX image of the 3D printed self-supporting sodium-ion battery anode material obtained in example 1.
Fig. 3 is a graph of the cycling performance of the 3D printed self-supporting sodium ion battery anode material from example 1 at a current density of 500 mA/g.
Fig. 4 is a graph of the cycling performance at 2A/g current density of the 3D printed self-supporting sodium ion battery anode material obtained in example 1.
Fig. 5 is a graph of the charge and discharge curves at a current density of 500 mA/g for the 3D printed self-supporting sodium ion battery negative electrode material obtained in example 1.
Detailed Description
Example 1
1. A self-supporting sodium-ion battery negative electrode material based on 3D printing is characterized by being prepared from the following components in percentage by weight:
chlorella 58
2. A preparation method of a self-supporting sodium-ion battery negative electrode material based on 3D printing comprises the following steps:
A. mixing PLA, pellets and white oil according to the formula amount, and then performing melt extrusion granulation by a double-screw extruder, wherein the process parameters of the double-screw extruder are that the temperature of each section is 123, 135, 142, 160, 166, 170, 165, 155 and 140 ℃, the die head temperature is 170 ℃, and the screw rotating speed is 50 rpm;
B. the obtained granules are pulled into a 3D printing wire rod by a single-screw wire rod extruder, the process parameters of the single-screw wire rod extruder are that the processing temperature is 180 ℃, the screw rotating speed is 20 rpm, and the water temperature of a water cooling first section is 40 ℃; the water temperature of the second section is 20 ℃;
C. b, printing the 3D printing wire rod obtained in the step B into an electrode plate structure on a bottom plate paved with carbon fiber epoxy resin prepreg (carbon fiber prepreg for short) by an FDM technology;
D. c, enabling the electrode plate structure obtained in the step C to be 1:2, placing the mixture in a beaker containing acetylacetonatovanadyl solution (60mol/L), and slowly stirring for 24 hours to obtain a 3D printed self-supporting sodium ion electrode plate structure;
E. at 5% (volume percent concentration) H 2 And C, placing the active substance on the structure of the vanadium modified chlorella electrode plate obtained in the step D and selenium powder with the mass ratio of 1:2 in a tube furnace under the Ar atmosphere of 95% (volume percentage concentration), setting the gas flow rate at 100 mL/min, the heating rate at 2 ℃ per min, and calcining at 600 ℃ for 4 hours to obtain the 3D printing self-supporting sodium ion battery cathode material.
Fig. 1 is a macro and micro topography of a 3D printed self-supporting sodium ion battery anode material. It can be seen from (a) of fig. 1 that the electrode sheet maintains a good shape after being calcined at a high temperature of 600 ℃. Fig. 1 (b-D) illustrates that vanadium, selenium, etc. have been uniformly attached to the electrode sheet structure for 3D printing. From the SEM-EDX image corresponding to FIG. 2, it can be seen that C, O, V, Se and other elements are present in the composite material, and the content of C is high.
The 3D printing self-supporting sodium ion battery cathode material prepared by the embodiment is used as a sodium ion battery cathode, a metal sodium sheet is used as a counter electrode, and 1 mol/L NaClO 4 the/EC (ethylene carbonate)/DMC (dimethyl carbonate) is used as electrolyte to assemble the button type battery. All assemblies were performed in an argon inert atmosphere glove box and tested for cycle performance. FIG. 3 shows that the electrode has a specific capacity of 194 mA h g after 700 cycles of charge and discharge under a current density of 0.5A/g -1 . FIG. 4 shows that the specific capacity of the electrode can be stabilized at 106 mAh g after 2000 times of charge-discharge cycles under the high current density of 2A/g -1 Coulombic efficiency approaches 100%. Fig. 5 is a charge-discharge curve of the electrode material at a current density of 0.5A/g, and it can be seen from the graph that the overlap of the charge-discharge curve is better from the second cycle after the electrode material is discharged for the first time, which shows that the electrode material has good cycle stability. Therefore, the 3D printing self-supporting sodium ion battery negative electrode material has high charge-discharge ratioCapacity, large current cycle characteristic and excellent long cycle stability, and has good application prospect.
Example 2
1. A self-supporting sodium-ion battery negative electrode material based on 3D printing is characterized by being prepared from the following components in percentage by weight:
chlorella 49
2. A preparation method of a self-supporting sodium-ion battery negative electrode material based on 3D printing comprises the following steps:
A. mixing ABS, small balls and white oil according to the formula ratio, and then performing melt extrusion granulation by a double-screw extruder, wherein the process parameters of the double-screw extruder are that the temperature of each section is 130, 145, 152, 170, 186, 200, 195, 190 and 185 ℃, the temperature of a die head is 180 ℃, and the rotating speed of a screw is 80 rpm;
B. the obtained granules are pulled into a 3D printing wire rod by a single-screw wire rod extruder, the process parameters of the single-screw wire rod extruder are that the processing temperature is 200 ℃, the screw rotating speed is 20 rpm, and the water temperature of a water cooling first section is 50 ℃; the water temperature of the second section is 25 ℃;
C. b, printing the 3D printing wire rod obtained in the step B into an electrode plate structure on a base plate paved with carbon fiber bismaleimide resin prepreg cloth through an FDM technology;
D. c, enabling the electrode plate structure obtained in the step C to be 1: 3, placing the mixture in a beaker containing 50mol/L sodium metavanadate solution, and slowly stirring for 24 hours to obtain a vanadium-modified 3D printing self-supporting sodium ion electrode plate structure;
E. at 5% H 2 And D, placing the active substance on the vanadium modified 3D printing self-supporting sodium ion electrode plate structure obtained in the step D and selenium powder with the mass ratio of 1:2 in a tubular furnace under the Ar atmosphere of 95%, setting the gas flow rate to be 80 mL/min, the heating rate to be 3 ℃ per min, and calcining for 3 hours at the temperature of 550 ℃, thus obtaining the 3D printing self-supporting sodium ion battery cathode material.
The 3D printing self-supporting sodium ion battery cathode material prepared by the embodiment is used as a sodium ion battery cathode, and the metal sodium sheet isCounter electrode, 1 mol/L NaClO 4 and/EC (ethylene carbonate)/DMC (dimethyl carbonate) is used as electrolyte to assemble the button type battery. All assemblies were performed in an argon inert atmosphere glove box and tested for cycle performance.
Example 3
1. A self-supporting sodium-ion battery negative electrode material based on 3D printing is characterized by being prepared from the following components in percentage by weight:
TPU/ABS(50wt%:50wt%) 38
chlorella 59
White oil 3
2. A preparation method of a self-supporting sodium-ion battery negative electrode material based on 3D printing comprises the following steps:
A. mixing TPU/ABS (50wt%:50wt%), pellets and white oil according to the formula ratio, and then performing melt extrusion granulation by a double-screw extruder, wherein the process parameters of the double-screw extruder are that the temperature of each section is 130, 145, 150, 165, 180, 190, 185, 180 and 180 ℃, the die head temperature is 170 ℃ and the screw rotating speed is 60 rpm;
B. the obtained granules are pulled into a 3D printing wire rod by a single-screw wire rod extruder, the process parameters of the single-screw wire rod extruder are 190 ℃, the screw rotation speed is 30 rpm, and the water temperature of the first water-cooling section is 40 ℃; the water temperature of the second section is 25 ℃;
C. b, printing the 3D printing wire rod obtained in the step B into an electrode plate structure on the bottom plate paved with the carbon fiber epoxy resin prepreg cloth through an FDM technology;
D. c, enabling the electrode plate structure obtained in the step C to be 1: 2.5 placing the mixture into a beaker containing ammonium metavanadate solution (60mol/L), and slowly stirring for 24 hours to obtain a vanadium-modified 3D printing self-supporting sodium ion electrode plate structure;
E. at 5% H 2 Placing the active substance on the vanadium modified 3D printing self-supporting sodium ion electrode plate structure obtained in the step D and selenium powder with the mass ratio of 1:2 in a tubular furnace under the Ar atmosphere of 95%, setting the gas flow at 70 mL/min, the heating rate at 2 ℃ per min, and calcining at 500 ℃ for 3.5 hours to obtain the 3D printing self-supporting sodium ion electric electrodeA cell anode material.
The 3D printing self-supporting sodium ion battery cathode material prepared by the embodiment is used as a sodium ion battery cathode, a metal sodium sheet is used as a counter electrode, and 1 mol/L NaClO 4 the/EC (ethylene carbonate)/DMC (dimethyl carbonate) is used as electrolyte to assemble the button type battery. All assemblies were performed in an argon inert atmosphere glove box and tested for cycle performance.
Example 4
1. A self-supporting sodium-ion battery negative electrode material based on 3D printing is characterized by being prepared from the following components in percentage by weight:
PLA/PBAT(50wt%:50wt%) 35
chlorella (Chlorella vulgaris) 60
White oil 5
2. A preparation method of a self-supporting sodium-ion battery negative electrode material based on 3D printing comprises the following steps:
A. mixing PLA/PBAT (50wt%:50wt%), pellets and white oil according to the formula amount, and then performing melt extrusion granulation by a double-screw extruder, wherein the process parameters of the double-screw extruder are that the temperature of each section is 130, 145, 150, 165, 180, 195, 190, 185, 180 and 180 ℃, the temperature of a die head is 180 ℃, and the rotating speed of a screw is 50 rpm;
B. the obtained granules are pulled into a 3D printing wire rod by a single-screw wire rod extruder, the process parameters of the single-screw wire rod extruder are that the processing temperature is 200 ℃, the screw rotating speed and the screw rotating speed are 30 rpm, and the water temperature of a water cooling first section is 60 ℃; the water temperature of the second section is 20 ℃;
C. b, printing the 3D printing wire rod obtained in the step B into an electrode plate structure on the bottom plate paved with the carbon fiber epoxy resin prepreg cloth through an FDM technology;
D. c, enabling the electrode plate structure obtained in the step C to be 1: 4, placing the mixture into a beaker containing vanadyl acetylacetonate (30mol/L), and slowly stirring for 24 hours to obtain a vanadium-modified 3D printing self-supporting sodium ion electrode plate structure;
E. at 5% H 2 D, printing the vanadium modified 3D obtained in the step D on active substances on the structure of the self-supporting sodium ion electrode plate and the obtained mixture in the presence of 95% ArAnd placing the selenium powder with the mass ratio of 1:2 in a tubular furnace, setting the gas flow at 70 mL/min, the heating rate at 5 ℃/min, and calcining at 520 ℃ for 4 h to obtain the 3D printing self-supporting sodium ion battery cathode material.
The 3D printing self-supporting sodium ion battery cathode material prepared by the embodiment is used as a sodium ion battery cathode, a metal sodium sheet is used as a counter electrode, and 1 mol/L NaClO 4 the/EC (ethylene carbonate)/DMC (dimethyl carbonate) is used as electrolyte to assemble the button type battery. All assemblies were performed in an argon inert atmosphere glove box and tested for cycle performance.
Claims (6)
1. A preparation method of a self-supporting sodium-ion battery cathode material based on 3D printing is characterized in that,
the composition is prepared from the following components in percentage by weight:
35-58 parts of matrix resin
41-60 parts of chlorella
0.1-5% of white oil
The method comprises the following steps:
A. mixing the matrix resin, the pellets and the white oil according to the formula ratio, and then melting, extruding and granulating through a double-screw extruder;
B. the obtained granules are drawn into a 3D printing wire rod through a single-screw wire rod extruder;
C. printing a 3D printing wire on a bottom plate paved with carbon fiber prepreg cloth into an electrode plate structure by a fused deposition modeling technology;
D. c, enabling the electrode plate structure obtained in the step C to be 1: 2-5, placing the mixture in a beaker containing a vanadium source solution, and slowly stirring for 24 hours to obtain a vanadium modified chlorella electrode plate structure;
E. d, calcining the electrode plate structure of the vanadium modified chlorella obtained in the step D and selenium powder at high temperature, and naturally cooling to room temperature to obtain a self-supporting sodium-ion battery negative electrode material;
the vanadium source is at least one selected from vanadyl acetylacetonate, sodium metavanadate and ammonium metavanadate;
the concentration of the vanadium source solution is 20-60 mg/L;
said calciningIs at 5% H 2 Placing active substances on the electrode plate structure and selenium powder with the mass ratio of 1:2 in a tubular furnace under the Ar atmosphere of/95%, setting the gas flow rate to be 50-100 mL/min, the heating rate to be 1-5 ℃/min, and calcining for 2-4 h at the temperature of 400-800 ℃.
2. The method for preparing the self-supporting sodium-ion battery negative electrode material based on 3D printing according to claim 1, wherein the matrix resin is at least one selected from polylactic acid, polybutylene adipate-terephthalate, acrylonitrile-butadiene-styrene and thermoplastic polyurethane.
3. The method for preparing the self-supporting sodium-ion battery negative electrode material based on 3D printing according to claim 1, wherein at least one of the chlorella is selected from chlorella aegypti, chlorella kei or chlorella ellipsoidea.
4. The preparation method of the self-supporting sodium-ion battery negative electrode material based on 3D printing is characterized in that the process parameters of the double-screw extruder are that the temperature of each section is 120-240 ℃, the temperature of a die head is 170-220 ℃, and the rotating speed of a screw is 10-180 rpm; the single-screw wire extruder has the technical parameters that the processing temperature is 60-250 ℃, the screw rotating speed is 10-180 rpm, and the water temperature of the first water cooling section is 25-65 ℃; the water temperature of the second section is 5-25 ℃.
5. The preparation method of the self-supporting sodium-ion battery anode material based on 3D printing is characterized in that the carbon fiber prepreg cloth is at least one selected from carbon fiber epoxy resin prepreg cloth and carbon fiber bismaleimide resin prepreg cloth.
6. The preparation method of the self-supporting sodium-ion battery negative electrode material based on 3D printing as claimed in claim 1, characterized in that the loading amount of active materials in the battery negative electrode material is 1-6 mg/cm 2 。
Priority Applications (1)
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