CN111697236B - Three-dimensional current collector with multi-level structure for protecting lithium metal negative electrode and preparation method thereof - Google Patents
Three-dimensional current collector with multi-level structure for protecting lithium metal negative electrode and preparation method thereof Download PDFInfo
- Publication number
- CN111697236B CN111697236B CN202010367985.7A CN202010367985A CN111697236B CN 111697236 B CN111697236 B CN 111697236B CN 202010367985 A CN202010367985 A CN 202010367985A CN 111697236 B CN111697236 B CN 111697236B
- Authority
- CN
- China
- Prior art keywords
- current collector
- dimensional current
- lithium
- spinning
- pan
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/43—Acrylonitrile series
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Nanotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Textile Engineering (AREA)
- General Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention belongs to the technical field of battery current collectors, and particularly relates to a three-dimensional current collector with a multi-level structure and applied to protection of a lithium metal negative electrode and a preparation method thereof. The synthesis raw materials of the three-dimensional current collector comprise polyacrylonitrile and 2-methylimidazole, the 2-methylimidazole is uniformly distributed in three-dimensional self-supporting spinning cloth prepared by electrostatic spinning by using an electrostatic spinning method, ZIF-8 grows in situ in the spinning cloth, so that the derived three-dimensional current collector PNCF @ ZnO with a hierarchical pore structure is obtained by carbonization, zinc oxide nanoparticles are uniformly distributed on a nano sheet of a honeycomb carbon material, the abundant and uniformly distributed zinc oxide nanoparticles provide good nucleation sites for lithium metal and cooperate with the hierarchical pore structure, so that a stable place is provided for deposition and stripping of the metal lithium, and the zinc oxide nanoparticles are used as the three-dimensional current collector of the metal lithium, so that the formation of lithium dendrites in the recycling process of the metal lithium cathode can be effectively inhibited, and the lithium cathode is protected.
Description
Technical Field
The invention belongs to the technical field of battery current collectors, and particularly relates to a three-dimensional current collector with a multi-level structure and applied to protection of a lithium metal negative electrode and a preparation method thereof.
Background
With the rapid development of economic society, people have increasingly severe dependence on energy and are eager for high-density energy storage equipment, which prompts the research and development of the next-generation secondary energy storage battery. The lithium metal battery taking the lithium metal sheet as the negative electrode is an ideal candidate scheme of the next generation high-density energy storage battery by virtue of excellent theoretical specific capacity (3860 mAh/g) and lower redox electromotive force (-3.04V). However, in practical applications, lithium metal batteries also have their own drawbacks such as low coulombic efficiency, short service life, and safety problems. The conventional lithium metal battery negative electrode can generate a large amount of lithium dendrites in the oxidation-reduction reaction process, and the lithium dendrites can continuously grow and penetrate through a diaphragm along with the increase of the working time, so that the safety problem is caused. Meanwhile, a large amount of 'dead lithium' is formed in the lithium metal negative electrode in the process of repeated lithium intercalation/deintercalation, and the 'dead lithium' causes the electrode to expand in volume indefinitely, so that the coulomb efficiency of the battery is low.
In response to the above problems with lithium metal batteries, researchers have made extensive efforts to solve the problems of lithium dendrites and negative electrode volume expansion. Among them, development of a novel electrolyte is considered as an effective method; researchers also propose that the cycle performance of the battery can be improved by adding a high polymer material layer between the electrolyte and the lithium metal negative electrode to form an artificial SEI film; the use of polymer gel electrolytes or all-solid electrolytes in batteries is also a good choice. Compared with electrolyte, the solid electrolyte has better mechanical property and thermodynamic stability, so the solid or gel electrolyte can effectively inhibit the generation of lithium dendrite and improve the long cycle performance of the battery.
However, the above-mentioned methods only solve the problem of lithium dendrites of the lithium metal negative electrode on one side, and are less helpful to solve the problem of the large volume expansion of the lithium metal negative electrode. The importance of the SEI film to the battery performance is self-evident since both electron charge transfer and redox reaction of lithium ions occur on the SEI film during battery cycling. However, the lithium metal negative electrode is "non-dominant" to cause huge volume expansion, so that an SEI film formed on the surface of the negative electrode is cracked to expose fresh lithium metal, and the lithium reacts with an electrolyte to form a new SEI film, so that the consumption of the lithium and the waste of the electrolyte are caused, and the coulombic efficiency and the long-cycle stability of the battery are negatively influenced. Therefore, three-dimensional cathode materials represented by foamed nickel and foamed copper are widely concerned, the materials have larger contact surfaces with electrolyte, richer sites are provided for lithium ion deposition, the volume expansion is effectively relieved by the reserved space in the materials, and the local current density is reduced by the mutually cross-linked conductive network. Although some success has been achieved, none of these methods inhibit lithium dendrite growth from a microscopic perspective.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a three-dimensional current collector with a multi-level structure for protecting a lithium metal negative electrode and a method for preparing the same, wherein the three-dimensional current collector is formed by an electrospinning method, and can effectively inhibit the formation of lithium dendrites.
The technical content of the invention is as follows:
the invention provides a three-dimensional current collector with a multi-level structure, which is applied to protecting a lithium metal cathode, wherein the three-dimensional current collector is prepared by using an electrostatic spinning technology and high-temperature carbonization, and the synthetic raw materials of the three-dimensional current collector comprise polyacrylonitrile, 2-methylimidazole and a zinc salt solution;
the three-dimensional current collector is characterized in that zinc oxide nanoparticles are distributed on a nano sheet of a honeycomb carbon material, the chemical formula of the three-dimensional current collector is named as PNCF @ ZnO, 2-methylimidazole is uniformly distributed in three-dimensional self-supporting spinning cloth prepared by electrostatic spinning by using an electrostatic spinning method, ZIF-8 grows in situ in the spinning cloth, and the three-dimensional current collector PNCF @ ZnO with a derived hierarchical pore structure is obtained by carbonization. The final form of lithium dendrites depends greatly on the distribution of the initial lithium crystal nuclei, and according to this theory, the three-dimensional structure negative electrode is compounded with a lithium-inducing nucleation material to uniformly distribute the lithium crystal nuclei.
The invention also provides a preparation method of the three-dimensional current collector with the multilevel structure, which is applied to protecting the lithium metal negative electrode, and the preparation method comprises the following steps:
1) dissolving polyacrylonitrile in an organic solvent, adding 2-methylimidazole, stirring for reaction, and inducing ZIF-8 to grow in situ in the spinning fiber;
2) carrying out electrostatic spinning on the reactant obtained in the step 1) to form spinning cloth PAN/2-IMZ, so that the 2-methylimidazole ligand is wrapped in polyacrylonitrile fibers;
3) soaking the spinning cloth PAN/2-IMZ in a zinc salt solution to enable zinc ions in the zinc salt solution to react with 2-methylimidazole in the spinning cloth, growing ZIF-8 nano-particles on fibers in the spinning cloth in situ, and drying to obtain PAN/ZIF-8;
4) placing PAN/ZIF-8 in the air for heating and low-temperature preoxidation to preoxidize polyacrylonitrile spinning; and then heating the polyacrylonitrile fiber in an inert atmosphere, and carbonizing the polyacrylonitrile fiber at high temperature to obtain carbon fiber, wherein ZIF-8 particles on the surface of the fiber are carbonized into a compound of zinc oxide and carbon, so that the three-dimensional current collector PNCF @ ZnO is finally obtained.
The mixing mass ratio of the polyacrylonitrile to the 2-methylimidazole in the step 1) is 4: (1-4);
step 1) the organic solvent comprises N, N-dimethylformamide;
the electrostatic spinning operation conditions in the step 2) comprise that the voltage environment is 7-10 KV, the spinning distance is 12-18 cm, and the flow rate is adjusted to 0.5-1 mL/h;
the zinc salt solution in the step 3) comprises a zinc acetate methanol solution, which is prepared by dissolving zinc acetate in a methanol solution, and the concentration of the zinc acetate is 5-15 moL/L;
and 4) the heating rate of the temperature rise is 1-5 ℃/min, the low-temperature preoxidation temperature is 200-240 ℃, and the high-temperature carbonization temperature is 580-620 ℃.
The invention has the following beneficial effects:
according to the three-dimensional current collector PNCF @ ZnO, 2-methylimidazole is uniformly distributed in three-dimensional self-supporting spinning cloth prepared by electrostatic spinning by using an electrostatic spinning technology, ZIF-8 grows in situ in the spinning cloth, so that the derived three-dimensional current collector PNCF @ ZnO with a multi-stage pore structure is obtained by carbonization, the special honeycomb structure is uniformly distributed on carbon fibers, zinc oxide nanoparticles are uniformly distributed on nano sheets of a honeycomb carbon material, the abundant and uniformly distributed zinc oxide nanoparticles provide good nucleation sites for lithium metal and cooperate with the multi-stage pore structure, a stable place is provided for deposition and stripping of the metal lithium, and the three-dimensional current collector is used as the three-dimensional current collector of the metal lithium, so that the formation of lithium dendrites in the recycling process of the metal lithium cathode can be effectively inhibited, and the lithium cathode is protected.
Drawings
FIG. 1 is a scanning electron microscope image of a spinning cloth PAN/2-IMZ;
FIG. 2 is a scanning electron microscope image of the as-spun fabric PAN/ZIF-8 after ZIF-8 growth;
FIG. 3 is a scanning electron microscope image of a three-dimensional current collector PNCF @ ZnO;
FIG. 4 shows the current density of 0.5 mA/cm for lithium-current collector half cells assembled with different current collectors2The capacity is 0.5 mAh/cm2Coulombic efficiency map for the lower cycle;
FIG. 5 is a scanning electron micrograph of lithium metal deposited on a copper foil;
FIG. 6 is a scanning electron micrograph of lithium metal deposited on carbon fibers;
FIG. 7 is a scanning electron microscope image of lithium metal deposited on a three-dimensional current collector PNCF @ ZnO with a multi-level structure;
fig. 8 is a cycle performance diagram of the assembled lithium iron phosphate full cell after pre-lithiation.
Detailed Description
The present invention is described in further detail in the following description of specific embodiments and the accompanying drawings, it is to be understood that these embodiments are merely illustrative of the present invention and are not intended to limit the scope of the invention, which is defined by the appended claims, and modifications thereof by those skilled in the art after reading this disclosure that are equivalent to the above described embodiments.
All the raw materials and reagents of the invention are conventional market raw materials and reagents unless otherwise specified.
Example 1
The preparation method of the three-dimensional current collector with the multilevel structure, which is applied to the protection of the lithium metal negative electrode, comprises the following steps:
1) dissolving 2g of polyacrylonitrile in 18 mLN, N-dimethylformamide, stirring at normal temperature for 1 hour, then adding 0.5 g of 2-methylimidazole, and continuing stirring for 24 hours to react;
2) performing electrostatic spinning on the reactant obtained in the step 1), assembling the reactant in an electrostatic spinning machine, adjusting the spinning voltage to 8 KV, the spinning receiving distance to 15 cm, adjusting the flow to 0.8 mL/h, and performing electrostatic spinning for 2h to obtain spinning cloth PAN/2-IMZ, wherein as shown in a scanning electron microscope image of the spinning cloth PAN/2-IMZ in figure 1, the spinning cloth PAN/2-IMZ is excellent in spinning appearance, uniform in appearance and is a fiber with the diameter of hundreds of nanometers;
3) preparing a zinc acetate methanol solution with the volume of 20 mL and the concentration of 5 mol/L, soaking the spinning cloth PAN/2-IMZ in the zinc acetate methanol solution for 0.5 h, taking out the soaked spinning cloth, cleaning the spinning cloth with methanol, and then drying the spinning cloth at the temperature of 60 ℃ in vacuum for 24h to obtain PAN/ZIF-8, wherein as shown in a scanning electron microscope image of the spinning cloth PAN/ZIF-8 with the ZIF-8 growing, the ZIF-8 can be seen to grow on the fiber uniformly;
4) and (3) placing the PAN/ZIF-8 in the air, gradually heating to 240 ℃ in a muffle furnace at a heating rate of 1 ℃/min, carrying out low-temperature preoxidation for 2h, then gradually heating to 600 ℃ at a heating rate of 1 ℃/min in an argon atmosphere, and carrying out high-temperature carbonization for 1h to obtain the three-dimensional current collector PNCF @ ZnO, wherein a scanning electron microscope image of the three-dimensional current collector PNCF @ ZnO is shown in figure 3, so that the three-dimensional current collector with a multi-stage structure is formed. The zinc oxide nano-particles are distributed on the nano-sheets of the honeycomb carbon material, and the honeycomb carbon nano-sheets are uniformly distributed on the surface of the hollow carbon fiber.
Example 2
1) Dissolving 2g of polyacrylonitrile in 18 mLN, N-dimethylformamide, stirring at normal temperature for 1 hour, then adding 1 g of 2-methylimidazole, and continuing stirring for 24 hours to react;
2) performing electrostatic spinning on the reactant obtained in the step 1), assembling the reactant in an electrostatic spinning machine, adjusting the spinning voltage to be 7 KV, the spinning receiving distance to be 12 cm, adjusting the flow to be 0.5 mL/h, and performing electrostatic spinning for 2h to obtain spinning cloth PAN/2-IMZ;
3) preparing a zinc acetate methanol solution with the volume of 20 mL and the concentration of 10 mol/L, soaking the spinning cloth PAN/2-IMZ in the zinc acetate methanol solution for 1h, taking out the soaked spinning cloth, cleaning the spinning cloth with methanol, and then drying the spinning cloth at 60 ℃ in vacuum for 24h to obtain PAN/ZIF-8;
4) and (2) placing the PAN/ZIF-8 in the air, gradually heating to 200 ℃ in a muffle furnace at a heating rate of 2 ℃/min, carrying out low-temperature pre-oxidation for 2h, then gradually heating to 580 ℃ at a heating rate of 2 ℃/min in an argon atmosphere, and carrying out high-temperature carbonization for 1h to obtain the three-dimensional current collector PNCF @ ZnO.
Example 3
1) Dissolving 2g of polyacrylonitrile in 18 mLN, N-dimethylformamide, stirring at normal temperature for 1 hour, then adding 2g of 2-methylimidazole, and continuing stirring for 24 hours to react;
2) performing electrostatic spinning on the reactant obtained in the step 1), assembling the reactant in an electrostatic spinning machine, adjusting the spinning voltage to 9 KV, the spinning receiving distance to 14 cm, adjusting the flow to 0.7 mL/h, and performing electrostatic spinning for 2h to obtain spinning cloth PAN/2-IMZ;
3) preparing a 15 mol/L zinc acetate methanol solution with the volume of 20 mL, soaking the spinning cloth PAN/2-IMZ in the zinc acetate methanol solution for 1h, taking out the soaked spinning cloth, cleaning the spinning cloth with methanol, and then drying the spinning cloth at 60 ℃ in vacuum for 24h to obtain PAN/ZIF-8;
4) and (2) placing the PAN/ZIF-8 in the air, gradually heating to 220 ℃ in a muffle furnace at a heating rate of 2 ℃/min, carrying out low-temperature pre-oxidation for 2h, then gradually heating to 600 ℃ at a heating rate of 4 ℃/min in an argon atmosphere, and carrying out high-temperature carbonization for 1h to obtain the three-dimensional current collector PNCF @ ZnO.
Example 4
1) Dissolving 2g of polyacrylonitrile in 18 mLN, N-dimethylformamide, stirring at normal temperature for 1 hour, then adding 2g of 2-methylimidazole, and continuing stirring for 24 hours to react;
2) performing electrostatic spinning on the reactant obtained in the step 1), assembling the reactant in an electrostatic spinning machine, adjusting the spinning voltage to 10KV, the spinning receiving distance to 18cm, adjusting the flow to 1 mL/h, and performing electrostatic spinning for 2h to obtain spinning cloth PAN/2-IMZ;
3) preparing a 15 mol/L zinc acetate methanol solution with the volume of 20 mL, soaking the spinning cloth PAN/2-IMZ in the zinc acetate methanol solution for 1h, taking out the soaked spinning cloth, cleaning the spinning cloth with methanol, and then drying the spinning cloth at 60 ℃ in vacuum for 24h to obtain PAN/ZIF-8;
4) and (2) placing the PAN/ZIF-8 in the air, gradually heating to 240 ℃ in a muffle furnace at a heating rate of 5 ℃/min, carrying out low-temperature pre-oxidation for 2h, then gradually heating to 620 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, and carrying out high-temperature carbonization for 1h to obtain the three-dimensional current collector PNCF @ ZnO.
The three-dimensional current collector PNCF @ ZnO prepared in the embodiment 1 is used for testing the electrochemical performance of a lithium-current collector half cell, and the electrochemical performance of an assembled lithium iron phosphate full cell after pre-lithiation is tested:
1. lithium-current collector half-cell: cutting a three-dimensional current collector PNCF @ ZnO into pole pieces with the diameter of 12 mm, assembling a lithium-current collector CR2032 type button half cell (Ar% > 99.99%, O%) in a glove box by taking a lithium piece as a counter electrode, taking a mixture (volume ratio is 1: 1) of 1mol/L bis (trifluoromethanesulfonyl) imide lithium, DOL and DME as electrolyte and taking a diaphragm as a common PP diaphragm2＜0.1 ppm，H2O is less than 0.1 ppm), the stability of the fiber under different current densities and different deposition capacities is tested by using a constant-current charging and discharging method, for comparison, a blank copper foil or a blank carbon fiber carbonized by spinning cloth is used as a current collector for test comparison, and the result analysis is as follows:
as shown in fig. 4, when a common copper foil or carbon fiber is used as a current collector, the cycle life of lithium metal deposition/stripping is only less than 100 hours or 200 hours, which is far shorter than that of the PNCF @ ZnO current collector material prepared by the invention. The PNCF @ ZnO current collector material prepared in example 1 can be stably cycled for more than 400 hours. The Coulomb efficiency of the PNCF @ ZnO current collector material prepared by the invention can be maintained at higher Coulomb efficiency when metal lithium is deposited/stripped, and 96.47% Coulomb efficiency is still obtained even after the metal lithium is circulated for 400 hours;
in order to further illustrate that the PNCF @ ZnO material can induce uniform deposition of metal lithium as a three-dimensional current collector, a lithium-current collector half cell is disassembled after electrochemical circulation, and the deposition condition of the metal lithium on the current collector is tested by a scanning electron microscope:
as shown in fig. 5, the lithium metal deposited on the general copper foil generates a large amount of lithium dendrite, dead lithium, and the deposition of lithium is very rough;
as shown in fig. 6, when the carbon fiber is used as a current collector, metal lithium can be deposited only in the pores between the fibers, and the metal lithium deposition on the carbon fiber is also uneven;
as shown in fig. 7, when the PNCF @ ZnO prepared by the present invention is used as a current collector, metal lithium can be deposited on the whole current collector very uniformly and in a multi-stage structure, and the generation of lithium dendrites is effectively inhibited.
2. Assembling the lithium iron phosphate full battery after pre-lithiation: will be commercial LiFePO4Mixing the carbon black, the conductive agent and the PVDF as the binder according to the amount of 150 mg, 18.7 mg and 18.7 mg, preparing the mixture into slurry by using 0.4 mLN-methyl pyrrolidone, uniformly coating the slurry on an aluminum foil, slightly drying the slurry, transferring the slurry to a vacuum drying oven at 55 ℃ for drying, and cutting the slurry into pole pieces with the diameter of 12 mm. And pre-lithiation is respectively carried out on the carbon fiber carbonized by the three-dimensional current collector PNCF @ ZnO, the copper foil and the blank spinning cloth. In a glove box in an argon atmosphere, lithium iron phosphate is used as a positive electrode, a pre-lithiated pole piece is used as a negative electrode, a diaphragm is a PP diaphragm, a mixture (volume ratio is 1: 1) of 1mol/L bis (trifluoromethanesulfonyl) imide lithium, DOL and DME is used as electrolyte, a CR2032 type button cell is assembled, the test voltage range is 2-4.2V, and the test result is as follows:
in order to evaluate the effect of the three-dimensional current collector PNCF @ ZnO in the full cell, after the same amount of metal lithium is deposited on different current collectors, the metal lithium is used as a negative electrode, lithium iron phosphate is used as a positive electrode to assemble the full cell, and the cycle performance of the cell is tested:
as shown in fig. 8, the capacity of the battery assembled by using copper foil or blank carbon fiber as the current collector of lithium metal is less than 80 mAh/g, which is much smaller than that of the battery assembled by using a three-dimensional current collector PNCF @ ZnO;
the battery assembled after the pre-lithiation of the three-dimensional current collector PNCF @ ZnO prepared by the invention has the specific capacity as high as 133.8mAh/g, and can be stably circulated for 100 circles, and the capacity retention rate is 91.7% after 100 circles.
The above tests fully demonstrate that the three-dimensional current collector PNCF @ ZnO for protecting a lithium metal negative electrode of the present invention has excellent effects.
Claims (6)
1. A preparation method of a three-dimensional current collector with a multilevel structure for protecting a lithium metal negative electrode is characterized by comprising the following steps:
1) dissolving polyacrylonitrile in an organic solvent, adding 2-methylimidazole, and stirring for reaction;
2) carrying out electrostatic spinning on the reactant obtained in the step 1) to form spinning cloth PAN/2-IMZ;
3) soaking the spinning cloth PAN/2-IMZ in a zinc salt solution, and then drying to obtain PAN/ZIF-8;
4) placing PAN/ZIF-8 in the air for heating and low-temperature pre-oxidation, then placing the PAN/ZIF-8 in an inert atmosphere for heating and high-temperature carbonization to obtain a three-dimensional current collector PNCF @ ZnO;
the three-dimensional current collector has a structure that zinc oxide nano particles are distributed on nano sheets of a honeycomb carbon material, and the honeycomb carbon nano sheets are uniformly distributed on the surface of the hollow carbon fiber.
2. The method for preparing the three-dimensional current collector with the multilevel structure according to claim 1, wherein the mixing mass ratio of the polyacrylonitrile and the 2-methylimidazole in the step 1) is 4: (1-4).
3. The method for preparing a three-dimensional current collector having a multilevel structure according to claim 1, wherein the organic solvent of step 1) comprises N, N-dimethylformamide.
4. The method for preparing the three-dimensional current collector with the multilevel structure according to claim 1, wherein the electrostatic spinning in the step 2) is performed under the conditions of a voltage environment of 7-10 KV, a spinning distance of 12-18 cm, and a flow rate of 0.5-1 mL/h.
5. The method for preparing the three-dimensional current collector with the multilevel structure as claimed in claim 1, wherein the zinc salt solution in step 3) comprises a methanol solution of zinc acetate, and the concentration of the methanol solution of zinc acetate is 5-15 moL/L.
6. The method for preparing the three-dimensional current collector with the multilevel structure according to claim 1, wherein the temperature rise rate of the temperature rise in the step 4) is 1-5 ℃/min, the temperature of the low-temperature pre-oxidation is 200-240 ℃, and the temperature of the high-temperature carbonization is 580-620 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010367985.7A CN111697236B (en) | 2020-04-30 | 2020-04-30 | Three-dimensional current collector with multi-level structure for protecting lithium metal negative electrode and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010367985.7A CN111697236B (en) | 2020-04-30 | 2020-04-30 | Three-dimensional current collector with multi-level structure for protecting lithium metal negative electrode and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111697236A CN111697236A (en) | 2020-09-22 |
| CN111697236B true CN111697236B (en) | 2021-12-14 |
Family
ID=72476899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010367985.7A Active CN111697236B (en) | 2020-04-30 | 2020-04-30 | Three-dimensional current collector with multi-level structure for protecting lithium metal negative electrode and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111697236B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114512674A (en) * | 2020-11-16 | 2022-05-17 | 比亚迪股份有限公司 | Negative pole piece and metal lithium battery |
| CN112593408A (en) * | 2020-11-27 | 2021-04-02 | 湖北省纤维检验局孝感分局(湖北省纤维制品检测中心孝感分中心) | Anti-ultraviolet non-woven film and preparation method thereof |
| CN112615004A (en) * | 2020-12-16 | 2021-04-06 | 西安交通大学 | Cellulose @ graphene composite carbon aerogel and preparation method and application thereof |
| CN112886019B (en) * | 2021-02-03 | 2022-08-02 | 山东大学 | High-stability three-dimensional MXene-COF-Li composite metal lithium negative electrode material and preparation method and application thereof |
| CN113036138B (en) * | 2021-03-09 | 2022-10-14 | 电子科技大学 | Preparation method and application of three-dimensional porous lithium-philic composite material |
| CN113130881A (en) * | 2021-04-12 | 2021-07-16 | 肇庆市华师大光电产业研究院 | Preparation method of lithium-sulfur battery cathode material |
| CN114068872A (en) * | 2021-10-13 | 2022-02-18 | 江苏恒力化纤股份有限公司 | Polymer nanofiber metal lithium composite negative electrode with double lithium affinity and preparation method thereof |
| CN114744209A (en) * | 2022-04-12 | 2022-07-12 | 华南师范大学 | Application of MOFs-based composite carbon nanofiber current collector in preparation of lithium battery without lithium cathode |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108767247A (en) * | 2018-07-02 | 2018-11-06 | 南京工业大学 | Preparation method and application of carbon-based metal organic framework MOF compound derivative material |
| CN109065854A (en) * | 2018-07-09 | 2018-12-21 | 华南师范大学 | A kind of preparation method of nano-carbon coated zinc oxide composite and the preparation method of electrode |
| CN109505035A (en) * | 2018-10-30 | 2019-03-22 | 肇庆市华师大光电产业研究院 | A kind of preparation method of lithium-sulfur cell diaphragm material |
| CN110078053A (en) * | 2019-05-16 | 2019-08-02 | 华南师范大学 | A kind of porous carbon materials and its preparation method and application applied to battery diaphragm coating |
| CN110137461A (en) * | 2019-05-10 | 2019-08-16 | 陕西科技大学 | Lithium ion battery cobalt/cobalt oxide carbon nano-fiber flexible electrode material and preparation method thereof derived from MOF |
| CN110295498A (en) * | 2019-04-15 | 2019-10-01 | 武汉理工大学 | The thin polymer film and its preparation method and application of metal organic frame modification |
-
2020
- 2020-04-30 CN CN202010367985.7A patent/CN111697236B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108767247A (en) * | 2018-07-02 | 2018-11-06 | 南京工业大学 | Preparation method and application of carbon-based metal organic framework MOF compound derivative material |
| CN109065854A (en) * | 2018-07-09 | 2018-12-21 | 华南师范大学 | A kind of preparation method of nano-carbon coated zinc oxide composite and the preparation method of electrode |
| CN109505035A (en) * | 2018-10-30 | 2019-03-22 | 肇庆市华师大光电产业研究院 | A kind of preparation method of lithium-sulfur cell diaphragm material |
| CN110295498A (en) * | 2019-04-15 | 2019-10-01 | 武汉理工大学 | The thin polymer film and its preparation method and application of metal organic frame modification |
| CN110137461A (en) * | 2019-05-10 | 2019-08-16 | 陕西科技大学 | Lithium ion battery cobalt/cobalt oxide carbon nano-fiber flexible electrode material and preparation method thereof derived from MOF |
| CN110078053A (en) * | 2019-05-16 | 2019-08-02 | 华南师范大学 | A kind of porous carbon materials and its preparation method and application applied to battery diaphragm coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111697236A (en) | 2020-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111697236B (en) | Three-dimensional current collector with multi-level structure for protecting lithium metal negative electrode and preparation method thereof | |
| CN110690420B (en) | Composite material cathode, battery and preparation method thereof | |
| CN108520985A (en) | Method for prolonging cycle life of zinc battery and application thereof | |
| CN108862235B (en) | Fibrous hollow hard carbon material for sodium ion battery cathode and preparation method thereof | |
| CN110010895B (en) | Carbon fiber loaded magnesium oxide particle cross-linked nanosheet array composite material and preparation method and application thereof | |
| CN112018361B (en) | Carbon cloth loaded carbon coated cobalt selenide nanosheet battery cathode material and preparation thereof | |
| CN114220947B (en) | Lithium metal battery negative electrode, current collector, preparation method of current collector and battery | |
| CN113690397B (en) | Zinc cathode pole piece and preparation method and application thereof | |
| CN113363465A (en) | Preparation method of lithium/potassium ion battery negative electrode material | |
| CN112750983A (en) | Three-dimensional composite lithium metal negative electrode, preparation method thereof and lithium battery | |
| CN110165179B (en) | Lithium battery negative electrode material, preparation method thereof and lithium battery containing negative electrode material | |
| CN115679380A (en) | Preparation method and application of crystal face oriented metal zinc | |
| CN113903891B (en) | Preparation method and application of amorphous carbon-based composite anode material containing metalloid lithium | |
| CN114203976A (en) | Mixed solution capable of improving stability of metal lithium cathode, preparation method and application | |
| CN113036097B (en) | Sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material and preparation method thereof | |
| CN111900373B (en) | Preparation method of lithium dendrite-resistant lithium metal battery cathode side separator material | |
| CN110592807B (en) | Thin film material for inhibiting growth of lithium dendrite and preparation method thereof | |
| CN116565216A (en) | Three-dimensional current collector for zinc ion battery, preparation and application thereof | |
| CN110649227A (en) | Three-dimensional composite potassium metal cathode and preparation method and application thereof | |
| CN116014146A (en) | Self-supporting biomass carbon current collector, composite current collector and application | |
| CN114583137A (en) | Method for modifying carbon surface by doping sulfur with phosphorus and application thereof | |
| CN112234194A (en) | Iodine modified MXene material and preparation method and application thereof | |
| CN113410451B (en) | Lithium metal negative electrode flexible protection material and preparation method thereof | |
| CN114497563B (en) | Zinc ion battery anode material constructed based on hot melting method, preparation and application thereof | |
| CN114744209A (en) | Application of MOFs-based composite carbon nanofiber current collector in preparation of lithium battery without lithium cathode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |