CN114551788A - Ion field/electric field controllable three-dimensional metal cathode and preparation method thereof - Google Patents
Ion field/electric field controllable three-dimensional metal cathode and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention discloses an ion field/electric field controllable three-dimensional metal cathode and a preparation method thereof, wherein the preparation method comprises the following steps: (1) configuring 3D printing ink: adding a metal-philic substance, a viscous agent, a conductive agent and/or an active substance into a solvent, and regulating and controlling the proportion of each component to obtain 3D printing ink with different compositions; (2) preparing a 3D printing three-dimensional metal cathode: and printing the 3D printing ink with different compositions into a three-dimensional current collector in a layer-by-layer superposed 3D printing mode, and performing post-treatment to obtain the three-dimensional current collector. Through 3D printing structure design and ink component optimization, effective regulation and control of an ion field and an electric field of a three-dimensional framework are achieved, growth of dendrites of a metal negative electrode is effectively inhibited, and the dendrite-free three-dimensional metal negative electrode with excellent cycle performance is obtained.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to an ion field/electric field controllable three-dimensional metal cathode and a preparation method thereof.
Background
Metal negative electrodes (lithium, sodium, magnesium, aluminum, potassium, zinc, etc.) have extremely high theoretical specific capacity and low reduction potential, and are considered to be one of the most promising negative electrode candidates in next-generation metal ion batteries. However, a large volume change of the metal negative electrode is easily caused by a side reaction such as hydrogen evolution during charge and discharge. Meanwhile, uncontrolled dendrite growth of the metal negative electrode will cause it to fall off the substrate, causing severe capacity fade. Particularly, the serious dendrite growth under large current may pierce through the diaphragm to cause short circuit of the battery, which brings potential safety hazard and seriously hinders the practical application of the metal cathode.
To date, a great deal of research has been devoted to solving the problem of dendrite growth for metallic cathodes. Among them, the three-dimensional metal negative electrode has been paid much attention by researchers because of its characteristics such as large specific surface area and high porosity. The large specific surface area of the three-dimensional metal cathode can effectively reduce local current density and is beneficial to uniform nucleation; meanwhile, the three-dimensional structure can bind metal in the porous structure, and the volume change of the porous structure in the charge and discharge process is effectively limited. However, three-dimensional structures are affected by electric fields, and the ion concentration inside the structure tends to assume a gradient distribution, resulting in metal ions preferentially nucleating and growing at the top of the ion concentration and rarely migrating below the structure. The uneven plating/stripping process caused by the ion concentration gradient will accelerate dendrite growth and reduce the cycle life of the battery. Therefore, the method for researching and improving the gradient distribution problem of the ions of the three-dimensional metal cathode has important significance for prolonging the cycle life of the three-dimensional metal cathode.
Disclosure of Invention
Aiming at the prior art, the invention provides an ion field/electric field controllable three-dimensional metal cathode and a preparation method thereof, which are used for solving the problems of gradient distribution of ions of the conventional three-dimensional metal cathode, dendritic crystal growth and low cycle life of a battery.
In order to achieve the purpose, the invention adopts the technical scheme that: the preparation method of the ion field/electric field controllable three-dimensional metal cathode is provided, and comprises the following steps:
(1) configuring 3D printing ink: adding a metal-philic substance, a viscous agent, a conductive agent and/or an active substance into a solvent, and regulating and controlling the proportion of each component to obtain 3D printing ink with different compositions;
(2) preparing a 3D printing three-dimensional metal cathode: and printing the 3D printing ink with different compositions into a three-dimensional current collector in a layer-by-layer superposed 3D printing mode, and performing post-treatment to obtain the three-dimensional current collector.
The 3D printing ink is characterized in that the storage modulus is larger than the loss modulus so as to ensure the stable shape after the printing is finished, and meanwhile, the ink has an obvious shear thinning behavior meeting the printing requirement. According to the invention, the three-dimensional metal cathode is prepared in a 3D printing mode, the three-dimensional structures with different content of the metal-philic substances are prepared by adjusting the content of the metal-philic substances in the ink, and the electric field/ion field of the three-dimensional current collector is adjusted in the 3D printing mode and the ink component regulation mode, so that the safety and the circulation stability of the metal ion battery are greatly improved. The addition of the metal-philic substance can influence the distribution of the ion field in the three-dimensional metal cathode structure and provide power for the migration of metal ions. In addition, the strong adsorbability of the metal-philic substance to the metal ions can be utilized to fix the migrated metal ions. At the same time, the lower nucleation overpotential caused by the metallophilic property makes the deposition behavior of the metal ions around it easier. Through the electric field and the ion field are adjusted in a coordinated mode, the deposition site of metal is changed, the problem that the metal grows on the upper layer closer to the diaphragm is effectively solved, and the penetration of dendrites on the upper layer on the diaphragm is avoided.
The addition of the metal-philic substance can influence the distribution of the ion field in the three-dimensional metal cathode structure and provide power for the migration of metal ions. In addition, the strong adsorbability of the metal-philic substance to the metal ions can be utilized to fix the migrated metal ions. At the same time, the lower nucleation overpotential caused by the metallophilic property makes the deposition behavior of the metal ions around it easier. Through the electric field and the ion field are adjusted in a coordinated mode, the deposition site of metal is changed, the problem that the metal grows on the upper layer closer to the diaphragm is effectively solved, and the penetration of dendrites on the upper layer on the diaphragm is avoided.
Further, the mass ratio of the metal-philic substance, the viscous agent, the conductive agent and the active substance in the 3D printing ink is 10: 1-10: 0-10.
Further, the metal-philic substance is at least one of gold, silver, copper, nickel, tin, titanium, copper-zinc alloy, copper-tin alloy, Mxene, graphene, carbon nanotubes, titanium dioxide, manganese dioxide, aluminum oxide, copper oxide, cobalt oxide, tin oxide, zinc sulfide, zinc selenide, zinc oxide, and polyacrylamide.
Further, the thickening agent is at least one of bacterial cellulose, cotton cellulose, wood pulp cellulose, polyvinylidene fluoride, polyvinyl alcohol, gas phase silicon dioxide, sodium alginate, potassium alginate, sodium carboxymethylcellulose, polymethacrylate, polyvinyl acetal and styrene butadiene latex.
Further, the conductive agent is at least one of gold, silver, copper, nickel, tin, Mxene, graphene, carbon nanotubes, carbon fibers, and conductive carbon black.
Further, the active material is at least one of lithium, sodium, magnesium, aluminum, potassium, zinc metal or their corresponding metal oxides, metal sulfides, metal carbides or metal phosphides.
Further, the solvent is at least one of deionized water, ethyl acetate, N-methylpyrrolidone, acetone, dimethyl sulfoxide, acetonitrile, cyclohexane, carbon tetrachloride, N-dimethylacetamide, N-dimethylformamide and tetrahydrofuran.
Furthermore, the 3D printing method is a direct ink writing method, the diameter of a printing needle head is 100-700 mu m, and the distance between printed silk strips is 100-700 mu m.
Further, post-treatment includes drying and loading of the metal; the drying method comprises heat conduction drying, convection heat conduction drying, vacuum drying, normal pressure drying, freeze drying, flash evaporation drying, microwave heating drying, and infrared radiation drying; the metal loading mode comprises electrodeposition, fused deposition and redox deposition.
The invention also provides the ion field/electric field controllable three-dimensional metal cathode prepared by the preparation method.
On the basis of the technical scheme, the invention can be further improved as follows.
The invention has the beneficial effects that:
1. according to the invention, through 3D printing structure design and ink component regulation, effective regulation and control of an ion field and an electric field of the three-dimensional metal negative electrode are realized, growth of dendritic crystals of the metal negative electrode is effectively inhibited, and the dendritic-crystal-free three-dimensional metal negative electrode with excellent cycle performance is obtained.
2. According to the invention, through the combination of simple 3D printing structure design and ink component adjustment, the ubiquitous tip effect caused by uneven ion/electron distribution in the metal cathode is improved, and the universal ink has universality on the design of the metal cathode with long cycle life.
3. The method has simple flow and convenient operation, and can be widely applied to the preparation of metal cathodes such as lithium, sodium, magnesium, aluminum, potassium, zinc and the like.
Drawings
Fig. 1 is an EDS test of a 3D printed three-dimensional current collector;
fig. 2 is an XRD test of a 3D printed three-dimensional metal cathode;
fig. 3 is a nucleation overpotential test of a half-cell assembled by 3D printing of a three-dimensional current collector;
fig. 4 is a cycle performance test of a symmetrical battery assembled by 3D printed three-dimensional metal cathodes.
Detailed Description
The following examples are provided to illustrate specific embodiments of the present invention.
Example 1
A preparation method of an ion field/electric field controllable three-dimensional metal cathode comprises the following steps:
(1) taking 10mL of deionized water as a solvent, sequentially adding 1g of pulp cellulose, 1g of carbon nano tube and 1g of silver powder, and dispersing by adopting a high-speed homogenizer to prepare first-component ink; adjusting the mass of the silver powder to be 0.5g, and preparing second component ink after dispersion; adjusting the mass of the silver powder to be 0.5g, and preparing third component ink after dispersion;
(2) printing three kinds of ink according to the sequence of a first component, a second component and a third component, wherein the diameter of a printed needle is 400 mu m, the printing pressure of an air compressor is controlled to be 22psi, the movement speed of a mechanical arm is 8mm/min, a 3D printing set three-dimensional current collector is obtained after a printed product is subjected to solvent removal, then, the surface of the 3D printing set three-dimensional current collector is galvanized by adopting a constant current deposition mode, the deposition time is controlled to be 1 hour, and the deposition current density is 10mA/cm2And washing and drying to obtain the 3D printed zinc metal cathode.
Example 2
A preparation method of an ion field/electric field controllable three-dimensional metal cathode comprises the following steps:
(1) taking 12mL of deionized water as a solvent, sequentially adding 1g of vinyl alcohol and 1g of graphene, and dispersing by adopting a high-speed homogenizer to prepare first-component ink; changing the mass of the graphene to be 0.5g, and dispersing to obtain second component ink; changing the mass of the graphene to 0.1g, and preparing a third component ink after dispersion;
(2) printing the three kinds of ink according to the sequence of a first component, a second component and a third component, wherein the diameter of a printed needle is 100 micrometers, the printing pressure is controlled to be 22psi by an air compressor, the movement speed of a mechanical arm is 8mm/min, removing a solvent from a printed product to obtain a 3D printed three-dimensional current collector, and then depositing lithium on the surface of the printed product in a melting deposition mode in a glove box to obtain the 3D printed lithium metal cathode.
Example 3
A preparation method of an ion field/electric field controllable three-dimensional metal cathode comprises the following steps:
(1) taking 10mL of deionized water as a solvent, sequentially adding 1g of flower cellulose, 2g of carbon nano tubes and 0.2g of silver nano particles into the solvent, and dispersing by adopting a high-speed homogenizer to prepare first-component ink; changing the mass of the carbon nano tube to be 1g, and dispersing to prepare second component ink;
(2) printing two kinds of ink according to the sequence of a first component and a second component, wherein the diameter of a printed needle is 700 mu m, the printing pressure of an air compressor is controlled to be 22psi, the movement speed of a mechanical arm is 8mm/min, a 3D printed three-dimensional current collector is obtained after freeze-drying a printed product, then, the surface of the printed product is galvanized by adopting a constant current deposition method, the deposition time is controlled to be 1 hour, and the deposition current density is 10mA/cm2And washing and drying to obtain the 3D printing zinc metal cathode.
Example 4
A preparation method of an ion field/electric field controllable three-dimensional metal cathode comprises the following steps:
(1) taking 10mL of N-methylpyrrolidone as a solvent, sequentially adding 2g of vinylidene fluoride, 3g of graphene and 8g of zinc powder, and dispersing by adopting a high-speed homogenizer to prepare first-component ink; changing the mass of the graphene to be 2g, and dispersing to prepare second component ink;
(2) and (3) printing the three-dimensional current collector by the two kinds of ink according to the sequence of the first component and the second component, wherein the diameter of a printed needle is 400 mu m, the printing pressure controlled by an air compressor is 22psi, the movement speed of a mechanical arm is 8mm/min, and the printed product is dried by heat to remove the solvent. And in a glove box, precipitating sodium on the surface of the metal cathode by adopting a fused deposition mode to obtain the 3D printing sodium metal cathode.
Examples of the experiments
The nucleation overpotential of the three-dimensional current collector obtained in example 1 is characterized in the form of a half-cell, and the working electrode has an area of 1 × 1cm2The counter electrode is a zinc foil with the same size, the electrolyte is 1M zinc trifluoromethanesulfonate, and the tested current density is 10mA/cm2The half cell exhibited a lower nucleation overpotential (28.6 mV).
The cycle performance of the 3D printed zinc metal cathode obtained in example 1 was characterized in a symmetrical cell format, the electrolyte was 1M zinc trifluoromethanesulfonate, and the current density tested was 1mA/cm2Capacity of 1mAh/cm2The symmetrical battery shows better cycle life, the cycle life reaches 600 hours, and the voltage hysteresis is less than 20 mV.
The nucleation overpotential of the three-dimensional current collector obtained in example 2 was characterized in the form of a half-cell, the working electrode was a 16mm diameter three-dimensional current collector, the counter electrode was a lithium sheet of the same size, the electrolyte was 1M lithium bis (trifluoromethanesulfonic acid) imide, and the current density tested was 10mA/cm2The half cell exhibited a very low nucleation overpotential (12.8 mV).
The cycling performance of the 3D printed lithium metal negative electrode obtained in example 2 was characterized in the form of a symmetrical cell with 1M lithium bistrifluoromethylsulfonimide electrolyte and a current density of 1mA/cm2Capacity of 1mAh/cm2The symmetrical cell shows good cycle life, the cycle life reaches 1000 hours, and the voltage hysteresis is 82 mV.
Using half-cellsThe nucleation overpotential of the three-dimensional current collector obtained in example 3 was characterized in the form of a working electrode, a counter electrode, a sodium sheet with the same size, an electrolyte, 1M zinc trifluoromethanesulfonate, and a current density of 10mA/cm for the test2The half cell exhibited a very low nucleation overpotential (12.0 mV).
The cycle performance of the 3D printed zinc metal cathode obtained in example 3 was characterized in the form of a symmetrical cell, the electrolyte was 1M zinc trifluoromethanesulfonate, and the current density tested was 1mA/cm2Capacity of 1mAh/cm2The symmetric cell showed good cycle life, up to 630 hours, with a voltage hysteresis of 43 mV.
The cycling performance of the 3D printed sodium metal negative electrode obtained in example 3 was characterized in the form of a symmetrical cell with 1M sodium hexafluorophosphate electrolyte and a current density of 1mA/cm as measured2Capacity of 1mAh/cm2The symmetrical cell shows good cycle life, which reaches 1000 hours, and the voltage hysteresis is 25 mV.
While the present invention has been described in detail with reference to the embodiments, it should not be construed as limited to the scope of the patent. Various modifications and changes may be made by those skilled in the art without inventive work within the scope of the appended claims.
Claims (10)
1. A preparation method of an ion field/electric field controllable three-dimensional metal cathode is characterized by comprising the following steps:
(1) configuring 3D printing ink: adding a metal-philic substance, a viscous agent, a conductive agent and/or an active substance into a solvent, and regulating the proportion of each component to obtain 3D printing ink with different compositions;
(2) preparing a 3D printing three-dimensional metal cathode: and printing the 3D printing ink with different compositions into a three-dimensional current collector in a layer-by-layer superposed 3D printing mode, and performing post-treatment to obtain the three-dimensional current collector.
2. The production method according to claim 1, characterized in that: the mass ratio of the metal-philic substance, the viscous agent, the conductive agent and the active substance in the 3D printing ink is 10: 1-10: 0-10.
3. The production method according to claim 1 or 2, characterized in that: the metal-philic substance is at least one of gold, silver, copper, nickel, tin, titanium, copper-zinc alloy, copper-tin alloy, Mxene, graphene, carbon nano tube, titanium dioxide, manganese dioxide, aluminum oxide, copper oxide, cobalt oxide, tin oxide, zinc sulfide, zinc selenide, zinc oxide and polyacrylamide.
4. The production method according to claim 1 or 2, characterized in that: the thickening agent is at least one of bacterial cellulose, cotton cellulose, wood pulp cellulose, polyvinylidene fluoride, polyvinyl alcohol, gas-phase silicon dioxide, sodium alginate, potassium alginate, sodium carboxymethylcellulose, polymethacrylate, polyvinyl acetal and styrene butadiene latex.
5. The production method according to claim 1 or 2, characterized in that: the conductive agent is at least one of gold, silver, copper, nickel, tin, Mxene, graphene, carbon nano tube, carbon fiber and conductive carbon black.
6. The production method according to claim 1 or 2, characterized in that: the active material is at least one of lithium, sodium, magnesium, aluminum, potassium and zinc metals or corresponding metal oxides, metal sulfides, metal carbides or metal phosphides thereof.
7. The production method according to claim 1 or 2, characterized in that: the solvent is at least one of deionized water, ethyl acetate, N-methylpyrrolidone, acetone, dimethyl sulfoxide, acetonitrile, cyclohexane, carbon tetrachloride, N-dimethylacetamide, N-dimethylformamide and tetrahydrofuran.
8. The production method according to claim 1 or 2, characterized in that: the 3D printing method is a direct ink writing method, the diameter of a printing needle head is 100-700 mu m, and the distance between printed silk strips is 100-700 mu m.
9. The production method according to claim 1 or 2, characterized in that: the post-treatment comprises drying and loading of metal; the drying mode comprises heat conduction drying, convection heat conduction drying, vacuum drying, normal pressure drying, freeze drying, flash evaporation drying, microwave heating drying and infrared radiation drying; the metal loading mode comprises electrodeposition, fused deposition and redox deposition.
10. The ion field/electric field controllable three-dimensional metal cathode prepared by the preparation method of any one of claims 1 to 9.
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